Structural and luminescence properties of RE (RE = Eu, Tb):(MgCa)2Bi4Ti5O20 ceramics

Rare-earth ions (Eu³⁺, Tb³⁺) activated magnesium calcium bismuth titanate [(MgCa)₂Bi₄Ti₅O₂₀] ceramics were prepared by conventional solid state reaction method for their structural and luminescence properties. By using XRD patterns, the structural properties of ceramic powders have been analyzed. Emission spectrum of Eu³⁺:(MgCa)₂Bi₄Ti₅O₂₀ ceramic powder has shown strong red emission at 615 nm (⁵D₀ → ⁷F₂) with an excitation wavelength λ_exci = 393 nm and Tb³⁺:(MgCa)₂Bi₄Ti₅O₂₀ ceramic powder has shown green emission at 542 nm (⁵D₄ → ⁷F₅) with an excitation wavelength λ_exci = 376 nm. In addition, from the measurements of scanning electron microscopy (SEM), Fourier transform-infrared (FTIR) and energy dispersive X-ray analysis (EDAX) results the morphology, structure and elemental analysis of these powder ceramics have been studied.     

Electrical and rheological percolation in poly(vinylidene fluoride)/multi‐walled carbon nanotube nanocomposites

Nanocomposites of poly(vinylidene fluoride) (PVDF) and multi‐walled carbon nanotubes (MWCNTs) were prepared through melt blending in a batch mixer (torque rheometer equipped with a mixing chamber). The morphology, rheological behavior and electrical conductivity were investigated through transmission electron microscopy, dynamic oscillatory rheometry and the two‐probe method. The nanocomposite with 0.5 wt% MWCNT content presented a uniform dispersion through the PVDF matrix, whereas that with 1 wt% started to present a percolated network. For the nanocomposites with 2 and 5 wt% MWCNTs the formation of this nanotube network was clearly evident. The electrical percolation threshold at room temperature found for this system was about 1.2 wt% MWCNTs. The rheological percolation threshold fitted from viscosity was about 1 wt%, while the threshold fitted from storage modulus was 0.9 wt%. Thus fewer nanotubes are needed to approach the rheological percolation threshold than the electrical percolation threshold. Copyright © 2010 Society of Chemical Industry     

Poly(dimethylsiloxane-urethane) membranes: effect of linear siloxane chain and caged silsesquioxane on gas transport properties

The effect of poly(dimethylsiloxane) (PDMS) or polypropylene glycol (PPG) linear chain and polyoctahedral oligosilsesquioxanes (POSS) cubic nanoparticles on surface and gas transport properties of poly(dimethylsiloxane-urethane) PDMS-PU or poly(propylene glycol-urethane) (PPG-PU) hybrid membranes were studied. PDMS-PU or PPG-PU hybrid membranes were prepared using PDMS-diol or PPG-diol as a chain extender and diisocyanate with POSS-amine macromonomer as a crosslinker. The macromer synthesized was characterized using FT-IR, ¹H-, ¹³C- and ²⁹Si-NMR spectroscopic methods. The hybrid membranes were characterized by CP-MAS ²⁹Si-NMR, DSC, contact angle, WAXD, AFM and density measurements. The glass transition temperature (Tg) of the hybrid membranes were determined by differential scanning calorimetry (DSC) and were found to be in the range of 176–189°C. The surface free energy was reduced by increasing the POSS-amine crosslinker content of the membranes. The AFM measurement showed phase separation of POSS-amine molecule and PDMS with the urethane matrix on the surfaces. The XRD profiles confirm that the membranes were highly amorphous in nature. The decrease in permeability was observed by increasing the concentration of POSS-amine incorporated hybrid membranes. The selectivities of O₂/N₂ and CO₂/N₂ gas pairs increased with an increase in the POSS concentration. This suggests that the selectivities were dependent mainly on the presence of urethane and ester functional groups in the crosslinker.     

Precursor gas chemistry determines the crystallinity of carbon nanotubes synthesized at low temperature

Despite significant progress in carbon nanotube (CNT) synthesis by thermal chemical vapor deposition (CVD), the factors determining the structure of the resulting carbon filaments and other graphitic nanocarbons are not well understood. Here, we demonstrate that gas chemistry influences the crystal structure of carbon filaments grown at low temperatures (500 °C). Using thermal CVD, we decoupled the thermal treatment of the gaseous precursors (C₂H₄/H₂/Ar) and the substrate-supported catalyst. Varying the preheating temperature of the feedstock gas, we observed a striking transition between amorphous carbon nanofibers (CNFs) and crystalline CNTs. These results were confirmed using both a hot-wall CVD system and a cold-wall CVD reactor. Analysis of the exhaust gases (by ex situ gas chromatography) showed increasing concentrations of specific volatile organic compounds (VOCs) and polycyclic aromatic hydrocarbons (PAHs) that correlated with the structural transition observed (characterized using high-resolution transmission electron microscopy). This suggests that the crystallinity of carbon filaments may be controlled by the presence of specific gas phase precursor molecules (e.g., VOCs and PAHs). Thus, direct delivery of these molecules in the CVD process may enable selective CNF or CNT formation at low substrate temperatures. The inherent scalability of this approach could impact many promising applications, especially in the electronics industry.     

Synthesis and electrocatalytic oxygen reduction activity of graphene-supported Pt3Co and Pt3Cr alloy nanoparticles

Graphene-supported Pt and Pt₃M (M = Co and Cr) alloy nanoparticles are prepared by ethylene glycol reduction method and characterized with X-ray diffraction and transmission electron microscopy. X-ray diffraction depicted the face-centered cubic structure of Pt in the prepared materials. Electron microscopic images show the high dispersion of metallic nanoparticles on graphene sheets. Electrocatalytic activity and stability of the materials is investigated by rotating-disk electrode voltammetry. Oxygen reduction activity of the Pt₃M/graphene is found to be 3–4 times higher than that of Pt/graphene. In addition, Pt₃M/graphene electrodes exhibited overpotential 45–70 mV lower than that of Pt/graphene. The high catalytic performance of Pt₃M alloys is ascribed to the inhibition of formation of (hydr) oxy species on Pt surface by the alloying elements. The fuel cell performance of the catalysts is tested at 353 K and 1 atm. Maximum power densities of 790, 875, and 985 mW/cm² are observed with graphene-supported Pt, Pt₃Co, and Pt₃Cr cathodes, respectively. The enhanced electrocatalytic performance of the Pt₃M/graphene (M = Co and Cr) compared to that of Pt/graphene makes them a viable alternative to the extant cathodes for energy conversion device applications.     

Anodic dissolution of U, Zr and U–Zr alloy and convolution voltammetry of Zr|Zr couple in molten LiCl–KCl eutectic

The anodic dissolution of U and Zr metal was studied in LiCl–KCl–UCl₃ and LiCl–KCl–ZrCl₄, respectively, at 773 K by cyclic voltammetry and compared with their respective dissolution behaviour in blank LiCl–KCl eutectic. The anodic dissolution of U–Zr alloy in LiCl–KCl–UCl₃ was also studied at 773 K to compare with the dissolution of U and Zr. The transfer coefficients evaluated by Tafel analysis and the method of Allen–Hickling for U and Zr dissolution were found to be in fair agreement with each other. U dissolution in LiCl–KCl–UCl₃ and Zr dissolution LiCl–KCl–ZrCl₄ were also studied by chronoamperometry and the diffusion coefficient value of U³⁺ was calculated to be in the range of 2.9 × 10⁻⁵ to 3.3 × 10⁻⁵ cm² s⁻¹ which is in agreement with those reported in literature. Convolution voltammetric analysis of Zr⁴⁺/Zr²⁺ redox couple in LiCl–KCl–ZrCl₄ was carried out for the first time to have a comprehensive understanding of the electrode kinetics.     

Design of Efficient Ce<Subscript>x</Subscript>M<Subscript>1−x</Subscript>O<Subscript>2−δ</Subscript> (M = Zr,Hf, Tb and Pr) Nanosized Model Solid Solutions for CO Oxidation

Abstract  

Nanosized Ce_xM_1−xO_2−δ (M = Zr, Hf, Tb and Pr) solid solutions were prepared by a modified coprecipitation method and thermally treated at different temperatures from 773 to 1073 K in order to ascertain the thermal behavior. The structural and textural properties of the synthesized samples were investigated by means of X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), BET surface area, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy (RS) techniques. The catalytic efficiency has been performed towards oxygen storage/release capacity (OSC) and CO oxidation activity. The characterization results indicated that the obtained solid solutions exhibit defective cubic fluorite structure. The solid solutions of ceria–hafnia, ceria–terbia and ceria–praseodymium exhibited good thermal stability up to 1073 K. A new Ce_0.6Zr_0.4O₂ phase along with Ce_0.75Zr_0.25O₂ was observed in the case of ceria–zirconia solid solution due to more Zr⁴⁺ incorporation in the ceria lattice at higher calcination temperatures. The reducibility of ceria has been increased upon doping with Zr⁴⁺, Hf⁴⁺, Tb^3+/4+ and Pr^3+/4+ cations. This enhancement is more in case of Hf⁴⁺ doped ceria. Among various solid solutions investigated, the ceria–hafnia combination exhibited better OSC and CO oxidation activity. The high efficiency of Ce–Hf solid solution was correlated with its superior bulk oxygen mobility and other physicochemical characteristics.     

Miscibility studies of sodium carboxymethylcellulose/poly(vinyl alcohol) blend membranes for pervaporation dehydration of isopropyl alcohol

Miscibility studies of sodium carboxymethylcellulose/poly(vinyl alcohol) (NaCMC/PVA) blends of different compositions (100/0, 80 : 20, 60 : 40, 50 : 50, 40 : 60, 20 : 80, and 0 : 100) were investigated using viscometric method. NaCMC, PVA, and their blend membranes were prepared by solution‐casting technique and were then crosslinked with glutaraldehyde (GA). The effect of blend composition on mechanical, swelling, and pervaporation results (flux and selectivity) was also investigated in this study. Attenuated total reflectance–Fourier transform infrared spectroscopy (ATR–FTIR) results showed that the blends are miscible over the entire studied composition range and further confirmed the crosslinking reaction with GA. FTIR studies reveal that the blends containing 50 : 50 (NaCMC/PVA) are an optimum miscible blend. Thermogravimetric analysis confirms that the thermal stability increased with increase in NaCMC content in NaCMC/PVA blend membrane. XRD and DSC showed a corresponding decrease in crystallinity and increase in melting point with increase in NACMC content, respectively. NaCMC/PVA blends of all the composition under study were used for dehydration of isopropyl alcohol at different compositions of IPA/water mixture (90 : 10, 87.5 : 12.5, 85 : 15, and 82.5 : 17.5) at 35°C. Swelling studies and PV results reveal that increase in NaCMC content in the blend leads to an increase in flux of water, whereas selectivity decreases. The optimum flux and selectivity were observed for the blend containing 50 : 50 NaCMC/PVA content at a feed ratio of 87.5 : 12.5 IPA/water. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of pro‐oxidants on biodegradation of polyethylene (LDPE) by indigenous fungal isolate,Aspergillus oryzae

Proxidant additives represent a promising solution to the problem of the environment contamination with polyethylene film litter. Pro‐oxidants accelerate photo‐ and thermo‐oxidation and consequent polymer chain cleavage rendering the product apparently more susceptible to biodegradation. In the present study, fungal strain, Aspergillus oryzae isolated from HDPE film (buried in soil for 3 months) utilized abiotically treated polyethylene (LDPE) as a sole carbon source and degraded it. Treatment with pro‐oxidant, manganese stearate followed by UV irradiation and incubation with A. oryzae resulted in maximum decrease in percentage of elongation and tensile strength by 62 and 51%, respectively, compared with other pro‐oxidant treated LDPE films which showed 45% (titanium stearate), 40% (iron stearate), and 39% (cobalt stearate) decrease in tensile strength. Fourier transform infrared (FTIR) analysis of proxidant treated LDPE films revealed generation of more number of carbonyl and carboxylic groups (1630–1840 cm⁻¹ and 1220–1340 cm⁻¹) compared with UV treated film. When these films were incubated with A. oryzae for 3 months complete degradation of carbonyl and carboxylic groups was achieved. Scanning electron microscopy of untreated and treated LDPE films also revealed that polymer has undergone degradation after abiotic and biotic treatments. This concludes proxidant treatment before UV irradiation accelerated photo‐oxidation of LDPE, caused functional groups to be generated in the polyethylene film and this resulted in biodegradation due to the consumption of carbonyl and carboxylic groups by A. oryzae which was evident by reduction in carbonyl peaks. Among the pro‐oxidants, manganese stearate treatment caused maximum degradation of polyethylene. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Purification and enzymatic properties of the extracellular and constitutive chitosanase produced by Bacillus subtilis RKY3

BACKGROUND: Purification and enzymatic properties of a chitosanase from Bacillus subtilis RKY3 have been investigated to produce a chitooligosaccharide. The enzyme reported was extracellular and constitutive, which was purified by two sequential steps including ammonium sulfate precipitation and ion exchange chromatography. RESULTS: Sodium dodecyl sulfate‐polyacrylamide gel electrophoresis of the purified chitosanase revealed one single band corresponding to a molecular weight of around 24 kDa. The highest chitosanase activity was found to be at pH 6.0 and at 60 °C. Although the mercaptide forming agents such as Hg²⁺ (10 mmol L^?1) and p‐hydroxymercuribenzoic acid (1 mmol L^?1, 10 mmol L^?1) significantly or totally inhibited the enzyme activity, its activity was enhanced by the presence of 10 mmol L^?1 Mn²⁺. The enzyme showed activity for hydrolysis of soluble chitosan and glycol chitosan, but colloidal chitin, carboxymethyl cellulose, crystalline cellulose, and soluble starch were not hydrolyzed. The analysis of chitosan hydrolysis by thin‐layer chromatography and viscosity variation revealed that the purified enzyme should be endosplitting‐type chitosanase. CONCLUSION: The chitosanase produced by Bacillus subtilis RKY3 was a novel chitosanlytic enzyme with relatively low molecular weight, which is a versatile enzyme for chitosan hydrolysis because it could hydrolyze soluble chitosan into a biofunctional oligosaccharide at a high level. Copyright © 2011 Society of Chemical Industry