Thermal Analysis of Rubbers and Rubbery Materials

Thermal analysis is a group of techniques in which a physical property of a substance is measured as a function of temperature, while the substance is subjected to a controlled temperature programme. In differential thermal analysis, the temperature difference that develops between a sample and an inert reference material is measured, when both are subjected to identical heat treatments. The related technique of differential scanning calorimetry relies on differences in energy required to maintain the sample and reference at an identical temperature.

Thermal Analysis of Rubbers and Rubbery Materials, a multi authored handbook, describes the use of this technique:

- For determining additives in rubbery materials
- In recycling of rubbers
- In understanding the interactions of rubber - fillers and the rubber matrix
- Characterisation of rubber nano-composites and other modified rubbers and their blends
- Instrumental techniques
- Crystallisation of rubbers

Thermal Analysis of Rubbers and Rubbery Materials is a must for everybody involved in material and product development, testing, processing, quality assurance, or failure analysis in industry and laboratories.

Preface

1. Introduction
References

2. Instrumental Techniques used for Thermal Analysis of Rubbers and Rubbery Materials
2.1 Introduction
2.2 Differential Thermal Analysis (DTA)
2.2.1 DTA Instrument
2.2.1 (a) Sample Holders
2.2.1 (b) Furnace and Furnace Temperature Programmers
2.2.1 (c ) Differential Temperature Detection System
2.2.1 (d) Low Level DC Voltage Amplifier
2.2.1 (e) Recorder
2.2.2 (f) Atmosphere Control
2.3 Differential Scanning Calorimetry (DSC)
2.3.1 Heat-flux DSC
2.3.2 Power Compensated DSC
2.3.3 Temperature Modulated DSC (TMDSC)
2.4 Thermogravimetry (TG)
2.4.1 Thermobalance
2.4.2 Temperature Detection in TG or TGA
2.4.3 Furnace and Furnace Temperature Programmers
2.4.4 Controlled Atmosphere
2.4.5 Sample Containers
2.4.6 Recorders
2.4.7 Software
2.5 Derivative Thermogravimetry (DTG)
2.6 Evolved Gas Analysis (EGA) or Evolved Gas Detection (EGD)
2.7 Thermomechanical Analysis (TMA) and Thermodilatometry (TD) or Thermodilatometric Analysis (TDA)
2.7.1 Parallel Plate Rheometry (PPR)
2.7.2 Fibre Tension Spectometry
2.7.3 Stress Relaxation Spectometry
2.8 Dynamic Mechanical Analysis (DMA)
2.8.1 Torsional Braid Analysis (TBA)
2.9 Thermally Stimulated Current (TSC)
2.9.1 Principle
2.10 Relaxation Map Analysis (RMA)
2.11 Differential Photo Calorimetery (DPC)
2.11.1 DPC Instrument
2.11.2 Principle of Operation
2.11.3 Uses of DPC
2.12 Dielectric Analysis (DEA) or Dielectric Thermal Analysis (DETA)
2.12.1 Technique
2.13 Newly Developed Thermal Analysis
2.14 New Combined Methods of Thermal Analysis
2.14.1 Coupled Thermogravimetry – Infra red Spectroscopy (TG-IR)
2.14.2 Coupled Thermogravimetry – Fourier Transform Infra red Spectroscopy (TG-FT-IR)
2.14.3 Coupled Thermogravimetry – Mass Spectrometry (TG-MS)
2.14.4 Coupled Thermogravimetry – Gas Chromatography (TG-GC)
2.14.5 Coupled TG-GC-IR
2.14.6 Coupled TG-GC-MS
2.15 Conclusion
Acknowledgements
References

3. Applications of DSC and TGA for the Characterisation of Rubbers and Rubbery Materials
3.1 Introduction
3.2 Differential Scanning Calorimetry of Rubbery Materials
3.2.1 Measurement of Specific Heat and Glass Transition Temperature
3.2.2 Significance of T8
3.2.3 Factors Affecting T8
3.2.4 Effect of Molecular Weight on T8
3.2.5 Effect of Polymer Architecture on T8
3.2.6 Effect of Composition, Morphology and Thermal History on the T8 of Polymers
3.2.7 Effect of Crosslinking of Rubbers on T8
3.2.8 Monitoring Vulcanisation of Rubber Using DSC
3.2.9 Characterisation of Melting and Crystallisation of Polymer
3.2.10 Decomposition of Polymer
3.2.11 Oxidation Induction Time
3.2.12 Other Miscellaneous Applications of DSC
3.3 Thermogravimetric Analysis of Rubbery Materials
3.3.1 Thermal Degradation and Stability of Rubbers by TGA
3.3.2 Compositional Characterisation of Rubbers by TGA
3.3.3 Study of Rubber Blend Compatibility Using TGA
3.3.4 Study of Rubber Degradation Kinetics Using TGa
3.3.5 Miscellaneous Applications of TGA
3.4 Conclusion
References

4. Dynamic Mechanical Analysis (DMA) for Characterisation of Polymers, Polymer Blends and Composites
4.1 Introduction
4.1.1 Mechanical Models Describing Viscoelasticity
4.1.2 Linear Viscoelastic Behaviour of Amorphous Polymers
4.1.3 Zones of Viscoelastic Behaviour
4.1.4 Time-Temperature Superposition Principle
4.2 Instrumentation
4.2.1 Working Principle of a Dynamic Mechanical Analyzer
4.2.2 Selecting a Clamp for a DMA Experiment
4.2.3 Running a DMA Experiment
4.3 Interpretation of Dynamic Mechanical Spectra of Polymers: Case Studies
4.3.1 Glassy Polymers
4.3.2 Cyrstalline Polymers
4.3.3 Elastomers
4.4 Dependence of Storage Modulas on Frequency and Strain
4.5 Various Other Applications
4.6 Conclusion
References

5. Characterisation of Rubbers, Polymers and their Composites Using TMA
5.1 Introduction
5.2 Instrumentation
5.3 Applications
5.3.1 Determination of T8
5.3.2 Effect of Plasticiser on T8
5.3.3 Creep and Stress Relaxation
5.3.4 Use of TMA- Parallel Plate Rheometer (PPR) for Curing of Thermoset Polymers
5.3.5 Evaluation of Crosslink Density by TMA
5.3.6 TMA for Fibre Analysis
5.3.7 Why Fibre Properties are Importatnt
5.3.8 TMA for the Analysis of Composites
5.4 Use of TMA in Industry
5.4.1 TMA in the Electronics Industry
5.4.2 TMA in the Automotive Industry
5.5 Conclusion
5.6 Acknowledgements
References

6. Micro-thermal Analysis of Rubbery Materials
6.1 Introduction
6.2 Basic Principles of µTA
6.3 Modes of Micro-thermal Analysis
6.4 Micro-thermal Analysis of Rubbery Material
6.5 Morphological Investigation in Polymer Blends
6.6 Thin Films/Coating on the Substrate
6.7 Multilayer Material Characterisation
6.7.1 Thermal Properties of Rubbery Micro-Particles
6.8 Thermal Characterisation of Micro-spheres
6.9 Powder Particle Characterisation
6.10 Characterisation of Micropores
6.11 Characterisation of Nanostructured Material
6.11.1 Micro-thermal Analysis Combined with Chemical Characterisation Techniques
6.12 Future Outlook
References

7. Miscibility, Morphology and Crystallisation Behaviour of Rubber Based Polymer Blends
7.1 Introduction
7.2 Miscibility and Cyrstallisation of Biodegradable Polymer/Rubber Polymer Blends
7.3 Morphology and Crystallistation of Polyamide/Rubber Polymer Blends
Acknowledgments
References

8. Thermal Characterisation of Polymer Nanocomposites
8.1 Introduction
8.2 Thermo-Gravimetric Analysis (TGA)
8.2.1 Introduction
8.2.2 The Apparatus
8.2.3 Methodology
8.2.4 Typical TGA Curves
8.2.5 Application of TGA in Nanocomposites Characterisation
8.3 Differential Scanning Calorimetry (DSC)
8.3.1 Conventional DSC
8.3.2 The Apparatus
8.3.3 Procedure
8.3.4 Typical Data
8.3.5 Temperature-Modulated DSC (TMDSC)
8.3.6 Applications of DSC for Thermal Characterisation of Polymer Nanocomposites
8.3.7 Applications of TMDSC for Thermal Characterisation of Polymer Nanocomposites
8.4 Other Characterisation Techniques
8.4.1 Thermal Conductivity
8.4.2 Micro-Thermal Analysis (µTA)
References

9. Thermal Analysis in Understanding Rubbery Matrix and Rubber-Filler Interactions
9.1 Introduction
9.2 Thermal Analysis and Investigation of Heterogeneous Materials
9.3 Structure-Properties Relationships in Particulate Filler/Rubbery Matrix Systems
9.4 Description of the Shape and Space Distribution of Filler Particles
9.5 Filler-to-Matrix and Filler-to-Filler Interactions as Investigated by Thermal Analysis
9.5.1 Thermogravimetry
9.5.2 Dielectric Thermal Analysis (DETA) and Thermoconductometry
9.5.3 Magnetic Thermal Analysis
9.5.4 Dynamic Mechanical Analysis
9.5.5 DTA and DSC
9.6 Concluding Remarks
References

10. Study of Crystallisation of Natural Rubber with Differential Scanning Calorimetry
10.1 Introduction
10.2 Crystallisation
10.2.1 Overall Crystallisation
10.2.2 Solution-grown Crystallisation
10.3 Stem Length and Stem Length Distribution
10.4 Effect of Fatty Acids
10.5 Summary
Acknowledgements
References

11. Thermal Properties of Chemically Modified Elastomers
11.1 Introduction
11.2 Hydrogenation
11.3 Epoxidation
11.4 Halogenation, Hydrohalogenation
11.5 Chemical Modification by Grafting
11.6 Chemical Modification by Introducting Ionic Groups
11.7 Miscellaneous
Summary
Acknowledgements
References

12. Thermal Analysis of Rubber Products
12.1 Introduction
12.2 Thermal Analysis of Rubber Based Vibration Control Devices
12.2.1 Introduction
12.2.2 Vibration Damping
12.2.3 Vibration Isolation
12.2.4 Selection of Rubbers for Vibration Damping
12.2.5 DMA for the Comparison of Different Rubber Based Shock Mounts
12.2.6 Interpenetrating Polymer Networks (IPN) as Vibration Dampers
12.2.7 Air Springs
12.3 Thermal Analysis of Rubber Seals
12.3.1 Introduction
12.3.2 Major Rubbers used for Seal Manufacturing
12.3.3 Role of Thermal Analysis in the Formula Reconstruction of Rubber Seals
12.3.4 Other Thermal Studies on Rubber Seals
12.3.5 Automotive Window Seal
12.4 Thermal Analysis of Rubber-Based Cable Sheathing Compounds
12.5 Thermal Analysis of Rubber-Based Adhesives
12.5.1 Introduction
12.5.2 Testing of Adhesives
12.6 Thermal Analysis of Rubber Based Insulators
12.7 Thermal Analysis of Thermal Interface Materials (TIM)
12.8 Thermal Analysis of Automobile Tyres
12.8.1 Introduction
12.8.2 Identification of Polymer in an Automobile Tyre Using Thermal Analysis
12.8.3 Isothermal TGA of Tyre Tread Compound
12.8.4 Thermal Analysis for the Development of a Tyre Tread Compound
12.9 Concluding Remarks
Acknowledgements
References

13. Thermal Analysis in Recycling of Waste Rubbery Materials
13.1 Introduction
13.2 Utilisation of Scrap Elastomers for Material Recovery
13.2.1 Characterisation of Recycled Rubber
13.2.2 Polymer Blends Containing Recycled Rubber
13.2.3 Recycled Rubber Modified Bitumen, Concrete and Composites
13.3 Pyrolytic Utilisation of Waste Rubber
13.3.1 Degradation and Recovery of Monomer, Gas and Carbon
13.3.2 Energy Recovery Through Incineration
13.4 Concluding Remarks
Acknowledgement
References

14. Thermal Analysis of Biological Molecules and Biomedical Polymers
14.1 Introduction
14.2 Structure and Phase Behaviour of Cells, Membranes and Lipid Bilayers Using TA
14.2.1 Lipid Blends and Alloys
14.2.2 Liposomes
14.2.3 Phospholipid Additive Interactions
14.3 Molecular Dynamics, Conformational Change and Swelling Behaviour of Biopolymers Using TA
14.3.1 Level of Hydration on Thermal Characteristics of Proteins
14.3.2 State of Water and Molecular Dynamics in Biomaterials by DSC
14.4 Collagen and Collagen Based Biomaterials
14.4.1 Denaturation of Collagen from Different Origins
14.4.2 Collagen Based Composite Biomaterial
14.5 Thermal Stability of Silk and Other Elastic Biomaterials
14.6 Thermal Characteristics of Biopolymers for Drug Delivery and Drug-Polymer Interaction
14.6.1 Protein-Protein, Protein-DNA and Protein-Ligand Interactions
14.7 Thermal Characteristics of Synthetic Hydrogels and Scaffolds for Tissue Engineering
14.8 Thermal Characteristics of Biomimetic Protein Based Hydrogels
Acknowledgements
References

Abbreviations
Index