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Intro
Polymer Science and Nanotechnology: Fundamentals and Applications
Copyright
Contents
Contributors
Preface
Part I: Polymer science
Chapter 1: Brief overview of polymer science
1.1. Basic concepts
1.2. Classification of polymers
1.2.1. Polymer structure
1.2.2. Polymerization techniques
1.2.3. Intermolecular forces
1.3. Natural vs synthetic polymers
References
Chapter 2: Nature and molecular structure of polymers
2.1. Natural vs synthetic polymers
2.2. Structure of polymers
2.2.1. Amorphous vs crystalline polymers
2.2.2. Primary structure
2.2.2.1. Monomer polarity
2.2.3. Secondary structure
2.2.3.1. Polymer chain configuration
2.2.4. Tertiary structure
2.3. Molecular weight
References
Chapter 3: Polymer synthesis
3.1. Step-growth polymerization
3.1.1. General characteristics
3.1.2. Polymerization of tri- and higher-order functional monomers
3.1.3. Polymer types and structure
3.2. Chain-growth polymerization
3.2.1. General characteristics
3.2.2. Polymerizability (thermodynamics)
3.2.2.1. Equilibrium
3.2.3. Stereochemistry of chain-growth polymerization
3.2.4. ``Living ́́versus ``controlled ́́polymerization
3.2.5. Free-radical polymerization
3.2.5.1. Conventional free-radical polymerization
Initiators
Initiation
Propagation
Termination
Inhibitors
Chain transfer
Chain transfer agents
3.2.6. Kinetics of chain-growth polymerization
3.2.6.1. Initiation
3.2.6.2. Propagation
3.2.6.3. Termination
3.2.6.4. Chain transfer
3.2.6.5. Rate of polymerization
3.2.6.6. Trommsdorff-Norrish effect or auto-acceleration or gel effect
3.2.7. Controlled/living radical polymerization
3.2.7.1. Nitroxide-mediated polymerization
3.2.7.2. Atom transfer radical polymerization
Monomer
Initiator.
Catalysts complex
Solvent
Temperature
3.2.7.3. Reversible addition-fragmentation chain transfer (RAFT) polymerization
RAFT procedure
RAFT mechanism
3.2.8. Ionic polymerization
3.2.8.1. Anionic polymerization
Overview
Solvent
Initiation
Electron transfer
Nucleophilic addition to the monomer double bond
Propagation
Termination
3.2.8.2. Cationic polymerization
Initiation
Bronsted acid
Lewis acid
Propagation
Termination
3.2.8.3. Group transfer polymerization
3.2.8.4. Ring-opening polymerization
Thermodynamics
Kinetics
3.2.8.5. Coordination polymerization
Ziegler-Natta catalysts
Termination
Metallocenes
3.2.8.6. Ring-opening metathesis polymerization
Catalysts
3.3. Solution polymerization
3.4. Suspension polymerization
3.4.1. Process description
3.4.2. Size control
3.4.3. Quality and morphology
3.5. Emulsion polymerization
3.5.1. Conventional emulsion polymerization
3.5.1.1. Miniemulsion
3.5.1.2. Microemulsion
Process description
Size control
3.5.2. Soapless emulsion polymerization
3.5.3. Dispersion polymerization
Further reading
Chapter 4: Copolymerization
4.1. Unspecified copolymers
4.2. Statistical copolymers
4.3. Random copolymers
4.4. Alternating copolymers
4.5. Periodic copolymers
4.6. Block copolymers
4.7. Graft copolymers
4.8. Kinetics of copolymerization
References
Chapter 5: Modification of polymers
5.1. Physical methods
5.1.1. Self-assembled monolayers
5.1.2. Radiation-induced surface modification
5.1.3. UV-irradiation
5.1.3.1. γ-Irradiation
5.1.3.2. Laser-induced surface modifications
5.2. Chemical modification of polymer
5.2.1. Common chemical reactions
5.2.2. PEGylation
5.2.3. Conjugation.
5.2.4. Method to make various polymeric architecture via chemical modification
References
Further reading
Chapter 6: Polymer characterization
6.1. Measurements of molecular weight
6.1.1. Gel-permeation chromatography
6.1.2. Osmometry
6.1.3. Viscosity
6.1.4. Static light scattering
6.1.5. Principle of nuclear magnetic resonance
6.1.6. NMR equipment
6.1.7. Proton (1H) NMR
6.1.8. Carbon (13C) NMR
6.1.9. Relaxation time
6.1.10. Proton-proton correlation spectroscopy and total correlation spectroscopy
6.1.11. Heteronuclear multiple quantum coherence spectroscopy and heteronuclear multiple bond correlation spectroscopy
6.1.12. Nuclear Overhauser effect spectroscopy
6.1.13. Diffusion ordered spectroscopy
References
Chapter 7: Polymer degradation and stability
7.1. Introduction
7.1.1. Aging and degradation
7.1.2. Influencing factors
7.1.2.1. Inherent factors
7.1.2.2. External factors
7.1.3. Evaluation and characterization
7.1.3.1. Evaluation
7.1.3.2. Characterization
7.2. Thermal and thermo-oxidative degradation
7.2.1. Thermal degradation
7.2.2. Thermo-oxidative degradation
7.2.2.1. Thermo-oxidation mechanism
7.2.2.2. Factors influencing thermo-oxidative degradation
7.2.3. Stabilization of thermal and thermo-oxidative degradation
7.2.3.1. Radical scavenger
7.2.3.2. Pro-antioxidant
7.3. Photolysis and photo-oxidative degradation
7.3.1. Photolysis
7.3.2. Photo-oxidative degradation
7.3.3. Stabilization of photolysis and photo-oxidative degradation
7.4. Hydrolysis and biodegradation
7.4.1. Hydrolysis
7.4.2. Biodegradation
7.4.3. Biodegradable polymers
7.5. Degradation and stabilization of polymer nanocomposites
References
Chapter 8: Polymer processing and rheology
8.1. Polymer processing
8.1.1. Mixing.
8.1.1.1. Polymer additives
8.1.1.2. Mixing mechanics
8.1.1.3. Mixing devices
8.1.2. Extrusion
8.1.2.1. Extrusion process
8.1.2.2. Single-screw extruder
8.1.2.3. Twin-screw extruder
8.1.2.4. Extrusion dies
8.1.3. Molding
8.1.3.1. Injection molding
8.1.3.2. Compression molding
8.1.3.3. Blow molding
8.1.3.4. Rotational molding
8.1.4. Calendering
8.1.4.1. Process
8.1.4.2. Arrangements of rolls
8.1.5. Coating
8.1.5.1. Fluid coating process
8.1.5.2. Methods
8.2. Polymer rheology
8.2.1. Relationship between polymer rheology and polymer processing
8.2.2. Non-Newtonian flow
8.2.3. Viscosity of polymer melts and solutions
8.2.4. Fitting functions for the flow and viscosity curves
8.2.4.1. Model function for ideal viscous flow behavior
8.2.4.2. Model function for shear-thinning and shear-thickening flow behavior
8.2.4.3. Model function for flow curves with a yield point
8.3. Rheometry
8.3.1. Capillary rheometer
8.3.2. Couette (concentric cylinder) rheometer
8.3.3. Cone-and-plate rheometer
References
Chapter 9: Thermal, mechanical, and electrical properties
9.1. Thermal analysis of polymers
9.1.1. The melting temperature of polymers
9.1.2. Glass transition temperature of polymers
9.1.3. Thermal conductivity of polymers
9.1.4. Thermal diffusivity
9.1.5. Techniques
9.2. Differential scanning calorimeter
9.2.1. Differential thermal analysis
9.2.2. Thermomechanical analysis
9.2.3. Thermogravimetry
9.2.4. Density measurements
9.3. Mechanical properties of polymers
9.3.1. Basic concepts of stress and strain
9.3.2. Stress-strain curve
9.3.3. Dynamic mechanical analysis
9.3.4. Viscoelastic behavior of polymers
9.3.5. Effects of structure and composition on mechanical properties
9.3.5.1. Molecular weight.
9.3.5.2. Cross-linking
9.3.5.3. Molecular configuration
9.3.5.4. Composition
9.4. Electrical properties of polymers
9.4.1. Conductive polymers
References
Chapter 10: Hydrogels
10.1. Introduction
10.2. Synthesis of hydrogels
10.2.1. Physically cross-linked hydrogels
10.2.1.1. Hydrogen bonds
10.2.1.2. Electrostatic interactions
10.2.1.3. Hydrophobic interactions
10.2.1.4. Crystallization
10.2.2. Chemically cross-linked hydrogels
10.2.2.1. Cross-linking by chemical reactions of complementary groups
10.2.2.2. Cross-linking by free radical polymerization
10.3. Characterization of hydrogels
10.3.1. Physical properties
10.3.2. Chemical properties
10.3.3. Mechanical properties
10.3.4. Rheological properties
10.3.5. Biological properties
10.4. Self-healing hydrogels
10.4.1. Physically self-healing hydrogels
10.4.1.1. Hydrogen bonds
10.4.1.2. Hydrophobic interactions
10.4.1.3. Metal-ligand coordination
10.4.1.4. Host-guest interactions
10.4.1.5. Combination of multiple intermolecular interactions
10.4.2. Chemically self-healing hydrogels
10.4.2.1. Phenylboronic ester complexation
10.4.2.2. Schiff base
10.4.2.3. Acylhydrazone bonds
10.4.2.4. Disulfide bonds
10.4.2.5. Other dynamic chemical bonds and reactions
10.5. Tough hydrogels
10.5.1. Homogeneous hydrogels
10.5.1.1. Tetra-PEG hydrogels
10.5.1.2. Slide-ring (SR) hydrogels
10.5.1.3. Radiation cross-linked hydrogels
10.5.2. Mechanical energy dissipating hydrogels
10.5.2.1. Double network (DN) hydrogels
10.5.3. Hydrogels based on a combination of both toughening mechanisms
10.5.3.1. Nanocomposite (NC) hydrogels
10.5.3.2. Macromolecular microspheres composite (MMC) hydrogels
References
Chapter 11: Biopolymers and natural polymers
11.1. Introduction.
11.2. Production of biopolymers.
Polymer Science and Nanotechnology: Fundamentals and Applications
Copyright
Contents
Contributors
Preface
Part I: Polymer science
Chapter 1: Brief overview of polymer science
1.1. Basic concepts
1.2. Classification of polymers
1.2.1. Polymer structure
1.2.2. Polymerization techniques
1.2.3. Intermolecular forces
1.3. Natural vs synthetic polymers
References
Chapter 2: Nature and molecular structure of polymers
2.1. Natural vs synthetic polymers
2.2. Structure of polymers
2.2.1. Amorphous vs crystalline polymers
2.2.2. Primary structure
2.2.2.1. Monomer polarity
2.2.3. Secondary structure
2.2.3.1. Polymer chain configuration
2.2.4. Tertiary structure
2.3. Molecular weight
References
Chapter 3: Polymer synthesis
3.1. Step-growth polymerization
3.1.1. General characteristics
3.1.2. Polymerization of tri- and higher-order functional monomers
3.1.3. Polymer types and structure
3.2. Chain-growth polymerization
3.2.1. General characteristics
3.2.2. Polymerizability (thermodynamics)
3.2.2.1. Equilibrium
3.2.3. Stereochemistry of chain-growth polymerization
3.2.4. ``Living ́́versus ``controlled ́́polymerization
3.2.5. Free-radical polymerization
3.2.5.1. Conventional free-radical polymerization
Initiators
Initiation
Propagation
Termination
Inhibitors
Chain transfer
Chain transfer agents
3.2.6. Kinetics of chain-growth polymerization
3.2.6.1. Initiation
3.2.6.2. Propagation
3.2.6.3. Termination
3.2.6.4. Chain transfer
3.2.6.5. Rate of polymerization
3.2.6.6. Trommsdorff-Norrish effect or auto-acceleration or gel effect
3.2.7. Controlled/living radical polymerization
3.2.7.1. Nitroxide-mediated polymerization
3.2.7.2. Atom transfer radical polymerization
Monomer
Initiator.
Catalysts complex
Solvent
Temperature
3.2.7.3. Reversible addition-fragmentation chain transfer (RAFT) polymerization
RAFT procedure
RAFT mechanism
3.2.8. Ionic polymerization
3.2.8.1. Anionic polymerization
Overview
Solvent
Initiation
Electron transfer
Nucleophilic addition to the monomer double bond
Propagation
Termination
3.2.8.2. Cationic polymerization
Initiation
Bronsted acid
Lewis acid
Propagation
Termination
3.2.8.3. Group transfer polymerization
3.2.8.4. Ring-opening polymerization
Thermodynamics
Kinetics
3.2.8.5. Coordination polymerization
Ziegler-Natta catalysts
Termination
Metallocenes
3.2.8.6. Ring-opening metathesis polymerization
Catalysts
3.3. Solution polymerization
3.4. Suspension polymerization
3.4.1. Process description
3.4.2. Size control
3.4.3. Quality and morphology
3.5. Emulsion polymerization
3.5.1. Conventional emulsion polymerization
3.5.1.1. Miniemulsion
3.5.1.2. Microemulsion
Process description
Size control
3.5.2. Soapless emulsion polymerization
3.5.3. Dispersion polymerization
Further reading
Chapter 4: Copolymerization
4.1. Unspecified copolymers
4.2. Statistical copolymers
4.3. Random copolymers
4.4. Alternating copolymers
4.5. Periodic copolymers
4.6. Block copolymers
4.7. Graft copolymers
4.8. Kinetics of copolymerization
References
Chapter 5: Modification of polymers
5.1. Physical methods
5.1.1. Self-assembled monolayers
5.1.2. Radiation-induced surface modification
5.1.3. UV-irradiation
5.1.3.1. γ-Irradiation
5.1.3.2. Laser-induced surface modifications
5.2. Chemical modification of polymer
5.2.1. Common chemical reactions
5.2.2. PEGylation
5.2.3. Conjugation.
5.2.4. Method to make various polymeric architecture via chemical modification
References
Further reading
Chapter 6: Polymer characterization
6.1. Measurements of molecular weight
6.1.1. Gel-permeation chromatography
6.1.2. Osmometry
6.1.3. Viscosity
6.1.4. Static light scattering
6.1.5. Principle of nuclear magnetic resonance
6.1.6. NMR equipment
6.1.7. Proton (1H) NMR
6.1.8. Carbon (13C) NMR
6.1.9. Relaxation time
6.1.10. Proton-proton correlation spectroscopy and total correlation spectroscopy
6.1.11. Heteronuclear multiple quantum coherence spectroscopy and heteronuclear multiple bond correlation spectroscopy
6.1.12. Nuclear Overhauser effect spectroscopy
6.1.13. Diffusion ordered spectroscopy
References
Chapter 7: Polymer degradation and stability
7.1. Introduction
7.1.1. Aging and degradation
7.1.2. Influencing factors
7.1.2.1. Inherent factors
7.1.2.2. External factors
7.1.3. Evaluation and characterization
7.1.3.1. Evaluation
7.1.3.2. Characterization
7.2. Thermal and thermo-oxidative degradation
7.2.1. Thermal degradation
7.2.2. Thermo-oxidative degradation
7.2.2.1. Thermo-oxidation mechanism
7.2.2.2. Factors influencing thermo-oxidative degradation
7.2.3. Stabilization of thermal and thermo-oxidative degradation
7.2.3.1. Radical scavenger
7.2.3.2. Pro-antioxidant
7.3. Photolysis and photo-oxidative degradation
7.3.1. Photolysis
7.3.2. Photo-oxidative degradation
7.3.3. Stabilization of photolysis and photo-oxidative degradation
7.4. Hydrolysis and biodegradation
7.4.1. Hydrolysis
7.4.2. Biodegradation
7.4.3. Biodegradable polymers
7.5. Degradation and stabilization of polymer nanocomposites
References
Chapter 8: Polymer processing and rheology
8.1. Polymer processing
8.1.1. Mixing.
8.1.1.1. Polymer additives
8.1.1.2. Mixing mechanics
8.1.1.3. Mixing devices
8.1.2. Extrusion
8.1.2.1. Extrusion process
8.1.2.2. Single-screw extruder
8.1.2.3. Twin-screw extruder
8.1.2.4. Extrusion dies
8.1.3. Molding
8.1.3.1. Injection molding
8.1.3.2. Compression molding
8.1.3.3. Blow molding
8.1.3.4. Rotational molding
8.1.4. Calendering
8.1.4.1. Process
8.1.4.2. Arrangements of rolls
8.1.5. Coating
8.1.5.1. Fluid coating process
8.1.5.2. Methods
8.2. Polymer rheology
8.2.1. Relationship between polymer rheology and polymer processing
8.2.2. Non-Newtonian flow
8.2.3. Viscosity of polymer melts and solutions
8.2.4. Fitting functions for the flow and viscosity curves
8.2.4.1. Model function for ideal viscous flow behavior
8.2.4.2. Model function for shear-thinning and shear-thickening flow behavior
8.2.4.3. Model function for flow curves with a yield point
8.3. Rheometry
8.3.1. Capillary rheometer
8.3.2. Couette (concentric cylinder) rheometer
8.3.3. Cone-and-plate rheometer
References
Chapter 9: Thermal, mechanical, and electrical properties
9.1. Thermal analysis of polymers
9.1.1. The melting temperature of polymers
9.1.2. Glass transition temperature of polymers
9.1.3. Thermal conductivity of polymers
9.1.4. Thermal diffusivity
9.1.5. Techniques
9.2. Differential scanning calorimeter
9.2.1. Differential thermal analysis
9.2.2. Thermomechanical analysis
9.2.3. Thermogravimetry
9.2.4. Density measurements
9.3. Mechanical properties of polymers
9.3.1. Basic concepts of stress and strain
9.3.2. Stress-strain curve
9.3.3. Dynamic mechanical analysis
9.3.4. Viscoelastic behavior of polymers
9.3.5. Effects of structure and composition on mechanical properties
9.3.5.1. Molecular weight.
9.3.5.2. Cross-linking
9.3.5.3. Molecular configuration
9.3.5.4. Composition
9.4. Electrical properties of polymers
9.4.1. Conductive polymers
References
Chapter 10: Hydrogels
10.1. Introduction
10.2. Synthesis of hydrogels
10.2.1. Physically cross-linked hydrogels
10.2.1.1. Hydrogen bonds
10.2.1.2. Electrostatic interactions
10.2.1.3. Hydrophobic interactions
10.2.1.4. Crystallization
10.2.2. Chemically cross-linked hydrogels
10.2.2.1. Cross-linking by chemical reactions of complementary groups
10.2.2.2. Cross-linking by free radical polymerization
10.3. Characterization of hydrogels
10.3.1. Physical properties
10.3.2. Chemical properties
10.3.3. Mechanical properties
10.3.4. Rheological properties
10.3.5. Biological properties
10.4. Self-healing hydrogels
10.4.1. Physically self-healing hydrogels
10.4.1.1. Hydrogen bonds
10.4.1.2. Hydrophobic interactions
10.4.1.3. Metal-ligand coordination
10.4.1.4. Host-guest interactions
10.4.1.5. Combination of multiple intermolecular interactions
10.4.2. Chemically self-healing hydrogels
10.4.2.1. Phenylboronic ester complexation
10.4.2.2. Schiff base
10.4.2.3. Acylhydrazone bonds
10.4.2.4. Disulfide bonds
10.4.2.5. Other dynamic chemical bonds and reactions
10.5. Tough hydrogels
10.5.1. Homogeneous hydrogels
10.5.1.1. Tetra-PEG hydrogels
10.5.1.2. Slide-ring (SR) hydrogels
10.5.1.3. Radiation cross-linked hydrogels
10.5.2. Mechanical energy dissipating hydrogels
10.5.2.1. Double network (DN) hydrogels
10.5.3. Hydrogels based on a combination of both toughening mechanisms
10.5.3.1. Nanocomposite (NC) hydrogels
10.5.3.2. Macromolecular microspheres composite (MMC) hydrogels
References
Chapter 11: Biopolymers and natural polymers
11.1. Introduction.
11.2. Production of biopolymers.