Compositional and Failure Analysis of Polymers A Practical Approach

by Scheirs, John

• ISBN13: 9780471625728
• ISBN10: 0471625728
• Edition: 1st
• Format: Paperback
• Copyright: 2000-10-03
• Publisher: WILEY

Summary

Intended as a practical guide for polymer technologists, engineers and analysts in the plastics, composites and rubber fields, this title describes a range of techniques and strategies for compositional and failure analysis of polymeric materials and products. Numerous examples illustrate the application of analytical methods for solving commonly encountered problems in the polymer industry. The reader is guided towards the most appropriate method of analysis and measurement and the most likely reasons for the failure. Areas covered include: * Migration and interaction of additives * Mechanical stress and stress cracking * Crazing and fracture * Residual stress and weld lines * Contamination and discoloration Numerous pedagogical methods, illustrative flow diagrams, figures and tables are used throughout the text to make it an invaluable guide to all analysts and polymer engineers in industrial or academic laboratories.

Author Biography

John Scheirs <I>ExcelPlas, Australia</I>

Table of Contents

Preface	xxxi
About the Author	xxxiii
Acknowledgements	xxxv
Glossary	xxxvii
A Methodology for Solving Polymer Problems	1	(20)
Introduction	1	(3)
Flow Diagram for Solving Polymer Problems	4	(8)
Accurately Identify and Characterize the Failure	4	(4)
Are the Cause(s) Obvious and Few in Number?	8	(1)
Has this `Same' Product been Successfully Produced Previously?	9	(1)
Is there a Pattern to the Failure Location?	9	(1)
Is there a Trend in the Timing of the Problem?	10	(1)
Is this a Recurring Problem?	10	(2)
Are there Relationships between the Type of Failure and other Factors?	12	(1)
What Changes could have Affected the Failed Product When Compared to a Reference Sample?	12	(1)
Dealing with Special Problem Classes	12	(3)
Elusive Problems	12	(2)
Complex Problems	14	(1)
Subtle Problems	14	(1)
Initial Production Problems	14	(1)
Recurring Problems	14	(1)
Catastrophic or Major Problems	14	(1)
Product Life Cycle	15	(2)
Checklist and Worksheet for Organizing the Problem-Solving Process	17	(4)
References	20	(1)
Sampling and Sample Preparation	21	(16)
Introduction	21	(1)
Sampling	22	(1)
Sample Storage	23	(1)
Sample Conditioning	23	(1)
Sample Preparation	24	(13)
Grinding	27	(1)
Dissolution/Precipitation	27	(1)
Preparation of Polymer Films	28	(1)
Preparing Films for IR Analysis	29	(1)
Preparing Films for DSC/TG Analysis	29	(1)
Melt Pressing of Films	29	(1)
Film Casting	30	(2)
Introduction	32	(1)
Solvent	32	(1)
Film removal	33	(1)
Artifacts of solvent casting	33	(1)
Microtoming	33	(1)
Miscellaneous Sample Types	34	(1)
Intractable Samples	35	(1)
Brittle Thermoset Samples	35	(1)
Viscous Samples	35	(1)
Paints	35	(1)
Thin Films	35	(1)
Rubbers	36	(1)
Case Study	36	(1)
References	36	(1)
Microscopy of Polymers	37	(34)
Optical Microscopy Techniques	37	(18)
Introduction	37	(1)
Sample Illumination	37	(1)
Transmitted Illumination	38	(1)
Near-vertical Illumination	38	(1)
Incident Illumination	39	(1)
Grazing Incident Illumination	39	(1)
Coaxial Illumination	40	(1)
Dark-Field Illumination	40	(1)
Phase Contrast	40	(1)
Polarized Optical Microscopy	40	(7)
Sample Preparation	47	(1)
Microtoming	47	(1)
Microtome knife selection	47	(1)
Glass knives	48	(1)
General microtoming hints	49	(1)
Microtoming artifacts	49	(1)
Selection and preparation of the sample to be microtomed	49	(1)
Problem samples (irregular shaped and soft samples)	50	(1)
Problems encountered during microtoming	51	(1)
Trouble-shooting microtoming problems	52	(1)
Polishing	52	(1)
Hints for the polishing of samples	53	(1)
Polishing versus microtoming	53	(1)
Preparation of composites	54	(1)
Electron Microscopy	55	(5)
Scanning Electron Microscopy	55	(1)
Mounting SEM Samples	56	(1)
Charge Neutralization	57	(1)
Low-Voltage SEM	57	(1)
Transmission Electron Microscopy	58	(1)
Sample Preparation for TEM	59	(1)
Electron-Beam Damage	59	(1)
Special Microscopic Techniques	60	(5)
Thermomicroscopy	61	(1)
UV Microscopy	62	(1)
Atomic Force Microscopy	63	(2)
Practical Examples of the Uses of Microscopy in Polymer Analysis	65	(6)
Identification of Inhomogeneous Melts during Processing	65	(1)
Investigating Mould-Temperature Effects	65	(2)
Evaluation of the Extent of In-Mould Orientation	67	(1)
Examination of Fracture Surfaces	67	(1)
Identifying Crack-Initiation Sites	67	(1)
Examination of Rubber-Modified Polymers	68	(1)
Assessment of Oxidized Polymers	68	(1)
Microscopy of Fibres	68	(1)
Fibre Finish	68	(1)
Internal Texture of Fibres	68	(1)
Failure Analysis of Fibres	69	(1)
Microvoids in Aramid Fibres	69	(1)
PET Fibres	70	(1)
Beam-Induced Heating	70	(1)
Study of Residual Stresses	70	(1)
References	70	(1)
Fourier-Transform Infrared Spectroscopic Analysis Methods for Polymers	71	(36)
Introduction	71	(2)
IR Artifacts	72	(1)
Contaminant Peaks	72	(1)
Interference Fringes	72	(1)
Spectral Subtraction	73	(1)
FTIR Techniques	73	(11)
Transmission Analysis	73	(1)
ATR Analysis	73	(5)
Diffuse Reflectance IR (DRIFT)	78	(3)
Reflectance-Absorption FTIR	81	(1)
Photoacoustic FTIR	81	(1)
FTIR Microspectroscopy	81	(1)
Introduction	81	(2)
Embedding Media	83	(1)
FTIR Mapping Techniques	83	(1)
Reflectance ETIR Microscopy	84	(1)
Thermomicroscopy-FTIR	84	(1)
Special IR Techniques	84	(3)
NIR Analysis	84	(2)
Raman-FTIR	86	(1)
Sample Preparation	87	(6)
Compression Moulding of Thin Films	87	(3)
KBr Preparation	90	(1)
Sample Supports	90	(2)
Pellets	92	(1)
Abrasion Method	92	(1)
FTIR Analysis of Difficult Sample Forms	93	(8)
Ground Polymers or Inorganic Ash	93	(1)
Polymer Fibres	94	(1)
Carbon-Filled Samples	94	(1)
Thin Films on Reflective Substrates	95	(1)
Irregularly Shaped Samples	96	(1)
Polymer Foams	97	(1)
Polymer Composites	97	(1)
Clear, Highly Elastomeric Samples	98	(2)
Thick Viscous Samples	100	(1)
Microsamples	100	(1)
Paints	100	(1)
Samples with Suspected Surface Contamination	101	(1)
Multilayer Samples	101	(1)
Interpreting and Validating FTIR Data	101	(4)
Introduction	101	(2)
Steps Involved in PVC and PVDC Identification	103	(1)
IR Identification of Styrenics	104	(1)
Distinguishing between Polyamides and Polyurethanes	104	(1)
Nylon Analysis	104	(1)
Derivatization Techniques	105	(2)
An Example of Derivatization	105	(1)
References	106	(1)
Thermal Analysis of Polymers	107	(40)
Introduction	107	(1)
Differential Scanning Calorimetry	108	(21)
Introduction	108	(1)
Representative Sampling	109	(1)
Sample Preparation for DSC	109	(1)
Effect of Sample Mass and Heating Rate	110	(1)
Advanced DSC Techniques	110	(1)
Information that can be Obtained by DSC Analysis	110	(1)
Thermal History	110	(2)
Melting Point	112	(1)
Glass Transition Temperature	113	(2)
Polymer Crystallinity	115	(1)
Crystallization Behaviour	116	(1)
Crystallization Kinetics	117	(1)
Cooling Rate of a Polymer Component	117	(1)
Physical Ageing	117	(2)
Detecting the Presence of Regrind	119	(1)
Evaluating Heat Ageing of Semicrystalline Polymers	119	(2)
Evaluating Heat Ageing of Amorphous Polymers	121	(1)
Evaluating Effects of Solvents on Amorphous Polymers	122	(1)
Unusual DSC Features	122	(1)
Cold Crystallization	123	(1)
Water-Related Phenomena	124	(1)
Secondary Melting Peaks	124	(3)
Unexpected Exothermic Deviations	127	(1)
DSC Behaviour of Common Polymers	127	(1)
Amorphous Polymers	127	(1)
PET	127	(1)
PPS	128	(1)
PBT	128	(1)
Nylon 6	128	(1)
Dynamic Mechanical Thermal Analysis	129	(2)
Dynamic Mechanical Rheological Testing	131	(1)
Thermomechanical Analysis	132	(1)
Glass Transition Temperature and its Determination	133	(5)
Introduction	133	(1)
Determining Tg	133	(5)
Thermogravimetry	138	(7)
Introduction	138	(1)
Isothermal TG	138	(1)
Important Experimental Factors	139	(2)
High-Resolution TG	141	(1)
TG---FTIR	141	(3)
Limitations of TG-FTIR	144	(1)
TG MS	144	(1)
Thermal Volatilization Analysis	145	(2)
References	145	(2)
Identification and Analysis of Polymers	147	(46)
Introduction	147	(6)
Density Measurement	147	(2)
Flammability Testing	149	(1)
Thermal Analysis and FTIR Spectroscopic Methods	150	(1)
Chemical Equivalency	151	(1)
Solubility Testing	151	(1)
Structural Information on Polymers	151	(2)
Molecular Weight Measurement	153	(1)
Examples of Analytical Techniques used for Common Polymers	153	(40)
ABS Analysis	153	(1)
Introduction	153	(1)
Determining the Rubber Content of ABS	154	(1)
Analysis of Weathered ABS	155	(1)
Epoxy Analysis	156	(1)
Introduction	156	(1)
FTIR and NMR Spectroscopies	157	(1)
High Performance Liquid Chromatography	157	(1)
UV Analysis	157	(1)
EVA Analysis	158	(1)
FTIR Spectroscopy	158	(1)
Thermogravimetry	158	(1)
TG-Titrimetry	159	(2)
TG MS	161	(1)
Thermal Volatilization Analysis	161	(1)
UV Spectrophotometry	161	(1)
Fluoropolymer Analysis	161	(1)
HIPS Analysis	162	(1)
Determining the Polybutadiene Content of HIPS	163	(2)
Liquid Crystal Polymer Analysis	165	(1)
Nylon Analysis	165	(1)
FTIR Spectroscopy	165	(1)
DSC	166	(1)
PBT Analysis	166	(1)
DSC	166	(1)
MW Determination	167	(1)
Polycarbonate Analysis	167	(1)
PE Analysis	168	(1)
FTIR Spectroscopy	168	(1)
Fractionation	169	(1)
PEEK Analysis	170	(1)
DSC	170	(1)
Determining Crystallinity	170	(1)
Crystallization Behaviour	171	(1)
Determining the Glass Transition	172	(1)
Thermal Degradation of PEEK	172	(1)
PET Analysis	172	(1)
Phenolic Resin Analysis	173	(1)
FTIR Spectroscopy	173	(1)
Chromatographic Techniques	174	(1)
Pyrolysis-GC-MS	174	(1)
TG-MS	174	(1)
PMMA Analysis	175	(1)
Polysulfone Analysis	175	(1)
PP Analysis	175	(1)
FTIR Spectroscopy	175	(1)
DSC	176	(1)
MW Fractionation	176	(1)
Analysing PP Copolymers	176	(1)
PPO Analysis	177	(1)
PPS analysis	177	(2)
PU Analysis	179	(1)
Introduction	179	(1)
Compositional Analysis of PUs by FTIR Spectroscopy	180	(2)
Sample Preparation for FTIR Spectroscopy	182	(1)
Identifying the Acid in the Ester Portion of PU	182	(1)
Determing NCO Content	182	(1)
Analysis of Hydrolytic Breakdown Products	183	(1)
DSC Analysis	184	(1)
Pyrolysis Methods	184	(1)
PVC Analysis	184	(1)
FTIR Spectroscopy	184	(1)
Analysis of Plasticizers	185	(1)
Determination of Impact Modifiers	185	(1)
MW Determination	186	(1)
Determination of Crystallinity	186	(1)
Determining the Glass Transition Temperature	187	(1)
Degree of Fusion of PVC	187	(1)
Degradation of PVC	187	(1)
SAN Analysis	188	(1)
Silicone Rubber Analysis	188	(1)
Thermoplastic PU Elastomer Analysis	188	(1)
Unsaturated Polyester Resin Analysis	189	(1)
References	189	(4)
Analysis of Blends, Copolymers and Oligomers	193	(22)
Polymer Blends	193	(8)
Introduction	193	(1)
Miscibility of Blends	194	(1)
Immiscible Blends	195	(1)
Compatibilization	196	(1)
Interpenetrating Networks	196	(1)
Determination of the Blend Miscibility and Blend Ratio	196	(1)
Analysis of Phase Dispersion in Polymer Blends	196	(2)
Examples of Techniques for Determining Blend Composition	198	(1)
Composition of LLDPE/LDPE Blends by DSC	198	(1)
Composition of Nory1™ Blends by DSC	199	(1)
Composition of Nory1™ Blends by Pyrolysis-Gas Chromatography	200	(1)
Copolymers	201	(5)
Introduction	201	(2)
Copolymer Analysis	203	(1)
Analysis of Block Copolymers	203	(2)
Microscopy of Copolymers	205	(1)
FTIR Spectroscopic Analysis of Copolymers	205	(1)
Oligomers	206	(9)
Introduction	206	(1)
Analysis Methods	207	(1)
HPLC	207	(1)
Supercritical Fluid Chromatography	208	(1)
Laser-Desorption/Fourier-Transform Mass Spectrometry	208	(1)
Oligomers in HDPE	208	(2)
Oligomers in PET	210	(2)
Oligomers in Silicone Polymers	212	(1)
Oligomers in PMMA	213	(1)
References	213	(2)
Identification and Analysis of Thermoset Elastomers	215	(15)
Thermogravimeny	215	(7)
FTIR Spectroscopic Analysis of Carbon-Filled Rubbers	222	(1)
Sample Preparation for FTIR Spectroscopy	222	(1)
Rubber Identification by Pyrolysis Methods	223	(1)
Pyrolysis-IR Spectroscopy	223	(1)
Pyrolysis-GC	223	(1)
Pyrolysis-GC-MS	223	(1)
Pyrolysis-MS	224	(1)
Analysis of Specific Rubber Types	224	(6)
SBR Analysis	224	(1)
PB Analysis	225	(1)
NBR Analysis	225	(1)
Polychloroprene Analysis	226	(1)
EPDM Analysis	226	(2)
Thermoplastic Elastomer Analysis	228	(1)
References	228	(2)
Analysis of `Difficult' or Intractable Polymer Samples	230	(10)
Introduction	230	(1)
FTIR Spectroscopic Techniques for Difficult Samples	230	(3)
DRIFT Analysis of Intractable Materials	231	(1)
Abrasion-DRIFT Analysis	231	(1)
Photoacoustic FTIR Spectroscopy	232	(1)
Pyrolysis of Intractable Samples	233	(3)
Pyrolysis of Small Samples	233	(1)
Manipulation of Pyrolytic Oils	234	(1)
Pyrolysis-IR Spectroscopy	234	(1)
Pyrolysis-GC-FTIR Spectroscopy	234	(1)
Rubber Pyrolysis	234	(2)
Vacuum Pyrolysis	236	(1)
Pyrolysis in the MS Ion Source	236	(1)
Thermogravimetry	236	(1)
Laser-Desorption Fourier-Transform Mass Spectrometry	237	(3)
References	239	(1)
Analysis of Additives in Polymers and Elastomers	240	(30)
Introduction	240	(1)
Grinding	241	(1)
Additive Extraction	242	(6)
Soxhlet Extraction	243	(1)
Soxtec™ Extraction	243	(1)
Reflux Extraction	243	(1)
Solvent Extraction of Polymer Films	244	(1)
Ultrasonic Extraction	244	(1)
Microwave-Assisted Extraction	245	(1)
Supercritical Fluid Extraction	246	(2)
Analysis Methods	248	(11)
UV Spectroscopic Analysis of Additives	248	(1)
IR Spectroscopic Analysis of Additives	248	(1)
GC Analysis of Additives	249	(1)
HPLC Analysis of Additives	249	(2)
GC-MS Analysis of Additives	251	(1)
SEC-GC-MS Analysis of Additives	252	(1)
Supercritical Fluid Chromatography Analysis of Additives	252	(2)
SFC-FTIR Spectroscopic Analysis of Additives	254	(1)
In situ Additive Detection in Polymers	254	(1)
XRF Analysis	254	(2)
Examples of the Use of XRF for Additive Analysis	256	(1)
Common elements	256	(1)
Uncommon elements	257	(1)
Specific element combinations	257	(1)
Important Considerations in XRF Analysis	258	(1)
Sample preparation	258	(1)
Experimental technique	258	(1)
Spectral interference	259	(1)
In situ Additive Analysis in Rubbers	259	(1)
Miscellaneous Examples of Additive Analysis Methods	260	(10)
Unknown Additive Analysis	260	(1)
Antistatic Additive Analysis	261	(1)
Thioester Additive Analysis	261	(1)
Oligomeric (`Non-Extractable') Additive Analysis	261	(1)
Carbon Black Determination	262	(2)
Filler Analysis	264	(1)
Furnace Ashing	264	(2)
Filler Content Quantification	266	(1)
Filler/Pigment Content Determination of Polyamides and Polyesters	266	(1)
Ash Analysis by FTIR Spectroscopy	267	(1)
Determination of Fibre Content and Distribution in Glass-Reinforced Composites	268	(1)
References	268	(2)
Analysis of Contaminants and Inclusions in Polymers	270	(34)
Introduction	270	(1)
Classes of Typical Contamination	271	(9)
Black Specks	271	(4)
Cellulosic Contamination	275	(1)
Metal Contamination	275	(2)
Polymeric Contamination	277	(1)
Additive Contamination	278	(1)
Contamination From Storage and Shipping Containers	279	(1)
Chemical Contamination	279	(1)
Miscellaneous Sources of Contamination	280	(1)
Techniques for Analysis of Contamination	280	(8)
Optical Microscopy	280	(1)
FTIR Microscopy	281	(1)
EDAX (X-Ray Microanalysis)	282	(1)
ESCA	283	(1)
Micro-XRF	283	(1)
Pyrolysis-GC	283	(1)
Thermogravimetry	284	(1)
TG-GC-MS	284	(1)
TP-SIP-MS	285	(1)
TOF-SIMS	285	(1)
Screening Polymer Batches for Contamination	286	(2)
Gel Particles and other Inclusions	288	(16)
Introduction	288	(3)
Gels in PE	291	(2)
Gels in PP	293	(1)
Gels in PVC	294	(1)
Oxidized Particles in Polymers	294	(1)
Gels due to Additives	295	(1)
Contamination-Related Gels	295	(1)
Foreign Polymer Gels	296	(1)
Analysis of Gel Imperfections	296	(1)
Polarized-Light Examination	296	(1)
Hot-Stage Microscopy	296	(2)
FTIR Microscopy	298	(2)
DSC Analysis	300	(1)
Micro-Ashing	300	(2)
Quantitying Gel Defects	302	(1)
References	302	(2)
Mechanical Failure Mechanisms of Polymers	304	(59)
Introduction	304	(6)
Tensile Failure	310	(1)
Shear Failure	310	(1)
Compressive Failure	311	(1)
Crazing	311	(2)
Introduction	311	(1)
Crazing in Rubber-Modified Polymers	311	(1)
Analysis of Crazing	312	(1)
Shear Banding	313	(2)
Introduction	313	(1)
Analysis of Shear Banding	314	(1)
Shear Deformation (Banding) versus Crazing	314	(1)
Creep	315	(2)
Introduction	315	(1)
Measuring Creep	316	(1)
Fatigue Failure	317	(7)
Introduction	317	(3)
Measuring Fatigue Resistance	320	(1)
Examples of Fatigue Behavior in Different Polymers	321	(1)
Fatigue of Polyacetal	321	(1)
Fatigue of Toughened Styrenic Polymers	321	(1)
Fatigue of Rubbers	321	(1)
Fatigue of Nylon	322	(1)
Fatigue of Short-Fibre-Reinforced Plastics	322	(1)
Fatigue of Continuous-Fibre Composites	322	(1)
Analysing Fatigue Fracture	323	(1)
Impact Fracture	324	(6)
Introduction	324	(1)
Measuring Impact Strength	325	(2)
Notch-Sensitivity	327	(1)
Temperature Sensitivity	328	(2)
Physical Ageing	330	(3)
Introduction	330	(2)
Common Polymers which Undergo Physical Ageing	332	(1)
PVC	332	(1)
PET	332	(1)
PPO	332	(1)
Physical Ageing of Rubber-Modified Glassy Polymers	333	(1)
Analysis of Physical Ageing	333	(1)
Failure Due to Temperature Effects	333	(3)
Maximum- and Minimum-Use Temperatures	333	(2)
Temperature Sensitivity of Creep Modulus	335	(1)
Thermal Shock	335	(1)
Failure Due to Improper Processing	336	(3)
Problems due to Excessive in-Mould Orientation	336	(1)
Melting and Moulding Temperatures	336	(1)
Was the Correct Mould Temperature Used?	337	(1)
Use of Regrind	338	(1)
General Examples of Polymer Failure	339	(13)
PVC	339	(1)
Brittle Failure in PVC	339	(2)
Thermal Degradation of PVC	341	(1)
Physical Ageing of PVC	341	(1)
Annealing	342	(1)
Impact Strength	342	(1)
Strain-Rate Effects on PVC	343	(1)
Embrittlement of PVC by Loss of Plasticizer	343	(1)
Stress Concentrations	344	(1)
Polycarbonate	344	(1)
Introduction	344	(1)
MW Reduction	345	(1)
Processing Conditions	345	(1)
Solvent-Induced Crystallization	346	(1)
Structural Flaws and Surface Stresses	347	(1)
Nylon	347	(1)
PET	347	(1)
PBT	348	(1)
PPS	348	(1)
Polyacetal	349	(1)
Impact-Modified Polymers	349	(1)
Epoxy Resins	350	(1)
Unsaturated Polyesters	350	(1)
Polyetherimide	350	(1)
Polysulfones	350	(1)
Thermoplastic Polyurethanes	351	(1)
PTFE	351	(1)
Failure of Short-Fibre-Glass-Reinforced Thermoplastics	351	(1)
Failure of Medical Plastics	352	(1)
Failure of Polymers and Elastomers by Explosive Decompression	352	(7)
Polymers Susceptible to ED Damage	355	(1)
Nature of ED Damage	356	(3)
Failure Analysis by Fractography	359	(4)
References	361	(2)
Chemical Attack of Polymers	363	(34)
Introduction	363	(2)
Factors Determining Chemical Resistance	365	(1)
Types of Chemical Attack	365	(26)
Hydrolytic Degradation of Polymers	365	(1)
Introduction	365	(2)
Hydrolysis of Poly(ethylene Terephthalate)	367	(1)
Hydrolysis of Polycarbonate	368	(1)
Hydrolysis of Polyacetals	369	(3)
Hydrolysis of Polyurethanes	372	(1)
Hydrolysis of Polyethersulfones	372	(1)
Hydrolysis of Thermosets	372	(1)
Hydrothermal Degradation of Composites	373	(1)
Hydrolysis During Steam Autoclaving of Polymers	373	(1)
Acid and Alkaline Attack	374	(1)
Introduction	374	(1)
Additives and Residues from Manufacturing Operations	374	(1)
Environmental Exposure	374	(1)
In vivo Situations	375	(1)
By-Products of Degradation	375	(1)
Service Use	375	(3)
Analysing for Acid Attack	378	(1)
Acid-Catalysed Hydrolysis	379	(2)
Alkaline Attack	381	(1)
Chemical Degradation by Strong Oxidizing Liquids	381	(1)
Ester-Interchange and Transesterification Reactions	382	(1)
Aminolysis	382	(3)
Rubber Degradation by Chloramines	385	(1)
Solvent Attack	385	(2)
Solvation	387	(1)
Salt Solutions	388	(1)
Catalysed Chemical Degradation	388	(1)
Microbial Chemical Degradation	389	(2)
Analysis Methods for Assessing Chemical Degradation	391	(4)
Introduction	391	(1)
Mechanical Tests	392	(1)
Swelling Tests	392	(1)
DMTA	393	(1)
Headspace Analysis	393	(1)
FTIR Spectroscopic Analysis	393	(1)
EDAX	394	(1)
Case Study	395	(2)
References	395	(2)
Oxidative Degradation of Polymers	397	(52)
Introduction	397	(13)
Factors Affecting Polymer Oxidation	401	(1)
Temperature	401	(1)
Branching (Tertiary Hydrogen Atoms)	402	(1)
Oxygen Diffusion	402	(1)
Polymer Unsaturation	403	(1)
Catalyst Residues	403	(1)
Stress	404	(1)
Effect of Oxidation on Polymer Properties	404	(1)
Molecular Weight	404	(1)
Mechanical Properties	405	(1)
Other Properties	406	(1)
Heterogeneous Oxidation	406	(1)
Metal-Catalysed Oxidation	406	(2)
Processing Degradation	408	(2)
Accelerated Ageing Techniques	410	(4)
Oven Ageing	411	(1)
Assessing Processing Degradation by Multipass Extrusion	411	(1)
Extrapolation of Oxidative Ageing Data	412	(1)
Some Problems with Arrhenius Extrapolations	412	(1)
Discontinuities in extrapolation plots due to polymer transitions	412	(1)
Temperature fluctuations in ovens used for accelerated ageing	413	(1)
Changes in `cage' effect with temperature	413	(1)
Sample non-uniformity	413	(1)
Differences in antioxidant solubility below and above the polymer Tm	413	(1)
Stress relaxation	413	(1)
Testing Methods	414	(35)
Melt-Flow Index	414	(1)
Residence-Time Melt-Flow Index	415	(1)
IR Spectroscopic Methods	416	(1)
Carbonyl Index	417	(1)
Limitations of Carbonyl Measurements	417	(1)
Derivation of Carbonyl and Hydroxyl Groups	418	(1)
Differential Scanning Calorimetry	419	(1)
Oxidative Induction Time (OIT)	420	(1)
Introduction	420	(2)
Limitations of the OIT Method	422	(2)
Extrapolation of OIT Data	424	(1)
Thermogravimetric Analysis	424	(1)
Gel Content of Oxidized Polymers	424	(2)
ESR Spectroscopy	426	(1)
XPS	426	(1)
Oxygen Uptake	426	(1)
Introduction	426	(1)
Shape of Oxygen-Uptake Curve	427	(1)
Constant-Volume and Constant-Pressure Instruments	428	(1)
Manometers/Manual Apparatus	428	(2)
Limitations of Oxygen Uptake	430	(1)
Hydroperoxide Detection	431	(1)
Introduction	431	(1)
Iodometric Method	432	(2)
Ferric Thiocyanate Method	434	(1)
Infrared Spectroscopic Methods	435	(1)
Chemiluminescence (CL)	435	(3)
Hydroperoxide Concentration by CL	438	(1)
Staining Techniques	439	(4)
References	443	(6)
Failure of Fibre-Reinforced Composites	449	(33)
Introduction	449	(3)
Fibre Adhesion in Composites	452	(2)
Analysis of Fibre Adhesion in Composites	453	(1)
Failure of Composites due to Manufacturing and Cure-Related Factors	454	(4)
Impurities in Commercial Thermosetting Resins	454	(2)
Advancement of Prepreg Resin During Storage	456	(1)
Distribution of Curing Agents	456	(1)
Premature Curing	456	(1)
Incomplete Curing	457	(1)
Cure Progression	458	(1)
Failure Behaviour of Composites	458	(13)
Types of Failure Mechanisms of Composites	459	(1)
De-bonding	459	(1)
Interlaminar Failure	459	(2)
Fibre Buckling	461	(1)
Fibre Pull-Out	461	(1)
Fibre Breakage	461	(1)
Cracking of Composites	462	(1)
Micro-cracking of Composites	462	(1)
Types of Loading Modes to which Composites are Subjected	463	(1)
Tensile Loading Failures	463	(1)
Compressive Loading Failures	464	(2)
Shear Loading Failures	466	(1)
Stress Rupture of Composites	467	(1)
Impact Damage of Composites	467	(2)
Fatigue Failure of Composites	469	(2)
Heat generation during fatigue	471	(1)
Creep of Composites	471	(1)
Failure of Composites due to Thermal Effects	471	(2)
Effects of Moisture on Composites	473	(1)
Hygrothermal Degradation of Composites	473	(1)
Analysis of Hygrothermal Degradation Problems	474	(1)
Chemical Attack on Composites	474	(1)
Environmental Stress Cracking	474	(1)
Oxidative Degradation	475	(1)
Photo-Oxidative Degradation of Fibre Reinforcements	475	(1)
Radiation Degradation of Composites	476	(1)
Failure Testing of Composites	476	(1)
Detecting Cracking in Composites	476	(1)
Fractography of Composites	477	(5)
Introduction	477	(1)
Specific Fractographic Examples	478	(1)
Tensile Failure	478	(1)
Mode-I Tension	479	(1)
Mode-II Shear	479	(1)
Quantifying the Fracture Surface	480	(1)
References	480	(2)
Problems Related to Additive in Polymers	482	(36)
Introduction	482	(1)
Blooming	482	(5)
Analysis	486	(1)
Sublimation	487	(1)
Analysis	488	(1)
Plateout	488	(1)
Analysis	489	(1)
Die Drool	489	(1)
Bleeding	490	(1)
Analysis	490	(1)
Additive Migration	491	(1)
Analysis	492	(1)
Additive Interactions	492	(4)
Antagonistic Additive Interactions	492	(3)
Physical Adsorption of Additives	495	(1)
Additive Decomposition	496	(6)
Thermal Decomposition of Nucleating Agents	496	(1)
Slip-Additive Degradation	497	(1)
Flame Retardants	497	(1)
Hindered-Amine Light Stabilizers	498	(1)
Pigments	498	(1)
Thermal Stability and Photostability of Pigments	498	(2)
Analysis of Pigments	500	(1)
Loss of Water of Hydration and Volatiles Formation	500	(1)
Pigment-Polymer Reactions	501	(1)
Additive-Induced Polymer Decomposition	502	(5)
Thermal Oxidation	502	(2)
Analysis	504	(1)
Photo-Oxidation	504	(1)
Analysis to Determine Catalytic Activity of TiO2 Pigments	505	(2)
Chain Cleavage by Nucleating Agents	507	(1)
Additive Dispersion Problems	507	(7)
Analysis	514	(1)
Effect of Additives on the Polymers Mechanical Properties	514	(1)
Pigment-Induced Distortion	515	(1)
Abrasion	516	(2)
References	516	(2)
Weathering of Polymers	518	(28)
Introduction	518	(4)
Preliminary Investigations	522	(1)
Detail the Problem	522	(1)
Sample Selection	522	(1)
Visual/Microscopic Inspection	523	(1)
Polymer Identification	523	(1)
Case Studies	523	(13)
PVC Window Frames and Sidings	523	(1)
Background	523	(3)
Decision Tree and Testing	526	(1)
Impact strength	526	(1)
FTIR spectroscopic analysis	527	(3)
Miscellaneous tests	530	(1)
Polyolefin Garden Furniture and Milk Crates	530	(1)
Background	530	(1)
Decision Tree and PP Testing	531	(5)
Decision Tree and HDPE Testing	536	(1)
Problems with Other Polymer Types and Applications	536	(5)
PP/EPDM Fenders	536	(1)
PMMA Glazing	537	(1)
PS	537	(1)
Acrylonitrile-Butadiene-Styrene Housings	538	(1)
Styrene-Acrylonitrile Car Grillls	539	(1)
Polyester/Glass Composite (`Fibreglass') Sheeting	539	(1)
Acrylic Surface Coatings	540	(1)
Polymer Weatherability Assessment (Accelerated Weathering)	541	(5)
Xenon-Arc Devices	542	(1)
The QUV Weathering Chamber	543	(1)
The SEPAP Weathering Chamber	543	(1)
Pitfalls in Accelerated Weathering Testing	544	(1)
References	545	(1)
Environmental Stress Cracking of Polymers	546	(41)
Introduction	546	(3)
ESC Mechanisms	549	(5)
Amorphous Plastics	549	(1)
Semicrystalline Polymers	550	(1)
The Stress Factor	550	(1)
Stress-Cracking Agents	550	(1)
Direct Stress Cracking (by Sorption)	551	(1)
Indirect Stress Cracking (by Desorption)	552	(2)
Degradative Stress Cracking	554	(1)
Special Applications where ESC is likely to Occur	554	(2)
Adhesive Bonding and Solvent Welding	554	(1)
Contact between Dissimilar Polymers	554	(1)
Welded Assemblies	555	(1)
Metal Inserts	555	(1)
Lubricated/Moving Parts	556	(1)
Testing Methods to Determine ESC Resistance	556	(5)
Constant-Deformation Test	556	(1)
Ball-Indentation Test (ISO-4600)	556	(1)
Bent-Strip Test Method (ISO-4599)	557	(1)
Polyolefin Bent-Strip Test (ASTM-D1693)	558	(1)
Constant-Load Test (ASTM-5397)	559	(1)
Spiral-Cone Method	560	(1)
Bottle ESCR Test	561	(1)
Surface-Tension and Solubility-Parameter Effects	561	(2)
Predicting ESC based on Solubility Parameters	562	(1)
Predicting ESC based on Weight Change	562	(1)
ESC Behaviour of Particular Polymers	563	(15)
Polycarbonate	563	(2)
Plasticizer Migration	565	(1)
Solvents	565	(1)
Fracture-Surface Analysis	566	(2)
Illustrative Case Studies for Stress Cracking of Polycarbonate	568	(1)
Case Study 1	568	(1)
Case Study 2	569	(1)
Case Study 3	569	(1)
Case Study 4	569	(1)
Case Study 5	569	(1)
Assessing the Stress-Cracking Resistance of PC	570	(1)
Styrenics	570	(1)
SAN	571	(1)
ABS	571	(1)
HIPS	571	(1)
Polyethylenes	572	(2)
Polypropylene	574	(1)
PMMA	574	(1)
Polyurethanes	575	(1)
PET	576	(1)
Nylons	576	(1)
PVC	576	(2)
PPO	578	(1)
Investigating an ESC Failure	578	(3)
Introduction	578	(1)
Measuring Residual Stress Levels in Moulded Parts	579	(1)
Fractography	580	(1)
Analytical Methods	581	(1)
ESC Case Study	581	(6)
References	585	(2)
Residual Stresses and Weld Lines in Polymers	587	(35)
Introduction	597
Protocol for Problem-Solving Processing Defects	587	(3)
Residual Stresses and Molecular Orientation	590	(17)
Introduction	590	(1)
Residual Stresses	590	(1)
Residual Strain near Sprue	590	(1)
Wall-thickness Variations	591	(1)
Molecular Orientation	592	(1)
Frozen-In Strain in Skin Layer	592	(1)
Determination of Residual Stresses	593	(1)
Layer-Removal Procedure for Flat Mouldings	593	(1)
Residual Stresses in Pipe Walls	594	(1)
Semi-Quantitative and Non-Quantitative Methods	594	(1)
Determination of Molecular Orientation	595	(1)
Heat Reversion	595	(1)
Solvent Immersion	596	(1)
Clear Mouldings	596	(1)
Microscopy	597	(1)
Birefringence Measurements	597	(2)
Chemical Stress-Cracking Agents	599	(2)
Case studies involving stress-cracking agents	601	(3)
Control of Residual Stresses and Molecular Orientation	604	(1)
Ageing Effects	604	(1)
Effects of Residual Stresses and Molecular Orientation on Properties	605	(1)
Practical Examples of Failures related to Residual Stress and/or Molecular Orientation	606	(1)
Weldlines	607	(10)
Introduction	607	(1)
Classification of Weldlines	608	(1)
Weldlines in Polyolefins	609	(1)
Weldlines in Caps and Cylindrical Mouldings	609	(1)
Flow Weldlines in Thin-Walled Containers	609	(1)
Appearance and Location of Weldlines	610	(1)
Strength of Weldlines	611	(1)
Factors Affecting Weldline Characteristics	611	(1)
Mould Design Aspects	611	(2)
Processing Variables	613	(1)
Effect of Additives on Weldline Strength	613	(1)
Effect of Polymer Type on Weldline Strength	613	(1)
Assessing the Contribution of Weldlines to Part Failure	614	(1)
Practical Examples of Weldline-Related Failures	614	(3)
Shrinkage and Warpage	617	(5)
Introduction	617	(1)
Factors Affecting Shrinkage and Warpage	617	(1)
Determination of Shrinkage and Warpage	618	(1)
References	619	(3)
Odour, Tainting and Outgassing Problems with Polymers	622	(25)
Odour Problems in Polymers	622	(10)
Introduction	622	(2)
Origins of Odour-Causing Compounds	624	(1)
Manufacturing Processes	624	(1)
Polyethylenes	624	(1)
Polyurethanes	625	(1)
Residual Monomer	626	(1)
Processing	626	(1)
Additives	627	(1)
Initiators	627	(1)
Chain-transfer agents	627	(1)
Plasticizers	628	(1)
Pigments	629	(1)
Stabilizers	629	(1)
Lubricants	629	(1)
Slip agents	629	(1)
Nucleating agents	630	(1)
Cross linking agents	630	(1)
Blowing agents	631	(1)
Curing	631	(1)
Use of Odour Adsorbers	631	(1)
Analysis Methods	631	(1)
Taste and Off-Flavours	632	(4)
Tainting of Plastic Containers	633	(1)
PET Bottles	633	(1)
HDPE Bottles	633	(1)
Adventitious additives	634	(1)
LDPE Bottles and Pouches	634	(1)
Taste Testing	635	(1)
Analytical Analysis of Off-Flavours	635	(1)
Out-Gassing	636	(4)
Introduction	636	(1)
Common Types of Out-Gassing	637	(1)
Formaldehyde Vapours	637	(1)
Emissions from Car Interiors	637	(1)
Outgassing from Synthetic Carpets	638	(1)
Process Solvents	639	(1)
Residual Monomer	639	(1)
Analysis of Organic Vapours Emitted from Polymers	640	(1)
Volatiles in Polymers and Their Detection	640	(7)
Volatiles	640	(1)
Analysis Methods	640	(1)
GC-MS	641	(1)
Head-Space Analysis	641	(1)
Evolved-Gas Analysis	642	(1)
TG-MS	642	(1)
Thermolysis-MS	643	(1)
Sample Handling	643	(1)
Simple-Trapping Methods	644	(1)
Comparison of Trapping Materials for Volatiles	644	(1)
Advanced Techniques	645	(1)
References	645	(2)
Adhesion Problems with Polymers and Interfaces	647	(23)
Introduction	647	(2)
Case Studies	649	(11)
Polyolefins	649	(1)
Surface Contamination of Polyolefins	650	(1)
Interfacial Adhesion in Composites	651	(2)
Investigation of the Adhesion Interface in Composites	653	(1)
Topography of the Interface	653	(1)
Weak Surface Layers	654	(1)
Chemical Nature of Reinforcement Surface	654	(1)
Detecting Residual Sizing Agent	654	(1)
Determining the Presence of Coupling Agents or Surface Treatment Materials	655	(1)
Moisture Diffusion in Composites	655	(1)
Analysis of Fibre-Matrix Adhesion	655	(1)
Sealant Failure	656	(1)
Chemical Attack of Silicones	657	(1)
Hydrolytic Deterioration of Silicone Sealants	657	(2)
Modes of Sealant Failure	659	(1)
Common Classes of Polymeric Adhesives	660	(2)
Epoxies	660	(1)
Polyurethanes	660	(1)
Cyanoacrylates	661	(1)
Silicone Sealants	661	(1)
Solvent Adhesives	661	(1)
Common Causes of Adhesive Failure	662	(8)
Topography	662	(1)
Weak Surface Layers	663	(1)
Oxidative Degradation	664	(1)
Chemical Attack	665	(1)
Cure-Related Factors	665	(2)
Gap-Filling Problems	667	(1)
Thermal Mismatch	667	(1)
Water Penetration	667	(1)
Entrapped Solvent	668	(1)
Stress	668	(1)
References	668	(2)
Voids, Blisters and Surface Defects	670	(22)
Voids	670	(13)
Introduction	670	(2)
Voids in Injection-Moulded Products	672	(3)
Voids in Rotomoulded Products	675	(2)
Voids due to Volatiles	677	(2)
Voids due to Welding	679	(1)
Voids in Composites	679	(1)
Voids in Two-Part Thermosetting Polymers	680	(1)
Voids in Sintered Components	680	(1)
Voids in Cable Insulation	681	(1)
Methodology for Problem Solving	681	(2)
Blisters	683	(6)
Introduction	683	(2)
Blisters due to Vapour Permeation	685	(1)
Blisters in Polymeric Surface Coatings (Paints)	686	(2)
Blisters in Polymer Composites	688	(1)
Surface Defects	689	(3)
Surface Blemishes	689	(1)
Weldline Surface Defects	689	(1)
Lenses in Films	690	(1)
Melt Fracture	690	(1)
Pin-Holing	690	(1)
Other Surface Defects	690	(1)
References	691	(1)
Discoloration of Polymers	692	(49)
Introduction	692	(5)
Steps for Polymer Discoloration Problem Solving	693	(3)
Some Difficulties in Studying Discoloration	696	(1)
Classification of Polymer Discoloration	696	(1)
Polyolefins	697	(19)
Antioxidant Conversion Products	698	(3)
General Analysis for AO Conversion Products	701	(5)
Antioxidant-Metal Ion Interactions	706	(2)
General Analysis for AO-Metal Ion Complexes	708	(1)
Antioxidant-TiO2 Interactions	709	(2)
Antioxidant-Acid Interactions	711	(1)
Storage Yellowing	711	(1)
Fabric Discoloration	712	(1)
General Analysis for NOx Yellowing	713	(1)
Cardboard Yellowing	713	(1)
Discoloration due to Amine-Based Additives	714	(1)
Aromatic Amines	714	(1)
Hindered-Amine Light Stabilizers	715	(1)
Antistatic Agents	715	(1)
Aromatic Polymers Containing Ph--O or Ph--N Linkages	716	(5)
Polycarbonate	716	(1)
Polyurethanes	717	(1)
Poly(Phenylene Oxide)	718	(2)
Unsaturated Polyesters	720	(1)
Polysulfones	720	(1)
Aromatic Polymers containing Ph-C=O or Ph-S Linkages	721	(5)
Poly(Ethylene Terephthalate)	721	(2)
Aliphatic Polyamides (Nylons)	723	(1)
Aromatic Polyamides (Aramids)	724	(1)
Poly(Phenylene Sulfide)	725	(1)
Nitrile Polymers	726	(3)
Polyacrylonitrile	726	(1)
Poly(Styrene-co-Acrylonitrile)	727	(1)
Acrylonitrile-Butadiene-Styrene	728	(1)
Vinyl Polymers	729	(4)
Poly(Vinyl Chloride)	729	(2)
Ethylene-Vinyl Acetate Copolymers	731	(2)
Poly(Vinylidene Fluoride)	733	(1)
Miscellaneous Polymers	733	(3)
Polystyrene	733	(1)
High-Impact Polystyrene	734	(1)
Poly(Methyl Methacrylate) and Photocured Acrylates	735	(1)
Polyoxymethylene	735	(1)
Radiation Yellowing	736	(5)
References	738	(3)
Index	741