Generalized entropy theory of glass-formation in fully flexible polymer melts.

The generalized entropy theory (GET) offers many insights into how molecular parameters influence polymer glass-formation. Given the fact that chain rigidity often plays a critical role in understanding the glass-formation of polymer materials, the GET was originally developed based on models of semiflexible chains. Consequently, all previous calculations within the GET considered polymers with some degree of chain rigidity. Motivated by unexpected results from computer simulations of fully flexible polymer melts concerning the dependence of thermodynamic and dynamic properties on the cohesive interaction strength (ϵ), the present paper employs the GET to explore the influence of ϵ on glass-formation in models of polymer melts with a vanishing bending rigidity, i.e., fully flexible polymer melts. In accord with simulations, the GET for fully flexible polymer melts predicts that basic dimensionless thermodynamic properties (such as the reduced thermal expansion coefficient and isothermal compressibility) are universal functions of the temperature scaled by ϵ in the regime of low pressures. Similar scaling behavior is also found for the configurational entropy density in the GET for fully flexible polymer melts. Moreover, we find that the characteristic temperatures of glass-formation increase linearly with ϵ and that the fragility is independent of ϵ in fully flexible polymer melts, predictions that are again consistent with simulations of glass-forming polymer melts composed of fully flexible chains. Beyond an explanation of these general trends observed in simulations, the GET for fully flexible polymer melts predicts the presence of a positive residual configurational entropy at low temperatures, indicating a return to Arrhenius relaxation in the low temperature glassy state.

• Publication year

  2016

• Venue

  Journal of Chemical Physics

• Publication date

  2016-12-05

• Fields of study

  Medicine, Materials Science, Physics

• Identifiers
  DOI 10.1063/1.4972412arXiv 1612.01555PMID 28010099
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Localization model description of diffusion and structural relaxation in glass-forming Cu–Zr alloys

  2016cited by this paper
• Entropy Theory of Polymer Glass-Formation in Variable Spatial Dimension.

  2016cited by this paper
• Influence of Cohesive Energy on Relaxation in a Model Glass-Forming Polymer Melt

  2016cited by this paper
• Influence of Cohesive Energy on the Thermodynamic Properties of a Model Glass-Forming Polymer Melt

  2016cited by this paper
• Qualitative change in structural dynamics of some glass-forming systems.

  2015cited by this paper
• Polymer Glass-Formation in Variable Dimension

  2015cited by this paper
• A unifying framework to quantify the effects of substrate interactions, stiffness, and roughness on the dynamics of thin supported polymer films.

  2015cited by this paper
• Quantitative relations between cooperative motion, emergent elasticity, and free volume in model glass-forming polymer materials

  2015cited by this paper
• Generalized Entropy Theory of Glass Formation in Polymer Melts with Specific Interactions

  2015cited by this paper
• Influence of Cohesive Energy and Chain Stiffness on Polymer Glass Formation

  2014cited by this paper
• String model for the dynamics of glass-forming liquids.

  2014cited by this paper
• Lattice cluster theory for polymer melts with specific interactions.

  2014cited by this paper
• Communication: Towards first principles theory of relaxation in supercooled liquids formulated in terms of cooperative motion.

  2014cited by this paper
• Interfacial mobility scale determines the scale of collective motion and relaxation rate in polymer films

  2014cited by this paper
• Advances in the generalized entropy theory of glass-formation in polymer melts.

  2014cited by this paper
• Thermodynamic scaling of dynamics in polymer melts: predictions from the generalized entropy theory.

  2013cited by this paper
• Using 20-million-year-old amber to test the super-Arrhenius behaviour of glass-forming systems

  2013cited by this paper
• The relationship of dynamical heterogeneity to the Adam-Gibbs and random first-order transition theories of glass formation.

  2013cited by this paper
• Development of minimal models of the elastic properties of flexible and stiff polymer networks with permanent and thermoreversible cross-links.

  2010cited by this paper
• Configurational and residual entropies of nonergodic crystals and the entropy's behavior on glass formation.

  2010cited by this paper
• Application of the entropy theory of glass formation to poly(alpha-olefins).

  2009cited by this paper
• Generalized Entropy Theory of Polymer Glass Formation

  2008cited by this paper
• LATTICE CLUSTER THEORY OF MULTICOMPONENT POLYMER SYSTEMS : CHAIN SEMIFLEXIBILITY AND SPECIFIC INTERACTIONS

  2007cited by this paper
• Universality of the dynamic crossover in glass-forming liquids: a "magic" relaxation time.

  2003cited by this paper
• Viscosity of silica

  2002cited by this paper
• Local elastic expansion model for viscous-flow activation energies of glass-forming molecular liquids.

  1996cited by this paper
• Entropy of glassy polymer melts: Comparison between Gibbs-DiMarzio theory and simulation.

  1996cited by this paper
• Effect of monomer structure and compressibility on the properties of multicomponent polymer blends and solutions: 1. Lattice cluster theory of compressible systems

  1991cited by this paper
• Dynamics of entangled linear polymer melts: A molecular‐dynamics simulation

  1990cited by this paper
• Molecular dynamics simulation for polymers in the presence of a heat bath.

  1986cited by this paper
• On the validity of the Flory–Huggins approximation for semiflexible chains

  1981cited by this paper
• Critical Density in Percolation Processes

  1970cited by this paper
• On the Temperature Dependence of Cooperative Relaxation Properties in Glass‐Forming Liquids

  1965cited by this paper
• Nature of the Glass Transition and the Glassy State

  1958cited by this paper
• The Nature of the Glassy State and the Behavior of Liquids at Low Temperatures.

  1948cited by this paper
• Die Abhängigkeit der Viscosität von der Temperatur bie unterkühlten Flüssigkeiten

  1926cited by this paper
• ANALYSIS OF RECENT MEASUREMENTS OF THE VISCOSITY OF GLASSES

  1925cited by this paper
• Das Temperaturabhangigkeitsgesetz der Viskositat von Flussigkeiten

  year unknowncited by this paper
• Development of Minimal Models of the Elastic Properties of Flexible and Stiff Polymer Networks with Permanent and Thermoreversible Cross-links

  year unknowncited by this paper

• Generalized entropy theory investigation of the relatively high segmental fragility of many glass-forming polymers.

  2025cites this paper
• Enhancing acrylamide-based polymer performance in high temperature drilling fluid: Role of isopentenol polyoxyethylene ether

  2025cites this paper
• Physical Origin of the Mass Dependence of Glass Transition Temperature and Fragility of Polymer Liquids

  2025cites this paper
• Machine learning of the architecture-property relationship in graft polymers.

  2025cites this paper
• Polynorbornenes Bearing Cyclic Fluoroalkyl Side Groups for Achieving High Glass Transition Temperature and Low Refractive Index

  2025cites this paper
• Glass Formation in Ring Polymer Melts Having Variable Knot Complexity and Molecular Mass

  2024cites this paper
• Crystal melting influenced by particle cooperativity of the liquid

  2024cites this paper
• Confinement effect of inter-arm interactions on glass formation in star polymer melts.

  2024cites this paper
• A Thermodynamic Perspective on Polymer Glass Formation

  2023cites this paper
• On the formation of metallic glass

  2023cites this paper
• Cracking the Kauzmann Paradox

  2023cites this paper
• Advances in the generalized entropy theory of polymer glass formation

  2023cites this paper
• Temperature Dependence of Structural Relaxation in Glass-Forming Liquids and Polymers

  2022influential citation
• The Kauzmann Transition to an Ideal Glass Phase

  2022cites this paper
• Energy renormalization for coarse-graining of thermomechanical behaviors of conjugated polymer

  2022cites this paper
• Deep glassy state dynamic data challenge glass models: Configurational entropy models

  2021cites this paper
• Dynamic heterogeneity, cooperative motion, and Johari–Goldstein β\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\beta

  2021cites this paper
• Systematic coarse-graining of epoxy resins with machine learning-informed energy renormalization

  2021cites this paper
• Glass transition and dynamics of semiflexible polymer brushes.

  2021cites this paper
• Influence of Side-Chain Length and Relative Rigidities of Backbone and Side Chains on Glass Formation of Branched Polymers

  2021cites this paper
• Thermal properties of polymer-penetrant mixtures

  2021cites this paper
• Deep glassy state dynamic data challenge glass models: Elastic models

  2021cites this paper
• Molecular Dynamics Study of Glass Formation in Polymer Melts with Varying Chain Stiffness

  2020cites this paper
• Energy Renormalization for Coarse‐Graining Polymers with Different Fragilities: Predictions from the Generalized Entropy Theory

  2020cites this paper
• Role of Cohesive Energy in Glass Formation of Polymers with and without Bending Constraints

  2020cites this paper
• Understanding Activation Volume in Glass-Forming Polymer Melts via Generalized Entropy Theory

  2020cites this paper
• Investigation of the Temperature Dependence of Activation Volume in Glass-Forming Polymer Melts under Variable Pressure Conditions

  2020cites this paper
• Glass Transition Phenomenon for Conjugated Polymers

  2019cites this paper
• Perspective: Configurational entropy of glass-forming liquids

  2019cites this paper
• Multiscale Modeling of Sub-Entanglement-Scale Chain Stretching and Strain Hardening in Deformed Polymeric Glasses

  2019cites this paper
• Configurational entropy of glass-forming liquids.

  2019cites this paper
• Energy renormalization for coarse-graining polymers having different segmental structures

  2019cites this paper
• Zero-temperature glass transition in two dimensions

  2018cites this paper
• Impact of higher order diagrams on phase equilibrium calculations for small molecules using lattice cluster theory

  2018cites this paper
• Tuning the Relaxation of Nanopatterned Polymer Films with Polymer-Grafted Nanoparticles: Observation of Entropy-Enthalpy Compensation.

  2018cites this paper
• String-like collective motion and diffusion in the interfacial region of ice.

  2017cites this paper
• Energy-Renormalization for Achieving Temperature Transferable Coarse-Graining of Polymer Dynamics.

  2017cites this paper
• Influence of Pressure on Glass Formation in a Simulated Polymer Melt

  2017cites this paper