Charge transfer in binary alloys and to impurities in iron

The energy density formalism in the Thomas-Fermi-Dirac approximation was used to study charge transfer in equiatomic binary ordered alloys and in dilute iron alloys. This method was applied outside of a core region around each nucleus; the inner region was treated by taking the electron density to be that given by free atom wave functions.The results for the equivolume charge transfer in binary alloys agreed satisfactorily with existing KKR-selfconsislent field calculations.For metalloid impurities in iron, the charge transfer to the impurity, and the variation of lattice parameter with concentration was computed. The latter compared fairly well with experiments.The theory explicitly displays the role of the electron density at the cell boundary in alloy formation and charge transfer effects. Alloy formation is visualized as a process in which atomic cells of the pure metals are expanded or compressed to the equilibrium cell volume of the alloy, bringing the cells together to form the alloy, and then allowing the electron distribution to relax.The general conclusion of this work is that modifying the TFD theory by using it only in regions where the electron density does not vary too rapidly, and using quantum theory results for the density close to the nuclei. provides a satisfactory method for studying charge transfer.     

Electron theory of long-wavelength concentration fluctuations in liquid metal alloys

Summary It is shown that long-wavelength concentration fluctuations in a binary liquid metal alloy are determined by a pair interchange free energyw, which is exactly given by the sum of an elastic strain term and of the concentration-concentration direct correlation function. The latter is evaluated in an alloy of homovalent components by electron screening theory in the pseudopotential approach of Shaw and Harrison and shown to be entirely determined by nonlocal terms reflecting charge transfer to the more electronegative alloy component. Numerical calculations for the liquid Na−K alloy show strong cancellation between the two contributions tow at all concentrations, in qualitative agreement with experiment.     

Effective interactions between concentration fluctuations and charge transfer in chemically ordering liquid alloys

Summary The correlations between long-wavelength fluctuations of concentration in a liquid binary alloy are determined by a balance between an elastic-strain free energy and an Ornstein-Zernike effective interaction. The latter is extracted from thermodynamic data in the case of the Li−Pb system, which is well known to chemically order with stoichiometric composition corresponding to Li₄Pb. Strong attractive interactions between concentration fluctuations near the composition of chemical ordering originate from electronic charge transfer, which is estimated from the electron-ion partial structure factors as functions of composition in the liquid alloy. In honour of Prof. Fausto Fumi on the occasion of his retirement from teaching.     

Al、Zn、Mn、Zr、Ca对Mg合金电子结构影响的第一性原理研究

应用密度泛函理论研究了合金元素Al、Zn、Mn、Zr、Ca对α-Mg合金电子结构的影响。对合金元素添加后的结构进行了优化。在稳定结构的基础上,通过对不同合金元素的形成能、态密度、布居分布、差分电荷密度的分析,认为引起合金性能变化的原因是各合金元素的电负性和原子半径的大小不同所致,对比了合金元素对材料电子结构的影响,从理论上解释了Zr、Ca强烈的合金强化、细化作用。     

Diffraction efficiency and energy transfer during hologram formation in reduced KNbO3

Volume phase-hologram formation by the photorefractive effect in KNbO₃ is accompanied by a stationary energy transfer between writing beams. The change in energy transfer by applying an electric field on the reduced crystals is shown to be due to an efficient increase in migration length which can reach values comparable or larger than the fringe spacing. It is demonstrated that photovoltaic contribution to the diffraction efficiency and energy transfer is rather small in reduced KNbO₃ and that diffusion of photogenerated free holes is the dominant charge transport for the photorefractive effect in unbiased crystals. The experimental results for diffraction efficiency and energy transfer as a function of grating spacing, electric field, light intensity and temperature is well described by a recent theory of Kukhtarev and Vinetskii.     

Simulated evolution process of core-shell microstructures

The evolution process of core-shell microstructures formed in monotectic alloys under the space environment condition was investigated by the numerical simulation method. In order to account for the effect of surface segregation on phase separation, Model H was modified by introducing a surface free energy term into the total free energy of alloy droplet. Three Fe-Cu alloys were taken as simulated examples, which usually exhibit metastable phase separation in undercooled and microgravity states. It was revealed by the dynamic simulation process that the formation of core-shell microstructures depends mainly on surface segregation and Marangoni convection. The phase separation of Fe65Cu35 alloy starts from a dispersed structure and gradually evolves into a triple-layer core-shell microstructure. Similarly, Fe50Cu50 alloy experiences a structural evolution process of "bicontinuous phase → quadruple-layer core-shell → triple-layer core-shell", while the microstructures of Fe35Cu65 alloy transfer from the dispersed structure into the final double-layer core-shell morphology. The Cu-rich phase always forms the outer layer because of surface segregation, whereas the internal microstructural evolution is controlled mainly by the Marangoni convection resulting from the temperature gradient.     

Measurement of the charge state distribution of field evaporated ions originating from alloys

The charge state distribution of field evaporated ions from the pure metals Mo, W, Au, Pt and from alloys of these elements has been determined as a function of the electric field strength. The change of the mean charge of these elements when desorbed from an alloy with a different evaporation field can be explained by the model of post ionization. The general validity of this model has also been tested for the change of the mean charge of iridium ions evaporated in the presence of adsorbed hydrogen.     

Ti-V系合金的结构、力学性质及电子结构的第一原理研究

采用基于密度泛函理论的第一原理方法,研究了Ti-V系合金Ti_3V, TiV和TiV_3的晶体结构,电子结构及力学性质.结果表明, TiV_3结构最稳定,其次是TiV,而Ti_3V稳定性最弱,但是, Ti_3V形成能力最强.三种合金的自间隙构型中,与Ti的自间隙构型相比,更容易形成V的自间隙构型;不管是Ti自间隙还是V自间隙, TiV_3的自间隙形成能均最大.力学性质的计算表明:三种合金均满足力学稳定性标准,且都为韧性材料;体模量及硬度计算表明, TiV_3的硬度最高,其次是TiV, Ti_3V的硬度最低,这与自间隙能的计算结果一致.电子结构计算表明:在费米能级处,三种合金均主要由Ti, V的p, d轨道电子提供态密度, TiV_3合金电子结构最稳定.差分电荷密度计算表明:在Ti_3V合金中,金属性强于共价性.在Ti_3V, TiV, TiV_3三种合金中,金属性逐渐减弱,共价性逐渐增强,合金变得稳定.     

Phase formation in ion bombarded metallic films

The interplay of several events, ranging from production, migration and interaction of defects, to irradiation enhanced atomic diffusion and chemical mixing, is responsible for phase formation in surface layers of ion bombarded metallic alloys. The problem is so complicated that even the interpretation and the prediction of extreme cases such as the attainment of a crystalline, or a glassy product are presently beyond the possibilities of first principle approaches, and empirical criteria have been proposed to this end. In this work we limit ourselves to the very beginning of phase formation, i.e. thenucleation stage, in the frame of an atomistic model. In a binary alloy, after formation of collision cascades, the relaxation to metastable equilibrium of the locally altered compositional profile due to preferential migration to the cascade-matrix interface of one alloy component, is schematized by charge transfer events As a result, dimers of an effective alloy are formed. Conditions specific of glass and respectively crystal formation are extracted from an analysis of surface and thermochemical properties of starting and effective alloys.     

Pd对Ti合金钝化影响的电子理论研究

采用递归法计算了Ti合金的电子态密度、环境敏感镶嵌能、费米能级等电子结构参量.计算发现Pd在晶体体内比在其表面的环境敏感镶嵌能高,说明Pd易于在 Ti合金表面偏聚.Pd在表面时,原子团簇形成能为负值,说明Pd以团簇形式分布于合金表面.态密度计算结果表明,Pd的局域态密度局限在很窄的能量范围内(-20—-15 eV),使Ti合金的总态密度在此区出现尖峰.该尖峰的存在降低了Ti合金的费米能级,于是表面含Pd较多的区域费米能级较低,含Pd少或不含Pd的区域费米能级较高.费米能级不同的两区域接触会形成微电池,在腐 关键词： Ti合金 钝化 电子结构 表面     

A new study on the catalytic mechanism of Fe-based alloys in diamond formation by Mössbauer spectroscopy

M?ssbauer spectroscopy has been used to systemically study the catalytic mechanism of Fe-based alloys in diamond formation at high temperature–high pressure (HTHP) for the first time. M?ssbauer spectra reveal the magnetic state of the 3d electrons of a Fe atom in the Fe-based alloy catalyst during diamond formation at HTHP. During carburization at lower temperatures than that required for diamond formation and diamond formation in the diamond-stability region using Fe-based alloys as a catalyst, both the quadrupole splitting QS and the isomer shift IS change from negative to positive, especially reaching a state in which they are zero. It was indicated that the state of the 3d-shell electrons of the iron atom changes greatly during carburization and diamond formation and that the incomplete 3d sub-bands of Fe atoms in the catalyst alloys could be filled up in proper order by electrons of interstitial carbon atoms. During diamond formation, the unpaired 3d-shell electrons of an iron atom in the Fe-based alloy absorb and interact with 2P_z electrons of the carbon atoms. There exist a Fe–C bonding and an electron charge transfer stage. The 2P_z electrons of the carbon atoms could be dragged into the metal atoms in the catalyst alloy and would make a transition of triangular (sp²π) hybridization of valence electrons to tetrahedral (sp³) hybridization of valence electrons (a transition of sp²π bonds of graphite to sp³ bonds of diamond), resulting in a transition of graphite structure to diamond. Although the conclusion of this study is strictly applicable only to Fe-based alloy catalysts, it could be considered more general because of the chemical similarities between the transition elements used as solvent catalysts for diamond synthesis. Received: 2 March 2001 / Accepted: 20 August 2001 / Published online: 2 October 2001     

Charge transfer and martensitic nucleation

Summary The microscopic interpretation of phase stability in alloys undergoing thermoelastic martensitic transformation involves a difficult nucleation problem. The strong dependence of the critical temperature for the onset of martensite on composition requires the introduction of nonclassical defective nuclei, of dynamic nature, to obtain reasonable estimates of the energy barrier to nucleation. Experimental data on β-Au−Zn-based alloys are organized in the framework of the atomistic model of the valence electron localization degree. The resulting charge transfer scheme is strictly correlated to elementary surface segregation events driven by elemental surface energy differences within the studied alloys. The connection between martensitic nucleation and charge transfer segregation is discussed, focusing on the physical meaning of the various energy terms entering the model. To speed up publication, the author of this paper has agreed to not receive the proofs for correction.     

The free growth criterion for grain initiation in TiB 2 inoculated γ-titanium aluminide based alloys

γ-titanium aluminide (γ-TiAl) based alloys enable for the design of light-weight and high-temperature resistant engine components. This work centers on a numerical study of the condition for grain initiation during solidification of TiB₂ inoculated γ-TiAl based alloys. Grain initiation is treated according to the so-called free growth criterion. This means that the free growth barrier for grain initiation is determined by the maximum interfacial mean curvature between a nucleus and the melt. The strategy presented in this paper relies on iteratively increasing the volume of a nucleus, which partially wets a hexagonal TiB₂ crystal, minimizing the interfacial energy and calculating the corresponding interfacial curvature. The hereby obtained maximum curvature yields a scaling relation between the size of TiB₂ crystals and the free growth barrier. Comparison to a prototypical TiB₂ crystal in an as cast γ-TiAl based alloy allowed then to predict the free growth barrier prevailing under experimental conditions. The validity of the free growth criterion is discussed by an interfacial energy criterion.     

Investigation of the effect of pressure on thermodynamic properties and thermoelastic phase transformation of CuAlNi alloys: A molecular dynamics study

Thermoelastic phase transformations and thermodynamic properties of CuAlNi alloys at 0, 1, 2 and 3 GPa pressures were investigated by using MD simulation in this study. The interactions between atoms were modelled by Sutton-Chen type of embedded atom method (SCEAM) that is based on many-body interaction. It was observed that thermoelastic phase transformation in the ternary alloy system occurred at the end of thermal process. Radial distribution function (RDF) was used in order to analysis the structures obtained from MD simulation using the simulation techniques’ thermodynamic parameters. The transformation temperatures, enthalpy and entropy of the ternary alloy system have been observed to be changing with the applied pressure. In addition, it was found that the elastic energy has been decreased about 22% by applied pressure whereas Gibbs free energy has been increased about 60% by applied pressure. The values of the thermodynamical parameters obtained in this study were observed to be in close agreement with the experimental study.     

Concentration dependence of thermodynamic,transport and surface properties in Ag–Cu liquid alloys

Thermodynamic, transport and surface properties of Ag–Cu liquid alloys have been investigated on the basis of a simple statistical model. The free energy of mixing, heat of mixing and entropy of mixing have been computed to understand the thermodynamic properties of Ag–Cu alloys in liquid state at 1,423 K. The concentration–concentration fluctuations in the long wavelength limit and the chemical short range order parameter have been determined to comprehend the microscopic and structural information of the alloy. The viscosity and surface tension of the alloy have been evaluated to analyze the transport and surface properties. The theoretical analysis reveals that the energy parameter is temperature dependent, and that Ag–Cu liquid alloy is a weakly interacting-phase separating system.     

Characteristic chemical shift of quasicrystalline alloy Al53Si27Mn20 studied by EELS and SXES

Chemical shifts of all constituent atoms for amorphous (Am), quasicrystalline (QC) and crystalline (Cryst) alloys of Al₅₃Si₂₇Mn₂₀ were investigated for the first time by high energy-resolution electron energy-loss spectroscopy (EELS) and soft-X-ray emission spectroscopy (SXES). Among Al L-shell excitation EELS spectra of Am, QC and Cryst alloys, only QC alloy showed an apparent chemical shift to the larger binding energy side by 0.4?eV. In Al-K_α and Si-K_α emission SXES spectra of these alloys, only QC alloy showed a chemical shift to the larger binding energy side by 4?eV for Al-K_α and 6?eV for Si-K_α. These chemical shift values are comparable to those of corresponding metal oxides. This indicates a smaller amount of valence charge at Al and Si atomic sites in QC alloy. On the other hand, Mn-L SXES spectra did not show any chemical shift. Therefore, the decreased charge from Al and Si sites should be distributed between atomic sites, indicating the presence of covalent bonding nature for QC ordered alloy.     

Al_xCrFeNiTi系高熵合金成分和弹性性质关系

为了探索Al_xCrFeNiTi系高熵合金组成成分和弹性性质的关系,结合固溶体特征参数和第一性原理计算,研究Al元素含量对Al_xCrFeNiTi (x=0, 0.5, 1, 2, 3, 4)合金结构和弹性性质的影响,并分析合金固溶体特征参数与弹性性质之间的关系.结果表明:Al_xCrFeNiTi系合金的价电子浓度随着Al含量的增加逐渐减小,合金在体心立方结构下的形成焓均低于面心立方结构,说明研究的Al_xCrFeNiTi系合金会形成单一的体心立方结构固溶体;合金的晶格常数和形成能力强弱随着Al含量的增加而增大,但合金的结构稳定性略有下降;当合金元素按照等原子比进行成分配比时,合金的原子尺寸差异最大; Al_xCrFeNiTi系合金中不同原子之间除了金属键结合外,还表现出一定的共价和离子键结合特征;对于Al_xCrFeNiTi系合金而言,随着热力学熵焓比的增大,合金体弹模量和韧性随之增大;随着合金混合焓的增加,合金在压缩方向的各向异性程度明显降低.热力学熵焓比和混合焓可作为Al_xCrFeNiTi系高熵合金成分设计的重要参数.     

Chemical shifts of metallic and non-metallic Al–Re–Si approximant crystals studied by EELS and SXES

Chemical shifts of approximant crystals of 1/0-Al₁₂Re (1/0-metallic), 1/1-Al₇₃Re₁₅Si₁₂ (1/1-metallic) and 1/1-Al₇₃Re₁₇Si₁₀ (1/1-non-metallic) were examined by using electron energy-loss spectroscopy (EELS) and soft-X-ray emission spectroscopy (SXES). Al L-shell excitation EELS spectra of these alloys showed an apparent chemical shift only for the 1/1-non-metallic alloy to the larger binding energy side by 0.2?eV. Al-Kα, Re-Mα and Si-Kα emission SXES spectra also showed a shift to the larger binding energy side only for 1/1-non-metallic alloy. 1/0-metallic and 1/1-metallic alloys did not show any chemical shift in EELS and SXES experiments. Chemical shifts were observed only in larger binding energy side compared with pure materials. This implies the decrease of valence charge at constituent atomic sites of 1/1-non-metallic alloy compared with 1/0-metallic, 1/1-metallic and pure materials. The decreased charges should distribute intermetallic sites, which should be related to a formation of covalent bonding among Al atomic sites reported by maximum-entropy method (MEM)/Rietveld analysis on this material. This relation between chemical shift and covalent bonding nature of this approximant alloy may support the presence of covalent bonding in Al-based quasicrystals.     

A self-consistent TB-LMTO-augmented space recursion method for disordered binary alloys

We developed a complete self-consistent TB-LMTO-Augmented space recursion (ASR) method for calculating configurational average properties of substitutionally disordered binary alloys. We applied our method to fcc based Cu-Ni, Ag-Pd for different concentrations of constituent elements and body-centered cubic based ferromagnetic Fe-V (50-50) alloy. For this systems we investigated the convergence of total energy and l-dependent potential parameters, charges, magnetic moment, energy moments of density of states with the number of iterations. Our results show good agreement with the existing calculations and also with the experimental results where it is available. The Madelung energy correction due to the charge transfer has also been included by the method developed by Ruban et al.     

Heats of formation of binary transition metal alloys

The heats of formation of disordered transition metal alloys are related to moments of the density of states within an analytical tight-binding model for the d band. The difference in bandwidth and in energy levels between the metals are two dominant effects on alloying. The d charge transfer is evaluated in a self consistent way from the knowledge of the partial densities of states.