Biocomposite proton‐exchange membrane electrolytes for direct methanol fuel cells

Poly(vinyl alcohol) (PVA)‐amino acid (AA) biocomposite membranes are prepared by blending PVA with AAs such as glycine, lysine (LY), and phenyl alanine followed by in situ crosslinking with citric acid (CA) and explored as a new class of biocomposite membrane electrolytes for direct methanol fuel cells (DMFCs). CA crosslinks with PVA through esterification offers adequate chemical, thermal, and morphological stability thereby produces methanol‐obstructing close‐packed polymeric network. These biocomposite membranes are characterized in terms of mechanical, thermal, sorption, and proton‐conducting properties. Hydrophilic nature of AA zwitterions significantly facilitates proton conduction and CA crosslinking mitigates methanol crossover through establishing appropriate balance between hydrophilic/hydrophobic domains. The rational design of membrane microstructure with proper arrangement of hydrophobic/hydrophilic domains is a key to enhance electrochemical selectivity of PVA‐AA/CA biocomposite membranes. Biocomposite membrane comprising LY exhibits nearly threefold higher electrochemical selectivity in relation to PVA/CA blend membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43514.     

Mechanical and thermal properties of wood fibers reinforced poly(lactic acid)/thermoplasticized starch composites

Thermoplasticized starch (TPS) filled poly(lactic acid) (PLA) blends are usually found to have low mechanical properties due to poor properties of TPS and inadequate adhesion between the TPS and PLA. The purpose of this study was to investigate the reinforcing effect of wood fibers (WF) on the mechanical properties of TPS/PLA blends. In order to improve the compatibility of wood with TPS/PLA blends, maleic anhydride grafted PLA (MA‐g‐PLA) copolymer was synthesized and used. TPS, TPS/PLA blends, and WF reinforced TPS/PLA composites were prepared by twin‐screw extrusion and injection molded. Scanning electron microscope and crystallinity studies indicated thermoplasticity in starch. WF at two different weight proportions, that is, 20% and 40% with respect to TPS content were taken and MA‐g‐PLA at 10% to the total weight was chosen to study the effect on mechanical properties. At 20% WF and 10% MA‐g‐PLA, the tensile strength exhibited 86% improvement and flexural strength exhibited about 106% improvement over TPS/PLA blends. Increasing WF content to 40% further enhanced tensile strength by 128% and flexural strength by 180% with respect to TPS/PLA blends. Thermal behavior of blends and composites was analyzed using dynamic mechanical analysis and thermogravimetric analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46118.     

The Importance of G Protein-Coupled Receptor Kinase 4 (GRK4) in Pathogenesis of Salt Sensitivity,Salt Sensitive Hypertension and Response to Antihypertensive Treatment

Salt sensitivity is probably caused by either a hereditary or acquired defect of salt excretion by the kidney, and it is reasonable to consider that this is the basis for differences in hypertension between black and white people. Dopamine acts in an autocrine/paracrine fashion to promote natriuresis in the proximal tubule and thick ascending loop of Henle. G-protein receptor kinases (or GRKs) are serine and threonine kinases that phosphorylate G protein-coupled receptors in response to agonist stimulation and uncouple the dopamine receptor from its G protein. This results in a desensitisation process that protects the cell from repeated agonist exposure. GRK4 activity is increased in spontaneously hypertensive rats, and infusion of GRK4 antisense oligonucleotides attenuates the increase in blood pressure (BP). This functional defect is replicated in the proximal tubule by expression of GRK4 variants namely p.Arg65Leu, p.Ala142Val and p.Val486Ala, in cell lines, with the p.Ala142Val showing the most activity. In humans, GRK4 polymorphisms were shown to be associated with essential hypertension in Australia, BP regulation in young adults, low renin hypertension in Japan and impaired stress-induced Na excretion in normotensive black men. In South Africa, GRK4 polymorphisms are more common in people of African descent, associated with impaired Na excretion in normotensive African people, and predict blood pressure response to Na restriction in African patients with mild to moderate essential hypertension. The therapeutic importance of the GRK4 single nucleotide polymorphisms (SNPs) was emphasised in the African American Study of Kidney Disease (AASK) where African-Americans with hypertensive nephrosclerosis were randomised to receive amlodipine, ramipril or metoprolol. Men with the p.Ala142Val genotype were less likely to respond to metoprolol, especially if they also had the p.Arg65Leu variant. Furthermore, in the analysis of response to treatment in two major hypertension studies, the 65Leu/142Val heterozygote predicted a significantly decreased response to atenolol treatment, and the 65Leu/142Val heterozygote and 486Val homozygote were associated in an additive fashion with adverse cardiovascular outcomes, independent of BP. In conclusion, there is considerable evidence that GRK4 variants are linked to impaired Na excretion, hypertension in animal models and humans, therapeutic response to dietary Na restriction and response to antihypertensive drugs. It may also underlie the difference in hypertension between different geographically derived population groups, and form a basis for pharmacogenomic approaches to treatment of hypertension.     

Influence of Distributed Particle Size on the Determination of the Parabolic Rate Constant for Oxidation by the Powder Method

The established analysis for the study of oxidation using powder specimens is based on the assumption of monosized particles. The experiments, however, are conducted on powders with a distributed particle size. Here we present a statistical approach for the calculation of the rate constant for oxidation. The results of the analysis are applied to new data on oxidation studies of dense powders of silicon carbonitride amorphous ceramics. The monosized model requires a wide range of values for the rate constant to fit the short term and the long-term data, leading to considerable ambiguity in the estimate of the parabolic rate constant, k _p, for oxidation. In contrast the statistical model fits over the entire range of data, yielding a much more reliable value for k _p. For example, the monosized approach gave a value in the range 19.7 × 10⁻¹⁸ < k _p < 2.7 × 10⁻¹⁸ m²/s. In contrast, the statistical model yields a specific value of 4.5 × 10⁻¹⁸ m²/s.     

Sintering and thermal expansion behaviors of glass and glass–YSZ composites as self-repairable seals for SOFC

Glass and glass–ceramics are used as sealants in solid oxide fuel cell (SOFC) because their thermophysical properties can be tailored to meet the stringent requirements of the SOFC stack. The processing, sintering, and thermal expansion behaviors of self-healing and non-crystallizing glass and glass containing 10%–30 wt.% non-reacting yttria-stabilized zirconia (YSZ) are studied. The addition of inert YSZ to glass significantly retarded the sintering behavior. Thermal expansion behaviors of glass and glass–YSZ are also measured to study the role of YSZ addition on the glass transition, softening point, and coefficient of thermal expansion (CTE). It is shown that the densification is controlled by the viscous sintering mechanism, in which the addition of YSZ increased the effective viscosity of the glass–YSZ as evident from higher glass transition and softening temperatures and decreased CTE. These results demonstrated that the addition of YSZ to glass is promising for achieving optimum thermophysical properties useful as seals for SOFC.     

Limits to the Stability of the Amorphous Nature of Polymer‐Derived HfSiCNO Compounds

Substituting silicon by transition metals in polymer‐derived ceramics (PDCs) holds the potential for a new class of polymer‐derived ceramics for ultrahigh‐temperature structural applications. We present experiments that show that the solid solubility of HfO₂ extends to Hf/Si ratio of <0.22. The materials are synthesized from (miscible) organic precursors. Similar to silicon‐based materials they remain amorphous after pyrolysis at 1000°C. Small‐angle X‐ray scattering and Raman spectra remain essentially unaltered. It is postulated that Hf, like Si, forms mixed‐bond tetrahedra with C, O, and N. The difference in the enthalpy of Hf‐based, and Si‐centered tetrahedra is calculated using single‐bond energies, reinforcing the feasibility of substituting Si with Hf or with Zr atoms. Such polymer‐based HfSiCNO compounds made directly from liquid organics, by a simple manufacturing process, may also be relevant to nanoscale dielectrics with low leakage electric charge in microelectronics applications.     

Impedance Spectroscopy and Dielectric Properties of Flash Versus Conventionally Sintered Yttria‐Doped Zirconia Electroceramics Viewed at the Microstructural Level

The defect chemistry‐modulated dielectric properties of dense yttria‐doped zirconia ceramics prepared by conventional sintering (at 1350°C–1500°C) and electric field‐assisted flash sintering (55 V/cm at 900°C) were studied by impedance spectroscopy. While the bulk dielectric properties from both sets of samples showed only small and insignificant changes in conductivity and permittivity, respectively, a huge increase of these properties was measured for the grain boundaries in the flash sintered specimens. A close analysis of these results suggests that flash sintering reduced grain‐boundary thickness (by about 30%), while increasing the concentration of oxygen vacancies near these interfaces (by about 49%). The underlying mechanism proposed is electric field‐assisted generation and accommodation of defects in the space‐charge layers adjacent to the grain surface. The changes in measured permittivity are attributed to the boundary thickness effect on capacitance, while conductivity involved variations in its defect density‐dependent intrinsic value, accounting for changes also observed in grain‐boundary relaxation frequencies. Therefore, in terms of modifications to the specific dielectric properties of these materials, the overall consequence of flash sintering was to considerably lower the semi‐blocking character of the grain boundaries.     

Can Die Configuration Influence Field‐Assisted Sintering of Oxides in the SPS Process?

Spark plasma sintering (SPS) is a high current, low voltage process. Nevertheless, the system voltage (3–10 V) can be large enough to produce significant fields across a thin, insulating sample. A lumped circuit model is analyzed to estimate the magnitude of this field in terms of the die geometry. Normalizing the sample voltage with respect to the system voltage, and the die wall thickness to the punch radius preserves generality of the results. It is predicted that if the latter ranges from 0.15 to 0.25, then 30% of the system voltage may be expressed across the sample. Thus, a sample thickness of about 1–2 mm may experience a field of 10–30 V/cm, which would be large enough to induce field‐assisted sintering in yttria‐stabilized zirconia. The results are corroborated with finite element analysis. The contact resistance is assumed to be negligible; finite values of the contact resistance would lead to fields that are higher than predicted.     

Electrospun gelatin/nylon‐6 composite nanofibers for biomedical applications

We describe the preparation and characterization of gelatin‐containing nylon‐6 electrospun fibers and their potential use as a bioactive scaffold for tissue engineering. The physicochemical properties of gelatin/nylon‐6 composite nanofibers were analyzed using field emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, TGA and contact angle and tensile measurements. FE‐SEM and TEM images revealed that the nanofibers were well oriented and showed a good incorporation of gelatin. FTIR spectroscopy and TGA also revealed that there was good interaction between the two polymers at the molecular level. The adhesion, viability and proliferation properties of osteoblast cells on the gelatin/nylon‐6 composite nanofibers were analyzed by an in vitro cell compatibility test. Our results suggest that the incorporation of gelatin can increase the cell compatibility of nylon‐6 and therefore the composite mat obtained has great potential in hard tissue engineering. © 2012 Society of Chemical Industry     

A green and facile one-pot synthesis of Ag–ZnO/RGO nanocomposite with effective photocatalytic activity for removal of organic pollutants

In this study, Ag–ZnO/reduced graphene oxide (Ag–ZnO/RGO) composite was synthesized by a green and facile one-step hydrothermal process. Aqueous suspension containing Ag and ZnO precursors with graphene oxide (GO) sheets was heated at 140 °C for 2 h. The morphology and structure of as-synthesized particles were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, and Photoluminescence (PL) spectroscopy which revealed the formation of composite of metal, metal oxide and RGO. It was observed that the presence of Ag precursor and GO sheets in the hydrothermal solution could sufficiently decrease the size of ZnO flowers. The hybrid nanostructure, with unique morphology, obtained from this convenient method (low temperature, less time, and less number of reagents) was found to have good photocatalytic and antibacterial activity. The perfect recovery of catalyst after reaction and its unchanged efficiency for cyclic use showed that it will be an economically and environmentally friendly photocatalyst.