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.     

Aminotetryls: Synthesis,spectral characterization,thermal decomposition and explosive properties

This paper describes the synthesis and spectral investigations of two amino derivatives of N-methyl-N-(2,4,6-trinitrophenyl)nitramine (tetryl). Also discussed are the results from thermal decomposition studies on the three explosives, viz. tetryl, 3-aminotetryl (3 AT) and 3,5-diaminotetryl (3,5 DAT) and preliminary work on the explosive properties of the last two compounds. The aminotetryls have been prepared by the amination of the corresponding chlorotetryls. The yield was 87% for 3 AT, but was only 33% for 3,5 DAT, probably due to steric crowding around the benzene nucleus. The mass spectra show interesting differences in the electron impact fragmentation patterns of the three tetryls with the M⁺ ion relative intensities following the order 3,5 DAT > 3 AT > tetryl, which could be due to (a) resonance stabilization and (b) hydrogen bonding effects. Evidence for the latter is also found in the infrared spectra of these compounds. Arrhenius kinetic parameters derived from thermal decomposition studies of the three compounds are presented and show that 3,5 DAT is thermally less stable than 3 AT. Explosive sensitiveness tests indicate that the diamino compound is the most sensitive, the trend being 3,5 DAT > 3 AT > tetryl. This is contrary to the generally found desensitizing influence of NH₂ groups on the thermal stability and explosive sensitiveness of trinitroaromatic energetic molecules. Mechanisms to account for the observed thermal decomposition behaviour and explosive sensitiveness patterns are discussed.     

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.     

Preparation and performance evaluation of poly (ether-imide) incorporated polysulfone hemodialysis membranes

Biocompatible Polysulfone (PSf) hemodialysis membranes were prepared by phase inversion technique using poly (ether-imide) (PEI) as the modification agent and Polyethylene glycol (PEG-200) as the pore former. The effect of PSf/PEI blend ratio on the morphology, hydrophilicity, water content, porosity, glass transition temperature, mechanical strength, biocompatibility and permeation rate of the prepared membranes were studied and were found to be improved significantly by the incorporation of PEI in the dope solution. The scanning electron microscopy (SEM) studies revealed that, incorporation of PEI resulted in the formation of spongy sub-layer and increased the connectivity of pores between sub-layer and bottom layer. The water content and permeation rate of the membranes of PSf/PEI blend membranes were increased considerably indicating the enhancement of hydrophilicity and it was supported by lower contact angle values of the blend membranes. The existence of single well defined Tg over entire composition established the compatibility between the components in blend membranes. The biocompatibility of membranes was investigated through protein adsorption, platelet adhesion and thrombus formation on the membrane surface. Anticoagulant activity of PSf/PEI blend membranes was evaluated by measuring the activated partial thrombin time (APTT), prothrombin time (PT), thrombin time (TT) and fibrinogen time (FT). The results revealed that antithrombogenicity of PSf/PEI blend membranes was increased significantly. The efficiency of these membranes in removal of urea, creatinine and vitamin B₁₂ were studied and found to be improved for blend membranes. Thus, it is worth mentioning to note that, the biocompatible PSf/PEI blend membranes prepared in this study would offer immense potential in hemodialysis.     

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.     

Epitaxial nucleation model for chiral-selective growth of single-walled carbon nanotubes on bimetallic catalyst surfaces

An epitaxial nucleation model for single-walled carbon nanotube (SWCNT) growth on bimetallic catalysts surfaces is reported in support of experimental observations of chiral enrichment. We model the bimetallic catalyst surfaces as a 2D (1 1 1) surface consisting of Ni or a combination of Ni and Fe atoms, with varying average bond length between nearest neighbor atoms which corresponds to the crystal structure of the alloys. The energies associated with nanotube cap formation on these various surfaces are calculated using density functional theory (DFT). We find that certain cap chiralities, such as (8, 4), are more stably bound to a surface that resembles a Ni_0.27Fe_0.73 bimetallic catalyst, whereas other chiralities, such as (9, 4), are more stable on a pure Ni surface. These results help explain the predominance of certain chiralities on specific bimetallic catalysts and provide a potential route to controlling the chirality of as-grown SWCNTs.     

Direct Ink-Jet Printing of Vertical Walls

Direct jet printing can assemble ceramic powder into a three dimensional shape by firing droplets of ink through a nozzle to build a multiple layered structure. As with stereolithography and selective laser sintering, the surface texture is expected to witness the layered assembly. The ability to create vertical walls by direct ink-jet printing was explored using a test piece based on a maze. The structure and topography are discussed in terms of droplet spreading and drying.     

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.