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Polymers
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Phase Transitions and Structures in Polymer Science
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Phase Transitions and Structures in Polymer Science

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Physics and Theory".

Deadline for manuscript submissions: closed (28 February 2023) | Viewed by 14198

Special Issue Editor

Dr. Hayoung Chung

E-Mail Website
Guest Editor
Department of Mechanical Engineering, School of Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Korea
Interests: computational mechanics; constitutive modeling; multiscale analysis; nonlinear elasticity; active materials (liquid crystal polymer); nanomechanics; topology optimization

Special Issue Information

Dear Colleagues,

Phase transition and accompanying structural change are essential topics in polymer science in both theory and application. However, the innate complexity of the material, reflected by diverse small-scale morphologies that often coexist, prevents the behavior from being fully understood. Meanwhile, recent decades have also witnessed a surge in innovative techniques that harness and manipulate such morphological changes, which opens a new research avenue to control the properties of the material. In this respect, a deeper understanding of the structure–property relationship, and further predicting it, are vital in polymer science and engineering. This Special Issue aims to disseminate theoretical and experimental work concerning phase transitions and structures in polymer science to provide relevant knowledge for readers and researchers rapidly. Theoretical and/or experimental investigations concerning all aspects of the phenomena are cordially welcomed. The list of potential research topics includes but is not limited to:

  • Analysis/modeling technique of polymer morphology, including multiscale analysis of polymeric behaviors;
  • The relationship between polymer morphology to material properties (structure–property relationship);
  • Diverse phase behaviors induced by polymer conformation change;
  • Phase transitions of non-classical polymers, e.g., polymer nanocomposites and liquid crystal polymers, just to name a few;
  • Control of macromolecular behavior of polymer, e.g., self-assembling copolymer;

Novel mechanical/electrical/chemical devices employing phase transition as their driving force.

Dr. Hayoung Chung
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • phase transition
  • phase diagram
  • polymer crystallization
  • polymer melting
  • polymer modification
  • liquid crystal polymer
  • copolymers
  • structure–property relationship
  • polymer morphology

Published Papers (7 papers)

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Research

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17 pages, 4929 KiB  
Article
Influence of Process Parameters on the Kinetics of the Micelle-to-Vesicle Transition and Ripening of Polystyrene-Block-Polyacrylic Acid
by Jil Mann, Julian K. Mayer, Georg Garnweitner and Carsten Schilde
Polymers 2023, 15(7), 1695; https://doi.org/10.3390/polym15071695 - 29 Mar 2023
Viewed by 1269
Abstract
Due to their ability to self-assemble into complex structures, block copolymers are of great interest for use in a wide range of future applications, such as self-healing materials. Therefore, it is important to understand the mechanisms of their structure formation. In particular, the [...] Read more.
Due to their ability to self-assemble into complex structures, block copolymers are of great interest for use in a wide range of future applications, such as self-healing materials. Therefore, it is important to understand the mechanisms of their structure formation. In particular, the process engineering of the formation and transition of the polymer structures is required for ensuring reproducibility and scalability, but this has received little attention in the literature. In this article, the influence of the addition rate of the selective solvent on the homogeneity of self-assembled vesicles of polystyrene-block-polyacrylic acid is demonstrated, as well as the influence of the reaction time and the mixing intensity on the morphology of the polymer structures. For example, it was demonstrated that the higher the mixing intensity, the faster the transition from micelle to vesicle. The experimental results are further supported by CFD simulations, which visually and graphically show an increase in shear rate and narrower shear rate distributions at higher stirring rates. Furthermore, it was demonstrated that the vesicle size is not only kinetically determined, since flow forces above a critical size lead to the deformation and fission of the vesicles. Full article
(This article belongs to the Special Issue Phase Transitions and Structures in Polymer Science)
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13 pages, 4243 KiB  
Article
Partial Miscibility and Concentration Distribution of Two-Phase Blends of Crosslinked NBR and PVC
by Yuka Komori, Aoi Taniguchi, Haruhisa Shibata, Shinya Goto and Hiromu Saito
Polymers 2023, 15(6), 1383; https://doi.org/10.3390/polym15061383 - 10 Mar 2023
Cited by 1 | Viewed by 1410
Abstract
We found that the blends of nitrile butadiene rubber (NBR) and polyvinyl chloride (PVC) exhibited lower critical solution temperature (LCST)-type phase behavior in which a single-phase blend tends to phase separate at elevated temperatures when the acrylonitrile content of NBR was 29.0%. The [...] Read more.
We found that the blends of nitrile butadiene rubber (NBR) and polyvinyl chloride (PVC) exhibited lower critical solution temperature (LCST)-type phase behavior in which a single-phase blend tends to phase separate at elevated temperatures when the acrylonitrile content of NBR was 29.0%. The tan δ peaks, which originated from the glass transitions of the component polymers measured by dynamic mechanical analysis (DMA), were largely shifted and broader in the blends when the blends were melted in the two-phase region of the LCST-type phase diagram, suggesting that NBR and PVC are partially miscible in the two-phase structure. The TEM-EDS elemental mapping analysis using a dual silicon drift detector revealed that each component polymer existed in the partner polymer-rich phase, and the PVC-rich domains consisted of aggregated small PVC particles the size of several ten nanometers. The partial miscibility of the blends was explained by the lever rule for the concentration distribution in the two-phase region of the LCST-type phase diagram. Full article
(This article belongs to the Special Issue Phase Transitions and Structures in Polymer Science)
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20 pages, 7702 KiB  
Article
Polymorph Stability and Free Energy of Crystallization of Freely-Jointed Polymers of Hard Spheres
by Miguel Herranz, Javier Benito, Katerina Foteinopoulou, Nikos Ch. Karayiannis and Manuel Laso
Polymers 2023, 15(6), 1335; https://doi.org/10.3390/polym15061335 - 07 Mar 2023
Cited by 3 | Viewed by 5072
Abstract
The free energy of crystallization of monomeric hard spheres as well as their thermodynamically stable polymorph have been known for several decades. In this work, we present semianalytical calculations of the free energy of crystallization of freely-jointed polymers of hard spheres as well [...] Read more.
The free energy of crystallization of monomeric hard spheres as well as their thermodynamically stable polymorph have been known for several decades. In this work, we present semianalytical calculations of the free energy of crystallization of freely-jointed polymers of hard spheres as well as of the free energy difference between the hexagonal closed packed (HCP) and face-centered cubic (FCC) polymorphs. The phase transition (crystallization) is driven by an increase in translational entropy that is larger than the loss of conformational entropy of chains in the crystal with respect to chains in the initial amorphous phase. The conformational entropic advantage of the HCP polymer crystal over the FCC one is found to be ΔschHCP−FCC≈0.331×10−5k per monomer (expressed in terms of Boltzmann’s constant k). This slight conformational entropic advantage of the HCP crystal of chains is by far insufficient to compensate for the larger translational entropic advantage of the FCC crystal, which is predicted to be the stable one. The calculated overall thermodynamic advantage of the FCC over the HCP polymorph is supported by a recent Monte Carlo (MC) simulation on a very large system of 54 chains of 1000 hard sphere monomers. Semianalytical calculations using results from this MC simulation yield in addition a value of the total crystallization entropy for linear, fully flexible, athermal polymers of Δs≈0.93k per monomer. Full article
(This article belongs to the Special Issue Phase Transitions and Structures in Polymer Science)
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12 pages, 5054 KiB  
Article
Temperature-Dependent Polymorphism and Phase Transformation of Friction Transferred PLLA Thin Films
by Jinghua Wu, Xing Chen, Jian Hu, Shouke Yan and Jianming Zhang
Polymers 2022, 14(23), 5300; https://doi.org/10.3390/polym14235300 - 04 Dec 2022
Cited by 1 | Viewed by 1292
Abstract
Poly(L-lactic acid) (PLLA) thin films with a highly oriented structure, successfully prepared by a fast friction transfer technique, were investigated mainly on the basis of synchrotron radiation wide-angle X-ray diffraction (WAXD) and Fourier transform infrared spectroscopy (FTIR). The crystalline structure of the highly [...] Read more.
Poly(L-lactic acid) (PLLA) thin films with a highly oriented structure, successfully prepared by a fast friction transfer technique, were investigated mainly on the basis of synchrotron radiation wide-angle X-ray diffraction (WAXD) and Fourier transform infrared spectroscopy (FTIR). The crystalline structure of the highly oriented PLLA film was remarkably affected by friction transfer temperatures, which exhibited various crystal forms in different friction temperature regions. Interestingly, metastable β-form was generated at all friction transfer temperatures (70–140 °C) between Tg and Tm, indicating that fast friction transfer rate was propitious to the formation of β-form. Furthermore, the relative content among β-, α′-, and α-forms at different friction temperatures was estimated by WAXD as well as FTIR spectroscopy. In situ temperature-dependent WAXD was applied to reveal the complicated phase transition behavior of PLLA at a friction transfer temperature of 100 °C. The results illustrated that the contents of β- and α′-forms decreased in turn, whereas the α-form increased in content due to partially melt-recrystallization or crystal perfection. Moreover, by immersing into a solvent of acetone, β-, α′-form were transformed into stable α-crystalline form directly as a consequence. The highly oriented structure was maintained with the chain perfectly parallel to friction transfer direction after acetone treatment, evidenced by polarized FTIR and polarized optical microscopy (POM) measurements. Full article
(This article belongs to the Special Issue Phase Transitions and Structures in Polymer Science)
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13 pages, 563 KiB  
Article
Exact Enumeration Approach to Estimate the Theta Temperature of Interacting Self-Avoiding Walks on the Simple Cubic Lattice
by Sing-Shuo Huang, Yu-Hsin Hsieh and Chi-Ning Chen
Polymers 2022, 14(21), 4536; https://doi.org/10.3390/polym14214536 - 26 Oct 2022
Cited by 2 | Viewed by 1028
Abstract
We compute the exact root-mean-square end-to-end distance of the interacting self-avoiding walk (ISAW) up to 27 steps on the simple cubic lattice. These data are used to construct a fixed point equation to estimate the theta temperature of the collapse transition of the [...] Read more.
We compute the exact root-mean-square end-to-end distance of the interacting self-avoiding walk (ISAW) up to 27 steps on the simple cubic lattice. These data are used to construct a fixed point equation to estimate the theta temperature of the collapse transition of the ISAW. With the Bulirsch–Stoer extrapolation method, we obtain accurate results that can be compared with large-scale long-chain simulations. The free parameter ω in extrapolation is precisely determined using a parity property of the ISAW. The systematic improvement of this approach is feasible by adopting the combination of exact enumeration and multicanonical simulations. Full article
(This article belongs to the Special Issue Phase Transitions and Structures in Polymer Science)
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Review

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26 pages, 5569 KiB  
Review
Recent Trends in Continuum Modeling of Liquid Crystal Networks: A Mini-Review
by Sanghyeon Park, Youngtaek Oh, Jeseung Moon and Hayoung Chung
Polymers 2023, 15(8), 1904; https://doi.org/10.3390/polym15081904 - 15 Apr 2023
Cited by 5 | Viewed by 1472
Abstract
This work aims to provide a comprehensive review of the continuum models of the phase behaviors of liquid crystal networks (LCNs), novel materials with various engineering applications thanks to their unique composition of polymer and liquid crystal. Two distinct behaviors are primarily considered: [...] Read more.
This work aims to provide a comprehensive review of the continuum models of the phase behaviors of liquid crystal networks (LCNs), novel materials with various engineering applications thanks to their unique composition of polymer and liquid crystal. Two distinct behaviors are primarily considered: soft elasticity and spontaneous deformation found in the material. First, we revisit these characteristic phase behaviors, followed by an introduction of various constitutive models with diverse techniques and fidelities in describing the phase behaviors. We also present finite element models that predict these behaviors, emphasizing the importance of such models in predicting the material’s behavior. By disseminating various models essential to understanding the underlying physics of the behavior, we hope to help researchers and engineers harness the material’s full potential. Finally, we discuss future research directions necessary to advance our understanding of LCNs further and enable more sophisticated and precise control of their properties. Overall, this review provides a comprehensive understanding of the state-of-the-art techniques and models used to analyze the behavior of LCNs and their potential for various engineering applications. Full article
(This article belongs to the Special Issue Phase Transitions and Structures in Polymer Science)
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25 pages, 3317 KiB  
Review
Sulfonated Block Copolymers: Synthesis, Chemical Modification, Self-Assembly Morphologies, and Recent Applications
by Claudia I. Piñón-Balderrama, César Leyva-Porras, Alain Salvador Conejo-Dávila and Erasto Armando Zaragoza-Contreras
Polymers 2022, 14(23), 5081; https://doi.org/10.3390/polym14235081 - 23 Nov 2022
Cited by 1 | Viewed by 1932
Abstract
Scientific research based on the self-assembly behavior of block copolymers (BCs) comprising charged-neutral segments has emerged as a novel strategy mainly looking for the optimization of efficiency in the generation and storage of electrical energy. The sulfonation reaction re- presents one of the [...] Read more.
Scientific research based on the self-assembly behavior of block copolymers (BCs) comprising charged-neutral segments has emerged as a novel strategy mainly looking for the optimization of efficiency in the generation and storage of electrical energy. The sulfonation reaction re- presents one of the most commonly employed methodologies by scientific investigations to reach the desired amphiphilic character, leading to enough ion concentration to modify and control the entire self-assembly behavior of the BCs. Recently, several works have studied and exploited these changes, inducing improvement on the mechanical properties, ionic conduction capabilities, colloidal solubility, interface activity, and stabilization of dispersed particles, among others. This review aims to present a description of recent works focused on obtaining amphiphilic block copolymers, specifically those that were synthesized by a living/controlled polymerization method and that have introduced the amphiphilic character by the sulfonation of one of the segments. Additionally, relevant works that have evidenced morphological and/or structural changes regarding the pristine BC as a result of the chemical modification are discussed. Finally, several emerging practical applications are analyzed to highlight the main drawbacks and challenges that should be addressed to overcome the development and understanding of these complex systems. Full article
(This article belongs to the Special Issue Phase Transitions and Structures in Polymer Science)
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