Thermal Analysis of Polymeric Materials: Methods and Developments, 2-Volume Set

Cover
Title Page
Copyright
Contents
Preface
Part I Methods
Chapter 1 Thermoanalytical Methods: Fundamental Principles and Features
1.1 Introduction
1.2 Classification of Thermoanalytical Techniques
1.2.1 Changes in Sample Property Subjected to Measurement
1.2.2 Temperature Program Modes
1.2.3 Recently Invented TA Techniques
1.3 Thermogravimetry (TG)
1.3.1 Instrumental and Principle
1.3.2 Kinetic Aspect
1.3.3 Interaction with Atmosphere
1.4 Differential Thermal Analysis (DTA) and Differential Scanning Calorimetry (DSC)
1.4.1 Instrumental Configuration and Principle
1.4.2 Heat Capacity Measurement
1.5 Thermomechanometry
1.5.1 Measurements Under Static Force Conditions
1.5.2 Measurements Under Modulated Force Conditions
1.6 Instrumental Calibrations
1.6.1 Temperature Calibration
1.6.2 Calibration of Physical Quantity and Baseline Correction
1.7 Factors Affecting Experimentally Resolved Thermoanalytical Curves
1.7.1 Sampling and Sample Mass
1.7.2 Heating Condition
1.7.3 Atmospheric Conditions
1.8 Remarks for Better Thermal Analysis
References
Chapter 2 Modulated Temperature Differential Scanning Calorimetry
2.1 Introduction
2.2 Typical Results of MTDSC
2.3 Methodology
2.3.1 Determination of a Complex Dynamic Heat Capacity
2.3.2 Mode of Modulation
2.3.3 Modulation Form
2.3.4 Applicability to (Quasi‐)Steady‐State Response
2.3.5 Calibration
2.3.6 Modulated‐Temperature Fast‐Scan Calorimetry
2.4 What Can Be Observed
2.4.1 Glass Transition as a Relaxation Phenomenon
2.4.2 Reversible Response with Heat Capacity Change and Reversible Phase Transition
2.4.3 Irreversible One‐Way Transition Kinetics
2.4.3.1 Modeling and Classification of Kinetics
2.4.3.2 Slow Kinetics: Crystallization and Chemical Reaction
2.4.3.3 Intermediate and Fast Kinetics of the First‐Order Phase Transitions
2.4.3.4 Separation of Different Types of Processes Proceeding Simultaneously
2.5 Conclusions
References
Chapter 3 Fast Scanning Calorimetry
3.1 Introduction
3.2 Development and Advancement of Fast Scanning Calorimetry
3.2.1 Fast Scanning Sensors
3.2.2 Temperature Calibration
3.2.2.1 The Thermometer and Thermal Lag
3.2.2.2 Static Temperature Gradients
3.2.2.3 Lateral Temperature Profile in Membrane‐Based Calorimeters
3.2.3 Heat Capacity and Transition Enthalpy Determination
3.2.4 The Sample
3.3 Selected Applications of FSC to Polymers
3.3.1 Glass Transition
3.3.2 Polymer Crystallization
3.3.2.1 Overall Crystallization Kinetics
3.3.2.2 Critical Cooling and Heating Rates
3.3.3 Melting–Recrystallization–Remelting; Multiple Melting Peaks
3.3.3.1 Superheating and Melting Kinetics
3.3.3.2 Isothermal Melting Kinetics and Recrystallization
3.3.4 Crystal Nucleation in Polymers
3.3.4.1 Tammann's Nuclei Development Method
3.3.4.2 Non‐isothermal Crystal Nucleation
3.3.4.3 Isothermal Crystal Nucleation
3.3.4.4 Growth and Dissolution of Crystal Nuclei
3.3.4.5 Heterogeneous Nucleation
3.3.5 Analysis of Thermally Unstable Materials
3.3.6 Other Applications
3.3.6.1 Protein Unfolding
3.3.6.2 Thermogravimetry by FSC
3.3.7 Combination of FSC with Other Analytical Techniques
3.3.7.1 Visualization of Polymer Crystallization by In situ Combination of Atomic Force Microscopy and Fast Scanning Calorimetry
3.3.7.2 Combination of Infrared Spectroscopy and Fast Scanning Chip Calorimetry
3.4 Outlook
Acknowledgments
List of Abbreviations
References
Chapter 4 Use of Different Temperature Control Techniques Coupled with FTIR Spectroscopy to Simultaneously Induce and Identify the Physical Properties, Chemical Reactions, and Thermal Degradation of Polymers
4.1 Introduction
4.2 Hyphenation of Various Temperature Control Techniques with FTIR Spectroscopy in Polymer Analysis
4.3 Simultaneous DSC‐FTIR Technique Used to Investigate the Alterations of Polymeric Materials
4.3.1 Introduction of DSC
4.3.2 Introduction of DSC‐FTIR Spectroscopy
4.3.3 DSC‐FTIR Coupled Instrument
4.3.4 Physical and Chemical Changes of Polymers Studied by DSC‐FTIR Technique
4.3.4.1 Physical Changes
4.3.4.2 Chemical Reactions: Crosslinking/Curing and Cyclization
4.3.4.3 Other Related Study
4.4 In Situ Real‐Time FTIR‐Temperature Controller Used to Assess the Changes of Polymeric Materials
4.4.1 Introduction of In Situ Real‐Time FTIR‐Temperature Controller
4.4.2 Chemical Reactions: Crosslinking and Curing Reactions
4.4.3 Chemical Reactions: Polymerization/Copolymerization
4.4.4 Chemical Reactions: Cyclization and Imidization
4.4.5 Physical Properties
4.5 Variable Temperature FTIR Study of the Changes of Polymeric Materials
4.5.1 Introduction of Variable Temperature FTIR Spectroscopy
4.5.2 Chemical Reactions: Curing Reactions and Crosslinking
4.5.3 Chemical Reactions: Thermal Degradation
4.5.4 Chemical Reactions: Cyclization and Polymerization
4.5.5 Conformational Change
4.6 TGA‐FTIR Technique Applied to Explore the Alterations of Polymeric Materials
4.6.1 Introduction of TGA‐FTIR Spectroscopy
4.6.2 TGA‐FTIR Coupled Instrument
4.6.3 Representative Examples of Thermal Decomposition
4.7 Conclusions and Future Perspectives
Acknowledgments
Conflict of Interest
References
Part II Fundamentals
Chapter 5 Glass Transition and Relaxation Phenomena
5.1 Introduction
5.2 Relaxation Phenomena in Glass‐Forming Liquids
5.2.1 Main (α) Relaxation Process
5.2.1.1 Response in the Time and Frequency Domain
5.2.1.2 Temperature Dependence of the Relaxation Time
5.2.1.3 Theoretical Approaches
5.2.2 Secondary Relaxations
5.2.3 The “Boson” Peak
5.2.4 Polymer‐Specific Relaxation
5.3 Glass Transition and Physical Aging
5.4 Perspective on the Connection Between Relaxation Phenomena and the Glass Transition and Physical Aging
5.4.1 Bulk Glasses
5.4.2 Glasses Under Geometrical Confinement
5.5 Conclusions
Acknowledgments
References
Chapter 6 Polymer Crystallization
6.1 Introduction
6.2 Key Features of Polymer Crystallization
6.3 Crystal Nucleation
6.4 Crystal Growth
6.5 Crystallization in Polymer Blends
6.6 Coupling Between Crystal and Amorphous Phases
6.7 Crystallization in Industrial Processing
6.8 Key Features of Flow Induced Crystallization
6.9 Concluding Remarks
References
Chapter 7 Kinetics of Cross‐Linking Polymerization (Curing)
7.1 Introduction
7.2 The Chemistry of Cross‐Linking
7.3 The Physics of Cross‐Linking
7.4 Kinetic Models
7.5 DSC Measurements
7.6 Model‐Fitting Kinetic Analysis
7.7 Isoconversional (Model‐Free) Kinetic Analysis
7.8 Variations of Isoconversional Activation Energy
7.9 Conclusions
References
Chapter 8 Heat Capacity of Polymeric Materials
8.1 Introduction
8.2 Instrumentation and Measurements
8.2.1 Adiabatic Calorimetry and Quantum Design Physical Property Measurement System
8.2.2 Differential Scanning Calorimetry
8.2.3 Temperature Modulated Calorimetry an Fast Scanning Calorimetry
8.3 Apparent Heat Capacity and Heat Capacity of Polymeric Materials
8.3.1 Experimental Apparent Heat Capacity and Heat Capacity
8.3.2 Heat Capacity of Solid‐State Polymers
8.3.3 Heat Capacity of Liquid State Polymers
8.4 Quantitative Thermal Analysis of Polymeric Materials Based on the Heat Capacity
8.5 Summary and Conclusions
References
Chapter 9 Thermo(oxidative) Stability of Polymeric Materials
9.1 Thermo(oxidative) Stability and Its Importance in Polymeric Materials
9.2 Polymeric Material Degradation Modes and Reaction Mechanisms
9.2.1 Thermal Degradation
9.2.2 Thermo‐Oxidative Degradation
9.3 Thermogravimetry of Polymeric Materials
9.3.1 Test Parameters
9.3.2 Determination of Activation Energy and Degradation Kinetics
9.4 Instrument Hyphenation in the Analysis of Evolved Gases
9.5 Differential Scanning Calorimetry
9.5.1 Oxidation Induction Time and Temperature
9.6 Lifetime Estimation
9.6.1 Accelerated Aging
9.7 Thermal Stability of Selected Polymer Groups
9.7.1 Thermal Stability of Polyamides
9.7.2 Thermal Stability of Blends and Elastomers
9.7.3 Thermal Stability of Composites
9.8 Tabulated Thermogravimetric Data for Selected Polymers
References
Part III Materials
Chapter 10 Liquid Crystalline Polymers
10.1 Introduction
10.2 Liquid Crystalline Polymers of Great Commercial Value
10.3 Rigid and Elastic Liquid Crystalline Polymer Networks
10.4 Liquid Crystalline Epoxy Resin
References
Chapter 11 Polymer Nanocomposites and Hybrid Materials
11.1 Introduction
11.2 A Brief Overview of Polymer Nanocomposites and Hybrid Materials
11.3 Various Synthesis Routes of Hybrid Polymer Nanocomposites
11.3.1 Ex Situ Method of Hybrid Polymer Nanocomposite Preparation Method
11.3.2 In Situ Method of Hybrid Polymer Nanocomposite Synthesis
11.4 Thermal Properties of Hybrid Polymer Nanocomposites
11.4.1 Glass Transition Temperature of Hybrid Polymer Nanocomposites
11.4.2 Melting Point Temperature of Hybrid Polymer Nanocomposites
11.4.3 Thermal Stability of Hybrid Polymer Nanocomposites
11.5 Applications of Thermal‐Resistant Hybrid Polymer Nanocomposites
11.6 Conclusions
References
Chapter 12 Biocomposites and Biomaterials
12.1 Introduction
12.2 The Application of Thermal Analysis Methods for Evaluation of Polymeric Biomaterials Properties
12.2.1 Thermogravimetry (TG) for Investigation of Polymeric Biomaterials
12.2.2 Hydrogels
12.2.3 Non‐porous Polymeric‐Based Structures
12.2.4 Drug‐Delivery Systems
12.2.5 The Influence of Sterilization Process on Polymer‐Based Biomaterials
12.3 Differential Scanning Calorimetry (DSC), Temperature‐Modulated DSC (TMDSC), and Fast Scanning Calorimetry (FSC)
12.3.1 Phase‐Change Materials (PCMs) as Thermal Energy Storage Systems in Injectable Bone Cements
12.3.2 The Influence of Sterilization on Biomaterials Properties
12.3.3 Hydrogels
12.4 Dynamic Mechanical Analysis (DMA)
12.4.1 Porous and Non‐porous Polymeric Structures
12.4.2 Fibers and Surgical Sutures
12.4.3 Film and Layer‐Like Implants – Skin Grafts, Proteins
12.4.4 Hydrogel‐Based Materials
12.5 Application of Thermal Analysis to Study the Properties of Biomaterials According to ISO and ASTM Standards
Acknowledgments
References
Chapter 13 Thermal Analysis Methods in Characterization of Polymer Additives
13.1 Polymer Additives: Anti‐aging Stabilizers
13.2 Polymer Additives: Plasticizers
13.3 Polymer Additives: Flame Retardants
13.4 Other Polymer Additives
13.5 Conclusions
References
Part IV Application
Chapter 14 Thermal Analysis in Polymer Recycling
14.1 Introduction
14.2 Plastics Recycling
14.2.1 General Recycling Routes in Plastic Wastes
14.3 Thermal Analysis Techniques
14.4 Thermal Analysis in Mechanical/Physical Recycling of Polymers
14.5 Thermal Analysis in Chemical Recycling of Polymers
14.6 Quality Control of Recycled Plastics with Thermal Analysis
14.7 Conclusions
Acknowledgments
References
Chapter 15 Application of Thermal Analysis Methods for Lifetime Prediction
15.1 Introduction
15.2 The Pioneers of Lifetime Prediction
15.3 Lifetime Prediction via Thermogravimetric Analysis
15.4 Lifetime Predictions Based on Long‐Term Experiments
15.5 Lifetime Prediction via Differential Scanning Calorimetry
15.6 Conclusion
References
Chapter 16 Thermal Analysis in Energy
16.1 Introduction
16.2 Thermal Analysis in Photovoltaic and Solar Cells
16.3 Polymer Electrolytes and Batteries
16.3.1 Thermal Energy Storage
16.3.2 Energy Recovery from Polymer Wastes
16.4 Biofuels Production and Characterization
16.5 Conclusions
Acknowledgments
References
Chapter 17 Thermal Analysis of Pharmaceutical Glasses Stabilized by Polymers
17.1 Introduction
17.2 Fundamental Properties of Polymers Used for Stabilizing Pharmaceutical Glasses
17.3 Manufacturing of ASDs
17.4 Miscibility Analysis of Drugs and Polymers Using DSC
17.5 Comparison with Solid‐state NMR in Terms of Evaluation of Mixing State
17.6 Physical Stabilization of Pharmaceutical Glasses
17.7 Summary
References
Chapter 18 Thermal Analysis in Aerospace and Automotive Sectors
18.1 Introduction
18.2 Composite Materials in Aerospace and Automotive Sectors
18.3 Thermal Analysis of Polymers and Rubbers
18.3.1 Thermophysical Analysis of Polymers by Differential Scanning Calorimetry (DSC)
18.3.1.1 DSC Analysis of a PA6GF30 Automotive Lever Containing Polystyrene (PS)
18.3.2 Thermomechanical Analysis of Polymers by Dynamic Mechanic Analysis (DMA)
18.3.2.1 DMA of a Differently Annealed GFRP Aircraft Engine Part
18.3.3 Thermo‐Analytical Methods Combined with Mass Spectrometry or Infrared Spectroscopy
18.3.3.1 Pyrolysis – Gas Chromatography/Mass Spectrometry (Py‐GC/MS)
18.3.3.2 Pyrolysis‐Mass Spectrometry (Py‐MS)
18.3.3.3 Thermal Desorption – Gas Chromatography Mass Spectrometry (TD‐GC/MS)
18.3.3.4 Headspace Solid‐Phase Microextraction‐Gas Chromatography/Mass Spectrometry (HS SPME‐GC/MS)
18.3.3.5 Thermogravimetric Analysis Coupled to Mass Spectrometry (TGA‐MS), to Gas Chromatography/Mass Spectrometry (TGA‐GC/MS) or to the Fourier‐Transform Infrared Spectroscopy (TGA‐FTIR)
18.4 Conclusions
Acknowledgments
References
Chapter 19 Thermo‐Analytical Techniques and Characterizations for Textile Fibers
19.1 Introduction
19.1.1 Limiting Oxygen Index (LOI)
19.1.2 Vertical and Horizontal Flammability Test
19.1.3 45° Flammability Test of Textile
19.1.4 UL94 Test for Synthetic Textile
19.2 Thermal Characterization Instruments
19.2.1 Thermo‐Gravimetry (TG) Analysis
19.2.2 DSC Analysis
19.2.3 Cone Calorimeter Test
19.2.4 TG–FTIR‐Integrated Thermal Analysis
19.2.5 Thermal Gravimetric Mass Spectroscopy (TG–MS)
19.2.6 Thermo‐Mechanical Analysis (TMA)
19.2.7 Dynamic Mechanical Analysis (DMA)
19.2.8 Heat Conduction and Radiation Test of Textiles
19.3 Conclusion
References
Index
EULA