Polymer Glass Formation: Role of Activation Free Energy, Configurational Entropy, and Collective Motion

Published on Feb 23, 2021in Macromolecules5.918
· DOI :10.1021/ACS.MACROMOL.0C02740
Wen-Sheng Xu13
Estimated H-index: 13
(CAS: Chinese Academy of Sciences),
Jack F. Douglas91
Estimated H-index: 91
(NIST: National Institute of Standards and Technology)
+ 0 AuthorsZhao-Yan Sun19
Estimated H-index: 19
(CAS: Chinese Academy of Sciences)
Source
Abstract
We provide a perspective on polymer glass formation, with an emphasis on models in which the fluid entropy and collective particle motion dominate the theoretical description and data analysis. The...
📖 Papers frequently viewed together
3 Citations
3 Citations
References309
Newest
#1Wen-Sheng Xu (CAS: Chinese Academy of Sciences)H-Index: 13
#2Jack F. Douglas (NIST: National Institute of Standards and Technology)H-Index: 91
Last. Xiaolei Xu (CAS: Chinese Academy of Sciences)H-Index: 7
view all 3 authors...
The influence of the monomer chemical structure and architecture on polymer glass formation has been long appreciated to be dominated by two principal molecular factors, namely, cohesive energy and...
5 CitationsSource
#1Gazi Mahmud (U of A: University of Alberta)H-Index: 1
#2Hao Zhang (U of A: University of Alberta)H-Index: 26
Last. Jack F. Douglas (NIST: National Institute of Standards and Technology)H-Index: 91
view all 3 authors...
Recent studies of structural relaxation in Cu-Zr metallic glass materials having a range of compositions and over a wide range of temperatures and in crystalline UO2 under superionic conditions have indicated that the localization model (LM) can predict the structural relaxation time τα of these materials from the intermediate scattering function without any free parameters from the particle mean square displacement ⟨r2⟩ at a caging time on the order of ps, i.e., the "Debye-Waller factor" (DWF)....
7 CitationsSource
#1Peter Lunkenheimer (University of Augsburg)H-Index: 70
#2Felix Humann (University of Augsburg)H-Index: 1
Last. Konrad Samwer (GAU: University of Göttingen)H-Index: 59
view all 4 authors...
A recently published analytical model describing and predicting elasticity, viscosity, and fragility of metallic melts is applied for the analysis of about 30 nonmetallic glassy systems, ranging from oxide network glasses to alcohols, low-molecular-weight liquids, polymers, plastic crystals, and even ionic glass formers. The model is based on the power-law exponent λ representing the steepness parameter of the repulsive part of the inter-atomic or inter-molecular potential and the thermal-expans...
3 CitationsSource
#1Wen-Sheng Xu (CAS: Chinese Academy of Sciences)H-Index: 13
#2Jack F. Douglas (NIST: National Institute of Standards and Technology)H-Index: 91
Last. Xiaolei Xu (CAS: Chinese Academy of Sciences)H-Index: 7
view all 4 authors...
The generalized entropy theory (GET) of glass formation provides an analytic framework for the structural relaxation time and thermodynamic properties of glass-forming polymers in terms of molecula...
9 CitationsSource
#1Wen-Sheng Xu (CAS: Chinese Academy of Sciences)H-Index: 13
#2Jack F. Douglas (NIST: National Institute of Standards and Technology)H-Index: 91
Last. Xiaolei Xu (CAS: Chinese Academy of Sciences)H-Index: 7
view all 4 authors...
Motivated by empirical observations suggesting that changes in the activation volume ΔV# upon varying temperature (T), determined from the pressure (P) dependence of the segmental structural relaxa...
10 CitationsSource
#1Wen-Sheng Xu (CAS: Chinese Academy of Sciences)H-Index: 13
#2Jack F. Douglas (NIST: National Institute of Standards and Technology)H-Index: 91
Last. Xiaolei Xu (CAS: Chinese Academy of Sciences)H-Index: 7
view all 3 authors...
The key role of chain flexibility in polymer glass formation has long been appreciated, but a fundamental understanding of how chain stiffness influences polymer glass formation remains elusive. In...
7 CitationsSource
#1Wen-Sheng Xu (CAS: Chinese Academy of Sciences)H-Index: 13
#2Wenjie Xia (NDSU: North Dakota State University)H-Index: 20
3 CitationsSource
#1Jinpeng Fan (Wesleyan University)H-Index: 1
#2Hamed Emamy (Columbia University)H-Index: 6
Last. Francis W. Starr (Wesleyan University)H-Index: 54
view all 5 authors...
While glass formation of linear chain polymer melts has widely been explored, comparatively little is known about glass formation in star polymer melts. We study the segmental dynamics of star polymer melts via molecular dynamics simulations and examine the cooperative nature of segmental motion in star melts. In particular, we quantify how the molecular architecture of star polymers, i.e., the number of arms and the length of those arms, affects the glass transition temperature Tg, the non-Gaus...
15 CitationsSource
#1Dong Han (CAS: Chinese Academy of Sciences)H-Index: 14
#2W. DanH-Index: 1
Last. Alessio ZacconeH-Index: 28
view all 8 authors...
A popular Adam--Gibbs scenario has suggested that the excess entropy of glass and liquid over crystal dominates the dynamical arrest at the glass transition with exclusive contribution from configurational entropy over vibrational entropy. However, an intuitive structural rationale for the emergence of frozen dynamics in relation to entropy is still lacking. Here we study these issues by atomistically simulating the vibrational, configurational, as well as total entropy of a model glass former o...
12 CitationsSource
#1Misaki Ozawa (University of Montpellier)H-Index: 16
#2Camille Scalliet (University of Montpellier)H-Index: 10
Last. Ludovic Berthier (University of Montpellier)H-Index: 73
view all 4 authors...
We perform stringent tests of thermodynamic theories of the glass transition over the experimentally relevant temperature regime for several simulated glass-formers. The swap Monte Carlo algorithm is used to estimate the configurational entropy and static point-to-set lengthscale, and careful extrapolations are used for the relaxation times. We first quantify the relation between configurational entropy and the point-to-set lengthscale in two and three dimensions. We then show that the Adam-Gibb...
23 CitationsSource
Cited By5
Newest
#1Qing-Zhi Zou (Donghua University)
#2Yihui Zhu (Donghua University)
Last. Gengxin Liu (Donghua University)H-Index: 8
view all 5 authors...
Abstract null null Melts of 3-dimensional dendritic beads-springs, namely coarse-grained soft-clusters, are studied by molecular dynamics simulations. The goal is to elucidate the unique dynamics of giant molecules, or generally speaking, 3-dimensional architectured polymers. When constituted by more than the critical number around 200 beads, soft-clusters cannot diffuse or relax far above their glass transition temperature, although relaxation can happen on the level of beads. Each soft-cluster...
Source
#1Jintian Luo (Donghua University)
#2Yihui Zhu (Donghua University)
Last. Gengxin Liu (Donghua University)H-Index: 8
view all 0 authors...
Source
#1Xiaolei Xu (CAS: Chinese Academy of Sciences)H-Index: 4
#1Xiaolei Xu (CAS: Chinese Academy of Sciences)H-Index: 7
Last. Wen-Sheng Xu (CAS: Chinese Academy of Sciences)H-Index: 13
view all 3 authors...
Source
#1Andrea GiuntoliH-Index: 4
#2Nitin K. HansogeH-Index: 4
Last. Sinan KetenH-Index: 34
view all 6 authors...
A persistent challenge in predictive molecular modeling of thermoset polymers is to capture the effects of chemical composition and degree of crosslinking (DC) on dynamical and mechanical properties with high computational efficiency. We established a new coarse-graining (CG) approach that combines the energy renormalization method with Gaussian process surrogate models of the molecular dynamics simulations. This allows a machine-learning informed functional calibration of DC-dependent CG force ...
#1Jack F. Douglas (NIST: National Institute of Standards and Technology)H-Index: 91
#2Wen-Sheng Xu (CAS: Chinese Academy of Sciences)H-Index: 13
Numerous experimental and computational studies have established that most liquids seem to exhibit a remarkable, yet poorly understood, property termed “thermodynamic scaling”, in which the structu...
Source