Threshold electrical switching in As45Te55-xInx and As50Te50-xInx glasses

The electrical switching behaviour of As₄₅Te_55-xIn_x (5≤x≤15) and As₅₀Te_50-xIn_x (2.5≤x≤11.5) has been studied over a wide range of compositions. These glasses are found to exhibit threshold switching. The composition dependence of switching voltage (V_t) has been found to exhibit a change in slope and a local minimum at compositions x=10 and 12.5 for As₄₅Te_55-xIn_x and x=7.5 and 10.8 for As₅₀Te_50-xIn_x, respectively. The slope change in V_t verses x and the local minimum have been identified using two network topological effects, namely the rigidity percolation threshold and the chemical threshold. Received: 23 August 2001 / Accepted: 27 August 2001 / Published online: 11 February 2002     

Preparation and Characterization of Chitosan Thin Films on Mixed-Matrix Membranes for Complete Removal of Chromium

Herein we present a new approach for the complete removal of Cr^VI species, through reduction of Cr^VI to Cr^III, followed by adsorption of Cr^III. Reduction of chromium from water is an important challenge, as Cr^IV is one of the most toxic substances emitted from industrial processes. Chitosan (CS) thin films were developed on plain polysulfone (PSf) and PSf/TiO₂ membrane substrates by a temperature-induced technique using polyvinyl alcohol as a binder. Structure property elucidation was carried out by X-ray diffraction, microscopy, spectroscopy, contact angle measurement, and water uptake studies. The increase in hydrophilicity followed the order: PSf < PSf/TiO₂ < PSf/TiO₂/CS membranes. Use of this thin-film composite membrane for chromium removal was investigated with regards to the effects of light and pH. The observations reveal 100 % reduction of Cr^VI to Cr^III through electrons and protons donated from OH and NH₂ groups of the CS layer; the reduced Cr^III species are adsorbed onto the CS layer via complexation to give chromium-free water.     

Development and characterization of fully bio‐based polybenzoxazine‐silica hybrid composites for low‐k and flame‐retardant applications

In the present work, new classes of bio‐based polybenzoxazines were synthesized using eugenol as phenol source and furfurylamine and stearylamine as amine sources separately through solventless green synthetic process routes and were further reinforced with varying percentages (1, 3, 5, and 10 wt%) of silica (from rice husk) to attain hybrid composites. The molecular structure, cure behaviour, thermal stability, dielectric properties, and flame‐retardant behaviour of both benzoxazine monomers and benzoxazine composites were characterized using appropriate modern analytical techniques. The eugenol‐based benzoxazines synthesized using furfurylamine (FBz) and stearylamine (SBz) were cured at 223°C and 233°C, respectively. The differential scanning calorimetry (DSC) data reveal the glass transition temperatures (T_g) of FBz and SBz were 157°C and 132°C, respectively, and the maximum decomposition temperature (T_max) as obtained from thermogravimetric analysis (TGA), were found to be 464°C and 398°C for FBz and SBz, respectively. The dielectric constants for FBz and SBz obtained at 1 MHz were 3.28 and 3.62, respectively. Furthermore, varying weight percentages (1, 3, 5, and 10 wt%) of 3‐mercaptopropyltrimethoxysilane (3‐MPTMS) functionalized bio‐silica reinforced the composite materials as evidenced by their improved thermal stability and lower dielectric constant. Data obtained from thermal and dielectric studies suggested that these polybenzoxazines could be used in the form of adhesives, sealants, and composites for high performance inter‐layer low‐k dielectric applications in microelectronics.     

Tuning the Gate‐Opening Pressure in a Switching pcu Coordination Network,X‐pcu‐5‐Zn,by Pillar‐Ligand Substitution

Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacities for gas‐storage applications than the related rigid porous coordination networks. To be of practical utility, the pressures at which switching occurs, the gate‐opening and gate‐closing pressures, must lie between the storage and delivery pressures. Here we study the effect of linker substitution to fine‐tune gate‐opening and gate‐closing pressure. Specifically, three variants of a previously reported pcu ‐topology MOF, X‐pcu‐5‐Zn , have been prepared: X‐pcu‐6‐Zn , 6 =1,2‐bis(4‐pyridyl)ethane (bpe), X‐pcu‐7‐Zn , 7 =1,2‐bis(4‐pyridyl)acetylene (bpa), and X‐pcu‐8‐Zn , 8 =4,4′‐azopyridine (apy). Each exhibited switching isotherms but at different gate‐opening pressures. The N₂, CO₂, C₂H₂, and C₂H₄ adsorption isotherms consistently indicated that the most flexible dipyridyl organic linker, 6 , afforded lower gate‐opening and gate‐closing pressures. This simple design principle enables a rational control of the switching behavior in adsorbent materials.     

Cyclotriphosphazene Fibre Reinforced Poly(benzoxazine-co-ε-caprolactam) Nanocomposites for Flame Retardant Applications

Cyclophosphazene nanotube(PZT) incorporated poly(benzoxazine-co-ε-caprolactam)(P(BZ-co-CPL)) nanocomposites were developed for improving flame retardant properties. The effects of PZT on the flammability properties of P(BZ-co-CPL) matrix were evaluated through UL-94 flammability test and limiting oxygen index(LOI). The UL-94 results of P(BZ-co-CPL)/PZT hybrid nanocomposites showed V-1 rating, whereas neat P(BZ-co-CPL) showed burning rating. The LOI values are increased from 25.4 to 31.4 for 1.5 wt% PZT incorporated P(BZ-co-CPL) nanocomposite systems. SEM was used to study the char morphology of P(BZ-co-CPL)/PZT after being exposed to UL-94 flammability test. Data from thermal studies indicate that the PZT incorporated P(BZ-co-CPL) systems possess better Tg and thermal degradation behavior when compared to the neat P(BZ-co-CPL). The values of dielectric constant are decreased with increasing temperature. From the values, it is ascertained that the P(BZ-co-CPL)/PZT systems exhibit stable dielectric behavior with regard to variation in temperature. The TEM images ascertain the uniform dispersion of PZT in the P(BZ-co-CPL) matrix.     

Synthesis and characterization of thermally stable and flame retardant hexakis(4-aminophenoxy)cyclotriphosphazene-based polyimide matrices

A new approach to the preparation of hexakis(4-aminophenoxy)cyclotriphosphazene (HACTP) based polyimide (PI) matrices is proposed, for improved thermal and flame retardant properties. HACTP was synthesized with good yield. The structure of HACTP was confirmed by various characterization techniques, such as FTIR, NMR, and mass Spectroscopy. Polyimide matrices were prepared by thermal imidization process using HACTP and dianhydrides using N-methyl pyrrolidone as a solvent. The successful formation of HACTP-based polyimide matrices was confirmed by the FTIR. Thermal properties of the PI were analyzed using DSC and TGA techniques. Data obtained from the thermal studies indicate that the HACTP-based PI possesses better thermal and flame retardant properties.     

Calcium-doped ceria/titanate tabular functional nanocomposite by layer-by-layer coating method

Ca-doped ceria (CDC)/tabular titanate (K_0.8Li_0.27Ti_1.73O₄, TT) UV-shielding functional nanocomposite with fairly uniform CDC coating layers was prepared through a polyelectrolyte-associated layer-by-layer (LbL) coating method. TT with lepidocrocite-like layered structure was used as the substrate, poly (diallyldimethylammonium chloride) (PDDA) was used as a coupling agent, CDC nanoparticles were used as the main UV-shielding component. CDC/TT nanocomposites with various coating layers of CDC were obtained through a multistep coating process. The phases were studied by X-ray diffraction. The morphology and coating quality were studied by scanning electron microscopy and element mapping of energy dispersive X-ray analysis. The oxidation catalytic activity, UV-shielding ability and using comfort were characterized by Rancimat test, UV-vis spectra and dynamic friction test, respectively. CDC/TT nanocomposites with low oxidation catalytic activity, high UV-shielding ability and good using comfort were finally obtained.     

Application of Bioassay-Guided Fractionation Coupled with a Molecular Approach for the Dereplication of Antimicrobial Metabolites

A systematically delineated dereplication approach was described based on genome mining and bioassay-guided fractionation using endophytic fungus Xylaria psidii FPL-52(S) isolated from leaves of Ficus pumila Linn., (Moraceae). A polyketide synthase gene-based molecular screening strategy by a degenerate oligonucleotide primer polymerase chain reaction technique coupled with a bioinformatic phylogenomic approach revealed the presence of an iterative polyketide synthase gene within the genome of Xylaria psidii FPL-52(S). Chemical dereplication of ethyl acetate extract derived from a submerged fermentation culture broth of Xylaria psidii FPL-52(S) by bioassay-guided chromatographic and hyphenated analytical spectroscopic techniques led to the identification of polyketide mycoalexin 3-O-methylmellein. Antimicrobial profiling and minimal inhibitory concentration values for 3-O-methylmellein were determined by disc diffusion and microbroth dilution techniques. Gram-positive bacteria, dermatophytic and phytopathogenic fungi were susceptible in terms of inhibition zone and minimum inhibitory concentration values when compared to co-assayed standards. Herein, we highlight and demonstrate an improved approach which facilitates efficient dereplication and effect-guided fractionation of antimicrobial metabolite(s). The present work flow serves as a promising dereplication tool to survey the biosynthetic potential of endophytic fungal diversity, thereby identifying the most promising strains and prioritizing them for novel polyketide-derived antimicrobial metabolite discovery.

     

Linear and nonlinear stability of double diffusive convection in a couple stress fluid–saturated porous layer

The linear and nonlinear stability of double diffusive convection in a layer of couple stress fluid–saturated porous medium is theoretically investigated in this work. Applying the linear stability theory, the criterion for the onset of steady and oscillatory convection is obtained. Emphasizing the presence of couple stresses, it is shown that their effect is to delay the onset of convection and oscillatory convection always occurs at a lower value of the Rayleigh number at which steady convection sets in. The nonlinear stability analysis is carried out by constructing a system of nonlinear autonomous ordinary differential equations using a truncated representation of Fourier series method and also employing modified perturbation theory with the help of self-adjoint operator technique. The results obtained from these two methods are found to complement each other. Besides, heat and mass transport are calculated in terms of Nusselt numbers. In addition, the transient behavior of Nusselt numbers is analyzed by solving the nonlinear system of ordinary differential equations numerically using the Runge–Kutta–Gill method. Streamlines, isotherms, and isohalines are also displayed.