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Polymers, Volume 9, Issue 2 (February 2017)

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Cover Story Combining two solutions of oppositely charged diblock copolymers with polyphosphobetaine led to the [...] Read more.
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Open AccessArticle Needleless Melt-Electrospinning of Biodegradable Poly(Lactic Acid) Ultrafine Fibers for the Removal of Oil from Water
Polymers 2017, 9(2), 3; doi:10.3390/polym9020003
Received: 1 December 2016 / Revised: 17 December 2016 / Accepted: 20 December 2016 / Published: 25 January 2017
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Abstract
As environmentally friendly and degradable material, Poly(lactic acid) (PLA) ultrafine fibers are promising candidates for the removal of oil from water. In this work, a self-established needleless melt-electrospinning process was used to produce PLA ultrafine fibers with diameters in the range of 800
[...] Read more.
As environmentally friendly and degradable material, Poly(lactic acid) (PLA) ultrafine fibers are promising candidates for the removal of oil from water. In this work, a self-established needleless melt-electrospinning process was used to produce PLA ultrafine fibers with diameters in the range of 800 nm–9 µm. In order to obtain ultrafine fibers, three types of hyperbranched polymers were respectively added into the melt for electrospinning. Effects of amount and molecular weight of the added hyperbranched polymers on average fiber diameter and its distribution, and contact angle were investigated. The prepared PLA ultrafine fibers exhibited superhydrophobicity with the contact angle as high as 156°, making it a potential candidate in marine oil spill recovery. The oil sorption capability of these fibers is as high as 159, 118, and 96 g/g for motor oil, crude oil, and diesel, respectively. Even after seven cycles of reuse, the fiber still maintained about 60% of its initial capacity of sorption. The kinetics of oil sorption in the film agrees very well with the pseudo-second-order kinetic model. This work is expected to promote the mass production and application of biodegradable PLA fibers in the treatment of marine oil spill pollution. Full article
(This article belongs to the Special Issue Polymeric Fibers)
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Open AccessArticle Improvement of Dielectric, Magnetic and Thermal Properties of OPEFB Fibre–Polycaprolactone Composite by Adding Ni–Zn Ferrite
Polymers 2017, 9(2), 12; doi:10.3390/polym9020012
Received: 1 November 2016 / Revised: 26 December 2016 / Accepted: 26 December 2016 / Published: 8 February 2017
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Abstract
The dielectric and magnetic behaviour and thermal properties of composites based on nickel–zinc ferrite (NZF) filler can be improved by the addition of various types of materials. Amongst others, ferrite–polymer composites have been subjected to a wide range of research, due to their
[...] Read more.
The dielectric and magnetic behaviour and thermal properties of composites based on nickel–zinc ferrite (NZF) filler can be improved by the addition of various types of materials. Amongst others, ferrite–polymer composites have been subjected to a wide range of research, due to their extensive applications: electromagnetic interference shielding, microwave absorption, electrodes and sensors. Currently, the interest in scientific and technical searches for the potential outcomes of ferrite–polymer materials due to their different uses in applications such as telecommunication applications, microwave devices and electromagnetic interference shielding has been growing stronger. The dielectric and magnetic behaviour and thermal properties for such composite materials depend on size, shape and the amount of filler addition. Nickel–zinc ferrite material was prepared using the conventional solid-state reaction technique. This study highlights the development of microwave-absorbing material from NZF by adding natural fibres, Oil Palm Empty Fruit Bunch (OPEFB) and polycaprolactone (PCL). OPEFB is considered in this study because it is a solid waste product of the oil palm milling process which is widely and cheaply available. The use of OPEFB in this product may save the environment from oil palm solid waste. A Thermal Hake blending machine was used in blending the powder structure of NZF + OPEFB + PCL, which made it homogeneous. These composites were characterized by the use of Fourier transform infrared (FTIR) spectrometry and scanning electron microscopy (SEM). The thermal degradation behaviour of the composites was analyzed using thermogravimetric analysis (TGA) and differential thermogravimetric (DTG) thermograms. The effective permittivity and effective permeability was obtained over a broad frequency range from 8 to 12 GHz at room temperature. It was observed that the values of effective permittivity and permeability increased as the content of NZF content increased. A rectangular waveguide connected to a microwave vector network analyser (PNA) (HP/Agilent model PNA E8364B) was employed in measuring the reflection coefficient S11 and transmission coefficient S21 parameters of composites for different percentages of NZF filler. This parameter was then used in calculating the microwave absorbing properties (dB). Full article
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Open AccessArticle Flexible Pressure Sensor Based on PVDF Nanocomposites Containing Reduced Graphene Oxide-Titania Hybrid Nanolayers
Polymers 2017, 9(2), 33; doi:10.3390/polym9020033
Received: 7 November 2016 / Revised: 19 December 2016 / Accepted: 13 January 2017 / Published: 26 January 2017
Cited by 1 | PDF Full-text (11792 KB) | HTML Full-text | XML Full-text
Abstract
A novel flexible nanocomposite pressure sensor with a tensile strength of about 47 MPa is fabricated in this work. Nanolayers of titanium dioxide (titania nanolayers, TNL) synthesized by hydrothermal method are used to reinforce the polyvinylidene fluoride (PVDF) by simple solution mixing. A
[...] Read more.
A novel flexible nanocomposite pressure sensor with a tensile strength of about 47 MPa is fabricated in this work. Nanolayers of titanium dioxide (titania nanolayers, TNL) synthesized by hydrothermal method are used to reinforce the polyvinylidene fluoride (PVDF) by simple solution mixing. A hybrid composite is prepared by incorporating the TNL (2.5 wt %) with reduced graphene oxide (rGO) (2.5 wt %) synthesized by improved graphene oxide synthesis to form a PVDF/rGO-TNL composite. A comparison between PVDF, PVDF/rGO (5 wt %), PVDF/TNL (5 wt %) and PVDF/rGO-TNL (total additives 5 wt %) samples are analyzed for their sensing, thermal and dielectric characteristics. The new shape of additives (with sharp morphology), good interaction and well distributed hybrid additives in the matrix increased the sensitivity by 333.46% at 5 kPa, 200.7% at 10.7 kPa and 246.7% at 17.6 kPa compared to the individual PVDF composite of TNL, confirming its possible application in fabricating low cost and light weight pressure sensing devices and electronic devices with reduced quantity of metal oxides. Increase in the β crystallinity percentage and removal of α phase for PVDF was detected for the hybrid composite and linked to the improvement in the mechanical properties. Tensile strength for the hybrid composite (46.91 MPa) was 115% higher than that of the neat polymer matrix. Improvement in the wettability and less roughness in the hybrid composites were observed, which can prevent fouling, a major disadvantage in many sensor applications. Full article
(This article belongs to the Special Issue Functionally Responsive Polymeric Materials)
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Open AccessArticle Methacrylate-Based Copolymers for Polymer Optical Fibers
Polymers 2017, 9(2), 34; doi:10.3390/polym9020034
Received: 28 November 2016 / Revised: 10 January 2017 / Accepted: 18 January 2017 / Published: 25 January 2017
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Abstract
Waveguides made of poly-methyl-methacrylate (PMMA) play a major role in the homogeneous distribution of display backlights as a matrix for solid-state dye lasers and polymer optical fibers (POFs). PMMA is favored because of its transparency in the visible spectrum, low price, and well-controlled
[...] Read more.
Waveguides made of poly-methyl-methacrylate (PMMA) play a major role in the homogeneous distribution of display backlights as a matrix for solid-state dye lasers and polymer optical fibers (POFs). PMMA is favored because of its transparency in the visible spectrum, low price, and well-controlled processability. Nevertheless, technical drawbacks, such as its limited temperature stability, call for new materials. In this work, the copolymerization technique is used to modify the properties of the corresponding homopolymers. The analytical investigation of fourteen copolymers made of methyl-methacrylate (MMA) or ethyl-methacrylate (EMA) as the basis monomer is summarized. Their polymerization behaviors are examined by NMR spectroscopy with subsequent copolymerization parameter evaluation according to Fineman-Ross and Kelen-Tüdös. Therefore, some r-parameter sets are shown to be capable of copolymerizations with very high conversions. The first applications as high-temperature resistant (HT) materials for HT-POFs are presented. Copolymers containing isobornyl-methacrylate (IBMA) as the comonomer are well-suited for this demanding application. Full article
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Open AccessArticle Influence of Biodegradable Polymer Properties on Antifouling Paints Activity
Polymers 2017, 9(2), 36; doi:10.3390/polym9020036
Received: 29 November 2016 / Revised: 17 January 2017 / Accepted: 20 January 2017 / Published: 25 January 2017
Cited by 1 | PDF Full-text (4122 KB) | HTML Full-text | XML Full-text
Abstract
The development of new antifouling paints requires understanding the parameters involved in antifouling activity and to develop new analytical tools for their evaluation. A series of biodegradable poly(ε-caprolactone-co-δ-valerolactone) copolymers varying by molecular weight and composition were synthesized, characterized and formulated as
[...] Read more.
The development of new antifouling paints requires understanding the parameters involved in antifouling activity and to develop new analytical tools for their evaluation. A series of biodegradable poly(ε-caprolactone-co-δ-valerolactone) copolymers varying by molecular weight and composition were synthesized, characterized and formulated as antifouling paints. The physico-chemical properties such as hydration, degradation, erosion and lixiviation of paints were studied. Microfouling (bacteria and microalgae) was observed by microscopic observations in a short delay, whereas macrofouling colonization was observed by visual inspection during one year. The antifouling activity of paints was modified by varying the composition and molecular weight of copolymer. The crystallinity appears to play a major role in antifouling activity, however the involvement of other properties such as hydration, degradation or erosion remains difficult to understand. Confocal laser scanning and scanning electron microscopes were used for the evaluation of antifouling paints. Results show that microalgae seem to be a pertinent indicator of antifouling activity. Full article
(This article belongs to the Special Issue Biodegradable Polymers)
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Open AccessArticle Polycondensation Resins by Flavonoid Tannins Reaction with Amines
Polymers 2017, 9(2), 37; doi:10.3390/polym9020037
Received: 6 December 2016 / Revised: 12 January 2017 / Accepted: 20 January 2017 / Published: 25 January 2017
Cited by 2 | PDF Full-text (4916 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Reaction of a condensed flavonoid tannin, namely mimosa tannin extract with a hexamethylene diamine, has been investigated. For that purpose, catechin was also used as a flavonoid model compound and treated in similar conditions. Solid-state cross-polarisation/magic-angle spinning (CP-MAS) carbon 13 nuclear magnetic resonance
[...] Read more.
Reaction of a condensed flavonoid tannin, namely mimosa tannin extract with a hexamethylene diamine, has been investigated. For that purpose, catechin was also used as a flavonoid model compound and treated in similar conditions. Solid-state cross-polarisation/magic-angle spinning (CP-MAS) carbon 13 nuclear magnetic resonance (13C NMR) and matrix assisted laser desorption ionisation time of flight (MALDI-ToF) mass spectroscopy studies revealed that polycondensation compounds leading to resins were obtained by the reaction of the amines with the phenolic hydroxy groups of the tannin. Simultaneously, a second reaction leading to the formation of ionic bonds between the two groups occurred. These new reactions have been shown to clearly lead to the reaction of several phenolic hydroxyl groups, and flavonoid unit oligomerisation, to form hardened resins. Full article
(This article belongs to the Special Issue Renewable Polymeric Adhesives)
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Open AccessArticle On the Pseudo Phase Diagram of Single Semi-Flexible Polymer Chains: A Flat-Histogram Monte Carlo Study
Polymers 2017, 9(2), 38; doi:10.3390/polym9020038
Received: 22 December 2016 / Revised: 17 January 2017 / Accepted: 19 January 2017 / Published: 25 January 2017
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Abstract
Local stiffness of polymer chains is instrumental in all structure formation processes of polymers, from crystallization of synthetic polymers to protein folding and DNA compactification. We present Stochastic Approximation Monte Carlo simulations—a type of flat-histogram Monte Carlo method—determining the density of states of
[...] Read more.
Local stiffness of polymer chains is instrumental in all structure formation processes of polymers, from crystallization of synthetic polymers to protein folding and DNA compactification. We present Stochastic Approximation Monte Carlo simulations—a type of flat-histogram Monte Carlo method—determining the density of states of a model class of single semi-flexible polymer chains, and, from this, their complete thermodynamic behavior. The chains possess a rich pseudo phase diagram as a function of stiffness and temperature, displaying non-trivial ground-state morphologies. This pseudo phase diagram also depends on chain length. Differences to existing pseudo phase diagrams of semi-flexible chains in the literature emphasize the fact that the mechanism of stiffness creation matters. Full article
(This article belongs to the Special Issue Semiflexible Polymers)
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Open AccessArticle Effects of Fumed Silica and Draw Ratio on Nanocomposite Polypropylene Fibers
Polymers 2017, 9(2), 41; doi:10.3390/polym9020041
Received: 1 December 2016 / Revised: 18 January 2017 / Accepted: 20 January 2017 / Published: 28 January 2017
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Abstract
Hydrophylic fumed silica AR974 was tested as a potential nanofiller for the production of composite isotactic polypropylene filaments/fibers (containing 0.25–2 vol % of nanoparticles) via melt compounding and subsequent hot drawing. The objectives of this study were as follows: (i) to investigate the
[...] Read more.
Hydrophylic fumed silica AR974 was tested as a potential nanofiller for the production of composite isotactic polypropylene filaments/fibers (containing 0.25–2 vol % of nanoparticles) via melt compounding and subsequent hot drawing. The objectives of this study were as follows: (i) to investigate the effects of the composition and the processing conditions on the microstructure and the thermal and mechanical properties of the produced fibers; (ii) to separate the effects of silica addition from those produced by fiber drawing; and (iii) to interpret the changes in the matrix molecular mobility (produced by silica and/or drawing). Scanning electron microscopy (SEM) evidenced a good dispersion of nanoparticles at fractions up to 0.5 vol % of the nanofiller. X-ray diffraction (XRD) analyses revealed the increase in crystallinity after drawing of both neat polypropylene (PP) and produced nanocomposite fibers. Consequently, tensile modulus and stress at break of the fibers were enhanced. Drawn fibers containing 0.25–0.5 vol % of nanofiller showed also a remarkable increase in the creep resistance. Loss modulus of drawn fibers showed a pronounced α-relaxation peak at about 65 °C; the higher the draw ratio, the higher the peak intensity. Thermal and mechanical properties of composite fibers were improved due to the combined effects of nanofiller reinforcement and fiber orientation produced during hot drawing. Both fumed silica and draw ratio were significantly effective on tensile modulus and tenacity of nanocomposite fibers up to 0.5 vol % of AR974. Full article
(This article belongs to the Special Issue Polymeric Fibers)
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Open AccessArticle Crystallization of Poly(ε-caprolactone) in Poly(vinylidene fluoride)/Poly(ε-caprolactone) Blend
Polymers 2017, 9(2), 42; doi:10.3390/polym9020042
Received: 10 December 2016 / Revised: 15 January 2017 / Accepted: 24 January 2017 / Published: 28 January 2017
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Abstract
The crystallization behavior of poly(ε-caprolactone) (PCL) in a poly(vinylidene fluoride) (PVDF)/PCL blend as well as on a highly orientated PVDF substrate was studied by means of POM, DSC and TEM. The results show that the miscibility of the PVDF/PCL blend and the spherulitic
[...] Read more.
The crystallization behavior of poly(ε-caprolactone) (PCL) in a poly(vinylidene fluoride) (PVDF)/PCL blend as well as on a highly orientated PVDF substrate was studied by means of POM, DSC and TEM. The results show that the miscibility of the PVDF/PCL blend and the spherulitic morphology of PVDF varies with the blend ratio. For all the compositions, the pre-existing PVDF crystals accelerated the crystallization of PCL because the PVDF exhibits very strong nucleation ability toward PCL as reflected by the occurrence of heteroepitaxy and the transcrystallization of PBA on the PVDF substrate. This is associated with the perfect lattice matching between the PBA and PVDF crystals. Full article
(This article belongs to the Special Issue Polymer Blends 2017)
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Open AccessArticle Ammoxidized Fenton-Activated Pine Kraft Lignin Accelerates Synthesis and Curing of Resole Resins
Polymers 2017, 9(2), 43; doi:10.3390/polym9020043
Received: 30 December 2016 / Revised: 19 January 2017 / Accepted: 22 January 2017 / Published: 28 January 2017
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Abstract
Ammoxidation of pine kraft lignin in aqueous 5 wt % ammonia affords a novel type of phenol substitute that significantly accelerates resole synthesis and curing as demonstrated for 40 wt % phenol replacement. Compared to non-ammoxidized lignin, which already shortens significantly the cooking
[...] Read more.
Ammoxidation of pine kraft lignin in aqueous 5 wt % ammonia affords a novel type of phenol substitute that significantly accelerates resole synthesis and curing as demonstrated for 40 wt % phenol replacement. Compared to non-ammoxidized lignin, which already shortens significantly the cooking time required to reach a resole viscosity of 1000 Pa·s (250 vs. 150 s) and reduces the typical curing B-time by about 25% at 100 °C, the use of ammoxidized lignin has an even more pronounced impact in this respect. Activation of lignin by Fenton-type oxidation prior to ammoxidation further boosts both synthesis and curing of the resole. This is presumably due to the intermediary formation of polyvalent cross-linkers like N,N,N-tris (methylol) trimethylene triamine triggered by saponification of a larger fraction of nitrogenous moieties present in such a treated lignin (ammonium salts, amide-type nitrogen, urea) and reaction of the released ammonia with formaldehyde. Except for the fact that phenol replacement by ammoxidized lignin results in a somewhat less brittle cured adhesive polymer and higher elastic modulus, the aforementioned acceleration in curing could no longer be observed in the presence of wood, where a significantly delayed wood-adhesive bond formation was observed for the lignin-containing adhesives as evident from the automated bonding evaluation system. Full article
(This article belongs to the Special Issue Renewable Polymeric Adhesives)
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Open AccessArticle Design of Dithiobenzoate RAFT Agent Bearing Hydroxyl Groups and Its Application in RAFT Polymerization for Telechelic Diol Polymers
Polymers 2017, 9(2), 44; doi:10.3390/polym9020044
Received: 30 December 2016 / Revised: 18 January 2017 / Accepted: 25 January 2017 / Published: 28 January 2017
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Abstract
RAFT polymerization is attractive for its reliability, facile operation, and high tolerance to a wide variety of monomers, functional groups, solvents, and temperatures. Herein, we report the RAFT-based synthesis of well-defined polymers bearing hydroxyl groups at two terminals by using various monomers. We
[...] Read more.
RAFT polymerization is attractive for its reliability, facile operation, and high tolerance to a wide variety of monomers, functional groups, solvents, and temperatures. Herein, we report the RAFT-based synthesis of well-defined polymers bearing hydroxyl groups at two terminals by using various monomers. We found that the molecular weight of obtained polymers was half that of a target value when a trithiocarbonate-type chain transfer agent (CTA) was used, suggesting that the polymers unexpectedly cleaved at the middle of the polymer chain as the reaction was proceeding. To address the problem, we synthesized a novel “dithiobenzoate”-type CTA, 2-[N-(2-hydroxyethyl)carbamoyl]prop-2-yl 4-hydroxydithiobenzoate (HECPHD), which bears hydroxyl groups at both terminals, and we succeeded in RAFT polymerization with various monomers without a cleavage of the polymers. Full article
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Open AccessArticle Theoretical Confirmation of the Quinone Methide Hypothesis for the Condensation Reactions in Phenol-Formaldehyde Resin Synthesis
Polymers 2017, 9(2), 45; doi:10.3390/polym9020045
Received: 20 December 2016 / Revised: 24 January 2017 / Accepted: 25 January 2017 / Published: 29 January 2017
Cited by 2 | PDF Full-text (2293 KB) | HTML Full-text | XML Full-text
Abstract
The mechanisms for the base-catalyzed condensation reactions in phenol-formaldehyde resin synthesis were investigated by using the density functional theory method. The structures of the intermediates and transition states, as well as the potential energy barriers of the involved reactions, were obtained. The hypothesis
[...] Read more.
The mechanisms for the base-catalyzed condensation reactions in phenol-formaldehyde resin synthesis were investigated by using the density functional theory method. The structures of the intermediates and transition states, as well as the potential energy barriers of the involved reactions, were obtained. The hypothesis of quinine methide (QM) formation was theoretically confirmed. Two mechanisms were identified for QM formation, namely E1cb (elimination unimolecular conjugate base) and water-aided intra-molecular water elimination. The latter is energetically more favorable and is proposed for the first time in this work. Based on the QM mechanism, the condensation should be a unimolecular reaction because the following condensation between an ionized species (dissociated phenol or hydroxymethylphenol) with QM is much faster. The previously proposed SN2 condensation mechanism was found to be not competitive over the QM mechanism due to a much higher energy barrier. The condensation reaction between neutral phenol or hydroxymethylphenol and QM was also found to be possible. The energy barrier of this reaction is close to or higher than that of QM formation. Therefore, the overall condensation reaction may appear to be bimolecular if such a reaction is incorporated. The theoretical calculations in this work rationalized the discrepant results reported in previous kinetics studies well. Full article
(This article belongs to the Special Issue Renewable Polymeric Adhesives)
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Open AccessArticle Study of Organosolv Lignins as Adhesives in Wood Panel Production
Polymers 2017, 9(2), 46; doi:10.3390/polym9020046
Received: 30 December 2016 / Revised: 20 January 2017 / Accepted: 26 January 2017 / Published: 29 January 2017
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Abstract
Organosolv lignins obtained from sugar maple bark and wood were studied as adhesives for wood particleboard production. Organosolv pulping of sugar maple wood and bark was carried out in the presence of Lewis acid FeCl3 as a catalyst. The organosolv lignins recovered
[...] Read more.
Organosolv lignins obtained from sugar maple bark and wood were studied as adhesives for wood particleboard production. Organosolv pulping of sugar maple wood and bark was carried out in the presence of Lewis acid FeCl3 as a catalyst. The organosolv lignins recovered from this process were investigated by determination of Klason plus acid-soluble lignin content, of sugars by HPLC analysis, and of ash content. Structural characterizations of these lignins were performed by Fourier-transform infrared (FT-IR) and by 31P NMR. The results of the latter studies indicate that the content of free phenolic groups was more important in bark than in wood lignin. The gel permeation chromatography (GPC) analyses results suggested that the weight-average molecular mass of wood lignin was higher than that of bark lignin. The studied organosolv lignins were used for the preparation of particleboards as recovered and in combination with glyoxal or isocyanate. It was found that sugar maple bark lignin, as such or modified with isocyanate, was a more efficient adhesive than its wood counterpart. On the contrary, it was the organosolv wood lignin combined with glyoxal which was a more efficient adhesive than its bark counterpart. In combination with isocyanate, it was the sugar maple bark organosolv lignin which was determined to have the best adhesive performance of all studied lignins. Full article
(This article belongs to the Special Issue Renewable Polymeric Adhesives)
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Open AccessArticle Effect of a Compatibilizer on the Morphology and Properties of Polypropylene/Polyethylentherephthalate Spun Fibers
Polymers 2017, 9(2), 47; doi:10.3390/polym9020047
Received: 6 December 2016 / Accepted: 26 January 2017 / Published: 2 February 2017
Cited by 1 | PDF Full-text (9974 KB) | HTML Full-text | XML Full-text
Abstract
Fibers spun by melt spinning of binary and ternary polypropylene/polyethylenetherephthalate blends have been produced and characterized in order to investigate the effect of a compatibilizer on their morphology and mechanical properties. The compatibilizer was a maleic anhydride-functionalized rubber copolymer. The effect of the
[...] Read more.
Fibers spun by melt spinning of binary and ternary polypropylene/polyethylenetherephthalate blends have been produced and characterized in order to investigate the effect of a compatibilizer on their morphology and mechanical properties. The compatibilizer was a maleic anhydride-functionalized rubber copolymer. The effect of the compatibilizer was well evident in the isotropic state, as the morphology became very fine, the size of the dispersed particles was very small, and the adhesion was better. The effect of the compatibilizer on the mechanical properties is very relevant, especially in the elongation at break. On the contrary, no relevant effect was observed in the anisotropic oriented fibers. Although the average diameter of the microfibrils of the dispersed phase of the compatibilized blend generated during the hot drawing was much smaller than that of the microfibrils of the same particles of the uncompatibilized blend, the mechanical properties were almost the same. This behavior has been attributed to the length of the smaller microfibrils of the ternary blends, which was lower that of the microfibrils of the binary blend. This has been explained in terms of reduced initial droplet size, and therefore of lesser possibility of stretching the droplets to very long fibrils in these samples. Full article
(This article belongs to the Special Issue Polymeric Fibers)
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Open AccessArticle Thermodynamics of a Compressible Maier-Saupe Model Based on the Self-Consistent Field Theory of Wormlike Polymer
Polymers 2017, 9(2), 48; doi:10.3390/polym9020048
Received: 20 December 2016 / Revised: 27 January 2017 / Accepted: 30 January 2017 / Published: 4 February 2017
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Abstract
This paper presents a theoretical formalism for describing systems of semiflexible polymers, which can have density variations due to finite compressibility and exhibit an isotropic-nematic transition. The molecular architecture of the semiflexible polymers is described by a continuum wormlike-chain model. The non-bonded interactions
[...] Read more.
This paper presents a theoretical formalism for describing systems of semiflexible polymers, which can have density variations due to finite compressibility and exhibit an isotropic-nematic transition. The molecular architecture of the semiflexible polymers is described by a continuum wormlike-chain model. The non-bonded interactions are described through a functional of two collective variables, the local density and local segmental orientation tensor. In particular, the functional depends quadratically on local density-variations and includes a Maier–Saupe-type term to deal with the orientational ordering. The specified density-dependence stems from a free energy expansion, where the free energy of an isotropic and homogeneous homopolymer melt at some fixed density serves as a reference state. Using this framework, a self-consistent field theory is developed, which produces a Helmholtz free energy that can be used for the calculation of the thermodynamics of the system. The thermodynamic properties are analysed as functions of the compressibility of the model, for values of the compressibility realizable in mesoscopic simulations with soft interactions and in actual polymeric materials. Full article
(This article belongs to the Special Issue Semiflexible Polymers)
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Open AccessArticle Polyion Complex Vesicles with Solvated Phosphobetaine Shells Formed from Oppositely Charged Diblock Copolymers
Polymers 2017, 9(2), 49; doi:10.3390/polym9020049
Received: 31 December 2016 / Revised: 24 January 2017 / Accepted: 30 January 2017 / Published: 4 February 2017
Cited by 2 | PDF Full-text (3860 KB) | HTML Full-text | XML Full-text
Abstract
Diblock copolymers consisting of a hydrophilic poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) block and either a cationic or anionic block were prepared from (3-(methacrylamido)propyl)trimethylammonium chloride (MAPTAC) or sodium 2-(acrylamido)-2-methylpropanesulfonate (AMPS). Polymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) radical polymerization using a PMPC macro-chain transfer
[...] Read more.
Diblock copolymers consisting of a hydrophilic poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) block and either a cationic or anionic block were prepared from (3-(methacrylamido)propyl)trimethylammonium chloride (MAPTAC) or sodium 2-(acrylamido)-2-methylpropanesulfonate (AMPS). Polymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) radical polymerization using a PMPC macro-chain transfer agent. The degree of polymerization for PMPC, cationic PMAPTAC, and anionic PAMPS blocks was 20, 190, and 196, respectively. Combining two solutions of oppositely charged diblock copolymers, PMPC-b-PMAPTAC and PMPC-b-PAMPS, led to the spontaneous formation of polyion complex vesicles (PICsomes). The PICsomes were characterized using 1H NMR, static abd dynamic light scattering, transmittance electron microscopy (TEM), and atomic force microscopy. Maximum hydrodynamic radius (Rh) for the PICsome was observed at a neutral charge balance of the cationic and anionic diblock copolymers. The Rh value and aggregation number (Nagg) of PICsomes in 0.1 M NaCl was 78.0 nm and 7770, respectively. A spherical hollow vesicle structure was observed in TEM images. The hydrodynamic size of the PICsomes increased with concentration of the diblock copolymer solutions before mixing. Thus, the size of the PICsomes can be controlled by selecting an appropriate preparation method. Full article
(This article belongs to the collection Polyelectrolytes)
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Open AccessArticle The Effect of Molar Mass and Charge Density on the Formation of Complexes between Oppositely Charged Polyelectrolytes
Polymers 2017, 9(2), 50; doi:10.3390/polym9020050
Received: 19 November 2016 / Revised: 11 January 2017 / Accepted: 19 January 2017 / Published: 4 February 2017
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Abstract
The interactions between model polyanions and polycations have been studied using frontal continuous capillary electrophoresis (FACCE) which allows the determination of binding stoichiometry and binding constant of the formed polyelectrolyte complex (PEC). In this work, the effect of the poly(l-lysine) (PLL)
[...] Read more.
The interactions between model polyanions and polycations have been studied using frontal continuous capillary electrophoresis (FACCE) which allows the determination of binding stoichiometry and binding constant of the formed polyelectrolyte complex (PEC). In this work, the effect of the poly(l-lysine) (PLL) molar mass on the interaction with statistical copolymers of acrylamide and 2-acrylamido-2-methyl-1-propanesulfonate (PAMAMPS) has been systematically investigated for different PAMAMPS chemical charge densities (15% and 100%) and different ionic strengths. The study of the ionic strength dependence of the binding constant allowed the determination of the total number of released counter-ions during the formation of the PEC, which can be compared to the total number of counter-ions initially condensed on the individual polyelectrolyte partners before the association. Interestingly, this fraction of released counter-ions, which was strongly dependent on the PLL molar mass, was almost independent of the PAMAMPS charge density. These findings are useful to predict the binding constant according to the molar mass and charge density of the polyelectrolyte partners. Full article
(This article belongs to the collection Polyelectrolytes)
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Open AccessArticle Hydrophilic Polyelectrolyte Multilayers Improve the ELISA System: Antibody Enrichment and Blocking Free
Polymers 2017, 9(2), 51; doi:10.3390/polym9020051
Received: 19 December 2016 / Revised: 17 January 2017 / Accepted: 24 January 2017 / Published: 12 February 2017
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Abstract
In this study, polyelectrolyte multilayers were fabricated on a polystyrene (PS) plate using a Layer-by-Layer (LbL) self-assembly technique. The resulting functional platform showed improved performance compared with conventional enzyme-linked immunosorbent assay (ELISA) systems. Poly(diallyldimethylammonium chloride) (PDDA) and poly(acrylic acid) (PAA) were used as
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In this study, polyelectrolyte multilayers were fabricated on a polystyrene (PS) plate using a Layer-by-Layer (LbL) self-assembly technique. The resulting functional platform showed improved performance compared with conventional enzyme-linked immunosorbent assay (ELISA) systems. Poly(diallyldimethylammonium chloride) (PDDA) and poly(acrylic acid) (PAA) were used as cationic and anionic polyelectrolytes. On the negatively-charged (PDDA/PAA)3 polyelectrolyte multilayers the hydrophilic PAA surface could efficiently decrease the magnitude of the noise signal, by inhibiting nonspecific adsorption even without blocking reagent adsorption. Moreover, the (PDDA/PAA)3 substrate covalently immobilized the primary antibody, greatly increasing the amount of primary antibody adsorption and enhancing the specific detection signal compared with a conventional PS plate. The calibration curve of the (PDDA/PAA)3 substrate showed a wide linear range, for concentrations from 0.033 to 33 nM, a large specific signal change, and a detection limit of 33 pM, even though the conventional blocking reagent adsorption step was omitted. The (PDDA/PAA)3 substrate provided a high-performance ELISA system with a simple fabrication process and high sensitivity; the system presented here shows potential for a variety of immunosensor applications. Full article
(This article belongs to the collection Polyelectrolytes)
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Open AccessArticle DFT Studies on cis-1,4-Polymerization of Dienes Catalyzed by a Cationic Rare-Earth Metal Complex Bearing an Ancillary PNP Ligand
Polymers 2017, 9(2), 53; doi:10.3390/polym9020053
Received: 17 December 2016 / Revised: 20 January 2017 / Accepted: 22 January 2017 / Published: 7 February 2017
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Abstract
Dnsity functional theory (DFT) calculations have been carried out for the highly selective cis-1,4-polymerization of butadiene catalyzed by a cationic rare-earth metal complex bearing an ancillary PNP ligand. It has been found that the chain initiation and propagation of butadiene polymerization occurs
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Dnsity functional theory (DFT) calculations have been carried out for the highly selective cis-1,4-polymerization of butadiene catalyzed by a cationic rare-earth metal complex bearing an ancillary PNP ligand. It has been found that the chain initiation and propagation of butadiene polymerization occurs via the favorable cis-1,4-insertion route. The trans-1,4 and 1,2-insertion are unfavorable both kinetically and thermodynamically. The chain growth follows the π-allyl-insertion mechanism. The analyses of energy decomposition of transition states indicate that the likelihood of rival insertion pathways is predominantly controlled by the interaction energy of butadiene with a metal center and the deformation energy of butadiene moiety. The electronic factor of the central metal has a decisive influence on the cis- vs. trans-insertion and the regioselectivity (cis-1,4- vs. cis-1,2-insertion) is mainly determined by steric hindrance. Tetrahydrofuran (THF) coordination made monomer insertion less favorable compared with THF-free case and had more noticeable impact on the trans-monomer insertion compared with the cis case. During the chain propagation, cis-insertion of monomer facilitates THF de-coordination and the THF molecule could therefore dissociate from the central metal. Full article
(This article belongs to the Special Issue Metal Complexes-Mediated Catalysis in Polymerization)
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Open AccessArticle Sustainable and Low Viscous 1-Allyl-3-methylimidazolium Acetate + PEG Solvent for Cellulose Processing
Polymers 2017, 9(2), 54; doi:10.3390/polym9020054
Received: 4 January 2017 / Revised: 3 February 2017 / Accepted: 4 February 2017 / Published: 16 February 2017
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Abstract
Developing sustainable, low viscous and efficient solvents are always advantageous to the processing/fabricating of cellulose materials in practical applications. To this end, in this work novel solvents were developed; ([Amim][CH3COO]/PEG) by dissolving polyethylene glycol 200 (PEG-200) in 1-allyl-3-methylimidazolium acetate ([Amim][CH3
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Developing sustainable, low viscous and efficient solvents are always advantageous to the processing/fabricating of cellulose materials in practical applications. To this end, in this work novel solvents were developed; ([Amim][CH3COO]/PEG) by dissolving polyethylene glycol 200 (PEG-200) in 1-allyl-3-methylimidazolium acetate ([Amim][CH3COO]). The solubilities of cellulose in [Amim][CH3COO]/PEG solvents were determined as a function of temperature, and the possible dissolution mechanism of cellulose in [Amim][CH3COO]/PEG solvent was investigated. The novel solvent exhibits outstanding advantages for good dissolution capacity of cellulose, such as low viscosity, negligible vapor pressure, and recycling capability. The [CH3COO] anion and the [Amim]+ cation of [Amim][CH3COO] in [Amim][CH3COO]/PEG-10 are the driving force for cellulose dissolution verified by the 13C NMR spectra. In addition, the regenerated cellulose films from [Amim][CH3COO]/PEG solvent were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and thermogravimetric analysis (TGA) to estimate their morphologies and structures. Full article
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Open AccessArticle Entropic Interactions between Two Knots on a Semiflexible Polymer
Polymers 2017, 9(2), 55; doi:10.3390/polym9020055
Received: 30 December 2016 / Revised: 27 January 2017 / Accepted: 31 January 2017 / Published: 9 February 2017
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Abstract
Two knots on a string can either be separated or intertwined, and may even pass through each other. At the microscopic scale, such transitions may occur spontaneously, driven by thermal fluctuations, and can be associated with a topological free energy barrier. In this
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Two knots on a string can either be separated or intertwined, and may even pass through each other. At the microscopic scale, such transitions may occur spontaneously, driven by thermal fluctuations, and can be associated with a topological free energy barrier. In this manuscript, we study the respective location of a trefoil ( 3 1 ) and a figure-eight ( 4 1 ) knot on a semiflexible polymer, which is parameterized to model dsDNA in physiological conditions. Two cases are considered: first, end monomers are grafted to two confining walls of varying distance. Free energy profiles and transition barriers are then compared to a subset of free chains, which contain exactly one 3 1 and one 4 1 knot. For the latter, we observe a small preference to form an intertwined state, which can be associated with an effective entropic attraction. However, the respective free energy barrier is so small that we expect transition events to occur spontaneously and frequently in polymers and DNA, which are highly knotted for sufficient strain lengths. Full article
(This article belongs to the Special Issue Semiflexible Polymers)
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Open AccessArticle A Biodegradable Microneedle Cuff for Comparison of Drug Effects through Perivascular Delivery to Balloon-Injured Arteries
Polymers 2017, 9(2), 56; doi:10.3390/polym9020056
Received: 5 January 2017 / Revised: 25 January 2017 / Accepted: 3 February 2017 / Published: 8 February 2017
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Abstract
Restenosis at a vascular anastomosis site is a major cause of graft failure and is difficult to prevent by conventional treatment. Perivascular drug delivery has advantages as drugs can be diffused to tunica media and subintima while minimizing the direct effect on endothelium.
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Restenosis at a vascular anastomosis site is a major cause of graft failure and is difficult to prevent by conventional treatment. Perivascular drug delivery has advantages as drugs can be diffused to tunica media and subintima while minimizing the direct effect on endothelium. This in vivo study investigated the comparative effectiveness of paclitaxel, sirolimus, and sunitinib using a perivascular biodegradable microneedle cuff. A total of 31 New Zealand white rabbits were used. Rhodamine was used to visualize drug distribution (n = 3). Sirolimus- (n = 7), sunitinib- (n = 7), and paclitaxel-loaded (n = 7) microneedle cuffs were placed at balloon-injured abdominal aortae and compared to drug-free cuffs (n = 7). Basic histological structures were not affected by microneedle devices, and vascular wall thickness of the device-only group was similar to that of normal artery. Quantitative analysis revealed significantly decreased neointima formation in all drug-treated groups (p < 0.001). However, the tunica media layer of the paclitaxel-treated group was significantly thinner than that of other groups and also showed the highest apoptotic ratio (p < 0.001). Proliferating cell nuclear antigen (PCNA)-positive cells were significantly reduced in all drug-treated groups. Sirolimus or sunitinib appeared to be more appropriate for microneedle devices capable of slow drug release because vascular wall thickness was minimally affected. Full article
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Open AccessArticle Trapping a Knot into Tight Conformations by Intra-Chain Repulsions
Polymers 2017, 9(2), 57; doi:10.3390/polym9020057
Received: 31 December 2016 / Revised: 7 February 2017 / Accepted: 8 February 2017 / Published: 10 February 2017
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Abstract
Knots can occur in biopolymers such as DNA and peptides. In our previous study, we systematically investigated the effects of intra-chain interactions on knots and found that long-range repulsions can surprisingly tighten knots. Here, we use this knowledge to trap a knot into
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Knots can occur in biopolymers such as DNA and peptides. In our previous study, we systematically investigated the effects of intra-chain interactions on knots and found that long-range repulsions can surprisingly tighten knots. Here, we use this knowledge to trap a knot into tight conformations in Langevin dynamics simulations. By trapping, we mean that the free energy landscape with respect to the knot size exhibits a potential well around a small knot size in the presence of long-range repulsions, and this potential can well lead to long-lived tight knots when its depth is comparable to or larger than thermal energy. We tune the strength of intra-chain repulsion such that a knot is weakly trapped. Driven by thermal fluctuations, the knot can escape from the trap and is then re-trapped. We find that the knot switches between tight and loose conformations—referred to as “knot breathing”. We use a Yukawa potential to model screened electrostatic interactions to explore the relevance of knot trapping and breathing in charged biopolymers. We determine the minimal screened length and the minimal strength of repulsion for knot trapping. We find that Coulomb-induced knot trapping is possible to occur in single-stranded DNA and peptides for normal ionic strengths. Full article
(This article belongs to the Special Issue Semiflexible Polymers)
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Open AccessArticle Visible Light-Induced Metal Free Surface Initiated Atom Transfer Radical Polymerization of Methyl Methacrylate on SBA-15
Polymers 2017, 9(2), 58; doi:10.3390/polym9020058
Received: 20 January 2017 / Revised: 7 February 2017 / Accepted: 8 February 2017 / Published: 10 February 2017
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Abstract
Surface-initiated atom transfer radical polymerization (SI-ATRP) is one of the most versatile techniques to modify the surface properties of materials. Recent developed metal-free SI-ATRP makes such techniques more widely applicable. Herein photo-induced metal-free SI-ATRP of methacrylates, such as methyl methacrylate, N-isopropanyl acrylamide,
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Surface-initiated atom transfer radical polymerization (SI-ATRP) is one of the most versatile techniques to modify the surface properties of materials. Recent developed metal-free SI-ATRP makes such techniques more widely applicable. Herein photo-induced metal-free SI-ATRP of methacrylates, such as methyl methacrylate, N-isopropanyl acrylamide, and N,N-dimethylaminoethyl methacrylate, on the surface of SBA-15 was reported to fabricate organic-inorganic hybrid materials. A SBA-15-based polymeric composite with an adjustable graft ratio was obtained. The structure evolution during the SI-ATRP modification of SBA-15 was monitored and verified by FT-IR, XPS, TGA, BET, and TEM. The obtained polymeric composite showed enhanced adsorption ability for the model compound toluene in aqueous conditions. This procedure provides a low-cost, readily available, and easy modification method to synthesize polymeric composites without the contamination of metal. Full article
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Open AccessArticle Mechanical and Electrical Properties of Sulfur-Containing Polymeric Materials Prepared via Inverse Vulcanization
Polymers 2017, 9(2), 59; doi:10.3390/polym9020059
Received: 5 December 2016 / Revised: 23 January 2017 / Accepted: 26 January 2017 / Published: 15 February 2017
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Abstract
Recently, new methods have been developed for the utilization of elemental sulfur as a feedstock for novel polymeric materials. One promising method is the inverse vulcanization, which is used to prepare polymeric structures derived from sulfur and divinyl comonomers. However, the mechanical and
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Recently, new methods have been developed for the utilization of elemental sulfur as a feedstock for novel polymeric materials. One promising method is the inverse vulcanization, which is used to prepare polymeric structures derived from sulfur and divinyl comonomers. However, the mechanical and electrical properties of the products are virtually unexplored. Hence, in the present study, we synthesized a 200 g scale of amorphous, hydrophobic as well as translucent, hyperbranched polymeric sulfur networks that provide a high thermal resistance (>220 °C). The polymeric material properties of these sulfur copolymers can be controlled significantly by varying the monomers as well as the feed content. The investigated comonomers are divinylbenzene (DVB) and 1,3-diisopropenylbenzene (DIB). Plastomers with low elastic content and high shape retention containing 12.5%–30% DVB as well as low viscose waxy plastomers with a high flow behavior containing a high DVB content of 30%–35% were obtained. Copolymers with 15%–30% DIB act, on the one hand, as thermoplastics and, on the other hand, as vitreous thermosets with a DIB of 30%–35%. Results of the thermogravimetric analysis (TGA), the dynamic scanning calorimetry (DSC) and mechanical characterization, such as stress–strain experiments and dynamic mechanical thermal analysis, are discussed with the outcome that they support the assumption of a polymeric cross-linked network structure in the form of hyper-branched polymers. Full article
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Open AccessArticle Novel Melt-Spun Polymer-Optical Poly(methyl methacrylate) Fibers Studied by Small-Angle X-ray Scattering
Polymers 2017, 9(2), 60; doi:10.3390/polym9020060
Received: 30 November 2016 / Revised: 6 February 2017 / Accepted: 8 February 2017 / Published: 13 February 2017
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Abstract
The structural properties of novel melt-spun polymer optical fibers (POFs) are investigated by small-angle X-ray scattering. The amorphous PMMA POFs were subjected to a rapid cooling in a water quench right after extrusion in order to obtain a radial refractive index profile. Four
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The structural properties of novel melt-spun polymer optical fibers (POFs) are investigated by small-angle X-ray scattering. The amorphous PMMA POFs were subjected to a rapid cooling in a water quench right after extrusion in order to obtain a radial refractive index profile. Four fiber samples were investigated with small-angle X-ray scattering (SAXS). The resulting distance-distribution functions obtained from the respective equatorial and meridional SAXS data exhibit a real-space correlation peak indicative of periodic cross-sectional and axial variations in the scattering density contrast. Simple model calculations demonstrate how the structural information contained particularly in the equatorial distance distribution function can be interpreted. The respective results are qualitatively verified for one of the fiber samples by comparison of the model curve with the measured SAXS data. Eventually, the study confirms that the cross-sectional variation of the (scattering-) density is the main reason for the formation of radial refractive-index profiles in the POFs. Full article
(This article belongs to the Special Issue Polymeric Fibers)
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Open AccessArticle Characterization of Comb-Shaped Copolymers by Multidetection SEC, DLS and SANS
Polymers 2017, 9(2), 61; doi:10.3390/polym9020061
Received: 13 October 2016 / Revised: 25 January 2017 / Accepted: 9 February 2017 / Published: 14 February 2017
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Abstract
PolyCarboxylate ether-based superplasticizers (PCEs) are a type of comb-shaped copolymers used as polymeric dispersants in cementitious materials. PCEs have a high degree of dispersity, which limits the suitability of conventional characterization techniques, such as Size Exclusion Chromatography (SEC). Properties of PCEs strongly depend
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PolyCarboxylate ether-based superplasticizers (PCEs) are a type of comb-shaped copolymers used as polymeric dispersants in cementitious materials. PCEs have a high degree of dispersity, which limits the suitability of conventional characterization techniques, such as Size Exclusion Chromatography (SEC). Properties of PCEs strongly depend on their molecular structure and a comprehensive characterization is needed to fully understand the structure–property relationships. PCEs with well-defined molecular structures were synthesized to study their solution conformation by SEC and scattering techniques. The combined use of SEC, dynamic light scattering and small-angle neutron scattering allowed us to demonstrate the validity of a scaling law describing the radius of gyration of comb-shaped copolymers as a function of their molecular structure. Moreover, we show that the use of SEC with standard calibration, although widely spread, is not adequate for PCEs. Full article
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Open AccessArticle Wide-Range Magnetoelectric Response on Hybrid Polymer Composites Based on Filler Type and Content
Polymers 2017, 9(2), 62; doi:10.3390/polym9020062
Received: 14 December 2016 / Revised: 16 January 2017 / Accepted: 9 February 2017 / Published: 14 February 2017
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Abstract
In order to obtain a wide-range magnetoelectric (ME) response on a ME nanocomposite that matches industry requirements, Tb0.3Dy0.7Fe1.92 (Terfenol-D)/CoFe2O4/P(VDF-TrFE) flexible films were produced by the solvent casting technique and their morphologic, piezoelectric, magnetic and magnetoelectric properties were investigated. The
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In order to obtain a wide-range magnetoelectric (ME) response on a ME nanocomposite that matches industry requirements, Tb0.3Dy0.7Fe1.92 (Terfenol-D)/CoFe2O4/P(VDF-TrFE) flexible films were produced by the solvent casting technique and their morphologic, piezoelectric, magnetic and magnetoelectric properties were investigated. The obtained composites revealed a high piezoelectric response (≈−18 pC·N−1) that is independent of the weight ratio between the fillers. In turn, the magnetic properties of the composites were influenced by the composite composition. It was found that the magnetization saturation values decreased with the increasing CoFe2O4 content (from 18.5 to 13.3 emu·g−1) while the magnetization and coercive field values increased (from 3.7 to 5.5 emu·g−1 and from 355.7 to 1225.2 Oe, respectively) with the increasing CoFe2O4 content. Additionally, the films showed a wide-range dual-peak ME response at room temperature with the ME coefficient increasing with the weight content of Terfenol-D, from 18.6 to 42.3 mV·cm−1·Oe−1. Full article
(This article belongs to the Special Issue Hybrid Polymeric Materials)
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Open AccessArticle Chemical Modification of Butyl Rubber with Maleic Anhydride via Nitroxide Chemistry and Its Application in Polymer Blends
Polymers 2017, 9(2), 63; doi:10.3390/polym9020063
Received: 24 November 2016 / Revised: 26 January 2017 / Accepted: 6 February 2017 / Published: 20 February 2017
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Abstract
Butyl rubber (isobutylene–isoprene–rubber, IIR) was functionalized in solution with a nitroxide moiety taking advantage of the unsaturations present in the isoprene units of IIR, and was further grafted with maleic anhydride (MA) or styrene–MA (SMA) to produce IIR-g-MA and IIR-g
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Butyl rubber (isobutylene–isoprene–rubber, IIR) was functionalized in solution with a nitroxide moiety taking advantage of the unsaturations present in the isoprene units of IIR, and was further grafted with maleic anhydride (MA) or styrene–MA (SMA) to produce IIR-g-MA and IIR-g-SMA. In one of the functionalization techniques used, the molecular structure of the IIR was preserved as the chain-breaking reactions are prevented from occurring. The resulting graft copolymers were tested as compatiblizers/impact modifiers blended with Nylon-6, and one of them was preliminarily tested as a coupling agent in the preparation of nanocomposites of IIR and an organo-clay. Blends of PA-6/IIR-g-MA exhibited a significant increase in impact resistance at increasing loads of the modified IIR, as well as a good rubber particle dispersion in the polyamide matrix. On the other hand, the performance of IIR-g-SMA as an impact modifier of PA, or as a coupling agent in the preparation of rubber-organoclay nanocomposites, is marginal. Full article
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Open AccessArticle Enhancement of Curcumin Bioavailability Using Nanocellulose Reinforced Chitosan Hydrogel
Polymers 2017, 9(2), 64; doi:10.3390/polym9020064
Received: 14 January 2017 / Revised: 3 February 2017 / Accepted: 7 February 2017 / Published: 15 February 2017
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Abstract
A unique biodegradable, superporous, swellable and pH sensitive nanocellulose reinforced chitosan hydrogel with dynamic mechanical properties was prepared for oral administration of curcumin. Curcumin, a less water-soluble drug was used due to the fact that the fast swellable, superporous hydrogel could release a
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A unique biodegradable, superporous, swellable and pH sensitive nanocellulose reinforced chitosan hydrogel with dynamic mechanical properties was prepared for oral administration of curcumin. Curcumin, a less water-soluble drug was used due to the fact that the fast swellable, superporous hydrogel could release a water-insoluble drug to a great extent. CO2 gas foaming was used to fabricate hydrogel as it eradicates using organic solvents. Field emission scanning electron microscope images revealed that the pore size significantly increased with the formation of widely interconnected porous structure in gas foamed hydrogels. The maximum compression of pure chitosan hydrogel was 25.9 ± 1 kPa and it increased to 38.4 ± 1 kPa with the introduction of 0.5% cellulose nanocrystals. In vitro degradation of hydrogels was found dependent on the swelling ratio and the amount of CNC of the hydrogel. All the hydrogels showed maximum swelling ratios greater than 300%. The 0.5% CNC-chitosan hydrogel showed the highest swelling ratio of 438% ± 11%. FTIR spectrum indicated that there is no interaction between drug and ingredients present in hydrogels. The drug release occurred in non-Fickian (anomalous) manner in simulated gastric medium. The drug release profiles of hydrogels are consistent with the data obtained from the swelling studies. After gas foaming of the hydrogel, the drug loading efficiency increased from 41% ± 2.4% to 50% ± 2.0% and release increased from 0.74 to 1.06 mg/L. The drug release data showed good fitting to Ritger-Peppas model. Moreover, the results revealed that the drug maintained its chemical activity after in vitro release. According to the results of this study, CNC reinforced chitosan hydrogel can be suggested to improve the bioavailability of curcumin for the absorption from stomach and upper intestinal tract. Full article
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Open AccessArticle Degradation of Polyester Polyurethane by Bacterial Polyester Hydrolases
Polymers 2017, 9(2), 65; doi:10.3390/polym9020065
Received: 1 November 2016 / Revised: 1 February 2017 / Accepted: 10 February 2017 / Published: 16 February 2017
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Abstract
Polyurethanes (PU) are widely used synthetic polymers. The growing amount of PU used industrially has resulted in a worldwide increase of plastic wastes. The related environmental pollution as well as the limited availability of the raw materials based on petrochemicals requires novel solutions
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Polyurethanes (PU) are widely used synthetic polymers. The growing amount of PU used industrially has resulted in a worldwide increase of plastic wastes. The related environmental pollution as well as the limited availability of the raw materials based on petrochemicals requires novel solutions for their efficient degradation and recycling. The degradation of the polyester PU Impranil DLN by the polyester hydrolases LC cutinase (LCC), TfCut2, Tcur1278 and Tcur0390 was analyzed using a turbidimetric assay. The highest hydrolysis rates were obtained with TfCut2 and Tcur0390. TfCut2 also showed a significantly higher substrate affinity for Impranil DLN than the other three enzymes, indicated by a higher adsorption constant K. Significant weight losses of the solid thermoplastic polyester PU (TPU) Elastollan B85A-10 and C85A-10 were detected as a result of the enzymatic degradation by all four polyester hydrolases. Within a reaction time of 200 h at 70 °C, LCC caused weight losses of up to 4.9% and 4.1% of Elastollan B85A-10 and C85A-10, respectively. Gel permeation chromatography confirmed a preferential degradation of the larger polymer chains. Scanning electron microscopy revealed cracks at the surface of the TPU cubes as a result of enzymatic surface erosion. Analysis by Fourier transform infrared spectroscopy indicated that the observed weight losses were a result of the cleavage of ester bonds of the polyester TPU. Full article
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Open AccessArticle Characterization of Responsive Hydrogel Nanoparticles upon Polyelectrolyte Complexation
Polymers 2017, 9(2), 66; doi:10.3390/polym9020066
Received: 10 January 2017 / Revised: 13 February 2017 / Accepted: 13 February 2017 / Published: 16 February 2017
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Abstract
Characterization of responsive hydrogels and their interaction with other molecules have significantly expanded our understanding of the functional materials. We here report on the response of poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAm-co-AAc) nanogels to the addition of the poly(allylamine hydrochloride)
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Characterization of responsive hydrogels and their interaction with other molecules have significantly expanded our understanding of the functional materials. We here report on the response of poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAm-co-AAc) nanogels to the addition of the poly(allylamine hydrochloride) (PAH) in aqueous dispersions. We find that the hydrodynamic radius and stability of nanogels are dependent on the PAH/nanogel stoichiometry. If the nanogel solution is titrated with very small aliquots of PAH, the nanogels decrease in radius until the equivalence point, followed by aggregation at suprastoichiometric PAH additions. Conversely, when titrated with large aliquots, the nanogel charge switches rapidly from anionic to cationic, and no aggregation is observed. This behavior correlates well with electrophoretic mobility measurements, which shows the nanogel charge transitioning from negative to positive upon PAH addition. The volume phase transition temperature (VPTT) of the nanogels is also measured to discover the effect of polyelectrolyte complexation on the deswelling thermodynamics. These data show that charge neutralization upon PAH addition decreases the VPTT of the nanogel at pH 6.5. However, if an excess amount of PAH is added to the nanogel solution, the VPTT shifts back to higher temperatures due to the formation of a net positive charge in the nanogel network. Full article
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Open AccessArticle Synthesis of Aggregation-Induced Emission-Active Conjugated Polymers Composed of Group 13 Diiminate Complexes with Tunable Energy Levels via Alteration of Central Element
Polymers 2017, 9(2), 68; doi:10.3390/polym9020068
Received: 27 December 2016 / Accepted: 13 February 2017 / Published: 16 February 2017
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Abstract
Conjugated polymers containing boron and gallium diiminate complexes were prepared with various electron-donating comonomers via pre- and post-complexation methods, respectively. From a comparison of emission quantum yields between solution and film states, it was seen that all polymers containing group 13 elements possessed
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Conjugated polymers containing boron and gallium diiminate complexes were prepared with various electron-donating comonomers via pre- and post-complexation methods, respectively. From a comparison of emission quantum yields between solution and film states, it was seen that all polymers containing group 13 elements possessed an aggregation-induced emission property. Additionally, the frontier orbital energies and the optical and electrochemical properties of the polymers can be tuned by altering a central element at the complex moieties as well as by changing a comonomer unit. In particular, it was demonstrated that the gallium atom can contribute to stabilizing the energy levels of the lowest unoccupied molecular orbitals, resulting in narrow band gaps of the conjugated polymers. This study presents the potential of gallium not only for preparing solid-state emissive conjugated polymers but also for fabricating low-band gap materials by employing the conjugated ligand. Full article
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Open AccessArticle Optical Properties and Amplified Spontaneous Emission of Novel MDMO-PPV/C500 Hybrid
Polymers 2017, 9(2), 71; doi:10.3390/polym9020071
Received: 25 January 2017 / Revised: 13 February 2017 / Accepted: 15 February 2017 / Published: 17 February 2017
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Abstract
The influence of the solvent nature on optical properties of poly[2-methoxy-5-3,7-dimethyloctyloxy-1,4-phenylenevinylene] (MDMO-PPV)/Coumarine 500 (C500) have been investigated. In addition, the amplified spontaneous emission (ASE) from MDMO-PPV and efficient energy transfer between the MDMO-PPV and C500 has been verified. The MDMO-PPV was dissolved in
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The influence of the solvent nature on optical properties of poly[2-methoxy-5-3,7-dimethyloctyloxy-1,4-phenylenevinylene] (MDMO-PPV)/Coumarine 500 (C500) have been investigated. In addition, the amplified spontaneous emission (ASE) from MDMO-PPV and efficient energy transfer between the MDMO-PPV and C500 has been verified. The MDMO-PPV was dissolved in aromatic and nonaromatic solvents, while the solution blending method was employed to prepare the MDMO-PPV:C500 hybrid. The quantum yield of the MDMO-PPV was found to increase with the reduction of a few factors such as polarity index of the solvent, absorption cross section (σa), emission cross section (σe), and extinction coefficient (εmax). The fluorescence spectra of the MDMO-PPV appears from two vibronic band transitions (0-0, 0-1) and the ASE occurs at 0-1 transition, which was verified by the ASE from MDMO-PPV. The MDMO-PPV in toluene exhibited the best ASE efficiency due to its high quantum yield compared with other solvents. Strong overlap between the absorption spectrum of MDMO-PPV and emission spectrum of C500 confirmed the efficient energy transfer between them. Moreover, the ASE for energy transfer of the MDMO-PPV:C500 hybrid was proved. Full article
(This article belongs to the Special Issue Polymer Blends 2017)
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Open AccessArticle Tailoring Copolymer Properties by Gradual Changes in the Distribution of the Chains Composition Using Semicontinuous Emulsion Polymerization
Polymers 2017, 9(2), 72; doi:10.3390/polym9020072
Received: 21 December 2016 / Revised: 31 January 2017 / Accepted: 13 February 2017 / Published: 22 February 2017
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Abstract
To design the properties of a copolymer using free radical polymerization, a semicontinuous process can be applied to vary the instantaneous copolymer composition along the conversion searching for a specific composition spectrum of copolymer chains, which can be termed as weight composition distribution
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To design the properties of a copolymer using free radical polymerization, a semicontinuous process can be applied to vary the instantaneous copolymer composition along the conversion searching for a specific composition spectrum of copolymer chains, which can be termed as weight composition distribution (WCD) of copolymer chains. Here, the styrene-n-butyl acrylate (S/BA) system was polymerized by means of a semicontinuous emulsion process, varying the composition of the comonomer feed to obtain forced composition copolymers (FCCs). Five different feeding profiles were used, searching for a scheme to obtain chains rich in S (looking for considerable modulus), and chains rich in BA (looking for large deformation) as a technique to achieve synergy in copolymer properties; the mechanostatic and dynamic characterization discloses the correspondence between WCD and the bulk properties. 1H-nuclear magnetic resonance (1H-NMR) analysis enabled the determination of the cumulative copolymer composition characterization, required to estimate the WCD. The static test (stress-strain) and dynamic mechanical analysis (DMA) were performed following normed procedures. This is the first report that shows very diverse mechanostatic performances of copolymers obtained using the same chemical system and global comonomer composition, forming a comprehensive failure envelope, even though the tests were carried out at the same temperature and cross head speed. The principles for synergic performance can be applied to controlled radical copolymerization, designing the composition variation in individual molecules along the conversion. Full article
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Open AccessArticle Polymer Conformation under Confinement
Polymers 2017, 9(2), 73; doi:10.3390/polym9020073
Received: 8 January 2017 / Revised: 28 January 2017 / Accepted: 13 February 2017 / Published: 20 February 2017
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Abstract
The conformation of polymer chains under confinement is investigated in intercalated polymer/layered silicate nanocomposites. Hydrophilic poly(ethylene oxide)/sodium montmorillonite, PEO/Na+-MMT, hybrids were prepared utilizing melt intercalation with compositions where the polymer chains are mostly within the ~1 nm galleries of the inorganic
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The conformation of polymer chains under confinement is investigated in intercalated polymer/layered silicate nanocomposites. Hydrophilic poly(ethylene oxide)/sodium montmorillonite, PEO/Na+-MMT, hybrids were prepared utilizing melt intercalation with compositions where the polymer chains are mostly within the ~1 nm galleries of the inorganic material. The polymer chains are completely amorphous in all compositions even at temperatures where the bulk polymer is highly crystalline. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) is utilized to investigate the conformation of the polymer chains over a broad range of temperatures from below to much higher than the bulk polymer melting temperature. A systematic increase of the gauche conformation relatively to the trans is found with decreasing polymer content both for the C–C and the C–O bonds that exist along the PEO backbone indicating that the severe confinement and the proximity to the inorganic surfaces results in a more disordered state of the polymer. Full article
(This article belongs to the Special Issue Hybrid Polymeric Materials)
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Open AccessArticle Enhanced Injection Molding Simulation of Advanced Injection Molds
Polymers 2017, 9(2), 77; doi:10.3390/polym9020077
Received: 13 January 2017 / Revised: 13 February 2017 / Accepted: 17 February 2017 / Published: 22 February 2017
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Abstract
The most time-consuming phase of the injection molding cycle is cooling. Cooling efficiency can be enhanced with the application of conformal cooling systems or high thermal conductivity copper molds. The conformal cooling channels are placed along the geometry of the injection-molded product, and
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The most time-consuming phase of the injection molding cycle is cooling. Cooling efficiency can be enhanced with the application of conformal cooling systems or high thermal conductivity copper molds. The conformal cooling channels are placed along the geometry of the injection-molded product, and thus they can extract more heat and heat removal is more uniform than in the case of conventional cooling systems. In the case of copper mold inserts, cooling channels are made by drilling and heat removal is facilitated by the high thermal conductivity coefficient of copper, which is several times that of steel. Designing optimal cooling systems is a complex process; a proper design requires injection molding simulations, but the accuracy of calculations depends on how precise the input parameters and boundary conditions are. In this study, three cooling circuit designs and three mold materials (Ampcoloy 940, 1.2311 (P20) steel, and MS1 steel) were used and compared using numerical methods. The effect of different mold designs and materials on cooling efficiency were examined using calculated and measured results. The simulation model was adjusted to the measurement results by considering the joint gap between the mold inserts. Full article
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Open AccessArticle Bond Performance of Sand Coated UHM CFRP Tendons in High Performance Concrete
Polymers 2017, 9(2), 78; doi:10.3390/polym9020078
Received: 30 December 2016 / Revised: 1 February 2017 / Accepted: 16 February 2017 / Published: 22 February 2017
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Abstract
The bond behaviour of novel, sand-coated ultra-high modulus (UHM) carbon fibre reinforced polymers (CFRP) tendons to high performance concrete (HPC) was studied by a combined numerical and experimental approach. A series of pull-out tests revealed that the failure type can vary between sudden
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The bond behaviour of novel, sand-coated ultra-high modulus (UHM) carbon fibre reinforced polymers (CFRP) tendons to high performance concrete (HPC) was studied by a combined numerical and experimental approach. A series of pull-out tests revealed that the failure type can vary between sudden and continuous pull-out depending on the chosen sand coating grain size. Measuring the same shear stress vs. tendon draw-in (τ-δ) curves in the same test set-up, for sand coated CFRP tendons with a longitudinal stiffness of 137 and 509 GPa, respectively, indicated that the absolute bond strength in both cases was not influenced by the tendon’s stiffness. However, the τ-δ curves significantly differed in terms of the draw-in rate, showing higher draw-in rate for the UHM CFRP tendon. With the aid of X-ray computed tomography (CT), scanning electron microscopy (SEM) and visual analysis methods, the bond failure interface was located between the CFRP tendon and the surrounding sand-epoxy layer. For further investigation, a simplified finite element analysis (FEA) of the tendon pull-out was performed using a cohesive surface interaction model and the software Abaqus 6.14. A parametric study, varying the tendon-related material properties, revealed the tendon’s longitudinal stiffness to be the only contributor to the difference in the τ-δ curves found in the experiments, thus to the shear stress transfer behaviour between the CFRP tendon and the concrete. In conclusion, the excellent bond of the sand-coated UHM CFRP tendons to HPC as well as the deeper insight in the bond failure mechanism encourages the application of UHM CFRP tendons for prestressing applications. Full article
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Review

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Open AccessReview Bulk Heterojunction Solar Cells Based on Blends of Conjugated Polymers with II–VI and IV–VI Inorganic Semiconductor Quantum Dots
Polymers 2017, 9(2), 35; doi:10.3390/polym9020035
Received: 15 October 2016 / Revised: 16 January 2017 / Accepted: 18 January 2017 / Published: 26 January 2017
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Abstract
Bulk heterojunction solar cells based on blends of quantum dots and conjugated polymers are a promising configuration for obtaining high-efficiency, cheaply fabricated solution-processed photovoltaic devices. Such devices are of significant interest as they have the potential to leverage the advantages of both types
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Bulk heterojunction solar cells based on blends of quantum dots and conjugated polymers are a promising configuration for obtaining high-efficiency, cheaply fabricated solution-processed photovoltaic devices. Such devices are of significant interest as they have the potential to leverage the advantages of both types of materials, such as the high mobility, band gap tunability and possibility of multiple exciton generation in quantum dots together with the high mechanical flexibility and large molar extinction coefficient of conjugated polymers. Despite these advantages, the power conversion efficiency (PCE) of these hybrid devices has remained relatively low at around 6%, well behind that of all-organic or all-inorganic solar cells. This is attributed to major challenges that still need to be overcome before conjugated polymer–quantum dot blends can be considered viable for commercial application, such as controlling the film morphology and interfacial structure to ensure efficient charge transfer and charge transport. In this work, we present our findings with respect to the recent development of bulk heterojunctions made from conjugated polymer–quantum dot blends, list the ongoing strategies being attempted to improve performance, and highlight the key areas of research that need to be pursued to further develop this technology. Full article
(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)
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Open AccessReview Recent Development on Narrow Bandgap Conjugated Polymers for Polymer Solar Cells
Polymers 2017, 9(2), 39; doi:10.3390/polym9020039
Received: 27 December 2016 / Revised: 20 January 2017 / Accepted: 23 January 2017 / Published: 28 January 2017
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Abstract
There have been exciting developments in the field of polymer solar cells (PSCs) as the potential competitor to the traditional silicon-based solar cells in the past decades. The most successful PSCs are based on the bulk hetero-junction (BHJ) structure, which contains a bicontinuous
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There have been exciting developments in the field of polymer solar cells (PSCs) as the potential competitor to the traditional silicon-based solar cells in the past decades. The most successful PSCs are based on the bulk hetero-junction (BHJ) structure, which contains a bicontinuous nanoscale interpenetrating network of a conjugated polymer and a fullerene blend. The power conversion efficiencies (PCEs) of BHJ PSCs have now exceeded 11%. In this review, we present an overview of recent emerging developments of narrow bandgap conjugated polymers for PSCs. We focus on a few important acceptors used in the donor-acceptor type conjugated polymers for highly efficient PSCs. We also reviewed the emerged donor-π-acceptor (D-π-A) side chains polymers. The band-gaps and energy levels as well as the photovoltaic performances of conjugated polymers are discussed. Full article
(This article belongs to the Special Issue Organic Photovoltaics 2016)
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Open AccessReview Engineering Cell Surfaces with Polyelectrolyte Materials for Translational Applications
Polymers 2017, 9(2), 40; doi:10.3390/polym9020040
Received: 11 December 2016 / Revised: 18 January 2017 / Accepted: 19 January 2017 / Published: 28 January 2017
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Abstract
Engineering cell surfaces with natural or synthetic materials is a unique and powerful strategy for biomedical applications. Cells exhibit more sophisticated migration, control, and functional capabilities compared to nanoparticles, scaffolds, viruses, and other engineered materials or agents commonly used in the biomedical field.
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Engineering cell surfaces with natural or synthetic materials is a unique and powerful strategy for biomedical applications. Cells exhibit more sophisticated migration, control, and functional capabilities compared to nanoparticles, scaffolds, viruses, and other engineered materials or agents commonly used in the biomedical field. Over the past decade, modification of cell surfaces with natural or synthetic materials has been studied to exploit this complexity for both fundamental and translational goals. In this review we present the existing biomedical technologies for engineering cell surfaces with one important class of materials, polyelectrolytes. We begin by introducing the challenges facing the cell surface engineering field. We then discuss the features of polyelectrolytes and how these properties can be harnessed to solve challenges in cell therapy, tissue engineering, cell-based drug delivery, sensing and tracking, and immune modulation. Throughout the review, we highlight opportunities to drive the field forward by bridging new knowledge of polyelectrolytes with existing translational challenges. Full article
(This article belongs to the collection Polyelectrolytes)
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Open AccessReview Theory of Semiflexible Filaments and Networks
Polymers 2017, 9(2), 52; doi:10.3390/polym9020052
Received: 31 December 2016 / Revised: 25 January 2017 / Accepted: 26 January 2017 / Published: 5 February 2017
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Abstract
We briefly review the recent developments in the theory of individual semiflexible filaments, and of a crosslinked network of such filaments, both permanent and transient. Starting from the free energy of an individual semiflexible chain, models on its force-extension relation and other mechanical
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We briefly review the recent developments in the theory of individual semiflexible filaments, and of a crosslinked network of such filaments, both permanent and transient. Starting from the free energy of an individual semiflexible chain, models on its force-extension relation and other mechanical properties such as Euler buckling are discussed. For a permanently crosslinked network of filaments, theories on how the network responds to deformation are provided, with a focus on continuum approaches. Characteristic features of filament networks, such as nonlinear stress-strain relation, negative normal stress, tensegrity, and marginal stability are discussed. In the new area of transient filament network, where the crosslinks can be dynamically broken and re-formed, we show some recent attempts for understanding the dynamics of the crosslinks, and the related rheological properties, such as stress relaxation, yield stress and plasticity. Full article
(This article belongs to the Special Issue Semiflexible Polymers)
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Open AccessReview Polymers in Carbon Dots: A Review
Polymers 2017, 9(2), 67; doi:10.3390/polym9020067
Received: 28 December 2016 / Accepted: 9 February 2017 / Published: 16 February 2017
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Abstract
Carbon dots (CDs) have been widely studied since their discovery in 2004 as a green substitute of the traditional quantum dots due to their excellent photoluminescence (PL) and high biocompatibility. Meanwhile, polymers have increasingly become an important component for both synthesis and modification
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Carbon dots (CDs) have been widely studied since their discovery in 2004 as a green substitute of the traditional quantum dots due to their excellent photoluminescence (PL) and high biocompatibility. Meanwhile, polymers have increasingly become an important component for both synthesis and modification of CDs to provide polymeric matrix and enhance their PL property. Furthermore, critical analysis of composites of CDs and polymers has not been available. Herein, in this review, we summarized the use of polymers in the synthesis and functionalization of CDs, and the applications of these CDs in various fields. Full article
(This article belongs to the Special Issue Renewable Polymeric Adhesives)
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Open AccessReview Bio-Based Adhesives and Evaluation for Wood Composites Application
Polymers 2017, 9(2), 70; doi:10.3390/polym9020070
Received: 31 December 2016 / Revised: 7 February 2017 / Accepted: 10 February 2017 / Published: 17 February 2017
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Abstract
There has been a rapid growth in research and innovation of bio-based adhesives in the engineered wood product industry. This article reviews the recent research published over the last few decades on the synthesis of bio-adhesives derived from such renewable resources as lignin,
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There has been a rapid growth in research and innovation of bio-based adhesives in the engineered wood product industry. This article reviews the recent research published over the last few decades on the synthesis of bio-adhesives derived from such renewable resources as lignin, starch, and plant proteins. The chemical structure of these biopolymers is described and discussed to highlight the active functional groups that are used in the synthesis of bio-adhesives. The potentials and drawbacks of each biomass are then discussed in detail; some methods have been suggested to modify their chemical structures and to improve their properties including water resistance and bonding strength for their ultimate application as wood adhesives. Moreover, this article includes discussion of techniques commonly used for evaluating the petroleum-based wood adhesives in terms of mechanical properties and penetration behavior, which are expected to be more widely applied to bio-based wood adhesives to better evaluate their prospect for wood composites application. Full article
(This article belongs to the Special Issue Renewable Polymeric Adhesives)
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Open AccessReview Theoretical Methods for Studying DNA Structural Transitions under Applied Mechanical Constraints
Polymers 2017, 9(2), 74; doi:10.3390/polym9020074
Received: 6 January 2017 / Accepted: 14 February 2017 / Published: 21 February 2017
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Abstract
Recent progress in single-molecule manipulation technologies has made it possible to exert force and torque on individual DNA biopolymers to probe their mechanical stability and interaction with various DNA-binding proteins. It was revealed in these experiments that the DNA structure and formation of
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Recent progress in single-molecule manipulation technologies has made it possible to exert force and torque on individual DNA biopolymers to probe their mechanical stability and interaction with various DNA-binding proteins. It was revealed in these experiments that the DNA structure and formation of nucleoprotein complexes by DNA-architectural proteins can be strongly modulated by an intricate interplay between the entropic elasticity of DNA and its global topology, which is closely related to the mechanical constraints applied to the DNA. Detailed understanding of the physical processes underlying the DNA behavior observed in single-molecule experiments requires the development of a general theoretical framework, which turned out to be a rather challenging task. Here, we review recent advances in theoretical methods that can be used to interpret single-molecule manipulation experiments on DNA. Full article
(This article belongs to the Special Issue Semiflexible Polymers)
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Open AccessReview Nanocarbons in Electrospun Polymeric Nanomats for Tissue Engineering: A Review
Polymers 2017, 9(2), 76; doi:10.3390/polym9020076
Received: 23 December 2016 / Accepted: 17 February 2017 / Published: 21 February 2017
Cited by 6 | PDF Full-text (6696 KB) | HTML Full-text | XML Full-text
Abstract
Electrospinning is a versatile process technology, exploited for the production of fibers with varying diameters, ranging from nano- to micro-scale, particularly useful for a wide range of applications. Among these, tissue engineering is particularly relevant to this technology since electrospun fibers offer topological
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Electrospinning is a versatile process technology, exploited for the production of fibers with varying diameters, ranging from nano- to micro-scale, particularly useful for a wide range of applications. Among these, tissue engineering is particularly relevant to this technology since electrospun fibers offer topological structure features similar to the native extracellular matrix, thus providing an excellent environment for the growth of cells and tissues. Recently, nanocarbons have been emerging as promising fillers for biopolymeric nanofibrous scaffolds. In fact, they offer interesting physicochemical properties due to their small size, large surface area, high electrical conductivity and ability to interface/interact with the cells/tissues. Nevertheless, their biocompatibility is currently under debate and strictly correlated to their surface characteristics, in terms of chemical composition, hydrophilicity and roughness. Among the several nanofibrous scaffolds prepared by electrospinning, biopolymer/nanocarbons systems exhibit huge potential applications, since they combine the features of the matrix with those determined by the nanocarbons, such as conductivity and improved bioactivity. Furthermore, combining nanocarbons and electrospinning allows designing structures with engineered patterns at both nano- and microscale level. This article presents a comprehensive review of various types of electrospun polymer-nanocarbon currently used for tissue engineering applications. Furthermore, the differences among graphene, carbon nanotubes, nanodiamonds and fullerenes and their effect on the ultimate properties of the polymer-based nanofibrous scaffolds is elucidated and critically reviewed. Full article
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