Editor’s Choice Articles

Editor’s Choice articles are based on recommendations by the scientific editors of MDPI journals from around the world. Editors select a small number of articles recently published in the journal that they believe will be particularly interesting to readers, or important in the respective research area. The aim is to provide a snapshot of some of the most exciting work published in the various research areas of the journal.

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12 pages, 2823 KiB  
Article
On the Use of Persian Gum for the Development of Antiviral Edible Coatings against Murine Norovirus of Interest in Blueberries
by Niloufar Sharif, Irene Falcó, Antonio Martínez-Abad, Gloria Sánchez, Amparo López-Rubio and María José Fabra
Polymers 2021, 13(2), 224; https://doi.org/10.3390/polym13020224 - 11 Jan 2021
Cited by 16 | Viewed by 2692
Abstract
In the last decades, berries have been identified as important vehicles for the transmission of foodborne viruses and different strategies are being explored to eliminate or reduce viral contamination in these fruits. The aim of this work was to develop novel edible coatings [...] Read more.
In the last decades, berries have been identified as important vehicles for the transmission of foodborne viruses and different strategies are being explored to eliminate or reduce viral contamination in these fruits. The aim of this work was to develop novel edible coatings with antiviral properties for inactivating and reducing murine norovirus (MNV). Firstly, the effect of gelatin (G) addition on Persian gum (PG) films was studied in terms of microstructural, mechanical, optical, and water barrier properties. The following PG:G ratios were considered: 100:0, 75:25, 50:50, 25:75, and 0:100. Microstructure analysis revealed the compatibility of both hydrocolloids since no phase separation was observed. The addition of G to PG films provided stiffer and more deformable films than pure PG, with lower water vapor permeability values. Specifically, films prepared with 50:50 PG:G ratio presented better mechanical and barrier performance. Interestingly, pure PG showed antiviral activity on murine norovirus, probably due to the presence of some impurities (mainly tannins). Adding allyl isothiocyanate (AITC) enhanced the PG antiviral activity at refrigerated temperatures in blueberries, not being affected by the AITC concentration. This effect was not observed at ambient temperature, probably due to the volatilization of AITC. Full article
(This article belongs to the Special Issue Sustainable Plastics for Active/Intelligent Food Packaging)
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21 pages, 5342 KiB  
Article
Role of pKA in Charge Regulation and Conformation of Various Peptide Sequences
by Raju Lunkad, Anastasiia Murmiliuk, Zdeněk Tošner, Miroslav Štěpánek and Peter Košovan
Polymers 2021, 13(2), 214; https://doi.org/10.3390/polym13020214 - 9 Jan 2021
Cited by 24 | Viewed by 3848
Abstract
Peptides containing amino acids with ionisable side chains represent a typical example of weak ampholytes, that is, molecules with multiple titratable acid and base groups, which generally exhibit charge regulating properties upon changes in pH. Charged groups on an ampholyte interact electrostatically with [...] Read more.
Peptides containing amino acids with ionisable side chains represent a typical example of weak ampholytes, that is, molecules with multiple titratable acid and base groups, which generally exhibit charge regulating properties upon changes in pH. Charged groups on an ampholyte interact electrostatically with each other, and their interaction is coupled to conformation of the (macro)molecule, resulting in a complex feedback loop. Their charge-regulating properties are primarily determined by the pKA of individual ionisable side-chains, modulated by electrostatic interactions between the charged groups. The latter is determined by the amino acid sequence in the peptide chain. In our previous work we introduced a simple coarse-grained model of a flexible peptide. We validated it against experiments, demonstrating its ability to quantitatively predict charge on various peptides in a broad range of pH. In the current work, we investigated two types of peptide sequences: diblock and alternating, each of them consisting of an equal number of amino acids with acid and base side-chains. We showed that changing the sequence while keeping the same overall composition has a profound effect on the conformation, whereas it practically does not affect total charge on the peptide. Nevertheless, the sequence significantly affects the charge state of individual groups, showing that the zero net effect on the total charge is a consequence of unexpected cancellation of effects. Furthermore, we investigated how the difference between the pKA of acid and base side chains affects the charge and conformation of the peptide, showing that it is possible to tune the charge-regulating properties by following simple guiding principles based on the pKA and on the amino acid sequence. Our current results provide a theoretical basis for understanding of the complex coupling between the ionisation and conformation in flexible polyampholytes, including synthetic polymers, biomimetic materials and biological molecules, such as intrinsically disordered proteins, whose function can be regulated by changes in the pH. Full article
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12 pages, 3285 KiB  
Article
New Functionalized Ionic Liquids Based on POSS for the Detection of Fe3+ Ion
by Wensi Li and Shengyu Feng
Polymers 2021, 13(2), 196; https://doi.org/10.3390/polym13020196 - 7 Jan 2021
Cited by 8 | Viewed by 2319
Abstract
This study reports a novel series of imidazolium ionic liquids (ILs) based on polyhedral oligomeric silsesquioxanes (POSS) towards effective detection of metal ions, especially Fe3+ ion. 1H, 13C, 29Si NMR, high resolution mass spectra (HRMS) and Fourier transform infrared spectra [...] Read more.
This study reports a novel series of imidazolium ionic liquids (ILs) based on polyhedral oligomeric silsesquioxanes (POSS) towards effective detection of metal ions, especially Fe3+ ion. 1H, 13C, 29Si NMR, high resolution mass spectra (HRMS) and Fourier transform infrared spectra (FTIR) were applied to confirm the structures of the ILs based on POSS (ILs-POSS). The three ILs-POSS were synthesized via a green chemistry approach—a thiol-ene “click” reaction without metal ions as catalysts. Furthermore, the spherical vesicle structures of the ILs-POSS were observed and caused by self-assembly behaviors. Through comprehensive characterizations, these ILs-POSS have performed excellent thermal stabilities and low glass transition temperatures. In addition, we found it very meaningful that the limits of detection (LODs) of the three ILs-POSS for the detection of the Fe3+ ion were 7.91 × 10−8 M, 1.2 × 10−7 M, and 1.2 × 10−7 M, respectively. These data illustrate that these ILs-POSS have great potential for the detection of the Fe3+ ion. In conclusion, this study not only prepared novel ILs-POSS, but also provided new materials as fluorescent sensors in the detection of Fe3+. Full article
(This article belongs to the Special Issue Silsesquioxane (POSS) Polymers, Copolymers and Nanoparticles)
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14 pages, 779 KiB  
Article
Protein Unfolding and Aggregation near a Hydrophobic Interface
by David March, Valentino Bianco and Giancarlo Franzese
Polymers 2021, 13(1), 156; https://doi.org/10.3390/polym13010156 - 3 Jan 2021
Cited by 26 | Viewed by 4024
Abstract
The behavior of proteins near interfaces is relevant for biological and medical purposes. Previous results in bulk show that, when the protein concentration increases, the proteins unfold and, at higher concentrations, aggregate. Here, we study how the presence of a hydrophobic surface affects [...] Read more.
The behavior of proteins near interfaces is relevant for biological and medical purposes. Previous results in bulk show that, when the protein concentration increases, the proteins unfold and, at higher concentrations, aggregate. Here, we study how the presence of a hydrophobic surface affects this course of events. To this goal, we use a coarse-grained model of proteins and study by simulations their folding and aggregation near an ideal hydrophobic surface in an aqueous environment by changing parameters such as temperature and hydrophobic strength, related, e.g., to ions concentration. We show that the hydrophobic surface, as well as the other parameters, affect both the protein unfolding and aggregation. We discuss the interpretation of these results and define future lines for further analysis, with their possible implications in neurodegenerative diseases. Full article
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12 pages, 4447 KiB  
Article
Influence of Humidity on Fatigue Performance of CFRP: A Molecular Simulation
by Bowen Li, Jianzhong Chen, Yong Lv, Li Huang and Xiaoyu Zhang
Polymers 2021, 13(1), 140; https://doi.org/10.3390/polym13010140 - 31 Dec 2020
Cited by 8 | Viewed by 3219
Abstract
The study on durability of carbon fiber reinforced plastics (CFRP) in complex environments is critical because of its wide applications. Herein, mechanical behavior of carbon fiber reinforced epoxy composites in the fatigue process were investigated under different humidity via molecular dynamics (MD) simulation [...] Read more.
The study on durability of carbon fiber reinforced plastics (CFRP) in complex environments is critical because of its wide applications. Herein, mechanical behavior of carbon fiber reinforced epoxy composites in the fatigue process were investigated under different humidity via molecular dynamics (MD) simulation method. Transversely isotropic atom based models were established to simulate the structure of CFRP at the atomistic level. Owing to the weak performance in vertical fiber direction, mechanical behavior in a 90° orientation was investigated. Mean stress and energy were both employed to describe the evolution of mechanical performance while mean squared displacement (MSD), radius of gyration (Rg), and free volume were performed to describe the evolution of structural change during the fatigue process. The results show that the humidity led to a weakened interfacial adhesive performance. Free volume became larger under cyclic load, which caused the water molecules to diffuse into the inside of epoxy resin. The distance between the matrix and fiber became larger in the dry system while it reduced because of the diffusion of water molecules in wet system. The rate of performance degradation decreased with the increase in humidity because of poor initial performance at high humidity. Full article
(This article belongs to the Section Polymer Composites and Nanocomposites)
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9 pages, 1532 KiB  
Article
Effect of Material Parameter of Viscoelastic Giesekus Fluids on Extensional Properties in Spinline and Draw Resonance Instability in Isothermal Melt Spinning Process
by Geunyeop Park, Jangho Yun, Changhoon Lee and Hyun Wook Jung
Polymers 2021, 13(1), 139; https://doi.org/10.3390/polym13010139 - 31 Dec 2020
Cited by 1 | Viewed by 2848
Abstract
The draw resonance instability of viscoelastic Giesekus fluids was studied by correlating the spinline extensional features and transit times of several kinematic waves in an isothermal melt spinning process. The critical drawdown ratios were critically dependent on the Deborah number (De, [...] Read more.
The draw resonance instability of viscoelastic Giesekus fluids was studied by correlating the spinline extensional features and transit times of several kinematic waves in an isothermal melt spinning process. The critical drawdown ratios were critically dependent on the Deborah number (De, the ratio of material relaxation time to process time) and a single material parameter (αG) of the Giesekus fluid. In the intermediate range of αG, the stability status changed distinctively with increasing De, i.e., the spinning system was initially stabilized and subsequently destabilized, as De increases. In this αG regime, the level of velocity and extensional-thickening rheological property in the spinline became gradually enhanced at low De and weakened at high De. The draw resonance onsets for different values of αG were determined precisely using a simple indicator composed of several kinematic waves traveling the entire spinline and period of oscillation. The change in transit times of kinematic waves for varying De adequately reflected the effect of αG on the change in stability. Full article
(This article belongs to the Special Issue Rheology and Processing of Polymers)
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16 pages, 10577 KiB  
Article
Stabilization of Palygorskite Aqueous Suspensions Using Bio-Based and Synthetic Polyelectrolytes
by Eduardo Ferraz, Luís Alves, Pedro Sanguino, Julio Santarén, Maria G. Rasteiro and José A. F. Gamelas
Polymers 2021, 13(1), 129; https://doi.org/10.3390/polym13010129 - 30 Dec 2020
Cited by 8 | Viewed by 2760
Abstract
Palygorskite is a natural fibrous clay mineral that can be used in several applications, for which colloidal stability in aqueous suspensions is a key point to improve its performance. In this study, methods of magnetic stirring, high-speed shearing, and ultrasonication, as well as [...] Read more.
Palygorskite is a natural fibrous clay mineral that can be used in several applications, for which colloidal stability in aqueous suspensions is a key point to improve its performance. In this study, methods of magnetic stirring, high-speed shearing, and ultrasonication, as well as different chemical dispersants, combined with these methods, namely carboxymethylcellulose, alginate, polyphosphate, and polyacrylate, were used to improve the dispersibility and the formation of stable suspensions of palygorskite in different conditions of pH. The stability and particle size of suspensions with a low concentration of palygorskite were evaluated by visual inspection, optical and electron microscopy, dynamic light scattering, and zeta potential measurements. Moreover, the palygorskite used in this work was initially characterized for its mineralogical, chemical, physical, and morphological properties. It was found that more stable suspensions were produced with ultrasonication compared to the other two physical treatments, with magnetic stirring being inefficient in all tested cases, and for higher pH values (pH of 12 and pH of 8, the natural pH of the clay) when compared to lower pH values (pH of 3). Remarkably, combined with ultrasonication, carboxymethylcellulose or in a lesser extent polyphosphate at near neutral pH allowed for the disaggregation of crystal bundles of palygorskite into individualized crystals. These results may be helpful to optimize the performance of palygorskite in several domains where it is applied. Full article
(This article belongs to the Special Issue Bio-Based Polyelectrolytes: Development and Applications)
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12 pages, 3035 KiB  
Article
A Kirigami Approach of Patterning Membrane Actuators
by Harti Kiveste, Rudolf Kiefer, Rain Eric Haamer, Gholamreza Anbarjafari and Tarmo Tamm
Polymers 2021, 13(1), 125; https://doi.org/10.3390/polym13010125 - 30 Dec 2020
Cited by 2 | Viewed by 2364
Abstract
Ionic electroactive polymer actuators are typically implemented as bending trilayer laminates. While showing high displacements, such designs are not straightforward to implement for useful applications. To enable practical uses in actuators with ionic electroactive polymers, membrane-type film designs can be considered. The significantly [...] Read more.
Ionic electroactive polymer actuators are typically implemented as bending trilayer laminates. While showing high displacements, such designs are not straightforward to implement for useful applications. To enable practical uses in actuators with ionic electroactive polymers, membrane-type film designs can be considered. The significantly lower displacement of the membrane actuators due to the lack of freedom of motion has been the main limiting factor for their application, resulting in just a few works considering such devices. However, bioinspired patterning designs have been shown to significantly increase the freedom of motion of such membranes. In this work, we apply computer simulations to design cutting patterns for increasing the performance of membrane actuators based on polypyrrole doped with dodecylbenzenesulfonate (PPy/DBS) in trilayer arrangements with a polyvinylidene fluoride membrane as the separator. A dedicated custom-designed device was built to consistently measure the response of the membrane actuators, demonstrating significant and pattern-specific enhancements of the response in terms of displacement, exchanged charge and force. Full article
(This article belongs to the Special Issue High-Functional Polymeric Materials)
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14 pages, 1310 KiB  
Article
Color Fixation Strategies on Sustainable Poly-Butylene Succinate Using Biobased Itaconic Acid
by Lidia G. Quiles, Julio Vidal, Francesca Luzi, Franco Dominici, Ángel Fernández Cuello and Pere Castell
Polymers 2021, 13(1), 79; https://doi.org/10.3390/polym13010079 - 28 Dec 2020
Cited by 4 | Viewed by 2111
Abstract
Biopo-lybutylene succinate (bioPBS) is gaining attention in the biodegradable polymer market due to its promising properties, such as high biodegradability and processing versatility, representing a potential sustainable replacement for fossil-based commodities. However, there is still a need to enhance its properties for certain [...] Read more.
Biopo-lybutylene succinate (bioPBS) is gaining attention in the biodegradable polymer market due to its promising properties, such as high biodegradability and processing versatility, representing a potential sustainable replacement for fossil-based commodities. However, there is still a need to enhance its properties for certain applications, with aesthetical and mechanical properties being a challenge. The aim of the present work is to improve these properties by adding selected additives that will confer bioPBS with comparable properties to that of current counterparts such as polypropylene (PP) for specific applications in the automotive and household appliances sectors. A total of thirteen materials have been studied and compared, being twelve biocomposites containing combinations of three different additives: a commercial red colorant, itaconic acid (IA) to enhance color fixation and zirconia (ZrO2) nanoparticles to maintain at least native PBS mechanical properties. The results show that the combination of IA and the coloring agent tends to slightly yellowish the blend due to the absorbance spectra of IA and also to modify the gloss due to the formation of IA nanocrystals that affects light scattering. In addition, for low amounts of IA (4 wt %), Young’s Modulus seems to be kept while elongation at break is even raised. Unexpectedly, a strong aging affect was found after four weeks. IA increases the hydrophilic behavior of the samples and thus seems to accelerate the hydrolization of the matrix, which is accompanied by an accused disaggregation of phases and an overall softening and rigidization effect. The addition of low amounts of ZrO2 (2 wt %) seems to provide the desired effect for hardening the surface while almost not affecting the other properties; however, higher amounts tends to form aggregates saturating the compounds. As a conclusion, IA might be a good candidate for color fixing in biobased polymers. Full article
(This article belongs to the Special Issue Sustainable Bio-Based Polymers: Towards a Circular Bioeconomy)
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14 pages, 7074 KiB  
Article
Calcium Silicate-Activated Gelatin Methacrylate Hydrogel for Accelerating Human Dermal Fibroblast Proliferation and Differentiation
by Fong-Sian Lin, Jian-Jr Lee, Alvin Kai-Xing Lee, Chia-Che Ho, Yen-Ting Liu and Ming-You Shie
Polymers 2021, 13(1), 70; https://doi.org/10.3390/polym13010070 - 27 Dec 2020
Cited by 19 | Viewed by 3564
Abstract
Wound healing is a complex process that requires specific interactions between multiple cells such as fibroblasts, mesenchymal, endothelial, and neural stem cells. Recent studies have shown that calcium silicate (CS)-based biomaterials can enhance the secretion of growth factors from fibroblasts, which further increased [...] Read more.
Wound healing is a complex process that requires specific interactions between multiple cells such as fibroblasts, mesenchymal, endothelial, and neural stem cells. Recent studies have shown that calcium silicate (CS)-based biomaterials can enhance the secretion of growth factors from fibroblasts, which further increased wound healing and skin regeneration. In addition, gelatin methacrylate (GelMa) is a compatible biomaterial that is commonly used in tissue engineering. However, it has low mechanical properties, thus restricting its fullest potential for clinical applications. In this study, we infused Si ions into GelMa hydrogel and assessed for its feasibility for skin regeneration applications by observing for its influences on human dermal fibroblasts (hDF). Initial studies showed that Si could be successfully incorporated into GelMa, and printability was not affected. The degradability of Si-GelMa was approximately 20% slower than GelMa hydrogels, thus allowing for better wound healing and regeneration. Furthermore, Si-GelMa enhanced cellular adhesion and proliferation, therefore leading to the increased secretion of collagen I other important extracellular matrix (ECM) remodeling-related proteins including Ki67, MMP9, and decorin. This study showed that the Si-GelMa hydrogels were able to enhance the activity of hDF due to the gradual release of Si ions, thus making it a potential candidate for future skin regeneration clinical applications. Full article
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17 pages, 2346 KiB  
Article
Tailored Interfaces in Fiber-Reinforced Elastomers: A Surface Treatment Study on Optimized Load Coupling via the Modified Fiber Bundle Debond Technique
by Julia Beter, Boris Maroh, Bernd Schrittesser, Inge Mühlbacher, Thomas Griesser, Sandra Schlögl, Peter Filipp Fuchs and Gerald Pinter
Polymers 2021, 13(1), 36; https://doi.org/10.3390/polym13010036 - 24 Dec 2020
Cited by 4 | Viewed by 2463
Abstract
The interface between the reinforcement and surrounding matrix in a fibrous composite is decisive and critical for maintaining component performance, durability, and mechanical structure properties for load coupling assessment, especially for highly flexible composite materials. The clear trend towards tailored solutions reveals that [...] Read more.
The interface between the reinforcement and surrounding matrix in a fibrous composite is decisive and critical for maintaining component performance, durability, and mechanical structure properties for load coupling assessment, especially for highly flexible composite materials. The clear trend towards tailored solutions reveals that an in-depth knowledge on surface treating methods to enhance the fiber–matrix interfacial interaction and adhesion properties for an optimized load transfer needs to be ensured. This research aims to quantify the effect of several surface treatments for glass fibers applied in endless fiber-reinforced elastomers with pronounced high deformations. Due to this, the glass fiber surface is directly modified with selected sizings, using a wet chemical treatment, and characterized according to chemical and mechanical aspects. For this purpose, the interfacial adhesion performance between fibers and the surrounding matrix material is investigated by a modified fiber pull-out device. The results clearly show that an optimized surface treatment improves the interface strength and chemical bonding significantly. The fiber pull-out test confirms that an optimized fiber–matrix interface can be enhanced up to 85% compared to standard surface modifications, which distinctly provides the basis of enhanced performances on the component level. These findings were validated by chemical analysis methods and corresponding optical damage analysis. Full article
(This article belongs to the Special Issue Advanced Rubber Composite)
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12 pages, 4722 KiB  
Article
Phase Equilibrium, Morphology, and Physico-Mechanics in Epoxy–Thermoplastic Mixtures with Upper and Lower Critical Solution Temperatures
by Alexey V. Shapagin, Nikita Yu. Budylin, Anatoly E. Chalykh, Vitaliy I. Solodilov, Roman A. Korokhin and Arkadiy A. Poteryaev
Polymers 2021, 13(1), 35; https://doi.org/10.3390/polym13010035 - 24 Dec 2020
Cited by 15 | Viewed by 2436
Abstract
The mutual solubility of epoxy oligomer with polysulfone (PSU) and polyethersulfone (PES) was studied by optical interferometry. Additionally, phase diagrams (PDs) were plotted and their evolution during the curing process was shown. The phase structures of modified hardened systems, as well as their [...] Read more.
The mutual solubility of epoxy oligomer with polysulfone (PSU) and polyethersulfone (PES) was studied by optical interferometry. Additionally, phase diagrams (PDs) were plotted and their evolution during the curing process was shown. The phase structures of modified hardened systems, as well as their tensile strengths, elastic moduli, and crack resistance, have been studied by scanning electron microscopy and physico-mechanical techniques. The effect of initial components’ mutual solubility on the phase structure and, subsequently, on the physico-mechanical properties of the composite material is shown. Differences in the structure and properties of the cured modified compositions depending on the type of PD (with Upper Critical Solution Temperature (UCST) for PSU and Lower Critical Solution Temperature (LCST) for PES) of the initial components are shown. Full article
(This article belongs to the Section Polymer Physics and Theory)
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13 pages, 4163 KiB  
Article
Glycolysis of Poly(Ethylene Terephthalate) Using Biomass-Waste Derived Recyclable Heterogeneous Catalyst
by Samson Lalhmangaihzuala, Zathang Laldinpuii, Chhakchhuak Lalmuanpuia and Khiangte Vanlaldinpuia
Polymers 2021, 13(1), 37; https://doi.org/10.3390/polym13010037 - 24 Dec 2020
Cited by 44 | Viewed by 6543
Abstract
Plastic production has increased by almost 200-fold annually from 2 million metric tons per year in 1950s to 359 million metric tons in 2018. With this rapidly increasing production, plastic pollution has become one of the most demanding environmental issues and tremendous efforts [...] Read more.
Plastic production has increased by almost 200-fold annually from 2 million metric tons per year in 1950s to 359 million metric tons in 2018. With this rapidly increasing production, plastic pollution has become one of the most demanding environmental issues and tremendous efforts have been initiated by the research community for its disposal. In this present study, we reported for the first time, a biomass-waste-derived heterogeneous catalyst prepared from waste orange peel for the depolymerisation of poly(ethylene terephthalate) (PET) to its monomer, bis(2-hydroxyethyl terephthalate) (BHET). The prepared orange peel ash (OPA) catalyst was well-characterised using techniques such as IR, inductively coupled plasma (ICP)-OES (Optical Emission Spectrometry), XRD, X-ray fluorescence (XRF), SEM, energy-dispersive X-ray spectroscopy (EDX), TEM, BET (Brunauer-Emmett-Teller) and TGA. The catalyst was found to be composed of basic sites, high surface area, and a notable type-IV N2 adsorption–desorption isotherm indicating the mesoporous nature of the catalyst, which might have eventually enhanced the rate of the reaction as well as the yield of the product. The catalyst completely depolymerises PET within 90 min, producing 79% of recrystallised BHET. The ability of reusing the catalysts for 5 consecutive runs without significant depreciation in the catalytic activity and its eco- and environmental-friendliness endorses this protocol as a greener route for PET recycling. Full article
(This article belongs to the Section Circular and Green Polymer Science)
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30 pages, 5422 KiB  
Review
Insight into the Structure and Dynamics of Polymers by Neutron Scattering Combined with Atomistic Molecular Dynamics Simulations
by Arantxa Arbe, Fernando Alvarez and Juan Colmenero
Polymers 2020, 12(12), 3067; https://doi.org/10.3390/polym12123067 - 21 Dec 2020
Cited by 16 | Viewed by 3488
Abstract
Combining neutron scattering and fully atomistic molecular dynamics simulations allows unraveling structural and dynamical features of polymer melts at different length scales, mainly in the intermolecular and monomeric range. Here we present the methodology developed by us and the results of its application [...] Read more.
Combining neutron scattering and fully atomistic molecular dynamics simulations allows unraveling structural and dynamical features of polymer melts at different length scales, mainly in the intermolecular and monomeric range. Here we present the methodology developed by us and the results of its application during the last years in a variety of polymers. This methodology is based on two pillars: (i) both techniques cover approximately the same length and time scales and (ii) the classical van Hove formalism allows easily calculating the magnitudes measured by neutron scattering from the simulated atomic trajectories. By direct comparison with experimental results, the simulated cell is validated. Thereafter, the information of the simulations can be exploited, calculating magnitudes that are experimentally inaccessible or extending the parameters range beyond the experimental capabilities. We show how detailed microscopic insight on structural features and dynamical processes of various kinds has been gained in polymeric systems with different degrees of complexity, and how intriguing questions as the collective behavior at intermediate length scales have been faced. Full article
(This article belongs to the Special Issue State-of-the-Art Polymer Science and Technology in Spain (2020,2021))
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23 pages, 4723 KiB  
Review
Advancements in the Blood–Brain Barrier Penetrating Nanoplatforms for Brain Related Disease Diagnostics and Therapeutic Applications
by Suresh Thangudu, Fong-Yu Cheng and Chia-Hao Su
Polymers 2020, 12(12), 3055; https://doi.org/10.3390/polym12123055 - 20 Dec 2020
Cited by 40 | Viewed by 7589
Abstract
Noninvasive treatments to treat the brain-related disorders have been paying more significant attention and it is an emerging topic. However, overcoming the blood brain barrier (BBB) is a key obstacle to most of the therapeutic drugs to enter into the brain tissue, which [...] Read more.
Noninvasive treatments to treat the brain-related disorders have been paying more significant attention and it is an emerging topic. However, overcoming the blood brain barrier (BBB) is a key obstacle to most of the therapeutic drugs to enter into the brain tissue, which significantly results in lower accumulation of therapeutic drugs in the brain. Thus, administering the large quantity/doses of drugs raises more concerns of adverse side effects. Nanoparticle (NP)-mediated drug delivery systems are seen as potential means of enhancing drug transport across the BBB and to targeted brain tissue. These systems offer more accumulation of therapeutic drugs at the tumor site and prolong circulation time in the blood. In this review, we summarize the current knowledge and advancements on various nanoplatforms (NF) and discusses the use of nanoparticles for successful cross of BBB to treat the brain-related disorders such as brain tumors, Alzheimer’s disease, Parkinson’s disease, and stroke. Full article
(This article belongs to the Special Issue Intelligent Polymeric Delivery System for Biomedical Applications)
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7 pages, 13804 KiB  
Communication
Fabrication and Biocompatibility of Electroconductive Silk Fibroin/PEDOT: PSS Composites for Corneal Epithelial Regeneration
by Promita Bhattacharjee and Mark Ahearne
Polymers 2020, 12(12), 3028; https://doi.org/10.3390/polym12123028 - 17 Dec 2020
Cited by 10 | Viewed by 2801
Abstract
The aim of this study was to develop matrices that can support human corneal epithelial cells and innervation by incorporating a conducting polymer, poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) (PEDOT:PSS), into silk fibroin (SF). Polyvinyl alcohol (PVA) was used as a crosslinking agent to enhance the [...] Read more.
The aim of this study was to develop matrices that can support human corneal epithelial cells and innervation by incorporating a conducting polymer, poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) (PEDOT:PSS), into silk fibroin (SF). Polyvinyl alcohol (PVA) was used as a crosslinking agent to enhance the mechanical properties of the matrices. The impact of PEDOT:PSS on the materials’ physical properties and cellular responses was examined. The electrical impedance of matrices decreased with increasing concentration of PEDOT:PSS suggesting improved electroconductivity. However, light transmittance also decreased with increasing PEDOT:PSS. Young’s modulus was unaffected by PEDOT:PSS but was increased by PVA. The viability of corneal epithelial cell on the matrices was unaffected by the incorporation of PEDOT:PSS except at the highest concentration tested 0.3% (w/v), which led to a cytotoxic response. These findings suggest that SF/PEDOT:PSS with a PEDOT:PSS concentration of 0.1–0.2% would be a suitable biomaterial for epithelium regeneration. Full article
(This article belongs to the Section Biomacromolecules, Biobased and Biodegradable Polymers)
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18 pages, 29825 KiB  
Article
Multiple-Color Reflectors Using Bichiral Liquid Crystal Polymer Films and Their Applications in Liquid Crystal Displays
by Cheng-Kai Liu, Ming-Hsien Li, Chi-Lun Ting, Andy Ying-Guey Fuh and Ko-Ting Cheng
Polymers 2020, 12(12), 3031; https://doi.org/10.3390/polym12123031 - 17 Dec 2020
Cited by 2 | Viewed by 2330
Abstract
Multiple-color reflectors using bichiral liquid crystal polymer films (BLCPFs) are investigated. The BLCPFs consist of alternate layers of two different single-pitch cholesteric liquid crystal (CLC) layers, named CLC#A and CLC#B. The thickness of each CLC layer equals its single pitch length. The optical [...] Read more.
Multiple-color reflectors using bichiral liquid crystal polymer films (BLCPFs) are investigated. The BLCPFs consist of alternate layers of two different single-pitch cholesteric liquid crystal (CLC) layers, named CLC#A and CLC#B. The thickness of each CLC layer equals its single pitch length. The optical properties in terms of reflections, reflection-wavelength ranges, and distributions of reflection spectra of the BLCPFs that result from the fixed pitch length of CLC#A along with the decrease of the pitch length of CLC#B are qualitatively simulated and investigated. The results indicate that the above optical properties of the BLCPFs depend on the LC birefringence and pitch lengths of CLC#A and CLC#B layers. The concept of fabrication method of the BLCPFs by using polymerizable CLCs and thin films of poly(vinylalcohol) or photoalignment materials is discussed. They have potential practical applications in functional color filters, asymmetrical transmission systems, etc., owing to the multiple reflection bands of BLCPFs. Moreover, the BLCPFs, which can enhance the color gamut and light-utilization efficiency of light sources/LC displays, are reported herein. Full article
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16 pages, 3638 KiB  
Article
Monitoring of Peroxide in Gamma Irradiated EVA Multilayer Film Using Methionine Probe
by Nina Girard-Perier, Magalie Claeys-Bruno, Sylvain R. A. Marque, Nathalie Dupuy, Fanny Gaston and Samuel Dorey
Polymers 2020, 12(12), 3024; https://doi.org/10.3390/polym12123024 - 17 Dec 2020
Cited by 4 | Viewed by 1567
Abstract
In this study, the oxidation of methionine is used as a proxy to model the gamma radiation-induced changes in single-use bags; these changes lead to the formation of acids, radicals, and hydroperoxides. The mechanisms of formation of these reactive species and of methionine [...] Read more.
In this study, the oxidation of methionine is used as a proxy to model the gamma radiation-induced changes in single-use bags; these changes lead to the formation of acids, radicals, and hydroperoxides. The mechanisms of formation of these reactive species and of methionine oxidation are discussed. With the help of reaction kinetics, the optimal conditions for the use of these single-use bags minimizing the impact of radical chemistry are highlighted. Biopharmaceutical bags gamma irradiated from 0 kGy to 260 kGy and aged from 0 to 36 months were filled with a methionine solution to follow the oxidation of the methionine. The methionine sulfoxide was measured with HPLC after different storage times (0, 3, 10, 14, 17, and 21 days). Three main results were analyzed through a design of experiments: the oxidative induction time, the methionine sulfoxide formation rate, and the maximum methionine sulfoxide concentration detected. A key aspect of the study is that it highlights that methionine is oxidized not necessarily directly by hydro(gen) peroxide but throughperacid, and likely peracetic acid. The answers to the design of experiments were considered to obtain the desirability domain for the optimization of the conditions of use for the single-use bags limiting the oxidation of methionine as well as the release of reactive species thereof. Full article
(This article belongs to the Section Polymer Chemistry)
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16 pages, 3413 KiB  
Article
Characterization of Porcine Urinary Bladder Matrix Hydrogels from Sodium Dodecyl Sulfate Decellularization Method
by Chen-Yu Kao, Huynh-Quang-Dieu Nguyen and Yu-Chuan Weng
Polymers 2020, 12(12), 3007; https://doi.org/10.3390/polym12123007 - 16 Dec 2020
Cited by 18 | Viewed by 3255
Abstract
Urinary bladder matrix (UBM) is one of the most studied extracellular matrixes (ECM) in the tissue engineering field. Although almost all of the UBM hydrogels were prepared by using peracetic acid (PAA), recent studies indicated that PAA was not a trustworthy way to [...] Read more.
Urinary bladder matrix (UBM) is one of the most studied extracellular matrixes (ECM) in the tissue engineering field. Although almost all of the UBM hydrogels were prepared by using peracetic acid (PAA), recent studies indicated that PAA was not a trustworthy way to decellularize UBM. A stronger detergent, such as sodium dodecyl sulfate (SDS), may help tackle this issue; however, its effects on the hydrogels’ characteristics remain unknown. Therefore, the objective of this study was to develop a more reliable protocol to decellularize UBM, using SDS, and to compare the characteristics of hydrogels obtained from this method to the widely employed technique, using PAA. The results indicated that SDS was superior to PAA in decellularization efficacy. Different decellularization methods led to dissimilar gelation kinetics; however, the methods did not affect other hydrogel characteristics in terms of biochemical composition, surface morphology and rheological properties. The SDS-treated hydrogels possessed excellent cytocompatibility in vitro. These results showed that the SDS decellularization method could offer a more stable and safer way to obtain acellular UBM, due to reducing immunogenicity. The hydrogels prepared from this technique had comparable characteristics as those from PAA and could be a potential candidate as a scaffold for tissue remodeling. Full article
(This article belongs to the Section Biomacromolecules, Biobased and Biodegradable Polymers)
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21 pages, 734 KiB  
Article
Direct Joule Heating as a Means to Efficiently and Homogeneously Heat Thermoplastic Prepregs
by Jochen Wellekötter and Christian Bonten
Polymers 2020, 12(12), 2959; https://doi.org/10.3390/polym12122959 - 11 Dec 2020
Cited by 6 | Viewed by 3242
Abstract
Although direct Joule heating is a known technique for heating carbon fiber reinforced plastics, it is a yet unexplored heating method for thermoplastic prepregs before back-injection molding. The knowledge obtained from resistance welding, for example, is not directly transferable because of considerably higher [...] Read more.
Although direct Joule heating is a known technique for heating carbon fiber reinforced plastics, it is a yet unexplored heating method for thermoplastic prepregs before back-injection molding. The knowledge obtained from resistance welding, for example, is not directly transferable because of considerably higher heated volumes and more complex shapes. In this study, the governing parameters and process limits are established for this method. The influences of the contacting, the materials used, and the size of the heated part are investigated with respect to the part temperature and heating efficiency. The findings show that the quality of heating is determined by the shape and size of the electrodes. Larger electrodes lead to a more homogeneous temperature distribution. Parts based on woven fabric can be heated more homogeneously because of the existence of intersections between rovings, generating contact between fibers. An increase in part width results in uneven heating behavior. Full article
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18 pages, 2685 KiB  
Review
Photo-Crosslinked Silk Fibroin for 3D Printing
by Xuan Mu, Jugal Kishore Sahoo, Peggy Cebe and David L. Kaplan
Polymers 2020, 12(12), 2936; https://doi.org/10.3390/polym12122936 - 9 Dec 2020
Cited by 56 | Viewed by 9084
Abstract
Silk fibroin in material formats provides robust mechanical properties, and thus is a promising protein for 3D printing inks for a range of applications, including tissue engineering, bioelectronics, and bio-optics. Among the various crosslinking mechanisms, photo-crosslinking is particularly useful for 3D printing with [...] Read more.
Silk fibroin in material formats provides robust mechanical properties, and thus is a promising protein for 3D printing inks for a range of applications, including tissue engineering, bioelectronics, and bio-optics. Among the various crosslinking mechanisms, photo-crosslinking is particularly useful for 3D printing with silk fibroin inks due to the rapid kinetics, tunable crosslinking dynamics, light-assisted shape control, and the option to use visible light as a biocompatible processing condition. Multiple photo-crosslinking approaches have been applied to native or chemically modified silk fibroin, including photo-oxidation and free radical methacrylate polymerization. The molecular characteristics of silk fibroin, i.e., conformational polymorphism, provide a unique method for crosslinking and microfabrication via light. The molecular design features of silk fibroin inks and the exploitation of photo-crosslinking mechanisms suggest the exciting potential for meeting many biomedical needs in the future. Full article
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10 pages, 2574 KiB  
Article
A Novel Silicon/Phosphorus Co-Flame Retardant Polymer Electrolyte for High-Safety All-Solid-State Lithium Ion Batteries
by Li Zeng, Lu Jia, Xingang Liu and Chuhong Zhang
Polymers 2020, 12(12), 2937; https://doi.org/10.3390/polym12122937 - 9 Dec 2020
Cited by 12 | Viewed by 4111
Abstract
Developing a solid polymer electrolyte with superior flame retardancy and lithium-ion transportation properties is still a challenge. Herein, an intrinsic silicon/phosphorus co-flame retardant polymer solid electrolyte was prepared by using polyethylene glycol (PEG) co-polymerized with silicon and phosphorus-containing monomers. Due to the synergistic [...] Read more.
Developing a solid polymer electrolyte with superior flame retardancy and lithium-ion transportation properties is still a challenge. Herein, an intrinsic silicon/phosphorus co-flame retardant polymer solid electrolyte was prepared by using polyethylene glycol (PEG) co-polymerized with silicon and phosphorus-containing monomers. Due to the synergistic flame-retardant effect of silicon and phosphorus elements, this polymer electrolyte exhibits excellent thermal stability and flame resistance. Moreover, the ionic conductivity of the electrolyte at 25 °C is as high as 2.98 × 10−5 S/cm when the mass ratio of LiN(SO2CF3)2 (LiTFSI) and the prepared polymer electrolyte is 10:1. What is more, the LiFePO4/Li all-solid-state battery assembled with this solid electrolyte can work stably at a high temperature of 60 °C and exhibits a specific capacity of 129.2 mAh/g at 0.2 C after 100 cycles, providing a promising application prospect for high-safety lithium-ion batteries. Full article
(This article belongs to the Special Issue Feature Papers of Green and Sustainable Chemistry in Polymer Science)
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14 pages, 1704 KiB  
Article
Drug-Eluting Biodegradable Implants for the Sustained Release of Bisphosphonates
by Cintya Dharmayanti, Todd A. Gillam, Desmond B. Williams and Anton Blencowe
Polymers 2020, 12(12), 2930; https://doi.org/10.3390/polym12122930 - 7 Dec 2020
Cited by 16 | Viewed by 3859
Abstract
Despite being one of the first-line treatments for osteoporosis, the bisphosphonate drug class exhibits an extremely low oral bioavailability (<1%) due to poor absorption from the gastrointestinal tract. To overcome this, and to explore the potential for sustained drug release, bioerodible poly(lactic [...] Read more.
Despite being one of the first-line treatments for osteoporosis, the bisphosphonate drug class exhibits an extremely low oral bioavailability (<1%) due to poor absorption from the gastrointestinal tract. To overcome this, and to explore the potential for sustained drug release, bioerodible poly(lactic acid) (PLA) and poly(D,L-lactide-co-glycolide) (PLGA) implants loaded with the bisphosphonate alendronate sodium (ALN) were prepared via hot-melt extrusion. The rate of drug release in vitro was modulated by tailoring the ratio of lactide to glycolide in the polymer and by altering the ALN-loading of the implants. All investigated implants exhibited sustained ALN release in vitro between 25 to 130 days, where implants of greater glycolide composition and higher ALN-loadings released ALN more rapidly. All PLGA implants demonstrated a sigmoidal release profile, characterised by an initial surface dissolution phase, followed by a period of zero-order drug diffusion, then relaxation or erosion of the polymer chains that caused accelerated release over the subsequent days. Contrastingly, the PLA implants demonstrated a logarithmic release profile, characterised by a gradual decrease in ALN release over time. Full article
(This article belongs to the Collection Polymers for Controlled Drug Release)
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18 pages, 11787 KiB  
Article
Micellar Carriers Based on Amphiphilic PEG/PCL Graft Copolymers for Delivery of Active Substances
by Justyna Odrobińska and Dorota Neugebauer
Polymers 2020, 12(12), 2876; https://doi.org/10.3390/polym12122876 - 30 Nov 2020
Cited by 10 | Viewed by 3429
Abstract
Amphiphilic copolymers of alkyne functionalized 2-hydroxyethyl methacrylate (AlHEMA) and poly(ethylene glycol) methyl ether methacrylate (MPEGMA) with graft or V-shaped graft topologies were synthesized. The functionalization of poly(ε-caprolactone) (PCL) with azide group enabled attachment to P(AlHEMA-co-MPEGMA) copolymers via a “click” alkyne-azide reaction. [...] Read more.
Amphiphilic copolymers of alkyne functionalized 2-hydroxyethyl methacrylate (AlHEMA) and poly(ethylene glycol) methyl ether methacrylate (MPEGMA) with graft or V-shaped graft topologies were synthesized. The functionalization of poly(ε-caprolactone) (PCL) with azide group enabled attachment to P(AlHEMA-co-MPEGMA) copolymers via a “click” alkyne-azide reaction. The introduction of PCL as a second side chain type in addition to PEG resulted in heterografted copolymers with modified properties such as biodegradability. “Click” reactions were carried out with efficiencies between 17–70% or 32–50% (for lower molecular weight PCL, 4000 g/mol, or higher molecular weight PCL, 9000 g/mol, respectively) depending on the PEG grafting density. The graft copolymers were self-assembled into micellar superstructures with the ability to encapsulate active substances, such as vitamin C (VitC), arbutin (ARB) or 4-n-butylresorcinol (4nBRE). Drug loading contents (DLC) were obtained in the range of 5–55% (VitC), 39–91% (ARB) and 42–98% (4nBRE). In vitro studies carried out in a phosphate buffer saline (PBS) solution (at pH 7.4 or 5.5) gave the maximum release levels of active substances after 10–240 min depending on the polymer system. Permeation tests in Franz chambers indicated that the bioactive substances after release by micellar systems penetrated through the artificial skin membrane in small amounts, and a majority of the bioactive substances remained inside the membrane, which is satisfactory for most cosmetic applications. Full article
(This article belongs to the Collection Polymers for Controlled Drug Release)
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14 pages, 7706 KiB  
Article
Phase Separation within a Thin Layer of Polymer Solution as Prompt Technique to Predict Membrane Morphology and Transport Properties
by Tatiana Anokhina, Ilya Borisov, Alexey Yushkin, Gleb Vaganov, Andrey Didenko and Alexey Volkov
Polymers 2020, 12(12), 2785; https://doi.org/10.3390/polym12122785 - 25 Nov 2020
Cited by 15 | Viewed by 2484
Abstract
In this work, the precipitation of a thin layer of a polymer solution was proposed to imitate the process of asymmetric membrane formation by a non-solvent induced phase separation (NIPS) technique. The phase inversion within the thin (<500 μm) and bulk (~2 cm) [...] Read more.
In this work, the precipitation of a thin layer of a polymer solution was proposed to imitate the process of asymmetric membrane formation by a non-solvent induced phase separation (NIPS) technique. The phase inversion within the thin (<500 μm) and bulk (~2 cm) layer of polyamic-acid (PAA) in N-methyl-2-pyrrolidone (NMP) by using water as non-solvent was considered. It was shown that polymer films formed within the “limited” layer of polymer solution showed a good agreement with the morphology of corresponded asymmetric flat-sheet membranes even in the case of three-component casting solution (PAA/NMP/EtOH). At the same time, the polymer films formed on the interface of two bulk phases (“infinite” regime) did not fully correspond to the membrane structure. It was shown that up to 50% of NMP solvent in PAA solution can be replaced by ethanol, which can have a renewable origin. By changing the ethanol content in the casting solution, the average size of transport pores can be varied in the range of 12–80 nm, and the liquid permeance from 16.6 up to 207 kg/m2∙h∙bar. To summarize, the precipitation of polymer solution within the thin layer can be considered a prompt technique and a powerful tool for fast screening and optimization of the complex composition of casting solutions using its small quantity. Furthermore, the prediction of membrane morphology can be done without casting the membrane, further post-treatment procedures, and scanning electron microscopy (SEM) analysis. Full article
(This article belongs to the Special Issue Advanced Polymeric Materials for Membrane Technology)
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10 pages, 1533 KiB  
Article
Tandem Mass-Remainder Analysis of Industrially Important Polyether Polyols
by Mahir Hashimov, Ákos Kuki, Tibor Nagy, Miklós Zsuga and Sándor Kéki
Polymers 2020, 12(12), 2768; https://doi.org/10.3390/polym12122768 - 24 Nov 2020
Cited by 3 | Viewed by 2092
Abstract
The characteristics of the polyalkylene oxide polyether polyols highly influence the properties of final polyurethane products. As a novel approach, in order to gain structural information, the recently invented data mining procedures, namely the Mass-remainder analysis (MARA) and the Multistep Mass-remainder analysis (M-MARA) [...] Read more.
The characteristics of the polyalkylene oxide polyether polyols highly influence the properties of final polyurethane products. As a novel approach, in order to gain structural information, the recently invented data mining procedures, namely the Mass-remainder analysis (MARA) and the Multistep Mass-remainder analysis (M-MARA) are successfully applied for the processing of tandem mass spectrometry (MS/MS) data of various industrially important polyether polyols. M-MARA yields an ultra-simplified graphical representation of the MS/MS spectra and sorts the product ions based on their double bond equivalent (DBE) values. The maximum DBE values unambiguously differentiate among the various polyether polyols. Accordingly, the characteristic DBE values were 0, 1 for the linear diol polyethers, 0, 1, 2 for the three-arm, and 0, 1 2, 3, 4 for the six-arm polyether polyols. In addition, it was also found that the characteristic collision energy necessary for the optimum fragmentation yield depended linearly on the molecular weight of the polyols. This relationship offers an easy way for instrument tuning to gain structural information. Full article
(This article belongs to the Section Polymer Analysis and Characterization)
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16 pages, 9992 KiB  
Article
Reliability of Free Inflation and Dynamic Mechanics Tests on the Prediction of the Behavior of the Polymethylsilsesquioxane–High-Density Polyethylene Nanocomposite for Thermoforming Applications
by Fouad Erchiqui, Khaled Zaafrane, Abdessamad Baatti, Hamid Kaddami and Abdellatif Imad
Polymers 2020, 12(11), 2753; https://doi.org/10.3390/polym12112753 - 21 Nov 2020
Cited by 2 | Viewed by 1923
Abstract
Numerical modeling of the thermoforming process of polymeric sheets requires precise knowledge of the viscoelastic behavior under conjugate effect pressure and temperature. Using two different experiments, bubble inflation and dynamic mechanical testing on a high-density polyethylene (HDPE) nanocomposite reinforced with polymethylsilsesquioxane HDPE (PMSQ–HDPE) [...] Read more.
Numerical modeling of the thermoforming process of polymeric sheets requires precise knowledge of the viscoelastic behavior under conjugate effect pressure and temperature. Using two different experiments, bubble inflation and dynamic mechanical testing on a high-density polyethylene (HDPE) nanocomposite reinforced with polymethylsilsesquioxane HDPE (PMSQ–HDPE) nanoparticles, material constants for Christensen’s model were determined by the least squares optimization. The viscoelastic identification relative to the inflation test seemed to be the most appropriate for the numerical study of thermoforming of a thin PMSQ–HDPE part. For this purpose, the finite element method was considered. Full article
(This article belongs to the Special Issue Rheology and Processing of Polymers)
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13 pages, 1793 KiB  
Article
Kinetic Study of the Thermal and Thermo-Oxidative Degradations of Polystyrene Reinforced with Multiple-Cages POSS
by Ignazio Blanco, Gianluca Cicala, Claudio Tosto and Francesco Agatino Bottino
Polymers 2020, 12(11), 2742; https://doi.org/10.3390/polym12112742 - 19 Nov 2020
Cited by 6 | Viewed by 2000
Abstract
A comprehensive kinetics degradation study is carried out on novel multiple cages polyhedral oligomeric silsesquioxane (POSS)/polystyrene (PS) composites at 5% (w/w) of POSS to assess their thermal behavior with respect to the control PS and other similar POSS/PS systems [...] Read more.
A comprehensive kinetics degradation study is carried out on novel multiple cages polyhedral oligomeric silsesquioxane (POSS)/polystyrene (PS) composites at 5% (w/w) of POSS to assess their thermal behavior with respect to the control PS and other similar POSS/PS systems studied in the past. The composites are synthesized by in situ polymerization of styrene in the presence of POSSs and characterized by 1H-NMR. The characteristics of thermal parameters are determined using kinetics literature methods, such as those developed by Kissinger and Flynn, Wall, and Ozawa (FWO), and discussed and compared with each other and with those obtained in the past for similar POSS/PS composites. A good improvement in the thermal stability with respect to neat polymer is found, but not with respect to those obtained in the past for polystyrene reinforced with single- or double-POSS cages. This behavior is attributed to the greater steric hindrance of the three-cages POSS compared with those of single- or double-cage POSS molecules. Full article
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22 pages, 7012 KiB  
Article
Composites Based on Poly(Lactic Acid) (PLA) and SBA-15: Effect of Mesoporous Silica on Thermal Stability and on Isothermal Crystallization from Either Glass or Molten State
by Tamara M. Díez-Rodríguez, Enrique Blázquez-Blázquez, Ernesto Pérez and María L. Cerrada
Polymers 2020, 12(11), 2743; https://doi.org/10.3390/polym12112743 - 19 Nov 2020
Cited by 15 | Viewed by 2740
Abstract
Several composites based on an L-rich poly(lactic acid) (PLA) with different contents of mesoporous Santa Barbara Amorphous (SBA-15) silica were prepared in order to evaluate the effect of the mesoporous silica on the resultant PLA materials by examining morphological aspects, changes in [...] Read more.
Several composites based on an L-rich poly(lactic acid) (PLA) with different contents of mesoporous Santa Barbara Amorphous (SBA-15) silica were prepared in order to evaluate the effect of the mesoporous silica on the resultant PLA materials by examining morphological aspects, changes in PLA phases and their transitions, and, primarily, the influence on some final properties. Melt extrusion was chosen for the obtainment of the composites, followed by quenching from the melt to prepare films. Completely amorphous samples were then attained, as deduced from X-ray diffraction and differential scanning calorimetry (DSC) analyses. Thermogravimetric analysis (TGA) results demonstrated that the presence of SBA-15 particles in the PLA matrix did not exert any significant influence on the thermal decomposition of these composites. An important nucleation effect of the silica was found in PLA, especially under isothermal crystallization either from the melt or from its glassy state. As expected, isothermal crystallization from the glass was considerably faster than from the molten state, and these high differences were also responsible for a more considerable nucleating role of SBA-15 when crystallizing from the melt. It is remarkable that the PLA under analysis showed very close temperatures for cold crystallization and its subsequent melting. Moreover, the type of developed polymorphs did not accomplish the common rules previously described in the literature. Thus, all the isothermal experiments led to exclusive formation of the α modification, and the observation of the α’ crystals required the annealing for long times at temperatures below 80 °C, as ascertained by both DSC and X-ray diffraction experiments. Finally, microhardness (MH) measurements indicated a competition between the PLA physical aging and the silica reinforcement effect in the as-processed amorphous films. Physical aging in the neat PLA was much more important than in the PLA matrix that constituted the composites. Accordingly, the MH trend with SBA-15 content was strongly dependent on aging times. Full article
(This article belongs to the Special Issue Biodegradable Polymer Nanocomposites)
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9 pages, 2006 KiB  
Communication
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://doi.org/10.3390/polym12112637 - 10 Nov 2020
Cited by 5 | Viewed by 2572
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 [...] Read more.
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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19 pages, 10959 KiB  
Article
Poly(3-Hydroxybutyrate)-Multiwalled Carbon Nanotubes Electrospun Scaffolds Modified with Curcumin
by Nader Tanideh, Negar Azarpira, Najmeh Sarafraz, Shahrokh Zare, Aida Rowshanghiyas, Nima Farshidfar, Aida Iraji, Moein Zarei and Miroslawa El Fray
Polymers 2020, 12(11), 2588; https://doi.org/10.3390/polym12112588 - 4 Nov 2020
Cited by 21 | Viewed by 3655
Abstract
Appropriate selection of suitable materials and methods is essential for scaffolds fabrication in tissue engineering. The major challenge is to mimic the structure and functions of the extracellular matrix (ECM) of the native tissues. In this study, an optimized 3D structure containing poly(3-hydroxybutyrate) [...] Read more.
Appropriate selection of suitable materials and methods is essential for scaffolds fabrication in tissue engineering. The major challenge is to mimic the structure and functions of the extracellular matrix (ECM) of the native tissues. In this study, an optimized 3D structure containing poly(3-hydroxybutyrate) (P3HB), multiwalled carbon nanotubes (MCNTs) and curcumin (CUR) was created by electrospinning a novel biomimetic scaffold. CUR, a natural anti-inflammatory compound, has been selected as a bioactive component to increase the biocompatibility and reduce the potential inflammatory reaction of electrospun scaffolds. The presence of CUR in electrospun scaffolds was confirmed by 1H NMR and Fourier-transform infrared spectroscopy (FTIR). Scanning electron microscopy (SEM) revealed highly interconnected porosity of the obtained 3D structures. Addition of up to 20 wt% CUR has enhanced mechanical properties of the scaffolds. CUR has also promoted in vitro bioactivity and hydrolytic degradation of the electrospun nanofibers. The developed P3HB-MCNT composite scaffolds containing 20 wt% of CUR revealed excellent in vitro cytocompatibility using mesenchymal stem cells and in vivo biocompatibility in rat animal model study. Importantly, the reduced inflammatory reaction in the rat model after 8 weeks of implantation has also been observed for scaffolds modified with CUR. Overall, newly developed P3HB-MCNTs-CUR electrospun scaffolds have demonstrated their high potential for tissue engineering applications. Full article
(This article belongs to the Special Issue Polymeric Materials for Regenerative Medicine and Advanced Structures)
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10 pages, 798 KiB  
Article
Hyperbranched Polyglycerols as Robust Up-Conversion Nanoparticle Coating Layer for Feasible Cell Imaging
by Mingcong Hao, Tongtong Wu, Qunzhi Chen, Xueyan Lian, Haigang Wu and Bingyang Shi
Polymers 2020, 12(11), 2592; https://doi.org/10.3390/polym12112592 - 4 Nov 2020
Cited by 6 | Viewed by 1680
Abstract
Owing to the wide spectrum of excitation wavelengths of up-conversion nanoparticles (UCNPs) by precisely regulating the percentage of doping elements, UCNPs have been emerging as bioimaging agents. The key drawback of UCNPs is their poor dispersibility in aqueous solution and it is hard [...] Read more.
Owing to the wide spectrum of excitation wavelengths of up-conversion nanoparticles (UCNPs) by precisely regulating the percentage of doping elements, UCNPs have been emerging as bioimaging agents. The key drawback of UCNPs is their poor dispersibility in aqueous solution and it is hard to introduce the chemical versatility of function groups. In our study, we present a robust and feasible UCNP modification approach by introducing hyperbranched polyglycerols (hbPGs) as a coating layer. When grafted by hbPGs, the solubility and biocompatibility of UCNPs are significantly improved. Moreover, we also systematically investigated and optimized the chemical modification approach of amino acids or green fluorescence protein (GFP), respectively, grafting onto hbPGs and hbPGs-g-UCNP by oxidizing the vicinal diol to be an aldehyde group, which reacts more feasibly with amino-containing functional molecules. Then, we investigated the drug-encapsulating properties of hbPGs-Arg with DOX and cell imaging of GFP-grafted hbPGs-g-UCNP, respectively. The excellent cell imaging in tumor cells indicated that hbPG-modification of UCNPs displayed potential for applications in drug delivery and disease diagnosis. Full article
(This article belongs to the Special Issue Polymers for Diagnostics and Therapy)
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21 pages, 65081 KiB  
Article
Polymer Conformations, Entanglements and Dynamics in Ionic Nanocomposites: A Molecular Dynamics Study
by Ahmad Moghimikheirabadi, Clément Mugemana, Martin Kröger and Argyrios V. Karatrantos
Polymers 2020, 12(11), 2591; https://doi.org/10.3390/polym12112591 - 4 Nov 2020
Cited by 10 | Viewed by 4092
Abstract
We investigate nanoparticle (NP) dispersion, polymer conformations, entanglements and dynamics in ionic nanocomposites. To this end, we study nanocomposite systems with various spherical NP loadings, three different molecular weights, two different Bjerrum lengths, and two types of charge-sequenced polymers by means of molecular [...] Read more.
We investigate nanoparticle (NP) dispersion, polymer conformations, entanglements and dynamics in ionic nanocomposites. To this end, we study nanocomposite systems with various spherical NP loadings, three different molecular weights, two different Bjerrum lengths, and two types of charge-sequenced polymers by means of molecular dynamics simulations. NP dispersion can be achieved in either oligomeric or entangled polymeric matrices due to the presence of electrostatic interactions. We show that the overall conformations of ionic oligomer chains, as characterized by their radii of gyration, are affected by the presence and the amount of charged NPs, while the dimensions of charged entangled polymers remain unperturbed. Both the dynamical behavior of polymers and NPs, and the lifetime and amount of temporary crosslinks, are found to depend on the ratio between the Bjerrum length and characteristic distance between charged monomers. Polymer–polymer entanglements start to decrease beyond a certain NP loading. The dynamics of ionic NPs and polymers is very different compared with their non-ionic counterparts. Specifically, ionic NP dynamics is getting enhanced in entangled matrices and also accelerates with the increase of NP loading. Full article
(This article belongs to the Special Issue Theory of Polymers at Interfaces)
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14 pages, 5629 KiB  
Article
In-Situ Observations of Microscale Ductility in a Quasi-Brittle Bulk Scale Epoxy
by Olivier Verschatse, Lode Daelemans, Wim Van Paepegem and Karen De Clerck
Polymers 2020, 12(11), 2581; https://doi.org/10.3390/polym12112581 - 3 Nov 2020
Cited by 10 | Viewed by 2522
Abstract
Fiber reinforced composite materials are typically comprised of two phases, i.e., the reinforcing fibers and a surrounding matrix. At a high volume fraction of reinforcing fibers, the matrix is confined to a microscale region in between the fibers (1–200 µm). Although these regions [...] Read more.
Fiber reinforced composite materials are typically comprised of two phases, i.e., the reinforcing fibers and a surrounding matrix. At a high volume fraction of reinforcing fibers, the matrix is confined to a microscale region in between the fibers (1–200 µm). Although these regions are interconnected, their behavior is likely dominated by their micro-scale. Nevertheless, the characterization of the matrix material (without reinforcing fibers) is usually performed on macroscopic bulk specimens and little is known about the micro-mechanical behavior of polymer matrix materials. Here, we show that the microscale behavior of an epoxy resin typically used in composite production is clearly different from its macroscale behavior. Microscale polymer specimens were produced by drawing microfibers from vitrifying epoxy resin. After curing, tensile tests were performed on a large set of pure epoxy microfiber specimens with diameters ranging from 30 to 400 µm. An extreme ductility was observed for microscale epoxy specimens, while bulk scale epoxy specimens showed brittle behavior. The microsized epoxy specimens had a plastic deformation behavior resulting in a substantially higher ultimate tensile strength (up to 380 MPa) and strain at break (up to 130 %) compared to their bulk counterpart (68 MPa and 8%). Polarized light microscopy confirmed a rearrangement of the internal epoxy network structure during loading, resulting in the plastic deformation of the microscale epoxy. This was further accompanied by in-situ electron microscopy to further determine the deformation behavior of the micro-specimens during tensile loading and make accurate strain measurements using video-extensometry. This work thus provides novel insights on the epoxy material behavior at the confined microscale as present in fiber reinforced composite materials. Full article
(This article belongs to the Special Issue Epoxy Resins and Composites)
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19 pages, 1764 KiB  
Article
Topological Disentanglement of Linear Polymers under Tension
by Michele Caraglio, Boris Marcone, Fulvio Baldovin, Enzo Orlandini and Attilio L. Stella
Polymers 2020, 12(11), 2580; https://doi.org/10.3390/polym12112580 - 3 Nov 2020
Cited by 6 | Viewed by 2251
Abstract
We develop a theoretical description of the topological disentanglement occurring when torus knots reach the ends of a semiflexible polymer under tension. These include decays into simpler knots and total unknotting. The minimal number of crossings and the minimal knot contour length are [...] Read more.
We develop a theoretical description of the topological disentanglement occurring when torus knots reach the ends of a semiflexible polymer under tension. These include decays into simpler knots and total unknotting. The minimal number of crossings and the minimal knot contour length are the topological invariants playing a key role in the model. The crossings behave as particles diffusing along the chain and the application of appropriate boundary conditions at the ends of the chain accounts for the knot disentanglement. Starting from the number of particles and their positions, suitable rules allow reconstructing the type and location of the knot moving on the chain Our theory is extensively benchmarked with corresponding molecular dynamics simulations and the results show a remarkable agreement between the simulations and the theoretical predictions of the model. Full article
(This article belongs to the Special Issue Semiflexible Polymers II)
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11 pages, 4507 KiB  
Article
Effects of SiO2 Filler in the Shell and Wood Fiber in the Core on the Thermal Expansion of Core–Shell Wood/Polyethylene Composites
by Lichao Sun, Haiyang Zhou, Guanggong Zong, Rongxian Ou, Qi Fan, Junjie Xu, Xiaolong Hao and Qiong Guo
Polymers 2020, 12(11), 2570; https://doi.org/10.3390/polym12112570 - 2 Nov 2020
Cited by 10 | Viewed by 2445
Abstract
The influence of nano-silica (nSiO2) and micro-silica (mSiO2) in the shell and wood fiber filler in the core on the thermal expansion behavior of co-extruded wood/polyethylene composites (Co-WPCs) was investigated to optimize the thermal expansion resistance. The cut Co-WPCs [...] Read more.
The influence of nano-silica (nSiO2) and micro-silica (mSiO2) in the shell and wood fiber filler in the core on the thermal expansion behavior of co-extruded wood/polyethylene composites (Co-WPCs) was investigated to optimize the thermal expansion resistance. The cut Co-WPCs samples showed anisotropic thermal expansion, and the thermal expansion strain and linear coefficient of thermal expansion (LCTE) decreased by filling the shell layer with rigid silica, especially nSiO2. Finite element analysis indicated that the polymer-filled shell was mainly responsible for the thermal expansion. The entire Co-WPCs samples exhibited a lower thermal expansion strain than the cut Co-WPCs samples due to protection by the shell. Increasing the wood fiber content in the core significantly decreased the thermal expansion strain and LCTE of the Co-WPCs. The Co-WPCs whose core layer was filled with 70% wood fiber exhibited the greatest anisotropic thermal expansion. Full article
(This article belongs to the Special Issue Recent Developments in Eco-Friendly Wood-Based Composites)
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10 pages, 1902 KiB  
Article
Re-Processing of Multilayer Plastic Materials as a Part of the Recycling Process: The Features of Processed Multilayer Materials
by Ville Lahtela, Shekhar Silwal and Timo Kärki
Polymers 2020, 12(11), 2517; https://doi.org/10.3390/polym12112517 - 28 Oct 2020
Cited by 20 | Viewed by 5186
Abstract
The weight of packaging materials will be increased with advanced innovations, such as multilayer plastic. The consequence of the advanced innovations is challenges in the following reuse activities. This study aimed to investigate the properties of multilayer plastic materials after recycling processes and [...] Read more.
The weight of packaging materials will be increased with advanced innovations, such as multilayer plastic. The consequence of the advanced innovations is challenges in the following reuse activities. This study aimed to investigate the properties of multilayer plastic materials after recycling processes and will increase the awareness of plastic packaging material for reuse options. In this research, the materials were produced from food packages by crushing them and treating them with injection molding equipment. The implementation of materials in the processing was tested, and the structural and mechanical characteristics of the produced plastic materials was evaluated and discussed. Based on the completed tests, plastic materials used in food packages have the clearest differences in the material features, for instance, the melt flow rate and elongation rate in the tensile test that varied between 2.96–48.4 g/10min and 2–289%, respectively. The variation in the characterizations ranged widely between the material structures. The results indicate that solid plastic packaging materials have better mechanical features compared to foil materials. The structural analysis of materials showed that multilayer plastic includes a wide spectrum of different elements within materials, creating a challenge for future recycling. Full article
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10 pages, 2862 KiB  
Communication
Characteristics of Thermosetting Polymer Nanocomposites: Siloxane-Imide-Containing Benzoxazine with Silsesquioxane Epoxy Resins
by Chih-Hao Lin, Wen-Bin Chen, Wha-Tzong Whang and Chun-Hua Chen
Polymers 2020, 12(11), 2510; https://doi.org/10.3390/polym12112510 - 28 Oct 2020
Cited by 11 | Viewed by 2577
Abstract
A series of innovative thermosetting polymer nanocomposites comprising of polysiloxane-imide-containing benzoxazine (PSiBZ) as the matrix and double-decker silsesquioxane (DDSQ) epoxy or polyhedral oligomeric silsesquioxane (POSS) epoxy were prepared for improving thermosetting performance. Thermomechanical and dynamic mechanical characterizations indicated that both DDSQ and POSS [...] Read more.
A series of innovative thermosetting polymer nanocomposites comprising of polysiloxane-imide-containing benzoxazine (PSiBZ) as the matrix and double-decker silsesquioxane (DDSQ) epoxy or polyhedral oligomeric silsesquioxane (POSS) epoxy were prepared for improving thermosetting performance. Thermomechanical and dynamic mechanical characterizations indicated that both DDSQ and POSS could effectively lower the coefficient of thermal expansion by up to approximately 34% and considerably increase the storage modulus (up to 183%). Therefore, DDSQ and POSS are promising materials for low-stress encapsulation for electronic packaging applications. Full article
(This article belongs to the Section Polymer Applications)
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14 pages, 5975 KiB  
Article
Topology Optimization of Metal and Carbon Fiber Reinforced Plastic (CFRP) Laminated Battery-Hanging Structure
by Jiaju Chen, Yanan Xu and Yunkai Gao
Polymers 2020, 12(11), 2495; https://doi.org/10.3390/polym12112495 - 27 Oct 2020
Cited by 7 | Viewed by 2694
Abstract
This study addressed the topology optimization of a carbon fiber reinforced plastic (CFRP) laminated battery-hanging structure of an electric vehicle. To accommodate parameterization for thickness and orientation of CFRP materials, the discrete material and thickness optimization (DMTO) technique was adopted. To include metal [...] Read more.
This study addressed the topology optimization of a carbon fiber reinforced plastic (CFRP) laminated battery-hanging structure of an electric vehicle. To accommodate parameterization for thickness and orientation of CFRP materials, the discrete material and thickness optimization (DMTO) technique was adopted. To include metal material as a reinforcement structure into the optimization simultaneously, the DMTO technique was extended here to achieve concurrent optimization of CFRP thickness topology, CFRP orientation selection and the topology of the metal reinforcement plate. Manufacturing constraints were applied, including suppressing intermediate void across the thickness direction of the laminate, contiguity constraint and the symmetrical layers. Sensitivities of the objective function were derived with respect to design variables. To calculate analytical sensitivities, finite element analysis was conducted and strain vectors were exported from a commercial software (ABAQUS) into a mathematical analysis tool (MATLAB). The design objective was to minimize the local displacement subject to the constraints of manufacturing and mass fraction. The mechanical performance of the optimized CFRP structure was compared with the original steel structure. To validate the optimization results, a prototype of the CFRP battery-hanging structure was fabricated and experimental testing was conducted. The results show that the total mass of the CFRP battery-hanging structure was reduced by 34.3% when compared with the steel one, while the mechanical property was improved by 25.3%. Full article
(This article belongs to the Special Issue Carbon Based on Fibers, Polymers and Composites)
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16 pages, 5605 KiB  
Article
Morphological Changes in Astrocytes by Self-Oxidation of Dopamine to Polydopamine and Quantification of Dopamine through Multivariate Regression Analysis of Polydopamine Images
by Anik Karan, Elnaz Khezerlou, Farnaz Rezaei, Leon Iasemidis and Mark A. DeCoster
Polymers 2020, 12(11), 2483; https://doi.org/10.3390/polym12112483 - 26 Oct 2020
Cited by 6 | Viewed by 2499
Abstract
Astrocytes, also known as astroglia, are important cells for the structural support of neurons as well as for biochemical balance in the central nervous system (CNS). In this study, the polymerization of dopamine (DA) to polydopamine (PDA) and its effect on astrocytes was [...] Read more.
Astrocytes, also known as astroglia, are important cells for the structural support of neurons as well as for biochemical balance in the central nervous system (CNS). In this study, the polymerization of dopamine (DA) to polydopamine (PDA) and its effect on astrocytes was investigated. The polymerization of DA, being directly proportional to the DA concentration, raises the prospect of detecting DA concentration from PDA optically using image-processing techniques. It was found here that DA, a naturally occurring neurotransmitter, significantly altered astrocyte cell number, morphology, and metabolism, compared to astrocytes in the absence of DA. Along with these effects on astrocytes, the polymerization of DA to PDA was tracked optically in the same cell culture wells. This polymerization process led to a unique methodology based on multivariate regression analysis that quantified the concentration of DA from optical images of astrocyte cell culture media. Therefore, this developed methodology, combined with conventional imaging equipment, could be used in place of high-end and expensive analytical chemistry instruments, such as spectrophotometry, mass spectrometry, and fluorescence techniques, for quantification of the concentration of DA after polymerization to PDA under in vitro and potentially in vivo conditions. Full article
(This article belongs to the Special Issue Biopolymers for Tissue Engineering)
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21 pages, 1956 KiB  
Article
Cellulose Nanofibers from a Dutch Elm Disease-Resistant Ulmus minor Clone
by Laura Jiménez-López, María E. Eugenio, David Ibarra, Margarita Darder, Juan A. Martín and Raquel Martín-Sampedro
Polymers 2020, 12(11), 2450; https://doi.org/10.3390/polym12112450 - 23 Oct 2020
Cited by 18 | Viewed by 2747
Abstract
The potential use of elm wood in lignocellulosic industries has been hindered by the Dutch elm disease (DED) pandemics, which have ravaged European and North American elm groves in the last century. However, the selection of DED-resistant cultivars paves the way for their [...] Read more.
The potential use of elm wood in lignocellulosic industries has been hindered by the Dutch elm disease (DED) pandemics, which have ravaged European and North American elm groves in the last century. However, the selection of DED-resistant cultivars paves the way for their use as feedstock in lignocellulosic biorefineries. Here, the production of cellulose nanofibers from the resistant Ulmus minor clone Ademuz was evaluated for the first time. Both mechanical (PFI refining) and chemical (TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation) pretreatments were assessed prior to microfluidization, observing not only easier fibrillation but also better optical and barrier properties for elm nanopapers compared to eucalyptus ones (used as reference). Furthermore, mechanically pretreated samples showed higher strength for elm nanopapers. Although lower nanofibrillation yields were obtained by mechanical pretreatment, nanofibers showed higher thermal, mechanical and barrier properties, compared to TEMPO-oxidized nanofibers. Furthermore, lignin-containing elm nanofibers presented the most promising characteristics, with slightly lower transparencies. Full article
(This article belongs to the Special Issue Nanocellulose Based Functional Materials)
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18 pages, 4177 KiB  
Article
Phase Equilibrium and Interdiffusion in Poly(Vinyl Methyl Ether)-Water System
by Uliana V. Nikulova and Anatoly E. Chalykh
Polymers 2020, 12(11), 2445; https://doi.org/10.3390/polym12112445 - 22 Oct 2020
Cited by 12 | Viewed by 2006
Abstract
The phase state diagram of the poly(vinyl methyl ether)-water system in a wide concentration range was obtained by the optical interferometry method. It was shown that this system was characterized by a complicated phase equilibrium with two lower critical solution temperatures, one of [...] Read more.
The phase state diagram of the poly(vinyl methyl ether)-water system in a wide concentration range was obtained by the optical interferometry method. It was shown that this system was characterized by a complicated phase equilibrium with two lower critical solution temperatures, one of which was located in the concentrated region at 21 °C, and the other one in the region of a dilute solution at 31 °C. In the framework of the Flory–Huggins theory, pair interaction parameters were calculated for different parts of the binodal curves, and an attempt was made to reverse simulate the diagram in different conditions. It was suggested that the unusual character of the diagram was associated with the formation of a complicated complex between PVME and water in the middle region of the compositions. Concentration profiles for different temperatures were constructed. For the first time for this system, the numerical values of the diffusion coefficients of poly(vinyl methyl ether) (PVME) into water and water in PVME were obtained. Concentration and temperature dependences of diffusion coefficients were constructed and analyzed. The kinetics of water sorption in PVME was plotted, the clustering integral was calculated, and the approximate number of molecules in a water cluster was estimated. It was shown that in the dilute solution region upon passing through the binodal curve, the interphase disappeared immediately, and the remaining fluctuation of the concentration decreased in size with time. The kinetics of this process was estimated from the change in the size of such a particle. Full article
(This article belongs to the Section Polymer Physics and Theory)
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11 pages, 2163 KiB  
Article
Axial Orientation of Co-Crystalline Phases of Poly(2,6-Dimethyl-1,4-Phenylene)Oxide Films
by Manohar Golla, Baku Nagendra, Christophe Daniel, Paola Rizzo and Gaetano Guerra
Polymers 2020, 12(10), 2394; https://doi.org/10.3390/polym12102394 - 17 Oct 2020
Cited by 9 | Viewed by 2326
Abstract
Films exhibiting co-crystalline (CC) phases between a polymer host and low-molecular-mass guest molecules are relevant for many applications. As is usual for semi-crystalline polymers, axially oriented films can give relevant information on the crystalline structure, both by Wide Angle X-ray diffraction fiber patterns [...] Read more.
Films exhibiting co-crystalline (CC) phases between a polymer host and low-molecular-mass guest molecules are relevant for many applications. As is usual for semi-crystalline polymers, axially oriented films can give relevant information on the crystalline structure, both by Wide Angle X-ray diffraction fiber patterns and by polarized Fourier-transform infrared spectroscopy. Axially oriented CC phases of poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) with 1,3,5-trimethylbenzene (mesitylene) can be simply obtained by the stretching of CC PPO films. In fact, due to the plasticization effect of this highly boiling guest, PPO orientation can occur in a stretching temperature range (170–175 °C) nearly 50 °C lower than that generally needed for PPO films (220–230 °C). This low stretching temperature range allows avoidance of polymer oxidation, as well as formation of the mesomorphic dense γ PPO phase. Axially oriented CC phases of PPO with toluene, i.e., with a more volatile guest, can be instead obtained by the stretching (in the same low temperature range: 170–175 °C) of CC PPO blend films with polystyrene. Full article
(This article belongs to the Section Polymer Physics and Theory)
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10 pages, 4516 KiB  
Communication
Urethane-Acrylate/Aramid Nanocomposites Based on Graphenic Materials. A Comparative Study of Their Mechanical Properties
by Israel Gago, Manuel del Río, Gerardo León and Beatriz Miguel
Polymers 2020, 12(10), 2388; https://doi.org/10.3390/polym12102388 - 16 Oct 2020
Cited by 1 | Viewed by 1974
Abstract
Urethane-acrylate thermoset resins (UATR) are a new type of polymeric matrix that have recently made a strong breakthrough in the composites sector. This is because of their properties, which make them an advantageous alternative to epoxy resins, especially if they are reinforced with [...] Read more.
Urethane-acrylate thermoset resins (UATR) are a new type of polymeric matrix that have recently made a strong breakthrough in the composites sector. This is because of their properties, which make them an advantageous alternative to epoxy resins, especially if they are reinforced with high-performance fibers such as aramids. Graphene-based nanocomposites are one of the most dynamic research fields in nanotechnology, because graphenic materials greatly improve the properties of traditional composites. This work represents a comparative study of the effect of adding three types of graphenic materials on the mechanical properties of UATR/aramid composites. Several UATR polymeric matrices were doped at 2% w/w with graphene nanoplatelets (GNPs), reduced graphene oxide (rGO) and pristine few-layer graphene (FLG), and reinforced with Twaron CT709 para-aramid fibers. The obtained laminates showed low density (1.38 g·cm−3), a high volumetric fiber–resin ratio (80:20), homogeneous dispersion of the nanoreinforcement, high reproducibility, and easy scalability. The tensile, flexural and impact strength properties of the undoped composite and the graphene-doped nanocomposites were determined. FLG-doped nanocomposites showed the highest increase in all the mentioned mechanical properties and attained a very significant relative improvement over the undoped laminate (up to 134.4% in aCU). Full article
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16 pages, 6769 KiB  
Article
Core-Shell Nanofibers of Polyvinylidene Fluoride-based Nanocomposites as Piezoelectric Nanogenerators
by Deepalekshmi Ponnamma, Mariem Mohammed Chamakh, Abdulrhman Mohmmed Alahzm, Nisa Salim, Nishar Hameed and Mariam Al Ali AlMaadeed
Polymers 2020, 12(10), 2344; https://doi.org/10.3390/polym12102344 - 13 Oct 2020
Cited by 30 | Viewed by 3995
Abstract
Flexible piezoelectric nanogenerators (PENG) are widely applied to harvest sustainable energy from multiple energy sources. The rational and simple design of PENG have great potential in soft electronics. Here we design a highly flexible PENG using the polyvinylidene fluoride (PVDF) and its copolymer, [...] Read more.
Flexible piezoelectric nanogenerators (PENG) are widely applied to harvest sustainable energy from multiple energy sources. The rational and simple design of PENG have great potential in soft electronics. Here we design a highly flexible PENG using the polyvinylidene fluoride (PVDF) and its copolymer, polyvinylidene hexafluoropropylene (PVDF-HFP) with two nanoarchitectures of semiconducting metal oxides, TiO2 and ZnO. The nanotubes of TiO2 and nanoflowers of ZnO are embedded in these different polymeric media by solvent mixing, and new fiber mats are generated by coaxial electrospinning technique. This process aligns the dipoles of polymers and nanomaterials, which is normally a pre-requisite for higher piezo potential. With excellent mechanical strength and flexibility, the tailored lightweight fiber mats are capable of producing good output voltage (a maximum of 14 V) during different mechanical vibrations at various frequencies and in response to human motions. The hybrid nanocomposite PENG is durable and inexpensive and has possible applications in wearable electronics. Full article
(This article belongs to the Special Issue Advances in Polymer Nanofibers)
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20 pages, 7258 KiB  
Article
The Effect of Dye and Pigment Concentrations on the Diameter of Melt-Electrospun Polylactic Acid Fibers
by N.K. Balakrishnan, K. Koenig and G. Seide
Polymers 2020, 12(10), 2321; https://doi.org/10.3390/polym12102321 - 11 Oct 2020
Cited by 22 | Viewed by 3557
Abstract
Sub-microfibers and nanofibers produce more breathable fabrics than coarse fibers and are therefore widely used in the textiles industry. They are prepared by electrospinning using a polymer solution or melt. Solution electrospinning produces finer fibers but requires toxic solvents. Melt electrospinning is more [...] Read more.
Sub-microfibers and nanofibers produce more breathable fabrics than coarse fibers and are therefore widely used in the textiles industry. They are prepared by electrospinning using a polymer solution or melt. Solution electrospinning produces finer fibers but requires toxic solvents. Melt electrospinning is more environmentally friendly, but is also technically challenging due to the low electrical conductivity and high viscosity of the polymer melt. Here we describe the use of colorants as additives to improve the electrical conductivity of polylactic acid (PLA). The addition of colorants increased the viscosity of the melt by >100%, but reduced the electrical resistance by >80% compared to pure PLA (5 GΩ). The lowest electrical resistance of 50 MΩ was achieved using a composite containing 3% (w/w) indigo. However, the thinnest fibers (52.5 µm, 53% thinner than pure PLA fibers) were obtained by adding 1% (w/w) alizarin. Scanning electron microscopy revealed that fibers containing indigo featured polymer aggregates that inhibited electrical conductivity, and thus increased the fiber diameter. With further improvements to avoid aggregation, the proposed melt electrospinning process could complement or even replace industrial solution electrospinning and dyeing. Full article
(This article belongs to the Special Issue Conductive Polymer Composites)
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10 pages, 2567 KiB  
Article
The Role of Interfacial Interactions on the Functional Properties of Ethylene–Propylene Copolymer Containing SiO2 Nanoparticles
by Iman Taraghi, Sandra Paszkiewicz, Izabela Irska, Krzysztof Pypeć and Elżbieta Piesowicz
Polymers 2020, 12(10), 2308; https://doi.org/10.3390/polym12102308 - 9 Oct 2020
Cited by 3 | Viewed by 1675
Abstract
In this paper, the mechanical properties, thermal stability, and transparency of ethylene–propylene copolymer (EPC) elastomer modified with various weight percentages (1, 3, and 5 wt.%) of SiO2 nanofillers have been studied. The nanocomposites were prepared via a simple melt mixing method. The [...] Read more.
In this paper, the mechanical properties, thermal stability, and transparency of ethylene–propylene copolymer (EPC) elastomer modified with various weight percentages (1, 3, and 5 wt.%) of SiO2 nanofillers have been studied. The nanocomposites were prepared via a simple melt mixing method. The morphological results revealed that the nanofillers were uniformly dispersed in the elastomer, where a low concentration of SiO2 (1 wt.%) had been added into the elastomer. The FTIR showed that there are interfacial interactions between EPC matrix and silanol groups of SiO2 nanoparticles. Moreover, by the addition of 1 wt.% of SiO2 in the EPC, the tensile strength and elongation at break of EPC increased by about 38% and 27%, respectively. Finally, all samples were optically transparent, and the transparency of the nanocomposites reduced by increasing the content of SiO2 nanoparticles. Full article
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12 pages, 2189 KiB  
Article
Electrodeposited Polyaniline Nanofibers and MoO3 Nanobelts for High-Performance Asymmetric Supercapacitor with Redox Active Electrolyte
by Wei Meng, Yanlin Xia, Chuanguo Ma and Xusheng Du
Polymers 2020, 12(10), 2303; https://doi.org/10.3390/polym12102303 - 8 Oct 2020
Cited by 18 | Viewed by 3759
Abstract
Transition molybdenum oxides (MoO3) and conductive polymer (polyaniline, PANI) nanomaterials were fabricated and asymmetric supercapacitor (ASC) was assembled with MoO3 nanobelts as negative electrode and PANI nanofibers as a positive electrode. Branched PANI nanofibers with a diameter of 100 nm [...] Read more.
Transition molybdenum oxides (MoO3) and conductive polymer (polyaniline, PANI) nanomaterials were fabricated and asymmetric supercapacitor (ASC) was assembled with MoO3 nanobelts as negative electrode and PANI nanofibers as a positive electrode. Branched PANI nanofibers with a diameter of 100 nm were electrodeposited on Ti mesh substrate and MoO3 nanobelts with width of 30–700 nm were obtained by the hydrothermal reaction method in an autoclave. Redox active electrolyte containing 0.1 M Fe2+/3+ redox couple was adopted in order to enhance the electrochemical performance of the electrode nano-materials. As a result, the PANI electrode shows a great capacitance of 3330 F g−1 at 1 A g−1 in 0.1 M Fe2+/3+/0.5 M H2SO4 electrolyte. The as-assembled ASC achieved a great energy density of 54 Wh kg−1 at power density of 900 W kg−1. In addition, it displayed significant cycle stability and its capacitance even increased to 109% of the original value after 1000 charge–discharge cycles. The superior performance of the capacitors indicates their promising application as energy storage devices. Full article
(This article belongs to the Special Issue Advances in Polymer Nanofibers)
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23 pages, 2549 KiB  
Article
Effect of Clay Nanofillers on the Mechanical and Water Vapor Permeability Properties of Xylan–Alginate Films
by Darrel S. Naidu and Maya J. John
Polymers 2020, 12(10), 2279; https://doi.org/10.3390/polym12102279 - 4 Oct 2020
Cited by 31 | Viewed by 3742
Abstract
In this study, xylan–alginate-based films were reinforced with nanoclays (bentonite or halloysite) by the solvent casting technique. The effect of the nanoclay loadings (1–5 wt %) on various properties—mechanical, optical, thermal, solubility, water sorption, and water vapor permeability (WVP)—of the xylan–alginate films were [...] Read more.
In this study, xylan–alginate-based films were reinforced with nanoclays (bentonite or halloysite) by the solvent casting technique. The effect of the nanoclay loadings (1–5 wt %) on various properties—mechanical, optical, thermal, solubility, water sorption, and water vapor permeability (WVP)—of the xylan–alginate films were examined for their application as food packaging materials. A 5 wt % loading of either bentonite or halloysite resulted in a 49% decrease of the WVP due to the impermeable nature of the silicate layers that make up both bentonite and halloysite. Thermal stability and solubility of the nanocomposite films were not significantly influenced by the presence of the nanoclays, whereas the optical properties were significantly improved when compared to neat xylan–alginate blend. In general, films reinforced with bentonite exhibited superior mechanical and optical properties when compared to both halloysite-based nanocomposite and neat films. Full article
(This article belongs to the Special Issue Multifunctional Ecocomposites)
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36 pages, 7444 KiB  
Review
Polysaccharide-Based In Situ Self-Healing Hydrogels for Tissue Engineering Applications
by Sheila Maiz-Fernández, Leyre Pérez-Álvarez, Leire Ruiz-Rubio, Jose Luis Vilas-Vilela and Senentxu Lanceros-Mendez
Polymers 2020, 12(10), 2261; https://doi.org/10.3390/polym12102261 - 1 Oct 2020
Cited by 35 | Viewed by 5567
Abstract
In situ hydrogels have attracted increasing interest in recent years due to the need to develop effective and practical implantable platforms. Traditional hydrogels require surgical interventions to be implanted and are far from providing personalized medicine applications. However, in situ hydrogels offer a [...] Read more.
In situ hydrogels have attracted increasing interest in recent years due to the need to develop effective and practical implantable platforms. Traditional hydrogels require surgical interventions to be implanted and are far from providing personalized medicine applications. However, in situ hydrogels offer a wide variety of advantages, such as a non-invasive nature due to their localized action or the ability to perfectly adapt to the place to be replaced regardless the size, shape or irregularities. In recent years, research has particularly focused on in situ hydrogels based on natural polysaccharides due to their promising properties such as biocompatibility, biodegradability and their ability to self-repair. This last property inspired in nature gives them the possibility of maintaining their integrity even after damage, owing to specific physical interactions or dynamic covalent bonds that provide reversible linkages. In this review, the different self-healing mechanisms, as well as the latest research on in situ self-healing hydrogels, is presented, together with the potential applications of these materials in tissue regeneration. Full article
(This article belongs to the Special Issue In-Situ Forming and Self-Healing Hydrogels)
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