C

ontents

Methodology of Thermo-oxidative Degradation

of Polymers....................................................................................1
1.1

TGA....................................................................................1
1.1.1 Methods Involving Maximisation of Rate................7
1.1.2 Method of Multiple Heating Rates [1315]...........10

1.2

Differential Scanning Calorimetry.....................................14

1.3

Evolved Gas Analysis (EGA)..............................................16

1.4

Pyrolysis-based Techniques................................................16

Carbon-Hydrogen-Type Polymers...............................................21
2.1

Polyethylene......................................................................21
2.1.1 Mechanism of Oxidative Degradation . .................21
2.1.2 Thermogravimetric Analysis (TGA).......................24
2.1.3 DSC.......................................................................28
2.1.4 Infrared (IR) Spectroscopy.....................................28
2.1.5 PyrolysisGas ChromatographyMass Spectrometry
(PyGCMS)..........................................................30

2.2

Polypropylene....................................................................33
2.2.1 Mechanism of Oxidative Degradation . .................33
2.2.2 IR Spectroscopy.....................................................35
2.2.3 Differential Scanning Calorimetry..........................37
2.2.3.1 Differential Scanning Calorimetry
Chemiluminescence ................................39

Thermo-oxidative Degradation of Polymers

2.2.4 DTA.......................................................................42
2.2.5 TGA.......................................................................42
2.2.6 PyGC . .................................................................42
2.2.7 Positron Annihilation Lifetime Spectroscopy..........44

2.3

Rubbers.............................................................................44

2.4

Polystyrene (PS) and Poly(-methyl styrene)......................45

Oxygen-Containing Polymers......................................................51
3.1

Polyoxymethylene..............................................................51

3.2

Polyphenylene Oxides (PPO).............................................54

3.3

Polyesters...........................................................................54
3.3.1 Polycarbonate........................................................54
3.3.2 Polyethylene Terephthalate (PETP).........................57
3.3.3 Polymethacrylates..................................................58
3.3.4 Styrenated Polyesters..............................................58
3.3.5 Phenol-formaldehyde (PF) Resins...........................62
3.3.6 Epoxy Resins..........................................................68
3.3.6.1 Thermogravimetric Analysis ...................70
3.3.6.2 Differential Scanning Calorimetry...........72
3.3.7 Ethylene Oxide-Propylene Oxide Copolymers........73
3.3.8 Ethylene Vinyl Acetate (EVA) Copolymers.............77
3.3.9 Phenolic Resins......................................................83

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Halogen-Containing Polymers.....................................................87
4.1

Polyvinyl Chloride (PVC)..................................................87

4.2

Chlorinated Natural Rubber..............................................89

4.3

Polytetrafluoroethylene (PTFE)..........................................89

Nitrogen-Containing Polymers....................................................97

Contents

5.1

Rigid Polyurethanes...........................................................97

5.2

Polyacrylonitrile..............................................................103

5.3

Polyimides (PI).................................................................105

5.4

Polyamides......................................................................112

5.5

Polycaprolactam..............................................................119

Silicon-Containing Polymers......................................................123

Abbreviations......................................................................................127
Index 131

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Thermo-oxidative Degradation of Polymers

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