Theory and Modeling of Polymer Nanocomposites

Preface
Contents
Contributors
1 Polymer Reference Interaction Site Model (PRISM) Theory and Molecular Simulation Studies of Polymer Nanocomposites
	1.1 Introduction
	1.2 Relevant Past Experimental and Computational Studies on PNCs
	1.3 PRISM Theory
		1.3.1 Basics
		1.3.2 Linking to Molecular Simulation
		1.3.3 Open-Source Package pyPRISM
	1.4 Past, Present, and Future of PRISM Theory-Based PNC Studies
	1.5 Limitations of PRISM Theory
	1.6 Conclusions
	References
2 Density Functional Theory-Based Modeling of Polymer Nanocomposites
	2.1 Introduction
	2.2 DFT Overview
	2.3 Applications of DFT to PNCs
		2.3.1 Polymers and Nanospheres
		2.3.2 Polymers and Nanorods
		2.3.3 Polymers and Nanoplatelets
	2.4 The SCF-DFT Approach
		2.4.1 Nanoparticles in Block Copolymers—Bulk and Films
		2.4.2 “Giant Surfactants”—Single-Ligand Nanoparticles
		2.4.3 “Hairy Nanoparticles”—Single-Component Assemblies and Mixtures with Polymers
	2.5 Summary and Outlook
	References
3 Coarse-Grained Modeling of Polymer Nanocomposites: Field-Theoretic Simulations
	3.1 Introduction
	3.2 Standard Field Theory—Compressible Diblock with Homopolymer
	3.3 Hybrid Particle-Field Theory— Explicit Nanospheres
	3.4 Field-Based Nanospheres and Finite-Segment Polymers
		3.4.1 Recent Results
	3.5 Field-Based Nanorods
		3.5.1 Recent Results
	3.6 Homopolymer Grafted Nanoparticles
	3.7 Complex Grafted Nanoparticles
		3.7.1 Recent Applications
	3.8 General Interparticle Potentials
		3.8.1 Adsorbing Diblock Copolymer
	3.9 Theoretically-Informed Langevin Dynamics (TILD)
		3.9.1 Recent Applications
	3.10 Comparison of the Different Methods
	3.11 Challenges and Area for Development
	References
4 Polymer Dynamics in Polymer- Nanoparticle Interface
	4.1 Introduction
	4.2 Polymer Dynamics Around Spherical or Anisotropic Nanoparticles
		4.2.1 Experiments
		4.2.2 Simulations
	4.3 Polymer Dynamics Around a Flat Surface
		4.3.1 Experiments
		4.3.2 Simulations
	4.4 Conclusions
	References
5 The Interfacial Layers Around Nanoparticle and Its Impact on Structural Relaxation and Glass Transition in Model Polymer Nanocomposites
	5.1 Introduction
	5.2 Modeling and Simulations
	5.3 Interfacial Zone Around Nanoparticles in Nanocomposites and Near Substrate in Thin Polymer Films
		5.3.1 Qualitative Description of the Influence of Interfacial Interactions on Mobility Near Interfaces
		5.3.2 Mobility Gradient Near Interfaces
		5.3.3 Density Gradient Near Interfaces and Its Scale ξρ
		5.3.4 Comparison Between Interfacial Mobility and Density Scales
	5.4 Effects of Bound Interfacial Layer Around NP and Near Substrate on Polymer Relaxation and Overall Tg
		5.4.1 Influence of Interface Interaction on Polymer Relaxation
		5.4.2 Effect of Interfacial Interaction Strength on Tg Estimates from Thermodynamic and Dynamic Methods
	5.5 Conclusions
	References
6 Multiscale Modeling Examples: New Polyelectrolyte Nanocomposite Membranes for Perspective Fuel Cells and Flow Batteries
	6.1 Introduction
	6.2 Multiscale Modeling of Polyelectrolyte Membranes and Their Transport Properties
	6.3 Confined Film Model of a Nanocomposite Membrane
	6.4 Atomistic Simulations of Nafion/Graphene Oxide Membranes
	6.5 Modeling of Doped Non-humidified Membranes
	6.6 Mesoscopic Simulations and Simulated Example: SPEEK Membrane
	6.7 Summary
	References
7 Explorations into the Mechanics of Hairy Nanoparticle Assemblies with Molecular Dynamics
	7.1 Introduction
	7.2 Energy Renormalization (ER) Approach to Coarse-Graining
		7.2.1 ER Methodology
		7.2.2 Validation of ER Approach
	7.3 Modeling of Hairy Nanoparticle Assemblies
		7.3.1 System Setup
		7.3.2 Simulation Protocols
		7.3.3 Mechanical Property Characterization
		7.3.4 Evaluating Polymer Conformational Behavior
	7.4 Mesoscale Modeling of aHNPs
		7.4.1 PMF-Based Approach
		7.4.2 Functional Form of Effective Interactions
	7.5 Conclusion
	References
8 Predicting Mechanical Properties Using Continuum Mechanics-Based Approach: Micro-mechanics and Finite Element Analysis
	8.1 Introduction
	8.2 Discrete-Medium Modeling Tools
	8.3 Continuous-Medium Modeling Tools
		8.3.1 Analytical Modeling: Micro-mechanics
		8.3.2 Comparison of the Different Analytical Micro-mechanical Models
		8.3.3 Laminate Plate Theory
	8.4 Computational Modeling: Finite Element Analysis (FEA)
		8.4.1 Computational Micro-mechanics
	8.5 Multiscale Modeling Concepts
		8.5.1 Bottom-Up Approach: Equivalent Continuum
		8.5.2 Top-Down Approach
		8.5.3 Concurrent Modeling
	8.6 Summary
	References
9 Modeling the Thermal Conductivity of Polymer-Inorganic Nanocomposites
	9.1 Introduction
	9.2 Thermal Conductivities of Typical Polymers and Fillers
		9.2.1 Polymers
		9.2.2 Fillers
	9.3 Analytical Theories and Micromechanical Models
		9.3.1 The Parallel and Series Models as the Upper and Lower Limit Estimates
		9.3.2 EMA for Spherical Fillers
		9.3.3 Non-spherical Fillers
		9.3.4 Bruggeman Model
		9.3.5 Combined Approaches
	9.4 Computer Simulations
		9.4.1 Finite Element Modeling
		9.4.2 Interfacial Thermal Resistance Modeling
		9.4.3 Multiscale Modeling
	9.5 Summary and Outlook
	References
10 Predicting the Optical and Electrical Properties of Polymer Nanocomposites
	10.1 Introduction
	10.2 Calculation of Optical Properties
		10.2.1 Mie Theory Applied to Polymer Nanocomposites
		10.2.2 The Discrete Dipole Approximation (DDA)
		10.2.3 Finite-Difference Time-Domain (FDTD) Method
	10.3 Calculation of Electrical Properties
		10.3.1 Resistor Network Models
		10.3.2 The Poisson-Nernst-Planck (PNP) Formalism
	10.4 Summary and Outlook
	References
11 Data-Driven Multiscale Science for Tire Compounding: Methods and Future Directions
	11.1 Introduction
		11.1.1 Early Laboratory Compound Design Concepts
		11.1.2 Chapter Scope
	11.2 Methods Framework
		11.2.1 Simple Representations of Filled Soft Composites
		11.2.2 Filler Microstructure Statistical Characterization and Stochastic Reconstruction
		11.2.3 Nanocomposite Properties and Statistical Study of the Representative Volume Element
		11.2.4 Summary
	11.3 Future Directions
		11.3.1 Material Informatics and Cheminformatics
		11.3.2 Machine Learning
		11.3.3 Summary
	References
Index