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Phase Transitions in Polymers and Polymer Morphologies

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

Deadline for manuscript submissions: closed (30 April 2021) | Viewed by 30182

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Prof. Dr. Yaroslav Kudryavtsev

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Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
Interests: polymer modification; macromolecular reactions; copolymers; microphase separation; self-assembly; phase diagrams; polymer-based nanocomposites
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Dear Colleagues,

The variety of morphologies observed in polymers reflects the complexity of phase transitions in these systems, where the ordering of structural units is constrained by their connectivity in long chains. For decades, the thermodynamic and kinetic peculiarities of crystallization, self-assembling, and phase separation have attracted researchers seeking to understand why and how these processes take place in polymer solutions, melts, and blends. In this Special Issue, we most welcome papers that try to reveal new polymer phases and microstructures and to search for the conditions for their formation and stability, thus enriching tools and strategies for the design of polymer materials. Of particular interest are the following topics:
- Selective modification of macromolecules to enhance their ordering ability;
- Self-assembling in multiblock, gradient, and statistical copolymers;
- Interplay between microphase separation and liquid-crystalline ordering;
- Effect of nanoparticles on phase transitions in polymer matrices;
- Polymer self-assembly in thermal, electric, magnetic, and other external fields.

Prof. Yaroslav Kudryavtsev
Guest Editor

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Keywords

self-assembly in polymers
polymer microstructures
phase diagrams
phase transition kinetics
polymer crystallization/melting
liquid crystallinity
liquid–liquid phase separation
polymer modification
copolymers

Published Papers (11 papers)

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Research

17 pages, 4436 KiB

Open AccessArticle

Multiblock Copolymers of Norbornene and Cyclododecene: Chain Structure and Properties

by Yulia I. Denisova, Georgiy A. Shandryuk, Marianna P. Arinina, Ivan S. Levin, Vsevolod A. Zhigarev, Maria L. Gringolts, Eugene Sh. Finkelshtein, Alexander Ya. Malkin and Yaroslav V. Kudryavtsev

Polymers 2021, 13(11), 1756; https://0-doi-org.brum.beds.ac.uk/10.3390/polym13111756 - 27 May 2021

Cited by 6 | Viewed by 2899

Abstract

We investigate the structure–property relations of the multiblock copolymers of norbornene with cyclododecene synthesized via the macromolecular cross-metathesis reaction between amorphous polynorbornene and semicrystalline polydodecenamer in the presence of the first-generation Grubbs catalyst. By adjusting the reaction time, catalyst amount, and composition of the initial system, we obtain a set of statistical multiblock copolymers that differ in the composition and average length of norbornene and dodecenylene unit sequences. Structural, thermal, and mechanical characterization of the copolymers with NMR, XRD, DSC (including thermal fractionation by successive self-nucleation and annealing), and rotational rheology allows us to relate the reaction conditions to the average length of crystallizable unit sequences, thicknesses of corresponding lamellas, and temperatures of their melting. We demonstrate that isolated dodecenylene units can be incorporated into crystalline lamellas so that even nearly random copolymers should retain crystallinity. Weak high-temperature endotherms observed in the multiblock copolymers of norbornene with cyclododecene and other cycloolefins could indicate that the corresponding systems are microphase-separated in the melt state. Full article

(This article belongs to the Special Issue Phase Transitions in Polymers and Polymer Morphologies)

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16 pages, 2738 KiB

Open AccessArticle

Phase Equilibria and Interdiffusion in Bimodal High-Density Polyethylene (HDPE) and Linear Low-Density Polyethylene (LLDPE) Based Compositions

by Ildar I. Salakhov, Anatoly E. Chalykh, Nadim M. Shaidullin, Alexey V. Shapagin, Nikita Yu. Budylin, Ramil R. Khasbiullin, Ilya E. Nifant’ev and Vladimir K. Gerasimov

Polymers 2021, 13(5), 811; https://0-doi-org.brum.beds.ac.uk/10.3390/polym13050811 - 06 Mar 2021

Cited by 7 | Viewed by 3025

Abstract

The compositions based on bimodal high-density polyethylene (HDPE, copolymer of ethylene with hexene-1) and in mixture with monomodal tercopolymer of ethylene with butene-1/hexene-1 (LLDPE, low-density polyethylene) have been studied. Phase equilibrium, thermodynamic parameters of interdiffusion in a wide range of temperatures and ratios of co-components were identified by refractometry, differential scanning calorimetry, optical laser interferometry, X-ray phase analysis. The phase state diagrams of the HDPE—LLDPE systems were constructed. It has been established that they belong to the class of state diagrams of “solid crystal solutions with unrestricted mixing of components”. The paired parameters of the components interaction and their temperature dependences were calculated. Thermodynamic compatibility of α-olefins in the region of melts and crystallization of one of the components has been shown. The kinetics of formation of interphase boundaries during crystallization of α-olefins has been analyzed. The morphology of crystallized gradient diffusion zones has been analyzed by optical polarization microscopy. The sizes of spherulites in different areas of concentration profiles and values of interdiffusion coefficients were determined. Full article

(This article belongs to the Special Issue Phase Transitions in Polymers and Polymer Morphologies)

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19 pages, 2979 KiB

Open AccessArticle

Long-Range Surface-Directed Polymerization-Induced Phase Separation: A Computational Study

by Shima Ghaffari, Philip K. Chan and Mehrab Mehrvar

Polymers 2021, 13(2), 256; https://0-doi-org.brum.beds.ac.uk/10.3390/polym13020256 - 14 Jan 2021

Cited by 3 | Viewed by 1752

Abstract

The presence of a surface preferably attracting one component of a polymer mixture by the long-range van der Waals surface potential while the mixture undergoes phase separation by spinodal decomposition is called long-range surface-directed spinodal decomposition (SDSD). The morphology achieved under SDSD is an enrichment layer(s) close to the wall surface and a droplet-type structure in the bulk. In the current study of the long-range surface-directed polymerization-induced phase separation, the surface-directed spinodal decomposition of a monomer–solvent mixture undergoing self-condensation polymerization was theoretically simulated. The nonlinear Cahn–Hilliard and Flory–Huggins free energy theories were applied to investigate the phase separation phenomenon. The long-range surface potential led to the formation of a wetting layer on the surface. The thickness of the wetting layer was found proportional to time t*^1/5 and surface potential parameter h₁^1/5. A larger diffusion coefficient led to the formation of smaller droplets in the bulk and a thinner depletion layer, while it did not affect the thickness of the enrichment layer close to the wall. A temperature gradient imposed in the same direction of long-range surface potential led to the formation of a stripe morphology near the wall, while imposing it in the opposite direction of surface potential led to the formation of large particles at the high-temperature side, the opposite side of the interacting wall. Full article

(This article belongs to the Special Issue Phase Transitions in Polymers and Polymer Morphologies)

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14 pages, 8457 KiB

Open AccessArticle

UCST Type Phase Boundary and Accelerated Crystallization in PTT/PET Blends

by Kousuke Sugeno, Satoshi Kokubun and Hiromu Saito

Polymers 2020, 12(11), 2730; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12112730 - 17 Nov 2020

Cited by 7 | Viewed by 2446

Abstract

We investigated the structure development and crystallization kinetics in the blends of poly(trimethylene terephthalate) (PTT) and poly(ethylene terephthalate) (PET) by polarized optical microscopy and light scattering. The crystallization of the blend was found to be faster and the size of the spherulites was much smaller than those of the neat component polymers by melt crystallization at low temperature of 180 °C. The discontinuous gap of the crystallization time with temperature was seen in the blends, suggesting phase transition at the temperature T_tr; e.g., the T_tr of the 60/40 PTT/PET was 215 °C. The crystallization was accelerated due to enhancement of the nucleation rate, and interconnected tiny spherulites were obtained at the temperature below the T_tr. The accelerated crystallization and the development of the interconnected structure might be attributed to the liquid-liquid phase separation via spinodal decomposition, due to existence of the upper critical solution temperature (UCST) type phase boundary. Full article

(This article belongs to the Special Issue Phase Transitions in Polymers and Polymer Morphologies)

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9 pages, 2006 KiB

Open AccessEditor’s ChoiceCommunication

Polymerization-Induced Microphase Separation with Long-Range Order in Melts of Gradient Copolymers

by Alexey A. Gavrilov and Alexander V. Chertovich

Polymers 2020, 12(11), 2637; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12112637 - 10 Nov 2020

Cited by 5 | Viewed by 2486

Abstract

In this work, we studied the question of whether it is possible to develop a one-step approach for the creation of microphase-separated materials with long-range order with the help of spontaneous gradient copolymers, i.e., formed during controlled copolymerization solely due to the large difference in the reactivity ratios. To that end, we studied the polymerization-induced microphase separation in bulk on the example of a monomer pair with realistic parameters based on styrene (S) and vinylpirrolydone (VP) by means of computer simulation. We showed that for experimentally reasonable chain lengths, the structures with long-range order start to appear at the conversion degree as low as 76%; a full phase diagram in coordinates (fraction of VP—conversion degree) was constructed. Rather rich phase behavior was obtained; moreover, at some VP fractions, order–order transitions were observed. Finally, we studied how the conversion degree at which the order–disorder transition occurs changes upon varying the maximum average chain length in the system. Full article

(This article belongs to the Special Issue Phase Transitions in Polymers and Polymer Morphologies)

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11 pages, 1807 KiB

Open AccessArticle

Phase Diagram for Ideal Diblock-Copolymer Micelles Compared to Polymerization-Induced Self Assembly

by Alexey A. Gavrilov, Ruslan M. Shupanov and Alexander V. Chertovich

Polymers 2020, 12(11), 2599; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12112599 - 05 Nov 2020

Cited by 7 | Viewed by 2748

Abstract

In this work we constructed a detailed phase diagram for the solutions of ideal diblock-copolymers and compared such diagram with that obtained during polymerization-induced self-assembly (PISA); a wide range of polymer concentrations as well as chain compositions was studied. As the length of the solvophobic block n_B increases (the length of the solvophilic block n_A was fixed), the transition from spherical micelles to cylinders and further to vesicles (lamellae) occurs. We observed a rather wide transition region between the spherical and cylindrical morphology in which the system contains a mixture of spheres and short cylinders, which appear to be in dynamic equilibrium; the transition between the cylinders and vesicles was found to be rather sharp. Next, upon increasing the polymer concentration in the system, the transition region between the spheres and cylinders shifts towards lower n_B/n_A values; a similar shift but with less magnitude was observed for the transition between the cylinders and vesicles. Such behavior was attributed to the increased number of contacts between the micelles at higher polymer volume concentrations. We also found that the width of the stability region of the cylindrical micelles for small polymer volume concentrations is in good quantitative agreement with the predictions of analytical theory. The obtained phase diagram for PISA was similar to the case of presynthesized diblock copolymer; however, the positions of the transition lines for PISA are slightly shifted towards higher n_B/n_A values in comparison to the presynthesized diblock copolymers, which is more pronounced for the case of the cylinders-to-vesicles transition. We believe that the reason for such behavior is the polydispersity of the core-forming blocks: The presence of the short and long blocks being located at the micelle interface and in its center, respectively, helps to reduce the entropy losses due to the insoluble block stretching, which leads to the increased stability of more curved micelles. Full article

(This article belongs to the Special Issue Phase Transitions in Polymers and Polymer Morphologies)

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16 pages, 5322 KiB

Open AccessArticle

Crystallization of Poly(ethylene)s with Regular Phosphoester Defects Studied at the Air–Water Interface

by Nazmul Hasan, Karsten Busse, Tobias Haider, Frederik R. Wurm and Jörg Kressler

Polymers 2020, 12(10), 2408; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12102408 - 19 Oct 2020

Cited by 5 | Viewed by 2643

Abstract

Poly(ethylene) (PE) is a commonly used semi-crystalline polymer which, due to the lack of polar groups in the repeating unit, is not able to form Langmuir or Langmuir–Blodgett (LB) films. This problem can be solved using PEs with hydrophilic groups arranged at regular distances within the polymer backbone. With acyclic diene metathesis (ADMET) polymerization, a tool for precise addition of polar groups after a certain interval of methylene sequence is available. In this study, we demonstrate the formation of Langmuir/LB films from two different PEs with regular phosphoester groups, acting as crystallization defects in the main chain. After spreading the polymers from chloroform solution on the water surface of a Langmuir trough and solvent evaporation, the surface pressure is recorded during compression under isothermal condition. These π-A isotherms, surface pressure π vs. mean area per repeat unit A, show a plateau zone at surface pressures of ~ (6 to 8) mN/m, attributed to the formation of crystalline domains of the PEs as confirmed by Brewster angle and epifluorescence microscopy. PE with ethoxy phosphoester defects (Ethoxy-PPE) forms circular shape domains, whereas Methyl-PPE-co-decadiene with methyl phosphoester defects and two different methylene sequences between the defects exhibits a film-like morphology. The domains/films are examined by atomic force microscopy after transferring them to a solid support. The thickness of the domains/films is found in the range from ~ (2.4 to 3.2) nm depending on the transfer pressure. A necessity of chain tilt in the crystalline domains is also confirmed. Grazing incidence X-ray scattering measurements in LB films show a single Bragg reflection at a scattering vector q_xy position of ~ 15.1 nm⁻¹ known from crystalline PE samples. Full article

(This article belongs to the Special Issue Phase Transitions in Polymers and Polymer Morphologies)

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12 pages, 2681 KiB

Open AccessArticle

Highly Sustainable and Completely Amorphous Hierarchical Ceramide Microcapsules for Potential Epidermal Barrier

by Joonsik Yoon, Minjoo Noh, Jun Bae Lee and Jun Hyup Lee

Polymers 2020, 12(9), 2166; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12092166 - 22 Sep 2020

Cited by 4 | Viewed by 3887

Abstract

As a main component of the stratum corneum, ceramides can construct protective lamellae to provide an epidermal barrier against dehydration or external microorganisms. However, as ceramide molecules can easily form the isolated crystalline phase through self-assembly due to the amphipathic nature of bioactive lipids, the effective incorporation of ceramides into liquid media is the remaining issue for controlled release. Here, we report an unprecedented effective strategy to fabricate a completely amorphous and highly sustainable hierarchical ceramide polymer microcapsule for promising epidermal barrier by using the interpenetrating and cooperative self-construction of conical amphiphiles with a different critical packing parameter. The self-constructed amorphous architecture of ceramides in polymer microcapsule is achieved by the facile doping of conical amphiphiles and subsequent in situ polymerization of shell polymer in the core-shell geometry. It is experimentally revealed that an irregular cooperative packing structure formed by adaptive hydrophobic–hydrophilic interactions of cylindrical ceramides and conical amphiphiles in the confined microcapsule geometry enables a completely amorphous morphology of ceramides to be realized during the spontaneous encapsulation process. Furthermore, this elegant approach affords a highly dispersible and uniform hierarchical amorphous ceramide microcapsule with a greatly enhanced long-term stability compared to conventional crystalline ceramides. Full article

(This article belongs to the Special Issue Phase Transitions in Polymers and Polymer Morphologies)

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14 pages, 3203 KiB

Open AccessArticle

Synchrotron and Raman Study of the Rotator Phases and Polymorphism in Tricosane Paraffin

by Enrique Blázquez-Blázquez, Rosa Barranco-García, María L. Cerrada, Juan C. Martínez and Ernesto Pérez

Polymers 2020, 12(6), 1341; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12061341 - 13 Jun 2020

Cited by 2 | Viewed by 2405

Abstract

A detailed study of the phase behavior of n-paraffin C₂₃H₄₈ has been performed by means of real-time variable-temperature experiments with synchrotron radiation. Two detectors were employed for simultaneous analysis of the small-angle (SAXS) and wide-angle X-ray-scattering (WAXS) regions. This paraffin presents a very interesting phase behavior, involving two crystal polymorphs, three rotator phases and the liquid state. The Ostwald rule of stages is invoked to find similarities of the rotator phases with the eventual transient mesomorphic structure in the multistage model of polymer crystallization. That study is complemented by variable-temperature Raman experiments covering frequencies down to 150 cm⁻¹. It was found that the low-frequency region is the most informative regarding the phase transitions, and specifically the intensity of the first overtone. From these analyses, several parameters are evaluated as function of temperature. Full article

(This article belongs to the Special Issue Phase Transitions in Polymers and Polymer Morphologies)

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18 pages, 880 KiB

Open AccessArticle

Liquid Crystal Ordering in the Hexagonal Phase of Rod-Coil Diblock Copolymers

by Mikhail A. Osipov, Maxim V. Gorkunov and Alexander A. Antonov

Polymers 2020, 12(6), 1262; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12061262 - 31 May 2020

Cited by 3 | Viewed by 2038

Abstract

Density functional theory of rod-coil diblock copolymers, developed recently by the authors, has been generalised and used to study the liquid crystal ordering and microphase separation effects in the hexagonal, lamellar and nematic phases. The translational order parameters of rod and coil monomers and the orientational order parameters of rod-like fragments of the copolymer chains have been determined numerically by direct minimization of the free energy. The phase diagram has been derived containing the isotropic, the lamellar and the hexagonal phases which is consistent with typical experimental data. The order parameter profiles as functions of temperature and the copolymer composition have also been determined in different anisotropic phases. Finally, the spatial distributions of the density of rigid rod fragments and of the corresponding orientational order parameter in the hexagonal phase have been calculated. Full article

(This article belongs to the Special Issue Phase Transitions in Polymers and Polymer Morphologies)

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11 pages, 3291 KiB

Open AccessArticle

Phase Behavior and Phase Diagram of Polystyrene-b-Poly(Perfluorooctylethyl Acrylates)

by Yu Shao, Hui Dai, Meng Zhao, Bin Li, Jianan Yao, Wen-Bin Zhang and Hui Li

Polymers 2020, 12(4), 819; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12040819 - 04 Apr 2020

Cited by 1 | Viewed by 2533

Abstract

Fluorocontaining polymers bearing special properties are unique and important materials in modern society. In this work, we focused on the phase behavior and phase diagram of poly(styrene-block-perfluorooctylethyl acrylate) with a volume fraction varying from 0.2 to 0.8. Small-angle X-ray scattering and transmission electron microscopy showed the phase formation in the sequence of hexagonally packed cylinders (HEX) to lamellar layers (LAM) to inverse hexagonally packed cylinders (iHEX) in this series of block polymers. Wide-angle X-ray diffraction experiments proved that the fluorodomains of the LAM phases and the matrix of iHEX phases contained layered structures formed by the crystallization of fluorosegments. During heating, the self-assembled lattice remained intact even after the melting of fluorodomain, with barely changed lattice parameters. Such hierarchical structural formation was understood by chain conformation and domain interaction, which may provide new insight into the molecular design of advanced materials. Full article

(This article belongs to the Special Issue Phase Transitions in Polymers and Polymer Morphologies)

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