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STAL1586035339 FM I
STAL1586035339 FM I
Plastics Additives
Advanced Industrial Analysis
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Table of Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
xi
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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
Chapter 3
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158
163
173
175
189
192
209
213
214
222
235
244
261
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263
264
266
275
278
282
299
300
300
301
301
301
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325
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335
341
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343
346
353
354
363
366
374
381
388
392
392
392
392
393
393
393
Table of Contents
Chapter 4
Chapter 5
vii
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408
409
411
420
422
439
441
443
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446
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447
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447
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458
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464
466
472
475
478
483
485
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501
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511
514
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519
521
532
541
546
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555
559
560
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563
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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
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573
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576
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600
605
606
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609
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624
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626
628
629
630
633
637
639
639
644
645
646
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651
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655
Table of Contents
Chapter 7
ix
Chapter 8
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667
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683
693
701
704
716
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721
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722
722
723
723
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732
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760
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760
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762
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767
778
778
780
785
789
790
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
xiii
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