Modelling diffusion-controlled kinetics in equilibrium and driven alloys

Summary We introduce a very simple model for thermally activated atomic migration on a lattice, and several techniques to handle it. For thermodynamical systems, the model can be used for simulating decomposition paths taking into account relevant metallurgical features. Close to equilibrium, the simplest mean-field approximation of the model can be linearized with respect to the departure from equilibrium; one then gets a microscopic interpretation of classical phenomenological coefficients, such as mobility, interfacial transfer coefficient, rate constants for the coupled relaxation of concentration and order fields. Further away from the equilibrium, the nonlinearities can be taken into account in a consistent way. For driven alloys, i.e. alloys submitted to external forcing, forced atomic migration is added to the model and new features emerge: the model is supported by several experimental results some of which confirmed its predictions a posteriori.     

Zirconium-based intermetallics as heterogeneous catalysts for the fischer-tropsch reaction: I. Zr-Ni-Co catalysts

Alloys of the general formula Zr₅₀Ni_xCO_50-x, where 0 ≦x≧ 50, have been prepared and used in the temperature range 300–400°C, in the pressure range 1–9 barg in a microtubular reactor for the reaction of hydrogen with carbon monoxide to give hydrocarbons. The alloys or intermetallic materials were prepared by argon arc melting, powdered by hydrogen decrepitation and characterised by means of optical microscopy (metallography), scanning electron microscopy with surface analysis and magnetic susceptibility measurements. The selectivity towards higher hydrocarbons increased with (i) increase in the total pressure and (ii) decrease in hydrogen content of the feed gases. The kinetics were found to be of the form: where m = 1.0 ± 0.2 and n = 0. The apparent energy of activation (E_a) lay in the range of 80–130 kJ mole^?1 and there appeared to be a compensation effect between E_a and the pre-exponential factor A. The turnover numbers for the reaction exhibited an activity maximum for alloys of composition around Zr₅₀Ni₄₀Co₂₀ and Zr₅₀Ni₃₀Co₂₀. Magnetic susceptibility measurements indicated that alloys changed their nature from moderately paramagnetic to strongly paramagnetic or even ferromagnetic after use and this is attributed to the conversion of zirconium to zirconium oxide during reaction with the attendant production of free 3d-transition metals. Derived catalysts prepared by air treatment of the hydrogen-decrepitated intermetallics behaved almost identically to the latter materials and gave similar magnetic susceptibility values to used hydrided materials.     

Effect of Fe on the high temperature oxidation of TiAl alloys

An alloy of 51.23Ti−48.73Al−0.4Fe (at.%) was oxidized at 800, 900 and 1000°C in air to determine the effect of Fe on oxidation. The scales formed consisted of an outer TiO₂ layer, an intermediate Al₂O₃ layer, and an inner mixed (TiO₂ Al₂O₃) layer, typical of conventional TiAl alloys. A small amount of dissolved Fe ions was weakly segregated in the outer TiO₂ layer and also in the inner (TiO₂−Al₂O₃) mixed layer. Ti₂AIN and TiN were detected in the scale in some instances. A thin, oxygen-affected Ti₃Al sublayer formed at the oxide-substrate interface. The overall oxidation kinetics and the scale morphology were not affected by Fe-addition.     

Site occupations and ordering behaviour of O phase in Ti2AlNb—based intermetallics

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Ni3Al中B和Mg的非平衡晶界共偏聚

在1023－1373K的初始温度和0.05-268.91K/s的冷速范围内，用Auger剖层分析确定含B和Mg的Ni3Al合金中B和Mg的非平衡晶界共偏聚行为，按照溶质－空位复合体迁移机制所导出的描述非平衡晶界偏聚的扩散速率方程解析表达式，很好地模拟了本实验结果，并确定了Ni3Al-B-Mg合金中B及B－空位复合体，Mg及Mg-空位复合体的扩散系数及复合体激活能。     

Kinetics of hydrogen absorption and desorption of magnesium nickel alloy

Reaction rates in the Mg₂Ni---H₂ system are still unclear, although they are needed for the process/optimization of hydrogen storage reactors. In this article, the rates of hydrogen absorption and desorption of the magnesium nickel alloy were investigated at different pressures up to 2.0 MPa using a constant-temperature thermogravimetric method. The powder of the alloy was microencapsulated with copper to improve the alloy properties (such as cycling strength) as a pretreatment. In the experiments, weight changes of the smallest amount possible of samples were monitored with the help of an ultra-accurate thermobalance, in order to avoid changes of the sample temperature due to the heat of the reaction. The reaction curves obtained revealed unique dependence of temperature and pressure and influence of thermal hysterisis. It is also possible that hydrogen-absorption and-desorption rates of this hydrogen storage alloy are expressed by the rate equation of first-order reversible reaction.     

含Zr多晶Ni3Al合金在不同热处理温度下的组织与性能

研究了冷轧多晶Ni3Al-(0．2％，0．6％，1．0％，1．5％)Zr(原子分数)合金在不同热处理温度(800-1100℃)下的显微组织和力学性能，结果表明，适当的热处理温度，可使无硼Ni3Al-Zr多晶合金获得优良的室温拉伸强度和塑性，随着热处理温度的升高，不同Zr含量Ni3Al合金的再结晶体积分数增加，再结晶晶粒尺寸增大，室温拉伸强度下降．随着合金中Zr含量的增加，再结晶温度降低，再结晶晶粒尺寸减小．不同Zr含量Ni3Al合金的拉伸塑性明显依赖于热处理温度，对于低Zr(0．2％)合金，在1000℃热处理后，拉伸塑性最佳；对于中Zr(0．6％)合金，在850℃热处理后，拉伸塑性达到最大值；对于高Zr(≥1．0％)合金，拉伸塑性峰值出现在900℃热处理下，当热处理温度超过900℃，拉伸塑性显著降低。     

Ni3Al合金中晶界与位错交互作用的研究

运用嵌入原子法势函数和静态驰豫最陡梯度的计算方法,原子模拟了Ni_3Al合金中晶界与位错的交互作用.主要研究了晶界与位错交互作用的能量特征、晶界结构单元的畸变行为和晶界附近位错的核心结构,并分析讨论了各种因素对它们的影响以及与Ni_3Al晶界韧脆行为之间的关系     

ATOMISTIC SIMULATIONS FOR Ni/Al INTERMETALLICS

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