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Polymers, Volume 11, Issue 9 (September 2019) – 157 articles

Cover Story (view full-size image): Hydrogels are polymer network systems containing a large amount of water in the matrix, and the development of hydrogels with special physical properties is based on the premise of ensuring good biocompatibility and biodegradability and should be more similar to bio-gels in terms of onlooker structure and biological function. This review introduces four such types of high-strength polymeric hydrogels and the mechanisms for improving their mechanical strength. The specific methods for imparting special physical properties to hydrogels and applications in the field of biomedicine such as cell culture, medical surgery, tissue engineering, and bio-inspired sensing materials are discussed. Moreover, the main reasons and contradictions for the limits of the current applications are explained. View this paper.
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16 pages, 4186 KiB  
Article
A Numerical and Experimental Study of Adhesively-Bonded Polyethylene Pipelines
by Antoine Guilpin, Geoffrey Franciere, Lewis Barton, Matthew Blacklock and Martin Birkett
Polymers 2019, 11(9), 1531; https://doi.org/10.3390/polym11091531 - 19 Sep 2019
Cited by 9 | Viewed by 5585
Abstract
Adhesive bonding of polyethylene gas pipelines is receiving increasing attention as a replacement for traditional electrofusion welding due to its potential to produce rapid and low-cost joints with structural integrity and pressure tight sealing. In this paper a mode-dependent cohesive zone model for [...] Read more.
Adhesive bonding of polyethylene gas pipelines is receiving increasing attention as a replacement for traditional electrofusion welding due to its potential to produce rapid and low-cost joints with structural integrity and pressure tight sealing. In this paper a mode-dependent cohesive zone model for the simulation of adhesively bonded medium density polyethylene (MDPE) pipeline joints is directly determined by following three consecutive steps. Firstly, the bulk stress-strain response of the MDPE adherend was obtained via tensile testing to provide a multi-linear numerical approximation to simulate the plastic deformation of the material. Secondly, the mechanical responses of double cantilever beam and end-notched flexure test specimens were utilised for the direct extraction of the energy release rate and cohesive strength of the adhesive in failure mode I and II. Finally, these material properties were used as inputs to develop a finite element model using a cohesive zone model with triangular shape traction separation law. The developed model was successfully validated against experimental tensile lap-shear test results and was able to accurately predict the strength of adhesively-bonded MPDE pipeline joints with a maximum variation of <3%. Full article
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<p>Specimen geometry for (<b>a</b>) the DCB test, and (<b>b</b>) the ENF test (dimensions in mm). Specimen breadth, <span class="html-italic">b</span> = 25 mm.</p>
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<p>Specimen geometry for single lap-shear adhesive joint (dimensions in mm). Specimen breadth, <span class="html-italic">b</span> = 25 mm.</p>
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<p>(<b>a</b>) Geometry and boundary conditions and (<b>b</b>) mesh detail for the single lap-shear adhesive joint (dimensions in mm).</p>
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<p>Triangular TSL with linear softening availble in ABAQUS<sup>®</sup>.</p>
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<p>Stress-strain curves for the MDPE adherend and numerical approximation for the FEM analysis.</p>
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<p>Load-displacement (<span class="html-italic">P–</span><span class="html-italic">δ</span>) responses for five specimens each of (<b>a</b>) DCB and (<b>b</b>) ENF tests.</p>
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<p>Fracture energy curves for (<b>a</b>) DCB and (<b>b</b>) ENF tests.</p>
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<p>Cohesive strength curves for (<b>a</b>) DCB and (<b>b</b>) ENF tests.</p>
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<p>Load displacement responses for tensile lap-shear tests.</p>
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<p>(<b>a</b>) Von Mises stress and (<b>b</b>) damage variable distribution (SDEG) contour plots for the lap-shear joint model.</p>
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<p>Progressive failure process of the adhesive layer in the lap-shear joint, (<b>a</b>) damage initiation at the overlap edges (SDEG-% = 0), (<b>b</b>) propagation towards the joint centre (SDEG-% ≈ 40), (<b>c</b>) joint failure (SDEG-% = 100).</p>
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<p>Load-displacement (<span class="html-italic">P–</span><span class="html-italic">δ</span>) responses of the lap-shear joint for numerical simulation, damage evolution (SDEG-%) and experimental tests.</p>
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16 pages, 6091 KiB  
Article
Mechanistic Insight into the Ring-Opening Polymerization of ε-Caprolactone and L-Lactide Using Ketiminate-Ligated Aluminum Catalysts
by Ya-Fan Lin and Nai-Yuan Jheng
Polymers 2019, 11(9), 1530; https://doi.org/10.3390/polym11091530 - 19 Sep 2019
Cited by 8 | Viewed by 3951
Abstract
The reactivity and the reaction conditions of the ring-opening polymerization of ε-caprolactone (ε-CL) and L-lactide (LA) initiated by aluminum ketiminate complexes have been shown differently. Herein, we account for the observation by studying the mechanisms on the basis of [...] Read more.
The reactivity and the reaction conditions of the ring-opening polymerization of ε-caprolactone (ε-CL) and L-lactide (LA) initiated by aluminum ketiminate complexes have been shown differently. Herein, we account for the observation by studying the mechanisms on the basis of density functional theory (DFT) calculations. The calculations show that the ring-opening polymerization of ε-CL and LA are rate-determined by the benzoxide insertion and the C–O bond cleavage step, respectively. Theoretical computations suggest that the reaction temperature of L–LA polymerization should be higher than that of ε-CL one, in agreement with the experimental data. To provide a reasonable interpretation of the experimental results and to give an insight into the catalyst design, the influence of the electronic, steric, and thermal effects on the polymerization behaviors will be also discussed in this study. Full article
(This article belongs to the Special Issue Catalytic Polymerization)
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<p>A series of aluminum ketiminate complexes bearing different substituents for the ring-opening polymerization of <span class="html-italic">ε</span>-caprolactone and <span class="html-italic">L</span>-lactide.</p>
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<p>Experimental data summary for the ring-opening polymerization of <span class="html-italic">ε</span>-caprolactone and <span class="html-italic">L</span>-lactide initiated by aluminum ketiminate complexes.</p>
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<p>Thirteen possible initial geometries considered in this study.</p>
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<p><span class="html-italic">ε</span>-Caprolactone coordinated aluminum complexes which bear L, L<sup>Cl</sup>, and L<sup>iPr</sup> ligand systems and arrange in a TBP fashion.</p>
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<p>Reaction profile and optimized structures of the L system. (Monomer: <span class="html-italic">ε</span>-caprolactone).</p>
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<p>Reaction profile and optimized structures of the L<sup>Cl</sup> system. (Monomer: <span class="html-italic">ε</span>-caprolactone).</p>
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<p>Reaction profile and optimized structures of the L<span class="html-italic"><sup>i</sup></span><sup>Pr</sup> system. (Monomer: <span class="html-italic">ε</span>-caprolactone).</p>
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<p><span class="html-italic">L</span>-lactide coordinated aluminum complexes which bear L, L<sup>Cl</sup>, and L<sup>iPr</sup> ligand systems and arrange in a TBP fashion.</p>
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<p>Reaction profile and optimized structures of the L system. (Monomer: <span class="html-italic">L</span>-lactide).</p>
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<p>Reaction profile and optimized structures of the L<sup>Cl</sup> system. (Monomer: <span class="html-italic">L</span>-lactide).</p>
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<p>Reaction profile and optimized structures of the L<span class="html-italic"><sup>i</sup></span><sup>Pr</sup> system. (Monomer: <span class="html-italic">L</span>-lactide).</p>
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<p>Four possible routes starting from four different triangular bipyramidal (TBP) monomer-coordinated aluminum isomers and follow the coordination-insertion mechanism.</p>
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13 pages, 1841 KiB  
Article
Improving Mechanical Properties for Extrusion-Based Additive Manufacturing of Poly(Lactic Acid) by Annealing and Blending with Poly(3-Hydroxybutyrate)
by Sisi Wang, Lode Daelemans, Rudinei Fiorio, Maling Gou, Dagmar R. D’hooge, Karen De Clerck and Ludwig Cardon
Polymers 2019, 11(9), 1529; https://doi.org/10.3390/polym11091529 - 19 Sep 2019
Cited by 53 | Viewed by 6566
Abstract
Based on differential scanning calorimetry (DSC), X-ray diffraction (XRD) analysis, polarizing microscope (POM), and scanning electron microscopy (SEM) analysis, strategies to close the gap on applying conventional processing optimizations for the field of 3D printing and to specifically increase the mechanical performance of [...] Read more.
Based on differential scanning calorimetry (DSC), X-ray diffraction (XRD) analysis, polarizing microscope (POM), and scanning electron microscopy (SEM) analysis, strategies to close the gap on applying conventional processing optimizations for the field of 3D printing and to specifically increase the mechanical performance of extrusion-based additive manufacturing of poly(lactic acid) (PLA) filaments by annealing and/or blending with poly(3-hydroxybutyrate) (PHB) were reported. For filament printing at 210 °C, the PLA crystallinity increased significantly upon annealing. Specifically, for 2 h of annealing at 100 °C, the fracture surface became sufficiently coarse such that the PLA notched impact strength increased significantly (15 kJ m−2). The Vicat softening temperature (VST) increased to 160 °C, starting from an annealing time of 0.5 h. Similar increases in VST were obtained by blending with PHB (20 wt.%) at a lower printing temperature of 190 °C due to crystallization control. For the blend, the strain at break increased due to the presence of a second phase, with annealing only relevant for enhancing the modulus. Full article
(This article belongs to the Special Issue 3D and 4D Printing of (Bio)Materials)
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<p>(<b>a</b>) Thermal curves, (<b>b</b>) Selected XRD curves, (<b>c</b>) Selected SEM images of cryo-fracture surface of PLA (poly(lactic acid)) samples before and after annealing (0.5 to 2 h, 80 or 100 °C); insert (<b>a1</b>): POM of neat PLA, (<b>a2</b>): POM of PLA—80 °C 0.5 h annealing; DSC characteristics are listed in <a href="#app1-polymers-11-01529" class="html-app">Table S3 of the SM</a>.</p>
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<p>(<b>a</b>) Modulus, (<b>b</b>) Tensile stress at maximum load, (<b>c</b>) Tensile strain at break (<b>d</b>) Notched impact strength (grey bars) and VST (Vicat softening temperature) (blue bars) of PLA samples with and without annealing at 80 °C or 100 °C.</p>
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<p>(<b>a</b>) Thermal curves, (<b>b</b>) Selected XRD curves, (<b>c</b>) Selected SEM images of PLA/PHB samples before and after annealing (between 0.5 and 2 h; 80 and 100 °C); additional DSC data are presented in <a href="#app1-polymers-11-01529" class="html-app">Table S3</a>.</p>
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<p>(<b>a</b>) Modulus, (<b>b</b>) Tensile stress at maximum load, (<b>c</b>) Tensile strain at break (<b>d</b>) Notched impact strength and VST for PLA/PHB (poly(3-hydroxybutyrate)) blends, shown with the results of neat PLA, black square in (<b>a</b>–<b>c</b>), red points in (<b>d</b>). Additional mechanical data are shown in <a href="#app1-polymers-11-01529" class="html-app">Table S4 of the SM</a>.</p>
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<p>(<b>a</b>) Processing scheme for PLA (poly(lactic acid))/PHB (poly(3-hydroxybutyrate)) filament fabrication prior to printing; (<b>b</b>) printing orientation scheme.</p>
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15 pages, 5892 KiB  
Article
Effect of the Chain Structure of Self-Emulsifying Polyester Sizing Agent on ILSS of Carbon Fiber/Unsaturated Polyester Resin Composites
by Zhenyu Wang, Huijun Guo, Hang Zhou, Xinfeng Ouyang, Di Jiang, Jianhua Li, Qipeng Guo, Jun Tang and Chuncai Yang
Polymers 2019, 11(9), 1528; https://doi.org/10.3390/polym11091528 - 19 Sep 2019
Cited by 13 | Viewed by 3739
Abstract
Herein, we report self-emulsifying anionic unsaturated polyester emulsions with different chain segments as novel sizing agents. The epoxy modified unsaturated polyester emulsions were synthesized via a self-emulsifying technique with no organic solvents. Emulsions were characterized by dynamic light scattering (DLS), Zeta potential, centrifuge, [...] Read more.
Herein, we report self-emulsifying anionic unsaturated polyester emulsions with different chain segments as novel sizing agents. The epoxy modified unsaturated polyester emulsions were synthesized via a self-emulsifying technique with no organic solvents. Emulsions were characterized by dynamic light scattering (DLS), Zeta potential, centrifuge, and cryo-scanning electron microscopy (Cryo-SEM). The results showed that the emulsions obtained were mono-dispersed nanospheres that had adequate colloidal stability. The maximum Zeta potential of the sizing agent is −52.88 mV. In addition, these emulsions were investigated as the sizing agents in order to improve interfacial adhesion between carbon fibers (CFs) and unsaturated polyester resin (UPR). Compared with the CFs sized with the commercial epoxy sizing agent, the interlaminar shear strength (ILSS) of CF/UPR composites from the CFs sized by these emulsion sizing agents with three different chain structures were enhanced by 25%, 29%, and 42%, respectively. The emulsion sizing agent composed of a flexible segment synthesized from adipic acid, neopentyl glycol, and maleic anhydride is most effective and can achieve the highest enhancement of the ILSS of CF/UPR composites. Full article
(This article belongs to the Section Polymer Applications)
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<p>FT-IR spectra for S1, S2 and S3.</p>
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<p><sup>1</sup>H-NMR spectra of S1 (<b>a</b>), S2 (<b>b</b>) and S3 (<b>c</b>).</p>
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<p>Pictures of S1, S2 and S3 before and after spun at 3000 r/min for 25 minutes (<b>a</b>), and storage at room temperature for 3 months (<b>b</b>).</p>
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<p>Images of the particle size and distribution of S1, S2, and S3.</p>
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<p>Zeta potential analysis.</p>
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<p>Cryo-SEM images of S1 (<b>a</b>), S2 (<b>b</b>) and S3 (<b>c</b>).</p>
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<p>TGA analyses of S1, S2 and S3.</p>
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<p>DSC curves of S1, S2 and S3.</p>
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<p>The surface energy of SC1, SC2, SC3 and epoxy sizing sized CFs.</p>
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<p>SEM micrographs of the CF surface: (<b>a</b>) unsized, (<b>b</b>) S1-sized, (<b>c</b>) S2-sized and (<b>d</b>) S-3 sized.</p>
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<p>ILSS of the CF/UPR composites (<b>a</b>), and Load-displacement curves of CF/UPR composite (<b>b</b>).</p>
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<p>Interfacial reaction mechanism diagram of CF sized by polyester sizing agent with UPR.</p>
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<p>SEM images of the composites: (<b>a</b>) S1 sized CF with UPR (<b>b</b>) S2 sized CF with UPR (<b>c</b>) S3 sized CF with UPR (<b>d</b>) commercial epoxy sizing sized CF with UPR.</p>
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<p>Synthetic route of polyester sizing agent S1.</p>
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<p>Sizing process of CF.</p>
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<p>Diagram of CF/UPR composite produce.</p>
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9 pages, 2882 KiB  
Article
Electrochemical Properties and Structure Evolution of Starch-Based Carbon Nanomaterials as Li-Ion Anodes with Regard to Thermal Treatment
by Marcelina Kubicka, Monika Bakierska, Krystian Chudzik, Małgorzata Rutkowska, Joanna Pacek and Marcin Molenda
Polymers 2019, 11(9), 1527; https://doi.org/10.3390/polym11091527 - 19 Sep 2019
Cited by 9 | Viewed by 3154
Abstract
The influence of the pyrolysis temperature on the structural, textural, and electrochemical properties of carbon aerogels obtained from potato, maize, and rice starches was analyzed. The carbonization of organic precursors, followed by gelatinization, exchange of solvent, and drying process, was carried out in [...] Read more.
The influence of the pyrolysis temperature on the structural, textural, and electrochemical properties of carbon aerogels obtained from potato, maize, and rice starches was analyzed. The carbonization of organic precursors, followed by gelatinization, exchange of solvent, and drying process, was carried out in an argon atmosphere at temperatures ranging from 600 °C to 1600 °C. The nanostructured carbons were characterized by X-ray powder diffraction (XRD) as well as N2-adsorption/desorption (N2-BET) methods. The electrochemical behavior of Li-ion cells based on the fabricated carbon anodes was investigated using the galvanostatic charge/discharge tests (GCDT) and electrochemical impedance spectroscopy (EIS). The results show that the thermal treatment stage has a crucial impact on the proper formation of the aerogel material’s porous structures and also on their working parameters as anode materials. The highest relative development of the external surface was obtained for the samples pyrolysed at 700 °C, which exhibited the best electrochemical characteristics (the highest specific capacities as well as the lowest charge transfer resistances). Full article
(This article belongs to the Special Issue Plant Polysaccharides Based Polymers)
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Figure 1
<p>X-ray diffraction patterns of carbon aerogels derived from (<b>a</b>) potato starch (PS), (<b>b</b>) maize starch (MS), and (<b>c</b>) rice starch (RS) carbonized at temperatures ranging from 600–1600 °C as well as (<b>d</b>) the correlation between interplanar spacing <span class="html-italic">d</span><sub>002</sub> and the carbonization temperature of all carbon aerogel (CAG) samples.</p>
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<p>Nitrogen adsorption-desorption isotherms for the samples from (<b>a</b>) CAG_PS, (<b>b</b>) CAG_MS, and (<b>c</b>) CAG_RS series.</p>
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<p>The rate capability of the (<b>a</b>) CAG_PS, (<b>b</b>) CAG_MS, and (<b>c</b>) CAG_RS based anodes at various C rates.</p>
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<p>Charge-discharge voltage profiles for the first and tenth cycles of (<b>a</b>) CAG_PS_700 (<b>b</b>) CAG_MS_700, and (<b>c</b>) CAG_RS_700 vs. (<b>d</b>) CAG_PS_1600, (<b>e</b>) CAG_MS_1600, and (<b>f</b>) CAG_RS_1600 at C/2 current rate.</p>
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<p>Nyquist plots for (<b>a</b>) Li/Li<sup>+</sup>/CAG_PS and (<b>b</b>) Li/Li<sup>+</sup>/CAG_MS cells with (<b>c</b>) the modeled equivalent circuits as well as the correlation between the R<sub>1</sub>, R<sub>SEI</sub>, and R<sub>CT</sub> resistances values of (<b>d</b>) CAG_PS and (<b>e</b>) CAG_RS anode materials in Li-ion cell and their pyrolysis temperature.</p>
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11 pages, 1948 KiB  
Article
Tailor-Made Specific Recognition of Cyromazine Pesticide Integrated in a Potentiometric Strip Cell for Environmental and Food Analysis
by Nashwa S. Abdalla, Abd El-Galil E. Amr, Aliaa S. M. El-Tantawy, Mohamed A. Al-Omar, Ayman H. Kamel and Nagy M. Khalifa
Polymers 2019, 11(9), 1526; https://doi.org/10.3390/polym11091526 - 19 Sep 2019
Cited by 19 | Viewed by 3286
Abstract
Screen-printed ion-selective electrodes were designed and characterized for the assessment of cyromazine (CYR) pesticide. A novel approach is to design tailor-made specific recognition sites in polymeric membranes using molecularly imprinted polymers for cyromazine (CR) determination (sensor I). Another sensor (sensor II) is the [...] Read more.
Screen-printed ion-selective electrodes were designed and characterized for the assessment of cyromazine (CYR) pesticide. A novel approach is to design tailor-made specific recognition sites in polymeric membranes using molecularly imprinted polymers for cyromazine (CR) determination (sensor I). Another sensor (sensor II) is the plasticized PVC membrane incorporating cyromazine/tetraphenyl borate ion association complex. The charge-transfer resistance and water layer reached its minimal by incorporating Polyaniline (PANI) solid-contact ISE. The designed electrodes demonstrated Nernstain response over a linear range 1.0 × 10−2–5.2 × 10−6 and 1.0 × 10−2–5.7 × 10−5 M with a detection limit 2.2 × 10−6 and 8.1 × 10−6 M for sensors I and II, respectively. The obtained slopes were 28.1 ± 2.1 (r2 = 0.9999) and 36.4 ± 1.6 (r2 = 0.9991) mV/decade, respectively. The results showed that the proposed electrodes have a fast and stable response, good reproducibility, and applicability for direct measurement of CYR content in commercial pesticide preparations and soil samples sprayed with CYR pesticide. The results obtained from the proposed method are fairly in accordance with those using the standard official method. Full article
(This article belongs to the Special Issue Polymers for Membrane Application)
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<p>Scheme of the different layers, and final design of the potentiometric strip cell.</p>
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<p>SEM images of (<b>a</b>) MIP and (<b>b</b>) NIP beads.</p>
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<p>FT-IR spectra for: (<b>a</b>) CYR; (<b>b</b>) DCP/MIP, (<b>c</b>) MIP/washed and (<b>d</b>) NIP beads.</p>
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<p>Potentiometric response curves of: (<b>A</b>) MIP/PANI-SCISE; and (<b>B</b>) TPB/CYR/PANI-SCISE in 50 mM acetate solution of pH 3.5.</p>
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<p>Water-layer tests for the CYR-ISE (<b>A</b>) MIP and (<b>B</b>) TPB, with/without PANI solid contact.</p>
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<p>Chronopotentiometry for CYR-ISE (<b>A</b>) MIP and (<b>B</b>) TPB, with/without PANI solid contact.</p>
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11 pages, 4267 KiB  
Article
Production of Novel Polygalacturonase from Bacillus paralicheniformis CBS32 and Application to Depolymerization of Ramie Fiber
by Md. Saifur Rahman, Yoon Seok Choi, Young Kyun Kim, Chulhwan Park and Jin Cheol Yoo
Polymers 2019, 11(9), 1525; https://doi.org/10.3390/polym11091525 - 19 Sep 2019
Cited by 20 | Viewed by 3835
Abstract
Polygalacturonase (EC. 3.2.1.15) is an enzyme that hydrolyzes the alpha-1,4 glycosidic bonds between galacturonic acid. In this study, an alkaline polygalacturonase producer Bacillus paralicheniformis CBS32 was isolated from kimchi (conventional Korean fermented food). The 16S rRNA sequence analysis of the isolated strain revealed [...] Read more.
Polygalacturonase (EC. 3.2.1.15) is an enzyme that hydrolyzes the alpha-1,4 glycosidic bonds between galacturonic acid. In this study, an alkaline polygalacturonase producer Bacillus paralicheniformis CBS32 was isolated from kimchi (conventional Korean fermented food). The 16S rRNA sequence analysis of the isolated strain revealed that it was 99.92% identical to B. paralicheniformis KJ 16LBMN01000156. The polygalacturonase from B. paralicheniformis CBS32 was named PN32, and the purified PN32 showed a 16.8% yield and a 33-fold purity compared to the crude broth. The molecular mass, 110 kDa, was determined by SDS-PAGE, and the active band was confirmed by zymography analysis. The N-terminal amino acid sequence residues of PN32 were determined to be Gly–Val–Lys–Glu–Val–X–Gln–Thr–Phe. In the sequence comparison, PN32 was suggested as a novel polygalacturonase, since the sequence was not matched with the previous reports. In an application study, enzymatic depolymerization of ramie was performed for fiber degumming, and the result showed that the PN32 had a 28% higher depolymerization compared to the commercial pectinase. Overall, based on the results, PN32 has high potential for industrial applications. Full article
(This article belongs to the Special Issue Microbial Production and Application of Biopolymers)
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<p>Neighbor-joining based phylogenetic on nearly complete 16S rRNA gene sequences showing relationships among CBS32 and closely related taxa of the genus <span class="html-italic">Bacillus</span>.</p>
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<p>(<b>a</b>) The elution profile of PN32 from the Sepharose CL 6B permeation column (1.5 × 30 cm); (<b>b</b>) SDS-PAGE and zymography of purified PN32. Lane M: Protein molecular weight marker; lane pure: Purified PN32 after chromatographic separation by the Sepharose CL 6B column.</p>
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<p>Comparison of the N-terminal amino acid sequence of existing polygalacturonase and PN32.</p>
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<p>(<b>a</b>) Optimum pH, (<b>b</b>) optimum temperature, (<b>c</b>) pH stability, and (<b>d</b>) thermal stability of purified PN32. To determine optimum pH, the reaction was carried out at 60 °C using different pH buffers (2–13.6). The pH stability of PN32 was performed at 4 °C for 24 h, and the relative activity was evaluated under standard assay conditions. To determine optimum temperature, the reaction was performed in an optimum pH (12.2) at different temperatures (30–100 °C), whereas the thermal stability was measured in the temperature range of 60–100 °C for 1 h. Each value is represented as the mean (n = 3).</p>
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<p>(<b>a</b>) Gum loss of the ramie fibers after 2 h treatment by polygalacturonase. The untreated (negative control) means that only a buffer was used, and the positive control means that treatment was done by commercial pectinase (from <span class="html-italic">Aspergillus niger</span>, Sigma-Aldrich, St. Louis, MO, USA). Ramie fibers were untreated and PN32-treated (100 U/mg). (<b>b</b>) Scanning electron micrographs of ramie fiber degradation by PN32. From left: Control and PN32-treated (100 U/mg). From top: Images at various magnifications (400× and 800×).</p>
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13 pages, 3555 KiB  
Article
Novel Antibacterial and Toughened Carbon-Fibre/Epoxy Composites by the Incorporation of TiO2 Nanoparticles Modified Electrospun Nanofibre Veils
by Cristina Monteserín, Miren Blanco, Nieves Murillo, Ana Pérez-Márquez, Jon Maudes, Jorge Gayoso, Jose Manuel Laza, Estíbaliz Hernáez, Estíbaliz Aranzabe and Jose Luis Vilas
Polymers 2019, 11(9), 1524; https://doi.org/10.3390/polym11091524 - 19 Sep 2019
Cited by 18 | Viewed by 3312
Abstract
The inclusion of electrospun nanofiber veils was revealed as an effective method for enhancing the mechanical properties of fiber-reinforced epoxy resin composites. These veils will eventually allow the incorporation of nanomaterials not only for mechanical reinforcement but also in multifunctional applications. Therefore, this [...] Read more.
The inclusion of electrospun nanofiber veils was revealed as an effective method for enhancing the mechanical properties of fiber-reinforced epoxy resin composites. These veils will eventually allow the incorporation of nanomaterials not only for mechanical reinforcement but also in multifunctional applications. Therefore, this paper investigates the effect of electrospun nanofibrous veils made of polyamide 6 modified with TiO2 nanoparticles on the mechanical properties of a carbon-fiber/epoxy composite. The nanofibers were included in the carbon-fiber/epoxy composite as a single structure. The effect of positioning these veils in different composite positions was investigated. Compared to the reference, the use of unmodified and TiO2 modified veils increased the flexural stress at failure and the fracture toughness of composites. When TiO2 modified veils were incorporated, new antibacterial properties were achieved due to the photocatalytic properties of the veils, widening the application area of these composites. Full article
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<p>Configurations of the developed composites.</p>
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<p>Storage modulus and tan δ of composites cured at a temperature of 90 °C.</p>
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<p>Scanning Electron Microscopy (SEM) images of (<b>a</b>) composite with PA6 veil and (<b>b</b>) composite with PA6 modified with 25 wt.% TiO<sub>2</sub> veil. The dotted lines show the veil presence on the composites.</p>
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<p>Dynamic differential scanning calorimetry (DSC) thermograms of the PA6 pellets, PA6 veil, and PA6 modified with 25 wt.% TiO<sub>2</sub> veil; (<b>a</b>) first scan and (<b>b</b>) second scan.</p>
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<p>Mode I test results. Load and mechanical energy normalized to specimen width as a function of displacement.</p>
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<p>Mode II test results. Load normalized to specimen width as a function of displacement.</p>
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<p>Antibacterial tests of composites with three veils of PA6, PA6 modified with 25% TiO<sub>2</sub>, and reference.</p>
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<p>SEM images of the fracture surface of the composite specimens with PA6 modified with 25% TiO<sub>2</sub> veils, (<b>a</b>) external part and (<b>b</b>) covered with resin. The dotted lines show the veil presence on the composites.</p>
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14 pages, 3923 KiB  
Article
Structure and Physicochemical Properties of Malate Starches from Corn, Potato, and Wrinkled Pea Starches
by Miaomiao Shi, Yue Jing, Liuzhi Yang, Xianqing Huang, Hongwei Wang, Yizhe Yan and Yanqi Liu
Polymers 2019, 11(9), 1523; https://doi.org/10.3390/polym11091523 - 19 Sep 2019
Cited by 19 | Viewed by 8545
Abstract
In this study, corn, potato, and wrinkled pea starches were esterified with malic acid under high temperatures for different lengths of time. The degree of substitution (DS), granule morphology, crystal structure, gelatinization properties, and the digestibility of the malate starch were investigated. Fourier [...] Read more.
In this study, corn, potato, and wrinkled pea starches were esterified with malic acid under high temperatures for different lengths of time. The degree of substitution (DS), granule morphology, crystal structure, gelatinization properties, and the digestibility of the malate starch were investigated. Fourier transform infrared spectroscopy (FT–IR) suggested that the malate starch showed a new infrared absorption peak near 1747 cm−1, indicating the occurrence of an esterification reaction. With an increasing treatment time, the degree of substitution (DS) of the malate starch displayed an increasing trend. Scanning electron microscopy (SEM) demonstrated a significant change in the surface structure of the starch granules. X-ray diffractometry (XRD) reflected that the crystal structure of the malate starches was destroyed. The thermogravimetric (TG) curves showed that the maximum heat loss rate of the malate starch was ahead of that of native starch, which caused the decreased degree of crystallinity. These properties of malate starch could allow it to be used for the purpose of starch modification to produce resistant starch and to provide new applications for starch. Full article
(This article belongs to the Special Issue Polymer Structure and Property)
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<p>DS (degree of substitution) of malate starch samples: (<b>A</b>) Corn starch, (<b>B</b>) Potato starch, (<b>C</b>) Pea starch. Different letters in the same chart represent significant differences between different samples (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Scanning electron microscopy of native starch and malate starch heat treated for different lengths of time (1000×).</p>
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<p>X-ray diffraction patterns of malate starch samples: (<b>A</b>) Corn starch, (<b>B</b>) Potato starch, (<b>C</b>) Pea starch.</p>
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<p>Fourier Transform Infrared Spectroscopy spectra of malate starch samples: (<b>A</b>) Corn starch, (<b>B</b>) Potato starch, (<b>C</b>) Pea starch.</p>
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<p>Fourier Transform Infrared Spectroscopy spectra of malate starch samples: (<b>A</b>) Corn starch, (<b>B</b>) Potato starch, (<b>C</b>) Pea starch.</p>
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<p>Thermal gravimetric analysis and derivative thermogravimetric analysis (TG/DTG) image of malate starch samples: (<b>A<sub>1</sub></b>) Corn starch TG, (<b>A<sub>2</sub></b>) Corn starch DTG, (<b>B<sub>1</sub></b>) Potato starch TG, (<b>B<sub>2</sub></b>) Potato starch DTG, (<b>C<sub>1</sub></b>) Pea starch TG, (<b>C<sub>2</sub></b>) Pea starch DTG.</p>
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11 pages, 1390 KiB  
Communication
PPG-Terminated Tetra-Carbamates as the Toughening Additive for Bis-A Epoxy Resin
by Ming Zhang, Mingqing Chen and Zhongbin Ni
Polymers 2019, 11(9), 1522; https://doi.org/10.3390/polym11091522 - 19 Sep 2019
Cited by 2 | Viewed by 3032
Abstract
We synthesized PPG-terminated tetra-carbamates as a new toughening additive for epoxy thermosets through facile addition reaction of hexamethylene diisocyanate (HDI) with poly(tetra-methylene glycols) (PTMG) and poly(propylene glycols) (PPG). The effects of prepared tetra-carbamates on the rheological behavior of neat epoxy resin were studied [...] Read more.
We synthesized PPG-terminated tetra-carbamates as a new toughening additive for epoxy thermosets through facile addition reaction of hexamethylene diisocyanate (HDI) with poly(tetra-methylene glycols) (PTMG) and poly(propylene glycols) (PPG). The effects of prepared tetra-carbamates on the rheological behavior of neat epoxy resin were studied along with the various cured properties of their modified epoxy systems. Four carbamate groups (–NHCOO–) endow the prepared additives not only with good intramolecular interactions, but also with optimal intermolecular interactions with epoxy polymers. This results in the suitable miscibility of the additives with the epoxy matrix for the formation of the typical biphasic structure of microparticles dispersed in the epoxy matrix via polymerization-induced microphase separation. The impact strength and critical stress concentration factor (KIC) of cured modified epoxy systems with the additives are significantly higher than those of unmodified epoxy systems, without sacrificing the processability (Tg) and flexural strength. The toughening mechanism is understood as a synergism combination among the phase separation mechanism, the in situ homogeneous toughening mechanism, and the particle cavitation mechanism. Full article
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<p>Synthetic pathway of tetra-carbamates.</p>
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<p>(<b>a</b>) FT-IR spectra of HDI, PTMG2000, PPG400 and HT2P4 at 25 °C; (<b>b</b>) DSC profile of PTMG2000 and HT2P4; (<b>c</b>) FT-IR spectra of crystalized PTMG2000 and melted PTMG2000, respectively.</p>
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<p>(<b>a</b>) Steady shear viscosity profiles of neat DER331, DER331/HT1P4 (10 wt %) and DER331/HT2P4 (10 wt %) as a function of shear rate at 25 °C; (<b>b</b>) Dynamic viscoelastic moduli vs. temperature by oscillatory shear for neat HT2P4, DER331/HT2P4 (10 wt %) blend at sweep cooling rate of 5 °C/min (strain = 3.125%, angular frequency = 1 rad/s, 25 mm parallel plate); (<b>c</b>) Dynamic viscoelastic moduli vs. time by oscillatory shear for neat DER331/TETA blend, DER331/TETA/HT1P4(10 wt %) blend, and DER331/TETA/HT2P4(10 wt %) blend at 60 °C (strain = 3.125%, angular frequency = 1 rad/s, 25 mm parallel plate); (<b>d</b>) Dynamic viscoelastic moduli vs. time by oscillatory shear for DER331/TETA/HT2P4 blends at different mass ratio of HT2P4 at 60 °C (strain = 3.125%, angular frequency = 1 rad/s, 25 mm parallel plate).</p>
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<p>Cured properties of the cured unmodified epoxy, modified epoxy with HT1P4 and HT2P4 at 2, 5 and 10 wt %, respectively (<b>a</b>) <span class="html-italic">T</span><sub>g</sub>; (<b>b</b>) Flexural strength and modulus; (<b>c</b>) Impact strength and <span class="html-italic">K</span><sub>IC</sub>; (<b>d</b>) SEM for modified epoxy with 10 wt % HT1P4; (<b>e</b>) SEM for modified epoxy with 2 wt % HT2P4; (<b>f</b>) SEM for modified epoxy with 5 wt % HT2P4; (<b>g</b>) SEM for modified epoxy with 10 wt % HT2P4.</p>
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25 pages, 5928 KiB  
Article
On the Evaluation of the Suitability of the Materials Used to 3D Print Holographic Acoustic Lenses to Correct Transcranial Focused Ultrasound Aberrations
by Marcelino Ferri, José María Bravo, Javier Redondo, Sergio Jiménez-Gambín, Noé Jiménez, Francisco Camarena and Juan Vicente Sánchez-Pérez
Polymers 2019, 11(9), 1521; https://doi.org/10.3390/polym11091521 - 19 Sep 2019
Cited by 11 | Viewed by 4815
Abstract
The correction of transcranial focused ultrasound aberrations is a relevant topic for enhancing various non-invasive medical treatments. Presently, the most widely accepted method to improve focusing is the emission through multi-element phased arrays; however, a new disruptive technology, based on 3D printed holographic [...] Read more.
The correction of transcranial focused ultrasound aberrations is a relevant topic for enhancing various non-invasive medical treatments. Presently, the most widely accepted method to improve focusing is the emission through multi-element phased arrays; however, a new disruptive technology, based on 3D printed holographic acoustic lenses, has recently been proposed, overcoming the spatial limitations of phased arrays due to the submillimetric precision of the latest generation of 3D printers. This work aims to optimize this recent solution. Particularly, the preferred acoustic properties of the polymers used for printing the lenses are systematically analyzed, paying special attention to the effect of p-wave speed and its relationship to the achievable voxel size of 3D printers. Results from simulations and experiments clearly show that, given a particular voxel size, there are optimal ranges for lens thickness and p-wave speed, fairly independent of the emitted frequency, the transducer aperture, or the transducer-target distance. Full article
(This article belongs to the Special Issue Polymer Materials for Holography)
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<p>Schematic sagittal cross section of the skull, representing the positions of target points (<b>P1</b>, <b>P2</b>, <b>P3</b>) and registration surfaces (<b>1</b>, <b>2</b>, <b>3</b>) considered in numerical simulations.</p>
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<p>(<b>a</b>) Photograph of the flat-lens manufactured by a stereolithographic 3D-printing technique using a photopolymer. (<b>b</b>) Scheme of the setup and equipment used for the experiments in water tank.</p>
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<p>Analytical estimation of the uncertainties in the phase recreated by the 3D lens at the holographic surface associated with the discretization of the domain in voxels per water wavelength, <span class="html-italic">n<sub>λ_water</sub></span>, (dashed), with the acoustic impedance of the lens when the definition of the thickness is approached by linear interpolation (dotted) and with possible differences between simulated and real values of the p-wave speed of the lens (continuous).</p>
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<p>Representation of the Cartesian model of the lenses implemented in the simulations at points P1 (<b>a</b>) and P2 (<b>b</b>), with respective thicknesses of 10, 18, and 40 voxels. Images (<b>c</b>–<b>e</b>) represent the 10-voxel thick polar lenses associated respectively with points P3 (<b>c</b>) P2 (<b>d</b>) and P1 (<b>e</b>).</p>
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<p>Focusing quality indicators calculated by simulation in water with 760 kHz, at points P1, P2, and P3, for concave (fast) and convex (slow) lenses. Indicators are as follows: (<b>a</b>) Longitudinal and (<b>b</b>) transverse deviation, (<b>c</b>) transverse and (<b>d</b>) total gyradius, (<b>e</b>) beam volume, and (<b>f</b>) energetic overlapping.</p>
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<p>Focusing quality indicators calculated by transcranial simulation with 760 kHz at points P1, P2, and P3, for concave (fast) and convex (slow) lenses. Indicators are as follows: (<b>a</b>) Longitudinal and (<b>b</b>) transverse deviation, (<b>c</b>) transverse and (<b>d</b>) total gyradius, (<b>e</b>) beam volume, (<b>f</b>) orientation, and (<b>g</b>) energetic overlapping.</p>
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<p>Focusing quality indicators calculated by simulation in water with 380 kHz, at points P1, and P2, for concave (fast) and convex (slow) lenses. Indicators are the following: (<b>a</b>) Longitudinal deviation, (<b>b</b>) transverse gyradius, (<b>c</b>) beam volume and (<b>d</b>) energetic overlapping.</p>
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<p>Focusing quality indicators calculated by transcranial simulation with 380 kHz at points P1 and P2, for concave (fast) and convex (slow) lenses. Indicators are as follows: (<b>a</b>) Longitudinal and (<b>b</b>) transverse deviation, (<b>c</b>) transverse gyradius, (<b>d</b>) beam volume, and (<b>e</b>) energetic overlapping.</p>
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<p>Results of the experimental validation test. (<b>a</b>) Experimental (red markers) and simulated (black continuous) normalized pressure field distribution measured at the axis of symmetry. Pressure field distribution in the sagittal plane, <span class="html-italic">P</span>(<span class="html-italic">x</span>,<span class="html-italic">z</span>), obtained (<b>b</b>) experimentally and (<b>c</b>) numerically. (<b>d</b>) Experimental (red markers) and simulated (black continuous) normalized pressure field distribution in the transverse direction <span class="html-italic">x</span> measured at the focal spot. Corresponding pressure distributions in the transverse plane, <span class="html-italic">P</span>(<span class="html-italic">x</span>,<span class="html-italic">y</span>), obtained (<b>e</b>) experimentally and (<b>f</b>) numerically.</p>
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<p>Numerically simulated pressure field distributions in the sagittal plane, <span class="html-italic">P</span>(x,z), obtained with two lenses generated from the same particular registered pattern. (<b>a</b>) Convex lens made of fluorinated ethylene propylene and (<b>b</b>) concave lens made of polylactic acid.</p>
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15 pages, 4916 KiB  
Article
Electrochemical Polymerization of PEDOT–Graphene Oxide–Heparin Composite Coating for Anti-Fouling and Anti-Clotting of Cardiovascular Stents
by Ming-Chien Yang, Hui-Ming Tsou, Yu-Sheng Hsiao, Yu-Wei Cheng, Che-Chun Liu, Li-Ying Huang, Xin-Yao Peng, Ting-Yu Liu, Ming-Chi Yung and Chuan-Chih Hsu
Polymers 2019, 11(9), 1520; https://doi.org/10.3390/polym11091520 - 18 Sep 2019
Cited by 27 | Viewed by 4446
Abstract
In this study, a novel hemocompatible coating on stainless steel substrates was prepared by electrochemically copolymerizing 3,4-ethylenedioxythiophene (EDOT) with graphene oxide (GO), polystyrene sulfonate (PSS), or heparin (HEP) on SUS316L stainless steel, producing an anti-fouling (anti-protein adsorption and anti-platelet adhesion) surface to avoid [...] Read more.
In this study, a novel hemocompatible coating on stainless steel substrates was prepared by electrochemically copolymerizing 3,4-ethylenedioxythiophene (EDOT) with graphene oxide (GO), polystyrene sulfonate (PSS), or heparin (HEP) on SUS316L stainless steel, producing an anti-fouling (anti-protein adsorption and anti-platelet adhesion) surface to avoid the restenosis of blood vessels. The negative charges of GO, PSS, and HEP repel negatively charged proteins and platelets to achieve anti-fouling and anti-clotting. The results show that the anti-fouling capability of the poly(3,4-ethylenedioxythiophene) (PEDOT)/PSS coating is similar to that of the PEDOT/HEP coating. The anti-fouling capability of PEDOT/GO is higher than those of PEDOT/HEP and PEDOT/PSS. The reason for this is that GO exhibits negatively charged functional groups (COO). The highest anti-fouling capability was found with the PEDOT/GO/HEP coating, indicating that electrochemical copolymerization of PEDOT with GO and HEP enhances the anti-fouling capability. Furthermore, the biocompatibility of the PEDOT coatings was tested with 3T3 cells for 1–5 days. The results show that all PEDOT composite coatings exhibited biocompatibility. The blood clotting time (APTT) of PEDOT/GO/HEP was prolonged to 225 s, much longer than the 40 s of pristine SUS316L stainless steel (the control), thus greatly improving the anti-blood-clotting capability of cardiovascular stents. Full article
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<p>SEM images of (<b>a</b>) SUS316L stainless steel, (<b>b</b>) poly(3,4-ethylenedioxythiophene) (PEDOT)/heparin (HEP), (<b>c</b>) PEDOT/polystyrene sulfonate (PSS), (<b>d</b>) PEDOT/graphene oxide (GO), and (<b>e</b>) PEDOT/GO/HEP.</p>
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<p>SEM images of the cross sections of (<b>a</b>) PEDOT/HEP, (<b>b</b>) PEDOT/PSS, (<b>c</b>) PEDOT/GO, and (<b>d</b>) PEDOT/GO/HEP.</p>
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<p>AFM images of (<b>a</b>) SUS316L, (<b>b</b>) PEDOT/HE, (<b>c</b>) PEDOT/PS, (<b>d</b>) PEDOT/GO, and (<b>e</b>) PEDOT/GO/HEP.</p>
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<p>XPS full spectra of PEDOT/PSS, PEDOT/HEP, PEDT/GO, and PEDOT/GO/HEP.</p>
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<p>C1s energy spectra of PEDOT/GO and PEDOT/PSS.</p>
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<p>C1s energy spectra of PEDOT/HEP and PEDOT/GO/HEP.</p>
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<p>N1s energy spectra of PEDOT/GO, PEDOT/HEP, and PEDOT/GO/HEP.</p>
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<p>Water contact angles of SUS316L, PEDOT/GO, PEDOT/PSS, PEDOT/HEP, and PEDOT/GO/HEP.</p>
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<p>Photographs of the grid area of PEDOT/GO/HEP-coated SUS316L stainless steel before (<b>a</b>) and after (<b>b</b>) the cross-cut tape testing method.</p>
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<p>Protein adsorption on SUS316L, PEDOT/PSS, PEDOT/HEP, PEDOT/GO, and PEDOT/GO/HEP.</p>
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<p>Platelet adhesion on SUS316L, PEDOT/PSS, PEDOT/HEP, PEDOT/GO, and PEDOT/GO/HEP.</p>
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<p>SEM images of human platelets adherent to (<b>a</b>) SUS316L, (<b>b</b>) PEDOT/HEP, (<b>c</b>) PEDOT/PSS, (<b>d</b>) PEDOT/GO, and (<b>e</b>) PEDOT/GO/HEP substrates.</p>
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<p>Coagulation times for the composite films.</p>
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<p>Biocompatibility of the composite films.</p>
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20 pages, 6731 KiB  
Article
Self-Healing Performance of Multifunctional Polymeric Smart Coatings
by Sehrish Habib, Adnan Khan, Muddasir Nawaz, Mostafa Hussein Ramadan Sliem, Rana Abdul Shakoor, Ramazan Kahraman, Aboubakr M. Abdullah and Atef Zekri
Polymers 2019, 11(9), 1519; https://doi.org/10.3390/polym11091519 - 18 Sep 2019
Cited by 56 | Viewed by 6805
Abstract
Multifunctional nanocomposite coatings were synthesized by reinforcing a polymeric matrix with halloysite nanotubes (HNTs) loaded with corrosion inhibitor (NaNO3) and urea formaldehyde microcapsules (UFMCs) encapsulated with a self-healing agent (linseed oil (LO)). The developed polymeric nanocomposite coatings were applied on the [...] Read more.
Multifunctional nanocomposite coatings were synthesized by reinforcing a polymeric matrix with halloysite nanotubes (HNTs) loaded with corrosion inhibitor (NaNO3) and urea formaldehyde microcapsules (UFMCs) encapsulated with a self-healing agent (linseed oil (LO)). The developed polymeric nanocomposite coatings were applied on the polished mild steel substrate using the doctor’s blade technique. The structural (FTIR, XPS) and thermogravimetric (TGA) analyses reveal the loading of HNTs with NaNO3 and encapsulation of UFMCs with linseed oil. It was observed that self-release of the inhibitor from HNTs in response to pH change was a time dependent process. Nanocomposite coatings demonstrate decent self-healing effects in response to the external controlled mechanical damage. Electrochemical impedance spectroscopic analysis (EIS) indicates promising anticorrosive performance of novel nanocomposite coatings. Observed corrosion resistance of the developed smart coatings may be attributed to the efficient release of inhibitor and self-healing agent in response to the external stimuli. Polymeric nanocomposite coatings modified with multifunctional species may offer suitable corrosion protection of steel in the oil and gas industry. Full article
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<p>Schematic representation of multifunctional nanocomposite coating concept.</p>
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<p>Schematic representation of complete experimental procedure adopted.</p>
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<p>Field emission scanning electron microscope (FE–SEM) analysis of: (<b>a</b>) halloysite nanotubes (HNTs), (<b>b</b>) HNTs loaded with NaNO<sub>3</sub>, (<b>c</b>) urea formaldehyde microcapsules/linseed oil (UFMC/LO), and (<b>e</b>,<b>g</b>) nanocomposite coatings; and EDX analysis of: (<b>d</b>) HNTs, (<b>f</b>) HNTs loaded with NaNO<sub>3</sub>, and (<b>h</b>) nanocomposite coatings.</p>
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<p>XRD analysis: (<b>a</b>) HNTs, (<b>b</b>) HNTs loaded with NaNO<sub>3</sub>, and (<b>c</b>) Nanocomposite coatings. Inset shows the XRD of UFMCs.</p>
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<p>Fourier transform infrared (FTIR) spectra of (<b>a</b>) HNTs, (<b>b</b>) NaNO<sub>3</sub>, (<b>c</b>) HNTs loaded with NaNO<sub>3</sub>, (<b>d</b>) nanocomposite coatings, and (<b>e</b>) UFMCs.</p>
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<p>XPS spectra of synthesized containers; (<b>a</b>,<b>b</b>) C1s and O1s spectrum of UFMCs, (<b>c</b>,<b>d</b>) O1s and Si2p spectrum of HNTs, and (<b>e</b>,<b>f</b>) survey spectrum of UFMCs and HNTs.</p>
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<p>Particle size analysis of the synthesized UFMCs.</p>
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<p>Thermogravimetric (TGA) curves: (<b>a</b>) pristine HNTs, (<b>b</b>) HNTs loaded with NaNO<sub>3</sub>, (<b>c</b>) encapsulated UFMCs, and (<b>d</b>) nanocomposite coatings.</p>
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<p>UV-Vis spectra of HNTs loaded with inhibitor immersed in 0.1M NaCl solution at various pH levels for different immersion time intervals, (<b>a</b>) 24 h, (<b>b</b>) 48 h, and (<b>c</b>) 72 h.</p>
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<p>SEM images of the scratched samples after different time intervals.</p>
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<p>Electrochemical impedance curves for scratched pure coating immersed in 3.5 wt% NaCl for different exposure times: (<b>a</b>) Nyquist plot, (<b>b</b>) bode plot, (<b>c</b>) phase angle plot, and (<b>d</b>) the applicable equivalent circuit for the data fitting.</p>
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<p>Electrochemical impedance curves for scratched plain coating immersed in 3.5 wt% NaCl for different exposure times where (<b>a</b>) Nyquist plot, (<b>b</b>) bode plot, (<b>c</b>) phase angle plot, and (<b>d</b>) the applicable equivalent circuit for the data fitting.</p>
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<p>Electrochemical impedance curves for scratched smart coating immersed in 3.5 wt% NaCl for different exposure times: (<b>a</b>) Nyquist plot, (<b>b</b>) bode plot, (<b>c</b>) phase angle plot, and (<b>d</b>) the applicable equivalent circuit for the data fitting.</p>
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21 pages, 5824 KiB  
Article
Fabrication and Evaluation of a Novel Non-Invasive Stretchable and Wearable Respiratory Rate Sensor Based on Silver Nanoparticles Using Inkjet Printing Technology
by Ala’aldeen Al-Halhouli, Loiy Al-Ghussain, Saleem El Bouri, Haipeng Liu and Dingchang Zheng
Polymers 2019, 11(9), 1518; https://doi.org/10.3390/polym11091518 - 18 Sep 2019
Cited by 41 | Viewed by 5541
Abstract
The respiration rate (RR) is a key vital sign that links to adverse clinical outcomes and has various important uses. However, RR signals have been neglected in many clinical practices for several reasons and it is still difficult to develop low-cost RR sensors [...] Read more.
The respiration rate (RR) is a key vital sign that links to adverse clinical outcomes and has various important uses. However, RR signals have been neglected in many clinical practices for several reasons and it is still difficult to develop low-cost RR sensors for accurate, automated, and continuous measurement. This study aims to fabricate, develop and evaluate a novel stretchable and wearable RR sensor that is low-cost and easy to use. The sensor is fabricated using the soft lithography technique of polydimethylsiloxane substrates (PDMS) for the stretchable sensor body and inkjet printing technology for creating the conductive circuit by depositing the silver nanoparticles on top of the PDMS substrates. The inkjet-printed (IJP) PDMS-based sensor was developed to detect the inductance fluctuations caused by respiratory volumetric changes. The output signal was processed in a Wheatstone bridge circuit to derive the RR. Six different patterns for a IJP PDMS-based sensor were carefully designed and tested. Their sustainability (maximum strain during measurement) and durability (the ability to go bear axial cyclic strains) were investigated and compared on an automated mechanical stretcher. Their repeatability (output of the sensor in repeated tests under identical condition) and reproducibility (output of different sensors with the same design under identical condition) were investigated using a respiratory simulator. The selected optimal design pattern from the simulator evaluation was used in the fabrication of the IJP PDMS-based sensor where the accuracy was inspected by attaching it to 37 healthy human subjects (aged between 19 and 34 years, seven females) and compared with the reference values from e-Health nasal sensor. Only one design survived the inspection procedures where design #6 (array consists of two horseshoe lines) indicated the best sustainability and durability, and went through the repeatability and reproducibility tests. Based on the best pattern, the developed sensor accurately measured the simulated RR with an error rate of 0.46 ± 0.66 beats per minute (BPM, mean ± SD). On human subjects, the IJP PDMS-based sensor and the reference e-Health sensor showed the same RR value, without any observable differences. The performance of the sensor was accurate with no apparent error compared with the reference sensor. Considering its low cost, good mechanical property, simplicity, and accuracy, the IJP PDMS-based sensor is a promising technique for continuous and wearable RR monitoring, especially under low-resource conditions. Full article
(This article belongs to the Special Issue Polymer-Based Flexible Printed Electronics and Sensors)
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<p>Development procedure for the fabrication and evaluation of the respiration rate (RR) sensor.</p>
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<p>Scanning electron microscope (SEM) microscopic image of the dispersed silver nanoparticles on the Polydimethylsiloxane (PDMS)substrate.</p>
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<p>Diagram of the six horseshoe patterns.</p>
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<p>The fabrication process of the respiratory rate sensors: (<b>a</b>) pouring the PDMS mixture on the fabric; (<b>b</b>) cured PDMS sample with embedded fabrics; (<b>c</b>) conductive pattern deposition using the inkjet printer; (<b>d</b>) pouring small drops of liquid metal at the pattern’s pads; (<b>e</b>) coating the circuit with 10 layers of PDMS; (<b>f</b>) sewing the conductive threads over the liquid metal; (<b>g</b>) developing PDMS incubators for the liquid metal and (<b>h</b>) sewing the sensor to the fabric belt. It should be noted that the presented pattern in the fabrication procedure here is just for demonstration.</p>
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<p>Schematic diagram of a Wheatstone circuit.</p>
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<p>The flow chart of the output signal from the developed sensor.</p>
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<p>Automated stretching system: (<b>a</b>) whole setup and (<b>b</b>) sensor mounted using the magnetic clamps.</p>
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<p>The relation between the number of steps and strain applied to the PDMS.</p>
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<p>Respiration simulator prototype.</p>
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<p>The inkjet-printed (IJP) PDMS-based sensor attached to a human at the upper part of the abdomen.</p>
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<p>The output voltage over time from the four selected patterns under 3% axial strain at 800 steps/s speed: (<b>a</b>) design #1, (<b>b</b>) design #3, (<b>c</b>) design #5, and (<b>d</b>) design #6.</p>
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<p>The output voltage of the sensor over time when placed on the simulator in two consecutive days under a volume strain of 17.3% and 154.2 BPM simulated by the respiratory simulator.</p>
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<p>The output voltage of the two sensors with identical design over time when placed on the simulator under a volume strain of 17.3% and 58.2 BPM simulated by the respiratory simulator.</p>
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<p>The respiratory signals derived by the developed IJP PDMS-based sensor and reference e-Health sensor. Signals were derived from subject 6 in <a href="#polymers-11-01518-t0A1" class="html-table">Table A1</a> in the sitting position.</p>
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20 pages, 25580 KiB  
Article
Electrospinning of Hyaluronan Using Polymer Coelectrospinning and Intermediate Solvent
by Lenka Vítková, Lenka Musilová, Eva Achbergerová, Antonín Minařík, Petr Smolka, Erik Wrzecionko and Aleš Mráček
Polymers 2019, 11(9), 1517; https://doi.org/10.3390/polym11091517 - 18 Sep 2019
Cited by 15 | Viewed by 3789
Abstract
In the current study, we present methods of sodium hyaluronate, also denoted as hyaluronan (HA), nanofiber fabrication using a direct-current (DC) electric field. HA was spun in combination with poly(vinyl alcohol) (PVA) and polyethylene oxide (PEO) and as a pure polymer. Nonaggressive solvents [...] Read more.
In the current study, we present methods of sodium hyaluronate, also denoted as hyaluronan (HA), nanofiber fabrication using a direct-current (DC) electric field. HA was spun in combination with poly(vinyl alcohol) (PVA) and polyethylene oxide (PEO) and as a pure polymer. Nonaggressive solvents were used due to the possible use of the fibers in life sciences. The influences of polymer concentration, average molecular weight (Mw), viscosity, and solution surface tension were analyzed. HA and PVA were fluorescent-labeled in order to examine the electrospun structures using fluorescence confocal microscopy. In this study, two intermediate solvent mixtures that facilitate HA electrospinning were found. In the case of polymer co-electrospinning, the effect of the surfactant content on the HA/PVA electrospinning process, and the effect of HA Mw on HA/PEO nanofiber morphology, were examined, respectively. Full article
(This article belongs to the Special Issue Polymer Biointerfaces)
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<p>Electrospinning device: (<b>a</b>) device scheme and (<b>b</b>) device used in experiments.</p>
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<p>Viscosity of HA/PVA blend solutions with BEC as a function of shear rate.</p>
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<p>Scanning Electron Microscopy (SEM) micrographs of electrospun structures obtained from HA/PVA blend solutions with BEC. BEC content (<b>a</b>) 0.033 wt.%. and (<b>b</b>) 0.065 wt.%.</p>
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<p>Fluorescence confocal microscope micrographs of electrospun structures obtained from Nile Blue A labeled HA 600 kDa and FITC labeled PVA 89–98 kDa aqueous solution with BEC content 0.065 wt.%. (<b>a</b>) Nile Blue A labeled HA visible. Emission spectrum 600–640 nm. (<b>b</b>) FITC labeled PVA visible. Emission spectrum 450–520 nm. (<b>c</b>) Both fluorescent labeled polymers visible—combined emission spectra.</p>
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<p>Fluorescence confocal microscope micrographs of electrospun structures obtained from Nile Blue A labeled HA 600 kDa and FITC labeled PVA 89–98 kDa aqueous solution with BEC content 0.065 wt.%. (<b>a</b>) Nile Blue A labeled HA visible. Emission spectrum 600–640 nm. (<b>b</b>) FITC labeled PVA visible. Emission spectrum 450–520 nm. (<b>c</b>) Both fluorescent labeled polymers visible—combined emission spectra.</p>
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<p>Viscosity of HA/PEO blend solutions as a function of shear rate.</p>
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<p>SEM micrographs of electrospun structures obtained from HA/PEO blend solutions. (<b>a</b>) HA 243 kDa, PEO 300 kDa. (<b>b</b>) HA 370 kDa, PEO 300 kDa. (<b>c</b>) HA 600 kDa, PEO 300 kDa. (<b>d</b>) HA 243 kDa, PEO 600 kDa. (<b>e</b>) HA 370 kDa, PEO 600 kDa. (<b>f</b>) HA 600 kDa, PEO 600 kDa.</p>
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<p>SEM micrographs of electrospun structures obtained from HA/PEO blend solutions. (<b>a</b>) HA 243 kDa, PEO 300 kDa. (<b>b</b>) HA 370 kDa, PEO 300 kDa. (<b>c</b>) HA 600 kDa, PEO 300 kDa. (<b>d</b>) HA 243 kDa, PEO 600 kDa. (<b>e</b>) HA 370 kDa, PEO 600 kDa. (<b>f</b>) HA 600 kDa, PEO 600 kDa.</p>
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<p>Fluorescence confocal microscope micrographs of electrospun structures obtained from the Nile Blue A Labeled HA 600 kDa and PEO 600 kDa aqueous solution. Emission spectrum: 600–640 nm.</p>
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<p>Solvent–mixture representation in Teas graph. 1: water; 2: IPA; 3: MeOH; 4: EtOH; 5: H2O:IPA 10:7; 6: H2O:EtOH:MeOH 5:5:1.</p>
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<p>Viscosity of HA solutions in intermediate solvents as a function of shear rate. (<b>a</b>) H<sub>2</sub>O:IPA in 10:7 weight ratio solvent mixture. (<b>b</b>) H<sub>2</sub>O:EtOH:MeOH in 5:5:1 weight ratio solvent mixture.</p>
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<p>SEM micrographs of electrospun structures obtained from H<sub>2</sub>O:IPA in 10:7 weight ratio solutions. (<b>a</b>) 3.2 wt.% HA <math display="inline"><semantics> <msub> <mi>M</mi> <mi mathvariant="normal">w</mi> </msub> </semantics></math> 600 kDa; (<b>b</b>) 2.3 wt.% HA <math display="inline"><semantics> <msub> <mi>M</mi> <mi mathvariant="normal">w</mi> </msub> </semantics></math> 600 kDa; (<b>c</b>) 1.3 wt.% HA <math display="inline"><semantics> <msub> <mi>M</mi> <mi mathvariant="normal">w</mi> </msub> </semantics></math> 600 kDa; (<b>d</b>) 2.9 wt.% HA <math display="inline"><semantics> <msub> <mi>M</mi> <mi mathvariant="normal">w</mi> </msub> </semantics></math> 1180 kDa; (<b>e</b>) 1.2 wt.% HA <math display="inline"><semantics> <msub> <mi>M</mi> <mi mathvariant="normal">w</mi> </msub> </semantics></math> 1180 kDa.</p>
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<p>SEM micrographs of electrospun structures obtained from H<sub>2</sub>O:EtOH:MeOH in 5:5:1 weight ratio solutions. (<b>a</b>) 2.8 wt.% HA <math display="inline"><semantics> <msub> <mi>M</mi> <mi mathvariant="normal">w</mi> </msub> </semantics></math> 600 kDa; (<b>b</b>) 2.4 wt.% HA <math display="inline"><semantics> <msub> <mi>M</mi> <mi mathvariant="normal">w</mi> </msub> </semantics></math> 600 kDa; (<b>c</b>) 2.2 wt.% HA <math display="inline"><semantics> <msub> <mi>M</mi> <mi mathvariant="normal">w</mi> </msub> </semantics></math> 1180 kDa; (<b>d</b>) 1.5 wt.% HA <math display="inline"><semantics> <msub> <mi>M</mi> <mi mathvariant="normal">w</mi> </msub> </semantics></math> 1180 kDa.</p>
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28 pages, 7385 KiB  
Article
Development of Polyoxymethylene/Polylactide Blends for a Potentially Biodegradable Material: Crystallization Kinetics, Lifespan Prediction, and Enzymatic Degradation Behavior
by Jianhua Li, Yatao Wang, Xiaodong Wang and Dezhen Wu
Polymers 2019, 11(9), 1516; https://doi.org/10.3390/polym11091516 - 18 Sep 2019
Cited by 15 | Viewed by 4184
Abstract
This paper reported the development of polyoxymethylene (POM)/polylactide (PLA) blends for a potentially biodegradable material. A series of POM/PLA blends at different weight ratios were prepared by melt extrusion with a twin-screw extruder, and their mechanical properties, crystallization behavior and kinetics, thermal degradation [...] Read more.
This paper reported the development of polyoxymethylene (POM)/polylactide (PLA) blends for a potentially biodegradable material. A series of POM/PLA blends at different weight ratios were prepared by melt extrusion with a twin-screw extruder, and their mechanical properties, crystallization behavior and kinetics, thermal degradation kinetics and stability, lifespan prediction and enzymatic degradation behavior were investigated extensively. POM and PLA were found to be partially miscible in the melt state at low temperature and become phase-separated at elevated temperatures, and their blends exhibited a typical lower critical solution temperature behavior. There were two distinct glass transition temperatures (Tg) observed for POM/PLA blends at any mass ratios when quenched from the homogeneous state, and both POM and PLA domains showed an apparent depression in their respective Tg’s in the blends. Owing to the partial miscibility between two domains, the tensile strength and impact toughness of POM/PLA blends gradually decreased with an increase of PLA content, but their flexural strength and modulus presented an increasing trend with PLA content. The studies on non-isothermal and isothermal crystallization behaviors of the blends indicated that the crystallization rates of the blends decreased continually with increasing the PLA content, confirming that the crystallization of POM domain was controlled by the molecular-confined mechanism. The introduction of PLA into POM not only led to a slight increase of thermal stability of POM domain at low PLA contents but also shortened the lifespan of the blends, favoring the natural degradation of the blends. The POM/PLA blends exhibited an improvement in partially biodegradable performance with an increase of PLA content and their mass loss reached up to 25.3 wt % at the end of 48-h enzymatic degradation when 50 wt % of PLA was incorporated. Full article
(This article belongs to the Special Issue Processing and Molding of Polymers)
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<p>(<b>a</b>) Cloud temperatures, (<b>b</b>) melting temperatures, (<b>c</b>) glass transition temperatures, and (<b>d</b>) XRD patterns of polyoxymethylene/polylactide (POM/PLA) blends at different mass ratios.</p>
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<p>(<b>a</b>,<b>b</b>) FTIR spectra of POM/PLA blends at different mass ratios; (<b>c</b>) schematic interaction between the POM and PLA molecules.</p>
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<p>(<b>a</b>) Tensile strength and Young’s moduli, (<b>b</b>) elongation at break, (<b>c</b>) flexural strength and moduli, and (<b>d</b>) Izod impact strength of pure POM and its blends with PLA.</p>
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<p>Raman spectra of pure POM, PLA and their blends.</p>
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<p>SEM micrographs of impact fracture surfaces of (<b>a</b>) pure POM and its blends with (<b>b</b>) 10 wt %, (<b>c</b>) 20 wt %, (<b>d</b>) 30 wt %, (<b>e</b>) 40 wt %, and (<b>f</b>) 50 wt % of PLA.</p>
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<p>(<b>a</b>) Storage moduli, (<b>b</b>) loss moduli, and (<b>c</b>,<b>d</b>) loss factors (tan δ) of pure POM, pure PLA, and their blends as a function of temperature.</p>
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<p>Differential scanning calorimetry (DSC) thermograms for the non-isothermal crystallization of (<b>a</b>) pure POM and its blends with (<b>b</b>) 10 wt %, (<b>c</b>) 20 wt %, and (<b>d</b>) 40 wt % of PLA at different cooling rates.</p>
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<p>Development of relative degree of crystallinity as a function of time for the non-isothermal crystallization of (<b>a</b>) pure POM and its blends with (<b>b</b>) 10 wt %, (<b>c</b>) 20 wt %, and (<b>d</b>) 40 wt % of PLA at different cooling rates.</p>
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<p>Avrami plots of ln[−ln(1 − <span class="html-italic">X<sub>t</sub></span>)] versus ln<span class="html-italic">t</span> for the non-isothermal crystallization of (<b>a</b>) pure POM and its blends with (<b>b</b>) 10 wt %, (<b>c</b>) 20 wt %, and (<b>d</b>) 40 wt % of PLA at different cooling rates.</p>
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<p>Development of relative degree of crystallinity as a function of time for the isothermal crystallization of (<b>a</b>) pure POM and its blends with (<b>b</b>) 10 wt %, (<b>c</b>) 20 wt %, and (<b>d</b>) 40 wt % of PLA at different crystallization temperatures.</p>
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<p>Avrami plots of ln[−ln(1 − <span class="html-italic">X<sub>t</sub></span>)] versus ln<span class="html-italic">t</span> for the isothermal crystallization of (<b>a</b>) pure POM and its blends with (<b>b</b>) 10 wt %, (<b>c</b>) 20 wt %, and (<b>d</b>) 40 wt % of PLA at different crystallization temperatures.</p>
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<p>Polarizing optical microscopic images of (<b>a</b>) pure POM and its blends with (<b>b</b>) 10 wt %, (<b>c</b>) 20 wt %, (<b>d</b>) 30 wt %, (<b>e</b>) 40 wt %, (<b>f</b>) 50 wt %, and (<b>g</b>) 60 wt % of PLA during the isothermal crystallization process.</p>
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<p>TGA and derivative thermogravimetric (DTG) thermograms of (<b>a</b>) pure POM, (<b>b</b>) pure PLA, and its blends with (<b>c</b>) 10 wt %, (<b>d</b>) 20 wt %, (<b>e</b>) 30 wt %, (<b>f</b>) 50 wt % of PLA during the isothermal crystallization process.</p>
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<p>Plots of lifespan as a function of temperature predicted by the Loop method for pure POM, PLA, and their blends.</p>
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<p>(<b>a</b>) Plots of mass loss as a function of degradation time and (<b>b</b>) plots of mass loss as a function of PLA content for POM/PLA blends.</p>
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<p>SEM micrographs of (<b>a</b>) pure POM, (<b>b</b>) pure PLA, and their blends with (<b>c</b>) 10 wt %, (<b>d</b>) 20 wt %, (<b>e</b>) 30 wt %, (<b>f</b>) 40 wt % and (<b>g</b>) 50 wt % PLA after enzymatic degradation.</p>
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17 pages, 2868 KiB  
Article
Aptamer-Functionalized Liposomes as a Potential Treatment for Basal Cell Carcinoma
by Anca N. Cadinoiu, Delia M. Rata, Leonard I. Atanase, Oana M. Daraba, Daniela Gherghel, Gabriela Vochita and Marcel Popa
Polymers 2019, 11(9), 1515; https://doi.org/10.3390/polym11091515 - 18 Sep 2019
Cited by 82 | Viewed by 5391
Abstract
More than one out of every three new cancers is a skin cancer, and the large majority are basal cell carcinomas (BCC). Targeted therapy targets the cancer’s specific genes, proteins, or tissue environment that contributes to cancer growth and survival and blocks the [...] Read more.
More than one out of every three new cancers is a skin cancer, and the large majority are basal cell carcinomas (BCC). Targeted therapy targets the cancer’s specific genes, proteins, or tissue environment that contributes to cancer growth and survival and blocks the growth as well as the spread of cancer cells while limiting damage to healthy cells. Therefore, in the present study AS1411 aptamer-functionalized liposomes for the treatment of BCC were obtained and characterized. Aptamer conjugation increased liposome size, suggesting that the presence of an additional hydrophilic molecule on the liposomal surface increased the hydrodynamic diameter. As expected, the negatively charged DNA aptamer reduced the surface potential of the liposomes. Vertical Franz diffusion cells with artificial membranes were used to evaluate the in vitro release of 5-fluorouracil (5-FU). The aptamer moieties increase the stability of the liposomes and act as a supplementary steric barrier leading to a lower cumulative amount of the released 5-FU. The in vitro cell viability, targeting capability and apoptotic effects of liposomes on the human dermal fibroblasts and on the basal cell carcinoma TE 354.T cell lines were also evaluated. The results indicate that the functionalized liposomes are more efficient as nanocarriers than the non-functionalized ones. Full article
(This article belongs to the Special Issue Polymeric Colloidal Systems in Nanomedicine)
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<p>Schematic illustration of the AS1411 aptamer-functionalized liposomes.</p>
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<p>The release profiles (%) of 5-FU from the non-functionalized liposomes. Diamonds—L1-5FU-10; squares—L3-5FU-10; triangles—L3-5FU-15, circles—L4-5FU-15.</p>
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<p>The cumulative amount that permeated through the model membrane per unit area (L1-5FU-10—open diamond; L4-5FU-15—open circle; L1Apt-5FU-10—full diamond; L4Apt-5FU-15—full circle).</p>
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<p>Hemolysis percentage after 90 (blue bar), 150 (red bar), and 300 min (green bar) exposure to L3Apt (<b>a</b>) and L3Apt-5FU-15 (<b>b</b>) liposomes sample.</p>
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<p>Viability of fibroblast cells after 72 h of incubation in culture media with L3Apt (with and without drug included) and L4Apt (with and without drug included).</p>
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<p>Viability of fibroblast cells after 24, 48, and 72 h of incubation in culture media with L4Apt (with and without drug included).</p>
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<p>Percentage distribution of the viable, dead, apoptotic, and preapoptotic cells at 8 h after the treatment with the aptamer-functionalized liposomes loaded or not loaded with 5-FUas quantified by annexin V-FITC and propidium iodide in apoptosis assay (flow cytometric method) according to every experimental treatment.</p>
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<p>Histograms of control cells (<b>a and c</b>), of the cells treated with liposomes loaded with fluorescein (<b>b</b>) and of the cells treated with aptamer-functionalized liposomes loaded with fluorescein (<b>d</b>) in order to evaluate their uptake by human dermal fibroblast (HDF) cells. M1—negative for fluorescein, no uptake; M2—positive for fluorescein, cells are loaded with liposomes or aptamer-functionalized liposomes labeled with fluorescein.</p>
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<p>Cell viability of TE 354.T cells as incubated with L4, L4-5FU-15, L4Apt, L4Apt-5FU-15 in doses of 25, 50, 75, and 100 µg lipids/mL for 24 h (<b>a</b>) and 48 h (<b>b</b>)and 5-FU in doses of 25, 50, 75, and 100 µg drug/mL for 24 and 48 h (<b>c</b>) determined by MTT test.</p>
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22 pages, 5624 KiB  
Article
Effect of Different Compatibilizers on Injection-Molded Green Fiber-Reinforced Polymers Based on Poly(lactic acid)-Maleinized Linseed Oil System and Sheep Wool
by Franciszek Pawlak, Miguel Aldas, Juan López-Martínez and María Dolores Samper
Polymers 2019, 11(9), 1514; https://doi.org/10.3390/polym11091514 - 17 Sep 2019
Cited by 23 | Viewed by 3989
Abstract
A method to modify polymers is that of introducing fibers in a matrix to produce a fiber-reinforced polymer (FRP). Consequently, the aim of this work was to study the compatibility effect of four coupling agents on wool FRP properties, using poly(lactic acid) plasticized [...] Read more.
A method to modify polymers is that of introducing fibers in a matrix to produce a fiber-reinforced polymer (FRP). Consequently, the aim of this work was to study the compatibility effect of four coupling agents on wool FRP properties, using poly(lactic acid) plasticized with maleinized linseed oil as polymer matrix. The content of wool assessed was 1 phr. The compatibilizers were (3-(2-aminoethylamino)propyl)-trimethoxysilane, trimethoxy (2-(7-oxabicyclo (4.1.0)hept-3-yl) ethyl) silane, tris(2-methoxyethoxy)(vinyl) silane and titanium (IV) (triethanolaminate)isopropoxide. Initially, wool was modified with coupling agents in an acetone/water (50/50) solution. Mechanical properties were evaluated by tensile and flexural properties, hardness by Shore D measurement and impact resistance by Charpy’s energy. Differential scanning calorimetry, dynamic thermo-mechanical analysis, and thermogravimetric analysis were conducted to evaluate the interaction among components and the effect of the coupling agents on the thermal properties of the original material. Color, wettability and scanning electron microscopy were used to describe physical and microstructural properties. Modification of fibers allows achieving improved mechanical properties and changes the thermal properties of the FRPs slightly. Coupling agent treatment helps to formulate PLA–MLO and sheep wool materials and to improve their performance, thereby creating a broader spectrum of applications for PLA maintaining the bio-based character of the material. Full article
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<p>Chemical structure of coupling agents: (<b>A</b>) (3-(2-aminoethylamino)propyl)-trimethoxysilane; (<b>B</b>) trimethoxy (2-(7-oxabicyclo(4.1.0)hept-3-yl)ethyl]silane; (<b>C</b>) tris(2-methoxyethoxy)(vinyl) silane; and (<b>D</b>) titanium (IV) (triethanolaminate)isopropoxide.</p>
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<p>Scheme of coupling reaction of wool with coupling agent (3-(2-aminoethylamino)propyl)-trimethoxysilane.</p>
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<p>Fourier transform infrared (FTIR) spectra of unmodified wool (UW) and wool modified with studied coupling agents (WA, WB, WC, WD).</p>
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<p>(<b>a</b>) Thermogravimetric analysis (TGA) and (<b>b</b>) first derivative of the TGA curve (DTG) of unmodified wool (UW) and wool modified with studied coupling agents (WA, WB, WC, WD).</p>
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<p>Typical stress–strain curves of PLA–wool FRP, and its corresponding toughness values. <sup>a–e</sup> Different letters show statistically significant differences between formulations (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>(<b>a</b>) Thermogravimetric analysis (TGA) and (<b>b</b>) first derivative of the TGA curve (DTG) of PLA–wool FRP.</p>
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<p>Differential scanning calorimetry (DSC) thermograms of PLA–wool FRP studied, the main transition temperatures are specified.</p>
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<p>DMTA analysis curves: (<b>a</b>) storage modulus and (<b>b</b>) loss factor for PLA–wool FRP.</p>
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<p>Scanning electron microscopy (SEM) images from impact fracture surface of (<b>a</b>) PLA–MLO; (<b>b</b>) PLA–MLO–UW; (<b>c</b>) PLA–MLO–WA; (<b>d</b>) PLA–MLO–WB; (<b>e</b>) PLA–MLO–WC; and (<b>f</b>) PLA–MLO–WD.</p>
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21 pages, 3209 KiB  
Article
Sulfonated Polystyrene Nanoparticles as Oleic Acid Diethanolamide Surfactant Nanocarriers for Enhanced Oil Recovery Processes
by Shalimar P. C. Caplan, Thaís B. G. Silva, Agatha D. S. Franscisco, Elizabeth R. Lachter and Regina S. V. Nascimento
Polymers 2019, 11(9), 1513; https://doi.org/10.3390/polym11091513 - 17 Sep 2019
Cited by 11 | Viewed by 4299
Abstract
The aim of this study is the evaluation of partially sulfonated polystyrene nanoparticles (SPSNP) efficiency as nanocarriers for a non-ionic surfactant, oleic acid diethanolamide (OADA), in the reduction of the surfactant losses and the increase of oil recovery. The synthesized oleic acid diethanolamide [...] Read more.
The aim of this study is the evaluation of partially sulfonated polystyrene nanoparticles (SPSNP) efficiency as nanocarriers for a non-ionic surfactant, oleic acid diethanolamide (OADA), in the reduction of the surfactant losses and the increase of oil recovery. The synthesized oleic acid diethanolamide was characterized by FTIR, 1H NMR, 13C NMR, surface tension (γ = 36.6 mN·m−1, CMC = 3.13 × 10−4 M) and interfacial tension of mineral oil/OADA aqueous solutions (IFTeq = 0.07 mN·m−1). The nanoparticles (SPSNP) were obtained by emulsion polymerization of styrene, DVB and sodium 4-styrenesulfonate (St-S) in the presence of OADA aqueous solution and were characterized by FTIR and PCS. The results show that the presence of ionic groups in the polymer structure promoted a better nanoparticles suspensions′ stability, smaller particles production and more pronounced IFT reduction. The SPSNP obtained with an OADA concentration twenty times its CMC and 0.012 mol % of St-S presented a particle size around 66 nm and can act as efficient nanocarriers decreasing the water/oil interfacial tension to low values (0.07 mN·m−1) along the time, when in contact with the oil. Transport and oil recovery tests of the nanocarriers systems in an unconsolidated sand porous medium test show that the SPSNP do inhibit surfactant adsorption onto sand particles surface and induced an increase of oil recovery of up to about 13% relative to the water flooding oil recovery, probably due to a synergistic effect between the nanoparticles and surfactant action at the water/oil interface. Full article
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<p>OADA synthesis scheme where the main chemical species involved were highlighted as <b>1</b>: Methyl oleate, <b>2</b>: diethanolamine and <b>3</b>: OADA.</p>
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<p>Oil displacement set-up scheme.</p>
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<p>FTIR spectrum of OADA.</p>
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<p><sup>1</sup>H NMR spectrum of OADA.</p>
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<p><sup>13</sup>C NMR-APT spectrum of OADA.</p>
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<p>Surface tension as a function of the logarithm of surfactant concentrations for the CMC determination.</p>
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<p>IFT as a function of surfactant concentration.</p>
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<p>Polystyrene nanoparticles FTIR spectra with different OADA and sulfonate contents: 30sulf20, 12sulf20, 0sulf10 and 0sulf20, whose polymerization formulations are described in <a href="#polymers-11-01513-t001" class="html-table">Table 1</a>.</p>
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<p>Influence of St-S content on SPSNP particle size prepared with different OADA concentrations: 10CMC and 20CMC.</p>
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<p>Influence of St-S content on the interfacial tension between 0.1 (<span class="html-italic">m</span>/<span class="html-italic">v</span>) % SPSNP suspensions in deionized water and mineral oil.</p>
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<p>Surface tension behavior over the time for systems containing 0.1 (<span class="html-italic">m</span>/<span class="html-italic">v</span>) %. Measurements were performed using the Wilhem plate method (temperature: 25 ± 0.5 °C).</p>
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<p>IFT behavior over time for systems containing 0.1 (<span class="html-italic">m</span>/<span class="html-italic">v</span>) % suspensions and mineral oil. Measurements were carried out using the Du Nouy method (temperature: 25 ± 0.5 °C).</p>
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<p>Interfacial tension (IFT) for the 12sulf20 SPSNP suspension (0.1 <span class="html-italic">m</span>/<span class="html-italic">v</span> %) and mineral oil as a function of time. Measurements were performed using Spinning Drop method.</p>
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<p>Influence of sulfonate groups on nanoparticles stabilization.</p>
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<p>Breakthrough curves for suspensions of 12sulf20 SPSNP and 30sulf20 SPSNP and OADA solution (0.2 <span class="html-italic">m</span>%/<span class="html-italic">v</span>%).</p>
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<p>Oil recovery as a function of pore volume injected. The tertiary oil recovery began after the injection of 3 PVs of water.</p>
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<p>Incremental oil recovery as function of pore volumes after the secondary oil recovery.</p>
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15 pages, 3821 KiB  
Article
Crystal Transition Behavior and Thermal Properties of Thermal-Energy-Storage Copolymer Materials with an n-Behenyl Side-Chain
by Yuchen Mao, Jin Gong, Meifang Zhu and Hiroshi Ito
Polymers 2019, 11(9), 1512; https://doi.org/10.3390/polym11091512 - 17 Sep 2019
Cited by 7 | Viewed by 3225
Abstract
In this paper, we synthesized MC(BeA-co-MMA) copolymer microcapsules through suspension polymerization. The pendent n-behenyl group of BeA is highly crystalline, and it acts as the side-chain in the structure of BeA-co-MMA copolymer. The highly crystalline n-behenyl side-chain [...] Read more.
In this paper, we synthesized MC(BeA-co-MMA) copolymer microcapsules through suspension polymerization. The pendent n-behenyl group of BeA is highly crystalline, and it acts as the side-chain in the structure of BeA-co-MMA copolymer. The highly crystalline n-behenyl side-chain provides BeA-co-MMA copolymer thermal-energy-storage capacity. In order to investigate the correlation between the thermal properties and crystal structure of the BeA-co-MMA copolymer, the effects of monomer ratio, temperature changing and the changing rate, as well as synthesis method were discussed. The monomer ratio influenced crystal transition behavior and thermal properties greatly. The DSC results proved that when the monomer ratio of BeA and MMA was 3:1, MC(BeA-co-MMA)3 showed the highest average phase change enthalpy ΔH (105.1 J·g–1). It indicated that the n-behenyl side-chain formed a relatively perfect crystal region, which ensured a high energy storage capacity of the copolymer. All the DSC and SAXS results proved that the amount of BeA had a strong effect on the thermal-energy-storage capacity of the copolymer and the long spacing of crystals, but barely on the crystal lamella. It was found that MMA units worked like defects in the n-behenyl side-chain crystal structure of the BeA-co-MMA copolymer. Therefore, a lower fraction of MMA, that is, a higher fraction of BeA, contributed to a higher crystallinity of the BeA-co-MMA copolymer, providing a better energy storage capacity and thermoregulation property. ST(BeA-co-MMA) copolymer sheets with the same ingredients as microcapsules were also prepared through light-induced polymerization aiming at clarifying the effect of the synthesis method. The results proved that the synthesis method mainly influenced the copolymer chemical component, but lightly on the crystal packing of the n-behenyl side-chain. Full article
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<p>Synthesis schemes of thermoregulation MC(BeA-<span class="html-italic">co</span>-MMA) copolymer (<b>a</b>), and the microcapsules and sheets prepared through suspension and light-induced polymerization, respectively (<b>b</b>). The phase transition between the crystal phase and the isotropic phase promises the energy storage capacity.</p>
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<p>DSC curves of MC(BeA-<span class="html-italic">co</span>-MMA) copolymer microcapsules and MC(BeA) in the cooling process measured at a cooling rate of 5 °C·min<sup>–1</sup>.</p>
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<p>SAXS patterns of MC(BeA-<span class="html-italic">co</span>-MMA) microcapsules and MC(BeA) measured at room temperature. Three diffraction peaks were shown for both MC(BeA) and MC(BeA-<span class="html-italic">co</span>-MMA).</p>
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<p>SAXS patterns of MC(BeA-<span class="html-italic">co</span>-MMA) microcapsules and MC(BeA) in the cooling process from the isotropic phase to the crystal phase at a cooling rate of 0.5 °C·min<sup>−1</sup>. The scale of intensity for each diagram is the same, aiming to give a clear understanding and direct comparison.</p>
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<p>DSC curves of the MC(BeA-<span class="html-italic">co</span>-MMA)3 microcapsule measured at different temperature changing rates (including 1 °C·min<sup>–1</sup>, 3 °C·min<sup>–1</sup>, 5 °C·min<sup>–1</sup> and 10 °C·min<sup>–1</sup>) in the cooling (left) and heating (right) processes.</p>
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<p>Schematic diagram of the phase transition behavior and crystal structure of MC(BeA-<span class="html-italic">co</span>-MMA) microcapsules with a crystalline <span class="html-italic">n</span>-behenyl side-chain.</p>
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<p>DSC curves of sheet samples for ST(BeA-<span class="html-italic">co</span>-MMA) copolymers with different monomer ratios and homopolymers ST(MMA) and ST(BeA) measured at a temperature changing rate of 5 °C·min<sup>–1</sup>.</p>
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<p>FTIR spectra of microcapsule and sheet samples for BeA-<span class="html-italic">co</span>-MMA copolymer and monomers MMA and BeA. (a) MMA, (b) BeA, (c) MC(BeA-<span class="html-italic">co</span>-MMA)5, (d) MC(BeA-<span class="html-italic">co</span>-MMA)3, (e) MC(BeA-<span class="html-italic">co</span>-MMA)1, (f) ST(BeA-<span class="html-italic">co</span>-MMA)5, (g) ST(BeA-<span class="html-italic">co</span>-MMA)3, and (h) ST(BeA-<span class="html-italic">co</span>-MMA)1.</p>
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<p>Wide-angle X-ray scatting (WAXS) patterns of ST(BeA-<span class="html-italic">co</span>-MMA) copolymer sheets and homopolymer ST(BeA) measured at room temperature.</p>
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13 pages, 2716 KiB  
Article
Preparation of Ag Doped Keratin/PA6 Nanofiber Membrane with Enhanced Air Filtration and Antimicrobial Properties
by Baolei Shen, Dongyu Zhang, Yujuan Wei, Zihua Zhao, Xiaofei Ma, Xiaodan Zhao, Shuo Wang and Wenxiu Yang
Polymers 2019, 11(9), 1511; https://doi.org/10.3390/polym11091511 - 16 Sep 2019
Cited by 35 | Viewed by 4368
Abstract
Coarse wool is a kind of goat wool that is difficult to further process in the textile industry due to its large diameter, dispersion, better strength, and less bending. Therefore, coarse wool is often discarded as waste or made into low-cost products. In [...] Read more.
Coarse wool is a kind of goat wool that is difficult to further process in the textile industry due to its large diameter, dispersion, better strength, and less bending. Therefore, coarse wool is often discarded as waste or made into low-cost products. In this work, keratin was extracted from coarse wool by a high-efficiency method, and then, an Ag-doped keratin/PA6 composite nanofiber membrane with enhanced filtration and antibacterial performance was prepared using HCOOH as solvent and reductant. HAADF-STEM (high-angle annular dark field-scanning transmission electron microscopy) shows that AgNPs are uniformly distributed in keratin/PA6 (30/70) nanofibers. TGA (Thermogravimetric Analysis) and DSC (Differential Scanning Calorimetry) were employed to investigate the thermal stability of composite membranes with different keratin and AgNP contents. The present keratin as a dopant with polyamide-6 (PA6) was found not only to improve air filtration efficiency but also to enhance water–vapour transmission (WVT). The addition of the Ag nanoparticles (AgNPs) gave a strong antibacterial activity to the composite membrane against Staphylococcus aureus (99.62%) and Escherichia coli (99.10%). Bacterial filtration efficiency (BFE) of the composite membrane against S. aureus and E. coli were up to 96.8% and 95.6%, respectively. All of the results suggested a great potential for coarse wool extraction and application in the air filtration field. Full article
(This article belongs to the Special Issue Smart Textile)
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<p>Schematic diagram of the wool keratin extraction and preparation of an electrospun keratin/PA6 air filtration membrane with antimicrobial function.</p>
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<p>SEM images of fibrous membranes with different concentrations of polymer mats: (<b>a</b>) Ker.0%/PA6, (<b>b</b>) Ker.30%/PA6′, (<b>c</b>) Ker.30%/PA6, (<b>d</b>) Ag.1%-Ker.30%/PA6, (<b>e</b>) Ag.10%-Ker.30/PA6, (<b>f</b>) Ker.50%/PA6, and (<b>g</b>) Ker.70%/PA6. The histograms show the distribution of fiber diameters corresponding to their SEM image. (<b>h</b>) TEM images, (<b>i</b>) HAADF-STEM (high-angle annular dark field-scanning transmission electron microscopy), and the corresponding EDS (energy dispersive spectrometer) mapping of the Ag, S, and N elements in composite nanofibers.</p>
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<p>Schematic diagram of the quality factor (QF), pore size diameter, and water–vapour transmission (WVT) of composite membranes: (<b>a</b>) the WVT of composite membranes and (<b>b</b>) the comprehensive filtration performance and pore size of composite membranes. Columns 1–7 represent Ker.0%/PA6, Ker.30%/PA6′, Ker.30%/PA6, Ag.1%-Ker.30%/PA6, Ag.10%-Ker.30/PA6, Ker.50%/PA6, and Ker.70%/PA6, respectively.</p>
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<p>Thermogravimetric Analysis (TGA) (<b>a</b>) and Derivative Thermogravimetry (DTG) (<b>b</b>) of as-prepared nanofiber films.</p>
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<p>Differential Scanning Calorimetry (DSC) thermograms of different AgNPs and keratin content of PA6 composite nanofiber films.</p>
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<p>Schematic diagrams of the antibacterial activity of composite nanofibers: (<b>a</b>–<b>c</b>) <span class="html-italic">E. coli</span> and (<b>d</b>–<b>f</b>) <span class="html-italic">S. aureus</span>. <a href="#polymers-11-01511-f006" class="html-fig">Figure 6</a>a,d, <a href="#polymers-11-01511-f006" class="html-fig">Figure 6</a>b,e, and <a href="#polymers-11-01511-f006" class="html-fig">Figure 6</a>c,f represent Ker.30%/PA6, Ag.1%-Ker.30%/PA6, and Ag.10%-Ker.30%/PA6, respectively. The right-hand images of <a href="#polymers-11-01511-f006" class="html-fig">Figure 6</a>a–f correspond to optical microscopic images.</p>
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23 pages, 2602 KiB  
Article
Statistical Copolymers of n-Butyl Vinyl Ether and 2-Chloroethyl Vinyl Ether via Metallocene-Mediated Cationic Polymerization. A Scaffold for the Synthesis of Graft Copolymers
by Stavros Zouganelis, Ioannis Choinopoulos, Ioannis Goulas and Marinos Pitsikalis
Polymers 2019, 11(9), 1510; https://doi.org/10.3390/polym11091510 - 16 Sep 2019
Cited by 7 | Viewed by 5232
Abstract
The cationic statistical copolymerization of n-butyl (be) and 2-chloroethyl vinyl ether (CEVE), is efficiently conducted using bis(η5-cyclopentadienyl)dimethyl zirconium (Cp2ZrMe2) in combination with tetrakis(pentafluorophenyl)borate dimethylanilinum salt [B(C6F5)4][Me2NHPh] [...] Read more.
The cationic statistical copolymerization of n-butyl (be) and 2-chloroethyl vinyl ether (CEVE), is efficiently conducted using bis(η5-cyclopentadienyl)dimethyl zirconium (Cp2ZrMe2) in combination with tetrakis(pentafluorophenyl)borate dimethylanilinum salt [B(C6F5)4][Me2NHPh]+, as an initiation system. The reactivity ratios are calculated using both linear graphical and non-linear methods. Structural parameters of the copolymers are obtained by calculating the dyad sequence fractions and the mean sequence length, which are derived using the monomer reactivity ratios. The glass transition temperatures (Tg) of the copolymers are measured by Differential Scanning Calorimetry (DSC), and the results are compared with predictions based on several theoretical models. The statistical copolymers are further employed as scaffolds for the synthesis of graft copolymers having poly(vinyl ether)s as a backbone and either poly(ε-caprolactone) (PCL) or poly(l-lactide) (PLLA) as side chains. Both the grafting “onto” and the grafting “from” methodologies are employed. The reaction sequence is monitored by Size Exclusion Chromatography (SEC), NMR and IR spectroscopies. The advantages and limitations of each approach are thoroughly examined. Full article
(This article belongs to the Special Issue Polymerizations Promoted by Metal Complexes)
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<p><sup>1</sup>H NMR spectrum of the statistical copolymers PBVE–<span class="html-italic">co</span>–PCEVE.</p>
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<p>Dyad monomer sequence distributions <span class="html-italic">X</span> = M<sub>BVE-BVE</sub> (●), <span class="html-italic">Y</span> = M<sub>CEVE-CEVE</sub> (▲) and <span class="html-italic">Z</span> = M<sub>BVE-CEVE</sub> (■)of the statistical copolymers.</p>
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<p>Johnston plot for the statistical copolymers.</p>
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<p>Barton plot for the statistical copolymers.</p>
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<p>Monitoring the synthesis of sample PBVE–<span class="html-italic">g</span>–PCL#2 via the grafting “onto” methodology by IR spectroscopy.</p>
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<p>Monitoring the synthesis of sample PBVE–<span class="html-italic">g</span>–PCL#2 via the grafting “onto” methodology by SEC.</p>
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<p>Monitoring the synthesis of sample PBVE–<span class="html-italic">g</span>–PCL#2 via the grafting “onto” methodology by <sup>1</sup>H NMR spectroscopy in CDCl<sub>3</sub>.</p>
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<p>Monitoring the synthesis of sample PBVE–<span class="html-italic">g</span>–PLLA #7 via the grafting “from” methodology by SEC.</p>
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<p>(<b>a</b>) Monitoring the synthesis of sample PBVE–<span class="html-italic">g</span>–PLLA #8 via the grafting “from” methodology by <sup>1</sup>H NMR spectroscopy in CDCl<sub>3</sub>; (<b>b</b>) Monitoring the synthesis of sample PBVE–<span class="html-italic">g</span>–PLLA #8 via the grafting “from” methodology by <sup>1</sup>H NMR spectroscopy in CDCl<sub>3</sub>.</p>
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<p>Synthesis of the statistical copolymers PBVE-co-CEVE.</p>
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<p>Synthesis of PBVE–<span class="html-italic">g</span>–PCL and PBVE–<span class="html-italic">g</span>–PLLA graft copolymers via the grafting “onto” methodology.</p>
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<p>Synthesis of PBVE–<span class="html-italic">g</span>–PCL and PBVE–<span class="html-italic">g</span>–PLLA graft copolymers via the grafting “from” methodology.</p>
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17 pages, 4076 KiB  
Article
Boron Removal from Aqueous Solutions by Using a Novel Alginate-Based Sorbent: Comparison with Al2O3 Particles
by Hary Demey, Jesus Barron-Zambrano, Takoua Mhadhbi, Hafida Miloudi, Zhen Yang, Montserrat Ruiz and Ana Maria Sastre
Polymers 2019, 11(9), 1509; https://doi.org/10.3390/polym11091509 - 16 Sep 2019
Cited by 34 | Viewed by 5459
Abstract
Boron removal was evaluated in the present work by using calcium alginate beads (CA) and a novel composite based on alginate–alumina (CAAl) as sorbents in a batch system. The effects of different parameters such as pH, temperature, contact time, and composition of alginate [...] Read more.
Boron removal was evaluated in the present work by using calcium alginate beads (CA) and a novel composite based on alginate–alumina (CAAl) as sorbents in a batch system. The effects of different parameters such as pH, temperature, contact time, and composition of alginate (at different concentrations of guluronic and mannuronic acids) on boron sorption were investigated. The results confirm that calcium alginate beads (CA) exhibited a better adsorption capacity in a slightly basic medium, and the composite alginate–alumina (CAAl) exhibited improved boron removal at neutral pH. Sorption isotherm studies were performed and the Langmuir isotherm model was found to fit the experimental data. The maximum sorption capacities were 4.5 mmol g−1 and 5.2 mmol g−1, using CA and CAAl, respectively. Thermodynamic parameters such as change in free energy (ΔG0), enthalpy (ΔH0), and entropy (ΔS0) were also determined. The pseudo-first-order and pseudo-second-order rate equations (PFORE and PSORE, respectively) were tested to fit the kinetic data; the experimental results can be better described with PSORE. The regeneration of the loaded sorbents was demonstrated by using dilute HCl solution (distilled water at pH 3) as eluent for metal recovery. Full article
(This article belongs to the Special Issue Algae-Based Polymers: Current Trends and Emerging Opportunities)
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<p>Scanning Electron Microscopy (SEM) images of the CAAl material: (<b>a</b>,<b>b</b>) Topography of the sorbent; (<b>c</b>) Energy Dispersive X-ray (EDX) analysis on the surface area of the sorbent, (<b>d</b>) Alumina particles immobilized in the alginate support.</p>
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<p>Influence of pH on boron removal. (<b>a</b>) Removal performances using alumina, CA and CAAl. materials (<b>b</b>) variation in pH (pH<sub>0</sub>: 3–12, [B]initial = 50 mg L<sup>−1</sup>, V = 100 mL, T room, 1 atm).</p>
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<p>Effect of sorbent dosage on boron removal. (<b>a</b>) Removal performances using an initial boron concentration of 5 mg L<sup>−1</sup> (<b>b</b>) Removal performances using an initial boron concentration of 25 mg L<sup>−1</sup> (pH<sub>0</sub>: 7, equilibrium pH 6.6, [B]initial = 5 mg·L<sup>−1</sup> and 25 mg·L<sup>−1</sup>, V = 100 mL, T room, 1 atm).</p>
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<p>Equilibrium studies. (<b>a</b>) Boron sorption isotherms using hydrogel and air-dried beads. (<b>b</b>) Sorption isotherms using different types of alginates (pH<sub>0</sub>: 11, equilibrium pH: 9.5–9.8, V = 100 mL, T room, 1 atm).</p>
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<p>Equilibrium studies for zinc removal using alumina and CAAl materials as sorbents (pH<sub>0</sub>: 4, equilibrium pH: 5.4, Sorbent Dosage: 1 g L<sup>−1</sup>, T room, 1 atm).</p>
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<p>Boron sorption kinetics using hydrogel and air-dried beads (pH<sub>0</sub>: 11, equilibrium pH: 9.5–9.8, [B]initial = 50 mg·L<sup>−1</sup>, 1.75 g of sorbent, V = 250 mL, T room, 1 atm).</p>
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<p>Elution of the sorbents using dilute solution of HCl as eluent. (AD: Air-dried sorbent, eluent: dilute HCl solution (distilled water at pH 3), [B]initial = 50 mg·L<sup>−1</sup>, V = 100 mL).</p>
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<p>Interaction of boric acid specie with hydroxyl groups of calcium alginate.</p>
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<p>Interaction of boric acid specie with hydroxyl groups of alumina.</p>
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<p>Interaction of tetra-hydroxy borate ions specie with hydroxyl groups of calcium alginate.</p>
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<p>Interaction of tetra-hydroxy borate ions specie with hydroxyl groups of alumina.</p>
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19 pages, 3903 KiB  
Article
Ion-Imprinted Polypropylene Fibers Fabricated by the Plasma-Mediated Grafting Strategy for Efficient and Selective Adsorption of Cr(VI)
by Zhengwei Luo, Jiahuan Xu, Dongmei Zhu, Dan Wang, Jianjian Xu, Hui Jiang, Wenhua Geng, Wuji Wei and Zhouyang Lian
Polymers 2019, 11(9), 1508; https://doi.org/10.3390/polym11091508 - 16 Sep 2019
Cited by 17 | Viewed by 3110
Abstract
To improve the adsorption selectivity towards hexavalent chromium anion (Cr(VI)), surface Cr(VI)-imprinted polypropylene (PP) fibers were fabricated by the plasma-mediated grafting strategy. Hence, a non-thermal Rradio frequency discharge plasma irradiation followed by a gaseous phase grafting was used to load acrylic acid (AA) [...] Read more.
To improve the adsorption selectivity towards hexavalent chromium anion (Cr(VI)), surface Cr(VI)-imprinted polypropylene (PP) fibers were fabricated by the plasma-mediated grafting strategy. Hence, a non-thermal Rradio frequency discharge plasma irradiation followed by a gaseous phase grafting was used to load acrylic acid (AA) onto PP fibers, which was afterwards amidated with triethylenetetramine and subjected to imprinting with a Cr(VI) template. The plasma irradiation conditions, i.e., gas species, output power, pressure, and time, were optimized and then the influence of grafting time, pressure, and temperature on the grafting degree of AA was investigated. Scanning electron microscopy and Fourier transform infrared spectroscopy were used for the characterization of pristine and modified fibers and to confirm the synthesis success. The hydrophilicity of modified fibers was greatly improved compared with pristine PP fibers. The adsorption thermodynamics and kinetics of Cr(VI) were investigated, as well as the elution efficiency and reusability. The prepared imprinted fibers showed superior adsorption selectivity to Cr(VI) compared with non-imprinted fibers. Finally, the stability of the imprinted fibers against the oxidation ability of Cr(VI) is discussed. Full article
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<p>Illustration of the experiment setup of the plasma-induced polymerization of AA.</p>
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<p>(<b>a</b>) The effect of the irradiation time on the weight loss of fibers and the effects of (<b>b</b>) the irradiation power, (<b>c</b>) pressure, and (<b>d</b>) time on the grafting degree of AA (grafting conditions: 150 Pa, 90 min, and 45 °C).</p>
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<p>The effects of (<b>a</b>) the pressure, (<b>b</b>) reaction time, and (<b>c</b>) temperature on the grafting degree of PA (plasma irradiation conditions: 120 W, 10 Pa, and 5 min).</p>
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<p>Relationship between the amidation efficiency of PAT and the grafting degree of PA.</p>
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<p>The effects of (<b>a</b>) the crosslinking agents, (<b>b</b>) time, (<b>c</b>) temperature, and (<b>d</b>) crosslinking agent concentration on the crosslinking degree of IPAT.</p>
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<p>SEM images of PP, PA, PAT, and IPAT fibers.</p>
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<p>FTIR spectra and elemental analyses of PP, PA, PAT, and IPAT.</p>
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<p>Water contact angle and hydrophilicity analysis of PP, PA, PAT, and IPAT.</p>
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<p>The effect of the pH on the adsorption capacity of IPAT towards Cr(VI).</p>
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<p>(<b>a</b>) The kinetics curve of Cr(VI) adsorption onto IPAT and the linearized (<b>b</b>) pseudo-first-order and (<b>c</b>) pseudo-second-order kinetics.</p>
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<p>(<b>a</b>) The effect of the initial Cr(VI) concentration on the adsorption capacity of Cr(VI) onto IPAT and the linearization of the (<b>b</b>) Langmuir and (<b>c</b>) Freundlich models.</p>
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<p>The effects of the competing ions on the adsorption selectivity of (<b>a</b>) IPAT and (<b>b</b>) NIPAT.</p>
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<p>(<b>a</b>) The elution efficiency after several elution cycles and (<b>b</b>) the regeneration efficiency of IPAT after 10 adsorption–desorption cycles.</p>
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<p>SEM images and FTIR spectra of dried IPAT loaded with Cr(VI).</p>
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<p>Schematic representation of the preparation process of ion-imprinted PP fibers (IPAT) (<b>i</b>: plasma treatment of PP fibers to form radicals; <b>ii</b>: grafting of acrylic acid (AA) on PP fibers to form AA-grafted PP (PA); <b>iii</b>: amidation of AA with triethylene tetramine (TETA) to form PAT; <b>iv</b>: imprinting of Cr(VI) template and crosslinking; <b>v</b>: elution of Cr(VI) template using a NaOH solution).</p>
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15 pages, 4575 KiB  
Article
Preparation of Phase Change Microcapsules with the Enhanced Photothermal Performance
by Sara Tahan Latibari, Jacco Eversdijk, Ruud Cuypers, Vassiliki Drosou and Mina Shahi
Polymers 2019, 11(9), 1507; https://doi.org/10.3390/polym11091507 - 16 Sep 2019
Cited by 17 | Viewed by 3616
Abstract
The performance of solar-thermal conversion systems can be improved by incorporation of encapsulated phase change materials. In this study, for the first time, CrodathermTM 60 as a phase change material (PCM) was successfully encapsulated within polyurea as the shell supporting material. While [...] Read more.
The performance of solar-thermal conversion systems can be improved by incorporation of encapsulated phase change materials. In this study, for the first time, CrodathermTM 60 as a phase change material (PCM) was successfully encapsulated within polyurea as the shell supporting material. While preparing the slurry samples, graphite nanoplatelet (GNP) sheets were also incorporated to enhance the thermal and photothermal properties of the prepared materials. The morphology and chemical properties of these capsules were characterized by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectrum, respectively. The results show the spherical-like and core-shell structure of capsules with an average diameter size of 3.34 μm. No chemical interaction was observed between the core and the supporting materials. The thermal characteristics of the microencapsulated PCMs (MEPCMs), analyzed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), indicate that the prepared samples with 0.1 weight percentage of GNP possess the latent heat of 95.5 J/g at the phase transition temperature of about 64 °C. Analyzing the rheological properties of the prepared slurry with 16 wt % of MEPCMs proves that the prepared material meet the requirements given by the heat transfer applications. The thermal storage capacity, good thermal stability, and improved photothermal performance of the prepared material make it a potential candidate for using in direct absorption solar thermal applications. Full article
(This article belongs to the Special Issue Polymers for Thermal Energy Conversion and Storage)
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<p>(<b>a</b>) Scheme of chemical interfacial reaction and structure of the prepared capsules; (<b>b</b>) from left to right Crodatherm60@polyurea-0.1%GNP, 0.1%GNP, Crodatherm60@polyurea-0.04%GNP, 0.04%GNP, Crodatherm60@polyurea.</p>
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<p>Photo-to-thermal conversion set-up.</p>
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<p>FTIR spectra of Cr60@polyurea-0.1%GNP and Cr60@Polyurea samples.</p>
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<p>(<b>a</b>,<b>b</b>) SEM images and; (<b>c</b>) particle size distribution of Cr60@Polyurea; (<b>d</b>,<b>e</b>) SEM images; and (<b>f</b>) particle size distribution of Cr60@Polyurea-0.1 wt %GNP.</p>
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<p>DSC curves of encapsulated Crodatherm60, polyurea, and capsules including polyuria-0.1%GNP.</p>
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<p>TGA graphs of Cr60, Cr60@polyurea, and Cr60@polyurea-0.1%GNP.</p>
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<p>Rheological behavior of 16 wt % Cr60@Polyurea-0.1%GNP slurry (<b>a</b>) viscosity versus shear rate at 25 °C; (<b>b</b>) viscosity versus temperature at constant shear rate 10 s<sup>−1</sup>.</p>
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<p>Transmittance spectra of (<b>a</b>) Cr60@polyurea, Cr60@polyurea-0.1 wt %GNP, and Cr60@polyurea-0.04 wt %GNP slurries at 45 ppm concentration; (<b>b</b>) slurries of water and Cr60@polyurea-0.1 wt %GNP with different concentrations.</p>
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<p>Photo-to-thermal conversion spectra of (<b>a</b>) water; (<b>b</b>) 0.1%GNP; (<b>c</b>) Cr60@Polyurea; and (<b>d</b>) Cr60@polyurea-0.1%GNP samples (h = the total height of the collector, y = the height distance from the illumination surface to the location of the adjusted thermocouple).</p>
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<p>Temperature change difference of Cr60@polyurea-0.1%GP samples.</p>
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<p>Specific heat of Cr60@polyurea-0.1%GNP slurry (16 wt %) and water [<a href="#B30-polymers-11-01507" class="html-bibr">30</a>].</p>
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14 pages, 7135 KiB  
Article
Poly-L-lysine as an Effective and Safe Desquamation Inducer of Urinary Bladder Epithelium
by Mojca Kerec Kos, Peter Veranič and Andreja Erman
Polymers 2019, 11(9), 1506; https://doi.org/10.3390/polym11091506 - 16 Sep 2019
Cited by 3 | Viewed by 3232
Abstract
Induced desquamation of urinary bladder epithelial cells, also called urothelial cells, is frequently used in studies of bladder epithelial regeneration and also in treating recurrent bacterial cystitis. Positively charged polymer chitosan is known to cause large-scale desquamation of terminally differentiated urothelial cells called [...] Read more.
Induced desquamation of urinary bladder epithelial cells, also called urothelial cells, is frequently used in studies of bladder epithelial regeneration and also in treating recurrent bacterial cystitis. Positively charged polymer chitosan is known to cause large-scale desquamation of terminally differentiated urothelial cells called umbrella cells. Aiming to compare the desquamation ability of another polycation poly-L-lysine, we studied the effect of this polymer on the functional and structural integrity of the urothelium in ex vivo and in vivo experiments. The urothelium was analyzed by measuring transepithelial electrical resistance, and the structural changes of its luminal surface were analyzed with scanning electron microscopy. The results revealed a selective and concentration-dependent desquamation effect of poly-L-lysine on superficial urothelial cells followed by quick regeneration of the urothelium, which functionally and structurally recovers in 2 to 3 h after poly-L-lysine–induced injury. Poly-L-lysine was thus proven to be a promising polymer to be used when desquamation of urothelial cells is required in basic and potentially clinical studies. Full article
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<p>Schematic outline of the ex vivo experiments. Poly-L-lysine (PLL) with molecular weight 30–70 kDa or 70–150 kDa was used. PB = phosphate buffer.</p>
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<p>Schematic design of in vivo experiments.</p>
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<p>Average values and standard deviations of relative TEER of the urothelium exposed for 15 min to 0.001% or 0.01% poly-L-lysine (PLL) with a molecular weight of 30–70 kDa or 70–150 kDa. At each experimental condition, measurements were performed on urinary bladders of three to four different animals. Exposure time to PLL is marked gray.</p>
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<p>Average values and standard deviations of relative TEER of the urothelium exposed for 30 min to 0.001% or 0.01% poly-L-lysine (PLL) with a molecular weight of 30–70 kDa or 70–150 kDa. At each experimental condition measurements were performed on urinary bladders of three different animals. Exposure time interval to PLL is marked gray.</p>
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<p>Representative SEM micrographs of the urothelium at the end of the 15 min treatment period with phosphate buffer (<b>A</b> and <b>A’</b>), with 0.001% PLL (30–70 kDa) (<b>B</b> and <b>B’</b>), or with 0.01% PLL (30–70 kDa) (<b>C</b> and <b>C’</b>) in ex vivo experiments. Images (<b>A’</b>, <b>B’</b> and <b>C’</b>) show key features of the urothelium at higher magnification. Image <b>A</b> shows intact urothelium and image <b>A’</b> shows polygonal terminally differentiated superficial cells (umbrella cells) with typically scalloped apical plasma membrane composing luminal surface of intact urothelium. In images <b>B</b> and <b>C</b>, the majority of the urothelium is desquamated (black asterisks) and in only some areas are umbrella cells still present (black arrows). In images <b>B’</b> and <b>C’</b>, desquamated areas of the urothelium are presented under higher magnification, where cells with microvilli (black asterisks in <b>B’</b>) and ropy ridges of apical membrane (white stars in <b>B’</b> and <b>C’</b>) are exposed on urothelial surface due to desquamation of umbrella cells. Only individual umbrella cells still remain on the urothelial surface after such treatment (white triangle in <b>C’</b>). Scale bars: 200 µm (<b>A</b>,<b>B</b>,<b>C</b>), 20 µm (<b>A’</b>), and 10 µm (<b>B’</b>,<b>C’</b>).</p>
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<p>Representative SEM micrographs of the urothelium at the end of the regeneration period after the urothelium was exposed to phosphate buffer (<b>A</b> and <b>A’</b>), 0.001% PLL (30–70 kDa) (<b>B</b> and <b>B’</b>) or to 0.01% PLL (30–70 kDa) (<b>C</b> and <b>C’</b>) in ex vivo experiments. Images <b>A’</b>, <b>B’</b> and <b>C’</b> show key features of the urothelium at higher magnification. Luminal surface of intact urothelium (<b>A</b>) consists of large, terminally differentiated superficial cells (umbrella cells) with specifically scalloped apical plasma membrane (<b>A’</b>). In images <b>B</b>, <b>B’</b>, <b>C</b>, and <b>C’</b>, the whole urothelial superficial layer was renewed after desquamation and composed of rare small cells with microvilli (white star in <b>C’</b>) and predominant cells with ropy ridges of apical plasma membrane (white asterisks in <b>B’</b> and <b>C’</b>) between undesquamated umbrella cells (black triangles in <b>C</b> and <b>B’</b>). Scale bars: 200 µm (<b>A</b>,<b>B</b>), 50 µm (<b>C</b>), 20 µm (<b>A’</b>), and 10 µm (<b>B’</b>,<b>C’</b>).</p>
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<p>Representative SEM micrographs of the urothelium in in vivo experiments after 15 min exposure to 0.001% PLL with molecular weights 30–70 kDa (<b>A</b> and <b>A’</b>) and 70–150 kDa (<b>B</b> and <b>B’</b>). Images <b>A’</b> and <b>B’</b> show key features of the urothelium at higher magnifications. In image <b>A</b>, only individual umbrella cells desquamate (black arrows), while in image <b>B</b> small groups of umbrella cells desquamate or have already been peeled off causing occasional small desquamated areas of the urothelium (white asterisks). Images <b>A’</b> and <b>B’</b> show desquamated areas of the urothelium (encircled with a white line in <b>B’</b>). Exposed former intermediate cells are smaller than umbrella cells and without scalloped apical plasma membrane revealing lower differentiation stage. Scale bars: 100 µm (<b>A</b>,<b>B</b>), 20 µm (<b>A</b>’,<b>B</b>’).</p>
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<p>Representative SEM micrographs of the urothelium in in vivo experiments after 15 min exposure to 0.01% PLL with molecular weight 30–70 kDa (<b>A</b> and <b>A’</b>) and 70–150 kDa (<b>B</b> and <b>B’</b>). Images <b>A’</b> and <b>B’</b> show key features of the urothelium at higher magnifications. In images <b>A</b> and <b>B</b> are seen large and predominant areas of the urothelium, where umbrella cells desquamated and, thus, intermediate cells are exposed on the surface. Some still attached umbrella cells, which did not undergo desquamation, are present on urothelial surface (white asterisks). In desquamated urothelial areas in images <b>A’</b> and <b>B’</b>, exposed intermediate cells as new superficial cells are small and with microvilli (white triangle in <b>B’</b>) or ropy ridges of apical plasma membrane (white stars in <b>A’</b>). Scale bars: 50 µm (<b>A</b>), 200 µm (<b>B</b>), 20 µm (<b>A’</b>), and 2 µm (<b>B’</b>).</p>
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16 pages, 7583 KiB  
Article
Simonkolleite Coating on Poly(Amino Acids) to Improve Osteogenesis and Suppress Osteoclast Formation in Vitro
by Shuyang Li, Xingtao Chen, Xiaomei Wang, Yi Xiong, Yonggang Yan, Zhi Tan, Xiaoyu Yang and Yuanye Li
Polymers 2019, 11(9), 1505; https://doi.org/10.3390/polym11091505 - 16 Sep 2019
Cited by 10 | Viewed by 3474
Abstract
Zinc can enhance osteoblastic bone formation and stimulate osteogenic differentiation, suppress the differentiation of osteoclast precursor cells into osteoclasts, and inhibit pathogenic bacterial growth in a dose-dependent manner. In this study, simonkolleite, as a novel zinc resource, was coated on poly (amino acids) [...] Read more.
Zinc can enhance osteoblastic bone formation and stimulate osteogenic differentiation, suppress the differentiation of osteoclast precursor cells into osteoclasts, and inhibit pathogenic bacterial growth in a dose-dependent manner. In this study, simonkolleite, as a novel zinc resource, was coated on poly (amino acids) (PAA) via suspending PAA powder in different concentrations of zinc chloride (ZnCl2) solution, and the simonkolleite-coated PAA (Zn–PAA) was characterized by SEM, XRD, FT-IR and XPS. Zinc ions were continuously released from the coating, and the release behavior was dependent on both the concentration of the ZnCl2 immersing solution and the type of soak solutions (SBF, PBS and DMEM). The Zn–PAA was cultured with mouse bone marrow stem cells (BMSCs) through TranswellTM plates, and the results indicated that the relative cell viability, alkaline phosphatase (ALP) activity and mineralization of BMSCs were significantly higher with Zn–PAA as compared to PAA. Moreover, the Zn–PAA was cultured with RAW264.7 cells, and the results suggested an inhibiting effect of Zn–PAA on the cell differentiation into osteoclasts. In addition, Zn–PAA exhibited an antibacterial activity against both S. aureus and E. coli. These findings suggest that simonkolleite coating with certain contents could promote osteogenesis, suppress osteoclast formation and inhibit bacteria, indicating a novel way of enhancing the functionality of synthetic bone graft material and identifying the underline principles for designing zinc-containing bone grafts. Full article
(This article belongs to the Special Issue Polymers for Bone Tissue Engineering)
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<p>(<b>A</b>) The XRD patterns of PAA–0.1M, PAA–0.05M, PAA–0.025M and PAA (the simonkolleite spectrum was derived from the standard PDF card No. 00-07-0155); (<b>B</b>) The FT-IR patterns of PAA–0.1M and PAA: (a) the enlarged view from wavenumbers 1050 to 700 cm<sup>−1</sup>, (b) the enlarged view from wavenumbers 550 to 440 cm<sup>−1</sup>; (<b>C</b>) The XPS spectrum of PAA–0.1M and PAA; and (<b>D</b>) the enlarged Zn 2p and Cl 1s regions of PAA–0.1M.</p>
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<p>The SEM analysis of the surface morphology of (<b>A</b>) PAA–0.1M, (<b>B</b>) PAA–0.05M, (<b>C</b>) PAA–0.025M and (<b>D</b>) PAA (white arrows represent simonkolleite crystals, the scale bar: 2 μm).</p>
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<p>The zinc ion release of PAA, PAA–0.1M, PAA–0.05M and PAA–0.025M in (<b>A</b>) DMEM, (<b>B</b>) PBS and (<b>C</b>) SBF after 1, 7, 14 and 21 days, as detected by AAS.</p>
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<p>The relative cell viability and morphology of BMSCs cultured with Zn–PAA and PAA. (<b>A</b>) The cell viability of BMSCs cultured with Zn–PAA and PAA at 1, 4 and 7 days detected by cck-8 kit. (* <span class="html-italic">p</span> &lt; 0.05 compared to PAA and PAA–0.1M); the morphology of BMSCs at 4 days of incubation cultured with (<b>B</b>) black control; (<b>C</b>) PAA; (<b>D</b>) PAA–0.025M; (<b>E</b>) PAA–0.05M; and (<b>F</b>) PAA–0.1M. The scale bar: 100 μm.</p>
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<p>The Alizarin Red S staining of BMSCs at 21 days under an optical microscope, and the ALP activity of BMSCs cultured with Zn–PAA and PAA for 7, 14 and 21 days. The Alizarin Red S staining of the BMSCs cultured with (<b>A</b>) control, (<b>B</b>) PAA, (<b>C</b>) PAA–0.025M, (<b>D</b>) PAA–0.05M and (<b>E</b>) PAA–0.1M; the scale bar: 100 μm; and their photographs in the Transwell plate under chambers (inserted); (<b>F</b>) the ALP activity of BMSCs (** <span class="html-italic">p</span> &lt; 0.05 compared to each other sample; * <span class="html-italic">p</span> &lt; 0.05 compared to the control, PAA or PAA–0.1M; # <span class="html-italic">p</span> &lt; 0.05 compared to the control or PAA).</p>
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<p>RAW264.7 cultured with (<b>A</b>) PAA–0.025M; (<b>B</b>) PAA–0.05M; (<b>C</b>) PAA–0.1M; (<b>D</b>) PAA and (<b>E</b>) control in a Transwell plate stimulated by 25 ng/mL RANKL at 5 days under an optical microscope; the scale bar: 100 μm; and (<b>E</b>) the relative osteoclasts’ formation rate of the Zn–PAA and PAA groups. (* <span class="html-italic">p</span> &lt; 0.05).</p>
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<p>The inhibition rate of Zn–PAA and PAA against <span class="html-italic">E. coli</span> and <span class="html-italic">S. aureus</span> after 24 h of cultivation. (* <span class="html-italic">p</span> &lt; 0.05 compared to PAA, ** <span class="html-italic">p</span> &lt; 0.05 compared to PAA–0.025M and PAA).</p>
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12 pages, 7619 KiB  
Article
Application of Xanthan Gum as a Pre-Treatment and Sharpness Evaluation for Inkjet Printing on Polyester
by Hongmei Cao, Li Ai, Zhenming Yang and Yawei Zhu
Polymers 2019, 11(9), 1504; https://doi.org/10.3390/polym11091504 - 16 Sep 2019
Cited by 21 | Viewed by 4092
Abstract
Inkjet printing on polyester fabric displays versatile environmental advantages. One of the significant benefits of inkjet printing is a dramatic enhancement of the printing quality. In this study, xanthan gum—a bio-based thickening agent accompanied by several salts—was adopted for the pretreatment of polyester [...] Read more.
Inkjet printing on polyester fabric displays versatile environmental advantages. One of the significant benefits of inkjet printing is a dramatic enhancement of the printing quality. In this study, xanthan gum—a bio-based thickening agent accompanied by several salts—was adopted for the pretreatment of polyester fabric aiming at improving the sharpness and color depth of inkjet printed patterns. The influences of four metal salts (NaCl, KCl, CaCl2 and MgCl2) on inkjet printing performance were studied. More importantly, a quantitative method for evaluating the sharpness of an inkjet printed pattern was established according to the characteristics of anisotropy and isotropy of diffusion and adsorption of ink droplets on a fiber surface. Results showed that xanthan gum along with a low dosage of bivalent salts can significantly improve the color depth (K/S value) and sharpness of the printed polyester fabrics. It is feasible to evaluate the sharpness of inkjet printed polyester fabrics using a five-stage system, selecting the inkjet ellipse coefficient (T) and inkjet ellipse area (S), which can provide a quantitative and rapid evaluation method for defining inkjet printing. Full article
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<p>Flowchart of printing process on the pretreated polyethylene terephthalate (PET) fabric.</p>
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<p>Flowchart of ink drop experiment on the pretreated PET fabric.</p>
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<p>Effect of salt concentration on the K/S value of inkjet printing.</p>
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<p>Effect of xanthan gum of treated PET fibers. (<b>a</b>) Change of weight ratio and air permeability of fibers. (<b>b</b>) Fourier transform infrared spectroscopy (FTIR) spectrum of fibers. (<b>c</b>) Scanning electron microscopy (SEM) image of fibers (×1000). Sample A was PET fibers treated using CaCl<sub>2</sub> and xanthan gum. Sample B was PET fibers treated by post-treatment. Sample C was untreated PET fibers.</p>
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<p>Effect of salt concentration on the width of warp printing direction.</p>
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<p>Effect of salt concentration on the width of weft printing direction.</p>
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17 pages, 4983 KiB  
Article
A Facile and Simple Method for Preparation of Novel High-Efficient Form-Stable Phase Change Materials Using Biomimetic–Synthetic Polydopamine Microspheres as a Matrix for Thermal Energy Storage
by Junkai Gao, Xi Tang, Zhengshou Chen, Han Ding, Yi Liu, Xuebin Li and Yan Chen
Polymers 2019, 11(9), 1503; https://doi.org/10.3390/polym11091503 - 15 Sep 2019
Cited by 17 | Viewed by 3312
Abstract
Polydopamine microspheres (PDAMs), synthesized using a biomimetic method, were used as a matrix for polyethylene glycol (PEG) to develop a novel high-efficient form-stable phase change material (PEG/PDAM) using a simple vacuum impregnation strategy. The PDAMs were first used as a support for the [...] Read more.
Polydopamine microspheres (PDAMs), synthesized using a biomimetic method, were used as a matrix for polyethylene glycol (PEG) to develop a novel high-efficient form-stable phase change material (PEG/PDAM) using a simple vacuum impregnation strategy. The PDAMs were first used as a support for the organic phase change materials, and the biomimetic synthesis of the PDAMs had the advantages of easy operation, mild conditions, and environmental friendliness. The characteristics and thermal properties of the PEG/PDAMs were investigated using SEM, FTIR, XRD, TGA, DSC, and XPS, and the results demonstrated that the PEG/PDAMs possessed favourable heat storage capacity, excellent thermal stability, and reliability, and the melting and freezing latent heats of PEG/PDAM-3 reached 133.20 ± 2.50 J/g and 107.55 ± 4.45 J/g, respectively. Therefore, the PEG/PDAMs possess great potential in real-world applications for thermal energy storage. Additionally, the study on the interaction mechanism between the PEG and PDAMs indicated that PEG was immobilized on the surface of PDAMs through hydrogen bonds between the PEG molecules and the PDAMs. Moreover, the PDAMs can also be used as a matrix for other organic materials for the preparation of form-stable phase change materials. Full article
(This article belongs to the Special Issue Polymers for Thermal Energy Conversion and Storage)
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<p>Schematic representation of the preparation process of polyethylene glycol (PEG)/polydopamine microspheres (PDAMs).</p>
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<p>TEM images of PDAMs (<b>a</b>,<b>b</b>), SEM image of PDAMs (<b>c</b>), PEG/PDAM-1 (<b>d</b>), PEG/PDAM-2 (<b>e</b>), and PEG/PDAM-3 (<b>f</b>).</p>
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<p>TEM images of PDAMs (<b>a</b>,<b>b</b>), SEM image of PDAMs (<b>c</b>), PEG/PDAM-1 (<b>d</b>), PEG/PDAM-2 (<b>e</b>), and PEG/PDAM-3 (<b>f</b>).</p>
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<p>N<sub>2</sub> adsorption/desorption isotherms of the PDAMs.</p>
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<p>Leakage test photographs of PEG, PEG/PDAM-1, PEG/PDAM-2, PEG/PDAM-3, and PEG/PDAM-4.: (<b>a</b>) pictures of samples before the thermal stability test; (<b>b</b>) pictures of samples after the thermal stability test; (<b>c</b>) pictures of leakage trace after the removal of samples.</p>
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<p>XRD patterns of PEG, PEG/PDAM-1, PEG/PDAM-2, PEG/PDAM-3, and PDAMs.</p>
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<p>FTIR spectra of PEG, PEG/PDAM-1, PEG/PDAM-2, PEG/PDAM-3, and PDAM.</p>
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<p>DSC curves of PEG and the samples.</p>
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<p>Formation mechanism of polydopamine.</p>
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<p>Inferred interaction mechanism between PEG and the PDAMs.</p>
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<p>DSC curves of PEG/PDAM-3 before and after the thermal cycle.</p>
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<p>TGA curves of PEG, PDAMs, and PEG/PDAM-3.</p>
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<p>XPS patterns of the PDAMs: (<b>a</b>) C, (<b>c</b>) O, and (<b>e</b>) N, and XPS patterns of 75% PEG/PDAM-3: (<b>b</b>) C, (<b>d</b>) O, and (<b>f</b>) N.</p>
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<p>XPS survey of the PDAMs and PEG/PDAM-3.</p>
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14 pages, 5091 KiB  
Article
Homocrystallization and Stereocomplex Crystallization Behaviors of As-Spun and Hot-Drawn Poly(l-lactide)/Poly(d-lactide) Blended Fibers During Heating
by Tien-Wei Shyr, Huan-Chieh Ko and Hsin-Lung Chen
Polymers 2019, 11(9), 1502; https://doi.org/10.3390/polym11091502 - 14 Sep 2019
Cited by 7 | Viewed by 3369
Abstract
A series of poly(l-lactide)/poly(d-lactide) blended chips (LDC), as-spun LD fibers (LDA) and hot-drawn LD fibers (LDH) were prepared for investigating the homocrystallization and stereocomplex crystallization behaviors of LDA and LDH fibers [...] Read more.
A series of poly(l-lactide)/poly(d-lactide) blended chips (LDC), as-spun LD fibers (LDA) and hot-drawn LD fibers (LDH) were prepared for investigating the homocrystallization and stereocomplex crystallization behaviors of LDA and LDH fibers during heating. Modulated differential scanning calorimetry (MDSC), hot stage polarized microscopy (HSPM), and real-time wide-angle X-ray diffraction (WAXD) were used for studying the crystallization and melting behaviors, fiber morphology, and crystalline structure evolution of the LDA and LDH fibers’ homocrystals and stereocomplex crystals during heating. The molecular chain orientations of the LDA and LDH fibers were obtained through spinning and improved through the hot drawing processes. When the molecular chain was oriented on the fiber axis, the homocrystals and stereocomplex crystals of the fibers began to form in turn as the heating temperature exceeded the glass transition temperature of the fiber. The side-by-side packing of the molecular chains was promoted by mixing the molecular chains with the extrusion screw during the spinning process, facilitating stereocomplex crystallization. When the LDA fiber was heated above the glass transition temperature of the fiber, movement of the fiber molecular chain—including molecular chain orientation and relaxation, as well as crystallization, melting, and recrystallization of homocrystals and stereocomplex crystals—were investigated through HSPM. MDSC and real-time WAXD were used to observe the molecular chains of the melted poly(l-lactide) and poly(d-lactide) homocrystals of the fibers rearranging and transiting to form stereocomplex crystals during heating. Full article
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<p>1D wide-angle X-ray diffraction (WAXD) profiles and 2D WAXD patterns for L<sub>C</sub>, D<sub>C</sub>, and LD<sub>C</sub> chips. (010), (110/200), (203), and (015) in green are related to homocrystal reflections; (110), (300/030), and (220) in red are related to stereocomplex crystal reflections.</p>
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<p>1D WAXD profiles and 2D WAXD patterns for as-spun fibers.</p>
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<p>Birefringence of as-spun (white) and hot-drawn (gray) fibers.</p>
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<p>1D WAXD profiles and 2D WAXD patterns for hot-drawn fibers. (110/200) and (203) are homocrystal reflections.</p>
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<p>Standard differential scanning calorimeter (DSC) thermal analyses of chips, as-spun fibers, and hot-drawn fibers. Samples were heated to 290 °C for 3 min at 10 °C/min and then cooled to 30 °C at 10 °C/min.</p>
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<p>Melting enthalpy of the homocrystal and the stereocomplex crystal of the chips, as-spun fibers, and hot-drawn fibers. (<b>a</b>) Δ<span class="html-italic">H</span><sub>m</sub> of a homocrystal and (<b>b</b>) Δ<span class="html-italic">H</span><sub>m</sub> of a stereocomplex crystal.</p>
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<p>Modulated DSC (MDSC) curves obtained at a heating rate of 2 °C/min, a period of 200 s, and an amplitude of 1 °C. (<b>a</b>) D<sub>A</sub>, (<b>b</b>) L5D<sub>A</sub>, and (<b>c</b>) L5DH.</p>
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<p>Polarized photographs of the as-spun L5D<sub>A</sub> fibers at elevated temperatures, taken at the temperature indicated below the image. Markers H and S represent the homocrystal and stereocomplex crystal, respectively.</p>
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<p>2D WAXD patterns and corresponding intensity curves of L5D<sub>A</sub> and L5D<sub>H</sub> fibers, captured at the temperature indicated in the image.</p>
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<p>2D WAXD patterns and corresponding intensity curves of L5D<sub>A</sub> and L5D<sub>H</sub> fibers, captured at the temperature indicated in the image.</p>
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