Polymer reference book

The aim of this book is to familiarise the reader with all aspects of the techniques used in the examination of polymers, covering chemical, physiochemical and purely physical methods of examination. It is the purpose of this book to describe the types of techniques now available to the polymer chemist and technician, and to discuss their capabilities, limitations and applications. All types of modern instrumentation are covered including those used in general quality control, research analysis, process monitoring and the mechanical, electrical, thermal and optical characteristics. Aspects such as automated analysis and computerised control of instruments are covered. The book is intended, therefore, for all staff, whether direct or peripheral, who are concerned with the instrumentation and methodology in the polymer laboratory including laboratory designers, engineers and chemists, and those concerned with the implementation of analytical specifi cations and process control limits. Practically all of the major newer instrumental techniques and many of the older classical techniques have been used to examine polymers and all of these are discussed in detail.

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Polymer Reference Book T.R. Crompton Rapra Technology Limited Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118 First Published in 2006 by Rapra Technology Limited Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK ©2006, Rapra Technology Limited All rights reserved. Except as permitted under current legislation no part of this publication may be photocopied, reproduced or distributed in any form or by any means or stored in a database or retrieval system, without the prior permission from the copyright holder. A catalogue record for this book is available from the British Library. Every effort has been made to contact copyright holders of any material reproduced within the text and the authors and publishers apologize if any have been overlooked. Typeset by Rapra Technology Limited Printed and bound by Lightning Source UK Limited ISBN: 098-1-84735-025-1 iContents Preface ......................................................................................................................... 1 1. Determination of Metals ....................................................................................... 7 1.1 Destructive Techniques ................................................................................ 7 1.1.1 Atomic Absorption Spectrometry .................................................... 7 1.1.2 Graphite Furnace Atomic Absorption Spectrometry ........................ 8 1.1.3 Atom Trapping Technique ............................................................... 9 1.1.4 Vapour Generation Atomic Absorption Spectrometry ................... 10 1.1.5 Zeeman Atomic Absorption Spectrometry .................................... 11 1.1.6 Inductively Coupled Plasma Atomic Emission Spectrometry ......... 14 1.1.7 Hybrid Inductively Coupled Plasma Techniques ............................ 22 1.1.8 Inductively Coupled Plasma Optical Emission Spectrometry– Mass Spectrometry ........................................................................ 23 1.1.9 Pre-concentration Atomic Absorption Spectrometry Techniques ... 25 1.1.10 Microprocessors ............................................................................ 26 1.11 Autosamplers ............................................................................................. 26 1.1.12 Applications: Atomic Absorption Spectrometric Determination of Metals ....................................................................................... 26 1.1.13 Visible and UV Spectroscopy ......................................................... 34 1.1.14 Polarography and Voltammetry .................................................... 34 1.1.15 Ion Chromatography .................................................................... 36 1.2 Non-destructive Methods .......................................................................... 43 1.2.1 X-ray Fluorescence Spectrometry .................................................. 43 1.2.2 Neutron Activation Analysis ......................................................... 49 References ........................................................................................................... 53 ii Polymer Reference Book 2. Non-metallic Elements ........................................................................................ 57 2.1 Instrumentation: Furnace Combustion Methods ........................................ 58 2.1.1 Halogens ....................................................................................... 58 2.1.2 Sulfur ............................................................................................ 58 2.1.3 Total Sulfur/Total Halogen ............................................................ 58 2.1.4 Total Bound Nitrogen ................................................................... 59 2.1.5 Nitrogen, Carbon, and Sulfur ....................................................... 59 2.1.6 Carbon, Hydrogen, and Nitrogen ................................................. 60 2.1.7 Total Organic Carbon ................................................................... 61 2.2 Oxygen Flask Combustion Methods .......................................................... 61 2.2.1 Total Halogens .............................................................................. 61 2.2.2 Sulfur ............................................................................................ 62 2.2.3 Oxygen Flask Combustion: Ion Chromatography ......................... 62 2.2.4 Instrumentation ............................................................................ 63 2.2.5 Applications .................................................................................. 63 2.3 Acid and Solid Digestions of Polymers ....................................................... 64 2.3.1 Chlorine ........................................................................................ 64 2.3.2 Nitrogen ....................................................................................... 65 2.3.3 Phosphorus ................................................................................... 65 2.3.4 Silica ............................................................................................. 66 2.4 X-ray Fluorescence Spectroscopy ............................................................... 66 2.5 Antec 9000 Nitrogen/Sulfur Analyser ........................................................ 67 References ........................................................................................................... 68 3. Functional Groups and Polymer Structure ........................................................... 71 3.1 Infrared and Near-Infrared Spectroscopy ................................................... 71 3.1.1 Instrumentation ............................................................................ 71 3.1.2 Applications .................................................................................. 71 3.2 Fourier Transform Near-Infrared Raman Spectroscopy ............................. 80 3.2.1 Theory .......................................................................................... 80 iii Contents 3.2.2 Instrumentation ............................................................................ 82 3.2.3 Applications .................................................................................. 82 3.3 Fourier Transform Infrared Spectroscopy .................................................. 85 3.3.1 Instrumentation ............................................................................ 85 3.3.2 Applications .................................................................................. 86 3.4 Nuclear Magnetic Resonance (NMR) Spectroscopy .................................. 89 3.4.1 Instrumentation ............................................................................ 89 3.4.2 Applications .................................................................................. 89 3.5 Proton Magnetic Resonance (PMR) Spectroscopy ..................................... 96 3.5.1 Instrumentation ............................................................................ 96 3.5.2 Applications .................................................................................. 97 3.6 Reaction Gas Chromatography ................................................................. 99 3.6.1 Instrumentation ............................................................................ 99 3.6.2 Applications .................................................................................. 99 3.7 Pyrolysis Gas Chromatography ............................................................... 108 3.7.1 Theory ........................................................................................ 108 3.7.2 Instrumentation .......................................................................... 108 3.7.3 Applications ................................................................................ 109 3.8 Pyrolysis Gas Chromatography–Mass Spectrometry ................................ 122 3.8.1 Instrumentation .......................................................................... 122 3.8.2 Applications ................................................................................ 125 3.9 Pyrolysis Gas Chromatography–Fourier Transform NMR Spectroscopy .... 126 3.10 High-Performance Liquid Chromatography ................................ 126 3.11 Mass Spectrometric Techniques ............................................................... 127 3.11.1 Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) .... 127 3.11.2 XPS ............................................................................................. 130 3.11.3 Tandem Mass Spectrometry (MS/MS) ......................................... 132 3.11.4 Fourier Transform Ion Cyclotron Mass Spectrometry ................. 132 3.11.5 MALDI-MS ................................................................................ 133 3.11.6 Radio Frequency Glow Discharge Mass Spectrometry ................ 134 iv Polymer Reference Book 3.12 Microthermal Analysis ............................................................................ 135 3.13 Atomic Force Microscopy ........................................................................ 136 3.13.1 Applications ................................................................................ 136 3.14 Scanning Electron Microscopy and Energy Dispersive Analysis using X-rays ............................................................................................ 139 References ......................................................................................................... 139 4. Examination of Polymer Surfaces and Defects ................................................... 165 4.1 Introduction ............................................................................................ 165 4.2 Electron Microprobe X-ray Emission Spectrometry ................................. 165 4.2.1 Applications ................................................................................ 166 4.3 NMR Micro-imaging ............................................................................... 168 4.4 Fourier Transform Infrared Spectroscopy ................................................ 168 4.4.1 Instrumentation .......................................................................... 169 4.4.2 Applications ................................................................................ 169 4.5 Diffusion Refl ectance FT-IR Spectroscopy (Spectra-Tech) ........................ 170 4.6 Attenuated Total Infrared Internal Refl ectance (ATR) Spectroscopy (Spectra-Tech) .......................................................................................... 171 4.7 External Refl ectance Spectroscopy (Spectra-Tech) .................................... 172 4.8 Photoacoustic Spectroscopy ..................................................................... 175 4.8.1 Instrumentation .......................................................................... 175 4.8.2 Applications ................................................................................ 176 4.9 X-ray Diffraction/Infrared Microscopy of Synthetic Fibres ...................... 180 4.10 Scanning Electrochemical Microscopy (SECM) ....................................... 184 4.11 Scanning Electron Microscopy (SEM) ...................................................... 184 4.12 Transmission Electron Microscopy (TEM) .............................................. 184 4.12.1 Electron Microscopy and Inverse Gas Chromatography ............. 184 4.12.2 Supersonic Jet Spectrometry ........................................................ 186 4.13 ToF SIMS ................................................................................................. 186 vContents 4.14 Laser-Induced Photoelectron Ionisation with Laser Desorption ............... 186 4.15 Atomic Force Microscopy ........................................................................ 187 4.16 Microthermal Analysis ............................................................................ 187 References ......................................................................................................... 187 5. Volatiles and Water ........................................................................................... 193 5.1 Gas Chromatography .............................................................................. 193 5.1.1 Instrumentation .......................................................................... 193 5.1.2 Applications ................................................................................ 198 5.2 High-Performance Liquid Chromatography ............................................ 201 5.2.1 Instrumentation .......................................................................... 201 5.2.2 Applications ................................................................................ 201 5.3 Polarography ........................................................................................... 202 5.3.1 Instrumentation ......................................................................... 202 5.3.2 Applications ................................................................................ 202 5.4 Headspace Analysis ................................................................................. 203 5.4.1 Instrumentation ......................................................................... 203 5.4.2 Applications ................................................................................ 204 5.5 Headspace Gas Chromatography–Mass Spectrometry ............................. 205 5.5.1 Instrumentation .......................................................................... 205 5.6 Purge and Trap Analysis .......................................................................... 206 5.6.1 Instrumentation .......................................................................... 206 References ......................................................................................................... 207 6. Fingerprinting Techniques ................................................................................. 209 6.1 Glass Transition Temperature (Tg) and Melting Temperature (Tm) ........... 209 6.2 Pyrolysis Techniques ................................................................................ 209 6.2.1 Conventional Pyrolysis Gas Chromatography ............................. 209 6.2.2 Laser Pyrolysis Gas Chromatography ......................................... 213 6.2.3 Photolysis Gas Chromatography ................................................. 213 6.2.4 Pyrolysis Mass Spectrometry ....................................................... 215 vi Polymer Reference Book 6.3 Infrared Spectroscopy .............................................................................. 216 6.3.1 Potassium Bromide Discs ............................................................ 217 6.3.2 Hot Pressed Film ......................................................................... 217 6.4 Pyrolysis Fourier Transform Infrared Spectroscopy ................................. 218 6.4.1 Theory ........................................................................................ 218 6.4.2 Instrumentation .......................................................................... 218 6.4.3 Applications ................................................................................ 218 6.5 Raman Spectroscopy ............................................................................... 221 6.6 Fourier Transform Near-Infrared Raman Spectroscopy ........................... 221 6.7 Radio Frequency and Low Discharge Mass Spectrometry ........................ 226 References ......................................................................................................... 226 7. Polymer Additives ............................................................................................. 229 7.1 IR and Raman Spectroscopy .................................................................... 229 7.1.1 Instrumentation .......................................................................... 229 7.1.2 Applications ................................................................................ 229 7.2 Ultraviolet Spectroscopy .......................................................................... 230 7.2.1 Instrumentation .......................................................................... 230 7.2.2 Applications ................................................................................ 230 7.3 Luminescence and Fluorescence Spectroscopy ......................................... 232 7.3.1 Instrumentation .......................................................................... 232 7.3.2 Applications ................................................................................ 233 7.4 Nuclear Magnetic Resonance Spectroscopy (NMR) ................................ 234 7.5 Mass Spectrometry .................................................................................. 234 7.5.1 Instrumentation .......................................................................... 234 7.5.2 Applications ............................................................................... 234 7.6 Gas Chromatography .............................................................................. 235 7.6.1 Instrumentation .......................................................................... 235 7.6.2 Applications ................................................................................ 235 vii 7.7 High-Performance Liquid Chromatography ............................................ 235 7.7.1 Theory ........................................................................................ 235 7.7.2 Instrumentation .......................................................................... 237 7.7.3 Applications ................................................................................ 244 7.8 Complementary Techniques ..................................................................... 245 7.8.1 HPLC with Mass Spectrometry ................................................... 245 7.8.2 HPLC with IR Spectroscopy ....................................................... 248 7.9 Ion Chromatography ............................................................................... 248 7.10 Supercritical Fluid Chromatography ........................................................ 248 7.10.1 Theory ........................................................................................ 248 7.10.2 Instrumentation .......................................................................... 249 7.10.3 Applications ................................................................................ 251 7.11 Thin-Layer Chromatography ................................................................... 252 7.11.1 Theory ........................................................................................ 252 7.11.2 Applications ................................................................................ 253 7.12 Polarography ........................................................................................... 253 7.12.1 Instrumentation .......................................................................... 253 7.12.2 Applications ................................................................................ 253 7.13 Pyrolysis Gas Chromatography–Mass Spectrometry ................................ 253 7.14 X-ray Photoelectron Spectroscopy ........................................................... 254 7.15 Secondary Ion Mass Spectrometry ........................................................... 254 7.16 X-ray Fluorescence Spectroscopy ............................................................. 254 7.17 Solvent Extraction Systems ...................................................................... 255 References ......................................................................................................... 255 8. Polymer Fractionation and Molecular Weight ................................................... 263 8.1 Introduction ............................................................................................ 263 8.2 High-Performance GPC and SEC ............................................................. 264 8.2.1 Theory ........................................................................................ 264 8.2.2 Applications ................................................................................ 272 Contents viii Polymer Reference Book 8.3 High-Performance Liquid Chromatography ............................................ 273 8.3.1 Instrumentation .......................................................................... 273 8.3.2 Applications ................................................................................ 274 8.4 Supercritical Fluid Chromatography ........................................................ 277 8.4.1 Theory ........................................................................................ 277 8.4.2 Instrumentation .......................................................................... 279 8.4.3 Applications ................................................................................ 279 8.5 Gas Chromatography .............................................................................. 282 8.6 Thin-Layer Chromatography ................................................................... 282 8.7 NMR Spectroscopy ................................................................................. 282 8.8 Osmometry .............................................................................................. 283 8.9 Light Scattering Methods ......................................................................... 283 8.10 Viscometry ............................................................................................... 285 8.11 Ultracentrifugation .................................................................................. 286 8.12 Field Desorption Mass Spectrometry ....................................................... 287 8.13 Capillary Electrophoresis ......................................................................... 287 8.14 Liquid Chromatography–Mass Spectrometry .......................................... 288 8.15 Ion Exchange Chromatography ............................................................... 288 8.16 Liquid Adsorption Chromatography ....................................................... 289 8.17 Time-of-Flight Secondary Ion Mass Spectrometry (ToF SIMS) ................. 289 8.18 MALDI-MS ............................................................................................. 289 8.19 Thermal Field Flow Fractionation ........................................................... 290 8.20 Desorption Chemical Ionisation Mass Spectrometry ................................ 290 8.21 Grazing Emission X-ray Fluorescence Spectrometry ................................ 290 References ......................................................................................................... 290 ix 9. Thermal and Chemical Stability ........................................................................ 305 9.1 Introduction ............................................................................................ 305 9.2 Theory ..................................................................................................... 306 9.2.1 Thermogravimetric Analysis ....................................................... 306 9.2.2 Differential Thermal Analysis ..................................................... 307 9.2.3 Differential Scanning Calorimetry ............................................... 307 9.2.4 Thermal Volatilisation Analysis ................................................... 310 9.2.5 Evolved Gas Analysis .................................................................. 310 9.3 Instrumentation ....................................................................................... 311 9.3.1 Instrumentation for TGA, DTA, and DSC .................................. 311 9.3.2 Instrumentation for TVA and EGA ............................................. 313 9.4 Applications ............................................................................................ 314 9.4.1 Thermogravimetric Analysis ....................................................... 314 9.4.2 TGA–FT-IR Spectroscopy and DSC–FT-IR Spectroscopy ............ 317 9.4.3 Differential Thermal Analysis ..................................................... 318 9.4.4 Differential Scanning Calorimetry ............................................... 318 9.4.5 Thermal Volatilisation Analysis ................................................... 320 9.4.6 EGA–TGA–Gas Chromatogravimetry and TGA–Gas Chromatography–Mass Spectrometry ........................ 321 9.4.7 Mass Spectrometric Methods ...................................................... 330 9.5 Examination of Thermal Stability by a Variety of Techniques .................. 362 9.6 Heat Stability of Polypropylene ............................................................... 362 9.6.1 Infl uence of Pigmentation and UV Stabilisation on Heat Ageing Life ......................................................................... 364 References ......................................................................................................... 373 10. Monitoring of Resin Cure ................................................................................. 385 10.1 Dynamic Mechanical Thermal Analysis ................................................... 385 10.1.1 Theory ........................................................................................ 385 10.1.2 Instrumentation .......................................................................... 385 10.1.3 Applications ................................................................................ 386 Contents xPolymer Reference Book 10.2 Dielectric Thermal Analysis ..................................................................... 387 10.2.1 Theory ........................................................................................ 387 10.2.2 Instrumentation .......................................................................... 388 10.2.3 Applications ................................................................................ 388 10.3 Differential Scanning Calorimetry ........................................................... 391 10.4 Fibre Optic Sensor to Monitor Resin Cure .............................................. 393 References ......................................................................................................... 393 11. Oxidative Stability ............................................................................................. 395 11.1 Theory and Instrumentation .................................................................... 395 11.2 Applications ............................................................................................ 395 11.2.1 Thermogravimetric Analysis ....................................................... 396 11.2.2 Differential Scanning Calorimetry ............................................... 396 11.2.3 Evolved Gas Analysis .................................................................. 399 11.2.4 Infrared Spectroscopy of Oxidised Polymers ............................... 400 11.2.5 Electron Spin Resonance Spectroscopy ........................................ 404 11.2.6 Matrix-Assisted Laser Desorption/Ionisation Mass Spectrometry ... 404 11.2.7 Imaging Chemiluminescence ....................................................... 404 References ......................................................................................................... 404 12. Examination of Photopolymers ......................................................................... 407 12.1 Differential Photocalorimetry .................................................................. 407 12.1.1 Theory ........................................................................................ 407 12.1.2 Instrumentation .......................................................................... 408 12.1.3 Applications ................................................................................ 409 12.2 Dynamic Mechanical Analysis ................................................................. 414 12.3 Infrared and Ultraviolet Spectroscopy ...................................................... 415 12.4 Gas Chromatography-Based Methods ..................................................... 415 References ......................................................................................................... 415 xi 13. Glass Transition and Other Transitions ............................................................. 417 13.1 Glass Transition ....................................................................................... 417 13.2 Differential Scanning Calorimetry ........................................................... 417 13.2.1 Theory ........................................................................................ 417 13.2.2 Instrumentation .......................................................................... 420 13.2.3 Applications ................................................................................ 420 13.3 Thermomechanical Analysis .................................................................... 420 13.3.1 Theory ........................................................................................ 420 13.3.2 Instrumentation .......................................................................... 420 13.3.3 Applications ................................................................................ 421 13.4 Dynamic Mechanical Analysis ................................................................. 422 13.4.1 Applications ................................................................................ 422 13.5 Differential Thermal Analysis and Thermogravimetric Analysis .............. 423 13.6 Nuclear Magnetic Resonance Spectroscopy ............................................. 423 13.7 Dielectric Thermal Analysis ..................................................................... 423 13.8 Other Transitions (alpha, beta, and gamma) ............................................ 423 13.8.1 Differential Thermal Analysis ..................................................... 423 13.8.2 Dynamic Mechanical Analysis .................................................... 424 13.8.3 Dielectric Thermal Analysis ........................................................ 427 13.8.4 Thermomechanical Analysis ........................................................ 430 13.8.5 Infrared Spectroscopy ................................................................. 430 References ......................................................................................................... 430 14. Crystallinity ....................................................................................................... 433 14.1 Theory ..................................................................................................... 433 14.2 Differential Scanning Calorimetry ........................................................... 433 14.2.1 Theory ........................................................................................ 433 14.2.2 Instrumentation ......................................................................... 434 14.2.3 Applications ................................................................................ 434 Contents xii Polymer Reference Book 14.3 Differential Thermal Analysis .................................................................. 438 14.3.1 Theory ........................................................................................ 438 14.3.2 Applications ................................................................................ 438 14.4 X-ray Powder Diffraction ........................................................................ 438 14.4.1 Applications ................................................................................ 438 14.5 Wide-Angle X-ray Scattering/Diffraction ................................................. 439 14.5.1 Applications ................................................................................ 439 14.6 Small Angle X-ray Diffraction Scattering and Positron Annihilation Lifetime Spectroscopy ......................................................... 440 14.6.1 Theory ........................................................................................ 440 14.6.2 Applications ................................................................................ 441 14.7 Static and Dynamic Light Scattering ........................................................ 441 14.7.1 Applications ................................................................................ 441 14.8 Infrared Spectroscopy .............................................................................. 442 14.8.1 Applications ................................................................................ 442 14.9 Nuclear Magnetic Resonance .................................................................. 444 14.9.1 Applications ................................................................................ 444 References ......................................................................................................... 445 15. Viscoelastic and Rheological Properties ............................................................. 453 15.1 Dynamic Mechanical Analysis ................................................................. 453 15.1.1 Theory ........................................................................................ 453 15.1.2 Instrumentation .......................................................................... 462 15.1.3 Applications ................................................................................ 463 15.2 Thermomechanical Analysis .................................................................... 472 15.2.1 Applications ................................................................................ 472 15.3 Dielectric Thermal Analysis ..................................................................... 474 15.3.1 Theory ........................................................................................ 474 15.3.2 Instrumentation .......................................................................... 474 15.3.3 Applications ................................................................................ 474 xiii 15.4 Further Viscoelastic Behaviour Studies ..................................................... 478 15.5 Further Rheology Studies ......................................................................... 479 References ......................................................................................................... 479 16. Thermal Properties ............................................................................................ 485 16.1 Linear Coeffi cient of Expansion ............................................................... 485 16.1.1 Dilatometric Method .................................................................. 485 16.2 Melting Temperature ............................................................................... 487 16.2.1 Thermal Methods ....................................................................... 487 16.2.2 Fisher-Johns Apparatus ............................................................... 489 16.3 Softening Point (Vicat) ............................................................................. 489 16.4 Heat Defl ection/Distortion Temperature .................................................. 489 16.4.1 Thermomechanical Analysis ........................................................ 489 16.4.2 Martens Method ......................................................................... 489 16.4.3 Vicat Softening Point Apparatus ................................................. 489 16.4.4 Dynamic Mechanical Analysis .................................................... 490 16.5 Brittleness Temperature (Low-Temperature Embrittlement) ..................... 490 16.6 Minimum Filming Temperature ............................................................... 490 16.7 Delamination Temperature ...................................................................... 490 16.8 Melt Flow Index ...................................................................................... 490 16.9 Heat of Volatilisation ............................................................................... 490 16.10 Thermal Conductivity .............................................................................. 490 16.11 Specifi c Heat ............................................................................................ 491 16.11.1 Transient Plane Source Technique ............................................... 491 16.11.2 Hot Wire Parallel Technique ....................................................... 491 16.12 Thermal Diffusivity ................................................................................. 491 16.13 Ageing in Air ........................................................................................... 491 References ......................................................................................................... 491 Contents xiv Polymer Reference Book 17. Flammability Testing ......................................................................................... 495 17.1 Combustion Testing and Rating of Plastics .............................................. 495 17.1.1 Introduction ................................................................................ 495 17.1.2 Mining Applications ................................................................... 498 17.1.3 Electrical Applications ................................................................ 499 17.1.4 Transportation Applications ....................................................... 500 17.1.5 Furniture and Furnishing Applications ........................................ 501 17.1.6 Construction Material Applications ............................................ 502 17.1.7 Other Fire-Related Factors .......................................................... 504 17.2 Instrumentation ....................................................................................... 505 17.3 Examination of Combustible Polymer Products ....................................... 505 17.4 Oxygen Consumption Cone Calorimetry ................................................. 507 17.5 Laser Pyrolysis–Time-of-Flight Mass Spectrometry .................................. 508 17.6 Pyrolysis–Gas Chromatography–Mass Spectrometry ............................... 508 17.7 Thermogravimetric Analysis .................................................................... 508 References ......................................................................................................... 509 18. Mechanical, Electrical, and Optical Properties .................................................. 517 18.1 Mechanical Properties of Polymers .......................................................... 517 18.1.1 Load-Bearing Characteristics of Polymers ................................... 518 18.1.2 Impact Strength Characteristics of Polymers ............................... 540 18.1.3 Measurement of Mechanical Properties in Polymers ................... 570 18.1.4 Properties of Polymer Film and Pipe ........................................... 584 18.1.5 Polymer Powders ........................................................................ 586 18.1.6 Physical Testing of Rubbers and Elastomers ................................ 591 18.2 Electrical Properties ................................................................................. 600 18.2.1 Volume and Surface Resistivity ................................................... 600 18.2.2 Dielectric and Dissipation Factor ................................................ 600 18.2.3 Dielectric Strength (Dielectric Rigidity) ....................................... 600 18.2.4 Surface Arc Resistance ................................................................ 600 18.2.5 Tracking Resistance .................................................................... 601 xv 18.3 Optical Properties and Light Stability ...................................................... 602 18.3.1 Stress Optical Analysis ................................................................ 602 18.3.2 Light Stability of Polyolefi ns ....................................................... 602 18.3.3 Effect of Pigments ....................................................................... 605 18.3.4 Effect of Pigments in Combination with a UV Stabiliser ............. 605 18.3.5 Effect of Carbon Black ................................................................ 613 18.3.6 Effect of Window Glass .............................................................. 614 18.3.7 Effect of Sunlight on Impact Strength .......................................... 615 18.3.8 Effect of Thickness ...................................................................... 615 18.3.9 Effect of Stress During Exposure ................................................. 616 18.3.10 Effect of Molecular Weight ......................................................... 618 18.3.11 Effect of Sunlight on the Surface Appearance of Pigmented Samples ...................................................................... 618 References ......................................................................................................... 620 19. Miscellaneous Physical and Chemical Properties ............................................... 631 19.1 Introduction ............................................................................................ 631 19.2 Particle Size Characteristics of Polymer Powders ..................................... 631 19.2.1 Methods Based on Electrical Sensing Zone (or Coulter Principle) .................................................................. 631 19.2.2 Laser Particle Size Analysers ....................................................... 634 19.2.3 Photon Correlation Spectroscopy (Autocorrelation Spectroscopy) ................................................... 636 19.2.4 Sedimentation ............................................................................. 637 19.2.5 Other Instrumentation ................................................................ 637 References ......................................................................................................... 638 20. Additive Migration from Packaged Commodities .............................................. 639 20.1 Polymer Additives .................................................................................... 640 20.2 Extraction Tests ....................................................................................... 642 References ......................................................................................................... 649 Contents xvi Polymer Reference Book Appendix 1 .............................................................................................................. 659 Instrument Suppliers .......................................................................................... 659 Thermal Properties of Polymers ......................................................................... 663 Mechanical Properties of Polymers .................................................................... 664 Physical Testing of Polymer Powders ................................................................. 667 Electrical Properties of Polymers ....................................................................... 666 Optical Properties of Polymers .......................................................................... 666 Physical Testing of Rubbers and Elastomers ...................................................... 666 Polymer Flammability Properties ....................................................................... 667 Addresses of Suppliers ....................................................................................... 670 Abbreviations and Acronyms ................................................................................... 683 Index ........................................................................................................................ 689 1Preface The aim of this book is to familiarise the reader with all aspects of the techniques used in the examination of polymers, covering chemical, physiochemical and purely physical methods of examination. It is the purpose of this book to describe the types of techniques now available to the polymer chemist and technician, and to discuss their capabilities, limitations and applications. All types of modern instrumentation are covered including those used in general quality control, research analysis, process monitoring and the mechanical, electrical, thermal and optical characteristics. Aspects such as automated analysis and computerised control of instruments are covered. The book is intended, therefore, for all staff, whether direct or peripheral, who are concerned with the instrumentation and methodology in the polymer laboratory including laboratory designers, engineers and chemists, and those concerned with the implementation of analytical specifi cations and process control limits. Practically all of the major newer instrumental techniques and many of the older classical techniques have been used to examine polymers and all of these are discussed in detail. The book covers not only instrumentation for the determination of metals, non metals, functional groups, polymer structural analysis and end-groups in the main types of polymers now in use commercially, but also the analysis of minor non-polymeric components of the polymer formulation, whether they be deliberately added, such as processing additives, or whether they occur adventitiously, such as residual volatiles and monomers and water. Fingerprinting techniques for the rapid identifi cation of polymers and methods for the examination of polymer surfaces and polymer defects are also discussed. Additionally, other features of polymer characterisation are discussed such as the determination of molecular weight, polymer fractionation techniques, chemical and thermal stability, resin cure, oxidative stability, photopolymers, glass and other transitions, crystallinity, viscoelasticity, rheological properties, thermal properties, fl ammability testing, particle size analysis and the measurement of the mechanical, electrical and optical properties of polymers. 2Polymer Reference Book Elemental analysis is now a well accepted method for the analysis of polymers and copolymers and their additive systems. Also, as so many different types of polymers are now used commercially it is advisable when attempting to identify a polymer and its additive system to classify it by fi rst carrying out an elemental analysis for metallic and non-metallic elements. Instrumentation discussed for carrying out these analyses include; atomic absorption spectrometry including its graphite furnace, atom trapping and vapour generation modifi cations, Zeeman atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry, visible ultraviolet spectroscopy, polarography and voltammetry, ion chromatography, x-ray fl uorescence spectroscopy and neutron activation analysis for metals (Chapter 1) and furnace combustion methods, oxygen fl ask combustion and x-ray fl uorescence spectroscopy for non-metallic elements (Chapter 2). Equally important, particularly in the case of copolymers, is the determination of functional groups. Frequently it is necessary to obtain a detailed picture of the microstructure of a polymer involving the determination of minor concentrations of functional and end-groups. Instrumentation discussed for carrying out this type of analysis (Chapter 3) includes, infrared and near infrared spectroscopy, Fourier transform infrared spectroscopy, NMR and PMR spectroscopy, and complimentary techniques such as reaction gas chromatography, pyrolysis gas chromatography mass spectrometry and pyrolysis gas chromatography - Fourier transform infrared spectroscopy. Recent work on the combination of pyrolysis with mass spectrometry and infrared spectroscopy is discussed in detail as well as work on new techniques for polymer characterisation such as time of fl ight secondary ion mass spectrometry (SIMS), x-ray photoelectron spectroscopy (XPS), tandem mass spectrometry (MS/MS), Fourier transform ion cyclotron mass spectrometry, matrix assisted laser description/ionisation mass spectrometry (MALDI/ MS), radiofrequency glow discharge mass spectrometry, microthermal analysis, atomic force microscopy

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