Upload
others
View
7
Download
0
Embed Size (px)
Citation preview
Sample Pages
Processing of Polymer Nanocomposites
Samuel Kenig
ISBN (Book): 978-1-56990-635-4 ISBN (E-Book): 978-1-56990-636-1
For further information and order see
www.hanserpublications.com (in the Americas)
www.hanser-fachbuch.de (outside the Americas)
© Carl Hanser Verlag, München
With the emergence of commercial nanomaterials like nanoclays, carbon nano-tubes, nanosilica, graphite nanoplatelets, cellulose nanocrystals, halloysite nano-tubes, layered double hydroxides, tungsten disulfide fullerenes and nanotubes, ceramic nanofillers, and the like, new potential routes have been opened to tailor polymers in the nanoscale range. Due to the large surface area of the nanosize particles, only small amounts are needed to cause significant changes in the me-chanical, physical, thermal, and electrical properties of polymer nanocomposites. When the surface area of the nanoparticles is modified, an additional dimension for the formulation of polymers arises, for a variety of applications.
The processing of nanocomposite polymers is the most important stage bridging the technology between the composition of the nanocomposites and their final properties and derived applications, due to the structuring during processing of the polymer at the nanoscale.
This book covers the fundamental aspects involved in the processing of thermo-plastics and thermoset nanocomposites, namely:
� Dispersion and distribution of nanoparticles using sonication, roll mixing, shear mixing, elongational mixing, solvent mixing, melt mixing, and in situ polymer-ization
� Functionalization of nanoparticles for compatibilization with various polymer systems
� Processing of polymer nanocomposites, including rheology as well as nanoparti-cles’ orientation development during extrusion and injection molding
� The effect of dispersion, functionalization, and processing technologies on orien-tation, morphology, and derived nanocomposite mechanical, thermal, electrical, and physical properties
Prof. Samuel KenigDecember 2018
Preface
Contents
List of Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IX
1 The Effect of Processing Conditions on the Dis per sion and Microstructure of Organoclay/Poly propylene Nanocomposites in Twin-Screw Extrusion . . . . . . . . . . . . . . . . . . 1Bruno Vergnes
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Experimental Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21.2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21.2.2 Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31.2.3 Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 Influence of the Processing Conditions (Internal Mixer) . . . . . . . . . . . . . 61.3.1 Influence of the Rotor Speed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61.3.2 Influence of the Mixing Time and the Temperature . . . . . . . . . . . 71.3.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.4 Application to Twin-Screw Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101.4.1 Influence of the Processing Conditions on the
Final Micro structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101.4.1.1 Influence of the Screw Speed . . . . . . . . . . . . . . . . . . . . . 101.4.1.2 Influence of the Feed Rate . . . . . . . . . . . . . . . . . . . . . . . . 111.4.1.3 Influence of the Barrel Temperature . . . . . . . . . . . . . . . 121.4.1.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.4.2 Changes in the Microstructure along the Screws . . . . . . . . . . . . . 151.4.3 Influence of the Screw Profile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181.4.4 How to Improve Dispersion and Exfoliation . . . . . . . . . . . . . . . . . 20
1.5 Toward Process Optimization through Modeling and Prediction of Microstructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
XII Contents
2 Ultrasound-assisted Processing of Nanocomposites . . . . . . . . . 29Avraam I. Isayev, Setareh Niknezhad, Jaesun Choi, and Jing Zhong
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.2 General Description of High-power Ultrasound . . . . . . . . . . . . . . . . . . . . 31
2.3 Overview of High-power Ultrasonic Irradiation of Media . . . . . . . . . . . . 332.3.1 Ultrasonic Cavitation in Liquid . . . . . . . . . . . . . . . . . . . . . . . . . . . 332.3.2 Overview of Ultrasonically-aided Processing of
Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342.3.3 Proposed Mechanism of Ultrasonic Irradiation of
Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.4 Development of Ultrasonically-aided Processing Technology . . . . . . . . . 41
2.5 Effect of Ultrasound on Polymer Nanocomposites . . . . . . . . . . . . . . . . . . 562.5.1 Nanocomposites Filled with Inorganic Filler Particles . . . . . . . . 562.5.2 Nanocomposites Filled with Carbonaceous Fillers . . . . . . . . . . . . 682.5.3 Mechanism of Ultrasonic Treatment in
Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
2.6 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3 Monitoring Dispersion and Re-agglomeration Phenomena During the Manufacture of Polymer Nanocomposites . . . . . . . . 97José A. Covas and Maria C. Paiva
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
3.2 Organoclays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 993.2.1 Dispersion of Layered Clays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1003.2.2 Monitoring the Development of Dispersion . . . . . . . . . . . . . . . . . 101
3.3 Carbon Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1053.3.1 Dispersion of Carbon Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . 1073.3.2 Monitoring the Development of Dispersion . . . . . . . . . . . . . . . . . 108
3.4 Graphene Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1123.4.1 Dispersion Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1133.4.2 Monitoring the Development of Dispersion . . . . . . . . . . . . . . . . . 115
3.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
XIIIContents
4 The Effect of Dispersion and Particle–Matrix Interactions on the Fatigue Behavior of Novel Epoxy/Halloysite Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121Martin H. Kothmann, Agustin Rios de Anda, Andreas Köppel, Rico Zeiler, Georg Tauer, Zhong Zhang, and Volker Altstädt
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4.2 Materials and Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1244.2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1244.2.2 HNTs’ Surface Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1254.2.3 Preparation of Epoxy/HNT Nanocomposites . . . . . . . . . . . . . . . . . 125
4.3 Characterization Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1264.3.1 Thermal and Static Mechanical Analyses . . . . . . . . . . . . . . . . . . . 1264.3.2 Fatigue Crack Propagation Investigation . . . . . . . . . . . . . . . . . . . . 128
4.3.2.1 Analytical Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1294.3.2.2 Experimental Procedure . . . . . . . . . . . . . . . . . . . . . . . . . 130
4.4 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1314.4.1 Multiscale Material Characterization . . . . . . . . . . . . . . . . . . . . . . 131
4.4.1.1 Particle Morphology and Particle Size Distribution . . . 1314.4.1.2 Characterization of the HNTs’ Modification . . . . . . . . . 1324.4.1.3 Dispersion of the HNTs . . . . . . . . . . . . . . . . . . . . . . . . . . 1354.4.1.4 Influence of Surface Modification on Interface
Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1354.4.1.5 Glass Transition Temperature . . . . . . . . . . . . . . . . . . . . . 136
4.4.2 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1374.4.2.1 Influence of Dispersion and Interface on the
Tensile Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1374.4.2.2 Influence of Dispersion and Interface on the
Fracture Toughness and Toughening Mechanisms . . . 1404.4.3 Fatigue Crack Propagation Behavior . . . . . . . . . . . . . . . . . . . . . . . 143
4.4.3.1 Influence of HNT Content . . . . . . . . . . . . . . . . . . . . . . . . 1444.4.3.2 Influence of HNT Surface Modification . . . . . . . . . . . . . 1464.4.3.3 Energy Dissipating Mechanisms . . . . . . . . . . . . . . . . . . 147
4.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
5 Effect of Melt Processing on Multi-Walled Carbon Nanotube Length . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157Brian Grady
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
5.2 Measurement of Nanotube Length . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
XIV Contents
5.3 Effect of Melt Processing on Nanotube Length . . . . . . . . . . . . . . . . . . . . . 1635.3.1 Mechanical Variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1635.3.2 Nanotube or Fluid Variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1655.3.3 Effect of Additives, Including Blending . . . . . . . . . . . . . . . . . . . . . 166
5.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
6 Microinjection Molding of Filler-Loaded Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171Shengtai Zhou, Andrew N. Hrymak, and Musa R. Kamal
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
6.2 Processing of Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
6.3 Microinjection Molding of Polymer Nanocomposites . . . . . . . . . . . . . . . . 1736.3.1 General Characteristics of the Microinjection Molding Process
and Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1736.3.2 Special Considerations in Microinjection Molding of Polymers
and Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1766.3.3 Typical Process–Structure Relationships of Microinjection
Moldings of Polymers and Polymer Nanocomposites . . . . . . . . . . 178
6.4 Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1806.4.1 Melting and Crystallization Behavior . . . . . . . . . . . . . . . . . . . . . . 1806.4.2 Thermal Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
6.5 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1846.5.1 Tensile Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1856.5.2 Nanoindentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1866.5.3 Dimensional Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
6.6 Electrical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1896.6.1 The Effect of Filler Type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1896.6.2 The Effect of the Polymer Matrix . . . . . . . . . . . . . . . . . . . . . . . . . . 1936.6.3 The Effect of Surface Modification of Electrically
Conductive Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1946.6.4 The Effect of Molding Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . 194
6.7 Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
7 Polymer Nanocomposites and Multilayer Nanocomposite Films by Coextrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201Rui Jian, Joey Mead, Carol Barry, and Claire Lepont
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2017.1.1 Electrical Conductivity of Polymer/Carbon Nanotube
Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
XVContents
7.1.2 Electromagnetic Interference of Polymer/Carbon Nanotube Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
7.1.3 Layer Multiplying Coextrusion Process . . . . . . . . . . . . . . . . . . . . . 206
7.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2077.2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2077.2.2 Coextrusion of Multilayer Samples . . . . . . . . . . . . . . . . . . . . . . . . 2087.2.3 Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
7.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2137.3.1 PS/CNT Compounds with Varied CNT Loadings . . . . . . . . . . . . . 213
7.3.1.1 Electrical Resistivity of Diluted PS/CNT Compounds . . 2137.3.1.2 Rheology of PS/CNT Compounds . . . . . . . . . . . . . . . . . . 2157.3.1.3 Multilayer Extruded Samples . . . . . . . . . . . . . . . . . . . . . 2177.3.1.4 Compounds with CNT Loading Above the Percolation
Region (5 wt%) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2187.3.1.5 Compounds with CNT Loading Near the Percolating
Region (3 wt%) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2207.3.2 Foamed Sheet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
7.3.2.1 Effect of Layer Multiplying on Sheet Morphology . . . . 2217.3.2.2 Multilayer PS/CNT-Filled PS Foam Sheet . . . . . . . . . . . 2237.3.2.3 Effect of CNT Content on Morphology . . . . . . . . . . . . . . 2257.3.2.4 Effect of Foaming Agent Content on Morphology . . . . . 226
7.3.3 EMI Shielding Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
7.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
8 The Effect of Foaming on the Properties of Carbon Nanotubes/Polymer Composites . . . . . . . . . . . . . . . . . . . 235Amir Ameli, Chul B. Park, and Petra Pötschke
8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
8.2 Conductive Filler/Polymer Nano composites (CPNs) . . . . . . . . . . . . . . . . . 237
8.3 Foaming of CPNs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2388.3.1 Gas-Melt Mixture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2398.3.2 Cell–Filler Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
8.4 Microstructure of CPN Foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2418.4.1 Batch-Foamed CPNs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2418.4.2 Foam-Injection-Molded CPNs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
8.5 Electrical Conductivity of CPN Foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2468.5.1 Batch-Foamed CPNs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2468.5.2 Foam-Injection-Molded CPNs . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
8.6 Dielectric Properties of CPN Foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
8.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
XVI Contents
9 The Effect of Solid-state Shear Processing on the Network Formation of Clay-based Polymer Nanocomposites . . . . . . . . . . 255Masami Okamoto
9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
9.2 Percolated Network Formation in PLSNCs . . . . . . . . . . . . . . . . . . . . . . . . 2579.2.1 Nanostructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2579.2.2 Flexibility of a Single MMT Layer . . . . . . . . . . . . . . . . . . . . . . . . . 2629.2.3 Volume-spanning Mesoscale Network . . . . . . . . . . . . . . . . . . . . . . 263
9.3 Network Structure and Rheological Properties in PLSNCs . . . . . . . . . . . 2649.3.1 Flocculation Control and Modulus Enhancement . . . . . . . . . . . . . 2649.3.2 Linear Viscoelastic Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2669.3.3 Relaxation Rate and Crystallization . . . . . . . . . . . . . . . . . . . . . . . . 2719.3.4 Nonlinear Shear Response . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2749.3.5 Analogy to Soft Colloids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2769.3.6 Reversibility of the Network Formation Process . . . . . . . . . . . . . 2769.3.7 Alignment of Silicate Layers in a Network . . . . . . . . . . . . . . . . . . 280
9.4 Interlayer Opening and Intercalated Nanocomposite Structure . . . . . . . 284
9.5 Novel Compounding Methods for Delamination of OMLFs . . . . . . . . . . . 288
9.6 Solid-state Shear Compounding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
9.7 Future Prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
10 Orientation Development During Processing of Nanocomposite Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297Samuel Kenig
10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
10.2 Earlier Studies Related to Flow-Induced Orientation of Elongated Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
10.3 Orientation Modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
10.4 Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
10.5 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30210.5.1 Materials Processes and Mechanical Characterization . . . . . . . . 30210.5.2 Shear Orientation by Parallel Plate Rheometer . . . . . . . . . . . . . . 30210.5.3 Elongational Orientation by Melt Drawing . . . . . . . . . . . . . . . . . . 304
10.6 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30510.6.1 Shear Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30510.6.2 Shear Orientation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30610.6.3 Elongational Orientation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30710.6.4 Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
10.7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
XVIIContents
11 Anomalous Viscoelastic Behaviors of Polymer Nanocomposites During Shear and Extensional Deformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313Esmaeil Narimissa, Rahul K. Gupta, and Sati N. Bhattacharya
11.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
11.2 Anomalous First Normal Stress Difference Behavior of PLA/NGP Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31411.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31411.2.2 Normal Force Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
11.3 Anomalous Uniaxial Extensional Deformation of PLA/NGP Nano composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32111.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32111.3.2 Extensional Viscosity Measurement . . . . . . . . . . . . . . . . . . . . . . . 32311.3.3 Application of Constitutive Equations for
Rheological Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
11.4 Temperature Causing Anomalous Shear Rheological Behavior . . . . . . . . 335
12 Polymer Nanocomposites Based on Layered Double Hydroxides (LDHs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343Sajid Naseem, Andreas Leuteritz, and Udo Wageknecht
12.1 Introduction to LDHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
12.2 Structural Aspects of LDHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34412.2.1 Brucite Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34412.2.2 Cation Substitution of LDHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34512.2.3 Interlayers of LDHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
12.3 Synthesis of LDHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34612.3.1 Co-precipitation Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34712.3.2 Anion Exchange Method (Indirect Method) . . . . . . . . . . . . . . . . . 34812.3.3 Calcination/Reconstruction Method (Memory Effect) . . . . . . . . . 34812.3.4 Other Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34912.3.5 Summary of LDH Synthesis Methods . . . . . . . . . . . . . . . . . . . . . . 34912.3.6 Thermal and Chemical Stabilities of Different LDHs . . . . . . . . . . 350
12.4 Applications of LDHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
12.5 Preparation of LDH/Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . 35212.5.1 In-Situ Synthesis Method for Polymer Nanocomposites . . . . . . . 352
12.5.1.1In-Situ LDH Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35212.5.1.2In-Situ Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
12.5.2 Solution Intercalation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35412.5.3 Melt Compounding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
XVIII Contents
12.5.4 Effect of Dispersion and Exfoliation of LDHs on LDH/Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
12.5.5 Sonicated Assisted Masterbatch (SAM) Melt Mixing . . . . . . . . . . 361
12.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
13 Polymer–Cellulose Nanocrystal (CNC) Nanocomposites . . . . . . 371Davood Bagheriasl and Pierre J. Carreau
13.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
13.2 CNC-reinforced Polymer Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373
13.3 Polymer–CNC Nanocomposite Processing Methods . . . . . . . . . . . . . . . . . 37413.3.1 Hydro-soluble or Hydro-dispersible Polymers . . . . . . . . . . . . . . . 37413.3.2 Non-hydro-soluble Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37513.3.3 In-situ Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37513.3.4 Compatibilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37613.3.5 Chemical Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37613.3.6 Solvent Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
13.4 Effect of CNCs on the Properties of Polymers . . . . . . . . . . . . . . . . . . . . . . 37713.4.1 Effect of CNCs on the Rheological Behavior of the Polymers . . . 37713.4.2 Small-amplitude Oscillatory Shear (SAOS) . . . . . . . . . . . . . . . . . . 37813.4.3 Steady Shear . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38013.4.4 Transient Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38113.4.5 Structure Build-up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38213.4.6 Effect of CNCs on the Mechanical and Thermal Properties
of Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38313.4.6.1 Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38313.4.6.2 Tensile Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38413.4.6.3 Dynamic Thermo-mechanical Properties . . . . . . . . . . . . 385
13.5 Applications for Polymer–CNC Nanocomposites . . . . . . . . . . . . . . . . . . . 387
13.6 Summary and Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
14 Cellulose Nanocrystals: Particles and Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395Wissam Abdallah and Musa R. Kamal
14.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
14.2 Cellulose and Cellulosic Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39714.2.1 Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39714.2.2 Cellulosic Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39814.2.3 Cellulose Nanocrystals (CNC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
14.2.3.1 Extraction Processes of CNC . . . . . . . . . . . . . . . . . . . . . . 399
XIXContents
14.2.3.2 Properties of CNC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40014.2.3.2.1 Mechanical Properties of CNC . . . . . . . . . . 40014.2.3.2.2 Thermal Properties of CNC . . . . . . . . . . . . 40114.2.3.2.3 Liquid Crystallinity Properties of CNC . . . 40114.2.3.2.4 Rheological Properties of CNC . . . . . . . . . . 40114.2.3.2.5 Optical Properties of CNC . . . . . . . . . . . . . 40214.2.3.2.6 Morphological Characteristics of CNC . . . 40214.2.3.2.7 Effects of Drying on the Properties
of CNC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
14.3 Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40714.3.1 Polymer–CNC Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
14.3.1.1 General Considerations in the Synthesis of Polymer–CNC Nanocomposites . . . . . . . . . . . . . . . . . . . 40814.3.1.1.1 Processing Methods . . . . . . . . . . . . . . . . . . 40814.3.1.1.2 Dispersion, Uniformity, and Interfacial
Interactions . . . . . . . . . . . . . . . . . . . . . . . . . 41014.3.1.2 Recent Products, Processes, and Properties . . . . . . . . . 413
14.3.1.2.1 Typical Polymer/CNC Nanocomposites . . 41314.3.1.2.2 Improvement of Nanocomposite
Mechanical Properties . . . . . . . . . . . . . . . . 41414.3.1.2.3 Thermal Properties of CNC-filled
Polymer Nanocomposites . . . . . . . . . . . . . . 41514.3.1.2.4 Rheological Properties of CNC-filled
Polymer Nanocomposites . . . . . . . . . . . . . . 41714.3.1.2.5 Crystallization Behavior of CNC-filled
Polymer Nanocomposites . . . . . . . . . . . . . . 42114.3.1.2.6 Barrier Properties of CNC-filled
Polymer Nanocomposites . . . . . . . . . . . . . . 42414.3.1.2.7 Templating with CNC . . . . . . . . . . . . . . . . . 42614.3.1.2.8 Challenges in the Use of Polymer–CNC
Nanocomposites . . . . . . . . . . . . . . . . . . . . . 42714.3.1.2.9 Water Sorption . . . . . . . . . . . . . . . . . . . . . . 42714.3.1.2.10 Nanocomposite Preparation . . . . . . . . . . . . 42814.3.1.2.11 Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
15 Processing and Properties of Carbon Nanotubes/Glass/ Epoxy Nano composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435Ryan J. Smith, Youssef K. Hamidi, and M. Cengiz Altan
15.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 436
15.2 Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44115.2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441
XX Contents
15.2.2 Batch Preparation and Prepreg Fabrication . . . . . . . . . . . . . . . . . 44215.2.3 Sample Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44215.2.4 Mechanical Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44315.2.5 Microstructural Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . 444
15.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44415.3.1 Effect of Nanotube Content on Composite Microstructure . . . . . 44415.3.2 Effect of Nanotube Content on Composite Mechanical
Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44615.3.3 Effect of Nanotube Type on Composite Microstructure . . . . . . . . 45015.3.4 Effect of Nanotube Type on Composite Mechanical
Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
15.4 Conclusions and Future Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
16 Processing Influence on Thermal Conductivity of Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463Andrzej Rybak
16.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
16.2 Thermal Conductivity Basics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46416.2.1 Thermal Conductivity of Neat Polymers . . . . . . . . . . . . . . . . . . . . 46416.2.2 Effect of Polymer Crystallinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46616.2.3 High Thermal Conductivity Fillers . . . . . . . . . . . . . . . . . . . . . . . . . 467
16.3 Factors Affecting Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . 46816.3.1 Processing Influence on Nanofiller Dispersion and
Thermal Conductivity of Nanocomposites . . . . . . . . . . . . . . . . . . . 46916.3.2 Particle Size and Shape Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47016.3.3 Effect of Nanofiller and Matrix Thermal Conductivity . . . . . . . . . 47216.3.4 Nanofiller–Matrix Interface Modification . . . . . . . . . . . . . . . . . . . 47316.3.5 Nanofiller Alignment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
16.4 Thermal Conductivity of Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . 47516.4.1 Nanocomposites with Carbon-based Fillers . . . . . . . . . . . . . . . . . 47516.4.2 Nanocomposites with Ceramic Nanofillers . . . . . . . . . . . . . . . . . . 47616.4.3 Nanocomposites with Metallic Nanoparticles . . . . . . . . . . . . . . . . 477
16.5 Modeling of Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47816.5.1 Theoretical Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47816.5.2 Correlation of Experimental Results with Models . . . . . . . . . . . . 482
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 489
10 1 The Effect of Processing Conditions in Twin-Screw Extrusion
�� 1.4�Application to Twin-Screw Extrusion
1.4.1� Influence of the Processing Conditions on the Final Micro structure
To test the influence of the processing conditions on the OMMT dispersion, a labo-ratory-scale extruder was chosen, the screw profile of which is shown in Figure 1.7. The screws have a diameter of 24 mm and a length of 960 mm (L/D = 40). The barrel is made up of 10 elements. The pre-blend of PP and PP-g-MA pellets is intro-duced into barrel 1, while the OMMT is fed into barrel 3, after the melting zone. Except for the first, all the barrel elements are set at 180 °C. After the melting zone, the screw profile consists of screw conveying elements, and five blocks of kneading discs, with various staggering angles. The formulation is kept constant and equal to 85 : 10 : 5 (PP–PP-g-MA–OMMT, in wt%).
Figure 1.7 Screw profile used in the experiments
1.4.1.1�Influence of the Screw SpeedIn a first step, the screw speed was varied between 100 and 1100 rpm, at a con-stant total feed rate of 2.6 kg/h. The results are presented in Figure 1.8. The disper-sion of the OMMT agglomerates improved when the screw speed increased, at least up to 600 rpm. Above this value, the dispersion was less efficient and larger ag-glomerates were present. Similarly, the yield stress (and thus exfoliation) increased up to around 400 rpm, and then stabilized at a lower level. Indeed, at high screw speed, a considerable overheating was observed: the final temperature increased from 192 to 238 °C between 100 and 1100 rpm. At 600 rpm, the temperature was high enough (222 °C) to induce thermal degradation of the organic modifier [22]. This was confirmed by a decrease in the interlamellar distance, from 3.8 to 3.6 nm, shown by XRD. Furthermore, the rheological characterizations showed that, above 300 rpm, a significant mechanical degradation of the matrix developed, resulting in a decrease in the weight average molecular weight, from 123 kg/mol for the virgin PP to 103 kg/mol at 1100 rpm [24]. Therefore, if an increase in screw speed helps to improve OMMT dispersion [25–29], it appears that excessively high speeds are not recommended for the preparation of nanocomposites.
111.4 Application to Twin-Screw Extrusion
Figure 1.8 Changes in area ratio (a) and appar-ent yield stress (b) with the screw speed (2.6 kg/h, 180 °C) (reprinted from [24])
1.4.1.2�Influence of the Feed RateThe experiments were carried out on the same lab-scale extruder, but with a slightly different screw profile. For these experiments, a masterbatch dilution method was chosen: in the first step, a 40 : 40 : 20 masterbatch (PP–PP-g-MA–OMMT, in wt%) was prepared. It was then diluted with PP in a second step, to obtain a final 85 : 10 : 5 nanocomposite. In this case, the pre-blend of masterbatch and PP pellets was intro-duced into the main hopper, that is, into barrel 1. The barrel temperature was set at 180 °C and the screw speed at 500 rpm in order to allow a wide range of variation of the feed rate. This high value of the screw speed was possible here because the selected screw profile was less severe than in the previous section. It is clearly shown in Figure 1.9 that an increase in feed rate induced an increase in area ratio and a decrease in apparent yield stress [30, 31]. In other words, the quality of the dispersion, both at the micro- and the nanoscale, decreased with the feed rate. In fact, an increase in the feed rate essentially affects the residence time, with a sharp decrease of the mean residence time and a narrowing of the distribution [10]. This link between residence time and exfoliation was also cited by Dennis et al. [32].
(a)
(b)
12 1 The Effect of Processing Conditions in Twin-Screw Extrusion
Consequently, the effect of the feed rate in the twin-screw extrusion is similar to that of the mixing time in the internal mixer (see Figure 1.5).
Figure 1.9 Changes in area ratio (a) and appar-ent yield stress (b) with the feed rate (500 rpm, 180 °C) (reprinted from [30])
The XRD measurements showed an intercalated structure, with an increase in the interlayer distance with feed rate, except at the lowest feed rate (3 kg/h) where this distance was less than that of the pristine OMMT [6]. Since the final temperature was about 210 °C, irrespective of the feed rate, we can imagine that the long resi-dence time at 3 kg/h (about 2 min) was responsible for a thermal degradation of the organic modifier.
1.4.1.3�Influence of the Barrel TemperatureMasterbatch dilution was also carried out, at 300 rpm and 3 kg/h, for a barrel temperature varying between 180 and 240 °C. The results are presented in Fig-
(a)
(b)
131.4 Application to Twin-Screw Extrusion
ure 1.10. The effect is similar to that of the feed rate, but less significant: an in-crease in barrel temperature increased the area ratio and decreased the yield stress. At high temperatures, the aggregates were larger, probably because the viscosity and thus the shear stresses were lower.
The XRD measurements indicated an intercalated structure (interlayer distance between 3.4 and 3.5 nm), except at 240 °C where it was lower (3.3 nm) than the pristine OMMT. In this last condition, the final temperature of the nanocomposite was about 260 °C, resulting in the destruction of the intercalant. The decrease of the apparent yield stress is, as for the area ratio, explained by the decrease of the stresses. To summarize, a high barrel temperature is detrimental to the quality of the dispersion of the OMMT, as already reported in the literature [5, 27, 33].
Figure 1.10 Changes in area ratio (a) and appar-ent yield stress (b) with the barrel temperature (300 rpm, 3 kg/h) (adapted from [6])
(a)
(b)
14 1 The Effect of Processing Conditions in Twin-Screw Extrusion
1.4.1.4�ConclusionsAs for the internal mixer, the results presenting the influences of the processing parameters (screw speed, feed rate, and barrel temperature) can be summarized when they are plotted versus the SME measured on the extruder (Figure 1.11). While the area ratio decreases steadily, the yield stress increases linearly up to 600 kWh/t and then stabilizes at a value of about 700 Pa.
Figure 1.11 Changes in area ratio (a) and apparent yield stress (b) with the specific mechanical energy (SME). (●): effect of screw speed, (○): effect of feed rate, (■): effect of barrel temperature (reprinted from [30])
Even if they were obtained on two different systems (direct OMMT dispersion and masterbatch dilution), the results of the internal mixer and the twin-screw ex-truder are interesting to compare. In Figure 1.12(a), we observe that the agglomer-ate dispersion is much worse on the twin-screw extruder. This is explained by the preparation of the masterbatch, where the high quantity of the OMMT (20 wt%) has led to the formation of large and solid agglomerates that are difficult to disperse thereafter. On the other hand, changes in yield stress with SME are in good agree-
(a)
(b)
1053.3 Carbon Nanotubes
Figure 3.3 Dispersion mechanism of layered organoclays into polymer matrices taking into account the possible collapse of the clay galleries due to the thermal degradation of the clay surfactant and polymer
�� 3.3�Carbon Nanotubes
Carbon nanotubes (CNTs) are formed by a hexagonal lattice of sp2 hybridized car-bon atoms wrapped into a cylindrical shape. CNTs can be formed as single-walled (SWCNTs) or multi-walled (MWCNTs), the former consisting of an individual graphene layer rolled up into a cylindrical shell with a diameter of 1–2 nm, whereas the latter contains several cylindrical shells coaxially arranged and stacked, sepa-rated by a distance of 0.34 nm. CNTs have outstanding mechanical and thermal properties, with typical values for a Young’s modulus of 1 TPa, tensile strength >50 GPa, thermal conductivity >3000 W m-1 K-1, and electrical conductivity in the range 106–107 S m-1. This set of excellent properties makes them attractive for applications in conductive polymer composites and adhesives, energy storage, thermal conductors, structural composite materials, microelectronics, etc. [33, 34]. However, in practice, it has been demonstrated that attaining full performance is not easy, not only because commercial CNTs contain impurities (e. g., metal cata-
106 3 Monitoring Dispersion and Re-agglomeration Phenomena During Manufacture
lyst particles and amorphous carbon), they also lack dimensional uniformity, form stable agglomerates, and are difficult to disperse in polymer matrices. This created a trough of disillusionment in the 2000s, and their commercial sustainability was questioned. In recent years, a better understanding of the chemical-physical char-acteristics and dispersion mechanisms, together with advances in manufacturing technologies and in surface functionalization, has promoted a new upsurge in the practical interest in CNTs.
The dispersion of carbon nanoparticles in polymeric matrices is difficult because:
� in the pristine state, p-p stacking and van der Waals interactions between indi-vidual tubes may lead to significant attraction and formation of stable agglomer-ates;
� MWCNTs grow as highly entangled agglomerates of several microns or even mil-limeters;
� the surface chemical inertia of CNTs due to the lack of chemical functionalities prevents the creation of strong interfaces with polymer molecules.
Interestingly, it is now generally accepted that perfectly dispersed CNTs are re-quired for maximum mechanical reinforcement; however, the existence of a few agglomerates is not always detrimental and may be necessary to build up an effec-tive conductive network. Consequently, the survival of initial agglomerates or the development of secondary agglomerates during mixing with a polymer may be advantageous for electrical conductivity. Therefore, understanding the dispersion mechanisms of CNTs is of major importance for the practical production of nano-composites with a tailored CNT dispersion extent to achieve optimal performance.
Dispersion of CNTs may be facilitated by surface modification of the particles and/or compatibilization with the polymer matrix (albeit this strategy may affect the transport properties). Chemical modification can be accomplished by non-covalent and covalent approaches [35, 36]. Through electrostatic, van der Waals, or p-p stacking interactions, the former enables the attachment and stabilization of dif-ferent functional groups at the surface of the CNTs without disturbing their carbon structure and electronic network. However, this method is unsuitable for melt mix-ing – which is the focus of this chapter – as the functionalization compounds are usually unstable at the typical polymer processing temperatures. Covalent func-tionalization involves bonding chemical groups to the carbon atoms of the CNTs’ surface, changing their hybridization state and decreasing their conjugation through the formation of covalent bonds. This method may induce surface damage and affect the electrical conductivity; however, if the covalent functionalization ap-proach is conveniently selected, the resulting functionalized CNTs are appropriate for melt mixing.
1073.3 Carbon Nanotubes
3.3.1�Dispersion of Carbon Nanotubes
The dispersion of CNTs in thermoplastic polymers during melt mixing has been the focus of numerous studies, using various types of mixing equipment and pro-cessing conditions. These studies converged to a number of general observations that enabled the build-up of phenomenological dispersion models such as that il-lustrated in Figure 3.4. Dispersion of the CNT agglomerates requires their wetting and infiltration by the polymer melt, reducing the agglomerate cohesion strength. The ease of infiltration of the polymer melt depends mainly on the agglomerate density and size [37], on the polymer interfacial tension [38], and viscosity. Pötschke and co-workers [39–42] found a correlation between dispersibility of CNTs and bulk density of the initial CNT agglomerates. Similarly, Salzano de Luna et al. [43] observed that CNT particles consisting of small and loosely packed clus-ters formed by interwoven bundles of combed yarns of nanotubes were easier to disperse than the reference denser commercial counterparts. Interfacial tension is not relevant when the hydrophobic CNTs are to be dispersed in polar polymers (e. g., polyamide, polycarbonate, polyimide). In the case of non-polar polymers (e. g., polyolefins), it is necessary to incorporate surface functionalities to the CNTs as mentioned above.
Figure 3.4 Dispersion mechanisms of CNT agglomerates in a polymer melt (adapted from [45, 48])
1314.4 Results and Discussion
After creating the ideal sharp crack tip, the threshold value of the fatigue crack propagation DKth is determined. For this purpose, DK is reduced with a constant DKgradient of -0.03 MPa·m1/2/mm until the da/dN value reaches 10-7 mm/cycle. Below DKth, no crack propagation occurs. In order to restart crack propagation, DK is increased rapidly by a given D(DK) of 0.03 MPa·m1/2. Finally, the fatigue crack propagation behavior is determined as a function of DK. In order to achieve it, DK is increased with a constant DKgradient of 0.03 MPa·m1/2/mm and the fatigue crack propagation rate da/dN is thus determined. These measurements were per-formed using a maximum a/w’ ratio of 0.8.
�� 4.4�Results and Discussion
4.4.1�Multiscale Material Characterization
4.4.1.1�Particle Morphology and Particle Size DistributionThe HNTs used herein are characterized by a homogenous nanotube morphology and are almost free of non-tubular impurities (Figure 4.5a). However, the as-re-ceived HNTs are strongly agglomerated and have to be dispersed prior to chemical modification. Figure 4.5b depicts an SEM image of HNTs after an ultrasonic treat-ment in aqueous solution. The agglomerates were broken and isolated HNTs were observed. In order to quantify the particle sizes, SEM pictures of dried droplets of a highly diluted HNT suspension were evaluated regarding the lengths and diame-ters of the HNTs (Figure 4.6). The particle lengths of the more than 400 character-ized HNTs range from 70 nm to 2200 nm with a median of 382 nm. The average length is 457 nm ± 291 nm. The diameter of the nanotubes ranges from 30 nm to 146 nm. The median is 67 nm and the average diameter is 67 nm ± 21 nm. Conse-quently, the average aspect ratio of the nanoparticles is approximately 7. The HNTs’ length distribution as well as the mean HNTs’ length remained unaffected by the HNTs’ dispersion carried out in the three-roll mill.
132 4 The Effect of Dispersion and Particle-Matrix Interactions on Fatigue Behavior
Figure 4.5 SEM images of HNTs (a) as-received and (b) isolated particles after the ultrasoni-cation process in water (200 W)
Figure 4.6 Particle length (a) and diameter distribution (b) of the HNTs after the ultrasonic treatment
4.4.1.2�Characterization of the HNTs’ ModificationThe results of the TGA analysis of unmodified, and TEOS (oHNTs)- and GOPTMOS (pHNTs)-modified HNTs are shown in Figure 4.7. The total mass loss of unmodified HNTs is 16.5 wt%. The first regime of the unmodified particles from 100 to 250 °C exposes a slight mass loss due to organic impurities absorbed on the HNTs’ sur-face. The decomposition of the surface hydroxyl groups is detected in the range from 250 to 550 °C. The modified HNTs show a similar behavior, whereas an addi-tional weight loss is observed at above 250 °C attributed to the decomposition of the grafted silanes to the HNTs’ surface. A grafting weight of 1.9 wt% is calculated for oHNTs and 2.1 wt% for pHNTs.
1334.4 Results and Discussion
Figure 4.7 TGA measurements of unmodi-fied and modified HNTs
Furthermore, FTIR measurements confirm the presence of the silanes on the HNTs’ surface (Figure 4.8). Compared to the spectrum of unmodified HNTs, the TEOS-modified HNTs (oHNTs) (Figure 4.8a) clearly show additional peaks at around 2800 to 3000 cm-1, which are characteristic of C–H vibrations and also present in the spectrum of the pristine silane. Similar results are obtained for GOPTMOS-mod-ified HNTs (pHNTs) (Figure 4.8b); however, in the pHNT spectrum, the peaks asso-ciated with the C–H bands hardly appear.
Figure 4.8 FTIR analysis of (a) oHNTs and (b) pHNTs in comparison to as-received HNTs
The silane grafting is also evidenced by XPS measurements as shown in Table 4.2. The carbon content of 4.3 wt% of the unmodified HNTs is due to organic impurities, which are also detected by TGA measurements. The oHNTs and pHNTs show an increased carbon content of 18.1 wt% and 10.8 wt%, respectively, indicating suc-cessful surface modification. XPS measurements show a decrease in the atomic contents of the silicon, aluminum, and oxygen components of the HNTs’ surface
134 4 The Effect of Dispersion and Particle-Matrix Interactions on Fatigue Behavior
[7]. By comparing the two types of modified HNTs, the increase in carbon content and decrease in oxygen content are less pronounced for pHNT as compared to oHNT. Since GOPTMOS consists of a lower number of carbon atoms and a higher number of oxygen atoms, these differences are thus reasonable.
Table 4.2 Surface Composition of HNTs in wt%, Determined by XPS Analyses
Atom HNT (as-received) oHNT (TEOS) pHNT (GOPTMOS)C 4.3 18.1 10.8Si 17.8 15.5 17.2Al 15.1 12.7 13.6O 62.7 53.7 58.4
The assumed chemical structure of the pHNT surface modification is depicted in Figure 4.9. Since the modification is carried out in an aqueous solution, the epoxy functionality is hydrolyzed during the grafting reaction [39].
Figure 4.9 Hydrolysis of the epoxy functionality during the silane grafting reaction in aqueous media, according to Horr et al. [39]
Finally, the real filler content of the nanocomposites was determined by TGA mea-surements, considering the determined weight loss of the HNTs of 16.5 wt% as seen in Table 4.3.
Table 4.3 Real HNTs’ Weight Fractions and Glass Transition Temperature of the Nano-composites
Intended content (wt%)
Unmodified HNTs oHNTs (TEOS) pHNTs (GOPTMOS)Content (wt%)
Tg (°C) Content (wt%)
Tg (°C) Content (wt%)
Tg (°C)
0 - 150 ± 1 - 150 ± 1 - 150 ± 1
1.25 1.2 ± 0.1 147 ± 1 1.4 ± 0.1 150 ± 1 1.3 ± 0.1 147 ± 1
2.5 2.4 ± 0.1 149 ± 1 2.9 ± 0.3 150 ± 1 2.3 ± 0.1 146 ± 1
5.0 4.8 ± 0.1 146 ± 1 4.8 ± 0.1 151 ± 1 4.4 ± 0.2 138 ± 1
1354.4 Results and Discussion
4.4.1.3�Dispersion of the HNTsThe morphologies of the nanocomposites are examined by scanning and transmis-sion electron microscopy techniques. SEM images of the fracture surfaces of the nanocomposites with the highest HNT contents (4.8 wt% HNTs, 4.8 wt% oHNTs, and 4.4 wt% pHNTs) provide a good overview of existing agglomerates (Figure 4.10a–c). The morphology of the nanocomposites filled with unmodified HNTs (im-age (a)) is characterized by a lot of agglomerates in the range of 5–10 µm. However, the surface treatment of the HNTs leads to less agglomeration as revealed by im-ages (b) and (c). For both modifications, TEOS and GOPTMOS, the number and the size of clusters are significantly reduced. TEM images (Figure 4.10d–f) support these observations by revealing big agglomerates in the case of unmodified HNTs and mainly individually separated HNTs for oHNTs and pHNTs. Regardless of the type of surface treatment, the HNTs’ dispersion is improved although the presence of some small agglomerates could not be avoided.
Figure 4.10 SEM (a–c) and TEM (d–f) micrographs of the nanocomposites containing 4.8 wt% unmodified HNTs (a and d), 4.8 wt% oHNTs (b and e), and 4.4 wt% pHNTs (c and f)
4.4.1.4�Influence of Surface Modification on Interface ChemistryIt is important to mention that the interface chemistry is highly influenced by the composition and molecular structure of the resin system. The anhydride cured ep-oxy network is characterized by a large number of polar groups, most importantly, the hydrophilic carbonyl groups corresponding to the methylhexahydrophthalic anhydride monomers. On the contrary, the bisphenol A backbone of the DGEBA monomers is highly hydrophobic. As a consequence, the interactions between the HNTs and the matrix are strongly affected by their compatibility, determined by the type of surface modifier.
2077.2 Experimental
decreased with increasing number of layers in the sheet. When Rahman et al. [58] studied the viscosity contrast effect on the foam morphology and layer integrity, they found that using a high viscosity resin for the film layer and a low viscosity resin for the foam layer produced better layer integrity. The film layer with the high viscosity acted as a confining layer, which helped reduce the cell size of the foamed layer as the nominal layer thickness decreased. Guo et al. [55, 56] investi-gated the extension rheology of different polyolefins and their blends to improve their foaming ability using multilayer coextrusion. These studies mostly focused on neat polymer foams without conductive filler networks.
In the work reported here, a multilayer coextrusion process was used to fabricate a polystyrene/CNT (PS/CNT) sheet to study the effect of multilayer coextrusion on the morphology evolution and conductivity of coextruded PS/CNT composites when the layer thickness varies from the macroscale to the sub-microscale. The effect of matrix viscosity on the morphology and resistivity was also studied. It was found that viscosity plays a role in the behavior and that low viscosity materials were more sensitive to layer multiplying, particularly at sub-micron layer thick-nesses. Additionally, the multilayer and foaming approaches were combined as an approach for improving EMI shielding. The multilayer coextrusion processes was used to extrude a sheet with alternating layers of a CNT-filled polymer foam and neat solid polymer. The main objective of this work was to investigate the effect of the number of layers, CNT content, and foaming agent content on the morphology of these materials. The EMI shielding properties were measured and correlated to the material morphology.
�� 7.2�Experimental
7.2.1�Materials
The CNTs were obtained as a commercially available 20 wt% polystyrene (PS)/CNT masterbatch (MB2020-00, Hyperion Catalysis). The CNTs were vapor-grown multi-wall carbon nanotubes with a reported diameter, length, and density of 10–15 nm, 1–10 μm, and 1750 kg/m3, respectively.
The CNT masterbatch was diluted with two commercially available polystyrenes: Ineos Nova 3601 (MI = 13.5 g/10 min, density = 1040 kg/m3, estimated mole-cular weight = 168,000 Da [59]) and Americas Styrenics LLC’s Styron 665 (MI = 1.5 g/10 min, density = 1040 kg/m3, molecular weight = 305,000 Da [60]). Since the molecular weight (MW) of Styron 665 was 1.8 times greater than the molecular weight of Nova 3601, these polystyrenes were designated as high MW PS and low MW PS, respectively.
208 7 Polymer Nanocomposites and Multilayer Nanocomposite Films by Coextrusion
The polystyrene (PS) compounds for the foamed layer were prepared by diluting the PS/CNT masterbatch with a commercially available polystyrene (Americas Styrenics LLC, grade: Styron 685D). This polystyrene was also used for the neat film layer. A commercial endothermic chemical foaming agent (Bergen Interna-tional, grade: Foamazol™ 95) was used to foam the PS/CNT layer. For this foaming agent, the suggested processing temperature for a maximum gas yield was 175 to 200 °C.
CNT-filled PS was fabricated by diluting the 20 wt% PS/CNT masterbatch to 3 and 5 wt% PS/CNT compounds using a co-rotating twin screw extruder (Leistritz, ZSE18HP-400). For the foamed trials, the PS–CNT masterbatch was diluted into compounds with 1.5, 3.0, and 6.0 wt% CNTs. The masterbatch and neat PS pellets were fed separately into the twin screw extruder by two volumetric feeders to pro-vide the correct CNT loadings. All compounds were prepared using a temperature profile of 150 to 200 °C (rear to die), a constant screw speed of 300 rpm, and an output of about 3.6 kg/h. The extrudate was cooled and pelletized for coextrusion.
7.2.2�Coextrusion of Multilayer Samples
The coextrusion line had two 25-mm Wayne single screw extruders (L/D = 30 : 1), two Zenith PEP gear pumps, a customized feedblock, and layer multiplying ele-ments (LMEs). The customized feedblock was designed to form a three-layer “sand-wich” profile (shown in Figure 7.1). Melt from the feedblock was fed into the LMEs, where the melt streams were split (1), stacked (2), and merged (3). The number of individual layers in the extrudate, N, was directly proportional to the number of LMEs, n, added to the coextrusion line:
(7.1)
Figure 7.1 (a) Layer multiplying coextrusion set-up and schematic plot of a horizontal layer multiplication process and (b) the relationship between number of layers and number of layer multiplying elements
2097.2 Experimental
For the PS/CNT systems, the twin screw compounded material was fed into both extruders of the coextrusion line and the two melt streams were pumped into the feedblock using gear pumps for tight control of the output. The PS/CNT sheet with nominal individual layers ranging from 3 to 8193 was fabricated using 0 to 12 LMEs. Table 7.1 lists the processing temperatures of LMEs and feedblock, num-ber of LMEs, and CNT concentration for each coextrusion trial. The output was held constant at about 2.4 kg/h and the feed ratio for the two extruders was 50 : 50. In order to analyze the effects of LMEs on the compounds, no sheet die was used in the process. All samples were directly extruded from the LMEs onto the roll stack. To achieve the optimal surface finish and efficient cooling, extruded melts were mounted and cooled on the chilling rolls with a rotation speed of 0.6 m/min.
Table 7.1 Processing Trials at Different Temperatures Utilizing 0 to 12 LMEs
Number of LMEs
Number of Layers
TLME = 210 °C TLME = 230 °CCNT Concentration (wt%) CNT Concentration (wt%)High MW PS Low MW PS High MW PS Low MW PS
0 3 3 3 5 5
3 17 – 3 – –
7 257 – 3 5 5
12 8193 3 3 5 5
For the foamed samples, the pellets of diluted PS/CNT material were first dry blended with the foaming agent and then extruded as the middle layer of the sand-wich structure that formed in the feedblock. The top and bottom layers (layers with a light color) of the sandwich structure were neat PS melt, which was extruded from another extruder. After passing through the feedblock, the three-layer melt stream was pumped through three different sets of LMEs (0, 2, and 3), which corresponded to 3, 9, and 17 layers of melt. The feed ratio for the two extruders was 50 : 50 and the output was held constant at about 2.31 × 10–3 m3/h. For the extruders, feedblock, and LMEs, the temperature was held constant at 190 °C; a lower temperature of 160 °C was used for the sheet die to create the high pressure drop needed for the foaming process. To achieve the optimal surface finish and a constant sample thickness (1.5 mm), extruded foam/film multilayer sheets were pulled at a rate of 0.6 m/min on the chill rolls. The cooling temperature was 60 °C. Specific CNT and foaming agent usage for each trial are listed in Table 7.2. Since CNTs were only present in the foamed layer, the CNT content was calculated with respect to the total polymer material based on the 50 : 50 feed ratio in the coextru-sion process.
210 7 Polymer Nanocomposites and Multilayer Nanocomposite Films by Coextrusion
Table 7.2 Processing Trials for the Foamed Multilayer Sheet
Number of Layers
Nominal Individual Layer Thickness
[CNT]* [Foaming Agent]**
(µm) (wt%) (vol%) (wt%) 3 750 0 0 1, 2, and 3
0.75 0.45 21.51 0.90 23.03 1.83 1, 2, and 3
9 187.5 3.03 1.83 217 93.75 0.75 0.45 2
1.51 0.90 23.03 1.83 1, 2, and 3
* CNT content was calculated based on the total volume of the polymer in the extrudate.** Foaming agent concentration was based on the weight of the foam layer.
7.2.3�Characterization
Thermal gravimetric analysis (TGA) was carried out (TA Instruments Q50). To determine the CNT content in the compounded material, approximately 20 mg of diluted PS/CNT compound was placed in the platinum testing pan and heated from room temperature to 300 °C at a heating rate of 20 °C/min. The CNT content was calculated based on the weight loss after burning off the polymer in a N2 atmosphere; neat PS was used as the baseline. The decomposition kinetics of the foaming agent was also performed using TGA [61]. A foaming agent pellet was first heated at a rate of 50 °C/min from about 20 °C to the processing temperature (190 °C) and then the isothermal test was conducted at 190 °C to measure the weight loss of foaming agent vs. time. The gas release during the process was estimated based on the weight reduction for the residence time of the coextrusion (6 minutes).
A capillary rheometer (Dynisco, LCR 7000) was used to characterize the flow be-havior of both the 3 wt% and 5 wt% PS/CNT compounds prepared by twin screw extrusion. In accordance with ASTM D3835, the apparent viscosity of the com-pounds was measured at shear rates of 5, 10, 20, 40, 100, and 200 s–1 and the two processing temperatures (210 and 230 °C). The data obtained from these measure-ments were corrected by the Weissenberg–Rabinowitsch correction to plot the corrected viscosity as a function of corrected shear rate.
Transmission electron microscopy (TEM) was used to characterize the dispersion, distribution, and orientation of the CNTs in the extrudate with different numbers of layers. The PS/CNT pellets were cut into ultrathin sections using a cryo-ultra-microtome (Leica, model: EM UC6) with a sharp glass knife and dropped on the
300 10 Orientation Development During Processing of Nanocomposite Polymers
increasing probability of CNTs to come into contact with each other [9, 10]. Thus, it was a matter of a trade-off between the aggregation rate and the disaggregation rate. Disentangled MWCNTs were easily oriented in the flow direction while the MWCNTs within the agglomerations did not undergo alignment. Thus, shear rate broke the agglomerations and released more dispersed CNTs that aligned. Hence, higher shear rates were linked to higher orientation. These results agree with what is presented in Equation (10.1). A study on orientation as a result of shear and elongational deformation found that part of an intertwined CNT bundle could be “oriented” as a whole with each individual CNT within the agglomerate randomly oriented after elongational flow, while the others separated into individual CNTs. Pegel et al [8] and Handge et al [9] showed that the alignment state of CNTs in polycarbonate following elongational flow tends to experience relaxation. The re-sults show that after 60 minutes, the orientation of the particles was random. Lele et al. [12] used X-ray diffraction to evaluate the flow-induced orientation of layered silicates in polypropylene compatibilized with maleic anhydride polypropylene. They demonstrated that clay tactoids were readily oriented in shear. He et al. [13] incorporated CNTs into natural rubber latex and followed their orientation during shear by Raman and TEM (transmission electron microscopy). They found that shear induced the CNTs’ alignment. Dykes et al. [14] showed by X-ray scattering measurements that nanoclays dispersed in polymers align relative to the flow direction and this depends on shear rate and applied strain amplitude, with almost no relaxation after flow cessation.
Recently, the principles of flow-induced orientation of elongated and rigid moieties were applied to nanoparticles by Kenig [15] in view of experimental results from the literature [7–13] that indicated that NCs or CNTs are oriented due to shear or elongation flows.
�� 10.3�Orientation Modelling
Jeffery [16] was the first to describe the orientation development of dilute elon-gated particles in a Newtonian fluid. Jeffery’s equation for simple shear is as follows:
(10.1)
where Ф'1 is the rate of angle change, Ф1 is the orientation angle, and the shear rate.
Integration of Equation (10.1) with time, t, results in Equation (10.2):
30110.3 Orientation Modelling
(10.2)
where B = (Rp2-1) / (Rp2+1), Rp is the aspect ratio of the elongated particle, and t the time of flow.
As Equation (10.2) suggests, the orientation angle (tangent) is related to the aspect ratio Rp and the product of shear rate and time – the total shear.
In the case of elongational flow, Jeffery’s equation for diluted concentrations and Newtonian fluid could be written as:
(10.3)
where ε’ is the elongation rate.
Integration of Equation (10.3) with respect to time leads to Equation (10.4):
(10.4)
where DR is the draw ratio equal to the product e' × t and the ratio D12/D2
2, where D1 is the initial extrudate diameter and D2 is the final drawn polymer diameter. l is the “orientability parameter” depending on the Rp and adopted from Erick-sen’s definition of anisotropic fluids [17].
As concluded from Equation (10.4), the orientation of an elongated particle in a simple elongational flow is related to the total elongation and the tendency of the particle to elongate in a specific fluid (the orientability parameter).
Finally, it was assumed that in high orientations (small tan Ф), the modulus of elasticity is inversely proportional to tanФ. Hence,
(10.5)
where K is the proportion constant.
Advanced models for the prediction of elongated particles (short fibers) orientation were suggested by Tucker and Folgar [18], especially to treat concentrated fiber compounds, taking into account fiber–fiber interactions. As nanocomposite melts are diluted in nature, the particles’ interaction is minimized and the main concern is the nanoparticle-polymer interactions, which will be investigated in the present work.
The modified Jeffery’s Equation (10.2), (10.4), and (10.5) will be the basis for the study on the orientation development of nanoparticles in elongation and shear flows.
302 10 Orientation Development During Processing of Nanocomposite Polymers
�� 10.4�Methodology
Assuming that the two basic flow mechanisms – elongation and shear – control the orientation development during the processing of thermoplastics, the following methodology was followed:
The elongation mechanism was investigated using a simple unidirectional melt drawing system. In this part of the study, the effect of draw-down ratio (total elon-gation strain) on the modulus of CNTs and INTs containing polycarbonate (to avoid crystallinity induced by the nanoparticles) was investigated.
The shear mechanism was studied in using a parallel plate rheometer where the total shear depends on the number of revolutions and rotation speed.
In both flows, the total elongation and shear strains were calculated and the result-ing orientation was determined using the elastic modulus (Equation (10.5)).
�� 10.5�Experimental
10.5.1�Materials Processes and Mechanical Characterization
Multiwalled carbon nanotubes (MWCNTs) (Nanocyl 7000 Belgium) with an elastic modulus of close to 1000 GPa, a strength of 10–65 GPa, a diameter of 10 nm, and a length of up to mms were used.
Multiwalled inorganic nanotubes (WS2 INTs) (NanoMaterials Israel) with an elastic modulus of 170 GPa, a strength of up to 16 GPa, a diameter of 80 nm, and a length of 1–20 μm were used.
Polycarbonate (Makrolon 2207) was compounded with a 15% CNTs masterbatch (Nanocyl PC1501) to obtain 1 wt% and 0.5 wt% CNTs/PC nanocomposites.
Polycarbonate was compounded with inorganic nanotubes (INTs). The compounds were prepared with a twin screw extruder (Prism).
The storage modulus was determined by a dynamic mechanical analyzer (DMA) at room temperature.
10.5.2�Shear Orientation by Parallel Plate Rheometer
Circular specimens were prepared by compression molding of compounded PC/NTs.
30310.5 Experimental
A parallel plate rheometer was used to apply pure shear stresses using controlled one-direction rotation and varying rotation speeds as shown in Figure 10.1.
Figure 10.1 Schematics of flow in a parallel plate rheometer
The shear rate of the parallel plate rheometer is given by
(10.6)
where (r) is the shear rate as a function of radius r, r is the radial distance from the center of the circular plate, W is the rotation speed, and h the thickness of the sheared material (Figure 10.2).
Figure 10.2 Schematics of the parallel plate rheometer
304 10 Orientation Development During Processing of Nanocomposite Polymers
To study the effects of shear on orientation, different total shears were applied on the molten nanocomposite melts. Following shear, the specimens were cooled to room temperature. DMA (dynamic mechanical analysis) tensile specimens were prepared from the circular specimens, as shown in Figure 10.3. The diameter of the circular disc was 25 mm. The specimens cut for the DMA measurements were 3 mm wide and 2 mm thick.
Figure 10.3 Location of specimens cut from the circular disc for DMA measurements
The shear rates, shear time, and total shear applied are given in Table 10.1.
Table 10.1 Different Shear Rates, Times, and Total Shear Applied on the Nanocomposite Melts
Run Angular velocity [rad/s]
Shear time [s] Total shear
1 0.027174 240 302 0.054348 240 603 0.081522 240 904 0.108696 240 1205 0.13587 240 150
6 0.217391 90 90
10.5.3�Elongational Orientation by Melt Drawing
The elongational flow was obtained by winding a polymer melt extrudate at differ-ent winding speeds, as shown in Figure 10.4.
37713.4 Effect of CNCs on the Properties of Polymers
13.3.6�Solvent Casting
In addition to those long, tedious, and costly preparation methods [31–36, 45], simple and efficient preparation methods, such as solvent casting, have been de-veloped [19, 20]. This is similar to that introduced for hydro-soluble polymers (Figure 13.2) with the exception of the use of a non-aqueous medium. It has been reported that CNCs are dispersible in N,N-dimethylformamide (DMF) [19–21], dimethyl sulfoxide (DMSO) [33], formic acid [46], dimethylacetamide (DMAc) [47], pyridine [48], and a few more solvents. Therefore, the use of one of these sol-vents is a practical way for preparing polymer–CNC nanocomposites comprising a soluble polymer in the mentioned solvent, such as PLA [19, 20] and polyamide [46]. This method can also be used to produce masterbatches to be mixed with commercial grade polymers via conventional melt-mixing processes to prepare final polymer–CNC nanocomposites [18, 21, 48]. Likewise, masterbatches of hydro-soluble polymer–CNCs can be obtained by solvent casting as mentioned earlier and then melt- or solution-mixing with non-hydro-soluble polymers to pre-pare the final nanocomposites [16, 35]. The non-hydro-soluble polymer, often used as a compatibilizer, could bring complexities to the final nanocomposites’ properties and it may not be desirable in terms of renewability, biocompatibility, and biodegradability [35]; or in some cases, it may countervail the reinforcing effect of the CNCs on the mechanical performances of the final nanocomposites [16, 47]. In addition, the miscibility of the compatibilizer with the polymer matrix is another concern.
�� 13.4� Effect of CNCs on the Properties of Polymers
13.4.1�Effect of CNCs on the Rheological Behavior of the Polymers
During the last few decades, rheology has been employed as a powerful tool to un-derstand the interactions between the components of polymer nanocomposites. The formation of an interconnected network of particles plays an important role on the rheological behavior of nanocomposites that can reveal the efficiency of the preparation method leading to a micro or nano dispersion. Therefore, the effects of CNCs on the rheological behavior of molten polymer nanocomposites can be as-cribed to the quality of the dispersion and distribution of CNCs within the studied matrices. Some of the useful rheological measurements that are sensitive to inter-actions between the nanoparticles are presented in the next sections.
378 13 Polymer–Cellulose Nanocrystal (CNC) Nanocomposites
13.4.2�Small-amplitude Oscillatory Shear (SAOS)
Transition from a liquid-like behavior for neat polymer matrices to a solid-like be-havior for nanocomposites and large increases of the dynamic rheological proper-ties, such as complex viscosity, storage and loss moduli for nanocomposites rela-tive to those of matrices, especially at low frequencies, are among the main effects caused by CNCs when they are nano-dispersed and well-distributed. Figure 13.4 clearly demonstrates these changes for solvent-cast PLA–CNC nanocomposites with different CNC loadings relative to the neat polymer matrix. The complex vis-cosity of the neat polymer matrix exhibits a long plateau, with a slight shear- thinning behavior at high frequencies (Figure 13.4a) and its storage modulus is typical of molten polymers with a terminal zone of slope equal to 2 on the log–log plot (Figure 13.4b). However, by incorporating CNCs, significant increases in the complex viscosity and storage modulus are observed, mainly at low frequencies, demonstrating clearly the strong effect of CNCs on the rheological properties of the polymer matrix. It is also worth mentioning that as the CNC concentration in-creases in the system, the possibility of agglomerate formation significantly in-creases and lower rheological properties may be expected as illustrated in Figure 13.4a and b for PLA containing 7 wt% CNCs compared to PLA with 6 wt% CNCs. The behavior of polymer nanocomposites in the low-frequency region is governed by the interactions between the nanoparticles and the formation of an intercon-nected network of nanoparticles [20]. At the percolation threshold, the nanocom-posites exhibit a transition from liquid- to solid-like behavior with a complex vis-cosity tending to infinity as the frequency goes to zero and plateau values for the elastic modulus. An estimation of the rheological percolation threshold can be obtained from SAOS data by plotting the complex viscosity as a function of the complex modulus as shown in Figure 13.4c for PLA and PLA–CNC. For the neat polymer matrix and composites with CNC contents below the rheological percola-tion threshold, no viscosity upturn is observed at low frequencies, while at larger CNC loadings, the unbounded viscosity is indicative of a percolating network and an apparent yield stress [18, 20, 49–52]. Therefore, the rheological percolation threshold would fall in the range of CNC loadings with no complex viscosity up-turn and the first point for which upturn is observed. Moreover, the modified Her-schel–Bulkley model can fit the SAOS data for samples with CNC contents above the percolation threshold concentration well:
(13.2)
where G* is the complex modulus, s0 is the apparent yield stress, g 0 is the strain amplitude, k is a constant, and n is the flow index [18]. Thus, the apparent yield stress can be determined from the modified Herschel–Bulkley model and used as a
37913.4 Effect of CNCs on the Properties of Polymers
measure of the CNC network strength. The higher the value of the apparent yield stress, the stronger the network. The rheological percolation threshold can be de-termined using storage modulus data at low frequencies as reported in Figure 13.4d for solvent-cast PLA–CNC nanocomposites with different CNC loadings [20]. Then, the following empirical power–law equation can be used to fit the data and obtain the rheological percolation threshold [53]:
(13.3)
where bcG and n are power–law constants, m is the CNC concentration (wt%), and mcG is the rheological percolation threshold (wt%) [20, 53]. A value of 0.68 wt% was reported for the rheological percolation threshold of solvent-cast PLA–CNC nano-composites [20].
Figure 13.4 SAOS data for PLA and PLA–CNC nanocomposites prepared via a solvent-casting method for various CNC loadings. (a) Complex viscosity, h*, and (b) storage modulus, G', ver-sus frequency, w, (c) h* versus complex modulus, G*, and (d) G' as a function of CNC loading. The lines in c and d are the fits of the modified Herschel–Bulkley model, Equation (13.2) and Equation (13.3), respectively (adapted from [20])
380 13 Polymer–Cellulose Nanocrystal (CNC) Nanocomposites
13.4.3�Steady Shear
Similar to the behavior shown in SAOS experiments, shear thinning without any plateau region and unbounded viscosity at low shear rates for polymer–CNC nano-composites are expected in steady-shear tests, while the neat polymer matrices usually exhibit a plateau region at low shear rates. Figure 13.5a illustrates the ef-fect of CNC content on the viscosity of PLA and PLA–CNC nanocomposites with different CNC loadings. A long plateau region for the matrix is observed, as ex-pected, while by the addition of CNCs, the plateau region disappears and a shear-thinning behavior is observed. At higher CNC contents, as the distance be-tween the particles decreases, the interactions between CNCs become stronger and the possibility of network formation increases; as a result, increased viscosity val-ues with a more pronounced shear-thinning behavior are observed for larger CNC loadings. For these samples, the shear viscosity significantly decreases with in-creasing shear rate (Figure 13.5a) indicating that the CNC network is broken down under shear [20]. Figure 13.5b compares the PLA–CNC systems with the same CNC concentrations, but for different preparation methods. A better dispersion and distribution contribute to a stronger CNC network and higher viscosity values are observed when the nanocomposite is prepared with a masterbatch method and melt-extruded utilizing a twin-screw extruder. However, the neat PLA and PLA–CNC composites prepared without a solvent-cast masterbatch, i. e., DMI and DME, exhibit very low viscosity values and almost a Newtonian behavior confirming that the direct melt-mixing method is not efficient in dispersing CNCs into the PLA matrix.
Figure 13.5 Steady-shear viscosity, h, versus shear rate, , for: (a) PLA, and PLA with 1 and 4 wt% CNCs prepared via a solvent-casting method [20], and (b) PLA, PLA–CNC composites prepared via direct melt mixing utilizing an internal mixer or a twin-screw extruder, and PLA–CNC nanocomposites prepared using solvent-cast PLA–CNC masterbatches that were melt-mixed with PLA employing an internal mixer or a twin-screw extruder [18]
38113.4 Effect of CNCs on the Properties of Polymers
13.4.4�Transient Behavior
Another rheological measurement that can be utilized to obtain information about the quality of the CNC dispersion, efficiency of the preparation method, and conse-quently, the existence and strength of the CNC network is the transient (also called start-up or stress growth) shear test. In this experiment, a sudden and constant shear rate is applied and the variation of the transient viscosity, , of the samples with time is monitored. Figure 13.6a depicts how CNCs can change the behavior of a PLA matrix in such measurements by comparing the variation of with time for PLA and PLA–CNC composites prepared with direct melt mixing and combined solvent-casting and melt mixing [18]. The neat matrix and the composites without a CNC network, i. e., those prepared with direct melt mixing, do not show any over-shoot due to the absence of any structure and their low viscoelasticity. For poly-mer–CNC nanocomposites prepared using a solvent-cast PLA–CNC masterbatch, however, overshoots are observed at the beginning of the tests and are attributed to the structure or network of CNCs within the polymer matrix [18, 20, 21]. These transient tests are destructive, and when the structure is broken down, the samples exhibit a steady-state viscosity. However, Figure 13.6b shows that when a reverse shear flow is suddenly imposed, the structure can be rebuilt depending on the rest
Figure 13.6 (a) Transient viscosity in shear stress growth as a function of time performed under a shear rate of 5 s–1 for PLA, PLA–CNC composites containing 4 wt% CNCs and prepared with direct melt mixing, batch and extrusion, and melt mixing of solvent-cast PLA–CNC master-batch with PLA, and (b) transient viscosity for the same samples in reverse flow tests right after the cessation of the first shear test, and after 1000 s rest time (adapted from [18])
time. If the rest time is sufficiently long, for example 1000 s as shown in Figure 13.6b, particle–particle interactions increase and, consequently, the structure is gradually rebuilt and eventually, the initial structure as before the shear test is re-covered [18, 20]. Again, for the PLA–CNC composites prepared with direct melt mixing, there was no evidence of CNC network formation after the rest time and
Symbols
3D conductive network 2063-D network structure 418– stacking 106β-form PP crystals 67γ-form crystals 60
A
acid hydrolysis of cellulose 399acoustic cavitation 30activation energy 270adhesion force 177adhesives 387AFM analysis 74agglomerate 10agglomerate dispersion 20agglomeration of CNTs 310alignment of CNTs 194alignment of nanofillers 474alternating foam/film structures 206anion exchange capacity 346anion exchange method 346anisotropy factor 299anomalous behaviors of N1 315anomaly in extensional viscosity 335anomaly in the percolation threshold
336apparent yield stress 5area ratio 4aspect ratio 98, 301atomic force microscopy (AFM) 160,
262, 373, 400automotive 387
average aspect ratio 132Avrami model 421
B
ball milling 122barrel reactor 45barrier property 424batch foaming 252batch mixer 172biaxial stretching 238biobased, biocompatible, and bio-
degradable 388biobased nucleating agent 415biocomposites 388biodegradable and biocompatible 396biomedical 387biomedical nanocellulose 388birefringence 402BN nanoflakes 471Brabender twin screw extruder 323breakage of single particles 122breakdown of agglomerates 48, 56Brownian motion 271bubble cavitation 84
C
calcination/reconstruction method 346capillary flow entrance pressure drop
315capillary rheometer 210capillary rheometry 102carbon nanotube length 157
Index
490 Index
carbon nanotubes (CNTs) 97, 105, 201, 297, 435
carboxyl-functionalized short MWCNTs 441
cast film 61catalysts 350cavitation phenomenon 32cell density 211, 225cell growth 226cell morphology 222cell size 225cellular morphology 251cellulose 395cellulose nanocrystals (CNC) 371, 396cellulose nanoparticles 396cellulosic nanoparticles 398characteristic relaxation time 325chemically modified CNC 411chiral nematic structure 401clay dispersion 100clay exfoliation 2CNC as a template 427CNT agglomerates 107CNT–CNT conductive network 202CNT-filled polymer foam 207CNT functionalization 438CNT length reduction 214CNT masterbatch 207CNTs 177CNTs dispersed in an aqueous
suspen sion 435CNTs in fiber-reinforced polymer
composites 440CNT surface area 438coaxial ultrasonic device 42cold crystallization temperature 384colloidal suspensions of CNCs 373compact tension (CT) 127complex dynamic viscosity 68complex viscosity 5, 58, 266, 378,
417compliance C 129conventional injection molding (CIM)
173conveying elements 10, 109
co-precipitation method 346core–shell structures 473covalent bonding 136covalent functionalization 106covalent silane coupling 122crack bridging 122crack deflection 122, 141crack pinning 141crack propagation 447crack tip opening displacement 128crater morphology 310critical energy release rate, GIC 128crystallinity 66, 180crystallization enthalpy 60crystallization half-time (t1/2) 273crystallization rate 423crystallization temperature 60, 181, 384curing agent/CNT/waterborne epoxy
mixture 442
D
Debye–Bueche theory 263degree of delamination 322degree of dispersion 98, 189delamination and exfoliation 256dielectric loss (tan d). 249differential scanning calorimetry (DSC)
180, 415, 421dilute elongated particles 300dimensional stability 187discrete dispersion 256disorientation kinetics 274dispersed montmorillonite (MMT) 258dispersion 10, 29dispersion and distribution 72, 380dispersion and distribution of CNCs 377dispersion and distribution of CNTs 82dispersion and exfoliation 476dispersion, distribution, and orientation
210dispersion of carbon nanotubes 158dispersion of CNC 428dispersion of CNTs 106, 435dispersion of fillers 172
491Index
dispersion of fillers by the ultrasonic treatment 38, 86
dispersion of nanotube bundles 452dispersion of NCs 1dispersion of the halloysite 122dispersive mixing 408dissolution and re-coprecipitation 349distributive mixing 408DMA tensile specimens 304draw ratio 301drug delivery 387DSC study 59dynamic loading 129dynamic mechanical analysis (DMA)
127dynamic mechanical thermal analysis
(DMTA) 385, 415dynamic modulus 129dynamic oscillatory shear 266dynamic storage modulus 264dynamic viscosity 58
E
E-glass/waterborne epoxy laminates reinforced 435
electrical conductivity 68, 105, 158, 178, 246, 247
electrical percolation threshold 39, 68, 69, 73, 77, 114, 206, 237
electrical properties 203electrical resistivity 173, 228electrical/thermal properties 172electromagnetic interference (EMI)
shielding 236electron tunneling 202electrospinning 428electrostatic discharge dissipation
202electrostatic discharge (ESD) protection
236elongated nanoparticles 298elongational flow 280elongational mixing 469elongation at break 58, 81, 127, 384
elongation flow 299elongation time 329EMI shielding 202, 204EMI shielding efficiency (SE) 212EM wave reflection 204energy-dissipating mechanisms 150energy of break-up 291epoxy nanocomposites 122epoxy resins 121ethylene–octene copolymer 166exfoliated graphene nanoplatelets (GNPs)
476exfoliation 2, 20, 100, 113extensional flow 159, 321extensional mixer 109extensional rheological percolation
threshold 335extensional rheometer 324extensional viscosity 314, 332extrudate swell 315
F
fast cooling 196fast Fourier transform (FFT) image
analysis 257fatigue and cyclic loading 123fatigue crack propagation (FCP) 123fatigue crack propagation rate da/dN
131feed rate 11filler–matrix interactions 424filler–polymer percolating 3D network
338fine open cell structure of poly-
caprolactone 205first normal stress difference (N1) 314,
315flame retardancy 344flame retardant products 255flexibility of smectite clay 262flexural modulus 450flexural strength 449flow-induced crystallization 182flow-induced orientation 280
492 Index
foam coextrusion 223foamed cellular structure of PP–MWCNTs
244foamed polymer/CNT 205foam injection molding 252food packaging 387fountain flow 299Fourier transform infrared (FTIR) 292Fourier transform infrared spectroscopy
(FTIR) 101, 126fracture surface 141fracture surface characteristics 446fracture toughness 122, 140, 439freeze drying 404friction force 177functionalized CNTs 110functionalized GNPs 116
G
gas barrier films 255Gaussian distribution 260glass transition/softening temperature
175glass transition temperature (Tg) 136,
385, 415GNP dispersion 114grafting of long-chain aliphatic
compounds 376graphene derivatives 97graphene oxide (GO) 112, 476graphite nanoplatelets (GNPs) 189graphite nanoplates (GNPs) 112grooved barrel reactor 45
H
halloysite nanotubes (HNTs) 122Halpin and Tai 264H-bonding 136heat transfer 176Hencky rates 329heterogeneous nucleating agent 423heterogeneous nucleation 224high aspect ratio 396
high cooling rates 175high-frequency electrical power 32high-frequency mechanical vibration 32high-power ultrasound 31high-resolution scanning electron
microscopy 127high-shear mixing 469high shear rates 174HRC (heat release capacity) 357hydro-dispersible polymers 374hydrodynamic stresses 101hydrothermal method 349
I
impact strength 66injection velocity 178, 185in-line NIR 102inorganic nanotubes (INTs) 297in-situ LDH synthesis 352in-situ polymerization 1, 30, 98, 359, 469inter- and intra-molecular hydrogen
bonds 372intercalation 4, 100interconnected cellulose nanoparticle
network 409interconnected network of nanoparticles
378interface chemistry 135interfacial adhesion 446interfacial interaction 194interfacial properties 124interfacial stress transfer 136interfacial tension 411interfacial thermal resistance 471intergallery spacing 99interlamellar distance 4interlaminar shear strength 435interlayer anion exchange 345interlayer spacing 346internal mixer 3, 47ion exchange 284ion-exchange materials 350ion-exchange reactions 99isothermal crystallization kinetics 421
493Index
K
K-BKZ model 332kneading 10, 80kneading zone 110
L
large-amplitude oscillatory shear (LAOS) 271
large anharmonicity in molecular vibrations 464
large surface area 396layer-by-layer (LbL) assembly 429layered clays 97layered double hydroxides (LDHs)
343layered silicate 99, 255layer multiplying elements (LMEs)
206LDH interlayer galleries 354length reduction 164length-to-diameter (aspect) ratio 157light scattering 402limiting oxygen index (LOI) 66linear viscoelastic response 257liquid crystalline polymers (LCPs)
298liquid crystallinity of cellulose nano-
crystals 401LLDPE/GNP 114load-bearing applications 255long MWCNTs 441loss modulus 266, 418low frequency storage modulus 420
M
magnetic-field 474management of heat dissipation 463masterbatch 11, 80, 84, 203mechanical properties 414mechanisms of heat conduction 483melt blending 172melt compounding intercalation 356
melting and crystallization 180melting point 415melting section 3melting temperature 180melting zone 10melt intercalation 256melt-mixing 1, 30, 98, 359, 469melt processing 157, 202, 409melt viscosity 158, 203melt yield stress 102mesostructure 257microinjection molding 171micromoldings 173microstructure 2, 18, 457microstructure and morphology 177minimum-to-maximum load ratio 129mixing sections 3mode I fracture toughness 128modeling of thermal conductivity 478modelling of orientation 298modification of the filler–matrix interface
473modulus of elasticity 301molding pressures 178molding temperatures 178mold temperature 185molecular orientation 185, 321montmorillonite 2, 99morphology 203, 207morphology evolution 222multilayer coextrusion 206multilayer structures 205multimetal LDHs 344multiwalled carbon nanotubes (MWCNTs)
157, 299multiwalled carbon nanotubes (MWCNTs)
nanocomposite foam 241multiwalled CNT (MWCNT)/epoxy
438
N
nano-capacitor 249nanocellular 241nanoclay dispersion 102
494 Index
nanocomposite laminates 435nanocomposite prepregs 435nanocrystalline cellulose 396nano-dielectric 249nanographite platelets (NGP) 315nanoindentation 184nanoindentation testing 177nano/microcellular foams 242nanoparticle agglomerates 98nanoparticle surface modification 98nanoscale toughening 152nanotube agglomerates 438, 447nanotube aspect ratio 455nanotube length reduction 158nanotube pullouts 455natural gas conversion reactions 350natural rubber/GNP 114nematic structure 401network density 137network formation of nanoparticles 418Newtonian fluid 300Nielsen 264nonlinear viscoelastic region 316normal stress differences 314nucleating effect of CNCs 384Nylon 6-based nanocomposites (N6CNs)
258
O
organo-clay network 268orientability parameter 301orientation development 298orientation parameter 299oriented shish-kebab structure 178oriented structure 178oscillatory rheometry 101oscillatory shear 26oscillatory shear flow 36oxygen transmission rate (OTR) 424
P
PA6/CNT 187PA6/expandable graphite (PA6/EG) 182
packaging materials 424parallel plate rheometer 302particle dispersion 124particle–matrix interaction 122particle–matrix interface 122particle–polymer interactions 315,
483particle–polymer surface interactions
411particle pull-out 142PBAT/GNP 314PC/CNT 178percolating filler network 409percolation threshold 158, 190, 213, 246,
318, 415, 470phonon scattering 464pHRR (peak heat release rate) 357physical foaming 236pinning and twisting 122PLA–CNC masterbatch 381PLA/GNP 314planar BN particles 477PLA/PCL 185plastic cavitation 151plastic deformation 122plastic void growth 143plastic zone 128, 144polarized light optical microscopy (PLOM)
177polyacrylonitrile/butadiene/styrene
(ABS)/CNT 204polycaprolactone (PCL)-grafted CNCs
375polycarbonate 302polycarbonate/CNT 203polyethylene oxide (PEO) 374polymer–clay interphase 100polymer–CNC nanocomposite 396polymer foaming 236polymethylmethacrylate (PMMA)/CNT
205polymethylmethacrylate (PMMA)/
polystyrene (PS) 167polystyrene/CNT 207polystyrene (PS)-grafted CNCs 375
495Index
polyurethane/CNT (PU/CNT) 195polyvinyl alcohol (PVOH) 374POM/CNT 178power consumption and torque change
78PP/clay 101PP/CNT 178PP/ethylenepropylene-diene rubber
(EPDM) (PP/EPDM) 184PP/GNP 191PP/halloysite nanotube (PP/HNT)
185preferential orientation 317preferential orientation of CNTs 178pre-intercalation method 349processability of nanocomposites 86processing-induced orientation 298processing temperature 203properties of LDH/polymer nano-
composites 358PS/CNT 178pseudo-solid-like behavior 267
R
radiation frequency 205Raman scattering 400Rayleigh scattering 276real permittivity (ε') 249rectangular hyperbola model 320reduced graphene oxide (rGO) 112relaxation process 270relaxation time 326renewable and biobased CNCs 373residence time 11, 101, 163, 203rheological and electrical percolation
threshold 70rheological percolation threshold
206, 378, 418rheological properties 417rod-like nanoparticles 371roll-mill mixing 469rotational relaxation rate 273rotation speed 163
S
scanning electron microscopy (SEM) 4, 160, 177, 402, 444
scattering of phonons 471screw configuration 80screw design 163screw profile 16screw speed 10secondary agglomerates 203, 218secondary agglomeration 111, 203selective localization 252SEM analysis 70SEM micrographs 60shear bands 151shear damping 327shear flow 159, 299shear-induced orientation 299shear rates 109shear stress 159shear thinning 401shielding efficiency (SE) 204simulation software 195single-walled carbon nanotubes
441skin layer 185small-amplitude oscillatory shear
(SAOS) 271small-angle light scattering 276small-angle neutron scattering
(SANS) 276, 402solid-state compounding 289solid-state shear 288solution blending 124solution casting 409solution intercalation method 354solution mixing 30, 359solvent exchange 125solvent mixing 469sonication 469sonication assisted masterbatch (SAM)
melt mixing 361sonication assisted mixing 361specific mechanical energy (SME)
3, 102, 163specific surface area 98
496 Index
sphere-shaped AlN 477spray drying 403spreading radial flow 299starch biopolymer 414steady and dynamic shear 313steady shear 271steady shear experiment 315steady shear tests 380steady shear viscosity 316stiffness of CNT/epoxy nanocomposites
438storage and loss moduli 102, 314, 325,
378storage modulus 60, 414, 417strain at break 186strain hardening 321strain-induced hardening 282stress intensity factor amplitude ΔK
129structure and morphology 74supercritical gas 236surface area to volume ratios of
microparts 176surface functionalization 409surface modification of CNC 428surface-modified nanoparticles 122surface roughness 142surface tension 165, 174surfactant-treated MWCNTs 439
T
TEM images 59tensile strength 66, 105, 127, 186, 384tensile tests 127ternary and quaternary LDHs 345thermal and chemical stabilities of LDHs
350thermal annealing 110thermal conductivity 105, 180, 464thermal contact resistance 464thermal gravimetric analysis (TGA) 210thermal interface resistance 483thermal stability 66, 344, 353, 415thermal transfer 464
thermogravimetric analysis (TGA) 103, 126, 180, 416
thickness of the skin layer 178three metal LDHs 344three-point bending short beam shear
test 443three-point bending tests 443three-roll mill 122, 126time of flight-secondary ion mass
spectrometry (TOF-SIMS) 103time–temperature superposition principle
267torque 78total elongation strain 299total shear strain 299toughening mechanism 142transmission electron micrograph 324transmission electron microscopy (TEM)
4, 127, 135, 160, 177, 210, 257, 300, 362, 402
tungsten disulfide (WS2) 297twin screw compounding 101twin screw extruder 98, 108, 159, 172,
302twin screw extrusion 1, 381two metal LDHs 344two-roll mixers 172
U
ultrasonic agitation 442ultrasonically-aided extrusion 34ultrasonically-aided injection molding
54ultrasonically-aided processing 29ultrasonically-assisted twin-screw
extruder 67ultrasonic compounding 75ultrasonic treatment 37, 125ultrasonic treatment of nanocomposites
85ultrasonic waves 29unidirectional melt drawing 302UV degradation protection 344
497Index
V
van der Waals forces 136, 202van der Waals interactions 99, 106variotherm system 175viscosity and orientability 308viscous shear stress 314volume and surface resistivity 79volume resistivity 211, 228
W
wall slip 174waterborne epoxy resin 441water sorption 427Weibull distribution 259WLF shift factor 274
X
X-band 227X-band frequency 227X-ray diffraction analysis 400X-ray diffraction (XRD) 4, 300X-ray photoelectron spectroscopy (XPS)
127X-ray scattering 400XRD patterns 59
Y
yield stresses 57Young’s modulus 63, 105, 127, 137, 186,
206, 384, 414