RAPRA REVIEW REPORTS - polymerjournals.com · RAPRA REVIEW REPORTS A Rapra Review Report comprises three sections, as follows: 1. A commissioned expert review, discussing a key topic

RAPRA REVIEW REPORTS

A Rapra Review Report comprises three sections, as follows:

1. A commissioned expert review, discussing a key topic of current interest, and referring to the References andAbstracts section. Reference numbers in brackets refer to item numbers from the References and Abstractssection. Where it has been necessary for completeness to cite sources outside the scope of the Rapra Abstractsdatabase, these are listed at the end of the review, and cited in the text as a.1, a.2, etc.

2. A comprehensive References and Abstracts section, resulting from a search of the Rapra Abstracts database.The format of the abstracts is outlined in the sample record below.

3. An index to the References and Abstracts section, derived from the indexing terms which are added to theabstracts records on the database to aid retrieval.

Item 1Macromolecules33, No.6, 21st March 2000, p.2171-83EFFECT OF THERMAL HISTORY ON THE RHEOLOGICALBEHAVIOR OF THERMOPLASTIC POLYURETHANESPil Joong Yoon; Chang Dae HanAkron,University

The effect of thermal history on the rheological behaviour of ester- andether-based commercial thermoplastic PUs (Estane 5701, 5707 and 5714from B.F.Goodrich) was investigated. It was found that the injectionmoulding temp. used for specimen preparation had a marked effect on thevariations of dynamic storage and loss moduli of specimens with timeobserved during isothermal annealing. Analysis of FTIR spectra indicatedthat variations in hydrogen bonding with time during isothermal annealingvery much resembled variations of dynamic storage modulus with timeduring isothermal annealing. Isochronal dynamic temp. sweep experimentsindicated that the thermoplastic PUs exhibited a hysteresis effect in theheating and cooling processes. It was concluded that the microphaseseparation transition or order-disorder transition in thermoplastic PUs couldnot be determined from the isochronal dynamic temp. sweep experiment.The plots of log dynamic storage modulus versus log loss modulus variedwith temp. over the entire range of temps. (110-190C) investigated. 57 refs.

GOODRICH B.F.USA

Accession no.771897

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Previous Titles Still AvailableVolume 1Report 3 Advanced Composites, D.K. Thomas, RAE, Farnborough.

Report 4 Liquid Crystal Polymers, M.K. Cox, ICI, Wilton.

Report 5 CAD/CAM in the Polymer Industry, N.W. Sandlandand M.J. Sebborn, Cambridge Applied Technology.

Report 8 Engineering Thermoplastics, I.T. Barrie, Consultant.

Report 11 Communications Applications of Polymers,R. Spratling, British Telecom.

Report 12 Process Control in the Plastics Industry,R.F. Evans, Engelmann & Buckham Ancillaries.

Volume 2Report 13 Injection Moulding of Engineering Thermoplastics,

A.F. Whelan, London School of Polymer Technology.

Report 14 Polymers and Their Uses in the Sports and LeisureIndustries, A.L. Cox and R.P. Brown, RapraTechnology Ltd.

Report 15 Polyurethane, Materials, Processing and Applications,G. Woods, Consultant.

Report 16 Polyetheretherketone, D.J. Kemmish, ICI, Wilton.

Report 17 Extrusion, G.M. Gale, Rapra Technology Ltd.

Report 18 Agricultural and Horticultural Applications ofPolymers, J.C. Garnaud, International Committee forPlastics in Agriculture.

Report 19 Recycling and Disposal of Plastics Packaging,R.C. Fox, Plas/Tech Ltd.

Report 20 Pultrusion, L. Hollaway, University of Surrey.

Report 21 Materials Handling in the Polymer Industry,H. Hardy, Chronos Richardson Ltd.

Report 22 Electronics Applications of Polymers, M.T.Goosey,Plessey Research (Caswell) Ltd.

Report 23 Offshore Applications of Polymers, J.W.Brockbank,Avon Industrial Polymers Ltd.

Report 24 Recent Developments in Materials for FoodPackaging, R.A. Roberts, Pira Packaging Division.

Volume 3Report 25 Foams and Blowing Agents, J.M. Methven, Cellcom

Technology Associates.

Report 26 Polymers and Structural Composites in CivilEngineering, L. Hollaway, University of Surrey.

Report 27 Injection Moulding of Rubber, M.A. Wheelans,Consultant.

Report 28 Adhesives for Structural and EngineeringApplications, C. O’Reilly, Loctite (Ireland) Ltd.

Report 29 Polymers in Marine Applications, C.F.Britton,Corrosion Monitoring Consultancy.

Report 30 Non-destructive Testing of Polymers, W.N. Reynolds,National NDT Centre, Harwell.

Report 31 Silicone Rubbers, B.R. Trego and H.W.Winnan,Dow Corning Ltd.

Report 32 Fluoroelastomers - Properties and Applications,D. Cook and M. Lynn, 3M United Kingdom Plc and3M Belgium SA.

Report 33 Polyamides, R.S. Williams and T. Daniels,T & N Technology Ltd. and BIP Chemicals Ltd.

Report 34 Extrusion of Rubber, J.G.A. Lovegrove, NovaPetrochemicals Inc.

Report 35 Polymers in Household Electrical Goods, D.Alvey,Hotpoint Ltd.

Report 36 Developments in Additives to Meet Health andEnvironmental Concerns, M.J. Forrest, RapraTechnology Ltd.

Volume 4Report 37 Polymers in Aerospace Applications, W.W. Wright,

University of Surrey.

Report 39 Polymers in Chemically Resistant Applications,D. Cattell, Cattell Consultancy Services.

Report 41 Failure of Plastics, S. Turner, Queen Mary College.

Report 42 Polycarbonates, R. Pakull, U. Grigo, D. Freitag, BayerAG.

Report 43 Polymeric Materials from Renewable Resources,J.M. Methven, UMIST.

Report 44 Flammability and Flame Retardants in Plastics,J. Green, FMC Corp.

Report 45 Composites - Tooling and Component Processing,N.G. Brain, Tooltex.

Report 46 Quality Today in Polymer Processing, S.H. Coulson,J.A. Cousans, Exxon Chemical International Marketing.

Report 47 Chemical Analysis of Polymers, G. Lawson, LeicesterPolytechnic.

Volume 5Report 49 Blends and Alloys of Engineering Thermoplastics,

H.T. van de Grampel, General Electric Plastics BV.

Report 50 Automotive Applications of Polymers II,A.N.A. Elliott, Consultant.

Report 51 Biomedical Applications of Polymers, C.G. Gebelein,Youngstown State University / Florida Atlantic University.

Report 52 Polymer Supported Chemical Reactions, P. Hodge,University of Manchester.

Report 53 Weathering of Polymers, S.M. Halliwell, BuildingResearch Establishment.

Report 54 Health and Safety in the Rubber Industry, A.R. Nutt,Arnold Nutt & Co. and J. Wade.

Report 55 Computer Modelling of Polymer Processing,E. Andreassen, Å. Larsen and E.L. Hinrichsen, Senter forIndustriforskning, Norway.

Report 56 Plastics in High Temperature Applications,J. Maxwell, Consultant.

Report 57 Joining of Plastics, K.W. Allen, City University.

Report 58 Physical Testing of Rubber, R.P. Brown, RapraTechnology Ltd.

Report 59 Polyimides - Materials, Processing and Applications,A.J. Kirby, Du Pont (U.K.) Ltd.

Report 60 Physical Testing of Thermoplastics, S.W. Hawley,Rapra Technology Ltd.

Volume 6Report 61 Food Contact Polymeric Materials, J.A. Sidwell,

Rapra Technology Ltd.

Report 62 Coextrusion, D. Djordjevic, Klöckner ER-WE-PA GmbH.

Report 63 Conductive Polymers II, R.H. Friend, University ofCambridge, Cavendish Laboratory.

Report 64 Designing with Plastics, P.R. Lewis, The Open University.

Report 65 Decorating and Coating of Plastics, P.J. Robinson,International Automotive Design.

Report 66 Reinforced Thermoplastics - Composition, Processingand Applications, P.G. Kelleher, New Jersey PolymerExtension Center at Stevens Institute of Technology.

Report 67 Plastics in Thermal and Acoustic Building Insulation,V.L. Kefford, MRM Engineering Consultancy.

Report 68 Cure Assessment by Physical and ChemicalTechniques, B.G. Willoughby, Rapra Technology Ltd.

Report 69 Toxicity of Plastics and Rubber in Fire, P.J. Fardell,Building Research Establishment, Fire Research Station.

Report 70 Acrylonitrile-Butadiene-Styrene Polymers,M.E. Adams, D.J. Buckley, R.E. Colborn, W.P. Englandand D.N. Schissel, General Electric Corporate Researchand Development Center.

Report 71 Rotational Moulding, R.J. Crawford, The Queen’sUniversity of Belfast.

Report 72 Advances in Injection Moulding, C.A. Maier,Econology Ltd.

Volume 7

Report 73 Reactive Processing of Polymers, M.W.R. Brown,P.D. Coates and A.F. Johnson, IRC in Polymer Scienceand Technology, University of Bradford.

Report 74 Speciality Rubbers, J.A. Brydson.

Report 75 Plastics and the Environment, I. Boustead, BousteadConsulting Ltd.

Report 76 Polymeric Precursors for Ceramic Materials,R.C.P. Cubbon.

Report 77 Advances in Tyre Mechanics, R.A. Ridha, M. Theves,Goodyear Technical Center.

Report 78 PVC - Compounds, Processing and Applications,J.Leadbitter, J.A. Day, J.L. Ryan, Hydro Polymers Ltd.

Report 79 Rubber Compounding Ingredients - Need, Theoryand Innovation, Part I: Vulcanising Systems,Antidegradants and Particulate Fillers for GeneralPurpose Rubbers, C. Hepburn, University of Ulster.

Report 80 Anti-Corrosion Polymers: PEEK, PEKK and OtherPolyaryls, G. Pritchard, Kingston University.

Report 81 Thermoplastic Elastomers - Properties and Applications,J.A. Brydson.

Report 82 Advances in Blow Moulding Process Optimization,Andres Garcia-Rejon,Industrial Materials Institute,National Research Council Canada.

Report 83 Molecular Weight Characterisation of SyntheticPolymers, S.R. Holding and E. Meehan, RapraTechnology Ltd. and Polymer Laboratories Ltd.

Report 84 Rheology and its Role in Plastics Processing,P. Prentice, The Nottingham Trent University.

Volume 8

Report 85 Ring Opening Polymerisation, N. Spassky, UniversitéPierre et Marie Curie.

Report 86 High Performance Engineering Plastics,D.J. Kemmish, Victrex Ltd.

Report 87 Rubber to Metal Bonding, B.G. Crowther, RapraTechnology Ltd.

Report 88 Plasticisers - Selection, Applications and Implications,A.S. Wilson.

Report 89 Polymer Membranes - Materials, Structures andSeparation Performance, T. deV. Naylor, The SmartChemical Company.

Report 90 Rubber Mixing, P.R. Wood.

Report 91 Recent Developments in Epoxy Resins, I. Hamerton,University of Surrey.

Report 92 Continuous Vulcanisation of Elastomer Profiles,A. Hill, Meteor Gummiwerke.

Report 93 Advances in Thermoforming, J.L. Throne, SherwoodTechnologies Inc.

Report 94 Compressive Behaviour of Composites,C. Soutis, Imperial College of Science, Technologyand Medicine.

Report 95 Thermal Analysis of Polymers, M. P. Sepe, Dickten &Masch Manufacturing Co.

Report 96 Polymeric Seals and Sealing Technology, J.A. Hickman,St Clair (Polymers) Ltd.

Volume 9

Report 97 Rubber Compounding Ingredients - Need, Theoryand Innovation, Part II: Processing, Bonding, FireRetardants, C. Hepburn, University of Ulster.

Report 98 Advances in Biodegradable Polymers, G.F. Moore &S.M. Saunders, Rapra Technology Ltd.

Report 99 Recycling of Rubber, H.J. Manuel and W. Dierkes,Vredestein Rubber Recycling B.V.

Report 100 Photoinitiated Polymerisation - Theory andApplications, J.P. Fouassier, Ecole Nationale Supérieurede Chimie, Mulhouse.

Report 101 Solvent-Free Adhesives, T.E. Rolando, H.B. FullerCompany.

Report 102 Plastics in Pressure Pipes, T. Stafford, RapraTechnology Ltd.

Report 103 Gas Assisted Moulding, T.C. Pearson, Gas Injection Ltd.

Report 104 Plastics Profile Extrusion, R.J. Kent, TangramTechnology Ltd.

Report 105 Rubber Extrusion Theory and Development,B.G. Crowther.

Report 106 Properties and Applications of ElastomericPolysulfides, T.C.P. Lee, Oxford Brookes University.

Report 107 High Performance Polymer Fibres, P.R. Lewis,The Open University.

Report 108 Chemical Characterisation of Polyurethanes,M.J. Forrest, Rapra Technology Ltd.

Volume 10

Report 109 Rubber Injection Moulding - A Practical Guide,J.A. Lindsay.

Report 110 Long-Term and Accelerated Ageing Tests on Rubbers,R.P. Brown, M.J. Forrest and G. Soulagnet,Rapra Technology Ltd.

Report 111 Polymer Product Failure, P.R. Lewis,The Open University.

Report 112 Polystyrene - Synthesis, Production and Applications,J.R. Wünsch, BASF AG.

Report 113 Rubber-Modified Thermoplastics, H. Keskkula,University of Texas at Austin.

Report 114 Developments in Polyacetylene - Nanopolyacetylene,V.M. Kobryanskii, Russian Academy of Sciences.

Report 115 Metallocene-Catalysed Polymerisation, W. Kaminsky,University of Hamburg.

Report 116 Compounding in Co-rotating Twin-Screw Extruders,Y. Wang, Tunghai University.

Report 117 Rapid Prototyping, Tooling and Manufacturing,R.J.M. Hague and P.E. Reeves, Edward MackenzieConsulting.

Report 118 Liquid Crystal Polymers - Synthesis, Properties andApplications, D. Coates, CRL Ltd.

Report 119 Rubbers in Contact with Food, M.J. Forrest andJ.A. Sidwell, Rapra Technology Ltd.

Report 120 Electronics Applications of Polymers II, M.T. Goosey,Shipley Ronal.

Volume 11

Report 121 Polyamides as Engineering Thermoplastic Materials,I.B. Page, BIP Ltd.

Report 122 Flexible Packaging - Adhesives, Coatings andProcesses, T.E. Rolando, H.B. Fuller Company.

Report 123 Polymer Blends, L.A. Utracki, National ResearchCouncil Canada.

Report 124 Sorting of Waste Plastics for Recycling, R.D. Pascoe,University of Exeter.

Report 125 Structural Studies of Polymers by Solution NMR,H.N. Cheng, Hercules Incorporated.

Report 126 Composites for Automotive Applications, C.D. Rudd,University of Nottingham.

Report 127 Polymers in Medical Applications, B.J. Lambert andF.-W. Tang, Guidant Corp., and W.J. Rogers, Consultant.

Report 128 Solid State NMR of Polymers, P.A. Mirau,Lucent Technologies.

Report 129 Failure of Polymer Products Due to Photo-oxidation,D.C. Wright.

Report 130 Failure of Polymer Products Due to Chemical Attack,D.C. Wright.

Report 131 Failure of Polymer Products Due to Thermo-oxidation,D.C. Wright.

Report 132 Stabilisers for Polyolefins, C. Kröhnke and F. Werner,Clariant Huningue SA.

Volume 12

Report 133 Advances in Automation for Plastics InjectionMoulding, J. Mallon, Yushin Inc.

Titles Available in the Current Volume

Infrared and RamanSpectroscopy of Polymers

ISBN: 1-85957-284-7

J. L. Koenig

(Case Western Reserve University)

Infrared and Raman Spectroscopy of Polymers

1

Contents

1. Introduction .............................................................................................................................................. 5

2. Elementary Theory of Vibrational Spectroscopy ................................................................................. 5

2.1 Selection Rules for IR Spectroscopy .............................................................................................. 6

2.2 Selection Rules for Raman Spectroscopy ....................................................................................... 6

3. Basis of Vibrational Spectroscopy as a Structural Tool ....................................................................... 6

3.1 Structural Dependence of Vibrational Frequencies ........................................................................ 6

4. Vibrational Spectroscopic Instrumentation .......................................................................................... 7

4.1 Types of IR Instrumentation ........................................................................................................... 7

4.1.1 Dispersive IR Instrumentation ............................................................................................ 74.1.2 FTIR Instrumentation ......................................................................................................... 74.1.3 Microscopic FTIR Instrumentation .................................................................................... 74.1.4 FTIR Imaging Instrumentation ........................................................................................... 84.1.5 Filter IR Instrumentation .................................................................................................... 84.1.6 Fibre-Optic IR Instrumentation .......................................................................................... 9

4.2 Types of Raman Instrumentation .................................................................................................... 9

4.2.1 Dispersive Raman Instrumentation .................................................................................... 94.2.2 Fourier Transform Raman Instrumentation ........................................................................ 94.2.3 Resonance Raman Instrumentation .................................................................................. 104.2.4 Surface-Enhanced Raman Instrumentation ...................................................................... 104.2.5 Raman Mapping and Imaging Instrumentation................................................................ 114.2.6 Fibre-Optic Raman Instrumentation................................................................................. 11

5. Sampling for Vibrational Spectroscopy ............................................................................................... 11

5.1 IR Sampling .................................................................................................................................. 11

5.1.1 Transmission Spectroscopy .............................................................................................. 125.1.2 Internal Reflection (or Attenuated Total Reflection (ATR)) (a.20) .................................. 125.1.3 External Reflection Spectroscopy .................................................................................... 135.1.4 Diffuse Reflectance FTIR (DRIFT) Spectroscopy........................................................... 135.1.5 Emission Spectroscopy ..................................................................................................... 135.1.6 Microsampling .................................................................................................................. 13

5.2 Sampling for Raman Spectroscopy ................................................................................................... 13

5.2.1 Microscopic Sampling in Raman Spectroscopy and Imaging ......................................... 14

6. Measuring Polymer Orientation with IR and Raman Spectroscopy ............................................... 14

6.1 IR Dichroism................................................................................................................................. 14

6.2 Raman Characterisation of Polymer Orientation ......................................................................... 15

7. IR and Raman Applications to Polymer Characterisation ................................................................ 16

7.1 Material Identification .................................................................................................................. 16


2

7.1.1 Additive Analysis ............................................................................................................. 167.1.2 Chromatographic Separation and Identification .............................................................. 17

7.2 Determination of the Chemical Structure of a Repeating Unit .................................................... 17

7.3 Crystalline and Conformational Structural Order in Polymers .................................................... 18

7.3.1 Introduction ...................................................................................................................... 187.3.2 Crystal Phases of Polymers .............................................................................................. 187.3.3 Complex Formation between Polymers and Complexing Agents ................................... 197.3.4 Conformational Analysis .................................................................................................. 197.3.5 Nematic Ordering in Polymer Dispersed Liquid Crystals ............................................... 19

7.4 Quantitative Analysis .................................................................................................................... 20

7.5 Copolymer Composition and Structure ........................................................................................ 21

7.6 Polymerisation Kinetics and Mechanism in Multicomponent Systems ....................................... 21

7.6.1 Approach .......................................................................................................................... 217.6.2 Examples Using IR Fibre Optics ...................................................................................... 217.6.3 Examples Using Raman Fibre Optics .............................................................................. 227.6.4 Examples Using Rapid Scan FTIR Spectroscopy ............................................................ 22

7.7 Polymer Blends.................................................................................................................................. 23

7.7.1 Utility of Polymer Blends ................................................................................................ 237.7.2 Miscible Blends ................................................................................................................ 23

7.7.2.1 Compatibilised Blends ........................................................................................ 237.7.2.2 Reactive Blends ................................................................................................... 23

7.8 Conducting Polymers .................................................................................................................... 24

7.9 Emulsion Polymers ....................................................................................................................... 24

7.10 Graft Polymers .............................................................................................................................. 25

7.11 Degradation of Polymers .............................................................................................................. 26

7.11.1 Degradation with Ionising Radiation ............................................................................... 267.11.2 Degradation by Photooxidation ........................................................................................ 267.11.3 Degradation by Thermal Oxidation Processes ................................................................. 277.11.4 Degradation by Chemical Exposure ................................................................................. 277.11.5 Analysis of Evolving Gases from Polymers .................................................................... 28

7.12 Orientation of Polymer Chains Due to External Perturbations .................................................... 28

7.12.1 Approach using Vibrational Spectroscopy ....................................................................... 287.12.2 Orientation Functions for Mechanical Deformation ........................................................ 297.12.3 Strain-Induced Crystallisation .......................................................................................... 297.12.4 Deformation-Induced Conformational Changes .............................................................. 307.12.5 Relaxation Processes after Drawing ................................................................................. 307.12.6 Electric Field Induced Reorientation of Polymers ........................................................... 307.12.7 Laser-Induced Orientation ................................................................................................ 30

7.13 Time-Resolved Spectroscopy ....................................................................................................... 30

7.14 Rheooptical FTIR Spectroscopy ................................................................................................... 31

7.15 Two-Dimensional IR (2D-IR) Spectroscopy ................................................................................ 31

7.16 Recycling of Polymers .................................................................................................................. 33


3

The views and opinions expressed by authors in Rapra Review Reports do not necessarily reflect those ofRapra Technology Limited or the editor. The series is published on the basis that no responsibility orliability of any nature shall attach to Rapra Technology Limited arising out of or in connection with anyutilisation in any form of any material contained therein.

7.17 Depth Profiling from Surfaces and Interfaces .............................................................................. 34

7.17.1 Optical Depth Profiling Using ATR-FTIR Spectroscopy................................................. 347.17.2 Depth Profiling Using Photoacoustic IR Spectroscopy ................................................... 347.17.3 Depth Profiling Using Confocal Raman Microspectroscopy .......................................... 35

7.18 FTIR Microspectroscopy .............................................................................................................. 36

7.19 FTIR Imaging ............................................................................................................................... 37

7.20 Raman Microimaging ................................................................................................................... 38

Additional References ................................................................................................................................... 39

Abbreviations ................................................................................................................................................. 41

References from the Rapra Abstracts Database .............................................................................................. 43

Subject Index ...................................................................................................................................................... 129


4


5

1 Introduction

Vibrational spectroscopy represents two physicallydifferent, yet complementary spectroscopictechniques: infrared (IR) and Raman spectroscopy.Vibrational spectroscopy is advantageous as ananalytical tool for polymers, because it provides awealth of information about complex macromoleculeswith respect to composition, structure, conformation,and intermolecular interactions utilising simplesampling techniques. Although both spectroscopicmethods have been successfully utilised for manyyears, recent advances in electronics, computertechnologies and sampling techniques make Fouriertransform IR (FTIR) and laser-excited Ramanspectroscopy powerful and versatile analytical tools.These spectroscopic methods utilise a broad range ofsampling techniques and do not require priorseparation techniques such as solvent extraction andthey do not require high vacuum. Low instrument cost,speed and simplicity make them cost effective forpolymer analysis. Additionally, the techniques aresuitable for quality and process control applications.

IR spectroscopy is one of the most powerfulspectroscopic tools available for the analysis of polymersystems (a.1). IR spectroscopy is molecularly specificwith high sensitivity. It is based on the absorption orattenuation by matter of electromagnetic radiation of aspecified motion of chemical bonds. Through quantumphysics, nature defines the absorption modes, theirlocations in the frequency spectrum and the amount ofenergy absorbed by each molecule. The absorbance at acharacteristic frequency is a measure of the concentrationof the chemical species being probed in the sample.

The Raman effect occurs when a sample is irradiatedby monochromatic light, causing a small fraction ofthe scattered radiation to exhibit shifted frequenciesthat correspond to the sample’s vibrational transitions.Ground-state molecules produce lines shifted toenergies lower than the source, while the slightlyweaker lines at higher frequency are due to moleculesin excited vibrational states. These lines, the result ofthe inelastic scattering of light by the sample, are calledStokes and anti-Stokes lines, respectively. Elasticcollisions result in Rayleigh scattering and appear asthe much more intense, unshifted component of thescattered light. The ratio of the intensities of the Stokesand anti-Stokes lines can be used to determine thetemperature of the sample.

In normal Raman scattering, a molecule is excited to avirtual state, which corresponds to a quantum levelrelating to the electron cloud distortion created by the

electric field of the incident light. A virtual state doesnot correspond to a real eigenstate (vibrational orelectronic energy level) of the molecule, but rather is asum over all eigenstates of the molecule.

Raman spectroscopy is now coming of age as a routineanalytical method. Advances in Raman technology havemeant that robust, user-friendly equipment can bemanufactured at a reasonable cost. Key features of theinstruments include high stability and optical efficiency,large frequency scan ranges, confocal and spatialresolution, mapping capability, rapid imaging, highresolution, and near IR (NIR) excitation to reduceinterfering fluorescence. These advances allow manyapplications of Raman spectroscopy and Ramanmicroscopic systems to polymer analysis.

2 Elementary Theory of VibrationalSpectroscopy

Vibrational spectra including IR and Raman result fromthe interactions of the vibrational motions of a moleculewith electromagnetic radiation (a.2). A simple harmonicoscillator model can describe these vibrationalinteractions. After separating the electroniccontributions, each molecule has an internal vibrationalenergy, U, which can be expressed in terms of thecoordinates and interbond forces between the atomsconstituting the molecule. A nonlinear moleculeconsisting of N atoms has 3N–6 degrees of freedom.Thus, a set of 3N–6 generalised coordinates, Gi, canbe found that completely describes the internal motionsof this nonlinear molecule. The internal energy of themolecule can be written as:

U = U(G1…Gi)

where i = 3N–6.

It can be shown that the internal energy can be written:

U U Qo ii

ii= + ∑1 2 2Λ

where Qi are a set of ith normal coordinates and Λii isa diagonal matrix. Thus, we have a system of weaklycoupled harmonic oscillators. The first term, Uo, is theinternal potential energy of the molecule in theequilibrium state. The second term represents thecontribution to the potential energy from thefundamental collective vibrational bands, while thecubic and higher terms are responsible for combination,difference, and overtone bands.


6

The decomposition of coupled harmonic oscillators intoa collection of independent oscillators is known as anormal mode expansion and the independent oscillatorsare called normal modes. Normal modes are definedas modes of vibration where the respective atomicmotions of the atoms are in ‘harmony’, i.e., they allreach their maximum and minimum displacements atthe same time. These normal modes can be expressedin terms of bond stretches and angle deformation(termed internal coordinates) and can be calculated byusing a procedure called normal coordinate analysis.

2.1 Selection Rules for IR Spectroscopy

A normal vibrational mode in a molecule may give riseto resonant IR absorption (or emission) ofelectromagnetic radiation only when the transition isinduced by the interaction of the electric vector, E, ofthe incident beam with the electric dipole moment, µi,of the molecule. That is, the dynamic dipole momentof the ith normal mode, δµi/δqi or µi, is nonzero. Theintensity of the transition is proportional to the squareof the transition dipole moment, i.e., the matrix elementof the electric dipole moment operator between the twoquantised vibrational levels involved.

2.2 Selection Rules for Raman Spectroscopy

Raman scattering is envisaged as the process ofreradiation of scattered light by dipoles induced (P)in the molecules by the incident light and modulatedby the vibrations of the molecules (a.3). In normalRaman scattering by molecules in isotropic media,the dipoles are simply those that result from the actionof the electric field component, E, of the incident lighton the molecules,

P = αE

where α is the molecular (dipole) polarisability.

The molecule will scatter light at the incident frequency.However, the molecule vibrates with its own uniquefrequencies. If these molecular motions produce changesin the polarisability, α, the molecule will further interactwith the light by superimposing its vibrationalfrequencies on the scattered light at either higher or lowerfrequencies. Raman scattering stems from the oscillatingpolarisability within a molecule as a function of vibrationand not from the permanent dipole of the molecule. Asa result, Raman spectra are less affected by dipoleinteractions and as a result show sharp, stable lines.

3 Basis of Vibrational Spectroscopyas a Structural Tool

Our primary interest is in determining the structureof polymers so we need to understand the molecularbasis of vibrational spectroscopy as a structural tool(a.4). The vibrational energy levels can be calculatedfrom first principles by using a technique callednormal coordinate analysis (a.5), and as a result someof the factors influencing spectra have beendiscovered.

The vibrational frequencies of a molecule depend on:

• Nature of the motion,

• Mass of the atoms,

• Detailed geometric arrangements,

• Nature of the chemical bonding, and

• Chemical and physical environment.

Vibrational techniques are particularly sensitive to thestructure of the macromolecules. A vast literatureexists from which group frequencies have beencorrelated with structural components of themolecules (a.6).

3.1 Structural Dependence ofVibrational Frequencies

A vibrational spectrum either is ordinarily recorded inwavenumbers (cm-1), the number of waves percentimetre. The relationship between ν and thewavelength, λ (µm), is

ν (cm-1) = (104) / λ (µm)

which can also be written

ν (cm-1) = 3 x 1010 Hz

The wavenumber scale is directly proportional to theenergy and the vibrational frequency of the molecule.

In wavenumbers

∆Evib = h cs ν (cm-1)

where ∆Evib is the vibrational energy level separation,h is Planck’s constant (6.62 x 10-34 J.S), and cs is thespeed of light (3 x 1010 cm/s).


7

The fundamental IR region arbitrarily extends from4,000 cm-1 to approximately 300 cm-1. The far-IRregion extends from 300 to 10 cm-1, and the observedbands are due to molecular torsional motions as wellas lattice and intermolecular modes. The low IR sourceenergy makes this region generally inaccessible exceptwith special instrumentation. The NIR region extendsfrom 14,000 to 4,000 cm-1 (0.7-2.5 µm) and theobserved bands consist of overtones and combinationsof fundamental mid-IR bands (a.7). The NIR isbecoming an important IR method, particularly inquality control.

4 Vibrational SpectroscopicInstrumentation

4.1 Types of IR Instrumentation

IR spectroscopic instrumentation is grouped intomultiplex (Fourier transform) and nonmultiplex(dispersive) methods. These two categories reflect themeans by which the spectra are acquired.

4.1.1 Dispersive IR Instrumentation

A dispersive IR instrument (such as a scanningspectrometer) utilises a grating or prism as awavelength separation device to resolve the IRradiation into individual wavelength components(referred to as spectral resolution elements). A meansis provided in the instrument, such as an exit slit, toisolate specific spectral resolution elements forpassage to the detector. The IR spectrum is obtainedby moving (scanning) the grating over a givenwavenumber region after passing through the sample.The intensity of the spectral resolution element isdetermined by the intensity of the source and thesensitivity of the detector.

Scanning IR spectrometers have a rich history of usebut they have a number of disadvantages arisingprimarily from the ‘step-wise’ nature in which thespectra are acquired. The optical dispersion process andthe entrance and exit slits limit the amount of energyfalling on the detector to a small fraction of the totalIR energy. Additionally, moving the grating or prismimposes strict mechanical tolerances on the opticalcomponents. With scanning spectrometers it is not easyto increase the signal-to-noise ratio (SNR) by multiplescanning, as it is difficult to reproduce precisely theposition of the grating.

4.1.2 FTIR Instrumentation

IR absorbance spectra have traditionally been recordedusing dispersive instruments but, since 1970, FTIRinstruments have been available that are capable ofcollecting high-quality spectra in a fraction of the timepreviously required with enhanced SNR andwavenumber accuracy. The key component of thesespectrometers is a Michelson interferometer, whichoperates on the principle of amplitude division of theincoming light. The mechanism is simple. Theincoming light is split inside an interferometer, onebeam going to an internal fixed mirror and the other tothe moving mirror. After reflection, the beamsrecombine inside the interferometer, undergoingconstructive and destructive interference, producing theinterferogram. The spectral information is containedin the interferogram. After the data are detected andstored, it is necessary to perform a mathematicaltransform operation (a Fourier transform) on the dataset to convert it into a conventional spectrum.

The primary advantage of multiplexing the spectralresolution elements in the IR is the improvement inthe SNR. The improvement arises because the detectorirradiance for each measurement is increased. Becausethe detector noise is constant and independent of thesource, the SNR is improved because the multiplexingdistributes the detector noise over the intensities ofmany spectral resolution elements. This distributionprocess lowers the noise in each spectral resolutionelement more so than if the spectral resolution elementis measured individually by step scanning.

Mid-IR measurements are typically performed usinga linear scan interferometer and appropriate samplingaccessory to guide the light to and from the sampleof interest.

4.1.3 Microscopic FTIR Instrumentation

FTIR microspectroscopy is a microanalyticaltechnique, which interfaces an FTIR spectrometer toan optical microscope. Regions of interest in the sampleare spatially isolated using the microscope’s apertures.It enables the IR spectrum of sampling regions downto about 10 µm resolution to be taken. Consequently,FTIR microscopy is ideal for compositional mappingand analysis of heterogeneous samples whose domainsizes are in the tens of micrometre range.

FTIR microscopes use x15 and x10 condensor lensesof the non-IR absorbing Cassegrainian type. They areconstructed from front surface mirrors and are mounted


8

on-axis so that the path for the visible light is parafocaland colinear with the IR light. The microscope stageis computer controlled with 1 µm steps. The sampleis not physically aperatured since the sample isspatially isolated from the microscope aperatures. ForIR microscopy, two apertures take up positions suchthat their images concide in the sample plane(redundant aperturing). The aperatures are a set ofcrossed knife blades in the form of a rectangle whichis of adjustable size.

The principal problem in IR microscopy is thepresence of scattered light due to diffraction whichlimits the spatial resolution by increasing the noise.Diffraction is significant when the aperturedimensions approach the wavelength of the IRradiation. The main effect of diffraction is that at smallaperature sizes, light spreads outside the specified areainto the surrounding region. As higher spatialresolution is sought, the problem increases, as theapertures are smaller, ultimately leading to loss ofspectral quality and photometric accuracy.

4.1.4 FTIR Imaging Instrumentation

FTIR imaging (as opposed to FTIR mapping) is amethod using two-dimensional array detectors and theimage is obtained in the ‘snap-shot’ mode, i.e., allelements of the field of view of the microscope arerecorded simultaneously. FTIR imaging is anoutstanding new tool for online materials monitoring.A spectroscopic imaging system consists of threecomponents: image capturing, image processing, anda visualisation system.

The spectral data obtained from IR imaging areanalysed to produce a variety of response factors whichare spatially expressed in terms of the individual datagrid coordinates. The data collection associated withthe spectroscopic mapping contains all of theinformation required to deconvolute the contributionsof the different species in the sample. Using a computer,one can analyse the entire spectral range at eachpositional coordinate or, for a given frequency, developa spatial image demonstrating the spatial distributionof an object-specific spectral feature (a.8).

The advantages of FTIR imaging are:

• Micro-spatial (~7 µm) chemical mapping ofheterogeneous complex samples,

• High sensitivity (ppm in many cases),

• High selectivity (IR spectra are fingerprints ofmolecules with many bands available),

• Rapid acquisition of data,

• Sample preparation is simple (optical microscopicmethods are generally useful),

• Experiment can be automated to trigger acquisitionas required and

• Images can be computer-enhanced for visualisationand interpretation.

FTIR imaging with a focal plane array (FPA) detectoris a new state-of-the-art multichannel (a.9) method ofsimultaneously recording the spectral image of asample as shown in Figure 1 (a.10).

The IR chemical imaging system measures chemically-specific IR spectra using a mercury cadmium telluride(HgCdTe) FPA detector which provides broadfrequency response (out to ~ 18 µm), high sensitivity(2 x 1011 cm Hz 1/2/Watt), and an operating temperatureof 40-60 K.

4.1.5 Filter IR Instrumentation

One IR spectroscopic system often used for industrialmonitoring is the ‘selective-wavelength’ spectrometer

Figure 1

Diagram of an FPA camera imaging system(x and y refer to axis)


9

or a ‘filtometer’ (a contraction of the terms ‘filter’ and‘photometer’). These devices consist of a source ofradiation, energy collecting optics, a beam chopper, asample compartment, another set of collection opticsand a radiation detector or detectors. Interference filtersprovide wavelength selection.

The basic function of band-pass optical filters is toefficiently transmit light within a chosen wavelengthband and effectively reject the wavelengths lyingoutside of this band. The ratio of the in-band (desired)transmitted energy to the out-of-band (undesired)transmitted energy is the single most importantparameter to be considered.

The electronics of the filtometer include power suppliesthat operate the source, control temperature and poweramplifiers and related circuits that convert detectorsignals to concentration values. The limitation of thistype of control instrumentation is primarily sensitivityparticularly when remote sensing, via emission, is thesampling method.

Filter IR instruments have found broad applications inprocess control in the past (a.11). By utilising a portableIR spectrometer, the characteristic chemical sensitivityand selectivity of IR measurements can be performedin the field to interrogate the composition of industrialsamples (a.12).

4.1.6 Fibre-Optic IR Instrumentation

IR-transmitting optical fibres are evanescent wavesensors using a mathematical deconvolution techniqueto extract the absorbances and follow theconcentrations of the components as they occur in bothlaboratory scale and process production. The fibre-opticprobe used can be placed at specific locations withinthe samples or at the surface. The specificity of thetechnique, the speed of data acquisition and theportability of equipment make this method ideal as atool to fundamentally probe polymer reactions andprocesses. Chalcogenide optical fibres are used to directIR radiation from an FTIR spectrometer through anattenuated total reflection (ATR) probe immersed in areactor and back to the spectrometer.

4.2 Types of Raman Instrumentation

The evolution of Raman instrumentation has beendramatic. After making difficult measurements withuncertain sources, the laser came along and Raman

became a revitalised field. This was followed by theavailability of computers, two-dimensional detectorsand filter devices to replace monochromaters. Only afew brief remarks will be made here with referencesgiven for the interested reader.

4.2.1 Dispersive Raman Instrumentation

The configuration for a Raman dispersive experimentbasically consists of five parts (laser, sample, dispersingelement, detector and computer) (a.13). Amonochromatic laser beam (excitation radiation) isfocused on the scattering sample. The scattered lightfrom the sample is focused on the entrance slit of amonochromator and dispersed. The dispersion elementdiscriminates between the strong elastic scattering(Rayleigh scattering) and the weak inelasticallyscattered light (Raman scattering) with differentfrequencies. A typical single monochromator providesstray light rejections of 10-5-10-6 (as a fraction of theRayleigh light that enters the spectrometer) limited bythe imperfections on the optical surfaces such asgratings. Double and triple monochromators are oftenrequired to obtain adequate stray light rejection.

The Raman spectrum is given by the detection of theintensity of the scattered, frequency-shifted light by aphotoelectric system. The resulting signal of thedetector is amplified and converted to a formappropriate for plotting as a function of frequency.

4.2.2 Fourier Transform Raman Instrumentation

The basic problem in Raman spectroscopy is theinefficiency of the Raman scattering; roughly only oneout of 108 incident photons is Raman scattered. This,coupled with the fact that most polymeric systems giverise to an interfering fluorescent background, leads toa real problem of detectibility. For example, if a systemcontains one part per million of an interfering systemwhich fluoresces under visible excitation, the sameincident flux of 108 photons will produce 100fluorescent photons which will completely mask theRaman signal. This fluorescence does not occur whenthe excitation frequency is below the electronic energylevels of the molecules. The recent development ofFourier transform Raman (FT-Raman) spectroscopy,using NIR excitation, drastically reduces the problemof fluorescent interference.

FT-Raman also benefits from advantages inherent tointerferometry: high collection efficiency, excellent


10

wavelength precision, easily variable resolution andspectral coverage, software developments in FTIR(a.14). The restrictions of FT-Raman arise from the lowSNR. The SNR is limited by detector noise rather thansignal shot noise. Detectors in the 1 to 2 µm region arenoisy. The result is an SNR comparable to that for asingle-channel dispersive system with equalmeasurement time (a.15).

FT-Raman spectroscopy became possible due to thecommercial availability of the Nd:YAG laser output at9395 cm-1. The Stokes-shifted Raman scattering occursin the 5000-9000 cm-1 spectral range, coincident withthe NIR region. Although the photon energy at 1076 nmis insufficient to cause fluorescence (which canoverwhelm the weak Raman scattering spectrum), theintensity of Raman scattering is diminished by a factorof ~22, in comparison to excitation at 488.0 nm (thelaser frequency of the Ar+ laser); this factor can becompensated for by increasing the excitation power.

To obtain good Raman spectra using the FT-Ramanmethod, the unwanted Rayleigh scattering must beremoved. Because of the nature of the Michelsoninterferometer, both Rayleigh and Raman-scatteredlight enter the system. Since the Rayleigh componentis from 106 to 108 times more intense than the Ramanscattering, it must be removed before it reaches thedetector, because a signal of this intensity drives thedetector into the distributive noise regime, resulting inhigh-frequency noise spread throughout thetransformed spectrum.

4.2.3 Resonance Raman Instrumentation

Resonance Raman spectroscopy occurs when the energyof the exciting beam is close to an electronic energy levelof the molecule and the excitation makes one term inthe sum of eigenstates dominate over all others.Resonance Raman spectroscopy takes place when thefrequency of the exciting line is similar to the absorptionfrequency of a chromophore in the sample. When thisoccurs, the electron cloud surrounding the molecule ismore readily distorted by the electric field of the incidentlight. The transition has a higher probability, and thereis an enhancement of the Raman process. The Ramansignal from the chromophore can be enhanced by sevenor eight orders of magnitude. The vibrational modesenhanced are dominated by vibrational bands that arepart of the chromophore responsible for the resonance.The resonance lines are generally totally symmetric anddistort the molecule along directions of electron densitychanges between the ground and the resonant electronicexcited state.

Ultraviolet Raman resonance (UVRR) spectroscopyprovides for chemical species identification from boththe characteristic vibrational structure and electronicspectra. The resonance enhancement also increases theabsolute sensitivity of detection, making it easier todetect the structures. The advantages of UVRRspectroscopy are high sensitivity, lack of fluorescenceand suitability for use in aqueous solutions.

Resonance Raman spectroscopy combines bothvibrational and electronic spectroscopies. Thevibrational spectrum at a particular excitationwavelength provides the first dimension. Theexcitation spectrum, the intensity of each vibrationalband as a function of the excitation wavelength,provides the second dimension. Since mostmolecules have resonance enhancement in the UV,this approach is quite general, but not universal. Theavailability of a range of excitation frequencies fromthe laser source makes exploitation of this form ofRaman scattering possible.

Detection of UVRR spectra is complicated by a numberof experimental difficulties: the photooxidation andphotodestruction of molecules, distortion of spectralinformation due to optical saturation phenomena andphotoinduced transients, and fluctuations of thescattered light intensity in inhomogeneous samples.

4.2.4 Surface-Enhanced Raman Instrumentation

In surface-enhanced Raman spectroscopy (SERS),increased Raman signals are observed from moleculesattached to metallic clusters ranging in size of the orderof tens of nanometres (a.16). Enhancements as high as1014 have been observed. These enhancement factorscan lead to single-molecule Raman spectroscopy (a.17).Using a Raman microscope the probe volume can beas small as 10 picolitres. Spectra can be measured witha one-second collection time.

In order to achieve large surface Raman signals, it isnecessary that the metal surfaces are specially preparedin one of several ways, which renders them rough orfinely divided on a length scale comparable to opticalwavelengths. Under favourable conditions, SERS-active metals enhance the surface Raman intensity byup to 105-fold, giving strong Raman signals.

The enhancement of Raman scattering at noble metal(gold, platinum, etc.) surfaces can be attributed to twofactors. One is an electromagnetic effect (discussedabove) observed for molecules near roughened noblemetal surfaces, and the second is a chemical interaction


11

between the absorbed molecule and the metal surface.The electromagnetic enhancement observed by SERSarises from the unique optical properties of noble metals.The zero oxidation electronic configurations of thesemetals are d10s1. The single s electron is well shieldedby the inner shell electrons and behaves as a free electron.In the visible region of the spectrum, this free electroncauses the dielectric constant of the metal to have a largenegative real component and a small imaginarycomponent. The large negative component of the realpart means that the electrons react very strongly toincident radiation and their displacement is such thatthe field due to the polarisation of the particles resistsfurther polarisation. The result is a resonance conditionthat absorbs energy from the incident light and creates alocally intense electric field within the metal particle.

When the incident radiation interacts with the surface,it causes the free electrons to oscillate with the incidentelectric field and polarises the noble metal particles.This creates a strong local electric field at the particlesurface known as a surface plasmon. When a moleculeis in close proximity to a noble metal particle themolecule is polarised by the electric field of the noblemetal particle. This leads to an enhancement of theRaman signal because the Raman scattering isproportional to the square of the local electric field.

4.2.5 Raman Mapping and ImagingInstrumentation

The ideal Raman spectrometer would consist of a high-dispersion, low-stray-light (where the scattered lightis low) single monochromator with a multichanneldetector. In the new generation of Raman instruments,a polychromator or spectrograph and a multichanneldetector are used instead of the monochromator andphotomultiplier. The entire spectrum is collectedsimultaneously using an array of detectors in whicheach element of the multichannel detector iscomparable in sensitivity to a single photomultiplier.The assumption is that all light incident on the detectoris correctly positioned with a single wavelengthincident upon each single detector. In this way, the timeneeded to record a spectrum is reduced markedly.Additionally, the simultaneous detection of thespectrum increases the accuracy of intensitymeasurements of different Raman bands and avoidserrors in interpreting accidental changes in thebackground due to laser fluctuations as Raman bands.Furthermore, multichannel detectors offer newpossibilities for investigation of photolabile systems(i.e., systems that degrade by photoirradiation), time-resolved experiments and chemical images.

The wavelength at a particular detector element isdetermined by the position of that element at the focalplane of the monochromator (the grating position). Inanother mode of operation, an acousto-optic tunablefilter (AOTF) is used rather than a monochromater. InRaman applications, the AOTF is used to spectrallyfilter the source (a.18). Under computer control, theAOTF is swept through a wavelength range and, atpredetermined intervals, images are recorded. For morerapid operation, the AOTF may be digitally tuned topredetermined frequencies where single frames maybe collected (a.19).

In practice, the AOTF is placed between the Ramanscatterer and a Si FPA detector yielding a no-movingparts Raman spectroscopic imager. The AOTF replacesthe dispersive monochromator and is operable between400 nm and 1900 nm. At each discrete wavelength acharge collection detector (CCD) frame is collected,digitised and stored. The size, wavelength range,wavelength increment and exposure time for eachimage frame maybe modified under computer control.Potentially, one can record one frame/second.

4.2.6 Fibre-Optic Raman Instrumentation

A dual-fibre optical probe has been developed forRaman spectroscopic monitoring of a number ofpolymer processes. In the dual-fibre configuration theinternal bundles transmit the light to the sample andthe outer fibres carry the signals back to thespectrometer for processing.

5 Sampling for VibrationalSpectroscopy

5.1 IR Sampling

One of the most attractive aspects of FTIR spectroscopyis its ability to deal with a great number of samplingtechniques, making it a versatile method which can beadapted to the study of a wide range of materials.

For IR spectroscopy, sample preparation has been alabour-intensive operation requiring some measure ofskill and experience. Conventional IR spectroscopy ismainly based on transmission measurements except forsamples for which the preparation of a thin layer isproblematic, inadequate, or prohibited. In these casesspecial sample preparation is required as indicated inSection 5.1.1, 5.1.2, etc. The main sampling techniquesmay be seen schematically in Figure 2.


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5.1.1 Transmission Spectroscopy

Transmission spectroscopy is the simplest and mostpopular mode for quantitative analysis. Radiation passesthrough the sample and is absorbed by a length equal tothe thickness of the sample in the direction of IRpropagation. The single beam intensity can be ratioedagainst a background collected without the sample andan absorbance spectrum obtained. The absorbance hasa simple linear relation to the concentration under mostconditions and can be used for quantitative analysis. Ingeneral, it delivers the highest SNR of all samplingtechniques and does not affect the spectral data in anymanner. No special sample handling techniques arerequired and quantitative data processing isstraightforward. However, films usually have to be thin,i.e., 1 to 100 µm. Such films can be prepared by solventcasting or compression moulding.

5.1.2 Internal Reflection (or Attenuated TotalReflection (ATR)) (a.20)

Attenuated reflection may be used for samples with noor low transmission or when sample geometry demands

it. The sample is brought into contact with an IR-transparent crystal of high refractive index. The IRbeam then traverses the length of the crystal whilepenetrating the sample with multiple internal reflectionsat the free crystal surface. Thus, depending on therefractive index and angle of incidence, the region ofthe sample examined is typically a 0.1-10 µm layerclose to the crystal. Spectral data is different from thatobtained in transmission and the signal does not varylinearly with concentration. Hence, calibration isrequired for quantitative studies.

Depth profiling is also a possibility using the ATRtechnique (a.21) and probed depth (i.e., how deep inthe sample the light probes) varies as

dn n

p

o

=−( )

λπ θ2 2 2 2 1 2

sin/ (1)

where dp is the probed depth, no and n are the refractiveindices of the ATR crystal and the sample respectively,θ is the angle of incidence and λ the wavelength ofradiation. Algorithms to extract depth of penetrationindependent of wavenumber have been developed(a.22, a.23).

Figure 2

IR sampling techniques for polymers


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5.1.3 External Reflection Spectroscopy

Reflection-absorption spectroscopy is an externalreflection technique that utilises an IR beam incident ata grazing angle. This allows for a convenient method tostudy polymers in contact with reflective (e.g., metal)surfaces. When IR light impinges on a metal surface, anelectrical field arises near the surface. The metallicsurface imposes a strict dipole moment selection rule,which demands that the incident light should have acomponent parallel to the plane of incidence (p- orparallel polarisation). The interaction between the sampleand the incident light is strong when the angle ofincidence is between 75° and 89° and approaches amaximum at 88°. For parallel-polarised incidentradiation, only the dipole moments of the surface speciesnormal substrate interact with the electric field. A detaileddiscussion of the technique has been published (a.24,a.25). It has been established that the sensitivity ofreflection absorption IR spectroscopy is greatly improvedwhen using a grazing incidence (65° or more). In theparticular case of thin layers (of organic or inorganicmaterial) deposited on a good reflecting surface such asa metal, a lower detection limit of a few nanometres inthickness can be achieved. The drawbacks include theappearance of asymmetric absorption modes and shiftingof mode frequencies that may be corrected by the use ofthe Kramers-Kronig transformation.

5.1.4 Diffuse Reflectance FTIR (DRIFT)Spectroscopy

Light impinging on a solid or powdered surface isdiffusively scattered in all directions and may bedirected to an IR detector. This technique is particularlyuseful if the sample is strongly scattering and weaklyabsorbing. A general theory for powdered samples wasdeveloped by Kubelka and Munk (a.26) and relates thesample concentration to the scattered radiationintensity. DRIFT spectroscopy requires little samplepreparation, is ideal for particulate substances and hasfast data collection with good SNR. However, someinformation is lost in the highly absorbing regions andthere is small band shape distortion. Quantitativeanalysis should be performed on the same particle size.DRIFT spectroscopy has been used to probe polymerlayers, fibres and polymers on metals (a.27).

5.1.5 Emission Spectroscopy

If collected correctly, emission spectra mirrorabsorbance spectra and can be collected even fromopaque samples. The material must not have thermalgradients, readsorption of emission, or self-adsorption.

5.1.6 Microsampling

As far as microspectroscopy is concerned, onlytransmission and reflection under near-normalincidence are initially implemented. The recent launchof specialised objectives provide the user withadditional techniques such as external reflection undergrazing angle and ATR.

5.2 Sampling for Raman Spectroscopy

The sampling techniques used in Raman spectroscopyare shown in Figure 3. A sample in any state can beexamined without difficulty by using Ramanspectroscopy. The laser beam is narrow, collimated, andunidirectional, so it can be manipulated in a variety ofways depending on the configuration of the sample.

Figure 3

Raman sampling techniques for polymers


14

For liquids, a cylindrical cell of glass or quartz withan optically flat bottom is positioned vertically inthe laser beam. For solids, the particular method useddepends on the transparency of the sample. For clearpellets or samples, right angle scattering is used.With translucent samples, it is helpful to drill a holein the sample pellet. Powdered samples can beanalysed by using front-surface reflection from asample holder consisting of a hole in the surface ofa metal block inclined at 60° with respect to thebeam. Injection moulded pieces, pipes, and tubing,blown films, cast sheets, and monofilaments can beexamined directly. One of the advantages of Ramansampling is that glass containers can be used whichcan be sealed if desired (a.29).

5.2.1 Microscopic Sampling in RamanSpectroscopy and Imaging

The incorporation of high-resolution optics in aRaman spectrometer allows sampling from areas ofless than 1 x 10-6 m in diameter. The addition of aconfocal microscope improves the axial resolution toa couple of microns. Those developments, along withthe introduction of notch filters and holographictransmission gratings, allow the reduction of theacquisition time of Raman spectra from minutes toseconds. The fast data collection combined with thehigh lateral and vertical resolutions makes possiblethe collection of Raman images with several micronspatial resolutions.

6 Measuring Polymer Orientationwith IR and Raman Spectroscopy

Orientation can be defined as the preferential alignment(either uniaxial or biaxial) of polymer chains orsegments when submitted to an external force. Theorientation induces significant changes in the propertiesboth positively and negatively.

A high degree of alignment is the basis of improvedmechanical, optical, and electrical properties in almostall polymers. Many factors influence the orientationbehaviour of polymer chains, including crystallinity,phase separation, free volume, chain rigidity, molecularfriction, interchain interactions and chainentanglements. Consequently, it is necessary tounderstand the correlations among molecular order,material properties, and fabrication procedures.Experimental characterisation of the degree and

direction of alignment is required in order to understandhow molecular design and processing strategies leadto the ultimate state of alignment. There are severalmethods available, including IR dichroism, X-raydiffraction, nuclear magnetic resonance (NMR),birefringence, polarised fluorescence, ultrasonicmeasurements, and polarised vibrational spectroscopies(IR and Raman). Of all these techniques, IR dichroismis one of the most frequently applied, since it isapplicable to many polymer systems, it can be used tomake measurements on the microscopic andmacroscopic scales, and it can specifically measureorientation of different phases (i.e., amorphous orcrystalline) in the same sample.

6.1 IR Dichroism

In general, IR absorption is caused by the interactionbetween the IR electric field vector and the moleculardipole transition moments related to the molecularvibrations. Absorption is at a maximum when theelectric field vector and the dipole transition momentare parallel to each other. In the case of perpendicularorientation, the absorption is zero. Directionalabsorptions are measured using polarised light. Theterms parallel and perpendicular refer to the orientationof the polarised beam with respect to a reference axis.For deformation studies, the reference axis correspondsto the stretching direction.

The IR dichroic ratio may be considered to becharacteristic of the directional orientation of thesegments of the molecule. For a polymer whosemolecular axis is oriented parallel to the spectrometersampling plane, the dichroic ratio, R, is defined as

RA

A=

⊥

||

where A|| is the absorbance parallel to the chain axis,and A⊥ is absorbance perpendicular to the chain axis.For highly oriented samples, the dichroic ratio mayapproach either infinity or zero, depending on thealignment of the transition-moment vector withrespect to the molecular chain axis. The alignmentof the chain segments can be determined fromdichroic ratio measurements if the inherentpolarisations are known (a.29). In general, A|| andA⊥ are determined successively by using a polariserthat is aligned parallel and perpendicular to thestretching direction. For samples that have a lowlevel of orientation, the magnitude of the dichroicratio is close to 1. In these cases of minimal


15

orientation, it is better to measure the dichroicdifference A||–A⊥ because it is a more sensitivemeasurement under these conditions.

One of the practical problems in the case of IRdichroism measurements arises from the requirementof low band absorbance (roughly lower than 0.7absorbance units) in order to permit use of the Beer-Lambert law. This condition implies use of very thinfilms in the range of 1 to 200 µm. NIR measurementsalleviate this problem.

6.2 Raman Characterisation of PolymerOrientation

Raman scattering arises from the interaction betweenradiation induced oscillating electric dipoles andmolecular vibrational modes. In general, the inducedpolarisability is not necessarily in the direction of theincident beam, and they are related by a second rangetensor, α, thus:

P = αE

or written in terms of the components:

Px = αxxEx + αxyEy + αxzEz

Py = αyxEx + αyyEy + αyzEz

Pz = αzxEx + αzyEy + αzzEz

where αxx, αyy and αzz are the components of theprincipal axes of the polarisability ellipsoid and αxy,αyz and αxz are the other components. A single crystalcan give up to six different spectra, depending on itsorientation towards the two directions of polarisationof the incident laser light.

Consequently, the Raman scattered light emanatingfrom even a random sample is polarised to a greater orlesser extent. For randomly oriented systems, thepolarisation properties are determined by the two tensorinvariants of the polarisation tensor, i.e., the trace andthe anisotropy. The depolarisation ratio is always lessthan or equal to 3/4. For a specific scattering geometry,this polarisation is dependent upon the symmetry ofthe molecular vibration giving rise to the line.

In solids, the problem of polarisation is morecomplicated, but the results are more rewarding (a.30).In solids, the molecular species are oriented withrespect to each other. Therefore, the molecular

polarisability ellipsoids are also oriented along definitedirections in the solid. Since the electric vector of theincident laser beam is polarised, the directionality inthe crystal can be utilised to excite and obtain Ramandata from each element of the polarisability ellipsoid.With the laser polarisation along z and collection alongz, a spectrum from the αzz component of the tensor isobtained. By rotating the analyser 90°, therebycollecting x polarised light while still exciting along z,αzx is obtained.

In the usual Raman experiment, the observations aremade perpendicular to the direction of the incidentbeam, which is plane polarised. The ‘depolarisationratio’ is defined as the intensity ratio of the twopolarised components of the scattered light which areparallel and perpendicular to the direction of thepropagation of the (polarised) incident light. Thepolarisation of the incident beam is perpendicular tothe plane of propagation and observation. For thisgeometry, the depolarisation ratio is defined as theintensity ratio:

ρ = VH/VV

where, for the right angle scattering experiment, V isperpendicular to the scattering plane and H is in thescattering plane. An alternate notation expressed interms of the laboratory coordinate system is:

A(BC)D

where A is the direction of travel of the incident beam,B and C are the polarisation of the incident and scatteredlight, respectively, and D is the direction in which theRaman scattered light is observed. Generally, theincoming beam is along the x axis, the scattered beamis along the z axis and the y axis is perpendicular to thescattering plane.

One of the major problems is the difficulty ofdetermining that the polarisation is scrambled whetherby scattering inhomogeneities in the sample itself orby the birefringence of the sample itself. Many spectrashow evidence of extensive depolarisation of both theincident and scattered light, and thus each spectrum isan indeterminate mixture of four different polarisations:the intended polarisation, the one resulting fromdepolarisation of the incident light, the one resultingfrom depolarisation of the scattered light, and (to alesser extent) the one resulting from depolarisation ofboth the incident and scattered light. When this occurs,little useful information is available from the individualpolarised spectra.


16

7 IR and Raman Applications toPolymer Characterisation

7.1 Material Identification

IR and Raman spectroscopy are the best methods forthe identification of unknown compounds if the spectraof the reference compounds are known. The ideaunderlying spectroscopic identification is that a patternof frequencies provides a ‘fingerprint’ of a particularmolecule and that this pattern of frequencies can berecognised when a spectral database is searched.Spectral comparison of an unknown sample foridentification is generally done by visual comparison(often with the computer as a tool) or by using cross-correlation techniques. With cross-correlationtechniques, an identification is performed bycalculating a matching score for the spectra of theunknown and an IR spectrum of a known compoundin the database. Additional spectra in the database areranked according to the matching score determined andthe spectroscopist must make a final determinationbased on his knowledge of the properties of theunknown sample relative to the chemicals with highmatching scores.

Independent of the type of scoring system used, thereis always a risk of obtaining a false identification result.Each measured spectra can match the frequencies ofseveral different molecules in addition to the matchwith the molecule actually present in the sample. Falseresults are caused by the accidental matching of thefrequencies of a chemical with no properties similar tothe unknown. An incorrect result is also obtained whenthe score due to random matching cannot be discernedfrom the score match due to matching of the real spectrain the sample. It is therefore useful to include otherinformation when interpreting the quality of the match,such as the chemistry involved in the unknown sample.The likelihood of accidental matches (and hence thelikelihood of false identification) increases if thespectral reproducibility is reduced.

The Sadtler division of Bio-Rad Laboratories (http://www.sadtler.com) has a product on compact disccontaining 175,000 IR and 3,300 Raman spectra. Fora subscription price the user gets the disc and an e-mailed code from Sadtler that opens the disc forsearches on one computer for a year. Once the codeopens the disc, the user may perform unlimited lookupson one computer for one year. A lookup retrievesspectra by names or structures for comparison. Inaddition, the user may perform unlimited searches toidentify or classify unknowns. Other databases for

polymer and additives are also available (166, 357)including one for fibres (376). For Ramanidentification, the databases are smaller because of thelimited history of collection of spectra but attempts arebeing made to bridge the gap (a.31).

7.1.1 Additive Analysis

Polymer additives are materials designed to enhanceor upgrade the performance or capabilities of basepolymers to achieve the optimal properties for a specificapplication (a.32). Plastics would not be able to performtheir diverse functions without the assistance of a verybroad range of plastics additives (a.33). Without them,some plastics would degrade during processing and,over time, the polymers would lose impact strength,discolour, and become statically charged, to list just afew problems. Additives not only overcome these andother limitations, but can also impart improvedperformance properties to the final product.

It is necessary to be able to identify and quantify theadditives in polymers and vibrational spectroscopyis a particularly useful approach to this problem.Compared with traditional chemical analyses,vibrational methods are nondestructive and are time-and cost-effective as well as more precise. A largenumber of examples exist in the literature. Forexample, antistatic agents (polyethylene glycol (PEG)in polyethylene (PE)) can be detected directly usingFTIR sampling (367). An IR spectroscopic techniquefor the analysis of stabilisers (2, 6-di-tert-butyl-4-methylphenol) in PE and ethylene-vinyl acetate (EVA)copolymer has been described (368). It is possible toquantify the amount of external and internal lubricants(stearic acid in polystyrene (PS)) (371). Fillers inpolymers can also be analysed (white rice husk ash(predominantly silica in polypropylene (PP)) (268).Raman spectroscopy has been used to detect residualmonomer in solid polymethyl methacrylate (PMMA)samples (326).

It is also possible to determine multiadditives in thesame sample using FTIR and multivariate analysismethods. For example, the simultaneous determinationof the concentrations of silica, erucamide andbutylhydroxytoluene in PE were measured using IRspectroscopy and suitable calibration models. Theconcentrations were between 20 and 1100 wt/ppm(366). A multiadditive method was developed forcharacterisation of an antiblocking agent (silica) andlubricant (erucamide) in molten low densitypolyethylene (LDPE) samples (324).


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A method for the determination of vulcanised rubberadditives by FTIR spectroscopy using partial least-squares regression (PLSR) for multivariate calibrationwas developed (264). Interestingly enough,photoacoustic FTIR spectroscopy was used tocharacterise tread lugs sectioned from two worn off-the-road tyres. The tyres had experienced similarservice but displayed significantly differentperformance in that ‘chipping/chunking’ was visiblein one tyre brand. The technique was also used toexamine a variety of rubber compounding ingredients,such as polymers and fillers, and model tyre compoundscontaining different levels of these ingredients (341).A long standing problem in analysing natural rubber(NR) is the determination of attached nitrogenouscompounds. Bands at 3280 and 1540 cm-1 diminishedwhen a fresh field latex was treated with enzymefollowed by washing in the presence of surfactant. Aband at 3320 cm-1 that remained after the treatmentindicated the presence of residual amino acids bondedto the hevea rubber particles (349).

A surface method of measurement of a sizing agent(partly hydrolysed polyvinyl alcohol) on the warp yarnsubstrate (polyester/cotton) using NIR diffusereflectance spectroscopy has been described (337). Apartial least-squares (PLS) modelling procedure useda frequency segment of the NIR spectrum that is mostsensitive to changes in size concentration relative tothe warp yarn.

7.1.2 Chromatographic Separation andIdentification

The combination of chromatography and IRspectroscopy provides a versatile tool for thecharacterisation of additives. High performance liquidchromatography-FTIR (HPLC-FTIR) interface systemsdeposit the output of a chromatograph on an IR opticalmedium, which is then scanned to provide data as atime-ordered set of spectra of the chromatogram (138).A spray-jet interface is used to deposit the effluent froma narrow-bore liquid chromatography (LC) column ona zinc selenide window. The deposited additives areanalysed by FTIR transmission microscopy, yieldingidentification limits in the low-nanogram range (215).Although it is not a real time analysis, it has theadvantages of total solvent removal before IR analysis,analysis of the total LC effluent as opposed toincremental fractions, and the ability to produce IRspectra at high SNR.

A powerful new method of additive extraction has beendeveloped termed supercritical fluid extraction/FTIR

spectroscopy (SFE/FTIR) (303). The SFE/FTIRtechnique has been applied to the analysis of fibrefinishes on fibre/textile matrices. Three different fibrepolymer types were examined (polyurethane (PU),polyamide (PA) and aramid), each requiring a differentfinish. Finishes ranged from a single-componentpolydimethylsiloxane (PDMS) oil to more complexmulticomponent finishes that included varioussurfactants, fatty acid esters and soaps, antioxidantsand oils.

7.2 Determination of the Chemical Structure ofa Repeating Unit

The most common type of structure determination isstructure verification. In this case, enough informationis available (perhaps on the basis of well-knownsynthetic reaction paths) to propose a probablestructure. The structure information which is achievedusing IR and Raman spectroscopy is usually sufficienthere. One of the fundamental problems in polymerscience is the determination of the chemical structureof the repeat unit; this moiety determines all of thechemical properties such as reactivity, stability andweatherability. Vibrational spectroscopic techniques areadvantageous as a method of determining structurebecause the methods are applicable to all polymersregardless of the state of order. The IR and Ramanspectroscopy methods are accurate, faster than chemicalanalysis and reduce exposure to irritating, toxic andcorrosive chemicals.

Bisphenol A phenoxy polymers and bisphenol Apolycarbonates were blended in solution. Chemicalchanges from aromatic to aliphatic carbonate groupswere monitored by FTIR as a function of time andtemperature (348).

The network structure of an epoxy resin system andthe course of reaction of bisphenol A diglycidyl etherwith 1-cyanoguanidine as curing agent dissolved indimethyl formamide in the presence of differentaccelerators were studied. Fractions of reactive groups,such as oxirane rings, primary and secondary hydroxylgroups, imide and nitrile groups, were detected asfunctions of epoxy consumption and reactionconditions. Structural tautomerism of the curing agent,the influence of water, the reaction of nitrile groupsand other structural features of the curing system wereexamined (354).

The compound n-butyllithium was the initiator andcyclohexane the solvent for high-vinyl polybutadienesproduced from anionic polymerisation. Complexing


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agents were used to change the mode of addition to1,2 or vinyl, 1,2-dipiperidinoethane and diglyme werevery effective, although their effectiveness decreasedwith temperature. The microstructure of the polymerswas characterised by Raman spectroscopy using theRaman active carbon-carbon double bond stretchingbands of cis and trans vinyl structures at 1640, 1650and 1664 cm-1, respectively. The amount of eachcomponent was measured using band areas (369).

An IR method was developed for determining thehydroxyl number in samples of polyesters formed bythe copolymerisation of a hydroxy-functional acrylicoligomer with adipic acid and 1, 6-hexanediol (370).

Oxazolidone-isocyanurate polymers were prepared byreacting five glycidyl ethers with 4, 4´-diisocyanato-diphenylmethane in the presence of 2-ethyl-4-methylimidazole. The degree of cure of the resins wasfollowed by IR spectroscopy by measuring the fractionof the isocyanurate to oxazolidone linkages (377).

7.3 Crystalline and Conformational StructuralOrder in Polymers

7.3.1 Introduction

IR and Raman spectra are particularly sensitive to theconfigurations and conformations of the polymermolecules. The variations in the conformational andconfigurational structures are reflected in specificobservable frequencies. Consequently, it is possible todetect and quantify the amounts of the conformationalisomers whether they be crystalline, liquid crystalline,or disordered (amorphous). The vibrationalspectroscopic approach to structural elucidation inpolymers relies on the comparison of vibrationalspectra of polymers containing specific conformationalstructures (incorporated into the polymer duringpolymerisation or by thermal or chemicalmodification), with spectra of models (polymers andsmall molecules) containing similar structurespresumed to be present in the polymers.

7.3.2 Crystal Phases of Polymers

Structural changes in the orthorhombic-to-hexagonalphase transition of PE crystals were investigated in thecourse of heating to the melting point. The IR andspectral patterns characteristic of the hexagonal phasewere confirmed. In particular, the bands characteristicof the disordered short trans segments (shorter than

five methylene units) and the bands of the kink ordouble gauche linkages were detected. The observationof the trans and gauche bands was confirmed as wellas the existence of conformationally disordered chainsin the hexagonal phase (195).

The defect density of states of the tight (110) fold inPE is calculated. Modes of the (110) fold calculated at1348, 1342 and 1288 cm-1 and are assigned to IR bandsat 1346-1347 cm-1 and 1342-1343 cm-1 and near 1295cm-1. The (110) folds (approximately g′g′ggtg) alsocontribute to the gtg/gtg′ bands at 1368 cm-1, whereg = +60° and g′ = -60° from the plane of the C-Cbackbone and t = trans. In contrast to the (200) fold,the (110) fold does not exhibit a localised gap modenear 700 cm-1. The observed IR bands are assigned tothe defect modes of the (110) fold (373). The (110)folds are folds in the crystal plane and (200) folds liealong the (200) crystal plane.

The phase transition in an ethylene-tetrafluoroethylenealternating copolymer from the orthorhombic to thehexagonal structure is a result of the generation andpropagation of conformational collective defects (182).

Syndiotactic poly-p-methylstyrene (PPMS) exhibitsvarious crystalline forms and clathrate structures. Bandsdue to the syndiotactic stereostructure and bands typicalof the two different chain conformations are observedin the crystalline structures as well as bands sensitiveto intermolecular interactions typical of the differentmodes of chain packing (350).

In polyamide 66, normalised absorbances of thebands at 924 and 1136 cm-1 were plotted againstdensity and the intercept at zero absorbance provideda density of 1.26 g/cm3, which was very close to thecrystalline density. The 924 and 1136 cm-1 bandsare assigned to the conformation in the amorphousphase. The assignments of the bands at 936 and 1200cm-1 to the conformation in the crystalline phasewere confirmed (31).

FTIR analysis provided a direct method for theevaluation of the amount of alpha and beta formcrystalline phases in syndiotactic PS, although bothcontain chains in the same conformation (trans-planar)(186). Syndiotactic PS was found to exhibit two distinctvibrational peaks in the Raman spectrum. The presenceof long all-trans sequences gives rise to a peak at about773 cm-1, whereas trans/gauche conformations resultin a separate peak at 798 cm-1. With increasing levels ofcrystallinity, the integrated intensity of the 773 cm-1

grows at the expense of the 798 cm-1. The relative area


19

under the all-trans fundamental band can be directlyrelated to the crystalline volume fraction (173).

Cyclohexa(p-phenylene sulfide) (CHPS) is a precursorof poly(p-phenylene sulfide) (PPS). The FTIR andRaman spectra of CHPS resemble those of amorphousPPS. Specific modes indicative of the crystal structureand band shifts are reported and a crystal structurechange in CHPS which was induced by pressure orheat is identified (84).

7.3.3 Complex Formation between Polymers andComplexing Agents

Interactions between polyvinyl chloride (PVC) andcyclohexanone or n-methyl-2-pyrrolidone generatedthe occurrence of local configurational changes. Theresults suggest that the interaction is restricted to adefinite number of polymer sites although noinformation as to the exact type of these sites can bedrawn. The number of interaction sites is higher forcyclohexanone than for N-methyl-2-pyrrolidone (181).

The IR spectrum of the delta phase of the syndiotacticPS/ethylbenzene complex predominantly involvedbands in the 920 to 960 cm-1 region arising from helicalstructures. The 934 and 943 cm-1 peaks behaved as adoublet, primarily due to the delta phase, with thesplitting increasing on annealing. The 940 cm-1 peakwas solely due to the gamma phase helix. Theseassignments provide the opportunity for using thesebands for further studies of complexation/decomplexation in systems of this type (89).

7.3.4 Conformational Analysis

A study of annealed polycarbonate showed that theheating process was primarily a modification oftrans-trans and trans-cis population of the carbonategroup, leading to a more stable structure with a lowerinternal energy. Ageing proceeded mainly byextremely local rearrangements compatible with adensified structure (177).

The IR characteristic bands at 1230/1250 cm-1 ofstereoregular polyacrylonitrile (PAN) are dependenton not only the configuration, but also on theconformation through the arrangements of theconfigurations on the polymer chain. The effect ofconfiguration and conformation on the IR results wasdetermined to be a function of the film preparationconditions (180).

Isotactic PS samples were shock-cooled andsubsequently freeze-dried from very dilute solutionsin benzene. FTIR studies on these samples indicatedthat there were conformational differences betweenthese samples and a normal isotactic PS. Comparisonof the IR spectra indicated that spectral changesoccurred at the bands near 1261, 1085-1050, 982, 923-906 and 550 cm-1. The changes in intensity of thecrystalline bands showed that the freeze-driedisotactic PS from a very dilute solution exhibited ahigher crystallinity than annealed samples (252).

The conformational structures of polycarbonate werestudied in the solid state and in solution. Based onthe temperature dependences of the IR spectra, bandssensitive to transitions between the trans-trans andtrans-cis conformations of the carbonate group wereidentified (361).

The conformers of the ethylene glycoxy moeity ofPET, have been studied in the amorphous andcrystalline regions. The profiles of the 382 cm-1 bandand the 1020 cm-1 band for a series of specimensannealed at different temperatures. Consistent resultswere obtained from both bands for the compositionsof the three conformers, i.e., the trans conformer inthe crystalline state and both the trans conformer andthe gauche conformer in the amorphous state (365).

Poly(ethylene 2,6-naphthalate) (PEN) filmcontaining alpha, beta and amorphous phases wereprepared, and the amorphous contribution digitallysubtracted to yield the characteristic spectra of theamorphous, alpha, and beta phases. In other words,the amorphous spectrum is determined by meltingthe polymer, so after subtraction, one knows thespectrum of all of them. The alpha crystal formadopts an all-trans conformation, while the betacrystal form adopts a conformation with appreciablegauche character. Conformational changes in PENoccur due to the rotation of the naphthalene ring aswell as rotation of the ethylene glycol units. Thenormalised absorbances of the bands at 824 and 814cm-1 were correlated to polymer density, and can beused to represent the amorphous and alphacrystalline phases, respectively (56).

7.3.5 Nematic Ordering in Polymer DispersedLiquid Crystals

Real-time FTIR was used to study the curing of a UV-curable prepolymer (NOA65) and its mixtures withliquid crystals. Curing reactions were examined as afunction of film thickness, temperature, and liquid


20

crystal content. While there was little dependence ofthe curing behaviour on the thickness of the film, theeffect of temperature was strong. Curing ratesexhibited a maximum around 325 K, whileconversions reached a plateau about 20 K higher.Liquid-crystal addition depressed the conversion.However, compared with the neat matrix, the finalconversion was significantly lower only for phase-separating concentrations. The rate of reactiondecreased, and the induction period for the onset ofpolymerising reactions increased, with increasingliquid-crystal concentration (38).

Nematic ordering can be observed and quantifiedbased on a change in a characteristic band of the liquidcrystal. Moreover, the phase separation and the onsetof nematic ordering can be temporarily resolved. Theconversion at phase separation decreased stronglywith an increase in liquid crystal content, while theconversion required for phase separation increasedwith increasing temperature. The fraction of liquidcrystal present as nematic droplets and total fractionof nematic domains in NOA65 were quantified fromchanges in the vibrational spectrum of the liquidcrystal (E7, which refers to the commercial label forthe liquid crystal) (37).

7.4 Quantitative Analysis

The primary result of IR transmission spectroscopyis the transmittance of the cell plus sample, (It)/(Io),

where Io is the intensity incident on the cell and It isthe intensity which leaves the cell, both measuredoutside the cell (Figure 4).

The absorbance is calculated as -log10 (It)/(Io) and isequated with EmCl, the molar absorption coefficient(Em) multiplied by the concentration (C) multipliedby the pathlength (l) through the liquid. This is theBeer-Lambert law.

The absorbance is a measure of energy lost from theradiation beam solely because of absorption by thesample. The experimental absorbance is a measureof the energy lost because of absorption by thesample, plus the energy lost because of reflectionfrom the interfaces of the cell plus the energy lostbecause of unexplained baseline errors. The energylost because of unexplained baseline errors may bepositive or negative.

Quantification requires knowledge of the beam paththrough the sample. Hence, the sample often needs tobe modified to allow for a known geometry. Spectralsubtraction, least square regression analysis, PLS andspectral deconvolution are some of the spectroscopictechniques widely used to quantify constituents in amulticomponent sample. For almost any type ofspectroscopic analysis, this is usually the first step. Itis especially important for polymers given thevariations in spectra for the same polymer due tomolecular weight, conformation, crystallinity, samplepreparation, age and sampling method.

Figure 4

Transmission IR sampling techniques


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7.5 Copolymer Composition and Structure

Direct measurement of absorbance of differentfunctional groups, measurement of end groups, analysisof specific interactions and monomer concentration canall be used to monitor quantitative copolymercomposition. Copolymer composition is determined byusing the absorbance intensity ratio of monomerspecific vibrational modes of vibration. A number ofcopolymer systems have been investigated:

Copolymer system item/no.

epichlorohydrin-gylicidyl ethers (28)

ethylene-acrylate (184)

EVA (72)

EVA (141)

ethylene-vinyl alcohol (258)

ethylene-propylene (110)

ethylene-propylene (123)

ethylene-propylene-diene (EPDM) (155)

acrylic/methyl methacrylate (124)

formaldehyde-phenol (127)

2-((phenylamino)carbonyl)-oxyethylmethacrylate (338)

maleic anhydride-styrene (343)

7.6 Polymerisation Kinetics and Mechanism inMulticomponent Systems

7.6.1 Approach

The synthesis of polymeric materials from lowermolecular weight materials usually involves IR orRaman characterisation at some stage. The completespectrum of a reacting species can lead to informationof the concentration of each species involved withoutthe need to stop the reaction or disturb it in any manner.The sample may be easily heated, exposed to UV, orexposed to electrical and magnetic fields or lasers withminor customisation of the sample holder (all in situand for most reactions) in real time. Hence, thesetechniques are used to characterise the polymerisationprocess for many systems.

Real-time chemical processing and analysis yieldsimprovement in product consistency and quality whilemaximising process efficiency. IR and Ramanspectroscopic techniques can be used for the study ofkinetics of copolymerisation and terpolymers. These

techniques are fast and can monitor the conversioncurves in real time. IR and Raman techniques candetermine in the course of the process thepolymerisation and copolymerisation rates in the courseof the process separately for each monomer bymeasuring variations in the intensity of IR and Ramanbands of the reacting groups.

In situ IR and Raman fibre optic probes can be placedat specific locations within the growing polymer totarget the evolution of polymerisation chemistries atthe surface or core of the process. The vibrationaltechniques of IR and Raman spectra permit betteridentification of spectral differences between monomerand polymer. The specificity of the technique, the speedof data acquisition and the portability of equipment allmake this method ideal as a tool to fundamentally probehow the distribution of individual chemical specieschange during the polymerisation. Its utility is inunderstanding the mechanism of a polymerisationincluding modifications including a catalyst or novelformulations and changes in the polymerisationconditions. The kinetic parameters can be evaluatedand the models for the polymerisation mechanismdeveloped. Isothermal experiments can be performedfor a series of reaction temperatures and used todetermine the overall activation energy of thepolymerisation reaction.

7.6.2 Examples Using IR Fibre Optics

Isobutylene polymerisation initiated by 1,2-epoxy-2,4,4-trimethylpentane (TMPO-1)/TiCl4 was studiedusing IR fibre optics. The initiating mechanism involvesthe formation of tertiary carbocations, by both SN1 andSN2 paths. From the linearity of the first-order plots ofmonomer consumption, and the near uniformity of thepolyisobutylene, it was concluded that livingpolymerisation conditions prevailed (i.e., notermination step) (32). The ATR head can monitor verylow concentrations (0.1 mmol/l) (49).

A linear-chained epoxy resin was formulated fromphenyl glycidyl ether and nadic methyl anhydride,catalysed by benzyldimethylamine (248). An IR fibre-optic probe was used to follow the conversion of athermosetting tetrafunctional epoxy resin in which thehardener was an aromatic diamine and a carboxylicdianhydride. A polymerisation system consisting of acycloaliphatic diepoxide, epoxidised natural rubber(ENR), glycidyl methacrylate (GMA) and a cationicphotoinitiator, triphenylsulfonium hexafluoro-antimonate, was studied (75). Multifunctional epoxy/amine formulations (Epon 825 plus 4,4'-methylene-


22

dianiline) were examined by NIR spectroscopy (276).The polymerisation of bisphenol A diglycidyl ether andtetraglycidyl diaminophenyl methane and amine curingagents, i.e., 4,4'-methylenedianiline and diamino-diphenyl sulfone, were studied using near IR methods(277). Using an embedded silica optical fibre monitoredin situ by evanescent wave spectroscopy, the epoxyring-opening and crosslinking reactions could befollowed in real time (217). IR-transmitting opticalfibres as evanescent wave sensors (59) were used tostudy rigid PU/polyisocyanurate foam formation usingnew catalysts promoting different phases of PU foam.

7.6.3 Examples Using Raman Fibre Optics

Raman fibre optics has been used to study the emulsionhomopolymerisations of styrene and n-butyl acrylate(35). An IR spectroscopic technique for the examinationof radical copolymerisations of acryl and vinylmonomers was developed. A comparative study of thecopolymerisation of model monomer pairs was madeusing monofunctional and polyfunctional compounds.The data established the role of structural-physicaltransformations, involved in the formation ofcrosslinked polymers, on the copolymerisation kineticsand on the nonuniformity of distribution of crosslinksin the copolymers formed (151). Raman fibre optics ofpolymerisation of acrylic terpolymers was also usedto monitor as well as an on-line measurement ofmorphology/composition (66). The high temperature(330 °C) cure reaction of 4-phenoxy-4'-phenyl-ethynylbenzophenone was monitored using amodulated fibre optic FT-Raman spectrometer (80).

The time-dependent evolution of the polymerisationand copolymerisation reactions of styrene/unsaturatedpolyester resin was characterised using opticallevitation with Raman spectroscopy (135). The n-butyllithium-initiated anionic polymerisation of styrenein ethylbenzene was measured using Ramanspectroscopy (214).

Raman experiments were performed on cationicphotopolymerisations of a divinyl ether initiated witha diaryliodonium salt of hexafluoroantimonatephotosensitised by anthracene. Isothermal Ramanexperiments were performed for a series of reactiontemperatures and were used to determine the overallactivation energy of the polymerisation reaction (240).

A Raman spectrophotometer was used to measure insitu the polymerisation rate of acrylamidephotoinitiated by hydrogen chromate anion in aqueoussolution upon irradiation by laser beam (ionised argon)

(363). Changes in the FT-Raman spectrum of 1,4-bis(3-quinolyl)buta-1,3-diyne as a function of gamma-raydosage are used to monitor the degree of monomer topolymer conversion in a solid-state topochemicalpolymerisation reaction (i.e., polymerisation directedby the solid-state structure) (315).

7.6.4 Examples Using Rapid Scan FTIRSpectroscopy

An IR technique can obtain spectra every 5-10 secondsof a reacting PU foam system having a giventemperature profile (360). The real-time IRspectroscopy method was found to be particularlyuseful for analysing high conversion kinetics. Resultswere obtained also for poly(ethylene glycol 200)dimethacrylate and poly(ethylene glycol 600)dimethacrylate (263).

FTIR spectroscopy was applied to the study ofpolymerisation kinetics of simultaneous inter-penetrating polymer networks composed of PU andvinyl ester resin (238). The comparison of vinyl esterresin with or without its pendant hydroxyl groups wasalso made to examine the intercomponent chemicalbinding effect.

The copolymerisation of N-cyclohexylmaleimide(CHMI) and methyl methacrylate (MMA) usingazobisisobutyronitrile as the initiator using rapid scanIR. Using the Mayo-Lewis equation, the reactivityratios of CHMI and MMA were calculated (64).

By measuring the presence of functional groups at finitedepths from the crystal surface by real time ATR-FTIRspectroscopy, the conversion during acrylatepolymerisations was measured. By varying the filmthickness, the reactivity of multiacrylates could bespatially resolved (262). The simultaneous monitoringof vinyl acetate (VA) and erucamide additiveconcentrations in EVA copolymers was undertakenwith NIR spectroscopy using an in-line flow cellattached to an extruder (130).

Monitoring the imidisation of a polyamic acid madefrom 3,3',4,4'-biphenyltetracarboxylic dianhydride(BPDA) and p-phenylenediamine (PDA) wasaccomplished using IR spectroscopy (115).

FTIR spectroscopy was used with a common kineticsprogram to monitor the two separate reactionsoccurring during thermal curing of acetylene-terminated polyisoimide prepolymer (242).


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By the use of NIR instrumentation designed specificallyfor the process environment, the isocyanate content ofa urethane polymerisation reaction is monitored in real-time (265).

The cure mechanism for curing triglycidyl p-aminophenol with diaminodiphenylsulfone was studied. Theconcentration of primary and secondary amine andepoxide groups were monitored directly as a functionof cure with NIR spectroscopy. In similar fashion,monitoring of the percent conversion of methylmethacrylate to PMMA in situ in a mould used short-wavelength NIR spectroscopy. NIR spectroscopy wasalso used to monitor conversion during conventional,anionic solution polymerisation of styrene and isopreneto homopolymers and block copolymers (314).

FTIR spectroscopy was used to study thepolymerisation of random copolymers of 4-vinylphenolwith n-alkyl methacrylates which were prepared by freeradical copolymerisation of 4-t-butyldimethyl-silyloxystyrene and the corresponding alkylmethacrylates in benzene at 60 °C using azobisiso-butyronitrile (AIBN) as an initiator (321). The thermalreaction of polyphenylene-1,2-dibromoethylene underargon flow was investigated using in situ kinetic IRspectroscopy (345).

Stopped-flow FTIR spectroscopy was used to followgroup transfer polymerisation (GTP) and cyclicoligomeric carbonate formation. The effect of catalyststructure, propagating end stereochemistry and degreeof polymerisation on the rate of monomer addition inGTP was investigated (329).

7.7 Polymer Blends

7.7.1 Utility of Polymer Blends

Many practical benefits can be obtained by blendingpolymers. Blending allows for the beneficial propertiesof two polymers to be combined in one material whileshielding their mutual drawbacks. Deviations in the ruleof mixing can lead to properties of the blend over andabove those of its components. Thus, processibility,chemical and environmental resistance, adhesion, andmechanical properties of polymer blends are superiorto those of their homopolymers.

The attractiveness of blending lies in the property-tailoring possibilities. However, most binary mixturesof polymers are not miscible on the molecular levelbecause the entropy of mixing is not favourable for

high molecular weight polymers. As most polymerpairs are immiscible, they form multiphase systemswith weak physical and chemical interactions acrossthe phase boundaries. As a result, immiscible blendsexhibit poor mechanical properties.

Miscibility in polymer blends results from the Gibbsfree energy of mixing (∆Gm) being a negative value.This term combines the effects of both entropy andenthalpy. It has been well established that the formergenerally has a weak contribution in the case ofpolymers because of their high molecular weight. Thelatter is related to interactions occurring at thesegmental level between polymers and mainlydominates the miscibility of the blends.

7.7.2 Miscible Blends

7.7.2.1 Compatibilised Blends

Compatible blends are two-phase materials withproperties controlled by the properties and geometryof each phase and the nature of the connectivitybetween phases (compatiblilisers modify/improve theinterface). In some cases, the addition of small amountsof an A/B copolymer compatibiliser will result in acompatibilised A-B blend morphology that hasimproved mechanical properties. The compatibiliser isconsidered to be located mainly at the interface betweenthe two immiscible polymers, where it induces localmiscibility. The compatibliser lowers the interfacialtension and allows the dispersion of the incompatibilehomopolymers into small, microscopic domains.

The following blends have been studied:

• PP-LDPE with poly(propylene-g-maleic anhydride)and poly(ethylene-co-vinyl alcohol) as in situreactive compatibilisers (117),

• PET-LDPE compatibilised with diethylmaleategrafted polyethylene (120), and

• EVA copolymer compatibilised with terpene-phenolresins (TPR) (165).

7.7.2.2 Reactive Blends

Reactive blending is an important method for thecompatibilisation of polymer blends. Two or moreimmiscible polymeric components are functionalisedwith chemical units that are coreactive. During melt


24

processing, the polymers chemically react to form acopolymer at the interface between the two phases. Thiscopolymer reduces the interfacial tension between thetwo phases, provides for better dispersion, andpromotes adhesion between the two phases.

A highly crosslinked epoxy resin was modified byreactive blending with bisphenol A polycarbonate. Thebisphenol A polycarbonate was dissolved at hightemperature in the uncured epoxy resin before thecuring process. The physical and chemical interactionsbetween the two components were studied by IR.Isothermal measurements showed that the presence ofpolycarbonate did not affect the overall curingmechanism but decreased both the initial reaction rateand the final conversion of reactants (278).

7.8 Conducting Polymers

The 2000 Nobel Prize in chemistry was awarded toHeeger, MacDiarmid and Shirakawa for turningpolymers which are traditionally insulators intoconductors. They found that by doping polyacetylene,it became conducting. This discovery resulted in theestablishment of new types of organic materials thatcombine the processing and mechanical advantages ofplastics with the electronic and optical properties ofmetals and inorganic semiconductors. Considerableeffort has been directed at determining the structuralbasis of this unusual observation.

The chemical structure of electrically conductingpolypyrrole films doped with p-toluene sulfonate anddodecyl sulfate was studied by FT-Raman spectroscopy.The spectra were compared with those from thecorresponding reduced polymers after dedoping andfound to be consistent with polaron and bipolarondescriptions of the electron transport mechanism inpolypyrrole (331).

Resonance Raman spectroscopy was used to investigatethe products formed upon iodine doping of cis-polyisoprene. Evidence for the production of polyeneswas found and that these are in part responsible for theincreased conductivity of iodine-doped cis-polyisoprene (374).

In situ Raman studies of the conducting and non-conducting poly-n-vinylcarbazole showed that theconducting polymer had a 3,3'-dicarbazyl structureformed by dimerisation at the 3,6 position. Theconducting polymer was also obtained by electrolysisof the nonconducting polymer dissolved in

dichloromethane. The conducting polymer obtained bythis method was found to have a similar structure tothat obtained by direct electrolysis of the monomer.These spectra showed that there were no significantstructural changes occurring in the conducting polymerduring the polymerisation process (292).

7.9 Emulsion Polymers

Emulsion polymerisation is characterised by the factthat a free radical initiator (usually water-soluble) isused to polymerise free radically polymerisablemonomers to give a water-insoluble polymer. The mainingredients of an emulsion polymerisation systeminclude monomer, dispersant, emulsifier and initiator.Water is often used as the dispersant. A water-insolublemonomer can be dispersed in water by means of anoil-in-water emulsifier and polymerised with a water-soluble initiator. Styrene, MMA and VA are systemsfor which emulsion polymerisation are commonly used.

An important characteristic of emulsion polymerisationis that, unlike other polymerisation processes, thepolymerisation rate and molecular weight can beincreased at the same time. This is due to thecompartmentalisation of the system that reduces theprobability of mutual termination of the propagatingradicals. The behaviour of this compartmentalisedsystem depends on the rate of exchange of speciesbetween the elements of the system.

Emulsion polymerisation gives particles in the diameterrange ~50-500 nm, with the ability to accurately controlparticle size. Particle stability is usually achievedthrough the use of surfactants.

The direct analysis of the organic phase of an emulsionpolymerisation is possible. Quantification involves usingthe bending mode peak of water, which makes up thebulk of the reaction medium, as an internal standard.The process is demonstrated for MMA but is generallyapplicable to emulsion polymerisations. It does notrequire the introduction of an extraneous internalstandard component into the reaction mixture (319).

FTIR spectroscopy was used to study hydrogen bondingin films of PU and core shell type polyacrylate-PUmicroemulsions. The effects of hydrogen bonding oncomposition and core shell ratio, and its relationship tocrosslinked structures (Type A and B) was revealed (60).

PS microspheres, produced by microemulsionpolymerisation, generally contain only one or a few


25

polymer chains, and may thus be termed single- orpauci-chain microspheres. Changes in chainconformation on heating were studied using in situFTIR spectroscopy (85).

The phase transition between micellar phases ofpolyethylene oxide-polypropylene oxide-polyethyleneoxide) (PEO-PPO-PEO) triblock copolymer in aqueoussolution was investigated as a function of temperatureusing FTIR spectroscopy. As the temperature increases,PO blocks appear to be stretched conformers withstrong interchain interactions, and the formation of ahydrophobic core in the micellar phase. The EO chainsare found to change to a more disordered structure withlow-chain packing density. Both the EO and PO blocksexhibit dehydration during the phase transition (78).

Using a thermal micro ATR/FTIR spectroscopic system,a quantitative investigation was made of the molecularinteractions in aqueous solutions of poly(N-isopropylacrylamide) (PNIPAAM). The results indicatedthat intermolecular interactions predominate betweenPNIPAAM and water at temperatures below the lowercritical solution temperature (LCST). However, abovethe LCST, PNIPAAM molecules in water are aggregatedbecause of intramolecular interactions and hydrophobicinteractions in the system (93).

The nature of the complexes formed by the interactionsbetween polyacrylic acid (PAA) and polymethacrylicacid (PMAA) with poly(4-vinylpyridine) and poly(2-vinylpyridine) in ethanol/water solution was studiedusing FTIR spectroscopy. The PMAA complexesinvolved hydrogen-bonding interactions, while therewas evidence of ionic interactions in the PAAcomplexes. This difference in the behaviour betweenthe complexes is attributed to the higher acidity of PAAcompared with that of PMAA (140).

The FTIR spectra were acquired as functions of watercontent in the range 2.6-38 wt% and temperatures inthe range 300-373 K for hydrated poly(2-hydroxyethylmethacrylate) (PHEMA). The results suggest two typesof water in the hydrogel polymer system, tightly-boundwater and loosely-bound water. At low concentrations,water was mainly hydrogen-bonded to the polymer(tightly-bound water). At water concentrations greaterthan 18 wt%, however, part of the water existed in adifferent form and behaved as loosely-bound water. Itwas also suggested that some of the water continuedto be hydrogen bonded to the polymer until at least atemperature of 373 K when the bulk water should haveevaporated. FTIR spectroscopy was found to yieldgreater site-specific insight into the local behaviour ofwater in hydrated PHEMA (185).

The partitioning of acrylonitrile between particles andthe aqueous phase of polybutadiene latex was measuredby Raman spectroscopy using rubber latex as substrate.Raman line intensities yielded the partition values inthe two phases (295).

7.10 Graft Polymers

Graft copolymers can be prepared by radical graftingof a polymerisable monomer A onto a reactive polymerbackbone B. As a result of the grafting reaction, acomplex product is obtained comprising the graftcopolymer AB, residual ungrafted polymer backboneB and homopolymer A.

The condensation grafting of polyethylenimine (PEI)onto poly(acrylamide-co-acrylic acid) (PAM-co-AA)was studied by FTIR spectroscopy. The reactionmechanism, which proceeded by a two-step reaction,involved the conversion of AA to acid chloride (AC)using thionyl chloride, followed by the condensationof AC onto PAM and with amine onto PEI to form thegraft copolymer (125).

The grafting of PP films by PAA was demonstrated tostart from the interface between the PP and thepolymerisation solvent. The results suggested that itshould be possible to control the location of graftingboth by the content of antioxidants and by theirextraction (322).

LDPE was functionalised in the bulk through dicumylperoxide-initiated grafting of dibutyl maleate andvinyltrimethoxysilane in the temperature range from140 to 200 °C (327).

The structure of EPDM grafted onto polyamide 66 wasanalysed by FTIR spectroscopy. Evidence indicated thepresence of cyclic imide groups, derived from graftedmaleic anhydride groupings (229).

Polyglycidyl methacrylate and their copolymersobtained by radical graft onto polyvinyl alcohol(PVAL) fibres were studied by IR spectroscopy. Thespectra regions sensitive to the sites of localisation ofthe chains of grafted poly(glycidyl methacrylate) arewithin 3600-3100, 1450-1300, 1120-1000 and 700-500 cm-1, which correspond to the stretching andbending OH vibrations, stretching carbon-oxygenvibrations, and torsional vibrations of the hydroxylgroups, respectively. On this basis, it was establishedthat grafted polyglycidyl methacrylate molecules arelinked to PVAL macromolecules via oxygen atomsof hydroxyl groups (255).


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The use of an intermediate barrier layer to vary thepenetration depth in an ATR experiment was used inprobing concentration profiles away from the interface,Application of this technique in the study of PMMA/PDMS graft copolymers deposited onto a copper oxidesurface indicated a preferential presence of the siloxanecomponent at the oxide interface; a concentrationgradient was observed to decrease with increasingdistance into the bulk of the sample film (275).

IR spectra of polycaproamide fibre, polyglycidylmethacrylate and polycaproamide fibre grafted withpolyglycidyl methacrylate were recorded. The spectralregions that were sensitive to localisation of the chainsof grafted polyglycidyl methacrylate were identified,i.e., 3500-3100/cm-1 (stretching vibrations of NHgroups), 1700-1500/cm-1 (Amide I and Amide IIabsorption bands), 1030-900/cm-1 (Amide IV) and 720-640/cm-1 (Amide V). It was found that polyglycidylmethacrylate was grafted to the macromolecules ofpolycaproamide via an amide nitrogen (308).

ATR-IR spectroscopy was used to characterise thegrafting of PP films by PAA. It was shown that graftingalways started from the interface between the PP andthe polymerisation solvent. The results suggested thatit should be possible to control the location of graftingboth by the content of antioxidants and by theirextraction (322).

LDPE was functionalised in the bulk through dicumylperoxide-initiated grafting of dibutyl maleate andvinyltrimethoxysilane in the temperature range from140 to 200 °C. The degree of grafting was determinedby IR spectroscopy. The total surface energy increasedwith grafting. The surface energy of the silane-graftedPE was found to be lower than that of dibutyl maleate-grafted PE (327).

7.11 Degradation of Polymers

The lifetime of many polymer products in use is limitedby oxidative degradation. Exposed samples are usuallynon-uniformly oxidised. At the macroscopic level, theheterogeneities can result from oxygen-diffusion-limited effects. If the rate of oxygen consumptionexceeds the rate of oxygen permeation, oxidationoccurs in the surface layers, whereas the core remainspractically unoxidised. The importance of this effectdepends on several parameters. First, intrinsicparameters are linked to material geometry (e.g.,sample thickness) coupled with the oxygenconsumption rate, which depends on the reactivity of

the polymer, the presence of additives, and the oxygenpermeability of the material. Second, extrinsicparameters such as the conditions of accelerated ageingand the oxygen pressure during ageing are important.

Oxidation is accelerated if the temperature is elevated.Exposure to optical and UV radiation can alsoaccelerate the degradation. Additionally, thethermooxidation and photooxidation are accelerated bygenerating chemical effects by the application ofmechanical forces (i.e., mechano-chemicaldegradation). Vibrational spectroscopy is particularlyuseful for studying the degradation processes as themeasurements can be made in real time.

7.11.1 Degradation with Ionising Radiation

IR spectroscopy was used to follow the ageingprocesses of two types of epoxy resins. Resin sampleswere exposed to ionising radiation and the effects atthe molecular level were determined. Aromatic aminecured resins were only slightly affected by the radiation,but those cured by alkyl diamines were more sensitiveand thus absorbed more water molecules (41).

The effect of radiation dose and the hydrolysisconditions on the chemical structure of electronirradiated PTFE was studied. Irradiation produced acidfluoride (COF) groups and, under ambient conditions,these hydrolysed with atmospheric humidity to formfree and associated carboxylic acid (COOH) groups.The concentrations of these groups were different inthe near-surface and bulk regions. The formation ofcarboxylic groups in different states of associationdepended on the hydrolysis conditions (146).

IR spectroscopic analysis showed that the treatment ofPAN films and fibres by gamma-irradiation led tocleavage of the polymer chains forming carbonyl-containing functional groups, the composition of whichdepended on the treatment conditions (330).

7.11.2 Degradation by Photooxidation

The photooxidative degradation of anhydride-curedepoxies was studied. The degradation washeterogeneous, the surface being much more affectedthan the bulk. The disappearance rate of aromaticgroups was dependent only upon their initialconcentration, while the formation kinetics of hydroxylgroups was determined by the diffusion of oxygen intothe material. The formation of hydrophilic products,


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acids, and alcohols was confirmed by chemicaltreatment, and it was concluded that their presence andhigh concentration at the surface could be responsiblefor the degradation of the insulating properties ofepoxies when used as electrical insulators (112).

PS films were exposed to radiation of long wavelength(above 300 nm) and short wavelength (253.7 nm) underatmospheric oxygen. Changes in the FTIR spectra ofthe photooxidised samples were followed. Theabsorption maxima which were found in the carbonyland hydroxyl regions of the IR were assigned, and thecorresponding photoproducts were identified (351).

IR spectroscopy was used to study the microstructureof propylene-ethylene copolymer samples taken fromseats which had degraded during storage or aged duringoutdoor exposure in an Olympic stadium in Barcelonaover a period of 2.5 years. The changes observedincluded increases in aldehyde and ketone groups anddecreases in unsaturation, peroxide, methyl andmethylene groups and isotacticity. The results indicatedthat the main processes taking place werephotooxidation and chain scission (189).

The photooxidation of a nonwoven PE fabric showedhydroperoxide, alcohol, aldehyde, ketone, carboxylicacid, and anhydride groups were formed as the productsof the photooxidation of the PE fabric and the relativeamount of carboxyl increased as the photooxidationprogressed. Distribution of the photooxidation productswas inhomogeneous between the two surfaces of thefabric. The UV radiation at 254 nm causedphotooxidation of PE. No photooxidation was observedin the fabric exposed to the UV radiation at 350 nmunder the same conditions (288).

PEO and polymethyl vinyl ether were UV irradiatedin hydrogen peroxide solutions. Hydroxy andhydroperoxy radicals accelerate the oxidativedegradation of these polymers. Hydroxy and possiblyhydroperoxy radicals can abstract hydrogen frommethylene groups in both polymers. As a result offurther oxidative reactions, different carbonyl, hydroxyand hydroperoxy groups are formed (297).

7.11.3 Degradation by Thermal OxidationProcesses

During thermal degradation of PAN over thetemperature range 150-590 °C, gaseous and volatileproducts were produced with simultaneous stabilisationof the structure of the residual material. The principal

decomposition reaction was linear polymerisation ofthe nitrile group, with cyclisation followed by extendedconjugation being a significant exothermic process.There was no evidence of the formation of oxygen-containing chromophores (113).

The thermooxidative degradation and SiOx filmformation of poly(vinyl imidazole-co-vinyltrimethoxysilane) on copper was investigated. Thermaldegradation of the copolymer was catalysed by copperin the film and at the substrate surface. Copper in thecopolymer film contributed to the formation of acopper-containing SiOx film during thermaldegradation. Copper oxides in the film interacted withthe SiOx film to form a copper-rich phase near the filmdefects and cracks (142).

The thermal degradation (in vacuo, up to 500 °C), of aVA-methacrylic acid copolymer having 65%alternating units, and of the correspondinghomopolymers, was studied. Polyvinyl acetate (PVA)copolymer crosslinks form due to double bondformation through deacetylation. PMAA generateslittle unsaturation, rather crosslinks by intermolecularanhydride formation. It decomposes above 350 °Cwhen the anhydride breaks down with substantial chainscission. In the copolymer, both types of crosslinkingreactions are disturbed by lactone formation betweenalternating VA and methacrylic acid units. The lactoneformation protects the VA units from deacetylation andcompetes strongly with anhydride formation (273).

The thermooxidative degradation of polyphenylenebibenzimidazole (PBI) and a blend of PBI with Ultem1000 polyetherimide was investigated. The FTIRspectra of the blend were analysed by subtractionspectroscopy, allowing the fate of the two blendcomponents to be selectively studied. No chemicalinteraction between the two components wasdetectable by FTIR spectroscopy during thedegradation process (323).

7.11.4 Degradation by Chemical Exposure

The mechanism responsible for the hardening ofhydrogenated nitrile rubber automotive seal compoundson prolonged exposure to automatic transmission fluidsat high temperature was investigated. The increase inhardness was found to result primarily from chemicalattack at the acrylonitrile sites. This chemical attackfirst resulted in the formation of isocyanide or isonitrileions. The proposed mechanism involved crosslinkingat the acrylonitrile sites through the formation ofisonitrile ions and the subsequent formation of imides.


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The isonitrile intermediate formed ionic bondsresulting in the formation of an ionomer once theconcentration became sufficiently high. Ultimatelythese ions crosslinked to form imides in the presenceof oxygen or water. It was proposed that the increasein hardness was due to the formation of the ionomerand the imides (154).

Differences in bands assigned to carbonyl groups andhydroxyl groups in PET films aged in water suggestedformation of different hydrogen-bonded species. Theautocatalytic nature of the hydrolysis in water wasconfirmed and evidence for the so-called‘chemicrystallisation effect’, with crystallinityincreasing with degradation, was observed (50).

7.11.5 Analysis of Evolving Gases from Polymers

A large number of different techniques are used toanalyse fire gases including gas chromatography, massspectrometry, and IR absorption. FTIR spectroscopycan be used for on-line quantification of evolved gasspecies during heating, burning, and smouldering ofthe sample. The use of FTIR spectroscopy enables anumber of the more important gases to be determinedcontinuously. Evolved gas analysis reveals features duemainly to the corresponding monomers or stable,volatile and low relative molecular weight degradationproducts. These gases include those of particularimportance to PU foam containing fires, e.g., hydrogencyanide, nitrogen oxides, hydrogen chloride andhydrogen bromide (from flame retardant additives) aswell as carbon monoxide and carbon dioxide whichare produced from all fires (236). The IR absorptionspectra are used to identify the individual gas specieswithin the fire gas mixture and the intensities of theabsorption bands are used to quantify the gasconcentrations.

Linear-temperature controlled pyrolysis withsubsequent analysis of the pyrolysates (volatiles andresidues) by FTIR spectroscopy can provideinformation on the thermal degradation mechanismsof polymers including aromatic polyesters (325).Thermal analysis of PS, poly-p-methylstyrene andpoly-α-methylstyrene was carried out using evolved-gas IR analysis (302).

On decomposition, the polybutylene terephthalate(PBT) polymers give off mainly water, carbon dioxide,butadiene, tetrahydrofuran (THF) and PBT oligomers.The flame retardants marginally increased the polymerdecomposition temperature (274).

7.12 Orientation of Polymer Chains Due toExternal Perturbations

7.12.1 Approach using Vibrational Spectroscopy

The elucidation of the mechanisms and dynamics ofsegmental mobility in polymers under the influence ofexternal perturbations can contribute to the optimisationof the engineering properties of technically importantpolymeric materials. Application of a uniaxial orbidirectional stretching is a common method of treatinga polymeric material to improve its mechanical end-use properties.

Generally, time-resolved IR spectroscopy has provedan extremely valuable tool to investigate the structuraldetails of molecular changes incurred by a polymerunder the influence of such an external perturbation.The ability to monitor and model such drawing andrelaxation processes would benefit greatly productquality and web efficiency.

FTIR and Raman spectroscopy are two of the fewtechniques providing data on the crystallisation,orientation and conformational changes of a polymerduring and after mechanical treatment.

Front-surface reflection IR spectroscopy is often usedto characterise the structure of drawn samples. Thisapproach provides the complete IR spectrum, includingthe highly absorbing bands that are often saturated intransmission spectra. ATR techniques are used to depthprofile the changes in orientation.

One approach to characterising the molecularorientation in both uniaxially and biaxially orientedsamples of PET makes use of the ratio of theabsorption bands near 1250 and 1725 cm-1, the firstof which shows parallel dichroism and the secondperpendicular dichroism. An equation is developedthat relates this ratio to the molecular orientation withrespect to the direction of measurement. Thus, it ispossible to determine individually the orientationfunctions with respect to the machine and transversedirections (131).

Several sources of error may influence the calculationsof chain orientation carried with the use of data fromIR dichroism experiments. Three specific problems arethe improper treatment of chain conformation, theimperfect polariser behaviour, and the inaccurateassumptions regarding the value of the angle betweena particular IR-active transition moment and thepolymer chain axis (309).


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7.12.2 Orientation Functions for MechanicalDeformation

FTIR spectroscopy was used to monitor orientationphenomena in highly crosslinked epoxy/aminenetworks during uniaxial deformation above their glasstransition temperature (Tg). The resins were preparedfrom the diglycidyl ether of bisphenol A and variouspolyether di- and triamines in order to examine theinfluence of the structure of the network formed. Themolecular orientation was studied in relation to networkdensity and structure. The orientation behaviour wasmainly determined by the flexibility of the polyetherchain and the homogeneity of the network structure.The epoxy resins were also subjected to successiveloading-unloading cycles. The results showed that theorientation of epoxy networks in their rubbery statewas completely reversible and that no significantfatigue due to gradual chain rupture occurred untilsample failure (253).

IR dichroism was used to study the orientationaldevelopment in the high-speed spinning of Nylon 66yarns. A relationship between IR dichroism andorientation factor was developed and a correlationbetween orientation measured by IR and X-raydiffraction demonstrated (372).

The orientation functions and dichroic difference datafor a commercial polyester-urethane from B.F. Goodrichshowed that, in static stretching, the soft domains reachedorientation saturation before the hard domains. On thetimescale of the static experiment, plasticisationdiminished the ability of both domains to reorient, whilethe plasticiser itself did not orient (55).

Micro-Raman spectroscopy was used to study thestructural changes which occur in the cold-drawingof HDPE. The cold-drawn structure was highlyorientated and a large decrease in the Ramanorthorhombic crystallinity was observed. The resultsindicated an ill-defined orthorhombic crystallinestructure with dislocations and disrupted crystalsformed by cold-drawing, possibly resulting frommolecules being pulled through the crystals. Nodisruption was observed in fibrils created duringenvironmental stress crack resistance (ESCR) tests at348 K. Temperature was an important parameter inthe crystalline phase recovery of the orthorhombiccrystallinity and when the cold-drawn HDPE wasannealed, the monoclinic phase disappeared (94). Therole of an ESCR detergent (active environment)during tensile deformation of PE samples was studied.IR spectroscopy indicated that the detergent waspredominantly present within the transition fronts of

the material. The results indicated that theenvironment penetrated the sample during the neckingprocess and stabilised crazing (99).

ATR-IR spectroscopy at various angles of incidencewas used to study ultradrawn films of PE. A gradientof molecular and crystalline structures was found fromthe surface into the core. The skin was highlyorthorhombic. Moving inside the film, both monoclinicand orthorhombic lattices coexisted. A new phase withisolated trans-planar sequences was observed in thecore. Various kinds of collective and oriented or isolatedconformational disorder were identified. A molecularmodel was proposed for the process of orientationduring drawing (346).

7.12.3 Strain-Induced Crystallisation

The morphology of the strain-induced crystallinematerial produced by drawing amorphous PET isdifferent from that of material obtained by thermalcrystallisation. Furthermore, it has been shown thatthermal crystallisation involves two distinct stages.The primary stage starts to become significant around90 °C not far above the Tg, and shows a sigmoidaldependence on log (time). The secondary stagebecomes significant only above about 140 °C andshows a linear dependence on log (time). Significantdifferences between samples with strain-inducedcrystallinity and one that was thermally crystallisedare observed (90).

Specular reflection spectra (spectra obtained usingspecular reflection sampling) was obtained from thesurface of uniaxially drawn PET samples. The overallorientation function and content of trans-conformersis calculated. The results are correlated with mechanicalmodulus and crystallinity values (251). In uniaxiallydrawn PET films the skeletal structures, such as the C-O bond in the ethylene glycol unit and the phenyl ring,are susceptible to deformation by mechanicalstretching, while the dynamic structural changes aroundthe methylene group are small. It was assumed that thebackbone of the polymer is responsible for the changeof the mechanical properties induced by the drawingof the film (158).

The structure of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) fibres exhibit three crystallinestructures: two orthorhombic, and one pseudo-hexagonal. The orthorhombic crystals with the c-axispreferentially orientate perpendicular to the fibre axis,and pseudo-hexagonal crystals are preferentiallyformed in the drawing process (114).


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7.12.4 Deformation-Induced ConformationalChanges

PVC films were stretched to various elongation ratiosand the dichroic behaviour of 615 and 637 cm-1 bandsof the IR spectrum were investigated. The evolution ofthe dichroic ratios and of the relative absorbance ofthe bands in the direction perpendicular to that ofstretching were compared so the occurrence of localchain orientation related to the conformational changefrom gttg-tt to gtgttt which occurs when PVC isstretched (51).

FTIR polarisation spectroscopy was used to study theorientational behaviour of the different constituents ofa liquid crystalline block copolymer (copolyester-imide) during uniaxial elongation at differenttemperatures. Differences in the degree of alignment(as well as in the response to the application of themechanical load) were observed. With increasingtemperature, the level of the applied stress and theinduced degree of orientation decreased, while thedifferences in the orientational behaviour of themesogen and the flexible spacer were retained (243).

7.12.5 Relaxation Processes after Drawing

Epoxy resin films were subject to various successiveloading-unloading cycles including elongation,recovery, annealing and stress relaxation to study thereversibility of the orientation during relaxationprocesses (197).

The relaxation of the segmental orientation and thechain extension in polycarbonate was studied by IRdichroism and heat shrinkage after a step straindeformation to a draw ratio of 1.75. This made itpossible to distinguish between local relaxationmechanisms and large-scale relaxation mechanisms ofthe molecular orientation. It was found that the averagerelaxation time for segmental orientation is shorter andmore temperature-dependent than the averagerelaxation time for the chain extension. The segmentalorientation relaxes almost totally at 170 °C (Tg 148 °C)before the chain extension even starts to relax (201).

7.12.6 Electric Field Induced Reorientation ofPolymers

Dipole reorientation under the influence of an electricfield has been studied in oriented Nylon 11 films withpolarised IR spectroscopy using the amide A (N-H

stretching) and amide I (carbonyl stretching) bands.Butterfly-shaped hysteresis loops were obtained fromgraphs of peak intensity versus applied electric fieldstrength. Time-dependent studies of the absorptionintensities show that both ordered and disorderedspecies switch towards the electric field direction withthe application of electric fields higher than the coercivefield. Upon field removal, only the disordered speciesshow orientation relaxation away from the fielddirection. Below the coercive field, neither speciesaligns with the field (231).

7.12.7 Laser-Induced Orientation

The laser-induced anisotropy in thin films ofcyanoazobenzene side-chain liquid crystallinepolytetradecanedioates, -dodecanedioates, and-adipates selectively deuterated at different positionswas investigated by FTIR. In polyesters with longmain-chain spacing (tetradecanedioates and dodecane-dioates), not only the light-sensitive azo chromophore,but also the main-chain methylene segment and to asmall extent the flexible spacer are preferentiallyoriented perpendicular to the laser light polarisation.The extent of orientation increases with increasingspacer length. Rapid-scan FTIR analysis performed online with laser irradiation reveals that the alignment ofthe aliphatic segments arises simultaneously with thechromophore orientation (143).

7.13 Time-Resolved Spectroscopy

Time-resolved IR spectroscopy is an extremelyvaluable tool to investigate the structural details ofmolecular changes incurred by a polymer under theinfluence of an external perturbation. The elucidationof the transient molecular changes during polymerdeformation is an important issue in polymerprocessing. The ability to monitor and modelmechanical drawing and relaxation processes benefitsproduct quality.

Time-resolved FTIR is used to study the structure anddynamics of ferroelectric liquid crystalline blockcopolymers. From analysis of the dynamic dichroismof the FTIR spectra, it was concluded that thecomponents in the PS microphase are oriented randomlywhile the liquid crystalline groups form an ordered phase.The switching is of an electroclinic type, in which thetilt angle and the mesogenic motion increase withtemperature, especially if the PS block is heated aboveTg. The orientation of the liquid crystalline block after


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heating to the isotropic phase is completely restored dueto the memory effect (i.e., reversible behaviour) of thepolymer microstructure (101).

Time-resolved FTIR spectroscopy measurements wereperformed under isothermal crystallisation conditionsto clarify the origin of the cocrystallisation and phasesegregation phenomena observed for a series of PEblends between the deuterated and hydrogenatedspecies, The degree of undercooling or the temperaturejump depth (i.e., the size of the temperature drop) fromthe molten state to the isothermal crystallisationtemperature was controlled (96).

7.14 Rheooptical FTIR Spectroscopy

IR spectroscopy can be coupled with the polarisationmodulation technique in order to characterise themolecular orientation in polymer films. A computer-controlled variable-temperature stretching machine isused, which allows monitoring of vibrational spectra andstress-strain diagrams during deformation of polymerfilms up to 523 K (355). Polarisation modulationimproves the SNR and minimises errors generated byrepositioning the sample or the polariser for a secondmeasurement. This technique is capable of measuringsmall dichroic effects with high sensitivity, even for verysmall sample draw ratios (291).

Phase-locked electronics are used to record thedynamic IR spectral change in-phase and out of phasewith the applied mechanical field. The methodprovides insight to the response to the external stresson the molecular and submolecular scale. RheoopticalFTIR spectroscopy is one of the few techniquesproviding data on the crystallisation, orientation andconformational changes of a polymer duringmechanical treatment (83). Two dimensionalcorrelation analysis is utilised to enhance theinformation derived from the vibrationalspectroscopic data.

The IR rheooptical technique was applied to study themolecular processes that take place along the stress-straincurve of PET yarns. The results indicate that the firstmodulus maximum marks the breakdown of theamorphous entanglement network and the start ofmolecular uncoiling by gauche-to-trans transitions. Inaddition, stress develops on the crystals and particularlyon tie molecules with a short contour length in theamorphous domains. Ultimately, molecular fracture oftaut-tie molecules (extended chains of polymers betweencrystals) causes the modulus to pass through a second

maximum. The chain ends of broken molecules recoilby trans-to-gauche transitions. Local stress accumulationwill lead eventually to yarn rupture (320).

The molecular orientation of the epoxy networks wasinvestigated using rheooptical FTIR spectroscopy anduniaxial deformation was carried out above and belowthe Tg. The effects of diol chain length and molar ratioon the mechanical properties and orientation parameterwere discussed (79).

For PS/poly(vinyl methyl ether) blends, the additionof poly(vinyl methyl ether) to the blend increases theorientation of the PS chains during the stretching (92).

Rheooptical FTIR spectra of a thermoplastic polyesterurethane and Nylon 6 films were recorded under avarying sinusoidal strain. The large bipolar bands inthe dichroic in-phase spectra, caused by large frequencyshifts of the original monopolar absorption bands, wereascribed to hydrogen bonds (102).

7.15 Two-Dimensional IR (2D-IR) Spectroscopy

The general experimental approach in 2D-spectroscopyinvolves the application of an external perturbation thatcan selectively excite various chemical components ofa given system. The excitation and subsequentrelaxation processes, which are manifested by changesin peak intensities, shifts in spectral frequencies andvariations in band shape, are monitored by a givenspectroscopic probe.

Two-dimensional-IR spectroscopy is a technique wherethe spectral intensity is plotted as a function of twoindependent spectral variables, e.g., frequency. The twoorthogonal axes of independent spectral variablesdefine a 2D spectral plane, and the spectral intensitymay be plotted along the third axis.

This approach can be used for probing the relationshipsbetween the molecular motions in IR spectroscopy.Two-dimensional-IR spectroscopy providesinformation that cannot be obtained by normal IRspectroscopy. Two-dimensional-IR can aid in theinterpretation of complex spectra, especially with thebroad overlapped peaks commonly encountered withpolymers. The advantage of this method is the abilityto separate overlapping bands and investigate the timesequence of certain spectral events (a.34).

The power of the 2D-IR spectroscopy approach resultsprimarily from an enhancement of the spectral


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resolution that has a physical origin. This effect relieson the dissimilarity between the responses of variousfunctionalities absorbing at distinct frequencies. Onecan also make band assignments between IR bands andbands in NIR and Raman spectra.

Two-dimensional-IR spectroscopy requires a series ofperturbation-dependent spectra. The types of physicalperturbations probed with this technique include:mechanical stress, applied potential, temperature,pressure, concentration and composition (a.35).

In 2D-IR spectroscopy, the sample is perturbedexternally to induce time-dependent fluctuations of theIR signal. The external perturbation can be anyperturbation source that can excite chemical species inthe system, including mechanical, optical, electrical,magnetic, chemical, thermal and acoustic perturbations.The reorientation of each functional group in the samplewith a unique rate, extent, and direction producesresolvable fluctuations in the dynamic IR intensities.The changes are recorded in the dynamic spectra inthe form of variation in the intensities, shifts of spectralband positions and changes in the shape of peaks.

Generalised 2D spectroscopy can handle spectralfluctuations as an arbitrary function of time or of anyother physical variables such as temperature, pressure,concentration and composition. Generalised 2D spectraemphasise spectral features not readily observable inconventional 1D spectra. It helps to probe the specificorder of certain spectral events taking place with thedevelopment of a controlling physical variable. Thegeneralised 2D approach is a qualitative method only;one can interpret only positions and signs of correlationpeaks. The absolute magnitude of these peaks cannotbe directly interpreted since they include informationon both the amplitude and phase changes at twodifferent frequencies (a.36).

A 2D experiment can be carried out using aconventional spectrometer by introducing a relativelyslow external perturbation applied to the system ofinterest. In a typical 2D experiment, a series ofperturbation-induced dynamic spectra are collected insome sequential order. Such a set of spectra may bereadily manipulated mathematically, with the use of asimple scheme of correlation analysis to yield thedesired 2D correlation spectra.

Two-dimensional NIR spectroscopy has been used forstudies on the composition-dependent spectral variationsin EVA copolymers. As a result, additional assignmentsof bands were made to ethylene units in amorphous,disordered, and orthorhombic crystalline phases (73).

Polyester-based PU elastomers contain hard and softdomains. It is desirable to characterise the molecularlevel interactions giving rise to the two domains, andto use this information to monitor chemical changes.The 2D correlation method provides a means by whichthe spectral information arising from the two domainscan be resolved using thermal perturbations (95).

Two-dimensional-IR spectra of glassy atactic PS revealthat while the main-chain backbone reorients in thedirection of applied strain, there also exist highlylocalised reorientational motions of phenyl side groupsoccurring independently of the main-chain realignment.This localised submolecular distortion is not observedat temperatures well above the glass transition (107).

Two-dimensional-IR spectra were used to study theorientation and the mobility of a ferroelectric liquidcrystal dimer during switching by an electric field. Thedetailed mutual arrangements of different molecularsegments (poly(siloxane), poly(methylene) chain,polysiloxane chain) in a smectic C phase were derivedfrom the static spectra. Temperature and electric fieldstrength dependencies of the mobility of these segmentswere established (163).

A 2D-IR spectroscopic study on dissociation andhydrogen bonds of Nylon 12 over a temperature rangeof 30-150 °C showed gradual weakening of inter- andintramolecular associative interactions and a decreaseof local order leading to the eventual fusion. (167). Theasynchronous 2D-NIR spectra indicate that the amidegroups with a free carbonyl oxygen appear first, andthen unassociated free amide and amide with free NHfollow as the temperature is increased (174).

Two-dimensional-IR spectroscopy was used to studythe N-H stretching and amide I/amide II region of melt-crystallised Nylon 11 thin films on Teflon substrates.The samples were mechanically oscillated at afrequency of 11 Hz. The dynamic spectra indicated thatthe N-H stretching region splits into two peaks.Analysis of 2D cross plots between the N-H stretchingregion and the amide I/amide II region showed that theprominent peak in the N-H stretching region (about3300 cm-1) was similar in morphological character tothe ordered peak of the amide I region. The amide IIregion resolved into two ordered and one disorderedpeak (254).

Two-dimensional-IR spectroscopy involvingmechanical excitation has been employed to study themechanical relaxation phenomena in an acrylonitrile-butadiene-styrene terpolymer (ABS) sample. The studyrevealed detailed information regarding the molecular


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segments involved in macroscopic mechanicalrelaxation. From the temperature dependence of thedynamic signals it is corroborated that in the ABSsample the polybutadiene rubber relaxes entirelyindependently from the styrene-acrylonitrile copolymer(SAN) matrix, and thus is present as a separate phasein the material (169).

A 2D-IR spectroscopic analysis on the dynamic spectraindicates that neat LDPE is comprised of three regions:an ordered crystalline region, a disordered liquid-likeregion, and a crystal/amorphous interfacial region. The1468 cm-1 peak in the methylene bending region isassigned to the all-trans structures which primarilyreside in the interfacial region. A variety of LDPEsamples with different additives were used in order todetermine how the additives influence the dynamicmechanical properties of each morphological phaseLPDE. It is found that talc associates with thecrystallites, EVA is distributed in all threemorphological phases of the LDPE, and pyrene isassociated only with the non-crystalline regions (218).

Two-dimensional-IR spectroscopic analysis was usedto monitor the submolecular orientational responses ofthe components of a semicrystalline 50/50 blend ofLDPE with perdeuterated HDPE to a small amplitude,uniaxial, 23.47 Hz, sinusoidal mechanical strain.Analysis of the data indicated that the crystalline partsof the two components reorient at different rates, withthe functional groups of the high density portionreorienting faster, in general, than those of the LDPEin response to the mechanical strain (316).

FT-Raman spectra were determined for atactic PS,poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and theirblends. Composition-dependent spectral variations ofthe blends were analysed using generalised 2-Dcorrelation spectroscopy to study the conformationalchanges and blend interactions. The 2D synchronouscorrelation analysis was able to discriminate betweenthe bands of PS and those of PPE, and was able todetect bands that were not readily identifiable in 1Dspectra. The main chain conformation of PS undergoesa drastic change on blending with PPE (57).

7.16 Recycling of Polymers

One of the main causes of the high costs of recyclingis sorting. It is essential to separate collected post-consumer waste in order to obtain plastics of onesingle type to feed the recycling process. The additionof chemical additives and new granular plastics can

only be done efficiently with the knowledge of allrelevant physical and chemical properties of thecollected basic material.

As physical methods are not sufficient, theidentification method has to monitor structural ormolecular properties of the polymers. The NIR spectralrange (700 to 2500 nm) allows the monitoring ofstructural or molecular properties of the plastic articlesunder investigation for recycling. The reducedabsorption in the NIR allows registration of spectra ofbulky plastics of practical interest in recycling. For fastscanning of the wavelength region of 1000 to 2200 nm,spectrometers based on AOTFs with a scan speed of1000 nm/ms are applied to identify the plastics in massconsumer products and household wastes (206).

On-line spectroscopic imaging requires high-speedsensors and short image processing steps. An opticalinstrument consisting of a high-throughput NIRspectrograph with an indium, gallium, arsenic(InGaAs)-array detector and specially designedcollection optics has been used to record spectra frompost-consumer packages located on an industrialconveyor belt (157). As these imaging systems generatelarge amounts of data, multivariate statistical techniquesare required to extract the important information fromthe multidimensional spectroscopic images (77). Thismeasuring technique is both economic and suitable forindustrial environments, at least for certain wastefractions (household plastics, hollow articles,engineering plastics). The visual distinction betweenthe spectra is demonstrated by aid of principalcomponent analysis (PCA) plots. A fuzzy neuralnetwork further classifies the spectra. The method isassessed to be suitable for on-line identification underindustrial conditions.

A spectroscopic NIR imaging system, using a FPAdetector, has been developed for remote and on-linemeasurements on a macroscopic scale. Multivariatestatistical techniques are required to extract theimportant information from the multidimensionalspectroscopic images. These techniques include PCAand linear discriminant analysis for supervisedclassification of spectroscopic image data (178).

A NIR spectrometer system has been described basedon optical fibres for absorption and reflexionmeasurements, an AOTF and a transputer system. It isable to detect 1,000 spectra per second and to identify20 pieces per second (209). The identification systemwas implemented and tested for a real-world applicationof plastic identification in municipal solid waste.


34

Automated sorting of post-consumer plastic waste wasachieved using a combination of fixed-filter NIR andneural network data analysis. Rapid and reliableidentification of polymers can be made. Theeffectiveness of the method was demonstrated forsorting PET, HDPE, and PVC (261).

The composition of recycled HDPE/virgin PP blendsprepared in a single-screw extruder have beenmonitored in-line at three different points by NIR (247).

The suitability of Raman spectroscopy for computerisedclassification of post-consumer plastics was evaluated.Plastics investigated were PET, PP, PS, PVC, HDPE andLDPE. It was found that Raman spectroscopy could beused to identify both HDPE and LDPE (81).

The composition of a polymeric material is of interestthroughout its useful life from process stream to productfabrication, and finally to post-consumer recycling. Itis desirable to know not only what types of materialsare present, but also their relative concentrations. Inmany cases, Raman spectroscopy can provide a quick,convenient and relatively inexpensive alternativeconventional analytical method for performing thesetypes of determinations (266).

7.17 Depth Profiling from Surfaces andInterfaces

7.17.1 Optical Depth Profiling Using ATR-FTIRSpectroscopy

ATR-FTIR spectroscopy is an optical depth profilingmethod in which a concentration or structural gradientis probed near the surface of a material, such as anadhesive, sealant or coating. Recently, a number ofimprovements have been made in the method (192).

In one method, by varying the thickness of a barrierfilm, different effective penetration depths are achieved(194). ATR-FTIR spectra of a laminate (PMMA/PVAL)were presented at different base layer thicknesses anddifferent angles of incidence on a zinc selenidesubstrate. By varying the thickness of the PMMAbarrier film, different effective penetration depths inthe PVAL were achieved to detect interfacialinteractions (245).

In another method, two internal reflection elements, Geand KRS-5, with an angle of incidence of 45 degrees,were used to obtain the depth profiles of the crystallinityof PP sheets from the surface to the bulk (204).

A metal overlayer ATR-FTIR technique whichmarkedly enhances the SNR of monolayer andsubmonolayer film spectra has been described. Themetals investigated were gold and aluminium, with asubstrate of polyether-urethane elastomer (375). Theuse of silver films under ATR geometry has improvedthe detection limit of the surface layer on polymerfilms. An enhancement factor of 10 and 2 is reportedfor polydimethylsiloxane and polycarbonaterespectively, compared to the conventional ATRtechnique (362).

ATR-FTIR was used to determine the concentration ofa chemical additive (cationic polyacrylamide resin)within a pulp fibre. The depth distribution of theadditive was determined by sputter etching the fibresurface. The obtained profile was comparedqualitatively with that obtained by the variable-angleATR-FTIR depth profiling method. Most of the additivewas located at the surface, with some distributed withinthe fibre (137).

7.17.2 Depth Profiling Using Photoacoustic IRSpectroscopy

Photoacoustic spectroscopy involves the modulationof IR radiation at a frequency in the acoustic range.The radiation strikes a sample and is subsequentlyturned into heat energy by nonradiative deexcitationprocesses (i.e., excitation is loss by thermal motion andnot by the emission of energy). Heat-generated thermalwaves then propagate to the sample surface andfacilitate the rapid expansion and contraction of acarrier gas. A microphone is used to sense the changein pressure in the enclosed cell.

As only photoacoustic spectroscopic (PAS) signalsgenerated within the thermal diffusion length aredetected, the method can be used to discriminate betweenthe surface and underlying layers of solid materials. PASis useful for probing penetration of about 1 x 10-5 m.The depth of detection is dependent on the thermal andoptical properties of the sample. Sampling depth in PASis determined by the mirror velocity of the interferometer.Low optical velocities will result in PAS signals fromdeep within the sample, while high optical velocitieswill allow thermal diffusion from the surface regions.The sampling depth increases (by a factor of about threeacross the wavenumber range 400-4000 cm-1) withdecreasing wavenumber.

In PAS, the time-resolved photoacoustic response tosinusoidally modulated incident source radiation has aphase delay which depends on the depth in the sample


35

from which the photoacoustic response originates.Use of a stepscanning interferometer circumvents thedifficulties arising when a single chopping frequencyis used for all wavelengths (a chopper is used tointerpret the beam at a single frequency). Step-scanphotoacoustic FTIR experiments can be used to collectinformation from selectable and constant depths fromthe sample surface.

FTIR step-scan photoacoustic spectroscopy was usedto study the composition of thermoplastic olefin films,as a function of depth below the surface. Experimentswere completed at various modulation frequencies,enabling a stratification model to be developed. Theuppermost layer (0-3 µm) showed large changes in talcand PP concentration, while the layer below showed asignificant decrease in both the phases. In the third layer(6-9 µm), all three phases showed the maximum values.In the fourth layer (9-12 µm), the talc concentrationreduced, whilst concentrations of elastomericcopolymer of ethylene and propylene (EPR) and PPwere observed, decreasing with depth (44).

FTIR photoacoustic spectroscopy was used for thestudy of the adsorption of poly(n-butyl methacrylate)from cyclohexane, benzene and carbon tetrachlorideonto alumina. The efficiency of adsorption increasedin the order cyclohexane, carbon tetrachloride,benzene, while methanol and tetrahydrofuran showednegative adsorption. Poly(n-butyl methacrylate) hada negative temperature coefficient of adsorption (126).

A step-scan FTIR photoacoustic phase-resolvedtechnique was used to depth profile micrometre-thicklayered plasma polymers (171).

Migration and concentration levels of sodiumdioctylsulfosuccinate (SDOSS) surfactant moleculesin silicone-modified 50%/50% styrene/butyl acrylatelatex were detected at the film-substrate and film-airinterfaces in mono- and double-layered films. TheSDOSS content was shown to be influenced by thepresence of trimethoxysilyl propylmethacrylatesiloxane (202).

Injection-moulded PP plates, with and withouttitanium dioxide pigment, were irradiated in amedium-accelerated photoageing device to theequivalent of 1 year of outdoor exposure.Photoacoustic FTIR spectra of photooxidised sampleswere analysed. The oxidation profiles monitored wereshown to arise from oxygen diffusion limitation andalso from the heterogeneous absorption of light bythe titanium dioxide-pigmented samples (336).

Dimensionally dependent changes are encountered inPVC weathering processes. Changes are observedduring outdoor photodegradation of PVC sidingcapstock (paint without additives such as pigments)formulations, as a function of exposure time andtitanium dioxide level. Profiles through the thicknessdimension were analysed to identify degradationspecies and depth distribution (76).

7.17.3 Depth Profiling Using Confocal RamanMicrospectroscopy

The depth and surface distribution of the PS grafts,crosslinker, and the sulfonation efficiency were studiedusing confocal Raman microspectroscopy. Highlygrafted samples had a homogeneous distribution ofgrafts and homogeneous sulfonation, whereas unevengraft distributions were observed in samples with lowand intermediate degrees of grafting. The crosslinkerconcentration in the interior of the film wasapproximately 50% of the surface concentration (61).

Confocal Raman microscopy was used for theinvestigation of variations in crosslinking with depthin thicknesses of up to 0.5 mm in UV-cured coatings.Variations of curing with depth in pigmentformulations, in thicknesses of up to 30 µm, wereobserved (62).

Confocal Raman spectroscopy was used to examinedepth or lateral profiles of the crosslinking process (e.g.,the reaction progress) in radiation curable coatings witha resolution of approximately 1 µm3. The potential ofconfocal Raman microscopy is demonstrated for theproblems of the inhibition of the radical polymerisationreaction by oxygen, the limited polymerisation reactionin deep layers due to the restricted penetration of UVlight (Lambert-Beer), the reaction in pigmentedcoatings and the distribution of UV stabilisersinteracting with the UV curing process (118).

Confocal Raman microprobe spectroscopy was used tocharacterise polyaniline/poly(N-vinyl carbazole),polypyrrole/poly(N-vinyl carbazole) and polypyrrole/polyaniline films (or reverse order of each pair in thefilms). Two types of film were observed, depending onthe conditions. Either the second polymer wasincorporated into the initially coated layer or a double-layer film with a well-defined interface was formed.Electrolysis of pyrrole and aniline monomer mixturesgave films rich in pyrrole when the pyrrole:aniline molarratios were greater than 0.12. However, polymerisationof N-vinyl carbazole and pyrrole monomer mixtures gaveonly polypyrrole over a wide range of molar ratios (121).


36

Confocal Raman microspectroscopy was used tomeasure local compositions along a direction that wasperpendicular to the original interface. Compositionprofiles generated by interdiffusion in the concentratedregime between polyphenylene oxide-polystyreneblend pairs were determined (128).

Depth profiling was carried out using confocal Ramanmicrospectroscopy to study PAN/PVAL and PAN/PAlaminates. The laminates were annealed at 65, 75 and90 °C. It was demonstrated that the degree of hydrogenbonding interaction between the nitrile and alcoholgroups near the interfacial region changes betweenlaminates annealed at different temperatures. Forcomparison, Raman mapping of a PAN-PVAL blendwas used to study the interactions between the polymersin this (disordered) system (147).

Confocal Raman microspectroscopy was used tocharacterise the chemical composition of clearcoats inpaint systems. Weathered and unweathered samples ofisolated acrylic/melamine and acrylic/urethaneclearcoats, polyester urethane clearcoats in weatheredand unweathered samples of a complete paint systemon plastic, and UV light cured acrylic clearcoats onpolycarbonate substrates were studied (149).

It was demonstrated that confocal Ramanmicrospectroscopy can be successfully used to studythe hydrogen bonding interactions between the esterand alcohol groups near the interfacial region. Variouslaminates have been studied and it is demonstrated thatPMMA layers with lower molecular weight show agreater degree of interpenetration for a given annealingtime (225).

7.18 FTIR Microspectroscopy

FTIR microspectroscopy, coupled with mappingtechniques, is an effective method for evaluatingdimensionally-dependent changes. The method is basedon the specificity of the IR spectrum and thedimensional resolution of the microscope. The keys tothe successful use of FTIR microscopy are experiencein sample preparation, an understanding of lightmicroscopy, and ingenuity in defining solutions.

The fatigue of NR and styrene-butadiene rubber (SBR)is an enormous industrial problem, as importantmechanical properties of these materials deterioratequickly when stressed. Although fatigue may describethe deterioration of certain material properties, it isgenerally believed that the term also describes failure

by cracking. In fact, abrasive wear is due to thecumulative growth of cracks by tearing under repetitiveloading. Therefore, the analysis and characterisationof cracks in NR are crucial to the development ofmaterial with improved fracture resistant properties.Several spectroscopic methods are available forcharacterising the crack tip region of the rubber on themolecular scale; FTIR microspectroscopy has beenused for this purpose (91).

FTIR microspectroscopy was applied for thecharacterisation of compositional heterogeneity of apolymer blend. For a polymer blend prepared by mixingPP and polycarbonate, the spatially specificcompositional heterogeneity could be easily identified(106).

Mapping the phases of PVAL and PVA blends wasaccomplished using FTIR microspectroscopy. Thedimensions, shapes, and distributions of the domainsare dependent on the initial composition of thepolymeric mixtures in solution. Specific interactionsbetween both homopolymers were observed (129).

Polyvinylidene fluoride (PVDF) samples, obtained bycasting from tetrahydrofuran (THF) solutions andsubmitted to various thermal treatments, were examinedby FTIR microspectroscopy. The analysis permittedexamination of microdomains of samples of differentmorphological characteristics and an indication of thepolymorphism of PVDF is obtained (213).

FTIR microspectroscopy was used to investigate thedrying of water-based acrylic polymer coatings on analuminised substrate. Changes in the absorbance peakheights were monitored as an indication of theremaining water content. The effects on drying ofhumidity, solids content, coating thickness and thepresence of coalescing agents were studied. Coalescingagents were found to increase drying time while aidingfilm formation. Drying time decreased with increasingsolids content and increased with increasing coatingthickness. As expected, relative humidity was found tohave an important effect on the drying process (246).

The interphase in PE fibre/epoxy resin matrixcomposites was studied by FTIR microspectroscopyusing a set up for investigation of the matrix as closeto the fibre as a few microns or less. It was shown thatmoisture present on the fibre surface could influencethe polymerisation reaction of the epoxy/anhydridematrix in an irreversible manner (249).

Model composites of Kevlar-49 and D-glass fibre/epoxy systems were analysed using FTIR micro-


37

spectroscopy. The interphase and specific fibre-matrixinteractions of the fibre-reinforced composites werecharacterised. The surfaces of both Kevlar-49 and D-glass fibres were found to affect the curing process incomposite samples significantly. The epoxy was foundto cure at an accelerated rate at the surface of thesefibres indicating strong interaction between the fibresand the matrices. Using FTIR microspectroscopy, theseinteractions were found to be preferential segregationof the epoxy on the Kevlar surface. It was alsodetermined that the amine group of the Kevlar fibreacted to catalyse the curing process (286).

FTIR mapping was used to study vinyl siding.Particular attention was paid to the determination, insingle mapping experiments, of the compositionalchanges associated with capstock to substrate transitionand to evaluation of the degradation species and levelobserved during weathering exposure throughout thethickness of the siding panel (153).

A combination of cryomicrotomy and FTIRmicroscopy was used to investigate chemical changesin unstrained sheets of PU caused by biodegradation(18 month subcutaneous ovine implant).Cryomicrotomy was used to obtain thin sections fromthe surface into the bulk, parallel to the plane of thesurface. FTIR microscopy was then used to detectchemical changes (156).

The effect of mechanical deformation on a UV-curedurethane-acrylate polymer and on a silicon carbide/urethane-acrylate model composite was studied by FTIRmicrospectroscopy. This technique was used for the firsttime to measure the width of the interfacial zone beyondwhich the fibre has no influence on the matrix (161).

FTIR microspectroscopy has proved useful incharacterising contaminants as small as 5 x 10-5 m indiameter in resins and cured films as well ascharacterising cured film surfaces (191).

Glass fibre strand was treated with gamma-methacryloxypropyltrimethoxysilane as a couplingagent and used to reinforce a vinylester resin. Theinterface was studied by FTIR spectroscopy andshowed that the silane was able to migrate into the resinand influence curing at a distance (200 µm) greater thanthe thickness of the interphase (328).

IR microspectroscopy was used to study the cellmembranes of a flexible PU foam and correlations weremade of absorbance values of methyl signals withabsolute thicknesses calculated from the interferencepatterns observed in the spectra (333).

A comparison is made of the polymer and liquid crystaldroplet regions within polymer-dispersed liquid crystalfilms using FTIR microspectroscopy. IR functionalgroup images of a droplet showed characteristictextures corresponding to the visual images of the samedroplet. The textures in the IR images changed withIR polarisation and with an applied electric field.Hysteresis was observed in the IR region as a functionof voltage and temperature (334).

IR microspectroscopy was used to generate functionalgroup images of liquid crystal (E7) droplets dispersedin poly-n-butyl methacrylate (PBMA). The spatialconcentration fluctuations that occurred within thesystem were studied as a function of time. Thisapproach was possible because spectral informationcould be obtained by focusing on regions of the orderof tens of micrometres. The peak intensities were usedas a measure of concentration of the components. Theamount of liquid crystal dissolved in the polymermatrix determined the extent to which the polymerwas plasticised, which in turn affected the shape andsize of the droplets. The growth of the domains atany temperature was also determined by whether thesystem was maintained above or below the Tg of thematrix. It was observed that the growth of the dropletsfollowed temporal power laws (i.e., time raised to apower of ~θn). The spatially resolved spectroscopicimages provided valuable insights into the phaseseparation process and the formation of microdropletsof E7 in PBMA (280).

7.19 FTIR Imaging

FTIR spectroscopic imaging microscopy is a techniquein which instrumentation is designed about an InSbmultichannel IR array detector, FPA detector and avariable-bandpass dielectric filter. The system may beconfigured for either macroscopic or microscopicapplications and high-fidelity, chemically specificimages may be acquired in real time. The functioningof the imaging microscope is demonstrated withsamples including PS microspheres, preparation oflipids and an amino acid embedded in KBr disks, anda tissue sample derived from a coronal slice of amonkey cerebellum (271).

The FTIR imaging method was extended to the real-time acquisition of images from systems varying withtime. Emphasis is given to the monitoring of thediffusion of a low molecular weight liquid crystalpentylcyanobiphenyl into a solid polybutylmethacrylate film (136).


38

An imaging spectrometer made measurements of thevisible and NIR absorption spectra of EVA copolymers.The NIR spectral images obtained clearly indicated thatthe EVA copolymers exhibited a high degree ofchemical inhomogeneity (105).

FTIR imaging is a powerful technique that can be usedto obtain spatially resolved chemical information froma large sample area in a relatively short time. However,temporal resolution of fast FTIR imaging is limited byrapid loss of data quality due to increased noise withfaster image acquisition. The application of theproposed schemes allows for improved SNRcharacteristics in the resulting data. These schemes aretested by monitoring the dissolution of a polymer film(poly (alpha-methyl styrene)) by a low molecularweight solvent (methyl isobutyl ketone (MIBK)). Atotal acquisition time of about 100 s is achieved,allowing the dissolution process to be monitored byusing image acquisitions separated by 3 minutes. Lownoise concentration profiles, linear solvent penetrationrate and polymer dissolution rate are measured. Thisresult represents an order of magnitude improvementover untreated data (47).

The FTIR imaging method was extended to the real-time acquisition of images from systems varying withtime. Emphasis is given to the monitoring of thediffusion of a low molecular weight liquid crystalpentylcyanobiphenyl into a solid polybutylmethacrylate film (136).

Fast FTIR imaging was used to study the distributionof chemical species and the degree of orientation insemi-crystalline systems. The systems investigatedwere PEG and blends of PEG with PEO, PMMA orPVA. The technique was shown to be useful fordetermining the distribution of species with differentmolecular weights and for determining the degree ofsegregation of the different blend components. Usingan IR polariser, the degree of orientation wasdetermined in the systems by generating spatiallyresolved dichroic ratio images (52).

FTIR imaging, combined with statistical methods, wasshown to be a valuable tool for determining phasecomposition in multiphase systems. A method forreducing liquid crystal solubility in production ofpolymer dispersed liquid crystals (PDLC) wasdeveloped which involved cooling a homogeneousliquid crystal/precursor matrix into the two-phaseregime, followed by fast matrix polymerisation. Theproposed procedure was tested by using a well-studiedPDLC system, NOA65 (a UV-curable optical adhesive)and E7 (a mixture of cyanobiphenyls). Liquid crystal

remaining dissolved in the matrix was sharply reducedby this method. Residual solubility of the matrixmaterial in liquid crystal domains was also decreased.While maintaining the same phase composition, themethod also allowed dispersion size to be tailoredaccording to needs as opposed to the invariablecorrelation between droplet size, solubility andpolymerisation rate inherent in the classicalpolymerisation-induced phase separation methods. Thisgeneral methodology could be usefully applied to othersystems (88).

7.20 Raman Microimaging

The incorporation of high-resolution optics in aRaman spectrometer allows sampling from areas ofless than 1 x 10-6 m in diameter. The addition of aconfocal microscope improves the axial resolution to2 x 10-6 m. Those developments, along with theintroduction of notch filters and holographictransmission gratings, allow the reduction of theacquisition time of Raman spectra from minutes toseconds. The fast data collection combined with thehigh lateral and vertical resolutions makes possiblescanning experiments in which the specimen isadvanced in 1 x 10-6 m size steps. Analysis of thespectra provides information on the spatialcomposition of the sample (139). Two alternativemethods of Raman imaging via global illuminationand via point illumination in combination withconfocal light collection can be applied to the studyof heterogeneous polymer systems (205). The effectsof spectrometer slit width, spatial resolution and thenumber of spectral variables of Raman line-imageswere studied. Depth of penetration and SNRconsiderations dominated the proper selection of slitwidth for the sample of PS spheres (10 µm diameter)embedded in an epoxy resin matrix. With the use ofdifferent microscope objectives to analyse the samesample region, the higher-magnification objectivegave better results, probably due merely to the largernumber of spectra processed (222).

Raman microimaging is used to estimate the effect ofthe silica filler on phase separation in binary polymerblends composed of brominated poly(isobutylene-co-para-methyl) styrene (BIMS) and butyl rubber (IIR).The domain sizes, relative concentration of polymercomponents within domains, and distribution ofparticulate silica filler and zinc stearate curative arecharacterised for blends of different compositions andhistory of ageing treatments. The presence of increasedconcentrations of precipitated silica results in better


39

polymer morphology since domain sizes are reduced.Increased temperature treatment also decreases domainsizes up to about 150 °C, but treatment at 200 °Cappears to induce separation of the elastomercomponents. Silica is usually found near the centres ofthe BIMS domains. There is little difference in silicadistribution before and after curing (33).

Using micro-Raman imaging three blends consistingof PP/PE/EPR copolymer, PBT/polycarbonate/LDPE,and SAN copolymer/styrene-maleic anhydridecopolymer/polydimethylphenylene oxide were studiedwith regard to compositional and morphologicalheterogeneities (221).

Additional References

a.1 J.L. Koenig, Spectroscopy of Polymers, 2ndEdition, Elsevier, Amsterdam, the Netherlands,1999, 77.

a.2 M. Diem, Introduction to Modern VibrationalSpectroscopy, Wiley, New York, NY, USA,1993.

a.3 J.R. Ferraro and K. Nakamoto, IntroductoryRaman Spectroscopy, Academic Press,Orlando, FL, USA, 1994.

a.4 J.L. Koenig, Spectroscopy of Polymers, 2ndEdition, Elsevier, Amsterdam, the Netherlands,1999, 147.

a.5 P.C. Painter, M.M. Coleman and J.L. Koenig,The Theory of Vibrational Spectroscopy andits Application to Polymeric Materials, JohnWiley & Sons, Inc., New York, NY, USA, 1982.

a.6 D. Lin-Vien, N. Colthup, W.G. Fateley and J.G.Grasselli, The Handbook of Infrared andRaman Characteristic Frequencies of OrganicMolecules, Academic Press, San Diego, CA,USA, 1991.

a.7 B.G. Osborne, T. Fearn and P.H. Hindle,Practical NIR Spectroscopy, LongmanScientific and Technical Publishers, Harlow,UK, 1993.

a.8 P.J. Treado and M.D. Morris, AppliedSpectroscopy Review, 1994, 29, 1.

a.9 E.N. Lewis, P.J. Treado, R.C. Reeder, G.M.Story, A.E. Dowrey, C. Marcott and I.W. Levin,Analytical Chemistry, 1995, 67, 3377.

a.10 E.N. Lewis and I.W. Levin, AppliedSpectroscopy, 1995, 49, 672.

a.11 N.C. Crabb and P.W.B. King in MolecularSpectroscopy in Process Analytical Chemistry,Eds., F. McLennan and B.R. Kowalski,Blackie, London, UK, 1995, 40.

a.12 D.C. Hassell and E.M. Bowman, AppliedSpectroscopy, 1998, 52, 18A.

a.13 D.A. Long, Raman Spectroscopy, McGraw-Hill, New York, NY, USA, 1977.

a.14 D.B. Chase and J.F. Rabolt, Ed., FourierTransform Raman Spectroscopy, AcademicPress, Orlando, FL, USA, 1994.

a.15 J. Zhao and R.L. McCreery, AppliedSpectroscopy, 1996, 50, 1209.

a.16 M. Moskvits, Reviews in Modern Physics,1985, 57, 783.

a.17 S. Nie and S. Emory, Science, 1997, 275, 1102.

a.18 P.J. Treado, I.W. Levin and E.N. Lewis, AppliedSpectroscopy, 1992, 46, 1211.

a.19 E.G. Bucher and J.W. Caranhan, AppliedSpectroscopy, 1999, 53, 603.

a.20 N.J. Harrick, Internal Reflection Spectroscopy,Wiley-Interscience, New York, NY, USA,1967.

a.21 M.R. Pereira and J. Yarwood, Journal ofPolymer Science: Polymer Physics Edition,1994, 32, 11, 1881.

a.22 J.B. Huang and M.W. Urban, AppliedSpectroscopy, 1992, 46, 1666.

a.23 J.B. Huang and M.W. Urban, AppliedSpectroscopy, 1993, 47, 973.

a.24 J.D. Swalen and J.F. Rabolt in FourierTransform Infrared Spectroscopy, Applicationsto Chemical Systems, Volume 4, Eds., J.R.Ferraro and L.J. Baslie, Academic Press, NewYork, NY, USA, 1985, 86.

a.25 W.G. Golden in Fourier Transform InfraredSpectroscopy, Applications to ChemicalSystems, Volume 4, Eds., J.R. Ferraro and L.J.Baslie, Academic Press, New York, NY, USA,1985, 140.

a.26 P. Kubelka and Z. Munk, Z. Tech. Physics,1931, 12, 593.


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a.27 S. Bistac, M.F. Vallat and J. Schultz, AppliedSpectroscopy, 1997, 51, 1823.

a.28 D.A.C. Compton and S.V. Compton, AppliedSpectroscopy, 1991, 45, 1587.

a.29 B. Jasse and J.L. Koenig, Journal ofMacromolecular Science: Reviews inMacromolecular Chemistry, 1997, C17, 1, 135.

a.30 D.I. Bower, Journal of Physics B: Atomic andMolecular Physics, 1976, 9, 3275.

a.31 P.J. Hendra and J.L. Agbenyega, The RamanSpectra of Polymers, Wiley, Chichester, UK,1993.

a.32 R. Gachter, H. Muller, Ed., Plastics AdditivesHandbook, 4th Edition, Hanser, Munich,Germany, 1994.

a.33 http://www.polymeradditives.com.

a.34 I. Noda, Applied Spectroscopy, 1993, 47, 1329.

a.35 I. Noda, A.E. Dowrey, C. Marcott and G.M.Story, Applied Spectroscopy, 2000, 54, 236A.

a.36 S. Ekgasit and H. Ishida, Applied Spectroscopy,1995, 49, 1243.


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ABS Acrylonitrile-butadiene-styreneterpolymer

AC Acid chloride

AIBN Azobisisobutyronitrile

AOTF Acousto-optic tunable filter

ATR Attenuated total reflection

BIMS Brominated poly(isobutylene-co-para methyl) styrene

BPDA 3´,3´,4,4´-biphenyltetracarboxylicdianhydride

CCD Charge collection detector

CHMI N-cyclohexylmaleimide

CHPS Cyclohexa(p-phenylene sulfide)

COF Acid fluoride group

COOH Carboxylic acid group

DRIFT Diffuse reflectance FTIR

ENR Epoxidised natural rubber

EPDM Ethylene-propylene-dieneterpolymer

EPR Ethylene-propylene copolymer

EVA Ethylene-vinyl acetate

FPA Focal plane array

FTIR Fourier transform infrared

GMA Glycidyl methacrylate

GTP Group transfer polymerisation

HDPE High density polyethylene

HPLC-FTIR High performance liquidchromatography - FTIR

IIR Butyl rubber

IR Infrared

LCST Lower critical solution temperature

MIBK Methyl isobutyl ketone

MMA Methyl methacrylate

NIR Near infrared

NMR Nuclear magnetic resonance

NR Natural rubber

PA Polyamide

PAA Polyacrylic acid

PAM-co-AA Poly(acrylamide-co-acrylic acid)

PAN Polyacrylonitrile

PBI Polyphenylene bibenzimidazole

PBMA Poly-n-butyl methacrylate

PBT Polybutylene terephthalate

PCA Principal component analysis

PDA p-phenylene diamine

PDLC Polymer dispersed liquid crystal

PDMS Polydimethyl siloxane

PDPE Low density polyethylene

PE Polyethylene

PEG Polyethylene glycol

PEI Polyethyleneimine

PEN Poly(ethylene naphthalate)

PEO Polyethylene oxide

PET Polyethylene terephthalate

PHEMA Poly(2-hydroxyethyl methacrylate)

PLS Partial least squares

PLSR Partial least squares regression

PMAA Polymethacrylic acid

PMMA Polymethyl methacrylate

PNIPAAM Poly(N-isopropylacrylamide)

PP Polypropylene

PPE Poly(2,6-dimethyl-1,4-phenyleneether)

PPMS Poly-p-methylstyrene

PPO Polypropylene oxide

PPS Poly(p-phenylene sulfide)

PS Polystyrene

PTFE Polytetrafluoroethylene

PU Polyurethane

PVA Polyvinyl alcohol

PVAL Polyvinyl alcohol

PVC Polyvinyl chloride

PVDF Polyvinylidene fluoride

SDOSS Sodium dioctylsulfosuccinate

SERS Surface-enhanced Ramanspectroscopy

SFE/FTIR Supercritical fluid extraction/FTIR

SNR Signal to noise ratio

Tg Glass transition temperature

THF Tetrahydrofuran

TMPO-1 1,2-epoxy-2,4,4-trimethylpentane

TPR Terpene-phenol resins

UVRR Ultraviolet Raman resonance

VA Vinyl acetate

Abbreviations


42

References and Abstracts

© Copyright 2001Rapra Technology Limited 43

References from the Rapra Abstracts Database

Item 1ACS Polymeric Materials Science and Engineering.Volume 75. Conference Proceedings.Orlando, FL., Fall 1996, p.106-107.RAMAN AND FTIR STUDIES OF THE EFFECTSOF DRAW RATIO AND SIDE CHAIN LENGTHON THE MOLECULAR ORIENTATION OFPOLYESTER FILMSVlassopoulos D; Petekidis G; Vogiatzis G; Kamitsos EI; Yiannopoulos Y; Bruggeman ACrete,Institute of Electronic Structure & Laser;Patras,Institute of Chemical Engineering & HighTemperature Processes; Foundation for Research andTechnology Hellas; Athens,National Hellenic ResearchFoundation; TNO Plastics & Rubber Research Institute(ACS,Div.of Polymeric Materials Science & Engng.)

Laser Raman and FTIR spectroscopy measurements werecombined to determine the degree of molecular orientationin uniaxially oriented polyester films, as a function of thedraw ratio, and so that the effects of side chain length canbe further quantified. The measurement of molecularorientation in liquid crystalline polymers is of highimportance because of its potential in obtaining ultra-highmodulus materials. A significant degree of molecularorientation along the stretching direction was identified.10 refs.

USA

Accession no.806758

Item 2Journal of Sol-Gel Science and Technology19, Nos.1-3, Dec.2000, p.403-7STRUCTURE OF HYBRID GELS BY DRIFT ANDNMR SPECTROSCOPIESFidalgo A; Nunes T G; Ilharco L MLisbon,Instituto Superior Tecnico

Hybrid inorganic-organic gels were prepared by the sol-gel process using tetraethoxysilane as precursor, mixedwith a low concentration of polytetrahydrofuran, underacid catalysis. The hybrid xerogels were characterisedby DRIFTS and solid state proton, carbon-13 andsilicon-29 NMR spectroscopies. The diffuse reflectanceIR (DRIFT) spectra indicated that the polymer wasresponsible for decreasing the number of free silanolgroups in comparison with pure silica. Solid state NMRspectra revealed the types of silicate structures formedand the conditions for establishing chemical bondsbetween the two phases, which were responsible forthe silica network flexibility. It was concluded that itwas possible to design a hybrid gel with tailoredproperties, even at very low polymer concentration, byselecting the appropriate preparation route. 10 refs.(10th International Workshop on Glass and Ceramics,

Hybrids and Nanocomposites from Gels, ‘Sol-Gel ‘99’,Yokohama, Japan, Sept.1999)EUROPEAN COMMUNITY; EUROPEAN UNION; PORTUGAL;WESTERN EUROPE

Accession no.805107

Item 3ACS Polymeric Materials Science and Engineering.Volume 75. Conference Proceedings.Orlando, FL., Fall 1996, p.70-1. 012ATR FT-IR SPECTROSCOPIC STUDIES OFMICROWAVE PLASMA REACTIONS OFIMIDAZOLE ON POLY(VINYL CHLORIDE)Schmitt B R; Kim H; Urban M WNorth Dakota State University(ACS,Div.of Polymeric Materials Science & Engng.)

This work focuses on imidazole reactions to polyvinylchloride (PVC), formation of reactive sites, reactionmechanisms, and quantitative analysis of the surfacespecies at various depths. For quantitative surface analysisATR FT-IR spectroscopy was used. For hot-pressed PVC,no imidazole reactions were detected on PVC surfacesunder argon and oxygen microwave plasma conditions.Under oxygen microwave plasma conditions, however,newly formed CH2 linkages are detected, resulting fromthe C-Cl bond cleavages. In solvent-cast PVC, imidazolemolecules react to PVC through a carbon-carbon doublecleavage of imidazole, and the formation of the esterlinkages between PVC and imidazole molecules.Quantitative analysis of imidazole reactions to solvent-cast PVC surfaces at various depths reveals that imidazolereactions take place within 0.8 microns from the surface.At surface depths of up to 1.2 microns, surfaceconcentration of imidazole reacted to PVC declines from0.37 x 10-6 mole/square centimetre to 0.17 x 10-6 mole/square centimetre. 8 refs.USA

Accession no.803055

Item 4ACS Polymeric Materials Science and Engineering.Volume 75. Conference Proceedings.Orlando, FL., Fall 1996, p.65-6. 012POLYOLEFIN CHARACTERIZATION OF FTIRTRANSMISSION SPECTROSCOPYBlitz J PEastern Illinois,University(ACS,Div.of Polymeric Materials Science & Engng.)

FTIR spectroscopy was used to measure polyethylene andpolypropylene isotacticity, specifically to provide data inthe relatively narrow, industrially important highisotacticity range. The FTIR data reported in this range iscorrelated with both NMR and solvent extraction


44 © Copyright 2001 Rapra Technology Limited

measurements. The present work demonstrates theusefulness of ordinary transmission FTIR spectroscopyin obtaining qualitative and quantitative data concerningshort chain branching in a variety of polyethylenes. It ispossible to obtain quantitative isotacticity values ofpolypropylene by transmission FTIR spectroscopy. FTIRhas particular advantages over NMR spectroscopy interms of cost and ease of use. In many instances, FTIRcan be utilised more readily than NMR. In other instances,more detailed structural information can still be providedby NMR than FTIR. 4 refs.USA

Accession no.803052

Item 5ACS Polymeric Materials Science and Engineering.Volume 75. Conference Proceedings.Orlando, FL., Fall 1996, p.63-4. 012SPECULAR REFLECTION FT-IR STUDIES OFTHE CONFORMATIONAL BEHAVIOUR OF PETCole K C; Guevremont J; Aiji A; Pellerin E;Dumoulin M MCanada,Industrial Materials Institute(ACS,Div.of Polymeric Materials Science & Engng.)

The use of front surface specular reflection Fourierinfrared spectroscopy was used to obtain information onmolecular conformation and orientation at the surface ofthick samples of drawn poly(ethylene terephthalate)(PETP). Reflectance spectra measured with polarisationparallel or perpendicular to the draw direction can bedecomposed into refractive index and absorption indexspectra, by means of the Kramers-Kronig transformation.The most interesting of the strong bands of PETP is thecarbonyl band. A mechanism for the conformationalchanges that take place on drawing PETP is proposed inwhich planar states are energetically favoured, the barrierto rotation is sufficiently low to allow a high probabilityof non-planar states. Drawing at 80 degrees Celsius causessignificant conversion of gauche to trans conformers inthe glycol segments, but it does not appear to have aneffect on the terephthalate groups. 12 refs.USA

Accession no.803051

Item 6ACS Polymeric Materials Science and Engineering.Volume 75. Conference Proceedings.Orlando, FL., Fall 1996, p.43. 012DETERMINING THE ORIENTATIONAL ORDEROF MEMBRANE-BOUND POLYPEPTIDES BYPOLARIZED ATIR-FTIRAxelsen P H; Citra M JPennsylvania,University(ACS,Div.of Polymeric Materials Science & Engng.)

The orientational order of polypeptide helices can becharacterised by polarised attenuated total internal

reflection Fourier transform infrared (PATIR-FTIR)spectroscopy. This requires an understanding of theevanescent electric field amplitudes, and these, theorientation of the vibrational transition moment relativeto the helix axis. A number of expressions used forcalculating evanescent electric field amplitudes insupported lipid membranes are discussed and their validitytested by measuring the infrared dichroism of poly-gamma-benzyl-L-glutamate and poly-beta-benzyl-L-aspartate under conditions in which their conformationand molecular order is known. The results suggest thatthe aspartyl and glutamyl peptides display differing valuesfor theta, despite similar amide absorption frequenciesand band shapes. The results also indicate that theabsorption intensities for these polymers in a lipidmembrane are self-consistent only if it assumed theelectric field amplitudes to be determined entirely by therefractive index of the bulk medium in which the crystalis immersed.USA

Accession no.803039

Item 7ACS Polymeric Materials Science and Engineering.Volume 75. Conference Proceedings.Orlando, FL., Fall 1996, p.39-40. 012HIGH-PRESSURE PHOTOACOUSTIC STEP-SCAN FT-IR SPECTROSCOPY OF POLYMERSPennington B D; Urban M WNorth Dakota State University(ACS,Div.of Polymeric Materials Science & Engng.)

The basis for high pressure photoacoustic spectroscopyand the resulting enhancement of the photoacoustic signalis described. An experimental setup has been designedwhich enhances the photoacoustic signal response, whichis attributed to the more efficient transfer of thephotoacoustic signal from the analysed specimen to themicrophone. In addition, phase analysis results can bederived from high pressure experiments in step-scanmode. The high pressure experiments were carried outusing thermoplastic olefin (TPO), silanol terminatedpolydimethylsiloxane (PDMS), and polyimide. In allcases intensity enhancements were detected as pressurerises. A comparison of the pressure effect on the relativesignal enhancement shows a less pronounced effect inthe liquid polymer (PDMS) than for the solid samples(TPO or polyimide). This is because the distance fromthe sample to the cell window is inversely proportionalto the photoacoustic signal intensity so that a rise in thisdistance parameter will result in a decreased photoacousticresponse. As pressure is applied to a specimen, specificvolume and inter-molecular distance change, resulting ina decrease in the physical dimensions of the sample, whichresults in the change in the photoacoustic signal intensityand the shift of the photoacoustic phase. 15 refs.USA

Accession no.803035



Item 8ACS Polymeric Materials Science and Engineering.Volume 75. Conference Proceedings.Orlando, FL., Fall 1996, p.11. 012QUANTITATIVE ASPECTS OF ATR ANDPHOTOACOUSTIC STEP-SCAN FT-IR ANDINTERFACIAL ANALYSIS OF POLYMERICFILMSUrban M WNorth Dakota State University(ACS,Div.of Polymeric Materials Science & Engng.)

There are significant implications arising from the abilityof stratifying polymer surfaces and interfaces usingattenuated total reflectance and photoacoustic step-scanFourier transform infrared (FTIR) spectroscopy.Theoretical concepts and experimental methods involvedin the stratification approach to polymer films arediscussed. Quantitative analysis of interfacial regions inmulti-layered polymers is given particular emphasis. Theutilisation of ATR and SS PAS, together with thestratification multi-layer concept, enables depth-profilingexperiments to be carried out on multi-layered polymerfilms. It also provides molecular level data relating tointerfacial interactions between the layers.USA

Accession no.803018

Item 9ACS Polymeric Materials Science and Engineering.Volume 75. Conference Proceedings.Orlando, FL., Fall 1996, p.11. 012SURFACE-ENHANCED AND FOURIER-TRANSFORM RAMAN SPECTROSCOPY OFPOLYMERSBoerio F J; Zhao W W; Tsai Y MCincinnati,University(ACS,Div.of Polymeric Materials Science & Engng.)

In order to determine the interfacial and bulk structure ofpolymers surface-enhanced (SERS) and Fourier-Transform Raman spectroscopy were utilised. Langmuir-Blodgett monolayers of PMDA/ODA polyimides wereformed by transferring monolayers of thedimethylhexadecylamine salt of the polyamide acid ontosilver island films. SERS spectra of 1- and 3-layer LBfilms of the salts were characterised by bands near 1400and 1620 cm-1 that were related to carboxylate speciesand to a stretching mode of the benzene rings, respectively,New bands related to isoimide and imide groups appearednear 1695 and 1800 cm-1 when the films were imidised.Characterisation of the curing of a model rubbercompound consisting of squalene (instead of naturalrubber), initiators, sulphur, accelerators, adhesionpromoters, anti-oxidants, and carbon black was achievedby using FT/Raman spectroscopy. Only one band, near1670 cm-1, was observed between 1500 and 1700 cm-1for short curing times. For longer curing times, new bandsattributed to conjugated double bonds were observed near

1646, 1640, 1628, 1600 and 1580 cm-1. Also, a new bandrelated to polysulphidic crosslinks appeared near 210 cm-1 after reaction for 15 minutes. After about 30 minutesthe intensity of this band reached a maximum. A modelfor the curing reaction was developed from theseobservations.USA

Accession no.803017

Item 10ACS Polymeric Materials Science and Engineering.Volume 75. Conference Proceedings.Orlando, FL., Fall 1996, p.8. 012RAMAN SPECTROSCOPY AND CRYSTALLINEPOLYMERS: THE POLYETHYLENESMandelkern L; Rufina G AInstitute of Molecular Biophysics; FAMU-FSU Collegeof Engineering(ACS,Div.of Polymeric Materials Science & Engng.)

An overview is given of some of the applications ofRaman spectroscopy that lead to an understanding ofthe factors that determine the phase structure ofcrystalline, flexible chain polymers. Emphasis is givento the polyethylenes of different moleculararchitectures and their corresponding oligomers, then-alkanes. The focus of the spectroscopic data is theinternal mode and LAM spectral regions. In order todetermine the crystallite thickness it is necessary toestablish Young’s modulus and to evaluate the validityof the basic relation that is involved. This studyillustrates the difficulty in determining the exactordered sequence length for polyethylene and forfolded n-alkanes and other oligomers and relates to theestablishing of integral fold periods. For a system ofstacked lamellae, an analysis of both the LAM andinternal modes can give the thickness of the interfacialregion. Data is presented which gives quantitativeagreement of the interfacial thickness, as determinedby either the Raman method or small-angle X-rayscattering. Studies of n-alkanes and polyethylenes inthe melt and in the crystalline state indicate that the1060 cm-1 band measures both the long trans sequencesin the crystalline state as well as short sequences inthe interphase and liquid-like regions. The persistenceof this band in the melt precludes its use in quantifyingthe level of crystallinity. For a high molecular weightlinear polyethylene it has been found that alpha adetermined from the band around 860 cm-1 was lessthan that determined from the 1303 em-1 band. It waspostulated that a fourth element of phase structure waspresent. The experimental findings for a large range ofmolecular weight polyethylenes have been confirmed,but an alternate explanation of these results can begiven that is consistent with the three basic elementsof phase structure. 16 refs.USA

Accession no.803015



Item 11Antec 2000.Conference proceedings.Orlando, Fl., 7th-11th May, 2000, paper 499CHARACTERIZATION OF POLYETHYLENEBLENDS BY USING NOVEL TECHNIQUESSUCH AS THE SUCCESSIVE SELF-NUCLEATION AND ANNEALING (SSA) ANDTHE FOURIER SELF-DECONVOLUTION IRSPECTROSCOPY (FSD-IR)Sierra J D; Ospina S; Montoya N; del Pilar Noriega M;Osswald T AInstituto de Capacitacion e.Investigacion del Plastico ydel Caucho; Wisconsin-Madison,University(SPE)

The characterisation of binary and ternary blends ofpolyethylenes by successive self-nucleation and annealing(SSA), and by Fourier self deconvolution infraredspectroscopy was investigated. The SSA investigation,which is capable of determining lamellar thicknessdistributions, short chain branching, and characterisinggrafted polymers, was done using a conventional heat flowcalorimeter. Self deconvolution is a Fourier transformmathematics technique to enhance the resolution betweenadjacent bands, to quantify linear low densitypolyethylene. It was concluded that SSA was a low-costalternative for the characterisation of novel metallocenepolymers. 7 refs.COLOMBIA; USA

Accession no.802029

Item 12Colloid & Polymer Science278, No.10. Oct.2000, p.946-53TIME-RESOLVED NEAR-INFRARED AND TWO-DIMENSIONAL NEAR-INFRAREDCORRELATION SPECTROSCOPIC STUDIESON POLYMERIZATION OF THE SILANECOUPLING AGENTPERFLUOROOCTYLTRIMETHOXYSILANEOgasawara T; Nara A; Okabayashi H; Nishio E;O’Connor C JNagoya,Institute of Technology; Nicolet Japan Corp.;Auckland,University

Both two-dimensional near infrared (2D NIR) and timeresolved near infrared (TR NIR) indicate the progress ofthe polymerisation process of perfluorooctyl-trimethoxysilane catalysed by hydrogen chloride inethanol. TR NIR was used to monitor the bands associatedwith water and ethanolic hydroxyl groups during thereaction. Consumption and release of water moleculeswas observed strongly in the initial reduction, followedby rapid increase of the band at 5164 reciprocalcentimetres. The band at 4825 reciprocal centimetres(associated with OH groups) increased throughout thereaction as a result of the hydrolysis of methoxy groupsand formation of silanols. 2D NIR allowed the observance,from calculated asynchronous spectral maps, of two

species of silanol groups whose behaviour during thereaction is considered. 33 refsJAPAN; NEW ZEALAND

Accession no.796713

Item 13Applied Spectroscopy54, No.9, Sept.2000, p.1384-90FT-RAMAN SPECTROSCOPICINVESTIGATIONS ON THE ORGANICCROSSLINKING IN HYBRID POLYMERS. I.MODEL REACTIONS OF SIMPLE EPOXIDESRiegel B; Kiefer W; Hofacher S; Schottner GWuerzburg,University; Fraunhofer-Institut fuerSilicatforschung

Model reactions of epoxypropane and epoxyhexane wereanalysed using Fourier Transform-Raman spectroscopy andCarbon-13 NMR spectroscopy to obtain information on thepossible products of ring opening in epoxy silane-based sol-gel derived hybrid polymers. A mixture of epoxyalkane,tetramethoxysilane and aluminium sec-butylate wasemployed to investigate behaviour during the sol-gel process.Raman band and NMR peak assignments for various reactionproducts are presented and discussed. 24 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.794693

Item 14Applied Spectroscopy54, No.8, Aug.2000, p.1192-202MEASUREMENT OF THE SENSITIVITY ANDPHOTOMETRIC ACCURACY OF FT-IRSPECTROMETERSBowie B T; Griffiths P RIdaho,University

A method is developed to investigate the sensitivity andphotometric accuracy of a Fourier transform infrared (FT-IR) spectrometer by statistically analysing a set of spectraof a 75 mu m thick film of PETP. These tests are applied tothree commercial FT-IR spectrometers. Although thephotometric accuracy of all three instruments is generallybetter than 0.1%, small artifacts that cannot be removedby signal averaging are often observed where strong bandsshould have a transmittance of less than 0.01%. Bindingof the moving mirror of one of the spectrometers appearsto degrade its performance. When the standard deviationof the noise on 100% lines is calculated conventionally,none of the instruments give efficient signal averaging after25 scans have been co-added, because of small slopes inthe baseline. By calculation of the noise level by successivedifference, signal averaging is improved, but even with thisapproach the noise level on one of the instruments doesnot decrease after 100 scans are averaged. 8 refs.USA

Accession no.789824



Item 15Polymer Science Series B42, Nos.5-6, May-June 2000, p.169-74IR SPECTROSCOPY STUDY OF POLYMERPOROSITYPakhomov P M; Kruglova E V; Khizhnyak S DTver,State University

IR spectroscopic method is developed for evaluating theporosity (concentration and size of pores) in polymers.PE and PAN films of various porosity are prepared fromthe solutions in liquid and solid paraffins. Theconcentration and maximum pore size in the bulk and ina surface layer of the samples are determined by IRspectroscopy in the transmission and reflection modes,respectively. The results obtained are in agreement withthe data of optical and atomic force microscopy. 12 refs.RUSSIA

Accession no.786845

Item 16Applied Spectroscopy54, No.7, July 2000, p.968-73INFRARED RHEO-OPTICS OF BOMBYX MORIFIBROIN FILM BY DYNAMIC STEP-SCAN FT-IR SPECTROSCOPY COMBINED WITHDIGITAL SIGNAL PROCESSINGSonoyama M; Nakano TTokyo,University of Agriculture & Technology; NipponBio-Rad Laboratories

Dynamic step-scan FTIR spectroscopy combined withsoftware-based digital signal processing(DSP) wasapplied for IR rheo-optical measurements of isotactic PPand regenerated Bombyx mori silk fibroin filmundergoing sinusoidal mechanical strain. Comparativemeasurements of dynamic IR spectra of PP film usingthe DSP-based method and two lock-in amplifiers(LIAs)indicated that a high signal-to-noise ratio(SNR) advantagewas attained by the DSP method combined with the LIAmethod. With the DSP technique, dynamic spectra ofBombyx mori silk fibroin film with high SNR weresuccessfully recorded in the whole mid-IR region in only30 min. The dynamic spectra revealed that stress-induceddynamic reorientation in fibroin film was mainly localisedin the segment with beta-sheet conformation and wasalmost synchronous with the applied mechanical strain.Two-dimensional correlation analyses of the dynamicspectra showed that the broad amide I band was resolvedinto three components whose positions were dependenton secondary structures, that the dynamic behaviour oftyrosine residues was extracted by separation of thefeature due to its aromatic side chains from the broadenvelope of the amide I band in the 2D asynchronousmap and that the dynamic behaviour of the amide A andB modes was the same as that of the amide II mode, whenthe mechanical strain was applied to fibroin film. 36 refs.JAPAN

Accession no.785947

Item 17Polymer41, No.24, 2000, p.8659-71RAMAN MICROSCOPIC STUDIES OF THEDISTRIBUTION OF THE FUNGICIDEFLUORFOLPET IN PLASTICISED PVC FILMSMura C; Yarwood J; Swart R; Hodge DSheffield,Hallam University; Avecia Ltd.

Confocal Raman microscopy was used to study thedistribution and redistribution (by leaching) of thefungicide Fluorfolpet (N-dichlorofluoromethyl-thiophthalimide, 5%) in PVC films containing variouslevels of DOP plasticiser. The distribution of both DOPand Fluorfolpet was found to be uneven on a micron scale,but there was no evidence of inhomogeneity ofdistribution of either of these on a macroscopic scale.There was little or no leaching of DOP into water.Leaching of Fluorfolpet from the films was observed andthe redistribution of Fluorfolpet molecules (measured bymapping and depth profiling) showed that this leachingdepended strongly on the DOP concentration or theamount of water penetrating the film. The results werediscussed. 51 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.784928

Item 18ACS Polymeric Materials: Science &Engineering.Spring Meeting 2000.Volume82.Conference proceedings.San Francisco, Ca., 26th-30th March 2000, p.404-5DEGRADATION OF POLYURETHANES ANDEPOXIES; STEP-SCAN PHOTOACOUSTIC FT-IR AND IR/RAMAN IMAGINGKim H; Urban M WCessna Aircraft Co.; Southern Mississippi,University(ACS,Div.of Polymeric Materials Science & Engng.)

Epoxy and polyurethane films were applied by sprayingto aluminium alloy substrates and exposed to UV light at60 C to accelerate the effect of UV exposure. The resultingdegradation was studied using step-scan Fourier transforminfrared (FTIR) spectroscopy, FTIR microscopy andRaman chemical imaging. The epoxy films formed cracksfollowing 5 weeks exposure, associated with a higherconcentration of primary amine groups, indicating higherdegradation, whilst in the non-cracked areas the intensityof the N-H deformation band at 1509 /cm increased,indicating diminished crosslinking reactions. In additionthe C-N bond stretching band at 1296 /cm decreased dueto C-N bond cleavage of tertiary amine groups. Theformation of polyurea was observed in the polyurethanecoating, attributed to crosslinking reactions of urethaneNH groups and NCO from the hexamethylenediisocyanate used for its synthesis. 10 refs.USA

Accession no.784762



Item 19ACS Polymeric Materials: Science &Engineering.Spring Meeting 2000.Volume82.Conference proceedings.San Francisco, Ca., 26th-30th March 2000, p.398-9MAPPING AND IMAGING ORIENTATION,CRYSTALLINITY AND CHEMICALCOMPOSITION IN POLYMER ARTICLESUSING INFRARED AND RAMANMICROSCOPIESEverall N J; Chalmers J M; Kidder L H; Lewis E N;Schaeberle M; Levin IICI plc; Spectral Dimensions Inc.; US,NationalInstitutes of Health(ACS,Div.of Polymeric Materials Science & Engng.)

The use of a fibre-coupled confocal Raman microscopeand an infrared microscope for both point mapping andglobal imaging in the study of spatial variations in polymerchemistry and morphology is illustrated by studies of thecuring of the UV-cured acrylate coatings, crystallinity indrawn polyethylene terephthalate (PET) film, molecularorientation in PET bottles, and the analysis of a PES/PEEScopolymer blended with epoxy resin and cured at elevatedtemperature. 8 refs.USA

Accession no.784759

Item 20ACS Polymeric Materials: Science &Engineering.Spring Meeting 2000.Volume82.Conference proceedings.San Francisco, Ca., 26th-30th March 2000, p.396-7INFRARED, RAMAN AND NEAR-INFRAREDSTUDIES ON STRUCTURE-PROPERTIESRELATIONSHIP IN HIGH DENSITY AND LOWDENSITY POLYETHYLENEOzaki Y; Amari T; Sasic S; Sato H; Shimoyama M;Kamiya T; Ninomiya TKwansei-Gakuin,University; Mitsubishi ChemicalCorp.; Hyogo,Prefectural Police Headquarters(ACS,Div.of Polymeric Materials Science & Engng.)

Infrared, near-infrared, and Raman spectroscopy wereused to study high density, linear low density (LLDPE),and low density polyethylene. Overlapping spectralbands were separated using the second derivative,principal component analysis, and two-dimensionalcorrelation analysis. A model was developed, usingpartial least squares regression, to calculate the densityof LLDPE. 1 ref.JAPAN

Accession no.784758

Item 21ACS Polymeric Materials: Science &Engineering.Spring Meeting 2000.Volume82.Conference proceedings.

San Francisco, Ca., 26th-30th March 2000, p.378-9STRATIFICATION PROCESSES IN LATEXES;ATR, PHOTOACOUSTIC, AND IR/RAMANIMAGING STUDIESZhao Y; Urban M WSouthern Mississippi,University(ACS,Div.of Polymeric Materials Science & Engng.)

The surface distribution of sodium dioctyl sulphosuccinateand sodium dodecylsulphate surfactant molecules in filmsformed from poly(styrene-co-n-butyl acrylate-co-methacrylic acid) latex was investigated using Fouriertransform infrared (FTIR) and Fourier transform Ramanspectroscopies, and surface morphology and depth profilingwere investigated using attenuated total reflectance FTIR.It was concluded that these techniques were effective forthe study of surfactant stratification during the latex filmformation. The concentration of surfactant aggregates wassignificantly higher at the film/air interface than at the film/substrate interface, with surfactant hydrophilic groupsexhibiting preferential parallel orientation, and hydrophobicgroups preferential perpendicular orientation to the latexfilm surface, the degree of orientation being surfactantstructure related. 21 refs.USA

Accession no.784750

Item 22Journal of Polymer Science: Polymer Physics Edition38, No.13, 1st July 2000, p.1773-87DIFFUSION MEASUREMENTS USING ATR-FTIR SPECTROSCOPY: ACETONE DIFFUSIONIN POLYPROPYLENE - USE OF PENETRANTFLUID PRESSURE TO IMPROVE SAMPLE-IRECONTACTYi X; Portnoy J; Pellegrino JUS,National Inst.of Standards & Technology

A simple method for improving the sample film to crystalcontact during measurement of the diffusion of liquidsinto polymer thin films is described using attenuated totalreflectance (ATR)-FTIR. The method is based oncontrolling the penetrant fluid pressure above a thresholdvalue (greater than 230 kilo Pascal) in the ATR flow cell.Using acetone in a commercial polypropylene film, thecalculated diffusion time constant was found to beconstant at pressures above this threshold value. It wasconcluded that the apparent good fit between experimentaldata and a model does not justify complete confidence inthe accuracy of the calculated diffusion time constant. Areasonable measure of consistency between experimentalconditions and the mass transfer and optical absorbancemodel assumptions was obtained by monitoring theabsorbance of the non-overlap polymer absorbance bands.This indicated whether the required intimate contactbetween the sample film and crystal was reached andmaintained. 16 refs.USA

Accession no.784616



Item 23Journal of Macromolecular Science BB39, No.3, 2000, p.387-95FTIR ANALYSIS OF NANOPARTICLES OFSYNDIOTACTIC POLYSTYRENE CONTAININGSINGLE AND/OR MULTIPLE CHAINSChen M; Fan Z; Bu HFudan,University

Samples of nanoparticles containing single and/ormultiple chains are prepared by precipitation from dilutesolutions of syndiotactic PS (s-PS). Vibrational spectraof the nanoparticles are determined at room temperatureand are compared with bulk s-PS. Significant changes inline shape and line width are observed in the spectra ofthe nanoparticles. Infrared analysis of the nanoparticlesalso indicates a faster crystallisation rate and highercrystallinity than for the bulk sample. 12 refs.CHINA

Accession no.784110

Item 24China Synthetic Rubber Industry23, No.4, July 2000, p.219-21ChineseCURING KINETICS OF PU ELASTOMERS BYFTIRZaifeng L; Zhenqin X; Caifeng D; Zhaolian G; Dehe L;Guanghua YQingdao,Institute of Chemical Technology;Beijing,University of Petroleum

The kinetics of curing reaction of PU elastomers isanalysed by in situ quantitative FTIR. The reactions,uncatalysed and catalysed by dibutyltin dilaurate(DBTDL), follow second-order kinetics at lowconversion. At high conversion, however, the second-order rate constants decrease with the increase of reactionextent, due to the influence of diffusion control. Thereaction kinetics parameters are given and the possiblereaction mechanism is further offered. DBTDL is aneffective positive catalyst for the reaction of -NCO with -OH. 8 refs.CHINA

Accession no.783773

Item 25Analytical Chemistry72, No.12, 15th June 2000, p.71R-9RINFRARED SPECTROSCOPYGillie J K; Hochlowski J; Arbuckle-Keil G AApplied Extrusion Technologies Inc.; AbbottLaboratories; Rutgers,University

This review on IR spectroscopy highlights three areas inwhich it has become increasingly important during thelast two years. These areas are two-dimensional infrared(2D IR) spectroscopy, combinatorial chemistry and humanhealth. This trend is quite evident in the abstracts

examined. The review is focused on articles publishedduring 1998 and 1999, but occasionally includes articlesfrom earlier work if they provide additional information.148 refs.USA

Accession no.783746

Item 26Journal of Applied Polymer Science77, No.4, 25th July 2000, p.764-75.IN SITU FTIR MEASUREMENT OF CARBONDIOXIDE SORPTION INTO POLY(ETHYLENETEREPHTHALATE) AT ELEVATED PRESSURESBrantley N H; Kazarian S G; Eckert C AGeorgia,Institute of Technology

Using poly(ethylene terephthalate) near-IR spectroscopywas used to investigate the sorption rate and solubility ofcarbon dioxide in the polymer at elevated pressures. Theeffects of carbon dioxide processing on the crystallinityof the poly(ethylene terephthalate) was also studied. 40refs.USA

Accession no.782739

Item 27Polymer41, No.18, 2000, p.6965-8INVESTIGATION OF GLASS FORMATION ANDPHYSICAL AGEING IN POLY(ETHYLENETEREPHTHALATE) BY FT-IR SPECTROSCOPYAtkinson J R; Biddlestone F; Hay J NBirmingham,University

The changes in chain conformation of PETP which occurduring glass formation and physical ageing were studiedusing FTIR spectroscopy. On cooling and on physicalageing, a change from the trans to the gaucheconformations of the ethylene units in PETP was foundto occur. This was at variance with the results of apreviously reported investigation. 12 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.782252

Item 28Polymer Testing19, No.4, 2000, p.415-7CHARACTERIZATION OFPOLYEPICHLOROHYDRIN ANDCOPOLYMERS OF EPICHLOROHYDRIN-GYLICIDYL ETHERS BY IR SPECTROSCOPYGlavcheev I; Sirashki G; Mateva RSofia,University of Chemical Technology &Metallurgy; Svistov,D.Tsenov Economic University

A study of the possibilities of using infra red spectra forthe characterisation of H-bonds formed as the result ofmacromolecular interactions and the most suitable



absorbencies to be used for qualitative and quantitativecalculation used epichlorohydrin, phenylglycidyl etherand butylglycidyl ether as its basis. A good agreementbetween chemical structure, oxygen atom content andcalculated H-bonds was found using IR spectra. 7 refs.BULGARIA; EASTERN EUROPE

Accession no.779577

Item 29Polymer Bulletin44, No.3, April 2000, p.293-300DETERMINATION OF SMALL INTERACTIONSIN POLYMER COMPOSITES BY MEANS OFFTIR AND DSCCanavate J; Pages P; Saurina J; Colom X; Carrasco FCatalunya,Universitat Politecnica; Girona,Universidad

A series of composites of polystyrene (PS) and blockpoly(styrene-butadiene) (SBS) prepared by extrusionblending in the injection screw and injection mouldingwere studied by Fourier transform infrared (FTIR)analysis. Moulded samples were then dissolved and castas a film and again studied using FTIR, with higher levelsof miscibility noted than on the original moulding. SBScontent of the samples was between 20 and 80 percent,with studies also completed on the pure polymers.Differences observed from simulated spectra of thepolymer composites were explained by interactionsbetween the two polymers due to partial miscibility.Corroboration of results was provided by calorimetrystudies. 16 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;WESTERN EUROPE

Accession no.779461

Item 30Macromolecules33, No.9, 2nd May 2000, p.3431-40FOURIER TRANSFORM INFRAREDSPECTROSCOPY OFPERFLUOROCARBOXYLATE POLYMERSPerusich S AAuburn,University

Perfluorocarboxylate polymers in the carboxylic methylester, potassium salt and carboxylic acid forms wereanalysed by FTIR transmission and ATR spectroscopies.Band assignments were made for most of the dominantpeaks. An absorbance band ratio, comparing the 555/cmC-F band to the 982/cm C-O-C ether band, was found tobe a direct measure of the equivalent weight of thepolymers. In addition, the transition from the methyl esterform to the acid form was determined by examining the2969/cm methyl ester band versus the broad 3200/cm band.Quantitative expressions were presented for use in thecomputation of equivalent weight and acid content basedon the FTIR thin film absorbance measurements. Thetechnique used provided a direct measure of the trade-off

between high anionic selectivity (high equivalent weight)and good conductivity (low equivalent weight). 7 refs.USA

Accession no.778456

Item 31Macromolecular Rapid Communications21, No.7, 12th May 2000, p.354-7IN SITU FTIR SPECTROSCOPIC STUDY OFTHE REGULARITY BANDS AND PARTIAL-ORDER MELTS OF ISOTACTICPOLY(PROPYLENE)Xinyuan Zhu; Deyue Yan; Hongxi Yao; Pingfang ZhuShanghai,Jiao Tong University

An experimental method was developed for thedetermination of the order of the regularity bands ofisotactic polypropylene, using fast heating Fouriertransform infrared spectroscopy, which resulted in the bandsbeing arranged in terms of the order degree, from high tolow: 940, 1220, 1167, 1303, 1350, 841, 998, 900, 808, 1100and 973 /cm. Partially ordered melt was formed when thecrystalline polymer melted, with the crystalline peakshifting to lower temperatures and the exothermic enthalpyincreasing, with decreasing degree of order. 23 refs.CHINA

Accession no.778334

Item 32Macromolecules33, No.10, 16th May 2000, p.3518-24REAL-TIME MID-IR MONITORING OF THEINITIATION AND PROPAGATION IN EPOXI-INITIATED LIVING ISOBUTYLENEPOLYMERIZATIONSMichel A J; Puskas J E; Brister L BWestern Ontario,University

The initiation and propagation of the polymerisation ofisobutylene (IB), initiated by 1,2-epoxy-2,4,4-trimethylpentane (TMPO-1)/TiCl4, was monitored in-situusing a fibre optic transmission mid-infrared probe.Polyether formation, the isomerisation of TMPO-1 into2,4,4-trimethylpentanal, and its complexation by TiCl4occurred simultaneously with the initiation of thepolymerisation. It is proposed that the initiating mechanisminvolves the formation of tertiary carbocations, by bothSN1 and SN2 paths. From the linearity of the first-orderplots of monomer consumption, and the near uniformityof the polyisobutylene, it was concluded that livingpolymerisation conditions prevailed. 16 refs.CANADA

Accession no.778280

Item 33157th ACS Rubber Division Meeting - Spring 2000.Conference preprints.



Dallas, Tx., 4th-6th April 2000, paper XVIIIRAMAN MICRO IMAGING OF POLYMERBLENDSAppel R; Zerda T W; Waddell W HTexas,Christian University; ExxonMobil Chemical Co.(ACS,Rubber Div.)

Raman microimaging is used to estimate the effect of thesilica filler on phase separation in binary polymer blendscomposed of BIMS and BR. The domain sizes, relativeconcentration of polymer components within domains,and distribution of particulate silica filler and zinc stearatecurative are characterised for blends of differentcompositions and history of ageing treatments. Thepresence of increased concentrations of precipitated silicaresults in better polymer morphology since domain sizesare reduced. Increased temperature treatment alsodecreases domain sizes up to about 150 deg.C, buttreatment at 200 deg.C appears to induce separation ofthe elastomer components. Silica is usually found nearthe centres of the BIMS domains. There is little differencein silica distribution before and after curing. 6 refs.USA

Accession no.778124

Item 34Polymer News25, No.5, May 2000, p.172-5FT-IR DEVICE FOR ON-LINE MONITORING OFCURE REACTIONS UNDER PRESSURECarotenuto G; Del Nobile A M; Nicolais LItaly,National Research Council; Naples,University

A special device is designed to study the effect of pressureon the kinetic behaviour of a commercial phenolic resinby IR spectroscopy (FTIR). Accurate and reproduciblespectra are generated, the characteristic IR peaks assignedand the reaction kinetics evaluated by monitoring the ratesof peak disappearance. The pressure has the effect toincrease both reaction rate and maximum conversionvalue. 6 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;WESTERN EUROPE

Accession no.778119

Item 35Macromolecular SymposiaVol.150, Feb.2000, p.121-6EMULSION (CO)POLYMERISATION OFSTYRENE AND BUTYL ACRYLATEMONITORED BY ON-LINE RAMANSPECTROSCOPYvan den Brink M; Pepers M; van Herk A M; German A LEindhoven,University of Technology

On-line, in-situ Raman spectroscopy was used to monitorthe solution homopolymerisations of styrene and n-butylacrylate. The results obtained were then applied to thestudy of the emulsion homopolymerisations of both

monomers. The data from the emulsionshomopolymerisations were then employed to calculatemonomer concentrations during the emulsioncopolymerisation of styrene and butyl acrylate. 15 refs.EUROPEAN COMMUNITY; EUROPEAN UNION;NETHERLANDS; WESTERN EUROPE

Accession no.777405

Item 36Macromolecular SymposiaVol.143, Aug.1999, p.323-36DIFFUSION OF ALCOHOLS AND WATER INPOLYAMIDE 11: A STUDY BY FOURIER-TRANSFORM NEAR-INFRAREDSPECTROSCOPYWu P; Siesler H WEssen,University

The diffusion of different deuterium-labelled (OD) lowmolecular weight alcohols and deuterium oxide inpolyamide 11 (PA11) was investigated by monitoring theNH/ND exchange in the polymer by Fourier transformnear-infrared spectroscopy (FTNIR). The resultsdemonstrate that the diffusion process of the differentpenetrants is strongly controlled by their molecularstructure and geometry. To characterise this phenomenonquantitatively, the diffusion coefficients for the differentdeuteration agents were determined for PA11.Furthermore, it was shown that with this technique theless ordered regions of the polymer could be separatedspectroscopically from the crystalline domains, which arenot accessible for the isotopically labelled diffusants. 27refs. (World Polymer Congress, 37th InternationalSymposium on Macromolecules, Gold Coast, Australia,12-17 July 1998)EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.770951

Item 37Macromolecules32, No.26, 28th Dec.1999, p.8989-95STUDYING POLY-DISPERSED LIQUID-CRYSTAL FORMATION BY FTIRSPECTROSCOPY. II. PHASE SEPARATION ANDORDERINGBhargava R; Shi-Qing Wang; Koenig J LCase Western Reserve University

It is shown that rapid scan FTIR is a powerful tool formonitoring physical changes (phase separation andnematic ordering). Phase separation was observed duringthe curing process by a scattering-induced change in theabsorbance spectrum of the sample. Nematic orderingcould be observed and quantified based on a change in acharacteristic band of the liquid crystal. Moreover, thephase separation and the onset of nematic ordering weretemporarily resolved. The conversion at phase separationdecreased strongly with an increase in liquid crystal



content, while the conversion required for phaseseparation increased with increasing temperature. Thefraction of liquid crystal present as nematic droplets andtotal fraction of nematic domains in the polymer dispersedliquid crystal were quantified from changes in thevibrational spectrum of the liquid crystal (E7). On thebasis of mass balance applied to the closed process, thephase diagram of the system could be determined as afunction of curing temperature. Solubility limits obtainedby this method agree well with results obtained by otherresearchers. The concept of a spectroscopic compositeplot that completely describes the formation process in apolymer dispersed liquid crystal is proposed. 36 refs. (Part1, previous paper, this journal, p.8982-8)USA

Accession no.766636

Item 38Macromolecules32, No.26, 28th Dec.1999, p.8982-8STUDYING POLYMER-DISPERSED LIQUID-CRYSTAL FORMATION BY FTIRSPECTROSCOPY. I. MONITORING CURINGREACTIONSBhargava R; Shi-Qing Wang; Koenig J LCase Western Reserve University

Real-time FTIR was used to study the curing of a UV-curable prepolymer (NOA65) and its mixtures with liquidcrystals. Curing reactions were examined as a functionof film thickness, temperature, and liquid crystal content.While there was little dependence of the curing behaviouron the thickness of the film, the effect of temperature wasstrong. Curing rates exhibited a maximum around 325K,while conversions reached a plateau about 20K higher.Liquid-crystal addition depressed the conversion.However, compared with the neat matrix, the finalconversion was significantly lower only for phase-separating concentrations. The rate of reaction decreased,and the induction period for the onset of polymerisingreactions increased, with increasing liquid-crystalconcentration. It is concluded that real-time FTIR is auseful tool for monitoring polymer-dispersed liquidcrystal formation and optimising curing conditions.NOA65 (from Norland Products Inc.) is a thiolene-chemistry curable prepolymer mixture of trimethylol-propane diallyl ether, trimethylolpropane tris(thiol),isophorone diisocyanate ester, and a benzophenonephotoinitiator. 34 refs.USA

Accession no.766635

Item 39Polymer41, No.8, 2000, p.2961-70FT-IR STUDIES OF SIDE CHAIN LIQUIDCRYSTALLINE THERMOPLASTIC ELASTOMERS

Nair B R; Gregoriou V G; Hammond P TMassachusetts Institute of Technology

The response of a PU with liquid crystals pendant to thesoft segments to an applied strain was studied using FTIRlinear dichroism. It was found that this complex materialfollowed the trend established in the literature for bothside chain liquid crystalline homopolymers andsegmented PUs. At low strains, the soft segments alignedwith strain, inducing an orientation in ‘lone’ hardsegments. Up to strains of 40%, the liquid crystallinemesogens aligned with the strain field and the hardsegments in hydrogen bonded domains alignedperpendicular to the field. At strains above 40%, arearrangement of the ordering was found that resulted insmectic layers and the hard segments aligning parallel tothe field. A model was proposed to represent these findingsand the cooperative movement of the differentmacromolecular components of the PU was considered.37 refs.USA

Accession no.766050

Item 40Journal of Biomaterials Science: Polymer Edition10, No.12, 1999, p.1289-302FTIR SPECTROSCOPIC INVESTIGATION ANDMODELLING OF SOLUTE/POLYMERINTERACTIONS IN THE HYDRATED STATEAm Ende M T; Peppas N APurdue University

Attenuated total reflectance infrared spectroscopy is usedto investigate possible interactions during transport ofoxyprenolol.HCL bovine scrum albumin, alpha-chymotrypsin and fibrinogen through polyacrylic acid andits random copolymeric gels. Carbonyl and carboxylateion peak shifts are used to identify drug/gel binding dueto electrostatic and hydrogen bond interactions betweenthe polymer carrier and the drugs tested. These findingsare used to interpret the decrease in calculated diffusioncoefficients of drugs diffusing through these gels and theassociated hindering of drug transport. A model isdeveloped to analyse this transport process as a functionof the binding heat of the drug with the polymer. 16 refs.USA

Accession no.765134

Item 41Journal of Polymer Science: Polymer Physics Edition38, No.2, 15th Jan.2000, p.329-40EPOXY-AMINE RETICULATES OBSERVED BYINFRARED SPECTROMETRY. II.MODIFICATIONS OF STRUCTURE AND OFHYDRATION ABILITIES AFTER IRRADIATIONIN A DRY ATMOSPHERENgono Y; Marechal YCEA/Grenoble



Infrared spectroscopy was used to follow the ageingprocesses of two epoxy resins. Resin samples wereexposed to ionising radiation and the effects at themolecular level, and how the resins modified theirhydration mechanisms was discussed. Aromatic aminecured resins are only slightly affected by the radiation,but those cured by alkyl diamines are more sensitive andthus absorb more water.molecules. 14 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.763885

Item 42Macromolecular Rapid Communications20, No.12, Dec.1999, p.607-11POLYELECTROLYTE COMPLEX LAYERS: APROMISING CONCEPT FOR ANTI-FOULINGCOATINGS VERIFIED BY IN-SITU ATR-FTIRSPECTROSCOPYMueller M; Rieser T; Lunkwitz K; Meier-Haack JDresden,Institute of Polymer Research

In-situ ATR FTIR spectroscopy was used to study theinteraction between the differently charged model proteinshuman serum albumin, lysozyme, immunoglobulin G andmultilayer assemblies, which were deposited byalternating adsorption of polyethyleneimine andpolyacrylic acid onto silicon crystals. Low adsorbedprotein amounts were observed if the top polyelectrolytelayer and the protein were equally charged, whereasenhanced protein adsorption occurred for electrostaticattraction between protein and top polyelectrolyte layer.18 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.761294

Item 43Macromolecules32, No.24, 30th Nov.1999, p.8161-6VIBRATION MODE INTERACTION IN THERAMAN SPECTRA OF POLY(1,6-BIS(N-CARBAZOLYL)-2,4-HEXADIYNE)Bloor D; Fehn TDurham,University; Bayreuth,University

The Raman spectrum of the above polydiacetylene wasre-examined and analysed in terms of the resonantinteraction of backbone and side-group vibration modes.FTIR Raman spectra were recorded for partially and fullypolymerised samples. These data complemented earlierstudies of the resonance-Raman spectra of partiallypolymerised crystals conducted at low temps. Themultipeaked spectrum, which was observed in the vicinityof the stretching vibration of the backbone carbon doublebond, was analysed using these results. A model thatincorporated the resonant interaction of the carbon double-bond mode with three vibrational modes of the carbazolyl

side groups was shown to provide a good fit to theavailable experimental data. 29 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;UK; WESTERN EUROPE

Accession no.760880

Item 44Polymer41, No.4, 2000, p.1597-606DISTRIBUTION OF INDIVIDUALCOMPONENTS IN THERMOPLASTICOLEFINS: STEP-SCAN FT-IRPHOTOACOUSTIC PHASE ANALYSISKiland B R; Urban M W; Ryntz R ANorth Dakota State University; Visteon AutomotiveSystems

Fourier transform infrared step-scan photoacousticspectroscopy was developed to study the composition ofthermoplastic olefin films, as a function of depth belowthe surface. Infrared bands associated with talc,polypropylene (PP), and ethylene-propylene rubber (EPR)were used as depth-profiling probes to identifyphotoacoustic signals. Experiments were done at variousmodulation frequencies, enabling a stratification modelto be developed. The uppermost layer (0-3 micrometre)showed large changes in talc and PP concentration, whilstthe layer below showed a significant decrease in both thephases. In the third layer (6-9 micrometre), all three phasesshowed the maximum values. In the fourth layer (9-12micrometre), the talc concentration reduced, whilstconcentrations of EPR and PP were observed, decreasingwith depth. 32 refs.USA

Accession no.760721

Item 45Applied Spectroscopy53, No.11, Nov.1999, p.1412-8IN-LINE NEAR-INFRARED MONITORING OFPOLYMER PROCESSING. I. PROCESS/MONITOR INTERFACE DEVELOPMENTReshadat R; Desa S; Joseph S; Mehra M; Stoev N;Balke S TToronto,University

Near-infrared inline monitoring of polymer processingmeans using an optical fibre-assisted spectrometer to obtainspectra of the polymer melt flowing through commonlyused processing equipment (an extruder). Conditions inthe extruder are typically 200 deg.C and 20 MPa. Thedesign of interfaces between the spectrometer and themolten polymer is shown. Three designs are shown, eachpermitting monitoring at a different location in the process:a melt-at-die interface, a melt-in-barrel interface and astrand interface. These designs are for monitoring justbefore the extruder exit, in the main barrel of the extruderand after the product exits from the extruder as a strand,



respectively. All these interfaces protect the inserted opticalfibre probe from the harsh environment within the extruderwhile permitting easy replacement or a probe withoutinterrupting the process. This latter characteristic is veryimportant because it permits easy probe repair as well asthe use of other types of probes (for monitoring colour orparticles, for example) to be used during a run. Examplesof near-infrared spectra obtained with each of the interfacesused with an immiscible blend of PE and PP are shown.Large differences in the spectra demonstrate that the designof the interface will affect multivariate analysis directed atcomposition prediction. Subsequent papers are directed atusing the melt-at-die interface for composition predictionand accounting for nonlinear relationships betweenabsorbance and concentration. 6 refs.

CANADA

Accession no.760231

Item 46Applied Spectroscopy53, No.11, Nov.1999, p.1398-402PLASTIC DEFORMATION OF POLYETHYLENESTUDIED BY INFRARED DICHROISMElkoun S; Seguela R; Depecker CLille,Universite des Sciences et Technologies; URACNRS

IR dichroism measurements are carried out to investigatethe plastic deformation mechanisms of homogeneous andheterogeneous ethylene copolymers issued from themetallocene and the Ziegler-Natta catalyses, respectively.The two copolymers having the same density displaysignificantly different plastic behaviour that should resultfrom different mechanisms of crystal slip. Suchmechanisms are analysed on the basis of the main crystalslip systems (100)(001) and (010)(001) having the highershear compliances. Attention is focused on the Schmidfactor, S, of the slip planes, which is the ratio of the shearstress acting on each slip plane to the applied tensile stress.From the orientation functions of the three crystallographicaxes of the orthorhombic unit cell, the Schmid factor ofthe two slip systems is determined as a function of plasticstrain. The heterogeneous copolymer exhibits somewhathigher data for the (010)(001) slip, which suggests apreferred activation of this system during the yielding stage.In contrast, the homogeneous copolymer displays closevalues for the two slip systems, indicating that plastic flowis more likely governed by a combined activation of thetwo slip systems and with eventual cross slip owing to thecommon (001) slip direction. 17 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.760229

Item 47Applied Spectroscopy53, No.11, Nov.1999, p.1313-22

TOWARDS FASTER FT-IR IMAGING BYREDUCING NOISEBhargava R; Ribar T; Koenig J LCase Western Reserve University

Fourier transform infrared (FT-IR) imaging is apowerful technique that can be used to obtain spatiallyresolved chemical information from a large sample areain a relatively short time. However, temporal resolutionof fast FT-IR imaging is limited by rapid of data qualitydue to increased noise) with faster image acquisition.Various coaddition schemes to reduce noise andimprove the quality of images acquired from suchsystems are presented. The application of the proposedschemes allows for improved signal-to-noise ratio(SNR) characteristics in the resulting data. Theseschemes are tested by monitoring the dissolution of apolymer film (poly alpha-methyl styrene) by a low-molecular-weight solvent (methyl isobutyl ketone(MIBK)). Pseudo coaddition improves the SNR byapproximately 45%, while the SNR for samplingcoaddition is found to scale as aproximately N0.5,where N is the number of coadded pixels. A totalacquisition time of about 100 s is achieved, allowingthe dissolution process to be monitored by using imageacquisit ions separated by 3 min. Low noiseconcentration profiles, linear solvent penetration rateand polymer dissolution rate are measured. Detectionlimits of approximately 5% and quantification limitsof ~20% are achieved using optimal coadditionstrategies. This result represents an order of magnitudeimprovement over untreated data. 25 refs.

USA

Accession no.760228

Item 48156th ACS Rubber Division Meeting - Fall 1999.Conference preprints.Orlando, Fl., 21st-23rd Sept.1999, paper 122RAMAN STUDY OF KINETICS OFGRAPHITISATION OF CARBON BLACKSZerda T W; Gruber TTexas,Christian University(ACS,Rubber Div.)

Raman spectra of laser heated carbon blacks provideinformation on the dynamics of graphitisation process.Continuous wave and pulsed-laser heating is used. Itis shown that two ordering mechanisms of distinctlydifferent reaction rates are present during the heattreatment. The mechanism dominating during the initialstages of graphitisation is characterised by a very fastrate. The rate during the later stages of the process,after the initial first couple of seconds is orders ofmagnitude slower. 8 refs.

USA

Accession no.759712



Item 49156th ACS Rubber Division Meeting - Fall 1999.Conference preprints.Orlando, Fl., 21st-23rd Sept.1999, paper 160REAL-TIME MONITORING OFPOLYMERISATION PROCESSES USING A MID-IR FIBREOPTIC PROBEPuskas J E; Michel A J; Brister L BWestern Ontario,University(ACS,Rubber Div.)

A novel fibreoptic mid-IR probe is developed for the real-time monitoring of polymerisation processes. The probeis equipped with two interchangeable heads: one is anattenuated total reflectance (ATR) head and the other oneis a transmission (TR) head. The TR head can monitorvery low concentrations (0.1 mmol/L). The ATR probe isused to monitor both homogeneous and heterogeneousisobutylene (IB) polymerisations by the disappearanceof the C=C double bond stretch at 1655 cm -1 and of theC-H stretch in the CH3- group at 1375 cm -1. Polymerformation is monitored by the appearance of the followingsignals characteristic of polyisobutylene (PIB): the 1230cm -1 band identified as the vibrations of the distortedcarbon tetrahedrons (-C(CH3)2- groups); the 1364/1391cm -1 asymmetrical doublet representing the C-H bendingof the t-butyl groups; and the 1470 cm-1 methylene‘scissoring’ vibration. The TR probe is used to monitorthe initiation step in a living IB polymerisation initiatedby 2-(2,2-dimethyl-propyl)-2-methyl-oxirane (TMPO-1)/TiCl4. The appearance of bands characteristic of aldehyde/ketone isomerisation products and polyethers at 1635,1665 and 1100 cm-1, respectively, is observed in real-time. The disappearance of the C-O-C stretching at 1260cm-1 can only be monitored in the absence of IB becauseof overlapping with the 1230 cm-1 band. Due to thesensitivity of the TR probe the 1655 cm-1 band is saturatedat the beginning of the polymerisation, so IB consumptionis followed by monitoring the 2nd overtone of the =CH2bending at 1780 cm-1. The results demonstrate theversatility and powerfulness of this new method. 8 refs.CANADA

Accession no.759419

Item 50Polymer Degradation and Stability67, No.1, 2000, p.149-58FTIR STUDY OF THE EFFECT OFHYDROLYTIC DEGRADATION ON THESTRUCTURE OF THIN PETP FILMSSammon C; Yarwood J; Everall NSheffield,Hallam University; ICI Research &Technology Centre

Thin films (about 100 nanometres) were prepared by spincasting. They were treated with pure water or 1%potassium hydroxide at 90C for up to 8 days. Changes inchemistry and morphology were followed using FTIR andReflection Absorption Infrared Spectroscopy. Dramatic

changes in the intensity of the characteristic carbon-hydrogen band were noted as a function of degradationof the samples degraded by both the water and the alkali.This was interpreted as resulting from a change in theenvironment of the aliphatic methyl groups andsubsequent extensive hydrogen bonding, due to anincrease in the numbers of hydrophilic end groups.Differences in bands assigned to carbonyl groups andhydroxyl groups suggested formation of differenthydrogen bonded species in the two systems. Theautocatalytic nature of the hydrolysis in pure water wasconfirmed and evidence for the so-called‘chemicrystallisation effect’, with crystallinity increasingwith degradation, was observed. The thin nature of thefilms allowed a spectroscopic insight into the morphologyof the degrading films as a function of treatment time. 26refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.758436

Item 51Polymer International48, No.11, Nov.1999, p.1108-12IRREVERSIBILITY OF STRETCHING-INDUCED LOCAL CONFORMATIONALCHANGES AS VERIFIED THROUGH AN FTIRDICHROISM STUDY FOR PVCGuarrotxena N; Millan J-LMadrid,Instituto de Ciencia y Tec.de Polim.

Polyvinyl chloride (PVC) films were stretched to variouselongation ratios and the dichroic behaviour of 615 and637 /cm bands of the infrared spectrum was investigated.The evolution of the dichroic ratios and of the relativeabsorbance of the bands in the direction perpendicular tothat of stretching were compared so that the occurrence oflocal chain orientation related to the conformational changeGTTG-TT to GTGTTT at mmr isotactic tetrads could bedifferentiating from the normal orientation of syndiotacticsequences, to confirm that this conformational changeoccurs when stretching PVC. 19 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;WESTERN EUROPE

Accession no.757990

Item 52Journal of Polymer Science: Polymer Physics Edition37, No.17, 1st Sept.1999, p.2353-9FAST FTIR IMAGING: A NEW TOOL FOR THESTUDY OF SEMICRYSTALLINE POLYMERMORPHOLOGYSnively C M; Koenig J LCase Western Reserve University

Fast FTIR imaging was used to study the distributionof chemical species and the degree of orientation insemi-crystalline systems. The systems investigatedwere pure poly(ethylene glycol) (PEG) and blends of



PEG with PEO, PMMA or PVAC. The technique wasshown to be useful for determining the distribution ofspecies with different molecular weights and fordetermining the degree of segregation of the differentblend components. Using an IR polariser, the degreeof orientation was determined in the systems bygenerating spatially-resolved dichroic ratio images. 20 refs.USA

Accession no.757179

Item 53Journal of Polymer Science: Polymer Physics Edition37, No.16, 15th Aug.1999, p.2261-8STUDYING ANOMALOUS DIFFUSION IN ALIQUID CRYSTAL/POLYMER SYSTEM USINGFAST FTIR IMAGINGSnively C M; Koenig J LCase Western Reserve University

Fast FTIR imaging showed that the diffusion of liquidcrystal 4-n-pentyl-4'-cyanobiphenyl into a poly(butylmethacrylate) matrix exhibited anomalous diffusionbehaviour. A fit to several models was attempted, butno single model described the observed diffusionbehaviour adequately. A simple mass uptake analysiswould have indicated that diffusion occurred accordingto Fick’s second law, whereas fast FTIR correctlyidentified the process as anomalous. 20 refs.USA

Accession no.757170

Item 54Macromolecules32, No.20, 5th Oct.1999, p.6807-12IN SITU SPECTROELECTROCHEMICALRAMAN STUDIES OF POLY(3,4-ETHYLENEDIOXYTHIOPHENE) (PEDT)Garreau S; Louarn G; Buisson J P; Froyer G; Lefrant SNantes,Institut des Materiaux

The results are reported of a spectroelectrochemicalstudy of the oxidative doping of PEDT carried out usingUV-vis-NIR optical absorption spectroscopy andresonance Raman scattering spectroscopy with twoexcitation lines, namely green (514 nm) and infrared(1064 nm). Changes in the Raman spectra duringdoping are interpreted in terms of modification ofelectronic distribution along the chain. Results ofvibrational calculations, determined using asymmetrised dynamical matrix model, are comparedwith experimental data and a coherent set of forceconstants related to the assignment of the Raman bandsand estimation of the polymer chain modificationduring doping is proposed. 17 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.756395

Item 55Macromolecules32, No.21, 19th Oct.1999, p.7147-55STATIC AND DYNAMIC FT-IR LINEARDICHROISM STUDIES OF PLASTICIZATIONEFFECTS IN A POLYURETHANE ELASTOMERGraff D K; Haochuan Wang; Palmer R A;Schoonover J RLos Alamos National Laboratory; Duke,University

The physical role of plasticisation was assessed bycombining FTIR data for plasticised Estane 5703 (apolyester-urethane from B.F.Goodrich) subjected tomechanical deformation with spectral differences as afunction of added plasticiser. The orientation functionsand dichroic difference data for Estane showed that, instatic stretching, the soft domains reached orientationsaturation before the hard domains. With added plasticiser,hydrogen bonding to the hard segments was disruptedand the Tg of the soft domain decreased, indicating thatplasticiser remained solubilised in the soft domain. Onthe time scale of the static experiment, plasticisationdiminished the ability of both domains to reorient, whilethe plasticiser itself did not orient. With added plasticiser,neither domain reached orientation saturation during thepre-stretching process and dynamic distortion resulted ina similar response from both domains. Bimodal bands inthe dynamic data indicated that the strain applied on arapid time scale (20 Hz) allowed resolution of thecomponents of differently oriented bands. 34 refs.

GOODRICH B.F.USA

Accession no.756264

Item 56Macromolecules32, No.19, 21st Sept.1999, p.6319-25STRUCTURAL AND CONFORMATIONALCHARACTERIZATION OF POLY(ETHYLENE2,6-NAPHTHALATE) BY INFRAREDSPECTROSCOPYVasanthan N; Salem D RTRI/Princeton

X-ray diffraction analysis showed that poly(ethylene 2,6-naphthalate) (PEN) film, annealed from 160 to 260 Ccrystallised in the alpha-crystal form, whilst crystallisationdirectly from the melt yielded the beta-crystal form whenthe crystallisation temperature (Tc) was greater than 200C, and in the alpha form at lower Tc. Infrared spectrafrom PEN samples containing alpha, beta, and amorphousphases were determined, and the amorphous contributiondigitally subtracted to yield characteristic spectra of theamorphous, alpha, and beta phases. It is proposed thatthe alpha crystal form adopts an all-trans conformation,whilst the beta crystal form adopts a conformation withappreciable gauche character. Conformational changes inPEN occurred due to the rotation of the naphthalene ringas well as rotation of the ethylene glycol units. The



normalised absorbances of the bands at 824 and 814 /cmwere correlated to polymer density, and could be used torepresent the amorphous and alpha crystalline phases,respectively. Using drawn PEN film, the assignment ofthe amorphous 1338 /cm band to the trans conformationwas studied. 32 refs.USA

Accession no.756087

Item 57Macromolecules32, No.19, 21st Sept.1999, p.6307-18TWO-DIMENSIONAL FOURIER TRANSFORMRAMAN CORRELATION SPECTROSCOPYSTUDIES OF POLYMER BLENDS:CONFORMATIONAL CHANGES AND SPECIFICINTERACTIONS IN BLENDS OF ATACTICPOLYSTYRENE AND POLY(2,6-DIMETHYL-1,4-PHENYLENE ETHER)Ren Y; Murakami T; Nishioka T; Nakashima K; Noda I;Ozaki YKwansei-Gakuin,University; Idemitsu PetrochemicalCo.Ltd.; Saga,University; Procter & Gamble Co.

Fourier transform Raman spectra were determined foratactic polystyrene (PS), poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and their blends, composition-dependent spectral variations of the blends being analysedusing generalised two-dimensional correlationspectroscopy to study the conformational changes andblend-interactions. The two-dimensional synchronouscorrelation analysis was able to discriminate between thebands of PS and those of PPE, and was able to detectbands which were not readily identifiable in one-dimensional spectra. The main chain conformation of PSunderwent a drastic change on blending with PPE.Abnormal behaviour of bands at 1448 and 1329 /cm wasattributed to backbone methylene vibrations, and of theband at 1070 /cm to C-C stretching vibration. Numerousout-of-phase band variations were observed. It wasconcluded that not only the phenyl ring of PS and PPE,but also the CH3 groups of PPE played an important rolein the formation of the blends. 41 refs.JAPAN; USA

Accession no.756086

Item 58Journal of Applied Polymer Science74, No.11, 9th Dec.1999, p.2703-15KINETIC STUDY OF PHENOLIC RESIN CUREBY IR SPECTROSCOPYCarotenuto G; Nicolais LNaples,University

Fourier transform infra red spectroscopy was used to studythe cure reaction and reaction kinetics of a commercialphenolic resin, using IR spectra in the absorbance mode.It was found that below 140 deg. centigrade that the

kinetics of the reaction followed the Jander kinetic modeland that a diffusive mechanism was in control. Above140 deg.C a homogenous first order reaction model bestdescribed the reaction, as indicated by analysis usingintegral methods on the isothermal data. Other modelstested, including diffusion controlled reactions, nucleationand growth kinetics and phase boundary movement didnot fit the observed data as well as the first orderhomogenous model. A proposal for a mechanistic modelfor the resol cure at temperatures greater than 140 deg.Cis made. 34 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;WESTERN EUROPE

Accession no.756012

Item 59Polyurethanes Expo ’99. Conference proceedings.Orlando, Fl., 12th-15th Sept.1999, p.303-11FIBRE OPTIC FTIR: A NOVEL PUR/PIRCATALYST DEVELOPMENT TOOLMcDaniel P L; Johnson G L; Kniss J G; Sabram K AAir Products & Chemicals Inc.(American Plastics Council,Alliance for thePolyurethanes Industry)

Development of new catalysts promoting differentphases of PU foam formation (blowing, gelling,crosslinking) is typically done using a series of physicaland handmix generated reactivity profile properties.The ability to understand the evolution of chemicalspecies associated with rigid PU/polyisocyanurate(PUR/PIR) foam formation has been historically onlyinferred based on their final distribution in the fullycured foam using FTIR or solid state carbon-13 NMR.Neither technique gives insight into the reactions asthey occur. Recently, the use of IR transmitting opticalfibres as evanescent wave sensors and a mathematicaldeconvolution technique (iterative targettransformation factor analysis) to extract and followthe isocyanate, urea, urethane and trimer concentrationsas they occur in both lab scale and machine scale foamproduction have been refined. The fibre optic probeused can be placed at specific locations within thegrowing foam to target the evolution of isocyanatechemistries at the surface or core of the foam. Thespecificity of the technique, speed of data acquisitionand portability of equipment all make this method idealas a tool to fundamentally probe how catalysts alterthe distribution of individual chemical species duringthe initial moments in foam formation. Its utility inunderstanding the mechanism whereby a novel newcatalyst, Polycat 48, improves dimensional stability ina HCFC-141b blown appliance formulation, isdemonstrated. The fibre optic FTIR results for Polycat48 are contrasted to a control catalyst blend of Polycat5 and Polycat 41 in the same formulation. 10 refs.USA

Accession no.755697



Item 60Journal of Polymer Science: Polymer Physics Edition37, No.19, 15th Sept. 1999, p.2642-50IR SPECTRA STUDIES OF CORE-SHELL TYPEWATERBOURNE POLYACRYLATE-POLYURETHANE MICROEMULSIONSDong A; Wan T; Feng S; Sun DEdited by: Tianjin,University

FTIR spectroscopy was used to study hydrogen bondingin films of polyurethane and core shell type polyacrylate-polyurethane microemulsions. The effects of hydrogenbonding on composition, core shell ratio and itsrelationship to crosslinked structures (Type A and B) wasrevealed. Shifts of the -NH and C=O stretching bands tohigher frequencies and the -NH bending bands to lowerfrequencies, with increase in acetone C=O number in thecore reveals that the hydrogen bonds are broken betweenthe soft and hard segments and those in the short rangeorder in the hard segment phase. 24 Refs.CHINA

Accession no.755231

Item 61Journal of Polymer Science: Polymer ChemistryEdition37, No.16, 15th Aug.1999, p.3317-27MICRO-RAMAN INVESTIGATIONS OF PVDF-BASED PROTON-CONDUCTING MEMBRANESMattsson B; Ericson H; Torell L M; Sundholm FChalmers University of Technology

Proton-conducting membranes were prepared by graftingpoly(vinylidene fluoride) (PVDF) with styrene followedby sulphonation. The depth and surface distribution ofthe polystyrene grafts and crosslinker, and thesulphonation efficiency were studied using confocalRaman microspectroscopy. Highly grafted samples had ahomogeneous distribution of grafts and homogeneoussulphonation, whereas uneven graft distributions wereobserved in samples with low and intermediate degreesof grafting. The crosslinker concentration in the interiorof the film was approximately 50% of the surfaceconcentration. Sulphonation efficiencies were poor at lowgraft levels, and were further inhibited by the presence ofdivinyl benzene crosslinker. At degrees of grafting inexcess of 60%, the sulphonation efficiency was notaffected by the crosslinker. The matrix polymer structurewas largely retained after irradiation, grafting, andsulphonation. 32 refs.SCANDINAVIA; SWEDEN; WESTERN EUROPE

Accession no.753415

Item 62Progress in Organic Coatings35, No.1-4, Aug.1999, p.197-204DEPTH PROFILING OF UV CURED COATINGSCONTAINING PHOTOSTABILIZERS BY

CONFOCAL RAMAN MICROSCOPYSchrof W; Beck E; Koniger R; Reich W; Schwalm RBASF AG

Confocal Raman microscopy combines chemicalinformation from vibrational spectroscopy with the spatialresolution of confocal microscopy. Examples of its use aregiven, including: the investigation of variation ofcrosslinking with depth in thicknesses of up to 0.5 mm inUV-cured coatings; variations of curing with depth inpigment formulations, in thicknesses of up to 30micrometre; and studies of the effect of UV light stabiliserson the UV curing of coating formulations. 11 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.752449

Item 63Journal of Applied Polymer Science74,No.3, 17th Oct.1999, p.532-40TETRAFUNCTIONAL EPOXYRESINS:MODELING THE CURING KINETICSBASED ON FTIR SPECTROSCOPY DATAMusto P; Martuscelli E; Ragosta G; Russo P; Villano PItaly,National Research Council

The curing kinetics of two thermosetting systems basedon a tetrafunctional epoxy resin are investigated byFourier transform infrared spectroscopy. Twoformulations are studied, in which the hardener is anaromatic diamine and a carboxylic dianhydride,respectively. The quantitative evaluation of the epoxyconversion is based on spectra collected in the near-infrared range (8000-4000 cm -1) as well as in the mediumIR range (4000-400 cm -1). The kinetic parametersevaluated in the above frequency intervals aresignificantly different. The reasons for such a discrepancyare critically discussed. Several kinetic models, based onthe widely employed Kamal approach, are applied toverify their predictive capability. Satisfactory results areobtained for the amine-cured system, particularly with amodified equation taking into account the autocatalyticnature of the process as well as a limiting diffusionaleffect. Less accurate results are achieved for theanhydride-cured system. 23 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;WESTERN EUROPE

Accession no.752308

Item 64Journal of Applied Polymer Science74,No.3, 17th Oct.1999, p.516-22REACTIVITY RATIOS OF N-CYCLOHEXYLMALEIMIDE ANDMETHYLMETHACRYLATE BY INFRAREDSPECTROSCOPYDong S; Wei Y; Zhang ZHarbin,Institute of Technology



The copolymerisation of N-cyclohexylmaleimide(CHMI) and methyl methacrylate (MMA) withazobisisobutyronitrile as the initiator is investigated.IR spectroscopy is applied to determine the copolymercompositions of the copolymers synthesised at 60, 70,80 and 90 deg.C while the conversions of thecopolymerisations are controlled to be below 10%.According to the Mayo-Lewis equation, the reactivityratios of N-cyclohexylmaleimide and methylmethacrylate are calculated. It is proved that N-cyclohexylmaleimide is less reactive, and the optimumtemperature of the copolymerisation is 80 deg C. 8 refs.CHINA

Accession no.752306

Item 65Macromolecules32, No.17, 24th Aug.1999, p.5552-60RAMAN SPECTROSCOPICCHARACTERISATION OF ASSOCIATION ANDTHERMOREVERSIBLE GELATION INAQUEOUS SYSTEMS OF POLY(N-ACETAMIDOACRYLAMIDE)Ostrovskii D; Jacobsson P; Nystrom B; Marstokk O;Kopperud H B MChalmers University of Technology; Oslo,University;Jotun AS

A study was made of self-association andthermoreversible gelation in aqueous solutions ofpoly(N-acetamidoacrylamide) using Ramanspectroscopy. The presence of polymer-polymercoordination was observed even at low concentrations,indicating polymer cluster formation. The influence ofsodium thiocyanate, as denaturant, on intermolecularand intramolecular interactions was also examined andthe effects of polymer concentration, level ofdenaturant addition and type of solvent, on gelformation evaluated. 41 refs.NORWAY; SCANDINAVIA; SWEDEN; WESTERN EUROPE

Accession no.752236

Item 66Macromolecular SymposiaVol.141, 1999, p.103-16RAMAN SPECTROSCOPY FOR POLYMERCHARACTERISATION IN AN INDUSTRIALENVIRONMENTEverall N; King BICI Wilton Research Centre

The versatility of Raman spectroscopy for the on-lineanalysis of polymers both in the laboratory and also in-situ on the production line is demonstrated and the benefitsand disadvantages of the technique as an on-line methodare considered. Application of the technique to an analysisof acrylic terpolymers, monitoring of polymerisation andon-line measurement of morphology/composition is

considered and difficult on-line sampling situations arebriefly discussed. 14 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.752092

Item 67Computational and Theoretical Polymer Science9, No.3/4, 1999, p.327-33CONFORMATIONAL DEPENDENCE OFRAMAN FREQUENCIES AND INTENSITIES INALKANES AND POLYETHYLENEKoglin E; Meier R JJulich,Institute of Applied Physical Chemistry; DSMResearch

Raman vibrational frequencies and intensities of octane,dodecane and hexadecane conformers were calculatedusing quantum mechanical ab initio methods. The resultsagreed with various trends observed in the experimentalspectra of alkanes, as well as several observations fromthe experimental Raman spectra of PEs. The data obtainedindicated that ab initio calculated Raman data on alkanesprovided valuable information regarding the interpretationof polymer Raman spectra, in particular informationconcerning issues where interpretation based onexperimental verification was not possible. 23 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;NETHERLANDS; WESTERN EUROPE

Accession no.750357

Item 68Antec ’99. Volume II. Conference proceedings.New York City, 2nd-6th May 1999, p.2502-6. 012MEASURING THE DIFFUSIVITY OFADDITIVES IN POLYMER FILMS USING INSITU FTIR-ATR SPECTROSCOPYGaghardi C A.; Muire L B; Hirt D EClemson,University(SPE)

In many polymer-film applications, additives migrate fromthe bulk of a film to the film surfaces. For these cases, it ismore realistic to measure the additive diffusivity in adiffusion-out mode rather than using a mass-sorption(diffusion-in) experiment. This is particularly true foradditives that are solids at the testing temperature. Thisresearch focuses on the evaluation of additive diffusivityin a diffusion-out mode via in situ FTIR-ATR spectroscopy,which has the advantage of requiring only small samplesof thin films. The technique is described, including methodsto obtain reproducible contacting pressure between a filmsample and an ATR crystal and to perform in situexperiments at elevated temperatures. Diffusivity resultsare presented for the migration of an erucamide slip agentin LLDPE films. 11 refs.USA

Accession no.749605



Item 69Antec ’99. Volume II. Conference proceedings.New York City, 2nd-6th May 1999, p.2429-32. 012INFRARED CHARACTERISATION OF VINYLCINNAMATE COPOLYMER BLENDS BEFOREAND AFTER UV EXPOSUREColeman M; Hu Y; Painter P CPennsylvania,State University(SPE)

During the past three years or so, chain connectivity andits effect on the free energy of mixing and phase behaviourof (co)polymer blends has been studied. IR spectroscopyhas been the primary tool because in carefully chosenmixtures it is possible to measure the fraction of hydrogenbonded groups present as a function of composition andtemperature. Attention is now turned to the effect ofcrosslinking one or both of the (co)polymers in the blendand the results of recent FTIR spectroscopic studies arepresented.

USA

Accession no.749591

Item 70Antec ’99. Volume II. Conference proceedings.New York City, 2nd-6th May 1999, p.2424-8. 012MOLECULAR ANALYSIS OF POLYMERS BYFTIR PHOTOACOUSTIC SPECTROSCOPYMcClelland J F; Jones R; Bajic SMTEC Photoacoustics Inc.; Iowa State University(SPE)

FTIR photoacoustic spectroscopy (PAS) has advantagesrelative to conventional IR techniques (transmission,reflection and emission) because it is non-destructive,does not involve sample preparation and can probesamples with compositional gradients and layers. Thetheory, instrumentation, methods and applications ofFTIR-PAS are discussed and results are presented onseveral polymer analyses based on FTIR-PAS. 4 refs.

USA

Accession no.749590

Item 71Antec ’99. Volume II. Conference proceedings.New York City, 2nd-6th May 1999, p.1937-41. 012IN-LINE MONITORING OF MULTIPLEADDITIVES IN POLYETHYLENE MELT USINGFIBRE-OPTIC SPECTROSCOPYLi J; Hansen M GTennessee,University(SPE)

The feasibility of simultaneous in-line monitoring ofadditives Irganox 1076, Irgafos 168, Tinuvin 622,erucamide and Armostat 310 is studied in molten LDPE.The near IR (NIR) and UV spectroscopic systems usedfor the determination of additives are described. Based

on Partial Least Square (PLS) multivariate regressionanalysis, calibration models are built for predicting theconcentrations of additives. It is found that some additivescan be predicted reliably. 7 refs.USA

Accession no.748748

Item 72Polymer Testing18, No.7, 1999, p.551-7DIRECT DETERMINATION OF VINYLACETATE CONTENT OF ETHYLENE-VINYLACETATE COPOLYMERS IN THICK FILMS BYINFRARED SPECTROSCOPYMeszlenyi G; Kortvelyessy GSzeviki Organic Chemistry Research Institute

An IR spectroscopic method was developed for thedetermination of vinyl acetate content in thick (about 100micrometres) films of EVAs. The A3460/A3610 ratio wasused for the quantitative analysis, the function of this ratioplotted against vinyl acetate content of the EVA filmsbeing a convex hyperbola. The technique was simple andrapid and did not require a complicated sample preparationprocedure. 11 refs.EASTERN EUROPE; HUNGARY

Accession no.748436

Item 73Applied Spectroscopy53, No.8, Aug.1999, p.919-26TWO-DIMENSIONAL NEAR-INFRAREDCORRELATION SPECTROSCOPY STUDIES ONCOMPOSITION-DEPENDENT SPECTRALVARIATIONS IN ETHYLENE/VINYL ACETATECOPOLYMERS: ASSIGNMENTS OF BANDS DUETO ETHYLENE UNITS IN AMORPHOUS,DISORDERED, AND ORTHORHOMBICCRYSTALLINE PHASESYanzhi Ren; Shimoyama M; Ninomiya T; MatsukawaK; Inoue H; Noda I; Osaki YKwansei-Gakuin,University; Hyogo,Prefectural PoliceHeadquarters; Osaka Municipal Technical ResearchInstitute; Procter & Gamble Co.

Results of the above studies are presented and discussedin relation to the potential of three powerful techniques,i.e. two-dimensional correlation analysis, the calculationof the second derivatives and calculation of regressioncoefficients in chemometrics, in examining the rathercomplex near-IR spectra. 22 refs.JAPAN; USA

Accession no.748410

Item 74Journal of Applied Polymer Science73, No.14, 29th Sept.1999, p.2837-47



FTIR QUANTITATIVE CHARACTERIZATIONOF CHEMICALLY MODIFIEDPOLYPROPYLENES CONTAINING SUCCINICGRAFTED GROUPSGarcia-Martinez J M; Laguna O; Areso S; Collar E PInstituto de Ciencia y Tecnologia de Polimeros

The grafting of succinic anhydride onto PPs was evaluatedquantitatively by FTIR spectroscopy. The relativeabsorbance values obtained from the IR spectra werecorrelated with grafting levels of the sample as determinedby an improved traditional hot titration method. Theresults obtained appeared to be valid for either atactic orisotactic modified PPs and suggested that a careful reviewshould be conducted of the use of this technique in thequantification of polar groups grafted onto polyolefins.37 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;WESTERN EUROPE

Accession no.747390

Item 75Journal of Applied Polymer Science73, No.8, 22nd Aug.1999, p1569-77UV CURING OF SURFACE COATING SYSTEMCONSISTING OF CYCLOALIPHATICDIEPOXIDE-ENR-GLYCIDYL METHACRYLATEBY CATIONIC PHOTOINITIATORS-CHARACTERIZATION OF THE CURED FILMBY FTIR SPECTROSCOPYKumar R N; Woo C K; Abusamah AMalaysia,Science University

Films were cast from a system consisting of acycloaliphatic diepoxide, epoxidised natural rubber(ENR), glycidyl methacrylate (GMA) and a cationicphotoinitiator, triphenylsulphonium hexafluoro-antimonate. The films were cured by UV radiation, andcharacterised using Fourier transform infraredspectroscopy. It was determined that the acrylic doublebonds, the epoxy groups of GMA, the isoprene doublebonds, the epoxy groups of ENR, and the epoxy groupsof the cycloaliphatic epoxide resin all participated inthe photoinitiated polymerisation and crosslinkingreactions resulting in an interpenetrating polymernetwork. 21 refs.MALAYSIA

Accession no.744182

Item 76Journal of Vinyl and Additive Technology5, No.2, June 1999, p.81-6FOURIER TRANSFORM INFRARED MICROSPECTROSCOPY MAPPING STUDIES OFWEATHERED PVC CAPSTOCK TYPEFORMULATIONS. II. OUTDOOR WEATHERINGIN PENNSYLVANIAGarcia D; Black J

Elf Atochem NA

FTIR micro spectroscopy, coupled with mappingtechniques, was shown to be an effective method forevaluating dimensionally-dependent changes such asthose encountered in PVC weathering processes. Themethod was based on the complexity and specificity ofthe IR spectrum and the dimensional resolution of themicroscope. A systematic FTIR study was conducted ofchanges observed during outdoor photodegradation ofPVC siding capstock formulations, as a function ofexposure time and titanium dioxide level. The results werecompared with previously-obtained accelerated QUVdata. Profiles through the thickness dimension wereanalysed to identify degradation species and depthdistribution. 14 refs.USA

Accession no.743282

Item 77Polymer Recycling3, No.4, 1997/1998, p.287-93QUALITATIVE AND QUANTITATIVECHARACTERISATION OF MIXED POLYMERSUSING NEAR-INFRARED-SPECTROSCOPY(NIR)Michaeli W; Plessmann K W; Andrassy B; Breyer K;Laufens PIKV; Aachen,University of Technology

Details are given of an experimental technique, (the PLS2method), which has been developed to determine thecomposition of mixed polymers using the NIR techniqueas a tool for the quality control of recycled plastics. PP/polystyrene blends were quantitively analysed, and theeffects of aluminium and paper contaminants wereevaluated. 9 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.742800

Item 78ACS Polymeric Materials Science &Engineering.Volume 80.Conference proceedings.Anaheim, Ca., Spring 1999, p.556-7IN-SITU FTIR INVESTIGATION ON CHAINCONFORMATION CHANGE UPON HEATINGFOR PAUCI-CHAIN POLYSTYRENEMICROSPHERE MADE BY MICROEMULSIONPOLYMERIZATIONWeihua Ming; Yiqiang Zhao; Jun Zhao; Shoukuan Fu;Jones F NFudan,University; Eastern Michigan,University(ACS,Div.of Polymeric Materials Science & Engng.)

Polystyrene microspheres, produced by microemulsionpolymerisation, generally contain only one or a fewpolymer chains, and may thus be termed single- or pauci-



chain microspheres. Changes in chain conformation onheating were studied using in-situ Fourier transforminfrared spectroscopy. Discontinuities in the relationshipbetween peak height and temperature were attributed tothe glass transition and changes in the phenyl ring stretchmode due to the formation of phenyl ring stacking. 12refs.CHINA; USA

Accession no.742138

Item 79Polymer Bulletin42, No.5, May 1999, p.579-86RHEO-OPTICAL FOURIER TRANSFORMINFRARED SPECTROSCOPY OF DIOL-MODIFIED DIGLYCIDYL ETHER OFBISPHENOL-A EPOXY RESINSScherzer TLeipzig,Institut fuer Oberflachenmodifizierung

Diol-modified epoxy resins were prepared from bisphenolA diglycidyl ether modified with alpha,omega-diols ofdifferent chain lengths and at different molar ratios. themolecular orientation of the epoxy networks wasinvestigated using rheooptical FTIR spectroscopy anduniaxial deformation was carried out above and belowthe glass transition temperature. The effects of diol chainlength and molar ratio on the mechanical properties andorientation parameter were discussed. 17 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.741938

Item 80Applied Spectroscopy53, No.6, June 1999, p.682-6IN SITU ANALYSIS OF A HIGH TEMPERATURECURE REACTION IN REAL TIME USINGMODULATED FIBRE-OPTIC FT-RAMANSPECTROSCOPYAust J F; Cooper J B; Wise K L; Jensen B JOld Dominion University; US,NASA,LangleyResearch Center

The high temperature (330C) cure reaction of 4-phenoxy-4'-phenylethynylbenzophenone was monitored using amodulated fibre-optic Fourier transform-Ramanspectrometer. Spectral evidence for two different reactionpathways (cyclisation and chain extension) is provided.The formation of a conjugated double bond system ofvarying chain lengths is indicated. 19 refs.USA

Accession no.741261

Item 81Applied Spectroscopy53, No.6, June 1999, p.672-81

POST-CONSUMER PLASTIC IDENTIFICATIONUSING RAMAN SPECTROSCOPYAllen V; Kalivas J H; Rodriguez R GIdaho,State University

The suitability of Raman spectroscopy, when used withK-nearest neighbours, library searching or cyclic subspaceregression, for computerised classification of post-consumer plastics was evaluated. Plastics investigatedwere PETP, PP, PS, PVC, HDPE AND LDPE.Modifications were made to the original cyclic subspaceregression algorithm for modelling multiple sampleproperties and the adapted algorithm employed to directlycompare the mechanisms of principal componentregression and the PLS2 form of partial least-squares. Itwas found that Raman spectroscopy could be used toidentify both HDPE and LDPE. 33 refs.USA

Accession no.741260

Item 82Applied Spectroscopy53, No.5, May 1999, p.557-64COMPARISON OF NEAR-INFRARED ANDRAMAN SPECTROSCOPY FOR THEDETERMINATION OF CHEMICAL ANDPHYSICAL PROPERTIES OF NAPHTHAMin-Sik Ku; Hoeil ChungSK Corp.

Near-infrared and FTIR Raman spectroscopy werecompared and evaluated for the quantitative analysis ofnaphtha using partial least-squares regression. 19 refs.SOUTH KOREA

Accession no.740339

Item 83ACS, Polymeric Materials Science and Engineering.Vol.76. Conference proceedings.San Francisco, Ca., Spring 1997, p.191-2. 012TOWARDS A BETTER UNDERSTANDING OFSEGMENTAL MOBILITY IN POLYMERSUNDER EXTERNAL PERTURBATIONS: TIME-RESOLVED FTIR-STUDIESAmeri A; Ekgasit S; Hendann C; Michel S; Wu P;Okretic S; Pfeifer F; Zebger I; Siesler H WEssen,University(ACS,Div.of Polymeric Materials Science & Engng.)

The elucidation of the mechanisms and dynamics ofsegmental mobility in polymers under the influence ofexternal perturbations can tremendously contribute to theimprovement of certain manufacturing processes or to theoptimisation of the engineering properties of technicallyimportant polymeric materials. Application of a uniaxialor bidirectional elongation, on the other hand, is acommon pretreatment of a polymeric material to improveits mechanical end-use properties. Generally, time-



resolved IR spectroscopy has proved an extremelyvaluable tool to investigate the structural details ofmolecular changes incurred by a polymer under theinfluence of such an external perturbation. The elucidationof the transient molecular changes during polymerdeformation is an important issue in polymer processing.In the film forming process, an amorphous sheet is castfrom the melt onto a cooled drum, followed by sequentialforward and sideways drawing at different temperaturesand heat setting in ovens. The ability to monitor and modelsuch drawing and relaxation processes would benefitgreatly product quality and web efficiency. Rheo-opticalFTIR spectroscopy is one of the few techniques providingdata on the crystallisation, orientation and conformationalchanges of a polymer during mechanical treatment. Toemphasise the potential of the technique, selectedexamples of rheo-optical measurements on industriallyrelevant thermoplastic and elastomeric polymers arepresented and interpreted in terms of their deformation,recovery and relaxation mechanisms. Where applicable,2D-correlation analysis is utilised to enhance theinformation derived from the vibrational spectroscopicdata. 3 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.737971

Item 84Polymer40, No.17, 1999, p.4723-31INFRARED AND RAMAN SPECTROSCOPY OFCYCLOHEXA(P-PHENYLENE SULPHIDE) ANDTHE POLYMER OBTAINED THEREFROMZimmerman D A; Koenig J L; Ishida HCase Western Reserve University

Cyclohexa(p-phenylene sulphide) (CHPS) was studied asa precursor of poly(p-phenylene sulphide) (PPS). TheFTIR and Raman spectra of CHPS were found to resemblethose of amorphous PPS closely. Specific modesindicative of the crystal structure and band shifts werereported. A crystal structure change in CHPS which wasinduced by pressure or heat was identified. Polymerisationof CHPS was carried out and the polymerised CHPSshowed a slightly higher crystallinity than that ofcommericial low molecular weight PPS with minimalbranching. 23 refs.USA

Accession no.737357

Item 85Colloid & Polymer Science277, No.4, April 1999, p.376-81FOURIER TRANSFORM INFRARED STUDY OFTHE PHASE TRANSITION IN AQUEOUSSOLUTIONS OF ETHYLENE OXIDE-PROPYLENE OXIDE TRIBLOCK COPOLYMER

Guo C; Liu H Z; Chen J YChinese Academy of Sciences

The phase transition between unimer and micellar phasesof polyethylene oxide-polypropylene oxide-polyethyleneoxide) (PEO-PPO-PEO) triblock copolymer PluronicP105 in aqueous solution is investigated as a function oftemperature using Fourier transform infraredspectroscopy. The transition of 8 wt.% Pluronic P105 inaqueous solution is found to occur at 25 deg.C. As thetemperature increases, PO blocks appear to be stretchedconformers with strong interchain interaction, and theformation of a hydrophobic core in the micellar phase.The EO chains are found to change to a more disorderedstructure with low-chain packing density from the unimerphase to the micellar phase. Both the EO and PO blocksexhibit dehydration during the phase transition. 20 refs.CHINA

Accession no.732300

Item 86Coloring Technology for Plastics.New York, N.Y., Plastics Design Library, 1999, p.197-207. 52MEASURING STABILISERS IN PIGMENTEDPLASTICS WITH NEAR-INFRAREDSPECTROSCOPYSolera P; Nirsberger M; Castillo NCiba Specialty Chemicals Corp.Edited by: Harris R M

Near-infrared (NIR) spectroscopy has become acommonplace analytical tool in the plastics industry. NIRtechniques have made quantification of many organiccomponents in polymer processing easy and quick. Thework presented outlines the methodology for using NIRto measure stabiliser levels in colour concentrates andnatural polymer formulations. Advantages and limitationsare considered as well as particle size and product form.4 refs.USA

Accession no.732217

Item 87Coloring Technology for Plastics.New York, N.Y., Plastics Design Library, 1999, p.191-5. 52PRACTICAL ANALYSIS TECHNIQUES OFPOLYMER FILLERS BY FOURIERTRANSFORM INFRARED SPECTROSCOPY(FTIR)Coles B J; Hall C JHauser Inc.Edited by: Harris R M

The identification of polymers by FTIR is often complicatedby the presence of fillers. However, for kaolin clay, FTIRanalysis should be able to identify the filler and predict its



concentration using a standard curve. The resultingpercentage is more reliable than a simple ash, which maychange the chemical composition of the filler. 2 refs.USA

Accession no.732216

Item 88Macromolecules32, No.8, 20th April 1999, p.2748-60FTIR IMAGING STUDIES OF A NEW TWO-STEPPROCESS TO PRODUCE POLYMERDISPERSED LIQUID CRYSTALSBhargava R; Shi-Qing Wang; Koenig J LCase Western Reserve University

A method for reducing liquid crystal solubility inproduction of polymer dispersed liquid crystals(PDLCs)was developed which involved cooling a homogeneousliquid crystal/precursor matrix into the two-phase regime,followed by fast matrix polymerisation. The proposedprocedure was tested by using a well-studied PDLCsystem, NOA65 (a UV-curable optical adhesive) and E7(a mixture of cyanobiphenyls). Liquid crystal remainingdissolved in the matrix was sharply reduced by thismethod. Residual solubility of the matrix material in liquidcrystal domains was also decreased. While maintainingthe same phase composition, the method also allowedtailoring dispersion size according to needs as opposedto the invariable correlation between droplet size,solubility and polymerisation rate inherent in the classicalpolymerisation-induced phase separation methods. Thisgeneral methodology could be usefully applied to othersystems. FTIR imaging, combined with statisticalmethods, was shown to be a valuable tool for determiningphase composition in multiphase systems. 49 refs.USA

Accession no.731938

Item 89Macromolecules32, No.8, 20th April 1999, p.2684-9CONFORMATIONALLY SENSITIVE INFRAREDVIBRATIONS OF THE SYNDIOTACTICPOLYSTYRENE/ETHYLBENZENE COMPLEXMoyses S; Spells S JSheffield,Hallam University

The 920 to 960/cm region of the IR spectrum of the deltaphase syndiotactic PS/ethylbenzene predominantlyinvolved bands arising from helical structures and wasstudied as a function of heating temp. Curve fitting anddeconvolution showed the necessity, for annealing temps.above 120C, of adding a third component at 940/cm topeaks at 934 and 943/cm. The 934 and 943/cm peaksbehaved as a doublet, primarily due to the delta phase, withthe splitting increasing on annealing. The 940/cm peak wassolely due to the gamma phase helix. These assignmentsprovided the opportunity for using these bands for further

studies of complexation/decomplexation in such systems.The reduction in absorbance of 934 and 943/cm peaksoccurred at a lower temp. than the rise in the 940/cmabsorbance and this was attributed to disordering of thedelta phase helices prior to reformation as gamma phasehelices. Similar measurements using deuteratedsyndiotactic PS also showed helix and zigzag bands, butwithout a predominantly delta phase helix peak. Solventpeaks in the deuterated syndiotactic PS/ethylbenzenesystem were used to monitor the delta to gamma phasetransition. In combination with DSC and TGA data, them.p. of the alpha phase was found to be depressed by 7Cfor the deuterated polymer, while the delta to gamma phasetemp. was shown to be about 24C higher. 26 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.731930

Item 90Polymer Preprints. Volume 40. Number 1. March 1999.Conference proceedings.Boston, Ma., March 1999, p.627-8. 012ELUCIDATION OF CRYSTALLINE STRUCTUREIN POLYETHYLENE TEREPHTHALATE BYEXTERNAL REFLECTION INFRAREDSPECTROSCOPYCole K C; Ajji A; Pellerin ECanada,National Research Council(ACS,Div.of Polymer Chemistry)

Despite countless studies of the microstructure of PETPand its relationship to process conditions and properties,the complex behaviour of this polymer is not fullyunderstood. While it is clear that it cannot be described interms of a simple two-phase (amorphous-crystalline)model, the nature of the third or intermediate phase is noteasy to define. The morphology of the ‘strain-inducedcrystalline’ material produced by drawing amorphous PETPis different from that of material obtained by thermalcrystallisation. Furthermore, it has been shown that thermalcrystallisation involves two distinct stages. The primarystage starts to become significant around 90 deg.C not farabove the glass transition temperature, and shows asigmoidal dependence on log (time). The secondary stagebecomes significant only above about 140 deg.C and showsa linear dependence on log (time). Front-surface reflectionIR spectroscopy is used to characterise the structure ofdrawn samples. This approach is particularly interestingbecause it provides the complete IR spectrum, includingthe highly absorbing bands that are often saturated intransmission spectra. Significant differences betweensamples with strain-induced crystallinity and one that wasthermally crystallised are observed. The study is extendedto samples thermally crystallised over a wider range ofconditions, in order to better understand the phenomenathat govern the crystallisation of PETP. 4 refs.CANADA

Accession no.730486



Item 91ACS Polymeric Materials Science & Engineering.Volume 74. Conference proceedings.New Orleans, La., Spring 1996, p.266-7. 012CRACK ANALYSIS OF UNFILLED NATURALRUBBER USING INFRAREDMICROSPECTROSCOPYNeumeister L A; Koenig J LCase Western Reserve University(ACS,Div.of Polymeric Materials Science & Engng.)

The fatigue of natural and styrene-butadiene rubbers isan enormous industrial problem, as important mechanicalproperties of these materials deteriorate quickly whenstressed. Although fatigue may describe the deteriorationof certain material properties, it is generally believed thatthe term also describes failure by cracking. In fact,abrasive wear is due to the cumulative growth of cracksby tearing under repetitive loading. Therefore, the analysisand characterisation of cracks in NR are crucial to thedevelopment of material with improved fracture resistantproperties. Several spectroscopic methods are availablefor characterising the crack tip region of the rubber onthe molecular scale. Attenuated total reflectance or ATR-IR has been used to characterise the structure of manydifferent polymers. For example, it has been used tocharacterise the structure of 1,2-polybutadiene as well asto study the reactions of polymers. Transmission has alsobeen well established as a viable technique for themolecular characterisation of transparent materialsincluding thin films of unfilled NR. Again the spectracan be used for quantitative and qualitativeexperimentation and analysis. 7 refs.USA

Accession no.724898

Item 92International Symposium on Orientation of Polymers:Application to Films and Fibres. Retec proceedings.Boucherville, Qc., 23rd-25th Sept.1998, p.573-74.8(11)32MOLECULAR ORIENTATION ANDRELAXATION STUDIES OF POLYMERS USINGPOLARISATION MODULATION INFRAREDSPECTROSCOPYPellerin C; Vrabie D G; Duchesne C; Bazuin C G;Brisson J; Pezolet M; Prud’homme R EQuebec,Universite Laval(SPE; NRC/IMI)

The apparatus is described and details given of its usewith PETP homopolymer, PS/poly(vinyl methyl ether)miscible blend and styrene-styrenesulphonic acidcopolymer/ethyl acrylate-4-vinylpyridine copolymerionomer blend with ionic interactions. Orientation andrelaxation curves were obtained for all three samples. Itis concluded that the technique is very efficient forobtaining curves with high precision. For these threesystems, the relaxation rate increases with temperature.

For PETP, a reorientation as a function of time wasobserved. This phenomenon is dependent on temperatureand draw ratio, and is probably due to the crystallisationof the sample. For the PS/poly(vinyl methyl ether) blend,the addition of poly(vinyl methyl ether) to the blendincreased the orientation of the PS chains during thestretching. For the ionomer blends, the orientation of bothtypes of chain was higher when the ionic contentincreased. 4 refs.CANADA

Accession no.724352

Item 93Polymer40, No.10, 1999, p.2619-24THERMAL MICRO ATR/FT-IRSPECTROSCOPIC SYSTEM FORQUANTITATIVE STUDY OF THE MOLECULARSTRUCTURE OF POLY(N-ISOPROPYLACRYLAMIDE) IN WATERShan-Yang Lin; Ko-Shao Chen; Liang Run-ChuTaipei,Veterans General Hospital; Tatung,Institute ofTechnology

A newly developed thermal micro attenuated totalreflection (ATR)/FTIR spectroscopic system with curvefitting program was used for the quantitative investigationof molecular interactions in aqueous solutions of poly(N-isopropylacrylamide) (PNIPAAM). The lower criticalsolution temperature (LCST) in water of the PNIPAAMstudied was found to be about 33C by cloud pointmeasurement, DSC and the thermal micro ATR/FTIRspectroscopic system. The results from the newspectroscopic system with curve fitting program indicatedthat intermolecular interactions might predominatebetween PNIPAAM and water at temperatures below theLCST but above the LCST, PNIPAAM molecules in waterwere aggregated because of intramolecular interactionswithin the PNIPAAM molecules and the hydrophobicinteractions in the system. 35 refs.TAIWAN

Accession no.724062

Item 94Polymer40, No.10, 1999, p.2569-86MORPHOLOGICAL CHARACTERISATION OFTHE CRYSTALLINE STRUCTURE OF COLD-DRAWN HDPE USED AS A MODEL MATERIALFOR THE ENVIRONMENTAL STRESSCRACKING (ESC) PHENOMENONLagaron J M; Dixon N M; Reed W; Pator J M; Kip B JDSM Research; BP Chemicals; Valladolid,Universidad

Micro-Raman spectroscopy was used in conjunctionwith mechanical deformation to study the structuralchanges which occur in the cold drawing of HDPE. Thecold drawn structure was highly orientated and a large



decrease in the Raman orthorhombic crystallinity wasseen. The results indicated an ill-defined orthorhombiccrystalline structure with dislocations and disruptedcrystals formed by cold drawing, possibly resulting frommolecules being pulled through the crystals. In-situRaman straining experiments, carried out on cold drawnHDPE at 240K, showed that further orthorhombiccrystalline disruption occurred with strain. No disruptionwas observed in fibrils created during environmentalstress crack resistance tests at 348K. Temperature wasan important parameter in the crystalline phase recoveryof the orthorhombic crystallinity and when the colddrawn HDPE was annealed, the monoclinic phasedisappeared. 47 refs.EUROPEAN COMMUNITY; EUROPEAN UNION;NETHERLANDS; SPAIN; UK; WESTERN EUROPE

Accession no.724059

Item 95ACS Polymeric Materials Science & Engineering,Spring Meeting 1998. Volume 78. Conferenceproceedings.Dallas, Tx., Spring 1998, p.24. 012ANALYSIS OF A POLYURETHANEELASTOMER USING THERMAL 2D FT-IRGraff D K; Wrobleski D A; Marsh A L; Kober E M;Smith M E; Schnoover J RLos Alamos National Laboratory(ACS,Div.of Polymeric Materials Science & Engng.)

PU-polyester elastomers contain hard and soft domainswhich give these materials unique structural and elasticproperties and lead to their use in various applications. Itis desirable to characterise the molecular level interactionsgiving rise to the two domains, and to use this informationto monitor chemical changes which take place in thepolymer as a function of exposure to agents known toeffect structural changes. IR spectroscopy has been usedto study polymeric structures, including PU elastomers,as the vibrational absorption bands characteristic ofdifferent functional groups are sensitive to changes in theirchemical environment. One difficulty in the applicationof IR spectroscopy to complex chemical systems has beenthe ambiguity of interpretation due to the limitations ofdifferent deconvolution techniques. The development ofa 2D correlation method has provided a means by whichconvoluted spectral information, such as that arising fromthe two domains of estane, can be resolved as a functionof some perturbation. A thermal 2D FT-IR study of estaneis presented. 2 refs.USA

Accession no.719142

Item 96ACS Polymeric Materials Science & Engineering,Spring Meeting 1998. Volume 78. Conferenceproceedings.Dallas, Tx., Spring 1998, p.22-3. 012

DYNAMIC OPTO-RHEOLOGICAL STUDY OFESTANE COPOLYMERS USING STEP-SCANFTIR SPECTROSCOPYWang H; Palmer R A; Graff D K; Schoonover J RDuke,University; Los Alamos National Laboratory(ACS,Div.of Polymeric Materials Science & Engng.)

Urethane copolymers generally consist of linear segmentsof PU and polyester (or polyether). At room temperature,these polymers undergo a microphase separation, in whichthe PU segments form hard domains while the polyestersegments form relatively soft domains that act as thecrosslinks between the hard cores. This morphologyprovides such copolymers distinctive thermal andmechanical properties which have led to an extensiverange of applications. A wide variety of techniques hasbeen utilised to characterise the microscopic (molecular)structure of polymeric materials, including those of PUsand urethane copolymers, since the knowledge of themicroscopic structure of these polymers is critical to theunderstanding of their macroscopic properties. Recently,a dynamic infrared opto-rheological method has beendeveloped which involves the combination of dynamicmechanical analysis and time-resolved IR spectroscopyto study the real time IR spectral changes in polymer filmsunder sinusoidal (or impulse) tensile stress of smallamplitude. Phase-locked electronics are used to recordthe dynamic infrared spectral change in-phase and in-quadrature with the applied mechanical field. The resultprovides insight to the response to the external stress onthe molecular and submolecular scale. While for relativelynarrow spectral ranges this experiment is efficientlycarried out by use of a dispersive spectrometer, formeasurements over broader spectral windows, the use ofstep-scan Fourier transform IR (S2FT-IR) has proved tobe more effective. Dynamic opto-rheology using S2FT-IR spectroscopy is applied to the urethane-ester copolymerEstane 5703. Dynamic in-phase and quadrature spectrain the mid-IR region at two orthogonal polarisations arecollected, and dynamic dichroic spectra calculated andinterpreted. 18 refs.USA

Accession no.719141

Item 97ACS Polymeric Materials Science & Engineering,Spring Meeting 1998. Volume 78. Conferenceproceedings.Dallas, Tx., Spring 1998, p.20-1. 012STEP SCAN PHOTOACOUSTIC FT-IRSPECTROSCOPY AND STRATIFICATIONPROCESSES IN THERMOPLASTIC OLEFINS(TPO)Stegge J M; Urban M WNorth Dakota State University(ACS,Div.of Polymeric Materials Science & Engng.)

The majority of methods used for analysis of complexsystems such as thermoplastic olefins (TPO) are



destructive. The technique that offers non-destructivefeatures and allows probing surfaces on a molecular levelfor interactions is step-scan photoacoustic FT-IR (S2 PASFTIR) spectroscopy. Although step-scan photoacousticFTIR experiments can be used to collect information fromselectable and constant depths from the sample surface,a possible limitation arising from this experiment is thecontamination of the signal from sample areas above thesampling depth. In order for a signal to be produced theheat generated must travel completely through the samplefrom the depth of origin to the sample surface. In an effortto overcome this limitation it is beneficial to spread thespectral information out over another dimension. This canbe accomplished by introducing a time dependence to thesignal detection, and monitoring the sample response toa perturbation. While various external perturbations,including mechanical, thermal and magnetic fieldvariation, have been employed or suggested to induce timedependence into a system, internal perturbations such asthe photothermal effect have been mostly neglected orunrecognised. Through the use of this type of perturbationa two-dimensional correlation analysis can be used to gainincreased spectral resolution or investigate componentinteraction. 12 refs.USA

Accession no.719140

Item 98ACS Polymeric Materials Science & Engineering,Spring Meeting 1998. Volume 78. Conferenceproceedings.Dallas, Tx., Spring 1998, p.18-9. 012MULTI-DIMENSIONAL SURFACE ANDINTERFACIAL ANALYSIS OF POLYMERS ANDCOATINGS; ATR, STEP-SCANPHOTOACOUSTIC, FT-IR/FT-RAMANIMAGINGUrban M WNorth Dakota State University(ACS,Div.of Polymeric Materials Science & Engng.)

Vibrational spectroscopy represents two physicallydifferent, yet complementary spectroscopic techniques:IR and Raman spectroscopy. Although both methods havebeen utilised for many years, recent advances inelectronics, computer technologies and sampling madeFourier transform infrared (FTIR) and Raman (FT-Raman) one of the most powerful and versatile analyticaltools. Enhanced sensitivity and surface selectivity allowsnon-invasive, no-vacuum molecular level analysis ofsurface and interfaces. Emphasis is placed on recentadvances in attenuated total reflectance (ATR), step-scanphotoacoustic (SS-PA), Fourier transform infrared (FT-IR) and FT-Raman microscopies, as utilised to the analysisof polymeric surfaces and interfaces. A combination ofthese probes allows detection of molecular level changesresponsible for macroscopic changes in three dimensionsfrom various depths. 7 refs.

USA

Accession no.719139

Item 99Polymer40, No.7, 1999, p.1629-36ROLE OF AN ACTIVE ENVIRONMENT OF USEIN AN ENVIRONMENTAL STRESS CRACKRESISTANCE (ESCR) TEST IN STRETCHEDPOLYETHYLENE: A VIBRATIONALSPECTROSCOPY AND SEM STUDYLagaron J M; Pastor J M; Kip B JDSM Research; Valladolid,Universidad

The role of an environmental stress crack resistance(ESCR) detergent (active environment) during tensiledeformation of PE samples was studied using Raman andIR spectroscopy. Raman spectroscopy was found not tobe suitable for detecting this environment inside thesample, but IR spectroscopy indicated that theenvironment was predominantly present within thetransition fronts of the material. A stress-inducedenvironment diffusion mechanism was suggested. SEMshowed differences in the deformation process betweendrawing in air or in detergent. The results indicated thatthe environment penetrated the sample during the neckingprocess and stabilised crazing. The molecular mechanismswere discussed. 14 refs.EUROPEAN COMMUNITY; EUROPEAN UNION;NETHERLANDS; SPAIN; WESTERN EUROPE

Accession no.714041

Item 100ACS Polymeric Materials Science and Engineering.Fall Meeting 1998. Volume 79. Conferenceproceedings.Boston, Mas., 23rd-27th Aug.1998, p.506-7. 012INFRARED SPECTROSCOPIC STUDY OFOXIDATION IN POLYURETHANE HARDSEGMENTSSkorich S R; Benz M EMedtronic Inc.

Previous studies have indicated that in vivo oxidation ofpolyether urethanes (PEUs) has involved depletion of thesoft segment of the material . The use of an attenuatedtotal reflectance (ATR) objective on the infrared (FTIR)microscope has allowed analysis of much smaller areason PU tubing samples removed from in vivo implantation.By means of the micro ATR, the differences between theIR spectra of clear vs. fissured areas of PEUs areenhanced, and IR peaks typical of fissured areas areobserved. Similar peaks were observed on fissured areasof a polycarbonate urethane (PCU) which shares the samehard segment with the PEUs. It became clear that the hardsegment was involved in the fissuring process as well asthe soft segment. Hard segments in both these materialswere based on 4,4'-methylene bis diisocyanate (MDI) and



1,4-butanediol (BDO). Two model diethyl carbamate(urethane) compounds are synthesised from 4,4'-methylene dianiline and 4,4'-diaminobenzophenone. Thespectra of these materials show the same sort of spectraldifferences as between the clear and fissured materialsabove. These compounds closely model the hard segmentof the above materials, and differ only in the oxidation toa carbonyl group of the central methylene group in themolecule. This implies that the same process is occurringin the PU hard segments, in addition to any soft segmentreactions. 6 refs.USA

Accession no.713291

Item 101Macromolecules31, No.25, 15th Dec.1998, p.9008-12MOLECULAR ORIENTATION AND DYNAMICSIN FERROELECTRIC DIBLOCK COPOLYMERSMONITORED BY FTIR SPECTROSCOPYMerenga A; Shilov S V; Kremer F; Mao G; Ober Ch K;Brehmer MLeipzig,University; St.Petersburg,Institute ofMacromol.Compounds; Cornell University;Wuppertal,Bergische Universitaet

In ferroelectric liquid crystalline block copolymers theproperties of ferroelectric liquid crystals are combinedwith those of diblock copolymers. Hence, one observesin these materials a microphase separation between theamorphous polymer (PS) and the ferroelectric liquidcrystal segment (a side chain containing oxybiphenylenenitrooxybenzoate groups). The latter group can beswitched by applying an external electric field. Timeresolved FTIR was used to study structure and dynamicsof these systems. From analysis of the dichroism of theFTIR spectra, it was concluded that the components inthe PS microphase are oriented randomly while the liquidcrystalline groups form an ordered phase. Time-resolvedmeasurements of the switching of the liquid crystallineblock were performed during the application of an externalelectric field. It may be shown that switching is of anelectroclinic type and that the tilt angle and the mesogenicmotion increase with temperature, especially if the PSblock is heated above Tg. The orientation of the liquidcrystalline block after heating to the isotropic phase iscompletely restored due to the memory effect of thepolymer microstructure. 12 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;RUSSIA; USA; WESTERN EUROPE

Accession no.711651

Item 102European Polymer Journal34, No.11, Nov.1998, p.1571-7DYNAMIC INFRARED SPECTROSCOPY, ATOOL TO DETECT HYDROGEN BONDS INPOLYMERS?

Kischel M; Kisters D; Strohe G; Veeman W SGerhard-Mercator Universitat

Dynamic infrared linear polarised spectra ofthermoplastic polyester urethane and nylon-6 films wererecorded under a varying sinusoidal strain. Dichroicspectra were calculated from the dynamic polarisedspectra. The large bipolar bands in the dichroic in-phasespectra, caused by large frequency shifts of the originalmonopolar absorption bands, were ascribed to hydrogenbonds. 29 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.709540

Item 103Polymer40, No.5, March 1999, p.1131-7POLYMERIZATION OF HYDROXYALKYLMETHACRYLATES CHARACTERIZED BYCOMBINATION OF FT-RAMAN AND STEP-SCAN FT-I.R. PHOTOACOUSTICSPECTROSCOPYKammer S; Albimsky K; Sandner B; Wartewig SHalle,Martin-Luther-Universitat

The free radical polymerisation of 2-hydroxyethylmethacrylate was studied by FT-Raman spectroscopy andthat of bisphenol-A-bis(2-hydroxypropyl methacrylate)was studied by this technique and also by FTIRphotoacoustic spectroscopy. Raman spectroscopy wasused to determine the conversion of C=C double bondsof the monomers exactly. 18 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.707124

Item 104Polymer Degradation and Stability62, No.2, 1998, p.395-401OXIDATION OF RUBBERS ANALYSED BYHORIZONTAL ATR/IR SPECTROSCOPYDelor F; Barrois-Oudin N; Duteurtre X; Cardinet C;Lemaire J; Lacoste JBlaise Pascal,Universite; Renault; Hutchinson

The analysis of rubbers containing large amounts ofcarbon black by IR spectroscopy is difficult ,particularly studies of their chemical evolution uponageing. The use of a horizontal ATR accessory equippedwith a germanium crystal is described. HorizontalATR(Ge)/FTIR analysis of both thermal- andphotooxidations of EPDM, polychloroprene and NBRwere first validated by conventional transmissionspectroscopy in the absence of carbon black. HorizontalATR(Ge) was then used with fully formulated rubberswith the aim of studying their long-term behaviour. Theeffects of temp., UV exposure, carbon black or stressas well as the oxidation profile across the materials on



the identification of carboxylic acid/carboxylate groupswere examined. 8 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.706569

Item 105Analytical Chemistry70, No.22, 15th Nov.1998, p.4701-8SIMULTANEOUS MULTISPECTRAL IMAGINGIN THE VISIBLE AND NEAR-INFRAREDREGION: APPLICATIONS IN DOCUMENTAUTHENTICATION AND DETERMINATION OFCHEMICAL INHOMOGENEITY OFCOPOLYMERSTran C D; Yan Cui; Smirnov SMarquette,University

A multispectral imaging spectrometer capable ofsimultaneously recording spectral images in the visibleand near-IR was developed. In this instrument, anacoustooptic tunable filter was used to diffract beams withorthogonal polarisation, one of them being detected by asilicon camera for the visible region, while the other beamwas detected in the near-IR region with a near-IR camera.Preliminary applications of the imaging spectrometerincluded measurements of the visible and near-IRabsorption spectra of ink used to print U.S. currency andstudies of EVA copolymers. The near-IR spectral imagesobtained clearly indicated that the EVA copolymersexhibited a high degree of chemical inhomogeneity. 22refs.USA

Accession no.704919

Item 106Polymer Analysis and Characterization. V. AppliedPolymer Symposium proceedings.Inuyama, 1st-4th June 1992, p.251-9. 91TCHARACTERISATION OF COATEDINTERFACES AND POLYMER BLENDS USINGFOURIER TRANSFORM INFRAREDMICROSPECTROSCOPYNishioka T; Teramae NIdemitsu Petrochemical Co.Ltd.(ISPAC)Applied Polymer Symposium 52

Fourier transform infrared microspectroscopy is appliedfor the characterisation of a coated interface and a polymerblend. The coated sample investigated is prepared bycoating a urethane paint on an ethylene-ethyl acrylatecopolymer whose ethyl-ester group is partially hydrolysed(EAA/EEA). It is demonstrated that a mixed phase isformed along the coated interface between the paint andthe EAA/EEA. Interaction between molecules of theurethane paint and the EAA/EEA is observed. For apolymer blend prepared by mixing PP and polycarbonate,

the spatially specific compositional heterogeneity couldbe easily identified. 18 refs.JAPAN

Accession no.704051

Item 107Polymer Analysis and Characterization. V. AppliedPolymer Symposium proceedings.Inuyama, 1st-4th June 1992, p.55-62. 91TTWO-DIMENSIONAL INFRARED STUDIES OFSUBMOLECULAR LEVEL DYNAMICS OFPOLYMERSNoda I; Dowrey A E; Marcott CProcter & Gamble Co.(ISPAC)Applied Polymer Symposium 52

Two-dimensional infrared (2D IR) spectroscopy is used toelucidate the submolecular-level dynamics of an amorphouspolymer under a dynamic deformation. In 2D IR, a polymersample is perturbed by a small-amplitude oscillatory strain,and the resulting dynamic fluctuation of IR signals is usedto construct a set of 2D correlation maps. These 2D mapsare especially suited for obtaining detailed information aboutlocal dynamics of submolecular constituents of the system.2D IR spectra of glassy atactic PS reveal that while the main-chain backbone reorients in the direction of applied strain,there also exist highly localised reorientational motions ofphenyl side groups occurring independently of the main-chain realignment. This localised submolecular distortion isnot strongly observed at temperatures well above the glass-to-rubber transition. 6 refs.USA

Accession no.704035

Item 108Synthetic Metals96, No.1, 15th July 1998, p.63-70SERS SPECTRA OF POLYANILINE THIN FILMSDEPOSITED ON ROUGH AG, AU AND CU.POLYMER FILM THICKNESS ANDROUGHNESS PARAMETER DEPENDENCE OFSERS SPECTRABaibarac M; Cochet M; Lapkowski M; Mihut L;Lefrant S; Baltog IRumania,National Institute of Material Physics;Nantes,Institut des Materiaux; Silesian TechnicalUniversity

SERS spectra under 1064 nm excitation were studied fortwo forms of polyaniline, one of the emeraldine base typeand the other of the emeraldine salt type to identify thechemical effects at the polymer/metal interface that areinvolved in the specific modifications of the SERSspectra. 19 refs.EASTERN EUROPE; EUROPEAN COMMUNITY; EUROPEANUNION; FRANCE; POLAND; RUMANIA; WESTERN EUROPE

Accession no.703351



Item 109International Composites Expo ’98. Conferenceproceedings.Nashville,Tn., 19th-21st Jan.1998, Session 21-D. 627UTILISING FOURIER TRANSFER NEARINFRARED (FT-NIR) TO MONITOR KEYCHEMICAL CHARACTERISTICS IN THEMANUFACTURE OF THERMOSET PLASTICSLandis L P; Cameron D GPremix Inc.; DHC Analysis Inc.(SPI,Composites Institute)

Thermoset plastic companies manufacture a variety ofproducts that utilise a complex array of ingredients andprocess environments. In a typical thermoset plastic,there could be over ten ingredients including resins,inorganic fillers, glass fibre, inhibitors, initiators, lowprofile additives, flame retardants, pigments and otherspecial additives. To help monitor and control themanufacture of thermoset plastics near IR methods andprotocols have been developed which are at least tentimes more precise than the wet chemical methods.Premix has been using Fourier Transform Near Infrared(FT-Near IR) in the quality assurance laboratory since1995 to measure key quality characteristics of some rawmaterials as well as resultant pastes. Wet chemicaltechniques (e.g. Karl Fischer Titration) for certainsamples have been replaced by FT-Near IR. It is a non-destructive method that can be applied on, at or in-line.It allows companies to reduce the use of costly anddangerous chemicals which are often needed in manytest methods, and realise significant savings throughimproved process control, product quality and wastereduction. 2 refs.USA

Accession no.702072

Item 110Applied Spectroscopy52, No.9, Sept.1998, p.1248-52APPLICATION OF SAPPHIRE FIBERS TO AN IRFIBER-OPTIC SENSOR FOR THEINVESTIGATION OF POLYMERS ATELEVATED TEMPERATUREGoetz R; Mizaikoff B; Kellner RVienna,University of Technology

The determination of the composition of ethylene-propylene copolymers at a temp. of 200C by means of anIR fibre-optic sensor based on sapphire fibres was studied.LDPE and PP were also investigated. Data are presentedon spectra of LDPE and PP at 200C obtained using thesensor, CH3/CH2 ratio after curve fitting versus C2content, ratio of absorbance at 2950 and 2852/cm versusC2 content and calibration graph of multivariatecalibration. 31 refs.AUSTRIA; WESTERN EUROPE

Accession no.700291

Item 111Applied Spectroscopy52, No.9, Sept.1998, p.1141-4NEAR-FIELD RAMAN SPECTRALMEASUREMENT OF POLYDIACETYLENENarita Y; Tadokoro T; Ikeda T; Saiki T; Mononobe S;Ohtsu MJASCO Corp.; Kanagawa,Academy of Science &Technology

Two-dimensional near-field Raman spectra andtopographic images of the polydiacetylene surface weremeasured simultaneously by using a near-field Ramanspectrometer. The spectra (located 100 nm apart) haddifferent spectral features. The peak intensity ratio of twoC:C peaks at 1520 and 1457/cm did not correlate withthe topographic image and showed differences in thesubwavelength scale. These differences could beinterpreted as spatial differences in the number ofsuccessive bonds on the polydiacetylene surface. Incontrast, the near-field Raman intensity of the C:C bondat 1457/cm correlated strongly with the topographicimage. This phenomenon could be interpreted as a changein the efficiency of collecting Raman scattering light. 26refs.JAPAN

Accession no.700289

Item 112Journal of Applied Polymer Science70, No.6, 7th Nov.1998, p.1221-37PHOTOOXIDATION OF ANHYDRIDE-CUREDEPOXIES: FTIR STUDY OF THEMODIFICATIONS OF THE CHEMICALSTRUCTUREOllier-Dureault; Gosse BSchneider Electric; CNRS-LEMD

The photooxidative degradation of anhydride-curedepoxies was studied using transmission Fourier transforminfrared and attenuated total reflection spectroscopy. Thedegradation was heterogeneous, the surface being muchmore affected from the bulk. Epoxies containingflexibilisers, which were rich in ester groups butcontaining fewer phenyl groups, degraded much morerapidly during the first hours of exposure than thosewithout flexibilisers. After 40 hours of irradiation, thedisappearance rate of aromatic groups was dependent onlyupon their initial concentration, whilst the formationkinetics of hydroxyl groups was determined by thediffusion of oxygen into the material. The formation ofhydrophilic products, acids, and alcohols was confirmedby chemical treatment, and it was concluded that theirpresence and high concentration at the surface could beresponsible for the degradation of the insulating propertiesof epoxies when used as electrical insulators. 20 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.700202



Item 113Journal of Polymer Science : Polymer ChemistryEdition36, No.14, Oct.1998, p.2503-12SPECTROSCOPIC INVESTIGATIONS OFPOLYACRYLONITRILE THERMALDEGRADATIONSurianarayanan M; Vijayaraghavan R; Raghavan K VIndia,Central Leather Research Institute; IndianInstitute of Chemical Technology

The thermal degradation of polyacrylonitrile wasinvestigated using Fourier transform infraredspectroscopy, high-resolution solid-state nuclearmagnetic resonance spectroscopy, pyrolysis gaschromatography, and elemental analysis. Over thetemperature range 150-590C, gaseous and volatileproducts were produced with simultaneous stabilisationof the structure of the residual material. The principledecomposition reaction was linear polymerisation ofthe nitrile group, with cyclisation followed by extendedconjugation being a significant exothermic process.There was no evidence of the formation of oxygen-containing chromophores. 29 refs.

INDIA

Accession no.699986

Item 114Journal of Polymer Science : Polymer Physics Edition36, No.14, Oct.1998, p.2471-82STRUCTURAL ANALYSIS OF POLY(3-HYDROXYBUTYRATE-CO-3-HYDROXYVALERATE) FIBERS PREPARED BYDRAWING AND ANNEALING PROCESSESFuruhashi Y; Ito H; Kikutani T; Yamamoto T; KimizuM; Cakmak MTokyo,Institute of Technology; Ishikawa,IndustrialResearch Institute; Akron,University

Wide-angle X-ray diffraction, density, infrareddichroism and birefringence measurements were usedto characterise the structure of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) fibres which had been preparedby drawing and annealing. Three crystalline structureswere present: two orthorhombic, and the third waspseudo-hexagonal. Both negative and positive values ofbirefringence were observed, being dependent upon thedrawing and annealing temperatures. The birefringenceof the amorphous phase was positive, decreasing withan increase in the annealing temperature. It wasconcluded that orthorhombic crystals with the c-axispreferentially orientated perpendicular to the fibre axis,and pseudo-hexagonal crystals were preferentiallyformed in the drawing process, irrespective of thetemperature. 15 refs.

JAPAN; USA

Accession no.699617

Item 1155th International Conference on Polyimides - NewTrends in Polyimide Science and Technology. Retecproceedings.Ellenville, N.Y., 2nd-4th Nov.1994, p.25. 43C4FTIR AND FLUORESCENCE MONITORING OFPOLYIMIDE FORMATIONWang F W; Hutton R S; Lowry R E; Wang T TUS,National Inst.of Standards & Technology; AT & TBell Laboratories; Rutgers,University(SPE,Plastics Analysis Div.; SPE,Mid-Hudson Section)

FTIR and fluorescence spectroscopy are used to monitorthe imidisation of a polyamic acid made from 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA), and fluorescence spectroscopyis used to monitor the imidisation of a polyamic acid madefrom 2,2-bis(3,4-dicarboxyphenyl hexafluoropropanedianhydride (6FDA) and p-phenylene diamine. A film ofthe polyamic acid made from BPDA and PDA is heatedin a nitrogen atmosphere for one hour at 75 deg.C, andthe thermal treatment is repeated at each of thetemperatures from 100 to 400 deg.C in 25 deg.Cincrements between successive thermal treatments. Aftereach treatment, the fluorescence and the excitation spectraof the film are taken at an excitation wavelength of 460nm and a fluorescence wavelength of 550 nm,respectively. Extended abstract only.USA

Accession no.698382

Item 116Polymer39, No.26, 1998, p.6899-904CELLULOSIC BLENDS WITHPOLY(ACRYLONITRILE):CHARACTERIZATION OF HYDROGEN BONDSUSING REGIOSELECTIVELY METHYLATEDCELLULOSE DERIVATIVESShin J-H; Kondo TJapan,Forestry & Forest Products Res.Inst.

Fourier transform infrared (FTir) spectroscopy was usedto characterise the hydrogen bonds, in terms of hydroxylregiochemistry, in blends of cellulose materials withpolyacrylonitrile (PAN). Regioselectively substitutedmethylcelluloses were used as the cellulose modelcompounds. Wide-angle x-ray diffraction studies of castfilms containing more than 50 wt% cellulose showed themto be highly amorphous, attributed to interaction betweenthe cellulose and PAN. FTir analysis showed that thehydrogen bonds in washed films were only between theC-6 position in the cellulose and the nitrile group of thePAN. This was in contrast with the as-cast films, wherethe residual dimethylacetamide solvent promotedadditional interaction between the two polymercomponents, resulting in enhanced miscibility. 28 refs.JAPAN

Accession no.697798



Item 117Polymer39, No.26, 1998, p.6807-17IN SITU COMPATIBILIZATION OFPOLYPROPYLENE-POLYETHYLENE BLENDS:A THERMOMECHANICAL ANDSPECTROSCOPIC STUDYTselios Ch; Bikiaris D; Maslis V; Panayiotou CThessaloniki,University

Polypropylene (PP) and low density polyethylene (LDPE)were melt blended in various proportions, withpoly(propylene-g-maleic anhydride) and poly(ethylene-co-vinyl alcohol) added in equal proportions as in situreactive compatibilisers. The compatibilisation reactionwas monitored by measuring the torque increase duringmixing and by Fourier transform infrared spectroscopy.Improvements in tensile strength, elongation at break andimpact strength were observed for all compatibilisedblends, and particularly for the blends which contained10 wt% compatibiliser. Scanning electron microscopy andRaman spectroscopy were used to investigate the blendmorphology. 71 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GREECE;WESTERN EUROPE

Accession no.697789

Item 118RadTech ’98. Conference proceedings.Chicago, Il., 19th-22nd April 1998, p.363-74. 895CHARACTERISATION OF RADIATIONCURABLE COATINGS BY CONFOCAL RAMANMICROSCOPYSchrof W; Beck E; Koniger R; Meisenburg U; MenzelK; Reich W; Schwalm RBASF AG(RadTech International)

Increasing amounts of radiation curable materials arebeing used in coating films for the surface refinement offurniture, wooden floor coverings, paper etc. ConfocalRaman spectroscopy is used to examine depth or lateralprofiles of the crosslinking process (e.g. the reactionprogress) in these coatings with a resolution ofapproximately 1 mu3. The potential of confocal Ramanmicroscopy is demonstrated for the problems of theinhibition of the radical polymerisation reaction byoxygen, the limited polymerisation reaction in deep layersdue to the restricted penetration of UV light (Lambert-Beer), the reaction in pigmented coatings and thedistribution of UV stabilisers interacting with the UVcuring process. 11 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.696928

Item 119Macromolecules31, No. 16, 11th Aug. 1998, p.5450-5

INFRARED DICHROISM AND SURFACECONFORMATIONAL DYNAMICS OFADSORBED POLY(DIMETHYLSILOXANE)Soga I; Granick SIllinois,University

Polymer conformations at a strongly adsorbing solid surfaceand their evolution with elapsed time during the adsorptionprocess were examined. Poly(dimethyl-siloxane) (weightaverage molecular weight 118000, polydispersity index 1.16)was allowed to adsorb onto oxidised germanium from dilutecarbon tetrachloride solutions. The mean backboneorientation was found to change even after the mass adsorbedhad saturated. It’s conformation was determined using IRdichroism spectroscopy in attenuated total reflection (FTIR-ATR). The dichroic ratio of the Si-O-Si and Si-methyl stretchvibrations showed the poly(dimethylsiloxane) backbone tobe preferentially horizontal to the surface (dichroic ratio about0.9 at early adsorption times) and to grow increasinglyflattened with increasing adsorption time. However, as theadsorbed amount increased with higher solutionconcentrations, the average orientation was less flattened.Chain flattening during the adsorption process was alsoslower, the higher the adsorbed amount, reflecting molecularcrowding within more densely occupied layers. Duringdesorption into the pure solvent, the evolution of the dichroicratio could be described by the hypothesis of a bimodalconfigurational distribution. 21 refs.USA

Accession no.696674

Item 120Polymer Bulletin41, No.2, Aug 1998, p.191-8CHARACTERISATION OF PET/LLDPE BLENDSCOMPATIBILIZED WITH DEM-GRAFTED-POLYETHYLENEMarquez L; Sabino M A; Rivero I ASimon Bolivar,Universidad

Blends of polyethylene terephthalate and linear low-density polyethylene were compatibilised usingdiethylmaleate grafted polyethylene, and characterisedusing Fourier transform infra-red spectroscopy,thermogravimetric analysis and scanning electronmicroscopy. Interactions between the components in theblends were observed, which affected the glycolsequences of the polyester and also improved the thermaloxidative stability of the blends. The introduction of thecompatibiliser resulted in a particle size reduction of thedispersed phase and better adhesion between the phaseand the matrix. 15 refs.VENEZUELA

Accession no.696610

Item 121Polymer39, No.20, 1998, p.4735-9



CHARACTERIZATION OFELECTROCHEMICALLY PRODUCED TWO-COMPONENT FILMS OF CONDUCTINGPOLYMERS BY RAMAN MICROSCOPYSacak M; Akbulut U; Batchelder D NLeeds,University

Polyaniline/poly(N-vinyl carbazole), polypyrrole/poly(N-vinyl carbazole) and polypyrrole/polyaniline films (orreverse order of each pair in the films) were synthesisedon platinum foil electrodes by sequential electrolysis.Confocal Raman microprobe spectroscopy was used tocharacterise both the solution sides and the electrode sidesof the films. Two types of film were observed, dependingon the conditions. Either the second polymer wasincorporated into the initially coated layer or a double-layer film with a well-defined interface was formed.Electrolysis of pyrrole and aniline monomer mixturesgave films rich in pyrrole when the pyrrole:aniline molarratios were greater than 0.12. However, polymerisationof N-vinyl carbazole and pyrrole monomer mixtures gaveonly polypyrrole over a wide range of molar ratios. 19refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.696557

Item 122Polymer39, No.20, 1998, p.4723-8ATTENUATED TOTAL REFLECTANCE CELLFOR ANALYSIS OF SMALL MOLECULEDIFFUSION IN POLYMER THIN FILMS WITHFOURIER-TRANSFORM INFRAREDSPECTROSCOPYBalik C M; Simendinger W HNorth Carolina,State University

A cell for characterising the diffusion of small moleculesthrough thin polymer films using attenuated totalreflectance (ATR) FTIR spectroscopy was described. Thecell was designed to be used with precast (commerciallyextruded) polymer films, thus enabling the as-processedtransport properties of the film to be studied. The cellwas used to measure the diffusion of carbon dioxide, amylacetate and limonene, and simultaneous diffusion of theindividual components from a 50/50 mixture of amylacetate and limonene through the thin polymer films(HDPE, LDPE and PS). Diffusion coefficients measuredwith the ATR technique compared favourably with valuesobtained from gravimetric measurements with the samepenetrants and polymer samples. 20 refs.USA

Accession no.696555

Item 123Polymer39, No.25, 1998, p.6589-96

CHARACTERISATION OF RANDOMPROPYLENE-ETHYLENE COPOLYMERFeng Y; Hay J NBirmingham,University

The comonomer sequence in a propylene-ethylenerandom copolymer was investigated using temperaturerising elution fractionation, nuclear magnetic resonancespectroscopy, Fourier transform infra-red spectroscopyand differential scanning calorimetry. There was a widerange of compositional heterogeneity, the compositioncomprising mainly long propylene sequences with anoccasional ethylene unit. The sequence distributions ofthe fractions did not fit either Bernoulli or first orderMarkovian statistics. The crystallisation kinetics andmelting behaviour were strongly influenced by theethylene content and the comonomer distribution. 33 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.694681

Item 124Polymer39, No.25, 1998, p.6533-9NEW ACRYLIC TITANIUM POLYMERS: II.SYNTHESIS AND CHARACTERIZATION OFORGANOTITANIUM POLYMERSCamail M; Humbert M; Margaillan A; Vernet J LToulon et du Var,Universite

The synthesis of acrylic organotitanium polymers by thecopolymerisation of acrylic organotitanium monomerswith methyl methacrylate via free-radical initiation inorganic solvents, or by esterification of the acid functionsof an acrylic polymer with titanium tetraalkoxide, wasinvestigated. These polymers have potential applicationas a marine anti-fouling coating. With a stoichiometricmolar ratio of titanium:carboxyl, a gel was formed. Thepreparation of an esterified polymer, soluble in the usualorganic solvents, required an excess of titaniumtetraalkoxide. The amount of excess required dependedupon the nature of the alkoxide, the concentration andthe nature of the polymer. 11 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.694674

Item 125European Polymer Journal34, No.8, Aug.1998, p.1199-205PREPARATION AND CHARACTERIZATION OFGRAFT COPOLYMERS OF POLYACRYLAMIDEAND POLYETHYLENIMINELi D; Zhu S; Pelton R HMcMaster University

The condensation grafting of polyethylenimine (PEI) ontopoly(acrylamide-co-acrylic acid) (PAM-co-AA) wasstudied. Fourier transform infra-red spectroscopy was



used to investigate the reaction mechanism, whichproceeded by a two-step reaction, involving theconversion of AA to acid chloride (AC) using thionylchloride, followed by the condensation of AC onto PAMand with amine onto PEI to form the graft copolymer.The condensation reaction was fast in formamide solution.The major factors determining the degree of grafting andthe chain structure were the AA content of PAM, themolecular weight of PEI and the ratio PEI:PAM. Proposedstructures of the graft copolymer chains are discussed.16 refs.

CANADA

Accession no.694435

Item 126Journal of Applied Polymer Science69, No.8, 22nd Aug. 1998, p.1669-74FOURIER TRANSFORM INFRARED-PHOTOACOUSTIC SPECTROSCOPY OFPOLY(N-BUTYL METHACRYLATE) ADSORBEDFROM SOLUTION ON ALUMINAPekel N; Guven OHacettepe,University

The adsorption of poly(n-butyl methacrylate) fromcyclohexane, benzene and carbon tetrachloride ontoalumina was qualitatively and quantitatively analysedusing Fourier transform infra-red-photoacousticspectroscopy. The efficiency of adsorption increasedin the order cyclohexane, carbon tetrachloride,benzene, whilst methanol and tetrahydrofuran showednegative adsorption. Poly(n-butyl methacrylate) had anegative temperature coefficient of adsorption. 12 refs.

TURKEY

Accession no.693610

Item 127Journal of Applied Polymer Science69, No.11, 12th Sept.1998, p.2175-85IR SPECTROSCOPY AS A QUANTITATIVE ANDPREDICTIVE ANALYSIS METHOD OFPHENOL-FORMALDEHYDE RESOL RESINSHolopainen T; Alvila L; Rainio J; Pakkanen T TJoensuu,University; Dynoresin Oy

A set of resin samples was characterised by IR and carbon-13 NMR spectroscopy. The suitability of IR spectroscopyfor the quantitative analysis of resins was evaluated bystatistical methods using the NMR reference data ascalibration. The values of interesting properties, e.g. theamount of free phenol and the formaldehyde-to-phenolmolar ratio, of the resins being similar to the calibrationresins were predicted from the IR spectra. The predictedresults were compared with those observed by carbon-13NMR spectroscopy. 15 refs.

FINLAND; SCANDINAVIA; WESTERN EUROPE

Accession no.692990

Item 128Macromolecular Rapid Communications19, No.8, Aug.1998, p.413-7DEVELOPMENT OF A SIMPLEEXPERIMENTAL METHOD TO MEASUREINTERPHASE COMPOSITION PROFILESGENERATED BY DIFFUSION IN POLYMERS.FURTHER RESULTS AND COMPARISON WITHRAMAN SPECTROSCOPYTomba P; Carella J M; Pastor J M; Fernandez M RINTEMA; Mar del Plata,Universidad Nacional;Valladolid,Universidad

Composition profiles generated by interdiffusion in theconcentrated regime between polyphenylene oxide-polystyrene blend pairs were experimentally determined bytwo techniques. Three-point bending moment measurementsover a convenient temperature range (dynamic mechanicalanalysis (DMA)) were used to determine interphasecomposition profiles. Confocal micro-Raman spectroscopywas also used to measure local compositions along a directionwhich was perpendicular to the original interface. The studyincluded some limiting cases to test accuracy, precision andflexibility of the DMA method. 4 refs.ARGENTINA; EUROPEAN COMMUNITY; EUROPEAN UNION;SPAIN; WESTERN EUROPE

Accession no.692051

Item 129Journal of Applied Polymer Science69, No.4, 25th July 1998, p.645-55MAPPING PHASES OF POLY(VINYLALCOHOL) AND POLY(VINYL ACETATE)BLENDS BY FTIR MICROSPECTROSCOPY ANDOPTICAL FLUORESCENCE MICROSCOPYDibbern-Brunelli D; Atvars T D Z; Joekes I; Barbosa V CCampinas,Universidade Estadual

Fluorescence optical microscopy (FOM) of poly(vinylalcohol) and poly(vinyl acetate) blends in compositions9/1, 1/1, and 1/9 (w/w) showed that these blends presentphase separation in the solid state. Each domain of thesolid samples was identified by FOM as poly(vinylalcohol)-richer domains by green fluorescence offluorescein and poly(vinyl acetate)-richer domains by theblue fluorescence of anthracene. The dimensions, shapes,and distributions of these domains were dependent on theinitial composition of the polymeric mixtures in solution.Specific interactions between both homopolymers werestudied using FTIR microspectroscopy, which allowedthe obtaining of spectra for both poly(vinyl alcohol)-richerand poly(vinyl acetate)-richer domains. 24 refs.BRAZIL

Accession no.689629

Item 130Antec ’98. Volume II. Conference proceedings.Atlanta, Ga., 26th-30th April 1998, p.2085-9. 012



IN-LINE FIBRE-OPTIC NEAR-INFRAREDSPECTROSCOPY: FEASIBILITY STUDIES FORTHE SIMULTANEOUS MONITORING OF VINYLACETATE AND ERUCAMIDE ADDITIVECONCENTRATIONS IN POLYETHYLENE-VINYL ACETATE COPOLYMERSVedula S; Hansen M G; Deshpande B JTennessee,University(SPE)

Feasibility studies for the simultaneous monitoring ofvinyl acetate (VA) and erucamide additive concentrationsin EVA copolymers are undertaken using near-infrared(NIR) spectroscopy. Two groups of samples, each groupcontaining different erucamide concentrations for a fixedVA concentration, are used. NIR spectra of flowing moltenpolymers are obtained in-line using a flow cell attachedto an extruder. The first derivatives of the NIR spectra inthe region 1900-2000 nm show overlapping peaks of VAand erucamide. These peaks are deconvoluted usingmultivariate analysis methods. 7 refs.

USA

Accession no.687493

Item 131Antec ’98. Volume II. Conference proceedings.Atlanta, Ga., 26th-30th April 1998, p.2223-7. 012NEW APPROACH TO THECHARACTERISATION OF MOLECULARORIENTATION IN UNIAXIALLY ANDBIAXIALLY STRETCHED SAMPLES OF PETPCole K C; Daly H B; Sanschagrin B; Nguyen K T;Ajji ACanada,National Research Council; Montreal,EcolePolytechnique(SPE)

The usual approach used to characterise the molecularorientation in biaxially oriented samples by IRspectroscopy is used to measure spectra withpolarisation in all three directions - machine, transverseand normal (or thickness). However, the lattermeasurement is rather difficult to make experimentally.A new approach to characterising the molecularorientation in both uniaxially and biaxially orientedsamples of PETP is employed. It makes use of the ratioof the absorption bands near 1250 and 1725 cm-1, thefirst of which shows parallel dichroism and the secondperpendicular dichroism. An equation is developed thatrelates this ratio to the molecular orientation withrespect to the direction of measurement. Thus it ispossible to determine individually the orientationfunctions with respect to the machine and transversedirections. The validity of functions determined in thisway is confirmed by comparison with birefringenceresults. 9 refs.

CANADA

Accession no.687420

Item 132Antec ’98. Volume II. Conference proceedings.Atlanta, Ga., 26th-30th April 1998, p.2215-8. 012PRACTICAL ANALYSIS TECHNIQUES OFPOLYMER FILLERS BY FOURIERTRANSFORM INFRARED SPECTROSCOPY(FTIR)Coles B J; Hall C JHauser Inc.(SPE)

The identification of polymers by FTIR is oftencomplicated by the presence of fillers. However for kaolinclay, an FTIR analysis should be able to identify the fillerand predict its concentration using a standard curve. Theresulting percentage is more reliable than a simple ash,which may change the chemical composition of the filler.2 refs.

USA

Accession no.687418

Item 133Polymer38, No.15, 1998, p.3327-33FTIR STUDY OF GRAFT COPOLYMERCOMPATIBILIZERS FOR BLENDS OFFUNCTIONALIZED POLYPROPYLENE ANDLIQUID-CRYSTALLINE POLYESTERSek D; Kaczmarczyk BPolish Academy of Sciences

FTIR spectroscopy was used to characterise mixtures ofPP functionalised with 6 wt% of acrylic acid (PPAA) andliquid crystalline polyester (PPAA contents of 50% or70%), graft copolymers of PPAA with the monomers fromwhich the polyester was derived (sebacic acid, 4,4'-dihydroxybiphenyl and d-hydroxybenzoic acid, againwith PPAA contents of 50% or 70%) and the fractionationproducts of the graft copolymers. The aim of theinvestigation was to study the structure of compatibilisersconsisting of the graft copolymers and the grafting wasfollowed by measuring changes in the amount ofcarboxylic and aliphatic-aromatic ester groups. the resultswere discussed. 3 refs.

EASTERN EUROPE; POLAND

Accession no.686650

Item 134Applied Spectroscopy52, No.5, May 1998, p.702-12ANALYSIS AS A FUNCTION OF TEMPERATUREOF THE DYNAMIC LINEAR INFRAREDDICHROISM SPECTRA OF ISOTROPIC ANDCOLD-DRAWN HIGH-DENSITYPOLYETHYLENELagaron J M; Steeman P A M; Kip B JDSM Research



A dynamic linear infrared dichroism study was carriedout as a function of temperature on isotropic and colddrawn HDPE using a rapid-scan setup. The dynamicin-phase dichroic spectrum and its components(parallel and perpendicular polarised spectra) wereanalysed. 15 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION;

NETHERLANDS; WESTERN EUROPE

Accession no.685291

Item 135Applied Spectroscopy52, No.5, May 1998, p.692-701INVESTIGATIONS OF RADICALPOLYMERISATION AND COPOLYMERISATIONREACTIONS IN OPTICALLY LEVITATEDMICRODROPLETS BY SIMULTANEOUSRAMAN SPECTROSCOPY, MIE SCATTERING,AND RADIATION PRESSURE MEASUREMENTSMusick J; Popp J; Trunk M; Kiefer WWurzburg,University

The combination of optical levitation with Ramanspectroscopy, elastic (Mie scattering), and radiationpressure measurements enables in-situ and real-timeinvestigation polymerisation and copolymerisationprocesses in microdroplets. The time-dependent evolutionof the polymerisation and copolymerisation reactions ofstyrene/unsaturated polyester resin was characterised byobserving the educt and product signals in the Ramanspectra. The size, the refractive index, and the wavelengthdependence of the optically levitated microparticle weredetermined from the position of the morphology-dependent resonances observed in Raman spectra, inelastic light scattering, and in radiation pressuremeasurements. 36 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.685290

Item 136Macromolecules31, No.11, 2nd June 1998, p.3753-5APPLICATION OF REAL TIME MID-INFRAREDFTIR IMAGING TO POLYMERIC SYSTEMS. I.DIFFUSION OF LIQUID CRYSTALS INTOPOLYMERSSnively C M; Koenig J LCase Western Reserve University

The FTIR imaging method was extended to the real-timeacquisition of images from systems varying with time.Emphasis is given to the monitoring of the diffusion of alow molecular weight liquid crystal pentylcyanobiphenylinto a solid polybutyl methacrylate film. 22 refs.

USA

Accession no.685003

Item 137Journal of Applied Polymer Science69, No.3, 18th July 1998, p.461-8APPLICATION OF ATR-FTIR SPECTROSCOPYCOMBINED WITH SPUTTER ETCHING FORDEPTH PROFILING OF A CHEMICALADDITIVE WITHIN A PULP FIBERTatsumi D; Yamauchi TKyoto,University

Attenuated total reflection-Fourier transform infra-red(ATR-FTIR) spectroscopy was used to determine theconcentration of a chemical additive (cationicpolyacrylamide resin) within a pulp fibre. The depthdistribution of the additive was determined by sputteretching the fibre surface. The obtained profile wascompared qualitatively with that obtained by the variable-angle ATR-FTIR depth profiling method. Most of theadditive was located at the surface, with some distributedwithin the fibre. It is concluded that the method can beused to clarify the distribution of other paper additiveswithin a pulp fibre, and that it can be applied to depthprofiling of minor components within a solid material.21 refs.JAPAN

Accession no.684061

Item 138Polymer Testing ’96. Conference proceedings.Shawbury, 5th-6th Sept.1996, paper 6. 57IDENTIFICATION OF ADDITIVES IN RUBBERAND PLASTIC MATERIALS BY COMBINEDLIQUID CHROMATOGRAPHY/INFRAREDSPECTROSCOPYSidwell JRapra Technology Ltd.(Rapra Technology Ltd.; Plastics & Rubber Weekly;European Plastics News)

The application of the Lab Connections LC TransformInterface for obtaining IR spectroscopic data on additivecomponents from polymeric systems separated bychromatographic means is discussed. Examinations basedon molecular size separation in solution using thetechniques of gel permeation chromatography and alsonormal phase and reverse phase high performance liquidchromatography are described. 2 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.683811

Item 139153rd ACS Rubber Division Meeting - Spring 1998.Conference preprints.Indianapolis, In., 5th-8th May,1998. Paper 7. 012APPLICATION OF RAMAN MICROIMAGING INCHARACTERISATION OF POLYMERSAppel R; Zerda T W



Texas,Christian University(ACS,Rubber Div.)

The incorporation of high-resolution optics in a Ramanspectrometer allows sampling from areas of less than onemicron in diameter. The addition of a confocal microscopeimproves the axial resolution to a couple of microns.Those developments, along with the introduction of notchfilters and holographic transmission gratings, allow thereduction of the acquisition time of Raman spectra fromminutes to seconds. The fast data collection combinedwith the high lateral and vertical resolutions makespossible scanning experiments in which the specimen isadvanced in micron size steps. Analysis of the spectraprovides information on the spatial composition of thesample. Phase separation in binary mixtures of twopolymers, Exxpro and Budene, is studied for differentcomposition of the blends. The average domain sizes aredetermined. 5 refs.USA

Accession no.683227

Item 140Polymer39, No.16, 1998, p.3631-40XPS AND FTIR STUDIES OF INTERACTIONS INPOLY(CARBOXYLIC ACID)/POLY(VINYLPYRIDINE) COMPLEXESXu Zhou; Goh S H; Lee S Y; Tan K LSingapore,National University

The nature of the complexes formed by the interactionsbetween polyacrylic acid (PAA) and polymethacrylic acid(PMAA) and with poly(4-vinylpyridine) and poly(2-vinylpyridine) in ethanol/water solution was studied usingFourier transform infra-red spectroscopy and x-rayphotoelectron spectroscopy. The PMAA complexesinvolved hydrogen-bonding interactions, whilst there wasevidence of ionic interactions in the PAA complexes. Thisdifference in the behaviour between the complexes isattributed to the higher acidity of PAA compared withthat of PMAA. 23 refs.SINGAPORE

Accession no.682246

Item 141Journal of Polymer Science : Polymer Physics Edition36, No.9, 15th July 1998, p.1529-37DISCRIMINATION OF ETHYLENE/VINYLACETATE COPOLYMERS WITH DIFFERENTCOMPOSITION AND PREDICTION OF THECONTENT OF VINYL ACETATE IN THECOPOLYMERS AND THEIR MELTING POINTSBY NEAR-INFRARED SPECTROSCOPY ANDCHEMOMETRICSShimoyama M; Hayano S; Matsukawa K; Inoue H;Ninomiya T; Ozaki YHyogo,Prefectural Police Headquarters; Bran &

Luebbe Co.Ltd.; Osaka,Municipal Technical ResearchInstitute; Kwansei-Gakuin,University

Near-infrared diffuse reflectance spectra were measuredby use of a rotating drawer for pellets of 12 kinds ofethylene-vinyl acetate copolymers with vinyl acetatecomonomer varying in the 7-44 wt% range. An attemptwas made to predict the melting points of thesecopolymers. The potential of near-infrared spectroscopywith that of Raman spectroscopy in the discrimination ofcopolymers and the prediction of their properties wasgiven. 23 refs.JAPAN

Accession no.681676

Item 142Journal of Applied Polymer Science68, No.5, 2nd May 1998, p.785-92INFRARED SPECTROSCOPIC STUDY OFSILICA FILM FORMATION ANDDECOMPOSITION OF VINYL SILANEDERIVATIVE BY HEAT TREATMENT. II. ONCOPPER SURFACEKim H; Jang JSeoul,National University

The thermooxidative degradation and SiOx film formationof poly(vinyl imidazole-co-vinyl trimethoxysilane) oncopper was investigated using Fourier transform infraredreflection and absorption spectroscopy. Thermaldegradation of the copolymer was catalysed by copper inthe film and at the substrate surface. Copper in thecopolymer film contributed to the formation of a copper-containing SiOx film during thermal degradation. Heattreatment caused defects in the copper-containing film,and copper corrosion proceeded through these defects.In a thickly coated sample, the film cracked because ofresidual stress, resulting in the formation of copper oxidesthrough the crack. Copper oxides in the film interactedwith the SiOx film to form a copper-rich phase in near tofilm defects and cracks. 33 refs.SOUTH KOREA

Accession no.679543

Item 143Macromolecules31, No. 7, 7th April 1998, p.2141-51SELECTIVELY DEUTERATED LIQUIDCRYSTALLINE CYANOAZOBENZENE SIDE-CHAIN POLYESTERS. III. INVESTIGATIONSOF LASER-INDUCED SEGMENTAL MOBILITYBY FOURIER TRANSFORM INFRAREDSPECTROSCOPYKulinna C; Hvilsted S; Hendann C; Siesler H W;Ramanujam P SRiso National Laboratory; Essen,University

The laser-induced anisotropy in thin films of an extensivenumber of cyanoazobenzene sidechain liquid crystalline



polytetradecanedioates, -dodecanedioates, and -adipatesselectively deuterated at different positions wasinvestigated by FTIR. The analysis of the segmentalorientation based on dichroic ratios of characteristicabsorption bands shows that, in polyesters with long main-chain spacing (tetradecanedioates and dodecanedioates),not only the light sensitive azo chromophore, but also themain-chain methylene segment and to a small extent theflexible spacer are preferentially oriented perpendicularto the laser light polarisation. The extent of orientationincreases with increasing spacer length. On the other hand,in the shorter adipates only the chromophore and thespacer are likewise oriented. Rapid-scan FTIR analysisperformed on-line with the laser irradiation reveals thatthe alignment of the aliphatic segments arisessimultaneously with the chromophore orientation.Temperature dependent IR investigations of the laser-induced orientation shows that the preservation of thephotoinduced anisotropy directly relates to the polyesterphase behaviour. Relevance to rewritable optical storageis suggested. 41 refs.DENMARK; EUROPEAN COMMUNITY; EUROPEAN UNION;GERMANY; SCANDINAVIA; WESTERN EUROPE

Accession no.679222

Item 144Colour Quantification: Adding Value With Instruments.Retec proceedings.Baltimore, MD, 15th-17th Sept.1997, paper 11. 52MEASURING STABILISERS IN PIGMENTEDPLASTICS WITH NEAR-INFRAREDSPECTROSCOPYSolera P; Nirsberger M; Castillo NCiba Specialty Chemicals Corp.(SPE,Color & Appearance Div.)

Near-infrared (NIR) spectroscopy has become acommonplace analytical tool in the plastics industry. NIRtechniques have made quantification of many organiccomponents in polymer processing easy and quick. Thework presented outlines the methodology for using NIR tomeasure stabiliser levels in colour concentrates and naturalpolymer formulations. Advantages and limitations areconsidered as well as particle size and product form. 4 refs.USA

Accession no.672730

Item 145Polymer Degradation and Stability58, Nos.1-2, 1997, p.15-31FTIR EMISSION SPECTROSCOPY APPLIED TOPOLYMER DEGRADATIONCelina M; Ottesen D K; Gillen K T; Clough R LSandia National Laboratories

The thermal degradation of some common polymers isinvestigated using IR emission spectroscopy. The potentialof the technique to contribute to polymer degradation

studies is demonstrated by measuring the spectroscopicchanges that occur during thermal degradation, oxidationor decomposition of polymers under air at temperaturesranging from 150 to 25 deg.C. Polymer types studiedinclude EPDM and nitrile rubbers (commercial materialscontaining some inorganic fillers), PMMA, PAN, PA, PVCand PS. The resulting qualitative changes in the polymersare easily detected, and are correlated with the currentknowledge on the degradation mechanisms of thesematerials. These include simple carbonyl formation andrelated oxidative reactions, weight loss and volatilisation,as well as formation of conjugation and specific polymerreactions. Some fundamental aspects and limitations of thetechnique are discussed to demonstrate the intrinsicdifficulties of attempting to determine precise emittancesand ultimately quantitative spectroscopic information.FTIR emission appears to be promising for studying insitu polymer degradation. 33 refs.USA

Accession no.668861

Item 146Polymer39, No.3, 1998, p.573-82FTIR. SPECTROSCOPY ON ELECTRONIRRADIATEDPOLYTETRAFLUOROETHYLENEFischer D; Lappan U; Hopfe I; Eichhorn K-J;Lunkwitz KDresden,Institute of Polymer Research

The effect of radiation dose and the hydrolysis conditionson the chemical structure of electron irradiated PTFE wasstudied by different methods of FTIR spectroscopy.Irradiation produced acid fluoride (COF) groups andunder ambient conditions, these hydrolysed withatmospheric humidity to form free and associatedcarboxylic acid (COOH) groups. The concentration ofthese groups was different in the near-surface regions andin the bulk phase. The formation of carboxylic groups indifferent states of association depended on the hydrolysisconditions. The results were discussed in detail. 9 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.665954

Item 147Applied Spectroscopy51, No.12, Dec.1997, p.1784-90DEPTH PROFILING STUDY OF EFFECT OFANNEALING TEMPERATURE ON POLYMER/POLYMER INTERFACES IN LAMINATESUSING CONFOCAL RAMANMICROSPECTROSCOPYHajatdoost S; Olsthoorn M; Yarwood JSheffield,Hallam University; Utrecht,University

The effect of annealing temperature on molecularinteractions at the interface of polymer laminates was



reported. Depth profiling was carried out using confocalRaman microspectroscopy to study polyacrylonitrile/polyvinyl alcohol and polyacrylonitrile/polyacrylic acidlaminates. The laminates were annealed at 65, 75 and 90C.It was demonstrated that the degree of hydrogen bondinginteraction between the nitrile and alcohol groups nearthe interfacial region changes between laminates annealedat different temperatures. For comparison, Ramanmapping of a polyacrylonitrile-polyvinyl alcohol blendwas used to study the interactions between the polymersin this (disordered) system. 29 refs.EUROPEAN COMMUNITY; EUROPEAN UNION;NETHERLANDS; UK; WESTERN EUROPE

Accession no.665697

Item 148Applied Spectroscopy51, No.11, Nov.1997, p.1736-40GENERALISED TWO-DIMENSIONAL FOURIERTRANSFORM INFRARED PHOTOACOUSTICSPECTRAL DEPTH-PROFILING ANALYSISJiang E Y; McCarthy W J; Drapcho D L;Crocombe R ABio-Rad Laboratories Inc.

A new application of generalised two-dimensionalcorrelation spectroscopy in photoacoustic depth-profilinganalysis. Both rapid-scan and step-scan photoacousticspectroscopy (obtained by using the software-baseddigital signal processing technique) of multilayer sampleswere used to calculate generalised two-dimensionalcorrelation maps. Advantages of this unambiguousanalysis method in enhancing spectral as well as depthresolutions, over conventional two-dimensionalcorrelation and other spectral depth-profiling methods,were discussed. 31 refs.USA

Accession no.665694

Item 149Polymer Degradation and Stability57, No.3, 1997, p.339-48CLEARCOAT ANALYSIS IN ISOLATED ANDMULTI-LAYER PAINT SYSTEMS BYCONFOCAL RAMAN MICROSCOPYDupuie J L; Weber W H; Scholl D J; Gerlock J LFord Motor Co.

Confocal Raman spectroscopy was used to characterisethe chemical composition of clearcoats in three paintsystems: weathered and unweathered samples of isolatedacrylic/melamine and acrylic/urethane clearcoats,polyester urethane clearcoats in weathered andunweathered samples of a complete paint system onplastic, and UV light cured acrylic clearcoats onpolycarbonate substrates. 11 refs.USA

Accession no.664076

Item 150Journal of Applied Polymer Science66, No.13, 26th Dec.1997, p.2465-73MEASURING WATER DIFFUSION IN POLYMERFILMS ON THE SUBSTRATE BY INTERNALREFLECTION FOURIER TRANSFORMINFRARED SPECTROSCOPYLinossier I; Gaillard F; Romand M; Feller J FLyon,Universite; Sud Bretagne,Universite

A method is presented based on multiple internalreflection-FTIR to measure the diffusion coefficients ofliquid in polymer, e.g. PMMA or PS, films applied to asubstrate. The experimental method here described wasdesigned primarily to measure in-situ liquid water massuptake and diffusion based on sorption kinetics, but itcan also be suitable for vapours, or for other liquids. 24refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.664045

Item 151Polymer Science Series B39, Nos.9-10, Sept.-Oct.1997, p.358-64IR SPECTROSCOPIC STUDY OF RADICALPOLYMERISATION KINETICSKurmaz S V; Roshchupkin V PRussian Academy of Sciences

An IR spectroscopic technique for the study of kineticsof radical copolymerisation of acryl and vinyl monomerswas developed. The technique is based on monitoring theconversion curves and determining copolymerisation ratesin the course of the process separately for each monomerby measuring variations in the intensity of IR absorptionbands of reacting vinylidene groups. A comparative studyof the copolymerisation of model monomer pairs usingmonofunctional and polyfunctional compounds provideddata on the role of structural-physical transformations,involved in the formation of crosslinked polymers, onthe copolymerisation kinetics and on the non-uniformityof distribution of crosslinks in the copolymers formed.17 refs.RUSSIA

Accession no.662893

Item 152Pigment & Resin Technology26, No.6, 1997, p.387-8POLYMER ANALYSIS USING NEAR INFRAREDSPECTROSCOPYBran & Luebbe Ltd.

The use of infrared spectroscopy for polymer analysis isdiscussed, with particular reference to developments inequipment from Bran & Luebbe. The company offers fourindividual instruments, each with its own specific area ofapplication for use at various stages in the manufacture



of polymeric materials. They are the InfraProver,InfraPrime, InfraAlyzer 600 and InfraAlyzer 200, thelatter representing the most recent breakthrough in thedevelopment technique, providing laboratories with theability to analyse solid, powdered, semi-solid and liquidmaterials with a single instrument. The use of eachinstrument is discussed, and examples of the use of someby industry are described.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.662760

Item 153Journal of Vinyl and Additive Technology3, No.3, Sept.1997, p.200-4FOURIER TRANSFORM INFRARED MICROSPECTROSCOPY MAPPING. APPLICATIONSTO THE VINYL SIDING INDUSTRYGarcia D; Black JElf Atochem NA

Applications of FTIR microspectroscopy mapping to thevinyl siding industry were examined. Particular attentionwas paid to determination, in single mapping experiments,of the compositional changes associated with capstockto substrate transition and to evaluation of the degradationspecies and level observed during weathering exposurethroughout the thickness of the siding panel. 4 refs.USA

Accession no.661984

Item 154152nd ACS Rubber Division Meeting, Fall 1997.Conference Preprints.Cleveland, Oh., 21st-24th Oct.1997, Paper 123, pp.19.012HNBR AND LONG-TERM SERVICEABILITY INMODERN AUTOMOTIVE LUBRICANTS. I.ANALYTICAL STUDYTripathy B S; Smith K CFederal-Mogul Corp.(ACS,Rubber Div.)

The mechanism responsible for the hardening ofhydrogenated nitri le rubber automotive sealcompounds on prolonged exposure to automatictransmission fluids at high temperature wasinvestigated using Fourier transform IR spectroscopy.The increase in hardness was found to result primarilyfrom chemical attack at the acrylonitrile (AN) sites.This chemical attack first resulted in the formation ofisocyanide or isonitrile ions. The proposed mechanisminvolved crosslinking at the AN sites through theformation of isonitrile ions and the subsequentformation of imides. The isonitrile intermediate formedionic bonds resulting in the formation of an ionomeronce the concentration became sufficiently high.Ultimately these ions crosslinked to form imides in the

presence of oxygen or water. It was proposed that theincrease in hardness was due to the formation of theionomer and the imides. 9 refs.

USA

Accession no.659564

Item 155152nd ACS Rubber Division Meeting, Fall 1997.Conference Preprints.Cleveland, Oh., 21st-24th Oct.1997, Paper 40, pp.10.012THERMAL AND SPECTROSCOPIC(VIBRATIONAL AND NUCLEAR MAGNETICRESONANCE) CHARACTERIZATION OFETHYLENE-PROPYLENE-DIENE (EPDM)ELASTOMERSWinter J M; Edmondson M S; Parikh D R;Mangold D J; Castille M JDuPont Dow Elastomers LLC(ACS,Rubber Div.)

The sequence distribution of EPM and EPDM samplesprepared using vanadium/aluminium chloride andmetallocene catalysts was studied by carbon-13 NMR andFourier transform IR spectroscopy. The influence ofsequence distribution on thermal properties was alsoinvestigated. 13 refs.

USA

Accession no.658294

Item 156Biomaterials18, No.21, 1997, p.1387-409IN-VIVO DEGRADATION OFPOLYURETHANES: TRANSMISSION-FTIRMICROSCOPIC CHARACTERISATION OFPOLYURETHANES SECTIONED BYCRYOMICROTOMYMcCarthy S J; Meijs G F; Mitchell N; Gunatillake P A;Heath G; Brandwood A; Schindhelm KCSIRO; New South Wales,University

A combination of cryomicrotomy and FTIR microscopywas used to investigate chemical changes in unstrainedsheets of Pellethane 2363-80A, Tecoflex EG80A andBiomer caused by biodegradation (18 monthsubcutaneous ovine implant). Cryomicrotomy was usedto obtain thin sections from the surface into the bulk,parallel to the plane of the surface. FTIR microscopy wasthen used to obtain infra red absorbance spectra.Comparisons between the IR spectra (by spectralsubtraction) from implant surface, implant interior andnon-implanted controls were used to detect chemicalchanges. SEM was used to assess microstructural changesowing to biodegradation. 94 refs.

AUSTRALIA

Accession no.657629



Item 157Applied Spectroscopy51, No.3, March 1997, p.362-8ONLINE POST CONSUMER PACKAGEIDENTIFICATION BY NIR SPECTROSCOPYCOMBINED WITH FUZZY ARTMAPCLASSIFIER IN INDUSTRIAL ENVIRONMENTFeldhoff R; Wienke D; Cammann K; Fuchs HMuenster,Institute of Chemical & Biochemical SensorResearch; Nijmegen,Catholic University;Muenster,University

An optical set-up consisting of a high-throughput near-IR (NIR) spectrograph with an InGaAs-array detector andspecially designed collection optics is used to recordspectra from post consumer packages located on anindustrial conveyor belt. NIR spectra of packages ofdifferent polymers (PE, PETP, PP, PS and PVC) and of acardboard/plastic compound are recorded between 900and 1700 nm with 6.3-ms integration time. The visualdistinction between the spectra is demonstrated by aid ofprincipal component analysis (PCA) plots. The spectraare further classified by a Fuzzy ARTMAP neuralnetwork. The method is assessed to be suitable for on-line identification under industrial conditions. 16 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;NETHERLANDS; WESTERN EUROPE

Accession no.656293

Item 158Applied Spectroscopy51, No.3, March 1997, p.346-9AMPLITUDE SPECTRUM APPROACH INDYNAMIC FT-IR SPECTROSCOPY OFUNIAXIALLY ORIENTED POLYETHYLENETEREPHTHALATE FILMS. I. DRAW RATIODEPENDENCESonoyama M; Shoda K; Katagiri G; Ishida HToray Research Center Inc.

A method of data manipulation using the dynamicmagnitude spectrum and the static absorbance spectrum isapplied to uniaxially drawn PETP films with five differentdraw ratios for the evaluation of the amplitude of dynamicstructural changes under a sinusoidal strain at the level ofa functional group. This analysis reveals that, in the drawnfilm, the skeletal structures, such as the C-O bond in theethylene glycol unit and the phenyl ring, are susceptible todeformation by mechanical stretching, while the dynamicstructural changes around the methylene group are small.It was assumed that the backbone of the polymer isresponsible for the change of the mechanical propertiesinduced by the drawing of the film. 24 refs.JAPAN

Accession no.656292

Item 159Macromolecular Rapid Communications

18, No.10, Oct.1997, p.903-9SIMPLE METHODS FOR ASSESSING THECONFORMATIONAL SENSITIVITY OF IRBANDS BY DICHROISMOu-Yang W-C; Chen H-LKaohsiung,National Institute of Technology;Taiwan,National Tsing Hua University

Two methods for evaluating the conformationalsensitivities of IR bands from the measurement of dichroicratio using PEEK as an example. Both methods werebased on the fact that the orientation function calculatedby all conformationally insensitive bands should beidentical. 11 refs.CHINA

Accession no.656202

Item 160Synthetic Metals89, No.2, Aug.1997, p.149-521320-NM EXCITED FT-RAMAN SPECTRA OFNA-DOPED TRANS-POLYACETYLENEJin-Yeol Kim; Ando S; Sakamoto A; Furukawa Y;Tasumi MTokyo,University

The Fourier transform-Raman spectra of trans-polyacetylene(t-PA) doped with sodium at variousconcentrations were observed with the 1320 nm laser line.Doping-induced Raman bands for lightly doped t-PA wereobserved for the first time. The observed wave numbersof the C:C and C-C stretch bands of lightly doped t-PAwere lower than those of the corresponding bands ofpristine t-PA, whereas the reverse was the case for heavilydoped t-PA. The origins of doping-induced Raman bandsare discussed in terms of solitons and polarons. 20 refs.JAPAN

Accession no.656141

Item 161Polymer38, No.22, 1997, p.5699-702EFFECTIVE WIDTH OF INTERFACE IN ASTRESSED MODEL POLYMER COMPOSITEMEASURED BY MICRO-FTIRLourie O; Wagner H D; Levin NWeizmann Institute of Science; Israel,Police HQMaterials Laboratory

The effect of mechanical deformation on a UV-curedurethane-acrylate polymer and on a silicon carbide/urethane-acrylate model composite was studied by micro-FTIR spectroscopy. This technique was used for the firsttime to measure the width of the interfacial zone beyondwhich the fibre has no influence on the matrix. the resultswere discussed. 14 refs.ISRAEL

Accession no.654334



Item 162Macromolecular SymposiaVol.119, July 1997, p.277-82FTIR AND ATR ANALYSES ON APOLYPROPYLENE (PP) SURFACE AFTERPLASMA TREATMENT IN THE STUDY OFCHITOSAN SURFACE GRAFTING TOIMPROVE PP DYEING BEHAVIOURRochery M; Lam T M; Crighton J SGEMTEX-ENSAIT; Leeds,University

The treatment of a PP film surface to improve its dyeingbehaviour was studied. A plasma treatment was carriedout to try to create oxidising groups on this surface, sothat it could be then easier to apply a specificpolysaccharide chitosan which is reported to be muchmore reactive than PP and easy to dye. A study about thevarious parameters of the plasma instrument wasnecessary to find the optimal treatment. The possibleformed oxidising groups were emphasised by FTIR andATR analyses. Chitosan was applied after the plasmatreatment and the dyeing result which was then observedwas quite encouraging in certain conditions. 8 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; UK;WESTERN EUROPE

Accession no.653741

Item 163Macromolecular SymposiaVol.119, July 1997, p.261-8ORDERING AND MOBILITY OFFERROELECTRIC LIQUID CRYSTAL DIMERAS STUDIED BY FTIR SPECTROSCOPY WITH2-D IR CORRELATION ANALYSISShilov S V; Skupin H; Kremer F; Wittig T; Zentel RSt.Petersburg,Institute of Macromol.Compounds;Leipzig,University; Mainz,University

Both a conservative rapid-scan FTIR technique and anovel step-scan FTIR technique with two-dimensionalanalysis were used to study the orientation and themobility of a ferroelectric liquid crystal dimer duringswitching under an electric field. The detailed mutualarrangements of different molecular segments (mesogen,poly(methylene) chain, polysiloxane chain) in a smecticC phase were derived from the static spectra. Temperatureand electric field strength dependencies of the mobilityof these segments are discussed. 18 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;RUSSIA; WESTERN EUROPE

Accession no.653739

Item 164Macromolecular SymposiaVol.119, July 1997, p.101-11APPLICATIONS OF PHOTOACOUSTIC STEP-SCAN FTIR SPECTROSCOPY TO POLYMERICMATERIALS

Gregoriou V G; Hapanowicz RPolaroid Corp.; Nicolet Instrument Corp.

Step-scan photoacoustic data are presented that prove theability of the technique to successfully isolate the infraredsignature on the top layer from the infrared spectrum ofthe bulk material, proving the sub-micron resolutioncapability of the method. Results are shown that underlinethe fact that the most serious problem in photoacousticspectroscopy is saturation at high absorptivities. 12 refs.USA

Accession no.653724

Item 165Macromolecular SymposiaVol.119, July 1997, p.89-100EVIDENCE OF ELECTRON ACCEPTOR-ELECTRON DONOR INTERACTIONS INTHERMOPLASTIC POLYMER BLENDS BYUSING FTIR-ATR SPECTROSCOPYBrogly M; Nardin M; Schultz JInstitut de Chimie des Surfaces et Interfaces

Specific interactions in binary blends of ethylene-vinylacetate copolymer with various low molecular weightterpene-phenol tackifying resins (TPR) weresystematically investigated, as a function of thecomposition of the blend and of the electron acceptorability of the resin, by using attenuated total reflectionFTIR spectroscopy. Molecular acid-base were evidencedbetween TPR hydroxyl groups and EVA carbonyl groups.Quantitative information on the fraction of acid-basebonded entities, the enthalpy and equilibrium constant ofpair formation were obtained. A crystalline transition ofthe EVA copolymer was observed and discussed in termsof enthalpy and entropy considerations based on FTIRand calorimetric DSC investigations. Fundamental resultsare then summarised to predict the interfacial reactivityof such polymer blends towards acid or basic substrates.16 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.653723

Item 166Macromolecular SymposiaVol.119, July 1997, p.65-77POLYMERS, ADDITIVES, SURFACTANTS ANDTHEIR MIXTURES: COMPUTER-BASEDSEARCH WITH SPECIAL FTIR LIBRARIESHummel D OCologne,University

The efficiency of selected search algorithms with specificFTIR libraries of application-defined chemical systemswas assessed. This investigation was done with a PC of850 MB/33 MHz, Windows 3.1 and the SPECTACLEprogram of LabControl/Cologne. The libraries contained



standardised FTIR spectra of 3601 defined polymers, 530industrial polymers and resins, 1969 additives (pigments,stabilisers, plasticisers, etc.), 1190 surfactants and 1614monomers, pyrolysates and educts. For searches, the datadensity was reduced to 4/cm. 21 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.653721

Item 167Macromolecular SymposiaVol.119, July 1997, p.49-63POTENTIAL OF TWO-DIMENSIONAL NEAR-INFRARED CORRELATION SPECTROSCOPYIN STUDIES OF PRE-MELTING BEHAVIOUR OFNYLON 12Ozaki Y; Yongliang Liu; Noda IKwansei-Gakuin,University; Procter & Gamble Co.

This review paper discusses the potential of generalisedtwo-dimensional near-infrared correlation spectroscopyin studies of pre-melting behaviour and hydrogen bondsof nylon 12. A study on dissociation and hydrogen bondsof N-methylacetamide is also reviewed as a modelcompound study of nylon 12. FTIR spectra were measuredover a temperature range of 30-150C where gradualweakening of inter- or intramolecular associativeinteractions and decrease of local order leading to theeventual fusion of nylon 12 crystals are observed. 24 refs.JAPAN; USA

Accession no.653720

Item 168Macromolecular SymposiaVol.119, July 1997, p.1-13APPLICATIONS OF TWO-DIMENSIONALCORRELATION SPECTROSCOPY IN DEPTH-PROFILING PHOTOACOUSTICSPECTROSCOPY, NEAR-INFRARED DYNAMICRHEO-OPTICS, AND SPECTROSCOPICIMAGING MICROSCOPYNoda I; Story G M; Dowrey A E; Reeder R C;Marcott CProcter & Gamble Co.

Some new developments of two-dimensionalspectroscopy are discussed. As a specific example, two-dimensional correlation analysis of a polymer laminatefilm using several different spectroscopic techniques ispresented. The versatility of this technique was developedusing depth-profiling photoacoustic spectroscopy, mid-and near-IR dynamic rheooptical developments, andspectroscopic imaging microscopy. Spatial and temporalvariations of near-IR spectra are effectively analysed bythe two-dimensional correlation technique. Step-scanningFTIR spectrometers provide an opportunity to obtaindesired spectral information often difficult to obtain bythe conventional rapid-scanning technique. 12 refs.

USA

Accession no.653717

Item 169Polymer38, No.21, 1997, p.5455-62STRUCTURE OF STYRENE-ACRYLONITRILE/BUTADIENE POLYMER STUDIED BY 2D-IRSPECTROSCOPYSteeman P A M; Meier R J; Simon A; Gast JDSM Research; Bruker Analytische MesstechnikGmbH

2D IR spectroscopy involving mechanical excitation isemployed to study the mechanical relaxation phenomenain an ABS sample, revealing detailed informationregarding the molecular segments involved inmacroscopic mechanical relaxation. From the temperaturedependence of the dynamic signals it is corroborated thatin the ABS sample the polybutadiene rubber relaxesentirely independently from the SAN matrix, and thus ispresent as a separate phase in the material. The rapid-scan variation developed to perform 2D IR experimentsoffers a significantly reduced measurement time incomparison with the step-scan mode of operation. Inparticular, in relation to research in the polymer field, inwhich case stress relaxation is expected to occur duringthe 2D IR experiment, this presents a major advantage.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;NETHERLANDS; WESTERN EUROPE

Accession no.652565

Item 170Applied Spectroscopy51, No.8, Aug.1997, p.1245-50STUDY OF IMPULSE POLYMER RHEO-OPTICSBY STEP-SCAN FT-IR TIME-RESOLVEDSPECTROSCOPYWang H; Palmer R A; Manning C JDuke,University; Manning Applied Technology

The applicability of step-scan impulse/response FT-IRspectroscopy to the rheo-optical study of polymer filmsis demonstrated by spectral measurements with isotacticPP. A novel piezoelectrically driven microrheometer isemployed to apply repetitive impulses to a polymersample while time-domain spectra are recorded by step-scan FT-IR spectroscopy. The traditional advantages ofFourier transform spectroscopy are retained whileproviding a second multiplex advantage for thecharacterisation of the time-dependence of the sampleresponse. Reproducible results, consistent with thefrequency-domain literature data and having good signal-to-noise ratio, are obtained. The spectral changes due tomolecular reorientation are found to be essentially as fastas the mechanical stretching, also consistent withfrequency-domain results. This is thought to be the firstreported step-scan FT-IR time-domain rheo-optical



measurement. This technique appears to be applicable toa variety of polymer samples. The advantages of time-domain measurements over frequency-domainmeasurements are briefly discussed. 33 refs.USA

Accession no.652416

Item 171Applied Spectroscopy51, No.8, Aug.1997, p.1238-44PHASE-RESOLVED DEPTH PROFILING OFTHIN-LAYERED PLASMA POLYMER FILMS BYSTEP-SCAN FOURIER TRANSFORMINFRARED PHOTOACOUSTICSPECTROSCOPYJiang E Y; Palmer R A; Barr N E; Morosoff NDuke,University; Missouri-Rolla,University

After reviewing the background of step-scaninterferometric photoacoustic spectroscopy, a step-scanFourier transform photoacoustic phase-resolved techniqueand its applications in depth profiling of micrometer-thicklayered plasma polymers are described. In particular, thepower of direct use of the photoacoustic phase spectrumin both qualitative and quantitative depth profiling of thelayered samples is extensively discussed. The effects ofboth spatial origin and intensity of a photoacoustic signalon its phase are explicitly analysed for both overlappingand distinctive, non-overlapping bands of thin-layeredplasma polymer samples. The phase spectrum techniqueis shown to be a very effective and efficient method ofspectral depth profiling analysis. 29 refs.USA

Accession no.652415

Item 172Applied Spectroscopy51, No.8, Aug.1997, p.1083-91IMPROVEMENTS IN USE OF ATTENUATEDTOTAL REFLECTION FOURIER TRANSFORMINFRARED DICHROISM FOR MEASURINGSURFACE ORIENTATION IN POLYMERSEverall N J; Bibby AICI Research & Technology Centre; Graseby-SpecacLtd.

Improvements in the use of attenuated total reflection (ATR)Fourier transform infrared (FT-IR) dichroism for measuringsurface orientation in polymer films are described for PETP.It is shown that normalising band intensifies relative to anondichroic band, prior to calculating dichroic ratios,eliminates the need to maintain identical contact areas/pressures when removing, rotating and reclamping samplesto the ATR element, which has been a major historicaldisadvantage of this technique. The normalisation is vital;it makes the calculated dichroic ratios largely insensitiveto variations in sample/prism contact area, and less sensitiveto uncertainties in the refractive indices and birefringence

of the polymer. For PETP, it is shown that the birefringencecan be neglected in the analysis, and a single approximaterefractive index used. This is a significant benefit since thebirefringence varies as a function of orientation andcrystallinity. Equations are derived which allow thecalculation of all second-order orientation parameters andthe averaged squared direction cosines, from the normalisedATR dichroic ratios. It is also shown how a single-reflectiondiamond ATR unit is an ideal tool for this work, since itallows small, hard, or irregularly shaped samples to beexamined without fear of damaging the ATR element. 16refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.652413

Item 173Macromolecules30, No.8, 21st April 1997, p.2400-7RAMAN VIBRATIONAL STUDIES OFSYNDIOTACTIC POLYSTYRENE. II. USE OFTHE FUNDAMENTAL VIBRATIONAL MODE ASA QUANTITATIVE MEASURE OFCRYSTALLINITY WITH ISOTROPICMATERIALKellar E J C; Evans A M; Knowles J; Gaiotis C;Andrews E HLondon,University,Queen Mary & Westfield College

Raman spectra were taken with the 514.5 nm line of anargon ion laser. Syndiotactic PS was found to exhibit twodistinct vibrational peaks in the Raman spectrumcorresponding to the fundamental vibrational mode. Thesefeatures were assigned to the symmetric phenyl ringbreathing mode coupled to the polymer backbone. Thepresence of long all-trans sequences gives rise to a peakat about 773/cm, whereas less well-defined trans/gaucheconformations result in a separate peak at 798/cm. Withincreasing levels of crystallinity, the integrated intensityof the former feature grows at the expense of the high-frequency feature. The use of a series of annealed isotropicfilms of glassy syndiotactic PS of increasing crystallinityand molten syndiotactic PS has made it possible toexamine the precise relationship between these twofeatures and other neighbouring vibrational peaks. Thelevel of crystallinity within each sample was determinedindependently using wide-angle X-ray scattering, DSCand IR spectroscopic measurements. Results indicate thatthe relative area under the all-trans fundamental band canbe directly related to the crystalline volume fraction withineach sample. It is proposed that this Raman vibrationalfeature centered around 773/cm can be used as aquantitative measure of crystallinity for syndiotactic PSonce the contribution from the all-trans sequences in themelt is subtracted from the spectrum. 44 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.651397



Item 174Macromolecules30, No.8, 21st April 1997, p.2391-9TWO-DIMENSIONAL NEAR-INFRARED (NIR)CORRELATION SPECTROSCOPY STUDY OFPREMELTING BEHAVIOUR OF NYLON 12Ozaki Y; Liu Y; Noda INishinomiya,Kwansei-Gakuin University; Procter &Gamble Co.

FT-NIR spectra of Nylon 12 in a cast film was measuredover a temperature range of 30-150C. The 2D NIRcorrelation analysis reveals that there are at least eightbands in the 6800-6100/cm region where the first overtoneof an NH stretching mode of Nylon 12 is expected toappear. They may be ascribed to free- and hydrogen-bonded NH groups in various environments. Theasynchronous 2D NIR correlation spectrum in the aboveregion indicates that the amide groups with a free carbonyloxygen appears first and then unassociated free amideand amide with free NH follow as the temperature inincreased. In the 6000-5500/cm region of the synchronousspectrum, four dominant autopeaks corresponding to thefirst overtones of the methylene stretching modes areobserved at 5840, 5770, 5680, and 5640/cm, and negativecross peaks are found between the 5770/cm band and therest. This observation, together with the careful inspectionof the dynamic NIR spectra, suggests that the band at5770/cm is due to the contribution of the CH stretchingvibration of an ordered or highly associated form of Nylon12, which decreases with temperature, while other NIRbands correspond to more disordered forms. 33 refs.JAPAN; USA

Accession no.651396

Item 175Journal of Vinyl and Additive Technology3, No.2, June 1997, p.126-9APPLICATIONS OF INFRAREDSPECTROSCOPY TO CUSTOMER PROBLEMSIN THE VINYL INDUSTRYGarcia DElf Atochem North America

This paper outlines procedures used in the identificationof typical PVC formulations, starting with the resin andproceeding to impact modifier, process aids, lubricants,stabiliser system and fillers. The emphasis is on FTIRmicroscopy as the most versatile approach requiring smallsamples and minimal to no sample preparation. Othercommonly used FTIR techniques are also outlined. Wetseparation protocols, applicability and limitations asrelated to FTIR analysis are discussed. Typical examplesinclude vinyl siding, packaging and bottle formulationsas well as contaminants often encountered in theseformulations and raw materials.USA

Accession no.650270

Item 176Kunststoffe Plast Europe87, No.7, July 1997, p.12-3NIR SPECTROSCOPY FOR THE ANALYSIS OFMIXED MATERIALSPahl M H; Grosse-Aschhoff M

Near infrared spectroscopy can be used to analyse theconcentrations of all the components of a PVC mixture.Unlike conventional methods for the analysis of mixtures,this technique is not limited to one “critical” component.NIR, after calibration, can analyse all the components ina single measuring operation. This technique is thereforeespecially suitable for analysing dry blends comprisingseveral components.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.648051

Item 177Polymer38, No.14, 1997, p.3435-40FTIR. INVESTIGATION OF STRUCTURALMODIFICATION OF POLYCARBONATEDURING THERMODYNAMICAL TREATMENTSHeymans NBruxelles,Universite

The effects of annealing and ageing on IR absorptionspectra of polycarbonate were studied. The effect ofannealing was primarily a modification of trans-trans andtrans-cis population of the carbonate group, leading to amore stable structure with a lower internal energy. Ageingproceeded mainly by extremely local rearrangementscompatible with a densified structure. Ageing was,however, accompanied by a slight change inconformational populations. The results were discussed.34 refs.BELGIUM; EUROPEAN COMMUNITY; EUROPEAN UNION;WESTERN EUROPE

Accession no.647751

Item 178Applied Spectroscopy51, No.6, June 1997, p.856-65APPLICATION OF A SPECTROSCOPICINFRARED FOCAL PLANE ARRAY(FPA)SENSOR FOR ON-LINE IDENTIFICATION OFPLASTIC WASTEvan den Broek W H A M; Wienke D; Melssen W J;Feldhoff R; Huth-Fehre T; Kantimm T; Buydens L M CNijmegen,Catholic University; Germany,Institute forBiochemical Sensor Research

A spectroscopic near-IR imaging system, using a FPAdetector, was developed for remote and on-linemeasurements on a macroscopic scale. On-linespectroscopic imaging requires high-speed sensors and



short image processing steps. The use of a FPA detectorin combination with fast chemometric software wasinvestigated. As these imaging systems generated so muchdata, multivariate statistical techniques were required toextract the important information from the multi-dimensional spectroscopic images. These techniquesincluded principal component analysis and lineardiscriminant analysis for supervised classification ofspectroscopic image data. The identification system wasconstructed, implemented and tested for a real-worldapplication of plastic identification in municipal solidwaste. 31 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;NETHERLANDS; WESTERN EUROPE

Accession no.647715

Item 179Journal of Polymer Science : Polymer Physics Edition35, No.9, 15th July 1997, p.1361-72INFRARED DICHROISM AND POLYMERORIENTATION IN ATTENUATED TOTALREFLECTION. THEORETICALCONSIDERATIONSBelali R; Vigoureux J M; Morvan JBesancon,University

The partial axial orientation model usually use for stronglyoriented polymers was adjusted to samples of weaklyaligned polymers and the parameters describing theorientation configuration were related to the dichroicratios in four particular molecular chain distributions, i.e.randomly, totally, partially and elliptically oriented. A newmethod that led to the determination of these dichroicratios from ATR spectra was developed. This method wasbased only on the use of three distinct polarisations ofthe beam. All the practical difficulties usually encounteredin the other methods were thus eliminated. 28 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.645643

Item 180Macromolecules30, No.6, 24th March 1997, p.1782-6SOLVENT CASTING EFFECT ON THEINFRARED CHARACTERISTIC ABSORPTIONBANDS (1230/1250/CM) OF STEREOREGULARISOTACTIC POLY(ACRYLONITRILE) FILMMinagawa M; Yoshida W; Kurita S; Takada S; Yoshii FYamagata,University; Japan,Atomic Energy ResearchInstitute

The solvent casting effect on the IR characteristicabsorption bands of stereoregular isotactic PAN film wasstudied in comparison with those of an atactic sample.The ratio of intensities of the title IR characteristic bandsof PAN film was strongly dependent on the kind of dipolaraprotic solvent used in the film preparation. A higher

intensity ratio was obtained when a good solvent such asdimethyl sulphoxide was used, whereas a lower value wasobtained when a poor solvent such as malononitrile wasused. A linear relationship between the intensity ratio ofthe IR bands and the dissolution power of nine differentkinds of dipolar organic solvents was found. The IRcharacteristic bands of stereoregular PAN was dependenton not only configuration, but also conformation throughthe difference of the molecular cohesion state in thesolvent-cast film. The effect of configuration andconformation on the IR results was quantitatively studiedas a function of the film preparation conditions. NMRand wide angle X-ray diffraction results are given inaddition to IR data. 15 refs.JAPAN

Accession no.639300

Item 181Macromolecular SymposiaVol.114, Feb.1997, p.151-7LOCAL MICROSTRUCTURE DEPENDENCE OFPVC INTERACTION WITH SOLVENTS. A FTIRVERIFICATIONGomez-Elvira J M; Tiemblo P; Martinez G; Millan JMadrid,Instituto de Ciencia y Tec.de Polim.

Interactions between PVC and either cyclohexanone orN-methyl-2-pyrrolidone were studied by FTIR. Theoccurrence of local configuration based PVC-solventinteractions, specifically, is demonstrated by studying,first, the changes in FTIR frequency of both the solventcarbonyl band and the PVC carbon-chlorine stretchingbands with the composition of PVC-solvent mixtures, and,secondly, the FTIR dichroic behaviour of the same bandsupon stretching PVC films containing traces of solvent.The results suggest that the interaction is restricted to adefinite number of polymer sites although no informationas to the exact type of these sites can be drawn. Thenumber of interaction sites is higher for cyclohexanonethan for N-methyl-2-pyrrolidone. The latter turns out tobe an original path to investigate polymer interactions. 8refs.EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;WESTERN EUROPE

Accession no.639107

Item 182Polymer38, No.11, May 1997, p.2753-8PHASE TRANSITION IN ETHYLENE-TETRAFLUOROETHYLENE (ETFE)ALTERNATING COPOLYMER. ASPECTROSCOPIC STUDYRadice S; Del Fanti N; Zerbi GAusimont; Milano,Politecnico

IR and Raman spectroscopy were used to investigate themechanism, at the molecular level, of the phase transition



in ethylene-tetrafluoroethylene alternating copolymerfrom the orthorhombic to the hexagonal structure. Thestudy indicated that the transition may result from thegeneration and propagation of conformational collectivedefects. The results were discussed. 22 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;WESTERN EUROPE

Accession no.638549

Item 183International Journal of Polymer Analysis andCharacterization3, No.2, 1997, p.145-58CHARACTERIZATION OF POLYETHYLENETEREPHTHALATE USING NEAR AND FARFTIR SPECTROSCOPYLachenal GUniversite Claude Bernard

The use of near-IR and far-IR spectroscopies forcharacterisation of PETP films was investigated. After abrief review of previous work, some examples oftransmission spectra of annealed PETP, showing complexchanges in the absorption bands, are presented. Near-IRspectroscopy was used to follow the crystallinity (orconformation) of thick PETP films without any samplepreparation. 40 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.637788

Item 184European Polymer Journal33, No.3, March 1997, p.375-9QUANTITATIVE IR SPECTROSCOPICANALYSIS OF ETHYLENE-ACRYLATECOPOLYMERSBuback M; Busch M; Droege T; Maehling F O;Prellberg CGottingen,University

IR spectroscopy was used for quantitative analysis of thecomposition of three ethylene-acrylate copolymers, i.e.ethylene-methyl acrylate, ethylene-butyl acrylate andethylene-2-ethylhexyl acrylate copolymers. Based on asimple model which explicitly considered vibrationalband intensities characteristic for CH and for C:O,copolymer composition could be derived from the ratioof C:O and CH integrated absorbances with a precisionof + or -3 mol %. It was not necessary to know the opticalpath length of the copolymer samples which weresubjected to IR analysis as pressed films. 15 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.636548

Item 185Colloid & Polymer Science

275, No.4, April 1997, p.323-32FOURIER TRANSFORM INFRARED STUDY OFPOLY(2-HYDROXYETHYLMETHACRYLATE)(PHEMA)Perova T S; Vij J K; Xu HDublin,University

The FTIR spectra in the wave number range 450-4500/cm of PHEMA were studied as functions of water contentin the range 38-2.6 wt % and temps. in the range 300-373K. The results showed changes in the intensities ofthe stretching frequencies of the carbonyl band, H-O-Hbending vibration and O-H stretching vibration with achange in water content and temp. The results confirmedtwo types of water in the hydrogel polymer system, tightlybound water and loosely bound water. At lowconcentrations, water was mainly hydrogen-bonded to thepolymer and was described as tightly-bound water. Atwater concentrations greater than 18 wt % , however, partof the water existed in a different form and behaved asloosely bound water. For concentrations over 30%, therewas some evidence that excess water behaved moreloosely bound somewhat like bulk water. IR spectroscopicresults supplemented those obtained by means of NMRby Smyth et al. and by dielectric spectroscopy. Theauthors’ results also suggested that some of the watercontinued to be hydrogen bonded to the polymer until atleast a temp. of 373K when the bulk water should haveevaporated. FTIR was found to yield greater site-specificinsight into the local behaviour of water in hydratedPHEMA. 25 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; IRELAND;WESTERN EUROPE

Accession no.636483

Item 186Journal of Polymer Science : Polymer Physics Edition35, No.7, May 1997, p.1055-66EVALUATION BY FOURIER TRANSFORMINFRARED SPECTROSCOPY OF THEDIFFERENT CRYSTALLINE FORMS INSYNDIOTACTIC POLYSTYRENE SAMPLESMusto P; Tavone S; Guerra G; De Rosa CItaly,National Research Council; Salerno,University;Napoli,Universita Federico II

FTIR spectra of syndiotactic PS semi-crystalline sampleswere examined by using the spectral subtraction approach.It was shown that FTIR analysis provided a direct methodfor the evaluation of the amount of alpha and beta formcrystalline phases, although both contain chains in thesame conformation (trans-planar). 50 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;WESTERN EUROPE

Accession no.635541

Item 187Polymer



38, No.9, 1997, p.2077-91RHEO-PHOTOACOUSTIC FTIR STUDIES OFTHERMAL HISTORY-STRAIN DEPENDENCE INPOLY(VINYLIDENE FLUORIDE)Ludwig B W; Urban M WNorth Dakota State University

The effect of thermal history on the morphology of PVDFwas studied and rheophotoacoustic FTIR spectroscopy wasused to measure changes in PVDF network permeabilityas a function of elongation. The rate at which PVDF wascooled from the melt and the morphological changes causedby annealing had a greater influence on the response of thenetwork to deformations than did molecular weight. Beforedeformation, the crystalline phase and individual crystalsize seemed to have the most effect on permeability butafter stresses were applied, the number of tie moleculesand their resistance to being pulled from their anchoringcrystals dominated the permeability of the network.Annealing PVDF within 20C of its melting point of 170Cincreased the yield stress and Young’s modulus. Similareffects occurred on reducing the cooling rate. 15 refs.USA

Accession no.634449

Item 188Polymer38, No.9, 1997, p.2067-75STUDY OF THE CONFORMATIONS OFPOLY(EPSILON-CAPROLACTAM) ANDPOLY(EPSILON-CAPROLACTAM)-POLYBUTADIENE BLOCK COPOLYMERS BYFTIR SPECTROSCOPY WITHPHOTOACOUSTIC DETECTION AND BYMICRO-RAMAN CONFOCAL SPECTROSCOPYSchmidt P; Fernandez M R; Pastor J M; Roda JCzech Republic,Academy of Sciences;Valladolid,Universidad; Czech Institute of ChemicalTechnology

FTIR spectroscopy with photoacoustic detection andmicro-Raman confocal spectroscopy were used to studythe conformations of poly(epsilon caprolactam) andpoly(epsilon-caprolactam)-polybutadiene blockcopolymers. In the block copolymers prepared by anionicpolymerisation, the fraction of the planar conformationof poly(epsilon-caprolactam) chains decreased withincreasing polybutadiene content. In the surface layersformed by rapid saw cutting and in the islands formed bymicrotome cutting, the content of the planar conformationwas lowered. This was substantially increased by watertreatment, especially at elevated temperatures. 15 refs.CZECH REPUBLIC; EUROPEAN COMMUNITY; EUROPEANUNION; SPAIN; WESTERN EUROPE

Accession no.634448

Item 189Revista de Plasticos Modernos

71, No.475, Jan.1996, p.42-8SpanishDETECTION OF DEGRADATIVEMICROSTRUCTURAL CHANGES INPROPYLENE-ETHYLENE COPOLYMERCOMPONENTS BY FT-IRSPECTROPHOTOMETRYPages P; Carrasco F; Romeu JCataluna,Universidad Politecnica; Girona,Universidad

Fourier transform IR spectrophotometry was used to studythe microstructure of propylene-ethylene copolymersamples taken from seats which had degraded duringstorage or aged during outdoor exposure in an Olympicstadium in Barcelona over a period of 2.5 years. Similarmicrostructural changes were observed for both types ofsample, but these changes were more intense in samplestaken from seats which had been subjected to the actionof UV irradiation during outdoor exposure. The changesobserved included increases in aldehyde and ketonegroups and decreases in unsaturation, peroxide, methyland methylene groups and isotacticity. The resultsindicated that the main processes taking place werephotooxidation and chain scission. 7 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;WESTERN EUROPE

Accession no.632273

Item 190Journal of Materials Science Letters16, No.6, 15th March 1997, p.445-7INFRARED SPECTROSCOPIC STUDIES OFTHE INTERACTION BETWEEN NATURALRUBBER AND CHLORINATED NATURALRUBBERCool J W; Edge S; Packham D EBath,University

The interactions that occur within a simple modelconsisting of NR and a chlorinated NR were studied usingSEM, supported by electron probe microanalysis. The 1:1wt% mixture of NR and chlorinated NR was not totallymiscible when cast from xylene. Heating at 170 C for 30min resulted in a dramatic change. The morphology ofthe film appeared to be homogeneous, and there wasevidence for some type of accelerated chemical oxidation,possibly in the isoprene units in the NR. 7 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.632154

Item 191RadTech ’96 North America. Volume 1. Conferenceproceedings.Nashville, Tn., 28th April-2nd May 1996, p.407-16. 895ATTENUATED TOTAL REFLECTANCE FTIRMICROSCOPY AS AN ANALYTICAL PROBLEMSOLVING TOOL



Buehner R WUCB Chemicals Corp.(RadTech International)

Fourier transform IR microscopy has proved useful incharacterising contaminants as small as 50 microns indiameter in resins and cured films as well as characterisingcured film surfaces. The keys to the successful use ofFTIR microscopy are experience in sample preparation,an understanding of light microscopy, and ingenuity indefining solutions. Examples are given of variousproblems that have been resolved using the attenuatedtotal reflectance FTIR microscope technique. 4 refs.USA

Accession no.628096

Item 192Journal of the Adhesive and Sealant Council. Volume 1.Fall 1996. Conference proceedings.San Francisco, Ca. 3rd-6th Nov.1996, p.521-33. 6A1ATTENUATED TOTAL REFLECTION FOURIERTRANSFORM INFRARED SPECTROSCOPY(ATR FTIR): USEFUL TOOL FOR MOLECULARANALYSIS OF ADHESIVES, SEALANTS ANDCOATINGSIshida HCase Western Reserve University(US,Adhesives & Sealants Council)

Attenuated total reflection (ATR) Fourier transforminfrared spectroscopy (FTIR) is a useful molecularcharacterisation technique for studying the surface regionof adhesives, sealants, and coatings. As examples ofchallenging samples, applications for carbon fibresurfaces and their interaction with an epoxy coating aredescribed. Special intensity enhancement observed oncarbon fibre surfaces allows the study of surface speciesof oxidised carbon fibres. Another and more uniqueapplication of ATR spectroscopy is optical depth profilingin which a concentration or structural gradient is probednear the surface of a material, such as an adhesive, sealantor coating. Two techniques have been developed. The firstmethod requires obtaining spectra at multiple angles andthe analysis is done at a single frequency. On the otherhand, the second method utilises multiple frequenciesfrom only one spectrum. This latter technique allows in-situ monitoring of structural or concentration changes asa function of time due to the short data acquisition time.Unlike traditional ATR depth profiling techniques, thenewly developed methods do not require a guessed profile,eliminating human errors. High spatial resolution and thequantitative nature of the analysis have beendemonstrated. 23 refs.USA

Accession no.626545

Item 193Applied Spectroscopy

50, No.12, Dec.1996, p.1500-4RAMAN MAPPING OF THE DENTIN/ADHESIVEINTERFACEWieliczka D M; Spencer P; Kruger M BMissouri,University

The degree of adhesive penetration into dentin was studiedby micro-Raman spectroscopic examination of the dentin/adhesive interface. In contrast to previous studies, theScotchbond multipurpose dentin adhesive penetrated lessthan 2 micrometres into the acid-etched and, thus,decalcified dentin. There was strong spectroscopic evidencethat, upon acid etching of the dentin surface, which wastypically performed immediately before the adhesive wasapplied, the collagen matrix collapsed upon itself. 21 refs.

3M CO.USA

Accession no.622477

Item 194Journal of Polymer Science : Polymer Physics Edition32, No.11, Aug.1994, p.1881-7DEPTH PROFILING OF POLYMER LAMINATESUSING FOURIER TRANSFORM (ATR)SPECTROSCOPY: THE BARRIER FILMTECHNIQUEPereira M R; Yarwood JDurham,University; Sheffield,Hallam University

FTIR-ATR spectra of a laminate (PMMA/polyvinylalcohol) were presented at different base layer thicknessesand different angles of incidence on a zinc selenidesubstrate. By varying the thickness of the PMMA barrierfilm, different effective penetration depths in the polyvinylalcohol were achieved. These results agreed well withthe calculated electric fields as a function of distance awayfrom the substrate surface. The work provided the basisfor depth profiling measurements to detect interfacialinteractions. 18 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.621617

Item 195Macromolecules29, No.23, 4th Nov.1996, p.7460-9STRUCTURAL INVESTIGATION OFORTHORHOMBIC-TO-HEXAGONAL PHASETRANSITION IN POLYETHYLENE CRYSTAL.EXPERIMENTAL CONFORMATION OF THECONFORMATIONALLY DISORDEREDSTRUCTURE BY X-RAY DIFFRACTION ANDINFRARED-RAMAN SPECTROSCOPICMEASUREMENTSTashiro K; Sasaki S; Kobayashi MOsaka,University

Structural changes in the orthorhombic-to-hexagonalphase transition of PE crystal was investigated by



measuring the DSC, X-ray diffraction, and IR and Ramanspectra for the geometrically-constrained ultradrawnsamples (gel film of Hizex Million 240M HMWPE andcommercial ultrahigh modulus fibre called Dyneema fromToyobo Co. Ltd.) in the course of heating up to the meltingtemperature. The IR and spectral patterns characteristicof the hexagonal phase were confirmed. In particular, thebands characteristic of the disordered short trans segments(shorter than five methylene units) and the bands of thekink or double gauche linkages were detected definitely.The degree of orientation of the averaged chain axis, asdetected from the temperature dependence of the X-rayfibre diagram, was reserved well enough even in thehexagonal phase, while the orientational degree of themethylene units, as detected from the polarised IR spectralmeasurements, was found to be lowered appreciably. Thisfinding, combined with the observation of the trans andgauche bands, has confirmed experimentally anddefinitely the existence of the conformationally disorderedchains in the hexagonal phase. 31 refs.JAPAN

Accession no.621218

Item 196Journal of Applied Polymer Science63, No.1, 3rd Jan.1997, p.89-101REACTION OF POLYACRYLIC ACID ANDMETAL OXIDES: INFRARED SPECTROSCOPICKINETIC STUDY AND SOLVENT EFFECTHo-Shing Wu; Heay-Chain Jone; Jiann-Wen HwangYuan Ze,Institute of Technology; Nan Pao ResinsChemical Co.Ltd.

IR spectroscopic studies were conducted of the reactionof polyacrylic acid(PAA) and metal oxides (zinc oxide,calcium oxide, cupric oxide, chromium oxide andaluminium oxide). Factors such as the amount of metaloxide, reaction time, solvents, type of metal oxides andtemp. were also evaluated to derive the optimumconditions for this reaction. The reactions of chromiumoxide and aluminium oxide were far from complete. Anextra solvent added to the reaction system could increasethe solubility of PAA and metal oxide in the solution tocause complete reaction. The reactivity of the reactionwas increased by using a hydrophilic solvent, particularlywater and methanol. Furthermore, the reaction rateincreased when temp. decreased. The reactivity of thereaction was proportional to the pH value of the metaloxide in the aqueous solution. 16 refs.CHINA; TAIWAN

Accession no.618376

Item 197Polymer37, No.26, 1996, p.5807-16FTIR-RHEOOPTICAL CHARACTERISATIONOF THE MOLECULAR ORIENTATION

BEHAVIOUR OF AMINE CURED EPOXYRESINS DURING CYCLIC DEFORMATIONScherzer TInstitut fuer Oberflaechenmodifizierung

Rheooptical FTIR spectroscopy was used to studymolecular orientation in highly crosslinked epoxy resinsbased on the diglycidyl ether of bisphenol A and apolyetherdiamine. The rheooptical characterisation ofthese resins during specific cyclic deformationexperiments below the Tg is reported. Epoxy resin filmswere subject to various successive loading-unloadingcycles including elongation, recovery, annealing and stressrelaxation to study the reversibility of the orientationduring relaxation processes. 33 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.617807

Item 198Macromolecules29, No. 22, 21st Oct. 1996, p.7124-9INVESTIGATION OF POLYMER DIFFUSION INHYDROGEL LAMINATES USING NEAR-FIELDFTIR SPECTROSCOPYSahlin J; Peppas N APurdue University

The role of diffusion in gel/gel adhesion was examinedby near-field FTIR microscopy. Using a near-field FTIRmicroscopy technique, compositional maps were obtainedwith improved spatial resolution and enhanced signal tonoise ratio. With this technique, the resolution wasenhanced by about a factor of 5. Polymer chain diffusionacross a gel/gel interface was a substantial mechanism ofadhesion. Diffusion of poly(ethylene glycol) free chainsacross poly(acrylic acid) gels was investigated. Thediffusivity of poly(ethylene glycol) was on the order of1/100,000,000 to 1/1000,000,000 sq.cm/s for theseswollen polymer gels. Poly(ethylene glycol) diffusivityin poly(acrylic acid) gels scaled to the -0.41 power of themolecular weight. This was similar to values reported forpolyethylene glycol diffusion in aqueous solution. 20 refs.USA

Accession no.617217

Item 199Applied Spectroscopy50, No.11, Nov.1996, p.1360-5DYNAMIC INFRARED LINEAR DICHROICSPECTRA OF PRESTRETCHEDPOLYPROPYLENEIngemey R A; Strohe G; Veeman W SDuisberg,Gerhard-Mercator University

DIRLD (dynamic infrared linear dichroic) spectra ofprestretched isotactic polypropylene were recorded. Theline shape features in the in-phase spectra are describedon the basis of frequency shifts and absorption amplitude



variations during the stretching cycle. Details such as thedichroism of the bands, direction of the shift, and changesin the absorption intensities must be considered to explainsigns and shapes of the DIRLD bands. Evidence for chainreorientations under stress was not found. The generalprincipal of frequency shifts and changes in absorptionintensities as the origin of DIRLD bands wasdemonstrated by spectral simulations. 34 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.616827

Item 200Polymer37, No. 21, Oct. 1996, p.4705-12CROSSLINKING COPOLYMERISATION OFEPOXY METHACRYLATES AS STUDIED BYFOURIER TRANSFORM RAMANSPECTROSCOPYSandner S; Kammer S; Wartewig SHalle,Martin-Luther-Universitat

Bisphenol A bis(2-hydroxypropyl methacrylate) wascopolymerised with methyl derivatives of styrene (alpha-methylstyrene, 4-methylstyrene and 60/40 3-methylstyrene/4-methylstyrene mixture) initiated by di-tert-butyl peroxide in the presence of 76 wt% of silicafiller (quartz) at 150C-200C. The Raman bands of thecarbon-carbon double bond stretching vibrations at 1630and 1637/cm were found to be suitable for determiningthe conversion of double bonds of the styrene andmethacrylate monomer simultaneously in dependence ofthe copolymerisation time. The carbonyl bands at 1702and 1718 /cm were not suitable for assessing conversionof carbon-carbon double bonds. Relevance topolymerisable diluents for use with bisphenol A bis(2-hydroxypropyl) methacrylate) in dental applications likerestorative composite materials, sealants and adhesives,is suggested. 18 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.616206

Item 201Macromolecules29, No. 19, 9th Sept. 1996, p.6256-61RELAXATION OF SEGMENTAL ORIENTATIONAND CHAIN EXTENSION INPOLYCARBONATE STUDIED BY INFRAREDDICHROISM AND SHRINKAGELundberg L; Stenberg B; Jansson J FStockholm,Royal Institute of Technology

The relaxation of the segmental orientation and the chainextension in polycarbonate (Makrolon 1143 from BayerAG) were studied by IR dichroism and heat shrinkageafter a step strain deformation to a draw ratio of 1.75.This makes it possible to distinguish between localrelaxation mechanisms (Rouse) and large-scale relaxation

mechanisms of the molecular orientation. It was foundthat the average relaxation time for segmental orientationis shorter and more temperature dependent than theaverage relaxation time for the chain extension. Thesegmental orientation relaxes almost totally at 170C (Tg148C) before the chain extension even starts to relax. 16refs.SCANDINAVIA; SWEDEN; WESTERN EUROPE

Accession no.616185

Item 202Journal of Applied Polymer Science62, No.11, 12th Dec.1996, p.1903-11SURFACE AND INTERFACIAL FOURIERTRANSFORM INFRARED SPECTROSCOPICSTUDIES OF LATEXES. XVI. QUANTITATIVEANALYSIS OF SURFACTANT INMULTILAYERED FILMSNiu B J; Urban M WNorth Dakota State University

Migration and concentration levels of sodiumdioctylsulphosuccinate(SDOSS) surfactant molecules insilicone-modified 50%/50% styrene/butyl acrylate latexwere detected at the film-substrate and film-air interfacesin mono- and double-layered films. The SDOSS contentwas shown to be influenced by the presence oftrimethoxysilyl propylmethacrylate siloxane. Quantitativepolarised ATR FTIR spectroscopy was used to analysethe content of the SDOSS molecules. 22 refs. (Pt.XV, ibid,p.1893-901)USA

Accession no.616095

Item 203Progress in Organic Coatings28, No.4, Aug.1996, p.279-83VIBRATIONAL SPECTROSCOPIC STUDY OFDISTRIBUTION OF SODIUM DODECYLSULPHATE IN LATEX FILMSAmalvy J I; Soria D BCIDEPINT; La Plata,Universidad Nacional

The migration of the surfactant sodium dodecyl sulphateto the film-air(F-A) and film-substrate(F-S) interfacesduring coalescence of a methyl methacrylate-ethylacrylate latex functionalised with methacrylic acid wasmonitored by IR and ATR-FTIR spectroscopic techniques.Both F-A and F-S interfaces showed surfactantenrichment, revealing a nearly parabolic distribution ofsurfactant throughout the film. 11 refs.ARGENTINA

Accession no.615836

Item 204Macromolecular Chemistry & Physics197, No.11, Nov.1996, p.3523-30



CHARACTERISATION OF THE DIFFERENCESIN THE CRYSTALLINITY FROM SURFACE TOBULK OF COMPRESSION-MOULDEDPOLYPROPYLENE SHEETS USINGATTENUATED TOTAL REFLECTION FOURIER-TRANSFORM IR SPECTROSCOPYKawamoto N; Mori H; Nitta K H; Yui N; Terano MJapan,Advanced Institute of Science & Technology

The crystallinities of compression-moulded PP sheetswere investigated by application of FTIR and ATR FTIRanalyses. Two internal reflection elements, Ge and KRS-5, with an angle of incidence of 45 degrees, were used toobtain the depth profiles of the crystallinity of PP sheetsfrom the surface to the bulk. The crystallinity in the regionfrom the surface to about 0.7 micrometre depth wassignificantly lower than that in the bulk. PP sheets withhigher comonomer content showed the same tendency,which was enhanced with decreasing moulding temp. 15refs.JAPAN

Accession no.615802

Item 205Applied Spectroscopy49, No. 10, Oct.1995, p.1411-30RAMAN IMAGING OF HETEROGENEOUSPOLYMERS: A COMPARISON OF GLOBALVERSUS POINT ILLUMINATIONMarkwort L; Kip B; Da Silva E; Roussel BDSM; Dilor SA

Two alternative methods of Raman imaging via globalillumination and via point illumination in combinationwith confocal light collection were applied to the studyof heterogeneous polymer systems. The spectral andspatial resolving power of the different techniques wasestimated experimentally. The influence of the depthresolution on the Raman image of a defined samplestructure was demonstrated in a mathematical simulation.Data are given for PE, PS, polyacrylate, and epoxy resins.23 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;NETHERLANDS; WESTERN EUROPE

Accession no.615631

Item 206R’95 - Recovery, Recycling, Re-Integration. VolumeIII: Mechanical Processes, Logistic Networks,Separation Technologies. Conference proceedings.Geneva, 1st-3rd Sept. 1995, p.III.230-5. 8(13)FAST ONLINE IDENTIFICATION OF PLASTICMATERIALS BY NEAR INFRAREDSPECTROSCOPYEisenreich N; Hrez J; Kull H; Mayer WFraunhofer-Institut fuer Chemische TechnologieEdited by: Barrage A; Edelmann X(EMPA; Swiss Federal Laboratories for Mat.Testing & Res.)

An economic method for recycling of plastics has toseparate the various types of polymeric materials. Asphysical methods are not sufficient, the identification hasto monitor structural or molecular properties of thepolymer. In the near infrared spectral range NIR (700 to2500 nm), molecules absorb light by overtone orcombination vibrations of the C-H, O-H, N-H and C-Obands. The reduced absorption in the NIR allowsregistration of spectra of bulky plastics of practical interestin recycling. Advantages of the NIR spectral rangecompared to the IR are: NIR-photo detectors, like Ge,InAs, or InGaAs photodiodes with fast response andhigher detectivity; and quartz fibre optics with lowattenuation. For fast scanning of the wavelength regionof 1000 to 2200 nm, two spectrometers are realised basedon acousto-optic tunable filters with a scan speed of 1000nm/ms and applied to identify the plastics in massconsumer products and household wastes. 16 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.615266

Item 207Journal of Materials Science Letters15, No.21, 1st Nov.1996, p.1908-11ANALYSIS OF STRESS CONCENTRATIONS INMULTI-FIBRE MICROCOMPOSITES BYMEANS OF RAMAN SPECTROSCOPYVan Den Heuvel P W J; Peijs T; Young R JEindhoven,University of Technology; UMIST;Manchester,University

Preliminary results are presented showing that Ramanspectroscopy makes it possible to measure stressconcentration factors in fibres adjacent to a fibre break.Use is made of a carbon/epoxy resin multi-fibremicrocomposite, in which five different carbon fibres arealigned parallel in a planar array at a predefined inter-fibre spacing in a dumbbell-shaped tensile bar. 16 refs.EUROPEAN COMMUNITY; EUROPEAN UNION;NETHERLANDS; UK; WESTERN EUROPE

Accession no.615176

Item 208China Synthetic Rubber Industry19, No.5, 1996, p.314-6ChineseAPPLICATION OF FT-RAMAN SPECTROSCOPYIN RUBBER ANALYSISWang G; Xu FShenyang,Rubber Industry Products Research Institute

The application of FT-Raman spectroscopy in the analysisof rubbers and related materials is discussed.Characteristics of FT-Raman spectroscopy were comparedwith FTIR. 23 refs.CHINA

Accession no.609956



Item 209Antec ’96. Volume III. Conference proceedings.Indianapolis, 5th-10th May 1996, p.3131-5FAST ON-LINE IDENTIFICATION OF PLASTICSBY NEAR-INFRARED SPECTROSCOPY FORUSE IN RECYCLING PROCESSESEisenreich N; Herz J; Kull H; Mayer W; Rhoe TFraunhofer-Institut fuer Chemische Technologie(SPE)

For economic recycling of plastics, various types ofpolymeric materials have to be separated in a short periodof time. The near-infrared spectral range allows themonitoring of structural or molecular properties of theplastic under investigation. The spectrometer systemdescribed is based on optical fibres for absorption andreflexion measurements, an acousto-optic tunable filterand a transputer system. It is able to detect 1,000 spectra/s and to identify 20 pieces/second. 10 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.609107

Item 210Polymer37, No.18, 1996, p.4009-24FOURIER TRANSFORM RAMAN STUDY OFTHE STRAIN-INDUCED CRYSTALLISATIONAND COLD CRYSTALLISATION OF NATURALRUBBERHealey A M; Hendra P J; West Y DSouthampton,University

Two NR samples (cured and uncured) were studied. Inall studies, the samples were stretched to 500% elongation.The Fourier-transform Raman spectrum of NR ispresented as a function of time of cold soaking at -25Cand of strain with respect to laser polarisation. Under bothsets of conditions, changes occur in the spectra that canbe attributed to crystallisation. Difference spectra showingonly those bands due to crystallisation (i.e. spectra ofcrystalline NR) are presented, which allows thecrystallisation process to be discussed with respect to theconditions under which crystallites are formed. Acombination of Fourier-transform Raman and Fourier-transform IR depolarisation spectra was used to deducepreliminary assignments for some of the vibrational bandsof natural rubber. 40 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.607325

Item 211Polymer37, No.15, 1996, p.3227-31ISOTACTICITY DETERMINATION OFPOLYPROPYLENE USING FT-RAMANSPECTROSCOPY

Sundell T; Fagerholm H; Crozier HAbo,Akademi University; Borealis Polymers Oy

Carbon-13 NMR was used as the reference method toenable comparison of FT-Raman and FTIR spectroscopiesas isotacticity determination methods. Calibration curvesrelating Raman scattering and IR absorption ratios to thecarbon-13 NMR results are presented. The repeatabilityfor both FT-Raman and FTIR measurements wascomparable to that of carbon-13 NMR analysis and therewas good correlation between between carbon-13 NMRand FT-Raman/FTIR results. The reliabilities of the threemethods are statistically evaluated and compared. 9 refs.FINLAND; SCANDINAVIA; WESTERN EUROPE

Accession no.606302

Item 212Composites Science & Technology56, No.7, 1996, p.749-54STUDY OF CARBON FIBRE STRAIN IN MODELCOMPOSITES BY RAMAN SPECTROSCOPYLeveque D; Auvray M HOffice National d’Etudes & de Recherches Aerosp.

The application of strain to the molecular structure ofcarbon fibre was shown to cause a linear shift of Ramanfrequencies. The magnitude of this shift increased withincreasing organisation of the fibre structure, from -7/cm/% for the T800HB intermediate modulus fibre to -11/cm/% for the M40B high modulus fibre. Ramanspectroscopy was shown to be a useful tool for identifyingthe different interfacial load transfer types from strainprofile observation in single fibre model composites undertensile loading, i.e. fibre debonding with or withoutfriction, and elastic stress transfer was well described bythe Cox model. The interfacial shear stress distribution,the possible friction coefficient and the longitudinalthermal residual strain were derived from the strainprofiles. 9 refs. (9th French National Colloquium onComposite Materials, Saint-Etienne, France, Nov.1994)EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.605822

Item 213Polymer International41, No.1, Sept.1996, p.35-41FTIR-MICROSPECTROSCOPY(FTIR-M) ANDDSC STUDIES OF POLYVINYLIDENEFLUORIDE(PVDF)Benedetti E; Catanorchi S; D’Allesio A; Moggi G;Vergamini P; Pracella M; Ciardelli FPisa,University; CNR

PVDF samples, obtained by casting from THF solutionsand submitted to various thermal treatments, wereexamined by FTIR-M and DSC. This type of analysispermitted examination of microdomains of samples of



different morphological characteristics and an indicationof the polymorphism of PVDF to be obtained. In somecases, the simultaneous presence of two or three formswas observed by comparison of FTIR-M and DSC traces.Vibrational spectra of single crystalline forms could berecorded by FTIR-M on phase homogeneousmicrodomains. 13 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;WESTERN EUROPE

Accession no.605759

Item 214Polymer37, No.16, 1996, p.3665-73ANIONIC POLYMERISATION OF STYRENEAND BUTADIENE INITIATED BY N-BUTYLLITHIUM IN ETHYLBENZENE:DETERMINATION OF THE PROPAGATIONRATE CONSTANTS USING RAMANSPECTROSCOPY AND GEL PERMEATIONCHROMATOGRAPHYAuguste S; Edwards H G M; Johnson A F; Meszena ZG; Nicol PBradford,University

The rate of monomer loss during the n-butyllithium-initiated anionic polymerisation of styrene in ethylbenzenewas measured using Raman spectroscopy. GPCmeasurements on the reaction products were used as anindirect method of obtaining the concentrations of thepropagating species involved in this reaction. The rate ofpropagation for styrene polymerisation was determinedin the temperature range 25-70 C, and for specified live-end concentrations. 34 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.604626

Item 215Analyst121, No.8, Aug.1996, p.1069-74POLYMER ANALYSIS BY COLUMN LIQUIDCHROMATOGRAPHY COUPLED SEMI-ON-LINE WITH FOURIER TRANSFORMINFRARED SPECTROMETRYSomsen G W; Rozendom E J E; Gooijer C; Velthorst NH; Brinkman U A TAmsterdam,Free University

Additives in polymers were identified by solvent-elimination based coupling of reversed-phase columnliquid chromatography(LC) and FTIR spectrometry. Aspray-jet interface was used to deposit the effluent froma narrow-bore LC column on a zinc selenide window.The deposited additives were analysed by FTIRtransmission microscopy, yielding identification limits inthe low-nanogram range. High-quality IR spectra wereobtained for components present in PVC and PP samples.

These spectra allowed the characterisation of the additivesby spectral library search and/or spectral interpretation.The usefulness of the spray-jet interface system for thecoupling of size exclusion chromatography(SEC) andFTIR spectrometry was examined on the basis of theanalysis of a PS standard mixture. Representative IRspectra of the SEC effluent indicated that the SEC-FTIRsystem could be used for the determination ofcompositional changes across the polymer MWD. 25 refs.EUROPEAN COMMUNITY; EUROPEAN UNION;NETHERLANDS; WESTERN EUROPE

Accession no.604342

Item 216Polymer Science Series A38, No.5, May 1996, p.517-24RAMAN SPECTROSCOPIC INVESTIGATIONOF THE ORIENTATION PROCESS OF LINEARPOLYETHYLENERussian Academy of Sciences

The potential of polarisation Raman spectroscopy inprobing the structure of oriented polymers was shownusing linear PE as the example. The evolution of theRaman spectra of PE in the course of drawing from theisotropic state to that with the highest attainableorientation was investigated. The mechanism of transitionfrom the lamellar structure to fibrillar one was shown tobe independent of the particular method of an isotropicsample preparation. The use of micro Raman attachmentmade it possible to study the structure in the neckingregion. The data obtained showed that the change inorientation of the polymer chains along the length of aneck was continuous. 18 refs.RUSSIA

Accession no.601403

Item 217Applied Spectroscopy50, No.7, July 1996, p.900-5IN SITU NEAR-IR CURE MONITORING OF AMODEL EPOXY MATRIX COMPOSITECossins S; Connell M; Cross B; Winter R; Kellar JSouth Dakota,School of Mines & Technology

The curing of an epoxy resin adjacent to an embeddedsilica optical fibre was monitored in situ by evanescentwave spectroscopy. The epoxy resin was partiallyfluorinated and had a lower refractive index than thesilica fibre. The lower refractive index of the epoxy resinallowed the silica optical fibre to be used as a waveguidefor the internal reflection of the near-IR light. The epoxyresin curing was determined as a function of time andtemp. by analysis of the near-IR spectrum from the epoxyadjacent to the fibre obtained by the interaction of theevanescent wave that occurred at each internal reflectionwith the low refractive index epoxy resin. The resultsobtained showed that epoxy ring-opening and



crosslinking reactions could be followed in real time.Treatment of the fibre with a silane coupling agent hadno observable effect on the curing reaction of the epoxyresin. 27 refs.USA

Accession no.600870

Item 218Polymer37, No.12, 1996, p.2335-43DYNAMIC TWO-DIMENSIONAL INFRA-REDSPECTROSCOPY OF THE CRYSTAL-AMORPHOUS INTERPHASE REGION IN LOW-DENSITY POLYETHYLENESinghal A; Fina L JRutgers,University

Dynamic two-dimensional FTIR was used to study thenature of the interphase in LDPE. A two-dimensionalcorrelation analysis on the dynamic spectra indicates thatneat LDPE is comprised of three regions, specifically, anordered crystalline region, a disordered liquid-like region,and a crystal/amorphous interfacial region. The 1468/cmpeak in the methylene bending region is assigned to all-trans structures which primarily reside in the interfacialregion. A variety of LDPE samples with different additivesare used in order to determine how the additives influencethe dynamic mechanical properties of each morphologicalphase. It is found that talc associates with the crystallites,ethylene vinyl acetate is distributed in all threemorphological phases of the LDPE, and pyrene isassociated only with the non-crystalline regions. 31 refs.USA

Accession no.599665

Item 219Macromolecules29, No.10, 6th May 1996, p.3515-20RAMAN VIBRATIONAL STUDIES OFSYNDIOTACTIC POLYSTYRENE. 1.ASSIGNMENTS IN A CONFORMATIONAL/CRYSTALLINITY SENSITIVE SPECTRALREGIONKellar E J C; Galiotis C; Andrews E HQueen Mary & Westfield College

A detailed analysis of the Raman spectrum ofsyndiotactic PS in the region 600-850/cm wasundertaken. As syndiotactic PS exhibits considerablepolymorphism, spectra of various preparations includingmelt-crystallised syndiotactic PS, solvent-crystallisedsyndiotactic PS and quenched glassy materials, werestudied. Peaks are assigned to conformational changesand sequences. Comparison with atactic PS is made.Study of the cross section of a compression mouldedplaque exhibiting a skin/core structure revealed thecontinuous way the structure varied with changingcrystallinity. The various physical forms of syndiotactic

PS and the routes for interchange amongst them areshown diagramatically. 28 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.597199

Item 220Synthetic Metals71, Nos.1-3, 1st April 1995, p.1825-6FTIR AND NIR-FT-RAMAN STUDY OFPOTENTIAL MOLECULARFERROMAGNETICS - POLY(DIACETYLENES)SUBSTITUTED WITH NITROXYL RADICALSShchegolikhin A N; Lazareva O L; Ovchinnikov A A;Spector V NMoscow,Institute of Chemical Physics

FTIR spectroscopy and near-infrared-FT-Ramanspectroscopy were used to study the molecular structuraltransformations which occurred during thermal treatmentof several nitroxyl substituted diacetylene monomers.These spectroscopic techniques were also used toinvestigate the solid state polymerisation reactions of thenitroxyl-substituted monomers, “classic” diacetylenes andof polydiacetylenes. The results were discussed. 7 refs.RUSSIA

Accession no.596062

Item 221Journal of Applied Polymer Science61, No.2, 11th July 1996, p.231-54MICRO-RAMAN IMAGING OFHETEROGENEOUS POLYMER SYSTEMS:GENERAL APPLICATIONS AND LIMITATIONSMarkwort L; Kip BDSM

Using micro-Raman imaging three blends consisting ofpolypropene/polyethene/ethene-propene copolymer,PBTP/polycarbonate/LDPE, and styrene-acrylonitrilecopolymer/styrene-maleic anhydride copolymer/polydimethylphenylene oxide were studied with regardto compositional and morphological heterogeneities. Thegeneral structure of PE fibres in an epoxy resin matrixwas also studied. 59 refs.EUROPEAN COMMUNITY; EUROPEAN UNION;NETHERLANDS; WESTERN EUROPE

Accession no.595775

Item 222Applied Spectroscopy50, No.6, June 1996, p.708-14EFFECTS OF SAMPLING PARAMETERS ONPRINCIPAL COMPONENTS ANALYSIS(PCA) OFRAMAN LINE IMAGESHayden C A; Morris M DMichigan,University



The effects of spectrometer slit width, spatial resolutionand number of spectral variables used for PCA analysis ofRaman line-images were studied. Depth of penetration andsignal-to-noise considerations dominated the properselection of slit width for the sample used in this study, 10-micrometre-diameter PS spheres embedded in an epoxyresin matrix. With the use of different microscope objectivesto analyse the same sample region, the higher-magnificationobjective gave better results, probably due merely to thelarger number of spectra processed. Finally, the number ofspectral variables could be reduced significantly beforedegradation of the PCA image had occurred, especially ifthe variables were carefully chosen. 9 refs.USA

Accession no.595341

Item 223Journal of Polymer Science : Polymer Physics Edition32, No.12, Sept.1994, p.2065-75FTIR-ATR STUDIES OF DRAWING ANDPOLING IN POLYMER BILAMINATE FILMSGang Chi Chen; Ji Su; Fina L JRutgers,University

FTIR-ATR spectroscopy was used to examine thestructural variations as a function of depth for drawn andpoled single nylon-11 and PVDF films and PVDF/nylon-11 bilaminates. Simple one-way drawing in PVDF andnylon-11 produced anisotropy in dipole orientation in theplane transverse to the draw direction. In both single andbilaminate films, the average direction of the amide planein nylon-11 and the CF2 dipoles in PVDF residues residedin the plane of the film, perpendicular to the subsequentpoling field direction as a result of one-way drawing. Thetransverse plane orientation was depth dependent innylon-11 in both single and bilaminate films and wasattributed to a surface-induced effect. Poling fields of 1.6MV/cm produced large differences between the surfacesof single films and the bilaminates. The PVDF and nylon-11 dipoles important in polarisation appeared to berandom at the interior interface of the drawn and poledbilaminates. The results were discussed. 36 refs.USA

Accession no.593532

Item 224Kautchuk und Gummi Kunststoffe49, No.5, May 1996, p.354-6DETERMINATION OF THE SOLUBILITY OFSULPHUR IN ELASTOMERS USING FOURIERTRANSFORM RAMAN SPECTROSCOPYBrimblecombe A; Hendra P J; Wallen P; Chapman A;Jackson K; Loadman J; Van Duin M; Kip B; Hofstraat JW; Schreurs HSouthampton,University; Malaysian Rubber Producers’Research Assn.; DSM Research; Akzo Nobel CentralResearch BV

Solubility of elemental sulphur in NR, EPDM, syntheticpolyisoprene and deproteinised NR was determined overa period of 5 days. By varying the amount of sulphuradded to the elastomers, heating the mixtures andanalysing them on cooling in a Fourier Transform Ramaninstrument, both the immediate and long-term solubilitycould be assayed. Some of the non-elastomericcomponents could influence the rate and level ofcrystallisation. 11 refs.EUROPEAN COMMUNITY; EUROPEAN UNION;NETHERLANDS; UK; WESTERN EUROPE

Accession no.592027

Item 225Applied Spectroscopy50, No.5, May 1996, p.558-63DEPTH PROFILING OF POLY(METHYLMETHACRYLATE), POLY(VINYL ALCOHOL)LAMINATES BY CONFOCAL RAMANMICROSPECTROSCOPYHajatdoost S; Yarwood JSheffield,Hallam University

It is demonstrated that this technique can be successfullyused to study the hydrogen bonding interaction betweenthe ester and alcohol groups near the interfacial region.Various laminates have been studied, and it isdemonstrated that the PMMA layers with lower molecularweight show a greater degree of interpretation for a givenannealing time.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.590639

Item 226Journal of Elastomers & Plastics28, No.2, April 1996, p.140-60QUANTITATIVE CHARACTERISATION OFPOLYMER STRUCTURE BY PHOTOACOUSTICFOURIER TRANSFORM INFRAREDSPECTROSCOPYParker J R; Waddell W HPPG Industries Inc.

The use of photoacoustic FTIR spectroscopy in quantitativeanalysis of polymers was investigated with reference todetermination of vinyl acetate in EVA, acrylonitrile in NBR,ethylene in EPDM, styrene in SBR and vinyl-butadiene inSBR. The results obtained indicated that, despite thetheoretical complexities of photoacoustic FTIRspectroscopy, simple quantitative relationships could befound for many of these polymer analyses. 24 refs.USA

Accession no.590610

Item 227Polymer37, No.8, 1996, p.1295-303



MONITORING OF REACTIVE PROCESSING BYREMOTE MID INFRA-RED SPECTROSCOPYMijovic J; Andjelic SBrooklyn,Polytechnic University

An alternative approach to remote mid infra-redspectroscopy is presented which utilises gold-coatedwaveguides instead of fibre optics and which could beused for in-situ real-time process control in practicallyany environment. The principle objects of the paper areto describe a novel experimental set-up for remote midinfra-red spectroscopy recently assembled in laboratory,and to demonstrate the qualitative and quantitativeanalysis of the remote mid infra-red data using amultifunctional epoxy/amine formulation as an example.18 refs.USA

Accession no.588252

Item 228Acta Polymerica47, No.4, April 1996, p.170-6FTIR SPECTROSCOPIC STUDIES ON THEINTERFACIAL REACTIONS OF OXAZOLINE-FUNCTIONALISED POLYMERSSchaefer R; Kressler J; Muelhaupt RFreiburg,Universitat

The interfacial reaction of immiscible polymeric systemscontaining oxazoline and carboxylic acid groups,respectively, was studied by FTIR spectroscopy and FTIRmicroscopy. A poly(butadiene-co-acrylonitrile) rubber,where the nitrile groups are partially converted tooxazoline groups, was thermally annealed in a two-layerspecimen with poly(ethylene-co-methacrylic acid). Theformation of the esteramide in the interface was measuredquantitatively by FTIR difference spectroscopy. 33 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.588230

Item 229Acta Polymerica47, No.4, April 1996, p.161-9SPECTROSCOPIC AND QUANTITATIVECHARACTERISATION OF VARIOUSFRACTIONS OF THE HETEROGENEOUSPOLYMER SYSTEM (EPDM-G-MALEICANHYDRIDE)-G-POLYAMIDE 66 USING HIGHRESOLUTION CARBON-13 SOLID STATE NMRAND IR TECHNIQUESvan der Velden G; Nelissen H; Veermans TDSM Research Bv

The structure of EPDM grafted onto polyamide 66 wasanalysed with high resolution solid state carbon-13 NMRand IR spectroscopy. Details about the EPDM rubberinclude the amount of rubber incorporated into this blend,the sequence analysis of the EPDM rubber and an estimate

of the type and amount of termonomer used (in this caseonly trans 1,4-hexadiene). The sample contains 20%EPDM rubber, 6% polyamide 66 grafted onto EPDMrubber and 74% neat polyamide 66. Some evidence wasobtained via IR spectroscopy for the presence of cyclicimide groups, derived from grafted maleic anhydridegroupings. No evidence for the use of a coupling agentcould be obtained from either the carbon-13 single pulseexcitation-magic angle spinning spectra of the interphaseenhanced polyamide 66 or from the isolated rubber phase.45 refs.EUROPEAN COMMUNITY; EUROPEAN UNION;NETHERLANDS; WESTERN EUROPE

Accession no.588229

Item 230Journal of Applied Polymer Science60, No.1, 4th April 1996, p.29-35STUDY OF DIFFUSION AND SORPTION OF BIS-(2-CHLOROETHYL)SULPHIDE (SM) AND BIS-(2-CHLOROETHYL)ETHER (OM) THROUGHPOLYPROPYLENE (PP) AND BIAXIAL-ORIENTED POLYPROPYLENE (BOPP) FILMSBY THE FTIR-ATR SPECTROSCOPIC METHODSemwal R P; Banerjee S; Chauhan L R; BhattacharyaA; Rao N B S NIndia,Defence Research & Development Organisation

Diffusion of sulphur mustard (SM) and oxygen mustard(OM) in PP and BOPP were measured using FTIR-ATRspectroscopy, which permits the study of the diffusion ofliquid through thin polymer films in-situ. Thetemperature-dependent diffusion coefficients of OM andSM for PP and BOPP were also reported; these were ingood agreement with values obtained by the weight gainmethod. Activation energy of diffusion was determinedby both methods. The polymer-penetrant interactionparameter and transport number were calculated for thesystem PP/OM and BOPP/OM by weight gain method.24 refs.INDIA

Accession no.585950

Item 231Journal of Polymer Science : Polymer Physics Edition34, No.4, March 1996, p.781-8ELECTRIC FIELD-INDUCED DIPOLEREORIENTATION IN ORIENTED NYLON 11 BYIN SITU INFRARED SPECTROSCOPYHsin Her Yu; Fina L JRutgers,University

Dipole reorientation under the influence of an electric fieldwas investigated in oriented nylon 11 films with polarisedIR spectroscopy for the amide A (N-H stretching) andamide I (carbonyl stretching) bands. Butterfly-shapedhysteresis loops were obtained from peak intensity versusapplied electric field strength. Least-squares Gaussian



curve fitting of the resolved multiple contributions to theamide I peak show that the components change in eithera continuously reducing S-shaped fashion, or in butterfly-shaped curves under ac poling fields. Time-dependentstudies of the absorption intensities show that both orderedand disordered species switch towards the electric fielddirection with the application of electric fields higher thanthe coercive field. Upon field removal, only the disorderedspecies show orientation relaxation away from the fielddirection. Below the coercive field, neither speciesresponds orientationally to the field. 12 refs.USA

Accession no.585313

Item 232Euradh ’94. Conference Proceedings.Mulhouse, 12th-15th Sept.1994, p.346-9. 9(12)4USE OF INTERNAL REFLECTION FTIRSPECTROSCOPY FOR IN-SITU STUDY OFWATER-POLYMER-SUBSTRATE SYSTEMSLinossier I; Gaillard F; Romand MLyon,Universite Claude Bernard(Societe Francaise du Vide; Institute of Materials;Dechema Institut)

Multiple internal reflection FTIR spectroscopy was used forthe in-situ determination of water diffusion coefficientthrough thin PMMA films. The technique was also used tostudy water uptake at the interface of an adhesive-substratesystem and the effect of surface treatment of the substrateon this parameter. These studies were done to assess adhesionloss and durability of polymer-substrate joints. 7 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.584869

Item 233Euradh ’94. Conference Proceedings.Mulhouse, 12th-15th Sept.1994, p.85-9. 9(12)4QUANTITATIVE I.R.R.A.S. ANALYSIS OF ACID-BASE INTERFACIAL INTERACTIONS INVARIOUS POLYMER/METAL MODELSYSTEMS: RELEVANCE TO ADHESIONBrogly M; Nardin M; Schultz JCentre de Recherches sur Physico-Chemie Surf.Sol.(Societe Francaise du Vide; Institute of Materials;Dechema Institut)

Ethylene-vinyl acetate copolymer, terpene-phenol resins,polyethylene oxide, PMMA and some of their blends weresolution cast on basic (aluminium oxide) and acidic(hydroxylated glass) substrates. Fourier transform infraredreflection absorption spectroscopy (IRRAS) was used todetermine both the nature and the free energy of interfacialadduct formation in the polymer/metal systems. Acorrelation between IRRAS and adhesive strength maybe used to predict both the acid-base work of adhesionand the density of interfacial interacting sites. 14 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.584819

Item 234Applied Spectroscopy50, No.3, March 1996, p.388-93DENSITY MAPPING IN POLY(ETHYLENETEREPHTHALATE) USING A FIBRE-COUPLEDRAMAN MICROPROBE AND PARTIAL LEAST-SQUARES CALIBRATIONEverall N; Davis K; Owen H; Pelletier M J; Slater JICI PLC

Partial least-squares analysis was used to calibrate Ramanmicroprobe spectra of PETP films in terms of density, togive insight into changes in crystallinity through the filmthickness. The microprobe uses a static multiplexedholographic grating to obtain the entire Raman spectrumin a single shot. 13 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.584714

Item 235Applied Spectroscopy50, No.3, March 1996, p.377-81DYNAMIC STEP-SCAN TWO-DIMENSIONALFOURIER TRANSFORM INFRARED STUDIESOF UNIAXIALLY DRAWN POLY(ETHYLENETEREPHTHALATE) FILMSonoyama M; Shoda K; Katagiri G; Ishida HToray Research Center Inc.

Dynamic two-dimensional IR spectra of uniaxially drawnPETP under a sinusoidal strain were examined. 39 refs.JAPAN

Accession no.584712

Item 236Cellular Polymers III. Conference proceedings.Coventry, 27th-28th April 1995, paper 3. 6124USE OF FTIR TO ANALYSE FIRE GASES FROMBURNING POLYURETHANE FOAMSPaul K TRapra Technology Ltd.(Rapra Technology Ltd.)

A large number of different techniques may be used toanalyse fire gases including gas chromatography, massspectrometry, infrared absorption, ion chromatography,chemiluminescence, specific ion electrodes as well asvarious colourmetric and titrametric techniques. The useof Fourier Transform Infrared Analysis (FTIR) enables anumber of the more important gases to be determinedcontinuously. These gases include those of particularimportance to polyurethane foam containing fires, e.g.hydrogen cyanide, nitrogen oxides, hydrogen chloride and



hydrogen bromide (from flame retardant additives) as wellas carbon monoxide and carbon dioxide which areproduced from all fires. The use and limitations of FTIRto analyse fire gases in general is discussed and the firegases produced by burning polyurethane foams ofdifferent types are compared. 4 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.583878

Item 237Journal of Materials Science31, No.4, 15th Feb.1996, p.851-60CHARACTERISATION OF PAN-BASEDCARBON FIBRES WITH LASER RAMANSPECTROSCOPY. I. EFFECT OF PROCESSINGVARIABLES ON RAMAN BAND PROFILESMelanitis N; Tetlow P L; Galiotis CQueen Mary & Westfield College

Laser Raman spectroscopy was used to characterise thestructure and morphology of a series of carbon fibres, to assessthe ultimate firing temperature and pregraphitisation drawingduring manufacture and to investigate the influence ofoxidative treatment upon the integrity of the fibre surface.Ten types of polyacrylonitrile-based carbon fibres of varyingmodulus, diameter and manufacturing method, wereexamined. All their spectral features were recorded andanalysed in terms of position, bandwidth and band intensity.The observed Raman spectra are discussed in detail and relatedto alterations in the conditions of manufacture. 49 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.581295

Item 238Journal of Applied Polymer Science59, No.9, 28th Feb.1996, p.1417-26POLYMERISATION KINETICS OFPOLYURETHANE AND VINYL ESTER RESININTERPENETRATING POLYMER NETWORKSBY USING FOURIER TRANSFORM INFRAREDSPECTROSCOPYLian Hua Fan; Chun Pu Hu; Zhi Ping Zhang; ShengKang YingEast China,University of Science & Technology

FTIR was applied to the study of polymerisation kineticsof simultaneous interpenetrating polymer networkscomposed of PU and vinyl ester resin at a temperature rangefrom 60-110C within 0.5h, in which the pendant hydroxylgroups were capped with acetyl groups to minimise thepossibility of chemical binding between the two networks.The comparison of vinyl ester resin with or without itspendant hydroxyl groups was also made to examine theintercomponent chemical binding effect. 18 refs.CHINA

Accession no.580925

Item 239Macromolecules29, No.1, 1st Jan.1996, p.239-46STUDY OF THE MECHANISM AND RATE OFBISMALEIMIDE CURE BY REMOTE IN-SITUREAL TIME FIBRE OPTIC NEAR-INFRAREDSPECTROSCOPYMijovic J; Andjelic SBrooklyn,Polytechnic University

The formulation comprised 4,4'-methylenebis-(maleimidobenzene) (Matrimid 5295) and 2,2'-diallylbisphenol A. In-situ real time study of the progressof the reaction was conducted in the temp. range from140 to 250C using remote fibre optic near IR spectroscopy.The signal was clean, free from noise, and remarkablyreproducible. The principal reaction observed was analternating copolymerisation involving maleimide andallyl double bonds. Maleimide homopolymerisation wasdetected only in the initial stages of reaction attemperatures above 200C. The extent of self-condensation(or etherification) of hydroxyl groups on the allylcomponent, which leads to crosslinking, was observed tovary with reaction temperature, suggesting a path to tailor-making networks with desired morphology and physical/mechanical properties. 23 refs.USA

Accession no.580381

Item 240Journal of Polymer Science : Polymer ChemistryEdition34, No.3, Feb.1996, p.403-11KINETICS OF CATIONICPHOTOPOLYMERISATIONS OF DIVINYLETHERS CHARACTERISED USING IN-SITURAMAN SPECTROSCOPYNelson E W; Scranton A BMichigan,State University

In-situ Raman spectroscopy experiments were used todetermine effective kinetic propagation constants for aseries of unsteady-state divinyl ether polymerisations atdifferent isothermal temperatures and light intensities. Aseries of Raman experiments were performed on cationicphotopolymerisations of a divinyl ether initiated with adiaryliodonium salt of hexafluoroantimonatephotosensitised by anthracene. Isothermal Ramanexperiments were performed for a series of reactiontemperatures and were used to determine the overallactivation energy of the polymerisation reaction. 20 refs.USA

Accession no.578838

Item 241Composite Interfaces3, No.3, 1995, p.221-30EFFECT OF THE MOLECULAR WEIGHT ON



THE SURFACE COMPOSITION OFPOLYCARBONATE/POLY(ETHYLENETEREPHTHALATE) BLENDS BY FOURIERTRANSFORM IR ATTENUATED TOTALREFLECTANCE SPECTROSCOPYKugo K; Watanabe E; Kitaura T; Nishino JKonan,University; Gunze Ltd.

The surface structure of melt-mixed blends of bisphenolA polycarbonate and PETP was investigated by FTIRattenuated total reflectance spectroscopy. Based on thepeak intensity of the aromatic carbonate band forpolycarbonate and the aliphatic ester band for PETP byusing germanium and KRS-5 ATR crystals, theenrichment of the PETP component in the surface layerof the polycarbonate/PETP blend films was observed.27 refs.JAPAN

Accession no.577664

Item 242Journal of Applied Polymer Science59, No.3, 18th Jan.1996, p.511-20DYNAMIC FTIR METHOD FOR DETERMININGTHE CURING TEMPERATURE RANGES OF ANACETYLENE-TERMINATED POLYISOIMIDEPREPOLYMERHuang W X; Wunder S LTemple University

To determine individual curing temperature ranges of theisoimide-imide isomerisation and crosslinking reactions,a rapid scan dynamic FTIR method was developed inwhich the two reactions were continuously monitored asthe sample was heated at constant rate. Isothermal kineticdata was obtained on FTIR spectrometers using their fastscan capability and GC-IR software. Dynamic FTIR wasused with a common kinetics program to monitor the twoseparate reactions occurring during thermal curing of theacetylene-terminated polyisoimide prepolymer ThermidIP-600 and to determine individual curing temperatureranges of the isoimide-imide isomerisation andcrosslinking reactions. Results were compared withdynamic FTIR and the dynamic DSC data obtained for amodel compound, IP-6001. 22 refs.USA

Accession no.577637

Item 243Polymer Bulletin36, No.1, Jan.1996, p.87-94RHEO-OPTICAL FOURIER TRANSFORMINFRARED SPECTROSCOPY OF A LIQUIDCRYSTALLINE BLOCK COPOLYMERZebger I; Pospiech D; Boehme F; Eichhorn K J; SieslerH WEssen,University; Dresden,Institute of PolymerResearch

Rheo-optical experiments were conducted in which FTIRpolarisation spectroscopy was used to investigate theorientational behaviour of the different constituents of aliquid crystalline block copolymer (copolyester-imide)during uniaxial elongation at different temps. The resultsexhibited differences in the degree of alignment as wellas in the response to the application of the mechanicalload. With increasing temp., the level of the applied stressand the induced degree of orientation decreased, whilethe differences in the orientational behaviour of themesogen and the flexible spacer were retained. 12 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.576734

Item 244Macromolecules28, No.24, 20th Nov.1995, p.8209-15SULPHONATED POLYSTYRENE IONOMERSNEUTRALISED BY BI- ANDMULTIFUNCTIONAL ORGANIC CATIONS. I.AN INFRARED SPECTROSCOPIC STUDYXiao-Dong Fan; Bazuin C GQuebec,Universite Laval

An FTIR investigation of lightly sulphonated PS blendedwith ten different organic small molecules containing bi-,tri-, and quadrifunctional amine or pyridine groups wasundertaken. Proton transfer from the sulphonic acidmoieties of the polymer to the nitrogen functions of thesmall molecules, giving rise to ion pairs and hence ioniccrosslinking, was clearly detected. the extent of protontransfer was correlated qualitatively with the relativebasicity of the small molecule. A quantitative calculationof the degree of proton transfer was performed, basedprimarily on the normalised area of the absorption bandand shoulder at 900-906/cm. The results range from about50% proton transfer or less to purine, 2,2'-pyridil,, and N-phenyl-1,4-phenylenediamine to almost complete protontransfer to 1,6-hexanediamine and 1,4-phenylenediamine.Other small molecules were 1,4-phenylenediamine, 4,4'-diaminodiphenylsulphone, 3,3-diaminobenzidine,hexamethylene tetramine and terpyridine. 31 refs.CANADA

Accession no.575981

Item 245Journal of Polymer Science : Polymer Physics Edition32, No.11, Aug.1994, p.1881-7DEPTH PROFILING OF POLYMER LAMINATESUSING FOURIER TRANSFORM (ATR)SPECTROSCOPY: THE BARRIER FILMTECHNIQUEPereira M R; Yarwood JDurham,University; Sheffield,Hallam University

FTIR-ATR spectra of a laminate (PMMA/polyvinylalcohol) were presented at different base layer thicknesses



and different angles of incidence on a zinc selenidesubstrate. By varying the thickness of the PMMA barrierfilm, different effective penetration depths in the polyvinylalcohol were achieved. These results agreed well withthe calculated electric fields as a function of distance awayfrom the substrate surface. The work provided the basisfor depth profiling measurements to detect interfacialinteractions. 18 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.573664

Item 246Antec ’95. Vol.II. Conference Proceedings.Boston, Ma., 7th-11th May 1995, p.2458-62. 012FTIR MICROSPECTROSCOPIC METHOD FORCHARACTERISING THE DRYING OF WATER-BASED COATINGSNedea C E; La H M; Campanelli J RDomco Industries Ltd.(SPE)

Fourier transform IR microspectroscopy was used toinvestigate the drying of water-based acrylic polymercoatings on an aluminised substrate. Changes in theabsorbance peak heights were monitored as an indicationof the remaining water content. The effects on drying ofhumidity, solids content, coating thickness and thepresence of coalescing agents were studied. Coalescingagents were found to increase drying time while aidingfilm formation. Drying time decreased with increasingsolids content and increased with increasing coatingthickness. As expected, relative humidity was found tohave an important effect on the drying process. 7 refs.

CANADA; USA

Accession no.571348

Item 247Antec ’95. Vol.II. Conference Proceedings.Boston, Ma., 7th-11th May 1995, p.2057-61. 012QUALITY MONITORING OF RECYCLEDPLASTICS WASTE DURING EXTRUSION. I. IN-LINE NEAR-INFRARED SPECTROSCOPYReshadat R; Cluett W R; Balke S T; Hall J WToronto,University; NIRSystems Inc.(SPE)

The composition of recycled HDPE/virgin PP blendsprepared in a single-screw extruder was monitored in-line at three different points by near-infrared spectroscopy.The data were interpreted by simple and multiple linearregression and multivariate methods. 5 refs.

CANADA; USA

Accession no.571279

Item 248Macromolecules

28, No.22, 23rd Oct.1995, p.7441-6FOURIER TRANSFORM INFRARED ANALYSISOF A LINEAR, ANHYDRIDE-CURED EPOXYTadros R; Timm D CNebraska,University

A linear-chained epoxy resin was formulated from phenylglycidyl ether and nadic methyl anhydride catalysed bybenzyldimethylamine. Intermolecular polymerisationswere modelled as a parallel set of propagation reactions.FTIR spectroscopy was used to determine theconcentrations of the oxirane, anhydride and estermoieties within the resin as a function of time for twoisothermal cures. Data analyses yielded the propagationrate constant as a function of temp. and the concentrationof initiator, including contributions from impurities withinthe resin. Results obtained compared favourably withmeasurements on fractionated resins, using GPC.Population density distributions are described by Poissonmolar distributions for this resin. 25 refs.USA

Accession no.569011

Item 249Composite Interfaces3, No.2, 1995, p.101-19PHYSICOCHEMICAL CHARACTERISATIONOF THE FIBRE/MATRIX INTERACTION INPOLYETHYLENE FIBRE/EPOXY MATRIXCOMPOSITES. II. CHARACTERISATION OFTHE INTERPHASE WITH FTIRMICROSPECTROSCOPYVan Mele B; Verdonck EBrussels,Free University

The interphase in PE fibre/epoxy resin matrix compositeswas studied by FTIR microspectroscopy using a set-upfor investigation of the matrix as close to the fibre as afew microns or less. It was shown that moisture presenton the fibre surface could influence the polymerisationreaction of the epoxy/anhydride matrix in an irreversiblemanner. This effect was enhanced for composites fromthe more hydrophilic PVAl fibre. The fibre/matrixinteraction in these thermoplastic fibre composites wasalso studied by DSC through characterisation of the fibremelting. A decreased ‘DSC interaction parameter’ wasfound if the composition of the interphase was changedby moisture. For a composite with an epoxy/amine matrix,on the other hand, the DSC interaction parameter wasunaffected by moisture from the fibre surface. 22 refs.(Pt.I, ibid, p.83-100)BELGIUM; EUROPEAN COMMUNITY; EUROPEAN UNION;WESTERN EUROPE

Accession no.566704

Item 250Polymer36, No.22, 1995, p.4233-8



RHEO-OPTICAL RAMAN STUDY OF CHAINDEFORMATION IN UNIAXIALLY STRETCHEDBULK POLYETHYLENERodriguez-Cabello J C; Merino J C; Jawhari T;Pastor J MValladolid,Universidad

A rheo-optical study was developed to examine the natureof the structural changes, other than chain orientation,that can appear during uniaxial drawing of PE samples.Stretching was performed at room temperature in samplesof melt crystallised HDPE and LDPE. Raman spectra weresimultaneously collected along with stress and strain datato gain insight into the molecular basis of the propertiesresulting from the mechanical process. The need for real-time studies was to detect possible transient occurrencesthat cannot be observed with non-rheo-optical studies.15 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;WESTERN EUROPE

Accession no.566487

Item 251Polymer36, No.17, 1995, p.3385-92ORIENTATION AND CONFORMATION INPOLY(ETHYLENE TEREPHTHALATE) WITHLOW DRAW RATIOS AS CHARACTERISED BYSPECULAR REFLECTION INFRAREDSPECTROSCOPYGuevremont J; Ajji A; Cole K C; Dumoulin M MCanada,National Research Council

A quantitative treatment of the specular reflection spectraobtained from the surface of uniaxially drawn PETPsamples was performed. A procedure for correcting forthe effect of surface irregularities is presented, and anoverall orientation function based on the orientation andcontent of trans-conformers is calculated. The results arecorrelated with mechanical modulus and crystallinityvalues. In addition, an unconventional dichroic ratioparameter based on a combination of two major bands isproposed. Results obtained from the Kramers-Kroniganalysis and directly from the reflection spectra arediscussed. Both are compared with the overall orientationfunction obtained before. 21 refs.CANADA

Accession no.564806

Item 252Macromolecular ReportsA32, No.7, 1995, p.1077-82FOURIER TRANSFORM INFRAREDSPECTROSCOPIC STUDY OF CONFORMATIONOF FREEZE-DRIED ISOTACTICPOLYSTYRENEDai Q; Liu X; Wang YNanjing,University

Isotactic PS samples were prepared by shock-cooling andsubsequent freeze-drying from very dilute solutions inbenzene. FTIR studies on these samples indicated thatthere were conformational differences between them anda normal isotactic PS. Comparison of the IR spectraindicated that spectral changes occurred at the bands near1261, 1085-1050, 982, 923-906 and 550/cm. The changesin intensities of the crystalline bands showed that thefreeze-dried isotactic PS from a very dilute solutionexhibited a higher crystallinity than the annealed sample.11 refs.CHINA

Accession no.564742

Item 253Journal of Applied Polymer Science58, No.3, 17th Oct.1995, p.501-14RHEO-OPTICAL FTIR SPECTROSCOPY OFEPOXY RESINSScherzer THalle,Martin-Luther-Universitat

The use of rheooptical FTIR spectroscopy to monitororientation phenomena in highly crosslinked epoxy/aminenetworks during uniaxial deformation above their Tg wasinvestigated. The resins were prepared from the diglycidylether of bisphenol-A and various polyether di- andtriamines in order to examine the influence of the structureof the network formed. The molecular orientation wasstudied in relation to network density and structure. Theorientation behaviour was mainly determined by theflexibility of the polyether chain and the homogeneity ofthe network structure. The epoxy resins were alsosubjected to successive loading-unloading cycles. Theresults showed that the orientation of epoxy networks intheir rubbery state was completely reversible and that nosignificant fatigue due to gradual chain rupture occurreduntil sample failure. 29 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.563380

Item 254Applied Spectroscopy49, No.8, Aug.1995, p.1073-8DYNAMIC TWO-DIMENSIONAL INFRAREDSPECTROSCOPY. I. MELT-CRYSTALLISEDNYLON 11Singhal A; Fina L JRutgers,University

Two-dimensional FTIR spectroscopy was used to studythe N-H stretching and amide I/amide II region of melt-crystallised nylon 11 thin films on Teflon substrates. Thesamples were dynamic mechanically oscillated at roomtemp. at a frequency of 11 Hz. A two-dimensionalcorrelation analysis on the dynamic spectra indicated thatthe N-H stretching region split into two peaks. Analysis



of two-dimensional crossplots between the N-H stretchingregion and the amide I/amide II region showed that theprominent peak in the N-H stretching region (about 3300/cm) was similar in morphological character to the orderedpeak of the amide I region. The amide II region resolvedinto two ordered and one disordered peak. 28 refs.USA

Accession no.563353

Item 255Polymer Science Series B37, Nos.5-6, May-June 1995, p.289-92IR SPECTROSCOPIC STUDY OF THESTRUCTURE OF POLY(VINYL ALCOHOL)-POLY(GLYCIDYL METHACRYLATE) GRAFTCOPOLYMERSBuslov D K; Korolik E V; Zhbankov R G; DruzhininaT V; Nazar’ina L A; Smolenskaya L MBelarus Academy of Sciences; Moscow,Textile Institute

PVAl, poly(glycidyl methacrylate) and their copolymer(obtained by radical graft polymerisation of glycidylmethacrylate onto PVAl fibres) were studied by IRspectroscopy. The spectrum of the graft copolymer wasalso obtained by mathematical modelling. The spectraregions sensitive to the sites of localisation of the kineticchains of grafted poly(glycidyl methacrylate) are foundwithin 3600-3100, 1450-1300, 1120-1000 and 700-500/cm, which correspond to the stretching and bending OHvibrations, stretching carbon-oxygen vibrations, andtorsional vibrations of the hydroxyl groups, respectively.It was established that grafted poly(glycidyl methacrylate)molecules are linked to PVAl macromolecules via oxygenatoms of hydroxyl groups. 12 refs.BELARUS; RUSSIA

Accession no.562450

Item 256Journal of Polymer Science : Polymer Physics Edition32, No.8, June 1994, p.1493-502FTIR STUDY OF PVDF IRRADIATED BYMEANS OF SWIFT HEAVY IONSBetz N; Le Moel A; Balanzat E; Ramillon J M;Lamotte J; Gallas J P; Jaskierowicz GDRECAM/SRSIM; CEA-CNRS; ISMRA;Palaiseau,Ecole Polytechnique

Fourier transform IR measurements were used toinvestigate PVDF films which had been irradiated bymeans of heavy ions (krypton ions) and electrons.Irradiation with krypton ions was carried out in thepresence of helium, hydrogen, deuterium and oxygen.Triple bonds were characteristic of krypton ion irradiation.Double bonds (isolated and conjugated) occurred withboth types of irradiation but concentrations were higherwith the krypton radiation. The results, including the roleof oxygen on the chemical modifications, were discussed.36 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.562089

Item 257Journal of Polymer Science : Polymer Physics Edition32, No.8, June 1994, p.1315-20FTIR ANALYSIS OF HYDROGEN BONDING INAMORPHOUS LINEAR AROMATICPOLYURETHANES. II. INFLUENCE OFSTYRENE SOLVENTWang F C; Feve M; Lam T M; Pascault J-PURA CNRS

FTIR studies were carried out on a polyurethane gelsynthesised by reacting the alpha,omega-hydroxy-terminated random copolyadipate of ethanediol andbutanediol with 4,4'-diphenylmethane diisocyanate insolution with 30% to 90% (w/w) of styrene. The resultsof studying N-H vibrations in the stretching and bendingregions showed that the N-H groups of the PU couldhydrogen bond with C=O groups and other groups in thissystem. Some of the aromatic rings of the styrene werehydrogen bonded with the N-H groups of the PU. Themole fractions of “free” N-H groups and of N-H groupshydrogen bonded to C=O groups and to the pi orbitals ofthe aromatic rings were calculated. 9 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.562071

Item 258Journal of Polymer Science : Polymer Physics Edition32, No.7, May 1994, p.1163-74RAMAN SPECTRAL STUDY OF SOLID ANDDISSOLVED POLY(VINYL ALCOHOL) ANDETHYLENE-VINYL ALCOHOL COPOLYMERCooney T F; Wang L; Sharma S K; Gauldie R W;Montana A JHawaii,University; Warner-Lambert Co.,NovonProducts Group

The Raman spectra of ethylene-vinyl alcohol copolymerand poly(vinyl alcohol) were measured and compared.The spectral changes that occurred during the dissolutionof poly(vinyl alcohol) in, and the precipitation of filmsof poly(vinyl alcohol) from, both water and deuteriumoxide were studied and the results were discussed. 46 refs.USA

Accession no.562058

Item 259Journal of Applied Polymer Science57, No.13, 26th Sept.1995, p.1585-94QUANTITATIVE ANALYSIS OFFLUOROCARBON POLYMER FINISHES ONWOOL BY FTIR SPECTROSCOPYChurch J S; Evans D J



CSIRO

Two contrasting IR spectroscopic techniques, ATR andphotoacoustic spectroscopy, were investigated as meansfor the determination of fluorocarbon polymer finisheson wool fabric. Based on the experimental conditionsused, the results of the photoacoustic spectroscopy methodare more characteristic of the bulk sample, while the ATRresults are more surface specific. Linear calibrationsbetween polymer addition, as determined by total fluorineanalysis, and the absorbance of the C-F stretching bandsof the normalised spectral data were obtained for a typicalcommercial fluorocarbon polymer. The quantitativemethods developed are used to help access the effects ofwear and the subsequent heating of fluorocarbon polymer-treated fabric samples. 21 refs.AUSTRALIA

Accession no.561437

Item 260Polymer Testing14, No.5, 1995, p.489-94QUANTITATIVE APPLICATION OF DRIFTSPECTROSCOPY: DETERMINATION OFCOMPOSITION OF SPECIAL ACRYLIC FIBRESPandey G C; Rao K V; Kumar AIndian Petrochemicals Corp.Ltd.

A fast, direct and non-destructive method involving nosample preparation was developed for recording a well-resolved and reproducible spectrum of special acrylic fibre(SAF), a precursor for carbon fibre using diffusereflectance infrared Fourier transform (DRIFT)spectroscopy. A novel method was developed fordetermining the composition of SAF containing bothacrylate and carboxylic acid comonomers. The specialfeature is that no standard samples (of knowncomposition) are required. 11 refs.INDIA

Accession no.559472

Item 261Polymer Engineering and Science35, No.12, June 1995, p.1011-5IDENTIFICATION OF PLASTIC WASTE USINGSPECTROSCOPY AND NEURAL NETWORKSScott D M; Waterland R LDu Pont de Nemours E.I.,& Co.Inc.

A new approach is described for the automated sorting ofpost-consumer plastic waste. It is shown that rapid andreliable identification of polymers can be achieved usinga combination of fixed-filter near-IR spectroscopy andneural network data analysis. The effectiveness of themethod is demonstrated for sorting PETP, HDPE, andPVC. 11 refs.USA

Accession no.558755

Item 262Macromolecules28, No.15, 17th July 1995, p.5163-6REAL-TIME ATTENUATED TOTALREFLECTANCE-FOURIER TRANSFORMINFRARED SPECTROSCOPY TO MONITORMULTIACRYLATE POLYMERISATIONREACTIONSDietz J E; Elliott B J; Peppas N APurdue,University

Real-time attenuated total reflectance FTIR spectroscopywas used to follow the conversion during acrylatepolymerisations by measuring the presence of functionalgroups at finite depths from the crystal surface. By varyingthe film thickness, the reactivity of multiacrylates couldbe spatially resolved. These results were compared withresults from different photocalorimetric studies. 22 refs.USA

Accession no.558238

Item 263Macromolecules28, No.11, 22nd May 1995, p.4040-3REAL-TIME INFRARED CHARACTERISATIONOF REACTION DIFFUSION DURINGMULTIFUNCTIONAL MONOMERPOLYMERISATIONSAnseth K S; Decker C; Bowman C NColorado,University; Ecole Nationale Superieure deChimie de Mulhouse

Reaction diffusion is defined as radicals moving bypropagating through unreacted double bonds and itssignificance, rather than segmental diffusion, in thetermination reaction is pointed out. Diethylene glycoldimethacrylate was polymerised by UV light. Initiationwas stopped at 18% conversion of double bonds and thedark reaction was monitored for 50s by real-time IRspectroscopy. The point at which reaction diffusion beganto dominate termination could be accurately determined.The reaction diffusion parameter was found to beindependent of the length of time the polymerisation wasmonitored in the dark. The method was found to beparticularly useful for analysing high conversion kinetics.Results were obtained also for poly(ethylene glycol 200)dimethacrylate and poly(ethylene glycol 600)dimethacrylate. By selecting these monomers, the rangeof glassy to rubbery polymer networks was spanned. 19refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;USA; WESTERN EUROPE

Accession no.557329

Item 264Applied Spectroscopy49, No.6, June 1995, p.747-53SIMULTANEOUS DETERMINATION OF



RUBBER ADDITIVES BY FTIRSPECTROPHOTOMETRY WITHMULTIVARIATE CALIBRATIONBlanco M; Coello J; Iturriaga H; Maspoch S; Bertran EBarcelona,Universidad Autonoma

A new method for the determination of vulcanised rubberadditives by FTIR spectrophotometry using partial least-squares regression (PLSR) for multivariate calibrationwas developed. The effect of various wavenumber rangesand the use of the absorbance and first-derivative spectralmodes on performance were studied by applying themethod to three different sample batches containingseveral additives in different proportions all of which wereresolved with satisfactory results. 15 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;WESTERN EUROPE

Accession no.555868

Item 265Polyurethanes ’94. Conference proceedings.Boston, Ma., 9th-12th Oct.1994, p.381-3. 43C6MONITORING THE PRODUCTION OFPOLYURETHANES WITH NEAR-INFRAREDSPECTROSCOPYHall J W; DeThomas F ANIRSystems Inc.(SPI,Polyurethane Div.)

By the use of near-infrared instrumentation designedspecifically for the process environment, the isocyanatecontent of a urethane polymerisation reaction is monitoredin real-time. A standard error of prediction of 0.15% isachieved. Real-time chemical process and analysis yieldsimprovement in product consistency and quality whilemaximising process efficiency. 4 refs.USA

Accession no.555628

Item 266Polyurethanes ’94. Conference proceedings.Boston, Ma., 9th-12th Oct.1994, p.375-80. 43C6APPLICATIONS OF RAMAN SCATTERING TOPLASTICS RECYCLING AND PROCESSMONITORINGBen-Amotz D; Laplant F; Jiang Y; Biermann TEdited by: Purdue,University; BASF Corp.(SPI,Polyurethane Div.)

The composition of a polymeric material is of interestthroughout its useful life. From process stream to productfabrication, and finally to post-consumer recycling, it isdesirable to know not only what types of materials arepresent, but also their relative concentrations. In many cases,Raman spectroscopy can provide a quick, convenient andrelatively inexpensive alternative conventional analyticalmethod for performing these types of determinations. 15 refs.USA

Accession no.555627

Item 267Polyurethanes ’94. Conference proceedings.Boston, Ma., 9th-12th Oct.1994, p.280-5. 43C6IMPROVED TECHNIQUE FOR THEDETERMINATION OF ISOCYANURATE ANDISOCYANATE CONVERSION BYPHOTOACOUSTIC FTIRBhattacharjee D; Engineer RDow Chemical Co.(SPI,Polyurethane Div.)

Conventional rigid polyisocyanurate foams blown withHCFC-141b often suffer from poorer compressivestrengths, dimensional stability and inferiorinflammability properties when compared to foams blownwith CFC-11. An improved isocyanurate conversion testby photoacoustic Fourier Transform Infra Red techniqueis introduced. The method is not limited topolyisocyanurate foam, as isocyanate conversion is animportant parameter to follow in PU foams as well,especially in all carbon dioxide blown foams. The methodis found to be quite reproducible and further statisticalanalysis to ensure the validity of this technique is underway. 8 refs.USA

Accession no.555511

Item 268Journal of Applied Polymer Science56, No.12, 20th June 1995, p.1557-60DETERMINATION OF FILLER CONTENT INTHERMOPLASTIC COMPOSITES BY FTIRANALYSISFuad M Y A; Yaakob I; Rusli O; Ishak Z A M;Omar A K MMalaysia,Standards & Industrial Research Inst.; SainsMalaysia,University

White rice husk ash (predominantly silica) wasincorporated as a filler (10, 20, 30 and 40% by weight)into PP homopolymer. Absorption peaks at 480, 621 and790/cm gave good linearity with increasing filler content.9 refs.MALAYSIA

Accession no.555101

Item 269Macromolecular SymposiaVol.94, May 1995, p.75-95DYNAMIC FTIR SPECTROSCOPY OFPOLYMER FILMS AND LIQUID CRYSTALSGregoriou V G; Palmer R ADurham,Duke University

The use of continuous-scan and step-scan FTIRspectroscopic techniques to study the dynamics of theresponse of polymer films and liquid crystals to externalperturbations is described. Results are presented for



HDPE, LDPE and SBR, and for pentylcyanobiphenyl andpentylcyanophenylcyclohexane liquid crystal molecules.14 refs.USA

Accession no.554082

Item 270Macromolecular SymposiaVol.94, May 1995, p.33-49ROLE OF VIBRATIONAL SPECTROSCOPY-MICROSCOPY TECHNIQUES IN POLYMERCHARACTERISATIONChalmers J M; Everall N JICI

Details are given of the use of IR and Raman microscopy/microprobe spectroscopic techniques for the spatially-resolved identification, study and characterisation ofpolymers. Chemical and physical propertycharacterisations are discussed. 35 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.554079

Item 271Applied Spectroscopy49, No.5, May 1995, p.672-8REAL-TIME, MID-INFRAREDSPECTROSCOPIC IMAGING MICROSCOPYUSING INDIUM ANTIMONIDE FOCAL-PLANEARRAY DETECTIONLewis E N; Levin I WUS,National Institutes of Health

A new approach to mid-IR spectroscopic imagingmicroscopy is described in which instrumentation isdesigned about an InSb multichannel, focal-plane arraydetector and a variable-bandpass dielectric filter. Thesystem may be configured for either macroscopic ormicroscopic applications and high-fidelity, chemicallyspecific images may be acquired in real time. With thedielectric filter used in this assembly, continuous tuningis provided for the IR 4000-2320/cm spectral region withspectral resolutions of about 35-18/cm at the extremes ofthis wavelength interval. The functioning of the imagingmicroscope is demonstrated with samples including PSmicrospheres, preparation of lipids and an amino acidembedded in KBr disks, and a tissue sample derived froma coronal slice of a monkey cerebellum. 10 refs.USA

Accession no.553706

Item 272147th Meeting, Spring 1995, Conference Preprints.Philadelphia, Pa., 2nd-5th May 1995, Paper 19, pp.34. 012USE OF PHOTOACOUSTIC FOURIERTRANSFORM INFRARED SPECTROSCOPY TO

QUANTITATIVELY CHARACTERISEPOLYMER STRUCTUREParker J R; Waddell W HPPG Industries Inc.,Chemicals Group(ACS,Rubber Div.)

The potential use of photoacoustic Fourier transform IRspectroscopy in the quantitative analysis of polymers wasexplored by studying the determination of vinyl acetatein EVA, acrylonitrile in nitrile rubber, ethylene in EPDM,and styrene and vinyl butadiene in SBR. Despite thetheoretical complexities of this technique, simplequantitative relationships could be found for many of thesepolymer analyses. 24 refs.USA

Accession no.552356

Item 273Polymer Degradation and Stability47, No.3, 1995, p.423-33THERMAL DEGRADATION OF VINYLACETATE-METHACRYLIC ACID COPOLYMERAND HOMOPOLYMERS. 1. AN FTIRSPECTROSCOPIC INVESTIGATION OFSTRUCTURAL CHANGES IN THE DEGRADINGMATERIALMcNeill I C; Ahmed S; Memetea LGlasgow,University

The thermal degradation in vacuo, up to 500C, of a vinylacetate-methacrylic acid copolymer having 65%alternating units, and of the corresponding homopolymers,was studied by reflection-absorption FTIR spectroscopy.PVAc crosslinks form due to double bond formationthrough deacetylation. Polymethacrylic acid generateslittle unsaturation, but crosslinks by intermolecularanhydride links. It decomposes above 350C when theanhydride breaks down with much chain scission. In thecopolymer, both types of crosslinking reactions aredisturbed by lactone formation between alternating vinylacetate and methacrylic acid units. The lactone formationprotects the vinyl acetate units from deacetylation andcompetes strongly with anhydride formation. Lactonegroups are thermally resistant and can be found in charredpolymer at 440C, next to aromatic rings. At 480C thelactone decomposes, helping the fusion of the aromaticrings in the strongly diminished char. 17 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.551478

Item 274Polymer Degradation and Stability47, No.3, 1995, p.413-21COMPARISON OF THE THERMALDEGRADATION PRODUCTS OFPOLY(BUTYLENE TEREPHTHALATE) ANDFLAME RETARDANT POLY(BUTYLENE



TEREPHTHALATE) FORMULATIONS USING APYROLYSIS FTIR CELLPellow-Jarman M; Hetem MSouthampton,University; General Electric PlasticsEurope

The two flame retardant materials contained two differentheavily brominated aromatic compounds. A simple FTIRpyrolysis cell was used for the evaluation. Ondecomposition, the PBTP polymers gave off mainly water,carbon dioxide, butadiene, THF and PBTP oligomers. Theflame retardants increased marginally the polymerdecomposition temperature. The merits of the testequipment are discussed. Results were consistent withprevious TGA results. 7 refs.EUROPEAN COMMUNITY; EUROPEAN UNION;NETHERLANDS; UK; WESTERN EUROPE

Accession no.551477

Item 275Applied Spectroscopy49, No.4, April 1995, p.513-9ATR SPECTROSCOPIC STUDY OF PMMA/PDMS GRAFT COPOLYMERS USING ABARRIER LAYER METHODMarand E; Smartt L MVirginia,Polytechnic Institute & State University

The use of an intermediate barrier layer to vary thepenetration depth in an ATR experiment was investigated.Both theoretical and experimental results suggested thatthis method could be useful in probing concentrationprofiles away from the interface, particularly in the caseof thin films, where variable-angle methods hadlimitations. Application of this technique in the study ofPMMA/PDMS graft copolymers deposited onto a copperoxide surface indicated a preferential presence of thesiloxane component at the oxide interface, a concentrationwhich tended to decrease with increasing distance intothe bulk of the sample film. 20 refs.USA

Accession no.550883

Item 276Macromolecules28, No.8, 10th April 1995, p.2797-806STUDY OF REACTION KINETICS BY NEAR-INFRARED SPECTROSCOPY. II. COMPARISONWITH DIELECTRIC SPECTROSCOPY OFMODEL AND MULTIFUNCTIONAL EPOXY/AMINE SYSTEMSMijovic J; Andjelic S; Yee C F W; Bellucci F; Nicolais LNew York,Polytechnic University; Napoli,Universita

An investigation of the kinetics of two non-polymer-forming epoxy/amine model systems and a polymer-forming multifunctional epoxy/amine formulation (Epon825 plus 4,4'-methylenedianiline) was carried out bydielectric and near-IR spectroscopy. Dielectric

measurements were performed in the frequency rangewhere polarisation by charge migration is the dominantmechanism and the extent of reaction was calculated fromthe measured variation in impedance during reactions.Near-IR spectroscopy was carried out in the frequencyrange between 7100 and 4000/cm, and the extent ofreaction was evaluated from the changes in thecharacteristic absorption peaks. Kinetic results determinedby dielectric and near-IR spectroscopy were in excellentagreement for all systems investigated. 19 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY; USA;WESTERN EUROPE

Accession no.550458

Item 277Macromolecules28, No.8, 10th April 1995, p.2787-96STUDY OF REACTION KINETICS BY NEAR-INFRARED SPECTROSCOPY. I.COMPREHENSIVE ANALYSIS OF A MODELEPOXY/AMINE SYSTEMMijovic J; Andjelic SNew York,Polytechnic University

The model compounds were 1,2-epoxy-3-phenoxypropane and aniline. In addition other materialswere used to help assign different absorption peaksobserved in the course of the investigation. These includedepoxy resin monomers, i.e. bisphenol A diglycidyl etherand tetraglycidyl diaminophenyl methane and aminecuring agents, i.e. 4,4'-methylenedianiline anddiaminodiphenyl sulphone. A comprehensive account ofthe origin, location, and shifts during reaction of all majoradsorption peaks in the spectral range between 4000 and7100/cm is provided. Reaction kinetics derived from thenear-IR data were in excellent agreement with the resultsobtained by high performance liquid chromatography.There was a discrepancy between the kinetic predictionsof near-IR and mid-IR analyses. It was established thatthe kinetics of epoxy/amine reactions can be accuratelydeduced from the near-IR data, while the standard mid-IR epoxy absorption band at 915/cm was not a uniquemeasure of the epoxy concentration, and hence itsutilisation in kinetic calculations is questionable unlessappropriate corrections are made. Evidence was presentedfor the formation of hydrogen bonding that is directlyrelated to a critical viscosity of the reactive mixture. 19refs.USA

Accession no.550457

Item 278Journal of Polymer Science : Polymer Physics Edition32, No.3, Feb.1994, p.395-408TOUGHENING OF A HIGHLY CROSS-LINKEDEPOXY RESIN BY REACTIVE BLENDINGWITH BISPHENOL A POLYCARBONATE. I.FTIR SPECTROSCOPY



Abbate M; Martuscelli E; Musto P; Ragosta G; ScarinziGCAMPEC; Italy,National Research Council

A highly crosslinked epoxy resin was modified by reactiveblending with bisphenol A polycarbonate. The bisphenolA polycarbonate was dissolved at high temperature in theuncured epoxy resin before the curing process. Thephysical and chemical interactions between the twocomponents were studied by FTIR spectroscopy and thereaction mechanisms were discussed. FTIR isothermalmeasurements showed that the presence of polycarbonatedid not affect the overall curing mechanism but decreasedboth the initial reaction rate and the final conversion ofreactants. 13 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;WESTERN EUROPE

Accession no.548582

Item 279Journal of Polymer Science : Polymer ChemistryEdition32, No.3, Feb.1994, p.485-93PHOTO- AND THERMOINITIATED OXIDATIONOF HIGH-IMPACT POLYSTYRENE. I.CHARACTERISATION BY FT-IRSPECTROSCOPYIsraeli Y; Lacoste J; Lemaire J; Singh R P; Sivaram SBlaise Pascal,Universite

The photo- and thermooxidative degradation of differentgrades of high-impact polystyrene containing variousamounts of polybutadiene were studied using FTIRspectroscopy. All samples gave similar oxidation products,but in varying quantities. The results are discussed. 17refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.548569

Item 280Applied Spectroscopy49, No.3, March 1995, p.267-72CHARACTERISATION OF POLYMER-DISPERSED LIQUID CRYSTAL SYSTEMS BYFTIR MICROSPECTROSCOPYChalla S R; Wang S Q; Koenig J LCase Western Reserve University

IR microspectroscopy was used to generate functionalgroup images of liquid crystal(E7) droplets dispersed inpoly-n-butyl methacrylate(PBMA). The spatialconcentration fluctuations that occurred within the systemwere studied as a function of time. This approach waspossible because spectral information could be obtainedby focusing on regions of the order of tens of micrometers.The peak intensities were used as a measure ofconcentration of the components. The amount of liquidcrystal dissolved in the polymer matrix determined the

extent to which the polymer was plasticised, which inturn affected the shape and size of the droplets. The growthof the domains at any temp. was also determined bywhether the system was maintained above or below theTg of the matrix. It was observed that the growth of thedroplets followed temporal power laws. The spatiallyresolved spectroscopic images provided valuable insightsinto the phase separation process and the formation ofmicrodroplets of E7 in PBMA. 20 refs.USA

Accession no.546736

Item 281Plastics & Rubber & Composites Processing &Applications23, No.1, 1995, p.11-9ANALYSIS OF COMPOSITE TEST METHODSUSING RAMAN SPECTROSCOPYYoung R J; Huang Y L; Gu X; Day R JUMIST; Manchester,University

Three test methods, the fragmentation, pull-out andmicrobond methods, were used to analyse themicromechanics for carbon fibre/epoxy composites andRaman spectroscopy was used to determine the variationof fibre strain with position along a carbon fibre in a resin.It was demonstrated that the latter technique was capableof revolutionising interpretation of compositemicromechanics and the different micromechanical testmethods. In particular, it was shown that the techniquecould be used to distinguish between elastic deformation,interfacial debonding and shear yielding of the matrix atthe interface. 19 refs. (FRC ’94, Institute of Materials,Newcastle, March 1994)EUROPEAN COMMUNITY; EUROPEAN UNION; UK;WESTERN EUROPE

Accession no.540316

Item 282Polymer36, No.2, 1995, p.251-7LOW-FREQUENCY RAMAN SPECTROSCOPYOF PLASTICALLY DEFORMED POLYMETHYLMETHACRYLATEAchibat T; Boukenter A; Duval E; Mermet A;Aboulfaraj M; Etienne S; G’Sell CUniversite Claude Bernard; Ecole des Mines de Nancy

Low-frequency Raman scattering (2-200/cm range) ofPMMA specimens plastically deformed in pure shear wascompared with that of undeformed samples. The mainobservation was an excess of Raman scattering in the 30-50/cm spectral range induced by plastic deformation. Thisexcess appeared to be strongly anisotropic and wasmaximum when the light polarisation was orthogonal tothe principal tensile strain component, i.e. to the chainorientation direction. The effect was still present, but witha weaker anisotropy, after mechanical cycling when the



macroscopic deformation was returned to zero byapplication of an opposite stress. These results wereinterpreted in terms of the non-continuous nature of thedisordered network on the nanometric scale. Theorientation of macromolecular strands induced by plasticdeformation was shown to be higher in the less cohesivespaces. 24 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.540286

Item 283Applied Spectroscopy48, No.11, Nov.1994, p.1410-8POLARISATION-DIVISIONINTERFEROMETRY: FAR-INFRAREDDICHROISMPolavarapu P L; Gang-Chi ChenVanderbilt University

A detailed report is given of the first far-infrared dichroismmeasurements using a polarisation-division interferometer(PDI) which uses a free-standing wire grid beamsplittermade of tungsten wires. The performance of the PDI wasevaluated by measuring the linear dichroism of orientedpolyvinylidene fluoride and circular dichroism of alpha-pinene, camphor and 3-methylcyclohexanone. Thedichroic multiplex advantage (ability to measuredichroism in the entire far-infrared region from a singlemeasurement) and throughput advantage aredemonstrated. These measurements establish the utilityof the PDI in measuring transmission and linear dichroismspectra simultaneously without the need for any additionalcomponents. 17 refs.USA

Accession no.539429

Item 284Polymer Bulletin34, No.1, Jan.1995, p.71-7DAMAGE OF POLYMERS STUDIED BY MICRO-FOURIER TRANSFORM RAMANSPECTROSCOPYJawhari T; Merino J C; Pastor J MValladolid,Universidad

The potential of micro-Fourier transform Ramanspectroscopy for examining specific localised regions inpolymeric materials with some degree of fluorescencewhen analysed by conventional Raman spectroscopy wasexamined. Analysis of characteristic bands of thevibrational spectra obtained in a small area damaged bya visible and near-IR laser beam in commercial PETPshowed a different conformer ratio than that observed ina non-irradiated zone. 32 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;WESTERN EUROPE

Accession no.538461

Item 285Journal of Adhesion46, Nos.1-4, 1994, p.227-41ZINC COATED STEEL/EPOXY ADHESIVESYSTEMS: INVESTIGATION OF THEINTERFACIAL ZONE BY FTIRSPECTROSCOPYGaillard F; Romand M; Verchere D; Hocquaux HCNRS; IRSID Unieux

FTIR spectroscopy was used for the analysis ofultrathin organic films on metals. FTIR in the reflectionmode (IRRAS) was used to study the interaction ofultrathin films of dicyandiamide (hardener of most one-pack epoxy resins) with various substrates, model onessuch as gold or zinc and industrial ones such as steeland zinc-coated steels. Pure zinc surfaces and, to alesser extent, zinc-coated steels are shown to react withdicyandiamide after heating at 180 C, as evidenced bythe frequency shift of the absorption band characteristicfor nitrile groups. Some mechanically tested specimensare then analysed, after failure, by FTIRmicrospectrometry. The spectra obtained,corresponding to the fracture initiation zone which isabout 100 micrometers in diameter, indicate thepresence of an ultrathin layer of modified polymer stillcovering the substrate. 28 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.531582

Item 286Journal of Adhesion46, Nos.1-4, 1994, p.91-102STUDY OF FIBRE-MATRIX INTERACTIONSVIA FTIR MICROSCOPY AND NMR IMAGINGMavrich A; Fondeur F; Ishida H; Koenig J L;Wagner H DCase Western Reserve University; Weizmann Instituteof Science

Model composites of Kevlar-49 and D-glass fibre/epoxy systems were analysed using NMR imaging andFTIR microscopy. The interphase and specific fibre-matrix interactions of the fibre-reinforced compositeswere characterised. The surfaces of both Kevlar-49 andD-glass fibres were found to affect the curing processin composite samples significantly. NMR imagesrevealed non-uniform cure of the matrix in thecomposites. The epoxy was found to cure at anaccelerated rate at the surface of these fibres indicatingstrong interaction between the fibres and the matrices.Using FTIR microscopy, these interactions were foundto be preferential segregation of the epoxy on theKevlar surface. It was also determined that the aminegroup of the Kevlar fibre acted to catalyse the curingprocess. 8 refs.ISRAEL; USA

Accession no.531574



Item 287Macromolecular Chemistry & Physics195, No.10, Oct.1994, p.3369-80RAMAN SPECTROSCOPIC STUDY OFHYDROGEN BONDING OF POLY-N-VINYL-2-PYRROLIDONE(PVP) IN HEAVY WATER ANDDIMETHYL SULPHOXIDETanaka N; Ito K; Kitano HKyoto,Institute of Technology; Toyama,University

The Raman spectra of solutions of PVP of molec.wt. 1000,10,000, 40,000 and 360,000 in heavy water and DMSOwere measured at various concentrations. PVP washydrated by heavy water in a different way from N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone(NMP),monomer analogues of PVP. The self-association ofDMSO molecules in the solution of PVP was found to bedifferent from that in the solution of NMP by usingdifference spectroscopy. These phenomena wereattributed to a net-like structure of concentrated solutionsof PVP. 29 refs.JAPAN

Accession no.530107

Item 288Journal of Environmental Polymer Degradation2, No.2, April 1994, p.153-60INFRARED SPECTROSCOPY STUDIES OF THEPHOTOOXIDATION OF A POLYETHYLENENONWOVEN FABRICMartin L K; Yang C QMarshall University; Georgia,University

The photooxidation of a nonwoven PE fabric wasinvestigated using FTIR photoacoustic spectroscopy.Hydroperoxide, alcohol, aldehyde, ketone, carboxylicacid, and anhydride groups were formed as the productsof the photooxidation of the PE fabric and the relativeamount of carboxyl among all carbonyls increased as thephotooxidation progressed. Distribution of thephotooxidation products was inhomogeneous between thetwo surfaces of the fabric. The highest degree ofphotooxidation occurred on the surface of the fabric usingthe UV radiation source, whereas the lowest degree ofphotooxidation was on the back surface of the fabric. ThePE nonwoven fabric showed a slower photooxidation ratethan the PP nonwoven fabric. The UV radiation at 254nm caused photooxidation of PE. No photooxidation wasobserved in the fabric exposed to the UV radiation at 350nm under the same conditions. 25 refs.USA

Accession no.529929

Item 289Macromolecules27, No.18, 29th Aug.1994, p.5220-2CHARACTERISATION OF SOLUTE DIFFUSIONIN A POLYMER USING ATR-FTIR

SPECTROSCOPY AND BULK TRANSPORTTECHNIQUESFarinas K C; Doh L; Venkatraman S; Potts R OCygnus Therapeutic Systems

ATR-FTIR spectroscopy was used to monitor the uptake ofurea into a silicone polymer. Analysis of the time-dependentchanges in the IR absorbances of urea and silicone leads toan estimate of the diffusion coefficient for urea that is inclose agreement with a value obtained using a bulk transportmethod (involving radiolabelled permeant). The siliconepolymer was medical grade silicone pressure-sensitiveadhesive (X7-4201). ATR-FTIR is proposed as a rapid andaccurate method of rapidly and accurately determining solutediffusion within a polymer matrix. 12 refs.USA

Accession no.529399

Item 290Synthetic Metals55, No.1, 15th March 1993, p.503-8IN SITU INTERNAL REFLECTION FTIRSTUDIES ON POLYMERISATION OFPOLYPHENYLENEKvarnstrom C; Nyback A-S; Ivaska AAbo,University

Electrochemical polymerisation involving simultaneousdoping of polyphenylene was studied using in-situ internalreflection FTIR spectroscopy. The results indicated thatthe polymer has a complex structure consisting ofcrosslinked short chains and oligomers in which thephenyl rings are ortho-, meta- and para-substituted. Thecurrent densities used for polymerisation were found tohave no effect on the coupling of phenyl rings. 12 refs.FINLAND; SCANDINAVIA; WESTERN EUROPE

Accession no.527763

Item 291Polymer35, No.12, June 1994, p.2538-41MOLECULAR ORIENTATION STUDIES INPOLYMER FILMS BY POLARISATIONMODULATION FTIR SPECTROSCOPYBuffeteau T; Desbat B; Besbes S; Nafati M; Bokobza LBordeaux,University; ESPCI

Measurements of molecular orientation in stretched filmsof polydimethylsiloxane using IR linear dichroism wereimproved by the introduction of polarisation modulationof the incident electromagnetic field. It was shown that, byimproving the signal-to-noise ratio and minimising errorsgenerated by repositioning the sample or the polariser fora second measurement, this technique was capable ofmeasuring small dichroic effects with high sensitivity, evenfor very small sample draw ratios. 14 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;WESTERN EUROPE

Accession no.526061



Item 292Polymer35, No.12, June 1994, p.2495-500RAMAN AND IR SPECTROSCOPY OFELECTROCHEMICALLY OBTAINEDCONDUCTING AND NON-CONDUCTING POLY-N-VINYLCARBAZOLESacak M; Akbulut U; Cheng C; Batchelder D NLeeds,University

Studies of the above spectra showed that the conductingpolymer had a 3,3'-dicarbazyl structure formed bydimerisation at the 3,6 position. An appropriatemechanism was proposed. The conducting polymer wasalso obtained by electrolysis of the non-conductingpolymer dissolved in dichloromethane. The conductingpolymer obtained by this method was found to have asimilar structure to that obtained by direct electrolysisof the monomer. The polymerisation was monitoredby use of a specially designed cell, with in situ Ramanspectra being taken from the electrode surface atdifferent intervals. These spectra showed that therewere no significant structural changes occurring in theconducting polymer during the polymerisation process.In addition, the Raman image of the conductingpolymer was taken by using the intense band whichwas located at 1600/cm. 33 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.526055

Item 293Macromolecular Chemistry & Physics195, No.9, Sept.1994, p.3261-70RAMAN SPECTROSCOPIC STUDY ON WATERIN AQUEOUS SOLUTIONS OF TEMPERATURE-RESPONSIVE POLYMERS: POLY(N-ISOPROPYLACRYLAMIDE) AND POLY(N-(3-ETHOXYPROPYL)ACRYLAMIDE)Terada T; Inaba T; Kitano H; Maeda Y; Tsukida NKyoto,University; Toyama,University

Property changes of water in the course of the temp.-responsive solution-aggregate transition phenomenon ofaqueous poly(N-isopropylacrylamide) and poly(N-(3-ethoxypropyl)acrylamide) solutions were studied byRaman spectroscopy. Upon the transition of polymersfrom coil to globule followed by the aggregation ofindividual polymer chains, the height ratio of the peaksat 3250 and 3400/cm, corresponding to the O-Hstretching of water molecules, was drastically changed.The contribution of small water domains included inpolymer aggregates (‘interstitial water’) to the changein the Raman spectra was considered. The effects ofpolymer concentration and molec.wt. of polymers onthe spectra were also examined. 14 refs.

JAPAN

Accession no.526038

Item 294Acta Polymerica45, No.4, July 1994, p.319-24FTIR SPECTROSCOPIC STUDIES ON THEHETEROGENEOUS TRANSFORMATION OFCELLULOSE I INTO CELLULOSE IIFengel D; Strobel CMunich,University

The heterogeneous transformation of cellulose I intocellulose II via sodium-cellulose I was carried out by alkalitreatment of cotton linters followed by stepwise washing.Two experimental series were conducted, one with sodiumhydroxide/water and the other with deuterated sodiumhydroxide/heavy water. Changes in the cellulose structurewere studied by FTIR spectroscopy. Various reactionssuch as the inclusion of alkali and water in the celluloselattice, splitting and new formation of inter- andintramolecular hydrogen bonds were examined withreference to the absorbance variations and wavenumbershifts of several bands. 27 refs.EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;WESTERN EUROPE

Accession no.524205

Item 295Applied Spectroscopy48, No.7, July 1994, p.900-3MONOMERS IN POLYMER DISPERSIONS. IV.PARTITION OF ACRYLONITRILE IN RUBBERLATEX AS STUDIED BY RAMANSPECTROSCOPYHergeth W D; Codella P JGeneral Electric Co.

The partitioning of acrylonitrile between particles and theaqueous phase of polybutadiene latex was measured byRaman spectroscopy using rubber latex as substrate.Overlapping peaks corresponding to acrylonitrile in thepolymer and aqueous phases were resolved with the useof a peak fit. Peak intensities yielded the partition valuesafter corrections for internal field effects in the two phases.23 refs.USA

Accession no.523456

Item 296Macromolecules27, No.2, 17th Jan.1994, p.545-52INFRARED SPECTROSCOPIC STUDY OFBLENDS OF POLY(STYRENE-CO-STYRENESULPHONIC ACID) WITHPOLY(STYRENE-CO-(4-VINYLPYRIDINE))Smith P; Eisenberg AMcGill University

Poly(styrene-co-styrenesulphonic acid) copolymerscontaining 2 to 10 mol % acidic units were mixed instoichiometric amounts of interacting groups with



poly(styrene-co-(4-vinylpyridine)) copolymers containing2 to 10 mol % basic units. FTIR spectroscopy revealedthat about 80-90% of the pyridine units in the blend wereprotonated, with the pyridinium ions hydrogen-bondedto the anion. An FTIR temp. study indicated that thepyridinium units were involved in an equilibriuminvolving the hydrogen-bonded pyridinium/sulphonateion pair and most likely the hydrogen-bonded but non-ionic acid/base pair. Previously reported mechanicalproperty measurements were interpreted in the light ofthese results. 38 refs.CANADA

Accession no.523004

Item 297Die Makromolekulare Chemie- MacromolecularsymposiaVol.84, July 1994, p.351-63OXIDATIVE DEGRADATION OF WATER-SOLUBLE POLYETHERS BY HYDROXY ANDHYDROPEROXY GENERATEDPHOTOCHEMICALLY: FTIR STUDIESKaczmarek H; Linden L A; Rabek J FCopernicus N.,University; Sweden,Royal Institute ofMedicine

Two water-soluble polyethers, polyethylene oxide andpolymethyl vinyl ether, were UV irradiated in hydrogenperoxide solutions. It was shown that hydroxy andhydroperoxy radicals accelerate oxidative degradation ofthese polymers. Hydroxy and probably hydroperoxyradicals can abstract hydrogen from methylene groups inboth polymers. As a result of further oxidative reactions,different carbonyl, hydroxy and hydroperoxy groups areformed. A mechanism for the formation of these groupsis proposed. 8 refs.EASTERN EUROPE; POLAND; SCANDINAVIA; SWEDEN;WESTERN EUROPE

Accession no.521510

Item 298Synthetic Metals64, No.1, May 1994, p.91-5TOTAL INTERNAL REFLECTANCE IRSPECTROSCOPY OF POLYPYRROLE ON ASILICON ELECTRODERangamani A G; McTigue P T; Verity BMelbourne,University; South Australia,University

A new experimental arrangement is described wherebythin films (about 1 micrometre thick) of polypyrrole wereelectrochemically deposited onto a silicon rod singlecrystal that formed an element of the cylindrical internalreflectance accessory of an FTIR spectrometer.Polypyrrole was deposited from acetonitrile solutionsof pyrrole in the presence of lithium perchlorate,tetrabutylammonium perchlorate and tetrabutyl-ammonium tetrafluoroborate. Excellent quality in situ

ATR FTIR spectra were obtained over a range ofpotentials, with no solvent interference, showingsystematic changes in spectra with the progressiveoxidation and reduction of the polymer film. Both anionsand cations were found in both oxidised and reducedpolypyrrole. 11 refs.

AUSTRALIA

Accession no.516463

Item 299Makromolekulare Chemie, Rapid Communications15, No.6, June 1994, p.467-73ANALYSIS OF ORIENTATIONAL RELAXATIONIN BINARY BLENDS OF UNIFORM PS BYRHEO-OPTICAL FOURIER-TRANSFORM IRSPECTROSCOPYSiesler H W; Hayes C; Bokobza L; Monnerie LEssen,University; ESPCI

Rheo-optical FTIR spectroscopy was used to measureorientation and orientational relaxation in binary blendsof long- and short-chain linear PS. Films were stretchedat constant strain rate at various temperatures above Tg.17 refs.

EUROPEAN COMMUNITY; FRANCE; GERMANY; WESTERN

EUROPE

Accession no.514364

Item 300Journal of Applied Polymer Science52, No.7, 16th May 1994, p.975-83SIMULTANEOUS MEASUREMENT OF WATERDIFFUSION, SWELLING AND CALCIUMCARBONATE REMOVAL IN A LATEX PAINTUSING FTIR-ATRBalik C M; Xu J RNorth Carolina,State University

An in-situ FTIR-ATR method was used to monitor thesorption processes of water and pH 1.3 sulphurous acidin two latex paints and the base polymer common toboth. The sorption kinetics could not be described bya simple Fickian model. The spectra also showedevidence of polymer swelling, which was confirmedin separate swelling measurements. Anomalousbehaviour was noted for the latex paint containingcalcium carbonate when exposed to sulphurous acid.The amount of water sorbed by this sample wentthrough a maximum, then decreased to a constant level.This was accompanied by similar variations in thedegree of swelling of the sample. These changes areexplained by the rapid loss of calcium carbonate fromthis particular paint upon exposure to acidic solutions,followed by structural rearrangement to fill in the voidsleft by the calcium carbonate particles. 19 refs.

USA

Accession no.511826



Item 301Macromolecular ReportsA31, Nos.3 & 4, 1994, p.261-70APPLICATION OF FTIR PHOTOACOUSTICSPECTROSCOPY IN THE DETERMINATION OFTHE LEVEL OF CHEMICAL MODIFICATIONOF JUTE FIBRESCherian X M; Satyamoorthy P; Andrew J J;Bhattacharya S KHindustan Lever Research Centre

FTIR photoacoustic spectroscopy was used to determinethe extent of acylation in acetylated jute samplesquantitatively and results were compared with thoseobtained by standard wet chemical titrimetricmeasurements. 12 refs.INDIA

Accession no.511745

Item 302Analyst119, No.4, April 1994, p.693-6ANALYSIS OF POLYMERS USING EVOLVED-GAS AND DIRECT-PYROLYSIS TECHNIQUESFares M M; Yalcin T; Hacaloglu J; Gungor A; Suzer SMiddle East,Technical University; Tubitak;Ankara,Bilkent University

Thermal analysis of PS, poly-p-methylstyrene and poly-alpha-methylstyrene was carried out using evolved-gasanalysis by IR and mass spectrometry and direct-pyrolysisanalysis by mass spectrometric techniques. Evolved-gasanalysis, both by IR and mass spectrometry, revealedfeatures due mainly to the corresponding monomers orstable, volatile and low relative molec.wt. degradationproducts. In direct-pyrolysis mass spectrometry, however,primary decomposition products and heavier fragmentssuch as dimers and trimers could also be detected. Theion-temp. profiles of the corresponding monomer ionsrevealed information about the thermal stability of thepolymers. 25 refs. (XXVIII Colloquium SpectroscopicumInternationale, York, UK, June/July 1993)TURKEY

Accession no.511583

Item 303Analytical Chemistry66, No.6, 15th March 1994, p.882-7FEASIBILITY OF EXTRACTION ANDQUANTIFICATION OF FIBRE FINISHES VIAON-LINE SUPERCRITICAL FLUIDEXTRACTION/FOURIER TRANSFORM IRSPECTROSCOPY(SFE/FTIR)Kirschner C H; Jordan S L; Taylor L T; Seemuth P DVirginia,Polytechnic Institute & State University;DuPont Co.

The SFE/FTIR technique was applied to analysis of fibrefinishes on fibre/textile matrices. Three different fibre

polymer types were examined (PU, polyamide andaramid), each requiring a different finish. Finishes rangedfrom a single-component polydimethylsiloxane oil tomore complex multicomponent finishes that includedvarious surfactants, fatty acid esters and soaps,antioxidants and oils. Off-line extraction showed all threefinishes to be over 89% extractable with pure carbondioxide. Calibration curves were established for the threefinishes, with relatively low error and reasonable detectionlimits. 6 refs.USA

Accession no.509562

Item 304IRC ’93/144th Meeting, Fall 1993. ConferenceProceedings.Orlando, Fl., 26th-29th Oct.1993, Paper 105, pp.28.012APPLICATIONS OF RAMAN SPECTROSCOPYTO THE ANALYSIS OF NATURAL RUBBERHendra P J; Jackson K D OSouthampton,University; Malaysian Rubber Producers’Research Assn.(ACS,Rubber Div.)

Applications of Fourier transform Raman spectroscopyto the analysis of NR are described. Of particular interestis the observation of main chain modifications duringvulcanisation and the ability to observe the conversion ofinsoluble to soluble sulphur under conditions appropriateto compounding and vulcanisation. The influence ofcrystallisation, both temperature and strain induced, onthe Raman spectrum of NR is also demonstrated. 9 refs.EUROPEAN COMMUNITY; UK; USA; WESTERN EUROPE

Accession no.505679

Item 305Polyolefins VIII. Conference Proceedings.Houston,Tx., 21st-24th Feb.1993, p.616-33. 42C1RAPID AND NON-DESTRUCTIVE QUALITYASSESSMENT OF POLYMERIC FILMS USINGNEAR-INFRARED SPECTROSCOPYMiller C EDupont Polymers(SPE,South Texas Section; SPE,ThermoplasticMaterials & Foams Div.)

The ability of near-infrared spectroscopy, combined withmultivariate statistics, to non-destructively determine theHDPE/LDPE ratio of PE blend films and the individuallayer thickness percentages of LDPE/nylon 6/ethylene-vinyl alcohol copolymer food packaging laminates isdemonstrated. 19 refs.USA

Accession no.504961

Item 306Polymer Testing13, No.1, 1994, p.25-34



CHARACTERISATION OF EPDM RUBBERMODIFIED WITH MALEIC ANHYDRIDE (MAH)BY DIFFUSE REFLECTANCE FTIR (DRIFT)Coutinho F M B; Ferreira M I PRio de Janeiro,Universidade Federal

A rapid technique for determining bound MAH contentin maleated EPDM rubbers was established. It is basedon the application of diffuse reflectance FTIR whichpermits the analysis of such products directly without anysample preparation other than removing unreactedmonomer and initiator. The spectrum obtained also allowsthe evaluation of the rubber’s relative oxidation extent.Baseline and band choices as well as calculation methodsrequired are discussed. 12 refs.BRAZIL

Accession no.503999

Item 307Journal of Applied Polymer Science51, No.7, 14th Feb.1994, p.1251-67POLARISED INTERNAL REFLECTANCESPECTROSCOPIC STUDIES OF ORIENTEDPOLY(ETHYLENE TEREPHTHALATE)Lofgren E A; Jabarin S AToledo,University

Polarised internal reflectance spectroscopy was used toevaluate molecular orientation and crystallinity of PETPfilm surfaces. Uniaxially and biaxially stretched sampleswere measured. All bands of interest were normalisedwith a reference band near 1410/cm, resulting fromphenylene ring vibrations. Normalisation was performedin order to overcome problems with sample contact andeffective thickness. Results using bands representingtrans and gauche rotamers at 1340 and 1370/cm,respectively, were related to data acquired using densityand birefringence techniques. Polarised internalreflectance spectroscopy was found to be well suited toinvestigations of polymer orientation and crystallinitysince it avoided limitations related to sample thicknessand clarity imposed by polarised transmission IRspectroscopy. Results agreed well with those obtainedby density, birefringence and refractive indexmeasurements. 34 refs.USA

Accession no.503928

Item 308Polymer Science Series A36, No.1, Jan.1994, p.48-51IR SPECTROSCOPIC STUDY OFPOLYCAPROAMIDE FIBRES WITH GRAFTEDPOLYGLYCIDYL METHACRYLATEKorolik E V; Buslov D K; Zhbankov R G; Mosina N Y;Nazar’ina L A; Druzhinina T V; Gal’braikh L SBelarus Academy of Sciences; Moscow,State TextileAcademy

IR spectra of polycaproamide fibre, polyglycidylmethacrylate and polycaproamide fibre grafted withpolyglycidyl methacrylate were recorded. Thecorresponding deconvolution spectra were calculated. Amodel spectrum of the graft copolymer was simulated.The spectral regions that were sensitive to localisation ofthe chains of grafted polyglycidyl methacrylate wereidentified, i.e. 3500-3100/cm (stretching vibrations of NHgroups), 1700-1500/cm (Amide I and Amide II absorptionbands), 1030-900/cm (Amide IV) and 720-640/cm(Amide V). It was found that polyglycidyl methacrylatewas grafted to the macromolecules of polycaproamidevia an amide nitrogen. 7 refs. (Full translation ofVys.Soed.A, 36, No.1, 1994, p.58-62)BELORUSSIA; CIS; COMMONWEALTH OF INDEPENDENTSTATES; RUSSIA

Accession no.503687

Item 309Applied Spectroscopy48, No.1, Jan.1994, p.72-8ANALYSIS OF SOME ERRORS IN THECALCULATION OF ORIENTATION FUNCTIONSFOR POLYMERS FROM INFRAREDDICHROISM MEASUREMENTSMyers C W; Cooper S LWisconsin,University; Delaware,University

Several sources of error may influence the calculationsof chain orientation carried with the use of data frominfrared dichroism experiments. Three specific problemsare the improper treatment of chain conformation, theimperfect polariser behaviour, and the inaccurateassumptions regarding the value of the angle between aparticular infrared-active transition moment and thepolymer chain axis. In this paper, a quantitative analysisis presented of the magnitudes of these errors for severalinfrared bands commonly employed to characterisepolymer orientation via infrared dichroism. 52 refs.USA

Accession no.503524

Item 310Journal of Polymer Science : Polymer Physics Edition32, No.1, 15th Jan.1994, p.29-35FTIR INVESTIGATION OF ION-DIPOLEINTERACTION IN STYRENE IONOMER/POLY(ETHYLENE OXIDE) BLENDSJong-Chul Lim; Jung-Ki Park; Hae-Young SongKorea,Advanced Institute of Science & Technology;Korea,Chungnam National University

FTIR was used to examine specific interactionscontributing to the partial miscibility in blends of styrene-sodium methacrylate copolymer and PEO. From the shiftsof carboxylate ion and ether group stretching bands, animportant specific interaction was found involving ion-dipole bonding between the ionic group in styrene



ionomer and the ether group in PEO. The asymmetricstretching vibration frequency of the carboxylate iongroup increases as the fractional amount of PEO in theblend is increased, while the symmetric stretchingfrequency is decreased. The ether group stretching bandis shifted to higher frequencies as the PEO content of theblend increases. From DSC and FTIR it was concludedthat ion-dipole interaction was the important mechanismthat determines miscibility in these styrene-sodiummethacrylate copolymer/PEO blends. 42 refs.KOREA

Accession no.502023

Item 311Journal of Polymer Science : Polymer Physics Edition32, No.2, 30th Jan.1994, p.383-6USE OF NEAR INFRARED (NIR)SPECTROSCOPY TO STUDY SPECIFICINTERACTIONS IN POLYMER BLENDSGhebremeskel Y; Fields J; Garton AConnecticut,University

With the use of model systems and blends ofpolycaprolactone and phenoxy resin, it is shown that dataobtained from the OH stretch overtone absorption in NIRis consistent with those from the OH stretch fundamentalin the mid-IR region. The advantages of NIR analysis ofspecific interactions are illustrated with spectra obtainedfrom thick films of blends of nylon 6 and the zinc salt ofsulphonated PS. 9 refs.USA

Accession no.501517

Item 312Polymer34, No.24, 1993, p.5099-105WATER ABSORPTION BY AN EPOXY RESINAND ITS EFFECT ON THE MECHANICALPROPERTIES AND INFRA-RED SPECTRADe’Neve B; Shanahan M E REcole Nationale Superieure des Mines de Paris

A filled epoxy resin used as a structural adhesive andbased on the diglycidyl ether of bisphenol A cured withdicyandiamide was subjected, in its bulk form, to ageingat 40, 55 and 70C and about 100% relative humidity.Gravimetric viscoelastomeric and FTIR studies wereeffected after various times of exposure to monitor wateringress and to link variations in mechanical behaviourwith chemical modifications occurring in the polymer.34 refs.EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.499766

Item 313Applied Spectroscopy47, No.11, Nov.1993, p.1747-50

MID-INFRARED SPECTRA FROM NEAR-INFRARED SPECTRA USING PARTIAL LEAST-SQUARESLew R; Balke S TToronto,University

Partial least-squares (PLS) was used to generate mid-infrared (MIR) spectra from near-infrared (NIR) spectra.The NIR spectra were obtained by in-line monitoring ofa molten blend of PE with PP during extrusion. Off-lineMIR spectra of blends were used to calibrate the PLSmethod, which was then employed to generate the MIRabsorbance spectrum of a 50:50-by-weight blend notincluded in the calibration set from its NIR spectrum. Thesynthesised MIR spectrum agreed very well with a directlymeasured one. 11 refs.CANADA

Accession no.497783

Item 314Macromolecules26, No.23, 8th Nov.1993, p.6237-42DETERMINATION OF SOLUTIONPOLYMERISATION KINETICS BY NEAR-INFRARED SPECTROSCOPY. I. LIVINGANIONIC POLYMERISATION PROCESSESLong T E; Liu H Y:Schell B A; Teegarden D M;Uerz D SEastman Kodak Co.

Near-IR spectroscopy (10000-4000/cm) was successfullyused to monitor conversion during conventional, anionicsolution polymerisation of styrene and isoprene tohomopolymers and block copolymers. The conversion ofthe vinyl protons in the monomer to methylene protonsin the polymer was easily monitored under conventional(10-20% solids) solution polymerisation conditions. Inaddition to the need for an inert probe, high samplingfrequencies were required since polymerisation timesranged from 5s in tetrahydrofuran to 20 minutes incyclohexane. Preliminary data indicate that near IR iscapable of detecting sequence distribution for taperedblock copolymers, geometric isomer content, andreactivity ratios for free-radical copolymerisation. 20 refs.USA

Accession no.497376

Item 315Macromolecules26, No.22, 25th Oct.1993, p.5954-8KINETICS OF DIACETYLENEPOLYMERISATION. AN FT-RAMAN STUDYKamath M; Kim W H; Li L; Kumar J; Tripathy S; BabuK N; Talwar S SMassachusetts,University; Indian Institute ofTechnology

Changes in the FT-Raman spectrum of 1,4-bis(3-quinolyl)buta-1,3-diyne as a function of gamma-ray



dosage is used to monitor the degree of monomer topolymer conversion in a solid-state topochemicalpolymerisation reaction. The relative intensities of thecharacteristic carbon-to-carbon triple bond peaks in thenonresonant FT-Raman spectra provide a nondestructivequantitative means to measure the conversion frommonomer to polymer. 36 refs.INDIA; USA

Accession no.497334

Item 316Journal of Polymer Science : Polymer Physics Edition31, No.12, Nov.1993, p.1769-77DYNAMIC RHEO-OPTICALCHARACTERISATION OF A LOW DENSITYPOLYETHYLENE/PERDEUTERATED HIGHDENSITY POLYETHYLENE BLEND BY TWODIMENSIONAL STEP-SCAN FTIRSPECTROSCOPYGregoriou V G; Noda I; Dowrey A E; Marcott C; ChaoJ L; Palmer R ADuke,University; Procter & Gamble Co.; IBM Corp.

Dynamic mechanical analysis coupled with polarisedstep-scan FTIR transmission and two-dimensionalcorrelation analysis was used to monitor the submolecularorientational responses of the components of asemicrystalline 50/50 blend of LDPE with perdeuteratedHDPE to a small amplitude uniaxial 23.47 Hz sinusoidalmechanical strain. Perdeuteration of the HDPE componentallowed the distinction of its response from that of theLDPE in the blend samples. Experiments were carriedout at room temp. Analysis of the data indicated that thecrystalline parts of the two components reorient atdifferent rates, with the functional groups of the highdensity portion reorienting faster, in general, than thoseof the LDPE in response to the mechanical strain. 29 refs.USA

Accession no.496076

Item 317Synthetic Metals59, No.2, July 1993, p.141-9CHARACTERISATION FROM XPS, FTIR ANDRAMAN SPECTROSCOPIES OF FILMS OFPOLY-P-PHENYLENE PREPARED BYELECTROPOLYMERISATION OF BENZENEDISSOLVED IN KETYL PYRIDINIUMCHLORIDE-ALUMINIUM TRICHLORIDEMELTING SALTLere-Porte J P; Radi M; Chorro C; Petrissans J;Sauvajol J L; Gonbeau D; Pfister-Guillouzo G; LouarnG; Lefrant SMontpellier,University; Pau,Universite;Nantes,Laboratoire de Physique Cristalline

X-ray photoelectron(XPS) studies of the above filmsshowed a small amount of residual chlorine. The shape

and strong intensity of the extrinsic part of thephotoluminescence could be related to a large amount ofstructural defects in the films, but the distribution of thesedefects was relatively homogeneous. Raman spectraclearly showed the presence of segments with smallconjugation lengths in the films. FTIR spectra showedthat the degree of polymerisation was smaller than thosereported for electrochemical oxidation of benzene insulphur dioxide at low temp. These results indicated thatthe films obtained by this technique showed somesimilarities with ‘Kovacic compounds’. 29 refs.EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.495093

Item 318Journal of Polymer Science : Polymer Physics Edition31, No.11, Oct.1993, p.1487-94PHYSICAL MODIFICATIONS OF PROPYLENE/ETHYLENE-PROPYLENE-DIENE-MONOMERRUBBER SURFACES. I. DETERMINATION OFSURFACE COMPOSITION AND SURFACEORDER BY FOURIER TRANSFORMINFRARED-ATTENUATED TOTALREFLECTANCEBonnerup C; Gatenholm PChalmers University of Technology

Results are presented of an investigation of the possibilityof using the FTIR-ATR technique for determining surfacecomposition and surface crystallinity of PP/EPDM blendscontaining varying amounts of EPDM. 37 refs.SCANDINAVIA; SWEDEN; WESTERN EUROPE

Accession no.494717

Item 319Applied Spectroscopy47, No.7, July 1993, p.928-32USE OF WATER AS AN INTERNAL STANDARDIN THE DIRECT MONITORING OF EMULSIONPOLYMERISATION BY FIBRE-OPTIC RAMANSPECTROSCOPYWang C; Vickers T J; Mann C KFlorida State University

The direct analysis of the organic phase of an emulsionpolymerisation is described. Quantification using thebending mode peak of water, which makes up the bulk ofthe reaction medium, as an internal standard is discussed.The process is demonstrated for methyl methacrylate butis generally applicable to emulsion polymerisations. Itdoes not require the introduction of an extraneous internalstandard component into the reaction mixture. 4 refs.USA

Accession no.490646

Item 320Journal of Applied Polymer Science



49, No.5, 5th Aug.1993, p.925-34MOLECULAR CHANGES IN PETP YARNSDURING STRETCHING MEASURED WITHRHEO-OPTICAL INFRARED SPECTROSCOPYAND OTHER TECHNIQUESvan den Heuvel C J M; Heuvel H M; Faassen W A;Veurink J; Lucas L JAkzo Research Laboratories

A method was developed for measuring IR spectra duringthe mechanical deformation of yarns. This rheoopticaltechnique was applied to study the molecular processesthat take place along the stress-strain curve of PETP yarns.The results were combined with data obtained from sizeexclusion chromatography and tensile measurements atelevated temperatures. The results indicate that the firstmodulus maximum marks the breakdown of theamorphous entanglement network and the start ofmolecular uncoiling by gauche-to-trans transitions. Inaddition, stress develops on the crystals and particularlyon tie molecules with a short contour length in theamorphous domains. Ultimately, molecular fracture oftaut-tie molecules causes the modulus to pass through asecond maximum. The chain ends of broken moleculesrecoil by trans-to-gauche transitions. Local stressaccumulation will lead eventually to yarn rupture.EUROPEAN COMMUNITY; NETHERLANDS; WESTERNEUROPE

Accession no.489164

Item 321Polymer34, No.14, July 1993, p.3010-8SYNTHESIS AND INFRA-REDSPECTROSCOPIC CHARACTERISATION OFRANDOM COPOLYMERS OF 4-VINYLPHENOLWITH N-ALKYL METHACRYLATESXu Y; Painter P C; Coleman M MPennsylvania,University

Random copolymers of 4-vinylphenol with n-alkylmethacrylates were prepared by free radicalcopolymerisation of 4-t-butyldimethylsilyloxystyrene andthe corresponding alkyl methacrylates in benzene at 60Cusing AIBN as initiator. Reactivity ratios were determinedby the Kelen-Tudos method. Selective removal of the t-butyldimethylsilyl protective group was effected bytetrabutylammonium fluoride in THF at ambienttemperature. The copolymers were characterised by IRspectroscopy. 20 refs.USA

Accession no.488248

Item 322Polymer34, No.14, July 1993, p.3004-9PHYSICOCHEMICAL CHARACTERISATIONOF POLYPROPYLENE FILMS GRAFTED BY

POLYACRYLIC ACID. I.Romero M A; Domard A; Petit DClaude Bernard,Universite; Centre de Recherche deVoreppe SA

ATR-IR spectroscopy was used to characterise the graftingof PP films by polyacrylic acid. A technique allowing theseparation of the grafted part from the unmodified partof the specimen was also used. The effects of pretreatmentof the films to remove additives were investigated. It wasshown that grafting always started from the interfacebetween the PP and the polymerisation solvent. The resultssuggested that it should be possible to control the locationof grafting both by the content of antioxidants and bytheir extraction. 27 refs.EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.488247

Item 323Polymer34, No.14, July 1993, p.2934-45FOURIER TRANSFORM INFRA-REDSPECTROSCOPY ON THETHERMOOXIDATIVE DEGRADATION OFPOLYBENZIMIDAZOLE AND OF APOLYBENZIMIDAZOLE/POLYETHERIMIDEBLENDMusto P; Karasz F E; MacKnight W JMassachusetts,University

The thermooxidative degradation of polyphenylenebibenzimidazole (PBI) and a blend of PBI with Ultem 1000polyetherimide (PEI) was investigated by Fourier transformIR (FTIR) spectroscopy, under conditions which allowedreal time monitoring of molecular changes taking placeduring the process. The data provided information on thekinetics and mechanism of degradation in its early stages.The FTIR spectra of the blend were analysed by subtractionspectroscopy, allowing the fate of the two blendcomponents to be selectively studied. No chemicalinteraction between PBI and PEI was detectable by FTIRduring the degradation process. 12 refs.

GENERAL ELECTRIC CO.USA

Accession no.488238

Item 324Antec ’92. Plastics: Shaping the Future. Volume 1.Conference Proceedings.Detroit, Mi., 3rd-7th May 1992, p.211-4. 012ON-LINE FTIR SPECTROSCOPICMEASUREMENT OF ERUCAMIDE AND SILICAIN MOLTEN LDPEFidler R AAutomatik Machinery Corp.(SPE)

The design of an on-line Fourier transform IR analyserand its application to the characterisation of an anti-



blocking agent (silica) and lubricant (erucamide) in LDPEsamples are described. 8 refs.USA

Accession no.483822

Item 325Makromolekulare Chemie194, No.6, June 1993, p.1545-59LINEAR-TEMPERATURE PROGRAMMEDPYROLYSIS OF THERMORESISTANTPOLYMERS - MASS AND FTIRSPECTROMETRIES. II. AROMATICPOLYESTERS AND COPOLYESTERSHummel D O; Neuhoff U; Bretz A; Duessel H JKoln,Universitat; Angewandte Spektrometrie Koeln eV

Results are presented of an investigation of the use oflinear-temp. controlled pyrolysis with subsequent analysisof the pyrolysates (volatiles and residues) by 18Velectron-impact mass spectrometry and FTIRspectrometry to provide information on the thermaldegradation mechanisms of aromatic polyesters, inparticular polyhydroxybenzoic acid and oxybenzoate-oxynaphthoate copolymer (Vectra). 13 refs.EUROPEAN COMMUNITY; GERMANY; WESTERN EUROPE

Accession no.483277

Item 326Makromolekulare Chemie194, No.6, June 1993, p.1527-36NON-DESTRUCTIVE DETERMINATION OFTHE RESIDUAL MONOMER CONTENT INPOLYMERS BY RAMAN SPECTROSCOPYDywan F; Hartmann B; Klauer S; Lechner M D; RuppR A; Woehlecke MOsnabruck,University

Raman spectroscopy was established by means of acomparative study and by calibration to be a suitable non-destructive method for determination of monomerconcentration in solid PMMA samples. Although theeffect of the internal field on the refractive index and onthe Raman intensity of a polymer solution in a monomerwas considered, the Raman scattering cross-section of thecarbonyl stretching vibration of the monomer was shownto be twice as large as that of the polymer. 42 refs.EUROPEAN COMMUNITY; GERMANY; WESTERN EUROPE

Accession no.483275

Item 327Journal of Applied Polymer Science48, No.9, 5th June 1993, p.1579-85CHARACTERISATION OF GRAFTEDPOLYETHYLENE BY CONTACT ANGLEHYSTERESIS AND ESCA STUDIESKonar J; Sen A K; Bhowmick A KIndian Institute of Technology; Fort Gloster Industries Ltd.

LDPE was functionalised in the bulk through dicumylperoxide-initiated grafting of dibutyl maleate andvinyltrimethoxysilane in the temp. range from 140 to200C. The functionalised surfaces were characterisedthrough contact angle and contact angle hysteresismeasurements as well as through ESCA studies. Thedegree of grafting was determined by IRspectrophotometry. From the ESCA patterns of themodified polymers, the atomic ratios of oxygen to carbonand silicon to carbon were calculated. Determination ofan empirical relation between contact angle hysteresis andthe oxygen-carbon ratio of the functionalised polymersurfaces was attempted. It was found that the contact anglevalue for PE decreased with increasing oxygen-carbonratio. Contact angle hysteresis increased with increase inthe degree of grafting. The total surface energy increasedwith grafting. The surface energy of the silane-graftedPE was found to be lower than that of dibutyl maleate-grafted PE. 13 refs.INDIA

Accession no.483225

Item 328Polymer34, No.11, 1993, p.2445-6INVESTIGATION OF THE INTERPHASE OF ASILANE-FINISHED GLASS FIBRE/VINYLESTER USING A MICROSCOPIC FTIRSPECTROMETERIkuta N; Suzuki Y; Maekawa Z; Hamada HOsaka Municipal Industrial Research Institute; NittoBoseki Co.Ltd.; Kyoto,Institute of Technology

Glass fibre strand was treated with gamma-methacryloxypropyltrimethoxysilane as coupling agentand used to reinforce a vinylester resin. The interface wasstudied by FTIR. Silane was able to migrate into the resinand influence curing at a distance (200 micrometres)greater than the thickness of the interphase. 3 refs.JAPAN

Accession no.481357

Item 329Makromolekulare Chemie194, No.5, May 1993, p.1249-72STOPPED-FLOW FOURIER TRANSFORMINFRARED STUDIES IN POLYMERCHEMISTRYBrittain W J; Aquino E C; Dicker I B; Brunelle D JAkron,University; Du Pont Merck Pharmaceutical Co.;GE Corporate R & D

The application of stopped-flow FTIR spectroscopy togroup transfer polymerisation(GTP) and cyclic oligomericcarbonate formation was studied. The effect of catalyststructure, propagating end stereochemistry and degree ofpolymerisation on the rate of monomer addition in GTPwas investigated. The main GTP termination process was



identified and characterised. Model reactions were usedto study kinetics of acyl ammonium salt formation andsubsequent conversion to urethane. The results were usedto develop further the mechanism of bisphenol-A-bischloroformate macrocyclisation. 44 refs.USA

Accession no.478673

Item 330Polymer Science Series A35, No.3, March 1993, p.311-4IR SPECTROSCOPIC STUDY OF THE EFFECTOF IONISING IRRADIATION ON THESTRUCTURE OF POLYACRYLONITRILEPlatonova N V; Klimenko I B; Maiburov S PSt.Petersburg,Textile & Light Industry Institute

IR spectroscopic analysis showed that the treatment ofpolyacrylonitrile films and fibres by gamma-irradiationled to cleavage of the polymer chains forming carbonyl-containing functional groups, the composition of whichdepended on the treatment conditions. The presence ofterminal methyl groups in the treated polymer wasdetected in its IR spectra only in the presence of residualbasic solvent. The occurrence of conformational changeswas revealed by the behaviour of the absorption bands.12 refs.RUSSIA

Accession no.478498

Item 331Polymer34, No.8, 1993, p.1649-52FOURIER TRANSFORM-RAMANSPECTROSCOPIC STUDY OF ELECTRICALLYCONDUCTING POLYPYRROLE FILMSJenden C M; Davidson R G; Turner T GAustralia,Defence Science & Technology Org.

The chemical structure of electrically conductingpolypyrrole films doped with p-toluene sulphonate anddodecyl sulphate was studied by Fourier Transform-Raman spectroscopy. The spectra were compared withthose from the corresponding reduced polymers afterdedoping and found to be consistent with polaron andbipolaron descriptions of the electron transportmechanism in polypyrrole. 15 refs.AUSTRALIA

Accession no.478461

Item 332Journal of Polymer Science : Polymer Physics Edition31, No.6, May 1993, p.677-92FT-RAMAN INVESTIGATION OF THETHERMAL CURING OF PMDA/ODA POLYAMICACIDSJohnson C; Wunder S L

Temple University

The effect of solvent (NMP/xylene) on the curingreactions of PMDA/ODA polyamic acids was investigatedin depth using Fourier transform-Raman spectroscopy.The solvent was found to have a dramatic effect both onthe rate of cure and on the final extent of conversion ofthe ring closure reaction. The kinetic data is shown to beconsistent with the concept that the amount of solventpresent in the films affects the rate of imidisation. 38 refs.USA

Accession no.478344

Item 333Cellular Polymers12, No.1, 1993, p.31-45IR SPECTROSCOPY OF SITE-DEPENDENTINHOMOGENEITIES IN CONVENTIONALFLEXIBLE PU FOAMSteger W E; Machill S; Herzog K; Gerhards R; JussofieI; Schator HDresden,University; Goldschmidt Th.,AG

An IR microscope was used to study the cell membranesof a flexible PU foam. Correlations were made ofabsorbance values of methyl signals with absolutethicknesses calculated from the interference patternsobserved in some spectra. 18 refs.EUROPEAN COMMUNITY; GERMANY; WESTERN EUROPE

Accession no.477183

Item 334Applied Spectroscopy47, No.3, March 1993, p.321-9ANALYSIS OF POLYMER-DISPERSED LIQUIDCRYSTALS BY IR SPECTROSCOPYMcFarland C A; Koenig J L; West J LCase Western Reserve University; Liquid CrystalInstitute

A comparison is made of the polymer and liquid crystaldroplet regions within polymer-dispersed liquid crystalfilms using FTIR microspectroscopy. IR functional groupimages of a droplet showed characteristic texturescorresponding to the visual images of the same droplet.The textures in the IR images changed with IR polarisationand with an applied electric field. Hysteresis was observedin the IR region as a function of voltage and temperature.USA

Accession no.476052

Item 335Polymer International31, No.4, 1993, p.391-6RAMAN SPECTROSCOPIC ANALYSIS OF THEMICROSTRUCTURES OF BUTADIENE-ACRYLONITRILE COPOLYMERSEdwards H G M; Johnson A F; Lewis I R; Cowie J M G



Bradford,University; Heriot-Watt University

The polybutadiene microstructures of a number ofcopolymers of butadiene and acrylonitrile were studiedby quantitative Raman spectroscopy and a comparisonwas made with IR studies of these copolymers. Theintensities of the v(C:C) and the v(CN) bands were alsoused to determine the amount of each monomer in thecopolymer. 24 refs.EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.474667

Item 336Polymer34, No.5, 1993, p.933-7ANALYSIS OF PHOTOOXIDATION OFPOLYMER MATERIALS BY PHOTOACOUSTICFTIRDelprat P; Gardette J LBlaise Pascal,Universite

Injection moulded PP plates, with and without titaniumdioxide pigment, were irradiated in a medium-acceleratedphotoageing device to the equivalent of 1 year of outdoorexposure. Photoacoustic FTIR spectra of photooxidisedsamples were recorded. They were analysed also bytransmission micro-FTIR analysis of cross-sectionedlayers. The oxidation profiles monitored were shown toarise from oxygen diffusion limitation and also from theheterogeneous absorption of light by the titanium dioxide-pigmented samples. The intensity of the carbonylabsorbance measured by photoacoustic FTIR wasdetermined and it was shown that the front layerdegradation monitored by both techniques had identicalvalues. This rapid and non-destructive technique may beused to quantitatively measure the surface degradationof aged polymers. 21 refs.EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.474356

Item 337Journal of The Textile Institute84,No.1,1993,p.85-98ON-LINE MEASUREMENT OF POLYVINYLALCOHOL SIZE ON WARP YARNS USING ANEAR-IR DIFFUSE REFLECTANCESPECTROSCOPY METHODGhosh S

Uniform application of size on warp yarns is essential toachieve desired weaving efficiency; however, currentlyno method is available to measure sizing materials on thewarp while it is being processed on a sizing machine. Amethod of on-line measurement of size on the warp usingnear-IR diffuse reflectance spectroscopy method isdescribed. A prediction model regression equation isdeveloped using a PLS modelling procedure using asegment of the near-IR spectrum which is most sensitive

to changes in size concentration on the warp. A discussionof the spectral region sensitive to the analyte (partlyhydrolysed polyvinyl alcohol) but less sensitive to thesubstrate (polyester/cotton) is provided. 8 refs.EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.472430

Item 338European Polymer Journal29,No.4,April 1993,p.475-81QUANTITATIVE ANALYSIS OF COPOLYMERSBY FOURIER TRANSFORM IRSPECTROSCOPYMao R; Huglin M B; Davis T PSalford,University; ICI

Quantitative analysis of a series of copolymers of 2-((phenylamino)carbonyl)oxyethyl methacrylate and 1-methyl-2-phenoxyethyl methacrylate was carried out byFTIR spectroscopy. Emphasis was placed on aspectsoptimising the accuracy of the technique. Theirreproducibility resulting from the use of cast films wasshown to be overcome when using solutions. The criteriafor solvent selection were established. Highly satisfactorycalibration was afforded by blends of the twohomopolymers in solution, thus providing an absolutecalibration and obviating the use of model compounds orcopolymers of known composition. 23 refs.EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.470745

Item 339Journal of Polymer Science : Polymer Physics Edition30,No.12,Nov.1992,p.1305-10ANALYSIS OF POLYMER FILMS BY DIFFUSEREFLECTANCE FTIR SPECTROSCOPY:CHARACTERISATION OF TERMINALCARBOXYL FUNCTIONALITIESde Donato P; Cases J M; Humbert B; Lutgen P;Feyder GINPL; Nancy,Universite

IR spectra of PETP films were obtained, with an excellentsignal-to-noise ratio, by diffuse reflectance measurementson a KBr matrix using FTIR spectroscopy. All the spectraexhibited a new band at 1684 cm/1, characteristic of theC = 0 stretching vibration of a terminal acidic function inthe presence of internal hydrogen bonds. These acidicfunctions may be used to monitor polymerisation rate.19 refs.EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.470191

Item 340Progress in Colloid & Polymer ScienceVol.90,1992,p.202-5FOURIER TRANSFORM INFRARED



SPECTROSCOPY STUDIES ON EPOXYNETWORKSScherzer T; Strehmel V; Taenzer W; Wartewig SMerseburg,Technische Hochschule

Epoxy networks based on the diglycidyl ether of bisphenolA cured with aliphatic diols of varying chain length inthe presence of magnesium perchlorate or with 4,4'-diaminodiphenylmethane and imidazole, respectively,were studied by FTIR spectroscopy. The effect of theaccelerator on the epoxy/amine system was investigated.10 refs. (29th Europhysics Conference onMacromolecular Physics,’Physics of PolymerNetworks’,European Physics Society/TechnicalUniversity Merseburg,Alexisbad/Harz, Germany,Sept.1991)EUROPEAN COMMUNITY; GERMANY; WESTERN EUROPE

Accession no.467804

Item 341Rubber Chemistry and Technology65,No.4,Sept./Oct.1992,p.836-50DIRECT CHARACTERISATION OF TYREMATERIALS BY PHOTOACOUSTICALINFRARED AND PROTON INDUCED X-RAYEMISSION SPECTROSCOPYWaddell W H; Parker J RPPG Industries Inc.

Photoacoustical Fourier transform IR spectroscopy andproton induced X-ray emission spectroscopy were usedto characterise tread lugs sectioned from two worn off-the-road tyres. The tyres had experienced similar servicebut displayed significantly different performance in that‘chipping/chunking’ was visible in one tyre brand. Thetwo techniques were also used to examine a variety ofrubber compounding ingredients, such as polymers andfillers, and model tyre compounds containing differentlevels of these ingredients. 39 refs.USA

Accession no.464954

Item 342Polymer33,No.23,1992,p.5085-9QUANTITATIVE ANALYSIS OF THE SI-HGROUPS FORMED ONPOLY(DIMETHYLSILOXANE) SURFACES. ANATR FTIR APPROACHGaboury S R; Urban M WNorth Dakota State University

Silane groups formed on the surface ofpolydimethylsiloxane elastomers by argon or nitrogen gasplasma treatments were determined. Kramers-Kronigtransformation of the ATR spectra of standard solutionscontaining Si-H species allowed construction ofcalibration plots which were independent of the angle ofincidence, crystal coverage and sample refractive index.

The Si-H concentrations of the plasma-treatedpolydimethylsiloxanes were calculated from thecalibration plots, and indicate that gas/plasma treatmentsof polydimethylsiloxane substrates result in Si-Hfunctionality gradients with higher concentrations nearthe elastomer surface. Relevance to biocompatibility isindicated. 23 refs.USA

Accession no.464495

Item 343European Polymer Journal28,No.9,Sept.1992,p.1147-50INFRARED SPECTROPHOTOMETRY OFMALEIC ANHYDRIDE TERPOLYMERSStaudner E; Kysela G; Turayova Z; Slyskova E;Brissova MSlovak Technical University

A modified internal standard method has been developedto determine the compositions of terpolymers of maleicanhydride with styrene and a methacrylate or an acrylate.The method involves IR spectrophotometry of thesamples. IR spectra are recorded by means of thepotassium bromide technique. The IR analysis is basedon integrated absorption of the anhydride and estercarbonyl groups. 9 refs.CZECHOSLOVAKIA; EASTERN EUROPE

Accession no.464393

Item 344Macromolecules25,No.24,23rd Nov.1992,p.6621-30FOURIER TRANSFORM INFRARED ANDELECTRON SPECTROSCOPY FOR CHEMICALANALYSIS STUDIES OF BLOCK COPOLYMERSOF STYRENE AND DIMETHYLSILOXANEChen X; Gardella J A; Kumler P LBuffalo,State University of New York; New York,StateUniversity

The surface segregation of poly(dimethylsiloxane) inchloroform solution cast films of styrene anddimethylsiloxane block copolymers in AB diblock as wellas ABA and BAB triblock types was investigated byESCA and ATR FTIR. Poly(dimethylsiloxane) surfacesegregation was mainly dependent on the architecture ofthe block copolymers and the poly(dimethylsiloxane)block length. AB-type diblock copolymers exhibited arelatively thicker pure poly(dimethylsiloxane) surfacelayer, and the surface segregation effects were detectedup to the ATR FTIR sampling depth. All three types ofblock copolymers presented much higherpoly(dimethylsiloxane) concentrations on their outermostsurface region (about 0.27A from the air interface) thanthe bulk materials.USA

Accession no.464314



Item 345Polymer Bulletin29,No.5,Nov.1992,p.527-33IN SITU INFRARED KINETIC STUDY OF THETHERMAL CONVERSION OFPOLYPHENYLENE-1,2-DIBROMOETHYLENETO POLYPHENYLENEACETYLENEPatel V L; Church S P; Khan NCourtaulds Research

The thermal reaction of polyphenylene-1,2-dibromoethylene under argon flow was investigated usingin situ kinetic IR spectroscopy. Between 200 and 250C,the reaction proceeded via elimination of hydrogenbromide to form a copolymer containing phenyleneacetylene linkages partially interrupted by brominatedunits. The activation energy was considerably below theC-Br bond dissociation energy. 5 refs.EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.462972

Item 346Polymer33,No.20,1992,p.4219-29STRUCTURE OR THE SKIN AND CORE OFULTRADRAWN POLYETHYLENE FILMS BYVIBRATIONAL SPECTROSCOPYAgosti E; Zerbi G; Ward I MMilano,Politecnico; Leeds,University

Films about 80 micrometres thick were studied by ATRIR spectroscopy at various angles of incidence, IRabsorption spectroscopy including polarised light andvariable temperature, and Raman spectroscopy underdifferent scattering geometries. The results wereinterpreted on the basis of the theoretical concepts ofthe lattice dynamics of ordered and disorderedpolymethylene systems previously worked out. Agradient of molecular and crystalline structures wasfound from the surface into the core. The skin was highlyorthorhombic. Moving inside the film, both monoclinicand orthorhombic lattices coexisted. A new phase withisolated trans-planar sequences was observed in the core.Various kinds of collective and oriented or isolatedconformational disorder were identified. A molecularmodel is proposed for the process of orientation duringdrawing. 47 refs.EUROPEAN COMMUNITY; ITALY; UK; WESTERN EUROPE

Accession no.462787

Item 347Macromolecules25,No.19,14th Sept.1992,p.5069-73POLYMER MUTUAL DIFFUSIONMEASUREMENTS USING INFRARED ATRSPECTROSCOPYvan Alsten J G; Lustig S RDu Pont de Nemours E.I.,& Co.Inc.

A technique for measuring mutual diffusion coefficientsof polymers in the melt using IR attenuated totalreflectance spectroscopy is described. This methodmeasures the dissolution of a polymeric diffusant into amatrix of another polymer and is applicable to anydiffusion couple with IR-distinguishable bands. In situmeasurements of the diffusion of various molecularweight polystyrenes (deuterated into a matrix ofhydrogenated) and the temp. dependence of the diffusionof PMMA (deuterated into hydrogenated) are presented.The method can operate from room temp. to 400C.Relevance to welding and bonding is indicated. 11 refs.USA

Accession no.462778

Item 348Macromolecules25,No.19,14th Sept.1992,p.4996-5001INFRARED AND THERMAL ANALYSISSTUDIES OF TRANSREACTIONS IN PHENOXY-POLYCARBONATE BLENDSYang X; Painter P C; Coleman M MPennsylvania,State University

Bisphenol A phenoxy polymers and bisphenol Apolycarbonates from a variety of sources and with differentmolec. wts. were blended in solution and cast. Changesfrom aromatic to aliphatic carbonate groups were monitoredby FTIR using a heating cell mounted inside the samplechamber. Significant ester exchange reactions were seenat temps as low as 160C. DSC revealed changes in Tg forrepeat scans. Differences between reactions occurring insolution blending and melt blending are discussed. 9 refs.USA

Accession no.462768

Item 349Journal of Natural Rubber Research7,No.2,p.152-5FTIR STUDIES ON AMINO GROUPS INPURIFIED HEVEA RUBBERAik-Hwee E;Tanaka Y;Seng-Neon GMALAYA,UNIVERSITY; TOKYO,UNIVERSITY OFAGRICULTURE & TECHNOLOGY

The FTIR spectrum of NR showed characteristic bandsof attached nitrogenous compounds at 3280 and 1540cm/1. These bands diminished if the fresh field latex wastreated with enzyme followed by washing in the presenceof surfactant. A band at 3320cm/1 that remained after thetreatment indicated the presence of residual amino acidsbonded to the rubber particles. 8 refs.JAPAN; MALAYSIA

Accession no.461830

Item 350Makromolekulare Chemie



193,No.9,Sept.1992,p.2413-20FTIR SPECTRA AND CHAIN CONFORMATIONSIN THE CRYSTALLINE FORMS ANDCLATHRATES OF SYNDIOTACTIC POLY-P-METHYLSTYRENEGuerra G;Dal Poggetto F;Iuliano M;Manfredi CNAPOLI,UNIVERSITA

IR spectra are reported for syndiotactic poly-p-methylstyrene (PPMS) samples exhibiting variouscrystalline forms and clathrate structures. Bands due tothe syndiotactic stereostructure, bands typical of the twodifferent chain conformations observed in the crystallinestructures, and bands sensitive to intermolecularinteractions typical of the different modes of chainpacking are pointed out. Observed similarities withsyndiotactic PS are indicated. A complete assignment viaFourier transform IR analysis of chain conformations ispresented for all the known crystalline forms andclathrates of syndiotactic PPMS. 18 refs.EUROPEAN COMMUNITY; ITALY; WESTERN EUROPE

Accession no.461408

Item 351Macromolecules25,No.16,3rd Aug.1992,p.4119-26POLYSTYRENE PHOTOOXIDATION. I.IDENTIFICATION OF THE IR-ABSORBINGPHOTOPRODUCTS FORMED AT SHORT ANDLONG WAVELENGTHSMailhot B;Gardette J-LBLAISE PASCAL,UNIVERSITE

PS (Gedex) films were exposed to radiation of longwavelength (above 300 nm) and short wavelength (253.7nm) under atmospheric oxygen. Changes in the FTIRspectra of the photooxidised samples were followed andseveral postirradiation treatments including chemicalderivatisation performed. HPLC analysed the lowmolec.wt. fragments that were obtained after extractionby methanol. The absorption maxima which were foundin the carbonyl and hydroxyl regions of the IR wereassigned, and the corresponding photoproducts wereidentified. 24 refs.EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.460096

Item 352SAMPE Journal28,No.4,July/Aug.1992,p.37-42EPOXY CURE MONITORING USING FIBRE-OPTIC RAMAN SPECTROSCOPYMyrick M L;Angel S M;Lyon R E;Vess T MLAWRENCE LIVERMORE NATIONALLABORATORY

The curing of an epoxy matrix used for wet-filament-wound composites was monitored using Raman

spectroscopy measured over fibre optics. The extent ofthe reaction of the epoxy resin (DER 332) as a functionof time was measured through changes in peak heights ofseveral vibrational modes. Temperature measurementswere made over the same fibre optics used to obtain thecure chemistry data by measuring the intensity of anti-Stokes Raman scattering from the epoxy resin. Bothsingle-fibre and dual-fibre probes were evaluated. 20 refs.USA

Accession no.460085

Item 353Applied Spectroscopy46,No.7,July 1992,p.1113-6ATR/IR SPECTROSCOPIC METHOD FORFOLLOWING PHOTO-POLYMER CURINGSnyder R W;Fuerniss S JIBM CORP.

A method for studying the photo-induced polymerisationof photoresists and solder masks at the substrate/photopolymer interface, using ATR and IR spectroscopyis described. The technique is especially useful for dryfilm photoresists and gives information on cure levelsaffected by exposure dose and photoresist thickness. Thephotoprocessing of Vacrel 8100 series solder mask andRiston 3100 series photoresists from Dupont are used asexamples. 23 refs.

DU PONT DE NEMOURS E.I.,& CO.INC.USA

Accession no.459390

Item 354Polymer33,No.7,1992.p.1370-3CARBON-13 LIQUID- AND SOLID-STATENUCLEAR MAGNETIC RESONANCE ANDINFRA-RED STUDIES OF AMINE-CUREDEPOXY RESINSFischer A;Schlothauer K;Pfitzmann A;Spevacek JCZECHOSLOVAK ACADEMY OFSCIENCES,INST.MACR.CHEM.;MERSEBURG,UNIVERSITY

The final network structure of an epoxy resin system andthe course of reaction of bisphenol a diglycidyl ether with1-cyanoguanidine as curing agent dissolved in dimethylformamide in the presence of different accelerators werestudied by liquid-state carbon-13 NMR spectroscopy,solid-state carbon-13 cross-polarisation/magic anglespinning NMR spectroscopy and IR spectroscopy.Fractions of reactive groups such as oxirane rings, primaryand secondary hydroxyl groups, imide and nitrile groupswere detected as functions of epoxy consumption andreaction conditions. Structural tautomerism of the curingagent, the influence of water, the reaction of nitrile groupsand other structural features of the curing system wereexamined. 11 refs.



CZECHOSLOVAKIA; EASTERN EUROPE; GERMANY

Accession no.452021

Item 355Die Makromolekulare Chemie- MacromolecularsymposiaNo.53,Jan.1992,p.89-103CHARACTERISATION OF POLYMERDEFORMATION BY RHEO-OPTICAL FOURIER-TRANSFORM INFRARED SPECTROSCOPYSiesler H WESSEN,UNIVERSITY

The above technique is explained with emphasis on anewly constructed computer-controlled variable-temp.stretching machine which allows monitoring ofvibrational spectra and stress-strain diagrams duringdeformation of polymer films up to 523K. Results aregiven for a polyetherurethane elastomer and PETP toidentify conformational changes and transitions, chainalignment and strain-induced crystallisation. 24 refs.(Presented at Polymer 91,Int.Symp.on Polymer Materials- Preparation,Characterisation & Properties. IUPAC,Macromolecular Div., Melbourne,Australia,10t-15thFeb.1991).

GERMANY

Accession no.448515

Item 356Materiaux & Techniques79,No.11-12,Nov-Dec.1991,p.69-72DETERMINATION OF 5-ETHYLIDENENORBORNENE (ENB) BYFOURIER-TRANSFORM INFRAREDSPECTROSCOPY (FTIR)EXXON CHEMICAL FRANCE; EXXONRESEARCH & ENGINEERING CO.

A sensitive Fourier transform infrared spectroscopicmethod for the determination of ENB content in ethylenepropylene diene (EPDM) copolymers is described indetail. It is applicable for ENB contents in the 0.1 to 10%weight range. The repeatability standard deviation of themethod is given as 0.020 and the reproducibility standarddeviation, 0.080 at the 5% weight level.

EUROPEAN COMMUNITY; FRANCE; USA; WESTERN

EUROPE

Accession no.445896

Item 357Shawbury, 1992, pp.iii,333. LS.300. 12ins. 14/5/92.9922RAPRA COLLECTION OF INFRARED SPECTRAOF RUBBERS, PLASTICS ANDTHERMOPLASTIC ELASTOMERSSidwell JRAPRA TECHNOLOGY LTD.

This collection of spectra includes both transmission andpyrolysate (condensed phase) spectra of a comprehensiverange of technically important rubber and plastic basedmaterials. Included are homopolymers, copolymers andblended materials, and pyrolysate spectra have bynecessity been obtained for crosslinked rubbers andthermoset materials. Materials are indexed under bothpolymer type and trade name. Photocopies of this sourceare not available. The publication can be purchased fromRapra’s Publication Sales group.EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.445621

Item 358Die Makromolekulare Chemie- MacromolecularsymposiaNo.52,Dec.1991,p.307-12DEGRADATION BEHAVIOUR OFPOLYURETHANE STUDIED BY LINEARTEMPERATURE PROGRAMMED PYROLYSISFTIR SPECTROSCOPYHerzog KDRESDEN,TECHNISCHE UNIVERSITAT

PU was produced from MDI and adipate esters. Its thermaldegradation was studied by an FTIR spectrometer withtwo measurement beams, i.e. the pyrolysis cell (in thesample beam) was connected to a gas cell (in the referencebeam). Stages in the decomposition process wereelucidated and degradation products were identified. 3refs. (9th Eur.Symp.on Polymer Spectroscopy (ESOPS9),Cologne,Germany, 25th-27th Sept.1990)GERMANY

Accession no.442543

Item 359Applied Spectroscopy45,No.7,Aug.1991,p.1193-8APPLICATION OF ATR-IR TO THE ANALYSISOF SURFACE STRUCTURE AND ORIENTATIONIN UNIAXIALLY DRAWN PETPWalls D JDU PONT CO.

A critical assessment was made of the use of ATR-IRspectroscopy for the study of the surface composition andorientation in uniaxially drawn PETP films. The use ofreference bands commonly used in such analyses wasexamined, paying particular attention to the possibledeleterious effects of sample orientation, incidentpolarisation and sample contact. The use of conventionalsampling procedures to obtain in-plane surface dichroismmeasurements is shown. 25 refs.USA

Accession no.432374

Item 360Polyurethanes 90.Conference Proceedings.



Orlando,Fl.,30th Sept-3rd Oct.1990,p.527-39. 43C6FT-IR - A PROBE INTO THE REACTIONKINETICS AND MORPHOLOGYDEVELOPMENT OF URETHANE FOAMSPriester R D;McClusky J V;O’Neill R E;Turner RB;Harthcock M A; Davis B LDOW CHEMICAL CO.(SPI,Polyurethane Div.)

An IR technique has been used to obtain spectra of areacting PU foam system having a given temperatureprofile every 5-10 seconds. Chemical reaction rates andmorphology development were evaluated using computerassisted spectral analysis to simultaneously monitor bothisocyanate disappearance and the evolution of urethaneand urea carbonyl absorbancies. Quantitation of theproducts vs. time is obtained via curve fitting anddeconvolution routines. Applications have been provenin a wide variety of cellular PU systems. 15 refs.USA

Accession no.432190

Item 361Polymer32,No.10,1991,p.1862-6CONFORMATIONAL STRUCTURE OFBISPHENOL A POLYCARBONATE STUDIED BYIR SPECTROSCOPYSchmidt P;Dybal J;Turska E;Kulczycki ACZECHOSLOVAK ACADEMY OF SCIENCES;POLISH ACADEMY OF SCIENCES

An IR spectroscopic study of the conformationalstructures of polycarbonate (Bistan AF) was carried outin the solid state and in solution. Based on the temperaturedependences of the IR spectra, bands sensitive totransitions between the trans-trans and trans-cisconformations of the carbonate group were identified. Anassignment of these bands to the specific molecularconformations of the polymer is proposed. 16 refs.CZECHOSLOVAKIA; EASTERN EUROPE; POLAND

Accession no.431935

Item 362Applied Spectroscopy45,No.5,June 1991,p.752-5IMPROVEMENT OF THE LIMITINGTHICKNESS OF THE MEASURABLE SURFACELAYER ON POLYMER FILMS USING FOURIERTRANSFORM IR ATTENUATED TOTALREFLECTION SPECTROSCOPY WITH THEUSE OF SILVER ISLAND FILMSNiahikawa Y;Ito Y;Fujiwara K;Shima TKONICA CORP.

The use of silver films under Kretschmann’s attenuatedtotal reflection geometry has improved the detection limitof the surface layer on polymer films. An enhancementfactor 10 and 2 is reported for polydimethylsiloxane and

polycarbonate respectively, compared to the conventionalATR technique. 14 refs.JAPAN

Accession no.428812

Item 363Polymer Communications32,No.8,1991,p.229-31RAMAN SPECTROSCOPY. AN ORIGINAL ANDNON-DESTRUCTIVE METHOD TODETERMINE THE RATE OF POLYMERISATIONPHOTOINITIATED BY LASER BEAMMailhot G;Philippart J L;Bolte MBLAISE PASCAL,UNIVERSITE

A Raman spectrophotometer was used to measure in situthe polymerisation rate of acrylamide photoinitiated byhydrogen chromate anion in aqueous solution uponirradiation by laser beam (ionised argon) . The progressof the reaction was monitored at 2930/cm, the absorptioncharacteristic of the polymer formed. The method wasfound to be reliable, but is limited to monomers whosepolymer is soluble in the reaction medium. 10 refs.EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.426029

Item 364Journal of Applied Polymer Science42,No.8,20th April 1991,p.2169-90ANALYSIS OF REACTION-INJECTION-MOULDED POLYURETHANES BY NEAR-INFRARED DIFFUSE REFLECTANCESPECTROSCOPYMiller C E;Eichinger B EWASHINGTON,UNIVERSITY

The ability of near-IR diffuse reflectance spectroscopyto characterise RIM PU elastomers was demonstrated.The specific effects of composition, density, phaseseparation, and moisture content on the near-IR spectrawere identified. The ability of near-IR spectroscopy tomake rapid assessments of physical properties isdiscussed. 52 refs.USA

Accession no.424385

Item 365Polymer Communications32,No.4,1991,p.125-8INFRA-RED DETERMINATION OFCONFORMERS OF POLYETHYLENETEREPHTHALATEYang X;Long F;Shen D;Qian RACADEMIA SINICA

An IR spectroscopic method is described for analysingquantitatively the conformers of the ethylene glycoxymoeity of PETP, in the amorphous and crystalline regions.



The method uses spectral band reconstructions of theprofiles of either the 382/cm band or the 1020/cm bandfor a series of specimens annealed at different temps.Consistent results were obtained from both bands for thecompositions of the three conformers, i.e. the transconformer in the crystalline state and both the transconformer and the gauche conformer in the amorphousstate. This demonstrates the reliability of the method. 13refs.CHINA

Accession no.422551

Item 366Applied Spectroscopy45,No.2,Feb.1991,p.173-7QUANTITATIVE ANALYSIS OF ADDITIVES INLOW-DENSITY POLYETHYLENE USINGINFRARED SPECTROSCOPY ANDMULTIVARIATE CALIBRATIONVigerust B;Kolset K;Nordenson S;HenriksenA;Kleveland KNORWAY,CENTRE FOR INDUSTRIAL RESEARCH;STATOIL AS

Multivariate calibration methods were used to establisha new method for measurement of three selected additivesin LDPE. The determination of the concentration of silica,erucamide and butylhydroxytoluene was based on IRspectroscopy and a calibration model. The concentrationswere between 20 and 1100 wt/ppm. Compared withtraditional chemical analyses, the new method was shownto be both time- and cost-effective and to be more precise.The method has potential for quality control of PE. 8 refs.NORWAY; SCANDINAVIA; WESTERN EUROPE

Accession no.421049

Item 367Analyst115,No.12,Dec.1990,p.1597-9FOURIER TRANSFORM IR SPECTROMETRICDETERMINATION OF POLYETHYLENEGLYCOL (ANTISTATIC AGENT) IN HDPEKumar TMOBIL CHEMICAL CO.

A direct IR method using Fourier transform IRspectroscopy for rapidly determining the low relativemolec.wt. PEG, Carbowax 400, in HDPE is described. Itdoes not require solvent extraction of PEG from PE andits speed and simplicity make it suitable for quality controlapplications. Measurements on HDPE containing PEGusing this technique are reported. 9 refs.USA

Accession no.419959

Item 368Plaste und Kautschuk

37,No.6,June 1990,p.185-6GermanIR SPECTROSCOPIC ANALYSIS OF JONOL INPOLYETHYLENE AND ETHYLENE-VINYLACETATE COPOLYMER FILMSWinterberg H;Brunn J;Fuehrling WMERSEBURG,TECHNISCHE HOCHSCHULE

An IR spectroscopic technique for the analysis of 2, 6-di-tert-butyl-4-methylphenol stabilisers in PE and EVAcfilms is described and its effectivenesss evaluated. 3 refs.EAST GERMANY; EASTERN EUROPE

Accession no.418941

Item 369Polymer32,No.2,1991,p.338-42RAMAN SPECTROSCOPICCHARACTERISATION OF HIGH-VINYLPOLYBUTADIENES PRODUCED FROMANIONIC POLYMERISATIONPoshyachinda S;Edwards H G M;Johnson A FBRADFORD,UNIVERSITY

n-Butyllithium was the initiator and cyclohexane thesolvent for the above polymerisation. Amongcomplexing agents used to change the mode of additionto 1,2 or vinyl, 1,2-dipiperidinoethane and diglymewere very effective, although their effectivenessdecreased with temp. The microstructure of thepolymers was characterised by Raman spectroscopyusing the Raman active carbon-carbon double bondstretching bands of vinyl, cis and trans structures at1640, 1650 and 1664/cm, respectively. A curve analysisprogram applied to the computerised data acquisitionenabled the band areas of each component band to beevaluated. 16 refs.EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.417574

Item 370Applied Spectroscopy44,No.10,Dec.1990,p.1719-21DETERMINATION OF HYDROXYL NUMBER INPOLYMERS BY INFRARED SPECTROSCOPYLee K A B;Hurley S M;Siepler R A;Mills RD;Handrich K A;Conway J JJOHNSON S.C.,& SON INC.

An infrared analysis method was developed fordetermining the hydroxyl number in samples of polyestersformed by the copolymerisation of a hydroxy-functionalacrylic oligomer with adipic acid and 1, 6-hexanediol.The method was shown to be sufficiently accurate, to befaster than chemical analysis and to reduce exposure toirritating, toxic and corrosive chemicals. 9 refs.USA

Accession no.417249



Item 371Analyst115,No.10,Oct.1990,p.1319-22FOURIER TRANSFORM INFRAREDSPECDTROMETRIC DETERMINATION OFSTEARIC ACID IN STYRENIC POLYMERSKumar TMOBIL CHEMICAL CO.

The use of additive isolation procedures and Fouriertransform IR spectrometry for quantifying external andinternal stearic acid lubricant in PS resins is discussedand advantages over previously-used techniques areconsidered. 13 refs.USA

Accession no.413159

Item 372Applied Spectroscopy44,No.7,Aug.1990,p.1137-42FIBRE STRUCTURE STUDY BY POLARISED IRATTENUATED TOTAL REFLECTIONSPECTROSCOPY: ORIENTATIONDEVELOPMENT OF NYLON 66 AT VARIOUSSPINNING SPEEDSSamanta S R;Lanier W W;Miller R W;Gibson M EMONSANTO CHEMICAL CO.

A study was made of orientational development in thehigh-speed spinning of high-viscosity and low-viscositynylon 66 yarns using IR dichroism. A relationship betweenIR dichroism and orientation factor was developed and arelationship between orientation measured by IR and X-ray diffraction demonstrated. These were used to obtainthe transition moment direction of a molecular vibration,which would otherwise be impossible to obtain by a singletechnique. 15 refs.USA

Accession no.411182

Item 373Polymer31,No.7,July 1990,p.1222-7VIBRATIONAL ANALYSIS OF THE TIGHT (110)FOLD IN POLYETHYLENEWolf S;Schmid C;Hagele P CULM,UNIVERSITY

The defect density of states of the tight (110) fold in PEis calculated using Green’s functions in the frequencyrange 500 to 1400/cm. Resonance modes of the (110) foldcalculated at 1348, 1342 and 1288/cm are assigned toinfrared bands at 1346-1347 and 1342-1343/cm and near1295/cm. It is shown that the (110) folds (approximatelyg’g’ggtg) also contribute to the gtg/gtg’ bands at 1368/cm. In contrast to the (200) fold, it does not exhibit alocalised gap mode near 700cm. The calculations allowthe observed IR bands to be assigned to the defect modesof the (110) fold without introducing the qualitative

concept of distorted gg conformations used in theliterature. 29 refs.EUROPEAN COMMUNITY; WEST GERMANY; WESTERNEUROPE

Accession no.403740

Item 374Polymer Communications31,No.7,July 1990,p.290-2EVIDENCE FOR THE CONDUCTIONMECHANISM IN IODINE-DOPED CIS-POLYISOPRENE RUBBER USING RESONANCERAMAN SPECTROSCOPYWilliams K P J;Gerrard D LBP RESEARCH CENTRE

Resonance Raman spectroscopy was used to investigatethe products formed upon iodine doping of cis-polyisoprene. Evidence for the production of polyeneswas found. It is suggested that these are in part responsiblefor the increased conductivity of iodine-doped cis-polyisoprene. A possible chemical reaction is postulatedfor polyene production. 18 refs.EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.403729

Item 375Applied Spectroscopy44,No.3,March/April 1990,p.512-8FT-IR METAL OVERLAYER ATRSPECTROSCOPY USING A COATEDELASTOMER BACKING MATERIALKhoo C G L;Ishida HCASE WESTERN RESERVE UNIVERSITY

A metal overlayer FT-IR-ATR technique which markedlyenhances the signal-noise ratio of monolayer andsubmonolayer film spectra is described. Experimentalevidence of the enhancement is given for, as examples, adeposited PVAc film of 0.5 or 5nm and a thin film ofadsorbed protein human serum albumin, estimated to beof the order of 5nm. The metals investigated were goldand aluminium, with a substrate of polyether-urethaneelastomer. 20 refs.USA

Accession no.401264

Item 376Applied Spectroscopy44,No.4,May 1990,p.543-9DEVELOPMENT OF ASPECTRAL DATA BASEFOR THE IDENTIFICATION OF FIBRES BY IRMICROSCOPYTungol M W;Bartick E G;Montaser AUS,FBI; WASHINGTON G.,UNIVERSITY

A detailed study of the application of IR microscopy forsingle fibre analysis was undertaken. A library of 43



polymer fibres, distinguishable by their IR spectra, wasconstructed. 23 refs.USA

Accession no.400336

Item 377British Polymer Journal22,No.2,1990,p.97-105STUDY OF THE FORMATION ANDCHARACTERISATION OF OXAZOLIDONE-ISOCYANURATE POLYMERS USINGDIFFERENTIAL SCANNING CALORIMETRYAND INFRARED SPECTROSCOPYLee Y S-K;Hodd K;Wright W W;Barton J MBRUNEL UNIVERSITY; UK,ROYAL AIRCRAFTESTABLISHMENT

The polymers were prepared by reacting five glycidylethers with 4, 4'-diisocyanatodiphenylmethane in thepresence of 2-ethyl-4-methylimidazole. The degree ofcure of the resins was followed by IR spectroscopy andDSC. The rates of the isocyanurate to oxazolidonelinkages were determined quantitatively by an infraredmethod and the glass transition temperatures of thepolymers were measured by DSC and dynamicmechanical thermal analysis. 16 refs.UK; EUROPEAN COMMUNITY

Accession no.394426

Subject Index

© Copyright 2001 Rapra Technology Limited 129

Subject Index

1,2-POLYBUTADIENE, 3692,6-DI-TERT-BUTYL-4-

METHYLPHENOL, 368

AABRASION RESISTANCE, 259ABSORBANCE, 259 264 337ABSORPTION, 5 36 87 96 102

127 132 154 164 169 199 260343

ABSORPTION COEFFICIENT,223 257 343

ABSORPTION SPECTRA, 6 151155 156 177 189 246 297 330343

ACCELERATED AGEING, 336ACCELERATED TEST, 18 76ACCELERATOR, 304 340 354ACETONE, 22 272ACETYL GROUP, 238ACETYLENE COPOLYMER, 345ACETYLENE TERMINATION,

242ACID, 2 193ACID FLUORIDE GROUP, 146ACID NUMBER, 152ACID-BASE INTERACTION, 165

233ACIDIC, 233ACOUSTOOPTICAL DEVICE,

152ACRYLAMIDE COPOLYMER,

125ACRYLAMIDE TERPOLYMER,

125ACRYLATE, 124 260ACRYLATE COPOLYMER, 184

343ACRYLIC ACID, 133ACRYLIC ACID COPOLYMER,

125 322ACRYLIC ACID TERPOLYMER,

125ACRYLIC COPOLYMER, 66ACRYLIC ESTER, 124ACRYLIC ESTER COPOLYMER,

184ACRYLIC RESIN, 246 280 282

319 326ACRYLONITRILE, 154 226 272

295ACRYLONITRILE

COPOLYMER, 221 228ACRYLONITRILE GROUP, 154

ACTIVATION ENERGY, 214 230240 242 312 345 347

ACTIVATOR, 304ACYL AMMONIUM, 329ACYLATION, 146 301ADDITIVE, 33 55 68 71 86 87 104

132 137 138 154 156 160 166176 189 202 203 212 215 246248 249 253 264 304 322 340341 354 366 371

ADHESION, 232 233 285ADHESIVE, 88 192 193 232 233

285 289ADIPATE COPOLYMER, 257ADSORPTION, 42 119 126AGEING, 27 33 41 104 112 154

177 189 312AGGREGATE, 93 293ALBUMIN, 375ALCOHOL, 36 288ALCOHOL GROUP, 147 225ALDEHYDE, 154 288ALDEHYDE GROUP, 189ALIGNMENT, 207 243ALIPHATIC, 79 133 241ALKALI, 294ALKALINE DEGRADATION, 50ALKANE, 10 67 189ALKENE, 189ALKYL HYDROXIDE, 36ALKYL METHACRYLATE

COPOLYMER, 321ALKYLBENZENE SULFONATE,

99ALLOTROPIC, 304ALTERNATING COPOLYMER,

182 273ALTERNATING

COPOLYMERISATION, 239ALTERNATING POLYMER, 182ALUMINA, 126 196ALUMINIUM, 375ALUMINIUM BUTOXIDE, 13ALUMINIUM CHLORIDE, 155ALUMINIUM FOIL, 246ALUMINIUM OXIDE, 110 126

196 233ALUMINIUM TRICHLORIDE,

317AMIDE, 154AMIDE COPOLYMER, 308AMIDE GROUP, 154AMINE, 197 227 248 249 253 277

340 354AMINE GROUP, 244 286

AMINO ACID, 349AMMONIA, 154 236AMORPHOUS, 26 52 73 90 107

116 142 257 350 365AMPHOTERIC, 233AMYL ACETATE, 122ANHYDRIDE, 248 249 288 343ANHYDRIDE GROUP, 273ANIONIC, 30 99ANIONIC POLYMERISATION,

188 214 314 369ANISOTROPY, 143 223 282ANNEALING, 23 56 89 94 147

177 183 187 197 225 252 316365

ANTHRACENE, 129ANTI-BLOCKING AGENT, 324

366ANTIFOULING, 42 124ANTIMONY COMPOUND, 271ANTIOXIDANT, 189 303 322 366APODISATION FUNCTION, 155AQUEOUS EMULSION, 246AQUEOUS PHASE, 295AQUEOUS SOLUTION, 65 85 93

258ARGON, 3 345AROMATIC, 89 133 202 241 252

257 271 302 303 325 371ARRHENIUS’S LAW, 58ATACTIC, 57 74 107 219 350AUTOXIDATION, 189AZOBISISOBUTYRONITRILE,

321

BBACK-SCATTERING, 247BANDWIDTH, 237BARRIER FILM, 194 245BARRIER LAYER, 275BASE, 233BEAMSPLITTER, 283BENZENE, 126 142 252 317 321BENZENE RING, 9 272BENZYL DIMETHYLAMINE,

248BIAXIAL ORIENTATION, 131

230BILAYER, 223BINARY BLEND, 11BINARY SYSTEM, 165BIOCOMPATIBILITY, 342BIODEGRADATION, 156BIPOLAR, 102

Subject Index


BIPOLARON, 331BIREFRINGENCE, 114BISMALEIMIDE COPOLYMER,

239BISPHENOL A, 197 241 312 340BISPHENOL A DIGLYCIDYL

ETHER, 79 354BISPHENOL A

POLYCARBONATE, 177 278361

BISPHENOL DIGLYCIDYLETHER, 79

BLEND, 11 29 45 52 57 92 106116 117 120 128 129 133 139165 166 218 221 229 233 241247 278 279 296 299 304 305310 311 313 316 318 323 348

BLOCK COPOLYMER, 101 188243 344

BLOCK POLYMERISATION, 314BOUND WATER, 185 246BRANCHING, 4 84BREAKAGE, 207BROMINATION, 345BROMINE COMPOUND, 274BULK, 9 17 146 164BUTADIENE, 226 272BUTADIENE COPOLYMER, 188

228BUTADIENE-ACRYLONITRILE

COPOLYMER, 104 154 226228 272 335

BUTADIENE-STYRENECOPOLYMER, 226 269 272

BUTANE ACRYLATE, 60BUTYL ACRYLATE

COPOLYMER, 35 184BUTYL ACRYLATE

TERPOLYMER, 21BUTYL GLYCIDYL ETHER, 28BUTYL HYDROXYTOLUENE,

366BUTYL METHACRYLATE

COPOLYMER, 321BUTYL METHACRYLATE

TERPOLYMER, 124BUTYL METHYLPHENOL, 368BUTYL RUBBER, 33BUTYLDIMETHYLSILYLOXY-

STYRENE COPOLYMER, 321BUTYLLITHIUM, 214

CCALCIUM CARBONATE, 300

304CALCIUM OXIDE, 196CALIBRATION, 110 127 141 176

211 234 247 259 264 283 303313 326 337 338 343

CALORIMETRY, 165CAMPHOR, 283CAPROLACTAM COPOLYMER,

308CAPSTOCK, 76 153CARBON 13, 2 13 127 155 229CARBON BLACK, 48 104 164

304CARBON DIOXIDE, 26 122 236

303CARBON DISULFIDE, 272CARBON FIBRE, 192 207 212

237 260CARBON FIBRE-REINFORCED

PLASTIC, 207 212 237 281CARBON MONOXIDE, 236CARBON TETRACHLORIDE,

126CARBON-13, 2 13 127 155 229

354CARBONATE, 241CARBONYL, 5 330CARBONYL GROUP, 41 50 93

103 154 165 297 343CARBOXY GROUP, 41CARBOXYL GROUP, 41 288 339CARBOXYLATE GROUP, 9CARBOXYLIC ACID, 228 260

288CARBOXYLIC ACID GROUP,

146 228CARBOXYLIC GROUP, 133CAST FILM, 29CASTING, 180 213CATALYST, 2 24 59 155 286CATIONIC POLYMERISATION,

240CAUSTIC SODA, 146CELLULAR MATERIAL, 59 360CELLULOSE, 116 294CETANE, 67CHAIN, 4 78 125 290CHAIN CONFORMATION, 27 51

57 78 309 350CHAIN DEFORMATION, 250CHAIN EXTENSION, 80 201CHAIN FOLDING, 373CHAIN LENGTH, 1 79 80 340CHAIN ORIENTATION, 51 119

195 199 223 250 309CHAIN PACKING, 350CHAIN SCISSION, 189 256 273

278 304 312 320 330CHAIN STRUCTURE, 10 78 125

350CHAR FORMATION, 273

CHEMICAL COMPOSITION, 1966 149 153

CHEMICAL DEGRADATION,154

CHEMICAL MODIFICATION, 941 61 79 108 115 146 196 220256 301 306 312 321 345

CHEMICAL PROPERTIES, 82108 152 154

CHEMICAL RESISTANCE, 154CHEMICAL SHIFT, 155CHEMICAL STRUCTURE, 2 10

19 36 43 54 56 70 72 74 79 8384 93 95 103 104 105 108 111116 122 123 124 125 133 138142 146 155 156 162 163 167174 177 182 189 192 354

CHEMICRYSTALLISATION, 50CHEMOMETRIC ANALYSIS, 73

141CHINA CLAY, 87 132CHITOSAN, 162CHLORINATED, 190CHLORINE, 317CHLOROFORM, 150CHROMATOGRAPHY, 113 138CHROMIUM OXIDE, 196CHROMOGEN, 143CHROMOPHORE, 143 218CIRCULAR DICHROISM, 101CLATHRATE, 350CLEARCOAT, 149CLOUD POINT, 93CLUSTER, 65 155 246COALESCENCE, 203 246COATING, 18 19 42 62 75 98 118

149 191 192 246 227 285COCATALYST, 155COERCIVE FIELD, 231COHESION, 180 282COLD CRYSTALLISATION, 210COLD DRAWN, 94 134COLLOIDAL PROPERTIES, 295COLOURANT, 189COLUMN CHROMATOGRAPHY,

215COMMINGLED, 77COMONOMER, 141 260COMPATIBILISER, 117 120 133COMPLEX, 42 89 140COMPLEX FORMATION, 140

181COMPLEXATION, 89COMPLEXING AGENT, 369COMPOSITE, 109 142 161 166

190 207 212 217 221 237 249279 281 286 328 352 357

COMPOSITION, 11 17 21 44 57

Subject Index


61 75 112 116 117 121 123 124128 129 133 141 165 278

COMPOUNDING, 304COMPOUNDING INGREDIENT,

341COMPRESSION MOULDED, 155COMPRESSION MOULDING, 86

144 159 204COMPUTER AIDED ANALYSIS,

155 247 356 369COMPUTER AIDED TESTING,

166 355 360COMPUTER PROGRAM, 166COMPUTER SIMULATION, 223COMPUTER SOFTWARE, 152COMPUTERISED ANALYSIS, 81CONCENTRATION

FLUCTUATION, 44 176CONCENTRATION GRADIENT,

44CONDENSATION, 127CONDENSATION REACTION,

12CONDENSED PHASE, 357CONDUCTIVE PLASTIC, 121

331CONDUCTIVE POLYMER, 121

298 345CONDUCTIVE RUBBER, 374CONFOCAL, 17 128 149 225CONFOCAL IMAGING, 62CONFORMATIONAL, 5 182 186

365CONFORMATIONAL

TRANSITION, 294 316 355361

CONJUGATED BOND, 304CONJUGATED POLYMER, 315

317 374CONTACT ANGLE, 327CONTAMINANT, 77 175COOLING, 27 88 155 187 224 247

252COPOLYESTER, 325COPOLYETHERSULFONE, 19COPOLYMER COMPOSITION,

72 73 110 155 184 188 204 321335 338 343

COPOLYMERISATION, 124 135142

COPPER, 108 142COPPER OXIDE, 142 196 275CORRELATION, 12 163 168 254

247 272CORRELATION

SPECTROSCOPY, 16 57 73148 167 168

COUPLING AGENT, 217 229 328

COVALENT BONDING, 154CRACKING, 91 156CRAZE RESISTANCE, 99CRAZING, 99CRITICAL CONCENTRATION,

154CRITICAL SOLUTION

TEMPERATURE, 93CROSS-POLARISATION, 354CROSSLINK, 9 13 58 61 75 151

154 332 377CROSSLINK DENSITY, 61 154

239 253 304CROSSLINKED, 60 75 151 197

253 278 290 304CROSSLINKED COPOLYMER,

61 200CROSSLINKING, 24 34 61 62 63

69 75 154 189 217 242 244 273328 377

CROSSLINKING AGENT, 61 151244

CROSSLINKING PHENOMENA,61 62 75 154

CROSSLINKING RATE, 62CRYOMICROTOMY, 156CRYSTAL, 6 187 223CRYSTAL STRUCTURE, 46 56

84 114 195 350CRYSTAL TRANSITION, 195CRYSTALLINE, 10 52 56 73 155

165 186 187CRYSTALLINITY, 19 23 31 46 52

56 84 90 94 97 114 129 155 165167 173 183 186 187 195 204218 219 223 234 241 251 252258 307 316 318 346 350 365373

CRYSTALLISATION, 23 26 50 5683 155 210 219 254 304 355

CRYSTALLISATION RATE, 123224

CRYSTALLISATIONTEMPERATURE, 56 155

CRYSTALLISED, 250CRYSTALLITE, 187 210CRYSTALLOGRAPHY, 134CUPRIC OXIDE, 196CURE, 58 353CURE RATE, 9 62 239 276 277

278 332CURE TEMPERATURE, 80CURE TIME, 200 304 354CURED, 149 197 312CURING, 9 19 24 34 38 62 63 75

88 118 149 161 191 217 278286 352 353 356

CURING AGENT, 24 59 61 151

154 197 248 249 253 276 277304 312 340 354

CURING REACTION, 62 75 239276 277

CURING SYSTEM, 75CURING TEMPERATURE, 37

242 304 354CYANOAZOBENZENE, 143CYANOBIPHENYL, 88CYANOGUANIDINE, 354CYCLIC DEFORMATION, 197CYCLIC VOLTAMMETRY, 298CYCLISATION, 80CYCLOHEXANE, 126CYCLOHEXAPHENYLENE

SULFIDE, 84CYCLOHEXYLMALEIMIDE

COPOLYMER, 64

DDATA DENSITY, 166DEACETYLATION, 273DEBONDING, 212DECALCIFICATION, 193DECANEDIOL, 79DECARBOXYLATION, 278DECOMPLEXATION, 89DECOMPOSITION, 113 189DECOMPOSITION

TEMPERATURE, 113 273 274DECONVOLUTION, 41DECYL METHACRYLATE

COPOLYMER, 321DEFORMATION, 55 79 94 99 107

161 169 187 197 253 281 282355

DEGRADATION, 27 33 41 50 76104 112 146 154 156 177 189

DEGRADATION PRODUCT, 76112 153 273 274 279 302 351358

DEGRADATION RATE, 112 323DEGRADATION

TEMPERATURE, 112DEGREE OF CONVERSION, 61

315DEGREE OF CRYSTALLINITY,

155 165 186 224DEGREE OF DISPERSION, 203DEGREE OF GRAFTING, 61 327DEGREE OF ORIENTATION, 52

307DEGREE OF

POLYMERISATION, 61 225241 257 293 315 317 329

DEGREE OF SWELLING, 300DEHYDROBROMINATION, 345

Subject Index


DEHYDROHALOGENAT, 374DENSITY, 20 59 114 234 250 307

364DENTIN, 193DEPOLARISATION, 210DEPROTECTION, 321DEPROTEINISATION, 224DEPTH PROFILING, 17 18 21 62

137 147 148 168 194 225 245336 344

DESILYLATION, 321DETERGENT, 99DEUTERATED, 36 143 347DEUTERATION, 89 258 294DEUTERIUM, 36 256 287 294DEUTERIUM OXIDE, 36 258DI-2-ETHYLHEXYL

PHTHALATE, 17DIACETYLENE, 220DIALLYL BISPHENOL

COPOLYMER, 239DIAMINODIPHENYLMETHANE,

340DIBLOCK COPOLYMER, 101

344DIBUTYL MALEATE

COPOLYMER, 327DIBUTYLTIN DILAURATE, 24DICHLOROETHYL ETHER, 230DICHLOROFLUOROMETHYL

THIOPHTHALIMIDE, 17DICHLOROMETHANE, 292DICHROIC RATIO, 52 102 143

179 251DICHROISM, 6 39 46 52 55 101

114 119 134 143 159 179 181197 199 201 283 359 372

DICUMYL PEROXIDE, 304 327DICYANDIAMIDE, 285 312DICYANODIAMIDE, 354DIELECTRIC SPECTROSCOPY,

276DIELS-ALDER REACTION, 273DIENE COPOLYMER, 335DIETHYL CARBAMATE, 100DIETHYL MALEATE

COPOLYMER, 120DIETHYLENE GLYCOL

DIMETHYL ETHER, 369DIFFERENTIAL SCANNING

CALORIMETRY, 11 23 29 5384 89 93 94 123 155 165 173188 195 213 249 310 348 377

DIFFERENTIAL THERMALANALYSIS, 11 23 29 53 84 8993 94 123 155 165 173 188 195213 249 310 348 377

DIFFUSION, 22 26 36 40 53 68 99

122 128 136 150 230 246 300312

DIFFUSION COEFFICIENT, 36122 150 230 232 289 347

DIFFUSIVITY, 26 68 198 347DIGITAL SIGNAL

PROCESSING, 16 148DIGLYCIDYL ETHER, 197 312

340DIGLYME, 369DIHYDROXYBIPHENYL, 133DIMER, 163 302DIMERISATION, 292DIMETHYL ACETAMIDE, 116DIMETHYL FORMAMIDE, 354DIMETHYL SULFOXIDE, 147

287DIMETHYLACETAMIDE, 116DIMETHYLOLPROPIONIC

ACID, 60DIMETHYLSILOXANE

COPOLYMER, 275 344DIOCTYL PHTHALATE, 17DIOL, 79 340DIPHENYLMETHANE

DIISOCYANATE, 377DIPIPERIDINOETHANE, 369DIPOLE INTERACTION, 310DIPOLE ORIENTATION, 223 231DIPROPYLENE GLYCOL, 246DISORDERED POLYMER, 73

147 195DISPERSION, 88 120 334DISPERSIVITY, 203DIVINYL BENZENE, 61DIVINYL ETHER, 240DODECANE, 67DODECANEDIOL, 79DODECYL SULFATE, 331DOMAIN, 39 55 88 129 213 280

293DOPANT, 160 298 331DOPING, 54 290 298 331 374DOUBLE BOND, 80 103 189 200

263 272 304DRAW RATIO, 1 92 94 201 216

251 291DRAWING, 99 114 158 216 223

235 237DRIFT SPECTROSCOPY, 2DRY BLEND, 176DRYING TIME, 246DURABILITY, 232DYNAMIC, 16 55 102 134 168

242 254DYNAMIC INFRARED LINEAR

DICHROISMSPECTROSCOPY, 199

DYNAMIC INFRAREDSPECTROSCOPY, 102

DYNAMIC MECHANICALANALYSIS, 128 316

DYNAMIC MECHANICALPROPERTIES, 254

DYNAMIC MECHANICALTHERMAL ANALYSIS, 251377

EEFFICIENT VULCANISATION,

304ELASTIC LIGHT SCATTERING,

135ELASTIC MODULUS, 10 79 187

216ELECTRIC FIELD, 6 101 163 194

223 231 245 334ELECTRICAL CONDUCTIVITY,

30 160 292 345 374ELECTRICAL PROPERTIES, 30

112 121 160 223 292 345ELECTROCHEMICAL

POLYMERISATION, 290ELECTROCHEMICAL

PROPERTIES, 54ELECTROCLINIC PROPERTIES,

101ELECTROINITIATED

POLYMERISATION, 121 290292 298 317

ELECTRON ACCEPTOR, 165ELECTRON BEAM

IRRADIATION, 256ELECTRON DONOR, 165 233ELECTRON IMPACT MASS

SPECTROSCOPY, 325ELECTRON IRRADIATION, 146ELECTRON MICROGRAPH, 99ELECTRON SCANNING

MICROSCOPY, 117 120ELECTRON SPECTROSCOPY

FOR CHEMICAL ANALYSIS,327 344

ELECTRON TRANSFER, 331ELECTROPOLYMERISATION,

121 292 298 317ELEMENTAL ANALYSIS, 259

272ELEVATED TEMPERATURE, 188

320ELONGATION, 51 181 187 197

243ELONGATION AT BREAK, 117

216EMERALDINE BASE, 108

Subject Index


EMERALDINE SALT, 108EMULSION, 60 246EMULSION

COPOLYMERISATION, 35EMULSION POLYMERISATION,

35 319END GROUP, 189 330 339ENGINEERING PLASTIC, 323ENTHALPY, 165 177 233 262ENVIRONMENTAL STRESS

CRACKING, 94 99EPICHLOROHYDRIN

GLYCIDYL ETHER, 28EPOXY COMPOUND, 13EPOXY GROUP, 75EPOXY METHACRYLATE

COPOLYMER, 200EPOXY RESIN, 18 41 63 75 79

112 197 205 207 217 221 222227 248 249 253 276 277 278281 285 286 312 340 352 354377

EPOXY SILANE, 13EPOXYHEXENE, 13EPOXYPROPANE, 13EPOXYTRIMETHYLPENTANE,

32EPSILON-CAPROLACTAM

COPOLYMER, 188EQUILIBRIUM CONSTANT, 165EQUIVALENT WEIGHT, 30ERUCAMIDE, 71 130 324 366ESTER, 154 241 248 343ESTER COPOLYMER, 243 325ESTER GROUP, 133 146 225ESTER URETHANE

COPOLYMER, 95 96ETCHING, 193ETHANOL, 12 140 146ETHENE COPOLYMER, 46 117

120 123 184 189 221ETHERETHERSULFONE

COPOLYMER, 19ETHERIFICATION, 354ETHERSULFONE COPOLYMER,

19ETHYL ACETATE, 60 187ETHYL ACRYLATE

COPOLYMER, 92 203ETHYL ACRYLATE

TETRAPOLYMER, 124ETHYL ALCOHOL, 12 140 146ETHYL BENZENE, 89ETHYL METHACRYLATE

COPOLYMER, 321ETHYL METHACRYLATE

TETRAPOLYMER, 124ETHYL METHYLIMIDAZOLE,

377ETHYL PYRROLIDONE, 287ETHYLENE, 226 272ETHYLENE COPOLYMER, 46

117 120 123 184 189 221 228327

ETHYLENE OXIDE, 152 248 354ETHYLENE OXIDE

COPOLYMER, 85ETHYLENE-ETHYL ACRYLATE

COPOLYMER, 106ETHYLENE-PROPYLENE

COPOLYMER, 44 110 123 155189

ETHYLENE-PROPYLENE-DIENE COPOLYMER, 356

ETHYLENE-PROPYLENE-DIENE TERPOLYMER, 104145 155 224 226 229 272 306318

ETHYLENE-TETRAFLUOROETHYLENE,182

ETHYLENE-VINYL ACETATECOPOLYMER, 72 73 87 105130 132 141 165 218 226 233270 272 368

ETHYLENE-VINYL ALCOHOLCOPOLYMER, 258 305

ETHYLENIMINETERPOLYMER, 125

ETHYLHEXYL ACRYLATECOPOLYMER, 184

ETHYLIDENE NORBORNENE,272 356

EVANESCENT WAVESPECTROSCOPY, 217

EVOLVED GAS ANALYSIS, 302EXCITATION, 108EXCLUSION

CHROMATOGRAPHY, 215257

EXPOSURE TIME, 154 189EXTRACTION, 4 272 303 322EXTRUDER, 45 247EXTRUDER BARREL, 247EXTRUDING, 29 45 68 86 130

144 176 189EXTRUSION, 29 45 68 86 130

144 176 189 247 313EXTRUSION MIXING, 247

FFACTOR ANALYSIS, 222 272FAR-INFRARED

SPECTROSCOPY, 183 283FAST FOURIER TRANSFORM,

52 53FATTY ACID ESTER, 303FERROELECTRIC, 163FERROELECTRIC POLYMER,

101FERROELECTRIC PROPERTIES,

231FERROMAGNETIC, 220FIBRE, 114 137 207 234 260 286

301 303 308 320 330 337 376FIBRE BUNDLE, 247FIBRE OPTIC, 110 152 227 319

352FIBRE SPACING, 207FIBRE STRUCTURE, 114FIBRE TREATMENT, 114FIBRE-REINFORCED PLASTIC,

207FIBRILLAR, 216FIBROIN, 16FIBROUS FILLER, 212 237 301FICK’S SECOND LAW, 53FIELD STRENGTH, 163 231FILLED, 312FILLER, 33 44 48 87 104 132 175

176 212 218 304 341FILLER CONTENT, 268FILM, 8 9 15 16 17 18 19 21 22 26

29 36 44 50 51 56 60 68 72 75102 108 116 121 122 136 142150 155 158 159 161 162 168171 175 177 180 181 183 184194 197 202 203 223 230 233234 235 241 251 256 258 262269 272 290 291 298 299 305311 317 322 330 331 339 344346 359 362 368 375

FILM FORMING, 21 246FIRING TEMPERATURE, 237FIRST-ORDER, 278FLAME RETARDANT, 274FLAMMABILITY, 236FLEXIBILITY, 10 128 253FLEXIBLE, 10 128FLOW, 46 250FLUID RESISTANCE, 154FLUORESCEIN, 129FLUORESCENCE, 129 266 284

304FLUORINATION, 217FLUORINE, 259FLUOROPOLYMER, 30 213FOAM, 59 236 267 333 360FOLDED CHAIN, 10FORMALDEHYDE, 127FORMULATION, 76 175 176 377FRACTION, 133 354FRACTIONATION, 123 133 229

Subject Index


FRACTURE, 79 270 285FRACTURE MORPHOLOGY, 33

50 120 135FRAGMENTATION, 281FREE RADICAL, 189FREE RADICAL

COPOLYMERISATION, 142238

FREE RADICALPOLYMERISATION, 103 124142 238

FREQUENCY SHIFT, 134 199FRICTION COEFFICIENT, 212FUNCTIONAL GROUP, 189 262

272 280 330 334FUNCTIONALISATION, 133 203

228 327FUNCTIONALITY, 30 165 233 339

GGALVANOSTATIC, 290GAMMA-IRRADIATION, 330GAS CHROMATOGRAPHY, 113GAS-PHASE, 122GASES, 122GEL, 2 124 198 257GEL CHROMATOGRAPHY, 242GEL PERMEATION

CHROMATOGRAPHY, 214242 248

GELATION, 65GERMANIUM, 104 241 290GLASS, 233GLASS FIBRE-REINFORCED

PLASTIC, 286 328GLASS TRANSITION

TEMPERATURE, 27 29 53 5578 107 128 140 165 177 197201 253 280 310 312 348 377

GLASSY, 79 150 173GLOW DISCHARGE

POLYMERISATION, 171GLYCIDYL AMINE, 277GLYCIDYL ETHER, 377GLYCIDYL METHACRYLATE

COPOLYMER, 255 308GLYCOL ETHER, 246GOLD, 108 227 285 375GRAFT, 61 78 125 133 162 322GRAFT COPOLYMER, 61 74 125

133 255 275 322GRAFT COPOLYMERISATION,

255 308 322GRAFT DENSITY, 125GRAFT POLYMERISATION, 61

125 229 327GRAFT YIELD, 61 74 125

GRAFTED, 125GRAFTING, 61 78 125 133 162GRAPHITE, 48GRATING, 234GRAVIMETRIC ANALYSIS, 113

120 122 312GROUP I METAL COMPOUND,

30GROUP TRANSFER

POLYMERISATION, 329

HHARD SEGMENT, 39 55HARDENER, 285HARDNESS, 154HEAT DEGRADATION, 113 145

189HEAT RESISTANCE, 113 189HEAT SHRINKAGE, 201HEAT TREATMENT, 114 142 259HEATING RATE, 242HEAVY ION, 256HEAVY WATER, 287 294HELICAL, 6 89 350HELIUM, 256HETEROGENEOUS, 229 294HEXADECANE, 67HEXADIENE, 229HEXAGONAL, 182 195HEXANEDIOL, 79HIGH CONVERSION, 263HIGH DENSITY

POLYETHYLENE, 20 81 94134 247 250 261 269 305 316

HIGH IMPACT POLYSTYRENE,279

HIGH PERFORMANCE LIQUIDCHROMATOGRAPHY, 138351

HIGH PRESSURE, 7 26HIGH TEMPERATURE, 80 110

278HINDERED AMINE, 86 144HOMOGENEITY, 253HOMOGENEOUS, 61 88 213 317HOMOPOLYMER, 129HOT PRESS MOULD, 3HUMAN SERUM ALBUMIN, 42HUMIDITY, 41 189 246HYDRATION, 41 287HYDROCHLORIC ACID, 12 236HYDROGEL, 40 185 198HYDROGEN, 256 297HYDROGEN BOND, 28 39 55

102 116 167 185 287 294 296339

HYDROGEN BONDING, 50 60

93 140 146 147 174 225 257276 277

HYDROGEN BROMIDE, 236 345HYDROGEN CHLORIDE, 12 236HYDROGEN CYANIDE, 236HYDROGEN PEROXIDE, 297HYDROGENATED

ACRYLONITRILEBUTADIENE RUBBER, 154

HYDROLYSIS, 142 146 154HYDROLYTIC DEGRADATION,

50HYDROPEROXIDE, 288HYDROPEROXY GROUP, 297HYDROPHILIC, 196 246 249 322HYDROPHOBIC, 93 322HYDROXY GROUP, 50 165 297HYDROXY VALERATE

COPOLYMER, 114HYDROXYBENZENE, 127HYDROXYBENZOIC ACID, 133HYDROXYBUTYRATE

COPOLYMER, 114HYDROXYETHYL ACRYLATE,

60HYDROXYL GROUP, 50 165 238

297 354HYDROXYL NUMBER, 152 370HYDROXYLATED, 233HYDROXYVALERATE

COPOLYMER, 114HYSTERESIS, 327 334

IIMAGING, 19 52 53 88 105 178

222 271IMIDAZOLE, 3 340IMIDE, 154 354IMIDE COPOLYMER, 243IMIDE GROUP, 9 229IMIDISATION, 9 115 332IMINE, 154IMMERSION, 154IMMISCIBLE, 45 228IMMUNOGLOBULIN G, 42IMPACT MODIFIER, 175IMPACT PROPERTIES, 117IMPACT STRENGTH, 117IMPURITY, 189 248IN-LINE, 247 313IN-SITU, 26 31 32 35 42 54 78 80

94 135 150 217 227 230 232240 290 292 300 345

IN-VIVO, 156INCIDENCE ANGLE, 194 245INDENTATION, 161INDIUM ANTIMONIDE, 271

Subject Index


INDIUM COMPOUND, 271INDUCTION PERIOD, 38INFRARED ABSORPTION, 130

151 156 177 258 356INFRARED DICHROISM, 114

134 309INFRARED IMAGING, 18 19INFRARED POLARISATION, 52INHOMOGENEITY, 105 234INITIATION, 32INITIATOR, 32 75 118 161 306INJECTION MOULDING, 29 97INSOLUBLE, 133INTENSITY, 7INTENSITY RATIO, 272INTERACTION PARAMETER,

230 249INTERDIFFUSION, 128 328INTERFACE, 108 128 147 161

193 203 212 215 218 232 233281 353

INTERFACIAL ADHESION, 198281

INTERFACIAL AGENT, 328INTERFACIAL BONDING, 233INTERFACIAL ENERGY, 233INTERFACIAL INTERACTION, 8

194 233 245 249INTERFACIAL LAYER

THICKNESS, 10 328INTERFACIAL

POLYMERISATION, 322INTERFACIAL PROPERTIES, 8

147 161 165 194 202 225 228229 233 285

INTERFACIAL STRUCTURE, 9INTERFACIAL WIDTH, 161INTERMOLECULAR BONDING,

140INTERMOLECULAR

COMPLEXATION, 140INTERMOLECULAR

INTERACTION, 65 93 181 273278 310 350

INTERMOLECULARREACTION, 248

INTERNAL REFLECTIONSPECTROSCOPY, 150 194 232245 290

INTERNAL ROTATION, 307INTERNAL STANDARD, 319INTERPENETRATING

POLYMER NETWORK, 75238

INTERPHASE, 10 128 218 229249 286 328

INTERPOLYMER, 140INTRAMOLECULAR

INTERACTION, 65 93INTRAMOLECULAR

VIBRATION, 257IODINE, 374ION, 154ION BEAM IRRADIATION, 256ION EXCHANGE RESIN, 30ION PAIR, 296IONIC BOND, 154 244IONIC INTERACTION, 92 140

154IONISATION, 244 330IONISING RADIATION, 256IONOMER, 92 154 244 310IRRADIATION, 41 146 315 322

330ISOBUTYLENE COPOLYMER,

33ISOCYANATE, 59ISOCYANIDE, 154ISOCYANURATE, 377ISOIMIDE GROUP, 9ISOMER, 27 365 369ISOMERISATION, 242ISOMERISM, 304 365 369ISONITRILE, 154ISOPHORONE DIISOCYANATE,

60ISOPHORONE DIISOCYANATE

COPOLYMER, 37 38ISOPROPYL GROUP, 93ISOTACTIC, 4 16 31 74 170 180

189 199 211 252ISOTHERMAL, 240 242 248 278

323ISOTROPIC, 53 94 134 216ITACONIC ACID, 260

JJUTE, 301

KKAOLIN, 87 132KETONE, 288KETONE GROUP, 189KETYL PYRIDINIUM

CHLORIDE, 317KINETIC, 24 26 32 38 41 48 58

112 123 150 151 186 196 214227 240 242 262 276 277 278279 286 300 323 332 345

KRYPTON ION, 256

LLACTONISATION, 273

LAMELLA, 10LAMELLAR, 94 216LAMINATE, 147 164 168 194 198

223 225 233 245 305LANGMUIR-BLODGETT FILM, 9LASER POLYMERISATION, 363LASER TREATMENT, 48LATEX, 21 202 203 295 300 349LATTICE, 21 202 203 294LAYER, 121 194 245LEAST-SQUARES ANALYSIS,

81 234LIGHT AGEING, 112LIGHT DEGRADATION, 18 104

112 189 279 297 336 351LIGHT INTENSITY, 240 247LIGHT SCATTERING, 135 304LIGHT STABILISER, 112 189LIMONENE, 122LINEAR DICHROISM, 134LINEAR DISCRIMINANT

ANALYSIS, 178LINEAR LOW, 247LINEAR LOW DENSITY

POLYETHYLENE, 20 86 120144

LINEAR REGRESSIONANALYSIS, 247 272

LIPID, 6LIQUID CHROMATOGRAPHY,

138 215 351LIQUID CRYSTAL, 37 38 39 53

88 136 243 269 280 334LIQUID CRYSTAL POLYMER,

101 133 143 163LIQUID CRYSTALLINE, 1 10 133LIQUID PHASE, 354LIQUID POLYMER, 7LIVING POLYMERISATION, 32

314 329LOAD TRANSFER, 212LOADING, 197 253LOSS FACTOR, 377LOSS TANGENT, 377LOW DENSITY

POLYETHYLENE, 20 71 81110 117 218 221 247 250 269305 316 324 327 366

LOW FREQUENCY, 282LOW TEMPERATURE, 43LOWER CRITICAL SOLUTION

TEMPERATURE, 93LUBRICANT, 154 175 176 324

371LYSOZYME, 42

Subject Index


MMACHINERY, 45 247MACROCYCLISATION, 329MAGIC ANGLE, 229 354MAGNESIUM PERCHLORATE,

340MAGNETIC PROPERTIES, 220MAIN CHAIN, 189 304MALEATION, 306MALEIC ANHYDRIDE, 306MALEIC ANHYDRIDE

COPOLYMER, 117 221 229343

MALEIC ANHYDRIDE GROUP,229

MAPPING, 17 19 76 129 147 148153 234

MATRIX, 53 161 278 286MECHANICAL DEFORMATION,

94 161MECHANICAL LOSS, 177MECHANICAL PROPERTIES, 1

10 16 28 36 46 55 79 91 92 9499 102 117 128 134 154 158161 177 187 197 199 201 207210 212 216 235 237 243 250251 253 259 278 281 282 285296 299 304 312 320 327 334

MECHANICAL RELAXATION,169

MELAMINE RESIN, 149MELAMINE-FORMALDEHYDE

RESIN, 149 221MELT, 10 31 187 219 247 254 324MELT BLEND, 247MELT MIX, 241MELT PROPERTIES, 31MELT STATE, 173MELTING, 155 165 249MELTING POINT, 89 141 187MELTING TEMPERATURE, 123

155MEMBRANE, 6 61 333MEMORY EFFECT, 101MERCAPTOBENZTHIAZOLE,

304MESOGEN, 39 101 163 243MESOMORPHIC, 350METAL, 108 285 375METAL ADHESION, 285METALLISATION, 108 285METALLISED, 227METALLOCENE, 155METHACRYLATE

COPOLYMER, 308 321 338343

METHACRYLIC ACID, 124

METHACRYLIC ACIDCOPOLYMER, 203 228 273

METHACRYLIC ACIDTERPOLYMER, 21 124

METHACRYLIC ACIDTETRAPOLYMER, 124

METHACRYLOXYPROPYLTRIMETHOXYSILANECOPOLYMER, 328

METHANOL, 126 196METHYL ACRYLATE

COPOLYMER, 166 184METHYL ALCOHOL, 126 196METHYL ANHYDRIDE, 248METHYL CELLULOSE, 116METHYL ETHYL KETONE, 154METHYL GROUP, 93 189 272 330METHYL ISOBUTYL KETONE,

47METHYL METHACRYLATE

COPOLYMER, 64 203 275METHYL METHACRYLATE

TERPOLYMER, 124METHYL METHACRYLATE

TETRAPOLYMER, 124METHYL PYRROLIDINONE,

332METHYL PYRROLIDONE, 60

287METHYL STYRENE

COPOLYMER, 33 200METHYLACETAMIDE, 167METHYLCELLULOSE, 116METHYLCYCLOHEXANONE,

283METHYLENE GROUP, 189 272

297METHYLENE BISPHENYLENE

DIMALEIMIDE, 239METHYLMETHACRYLATE

COPOLYMER, 64 203METHYLPHENOXYETHYL

METHACRYLATECOPOLYMER, 338

METHYLSTYRENECOPOLYMER, 33 200

MICROBOND, 281MICROCOMPOSITE, 207MICRODOMAIN, 213MICRODROPLET, 135MICROEMULSION, 60MICROGRAPHY, 156MICROHARDNESS, 154MICROMECHANICAL, 161 281MICROPHASE SEPARATION,

101MICROPROBE, 121 234MICROSPHERE, 78 271

MICROSTRUCTURE, 156 181189 223 235 335 369

MICROTOME, 188MICROWAVE, 3MIGRATION, 202 203 218 304MISCIBILITY, 29 92 116 310MIXING, 29 176 247 347 348MIXTURE, 122 129 166 224MODEL COMPOUND, 9 13 94

151 167 242 276 277 304 341MODIFICATION, 79 196 233 278MODULUS, 1 134 212 237MOISTURE CONTENT, 152 185

249 364MOLAR RATIO, 79 121 127 229MOLE FRACTION, 257 343MOLE RATIO, 79 121 127MOLECULAR

CONFIGURATION, 27 51 5657 67 78 89 119 177 180 182183 188 195 218 219 251 252309 330 346 350 361 365 369373

MOLECULAR DISORDER, 189MOLECULAR INTERACTION, 8

65 93 147 278 311MOLECULAR MASS, 10 30 32

52 69 119 165 187MOLECULAR MOBILITY, 17

163MOLECULAR MOTION, 83 101MOLECULAR ORDER, 163 167MOLECULAR ORIENTATION, 1

5 19 79 91 92 94 101 102 119131 134 163 179 197 201 251253 291 307 316 355 372

MOLECULAR PACKING, 350MOLECULAR

REARRANGEMENT, 177 316MOLECULAR RELAXATION, 92MOLECULAR VIBRATION, 272MOLECULAR WEIGHT, 10 30 32

52 69 84 119 165 187 225 241257 293 314 321 347 367

MONOCLINIC, 94MONOFUNCTIONAL, 151MONOLAYER, 9 375MONOMER, 12 84 124 141 151

166 214 220 229 272MONOMER INSERTION, 155MONOMER REACTIVITY, 64MORPHOLOGICAL

PROPERTIES, 19 21 33 50 5266 94 117 120 135 187 203 213218 221 237 247 254 270 323346 360

MOULDING, 86 144 159 204MULTI COMPONENT, 166

Subject Index


MULTI FIBRE, 207MULTIFUNCTIONAL, 227 263MULTILAYER, 8 42 148 149 202MULTI PHASE, 88MULTIPLE INTERNAL

REFLECTANCESPECTROSCOPY, 150 232

NN-CYCLOHEXYL-2-

BENZOTHIAZOLESALFENAMIDE, 304

NADIC METHYL ANHYDRIDE,248

NANOPARTICLE, 23NAPHTHA, 82NATURAL RUBBER, 91 190 210

224 304 349NEAR-INFRARED

CORRELATIONSPECTROSCOPY, 73 167

NEAR-INFRAREDSPECTROSCOPY, 20 77 82 86105 109 141 144 152 157 168174 176 183 206 209 217 239247 265 276 277 305 311 313

NEMATIC, 37 53NEOPRENE, 104NETWORK STRUCTURE, 278

354NEURAL NETWORK, 157NEUTRALISATION, 244NITRIC OXIDE, 236NITRILE, 354NITRILE GROUP, 147 228 260

285NITRILE RUBBER, 104 154 228

272NITROGEN COPOLYMER, 335NITROGEN DIOXIDE, 236NITROGEN OXIDE, 236NITROGEN-CONTAINING

POLYMER, 42 287 292 293NITROXYL RADICAL, 220NOISE REDUCTION, 47NON-DESTRUCTIVE TESTING,

70 109 139 232 260 305 326336 341 363

NUCLEAR MAGNETICRESONANCE, 2 4 13 113 123127 154 155 180 211 229 286321 354

NUCLEOPHILIC, 154

OOCTANE, 67OCTANEDIOL, 79OIL, 303OIL ABSORPTION, 154OLEFIN, 7OLEFIN GROUP, 103OLIGOMER, 10 290 329ON-LINE INSPECTION

SYSTEM, 152ON-LINE MEASUREMENT, 178

303OPACITY, 247OPTIC FIBRE, 110 152 227 247

319 352OPTICAL DENSITY, 260 330OPTICAL FIBRE, 45 49 59 71 80

217OPTICAL LEVITATION, 135OPTICAL MICROSCOPY, 15 129

162OPTICAL PROPERTIES, 16 114

129 135 136 159 205 221 243247 253 267 269 270 283 284299 315 330 376

OPTICAL RECORDING MEDIA,143

OPTICAL STORAGE, 143OPTIMISATION, 162 196 338OPTORHEOLOGICAL

PROPERTIES, 96ORIENTATION, 1 39 46 51 52 55

79 83 90 114 119 131 143 158159 172 195 199 201 216 243250 270 282 291 299 346 359372

ORIENTATION FACTOR, 372ORIENTATION FUNCTION, 251ORIENTATIONAL, 6ORIENTED, 283ORTHORHOMBIC, 73 94 182

195OVERLAYING, 375OXAZOLIDONE, 377OXAZOLINE, 228OXIDATION, 54 100 104 112 120

142 154 189 237 279 306OXIDATIVE DEGRADATION,

54 100 104 154 162 189 237279 297

OXIDISATION, 162 189OXIRANE, 152 248 354OXIRANE COPOLYMER, 85OXYBENZOATE COPOLYMER,

325OXYDIANILINE, 332

OXYGEN, 3 154 256OXYGEN MUSTARD, 230OXYGEN UPTAKE, 336OXYNAPHTHOATE

COPOLYMER, 325OZONE, 189

PPACKAGING FILM, 272PAINT, 62 106 149 300PARACRYSTALLINE, 52 186PARTIAL LEAST SQUARES, 82

247 272 313 337PARTICLE SIZE, 77 86 120 135

144 176PARTITIONING, 295PEAK INTENSITY, 154 241PENDANT GROUP, 238PENTACYANOBIPHENYL, 136PENTYLCYANOBIPHENYL, 53

269PENTYLCYANOPHENYL

CYCLOHEXANE, 269PERDEUTERATION, 316PERFLUOROOCTYL GROUP, 12PERMEABILITY, 150 187PERMEATION, 36PEROXIDE GROUP, 189PH, 196 300PHASE BEHAVIOUR, 7 93 94

129 143 163 164 186 199 218219 229

PHASE DIAGRAM, 37PHASE SEGREGATION, 247PHASE SEPARATION, 33 88 101

129 280 323 344 364PHASE SHIFT, 7PHASE STRUCTURE, 10 88 213PHASE TRANSITION, 37 89 93

182 195 219 223PHENOL, 127PHENOL FORMALDEHYDE

RESIN, 58PHENOL-FORMALDEHYDE

RESOL RESIN, 127PHENOLIC RESIN, 34PHENOXY COPOLYMER, 348PHENOXY RESIN, 311 348PHENOXYPHENYLETHYNYL

BENZOPHENONE, 80PHENYL GLYCIDYL ETHER, 28

248PHENYLAMINOCARBONYLOXY-

ETHYL METHACRYLATECOPOLYMER, 338

PHENYLENE ACETYLENE

Subject Index


COPOLYMER, 345PHOTOCALORIMETRY, 262PHOTOCHEMICAL

DEGRADATION, 112 297PHOTOCHEMICAL STABILITY,

112PHOTOCROSSLINKING, 75PHOTOCURING, 75PHOTODECOMPOSITION, 112PHOTODEGRADATION, 76 112PHOTOINDUCED, 143PHOTOINITIATOR, 75 118 161PHOTOLUMINESCENCE, 317PHOTOMICROGRAPHY, 156PHOTOOXIDATION, 112 288PHOTOOXIDATIVE

DEGRADATION, 104 112 189279 336

PHOTOOXIDATIVE STABILITY,112

PHOTOPOLYMERISATION, 75240 263 353 363

PHOTORESIST, 353PHOTOSENSITISATION, 240PHOTOSTABILISER, 62PHYSICAL AGEING, 27PHYSICAL PROPERTIES, 45 82

141 151 152 187 270 364PHYSICOCHEMICAL

PROPERTIES, 249 322PHYSICOMECHANICAL

PROPERTIES, 28PIGMENT, 86 166PINENE, 283PLANAR, 5 188PLASMA, 3PLASMA POLYMERISATION,

171PLASMA TREATMENT, 162 342PLASTICISATION, 154 280 312PLASTICISER, 17 55 166PLASTICITY, 282PLATINUM, 121POLAR GROUP, 74POLARISATION, 5 6 108 179 223

243 282 291 334 359POLARISATION DIVISION

INTERFEROMETRY, 283POLARISATION MODULATION,

92POLARISED LIGHT, 346POLARISER, 52POLARON, 160 331POLING, 223 231POLY-ALPHA-

METHYLSTYRENE, 302 350POLY-N-VINYL CARBAZOLE,

121

POLY-P-METHYLSTYRENE, 302POLY-P-PHENYLENE, 317POLYACETAMIDO

ACRYLAMIDE, 65POLYACETYLENE, 160 345POLYACRYLAMIDE, 137 293

363POLYACRYLATE, 60 202 205 262POLYACRYLIC, 42 118 149 184

185 196 202 203 246 260 280282 319 326

POLYACRYLIC ACID, 40 42 147196 198

POLYACRYLIC ESTER, 202 205POLYACRYLONITRILE, 113 116

145 147 180 237 330 376POLYALKENE, 4 16 67 74 89 97

110 204POLYAMIC ACID, 115 332POLYAMIDE, 86 144 145 254 303

372POLYAMIDE-11, 36 223 231 254POLYAMIDE-12, 167 174POLYAMIDE-6, 102 305 311 376POLYAMIDE-6,12, 376POLYAMIDE-6,6, 229 372 376POLYANILINE, 108 121POLYBENZIMIDAZOLE, 323POLYBENZOPHENONE, 80POLYBENZYL ASPARTATE, 6POLYBENZYL GLUTAMATE, 6POLYBISPHENOL-A, 276 277POLYBISPHENOL A

BISHYDROXYPROPYLMETHACRYLATE, 103

POLYBISQUINOLYLBUTADIYNE,315

POLYBUTADIENE, 214 279 295335

POLYBUTYL ACRYLATE, 35 202POLYBUTYL METHACRYLATE,

53 126 136 280POLYBUTYLENE, 32 49POLYBUTYLENE

TEREPHTHALATE, 221 274POLYCAPROLACTONE, 311POLYCARBONATE, 83 149 177

201 221 241 329 348 361 362POLYCARBOXYLATE, 30POLYCARBOXYLIC ACID, 140POLYCHLOROPRENE, 104POLYDIACETYLENE, 43 111 220

315POLYDIETHYLENE GLYCOL

DIMETHACRYLATE, 263POLYDIMETHYL PHENYLENE

ETHER, 57POLYDIMETHYL PHENYLENE

OXIDE, 221POLYDIMETHYL SILOXANE, 7

83 119 291 362POLYDIVINYL ETHER, 240POLYELECTROLYTE, 42POLYENE, 374POLYEPICHLOROHYDRIN, 28POLYEPOXIDE, 18 41 63 75 79

112 197 205 207POLYEPSILON-

CAPROLACTAM, 188POLYESTER FILM, 1POLYESTERIMIDE, 243POLYETHER, 2 297POLYETHER ACRYLATE, 118POLYETHER DIAMINE, 197POLYETHER ETHERKETONE,

159POLYETHER SULFONE, 270POLYETHERIMIDE, 323POLYETHERURETHANEUREA,

355POLYETHOXYPROPYL-

ACRYLAMIDE, 293POLYETHYLENE, 4 10 11 20 45

46 67 70 71 81 86 94 99 110120 134 144 148 157 164 195205 206 216 218 221 247 249250 261 266 269 288 305 313316 324 327 346 366 368 373

POLYETHYLENE GLYCOL, 52198 367

POLYETHYLENE GLYCOLDIMETHACRYLATE, 263

POLYETHYLENE IMINE, 42 125POLYETHYLENE

NAPHTHALATE, 56POLYETHYLENE OXIDE, 52 85

233 297 309 310POLYETHYLENE

TEREPHTHALATE, 5 19 2627 50 81 90 92 120 131 157158 164 183 234 235 241 251261 266 284 307 320 339 355359 365 376

POLYFLUOROCARBON, 259POLYFLUOROETHYLENE, 146POLYFUNCTIONAL, 151POLYGLYCIDYL

METHACRYLATE, 255POLYHEXADIYNE, 43POLYHYDROXYBENZOIC

ACID, 325POLYHYDROXYETHYL

METHACRYLATE, 103 185POLYIMIDE, 7 9 115 332POLYIONENE, 92 154POLYISOBUTYLENE, 32 49

Subject Index


POLYISOCYANURATE, 59 267POLYISOIMIDE, 242POLYISOPRENE, 224 314 374POLYISOPROPYL

ACRYLAMIDE, 93 293POLYLAURYLLACTAM, 174POLYMER DISPERSED LIQUID

CRYSTAL, 37 38 88 280POLYMER MELT, 152POLYMERIC ADDITIVE, 137POLYMERIC ANTISTATIC

AGENT, 367POLYMERIC COMPATIBILISER,

133POLYMERISATION, 32 35 38 49

66 75 80 88 103 108 121 124135 142 151 155 171 188 214240 249 262 290 321 322

POLYMERISATION CATALYST,155 329

POLYMERISATION INITIATOR,214 238 240 321 327

POLYMERISATION KINETICS,32 38 151 238 263 314 315 363

POLYMERISATIONMECHANISM, 32 239 263 292308 314 322 329

POLYMERISATION MODIFIER,369

POLYMERISATION RATE, 88322 329 339

POLYMERISATIONTEMPERATURE, 103 321

POLYMERISATION TIME, 103POLYMETHACRYLATE, 185POLYMETHACRYLIC ACID, 140

273POLYMETHYL

METHACRYLATE, 52 145 150164 194 225 232 233 245 282319 326 347

POLYMETHYL STYRENE, 302350

POLYMETHYL VINYL ETHER,297

POLYMETHYLENE, 163POLYMETHYLENE OXIDE, 309POLYMORPHISM, 186 213 219POLYOLEFIN, 4 16 67 74 89 97

110 204 215 249 252 271 302318 366 371

POLYORGANOSILOXANE, 7POLYOXYETHYLENE, 85POLYOXYMETHYLENE, 309POLYPARAPHENYLENE

SULFIDE, 84POLYPEPTIDE, 6POLYPERFLUOROCARBOXYLATE,

30POLYPHENYLENE, 290 317POLYPHENYLENE

ACETYLENE, 345POLYPHENYLENE

BIBENZIMIDAZOLE, 323POLYPHENYLENE

DIBROMOETHYLENE, 345POLYPHENYLENE ETHER, 128POLYPHENYLENE OXIDE, 128POLYPROPYLENE, 4 16 22 31 44

45 70 74 77 81 97 110 117 133157 162 164 170 199 204 221

POLYPROPYLENE OXIDE, 85128

POLYPYRROLE, 121 298 331POLYSACCHARIDE, 162POLYSILOXANE, 163 291POLYSTYRENE, 23 29 35 57 77

78 81 89 92 107 128 135 145150 157 173 186 202 205 214215 219 222 252 266 271 279299 302 311 314 344 347 350351 371

POLYSTYRENESULFONATE,244

POLYSULFIDE, 9POLYTETRAFLUOROETHYLENE,

146 270POLYTETRAHYDROFURAN, 2POLYTETRAMETHYLENE

OXIDE, 2POLYTHIOETHER, 9POLYTHIOPHENE, 54POLYURETHANE, 18 39 55 59 60

100 102 106 149 156 206 236238 257 265 266 267 303 333355 358 360 375

POLYURETHANE ACRYLATE,161

POLYURETHANEDIACRYLATE, 161

POLYURETHANE ELASTOMER,24 55 95 156 364 375

POLYVINYL, 175POLYVINYL ACETATE, 52 129

273POLYVINYL ALCOHOL, 129 147

194 225 245 249 255 258 337POLYVINYL CARBAZOLE, 121

292POLYVINYL CHLORIDE, 3 17 51

76 81 145 153 157 175 176 181206 215 261 376

POLYVINYL CYANIDE, 113 116POLYVINYL ESTER, 238 328POLYVINYL HALIDE, 3 51POLYVINYL METHYL ETHER,

92POLYVINYL PYRIDINE, 140POLYVINYL PYRROLIDONE,

287POLYVINYLBENZENE, 29 57 77

78 128 135 186POLYVINYLIDENE CHLORIDE,

376POLYVINYLIDENE FLUORIDE,

61 187 213 223 256 283POTASSIUM BROMIDE, 339 343POTASSIUM COMPOUND, 30POTENTIOSTATIC, 290POWER LAW, 53 280PREGRAPHITISATION, 237PREHEAT, 167 174PREMELTING, 167 174PREPARATION, 278PREPOLYMER, 242PRESSURE-SENSITIVE

ADHESIVE, 289PRESTRETCHING, 199PRETREATMENT, 82 322PRINCIPAL COMPONENTS

ANALYSIS, 178 222PROBE, 247 314 352PROCESS CONTROL, 152 227

314PROCESSING, 204 237PROCESSING AID, 175PROOFED FABRIC, 259PROPAGATION, 32 214 248 329PROPAGATION RATE

CONSTANT, 214 240PROPENE COPOLYMER, 74 117

123 189 204 221PROPYL ETHER, 246PROPYLENE COPOLYMER, 74

117 123 189 204 221PROPYLENE GLYCOL, 246PROPYLENE-ETHYLENE

COPOLYMER, 110 123 189PROTEIN, 42PROTON, 341PROTON CONDUCTING, 61PROTON TRANSFER, 244PROTONATION, 296PSEUDO CROSSLINK, 154PULSE EXCITATION, 229PYRENE, 218PYROLYSATE, 166PYROLYSIS, 274 302 325 358PYROLYSIS GAS

CHROMATOGRAPHY, 113PYROMELLITIC

DIANHYDRIDE, 332PYRROLE POLYMER, 121

Subject Index


QQUALITY CONTROL, 14 77 109

128 152 247 356 366 367QUANTITATIVE ANALYSIS, 3 4

8 72 74 126 176 184 202 226272 338 356

QUANTUM MECHANICS, 67QUATERNARY AMMONIUM

GROUP, 244QUENCHING, 177 219

RRADIATION CURING, 118 191RADIATION DEGRADATION,

330RADIATION DOSE, 146RADICAL POLYMERISATION,

124 135 151RADIO LABELLING, 289RAMAN SCATTERING, 9 108

304RANDOM COPOLYMER, 123

321RAPID HEATING, 31RAPID SCAN, 134 148 163RATE CONSTANT, 24 58 228 248

345RATE OF POLYMERISATION, 88REACTION INJECTION

MOULD, 364REACTION MOULD, 364REACTION RATE, 278 360REACTIVE BLENDING, 278REACTIVE PROCESSING, 227REACTIVE SITE, 3REACTIVITY, 165 189 196 262

354REACTIVITY RATIO, 64 314 321REAL TIME, 38 80 135 227 250

262 263 271 323RECYCLING, 77 157 209 247 261REDOX STATE, 298REDUCTION, 331REFLECTANCE, 5 247REFLECTANCE

SPECTROSCOPY, 6 21 49 112137 172 192 307

REFLECTION ABSORPTIONSPECTROSCOPY, 50 233 273

REFRACTIVE INDEX, 5 6 135217 326

REGIOCHEMISTRY, 116REGIOSELECTIVITY, 116REGRESSION ANALYSIS, 58 73

81 82 141 247 264 272REINFORCED PLASTIC, 109 161

166 190 207 212 217 221 237249 279 281 286 328 352 357

RELATIVE HUMIDITY, 246 312RELAXATION RATE, 92RELAXATION TIME, 201REORIENTATION, 16 199RESIDUAL MONOMER, 306 326RESIDUAL SOLVENT, 330RESIDUAL UNSATURATION,

154RESOLUTION, 164 222RESONANCE, 135 374REVERSE PHASE, 215REVERSIBLE, 65 197 253RHEOLOGICAL PROPERTIES,

16 96 117 170 243 253 304RICE HUSK ASH, 268RING OPENING, 13 217RING-CLOSURE, 332ROTATIONAL ISOMER, 307ROTATIONAL ISOMERIC STATE

THEORY, 309ROUGHNESS, 108

SSAPPHIRE, 110SATURATED POLYESTER, 133

143 183 284 325 353 365SATURATION, 164SAW, 188SCANNING ELECTRON

MICROSCOPY, 99 117 120156

SCRAP POLYMER, 81SCREW SPEED, 247SEAL, 154 192 200SEBACIC ACID, 133SECTIONING, 156SEGMENT, 163SEGMENTAL MOBILITY, 83 143SEGMENTAL ORIENTATION,

143 201SEGREGATION, 286 344SELECTIVITY, 30 116SELF-ASSOCIATION, 65 287SELF-DRYING, 86 144SEMI-EFFICIENT

VULCANISATION, 304SEMICRYSTALLINE, 26 52 186SENSOR, 110 178SEPARATION, 206 209SEQUENCE ANALYSIS, 10 123SEQUENCE DISTRIBUTION,

123 155 229 314SEQUENTIAL ELECTROLYSIS,

121SERVICE PROPERTIES, 341

SHEAR, 282SHEAR PROPERTIES, 281SHEAR STRESS, 212SHEAR YIELDING, 281SHEET, 156 204SHORT CHAIN, 4SHORT ITEM, 144 164 190 279SIDE CHAIN, 1 39SIDING, 76 153 175SIGNAL TRANSMISSION, 7SILANE COPOLYMER, 327SILANOL, 2 7SILICA, 33 142 217 268 304 324

366SILICATE, 44SILICON, 42SILICON CARBIDE FIBRE-

REINFORCED PLASTIC, 161SILICON DIOXIDE, 33 142SILICON-29, 2SILICONE COPOLYMER, 275SILICONE POLYMER, 163 289

291 303SILOXANE, 202SILOXANE COPOLYMER, 275SILVER, 9 108 362SIMULTANEOUS

INTERPENETRATINGPOLYMER NETWORK, 238

SINGLE CRYSTAL, 213 373SINGLE FIBRE, 161 212SINGLE SITE CATALYSIS, 155SINGLE-SCREW EXTRUDER,

247SIZE EXCLUSION

CHROMATOGRAPHY, 215257

SKIN-CORE MORPHOLOGY,346

SLIP AGENT, 366SMALL ANGLE X-RAY

SCATTERING, 10SMECTIC, 39 163SMOKE CHAMBER, 236SODIUM, 160SODIUM BOROHYDRIDE, 288SODIUM CELLULOSATE, 294SODIUM DIOCTYL

SULFOSUCCINATE, 21 202SODIUM DODECYLSULFATE,

21SODIUM HYDROXIDE, 146 288

294SODIUM METHACRYLATE

COPOLYMER, 310SODIUM THIOCYANATE, 65SOFT SEGMENT, 39 55SOFTWARE, 148 152 242

Subject Index


SOL-GEL, 13SOLID, 129 258 326SOLID PHASE, 7SOLID STATE, 2 113 129 229 354

361SOLID STATE

POLYMERISATION, 220 315SOLIDS CONTENT, 246SOLITON, 160SOLUBILITY, 17 26 37 55 88 124

133 180 196 224 304SOLUTION CASTING, 233 344SOLUTION POLYMERISATION,

35 321 363SOLUTION PROPERTIES, 287

293SOLVENT, 47 65 89 150 154 196

257 321 322 330 332 338SOLVENT ABSORPTION, 154SOLVENT CAST, 3 180 298SOLVENT EXTRACTION, 4 272SORPTION, 26 150 230 300SPACER, 243SPACER LENGTH, 143SPECIFIC VOLUME, 150SPECIFICATION, 356SPECTRAL SUBTRACTION,

156 186 189 323SPECULAR REFLECTANCE, 5

247 251SPHERULITE, 52 187SPRAY DRYING, 86 144SPUTTER ETCHING, 137SQUALENE, 9STABILISER, 62 86 144 166 175

176 189 368STABILITY, 113 189STANDARDISATION, 166STATIC ABSORPTION, 96 169STATISTICAL EXPERIMENTAL

DESIGN, 211STEARIC ACID, 304 371STEEL, 285STEP POLYMERISATION, 238STEP SCANNING, 8 18 163 168STEP-SCAN FTIR

SPECTROSCOPY, 7 164 235STEP-SCAN PHOTOACOUSTIC

SPECTROSCOPY, 7 18 44 103148

STEREOCHEMISTRY, 219 258329

STEREOREGULARITY, 211STEREOSEQUENCE

DISTRIBUTION, 219STERIC HINDRANCE, 154STOICHIOMETRY, 154 165 296STOPPED-FLOW

SPECTROSCOPY, 329STORAGE, 189STRAIN, 16 39 51 55 94 102 134

161 187 210 212 235 250 281282 304

STRAIN-HARDENING, 210STRAND, 247STRATIFICATION, 8STRESS, 99 154 187 199 243 250

282STRESS CONCENTRATION,

207STRESS CRACK RESISTANCE,

99STRESS RELAXATION, 92 197

201STRESS TRANSFER, 161 212STRESS-INDUCED

ENVIRONMENTDIFFUSION, 99

STRESS-STRAIN PROPERTIES,79 161 187 197 207 250 282299 320 355

STRETCH, 1 9 55 92 99 102 199291

STRUCTURAL ADHESIVE, 312STRUCTURAL PROPERTIES, 4

58 151 177 250STRUCTURE-PROPERTY

RELATIONSHIP, 79STYRENE, 60 226 257 272STYRENE COPOLYMER, 35 61

92 101 221 296 310 343 344STYRENE TERPOLYMER, 21STYRENE-BUTADIENE-

STYRENE BLOCKCOPOLYMER, 29

STYRENE-METHACRYLICACID COPOLYMER, 310

STYRENESULFONIC ACIDCOPOLYMER, 92 296

STYRENESULPHONIC ACIDCOPOLYMER, 92 296

SUBMICRON, 164SUBSTRATE, 149 150 153 165

194 202 232 233 245 246 285290

SUCCINIC ANHYDRIDECOPOLYMER, 74

SULFONATION, 61 311SULFUR, 224 304SULFUR DIOXIDE, 236SULFUR MUSTARD, 230SULFUROUS ACID, 300SUPERCRITICAL FLUID, 26 303SURFACE, 3 17 121 146 194 245SURFACE ACTIVE AGENT, 21

166 202 203 303

SURFACE ANALYSIS, 21 285342 344 359 362 375

SURFACE CRACKING, 156SURFACE ENERGY, 327SURFACE ENHANCED RAMAN

SCATTERING, 9 108SURFACE MODIFICATION, 342SURFACE MORPHOLOGY, 21SURFACE PROPERTIES, 8 21

156 202 204 241 259 288 318327

SURFACE STRUCTURE, 21 111241 318 359

SURFACE TREATMENT, 108 162193 232 237 285 303 322 342

SURFACTANT, 21 166 202 203303 349

SURGICAL ADHESIVE, 193 200SYNDIOTACTIC, 23 89 173 186

219 350SYNTHESIS, 2 35 88 115 124 125

214 240 319SYNTHETIC FIBRE-

REINFORCED PLASTIC, 221249

SYNTHETIC RUBBER, 224

TTACKIFIER, 165TACTICITY, 129 180 211 219 350TAPERED, 314TAUTOMERISM, 354TEMPERATURE, 26 53 77 89 94

128 134 147 154 155 163 165176 177 185 188 189 196 204217 240 243 246 248 280 302304 312 323 325 327 345

TEMPERATURE DEPENDENCE,56 78 112 113 114 126 146 163167 182 230 279 334 361

TEMPERATURE RANGE, 128167 214 238 240 242

TEMPERATURE RISINGELUTION FRACTIONATION,123

TEMPERATURE SENSITIVITY,293

TENSILE DRAWING, 99TENSILE MODULUS, 320TENSILE PROPERTIES, 46 79

117 161 207 212 237 251 282320 355

TENSILE STRAIN, 161TENSILE STRENGTH, 79 117TERMONOMER, 229TERNARY BLEND, 11

Subject Index


TERPENE PHENOL RESIN, 165233

TERPOLYMER, 66 343TETRABUTYLAMMONIUM

FLUORIDE, 321TETRACHLOROMETHANE, 126TETRAETHOXYSILANE, 2TETRAHYDROFURAN, 84 126

175 213 321TETRAMETHOXYSILANE, 13TETRAMETHYLTHIURAM

DISULFIDE, 304THERMAL ANALYSIS, 23 84

113 155 242 302 323THERMAL ANNEALING, 177

228THERMAL CONVERSION, 345THERMAL CURING, 242THERMAL DEGRADATION, 113

145 189 273 274 279 358THERMAL POLYMERISATION,

80THERMAL PROPERTIES, 29 53

93 113 120 128 141 155 165174 197 212 304

THERMAL STABILITY, 113 189302 325

THERMAL TRANSITION, 53THERMAL TREATMENT, 213

220THERMODYNAMIC

PROPERTIES, 177THERMOGRAVIMETRIC

ANALYSIS, 89 113 120 274323

THERMOMECHANICALPROPERTIES, 28 117 177

THERMOOXIDATION, 120 142THERMOOXIDATIVE

DEGRADATION, 104 279 323THERMOOXIDATIVE

STABILITY, 120THERMOPLASTIC

ELASTOMER, 39 304 364THERMOPLASTIC RUBBER, 39THERMOREVERSIBLE, 65THICK FILM, 72THIN FILM, 50 108 122 142 155

230 232 254 272 275 285 362THIOLENE, 38TIE MOLECULE, 187TIME DEPENDENCE, 112 135

352TIME RESOLVED

SPECTROSCOPY, 101TITANIA, 76TITANIUM ALKOXIDE, 124TITANIUM DIOXIDE, 76

TITANIUM TETRAALKOXIDE,124

TOLUENE, 133TOLUENE SULFONATE, 331TOPOCHEMICAL

POLYMERISATION, 315TOPOGRAPHY, 111TORQUE, 304TOUGHENING, 278TOUGHNESS, 278TRANS-POLYACETYLENE, 160TRANSESTERIFICATION, 348TRANSFORMATION, 151TRANSITION PHENOMENA, 31

216 309TRANSITION PROPERTIES, 216TRANSITION TEMPERATURE,

53 163TRANSMISSION ELECTRON

MICROSCOPY, 117 120 221TRANSMISSION FLUID, 154TRANSMISSION

SPECTROSCOPY, 4 104 146156 183 357

TRANSPARENCY, 247TRANSPORT COEFFICIENT,

230TRANSPORT NUMBER, 230TREAD, 341TRIAD, 155TRIBLOCK COPOLYMER, 85

344TRIMER, 302TRIMETHYLOLPROPANE

DIALLYL ETHERCOPOLYMER, 37 38

TRIMETHYLOLPROPANETRISTHIOL COPOLYMER,37 38

TUNGSTEN, 283TWISTON, 182TWO-DIMENSIONAL, 25 57 73

95 111 148 163 167 168 169174 218 235 254

TWO-LAYER, 194 245TWO-PART, 121TYRE, 139 341

UULTRA-THIN, 285ULTRADRAWN, 195 346ULTRAVIOLET CURING, 38 62

75 88 118ULTRAVIOLET IRRADIATION,

18 149 288 297ULTRAVIOLET

POLYMERISATION, 38 75 263

ULTRAVIOLETSPECTROSCOPY, 71

UNFILLED, 91 154UNIAXIAL, 79 235 243 253UNIAXIAL ORIENTATION, 1

251 359UNIAXIAL STRETCHING, 250UNIAXIALLY ORIENTED, 158UNIDIRECTIONAL, 223UNLOADING, 197UNSATURATED POLYESTER,

135 328 370UNSATURATION, 154 189UREA, 333URETHANE, 333URETHANE COPOLYMER, 96URETHANE DIACRYLATE

OLIGOMER, 161

VVANADIUM, 155VAPOUR, 150VARIATION COEFFICIENT, 176VINYL ACETATE, 72 130 141 226

272VINYL ACETATE COPOLYMER,

273VINYL ALCOHOL

COPOLYMER, 117 255VINYL CHLORIDE

COPOLYMER, 166VINYL CONTENT, 272 369VINYL CYANIDE, 154VINYL ESTER RESIN, 328VINYL GROUP, 272VINYL IMIDAZOLE

COPOLYMER, 142VINYL PHENOL COPOLYMER,

321VINYL PYRIDINE

COPOLYMER, 92 296VINYL SILANE, 142VINYL SILANE COPOLYMER,

142VINYL TOLUENE

COPOLYMER, 200VINYLIDENE FLUORIDE

COPOLYMER, 61VINYLPYRIDINE COPOLYMER,

92VINYLTRIMETHOXYSILANE

COPOLYMER, 142 327VIRGIN POLYMER, 247VISCOELASTIC PROPERTIES,

312VISCOELASTICITY, 312

Subject Index


VISCOSITY, 276 277 372VOLATILE, 189 302 325VOLUME CHANGE, 154VOLUME FRACTION, 165 192VULCANISATE, 304VULCANISATION, 154 304VULCANISATION TIME, 200VULCANISED, 264

WWATER, 17 36 93 140 146 150 154

185 196 232 246 258 287 293294 319 354

WATER ABSORPTION, 150 312WATER BINDING, 246WATER CONTENT, 185 246WATER PERMEABILITY, 150

300WATER RESISTANCE, 50WATER SOLUBLE, 297WAVE NUMBER, 154 189 264

WAVEGUIDE, 217 227WAVELENGTH, 135 141 247WEAR, 259WEATHER RESISTANCE, 76 149

153 189WEIGHT GAIN, 230WET SEPARATION, 175WIDE ANGLE, 94 114 116 173

180 186WIDTH, 161WINDOW FRAME, 176WOOL, 259

XX-RAY DIFFRACTION, 56 114

116 186 372X-RAY EMISSION

SPECTROMETRY, 341X-RAY FIBRE DIAGRAM, 195X-RAY PHOTOELECTRON

SPECTROSCOPY, 140 317

X-RAY SCATTERING, 10 56 94114 116 173 180 186

XENON ARC, 149XEROGEL, 2XYLENE, 133

YYARN, 320 337 372YIELD STRESS, 187YOUNG’S MODULUS, 10 79 187

216 237 312

ZZINC, 285ZINC OXIDE, 196 304ZINC SALT, 311ZINC SELENIDE, 194 215 245ZINC STEARATE, 33

Subject Index
