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21.
In this paper, we describe a procedure for the processing of SiC-whisker-reinforced MoSi2 composites via tape casting. Based on the characteristics of SiC whiskers and MoSi2 powder in aqueous and nonaqueous solvents, a slip formulation (solvent, dispersant, binder, etc.) has been developed. The formulation developed allows for a uniform distribution of SiC whiskers in the matrix, easy separation of the tapes from the polymeric carrier, convenient control of both tape thickness and orientation of SiC whiskers, and a low binder burnout temperature. The latter is important for the prevention of the oxidation of MoSi2 powder during the binder burnout in an oxidizing atmosphere. 相似文献
22.
The results of conversion determinations on the products from Powhatan No.5 coal liquefied in an autoclave and in a high-pressure, high-temperature e.s.r. cavity are reported. Oil, asphaltene and preasphaltene yields, and overall conversion have been determined for Powhatan No.5 coal samples liquefied in tetralin, SRC-11 heavy distillate, and naphthalene at temperatures from 400 to 480 ° C in both reactor systems. The concept of reaction severity is introduced and used to formalize the relation between the effect of temperature and reaction time on oil yield and conversion. Oil is the predominant product in liquefaction in tetralin or naphthalene, asphaltene is the major product of liquefaction in SRC-II heavy distillate. Retrogressive reaction (THF-insoluble product formation) becomes severe when SRC-II heavy distillate is the liquefaction solvent and residence time of >10 min are used at temperatures >450 °C. Preasphaltenes appear to be the only intermediate species in Powhatan No.5 liquefaction. 相似文献
23.
The reactivity of hexamethylphosphorus triamide, (P[N? (CH3)2]3) (HPT), with cotton cellulose was examined under various conditions. HPT was found to react readily with the cellulose to produce a cellulose phosphite and/or phosphate ester having approximately one acidic hydrogen atom per phosphorus atom. The reaction of HPT with cotton cellulose was efficiently catalyzed by dimethylamine hydrochloride (1%). The phosphorus content imparted by the catalyzed reaction on cotton fabrics was approximately twice that imparted by the uncatalyzed reaction. Flame resistance of the treated fabrics ranged from fair to excellent. The treated fabrics also exhibited ion exchange properties and some crosslinking. 相似文献
24.
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. 相似文献
25.
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. 相似文献
26.
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. 相似文献
27.
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 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. 相似文献
28.
Hyunjun Kim Brahim Akdim James Park Woo-Yong Jang Randall S. Hay Augustine M. Urbas Christopher Woodward 《Journal of the American Ceramic Society》2021,104(11):5659-5670
High-throughput computation, based on density functional theory (HT-DFT), is used to predict the bounds for optical transparency, from the ultraviolet to the infrared, for materials in the pyrochlore family. The HT-DFT approach adopted here uses an initial screening from Materials-Project database, with millions of calculated properties. Band gaps and phonon spectra were calculated from selected pyrochlore crystal structures taken from the Materials Project database. Short and long wavelength bounds for optical transparency were calculated for chemistries with stable, cubic structures. The calculations predict that La2Ce2O7 has one of the broadest range of transparency for the pyrochlore family. Based on these calculations, dense polycrystalline samples of La2Ce2O7 were produced by sintering and hot-isostatic pressing. Transparency was characterized by methods that did not require large samples with high optical quality, obtaining 7.15 and 7.5 µm at 95% and 90% normalized transmittance, respectively. Bandgap calculations suggest a lower bound of UV transparency cut-off of 0.3 µm. The infrared wavelength cut-off is higher than that reported for other pyrochlores, and higher than for yttria, zirconia, or other common infrared transparent ceramics. We discuss our prediction and characterization methods as well as the suitability of pyrochlores for mid- and far-infrared optical applications. 相似文献
29.
A figure of merit (FOM) has been developed to define the quality of ceramic (e.g., ZrO2) coatings on metal and alloy [Type 304SS and Alloy 600] surfaces. Zirconia (ZrO2) coatings were developed as a means of protecting the metal/alloy surfaces from stress corrosion cracking (SCC) in boiling water reactor (BWR) primary heat transport circuits, by inhibiting the cathodic reaction (reduction of oxygen and hydrogen peroxide) on the surface external to the crack. The distribution of pores in the coating plays an important role in corrosion prevention, such that the lower the porosity of the coating, the better the protection afforded to the system against SCC. Since the reactors operate at high temperature (e.g., at 288 °C under full power conditions), the temperature dependence of the FOM was investigated. The figure of merit (FOM) was developed by measuring impedance data over a wide range of frequency (10 mHz-5 kHz) at temperatures of 25, 100, 200, and 288 °C in hydrogenated, buffered solutions, with the hydrogen electrode reaction (HER) being used as a “fast” redox couple. An “equivalent circuit” analog was first developed from the bare surface impedance data and this analog was then employed in a second step to model the pore bottom in defining the pore distribution on the coated surface. A lognormal distribution (LND) of the pores was assumed and the parameters of the LND were determined using a constrained optimization technique to fit the model to the experimental data for the coated surface at different temperatures. The results suggest that, as temperature increases, the coating becomes more porous, making the substrate more susceptible to corrosion cracking. At 288 °C, 87% of the SS and 85% of the Ni-alloy surfaces become porous with the pore radius varying from 0.0001 cm to 0.01 cm. 相似文献
30.
Renata FurtunaSilvia Curteanu Florin Leon 《Engineering Applications of Artificial Intelligence》2011,24(5):772-785
This paper presents an original software implementation of the elitist non-dominated sorting genetic algorithm (NSGA-II) applied and adapted to the multi-objective optimization of a polysiloxane synthesis process. An optimized feed-forward neural network, modeling the variation in time of the main parameters of the process, was used to calculate the vectorial objective function of NSGA-II, as an enhancement to the multi-objective optimization procedure. An original technique was utilized in order to find the most appropriate parameters for maximizing the performance of NSGA-II. The algorithm provided the optimum reaction conditions (reaction temperature, reaction time, amount of catalyst, and amount of co-catalyst), which maximize the reaction conversion and minimize the difference between the obtained viscometric molecular weight and the desired molecular weight. The algorithm has proven to be able to find the entire non-dominated Pareto front and to quickly evolve optimal solutions as an acceptable compromise between objectives competing with each other. The use of the neural network makes it also suitable to the multi-objective optimization of processes for which the amount of knowledge is limited. 相似文献