Glassy feature in melts of 3-dimensional architectured polymer blends

Zhu, Yunmin; Luo, Jintian; Zou, Qianli; Ouyang, Xikai; Ruan, Yifu; Liu, Yuchu; Liu, Gengxin

doi:10.1016/j.polymer.2021.124336

Cited by 11 publications

(16 citation statements)

References 59 publications

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“…Understanding glass transition in polymer-related materials is a yet unsolved issue in polymer physics due to their diverse architectures and topological constraints, which are ubiquitous in living organisms and industrial synthesis. − Molecular internal structures and their topological constraints have been found to give rise to many unique structural, dynamic and rheological properties in linear chains, − rings, − and nanocomposites. − Furthermore, much effort has been devoted to the study of glass-forming polymers driven by different topological interactions, including transient interpenetration in rings, intrachain knot complexities, , and chemical linking in giant molecular clusters. , …”

Section: Introductionmentioning

confidence: 99%

Glass Formation in Mechanically Interlocked Ring Polymers: The Role of Induced Chain Stiffness

Zhang

2023

Macromolecules

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Polymer-related materials exhibit rich glassy behaviors at different length scales due to their various molecular structures and topological constraints. Recent studies have identified transient interpenetration of the long-chain rings contributing to dynamic arrest on the center-of-mass level. Interpenetration of rings is proposed as an approach to facilitate glass formation in polymer melts. In this work, inspired by recent advances in the synthesis of mechanically interlocked polymers, we investigate glass transition on the nanometer-scale segments influenced by permanent interpenetration of rings using molecular dynamics simulations. We find that decreasing chain length in the mechanically interlocked system is equivalent to inducing an effective chain stiffness on the subrings. The induced stiffness provides a unified explanation for these unique structural features and transient dynamic arrest in the system of interlocked rings with rather short chains. Further, a crossover is observed in the scaling relation between localization and glassy depth upon cooling. Our work reveals a dynamic transition from weak to strong caging at the crossover temperature. According to the localization model, we demonstrate that the chain stiffness increases the critical temperature and oscillation distance, which therefore leads to more fragile dynamics and a deeper glassy state. These findings are consistent with the predictions of molecular simulations and theories for polymers with real local stiffness. Our work deepens the understanding of the role of induced stiffness on glass transition, and it opens up a new direction to design rich glass materials by manipulating stiffness through mechanical bonds.

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Section: Introductionmentioning

confidence: 99%

Glass Formation in Mechanically Interlocked Ring Polymers: The Role of Induced Chain Stiffness

Zhang

2023

Macromolecules

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“…The emergence of unconventional phases in single-component molecular systems is a recent event that links molecular symmetry/design with molecular interactions/close-packing. , To date, such phases include 2D tilings, , 3D networks, − and spherical-packing such as Frank–Kasper A15 phase and sigma phase, − Z phase, Laves C14 and C15 phases, − etc. Recently, a deliberate pairing of giant molecules has led to peculiar self-sorting behavior which opens an avenue for constructing complex soft lattices, such as binary crystal phases − and decagonal quasicrystals, with intriguing dynamic properties . Despite these successes, molecular isomerism has not yet been well exploited in generating unconventional phases.…”

Section: Introductionmentioning

confidence: 99%

“…31,32 To date, such phases include 2D tilings, 33,34 3D networks, 35−41 and spherical-packing such as Frank−Kasper A15 phase and sigma phase, 42−55 Z phase, 56 Laves C14 and C15 phases, 57−63 molecules has led to peculiar self-sorting behavior which opens an avenue for constructing complex soft lattices, such as binary crystal phases 64−67 and decagonal quasicrystals, 68 with intriguing dynamic properties. 69 Despite these successes, molecular isomerism has not yet been well exploited in generating unconventional phases. Herein, we report the synthesis, assembly, and phase behaviors of a full set of regioisomeric Janus nanograins based on POSS with distinct core symmetry, namely, B 2 DB 2 where B stands for iso-butyl-functionalized polyhedral oligomeric silsesquioxanes (POSS) and D stands for dihydroxyl-functionalized POSS.…”

Section: ■ Introductionmentioning

confidence: 99%

Leveraging Macromolecular Isomerism for Phase Complexity in Janus Nanograins

et al. 2023

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It remains intriguing whether macromolecular isomerism, along with competing molecular interactions, could be leveraged to create unconventional phase structures and generate considerable phase complexity in soft matter. Herein, we report the synthesis, assembly, and phase behaviors of a series of precisely defined regioisomeric Janus nanograins with distinct core symmetry. They are named B2DB2 where B stands for iso-butyl-functionalized polyhedral oligomeric silsesquioxanes (POSS) and D stands for dihydroxyl-functionalized POSS. While BPOSS prefers crystallization with a flat interface, DPOSS prefers to phase-separate from BPOSS. In solution, they form 2D crystals owing to strong BPOSS crystallization. In bulk, the subtle competition between crystallization and phase separation is strongly influenced by the core symmetry, leading to distinct phase structures and transition behaviors. The phase complexity was understood based on their symmetry, molecular packing, and free energy profiles. The results demonstrate that regioisomerism could indeed generate profound phase complexity.

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“…The governing factor seems to be their sizes (diameters)—once above a critical diameter, the giant molecule can no longer diffuse, and its relaxation time increases by a factor of at least 10 8 times, resulting in an elastic plateau. [ 19–22 ]…”

Section: Introductionmentioning

confidence: 99%

“…The governing factor seems to be their sizes (diameters)-once above a critical diameter, the giant molecule can no longer diffuse, and its relaxation time increases by a factor of at least 10 8 times, resulting in an elastic plateau. [19][20][21][22] Figure 1. Giant molecules synthesized from various molecular nanoparticles (Reproduced with permission.…”

Section: Introductionmentioning

confidence: 99%

Recent Progress on the Rheology of Giant Molecules

Liu

Yan

Guo

et al. 2022

Macro Chemistry & Physics

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Giant molecules are a new class of precise macromolecules whose constructing blocks are molecular nanoparticles, such as polyhedral oligomeric silsesquioxane (POSS), fullerene (C 60 ), etc., connected by different types of links with various molecular topologies in soft matter. These blocks are connected in 3D instead of chain-like. Thus, the dynamics of giant molecules cannot be described by the entanglement-dominated "reptation" dynamics, nor by the volume-fraction-determined caging effect as in the colloidal domain. Instead, they demonstrate different kinetics which are highly dependent on their sizes (diameters), bridging the conventional polymeric and colloidal systems. Further investigations into its unique dynamics will not only offer new properties for developing novel materials, but will also provide a deeper insight into the general principles of glass formation. In this review, the definition of giant molecules, their assemblies as well as their structural features are first introduced. The general dynamics of other systems, including the conventional polymeric and colloidal systems are briefly summarized. The recent progress of the rheological study of giant molecules is then focused upon. Finally, perspectives on this direction are proposed.

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Glassy feature in melts of 3-dimensional architectured polymer blends

Cited by 11 publications

References 59 publications

Glass Formation in Mechanically Interlocked Ring Polymers: The Role of Induced Chain Stiffness

Glass Formation in Mechanically Interlocked Ring Polymers: The Role of Induced Chain Stiffness

Leveraging Macromolecular Isomerism for Phase Complexity in Janus Nanograins

Recent Progress on the Rheology of Giant Molecules

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