2014/09/24 by Wen-Sheng Xu, Wen‐Sheng Xu, Karl F. Freed · 2 citations
Engineering · Materials Science · Physics and Astronomy · #Bending stiffness #Composite material #Computer science #Configuration entropy #Fragility #Glass transition #Isobaric process #Material Dynamics and Properties #Materials science #Molecule #Phase Equilibria and Thermodynamics #Physics #Polymer #Polymer crystallization and properties #Quantum mechanics #Statistical physics #Stiffness #Thermodynamics #cond-mat.soft #k-nearest neighbors algorithm #van der Waals force
paper · pdf · doi:10.1021/ma501581u
12 pages, 14 figures with Supporting Information, to appear in Macromolecules
arxiv created 2014/09/24 · openalex publication_date 2014/09/30 · arxiv updated 2015/06/23 · openalex created_date 2016/06/24 · openalex updated_date 2026/08/05
The generalized entropy theory is applied to assess the joint influence of the microscopic cohesive energy and chain stiffness on glass formation in polymer melts using a minimal model containing a single bending energy and a single (monomer averaged) nearest neighbor van der Waals energy. The analysis focuses on the combined impact of the microscopic cohesive energy and chain stiffness on the magnitudes of the isobaric fragility parameter m P and the glass transition temperature T g . The computations imply that polymers with rigid structures and weak nearest neighbor interactions are the most fragile, while T g becomes larger when the chains are stiffer and/or nearest neighbor interactions are stronger. Two simple fitting formulas summarize the computations describing the dependence of m P and T g on the microscopic cohesive and bending energies. The consideration of the combined influence of the microscopic cohesive and bending energies leads to the identification of some important design concepts, such as iso-fragility and iso- T g lines, where, for instance, iso-fragility lines are contours with constant m P but variable T g . Several thermodynamic properties are found to remain invariant along the iso-fragility lines, while no special characteristics are detected along the iso- T g lines. Our analysis supports the widely held view that fragility provides more fundamental insight for the description of glass formation than T g .