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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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42 pages, 12062 KiB  
Review
FDM-Based 3D Printing of Polymer and Associated Composite: A Review on Mechanical Properties, Defects and Treatments
by Sachini Wickramasinghe, Truong Do and Phuong Tran
Polymers 2020, 12(7), 1529; https://doi.org/10.3390/polym12071529 - 10 Jul 2020
Cited by 480 | Viewed by 33485
Abstract
Fused deposition modelling (FDM) is one of the fastest-growing additive manufacturing methods used in printing fibre-reinforced composites (FRC). The performances of the resulting printed parts are limited compared to those by other manufacturing methods due to their inherent defects. Hence, the effort to [...] Read more.
Fused deposition modelling (FDM) is one of the fastest-growing additive manufacturing methods used in printing fibre-reinforced composites (FRC). The performances of the resulting printed parts are limited compared to those by other manufacturing methods due to their inherent defects. Hence, the effort to develop treatment methods to overcome these drawbacks has accelerated during the past few years. The main focus of this study is to review the impact of those defects on the mechanical performance of FRC and therefore to discuss the available treatment methods to eliminate or minimize them in order to enhance the functional properties of the printed parts. As FRC is a combination of polymer matrix material and continuous or short reinforcing fibres, this review will thoroughly discuss both thermoplastic polymers and FRCs printed via FDM technology, including the effect of printing parameters such as layer thickness, infill pattern, raster angle and fibre orientation. The most common defects on printed parts, in particular, the void formation, surface roughness and poor bonding between fibre and matrix, are explored. An inclusive discussion on the effectiveness of chemical, laser, heat and ultrasound treatments to minimize these drawbacks is provided by this review. Full article
(This article belongs to the Section Polymer Processing and Engineering)
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24 pages, 4634 KiB  
Article
Biodegradation of Crystalline Cellulose Nanofibers by Means of Enzyme Immobilized-Alginate Beads and Microparticles
by Arnaud Kamdem Tamo, Ingo Doench, Aliuska Morales Helguera, Daniel Hoenders, Andreas Walther and Anayancy Osorio Madrazo
Polymers 2020, 12(7), 1522; https://doi.org/10.3390/polym12071522 - 9 Jul 2020
Cited by 39 | Viewed by 5203
Abstract
Recent advances in nanocellulose technology have revealed the potential of crystalline cellulose nanofibers to reinforce materials which are useful for tissue engineering, among other functions. However, the low biodegradability of nanocellulose can possess some problems in biomedical applications. In this work, alginate particles [...] Read more.
Recent advances in nanocellulose technology have revealed the potential of crystalline cellulose nanofibers to reinforce materials which are useful for tissue engineering, among other functions. However, the low biodegradability of nanocellulose can possess some problems in biomedical applications. In this work, alginate particles with encapsulated enzyme cellulase extracted from Trichoderma reesei were prepared for the biodegradation of crystalline cellulose nanofibers, which carrier system could be incorporated in tissue engineering biomaterials to degrade the crystalline cellulose nanoreinforcement in situ and on-demand during tissue regeneration. Both alginate beads and microparticles were processed by extrusion-dropping and inkjet-based methods, respectively. Processing parameters like the alginate concentration, concentration of ionic crosslinker Ca2+, hardening time, and ionic strength of the medium were varied. The hydrolytic activity of the free and encapsulated enzyme was evaluated for unmodified (CNFs) and TEMPO-oxidized cellulose nanofibers (TOCNFs) in suspension (heterogeneous conditions); in comparison to solubilized cellulose derivatives (homogeneous conditions). The enzymatic activity was evaluated for temperatures between 25–75 °C, pH range from 3.5 to 8.0 and incubation times until 21 d. Encapsulated cellulase in general displayed higher activity compared to the free enzyme over wider temperature and pH ranges and for longer incubation times. A statistical design allowed optimizing the processing parameters for the preparation of enzyme-encapsulated alginate particles presenting the highest enzymatic activity and sphericity. The statistical analysis yielded the optimum particles characteristics and properties by using a formulation of 2% (w/v) alginate, a coagulation bath of 0.2 M CaCl2 and a hardening time of 1 h. In homogeneous conditions the highest catalytic activity was obtained at 55 °C and pH 4.8. These temperature and pH values were considered to study the biodegradation of the crystalline cellulose nanofibers in suspension. The encapsulated cellulase preserved its activity for several weeks over that of the free enzyme, which latter considerably decreased and practically showed deactivation after just 10 d. The alginate microparticles with their high surface area-to-volume ratio effectively allowed the controlled release of the encapsulated enzyme and thereby the sustained hydrolysis of the cellulose nanofibers. The relative activity of cellulase encapsulated in the microparticles leveled-off at around 60% after one day and practically remained at that value for three weeks. Full article
(This article belongs to the Special Issue Natural Polymer Based Micro and Nanoparticles)
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18 pages, 3146 KiB  
Review
Present Status in Polymeric Mouthguards. A Future Area for Additive Manufacturing?
by Ana M. Sousa, Ana C. Pinho, Ana Messias and Ana P. Piedade
Polymers 2020, 12(7), 1490; https://doi.org/10.3390/polym12071490 - 3 Jul 2020
Cited by 23 | Viewed by 9214
Abstract
Athletes from contact sports are more prone to orofacial injuries because of the exposure to possible shocks and collisions derived from physical proximity. The use of protector polymeric mouthguards proved to be useful in the prevention of the described injuries. There are different [...] Read more.
Athletes from contact sports are more prone to orofacial injuries because of the exposure to possible shocks and collisions derived from physical proximity. The use of protector polymeric mouthguards proved to be useful in the prevention of the described injuries. There are different types of mouthguards with varying ranges of protection and prices, but they are all made from polymers and share the same propose: to absorb and dissipate the impact energy resulting from the shocks. As they are used inside the mouth, they should not impair breathing and speaking nor compromise the comfort of the athlete. However, the ideal mouthguard is yet to be created. The choice of the most appropriate polymeric material and the standard required properties have not yet been reported. Regardless of the numerous studies in this field, normalized control parameters for both material characterization and mouthguard fabrication are absent. This paper aims to present a review of the current types of available mouthguards and their properties/characteristics. Moreover, a detailed description of the most common polymers for the fabrication of mouthguards, together with the manufacturing techniques, are discussed. Full article
(This article belongs to the Special Issue Polymer Connect: Polymer Science and Composite Materials)
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11 pages, 5405 KiB  
Article
Internal Residual Strain Measurements in Carbon Fiber-Reinforced Polymer Laminates Curing Process Using Embedded Tilted Fiber Bragg Grating Sensor
by Ke-Ping Ma, Chao-Wei Wu, Yao-Tung Tsai, Ya-Chun Hsu and Chia-Chin Chiang
Polymers 2020, 12(7), 1479; https://doi.org/10.3390/polym12071479 - 1 Jul 2020
Cited by 6 | Viewed by 2608
Abstract
Carbon fiber reinforced plastics (CFRP) have many mechanical properties that are superior to those of conventional structural materials and are becoming more and more widely used. Monitoring the curing process used to produce such composite material is important to ensure the quality of [...] Read more.
Carbon fiber reinforced plastics (CFRP) have many mechanical properties that are superior to those of conventional structural materials and are becoming more and more widely used. Monitoring the curing process used to produce such composite material is important to ensure the quality of the process, especially for the characterization of residual strains after the material has been manufactured. In this study, we present a tilted fiber Bragg grating (TFBG) sensor used to monitor the curing of CFRP composite materials. The TFBG sensor was embedded into the layers of CFRP laminates to study the curing residual strain of the laminates. The experimental results showed that the curing residual stress was about −22.25 MPa, the axial residual strain was −281.351 με, and lateral residual strain of 89.91 με. The TFBG sensor was found to be sensitive to the curing residual strain of the CFRP, meaning that it has potential for use in applications involving composite curing processes. Moreover, it is indeed possible to improve the properties of composite materials via the optimization and monitoring of their curing parameters. Full article
(This article belongs to the Special Issue Selected Papers from IMETI 2021)
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15 pages, 3804 KiB  
Article
Reinforcement of Epoxy Composites with Application of Finely-ground Ochre and Electrophysical Method of the Composition Modification
by Amirbek Bekeshev, Anton Mostovoy, Lyazzat Tastanova, Yulia Kadykova, Svetlana Kalganova and Marina Lopukhova
Polymers 2020, 12(7), 1437; https://doi.org/10.3390/polym12071437 - 27 Jun 2020
Cited by 30 | Viewed by 3562
Abstract
The conducted studies have proven the possibility of the directed control of operational properties of epoxy composites, due to the addition of finely-ground ocher into their composition, and the use of microwave modification of the epoxy composition. The rational content of ocher as [...] Read more.
The conducted studies have proven the possibility of the directed control of operational properties of epoxy composites, due to the addition of finely-ground ocher into their composition, and the use of microwave modification of the epoxy composition. The rational content of ocher as a modifying additive (0.5 parts by mass) and a filler (75 parts by mass) of the epoxy composition has been selected, which ensures the improvement of the studied complex of physical-mechanical properties. It has been proven that ocher affects the structure formation processes and the structure of the epoxy composite, thus increasing its thermal, heat and fire resistance. During the research, the application efficiency has been proven, and the optimal parameters of the microwave modification (power—350 W; duration—30 s) of epoxy compositions filled with ocher, which increase physical-mechanical characteristics of composites, have been selected. Full article
(This article belongs to the Special Issue Epoxy Resins and Composites)
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15 pages, 4949 KiB  
Article
Effects of a Reactive Phosphorus–Sulfur Containing Flame-Retardant Monomer on the Flame Retardancy and Thermal and Mechanical Properties of Unsaturated Polyester Resin
by Kang Dai, Zhenzhen Deng, Guyue Liu, Yutong Wu, Wenbin Xu and Yuan Hu
Polymers 2020, 12(7), 1441; https://doi.org/10.3390/polym12071441 - 27 Jun 2020
Cited by 17 | Viewed by 3567
Abstract
A novel reactive phosphorus and sulfur-containing monomer (bis(acryloxyethyldiphenylphosphate)sulfone, BADPS) was synthesized to enhance the comprehensive performance of unsaturated polyester resin (UPR), and corresponding flame-retardant unsaturated polyester resins (FR-UPRs) with various amounts of BADPS were prepared by radical bulk polymerization. The flame retardancy and [...] Read more.
A novel reactive phosphorus and sulfur-containing monomer (bis(acryloxyethyldiphenylphosphate)sulfone, BADPS) was synthesized to enhance the comprehensive performance of unsaturated polyester resin (UPR), and corresponding flame-retardant unsaturated polyester resins (FR-UPRs) with various amounts of BADPS were prepared by radical bulk polymerization. The flame retardancy and thermal and mechanical properties of the UPR samples were investigated by limiting oxygen index (LOI) measurements, cone calorimetry, differential scanning calorimetry (DSC), a thermogravimetric analysis (TGA), and a tension test. The results showed that the introduction of BADPS remarkably enhanced the flame resistance and high-temperature stability, as well as the tensile performance of UPR. Scanning electron microscopy (SEM), Fourier transform infrared (FTIR), and Raman spectroscopy studies revealed that BADPS can efficaciously promote the formation of UPR char residue with an improved microstructure and increased graphitization degree, which enhancedthe high-temperature stability and char yield of UPR. Additionally, a thermogravimetry-Fourier transform infrared (TG-FTIR) analysis corroborated that the evolution of combustible volatiles from UPR decomposition was substantially restrained by the incorporation of BADPS, which is beneficial for the suppression of fire hazards in UPR. Full article
(This article belongs to the Collection Fire and Polymers)
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12 pages, 924 KiB  
Article
Potential Use of Wollastonite as a Filler in UF Resin Based Medium-Density Fiberboard (MDF)
by Hamid R. Taghiyari, Ayoub Esmailpour, Roya Majidi, Jeffrey J. Morrell, Mohammad Mallaki, Holger Militz and Antonios N. Papadopoulos
Polymers 2020, 12(7), 1435; https://doi.org/10.3390/polym12071435 - 27 Jun 2020
Cited by 23 | Viewed by 3576
Abstract
Urea-formaldehyde (UF) resins are primary petroleum-based, increasing their potential environmental footprint. Identifying additives to reduce the total amount of resin needed without adversely affecting the panel properties could reduce these impacts. Wollastonite is a mineral containing calcium and silica that has been used [...] Read more.
Urea-formaldehyde (UF) resins are primary petroleum-based, increasing their potential environmental footprint. Identifying additives to reduce the total amount of resin needed without adversely affecting the panel properties could reduce these impacts. Wollastonite is a mineral containing calcium and silica that has been used as an additive in a variety of materials and may be useful as a resin extender. Nanoscale wollastonite has been shown to enhance the panel properties but is costly. Micron-scale wollastonite may be a less costly alternative. Medium-density fiberboards were produced by blending a hardwood furnish with UF alone, micron-sized wollastonite alone, or a 9:1 ratio of UF to wollastonite. Panels containing of only wollastonite had poor properties, but the properties of panels with 9:1 UF/wollastonite were similar to the UF-alone panels, except for the internal bond strength. The results suggest that small amounts of micron-sized wollastonite could serve as a resin extender. Further studies are suggested to determine if the micron-sized material has similar positive effects on the resin curing rate. Full article
(This article belongs to the Special Issue Recent Developments in Eco-Friendly Wood-Based Composites)
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15 pages, 3374 KiB  
Article
A Highly Sensitive and Flexible Capacitive Pressure Sensor Based on a Porous Three-Dimensional PDMS/Microsphere Composite
by Young Jung, Wookjin Lee, Kyungkuk Jung, Byunggeon Park, Jinhyoung Park, Jongsoo Ko and Hanchul Cho
Polymers 2020, 12(6), 1412; https://doi.org/10.3390/polym12061412 - 24 Jun 2020
Cited by 70 | Viewed by 6802
Abstract
In recent times, polymer-based flexible pressure sensors have been attracting a lot of attention because of their various applications. A highly sensitive and flexible sensor is suggested, capable of being attached to the human body, based on a three-dimensional dielectric elastomeric structure of [...] Read more.
In recent times, polymer-based flexible pressure sensors have been attracting a lot of attention because of their various applications. A highly sensitive and flexible sensor is suggested, capable of being attached to the human body, based on a three-dimensional dielectric elastomeric structure of polydimethylsiloxane (PDMS) and microsphere composite. This sensor has maximal porosity due to macropores created by sacrificial layer grains and micropores generated by microspheres pre-mixed with PDMS, allowing it to operate at a wider pressure range (~150 kPa) while maintaining a sensitivity (of 0.124 kPa−1 in a range of 0~15 kPa) better than in previous studies. The maximized pores can cause deformation in the structure, allowing for the detection of small changes in pressure. In addition to exhibiting a fast rise time (~167 ms) and fall time (~117 ms), as well as excellent reproducibility, the fabricated pressure sensor exhibits reliability in its response to repeated mechanical stimuli (2.5 kPa, 1000 cycles). As an application, we develop a wearable device for monitoring repeated tiny motions, such as the pulse on the human neck and swallowing at the Adam’s apple. This sensory device is also used to detect movements in the index finger and to monitor an insole system in real-time. Full article
(This article belongs to the Section Polymer Composites and Nanocomposites)
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16 pages, 1853 KiB  
Article
An Innovative Method for the Recycling of Waste Carbohydrate-Based Flours
by Carola Esposito Corcione, Raffaella Striani, Francesca Ferrari, Paolo Visconti, Daniela Rizzo and Antonio Greco
Polymers 2020, 12(6), 1414; https://doi.org/10.3390/polym12061414 - 24 Jun 2020
Cited by 10 | Viewed by 2460
Abstract
This work represents an innovative study that, for the first time, explores the possibility to use waste flours to produce thermoplastic polymeric bio-films. To the best of our knowledge, this is the first time that waste flours, derived from bakeries, pizzerias or pasta [...] Read more.
This work represents an innovative study that, for the first time, explores the possibility to use waste flours to produce thermoplastic polymeric bio-films. To the best of our knowledge, this is the first time that waste flours, derived from bakeries, pizzerias or pasta factories, have been proposed for the production of bio-polymers, as a replacement of neat starch. To this aim, durum waste flour derived from a pasta factory, soft waste flour derived from pizzerias and neat maize starch used as control material were firstly analyzed from dimensional, morphological and chemical points of view. Afterwards, waste flour films were produced by the addition of a nature-based plasticizer, glycerol. Mechanical characterization of the plasticized thermoplastic films, produced by compression molding, evidenced low performances, even in the case of the neat maize starch. In order to improve the mechanical properties, the possibility to include polylactic acid and cardanol-based plasticizer was also investigated. Mass transport properties of all the produced bio-films were investigated by measuring their water vapor permeability and hygroscopic absorption. The durability properties of the bio-films were assessed by accelerated ageing tests, while the bio-degradability of the waste-based films was evaluated by measuring the solubility and the degradation in water. The physicochemical analyses of the novel bio-films evidenced good mechanical properties; specifically, the waste-based films showed a lower hygroscopic absorption and water solubility than those of the blends containing neat starch. Full article
(This article belongs to the Special Issue Eco-Innovative Engineering of the Polymer Material’s Life Cycle)
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14 pages, 3754 KiB  
Article
Transdermal Composite Microneedle Composed of Mesoporous Iron Oxide Nanoraspberry and PVA for Androgenetic Alopecia Treatment
by Jen-Hung Fang, Che-Hau Liu, Ru-Siou Hsu, Yin-Yu Chen, Wen-Hsuan Chiang, Hui-Min David Wang and Shang-Hsiu Hu
Polymers 2020, 12(6), 1392; https://doi.org/10.3390/polym12061392 - 22 Jun 2020
Cited by 45 | Viewed by 5989
Abstract
The transdermal delivery of therapeutic agents amplifying a local concentration of active molecules have received considerable attention in wide biomedical applications, especially in vaccine development and medical beauty. Unlike oral or subcutaneous injections, this approach can not only avoid the loss of efficacy [...] Read more.
The transdermal delivery of therapeutic agents amplifying a local concentration of active molecules have received considerable attention in wide biomedical applications, especially in vaccine development and medical beauty. Unlike oral or subcutaneous injections, this approach can not only avoid the loss of efficacy of oral drugs due to the liver’s first-pass effect but also reduce the risk of infection by subcutaneous injection. In this study, a magneto-responsive transdermal composite microneedle (MNs) with a mesoporous iron oxide nanoraspberry (MIO), that can improve the drug delivery efficiency, was fabricated by using a 3D printing-molding method. With loading of Minoxidil (Mx, a medication commonly used to slow the progression of hair loss and speed the process of hair regrowth), MNs can break the barrier of the stratum corneum through the puncture ability, and control the delivery dose for treating androgenetic alopecia (AGA). By 3D printing process, the sizes and morphologies of MNs is able to be, easily, architected. The MIOs were embedded into the tip of MNs which can deliver Mx as well as generate mild heating for hair growth, which is potentially attributed by the expansion of hair follicle and drug penetration. Compared to the mice without any treatments, the hair density of mice exhibited an 800% improvement after being treated by MNs with MF at 10-days post-treatment. Full article
(This article belongs to the Special Issue Advanced Polymer Nanocomposites)
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45 pages, 3261 KiB  
Review
Stimuli-Responsive Polymeric Nanocarriers for Drug Delivery, Imaging, and Theragnosis
by Sabya Sachi Das, Priyanshu Bharadwaj, Muhammad Bilal, Mahmood Barani, Abbas Rahdar, Pablo Taboada, Simona Bungau and George Z. Kyzas
Polymers 2020, 12(6), 1397; https://doi.org/10.3390/polym12061397 - 22 Jun 2020
Cited by 291 | Viewed by 15230
Abstract
In the past few decades, polymeric nanocarriers have been recognized as promising tools and have gained attention from researchers for their potential to efficiently deliver bioactive compounds, including drugs, proteins, genes, nucleic acids, etc., in pharmaceutical and biomedical applications. Remarkably, these polymeric nanocarriers [...] Read more.
In the past few decades, polymeric nanocarriers have been recognized as promising tools and have gained attention from researchers for their potential to efficiently deliver bioactive compounds, including drugs, proteins, genes, nucleic acids, etc., in pharmaceutical and biomedical applications. Remarkably, these polymeric nanocarriers could be further modified as stimuli-responsive systems based on the mechanism of triggered release, i.e., response to a specific stimulus, either endogenous (pH, enzymes, temperature, redox values, hypoxia, glucose levels) or exogenous (light, magnetism, ultrasound, electrical pulses) for the effective biodistribution and controlled release of drugs or genes at specific sites. Various nanoparticles (NPs) have been functionalized and used as templates for imaging systems in the form of metallic NPs, dendrimers, polymeric NPs, quantum dots, and liposomes. The use of polymeric nanocarriers for imaging and to deliver active compounds has attracted considerable interest in various cancer therapy fields. So-called smart nanopolymer systems are built to respond to certain stimuli such as temperature, pH, light intensity and wavelength, and electrical, magnetic and ultrasonic fields. Many imaging techniques have been explored including optical imaging, magnetic resonance imaging (MRI), nuclear imaging, ultrasound, photoacoustic imaging (PAI), single photon emission computed tomography (SPECT), and positron emission tomography (PET). This review reports on the most recent developments in imaging methods by analyzing examples of smart nanopolymers that can be imaged using one or more imaging techniques. Unique features, including nontoxicity, water solubility, biocompatibility, and the presence of multiple functional groups, designate polymeric nanocues as attractive nanomedicine candidates. In this context, we summarize various classes of multifunctional, polymeric, nano-sized formulations such as liposomes, micelles, nanogels, and dendrimers. Full article
(This article belongs to the Special Issue Polymeric Materials for Drug Delivery Application)
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15 pages, 2720 KiB  
Article
Synthesis and Characterization of a 2,3-Dialkoxynaphthalene-Based Conjugated Copolymer via Direct Arylation Polymerization (DAP) for Organic Electronics
by Ignacio A. Jessop, Aylin Chong, Linda Graffo, María B. Camarada, Catalina Espinoza, Felipe A. Angel, Cesar Saldías, Alain Tundidor-Camba and Claudio A. Terraza
Polymers 2020, 12(6), 1377; https://doi.org/10.3390/polym12061377 - 19 Jun 2020
Cited by 10 | Viewed by 2879
Abstract
Poly[(5,5’-(2,3-bis(2-ethylhexyloxy)naphthalene-1,4-diyl)bis(thiophene-2,2′-diyl))-alt-(2,1,3-benzothiadiazole-4,7-diyl)] (PEHONDTBT) was synthesized for the first time and through direct arylation polymerization (DAP) for use as p-donor material in organic solar cells. Optimized reaction protocol leads to a donor-acceptor conjugated polymer in good yield, with less structural defects than its [...] Read more.
Poly[(5,5’-(2,3-bis(2-ethylhexyloxy)naphthalene-1,4-diyl)bis(thiophene-2,2′-diyl))-alt-(2,1,3-benzothiadiazole-4,7-diyl)] (PEHONDTBT) was synthesized for the first time and through direct arylation polymerization (DAP) for use as p-donor material in organic solar cells. Optimized reaction protocol leads to a donor-acceptor conjugated polymer in good yield, with less structural defects than its analog obtained from Suzuki polycondensation, and with similar or even higher molecular weight than other previously reported polymers based on the 2,3-dialkoxynaphthalene monomer. The batch-to-batch repeatability of the optimized DAP conditions for the synthesis of PEHONDTBT was proved, showing the robustness of the synthetic strategy. The structure of PEHONDTBT was corroborated by NMR, exhibiting good solubility in common organic solvents, good film-forming ability, and thermal stability. PEHONDTBT film presented an absorption band centered at 498 nm, a band gap of 2.15 eV, and HOMO and LUMO energy levels of −5.31 eV and −3.17 eV, respectively. Theoretical calculations were performed to understand the regioselectivity in the synthesis of PEHONDTBT and to rationalize its optoelectronic properties. Bilayer heterojunction organic photovoltaic devices with PEHONDTBT as the donor layer were fabricated to test their photovoltaic performance, affording low power-conversion efficiency in the preliminary studies. Full article
(This article belongs to the Section Polymer Chemistry)
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14 pages, 2915 KiB  
Article
Light Processable Starch Hydrogels
by Camilla Noè, Chiara Tonda-Turo, Annalisa Chiappone, Marco Sangermano and Minna Hakkarainen
Polymers 2020, 12(6), 1359; https://doi.org/10.3390/polym12061359 - 17 Jun 2020
Cited by 47 | Viewed by 7671
Abstract
Light processable hydrogels were successfully fabricated by utilizing maize starch as raw material. To render light processability, starch was gelatinized and methacrylated by simple reaction with methacrylic anhydride. The methacrylated starch was then evaluated for its photocuring reactivity and 3D printability by digital [...] Read more.
Light processable hydrogels were successfully fabricated by utilizing maize starch as raw material. To render light processability, starch was gelatinized and methacrylated by simple reaction with methacrylic anhydride. The methacrylated starch was then evaluated for its photocuring reactivity and 3D printability by digital light processing (DLP). Hydrogels with good mechanical properties and biocompatibility were obtained by direct curing from aqueous solution containing lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP) as photo-initiator. The properties of the hydrogels were tunable by simply changing the concentration of starch in water. Photo-rheology showed that the formulations with 10 or 15 wt% starch started curing immediately and reached G’ plateau after only 60 s, while it took 90 s for the 5 wt% formulation. The properties of the photocured hydrogels were further characterized by rheology, compressive tests, and swelling experiments. Increasing the starch content from 10 to 15 wt% increased the compressive stiffness from 13 to 20 kPa. This covers the stiffness of different body tissues giving promise for the use of the hydrogels in tissue engineering applications. Good cell viability with human fibroblast cells was confirmed for all three starch hydrogel formulations indicating no negative effects from the methacrylation or photo-crosslinking reaction. Finally, the light processability of methacrylated starch by digital light processing (DLP) 3D printing directly from aqueous solution was successfully demonstrated. Altogether the results are promising for future application of the hydrogels in tissue engineering and as cell carriers Full article
(This article belongs to the Collection Sustainable Polymeric Materials from Renewable Resources)
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22 pages, 4131 KiB  
Review
Solar Cells for Indoor Applications: Progress and Development
by Swarup Biswas and Hyeok Kim
Polymers 2020, 12(6), 1338; https://doi.org/10.3390/polym12061338 - 12 Jun 2020
Cited by 74 | Viewed by 8121
Abstract
The Internet of things (IoT) has been rapidly growing in the past few years. IoT connects numerous devices, such as wireless sensors, actuators, and wearable devices, to optimize and monitor daily activities. Most of these devices require power in the microwatt range and [...] Read more.
The Internet of things (IoT) has been rapidly growing in the past few years. IoT connects numerous devices, such as wireless sensors, actuators, and wearable devices, to optimize and monitor daily activities. Most of these devices require power in the microwatt range and operate indoors. To this end, a self-sustainable power source, such as a photovoltaic (PV) cell, which can harvest low-intensity indoor light, is appropriate. Recently, the development of highly efficient PV cells for indoor applications has attracted tremendous attention. Therefore, different types of PV materials, such as inorganic, dye-sensitized, organic, and perovskite materials, have been employed for harvesting low-intensity indoor light energy. Although considerable efforts have been made by researchers to develop low-cost, stable, and efficient PV cells for indoor applications, Extensive investigation is necessary to resolve some critical issues concerning PV cells, such as environmental stability, lifetime, large-area fabrication, mechanical flexibility, and production cost. To address these issues, a systematic review of these aspects will be highly useful to the research community. This study discusses the current status of the development of indoor PV cells based on previous reports. First, we have provided relevant background information. Then, we have described the different indoor light sources, and subsequently critically reviewed previous reports regarding indoor solar cells based on different active materials such as inorganic, dye-sensitized, organic, and perovskite. Finally, we have placed an attempt to provide insight into factors needed to further improve the feasibility of PV technology for indoor applications. Full article
(This article belongs to the Special Issue Photovoltaic Semiconductor Materials)
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14 pages, 1439 KiB  
Review
The Modelling of Extrusion Processes for Polymers—A Review
by Marko Hyvärinen, Rowshni Jabeen and Timo Kärki
Polymers 2020, 12(6), 1306; https://doi.org/10.3390/polym12061306 - 8 Jun 2020
Cited by 65 | Viewed by 17219
Abstract
Extrusion processes are widely used in industries that aim to produce advanced solutions for increasingly sophisticated demands in the plastic, food, and pharmaceutical sectors. Though the process has been in use since the 1930s, limited information is available on the analytical computation of [...] Read more.
Extrusion processes are widely used in industries that aim to produce advanced solutions for increasingly sophisticated demands in the plastic, food, and pharmaceutical sectors. Though the process has been in use since the 1930s, limited information is available on the analytical computation of extrusion. Generally, production has been carried out based on empirical experience and trial-and-error approaches. The development of industrial operations is, however, best addressed by modelling the processes involved, and the flow of polymer melts and fibers in extruders has been subjected to some previous studies. Also included an overview of design of a die as well as challenges in sheet/film production. This article systematically and critically reviews the literature related to the process design, machine design, process parameters, flow models, and flow analysis of extrusion with a focus on modelling the extrusion of composite materials. Full article
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19 pages, 4217 KiB  
Article
Mechanical Behavior of Melt-Mixed 3D Hierarchical Graphene/Polypropylene Nanocomposites
by Karolina Gaska, Georgia C. Manika, Thomas Gkourmpis, Davide Tranchida, Antonis Gitsas and Roland Kádár
Polymers 2020, 12(6), 1309; https://doi.org/10.3390/polym12061309 - 8 Jun 2020
Cited by 14 | Viewed by 3250
Abstract
The mechanical properties of novel low percolation melt-mixed 3D hierarchical graphene/polypropylene nanocomposites are analyzed in this study. The analysis spans a broad range of techniques and time scales, from impact to tensile, dynamic mechanical behavior, and creep. The applicability of the time–temperature superposition [...] Read more.
The mechanical properties of novel low percolation melt-mixed 3D hierarchical graphene/polypropylene nanocomposites are analyzed in this study. The analysis spans a broad range of techniques and time scales, from impact to tensile, dynamic mechanical behavior, and creep. The applicability of the time–temperature superposition principle and its limitations in the construction of the master curve for the isotactic polypropylene (iPP)-based graphene nanocomposites has been verified and presented. The Williams–Landel–Ferry method has been used to evaluate the dynamics and also Cole–Cole curves were presented to verify the thermorheological character of the nanocomposites. Short term (quasi-static) tensile tests, creep, and impact strength measurements were used to evaluate the load transfer efficiency. A significant increase of Young’s modulus with increasing filler content indicates reasonably good dispersion and adhesion between the iPP and the filler. The Young’s modulus results were compared with predicted modulus values using Halpin–Tsai model. An increase in brittleness resulting in lower impact strength values has also been recorded. Full article
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23 pages, 6201 KiB  
Article
Design of Waterborne Asymmetric Block Copolymers as Thermoresponsive Materials
by Gordana Siljanovska Petreska, Christof van Sluijs, Clemens Auschra and Maria Paulis
Polymers 2020, 12(6), 1253; https://doi.org/10.3390/polym12061253 - 30 May 2020
Viewed by 2805
Abstract
AB diblock waterborne copolymers made of styrene (St) and 2-ethylhexyl acrylate (2EHA) were synthesized by means of two-step reversible addition fragmentation chain transfer (RAFT) (mini)emulsion polymerization. Monofunctional asymmetric RAFT agent was used to initiate the polymerization. The hard polystyrene “A” block was synthesized [...] Read more.
AB diblock waterborne copolymers made of styrene (St) and 2-ethylhexyl acrylate (2EHA) were synthesized by means of two-step reversible addition fragmentation chain transfer (RAFT) (mini)emulsion polymerization. Monofunctional asymmetric RAFT agent was used to initiate the polymerization. The hard polystyrene “A” block was synthesized via miniemulsion polymerization followed by 2EHA pre-emulsion feeding to form the soft “B” block. Polymerization kinetics and the evolution of the molecular weight distribution were followed during synthesis of both initial and final block copolymers. DSC measurements of the block copolymers revealed the existence of two glass transition temperatures (Tgs) and thus the occurrence of two-phase systems. Microscopic techniques (atomic force microscopy (AFM) and transmission electron microscopy (TEM)) were used to study the phase separation within the particles in the latex form, after film formation at room temperature cast directly from the latex and after different post-treatments well above the Tg of the hard-polystyrene domains, when complete particle coalescence had occurred. The morphological differences observed after different annealing temperatures were correlated with the mechanical properties analyzed by DMTA measurements. Finally, the differences found in the mechanical properties of the block copolymers annealed at different temperatures were correlated to their heat seal application results. Full article
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18 pages, 4701 KiB  
Article
Designing Imidazolium Poly(amide-amide) and Poly(amide-imide) Ionenes and Their Interactions with Mono- and Tris(imidazolium) Ionic Liquids
by Kathryn E. O’Harra, Danielle M. Noll, Irshad Kammakakam, Emily M. DeVriese, Gala Solis, Enrique M. Jackson and Jason E. Bara
Polymers 2020, 12(6), 1254; https://doi.org/10.3390/polym12061254 - 30 May 2020
Cited by 7 | Viewed by 3877
Abstract
Here we introduce the synthesis and thermal properties of a series of sophisticated imidazolium ionenes with alternating amide-amide or amide-imide backbone functionality, and investigate the structural effects of mono(imidazolium) and unprecedented tris(imidazolium) ionic liquids (ILs) in these ionenes. The new set of poly(amide-amide) [...] Read more.
Here we introduce the synthesis and thermal properties of a series of sophisticated imidazolium ionenes with alternating amide-amide or amide-imide backbone functionality, and investigate the structural effects of mono(imidazolium) and unprecedented tris(imidazolium) ionic liquids (ILs) in these ionenes. The new set of poly(amide-amide) (PAA) and poly(amide-imide) (PAI) ionenes represent the intersection of conventional high-performance polymers with the ionene archetype–presenting polymers with alternating functional and ionic elements precisely sequenced along the backbone. The effects of polymer composition on the thermal properties and morphology were analyzed. Five distinct polymer backbones were synthesized and combined with a stoichiometric equivalent of the IL 1-benzyl-3-methylimidazolium bistriflimide ([Bnmim][Tf2N]), which were studied to probe the self-assembly, structuring, and contributions of intermolecular forces when IL is added. Furthermore, three polyamide (PA) or polyimide (PI) ionenes with simpler xylyl linkages were interfaced with [Bnmim][Tf2N] as well as a novel amide-linked tris(imidazolium) IL, to demonstrate the structural changes imparted by the inclusion of functional, ionic additives dispersed within the ionene matrix. This work highlights the possibilities for utilizing concepts from small molecules which exhibit supramolecular self-assembly to guide creative design and manipulate the structuring of ionenes. Full article
(This article belongs to the Special Issue Innovative Polymer Electrolytes)
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19 pages, 6844 KiB  
Article
Calorimetric and Dielectric Study of Renewable Poly(hexylene 2,5-furan-dicarboxylate)-Based Nanocomposites In Situ Filled with Small Amounts of Graphene Platelets and Silica Nanoparticles
by Olawale Monsur Sanusi, Lazaros Papadopoulos, Panagiotis A. Klonos, Zoi Terzopoulou, Nourredine Aït Hocine, Abdelkibir Benelfellah, George Z. Papageorgiou, Apostolos Kyritsis and Dimitrios N. Bikiaris
Polymers 2020, 12(6), 1239; https://doi.org/10.3390/polym12061239 - 29 May 2020
Cited by 24 | Viewed by 3558
Abstract
Poly(hexylene 2,5 furan-dicarboxylate) (PHF) is a relatively new biobased polyester prepared from renewable resources, which is targeted for use in food packaging applications, owing to its great mechanical and gas barrier performance. Since both properties are strongly connected to crystallinity, the latter is [...] Read more.
Poly(hexylene 2,5 furan-dicarboxylate) (PHF) is a relatively new biobased polyester prepared from renewable resources, which is targeted for use in food packaging applications, owing to its great mechanical and gas barrier performance. Since both properties are strongly connected to crystallinity, the latter is enhanced here by the in situ introduction in PHF of graphene nanoplatelets and fumed silica nanoparticles, as well as mixtures of both, at low amounts. For this investigation, we employed Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and dielectric spectroscopy (BDS). The fillers were found to improve crystallization in both the rate (increasing Tc) and fraction (CF), which was rationalized via the concept of fillers acting as crystallization agents. This action was found stronger in the case of graphene as compared to silica. BDS allowed the detection of local and segmental dynamics, in particular in PHF for the first time. The glass transition dynamics in both BDS (α relaxation) and DSC (Tg) are mainly dominated by the relatively high CF, whereas in the PHF filled uniquely with silica strong spatial confinement effects due to crystals were revealed. Finally, all samples demonstrated the segmental-like dynamics above Tg, which screens the global chain dynamics (normal mode). Full article
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15 pages, 3326 KiB  
Article
Controlled Synthesis of Poly(pentafluorostyrene-ran-methyl methacrylate) Copolymers by Nitroxide Mediated Polymerization and Their Use as Dielectric Layers in Organic Thin-film Transistors
by Alexander J. Peltekoff, Mathieu N. Tousignant, Victoria E. Hiller, Owen A. Melville and Benoît H. Lessard
Polymers 2020, 12(6), 1231; https://doi.org/10.3390/polym12061231 - 29 May 2020
Cited by 11 | Viewed by 4266
Abstract
A library of statistically random pentafluorostyrene (PFS) and methyl methacrylate (MMA) copolymers with narrow molecular weight distributions was produced, using nitroxide mediated polymerization (NMP) to study the effect of polymer composition on the performance of bottom-gate top-contact organic thin-film transistors, when utilized as [...] Read more.
A library of statistically random pentafluorostyrene (PFS) and methyl methacrylate (MMA) copolymers with narrow molecular weight distributions was produced, using nitroxide mediated polymerization (NMP) to study the effect of polymer composition on the performance of bottom-gate top-contact organic thin-film transistors, when utilized as the dielectric medium. Contact angle measurements confirmed the ability to tune the surface properties of copolymer thin films through variation of its PFS/MMA composition, while impedance spectroscopy determined the effect of this variation on dielectric properties. Bottom-gate, top-contact copper phthalocyanine (CuPc) based organic thin-film transistors were fabricated using the random copolymers as a dielectric layer. We found that increasing the PFS content led to increased field-effect mobility, until a point after which the CuPc no longer adhered to the polymer dielectric. Full article
(This article belongs to the Special Issue Controlled Polymerization)
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13 pages, 4976 KiB  
Article
Development of Poly(l-Lactic Acid)-Based Bending Actuators
by Daniela M. Correia, Liliana C. Fernandes, Bárbara D.D. Cruz, Gabriela Botelho, Verónica de Zea Bermudez and Senentxu Lanceros-Méndez
Polymers 2020, 12(5), 1187; https://doi.org/10.3390/polym12051187 - 22 May 2020
Cited by 8 | Viewed by 3491
Abstract
This work reports on the development of bending actuators based on poly(l-lactic acid) (PLLA)/ionic liquid (IL) blends, through the incorporation of 40% wt. of the 1-ethyl-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][TFSI]) IL. The films, obtained by solvent casting at room temperature and 50 °C, [...] Read more.
This work reports on the development of bending actuators based on poly(l-lactic acid) (PLLA)/ionic liquid (IL) blends, through the incorporation of 40% wt. of the 1-ethyl-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][TFSI]) IL. The films, obtained by solvent casting at room temperature and 50 °C, were subjected to several post-thermal treatments at 70, 90, 120 and 140 °C, in order to modify the crystallinity of the films. The influence of the drying temperature and of [Emim][TFSI] blending on the morphological, structural, mechanical and electrical properties of the composite materials were studied. The IL induced the formation of a porous surface independently of the processing conditions. Moreover, the [Emim][TFSI] dopant and the post-thermal treatments at 70 °C promoted an increase of the degree of crystallinity of the samples. No significant changes were observed in the degree of crystallinity and Young Modulus for samples with thermal treatment between 70 and 140 °C. The viability of the developed high ionic conductive blends for applications as soft actuators was evaluated. A maximum displacement of 1.7 mm was achieved with the PLLA/[Emim][TFSI] composite prepared at 50 °C and thermally treated at 140 °C, for an applied voltage of 10 Vpp, at a frequency of 100 mHz. This work highlights interesting avenues for the use of PLLA in the field of actuators. Full article
(This article belongs to the Special Issue Conducting Polymers for Advanced Applications)
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24 pages, 3183 KiB  
Review
Chitosan-Based Drug Delivery System: Applications in Fish Biotechnology
by Yuanbing Wu, Ania Rashidpour, María Pilar Almajano and Isidoro Metón
Polymers 2020, 12(5), 1177; https://doi.org/10.3390/polym12051177 - 21 May 2020
Cited by 66 | Viewed by 7665
Abstract
Chitosan is increasingly used for safe nucleic acid delivery in gene therapy studies, due to well-known properties such as bioadhesion, low toxicity, biodegradability and biocompatibility. Furthermore, chitosan derivatization can be easily performed to improve the solubility and stability of chitosan–nucleic acid polyplexes, and [...] Read more.
Chitosan is increasingly used for safe nucleic acid delivery in gene therapy studies, due to well-known properties such as bioadhesion, low toxicity, biodegradability and biocompatibility. Furthermore, chitosan derivatization can be easily performed to improve the solubility and stability of chitosan–nucleic acid polyplexes, and enhance efficient target cell drug delivery, cell uptake, intracellular endosomal escape, unpacking and nuclear import of expression plasmids. As in other fields, chitosan is a promising drug delivery vector with great potential for the fish farming industry. This review highlights state-of-the-art assays using chitosan-based methodologies for delivering nucleic acids into cells, and focuses attention on recent advances in chitosan-mediated gene delivery for fish biotechnology applications. The efficiency of chitosan for gene therapy studies in fish biotechnology is discussed in fields such as fish vaccination against bacterial and viral infection, control of gonadal development and gene overexpression and silencing for overcoming metabolic limitations, such as dependence on protein-rich diets and the low glucose tolerance of farmed fish. Finally, challenges and perspectives on the future developments of chitosan-based gene delivery in fish are also discussed. Full article
(This article belongs to the Special Issue Functional Chitosan-Based Composites)
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11 pages, 1953 KiB  
Article
Correlation between Mechanical Properties and Processing Conditions in Rubber-Toughened Wood Polymer Composites
by Valentina Mazzanti, Lorenzo Malagutti, Andrea Santoni, Francesca Sbardella, Andrea Calzolari, Fabrizio Sarasini and Francesco Mollica
Polymers 2020, 12(5), 1170; https://doi.org/10.3390/polym12051170 - 20 May 2020
Cited by 17 | Viewed by 2913
Abstract
The use of wood fibers is a deeply investigated topic in current scientific research and one of their most common applications is as filler for thermoplastic polymers. The resulting material is a biocomposite, known as a Wood Polymer Composite (WPC). For increasing the [...] Read more.
The use of wood fibers is a deeply investigated topic in current scientific research and one of their most common applications is as filler for thermoplastic polymers. The resulting material is a biocomposite, known as a Wood Polymer Composite (WPC). For increasing the sustainability and reducing the cost, it is convenient to increase the wood fiber content as much as possible, so that the polymeric fraction within the composite is thereby reduced. On the other hand, this is often thwarted by a sharp decrease in toughness and processability—a disadvantage that could be overcome by compounding the material with a toughening agent. This work deals with the mechanical properties in tension and impact of polypropylene filled with 50 wt.% wood flour, toughened with different amounts (0%, 10%, and 20%) of a polypropylene-based thermoplastic vulcanizate (TPV). Such properties are also investigated as a function of extrusion processing variables, such as the feeding mode (i.e., starve vs. flood feeding) and screw speed. It is found that the mechanical properties do depend on the processing conditions: the best properties are obtained either in starve feeding conditions, or in flood feeding conditions, but at a low screw speed. The toughening effect of TPV is significant when its content reaches 20 wt.%. For this percentage, the processing conditions are less relevant in governing the final properties of the composites in terms of the stiffness and strength. Full article
(This article belongs to the Special Issue Wood Plastic Composites)
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11 pages, 2565 KiB  
Article
Optimization and Quality Evaluation of the Interlayer Bonding Performance of Additively Manufactured Polymer Structures
by Patrick Striemann, Daniel Hülsbusch, Michael Niedermeier and Frank Walther
Polymers 2020, 12(5), 1166; https://doi.org/10.3390/polym12051166 - 19 May 2020
Cited by 25 | Viewed by 2960
Abstract
The application of additive manufacturing changes from prototypes to series production. In order to fulfill all requirements of series production, the process and the material characteristics must be known. The machine operator of additive manufacturing systems is both a component and a material [...] Read more.
The application of additive manufacturing changes from prototypes to series production. In order to fulfill all requirements of series production, the process and the material characteristics must be known. The machine operator of additive manufacturing systems is both a component and a material producer. Nevertheless, there is no standardized procedure for the manufacturing or testing of such materials. This includes the high degree of anisotropy of additively manufactured polymers via material extrusion. The interlayer bonding performance between two layers in the manufacturing direction z is the obvious weakness that needs to be improved. By optimizing this interlayer contact zone, the overall performance of the additively manufactured polymer is increased. This was achieved by process modification with an infrared preheating system (IPS) to keep the temperature of the interlayer contact zone above the glass transition temperature during the manufacturing process. Combining destructive and non-destructive testing methods, the process modification IPS was determined and evaluated by a systematic approach for characterizing the interlayer bonding performance. Thereby, tensile tests under quasi-static and cyclic loading were carried out on short carbon fiber-reinforced polyamide (SCFRP). In addition, micro-computed tomography and microscopic investigations were used to determine the process quality. The IPS increases the ultimate interlayer tensile strength by approx. 15% and shows a tendency to significantly improved the fatigue properties. Simultaneously, the analysis of the micro-computed tomography data shows a homogenization of the void distribution by using the IPS. Full article
(This article belongs to the Special Issue Functional Polymers in Additive Manufacturing)
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10 pages, 648 KiB  
Review
Lignin as a UV Light Blocker—A Review
by Hasan Sadeghifar and Arthur Ragauskas
Polymers 2020, 12(5), 1134; https://doi.org/10.3390/polym12051134 - 15 May 2020
Cited by 200 | Viewed by 12251
Abstract
Lignin is the by-product of pulp and paper industries and bio-refining operations. It is available as the leading natural phenolic biopolymer in the market. It has chromophore functional groups and can absorb a broad spectrum of UV light in range of 250–400 nm. [...] Read more.
Lignin is the by-product of pulp and paper industries and bio-refining operations. It is available as the leading natural phenolic biopolymer in the market. It has chromophore functional groups and can absorb a broad spectrum of UV light in range of 250–400 nm. Using lignin as a natural ingredient in sunscreen cream, transparent film, paints, varnishes and microorganism protection has been actively investigated. Both in non-modified and modified forms, lignin provides enhancing UV protection of commercial products with less than a 10% blend with other material. In mixtures with other synthetic UV blockers, lignin indicated synergic effects and increased final UV blocking potential in compare with using only synthetic UV blocker or lignin. However, using lignin as a UV blocker is also challenging due to its complex structure, polydispersity in molecular weight, brownish color and some impurities that require more research in order to make it an ideal bio-based UV blocker. Full article
(This article belongs to the Special Issue Progress in Lignin Value-Added Polymers)
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22 pages, 2905 KiB  
Review
Production of Sustainable and Biodegradable Polymers from Agricultural Waste
by Chrysanthos Maraveas
Polymers 2020, 12(5), 1127; https://doi.org/10.3390/polym12051127 - 14 May 2020
Cited by 188 | Viewed by 23576
Abstract
Agro-wastes are derived from diverse sources including grape pomace, tomato pomace, pineapple, orange, and lemon peels, sugarcane bagasse, rice husks, wheat straw, and palm oil fibers, among other affordable and commonly available materials. The carbon-rich precursors are used in the production bio-based polymers [...] Read more.
Agro-wastes are derived from diverse sources including grape pomace, tomato pomace, pineapple, orange, and lemon peels, sugarcane bagasse, rice husks, wheat straw, and palm oil fibers, among other affordable and commonly available materials. The carbon-rich precursors are used in the production bio-based polymers through microbial, biopolymer blending, and chemical methods. The Food and Agriculture Organization (FAO) estimates that 20–30% of fruits and vegetables are discarded as waste during post-harvest handling. The development of bio-based polymers is essential, considering the scale of global environmental pollution that is directly linked to the production of synthetic plastics such as polypropylene (PP) and polyethylene (PET). Globally, 400 million tons of synthetic plastics are produced each year, and less than 9% are recycled. The optical, mechanical, and chemical properties such as ultraviolet (UV) absorbance, tensile strength, and water permeability are influenced by the synthetic route. The production of bio-based polymers from renewable sources and microbial synthesis are scalable, facile, and pose a minimal impact on the environment compared to chemical synthesis methods that rely on alkali and acid treatment or co-polymer blending. Despite the development of advanced synthetic methods and the application of biofilms in smart/intelligent food packaging, construction, exclusion nets, and medicine, commercial production is limited by cost, the economics of production, useful life, and biodegradation concerns, and the availability of adequate agro-wastes. New and cost-effective production techniques are critical to facilitate the commercial production of bio-based polymers and the replacement of synthetic polymers. Full article
(This article belongs to the Special Issue Biodegradable and Sustainable Polymers)
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14 pages, 2228 KiB  
Article
Graphene Oxide Composite for Selective Recognition, Capturing, Photothermal Killing of Bacteria over Mammalian Cells
by Gang Ma, Junjie Qi, Qifan Cui, Xueying Bao, Dong Gao and Chengfen Xing
Polymers 2020, 12(5), 1116; https://doi.org/10.3390/polym12051116 - 13 May 2020
Cited by 24 | Viewed by 4069
Abstract
The multifunctional photothermal therapy (PTT) platform with the ability to selectively kill bacteria over mammalian cells has received widespread attention recently. Herein, we prepared graphene oxide-amino(polyethyleneglycol) (GO-PEG-NH2) while using the hydrophobic interaction between heptadecyl end groups of 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[amino(polyethyleneglycol)] (DSPE-PEG-NH2) [...] Read more.
The multifunctional photothermal therapy (PTT) platform with the ability to selectively kill bacteria over mammalian cells has received widespread attention recently. Herein, we prepared graphene oxide-amino(polyethyleneglycol) (GO-PEG-NH2) while using the hydrophobic interaction between heptadecyl end groups of 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[amino(polyethyleneglycol)] (DSPE-PEG-NH2) and graphene oxide (GO). Based on GO-PEG-NH2, the versatile PTT system was constructed with simultaneous selective recognition, capturing, and photothermal killing of bacteria. When the cells undergo bacterial infection, owing to the poly(ethylene glycol) (PEG) chains and positively charged amino groups, GO-PEG-NH2 can specifically recognize and capture bacteria in the presence of cells. Meanwhile, the stable photothermal performance of GO-PEG-NH2 enables the captured bacteria to be efficiently photothermally ablated upon the irradiation of 808 nm laser. Besides, the GO-PEG-NH2 is highly stable in various biological media and it exhibits low cytotoxicity, suggesting that it holds great promise for biological applications. This work provides new insight into graphene-based materials as a PTT agent for the development of new therapeutic platforms. Full article
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28 pages, 3967 KiB  
Review
A Review on Barrier Properties of Poly(Lactic Acid)/Clay Nanocomposites
by Shuvra Singha and Mikael S. Hedenqvist
Polymers 2020, 12(5), 1095; https://doi.org/10.3390/polym12051095 - 11 May 2020
Cited by 63 | Viewed by 6897
Abstract
Poly(lactic acid) (PLA) is considered to be among the best biopolymer substitutes for the existing petroleum-based polymers in the field of food packaging owing to its renewability, biodegradability, non-toxicity and mechanical properties. However, PLA displays only moderate barrier properties to gases, vapors and [...] Read more.
Poly(lactic acid) (PLA) is considered to be among the best biopolymer substitutes for the existing petroleum-based polymers in the field of food packaging owing to its renewability, biodegradability, non-toxicity and mechanical properties. However, PLA displays only moderate barrier properties to gases, vapors and organic compounds, which can limit its application as a packaging material. Hence, it becomes essential to understand the mass transport properties of PLA and address the transport challenges. Significant improvements in the barrier properties can be achieved by incorporating two-dimensional clay nanofillers, the planes of which create tortuosity to the diffusing molecules, thereby increasing the effective length of the diffusion path. This article reviews the literature on barrier properties of PLA/clay nanocomposites. The important PLA/clay nanocomposite preparation techniques, such as solution intercalation, melt processing and in situ polymerization, are outlined followed by an extensive account of barrier performance of nanocomposites drawn from the literature. Fundamentals of mass transport phenomena and the factors affecting mass transport are also presented. Furthermore, mathematical models that have been proposed/used to predict the permeability in polymer/clay nanocomposites are reviewed and the extent to which the models are validated in PLA/clay composites is discussed. Full article
(This article belongs to the Special Issue Performance and Application of Novel Biocomposites)
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20 pages, 2506 KiB  
Review
Functional Micro- and Nanofibers Obtained by Nonwoven Post-Modification
by Tomasz Kowalczyk
Polymers 2020, 12(5), 1087; https://doi.org/10.3390/polym12051087 - 10 May 2020
Cited by 23 | Viewed by 3708
Abstract
Micro- and nanofibers are historically-known materials that are continuously reinvented due to their valuable properties. They display promise for applications in many fields, from tissue engineering to catalysis or sensors. In the first application, micro- and nanofibers are mainly produced from a limited [...] Read more.
Micro- and nanofibers are historically-known materials that are continuously reinvented due to their valuable properties. They display promise for applications in many fields, from tissue engineering to catalysis or sensors. In the first application, micro- and nanofibers are mainly produced from a limited library of biomaterials with properties that need alteration before use. Post-modification is a very effective method for attaining on-demand features and functions of nonwovens. This review summarizes and presents methods of functionalization of nonwovens produced by electrostatic means. The reviewed modifications are grouped into physical methods, chemical modification, and mixed methods. Full article
(This article belongs to the Special Issue Functional Electrospun Nanofibers)
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14 pages, 11699 KiB  
Article
Poly (vinyl alcohol)/β-Cyclodextrin Composite Fiber with Good Flame Retardant and Super-Smoke Suppression Properties
by Cheng-Yuan Xing, Shi-Lin Zeng, Shi-Kai Qi, Meng-Jin Jiang, Long Xu, Li Chen, Sheng Zhang and Bang-Jing Li
Polymers 2020, 12(5), 1078; https://doi.org/10.3390/polym12051078 - 8 May 2020
Cited by 16 | Viewed by 3655
Abstract
Fibers with good flame retardant (FR) and smoke suppression performances are highly desirable for the purpose of eliminating fire hazard. This study developed a novel FR fiber by wet-spinning poly (vinyl alcohol)/β-cyclodextrin (PVA/βCD) composite fiber and crosslinking it with hexamethylene diisocyanate (HDI). βCDs [...] Read more.
Fibers with good flame retardant (FR) and smoke suppression performances are highly desirable for the purpose of eliminating fire hazard. This study developed a novel FR fiber by wet-spinning poly (vinyl alcohol)/β-cyclodextrin (PVA/βCD) composite fiber and crosslinking it with hexamethylene diisocyanate (HDI). βCDs showed good compatibility with PVA matrix, and the resulting PVA/CD/HDI fibers showed mechanical strength at the same level as natural cotton fiber. The PVA/CD/HDI fibers also showed excellent flame retardance (the LOI value of PVA/CD/HDI could reach 41.7%, and their peak of heat release (PHRR) could be reduced by up to 77.7% by neat PVA), and super-smoke suppression (the value of total smoke production (TSP) was only 28.6% compared to PVA). These dramatic reductions of fire hazard were ascribed to the char formation of βCD and crosslinking structure of PVA/CD/HDI, which formed a compact char layer during combustion, thus preventing heat transmission and smoke release. Full article
(This article belongs to the Special Issue Advances in Flame Retardant Polymeric Materials)
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23 pages, 2446 KiB  
Review
Activation Energies and Temperature Dependencies of the Rates of Crystallization and Melting of Polymers
by Sergey Vyazovkin
Polymers 2020, 12(5), 1070; https://doi.org/10.3390/polym12051070 - 7 May 2020
Cited by 57 | Viewed by 7868
Abstract
The objective of this review paper is to survey the phase transition kinetics with a focus on the temperature dependence of the rates of crystallization and melting, as well as on the activation energies of these processes obtained via the Arrhenius kinetic treatment, [...] Read more.
The objective of this review paper is to survey the phase transition kinetics with a focus on the temperature dependence of the rates of crystallization and melting, as well as on the activation energies of these processes obtained via the Arrhenius kinetic treatment, including the treatment by isoconversional methods. The literature is analyzed to track the development of the basic models and their underlying concepts. The review presents both theoretical and practical considerations regarding the kinetic analysis of crystallization and melting. Both processes are demonstrated to be kinetically complex, and this is revealed in the form of nonlinear Arrhenius plots and/or the variation of the activation energy with temperature. Principles which aid one to understand and interpret such results are discussed. An emphasis is also put on identifying proper computational methods and experimental data that can lead to meaningful kinetic interpretation. Full article
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30 pages, 7109 KiB  
Review
Water-Soluble Photoinitiators in Biomedical Applications
by Wiktoria Tomal and Joanna Ortyl
Polymers 2020, 12(5), 1073; https://doi.org/10.3390/polym12051073 - 7 May 2020
Cited by 148 | Viewed by 24357
Abstract
Light-initiated polymerization processes are currently an important tool in various industrial fields. The advancement of technology has resulted in the use of photopolymerization in various biomedical applications, such as the production of 3D hydrogel structures, the encapsulation of cells, and in drug delivery [...] Read more.
Light-initiated polymerization processes are currently an important tool in various industrial fields. The advancement of technology has resulted in the use of photopolymerization in various biomedical applications, such as the production of 3D hydrogel structures, the encapsulation of cells, and in drug delivery systems. The use of photopolymerization processes requires an appropriate initiating system that, in biomedical applications, must meet additional criteria such as high water solubility, non-toxicity to cells, and compatibility with visible low-power light sources. This article is a literature review on those compounds that act as photoinitiators of photopolymerization processes in biomedical applications. The division of initiators according to the method of photoinitiation was described and the related mechanisms were discussed. Examples from each group of photoinitiators are presented, and their benefits, limitations, and applications are outlined. Full article
(This article belongs to the Special Issue Biomedical Polymer Materials II)
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25 pages, 4090 KiB  
Review
Potential Natural Fiber Polymeric Nanobiocomposites: A Review
by K. M. Faridul Hasan, Péter György Horváth and Tibor Alpár
Polymers 2020, 12(5), 1072; https://doi.org/10.3390/polym12051072 - 7 May 2020
Cited by 155 | Viewed by 15656
Abstract
Composite materials reinforced with biofibers and nanomaterials are becoming considerably popular, especially for their light weight, strength, exceptional stiffness, flexural rigidity, damping property, longevity, corrosion, biodegradability, antibacterial, and fire-resistant properties. Beside the traditional thermoplastic and thermosetting polymers, nanoparticles are also receiving attention in [...] Read more.
Composite materials reinforced with biofibers and nanomaterials are becoming considerably popular, especially for their light weight, strength, exceptional stiffness, flexural rigidity, damping property, longevity, corrosion, biodegradability, antibacterial, and fire-resistant properties. Beside the traditional thermoplastic and thermosetting polymers, nanoparticles are also receiving attention in terms of their potential to improve the functionality and mechanical performances of biocomposites. These remarkable characteristics have made nanobiocomposite materials convenient to apply in aerospace, mechanical, construction, automotive, marine, medical, packaging, and furniture industries, through providing environmental sustainability. Nanoparticles (TiO2, carbon nanotube, rGO, ZnO, and SiO2) are easily compatible with other ingredients (matrix polymer and biofibers) and can thus form nanobiocomposites. Nanobiocomposites are exhibiting a higher market volume with the expansion of new technology and green approaches for utilizing biofibers. The performances of nanobiocomposites depend on the manufacturing processes, types of biofibers used, and the matrix polymer (resin). An overview of different natural fibers (vegetable/plants), nanomaterials, biocomposites, nanobiocomposites, and manufacturing methods are discussed in the context of potential application in this review. Full article
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15 pages, 3442 KiB  
Article
Effect of Bis (2-Aminoethyl) Adipamide/Adipic Acid Segment on Polyamide 6: Crystallization Kinetics Study
by Yu-Hao Chen, Palraj Ranganathan, Chin-Wen Chen, Yi-Huan Lee and Syang-Peng Rwei
Polymers 2020, 12(5), 1067; https://doi.org/10.3390/polym12051067 - 6 May 2020
Cited by 12 | Viewed by 3453
Abstract
The crystallization behavior of novel polyamide 6 (PA6) copolyamides with different amounts of bis (2-aminoethyl) adipamide/adipic acid (BAEA/AA) segment was investigated. The wide-angle X-ray diffraction (WAXD) results showed that as the amount of BAEA/AA segment increased to 10 mole%, the crystalline forms of [...] Read more.
The crystallization behavior of novel polyamide 6 (PA6) copolyamides with different amounts of bis (2-aminoethyl) adipamide/adipic acid (BAEA/AA) segment was investigated. The wide-angle X-ray diffraction (WAXD) results showed that as the amount of BAEA/AA segment increased to 10 mole%, the crystalline forms of all PA6 copolyamide were transferred from the stable α-form to the unstable γ-form because of the complex polymer structure. According to studies of crystallization kinetics, the Avrami exponent (n) values for all copolyamide samples ranged from 1.43 to 3.67 under isothermal conditions, implying that the crystallization is involved in the two- to three-dimensional growth at a high temperature of isothermal condition. The copolyamides provided a slower crystallization rate and higher crystallization activation energy (ΔEa) than neat PA6. Polyamide containing 10 mole% of BEAE/AA content exhibited a unique crystallization behavior in the coexistence of the α and γ forms. These results deepen our understanding of the relationship between BAEA/AA content, crystal structure, and its crystallization behavior in low-melting PA6, and they make these types of copolyamides useful for their practical application. Full article
(This article belongs to the Special Issue Thermal Analysis of Polymer Materials)
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15 pages, 3999 KiB  
Article
Preparation of Tri(alkenyl)functional Open-Cage Silsesquioxanes as Specific Polymer Modifiers
by Katarzyna Mituła, Michał Dutkiewicz, Julia Duszczak, Monika Rzonsowska and Beata Dudziec
Polymers 2020, 12(5), 1063; https://doi.org/10.3390/polym12051063 - 6 May 2020
Cited by 7 | Viewed by 2955
Abstract
The scientific reports on polyhedral oligomeric silsesquioxanes are mostly focused on the formation of completely condensed T8 cubic type structures and recently so-called double-decker derivatives. Herein, we report on efficient synthetic routes leading to trifunctionalized, open-cage silsesquioxanes with alkenyl groups of varying [...] Read more.
The scientific reports on polyhedral oligomeric silsesquioxanes are mostly focused on the formation of completely condensed T8 cubic type structures and recently so-called double-decker derivatives. Herein, we report on efficient synthetic routes leading to trifunctionalized, open-cage silsesquioxanes with alkenyl groups of varying chain lengths from -vinyl to -dec-9-enyl and two types of inert groups (iBu, Ph) at the silsesquioxane core. The presented methodology was focused on hydrolytic condensation reaction and it enabled obtaining titled compounds with high yields and purity. A parallel synthetic methodology that was based on the hydrosilylation reaction was also studied. Additionally, a thorough characterization of the obtained compounds was performed, also in terms of their thermal stability, melting and crystallization temperatures (TGA and DSC) in order to show the changes in the abovementioned parameters dependent on the type of reactive as well as inert groups at Si-O-Si core. The presence of unsaturated alkenyl groups has a profound impact on the application potential of these systems, i.e., as modifiers or comonomers for copolymerization reaction. Full article
(This article belongs to the Special Issue Silsesquioxane (POSS) Polymers, Copolymers and Nanoparticles)
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25 pages, 4922 KiB  
Article
Ecological Design of New Efficient Energy-Performance Construction Materials with Rigid Polyurethane Foam Waste
by Raúl Briones-Llorente, Ricardo Barbosa, Manuela Almeida, Eduardo Atanasio Montero García and Ángel Rodríguez Saiz
Polymers 2020, 12(5), 1048; https://doi.org/10.3390/polym12051048 - 3 May 2020
Cited by 17 | Viewed by 3502
Abstract
An ecological mortar is designed from industrial sub-products, with the objective of utilizing both the slag residues, generated during steel manufacturing processes, and the waste from Polyurethane Foam (PF) panels, generated during refrigerator chamber manufacturing processes. The ecological mortar design involves the dosing [...] Read more.
An ecological mortar is designed from industrial sub-products, with the objective of utilizing both the slag residues, generated during steel manufacturing processes, and the waste from Polyurethane Foam (PF) panels, generated during refrigerator chamber manufacturing processes. The ecological mortar design involves the dosing of Electric Arc Furnace (EAF) slag, together with finely ground Polyurethane Foam, cement, and additives. An energy efficient prefabricated block is designed with the mortar, for use in construction, and its energy performance is assessed as a material inserted within the envelope of a service sector (hospital) building, either as an exterior skin, or as an enclosing component within the façade interior. The main contribution of this research is the characterization of the thermo-physical and mechanical properties of a new prefabricated panel made with recycled materials. The full characterization of the properties of these new materials is presented and discussed. The new prefabricated panel demonstrates adequate thermo-mechanical characteristics as a substitute for traditional materials, while improving the sustainability of the building. As a secondary objective, the energy behaviour of the new panels when integrated in a real building is presented by means of a case study simulation. The use of computational thermal simulation confirmed that the properties of the prefabricated block influenced the annual thermal demand of the building for heating and cooling. Improvements to the thermal inertia of the building envelope were also confirmed with the inclusion of PF waste, giving the mortar an energy performance that was similar to conventional materials, in such a way that its use in façade construction may be validated, in addition to its environmental benefits, due to it having been manufactured with critical recycled industrial waste such as EAF slag and PF, thereby contributing to both the circular economy and sustainable development. Full article
(This article belongs to the Special Issue Polymers and the Circular Economy Model)
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14 pages, 4399 KiB  
Article
Preparation of Nanocomposite-Based High Performance Organic Field Effect Transistor via Solution Floating Method and Mechanical Property Evaluation
by Youn Kim, Yeon Ju Kwon, Seungwan Ryu, Cheol Jin Lee and Jea Uk Lee
Polymers 2020, 12(5), 1046; https://doi.org/10.3390/polym12051046 - 2 May 2020
Cited by 5 | Viewed by 3235
Abstract
We demonstrate that using nanocomposite thin films consisting of semiconducting polymer, poly(3-hexylthiophene) (P3HT), and electrochemically exfoliated graphene (EEG) for the active channel layer of organic field-effect transistors (OFETs) improves both device performances and mechanical properties. The nanocomposite film was developed by directly blending [...] Read more.
We demonstrate that using nanocomposite thin films consisting of semiconducting polymer, poly(3-hexylthiophene) (P3HT), and electrochemically exfoliated graphene (EEG) for the active channel layer of organic field-effect transistors (OFETs) improves both device performances and mechanical properties. The nanocomposite film was developed by directly blending P3HT solution with a dispersion of EEG at various weight proportions and simply transferring to an Si/SiO2 substrate by the solution floating method. The OFET based on P3HT/EEG nanocomposite film showed approximately twice higher field-effect mobility of 0.0391 cm2·V−1·s−1 and one order of magnitude greater on/off ratio of ~104 compared with the OFET based on pristine P3HT. We also measured the mechanical properties of P3HT/EEG nanocomposite film via film-on-elastomer methods, which confirms that the P3HT/EEG nanocomposite film exhibited approximately 2.4 times higher modulus (3.29 GPa) than that of the P3HT film (1.38 GPa), while maintaining the good bending flexibility and durability over 10.0% of bending strain and bending cycles (1000 cycles). It was proved that the polymer hybridization technique, which involves adding EEG to a conjugated polymer, is a powerful route for enhancing both device performances and mechanical properties while maintaining the flexible characteristics of OFET devices. Full article
(This article belongs to the Special Issue Polymer and Carbon Materials Engineering)
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26 pages, 6064 KiB  
Article
One-Step Preparation of Antifouling Polysulfone Ultrafiltration Membranes via Modification by a Cationic Polyelectrolyte Based on Polyacrylamide
by Tatiana V. Plisko, Alexandr V. Bildyukevich, Katsiaryna S. Burts, Sergey S. Ermakov, Anastasia V. Penkova, Anna I. Kuzminova, Maria E. Dmitrenko, Tatiana A. Hliavitskaya and Mathias Ulbricht
Polymers 2020, 12(5), 1017; https://doi.org/10.3390/polym12051017 - 30 Apr 2020
Cited by 20 | Viewed by 3558
Abstract
A novel method for one-step preparation of antifouling ultrafiltration membranes via a non-solvent induced phase separation (NIPS) technique is proposed. It involves using aqueous 0.05–0.3 wt.% solutions of cationic polyelectrolyte based on a copolymer of acrylamide and 2-acryloxyethyltrimethylammonium chloride (Praestol 859) as a [...] Read more.
A novel method for one-step preparation of antifouling ultrafiltration membranes via a non-solvent induced phase separation (NIPS) technique is proposed. It involves using aqueous 0.05–0.3 wt.% solutions of cationic polyelectrolyte based on a copolymer of acrylamide and 2-acryloxyethyltrimethylammonium chloride (Praestol 859) as a coagulant in NIPS. A systematic study of the effect of the cationic polyelectrolyte addition to the coagulant on the structure, performance and antifouling stability of polysulfone membranes was carried out. The methods for membrane characterization involved scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), contact angle and zeta-potential measurements and evaluation of the permeability, rejection and antifouling performance in human serum albumin solution and surface water ultrafiltration. It was revealed that in the presence of cationic polyelectrolyte in the coagulation bath, its concentration has a major influence on the rate of “solvent–non-solvent” exchange and thus also on the rate of phase separation which significantly affects membrane structure. The immobilization of cationic polyelectrolyte macromolecules into the selective layer was confirmed by FTIR spectroscopy. It was revealed that polyelectrolyte macromolecules predominately immobilize on the surface of the selective layer and not on the bottom layer. Membrane modification was found to improve the hydrophilicity of the selective layer, to increase surface roughness and to change zeta-potential which yields the substantial improvement of membrane antifouling stability toward natural organic matter and human serum albumin. Full article
(This article belongs to the Special Issue Advances in Polymeric Membranes)
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27 pages, 6394 KiB  
Article
Enhancement of Oil Palm Waste Nanoparticles on the Properties and Characterization of Hybrid Plywood Biocomposites
by Arif Nuryawan, C. K. Abdullah, Che Mohamad Hazwan, N. G. Olaiya, Esam Bashir Yahya, Iwan Risnasari, Nanang Masruchin, M. S. Baharudin, Hasmawi Khalid and H. P. S. Abdul Khalil
Polymers 2020, 12(5), 1007; https://doi.org/10.3390/polym12051007 - 27 Apr 2020
Cited by 25 | Viewed by 4718
Abstract
Using oil palm trunk (OPT) layered with empty fruit bunch (EFB), so-called hybrid plywood enhanced with palm oil ash nanoparticles, with phenol-formaldehyde (PF) resin as a binder, was produced in this study. The phenol-formaldehyde (PF) resins filled with different loading of oil palm [...] Read more.
Using oil palm trunk (OPT) layered with empty fruit bunch (EFB), so-called hybrid plywood enhanced with palm oil ash nanoparticles, with phenol-formaldehyde (PF) resin as a binder, was produced in this study. The phenol-formaldehyde (PF) resins filled with different loading of oil palm ash (OPA) nanoparticles were prepared and used as glue for layers of the oil palm trunk (OPT) veneer and empty fruit bunch fibre mat. The resulting hybrid plywood produced was characterised. The physical, mechanical, thermal, and morphological properties of the hybrid plywood panels were investigated. The results obtained showed that the presence of OPA nanoparticles significantly affected the physical, mechanical, and thermal properties of the plywood panels. Significant improvements in dimension from water absorption and thickness swelling experiments were obtained for the plywood panels with the highest OPA nanoparticles loading in PF resin. The mechanical properties indicated that plywood composites showed improvement in flexural, shear, and impact properties until a certain loading of OPA nanoparticles in PF resin. Fracture surface morphology also showed the effectiveness of OPA nanoparticles in the reduction of layer breakage due to force and stress distribution. The thermal stability performance showed that PF filled OPA nanoparticles contributed to the thermal stability of the plywood panels. Therefore, the results obtained in this study showed that OPA nanoparticles certainly improved the characteristic of the hybrid plywood. Full article
(This article belongs to the Special Issue Multifunctional Ecocomposites)
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11 pages, 2759 KiB  
Article
Preparation and Characteristics of Wet-Spun Filament Made of Cellulose Nanofibrils with Different Chemical Compositions
by Chan-Woo Park, Ji-Soo Park, Song-Yi Han, Eun-Ah Lee, Gu-Joong Kwon, Young-Ho Seo, Jae-Gyoung Gwon, Sun-Young Lee and Seung-Hwan Lee
Polymers 2020, 12(4), 949; https://doi.org/10.3390/polym12040949 - 19 Apr 2020
Cited by 11 | Viewed by 3558
Abstract
In this study, wet-spun filaments were prepared using lignocellulose nanofibril (LCNF), with 6.0% and 13.0% of hemicellulose and lignin, respectively, holocellulose nanofibril (HCNF), with 37% hemicellulose, and nearly purified-cellulose nanofibril (NP-CNF) through wet-disk milling followed by high-pressure homogenization. The diameter was observed to [...] Read more.
In this study, wet-spun filaments were prepared using lignocellulose nanofibril (LCNF), with 6.0% and 13.0% of hemicellulose and lignin, respectively, holocellulose nanofibril (HCNF), with 37% hemicellulose, and nearly purified-cellulose nanofibril (NP-CNF) through wet-disk milling followed by high-pressure homogenization. The diameter was observed to increase in the order of NP-CNF ≤ HCNF < LCNF. The removal of lignin improved the defibrillation efficiency, thus increasing the specific surface area and filtration time. All samples showed the typical X-ray diffraction pattern of cellulose I. The orientation of CNFs in the wet-spun filaments was observed to increase at a low concentration of CNF suspensions and high spinning rate. The increase in the CNF orientation improved the tensile strength and elastic modulus of the wet-spun filaments. The tensile strength of the wet-spun filaments decreased in the order of HCNF > NP-CNF > LCNF. Full article
(This article belongs to the Special Issue Nanocellulose Based Functional Materials)
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22 pages, 2274 KiB  
Review
Recent Advances in Tissue Adhesives for Clinical Medicine
by Liangpeng Ge and Shixuan Chen
Polymers 2020, 12(4), 939; https://doi.org/10.3390/polym12040939 - 18 Apr 2020
Cited by 91 | Viewed by 12138
Abstract
Tissue adhesives have attracted more attention to the applications of non-invasive wound closure. The purpose of this review article is to summarize the recent progress of developing tissue adhesives, which may inspire researchers to develop more outstanding tissue adhesives. It begins with a [...] Read more.
Tissue adhesives have attracted more attention to the applications of non-invasive wound closure. The purpose of this review article is to summarize the recent progress of developing tissue adhesives, which may inspire researchers to develop more outstanding tissue adhesives. It begins with a brief introduction to the emerging potential use of tissue adhesives in the clinic. Next, several critical mechanisms for adhesion are discussed, including van der Waals forces, capillary forces, hydrogen bonding, static electric forces, and chemical bonds. This article further details the measurement methods of adhesion and highlights the different types of adhesive, including natural or biological, synthetic and semisynthetic, and biomimetic adhesives. Finally, this review article concludes with remarks on the challenges and future directions for design, fabrication, and application of tissue adhesives in the clinic. This review article has promising potential to provide novel creative design principles for the generation of future tissue adhesives. Full article
(This article belongs to the Special Issue Advanced Polymeric Biomaterials for Tissue Engineering)
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15 pages, 4790 KiB  
Article
Bio-Based Coatings for Food Metal Packaging Inspired in Biopolyester Plant Cutin
by José J. Benítez, Sonja Osbild, Susana Guzman-Puyol, Antonio Heredia and José A. Heredia-Guerrero
Polymers 2020, 12(4), 942; https://doi.org/10.3390/polym12040942 - 18 Apr 2020
Cited by 14 | Viewed by 5417
Abstract
Metals used for food canning such as aluminum (Al), chromium-coated tin-free steel (TFS) and electrochemically tin-plated steel (ETP) were coated with a 2–3-µm-thick layer of polyaleuritate, the polyester resulting from the self-esterification of naturally-occurring 9,10,16-trihydroxyhexadecanoic (aleuritic) acid. The kinetic of the esterification was [...] Read more.
Metals used for food canning such as aluminum (Al), chromium-coated tin-free steel (TFS) and electrochemically tin-plated steel (ETP) were coated with a 2–3-µm-thick layer of polyaleuritate, the polyester resulting from the self-esterification of naturally-occurring 9,10,16-trihydroxyhexadecanoic (aleuritic) acid. The kinetic of the esterification was studied by FTIR spectroscopy; additionally, the catalytic activity of the surface layer of chromium oxide on TFS and, in particular, of tin oxide on ETP, was established. The texture, gloss and wettability of coatings were characterized by AFM, UV-Vis total reflectance and static water contact angle (WCA) measurements. The resistance of the coatings to solvents was also determined and related to the fraction of unreacted polyhydroxyacid. The occurrence of an oxidative diol cleavage reaction upon preparation in air induced a structural modification of the polyaleuritate layer and conferred upon it thermal stability and resistance to solvents. The promoting effect of the tin oxide layer in such an oxidative cleavage process fosters the potential of this methodology for the design of effective long-chain polyhydroxyester coatings on ETP. Full article
(This article belongs to the Special Issue Sustainable Bio-Based Polymers: Towards a Circular Bioeconomy)
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38 pages, 2947 KiB  
Review
Recent Advances in Bioplastics: Application and Biodegradation
by Tanja Narancic, Federico Cerrone, Niall Beagan and Kevin E. O’Connor
Polymers 2020, 12(4), 920; https://doi.org/10.3390/polym12040920 - 15 Apr 2020
Cited by 191 | Viewed by 25897
Abstract
The success of oil-based plastics and the continued growth of production and utilisation can be attributed to their cost, durability, strength to weight ratio, and eight contributions to the ease of everyday life. However, their mainly single use, durability and recalcitrant nature have [...] Read more.
The success of oil-based plastics and the continued growth of production and utilisation can be attributed to their cost, durability, strength to weight ratio, and eight contributions to the ease of everyday life. However, their mainly single use, durability and recalcitrant nature have led to a substantial increase of plastics as a fraction of municipal solid waste. The need to substitute single use products that are not easy to collect has inspired a lot of research towards finding sustainable replacements for oil-based plastics. In addition, specific physicochemical, biological, and degradation properties of biodegradable polymers have made them attractive materials for biomedical applications. This review summarises the advances in drug delivery systems, specifically design of nanoparticles based on the biodegradable polymers. We also discuss the research performed in the area of biophotonics and challenges and opportunities brought by the design and application of biodegradable polymers in tissue engineering. We then discuss state-of-the-art research in the design and application of biodegradable polymers in packaging and emphasise the advances in smart packaging development. Finally, we provide an overview of the biodegradation of these polymers and composites in managed and unmanaged environments. Full article
(This article belongs to the Special Issue Recent Advances in Bioplastics II)
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13 pages, 3053 KiB  
Article
Preparation of PVA Fluorescent Gel and Luminescence of Europium Sensitized by Terbium (III)
by Yifan Wei, Zhengquan Fu, Hao Zhao, Ruiqi Liang, Chengyu Wang, Di Wang and Jian Li
Polymers 2020, 12(4), 893; https://doi.org/10.3390/polym12040893 - 12 Apr 2020
Cited by 12 | Viewed by 3501
Abstract
Polyvinyl alcohol (PVA) gel has a very wide range of applications in agriculture, military, industry, and other fields. As a widely used water-soluble polymer, PVA has good mechanical properties, excellent spinnability, good hydrophilicity, remarkable physical and chemical stability, good film formation, is non-polluting, [...] Read more.
Polyvinyl alcohol (PVA) gel has a very wide range of applications in agriculture, military, industry, and other fields. As a widely used water-soluble polymer, PVA has good mechanical properties, excellent spinnability, good hydrophilicity, remarkable physical and chemical stability, good film formation, is non-polluting, and exhibits good natural degradation and biocompatibility. It is an ideal gel preparation material. Incorporation of rare-earth elements into PVA polymers can be used to prepare rare-earth luminescent gel materials. Results show that the luminescent efficiency of complexes is mainly related to their structure, ligand substituents, synergists, and the electronic configuration of doped rare-earth ions. Fluorescent gel films were prepared by adding europium, terbium, and europium/terbium co-doped into PVA, and their fluorescence properties were compared and analyzed. It was found that, in addition to the above factors, the sensitization of terbium to europium, and the fluorescence-quenching effect of hydroxyl groups, will influence the fluorescence properties. This has opened a new route for the application of rare-earth materials and may have value in the field of new materials. Full article
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15 pages, 1648 KiB  
Article
Supramolecular Dimerization in a Polymer Melt from Small-Angle X-ray Scattering and Rheology: A Miscible Model System
by Mariapaola Staropoli, Margarita Kruteva, Jürgen Allgaier, Andreas Wischnewski and Wim Pyckhout-Hintzen
Polymers 2020, 12(4), 880; https://doi.org/10.3390/polym12040880 - 10 Apr 2020
Cited by 2 | Viewed by 2701
Abstract
We present a structural and dynamic study on the simplest supramolecular hetero-association, recently investigated by the authors to prepare architectural homogeneous structures in the melt state, based on the bio-inspired hydrogen-bonding of thymine/diaminotriazine (thy–DAT) base-pairs. In the combination with an amorphous low T [...] Read more.
We present a structural and dynamic study on the simplest supramolecular hetero-association, recently investigated by the authors to prepare architectural homogeneous structures in the melt state, based on the bio-inspired hydrogen-bonding of thymine/diaminotriazine (thy–DAT) base-pairs. In the combination with an amorphous low Tg poly(butylene oxide) (PBO), no micellar structures are formed, which is expected for nonpolar polymers because of noncompatibility with the highly polar supramolecular groups. Instead, a clear polymer-like transient architecture is retrieved. This makes the heterocomplementary thy–DAT association an ideal candidate for further exploitation of the hydrogen-bonding ability in the bulk for self-healing purposes, damage management in rubbers or even the development of easily processable branched polymers with built-in plasticizer. In the present work, we investigate the temperature range from Tg + 20 °C to Tg + 150 °C of an oligomeric PBO using small-angle X-ray scattering (SAXS) and linear rheology on the pure thy and pure DAT monofunctionals and on an equimolar mixture of thy/DAT oligomers. The linear rheology performed at low temperature is found to correspond to fully closed-state dimeric configurations. At intermediate temperatures, SAXS probes the equilibrium between open and closed states of the thy–DAT mixtures. The temperature-dependent association constant in the full range between open and closed H-bonds and an enhancement of the monomeric friction coefficient due to the groups is obtained. The thy–DAT association in the melt is more stable than the DAT–DAT, whereas the thy–thy association seems to involve additional long-lived interactions. Full article
(This article belongs to the Special Issue Multifunctional Supramolecular Polymers)
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14 pages, 3380 KiB  
Article
Injectable Click Polypeptide Hydrogels via Tetrazine-Norbornene Chemistry for Localized Cisplatin Release
by Zhen Zhang, Chaoliang He and Xuesi Chen
Polymers 2020, 12(4), 884; https://doi.org/10.3390/polym12040884 - 10 Apr 2020
Cited by 11 | Viewed by 4782
Abstract
Injectable, covalently cross-linked hydrogels have been widely investigated in drug delivery systems due to their superior mechanical properties and long-term stability. Conventional covalently cross-linked hydrogels are formed by chemical reactions that may interfere with natural biochemical processes. In this work, we developed an [...] Read more.
Injectable, covalently cross-linked hydrogels have been widely investigated in drug delivery systems due to their superior mechanical properties and long-term stability. Conventional covalently cross-linked hydrogels are formed by chemical reactions that may interfere with natural biochemical processes. In this work, we developed an injectable polypeptide hydrogel via an inverse electron demand Diels-Alder reaction between norbornene modified poly(L-glutamic acid) (PLG-Norb) and tetrazine functionalized four-arm poly(ethylene glycol) (4aPEG-T) for localized release of cisplatin (CDDP). The rapid and bioorthogonal click reaction allowed for hydrogel formation within a few minutes after mixing the two polymer solutions in phosphate buffer saline (PBS). Dynamic mechanical analysis suggested that the storage modulus of the hydrogel could be readily tuned by changing the polymer concentration and the molar ratio of the two functional groups. The carboxyl groups of PLG-Norb were used to form polymer–metal complexation with CDDP, and the controlled release of the antitumor drug was achieved in PBS. The CDDP-loaded hydrogel displayed an antitumor effect against MCF-7 cells in vitro, through S phase cell cycle arrest. After subcutaneous injection in rats, the hydrogel was rapidly formed in situ and showed good stability in vivo. In an MCF-7-bearing nude mice model, the CDDP-loaded hydrogel exhibited an improved antitumor effect with reduced systemic toxicity. Overall, the injectable click polypeptide hydrogel shows considerable potential as a platform for localized and sustained delivery of antitumor drugs. Full article
(This article belongs to the Special Issue Polypeptide Polymers)
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11 pages, 6348 KiB  
Article
A Simplified 2D Numerical Simulation of Photopolymerization Kinetics and Oxygen Diffusion–Reaction for the Continuous Liquid Interface Production (CLIP) System
by Kentaro Taki
Polymers 2020, 12(4), 875; https://doi.org/10.3390/polym12040875 - 10 Apr 2020
Cited by 14 | Viewed by 3308
Abstract
Additive manufacturing is a versatile technology for producing customized 3D products. In 2015, the Continuous Liquid Interface Production (CLIP) system was developed as a part of projection-type, UV-curable resin 3D printers. The CLIP system utilized the dead zone where oxygen inhibition occurs and [...] Read more.
Additive manufacturing is a versatile technology for producing customized 3D products. In 2015, the Continuous Liquid Interface Production (CLIP) system was developed as a part of projection-type, UV-curable resin 3D printers. The CLIP system utilized the dead zone where oxygen inhibition occurs and prevents the UV-cured product from adhering to the UV illumination window. The CLIP system successfully produced complex shapes in a short time. This study investigated how the relationship between the photopolymerization rate, oxygen inhibition rate, and oxygen diffusion rate affects the shape of the product by means of a numerical simulation of the photopolymerization kinetics with oxygen diffusion and reaction. The results indicate that the vertical production speed and transmittance of UV light are crucial to controlling the conversion and shape precision of products. Full article
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17 pages, 2607 KiB  
Article
Impact of Current and Temperature on Extremely Low Loading Epoxy-CNT Conductive Composites
by Brian Earp, Jonathan Phillips, Dragoslav Grbovic, Stephen Vidmar, Matthew Porter and Claudia C. Luhrs
Polymers 2020, 12(4), 867; https://doi.org/10.3390/polym12040867 - 10 Apr 2020
Cited by 8 | Viewed by 2521
Abstract
Carbon nanotube (CNT) conductive composites have attracted significant attention for their potential use in applications such as electrostatic dissipation and/or electromagnetic interference shielding. The focus of this work is to evaluate resistivity trends of extremely low loading (<0.1 wt%) epoxy-CNT composites that lack [...] Read more.
Carbon nanotube (CNT) conductive composites have attracted significant attention for their potential use in applications such as electrostatic dissipation and/or electromagnetic interference shielding. The focus of this work is to evaluate resistivity trends of extremely low loading (<0.1 wt%) epoxy-CNT composites that lack a connected CNT network, but still present electrical conductivity values appropriate for those uses. The impact of current, temperature, and cycle life on electrical properties are here identified and tied to possible performance limits. At extremely low loadings, the CNT content is not sufficient to form a completely interconnected grid, thus, electrons must travel through insulating media. While still in the semi-conductor range, resistivity values are observed to decrease with increasing direct current and demonstrate a non-ohmic behavior. CNT epoxy composites were subjected to elevated currents and/or temperatures over diverse periods of time to examine impacts on resistivity. Microstructural analyses of composite samples were conducted to observe signs of damage for specimens taken to extreme temperatures/currents. An understanding of the electrical conductivity characteristics of extremely low loading epoxy-CNT composites and their failure mechanisms will aid in understanding risks associated with their use in challenging environments that may include high temperatures, high currents, and/or high frequencies. Full article
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14 pages, 4016 KiB  
Article
Highly Deformable Porous Electromagnetic Wave Absorber Based on Ethylene–Propylene–Diene Monomer/Multiwall Carbon Nanotube Nanocomposites
by Hasti Bizhani, Ali Asghar Katbab, Emil Lopez-Hernandez, Jose Miguel Miranda and Raquel Verdejo
Polymers 2020, 12(4), 858; https://doi.org/10.3390/polym12040858 - 8 Apr 2020
Cited by 16 | Viewed by 3357
Abstract
The need for electromagnetic interference (EMI) shields has risen over the years as the result of our digitally and highly connected lifestyle. This work reports on the development of one such shield based on vulcanized rubber foams. Nanocomposites of ethylene–propylene–diene monomer (EPDM) rubber [...] Read more.
The need for electromagnetic interference (EMI) shields has risen over the years as the result of our digitally and highly connected lifestyle. This work reports on the development of one such shield based on vulcanized rubber foams. Nanocomposites of ethylene–propylene–diene monomer (EPDM) rubber and multiwall carbon nanotubes (MWCNTs) were prepared via hot compression molding using a chemical blowing agent as foaming agent. MWCNTs accelerated the cure and led to high shear-thinning behavior, indicative of the formation of a 3D interconnected physical network. Foamed nanocomposites exhibited lower electrical percolation threshold than their solid counterparts. Above percolation, foamed nanocomposites displayed EMI absorption values of 28–45 dB in the frequency range of the X-band. The total EMI shielding efficiency of the foams was insignificantly affected by repeated bending with high recovery behavior. Our results highlight the potential of cross-linked EPDM/MWCNT foams as a lightweight EM wave absorber with high flexibility and deformability. Full article
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38 pages, 2616 KiB  
Review
Proteins and Peptides as Important Modifiers of the Polymer Scaffolds for Tissue Engineering Applications—A Review
by Katarzyna Klimek and Grazyna Ginalska
Polymers 2020, 12(4), 844; https://doi.org/10.3390/polym12040844 - 6 Apr 2020
Cited by 117 | Viewed by 9326
Abstract
Polymer scaffolds constitute a very interesting strategy for tissue engineering. Even though they are generally non-toxic, in some cases, they may not provide suitable support for cell adhesion, proliferation, and differentiation, which decelerates tissue regeneration. To improve biological properties, scaffolds are frequently enriched [...] Read more.
Polymer scaffolds constitute a very interesting strategy for tissue engineering. Even though they are generally non-toxic, in some cases, they may not provide suitable support for cell adhesion, proliferation, and differentiation, which decelerates tissue regeneration. To improve biological properties, scaffolds are frequently enriched with bioactive molecules, inter alia extracellular matrix proteins, adhesive peptides, growth factors, hormones, and cytokines. Although there are many papers describing synthesis and properties of polymer scaffolds enriched with proteins or peptides, few reviews comprehensively summarize these bioactive molecules. Thus, this review presents the current knowledge about the most important proteins and peptides used for modification of polymer scaffolds for tissue engineering. This paper also describes the influence of addition of proteins and peptides on physicochemical, mechanical, and biological properties of polymer scaffolds. Moreover, this article sums up the major applications of some biodegradable natural and synthetic polymer scaffolds modified with proteins and peptides, which have been developed within the past five years. Full article
(This article belongs to the Special Issue Biodegradable Polymer Scaffolds for Tissue Engineering)
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