Sulfur exchange on Co---Mo/Al2O3 hydrodesulfurization catalyst using S radioisotope tracer

A commercial Co---Mo/Al₂O₃ catalyst was labeled with the radioisotope ³⁵S in hydrodesulfurization (HDS) of ³⁵S-labeled dibenzothiophene (³⁵S-DBT) in a high-pressure flow reactor at 50 kg/cm². Then, HDS of 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) or sulfur exchange of H₂S were carried out on the labeled catalyst at 50 kg/cm² and 260–360°C. The amounts of labile sulfur participating in the reaction were determined from the radioactivity of ³⁵S---H₂S released from the ³⁵S-labeled catalyst. In the HDS reactions, the amount of labile sulfur participating in the reaction decreased in the order: DBT> 4-MDBT> 4,6-DMDBT. In the sulfur exchange reaction with H₂S, the adsorption of H₂S on the catalyst reached saturation above a H₂S partial pressure of 0.36 kg/cm². It was suggested that the release of H₂S from the labile sulfur may be the rate determining step of the HDS reaction.     

Effect of zeolite in surface discharge plasma on the decomposition of toluene

Toluene was decomposed in a surface discharge plasma reactor packed with various zeolites. The positioning effect of the zeolite bed was also investigated Reactor-B, in which the zeolite bed was located upstream, performed much better than Reactor-A, in which the zeolite bed was located downstream. Furthermore, the decomposition efficiency in Reactor-B increased with the capacity for toluene adsorption on zeolite, while that in Reactor-A did not. The toluene adsorbed in micropores was not decomposed effectively by direct electron impact, but was decomposed by active oxygen species generated in the plasma zone on the zeolite surface. A good correlation was also observed between toluene decomposition and ozone consumption in the downward-type reactor.     

The effect of the N-linked glycans on structural features and physicochemical functions of soybean β-conglycinin homotrimers

β-Conglycinin is a trimeric protein consisting of three subunits, α,α′,and β, which are N-glycosylated. The α and α′ subunits contain extension regions in addition to core regions common to all subunits. We purified homogeneous trimers consisting of only α, α′, or β from mutant soybean cultivars containing β-conglycinin lacking one or two subunits: α homotrimers from an α′-lacking mutant, α′ homotrimers from an α-lacking mutant, and β homotrimers from an α-and α′-lacking mutant. Structural features and physicochemical functions of the three homotrimers were examined and compared with those of recombinant homotrimers having no N-linked glycans. The native homotrimers have secondary structures very similar to those of the recombinant ones. In analogy with the recombinant homotrimers, the native ones exhibit different thermal stabilities from one another (β>α′>α), and the native α and α′ homotrimers exhibit better solubility, emulsifying ability, and heat-induced association than the native β homotrimer. Further, the N-linked glycans contribute to solubilities of the three subunits at low ionic strength (μ=0.08) and to the emulsifying ability of the native β homotrimer. N-Linked glycans also prevent heat-induced associations of the native α and α′ homotrimers but do not contribute to the secondary structure and the thermal stability of β-conglycinin.     

High-strength–high-modulus polyimide fibers II. Spinning and properties of fibers

The polyimides based on 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) described in Part I of this series were dissolved in p-chlorophenol and spun into fibers using a coagulating bath of ethanol. The fibers as spun had in general low tenacities and low moduli, but a heat treatment at 300–500°C under tension produced a remarkable increase in strength and modulus, and fibers with a tensile strength of 26 g/den (3.1 GPa) and an initial modulus higher than 1,000 g/den (120 GPa) could be obtained. Thus, the annealed fibers of polyimides are comparable to aramid fibers in mechanical properties. To heating in air and in the saturated steam, the polyimide fibers showed higher resistance than the aramid fibers. The polyimide fibers surpassed the aramid fibers in resistance to acid treatment and ultraviolet (UV) irradiation, but were inferior in resistance to alkali treatment. The annealed fibers of polyimides displayed distinct X-ray diffraction patterns. The chain repeat distance of 20.5 Å determined on the fibers of polyimide prepared from BPDA and o-tolidine, and 20.6 Å determined on the fibers of polyimide derived from BPDA and 3,4′-diaminodiphenyl ether are reasonable when the dimensions of monomeric units and the shapes of the molecular chains are considered. The X-ray reflections of both polyimide fibers were indexed satisfactorily on the basis of postulated unit cells.     

Application of polymerizable surfactant in the preparation of polystyrene/nano-Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> composite

Monooctadecyl maleate, as a polymerizable surfactant, was synthesized by the mono-esterification of maleic anhydride and octadecanol, and was utilized to surface-modify nano-Fe₃O₄ particles. A polymerizable magnetic fluid was obtained by directly dispersing modified nano-Fe₃O₄ particles into styrene monomer, and the polystyrene/nano-Fe₃O₄ composite was prepared through free radical polymerization of polymerizable magnetic fluid. The structure and dispersion status in different dispersion phases of modified nano-Fe₃O₄ particles were studied by Fourier transform infrared (FTIR) spectrometry, X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The experimental results show that the nano-Fe₃O₄ particles modified by monooctadecyl maleate with the size of about 7–10 nm can be uniformly dispersed into styrene and fixed in the composite during the procedure of polymerization. Thermogravimetric analysis (TGA) and vibrating sample magnetometry (VSM) indicate that the thermal stability of polystyrene/nano-Fe₃O₄ composite is improved compared to that of pure polystyrene, and the composite is a sort of superparamagnetic materials.     

Preparation of highly crystalline nanofibers on Fe and Fe-Ni catalysts with a variety of graphene plane alignments

The present study confirmed that highly crystalline nanofibers with controlled structure may be prepared over Fe and Fe-Ni alloy catalysts. The degree of graphitization of various carbon nanofibers (CNFs) was analyzed by using C(0 0 2) peaks from the XRD profiles. The C(0 0 2) peaks of CNFs over Fe catalyst shifted to higher angle and became narrower as the preparation temperature increased from 560 to 620 °C. Tubular CNFs prepared at temperature higher than 630 °C showed lower 2θ angles compared to those of platelet fibers. CNFs prepared over Fe-Ni catalysts tended to resemble those prepared over Fe catalysts. The degree of graphitization of platelet CNFs resembled natural graphite, while d_0 0 2 of the tubular CNFs showed values below the 3.39 Å reported as a theoretical minimum for a cylindrical alignment. Lc_0 0 2 of platelet and tubular CNFs increased by heat treatment at 2000 and 2800 °C though d_0 0 2 changed little. A transverse section of platelet and tubular CNFs had a hexagonal shape, not a round shape. The hexagonal column allows AB stacking of hexagonal planes that can give perfect hexagonal alignment.     

Novel CO2 Absorbents Using Lithium-Containing Oxide

We have discovered a series of lithium-containing oxides that immediately react with ambient carbon dioxide (CO₂) up to 700°C. The products react and return reversibly to the oxides at a temperatures higher than about 700°C. The absorption capacity surpasses that of other CO₂ absorbents by a factor of 10. Utilizing these absorbents, the possibility of a CO₂ separation system that operates at around 500°C is proposed. It is generally believed that a CO₂ separation process operable at temperatures higher than 500°C has the special benefit of a small energy penalty. Moreover, the absorption also proceeds at ambient temperature in the atmospheric environment. This property offers the possibility of many other applications, such as air cleaners or cartridges. Therefore, we think these materials have the potential to make a valuable contribution to the realization of CO₂ emission control.     

Nonlinear effects on spin waves in3He-4He dilute solutions

Spin dynamics of³He-⁴He dilute solution have been studied in the collisionless regime by NMR methods. In cw NMR experiments, we observed spin waves in a magnetic field gradient. The frequency difference between the first mode and the others obeyed a two-thirds power law in the strength of the field gradient. By using a pulsed NMR method, nonlinear spin dynamics were studied. We observed the large amplitude spin waves after an rf pulse. The frequency of each spin-wave mode depended on the tipping angle. By using the parameter determined in the present experiment, the numerical calculated results based on Leggett-Rice theory are in good agreement with the results of the pulsed NMR experiments.     

Hydrogen entry into steel during atmospheric corrosion process

Hydrogen entry and permeation into iron were measured by an electrochemical method during atmospheric corrosion reaction. The hydrogen permeation was enhanced on passive films because the hydrogen adsorption increased by the hydrogen evolution mechanism which is different from that on a bear iron surface. The permeation rate during a wet and dry corrosion cycle showed a maximum in the drying process depending upon the surface pH and the corrosion potential. The pollutant such as Na₂SO₃ which decreases the pH and the corrosion potential causes an increase in the permeation rate. The mechanism of the change in the permeation rate during the wet and dry cycles is explained by the polarization diagram of the electrode covered by thin water layer.     

Gas barrier properties and periodically fractured surface of thin DLC films coated on flexible polymer substrates

Thin DLC films coated on polymer surfaces are attracting considerable attention due to their wide applications and their interesting surface properties. When DLC films were coated on polymers, the resulting DLC-polymer composites are highly functionalized materials, some of which presenting dramatically improved gas barrier properties.In this paper, we will introduce several commonly used polymers including polyethylene terephthalate (PET), polyethylene (PE) and polypropylene (PP) for semi-crystalline polymers, and polymethyl methacyrlate (PMMA) for an amorphous polymer. The polymers were coated with thin DLC films and the gas barrier properties of the resulting DLC-polymer composites were investigated. Some of the DLC-polymer composites dramatically improved their gas barrier properties while they presented horizontal crack lines and vertical micro-buckling lines on the DLC surface when stretched to a certain strain. The gas barrier properties of the DLC-polymer composites with fractured DLC surface were also studied. It was found that the gas barrier property of the polymer substrates with lower residual strains was less damaged, when the substrates were mechanically deformed, than that of the polymer substrates with higher residual strains. When the number of the cracks increases, the strain imposed on each crack decreases, since the overall deformation is almost equally distributed to each crack while the crack spacing of each crack becomes shorter. Thus, it was found that the degradation of the gas barrier property after mechanical deformation is dependent on the residual strain of the polymers and the number of cracks on DLC films.