Istituto dei Sistemi Complessi, Consiglio Nazionale delle Ricerche, 00185 Rome, Italy.
Department of Chemical, Materials and Production Engineering, University of Naples Federico II, Piazzale Tecchio 80, 80125 Naples, Italy.
Int J Mol Sci. 2022 May 10;23(10):5316. doi: 10.3390/ijms23105316.
In the recent years a considerable effort has been devoted to foster the understanding of the basic mechanisms underlying the dynamical arrest that is involved in glass forming in supercooled liquids and in the sol-gel transition. The elucidation of the nature of such processes represents one of the most challenging unsolved problems in the field of material science. In this context, two important theories have contributed significantly to the interpretation of these phenomena: the Mode-Coupling theory (MCT) and the Percolation theory (PT). These theories are rooted on the two pillars of statistical physics, universality and scale laws, and their original formulations have been subsequently modified to account for the fundamental concepts of Energy Landscape (EL) and of the universality of the fragile to strong dynamical crossover (FSC). In this review, we discuss experimental and theoretical results, including Molecular Dynamics (MD) simulations, reported in the literature for colloidal and polymer systems displaying both glass and sol-gel transitions. Special focus is dedicated to the analysis of the interferences between these transitions and on the possible interplay between MCT and PT. By reviewing recent theoretical developments, we show that such interplay between sol-gel and glass transitions may be interpreted in terms of the extended F13 MCT model that describes these processes based on the presence of a glass-glass transition line terminating in an A3 cusp-like singularity (near which the logarithmic decay of the density correlator is observed). This transition line originates from the presence of two different amorphous structures, one generated by the inter-particle attraction and the other by the pure repulsion characteristic of hard spheres. We show here, combining literature results with some new results, that such a situation can be generated, and therefore experimentally studied, by considering colloidal-like particles interacting via a hard core plus an attractive square well potential. In the final part of this review, scaling laws associated both to MCT and PT are applied to describe, by means of these two theories, the specific viscoelastic properties of some systems.
近年来,人们投入了相当大的努力来理解玻璃形成动力学的基本机制,这些机制涉及过冷液体和溶胶-凝胶转变中的动力学停滞。阐明这些过程的本质是材料科学领域最具挑战性的未解决问题之一。在这种情况下,两种重要的理论对这些现象的解释做出了重要贡献:模式耦合理论(MCT)和渗流理论(PT)。这些理论植根于统计物理学的两个支柱:普遍性和标度律,它们的原始形式随后进行了修改,以解释能量景观(EL)的基本概念和脆弱到强动力学交叉(FSC)的普遍性。在这篇综述中,我们讨论了文献中报道的胶体和聚合物系统中同时存在玻璃和溶胶-凝胶转变的实验和理论结果。特别关注这些转变之间的干扰以及 MCT 和 PT 之间可能的相互作用。通过回顾最近的理论发展,我们表明,这种溶胶-凝胶和玻璃转变之间的相互作用可以用扩展的 F13 MCT 模型来解释,该模型基于存在玻璃-玻璃转变线来描述这些过程,该线终止于 A3 样的尖角奇点(在该奇点附近观察到密度相关函数的对数衰减)。该转变线源于两种不同的非晶态结构,一种是由粒子间的吸引力产生的,另一种是由硬球特有的纯排斥力产生的。我们在这里结合文献结果和一些新结果表明,可以通过考虑通过硬芯加吸引力方阱势相互作用的类胶体粒子来产生这种情况,并因此进行实验研究。在本综述的最后一部分,应用 MCT 和 PT 相关的标度律,用这两种理论描述了一些系统的特定粘弹性特性。