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 COMPREHENSIVE
ANALYTICAL CHEMISTRY
VOLUME 53
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, The Netherlands
Linacre House, Jordan Hill, Oxford OX2 8DP, UK

First edition 2008

Copyright r 2008 Elsevier B.V. All rights reserved

No part of this publication may be reproduced, stored in a retrieval system or transmitted in any
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Notice
No responsibility is assumed by the publisher for any injury and/or damage to persons or property
as a matter of products liability, negligence or otherwise, or from any use or operation of any
methods, products, instructions or ideas contained in the material herein. Because of rapid advances
in the medical sciences, in particular, independent verification of diagnoses and drug dosages should
be made

British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library

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ISBN: 978-0-444-53056-1
ISSN: 0166-526X

For information on all Elsevier publications

visit our website at books.elsevier.com

Printed and bound in Hungary

08 09 10 11 12 10 9 8 7 6 5 4 3 2 1
 ADVISORY BOARD

Joseph A. Caruso
University of Cincinnati, Cincinnati, OH, USA
Hendrik Emons
Joint Research Centre, Geel, Belgium
Gary Hieftje
Indiana University, Bloomington, IN, USA
Kiyokatsu Jinno
Toyohashi University of Technology, Toyohashi, Japan
Uwe Karst
University of Münster, Münster, Germany
György Marko-Varga
AstraZeneca, Lund, Sweden
Janusz Pawliszyn
University of Waterloo, Waterloo, Ont., Canada
Susan Richardson
US Environmental Protection Agency, Athens, GA, USA
Wilson & Wilson’s
COMPREHENSIVE
ANALYTICAL CHEMISTRY

Edited by
D. BARCELÓ
Research Professor
Department of Environmental Chemistry
IIQAB-CSIC
Jordi Girona 18-26
08034 Barcelona
Spain
 Wilson & Wilson’s
COMPREHENSIVE
ANALYTICAL CHEMISTRY
MOLECULAR CHARACTERIZATION AND ANALYSIS OF POLYMERS

VOLUME 53

Edited by
JOHN M. CHALMERS
VS Consulting, 14 Croft Hills,
Tame Bridge,
Stokesley TS9 5NW, UK

PROF. Dr ROBERT J. MEIER

Institut für Agrosphere, ICG-4,
Forschungszentrum Jülich GmbH,
D-52425 Jülich,
Germany

Amsterdam  Boston  Heidelberg  London

New York  Oxford  Paris  San Diego
San Francisco  Singapore  Sydney  Tokyo
This page intentionally left blank
 CONTENT S

Contributors to Volume 53 xiii

Volumes in the Series xv
Preface xix
Series Editor’s Preface xxi

SECTION I: INTRODUCTION

1. Introduction 3
John M. Chalmers and Robert J. Meier
1. The Analytical Competence 3
2. Contents and Structure 6
3. Practical Considerations in the Multi-Technique Approach 11
References 12

2. Polymer Chemistry and Microstructure 13

Jacques Devaux and Sophie Demoustier-Champagne
1. Introduction 14
2. Polymer: Definitions 15
3. From Molecules to Macromolecules 25
4. Fundamentals of Polymer Chemistry 34
5. Polymer Degradation 58
6. Summary 62
References 62

3. Polymeric Materials: Composition, Uses and Applications 65

J.P. Candlin
1. Introduction 65
2. Mode of Polymerisation 66
3. Polymer Materials: Types and Forms 68
4. Polymer Additives 87
5. Summary 117
Bibliography 118

vii
viii Contents

SECTION II: POLYMER CHAIN ANALYSIS

4. Chain Structure Characterization 123

Gregory Beaucage and Amit S. Kulkarni
1. Introduction to Structure in Synthetic Macromolecules 123
2. Local Structure and Its Ramifications 134
3. Summary 165
References 166

5. Chain End Characterisation 171

Anthony T. Jackson and Duncan F. Robertson
1. Introduction 171
2. End Groups in Free Radical Polymers 175
3. End Groups in Condensation Polymers 182
4. End Groups in Polymers from Ionic
Polymerisation 194
5. Closing Remarks 201
Acknowledgements 201
References 201

6. Determination of Molecular Weights and

Their Distributions 205
Simone Wiegand and Werner Köhler
1. Introduction 205
2. Distribution Functions and Averages 208
3. Methods Based on Colligative Properties 212
4. Viscometry 218
5. Scattering Techniques 220
6. Liquid Chromatography 228
7. Analytical Ultracentrifuge 235
8. Other Methods 237
9. Practical Examples 241
10. Conclusion 247
Acknowledgements 248
References 248

SECTION III: POLYMER MORPHOLOGY AND STRUCTURE

7. Phase Structure and Morphology 255

Rufina G. Alamo
1. Phase Structure and Morphology 255
2. Supermolecular Morphology 274
 Contents ix

3. Concluding Remarks 286

Acknowledgements 287
References 287

8. Characterization of Molecular Orientation 295

Thierry Lefèvre, Christian Pellerin and Michel Pézolet
1. Introduction 295
2. Theory 297
3. Birefringence 301
4. Infrared Linear Dichroism (IRLD) 305
5. Raman Spectroscopy and Microspectroscopy 313
6. Fluorescence Spectroscopy 322
7. NMR Spectroscopy 325
8. X-Ray Diffraction and Absorption 328
9. Conclusion 333
References 333

9. Polymer Networks: Elastomers 337

B. Erman and J.E. Mark
1. Introduction 338
2. Structure of a Typical Network 339
3. Elementary and More Advanced Molecular Theories 341
4. Phenomenological Theories 351
5. Some Relevant Simulations 352
6. Swelling of Networks and Responsive Gels 356
7. Enthalpic and Entropic Contributions to Rubber Elasticity:
The Force–Temperature Relations 358
8. Multimodal Elastomers 359
9. Liquid–Crystalline Elastomers 365
10. Novel Reinforced Elastomers 370
11. Further Comments on Some Characterization Techniques 374
Acknowledgement 376
References 377

SECTION IV: POLYMER DEGRADATION

10. Polymer Degradation and Oxidation: An Introduction 387

John M. Chalmers and Robert J. Meier
1. Introduction 388
2. Standard Tests and Comparative Methods 390
3. Spectroscopic Techniques 402
4. Thermal Methods 436
5. Chromatographic Analysis 442
6. Closing Remarks 447
Acknowledgement 448
References 448
x Contents

11. The Role of Oxidation in Degradation of Polymers:

The Relation of Oxidation to the Light Emission from
Oxidized Polymers 451
Jozef Rychlý and Lyda Matisová-Rychlá
1. Introduction, Historical Overview and Terminology Associated with the
Degradation and Ageing of Polymers 452
2. Methodology and Analytical Techniques in Polymer Stability Studies 461
3. Mechanisms Leading to the Light Emission from Thermally Oxidized Polymers
(Chemiluminescence), Similarities and Differences within Respective
Groups of Polymers 463
4. General Classification of Chemiluminescence from Polymers 471
5. Comparison of Chemiluminescence for Isothermal and Non-Isothermal
Conditions with those Obtained by DSC 476
6. The Effect of Initial Molar Mass on Chemiluminescence Runs 478
7. The Effect of Temperature on Chemiluminescence Intensity; The Mutual
Relation of Isothermal and Non-Isothermal Studies 480
8. Relaxation Experiments (Jump Changes of Concentration of Oxygen,
Temperature and Humidity) and Rate Constants of Respective Elementary
Reaction Steps 482
9. The Effect of Antioxidants and Polymer Stabilizers 483
10. Isothermal Kinetics of Polymers Oxidation and Its Relation to the
Concentration of Oxygen in Surrounding Atmosphere 487
11. The Effect of Alkaline Additives on Chemiluminescence Runs:
A Possible Impact 490
12. Conclusions and Outline of the Further Perspectives 493
Acknowledgements 496
References 496

12. ESR and ESR Imaging Methods for the Study of Oxidative
Polymer Degradation 499
Shulamith Schlick and Krzysztof Krucza"a
1. Introduction: Polymer Degradation in the Presence of Oxygen 500
2. Fundamentals of ESR and ESR Imaging 504
3. ESR as a Tool for the Study of Polymer Degradation 513
4. ESR Imaging: A Nondestructive Method for Spatially Resolved Polymer
Degradation 517
5. Concluding Remarks 521
Acknowledgements 521
References 522

SECTION V: POLYMER PRODUCT ANALYSIS

13. Spatial Imaging/Heterogeneity 527

Peter Wilhelm and Boril Chernev
1. Introduction 527
2. Raman and FTIR Microscopy 529
 Contents xi

3. Examples of Heterogeneous Polymers Investigated by IR and Raman Microscopy 538

4. Other Methods and Comparison of Methods 550
5. Conclusions 557
References 558

14. Additive Analysis 561

John Sidwell
1. Introduction 562
2. Analytical Techniques for Additive Analysis 563
3. Analysis of Specific Additives 573
4. Future Developments in Analytical Methodology 603
References 605

15. Failure, Defect, and Contaminant Analysis 607

James D. Rancourt, Jennifer Brooks, Sue Mecham,
Alan Sentman, Brian Starr and Jason Todd
1. Introduction 607
2. Case Studies 608
3. Summary 673
References 674

16. Surface Analysis 675

John M. Chalmers and Robert J. Meier
1. Introduction 675
2. A Surface and Spatial Resolution 676
3. Adhesion 677
4. Polymer Degradation 679
5. Polymer Fracture 679
6. Characterizing Polymer Surfaces 679
7. Delamination 679
8. Cure 681
9. Closing Remark 682
References 682

SECTION VI: POLYMER AND POLYMER PRODUCT DEVELOPMENT:

SUPPORT TECHNIQUES

17. The Supporting Role of Molecular Modelling and

Computational Chemistry in Polymer Analysis 685
John Kendrick
1. Introduction 686
2. Methodologies 687
3. Infrared and Raman Spectroscopy 693
4. Photoelectron Spectroscopy and Auger Electron Spectroscopy (AES) 703
xii Contents

5. Mass Spectrometry 712

6. X-Ray Diffraction 718
7. Nuclear Magnetic Resonance 722
8. Electron Spin Resonance 727
9. Summary 729
References 730

18. High-Throughput Analysis 735

Robert J. Meier
1. Introduction 735
2. Some General Considerations on MTE and the Corresponding
Analytical Needs 737
3. Analytical Techniques for Medium-Throughput Polymer Analysis 740
4. Outlook 742
References 743

Subject Index 745

See Color Plate Section at the End of This Book
 CONTRIBUTORS TO VOLUME 53

Rufina G. Alamo
FAMU/FSU College of Engineering, Department of Chemical and Biomedical Engineering, 2525
Pottsdamer St., Tallahassee FL 32310, USA

Gregory Beaucage
Department of Chemical and Materials Engineering, University of Cincinnati,
Mail location 12, Cincinnati, OH, 45221-0112, USA

Jennifer Brooks
Polymer Solutions Incorporated, 2903C Commerce Street, Blacksburg, Virginia 24060, USA

J.P. Candlin
4 Rudby Lea, Hutton Rudby, Yarm, TS15 0JZ, UK

John M. Chalmers
VS Consulting, 14 Croft Hills, Tame Bridge, Stokesley, TS9 5NW, UK

Boril Chernev
Centre for Electron Microscopy and Nanoanalysis, Steyrergasse 17, A-8010 Graz, Austria

Sophie Demoustier-Champagne
Université catholique de Louvain, Unité de Chimie et de Physique des Hauts polymères (POLY),
Croix du Sud, 1. B-1348 Louvain-la-Neuve, Belgium

Jacques Devaux
Université catholique de Louvain, Unité de Chimie et de Physique des Hauts polymères (POLY),
Croix du Sud, 1. B-1348 Louvain-la-Neuve, Belgium

B. Erman
Department of Chemical and Biological Engineering, Koc University, Rumeli Feneri Yolu 34450
Istanbul, Turkey

Anthony T. Jackson
AkzoNobel CARG, 137 Jiangtian East Road, Songjiang Industrial Estate, Shanghai 201600, P.R.
China

John Kendrick
Institute of Pharmaceutical Innovation, Bradford University, BD7 1DP, UK

Werner Köhler
Physikalisches Institut, Universität Bayreuth, D-95440 Bayreuth, Germany

Krzysztof Krucza"a
Faculty of Chemistry, Jagiellonian University, 30-060 Krakow, Poland

Amit S. Kulkarni
Department of Chemical and Materials Engineering, University of Cincinnati, Mail location 12,
Cincinnati, OH 45221-0112, USA

xiii
xiv Contributors to Volume 53

Thierry Lefèvre
Département de chimie, Université Laval, Québec, QC, G1V 0A6, Canada

J.E. Mark
Department of Chemistry, Crosley Tower, Martin Luther King Drive, University of Cincinnati,
Cincinnati, OH 45221-0172, USA

Lyda Matisová-Rychlá
Polymer Institute, Centre of Excellence for Degradation of Biopolymers, the Slovak Academy of
Sciences, 842 36 Bratislava, Slovakia

Sue Mecham
Polymer Solutions Incorporated, 2903C Commerce Street, Blacksburg, Virginia 24060, USA

Robert J. Meier
DSM Research, P.O. Box 18, 6160 MD Geleen, The Netherlands; Institut für Agrosphere, ICG-4,
Forschungszentrum Jülich GmbH, D-52425 Jülich, Germany

Christian Pellerin
Département de chimie, Université de Montréal, Montréal, QC, H3C 3J7, Canada

Michel Pézolet
Département de chimie, Pavillon Alexandre-Vachon, local 1084D, Univeristé Laval, Québec,
G1V 0A6, Canada

James D. Rancourt
Polymer Solutions Incorporated, 2903C Commerce Street, Blacksburg, Virginia 24060, USA

Duncan F. Robertson
Intertek-MSG, D131, Wilton Centre, Wilton, Redcar, Cleveland, TS10 4RF, UK

Jozef Rychlý
Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 842 36 Bratislava, Slovakia.

Shulamith Schlick
Department of Chemistry and Biochemistry, University of Detroit Mercy, 4001 West McNichols
Road, Detroit, Michigan 48221-3038, USA

Alan Sentman
Polymer Solutions Incorporated, 2903C Commerce Street, Blacksburg, Virginia 24060, USA

John Sidwell
Smithers Rapra Technology Ltd., Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK

Brian Starr
Polymer Solutions Incorporated, 2903C Commerce Street, Blacksburg, Virginia 24060, USA

Jason Todd
Polymer Solutions Incorporated, 2903C Commerce Street, Blacksburg, Virginia 24060, USA

Simone Wiegand
Forschungszentrum Jülich, IFF – Weiche Materie, Postfach 1913, 52425 Jülich, Germany

Peter Wilhelm
Research Institute for Electron Microscopy, Graz University of Technology, Steyrergasse 17,
A-8010 Graz, Austria
 VOLUMES IN THE SERIES

Vol. 1A Analytical Processes

Gas Analysis
Inorganic Qualitative Analysis
Organic Qualitative Analysis
Inorganic Gravimetric Analysis
Vol. 1B Inorganic Titrimetric Analysis
Organic Quantitative Analysis
Vol. 1C Analytical Chemistry of the Elements
Vol. 2A Electrochemical Analysis
Electrodeposition
Potentiometric Titrations
Conductometric Titrations
High-Frequency Titrations
Vol. 2B Liquid Chromatography in Columns
Gas Chromatography
Ion Exchangers
Distillation
Vol. 2C Paper and Thin Layer Chromatography
Radiochemical Methods
Nuclear Magnetic Resonance and Electron Spin Resonance Methods
X-ray Spectrometry
Vol. 2D Coulometric Analysis
Vol. 3 Elemental Analysis with Minute Sample
Standards and Standardization
Separation by Liquid Amalgams
Vacuum Fusion Analysis of Gases in Metals
Electroanalysis in Molten Salts
Vol. 4 Instrumentation for Spectroscopy
Atomic Absorption and Fluorescence Spectroscopy
Diffuse Reflectance Spectroscopy
Vol. 5 Emission Spectroscopy
Analytical Microwave Spectroscopy
Analytical Applications of Electron Microscopy
Vol. 6 Analytical Infrared Spectroscopy
Vol. 7 Thermal Methods in Analytical Chemistry
Substoichiometric Analytical Methods
Vol. 8 Enzyme Electrodes in Analytical Chemistry
Molecular Fluorescence Spectroscopy
Photometric Titrations
Analytical Applications of Interferometry
Vol. 9 Ultraviolet Photoelectron and Photoion Spectroscopy
Auger Electron Spectroscopy
Plasma Excitation in Spectrochemical Analysis

xv
xvi Volumes in the Series

Vol. 10 Organic Spot Tests Analysis

The History of Analytical Chemistry
Vol. 11 The Application of Mathematical Statistics in Analytical Chemistry Mass
Spectrometry Ion Selective Electrodes
Vol. 12 Thermal Analysis
Part A. Simultaneous Thermoanalytical Examination by Means of the
Derivatograph
Part B. Biochemical and Clinical Application of Thermometric and Thermal
Analysis
Part C. Emanation Thermal Analysis and other Radiometric Emanation
Methods
Part D. Thermophysical Properties of Solids
Part E. Pulse Method of Measuring Thermophysical Parameters
Vol. 13 Analysis of Complex Hydrocarbons
Part A. Separation Methods
Part B. Group Analysis and Detailed Analysis
Vol. 14 Ion-Exchangers in Analytical Chemistry
Vol. 15 Methods of Organic Analysis
Vol. 16 Chemical Microscopy
Thermomicroscopy of Organic Compounds
Vol. 17 Gas and Liquid Analysers
Vol. 18 Kinetic Methods in Chemical Analysis Application of Computers in
Analytical Chemistry
Vol. 19 Analytical Visible and Ultra-violet Spectrometry
Vol. 20 Photometric Methods in Inorganic Trace Analysis
Vol. 21 New Developments in Conductometric and Oscillometric Analysis
Vol. 22 Titrimetric Analysis in Organic Solvents
Vol. 23 Analytical and Biomedical Applications of Ion-Selective Field-Effect
Transistors
Vol. 24 Energy Dispersive X-ray Fluorescence Analysis
Vol. 25 Preconcentration of Trace Elements
Vol. 26 Radionuclide X-ray Fluorecence Analysis
Vol. 27 Voltammetry
Vol. 28 Analysis of Substances in the Gaseous Phase
Vol. 29 Chemiluminescence Immunoassay
Vol. 30 Spectrochemical Trace Analysis for Metals and Metalloids
Vol. 31 Surfactants in Analytical Chemistry
Vol. 32 Environmental Analytical Chemistry
Vol. 33 Elemental Speciation – New Approaches for Trace Element Analysis
Vol. 34 Discrete Sample Introduction Techniques for Inductively Coupled Plasma
Mass Spectrometry
Vol. 35 Modern Fourier Transform Infrared Spectroscopy
Vol. 36 Chemical Test Methods of Analysis
Vol. 37 Sampling and Sample Preparation for Field and Laboratory
Vol. 38 Countercurrent Chromatography: The Support-Free Liquid Stationary Phase
Vol. 39 Integrated Analytical Systems
Vol. 40 Analysis and Fate of Surfactants in the Aquatic Environment
Vol. 41 Sample Preparation for Trace Element Analysis
Vol. 42 Non-destructive Microanalysis of Cultural Heritage Materials
Vol. 43 Chromatographic-Mass Spectrometric Food Analysis for Trace
Determination of Pesticide Residues
Vol. 44 Biosensors and Modern Biospecific Analytical Techniques
Vol. 45 Analysis and Detection by Capillary Electrophoresis
Vol. 46 Proteomics and Peptidomics: New Technology Platforms Elucidating
Biology
 Volumes in the Series xvii

Vol. 47 Modern Instrumental Analysis

Vol. 48 Passive Sampling Techniques in Environmental Monitoring
Vol. 49 Electrochemical (Bio) Sensor Analysis
Vol. 50 Analysis, Fate and Removal of Pharmaceuticals in the Water Cycle
Vol. 51 Food Contaminants and Residue Analysis
Vol. 52 Protein Mass Spectrometry
This page intentionally left blank
 PREFACE

When, over three years ago, we were asked to commission a book on polymer
analysis, our initial reaction was to decline, since we both believed that there was
enough excellent books already published that dealt with the subject matter.
However, we then contemplated that most existing books cover the subject from
a technique point of view, that is, they tend to have a format in which individual
chapters focus specifically on a single technique, such as mass spectrometry,
nuclear magnetic resonance, vibrational spectroscopy, thermal analysis methods,
chromatographic methods, etc. Occasionally, the scope is wider, if we can put it
that way, but in these cases the focus is on a particular segment of the world of
polymers. It was during our discussions on this viewpoint when our industrial
experience kicked in, for which we recognised that the paramount desire of the
‘‘customer for polymer molecular characterization and analysis’’ is that of
problem solving, not of championing a single or set of particular techniques.
What these customers ideally require is a solution or information that enables
them to solve or overcome a problem on a timescale that is relevant to the
customers’ business needs, whether they be research-related, production-related,
property-related, service-related, marketing-related, competitive product defor-
mulation,y It was with this mindset that we agreed to try to commission a book,
the result of which you have in front of you, in which each chapter addresses a
particular problem or property, for example, chain structure or chain end
characterization, polymer degradation, molecular orientation, product failure,y,
and in which the techniques were secondary, that is ‘‘a means to an end’’ rather
than ‘‘how can I solve this problem/measure this property by the technique for
which I am a recognised specialist?’’ The task we set for many of our authors was
therefore often a very difficult one: that of providing as balanced a viewpoint as
possible of the various techniques and methods that may be used to tackle a
particular problem or property characterization, and how they may optimally
complement each other, and their comparative limitations and strengths.
This was our ultimate aim; that is, a text from which the essential information
to tackle a problem, for which polymer analysis is required, could be readily
distilled from its pages, and from which the supportive, confirmatory and
complementary positions of the various measurement techniques could be
readily grasped.

xix
xx Preface

Our industrial experience should have forewarned us: while it is relatively

easy to find well-recognised technique specialists, it did turn out, however, to be
not trivial to find authors fully comfortable with covering the issues and all
techniques from a problem-solving/property-related point of view. Some
chapters might, therefore, from some specialist readers and reviewers percep-
tions, still have some missing issues albeit relevant. In other cases, for example,
polymer degradation, optimum coverage has been achieved by including
multiple chapters. Nevertheless, considering all the possible topics to be covered
and the complexity of the issues involved, we believe most topics are well
covered by the contributing authors, and, notwithstanding, we believe the
coverage is comprehensive, and provides a unique text on the molecular
characterization and analysis of polymers, and approaches our ideal closely.
As intimated above, reaching this point, that is publication of this book, has
not been a straightforward task; the road has been sometimes rocky, with various
professional and personal problems causing both the need to refine our original
outline and the need along the way to commission late in the project new
authors. To all our chapter authors, we are therefore truly indebted. For those
whose chapters we have ‘‘sat on’’ for nearly two years, we especially thank you
for your understanding and patience! For those who ‘‘stepped into the breach’’
near the end, we especially thank you for coming to our aid! We are also very
thankful to the publishers, Elsevier Science B.V., for their patience too!
This book is divided up into sections. The first three chapters provide a
background; sections that follow contain chapters dealing with polymer chain
analysis, polymer morphology and structure, polymer degradation, polymer
product analysis and support techniques. These are listed in more detail in
Chapter 1, which also expands more fully on our industrial perception of the
requirements for competence and appreciation in all techniques and methods for
polymer molecular characterization and analysis. We hope you find this book of
value and its approach both unique and technically informative and useful.
John Chalmers
Robert J. Meier
November 2008
 S ER I E S E D I TOR ’ S P R E F A CE

This volume on ‘‘Molecular Characterization and Analysis of Polymers’’ has been

edited by John M. Chalmers and Robert J. Meier, both of whom have considerable
experience in the industrial sector. They have compiled a broad compilation of
chapters on the various aspects of polymer analysis and placed a clear and useful
emphasis on problem solving, rather than on the techniques used.
The first three chapters layout the background; the following chapters deal
with polymer chemistry and microstructure and polymeric materials, polymer
chain analysis, polymer morphology and structure, polymer degradation,
polymer product analysis, and polymer product development support techni-
ques. The book contains a considerable amount of information on the techniques
and methods used for polymer molecular characterization and analysis. Various
techniques covered include analytical options for polymer product analysis, like
size exclusion chromatography, thermal methods, nuclear magnetic resonance
spectroscopy, electron spin resonance spectroscopy, mass spectrometry, infrared
spectroscopy, gas chromatography-mass spectrometry and liquid chromatogra-
phy-mass spectrometry.
The book is a useful addition to the Comprehensive Analytical Chemistry series
and it is the first on the topic of polymer analysis in the series. A tremendous
effort was made by the editors to achieve this compilation and as they say in their
Preface ‘‘the road has been sometimes rocky’’.
Thanks to the editors and all contributing authors for their time and efforts in
preparing this comprehensive compilation of research papers that will make this
book on molecular characterization and analysis of polymers a unique reference
in this field.

D. Barceló
Barcelona, April 14, 2008

xxi
This page intentionally left blank
 SECTION I:
Introduction
This page intentionally left blank
 CHAPT ER 1
Introduction
John M. Chalmers and Robert J. Meier

Contents 1. The Analytical Competence 3

2. Contents and Structure 6
3. Practical Considerations in the Multi-Technique Approach 11
References 12

1. THE ANALYTICAL COMPETENCE

Polymers are around us everywhere, and their industrial production is a major

activity of the chemical industry throughout the world. As a consequence, there
is a significant support related R&D (research and development) activity within
both academia and industry. This applies to the search for new catalysts,
synthesis of new polymers, as well as attempts to produce new polymer chain
architectures, formulations, and finally the processing and shaping of polymers.
Few polymers are used in their pure form: additives and fillers, including fibres,
are commonly added to arrive at a material with the desired lifetime use
properties. Polymers can be functionalised to improve certain properties such as
adhesion or to make them suitable for use in a particular application, such as an
electronic component or aerospace application. To verify that the polymer chain
synthesized is what was expected, or in order to relate polymer properties to the
structure of the material, one needs polymer analysis and characterisation tools.
Analysis can be thought of as the breaking up of anything complex; it is the
contrary of synthesis, and can sometimes be referred to as such as ‘reverse
engineering’. Characterisation is the determination of properties, such as form,
chemical structure, colour, etc. Morphology is the science of form. The build-up of
a polymeric sample in terms of amorphous and crystalline domains, three-
dimensional networks, spherulites or other structural units, or the presence and
distribution of glass-fibres or other filler material, constitutes the morphology of
the sample. Morphological characterisation thus is a key means to establish
structure–property relations.

Comprehensive Analytical Chemistry, Volume 53 r 2008 Elsevier B.V.

ISSN: 0166-526X, DOI 10.1016/S0166-526X(08)00401-7 All rights reserved.

3
4 John M. Chalmers and Robert J. Meier

Traditionally, analysis and, to a lesser extent, characterisation, have

been viewed from the viewpoint of expertise in an individual technique,
e.g., spectroscopy of polymers (infrared (IR) and Raman spectroscopies, mass
spectrometry (MS) and nuclear magnetic resonance (NMR) spectroscopy),
thermal properties of polymers (differential scanning calorimetry (DSC) and
thermogravimetric analysis (TGA)), surface characterisation (e.g., secondary ion
mass spectrometry (SIMS) and atomic force microscopy (AFM)), etc. However,
particularly in an industrial context, problem solving is primarily what product
group customers of analytical groups are interested in and the technique
expertises should be considered as supporting activities. Moreover, in academic
groups those that synthesize polymers based on newly developed catalysts often
want to undertake their own analyses. Such groups are essentially interested in
appropriate answers from polymer analysis and characterisation, not in building
up expertise in individual analytical techniques.
What is needed primarily for problem solving and general analytical support
is an analytical/characterisation science competence. The competence in polymer
analysis is the capability to analyse polymers for constituents and properties,
each in relation to the questions or interests from the customer. Whereas in
academic synthetic groups the customer and the analyst may be one and the
same person, in industry the customer is usually a different person, often with
conflicting priorities of timescale. Defined as a competence, the traditional
individual expertises, e.g., microscopy, spectroscopy, thermal analysis, etc.,
are considered as supporting the competence. Foremost is the capability to
investigate, analyse and characterise, the polymer, both effectively and effi-
ciently. ‘‘What do we want to know about the polymer?’’ is the question
that comes first, whereas the technique and therewith the required expertise
comes second. This, obviously, is not meant to suggest that an expertise in a
specific technique is not important; in many cases the involvement of a
technique expert is vital. However, in both the industrial environment as well as
in academic synthetic and materials research groups, the problem solving
capability is the key issue. With which technique the problem is going to be
solved is less relevant. In most real cases all that matters is whether a problem
is addressed appropriately, both in terms of the solution information and its
derived timescale; this might, for example, in a failure analysis, simply be
identifying cause and not a detailed reason. Important components of the
solution may be any one or a combination of accuracy or precision really
required, overall time to obtain the results, price per analysis, etc. Accuracy is
mentioned at this point because the traditional expert has the tendency to strive
for results that are scientifically the best. This, however, is often not required.
This requires experts who are well trained in analytical competence thinking.
Precision is sometimes much more important than accuracy in a quality
assurance measurement.
The key appreciation here is the difference between technique expertise and
analytical competence. While retaining the necessary expertise on individual
techniques, understanding of the customer questions and aims (the problem
setting) is paramount. Understanding of the strengths, weaknesses and
 Introduction 5

limitations of different techniques is an integral part of optimal performance in

a competence. The level of technique expertise required will likely vary from
one situation to the other. The requirement on technique expertise does not
imply that in each laboratory where an analytical competence is required, a
high-level analytical expertise level is required. What is required is the set of
skills to provide analyses up to the level required and appropriate to the
problem, and perhaps its value of solution. Whether equipment is in-house or
elsewhere does not have to matter, as long as it is available when required for
problem solving.
Having said this, it was felt therefore that there is a need for a book
addressing analysis and characterisation of polymers from the point of view of
what we wish to call the primary analytical question. Many excellent textbooks
and reference works exist which address one or more individual analytical
techniques, see, for example, references [1–10]. These books form the basis of the
knowledge of the technique expert. They also contain many excellent and varied
examples on successful applications of analytical techniques to polymer analysis
and characterisation. There are also books which address the multitude of
analytical techniques applied in polymer analysis, see, for example, references
[11–24]. However, a synthetic chemist may wish to know the constitution of
his/her polymer chain, a material scientist may want to find out the reasons
why a fabricated sample had failed. What technique is best or optimal to study
chain constitution will depend on the situation. Polymer failure may result from
morphological features, which needs to be avoided, a contaminant, a surface
property degradation, etc. When a sample has been processed, e.g., a film blown,
molecular orientation may be the key parameter to be studied. A formulation
scientist may wish to know why an additive from a different supplier performs
differently. It is from such points of view that polymer analysis and chara-
cterisation is addressed in this book.
The aim of this book is therefore to present and discuss modern approaches
and strategies to polymer characterisation and analysis. As appropriate, however,
space will be given to theory, practice and instrumentation. While state-of-the-art
characterisation methods will feature highly, conventional use of analytical
techniques will also be well covered. The emphasis however, whenever possible,
will be pragmatic and problem solving and property determination led,
illustrated by ‘real-world’ application examples. As suggested above, the real
accuracy or precision required, the time allowed to arrive at a satisfactory result,
and the monetary/manpower budget available to obtain meaningful results are
all integral elements when the intention is to run an analytical competence in
optima forma. Therefore, the emphasis must be on the synergistic, complementary,
effective and efficient usage of characterisation techniques and tools and
analytical methodology, expertise and skill; it cannot be technique led. Foremost
must be the property characterisation, the problem solution and effective
polymer analysis; techniques provide the means, and per se should not be the
driver! The materials covered in this book will be organic polymers; biopolymer
and inorganic polymer characterisations are not considered. The characterisa-
tions will focus on polymer and polymer product microstructure and
6 John M. Chalmers and Robert J. Meier

composition; the discussions will not feature bulk property measurements, e.g.,
mechanical, electrical.
The emphasis is on commercial materials and formulations. The reason is that
commercial materials are rarely pure materials. A pure homopolymer is a rare
species in the ‘real-world’ materials. To arrive at the desired material’s properties,
either a copolymer is used, sometimes a blend or a dispersion, or additives or
filler materials including rubber particles, carbon black or fibres of various type
and make may be added, and are thus commonplace in commercial products.
This implies a more complex constitution and morphology than expected
for pure polymers. However, obviously, the methods described herein can be
applied to pure, unmodified, polymers as well.

2. CONTENTS AND STRUCTURE

In contrast to a book describing contributions of individual techniques, there is
undoubtedly not a single way to structure the approach to be dealt with in this
book. The approach taken is as follows. A polymer material consists of individual
polymer chains, and all together these make the material and its morphology,
which in turn relate to the material’s properties. A cluster of chapters addressing
the individual chain characteristics was therefore thought appropriate, followed
by another cluster on morphology. As mentioned before, as most polymeric
materials for practical use are not pure polymers, a third cluster was formed
dealing with analysis of the product, which includes issues such as additives and
surface characteristics.
Consequently, this book comprises six sections. The first section serves as an
Introduction, it includes this chapter and the next two chapters, which deal with
the basics of polymer chemistry and microstructure (Chapter 2) and polymeric
materials and their composition, uses and application (Chapter 3). The next
section (Polymer Chain Analysis: Chapters 4–6) relates to polymer chain analysis
(chain structure characterisation, chain end characterisation and molecular
weight and distribution). The third section (Polymer Morphology and Structure)
that deals with polymer morphology and structure is subdivided into phase
structure and morphology (Chapter 7), molecular orientation (Chapter 8) and
polymer networks (Chapter 9). Chapters 10–12, the fourth section (Polymer
Degradation), cover approaches to study and investigate polymer degradation.
The next section, Polymer Product Analysis, covers spatial imaging and
heterogeneity (Chapter 13), analysis of additives (Chapter 14), failure, defect
and contaminant analysis (Chapter 15) and concludes with a short chapter on
surface analysis (Chapter 16). The final section, which we have called Polymer
and Polymer Product Development: Support Techniques, considers the role of
computational chemistry and molecular modelling in supporting polymer
analysis (Chapter 17), and high-throughput analysis (Chapter 18).
The polymer characteristics addressed within these clusters are presented
below in Table 1. Table 1 presents an overview of the many analytical/
characterisation techniques and methods used for the molecular characterisation
 Introduction 7

Table 1 (a) Summary of the techniques used for molecular analysis and characterisation of
polymers. The techniques and methods listed have been mostly picked from those mentioned in
the chapters within this book; the order in which they appear is random, and does not reflect
their relative importance or their order of most common use, particularly since they are most
frequently used in synergistic, confirmatory and/or complementary combinations. (b)
Abbreviation and acronym definitions for techniques cited in Table 1(a).

(a):

Polymer Property to be analysed/ Suitable/primary

characterised techniques/methods

Polymer chain structure:

monomer, comonomer NMR, IR, Raman
type and composition
degree of polymerisation NMR
(dp)
conformation (e.g., trans- NMR, IR, Raman
gauche), isomerism (e.g.,
cis-trans)
tacticity, stereoregularity NMR, IR
chain lengths (persistence, SANS
Kuhn unit)
branching (e.g., short- SEC, GPC, NMR, rheology,
chain, long-chain, hyper-, SANS, SAXS
star, ladder, brushes)
unsaturation NMR, Raman, IR
copolymer sequencing NMR, IR
end-group analysis NMR, MS, MALDI-MS, IR,
Raman, chemical
titration
cross-linking indirect techniques,
including s-NMR, gel-
point determination,
rheology, LC-MS
techniques can in part be
applied
molecular weight, GPC/SEC, MALDI-MS,
molecular weight membrane osmometry,
distribution vapour pressure
osmometry, viscometry,
light scattering, TDFRS,
SAXS, SANS, SEC-
HPLC, SEC-MS, SEC-IR,
FFF, ultracentrifugation,
MALDI-TOF-MS, NMR,
capillary electrophoresis
8 John M. Chalmers and Robert J. Meier

Table 1 (Continued )

(a):

Polymer Property to be analysed/ Suitable/primary

characterised techniques/methods

Polymer material/product
characterisation:
crystallinity, amorphous WAXS, WAXD, SAXS,
content, phase analysis SALLS, density, DSC, IR,
Raman, s-NMR, AFM,
optical microscopy, SEM,
TEM
molecular orientation WAXD, s-NMR, IR,
Raman, fluorescence
spectroscopy,
birefringence
degradation, oxidation CL, ESR, ESRI, IR/IR
microscopy, Raman/
Raman-microscopy,
GC-IR, EGA-IR, Py-IR,
Py-GC-IR, UV, visible
spectroscopy,
fluorescence/
phosphorescence,
MS, MALDI-TOF-MS,
GC-MS, Py-MS, Py-GC-
MS, GPC, SEC, GPC-MS,
GPC-IR, s-NMR, NMR,
TA, DSC, TGA,
oxidative-induction time
(DSC), DPC, TGA-IR,
TGA-MS, GC, IGC, LC,
LC-CC, HPLC, LC-IR,
LC-MS, XPS, SIMS,
optical microscopy,
oxygen uptake, carbonyl
index (IR), iodometric
test, titration, staining,
MFI
Product analysis:
polymer network s-NMR, gelation, swelling,
birefringence, IR, NMR,
STM, SANS, Brillouin
scattering, pulse-
propagation
 Introduction 9

Table 1 (Continued )

(a):

Polymer Property to be analysed/ Suitable/primary

characterised techniques/methods

surface analysis optical microscopy, XPS

(ESCA), IR-ATR, Raman,
AFM, SIMS, LEIS, IR
spatial heterogeneity optical microscopy,
IR-microscopy, Raman-
microscopy, TOF-SIMS,
NIR-imaging, SNOM,
MRI, ESRI, mXRF, PES,
LEIS, RIS
additive analysis AAS, GC, GC-MS, IR,
HPLC, LC-MS, ICP-AES,
SEM, TGA, XRF, NMR
failure, defect, optical microscopy, IR,
contaminant analysis Raman, XRF, DSC, TGA,
NMR, SEM, SEM-EDS,
XPS, SIMS, GPC/SEC,
ICP-MS, GC-MS, LC-MS,
AFM

(b)

AAS Atomic absorption spectrometry

AFM Atomic force microscopy
ATR Attenuated total reflection
CL Chemiluminescence
DPC Differential photocalorimetry
DSC Differential scanning calorimetry
EDS Energy dispersive spectroscopy
EGA Evolved gas analysis
ESCA Electron spectroscopy for chemical analysis
ESR Electron spin resonance spectroscopy
ESRI Electron spin resonance imaging
FFF Field-flow fractionation
GC Gas chromatography
GPC Gel permeation chromatography
HPLC High-performance liquid chromtography
IGC Inverse gas chromatography
ICP-AES Inductively coupled plasma atomic emission spectroscopy
ICP-MS Inductively coupled plasma mass spectrometry
IR Infrared
LC Liquid chromatography
LC-CC Liquid chromatography under critical conditions
10 John M. Chalmers and Robert J. Meier

Table 1 (Continued )

(b)

LEIS Laser enhanced ionisation spectroscopy

MALDI-TOF-MS Matrix-assisted laser desorption time-of-flight mass spectrometry
MFI Melt flow index
MRI (Nuclear) magnetic resonance imaging
MS Mass spectrometry
NIR Near-infrared spectroscopy
NMR Nuclear magnetic resonance spectroscopy
PES Photoelectron spectroscopy
Py Pyrolysis
RIS Resonance ionisation spectroscopy
SALLS Small-angle laser light scattering
SANS Small-angle neutron scattering
SAXS Small-angle X-ray scattering
SEC Size exclusion chromatography
SEM Scanning electron microscopy
SIMS Secondary ion mass spectroscopy
s-NMR Solid state nuclear magnetic resonance spectroscopy
SNOM Scanning near-field optical microscopy
STM Scanning tunnelling microscopy
TA Thermal analysis
TDFRS Thermal diffusion forced Rayleigh scattering
TEM Transmission electron microscopy
TGA Thermogravimetric analysis
ToF Time-of-flight
WAXD Wide-angle X-ray diffraction
WAXS Wide-angle X-ray scattering
XPS X-ray photoelectron spectroscopy
XRF X-ray fluorescence spectroscopy
mXRF micro-X-ray fluorescence spectroscopy

and analysis of polymers and polymer formulations and products. While one or
two techniques/methods may be dominant in a particular area, it can be readily
seen that several to many can be applied depending on the information required
and the depth of problem solving and understanding that is needed, along with
the suitable or most common analytical techniques. The requirement and need
for a multi-technique attack on a problem or study is probably most exemplified
in the chapter on polymer failure (Chapter 15) and polymer degradation
(see Chapter 10); in the latter many of the references cited used five or more
analytical/characterisation tools in the investigation. The need for a multi-
technique approach is an even more prominent need in the study of polymer
morphology, although perhaps less often practised in single studies. A key
 Introduction 11

feature here obviously is the various length scales involved, from single chain
conformation and configuration (as they co-determine the possibility of certain
larger structures to be formed) to crystalline lamellae, shperulites, etc. Key issues
when polymer chain analysis or polymeric materials characterisation is applied is
the choice of property to analyse, and when selected, which is the most suitable
technique given the question to be addressed and circumstances, e.g., business
pressure (availability, price, accuracy, speed).

3. PRACTICAL CONSIDERATIONS IN THE MULTI-TECHNIQUE

APPROACH

Whereas several techniques may thus be used to study a certain characteristic of a

polymer sample, for instance IR and Raman spectroscopy and X-ray diffraction as
well as NMR may be used to determine or infer the crystallinity level of a sample,
different techniques work differently and therefore usually do not measure the
same. What this means is that crystallinity levels obtained from the same sample
may differ when a different technique is applied, see, for example, ref. [23] and
chapter 7 and references therein. However, these differences do not necessarily
imply one technique being better than another. In fact these differences may
contain useful information on the sample (see, for example, ref. [25]).
This brings us to the point of considering the suitability of a technique with
respect to a certain analysis, particularly from an industrialist’s or contract
laboratory viewpoint. This is a very important consideration, as this is not a priori
straightforward. There are a number of factors influencing the choice. We will
mention just a few of these in arbitrary order:

(i) When, for whatever reason, one does not wish to be involved in further
method development but just apply a technique, this means that the
technique must have been applied to the problem of interest before, or it
must be essentially a trivial translation from a previously demonstrated
application. Example: IR spectrum of an unknown, NMR can do the job;
X-ray crystallinity.
(ii) Does the technique need to be applied on a lab-scale or in-process? Does
the technique have to be applied off-, at-, in- or on-line?
(iii) Is cost of analysis relevant?
(iv) What is the accuracy/precision required?
(v) Is concentration/composition to be measured?
(vi) Is speed important?
(vii) Do you have the equipment available (in-house or otherwise readily
available)?
(viii) If such as a failure analysis, is it just satisfactory to identify the cause, or
does reason matter too?

The chapters following in this book should, we hope, enable one to obtain an
objective assessment and comparison of the most appropriate polymer molecular
12 John M. Chalmers and Robert J. Meier

characterisation or analysis tool according to the problem solving circumstances.

The reader will be able to obtain experts’ overviews of the range of tools, and
their strengths, convenience of use and limitations, necessary to characterise or
analyse the molecular structure, composition and properties of polymers and
their formulated products.

REFERENCES
1 I. Ando and T. Asakura, Solid State NMR of Polymers, Elsevier, Amsterdam, 1998.
2 F. Bovey and P. Mirau, NMR of Polymers, Elsevier, Amsterdam, 1996.
3 J.M. Chalmers and P.R. Griffiths (Eds.), Handbook of Vibrational Spectroscopy, Vol. 4, Wiley,
Chichester, 2002.
4 N.J. Everall, J.M. Chalmers and P.R. Griffiths (Eds.), Vibrational Spectroscopy of Polymers: Principles
and Practice, Wiley, Chichester, 2007.
5 P. Worsfold, A. Townshend and C. Poole (Eds.), Encyclopedia of Analytical Science, 2nd ed.,
Academic Press, London, 2004.
6 D. Briggs, Surface Analysis of Polymers by XPS and Static SIMS, Cambridge University Press,
Cambridge, 1998.
7 S. Schlick (Ed.), Advanced ESR Methods in Polymer Research, Wiley, Chichester, 2006.
8 W.M. Groenewoud (Ed.), Characterisation of Polymers by Thermal Analysis, Elsevier, Amsterdam,
2001.
9 I. Wilson, C. Poole and M. Cooke (Eds.), Encyclopedia of Separation Science, Academic Press, London,
2000.
10 G. Montaudo and R.P. Lattimer, Mass Spectrometry of Polymers, CRC Press, Boca Raton, 2001.
11 B.J. Hunt and M.I. James (Eds.), Polymer Characterisation, Blackie Academic & Professional,
Glasgow, 1993.
12 J.L. Koenig, Spectroscopy of Polymers, 2nd ed., Elsevier Science, New York, 1999.
13 J.I. Kroschwitz (Ed.), Polymers: Polymer Characterization and Analysis, Wiley, New York, 1990.
14 J.I. Kroschwitz, Concise Encyclopedia of Polymer Science and Engineering, Wiley, New York, 1998.
15 Polymers and Rubbers. In: R.A. Meyers (Ed.), Encyclopedia of Analytical Chemistry, Wiley,
Chichester, 2002.
16 H.F. Mark (Ed.), Encyclopedia of Polymer Science and Technology, 3rd ed., Wiley-VCH, Weinheim,
2004.
17 J.C.J. Bart, Additives in Polymers: Industrial Analysis and Applications, Wiley, Chichester, 2005.
18 J. Scheirs, Compositional and Failure Analysis of Polymers: A Practical Approach, Wiley, Chichester,
2000.
19 J. Haslam, H.A. Willis and D.C.M. Squirrell, Identification and Analysis of Plastics, 2nd ed.,
Buterworth, London, 1972.
20 J.I. Kroschwitz (Ed.), Concise Encyclopedia of Polymer Science and Engineering, Wiley, Chichester, 1998.
21 R.A. Pethrick and J.V. Dawkins (Eds.), Modern Techniques for Polymer Characterisation, Wiley,
Chichester, 1999.
22 M. Bolgar, J. Hubbal, J. Groger and S. Meronek, Handbook for the Chemical Analysis of Plastic and
Polymer Additives, CRC Press, Boca Raton, 2007.
23 D. Campbell, R.A. Pethrick and J.R. White, Polymer Characterization: Physical Techniques, 2nd ed.,
CRC Press, Boca Raton, 2000.
24 R.A. Prethrick, Polymer Structure Characterization from Nano to Macro Organization, RSC Publishing,
Cambridge, 2007.
25 R.J. Lehnert, P.J. Hendra, N. Everall and N.J. Clayden, Comparative quantitative study on the
crystallinity of poly(tetrafluoroethylene) including Raman, infra-red and F nuclear magnetic
resonance spectroscopy, Polymer, 38(7) (1997) 1521–1535.
 CHAPT ER 2
Polymer Chemistry and
Microstructure
Jacques Devaux and Sophie Demoustier-Champagne

Contents 1. Introduction 14
2. Polymer: Definitions 15
2.1 Monomers, chain length, length distribution 15
2.2 Thermoplastics and thermosets 17
2.3 Thermal transitions and properties 17
2.4 Microstructure 21
3. From Molecules to Macromolecules 25
3.1 Chain length and entanglements 27
3.2 End groups 27
3.3 Chain substituents 28
3.4 Spatial arrangements 28
4. Fundamentals of Polymer Chemistry 34
4.1 Chain polymerisation vs. step polymerisation 34
4.2 Types of chain polymerisations and polymers
synthesized — keypoints of mechanisms, kinetics 35
4.3 Radical chain polymerisations 35
4.4 Ionic polymerisations — active species 42
4.5 Olefin polymerisation processes 45
4.6 Processes for polyolefin syntheses 48
4.7 Copolymers 50
4.8 Types of step polymerisations and polymers
synthesized — keypoints of mechanisms, kinetics 53
5. Polymer Degradation 58
6. Summary 62
References 62

Comprehensive Analytical Chemistry, Volume 53 r 2008 Elsevier B.V.

ISSN: 0166-526X, DOI 10.1016/S0166-526X(08)00402-9 All rights reserved.

13
14 Jacques Devaux and Sophie Demoustier-Champagne

1. INTRODUCTION

‘‘A material is a solid used by man to produce items that constitute the support
for his living environment’’ [1]. Such a definition, although restrictive as it
excludes liquids, is simple enough. It might imply however, on the one hand, that
materials as such only existed from the beginning of mankind, moreover, on the
other hand, that the usual three classes of ‘‘materials’’ — ceramics, metals and
polymers — have always coexisted. Indeed, most of the earth’s terrestrial crust
is made of minerals, the majority of which are considered to be ceramics,
that is, ‘‘resulting from the combination of a limited number of metallic elements
(Si, Ca, Mg, Al, Ti, etc.) with non-metallic elements, most commonly oxygen’’ [1].
Ceramic materials marked the so-called ‘‘Stone Ages’’, the earliest stages of
civilisation.
A few pure (native) metals have existed as materials from the first ages of
mankind, namely those that have a high oxido-reduction potential, which
protects against oxidation by atmospheric oxygen (e.g., gold, platinum, silver,y).
Their bright colour and inalterability led humans to use them in jewellery.
However, geological science tells us that huge amounts of natural metals exist in
the earth’s nucleus (e.g., Si, Al, Fe, Ni, etc.), which constitute the main part of the
earth’s mass. Being oxidised through reaction with oxygen, landmarks in
civilisation’s progress (bronze age, iron age) are labelled by mankind’s mastering
of more and more complex metal productions (reduction).
Natural polymers are far more complex materials, being exclusively
‘‘organic’’, that is, products of life (cellulose, proteins, DNA,y). Nevertheless,
as nature seems to have formed (size, weight, hardness, etc.) several natural
polymers (wood, bones, ivory, etc.) in such a way as to be almost immediately
usable by our ancestors, they were most probably the bases of the first human
tools. The commonly widespread conception that polymers are the youngest
‘‘materials’’ in the historical world is not true, but, strictly speaking, only applies
to synthetic polymers, which were discovered about 100 years ago, early in the
XXth century.
Polymers are undoubtedly ‘‘materials’’. Knowledge and understanding of
their properties belongs to the so-called field of ‘‘Materials Science’’. Study and
understanding of their formation, properties and performance characteristics
involves chemistry, physico-chemistry and physics, the latter including
mechanics, optics, electricity, etc. Material’s knowledge is not limited to the
aforementioned fields of science, but includes also technological properties,
which are most often used for their classification: strength, hardness, transpar-
ency, conductivity, etc. Materials science is thus built on complex interrelation-
ships between such fields, see Figure 1.
Few properties, if any, depend directly and only on the chemistry. Indeed, as
shown in Figure 1, the ‘‘route’’ implies that it is chemistry that influences (micro-)
structure, which, in turn, governs properties. Processing, which is not often
classified as a ‘‘science’’ but as ‘‘engineering’’, has to find its place in the picture,
since it is the normal way to go from a macromolecule to a product with the
desired properties.
 Polymer Chemistry and Microstructure 15

Processing

Synthesis Characterisation Microstructure

Properties

Figure 1 Polymers in materials science: Interrelationships between synthesis, processing,

microstructure, properties and characterisation.

Characterisation covers a wide field of science and technology and interacts

from the synthesis stage through the analysis of structure to the determination of
properties. Characterisation allows one to observe, control and model (including
‘‘closed-loop’’ backward interaction) all the complex interrelationships of
materials science.

2. POLYMER: DEFINITIONS

2.1 Monomers, chain length, length distribution

The word ‘‘polymer’’ (first proposed by Berzelius in 1833) is made of ‘‘poly’’ from
the ancient Greek word ‘‘poluB’’ meaning ‘‘many’’ and ‘‘meroB’’ meaning ‘‘part’’.
Polymers are molecules built up from numerous identical chemical ‘‘units’’
spatially repeated to form a chain. From the early times and still nowadays, a
distinction is often made between ‘‘natural’’ and ‘‘synthetic’’ polymers, but it is
somewhat artificial as natural polymers can now sometimes be synthesized
(e.g., synthetic ‘‘natural rubber’’) and some synthetic polymers, which are never
found in nature, can be synthesized by natural ways (enzymatic syntheses).
Nevertheless, synthetic polymers are most often made from monomers
(from ancient Greek ‘‘monoB’’ meaning single), which are precursor molecules of
a polymer chain. When only a few monomers are joined to form a chain, they
are called oligomers (from ‘‘oligoB’’ a few, in ancient Greek). Despite this
distinction between oligomers and polymers is rather ill defined, one generally
conceives that polymer chains exhibit high molecular masses ranging from 104 to
about 107, the masses of oligomers being conventionally limited to below about
104. Polymer is also a word the use of which is restricted to chemical compounds
based on covalent links, chemically stable at ambient conditions. Most often
polymers are made from carbon and hydrogen or hydrocarbon derivatives (with
oxygen, nitrogen, sulfur, halogens,y) (Table 1). But, they are sometimes based on
inorganic backbone atoms (silicon, nitrogen and phosphorous,y).
From the above considerations, it appears that chain length is a main
characteristic of polymers. Natural macromolecules, particularly in living bodies,
can exhibit exact lengths, thus exact molecular masses. For instance haemoglobin
molecular mass is known to within one dalton. However, a synthetic polymer
16 Jacques Devaux and Sophie Demoustier-Champagne

Table 1 Examples of some ‘‘natural’’ and ‘‘synthetic’’ polymers

Name of polymer Formula Approximate

date of
invention

Polyethylene 1935
C C
H2 H2 n

Polypropylene 1954
(isotactic) C CH
H2
n
CH3

Poly(methyl O C O CH3 1935

methacrylate)
(PMMA) C C
H2 n
CH3

Poly(vinyl chloride) 1872

(PVC) C CH
H2 n
Cl

Polystyrene 1925
C CH
H2 n

Poly(ethylene 1941
terephthalate) (PET) H O C C O C C OH
H2 H2
n
O O

Poly(hexamethylene O O 1938
adipamide)
(Nylon 66) H N C N C C C OH
H H2 6 H H2 4
n

Cellulose H2 Natural
C OH H OH polymer
O
H O HO H H
O HO H H H
O
H OH C OH n
H2
 Polymer Chemistry and Microstructure 17

sample contains chains having a wide distribution of chain length. The breadth of
the molecular mass1 distribution depends on the synthesis process. Therefore, it
is necessary to define average molecular masses to characterize a polymer
sample. The simplest method — the number average molecular mass or Mn — is
an arithmetic average based on the total mass of a sample divided by the total
number of molecules in this sample.
For correlation with most physical properties (mechanical strength, optical
scattering), mass average molecular mass of a polymer ‘‘Mw ’’ appears more
satisfactory. Higher-power averages like z-average molecular mass ‘‘Mz ’’ seem to
better correlate with rheological properties. Expressions of Mn ; Mw and Mz are
P P 2 P 3
ni mi ni mi ni mi
Mn ¼ P
i
n
Mw ¼ P
i
nm
Mz ¼ P
i
n m2
i i i i i
i i i

where ni and mi are the number and the molecular mass of molecules containing i
units, respectively.
A measure of the breadth of the molecular mass distribution is given by the
ratios of molecular mass averages. The most commonly used ratio Mw =Mn ¼ H,
is called the polydispersity index. Wiegand and Köhler discuss the determination
of molecular masses (weights) and their distributions in Chapter 6.

2.2 Thermoplastics and thermosets

Thousands of polymers have been synthesized and more are likely to be
produced in the future. Fortunately, all polymers can be divided into two major
groups based on their thermal processing behaviour. Some polymers behave as
(viscous) liquids upon heating and can be re-processed, almost indefinitely.
These are classified as ‘‘thermoplastics’’ (from the ancient Greek prefix ‘‘yermo’’
for ‘‘heat’’). Some major commercial examples are polystyrene (PS), polyethylene,
polypropylene and poly(vinyl chloride) (PVC). Other polymers keep their
(definitive) shape after a first heating step during synthesis or subsequent
treatment. These are called ‘‘thermosets’’. Once formed the crosslinked networks
resist heat and solvent attack. Such properties make thermosets suitable materials
for composites, coatings and many adhesive applications. Major examples of
thermosets include epoxy resins, phenol-formaldehyde resins, urea/melamine
formaldehyde resins and unsaturated polyesters.

2.3 Thermal transitions and properties

2.3.1 Glass transition
Matter is made from atoms or molecules, for which the spatial arrangements
depend on cohesion (energy from interaction forces) and thermal energy, which
is proportional to temperature. Weak cohesion and/or high temperatures lead to

1
The notation M is used here for molecular masses, while X is used for chain lengths (or ‘‘degrees of
polymerization’’). M ¼ XMO with MO, the molecular mass of one unit in the polymer chain.
18 Jacques Devaux and Sophie Demoustier-Champagne

gases, while, in contrast, high cohesion and/or low temperatures yields solids,
with liquids as an intermediate state. There are rather limited differences
between liquid and solid states as specific masses of solids are usually only about
15% higher than those of corresponding liquids. Inside liquids, due to the rather
low level of empty volume (the so-called ‘‘free volume’’), molecules can move
due to ‘‘concerted’’ movements of the neighbouring molecules.
Upon cooling down a liquid, the ratio between the thermal and the cohesion
energy decreases, molecules become closer to each other and the free volume
decreases. Thermal energy, which leads to molecular mobility, becomes lower,
and attraction and repulsion forces between molecules begin to play a more
significant role. When these latter forces predominate over thermal energy, an
equilibrium is usually reached between them leading to ordered (crystalline)
structures. However, this is only the case when the time needed for molecular
movement (the so-called ‘‘characteristic time’’) is lower than that of cooling.
When no extended ordering can occur and/or if molecular movements are
extremely slow (very big and/or branched molecules) and/or if the cooling is
very fast, ordering remains limited to rather small ‘‘domains’’ of molecules. The
solid is said to be ‘‘amorphous’’ and retains in the solid state, the rather
disordered microstructure (including the free volume) of a liquid. Figure 2 shows
how atomic organisation changes with temperature.
The temperature at which a liquid (highly viscous, or even rubbery for very
high molecular masses) becomes an amorphous solid (rigid, stiff, often brittle) on
cooling (or vice versa an amorphous solid becomes liquid on heating) is called
the glass transition and noted Tg (Figure 3). In the glassy state, thus below Tg,
very few molecular movements (group rotations, vibrations) are allowed. Above
Tg, large-scale motions involving the whole macromolecule (translations,
repetations) become possible.
It has to be noticed that no isothermal volume contraction on cooling or
volume expansion on heating is associated with Tg, contrary to crystallisation or
melting. The latter is a true first-order transition exhibiting a discontinuity in

Figure 2 Evolution of atomic organisation with increasing temperature. Reproduced from

Mercier, Zambelli and Kurz [1], Elsevier (2002) with permission of Elsevier. Copyright Elsevier
2002.
 Polymer Chemistry and Microstructure 19

Figure 3 Curves of specific volumes vs. temperature for poly(vinyl acetate) measured on
cooling. Equilibrium values measured 0.02 h and 100 h after cooling, as indicated. Tgu and T g
are glass transitions respectively at fast and slow cooling rate. Reproduced from Ref. [2] with
permission of John Wiley & Sons, Inc.

thermodynamic variables. Despite the discontinuity occurring only in the first

derivative of thermodynamic variables, Tg is not a true ‘‘second-order’’ transition
as it also depends on kinetics. Figure 3 also shows how Tg moves with cooling
rate for a sample of poly(vinyl acetate). Tg is said to be a ‘‘kinetic transition’’.

2.3.2 Crystallisation-melting temperature

The commonest state of the solid matter is the crystal. A crystalline solid is made
of a periodic arrangement of atoms (or small molecules) in the three dimensions
of space. A (single) crystal is a very ordered state formed by the juxtaposition of
numerous identical ‘‘unit cells’’ (parallelepipedic volume containing one atom or
one small molecule). A crystal structure is characterised by its symmetry [1].
Due to the length of the macromolecules, the existence of single crystals of
polymers has remained a controversy for a long time. Soon after World War II,
microscopic polymer ‘‘single crystals’’ were obtained by very slow cooling from
20 Jacques Devaux and Sophie Demoustier-Champagne

Figure 4 Scheme of chain folding in polymer crystals.

dilute solutions. Upon cooling from the liquid state at a suitable rate, polymers
whose chain segments (including a few repeat units) exhibit symmetry elements
of high enough order, can thus crystallise. Such a crystallisation goes along with
long-range ordering. The determination of the ‘‘unit cell’’ led to the conclusion
that, within such a single crystal, one macromolecule encompasses many ‘‘unit
cells’’, which, itself, includes only one or a few ‘‘repeat units’’.
Moreover, upon examination by electron diffraction, it appeared also that in
these ‘‘single crystals’’, the chain axis was perpendicular to the largest faces,
thus, that the chains are oriented in the ‘‘thickness’’ direction. However, as such
thicknesses are much smaller than extended-chain lengths, a model of ‘‘chain
folding’’ was established for forming such polymer crystals (Figure 4). As a
consequence of chain folding, besides the inclusion of chain ends, these ‘‘single
crystals’’ exhibit at a minimum a certain amount of defects at their surface. This is
a reason why polymers are never 100% crystalline.
In polymers crystallised from the melt, lamellae were observed by electron
microscopy, whose thickness are of the same order of magnitude as ‘‘single
crystals’’ obtained from solution (Figure 5). Crystal ‘‘unit cells’’ within these
lamellae are comparable to those of single crystals and the chains are also
oriented in the thickness direction. Therefore, the same model of chain folding
was applied to melt-crystallised polymers. However, lamellae are, by far, less
perfect structures than ‘‘single crystals’’ and each individual polymer chain gives
rise to only a limited number of ‘‘folds’’, its remaining part (the so-called ‘‘tie’’)
protrudes from the lamella and remains in an amorphous phase. By this way, the
crystallinity of melt-crystallised polymers lie within a range extending from 85%
to 90% for very regular and flexible polyethylene chains down to about 30–40%
maximum for most other crystallisable polymers. Polymers are often said to be
‘‘semi-crystalline’’, whereas ‘‘partly crystalline’’ should be more correct.
By optical microscopy (OM), birefringent structures are observed in semi-
crystalline polymers, characterized by ‘‘Maltese-crosses’’ under crossed polars as
seen in Figure 6. As these structures grow symmetrically in three dimensions
 Polymer Chemistry and Microstructure 21

Figure 5 Electron micrograph of a portion of melt crystallised polyethylene spherulite by

transmission electron microscopy (TEM) showing lamellae. Reproduced from Ref. [3] with
permission of John Wiley & Sons, Inc.

from a nucleus, they are called ‘‘spherulites’’. Upon examination, they appear
to be formed of ‘‘fibrils’’ growing from the nucleus. These fibrils include
several lamellae most often linked by tie-molecules going from one lamella to its
neighbour.
In semi-crystalline polymers, ordered structures appear at different dimen-
sional levels
1. the crystal cell
2. the lamella
3. the fibril
4. the spherulite.
Such a complex microstructure is illustrated in Figure 7.

2.4 Microstructure
2.4.1 Linear and branched homopolymers
Polymers that are built from the repetition of identical ‘‘repeat units’’ are called
‘‘homopolymers’’ (from ancient Greek ‘‘òmoB’’ ¼ same).2 Linear homopolymer
chains are obtained upon linking chemically identical units exclusively at both
ends. However, repeat units are not always symmetrical in the chain direction.
Depending on the orientation of the repeat unit, different microstructural

2
Copolymers that are made from the repetition of two (or a very few) different units will be the subject of a later
paragraph.
22 Jacques Devaux and Sophie Demoustier-Champagne

Figure 6 Spherulites of isotactic poly-1-butene (a, during growth) and of polyethylene (b,
after completion) by optical microscopy (OM) under crossed polars. Reproduced from Ref. [3]
with permission of John Wiley & Sons, Inc.

Growth Intercrystalline tie chain

(amorphous)
Crystalline lamellae

Amorphous phase
Nucleating seed

Figure 7 Scheme of the internal structure of a spherulite. Reproduced from Mercier,

Zambelli and Kurz [1], Elsevier (2002) with permission of Elsevier. Copyright Elsevier 2002.
 Polymer Chemistry and Microstructure 23

CH3 CH3 CH3 CH3 CH3

C C C C C C C C C C
H2 H H2 H H H2 H2 H H2 H

A B C A
Figure 8 Schemes of (A) ‘‘head–tail’’, (B) ‘‘head–head’’ and (C) ‘‘tail–tail’’ microstructural
arrangements in polypropylene.

SCB Dendrimer

LCB Hyperbranched

Figure 9 Examples of branching in polymers LCB (long-chain branched, e.g., LDPE) and SCB
(short-chain branched, e.g., LLDPE), dendrimer and hyperbranched.

arrangements — ‘‘head–head’’, ‘‘head–tail’’ or ‘‘tail–tail’’ — can occur

(1D microstructure); these are called positional isomers (Figure 8).
Due to either accidental or intentional events during the synthesis, branching
points can occur along the chain (2D microstructure). Although this needs the
presence at the branching point of, stricto sensu, a ‘‘non-identical’’ unit, these
macromolecules remain classified as homopolymers.
Branching can also give rise to either the so-called ‘‘long-chain branching’’
(LCB) or ‘‘short-chain branching’’ (SCB), see Figure 9. Such terms are of importance
particularly for polyethylene as they describe the only3 small ‘‘chemical’’ difference
between technologically highly different low-density (LDPE) and linear low-
density (LLDPE) polyethylenes. Except for polyethylene, the distinction between
LCB and SCB is somewhat controversial as it can depend on several characteristics
or even on the capacity of the characterisation method itself.
From the branching point three or more chains can arise. This depends on
the so-called ‘‘functionality’’ of the ‘‘monomer’’ at the branching point (the
‘‘branching unit’’). This functionality can be defined as the number of molecules
(monomers, branches) actually linked to one branching unit. This definition can
be extended to monomers purposely inserted into a chain to create branching. In
this case the definition of functionality is generalized to the number of monomers
that can link to the considered unit. ‘‘Normal’’ monomers have thus a
functionality of 2. Branching units can exhibit functionalities of 3, 4 or more.

3
End groups are not taken into account here.
24 Jacques Devaux and Sophie Demoustier-Champagne

2.4.2 Dendrimers and hyperbranched polymers

Highly non-linear homopolymers can even be synthesized exclusively from
monomers of functionality higher than 2. Dendrimers (from ancient Greek
‘‘dendron’’ ¼ tree) are obtained when all the reaction sites of each branch links to
another one and when all branches exhibit the same length. Whereas,
hyperbranched (HB) polymers result from incomplete reaction of each multi-
functional monomer, see Figure 9.

2.4.3 Crosslinked homopolymers

As the number of branching points per chain increases, (when it becomes W2) an
almost infinite network of covalent bonds can be created. Strictly all the system
belongs to only one giant macromolecule. The polymer becomes insoluble and
infusible; it is said to be ‘‘crosslinked’’.
Even if, formally, an infinite network of covalent bonds can give rise to a 2D
infinite structure (when grown onto a surface, for instance), crosslinked polymers
are generally considered as 3D structures. Such crosslinked structures can be
made either by using monomers exhibiting functionalities higher than 2
(thermosets like polyepoxides, phenolics), or by inducing a reaction of preformed
linear chains with ‘‘bridging’’ molecules (e.g., vulcanisation of natural rubber)
(Figure 10).
Crosslinked 3D networks are normally amorphous,4 infusible and insoluble.
Solvents can only swell networks. However, polymers resulting from polymer-
isation of molecules of functionality higher than 2 can remain soluble during the
course of synthesis, below a certain ‘‘critical conversion value’’. Above this state,
‘‘gelation’’ occurs. Even in this state, the system remains partially soluble. It can
be separated by solvent extraction into two phases: the soluble phase is called the
‘‘sol’’ and the insoluble phase the ‘‘gel’’. As the monomer conversion proceeds,
the amount of ‘‘sol’’ decreases, while the amount of ‘‘gel’’ increases. The
behaviour of crosslinkable amorphous systems during their synthesis can be
described in the so-called time–temperature transformation or ‘‘TTT diagram’’
(Figure 11). It has to be noticed that such a TTT diagram can only be used in the
direction of increasing time (transformation). A particular characterisation of a
crosslinked system is the determination of the crosslink density. Access to the
measurement of such crosslink densities is possible through models requiring
determining the swelling of these systems.

2.4.4 Linear and branched copolymers

Copolymers are built from the repetition of two (or more) ‘‘repeat units’’.
Depending on the spatial arrangement of those units (e.g., A and B) along the
chain (sequencing), various types of copolymers can be made: alternating, block,
random (or statistical), branched, crosslinked (see Figure 12).
More sophisticated microstructures are sometimes synthesized, but the highly
complex chain sequencing encountered in natural copolymers, like proteins or

4
Depending on the mobility of chain segments, some crystallisation can occur in crosslinked systems.
 Polymer Chemistry and Microstructure 25

C CH C C C CH
H2 H2 H H2

Cross-link

C C
H2 H CH C
H2
A

C CH C CH C C C
H2 H2 H2 H H2

CH3
CH C C C
H H2
B S

S
C C C C
H2 H H
CH3

Figure 10 Examples of crosslinked polymers (A, polyfunctional; B, vulcanised).

enzymes, are still not accessible to chemical synthesis at the beginning of the
third millennium. Several physical properties of copolymers are directly or
indirectly dependent upon the distribution of sequences. The phase behaviour
(microphase separation) in block copolymers is linked to the mutual insolubility/
solubility of the sequences. This will be discussed further.

3. FROM MOLECULES TO MACROMOLECULES

As mentioned previously, chemistry and physico-chemistry play major roles in

polymer microstructure, and, as a consequence, on polymer properties. The
characterisation of several chemical parameters of polymer chains is thus of
paramount importance for controlling the final properties of polymer materials
 Chain length or molecular masses
J Entanglement

J Concentration and type of end groups

 Nature of chain substituents

26 Jacques Devaux and Sophie Demoustier-Champagne

UNGELLED GLASS
GELLED GLASS

GELATION

GLASS
TIME TO GELATION AND VITRIFICATION

VITRIFICATION

RUBBER

LIQUID GELATION

Tgg Tg∞
CURE TEMPERATURE, TCURE
Figure 11 Example of time–temperature transformation (TTT) diagram. (Increasing time in
vertical direction). Reprinted from Roller and Gillham [4], published by the Federation of
Societies for Coatings Technology, with permission of publisher.

A A B A A B B B A B B A Random

B A B A B A B A B A B A Alternate

A A A A A B B B B B B B Block or sequenced

A A A A A A A A A A A A
Branched
B B
B B
B

Figure 12 Examples of microstructures of copolymers.

 Polymer Chemistry and Microstructure 27

 Spatial arrangement
J Cis–trans isomerism
J Chain configuration

J Chain conformation

The chain structure (length, entanglement, branching, tacticity,y) of polymers

is discussed further in the next chapter (Chapter 4) by Beaucage and Kulkarni.

3.1 Chain length and entanglements

An important chemical characteristic of a polymer is the chain length. Chain length
strongly influences the thermal properties as illustrated in Table 2 for several
aliphatic compounds of different lengths. Detailed studies have been published on
the influence of chain length on melting temperatures of various polymers [5] or on
Tg and Tm (melting temperature) of aromatic polymers [6].
Above a characteristic chain length polymer chains may (depending on
the rigidity of the polymer backbone and/or on processing (stretching))
undergo the formation of entanglements. These entanglements mainly govern
rheological properties and several mechanical (viscoelastic) properties. A less
known, and indirect, effect of such entanglements is a lowering of ‘‘pure’’ thermal
stability of polymers as compared with corresponding lower mass compounds
(non-entangled). As an example, in absence of oxygen, linear polyethylene starts
degrading at about 3001C, while hexadecane can resist up to 5001C [7].

3.2 End groups

A useful relationship can be written between molecular mass and end group
concentration for linear polymers. Indeed, as there are exactly two end groups

Table 2 Influence of chain length on melting point, T, of aliphatic compounds H–(CH2)n–H

n Name Melting T (1C)

1 Methane 182.4
2 Ethane 182.8
3 Propane 189,9
4 Butane 138.3
5 Pentane 129.7
6 Hexane 95.0
8 Octane 56.5
10 Decane 29.7
12 Dodecane 9.6
18 Octadecane 28.0
30 Triacontane 65.5
EN Polyethylene 110–135
Another Random Scribd Document
with Unrelated Content
 While the shaving was in progress this morning and three of the
men were trying to shave by the aid of one little cracked mirror
about three inches by two in size, Brat, the despatch-rider attached
to the squadron, said to the inimitable Cowdie,

"I hope you finished that letter last night, old man. You finished up
all that two inches of candle I lent you. It must have been a long
letter you wrote."

"No, I didn't quite finish it," replied Cowdie quietly.

"Was it another letter to your little girl in Old Blighty?"

"No, it was a short letter to mother," replied the Spare Part in a

choking voice.

"Dear me! And you didn't finish it?"

"No," came the quiet answer, as Cowdie began to attack his upper
lip, which was all quivering with apparent emotion.

"What did you say, then?"

"I said, 'Dear Mother,--I am sending you five shillings, but not this
week.'"

At this a burst of laughter from the whole party called forth the ire
of Old Snorty, who was passing by, for he had been up early, with
several squads of air-mechanics, seeing off "B" Flight, who were
paying another early morning visit to the enemy.

"A little less noise there, Number Seven, or some of you'll be in the
guard room. How the deuce can we hear when 'B' Flight's coming in,
if you kick up a row like that?"

"Old Snorty seems to have something on his mind this morning,

doesn't he?" said some one. "'B' Flight won't be back for a couple of
hours yet."

So the men were quiet for a whole minute after that until the
sergeant-major, having passed out of earshot, and there still being
three minutes left for parade, the men returned to their chaff and
titter, Brat leading off again by saying:

"That letter of yours, Cowdie, reminds me of another chap who

worked alongside of me near St. Pierre with the --th Squadron. He
once wrote a letter to his mother as follows:

"'Dear Mother,--Enclosed please find fifteen shillings. I cannot.

"'Your affectionate son,
John.'"

And the joke was reckoned so good in our squadron that we raised
the money for the poor chap, and he sent it after all."

"Fall in!" came a stentorian shout, as Brat finished telling this yarn.
And the men of Number Seven doubled up to fall in on the left, and
answer their names to the early morning roll, for another day had
begun, and more than one man of that small crowd was to prove
himself a hero before another sun should come up out of the
German lines beyond Ginchy, and set in blood-red clouds behind the
British lines.

Some two hours after that, as the men busy about the labours of
the day, which in an aerodrome, under active service conditions,
range from the rigging of a defective aeroplane, mending struts,
replacing controls, preparing ammunition dumps, to the taking down
of a R.A.F. engine, and while "A" Flight was returning from a
reconnaissance, and "C" Flight was preparing to go up and over the
lines on a bombing raid, Grenfell, the orderly officer at the
aerodrome 'phone, received a broken message from somewhere
near Ginchy.

The message had to do with the crash of a British 'plane

somewhere in front or just behind the first line trenches, but a
terrific bombardment being concentrated on the place at the time
the message suddenly ceased, as though the wires had been
broken, or the speaker at the other end put out of action.

A minute later Snorty came dashing down towards the spot where
Number Seven squad were working.

"Where is Brat?" he shouted.

"Over there, sir, in the transport shed," replied Cowdie.

"Fetch him at once!"

And Cowdie dashed off to find his chum, bringing him back a
moment later.

"Bratby!" shouted Snorty, giving the despatch-rider his full name

for once, as he saw the two doubling up.

"Yes, sir," came the answer smartly.

"You know the observing officer's dug-out near Ginchy?"

"The place where I carried the despatches the other day, sir?"

"Exactly."

"Yes, sir, I know it."

"Good! Go there at once. The wires are snapped again, and we

have received a broken message through which stopped in the
middle. One of our 'planes has come down. It must be part of 'B'
Flight, for they're not in yet. Go there at once, take this message to
the officer or senior N.C.O. in charge, and get the full message from
him. Learn what you can while you are there, and come back at
once, so that we may send out a breakdown gang for the machine,
if not too late."

"Right, sir."

"Mind, we want the exact location of the machine, and you must
try to find out if it is a bad crash, and what has become of the pilot
and observer."

"Yes, sir."

"Now get off at once. It is five minutes since the machine crashed.
And be careful now. There are some nasty corners there, and the
Germans are shelling the Ginchy lines 'hell for leather' this morning."

Then, catching sight of Cowdie, for whom he had rather a soft

place in his rugged heart, the Sergeant-Major added,

"Better take the 'Spare Part' with you. You may need a second
man."

"Right, sir."

The next moment the two chums, happy as schoolboys because

they were entrusted with a dangerous commission, had the "New
Triumph" out of the shed. Then, with Cowdie seated on the carrier,
Brat on the saddle, away they went, past the aerodrome sentries,
out at the gate, and down the road towards the trenches.

"Zinc-zinc-a-bonck-rep-r-r-r-r!"

But, alas, it was an adventure which was to prove something more

than a joy ride, before another two hours were past.
 It was a clear sunny morning as they pattered along, wondering
much what new venture it was that awaited them. Over there
towards Ginchy the air was thick with bursting shells, and the clear,
blue sky was marked in a score of places at once by aeroplanes and
kite balloons, whilst round about them were splashes of fire, and
floating milk-white cloudlets where the shells burst, as the Huns tried
to bring down our "birds."

An air-fight was in progress already over Ginchy; two Fokkers

which had ventured near the British lines were being countered and
chased by several of our Sopwiths. They were two of the very same
Fokkers which had chased Dastral and the remnant of "B" Flight
after their drums of ammunition were all used up.

But Dastral, where was he at this moment? This was the thought
that was uppermost in the minds of the two men as they whizzed
down the Ginchy road, leaving Bazentin on their left. For of all the
pilots of the --th Squadron, Dastral was the greatest favourite with
the men. He was so brilliant and daring that they felt they could not
afford to lose him.

"I hope it isn't Dastral who has crashed, Cowdie," said Brat.

"I hope not," replied Cowdie, feeling at the time somehow that it
could be no one else.

"'B' Flight ought to have returned some time ago now. I'm very
much afraid they've met their match this time. We could afford to
lose half a dozen men rather than the Commander of 'B' Flight."

"Perhaps he's met Himmelman," urged the man on the carrier,

steadying himself for the next heavy jolt, for the last one had nearly
thrown him off, and the bad places were becoming more and more
plentiful as they neared the lines.

"He will meet him some day, and there'll be a deuce of a fight. Just
mark my words. There isn't room for two lords of the air, not in
these parts, and one of them will go under."

"Well, I hope it will be the Boche."

"So it will be if they meet on equal terms, but the German air-fiend
is a wily brute."

"Whiz-z-z! Bang-g-g!" came a shell at that moment, striking the

ground not thirty yards away from them, and sending both men and
motor-cycle spinning into the ditch by the very concussion.

"Not hurt, are you, Cowdie?" asked Brat, as he scrambled out of

the ditch first, and ran to help his friend.

"No, but it was a very near thing that. Another few inches and that
would have been the end of the regimental 'spare part.' Look here!"
and Cowdie showed a rent in his tunic where a piece of shrapnel had
torn away six inches of it behind the left shoulder.

Fortunately, though both were shaken, neither of the men had

been actually hit It was a marvellous escape, however, one of those
things one cannot account for. Though the machine had been badly
knocked about and splintered, it had received no vital injury, and,
after straightening out a few spokes, and cutting away a few more
they mounted again and proceeded a little further.

"Halt Who goes there?" came the shout as they pattered up to the
support trenches.

They halted and dismounted, and after telling their business were
allowed to proceed, but they were cautioned that the road ahead
was full of shell holes, and that they would not be able to ride much
further. They would certainly be stopped at the reserve trenches.

Once more they started, their heads throbbing and aching with the
noise of the terrific bombardment which was proceeding, for they
were now in the super-danger zone, and shells were screaming
overhead every few seconds, and many were bursting on their left
and on their right.

Again they were halted, this time by a sentry near the second line
trenches, and were absolutely refused permission to proceed further
till they explained to the officer of the company commanding the
trench what their errand was.

"Wires broken, did you say?"

"Yes, sir."

"Nearly all the wires to the front line trenches in this sector have
been broken. We have had the engineers out all the morning
mending them."

"There is news of one of our fighting 'planes having crashed

somewhere over there, half an hour ago, sir," said Bratby, "and we
have been ordered to proceed as near as possible to the place, to
find out what has happened, as the aerodrome wire has been
snapped."

"An aeroplane crashed, did you say?" asked the officer.

"Yes, sir."

"There have been half a dozen of them down in front of us since

seven o'clock this morning; most of them German, I think."

"This was one of ours, sir."

"Yes, I saw it. There were two of them came down about the same
time, but the other one fell by our support trenches and the pilot
and observer were saved."

"And the other one, sir?"

 "Oh, there is no hope for that one. She came down over there near
our front line trench, and she was blazing when she crashed. We
could not get at her, or at least we kept the men back who
volunteered, as the Germans turned their machine guns on her
directly she hit the ground and swept the spot for twenty minutes."

"The devils!" ejaculated Brat, looking more serious than he had

ever looked in his life, while a strange light shone in Cowdie's eyes.

"We were told that we must get to the dug-out of Captain Grenfell,
somewhere in the front line trench."

"Oh, very well; but you fellows go at your own risk. The Boches
have been shelling the place like hell most of the time since
daybreak."

"We're quite prepared to take the risk, sir!" replied Cowdie.

"Come this way, then, and mind that corner. We call it Hell-fire
Corner these days, for we have lost more men there than at any
other point," replied the officer.

A few minutes later he handed them over to a sergeant, with

instructions to conduct them to the dug-out where Captain Grenfell
and his two operators still held on to the end of the broken wires. No
messages had come through for some time, but several squads of
Royal Engineers were busy crawling out in the open and trying to
find the loose ends in order to restore communication.

When they arrived there Captain Grenfell gave them the full text of
the message which he had tried to get through, and pointed out to
them the place where the ruins of the aeroplane lay, for they were
still smoking.

"But the pilot, sir, where is he? And where is the observer? They
were the best men in the Squadron, and their loss will be felt
greatly, for Lieutenant Dastral was reckoned the best pilot in France,
and great things were expected from him in the near future," said
Brat.

For answer the Captain shrugged his shoulders and made a gesture
which seemed to indicate that he feared the case was hopeless.

"Their bodies must be somewhere over there. Several of our men

volunteered to go over to rescue them, but every man who went
over the top went to his death, until the O.C. refused permission for
any more to attempt it, for he said he could not spare the men."

While they were thus discussing the matter, one of the sentries a
little further down the trench gave an alarm:

"Cloud of gas or fog coming over, sir, from the German lines!"

Brat and Cowdie, at these words, peeped over the edge of the
parapet, and saw, about a quarter of a mile away, a dense yellowish
vapour coming slowly onward from a point where the enemy's lines
curved round and faced the British lines from almost due south-east.
The order was passed quickly down the lines for the men to don
their gas-helmets, but the C.O. coming along the trench shortly
afterwards, remarked that it could not possibly be gas, for, from the
direction whence it came, it would pass onwards over a portion of
the enemy's lines at a spot where the trenches curved back again
and made a salient. At this point the lines twisted and bent
themselves into many curious salients, for the last advance had not
thoroughly straightened out the position.

"The Germans are not such fools as to gas their own men, Grenfell,
what do you say?" remarked the officer commanding the trench to
Grenfell, who had come out of his dug-out to get a view of the
cloud.

"No, sir. There must be some other reason."

 "Yes, and the reason is, I think, a change of wind which is bringing
on a dense fog."

"You are quite right, sir," added the other, after regarding the air
and sky for some ten seconds. "There has been a sudden change of
wind, and a dense local fog is coming up from the valley. The whole
landscape will be blotted out in a few minutes."

"You're right, Grenfell," replied the officer. Then, turning to his

orderly-sergeant, he called out:

"Pass the order for the men to stand-to! There is no telling but that
the Boches may come over the top with the fog, and try to surprise
us."

"Yes, sir," came the reply smartly, and the sergeant, saluting,
disappeared along the trench, calling out the men from the dug-
outs, and ordering a general "stand-to."

The chance was too good to be lost. Cowdie gave Brat a dig in the
ribs, and whispered to him,

"Now is the time. See, the fog thickens, and it is nearly up to the
wrecked aeroplane. Let's go over, or the Boches will be there first.
They're sure to try it on. What say you?"

"I'm with you, old man, but it will be an awful job. Have you got
your revolver loaded, for we've got nothing else?"

"Yes," replied his chum, feeling that his weapon was safe in the
leather case, which hung at his left side.

"Come on, then; we haven't a second to lose."

The next instant they were over the top, and making a dash for the
spot already hidden in the fog.
 "Come back there, you fellows!" cried a sergeant of the Wiltshires,
whose company lined the trench. "Where the deuce are you going
to?"

"To save Lieutenant Dastral and his observer, sergeant! Don't let
your men fire on us. We'll be back in five minutes," shouted Bratby.

"Devil a bit of use you fellows throwing your lives away like that.
The Boches are sure to attack under cover of the fog. Come back,
the pilot must have been dead an hour. The machine was ablaze
when it crashed," called the sergeant again.

To this they returned no answer, but scampered as fast as they

could across the broken ground, creeping under barbed wire, and
stumbling into shell holes, for the ground had been torn and rent by
the morning's bombardment, and huge gaps had been made in the
barbed wire defences.

Now, when Dastral, his ammunition expended, his machine

damaged to such an extent that it scarcely held together, had
reached the British lines that morning, after the brilliant
reconnaissance he had carried out with his Flight, he made a steep
gradient to get to earth at the first possible landing-place, but even
as he made the attempt he knew he would fail. The wasp's fuselage
was plugged in a hundred places. The petrol feed had been severed
by shrapnel, and a shell from the German lines, hitting the reserve
petrol tank, set it ablaze, just at the moment when he was making
for the ground.

Half-blinded by the flames and scorched by the heat, he,

nevertheless, held the joystick firmly, and tried to reach his
objective, but, when near the trenches, the machine nose-dived and
crashed, side-slipping to the earth, so that the left aileron struck the
ground first. Then she rolled over, and crumpled up. She did not
strike the ground with any great force, because Dastral had kept her
so well in hand.
 Disentangling himself from the wreckage first, bruised, and burnt,
he yet remembered Jock, who had received still greater injury.

"Jock!" he called. "Are you hurt?"

But no reply came from the unconscious observer, who lay under
the wreckage which was now in flames.

"Come along, old man! Pull yourself together. The Huns are sure to
turn their machine guns upon us in a few seconds."

Even as he spoke there came the dreaded sound, which told that
the infernal Huns had opened fire upon the wreckage.

"Rep-p-p! Rep-r-r-r-r-r!"

A howl of rage went up from the British trenches at this act of

cowardice, which permitted men to turn their guns upon wounded
officers, entangled in the wreckage of a burning aeroplane.

"Come on, boys, let's give 'em 'ell!" shouted some of the Wiltshires,
when they saw what was happening, and at least a dozen men
sprang out of the British trenches of their own free will in a useless
attempt to save the lives of the aviators, but every man fell long
before he gained the spot where the wreckage lay.

Dastral, however, kept cool, and seeing a pilot's boot projecting

from under the blazing he seized it, and tugged away, until the
unconscious form of his chum lay at his feet. Then, heedless of the
bullets still whizzing around him, he dragged his comrade quickly
into the friendly shelter of a huge crater, a dozen yards away. Even
as he rolled over into the hollow, after throwing Jock in first, his
thick, leather pilot's coat was pierced by several bullets, and he
himself was wounded again.

Still cheerful, however, he bandaged his wound, then endeavoured

to rouse Jock, but all his efforts failed.
 So he searched him, found several wounds, bound them up as well
as he could with the emergency lint and bandages which every
soldier on active service carries in the lining of his coat. Then,
through sheer loss of blood he fainted away, and lay there he knew
not how long, for he was thoroughly exhausted, and felt that he was
dying.

As he slumbered, sheltered in that little hollow from the direct fire

of the enemy, he became feverish, and dreamt wild, fantastic
dreams. With Jock beside him he sailed away on the hornet, over
distant lands, where the skies were blue and the sun shone bright
and the atmosphere was pleasant and warm.

Here there were no Germans to worry them with shrapnel and

bullets, but calmly and serenely they sailed over huge forests and
deserts, swamps and islands, which studded the deep blue sea far
below them, like gems set in emerald. Now they were in the tropics,
skimming along over huge palm trees, and lagoons that opened out
into the sea. Great monsters basked in the sunlight on the banks of
the rivers and lagoons, and on the shores of the sea. They were in
an unknown land discovering strange places. Just such a trip it was
as Jock and he had often talked about, when, the day's work done,
they had settled in the comfortable arm-chairs in the officers' mess
at the aerodrome near Contalmaison.

Often they had talked of these things, and the trips they were
going to make in the happy years to come, when the fighting was all
over, and the smoke of battle had blown away, and the liberties of
mankind had been won back from the tyrants of these latter days.

Thus he dreamt, for he was feverish, while over him the shells
burst, and the great guns thundered, and all around, upon the wide-
stretched battlefields, the dead and the dying lay. And always he
was parched and thirsty, and sometimes he would turn and say to
Jock:
 "There, far below us in the desert, Jock, I can see an oasis, with
pools of cold refreshing water, and a cluster of tall trees, where we
shall find dates and figs. Let us go down, Jock."

But the vision would fade before he reached the promised land,
and the cup of water was dashed from his lips, and the goblet
broken. Again he would see across the desert, which now seemed
interminable, mystic and wonderful lakes of fresh water. But always
he was mocked, and again and again those horrid German guns
would thunder out from far below and forbid them to land.

Suddenly from out of the midst of his dream, he heard some one
calling his name.

"Dastral! Lieutenant Dastral!"

He turned uneasily in his sleep; then he woke with a start, and

looked about him. His brow was flushed, his head burned as though
it were on fire, and his eyes glittered. All seemed dark, for the
landscape was blotted out by a dark cloud.

Half regaining consciousness he murmured:

"Where am I? Who called me?" But while he wondered, his hand

touched something, and he shrank back startled. It was Jock's poor
wounded and bruised body that he had touched. Then he
remembered it all. The flight over the German lines; the attack
which had been made upon them by a whole German squadron; the
fierce fight and the dash back, followed by a cloud of Fokkers and
Aviatiks. Then the crash----. Yes he remembered it all now, and Jock,
poor Jock must be dead, for he had not moved, and they must have
been there for hours, days perhaps--at least, it seemed so, for it was
dark as night, and it was morning when they crashed.

Then again he heard that welcome sound, a human voice, and it

called him by name.
 "Dastral! Lieutenant Dastral, where are you?"

And he feebly answered with all his strength.

"Here! Here! For heaven's sake help us!"

The next instant two burly forms came stumbling and rolling down
the crater, for Cowdie and Brat had just arrived at the spot, and as
yet scarcely an hour had elapsed since the crash. Strong arms were
put around the pilot, which raised him up, for he had fallen down
again, after his effort to rise. He had just time to murmur something,
and point to the unconscious form of his observer, when he relapsed
into unconsciousness again.

"Thank God we have found you both, sir!" exclaimed a strong

voice, which seemed to resound again and again through his being.

As the thick fog came on, the firing had been suspended for a
moment. It was a strange, weird silence that seemed to presage a
coming storm. Cowdie was the first to read its meaning.

"Quick, Brat!" he cried. "They're going to attack. We must make a

dash for it."

It was only too true. Scarcely had they reached the top of the
crater, and proceeded a dozen yards with their heavy burdens, when
they heard the sound of voices.

"Hist! What was that?"

They paused for a moment, and waited, but it seemed to them that
their panting and the loud thumping of their hearts would betray
them. How far had they to go yet? they asked each other. Then, with
a shudder, Cowdie turned and began to retrace his steps, whispering
to his comrade:
 "We have come the wrong way. Those are the German trenches
over there, and look, they are forming up over the top ready to
attack."

"Good heavens! Then we are lost," replied his comrade.

"No, we may yet be in time. Come along. It cannot be far."

With his keen blue eyes Cowdie peered through the gloom, for
Cowdie, the "spare part," had been the first to make the discovery.
He had seen the shadowy forms of the Germans not twenty yards
away. Fortunately, they had not been observed as yet, but they were
not out of danger. They had regained their right direction, however.
The British trenches were not more than seventy yards away.

On they stumbled, over the broken ground, through pools of water,

and soon they reached the tangled wire. Exhausted they were ready
to sink with fatigue, yet they held out. But their hands were bleeding
and torn by the wire, and their clothing was in shreds.

Suddenly they heard the sound of voices behind them. Low voices
called to each other, and the tramp of feet was also heard.

"They are advancing. Quick! quick!" shouted Cowdie.

Then, knowing that the British trenches could not be more than
thirty yards in front of him, he called out:

"Stand-to! The Huns are attacking!"

The next instant a blaze of fire lit up the fog, as a dozen Very lights
were fired up from the British trenches. The two figures of the men
carrying the unconscious pilot and observer were clearly outlined.
The sergeant of the Wiltshires shouted to his men:

"Don't fire! They are the R.F.C. men bringing in their officers."
 The firing, however, came from a different direction, for the
Germans, baulked of their prey, and seeing who had given them
away, opened fire, and Cowdie stumbled into the British first-line
trench into the arms of the sergeant of the Wiltshires, carrying his
burden to the last. He was dead, shot through the heart. He had
made the supreme sacrifice to save the man he loved.

With a wild cheer the British received the welcome order to charge,
and the last thing that Brat remembered was that cheer, as the men
swept by him, and he also sank down with his load.

Next day they buried Cowdie, "the regimental spare part." Gently
they laid him to rest in a little graveyard by a shattered church,
behind the British lines. And over his grave the bugles of the
Wiltshires sounded the solemn notes of the "Last Post." And his
comrades in Number 7 tent fired three volleys over the hero's grave,
just as in the olden days, two thousand years ago, AEneas and his
comrades, when they buried the hero Misenus, called his name
thrice into the shades.

And Bratby, he recovered from his wounds, and, to-day, upon his
breast he wears the ribbons of the Military Medal.

Dastral and Jock also recovered from their wounds, for their work
was not yet done, and six weeks later were back from sick leave,
preparing once more to strafe the Huns.

CHAPTER VIII
THE RAID ON KRUPPS
 IT was a dark night, some two or three hours before dawn, when
Air-Mechanic Pearson, one of the outer sentries at the aerodrome
near Contalmaison, thought he heard the whirr of propellers
somewhere in the dark skies above.

For a few seconds he peered up into the gloomy heavens, trying to

locate the sound, for he was very much puzzled, and could not
account for the sound on such a night.

"They can't be aeroplanes returning from over the lines," he told

himself, "or we should have had notice to light the flares. It will be a
sheer impossibility to land without a crash on a dark night like this."

Again he listened, and he thought the droning sound settled down

into the throb of engines. He was anxious, however, not to call out
the guard on a false alarm, for he had once been severely
reprimanded for so doing.

"They cannot be hostile 'planes attempting an early morning raid; it

is far too thick. It would be like a nigger trying to find a black cat in
a dark cellar," he muttered.

A quarter of a minute later, however, he thought he had discovered

the real cause, for the throbbing of aerial engines could now be
distinctly heard.

"It's a Zeppelin!" he exclaimed. "They're going to find the

aerodrome with their search-light, and bomb the place, then make
off before our machines can get up," and he instantly yelled out at
the top of his voice, "Turn out, guard!"

The alarm was caught up, passed on to the next sentry, who
repeated it, and the next moment, after turning out the main guard,
the sergeant came running up, and asked:

"What's the matter, Pearson?"

 "Zeppelin approaching from the eastward, sergeant!" replied the
air-mechanic.

"Zeppelin, man! What the deuce do you mean? Where is it?"

"Up there, sergeant. I can hear it quite plainly now."

"By Jove, so can I!"

The next moment the sergeant was back in the guard-room. From
thence he dashed into the orderly-room, and knocked at the inner
door, where the orderly officer for the night was on duty.

"Come in," cried the officer in answer to the knocking. Then, as the
sergeant, all puffed with his exertion, entered and saluted, he said:

"What's the matter, sergeant?"

"Zeppelin approaching from over the German lines, sir. Hadn't we

better 'phone to the anti-aircraft guns, and the searchlights to pick
up the raider before he bombs the place?" for to the sergeant's
mind, visions of falling bombs and terrific explosions were present.

"Zeppelin?" laughed the orderly officer.

"Yes, sir. I can hear the engines as plainly as possible outside."

"No, you're mistaken. It's the 'Gertie' returning. She's been out on
secret service work behind the German lines. I've been expecting
her for a couple of hours. Not a word of this to the men, now. I am
expecting a secret service man back before dawn, and the 'Gertie's'
been to fetch him. Picked him up at some secret place in the dark,
far behind the enemy's lines."

Now, the "Gertie" was a baby-airship detailed for special service,

and not the least important part of her work was the secret
journeying to and fro, across the German lines, to quiet rural places,
where, in the dark, she dropped messages, carrier pigeons, etc., and
occasionally brought back some daring member of the British Secret
Service, who had been collecting information behind the enemy's
lines.

By this time the orderly officer was out on the aerodrome, and the
squads of air-mechanics were being roused by the orderly sergeant.
Suddenly there came a cry from one of the guard.

"Airship signalling to the aerodrome, sir!"

"What signal was that?" demanded the officer.

"Two green lights and a red, sir, over there, half a mile away,"
came the reply.

"That's right. It's the 'Gertie' trying to find the landing place. Flight-
sergeant, where are you?"

"Here, sir," came the answer, as the aerodrome flight-sergeant, just

roused by the alarm, rushed up, without putties or tunic on.

"Light the usual flares at the landing-place, and give the Brigade
colours as well."

"Yes, sir."

And the next instant he had disappeared into the darkness again to
hurry up the air-mechanics and to light the flares. The "Gertie" had
very nearly found her mark, having over-shot it but half a mile or so
in the pitchy darkness, which was a very creditable performance.

As soon as the flares were lighted, her engines, which had been
shut off, were heard again, as she gradually came nearer and nearer,
until, when right overhead, she began to descend slowly.
 "There she comes! This way, lads!" cried the stentorian voice of
Snorty, whose piercing eyes were amongst the first to spot the
looming mass overhead.

"Steady, there, steady!" came the next order, as the ropes and
drags were lowered, and the men made a scramble for them. And,
in a very short space of time the baby-airship was made fast, and
from the single gondola, in which five men were cooped, some one
leapt out, who held in his hand a bundle of documents.

"Captain Scott, I believe, sir," said the orderly officer stepping

forward.

"Yes. Are you Lieutenant Grenfell?"

"Yes, sir." And with that the two men went off together to the
private room of the orderly officer.

The newcomer was the bearer of some important plans and

sketches, to obtain which he had risked his life every hour of the day
and night during the past three weeks. They were nothing less than
detailed plans of the great German arsenal at Krupps', for which the
Commanding Officer had been anxiously waiting. For some time
previously, the C.O. had received from the War Office, through the
General Headquarters in the field, a peremptory order, something
like the following:--

"To the Officer Commanding,

"--th Squadron, Royal Flying Corps.

"It is of vital importance that the enemy's supply of munitions

should be hampered and restricted as far as possible, in view of the
offensive to be undertaken shortly. As soon, therefore, as the
necessary plans and papers reach you, you will detail one of your
best flights, under your most capable Flight-Commander, to carry out
the first raid on the enemy's main arsenal at Krupp'."

This document, signed by one of the generals commanding in the

field, had been in the hands of the Squadron-Commander for some
days, and he had been eagerly awaiting the arrival of the promised
plans and sketches. As soon, therefore, as the orderly officer
received them, he sent Brat, the despatch-rider, with his motor cycle
and side car to the C.O.'s quarters. And ten minutes later that
distinguished person was leaving the officers' quarters on his way to
the aerodrome.

Having arrived, after ten minutes' chat with the officer belonging to
the secret service, his first words were:

"Grenfell, ask Flight-Commander Dastral to come down at once."

"Yes, sir."

And on his next journey, Brat fetched Dastral down from his bunk
at the mess to join the party.

"Dastral," was the first word from the C.O. as soon as the daring
young pilot entered.

"Yes, sir," replied the Flight-Commander, saluting smartly.

"Here's something for you after your own heart."

"What is that, sir?" asked the youth, smiling.

"The promised raid on Krupps'. How would you like to undertake it

with your flight? You have often spoken about it."

"Nothing would please me better, sir."

 "And the other fellows belonging to your flight, what about them?"

"They would follow me anywhere, sir!"

"Gad, I believe they would, for they all worship you. I believe
they'd follow you to 'Gulfs,' if you led them there."

Dastral laughed, and repeated his avowal, that he would be only

too pleased to start at dawn should the weather conditions prove
good enough.

"Right!" exclaimed the major. "Then, you'd better spend the next
two hours with Captain Scott here, and with your men. Get
thoroughly hold of these plans, and fix them in your mind."

So, while breakfast was laid for the Intelligence officer, Dastral got
his men together, including Mac and Jock. Afterwards the eight men
who were going into action carefully laid their plans, arranging a
code of signals and the method of attack, should they succeed in
reaching their destination. Then they went over to the sheds,
examined and tested the machines, saw them loaded up with bombs
and drums of ammunition. The guns, compasses, etc., were then
shipped and everything was ready.

Dastral looked at his watch. In an hour it would be dawn.

"We must be off, boys. We must cros the German lines before
daybreak."

"Right, sir," replied the others, "We can be ready in ten minutes."

Then, having previously breakfasted, they put on their thick leather

coats, pilots' boots and helmets, and made ready. The C.O. came
down to wish them godspeed and a safe return. The probable time
of their return was fixed, and it was arranged that an escort should
meet them on their way back to defend them from hostile aircraft,
lest any of them should be in difficulties, and unable, through
damaged machines or lack of ammunition, to fight their way home.

"Stand by! Contact, switch off!" came the order.

The propellors were swung vigorously once or twice, then, one

after another, the engines broke into their mighty song, and the
machines taxied off into the darkness across the aerodrome, and as
the joy-stick was pulled over each 'plane sprang into the air, and
began its long voyage.

"Good-bye, and good luck!" shouted the C.O. as each man taxied
off, and as a parting salute, each pilot raised his gloved hand from
the controls for an instant.

Four hundred miles, that was the distance of the double journey.
Two hundred miles of enemy territory to be traversed before they
reached their objective; then, another two hundred back again to
safety; and no chance of a landing to remedy even the slightest
defect. That was the prospect before these daring aviators, as they
sallied forth on their dangerous errand this morning about half an
hour before the first faint whisper of dawn came up out of the east.

No wonder the Commanding Officer of the Squadron, as he

watched them depart, turned to his companions and said:

"A perilous venture, isn't it, for the boys?"

"You're right, sir," replied the orderly officer. "I hope not one of
them will lose the number of his mess before nightfall."

"Ah, well. We have had some vacant chairs in the mess lately. Four
hundred miles," he was heard to remark as he turned on his heels
and went back to his room.

He was a kindly, considerate commander, for he had that rare

quality which combined firmness with kindness, and because of that
he was loved by all his men.

The adventurers crossed the German lines at seven thousand feet,

and in the darkness the enemy's searchlights failed to find them, so
they were well away for once. There was just a little doubt in
Dastral's mind about the weather conditions when he started, as the
success of the venture depended very much upon the visibility. At
present, however, the dull cloudy weather was in their favour, if only
it might clear up later.

He was therefore very pleased when, having left the enemy's lines
some thirty or forty miles behind, the first tinge of dawn lit up the
sky in front of them, showing the horizon clearly. The wind had
changed during the last hour, and, though it grew colder, it became
much brighter.

Once or twice the Flight-Commander looked round at his followers,

casting a critical eye upon the whole flight.

"Thank goodness, the engines seem to be running well. Everything

depends on them," he murmured.

His own machine was a double-seater type with the observer's car
projecting right in front of the engine, a powerful twelve-cylindered
R.A.F.

A little later Jock, speaking through the tube, shouted:

"Shots on the left, Dastral!" and he pointed to a spot far down

below, for the landscape had opened out now, and they had been
spotted for the first time.

Dastral looked down, and saw several rapid flashes, away down on
the left, where a battery of "Archies," having found them, had
opened fire.
 In front of the machine which was leading the flight, Dastral saw
several black bursts of smoke, and in the centre of each burst was a
yellow glare.

"Ah, the Boches have found the range to a nicety!" yelled Dastral
to Jock. "Look out! We must dive."

Then, pulling over the controls, the hornet dipped at the head,
doing a neat little nose-dive of some five hundred feet, throwing the
enemy's range out of gear, and compelling him to readjust his sights.

As he dived, the others, with an eye always on their leader,

followed him, and the whole flight dived clean underneath a mass of
curtain fire, intended to bar their progress. So cleverly was it all
done that they all escaped without a scratch.

The Commander looked down at those batteries still spitting fire.

With not a little contempt he regarded them. They could not touch
him, for already, before they could readjust their fire, the whole
flight was out of range, for the engines were now doing well, and a
speed of a hundred and twenty miles an hour had been worked up.

At another time Dastral would like to have dived down to within

five hundred feet of those German guns, and put them out of action,
but he had other work on hand today; work which would take all his
time and skill to complete satisfactorily, and to bring his men back to
safety. Even if Himmelman himself should attack him now, he must
refuse him battle, unless compelled to fight for mere safety. His
present duty was to bomb the great arsenal at Krupps', and, as far
as possible, leave the principal buildings nothing but a heap of
smoking ruins. So he opened out the throttle of his engine to the
full, and for the first time reached one hundred and twenty-five
miles an hour, not a very bad speed when you are loaded up with
heavy missiles.

They had been flying for an hour now, and had climbed higher and
higher until they were at nine thousand feet. It was bitterly cold, and
already their feet and hands were numbed. What would they be like
in another two hours?

An hour and a half passed, and shortly afterwards Jock shouted:

"The Rhine! The Rhine!"

Nor indeed was he mistaken. He had been eagerly searching for

the famous stream that runs through the German Fatherland, and of
which the Hun is so proud. And now, there it was, a little way ahead
of them, running through the landscape like a silver thread.

Soon they were over the stately river, and Dastral, knowing that
the road was as plain as a pikestaff now if the weather kept clear, no
longer heeded his compass, but, wheeling smartly to his left,
followed the stream on its way to the sea.

"What town is that?" shouted the pilot, as a vast assembly of

houses and spires came into view.

"Coblentz," replied the observer, with his finger on the waterproof

map.

"Better look out for trouble, hadn't we?"

"Yes, the Ehrenbreitstein Forts are down below; just a little way
ahead on the left. They have plenty of guns down there."

This place, called the Gibraltar of Central Europe, is a towering

fortification, overlooking the town of Coblentz, and defending the
line of the Rhine. The river runs between the fort and the town, and
the two are connected by a bridge of boats.

"Better skirt the town, else they will think we are going to attack
the place, and some of our fellows might get winged."
 "Poch! They can't hit us. All their best gunners are miles away at
the front. Let's go straight on. We shall be out of their range in five
minutes."

Before they reached the town the white puffs of the 77's made a
line of smoke ahead of them, and, intermingled with this, they saw
the black cloudlets caused by the bursting of the enemy's 105 calibre
shells. In fact they were ringed with a curtain of shell fire.

Dastral gave the signal by a sudden clip of his 'plane, which was
leading.

"Ninety degrees left and dip 500 feet!"

The Flight-Commander led the way through a gap in the curtain

fire, and the rest followed, swerving rapidly to the left, then down,
down in a fearful nose-dive of hundreds of feet, before they
flattened out.

"Bravo! Well done, boys!" yelled the leader, waving his hand to the
daring men behind. For they had outclassed the Boche, and before
he could rectify his aim, the machines were out of range once more.

On the other side of the town, however, they came in for the same
treatment, but they once more evaded the enemy's fire, and soon
they left the town of Coblentz, with its Denkmal of Wilhelm der
Grosse, and the forts of Ehrenbreitstein behind them.

"Three hundred shots for nothing, Jock," shouted Dastral, who was
highly pleased with himself.

Jock did not hear, however, for the wind carried the words away,
and the observer was otherwise engaged, searching the skies with
his glasses. A moment later, however, having discovered what he
was looking for, he turned and shouted:

"One, two, three of them climbing to attack us!"

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