PLASTICS ADDITIVES

This page intentionally left blank

Plastics Additives
Advanced Industrial Analysis

By

Jan C.J. Bart

DSM 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 providing
the cover image Analytical Website.
ISBN 1-58603-533-9
Library of Congress Control Number: 2005931631
Publisher
IOS Press
Nieuwe Hemweg 6B
1013 BG Amsterdam
Netherlands
fax: +31 20 687 0019
e-mail: order@iospress.nl

Distributor in the UK and Ireland

Gazelle Books
Falcon House
Queen Square
Lancaster LA1 1RN
United Kingdom
fax: +44 1524 63232

Distributor in the USA and Canada

IOS Press, Inc.
4502 Rachael Manor Drive
Fairfax, VA 22032
USA
fax: +1 703 323 3668
e-mail: iosbooks@iospress.com

LEGAL NOTICE
The 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 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chapter 1

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

1.1. Direct Ultraviolet/Visible Spectrophotometry . . . . . . .
1.1.1. Vapour-phase Ultraviolet Absorption Spectrometry
1.2. Solid-state Vibrational Spectroscopies . . . . . . . . . . .
1.2.1. Mid-infrared Spectroscopic Analysis . . . . . . . .
1.2.2. Near-infrared Spectroscopy . . . . . . . . . . . . .
1.2.3. Raman Spectroscopic Techniques . . . . . . . . . .
1.3. Photoacoustic Spectroscopy . . . . . . . . . . . . . . . . .
1.4. Emission Spectroscopy . . . . . . . . . . . . . . . . . . .
1.4.1. Infrared Emission Spectroscopy . . . . . . . . . .
1.4.2. Molecular Fluorescence Spectroscopy . . . . . . .
1.4.3. Phosphorescence Spectroscopy . . . . . . . . . . .
1.4.4. Chemiluminescence . . . . . . . . . . . . . . . . .
1.5. Nuclear Spectroscopies . . . . . . . . . . . . . . . . . . .
1.5.1. Solid-state NMR Spectroscopy . . . . . . . . . . .
1.5.2. Nuclear Quadrupole Resonance . . . . . . . . . . .
1.5.3. Electron Spin Resonance Spectroscopy . . . . . .
1.5.4. Mssbauer Spectroscopy . . . . . . . . . . . . . .
1.6. Dielectric Loss Spectroscopy . . . . . . . . . . . . . . . .
1.7. Ultrasonic Spectroscopy . . . . . . . . . . . . . . . . . . .
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . .
General Spectroscopy . . . . . . . . . . . . . . . .
Direct UV/VIS Spectrophotometry . . . . . . . . .
Infrared Spectroscopy . . . . . . . . . . . . . . . .
Near-infrared Spectroscopy . . . . . . . . . . . . .
Raman Spectroscopy . . . . . . . . . . . . . . . . .
Photoacoustics . . . . . . . . . . . . . . . . . . . .
Emission Spectroscopy . . . . . . . . . . . . . . .
NMR Spectroscopy . . . . . . . . . . . . . . . . .
Electron Spin Resonance Spectroscopy . . . . . .
Dielectric Spectroscopy . . . . . . . . . . . . . . .
Polymer Characterisation . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . .

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

xv
1
4
10
11
14
34
52
66
72
72
75
81
82
94
95
110
112
120
123
127
129
129
129
129
130
130
130
131
131
131
131
131
132
v

vi

Chapter 2

Table of Contents

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

2.1. Thermal Analysis Techniques . . . . . . . . . . . . . . . . . . . . . .
2.1.1. Differential Scanning Calorimetry . . . . . . . . . . . . . . .
2.1.2. Differential Thermal Analysis . . . . . . . . . . . . . . . . . .
2.1.3. Thermogravimetric Analysis . . . . . . . . . . . . . . . . . .
2.1.4. Simultaneous Thermal Analysis Methods . . . . . . . . . . .
2.1.5. (Multi)hyphenated Thermal Analysis Techniques . . . . . . .
2.1.6. Thermal Microscopy . . . . . . . . . . . . . . . . . . . . . . .
2.1.7. Thermoluminescence . . . . . . . . . . . . . . . . . . . . . .
2.2. Pyrolysis Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1. PyrolysisGas Chromatography . . . . . . . . . . . . . . . . .
2.2.2. PyrolysisMass Spectrometry . . . . . . . . . . . . . . . . . .
2.2.3. PyrolysisGas ChromatographyMass Spectrometry . . . . .
2.2.4. PyrolysisFourier Transform Infrared Spectroscopy . . . . . .
2.2.5. PyrolysisGas ChromatographyFourier Transform Infrared
Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.6. PyrolysisGas ChromatographyAtomic Emission Detection
2.2.7. Temperature-programmed Pyrolysis . . . . . . . . . . . . . .
2.3. Thermal Volatilisation and Desorption Techniques . . . . . . . . . .
2.3.1. Thermal Separation Techniques . . . . . . . . . . . . . . . . .
2.3.2. Direct Solid Sampling Techniques for Gas Chromatography .
2.3.3. Thermal DesorptionMass Spectrometric Techniques . . . . .
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Thermal Analysis . . . . . . . . . . . . . . . . . . . . . . . .
Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Thermal Desorption . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Chapter 3

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

158
163
173
175
189
192
209
213
214
222
235
244
261

.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.

263
264
266
275
278
282
299
300
300
301
301
301

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

3.1. Lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. Laser Ablation . . . . . . . . . . . . . . . . . . . . . . . .
3.2.1. Laser Ablation Plasma Source Spectrometry . . .
3.3. Laser Spectroscopy . . . . . . . . . . . . . . . . . . . . . .
3.3.1. Laser-induced Atomic and Molecular Fluorescence
Spectrometry . . . . . . . . . . . . . . . . . . . . .
3.3.2. Laser-induced Breakdown Spectroscopy . . . . . .
3.4. Laser Desorption/Ionisation Methods . . . . . . . . . . . .
3.4.1. Laser Desorption Mass Spectrometry . . . . . . . .
3.4.2. Laser Ionisation . . . . . . . . . . . . . . . . . . .
3.4.3. Decoupled Laser Desorption/Ionisation . . . . . .
3.4.4. Matrix-assisted Laser Desorption/Ionisation . . . .
3.4.5. Laser Microprobe Mass Spectrometry . . . . . . .
3.5. Laser Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . .
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . .
Lasers . . . . . . . . . . . . . . . . . . . . . . . . .
Laser Ablation . . . . . . . . . . . . . . . . . . . .
Laser Spectroscopy/Spectrometry . . . . . . . . . .
Laser-induced Chemistry . . . . . . . . . . . . . .
Laser Safety . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . .

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

325
331
335
341

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

343
346
353
354
363
366
374
381
388
392
392
392
392
393
393
393

Table of Contents

Chapter 4

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

4.1. Electron Spectroscopy . . . . . . . . . . . . . .
4.1.1. Auger Electron Spectroscopy . . . . . .
4.1.2. X-ray Photoelectron Spectroscopy . . .
4.2. Surface Mass Spectrometry . . . . . . . . . . .
4.2.1. Secondary Ion Mass Spectrometry . . .
4.2.2. Secondary Neutral Mass Spectrometry .
4.3. Ion Scattering Techniques . . . . . . . . . . . .
4.3.1. Low-energy Ion Scattering . . . . . . .
4.3.2. Rutherford Backscattering Spectroscopy
Bibliography . . . . . . . . . . . . . . . . . . .
Surface Characterisation . . . . . . . . .
Electron Spectroscopy . . . . . . . . . .
Surface Mass Spectrometry . . . . . . .
Ion Scattering Techniques . . . . . . . .
References . . . . . . . . . . . . . . . . . . . .

Chapter 5

vii

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

408
409
411
420
422
439
441
443
444
446
446
447
447
447
447

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

5.1. Chemical Microanalysis . . . . . . . . . . . . . . .
5.2. Microscopy and Imaging Techniques . . . . . . . .
5.3. Light Microscopy . . . . . . . . . . . . . . . . . .
5.3.1. Conventional Optical Microscopy . . . . .
5.3.2. Ultraviolet Microscopy . . . . . . . . . . .
5.3.3. Fluorescence Microscopy . . . . . . . . . .
5.3.4. Confocal and Laser Microscopy . . . . . .
5.4. Electron Microscopy . . . . . . . . . . . . . . . . .
5.4.1. Scanning Electron Microscopy . . . . . . .
5.4.2. Transmission Electron Microscopy . . . . .
5.4.3. Analytical Electron Microscopy . . . . . .
5.5. Scanning Probe Microscopy Techniques . . . . . .
5.5.1. Atomic Force Microscopy . . . . . . . . . .
5.5.2. Near-field Scanning Optical Microscopy . .
5.5.3. Scanning Kelvin Microscopy . . . . . . . .
5.6. Microspectroscopic Imaging of Additives . . . . .
5.6.1. UV/Visible Microspectroscopy . . . . . . .
5.6.2. Infrared Microspectroscopy and Imaging .
5.6.3. Laser-Raman Microprobe and Microscopy .
5.6.4. Fluorescence and Luminescence Imaging .
5.7. Magnetic Resonance Imaging . . . . . . . . . . . .
5.7.1. Nuclear Magnetic Resonance Imaging . . .
5.7.2. Electron Spin Resonance Imaging . . . . .
5.8. X-ray Microscopy and Microspectroscopy . . . . .
5.8.1. X-ray Microradiography . . . . . . . . . . .
5.8.2. Scanning X-ray Microscopy . . . . . . . . .
5.8.3. X-ray Microfluorescence . . . . . . . . . .
5.8.4. Micro X-ray Photoelectron Spectroscopy .
5.9. Ion Imaging of Additives . . . . . . . . . . . . . .
5.9.1. Laser-microprobe Mapping . . . . . . . . .
5.9.2. Imaging Secondary Ion Mass Spectrometry

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

458
460
464
466
472
475
478
483
485
494
497
501
504
511
514
514
519
521
532
541
546
547
555
559
560
561
563
564
566
566
567

viii

Table of Contents

Bibliography . . . . . . . . . . . . .
Light Microscopy . . . . . .
Electron Microscopy . . . . .
Scanning Probe Microscopy .
Near-field Optics . . . . . . .
Microbeam Analysis . . . . .
Microspectroscopy . . . . . .
Imaging/Image Analysis . . .
Polymer Microscopy . . . . .
General . . . . . . . . . . . .
References . . . . . . . . . . . . . .
Chapter 6

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

573
573
573
574
574
574
575
575
575
576
576

Quantitative Analysis of Additives in Polymers . . . . . . . . . . . . . . . . . 597

6.1. Sampling Procedures for Quantitative Analysis of Polymer/Additive
Packages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.1.1. Quantitative Analysis of Mineral Filled Engineering Plastics . . .
6.1.2. Reverse Engineering of Cured Rubber Compounds . . . . . . . .
6.1.3. Determination of Additive Blends in Polymers . . . . . . . . . .
6.2. Quantitative Solvent and Thermal Extraction . . . . . . . . . . . . . . .
6.2.1. Extraction and Quantification of Polyolefin Additives . . . . . . .
6.2.2. Supercritical Fluid Extraction . . . . . . . . . . . . . . . . . . . .
6.2.3. Quantification of Antioxidants in Polyolefins . . . . . . . . . . .
6.2.4. Determination of Plasticisers by Solvent and Thermal Extraction
6.2.5. Oil-extended EPDM . . . . . . . . . . . . . . . . . . . . . . . . .
6.2.6. Migration Rates of Phthalate Esters from Soft PVC Products . . .
6.3. Quantitative Chromatographic Methods . . . . . . . . . . . . . . . . . .
6.3.1. Quantitative Gas Chromatography . . . . . . . . . . . . . . . . .
6.3.2. Quantitative Liquid Chromatography . . . . . . . . . . . . . . . .
6.3.3. Quantitative Supercritical Fluid Chromatography . . . . . . . . .
6.3.4. Quantitative Thin-layer Chromatography . . . . . . . . . . . . .
6.4. Quantitative Spectroscopic Techniques . . . . . . . . . . . . . . . . . . .
6.4.1. Quantitative Ultraviolet/Visible Spectrophotometry . . . . . . . .
6.4.2. Quantitative Fluorescence Spectroscopy . . . . . . . . . . . . . .
6.4.3. Quantitative Infrared Spectroscopy . . . . . . . . . . . . . . . . .
6.4.4. Quantitative Near-infrared Spectroscopy . . . . . . . . . . . . . .
6.4.5. Quantitative Raman Spectroscopy . . . . . . . . . . . . . . . . .
6.4.6. Quantitative Nuclear Magnetic Resonance Methods . . . . . . . .
6.5. Quantitative Mass Spectrometric Techniques . . . . . . . . . . . . . . .
6.6. Quantitative Surface Analysis Techniques . . . . . . . . . . . . . . . . .
6.7. Quantitative Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . .
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
General Quantitative Analysis . . . . . . . . . . . . . . . . . . . .
Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . .
Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . .
Surface Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chemometric Techniques . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

600
605
606
606
609
613
614
615
619
623
624
624
626
628
629
630
633
637
639
639
644
645
646
647
651
653
654
654
654
654
655
655
655
655
655

Table of Contents

Chapter 7

ix

Process Analytics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663

7.1. In-process Analysers . . . . . . . . . . . . . . . . . . . . . . . .
7.2. Process Spectroscopy . . . . . . . . . . . . . . . . . . . . . . .
7.2.1. Remote Spectroscopy . . . . . . . . . . . . . . . . . . .
7.2.2. Process Electronic Spectroscopy . . . . . . . . . . . . .
7.2.3. Mid-infrared Process Analysis of Polymer Formulations
7.2.4. Near-infrared Spectroscopic Process Analysis . . . . . .
7.2.5. Process Raman Spectroscopy . . . . . . . . . . . . . . .
7.2.6. Process Nuclear Magnetic Resonance . . . . . . . . . .
7.2.7. Acoustic Emission Technology . . . . . . . . . . . . . .
7.2.8. Real-time Dielectric Spectroscopy . . . . . . . . . . . .
7.3. Process Chromatography . . . . . . . . . . . . . . . . . . . . .
7.4. In Situ Elemental Analysis . . . . . . . . . . . . . . . . . . . . .
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Process Analytical Chemistry . . . . . . . . . . . . . . .
Process Spectroscopy . . . . . . . . . . . . . . . . . . .
Process Data Analysis . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Chapter 8

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

667
675
677
679
683
693
701
704
716
719
720
721
722
722
722
723
723

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

8.1.
8.2.
8.3.
8.4.

Status of Existing Methods for Polymer/Additive Analysis . . . . . . .

In-polymer Additive Analysis: Method Development and Optimisation
Certified Reference Materials . . . . . . . . . . . . . . . . . . . . . . .
Analytical Method Validation Approaches . . . . . . . . . . . . . . . .
8.4.1. Analytical Performance Parameters . . . . . . . . . . . . . . . .
8.4.2. Interlaboratory Collaborative Studies . . . . . . . . . . . . . . .
8.4.3. Validation of Antioxidant Migration Testing . . . . . . . . . . .
8.5. Total Validation Process . . . . . . . . . . . . . . . . . . . . . . . . . .
8.5.1. Software/Hardware Validation/Qualification . . . . . . . . . . .
8.5.2. System Suitability . . . . . . . . . . . . . . . . . . . . . . . . .
8.6. Rational Step-by-step Method Development and Validation for
Polymer/Additive Analysis . . . . . . . . . . . . . . . . . . . . . . . .
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Method Development and Validation . . . . . . . . . . . . . . .
Reference Materials . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

732
732
736
746
751
755
757
757
758
760

.
.
.
.
.

.
.
.
.
.

760
762
762
762
762

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

Acronyms of Techniques . . . . . . . . . . . . . .
Chemical Nomenclature . . . . . . . . . . . . . . .
Polymers and Products . . . . . . . . . . . .
Additives/Chemicals . . . . . . . . . . . . .
Physical and Mathematical Symbols . . . . . . . .
Physical and Mathematical Greek Symbols
General Abbreviations . . . . . . . . . . . . . . . .

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

767
778
778
780
785
789
790

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

This page intentionally left blank

Preface
Modern polymer/additive deformulation is essentially carried out according to three different approaches, in
increasing order of sophistication, namely analysis of analytes separated from the polymer (typically an extract), of analytes and polymer in solution, or directly in-polymer (solid state or melt). The current status of
conventional, indirect, methods of deformulation of polymer/additive extracts and dissolutions has recently
been described in a comprehensive fashion. However, there is an impelling need to tackle polymer/additive
deformulations strategically in an ever-increasing order of sophistication in analytical ingenuity, from indirect
to direct analysis procedures, from macro to micro, from slow to rapid, from close to remote, from lab to
process. Established wet chemical routes for low-molecular-weight additives are frequently no option for analytical problems of considerable complexity (high-molecular-weight additives, grafting, incorporation in the
polymer backbone, reactive systems, etc.) or in case of surface analysis, microanalysis and spatially resolved
analysis. Profiling, process analysis, product safety, quality assurance and industrial troubleshooting all benefit
from direct analysis modes.
In recent years, techniques for direct analysis of the non-polymer components have developed apace and
it has become increasingly important for scientists, engineers and technicians to have a basic grounding in
these methods. This treatise is concerned with the in situ characterisation of additives embedded in a broad
variety of polymeric matrices and evaluates critically the extensive problem-solving experience and state-ofthe-art in the polymer industry. Despite well-deserved attention and considerable efforts direct polymer/additive
analysis (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 by
focusing on a wide array of applications in R&D, production, quality control and technical service. The book
describes the fundamental characteristics of the arsenal of techniques utilised industrially in direct relation
to application in real-life polymer/additive analysis. Instrumental methods are categorised according to general 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 are
analysed 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 recent
developments 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 focus
on the analysis of additives in polymers.
As an alternative to wet chemical routes of analysis, this monograph deals mainly with the direct deformulation of solid polymer/additive compounds. In Chapter 1 in-polymer spectroscopic analysis of additives by
means 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 volatiles
from polymeric material by means of (hyphenated) thermal analysis, pyrolysis and thermal desorption techniques. Use and applications of various laser-based techniques (ablation, spectroscopy, desorption/ionisation
and pyrolysis) to polymer/additive analysis are described in Chapter 3 and are critically evaluated. Chapter 4
gives particular emphasis to the determination of additives on polymeric surfaces. The classical methods of
xi

xii

Preface

surface analysis (electron spectroscopy, surface mass spectrometry and ion scattering techniques) are applied
to practical cases. A variety of options for (surface) microanalysis and spatially resolved analysis by means
of microscopy, microspectroscopy, spectromicroscopy, and imaging techniques, as applied to polymer/additive
materials, are discussed in Chapter 5. Quantitative analysis (Chapter 6) in an essential part of polymer/additive
analysis, in particular in the industrial environment. For quantitation, the separation procedure can be the most
important factor for success or failure of the analysis. While this analytical task is recognised to be considerably
more difficult than the qualitative analysis of previous chapters, recent round-robins indicate the need for critical 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 status
of 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 method
development 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 individually. To facilitate rapid scanning the text has been provided with eye-catchers. Each chapter concludes with
up-to-date references to the primary literature (no patent literature) and a critical list of recommended general
reading (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 to
both instrumental methods and analytes. Although every effort has been made to keep the book up-to-date with
the latest methodological developments this report represents only work in evolution and contains suggestions
for future improvements. In J.R. Thorbeckes words De tijd om alles te zeggen is nog niet gekomen, or Time
is 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 in
materials characterisation, heterogeneous catalysis and product development who has gained broad industrial
experience (Monsanto, Montedison, DSM) in various countries. The contents of this book derive from the
authors experience as a previous Head of an Analytical Research Department concerned with polyolefins and
engineering 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), researched
extensively 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 Universities
of Leeds (Colour Chemistry) and Oxford (Material Science), visiting scientist at the Institut de Recherches
sur 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 Plastics
Engineers, the Institute of Materials and Associazione Italiana delle Macromolecole.

xiii

This page intentionally left blank

Acknowledgements
This monograph describes the current state-of-the-art in direct polymer/additive analysis. The high degree of
creativity and ingenuity within the international scientific community is both amazing and inspiring. The size
of the book shows the high overall productivity in academia and in industry. Yet, only a fraction of the pertinent
literature was cited.
The author wishes to thank in particular DSM for actively stimulating the work, for granting permission
for 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 Research
have 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 issues
with endless patience, it would not have been possible to complete this work successfully. The author has not
failed to disturb relatives and friends during the many years of preparation of this text, notably in Bucharest
and 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 and
thanks editor and members of staff at IOS Press for their professional assistance and guidance from manuscript
to printed volume. The kind permission granted by journal publishers, book editors and equipment producers to
use illustrations and tables from other sources is gratefully acknowledged. The exact references are given in the
figure and table captions. Every effort has been made to contact copyright holders of any material reproduced
within 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 the
editor. No responsibility or liability of any nature shall attach to DSM arising out of or in connection with any
utilisation in any form of any material contained therein.

xv