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Synthesis, Characterization and Application of Polymer-Based Materials

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: 30 September 2024 | Viewed by 11989

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Special Issue Editors

Dr. Nadya Vasileva Dencheva

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Guest Editor

IPC-Institute for Polymers and Composites, Department of Polymer Engineering, University of Minho, Campus de Azurem, 4800-058 Guimaraes, Portugal
Interests: polymer chemistry; activated anionic polymerization; reactive microencapsulatioin; hybrid polymer powders; molecular imprinting; enzyme immobilization and compartmentalization; polymer-assisted multienzyme systems; biocatalysis

Dr. Zlatan Denchev

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Guest Editor

IPC-Institute for Polymers and Composites, Department of Polymer Engineering, University of Minho, Campus de Azurem, 4800-058 Guimaraes, Portugal
Interests: polymer chemistry; reactive microencapsulation; reactive processing; polymer micro- and nanocomposites; polymer crystallization; synchrotron wide- and small-angle X-ray scattering of polymers; spectroscopy of polymers; mechanical testing of polymer composites

Special Issue Information

Dear Colleagues,

Numerous commodities and advanced materials of industrial importance used for structural or functional applications are composed of polymers as their basic constituent. Generally, polymer-based materials (PBMs) contain two or more phases or components with properly chosen morphologies and specific interfacial bonding. The aim of this combination is to achieve the desired set of properties necessary for a certain area of application. Examples could be all types of polymer composites, in which a polymer matrix is mechanically reinforced by organic or inorganic, macro- or microsized, variously shaped structures. Furthermore, polymer hybrids characterized by an interaction between their constituents at the submicron and molecular levels exist, thereby producing properties not existing in either of them. PBMs may be based on natural, synthetic or recycled materials, as well as on conjugates between polymers and biologically active molecules, e.g., proteins, enzymes, DNA, and RNA, among others. The areas of application of PBMs are abundant and vast, stretching from self-cleaning, self-healing, conductive, magnetic, and energy-shielding polymers to polymer-supported biocatalysts, functional polymer hydrogels, and drug-delivery and food-stabilizing systems.

Recent advances in polymerization chemistry, polymer assembly, and conventional and non-conventional polymer processing techniques have resulted in a great number of PBMs with tailored properties and potential applications at various scales. This is achieved by careful control of the morphology and the structure–properties relationship, requiring advanced structural characterization.

The aim of this Special Issue of Molecules is to present a selection of research papers and reviews exemplifying the new trends in the synthesis, characterization and application of PBMs. Potential topics include, but are not limited to:

Synthesis of polymer-based materials with tailored properties;
Structure–properties relationship in polymer-based materials;
Advanced characterization of polymer-based materials;
Non-conventional processing of polymer-based materials;
Polymer-based materials with natural and/or biodegradable constituents;
Polymer-based materials as supports for bioactive molecules;
Applications of polymer-based materials in biology, medicine or food industries;
Stimuli-responsive polymer-based materials;
Polymer-based materials in engineering and electronics.

Dr. Nadya Vasileva Dencheva
Dr. Zlatan Denchev
Guest Editors

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. Molecules 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

synthetic, natural and sustainable polymer-based materials
polymer composites
polymer hybrids
multifunctional and smart polymer materials
structure-properties relationship in polymer systems
advanced characterization of polymer multiphase systems
polymer synthesis and reactive processing
polymer-based supports for bioactive molecules
applications of polymer-based materials
hydrophilic polymer systems

Published Papers (9 papers)

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Research

Jump to: Review

13 pages, 4015 KiB

Open AccessArticle

Control of Pore Sizes in Epoxy Monoliths and Applications as Sheet-Type Adhesives in Combination with Conventional Epoxy and Acrylic Adhesives

by Yoshiyuki Kamo and Akikazu Matsumoto

Molecules 2024, 29(9), 2059; https://doi.org/10.3390/molecules29092059 - 29 Apr 2024

Viewed by 196

Abstract

Materials with monolithic structures, such as epoxy monoliths, are used for a variety of applications, such as for column fillers in gas chromatography and HPLC, for separators in lithium-ion batteries, and for precursor polymers for monolith adhesion. In this study, we investigated the fabrication of epoxy monoliths using 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C) as the tetrafunctional epoxy and 4,4′-methylenebis(cyclohexylamine) (BACM) as the amine curing agent to control pore diameters using polyethylene glycols (PEGs) of differing molecular weights as the porogenic agents. We fabricated an epoxy monolith with micron-order pores and high strength levels, and which is suitable for the precursors of composite materials in cases where smaller PEGs are used. We discussed the effects of the porous structures of monoliths on their physical properties, such as tensile strength, elongation, elastic modulus, and glass transition temperatures. For example, epoxy monoliths prepared in the presence of PEGs exhibited an elastic modulus less than 1 GPa at room temperature and Tg values of 175–187 °C, while the epoxy bulk thermoset produced without any porogenic solvent showed a high elastic modulus as 1.8 GPa, which was maintained at high temperatures, and a high Tg of 223 °C. In addition, the unique adhesion characteristics of epoxy monolith sheets are revealed as a result of the combinations made with commercial epoxy and acrylic adhesives. Epoxy monoliths that are combined with conventional adhesives can function as sheet-type adhesives purposed with avoiding problems when only liquid-type adhesives are used. Full article

(This article belongs to the Special Issue Synthesis, Characterization and Application of Polymer-Based Materials)

28 pages, 6794 KiB

Open AccessArticle

The New Elastomeric Compounds Made of Butyl Rubber Filled with Phyllosilicates, Characterized by Increased Barrier Properties and Hydrophobicity and Reduced Chemical Degradation

by Aleksandra Smejda-Krzewicka, Emilia Irzmańska, Konrad Mrozowski, Agnieszka Adamus-Włodarczyk, Natalia Litwicka, Krzysztof Strzelec and Małgorzata I. Szynkowska-Jóźwik

Molecules 2024, 29(6), 1306; https://doi.org/10.3390/molecules29061306 - 15 Mar 2024

Viewed by 651

Abstract

The aim of the study was to produce new elastomeric materials containing butyl rubber (IIR) filled with silica and phyllosilicates (vermiculite, montmorillonite, perlite or halloysite tubes) with enhanced hydrophobicity and barrier properties and reduced chemical degradation. It was found that the filler type had a significant impact on the degree of cross-linking of butyl rubber and the properties of its vulcanizates. The highest degree of cross-linking and the highest mechanical strength were achieved for IIR composites filled with Arsil with perlite or halloysite tubes. The highest surface hydrophobicity (119°) was confirmed for the IIR vulcanizates with Arsil and montmorillonite. All tested samples showed high barrier properties because both the gas diffusion rate coefficient and the permeability coefficient reached low values. Both unfilled and filled IIR vulcanizates retained chemical resistance in contact with methanol for 480 min. Hour-long contact of a polar solvent (methanol) with each of the vulcanizates did not cause material degradation, while the presence of a non-polar solvent (n-heptane) worsened the mechanical parameters by up to 80%. However, the presence of fillers reduced the chemical degradation of vulcanizates (in the case of cured IIR filled with Arsil and halloysite tubes by 40% compared to the composite without fillers). Full article

(This article belongs to the Special Issue Synthesis, Characterization and Application of Polymer-Based Materials)

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25 pages, 9852 KiB

Open AccessArticle

Graphene Modification by Curcuminoids as an Effective Method to Improve the Dispersion and Stability of PVC/Graphene Nanocomposites

by Sławomir Wilczewski, Katarzyna Skórczewska, Jolanta Tomaszewska, Magdalena Osial, Agnieszka Dąbrowska, Kostiantyn Nikiforow, Piotr Jenczyk and Hubert Grzywacz

Molecules 2023, 28(8), 3383; https://doi.org/10.3390/molecules28083383 - 11 Apr 2023

Cited by 4 | Viewed by 1372

Abstract

A large amount of graphene-related research is its use as a filler for polymer composites, including thin nanocomposite films. However, its use is limited by the need for large-scale methods to obtain high–quality filler, as well as its poor dispersion in the polymer matrix. This work presents polymer thin-film composites based on poly(vinyl chloride) (PVC) and graphene, whose surfaces were modified by curcuminoids. TGA, UV–vis, Raman spectroscopy, XPS, TEM, and SEM methods have confirmed the effectiveness of the graphene modification due to π–π interactions. The dispersion of graphene in the PVC solution was investigated by the turbidimetric method. SEM, AFM, and Raman spectroscopy methods evaluated the thin-film composite’s structure. The research showed significant improvements in terms of graphene’s dispersion (in solutions and PVC composites) following the application of curcuminoids. The best results were obtained for materials modified with compounds obtained from the extraction of the rhizome of Curcuma longa L. Modification of the graphene’s surface with these compounds also increased the thermal and chemical stability of PVC/graphene nanocomposites. Full article

(This article belongs to the Special Issue Synthesis, Characterization and Application of Polymer-Based Materials)

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26 pages, 6101 KiB

Open AccessArticle

Synthesis of Novel Polymer-Assisted Organic-Inorganic Hybrid Nanoflowers and Their Application in Cascade Biocatalysis

by Joana F. Braz, Nadya V. Dencheva, Marc Malfois and Zlatan Z. Denchev

Molecules 2023, 28(2), 839; https://doi.org/10.3390/molecules28020839 - 14 Jan 2023

Cited by 4 | Viewed by 1547

Abstract

This study reports on the synthesis of novel bienzyme polymer-assisted nanoflower complexes (PANF), their morphological and structural characterization, and their effectiveness as cascade biocatalysts. First, highly porous polyamide 6 microparticles (PA6 MP) are synthesized by activated anionic polymerization in solution. Second, the PA6 MP are used as carriers for hybrid bienzyme assemblies comprising glucose oxidase (GOx) and horseradish peroxidase (HRP). Thus, four PANF complexes with different co-localization and compartmentalization of the two enzymes are prepared. In samples NF GH/PA and NF GH@PA, both enzymes are localized within the same hybrid flowerlike organic-inorganic nanostructures (NF), the difference being in the way the PA6 MP are assembled with NF. In samples NF G/PAiH and NF G@PAiH, only GOx is located in the NF, while HRP is preliminary immobilized on PA6 MP. The morphology and the structure of the four PANF complexes have been studied by microscopy, spectroscopy, and synchrotron X-ray techniques. The catalytic activity of the four PANF was assessed by a two-step cascade reaction of glucose oxidation. The PANF complexes are up to 2–3 times more active than the free GOx/HRP dyad. They also display enhanced kinetic parameters, superior thermal stability in the 40–60 °C range, optimum performance at pH 4–6, and excellent storage stability. All PANF complexes are active for up to 6 consecutive operational cycles. Full article

(This article belongs to the Special Issue Synthesis, Characterization and Application of Polymer-Based Materials)

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18 pages, 4606 KiB

Open AccessArticle

Can Biomass Mastication Assist the Downstreaming of Polyhydroxyalkanoates Produced from Mixed Microbial Cultures?

by Hiléia K.S. Souza, Mariana Matos, Maria A.M. Reis, José A. Covas and Loïc Hilliou

Molecules 2023, 28(2), 767; https://doi.org/10.3390/molecules28020767 - 12 Jan 2023

Cited by 2 | Viewed by 1117

Abstract

Polyhydroxyalkanoates (PHAs) are natural polyesters which biodegrade in soils and oceans but have more than double the cost of comparable oil-based polymers. PHA downstreaming from its biomass represents 50% of its overall cost. Here, in an attempt to assist downstreaming, mastication of wet biomasses is tested as a new mechanical continuous biomass pretreatment with potential for industrial upscaling. Downstreaming conditions where both product recovery and purity are low due to the large amount of treated wet biomass (50% water) were targeted with the following process: extraction of 20 g in 100 mL solvent at 30 °C for 2 h, followed by 4.8 h digestion of 20 g in 0.3 M NaOH. Under the studied conditions, NaOH digestion was more effective than solvent extraction in recovering larger PHA amounts, but with less purity. A nearly 50% loss of PHA was seen during digestion after mastication. PHAs downstreamed by digestion with large amounts of impurities started to degrade at lower temperatures, but their melt elasticity was thermally stable at 170 °C. As such, these materials are attractive as fully PHA-compatible processing aids, reinforcing fillers or viscosity modifiers. On the other hand, wet biomass mastication before solvent extraction improves PHA purity and thermal stability as well as the melt rheology, which recovers the viscoelasticity measured with a PHA extracted from a dried biomass. Full article

(This article belongs to the Special Issue Synthesis, Characterization and Application of Polymer-Based Materials)

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11 pages, 3458 KiB

Open AccessArticle

Fluorine-Containing Flow Modifier for BN/PPS Composites Enabled by Low Surface Energy

by Bo Cao, Xiaodan Huang, Wenxiang Zhang and Peng Wu

Molecules 2022, 27(22), 8066; https://doi.org/10.3390/molecules27228066 - 20 Nov 2022

Cited by 1 | Viewed by 1164

Abstract

In this study, a fluorine-containing flow modifier (Si-DF) with low surface energy is successfully synthesized, which is applied to fabricate ideal electronic packaging materials (BN/PPS composites) with high thermal conductivity, excellent dielectric properties, processability, and toughness by conventional melt blending. Si-DPF is located at the interface between the BN fillers and the PPS matrix, which not only improves the dispersion of BN fillers but also strengthens the interaction. With the help of 5 wt% Si-DF, BN/PPS/Si-DF (70/25/5) still exhibits the high thermally conductive coefficient (3.985 W/m·K) and low dielectric constant (3.76 at 100 MHz) although BN fillers are loaded as high as 70 wt%. Moreover, the sample processes a lower stable torque value (2.5 N·m), and the area under the stress–strain curves is also increased. This work provides an efficient way to develop high-performance polymer-based composites with high thermally conductive coefficients and low dielectric constants for electronic packaging applications. Full article

(This article belongs to the Special Issue Synthesis, Characterization and Application of Polymer-Based Materials)

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Review

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32 pages, 12307 KiB

Open AccessReview

Polymer Composites in 3D/4D Printing: Materials, Advances, and Prospects

by Ayyaz Mahmood, Fouzia Perveen, Shenggui Chen, Tayyaba Akram and Ahmad Irfan

Molecules 2024, 29(2), 319; https://doi.org/10.3390/molecules29020319 - 09 Jan 2024

Viewed by 2303

Abstract

Additive manufacturing (AM), commonly referred to as 3D printing, has revolutionized the manufacturing landscape by enabling the intricate layer-by-layer construction of three-dimensional objects. In contrast to traditional methods relying on molds and tools, AM provides the flexibility to fabricate diverse components directly from digital models without the need for physical alterations to machinery. Four-dimensional printing is a revolutionary extension of 3D printing that introduces the dimension of time, enabling dynamic transformations in printed structures over predetermined periods. This comprehensive review focuses on polymeric materials in 3D printing, exploring their versatile processing capabilities, environmental adaptability, and applications across thermoplastics, thermosetting materials, elastomers, polymer composites, shape memory polymers (SMPs), including liquid crystal elastomer (LCE), and self-healing polymers for 4D printing. This review also examines recent advancements in microvascular and encapsulation self-healing mechanisms, explores the potential of supramolecular polymers, and highlights the latest progress in hybrid printing using polymer–metal and polymer–ceramic composites. Finally, this paper offers insights into potential challenges faced in the additive manufacturing of polymer composites and suggests avenues for future research in this dynamic and rapidly evolving field. Full article

(This article belongs to the Special Issue Synthesis, Characterization and Application of Polymer-Based Materials)

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29 pages, 21306 KiB

Open AccessReview

Synthesis and Applications of Hybrid Polymer Networks Based on Renewable Natural Macromolecules

by Dariya Getya and Ivan Gitsov

Molecules 2023, 28(16), 6030; https://doi.org/10.3390/molecules28166030 - 12 Aug 2023

Viewed by 1148

Abstract

Macromolecules obtained from renewable natural sources are gaining increasing attention as components for a vast variety of sustainable polymer-based materials. Natural raw materials can facilitate continuous-flow production due to their year-round availability and short replenishment period. They also open new opportunities for chemists and biologists to design and create “bioreplacement” and “bioadvantaged” polymers, where complex structures produced by nature are being modified, upgraded, and utilized to create novel materials. Bio-based macromonomers are expected not only to compete with but to replace some petroleum-based analogs, as well. The development of novel sustainable materials is an ongoing and very dynamic process. There are multiple strategies for transforming natural macromolecules into sophisticated value-added products. Some methods include chemical modification of macromolecules, while others include blending several components into one new system. One of the most promising approaches for incorporating renewable macromolecules into new products is the synthesis of hybrid networks based on one or more natural components. Each one has unique characteristics, so its incorporation into a network brings new sustainable materials with properties that can be tuned according to their end-use. This article reviews the current state-of-the-art and future potential of renewable natural macromolecules as sustainable building blocks for the synthesis and use of hybrid polymer networks. The most recent advancements and applications that involve polymers, such as cellulose, chitin, alginic acid, gellan gum, lignin, and their derivatives, are discussed. Full article

(This article belongs to the Special Issue Synthesis, Characterization and Application of Polymer-Based Materials)

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23 pages, 7248 KiB

Open AccessReview

The Synthesis and Polymer-Reinforced Mechanical Properties of SiO₂ Aerogels: A Review

by Wang Zhan, Le Chen, Qinghong Kong, Lixia Li, Mingyi Chen, Juncheng Jiang, Weixi Li, Fan Shi and Zhiyuan Xu

Molecules 2023, 28(14), 5534; https://doi.org/10.3390/molecules28145534 - 20 Jul 2023

Cited by 4 | Viewed by 1716

Abstract

Silica aerogels are considered as the distinguished materials of the future due to their extremely low thermal conductivity, low density, and high surface area. They are widely used in construction engineering, aeronautical domains, environmental protection, heat storage, etc. However, their fragile mechanical properties are the bottleneck restricting the engineering application of silica aerogels. This review briefly introduces the synthesis of silica aerogels, including the processes of sol–gel chemistry, aging, and drying. The effects of different silicon sources on the mechanical properties of silica aerogels are summarized. Moreover, the reaction mechanism of the three stages is also described. Then, five types of polymers that are commonly used to enhance the mechanical properties of silica aerogels are listed, and the current research progress is introduced. Finally, the outlook and prospects of the silica aerogels are proposed, and this paper further summarizes the methods of different polymers to enhance silica aerogels. Full article

(This article belongs to the Special Issue Synthesis, Characterization and Application of Polymer-Based Materials)

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