BASICS OF

POLYMERS,
VOLUME II
 BASICS OF
POLYMERS,
VOLUME II
Instrumental Methods of Testing

MURALISRINIVASAN NATAMAI
SUBRAMANIAN
Basics of Polymers, Volume II: Instrumental Methods of Testing
Copyright © Momentum Press®, LLC, 2019.

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First published in 2019 by

Momentum Press®, LLC
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ISBN-13: 978-1-94944-901-3 (print)

ISBN-13: 978-1-94944-902-0 (e-book)

Momentum Press Plastics and Polymers Collection

Collection ISSN: 2377-4193

Collection eISSN: 2377-4207

DOI: 10.5643/9781949449020

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 Abstract

Wide-range polymer materials require polymer testing, which is associ-

ated with public and economic factors. Perhaps in no other aspect of the
materials is there a great need for a dispassionate and rigorous a­ nalysis
because of the characteristics of a polymer. Polymer testing with instru-
mental methods are reliable with respect to technological options and
economics of the operations. Polymer testing is long established and
highly successful. However, the variations in the raw materials and addi-
tives, yet not without particular problems such as variations in molecular
weight, result in quality problems in the product.

KEY WORDS

additive; calorimetry; chromatography; Fourier transform; molecular weight;

spectroscopy; testing; thermal analysis
 Contents

List of Figures xi
Preface xiii
Acknowledgments xv
Chapter 1 Introduction 1
1.1. Objective: Polymer Testing 1
1.2. Necessity of Instrumental Methods 2
1.3. Specialization 3
Chapter 2 Importance of Polymer Testing 5
2.1. Polymers 6
2.1.1. Chemical Aspects 6
2.1.2. Architectural Aspects 6
2.2. Polymer Properties 7
2.3. Functionality Type Distribution 8
2.4. Chemical Composition Distribution 8
2.5. Physical Properties 8
2.6. Chemical Properties 9
2.7. Thermal Properties 10
2.8. Rheological Properties 10
2.9. Additives 10
2.10. Testing of Additives 11
2.11. Instrumental Methods and Their Role 12
2.12. Spectroscopy 13
2.13. Chromatography 14
2.14. Thermal Analysis 14
2.15. Rheological Measurements 15
2.16. Other Measurements 15
2.17. Chemical Methods versus Instrumental Methods 15
2.18. Importance of Instrumental Methods 16
viii  •  CONTENTS

Chapter 3 Spectroscopic Techniques 21

3.1. Spectrophotometric Analysis 22
3.2. Fourier Transform 22
3.3. Ultraviolet and Visible Absorption Spectroscopy 23
3.4. Near-Infrared (NIR) Spectroscopy 24
3.4.1. Industrial Applications 24
3.4.2. Advantages 25
3.4.3. Disadvantage 26
3.5. Infrared Spectroscopy 26
3.5.1. Basics 26
3.5.2. Fourier Transform Infrared
Spectrophotometer28
3.5.3. Instrumentation 28
3.5.4. Interferometry 30
3.5.5. Attenuated Total Reflectance 31
3.5.6. Importance of Infrared Spectroscopy 32
3.5.7. Identification of Unknown Compounds 32
3.5.8. Elemental Analysis 33
3.5.9. Quantitative Analysis 33
3.5.10. Molecular Structure 34
3.5.11. Infrared Spectrum 34
3.5.12. Shortcomings 37
3.5.13. Some of the advantages of FTIR are 38
3.6. Mass Spectrometry 38
3.6.1. Instrumentation 39
3.6.2. Mass Spectrometry and Polymers 40
3.6.3. Pyrolysis–Mass Spectrometry 40
3.6.4. Secondary Ion Mass Spectrometry 41
3.6.5. Electrospray Ionization 42
3.6.6. Field Desorption Mass Spectrometry 43
3.6.7. Matrix-Assisted Laser
Desorption Ionization Time-of-Flight 43
3.6.8. Shortcomings 46
3.6.9. Advantages 47
3.7. Nuclear Magnetic Resonance Spectroscopy 48
3.7.1. Basics 48
3.7.2. NMR Spectrum 51
3.7.3. Solvents 52
3.7.4. Proton 1H NMR Spectrum 53
3.7.5. Carbon 13C NMR Spectrum 54
3.7.6. Fluorine 19F NMR Spectrum 56
3.7.7. Shortcomings 56
3.7.8. Advantages 58
 CONTENTS  •   ix

3.8. Raman Spectroscopy 58

3.8.1. Importance of the Raman Spectrum 62
3.8.2. Shortcomings 62
3.8.3. Advantages 62
Chapter 4 Chromatographic Techniques 77
4.1. High-Performance Liquid
Chromatography 79
4.1.1. Instrumentation 79
4.1.2. Reverse Phase HPLC 80
4.1.3. Mobile Phase 82
4.1.4. Stationary Phase 82
4.1.5. Elution 82
4.1.6. Column 83
4.1.7. Mechanism of Retention 83
4.1.8. Chromatogram 84
4.1.9. Advantages 84
4.1.10. Shortcomings 84
4.2. Size Exclusion Chromatography 85
4.2.1. Instrumentation 86
4.2.2. Detectors 86
4.2.3 Effects on Column Packing 87
4.2.4. Effects on Velocity 88
4.2.5. Solvents Effect 89
4.2.6. Calibration 89
4.2.7. Plate Count 90
4.2.8. Role of SEC 91
4.2.9. Shortcomings 94
4.2.10. Advantages 95
4.3. Gas Chromatography 96
4.3.1. Thermal Fragmentation 96
4.3.2. Instrumentation 97
4.3.3. Analyte Separation and
Quantitative Determination  98
4.3.4. Shortcomings 99
4.3.5. Advantages 99
Chapter 5 Thermal Analysis 107
5.1. Thermogravimetric Analysis (TGA) 108
5.1.1. Importance of Thermal Analysis 109
5.1.2. Instrumentation 110
5.1.3. Essentials of Thermogravimetric
Instrument 112
5.1.4. Advantages 113
x  •  CONTENTS

5.2. Differential Scanning Calorimetry (DSC) 113

5.2.1. Basics 114
5.2.2. Instrumentation 114
5.2.3. Advantages 117
Chapter 6 Other Essential Instrumental Methods
of Analysis 121
6.1. Heat Stability Test 121
6.2. Gel Content Determination 122
6.3. Microscopy 123
6.4. Scanning Electron Microscopy 124
6.5. Transmission Electron Microscopy (TEM) 126
6.6. Atomic Force Microscopy (AFM) 127
6.7. Small-Angle X-ray Scattering (SAXS) 127
6.8. Viscometric Determination of Molecular Weight 128
6.9. Ultracentrifugation 129
6.10. Light Scattering Technique 130
6.11. Supercritical Fluid Extraction (SFE) 132
6.11.1. Advantages 133
Chapter 7 Future Trends 139
7.1. Role of Polymer Testing 140
7.2. Quality Control 140
7.3. Developments in Polymer Testing 141
7.4. Driving Forces 141
7.5. Requirements and Challenges 141
About the Author 145
Index 147
 List of Figures

Figure 3.1. Spectral noise waveforms before Fourier transform

to wave forms after Fourier transform 22
Figure 3.2. UV−VIS spectra of pure PU showing absorption peaks 23
Figure 3.3. NIR spectra of a copolymer 25
Figure 3.4. FTIR spectrophotometer 28
Figure 3.5. FTIR—light absorbing mediums in cell 30
Figure 3.6. IR spectrum of high-density polyethylene 35
Figure 3.7. FTIR spectra of PVDF powder 36
Figure 3.8. Mass spectra flow diagram 40
Figure 3.9. Mass spectra of polystyrene samples with nominal
molecular weight: (a) 330,000, (b) 600,000, and
(c) 900,000 45
Figure 3.10. The mass spectrum of polystyrene with a nominal
molecular weight of 90,000 47
Figure 3.11. Energy gap between the transitions and the spectra 49
Figure 3.12. Relationship between magnetic dipole, magnetic
field, and gravitational direction 50
Figure 3.13. Principle of NMR 50
Figure 3.14. Opposite to NMR—in which magnetization is stable
and the coil loop rotates 51
1
Figure 3.15. H NMR spectra of diazocine-containing
poly(arylene ether sulfone) copolymers in THF.
Spectra 1 (diazocine/sulfone 1.0/0), and spectra 2 is not
shown due to its insolubility in THF 53
Figure 3.16. 13C NMR spectrum of PUR 55
13
Figure 3.17. C NMR spectra of PMMA 56
Figure 3.18. F NMR spectra of PVDF powder 57
xii  •   LIST OF FIGURES

Figure 3.19. Solution-state 19F NMR spectrum of PVDF

dissolved in dimethylsulfoxide 57
Figure 3.20. Raman effects from Raman spectra 60
Figure 3.21. NIR–FT Raman spectrum of polyacrylamide 61
Figure 4.1. Chromatography with column and detector 78
Figure 4.2. High-performance liquid chromatography (HPLC)
with auto sampler. (A) Mobile phase mixed after
the auto sampler. (B) Mobile phase mixed before
the auto sampler 80
Figure 4.3. Reverse phase HPLC fractionation of polystyrene 81
Figure 4.4. Size exclusion chromatography (SEC) flow diagram 87
Figure 4.5. Injected polymer solution in column according to size 92
Figure 4.6. Chromatograms of the polystyrene (PS) sample at
different temperatures near the critical condition 93
Figure 4.7. SEC chromatogram of poly(tetramethylene ethylene
glycol) plotted with logarithmic scale (weight fraction
versus molecular weight) and linear scale(relative
number fraction versus the square root of molecular
weight) 94
Figure 4.8. Gas chromatography (GC) 97
Figure 5.1. Thermogravimetric instrument for thermal analysis 110
Figure 5.2. Thermogravimetric curve 111
Figure 5.3. TGA curves of PP 112
Figure 5.4. Differential scanning calorimeter 115
Figure 5.5. Thermal events of differential scanning calorimetry 116
Figure 5.6. Differential scanning calorimetry traces of pure
poly(methylmethacrylate) (PMMA) 117
Figure 6.1. Heat stability oven for testing of polymer stability 122
Figure 6.2.  SEM images showing (a) discrete particles forming
using 1 percent acid-terminated perfluoropolyether as
polymer stabilizer and 0.5 percent AIBN and (b)
stringlike structure formed using 2.5 percent AIBN 125
Figure 6.3.  Transmission electron micrograph of colloidal silica
particles 126
Figure 6.4.  (A) Light scattering technique—wide angle
(B) Light scattering technique—small angle 131
 Preface

The book series on the basics of polymers is a result of phenomenal growth

in polymers and additives. Basics of Polymer Testing—Vol II discusses the
fundamental principles of polymer testing by instrumental methods. This
is a practical reference that provides an in-depth description of methods
useful for polymers and additive testing.
Basics of Polymer Testing—Vol II outlines the general methods of in-
strumental testing of polymers and additives. Emphasis has been placed on
general principles, and much attention has been given to practical meth-
ods. The book presents a comprehensive approach to all aspects, from fun-
damentals to applications. It is designed more on scientific concepts to fill
the gap between laboratory testing and instrumental methods.
The book will be useful to polymer, materials, chemical, and other
engineers as well as polymer chemists and physicists. Students will bene-
fit from using it as a handbook on instrumental methods and as a general
reference on polymers.
 Acknowledgments

I wish to express my deep gratitude to my professors for their valu-

able guidance during my studies. I also especially thank Mr. Joel Stein,
Ms. Rene Caroline, Ms. Charlene Kronstedt, and others of Momentum
Press. Many thanks to my wife (Mrs. Himachala Ganga) and my sons
(Venkatasubramanian and Sailesh), who worked hard with me to get
this book finished on time. Finally, I sincerely thank my parents, who
brought me into the world to enhance my writing, and, above all, Lord
Nataraja and my intimate teacher Lord Subramanyam.
Dr. Muralisrinivasan Natamai Subramanian
India
 CHAPTER 1

Introduction

OVERVIEW

The characterization of all aspects of a polymer is enough to predict its

performance. Instrumental methods help to find significant changes in
composition or manufacturing process. For the desired performance, a
meaningful characterization, based on selection from all possible molec-
ular and structural parameters, will ensure that the testing is done with
an economically feasible amount. There are inherent complications with
chemical methods due to insolubility of polymer in a majority of solvents.
Introduction of instrumental methods will enable the characterization of
various polymer properties through a series of interfaced instruments.
However, the success of characterization requires in-depth knowledge
of polymer. Instrumental methods require careful calibration to produce
meaningful results.

1.1.  OBJECTIVE: POLYMER TESTING

The main role of polymer testing is as a controlling tool that supports the
development of chemical engineering and technology for production of
polymers and chemicals. Polymer testing procedures provide information
about the polymer, its properties, and additives. Product life-cycle anal-
ysis is impossible without the testing of components and products. The
development of the standards and specifications to be used in industry is
strongly based on the evidence obtained by testing controlled by chemical
methods. Polymer testing is the only way to identify the environmental
friendliness of new methods, processes, and products (Lewis 1996).
2  •   BASICS OF POLYMERS, VOLUME II

1.2.  NECESSITY OF INSTRUMENTAL METHODS

Characterization of polymers is inherently a more difficult process com-

pared with other processes such as separation, filtration, and fractionation
(Billmeyer 1975). Polymer samples are always a more or less complicated
mixture of polymer and additives in some sort of a matrix. In view of
this complexity, polymer testing is used to monitor and control the poly-
mer and additives as raw materials (Rodriguez 1996). For identification,
a comparison with the known physicochemical parameters and the known
spectra is still the basic approach. Data is obtained through automatic in-
strumentation and high-throughput technology forces where instrumen-
tal methods are the main tools for further development (Sheldon 1994).
Polymer testing helps reveal the processing characteristics, and this could
result in an approach to select the proper identification and characteri-
zation methods. Polymer testing involves innovations with the continued
development of polymers. It helps to meet the requirements in processing
and applications. It determines the applications with instrumental tech-
niques that measure and control technology. Instrumental methods require
small samples from the volume of samples. They are fast and the results
are reliable.
Polymer testing should involve easy and safe use of instruments in the
laboratory. It should be adopted with all specific limits related to charac-
terization, measurement, and calibration. Pretesting and process optimi-
zation are controlled by the best overview of the process. Polymer testing
should be functionally oriented, particularly emphasizing measurement
integration within an ergonomic working environment.
Instrumental methods help in the following:

• Determination of the processing behavior

• Processability evaluation
• Development of formulation
• Compounding
• Determination of the influences of additives

Polymer testing involves tests through all stages of processing of the

complexity of polymers and their blends which are to be subjected to con-
tinuous development in terms of technology of measurement. Polymer
testing is required for a more accurate determination of processing char-
acteristics such as viscosity, homogeneity, and additive dispersion (Deanin
1978; Gearhart and Ball 1965; Stepek and Daoust 1983).
 Introduction  •   3

1.3. SPECIALIZATION

The advantages of instrumental methods are as follows:

• The amount of polymer or additive sample required is extremely

small. A few milligrams suffice, in many cases, to complete the
quantitative analysis.
• A minimum amount of preparation of the sample for analysis is
required. Simultaneous identification of the polymer and determi-
nation of their additive concentration is also possible.
• The testing sensitivity is great in terms of identifying the concen-
trations that may be contained even to a minimum level present in
polymer matrices or blends.
• The precision and accuracy of analysis for polymer and additives
occurring in concentrations of 0.001 to 0.0001 are valuable, for in
many instances the instrumental methods provide the practicable
means of determination.
• The rapidity of the method, where applicable, in general, saves a
considerable portion of the time and cost required for chemical
analysis.

Instrumental methods provide the following:

• Detailed structural analysis of polymer products

• Quality assurance/quality control (QA/QC) support in polymer
production
• Defect analysis
• Identification of small differences between the chemical structures
of polymers
• Analysis of additives in polymers
• Qualitative identification of polymer additives

Instrumental methods of polymer testing play an important role in

identifying correct and concrete polymer properties (Wampler 1995;
Wang and Smith 1996). They help to control the initial parameters of poly-
mer, either in synthesis or in determining the properties of end products.
Hence, it is necessary to understand the polymer matrix and the basics of
the instrument that is necessary in order to understand the polymer prop-
erties. Many instrumental methods require the concepts of qualitative and
quantitative performance as a driving force.
4  •   BASICS OF POLYMERS, VOLUME II

REFERENCES

Billmeyer, Jr., F.W. 1975. “Introductory Remarks to Polymer Characterization

Chapters.” In Characterization of Materials in Research: Ceramics and Poly-
mers, eds. J.J. Burke and V. Weiss. Syracuse, NY: Syracuse University Press.
Deanin, R.D. 1978. “Chapter 4.” In Additives for Plastics, ed. R.B. Seymour.
Vol. 1. New York, NY: Academic Press, pp. 404–408.
Gearhart, W.M., and F.M. Ball. 1965. “Plasticizers for Cellulosics.” In Plasticizers
Technology, ed. P.F. Bruins. Vol. 1. New York, NY: Reinhold, p. 186.
Lewis, F.L. 1986. Optimal Estimation. New York, NY: Wiley.
Rodriguez, F. 1996. Principles of Polymer Systems. Philadelphia, PA: Taylor &
Francis, p. 2.
Sheldon, R.A. 1994. “Consider the Environmental Quotient.” Chemtech 3, p. 38.
Stepek, J., and H. Daoust. 1983. “Plasticizers.” In Additives for Plastics, eds. J. ­Stepek
and H. Daoust. New York, NY: Springer-Verlag, pp. 23–27.
Wampler, T.P. 1995. “Analytical Pyrolysis: An Overview.” In Analytical Pyrolysis
Handbook, ed. T.P. Wampler. New York, NY: Marcel Dekker, pp. 1–3.
Wang, F.C.-Y., and P.B. Smith. 1996. “Quantitative Analysis and Structure
­Determination of Styrene/Methyl Methacrylate Copolymers by Pyrolysis Gas
Chromatography.” Analytical Chemistry 68, pp. 3033–37.
 Index

A high-performance liquid chroma-

Absorption, 35 tography, 79
Additives, 10–11, 95 advantages, 84
testing of, 11–12 chromatogram, 84
Adsorption type chromatography, 83 column, 83
Amorphous polymers, 98 elution, 82–83
Analytes instrumentation, 79–80
diffusion, 132 mechanism of retention,
separation and quantitative deter- 83–84
mination, 98–99 mobile phase, 82
Atomic force microscopy (AFM), reverse phase, 80–82
127 shortcomings, 84–85
Attenuated total reflectance, 31–32 stationary phase, 82
Attenuated total reflection overview, 77–79
Fourier transform infrared size exclusion chromatography,
spectroscopy (ATR-FTIR), 31 85–86
advantages, 95–96
C calibration, 89–90
Carbon-13 nuclear magnetic column packing, effects on,
resonance (13C NMR), 14 87–88
spectrum, 54–56 detectors, 86–87
Chemical composition distribution instrumentation, 86
(CCD), 8, 89 plate count, 90–91
Chemical versus instrumental role of, 91–94
methods, 15–16 shortcomings, 94–95
Chromatogram, 84 solvents effect, 89
Chromatographic techniques velocity, effects on, 88–89
gas chromatography, 96 Chromatography, 14
advantages, 99 Collisionally activated dissociation
analyte separation and quantita- (CAD), 44
tive determination, 98–99 Colorimetry, 23
instrumentation, 97–98 Columns
shortcomings, 99 packing, effects on, 87–88
thermal fragmentation, 96–97 for polymer separation, 83
148  •   Index
Controlled-current electrolytic
(CCE) flow cell, 42
Conventional microscopy methods,
123
Copolymers, 6, 8
Crystal quartz, 29
D Gel content determination,
Desorption, 132
Differential scanning calorimetry
(DSC), 113–114
advantages, 117–118
basics, 114
instrumentation, 114–117
E Heat stability test, 121–122
Einstein viscosity law, 92
Electromagnetic radiation, 37
Electrospray ionization (ESI),
42–43
Electrospray mass spectrometry
(ESMS), 42–43
Elemental analysis, 33
Elution, 82–83
Endothermic transition, 115
Enthalpy, 14
Entropy, 14
F stationary phase, 82
Fast Fourier algorithm, 30
Field desorption mass
spectrometry (FDMS), 43
Filler, 11
Fluorescence, 59
Fluorine 19F NMR spectrum, 56
Fourier transform (FT), 22
Fourier transform infrared (FTIR)
spectroscopy, 13
Fourier transform infrared
spectrophotometer, 28
Functionality type distribution, 8
G infrared spectrum, 34–37
Gas chromatography (GC), 39, 96
advantages, 99
analyte separation and quantita-
tive determination, 98–99
instrumentation, 97–98
shortcomings, 99
thermal fragmentation, 96–97
Gas–solid chromatography (GSC)
mode, 99
122–123
Gel filtration, 86
Gel permeation chromatography.
See Size exclusion
chromatography (SEC)
H
High-performance liquid
chromatography (HPLC), 39,
79
advantages, 84
chromatogram, 84
column, 83
elution, 82–83
instrumentation, 79–80
mechanism of retention, 83–84
mobile phase, 82
reverse phase, 80–82
shortcomings, 84–85
Homopolymers, 6
I
Infrared spectroscopy
attenuated total reflectance,
31–32
basics, 26–27
elemental analysis, 33
Fourier transform infrared spec-
trophotometer, 28
identification of unknown com-
pounds, 32–33
importance of, 32
instrumentation, 28–30
interferometry, 30–31

molecular structure, 34
quantitative analysis, 33–34
shortcomings, 37
some advantages of FTIR, 38
Infrared spectrum, 34–37
Instrumental methods
advantages of, 3
of analysis
atomic force microscopy, 127
gel content determination,
122–123
heat stability test, 121–122
light scattering technique,
130–132
microscopy, 123–124
overview, 121
scanning electron microscopy,
124–125
small-angle x-ray scattering,
127–128
supercritical fluid extraction,
132–133
transmission electron micros-
copy, 126–127
ultracentrifugation, 129–130
viscometric determination of
molecular weight, 128–129
chemical methods versus, 15–16
importance of, 16–17
necessity of, 2
and their role, 12–13
Inter molecular effects, 34
Interferometry, 30–31
Internal reflection element
(IRE), 31
Intramolecular effects, 34
L
Lambert–Beer law, 23
Light scattering, 13
Light scattering technique,
130–132
Liquid chromatographic (LC), 80
Low angular light scattering
(LALLS), 89
Index  •   149
M
Macromolecules, 6
Magnetization, 50
Mark–Houwink–Sakurada
relationship, 129
Mass per charge, 40
Mass spectrometry (MS), 38–39
advantages, 47
electrospray ionization, 42–43
field desorption mass spectrom-
etry, 43
instrumentation, 39–40
matrix-assisted laser desorption
ionization time-of-flight,
43–46
and polymers, 40
pyrolysis, 40–41
secondary ion, 41–42
shortcomings, 46–47
Matrix-assisted laser desorption
ionization time-of-flight
(MALDI-TOF-MS), 43–46
Melt flow index, 15
Melt index (MI), 13
Melt viscosity, 10
Michelson interferometer, 28
Microscopy, 123–124
Mobile phase HPLC, 82
Molar mass distribution (MMD), 89
Molecular spins, 50
Molecular structure, 34
Molecular weight, viscometric
determination of, 128–129
Monomer, 7
Multiangular laser light scattering
(MALLS) photometer, 89
Multiple quantum transitions, 48
N
Near-infrared (NIR) spectroscopy
advantages, 25–26
disadvantage, 26
industrial applications, 24–25
Nonaqueous reverse phase LC,
81–82
150  •   Index
Nuclear magnetic resonance
spectroscopy, 14, 48
advantages, 58
basics, 48–51
carbon 13C NMR spectrum,
54–56
fluorine 19F NMR spectrum, 56
proton 1H NMR spectrum, 53
shortcomings, 56–58
solvents, 52
spectrum, 51–52
Nuclear relaxation times, 52
O Polyurethane (PUR), 54
Ohm’s law, 114
Oligomeric molecules, 83
One-pack additives, 11
Osmometry, 13
Ostwald viscometer, 129
P Pulsed FT 13C NMR, 54
Planck’s constant, 49
Polyacrylamide (PA), carbonyl
stretching vibration of, 60
Polymer testing, 1
importance of
additives, 10–11
chemical composition distribu-
tion, 8
chemical methods versus in-
strumental methods, 15–16
chemical properties, 9–10
chromatography, 14
functionality type distribution,
8 Rayleigh scattering, 131
importance of instrumental
methods, 16–17
instrumental methods and their
role, 12–13
other measurements, 15
overview, 5–6
physical properties, 8–9
polymers, 6–7
properties, 7–8
rheological measurements, 15
rheological properties, 10
spectroscopy, 13–14
testing of additives, 11–12
thermal analysis, 14–15
thermal properties, 10
Polymers, 6–7
architectural aspects, 6–7
chemical aspects, 6
mass spectrometry and, 40
properties, 7–8
Polymethylmethacrylate (PMMA),
55, 116, 124
Polystyrene fractionation, 81
Polyvinylidene fluoride (PVDF)
powder, 56
Post-source decay (PSD), 44
Potassium bromide (KBr), 35
Powdered additives, 11
Proton 1H NMR spectrum, 53
Pyrolysis–mass spectrometry, 40–41
Q
Quantitative analysis, 33–34
R
Radio-driven temperature control
system, 121
Raman scattering process, 59
Raman spectroscopy, 58–62
advantages, 62–63
importance of, 62
shortcomings, 62
Reproducibility of peak, 89
Retention mechanism, of
macromolecule, 83–84
Reverse phase HPLC, 80–82
S
Scanning electron microscopy
(SEM), 124–125
Secondary ion mass spectrometry
(SIMS), 41–42

Shearing process, 10
Silicon, 29
Single interferogram, 31
Size exclusion chromatography
(SEC), 85–86
advantages, 95–96
calibration, 89–90
column packing, effects on, 87–88
detectors, 86–87
instrumentation, 86
plate count, 90–91
role of, 91–94
shortcomings, 94–95
solvents effect, 89
velocity, effects on, 88–89
Size exclusion chromatography, 13
Small-angle light scattering
technique, 132
Small-angle x-ray scattering
(SAXS), 127–128
Soft ionization technique. See
Electrospray ionization (ESI)
Softening point, 11
Solid-state 19F magnetic angle
spinning (MAS), 56
Solubility tests, 13
Solvents, 52
Spectrophotometric analysis, 22
Spectroscopic techniques
Fourier transform, 22
infrared spectroscopy
attenuated total reflectance,
31–32
basics, 26–27
elemental analysis, 33
Fourier transform infrared
spectrophotometer, 28
identification of unknown com-
pounds, 32–33
importance of, 32
infrared spectrum, 34–37
instrumentation, 28–30
interferometry, 30–31
molecular structure, 34
quantitative analysis, 33–34
Index  •   151
shortcomings, 37
some advantages of FTIR, 38
mass spectrometry, 38–39
advantages, 47
electrospray ionization, 42–43
field desorption mass
­spectrometry, 43
instrumentation, 39–40
matrix-assisted laser ­desorption
ionization time-of-flight,
43–46
and polymers, 40
pyrolysis, 40–41
secondary ion, 41–42
shortcomings, 46–47
near-infrared (NIR) spectroscopy
advantages, 25–26
disadvantage, 26
industrial applications, 24–25
nuclear magnetic resonance
spectroscopy, 48
advantages, 58
basics, 48–51
carbon 13C NMR spectrum,
54–56
fluorine 19F NMR
spectrum, 56
proton 1H NMR spectrum, 53
shortcomings, 56–58
solvents, 52
spectrum, 51–52
overview, 21
Raman spectroscopy, 58–62
advantages, 62–63
importance of, 62
shortcomings, 62
spectrophotometric analysis, 22
ultraviolet and visible absorption
spectroscopy, 23–24
Spectroscopy, 13–14
Spectrum, NMR, 51–52
Static light scattering, 132
Stationary phase HPLC, 82
Supercritical fluid extraction
(SFE), 132–133
152  •   Index
T Topology, 6
Tetrahydrofuran (THF), 53
Thermal analysis, 14–15
differential scanning calorimetry,
113–114
advantages, 117–118
basics, 114
instrumentation, 114–117
importance of, 109–110
overview, 107–108
thermogravimetric analysis,
108–109
advantages, 113
essentials of, 112–113
instrumentation, 110–112
Thermal fragmentation, 96–97
Thermogravimetric analysis
(TGA), 108–109
advantages, 113
essentials of, 112–113
instrumentation, 110–112
Transmission electron microscopy
(TEM), 13, 126–127
U
Ubbelohde viscometer, 129
Ultracentrifugation, 129–130
Ultraviolet and visible absorption
(UV–VIS) spectroscopy,
23–24
V
Valorization, 7
Vibrational techniques, 21
Viscometric determination of
molecular weight, 128–129
Viscometry, 13
Viscosity, measurement of, 15
X
X-ray scattering, 13
 OTHER TITLES IN OUR PLASTICS
AND POLYMERS COLLECTION
• Basics of Polymers: Fabrication and Processing Technology
by Muralisrinivasan Subramanian
• Basics of Polymers: Materials and Synthesis by Muralisrinivasan Subramanian
• Basics of Polymers, Volume I: Testing and Characterization
by Muralisrinivasan Subramanian

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