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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15 pages, 6550 KiB  
Article
Free Vibration Analysis of a Tunable Micro-Fabrication Device Comprising Asymmetric L-Shaped Membranes
by Cheng-Hua Xiong, Lian-Gui He, Kao-Hao Chang and Chang-Wei Huang
Polymers 2023, 15(10), 2293; https://doi.org/10.3390/polym15102293 - 12 May 2023
Viewed by 1121
Abstract
Membrane sensors have been widely used in various fields owing to their multifunctionality and cost-effectiveness. However, few studies have investigated frequency-tunable membrane sensors, which could enable versatility in the face of different device requirements while retaining high sensitivity, fast response times, and high [...] Read more.
Membrane sensors have been widely used in various fields owing to their multifunctionality and cost-effectiveness. However, few studies have investigated frequency-tunable membrane sensors, which could enable versatility in the face of different device requirements while retaining high sensitivity, fast response times, and high accuracy. In this study, we propose a device comprising an asymmetric L-shaped membrane with tunable operating frequencies for microfabrication and mass sensing applications. The resonant frequency could be controlled by adjusting the membrane geometry. To fully understand the vibration characteristics of the asymmetric L-shaped membrane, the free vibrations of the membrane are first solved by a semi-analytical treatment combining domain decomposition and variable separation methods. The finite-element solutions confirmed the validity of the derived semi-analytical solutions. Parametric analysis results revealed that the fundamental natural frequency decreases monotonically with the increase in length or width of the membrane segment. Numerical examples revealed that the proposed model can be employed to identify suitable materials for membrane sensors with specific frequency requirements under a given set of L-shaped membrane geometries. The model can also achieve frequency matching by changing the length or width of membrane segments given a specified membrane material. Finally, performance sensitivity analyses for mass sensing were carried out, and the results showed that the performance sensitivity was up to 0.7 kHz/pg for polymer materials under certain conditions. Full article
(This article belongs to the Special Issue Polymeric Membranes: Design, Processing and Application)
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16 pages, 2680 KiB  
Article
Behavior Characteristics and Thermal Energy Absorption Mechanism of Physical Blowing Agents in Polyurethane Foaming Process
by Haozhen Wang, Yingshu Liu and Lin Lin
Polymers 2023, 15(10), 2285; https://doi.org/10.3390/polym15102285 - 12 May 2023
Cited by 1 | Viewed by 1552
Abstract
Polyurethane rigid foam is a widely used insulation material, and the behavior characteristics and heat absorption performance of the blowing agent used in the foaming process are key factors that affect the molding performance of this material. In this work, the behavior characteristics [...] Read more.
Polyurethane rigid foam is a widely used insulation material, and the behavior characteristics and heat absorption performance of the blowing agent used in the foaming process are key factors that affect the molding performance of this material. In this work, the behavior characteristics and heat absorption of the polyurethane physical blowing agent in the foaming process were studied; this is something which has not been comprehensively studied before. This study investigated the behavior characteristics of polyurethane physical blowing agents in the same formulation system, including the efficiency, dissolution, and loss rates of the physical blowing agents during the polyurethane foaming process. The research findings indicate that both the physical blowing agent mass efficiency rate and mass dissolution rate are influenced by the vaporization and condensation process of physical blowing agent. For the same type of physical blowing agent, the amount of heat absorbed per unit mass decreases gradually as the quantity of physical blowing agent increases. The relationship between the two shows a pattern of initial rapid decrease followed by a slower decrease. Under the same physical blowing agent content, the higher the heat absorbed per unit mass of physical blowing agent, the lower the internal temperature of the foam when the foam stops expanding. The heat absorbed per unit mass of the physical blowing agents is a key factor affecting the internal temperature of the foam when it stops expanding. From the perspective of heat control of the polyurethane reaction system, the effects of physical blowing agents on the foam quality were ranked in order from good to poor as follows: HFC-245fa, HFC-365mfc, HFCO-1233zd(E), HFO-1336mzzZ, and HCFC-141b. Full article
(This article belongs to the Special Issue Advanced Study on Polyurethane)
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20 pages, 8356 KiB  
Article
Thermo-Mechanical Recyclability of Additively Manufactured Polypropylene and Polylactic Acid Parts and Polypropylene Support Structures
by Niko Nagengast, Christian Bay, Frank Döpper, Hans-Werner Schmidt and Christian Neuber
Polymers 2023, 15(10), 2291; https://doi.org/10.3390/polym15102291 - 12 May 2023
Cited by 3 | Viewed by 1529
Abstract
Polymers have a reputation for several advantageous characteristics like chemical resistance, weight reduction, and simple form-giving processes. The rise of additive manufacturing technologies such as Fused Filament Fabrication (FFF) has introduced an even more versatile production process that supported new product design and [...] Read more.
Polymers have a reputation for several advantageous characteristics like chemical resistance, weight reduction, and simple form-giving processes. The rise of additive manufacturing technologies such as Fused Filament Fabrication (FFF) has introduced an even more versatile production process that supported new product design and material concepts. This led to new investigations and innovations driven by the individualization of customized products. The other side of the coin contains an increasing resource and energy consumption satisfying the growing demand for polymer products. This turns into a magnitude of waste accumulation and increased resource consumption. Therefore, appropriate product and material design, taking into account end-of-life scenarios, is essential to limit or even close the loop of economically driven product systems. In this paper, a comparison of virgin and recycled biodegradable (polylactic acid (PLA)) and petroleum-based (polypropylene (PP) & support) filaments for extrusion-based Additive Manufacturing is presented. For the first time, the thermo-mechanical recycling setup contained a service-life simulation, shredding, and extrusion. Specimens and complex geometries with support materials were manufactured with both, virgin and recycled materials. An empirical assessment was executed through mechanical (ISO 527), rheological (ISO 1133), morphological, and dimensional testing. Furthermore, the surface properties of the PLA and PP printed parts were analyzed. In summary, PP parts and parts from its support structure showed, in consideration of all parameters, suitable recyclability with a marginal parameter variance in comparison to the virgin material. The PLA components showed an acceptable decline in the mechanical values but through thermo-mechanical degradation processes, rheological and dimensional properties of the filament dropped decently. This results in significantly identifiable artifacts of the product optics, based on an increase in surface roughness. Full article
(This article belongs to the Special Issue Progress in 3D Printing)
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19 pages, 7685 KiB  
Article
Calculation of Strain Energy Density Function Using Ogden Model and Mooney–Rivlin Model Based on Biaxial Elongation Experiments of Silicone Rubber
by Yoshihiro Yamashita, Hideyuki Uematsu and Shuichi Tanoue
Polymers 2023, 15(10), 2266; https://doi.org/10.3390/polym15102266 - 11 May 2023
Cited by 4 | Viewed by 3006
Abstract
Strain energy density functions are used in CAE analysis of hyperelastic materials such as rubber and elastomers. This function can originally be obtained only by experiments using biaxial deformation, but the difficulty of such experiments has made it almost impossible to put the [...] Read more.
Strain energy density functions are used in CAE analysis of hyperelastic materials such as rubber and elastomers. This function can originally be obtained only by experiments using biaxial deformation, but the difficulty of such experiments has made it almost impossible to put the function to practical use. Furthermore, it has been unclear how to introduce the strain energy density function necessary for CAE analysis from the results of biaxial deformation experiments on rubber. In this study, parameters of the Ogden and Mooney–Rivlin approximations of the strain energy density function were derived from the results of biaxial deformation experiments on silicone rubber, and their validity was verified. These results showed that it is best to determine the coefficients of the approximate equations for the strain energy density function after 10 cycles of repeated elongation of rubber in an equal biaxial deformation state, followed by equal biaxial elongation, uniaxial constrained biaxial elongation, and uniaxial elongation to obtain these three stress–strain curves. Full article
(This article belongs to the Section Polymer Analysis and Characterization)
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18 pages, 33150 KiB  
Article
Additive Manufacturing of Biodegradable Hemp-Reinforced Polybutylene Succinate (PBS) and Its Mechanical Characterization
by Antonia Dönitz, Anton Köllner, Tim Richter, Oliver Löschke, Dietmar Auhl and Christina Völlmecke
Polymers 2023, 15(10), 2271; https://doi.org/10.3390/polym15102271 - 11 May 2023
Cited by 6 | Viewed by 2083
Abstract
The additive manufacturing of natural fibre-reinforced polymers is a pivotal method in developing sustainable engineering solutions. Using the fused filament fabrication method, the current study investigates the additive manufacturing of hemp-reinforced polybutylene succinate (PBS) alongside its mechanical characterization. Two types of hemp reinforcement [...] Read more.
The additive manufacturing of natural fibre-reinforced polymers is a pivotal method in developing sustainable engineering solutions. Using the fused filament fabrication method, the current study investigates the additive manufacturing of hemp-reinforced polybutylene succinate (PBS) alongside its mechanical characterization. Two types of hemp reinforcement are considered: short fibres (max. length smaller than 2 mm) and long fibres (max. length smaller than 10 mm), which are compared against non-reinforced (pure) PBS. A detailed analysis is performed regarding the determination of suitable 3D printing parameters (overlap, temperature, nozzle diameter). In a comprehensive experimental study, additionally to general analyses regarding the influence of hemp reinforcement on the mechanical behaviour, the effect of printing parameters is determined and discussed. Introducing an overlap in the additive manufacturing of the specimens results in improved mechanical performance. The study highlights that the Young’s modulus of PBS can be improved by 63% by introducing hemp fibres in conjunction with overlap. In contrast, hemp fibre reinforcement reduces the tensile strength of PBS, while this effect is less pronounced considering overlap in the additive manufacturing process. Full article
(This article belongs to the Special Issue Additive Manufacturing of (Bio) Polymeric Materials)
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10 pages, 1887 KiB  
Article
Electropositive Membrane Prepared via a Simple Dipping Process: Exploiting Electrostatic Attraction Using Electrospun SiO2/PVDF Membranes with Electronegative SiO2 Shell
by Dalsu Choi, Cheol Ho Lee, Han Bi Lee, Min Wook Lee and Seong Mu Jo
Polymers 2023, 15(10), 2270; https://doi.org/10.3390/polym15102270 - 11 May 2023
Cited by 1 | Viewed by 1614
Abstract
This research aimed to develop a simple and cost-effective method for fabricating electropositive membranes for highly efficient water filtration. Electropositive membranes are novel functional membranes with electropositive properties and can filter electronegative viruses and bacteria using electrostatic attraction. Because electropositive membranes do not [...] Read more.
This research aimed to develop a simple and cost-effective method for fabricating electropositive membranes for highly efficient water filtration. Electropositive membranes are novel functional membranes with electropositive properties and can filter electronegative viruses and bacteria using electrostatic attraction. Because electropositive membranes do not rely on physical filtration, they exhibit high flux characteristics compared with conventional membranes. This study presents a simple dipping process for fabricating boehmite/SiO2/PVDF electropositive membranes by modifying an electrospun SiO2/PVDF host membrane using electropositive boehmite nanoparticles (NPs). The surface modification enhanced the filtration performance of the membrane, as revealed by electronegatively charged polystyrene (PS) NPs as a bacteria model. The boehmite/SiO2/PVDF electropositive membrane, with an average pore size of 0.30 μm, could successfully filter out 0.20 μm PS particles. The rejection rate was comparable to that of Millipore GSWP, a commercial filter with a pore size of 0.22 μm, which can filter out 0.20 μm particles via physical sieving. In addition, the water flux of the boehmite/SiO2/PVDF electropositive membrane was twice that of Millipore GSWP, demonstrating the potential of the electropositive membrane in water purification and disinfection. Full article
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23 pages, 7694 KiB  
Article
Preparation of Eco-Friendly Chelating Resins and Their Applications for Water Treatment
by Nicoleta Mirela Marin, Georgiana Dolete, Ludmila Motelica, Roxana Trusca, Ovidiu Cristian Oprea and Anton Ficai
Polymers 2023, 15(10), 2251; https://doi.org/10.3390/polym15102251 - 10 May 2023
Cited by 2 | Viewed by 2106
Abstract
In the present study, two chelating resins were prepared and used for simultaneous adsorption of toxic metal ions, i.e., Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, [...] Read more.
In the present study, two chelating resins were prepared and used for simultaneous adsorption of toxic metal ions, i.e., Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, and Pb2+ (MX+). In the first step, chelating resins were prepared starting with styrene-divinylbenzene resin, a strong basic anion exchanger Amberlite IRA 402(Cl) with two chelating agents, i.e., tartrazine (TAR) and amido black 10B (AB 10B). Key parameters such as contact time, pH, initial concentration, and stability were evaluated for the obtained chelating resins (IRA 402/TAR and IRA 402/AB 10B). The obtained chelating resins show excellent stability in 2M HCl, 2M NaOH, and also in ethanol (EtOH) medium. The stability of the chelating resins decreased when the combined mixture (2M HCl:EtOH = 2:1) was added. The above-mentioned aspect was more evident for IRA 402/TAR compared to IRA 402/AB 10B. Taking into account the higher stability of the IRA 402/TAR and IRA 402/AB 10B resins, in a second step, adsorption studies were carried out on complex acid effluents polluted with MX+. The adsorption of MX+ from an acidic aqueous medium on the chelating resins was evaluated using the ICP-MS method. The following affinity series under competitive analysis for IRA 402/TAR was obtained: Fe3+(44 µg/g) > Ni2+(39.8 µg/g) > Cd2+(34 µg/g) > Cr3+(33.2 µg/g) > Pb2+(32.7 µg/g) > Cu2+ (32.5 µg/g) > Mn2+(31 µg/g) > Co2+(29 µg/g) > Zn2+ (27.5 µg/g). While for IRA 402/AB 10B, the following behavior was observed: Fe3+(58 µg/g) > Ni2+(43.5 µg/g) > Cd2+(43 µg/g) > Cu2+(38 µg/g) > Cr3+(35 µg/g) > Pb2+(34.5 µg/g) > Co2+(32.8 µg/g) > Mn2+(33 µg/g) > Zn2+(32 µg/g), consistent with the decreasing affinity of MX+ for chelate resin. The chelating resins were characterized using TG, FTIR, and SEM analysis. The obtained results showed that the chelating resins prepared have promising potential for wastewater treatment in the context of the circular economy approach. Full article
(This article belongs to the Section Polymer Applications)
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17 pages, 4073 KiB  
Article
In Vitro Evaluation of Biphasic Calcium Phosphate Scaffolds Derived from Cuttlefish Bone Coated with Poly(ester urea) for Bone Tissue Regeneration
by Patrícia Pereira, Ana S. Neto, Ana S. Rodrigues, Inês Barros, Catarina Miranda, João Ramalho-Santos, Luís Pereira de Almeida, José M. F. Ferreira, Jorge F. J. Coelho and Ana C. Fonseca
Polymers 2023, 15(10), 2256; https://doi.org/10.3390/polym15102256 - 10 May 2023
Cited by 2 | Viewed by 1793
Abstract
This study investigates the osteogenic differentiation of umbilical-cord-derived human mesenchymal stromal cells (hUC-MSCs) on biphasic calcium phosphate (BCP) scaffolds derived from cuttlefish bone doped with metal ions and coated with polymers. First, the in vitro cytocompatibility of the undoped and ion-doped (Sr2+ [...] Read more.
This study investigates the osteogenic differentiation of umbilical-cord-derived human mesenchymal stromal cells (hUC-MSCs) on biphasic calcium phosphate (BCP) scaffolds derived from cuttlefish bone doped with metal ions and coated with polymers. First, the in vitro cytocompatibility of the undoped and ion-doped (Sr2+, Mg2+ and/or Zn2+) BCP scaffolds was evaluated for 72 h using Live/Dead staining and viability assays. From these tests, the most promising composition was found to be the BCP scaffold doped with strontium (Sr2+), magnesium (Mg2+) and zinc (Zn2+) (BCP-6Sr2Mg2Zn). Then, samples from the BCP-6Sr2Mg2Zn were coated with poly(ԑ-caprolactone) (PCL) or poly(ester urea) (PEU). The results showed that hUC-MSCs can differentiate into osteoblasts, and hUC-MSCs seeded on the PEU-coated scaffolds proliferated well, adhered to the scaffold surfaces, and enhanced their differentiation capabilities without negative effects on cell proliferation under in vitro conditions. Overall, these results suggest that PEU-coated scaffolds are an alternative to PCL for use in bone regeneration, providing a suitable environment to maximally induce osteogenesis. Full article
(This article belongs to the Special Issue Development and Application of Polymer Scaffolds)
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18 pages, 6747 KiB  
Article
Renewable Poly(Lactic Acid)Lignocellulose Biocomposites for the Enhancement of the Water Retention Capacity of the Soil
by Dalila Rubicela Cruz Fabian, Silvie Durpekova, Miroslava Dusankova, Jaroslav Cisar, Petra Drohsler, Ondrej Elich, Marketa Borkova, Jarmila Cechmankova and Vladimir Sedlarik
Polymers 2023, 15(10), 2243; https://doi.org/10.3390/polym15102243 - 9 May 2023
Cited by 6 | Viewed by 1552
Abstract
This manuscript details the preparation and characterization of a renewable biocomposite material intended as a soil conditioner based on low-molecular-weight poly(lactic acid) (PLA) and residual biomass (wheat straw and wood sawdust). The swelling properties and biodegradability of the PLA-lignocellulose composite under environmental conditions [...] Read more.
This manuscript details the preparation and characterization of a renewable biocomposite material intended as a soil conditioner based on low-molecular-weight poly(lactic acid) (PLA) and residual biomass (wheat straw and wood sawdust). The swelling properties and biodegradability of the PLA-lignocellulose composite under environmental conditions were evaluated as indicators of its potential for applications in soil. Its mechanical and structural properties were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). Results showed that the incorporation of lignocellulose waste material into PLA increased the swelling ratio of the biocomposite by up to 300%. The application of the biocomposite of 2 wt% in soil enhanced its capacity for water retention by 10%. In addition, the cross-linked structure of the material proved to be capable of swelling and deswelling repeatedly, indicating its good reusability. Incorporating lignocellulose waste in the PLA enhanced its stability in the soil environment. After 50 days of the experiment, almost 50% of the sample had degraded in the soil. Full article
(This article belongs to the Section Biomacromolecules, Biobased and Biodegradable Polymers)
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14 pages, 6743 KiB  
Article
Study on the Effect of Core-Shell Abaca Vascular Carriers on the Self-Healing and Mechanical Properties of Thermoset Panels
by K. Venkata Chalapathi, M. N. Prabhakar and Jung-il Song
Polymers 2023, 15(10), 2245; https://doi.org/10.3390/polym15102245 - 9 May 2023
Cited by 1 | Viewed by 1207
Abstract
Self-healing panels were prepared using vinyl ester (VE) and vascular abaca fibers (unidirectional) through the hand lay-up process. Initially, two sets of abaca fibers (AF) were prepared by filling the healing resin VE and hardener and stacking both core-filled unidirectional fibers in a [...] Read more.
Self-healing panels were prepared using vinyl ester (VE) and vascular abaca fibers (unidirectional) through the hand lay-up process. Initially, two sets of abaca fibers (AF) were prepared by filling the healing resin VE and hardener and stacking both core-filled unidirectional fibers in a 90° direction to obtain sufficient healing. The experimental results demonstrated that the healing efficiency increased by approximately 3%. SEM-EDX analysis further confirmed the healing process by exhibiting spill-out resin and the respective fibers’ major chemical elements at the damaged site after self-healing. The tensile, flexural, and Izod impact strengths of self-healing panels indicated improved strengths of 7.85%, 49.43%, and 53.84%, respectively, compared with fibers with empty lumen-reinforced VE panels due to the presence of a core and interfacial bonding between the reinforcement and matrix. Overall, the study proved that abaca lumens could effectively serve as healing carriers for thermoset resin panels. Full article
(This article belongs to the Topic Advanced Carbon Fiber Reinforced Composite Materials)
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22 pages, 5980 KiB  
Review
Shear Thickening Fluid and Its Application in Impact Protection: A Review
by Haiqing Liu, Kunkun Fu, Xiaoyu Cui, Huixin Zhu and Bin Yang
Polymers 2023, 15(10), 2238; https://doi.org/10.3390/polym15102238 - 9 May 2023
Cited by 10 | Viewed by 6410
Abstract
Shear thickening fluid (STF) is a dense colloidal suspension of nanoparticles in a carrier fluid in which the viscosity increases dramatically with a rise in shear rate. Due to the excellent energy absorption and energy dissipation of STF, there is a desire to [...] Read more.
Shear thickening fluid (STF) is a dense colloidal suspension of nanoparticles in a carrier fluid in which the viscosity increases dramatically with a rise in shear rate. Due to the excellent energy absorption and energy dissipation of STF, there is a desire to employ STFs in a variety of impact applications. In this study, a comprehensive review on STFs’ applications is presented. First, several common shear thickening mechanisms are discussed in this paper. The applications of different STF impregnated fabric composites and the STF’s contributions on improving the impact, ballistic and stab resistance performance have also been presented. Moreover, recent developments of STF’s applications, including dampers and shock absorbers, are included in this review. In addition, some novel applications (acoustic structure, STF-TENG and electrospun nonwoven mats) based on STF are summarized, to suggest the challenges of future research and propose some more deterministic research directions, e.g., potential trends for applications of STF. Full article
(This article belongs to the Section Polymer Composites and Nanocomposites)
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14 pages, 3623 KiB  
Article
Improvement of Natural Polymeric Films Properties by Blend Formulation for Sustainable Active Food Packaging
by Emanuela Drago, Roberta Campardelli, Alberto Lagazzo, Giuseppe Firpo and Patrizia Perego
Polymers 2023, 15(9), 2231; https://doi.org/10.3390/polym15092231 - 8 May 2023
Cited by 5 | Viewed by 2496
Abstract
Active packaging manufactured with biopolymers extracted from agri-food waste is one of the most innovative and eco-sustainable strategies for maintaining food quality. However, biopolymers often present poor performances, which hinders their competitiveness compared with plastics. This work focused on developing and optimizing a [...] Read more.
Active packaging manufactured with biopolymers extracted from agri-food waste is one of the most innovative and eco-sustainable strategies for maintaining food quality. However, biopolymers often present poor performances, which hinders their competitiveness compared with plastics. This work focused on developing and optimizing a natural polymeric blend produced by solvent casting based on zein and chitosan to improve the pure biopolymers’ properties. The best results were obtained by blending zein and chitosan in a 1:2 weight ratio. The films were characterized in terms of morphology, mechanical and oxygen barrier properties, thermal stability, transparency and wettability. The blend production allowed us to obtain lower brittleness and lower stiffness materials compared with pure polymer films, with oxygen permeability values two orders of magnitude lower than pure zein, better optical properties with respect to pure chitosan and good thermal stability. The wettability properties of the blend did not result in being altered with respect to the single polymer, which was found to have hydrophilic behavior, highlighting the strong influence of glycerol used as a plasticizer. The results suggested that the polymer blending strategy is a viable and cost-effective method for producing packaging materials as alternatives to plastics. Full article
(This article belongs to the Special Issue Polymers in Food Technology and Food Packaging)
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12 pages, 4714 KiB  
Article
Bio-Inspired Magnetically Controlled Reversibly Actuating Multimaterial Fibers
by Muhammad Farhan, Daniel S. Hartstein, Yvonne Pieper, Marc Behl, Andreas Lendlein and Axel T. Neffe
Polymers 2023, 15(9), 2233; https://doi.org/10.3390/polym15092233 - 8 May 2023
Cited by 1 | Viewed by 1340
Abstract
Movements in plants, such as the coiling of tendrils in climbing plants, have been studied as inspiration for coiling actuators in robotics. A promising approach to mimic this behavior is the use of multimaterial systems that show different elastic moduli. Here, we report [...] Read more.
Movements in plants, such as the coiling of tendrils in climbing plants, have been studied as inspiration for coiling actuators in robotics. A promising approach to mimic this behavior is the use of multimaterial systems that show different elastic moduli. Here, we report on the development of magnetically controllable/triggerable multimaterial fibers (MMFs) as artificial tendrils, which can reversibly coil and uncoil on stimulation from an alternating magnetic field. These MMFs are based on deformed shape-memory fibers with poly[ethylene-co-(vinyl acetate)] (PEVA) as their core and a silicone-based soft elastomeric magnetic nanocomposite shell. The core fiber provides a temperature-dependent expansion/contraction that propagates the coiling of the MMF, while the shell enables inductive heating to actuate the movements in these MMFs. Composites with mNP weight content ≥ 15 wt% were required to achieve heating suitable to initiate movement. The MMFs coil upon application of the magnetic field, in which a degree of coiling N = 0.8 ± 0.2 was achieved. Cooling upon switching OFF the magnetic field reversed some of the coiling, giving a reversible change in coiling ∆n = 2 ± 0.5. These MMFs allow magnetically controlled remote and reversible actuation in artificial (soft) plant-like tendrils, and are envisioned as fiber actuators in future robotics applications. Full article
(This article belongs to the Special Issue Frontier in Magneto-/ Electro-Active Elastomers)
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22 pages, 3023 KiB  
Article
Synthesis and Micellization Behavior of Amphiphilic Block Copolymers of Poly(N-vinyl Pyrrolidone) and Poly(Benzyl Methacrylate): Block versus Statistical Copolymers
by Nikoletta Roka and Marinos Pitsikalis
Polymers 2023, 15(9), 2225; https://doi.org/10.3390/polym15092225 - 8 May 2023
Cited by 1 | Viewed by 1810
Abstract
Block copolymers of N-vinyl pyrrolidone (NVP) and benzyl methacrylate (BzMA), PNVP-b-PBzMA, were prepared by RAFT polymerization techniques and sequential addition of monomers. The copolymers were characterized by Size Exclusion Chromatography (SEC) and NMR spectroscopy. Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA) [...] Read more.
Block copolymers of N-vinyl pyrrolidone (NVP) and benzyl methacrylate (BzMA), PNVP-b-PBzMA, were prepared by RAFT polymerization techniques and sequential addition of monomers. The copolymers were characterized by Size Exclusion Chromatography (SEC) and NMR spectroscopy. Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA) and Differential Thermogravimetry (DTG) were employed to study the thermal properties of these copolymers. The micellization behavior in THF, which is a selective solvent for the PBzMA blocks, was examined. For comparison the self-assembly properties of the corresponding statistical copolymers, PNVP-stat-PBzMA, were studied. In addition, the association behavior in aqueous solutions was analyzed for the block copolymers, PNVP-b-PBzMA. In this case, the solvent is selective for the PNVP blocks. Dilute solution viscometry, static (SLS) and dynamic light scattering (DLS) were employed as the tools to investigate the micellar assemblies. The efficient encapsulation of the hydrophobic curcumin within the micellar core of the supramolecular structures in aqueous solutions was demonstrated by UV-Vis spectroscopy and DLS measurements. Full article
(This article belongs to the Special Issue Block Copolymers: Self-Assembly and Applications)
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12 pages, 8616 KiB  
Article
In-Process Orbiting Laser-Assisted Technique for the Surface Finish in Material Extrusion-Based 3D Printing
by Pu Han, Sihan Zhang, Zhong Yang, M. Faisal Riyad, Dan O. Popa and Keng Hsu
Polymers 2023, 15(9), 2221; https://doi.org/10.3390/polym15092221 - 8 May 2023
Cited by 1 | Viewed by 1378
Abstract
Material extrusion-based polymer 3D printing, one of the most commonly used additive manufacturing processes for thermoplastics and composites, has drawn extensive attention due to its capability and cost effectiveness. However, the low surface finish quality of the printed parts remains a drawback due [...] Read more.
Material extrusion-based polymer 3D printing, one of the most commonly used additive manufacturing processes for thermoplastics and composites, has drawn extensive attention due to its capability and cost effectiveness. However, the low surface finish quality of the printed parts remains a drawback due to the nature of stacking successive layers along one direction and the nature of rastering of the extruded tracks of material. In this work, an in-process thermal radiation-assisted, surface reflow method is demonstrated that significantly improves the surface finish of the sidewalls of printed parts. It is observed that the surface finish of the printed part is drastically improved for both flat and curved surfaces. The effect of surface reflow on roughness reduction was characterized using optical profilometry and scanning electron microscopy (SEM), while the local heated spot temperature was quantified using a thermal camera. Full article
(This article belongs to the Special Issue Progress in 3D Printing)
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12 pages, 5706 KiB  
Article
Preventing the Distortion of CoO6 Octahedra of LiCoO2 at High-Voltage Operation of Lithium-Ion Battery: An Organic Surface Reinforcement
by Fu-Ming Wang
Polymers 2023, 15(9), 2211; https://doi.org/10.3390/polym15092211 - 6 May 2023
Cited by 1 | Viewed by 1636
Abstract
Lithium cobalt oxide (LiCoO2, LCO) has been widely used in electronic markets due to its high energy density and wide voltage range applications. Recently, high-voltage (HV, >4.5 V) operation has been required to obey the requirements of high energy density and [...] Read more.
Lithium cobalt oxide (LiCoO2, LCO) has been widely used in electronic markets due to its high energy density and wide voltage range applications. Recently, high-voltage (HV, >4.5 V) operation has been required to obey the requirements of high energy density and cycle life in several applications such as electric vehicles and energy storage. However, the HV operation causes structure instability due to the over de-lithiation of LCO, as well as decomposing common carbonate solvents, thereby incurring the decay of battery performance. Moreover, a distortion of the CoO6 octahedra of LCO during de-lithiation induces a rehybridization of the Co 3d and O 2p orbitals. According to above reasons, decreasing the Co-O covalent bond promptly triggers high risks that significantly limit further use of LCO. In this research, an organic surface reinforcement by using bismaleimide–uracil (BU) that electrochemically forms a cathode electrolyte interphase (CEI) on LCO was explored. The results of electrochemical impedance spectroscopy and battery performance, such as the c-rate and cyclability tests, demonstrated that the modified CEI formed from BU significantly prevents the distortion of CoO6 octahedra. X-ray photoelectronic spectroscopy and in situ XAS indicated less LiF formation and higher bond energy of Co-O improved. Finally, the differential scanning calorimetry showed the onset temperature of decomposition of LCO was extended from 245 to 270 °C at 100% state of charge, which is about a 25 °C extension. The exothermic heat of LCO decreased by approximately 30% for high-safety use. This research confirms that the BU is eligible for high voltage (>4.5 V) LCO and presents outstanding electrochemical properties and safety performances. Full article
(This article belongs to the Special Issue Polymer Composite Materials for Energy Storage)
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17 pages, 9834 KiB  
Article
Effect of 3D Printing Process Parameters and Heat Treatment Conditions on the Mechanical Properties and Microstructure of PEEK Parts
by Honglei Zhen, Bin Zhao, Long Quan and Junyu Fu
Polymers 2023, 15(9), 2209; https://doi.org/10.3390/polym15092209 - 6 May 2023
Cited by 5 | Viewed by 2466
Abstract
Fused deposition modeling (FDM) processed Poly-ether-ether-ketone (PEEK) materials are widely used in aerospace, automobile, biomedical, and electronics industries and other industries due to their excellent mechanical properties, thermal properties, chemical resistance, wear resistance, and biocompatibility, etc. However, the manufacture of PEEK materials and [...] Read more.
Fused deposition modeling (FDM) processed Poly-ether-ether-ketone (PEEK) materials are widely used in aerospace, automobile, biomedical, and electronics industries and other industries due to their excellent mechanical properties, thermal properties, chemical resistance, wear resistance, and biocompatibility, etc. However, the manufacture of PEEK materials and parts utilizing the FDM process faces the challenge of fine-tuning a list of process parameters and heat treatment conditions to reach the best-suiting mechanical properties and microstructures. It is non-trivial to make the selection only according to theoretical analysis while counting on a vast number of experiments is the general situation. Therefore, in this paper, the extrusion rate, filling angle, and printing orientation are investigated to adjust the mechanical properties of 3D-printed PEEK parts; then, a variety of heat treatment conditions were applied to tune the crystallinity and strength. The results show that the best mechanical performance is achieved at 1.0 times the extrusion rate, varied angle cross-fillings with ±10° intervals, and vertical printing. Horizontal printing performs better with reduced warpage. Additionally, both crystallinity and mechanical properties are significantly improved after heat treatment, and the best state is achieved after holding at 300 °C for 2 h. The resulting tensile strength is close to 80% of the strength of injection-molded PEEK parts. Full article
(This article belongs to the Special Issue Mechanical and Physical Properties of 3D Printed Polymer Materials)
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11 pages, 22113 KiB  
Article
On-Chip 3D Printing of Polymer Waveguide-Coupled Single-Photon Emitter Based on Colloidal Quantum Dots
by Gia Long Ngo, Long Nguyen, Jean-Pierre Hermier and Ngoc Diep Lai
Polymers 2023, 15(9), 2201; https://doi.org/10.3390/polym15092201 - 6 May 2023
Cited by 1 | Viewed by 1599
Abstract
In the field of quantum technology, there has been a growing interest in fully integrated systems that employ single photons due to their potential for high performance and scalability. Here, a simple method is demonstrated for creating on-chip 3D printed polymer waveguide-coupled single-photon [...] Read more.
In the field of quantum technology, there has been a growing interest in fully integrated systems that employ single photons due to their potential for high performance and scalability. Here, a simple method is demonstrated for creating on-chip 3D printed polymer waveguide-coupled single-photon emitters based on colloidal quantum dots (QDs). By using a simple low-one photon absorption technique, we were able to create a 3D polymeric crossed-arc waveguide structure with a bright QD on top. These waveguides can conduct both excitation laser and emitted single photons, which facilitates the characterization of single-photon signals at different outputs with a conventional confocal scanning system. To optimize the guiding effect of the polymeric waveguide structures, comprehensive 3D finite-difference time-domain simulations were performed. Our method provides a straightforward and cost-effective way to integrate high-performance single-photon sources with on-chip photonic devices, enabling scalable and versatile quantum photonic circuits for various applications. Full article
(This article belongs to the Section Polymer Applications)
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12 pages, 2173 KiB  
Article
Polypropylene Degradation on Co-Rotating Twin-Screw Extruders
by Matthias Altepeter, Volker Schöppner, Sven Wanke, Laura Austermeier, Philipp Meinheit and Leon Schmidt
Polymers 2023, 15(9), 2181; https://doi.org/10.3390/polym15092181 - 4 May 2023
Cited by 1 | Viewed by 1716
Abstract
Nowadays, usable plastic materials with defined properties are created by blending additives into the base polymer. This is the main task of compounding on co-rotating twin-screw extruders. The thermal and mechanical stress occurring in the process leads to a mostly irreversible damage to [...] Read more.
Nowadays, usable plastic materials with defined properties are created by blending additives into the base polymer. This is the main task of compounding on co-rotating twin-screw extruders. The thermal and mechanical stress occurring in the process leads to a mostly irreversible damage to the material. Consequently, the properties of the polymer melt and the subsequent product are affected. The material degradation of polypropylene (PP) on a 28 mm twin-screw extruder has already been studied and modeled at Kunststofftechnik Paderborn. In this work, the transferability of the previous results to other machine sizes and polypropylene compounds were investigated experimentally. Therefore, pure polypropylene was processed with screw diameters of 25 mm and 45 mm. Furthermore, polypropylene compounds with titanium dioxide as well as carbon fibers were considered on a 28 mm extruder. In the course of the evaluation of the pure polypropylene, the melt flow rates of the samples were measured and the molar masses were calculated on this basis. The compounds were analyzed by gel permeation chromatography. As in the previous investigations, high rotational speeds, low throughputs and high melt temperatures lead to a higher material degradation. In addition, it is illustrated that the previously developed model for the calculation of material degradation is generally able to predict the degradation even for different machine sizes by adjusting the process coefficients. In summary, this article shows that compounders can use the recommendations for action and the calculation model for the material degradation of polypropylene, irrespective of the machine size, to design processes that are gentle on the material. Full article
(This article belongs to the Special Issue Durability and Degradation of Polymeric Materials II)
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10 pages, 2226 KiB  
Article
Influence of Incorporating Recycled Windshield Glass, PVB-Foil, and Rubber Granulates on the Properties of Geopolymer Composites and Concretes
by Van Su Le, Katarzyna Ewa Buczkowska, Roberto Ercoli, Kinga Pławecka, Narcisa Mihaela Marian and Petr Louda
Polymers 2023, 15(9), 2122; https://doi.org/10.3390/polym15092122 - 29 Apr 2023
Cited by 1 | Viewed by 1426
Abstract
Waste materials from the automotive industries were re-used as aggregates into metakaolin-based geopolymer (GP), geopolymer mortar (GM), and Bauhaus B20-based concrete composite (C). Specifically, the study evaluates the ability of windshield silica glass (W), PVB-Foils (P), and rubber granulates (G) to impact the [...] Read more.
Waste materials from the automotive industries were re-used as aggregates into metakaolin-based geopolymer (GP), geopolymer mortar (GM), and Bauhaus B20-based concrete composite (C). Specifically, the study evaluates the ability of windshield silica glass (W), PVB-Foils (P), and rubber granulates (G) to impact the mechanical and thermal properties. The addition of the recovered materials into the experimental geopolymers outperformed the commercially available B20. The flexural strength reached values of 7.37 ± 0.51 MPa in concrete with silica glass, 4.06 ± 0.32 in geopolymer malt with PVB-Foils, and 6.99 ± 0.82 MPa in pure geopolymer with rubber granulates; whereas the highest compressive strengths (бc) were obtained by the addition of PVB-Foils in pure geopolymer, geopolymer malt, and concrete (43.16 ± 0.31 MPa, 46.22 ± 2.06 MPa, and 27.24 ± 1.28 MPa, respectively). As well PVB-Foils were able to increase the impact strength (бi) at 5.15 ± 0.28 J/cm2 in pure geopolymer, 5.48 ± 0.41 J/cm2 in geopolymer malt, and 3.19 ± 0.14 J/cm2 in concrete, furnishing a significant improvement over the reference materials. Moreover, a correlation between density and thermal conductivity (λ) was also obtained to provide the suitability of these materials in applications such as insulation or energy storage. These findings serve as a basis for further research on the use of waste materials in the creation of new, environmentally friendly composites. Full article
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15 pages, 4720 KiB  
Article
Antibacterial and Physicochemical Properties of Orthodontic Resin Cement Containing ZnO-Loaded Halloysite Nanotubes
by Jeong-Hye Seo, Kwang-Mahn Kim and Jae-Sung Kwon
Polymers 2023, 15(9), 2045; https://doi.org/10.3390/polym15092045 - 25 Apr 2023
Cited by 2 | Viewed by 1259
Abstract
Demineralized white lesions are a common problem when using orthodontic resin cement, which can be prevented with the addition of antibacterial substances. However, the addition of antibacterial substances such as zinc oxide alone may result in the deterioration of the resin cement’s functions. [...] Read more.
Demineralized white lesions are a common problem when using orthodontic resin cement, which can be prevented with the addition of antibacterial substances. However, the addition of antibacterial substances such as zinc oxide alone may result in the deterioration of the resin cement’s functions. Halloysite nanotubes (HNTs) are known to be biocompatible without adversely affecting the mechanical properties of the material while having the ability to load different substances. The purpose of this study was to prepare orthodontic resin cement containing HNT fillers loaded with ZnO (ZnO/HNTs) and to investigate its mechanical, physical, chemical, and antibacterial properties. A group without filler was used as a control. Three groups containing 5 wt.% of HNTs, ZnO, and ZnO/HNTs were prepared. TEM and EDS measurements were carried out to confirm the morphological structure of the HNTs and the successful loading of ZnO onto the HNTs. The mechanical, physical, chemical, and antibacterial properties of the prepared orthodontic resin cement were considered. The ZnO group had high flexural strength and water absorption but a low depth of cure (p < 0.05). The ZnO/HNTs group showed the highest shear bond strength and film thickness (p < 0.05). In the antibacterial test, the ZnO/HNTs group resulted in a significant decrease in the biofilm’s metabolic activity compared to the other groups (p < 0.05). ZnO/HNTs did not affect cell viability. In addition, ZnO was cytotoxic at a concentration of 100% in the extract. The nanocomposite developed in this study exhibited antimicrobial activity against S. mutans while maintaining the mechanical, physical, and chemical properties of orthodontic resin cement. Therefore, it has the potential to be used as an orthodontic resin cement that can prevent DWLs. Full article
(This article belongs to the Special Issue Advanced Polymeric Materials for Dental Applications II)
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20 pages, 3994 KiB  
Article
Statistical Copolymers of N–Vinylpyrrolidone and 2–Chloroethyl Vinyl Ether via Radical RAFT Polymerization: Monomer Reactivity Ratios, Thermal Properties, and Kinetics of Thermal Decomposition of the Statistical Copolymers
by Nikolaos V. Plachouras and Marinos Pitsikalis
Polymers 2023, 15(8), 1970; https://doi.org/10.3390/polym15081970 - 21 Apr 2023
Viewed by 2675
Abstract
The radical statistical copolymerization of N–vinyl pyrrolidone (NVP) and 2–chloroethyl vinyl ether (CEVE) was conducted using the Reversible Addition–Fragmentation chain Transfer (RAFT) polymerization technique, employing [(O–ethylxanthyl)methyl]benzene (CTA-1) and O–ethyl S–(phthalimidylmethyl) xanthate (CTA-2) as the Chain Transfer Agents (CTAs), leading to P(NVP–stat–CEVE) products. [...] Read more.
The radical statistical copolymerization of N–vinyl pyrrolidone (NVP) and 2–chloroethyl vinyl ether (CEVE) was conducted using the Reversible Addition–Fragmentation chain Transfer (RAFT) polymerization technique, employing [(O–ethylxanthyl)methyl]benzene (CTA-1) and O–ethyl S–(phthalimidylmethyl) xanthate (CTA-2) as the Chain Transfer Agents (CTAs), leading to P(NVP–stat–CEVE) products. After optimizing copolymerization conditions, monomer reactivity ratios were estimated using various linear graphical methods, as well as the COPOINT program, which was applied in the framework of the terminal model. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the monomers’ mean sequence lengths. Thermal properties of the copolymers were studied by Differential Scanning Calorimetry (DSC) and kinetics of their thermal degradation by Thermogravimetric Analysis (TGA) and Differential Thermogravimetry (DTG), applying the isoconversional methodologies of Ozawa–Flynn–Wall (OFW) and Kissinger–Akahira–Sunose (KAS). Full article
(This article belongs to the Special Issue State-of-the-Art Polymer Science and Technology in Greece II)
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19 pages, 751 KiB  
Review
Exploiting Polyhydroxyalkanoates for Biomedical Applications
by Vipin Chandra Kalia, Sanjay K. S. Patel and Jung-Kul Lee
Polymers 2023, 15(8), 1937; https://doi.org/10.3390/polym15081937 - 19 Apr 2023
Cited by 8 | Viewed by 3793
Abstract
Polyhydroxyalkanoates (PHA) are biodegradable plastic. Numerous bacteria produce PHAs under environmental stress conditions, such as excess carbon-rich organic matter and limitations of other nutritional elements such as potassium, magnesium, oxygen, phosphorus, and nitrogen. In addition to having physicochemical properties similar to fossil-fuel-based plastics, [...] Read more.
Polyhydroxyalkanoates (PHA) are biodegradable plastic. Numerous bacteria produce PHAs under environmental stress conditions, such as excess carbon-rich organic matter and limitations of other nutritional elements such as potassium, magnesium, oxygen, phosphorus, and nitrogen. In addition to having physicochemical properties similar to fossil-fuel-based plastics, PHAs have unique features that make them ideal for medical devices, such as easy sterilization without damaging the material itself and easy dissolution following use. PHAs can replace traditional plastic materials used in the biomedical sector. PHAs can be used in a variety of biomedical applications, including medical devices, implants, drug delivery devices, wound dressings, artificial ligaments and tendons, and bone grafts. Unlike plastics, PHAs are not manufactured from petroleum products or fossil fuels and are, therefore, environment-friendly. In this review, a recent overview of applications of PHAs with special emphasis on biomedical sectors, including drug delivery, wound healing, tissue engineering, and biocontrols, are discussed. Full article
(This article belongs to the Special Issue Renewable and Biodegradable Polymer-Based Materials and Applications)
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22 pages, 5743 KiB  
Review
Investigation of Polymer Aging Mechanisms Using Molecular Simulations: A Review
by Fan Zhang, Rui Yang and Diannan Lu
Polymers 2023, 15(8), 1928; https://doi.org/10.3390/polym15081928 - 18 Apr 2023
Cited by 12 | Viewed by 3547
Abstract
Aging has a serious impact on the properties of functional polymers. Therefore, it is necessary to study the aging mechanism to prolong the service and storage life of polymer-based devices and materials. Due to the limitations of traditional experimental methods, more and more [...] Read more.
Aging has a serious impact on the properties of functional polymers. Therefore, it is necessary to study the aging mechanism to prolong the service and storage life of polymer-based devices and materials. Due to the limitations of traditional experimental methods, more and more studies have adopted molecular simulations to analyze the intrinsic mechanisms of aging. In this paper, recent advances in molecular simulations of the aging of polymers and their composites are reviewed. The characteristics and applications of commonly used simulation methods in the study of the aging mechanisms (traditional molecular dynamics simulation, quantum mechanics, and reactive molecular dynamics simulation) are outlined. The current simulation research progress of physical aging, aging under mechanical stress, thermal aging, hydrothermal aging, thermo-oxidative aging, electric aging, aging under high-energy particle impact, and radiation aging is introduced in detail. Finally, the current research status of the aging simulations of polymers and their composites is summarized, and the future development trend has been prospected. Full article
(This article belongs to the Special Issue Aging of Polymer Materials)
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14 pages, 3732 KiB  
Article
Stabilization and Valorization of Beer Bagasse to Obtain Bioplastics
by Daniel Castro-Criado, Johar Amin Ahmed Abdullah, Alberto Romero and Mercedes Jiménez-Rosado
Polymers 2023, 15(8), 1877; https://doi.org/10.3390/polym15081877 - 14 Apr 2023
Cited by 4 | Viewed by 1928
Abstract
Beer bagasse is a residue produced in large quantities, though it is undervalued in the industry. Its high protein and polysaccharide content make it attractive for use in sectors such as the manufacture of bioplastics. However, its high water content makes it necessary [...] Read more.
Beer bagasse is a residue produced in large quantities, though it is undervalued in the industry. Its high protein and polysaccharide content make it attractive for use in sectors such as the manufacture of bioplastics. However, its high water content makes it necessary to stabilize it before being considered as a raw material. The main objective of this work was to evaluate the stabilization of beer bagasse and the production of bioplastics from it. In this sense, different drying methods (freeze-drying and heat treatment at 45 and 105 °C) were studied. The bagasse was also characterized physicochemically to evaluate its potential. In addition, bagasse was used in combination with glycerol (plasticizer) to make bioplastics by injection molding, analyzing their mechanical properties, water absorption capacity and biodegradability. The results showed the great potential of bagasse, presenting a high content of proteins (18–20%) and polysaccharides (60–67%) after its stabilization, with freeze-drying being the most suitable method to avoid its denaturation. Bioplastics present appropriate properties for use in applications such as horticulture and agriculture. Full article
(This article belongs to the Special Issue Polymers for Recycling and Valorization of Soft and Hard Materials)
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10 pages, 5443 KiB  
Article
Time–Concentration Superposition for Linear Viscoelasticity of Polymer Solutions
by Can-Qi Li, Horst Henning Winter, Yuan-Qi Fan, Geng-Xin Xu and Xue-Feng Yuan
Polymers 2023, 15(7), 1807; https://doi.org/10.3390/polym15071807 - 6 Apr 2023
Viewed by 2261
Abstract
The concentration dependence of linear viscoelastic properties of polymer solutions is a well-studied topic in polymer physics. Dynamic scaling theories allow qualitative predictions of polymer solution rheology, but quantitative predictions are still limited to model polymers. Meanwhile, the scaling properties of non-model polymer [...] Read more.
The concentration dependence of linear viscoelastic properties of polymer solutions is a well-studied topic in polymer physics. Dynamic scaling theories allow qualitative predictions of polymer solution rheology, but quantitative predictions are still limited to model polymers. Meanwhile, the scaling properties of non-model polymer solutions must be determined experimentally. In present paper, the time–concentration superposition (TCS) of experimental data is shown to be a robust procedure for studying the concentration scaling properties of binary and ternary polymer solutions. TCS can not only identify whether power law scaling may exist or not, and over which concentration range, but also unambiguously estimate the concentration scaling exponents of linear viscoelastic properties for a range of non-model polymer solutions. Full article
(This article belongs to the Special Issue Advances in Rheology of Polymers)
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32 pages, 2540 KiB  
Review
Microbial Exopolysaccharide Composites in Biomedicine and Healthcare: Trends and Advances
by Vishal Ahuja, Arvind Kumar Bhatt, J. Rajesh Banu, Vinod Kumar, Gopalakrishnan Kumar, Yung-Hun Yang and Shashi Kant Bhatia
Polymers 2023, 15(7), 1801; https://doi.org/10.3390/polym15071801 - 6 Apr 2023
Cited by 14 | Viewed by 4615
Abstract
Microbial exopolysaccharides (EPSs), e.g., xanthan, dextran, gellan, curdlan, etc., have significant applications in several industries (pharma, food, textiles, petroleum, etc.) due to their biocompatibility, nontoxicity, and functional characteristics. However, biodegradability, poor cell adhesion, mineralization, and lower enzyme activity are some other factors that [...] Read more.
Microbial exopolysaccharides (EPSs), e.g., xanthan, dextran, gellan, curdlan, etc., have significant applications in several industries (pharma, food, textiles, petroleum, etc.) due to their biocompatibility, nontoxicity, and functional characteristics. However, biodegradability, poor cell adhesion, mineralization, and lower enzyme activity are some other factors that might hinder commercial applications in healthcare practices. Some EPSs lack biological activities that make them prone to degradation in ex vivo, as well as in vivo environments. The blending of EPSs with other natural and synthetic polymers can improve the structural, functional, and physiological characteristics, and make the composites suitable for a diverse range of applications. In comparison to EPS, composites have more mechanical strength, porosity, and stress-bearing capacity, along with a higher cell adhesion rate, and mineralization that is required for tissue engineering. Composites have a better possibility for biomedical and healthcare applications and are used for 2D and 3D scaffold fabrication, drug carrying and delivery, wound healing, tissue regeneration, and engineering. However, the commercialization of these products still needs in-depth research, considering commercial aspects such as stability within ex vivo and in vivo environments, the presence of biological fluids and enzymes, degradation profile, and interaction within living systems. The opportunities and potential applications are diverse, but more elaborative research is needed to address the challenges. In the current article, efforts have been made to summarize the recent advancements in applications of exopolysaccharide composites with natural and synthetic components, with special consideration of pharma and healthcare applications. Full article
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24 pages, 10193 KiB  
Article
Fatigue and Wear Performance of Autoclave-Processed and Vacuum-Infused Carbon Fibre Reinforced Polymer Gears
by Zoran Bergant, Roman Šturm, Damijan Zorko and Borut Černe
Polymers 2023, 15(7), 1767; https://doi.org/10.3390/polym15071767 - 1 Apr 2023
Cited by 1 | Viewed by 2069
Abstract
This study focuses on investigating the fatigue and wear behaviour of carbon fibre reinforced polymer (CFRP) gears, which have shown promising potential as lightweight and high-performance alternatives to conventional gears. The gears were fabricated via an autoclave process using an 8-layer composite made [...] Read more.
This study focuses on investigating the fatigue and wear behaviour of carbon fibre reinforced polymer (CFRP) gears, which have shown promising potential as lightweight and high-performance alternatives to conventional gears. The gears were fabricated via an autoclave process using an 8-layer composite made of T300 plain weave carbon fabric and ET445 resin and were tested in pair with a 42CrMo4 steel pinion and under nominal tooth bending stress ranging from 60 to 150 MPa. In-situ temperature monitoring was performed, using an infrared camera, and wear rates were regularly assessed. The result of the wear test indicates adhesive wear and three-body abrasion wear mechanisms between the CFRP gears and the steel counterpart. A finite element analysis was performed to examine the in-mesh contact and root stress behaviour of both new and worn gears at various loads and a specified running time. The results point to a substantial divergence from ideal meshing and stress conditions as the wear level is increased. The fatigue results indicated that the CFRP gears exhibited superior performance compared to conventional plastic and composite short-fibrous polymer gears. The described composite gear material was additionally compared with two other composite configurations, including an autoclave-cured T700S plain weave prepreg with DT120 toughened resin and a vacuum-impregnated T300 spread plain weave carbon fabric with LG 900 UV resin. The study found that the use of the T700S-DT120 resulted in additional improvements. Full article
(This article belongs to the Special Issue Failure of Polymer Composites)
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13 pages, 7209 KiB  
Article
Influence on Elastic Wave Propagation Behavior in Polymers Composites: An Analysis of Inflection Phenomena
by Guoqiang Luo, Pu Cheng, Yin Yu, Xiangwei Geng, Yue Zhao, Yulong Xia, Ruizhi Zhang and Qiang Shen
Polymers 2023, 15(7), 1680; https://doi.org/10.3390/polym15071680 - 28 Mar 2023
Viewed by 1314
Abstract
Particulate polymer composites (PPCs) are widely applied under different elastic wave loading conditions in the automobile, aviation, and armor protection industries. This study investigates the elastic wave propagation behavior of a typical PPC, specifically a Cu/poly (methyl methacrylate) (PMMA) composite, with [...] Read more.
Particulate polymer composites (PPCs) are widely applied under different elastic wave loading conditions in the automobile, aviation, and armor protection industries. This study investigates the elastic wave propagation behavior of a typical PPC, specifically a Cu/poly (methyl methacrylate) (PMMA) composite, with a wide range of particle contents (30–65 vol. %) and particle sizes (1–100 μm). The results demonstrate an inflection phenomenon in both the elastic wave velocity and attenuation coefficient with increasing volume content. In addition, the inflection point moves to the direction of low content with the increase in particle size. Notably, the elastic wave velocity, attenuation, and wavefront width significantly increased with the particle size. The inflection phenomenon of elastic wave propagation behavior in PPCs is demonstrated to have resulted from particle interaction using the classical scattering theory and finite element analysis. The particle interaction initially intensified and then reduced with increasing particle content. This study elucidates the underlying mechanism governing the elastic wave propagation behavior of high particle content PPCs and provides guidelines for the design and application of wave-absorbing composites. Full article
(This article belongs to the Special Issue Mechanical Properties of Polymer Composites II)
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16 pages, 3109 KiB  
Article
π-Electron-Extended Triazine-Based Covalent Organic Framework as Photocatalyst for Organic Pollution Degradation and H2 Production from Water
by Jing Han Wang, Taher A. Gaber, Shiao-Wei Kuo and Ahmed F. M. EL-Mahdy
Polymers 2023, 15(7), 1685; https://doi.org/10.3390/polym15071685 - 28 Mar 2023
Cited by 9 | Viewed by 2266
Abstract
Herein, we report the efficient preparation of π-electron-extended triazine-based covalent organic framework (TFP-TPTPh COF) for photocatalysis and adsorption of the rhodamine B (RhB) dye molecule, as well as for photocatalytic hydrogen generation from water. The resultant TFP-TPTPh COF exhibited remarkable porosity, excellent crystallinity, [...] Read more.
Herein, we report the efficient preparation of π-electron-extended triazine-based covalent organic framework (TFP-TPTPh COF) for photocatalysis and adsorption of the rhodamine B (RhB) dye molecule, as well as for photocatalytic hydrogen generation from water. The resultant TFP-TPTPh COF exhibited remarkable porosity, excellent crystallinity, high surface area of 724 m2 g−1, and massive thermal stability with a char yield of 63.41%. The TFP-TPTPh COF demonstrated an excellent removal efficiency of RhB from water in 60 min when used as an adsorbent, and its maximum adsorption capacity (Qm) of 480 mg g−1 is among the highest Qm values for porous polymers ever to be recorded. In addition, the TFP-TPTPh COF showed a remarkable photocatalytic degradation of RhB dye molecules with a reaction rate constant of 4.1 × 10−2 min−1 and an efficiency of 97.02% under ultraviolet–visible light irradiation. Furthermore, without additional co-catalysts, the TFP-TPTPh COF displayed an excellent photocatalytic capacity for reducing water to generate H2 with a hydrogen evolution rate (HER) of 2712 μmol g−1 h−1. This highly active COF-based photocatalyst appears to be a useful material for dye removal from water, as well as solar energy processing and conversion. Full article
(This article belongs to the Special Issue Polymers: Environmental Aspects)
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14 pages, 4502 KiB  
Article
Supramolecular Linear-Dendritic Nanoreactors: Synthesis and Catalytic Activity in “Green” Suzuki-Miyaura Reactions
by Xin Liu, F. Max Yavitt and Ivan Gitsov
Polymers 2023, 15(7), 1671; https://doi.org/10.3390/polym15071671 - 28 Mar 2023
Cited by 1 | Viewed by 1448
Abstract
This study describes the synthesis of novel amphiphilic linear-dendritic block copolymers and their self-assembly in water to form supramolecular nanoreactors capable of catalyzing Suzuki-Miyaura coupling reactions under “green” conditions. The block copolymers were formed through copper(I)-catalyzed alkyne-azide cycloaddition between azide functionalized poly(benzyl ether) [...] Read more.
This study describes the synthesis of novel amphiphilic linear-dendritic block copolymers and their self-assembly in water to form supramolecular nanoreactors capable of catalyzing Suzuki-Miyaura coupling reactions under “green” conditions. The block copolymers were formed through copper(I)-catalyzed alkyne-azide cycloaddition between azide functionalized poly(benzyl ether) dendrons as the perfectly branched blocks, as well as bis-alkyne modified poly(ethylene glycol), PEG, as the linear block. A first-generation poly(benzyl ether) dendron (G1) was coupled to a bis-alkyne modified PEG with molecular mass of 5 kDa, forming an ABA copolymer (G1)2-PEG5k-(G1)2 (yield 62%), while a second-generation dendron (G2) was coupled to a 11 kDa bis-alkyne modified PEG to produce (G2)2-PEG11k-(G2)2 (yield 49%). The structural purity and low dispersity of the linear-dendritic copolymers were verified by size-exclusion chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Their self-assembly was studied by dynamic light scattering, showing that (G1)2-PEG5k-(G1)2 and (G2)2-PEG11k-(G2)2 formed single populations of micelles (17 nm and 37 nm in diameter, respectively). The triazole rings located at the boundaries between the core and the corona are efficient chelating groups for transition metals. The ability of the micelles to complex Pd was confirmed by 1H NMR, transmission electron microscopy, and inductively coupled plasma. The catalytic activity of the supramolecular linear-dendritic/Pd complexes was tested in water by model Suzuki-Miyaura reactions in which quantitative yields were achieved within 3 h at 40 °C, while, at 17 °C, a yield of more than 70% was attained after 17 h. Full article
(This article belongs to the Special Issue Stimuli-Responsive Polymers)
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21 pages, 6804 KiB  
Article
Damage Monitoring of Composite Adhesive Joint Integrity Using Conductivity and Fiber Bragg Grating
by Chow-Shing Shin and Liang-Wei Chen
Polymers 2023, 15(6), 1575; https://doi.org/10.3390/polym15061575 - 22 Mar 2023
Viewed by 1754
Abstract
Adhesive joints possess a number of advantages over traditional joining methods and are widely used in composite structures. Conventional non-destructive examination techniques do not readily reveal joint degradation before the formation of explicit defects. Embedded fiber Bragg grating (FBG) sensors and the resistance [...] Read more.
Adhesive joints possess a number of advantages over traditional joining methods and are widely used in composite structures. Conventional non-destructive examination techniques do not readily reveal joint degradation before the formation of explicit defects. Embedded fiber Bragg grating (FBG) sensors and the resistance of carbon nanotube (CNT)-doped conductive joints have been proposed to monitor the structural integrity of adhesive joints. Both techniques will be employed and compared in the current work to monitor damage development in adhesive joints under tensile and cyclic fatigue loading. Most of the previous works took measurements under an applied load, which by itself will affect the monitoring signals without the presence of any damage. Moreover, most FBG works primarily relied on the peak shifting phenomenon for sensing. Degradation of adhesive and inter-facial defects will lead to non-uniform strain that may chirp the FBG spectrum, causing complications in the peak shifting measurement. In view of the above shortfalls, measurements are made at some low and fixed loads to preclude any unwanted effect due to the applied load. The whole FBG spectrum, instead of a single peak, will be used, and a quantitative parameter to describe spectrum changes is proposed for monitoring purposes. The extent of damage is revealed by a fluorescent penetrant and correlated with the monitoring signals. With these refined techniques, we hope to shed some light on the relative merits and limitations of the two techniques. Full article
(This article belongs to the Special Issue Structural Integrity Assessment on Polymers and Composites)
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14 pages, 5961 KiB  
Article
The Hypervelocity Impact Behavior and Energy Absorption Evaluation of Fabric
by Huadong Xu, Dong Yu, Jiaxin Cui, Zhixin Shi, Di Song and Changqing Miao
Polymers 2023, 15(6), 1547; https://doi.org/10.3390/polym15061547 - 21 Mar 2023
Cited by 1 | Viewed by 1552
Abstract
In this work, the mechanical behavior and energy absorption characteristics of flexible fabric under hypervelocity impact (HVI) were investigated. Basalt fabric, ultra-high molecular weight polyethylene (UHMWPE) fabric, and aluminum alloy (Al) plate were chosen to be the sample materials for their excellent mechanical [...] Read more.
In this work, the mechanical behavior and energy absorption characteristics of flexible fabric under hypervelocity impact (HVI) were investigated. Basalt fabric, ultra-high molecular weight polyethylene (UHMWPE) fabric, and aluminum alloy (Al) plate were chosen to be the sample materials for their excellent mechanical properties and applicative prospect in spacecraft shielding. HVI experiments had been conducted with the help of a two-stage light-gas gun facility, wherein Al projectile with 3.97 mm diameter was launched at velocities in the range 4.1~4.3 km/s. Impact conditions and areal density were kept constant for all targets. The microstructural damage morphology of fiber post-impact was characterized using a scanning electron microscope (SEM). Analysis results show that a brittle fracture occurred for Basalt fiber during HVI. On the contrary, the ductile fractures with large-scale plastic deformation and apparent thermal softening/melting of the material had happened on the UHMWPE fiber when subjected to a projectile impact. According to the HVI shielding performance and microstructural damage analysis results, it can be inferred that ductile fractures and thermal softening/melting of the material were the prevailing energy absorption behaviors of UHMWPE fabric, which leads to absorbing more impact energy than Basalt fabric and eventually, contributes the superior shielding performance. Full article
(This article belongs to the Special Issue Fiber-Reinforced Polymers and Lightweight Structures)
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16 pages, 2408 KiB  
Article
Processing, Characterization and Disintegration Properties of Biopolymers Based on Mater-Bi® and Ellagic Acid/Chitosan Coating
by Carolina Villegas, Sara Martínez, Alejandra Torres, Adrián Rojas, Rocío Araya, Abel Guarda and María José Galotto
Polymers 2023, 15(6), 1548; https://doi.org/10.3390/polym15061548 - 21 Mar 2023
Cited by 3 | Viewed by 2072
Abstract
Among the most promising synthetic biopolymers to replace conventional plastics in numerous applications is MaterBi® (MB), a commercial biodegradable polymer based on modified starch and synthetic polymers. Actually, MB has important commercial applications as it shows interesting mechanical properties, thermal stability, processability [...] Read more.
Among the most promising synthetic biopolymers to replace conventional plastics in numerous applications is MaterBi® (MB), a commercial biodegradable polymer based on modified starch and synthetic polymers. Actually, MB has important commercial applications as it shows interesting mechanical properties, thermal stability, processability and biodegradability. On the other hand, research has also focused on the incorporation of natural, efficient and low-cost active compounds into various materials with the aim of incorporating antimicrobial and/or antioxidant capacities into matrix polymers to extend the shelf life of foods. Among these is ellagic acid (EA), a polyphenolic compound abundant in some fruits, nuts and seeds, but also in agroforestry and industrial residues, which seems to be a promising biomolecule with interesting biological activities, including antioxidant activity, antibacterial activity and UV-barrier properties. The objective of this research is to develop a film based on commercial biopolymer Mater-Bi® (MB) EF51L, incorporating active coating from chitosan with a natural active compound (EA) at two concentrations (2.5 and 5 wt.%). The formulations obtained complete characterization and were carried out in order to evaluate whether the incorporation of the coating significantly affects thermal, mechanical, structural, water-vapor barrier and disintegration properties. From the results, FTIR analysis yielded identification, through characteristic peaks, that the type of MB used is constituted by three polymers, namely PLA, TPS and PBAT. With respect to the mechanical properties, the values of tensile modulus and tensile strength of the MB-CHI film were between 15 and 23% lower than the values obtained for the MB film. The addition of 2.5 wt.% EA to the CHI layer did not generate changes in the mechanical properties of the system, whereas a 5 wt.% increase in ellagic acid improved the mechanical properties of the CHI film through the addition of natural phenolic compounds at high concentrations. Finally, the disintegration process was mainly affected by the PBAT biopolymer, causing the material to not disintegrate within the times indicated by ISO 20200. Full article
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14 pages, 4944 KiB  
Article
Deep Transfer Learning Approach for Localization of Damage Area in Composite Laminates Using Acoustic Emission Signal
by Jingyu Zhao, Weihua Xie, Dong Yu, Qiang Yang, Songhe Meng and Qihui Lyu
Polymers 2023, 15(6), 1520; https://doi.org/10.3390/polym15061520 - 19 Mar 2023
Cited by 4 | Viewed by 1878
Abstract
Intelligent composite structures with self-aware functions are preferable for future aircrafts. The real-time location of damaged areas of composites is a key step. In this study, deep transfer learning was used to achieve the real-time location of damaged areas. The sensor network obtained [...] Read more.
Intelligent composite structures with self-aware functions are preferable for future aircrafts. The real-time location of damaged areas of composites is a key step. In this study, deep transfer learning was used to achieve the real-time location of damaged areas. The sensor network obtained acoustic emission signals from different damaged areas of the aluminum alloy plate. The acoustic emission time-domain signal is transformed into the input image by continuous wavelet transform. The convolutional neural network-based model automatically localized the damaged area by extracting features from the input image. A small amount of composite acoustic emission data was used to fine-tune some network parameters of the basic model through transfer learning. This enabled the model to classify the damaged area of composites. The accuracy of the transfer learning model trained with 900 samples is 96.38%, which is comparable to the accuracy of the model trained directly with 1800 samples; the training time of the former is only 17.68% of that of the latter. The proposed method can be easily adapted to new composite structures using transfer learning and a small dataset, providing a new idea for structural health monitoring. Full article
(This article belongs to the Special Issue Fiber-Reinforced Polymers and Lightweight Structures)
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17 pages, 6111 KiB  
Article
Effect of Aging on Unidirectional Composite Laminate Polyethylene for Body Armor
by Amy Engelbrecht-Wiggans, Zois Tsinas, Ajay Krishnamurthy and Amanda L. Forster
Polymers 2023, 15(6), 1347; https://doi.org/10.3390/polym15061347 - 8 Mar 2023
Cited by 2 | Viewed by 1464
Abstract
The construction of ballistic-resistant body armor is experiencing an increasing use of flexible unidirectional (UD) composite laminates that comprise multiple layers. Each UD layer contains hexagonally packed high-performance fibers with a very low modulus matrix (sometimes referred to as binder resins). Laminates are [...] Read more.
The construction of ballistic-resistant body armor is experiencing an increasing use of flexible unidirectional (UD) composite laminates that comprise multiple layers. Each UD layer contains hexagonally packed high-performance fibers with a very low modulus matrix (sometimes referred to as binder resins). Laminates are then made from orthogonal stacks of these layers, and these laminate-based armor packages offer significant performance advantages over standard woven materials. When designing any armor system, the long-term reliability of the armor materials is critical, particularly with regard to stability with exposure to temperature and humidity, as these are known causes of degradation in commonly used body armor materials. To better inform future armor designers, this work investigates the tensile behavior of an ultra-high molar mass polyethylene (UHMMPE) flexible UD laminate that was aged for at least 350 d at two accelerated conditions: 70 °C at 76% relative humidity (RH) and 70 °C in a desiccator. Tensile tests were performed at two different loading rates. The mechanical properties of the material after ageing demonstrated less than 10% degradation in tensile strength, indicating high reliability for armor made from this material. Full article
(This article belongs to the Special Issue Durability and Degradation of Polymeric Materials II)
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14 pages, 2185 KiB  
Article
Feasibility of Valorization of Post-Consumer Recycled Flexible Polypropylene by Adding Fumed Nanosilica for Its Potential Use in Food Packaging toward Sustainability
by Eliezer Velásquez, Carol López de Dicastillo, Cristian Patiño Vidal, Guillermo Copello, Cristopher Reyes, Abel Guarda and María José Galotto
Polymers 2023, 15(5), 1081; https://doi.org/10.3390/polym15051081 - 21 Feb 2023
Cited by 4 | Viewed by 1663
Abstract
The food industry has a current challenge of increasing the recycling of post-consumer plastics to reduce plastic waste towards a circular economy, especially flexible polypropylene, which is highly demanded in food packaging. However, recycling post-consumer plastics is limited because service life and reprocessing [...] Read more.
The food industry has a current challenge of increasing the recycling of post-consumer plastics to reduce plastic waste towards a circular economy, especially flexible polypropylene, which is highly demanded in food packaging. However, recycling post-consumer plastics is limited because service life and reprocessing degrade their physical-mechanical properties and modify the migration of components from the recycled material to the food. This research evaluated the feasibility of valorization of post-consumer recycled flexible polypropylene (PCPP) by incorporating fumed nanosilica (NS). For this purpose, the effect of concentration and type (hydrophilic and hydrophobic) of NS on the morphological, mechanical, sealing, barrier and overall migration properties of PCPP films was studied. Incorporating NS improved Young’s modulus and, more significantly, tensile strength at 0.5 wt% and 1 wt%, where a better particle dispersion was confirmed by EDS-SEM, but it diminished elongation at breakage of the films. Interestingly, NS tended to increase the seal strength of PCPP nanocomposite films more significantly at higher NS content, showing a seal failure of the adhesive peel type which is preferred for flexible packaging. NS at 1 wt% did not affect the water vapor and oxygen permeabilities of the films. Overall migration of PCPP and nanocomposites exceeded the limit value of 10 mg dm−2 allowed by European legislation at the studied concentrations of 1% and 4 wt%. Nonetheless, NS reduced the overall migration of PCPP from 17.3 to 15 mg dm−2 in all nanocomposites. In conclusion, PCPP with 1 wt% of hydrophobic NS presented an improved overall performance of the studied packaging properties. Full article
(This article belongs to the Special Issue Polymers for Recycling and Valorization of Soft and Hard Materials)
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21 pages, 497 KiB  
Review
Hydrothermal Ageing of Glass Fibre Reinforced Vinyl Ester Composites: A Review
by James Thomason and Georgios Xypolias
Polymers 2023, 15(4), 835; https://doi.org/10.3390/polym15040835 - 8 Feb 2023
Cited by 6 | Viewed by 2300
Abstract
The use of glass fibre-reinforced polymer (GFRP) composites in load-carrying constructions has significantly increased over the last few decades. Such GFRP composite structures may undergo significant changes in performance as a consequence of long-term environmental exposure. Vinyl ester (VE) resins are a class [...] Read more.
The use of glass fibre-reinforced polymer (GFRP) composites in load-carrying constructions has significantly increased over the last few decades. Such GFRP composite structures may undergo significant changes in performance as a consequence of long-term environmental exposure. Vinyl ester (VE) resins are a class of thermosetting polymers increasingly being used in such structural composites. This increasing use of VE-based GFRPs in such applications has led to an increasing need to better understand the consequences of long-term environmental exposure on their performance. The reliable validation of the environmental durability of new VE-based GFRPs can be a time- and resource-consuming process involving costly testing programs. Accelerated hydrothermal ageing is often used in these investigations. This paper reviews the relevant literature on the hydrothermal ageing of vinyl ester-based GFRP with special attention to the fundamental background of moisture-induced ageing of GFRP, the important role of voids, and the fibre-matrix interface, on composite mechanical performance. Full article
(This article belongs to the Special Issue Durability and Degradation of Polymeric Materials II)
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20 pages, 3343 KiB  
Article
Enzyme-Catalyzed Polymerization of Kraft Lignin from Eucalyptus globulus: Comparison of Bacterial and Fungal Laccases Efficacy
by Luisa García-Fuentevilla, Gabriela Domínguez, Raquel Martín-Sampedro, Manuel Hernández, María E. Arias, José I. Santos, David Ibarra and María E. Eugenio
Polymers 2023, 15(3), 513; https://doi.org/10.3390/polym15030513 - 18 Jan 2023
Cited by 2 | Viewed by 2239
Abstract
Kraft lignin, a side-stream from the pulp and paper industry, can be modified by laccases for the synthesis of high added-value products. This work aims to study different laccase sources, including a bacterial laccase from Streptomyces ipomoeae (SiLA) and a fungal laccase from [...] Read more.
Kraft lignin, a side-stream from the pulp and paper industry, can be modified by laccases for the synthesis of high added-value products. This work aims to study different laccase sources, including a bacterial laccase from Streptomyces ipomoeae (SiLA) and a fungal laccase from Myceliophthora thermophila (MtL), for kraft lignin polymerization. To study the influence of some variables in these processes, a central composite design (CCD) with two continuous variables (enzyme concentration and reaction time) and three levels for each variable was used. The prediction of the behavior of the output variables (phenolic content and molecular weight of lignins) were modelled by means of response surface methodology (RSM). Moreover, characterization of lignins was performed by Fourier-transform infrared (FTIR) spectroscopy and different nuclear magnetic resonance (NMR) spectroscopy techniques. In addition, antioxidant activity was also analyzed. Results showed that lignin polymerization (referring to polymerization as lower phenolic content and higher molecular weight) occurred by the action of both laccases. The enzyme concentration was the most influential variable in the lignin polymerization reaction within the range studied for SiLA laccase, while the most influential variable for MtL laccase was the reaction time. FTIR and NMR characterization analysis corroborated lignin polymerization results obtained from the RSM. Full article
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44 pages, 19950 KiB  
Review
Hybridization of Wide-Angle X-ray and Neutron Diffraction Techniques in the Crystal Structure Analyses of Synthetic Polymers
by Kohji Tashiro, Katsuhiro Kusaka, Hiroko Yamamoto, Takaaki Hosoya, Shuji Okada and Takashi Ohhara
Polymers 2023, 15(2), 465; https://doi.org/10.3390/polym15020465 - 16 Jan 2023
Cited by 1 | Viewed by 2141
Abstract
The development in the crystal structure analysis of synthetic polymers using the hybridized combination of wide-angle X-ray and neutron diffraction (WAXD and WAND, respectively) techniques has been reviewed with many case studies performed by the authors. At first, the technical development was reviewed, [...] Read more.
The development in the crystal structure analysis of synthetic polymers using the hybridized combination of wide-angle X-ray and neutron diffraction (WAXD and WAND, respectively) techniques has been reviewed with many case studies performed by the authors. At first, the technical development was reviewed, in which the usage of high-energy synchrotron X-ray source was emphasized for increasing the total number of the observable diffraction peaks, and several examples were introduced. Secondly, the usage of the WAND method was introduced, in which the successful extraction of hydrogen atomic positions was described. The third example is to show the importance for the hybrid combination of these two diffraction methods. The quantitative WAXD data analysis gave the crystal structures of at-poly(vinyl alcohol) (at-PVA) and at-PVA-iodine complex. However, the thus-proposed structure models were found not to reproduce the observed WAND data very much. The reason came from the remarkable difference in the atomic scattering powers of the constituting atomic species between WAXD and WAND phenomena. The introduction of statistical disorder solved this serious problem, which reproduced both of the observed WAXD and WAND data consistently. The more systematic combination of WAXD and WAND methods, or the so-called X-N method, was applied also to the quantitative evaluation of the bonded electron density distribution along the skeletal chains, where the results about polydiacetylene single crystals were presented as the first successful study. Finally, the application of WAND technique in the trace of structural changes induced under the application of external stress or temperature was described. The future perspective is described for the development of structural science of synthetic polymers on the basis of the combined WAXD/WAND techniques. Full article
(This article belongs to the Special Issue State-of-the-Art Polymer Science and Technology in Japan (2021,2022))
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16 pages, 3086 KiB  
Article
Insight into Degrading Effects of Two Fungi on Polyurethane Coating Failure in a Simulated Atmospheric Environment
by Xiangping Hao, Kexin Yang, Dawei Zhang and Lin Lu
Polymers 2023, 15(2), 328; https://doi.org/10.3390/polym15020328 - 9 Jan 2023
Cited by 1 | Viewed by 1675
Abstract
Two different fungi, Talaromyces funiculosus (T. funiculosus) and Phanerochaete chrysosporium (P. chrysosporium), were collected from the Xishuangbanna atmospheric corrosion site and incubated on a polyurethane (PU) coating at 30 °C for two weeks under 95% relative humidity (RH). The biodegrading [...] Read more.
Two different fungi, Talaromyces funiculosus (T. funiculosus) and Phanerochaete chrysosporium (P. chrysosporium), were collected from the Xishuangbanna atmospheric corrosion site and incubated on a polyurethane (PU) coating at 30 °C for two weeks under 95% relative humidity (RH). The biodegrading effects of these fungi on the coating failure were investigated from aspects of metabolism and electrochemistry. The results showed that T. funiculosus contributed more to the degradation of the PU coating failure than P. chrysosporium, and two factors played dominant roles. First, the weight of the T. funiculosus mycelium was nearly 3 times more than that of P. chrysosporium, indicating there was more substrate mycelium of T. funiculosus deep into the coatings to get more nutrition in atmospheric during colonization. Second, T. funiculosus secreted carboxylic acids, such as citric, propanoic, succinic, and tartaric acids, and accelerated the hydrolysis of the ester and urethane bonds in the PU coatings. As a result, the mycelium of T. funiculosus readily penetrated the interface of the coating and substrate resulting in a rapid proliferation. Thus, the |Z|0.01Hz value of the coating decreased to 5.1 × 104 Ω·cm2 after 14 days of colonization by T. funiculosus while the value remained at 7.2 × 107 Ω·cm2 after colonization by P. chrysosporium. These insights suggest that the biodegradation process in simulated atmospheric environments would provide theoretical guidance and directions for the design of antifungal PU coatings. Full article
(This article belongs to the Special Issue Durability and Degradation of Polymeric Materials II)
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9 pages, 2286 KiB  
Article
Self- and Cross-Fusing of Furan-Based Polyurea Gels Dynamically Cross-Linked with Maleimides
by Takuya Kumakura, Kenji Takada and Tatsuo Kaneko
Polymers 2023, 15(2), 341; https://doi.org/10.3390/polym15020341 - 9 Jan 2023
Cited by 1 | Viewed by 1635
Abstract
Bio-based polyureas (PUs) with main-chain furan rings were synthesized by the polyaddition of 2,5-bis(aminomethyl)furan with various diisocyanates, such as methylene diphenyl diisocyanate. Several PU’s were soluble in polar organic solvents, and were cast to form thermomechanically stable films with softening temperatures of over [...] Read more.
Bio-based polyureas (PUs) with main-chain furan rings were synthesized by the polyaddition of 2,5-bis(aminomethyl)furan with various diisocyanates, such as methylene diphenyl diisocyanate. Several PU’s were soluble in polar organic solvents, and were cast to form thermomechanically stable films with softening temperatures of over 100 °C. The furan rings of the PU main chains underwent a dynamic Diels-Alder (DA) reaction with bismaleimide (BMI) cross-linkers. While the mixed solution of PU and BMI did not show any apparent signs of reaction at room temperature, the DA reaction proceeded to form gels upon heating to 60 °C, which became a solution again by further heating to 80 °C (retro-DA reaction). The solution phase was maintained by rapid quenching from 80 °C to room temperature, while the gel was reformed upon slow cooling. The recovered gels exhibited self-healing properties. A scratch made by a hot knife at temperatures above 80 °C disappeared spontaneously. When two different gels were cut using a knife at room temperature, placed in contact with each other, and heated to 60 °C, they fused. The ability to control the DA/retro-DA reaction allowed gels of varying composition to heal. Full article
(This article belongs to the Special Issue State-of-the-Art Polymer Science and Technology in Japan (2021,2022))
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15 pages, 2393 KiB  
Article
Studying the Physical and Chemical Properties of Polydimethylsiloxane Matrix Reinforced by Nanostructured TiO2 Supported on Mesoporous Silica
by Sari Katz, Noa Lachman, Nir Hafif, Lilach Rosh, Alexander Pevzner, Amir Lybman, Tal Amitay-Rosen, Ido Nir and Hadar Rotter
Polymers 2023, 15(1), 81; https://doi.org/10.3390/polym15010081 - 25 Dec 2022
Cited by 6 | Viewed by 2922
Abstract
In this study, a reactive adsorbent filler was integrated into a polymeric matrix as a novel reactive protective barrier without undermining its mechanical, thermal, and chemical properties. For this purpose, newly synthesized TiO2/MCM/polydimethylsiloxane (PDMS) composites were prepared, and their various properties [...] Read more.
In this study, a reactive adsorbent filler was integrated into a polymeric matrix as a novel reactive protective barrier without undermining its mechanical, thermal, and chemical properties. For this purpose, newly synthesized TiO2/MCM/polydimethylsiloxane (PDMS) composites were prepared, and their various properties were thoroughly studied. The filler, TiO2/MCM, is based on a (45 wt%) TiO2 nanoparticle catalyst inside the pores of ordered mesoporous silica, MCM-41, which combines a high adsorption capacity and catalytic capability. This study shows that the incorporation of TiO2/MCM significantly enhances the composite’s Young’s modulus in terms of tensile strength, as an optimal measurement of 1.6 MPa was obtained, compared with that of 0.8 MPa of pristine PDMS. The composites also showed a higher thermal stability, a reduction in the coefficient of thermal expansion (from 290 to 110 ppm/°C), a 25% reduction in the change in the normalized specific heat capacity, and an increase in the thermal degradation temperatures. The chemical stability in organic environments was improved, as toluene swelling decreased by 40% and the contact angle increased by ~15°. The enhanced properties of the novel synthesized TiO2/MCM/PDMS composite can be used in various applications where a high adsorption capacity and catalytic/photocatalytic activity are required, such as in protective equipment, microfluidic applications, and chemical sensor devices. Full article
(This article belongs to the Special Issue Durability and Degradation of Polymeric Materials II)
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26 pages, 7618 KiB  
Article
Plastic Deformation of High Density Polyethylene with Extended-Chain Crystal Morphology
by Alina Vozniak and Zbigniew Bartczak
Polymers 2023, 15(1), 66; https://doi.org/10.3390/polym15010066 - 24 Dec 2022
Cited by 4 | Viewed by 2711
Abstract
Samples of polyethylene with extended-chain crystal morphology, obtained by crystallization under high pressure, were subjected to uniaxial compression to various strains. Accompanying structural changes were analyzed using scanning electron microscopy. At the true strain of e = 0.2–0.3 the microbuckling instability was observed [...] Read more.
Samples of polyethylene with extended-chain crystal morphology, obtained by crystallization under high pressure, were subjected to uniaxial compression to various strains. Accompanying structural changes were analyzed using scanning electron microscopy. At the true strain of e = 0.2–0.3 the microbuckling instability was observed in longitudinally loaded lamellae, resulting in the formation of angular kinks. This induced a rapid reorientation of the lamellae, facilitating their further deformation by crystallographic slip. Microbuckling instability was found to occur earlier than in samples with folded-chain crystal morphology (e = 0.3–0.4) due to a smaller ratio of the amorphous to crystalline layer thickness. SEM observations demonstrated that the microbuckling instability begins with small undulation in long lamellae. Sharp angular lamellar kinks develop from the initial undulation through intense plastic deformation by crystallographic slip along the chain direction. The same slip system was found to operate throughout the kink, including the tip region as well as both limbs. In contrast to thin folded-chain lamellae that often undergo fragmentation during deformation, the thick extended-chain lamellae deform stably by chain slip and retain their continuity up to high strains, e > 1.6. This stability of deformation is related to the large thickness of extended-chain lamellae. Full article
(This article belongs to the Special Issue Plastics II)
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24 pages, 7223 KiB  
Review
Review on Heat Generation of Rubber Composites
by Ying Liu, Wenduo Chen and Dazhi Jiang
Polymers 2023, 15(1), 2; https://doi.org/10.3390/polym15010002 - 20 Dec 2022
Cited by 5 | Viewed by 3184
Abstract
Rubber composites are extensively used in industrial applications for their exceptional elasticity. The fatigue temperature rise occurs during operation, resulting in a serious decline in performance. Reducing heat generation of the composites during cyclic loading will help to avoid substantial overheating that most [...] Read more.
Rubber composites are extensively used in industrial applications for their exceptional elasticity. The fatigue temperature rise occurs during operation, resulting in a serious decline in performance. Reducing heat generation of the composites during cyclic loading will help to avoid substantial overheating that most likely results in the degradation of materials. Herein, we discuss the two main reasons for heat generation, including viscoelasticity and friction. Influencing factors of heat generation are highlighted, including the Payne effect, Mullins effect, interface interaction, crosslink density, bond rubber content, and fillers. Besides, theoretical models to predict the temperature rise are also analyzed. This work provides a promising way to achieve advanced rubber composites with high performance in the future. Full article
(This article belongs to the Special Issue Polymer Composite Analysis and Characterization II)
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15 pages, 10839 KiB  
Article
Advances in Rubber Compounds Using ZnO and MgO as Co-Cure Activators
by Md Najib Alam, Vineet Kumar and Sang-Shin Park
Polymers 2022, 14(23), 5289; https://doi.org/10.3390/polym14235289 - 3 Dec 2022
Cited by 17 | Viewed by 5694
Abstract
Zinc oxide performs as the best cure activator in sulfur-based vulcanization of rubber, but it is regarded as a highly toxic material for aquatic organisms. Hence, the toxic cure activator should be replaced by a non-toxic one. Still, there is no suitable alternative [...] Read more.
Zinc oxide performs as the best cure activator in sulfur-based vulcanization of rubber, but it is regarded as a highly toxic material for aquatic organisms. Hence, the toxic cure activator should be replaced by a non-toxic one. Still, there is no suitable alternative industrially. However, binary activators combining ZnO and another metal oxide such as MgO can largely reduce the level of ZnO with some improved benefits in the vulcanization of rubber as investigated in this research. Curing, mechanical, and thermal characteristics were investigated to find out the suitability of MgO in the vulcanization of rubber. Curing studies reveal that significant reductions in the optimum curing times are found by using MgO as a co-cure activator. Especially, the rate of vulcanization with conventional 5 phr (per hundred grams) ZnO can be enhanced by more than double, going from 0.3 Nm/min to 0.85 Nm/min by the use of a 3:2 ratio of MgO to ZnO cure activator system that should have high industrial importance. Mechanical and thermal properties investigations suggest that MgO as a co-cure activator used at 60% can provide 7.5% higher M100 (modulus at 100% strain) (0.58 MPa from 0.54 MPa), 20% higher tensile strength (23.7 MPa from 19.5 MPa), 15% higher elongation at break (1455% from 1270%), 68% higher fracture toughness (126 MJ/m3 from 75 MJ/m3), and comparable thermal stability than conventionally using 100 % ZnO. Especially, MgO as a co-cure activator could be very useful for improving the fracture toughness in rubber compounds compared to ZnO as a single-site curing activator. The significant improvements in the curing and mechanical properties suggest that MgO and ZnO undergo chemical interactions during vulcanization. Such rubber compounds can be useful in advanced tough and stretchable applications. Full article
(This article belongs to the Special Issue Advances in Functional Rubber and Elastomer Composites)
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21 pages, 7289 KiB  
Article
Efficient Physical Mixing of Small Amounts of Nanosilica Dispersion and Waterborne Polyurethane by Using Mild Stirring Conditions
by María Echarri-Giacchi and José Miguel Martín-Martínez
Polymers 2022, 14(23), 5136; https://doi.org/10.3390/polym14235136 - 25 Nov 2022
Cited by 2 | Viewed by 1808
Abstract
Good dispersion of nanosilica particles in waterborne polyurethane was obtained by mild mechanical stirring when 0.1–0.5 wt.% nanosilica in aqueous dispersion was added. The addition of small amounts of nanosilica produced more negative Z-potential values, increased the surface tension and decreased the Brookfield [...] Read more.
Good dispersion of nanosilica particles in waterborne polyurethane was obtained by mild mechanical stirring when 0.1–0.5 wt.% nanosilica in aqueous dispersion was added. The addition of small amounts of nanosilica produced more negative Z-potential values, increased the surface tension and decreased the Brookfield viscosity, as well as the extent of shear thinning of the waterborne polyurethane. Depending on the amount of nanosilica, the particle-size distributions of the waterborne polyurethanes changed differently and the addition of only 0.1 wt.% nanosilica noticeably increased the percentage of the particles of 298 nm in diameter. The DSC curves showed two melting peaks at 46 °C and 52 °C, as well as an increase in the melting enthalpy. In addition, when nanosilica was added, the crystallization peak of the waterborne polyurethane was displaced to a higher temperature and showed higher enthalpy. Furthermore, the addition of 0.1–0.5 wt.% nanosilica displaced the temperature of decomposition of the soft domains to higher temperatures due to the intercalation of the particles among the soft segments; this led to a change in the degree of phase separation of the waterborne polyurethanes. As a consequence, improved thermal stability and viscoelastic and mechanical properties of the waterborne polyurethanes were obtained. However, the addition of small amounts of nanosilica was detrimental for the wettability and adhesion of the waterborne polyurethanes due to the existence of acrylic moieties on the nanosilica particles, which seemed to migrate to the interface once the polyurethane was cross-linked. In fact, the final T-peel strength values of the joints made with the waterborne polyurethanes containing nanosilica were significantly lower than the one obtained with the waterborne polyurethane without nanosilica; the higher the nanosilica content, the lower the final adhesion. The better the nanosilica dispersion in the waterborne polyurethane+nanosilica, the higher the final T-peel strength value. Full article
(This article belongs to the Special Issue Advances in Multifunctional Polymer-Based Nanocomposites)
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22 pages, 7308 KiB  
Article
The Influence of Different Sustainable Silk-Based Fillers on the Thermal and Mechanical Properties of Polylactic Acid Composites
by José Miguel Ferri, Miguel Aldas, Emilio Rayon, Maria Dolores Samper and Antonio Abel Lozano-Pérez
Polymers 2022, 14(22), 5016; https://doi.org/10.3390/polym14225016 - 18 Nov 2022
Cited by 4 | Viewed by 2088
Abstract
In this work, different silk fillers combined with maleinized corn oil (MCO), as environmentally friendly plasticizers, were used to modify the mechanical and thermal properties of polylactic acid (PLA) composites. Melt extrusion and injection were used to obtain samples with a content of [...] Read more.
In this work, different silk fillers combined with maleinized corn oil (MCO), as environmentally friendly plasticizers, were used to modify the mechanical and thermal properties of polylactic acid (PLA) composites. Melt extrusion and injection were used to obtain samples with a content of 10 wt.% of MCO and 0.5 phr of different silk fillers: crushed silk (CS), silk fibroin microparticles (SFM), and silk fibroin nanoparticles (SFN). PLA formulation with 10 wt.% of MCO and 0.5 g of CS per hundred grams of composite (phr) showed the highest increase in mechanical ductile properties with an increase in elongation at break of approximately 1400%, compared with PLA. Differential scanning calorimetry (DSC) showed a decrease of 2 °C in their glass transition temperature with the addition of different silk fillers. In addition, SFM and SFN increase the degree of crystallinity of PLA. This increment was also confirmed by infrared spectroscopy analysis. Field emission scanning electron microscopy (FESEM) images revealed a good dispersion of the different silk fillers. Among them, PLA formulation with 10 wt.% MCO and 0.5 phr of SFN, showed an optimal balance between maximum resistance and elongation at break, with 52.0 MPa and 10.8%, respectively, improving elongation at break by 635%. Furthermore, all samples were satisfactorily disintegrated under composting conditions. Full article
(This article belongs to the Special Issue Polylactic Acid (PLA)-Based Materials)
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24 pages, 5772 KiB  
Article
Bio-Based Electrospun Fibers from Chitosan Schiff Base and Polylactide and Their Cu2+ and Fe3+ Complexes: Preparation and Antibacterial and Anticancer Activities
by Milena Ignatova, Ina Anastasova, Nevena Manolova, Iliya Rashkov, Nadya Markova, Rositsa Kukeva, Radostina Stoyanova, Ani Georgieva and Reneta Toshkova
Polymers 2022, 14(22), 5002; https://doi.org/10.3390/polym14225002 - 18 Nov 2022
Cited by 6 | Viewed by 1756
Abstract
The Schiff base derivative (Ch-8Q) of chitosan (Ch) and 8-hydroxyquinoline-2-carboxaldehyde (8QCHO) was prepared and fibrous mats were obtained by the electrospinning of Ch-8Q/polylactide (PLA) blend solutions in trifluoroacetic acid (TFA). Complexes of the mats were prepared by immersing them in a solution of [...] Read more.
The Schiff base derivative (Ch-8Q) of chitosan (Ch) and 8-hydroxyquinoline-2-carboxaldehyde (8QCHO) was prepared and fibrous mats were obtained by the electrospinning of Ch-8Q/polylactide (PLA) blend solutions in trifluoroacetic acid (TFA). Complexes of the mats were prepared by immersing them in a solution of CuCl2 or FeCl3. Electron paramagnetic resonance (EPR) analysis was performed to examine the complexation of Cu2+(Fe3+) in the Ch-8Q/PLA mats complexes. The morphology of the novel materials and their surface chemical composition were studied by scanning electron microscopy (SEM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The performed microbiological screening demonstrated that in contrast to the neat PLA mats, the Ch-8Q-containing mats and their complexes were able to kill all S. aureus bacteria within 3 h of contact. These fibrous materials had efficiency in suppressing the adhesion of pathogenic bacteria S. aureus. In addition, Ch-8Q/PLA mats and their complexes exerted good anticancer efficacy in vitro against human cervical HeLa cells and human breast MCF-7 cells. The Ch-8Q-containing fibrous materials had no cytotoxicity against non-cancer BALB/c 3T3 mouse fibroblast cells. These properties render the prepared materials promising as wound dressings as well as for application in local cancer treatment. Full article
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21 pages, 6288 KiB  
Article
Influence of Binder Composition and Material Extrusion (MEX) Parameters on the 3D Printing of Highly Filled Copper Feedstocks
by Mahrukh Sadaf, Santiago Cano, Joamin Gonzalez-Gutierrez, Mario Bragaglia, Stephan Schuschnigg, Christian Kukla, Clemens Holzer, Lilla Vály, Michael Kitzmantel and Francesca Nanni
Polymers 2022, 14(22), 4962; https://doi.org/10.3390/polym14224962 - 16 Nov 2022
Cited by 10 | Viewed by 2683
Abstract
This work aims to better understand the type of thermoplastic binders required to produce highly loaded copper filaments that can be successfully printed via low-cost filament-based material extrusion (MEX). Compounding feedstock material with 55 vol.% of copper and three multi-component binder systems has [...] Read more.
This work aims to better understand the type of thermoplastic binders required to produce highly loaded copper filaments that can be successfully printed via low-cost filament-based material extrusion (MEX). Compounding feedstock material with 55 vol.% of copper and three multi-component binder systems has been performed. The MEX behavior of these feedstocks was evaluated by depositing material at different speeds and appropriately selecting the extrusion temperature depending on the binder composition. The rest of the MEX parameters remained constant to evaluate the printing quality for the different feedstocks. Printable filaments were produced with low ovality and good surface quality. The filaments showed good dispersion of the powder and polymeric binder system in SEM analysis. The feedstock mechanical properties, i.e., the tensile strength of the filament, were sufficient to ensure proper feeding in the MEX machine. The viscosity of the feedstock systems at the adjusted printing temperatures lies in the range of 102–103 Pa·s at the shear rate of 100–1000 s−1, which appears to be sufficient to guarantee the correct flowability and continuous extrusion. The tensile properties vary greatly (e.g., ultimate tensile strength 3–9.8 MPa, elongation at break 1.5–40.5%), and the most fragile filament could not be reliably printed at higher speeds. Micrographs of the cross-section of printed parts revealed that as the printing speed increased, the porosity was minimized because the volumetric flow of the feedstock material increased, which can help to fill pores. This study offers new insights into the feedstock requirements needed to produce low-cost intricate copper components of high quality in a reliable and efficient manner. Such components can find many applications in the electronics, biomedical, and many other industries. Full article
(This article belongs to the Special Issue Sustainable Polymeric Composites: Fabrication and Application)
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