Studies on the effect of thiuram disulfide on NR vulcanization accelerated by thiazole-based accelerator systems

Thiuram disulfides form synergistic combinations with thiazole and thiazole-based accelerators, namely, N-cyclohexy-2-benzothiazole sulfenamide (CBS), 2-mercaptobenzothiazole(MBT), and 2-mercaptobenzothiazyl disulfide (MBTS). Unfortunately, widely used thiuram disulfides (TD) generate carcinogenic N-nitrosoamine. It is reported that the nitrosamines from N-methylpiperazine and dibenzylamine are free from this menace. So, some investigations were carried out with the binary combinations of each of bis(N-methylpiperazino)thiuram disulfide (MPTD), tetrabenzylthiuram disulnde (TBzTD), and tetramethyl-thiuram disulfide (TMTD) separately with CBS, MBT, and MBTS. It was observed that all the TD are activated by the CBS, MBT, or MBTS in the combinations studied. The intensity of activation is manifested in the enhancement of torque, modulus, tensile strength, cure rate, hardness, and decrease of elongation at break values and is very much dependent upon the ratio of the accelerators used. Considering the torque, modulus, tensile strength, and the elongation at break values, it apears that MPTD and TBzTD are capable of competing with the hitherto unbeaten TMTD as suitable accelerators for the vulcanization of rubber. Some investigations in respect to heat- and age-resistance behavior have also been carried out and the observed differences in the activities of various binary combinations have been explained through a mechanism. The results obtained with filled vulcanizates indicate that the binary systems comprising TD and MBTS provide fruitful results of which the TBzTD–MBTS combination seems to give the best cure and physical data for practical vulcanizates. © 1996 John Wiley & Sons, Inc.     

CFD analysis of water gas shift membrane reactor

Fuel cell based modular power generation can be achieved by miniaturization and process intensification of equipments in the process. Fuel cells require hydrogen rich gas which can be generated through reforming and water gas shift reaction. The water gas shift reactor being kinetically limited occupies more volume to achieve the required CO conversion. A membrane reactor integrates the reaction and hydrogen separation stages and hence reduces the volume requirement. Computational Fluid Dynamics offers virtual prototyping of the reactor and thus helps in design, optimization and scale up of reactors. In this study customized User Defined Functions (UDFs) were developed to analyze the performance of low temperature water gas shift membrane reactor. The models were validated using literature data for the parameters – synthesis gas compositions, time factor, sweep flow rate and steam to CO ratio. The effect of all these parameters on the reactor was analyzed for CO conversion, H₂ recovery, DaPe, concentration polarization, concentration profiles and conversion index. The simulations have showed that the UDFs developed were capable of simulating the membrane reactor and this can be used for the design and optimization of the membrane reactor for any process conditions.     

Chitosan/poly(dimethylaminoethylmethacrylate-co-hydroxyethylacrylate) based semi-IPN hydrogels and silver nanocomposites: Synthesis,evaluation of amoxicillin release studies,and antibacterial studies

To fabricate new smart materials that can deliver both the pharmaceutically active molecules and metal nanoparticles, we have formulated chitosan-based semi-IPN hydrogels and their silver nanocomposites (Ag NCs) along with amoxicillin (AMX). Semi-IPN hydrogels and their Ag NCs were synthesized from chitosan, dimethylamino ethyl methacrylate and 2-hydroxyethyl methacrylate via simple-free radical polymerization method and reducing with NaBH₄. The resultant formulations were evaluated for in vitro release of AMX, anti-bacterial studies and DNA cleavage studies. The hydrogels with AMX-derived silver nanoparticles (Ag NPs) show better ability to cleave DNA and anti-microbial activity than individual AMX and Ag NPs.     

Non-catalytic vanadium removal from vanadyl etioporphyrin (VO-EP) using a mixed solvent of supercritical water and toluene: A kinetic study

Reaction kinetics and mechanisms of the decomposition of vanadyl etioporphyrin (VO-EP), the most common metal compounds present in heavy crude, were studied in a mixed solvent of supercritical water (SCW) and toluene without the addition of any catalyst, H₂ or H₂S to remove vanadium. The aim of this study was to remove vanadium an environmentally benign way from VO-EP at a high extent and in a short reaction time. The experiments were conducted in an 8.8 mL batch reactor fabricated from Hastelloy C-276. The capability of SCW to remove vanadium from VO-EP was discovered at temperatures of 410–490 °C and a water partial pressure (WPP) of 25 MPa. Experimental results revealed that the overall VO-EP conversion was 90.51% at a temperature of 490 °C, WPP of 25 MPa and reaction time of 180 min. Under the same reaction conditions, approximately 80.26% vanadium was removed by reaction with SCW. The global reaction followed first order kinetics, with Arrhenius parameters of activation energy 8.93 kcal/mol and a pre-exponential factor 5.66 s^?1. A kinetic model of demetallation that well-fit the experimental results, was proposed. The reaction kinetics may be critically explained in terms of free radical mechanism. The obtained results suggest that SCW is capable of removing vanadium from VO-EP.     

Studies on phytosterol oxides. II: Content in some vegetable oils and in French fries prepared in these oils

Hydrogenated rapeseed oil/palm oil blend, sunflower oil and high-oleic sunflower oil, and French fries fried in these oils were assessed for contents of sterol oxidation products. Different oxidation products of phytosterols (7α- and 7β-hydroxy-sito-and campesterol, 7-ketosito- and 7-ketocampesterol, 5α,6α-epoxy-sito- and campesterol, 5β,6β-epoxy-sito-and campesterol, dihydroxysitosterol and dihydroxycampesterol) were identified and quantiated by gas chromatography (GC) and GC-mass spectroscopy. Rapeseed oil/palm oil blend contained 41 ppm total sterol oxides before frying operations. After two days of frying, this level was increased to 60 ppm. Sunflower oil and high-oleic sunflower oil had 40 and 46 ppm sterol oxides, respectively, before frying operations. After two days of frying operations, these levels increased to 57 and 56 ppm, respectively. In addition to campesterol and sitosterol oxidation products, small amounts of 7α- and 7β-hydroxystigmasterol were detected in the oil samples. Total sterol oxides in the lipids of French fries fried at 200°C in rapeseed oil/palm oil blend, sunflower oil, and high-oleic sunflower oil were 32, 37, and 54 ppm, respectively. The levels of total oxidized sterols, calculated per g sample, ranged from 2.4 to 4.0 ppm. In addition to the content of phytosterol oxides, full scan mass spectra of several oxidation products of stigmasterol are reported for the first time. Part of these results were presented at the 86th Annual Meeting of the AOCS, May 7–11, 1995, San Antonio, TX.     

Effect of Porosity on Structure,Young's Modulus,and Thermal Conductivity of SiC Foams by Direct Foaming and Gelcasting

The study demonstrates the aqueous processing of solid‐state‐sintered SiC foams by gelcasting technique. Aside from increasing strength of green bodies, gelcasting monomers were the source of carbon additive which helped in sintering of SiC foams. Sintered foams with the relative density (RD) between 0.44 and 0.11 were processed by direct foaming of SiC slurries followed by gelcasting and sintering. Structural analysis by X‐ray tomography showed the presence of spherical pores with bimodal pore size distribution and the proportion of large size cell and their interconnectivity increased in low RD foams. SEM study revealed that decreased RD resulted in gradual changes in the strut microstructure from the grains with faceted interface to smooth interfaced grains. The analysis of changes in Young's modulus and thermal conductivity with RD were in agreement with the Ashby model for open cell foams.     

Water absorption,residual mechanical and thermal properties of hydrothermally conditioned nano-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> enhanced glass fiber reinforced polymer composites

The durability of the nano-Al₂O₃ enhanced glass fiber reinforced polymer (GFRP) composites in hydrothermal environment is necessary for hydro/hygro thermal applications. The present investigation emphasizes the effect of nano-Al₂O₃ filler concentration on moisture absorption kinetics, residual mechanical and thermal properties of hydrothermally treated GFRP nano-composites. Nano-Al₂O₃ particles were mixed with epoxy matrix through temperature assisted magnetic stirrer and followed by ultrasonic treatment. It has been observed that, the addition of 0.1 wt% of nano-Al₂O₃ into the GFRP nano-composites reduces the moisture diffusion coefficient by 10%, as well as improves the flexural residual strength by 16% and interlaminar residual shear strength by 17% as compared to the neat epoxy GFRP composites. However, the glass transition temperature has not been improved by the addition of nano-Al₂O₃ filler. Weibull design parameters have been determined for dry and hydrothermally conditioned nano-composites. A good agreement between the experimental and the simulated stress–strain results has been observed. The interface failure mechanism has been evaluated by field emission scanning electron microscope to support the new findings.     

STUDIES ON THE ADSORPTION OF FURFURAL FROM AQUEOUS SOLUTION ONTO LOW-COST BAGASSE FLY ASH

The present study deals with the sorptive removal of furfural from aqueous solution by carbon-rich bagasse fly ash (BFA). Batch studies were performed to evaluate the influence of various experimental parameters, namely, initial pH (p H ₀), adsorbent dose, contact time, initial concentration, and temperature on the removal of furfural. Optimum conditions for furfural removal were found to be p H ₀ ≈ 5.5, adsorbent dose ≈4 g/L of solution, and equilibrium time ≈4 h. The adsorption followed pseudo-second-order kinetics. The effective diffusion coefficient of furfural is of the order of 10^?13 m²/s. Equilibrium adsorption data on BFA was analyzed by Freundlich, Langmuir, Dubnin-Radushkevich, Redlich-Peterson, and Temkin isotherm equations using regression and error analysis. The Redlich-Peterson isotherm was found to best represent the data for furfural adsorption onto BFA. Adsorption of furfural on BFA is favorably influenced by a decrease in the temperature of the operation. Values of the change in entropy (ΔS ⁰) and heat of adsorption (ΔH ⁰) for furfural adsorption on BFA were negative. The high negative value of change in Gibbs free energy (ΔG ⁰) indicates the feasible and spontaneous adsorption of furfural on BFA.     

Size Distribution and Morphology of Liposome Aerosols Generated By Two Methodologies

Pulmonary delivery of sustained release formulations needs drug encapsulation in a suitable matrix, as well as the generation of aerosols with high lung penetration and suitable release characteristics. Nanometer sized liposomes offer the potential for biocompatibility, controlled release and easy internalization in the lung. For uniform dose delivery and drug release kinetics, it is of interest to understand generation techniques to obtain aerosols containing nearly monodispered nanometer sized dry particles. Two aerosolization techniques, air-jet atomization and electrohydrodynamic atomization (EHDA) were studied to identify conditions under which the inclusion of one-liposome-per-drop could be achieved. In air-jet atomization, low lipid concentrations resulted in a unimodal aerosol with a median mobility diameter of 94 (± 3.5) nm, while higher concentrations led to larger median diameters, implying possible inclusion of multiple liposomes per drop. In EHDA, tuning drop sizes in the range of 130 to 200 nm, as well as the use of high lipid concentrations, resulted in a bimodal aerosol distribution, with peaks at 35 and 100 nm mobility diameters. TEM images of the liposome aerosol from EDHA showed fused liposomes, resulting in cylindrical structures with different physical diameters. It was hypothesized that deformation of liposomes to cylindrical structures in the micro-capillary liquid tip of the electrospray, and interactions along the axial or cross sectional surfaces led to dry particles with different mobility sizes.     

Utilization of bagasse fly ash for carbon–zeolite composite preparation

Bagasse fly ash (BFA), a solid waste from sugar cane industries, contains significant amount of carbon as well as silica. The coarse particles with high carbon content can be separated and further activated to produce BFA-based activated carbon, while silica content can be extracted from fine BFA particles to be used for zeolite crystallization. The zeolite crystal may be grown on a suitable solid surface to create a zeolitic composite. In this study, silicate extract from fine BFA particles were combined with pretreated carbon rich coarse BFA particles in a hydrothermal crystallization process to produce particular carbon–zeolite composites. The carbon rich particles could be subjected to any necessary activation or surface treatment before being used in the composite preparation. Meanwhile, a simple method based on thermogravimetry is proposed to evaluate the zeolite particles distribution on the carbon surface. Furthermore, the composite ability for treating mixed organic and inorganic pollutants in aqueous solution has been investigated.