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Polymers, Volume 8, Issue 12 (December 2016)

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Cover Story After the exciton is created due to photoexcitation in the conjugated polymer, the dipole moment [...] Read more.
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Open AccessArticle Core/Shell Conjugated Polymer/Quantum Dot Composite Nanofibers through Orthogonal Non-Covalent Interactions
Polymers 2016, 8(12), 408; doi:10.3390/polym8120408
Received: 3 October 2016 / Revised: 21 November 2016 / Accepted: 22 November 2016 / Published: 24 November 2016
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Abstract
Nanostructuring organic polymers and organic/inorganic hybrid materials and controlling blend morphologies at the molecular level are the prerequisites for modern electronic devices including biological sensors, light emitting diodes, memory devices and solar cells. To achieve all-around high performance, multiple organic and inorganic entities,
[...] Read more.
Nanostructuring organic polymers and organic/inorganic hybrid materials and controlling blend morphologies at the molecular level are the prerequisites for modern electronic devices including biological sensors, light emitting diodes, memory devices and solar cells. To achieve all-around high performance, multiple organic and inorganic entities, each designed for specific functions, are commonly incorporated into a single device. Accurate arrangement of these components is a crucial goal in order to achieve the overall synergistic effects. We describe here a facile methodology of nanostructuring conjugated polymers and inorganic quantum dots into well-ordered core/shell composite nanofibers through cooperation of several orthogonal non-covalent interactions including conjugated polymer crystallization, block copolymer self-assembly and coordination interactions. Our methods provide precise control on the spatial arrangements among the various building blocks that are otherwise incompatible with one another, and should find applications in modern organic electronic devices such as solar cells. Full article
(This article belongs to the Special Issue Conjugated Polymers 2016)
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Open AccessArticle What Happens When Threading is Suppressed in Blends of Ring and Linear Polymers?
Polymers 2016, 8(12), 409; doi:10.3390/polym8120409
Received: 27 October 2016 / Revised: 15 November 2016 / Accepted: 18 November 2016 / Published: 25 November 2016
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Abstract
Self-diffusivity of a large tracer ring polymer, Dr, immersed in a matrix of linear polymers with Nl monomers each shows unusual length dependence. Dr initially increases, and then decreases with increasing Nl. To understand the relationship between
[...] Read more.
Self-diffusivity of a large tracer ring polymer, D r , immersed in a matrix of linear polymers with N l monomers each shows unusual length dependence. D r initially increases, and then decreases with increasing N l . To understand the relationship between the nonmonotonic variation in D r and threading by matrix chains, we perform equilibrium Monte Carlo simulations of ring-linear blends in which the uncrossability of ring and linear polymer contours is switched on (non-crossing), or artificially turned off (crossing). The D r 6 . 2 × 10 7 N l 2 / 3 obtained from the crossing simulations, provides an upper bound for the D r obtained for the regular, non-crossing simulations. The center-of-mass mean-squared displacement ( g 3 ( t ) ) curves for the crossing simulations are consistent with the Rouse model; we find g 3 ( t ) = 6 D r t . Analysis of the polymer structure indicates that the smaller matrix chains are able to infiltrate the space occupied by the ring probe more effectively, which is dynamically manifested as a larger frictional drag per ring monomer. Full article
(This article belongs to the Special Issue Semiflexible Polymers)
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Open AccessArticle Microfluidic Synthesis of Actuating Microparticles from a Thiol-Ene Based Main-Chain Liquid Crystalline Elastomer
Polymers 2016, 8(12), 410; doi:10.3390/polym8120410
Received: 17 October 2016 / Revised: 10 November 2016 / Accepted: 16 November 2016 / Published: 25 November 2016
Cited by 1 | PDF Full-text (2123 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
In this article the microfluidic synthesis of strongly actuating particles on the basis of a liquid crystalline main-chain elastomer is presented. The synthesis is carried out in a capillary-based co-flow microreactor by photo-initiated thiol-ene click chemistry of a liquid crystalline monomer mixture. These
[...] Read more.
In this article the microfluidic synthesis of strongly actuating particles on the basis of a liquid crystalline main-chain elastomer is presented. The synthesis is carried out in a capillary-based co-flow microreactor by photo-initiated thiol-ene click chemistry of a liquid crystalline monomer mixture. These microparticles exhibit a deformation from a spherical to a rod-like shape during the thermal-initiated phase transition of the liquid crystalline elastomer (LCE) at which the particles’ aspect ratio is almost doubled. Repeated contraction cycles confirm the complete reversibility of the particles’ actuation properties. The transition temperature of the LCE, the temperature range of the actuation process as well as the magnitude of the particles’ aspect ratio change are studied and controlled by the systematic variation of the liquid crystalline crosslinker content in the monomer mixture. Especially the variable actuation properties of these stimuli-responsive microparticles enable the possibility of an application as soft actuators or sensors. Full article
(This article belongs to the Special Issue Polymeric Soft Actuators)
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Open AccessArticle Semi-Interpenetrating Polymer Networks with Predefined Architecture for Metal Ion Fluorescence Monitoring
Polymers 2016, 8(12), 411; doi:10.3390/polym8120411
Received: 26 September 2016 / Revised: 13 November 2016 / Accepted: 23 November 2016 / Published: 29 November 2016
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Abstract
The development of new synthetic approaches for the preparation of efficient 3D luminescent chemosensors for transition metal ions receives considerable attention nowadays, owing to the key role of the latter as elements in biological systems and their harmful environmental effects when present in
[...] Read more.
The development of new synthetic approaches for the preparation of efficient 3D luminescent chemosensors for transition metal ions receives considerable attention nowadays, owing to the key role of the latter as elements in biological systems and their harmful environmental effects when present in aquatic media. In this work, we describe an easy and versatile synthetic methodology that leads to the generation of nonconjugated 3D luminescent semi-interpenetrating amphiphilic networks (semi-IPN) with structure-defined characteristics. More precisely, the synthesis involves the encapsulation of well-defined poly(9-anthrylmethyl methacrylate) (pAnMMA) (hydrophobic, luminescent) linear polymer chains within a covalent poly(2-(dimethylamino)ethyl methacrylate) (pDMAEMA) hydrophilic polymer network, derived via the 1,2-bis-(2-iodoethoxy)ethane (BIEE)-induced crosslinking process of well-defined pDMAEMA linear chains. Characterization of their fluorescence properties demonstrated that these materials act as strong blue emitters when exposed to UV irradiation. This, combined with the presence of the metal-binding tertiary amino functionalities of the pDMAEMA segments, allowed for their applicability as sorbents and fluorescence chemosensors for transition metal ions (Fe3+, Cu2+) in solution via a chelation-enhanced fluorescence-quenching effect promoted within the semi-IPN network architecture. Ethylenediaminetetraacetic acid (EDTA)-induced metal ion desorption and thus material recyclability has been also demonstrated. Full article
(This article belongs to the Special Issue Young Talents in Polymer Science)
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Open AccessArticle Water-Blown Polyurethane Foams Showing a Reversible Shape-Memory Effect
Polymers 2016, 8(12), 412; doi:10.3390/polym8120412
Received: 10 October 2016 / Revised: 14 November 2016 / Accepted: 18 November 2016 / Published: 28 November 2016
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Abstract
Water-blown polyurethane (PU) foams are of enormous technological interest as they are widely applied in various fields, i.e., consumer goods, medicine, automotive or aerospace industries. The discovery of the one-way shape-memory effect in PU foams provided a fresh impetus for extensive investigations on
[...] Read more.
Water-blown polyurethane (PU) foams are of enormous technological interest as they are widely applied in various fields, i.e., consumer goods, medicine, automotive or aerospace industries. The discovery of the one-way shape-memory effect in PU foams provided a fresh impetus for extensive investigations on porous polymeric actuators over the past decades. High expansion ratios during the shape-recovery are of special interest when big volume changes are required, for example to fill an aneurysm during micro-invasive surgery or save space during transportation. However, the need to program the foams before each operation cycle could be a drawback impeding the entry of shape-memory polymeric (SMP) foams to our daily life. Here, we showed that a reversible shape-memory effect (rSME) is achievable for polyurethane water-blown semicrystalline foams. We selected commercially available crystallizable poly(ε-caprolactone)-diols of different molecular weight for foams synthesis, followed by investigations of morphology, thermal, thermomechanical and shape-memory properties of obtained compositions. Densities of synthesized foams varied from 110 to 180 kg∙m−3, while peak melting temperatures were composition-dependent and changed from 36 to 47 °C, while the melting temperature interval was around 15 K. All semicrystalline foams exhibited excellent one-way SME with shape-fixity ratios slightly above 100% and shape-recovery ratios from the second cycle of 99%. The composition with broad distribution of molecular weights of poly(ε-caprolactone)-diols exhibited an rSME of about 12% upon cyclic heating and cooling from Tlow = 10 °C and Thigh = 47 °C. We anticipate that our experimental study opens a field of systematic investigation of rSMEs in porous polymeric materials on macro and micro scale and extend the application of water-blown polyurethane foams to, e.g., protective covers with zero thermal expansion or even cushions adjustable to a certain body shape. Full article
(This article belongs to the Special Issue Polymeric Soft Actuators)
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Open AccessArticle Diffusive Motion of Linear Microgel Assemblies in Solution
Polymers 2016, 8(12), 413; doi:10.3390/polym8120413
Received: 13 October 2016 / Revised: 8 November 2016 / Accepted: 21 November 2016 / Published: 29 November 2016
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Abstract
Due to the ability of microgels to rapidly contract and expand in response to external stimuli, assemblies of interconnected microgels are promising for actuation applications, e.g., as contracting fibers for artificial muscles. Among the properties determining the suitability of microgel assemblies for actuation
[...] Read more.
Due to the ability of microgels to rapidly contract and expand in response to external stimuli, assemblies of interconnected microgels are promising for actuation applications, e.g., as contracting fibers for artificial muscles. Among the properties determining the suitability of microgel assemblies for actuation are mechanical parameters such as bending stiffness and mobility. Here, we study the properties of linear, one-dimensional chains of poly(N-vinylcaprolactam) microgels dispersed in water. They were fabricated by utilizing wrinkled surfaces as templates and UV-cross-linking the microgels. We image the shapes of the chains on surfaces and in solution using atomic force microscopy (AFM) and fluorescence microscopy, respectively. In solution, the chains are observed to execute translational and rotational diffusive motions. Evaluation of the motions yields translational and rotational diffusion coefficients and, from the translational diffusion coefficient, the chain mobility. The microgel chains show no perceptible bending, which yields a lower limit on their bending stiffness. Full article
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Open AccessArticle Intrinsic Delocalization during the Decay of Excitons in Polymeric Solar Cells
Polymers 2016, 8(12), 414; doi:10.3390/polym8120414
Received: 27 September 2016 / Revised: 24 November 2016 / Accepted: 24 November 2016 / Published: 30 November 2016
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Abstract
In bulk heterojunction polymer solar cells, external photoexcitation results in localized excitons in the polymer chain. After hot exciton formation and subsequent relaxation, the dipole moment drives the electron to partially transfer to extended orbitals from the original localized ones, leading to self-delocalization.
[...] Read more.
In bulk heterojunction polymer solar cells, external photoexcitation results in localized excitons in the polymer chain. After hot exciton formation and subsequent relaxation, the dipole moment drives the electron to partially transfer to extended orbitals from the original localized ones, leading to self-delocalization. Based on the dynamic fluorescence spectra, the delocalization of excitons is revealed to be an intrinsic property dominated by exciton decay, acting as a bridge for the exciton to diffuse in the polymeric solar cell. The modification of the dipole moment enhances the efficiency of polymer solar cells. Full article
(This article belongs to the Special Issue Conjugated Polymers 2016)
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Open AccessArticle Characterization of Epoxy Composites Reinforced with Wax Encapsulated Microcrystalline Cellulose
Polymers 2016, 8(12), 415; doi:10.3390/polym8120415
Received: 19 October 2016 / Revised: 16 November 2016 / Accepted: 22 November 2016 / Published: 30 November 2016
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Abstract
The effect of paraffin wax encapsulated microcrystalline cellulose (EMC) particles on the mechanical and physical properties of EMC/epoxy composites were investigated. It was demonstrated that the compatibility between cellulose and epoxy resin could be maintained due to partial encapsulation resulting in an improvement
[...] Read more.
The effect of paraffin wax encapsulated microcrystalline cellulose (EMC) particles on the mechanical and physical properties of EMC/epoxy composites were investigated. It was demonstrated that the compatibility between cellulose and epoxy resin could be maintained due to partial encapsulation resulting in an improvement in epoxy composite mechanical properties. This work was unique because it was possible to improve the physical and mechanical properties of the EMC/epoxy composites while encapsulating the microcrystalline cellulose (MCC) for a more homogeneous dispersion. The addition of EMC could increase the stiffness of epoxy composites, especially when the composites were wet. The 1% EMC loading with a 1:2 ratio of wax:MCC demonstrated the best reinforcement for both dry and wet properties. The decomposition temperature of epoxy was preserved up to a 5% EMC loading and for different wax:MCC ratios. An increase in wax encapsulated cellulose loading did increase water absorption but overall this absorption was still low (<1%) for all composites. Full article
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Open AccessArticle Nanoclays for Lipase Immobilization: Biocatalyst Characterization and Activity in Polyester Synthesis
Polymers 2016, 8(12), 416; doi:10.3390/polym8120416
Received: 13 July 2016 / Revised: 24 November 2016 / Accepted: 28 November 2016 / Published: 1 December 2016
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Abstract
The immobilization of Candida antarctica lipase B (CALB) was performed by physical adsorption on both neat and organo-modified forms of sepiolite and montmorillonite. The influence of different parameters, e.g., solvent, enzyme loading, cross-linking, and type of clay support, on immobilization efficiency and catalyst
[...] Read more.
The immobilization of Candida antarctica lipase B (CALB) was performed by physical adsorption on both neat and organo-modified forms of sepiolite and montmorillonite. The influence of different parameters, e.g., solvent, enzyme loading, cross-linking, and type of clay support, on immobilization efficiency and catalyst hydrolytic activity has been investigated. The highest hydrolytic activities were obtained for CALB immobilized on organo-modified clay minerals, highlighting the beneficial effect of organo-modification. The esterification activity of these CALB/organoclay catalysts was also tested in the ring-opening polymerization of ε-caprolactone. The polymerization kinetics observed for clay-immobilized catalysts confirmed that CALB adsorbed on organo-modified montmorillonite (CALB/MMTMOD) was the highest-performing catalytic system. Full article
(This article belongs to the Special Issue Enzymatic Polymer Synthesis)
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Open AccessArticle Isothermal Cold Crystallization, Heat Resistance, and Tensile Performance of Polylactide/Thermoplastic Polyester Elastomer (PLA/TPEE) Blends: Effects of Annealing and Reactive Compatibilizer
Polymers 2016, 8(12), 417; doi:10.3390/polym8120417
Received: 17 October 2016 / Revised: 12 November 2016 / Accepted: 28 November 2016 / Published: 8 December 2016
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Abstract
The combined influences of crystallinity and reactive compatibilizer—a multifunctional epoxide (ADR)—on morphology, tensile performance, and heat resistance of polylactide/thermoplastic polyester elastomer (PLA/TPEE) (80/20) blends were investigated. Annealing involved an isothermal cold crystallization of PLA matrix was performed to increase crystallinity of the samples.
[...] Read more.
The combined influences of crystallinity and reactive compatibilizer—a multifunctional epoxide (ADR)—on morphology, tensile performance, and heat resistance of polylactide/thermoplastic polyester elastomer (PLA/TPEE) (80/20) blends were investigated. Annealing involved an isothermal cold crystallization of PLA matrix was performed to increase crystallinity of the samples. First, isothermal cold crystallization kinetics were investigated using differential scanning calorimetry measurement. It was found that the addition of ADR decreased the crystallization rate of the samples. The maximum crystallinity of the annealed samples also decreased from 40% to 34% while ADR loading increased from zero to 1.0 phr. Furthermore, influence of crystallinity on mechanical performances of the PLA/TPEE sample was researched. The heat resistance of the sample showed a significant enhancement while increasing its crystallinity. Meanwhile, the tensile ductility of the crystallized PLA/TPEE sample became very poor due to the embrittlement with increased crystallinity and the incompatibility between PLA and TPEE. However, the annealed PLA/TPEE/ADR samples with high crystallinity kept a higher tensile ductility because ADR greatly improved the interfacial compatibility. Differences in tensile fracture behaviors of the quenched and annealed PLA/TPEE samples with and without ADR were discussed in detail. At last, crystallized PLA/TPEE/ADR blends with excellent heat resistance and high tensile ductility were obtained by annealing and reactive compatibilization. Full article
(This article belongs to the Special Issue Polymer Blends 2017)
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Open AccessArticle Hydrogel Layers on the Surface of Polyester-Based Materials for Improvement of Their Biointeractions and Controlled Release of Proteins
Polymers 2016, 8(12), 418; doi:10.3390/polym8120418
Received: 11 November 2016 / Revised: 24 November 2016 / Accepted: 28 November 2016 / Published: 2 December 2016
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Abstract
The modification of bioresorbable polyester surfaces in order to alter their biointeractions presents an important problem in biomedical polymer science. In this study, the covalent modification of the surface of poly(lactic acid)-based (PLA-based) films with poly(acryl amide) and sodium alginate hydrogels was performed
[...] Read more.
The modification of bioresorbable polyester surfaces in order to alter their biointeractions presents an important problem in biomedical polymer science. In this study, the covalent modification of the surface of poly(lactic acid)-based (PLA-based) films with poly(acryl amide) and sodium alginate hydrogels was performed to change the non-specific polyester interaction with proteins and cells, as well as to make possible the covalent attachment of low-molecular weight ligands and to control protein release. The effect of such modification on the film surface properties was studied. Parameters such as swelling, water contact angle, surface area, and binding capacity of low-molecular weight substances were evaluated and compared. The comparative study of adsorption of model protein (BSA) on the surface of non-modified and modified films was investigated and the protein release was evaluated. Cell viability on the surface of hydrogel-coated films was also tested. The developed approach could be applied for the modification of PLA-based scaffolds for tissue engineering and will be further studied for molecular-imprinting of biomolecules on the surface of polyester-based materials for control of biointeractions. Full article
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Open AccessArticle New Flexible Flame Retardant Coatings Based on Siloxane Resin and Ethylene-Vinyl Chloride Copolymer
Polymers 2016, 8(12), 419; doi:10.3390/polym8120419
Received: 17 July 2016 / Revised: 18 November 2016 / Accepted: 29 November 2016 / Published: 2 December 2016
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Abstract
This work presents the effectiveness of a phosphorus-containing flame retardant based on siloxane resin and ethylene-vinyl chloride copolymer as a back-coating of fabrics. The possibility of improving flame retardant efficiency of this composition by introducing fumed silica, montmorillonite, carbon nanotubes, and graphite was
[...] Read more.
This work presents the effectiveness of a phosphorus-containing flame retardant based on siloxane resin and ethylene-vinyl chloride copolymer as a back-coating of fabrics. The possibility of improving flame retardant efficiency of this composition by introducing fumed silica, montmorillonite, carbon nanotubes, and graphite was evaluated. The effect of each additive on the efficiency of the composition was examined separately. Flammability tests of flame retardant-coated fabrics (natural and synthetic) were carried out using pyrolysis combustion flow calorimetry (PCFC), cone calorimetry, and limiting oxygen index determination. An assessment of the ignitability of upholstered furniture containing flame retardant fabric, resistance to washing, antifungal activity, and some of the utility properties of the final newly-developed flame-retardant coating was conducted. Full article
(This article belongs to the Special Issue Recent Advances in Flame Retardancy of Textile Related Products)
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Open AccessArticle An Investigation of the High Performance of a Novel Type of Benzobisoxazole Fiber Based on 3,3-Diaminobenzidine
Polymers 2016, 8(12), 420; doi:10.3390/polym8120420
Received: 19 August 2016 / Revised: 25 November 2016 / Accepted: 28 November 2016 / Published: 13 December 2016
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Abstract
The mechanical and thermal properties of poly{2,6-diimidazo[4,5-b:4′5′-e] pyridinylene-1,4(2,5-dihydroxy) phenylene} (PIPD)-3,3-diaminobenzidine (DAB) fibers were analyzed. Compared to other types of benzimidazole fiber structures and properties, PIPD-DAB is distinguished by a unique combination of strength, tensile modulus, and thermal properties. The PIPD polymer was prepared
[...] Read more.
The mechanical and thermal properties of poly{2,6-diimidazo[4,5-b:4′5′-e] pyridinylene-1,4(2,5-dihydroxy) phenylene} (PIPD)-3,3-diaminobenzidine (DAB) fibers were analyzed. Compared to other types of benzimidazole fiber structures and properties, PIPD-DAB is distinguished by a unique combination of strength, tensile modulus, and thermal properties. The PIPD polymer was prepared from 2,3,5,6-tetra-aminopyridine (TAP) and 2,5-dihydroxyterephthalic acid (DHTA) in polyphosphoric acid (PPA). In order to enhance the tensile strength and modulus, a third comonomer, 3,3-diaminobenzidine (DAB), was incorporated into the PIPD molecular structure. The change in molecular structure was recorded using Fourier-transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and wide angle X-ray diffraction (WAXD). Compared to the PIPD fibers (average tensile strength of PIPD is 3.9 GPa, average tensile modulus of PIPD is 287 GPa), the tensile strength and modulus of PIPD-DAB increased to 4.2 and 318 GPa, respectively. In addition, the thermal decomposition temperature of the PIPD fibers is enhanced by 35 °C, due to the incorporated DAB. PIPD-DAB is a promising material for use under high tensile loads and/or high temperatures. Full article
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Open AccessArticle Miscibility, Morphology and Crystallization Behavior of Poly(Butylene Succinate-co-Butylene Adipate)/Poly(Vinyl Phenol)/Poly(l-Lactic Acid) Blends
Polymers 2016, 8(12), 421; doi:10.3390/polym8120421
Received: 10 October 2016 / Revised: 23 November 2016 / Accepted: 1 December 2016 / Published: 6 December 2016
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Abstract
Amorphous poly(vinyl phenol) (PVPh) is introduced into poly(butylene succinate-co-butylene adipate)/poly(l-lactic acid) (PBSA/PLLA) blends via solution casting. Fourier transform infrared spectroscopy (FTIR) analysis verifies that intermolecular hydrogen bonding formed in PBSA/PVPh/PLLA blends. The miscibility between PBSA and PLLA is improved
[...] Read more.
Amorphous poly(vinyl phenol) (PVPh) is introduced into poly(butylene succinate-co-butylene adipate)/poly(l-lactic acid) (PBSA/PLLA) blends via solution casting. Fourier transform infrared spectroscopy (FTIR) analysis verifies that intermolecular hydrogen bonding formed in PBSA/PVPh/PLLA blends. The miscibility between PBSA and PLLA is improved with PVPh incorporation as evidenced by approaching Tgs of the two components. When PVPh content reaches up to 50 wt %, the blend sample exhibits only one Tg, meaning complete miscibility between PBSA and PLLA. The improved miscibility of PBSA/PLLA blends is further confirmed by scanning electron microscope (SEM). Typical “see-island” phase separation structure for PBSA/PLLA blend transforms into homogenous phase structure for blend samples with 5 wt % PVPh and above. Non-isothermal crystallization analysis shows that the crystallization temperature and crystallization enthalpy of PBSA decrease with PVPh addition, and those of PLLA also show a decreasing trend. Isothermal crystallization rate of PBSA in blend samples distinctly decreases with PVPh incorporation, whereas that of PLLA in blend samples increases slightly with PVPh addition. Wide angle X-ray diffraction (WAXD) analysis indicated that PLLA in blend samples remained partly crystallized, while PBSA turned into amorphous state with increasing PVPh contents. Full article
(This article belongs to the Special Issue Polymer Blends 2017)
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Open AccessArticle Investigating the Synergistic Effects of Combined Modified Alginates on Macrophage Phenotype
Polymers 2016, 8(12), 422; doi:10.3390/polym8120422
Received: 30 September 2016 / Revised: 17 November 2016 / Accepted: 1 December 2016 / Published: 6 December 2016
Cited by 1 | PDF Full-text (5031 KB) | HTML Full-text | XML Full-text
Abstract
Understanding macrophage responses to biomaterials is crucial to the success of implanted medical devices, tissue engineering scaffolds, and drug delivery vehicles. Cellular responses to materials may depend synergistically on multiple surface chemistries, due to the polyvalent nature of cell–ligand interactions. Previous work in
[...] Read more.
Understanding macrophage responses to biomaterials is crucial to the success of implanted medical devices, tissue engineering scaffolds, and drug delivery vehicles. Cellular responses to materials may depend synergistically on multiple surface chemistries, due to the polyvalent nature of cell–ligand interactions. Previous work in our lab found that different surface functionalities of chemically modified alginate could sway macrophage phenotype toward either the pro-inflammatory or pro-angiogenic phenotype. Using these findings, this research aims to understand the relationship between combined material surface chemistries and macrophage phenotype. Tumor necrosis factor-α (TNF-α) secretion, nitrite production, and arginase activity were measured and used to determine the ability of the materials to alter macrophage phenotype. Cooperative relationships between pairwise modifications of alginate were determined by calculating synergy values for the aforementioned molecules. Several materials appeared to improve M1 to M2 macrophage reprogramming capabilities, giving valuable insight into the complexity of surface chemistries needed for optimal incorporation and survival of implanted biomaterials. Full article
(This article belongs to the Special Issue Young Talents in Polymer Science)
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Open AccessArticle Polyetheretherketone Hybrid Composites with Bioactive Nanohydroxyapatite and Multiwalled Carbon Nanotube Fillers
Polymers 2016, 8(12), 425; doi:10.3390/polym8120425
Received: 25 October 2016 / Revised: 29 November 2016 / Accepted: 2 December 2016 / Published: 8 December 2016
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Abstract
Polyetheretherketone (PEEK) hybrid composites reinforced with inorganic nanohydroxyapatite (nHA) and multiwalled carbon nanotube (MWNT) were prepared by melt-compounding and injection molding processes. The additions of nHA and MWNT to PEEK were aimed to increase its elastic modulus, tensile strength, and biocompatibility, rendering the
[...] Read more.
Polyetheretherketone (PEEK) hybrid composites reinforced with inorganic nanohydroxyapatite (nHA) and multiwalled carbon nanotube (MWNT) were prepared by melt-compounding and injection molding processes. The additions of nHA and MWNT to PEEK were aimed to increase its elastic modulus, tensile strength, and biocompatibility, rendering the hybrids suitable for load-bearing implant applications. The structural behavior, mechanical property, wettability, osteoblastic cell adhesion, proliferation, differentiation, and mineralization of the PEEK/nHA-MWNT hybrids were studied. X-ray diffraction and SEM observation showed that both nHA and MWNT fillers are incorporated into the polymer matrix of PEEK-based hybrids. Tensile tests indicated that the elastic modulus of PEEK can be increased from 3.87 to 7.13 GPa by adding 15 vol % nHA and 1.88 vol % MWNT fillers. The tensile strength and elongation at break of the PEEK/(15% nHA)-(1.88% MWNT) hybrid were 64.48 MPa and 1.74%, respectively. Thus the tensile properties of this hybrid were superior to those of human cortical bones. Water contact angle measurements revealed that the PEEK/(15% nHA)-(1.88% MWNT) hybrid is hydrophilic due to the presence of nHA. Accordingly, hydrophilic PEEK/(15% nHA)-(1.88% MWNT) hybrid promoted the adhesion, proliferation, differentiation, and mineralization of murine MC3T3-E1 osteoblasts on its surface effectively on the basis of cell culture, fluorescence microscopy, MTT assay, WST-1 assay, alkaline phosphatase activity, and Alizarin red staining tests. Thus the PEEK/(15% nHA)-(1.88% MWNT) hybrid has the potential to be used for fabricating load-bearing bone implants. Full article
(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)
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Open AccessArticle Hydrodynamic Interactions and Entanglements of Polymer Solutions in Many-Body Dissipative Particle Dynamics
Polymers 2016, 8(12), 426; doi:10.3390/polym8120426
Received: 16 November 2016 / Revised: 5 December 2016 / Accepted: 6 December 2016 / Published: 9 December 2016
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Abstract
Using many-body dissipative particle dynamics (MDPD), polymer solutions with concentrations spanning dilute and semidilute regimes are modeled. The parameterization of MDPD interactions for systems with liquid–vapor coexistence is established by mapping to the mean-field Flory–Huggins theory. The characterization of static and dynamic properties
[...] Read more.
Using many-body dissipative particle dynamics (MDPD), polymer solutions with concentrations spanning dilute and semidilute regimes are modeled. The parameterization of MDPD interactions for systems with liquid–vapor coexistence is established by mapping to the mean-field Flory–Huggins theory. The characterization of static and dynamic properties of polymer chains is focused on the effects of hydrodynamic interactions and entanglements. The coil–globule transition of polymer chains in dilute solutions is probed by varying solvent quality and measuring the radius of gyration and end-to-end distance. Both static and dynamic scaling relations for polymer chains in poor, theta, and good solvents are in good agreement with the Zimm theory with hydrodynamic interactions considered. Semidilute solutions with polymer volume fractions up to 0.7 exhibit the screening of excluded volume interactions and subsequent shrinking of polymer coils. Furthermore, entanglements become dominant in the semidilute solutions, which inhibit diffusion and relaxation of chains. Quantitative analysis of topology violation confirms that entanglements are correctly captured in the MDPD simulations. Full article
(This article belongs to the Special Issue Computational Modeling and Simulation in Polymer)
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Open AccessArticle Polysarcosine-Based Lipids: From Lipopolypeptoid Micelles to Stealth-Like Lipids in Langmuir Blodgett Monolayers
Polymers 2016, 8(12), 427; doi:10.3390/polym8120427
Received: 17 October 2016 / Revised: 24 November 2016 / Accepted: 2 December 2016 / Published: 9 December 2016
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Abstract
Amphiphiles and, in particular, PEGylated lipids or alkyl ethers represent an important class of non-ionic surfactants and have become key ingredients for long-circulating (“stealth”) liposomes. While poly-(ethylene glycol) (PEG) can be considered the gold standard for stealth-like materials, it is known to be
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Amphiphiles and, in particular, PEGylated lipids or alkyl ethers represent an important class of non-ionic surfactants and have become key ingredients for long-circulating (“stealth”) liposomes. While poly-(ethylene glycol) (PEG) can be considered the gold standard for stealth-like materials, it is known to be neither a bio-based nor biodegradable material. In contrast to PEG, polysarcosine (PSar) is based on the endogenous amino acid sarcosine (N-methylated glycine), but has also demonstrated stealth-like properties in vitro, as well as in vivo. In this respect, we report on the synthesis and characterization of polysarcosine based lipids with C14 and C18 hydrocarbon chains and their end group functionalization. Size exclusion chromatography (SEC) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analysis reveals that lipopeptoids with a degree of polymerization between 10 and 100, dispersity indices around 1.1, and the absence of detectable side products are directly accessible by nucleophilic ring opening polymerization (ROP). The values for the critical micelle concentration for these lipopolymers are between 27 and 1181 mg/L for the ones with C18 hydrocarbon chain or even higher for the C14 counterparts. The lipopolypeptoid based micelles have hydrodynamic diameters between 10 and 25 nm, in which the size scales with the length of the PSar block. In addition, C18PSar50 can be incorporated in 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) monolayers up to a polymer content of 3%. Cyclic compression and expansion of the monolayer showed no significant loss of polymer, indicating a stable monolayer. Therefore, lipopolypeptoids can not only be synthesized under living conditions, but my also provide a platform to substitute PEG-based lipopolymers as excipients and/or in lipid formulations. Full article
(This article belongs to the Special Issue Young Talents in Polymer Science)
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Open AccessArticle Real-Time Packing Behavior of Core-Shell Silica@Poly(N-isopropylacrylamide) Microspheres as Photonic Crystals for Visualizing in Thermal Sensing
Polymers 2016, 8(12), 428; doi:10.3390/polym8120428
Received: 5 November 2016 / Revised: 29 November 2016 / Accepted: 6 December 2016 / Published: 10 December 2016
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Abstract
We grafted thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) brushes from monodisperse SiO2 microspheres through surface-initiated atom transfer radical polymerization (SI ATRP) to generate core-shell structured SiO2@PNIPAM microspheres (SPMs). Regular-sized SPMs dispersed in aqueous solution and packed as photonic crystals (PCs) in
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We grafted thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) brushes from monodisperse SiO2 microspheres through surface-initiated atom transfer radical polymerization (SI ATRP) to generate core-shell structured SiO2@PNIPAM microspheres (SPMs). Regular-sized SPMs dispersed in aqueous solution and packed as photonic crystals (PCs) in dry state. Because of the microscale of the SPMs, the packing behavior of the PCs in water can be observed by optical microscopy. By increasing the temperature above the lower critical solution temperature (LCST) of PNIPAM, the reversible swelling and shrinking of the PNIPAM shell resulted in dispersion and precipitation (three-dimensional aggregation) of the SPM in aqueous solution. The SPMs were microdispersed in a water layer to accommodate the aggregation along two dimensions. In the microdispersion, the SPMs are packed as PCs with microscale spacing between SPMs below the LCST. When the temperature is increased above the LCST, the microdispersed PCs exhibited a close-packed arrangement along two dimensions with decreased spacing between SPMs. The change in spacing with increasing temperature above the LCST resulted in a color change from red to blue, which could be observed by the naked eye at an incident angle. Thus, the SPM array could be applied as a visual temperature sensor. Full article
(This article belongs to the Special Issue Polymers for Chemosensing)
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Open AccessArticle Microsphere-Based Hierarchically Juxtapositioned Biphasic Scaffolds Prepared from Poly(Lactic-co-Glycolic Acid) and Nanohydroxyapatite for Osteochondral Tissue Engineering
Polymers 2016, 8(12), 429; doi:10.3390/polym8120429
Received: 12 October 2016 / Revised: 18 November 2016 / Accepted: 5 December 2016 / Published: 10 December 2016
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Abstract
This study aims to prepare biphasic osteochondral scaffolds based on seamless joining of sintered polymer and polymer/ceramic microspheres for co-culture of chondrocytes and bone marrow stem cells (BMSCs). Poly(lactide-co-glycolide) (PLGA) microspheres and 10% nanohydroxyapatite (nHAP)-incorporated PLGA (PGA/nHAP) microspheres were prepared through
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This study aims to prepare biphasic osteochondral scaffolds based on seamless joining of sintered polymer and polymer/ceramic microspheres for co-culture of chondrocytes and bone marrow stem cells (BMSCs). Poly(lactide-co-glycolide) (PLGA) microspheres and 10% nanohydroxyapatite (nHAP)-incorporated PLGA (PGA/nHAP) microspheres were prepared through the oil-in-water precipitation method. Virgin (V) and composite (C) scaffolds were prepared from 250–500 µm PLGA and PLGA/nHAP microspheres, respectively, while osteochondral (OC) scaffolds were fabricated through the combination of V and C scaffolds. Physico-chemical properties of scaffolds were characterized through microscopic-spectroscopic evaluations. The effect of nHAP in scaffolds was investigated through thermogravimetric analysis and mechanical testing, while surface hydrophobicity was tested through contact angle measurements. Rabbit chondrocytes and BMSCs were used for cell culture, and cell morphology and proliferation were determined from SEM and DNA assays. Alizarin red and Alcian blue stains were used to identify the in vitro bone and cartilage tissue-specific regeneration, while cetylpyridinium chloride was used to quantitatively estimate calcium in mineralized bone. For co-culture in OC scaffolds, BMSCs were first seeded in the bone part of the scaffold and cultured in osteogenic medium, followed by seeding chondrocytes in the cartilage part, and cultured in chondrocyte medium. High cell viability was confirmed from the Live/Dead assays. Actin cytoskeleton organization obtained by DAPI-phalloidin staining revealed proper organization of chondrocytes and BMSCs in OC scaffolds. Immunofluorescent staining of bone (type I collagen and osteocalcin (OCN)) and cartilage marker proteins (type II collagen (COL II)) confirmed cellular behavior of osteoblasts and chondrocytes in vitro. Using an ectopic osteochondral defect model by subcutaneous implantation of co-cultured OC scaffolds in nude mice confirmed cell proliferation and tissue development from gross view and SEM observation. IF staining of OCN and COL II in the bone and cartilage parts of OC scaffolds and tissue-specific histological analysis exhibited a time-dependent tissue re-modeling and confirmed the potential application of the biphasic scaffold in osteochondral tissue engineering. Full article
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Open AccessArticle All-Inorganic Intumescent Nanocoating Containing Montmorillonite Nanoplatelets in Ammonium Polyphosphate Matrix Capable of Preventing Cotton Ignition
Polymers 2016, 8(12), 430; doi:10.3390/polym8120430
Received: 29 October 2016 / Revised: 5 December 2016 / Accepted: 8 December 2016 / Published: 10 December 2016
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Abstract
In the present manuscript a new concept of completely inorganic intumescent flame retardant nanocoating comprised of sodium montmorillonite nanoplatelets embedded in an ammonium polyphosphate matrix has been investigated using cotton as model substrate. The coating, deposited by multistep adsorption from diluted water-based suspensions/solutions,
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In the present manuscript a new concept of completely inorganic intumescent flame retardant nanocoating comprised of sodium montmorillonite nanoplatelets embedded in an ammonium polyphosphate matrix has been investigated using cotton as model substrate. The coating, deposited by multistep adsorption from diluted water-based suspensions/solutions, homogenously cover each cotton fibers with average thicknesses below 50 nm and add-on up to 5% in weight. Combustion characterization evidences the interesting properties: indeed, the so-treated fabrics reached self-extinguishing during horizontal flame spread tests. Furthermore, when the coating add-on reaches 5%, no ignition has been observed during cone calorimetry tests under 35 kW/m2 heat flux. Residue analyses pointed out the formation of an expanded all-inorganic coating capable of greatly improving char formation by exerting barrier function towards volatile release and heat transfer. Full article
(This article belongs to the Special Issue Young Talents in Polymer Science)
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Open AccessArticle The Effect of Thermal History on the Fast Crystallization of Poly(l-Lactide) with Soluble-Type Nucleators and Shear Flow
Polymers 2016, 8(12), 431; doi:10.3390/polym8120431
Received: 14 October 2016 / Revised: 24 November 2016 / Accepted: 1 December 2016 / Published: 10 December 2016
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Abstract
The N1,N1ʹ-(ethane-1,2-diyl)bis(N2-phenyloxalamide) (OXA) is a soluble-type nucleator with a dissolving temperature of 230 °C in poly(l-lactic acid) (PLLA) matrix. The effect of thermal history and shear flow on the crystallization behavior of the
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The N1,N1ʹ-(ethane-1,2-diyl)bis(N2-phenyloxalamide) (OXA) is a soluble-type nucleator with a dissolving temperature of 230 °C in poly(l-lactic acid) (PLLA) matrix. The effect of thermal history and shear flow on the crystallization behavior of the PLLA/OXA samples was investigated by rheometry, polarized optical microscopy (POM), differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), and scanning electron microscopy (SEM). The crystallization process of the PLLA/OXA-240 sample (i.e., pre-melted at 240 °C) was significantly promoted by applying a shear flow, e.g., the onset crystallization time (tonset) of the PLLA at 155 °C was reduced from 1600 to 200 s after shearing at 0.4 rad/s for even as short as 1.0 s, while the crystallinity (Xc) was increased to 40%. Moreover, the tonset of the PLLA/OXA-240 sample is 60%–80% lower than that of the PLLA/OXA-200 sample (i.e., pre-melted at 200 °C) with a total shear angle of 2 rad, indicating a much higher crystallization rate of the PLLA/OXA-240 sample. A better organization and uniformity of OXA fibrils can be obtained due to a complete pre-dissolution in the PLLA matrix followed by shear and oscillation treatments. The well dispersed OXA fibrils and flow-induced chain orientation are mainly responsible for the fast crystallization of the PLLA/OXA-240 samples. In addition, the shear flow created some disordered α′-form crystals in the PLLA/OXA samples regardless of the thermal history (200 or 240 °C). Full article
(This article belongs to the Special Issue Young Talents in Polymer Science)
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Open AccessArticle Dynamic and Static Behavior of Hollow-Core FRP-Concrete-Steel and Reinforced Concrete Bridge Columns under Vehicle Collision
Polymers 2016, 8(12), 432; doi:10.3390/polym8120432
Received: 3 November 2016 / Revised: 1 December 2016 / Accepted: 7 December 2016 / Published: 13 December 2016
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Abstract
This paper presents the difference in behavior between hollow-core fiber reinforced polymer-concrete-steel (HC-FCS) columns and conventional reinforced concrete (RC) columns under vehicle collision in terms of dynamic and static forces. The HC-FCS column consisted of an outer FRP tube, an inner steel tube,
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This paper presents the difference in behavior between hollow-core fiber reinforced polymer-concrete-steel (HC-FCS) columns and conventional reinforced concrete (RC) columns under vehicle collision in terms of dynamic and static forces. The HC-FCS column consisted of an outer FRP tube, an inner steel tube, and a concrete shell sandwiched between the two tubes. The steel tube was hollow inside and embedded into the concrete footing with a length of 1.5 times the tube diameter while the FRP tube stopped at the top of footing. The RC column had a solid cross-section. The study was conducted through extensive finite element impact analyses using LS-DYNA software. Nine parameters were studied including the concrete material model, unconfined concrete compressive strength, material strain rate, column height-to-diameter ratio, column diameter, column top boundary condition, axial load level, vehicle velocity, and vehicle mass. Generally, the HC-FCS columns had lower dynamic forces and higher static forces than the RC columns when changing the values of the different parameters. During vehicle collision with either the RC or the HC-FCS columns, the imposed dynamic forces and their equivalent static forces were affected mainly by the vehicle velocity and vehicle mass. Full article
(This article belongs to the Special Issue Selected Papers from “SMAR 2015”)
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Open AccessArticle Study on Hydrogen Sensitivity of Ziegler–Natta Catalysts with Novel Cycloalkoxy Silane Compounds as External Electron Donor
Polymers 2016, 8(12), 433; doi:10.3390/polym8120433
Received: 9 November 2016 / Revised: 2 December 2016 / Accepted: 8 December 2016 / Published: 16 December 2016
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Abstract
Two novel cycloalkoxy silane compounds (ED1 and ED2) were synthesized and used as the external electron donors (EEDs) in Ziegler–Natta catalysts with diethyl 2,3-diisopropylsuccinate as internal electron donor. The results indicated that the Ziegler–Natta catalysts using ED1 and ED2 as EEDs had high
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Two novel cycloalkoxy silane compounds (ED1 and ED2) were synthesized and used as the external electron donors (EEDs) in Ziegler–Natta catalysts with diethyl 2,3-diisopropylsuccinate as internal electron donor. The results indicated that the Ziegler–Natta catalysts using ED1 and ED2 as EEDs had high catalytic activities and good stereoselectivities. The melt flow rate (MFR) and gel permeation chromatography (GPC) results revealed that the obtained polypropylene has higher MFR and lower average molecular weights than the commercial EED cyclohexyl methyl dimethoxysilane. The differential scanning calorimetry (DSC) results indicated that new isospecific active centers formed after the introduction of new external donors. The work implied that the novel EEDs could improve the hydrogen sensitivities of the catalyst system and obtain polymers with high melt flow rate. Full article
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Open AccessArticle Temperature-, pH- and CO2-Sensitive Poly(N-isopropylacryl amide-co-acrylic acid) Copolymers with High Glass Transition Temperatures
Polymers 2016, 8(12), 434; doi:10.3390/polym8120434
Received: 14 November 2016 / Revised: 6 December 2016 / Accepted: 7 December 2016 / Published: 14 December 2016
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Abstract
A series of poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAAm-co-PAA) random copolymers were synthesized through free radical copolymerization in MeOH. The incorporation of the acrylic acid units into PNIPAAm tended to enhance the glass transition temperature (Tg), due
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A series of poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAAm-co-PAA) random copolymers were synthesized through free radical copolymerization in MeOH. The incorporation of the acrylic acid units into PNIPAAm tended to enhance the glass transition temperature (Tg), due to strong intermolecular hydrogen bonding between the amide groups of PNIPAAm and the carboxyl groups of PAA, as observed using 1H nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopic analyses. The lower critical solution temperature (LCST) increased upon increasing the pH of the aqueous solution containing PNIPAAm-co-PAA because the COOH groups of the PAA segment dissociated into COO groups, enhancing the solubility of the copolymer. In addition, high-pressure differential scanning calorimetry revealed that the LCSTs of all the aqueous solutions of the copolymers decreased upon increasing the pressure of CO2, suggesting that CO2 molecules had displaced H2O molecules around the polar CONH and COOH groups in PNIPAAm-co-PAA, thereby promoting the hydrophobicity of the copolymers in the aqueous solution. In addition, the values of Tg of a film sample increased upon treatment with supercritical CO2, implying that intermolecular interactions in the copolymer had been enhanced after such treatment. Full article
(This article belongs to the Special Issue Functionally Responsive Polymeric Materials)
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Open AccessArticle Influence of a Crosslinker Containing an Azo Group on the Actuation Properties of a Photoactuating LCE System
Polymers 2016, 8(12), 435; doi:10.3390/polym8120435
Received: 15 October 2016 / Revised: 6 December 2016 / Accepted: 8 December 2016 / Published: 14 December 2016
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Abstract
Photoactuating liquid crystalline elastomers (LCE) are promising candidates for an application as artificial muscles in microdevices. In this work, we demonstrate that by optimizing (1) the illumination conditions and (2) the mixture of azo monomer and azo crosslinker, thick films of an all-azo
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Photoactuating liquid crystalline elastomers (LCE) are promising candidates for an application as artificial muscles in microdevices. In this work, we demonstrate that by optimizing (1) the illumination conditions and (2) the mixture of azo monomer and azo crosslinker, thick films of an all-azo LCE can be prepared, which show a strong length change without bending during photoactuation. This becomes possible by working with white light (about 440 nm), whose absorption is low, leading to a large penetration depth. By adding an azo crosslinker to a previously prepared system, several improvements of the actuation properties—like a stronger photoactuation at lower operational temperatures—could be achieved. In addition, films of different crosslinker concentrations and thicknesses were produced by photopolymerization at varying temperatures within a magnetic field, and their thermo- and photoresponsive behavior was investigated. An extraordinarily strong maximal thermal actuation of 46% and—by exposure to white light at 70 °C—a photoresponsive change in length of up to 40% in just about 13 s could be obtained. Even densely crosslinked samples were still able to photoactuate remarkably. Isothermal back-deformation could either be achieved by irradiation with red light (7 min) or by keeping the film in the dark (13 min). Full article
(This article belongs to the Special Issue Polymeric Soft Actuators)
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Open AccessArticle Healing of Early Stage Fatigue Damage in Ionomer/Fe3O4 Nanoparticle Composites
Polymers 2016, 8(12), 436; doi:10.3390/polym8120436
Received: 31 October 2016 / Revised: 28 November 2016 / Accepted: 6 December 2016 / Published: 15 December 2016
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Abstract
This work reports on the healing of early stage fatigue damage in ionomer/nano-particulate composites. A series of poly(ethylene-co-methacrylic acid) zinc ionomer/Fe3O4 nanoparticle composites with varying amounts of ionic clusters were developed and subjected to different levels of fatigue
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This work reports on the healing of early stage fatigue damage in ionomer/nano-particulate composites. A series of poly(ethylene-co-methacrylic acid) zinc ionomer/Fe3O4 nanoparticle composites with varying amounts of ionic clusters were developed and subjected to different levels of fatigue loading. The initiated damage was healed upon localized inductive heating of the embedded nanoparticles by exposure of the particulate composite to an alternating magnetic field. It is here demonstrated that healing of this early stage damage in ionomer particulate composites occurs in two different steps. First, the deformation is restored by the free-shrinkage of the polymer at temperatures below the melt temperature. At these temperatures, the polymer network is recovered thereby resetting the fatigue induced strain hardening. Then, at temperatures above the melting point of the polymer phase, fatigue-induced microcracks are sealed, hereby preventing crack propagation upon further loading. It is shown that the thermally induced free-shrinkage of these polymers does not depend on the presence of ionic clusters, but that the ability to heal cracks by localized melting while maintaining sufficient mechanical integrity is reserved for ionomers that contain a sufficient amount of ionic clusters guaranteeing an acceptable level of mechanical stability during healing. Full article
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Open AccessArticle Creep and Recovery Behaviour of Polyolefin-Rubber Nanocomposites Developed for Additive Manufacturing
Polymers 2016, 8(12), 437; doi:10.3390/polym8120437
Received: 17 October 2016 / Revised: 6 December 2016 / Accepted: 7 December 2016 / Published: 15 December 2016
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Abstract
Nanocomposite application in automotive engineering materials is subject to continual stress fields together with recovery periods, under extremes of temperature variations. The aim is to prepare and characterize polyolefin-rubber nanocomposites developed for additive manufacturing in terms of their time-dependent deformation behaviour as revealed
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Nanocomposite application in automotive engineering materials is subject to continual stress fields together with recovery periods, under extremes of temperature variations. The aim is to prepare and characterize polyolefin-rubber nanocomposites developed for additive manufacturing in terms of their time-dependent deformation behaviour as revealed in creep-recovery experiments. The composites consisted of linear low density polyethylene and functionalized rubber particles. Maleic anhydride compatibilizer grafted to polyethylene was used to enhance adhesion between the polyethylene and rubber; and multi-walled carbon nanotubes were introduced to impart electrical conductivity. Various compositions of nanocomposites were tested under constant stress in creep and recovery. A four-element mechanistic Burger model was employed to model the creep phase of the composites, while a Weibull distribution function was employed to model the recovery phase of the composites. Finite element analysis using Abaqus enabled numerical modelling of the creep phase of the composites. Both analytical and numerical solutions were found to be consistent with the experimental results. Creep and recovery were dependent on: (i) composite composition; (ii) compatibilizers content; (iii) carbon nanotubes that formed a percolation network. Full article
(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)
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Open AccessArticle Electroosmotic Flow in Mixed Polymer Brush-Grafted Nanochannels
Polymers 2016, 8(12), 438; doi:10.3390/polym8120438
Received: 3 November 2016 / Revised: 10 December 2016 / Accepted: 12 December 2016 / Published: 16 December 2016
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Abstract
Mixed polymer brush-grafted nanochannels—where two distinct species of polymers are alternately grafted on the inner surface of nanochannels—are an interesting class of nanostructured hybrid materials. By using a coarse-grained molecular dynamics simulation method, we are able to simulate the electrokinetic transport dynamics of
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Mixed polymer brush-grafted nanochannels—where two distinct species of polymers are alternately grafted on the inner surface of nanochannels—are an interesting class of nanostructured hybrid materials. By using a coarse-grained molecular dynamics simulation method, we are able to simulate the electrokinetic transport dynamics of the fluid in such nanochannels as well as the conformational behaviors of the mixed polymer brush. We find that (1) the brush adopts vertically-layered and longitudinally-separated structures due to the coupling of electroosmotic flow (EOF) and applied electric field; (2) the solvent quality affects the brush conformations and the transport properties of the EOF; (3) the EOF flux non-monotonically depends on the grafting density, although the EOF velocity in the central region of the channel monotonically depends on the grafting density. Full article
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Open AccessArticle Synthesis of Polythiophene–Fullerene Hybrid Additives as Potential Compatibilizers of BHJ Active Layers
Polymers 2016, 8(12), 440; doi:10.3390/polym8120440
Received: 11 November 2016 / Revised: 9 December 2016 / Accepted: 13 December 2016 / Published: 18 December 2016
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Abstract
Perfluorophenyl functionalities have been introduced as side chain substituents onto regioregular poly(3-hexyl thiophene) (rr-P3HT), under various percentages. These functional groups were then converted to azides which were used to create polymeric hybrid materials with fullerene species, either C60 or C
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Perfluorophenyl functionalities have been introduced as side chain substituents onto regioregular poly(3-hexyl thiophene) (rr-P3HT), under various percentages. These functional groups were then converted to azides which were used to create polymeric hybrid materials with fullerene species, either C60 or C70. The P3HT–fullerene hybrids thus formed were thereafter evaluated as potential compatibilizers of BHJ active layers comprising P3HT and fullerene based acceptors. Therefore, a systematic investigation of the optical and morphological properties of the purified polymer–fullerene hybrid materials was performed, via different complementary techniques. Additionally, P3HT:PC70BM blends containing various percentages of the herein synthesized hybrid material comprising rr-P3HT and C70 were investigated via Transmission Electron Microscopy (TEM) in an effort to understand the effect of the hybrids as additives on the morphology and nanophase separation of this typically used active layer blend for OPVs. Full article
(This article belongs to the Special Issue Hybrid Polymeric Materials)
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Open AccessArticle A Highly Hydrophilic and Biodegradable Novel Poly(amide-imide) for Biomedical Applications
Polymers 2016, 8(12), 441; doi:10.3390/polym8120441
Received: 9 November 2016 / Revised: 9 December 2016 / Accepted: 13 December 2016 / Published: 19 December 2016
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Abstract
A novel biodegradable poly(amide-imide) (PAI) with good hydrophilicity was synthesized by incorporation of l-glycine into the polymer chain. For comparison purposes, a pure PAI containing no l-glycine was also synthesized with a three-step method. In this study, we evaluated the novel
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A novel biodegradable poly(amide-imide) (PAI) with good hydrophilicity was synthesized by incorporation of l-glycine into the polymer chain. For comparison purposes, a pure PAI containing no l-glycine was also synthesized with a three-step method. In this study, we evaluated the novel PAI’s thermal stability, hydrophilicity, solubility, biodegradability and ability to support bone marrow mesenchymal stem cell (BMSC) adhesion and growth by comparing with the pure PAI. The hydrophilic tests demonstrated that the novel PAI has possible hydrophilicity at a 38° water contact angle on the molecule surface and is about two times more hydrophilic than the pure PAI. Due to an extra unit of l-glycine in the novel PAI, the average degradation rate was about 2.4 times greater than that of the pure PAI. The preliminary biocompatibility studies revealed that all the PAIs are cell compatible, but the pure PAI exhibited much lower cell adhesion than the l-glycine-incorporated novel PAI. The hydrophilic surface of the novel PAI was more suitable for cell adhesion, suggesting that the surface hydrophilicity plays an important role in enhancing cell adhesion and growth. Full article
(This article belongs to the Special Issue Biodegradable Polymers)
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Open AccessArticle Investigations on Green Blends Comprising Biodegradable Polymer and Ionic Liquid
Polymers 2016, 8(12), 444; doi:10.3390/polym8120444
Received: 12 October 2016 / Revised: 13 December 2016 / Accepted: 14 December 2016 / Published: 21 December 2016
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Abstract
The green blends of an ionic liquid, 1-ethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide {[EPrI][TFSI]}, and a biodegradable polymer, poly(3-hydroxybutyrate) (PHB), were investigated in this study. The influence of an ionic liquid on the crystallization behaviors of a biodegradable polymer was explored. In the blends, the presence of
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The green blends of an ionic liquid, 1-ethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide {[EPrI][TFSI]}, and a biodegradable polymer, poly(3-hydroxybutyrate) (PHB), were investigated in this study. The influence of an ionic liquid on the crystallization behaviors of a biodegradable polymer was explored. In the blends, the presence of [EPrI][TFSI] decreased the Tg and Tm of PHB. Incorporating [EPrI][TFSI] in the blends reduced the degree of crystallinity of PHB, inferring that the [EPrI][TFSI] weakened the crystallization of PHB. It further showed retarded isothermal and non-isothermal crystallization for PHB with the presence of [EPrI][TFSI]. The smaller K and 1/t0.5 estimated by the Avrami equation for the blends indicated that [EPrI][TFSI] weakened the isothermal crystallization of PHB with exhibiting the slower crystallization rate. The present study also discussed non-isothermal crystallization of the blends. We found that the Mo model, which is generally used to discuss the non-isothermal crystallization, adequately described the non-isothermal behaviors of the [EPrI][TFSI]/PHB blends. By increasing the [EPrI][TFSI] content, the rate-related parameter F(T) systematically increased, inferring a decreased crystallization rate of PHB with the addition of [EPrI][TFSI] in the blends. The FTIR results suggested an ion–dipole interaction between [EPrI][TFSI] and PHB. This proposes the occurrence of possible complexation between [EPrI][TFSI] and PHB. Full article
(This article belongs to the Special Issue Polymer Blends 2017)
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Open AccessArticle Design of Graphene- and Polyaniline-Containing Functional Polymer Hydrogel as a New Adsorbent for Removal of Chromium (VI) Ions
Polymers 2016, 8(12), 445; doi:10.3390/polym8120445
Received: 24 October 2016 / Revised: 8 December 2016 / Accepted: 16 December 2016 / Published: 21 December 2016
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Abstract
Hydrogels find applications in various fields, and the ever-growing spectrum of available monomers, crosslinking, and nanotechnologies widen the application of polymer hydrogels. Herein, we describe the preparation of a new graphene (G)- and polyaniline (PANI)-containing functional polymer gel (G/PANI/FG) through a facile crosslinking
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Hydrogels find applications in various fields, and the ever-growing spectrum of available monomers, crosslinking, and nanotechnologies widen the application of polymer hydrogels. Herein, we describe the preparation of a new graphene (G)- and polyaniline (PANI)-containing functional polymer gel (G/PANI/FG) through a facile crosslinking copolymerization approach. Several characterization techniques such as field-emission scanning electron microscopy, Fourier-transform infrared, and X-ray photoelectron spectroscopy were employed to understand the physicochemical characteristics of the G/PANI/FG. The new G/PANI/FG was used as an adsorbent for chromium (VI) and exhibited the highest Cr (VI) removal efficiency (~97%). The inclusion of G and PANI in the gel results in high surface area, 3D porous structure, and Cr (VI)-chelating amine sites, which enhanced the Cr (VI) removal efficiency and thermal stability of the gel adsorbent. The results of our study revealed that G/PANI/FG is suited for the removal of Cr (VI) from aqueous solution. Full article
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Open AccessArticle Transient Thermal Tensile Behaviour of Novel Pitch-Based Ultra-High Modulus CFRP Tendons
Polymers 2016, 8(12), 446; doi:10.3390/polym8120446
Received: 24 October 2016 / Revised: 5 December 2016 / Accepted: 6 December 2016 / Published: 21 December 2016
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Abstract
A novel ultra-high modulus carbon fibre reinforced polymer (CFRP) prestressing tendon made from coal tar pitch-based carbon fibres was characterized in terms of high temperature tensile strength (up to 570 °C) with a series of transient thermal and steady state temperature tensile tests.
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A novel ultra-high modulus carbon fibre reinforced polymer (CFRP) prestressing tendon made from coal tar pitch-based carbon fibres was characterized in terms of high temperature tensile strength (up to 570 °C) with a series of transient thermal and steady state temperature tensile tests. Digital image correlation was used to capture the high temperature strain development during thermal and mechanical loading. Complementary thermogravimetric (TGA) and dynamic mechanical thermal (DMTA) experiments were performed on the tendons to elucidate their high temperature thermal and mechanical behaviour. The novel CFRP tendons investigated in the present study showed an ambient temperature design tensile strength of 1400 MPa. Their failure temperature at a sustained prestress level of 50% of the design tensile strength was 409 °C, which is higher than the failure temperature of most fibre reinforced polymer rebars used in civil engineering applications at similar utilisation levels. This high-temperature tensile strength shows that there is potential to use the novel high modulus CFRP tendons in CFRP pretensioned concrete elements for building applications that fulfill the fire resistance criteria typically applied within the construction industry. Full article
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Review

Jump to: Research

Open AccessReview Dynamics of Polymer Translocation: A Short Review with an Introduction of Weakly-Driven Regime
Polymers 2016, 8(12), 424; doi:10.3390/polym8120424
Received: 14 October 2016 / Revised: 25 November 2016 / Accepted: 1 December 2016 / Published: 7 December 2016
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Abstract
As emphasized in a recent review (by V.V. Palyulin, T. Ala-Nissila, R. Metzler), theoretical understanding of the unbiased polymer translocation lags behind that of the (strongly) driven translocation. Here, we suggest the introduction of a weakly-driven regime, as described by the linear
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As emphasized in a recent review (by V.V. Palyulin, T. Ala-Nissila, R. Metzler), theoretical understanding of the unbiased polymer translocation lags behind that of the (strongly) driven translocation. Here, we suggest the introduction of a weakly-driven regime, as described by the linear response theory to the unbiased regime, which is followed by the strongly-driven regime beyond the onset of nonlinear response. This provides a concise crossover scenario, bridging the unbiased to strongly-driven regimes. Full article
(This article belongs to the Special Issue Young Talents in Polymer Science)
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Open AccessReview Applications of Solid-State NMR Spectroscopy for the Study of Lipid Membranes with Polyphilic Guest (Macro)Molecules
Polymers 2016, 8(12), 439; doi:10.3390/polym8120439
Received: 8 November 2016 / Revised: 1 December 2016 / Accepted: 8 December 2016 / Published: 16 December 2016
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Abstract
The incorporation of polymers or smaller complex molecules into lipid membranes allows for property modifications or the introduction of new functional elements. The corresponding molecular-scale details, such as changes in dynamics or features of potential supramolecular structures, can be studied by a variety
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The incorporation of polymers or smaller complex molecules into lipid membranes allows for property modifications or the introduction of new functional elements. The corresponding molecular-scale details, such as changes in dynamics or features of potential supramolecular structures, can be studied by a variety of solid-state NMR techniques. Here, we review various approaches to characterizing the structure and dynamics of the guest molecules as well as the lipid phase structure and dynamics by different high-resolution magic-angle spinning proton and 13C NMR experiments as well as static 31P NMR experiments. Special emphasis is placed upon the incorporation of novel synthetic polyphilic molecules such as shape-persistent T- and X-shaped molecules as well as di- and tri-block copolymers. Most of the systems studied feature dynamic heterogeneities, for instance those arising from the coexistence of different phases; possibilities for a quantitative assessment are of particular concern. Full article
(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)
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