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Polymers, Volume 10, Issue 11 (November 2018)

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Cover Story (view full-size image) The tandem ring-opening metathesis polymerization (ROMP)/cross-metathesis (CM) of some cyclic [...] Read more.
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Open AccessArticle Synthesis and Properties of Novel Polyurethanes Containing Long-Segment Fluorinated Chain Extenders
Polymers 2018, 10(11), 1292; https://doi.org/10.3390/polym10111292
Received: 30 October 2018 / Revised: 19 November 2018 / Accepted: 19 November 2018 / Published: 21 November 2018
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Abstract
In this study, novel biodegradable long-segment fluorine-containing polyurethane (PU) was synthesized using 4,4′-diphenylmethane diisocyanate (MDI) and 1H,1H,10H,10H-perfluor-1,10-decanediol (PFD) as hard segment, and polycaprolactone diol (PCL) as a biodegradable soft segment. Nuclear magnetic resonance (NMR) was used to perform 1H NMR, 19F [...] Read more.
In this study, novel biodegradable long-segment fluorine-containing polyurethane (PU) was synthesized using 4,4′-diphenylmethane diisocyanate (MDI) and 1H,1H,10H,10H-perfluor-1,10-decanediol (PFD) as hard segment, and polycaprolactone diol (PCL) as a biodegradable soft segment. Nuclear magnetic resonance (NMR) was used to perform 1H NMR, 19F NMR, 19F–19F COSY, 1H–19F COSY, and HMBC analyses on the PFD/PU structures. The results, together with those from Fourier transform infrared spectroscopy (FTIR), verified that the PFD/PUs had been successfully synthesized. Additionally, the soft segment and PFD were changed, after which FTIR and XPS peak-differentiation-imitating analyses were employed to examine the relationship of the hydrogen bonding reaction between the PFD chain extender and PU. Subsequently, atomic force microscopy was used to investigate the changes in the microphase structure between the PFD chain extender and PU, after which the effects of the thermal properties between them were investigated through thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. Finally, the effects of the PFD chain extender on the mechanical properties of the PU were investigated through a tensile strength test. Full article
(This article belongs to the Special Issue Functional Polyurethanes – In Memory of Prof. József Karger-Kocsis)
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Open AccessArticle Tribological Behavior of Nanocomposites Based on UHMWPE Aged in Simulated Synovial Fluid
Polymers 2018, 10(11), 1291; https://doi.org/10.3390/polym10111291
Received: 24 October 2018 / Revised: 16 November 2018 / Accepted: 19 November 2018 / Published: 21 November 2018
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Abstract
Ultra High molecular weight polyethylene (UHMWPE) suffers wear degradation in total joint replacements and it needs to be improved. Thus, we enhanced wear resistance of UHMWPE with carbon nanofiller and paraffin oil and studied its tribological behavior in Simulated Synovial Fluid (SSF) for [...] Read more.
Ultra High molecular weight polyethylene (UHMWPE) suffers wear degradation in total joint replacements and it needs to be improved. Thus, we enhanced wear resistance of UHMWPE with carbon nanofiller and paraffin oil and studied its tribological behavior in Simulated Synovial Fluid (SSF) for 60 days at 37 °C to reproduce the conditions of a real joint. Ageing in biological fluid accelerates the wear action but nanocomposite exhibited a higher wear resistance compared to UHMWPE because of its higher structural homogeneity. Carbon nanofiller closes the porosity of UHMWPE hindering SSF to penetrate inside. Wear resistance of the nanocomposite with 1.0 wt.% of CNF improved of 65% (before ageing) and of 70% (after 60 days in SSF) with respect to pure UHMWPE. Full article
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Open AccessReview Synthesis and Properties of Gelatin Methacryloyl (GelMA) Hydrogels and Their Recent Applications in Load-Bearing Tissue
Polymers 2018, 10(11), 1290; https://doi.org/10.3390/polym10111290
Received: 21 October 2018 / Revised: 15 November 2018 / Accepted: 16 November 2018 / Published: 21 November 2018
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Abstract
Photocrosslinked gelatin methacryloyl (GelMA) hydrogels have attracted great concern in the biomedical field because of their good biocompatibility and tunable physicochemical properties. Herein, different approaches to synthesize GelMA were introduced, especially, the typical method using UV light to crosslink the gelatin-methacrylic anhydride (MA) [...] Read more.
Photocrosslinked gelatin methacryloyl (GelMA) hydrogels have attracted great concern in the biomedical field because of their good biocompatibility and tunable physicochemical properties. Herein, different approaches to synthesize GelMA were introduced, especially, the typical method using UV light to crosslink the gelatin-methacrylic anhydride (MA) precursor was introduced in detail. In addition, the traditional and cutting-edge technologies to characterize the properties of GelMA hydrogels and GelMA prepolymer were also overviewed and compared. Furthermore, the applications of GelMA hydrogels in cell culture and tissue engineering especially in the load-bearing tissue (bone and cartilage) were summarized, followed by concluding remarks. Full article
(This article belongs to the Special Issue Biopolymers and Biobased Polymers: Chemistry and Engineering)
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Open AccessArticle Multiscale Modeling of Structure, Transport and Reactivity in Alkaline Fuel Cell Membranes: Combined Coarse-Grained, Atomistic and Reactive Molecular Dynamics Simulations
Polymers 2018, 10(11), 1289; https://doi.org/10.3390/polym10111289
Received: 27 October 2018 / Revised: 15 November 2018 / Accepted: 17 November 2018 / Published: 20 November 2018
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Abstract
In this study, molecular dynamics (MD) simulations of hydrated anion-exchange membranes (AEMs), comprised of poly(p-phenylene oxide) (PPO) polymers functionalized with quaternary ammonium cationic groups, were conducted using multiscale coupling between three different models: a high-resolution coarse-grained (CG) model; Atomistic Polarizable Potential [...] Read more.
In this study, molecular dynamics (MD) simulations of hydrated anion-exchange membranes (AEMs), comprised of poly(p-phenylene oxide) (PPO) polymers functionalized with quaternary ammonium cationic groups, were conducted using multiscale coupling between three different models: a high-resolution coarse-grained (CG) model; Atomistic Polarizable Potential for Liquids, Electrolytes and Polymers (APPLE&P); and ReaxFF. The advantages and disadvantages of each model are summarized and compared. The proposed multiscale coupling utilizes the strength of each model and allows sampling of a broad spectrum of properties, which is not possible to sample using any of the single modeling techniques. Within the proposed combined approach, the equilibrium morphology of hydrated AEM was prepared using the CG model. Then, the morphology was mapped to the APPLE&P model from equilibrated CG configuration of the AEM. Simulations using atomistic non-reactive force field allowed sampling of local hydration structure of ionic groups, vehicular transport mechanism of anion and water, and structure equilibration of water channels in the membrane. Subsequently, atomistic AEM configuration was mapped to ReaxFF reactive model to investigate the Grotthuss mechanism in the hydroxide transport, as well as the AEM chemical stability and degradation mechanisms. The proposed multiscale and multiphysics modeling approach provides valuable input for the materials-by-design of novel polymeric structures for AEMs. Full article
(This article belongs to the Special Issue Multiscale Modeling of Polymers)
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Open AccessArticle High-Performance Biobased Unsaturated Polyester Nanocomposites with Very Low Loadings of Graphene
Polymers 2018, 10(11), 1288; https://doi.org/10.3390/polym10111288
Received: 30 October 2018 / Revised: 17 November 2018 / Accepted: 17 November 2018 / Published: 20 November 2018
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Abstract
Graphene-reinforced tung oil (TO)-based unsaturated polyester nanocomposites were prepared via in situ melt polycondensation intergrated with Diels–Alder addition. Functionalized graphene sheets derived from graphene oxide (GO) were then extracted from the obtained nanocomposites and carefully characterized. Furthermore, dispersion state of the graphene nanosheets [...] Read more.
Graphene-reinforced tung oil (TO)-based unsaturated polyester nanocomposites were prepared via in situ melt polycondensation intergrated with Diels–Alder addition. Functionalized graphene sheets derived from graphene oxide (GO) were then extracted from the obtained nanocomposites and carefully characterized. Furthermore, dispersion state of the graphene nanosheets in the cured polymer composites and ultimate properties of the resultant biobased nanocomposites were investigated. Mechanical and thermal properties of the TO-based unsaturated polyester resin (UPR) were greatly improved by the incorporation of GO. For example, at the optimal GO content (only 0.10 wt %), the obtained biobased nanocomposite showed tensile strength and modulus of 43.2 MPa and 2.62 GPa, and Tg of 105.2 °C, which were 159%, 191%, and 49.4% higher than those of the unreinforced UPR/TO resin, respectively. Compared to neat UPR, the biobased UPR nanocomposite with 0.1 wt % of GO even demonstrated superior comprehensive properties (comparable stiffness and Tg, while better toughness and thermal stability). Therefore, the developed biobased UPR nanocomposites are very promising to be applied in structural plastics. Full article
(This article belongs to the Special Issue Graphene-Polymer Composites II)
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Open AccessArticle Sulfonated Binaphthyl-Containing Poly(arylene ether ketone)s with Rigid Backbone and Excellent Film-Forming Capability for Proton Exchange Membranes
Polymers 2018, 10(11), 1287; https://doi.org/10.3390/polym10111287
Received: 26 October 2018 / Revised: 16 November 2018 / Accepted: 16 November 2018 / Published: 19 November 2018
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Abstract
Sterically hindered (S)-1,1′-binaphthyl-2,2′-diol had been successfully copolymerized with 4,4′-sulfonyldiphenol and 4,4′-difluorobenzophenone to yield fibrous poly(arylene ether ketone)s (PAEKs) containing various amounts of binaphthyl unit, which was then selectively and efficiently sulfonated using ClSO3H to yield sulfonated poly(arylene ether ketone)s (SPAEKs) with [...] Read more.
Sterically hindered (S)-1,1′-binaphthyl-2,2′-diol had been successfully copolymerized with 4,4′-sulfonyldiphenol and 4,4′-difluorobenzophenone to yield fibrous poly(arylene ether ketone)s (PAEKs) containing various amounts of binaphthyl unit, which was then selectively and efficiently sulfonated using ClSO3H to yield sulfonated poly(arylene ether ketone)s (SPAEKs) with ion exchange capacities (IECs) ranging from 1.40 to 1.89 mmol·g−1. The chemical structures of the polymers were confirmed by 2D 1H–1H COSY NMR and FT-IR. The thermal properties, water uptake, swelling ratio, proton conductivity, oxidative stability and mechanical properties of SPAEKs were investigated in detail. It was found that the conjugated but non-coplanar structure of binaphthyl unit endorsed excellent solubility and film-forming capability to SPAEKs. The SPAEK-50 with an IEC of 1.89 mmol·g−1 exhibited a proton conductivity of 102 mS·cm−1 at 30 °C, much higher than that of the state-of-the-art Nafion N212 membrane and those of many previously reported aromatic analogs, which may be attributed to the likely large intrinsic free volume of SPAEKs created by the highly twisted chain structures and the desirable microscopic morphology. Along with the remarkable water affinity, thermal stabilities and mechanical properties, the SPAEKs were demonstrated to be promising proton exchange membrane (PEM) candidates for potential membrane separations. Full article
(This article belongs to the Special Issue Polymeric Materials for Electrochemical Energy Conversion and Storage)
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Open AccessArticle Direct Growth of a Polypyrrole Aerogel on Hollow CuS Hierarchical Microspheres Yields Particles with Excellent Electromagnetic Wave Properties
Polymers 2018, 10(11), 1286; https://doi.org/10.3390/polym10111286
Received: 25 October 2018 / Revised: 15 November 2018 / Accepted: 16 November 2018 / Published: 19 November 2018
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Abstract
A current hot topic in polymer science is the development of electromagnetic wave-absorbing materials with desired properties (i.e., proper impedance matching and strong attenuation capability), but it presents a considerable challenge. In this work, solvothermal, and self-assembled polymerization were employed for the controlled [...] Read more.
A current hot topic in polymer science is the development of electromagnetic wave-absorbing materials with desired properties (i.e., proper impedance matching and strong attenuation capability), but it presents a considerable challenge. In this work, solvothermal, and self-assembled polymerization were employed for the controlled fabrication of a uniform polypyrrole (PPy) aerogel coated on hollow CuS hierarchical microspheres ([email protected]). The PPy coating thickness of the heterostructure could be tuned by varying the feeding weight ratios of CuS/pyrrole monomer. The electromagnetic wave absorption properties of the [email protected] composites were estimated to be in the frequency range 2–18 GHz. The as-prepared Sample B (fabricated by the addition of 35 mg CuS) showed a maximum reflection loss (RL) of −52.85 dB at a thickness of 2.5 mm. Moreover, an ultra-wide effective bandwidth (RL ≤ −10 dB) from 9.78 to 17.80 GHz (8.02 GHz) was achieved. Analysis of the electromagnetic properties demonstrated that the [email protected] had a remarkable enhancement compared to pure CuS platelet-based spheres and pure PPy, which can be attributed to the increased relatively complex permittivity and the promoted dielectric loss by the intense interfacial dielectric polarizations. We believe that the as-fabricated [email protected] can be a good reference for the fabrication of lightweight and optimal broadband absorbers. Full article
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Open AccessArticle Green Processes for Green Products: The Use of Supercritical CO2 as Green Solvent for Compatibilized Polymer Blends
Polymers 2018, 10(11), 1285; https://doi.org/10.3390/polym10111285
Received: 25 September 2018 / Revised: 23 October 2018 / Accepted: 26 October 2018 / Published: 19 November 2018
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Abstract
Polycaprolactone-g-glycidyl methacrylate (PCL-g-GMA), a reactive interfacial agent for PCL-starch blends, is synthesized using supercritical carbon dioxide (scCO2) as reaction medium and relatively high molecular weight PCL (Mw = 50,000). Higher GMA and radical initiator intakes [...] Read more.
Polycaprolactone-g-glycidyl methacrylate (PCL-g-GMA), a reactive interfacial agent for PCL-starch blends, is synthesized using supercritical carbon dioxide (scCO2) as reaction medium and relatively high molecular weight PCL (Mw = 50,000). Higher GMA and radical initiator intakes lead to higher functionalization degrees (FD) for PCL-g-GMA samples. A mathematical model is developed to describe the correlation between monomer and initiator intake and FD values. The model shows an excellent R2-value (0.978), which implies a good fit of the experimental data. Comparison of this model with a similar one for the reaction in the melt clearly indicates a better reaction efficiency in scCO2. Furthermore, GPC results show that less degradation occurred for samples made in scCO2. Finally, the use of the PCL-g-GMA made in scCO2 (as interfacial agent) in ternary blend of PCL/starch/PCL-g-GMA results in better mechanical properties with respect to those obtained by using the same graft-copolymer as prepared in the melt. Full article
(This article belongs to the Special Issue Bio-Based Resins and Crosslinked Polymers from Renewable Resources)
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Open AccessArticle Isothermal Crystallization and Rheology Properties of Isotactic Polypropylene/Bacterial Cellulose Composite
Polymers 2018, 10(11), 1284; https://doi.org/10.3390/polym10111284
Received: 15 October 2018 / Revised: 15 November 2018 / Accepted: 15 November 2018 / Published: 18 November 2018
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Abstract
Bacterial cellulose (BC) is a new kind of cellulose with great potential in enhancing preparation of isotactic Polypropylene (iPP) composites, which have been found with excellent performance. However, the interface compatibility between BC and iPP is poor. In this study, iPP/BC composites were [...] Read more.
Bacterial cellulose (BC) is a new kind of cellulose with great potential in enhancing preparation of isotactic Polypropylene (iPP) composites, which have been found with excellent performance. However, the interface compatibility between BC and iPP is poor. In this study, iPP/BC composites were prepared by solution mixing. Esterification modified BC (CO) and Maleic anhydride grafted polypropylene (MAPP) added as a compatibilizer was both used to improve the interfacial compatibility of the iPP/BC composites. The rheology and isothermal crystallization behavior of the composites was tested and discussed. The result shows that the complex viscosity and storage modulus of the composite significantly increase in the rule iPP, iPP/BC2, iPP/CO2, and M-iPP/BC3, which indicates that the compatibility of the composite increases as this rule. According to the isothermal crystallization kinetics result, the crystal growth mode of iPP was not affected by the addition of BC and the interfacial compatibility. The spherulite growth rate of the iPP/BC composite increases with increasing crystallization temperature. Especially, the value decreases as the same rule with the complex viscosity and storage modulus of the composite at the same isothermal crystallization temperature. These results suggest that the interface compatibility of iPP/BC composites is greatly improved and the interface compatibility of the M-iPP/BC3 is better than the iPP/CO2. Full article
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Open AccessArticle Effect of Compatibilizer on the Interface Bonding of Graphene Oxide/Polypropylene Composite Fibers
Polymers 2018, 10(11), 1283; https://doi.org/10.3390/polym10111283
Received: 17 October 2018 / Revised: 14 November 2018 / Accepted: 15 November 2018 / Published: 18 November 2018
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Abstract
To improve the interfacial bonding and thermal stability of graphene oxide (GO)/polypropylene (PP) composite fibers, a composite fiber with PP as the matrix, GO as reinforcement and maleic anhydride-grafted PP (PP-g-MAH) as a compatibilizer was prepared by a simple and efficient melt-blending method. [...] Read more.
To improve the interfacial bonding and thermal stability of graphene oxide (GO)/polypropylene (PP) composite fibers, a composite fiber with PP as the matrix, GO as reinforcement and maleic anhydride-grafted PP (PP-g-MAH) as a compatibilizer was prepared by a simple and efficient melt-blending method. The GO content was 0.0–5.0 wt %. According to the Fourier Transform Infrared (FT-IR) spectroscopy results, the interfacial bonding in the PP/MAH/GO composite fibers was improved. The Dynamic Mechanical Analysis (DMA) results show that the addition of GO resulted in better interfacial adhesion and higher storage modulus (E′). The loss modulus (E″) of the PP/MAH/GO-x composite fibers increased with increasing amount of added GO, whereas the loss factor (tan δ) decreased. GO and PP-g-MAH were analyzed by Thermogravimetric Analysis (TGA). The thermal stability of the composite fibers was improved compared to PP. Differential Scanning Calorimetry (DSC) analysis showed that the addition of PP-g-MAH to the composite fiber improved the interfacial bonding of GO in the PP matrix. Thus, compatibility between the two components was obtained. Based on the Scanning Electron Microscopy (SEM) results, the PP fibers exhibited relative orientation due to the strong crystalline morphology. The rough section, PP/GO blend fiber exhibits a very clear phase separation morphology due to the incompatibility between the two and the compatibility of GO and PP in PP/MAH/GO-3 composite fiber is improved, resulting in the interface between the two has improved. Full article
(This article belongs to the Special Issue Graphene-Polymer Composites II)
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Open AccessArticle Synthesis of Nitrogen-Doped Lignin/DES Carbon Quantum Dots as a Fluorescent Probe for the Detection of Fe3+ Ions
Polymers 2018, 10(11), 1282; https://doi.org/10.3390/polym10111282
Received: 24 September 2018 / Revised: 30 October 2018 / Accepted: 15 November 2018 / Published: 17 November 2018
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Abstract
Carbon quantum dots (CQDs) as a rising star of carbon nanomaterials have extensive applications due to their excellent characteristics. In this work, we introduce a simple and green method to prepare nitrogen-doped lignin carbon quantum dots (N-L-CQDs) by using alkali lignin carbon sources [...] Read more.
Carbon quantum dots (CQDs) as a rising star of carbon nanomaterials have extensive applications due to their excellent characteristics. In this work, we introduce a simple and green method to prepare nitrogen-doped lignin carbon quantum dots (N-L-CQDs) by using alkali lignin carbon sources and deep eutectic solvent (DES) as solution and nitrogen source. The physiochemical characterization results suggested that N-L-CQDs with diameters ranging from 4 to 12 nm were successfully synthesized. The optical properties data indicated that the as-prepared N-L-CQDs with a quantum yield of 7.95% exhibited excellent optoelectronic properties, excitation-dependent and pH stability. After that, we have investigated the N-L-CQDs used as fluorescent probes to detect iron ions, which suggested that the as-prepared N-L-CQDs exhibited excellent sensitivity and selectivity for Fe3+ with a detection limit of 0.44 μM. Besides, cytotoxicity of N-L-CQDs was also evaluated by MTT assay. These results demonstrated that the as-prepared N-L-CQDs with excellent properties have potential applications in environment and biomedicine. Full article
(This article belongs to the Special Issue Lignin Polymers: Structures, Reactions and Applications)
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Open AccessArticle A Novel Ziegler–Natta-Type Catalytic System—TiCl4/2,2′-Dimethoxy-1,1′-Binaphthalene/Et3Al2Cl3/Bu2Mg for Production of Ultrahigh Molecular Weight Polyethylene Nascent Reactor Powders, Suitable for Solvent-Free Processing
Polymers 2018, 10(11), 1281; https://doi.org/10.3390/polym10111281
Received: 29 October 2018 / Revised: 14 November 2018 / Accepted: 15 November 2018 / Published: 17 November 2018
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Abstract
A series of ultrahigh molecular weight polyethylenes with viscosity-average molecular weights in the range of 1.6–5.6 × 106 have been prepared by using a novel Ziegler–Natta-type catalytic system—TiCl4/2,2′-dimethoxy-1,1′-binaphthalene/Et3Al2Cl3/Bu2Mg at different temperatures ( [...] Read more.
A series of ultrahigh molecular weight polyethylenes with viscosity-average molecular weights in the range of 1.6–5.6 × 106 have been prepared by using a novel Ziegler–Natta-type catalytic system—TiCl4/2,2′-dimethoxy-1,1′-binaphthalene/Et3Al2Cl3/Bu2Mg at different temperatures (Tpoly) in the range between 10 and 70 °C in toluene. The morphology of the nascent reactor powders has been studied by scanning electron microscopy, wide-angle X-ray diffraction, and the DSC melting behavior. Polymers are suitable for the modern processing methods—the solvent-free solid-state formation of super high-strength (tensile strength over 1.8–2.5 GPa) and high-modulus (elastic modulus up to 136 GPa) oriented film tapes. With decrease of Tpoly, the drawability of the reactor powders increased significantly. Full article
(This article belongs to the Special Issue Olefin Polymerization and Polyolefin)
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Open AccessArticle The Influence of Shape Memory Alloy Volume Fraction on the Impact Behavior of Polymer Composites
Polymers 2018, 10(11), 1280; https://doi.org/10.3390/polym10111280
Received: 23 October 2018 / Revised: 6 November 2018 / Accepted: 13 November 2018 / Published: 16 November 2018
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Abstract
The low-velocity impact behavior of Shape Memory Alloy (SMA) reinforced resin matrix polymers is investigated and the influence of the SMA volume fraction on the impact performance of polymer composites is considered for the first time, which are the highlights in this paper. [...] Read more.
The low-velocity impact behavior of Shape Memory Alloy (SMA) reinforced resin matrix polymers is investigated and the influence of the SMA volume fraction on the impact performance of polymer composites is considered for the first time, which are the highlights in this paper. Firstly, 12 kinds of polymer composite specimens with different SMA volume fractions are fabricated in terms of the SMA layup spacing, SMA diameter, and the interaction between the two. Secondly, a low-velocity impact test is carried out in order to study the impact performances of the above polymer composites. Finally, the damage morphology of the specimen after impact is observed by the visualization method and the low-velocity impact performance of the 12 kinds of polymer composites is analyzed on the basis of the force and energy history curve. Full article
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Open AccessArticle Thermal–Mechanical Coupling Behavior of Directional Polymethylmethacrylate under Tension and Compression
Polymers 2018, 10(11), 1279; https://doi.org/10.3390/polym10111279
Received: 25 September 2018 / Revised: 30 October 2018 / Accepted: 13 November 2018 / Published: 16 November 2018
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Abstract
In this work, the quasi-static and dynamic mechanical behavior of directional polymethylmethacrylate is investigated under conditions of uniaxial compression and tension. The main purpose of this investigation is to discuss the effect of strain rate and temperature on the deformation characteristics and failure [...] Read more.
In this work, the quasi-static and dynamic mechanical behavior of directional polymethylmethacrylate is investigated under conditions of uniaxial compression and tension. The main purpose of this investigation is to discuss the effect of strain rate and temperature on the deformation characteristics and failure of such material. Research was carried out with the use of an electric universal testing machine and split Hopkinson bars, which were equipped with high- and low-temperature control systems. The experimental methods for studying the tensile and compressive response of polymer materials under different testing conditions were validated by one-dimensional stress wave theory and digital-image correlation technique. The finite deformation stress–strain behaviors of the samples under different loading condition were obtained with a constant temperature ranging from 218 to 373 K. The experimental results showed that the uniaxial tensile and compressive behaviors of directional polymethylmethacrylate under finite deformation are strongly dependent on temperature, decreased tensile and compressive stress of the material under different strain levels, and increased temperature. Meanwhile, the dynamic tensile and compressive stresses of the material are much higher than the quasi-static stresses, showing the strain-rate strengthening effect. Moreover, the tensile and compressive mechanical behavior of directional polymethylmethacrylate has significant asymmetry. Finally, a visco-hyperelastic model is established to predict the rate-dependence mechanical behavior of directional polymethylmethacrylate at different temperatures. Full article
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Open AccessReview Natural Polymers for Organ 3D Bioprinting
Polymers 2018, 10(11), 1278; https://doi.org/10.3390/polym10111278
Received: 18 September 2018 / Revised: 17 October 2018 / Accepted: 19 October 2018 / Published: 16 November 2018
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Abstract
Three-dimensional (3D) bioprinting, known as a promising technology for bioartificial organ manufacturing, has provided unprecedented versatility to manipulate cells and other biomaterials with precise control their locations in space. Over the last decade, a number of 3D bioprinting technologies have been explored. Natural [...] Read more.
Three-dimensional (3D) bioprinting, known as a promising technology for bioartificial organ manufacturing, has provided unprecedented versatility to manipulate cells and other biomaterials with precise control their locations in space. Over the last decade, a number of 3D bioprinting technologies have been explored. Natural polymers have played a central role in supporting the cellular and biomolecular activities before, during and after the 3D bioprinting processes. These polymers have been widely used as effective cell-loading hydrogels for homogeneous/heterogeneous tissue/organ formation, hierarchical vascular/neural/lymphatic network construction, as well as multiple biological/biochemial/physiological/biomedical/pathological functionality realization. This review aims to cover recent progress in natural polymers for bioartificial organ 3D bioprinting. It is structured as introducing the important properties of 3D printable natural polymers, successful models of 3D tissue/organ construction and typical technologies for bioartificial organ 3D bioprinting. Full article
(This article belongs to the Special Issue Additive Manufacturing of Polymeric Materials)
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Open AccessArticle Difference in Macroscopic Morphologies of Amylosic Supramolecular Networks Depending on Guest Polymers in Vine-Twining Polymerization
Polymers 2018, 10(11), 1277; https://doi.org/10.3390/polym10111277
Received: 5 November 2018 / Revised: 13 November 2018 / Accepted: 15 November 2018 / Published: 16 November 2018
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Abstract
Amylose, a natural polysaccharide, acts as a host molecule to form supramolecular inclusion complexes in its enzymatically formation process, that is, phosphorylase-catalyzed enzymatic polymerization using the α-d-glucose 1-phosphate monomer and the maltooligosaccharide primer, in the presence of appropriate guest polymers (vine-twining [...] Read more.
Amylose, a natural polysaccharide, acts as a host molecule to form supramolecular inclusion complexes in its enzymatically formation process, that is, phosphorylase-catalyzed enzymatic polymerization using the α-d-glucose 1-phosphate monomer and the maltooligosaccharide primer, in the presence of appropriate guest polymers (vine-twining polymerization). Furthermore, in the vine-twining polymerization using maltooligosaccharide primer-grafted polymers, such as maltoheptaose (G7)-grafted poly(γ-glutamic acid) (PGA), in the presence of poly(ε-caprolactone) (PCL), the enzymatically elongated amylose graft chains have formed inclusion complexes with PCL among the PGA main-chains to construct supramolecular networks. Either hydrogelation or aggregation as a macroscopic morphology from the products was observed in accordance with PCL/primer feed ratios. In this study, we evaluated macroscopic morphologies from such amylosic supramolecular networks with different guest polymers in the vine-twining polymerization using G7-grafted PGA in the presence of polytetrahydrofuran (PTHF), PCL, and poly(l-lactide) (PLLA). Consequently, we found that the reaction mixture using PTHF totally turned into a hydrogel form, whereas the products using PCL and PLLA were aggregated in the reaction mixtures. The produced networks were characterized by powder X-ray diffraction and scanning electron microscopic measurements. The difference in the macroscopic morphologies was reasonably explained by stabilities of the complexes depending on the guest polymers. Full article
(This article belongs to the Special Issue Polysaccharides)
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Open AccessArticle Surface-Induced Nanostructures and Phase Diagrams of ABC Linear Triblock Copolymers under Spherical Confinement: A Self-Consistent Field Theory Simulation
Polymers 2018, 10(11), 1276; https://doi.org/10.3390/polym10111276
Received: 23 October 2018 / Revised: 8 November 2018 / Accepted: 14 November 2018 / Published: 16 November 2018
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Abstract
We investigate the nanostructures and phase diagrams of ABC linear triblock copolymers confined in spherical cavities by using real-space self-consistent field theory. Various 3D morphologies, such as spherical concentric lamellae, dumbbell-like cylinder, and rotational structures, are identified in the phase diagrams, which are [...] Read more.
We investigate the nanostructures and phase diagrams of ABC linear triblock copolymers confined in spherical cavities by using real-space self-consistent field theory. Various 3D morphologies, such as spherical concentric lamellae, dumbbell-like cylinder, and rotational structures, are identified in the phase diagrams, which are constructed on the basis of the diameters of spherical cavities and the interaction between the polymers and preferential surfaces. We designate specific monomer-monomer interactions and block compositions, with which the polymers spontaneously form a cylindrical morphology in bulk, and firstly study morphology transformation with a neutral surface when a confining radius progressively increases. We then focus on phase morphologies under the preferential surfaces and consolidate them into phase diagrams. The spherical radius and the degree of preferential interactions can obviously induce the formation of a cylindrical morphology. Theoretical results correspond to an amount of recent experimental observations to a high degree and contribute to synthesising functional materials. Full article
(This article belongs to the Special Issue Polymer in Confinement)
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Open AccessArticle Fabrication of Carbohydrate Chips Based on Polydopamine for Real-Time Determination of Carbohydrate–Lectin Interactions by QCM Biosensor
Polymers 2018, 10(11), 1275; https://doi.org/10.3390/polym10111275
Received: 17 October 2018 / Revised: 8 November 2018 / Accepted: 12 November 2018 / Published: 16 November 2018
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Abstract
A novel approach for preparing carbohydrate chips based on polydopamine (PDA) surface to study carbohydrate–lectin interactions by quartz crystal microbalance (QCM) biosensor instrument has been developed. The amino-carbohydrates were immobilized on PDA-coated quartz crystals via Schiff base reaction and/or Michael addition reaction. The [...] Read more.
A novel approach for preparing carbohydrate chips based on polydopamine (PDA) surface to study carbohydrate–lectin interactions by quartz crystal microbalance (QCM) biosensor instrument has been developed. The amino-carbohydrates were immobilized on PDA-coated quartz crystals via Schiff base reaction and/or Michael addition reaction. The resulting carbohydrate-chips were applied to QCM biosensor instrument with flow-through system for real-time detection of lectin–carbohydrate interactions. A series of plant lectins, including wheat germ agglutinin (WGA), concanavalin A (Con A), Ulex europaeus agglutinin I (UEA-I), soybean agglutinin (SBA), and peanut agglutinin (PNA), were evaluated for the binding to different kinds of carbohydrate chips. Clearly, the results show that the predicted lectin selectively binds to the carbohydrates, which demonstrates the applicability of the approach. Furthermore, the kinetics of the interactions between Con A and mannose, WGA and N-Acetylglucosamine were studied, respectively. This study provides an efficient approach to preparing carbohydrate chips based on PDA for the lectin–carbohydrate interactions study. Full article
(This article belongs to the Special Issue Polymer Based Bio-Sensors)
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Open AccessArticle Molecular Dynamics Simulations of Molecular Diffusion Equilibrium and Breakdown Mechanism of Oil-Impregnated Pressboard with Water Impurity
Polymers 2018, 10(11), 1274; https://doi.org/10.3390/polym10111274
Received: 30 October 2018 / Revised: 13 November 2018 / Accepted: 15 November 2018 / Published: 16 November 2018
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Abstract
The water molecule migration and aggregation behaviors in oil-impregnated pressboard are investigated by molecular dynamics simulations in combination with Monte Carlo molecular simulation technique. The free energy and phase diagram of H2O-dodecylbenzene (DDB) and H2O-cellulose mixtures are calculated by [...] Read more.
The water molecule migration and aggregation behaviors in oil-impregnated pressboard are investigated by molecular dynamics simulations in combination with Monte Carlo molecular simulation technique. The free energy and phase diagram of H2O-dodecylbenzene (DDB) and H2O-cellulose mixtures are calculated by Monte Carlo technique combined with the modified Flory-Huggins model, demonstrating that H2O molecules can hardly dissolved with infinitesimal content in cellulose system at temperature lower than 650 K, based on which the oil/cellulose layered structure with water impurity representing three-phase coexistence in oil-impregnated pressboard are modeled and performed for molecular dynamics. The molecular dynamics of H2O/DDB/cellulose three-phase mixture simulating oil-paper insulating system with H2O impurity indicates that DDB molecules can thermally intrude into the cellulose-water interface so as to separate the water phase and cellulose fiber. The first-principles electronic structure calculations for local region of H2O/DDB interface show that H2O molecules can introduce bound states to trap electrons and acquire negative charges, so that they will obtain sufficient energy from applied electric field to break DDB molecular chain by collision, which are verified by subsequent molecular dynamics simulations of H2O/DDB interface model. The electric breakdown mechanism under higher than 100 kV/m electric field is presented based on the further first-principles calculations of the produced carbonized fragments being dissolved and diffusing in DDB phase. The resulted broken DDB fragments will introduce impurity band between valence and conduction bands of DDB system, evidently decreasing bandgap as to that of conducting materials in their existence space. The conductance channel of these carbonized DDB fragments will eventually be formed to initiate the avalanche breakdown process by the cycle-feedback of injected charge carriers with carbonized channels. Full article
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Open AccessArticle Synthesis and Characterization of BaTiO3/Polypyrrole Composites with Exceptional Dielectric Behaviour
Polymers 2018, 10(11), 1273; https://doi.org/10.3390/polym10111273
Received: 21 October 2018 / Revised: 8 November 2018 / Accepted: 12 November 2018 / Published: 16 November 2018
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Abstract
Higher concentrations of ceramic fillers induce brittleness in the ceramic/polymer hybrids which restrict their applications to limited fields especially when such hybrids are prepared for their use as dielectrics. We have synthesized and characterized different BaTiO3-polypyrrole (PPy) composites by changing the [...] Read more.
Higher concentrations of ceramic fillers induce brittleness in the ceramic/polymer hybrids which restrict their applications to limited fields especially when such hybrids are prepared for their use as dielectrics. We have synthesized and characterized different BaTiO3-polypyrrole (PPy) composites by changing the concentration of BaTiO3 from 1% by weight of PPy taken to 5 wt % to explore its effect on the dielectric parameters of the final product and found that the BaTiO3-polypyrrole composite with weight ratio of 0.05:1 exhibited highest dielectric constant, lowest dielectric loss and thermally most stable. All the composites were prepared using in-situ polymerization of pyrrole in an aqueous dispersion of low content of BaTiO3 in the presence of small amount of Hydrochloric acid. These composites were characterized for their microstructure and crystallinity by X-ray diffractometer (XRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM) while thermal stability by thermo gravimetric (TGA) analysis. An impedance analyser (LCR meter) was utilized to investigate the dielectric parameters. FT-IR data confirmed the presence of the two phases and their interaction, inferred from the shifting of normal PPy peaks. The data obtained from XRD confirmed the presence of crystallites of 2.8 to 5 nm with dominant crystallinity of the filler, TGA analysis (25 to 600 °C) confirmed the higher thermal stability induced on successive addition of the filler into the prepared composites as compared to that of pure PPy in a wide temperature range which is unusual for such a low % age addition of the filler. The SEM analysis together with XRD results reveal that the successive introduction of BaTiO3 particles produced crystallites of 2 to 5 nm size which bonded together and changed the hemispherical shaped larger grains of the matrix to regular shaped smaller grains. The dielectric constant of the composites was enhanced with filler contents from 178 to 522 at 1 MHz for 1 wt % and 5 wt % BaTiO3 respectively. It was concluded that the introduction of BaTiO3 into the polymer matrix with this new procedure has greatly affected the polymerization process, thermal stability, morphology and dielectric properties of the host matrix and has resulted in a novel series of the composites which may have broad applications. Full article
(This article belongs to the Special Issue Polymers: Design, Function and Application)
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Open AccessArticle ZnO Quantum Dots Modified by pH-Activated Charge-Reversal Polymer for Tumor Targeted Drug Delivery
Polymers 2018, 10(11), 1272; https://doi.org/10.3390/polym10111272
Received: 25 October 2018 / Revised: 9 November 2018 / Accepted: 12 November 2018 / Published: 15 November 2018
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Abstract
In this paper, we reported a pH responsive nano drug delivery system (NDDS) based on ZnO quantum dots (QDs) for controlled release of drugs. Zwitterionic poly(carboxybetaine methacrylate) (PCBMA) and poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) were introduced to modify ZnO QDs, which can help enhance [...] Read more.
In this paper, we reported a pH responsive nano drug delivery system (NDDS) based on ZnO quantum dots (QDs) for controlled release of drugs. Zwitterionic poly(carboxybetaine methacrylate) (PCBMA) and poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) were introduced to modify ZnO QDs, which can help enhance water stability, increase blood circulation time, and promote endocytosis. After tuning of PCBMA/PDMAEMA ratios, the [email protected](CBMA-co-DMAEMA) nanoplatform shows a sensitive switch from strong protein adsorption resistance (with negatively charged surface) at physiological pH to strong adhesion to tumor cell membranes (with positively charged surface) at the slightly acidic extracellular pH of tumors. Anti-cancer drug, Doxorubicin (DOX), molecules were demonstrated to be successfully loaded to [email protected](CBMA-co-DMAEMA) with a relatively large drug loading content (24.6%). In addition, [email protected](CBMA-co-DMAEMA) loaded with DOX can achieve lysosomal acid degradation and release of DOX after endocytosis by tumor cells, resulting in synergistic treatment of cancer, which is attributed to a combination of the anticancer effect of Zn2+ and DOX. Full article
(This article belongs to the Special Issue Functionally Responsive Polymeric Materials II)
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Open AccessArticle Hybrid Materials Based on l,d-Poly(lactic acid) and Single-Walled Carbon Nanotubes as Flexible Substrate for Organic Devices
Polymers 2018, 10(11), 1271; https://doi.org/10.3390/polym10111271
Received: 9 October 2018 / Revised: 8 November 2018 / Accepted: 8 November 2018 / Published: 15 November 2018
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Abstract
We report on the application of l,d-poly(lactic acid) (l,d-PLA) with dispersed Single-Walled Carbon Nanotubes (SWCN) as a flexible translucent electrode for organic devices. We used commercially available nanotubes in various weight ratios from 0 to 8% dispersed in chloroform polymeric [...] Read more.
We report on the application of l,d-poly(lactic acid) (l,d-PLA) with dispersed Single-Walled Carbon Nanotubes (SWCN) as a flexible translucent electrode for organic devices. We used commercially available nanotubes in various weight ratios from 0 to 8% dispersed in chloroform polymeric solution by ultrasonication and were drop cast. The created hybrid materials were investigated by differential scanning calorimetry to determine the influence of SWCN content on the thermal behavior, while polarizing optical microscope was used to find the effect of mechanical deformations on the textures. Drop-cast films were studied by optical transmittance, conductivity, dielectric properties and by thermal imaging under applied potential. Thermal imaging provided evidence of visible voltage-activated conduction. Simple mechanical deformation such as bending with stretching at edge to ca. 90 and elongation test were performed. Moreover, interactions between l,d-poly(lactic acid) and SWCN were investigated by FT-IR and NMR spectroscopy. Finally, we can conclude that the thermographic examination of created films permits fast, simple and inexpensive localization of defects on the surface of l,d-PLA:SWCN film, together with the electrical properties of the films. Full article
(This article belongs to the Special Issue Polymer-CNT Nanocomposites)
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Open AccessArticle Thermal Properties of TiO2NP/CNT/LDPE Hybrid Nanocomposite Films
Polymers 2018, 10(11), 1270; https://doi.org/10.3390/polym10111270
Received: 14 October 2018 / Revised: 12 November 2018 / Accepted: 12 November 2018 / Published: 15 November 2018
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Abstract
This work aims to investigate the effect of hybrid filler concentration on the thermal stability of low-density polyethylene (LDPE) matrices. LDPE-based composite films were synthesized by melt mixing, followed by compression molding, to study the influence of titanium oxide nanoparticles (TONPs) and/or multi-walled [...] Read more.
This work aims to investigate the effect of hybrid filler concentration on the thermal stability of low-density polyethylene (LDPE) matrices. LDPE-based composite films were synthesized by melt mixing, followed by compression molding, to study the influence of titanium oxide nanoparticles (TONPs) and/or multi-walled carbon nanotubes (CNTs) on the thermal properties of LDPE matrices. Fourier transform infrared (FTIR) spectroscopy confirmed the slight increase in the band intensities after TONP addition and a remarkable surge after the incorporation of CNTs. The value of crystallization temperature (Tc) was not modified after incorporating TONPs, while an enhancement was observed after adding the hybrid fillers. The melting temperature (Tm) was not changed after introducing the CNTs and CNT/TONP hybrid fillers. The percentage crystallinity (Xc %) was increased by 4% and 6%, after incorporating 1 wt % and 3 wt % CNTs, respectively. The TONP incorporation did not modify the Xc %. Moreover, thermal gravimetric analysis (TGA) thermograms confirmed the increased thermal stability after introducing CNTs and hybrid fillers compared to TONP incorporation. Full article
(This article belongs to the Special Issue Thermal Properties and Applications of Polymers)
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Open AccessArticle Therapeutic Effect and Metabolic Mechanism of A Selenium-Polysaccharide from Ziyang Green Tea on Chronic Fatigue Syndrome
Polymers 2018, 10(11), 1269; https://doi.org/10.3390/polym10111269
Received: 8 October 2018 / Revised: 12 November 2018 / Accepted: 12 November 2018 / Published: 15 November 2018
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Abstract
Ziyang green tea was considered a medicine food homology plant to improve chronic fatigue Ssyndrome (CFS) in China. The aim of this research was to study the therapeutic effect of selenium-polysaccharides (Se-TP) from Ziyang green tea on CFS and explore its metabolic mechanism. [...] Read more.
Ziyang green tea was considered a medicine food homology plant to improve chronic fatigue Ssyndrome (CFS) in China. The aim of this research was to study the therapeutic effect of selenium-polysaccharides (Se-TP) from Ziyang green tea on CFS and explore its metabolic mechanism. A CFS-rats model was established in the present research and Se-TP was administrated to evaluate the therapeutic effect on CFS. Some serum metabolites including blood urea nitrogen (BUN), blood lactate acid (BLA), corticosterone (CORT), and aldosterone (ALD) were checked. Urine metabolites were analyzed via gas chromatography-mass spectrometry (GC-MS). Multivariate statistical analysis was also used to check the data. The results selected biomarkers that were entered into the MetPA database to analyze their corresponding metabolic pathways. The results demonstrated that Se-TP markedly improved the level of BUN and CORT in CFS rats. A total of eight differential metabolites were detected in GC-MS analysis, which were benzoic acid, itaconic acid, glutaric acid, 4-acetamidobutyric acid, creatine, 2-hydroxy-3-isopropylbutanedioic acid, l-dopa, and 21-hydroxypregnenolone. These differential metabolites were entered into the MetPA database to search for the corresponding metabolic pathways and three related metabolic pathways were screened out. The first pathway was steroid hormone biosynthesis. The second was tyrosine metabolism, and the third was arginine-proline metabolism. The 21-hydroxypregnenolone level of rats in the CFS group markedly increased after the Se-TP administration. In conclusion, Se-TP treatments on CFS rats improved their condition. Its metabolic mechanism was closely related to that which regulates the steroid hormone biosynthesis. Full article
(This article belongs to the Special Issue Polysaccharides)
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Open AccessArticle Synthesis of Phosphated K-Carrageenan and Its Application for Flame-Retardant Waterborne Epoxy
Polymers 2018, 10(11), 1268; https://doi.org/10.3390/polym10111268
Received: 18 October 2018 / Revised: 10 November 2018 / Accepted: 12 November 2018 / Published: 15 November 2018
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Abstract
In this paper, phosphated K-carrageenan (P-KC) was obtained by reacting POCl3 with the renewable source K-carrageenan (KC). P-KC and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) were added into waterborne epoxy (EP) to improve its flame retardancy. The structure of P-KC was studied comprehensively using Fourier transform [...] Read more.
In this paper, phosphated K-carrageenan (P-KC) was obtained by reacting POCl3 with the renewable source K-carrageenan (KC). P-KC and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) were added into waterborne epoxy (EP) to improve its flame retardancy. The structure of P-KC was studied comprehensively using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), thermo-gravimetric analysis (TGA), showing the successful synthesis of P-KC. The flame retardancy of the EP was evaluated by the cone calorimeter test. The results showed that different mass ratios of DOPO and P-KC affected the flame retardancy of EP. When the mass ratio of DOPO and P-KC was 2:1, total heat release (THR) and total smoke production (TSP) decreased by 48.7% and 37.4%, respectively. The microstructures of residue char were observed by FTIR and scanning electron microscopy (SEM), indicating that the flame-retardant waterborne epoxy (FR-EP) system held a more cohesive and denser char structure. The char inhibited the diffusion of heat and oxygen, which played a key role in the flame retardancy. Full article
(This article belongs to the Special Issue Multi-functional Polymer Composites and Structures)
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Open AccessReview Biosynthesis and Characteristics of Aromatic Polyhydroxyalkanoates
Polymers 2018, 10(11), 1267; https://doi.org/10.3390/polym10111267
Received: 17 October 2018 / Revised: 5 November 2018 / Accepted: 9 November 2018 / Published: 14 November 2018
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Abstract
Polyhydroxyalkanoates (PHAs) are polyesters synthesized by bacteria as a carbon and energy storage material. PHAs are characterized by thermoplasticity, biodegradability, and biocompatibility, and thus have attracted considerable attention for use in medical, agricultural, and marine applications. The properties of PHAs depend on the [...] Read more.
Polyhydroxyalkanoates (PHAs) are polyesters synthesized by bacteria as a carbon and energy storage material. PHAs are characterized by thermoplasticity, biodegradability, and biocompatibility, and thus have attracted considerable attention for use in medical, agricultural, and marine applications. The properties of PHAs depend on the monomer composition and many types of PHA monomers have been reported. This review focuses on biosynthesized PHAs bearing aromatic groups as side chains. Aromatic PHAs show characteristics different from those of aliphatic PHAs. This review summarizes the types of aromatic PHAs and their characteristics, including their thermal and mechanical properties and degradation behavior. Furthermore, the effect of the introduction of an aromatic monomer on the glass transition temperature (Tg) of PHAs is discussed. The introduction of aromatic monomers into PHA chains is a promising method for improving the properties of PHAs, as the characteristics of aromatic PHAs differ from those of aliphatic PHAs. Full article
(This article belongs to the Special Issue Aromatic Polymers)
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Open AccessArticle Enzymatic Degradation of Star Poly(ε-Caprolactone) with Different Central Units
Polymers 2018, 10(11), 1266; https://doi.org/10.3390/polym10111266
Received: 19 October 2018 / Revised: 9 November 2018 / Accepted: 11 November 2018 / Published: 14 November 2018
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Abstract
Four-arm star poly(ε-caprolactone) with a central poly(ethylene glycol) PEG unit bridged with 2,2-bis(methyl) propionic acid, (PCL)2-b-PEG-b-(PCL)2, and six-arm star PCL homopolymer with a central dipentaerythritol units were hydrolysed using a lipase from Pseudomonas [...] Read more.
Four-arm star poly(ε-caprolactone) with a central poly(ethylene glycol) PEG unit bridged with 2,2-bis(methyl) propionic acid, (PCL)2-b-PEG-b-(PCL)2, and six-arm star PCL homopolymer with a central dipentaerythritol units were hydrolysed using a lipase from Pseudomonas cepacia and the Thermobifida cellulosilytica cutinase Thc_Cut1. For comparative analysis, Y-shaped copolymers containing methylated PEG bridged with bisMPA, MePEG-(PCL)2, and linear triblock copolymers PCL-b-PEG-b-PCL were also subjected to enzymatic hydrolysis. The hydrophilic nature of the polymers was determined using contact angle analysis, showing that a higher PEG content exhibited a lower contact angle and higher surface wettability. Enzymatic hydrolysis was monitored by % mass loss, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). A higher rate of mass loss was found for lipase catalysed hydrolysis of those polymers with the highest PEG content, leading to significant surface erosion and increase in crystallinity within the first two days. Liquid chromatography (LC) and size exclusion chromatography (SEC) of samples incubated with the cutinase showed a significant decrease in molecular weight, increase in dispersity, and release of ε-CL monomer units after 6 h of incubation. Full article
(This article belongs to the Special Issue Biocatalytic Functionalization and Degradation of Synthetic Polymers)
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Open AccessArticle Synergistic Effects of Bitumen Plasticization and Microwave Treatment on Short-Term Devulcanization of Ground Tire Rubber
Polymers 2018, 10(11), 1265; https://doi.org/10.3390/polym10111265
Received: 28 September 2018 / Revised: 9 November 2018 / Accepted: 11 November 2018 / Published: 13 November 2018
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Abstract
Ground tire rubber (GTR) was mechano-chemically modified with road bitumen 160/220 and subsequently treated using a microwave radiation. The combined impact of bitumen 160/220 content and microwave treatment on short-term devulcanization of GTR was studied by thermal camera, wavelength dispersive X-ray fluorescence spectrometry [...] Read more.
Ground tire rubber (GTR) was mechano-chemically modified with road bitumen 160/220 and subsequently treated using a microwave radiation. The combined impact of bitumen 160/220 content and microwave treatment on short-term devulcanization of GTR was studied by thermal camera, wavelength dispersive X-ray fluorescence spectrometry (WD-XRF), static headspace, and gas chromatography-mass spectrometry (SHS-GC-MS), thermogravimetric analysis combined with Fourier transform infrared spectroscopy (TGA-FTIR), oscillating disc rheometer and static mechanical properties measurements. The obtained results showed that bitumen plasticizer prevents oxidation of GTR during microwave treatment and simultaneously improves processing and thermal stability of obtained reclaimed rubber. Full article
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Open AccessArticle Preparation and Properties of SBS-g-GOs-Modified Asphalt Based on a Thiol-ene Click Reaction in a Bituminous Environment
Polymers 2018, 10(11), 1264; https://doi.org/10.3390/polym10111264
Received: 18 September 2018 / Revised: 5 November 2018 / Accepted: 6 November 2018 / Published: 13 November 2018
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Abstract
Styrene-butadiene styrene graphene oxide nanoplatelets (SBS-g-GOs)-modified asphalt was prepared by reacting thiolated GOs (GOs-SH) with SBS in asphalt using a thiol-ene click reaction. The temperature resistance and mechanical properties of asphalts were analyzed by dynamic shear rheology (DSR) and multiple-stress creep-recovery (MSCR) tests, [...] Read more.
Styrene-butadiene styrene graphene oxide nanoplatelets (SBS-g-GOs)-modified asphalt was prepared by reacting thiolated GOs (GOs-SH) with SBS in asphalt using a thiol-ene click reaction. The temperature resistance and mechanical properties of asphalts were analyzed by dynamic shear rheology (DSR) and multiple-stress creep-recovery (MSCR) tests, which revealed that an optimum amount of GOs-SH (0.02%) can effectively improve the low temperature and anti-rutting performance of SBS asphalt. Segregation experiments showed that SBS-g-GOs possessed good stability and dispersion in base asphalt. Fluorescence microscopy results revealed that the addition of GOs-SH promoted the formation of SBS network structure. Textural and morphological characterization of GOs-SH and SBS were achieved by Fourier transform infra-red (FT-IR) spectroscopy, energy-dispersive X-ray spectroscopy (EDX), atomic-force microscopy (AFM), X-ray diffraction (XRD), and scanning electron microscopy (SEM), while surface chemical composition was tested by X-ray photoelectron spectroscopy (XPS). Based on textural characterization data, a suitable reaction mechanism was proposed that involved the preferential reaction between GOs-SH and 1,2 C=C of SBS. The currently designed GOs-SH incorporated asphalt via thiol-ene click reaction provides new ideas for the preparation of modified asphalt with enhanced mechanical properties for target-oriented applications. Full article
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Open AccessArticle Study of Physical and Degradation Properties of 3D-Printed Biodegradable, Photocurable Copolymers, PGSA-co-PEGDA and PGSA-co-PCLDA
Polymers 2018, 10(11), 1263; https://doi.org/10.3390/polym10111263
Received: 15 October 2018 / Revised: 5 November 2018 / Accepted: 9 November 2018 / Published: 13 November 2018
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Abstract
As acrylated polymers become more widely used in additive manufacturing, their potential applications toward biomedicine also raise the demand for biodegradable, photocurable polymeric materials. Polycaprolactone diacrylate (PCLDA) and poly(ethylene glycol) diacrylate (PEGDA) are two popular choices of materials for stereolithography (SLA) and digital [...] Read more.
As acrylated polymers become more widely used in additive manufacturing, their potential applications toward biomedicine also raise the demand for biodegradable, photocurable polymeric materials. Polycaprolactone diacrylate (PCLDA) and poly(ethylene glycol) diacrylate (PEGDA) are two popular choices of materials for stereolithography (SLA) and digital light processing additive manufacturing (DLP-AM), and have been applied to many biomedical related research. However, both materials are known to degrade at a relatively low rate in vivo, limiting their applications in biomedical engineering. In this work, biodegradable, photocurable copolymers are introduced by copolymerizing PCLDA and/or PEGDA with poly(glycerol sebacate) acrylate (PGSA) to form a network polymer. Two main factors are discussed: the effect of degree of acrylation in PGSA and the weight ratio between the prepolymers toward the mechanical and degradation properties. It is found that by blending prepolymers with various degree of acrylation and at various weight ratios, the viscosity of the prepolymers remains stable, and are even more 3D printable than pure substances. The formation of various copolymers yielded a database with selectable Young’s moduli between 0.67–10.54 MPa, and the overall degradation rate was significantly higher than pure substance. In addition, it is shown that copolymers fabricated by DLP-AM fabrication presents higher mechanical strength than those fabricated via direct UV exposure. With the tunable mechanical and degradation properties, the photocurable, biodegradable copolymers are expected to enable a wider application of additive manufacturing toward tissue engineering. Full article
(This article belongs to the Special Issue Smart Polymers)
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