PLASTICS ADDITIVES

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Plastics AdditivesAdvanced Industrial Analysis

By

Jan C.J. BartDSM Research, The Netherlands

Amsterdam Berlin Oxford Tokyo Washington, DC

2006, The author.

All rights reserved. No part of this book may be reproduced, stored in a retrieval system,or transmitted, in any form or by any means, without prior written permission from the publisher.

The author and the publisher wish to thank Adri Geeve, DSM Coating Resins B.V. (Zwolle, The Netherlands) for providingthe cover image Analytical Website.

ISBN 1-58603-533-9Library of Congress Control Number: 2005931631

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LEGAL NOTICEThe publisher is not responsible for the use which might be made of the following information.

PRINTED IN THE NETHERLANDS

Table of Contents

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi

About the Author . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xv

Chapter 1 In-Polymer Spectroscopic Analysis of Additives . . . . . . . . . . . . . . . . 1

1.1. Direct Ultraviolet/Visible Spectrophotometry . . . . . . . . . . . . . . . . 41.1.1. Vapour-phase Ultraviolet Absorption Spectrometry . . . . . . . . . 10

1.2. Solid-state Vibrational Spectroscopies . . . . . . . . . . . . . . . . . . . . 111.2.1. Mid-infrared Spectroscopic Analysis . . . . . . . . . . . . . . . . . 141.2.2. Near-infrared Spectroscopy . . . . . . . . . . . . . . . . . . . . . . 341.2.3. Raman Spectroscopic Techniques . . . . . . . . . . . . . . . . . . . 52

1.3. Photoacoustic Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 661.4. Emission Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

1.4.1. Infrared Emission Spectroscopy . . . . . . . . . . . . . . . . . . . 721.4.2. Molecular Fluorescence Spectroscopy . . . . . . . . . . . . . . . . 751.4.3. Phosphorescence Spectroscopy . . . . . . . . . . . . . . . . . . . . 811.4.4. Chemiluminescence . . . . . . . . . . . . . . . . . . . . . . . . . . 82

1.5. Nuclear Spectroscopies . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941.5.1. Solid-state NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . 951.5.2. Nuclear Quadrupole Resonance . . . . . . . . . . . . . . . . . . . . 1101.5.3. Electron Spin Resonance Spectroscopy . . . . . . . . . . . . . . . 1121.5.4. Mssbauer Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . 120

1.6. Dielectric Loss Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 1231.7. Ultrasonic Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127

Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129General Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 129Direct UV/VIS Spectrophotometry . . . . . . . . . . . . . . . . . . 129Infrared Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 129Near-infrared Spectroscopy . . . . . . . . . . . . . . . . . . . . . . 130Raman Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 130Photoacoustics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130Emission Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . 131NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 131Electron Spin Resonance Spectroscopy . . . . . . . . . . . . . . . 131Dielectric Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . 131Polymer Characterisation . . . . . . . . . . . . . . . . . . . . . . . 131

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132

v

vi Table of Contents

Chapter 2 Polymer/Additive Analysis by Thermal Methods . . . . . . . . . . . . . . . . 155

2.1. Thermal Analysis Techniques . . . . . . . . . . . . . . . . . . . . . . . . . 1582.1.1. Differential Scanning Calorimetry . . . . . . . . . . . . . . . . . . 1632.1.2. Differential Thermal Analysis . . . . . . . . . . . . . . . . . . . . . 1732.1.3. Thermogravimetric Analysis . . . . . . . . . . . . . . . . . . . . . 1752.1.4. Simultaneous Thermal Analysis Methods . . . . . . . . . . . . . . 1892.1.5. (Multi)hyphenated Thermal Analysis Techniques . . . . . . . . . . 1922.1.6. Thermal Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 2092.1.7. Thermoluminescence . . . . . . . . . . . . . . . . . . . . . . . . . 213

2.2. Pyrolysis Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2142.2.1. PyrolysisGas Chromatography . . . . . . . . . . . . . . . . . . . . 2222.2.2. PyrolysisMass Spectrometry . . . . . . . . . . . . . . . . . . . . . 2352.2.3. PyrolysisGas ChromatographyMass Spectrometry . . . . . . . . 2442.2.4. PyrolysisFourier Transform Infrared Spectroscopy . . . . . . . . . 2612.2.5. PyrolysisGas ChromatographyFourier Transform Infrared

Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2632.2.6. PyrolysisGas ChromatographyAtomic Emission Detection . . . 2642.2.7. Temperature-programmed Pyrolysis . . . . . . . . . . . . . . . . . 266

2.3. Thermal Volatilisation and Desorption Techniques . . . . . . . . . . . . . 2752.3.1. Thermal Separation Techniques . . . . . . . . . . . . . . . . . . . . 2782.3.2. Direct Solid Sampling Techniques for Gas Chromatography . . . . 2822.3.3. Thermal DesorptionMass Spectrometric Techniques . . . . . . . . 299Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300

Thermal Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 300Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301Thermal Desorption . . . . . . . . . . . . . . . . . . . . . . . . . . 301

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301

Chapter 3 Lasers in Polymer/Additive Analysis . . . . . . . . . . . . . . . . . . . . . . . 325

3.1. Lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3253.2. Laser Ablation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331

3.2.1. Laser Ablation Plasma Source Spectrometry . . . . . . . . . . . . 3353.3. Laser Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341

3.3.1. Laser-induced Atomic and Molecular FluorescenceSpectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343

3.3.2. Laser-induced Breakdown Spectroscopy . . . . . . . . . . . . . . . 3463.4. Laser Desorption/Ionisation Methods . . . . . . . . . . . . . . . . . . . . . 353

3.4.1. Laser Desorption Mass Spectrometry . . . . . . . . . . . . . . . . . 3543.4.2. Laser Ionisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3633.4.3. Decoupled Laser Desorption/Ionisation . . . . . . . . . . . . . . . 3663.4.4. Matrix-assisted Laser Desorption/Ionisation . . . . . . . . . . . . . 3743.4.5. Laser Microprobe Mass Spectrometry . . . . . . . . . . . . . . . . 381

3.5. Laser Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392

Lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392Laser Ablation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392Laser Spectroscopy/Spectrometry . . . . . . . . . . . . . . . . . . . 392Laser-induced Chemistry . . . . . . . . . . . . . . . . . . . . . . . 393Laser Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393

Table of Contents vii

Chapter 4 Surface Analytical Techniques for Polymer/Additive Formulations . . . . . 403

4.1. Electron Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4084.1.1. Auger Electron Spectroscopy . . . . . . . . . . . . . . . . . . . . . 4094.1.2. X-ray Photoelectron Spectroscopy . . . . . . . . . . . . . . . . . . 411

4.2. Surface Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . 4204.2.1. Secondary Ion Mass Spectrometry . . . . . . . . . . . . . . . . . . 4224.2.2. Secondary Neutral Mass Spectrometry . . . . . . . . . . . . . . . . 439

4.3. Ion Scattering Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . 4414.3.1. Low-energy Ion Scattering . . . . . . . . . . . . . . . . . . . . . . 4434.3.2. Rutherford Backscattering Spectroscopy . . . . . . . . . . . . . . . 444Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446

Surface Characterisation . . . . . . . . . . . . . . . . . . . . . . . . 446Electron Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 447Surface Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . 447Ion Scattering Techniques . . . . . . . . . . . . . . . . . . . . . . . 447

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447

Chapter 5 Microscopy and Microanalysis of Polymer/Additive Formulations . . . . . . 455

5.1. Chemical Microanalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4585.2. Microscopy and Imaging Techniques . . . . . . . . . . . . . . . . . . . . . 4605.3. Light Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464

5.3.1. Conventional Optical Microscopy . . . . . . . . . . . . . . . . . . 4665.3.2. Ultraviolet Microscopy . . . . . . . . . . . . . . . . . . . . . . . . 4725.3.3. Fluorescence Microscopy . . . . . . . . . . . . . . . . . . . . . . . 4755.3.4. Confocal and Laser Microscopy . . . . . . . . . . . . . . . . . . . 478

5.4. Electron Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4835.4.1. Scanning Electron Microscopy . . . . . . . . . . . . . . . . . . . . 4855.4.2. Transmission Electron Microscopy . . . . . . . . . . . . . . . . . . 4945.4.3. Analytical Electron Microscopy . . . . . . . . . . . . . . . . . . . 497

5.5. Scanning Probe Microscopy Techniques . . . . . . . . . . . . . . . . . . . 5015.5.1. Atomic Force Microscopy . . . . . . . . . . . . . . . . . . . . . . . 5045.5.2. Near-field Scanning Optical Microscopy . . . . . . . . . . . . . . . 5115.5.3. Scanning Kelvin Microscopy . . . . . . . . . . . . . . . . . . . . . 514

5.6. Microspectroscopic Imaging of Additives . . . . . . . . . . . . . . . . . . 5145.6.1. UV/Visible Microspectroscopy . . . . . . . . . . . . . . . . . . . . 5195.6.2. Infrared Microspectroscopy and Imaging . . . . . . . . . . . . . . 5215.6.3. Laser-Raman Microprobe and Microscopy . . . . . . . . . . . . . . 5325.6.4. Fluorescence and Luminescence Imaging . . . . . . . . . . . . . . 541

5.7. Magnetic Resonance Imaging . . . . . . . . . . . . . . . . . . . . . . . . . 5465.7.1. Nuclear Magnetic Resonance Imaging . . . . . . . . . . . . . . . . 5475.7.2. Electron Spin Resonance Imaging . . . . . . . . . . . . . . . . . . 555

5.8. X-ray Microscopy and Microspectroscopy . . . . . . . . . . . . . . . . . . 5595.8.1. X-ray Microradiography . . . . . . . . . . . . . . . . . . . . . . . . 5605.8.2. Scanning X-ray Microscopy . . . . . . . . . . . . . . . . . . . . . . 5615.8.3. X-ray Microfluorescence . . . . . . . . . . . . . . . . . . . . . . . 5635.8.4. Micro X-ray Photoelectron Spectroscopy . . . . . . . . . . . . . . 564

5.9. Ion Imaging of Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . 5665.9.1. Laser-microprobe Mapping . . . . . . . . . . . . . . . . . . . . . . 5665.9.2. Imaging Secondary Ion Mass Spectrometry . . . . . . . . . . . . . 567

viii Table of Contents

Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573Light Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . 573Electron Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 573Scanning Probe Microscopy . . . . . . . . . . . . . . . . . . . . . . 574Near-field Optics . . . . . . . . . . . . . . . . . . . . . . . . . . . . 574Microbeam Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . 574Microspectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . 575Imaging/Image Analysis . . . . . . . . . . . . . . . . . . . . . . . . 575Polymer Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 575General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576

Chapter 6 Quantitative Analysis of Additives in Polymers . . . . . . . . . . . . . . . . . 5976.1. Sampling Procedures for Quantitative Analysis of Polymer/Additive

Packages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6006.1.1. Quantitative Analysis of Mineral Filled Engineering Plastics . . . . 6056.1.2. Reverse Engineering of Cured Rubber Compounds . . . . . . . . . 6066.1.3. Determination of Additive Blends in Polymers . . . . . . . . . . . 606

6.2. Quantitative Solvent and Thermal Extraction . . . . . . . . . . . . . . . . 6096.2.1. Extraction and Quantification of Polyolefin Additives . . . . . . . . 6136.2.2. Supercritical Fluid Extraction . . . . . . . . . . . . . . . . . . . . . 6146.2.3. Quantification of Antioxidants in Polyolefins . . . . . . . . . . . . 6156.2.4. Determination of Plasticisers by Solvent and Thermal Extraction . 6196.2.5. Oil-extended EPDM . . . . . . . . . . . . . . . . . . . . . . . . . . 6236.2.6. Migration Rates of Phthalate Esters from Soft PVC Products . . . . 624

6.3. Quantitative Chromatographic Methods . . . . . . . . . . . . . . . . . . . 6246.3.1. Quantitative Gas Chromatography . . . . . . . . . . . . . . . . . . 6266.3.2. Quantitative Liquid Chromatography . . . . . . . . . . . . . . . . . 6286.3.3. Quantitative Supercritical Fluid Chromatography . . . . . . . . . . 6296.3.4. Quantitative Thin-layer Chromatography . . . . . . . . . . . . . . 630

6.4. Quantitative Spectroscopic Techniques . . . . . . . . . . . . . . . . . . . . 6336.4.1. Quantitative Ultraviolet/Visible Spectrophotometry . . . . . . . . . 6376.4.2. Quantitative Fluorescence Spectroscopy . . . . . . . . . . . . . . . 6396.4.3. Quantitative Infrared Spectroscopy . . . . . . . . . . . . . . . . . . 6396.4.4. Quantitative Near-infrared Spectroscopy . . . . . . . . . . . . . . . 6446.4.5. Quantitative Raman Spectroscopy . . . . . . . . . . . . . . . . . . 6456.4.6. Quantitative Nuclear Magnetic Resonance Methods . . . . . . . . . 646

6.5. Quantitative Mass Spectrometric Techniques . . . . . . . . . . . . . . . . 6476.6. Quantitative Surface Analysis Techniques . . . . . . . . . . . . . . . . . . 6516.7. Quantitative Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 653

Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 654General Quantitative Analysis . . . . . . . . . . . . . . . . . . . . . 654Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 654Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . 654Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 655Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . 655Surface Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 655Chemometric Techniques . . . . . . . . . . . . . . . . . . . . . . . 655

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 655

Table of Contents ix

Chapter 7 Process Analytics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663

7.1. In-process Analysers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6677.2. Process Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675

7.2.1. Remote Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 6777.2.2. Process Electronic Spectroscopy . . . . . . . . . . . . . . . . . . . 6797.2.3. Mid-infrared Process Analysis of Polymer Formulations . . . . . . 6837.2.4. Near-infrared Spectroscopic Process Analysis . . . . . . . . . . . . 6937.2.5. Process Raman Spectroscopy . . . . . . . . . . . . . . . . . . . . . 7017.2.6. Process Nuclear Magnetic Resonance . . . . . . . . . . . . . . . . 7047.2.7. Acoustic Emission Technology . . . . . . . . . . . . . . . . . . . . 7167.2.8. Real-time Dielectric Spectroscopy . . . . . . . . . . . . . . . . . . 719

7.3. Process Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . 7207.4. In Situ Elemental Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 721

Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 722Process Analytical Chemistry . . . . . . . . . . . . . . . . . . . . . 722Process Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 722Process Data Analysis . . . . . . . . . . . . . . . . . . . . . . . . . 723

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 723

Chapter 8 Modern Analytical Method Development and Validation . . . . . . . . . . . 731

8.1. Status of Existing Methods for Polymer/Additive Analysis . . . . . . . . . 7328.2. In-polymer Additive Analysis: Method Development and Optimisation . . 7328.3. Certified Reference Materials . . . . . . . . . . . . . . . . . . . . . . . . . 7368.4. Analytical Method Validation Approaches . . . . . . . . . . . . . . . . . . 746

8.4.1. Analytical Performance Parameters . . . . . . . . . . . . . . . . . . 7518.4.2. Interlaboratory Collaborative Studies . . . . . . . . . . . . . . . . . 7558.4.3. Validation of Antioxidant Migration Testing . . . . . . . . . . . . . 757

8.5. Total Validation Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7578.5.1. Software/Hardware Validation/Qualification . . . . . . . . . . . . . 7588.5.2. System Suitability . . . . . . . . . . . . . . . . . . . . . . . . . . . 760

8.6. Rational Step-by-step Method Development and Validation forPolymer/Additive Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . 760Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 762

Method Development and Validation . . . . . . . . . . . . . . . . . 762Reference Materials . . . . . . . . . . . . . . . . . . . . . . . . . . 762

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 762

Appendix: List of Symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 767

Acronyms of Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . 767Chemical Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778

Polymers and Products . . . . . . . . . . . . . . . . . . . . . . . . . 778Additives/Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . 780

Physical and Mathematical Symbols . . . . . . . . . . . . . . . . . . . . . 785Physical and Mathematical Greek Symbols . . . . . . . . . . . . . 789

General Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 790

Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 793

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Preface

Modern polymer/additive deformulation is essentially carried out according to three different approaches, inincreasing order of sophistication, namely analysis of analytes separated from the polymer (typically an ex-tract), of analytes and polymer in solution, or directly in-polymer (solid state or melt). The current status ofconventional, indirect, methods of deformulation of polymer/additive extracts and dissolutions has recentlybeen described in a comprehensive fashion. However, there is an impelling need to tackle polymer/additivedeformulations strategically in an ever-increasing order of sophistication in analytical ingenuity, from indirectto direct analysis procedures, from macro to micro, from slow to rapid, from close to remote, from lab toprocess. Established wet chemical routes for low-molecular-weight additives are frequently no option for an-alytical problems of considerable complexity (high-molecular-weight additives, grafting, incorporation in thepolymer backbone, reactive systems, etc.) or in case of surface analysis, microanalysis and spatially resolvedanalysis. Profiling, process analysis, product safety, quality assurance and industrial troubleshooting all benefitfrom direct analysis modes.

In recent years, techniques for direct analysis of the non-polymer components have developed apace andit has become increasingly important for scientists, engineers and technicians to have a basic grounding inthese methods. This treatise is concerned with the in situ characterisation of additives embedded in a broadvariety of polymeric matrices and evaluates critically the extensive problem-solving experience and state-of-the-art in the polymer industry. Despite well-deserved attention and considerable efforts direct polymer/additiveanalysis (without separation) has not yet turned into a great many general and routinely workable concepts.Nevertheless, the future foresees a greater share for in-polymer analysis.

This book, containing an outline of the principles and characteristics of relevant instrumental techniques(without unnecessary detail), provides an in-depth overview of various aspects of direct additive analysis byfocusing on a wide array of applications in R&D, production, quality control and technical service. The bookdescribes the fundamental characteristics of the arsenal of techniques utilised industrially in direct relationto application in real-life polymer/additive analysis. Instrumental methods are categorised according to gen-eral deformulation principles with emphasis on promoting understanding and on effective problem solving.The chapters are replete with selected and more common applications illustrating why particular additives areanalysed by a specific method. The value of the book stays in the applications.

In Plastics Additives: Advanced Industrial Analysis the author has attempted to bring together many recentdevelopments in the field in order to provide the reader with valuable insight into current trends and thinking.For each individual technique more excellent textbooks are available, properly referenced, albeit with less focuson the analysis of additives in polymers.

As an alternative to wet chemical routes of analysis, this monograph deals mainly with the direct deformu-lation of solid polymer/additive compounds. In Chapter 1 in-polymer spectroscopic analysis of additives bymeans of UV/VIS, FTIR, near-IR, Raman, fluorescence spectroscopy, high-resolution solid-state NMR, ESR,Mssbauer and dielectric resonance spectroscopy is considered with a wide coverage of experimental data.Chapter 2 deals mainly with thermal extraction (as opposed to solvent extraction) of additives and volatilesfrom polymeric material by means of (hyphenated) thermal analysis, pyrolysis and thermal desorption tech-niques. Use and applications of various laser-based techniques (ablation, spectroscopy, desorption/ionisationand pyrolysis) to polymer/additive analysis are described in Chapter 3 and are critically evaluated. Chapter 4gives particular emphasis to the determination of additives on polymeric surfaces. The classical methods of

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surface analysis (electron spectroscopy, surface mass spectrometry and ion scattering techniques) are appliedto practical cases. A variety of options for (surface) microanalysis and spatially resolved analysis by meansof microscopy, microspectroscopy, spectromicroscopy, and imaging techniques, as applied to polymer/additivematerials, are discussed in Chapter 5. Quantitative analysis (Chapter 6) in an essential part of polymer/additiveanalysis, in particular in the industrial environment. For quantitation, the separation procedure can be the mostimportant factor for success or failure of the analysis. While this analytical task is recognised to be considerablymore difficult than the qualitative analysis of previous chapters, recent round-robins indicate the need for criti-cal self-inspection of the polymer analytical community. In Chapter 7 the various tools for in-process analysis(UV/VIS, mid-IR, near-IR, Raman and low-resolution NMR) are applied to polymer melts. The current statusof polymer/additive analytical methodology is described in Chapter 8 and optimisation procedures are outlined.The lack of certified reference materials hampers analytical method validation. A rational step-by-step methoddevelopment and validation approach to polymer/additive analysis is described.

Each chapter of this monograph is essentially self-contained. The reader may consult any sub-chapter indi-vidually. To facilitate rapid scanning the text has been provided with eye-catchers. Each chapter concludes withup-to-date references to the primary literature (no patent literature) and a critical list of recommended generalreading (books, reviews) for greater insight. The majority of references in the text are from recent publications(19802003 and beyond). The book ends with a glossary of symbols and an index compiled with respect toboth instrumental methods and analytes. Although every effort has been made to keep the book up-to-date withthe latest methodological developments this report represents only work in evolution and contains suggestionsfor future improvements. In J.R. Thorbeckes words De tijd om alles te zeggen is nog niet gekomen, or Timeis not yet ripe to tell everything.

Geleen, December 2004

About the Author

Jan C. J. Bart (PhD Structural Chemistry, University of Amsterdam) is a senior scientist with a wide interest inmaterials characterisation, heterogeneous catalysis and product development who has gained broad industrialexperience (Monsanto, Montedison, DSM) in various countries. The contents of this book derive from theauthors experience as a previous Head of an Analytical Research Department concerned with polyolefins andengineering plastics at a major plastics producer and are also based on an extensive evaluation of the literature.Dr. Bart has held several teaching assignments (Universities of Amsterdam, Sassari and Pavia), researchedextensively in both academic and industrial areas, and authored over 250 scientific papers and chapters in books;he is also author of the related monograph on Additives in Polymers. Industrial Analysis and Applications,John Wiley & Sons, Chichester (2005). Dr. Bart has acted as Ramsay Memorial Fellow at the Universitiesof Leeds (Colour Chemistry) and Oxford (Material Science), visiting scientist at the Institut de Recherchessur la Catalyse (CNRS, Villeurbanne), and Meyerhoff Visiting Professor at the Weizmann Institute of Science(Rehovoth, Israel), and held an Invited Professorship at the University of Science and Technology of China(Hefei, PRC). He is currently a Full Professor of Industrial Chemistry at the University of Messina (Italy).

He is also a member of the Royal Dutch Chemical Society, Royal Society of Chemistry, Society of PlasticsEngineers, the Institute of Materials and Associazione Italiana delle Macromolecole.

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Acknowledgements

This monograph describes the current state-of-the-art in direct polymer/additive analysis. The high degree ofcreativity and ingenuity within the international scientific community is both amazing and inspiring. The sizeof the book shows the high overall productivity in academia and in industry. Yet, only a fraction of the pertinentliterature was cited.

The author wishes to thank in particular DSM for actively stimulating the work, for granting permissionfor publication and financial support. The author thanks colleagues (at DSM Research) and former colleagues(now at SABIC Europe) for reviewing various chapters of the book. Information Services at DSM Researchhave been crucial in providing much needed access to literature. Each chapter saw many revised versions.Without the expert help and endurance of Mrs. Coba Hendriks, who produced many word-processed issueswith endless patience, it would not have been possible to complete this work successfully. The author has notfailed to disturb relatives and friends during the many years of preparation of this text, notably in Bucharestand Messina. Without their understanding and hospitality this book would never have been finished.

The author expresses his gratitude to peer reviewers of this project for recommendation to the publisher andthanks editor and members of staff at IOS Press for their professional assistance and guidance from manuscriptto printed volume. The kind permission granted by journal publishers, book editors and equipment producers touse illustrations and tables from other sources is gratefully acknowledged. The exact references are given in thefigure and table captions. Every effort has been made to contact copyright holders of any material reproducedwithin the text and the author apologises if any have been overlooked.

Jan C. J. Bart

Geleen, December 2004

Disclaimer:The views and opinions expressed by the author do not necessarily reflect those of DSM Research or theeditor. No responsibility or liability of any nature shall attach to DSM arising out of or in connection with anyutilisation in any form of any material contained therein.

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