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Polymers, Volume 9, Issue 3 (March 2017)

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Cover Story Successful gene therapy relies on the development of efficient and biocompatible delivery vectors. [...] Read more.
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Open AccessArticle Antibacterial Property and Cytotoxicity of a Poly(lactic acid)/Nanosilver-Doped Multiwall Carbon Nanotube Nanocomposite
Polymers 2017, 9(3), 100; doi:10.3390/polym9030100
Received: 17 November 2016 / Accepted: 8 March 2017 / Published: 10 March 2017
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Abstract
A novel method was used to synthesize a nanosilver-doped multiwall carbon nanotube (MWCNT-Ag), and subsequently, the novel poly(lactic acid) (PLA)- and MWCNT-Ag-based biocompatible and antimicrobial nanocomposites were prepared by melt blending. Based on energy dispersive X-ray spectrometry images, an MWCNT-Ag was successfully synthesized.
[...] Read more.
A novel method was used to synthesize a nanosilver-doped multiwall carbon nanotube (MWCNT-Ag), and subsequently, the novel poly(lactic acid) (PLA)- and MWCNT-Ag-based biocompatible and antimicrobial nanocomposites were prepared by melt blending. Based on energy dispersive X-ray spectrometry images, an MWCNT-Ag was successfully synthesized. The effect of the MWCNT-Ag on the PLA bionanocomposites was investigated by evaluating their thermal and mechanical properties, antifungal activity, and cytotoxicity. The nanocomposites exhibited a high degree of biocompatibility with the MWCNT-Ag content, which was less than 0.3 phr. Furthermore, tensile strength testing, thermogravimetric analysis, differential scanning calorimetry, and antibacterial evaluation revealed that the tensile strength, thermostability, glass transition temperature, and antibacterial properties were enhanced by increasing the MWCNT-Ag content. Finally, hydrolysis analysis indicated that the low MWCNT-Ag content could increase the packing density of PLA. Full article
(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)
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Open AccessArticle Optical Characterization of Doped Thermoplastic and Thermosetting Polymer-Optical-Fibers
Polymers 2017, 9(3), 90; doi:10.3390/polym9030090
Received: 25 November 2016 / Revised: 22 February 2017 / Accepted: 1 March 2017 / Published: 4 March 2017
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Abstract
The emission properties of a graded-index thermoplastic polymer optical fiber and a step-index thermosetting one, both doped with rhodamine 6G, have been studied. The work includes a detailed analysis of the amplified spontaneous emission together with a study of the optical gains and
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The emission properties of a graded-index thermoplastic polymer optical fiber and a step-index thermosetting one, both doped with rhodamine 6G, have been studied. The work includes a detailed analysis of the amplified spontaneous emission together with a study of the optical gains and losses of the fibers. The photostability of the emission of both types of fibers has also been investigated. Comparisons between the results of both doped polymer optical fibers are presented and discussed. Full article
(This article belongs to the Special Issue Polymeric Fibers)
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Open AccessArticle Potassium Iodide-Functionalized Polyaniline Nanothin Film Chemiresistor for Ultrasensitive Ozone Gas Sensing
Polymers 2017, 9(3), 80; doi:10.3390/polym9030080
Received: 20 January 2017 / Revised: 19 February 2017 / Accepted: 21 February 2017 / Published: 24 February 2017
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Abstract
Polyaniline (PANI) nanostructures have been widely studied for their sensitivity to atmospheric pollutants at ambient conditions. We recently showed an effective way to electropolymerize a PANI nanothin film on prefabricated microelectrodes, and demonstrated its remarkable sensing performance to be comparable to that of
[...] Read more.
Polyaniline (PANI) nanostructures have been widely studied for their sensitivity to atmospheric pollutants at ambient conditions. We recently showed an effective way to electropolymerize a PANI nanothin film on prefabricated microelectrodes, and demonstrated its remarkable sensing performance to be comparable to that of a one-dimensional nanostructure, such as PANI nanowires. In this work, we report further progress in the application of the PANI nanothin film chemiresistive sensor for the detection of ozone (O3) by modifying the film with potassium iodide (KI). The KI-PANI sensor exhibited an excellent sensitivity to O3 (8–180 ppb O3 concentration rage) with a limit of detection of 230 ppt O3, and exquisite selectivity against active chemicals such as nitrogen dioxide (NO2) and sulfur dioxide (SO2). The sensing mechanism of the sensor relied on iodometric chemistry of KI and O3, producing triiodide ( I 3 ) that partially doped and increased electrical conductivity of the PANI film. The sensitivity and selectivity of the KI-functionalized PANI film demonstrates the potential use for KI-PANI-based O3 sensing devices in environmental monitoring and occupational safety. Full article
(This article belongs to the Special Issue Polymers for Chemosensing)
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Open AccessArticle Thermoreversible Cross-Linking of Furan-Containing Ethylene/Vinyl Acetate Rubber with Bismaleimide
Polymers 2017, 9(3), 81; doi:10.3390/polym9030081
Received: 19 January 2017 / Revised: 14 February 2017 / Accepted: 22 February 2017 / Published: 25 February 2017
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Abstract
A proof of principle for the use of Diels–Alder (DA) chemistry as a thermoreversible cross-linking tool for ethylene–vinyl acetate (EVA) rubber is demonstrated using two differently prepared amorphous furan-functionalized EVA rubbers. The first is an EVFM terpolymer of ethylene, vinyl acetate, and furfuryl
[...] Read more.
A proof of principle for the use of Diels–Alder (DA) chemistry as a thermoreversible cross-linking tool for ethylene–vinyl acetate (EVA) rubber is demonstrated using two differently prepared amorphous furan-functionalized EVA rubbers. The first is an EVFM terpolymer of ethylene, vinyl acetate, and furfuryl methacrylate. The second is an EVA-g-furan product, resulting from the reaction of maleated EVA with furfurylamine. Both furan-containing EVA rubbers have been cross-linked with bismaleimide (BM) via a DA coupling reaction to yield final products with similar cross-link density. The BM cross-linked EVFM terpolymer products display rubber properties similar to the ones of peroxide-cured EVA rubbers with similar cross-link densities, whereas the rubber properties of the BM cross-linked EVA-g-furan correspond to those of a rubber with a higher cross-link density. The preparation of the EVA-g-furan was up-scaled to a small internal mixer, which also allowed compounding with carbon black and mineral oil in the same step. Compounding with carbon black results in reinforcement of the EVA rubber (i.e., enhanced strength), and does not interfere with the reprocessing via the retro DA reaction. Full article
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Open AccessArticle Synthesis and Characterization of Methyl Cellulose/Keratin Hydrolysate Composite Membranes
Polymers 2017, 9(3), 91; doi:10.3390/polym9030091
Received: 25 January 2017 / Revised: 24 February 2017 / Accepted: 1 March 2017 / Published: 4 March 2017
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Abstract
It is known that aqueous keratin hydrolysate solutions can be produced from feathers using superheated water as solvent. This method is optimized in this study by varying the time and temperature of the heat treatment in order to obtain a high solute content
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It is known that aqueous keratin hydrolysate solutions can be produced from feathers using superheated water as solvent. This method is optimized in this study by varying the time and temperature of the heat treatment in order to obtain a high solute content in the solution. With the dissolved polypeptides, films are produced using methyl cellulose as supporting material. Thereby, novel composite membranes are produced from bio-waste. It is expected that these materials exhibit both protein and polysaccharide properties. The influence of the embedded keratin hydrolysates on the methyl cellulose structure is investigated using Fourier transform infrared spectroscopy (FTIR) and wide angle X-ray diffraction (WAXD). Adsorption peaks of both components are present in the spectra of the membranes, while the X-ray analysis shows that the polypeptides are incorporated into the semi-crystalline methyl cellulose structure. This behavior significantly influences the mechanical properties of the composite films as is shown by tensile tests. Since further processing steps, e.g., crosslinking, may involve a heat treatment, thermogravimetric analysis (TGA) is applied to obtain information on the thermal stability of the composite materials. Full article
(This article belongs to the Special Issue Bio-inspired and Bio-based Polymers)
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Open AccessArticle Exploring the Limits of the Geometric Copolymerization Model
Polymers 2017, 9(3), 101; doi:10.3390/polym9030101
Received: 4 February 2017 / Revised: 7 March 2017 / Accepted: 8 March 2017 / Published: 13 March 2017
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Abstract
The geometric copolymerization model is a recently introduced statistical Markov chain model. Here, we investigate its practicality. First, several approaches to identify the optimal model parameters from observed copolymer fingerprints are evaluated using Monte Carlo simulated data. Directly optimizing the parameters is robust
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The geometric copolymerization model is a recently introduced statistical Markov chain model. Here, we investigate its practicality. First, several approaches to identify the optimal model parameters from observed copolymer fingerprints are evaluated using Monte Carlo simulated data. Directly optimizing the parameters is robust against noise but has impractically long running times. A compromise between robustness and running time is found by exploiting the relationship between monomer concentrations calculated by ordinary differential equations and the geometric model. Second, we investigate the applicability of the model to copolymerizations beyond living polymerization and show that the model is useful for copolymerizations involving termination and depropagation reactions. Full article
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Open AccessArticle Preparation of RF-(VM-SiO2)n-RF/AM-Cellu Nanocomposites, and Use Thereof for the Modification of Glass and Filter Paper Surfaces: Creation of a Glass Thermoresponsive Switching Behavior and an Efficient Separation Paper Membrane
Polymers 2017, 9(3), 92; doi:10.3390/polym9030092
Received: 25 December 2016 / Revised: 27 February 2017 / Accepted: 1 March 2017 / Published: 4 March 2017
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Abstract
Fluoroalkyl end-capped vinyltrimethoxysilane oligomeric silica/alkyl-modified cellulose (AM-Cellu) nanocomposites [RF-(CH2-CHSiO2)n-RF/AM-Cellu; n = 2, 3; RF = CF(CF3)OC3F7] were prepared by the sol-gel reactions of the corresponding oligomer
[...] Read more.
Fluoroalkyl end-capped vinyltrimethoxysilane oligomeric silica/alkyl-modified cellulose (AM-Cellu) nanocomposites [RF-(CH2-CHSiO2)n-RF/AM-Cellu; n = 2, 3; RF = CF(CF3)OC3F7] were prepared by the sol-gel reactions of the corresponding oligomer [RF-(CH2-CHSi(OMe)3)n-RF] in the presence of AM-Cellu. The nanocomposites thus obtained were applied to the surface modification of glass to exhibit a highly oleophobic/superhydrophilic characteristic on the modified surface at 20 °C. Interestingly, a temperature dependence of contact angle values of dodecane and water was observed on the modified surface at 20~70 °C, and the dodecane contact angle values were found to decrease with increasing the temperatures from 20 to 70 °C to provide from highly oleophobic to superoleophilic characteristics on the surface. On the other hand, the increase of the water contact angle values was observed with the increase in the temperatures under similar conditions to supply superhydrophilic to superhydrophobic characteristics on the modified surface. The corresponding nanocomposites were also applied to the surface modification of the filter paper under similar conditions to afford a superoleophilic/superhydrophobic characteristic on the surface. It was demonstrated that the modified filter paper is effective for the separation membrane for W/O emulsion to isolate the transparent colorless oil. Full article
(This article belongs to the Special Issue Polymer Blends 2017)
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Open AccessArticle Preparation and Application of Starch/Polyvinyl Alcohol/Citric Acid Ternary Blend Antimicrobial Functional Food Packaging Films
Polymers 2017, 9(3), 102; doi:10.3390/polym9030102
Received: 9 February 2017 / Revised: 6 March 2017 / Accepted: 10 March 2017 / Published: 14 March 2017
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Abstract
Ternary blend films were prepared with different ratios of starch/polyvinyl alcohol (PVA)/citric acid. The films were characterized by field emission scanning electron microscopy (FE-SEM), thermogravimetric analysis, as well as Fourier transform infrared (FTIR) analysis. The influence of different ratios of starch/polyvinyl alcohol (PVA)/citric
[...] Read more.
Ternary blend films were prepared with different ratios of starch/polyvinyl alcohol (PVA)/citric acid. The films were characterized by field emission scanning electron microscopy (FE-SEM), thermogravimetric analysis, as well as Fourier transform infrared (FTIR) analysis. The influence of different ratios of starch/polyvinyl alcohol (PVA)/citric acid and different drying times on the performance properties, transparency, tensile strength (TS), water vapor permeability (WVP), water solubility (WS), color difference (ΔE), and antimicrobial activity of the ternary blends films were investigated. The starch/polyvinyl alcohol/citric acid (S/P/C1:1:0, S/P/C3:1:0.08, and S/P/C3:3:0.08) films were all highly transparent. The S/P/C3:3:0.08 had a 54.31 times water-holding capacity of its own weight and its mechanical tensile strength was 46.45 MPa. In addition, its surface had good uniformity and compactness. The S/P/C3:1:0.08 and S/P/C3:3:0.08 showed strong antimicrobial activity to Listeria monocytogenes and Escherichia coli, which were the food-borne pathogenic bacteria used. The freshness test results of fresh figs showed that all of the blends prevented the formation of condensed water on the surface of the film, and the S/P/C3:1:0.08 and S/P/C3:3:0.08 prevented the deterioration of figs during storage. The films can be used as an active food packaging system due to their strong antibacterial effect. Full article
(This article belongs to the Special Issue Bio-inspired and Bio-based Polymers)
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Open AccessArticle Cell Proliferation on Polyethylene Terephthalate Treated in Plasma Created in SO2/O2 Mixtures
Polymers 2017, 9(3), 82; doi:10.3390/polym9030082
Received: 3 January 2017 / Revised: 20 February 2017 / Accepted: 22 February 2017 / Published: 25 February 2017
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Abstract
Samples of polymer polyethylene terephthalate were exposed to a weakly ionized gaseous plasma to modify the polymer surface properties for better cell cultivation. The gases used for treatment were sulfur dioxide and oxygen of various partial pressures. Plasma was created by an electrodeless
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Samples of polymer polyethylene terephthalate were exposed to a weakly ionized gaseous plasma to modify the polymer surface properties for better cell cultivation. The gases used for treatment were sulfur dioxide and oxygen of various partial pressures. Plasma was created by an electrodeless radio frequency discharge at a total pressure of 60 Pa. X-ray photoelectron spectroscopy showed weak functionalization of the samples’ surfaces with the sulfur, with a concentration around 2.5 at %, whereas the oxygen concentration remained at the level of untreated samples, except when the gas mixture with oxygen concentration above 90% was used. Atomic force microscopy revealed highly altered morphology of plasma-treated samples; however, at high oxygen partial pressures this morphology vanished. The samples were then incubated with human umbilical vein endothelial cells. Biological tests to determine endothelialization and possible toxicity of the plasma-treated polyethylene terephthalate samples were performed. Cell metabolic activity (MTT) and in vitro toxic effects of unknown compounds (TOX) were assayed to determine the biocompatibility of the treated substrates. The biocompatibility demonstrated a well-pronounced maximum versus gas composition which correlated well with development of the surface morphology. Full article
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Open AccessArticle Au Nanoparticles Immobilized on Honeycomb-Like Polymeric Films for Surface-Enhanced Raman Scattering (SERS) Detection
Polymers 2017, 9(3), 93; doi:10.3390/polym9030093
Received: 24 January 2017 / Revised: 28 February 2017 / Accepted: 2 March 2017 / Published: 6 March 2017
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Abstract
We have successfully developed novel surface-enhanced Raman scattering (SERS) substrates with three-dimensional (3D) porous structures for effectively improving the sensitivity and reproducibility of SERS, which can rapidly detect small molecules (rhodamine 6G as an example). Periodical arrays of the honeycomb-like substrates were fabricated
[...] Read more.
We have successfully developed novel surface-enhanced Raman scattering (SERS) substrates with three-dimensional (3D) porous structures for effectively improving the sensitivity and reproducibility of SERS, which can rapidly detect small molecules (rhodamine 6G as an example). Periodical arrays of the honeycomb-like substrates were fabricated by self-assembling polyurethane-co-azetidine-2,4-dione (PU-PAZ) polymers. PU-PAZ comprising amphiphilic dendrons could stabilize the phase separation between the water droplets and polymer solution, and then organize into regular porous structures during the breath figure method. Subsequently, SERS substrates were fabricated by immobilizing gold nanoparticles (AuNPs) onto the honeycomb-like films with various 3D porous structures, controlled by the different PU-PAZ concentrations and relative humidities. Results show that surface enhancement factors of honeycomb-like substrates were 20 times higher than that of flat-film substrates (control group) due to enormous hot-spots resonance effects by the 3D porous structure, verified through Raman mapping at various positions of the z-axis. Furthermore, the particle size effects were evaluated by immobilized 12 and 67 nm of AuNPs on the honeycomb-like substrates, indicating larger AuNPs could induce more pronounced hot-spots effects. The generation of hot-spots resonance to enhance Raman intensity is strongly dependent on the diameter of AuNPs and the pore size of the honeycomb-like and 3D porous substrates for label-free and rapid SERS detection. Full article
(This article belongs to the Special Issue Polymers for Chemosensing)
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Open AccessArticle Unusual Emission of Polystyrene-Based Alternating Copolymers Incorporating Aminobutyl Maleimide Fluorophore-Containing Polyhedral Oligomeric Silsesquioxane Nanoparticles
Polymers 2017, 9(3), 103; doi:10.3390/polym9030103
Received: 30 November 2016 / Revised: 8 March 2017 / Accepted: 13 March 2017 / Published: 15 March 2017
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Abstract
In this study, we synthesized an unusual 2-aminobutyl maleimide isobutyl polyhedral oligomeric silsesquioxane (MIPOSS-NHBu) monomer lacking conventional fluorescent groups. We then prepared poly(styrene-alt-2-aminobutyl maleimide isobutyl POSS) [poly(S-alt-MIPOSS-NHBu)] and poly(4-acetoxystyrene-alt-2-aminobutyl maleimide isobutyl POSS) [poly(AS-alt-MIPOSS-NHBu)] copolymers through
[...] Read more.
In this study, we synthesized an unusual 2-aminobutyl maleimide isobutyl polyhedral oligomeric silsesquioxane (MIPOSS-NHBu) monomer lacking conventional fluorescent groups. We then prepared poly(styrene-alt-2-aminobutyl maleimide isobutyl POSS) [poly(S-alt-MIPOSS-NHBu)] and poly(4-acetoxystyrene-alt-2-aminobutyl maleimide isobutyl POSS) [poly(AS-alt-MIPOSS-NHBu)] copolymers through facile free radical copolymerizations using azobisisobutyronitrile as the initiator and tetrahydrofuran as the solvent. A poly(4-hydroxystyrene-alt-2-aminobutyl maleimide isobutyl POSS) [poly(HS-alt-MIPOSS-NHBu)] copolymer was prepared through acetoxyl hydrazinolysis of poly(AS-alt-MIPOSS-NHBu). We employed 1H, 13C, and 29Si nuclear magnetic resonance spectroscopy; Fourier transform infrared spectroscopy; differential scanning calorimetry; and photoluminescence spectroscopy to investigate the structures and the thermal and optical properties of the monomers and novel POSS-containing alternating copolymers. Intramolecular hydrogen bonding between the amino and dihydrofuran-2,5-dione group and clustering of the locked C=O groups from the POSS nanoparticles in the MIPOSS-NHBu units restricted the intramolecular motion of the polymer chain, causing it to exhibit strong light emission. As a result, the MIPOSS-NHBu monomer and the poly(AS-alt-MIPOSS-NHBu) copolymer both have potential applicability in the detection of metal ions with good selectivity. Full article
(This article belongs to the Special Issue Polymers for Chemosensing)
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Open AccessArticle Synthesis of Aluminum Complexes Bearing 8-Anilide-5,6,7-trihydroquinoline Ligands: Highly Active Catalyst Precursors for Ring-Opening Polymerization of Cyclic Esters
Polymers 2017, 9(3), 83; doi:10.3390/polym9030083
Received: 6 February 2017 / Revised: 24 February 2017 / Accepted: 25 February 2017 / Published: 1 March 2017
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Abstract
The stoichiometric reactions of 8-(2,6-R1-4-R2-anilide)-5,6,7-trihydroquinoline (LH) with AlR3 (R = Me or Et) afforded the aluminum complexes LAlR2 (Al1Al5,Al1: R1 = iPr, R2 = H, R
[...] Read more.
The stoichiometric reactions of 8-(2,6-R1-4-R2-anilide)-5,6,7-trihydroquinoline (LH) with AlR3 (R = Me or Et) afforded the aluminum complexes LAlR2 (Al1Al5,Al1: R1 = iPr, R2 = H, R = Me; Al2: R1 = Me, R2 = H, R = Me; Al3: R1 = H, R2 = H, R = Me; Al4: R1 = Me, R2 = Me, R = Me; Al5: R1 = Me, R2 = Me, R = Et) in high yields. All aluminum complexes were characterized by NMR spectroscopy and elemental analysis. The molecular structures of complexes Al4 and Al5 were determined by single-crystal X-ray diffractions and revealed a distorted tetrahedral geometry at aluminum. In the presence of BnOH, complexes Al1Al5 efficiently initiated the ring-opening homopolymerization of ε-caprolactone (ε-CL) and rac-lactide (rac-LA), respectively, in a living/controlled manner. Full article
(This article belongs to the Special Issue Tailored Polymer Synthesis by Advanced Polymerization Techniques)
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Open AccessArticle Monitoring Moisture Damage Propagation in GFRP Composites Using Carbon Nanoparticles
Polymers 2017, 9(3), 94; doi:10.3390/polym9030094
Received: 31 December 2016 / Revised: 22 February 2017 / Accepted: 24 February 2017 / Published: 8 March 2017
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Abstract
Glass fiber reinforced polymer (GFRP) composites are widely used in infrastructure applications including water structures due to their relatively high durability, high strength to weight ratio, and non-corrosiveness. Here we demonstrate the potential use of carbon nanoparticles dispersed during GFRP composite fabrication to
[...] Read more.
Glass fiber reinforced polymer (GFRP) composites are widely used in infrastructure applications including water structures due to their relatively high durability, high strength to weight ratio, and non-corrosiveness. Here we demonstrate the potential use of carbon nanoparticles dispersed during GFRP composite fabrication to reduce water absorption of GFRP and to enable monitoring of moisture damage propagation in GFRP composites. GFRP coupons incorporating 2.0 wt % carbon nanofibers (CNFs) and 2.0 wt % multi-wall carbon nanotubes (MWCNTs) were fabricated in order to study the effect of moisture damage on mechanical properties of GFRP. Water absorption tests were carried out by immersing the GFRP coupons in a seawater bath at two temperatures for a time period of three months. Effects of water immersion on the mechanical properties and glass transition temperature of GFRP were investigated. Furthermore, moisture damage in GFRP was monitored by measuring the electrical conductivity of the GFRP coupons. It was shown that carbon nanoparticles can provide a means of self-sensing that enables the monitoring of moisture damage in GFRP. Despite the success of the proposed technique, it might not be able to efficiently describe moisture damage propagation in GFRP beyond a specific threshold because of the relatively high electrical conductivity of seawater. Microstructural investigations using Fourier Transform Infrared (FTIR) explained the significance of seawater immersion time and temperature on the different levels of moisture damage in GFRP. Full article
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Open AccessArticle Superiorly Plasticized PVC/PBSA Blends through Crotonic and Acrylic Acid Functionalization of PVC
Polymers 2017, 9(3), 84; doi:10.3390/polym9030084
Received: 12 January 2017 / Revised: 15 February 2017 / Accepted: 22 February 2017 / Published: 1 March 2017
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Abstract
Superior plasticization efficiency was achieved by a grafting from functionalization of the PVC backbone. This was deduced to a synergistic effect of internal plasticization and improved intermolecular interactions between PVC and an oligomeric poly(butylene succinate-co-adipate) (PBSA) plasticizer. A mild grafting process
[...] Read more.
Superior plasticization efficiency was achieved by a grafting from functionalization of the PVC backbone. This was deduced to a synergistic effect of internal plasticization and improved intermolecular interactions between PVC and an oligomeric poly(butylene succinate-co-adipate) (PBSA) plasticizer. A mild grafting process for functionalization of the PVC chain by crotonic acid (CA) or acrylic acid (AA) was used. The formation of PVC-g-CA and PVC-g-AA was confirmed by FTIR and 1H NMR. Grafting with the seemingly similar monomers, CA and AA, resulted in different macromolecular structures. AA is easily homopolymerized and long hydrophilic poly(acrylic acid) grafts are formed resulting in branched materials. Crotonic acid does not easily homopolymerize; instead, single crotonic acid units are located along the PVC chain, leading to basically linear PVC chains with pendant crotonic acid groups. The elongation of PVC-g-CA and PVC-g-AA in comparison to pure PVC were greatly increased from 6% to 128% and 167%, respectively, by the grafting reactions. Blending 20% (w/w) PBSA with PVC, PVC-AA or PVC-CA further increased the elongation at break to 150%, 240% and 320%, respectively, clearly showing a significant synergistic effect in the blends with functionalized PVC. This is a clearly promising milestone towards environmentally friendly flexible PVC materials. Full article
(This article belongs to the Special Issue Polymer Blends 2017)
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Open AccessArticle Microwave Assisted Reduction of Pt-Catalyst by N-Phenyl-p-Phenylenediamine for Proton Exchange Membrane Fuel Cells
Polymers 2017, 9(3), 104; doi:10.3390/polym9030104
Received: 8 January 2017 / Revised: 7 March 2017 / Accepted: 8 March 2017 / Published: 15 March 2017
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Abstract
The presence of N-phenyl-p-phenylenediamine (PPDA: a dimer of aniline) during microwave (MW) irradiation can significantly improve Pt-loading on the XC72 carbon matrix as a catalyst support of proton exchange membrane fuel cells (PEMFCs). PPDA is converted to an emeraldine base
[...] Read more.
The presence of N-phenyl-p-phenylenediamine (PPDA: a dimer of aniline) during microwave (MW) irradiation can significantly improve Pt-loading on the XC72 carbon matrix as a catalyst support of proton exchange membrane fuel cells (PEMFCs). PPDA is converted to an emeraldine base state during MW-assisted redox reaction, which is characterized by both FTIR and Raman spectra. The increased degree of conjugation from the formation of quinone-state of PPDA is confirmed by UV-VIS spectra. TEM micrographs and residue weights obtained from the TGA thermograms illustrate the particle size and Pt-loading percent of Pt nanoparticles (NPs) after MW irradiation, respectively. X-ray diffraction patterns indicate Pt NPs are successfully loaded on XC72 by MW irradiation corresponding to hydrothermal method. The single cell performance demonstrates an increasing power and maximum current density when Pt-catalyst of membrane exchanged assembly (MEA) is prepared by MW-assisted reduction in the presence of PPDA. Full article
(This article belongs to the Special Issue Metal Complexes-Mediated Catalysis in Polymerization)
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Open AccessArticle Improvement of Interfacial Adhesion by Bio-Inspired Catechol-Functionalized Soy Protein with Versatile Reactivity: Preparation of Fully Utilizable Soy-Based Film
Polymers 2017, 9(3), 95; doi:10.3390/polym9030095
Received: 8 February 2017 / Accepted: 2 March 2017 / Published: 7 March 2017
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Abstract
The development of materials based on renewable resources with enhanced mechanical and physicochemical properties is hampered by the abundance of hydrophilic groups because of their structural instability. Bio-inspired from the strong adhesion ability of mussel proteins, renewable and robust soy-based composite films were
[...] Read more.
The development of materials based on renewable resources with enhanced mechanical and physicochemical properties is hampered by the abundance of hydrophilic groups because of their structural instability. Bio-inspired from the strong adhesion ability of mussel proteins, renewable and robust soy-based composite films were fabricated from two soybean-derived industrial materials: soluble soybean polysaccharide (SSPS) and catechol-functionalized soy protein isolate (SPI-CH). The conjugation of SPI with multiple catechol moieties as a versatile adhesive component for SSPS matrix efficiently improved the interfacial adhesion between each segment of biopolymer. The biomimetic adherent catechol moieties were successfully bonded in the polymeric network based on catechol crosslinking chemistry through simple oxidative coupling and/or coordinative interaction. A combination of H-bonding, strong adhesion between the SPI-CH conjugation and SSPS matrix resulted in remarkable enhancements for mechanical properties. It was found that the tensile strength and Young’s modulus was improved from 2.80 and 17.24 MPa of unmodified SP film to 4.04 and 97.22 MPa of modified one, respectively. More importantly, the resultant films exhibited favorable water resistance and gas (water vapor) barrier performances. The results suggested that the promising way improved the phase adhesion of graft copolymers using catechol-functionalized polymers as versatile adhesive components. Full article
(This article belongs to the Special Issue Bio-inspired and Bio-based Polymers)
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Open AccessArticle Mononuclear Nickel(II) Complexes with Schiff Base Ligands: Synthesis, Characterization, and Catalytic Activity in Norbornene Polymerization
Polymers 2017, 9(3), 105; doi:10.3390/polym9030105
Received: 23 February 2017 / Revised: 13 March 2017 / Accepted: 13 March 2017 / Published: 16 March 2017
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Abstract
The nickel(II) catalyst has manifested higher catalytic activity compared to that of other late transition metal catalysts for norbornene polymerization. Therefore, several structurally similar trans-nickel(II) compounds of N,O-chelate bidentate ligands were synthesized and characterized. Both the electronic effect and
[...] Read more.
The nickel(II) catalyst has manifested higher catalytic activity compared to that of other late transition metal catalysts for norbornene polymerization. Therefore, several structurally similar trans-nickel(II) compounds of N,O-chelate bidentate ligands were synthesized and characterized. Both the electronic effect and the steric hindrance influence polymerization. The molecular structures of 2, 4 and 5 were further confirmed by single-crystal X-ray diffraction. Full article
(This article belongs to the Special Issue Metal Complexes-Mediated Catalysis in Polymerization)
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Open AccessArticle Pressure Analysis of Dynamic Injection Molding and Process Parameter Optimization for Reducing Warpage of Injection Molded Products
Polymers 2017, 9(3), 85; doi:10.3390/polym9030085
Received: 19 October 2016 / Revised: 24 January 2017 / Accepted: 23 February 2017 / Published: 7 March 2017
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Abstract
Plastic injection molding technology is one of the important technologies for the manufacturing industry. In this paper, a numerical dynamic injection molding technology (DIMT) is presented, which is based on the finite element (FE) method. This numerical simulation method introduces a vibrational force
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Plastic injection molding technology is one of the important technologies for the manufacturing industry. In this paper, a numerical dynamic injection molding technology (DIMT) is presented, which is based on the finite element (FE) method. This numerical simulation method introduces a vibrational force into the conventional injection molding technology (CIMT). Some meaningful work has been executed for investigating the mechanical evolution behavior of DIMT. As the basis for illustrating the mechanism in warpage optimization results, dynamic parameter analysis on the rule of pressure response is performed in detail. In the warpage optimization work, three kinds of structure with different molding materials are selected as the comparison. The final warpage of each product is efficiently minimized by using a Gaussian process-based sequential optimization method. From the further discussions, the features of DIMT in improving the molding quality are revealed, indicating that it may not be appropriate for geometrically large structures. This study has significant meaning for the actual injection molding industry. Full article
(This article belongs to the Special Issue Computational Modeling and Simulation in Polymer)
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Open AccessArticle Correlation of Microstructure, Rheological and Morphological Characteristics of Synthesized Polypropylene (PP) Reactor Blends Using Homogeneous Binary Metallocene Catalyst
Polymers 2017, 9(3), 75; doi:10.3390/polym9030075
Received: 14 January 2017 / Revised: 7 February 2017 / Accepted: 16 February 2017 / Published: 24 February 2017
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Abstract
A novel binary homogeneous catalyst system based on (I): rac-Me2Si(2-Me-4-PhIn)2ZrCl2 and (II): (2-PhIn)2ZrCl2 catalysts at various molar ratios was utilized for the synthesis of polypropylene (PP) reactor blends with bimodal molecular weight distribution (MWD).
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A novel binary homogeneous catalyst system based on (I): rac-Me2Si(2-Me-4-PhIn)2ZrCl2 and (II): (2-PhIn)2ZrCl2 catalysts at various molar ratios was utilized for the synthesis of polypropylene (PP) reactor blends with bimodal molecular weight distribution (MWD). The results of gel permeation chromatography analyses revealed that the catalyst (I) was responsible for the production of i-PP with high molecular weight (MW) while the individual use of catalyst (II) led to the production of an elastomeric PP with relatively low MW. However, application of the binary catalyst system led to high MW bimodal MWD products being highly dependent on the catalysts’ molar ratios. Increasing the molar ratio of catalyst (II) to catalyst (I) resulted in a notable enhancement of the products’ complex viscosity due to the increased MW, a higher level of chains’ entanglements and formation of amorphous blocks along the polymer chains. All products exhibited a single relaxation that shifted towards longer times upon changing the catalysts’ molar ratios. Scanning electron microscopy results revealed that the fracture surface of the blends, synthesized by the binary catalyst system, became more heterogeneous in comparison with the products obtained by the individual use of the catalyst (I). The observed heterogeneity was found to increase by increasing the amount of catalyst (II). Such morphological change was further corroborated by the dynamic rheological data, indicating a promising correlation between the linear rheological results and the morphological features of the synthesized PP reactor blends. Full article
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Open AccessArticle Synthesis of Dimethyl-Substituted Polyviologen and Control of Charge Transport in Electrodes for High-Resolution Electrochromic Displays
Polymers 2017, 9(3), 86; doi:10.3390/polym9030086
Received: 7 January 2017 / Revised: 17 February 2017 / Accepted: 26 February 2017 / Published: 3 March 2017
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Abstract
Electrochromic (EC) polymers such as polyviologens have been attracting considerable attention as wet-processable electrodes for EC displays, thanks to their brilliant color change accompanied with reversible redox reactions. To establish wider usage, achieving multicolor and high-resolution characteristics is indispensable. In this paper, we
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Electrochromic (EC) polymers such as polyviologens have been attracting considerable attention as wet-processable electrodes for EC displays, thanks to their brilliant color change accompanied with reversible redox reactions. To establish wider usage, achieving multicolor and high-resolution characteristics is indispensable. In this paper, we demonstrated that the introduction of substituents such as methyl groups into bipyridine units changed the stereostructure of the cation radicals, and thus shifted the color (e.g., ordinary purple to blue). Also, by relaxing excessive π-stacking between the viologen moieties, the response rate was improved by a factor of more than 10. The controlled charge transport throughout the polyviologen layer gave rise to the fabrication of EC displays which are potentially suitable for the thin film transistor (TFT) substrate as the counter electrodes with submillimeter pixels. The findings can be versatilely used for the new design of polyviologens with enhanced electrochemical properties and high-resolution, multicolor EC displays. Full article
(This article belongs to the Special Issue Electroactive Polymers and Gels)
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Open AccessArticle Crystal Structure Evolution of UHMWPE/HDPE Blend Fibers Prepared by Melt Spinning
Polymers 2017, 9(3), 96; doi:10.3390/polym9030096
Received: 9 January 2017 / Revised: 6 March 2017 / Accepted: 7 March 2017 / Published: 9 March 2017
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Abstract
Ultra-high molecular weight polyethylene (UHMWPE) and high-density polyethylene (HDPE) blend fibers with the highest tensile strength of 1.13 GPa were prepared by a melt spinning process. The mechanical behavior and crystal structure of the as-spun filaments and fibers were studied by differential scanning
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Ultra-high molecular weight polyethylene (UHMWPE) and high-density polyethylene (HDPE) blend fibers with the highest tensile strength of 1.13 GPa were prepared by a melt spinning process. The mechanical behavior and crystal structure of the as-spun filaments and fibers were studied by differential scanning calorimetry (DSC), scanning electron microscopy (SEM), X-ray diffraction (XRD), sound velocity orientation testing, and tensile testing. The orientation degree, crystallinity, tensile strength, and initial modulus of the fibers increased with the increasing of the draw ratios. The grain size was shortened in the radial direction and elongated in the axial direction. The results suggested that the improvement of the tensile strength and initial modulus was a result of the compact crystal structure formed by slender grains composed of highly oriented molecular chains. Blending with HDPE could improve the formation of a slender and compact crystal structure, and the tensile strength and initial modulus of the blend fibers were higher. Full article
(This article belongs to the Special Issue Polymer Blends 2017)
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Open AccessArticle Preparation and Characterization of Epoxy Resin Cross-Linked with High Wood Pyrolysis Bio-Oil Substitution by Acetone Pretreatment
Polymers 2017, 9(3), 106; doi:10.3390/polym9030106
Received: 16 February 2017 / Revised: 8 March 2017 / Accepted: 10 March 2017 / Published: 15 March 2017
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Abstract
The use of cost effective solvents may be necessary to store wood pyrolysis bio-oil in order to stabilize and control its viscosity, but this part of the production system has not been explored. Conversely, any rise in viscosity during storage, that would occur
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The use of cost effective solvents may be necessary to store wood pyrolysis bio-oil in order to stabilize and control its viscosity, but this part of the production system has not been explored. Conversely, any rise in viscosity during storage, that would occur without a solvent, will add variance to the production system and render it cost ineffective. The purpose of this study was to modify bio-oil with a common solvent and then react the bio-oil with an epoxy for bonding of wood without any loss in properties. The acetone pretreatment of the bio-oil/epoxy mixture was found to improve the cross-linking potential and substitution rate based on its mechanical, chemical, and thermal properties. Specifically, the bio-oil was blended with epoxy resin at weight ratios ranging from 2:1 to 1:5 and were then cured. A higher bio-oil substitution rate was found to lower the shear bond strength of the bio-oil/epoxy resins. However, when an acetone pretreatment was used, it was possible to replace the bio-oil by as much as 50% while satisfying usage requirements. Extraction of the bio-oil/epoxy mixture with four different solvents demonstrated an improvement in cross-linking after acetone pretreatment. ATR-FTIR analysis confirmed that the polymer achieved a higher cross-linked structure. DSC and TGA curves showed improved thermal stability with the addition of the acetone pretreatment. UV-Vis characterization showed that some functional groups of the bio-oil to epoxy system were unreacted. Finally, when the resin mixture was utilized to bond wood, the acetone pretreatment coupled with precise tuning of the bio-oil:epoxy ratio was an effective method to control cross-linking while ensuring acceptable bond strength. Full article
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Open AccessArticle Bio-Inspired Polymer Membrane Surface Cleaning
Polymers 2017, 9(3), 97; doi:10.3390/polym9030097
Received: 22 February 2017 / Revised: 2 March 2017 / Accepted: 5 March 2017 / Published: 9 March 2017
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Abstract
To generate polyethersulfone membranes with a biocatalytically active surface, pancreatin was covalently immobilized. Pancreatin is a mixture of digestive enzymes such as protease, lipase, and amylase. The resulting membranes exhibit self-cleaning properties after “switching on” the respective enzyme by adjusting pH and temperature.
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To generate polyethersulfone membranes with a biocatalytically active surface, pancreatin was covalently immobilized. Pancreatin is a mixture of digestive enzymes such as protease, lipase, and amylase. The resulting membranes exhibit self-cleaning properties after “switching on” the respective enzyme by adjusting pH and temperature. Thus, the membrane surface can actively degrade a fouling layer on its surface and regain initial permeability. Fouling tests with solutions of protein, oil, and mixtures of both, were performed, and the membrane’s ability to self-clean the fouled surface was characterized. Membrane characterization was conducted by investigation of the immobilized enzyme concentration, enzyme activity, water permeation flux, fouling tests, porosimetry, X-ray photoelectron spectroscopy, and scanning electron microscopy. Full article
(This article belongs to the Special Issue Bio-inspired and Bio-based Polymers)
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Open AccessArticle Shape Memory Investigation of α-Keratin Fibers as Multi-Coupled Stimuli of Responsive Smart Materials
Polymers 2017, 9(3), 87; doi:10.3390/polym9030087
Received: 24 January 2017 / Accepted: 28 February 2017 / Published: 3 March 2017
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Abstract
Like the water responsive shape memory (SM) effect of β-keratin bird feathers, α-keratin hairs either existing broadly in nature are found responsive to many types of coupled stimuli in SM behaviors. In this article, α-keratin hairs were investigated for the combined stimuli of
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Like the water responsive shape memory (SM) effect of β-keratin bird feathers, α-keratin hairs either existing broadly in nature are found responsive to many types of coupled stimuli in SM behaviors. In this article, α-keratin hairs were investigated for the combined stimuli of thermo-solvent, solvent-solvent, and UV (radiation)-reductant sensitive SM abilities. The related netpoints and switches from the hair molecular networks were identified. The experimental results showed that α-keratin hairs manifested a higher ability of shape fixation under thermal stimulus followed with the stimuli of solvent and UV-radiation. Shape recovery from the hair with a temporarily fixed shape showed a higher recovery ability using solvent than the stimuli of heat and UV-radiation. The effects of coupled stimuli on hair’s shape fixation and recovery and on variations of the crystal, disulfide, and hydrogen bonds were studied systematically. A structural network model was thereafter proposed to interpret the multi-coupled stimuli sensitive SM of α-keratin hair. This original study is expected to provide inspiration for exploring other natural fibers to reveal related smart functions and for making more types of remarkable adapted synthetic materials. Full article
(This article belongs to the Special Issue Functionally Responsive Polymeric Materials)
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Open AccessArticle Competitive Stereocomplexation and Homocrystallization Behaviors in the Poly(lactide) Blends of PLLA and PDLA-PEG-PDLA with Controlled Block Length
Polymers 2017, 9(3), 107; doi:10.3390/polym9030107
Received: 18 January 2017 / Revised: 9 March 2017 / Accepted: 12 March 2017 / Published: 15 March 2017
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Abstract
Stereocomplex poly(lactide) (PLA) was obtained by solution blending of linear PLLA and PDLA-PEG-PDLA. Effects of the L/D ratios, PEG block, and PDLA block on stereocomplexation of the blends are systemically discussed. The full stereocomplex PLA can be acquired by solution blending when L/D
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Stereocomplex poly(lactide) (PLA) was obtained by solution blending of linear PLLA and PDLA-PEG-PDLA. Effects of the L/D ratios, PEG block, and PDLA block on stereocomplexation of the blends are systemically discussed. The full stereocomplex PLA can be acquired by solution blending when L/D ratios are in the range of 7/3–5/5. The experiment results demonstrated that the stereocomplex degree of PLLA/PDLA-PEG-PDLA prepared by melt blending was closely related to the PEG block and PDLA block. POM results indicated that the blends with high L/D ratio showed large disordered spherulites, and the typical Maltese cross pattern was observed as the L/D ratios decreased. The results of PEG block on the stereocomplexation of PLLA/PDLA-PEG-PDLA revealed that the PEG blocks possessed two sides: accelerating agent for the mobility of polymer chains and decreasing nucleation capacity due to their diluting effect. The effect of PDLA block on the stereocomplexation of the blends was also well investigated. The results showed that the crystallization of sc-crystallites and hc-crystallites in the PLLA/PDLA-PEG4k-PDLA blends with different PDLA blocks presents an obvious competition relationship, and this is not beneficial to the formation of sc-crystallites with increasing PDLA block. The melting behavior of PLLA/PDLA-PEG4k-PDLA with different PDLA blocks after isothermal crystallization showed that the blends could achieve full stereocomplex when the crystallization temperature exceeded 160 °C, and a crystallite with high perfection could be formed as the crystallization temperature increased. This study systemically investigated the effects of the L/D ratios, PEG block, PDLA block, and crystallization conditions on stereocomplex crystallization of PLLA/PDLA-PEG-PDLA blends, which can provide potential approaches to control the microstructure and physical performances of PLLA/PDLA-PEG-PDLA blends. Full article
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Open AccessArticle Programming of One- and Two-Step Stress Recovery in a Poly(ester urethane)
Polymers 2017, 9(3), 98; doi:10.3390/polym9030098
Received: 3 February 2017 / Revised: 6 March 2017 / Accepted: 6 March 2017 / Published: 10 March 2017
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Abstract
This work demonstrates that phase-segregated poly(ester urethane) (PEU) with switching segments of crystallizable poly(1,4-butylene adipate) (PBA) can be programmed to generate two separate stress recovery events upon heating under constant strain conditions. For programming, two elongations are applied at different temperatures, followed by
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This work demonstrates that phase-segregated poly(ester urethane) (PEU) with switching segments of crystallizable poly(1,4-butylene adipate) (PBA) can be programmed to generate two separate stress recovery events upon heating under constant strain conditions. For programming, two elongations are applied at different temperatures, followed by unloading and cooling. During the adjacent heating, two-step stress recovery is triggered. The results indicate that the magnitude of the stress recovery signals corresponds to the recovery of the two deformation stresses in reverse order. As demonstrated by further experiments, twofold stress recovery can be detected as long as the elongation at higher temperature exceeds the strain level of the deformation at lower temperature. Another finding includes that varying the lower deformation temperature enables a control over the stress recovery temperature and thus the implementation of so-called “temperature-memory effects”. Moreover, exerting only one elongation during programming enables a heating-initiated one-step stress recovery close to the deformation temperature. Based on these findings, such polymers may offer new technological opportunities in the fields of active assembly when used as fastening elements and in functional clothing when utilized for compression stockings. Full article
(This article belongs to the Special Issue Functionally Responsive Polymeric Materials)
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Open AccessArticle Chiral MnIII (Salen) Covalently Bonded on Modified ZPS-PVPA and ZPS-IPPA as Efficient Catalysts for Enantioselective Epoxidation of Unfunctionalized Olefins
Polymers 2017, 9(3), 108; doi:10.3390/polym9030108
Received: 7 February 2017 / Revised: 3 March 2017 / Accepted: 15 March 2017 / Published: 17 March 2017
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Abstract
Chiral MnIII (salen) complex supported on modified ZPS-PVPA (zirconium poly(styrene-phenylvinylphosphonate)) and ZPS-IPPA (zirconium poly(styrene-isopropenyl phosphonate)) were prepared using –CH2Cl as a reactive surface modifier by a covalent grafting method. The supported catalysts showed higher chiral induction (ee: 72%–83%) compared
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Chiral MnIII (salen) complex supported on modified ZPS-PVPA (zirconium poly(styrene-phenylvinylphosphonate)) and ZPS-IPPA (zirconium poly(styrene-isopropenyl phosphonate)) were prepared using –CH2Cl as a reactive surface modifier by a covalent grafting method. The supported catalysts showed higher chiral induction (ee: 72%–83%) compared with the corresponding homogeneous catalyst (ee: 54%) for asymmetric epoxidation of α-methylstrene in the presence of 4-phenylpyridine N-oxide (PPNO) as axial base using NaClO as an oxidant. ZPS-PVPA-based catalyst 1, with a larger pore diameter and surface area, was found to be more active than ZPS-IPPA-based catalyst 2. In addition, bulkier alkene-like indene, was efficiently epoxidized with these supported catalysts (ee: 96%–99%), the results were much higher than those for the homogeneous system (ee: 65%). Moreover, the prepared catalysts were relatively stable and can be recycled at least eight times without significant loss of activity and enantioselectivity. Full article
(This article belongs to the Special Issue Metal Complexes-Mediated Catalysis in Polymerization)
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Open AccessArticle Demixing by a Nematic Mean Field: Coarse-Grained Simulations of Liquid Crystalline Polymers
Polymers 2017, 9(3), 88; doi:10.3390/polym9030088
Received: 29 December 2016 / Accepted: 24 February 2017 / Published: 3 March 2017
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Abstract
Liquid crystalline polymers exhibit a particular richness of behaviors that stems from their rigidity and their macromolecular nature. On the one hand, the orientational interaction between liquid-crystalline motifs promotes their alignment, thereby leading to the emergence of nematic phases. On the other hand,
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Liquid crystalline polymers exhibit a particular richness of behaviors that stems from their rigidity and their macromolecular nature. On the one hand, the orientational interaction between liquid-crystalline motifs promotes their alignment, thereby leading to the emergence of nematic phases. On the other hand, the large number of configurations associated with polymer chains favors formation of isotropic phases, with chain stiffness becoming the factor that tips the balance. In this work, a soft coarse-grained model is introduced to explore the interplay of chain stiffness, molecular weight and orientational coupling, and their role on the isotropic-nematic transition in homopolymer melts. We also study the structure of polymer mixtures composed of stiff and flexible polymeric molecules. We consider the effects of blend composition, persistence length, molecular weight and orientational coupling strength on the melt structure at the nano- and mesoscopic levels. Conditions are found where the systems separate into two phases, one isotropic and the other nematic. We confirm the existence of non-equilibrium states that exhibit sought-after percolating nematic domains, which are of interest for applications in organic photovoltaic and electronic devices. Full article
(This article belongs to the Special Issue Semiflexible Polymers)
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Open AccessArticle Synthesis, Property Characterization and Photocatalytic Activity of the Polyaniline/BiYTi2O7 Polymer Composite
Polymers 2017, 9(3), 69; doi:10.3390/polym9030069
Received: 13 December 2016 / Revised: 1 February 2017 / Accepted: 9 February 2017 / Published: 23 February 2017
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Abstract
A new polyaniline/BiYTi2O7 polymer composite was synthesized by chemical oxidation in-situ polymerization method for the first time. The effect of polyaniline doping on structural and catalytic properties of BiYTi2O7 was reported. The structural properties of novel polyaniline/BiYTi
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A new polyaniline/BiYTi2O7 polymer composite was synthesized by chemical oxidation in-situ polymerization method for the first time. The effect of polyaniline doping on structural and catalytic properties of BiYTi2O7 was reported. The structural properties of novel polyaniline/BiYTi2O7 have been characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV-Vis DRS. The results showed that BiYTi2O7 crystallized well with the pyrochlore-type structure, stable cubic crystal system by space group Fd3m. The lattice parameter or band gap energy of BiYTi2O7 was found to be a = 10.2132 Å or 2.349 eV, respectively. The novel polyaniline/BiYTi2O7 polymer composite possessed higher catalytic activity compared with BiYTi2O7 or nitrogen doped TiO2 for photocatalytic degradation of Azocarmine G under visible light irradiation. Additionally, the Azocarmine G removal efficiency was boosted from 3.0% for undoped BiYTi2O7 to 78.0% for the 10% polyaniline-modified BiYTi2O7, after only 60 min of reaction. After visible light irradiation for 330 min with polyaniline/BiYTi2O7 polymer composite as photocatalyst, complete removal and mineralization of Azocarmine G was observed. The photocatalytic degradation of Azocarmine G followed first-order reaction kinetics. Ultimately, the promoter action of H2O2 for photocatalytic degradation of AG with BiYTi2O7 as catalyst in the wastewater was discovered. Full article
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Open AccessArticle Buckling a Semiflexible Polymer Chain under Compression
Polymers 2017, 9(3), 99; doi:10.3390/polym9030099
Received: 16 January 2017 / Revised: 2 March 2017 / Accepted: 3 March 2017 / Published: 11 March 2017
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Abstract
Instability and structural transitions arise in many important problems involving dynamics at molecular length scales. Buckling of an elastic rod under a compressive load offers a useful general picture of such a transition. However, the existing theoretical description of buckling is applicable in
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Instability and structural transitions arise in many important problems involving dynamics at molecular length scales. Buckling of an elastic rod under a compressive load offers a useful general picture of such a transition. However, the existing theoretical description of buckling is applicable in the load response of macroscopic structures, only when fluctuations can be neglected, whereas membranes, polymer brushes, filaments, and macromolecular chains undergo considerable Brownian fluctuations. We analyze here the buckling of a fluctuating semiflexible polymer experiencing a compressive load. Previous works rely on approximations to the polymer statistics, resulting in a range of predictions for the buckling transition that disagree on whether fluctuations elevate or depress the critical buckling force. In contrast, our theory exploits exact results for the statistical behavior of the worm-like chain model yielding unambiguous predictions about the buckling conditions and nature of the buckling transition. We find that a fluctuating polymer under compressive load requires a larger force to buckle than an elastic rod in the absence of fluctuations. The nature of the buckling transition exhibits a marked change from being distinctly second order in the absence of fluctuations to being a more gradual, compliant transition in the presence of fluctuations. We analyze the thermodynamic contributions throughout the buckling transition to demonstrate that the chain entropy favors the extended state over the buckled state, providing a thermodynamic justification of the elevated buckling force. Full article
(This article belongs to the Special Issue Semiflexible Polymers)
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Open AccessArticle The Influence of pH on the Melamine-Dimethylurea-Formaldehyde Co-Condensations: A Quantitative 13C-NMR Study
Polymers 2017, 9(3), 109; doi:10.3390/polym9030109
Received: 22 February 2017 / Revised: 13 March 2017 / Accepted: 15 March 2017 / Published: 17 March 2017
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Abstract
1,3-dimethylurea (DMU) was used to mimic urea and to model melamine-urea-formaldehyde (MUF) co-condensation reactions. The products of 1,3-dimethylurea-formaldehyde (DMUF), melamine-formaldehyde (MF), and melamine-1,3-dimethylurea-formaldehyde (MDMUF) reactions under alkaline and weak acidic conditions were compared by performing quantitative carbon-13 nuclear magnetic resonance (13C-NMR)
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1,3-dimethylurea (DMU) was used to mimic urea and to model melamine-urea-formaldehyde (MUF) co-condensation reactions. The products of 1,3-dimethylurea-formaldehyde (DMUF), melamine-formaldehyde (MF), and melamine-1,3-dimethylurea-formaldehyde (MDMUF) reactions under alkaline and weak acidic conditions were compared by performing quantitative carbon-13 nuclear magnetic resonance (13C-NMR) analysis. The effect of pH on the co-condensation reactions was clarified. With the presence of the methyl groups in DMU, the appearance or absence of the featured signal at 54–55 ppm can be used to identify the co-condensed methylene linkage –N(–CH3) –CH2–NH–. Under alkaline condition, MDMUF reactions produced primarily MF polymers and the featured signal at 54–55 ppm was absent. Even though the co-condensations concurrently occurred, undistinguishable and very minor condensed structures with ether linkage were formed. Differently, under weak acidic condition, the relative content of co-condensed methylene carbons accounts for over 40%, indicating the MDMUF co-condensation reactions were much more competitive than the self-condensations. The formation of reactive carbocation intermediate was proposed to rationalize the results. Full article
(This article belongs to the collection Polymeric Adhesives)
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Open AccessArticle RAFT Polymerization of Styrene and Maleimide in the Presence of Fluoroalcohol: Hydrogen Bonding Effects with Classical Alternating Copolymerization as Reference
Polymers 2017, 9(3), 89; doi:10.3390/polym9030089
Received: 23 January 2017 / Accepted: 1 March 2017 / Published: 3 March 2017
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Abstract
The impacts of hydrogen bonding on polymerization behavior has been of interest for a long time; however, universality and in-depth understanding are still lacking. For the first time, the effect of hydrogen bonding on the classical alternating-type copolymerization of styrene and maleimide was
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The impacts of hydrogen bonding on polymerization behavior has been of interest for a long time; however, universality and in-depth understanding are still lacking. For the first time, the effect of hydrogen bonding on the classical alternating-type copolymerization of styrene and maleimide was explored. N-phenylmaleimide (N-PMI)/styrene was chosen as a model monomer pair in the presence of hydrogen bonding donor solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), which interacted with N-PMI via hydrogen bonding. Reversible addition-fragmentation chain transfer polymerization (RAFT) technique was used to guarantee the “living” polymerization and thus the homogeneity of chain compositions. In comparison with the polymerization in nonhydrogen bonding donor solvent (toluene), the copolymerization in HFIP exhibited a high rate and a slight deviation from alternating copolymerization tendency. The reactivity ratios of N-PMI and St were revealed to be 0.078 and 0.068, respectively, while the reactivity ratios in toluene were 0.026 and 0.050. These interesting results were reasonably explained by using computer simulations, wherein the steric repulsion and electron induction by the hydrogen bonding between HFIP and NPMI were revealed. This work first elucidated the hydrogen bonding interaction in the classical alternating-type copolymerization, which will enrich the research on hydrogen bonding-induced polymerizations. Full article
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Open AccessCommunication Influence of Substituent Chain Branching on the Transfection Efficacy of Cyclopropenium-Based Polymers
Polymers 2017, 9(3), 79; doi:10.3390/polym9030079
Received: 6 January 2017 / Revised: 13 February 2017 / Accepted: 21 February 2017 / Published: 24 February 2017
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Abstract
The realization of gene therapy relies on the development of delivery vectors with high efficiency and biocompatibility. With a multitude of structures accessible, the core challenge is precisely tuning vector structure to probe and optimize structure–property relationships. Employing a modular strategy, two pairs
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The realization of gene therapy relies on the development of delivery vectors with high efficiency and biocompatibility. With a multitude of structures accessible, the core challenge is precisely tuning vector structure to probe and optimize structure–property relationships. Employing a modular strategy, two pairs of cationic polymers based on the trisaminocyclopropenium (TAC) ion were synthesized where the substituents differ in the degree of alkyl chain branching. All TAC-based polymers exhibited higher transfection efficiencies than the untreated controls, with variable in vitro toxicities. Considering both cytotoxicity and transfection efficacy, an optimal nonviral vector was identified. Our studies highlight the importance of exercising precise control over polymer structure, both in terms of backbone identity and substituent nature, and the necessity of a robust, modular platform from which to study them. Full article
(This article belongs to the Special Issue Young Talents in Polymer Science)
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Open AccessArticle Preparation of Microporous Polypropylene/Titanium Dioxide Composite Membranes with Enhanced Electrolyte Uptake Capability via Melt Extruding and Stretching
Polymers 2017, 9(3), 110; doi:10.3390/polym9030110
Received: 22 February 2017 / Revised: 16 March 2017 / Accepted: 16 March 2017 / Published: 17 March 2017
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Abstract
In this work, a blending strategy based on compounding the hydrophilic titanium dioxide (TiO2) particles with the host polypropylene (PP) pellets, followed by the common membrane manufacture process of melt extruding/annealing/stretching, was used to improve the polarity and thus electrolyte uptake
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In this work, a blending strategy based on compounding the hydrophilic titanium dioxide (TiO2) particles with the host polypropylene (PP) pellets, followed by the common membrane manufacture process of melt extruding/annealing/stretching, was used to improve the polarity and thus electrolyte uptake capability of the PP-based microporous membranes. The influence of the TiO2 particles on the crystallinity and crystalline orientation of the PP matrix was studied using differential scanning calorimetry (DSC), X-ray diffraction (XRD), and infrared dichroic methods. The results showed that the TiO2 incorporation has little influence on the oriented lamellar structure of the PP-based composite films. Investigations of the deformation behavior indicated that both the lamellar separation and interfacial debonding occurred when the PP/TiO2 composite films were subjected to uniaxial tensile stress. The scanning electron microscopy (SEM) observations verified that two forms of micropores were generated in the stretched PP/TiO2 composite membranes. Compared to the virgin PP membrane, the PP/TiO2 composite membranes especially at high TiO2 loadings showed significant improvements in terms of water vapor permeability, polarity, and electrolyte uptake capability. The electrolyte uptake of the PP/TiO2 composite membrane with 40 wt % TiO2 was 104%, which had almost doubled compared with that of the virgin PP membrane. Full article
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Open AccessArticle Reaction-Multi Diffusion Model for Nutrient Release and Autocatalytic Degradation of PLA-Coated Controlled-Release Fertilizer
Polymers 2017, 9(3), 111; doi:10.3390/polym9030111
Received: 15 December 2016 / Revised: 9 March 2017 / Accepted: 15 March 2017 / Published: 22 March 2017
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Abstract
A mathematical model for the reaction-diffusion equation is developed to describe the nutrient release profiles and degradation of poly(lactic acid) (PLA)-coated controlled-release fertilizer. A multi-diffusion model that consists of coupled partial differential equations is used to study the diffusion and chemical reaction (autocatalytic
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A mathematical model for the reaction-diffusion equation is developed to describe the nutrient release profiles and degradation of poly(lactic acid) (PLA)-coated controlled-release fertilizer. A multi-diffusion model that consists of coupled partial differential equations is used to study the diffusion and chemical reaction (autocatalytic degradation) simultaneously. The model is solved using an analytical-numerical method. Firstly, the model equation is transformed using the Laplace transformation as the Laplace transform cannot be inverted analytically. Numerical inversion of the Laplace transform is used by employing the Zakian method. The solution is useful in predicting the nutrient release profiles at various diffusivity, concentration of extraction medium, and reaction rates. It also helps in explaining the transformation of autocatalytic concentration in the coating material for various reaction rates, times of reaction, and reaction-multi diffusion. The solution is also applicable to the other biodegradable polymer-coated controlled-release fertilizers. Full article
(This article belongs to the Special Issue Biodegradable Polymers)
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Open AccessArticle Epoxy-Based Shape-Memory Actuators Obtained via Dual-Curing of Off-Stoichiometric “Thiol–Epoxy” Mixtures
Polymers 2017, 9(3), 113; doi:10.3390/polym9030113
Received: 14 February 2017 / Revised: 10 March 2017 / Accepted: 16 March 2017 / Published: 21 March 2017
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Abstract
In this work, epoxy-based shape-memory actuators have been developed by taking advantage of the sequential dual-curing of off-stoichiometric “thiol–epoxy” systems. Bent-shaped designs for flexural actuation were obtained thanks to the easy processing of these materials in the intermediate stage (after the first curing
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In this work, epoxy-based shape-memory actuators have been developed by taking advantage of the sequential dual-curing of off-stoichiometric “thiol–epoxy” systems. Bent-shaped designs for flexural actuation were obtained thanks to the easy processing of these materials in the intermediate stage (after the first curing process), and successfully fixed through the second curing process. The samples were programmed into a flat temporary-shape and the recovery-process was analyzed in unconstrained, partially-constrained and fully-constrained conditions using a dynamic mechanical analyzer (DMA). Different “thiol–epoxy” systems and off-stoichiometric ratios were used to analyze the effect of the network structure on the actuation performance. The results evidenced the possibility to take advantage of the flexural recovery as a potential actuator, the operation of which can be modulated by changing the network structure and properties of the material. Under unconstrained-recovery conditions, faster and narrower recovery-processes (an average speed up to 80%/min) are attained by using materials with homogeneous network structure, while in partially- or fully-constrained conditions, a higher crosslinking density and the presence of crosslinks of higher functionality lead to a higher amount of energy released during the recovery-process, thus, increasing the work or the force released. Finally, an easy approach for the prediction of the work released by the shape-memory actuator has been proposed. Full article
(This article belongs to the Special Issue Functionally Responsive Polymeric Materials)
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Open AccessArticle Applications of Three Dithienylpyrroles-Based Electrochromic Polymers in High-Contrast Electrochromic Devices
Polymers 2017, 9(3), 114; doi:10.3390/polym9030114
Received: 3 March 2017 / Revised: 16 March 2017 / Accepted: 20 March 2017 / Published: 22 March 2017
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Abstract
Three dithienylpyrroles (1-(4-(methylthio)phenyl)-2,5-di(thiophen-2-yl)-pyrrole (MPS), 1-(4-methoxyphenyl)-2,5-di(thiophen-2-yl)-pyrrole (MPO), and 4-(2,5-di(thiophen-2-yl)-pyrrol-1-yl)benzonitrile (ANIL)) were synthesized and their corresponding polydithienylpyrroles (PSNS) were electrosynthesized using electrochemical polymerization. Spectroelectrochemical studies indicated that poly(1-(4-(methylthio)phenyl)-2,5-di(thiophen-2-yl)-pyrrole) (PMPS) film was green, dark green, and brown in the neutral, oxidation, and highly oxidized state, respectively.
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Three dithienylpyrroles (1-(4-(methylthio)phenyl)-2,5-di(thiophen-2-yl)-pyrrole (MPS), 1-(4-methoxyphenyl)-2,5-di(thiophen-2-yl)-pyrrole (MPO), and 4-(2,5-di(thiophen-2-yl)-pyrrol-1-yl)benzonitrile (ANIL)) were synthesized and their corresponding polydithienylpyrroles (PSNS) were electrosynthesized using electrochemical polymerization. Spectroelectrochemical studies indicated that poly(1-(4-(methylthio)phenyl)-2,5-di(thiophen-2-yl)-pyrrole) (PMPS) film was green, dark green, and brown in the neutral, oxidation, and highly oxidized state, respectively. The incorporation of a MPS unit into the PSNS backbone gave rise to a darker color than those of the MPO and ANIL units in the highly oxidized state. The PMPS film showed higher ΔTmax (54.47% at 940 nm) than those of the PMPO (43.87% at 890 nm) and PANIL (44.63% at 950 nm) films in an ionic liquid solution. Electrochromic devices (ECDs) employing PMPS, PMPO, and PANIL as anodic layers and poly(3,4-(2,2-diethypropylenedioxy)thiophene)(PProDOT-Et2) as a cathodic layer were constructed. PMPO/PProDOT-Et2 ECD showed the highest ΔTmax (41.13%) and coloration efficiency (674.67 cm2·C1) at 626 nm, whereas PMPS/PProDOT-Et2 ECD displayed satisfactory ΔTmax (32.51%) and coloration efficiency (637.25 cm2·C1) at 590 nm. Repeated cyclic voltammograms of PMPS/PProDOT-Et2, PMPO/PProDOT-Et2, and PANIL/PProDOT-Et2 ECDs indicated that ECDs had satisfactory redox stability. Full article
(This article belongs to the Special Issue Electroactive Polymers and Gels)
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Review

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Open AccessReview Self-Assembled Organic Materials for Photovoltaic Application
Polymers 2017, 9(3), 112; doi:10.3390/polym9030112
Received: 23 January 2017 / Revised: 10 March 2017 / Accepted: 15 March 2017 / Published: 21 March 2017
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Abstract
Organic photovoltaic cells based on bulk-heterojunction architecture have been a topic of intense research for the past two decades. Recent reports on power conversion efficiency surpassing 10% suggest these devices are a viable low-cost choice for a range of applications where conventional silicon
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Organic photovoltaic cells based on bulk-heterojunction architecture have been a topic of intense research for the past two decades. Recent reports on power conversion efficiency surpassing 10% suggest these devices are a viable low-cost choice for a range of applications where conventional silicon solar cells are not suitable. Further improvements in efficiency could be achieved with the enhanced interaction between the donor and acceptor components. Effective utilization of supramolecular interactions to tailor and manipulate the communication between the components in the blend is a good strategy towards this end. Literature reports suggest that the long-term stability of organic solar cells, a major hurdle for commercial applications, can also be partially addressed by generating stable supramolecular nanostructures. In this review, we have made an attempt to summarize advances in small molecule, oligomer and polymer based systems, wherein supramolecular interactions such as hydrogen-bonding, pi-pi stacking, and dipole-dipole are explored for realizing stable and efficient bulk-heterojunction solar cells. Full article
(This article belongs to the Special Issue Organic Photovoltaics 2016)
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