Top-Seeded Melt-Growth of YBa2Cus3Ox Crystals for Neutron Diffraction Studies

We have grown cubic centimeter-size crystals of YBa₂Cu₃O _x suitable for neutron studies, by a top-seeded melt-growth technique. Growth conditions were optimized with an eye toward maximizing phase purity. It was found that the addition of 2% Y₂BaCuO₅ and 0.5% Pt (by mass) were required to prevent melt loss and to obtain the highest crystallinity. A neutron diffraction study on a mosaic of six such crystals found that the final Y₂BaCuO₅ concentration was 5%, while other impurity phases comprised less than 1% by volume. The oxygen content was set to x = 6.5, the crystals were detwinned, and then carefully annealed to give the well-ordered ortho-II phase. The neutron study determined that 70% of the mosaic's volume was in the majority orthorhomic domain. The neutron (006) and (110) rocking curve widths were ～1° per crystal and ～2.2° for the mosaic, and the oxygen chain correlation lengths were >100 Å in the a- and b-directions and ～50 Å in the c-direction.     

Relationship between the genomic organization and the overlapping embryonic expression patterns of the zebrafish dlx genes

To understand the relationship between the expression and the genomic organization of the zebrafish dlx genes, we have determined the genomic structure of the dlx2 and dlx4 loci. This led to the identification of the zebrafish dlx1 and dlx6 genes, which are closely linked to dlx2 and dlx4, respectively. Therefore, the inverted convergent configuration of Dlx genes is conserved among vertebrates. Analysis of the expression patterns of dlx1 and dlx6 showed striking similarities to those of dlx2 and dlx4, respectively, the genes to which they are linked. Furthermore, the expression patterns of dlx3 and dlx7, which likely constitute a third pair of convergently transcribed genes, are indistinguishable. Thus, the overlapping expression patterns of linked Dlx genes during embryonic development suggest that they share cis-acting sequences that control their spatiotemporal expression. The evolutionary conservation of the genomic organization and combinatorial expression of Dlx genes in distantly related vertebrates suggest tight control mechanisms that are essential for their function during development.     

Plasma-Assisted Nitriding of Aluminum-Alloy Parts

Plasma-assisted nitriding of aluminum alloys promises to become a suitable alternative to variants of thermochemical treatment used for raising the wear resistance of these materials especially from the standpoint of the environmental effect. Process performed in vacuum with the use of nitrogen and an argon-hydrogen mixture as the process gas provides for the formation of a layer of compounds (aluminum nitrides) with enhanced hardness on various aluminum alloys. However, until the present the process has been used only at the laboratory scale. No data can be found in the literature, for example, on the effect of the batch size on the uniformity of the thickness of the nitrided layer or on the wear resistance of parts from aluminum alloys. The present work is a study of plasma-assisted nitriding of commercially produced parts (pistons) fabricated from an aluminum alloy. The parameters of the process are chosen after the determining optimum conditions for preliminary sputtering treatment. Special attention is devoted to provision of temperature uniformity within a batch and the possibility of improving the surface quality by increasing the thickness of the compound layer. The topography of the surface and the thickness, chemical composition, and hardness of the compound layer are studied by the methods of scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS), metallography, and measurement of ultramicrohardness. The performance characteristics of untreated, nitrided, and anodized pistons are evaluated with the help of vibration wear tests with a rider fabricated from a standard material. The results of the tests show that the wear resistance of some nitrided pistons is comparable to that of anodized parts.     

X-ray microtomography (microCT) of the progression of sulfate attack of cement paste

High-resolution X-ray computed tomography (i.e., microCT or microtomography) was used to study the sulfate attack of cylinders of Type I cement paste cast with water-cement (w/c) ratios of 0.45, 0.50 and 0.60. Damage levels in samples exposed to a Na₂SO₄ solution with 10,000 ppm sulfate ion concentration were qualitatively rated from 0 (no damage) to 4 (extreme damage) based upon visual examination of the samples' exteriors and microtomography of the samples' interiors. The greater the w/c ratio, the more rapid the onset of sulfate damage. The corners of the cylinders appeared to be particularly susceptible to spalling, and damage may have continued into the cement paste by formation of subsurface cracks.     

Alumina-, niobia-, and niobia/alumina-supported NiMoS catalysts: Surface properties and activities in the hydrodesulfurization of thiophene and hydrodenitrogenation of 2,6-dimethylaniline

The activity of NiMoS catalysts supported on niobia, alumina, and niobia/alumina was compared for the thiophene hydrodesulfurization (HDS) and 2,6-dimethylaniline (2,6-DMA) hydrodenitrogenation (HDN) reactions. To evaluate the acidity of the supports and identify the nature of the sulfide sites, adsorption of 2,6-dimethylpyridine, pyridine, and CO was performed and followed by IR spectroscopy. This study has shown that with niobia as a support, the activity of NiMoS catalysts in thiophene HDS and in HDN of 2,6-DMA was no longer promoted by the synergy between Ni and Mo. The absence of synergy between molybdenum and nickel on niobia can be explained by the strong interaction of each metal with niobia at the expense of interaction with each other. Moreover, it has been shown that on a niobia/alumina support, the formation of the NiMoS phase can be directly linked to the presence of alumina not covered by niobia. However, niobia is an interesting support for the HDN of 2,6-DMA, because it favors the formation of xylene through direct ammonia elimination involving low H₂ consumption. The activity for xylene formation on niobia is linked to the electron-deficient nature of the Mo sulfide site, as demonstrated by CO adsorption followed by IR.     

聚丙烯结构壁管专用料的开发

阐述了塑料结构壁管的基本情况和国内外现状．重点就扬子石油化工股份有限公司研究院研制的聚丙烯结构壁管专用料的情况进行了介绍。     

Reductive alkylation of illinois No. 6 coal. 1H and 13C n.m.r. spectra of the 13C-enriched alkylation products

The reductive alkylation of Illinois No. 6 coal has been carried out using potassium and naphthalene in tetrahydrofuran and methyl-¹³C and butyl-1 -¹³C iodides to alkylate the resultant polyanion. The soluble products of the reductive alkylation reaction were isolated by extraction and chromatography. Proton and carbon n.m.r. spectra were recorded. The intense resonance signal at δ3.95 which appears in the proton n.m.r. spectra of Illinois No. 6 coal butylated with unenriched butyl iodide is split into a doublet by the ¹³C nuclei. Similar results were obtained for the methylation products. The chemical shift and coupling interaction establish that aryl ethers are a very important constituent of the alkylated coal. The carbon n.m.r. spectra of the coal alkylated with ¹³C-enriched alkyl iodides are intense. The resonances of the C-alkylation products appear in a single broad band with a maximum intensity in spectral regions compatible with the formation of the reductive alkylation products of certain polynuclear aromatic hydrocarbons or the base-catalysed alkylation of certain benzylic carbon atoms. The resonances of the N -alkylation products appear in two distinct bands. These resonances are tentatively assigned to amines produced as a result of reductive alkylation of heterocyclic compounds. The resonances of the 0-alkylation products appear in three distinct bands which can be assigned to alkyl aryl ethers, alkyl aryl ethers with substituents at the adjacent positions, and to alkyl carboxylates. The ratio of ethers to carboxylates in the soluble alkylation products was determined to be 7.8 for butylation and 8.0 for methylation. The Chromatographic fractions contain different amounts of C-, N-, and 0-alkylation products. This finding suggests that the coal structure is not highly uniform.     

Solid state magnetic resonance spectra of Illinois No. 6 coal and some reductive alkylation products

Illinois No. 6 coal and its reductive methylation and butylation products have been studied by magnetic resonance techniques. Conventional CP-MAS¹³Cn.m.r. spectroscopy indicates that 62% of the carbon atoms in the coal are aromatic and that about 6% of the carbon atoms are carbonyl. Esters are more abundant than carboxylic acids. The resonances of methoxy groups and other novel etheric carbon atoms are apparent in the high field region. Dipolar dephasing experiments suggest that methyl carbon atoms constitute no more than 16% of the carbon, methylene and methine carbon atoms about 14% and quaternary aliphatic carbon atoms about 2%. The dipolar dephasing experiments in conjunction with previous work also permit estimates of the hydrogen atom distribution. The THF-insoluble products obtained in the reductive alkylation reactions with¹³C-enriched alkylating agents contain paramagnetic and ferromagnetic substances that adversely influence the solid state n.m.r. spectra. However, good ¹³C n.m.r. spectra were obtained after these substances were extracted with aqueous hydrochloric acid. The O:C alkylation ratios are 1.2 and 1.0 for methylation and butylation, respectively. Dipolar dephasing experiments establish that the decay constants of functional groups in the whole coal and of C- and O-methyl-¹³C and C- and O-butyl-1 -¹³C nuclei in the labelled coal molecules are very similar to those of reference compounds. These findings suggest that the decay constants measured for the ¹³C nuclei in coals and coal-derived solids provide reliable information about their degree of substitution.     

Reductive alkylation of Illinois No. 6 coal in liquid ammonia

The reductive alkylation of Illinois No. 6 coal was investigated using alkali metals and alkyl halides in liquid ammonia. Potassium is the most effective reducing agent and butyl iodide is the most effective alkylating agent for the preparation of coal alkylate that is soluble in tetrahydrofuran. The overall yield of soluble product is often improved through the reaction of the tetrahydrofuran-insoluble portion of the initial reaction products with an alkylating agent in the presence of tetrabutylammonium hydroxide. The infrared spectra of these materials suggest that the phase transfer agent catalyses the esterification of residual carboxylic acid functions. The intermolecular interactions between such acid groups and acceptor groups markedly restrict the solubility of the coal alkylate. The gel permeation chromatograms of the soluble reaction products are essentially featureless with only modest maxima at short and long elution volumes. The proton and carbon nuclear magnetic resonance spectra of the reductive methylation products, prepared using methyl-¹³C iodide, suggest that carbon alkylation exceeds oxygen alkylation and that the alkylation of phenolic groups is the dominant O-alkylation reaction. The spectra also suggest that fewer ethers are cleaved in the reaction in liquid ammonia than under the conditions of the Sternberg reaction.     

Ruthenium tetroxide catalysed oxidation of Illinois No. 6 coal: The formation of volatile monocarboxylic acids

Ruthenium tetroxide selectively oxidizes activated aromatic compounds under mild conditions and has been used for the catalytic oxidation of several different coals. The quantities of the volatile monocarboxylic acids with 2–6 carbon atoms have been determined by an isotope dilution technique. The amount of ethanoic acid ranges from 1 to 3mol/100C and the quantities of propanoic acid, and butanoic acid exceed 0.1 mol/100C. Methylpropanoic, pentanoic, 2-methylbutanoic, 3-methylbutanoicand hexanoic acid are formed in lesser amounts. The outcome of the experiment depends upon whether or not the coal has been extracted prior to oxidation. The results for Illinois No. 6 coal expressed in moles of ethanoic acid produced/l00C illustrate this feature: raw whole coal, 1.9; coal extracted by the method of Hayatsu and co-workers, 1.0. Dehydrogenation with benzoquinone prior to oxidation increases the yield of ethanoic acid to $\text{sol1.5mol}\text{100C.}$ The amounts of ethanoic acid obtained from the other extracted coals are 1.0 for Texas lignite, 1.2 for Rawhide subbituminous, 3.4 for Pittsburgh No. 8, 3.3 for a higher ranking bituminous coal (PSOC 726) and 0.7 for an anthracite (PSOC872). The results obtained in this study are compared with related information concerning the distribution of alkyl groups within coal by other methods.