Non-isothermal short-range-order kinetics of binary alloys as influenced by solute-vacancy complexes

A model describing the roles of bound and unbound vacancies is proposed in order to predict defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. This is an alternative treatment of a previous approach. The model has been applied to the differential scanning calorimetry (DSC) curves of Cu-5 at.% Zn quenched from different temperatures. An expression to calculate the activation energy for migration of solute-vacancy complexes was also developed which make use of DSC trace data. A value of 89.12±0.32 kJ mol^-1 was obtained for the above alloy. The relative contribution of bound and unbound vacancies to partition of effective activation energy corresponding to the ordering process as influenced by quenching temperature was also assessed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Mossbauer investigations of corrosion environment influence on Fe valence states in oxide films of zirconium alloys

Mössbauer investigations about iron atom redistribution in oxide films of zirconium alloys subjected to corrosion at 500°C in pure oxygen and water pair have been analysed. The alloys were also subjected to autoclave conditions at a pressure of 10.0 MPa and autoclave conditions at 350°C and at a pressure of 16.8 MPa, using distilled water and water with additives of lithium and fluorine. It is shown that, depending on the corrosion environment, various compounds of iron, such as α-Fe₂O₃, Fe₃O₄, and FeO, as solid solutions of iron in ZrO₂ are formed in oxide films.     

Mössbauer effect study of the decagonal quasicrystal Al65Co15Cu20

The ⁵⁷Fe Mössbauer effect study at 5.0 K and in an external magnetic field of 9.0 T on a high-quality stable decagonal quasicrystal Al₆₅Co₁₅Cu_19.9Fe_0.1 is presented. It is shown that the iron atoms are located in two distinct classes of sites. The values of the principal component of the electric field gradient tensor and the asymmetry parameter at these sites are, respectively, ?1.90(10)?×?10²¹ V/m², 0.97(15) and ?3.95(12)?×?10²¹ V/m², 0.00(17).     

STM/AFM studies of the evolution of morphology of electroplated Ni/W alloys

The surface morphology evolution of Ni/W alloys was studied, as a function of the alloy composition. Using the modified plating baths developed in our laboratory recently, electroplated Ni/W alloys with different W content, in the range of 7–67 atom percent (a/o), can be obtained. This was found to lead to different structures, ranging from polycrystalline fcc-Ni type structure to amorphous, followed by orthorhombic with increasing W content in the alloy. Powder XRD was studied to determine the crystal structures. Ex situ STM, AFM and SEM were used to study in detail the surface morphologies of the different alloys, and their evolution with increasing W content.

The important findings are that a mixture of two crystalline forms can give rise to an amorphous structure. Hillocks that are usually a characteristic of epitaxial growth can also exist in the amorphous alloys. Oriented scratches caused by stress can also be formed.

Up to 20 a/o of W is deposited in the alloys in crystalline form, with the fcc-Ni type structure. Between 20 and about 40 a/o an amorphous structure is observed, and above that an orthorhombic crystal structure is seen, which is characteristic of the NiW binary alloy. Careful choice of the composition of the plating bath allowed us to deposit an alloy containing 67 a/o W, which corresponds to the composition NiW₂.     

High-throughput concept for tailoring switchable mirrors

The optical properties, the switching kinetics and the lifetime of hydrogen switchable mirrors based on Mg-Ni alloys are determined with particular regard to the composition of the optically active metal-hydride layer in combination with the thickness of the catalytic capping layer. For this, a high-throughput experiment is introduced. The switching kinetics and the reversibility of switchable mirrors are strongly thickness dependent, though the details hinge on the fine structure of the clustered capping layer. Therefore, the kinetics is correlated with the surface structures of Pd on Mg_yNi_1−y as investigated by scanning tunneling microscopy. The results are explained by the so-called strong metal-support interaction (SMSI) state, characterized by a complete encapsulation of the capping layer clusters by oxidized species originating from the support. The SMSI-effect is less important with increasing Pd-layer thickness, and is suppressed by a good wetting of the Pd-clusters on the optically active film. This explains the critical thickness for the catalyzed hydrogen uptake observed in many switchable mirror systems. Moreover, the degradation of the kinetics during cycling is found to depend on the Pd-layer thickness and on the gas environment. Only films, covered with at least 15 nm Pd, show small degradation caused by the SMSI-effect. The SMSI-effect is partly reversible: after changing the gas environment from hydrogen to oxygen, the oxide on the Pd-clusters can be partly removed.     

Effect of carbon content on the microstructure and the cracking susceptibility of Fe-based laser-clad layer

The laser cladding of Fe-based alloys on a medium carbon steel substrate was performed using a CO₂ laser and Ar shielding gas that was blown into a molten pool. The microstructure and cracking susceptibility of the laser-clad layers were studied in terms of carbon additions. Results show that the small change of the carbon content in the alloy powders can obviously change the microstructure and properties of the layers. When the carbon content is in the range of 0.3–0.4 wt.%, the decrease of the carbon content in alloy powders will increase the hardness and toughness of the layers simultaneously under the same process parameters. As a result, crack-free coatings with high hardness can be obtained. As the carbon content increases from 0.2 wt.% to 0.4 wt.%, the segregation ratio of chromium increases, while the segregation ratios of nickel, manganese, and silicon first decrease and then increase. At the same time, a new designing principle concerning the composition and microstructure has been put forward, and the principal mechanisms of strengthening and toughening of the layers are fine-grain strengthening and low carbon martensitic phase transformation strengthening.     

Catalytic Activity of Nickel Alloys in Anodic Oxidation of the Hypophosphite Ion as a Function of Their Composition

The rate of anodic oxidation of the hypophosphite ion on alloys Ni-P, Ni-B, and Ni-Mo-P is studied as a function of their composition and structure. The organic compounds that are customarily used to stabilize electrolytes of electroless nickel plating are shown to come useful when controlling composition of the Ni-P coatings at the expense of their different influence on the rates of partial processes of deposition of the alloy components. The formation of catalytic activity of such coatings is affected mostly by a structural factor. With alloys Ni-P, Ni-B, and Ni-Mo-P, whose composition was varied by altering the concentration of the source of the alloying component, dependence of catalytic activity of the surface on the composition is defined mainly by an electronic factor.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 972–980.Original Russian Text Copyright © 2005 by Sotskaya, Dolgikh, Ryabinina.     

Exact thermodynamic behavior of a generalized spin-isospin ising system on the Bethe lattice

We study a generalized Ising system consisting of a Bethe lattice on every site of which two spin-1/2 and two isospin-1/2 (or atomic species A) states can be realized, the spin-species interacting with appropriate nearest neighbor couplings. The system is equivalent to that of four states per site and we obtain its exact thermodynamic behavior. The case of a fixed concentration of species is the annealed or liquid magnetic binary alloy. The temperature dependence of the short-range-order (SRO) parameter of such systems is obtained as an application of the theory and discussed in connection with relevant material from the literature. When fixing both the concentration and the nearest neighbor spatial correlation of the species, we obtain Eggarter's formulas for the frozen-in species problem, which therefore are only approximately valid even on the Bethe lattice.     

铜铝合金中γ_2相沉淀的分析电镜研究

Cu-12.7(wt)%Al合金从900℃高温淬至365℃～500℃温度范围等温不同时间(30秒至15分钟)的试样中形成了大量树枝状的γ_2相沉淀粒子。应用配有X线能谱仪(XEDS)和电子能量损失谱仪(EELS)的分析电子显微镜(JEOL JEM-2000FX型)对上还试样研究,结果表明:这些γ_2相粒子具有富铝的“核心”,长大到粒子线度大于约800nm后以不稳定方式生长成“花朵”状。生长过程中伴随着溶质元素Al由基体向γ_2相内的富集。而且在γ_2相粒子内部呈现出Spinodal分解组织的形貌特征,表明γ_2粒子内形成了化学成分调幅。EELS分析表明试样含氧。     

(TiNi)_x(x=2~4)团簇结构和电子结构

从团簇角度对TiNi形状记忆合金进行了量子化学从头算研究。设计并优化了等原子比(TiNi)x(x=2~4)簇的多种可能几何结构,并对较稳定构型进行电子结构的分析。结果表明,等原子比的(TiNi)n团簇以TiNi成键为主要分子骨架,小团簇有较多能量接近的异构体,TiTi成键对能量降低有较大贡献。