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Polymers, Volume 13, Issue 24 (December-2 2021) – 199 articles

Cover Story (view full-size image): A model of the polymerization process during the formation of opposing polymer brushes was designed and investigated. Monte Carlo simulations using the dynamic lattice liquid model were employed using a dedicated parallel machine ARUZ in a large size and time scale. The chains were increasingly compressed for high grafting densities, and there was surprisingly little interpenetration of chains from opposite surfaces. View this paper
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9 pages, 6273 KiB  
Article
Polymer-Templated Durable and Hydrophobic Nanostructures for Hydrogen Gas Sensing Applications
by Mohammad Kamal Hossain and Qasem Ahmed Drmosh
Polymers 2021, 13(24), 4470; https://doi.org/10.3390/polym13244470 - 20 Dec 2021
Cited by 1 | Viewed by 2289
Abstract
A simple and hands-on one-step process has been implemented to fabricate polymer-templated hydrophobic nanostructures as hydrogen gas sensing platforms. Topographic measurements have confirmed irregular hills and dips of various dimensions that are responsible for creating air bubble pockets that satisfy the Cassie–Baxter state [...] Read more.
A simple and hands-on one-step process has been implemented to fabricate polymer-templated hydrophobic nanostructures as hydrogen gas sensing platforms. Topographic measurements have confirmed irregular hills and dips of various dimensions that are responsible for creating air bubble pockets that satisfy the Cassie–Baxter state of hydrophobicity. High-resolution field-emission scanning electron microscopy (FESEM) has revealed double-layer structures consisting of fine microscopic flower-like structures of nanoscale petals on the top of base nanostructures. Wetting contact angle (WCA) measurements further revealed the contact angle to be ~142.0° ± 10.0°. Such hydrophobic nanostructures were expected to provide a platform for gas-sensing materials of a higher surface area. From this direction, a very thin layer of palladium, ca. 100 nm of thickness, was sputtered. Thereafter, further topographic and WCA measurements were carried out. FESEM micrographs revealed that microscopic flower-like structures of nanoscale petals remained intact. A sessile drop test reconfirmed a WCA of as high as ~130.0° ± 10.0°. Due to the inherent features of hydrophobic nanostructures, a wider surface area was expected that can be useful for higher target gas adsorption sites. In this context, a customized sensing facility was set up, and H2 gas sensing performance was carried out. The surface nanostructures were found to be very stable and durable over the course of a year and beyond. A polymer-based hydrophobic gas-sensing platform as investigated in this study will play a dual role in hydrophobicity as well as superior gas-sensing characteristics. Full article
(This article belongs to the Special Issue Synthesis, Processing, Structure and Properties of Polymer Materials)
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16 pages, 5671 KiB  
Article
Poly(ionic liquid) Based Composite Electrolytes for Lithium Ion Batteries
by Robert Löwe, Thomas Hanemann, Tatiana Zinkevich and Andreas Hofmann
Polymers 2021, 13(24), 4469; https://doi.org/10.3390/polym13244469 - 20 Dec 2021
Cited by 4 | Viewed by 3363
Abstract
Polymerized ionic liquids (PIL) are an interesting substance class, which is discussed to transfer the outstanding properties and tunability of ionic liquids into a solid material. In this study we extend our previous research on ammonium based PIL and discuss the influence of [...] Read more.
Polymerized ionic liquids (PIL) are an interesting substance class, which is discussed to transfer the outstanding properties and tunability of ionic liquids into a solid material. In this study we extend our previous research on ammonium based PIL and discuss the influence of additives and their usability as polymer electrolyte membranes for lithium ion batteries. The polymer electrolyte is thereby used as replacement for the commercially widespread system of a separator that is soaked with liquid electrolyte. The influence of the material composition on the ionic conductivity (via electrochemical impedance spectroscopy) and the diffusion coefficients (via pulsed-field-gradient nuclear magnetic resonance spectroscopy) were studied and cell tests with adapted membrane materials were performed. High amounts of the additional ionic liquid (IL) MPPyrr-TFSI (1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide) increased the ionic conductivity of the materials up to 1.3·10−4 S·cm−1 but made the usage of a cross-linker necessary to obtain mechanically stable membranes. The application of liquid electrolyte mixtures with ethylene carbonate (EC) and MPPyrr-TFSI decreased ionic conductivity values down to the 10−9 S·cm−1 range, but increased 7Li diffusion coefficients with increasing amounts of EC up to 1.7·10−10 m2·s−1. Cell tests with two membrane mixtures proofed that it is possible to build electrolyte membranes on basis of the polymerized ionic liquids, but also showed that further research is necessary to ensure stable and efficient cell cycling. Full article
(This article belongs to the Special Issue Advance in New Energy Materials and Devices)
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25 pages, 6310 KiB  
Article
Finite Element Analysis of Glass Fiber-Reinforced Polymer-(GFRP) Reinforced Continuous Concrete Beams
by Hazem Ahmad, Amr Elnemr, Nazam Ali, Qudeer Hussain, Krisada Chaiyasarn and Panuwat Joyklad
Polymers 2021, 13(24), 4468; https://doi.org/10.3390/polym13244468 - 20 Dec 2021
Cited by 7 | Viewed by 2828
Abstract
Fiber-reinforced concrete (FRC) is a competitive solution for the durability of reinforced structures. This paper aims to observe the moment redistribution behavior occurring due to flexural and shear loading in Glass Fiber-Reinforced Polymer- (GFRP) reinforced continuous concrete beams. A rectangular cross-section was adopted [...] Read more.
Fiber-reinforced concrete (FRC) is a competitive solution for the durability of reinforced structures. This paper aims to observe the moment redistribution behavior occurring due to flexural and shear loading in Glass Fiber-Reinforced Polymer- (GFRP) reinforced continuous concrete beams. A rectangular cross-section was adopted in this study with dimensions of 200 mm in width and 300 mm in depth with a constant shear span-to-depth ratio of 3. The reinforcement ratio for the top and bottom were equal at sagging and hogging moment regions. A finite element model was created using Analysis System (ANSYS) and validated with the existing experimental results in the literature review. Based on the literature review, the parametric study was conducted on twelve beam specimens to evaluate the influence of concrete compressive strength, transversal GFRP stirrups ratio, and longitudinal reinforcement ratio on the redistribution of the moment in beams. Several codes and guidelines adopted different analytical models. The Canadian Standards Association (CSA) S806 adopted the modified compression field theory in predicting the shear capacity of the simply supported beams. Recently, various researchers encountered several factors and modifications to account for concrete contribution, longitudinal, and transverse reinforcement. A comparison between the predicting shear capacity of the generated finite element model, the analytical model, and the existing data from the literature was performed. The generated finite element model showed a good agreement with the experimental results, while the beam specimens failed in shear after undergoing significant moment redistribution from hogging to sagging moment region. The moment distribution observed about 21.5% from FEM of beam specimen GN-1.2-0.48-d, while the experimental results achieved 24% at failure load. For high strength concrete presented in beam specimen GH-1.2-0.63-d, the result showed about 20.2% moment distribution, compared to that achieved experimentally of 23% at failure load. Full article
(This article belongs to the Special Issue Polymer Concrete and Composites)
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16 pages, 5081 KiB  
Article
Aging of 3D Printed Polymers under Sterilizing UV-C Radiation
by Catalin Gheorghe Amza, Aurelian Zapciu, Florin Baciu, Mihai Ion Vasile and Diana Popescu
Polymers 2021, 13(24), 4467; https://doi.org/10.3390/polym13244467 - 20 Dec 2021
Cited by 20 | Viewed by 3559
Abstract
In the context of the COVID-19 pandemic, shortwave ultraviolet radiation with wavelengths between 200 nm and 280 nm (UV-C) is seeing increased usage in the sterilization of medical equipment, appliances, and spaces due to its antimicrobial effect. During the first weeks of the [...] Read more.
In the context of the COVID-19 pandemic, shortwave ultraviolet radiation with wavelengths between 200 nm and 280 nm (UV-C) is seeing increased usage in the sterilization of medical equipment, appliances, and spaces due to its antimicrobial effect. During the first weeks of the pandemic, healthcare facilities experienced a shortage of personal protective equipment. This led to hospital technicians, private companies, and even members of the public to resort to 3D printing in order to produce fast, on-demand resources. This paper analyzes the effect of accelerated aging through prolonged exposure to UV-C on mechanical properties of parts 3D printed by material extrusion (MEX) from common polymers, such as polylactic acid (PLA) and polyethylene terephthalate-glycol (PETG). Samples 3D printed from these materials went through a 24-h UV-C exposure aging cycle and were then tested versus a control group for changes in mechanical properties. Both tensile and compressive strength were determined, as well as changes in material creep properties. Prolonged UV-C exposure reduced the mechanical properties of PLA by 6–8% and of PETG by over 30%. These findings are of practical importance for those interested in producing functional MEX parts intended to be sterilized using UV-C. Scanning electron microscopy (SEM) was performed in order to assess any changes in material structure. Full article
(This article belongs to the Special Issue Fatigue and Aging Degradation of Polymeric Materials)
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19 pages, 9764 KiB  
Article
Investigation of Crystallization and Relaxation Effects in Coarse-Grained Polyethylene Systems after Uniaxial Stretching
by Dirk Grommes, Martin R. Schenk, Olaf Bruch and Dirk Reith
Polymers 2021, 13(24), 4466; https://doi.org/10.3390/polym13244466 - 20 Dec 2021
Cited by 3 | Viewed by 2391
Abstract
In this study, we investigate the thermo-mechanical relaxation and crystallization behavior of polyethylene using mesoscale molecular dynamics simulations. Our models specifically mimic constraints that occur in real-life polymer processing: After strong uniaxial stretching of the melt, we quench and release the polymer chains [...] Read more.
In this study, we investigate the thermo-mechanical relaxation and crystallization behavior of polyethylene using mesoscale molecular dynamics simulations. Our models specifically mimic constraints that occur in real-life polymer processing: After strong uniaxial stretching of the melt, we quench and release the polymer chains at different loading conditions. These conditions allow for free or hindered shrinkage, respectively. We present the shrinkage and swelling behavior as well as the crystallization kinetics over up to 600 ns simulation time. We are able to precisely evaluate how the interplay of chain length, temperature, local entanglements and orientation of chain segments influences crystallization and relaxation behavior. From our models, we determine the temperature dependent crystallization rate of polyethylene, including crystallization onset temperature. Full article
(This article belongs to the Special Issue Coarse-Grained Models for Polymers)
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27 pages, 9453 KiB  
Article
Ion-Conducting Flexible Thin Films of Composites from Poly(ethylene oxide) and Nematic Liquid Crystals E8—Characterization by Impedance and Dielectric Relaxation Spectroscopy
by Georgi B. Hadjichristov, Todor E. Vlakhov, Yordan G. Marinov and Nicola Scaramuzza
Polymers 2021, 13(24), 4465; https://doi.org/10.3390/polym13244465 - 20 Dec 2021
Cited by 4 | Viewed by 2522
Abstract
Complex electrical impedance and dielectric spectroscopy were applied to study the dielectric relaxations and their thermal behavior in ion-conducting composites/complexes from polymer poly(ethylene oxide) (PEO) and E8 nematic liquid crystals (LCs), at the compositional ratio PEO:E8 = 70:30 wt%. Flexible thin films of [...] Read more.
Complex electrical impedance and dielectric spectroscopy were applied to study the dielectric relaxations and their thermal behavior in ion-conducting composites/complexes from polymer poly(ethylene oxide) (PEO) and E8 nematic liquid crystals (LCs), at the compositional ratio PEO:E8 = 70:30 wt%. Flexible thin films of PEO/E8 with a thickness of 150 μm were inspected, as well as such films from Na+ ion-conducting electrolyte PEO/E8/NaIO4 with the same PEO:E8 compositional ratio, but additionally containing 10 wt.% from the salt sodium metaperiodate (NaIO4) as a dopant of Na+ ions. The molecular dynamics, namely the dielectric relaxation of PEO/E8 and PEO/E8/NaIO4, were characterized through analyses of complex impedance and dielectric spectra measured in the frequency range of 1 Hz–1 MHz, under variation of temperature from below to above the glass-transition temperature of these composites. The relaxation and polarization of dipole formations in PEO/E8 and PEO/E8/NaIO4 were evidenced and compared in terms of both electrical impedance and dielectric response depending on temperature. The results obtained for molecular organization, molecular relaxation dynamics, and electric polarization in the studied ion-conducting polymer/LC composites/complexes can be helpful in the optimization of their structure and performance, and are attractive for applications in flexible organic electronics, energy storage devices, and mechatronics. Full article
(This article belongs to the Special Issue Advanced Polymeric Films)
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14 pages, 2898 KiB  
Article
Development of Cerium Oxide/Corncob Nanocomposite: A Cost-Effective and Eco-Friendly Adsorbent for the Removal of Heavy Metals
by Sidra Gran, Rukhsanda Aziz, Muhammad Tariq Rafiq, Maryam Abbasi, Abdul Qayyum, Ashraf Y. Elnaggar, Hussein H. Elganzory, Zeinhom M. El-Bahy and Enas E. Hussein
Polymers 2021, 13(24), 4464; https://doi.org/10.3390/polym13244464 - 20 Dec 2021
Cited by 7 | Viewed by 2741
Abstract
This research aims to assess the efficiency of the synthesized corncob as a cost-effective and eco-friendly adsorbent for the removal of heavy metals. Therefore, to carry out the intended research project, initially, the corncob was doped with nanoparticles to increase its efficiency or [...] Read more.
This research aims to assess the efficiency of the synthesized corncob as a cost-effective and eco-friendly adsorbent for the removal of heavy metals. Therefore, to carry out the intended research project, initially, the corncob was doped with nanoparticles to increase its efficiency or adsorption capacity. The prepared adsorbent was evaluated for the adsorption of cadmium (Cd) and chromium (Cr) from aqueous media with the batch experiment method. Factors that affect the adsorption process are pH, initial concentration, contact time and adsorbent dose. The analysis of Cd and Cr was performed by using atomic absorption spectrometry (AAS), while the characterization of the adsorbent was performed using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The results showed that there is a significant difference before and after corncob activation and doping with CeO2 nanoparticles. The maximum removal for both Cd and Cr was at a basic pH with a contact time of 60 min at 120 rpm, which is 95% for Cd and 88% for Cr, respectively. To analyze the experimental data, a pseudo-first-order kinetic model, pseudo-second-order kinetic model, and intra-particle diffusion model were used. The kinetic adsorption studies confirmed that the experimental data were best fitted with the pseudo-second-order kinetic model (R2 = 0.989) and intra-particle diffusion model (R2 = 0.979). This work demonstrates that the cerium oxide/corncob nanocomposite is an inexpensive and environmentally friendly adsorbent for the removal of Cd and Cr from wastewater. Full article
(This article belongs to the Special Issue Advances in Polymer Composites)
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16 pages, 5571 KiB  
Article
Rice Hull-Derived Carbon for Supercapacitors: Towards Sustainable Silicon-Carbon Supercapacitors
by Changwei Li, Honglei Chen, Liqiong Zhang, Shenghui Jiao, Huixin Zhang, Junliu Zhang, Peng Li, Yubo Tao and Xin Zhao
Polymers 2021, 13(24), 4463; https://doi.org/10.3390/polym13244463 - 20 Dec 2021
Cited by 11 | Viewed by 2948
Abstract
A simple and effective mixing carbonization-activation process was developed to prepare rice hull-derived porous Si–carbon materials. The morphologies and pore structures of the materials were controlled effectively without any loading or additions at various carbonization temperatures. The structures of the samples changed from [...] Read more.
A simple and effective mixing carbonization-activation process was developed to prepare rice hull-derived porous Si–carbon materials. The morphologies and pore structures of the materials were controlled effectively without any loading or additions at various carbonization temperatures. The structures of the samples changed from large pores and thick walls after 800 C carbonization to small pores and thin walls after 1000 C carbonization. An additional alkali activation–carbonization process led to coral reef-like structures surrounded by squama in the sample that underwent 900 C carbonization (Act-RH-900). This optimal material (Act-RH-900) had a large specific surface area (768 m2 g−1), relatively stable specific capacitance (150.8 F g−1), high energy density (31.9 Wh kg−1), and high-power density (309.2 w kg−1) at a current density of 0.5 A g−1 in 1 M KOH electrolyte, as well as a good rate performance and high stability (capacitance retention > 87.88% after 5000 cycles). The results indicated that Act-RH-900 is a promising candidate for capacitive applications. This work overcomes the restrictions imposed by the complex internal structure of biomass, implements a simple reaction environment, and broadens the potential applicability of biomass waste in the field of supercapacitors. Full article
(This article belongs to the Special Issue Advances in Processing of Bio-Based Polymeric Materials)
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16 pages, 3817 KiB  
Article
Manufacturing and Characterization of Environmentally Friendly Wood Plastic Composites Using Pinecone as a Filler into a Bio-Based High-Density Polyethylene Matrix
by Maria del Carmen Morcillo, Ramón Tejada, Diego Lascano, Daniel Garcia-Garcia and David Garcia-Sanoguera
Polymers 2021, 13(24), 4462; https://doi.org/10.3390/polym13244462 - 20 Dec 2021
Cited by 3 | Viewed by 3787
Abstract
The use of wood plastic composites (WPC) is growing very rapidly in recent years, in addition, the use of plastics of renewable origin is increasingly implemented because it allows to reduce the carbon footprint. In this context, this work reports on the development [...] Read more.
The use of wood plastic composites (WPC) is growing very rapidly in recent years, in addition, the use of plastics of renewable origin is increasingly implemented because it allows to reduce the carbon footprint. In this context, this work reports on the development of composites of bio-based high density polyethylene (BioHDPE) with different contents of pinecone (5, 10, and 30 wt.%). The blends were produced by extrusion and injection-molded processes. With the objective of improving the properties of the materials, a compatibilizer has been used, namely polyethylene grafted with maleic anhydride (PE-g-MA 2 phr). The effect of the compatibilizer in the blend with 5 wt.% has been compared with the same blend without compatibilization. Mechanical, thermal, morphological, colorimetric, and wettability properties have been analyzed for each blend. The results showed that the compatibilizer improved the filler–matrix interaction, increasing the ductile mechanical properties in terms of elongation and tensile strength. Regarding thermal properties, the compatibilizer increased thermal stability and improved the behavior of the materials against moisture. In general, the pinecone materials obtained exhibited reddish-brown colors, allowing their use as wood plastic composites with a wide range of properties depending on the filler content in the blend. Full article
(This article belongs to the Collection Sustainable Plastics)
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16 pages, 2338 KiB  
Article
Hydrogels Based on Alginates and Carboxymethyl Cellulose with Modulated Drug Release—An Experimental and Theoretical Study
by Cătălina Anișoara Peptu, Elena Simona Băcăiță, Corina-Lenuta Savin (Logigan), Marian Luțcanu and Maricel Agop
Polymers 2021, 13(24), 4461; https://doi.org/10.3390/polym13244461 - 20 Dec 2021
Cited by 7 | Viewed by 2505
Abstract
New hydrogels films crosslinked with epichlorohydrin were prepared based on alginates and carboxymethyl cellulose with properties that recommend them as potential drug delivery systems (e.g., biocompatibility, low toxicity, non-immunogenicity, hemostatic activity and the ability to absorb large amounts of water). The characterization of [...] Read more.
New hydrogels films crosslinked with epichlorohydrin were prepared based on alginates and carboxymethyl cellulose with properties that recommend them as potential drug delivery systems (e.g., biocompatibility, low toxicity, non-immunogenicity, hemostatic activity and the ability to absorb large amounts of water). The characterization of their structural, morphological, swelling capacity, loading/release and drug efficiency traits proved that these new hydrogels are promising materials for controlled drug delivery systems. Further, a new theoretical model, in the framework of Scale Relativity Theory, was built with to offer insights on the release process at the microscopic level and to simplify the analysis of the release process. Full article
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11 pages, 2670 KiB  
Article
Use of Novel Non-Toxic Bismuth Catalyst for the Preparation of Flexible Polyurethane Foam
by Said El Khezraji, Suman Thakur, Mustapha Raihane, Miguel Angel López-Manchado, Larbi Belachemi, Raquel Verdejo and Mohammed Lahcini
Polymers 2021, 13(24), 4460; https://doi.org/10.3390/polym13244460 - 20 Dec 2021
Cited by 2 | Viewed by 4707
Abstract
Foam products are one of the largest markets for polyurethane (PU) and are heavily used in many sectors. However, current PU formulations use highly toxic and environmentally unfriendly production processes. Meanwhile, the increasing environmental concerns and regulations are intensifying the research into green [...] Read more.
Foam products are one of the largest markets for polyurethane (PU) and are heavily used in many sectors. However, current PU formulations use highly toxic and environmentally unfriendly production processes. Meanwhile, the increasing environmental concerns and regulations are intensifying the research into green and non-toxic products. In this study, we synthesized flexible polyurethane foam (PUF) using different weight percentages (0.025%, 0.05% and 0.1%) of a non-toxic bismuth catalyst. The bismuth-catalyzed foams presented a well evolved cellular structure with an open cell morphology. The properties of the bismuth-catalyzed flexible PUF, such as the mechanical, morphological, kinetic and thermal behaviors, were optimized and compared with a conventional tin-catalyzed PUF. The bismuth-catalyst revealed a higher isocyanate conversion efficiency than the stannous octoate catalyst. When comparing samples with similar densities, the bismuth-catalyzed foams present better mechanical behavior than the tin-catalyzed sample with similar thermal stability. The high solubility of bismuth triflate in water, together with its high Lewis acidity, have been shown to benefit the production of PU foams. Full article
(This article belongs to the Special Issue Advanced Cellular Polymers)
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19 pages, 3554 KiB  
Article
New Construction of Functionalized CuO/Al2O3 Nanocomposite-Based Polymeric Sensor for Potentiometric Estimation of Naltrexone Hydrochloride in Commercial Formulations
by Amal M. Al-Mohaimeed, Gamal A. E. Mostafa and Maha F. El-Tohamy
Polymers 2021, 13(24), 4459; https://doi.org/10.3390/polym13244459 - 20 Dec 2021
Cited by 6 | Viewed by 2714
Abstract
Electrically conductive polymeric nanocomposites with nanoparticles are adaptable types of nanomaterials that are prospective for various applications. The extraordinary features of copper oxide (CuO) and aluminium oxide (Al2O3) nanostructures, encourages extensive studies to prospect these metal oxide nanocomposites as [...] Read more.
Electrically conductive polymeric nanocomposites with nanoparticles are adaptable types of nanomaterials that are prospective for various applications. The extraordinary features of copper oxide (CuO) and aluminium oxide (Al2O3) nanostructures, encourages extensive studies to prospect these metal oxide nanocomposites as potential electroactive materials in sensing and biosensing applications. This study suggested a new CuO/Al2O3 nanocomposite-based polymeric coated wire membrane sensor for estimating naltrexone hydrochloride (NTX) in commercial formulations. Naltrexone hydrochloride and sodium tetraphenylborate (Na-TPB) were incorporated in the presence of polymeric polyvinyl chloride (PVC) and solvent mediator o-nitrophenyloctyl ether (o-NPOE) to form naltrexone tetraphenylborate (NTX-TPB) as an electroactive material. The modified sensor using NTX-TPB-CuO/Al2O3 nanocomposite displayed high selectivity and sensitivity for the discrimination and quantification of NTX with a linearity range 1.0 × 10−9–1.0 × 10−2 mol L−1 and a regression equation EmV = (58.25 ± 0.3) log [NTX] + 754.25. Contrarily, the unmodified coated wire sensor of NTX-TPB exhibited a Nernstian response at 1.0 × 10−5–1.0 × 10−2 mol L−1 and a regression equation EmV = (52.1 ± 0.2) log [NTX] + 406.6. The suggested modified potentiometric system was validated with respect to various criteria using the methodology recommended guidelines. Full article
(This article belongs to the Special Issue Metal- and Metal Hybrid-Filled Polymer Nanocomposites)
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16 pages, 8145 KiB  
Article
Preparation of Homopolymer, Block Copolymer, and Patterned Brushes Bearing Thiophene and Acetylene Groups Using Microliter Volumes of Reaction Mixtures
by Joanna Smenda, Karol Wolski, Kamila Chajec and Szczepan Zapotoczny
Polymers 2021, 13(24), 4458; https://doi.org/10.3390/polym13244458 - 19 Dec 2021
Cited by 4 | Viewed by 2924
Abstract
The synthesis of surface-grafted polymers with variable functionality requires the careful selection of polymerization methods that also enable spatially controlled grafting, which is crucial for the fabrication of, e.g., nano (micro) sensor or nanoelectronic devices. The development of versatile, simple, economical, and eco-friendly [...] Read more.
The synthesis of surface-grafted polymers with variable functionality requires the careful selection of polymerization methods that also enable spatially controlled grafting, which is crucial for the fabrication of, e.g., nano (micro) sensor or nanoelectronic devices. The development of versatile, simple, economical, and eco-friendly synthetic strategies is important for scaling up the production of such polymer brushes. We have recently shown that poly (3-methylthienyl methacrylate) (PMTM) and poly (3-trimethylsilyl-2-propynyl methacrylate) (PTPM) brushes with pendant thiophene and acetylene groups, respectively, could be used for the production of ladder-like conjugated brushes that are potentially useful in the mentioned applications. However, the previously developed syntheses of such brushes required the use of high volumes of reagents, elevated temperature, or high energy UV-B light. Therefore, we present here visible light-promoted metal-free surface-initiated ATRP (metal-free SI-ATRP) that allows the economical synthesis of PMTM and PTPM brushes utilizing only microliter volumes of reaction mixtures. The versatility of this approach was shown by the formation of homopolymers but also the block copolymer conjugated brushes (PMTM and PTPM blocks in both sequences) and patterned films using TEM grids serving as photomasks. A simple reaction setup with only a monomer, solvent, commercially available organic photocatalyst, and initiator decorated substrate makes the synthesis of these complex polymer structures achievable for non-experts and ready for scaling up. Full article
(This article belongs to the Special Issue Polymer Brushes: Synthesis, Properties and Structure)
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13 pages, 1278 KiB  
Article
Development of a Weighted Barite-Free Formate Drilling Mud for Well Construction under Complicated Conditions
by Valentin Morenov, Ekaterina Leusheva and Tianle Liu
Polymers 2021, 13(24), 4457; https://doi.org/10.3390/polym13244457 - 19 Dec 2021
Cited by 5 | Viewed by 3313
Abstract
Construction of oil and gas wells at offshore fields often involves high formation pressure and the presence of swellable clay rocks in the section. In addition, productivity preservation is also an important aspect. For this purpose, it is necessary to reduce the solids [...] Read more.
Construction of oil and gas wells at offshore fields often involves high formation pressure and the presence of swellable clay rocks in the section. In addition, productivity preservation is also an important aspect. For this purpose, it is necessary to reduce the solids content of the drilling mud. The purpose of this work is to develop, improve, and study compositions of weighted drilling muds with low content of solids, on the basis of organic salts of alkali metals and polymers for the construction of wells prone to rock swelling and/or cavings, as well as drilling fluids for drilling-in the formation. In order to achieve the set goal the following is required: Analysis of existing drilling muds of higher density for drilling wells in unstable rock intervals and for drilling in the productive formation; analysis of experience in using drilling systems on the formic acid salts base and substantiation of requirements for flushing fluids during well construction; development and investigation of drilling mud compositions on the formate base; and the evaluation of inhibiting effect of systems containing organic salts, polymer reagents, and calcium carbonate on clay samples. The developed drilling mud is characterized by a high inhibiting ability that allows minimized mud-weighting by the natural solid phase. This reduces the volume of prepared mud and facilitates the regulation of its properties by reducing the dispersion of drilled cuttings; it eliminates problems related to hydration and the swelling of active clay rocks; and stabilizes unstable argillites prone to caving. The low solids content, low filtration rates, and inhibitory nature of the mud allows high stability of the rheological properties of the mud, and preserves oil and gas reservoir productivity under conditions of elevated formation pressure. Full article
(This article belongs to the Special Issue Geopolymers - Design, Preparation, Applications)
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27 pages, 4761 KiB  
Review
Copolymerization of Ethylene with Selected Vinyl Monomers Catalyzed by Group 4 Metal and Vanadium Complexes with Multidentate Ligands: A Short Review
by Marzena Białek and Julia Fryga
Polymers 2021, 13(24), 4456; https://doi.org/10.3390/polym13244456 - 19 Dec 2021
Cited by 5 | Viewed by 3909
Abstract
This paper gives a short overview of homogeneous post-metallocene catalysts based on group 4 metal and vanadium complexes bearing multidentate ligands. It summarizes the catalytic behavior of those catalysts in copolymerization of ethylene with 1-olefins, with styrenic monomers and with α,ω-alkenols. The review [...] Read more.
This paper gives a short overview of homogeneous post-metallocene catalysts based on group 4 metal and vanadium complexes bearing multidentate ligands. It summarizes the catalytic behavior of those catalysts in copolymerization of ethylene with 1-olefins, with styrenic monomers and with α,ω-alkenols. The review is focused on finding correlations between the structure of a complex, its catalyst activity and comonomer incorporation ability, as well as the microstructure of the copolymer chains. Full article
(This article belongs to the Special Issue Polymers Synthesis and Characterization)
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23 pages, 6766 KiB  
Article
Highly Stretchable Bacterial Cellulose Produced by Komagataeibacter hansenii SI1
by Izabela Cielecka, Małgorzata Ryngajłło, Waldemar Maniukiewicz and Stanisław Bielecki
Polymers 2021, 13(24), 4455; https://doi.org/10.3390/polym13244455 - 19 Dec 2021
Cited by 11 | Viewed by 3187
Abstract
A new strain of bacteria producing cellulose was isolated from Kombucha and identified as Komagataeibacter hansenii, named SI1. In static conditions, the strain synthesises bacterial nanocellulose with an improved ability to stretch. In this study, utilisation of various carbon and nitrogen sources [...] Read more.
A new strain of bacteria producing cellulose was isolated from Kombucha and identified as Komagataeibacter hansenii, named SI1. In static conditions, the strain synthesises bacterial nanocellulose with an improved ability to stretch. In this study, utilisation of various carbon and nitrogen sources and the impact of initial pH was assessed in terms of bacterial nanocellulose yield and properties. K. hansenii SI1 produces cellulose efficiently in glycerol medium at pH 5.0–6.0 with a yield of 3.20–3.60 g/L. Glucose medium led to the synthesis of membrane characterised by a strain of 77%, which is a higher value than in the case of another Komagataeibacter species. Supplementation of medium with vitamin C results in an enhanced porosity and improves the ability of bacterial nanocellulose to stretch (up to 123%). The properties of modified membranes were studied by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction and mechanical tests. The results show that bacterial nanocellulose produced in SH medium and vitamin C-supplemented medium has unique properties (porosity, tensile strength and strain) without changing the chemical composition of cellulose. The method of production BNC with altered properties was the issue of Polish patent application no. P.431265. Full article
(This article belongs to the Special Issue Functional Natural-Based Polymers)
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19 pages, 9467 KiB  
Article
Non-Isothermal Free-Surface Viscous Flow of Polymer Melts in Pipe Extrusion Using an Open-Source Interface Tracking Finite Volume Method
by Célio Fernandes, Ahmad Fakhari and Željko Tukovic
Polymers 2021, 13(24), 4454; https://doi.org/10.3390/polym13244454 - 19 Dec 2021
Cited by 6 | Viewed by 2311
Abstract
Polymer extrudate swelling is a rheological phenomenon that occurs after polymer melt flow emerges at the die exit of extrusion equipment due to molecular stress relaxations and flow redistributions. Specifically, with the growing demand for large scale and high productivity, polymer pipes have [...] Read more.
Polymer extrudate swelling is a rheological phenomenon that occurs after polymer melt flow emerges at the die exit of extrusion equipment due to molecular stress relaxations and flow redistributions. Specifically, with the growing demand for large scale and high productivity, polymer pipes have recently been produced by extrusion. This study reports the development of a new incompressible non-isothermal finite volume method, based on the Arbitrary Lagrangian–Eulerian (ALE) formulation, to compute the viscous flow of polymer melts obeying the Herschel–Bulkley constitutive equation. The Papanastasiou-regularized version of the constitutive equation is employed. The influence of the temperature on the rheological behavior of the material is controlled by the Williams–Landel–Ferry (WLF) function. The new method is validated by comparing the extrudate swell ratio obtained for Bingham and Herschel–Bulkley flows (shear-thinning and shear-thickening) with reference data found in the scientific literature. Additionally, the essential flow characteristics including yield-stress, inertia and non-isothermal effects were investigated. Full article
(This article belongs to the Special Issue Advanced Polymer Simulation and Processing)
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12 pages, 2055 KiB  
Article
Preparation of Graphene Oxide/Cellulose Composites with Microcrystalline Cellulose Acid Hydrolysis Using the Waste Acids Generated by the Hummers Method of Graphene Oxide Synthesis
by Yuanyuan Miao, Xiuya Wang, Yixing Liu, Zhenbo Liu and Wenshuai Chen
Polymers 2021, 13(24), 4453; https://doi.org/10.3390/polym13244453 - 19 Dec 2021
Cited by 15 | Viewed by 3278
Abstract
The Hummers method is the most commonly used method to prepare graphene oxide (GO). However, many waste acids remain in the raw reaction mixture after the completion of this reaction. The aim of this study was to reuse these waste acids efficiently. In [...] Read more.
The Hummers method is the most commonly used method to prepare graphene oxide (GO). However, many waste acids remain in the raw reaction mixture after the completion of this reaction. The aim of this study was to reuse these waste acids efficiently. In this study, microcrystalline cellulose (MCC) was directly dissolved in the mixture after the high-temperature reaction of the Hummers method. The residual acid was used to hydrolyze MCC, and the graphene oxide/microcrystalline cellulose (GO/MCC) composites were prepared, while the acid was reused. The effects of MCC addition (0.5 g, 1.0 g, and 1.5 g in 20 mL) on the properties of the composites were discussed. The structure, composition, thermal stability, and hydrophobicity of GO/MCC composites were characterized and tested by SEM, XRD, FTIR, TG, and contact angle tests. The results showed that MCC could be acid hydrolyzed into micron and nano-scale cellulose by using the strong acidity of waste liquid after GO preparation, and it interacted with the prepared GO to form GO/MCC composites. When the addition amount of MCC was 1 g, the thermal stability of the composite was the highest due to the interaction between acid-hydrolyzed MCC and GO sheets. At the same time, the hydrophobic property of the GO/MCC composite is better than that of the GO film. The freeze-dried GO/MCC composites are more easily dispersed in water and have stronger stability. Full article
(This article belongs to the Special Issue Advances in Graphene-Based Nanocomposites)
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16 pages, 5166 KiB  
Article
A Versatile Equilibrium Method for the Synthesis of High-Strength, Ladder-like Polyphenylsilsesquioxanes with Finely Tunable Molecular Parameters
by Tatyana O. Ershova, Anton A. Anisimov, Maxim N. Temnikov, Maxim A. Novikov, Mikhail I. Buzin, Galina G. Nikiforova, Yulia S. Dyuzhikova, Ivan E. Ushakov, Olga I. Shchegolikhina and Aziz M. Muzafarov
Polymers 2021, 13(24), 4452; https://doi.org/10.3390/polym13244452 - 18 Dec 2021
Cited by 9 | Viewed by 2684
Abstract
A versatile equilibrium method for synthesizing ladder-like polyphenylsilsesquioxanes (L-PPSQs) with various molecular weights (from 4 to 500 kDa) in liquid ammonia was developed. The effect of diverse parameters, such as temperature, monomer concentration, reaction time, addition or removal of water from the reaction [...] Read more.
A versatile equilibrium method for synthesizing ladder-like polyphenylsilsesquioxanes (L-PPSQs) with various molecular weights (from 4 to 500 kDa) in liquid ammonia was developed. The effect of diverse parameters, such as temperature, monomer concentration, reaction time, addition or removal of water from the reaction medium, on the polycondensation process was determined. The molecular weight characteristics and structure of the L-PPSQ elements obtained were determined by GPC, 1H, 29Si NMR, IR spectroscopy, viscometry, and PXRD methods. The physicochemical properties of L-PPSQs were determined by TGA and mechanical analyses. Full article
(This article belongs to the Special Issue Organosilicon Polymers: From New Structures towards New Properties)
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18 pages, 7142 KiB  
Article
New Considerations on the Determination of the Apparent Shear Viscosity of Polymer Melt with Micro Capillary Dies
by Wangqing Wu, Ke Zeng, Baishun Zhao, Fengnan Duan and Fengze Jiang
Polymers 2021, 13(24), 4451; https://doi.org/10.3390/polym13244451 - 18 Dec 2021
Cited by 3 | Viewed by 2532
Abstract
Capillary rheometers have been widely used for the rheological measurement of polymer melts. However, when micro capillary dies are used, the results are usually neither accurate nor consistent, even under the same measurement conditions. In this work, theoretical modeling and experimental studies were [...] Read more.
Capillary rheometers have been widely used for the rheological measurement of polymer melts. However, when micro capillary dies are used, the results are usually neither accurate nor consistent, even under the same measurement conditions. In this work, theoretical modeling and experimental studies were conducted for a more profound understanding of the mechanism by which the initial and boundary conditions influence the inaccuracy in the apparent shear viscosity determination with micro capillary dies (diameters: 500 μm, 200 μm, 100 μm). The results indicate that the amount of polymer initially in the barrel, the pre-compaction pressure and the capillary die diameter have a significant influence on the development of the micro scale inlet pressure, which directly determines the accuracy of the measurement at low and medium shear rates. The varying melt compressibility was confirmed to be the main factor directly related to the inaccuracy in the micro scale apparent shear viscosity determination. It is suggested that measures such as reducing the amount of polymer initially in the barrel and increasing the pre-compaction pressure could be used to reduce the measurement inaccuracy. Full article
(This article belongs to the Special Issue Polymer Dynamics: Bulk and Nanoconfined Polymers)
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13 pages, 3616 KiB  
Article
The Relationship between Crystal Structure and Mechanical Performance for Fabrication of Regenerated Cellulose Film through Coagulation Conditions
by Tessei Kawano, Satoshi Iikubo and Yoshito Andou
Polymers 2021, 13(24), 4450; https://doi.org/10.3390/polym13244450 - 18 Dec 2021
Cited by 7 | Viewed by 3047
Abstract
Cellulose films regenerated from aqueous alkali–urea solution possess different properties depending on coagulation conditions. However, the correlation between coagulant species and properties of regenerated cellulose (RC) films has not been clarified yet. In this study, RC films were prepared from cellulose nanofiber (CNF) [...] Read more.
Cellulose films regenerated from aqueous alkali–urea solution possess different properties depending on coagulation conditions. However, the correlation between coagulant species and properties of regenerated cellulose (RC) films has not been clarified yet. In this study, RC films were prepared from cellulose nanofiber (CNF) and microcrystalline cellulose (MCC) under several coagulation conditions. Cellulose dissolved in aqueous LiOH–urea solution was regenerated using various solvents at ambient temperature to investigate the effects of their dielectric constant on the properties of RC film. The crystal structure, mechanical properties, and surface morphology of prepared RC films were analyzed using X-ray diffraction (XRD), tensile tester, and atomic probe microscopy (AFM), respectively. It is revealed that the preferential orientation of (110) and (020) crystal planes, which are formed by inter- and intramolecular hydrogen bonding in cellulose crystal regions, changed depending on coagulant species. Furthermore, we found out that tensile strength, elongation at break, and crystal structure properties of RC films strongly correlate to the dielectric constant of solvents used for the coagulation process. This work, therefore, would be able to provide an indicator to control the mechanical performance of RC film depending on its application and to develop detailed researches on controlling the crystal structure of cellulose. Full article
(This article belongs to the Special Issue Mechanical Performance and Modelling of Polymeric Materials)
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20 pages, 5988 KiB  
Article
Application of Failure Criteria on Plywood under Bending
by Miran Merhar
Polymers 2021, 13(24), 4449; https://doi.org/10.3390/polym13244449 - 18 Dec 2021
Cited by 3 | Viewed by 2513
Abstract
In composite materials, the use of failure criteria is necessary to determine the failure forces. Various failure criteria are known, from the simplest ones that compare individual stresses with the corresponding strength, to more complex ones that take into account the sign and [...] Read more.
In composite materials, the use of failure criteria is necessary to determine the failure forces. Various failure criteria are known, from the simplest ones that compare individual stresses with the corresponding strength, to more complex ones that take into account the sign and direction of the stress, as well as mutual interactions of the acting stresses. This study investigates the application of the maximum stress, Tsai-Hill, Tsai-Wu, Puck, Hoffman and Hashin criteria to beech plywood made from a series of plies of differently oriented beech veneers. Specimens were cut from the manufactured boards at various angles and loaded by bending to failure. The mechanical properties of the beech veneer were also determined. The specimens were modelled using the finite element method with a composite modulus and considering the different failure criteria where the failure forces were calculated and compared with the measured values. It was found that the calculated forces based on all failure criteria were lower than those measured experimentally. The forces determined using the maximum stress criterion showed the best agreement between the calculated and measured forces. Full article
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16 pages, 9628 KiB  
Article
Relationships between the Decomposition Behaviour of Renewable Fibres and Their Reinforcing Effect in Composites Processed at High Temperatures
by Janez Slapnik, Thomas Lucyshyn and Gerald Pinter
Polymers 2021, 13(24), 4448; https://doi.org/10.3390/polym13244448 - 18 Dec 2021
Cited by 5 | Viewed by 2053
Abstract
Engineering polymers reinforced with renewable fibres (RF) are an attractive class of materials, due to their excellent mechanical performance and low environmental impact. However, the successful preparation of such composites has proven to be challenging due to the low thermal stability of RF. [...] Read more.
Engineering polymers reinforced with renewable fibres (RF) are an attractive class of materials, due to their excellent mechanical performance and low environmental impact. However, the successful preparation of such composites has proven to be challenging due to the low thermal stability of RF. The aim of the present study was to investigate how different RF behaves under increased processing temperatures and correlate the thermal properties of the fibres to the mechanical properties of composites. For this purpose, hemp, flax and Lyocell fibres were compounded into polypropylene (PP) using a co-rotating twin screw extruder and test specimens were injection moulded at temperatures ranging from 180 °C to 260 °C, with 20 K steps. The decomposition behaviour of fibres was characterised using non-isothermal and isothermal simultaneous thermogravimetric analysis/differential scanning calorimetry (TGA/DSC). The prepared composites were investigated using optical microscopy (OM), colorimetry, tensile test, Charpy impact test, dynamic mechanical analysis (DMA) and melt flow rate (MFR). Composites exhibited a decrease in mechanical performance at processing temperatures above 200 °C, with a steep decrease observed at 240 °C. Lyocell fibres exhibited the best reinforcement effect, especially at elevated processing temperatures, followed by flax and hemp fibres. It was found that the retention of the fibre reinforcement effect at elevated temperatures can be well predicted using isothermal TGA measurements. Full article
(This article belongs to the Special Issue Polymers from Renewable Sources and Their Mechanical Reinforcement)
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24 pages, 6290 KiB  
Article
Sandwich-Structured, Hydrophobic, Nanocellulose-Reinforced Polyvinyl Alcohol as an Alternative Straw Material
by Chun-Tu Chou, Shih-Chen Shi and Chih-Kuang Chen
Polymers 2021, 13(24), 4447; https://doi.org/10.3390/polym13244447 - 18 Dec 2021
Cited by 8 | Viewed by 2993
Abstract
An environmentally friendly, hydrophobic polyvinyl alcohol (PVA) film was developed as an alternative to commercial straws for mitigating the issue of plastic waste. Nontoxic and biodegradable cellulose nanocrystals (CNCs) and nanofibers (CNFs) were used to prepare PVA nanocomposite films by blade coating and [...] Read more.
An environmentally friendly, hydrophobic polyvinyl alcohol (PVA) film was developed as an alternative to commercial straws for mitigating the issue of plastic waste. Nontoxic and biodegradable cellulose nanocrystals (CNCs) and nanofibers (CNFs) were used to prepare PVA nanocomposite films by blade coating and solution casting. Double-sided solution casting of polyethylene-glycol–poly(lactic acid) (PEG–PLA) + neat PLA hydrophobic films was performed, which was followed by heat treatment at different temperatures and durations to hydrophobize the PVA composite films. The hydrophobic characteristics of the prepared composite films and a commercial straw were compared. The PVA nanocomposite films exhibited enhanced water vapor barrier and thermal properties owing to the hydrogen bonds and van der Waals forces between the substrate and the fillers. In the sandwich-structured PVA-based hydrophobic composite films, the crystallinity of PLA was increased by adjusting the temperature and duration of heat treatment, which significantly improved their contact angle and water vapor barrier. Finally, the initial contact angle and contact duration (at the contact angle of 20°) increased by 35% and 40%, respectively, which was a significant increase in the service life of the biodegradable material-based straw. Full article
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32 pages, 4131 KiB  
Article
Kinetics, Isotherm and Thermodynamic Studies for Efficient Adsorption of Congo Red Dye from Aqueous Solution onto Novel Cyanoguanidine-Modified Chitosan Adsorbent
by Nouf F. Al-Harby, Ebtehal F. Albahly and Nadia A. Mohamed
Polymers 2021, 13(24), 4446; https://doi.org/10.3390/polym13244446 - 18 Dec 2021
Cited by 47 | Viewed by 3075
Abstract
Novel Cyanoguanidine-modified chitosan (CCs) adsorbent was successfully prepared via a four-step procedure; first by protection of the amino groups of chitosan, second by insertion of epoxide rings, third by opening the latter with cyanoguanidine, and fourth by restoring the amino groups through elimination [...] Read more.
Novel Cyanoguanidine-modified chitosan (CCs) adsorbent was successfully prepared via a four-step procedure; first by protection of the amino groups of chitosan, second by insertion of epoxide rings, third by opening the latter with cyanoguanidine, and fourth by restoring the amino groups through elimination of the protection. Its structure and morphology were checked using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The adsorption capacity of CCs for Congo Red (CR) dye was studied under various conditions. It decreased significantly with the increase in the solution pH value and dye concentration, while it increased with increasing temperature. The adsorption fitted to the pseudo-second order kinetic model and Elovich model. The intraparticle diffusion model showed that the adsorption involved a multi-step process. The isotherm of CR dye adsorption by CCs conforms to the Langmuir isotherm model, indicating the monolayer nature of adsorption. The maximum monolayer coverage capacity, qmax, was 666.67 mg g−1. Studying the thermodynamic showed that the adsorption was endothermic as illustrated from the positive value of enthalpy (34.49 kJ mol−1). According to the values of ΔG°, the adsorption process was spontaneous at all selected temperatures. The value of ΔS° showed an increase in randomness for the adsorption process. The value of activation energy was 2.47 kJ mol−1. The desorption percentage reached to 58% after 5 cycles. This proved that CCs is an efficient and a promising adsorbent for the removal of CR dye from its aqueous solution. Full article
(This article belongs to the Special Issue Novel Wastewater Treatment Applications Using Polymeric Materials)
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11 pages, 480 KiB  
Review
Polymer-Based Bone Substitutes in Periodontal Infrabony Defects: A Systematic Evaluation of Clinical Studies
by Florin Onisor, Simion Bran, Ileana Mitre, Alexandru Mester, Andrada Voina-Tonea, Gabriel Armencea and Mihaela Baciut
Polymers 2021, 13(24), 4445; https://doi.org/10.3390/polym13244445 - 18 Dec 2021
Cited by 5 | Viewed by 1980
Abstract
Background and Objectives: The aim was to systematically review the available literature regarding the use of polymers as a bone substitute for the treatment of periodontal infrabony defect. Materials and methods: Three databases (PubMed, Scopus and Web of Science) were searched to find [...] Read more.
Background and Objectives: The aim was to systematically review the available literature regarding the use of polymers as a bone substitute for the treatment of periodontal infrabony defect. Materials and methods: Three databases (PubMed, Scopus and Web of Science) were searched to find all relevant studies published in English from inception until September 2021 using a combination of keywords. The inclusion criteria consisted of human clinical studies which reported the use of a polymer-based bone substitute in the treatment of infrabony defects. Results: 164 studies were provided from the databases. Of these, five articles were eligible and reported favorable outcome in terms of probing depth, clinical attachment gain and defect fill at the follow-up (3 months and 6 months). Conclusions: Polymer based-bone substitutes may represent a useful alternative in treating infrabony defects. Due to the limited number of studies, more research is needed to sustain the advantages of these products. Full article
(This article belongs to the Special Issue Biomaterials in Medical Applications)
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13 pages, 3720 KiB  
Article
Characterization of Polyhydroxybutyrate-Based Composites Prepared by Injection Molding
by Marcos M. Hernandez, Nevin S. Gupta, Kwan-Soo Lee, Aaron C. Pital, Babetta L. Marrone, Carl N. Iverson and Joseph H. Dumont
Polymers 2021, 13(24), 4444; https://doi.org/10.3390/polym13244444 - 18 Dec 2021
Cited by 3 | Viewed by 2272
Abstract
The waste generated by single-use plastics is often non-recyclable and non-biodegradable, inevitably ending up in our landfills, ecosystems, and food chain. Through the introduction of biodegradable polymers as substitutes for common plastics, we can decrease our impact on the planet. In this study, [...] Read more.
The waste generated by single-use plastics is often non-recyclable and non-biodegradable, inevitably ending up in our landfills, ecosystems, and food chain. Through the introduction of biodegradable polymers as substitutes for common plastics, we can decrease our impact on the planet. In this study, we evaluate the changes in mechanical and thermal properties of polyhydroxybutyrate-based composites with various additives: Microspheres, carbon fibers or polyethylene glycol (2000, 10,000, and 20,000 MW). The mixtures were injection molded using an in-house mold attached to a commercial extruder. The resulting samples were characterized using microscopy and a series of spectroscopic, thermal, and mechanical techniques. We have shown that the addition of carbon fibers and microspheres had minimal impact on thermal stability, whereas polyethylene glycol showed slight improvements at higher molecular weights. All of the composite samples showed a decrease in hardness and compressibility. The findings described in this study will improve our understanding of polyhydroxybutyrate-based composites prepared by injection molding, enabling advancements in integrating biodegradable plastics into everyday products. Full article
(This article belongs to the Special Issue Mechanical Performance of Sustainable Bio-Based Compounds)
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13 pages, 1054 KiB  
Article
Organosolv Lignin Barrier Paper Coatings from Waste Biomass Resources
by Gregor Lavrič, Aleksandra Zamljen, Janja Juhant Grkman, Edita Jasiukaitytė-Grojzdek, Miha Grilc, Blaž Likozar, Diana Gregor-Svetec and Urška Vrabič-Brodnjak
Polymers 2021, 13(24), 4443; https://doi.org/10.3390/polym13244443 - 17 Dec 2021
Cited by 8 | Viewed by 3010
Abstract
The aim of the study was to isolate lignin from organosolv, beech tree (Fagus sylvatica), and Japanese knotweed (Reynoutria japonica), to use it for paper surface and to replace part of the non-renewable product resources with bio-based ones. A [...] Read more.
The aim of the study was to isolate lignin from organosolv, beech tree (Fagus sylvatica), and Japanese knotweed (Reynoutria japonica), to use it for paper surface and to replace part of the non-renewable product resources with bio-based ones. A total of nine coated samples with different lignin formulations and starch were compounded, prepared, and evaluated. The basic (grammage, thickness, specific density), mechanical (elongation at break, tensile, burst and tear indices), and barrier properties (contact angle, water penetration, water vapour permeability, kit test) of the coated papers were investigated. The analysis showed no significant difference in tensile properties between uncoated and coated samples. Furthermore, the decrease in water vapour transmission rate and the lower contact angle for coated samples were nevertheless confirmed. The novel coating materials show promising products with very good barrier properties. Finally, the correlation between structural, morphological, and (other) natural lignin-based factors was revealed, highlighting the importance of parameters such as the equivalence ratio of aliphatic and phenolic hydroxyl groups or the average molecular weight. Tuning functionality by design could optimise performance in the future. Full article
(This article belongs to the Special Issue Stabilization of Bio-Based Polymeric Materials)
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14 pages, 22602 KiB  
Article
3D Bioprinting of Polycaprolactone-Based Scaffolds for Pulp-Dentin Regeneration: Investigation of Physicochemical and Biological Behavior
by Zohre Mousavi Nejad, Ali Zamanian, Maryam Saeidifar, Hamid Reza Vanaei and Mehdi Salar Amoli
Polymers 2021, 13(24), 4442; https://doi.org/10.3390/polym13244442 - 17 Dec 2021
Cited by 38 | Viewed by 4902
Abstract
In this study, two structurally different scaffolds, a polycaprolactone (PCL)/45S5 Bioglass (BG) composite and PCL/hyaluronic acid (HyA) were fabricated by 3D printing technology and were evaluated for the regeneration of dentin and pulp tissues, respectively. Their physicochemical characterization was performed by field emission [...] Read more.
In this study, two structurally different scaffolds, a polycaprolactone (PCL)/45S5 Bioglass (BG) composite and PCL/hyaluronic acid (HyA) were fabricated by 3D printing technology and were evaluated for the regeneration of dentin and pulp tissues, respectively. Their physicochemical characterization was performed by field emission scanning electron microscopy (FESEM) equipped with energy dispersive spectroscopy (EDS), Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), atomic force microscopy (AFM), contact angle, and compressive strength tests. The results indicated that the presence of BG in the PCL/BG scaffolds promoted the mechanical properties, surface roughness, and bioactivity. Besides, a surface treatment of the PCL scaffold with HyA considerably increased the hydrophilicity of the scaffolds which led to an enhancement in cell adhesion. Furthermore, the gene expression results showed a significant increase in expression of odontogenic markers, e.g., dentin sialophosphoprotein (DSPP), osteocalcin (OCN), and dentin matrix protein 1 (DMP-1) in the presence of both PCL/BG and PCL/HyA scaffolds. Moreover, to examine the feasibility of the idea for pulp-dentin complex regeneration, a bilayer PCL/BG-PCL/HyA scaffold was successfully fabricated and characterized by FESEM. Based on these results, it can be concluded that PCL/BG and PCL/HyA scaffolds have great potential for promoting hDPSC adhesion and odontogenic differentiation. Full article
(This article belongs to the Special Issue Polymers and Their Application in 3D Printing)
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19 pages, 2773 KiB  
Article
A Multi-Analytical Approach for Studying the Effect of New LED Lighting Systems on Modern Paints: Chemical Stability Investigations
by Valentina Pintus, Ferenc Szabó, Dávid Noel Tóth, Karin Wieland, Péter Csuti, Marta Anghelone, Ottavia Santorelli, Carlotta Salvadori, Christoph Haisch, Katja Sterflinger and Manfred Schreiner
Polymers 2021, 13(24), 4441; https://doi.org/10.3390/polym13244441 - 17 Dec 2021
Viewed by 2374
Abstract
This study aims to investigate the chemical stability of some modern paint samples exposed to a new Light Emitting Diode (LED)-lighting system and a halogen lamp by using micro-attenuated total reflectance of Fourier transform infrared spectroscopy (µ-ATR-FTIR), µ-Raman, pyrolysis—gas chromatography/mass spectrometry (Py-GC/MS), and [...] Read more.
This study aims to investigate the chemical stability of some modern paint samples exposed to a new Light Emitting Diode (LED)-lighting system and a halogen lamp by using micro-attenuated total reflectance of Fourier transform infrared spectroscopy (µ-ATR-FTIR), µ-Raman, pyrolysis—gas chromatography/mass spectrometry (Py-GC/MS), and thermally assisted hydrolysis and methylation of GC/MS (THM-GC/MS). Those investigations were performed before and after the exposure of the samples to lightings for 1250, 2400, 3300, and 5000 h. The results obtained with µ-Raman spectroscopy show the high stability of the selected inorganic pigments after the exposure to the lighting systems; while similar to the UV/Vis/NIR results reported in a previous study, µ-ATR-FTIR and THM-GC/MS results evidence greater chemical changes occurring principally on the linseed oil binder-based mock-ups among the acrylic and alkyd-based samples. Moreover, principal component analyses (PCA) and hierarchical cluster analyses (HCA) of THM-GC/MS results highlight that those changes were mostly dependent on the exposure time and on the type of pigment, while being independent of the lighting system used. Finally, semi-quantitative µ-ATR-FTIR results show slight pigment enrichment at the paint surface due to the auto and photo-oxidative degradation of the linseed oil binder. Full article
(This article belongs to the Special Issue Polymeric Materials in Modern-Contemporary Art)
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