Modeling study of migration-driven lateral instability in autocatalytic systems

The lateral stability of reaction fronts in simple autocatalytic models with the components carrying various charges is investigated when the system is exposed to an inhomogeneous electric field parallel to the direction of propagation. The enhanced migrational flux of the reactant destabilizes the planar front giving rise to a cellular structure because the electric field strength is greater on the reactant side of the reaction front. The onset of instability depends not only on the charge difference between the reactant and the autocatalyst but also on the variation of specific conductance in the course of the reaction, which results in a difference in electric field strength on the opposite sides of the reaction front.     

超重力反应结晶法制备纳米ZnS正交试验研究

本文采用超重力反应结晶法制备纳米硫化锌粒子,以反应物浓度、反应温度、初始pH值、RPBR转速、气液流量比为影响因素,分别选取2个水平,进行正交试验研究,考察了各因素对产品粒径影响的程度.结果表明:各因素对产品粒径影响的显著性顺序为:反应温度＞气液流量比＞RPBR转速＞初始pH值＞反应物浓度.其中,反应温度和气液流量比对产品粒径有显著影响,RPBR转速和初始pH值对产品粒径有一定影响,而反应物浓度则基本无影响.这为制备可控粒径的纳米ZnS提供了理论依据.     

The effects of flow rate and particle shape on the convective diffusion to a solid catalytic particle

Summary The flow of a fluid, containing a reactant, past a solid catalytic particle on which a reaction takes place is considered for large Péclet number. The concentration of the reactant is given by the diffusion boundary-layer equation, and this is solved in the case when the rate of reaction on the particle surface and the rate of diffusion of reactant onto the surface are of the same order of magnitude.For a spherical particle, a series solution for the concentration is found for the case of Stokes flow, and numerical solutions are found for Stokes flow and for flow at higher Reynolds numbers (up to Re=10). To examine the effect of particle shape, numerical solutions are found for prolate and oblate spheroids in Stokes flow.     

Asymptotic analysis and effect of reaction order on a reversible gas-solid system with fast reaction

The development of approximate methods for the equations describing noncatalytic reversible gas-solid systems with fast reactions are investigated by means of perturbation techniques and series solutions. The effect of the reaction orders, when the back reaction is not neglected, on the existence of a moving boundary is also discussed. It is shown that a moving boundary exists only when the reversible reaction rate is independent of the reactant solid concentration.Estimates for conversion times are also obtained for the cases where all the reaction orders are non-zero and where the kinetics is independent of the reactant and product solids. These approximate solutions may find application, for example, in computational models of ironmaking blast furnaces.     

How does a single Pt nanocatalyst behave in two different reactions? A single-molecule study

Using single-molecule microscopy of fluorogenic reactions we studied Pt nanoparticle catalysis at single-particle, single-turnover resolution for two reactions: one an oxidative N-deacetylation and the other a reductive N-deoxygenation. These Pt nanoparticles show distinct catalytic kinetics in these two reactions: one following noncompetitive reactant adsorption and the other following competitive reactant adsorption. In both reactions, single nanoparticles exhibit temporal activity fluctuations attributable to dominantly spontaneous surface restructuring. Depending on the reaction sequence, single Pt nanoparticles may or may not show activity correlations in catalyzing both reactions, reflecting the structure insensitivity of the N-deacetylation reaction and the structure sensitivity of the N-deoxygenation reaction.     

三聚氰胺和腰果壳油改性酚醛树脂的研究

用腰果壳油和三聚氰胺对酚醛树脂进行改性,可用作刹车片中各种基料的胶粘剂。研究了反应物配比、催化剂用量和反应时间等因素对改性树脂性能的影响,确定了最佳配比和生产工艺,并成功的应用于工业生产。     

氧化镁真空碳热还原法炼镁的工艺研究

采用物料失重率、金属Mg还原率、X射线衍射(XRD)与扫描电子显微镜(SEM)等手段与方法,研究了真空条件下氧化镁碳热还原温度、物料造球成型压力、物料配比、碳热还原保温时间以及催化剂对氧化镁碳热还原法炼镁工艺的影响。研究结果表明,在30~100 Pa时,碳热还原温度高于1553 K,控制物料压块压力为8 MPa,此时物料失重率最大,最有利于氧化镁的还原。随着焦煤还原剂与氧化镁摩尔比以及碳热还原时间的增加,碳热还原反应速率加大,还原率提高,但是变化效果不明显,加入氟盐CaF2后,物料失重率明显提高,添加CaF2的质量超过物料总质量的3%时,物料失重率超过95%,还原率也相应大幅提高。因此,选择适当的焦煤还原剂与氧化镁摩尔比值以及碳热还原时间,添加超过3%CaF2,将有利于该法炼镁过程的顺利进行与金属Mg还原率的提高。此研究为真空碳热法从氧化镁中提取金属Mg工艺提供了很好的实验依据。     

合成PEN的酯交换反应工艺优化研究

以 2 ,6 萘二甲酸二甲酯和乙二醇为原料 ,Zn(AC) 2 为催化剂 ,在选定的反应条件下 ,研究了合成PEN(聚 2 ,6 萘二甲酸乙二醇酯 )的酯交换反应。详细论述了温度、催化剂浓度、反应时间、反应物摩尔配比等反应因素对NDC和EG酯交换反应的影响 ;确定了酯交换反应优化工艺条件     

医药中间体5-氨基-2,4,6-三碘异酞酸的合成研究

以5-硝基-异酞酸为原料,通过还原、碘取代反应,生成5-氨基-2,4,6-三碘异酞酸.重点对碘取代反应中反应介质、碘化剂的选取及碘化剂用量、反应温度、反应时间等参数及精制方法对反应得率影响进行了讨论,确定了最佳配方和工艺条件.     

失水山梨醇倍半油酸酯的合成

考察了合成乳化剂失水山梨醇倍半油酸酯（ＡｒｌａｃｅｌＣ）的原料配比、反应温度、反应时间、催化剂用量对产品性能的影响，并找到了最佳反应条件．     

Combustion synthesis of advanced materials: Part I. Reaction parameters

An explanation of combustion (self propagating high temperature) synthesis (SHS) is given together with a historical perspective of the examination of such exothermic reactions. The application of thermochemical functions has been used to predict theoretically the maximum adiabatic temperature, T_ad. This, combined with a knowledge of the ignition temperature, T_ig, and the actual combustion temperature, T_c, has been used to determine the heat loss from the SHS reaction and the amount of heat needed to raise the adjacent, cold, reactant layer to the ignition temperature in order to maintain the self sustaining nature of the propagating mode of the reaction. The pertinent reaction parameters that control self propagating high temperature (combustion) synthesis reactions have been examined. These include: reactant particle size and shape; powder mixing and compaction; green density; reaction stoichiometry; impurities; volatiles and diluents; reaction environment; mode and technique of ignition; heating rate; and the effect of these parameters on the generation of heat, exothermicity and control of the SHS reaction.     

反应物量对燃烧合成Ni-Zn铁氧体粉的影响

为探讨燃烧合成法制备Ni0.4Zn0.6Fe2O4粉末工业化放大合成的可行性,研究不同反应物量对燃烧合成制备的Ni0.4Zn0.6Fe2O4粉体及烧结后产物的物相、微观形貌及磁性能的影响,对终产物进行XRD、SEM和EDS分析,对样品经行磁性能测试.结果表明:Fe-Fe2O3-Zn O-Ni O体系燃烧合成过程是以扩散-溶解-析出机制进行的,燃烧反应在非平衡条件下进行,燃烧产物的主要物相为Ni-Zn铁氧体,其中存在Zn O及一些铁的氧化物的杂质,产物经热处理后物相全部转变为尖晶石结构;随着反应物量的增加,产物颗粒尺寸增大,均匀度增加,反应物量的增加对产物的磁性能影响不大;随着反应物量的增加,饱和磁化强度逐渐增加,矫顽力基本不变,反应物量为1 500 g时制备的产品磁性能最佳,具有较高的饱和磁化强度Ms=63.72 emu/g和较低的矫顽力Hc=15.61 Oe.     

Influence of reactant concentrations and solution acidity on the complexation of 188Re with 1-hydroxyethane-1,1-diphosphonic acid

Specific features of the complexation of ¹⁸⁸Re with 1-hydroxyethane-1,1-diphosphonic acid (HEDP) were studied in relation to the solution acidity and reactant concentrations. The reaction rate and efficiency of the complexation of ¹⁸⁸Re with HEDP increase with decreasing pH. A decrease in the reactant concentrations leads to a decrease in the reaction rate and in the efficiency of binding of ¹⁸⁸Re with HEDP. The maximal binding of ¹⁸⁸Re with HEDP is attained at pH 2.70, HEDP concentration of 117 μmol ml⁻¹, and SnCl₂ and ascorbic acid concentrations of 10 μmol ml⁻¹. The results obtained can serve as basis for further optimization of the reaction conditions. Original Russian Text ? V.M. Petriev, 2008, published in Radiokhimiya, 2008, Vol. 50, No. 2, pp. 173–177.     

Welding TiB2 Ceramics and Metal Mo with Combustion Reaction Technology

Combustion reaction welding, one promising method to weld ceramics and metals, was used to weld TiB2 and Mo. The results showed that the reacted products through combustion reaction were TiB2 and MoB when the Mo contents in reactants were 20 wt pct and 40 wt pct while there was Mo besides MoB and TiB2 when there were 60 wt pct and 80 wt pct Mo in reactants. Diffusion of elements occurred at the interfaces of the two substrates. The interfaces between the reacted and the two substrates were indistinct after being welded. The welding temperature strongly affected properties of the samples. The value of bending strength of the sample with 80 wt pct Mo in reactant welded at 1500℃ was the highest, 368.52 MPa. The highest value of shear strength among all the samples was that of the one with 40 wt pct Mo in reactant welded at 1500℃, 50.97 MPa.     

The formation of TiC/Al2O3 microstructures by a self-propagating high-temperature synthesis reaction

The effect of processing variables on reaction rate and ceramic microstructure are examined for the self-propagating high-temperature synthesis reaction 3TiO₂+4Al+3C 3TiC+2Al₂O₃. Reaction controlling methods used are reactant particle size, the use of diluents (to lower the combustion temperature) and the use of reactant preheating (to increase the combustion temperature). The ceramic microstructure has an unusual laminar structure which is generally only observed during unstable combustion wave propagation.     

Combustion reaction of Ti–Al–C–N system

The combustion reaction of Ti–Al–C–N system was investigated by using Ti powders and one CNx precursor powder as reactant powder blends. The reactant powder blends ratio was adjusted to obtain different materials. The phase composition of the samples was investigated by X-ray diffraction (XRD). The microstructure of the samples was observed by scanning electron microscopy (SEM). The result showed that Ti₂Al(C, N)–TiAlx, AlN–Ti(C, N) and Ti₃Al(C, N)₂–TiC composites can be fabricated by changing the reactant powder blends ratio.     

Shock synthesis and synthesis-assisted shock consolidation of suicides

Shock-induced chemical synthesis and synthesis-assisted consolidation of high-temperature materials (suicides) were investigated. Niobium, molybdenum, and titanium powders mixed with silicon powders were chosen as reactant materials for shock-induced synthesis of silicides. In parallel experiments, these reactant materials were also respectively mixed with inert intermetallic compound powders of NbSi₂, MoSi₂, and Ti₅Si₃ in different proportions and were shock consolidated. Shock processing was carried out using a modification of the experimental set-up developed by Sawaoka and Akashi. The shock waves were generated in the materials by the impact of a flyer plate at a velocity of 2 km sec^–1. An explosive plane-wave generator was used to initiate the main explosive charge to accelerate the flyer plate. The passage of shock waves of sufficient pressure and temperature induced a highly exothermic and self-sustaining reaction between reactant materials. The shock-synthesized intermetallic compounds and the heat of reaction enhanced bonding between inert matrix materials. The proportion of reactant powder mixtures blended with inert intermetallic materials plays a very important role in the synthesis-assisted consolidation process. Characterization of compacts was done by optical microscopy, scanning electron microscopy, and X-ray diffraction. A preliminary analysis of shock-induced chemical reactions is conducted; it predicts a 30% increase in shock pressure and shock-wave velocity over those in unreacted powders. For shock synthesis, the profuse formation of voids indicates that melting of the material occurred; in contrast, unreacted regions did not exhibit porosity.     

反应物结构对酚醛凝胶及其气凝胶的影响

为研究反应物酚与醛的结构对酚醛凝胶过程及其气凝胶结构的影响,采用不同的酚与醛制备出了多种气凝胶。研究了反应物结构对凝胶过程的影响,并通过扫描电镜和孔径分析仪等仪器详细研究了气凝胶的结构。结果表明,酚醛反应的凝胶时间受反应物的活性及位阻效应共同影响,反应体系选择不当可能导致无法凝胶。采用不同的酚-醛体系,所得气凝胶结构也...     

液膜用油溶性络合剂的合成

提出了一种可用于乳状液膜分离稀土的油溶性氨羧络合剂的合成方法，讨论了反应物摩尔比，反应温度，等因素的影响。     

Spectrophotometric tool for the determination of the total carboxylate content in proteins; molar extinction coefficient of the enol ester from Woodward's reagent K reacted with protein carboxylates

A number of relevant properties of Woodward's reagent K have been determined, such as the stability of the reactant and the optimal reaction conditions of the reactant with protein carboxylates. A Woodward's reagent K stock solution was stable at 4 degrees C for prolonged time, whereas upon storage at 22 degrees C, almost 20% of the reactive compound was lost within 1 week. The pH-dependency of the spontaneous degradation reaction of Woodward's reagent K was studied and was shown to be base-mediated. A molar extinction coefficient of 3150 M(-1) cm(-1) at 269 nm for the enol ester resulting from the reaction between Woodward's reagent K and the protein carboxylates was established using the conditions laid out in this work. This value was validated using a variety of proteins that were modified by Woodward's reagent K. In addition, upon methylation of the carboxylates of a single protein, ovalbumin in this case, the degree of modification could be determined accurately and was confirmed by cation exchange chromatography elution profiles.