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31st Annual
International Symposium on Polymer Analysis and Characterization
Book of Abstracts
June 3-6, 2018
North Bethesda, Maryland, USA
ISPAC 2018
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ISPAC 2018
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ISPAC 2018
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What is ISPAC?
ISPAC stands for International Symposium on Polymer Analysis and Characterization. It is a non-profit scientific organization formed to provide an international forum for the presentation of recent advances in the field of polymer analysis and characterization methodologies. This unique Symposium brings together analytical chemists and polymers scientists involved in the analysis and characterization of polymeric materials. Meetings are held annually, rotating to venues in the USA, Europe and Asia.
ISPAC sessions comprise a two and a half day program with invited lectures, submitted lectures, poster sessions, discussions and information exchange on polymer analysis and characterization approaches, techniques and applications. Invited talks include state-of-the art developments. Each session features lectures and a 30 minute open discussion period. The participants typically come from academic, industrial, and government settings and work with different aspects of polymer analysis and characterization approaches, techniques and applications. It will be useful to network with one another, exchanging information and tips about different techniques, and learning about the latest developments.
Lecturers are urged to include introductory material in their presentation to bring participants "up to speed", and are allotted the time to accomplish this. The discussion periods allow for extended interaction among the lecturers and the conference participants.
If your work involves any aspect of polymer characterization, physical testing, materials analysis, or polymers in general, please consider attending this conference. You are welcome to submit a contributed oral paper or a poster.
ISPAC 2018
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Save the Date : ISPAC 2019
Date: June 2nd (SUN) to 5th (WED) Location: Miyagi Zao Royal Hotel
(http://www.daiwaresort.jp.e.zr.hp.transer.com/zaou/index.html/)
ISPAC 2018
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ISPAC Governing Board
Wayne F. Reed, Tulane University, USA; [email protected], ISPAC GB Chair for the Americas, ISPAC-2013 Chair
G. Julius Vancso, University of Twente, The Netherlands; [email protected], ISPAC GB Chair for Europe and Asia, ISPAC-2012 Chair
Taihyun Chang, Pohang University of Science and Technology, Republic of Korea; [email protected]
H.N. Cheng, USDA Southern Regional Research Center, USA; [email protected]
A. Willem deGroot, Dow Chemical Co., USA; [email protected], ISPAC-2015 Chair
Nikos Hadjichristidis, KAUST, King Abdullah University of Science and Technology, Saudi Arabia; [email protected]
Josef Janca, Institute of Scientific Instruments, Academy of Sciences of the Czech Republic, Brno, Czech Republic; [email protected]
Yeng Ming Lam, NTU-MSE, Singapore, [email protected], ISPAC 2016 Symposium Chair
Harald Pasch, University of Stellenbosch, South Africa; [email protected]
Clemens Schwarzinger, Johannes Kepler University, Linz, Austria; [email protected], ISPAC 2017 Symposium Chair
Associate Member of the Governing Board
Hiroshi Jinnai, Tohoku University, Japan, [email protected]
Emeritus Members of the Governing Board
Howard Barth, DuPont Co., USA, ISPAC Founding Chair Emeritus
Guy Berry, Carnegie Mellon University, USA; [email protected], ISPAC GB Honorary Chair Emeritus
Stephen T. Balke, University of Toronto, Canada
Oscar Chiantore, University of Torino, Italy, [email protected]
John V. Dawkins, Loughborough University, UK
Marguerite Rinaudo, CERMAV-CNRS, France, [email protected], ISPAC-2014 Chait
Pavel Kratochvil, Institute of Macromolecular Chemistry, Czech Republic
Sadao Mori, Mie University, Japan
Petr Munk, University of Texas at Austin, USA
ISPAC 2018
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ISPAC 2018 Organizing Committee
Ronald Jones (Symposium Chair) – NIST, [email protected]
Kathryn Beers - NIST, [email protected]
Willem deGroot – DowDupont, [email protected]
Alexander Norman – ExxonMobil, [email protected]
Peter Olmsted – Georgetown University, [email protected]
Lawrence Sita – University of Maryland, [email protected]
Andre Striegel – NIST, [email protected]
ISPAC 2018 – Sunday, June 3, 2018
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ISPAC Short Courses Emerging Trends in Polymer Characterization 7:45 AM Breakfast – Linden Oak 8:00 Registration, All Day – Brookside Foyer
Neutron and X-ray Techniques
Brookside A
Advances in Polymer Characterization Brookside B
9:00 Elastic Scattering Methods for Characterizing Structure Michael Hore, Case Western Reserve University
Introduction to interaction-based separations: IC, LCCC and 2D-LC Taihyun Chang, Pohang University
10:30 Break
10:45 Inelastic scattering methods for characterizing mobility Yun Liu, NIST
Introduction to size-based separations: SEC, HDC, FFF, and detection methods Andre Striegel, NIST
12:15 PM Lunch (Linden Oak)
1:00 Imaging Soft Materials with X-rays and Neutrons Daniel Hussey, NIST
Emerging Trends in Rheology Anthony Kotula, NIST
2:30 Break
2:45 Rheology and Small Angle Scattering Kathleen Weigandt, NIST
Polymer Science and Advanced Solid State NMR Ryan Nieuwendaal, NIST
6:00 Reception – Forest Glen
ISPAC 2018 – Monday, June 4, 2018
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7:00 AM Registration, All Day – Grand Foyer
Vendor Exhibition, All Day – Grand Foyer 7:00 AM Breakfast – Salon H
8:00 AM Opening Remarks – Dr. Ronald Jones and Prof. Wayne Reed (Salon F/G) 8:15 AM Materials Science at NIST – Dr. Eric Lin, Director, Material Measurement
Laboratory, NIST (Salon F/G)
Advances in Polymer and Soft Materials Rheology Plenary Lectures – Salon F/G 8:30 AM M.01 - DowDuPont Lecture
Polyethylene topology and rheology control for recycling applications Jaap den Doelder, DowDuPont
9:00 AM M.02 - Predicting the Linear and Non-Linear Rheology of Polydisperse Linear Polymers Daniel Read, University of Leeds
9:30 AM M.03 - Toward in situ morphology characterization of polymeric fluids under arbitrary processing flows Matthew Helgeson, University of California Santa Barbara
10:00 AM Rheology Discussion Panel
10:30 AM Refreshments
Deformation of Soft Materials Salon F
Characterization with Chromatography Salon G
11:00 AM M.11 – Rheo-Raman microscopy for polymer crystallization characterization – A. Kotula
M.15 – Comparison of fast SEC and UHP SEC for the second dimension in two-dimensional liquid chromatography of polymers – E. Uliyanchenko
11:20 AM M.12 – Effects of Orientation and Deformation Mode in Dynamic Mechanical Analysis of Engineered Materials – S. Cotts
M.16 – Understanding Polymer Structure by Interaction Polymer Chromatography - C.J.Rasmussen
ISPAC 2018 – Monday, June 4, 2018
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11:40 AM M.13 – Selective Cell Adhesion on Peptide-Polymer Nano-Fiber Mats - G. Kaur
M.17 – Light Scattering without Refractive Index Increment: A New Approach to Calibrate SEC-Light Scattering Setups – D. Lohmann
12:00 PM M.14 – Viscoelastic behavior of polyelectrolyte complexes across coacervate-precipitate transition regime – S. Ali
M.18 – Fast Separations of Synthetic Polymers Using Advanced Polymer Chromatography (APC) - Janco, M.
12:20 PM Buffet Lunch - Salon H
12:30 PM
Poster Setup
V.1 – Ondax (sponsored presentation) Salon G
12:50 PM V.2 – Tosoh (sponsored presentation) Salon G
1:10 PM V.3 – Waters (sponsored presentation) Salon G
Advancing Materials Science with Big Data Plenary Lectures - Salon F/G
2:00 PM M.04 – Scoping the Polymer Genome: A Roadmap for Rational Polymer Dielectrics Design and Beyond Rampi Ramprasad, Georgia Institute of Technology
2:30 PM M.05 – Towards Polymer Informatics: Databases, Infrastructure and Beyond Debra Audus, NIST
3:00 PM M.06 – Materials-Specific Considerations for Machine Learning Bryce Meredig, Citrine Informatics
3:30 PM Big Data Discussion Panel 4:00 PM Refreshments
ISPAC 2018 – Monday, June 4, 2018
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Computation and Characterization Salon F
Molecular Control and Characterization Salon G
4:30 M.21 – From Data Science to Data Stories: Automating advanced analytics for R&D and manufacturing – G. Smits
M.24 – Perfect Polystyrene Sulfonate: Synthesis, Characterization and Self Diffusion in Ternary Solutions – P. Balding
4:50 PM M.22 – typyPRISM: A Computational Tool for Liquid-State Theory Calculations of Macromolecular Materials – T. Martin
M.25 – Conformational control of tethered functionalized mPEO on anatase nanocrystals surface – R. Simonutti
5:10 PM M.23 – TBA - F. Vargas Lara M.26 – Preparation and Characterization of Polyurethanes from Carbohydrates – H. N. Cheng
Poster Exhibition
White Oak A Heavy hors d’ouevres and Open Bar
6:30 – 9:00
ISPAC 2018 – Tuesday, June 5, 2018
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7:00 AM Registration, All Day – Grand Foyer
Vendor Exhibition, All Day – Grand Foyer 7:00 AM Breakfast – Salon H
Advances in Chromatography and Spectroscopy Plenary Lectures - Salon F/G
8:00 AM T.01 – Correlated polymer characterization via SEC-IR Detection with a new QCL Laser Spectrometer and SEC-NMR with a new 60 MHz MR-NMR Spectrometer Jennifer Kubel, Karlsruhe Institute of Technology
8:30 AM T.02 – Characterization of Complex Synthetic Polymers by Advanced Separations and Detection Techniques David Meunier, DowDuPont
9:00 AM T.03 – HPLC Characterization of Block Copolymers Taihyun Chang, Pohang University of Science and Technology
9:30 AM Chromatography and Spectroscopy Discussion Panel
10:00 AM Refreshments
Condensed Phases Salon F
Macromolecular Architectures Salon G
10:30 AM T.11 – Two-Dimensional Terahertz (2D THz) Raman Correlation Spectroscopy Study of the Crystallization of Bioplastics – I. Noda
T.15 – Synthesis and Characterization of Polyolefins with Precise Control of Branch Frequency and Branch Length – S. V. Orski
10:50 AM T.12 – Imaging Orientation Angles and Order Parameters of Semicrystalline Polymers by Polarization IR and Raman – Y. Lee
T.16 – Functional electrospun membranes featuring grafted polymer brushes: The characterization challenge – Y. Liu
11:10 AM T.13 – Multiple Order-to-Order Transitions within Ultrathin Films of Sugar-Polyolefin Amphiphilic Conjugates – S. R. Nowak
T.17 – Characterization of the chemical composition distribution of 1-octene based POP/POE by HPLC – J. H. Arndt
ISPAC 2018 – Tuesday, June 5, 2018
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11:30 PM T.14 – Liquid-solid transitions of a repulsive system with also a short-range attractive potential – G. Yuan
T.18 – Striving for Perfection: “Defect”-Free Polymer Networks for Improved Metrology – J. Sarapas
11:50 PM
Buffet Lunch – Salon H
ISPAC Leaders of R&D Panel Discussion
“The Next Generation of Characterization Needs in Polymer Science” Salon F/G 1:15 PM Pat Brant (ExxonMobil), Naryan Ramesh (DowDuPont), Raj Krishnaswamy
(Braskem North America), Peter Maziarz (Pfizer Consumer Health) Discussion Leader: Eric Lin, NIST
Macromolecular Architectures Plenary Lectures - Salon F/G
2:30 PM T.04 – ExxonMobil Lecture Molecular Engineering with Anionic Polymerization Lian Hutchings, Durham University
3:00 PM T.05 – New Opportunities for Precision Polyolefins: Design, Characterization and Dynamic Behavior of Nanostructured Polyolefin Block Copolymers Lawrence Sita, University of Maryland
3:30 PM T.06 - Polyhomologation: A Powerful Tool Towards Well-Defined Polyethylene-Based Polymeric Materials Nikos Hadjichristidis, KAUST
4:00 PM Architectures Discussion Panel
4:30 PM Break
ISPAC 2018 – Tuesday, June 5, 2018
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Condensed Phase Spectroscopy Salon F
Advances in Chromatography Salon G
5:00 PM T.21 – Bulk heterojunction interfacial structure from REDOR NMR – R. Nieuwendaal
T.25 – Characterization of branched polycarbonate by comprehensive two-dimensional liquid chromatography with multi-detector setup and correlation with Monte-Carlo simulations – N. Appel
5:20 PM T.22 – Characterization of modified silicas with industrial interest – A. M. Netto
T.26 – Valorisation of multi-dimensional analytical approaches to unlock complex products characterization. The particular case of apolar commercial synthetic polymers – J. Desport
5:40 PM T.23 – Relating Post Yield Mechanical Behavior in Polyethylenes to Spatially-varying Molecular Deformation Using Infrared Spectroscopic Imaging: Homopolymers – P. Mukherjee
T.27 – Size Exclusion Chromatography Characterization of Poly(Ester Urethane) Degradation Products – D. Yang
6:00 PM T.24 - Influencing liquid crystalline gel formation in cellulose ionic liquid solutions by adding water and nanoparticles – A. Rajeev
T.28 – Polymer separation beyond SEC – expanding the range from molecules to particles – R. Reed
6:30 PM ISPAC Social Hour Grand Ballroom Veranda Hors d’Ouevres and Open Bar
7:30 PM 2018 ISPAC Banquet Ballroom E
ISPAC 2018 – Wednesday, June 6, 2018
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7:00 AM Registration, All Day 7:00 AM Breakfast
Emerging Methods in Scattering Plenary Lectures - Salon F/G
8:00 AM W.01 - Wyatt Technology Lecture Structure and Dynamics in Polymer Grafted Nanoparticle Systems Michael Hore, Case Western Reserve University
8:30 AM W.02 – Recent Advances in X-ray Scattering Methods for Soft Materials Kevin Yager, Brookhaven National Laboratory
9:00 AM W.03 – Pfizer Consumer Healthcare Lecture Soft matter structure measurement by Polarized Resonant Soft X-ray Scattering Dean DeLongchamp, NIST
9:30 AM Scattering Discussion Panel 10:00 AM Refreshment Pause/Lunch Pickup
Tour of the National Institute of Standards and Technology (NIST) Participants must register for tour through ISPAC website prior to meeting to meet security requirements.
10:30 AM Bus pickup at Marriot Main Lobby 11:15 AM NIST Integrating Sphere Laboratory 12:00 PM Lunch at NIST Cafeteria (not included in registration)
Walk thru NIST Museum 1:15 PM Trace Contraband Detection Laboratory 2:00 PM NIST Center for Neutron Research 3:00 PM Arrive at Marriot
End of 2018 ISPAC meeting, see you in Japan!!
ISPAC 2018 – Plenary : Advances in Polymer and Soft Materials Rheology
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DowDuPont Lecture
M.1 - Polyethylene topology and rheology control for recycling applications
Jaap den Doelder
Performance Plastics R&D, Dow Benelux BV, Terneuzen, The Netherlands. [email protected]
Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The
Netherlands. [email protected]
Transforming polymer pellets into desired products like films and bottles requires tailored
viscoelastic polymer properties. The base rheology can be predicted from molecular structure,
including features such as molar mass distributions coupled to long-chain branching topology
distributions. This can be connected back to the chemistry and processes used to manufacture
the pellets. Examples of this process-to-product connectivity will be given in this talk for
industrial solution and high-pressure ethylene polymerization.
Thermoplastic polymers like polyethylene can be remolten and extruded multiple times. As
such, they are very suitable to feature in mechanical recycling applications, which is an area of
strongly growing society interest. Current applications however are limited due to lack of
knowledge and control of recycled polymer grade performance. We will present two scenarios
where the molecular rheology framework, as used before for virgin polymers, is applied to
predict the processability performance of recycled material. The first case deals with post-
consumer HDPE blend viscosity predictions. The second example quantifies the rheological
implications of structural modification and degradation during high-temperature extrusion of
LDPE. This methodology brings added control to mechanical recycling and thus opens up a
growing spectrum of applications for recycled polymers.
ISPAC 2018 – Plenary : Advances in Polymer and Soft Materials Rheology
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M.2 - Predicting the Linear and Non-Linear Rheology of Polydisperse
Linear Polymers
Daniel J. Read, Chinmay Das, Victor A.H. Boudara
School of Mathematics, University of Leeds, Leeds, LS2 9JT, U.K. [email protected]
The last fifty (yes, fifty!) years have seen an enormous amount of progress in predicting the
flow behavior of entangled polymeric materials. Building on the pioneering work of de
Gennes, Edwards and Doi, the dynamics of polymers are understood in terms of the “tube
model” (or related theories), which predict relaxation processes such as reptation, contour
length fluctuations, and constraint release; and, for rapid non-linear deformations, stretch
relaxation of the polymer chains. Academic studies have typically (and successfully) focused
on idealized polymeric systems: nearly monodisperse polymers, or mixtures of two or three
molecular weights. However, industrial polymer resins are almost always polydisperse, often
strongly so. This drives the question: for a given, known, distribution of molecular weight,
can we predict the linear, and non-linear, rheology?
Most schemes for predicting linear rheology of polydisperse polymers have built on the
“double reptation” formalism (see [1] for a summary). This predicts the relaxation of the
mixture from the relaxation profiles of the individual components, but crucially assumes that
the relaxation spectrum of one polymer is not affected by being mixed with the others. This
assumption is certainly wrong for the simplest “polydisperse” polymer, a bidisperse mixture
of just two molecular weights (but broad polydispersity often masks these errors).
We will present two developments from our group: (i) a computational algorithm for
predicting the linear rheology of arbitrary mixtures of linear polymers, which builds upon
our recent work on bidisperse polymers, and (ii) a simple “toy” constitutive equation which
can be used to predict non-linear flow behavior in shear and extension of bidisperse, and
polydisperse, polymers.
[1] Dealy, J. M., D. J. Read, and R. G. Larson, “Structure and rheology of molten polymers:
from structure to flow behavior and back again” (Carl Hanser Verlag GmbH & Co. KG,
Munchen, 2018).
ISPAC 2018 – Plenary : Advances in Polymer and Soft Materials Rheology
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M.3 - Toward in situ morphology characterization of polymeric fluids
under arbitrary processing flows
Matthew E. Helgeson
Department of Chemical Engineering, University of California Santa Barbara, Santa Barbara, CA USA.
In situ small angle neutron scattering under flow (flow-SANS) has become a critical tool for
measuring and formulating processing-structure-property relationships of polymeric fluids.
However, sample environments and associated measurement methods for flow-
SANS/SAXS have largely limited these measurements to steady state flows and simple
rheometric deformations (pure shearing or elongation) that fail to capture the complex
nonlinear and time-varying deformations encountered during polymer processing. Recently,
significant advances in neutron detection as well as the design of new fluidic devices have
opened up new capabilities for probing complex, time-varying deformations that more
reliably emulate real processing flows. Here, we will summarize the key advances leading
to these capabilities, and illustrate their usefulness with two examples involving the flow-
induced structuring in polymer nanocomposites. In the first example, we use time-resolved
rheo-SANS, involving simultaneous flow-SANS and rheological measurement, to explore
the kinetics and mechanics of shear-induced aggregation of nanoparticle suspensions in
associative polymers during startup and cessation. The results show that, over a wide range
of conditions, clustering is dominated by competition of hydrodynamic interactions and
Brownian motion of the dispersed nanoparticles, rather than by polymer normal stresses as
originally proposed. In the second, we use a newly developed fluidic four-roll mill (FFoRM)
in order to probe how the flow-induced alignment of rodlike nanoparticles in polymer
solutions depends on the type of applied deformation.
Figure 1: Schematic illustrating the fluidic four roll mill (FFoRM) and its use in flow visualization and SANS
measurements on polymeric fluids during complex flows.
FFoRM Flow visualization SANS
ISPAC 2018 - Session: Deformation of Soft Materials
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M.11 - Rheo-Raman microscopy for polymer crystallization
characterization
A.P. Kotula
Materials Science and Engineering Division, NIST, Gaithersburg, MD; [email protected]
Polymer processing requires a deep understanding of the connection between
viscoelastic polymer flow and the mechanical properties of the final product. Therefore,
instrumentation that can simultaneously measure flow properties and physicochemical
changes in materials is crucial to explaining structure-process-property relationships in
polymers. Chemical information such as composition, bond formation or scission, and
molecular conformation affect the rheological properties of polymers; this critical chemical
information can be obtained via vibrational spectroscopic techniques such as infrared (IR)
or Raman spectroscopy. Attenuated total reflection IR measurements on a rheometer are
limited by a short penetration depth into the sample (order 1 μm) and water absorption.
Because Raman spectroscopy does not have these limitations, techniques for coupling
Raman spectroscopy and rheology are desirable.
Given this need, we have developed an instrument for simultaneous measurements
of rheology, Raman spectroscopy, and polarized optical microscopy which we call the rheo-
Raman microscope.[1] The instrument combines a stress-controlled rheometer with a Raman
spectrometer and optical microscope via a transparent glass base. Features in the Raman
spectra can be quantitatively correlated with crystallinity via comparison with differential
scanning calorimetry measurements, and epi-illumination imaging using crossed-polarizers
reveals the size and orientation of birefringent structures in the sample.
The rheo-Raman microscope is especially useful in characterizing the relationship
between crystallinity and rheology during polymer crystallization. We demonstrate this
capability by measuring the isothermal crystallization of polycaprolactone (PCL), an
aliphatic polyester commonly used in the additive manufacturing of biomedical implants.
Our measurements allow us to critically assess the various models currently used to relate
crystallinity to rheology as well as develop novel phenomenological models that can be used
to explain crystallization via percolation-type phenomena.[2] We find that a general effective
medium equation can be used to characterize the relationship between viscoelasticity and
crystallinity.
We further apply our simultaneous measurement technique to characterize the
crystallization of high-density polyethylene. Quiescent crystallization measurements
indicate differences in the sensitivity of Raman spectra compared to the appearance of
birefringent structures in optical microscopy, as well as the sensitivity of the viscoelastic
shear modulus to small increases in the degree of crystallinity during crystallization. We
apply the effective medium model to determine the crystalline fractions where mechanical
percolation occurs.
References
[1] – A.Kotula, M.Meyer, F.de Vito, J.Plog, A.Hight-Walker, and K.Migler, Rev.Sci.Inst. 87, 105105 (2016).
[2] – A.Kotula and K.Migler, J. Rheol. 62, 343 (2018).
ISPAC 2018 - Session: Deformation of Soft Materials
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M.12 - Effects of Orientation and Deformation Mode in Dynamic Mechanical
Analysis of Engineered Materials
Sarah Cotts
TA Instruments
Dynamic Mechanical Analysis (DMA) is widely used to characterize glass transition behavior of
polymeric materials. By monitoring changes in viscoelastic properties as a function of
temperature, DMA is more sensitive to glass transition than any other technique. In addition, it
provides insights into microstructure and bulk physical properties. Therefore, DMA is especially
valuable in characterizing engineered materials with complex morphologies created by their
processing. The testing shown here includes traditional thermoplastics and polymer composites
with varying degrees of molecular orientation and macro orientation, and examines the effects of
the orientation on the DMA measurements through the glass transition, using varying
deformation modes to either highlight or minimize those effects. Samples generated using
additive manufacturing (3D printing) are also studied using DMA. 3D printing is becoming a
popular technique for rapid prototyping or generating parts quickly and inexpensively. The
material can have significant orientation on the micro scale or macro scale, depending on the
process and the material. Mechanical measurements like tensile stress detect the effect on the
bulk properties, but Dynamic Mechanical Analysis adds further understanding into the
morphologies of 3D printed materials by the observing the changes in viscoelasticity, damping,
and glass transition temperature range with varying orientation.
ISPAC 2018 - Session: Deformation of Soft Materials
23
M.13 - Selective Cell Adhesion on Peptide-Polymer Nano-Fiber Mats
G. Kaur#, S. Kumari, P. Saha, S. Patil, S. Ganesh, S. Verma*
#Department of Pharmaceutical Sciences, College of Pharmacy, Texas A&M University, Reynolds Medical
Building, TAMU Mailstop 1114, College Station, Texas 77843, United States
*Department of Chemistry, Indian Institute of Technology, Kanpur, India-208016
Email: [email protected]
The electrospun nanofibers are valuable for a number of applications ranging from
catalysis to drug delivery. At times, the lack of biocompatibility, biodegradability and
hydrophobicity presents hindrance in their use in biological applications. Aromatic amino acids
are veritable precursors for biocompatible nanofibers, which could also be chemically modified
with suitable addressable recognition tags to invoke specific binding events. This study presents
an attractive strategy for constructing electrospun fibrous nanomats from dityrosine based folic
acid conjugate and polycaprolactone (PCL) to afford a new hybrid material displaying excellent
tensile properties, biocompatibility and cell adhesion. We demonstrate that appropriate choice of
peptide-to-polymer ratio gave mats with sufficient hydrophilic, better mechanical properties and
allowed favorable interaction of folate receptor presenting cells with nanomats, while the ones
lacking folate receptor did not exhibit binding. Such selectivity could be possibly invoked for
separation and also for custom synthesis of nanomats for healthcare applications.
Figure 1: A working model for peptide-polymer mats
References
[1] - G. Kaur, A. Shukla, S. Sivakumar and S. Verma, J. Pept. Sci. 21, 248 (2015).
[2] - J. J. Castillo, W., E. Svendsen, N. Rozlosnik, P. Escobar, F. Martínez and J. Castillo-León, Analyst 138, 1026
(2013).
ISPAC 2018 - Session: Deformation of Soft Materials
24
M.14 - Viscoelastic behavior of polyelectrolyte complexes across
coacervate-precipitate transition regime
S. Ali and V.M Prabhu
Material Measurement Laboratory, National Institute of Standards and Technology, 100
Bureau Drive, Gaithersburg, Maryland 20899, United States
Email: [email protected]
Complexation between anionic and cationic polyelectrolytes results in solid-like
precipitates or liquid-like coacervate depending on the added salt in the aqueous medium
[1]. Understanding the boundary between these polymer-rich phases and the associated
changes in the polymer relaxation in the complexes across the phase transition regime is
fundamentally important for their various technological applications including surgical wet
adhesives, tissue engineering, food processing and packaging. This presentation will
describe the relaxation dynamics probed over a wide timescale by measuring viscoelastic
spectra and zero-shear viscosities at varying temperatures and salt concentrations of
complexes from coacervate to near-precipitate. The complexes exhibit time-temperature
superposition (TTS) at all salt concentrations, which is further supported by small angle
neutron scattering measurements. Moreover, the range of overlapped-frequencies for time-
temperature-salt superposition (TTSS) strongly depends on the salt concentration (Cs) and
gradually shifts to higher frequencies as Cs is decreased. These observations are further
analyzed using the main results of the sticky-Rouse model [2].
References [1] Q. Wang and J. B. Schlenoff, Macromolecules 47, 3108 (2014)
[2] S. Ali and V. M. Prabhu, Gels 4(1), 11 (2018)
ISPAC 2018 - Session: Characterization with Chromatography
25
M.15 - Comparison of fast SEC and UHP SEC for the second dimension in
two-dimensional liquid chromatography of polymers
Elena Uliyanchenko, Stijn Rommens
SABIC, Plasticslaan 1, 4612 PX Bergen op Zoom, the Netherlands, [email protected]
Two-dimensional liquid chromatography (2D LC) is an important characterization technique for
polymers. 2D LC can provide information on two macromolecular distributions and their mutual
dependence that allows for deeper understanding of structure-properties relationships of the
polymers. This, in turn, accelerates the development of new materials with specific set of
properties meeting the needs of the modern society.
The most common comprehensive 2D LC approach combines chemical-composition based
separation by gradient-elution liquid chromatography as a first dimension (D1) and a size-based
separation by size-exclusion chromatography (SEC) as a second dimension (D2). This setup
requires a labour-intensive method development and optimization of multiple experimental
parameters. The main limiting factor is the D2 analysis speed, which needs to be very fast in order
to maintain the quality of the D1 separation. However, the separation speed in D2 is restricted in
practice by the column material stability and by the minimum acceptable efficiency in D2.
Typically, wide-bore short SEC columns are used at a very high flow rates and a satisfactory D2
separations can be achieved within 2.5 – 3 min. At these conditions, the solvent consumption is
very high and the total 2D analysis time can reach 3-4 hours. An alternative could be the use of
ultra-high pressure size-exclusion chromatography (UHP SEC) in D2. UHP SEC columns are
made of smaller (sub 3-m) silica-organic hybrid particles that can withstand higher pressures and
therefore they can be run at higher linear velocities without significant efficiency loss. This allows
for smaller column dimensions, lower flow rates, and therefore, for reduction of solvent
consumption, higher environmental sustainability and reduced costs. The separation time in D2
can be shortened to approximately 1 min and the total analysis time can be decreased to about 1
hour. Thus, applications of such columns in 2D LC setup seem to be beneficial. However, different
stationary phase chemistry and smaller dimensions of such columns may cause some additional
practical challenges.
In this study, we compare the performance of fast SEC and UHP SEC for rapid polymer analysis
and address challenges associated with the use of both types of columns. The influence of
parameters such as polymer molecular weight and injection volume on the separation efficiency is
studied. Based on the theoretical considerations and practical data we highlight potential and
drawbacks of both fast SEC and UHP SEC for the applications in 2D LC. Finally, we provide a
guideline for the use of these columns in 2D LC of polymers.
ISPAC 2018 - Session: Characterization with Chromatography
26
M.16 - Understanding Polymer Structure by Interaction Polymer
Chromatography
Christopher J. Rasmussen1, Yefim Brun2
1. DuPont Science & Innovation 2. DuPont Industrial Bioscience, Wilmington, DE.
A defining characteristic of polymers is the polydispersity of chain lengths. Revealing the
molecular weight distribution enables a full understanding of how molecular properties can
affect end-use and material properties. Size Exclusion Chromatography (SEC) is an
analytical technique capable of resolving a polymer’s molecular weight distribution, and as
such, in an indispensable tool for polymer chemists. However, molecular weight is only one
distributed property that can characterize a given polymer. Additional complexities such as
functional end groups, substituted side groups, and comonomer composition, all exist as
distributed properties. SEC is, at best, not sensitive to these properties, and at worst,
invalidated by them. And while other spectrometric techniques such as NMR, FTIR, and MS
provide invaluable averages, a separation technique is required to quantify any distributed
property.
In this talk, a simple theoretical framework for Interaction Polymer Chromatography (IPC)
will be introduced. IPC is a collection of chromatographic methods that rely on the
interaction of polymer analyte and a stationary phase by enthalpic adsorption forces, rather
than steric exclusion as is the case for SEC. Separations can thus be designed to minimize or
eliminate retention by molecular weight, and reveal the underlying molecular properties that
define a polymer’s structure. Cases covered include end group characterization of
functionalized poly(ethylene glycol) stars, distribution of comonomer in acrylate
copolymers, and determination of structure parameters such the blockiness “B-value” for
transesterified polyesters.
ISPAC 2018 - Session: Characterization with Chromatography
27
M.17 - Light Scattering without Refractive Index Increment
A New Approach to Calibrate SEC-Light Scattering Setups
D. Lohmann1 , W. Radke2, J. Preis2, S. Lavric3
1PSS USA Inc, Amherst, MA, 2PSS GmbH, Mainz, Germany, 3 Melamin d.d., Kocevje, Slovenia
Size exclusion chromatography (SEC) with light scattering detection (SEC-LS) has
become a popular method for polymer characterization. In contrast to conventional SEC,
which yields molar masses only relative to a calibration curve, SEC-LS can provide absolute
molar masses at each elution volume. This allows determining true molar mass distributions
and molar mass averages. SEC-LS requires use of a light scattering instrument in conjunction
with a concentration detector, typically a RI detector. The primary information obtained by
the detectors are voltages, which have to be converted to the respective physical property
measured.
At present, calibration of SEC-light scattering detectors is either achieved by
calibration using a reference liquid of known Rayleigh ratio, e.g. toluene, or by using well-
characterized polymer standards for calibration. It needs to be understood that true molar
masses are obtained by SEC-light scattering, even if the standards used to calibrate the SEC-
light scattering setup are not of identical chemical structure as the analyte. This in in contrast
to conventional SEC. If calibration is performed using a polymer standard, the molar mass
and the specific refractive index increment, dn/dc, of the standard needs to be known. For
molar mass determination of unknown analytes, knowledge of their refractive index
increment, dn/dc is also required
Unfortunately, the correct refractive increment is often unknown in the solvent
applied, or its determination is difficult, e.g. in mixed solvents or in solvents containing salts
or additives. The present contribution will describe an alternative approach to calibrate an
SEC-LS setup and to determine the molar mass of a unknown analytes, requiring neither the
refractive index increment of the sample, nor of the polymer used for calibration. Only the
molar mass of the calibrant and the concentrations of the calibrant and the unknown samples
are required. The new calibration approach does not require any refractive index increment,
Consequently, experimental difficulties arising from preferential solvation as they are
present in ternary systems (mixed solvent, salt containing eluents) are eliminated.
Besides the theoretical approach, the contribution will provide experimental results, in
organic as well as aqueous solvent, proving the suitability of the new approach.
ISPAC 2018 - Session: Characterization with Chromatography
28
M.18 - Fast Separations of Synthetic Polymers Using Advanced Polymer
Chromatography (APC)
M. Jančo
Dow Chemical, 400 Arcola Road, Collegeville, PA 19426, e-mail: [email protected]
Size Exclusion Chromatography (SEC) is the preferred method for the determination
of the molecular weight parameters of synthetic polymers as a result of its universality,
reliability, reproducibility and low sample consumption. To achieve sufficient resolution of
separated species, the column sets are composed of at least two, and more often, three
analytical columns (300 x 7.5-10 mm ID). Typical flow rates are 1 - 2 mL/min in order not
to damage the column packing by exceeding its back pressure limit. Therefore, resulting
SEC separation run times are often in range of 30 to 60 min.
Substantial acceleration of SEC separations remains difficult to achieve due to
column packing pressure limitations. Short and wide diameter SEC columns (50 x 25 mm
ID) that allow high eluent flow rates (typically 5 to 10 mL/min) while still running at
moderate backpressure are the only present solution to speed up SEC separations [1]. A
limitation to this approach is lower resolution of the separation.
Advanced Polymer Chromatography (APC) is a newly developed disruptive
technology allowing separation of synthetic polymers with very short analysis times and
improved resolution [2]. Using a Waters ACQUITY APC system and BEH APC columns
packed with 1.7-2.5 μm particles with pore size ranging from 45 to 900 Å, size based
separations of 16 component mixture of narrow PS standards can be achieved in less than 6
minutes (Figure 1). Power of APC in speed, resolution, precision and sustainability will be
compared to conventional SEC. APC of polymers soluble in aqueous buffers will be also
presented.
Figure 1: APC chromatogram of 16 component mixture of PS standards obtained on three BEH XT columns
(150x4.6 mm id) packed with 2.5 m BEH particles in THF using RI detection. Flow rate: 1ml/min.
References
[1] http://www.polymer.de/products/columns-forgpcsecgfc/gpcsec-highspeed-columns.html
[2] M. Janco, J. Alexander, E. Bouvier, D. Morrison, J. Sep. Sci., 2012, 36, p. 2718-2727
ISPAC 2018 – Vendor Presentation : Waters
29
V.1 -Utilization of Advanced Polymer Chromatography coupled with Light
Scattering Detectors for the Advancement of Material Science
Jennifer Gough, Robert Birdsall, Isabelle François, Michael Jones, Michael O’Leary, Jean-
Michel Plankeele, Ben MacCreath, and Damian Morrison
Scientific Operations, Waters Corporation, USA, [email protected]
The need for comprehensive characterization in materials science usually involves a vast
array of techniques such as spectroscopy, thermal analysis, and chromatography. The novel
design of the Waters ACQUITY Advanced Polymer Chromatography (APC) system has been
shown to efficiently yield both high resolution and high speed size exclusion chromatography
(SEC). This separation technique, coupled to a variety of low dispersion detectors, enables the
technique to become more widely used in academic research and material science to solve the
most challenging problems. In this presentation, we will show the expansion of the Waters
APC technique to hyphenation with light scattering (LS) detection. In addition to the LS
detection, the newest applications will be presented from academic researchers and include
work such as the analysis of lignins, polymer microstructures, and highly functional polymers.
Case studies will further be presented that focus the use of this technique for the analysis of
synthetic polymers and biopolymers.
[1] - Provder, Theodore; Urban, Marek W.; Barth, Howard G., Hyphenated Techniques in Polymer
Characterization, American Chemical Society, 1994.
ISPAC 2018 – Plenary: Advancing Materials Science with Big Data
30
M.04 - Scoping the Polymer Genome: A Roadmap for Rational Polymer
Dielectrics Design and Beyond
Rampi Ramprasad
Georgia Institute of Technology
http://ramprasad.mse.gatech.edu
The Materials Genome Initiative (MGI) has heralded a sea change in the philosophy of materials
design. In an increasing number of applications, the successful deployment of novel materials has
benefited from the use of computational methodologies, data descriptors, and machine learning.
Extensive efforts over the last few years have seen the fruitful application of MGI principles toward
the accelerated discovery of attractive polymer dielectrics for capacitive energy storage [1]. Here, we
review these efforts, highlighting the importance of computational data generation and screening,
targeted synthesis and characterization, polymer fingerprinting and machine-learning prediction
models, and the creation of an online Polymer Informatics platform
(https://www.polymergenome.org) to guide ongoing and future polymer discovery and design. We
lay special emphasis on the fingerprinting of polymers in terms of their genome or constituent atomic
and molecular fragments [2], an idea that pays homage to the pioneers of the human genome project
who identified the basic building blocks of the human DNA. By scoping the polymer genome, we
present an essential roadmap for the design of polymer dielectrics, and provide future perspectives
and directions for expansions to other polymer subclasses and properties.
[1] A. Mannodi-Kanakkithodi, A. Chandrasekaran, C. Kim, T. D. Huan, G. Pilania, V. Botu, R.
Ramprasad, “Scoping the Polymer Genome: A Roadmap for Rational Polymer Dielectrics Design
and Beyond”, Materials Today, in press (2017).
[2] R. Ramprasad, R. Batra, G. Pilania, A. Mannodi-Kanakkithodi, C. Kim, “Machine Learning and
Materials Informatics: Recent Applications and Prospects”, npj Computational Materials 3, 54
(2017).
ISPAC 2018 – Plenary: Advancing Materials Science with Big Data
31
Braskem Lecture
M.05 -Towards Polymer Informatics: Databases, Infrastructure and
Beyond
Debra Audus,6 Roselyne Tchoua,1,2 Kyle Chard,1 Logan Ward,1 Jian Qin,3 Joshua
Lequieu,4 Juan de Pablo,5 Ian Foster1,2 1Computation Institute, University of Chicago, Chicago, Illinois, USA.
2Department of Computer Science, University of Chicago, Chicago, Illinois, USA. 3Department of Chemical Engineering, Stanford University, Stanford, California, USA.
4Materials Research Laboratory, University of California, Santa Barbara, Santa Barbara, California, USA. 5Institute for Molecular Engineering, University of Chicago, Chicago, Illinois, USA.
6Materials Science and Engineering Divison, National Institute of Standards and Technology, Gaithersburg,
Maryland, USA. [email protected]
Polymer informatics has the potential to revolutionize material discovery by reducing both
the development time and cost [1]. However, in order to achieve such a goal, significant
barriers still remain---a lack of large, accessible datasets, a lack of infrastructure to support
the sharing of data and code, among others. We aim to reduce and eliminate such barriers.
Regarding the lack of datasets, we have developed information extraction pipelines to
harness the vast quantities of valuable experimental polymer data trapped in the literature.
Initially, we developed the largest Flory-Huggins parameter database using
crowdsourcing. Through this process, we determined that the use of human effort was
suboptimal as over half of the reviewed journal articles contained no relevant data. Turning
to machine learning, we found that we could significantly reduce this burden by having the
computer identify the most promising articles. After these initial promising results, we opted
to further reduce human input, which although necessary, is a limitation for collecting the
data for polymer informatics. Specifically, we used natural language processing software
coupled with specially designed software modules to extract grass transition temperatures
with minimal human input; ultimately, we extracted over 250 glass transition temperatures.
In line with the goals of polymer informatics, all of the resulting data is freely available at
http://pppdb.uchicago.edu. Finally, I will highlight some of the other efforts at NIST that
aim to reduce the barriers to polymer informatics including the development of a more
efficient code for computing hydrodynamics properties of polymers called ZENO [2] and a
pilot project under the NIST center for excellence, CHiMaD [3], in collaboration with ACS
and RSC to release virtual issues in multiple journals where the polymer data is published
along with the journal article.
References [1] D.J. Audus, J.J. de Pablo. ACS Macro Lett. 2017 6: p. 1078-1082.
[2] D. Juba, D.J. Audus, J.F. Douglas, M. Mascagni, W. Keyrouz. J. Res. NIST 2017 122.
[3] http://chimad.northwestern.edu/
ISPAC 2018 – Plenary: Advancing Materials Science with Big Data
32
M.06 -Materials-Specific Considerations for Machine Learning
Bryce Meredig
Citrine Informatics, San Francisco, CA
The use of of machine learning (ML) is rapidly expanding within materials science, to the
point that “vanilla” applications of ML are becoming commoditized—much like what has
happened with simple density functional theory calculations. If a few lines of python, using
open-source libraries, are sufficient to train a reasonable model for superconducting Tc, it
is worth asking a provocative question: What is missing for ML to unlock a Nobel-caliber
discovery?
In this talk, we will outline a set of key considerations for applying ML to materials design
problems. We will begin with an introduction of how materials are, across many
dimensions, fundamentally different from more common application areas for ML. We
then explore the question above, focusing on these underlying issues: (1) data
infrastructure and access to training data; (2) representations of materials for input to
machine learning; (3) how ML models may be used to guide materials discovery; (4)
quantifying the predictive accuracy of materials property models; and (5) treating
inherently hierarchical, multiscale materials phenomena with ML.
ISPAC 2018 – Session: Computation and Characterization
33
M.21 - From Data Science to Data Stories: Automating advanced
analytics for R&D and manufacturing.
Guido F. Smits
Ph. D., Chief Scientific Officer at DataStories Int. NV, [email protected]
Advanced Predictive analytics is gaining importance and proven impact in many areas
despite some of the hype. Surprisingly, the data science universe and the business universe
keep co-existing without too much overlap. We claim that data-driven solutions will see a
greater success in business and industry only when they are understood and internalized by
domain experts (not just data scientists), and when domain experts can generate and take
ownership of the solutions themselves with minimal effort. This also requires that
predictive analytics outcomes are communicated to domain experts in human language
with a narrative; otherwise they have little chance to be sustainably deployed.
We willl show some specific examples of what is possible both in new product design and
in manufacturing.
ISPAC 2018 – Session: Computation and Characterization
34
M.22 – typyPRISM: A Computational Tool for
Liquid-State Theory Calculations of Macromolecular Materials
Tyler B. Martin1, Thomas E. Gartner III2, Ronald L. Jones1, Chad R. Snyder1, Arthi
Jayaraman2
National Institute of Standards and Technology, Gaithersburg, MD
Chemical and Biological Engineering, University of Delaware, DE
Polymer Reference Interaction Site Model (PRISM) theory describes the equilibrium spatial-
correlations of liquid-like polymer systems including melts, blends, solutions, block
copolymers, ionomers, polyelectrolytes, liquid crystal forming polymers and
nanocomposites. Using PRISM theory, one can calculate thermodynamic (second virial
coefficient, χ interaction parameters, potential of mean force) and structural (pair correlation
functions, structure factor) information for these macromolecular materials. Here, we present
a Python-based, open-source framework, typyPRISM, for conducting PRISM theory
calculations. This framework aims to simplify PRISM-based studies by providing a user-
friendly scripting interface for setting up and numerically solving the PRISM equations.
typyPRISM also provides data structures, functions, and classes that streamline PRISM
calculations, allowing typyPRISM to be extended for use in other tasks such as the coarse-
graining of atomistic simulation force-fields or the modeling of experimental scattering data.
The goal of providing this framework is to reduce the barrier to correctly and appropriately
using PRISM theory and to provide a platform for rapid calculations of the structure and
thermodynamics of polymeric fluids and nanocomposites.
ISPAC 2018 – Session: Computation and Characterization
35
M.23 – Abstract TBA
L. Fernando Vargas Lara
Georgetown University, Georgetown, DC
ISPAC 2018 – Session: Molecular Control and Characterization
36
M. 24 - Perfect Polystyrene Sulfonate: Synthesis, Characterization and
Self Diffusion in Ternary Solutions
P. Balding1, R. Cueto2, P.S. Russo1,3
1School of Chemistry and Biochemistry, Georgia Institute of Technology
2Department of Chemistry and Macromolecular Studies Group, Louisiana State 3School of Materials Science and Engineering, Georgia Institute of Technology
Sodium Polystyrene Sulfonate (NaPSS) is a model polyelectrolyte that is widely studied both
experimentally and theoretically. The traditional synthesis of NaPSS by the sulfonation of
polystyrene results in an imperfect material that is still commonly used to experimentally
understand polyelectrolyte systems. The need for better polyelectrolytes has driven our
research to synthesize perfectly sulfonated NaPSS by aqueous ATRP. Reaction control,
synthetic repeatability, desired molecular weight and low polydispersity are obtained
through an interplay of reaction variables such as pH, methanol cosolvent content, added
NaCl as a deactivator species, Cu(I)/L to initiator ratio, type of ligand and deactivator. The
monomer to initiator ratio was held fixed in order to understand how various ATRP side
reactions effect the final polymer properties.
Characterization of reaction progress by 1H NMR showed that monomer conversion and
reaction kinetics were heavily dictated by adjustments in certain reaction variables. Kinetics
and conversion both increased significantly by varying reaction pH from 6-7 to 12-13.
Increasing the methanol solvent composition showed a decrease in kinetics and conversion
while added deactivator in the form of NaCl showed a maximum in conversion and kinetics
at concentrations equivalent to the Cu(I)/L used.
Characterization of polymer size and architecture was obtained by aqueous GPC-MALS-
DLS. Desired molecular weight from the fixed monomer to initiator ratio was obtained at a
reaction pH of 6-7 but an order of magnitude increase was found at a pH of 12-13. Similarly
increasing the methanol decreased the molecular weight over a given reaction period and
added salt again showed a maxima in molecular weight at equivalent Cu(I)/L concentrations.
Analysis of the dimensionless ratio between Rg and Rh along with conformation plots
confirmed the linear random coil nature of the NaPSS polymer in good solvent conditions.
Self-diffusion measurements of NaPSS was measured by fluorescence photobleaching
recovery. FITC-labelled NaPSS showed an increase in self-diffusion as a function of
increased NaCl concentration. Diffusion of FITC-labelled NaPSS through a matrix of
dissolved, unlabelled NaPSS proves to be a complex problem. As a function of matrix
concentration and molecular weight the diffusion of the labelled NaPSS did not scale
according to theoretical predictions [1], [2].
References
[1] – A.V. Dobrynin, R.H. Colby and M. Rubinstein, Macromolecules. 28, 6 (1995).
[2] – M. Muthukumar, J. Chem. Phys. 107, 2619 (1997).
ISPAC 2018 – Session: Molecular Control and Characterization
37
M.25 - Conformational control of tethered functionalized mPEO on
anatase nanocrystals surface
M.Tawfilas, M. Mauri and R. Simonutti
aDepartment of Materials Science, University of Milano-Bicocca, via R. Cozzi 55, 20125 Milan, Italy
email: [email protected]
Improving nanocomposite materials performance it is strongly desired[1]. To reach this goal
it is necessary to work on the surface ligand engineering, an effective tool since it plays a
major role against the trickiest issue related to this kind of materials: the incompatibility of
the organic/inorganic phase. The introduction of a thin polymeric layer enables a good
dispersion of the inorganic nanocrystals (NCs) in solvents and matrixes in which bare
particles aggregate and precipitate. Thanks to the control over the graft density (σ) and the
grafted chains molecular weight (N) it is possible to control morphology of the dispersions
in matrix[2]. Defining the conformation of the grafted polymer, that can be brush or
mushroom, improves the solubility of the nanocomposite into polymer matrixes and gives
specific properties to the final material[3]. In our contribution we explored the grafting-to
approach (Fig.1) of polyethylene oxide monomethylether (mPEO) chains, of different
molecular weights (Mw, 102-104 gmol-1), functionalized with three anchoring groups:
alcoholic, carboxylic and phosphate end group. The grafting reactions have been made using
two different solvents (water and dichloromethane) in order to manage the environment in
which the polymer and the NCs surface react. Anatase NCs (<10nm) are synthesized via
solvothermal technique and fully characterized with transmission electron microscopy
(TEM), dynamic light scattering (DLS), X ray diffraction (XRD), Z-Potential and N2
adsorption. The functionalized mPEO samples are characterized with nuclear magnetic
resonance (NMR) and Furrier transform infra-red spectroscopy (FTIR), while the grafted
polymers are quantitatively defined through thermogravimetric analysis. It is observed the
effect of the anchoring group at low Mw on σ that is strictly related to the enthalpy gain due
to the bond formation at the NCs surface. At higher Mw the enthalpy gain is overwhelmed
by the entropic cost due to the disadvantaged chain stretching bringing low σ. In order to
describe the regime of the anchored polymers, we can assume that a single grafted chain acts
as a rigid sphere; calculating a theoretical mean distance between two chains as two times
the radius of gyration (2Rg) and an experimental mean distance (Dm), deducted by TGA and
BET analysis it is possible to define a brush regime when Dm<2Rg, vice versa when Dm ≥2Rg
the mushroom regime is described. Thus gives us a full control over σ and the polymer
conformation on spherical NCs.
Figure 1: Representation of the grafting-to approach applied in this work for mPEO on anatase NCs.
References
[1] - Li Y, Krentz TM, Wang L, Benicewicz BC, Schadler LS., ACS Appl. Mater. Interfaces 2014, 6,
6005−6021
[2] - Kumar SK, Jouault N, Benicewicz B, Neely T.. Macromolecules. 2013;46(9):3199-3214.
[3] - Brittain WJ, Minko S., J Polym. Sci. Part A Polym. Chem. 2007;45(16):3505-3512.
ISPAC 2018 – Session: Molecular Control and Characterization
38
M. 26 - Preparation and Characterization of Polyurethanes from
Carbohydrates
H. N. Cheng1, Atanu Biswas2
1Southern Regional Research Center, USDA Agricultural Research Service,
1100 Robert E. Lee Blvd., New Orleans, LA 70124, USA 2National Center for Agricultural Utilization Research, USDA Agricultural Research Service,
1815 N. University St., Peoria, IL 61604, USA
Email: [email protected]
Carbohydrates represent a useful platform for the generation of polymers from agro-based
sustainable and renewable resources. Indeed, many derivatives of carbohydrate polymers are
known and available as commercial products [1]. One of the ways to derivatize a
carbohydrate is convert it into a polyurethane, replacing a petroleum-based polyol and
thereby rendering the final product more biodegradable and sustainable [2-4].
Polyurethanes, of course, are well-known for their many commercial uses, e.g., foams,
elastomers, adhesives, surface coatings, and synthetic fibers [5].
In our efforts to develop green polymer technologies, we have coupled the use of
carbohydrates in polyurethane synthesis with microwave-assisted reactions [6-8]. In our
latest work [9], we have concentrated on sucrose, which is inexpensive and widely available.
Thus, we have synthesized polyurethanes from sucrose and toluene diisocyanate (TDI)
through microwave technology. As expected, the sucrose/TDI ratio has a large effect on the
degree of crosslinking of the product. Relative to conventional heat, microwave-assisted
synthesis has been found to significantly decrease the reaction time and save energy.
Through the incorporation of a second material in a semi-interpenetrating polymer networks,
appropriate modifications of the mechanical properties of the polyurethane can be achieved.
Characterization of the polymers has been conducted with 13C NMR, FT-IR, SEC, and
thermal analysis.
References
[1] J.N. BeMiller and R. L. Whistler. Industrial Gums, 3rd ed. Academic Press, San Diego, CA, 1993.
[2] Y. Li, X. Luo and S. Hu. Bio-based Polyols and Polyurethanes. Springer, Cham, CH, 2015.
[3] F. Zia, K. M. Zia, M. Zuber, S. Kamal, and N. Aslam. Starch based polyurethanes: A critical review
updating recent literature. Carbohydr. Polym. 134, 784 (2015).
[4] N. J. Sangeetha, A. M. Retna, Y. J. Joy, and A. Sophia. A review on advanced methods of polyurethane
synthesis based on natural resources. J. Chem. Pharm. Sci. 7, 242 (2014).
[5] M. Szycher, Szycher’s Handbook of Polyurethanes, 2nd ed. CRC Press, Boca Raton, FL, 2013.
[6] A. Biswas, S. Kim, Z. He, and H. N. Cheng. Microwave-assisted synthesis and characterization of
polyurethanes from TDI and starch. Int. J. Polym. Anal. Charac. 20, 1 (2015).
[7] A. Biswas, M. Appell, Z. Liu, and H. N. Cheng. Microwave-assisted synthesis of cyclodextrin
polyurethanes. Carbohydr. Polym. 133, 74 (2015).
[8] H. N. Cheng, R.F. Furtado, C.R. Alves, M.S.R. Bastos, S. Kim, and A. Biswas. Novel polyurethanes
from xylan and TDI: Preparation and characterization. Int. J. Polym. Anal. Charac. 22, 35 (2017).
[9] A. Biswas, S. Kim, A. Gómez, M. Buttrum, V. Boddu, and H.N. Cheng. Microwave-assisted synthesis
of sucrose polyurethanes and their semi-IPN’s with polycaprolactone and soybean oil. Ind. Eng. Chem.
Res., accepted; https://pubs.acs.org/doi/10.1021/acs.iecr.7b04059.
ISPAC 2018 - Plenary: Advances in Chromatography and Spectroscopy
39
T.01 - Correlated polymer characterization via SEC-IR Detection with a
new QCL Laser Spectrometer and SEC-NMR with a new 60 MHz MR-
NMR Spectrometer
Jennifer Kübel, Johannes Höpfner, Carlo Botha, Sascha Morlock, and Manfred Wilhelm
Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT),
Karlsruhe, Germany, [email protected]
Polymers have three important molecular characteristics: the molecular weight
distribution (MWD), the chemical composition and the topology. The MWD is usually
determined using size exclusion chromatography (SEC). SEC detectors commonly in use,
such as refractive index detectors, light scattering or viscometers, do not provide information
about the chemistry or topology. This information is normally gained separately using
spectroscopic methods.
Coupling IR or NMR spectroscopy with SEC is a promising approach to gain this
correlated information. [1] An inherent problem to this pairing is the normally very high
solvent signals, which arise from the low sample concentration necessary for SEC
separation. Previously, we developed an online SEC-FTIR coupling using a standard
research FTIR spectrometer, specially constructed flow cells and mathematical solvent
suppression of the solvent signals. [2] For an even higher sensitivity, different infrared light
sources are needed. We now present results from a SEC coupled with an IR spectrometer
using a tunable Quantum Cascade Laser (QCL) light source, which has a higher light
intensity, but a limited bandwidth. [3] A table-top 60 MHz MR-NMR spectrometer equipped
with a permanent magnet was also coupled with SEC to make online measurements. [4] The
resulting S/N ratio is sufficient for online MR-NMR-SEC measurements. The method
development for SEC-QCL-IR and MR-NMR-SEC including the general setup, flow cells
and solvent suppression will be presented. [3,4]
Figure 1. Comparison of online SEC-FTIR and SEC-QCL-IR measurements. [3] References
[1] H. Pasch, Hyphenated separation techniques for complex polymers, Polym. Chem. 2013, 4, 2628.
[2] T.F. Beskers, T. Hofe, M. Wilhelm, Macromol. Rapid Commun. 2012, 33, 1747-1752; T.F. Beskers, T.
Hofe, M. Wilhelm, Polym. Chem. 2015, 6, 128-142.
[3] S. Morlock, J. M. Kuebel, T.F. Beskers, B. Lendl, M. Wilhelm, Macromol. Rapid Commun. 2018,
1700307.
[4] J. Höpfner, K.-F. Ratzsch, C. Botha, M. Wilhelm, Macromol. Rapid Commun. 2018, 1700766.
ISPAC 2018 - Plenary: Advances in Chromatography and Spectroscopy
40
T.02 - Characterization of Complex Synthetic Polymers by Advanced
Separations and Detection Techniques
David M. Meunier
The Dow Chemical Company, Core R&D, Analytical Sciences, Midland, MI
Polymer structure dictates properties, and ultimately performance, in the market place.
Elucidation of structural differences among polymer samples is therefore critical for defining
structure-property relationships and process-structure relationships. Although often simply
depicted as a structural repeat unit enclosed in parentheses with a subscripted “n”, synthetic
polymers are actually complex mixtures of similar species. For example, a polyethylene
sample, depicted simply as repeating ethylene units, as in –(CH2-CH2)n–, can include
overlapping distributions in molar mass, chemical composition, branching topology,
functionality type (e. g., end groups), block architecture and microstructure. In fact, virtually
all commercial synthetic polymers contain at least two overlapping distributions of structural
heterogeneity, while many, especially copolymers, exhibit more than two. Because they
comprise complex mixtures of overlapping distributions, gaining insight into the structural
diversity of polymer samples requires advanced separations and detection techniques.
Several approaches for elucidating structural heterogeneity in synthetic polymers will be
highlighted in this talk. Used alone or in combinations, separations techniques like size
exclusion chromatography, field flow fractionation and liquid adsorption chromatography
have been developed and applied to many industrial polymers. Combinations of detectors
including concentration, composition and molecular weight/size sensitive are utilized in
conjunction with single or multidimensional separations to provide even greater insight.
Several examples of application and development of these approaches for characterization
of synthetic polymers and particles will be presented and discussed.
ISPAC 2018 - Plenary: Advances in Chromatography and Spectroscopy
41
T.03 - HPLC Characterization of Block Copolymers
Taihyun Chang Department of Chemistry and Division of Advanced Materials Science, POSTECH, Pohang, Korea
Block copolymers have been a subject of intensive research in the last few decades due to
their formation of ordered nanophases that can be used as templates for various applications
in nanotechnology. Block copolymers are also used in structural materials such as
thermoplastic elastomers or high impact polymers. They are usually prepared by controlled
polymerization methods such as anionic polymerization or controlled radical polymerization
to produce a well-defined block structure in the polymer chains. For the molecular
characterization of block copolymers, Size exclusion chromatography (SEC) has been used
routinely, but it often fails to elucidate the details due to their size dependent separation and
large band broadening. Other chromatographic methods can do a better job in the
characterization of block copolymers. For examples, liquid chromatography at the critical
condition (LCCC) successfully characterized individual block in block copolymers.[1]
Interaction chromatography (IC) is effective to fractionate homopolymer byproducts from
the block copolymers[2] and able to fractionate individual blocks into narrower fractions.[3]
In this talk, our efforts on the detailed characterization of block copolymers will be
presented.
References
[1] W. Lee, D. Cho, T. Chang, K.J. Hanley and T.P. Lodge, Macromolecules 34, 2353 (2001) [2] S. Park; I. Park, T. Chang, C.Y. Ryu, J. Am. Chem. Soc. 126, 8906 (2004)
[3] S. Park, D. Cho, J. Ryu, K. Kwon, W. Lee, T. Chang, Macromolecules 35, 5974 (2002)
[4] K. Im, H.-W. Park, Y. Kim, B. Chung, M. Ree, T. Chang, Anal. Chem. 79, 1067 (2007)
[5] S. Lee, H. Choi, T. Chang, B. Staal, Anal. Chem. Submitted
Figure 2. NP-TGIC x NP-LCCC 2D-LC
chromatogram of StyroluxTM [5] Figure 1. NP-TGIC x RPLC 2D-LC
chromatogram of low MW PS-b-PI [4]
ISPAC 2018 - Session: Condensed Phases
42
T.11 - Two-Dimensional Terahertz (2D THz) Raman Correlation
Spectroscopy Study of the Crystallization of Bioplastics
I. Noda1,2, A. Roy3, J. T. A. Carriere3 D. B. Chase1, J. F. Rabolt1
1Department of Materials Science and Engineering, University of Delaware, Newark, DE
19716, U.S.A. [email protected] 2Danimer Scientific, Bainbridge, GA 39817, U.S.A.
3Ondax, Monrovia, CA91016, GA 39817, U.S.A.
Raman spectroscopy was used to study the evolution of crystalline states of biodegradable
poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate] or PHBHx copolymer produced
by microbial biosynthesis [1]. The low-frequency Raman spectral region has become readily
accessible with the introduction of highly efficient optical notch filter technology, [2]. Thus,
Raman bands associated with the lattice mode vibrations of crystalline lamellae were
detected in the very low frequency/THz region, in addition to the conventional fingerprint
region bands [3].
Two-dimensional correlation analysis was applied to the time-dependent evolution of Raman
spectra during the isothermal crystallization of PHBHx. Simultaneous Raman measurement
of both carbonyl stretching and low-frequency crystalline lattice mode regions made it
possible to carry out the highly informative hetero-mode correlation analysis [4].
Coordinated dynamic variations in the spectral features were observed with the
crystallization process, and surprisingly detailed mechanisms for the development of
crystalline structures were revealed.
The crystallization process of PHBHx involves: i) the early nucleation stage, ii) the primary
growth of well-ordered crystals accompanied by the reduction of the amorphous component,
and finally iii) the secondary crystal growth most likely occurring in the inter-lamellar
region. Interestingly, the development of a fully formed lamellar structure comprised of 21
helices is detected not simultaneously but after the primary growth of crystals. In the later
stage, secondary inter lamellar space crystallization occurs after the full formation of packed
helices comprising the lamellae.
References
[1] – I. Noda, P.R. Green, M.M. Satkowski and L.A. Schechtman., Biomacromolecules. 6, 580 (2005).
[2] – J.T.A. Carrier, F. Havermeyer, R.A. Heyler, Proc. SPIE 9073, 90730K (2014).
[3] – I. Noda, A. Roy, J. Carriere, B.J. Sobieski, D.B. Chase, J.F. Rabolt, Appl, Spectrosc. 71, 1427 (2017).
[4] – I. Noda, Frontiers of Molecular Spectroscopy, 2nd ed, J. Laane, Ed. Pp.45-75, Elsevier, Amsterdam,
2018).
ISPAC 2018 - Session: Condensed Phases
43
T.12 - Imaging Orientation Angles and Order Parameters of
Semicrystalline Polymers by Polarization IR and Raman
Young Jong Lee1, Jeremy Rowlette2
1NIST, [email protected], 2Daylight Solutions
Molecular alignment at the atomic level or the meso- and macroscopic levels can cause not
only directionality of a bulk property but also new unique properties of materials.
Understanding of the spatial heterogeneity and hierarchy in molecular orientation at each
level will help to find how the molecular orientation affects the resulting biological,
chemical, and mechanical properties of macromolecular materials. Therefore, accurate
measurement of molecular orientation with a spatial resolving power becomes critical to
understanding and optimization of the unique and directional properties of various complex
materials, such as bones, liquid crystals, silks, and polymers.
Figure 1: BCARS image of a high-density polyethylene film and 3D molecular orientations determined from
the polarization controlled BCARS hyperspectral images along the yellow dashed line. The red and green
colors represent the C-C and C-H stretching modes, respectively.
In this talk, I describe a new approach to non-iteratively determine the 3D angles and the
orientational order parameter without assuming a model function for an ODF. This method
is based on polarization-dependent IR and Raman signals of two non-parallel vibrational
modes. I will show how to determine the 3D angles and the second order parameter using
straightforward formula without iterative calculation. I demonstrate that this method can be
used to measure the 3D angles and order parameters at each image pixel of semicrystalline
polymers with a diffraction-limited spatial resolution.
References
[1] Y. J. Lee, Opt. Express, 23, 29279 (2015).
[2] Y. J. Lee, C. R. Snyder, A. M. Forster, M. T. Cicerone, W. -l. Wu, ACS Macro Lett., 1, 1347 (2012).
ISPAC 2018 - Session: Condensed Phases
44
T.13 - Multiple Order-to-Order Transitions within Ultrathin Films of
Sugar-Polyolefin Amphiphilic Conjugates
S. R. Nowak1, K. Yager2, L. R. Sita1*
1 Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland
20742, United States 2 Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United
States
The development of nanostructured ‘smart’ materials that can respond to external stimuli on
practical time scales and moderate conditions remains a challenge and is a topic of great
academic and industrial interest. For thermoresponsive systems in the solid-state, the goal of
establishing extremely low kinetic barriers for order-to-order nanostructural transitions has
not yet been reached. This presentation will demonstrate the synthesis and characterization
of a new class of low molecular weight atactic sugar-polyolefin hybrid conjugates that can
meet this challenge. These amphiphilic hybrid conjugates consist of hydrophobic end-group-
functionalized poly(alpha-olefinate) (xPAO) “tails” chemically tethered to hydrophilic
saccharide “head” groups and display organized nanostructures within ultra-thin films with
sub-10 nm features. We previously reported that the conjugate consisting of the disaccharide
(D)-(+)-Cellobiose as the head group and atactic polypropylene (aPP) as the tail (CB-aPP)
undergoes a unique reorientation of self-assembled domains upon thermal annealing at
physiological temperatures. Herein we report that these conjugates display a rich and
dynamic self-assembly behavior in the form of multiple ‘order-to-order’ phase transitions
within ultrathin-films (< 100 nm), which were investigated by GISAXS with a synchrotron
x-ray source as a function of temperature. These results demonstrate the utility of sugar-
polyolefin conjugates as nanostructured smart materials for nanotechnological applications.
References
[1] –T. S. Thomas, W., Hwang, and L. R. Sita, Angew. Chem. Int. Ed. 55, 4683 (2016).
[2] – S. R. Nowak, W., Hwang, and L. R. Sita, J. Am. Chem. Soc. 139, 5281 (2017).
ISPAC 2018 - Session: Condensed Phases
45
T.14 - Liquid-solid transitions of a repulsive system with also a short-
range attractive potential
G. Yuan1, 2, J. Luo,3 C. Zhao,4 C. C. Han5
1Georgetown university. 2NIST center for neutron research, [email protected]. 3Institute of
Chemistry, Chinese Academy of Sciences, [email protected] 4Ningbo University,
[email protected]. 5Shenzhen university, [email protected]
The liquid-solid transitions problem is approached from a very fundamental way---build a
model system with simple and tunable inter-particle potential, then investigate the effect of
the inter-particle potential (mainly the attractive part) on the transitions, which includes
gelation at low packing density and glass formation at high packing density. Inter-particle
attraction is tuned by mixed suspensions of large hard colloid and adsorptive small soft
microgel, in which small microgels can either serve as bridges to connect neighbouring large
particles thus to introduce the bridging attraction, or serve as stabilizers fully covered on the
surface of large particles. With neutron scattering and rheology techniques, we determined
the boundaries of various state-transitions (Figure 1) and describe the characters of these
transitions, from structural, dynamical, and thermodynamic point of views. Our results
indicate that the attraction force between the added small polymers and the large particles
(or the origin of effective inter-particle potentials, or maybe the very details of attractive
potentials) have a fundamental impact on the mechanism of liquid-solid transition [1, 2].
Figure 1: A framework of state transition and schematic illustration of PS microsphere and PNIPAM
microgel structures.
References
[1] G. Yuan, H. Cheng and C. C. Han, Polymer. 131, 272 (2017).
[2] J, Luo, G. Yuan, C. Zhao, C. C. Han, J. Chen and Y. Liu, Soft Matter. 11, 2494 (2015).
ISPAC 2018 - Session: Macromolecular Architectures
46
T.15 - Synthesis and Characterization of Polyolefins with Precise Control
of Branch Frequency and Branch Length
S. V. Orski1, L. A. Kassekert2, W. S. Farrell1, M. A. Hillmyer2, and K. L. Beers1
1 Materials Science & Engineering Division, National Institute of Standards & Technology (NIST),
Gaithersburg, Maryland 20899, United States 2 Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455-0431, United States
Separations of commercial polyolefins, which often involve mixtures and
copolymers of linear, short-chain branched, and long-chain branched polyethylenes, can be
very challenging to optimize as species with similar hydrodynamic sizes or solubility often
co-elute using various chromatographic methods. To better understand the effects of
polyolefin structure on the dilute solution properties of polyolefins, a family of highly
controlled short-chain branched polyolefins with control of alkyl branch frequency and
branch length were synthesized by ring-opening metathesis polymerization (ROMP) of alkyl
substituted cyclooctene monomers. This synthetic approach utilizes strained cyclic alkenes
to generate controlled, regioregular polyalkenamers. Quantitative post-polymerization
hydrogenation generates the final branched polyolefins with ideal head-to-tail addition of
monomer, resulting in a fixed branch frequency and branch length across the molar mass
distribution.
A series of linear polyolefins with comparable molar masses, but varied short-chain
branch length, were analysed by ambient and high temperature size exclusion
chromatography (SEC) with differential refractive index, viscometric, and multi-angle light
scattering detectors to quantify molar mass, molar mass distribution, intrinsic viscosity ([η]),
and radius of gyration (Rg) of each polymer. An additional flow-through infrared detector
also measured the degree of short-chain branching across the elution curve. A systematic
decrease of intrinsic viscosity is observed with increasing branch length across the entire
molar mass distribution. These regularly branched polyolefins can potentially serve as useful
standards to calibrate the short-chain branching distribution of polyolefins with higher
branching content as well as the branching index correction factor as a function of molar
mass. Such calibrations will help improve accuracy in measurements of long-chain and
short-chain branching distributions in polyolefins, especially in samples that contain both
types of branching.
Figure 1: Intrinsic viscosity of the model branched polyolefins as a function of molar mass.
ISPAC 2018 - Session: Macromolecular Architectures
47
T.16 - Functional electrospun membranes featuring grafted polymer
brushes: The characterization challenge
Yan Liu1,2, Jinghong Ma2, G. Julius Vancso1,2
(1) University of Twente, Materials Science and Technology of Polymers, MESA+ Institute for
Nanotechnology, Enschede, the Netherlands; [email protected]; (2) Donghua University, Shanghai, PRC
We report on the preparation, characterization, and catalytic activity of microporous
membranes consisting of of polycaprolactone (PCL) microfibers featuring gel-brush layers
of poly(hydroxyethyl methacrylate) (PHEMA). The brush coating on the fibers of these
membranes was loaded by Pd nanoparticles (NP) by in-situ reduction of Pd2+, coordinated
to carboxylate groups in the brush [1]. Reaction was performed in aqueous Pd(NO3)2
electrolytes by using NaBH4. Gel-brushes were obtained via surface-initiated ATRP
polymerization. The membrane mats prior to functionalization were fabricated by
electrospinning of PCL solutions. The PCL included mixtures of Br terminated PCL chains
with non-functional polymer. Electrospun fibers thus featured Br at their surface, which
functioned as initiators, and allowed us to polymerize polymer gel-brushes on the fibers. (A
scheme is appended showing the steps of the preparation.) We used FTIR, wettability
measurements, surface morphology imaging by TEM and SEM and thermal analysis to
characterize the membranes.
The membranes obtained had a large specific surface area and high porosity, which enabled
high concentrations of metal nanoparticle loadings. The membranes obtained showed
pronounced catalytic activity due to the presence of Pd NPs, which were stabilized by the
brush. As a proof-of-principle experiment we performed catalytic reduction of 4-nitrophenol
to 4-aminophenol in continuous flow-through catalysis.
References
[1] Benetti, E.M., Sui, X., Zapotoczny, S., Julius Vancso, G. Surface-grafted gel-brush/metal nanoparticle
hybrids (2010) Advanced Functional Materials, 20 (6), pp. 939-944.
ISPAC 2018 - Session: Macromolecular Architectures
48
T.17 - Characterization of the chemical composition distribution of 1-
octene based POP/POE by HPLC
J.H. Arndt1, R. Brüll1, T.Macko1, P. Garg2, J. Tacx2
1 Fraunhofer Institute for Structural Durability and System Reliability, Plastics Division, Schlossgartenstrasse
6, 64289 Darmstadt, Germany, 2 SABIC Technology & Innovation, STC Geleen, P.O. Box 319, 6160 AH
Geleen, The Netherlands
Ethylene/1-octene (EO) copolymers with high 1-octene content, marketed as polyolefin
plastomers (POP) and elastomers (POE), are materials of ever rising popularity and
commercial importance. Their chemical composition distribution (CCD) i.e., the distribution
of 1-octene units among individual macromolecules, has never been systematically studied.
An important reason is the low crystallinity of many of these materials, oftentimes
precluding the use of crystallization-based separation techniques such as analytical
temperature rising elution fractionation (a-TREF) [1] or crystallization analysis fractionation
(CRYSTAF) [2].
The more recently established high temperature high performance liquid chromatography
(HT-HPLC) [3,4] has no such limitations and thus holds potential to study the CCD. For this
study nine POP/POE samples covering a wide compositional range were selected. Different
solvent combinations were tested in order to identify the one giving the highest resolution
i.e., the biggest separation of molecules of different 1-octene content. The study shows a
good agreement between the CCD of the samples calculated theoretically based on
Stockmayer distributions and the CCD obtained experimentally.
Acknowledgments: The authors would like to thank C. Melian and R. Chitta for NMR and
aTREF measurements contributing to this work.
References
[1] M. Zhang, D.T. Lynch, and S.E. Wanke, J. Appl. Polym. Sci. 75, 960 (2000).
[2] B. Monrabal, N. Mayo and R. Cong, Macromol. Symp. 312, 115 (2012).
[3] T. Macko and H. Pasch, Macromolecules 42, 6063 (2009).
[4] T. Macko, R. Brüll, R.G. Alamo, Y. Thomann, V. Grumel, Polymer 50, 5443 (2009).
ISPAC 2018 - Session: Macromolecular Architectures
49
T.18 - Striving for Perfection: “Defect”-Free Polymer Networks for
Improved Metrology
J.M. Sarapas, E.P. Chan, D.N. Vaccarello, E.M. Rettner, K.L. Beers
National Institute of Standards and Technology; [email protected]
Polymer networks are ubiquitous across academia and industry, providing solutions and
platforms to address problems ranging from biotherapeutics to commodity rubbers. Despite
their broad application, networks are often engineered in such a way that promotes local
heterogeneities, which can complicate or even drive the resulting properties. Here, we target
the synthesis of extremely soft entanglement-free materials by employing a bottlebrush
polymer architecture between crosslinks.[1] This was achieved through ring-opening
metathesis polymerization (ROMP) of mono- and di-norbornene functionalized poly(n butyl
acrylate) (PnBA). By varying the ratio of mono-norbornene macromonomer to di-
norbornene crosslinker, networks with dramatically different properties were generated.
Network moduli were determined in the dry state, with values ranging from 1 to 10 kPa,
approaching the softest known bulk networks. Importantly, network modulus scaled with
estimated crosslinking density through an exponent of -0.81, in good agreement with rubber
elasticity. Swelling ratios were also correlated to dry state modulus, revealing an exponential
relationship again in good agreement for general polymer networks. These results indicate
that bottlebrush polymer networks follow the same fundamental physics as non-brush
networks while mitigating entanglements, highlighting their potential as model materials to
better inform industrial and academic materials.
Figure 1: Depiction of bottlebrush polymer network formation.
References
[1] - J.M. Sarapas, E.P. Chan, E.M. Rettner, K.L. Beers, Macromolecules 51, 2359-2366 (2018).
ISPAC 2018 - Plenary: Molecular Architectures
50
T.04 - Molecular Engineering with Anionic Polymerization
Professor Lian R Hutchings
Durham Centre for Soft Matter, Department of Chemistry, Durham University, Durham, DH1 3LE. United
Kingdom.
Anionic polymerization is well-known for its fine control of molecular structure and has
been widely adopted for the synthesis of a variety of molecular architectures. Anionic
polymerization also lends itself well to the synthesis of copolymers with precise sequence
distributions. We present recent highlights of research at Durham University in two broad
areas – i) the synthesis of long-chain branched (co)polymers and ii) the synthesis of
sequence-controlled copolymers.
In the first case we will review the synthesis of complex branched (co)polymers by the
“macromonomer” approach1 and highlight the use of temperature gradient interaction
chromatography (TGIC) as useful characterization tool2,3. We will also describe the
synthesis of randomly branched polymers by anionic chain transfer polymerization.
In the second case we will describe the synthesis of a series of copolymers including perfect
alternating copolymers, sequence-controlled terpolymers and telechelic polymers4.
Moreover, in each case, the resulting sequence is entirely controlled by copolymerization
kinetics with all monomers present from the start on the reaction. As such these
copolymerization reactions are effectively a contrived statistical copolymerization whereby
all monomers undergo polymerisation simultaneously in what we (and others) have
described as a “fire and forget” approach. Sequence analysis in many cases relies on careful
MALDI-ToF MS characterization.
References
1. Hutchings, L. R.; Agostini, S.; Hamley, I. W.; Hermida-Merino, D. Macromolecules 2015, 48, 8806.
2. Hutchings, L. R.; Kimani, S. M.; Hoyle, D. M.; Read, D. J.; Das, C.; McLeish, T. C. B.; Chang, T.; Lee, H.;
Auhl, D. In Silico Molecular Design, Synthesis, Characterization, and Rheology of Dendritically Branched
Polymers: Closing the Design Loop. ACS Macro Letters 2012, 1, 404.
3. Hutchings, L. R. Complex Branched Polymers for Structure-Property Correlation Studies: The Case for
Temperature Gradient Interaction Chromatography Analysis. Macromolecules 2012, 45, 5621.
4. Hutchings, L. R.; Brooks, P. P.; Parker, D.; Mosely, J. A.; Sevinc, S. Monomer Sequence Control via Living
Anionic Copolymerization: Synthesis of Alternating, Statistical, and Telechelic Copolymers and Sequence
Analysis by MALDI ToF Mass Spectrometry Macromolecules 2015, 48, 610.
ISPAC 2018 - Plenary: Molecular Architectures
51
T.05 - New Opportunities for Precision Polyolefins: Design,
Characterization and Dynamic Behavior of Nanostructured Polyolefin
Block Copolymers
Lawrence R. Sita
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD USA.
Abstract: Living coordinative chain transfer polymerization (LCCTP) is a new
polymerization process that can provide access to a large variety of ‘precision polyolefins’
of tunable molecular weight, very narrow polydispersity, and quantitative end-group
functionalization from readily available and inexpensive α-olefin monomers. This talk will
provide an overview of recent studies by our group that have served to expand the structural
range and bulk properties of: 1) microphase-separated polyolefin-polyolefin block
copolymers, 2) atactic-isotactic stereoblock, sterogradient and stereoirregular polyolefin
block copolymers, and 3) microphase-separated (sub-10 nm) sugar-polyolefin conjugates.
An arsenal of spectroscopic and analytical methods have been employed to establish the
nanostructured morphologies and the dynamic behavior of these materials, including
reversible order-to-order and disorder-to-order phase transitions within the bulk solid state
and ultrathin films.
ISPAC 2018 - Plenary: Molecular Architectures
52
T.06 - Polyhomologation: A Powerful Tool Towards Well-
Defined Polyethylene-Based Polymeric Materials
Nikos Hadjichristidis
King Abdullah University of Science and Technology (KAUST), Physical Sciences and Engineering Division, Catalysis Center, Polymer Synthesis Laboratory, Thuwal, Saudi Arabia
Polyethylene (PE) is and will continue to be the most widely used industrial polymer in
the world, benefiting from its product versatility, hydrophobicity, mechanical strength,
flexibility, resistance to the harsh environment, easy processability, recyclability, along with
low cost. Covalently linked to PE (block copolymers) polar blocks, such as polystyrene,
poly(methyl methacrylate), polycaprolactone, polyethyleneoxide and polypeptides offers
significant improvements in adhesion and compatibility of PE with other polar polymers and
thus broadens its applications. Consequently, the design/synthesis of block copolymers of
PE with polar chains is important to both academia and industry.
In 1997, Shea and co-workers1, inspired from the well-known in organic chemistry
homologation reaction, discovered a borane initiated/mediated C1 living polymerization of
dimethylsulfoxonium. This C1 polymerization, coined by Shea polyhomologation, has been
proven as an efficient tool to synthesize well-defined and perfectly linear hydroxyl-
terminated polyethylene. The OH-terminated PE can be used either as macroinitiator for ROP
of cyclic ethers/esters or for living/radical after transformation, to afford well defined
PE/polar block copolymers with perfectly linear PE and high molecular weight homogeneity.
Along these lines the synthesis of PE-based materials (homo/block copolymers,
hybrids with silica) will be discussed, as well as their potential applications (e. g. PE
reinforcing agents and Aggregation Induced Emission).2-14 Novel powerful procedures are
needed for the analysis/characterization of these complex PE-based macromolecular
architectures.
[1] Luo, J., Shea, K. J. Acc. Chem. Res. 2010, 43, 1420-1433.
[2] Zhang, H., Alkayal, N., Gnanou, Y., Hadjichristidis, N. Chem. Commun. 2013, 49, 8952-8954.
[3] Zhang, H., Gnanou, Y., Hadjichristidis, N. Polym. Chem. 2014, 5, 6431-6434.
[4] Zhang, H., Alkayal, N., Gnanou, Y., Hadjichristidis, N. Macrom. Rapid Commun. 2014, 35, 378-390.
[5] Alkayal, N., Hadjichristidis, N. Polym. Chem. 2015, 6, 4921-4926.
[6] Zhang, Z., Zhang, H., Gnanou, Y., Hadjichristidis, N. Chem. Commun. 2015, 51, 9936-9938.
[7] Zhang, H., Gnanou, Y., Hadjichristidis, N. Macromolecules 2015, 48, 3556-3562.
[8] Wang, D., Zhang, Z., Hadjichristidis, N. ACS Macro Letters 2016, 5, 387-390.
[9] Zhang, H., Hadjichristidis, N. Macromolecules 2016, 49, 1590-1596.
[10] Zheng, Z., Altaher, M., Zhang, H., Wang, D., Hadjichristidis, N. Macromolecules 2016, 49, 2630-
2638.
[11] Wang, D., Hadjichristidis, N. Chem. Comm. 2017, 53, 1196-1199
[12] Wang, D., Zhang, Z., Hadjichristidis, N. Polym. Chem., 2017, 8, 4062-4073.
[13] Jiang, Y., Zhang, Z., Wang, D., Hadjichristidis, N. Macromolecules 2018, 51, 3193-3202.
[14] Zapsas, G., Ntetsikas, K., Kim, J., Bilalis, P., Gnanou, Y., Hadjichristidis, N., Polym. Chem. 2018,
9, 1061-1065.
ISPAC 2018 - Session: Condensed Phase Spectroscopy
53
T.21 – Bulk heterojunction interfacial structure from REDOR NMR
R. C. Nieuwendaal1, D. M. DeLongchamp1, L. J. Richter1, C. R. Snyder1, R. L. Jones1, S.
Engmann1, A. Herzing1, M. Heeney2, Z. Fei2, A. B. Sieval3, J. C. Hummelen3, D. Reid4, J.
J. dePablo4,
1Materials Measurement Laboratory, National Institute of Standards and Technology, 100 Bureau Drive,
Gaithersburg, MD, 2Department of Chemistry, Imperial College, London SW7 2AZ, England, 3Stratingh
Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands, 4Institute for Molecular Engineering, University of Chicago, Chicago IL, 60637. [email protected]
Robust relationships between structure and function are generally lacking in organic
photovoltaic (OPV) thin film active layers. To predict performance there exists a need for
tools that can measure structure on length scales fine enough to be relatable to inter-
molecular energy transfer. Electron microscopy lacks sufficient spatial resolution due to a
lack of electron density contrast, and scattering curves can be ambiguous because there
typically is not a unique fitting model.
In this talk, I will give highlights of recent 13C {2H} rotational echo double resonance
(REDOR) measurements to characterize the donor/acceptor interfaces in bulk heterojunction
thin films. Heteronuclear couplings are measured between 13C nuclei on the acceptor C60
cage and thiophene hydrogens on the donor main chain, which has been isotopically enriched
with 2H. I will discuss models of the interface that are used to fit the REDOR dephasing
curve, and the constraints that these models have on local composition and packing. We will
also show that the REDOR measurements can help solve the mystery of which model to use
in fitting small angle neutron scattering curves.
Figure 1: Heteronuclear dipolar couplings measured at the donor/acceptor interface with REDOR NMR.
ISPAC 2018 - Session: Condensed Phase Spectroscopy
54
T.22 - Characterization of modified silicas with industrial interest
A. A. Bernardes, A. Marchi Netto, M. S. L. Miranda and R. Brambilla
I&T, Braskem S.A., Via Oeste, lote 5, Triunfo-RS, 95853-001,Brazil
Hybrid silicas prepared by sol-gel process have found several applications, for
example, as support in metallocene catalysis for olefin polymerization. Silica support allows
better distribution of catalytic sites, leading to polymers with well-controlled molar mass and
polydispersity. Therefore, a non-hydrolytic silica sol-gel route was developed encompassing
catalyzed polymerization of tetraethoxysilane (TEOS), silicon tetrachloride (SiCl4) and
different contents of octadecyltrimethoxysilane (ODS) [1].
The produced silicas were characterized by a set of key analytical technics. ATR-
FTIR and DRIFTS evidenced the formation of new siloxane groups (Si-O-Si) and the
presence of isolated, vicinal and germinal silanol groups on the silica surface; a solution 29Si-
NMR experiment detailed different 29Si species in the hybrid material. The silanol groups
could be elucidated through a 1H-MAS-NMR experiment, with bands attributed to H-
bounded hydroxyls, aliphatics and isolated silanol protons [2].
Predominance of gauche defects over trans conformation of the alkyl chain were
investigated by 13C-CP/MAS-NMR, although increasing the order as increasing the
octadecylsilane. Complementarily, 29Si-CP/MAS-NMR experiments revealed the nature of
the functional species on the modified silicas surface and hydroxyl groups neighborhood [2].
Finally, SEM images revealed no changes on morphology after the silica modification.
10 8 6 4 2 0 -2 -4
(b)
Chemical shift [ppm]
H-bonded
hydroxyls Isolated silanols
Methyl and methylene groups
(a)
50 40 30 20 10 0 -10
1, 18
Chemical shift [ppm]
3 - 16
Trans
Gauche
2, 17
O
SiO
O
CH2 CH2 (CH2) CH214
CH3
1 2 3-16 17 18
(b)
(a)
(d)
(c)
(e)
(f)
50 0 -50 -100 -150 -200
Q4
Q3
-15 -30 -45 -60 -75
T3
T2
(b)
Chemical shift [ppm]
(a)
(d)
(c)
(g)
(e)
(f)
Q2
Figure 1: Solid-state NMR spectra of the modified silicas (all of them with the
organic content increasing from down to up): a) 1H-MAS-NMR b) 13C-
CP/MAS-NMR c) 29Si-CP/MAS-NMR
Any of these individual techniques proved to be invaluable for the complete
characterization of the hybrid material [3]. Ongoing, metallocene catalyst is being
immobilized at these supports for olefin copolymerization trials.
A. A. Bernardes thanks CNPq-RHAE (472571/2014) for financial support.
References
[1] - K. Albert and E. Bayer, Journal of Chromatography 544, 345-370 (1991)
[2] - L. Bourget et al, Journal of Non-Crystalline Solids 242, 81-91 (1998)
[3] - A. A. Bernardes et al, Journal of Non-Crystalline Solids 466, 8-14 (2017)
a) b) c)
ISPAC 2018 - Session: Condensed Phase Spectroscopy
55
T.23 - Relating Post Yield Mechanical Behavior in Polyethylenes to
Spatially-varying Molecular Deformation Using Infrared Spectroscopic
Imaging: Homopolymers
Prabuddha Mukherjeea, Ayanjeet Ghosh a, Nicolas Spegazzinia, Mark J Lambornb, Masud
M Monwarb, Paul J DesLauriersb* and Rohit Bhargava*ac
aBeckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign,
Urbana, IL 61801, USA bChevron Phillips Chemical Company LP, Bartlesville, OK 74004, USA
cDepartments of Bioengineering, Chemical and Biomolecular Engineering, Electrical and Computer
Engineering, Mechanical Science and Engineering and Chemistry, University of Illinois at Urbana-
Champaign, Urbana, IL 61801, USA
email: [email protected]
Stress-strain curves derived from tensile specimens are the primary characteristic of bulk
polymers’ mechanical properties. Current tools, however, cannot provide molecular insights
from this single bulk measurement. Hence, we use Fourier transform infrared (FT-IR)
spectroscopic imaging to optically and non-destructively measure molecular structure and
its spatial dependence in tensile specimens in high density polyethylene homopolymers. To
overcome the limitations of FT-IR imaging, we use an emerging approach involving the use
of tunable quantum cascade lasers that allows imaging through thick samples and facile
polarized light imaging. Crystal structure and orientation are obtained from spatially varying
measurements of molecular properties in the necking region. Local molecular
(re)arrangements to characterize mechanical properties of drawn samples are deduced from
spectral data. A modified Eyring model was developed to quantitatively understand spatial
dependence in terms of a conformational volume. We report the strain rise in high density
polyethylene homopolymers is governed by the degree of association between the crystalline
domains. Together, the new measurement technology and analysis reported here can relate
molecular composition, microscopic gradients and orientation to bulk mechanical properties
of semi-crystalline polymers.
Schematic illustration of how the spatial variation of molecular response in a polymer can be used to evaluate
mechanical properties spectroscopy and imaging. (Left) The physical process of necking, demonstrating the
focus of the study on the necking region. (Middle) A representative stress-strain curve for HDPE overlaid on
the cartoon of a necked polymer. (Right) Drawn tensile samples exhibit optical anisotropy beyond the yield
point that arises from molecular reorganization and are seen in polarized infrared spectra. Anisotropy
measurements by imaging allows visualization of the spatial distribution of molecular orientation in the entire
sample, with localized sensitivity.
ISPAC 2018 - Session: Condensed Phase Spectroscopy
56
T.24 - Influencing liquid crystalline gel formation in cellulose ionic liquid
solutions by adding water and nanoparticles
Ashna Rajeev, Abhijt P Deshpande, Basavaraja M. Gurappa
Polymer Engineering and Colloidal Science Lab, Dept of Chemical Engineering,
Indian Institute of Technology Madras, India. 600036
Liquid crystalline gels find application in different fields such as, display and storage
devises, sensors etc. Recently, it was reported that cellulose dissolved in 1-ethyl-3-
methylimidazolium acetate (EmimAc) shows sol-gel transition accompanied by a liquid
crystalline phase transition at high cellulose concentrations [1].
In this work we report the preparation of liquid crystalline gel phase from cellulose/ionic
liquid solutions by altering the solvent environment due to the addition of water which is an
anti-solvent for cellulose. We studied the characteristics of cellulose/ionic liquid/ water
mixtures at 5-15 wt% of cellulose concentrations by combining rheological and polarisation
optical microscopy observations. We observed the formation of non-aligned Cholesteric
liquid crystalline phase at low cellulose concentration and spherulite-like assemblies at high
cellulose concentration. Further we investigated the enhancement of gel properties by
incorporating spherical as well as shape anisotropic nanoparticles at different nanoparticle:
cellulose weight ratios, into the cellulose/ionic liquid/water gel matrix.
Figure 1: Polarization optical microscopy image showing non-aligned holesteric liquid crystalline phase in
10 wt% cellulose/BmimCl solution.
References
[1] – H. Song et al., Biomacromolecules, 12, 1087 (2011).
ISPAC 2018 - Session: Advances in Chromatography
57
T.25 - Characterization of branched polycarbonate by comprehensive
two-dimensional liquid chromatography with multi-detector setup and
correlation with Monte-Carlo simulations
Nico Apel1, Elena Uliyanchenko2, Vaidyanath Ramakrishnan2, Tibor Macko1, Robert
Brüll1
1Fraunhofer Institute for Structural Durability and System Reliability (LBF), Division Plastics, Group
Material Analytics, Schlossgartenstr. 6, 64289 Darmstadt, Germany, [email protected] 2SABIC, Plasticslaan 1, 4612 PX Bergen op Zoom, the Netherlands
Branching is often applied to influence rheological properties of plastics. Exemplarily,
branching increases polymer melt elasticity at low shear rates and reduces viscosity at high
shear rates (shear thinning) and as a result the processing of plastics as well as its final
properties are influenced by branching. In this sense branching is an important driver of
material innovation, and appropriate analytical protocols are required to determine these
parameters.
Because branching distribution coexists with other molecular distributions (e.g. with regard
to molecular weight and functionality-type) such materials are very complex in their
composition. Thus, an in-depth characterization of branched polymers requires an adequate
combination of multiple analytical techniques. While separations based on molecular size
and end-group type are relatively straightforward, by size-exclusion chromatography (SEC)
and liquid chromatography at critical conditions (LCCC), respectively, to date no specific
technique for a separation based on branching level available.
In this work, we describe two-dimensional liquid chromatography analysis of branched
polycarbonate. Utilizing differences in end-group composition and in the hydrodynamic
volume between branched and linear chains, we were able to achieve a separation of
structures with different branching levels [1]. In the first dimension, a shallow solvent
gradient was applied with a mobile phase composition in proximity to the critical point of
adsorption allowing for a separation according to end-groups [1]. This separation was then
hyphenated to SEC as a second dimension and complimented with a multi-detector setup
(UV, refractive index, light scattering detectors and a viscometer) [2]. This allowed access
to (semi)quantitative information on the end-group, molecular weight and branching
distributions in the sample. The resulting experimental data were then correlated with
Monte-Carlo simulations of the polymerisation of branched sample validating the underlying
simulation model [2].
References
[1] Apel, N.; Uliyanchenko, E.; Moyses, S.; Rommens, S.; Wold, C.; Macko, T.; Brüll, R. Separation of
Branched Poly(bisphenol A)carbonate Structures by Solvent Gradient at Near-Critical Conditions and
Two-Dimensional Liquid Chromatography. Anal. Chem. 2018, accepted, DOI:
10.1021/acs.analchem.8b00618
[2] Apel, N.; Ramakrishnan, V.; Uliyanchenko, E.; Moyses, S.; Rommens, S.; Wold, C.; Macko, T.; Brüll,
R., Correlation between Comprehensive 2D Liquid Chromatography and Monte- Carlo Simulations for
Branched Polymers. 2018, Submitted to Macromolecules.
ISPAC 2018 - Session: Advances in Chromatography
58
T.26 - Valorisation of multi-dimensional analytical approaches to unlock
complex products characterization. The particular case of apolar
commercial synthetic polymers.
Jessica S. Desport1, Gilles Frache1, Marcel Wirtz2
1Materials Research and Technology Department, Luxembourg Institute of Science and Technology,
Belvaux, Luxembourg 2Goodyear Innovation Center Luxembourg, Colmar‐Berg, Luxembourg
At first sight, liquid adsorption chromatography and polymers look rather mismatched since
polymers are a mixture of congeners having different length and thus retention time is
strongly affected by the number of repeated units of a given chain. Despite this apparent
incompatibility, efforts have been made to develop methods addressing a separation
exclusively based on chemical nature or architecture. However, analysis consistency is often
being significantly affected by samples complexity. Indeed, modern advances in
macromolecular synthesis have delivered a path toward more complex structures and
architectures. As a result, conventional analytical techniques, like chromatography or mass
spectrometry, taken individually, may only provide with a partial picture of the sample. This
is all the more important when considering commercial products. Indeed, commercial
polymeric materials are typically heterogeneous both in terms of mass and chemical
distributions. Besides, they often consist of a mixture, including additives such as anti-
oxydants, or modifiers. In this work, characterization of industrial polymer products was
addressed. Implementing a suitable coupling of analytical tools appeared to provide the most
powerful and comprehensive strategy to achieving product breakdown and in-depth
molecular elucidation (Figure 1). Two-dimensional chromatography (LCCxGPC,
GPECxGPC, LCCxLCC) was used as core technique to achieve molecules separation based
on size and chemical nature while mass spectrometry permitted the identification of the
different molecular populations. The particular apolar nature of the samples required a
screening of ionization techniques (MALDI, ESI), analyzers (Orbitrap, TOF), as well as
sample preparation to optimize intact ions detection. All data generated were processed as
material “fingerprints”, either via contour plot images or Kendrick plots, allowing for a fast
and valuable comparison of commercial batches.
Figure 1: Multi-dimensional analytical toolbox for advanced polymer characterization.
ISPAC 2018 - Session: Advances in Chromatography
59
T. 27 - Size Exclusion Chromatography Characterization of Poly(Ester
Urethane) Degradation Products
Dali Yang
MST-7: Engineered Materials, MST Division, Los Alamos National laboratory
Los Alamos, NM 87545, USA, [email protected]
Poly(ester urethane) (PEU) is a multiblock copolymer obtained by the polymerization of
4,4’-diphenylmethane diisocyanate (MDI) chain-extended with 1,4-butanediol (BDO) as
the rigid hard segment and polybutylene adipate (PBA) as the flexible soft segment. With
these two segments, the polymer exhibits good abrasion resistance, high elongation, low
temperature flexibility. It can be processed by means of solution coating, extrusion, and
melt coating. Therefore, these polymers are widely used as adhesive for inks and lacquers,
fabric coating, binder for magnetic media[1], and composite material formation[2]. Recent
years, poly(ester urethane) gains more and more interests in biomedical applications and
biomaterial fields because of its elasticity, sufficient mechanical strength and
biodegradability[3]. It is essential to understand these properties change as the material
ages and to identify the chemical degradation mechanisms. Over the years, numerous
studies have been conducted and have determined several mechanisms of degrading the
poly(ester urethanes) depending on exposure environments, such as hydrolysis and non-
hydrolysis reactions caused by the presence of moisture or/and oxidant.[4] To accelerate
the aging processes in experiments, the polymers are often aged under elevated
temperatures resulting in chain scissions and branched structures, which make the
identification of the chemical structures of the degraded products challenging.
Figure 1: Chemical structure of Estane – a type of poly(ester urethane) polymers.
In this contribution, we systematically characterized a set of naturally aged Estanes with the
molecular weight ranging from 135 – 20 kDa. The combination of size exclusion
chromatography with UV/Vis, viscometer, MALS detectors allows us to fully analyze the
degraded polymers, leading to new information about (i) chemical structures of oligomer
and polymer fractions, (ii) Mark-Houwink correlations, and (iii) their dn/dc values. This
work was supported by the US Department of Energy through the Los Alamos National
Laboratory Enhanced Surveillance Program.
1. References
2. [1] https://plastics.ulprospector.com/datasheet/e122063/estane-5703-tpu.
3. [2] Salazar MR, Pack RT. J of Polymer Science: Part B: Polymer Physics. 2002;40:8; and Salazar M, R.,
Kress JD, Lightfoot JM, Russell BG, Rodin WA, Woods L. Polymer Degrdation and Stability. 2009;94:9.
4. [3] Pierce B. F., Brown A. H., Sheares V. V. Macromolecules, 2008;14:8; Mou Z., Y.-X Chen E., ACS
Sustainable Chem. Eng., 2016;4:12; Fang J., Ye S.H., Huang Y.X., Mo X.M., Wagner W. R. Acta
Biomater. 2014;10:11; Gugerell A., Kober J., Laube T., Walter T. et al. POLS ONE, 2014;9(3):14.
5. [4] Brown D. W., Lowry R. E., Smith L. E. Macromolecules, 1980;13:8 and Jellinek, H. H. G.,
Wang, T. J. Y. Journal of Polymer Science 1973;11:16.
NH
C
O
O
H2C
NH
C
O
OC
COO
O
O
O
m = 1-3n = 4-6
PolyesterSo SegmentPolyurethane(MDI)HardSegment
ISPAC 2018 - Session: Advances in Chromatography
60
T.28 - Polymer separation beyond SEC – expanding the range
from molecules to particles
Robert Reed1, Bassem Sabagh2, Paul Clarke2, Gerhard Heinzmann3
1) Postnova Analytics Inc, Salt Lake City, UT, USA,
2) Postnova Analytics UK Ltd, Malvern, UK,
3) Postnova Analytics GmbH, Landsberg, Germany
Size exclusion chromatography (SEC or GPC) is an immensely useful and valuable tool for
polymer solution characterization. However, despite its universality, the characterization of
polymers in solution for molecular weight and size/structural information by SEC is highly
restricted by the requirement that the polymer is fully dissolved in the mobile phase and has
no interaction with the column packing material. Furthermore, any formation of polymer
particles or other supramolecular structures such as vesicles (polymersomes) results in
erroneous or incomplete size or molecular weight distributions.
As SEC cannot be used after the formation of polymer latex or other supramolecular
structures means we must resort to batch techniques such as static light scattering (MALS)
or dynamic light scattering (DLS). These batch techniques yield very limited information
about the distribution of molecular weight or size and furthermore may give misleading
information due to the weighting of the data by larger species.
This paper describes and presents a flow technique to complement SEC that can separate
polymers and polymer structures in solution or suspension and can be coupled on-line to
DLS and MALS to get accurate distribution information. We will show several examples of
how highly valuable analytical data can be obtained from polymers, polymer latex, polymer
particles and polymer vesicles that is not obtainable in any other way.
ISPAC 2018 - Session: Advances in Chromatography
61
Wyatt Technologies Lecture
W.01 - Structure and Dynamics in Polymer-Grafted Nanoparticle
Systems
Michael J. A. Hore, Yuan Wei, and Yifan Xu
Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, OH
USA. [email protected]
When grafted to spherical nanoparticles, polymers can adopt a variety of conformations
depending on the nanoparticle size and polymer grafting density.[1] At moderate grafting
densities, a high concentration of polymer near the nanoparticle (“concentrated polymer
brush”, CPB region) core creates confinement effects that cause the polymer chain to be
stretched, with a thickness that scales with the degree of polymerization (N) as h ~ N0.8. Past
a cutoff distance rc, that can be calculated by scaling theories, the concentration decreases
with increasing distance from the core (“semi-dilute polymer brush”, SDPB region) and the
polymer chain adopts a more random conformation. In this talk, we discuss recent progress
in characterizing the structure and dynamics of polymers that are grafted to spherical
nanoparticles by small-angle neutron scattering (SANS) and neutron spin echo spectroscopy
(NSE), respectively. New core-shell-chain (CSC) and core-chain-chain (CCC) form factors,
which account for excluded volume in the polymer chains, are able to capture the predictions
from scaling theories, and are in good agreement with scaling relationships observed from
dynamic light scattering (DLS) and electron micrograph analysis.[2] NSE measurements
show that the confinement experienced in the CPB region can have a significant impact on
the relaxation dynamics of the polymers, which may in turn have implications for the
processing and mechanical properties of nanocomposites containing such particles.
Figure 1: Selective deuteration scheme utilized to measure structure and dynamics in the concentrated
polymer brush (CPB) and semi-dilute polymer brush (SDPB) regions of polymer-grafted silica nanoparticles.
References [1] W. R. Lenart and M. J. A. Hore, Nano-Structures & Nano-Objects 2017 (in press).
[2] M. J. A. Hore, J. Ford. K. Ohno, R. J. Composto, and B. Hammouda, Macromolecules 2013, 46, 9341-
9348.
ISPAC 2018 - Session: Advances in Chromatography
62
W.02 - Recent Advances in X-ray Scattering Methods for Soft Materials
Kevin G. Yager
Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY USA. [email protected]
X-ray scattering methods have been used to great effect in the study of polymer materials,
from resolving the nanoscale morphology of self-assembling materials to quantifying the
molecular packing of semiconducting polymers. This talk will discuss recent efforts to
further expand the utility of x-ray scattering in the study of soft materials. While traditional
scattering focuses on the ensemble average, emerging techniques that emphasize variability
can undercover additional information. Variance along scattering rings can be analyzed to
extract hidden information about grain structure. Angular correlation methods can be
combined with coherent scattering to amplify the signal from the sample above background.
New methods for improving data quality will also be discussed. X-ray detector images can
be ‘healed’ in a physically meaningful-way, and grazing-incidence scattering (GISAXS)
images can be ‘unwarped’ by either altering measurement geometry or through data analysis.
Finally, recent work in the use of deep learning to analyze scattering images will be
presented.
ISPAC 2018 - Session: Advances in Chromatography
63
Pfizer Consumer Healthcare Lecture
W.03 - Soft matter structure measurement by Polarized Resonant
Soft X-ray Scattering
Dean M. DeLongchamp
National Institute of Standards and Technology, Gaithersburg, MD
In many applications of soft matter, the connection between structure and performance is
complex, and conventional structure measurements are not sufficient to provide a
predictive structural model. Nanoscale variations in molecular orientation and composition,
particularly in amorphous regions, are thought to be critical, but few techniques can probe
them. I will describe our approach to polarized resonant soft X-ray scattering (P-RSoXS),
which combines principles of spectroscopy, small-angle scattering, real-space imaging, and
molecular simulation to produce a molecular scale structure measurement for soft materials
and complex fluids. Progress and designs for a new P-RSoXS beamline will be shown.
Results from model systems including commodity plastics, block copolymers, and organic
photovoltaics blends will be discussed. An emphasis will be placed on connections
between P-RSoXS and small angle neutron scattering (SANS), including different contrast
approaches, different experimental considerations, and unique measurement capabilities of
each technique.
ISPAC 2018 – Poster Session
64
P.01 - (LF)TD-NMR FOR THE STUDY OF POLYMERIC NETWORKS
Denise Besghini, Michele Mauri, Roberto Simonutti,
Department of Materials Science, University of Milano-Bicocca, via R. Cozzi 55, 20125
Milan
Polymer networks, including rubbers and hydrogels, are ubiquitous materials. The
determination of their structure-property relationship is fundamental for their rational
improvement. Low Field (LF) Time Domain (TD) Nuclear Magnetic Resonance (NMR) is
a powerful technique to probe molecular-level dynamics, through 1H relaxation times T1 e
T2. Important variations in chain dynamics, such as phase transitions, can be easily monitored
with the study of T2 at varying temperatures. In Figure 1, a methylated cellulose
thermogelating material1 shows increased T2 upon temperature increase, followed by a
sudden drop at the gelation point. The reversibility of the process, the formation of a
metastable phase and the associated hysteresis phenomena can be monitored, obtaining
results in line with rheological testing.
Left: T2 relaxation time of methylcellulose gels during a temperature cycle (from 10 to 75 °C). Right,
distribution of dipolar coupling in an heterogeneous reversibly crosslinked rubber, compared to a more
homogeneous sample.
TD-NMR can also measure dipolar couplings (Dres), which are linearly proportional to
crosslinks density (CLD), according to the equation 𝐶𝐿𝐷 =𝐷𝑟𝑒𝑠
4𝜋𝐴. This has been exploited to
measure the evolution of crosslinking in conventional rubbers and their blends,2.and to prove
the formation of polar crosslinks clusters in more innovative modified EPDM rubbers
crosslinked via reversible Diels-Alder chemistry3. Figure 1 (right) highlights the bimodal
distribution of Dres in an heterogeneous system as compared to a more homogeneous one.
Access to CLD distribution is the most outstanding advantage of TD-NMR compared to
traditional method for the determination of CLD, such as equilibrium swelling
measurements. These examples highlight that TD-NMR is a comprehensive tool to
characterize in details polymeric networks, making it suitable for both academic and
industrial applications.
1. P. Nasatto, F. Pignon, J. Silveira, M. Duarte, M. Noseda and M. Rinaudo, Polymers, 2015, 7, 777.
2. M. K. Dibbanti, M. Mauri, L. Mauri, G. Medaglia and R. Simonutti, Journal of Applied Polymer
Science, 2015, 132, n/a-n/a.
3. L. M. Polgar, E. Hagting, P. Raffa, M. Mauri, R. Simonutti, F. Picchioni and M. van Duin,
Macromolecules, 2017, 50, 8955-8964.
ISPAC 2018 – Poster Session
65
P.02 - Crystallization and Alkaline Hydrolysis Studies of Poly(3-
hydroxybutyrate)
N. Vasanthan , A. Tappadiya
Department of Chemistry and Biochemistry, Long Island University, One University Plaza, Brooklyn, NY
11201, [email protected]
Poly(3-hydroxybutyrate) (PHB) is a microbially synthesized polymer, which is often
purified by alkaline treatment. The effect of microstructure on alkaline hydrolysis has been
studied by varying concentration of base and the temperature. The morphologies of PHB
films before and after degradation were evaluated using DSC and FTIR spectroscopy. The
hydrolytic degradation study by weight loss measurement revealed that the crystallinity of
PHB greatly decreased the hydrolytic ability of PHB. The crystallization of PHB and the
effect of base on hydrolysis was investigated by time dependent FTIR spectroscopy. The
normalized absorbance of 3010 cm-1 and 1183 cm-1 were used to characterize the crystalline
and the amorphous phases of PHB, shown in Figure 1. FTIR spectroscopy reveal that the
extent of hydrolysis decreased with increasing crystallinity. The crotonic acid was detected
as a major product after hydrolysis, confirmed by UV/Visible and proton NMR
spectroscopy. The normalized absorbance of the crystalline band at 3010 cm-1 band remained
constant, suggesting that there is no significant change in crystallinity with degradation. The
normalized amorphous band at 1183 cm-1 showed a decrease in absorbance ratio, suggesting
degradation of the amorphous phase.
.
Figure 1: FTIR spectra of PHB films cold crystallized at different temperatures in the region (a)1500-900 cm-
1 and (b) 3050-2850 cm-1.
References
1. Doi Y, Steinbuchel A, Eds. Biopolymer, Polyesters I-Biological Systems and Biotechnological Production;
John Wiley and Sons: Weinheim, Germany, 2001;3
2. Gross RA, Kalra B. Biodegradable polymers for the Environment Science 2002;297:803-7.
3. Matsusaki H, Abe H, Doi Y. Biomacromolecules 2000;1:17.
4. Steinbuchel A, Valentine H E. FEMS Microbiol Lett 1995;128:219.
5. Tapadiya, A, Vasanthan, N. International Journal of Biological Macromolecules, 2017, 102, 1130
ISPAC 2018 – Poster Session
66
P.03 - Use of Cottonseed Protein in Wood Adhesives
H. N. Cheng, Zhongqi He, and Michael K. Dowd
Southern Regional Research Center, USDA Agricultural Research Service,
1100 Robert E. Lee Blvd., New Orleans, LA 70124, USA
Email: [email protected]
Wood adhesives are industrially important materials used to bond wood products together.
Currently most wood adhesives are based on formaldehyde resins and polyurethanes. In
the past 20 years, there has been increasing attention paid to green technologies, which is
reinforced by the environmental concern regarding formaldehyde and the desire to move
away from petroleum derived raw materials. As a result, there is growing interest in using
agro-based materials as wood adhesives, particularly soy proteins [1,2].
Another material studied as a bio-based wood adhesive is cottonseed protein, which has
been found to have good dry adhesive strength and hot water resistance [3]. In this
presentation, a selected review will be made of the recent developments relating to
cottonseed protein and its applications in wood adhesives. In particular, the addition of
denaturants to cottonseed protein isolate (CPI, >85% protein), such as sodium dodecyl
sulfate, guanidine hydrochloride, and urea, has been found to improve dry adhesive
strength but not hot water resistance [4]. The addition of selected amino acids [5], low-
molecular-weight carboxylic acids [5], or phosphorus-containing compounds [6] to CPI
have been shown to enhance dry adhesive strength, and the addition of phosphorus
compounds has been found to improve hot water resistance [6]. Blends of cottonseed
protein and soy protein with xylan, starch, and cellulose have been studied; in several
cases, adhesive performance was retained even when the cottonseed or soy protein was
mixed with up to 50-75% polysaccharide [7]. A lot of work has also been done on water-
or buffer-washed cottonseed meals; their adhesive performance was found to be
comparable to that of CPI [8-11], which would reduce the cost of manufacturing the
adhesive. Since one factor in new product development is performance/cost ratio, an
increase in adhesive performance or a decrease in cost would likely improve the chances of
a product reaching the marketplace.
References: [1] A. Pizzi and K.L. Mittal (eds.). Wood adhesives. CRC Press, Boca Raton, FL, 2011.
[2] Z. He (ed.). Bio-based wood adhesives: preparation, characterization, and testing. CRC Press, Boca
Raton, FL, 2017.
[3] H.N. Cheng, M.K. Dowd and Z He. Ind. Crop Prod. 46, 399 (2013).
[4] H.N. Cheng, C. Ford, M.K. Dowd and Z. He. J. Adhes. Sci. Technol. 31, 2657 (2017).
[5] H.N. Cheng, C. Ford, M.K. Dowd and Z. He. Int. J. Adhes. Adhes. 68, 156–160 (2016).
[6] H.N. Cheng, C. Ford, M.K. Dowd and Z. He. Int. J. Adhes. Adhes. 77, 51 (2017).
[7] H.N. Cheng, C. Ford, M.K. Dowd and Z. He. Ind. Crop Prod. 85, 324 (2016).
[8] Z. He, D.C. Chapital, H.N. Cheng and M.K. Dowd. Int. J. Adhes. Adhes. 50, 102 (2014).
[9] Z. He, H.N. Cheng, D.C. Chapital and M.K. Dowd. J. Am. Oil Chem. Soc. 91, 151 (2014).
[10] Z. He, D.C. Chapital, H.N. Cheng and O.M. Modesto. J. Adhes. Sci. Technol. 30, 2109 (2016).
[11] Z. He, H.N. Cheng, K.T. Klasson, O.M. Olanya and J. Uknalis. Polymers 9, 675 (2017).
ISPAC 2018 – Poster Session
67
P.04 - Interface evolution during reaction between incompatible polymer
layers
G. Yuan1,2, M. Wang3, C. C. Han4
1Georgetown university, 2NIST center for neutron research, [email protected]; 3Institute of
Chemistry, Chinese Academy of Sciences, [email protected]; 4Shenzhen university,
Bisphenol-A polycarbonate (PC) and amorphous polyamide (aPA) were used as reactive
system to study the interfacial interchange reaction between condensation polymers [1, 2].
Aminolysis is the main process during thermal annealing at 160 – 180 oC. The
simultaneously scission of PC chains and formation of PC-aPA copolymer chains during the
reaction process, act as interfacial compatibilization agents between incompatible
homopolymers. The reaction kinetics was probed by Fourier transform infrared and the
interfacial morphology development was analyzed by neutron reflectometry and atomic
force microscopy. The influence of a reactive compatibilizer, hyperbranched
polyethylenimine, on the interfacial fracture toughness was also demonstrated by augmented
double cantilever beam method (Figure 1). With the well-controlled miscibility between PC
and aPA, an excellent multi-layered composite material can be formed, in which PC
decreases water take-up of aPA, whereas aPA enhances the solvent resistance of PC.
Figure 1: Fracture energy, Gc , as a function annealing time in planar layer samples with and without hPEI at
the interface.
[1] M.Wang, G. Yuan and C.C. Han, Polymer. 54, 3612 (2013).
[2] M.Wang, G. Yuan and C.C. Han, Chinese Journal of Polymer Science, 33, 652 (2015).
ISPAC 2018 – Poster Session
68
P.05 - Application of gel time measurement and high-performance liquid
chromatography to describe the storage stability of resole resin solutions
S. Blaschke1, C. Schwarzinger1, A. Heidegger2, V. Föge2, F. Nickel2
1Institute for Chemical Technology of Organic Materials, Johannes Kepler University Linz,
Altenbergerstrasse 69, 4040 Linz, Austria, 2Miba Frictec GmbH, Peter Mitterbauer Strasse, 4661 Roitham,
Austria
The polycondensation of thermosetting phenolic resin solutions is a highly temperature
dependent reaction. Therefore, the temperature of storage has a strong influence on the shelf
life. While other stability studies based their investigations on the study of the change in
viscosity and molecular weight distribution [1] or infrared spectroscopy (FT-IR) and
dynamic scanning calorimetry (DSC) [2], simple gel time measurements proved to be
sufficient. It could be shown that commercial resole resin solutions can be fitted into
Arrhenius like models to extrapolate the temperature dependent changes of the liquid
material over arbitrary temperature range.
Figure 1: Arrhenius plot (I) based on the decrease in gel time during storage for three different commercial
resole resins and corresponding plot (II) illustrating a comparison of storage stability of those three resins.
Additional high-performance liquid chromatography (HPLC) studies of the content of free
monomers revealed that the change in the content of free phenol seems to correlate with the
change in gel time during storage, while the content of free formaldehyde decreases in
another pattern.
References
[1] M. K. Gupta and R. R. Hindersinn, Polym. Eng. Sci. 27, 976 (1987).
[2] H. L. Wu, D. Z. Zhang, X. Wang and S. P. Lu, J. East China Univ. Sci. Technol. 43, 335 (2017).
ISPAC 2018 – Poster Session
69
P.06 - pyPRISM: A Computational Tool for
Liquid-State Theory Calculations of Macromolecular Materials
Tyler B. Martin,1 Thomas E. Gartner III,2 Ronald L. Jones,1 Chad R. Snyder,1 Arthi
Jayaraman2,3
[email protected], 1National Institute of Standards and Technology, 2Chemical and Biomolecular
Engineering, University of Delaware, 3Materials Science and Engineering, University of Delaware
Polymer Reference Interaction Site Model (PRISM) theory describes the equilibrium spatial-
correlations of liquid-like polymer systems including melts, blends, solutions, block
copolymers, ionomers, polyelectrolytes, liquid crystal forming polymers and
nanocomposites. Using PRISM theory, one can calculate thermodynamic (second virial
coefficient, χ interaction parameters, potential of mean force) and structural (pair correlation
functions, structure factor) information for these macromolecular materials. Here, we
present a Python-based, open-source framework, pyPRISM, for conducting PRISM
theory calculations.[1,2] This framework aims to simplify PRISM-based studies by
providing a user-friendly scripting interface for setting up and numerically solving the
PRISM equations. pyPRISM also provides data structures, functions, and classes that
streamline PRISM calculations, allowing pyPRISM to be extended for use in other tasks
such as the coarse-graining of atomistic simulation force-fields or the modeling of
experimental scattering data. The goal of providing this framework is to reduce the barrier
to correctly and appropriately using PRISM theory and to provide a platform for rapid
calculations of the structure and thermodynamics of polymeric fluids and nanocomposites.
Figure 1: pyPRISM graphic (top) and example results for a polymer nanocomposite.
[1] – Martin, T.B.; Gartner, T.E III; Jones, R.L.; Snyder, C.R.; Jayaraman, A.; pyPRISM: A Computational
Tool for Liquid State Theory Calculations of Macromolecular Materials, Macromolecules,
10.1021/acs.macromol.8b00011
[2] – https://github.com/usnistgov/pyprism, http://pyprism.readthedocs.io
ISPAC 2018 – Poster Session
70
P.07 - Thermal-Gradient NMR of EPDM: A way to learn about the
mechanism of separation of Hypercarb columns?!
F. Malz1, R. Brüll1, Z. Zhou2, R. Cong3, D. Mekap3, W. deGroot3
1Fraunhofer Institute for Structural Durability and System Reliability, Division Plastics, Germany, 2Core
R&D Analytical Sciences, The Dow Chemical Company, US, 3Performance Plastics Characterization and
Testing Group, The Dow Chemical Company, US
High temperature liquid chromatography (HT-LC) has emerged as an important analytical
tool to analyze polyolefins in terms of their chemical composition distributions [1,2,3]. The
method separates the macromolecules according to the differences in their interactions, in
solution, with a graphite stationary phase. It is vital to gain insight into the nature of these
interactions. To achieve this goal high-temperature nuclear magnetic resonance spectroscopy
(HT-NMR) can be applied in a unique manner in the form of thermal-gradient NMR (TG-
NMR) [4]. The result of a TG-NMR experiment is a course of signal intensity as a function
of the temperature. Recently, the interaction of ethylene homopolymer with graphite was
monitored by TG-NMR for the first time [5].
Figure 1: Results from TG-NMR of PE in ODCB-d4, blue: without graphite, red: with graphite.
The investigation was extended to EPDM terpolymers. The EPDM separation depends on
the content of E and ENB. Therefore, EPDM samples with different ENB contents were
analyzed by TG-NMR. The objective of this research work was to analyze differences in the
TG-NMR traces of the different EPDM samples.
References
[1] – D. Mekap, T. Macko, R. Brüll., R. Cong, A.W. deGroot and A.R. Parrott, Ind. Eng. Chem. Res. 53,
15183 (2014).
[2] – A.W. deGroot, D. Gillespie, R. Cong, Z. Zhou and R. Paradkar, chapter 5 “Molecular Structural
Characterization of Polyethylene” in Handbook of Industrial Polyethylene and Technology: Definitive Guide
to Manufacturing, Properties, Processing, Applications and Markets, Wiley, 2017.
[3] – R. Cong, A.W. deGroot, A.R Parrott, W. Yau, L. Hazlitt, R. Brown, M. Miller and Z. Zhou,
Macromolecules 44, 3062 (2011)
[4] – Z. Zhou, R. Cong, Y. He, M. Paradkar, M. Demirors, M. Cheatham and A.W. deGroot, Macromol.
Symp. 312, 88 (2012)
[5] – D. Mekap, F. Malz, R. Brull, Z. Zhou, R. Cong, A.W. deGroot and A.R. Parrott, Macromolecules 47,
7939 (2014)
ISPAC 2018 – Poster Session
71
P.08 - Analysis and quantification of polycarbonate end-groups by liquid
chromatography at critical conditions
Elena Uliyanchenko1, Stijn Rommens1, Nico Apel2, Robert Brüll2
1SABIC, Plasticslaan 1, 4612 PX Bergen op Zoom, the Netherlands, [email protected]
2Fraunhofer Institute for Structural Durability and System Reliability (LBF), Division Plastics, Group Material
Analytics, Schlossgartenstr. 6, 64289 Darmstadt, Germany
Knowledge on end-group functionality and their distribution in polymers is very important in
industrial material development: specific functional groups may serve as compatibilizers for
otherwise immiscible polymer blends, they may be used to modify material properties or to
facilitate further reactions e.g., to produce block copolymers. Furthermore, end-cappping may be
introduced during the polymerization to control molecular weight and to minimize the presence of
reactive groups, which prevents degradation and, thus, extends durability of the final materials. In
all these cases, monitoring the content and type of end-group functionalities is important, as this
information directly relates to the properties of the materials (structure-property relationship).
In addition to end-group distribution, almost all polymers exhibit a distribution with regard to
molecular weight, which complicates their characterization. Liquid chromatography at critical
conditions (LCCC) is a unique technique that allows separating polymers based on end-groups
excluding the influences of molecular weight on the elution time. The separation occurs at the
thermodynamic equilibrium conditions where enthalpic and entropic contributions compensate
each other. For each type of polymer, this happens at a specific combination of stationary phase,
mobile phase and temperature. Thus, determination of the critical conditions is usually challenging
and time-consuming.
In this study we discuss LCCC separation of poly (bisphenol A carbonate) (PC) and its applications
in industry. Although LCCC for PC was described earlier [1], this separation had limited practical
use, as it was not able to measure all end-group combinations present in a common PC sample. In
this work we further explore and optimize LCCC separation of PC and demonstrate the possibility
to detect additional end-groups and structures. Moreover, we apply this method to quantify
different functionality types and compare the results with those from other analytical techniques.
In a next step, this LCCC separation is coupled to size-exclusion chromatography in a two-
dimensional setup to additionally obtain molecular weight data for each type of polymer chains.
The extracted information provides valuable insights into material properties (e.g. aging) as well
as the underlying production processes (e.g. end-capping efficiency) and, thus, facilitates a
material optimization based on the molecular structure of the PC.
1. References
[1] L. Coulier, E.R. Kaal, Th. Hankemeier, J. Chromatogr. A, 1130 (2006) 34-42
ISPAC 2018 – Poster Session
72
P.09 - Analysis of charge states of water soluble polymers by
Capillary electrophoresis
Mitsuyoshi Kawashima1), Yoshiomi Hiroi1)
Koutatsu Matsubara1), Katsumi Chikama1)
1)Nissan Chemical Industries, LTD [email protected]
Introduction In recent years, water soluble polymers are used in various material fields.
Their polymer structures are analyzed by NMR, FT-IR, and size exclusion chromatography
(SEC), but it is difficult to analyze their charge states that seems to strongly influence of
material properties. Capillary electrophoresis (CE) is an analytical technique that separates
ions by their electrophoretic mobilities and often used for separation of biopolymers[1].
Therefore, we have applied CE to the charged synthetic polymers, and discussed the
relationship between charge state and mobility.
Experiment Amphoteric polymers comprising a cationic and an anionic monomer were
synthesized (Figure1). The different charge polymers were obtained by changing the charging
ratio of monomers. They were analyzed by capillary zone electrophoresis (CZE) and the
mobilities were calculated. The electrophoresis solution was 20 mM sodium tetraborate
decahydrate (pH 9.3). The capillary temperature was 25 ° C, the voltage was applied at 30
kV.
Results and Discussion It was revealed that as the proportion of anionic monomer increased,
the mobility(absolute value) of the polymer increased. It shows that the mobility depends on
the charge state of the polymer. Furthermore, plotting charging ratio of the monomer and the
mobility of the polymer revealed that they were correlated (Figure2). This indicates that the
separation of CZE is dominated by the charge state of the polymer.
Figure 1: (Left) Amphoteric polymer. (R1=Anion unit, R2=Cation unit and (Right) Charging ratio and mobility
[1] - Vladislav Dolník, Electrophoresis, 20, 3106~3115 (1999)
ISPAC 2018 – Poster Session
73
P.10 - Liquid Chromatography with porous graphitic carbon as stationary
phase for the characterization of stabilizers David Kot, Nico Apel, Tibor Macko, Robert Brüll
Fraunhofer Institute for Structural Durability and System Reliability LBF, Schlossgartenstraße 6, 64289
Darmstadt; [email protected]
Stabilizers play a very important role throughout the entire life cycle of synthetic polymers.
They are introduced to prevent oxidation occurring in processing such as extrusion or injection
molding due to aging caused by shear and extensional flow and resulting in relaxation processes
which may lead to shrinkage or warpage of the polymer material. Other stabilizers also inhibit
photooxidation triggered by light or prevent chemical aging like hydrolysis, post-condensation
or post-polymerization. These stabilizers interrupt the circle of degradation, either by absorbing
UV light or reacting with initially formed degradation products and, thus, preventing their
propagation. Some stabilizers combine even more than one desired effect, inhibiting both the
thermal and the oxidative degradation. That has led to a variety of different stabilizers ranging
from processing stabilizers, phenolic antioxidants and hindered amine (light) stabilizers. In
order to further extend the lifetime of the polymers, the synthesis and the modification of
existing stabilizers has been pushed forward in the last years. Exemplarily, stabilizers have been
developed with increased molecular weights (oligomers) reducing the tendency to migrate in a
synthetic material, or stabilizers which are functionalized several times and in this way stronger
inhibit degradation.
This constant change in the portfolio of stabilizers requires the continuous development of
appropriate analytical methods for their characterization. The growing need for quantitative
characterization as well as the possibility to separate a variety of stabilizers in a one-shot
approach have made liquid chromatography (LC) the method of choice. Till now reversed
phases and normal phases have routinely been used as stationary phase for the separation and
identification of stabilizers in LC measurements [1]. For some stabilizers, and especially the
ones exhibiting higher molecular weights, no chromatographic methods exist, which allow a
satisfying separation and quantitative determination applying these stationary phases.
Therefore, another stationary phase was tested and can serve as an appropriate material, namely
porous graphitic carbon allows the application of elevated temperatures because of the robust
carbon material which is even stable at temperature as high as 160 °C [2]. The specific
interaction between porous graphitic carbon and stabilizers is a key for their separation and
identification.
We will show the separation of a number of selected stabilizers with LC using the porous
graphitic carbon as stationary phase for the first time. Separation of different phenolic
antioxidants, UV stabilizers as well as process stabilizers from each other will be presented.
Moreover, separation of high molecular weight hindered amine stabilizers at elevated
temperatures, which could not be achieved before using others stationary phases, will be
described.
References
[1] M. S. Dopico-García, R. Noguerol-Cal, M. M. Castro-López, M. C. Cela-Pérez, E. Piñón-Giz, J. M. López-
Vilariño, M. V. González-Rodríguez, Cent. Eur. J. Chem. 10, 3 (2012)
[2] Thermo Scientific, Hypercarb Columns, Applications Notebook, Issue 1, June 2009
ISPAC 2018 – Poster Session
74
P.11 - Tackling Industrial Needs Using Multi-Detector Size Exclusion and
Hydrodynamic Chromatography
A. K. Brewer1
Arkema Inc, King of Prussia, PA, [email protected]
Since their inception the principle uses of size-exclusion chromatography (SEC) and
hydrodynamic chromatography (HDC) have been to determine the molar mass averages and
distributions of natural and synthetic polymers and the characterization of mono- and
polydisperse particles, respectively. In general these properties have been characterized
through the application of calibration curves via a single-detector instrumental set-up e.g. SEC-
refractive index (RI) or HDC/SEC-UV. Over the years, as the complexity of polymers and
particles has increased, the ability to obtain accurate and precise distributions of both their
physical and chemical properties has led to the implementation of multi-detector size-based
separation techniques.
Here, we will discuss two different size-based separation techniques (SEC and HDC) coupled
to a multi-detector system consisting of, multi-angle light scattering (MALS), quasi-elastic
light scattering (QELS), differential viscometry (VISC) and differential refractory (RI). The
multi-detector SEC set-up will be used to determine the solution based macromolecular
properties such as; absolute molar mass, polymeric size (radius of gyration, hydrodynamic
radius, and viscometeric radius), polymer branching and their distributions of high molar mass
polymers. The characteristics obtained from these experiments as well as supporting
experiments, e.g. batch mode MALS and rheology, allow for the study of the effects of changes
in molar mass, chemical composition, and polymer branching on end-use properties and
polymer performance.
The multi-detector HDC set-up will be applied to the characterization of latex particles, as
several factors influence their end-use applications, including the size and shape of the latex
particles and their aggregates. Characterizing the size and shape of these particles by methods
such as SEC, microscopy or other particle size methodologies is challenging. Issues with SEC
analyses occur due to the large size of the particles as well as their sometimes fragile
morphology, while microscopy issues are chiefly due to the inability to analyze the particles in
their natural aqueous state. Multi-Detector HDC will be used for the determination of size,
shape and morphology across the elution profile of latex particles. This approach will also be
used to characterize flocculated latex particles arising from samples varying in pH and age.
The multi-detector HDC approach results are comparable to those obtained by atomic force
microscopy and rheology.
ISPAC 2018 – Poster Session
75
P.12 - Asymmetric flow field flow fractionation – gaining insight into long
chain branching of PP
J.H. Arndt1, R. Brüll1, G.P. Horchler1, T. Macko1, A. de Azeredo2, M.E. Cangussu2, A.
Lobo2, A. Simanke2
1Fraunhofer Institute for Structural Durability and System Reliability, Plastics Division, Schlossgartenstrasse
6, 64289 Darmstadt, Germany, 2Braskem SA, Via Oeste, Lote 5, Passo Raso, Triunfo, 95853, RS, Brasil
Long chain branching (LCB) is an important molecular metric which determines the
viscoelastic properties of the polymer melt [1]. In the case of polypropylene LCB is
introduced to improve the limitations of the material resulting from the molecular weight
distribution. The incorporation can be achieved by using suitable catalysts during
polymerization or by post reactor modification via physical or chemical processes [1, 2].
With the aim to understand and optimize the introduction of LCB a detailed knowledge about
its distribution along the molar mass axis is mandatory. Asymmetric flow field flow analysis,
AF4, is a fractionation approach which overcomes the shortcomings of size exclusion
chromatography with regard to peculiar co-elution of branched and low molecular weight
fractions [3-6].
Figure 1: (Left) Elution profile and molar masses as a function of elution time for a PP sample containing
LCB and (right) radius of gyration as a function of molar mass obtained from AF4.
References
[1] J. Tian, W. Yu, C. Zhou, Polymer 47, 7962 (2006).
[2] E. Borsig, M. van Duin, A.D. Gotsis, F. Picchioni, Eur. Polym. J. 44, 200 (2008).
[3] S. Podzimek, T. Vlcek, C. Johann, J. Appl. Polym. Sci. 81, 1588 (2001).
[4] T. Otte, H. Pasch, R. Brüll, T. Macko, Macromol. Chem. Phys. 212, 401 (2011).
[5] H. Pasch, A.C. Makan, H. Chirowodza, N. Ngaza, W. Hiller, Anal. Bioanal. Chem. 406, 1585 (2014).
[6] H. Pasch, M. I. Malik, Advanced Separation Techniques for Polyolefins, Springer International Publishing,
Cham, 2009.
ISPAC 2018 – Poster Session
76
P.13 - Asymmetric flow field flow fractionation – a novel approach for
routine analysis of polyolefins
J.H. Arndt1, R. Brüll1, G.P. Horchler1, T. Macko1, D. Mekap2, E.P.C. Mes2, D.T. Gillespie3,
D. Meunier3, W. de Groot3
1Fraunhofer Institute for Structural Durability and System Reliability, Plastics Division, 2The Dow Chemical
Company, Herbert H. Dowweg 5, 4542 NM Hoek, Netherlands, 3Performance Plastics Characterization and
Testing Group, The Dow Chemical Company, 2301 Brazosport Blvd., Freeport, TX 77541, US
The distributions with regard to molar mass (MMD) and long chain branching (LCBD) are
important molecular metrics of polyolefins. Size exclusion chromatography is currently well
established in routine analysis for their determination. Yet, the separation principle based on
diffusion in a porous stationary phase entails limitations, such as peculiar co-elution, shear
degradation and the exclusion limit [1,2]. Asymmetric flow field flow fractionation (AF4) poses
an attractive alternative technique, overcoming these deficits [3]. Yet, operating AF4 at
temperatures as high as 160 °C [4,5] has long been a challenge due to the limited durability of
the membrane.
Efforts in this regard have led to significant progress, thus for the first time enabling to probe
the effects of various flow profiles on the separation efficiency.
Fig. 1 Results of AF4 analyses of a narrowly distributed polyethylene sample, using a two-step linear cross flow
gradient (a) or a one step exponential gradient (b) respectively.
References
[1] A.W. deGroot, W.J. Hamre, J. Chromatogr. 1993, 648, 33.
[2] S. Podzimek, Macromol. Symp. 2013, 330, 81.
[3] J.C. Giddings, Science 1993, 260, 1456.
[4] E.P.C. Mes, H. de Jonge, T. Klein, RR. Welz, D.T. Gillespie, J. Chromatogr. A 2007, 1154, 319.
[5] T. Otte, H. Pasch, T. Macko, R. Brüll, F..J. Stadler, J. Kaschta, F. Becker, M. Buback, J. Chromatogr. A
2011, 1218, 4257.
a) b)
ISPAC 2018 – Poster Session
77
P.14 - The Characterization of Polyamide Aging by Means of Pyrolysis-
GC-MS
A. Ibrahimi Berisha, C. Schwarzinger Institute for Chemical Technology of Organic Materials, Johannes Kepler University, Austria;
Polyamides play an important role in our daily lives and are used in a very versatile way,
especially when tough, highly stable materials are desired.
The aim of this work is to artificially age polyamides under different conditions such as high
oxygen pressure, increased temperature and various liquids for 1 to 10 days [1]. The
polymers were hereafter analyzed with Pyrolysis GC-MS. It could be shown that aging in
general leads to the formation of new pyrolysis products compared to virgin material and
that depending on the liquids used other breakdown products can be identified suggesting
different aging mechanisms.
Figure 1 shows the aging of polyamide 6.6 as seen by pyrolysis-GC-MS when the sample is
aged in water. Main pyrolysis product in all cases is cyclopentanone (4) and after aging 2-
pyrrolidinone (7), 2-piperidone (9) can be found. The amount of caprolactame (11), the
monomer for polyamide 6, is also increased. The results in salt water are very similar,
whereas the use of sodium hypochlorite solution seems to favor a different degradation
mechanism.
Figure 1: Py-GC-MS analysis of PA-6.6 before and after aging for 1,3, and 10 days.
References
[1] - C. Schwarzinger, I. Hintersteiner, B. Schwarzinger, W. Buchberger, B. Moser: “Analytical pyrolysis in
the determination of the aging of polyethylene”; J. Anal. Appl. Pyrol. 113 (2015) 315-322.
ISPAC 2018 – Poster Session
78
P.15 - Asymmetric flow field flow fractionation – new perspectives for
routine analysis of polyolefins
J.H. Arndt1, R. Brüll1, G.P. Horchler1, T. Macko1, Y. Yu2
1Fraunhofer Institute for Structural Durability and System Reliability, Plastics Division, Schlossgartenstrasse 6,
64289 Darmstadt, Germany, 2Chevron Phillips Chemical Company LP, Bartlesville Research & Technology
Center Bartlesville, OK 74003, USA
Size exclusion chromatography coupled with multi-angle light scattering (SEC-MALS) is
widely used to analyze the molar mass distribution and long-chain branching (LCB) of
polyolefins. [1,2] The fractionation is based on the exclusion of macromolecules from a porous
stationary phase according to their hydrodynamic volume. Due to the separation principle,
fundamental limitations are inherent to SEC and cannot be overcome. These include peculiar
co-elution, shear degradation and the size exclusion limit [3,4]. On the other side, asymmetric
flow field flow fractionation (AF4) enables to overcome these drawbacks due to the absence of
any stationary phase [5-7]. Thus, ultra-high molar mass fractions can be studied as well as the
content of long-chain branching along the molar mass distribution.
a
)
b
)
Fig. 1 Elution profile and molar masses as a function of elution time (a) as well as radius of gyration as a
function of molar mass (b, indicative of LCB) obtained from AF4 analysis of a long-chain branched
polyethylene sample containing ultrahigh molar mass material.
References
[1] P.J. Wyatt, Anal. Chim Acta, 1993, 1, 272.
[2] Y. Yu, P.J. DesLauriers, D.C. Rehlfing, Polymer, 2005, 46, 5165.
[3] A.W. deGroot, WJ. Hamre, J. Chromatogr. 1993, 648, 33.
[4] S. Podzimek, Macromol. Symp. 2013, 330, 81.
[5] J.C. Giddings, Science 1993, 260, 1456.
[6] E.P.C. Mes, H. de Jonge, T. Klein, R.R. Welz, D.T. Gillespie, J. Chromatogr. A 2007, 1154, 319.
[7] T. Otte, H. Pasch, T. Macko, R. Brüll, F..J. Stadler, J. Kaschta, F. Becker, M. Buback, J. Chromatogr. A
2011, 1218, 4257.
ISPAC 2018 – Poster Session
79
P.16 - Stepwise Elution of Methylcellulose Esters with increasing DSMe by
NP-HPLC
Patrick Sudwischer, Anika Wubben, Inga Unterieser, Julia Cuers, Petra Mischnick
Technische Universität Braunschweig, Institute of Food Chemistry, Germany
The physicochemical properties of cellulose ethers depend on the molecular weight
distribution, the degree of substitution (DS), and also on the distribution of the substituents
in the glucosyl unit and over the polymer chains. The chemical modification of cellulose
does not necessarily proceed uniformly over the entire material. This results in
heterogeneities with respect to the distribution of substituents. For a detailed analysis of the
1st order heterogeneity, the material must be fractionated according to DS. Preparative
chromatography of cellulose ethers, for instance methyl cellulose (MC), is hampered by the
viscosity of the solutions [1]. Furthermore, MC can be regarded as a very complex
copolymer which has a continuum of critical eluent compositions in the chromatographic
fractionation [2].
MCs of various DSMe were separated on a normal phase (silica gel) HPLC with a
gradient of 2-propanol (2-PrOH) in dichloromethane (DCM). Prior to chromatography, all
free OH were converted to 4-methoxybenzoates. This transformation results in a reduction
of viscosity and increase in the chemical difference of the polymer chains. Furthermore, a
chromophore is introduced in the polymer which enables detection by UV light of the
4-methoxybenzoate derivatives.
Figure 2: left : Correlation of the DSMe and % 2-PrOH in DCM, required to elute MeOBzMC from
silica gel, right : Exponential approximation of the 2-PrOH steps in DCM in the HPLC gradient
system with determination of the DSMe of the peaks from the CPA curve.
A set of nine cellulose derivatives in the range of DS(Me/MeOBz) = 0/3.0 to 3.0/0 showed
increasing retention with an increasing DSMe in NP-chromatography. Elution required an
increasing amount of 2-PrOH in DCM to elute it from silica gel (Fig. 1 left). The Separation
with gradient chromatography depends on an absorption/desorption mechanism (Fig. 1
right).
References
[1] R. Adden et al., Macromol. Chem. Phys. 207 (2006) 954 – 965
[2] P. Kilz et al., Anal. Bioanal. Chem. 407 (2015) 193 – 215
ISPAC 2018 – Poster Session
80
P.17 - Expediting 2D-LC Separations of Synthetic Polymers Using
Advanced Polymer Chromatography (APC) M. Jančo1, L. Bai2
1 Analytical Sciences, Core R&D, the Dow Chemical Company, Collegeville, PA, USA,
[email protected] 2 Home and Personal Care R&D, Collegeville, PA, USA
Analysis of synthetic polymers often utilizes size exclusion chromatography
(SEC) and interactive high performance liquid chromatography (HPLC) to reveal
molecular weight and chemical compositional distributions, respectively. The traditional
SEC and HPLC methods are time-consuming, resulting in long separations when
coupled in 2D-LC mode. In spite of the improved resolution of 2D-LC separations, the
longer analysis time has hindered wide-spread adoption of 2D technique in fast-pace
industry settings.
In this work, sub-3 micron particle column technology for polymer SEC (Waters
ACQUITYTM Advanced Polymer Chromatography, APC) and sub-2 micron particle
column for UHPLC are used for 2D-LC separations in the LC X SEC format. The
improved efficiency provided by the APC columns allows for significant reduction of
the overall analysis time. Several examples are given to illustrate the application in the
analysis of synthetic polymers.
On the other hand, aiming to improve the efficiency and increase throughput in
the first dimension (the interactive HPLC dimension), this work also evaluates the use
of sub-2 micron particle columns using ultrahigh-pressure liquid chromatography
(UHPLC). Using narrow polystyrene standards with molecular weights ranging from 5k-
1M, we compared the peak widths generated from the use of columns packed with 10
µm, 5 µm, 3.5 µm, and 1.7 µm particles. The peak widths are shown to get narrower as
particle sizes become smaller when other parameters remain constant. The increased
peak capacity helps to gain resolution in the LC dimension. However, there are also
potential issues in using sub-2 micron particle columns in comprehensive 2D-LC
separations: when the 1st dimension peaks are so narrow that they do not allow sufficient
number of slices (more than 3 slices) to be sampled across each peak. Therefore the
shape/width of the peak reconstructed by 2D-LC software using a limited number of
slices remains questionable.
In conclusion, ultra-high pressure 2D-LC (UHPLCxAPC) utilizing small particle
size columns has shown the potential to significantly shorten the runtime of 2D-LC,
making this technique a practical tool for industrial use. The increased peak capacity can
provide better resolution for such separations. However, cautions need to be taken in
situations when the number of slices across the eluting peaks are limited.
ISPAC 2018 – Poster Session
81
P.18 - Crystallization and Alkaline Hydrolysis Studies of Poly(3-
hydroxybutyrate)
N. Vasanthan , A. Tappadiya
Department of Chemistry and Biochemistry, Long Island University, One University Plaza, Brooklyn, NY
11201, [email protected]
Poly(3-hydroxybutyrate) (PHB) is a microbially synthesized polymer, which is often
purified by alkaline treatment. The effect of microstructure on alkaline hydrolysis has been
studied by varying concentration of base and the temperature. The morphologies of PHB
films before and after degradation were evaluated using DSC and FTIR spectroscopy. The
hydrolytic degradation study by weight loss measurement revealed that the crystallinity of
PHB greatly decreased the hydrolytic ability of PHB. The crystallization of PHB and the
effect of base on hydrolysis was investigated by time dependent FTIR spectroscopy. The
normalized absorbance of 3010 cm-1 and 1183 cm-1 were used to characterize the crystalline
and the amorphous phases of PHB, shown in Figure 1. FTIR spectroscopy reveal that the
extent of hydrolysis decreased with increasing crystallinity. The crotonic acid was detected
as a major product after hydrolysis, confirmed by UV/Visible and proton NMR
spectroscopy. The normalized absorbance of the crystalline band at 3010 cm-1 band remained
constant, suggesting that there is no significant change in crystallinity with degradation. The
normalized amorphous band at 1183 cm-1 showed a decrease in absorbance ratio, suggesting
degradation of the amorphous phase.
.
Figure 1: FTIR spectra of PHB films cold crystallized at different temperatures in the region (a)1500-900 cm-
1 and (b) 3050-2850 cm-1.
References
6. Doi Y, Steinbuchel A, Eds. Biopolymer, Polyesters I-Biological Systems and Biotechnological Production;
John Wiley and Sons: Weinheim, Germany, 2001;3
7. Gross RA, Kalra B. Biodegradable polymers for the Environment Science 2002;297:803-7.
8. Matsusaki H, Abe H, Doi Y. Biomacromolecules 2000;1:17.
9. Steinbuchel A, Valentine H E. FEMS Microbiol Lett 1995;128:219.
10. Tapadiya, A, Vasanthan, N. International Journal of Biological Macromolecules, 2017, 102, 1130
ISPAC 2018 – Poster Session
82
P.19 - Thermo-Responsive Monosaccharide-Polyolefin Amphiphilic
Conjugates Displaying Order-Order Transitions
K. K. Lachmayr1, T. S. Thomas1, K. Yager2, L. R. Sita1*
1 Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland
20742, United States 2 Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United
States
The self-assembly of amphiphiles gives rise to important scientific and industrial
materials. Thus, the ability to design new classes of molecular and macromolecular
amphiphilic building blocks tunable, well-defined nanostructures is highly desirable. We
have previously reported the use of end-group functionalized poly(α-olefinates) (xPAOs)
as a highly versatile class of non-polar building blocks for amphiphilic materials made
through living coordinate chain-transfer polymerization (LCCTP) Herein, we report the
use of xPAOs in sugar-polyolefin conjugates, specifically consisting of β-D-Galactose as
the sugar “head” group chemically linked to an atactic polypropylene “tail” (Gal-aPP).
This system displays rich phase behavior within ultrathin films with multiple order-to-
order transitions upon heating. Additionally, upon cooling from above the order-disorder
transition temperature, a novel body centered cubic phase can be accessed. These results
demonstrate the ability of sugar-polyolefin conjugates to be used as a thermo-responsive
‘smart’ materials.
References
[1] –T. S. Thomas, W. Hwang, and L. R. Sita, Angew. Chem. Int. Ed. 55, 4683 (2016).
ISPAC 2018 – Poster Session
83
P.20 - The Use of 2-D Chromatographic Techniques to Interpret
Macromolecular Structures
J. McConville1, D. Lohmann1, W. Radke2, P. Kilz2
1 PSS USA Inc, Amherst, MA, USA, 2 PSS GmbH, Mainz, Germany
The task of characterizing polymeric materials has become more challenging as advances in
polymer synthesis gave rise to a variety of novel complex materials with predetermined
chemical composition, functionality and architecture. The molar mass, the chemical
composition, the architecture and other parameters are fine-tuned for optimal structure-
property function relationships. No single analytical technique alone provides adequate
information regarding these different distributions.
The coexistence of these property distributions require multidimensional (combined)
chromatographic methods. 2-D Chromatography combines the separation power of two
different chromatographic techniques, e.g. HPLC and GPC/SEC.
Accurate and precise results can be directly derived for each sample component in a single
2-D run, e.g. molar mass, chemical composition, end group, functionality, degree of
branching, architecture, aggregation, etc., depending on the specificity of the selected
separation techniques.
Different application examples obtained with various hyphenations will be presented.
Optimization of the on-line setup with respect to ease-of-use and fully automated transfer
from the first to the second dimension will be discussed. Options for data presentation using
different plot and evaluation types and access to the final results will also be shown.
ISPAC 2018 – Poster Session
84
P.21 - Synthesis, Characterization and Application of reversible Ultra-
hydrophobic Polymer Surfaces
D. Lohmann3, T. Hofe2, K. Oleschko2, M. Stamm1, P. Uhlmann1,
1 Leibniz Institute of Polymer Research Dresden, Department Nanostructured Materials, Dresden, Germany,
2 PSS GmbH, Mainz, Germany, 3 PSS USA Inc, Amherst, MA, USA
The ultra-hydrophobic properties of a lotus leaf are based on a hierarchal surface structure.
This structure can be perfectly modelled by the use of a polymer particle in the µm range and a tri-
block polymer coating in the nm range. Multifunctional polymer surfaces based on this structure
exhibit ultra-hydrophobic and super-hydrophilic behaviour. To realize multi-functionality it is
necessary to combine the different functionalities in one polymer molecule. This is achieved by the
production of core-shell-nanoparticle layers on a variety of surfaces which lead to easy-to-clean or
self-cleaning properties.
The synthesis of the tri-block copolymers using controlled living polymerization techniques
and the preparation of the core-shell-nanoparticles will be presented.
In addition, modern LC techniques to determine the molar mass and the composition of the polymers
will be introduced, including the advantages and possibilities of 2-dimensional separation techniques
including FT-IR identification.
The synthesized tri-block polymers consist of a block responsible for the anchoring to the
substrate, a “hydrophilic” block and a “hydrophobic” block. This offers the possibility to combine
the anchoring to a substrate with reversible switching of the wetting behavior in one molecule. The
wetting behavior of the prepared tri-block polymer brushes can be switched by external stimuli.
Super-hydrophilic and ultra-hydrophobic surface behavior was achieved and will be discussed as a
function of grafting density, molar mass and composition. .
Applications for the possible industrial use of these new surface properties will be shown.
ISPAC 2018 – Poster Session
85
P.22 - Thermo-Responsive Monosaccharide-Polyolefin Amphiphilic
Conjugates Displaying Order-Order Transitions
K. K. Lachmayr1, T. S. Thomas1, K. Yager2, L. R. Sita1*
1 Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland
20742, United States 2 Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United
States
The self-assembly of amphiphiles gives rise to important scientific and industrial materials.
Thus, the ability to design new classes of molecular and macromolecular amphiphilic
building blocks tunable, well-defined nanostructures is highly desirable. We have
previously reported the use of end-group functionalized poly(α-olefinates) (xPAOs) as a
highly versatile class of non-polar building blocks for amphiphilic materials made through
living coordinate chain-transfer polymerization (LCCTP) Herein, we report the use of
xPAOs in sugar-polyolefin conjugates, specifically consisting of β-D-Galactose as the
sugar “head” group chemically linked to an atactic polypropylene “tail” (Gal-aPP). This
system displays rich phase behavior within ultrathin films with multiple order-to-order
transitions upon heating. Additionally, upon cooling from above the order-disorder
transition temperature, a novel body centered cubic phase can be accessed. These results
demonstrate the ability of sugar-polyolefin conjugates to be used as a thermo-responsive
‘smart’ materials.
References
[1] –T. S. Thomas, W. Hwang, and L. R. Sita, Angew. Chem. Int. Ed. 55, 4683 (2016).
ISPAC 2018 – Poster Session
86
P.23 - Controlled Deuteration in Polyethylene via Polyhomologation
W. S. Farrell, K. L. Beers
National Institute of Standards and Technology, [email protected]
The use of deuterium labelling in conjunction with small angle neutron scattering (SANS)
provides a powerful method to probe the confirmation of semicrystalline polymers,
especially in regard to tie-chain estimation. Although polyethylene is the most widely
consumed polyolefin, and such investigations are of great industrial interest, preparation of
polyethylene with deuterium labeling has been challenging historically, either not allowing
for high degrees of deuteration, or not permitting labeling of selective portions of the
polymer chain, such as chain-ends. In this work, we demonstrate a new route to deuterated
polyethylene using polyhomologation to prepare well-defined polyethylene with
controllable amount of deuteration which is uniform across the molar mass distribution.
This initial investigation has been extended to include selective deuterium labeling of
chain-ends as well, which should enable identification of chain-end location in
semicrystalline polyethylene by SANS. Furthermore, the deuterated polyethylene
produced is hydroxy-terminated, making these functional polymers candidates for the
preparation of more complex architectures, such as deuterated polyethylene bottlebrush
polymers.
ISPAC 2018 – Poster Session
87
P.24 - The best of both worlds: combining multi-detector GPC
and UPLC to achieve complex polymer characterization
at ULPLC speeds and resolutions
V. Shahi1, M.R. Pothecary1, C. Schindler1, J.D. Stenson2, L. Meeker2, B. MacCreath2
1Malvern Panalytical, Houston, Tx, USA, 2Waters Corporation, Milford, MA, USA
Gel-permeation chromatography (GPC) is the most widely used tool for the measurement of
molecular weight and molecular weight distribution of natural and synthetic polymers.
Advanced detectors such as light scattering are increasingly used to overcome the limitations
of conventional GPC measurements and offer absolute molecular weight. A viscometer
measures intrinsic viscosity, a key structure factor that can be used to calculate branching
levels and can be combined with molecular weight data to calculate hydrodynamic radius.
In combination these data allow detailed structural information of a polymer to be generated
in a single GPC measurement which can be compared with other samples in Mark-Houwink
plots. This can be used to study substitution or branching levels.
Typical analytical SEC measurements can take approximately 25 to 45 minutes and consume
25 to 45 ml of solvent. This is time-consuming and can be expensive in terms of solvent.
Ultra-high pressure liquid chromatography (UPLC) systems use novel SEC column gel
technologies with robust, small particles (<3 µm) to achieve similar or better sample
resolution using smaller columns. This increases productivity, while significantly reducing
run-time and cost. An additional benefit of the reduced solvent use is to effectively make
UPLC a ‘greener’ technology than traditional analytical SEC.
Until recently issues with band-broadening, or dispersion, limited the ability to connect
multi-detector and UPLC system as the loss in resolution and data quality was too great. In
this presentation, we will show how Malvern’s OMNISEC REVEAL and the Waters
Acquity APC systems can now be combined to bring complete multi-detector measurements
at UPLC resolutions and efficiencies. This talk will include a discussion of the pitfalls of
combining these two techniques and a range of measurements to show how a large number
of applications can now be addressed in this manner.
ISPAC 2018 – Poster Session
88
P.26 - One-pot synthesis and characterization of “designer” delivery
systems for controlled release of therapeutic agents.
Vidya Chamundeswari Narasimhan1, Joachim Say Chye Loo1, 2.
1 School of Materials Science and Engineering, Nanyang Technological University, Singapore.
2 Singapore Centre for Environmental Life Sciences Engineering, Nanyang Technological University,
Singapore.
Email: [email protected]
Micro particles and nanofibers are attractive candidates for drug delivery applications owing
to their tunability for targeted and sustained drug release. Our research focuses on
encapsulation techniques to enable for controlled and sustained release of therapeutic agents,
and materials characterization. These carriers are fabricated using a combination of natural,
synthetic and food grade polymers. During the development of our technologies, the long-
term economic viability, employing green manufacturing and scalable techniques, were
taken into consideration while minimizing negative effects to both human health and the
environment. We have developed multi-layered particles, floatable microcapsules, and
hydrophilic-hydrophobic (core-shell) particles and electrospun 3-dimensional and bi-layered
scaffolds for drug delivery applications. All the carrier systems were subjected to
morphological, rheological and chemical characterizations to ensure the successful
encapsulation of bioactive agents. With these inventions, we demonstrated how these
distinctive “designer” systems can modulate the release profiles of anticancer drugs, and
how co-delivery can potentially provide better antitumor response and enhance rate of repair
of damaged tissues. Currently these systems can facilitate sustained release of biomolecules
for applications in bone infections; gastrointestinal release, magnetic diagnostics,
musculoskeletal regeneration and cancer therapy. These technologies hold an immense
potential in the field of regenerative medicine and biomaterials.
References:
1. V Narasimhan, YS Lui, YJ Chuah, JS Tan, D Wang, SCJ Loo. Sustained Releasing Sponge-like 3D
Scaffolds for Bone Tissue Engineering Applications. 2017. Accepted Biomedical Materials
2. JS Baek, CC Choo, NS Tan, SCJ Loo. Sustained-releasing Hollow Microparticles with Dual-
anticancer Drugs Elicit Greater Shrinkage of Tumor Spheroids. 2017. 8: 80841-80852. Oncotarget
3. HM Tay, S Kharel, R Dalan, ZJ Chen, KK Tan, B Boehm, SCJ Loo, HW Hou. Rapid purification
of sub-micron particles for enhanced drug release and microvesicles isolation. 2017. 9, e434 NPG
Asia Material 4. JS Baek, EW Yeo, YH Lee, NS Tan, SCJ Loo. Controlled Releasing Nano-encapsulating
Microcapsules to Combat Inflammatory Diseases. 2017. 11:1707-1717 Drug Design, Development
and Therapy 5. S Kharel, WL Lee, XY Lee, SCJ Loo. Osmogen-Mediated One-Step Technique of Fabricating
Hollow Microparticles for Encapsulation and Delivery of Bioactive Molecules. 2017. 17, 1600328
Macromolecular Bioscience 6. N Yang, K Sampathkumar, SCJ Loo. Recent Advances in Complementary and Replacement
Therapy with Nutraceuticals in Combating Gastrointestinal Illnesses. 2017. 36: 968-979. Clinical
Nutrition
Author Index
89
A Ali, S. .................................................... 24
Apel, N...................................... 57, 71, 73
Arndt, J.H. .......................... 48, 75, 76, 78
Audus, D. .............................................. 31
Azeredo, A. de ...................................... 75
B Bai, L. ................................................... 80
Beers, K. L. ..................................... 46, 86
Beers, K.L. ............................................ 49
Berisha, A. I. ......................................... 77
Bernardes, A. A. ................................... 54
Besghini, D. .......................................... 64
Bhargava, R. ......................................... 55
Birdsall, R. ............................................ 29
Biswas, Atanu ....................................... 38
Blaschke, S. .......................................... 68
Botha, C. ............................................... 39
Boudara, V. A. H. ................................. 19
Brambilla, R.......................................... 54
Brewer, A. K. ........................................ 74
Brüll, R. ...... 48, 57, 70, 71, 73, 75, 76, 78
Brun, Y. ................................................ 26
C Cangussu, M.E. ..................................... 75
Carriere, J. T. A. ................................... 42
Chan, E.P. ............................................. 49
Chang, T. .............................................. 41
Chard, K................................................ 31
Cheng, H. N. ................................... 38, 66
Chikama, K. .......................................... 72
Clarke, P. .............................................. 60
Cong, R. ................................................ 70
Cotts, S.................................................. 22
Cuers, J. ................................................ 79
D Das, C. .................................................. 19
de Groot, W. ......................................... 76
de Pablo, J. ............................................ 31
deGroot, W. .......................................... 70
DeLongchamp, D. M. ........................... 63
den Doelder, J. ...................................... 18
Deshpande, A. P. .................................. 56
DesLauriers, P. J. .................................. 55
Desport, J. S. ......................................... 58
Dowd, M. K. ......................................... 66
F Farrell, W. S.................................... 46, 86
Föge, V. ................................................ 68
Foster, I. ................................................ 31
Frache, G. ............................................. 58
François, I. ............................................ 29
G Ganesh, S. ............................................. 23
Garg, P. ................................................. 48
Gartner III, T. E. ............................. 34, 69
Ghosh, A. .............................................. 55
Gillespie, D.T. ...................................... 76
Gough, J. .............................................. 29
Gurappa, B. M. ..................................... 56
H Hadjichristidis, N. ................................ 52
Han, C. C. ............................................. 67
Han, C.C. .............................................. 45
He, Z. .................................................... 66
Heidegger, A. ....................................... 68
Heinzmann, G. ...................................... 60
Helgeson, M. E. .................................... 20
Hillmyer, M. A. .................................... 46
Hiroi, Y. ................................................ 72
Hofe, T. ................................................ 84
Höpfner, J. ............................................ 39
Horchler, G.P. ........................... 75, 76, 78
Hore, M. J. A. ....................................... 61
Hutchings, L. R. ................................... 50
J Jančo, M. ........................................ 28, 80
Jayaraman, A. ................................. 34, 69
Jones, M. .............................................. 29
Jones, R. L. ..................................... 34, 69
K Kassekert, L. A. .................................... 46
Kaur, G. ................................................ 23
Kawashima, M. .................................... 72
Kilz, P. .................................................. 83
Kot, D. .................................................. 73
Kotula, A. P. ......................................... 21
Kübel, J. ................................................ 39
Kumari, S. ............................................ 23
L Lachmayr, K. K. ............................. 82, 85
Lamborn, M. J. ..................................... 55
Lavric, S. .............................................. 27
Lee, Y. J. .............................................. 43
Lequieu, J. ............................................ 31
Liu, Y. .................................................. 47
Author Index
90
Lobo, A. ................................................ 75
Lohmann, D. ............................. 27, 83, 84
Loo, J. S. C. .......................................... 88
Luo, J. ................................................... 45
M Ma, J. .................................................... 47
MacCreath, B. ................................. 29, 87
Macko, T. ............... 48, 57, 73, 75, 76, 78
Malz, F. ................................................. 70
Martin, T. B. ................................... 34, 69
Matsubara, K. ....................................... 72
Mauri, M. ........................................ 37, 64
McConville, J. ...................................... 83
Meeker, L. ............................................ 87
Mekap, D. ....................................... 70, 76
Meredig, B. ........................................... 32
Mes, E.P.C. ........................................... 76
Meunier, D. ........................................... 76
Meunier, D. M. ..................................... 40
Miranda, S. L. ....................................... 54
Mischnick, P. ........................................ 79
Monwar, M. M. .................................... 55
Morlock, S. ........................................... 39
Morrison, D. ......................................... 29
Mukherjee, P. ....................................... 55
N Narasimhan, V. C. ................................ 88
Netto, A. M. .......................................... 54
Nickel, F. .............................................. 68
Noda, I. ................................................. 42
Nowak, S. R. ......................................... 44
O O’Leary, M. .......................................... 29
Oleschko, K. ......................................... 84
Orski, S. V. ........................................... 46
P Patil, S. ................................................. 23
Plankeele, J.-M. .................................... 29
Pothecary, M. R. ................................... 87
Prabhu, V.M ......................................... 24
Preis, J. ................................................. 27
Q Qin, J. ................................................... 31
R Rabolt, J. F. ........................................... 42
Radke, W. ....................................... 27, 83
Rajeev, A. ............................................. 56
Ramakrishnan, V. ................................. 57
Ramprasad, R. ...................................... 30
Rasmussen, C. J. .................................. 26
Read, D. J. ............................................ 19
Reed, R. ................................................ 60
Rettner, E.M. ........................................ 49
Rommens, S. .................................. 25, 71
Rowlette, J. ........................................... 43
Roy, A. ................................................. 42
S Sabagh, B. ............................................ 60
Saha, P. ................................................. 23
Sarapas, J.M. ........................................ 49
Schindler, C. ......................................... 87
Schwarzinger, C. ............................ 68, 77
Shahi, V. ............................................... 87
Simanke, A. .......................................... 75
Simonutti, R. .................................. 37, 64
Sita, L. R. ........................... 44, 51, 82, 85
Smits, G. F. .......................................... 33
Snyder, C. R. .................................. 34, 69
Spegazzini, N. ...................................... 55
Stamm, M. ............................................ 84
Stenson, J. D. ........................................ 87
Sudwischer, P. ...................................... 79
T Tacx, J. ................................................. 48
Tappadiya, A. ................................. 65, 81
Tawfilas, M. ......................................... 37
Tchoua, R. ............................................ 31
Thomas, T. S. ................................. 82, 85
U Uhlmann, P. .......................................... 84
Uliyanchenko, E. ...................... 25, 57, 71
Unterieser, I. ......................................... 79
V Vaccarello, D.N. ................................... 49
Vancso, G. J. ........................................ 47
Vargas Lara, L. F. ................................ 35
Vasanthan, N. ................................. 65, 81
Verma, S. .............................................. 23
W W. Radke .............................................. 83
Wang, M. .............................................. 67
Ward, L. ............................................... 31
Wei, Y. ................................................. 61
Wilhelm, M. ......................................... 39
Wirtz, M. .............................................. 58
Wubben, A. .......................................... 79
X Xu, Y. ................................................... 61
Author Index
91
Y Yager, K.................................... 44, 82, 85
Yager, K. G. .......................................... 62
Yang, D. ................................................ 59
Yu, Y. ................................................... 78
Yuan, G. ......................................... 45, 67
Z Zhao, C. ................................................ 45
Zhou, Z. ................................................ 70