Characterisation of Polymers, Volume 1

Characterisation of Polymers, Volume 1

Author: T.R.Crompton
ISBN 978-1-84735-123-4 
This book is intended to be a complete compendium of the types of methodology that have evolved for the determination of the chemical composition of polymers.

Volume 1 covers the methodology used for the determination of metals, non-metals and organic functional groups in polymers, and for the determination of the ratio in which different monomer units occur in copolymers. The techniques available for composition determination of homopolymers and copolymers and other recent modern techniques such as X-ray photoelectron spectroscopy, atomic force microscopy, microthermal analysis and scanning electron microscopy and energy dispersive analysis using X-rays are also included. The structure and microstructure of polymers, copolymers and rubbers are dealt with in Volume 2. More detailed aspects, such as sequencing of monomer units in copolymers, end-group analysis, tacticity and stereochemical determinations, are also dealt with in this subsequent volume.

This book gives an up-to-date and thorough exposition of the state-of-the-art theories and availability of instrumentation needed to effect chemical and physical analysis of polymers. This is supported by approximately 1200 references. The book should be of great interest to all those engaged in the subject in the industry, university research.


1. Determination of Metals
1.1 Destructive Techniques
1.1.1 Atomic Absorption Spectrometry
1.1.2 Graphite Furnace Atomic Absorption Spectrometry
1.1.3 Atom Trapping Technique
1.1.4 Vapour Generation Atomic Absorption Spectrometry
1.1.5 Zeeman Atomic Absorption Spectrometry
1.1.6 Inductively Coupled Plasma Atomic Emission Spectrometry
1.1.7 Hybrid Inductively Coupled Plasma Techniques
1.1.8 Inductively Coupled Plasma Optical Emission Spectrometry–Mass Spectrometry
1.1.9 Pre-concentration Atomic Absorption Spectrometry Techniques
1.1.10 Microprocessors
1.1.11 Autosamplers
1.1.12 Applications: Atomic Absorption Spectrometric Determination of Metals
1.1.13 Visible and UV Spectroscopy
1.1.14 Polarography and Voltammetry
1.1.15 Ion Chromatography
1.2 Non-destructive Methods
1.2.1 X-ray Fluorescence Spectrometry
1.2.2 Neutron Activation Analysis
Method 1.1 Determination of Traces of Cadmium, Chromium, Copper, Iron, Lead, Manganese, Nickel, and Zinc in Polymers. Ashing – Atomic Absorption Spectrometry
Method 1.2 Determination of Traces of Arsenic in Acrylic Fibres Containing Antimony Trioxide Fire Retardant Agent. Acid Digestion, Atomic Absorption Spectrometry
Method 1.3 Determination of Vanadium Catalyst Residues in Ethylene-propylene Rubber. Ashing – spectrophotometric Procedure

2. Determination of Non-metallic Elements
2.1 Halogens
2.1.1 Combustion Methods
2.1.2 Oxygen Flask Combustion
2.1.3 Alkali Fusion Methods
2.1.4 Physical Methods for Determining Halogens
2.2 Sulfur
2.2.1 Combustion Methods
2.2.2 Sodium Peroxide Fusion
2.2.3 Oxygen Flask Combustion
2.3 Phosphorus
2.3.1 Acid Digestion
2.3.2 Oxygen Flask Combustion
2.4 Nitrogen
2.4.1 Combustion Methods
2.4.2 Acid Digestion
2.4.3 Physical Method for the Determination of Total Nitrogen
2.5 Silica
2.6 Boron
2.7 Total Organic Carbon
2.8 Total Sulfur/Total Halogen
2.9 Nitrogen, Carbon, and Sulfur
2.10 Carbon, Hydrogen, and Nitrogen
2.11 Oxygen Flask Combustion: Ion Chromatography
2.12 X-ray Fluorescence Spectroscopy
2.13 Thermogravimetric Analysis
Method 2.1 Determination of Chlorine in Polymers Containing Chloride and Sulfur and/or Phosphorus and/or Fluorine. Oxygen Flask Combustion – Mercurimetric Titration
Method 2.2 Determination of Chlorine in Chlorobutyl and Other Chlorine Containing Polymers. Oxygen Flask Combustion – Turbidimetry
Method 2.3 Determination of Up to 80% Chlorine, Bromine and Iodine in Polymers. Oxygen Flask Combustion – Titration
Method 2.4 Determination of Fluorine in Fluorinated Polymers. Oxygen Flask Combustion - Spectrophotometric Procedure
Method 2.5 Determination of Traces of Chlorine in Polyalkenes and Polyalkene Copolymers. Sodium Carbonate Fusion – Titration Procedure
Method 2.6 Determination of Macro-amounts of Sulfur in Polymers. Sodium Peroxide Fusion - Titration Procedure
Method 2.7 Determination of Sulfur in Polymers. Oxygen Flask Combustion – Titration Procedure
Method 2.8 Determination of Sulfur in Polymers. Oxygen Flask Combustion – Photometric Titration Procedure
Method 2.9 Micro Determination of Phosphorus in Polymers. Acid Digestion – Spectrophotometric Method
Method 2.10 Determination of Low Levels of Phosphorus in Polymers. Oxygen Flask Combustion – Spectrophotometric Method
Method 2.11 Determination of 2-13% Phosphorus in Polymers. Oxygen Flask Combustion – Spectrophotometric Method
Method 2.12 Determination of Between 0.002% and 75% Organic Nitrogen in Polymers. Kjeldahl Digestion – Spectrometric Indophenol Blue Method
Method 2.13 Determination of 1 to 90% Organic Nitrogen in Polymers. Kjeldahl Digestion – Boric Acid Titration Method
Method 2.14 Qualitative Detection of Elements in Polymers. Oxygen Flask Combustion

3. Determination of Functional Groups in Polymers
3.1 Hydroxy Groups
3.1.1 Acetylation and Phthalation Procedures
3.1.2 Spectrophotometric Methods
3.1.3 Nuclear Magnetic Resonance Spectrometry
3.1.4 Infrared Spectroscopy
3.1.5 Direct Injection Enthalpimetry
3.1.6 Kinetic Method – Primary and Secondary Hydroxyl Groups
3.1.7 Miscellaneous Techniques
3.2 Carboxyl Groups
3.2.1 Titration Method
3.2.2 Nuclear Magnetic Resonance Spectroscopy
3.2.3 Pyrolysis Gas Chromatography – Mass Spectrometry
3.2.4 Infrared Spectroscopy
3.2.5 Miscellaneous
3.3 Carbonyl Groups
3.4 Ester Groups
3.4.1 Saponification Methods
3.4.2 Zeisel Hydriodic Acid Reduction Methods
3.4.3 Pyrolysis Gas Chromatography
3.4.4 Infrared Spectroscopy
3.4.5 Nuclear Magnetic Resonance Spectroscopy
3.4.6 Gas Chromatography
3.4.7 Isotope Dilution Method
3.6 Alkoxy Groups
3.6.1 Infrared Spectroscopy
3.6.2 Nuclear Magnetic Resonance Spectroscopy
3.6.3 Miscellaneous Methods
3.7 Oxyalkylene Groups
3.7.1 Cleavage – Gas Chromatography
3.7.2 Pyrolysis Gas Chromatography
3.7.3 Infrared Spectroscopy
3.7.4 Nuclear Magnetic Resonance Spectroscopy
3.8 Anhydride Groups
3.9 Total Unsaturation
3.9.1 Hydrogenation Methods
3.9.2 Halogenation Methods
3.9.3 Iodine Monochloride Procedures
3.9.4 Infrared Spectroscopy
3.9.5 Nuclear Magnetic Resonance Spectroscopy
3.9.6 Pyrolysis Gas Chromatography
3.10 Ethylene Glycol, 1,4-Butane Diol, Terephthalic Acid and Isophthalic Acid Repeat Units in Terylene
3.11 Oxirane Rings
3.12 Amino Groups
3.13 Amido and Imido Groups
3.13.1 Alkali Fusion Reaction Gas Chromatography
3.14 Nitrile Groups
3.14.1 Determination of Bound Nitrile Groups in Styrene – Acrylonitrile Copolymers
3.15 Nitric Ester Groups
3.16 Silicon Functions
Method 3.1 Determination of Hydroxyl Groups in Polyethylene Glycol. Silation – Spectrophotometry
Method 3.2 Determination of Hydroxyl Number of Glycerol-Alkylene Oxide Polyethers and Butane, 1,4-Diol Adipic Acid Polyesters. Direct Injection Enthalpimetry
Method 3.3 Determination of Primary and Secondary Hydroxyl Groups in Ethylene Oxide Tipped Glycerol-Propylene Oxide Condensates.
Method 3.4 Determination of Compositional Analysis of Methylmethacrylate - Methacrylic Acid Copolymers. Fourier Transform 13C-NMR Spectroscopy
Method 3.5 Identification of Acrylic Acid and Methacrylic Acid in Acrylic Copolymers. Propylation - Pyrolysis - Gas Chromatography
Method 3.6 Determination of Amino Groups in Aromatic Polyamides, Polyimides and Polyamides-imides. Potassium Hydroxide Fusion Gas Chromatography

4.Monomer Ratios in Copolymers
4.1 Olefinic Copolymers
4.1.1 Ethylene-propylene
4.2 Pyrolysis Gas Chromatography
4.2.1 Pyrolysis – Infrared Spectroscopy
4.2.2 Ethylene – Butane-1 Copolymers
4.2.3 Ethylene – Hexane-1
4.2.4 Other Olefin Polymers
4.2.5 Ethylene – Vinyl Acetate Copolymers
4.3 Vinyl Chloride Copolymers
4.3.1 Vinyl Chloride – Vinyl Acetate
4.3.2 Vinylidene Chloride – Vinyl Chloride
4.4 Styrene Copolymers
4.4.1 Styrene Acrylate and Styrene Methacrylate
4.4.2 Styrene – Methacrylate and Styrene – Methyl Methacrylate Copolymers
4.4.3 Styrene Acrylic Acid Copolymer NMR Spectroscopy
4.4.4 Styrene Methacrylate Copolymers, NMR Spectroscopy
4.4.5 Styrene-n-butyl Acrylate Copolymers
4.4.6 Styrene Methacrylate Copolymers
4.4.7 Miscellaneous Styrene Copolymers
4.4.8 Vinyl Acetate – Methyl Acrylate NMR Spectroscopy
4.5 Butadiene-based Polymers
4.5.1 Styrene Butadiene and Polybutadiene
4.6 Styrene-butadiene-acrylonitrile
4.7 Vinylidene Chloride – Methacrylonitrile and Vinylidene Chloride Cyanovinylacetate Copolymers
4.8 Acrylonitrile-cis (or Trans) Penta-1,3-diene
4.9 Hexafluoropropylene – Vinylidene Fluoride
4.9.1 19F-NMR
4.9.2 Pyrolysis – Gas Chromatography
4.10 Ethylene Glycol Terephthalic Acid, Ethylene Glycol Hydroxyl Benzoic Acid
4.11 Ethylene Oxide Copolymers
4.11.1 Ethylene Oxide – Propylene Oxide
4.11.2 Ethylene Oxide – Polyacetal
4.12 Maleic Anhydride Copolymers
4.13 Acrylamide – Methacryloyl Oxyethyl Ammonium Chloride and Acrylamid – Acyloxyethyl Ammonium Chloride

5. Analysis of Homopolymers
5.1 Infrared Spectroscopy
5.1.1 Determination of Low Concentrations of Methyl Groups in Polyethylene
5.1.2 Bond Rupture in HDPE
5.2 Fourier Transform Infrared (FTIR) Spectroscopy
5.2.1 Instrumentation
5.3 Fourier Transform Raman Spectroscopy
5.3.1 Theory
5.3.2 Applications
5.4 Mass Spectrometry
5.4.1 Time-of-Flight Secondary Ion Mass Spectrometry
5.4.2 Tandem Mass Spectrometry
5.4.3 Matrix Assisted Laser Desorption/Ionisation Mass Spectrometry
5.4.4 Fourier Transform Ion Cyclotron Mass Spectrometry
5.4.5 Fast Atom Bombardment Mass Spectrometry
5.5 Gross Polarisation Magic Angle Spinning 13C and 15N
5.5.1 Solid State Nuclear Magnetic Resonance Spectroscopy
5.6 Gas Chromatography – Mass Spectrometry
5.7 Proton Magnetic Resonance Spectroscopy
5.8 Electron Spin Resonance Spectroscopy
5.9 Infrared Spectra

6. Analysis of Copolymers
6.1 Infrared Spectroscopy
6.2 Fourier Transform Infrared Spectroscopy
6.3 Raman Spectroscopy
6.4 Mass Spectrometry
6.4.1 Radio Frequency Glow Discharge Mass Spectrometry
6.4.2 Fast Atom Bombardment Mass Spectrometry
6.4.3 Laser Desorption – Ion Mobility Spectrometry
6.4.4 Gas Chromatography – Mass Spectrometry
6.4.5 Matrix-assisted Laser Desorption/Ionisation (MALDI) Mass Spectrometry
6.5 NMR and Proton Magenetic Resonance Spectroscopy
6.6 Pyrolysis Techniques
6.7 Other Techniques

7. X-Ray Photoelectron Spectroscopy
7.1 Bulk Polymer Structural Studies
7.2 Adhesion Studies
7.3 Carbon Black Studies
7.4 Particle Identification
7.5 Pyrolysis Studies
7.6 Surface Studies
7.7 Applications in Which Only XPS is Used
7.8 Applications in Which Both XPS and ToF-SIMS are Used

8. Atomic Force Microscopy and Microthermal Analysis
8.1 Atomic Force Microscopy
8.1.1 Polymer Characterisation Studies and Polymer Structure
8.1.2 Morphology
8.1.3 Surface Defects
8.1.4 Adhesion Studies
8.1.5 Polydispersivity
8.1.6 Sub-surface Particle Studies
8.1.7 Size of Nanostructures
8.1.8 Visualisation of Molecular Chains
8.1.9 Compositional Mapping
8.1.10 Surface Roughness
8.1.11 Microphase Separation
8.1.12 Phase Transition
8.1.13 Shrinkage
8.2 Microthermal Analysis
8.2.1 Morphology
8.2.2 Topography
8.2.3 Glass Transition
8.2.4 Depth Profiling Studies
8.2.5 Phase Separation Studies

9. Multiple Technique Polymer Studies
9.1 FTIR – Nuclear Magnetic Resonance (NMR) Spectroscopy
9.2 Other Technique Combinations

10. Scanning Electron Microscopy and Energy Dispersive Analysis Using X-rays

Appendix 1. Instument Suppliers
Appendix 2. Suppliers of Flammability Properties Instruments
Appendix 3. Address of Suppliers
Subject Index