Resistance and Stability of Polymers

Preface

Table of Contents

1 Principles of Aging

1.1 An Introduction to Polymers

1.1.1 Thermoplastics

1.1.2 Thermoplastic Elastomers

1.1.3 Elastomers

1.1.4 Thermosets (EP Resins)

1.1.4.1 Epoxy Resins (EP Resins)

1.1.4.2 Phenolic Resins (PF Resin)

1.1.4.3 Unsaturaded Polyesters (UP Resins)

1.1.4.4 Vinyl Ester Resin (VE Resin)

1.2 General Remarks, Definition of Terms

1.2.1 Definition of Aging

1.2.2 Additional Concepts

1.3 Short and Long-Term Behavior

1.3.1 Softening Behavior

1.3.2 Aging Behavior

1.3.3 Chemical Aging Processes (Chemical Degradation)

1.3.4 Physical Aging Processes and Physical Aging

1.3.4.1 Physical Aging Processes

1.3.4.2 Physical Aging

1.4 Influencing Factors

1.4.1 Effect of Temperature

1.4.1.1 Accelerative Effect of Temperature

1.4.1.2 Chemical Degradation

1.4.1.3 Physical Aging Processes

1.4.2 Effects of Oxygen

1.4.2.1 Chemical Degradation

1.4.2.2 Physical Aging Processes - Chemo-Crystallization

1.4.2.3 Effects of Ozone

1.4.3 Influence of Water

1.4.3.1 Chemical Degradation (Hydrolysis)

1.4.3.2 Physical Aging Processes

1.4.3.3 Mechanical Effects of Water

1.4.4 Influence of Mechanical Load

1.4.5 Influence of Chemical and Physical Structure

1.4.5.1 Influence of Chemical Structure

1.4.5.2 Influence of Physical Structure

1.4.6 Influence of Production Method, Catalyst Residue, and Metallic Contaminations

1.4.7 Additives

1.4.7.1 Glass Fibers

1.4.7.2 Fillers

1.4.7.3 Pigments

1.4.7.4 Influence of Chemical Purity

1.4.7.5 Flame Retardation Using Halogen Compounds

1.4.8 Effect of Radiation

1.4.8.1 Ultraviolet Radiation

1.4.8.2 Ionizing Radiation

1.4.9 Atmospheric Effects

1.4.9.1 UV Light

1.4.9.2 Temperature

1.4.9.3 Humidity, Water

1.4.9.4 Corrosive Gases

1.4.9.5 Solid Contaminations

1.4.9.6 Material History

1.4.10 Influence of Chemicals

1.4.10.1 Chemical Media Influence, Solvolysis

1.4.10.2 Physical Media Influence

1.4.11 Biological Influences

1.5 Influence of Processing and Application

1.5.1 Aging during Processing

1.5.2 Aging during Service

1.6 Service Life Prediction

1.6.1 Prerequisites for Service Life Predictions

1.6.1.1 Determining Influencing Factors

1.6.1.2 Characterizing Damage Condition

1.6.1.3 Range of Extrapolation

1.6.2 Models for Service Life Prediction

1.6.2.1 Phenomenological Description of Aging

1.6.2.2 Standardized Processes

1.6.2.3 Models for Changes in Properties with Time

1.6.2.4 Arrhenius Equation

1.6.2.5 Time-Temperature Shift

1.6.3 Dimensioning to Meet a Specific Service Life

1.6.3.1 Reduction Factors

1.6.3.2 Service Life for Technical Parts Under Mainly Static Loads

1.6.3.3 Service Life Under Dynamic Load

1.6.3.4 Service Life of Pipes

2 Testing Methods

2.1 General Remarks

2.1.1 Methods for Testing Service Life

2.1.1.1 Simulation of Actual Conditions

2.1.1.2 Accelerated Tests

2.1.1.3 Equivalence of Radiant Energy Effect

2.1.1.4 Parallel Aging

2.1.2 Aging Criteria

2.1.3 Measurement Methods

2.1.3.1 Appearance and Surface Properties

2.1.3.2 Mechanical Properties

2.1.3.3 Change in Chemical (Molecular) Structure

2.1.3.4 Measuring the Effectiveness of Antioxidants

2.1.3.5 Identification of Stabilizers and Their Concentration

2.1.3.6 Change in Physical Structure

2.1.3.7 Additional Methods

2.2 Weathering

2.2.1 Selecting a Testing Method

2.2.2 Influencing Factors

2.2.2.1 Specimen Color

2.2.2.2 Radiation

2.2.2.3 Temperature

2.2.2.4 Moisture

2.2.2.5 Climates

2.2.2.6 Boundary Layer Climates

2.2.2.7 Additional Influencing Factors in Weathering

2.2.3 Natural Weathering

2.2.3.1 Outdoor Weathering

2.2.3.2 Irradiation in Field Tests Under Window Glass

2.2.3.3 Others

2.2.4 Artificial Weathering

2.2.4.1 Irradiation Sources

2.2.4.2 Test Specifications

2.2.4.3 Process Monitoring Equipment

2.2.5 Comparability of Outdoor Weathering and Artificial Weathering

2.2.6 Simulation of Acid Precipitation: ADF Test

2.2.7 Light Exposure and Weathering of Foam Materials

2.2.8 Weathering of Rubber

2.2.8.1 Static Ozone Chamber Test

2.2.8.2 Dynamic Ozone Chamber Test

2.3 Resistance to Ionizing Radiation

2.4 Thermal and Thermal Oxidative Resistance

2.4.1 Short-Term Temperature Influence

2.4.2 Long-Term Temperature Influence

2.4.2.1 Selecting a Test Method

2.4.2.2 Oven Aging

2.4.2.3 Oxidative Induction Time and Temperature (OIT)

2.4.2.4 Creep Rupture Tests

2.4.2.5 Thermal-Oxidative Resistance of Elastomers

2.5 Chemical Resistance

2.5.1 Definition of Chemical Resistance

2.5.2 Field Tests and Experience

2.5.3 Immersion Test

2.5.4 Creep Rupture Tests

2.5.5 Stress-Cracking Resistance

2.5.5.1 Stress States in Component Parts

2.5.5.2 Stress Cracking Resistance of Plastics under Media Contact

2.6 Biological Resistance

2.6.1 Testing Resistance to Microorganisms

2.6.2 Compostability of Biodegradable Plastics

2.6.2.1 Framing Standards for Product Requirements

2.6.2.2 Standards Describing Testing Procedures

2.6.3 Biocompatibility Tests

2.7 Standards, UL Cards

2.7.1 Standards

2.7.1.1 General Standards

2.7.1.2 Weathering

2.7.1.3 Ionizing Radiation

2.7.1.4 Thermal and Thermal Oxidative Resistance

2.7.1.5 Chemical Resistance

2.7.1.6 Biological Resistance

2.7.2 Plastics Recognition Yellow Cards

2.8 Catalogue of Requirements

2.8.1 Apparatus, Containers, Pipes, Tanks

2.8.2 Building Construction

2.8.3 Electrical Engineering

2.8.3.1 Thermal Aging in Cables

2.8.3.2 Stress Cracking Resistance in Cables

2.8.4 Automotive

2.8.4.1 Loads on Vehicles

2.8.4.2 Tests for Weathering Resistance

2.8.4.3 Airbag Modules

2.8.4.4 PUR Semi-Rigid Foam

2.8.4.5 Graying Test

2.8.4.6 Environmental Simulation Tests for Fuel-Carrying Plastics Components

2.8.5 Medical Technology

2.8.6 Rubber and Plastic Hoses

3 Stabilization

3.1 Basic Principles

3.1.1 Market Development

3.1.2 Basic Principles of Stabilization

3.1.3 Influencing Factors

3.1.3.1 Fillers

3.1.3.2 Noxious Gases

3.1.3.3 Effect of Acids

3.2 Antioxidants

3.2.1 Primary Antioxidants (H Donors and Radical Interceptors)

3.2.1.1 Phenolic Antioxidants

3.2.1.2 Lactones

3.2.1.3 Sterically Hindered Amines (HAS)

3.2.1.4 Aromatic Amines

3.2.1.5 Hydroxylamines

3.2.2 Secondary Antioxidants (Hydroperoxide Decomposers)

3.2.2.1 Phosphites and Phosphonites

3.2.2.2 Thio Stabilizers

3.2.3 Bifunctional Stabilizers

3.2.4 Stabilizer Blends

3.3 Thermostabilizers, PVC Stabilizers

3.4 Light Stabilizers

3.4.1 UV Absorbers

3.4.2 Quenchers

3.4.3 Radical Scavengers and Hydroperoxide Decomposers

3.5 Bio-Stabilizers

3.6 Other Stabilizers

3.6.1 Lubricants

3.6.2 Other Additives

3.6.3 Metal Deactivators, Complexing Agents

3.6.4 Hydrolysis Stabilizers

3.7 Stabilization of Individual Polymers

3.7.1 Polyolefins

3.7.1.1 Thermal Oxidation

3.7.1.2 Light Protection

3.7.2 Styrene Polymers

3.7.2.1 Thermal Oxidation

3.7.2.2 Light Stabilization

3.7.3 Polycarbonate and Blends

3.7.3.1 Thermal Oxidation

3.7.3.2 Light Protection

3.7.3.3 Hydrolysis Stabilizers

3.7.4 Polymethyl Methacrylate

3.7.4.1 Thermal Oxidation

3.7.4.2 Light Protection

3.7.5 Polyvinyl Chloride

3.7.5.1 Thermal Degradation

3.7.5.2 Light Protection

3.7.6 Polyoxymethylene

3.7.6.1 End Group Stabilization

3.7.6.2 Integration of Comonomers

3.7.6.3 Stabilization against Thermal-Oxidative Degradation

3.7.6.4 Light Protection

3.7.7 Thermoplastic Polyester

3.7.7.1 Thermal Degradation during Processing

3.7.7.2 Thermal Oxidation

3.7.7.3 Thermal Oxidation of Polyethylene Terephthalate

3.7.7.4 Light Protection

3.7.7.5 Hydrolysis

3.7.8 Polyamides

3.7.8.1 Thermal Oxidation

3.7.8.2 Light Protection

3.7.8.3 Semi-Aromatic and Aromatic Polyamides

3.7.9 Cellulose and its Derivatives

3.7.9.1 Thermal Loading and Oxidation

3.7.9.2 Light Protection

3.7.10 Polyurethanes

3.7.10.1 Thermal Oxidation

3.7.10.2 Light Protection

3.7.10.3 Hydrolysis

3.7.11 Thermoplastic Polyurethanes

3.7.12 Tetrafluoroethylene-Ethylene Copolymer

3.7.13 High-Temperature Thermoplastics

3.7.13.1 Polyarylate

3.7.13.2 Polyphenylene Ether and Blends

3.7.13.3 Polyphenylene Sulfide

3.7.14 Thermosets

3.7.14.1 Storage Stability Prior to Processing

3.7.14.2 Molding Materials: Curing

3.7.14.3 Molding Materials: Structural Aspects

3.7.14.4 Design Aspects

3.7.15 Elastomers

3.7.15.1 Thermal Oxidation

3.7.15.2 Light Protection

3.8 Stabilization of Recycled Materials

4 Processing

4.1 Processing Influencing Service Properties

4.1.1 Influencing Parameters

4.1.1.1 Processing Parameters

4.1.1.2 Process Steps

4.1.1.3 Plastics Composition

4.1.1.4 Influence of Metallic Contaminations

4.1.1.5 Influence of Catalyst Residues

4.1.1.6 Influence of the Atmosphere

4.1.2 Processing Thermoplastics

4.1.2.1 Manufacturing Molding Compounds

4.1.2.2 Extrusion

4.1.2.3 Injection Molding

4.1.2.4 Forming Processes

4.1.2.5 Cast Molding

4.2 Recycling

4.3 Behavior of Individual Polymers

4.3.1 Polyolefins

4.3.1.1 Influence of Manufacturing Processes and Catalysts

4.3.1.2 Polyethylene

4.3.1.3 Polypropylene

4.3.2 Styrene Copolymers

4.3.2.1 Polystyrene

4.3.2.2 ABS

4.3.3 Polycarbonate

4.3.4 Polymethyl Methacrylate

4.3.4.1 Thermal Stability of PMMA

4.3.5 Polyvinyl Chloride

4.3.6 Polyoxymethylene

4.3.7 Thermoplastic Polyester

4.3.7.1 Polybutylene Terephthalate

4.3.7.2 Polyethylene Terephthalate

4.3.8 Polyamides

4.3.8.1 Polyamide 6 and Polyamide 66

4.3.8.2 Polyamide 46

4.3.8.3 Polyamide 11 and 12

4.3.8.4 Fiber Manufacture

4.3.9 Fluoropolymers

4.3.9.1 Polytetrafluoroethylene

4.3.9.2 Polytrifluorochloroethylene

4.3.9.3 Polyvinylidene Fluoride

4.3.9.4 Polyvinyl Fluoride

4.3.10 High-Temperature Thermoplastics

4.3.10.1 Polyphenylene Sulfide

4.3.10.2 Other High-Temperature Thermoplastics

4.3.11 Polyurethane

4.3.12 Thermosets

4.3.12.1 Processing Thermosets

4.3.12.2 Curing of Thermosets

4.3.12.3 Influence of Fiber Reinforcement

4.3.12.4 Polyester Resins

4.3.12.5 Epoxy Resins

4.3.12.6 Condensation Resins

5 Applications

5.1 Material Selection Based on Service Life

5.2 Resistance to Atmospheric Influences

5.2.1 Determining Factors

5.2.1.1 Influence of Light: Light-Induced Degradation

5.2.1.2 Influence of Humidity and Moisture

5.2.2 Weathering Resistance in Individual Polymers

5.2.2.1 Polyolefins

5.2.2.2 Polymerized Styrenes

5.2.2.3 Polycarbonate and Blends

5.2.2.4 Polymethyl Methacrylate

5.2.2.5 Polyvinyl Chloride

5.2.2.6 Polyoxymethylene

5.2.2.7 Thermoplastic Polyester

5.2.2.8 Polyamides

5.2.2.9 Cellulose and Derivatives

5.2.2.10 Fluoropolymers

5.2.2.11 High-Temperature Thermoplastics

5.2.2.12 Thermoplastic Elastomers

5.2.2.13 Elastomers

5.2.2.14 Polyurethane

5.2.2.15 Thermosets

5.3 Resistance to Ionizing Radiation

5.3.1 Basic Principles

5.3.2 Mechanisms

5.3.2.1 Radiation Curing

5.3.2.2 Degradation

5.3.3 Influencing Factors

5.3.3.1 Influence of the Irradiation Source

5.3.3.2 Influence of the Dose Rate

5.3.3.3 Influence of Atmosphere

5.3.3.4 Influence of Temperature

5.3.3.5 Influence of Fillers

5.3.3.6 Influence of Stabilizers

5.3.4 Applying Radiation Technology to Plastics

5.3.4.1 Targeted Crosslinking in Plastics

5.3.4.2 Sterilizing Plastics

5.3.5 Stabilization and Sensibilization

5.3.5.1 Stabilization

5.3.5.2 Sensibilization

5.3.6 Resistance to Ionizing Radiation

5.3.7 Behavior of Individual Polymers under Ionizing Radiation

5.3.7.1 Polyolefins

5.3.7.2 Styrene Polymers

5.3.7.3 Polycarbonate

5.3.7.4 Polymethyl Methacrylate

5.3.7.5 Polyvinyl Chloride

5.3.7.6 Polyvinyl Alcohol

5.3.7.7 Polyoxymethylene

5.3.7.8 Thermoplastic Polyester

5.3.7.9 Polyamide

5.3.7.10 Cellulose and Its Derivatives

5.3.7.11 High-Temperature Thermoplastics

5.3.7.12 Thermoplastic Polyurethane

5.3.7.13 Elastomers

5.3.8 Resistance to Laser Radiation

5.3.9 Radiation in the Earth’s Lower Orbit

5.4 Thermal and Thermal-Oxidative Degradation

5.4.1 Continuous Operating Temperature Based on Empirical Data

5.4.2 Explanation of Concepts

5.4.2.1 Differentiating Thermal and Thermal-Oxidative Degradation

5.4.2.2 Annealing

5.4.3 Behavior of Individual Polymers

5.4.3.1 Polyolefins

5.4.3.2 Styrene Polymers

5.4.3.3 Polycarbonate and Blends

5.4.3.4 Polymethyl Methacrylate

5.4.3.5 Polyvinyl Chloride

5.4.3.6 Polyoxymethylene

5.4.3.7 Thermoplastic Polyester

5.4.3.8 Polyamide

5.4.3.9 Cellulose and its Derivatives

5.4.3.10 Fluoropolymers

5.4.3.11 High-Temperature Thermoplastics

5.4.3.12 Thermoplastic Elastomers

5.4.3.13 Elastomers

5.4.3.14 Polyurethanes

5.4.3.15 Thermosets

5.4.3.16 Siloxanes

5.4.4 Short-Term Peak Temperature Loads

5.5 Resistance to Chemical Attack

5.5.1 Diffusion Processes during Chemical Attack

5.5.1.1 Interaction and Transport Mechanisms

5.5.1.2 Water Absorption

5.5.2 Influencing Factors

5.5.2.1 Plastics

5.5.2.2 Effective Media

5.5.2.3 Temperature

5.5.2.4 Residence Time

5.5.2.5 Concentration

5.5.2.6 Material Specific Factors

5.5.3 Physically and Chemically Active Media

5.5.3.1 Physically Active Medium

5.5.3.2 Chemical Reactions - Chemically Active Medium

5.5.4 Resistance to Stress Cracking

5.5.5 Hydrolysis

5.5.6 Creep Behavior

5.5.6.1 Influence of Temperature

5.5.6.2 Influence of Ambient Conditions

5.5.6.3 Influence of the Medium

5.5.6.4 Influence of the Material

5.5.6.5 Influence of Processing

5.5.6.6 Influence of Stabilizers

5.5.7 Ways of Improving Chemical Resistance

5.5.8 Resistance of Reinforcing Fibers

5.5.8.1 Glass Fibers

5.5.8.2 Carbon Fibers

5.5.8.3 Aramid Fibers

5.5.8.4 Chemical Resistance of Glass Fiber Reinforced Plastics

5.5.9 Behavior of Individual Polymers

5.5.9.1 Polyolefins

5.5.9.2 Styrene Polymers

5.5.9.3 Polycarbonate and Blends

5.5.9.4 Polymethyl Methacrylate

5.5.9.5 Polyvinyl Chloride

5.5.9.6 Polyoxymethylene

5.5.9.7 Thermoplastic Polyester

5.5.9.8 Polyamides

5.5.9.9 Cellulose and its Derivatives

5.5.9.10 Fluoropolymers

5.5.9.11 High-Temperature Thermoplastics

5.5.9.12 Thermoplastic Elastomers

5.5.9.13 Elastomers

5.5.9.14 Polyurethane

5.5.9.15 Thermosets

5.6 Biological Resistance and Biodegradability

5.6.1 Main Principles

5.6.1.1 Micro- and Macrobiological Damage, Biological Degradation

5.6.1.2 Influencing Factors

5.6.1.3 Protecting Plastics Against Attack by Microorganisms

5.6.2 Biodegradable Plastics

5.6.2.1 Degradable Petroleum-Based Biopolymers

5.6.2.2 Degradable Bio-Based Biopolymers

5.6.2.3 Non-Degradable Bio-Based Biopolymers

5.6.2.4 Blends and Copolymers from Various Groups of Raw and Manufactured Materials

5.6.2.5 Biodegradability and Compostability

5.6.2.6 Oxo-Degradability

5.6.3 Biocompatibility and Biomedical Applications

5.6.3.1 Use of Biodegradable Plastics in Medical Technology

5.6.3.2 Sterilization

5.6.3.3 Catalysts in Biological Media

5.6.4 Resistance of Individual Polymers to Biological Media

5.6.4.1 Polyethylene

5.6.4.2 Polypropylene

5.6.4.3 Styrene Polymers

5.6.4.4 Polyoxymethylene

5.6.4.5 Polyvinyl Chloride

5.6.4.6 Vinyl Chloride-Vinyl Acetate Copolymers

5.6.4.7 Polymethyl Methacrylate

5.6.4.8 Polyvinyl Alcohol

5.6.4.9 Polycarbonate

5.6.4.10 Cellulose and its Derivatives

5.6.4.11 Polyamide

5.6.4.12 Polyester

5.6.4.13 Polyurethanes and Thermoplastic Polyurethanes

5.6.4.14 Polyurethane Urea

5.6.4.15 Fluoropolymers

5.6.4.16 Polyether Ether Ketone

5.6.4.17 Polysiloxane

5.6.4.18 Elastomers

5.6.4.19 Thermosets

6 Mechanical Behavior of Fiber Reinforced Plastics

6.1 Long-Term Mechanical Behavior of Fiber Reinforced Plastics

6.1.1 Creep

6.2 Creep Strength

6.2.1 Description

6.2.2 Unidirectional Fiber Composite Profiles

6.2.3 Laminates

6.2.4 Miner’s Rule

6.3 Cyclic Load

6.4 Concept of Creep and Fatigue Life Prediction for Polymer Composites

6.4.1 Master Curve of CSR Strength

6.4.2 Master Curve of Creep Strength

6.4.3 Master Curve of Fatigue Strength for Zero Stress Ratio

6.4.4 Prediction of Fatigue Strength for Arbitrary Frequency, Stress Ratio, and Temperature

6.4.5 Tensile and Flexural Static Strength

6.4.6 Creep Strength

6.4.7 Fatigue Strength for Zero Stress Ratio

6.4.8 Fatigue Strength for Arbitrary Stress Ratio

Plastics, Rubbers and Their Acronyms

Other Abbreviations

A Tables of Chemical Resistance

A.1 Polyolefins

A.1.1 Resistance Factors of Polyolefin Pipes

A.1.2 Tables of Chemical Resistance for Polyolefins

A.1.3 List of Exposure Media (as Established by the German Institute for Civil Engineering, DIBt)

A.1.3.1 Preliminary Remarks

A.1.3.2 List of Exposure Media for Polyolefins

A.2 Styrene Polymers

A.2.1 Chemical Resistance of Styrene Polymers

A.2.2 Media Causing Stress Cracking in Styrene Polymers

A.3 Polycarbonate and Polymethyl Methacrylate

A.3.1 Chemical Resistance of Polycarbonate

A.3.2 Polymethyl Methacrylate

A.3.2.1 Chemical Resistance

A.3.2.2 Stress Cracking Resistance

A.4 Thermoplastic Polyester

A.5 Polyoxymethylene

A.6 Polyamides

A.6.1 Chemical Resistance for PA 6 and PA 66

A.6.2 Chemical Resistance of Polyamide 46, 610, and 612

A.6.3 Chemical Resistance for Other Polyamides

A.7 Cellulose and Derivates

A.8 Polyvinyl Chloride

A.8.1 Resistance Factors for PVC Pipes

A.8.2 Chemical Resistance of PVC

A.8.3 List of Exposure Media for PVC Provided by the German Institute for Construction Technology

A.9 Polyphenylene Sulfide (PPS)

A.10 Polyetherimide (PEI)

A.11 Polyimide (PI), Polyamide Imide (PAI), Polyphenylene Ether (PPE), Polyether Ether Ketone (PEEK)

A.12 Polyethersulfone (PES) and Polysulfone (PSF)

A.13 Fluoropolymers

A.13.1 Chemical Resistance of Fluoropolymers

A.13.2 Chemical Resistance of PTFE

A.13.3 Chemical Resistance of PVDF

A.13.4 List of Exposure Media for PVDF (Provided by DIBt)

A.14 Liquid Crystalline Polymers (LCP)

A.15 Polyurethanes

A.15.1 Polyurethanes

A.15.2 Thermoplastic Polyurethanes (TPU)

A.15.2.1 Swelling Behavior of TPU in Various Solvents

A.15.2.2 Chemical Resistance of TPU

A.16 Elastomers

A.16.1 Chemical Resistance of Materials for Tubes and Hoses

A.16.2 Chemical Resistance of Elastomers

A.17 Thermosets

A.17.1 Chemical Resistance of Thermosets

A.17.2 List of Exposure Media for Chemical Barrier Layers Provided by the DIBt

A.17.2.1 Preliminary Remarks Regarding Immersion Media in Lists 40-2.1.1 to 40-2.1.3

A.17.2.2 List of Exposure Media 40-20.1.1

A.17.2.3 List of Exposure Media 40-20.1.2

A.17.2.4 List of Exposure Media 40-20.1.3

A.17.2.5 Lists of Exposure Media 40-3.2 and 40-3.4: Glass Fiber Reinforced Laminates with Thermoplastic Coating of PP and PVC-U

A.18 Chemical Resistance in CAMPUS

Bibliography

Index