Surface tension modelling of liquid Cd–Sn–Zn alloys

The thermodynamic model in conjunction with Butler equation and the geometric models were used for the surface tension calculation of Cd–Sn–Zn liquid alloys. Good agreement was found between the experimental data for limiting binaries and model calculations performed with Butler model. In the case of ternary alloys, the surface tension variation with Cd content is better reproduced in the case of alloys lying on vertical sections defined by high Sn to Zn molar fraction ratio. The calculated surface tension is in relatively good agreement with the available experimental data. In addition, the surface segregation of liquid ternary Cd–Sn–Zn and constituent binaries has also been calculated.     

Equilibrium and kinetic surface segregations in Cu–Sn thin films

Equilibrium and kinetic surface segregations in Cu–Sn thin films are simulated based on the modified Darken model for a finite sized system. The simulations are carried out for all compositional ranges and film thicknesses. The segregation energy and the interaction parameter for the simulation are determined respectively by the Miedema model and from the thermodynamic data used for the Cu–Sn phase diagram calculation. The strong negative interaction parameter restrains Sn surface segregation in the Cu–Sn system. The size effect on surface segregation depends on the segregation energy, interaction parameter, initial bulk concentration, temperature and film thickness.     

Equilibrium segregation in a ternary solution: A model for temper embrittlement

Whereas experimental evidence has established that temper embrittlement is due to the simultaneous intergranular segregation of some impurities I (Sb, P, As Sn, ...) and of metallic alloying elements M (Ni, Cr, Mn, ...), all the theories of this phenomenon have failed so far to rationalize the role of the alloying elements, i.e. essentially to explain why they are necessary for the segregation of the impurities to occur. The thermodynamical formalism of equilibrium segregation, when taking into account the interaction of M and I atoms in an iron base solid solution can explain this behaviour. The simplest analytical treatment of such interaction based on the regular solution model is developed. The values of the interaction coefficients between the various atoms, as evaluated from the enthalpies of mixing of the intermetallic compounds, appear consistent with the value deduced from segregation measurements. The model is shown to allow a comprehensive interpretation of the segregation behaviour of various binary and ternary solutions, in particular the iron base systems. Eventually the role of bi-dimensional compound formation in the segregation process is considered.     

Experimental investigation and thermodynamic calculation of the Bi-Ga-Sn phase equilibria

Binary thermodynamic data, successfully used for phase diagram calculations of binary systems Bi-Ga, Bi-Sn, and Ga-Sn, were used for prediction of phase equilibria in ternary Bi-Ga-Sn system. The thermodynamic functions, such as enthalpy of formation and activity, were calculated using the Redlich-Kister-Muggianu model and compared with experimental data reported in the literature. The liquidus surface, invariant equilibria and three vertical sections with molar ratio Ga:Sn=1, Bi:Sn=1 and Bi:Ga=1 of the Bi-Ga-Sn ternary system were calculated by the CALPHAD method. Alloys, situated along three calculated vertical sections, were investigated by Differential Scanning Calorimetry (DSC). The experimentally determined phase transition temperatures were compared with calculation results and good mutual agreement was noticed.     

Segregation of tin on (111) and (100) surfaces of copper

Surface segregation of Sn in Cu is measured at (111) and (100) surfaces by means of AES and LEED. In the case of at temperature measurements and no cosegregation of impurities occurring, equilibrium segregation is accomplished for Sn bulk concentrations between 40 and 4300 at ppm and temperatures of 800 to 1230 K. The maximum segregation level of Sn corresponds to a (√3 × √3)R30° structure for the (111) surface and a p(2 × 2) structure for the (100) surface. For theoretical analysis, the Langmuir-McLean equation has to be modified. No difference in segregation enthalpies for both surface orientations is found within the experimental error. The mean segregation enthalpy is determined to ΔH = ?(53 ± 5) kJ/g-atom.     

Surface segregation in liquid GaSn alloys by AES

The surface segregation of Sn in liquid GaSn alloys has been studied by Auger electron spectroscopy as a function of bulk concentration at 350° C. The Sn was found to be strongly adsorbed at the surface. The surface concentrations of Sn and Ga were calculated from the Auger measurements using inelastic mean free paths and backscattering factors estimated in recent theoretical work. The values found for the surface concentrations are essentially in agreement with those deduced from surface tension measurements using Gibbs adsorption theory. This result supports a monolayer adsorption distribution in the GaSn system.     

Peculiarities of segregation phenomena at the surface of Pd x V1 − x alloys in an oxygen medium

The elemental composition and the nature of the chemical bond at the surface of two vanadium-palladium alloys are studied as functions of the sample warm-up temperature by x-ray photoelectron spectroscopy. The obtained results are explained in the framework of segregation theories for ternary systems of strongly diluted solutions.     

A method for the study of surface segregation in multicomponent alloys

A simple algorithm for the determination of segregation profiles in multicomponent systems based on a mean field formalism and a quantum approximate method for the energetics is introduced. The method is described and applied to two ternary systems, concentrating on the changes in segregation patterns relative to the corresponding binary cases.     

Surface segregation and oxidation studies on Cu-Ni-Sn and Ag-Cu-Ge ternary alloys

Surface segregation and oxidation of Cu-9.7at%Ni-2.3at%Sn and Ag-39at%Cu-1.6at%Ge ternary alloys have been carried out employing XPS and AES techniques. Segregation of both Ni and Sn have been observed on the surface of Cu-Ni-Sn alloy. On oxidation of this alloy at 500 K, Cu₂O, NiO and SnO have been observed and on heating the oxidized alloy in vacuum to 600 K, Cu₂O was reduced to Cu through a displacement reaction involving Ni. Further heating to 750 K showed only SnO₂ along with the reduction of NiO to Ni. The Ag-Cu-Ge alloy showed segregation of both Ag and Ge to the surface. On oxidation at 500 K, only Cu₂O and GeO have been observed. Heating of the oxidized surface to 700 K in vacuum showed desorption of GeO, coupled with the reduction of Cu₂O to Cu, thereby leaving the alloy surface clean.     

First-principles investigations of the Ni3Sn alloy at steam reforming conditions

The structure and surface composition of a Ni₃Sn alloy at conditions relevant for the steam reforming reaction was investigated using density functional theory calculations. Both the flat Ni₃Sn(0 0 0 1) surface and a surface with steps in the closed packed direction [1 0  0]were considered. The adsorption geometries and energies of the species CO, C, OH and H were calculated. Chemical potentials were used to map out which adsorbates are on the surface under varying conditions. It was found that adsorbates preferably bind to Ni as nearest neighbor with Sn as second-nearest neighbor. The binding energy is slightly stronger than on pure Ni. Adsorbate binding to Sn was found to be very unfavorable. Binding free energies indicate that at high temperature the alloy surface will be predominantly covered by CO and C, and at low temperatures one may find H and almost no OH. Even though the nominal composition of the investigated alloy is Ni₃Sn, the surface composition may differ significantly depending on temperature and pressure of the gas phase. This effect was investigated by calculating segregation energies both in the absence and in the presence of adsorbates. For the flat surface, it was found that only the bulk termination is present under relevant conditions. In contrast, it was found that for steps preferential adsorption of CO and C on Ni sites may lead to adsorption-induced segregation at temperatures below 400 °C. When taking segregation into account, the most stable Ni₃Sn surfaces will not bind CO or C at the same condition that Ni does. This is in excellent agreement with the previously proven ability of Ni-Sn alloys to inhibit graphite formation.     

Effect of temperature on surface composition of Cu-Sn and Ag-Sn alloys; an ESCA study

Cu-Sn and Ag-Sn alloys containing 5% Sn were studied by ESCA. The heats of surface segregation of Sn obtained from equilibrium measurements of the surface composition as a function of temperature were found to be 12.0 ± 1.0 and 3.5 ± 1.0 kcal/mol for Cu-Sn and Ag-Sn alloys, respectively. These results are compared with the predictions of existing theories. Possible reasons for the difference between the experimental result and theoretical prediction are also discussed.     

Effects of rapid thermal annealing on crystallinity and Sn surface segregation of Ge_(1-x)Sn_x films on Si(100) and Si(111)

Germanium-tin films with rather high Sn content(28.04% and 29.61%) are deposited directly on Si(100) and Si(111)substrates by magnetron sputtering. The mechanism of the effect of rapid thermal annealing on the Sn surface segregation of Ge_(1-x)Sn_x films is investigated by x-ray photoelectron spectroscopy(XPS) and atomic force microscopy(AFM). The x-ray diffraction(XRD) is also performed to determine the crystallinities of the Ge_(1-x)Sn_x films. The experimental results indicate that root mean square(RMS) values of the annealed samples are comparatively small and have no noticeable changes for the as-grown sample when annealing temperature is below 400℃. The diameter of the Sn three-dimensional(3 D) island becomes larger than that of an as-grown sample when the annealing temperature is 700℃. In addition, the Sn surface composition decreases when annealing temperature ranges from 400℃ to 700℃. However, Sn bulk compositions in samples A and B are kept almost unchanged when the annealing temperature is below 600℃. The present investigation demonstrates that the crystallinity of Ge_(1-x)Sn_x/Si(111) has no obvious advantage over that of Ge_(1-x)Sn_x/Si(100) and the selection of Si(111) substrate is an effective method to improve the surface morphologies of Ge_(1-x)Sn_x films. We also find that more severe Sn surface segregation occurs in the Ge_(1-x)Sn_x/Si(111) sample during annealing than in the Ge_(1-x)Sn_x/Si(100) sample.     

深过冷Cu60Sn30Pb10偏晶合金的快速凝固

实现了大体积Cu₆₀Sn₃₀Pb₁₀偏晶合金的深过冷与快速凝固. 实验获得的最大过冷度为173 K(0.17T_L). 凝固组织发生了明显的宏观偏析,XRD分析表明,试样上部是由固溶体(Sn),(Pb)相和金属间化合物ε(Cu₃Sn)相组成的三相区,下部为富(Pb)相区. 在小过冷条件下,三相区中ε(Cu₃Sn)相的凝固组织为粗大的枝晶,随着过冷度的增大,ε(Cu₃Sn)相细化成层片状组织,且层片间距随过冷度的增大而减小,而(Sn),(Pb)两相始终以离异共晶的方式存在. 富(Pb)相区中分布有少量的ε(Cu₃Sn)枝晶,枝晶长度随过冷度的增大而增大,且在大过冷条件下发生碎断. (Sn)相在ε(Cu₃Sn)相表面形核、长大,其形态类似于包晶凝固组织. 关键词： 深过冷 快速凝固 偏晶合金 层片组织     

银—锡—铝三元系合金相图

用X射线方法测定了银-锡-铝三元系合金相图。合金含量从30wt.％Sn到纯锡,从30wt.％Al到纯铝。同时,对此三元系的富银角(<30wt.％Sn,<30wt.％Al)相图的γ相区,ζ+δ相区和β+γ+δ相区重新做了测定。室温相截面由六个单相(即α,μ,β,γ,Sn和δ)相区,八个双相(即α+μ,α+β,β+μ,β+γ,γ+Sn,β+Sn,β+δ及Sn+δ)相区,和三个三相(即α+β+μ,β+γ+Sn及β+Sn+δ)相区所构成。所有单相与三个二元系的单相一致,没有新相出现。     

第一性原理研究Nb、Sn、Cu、Fe和Cr对Zr (0001)晶面抗疖状腐蚀性能的影响

采用密度泛函理论研究Nb、Sn、Cu、Fe和Cr 5种合金元素对氧在Zr(0001)晶面吸附能的影响, 发现Nb、Sn和Cu会促进氧在Zr(0001)晶面吸附, Fe和Cr对氧吸附的影响因吸附的位置不同而存在差异。研究5种合金元素对氧化后Zr(0001)晶面化学键的破坏情况, 发现Nb对Zr(0001)晶面破坏程度最小而且可以迅速复原, Sn可以使(0001)晶面相邻的两个化学键都变长, 对晶面的破坏性大。最后讨论5种合金元素在Zr(0001)晶面的偏聚能, 发现Sn、Fe和Cr偏聚能为负值, 容易偏聚到Zr(0001)晶面, 而Nb和Cu偏聚能为正值, 不易在Zr(0001)晶面偏聚。综合以上分析, Nb可以促进氧在Zr(0001)晶面的吸附行为, 氧化后(0001)晶面可以快速复原, 从而阻碍其他氧原子进入, 抑制疖状腐蚀的发生。Sn容易偏聚到Zr(0001)晶面, 可以促进氧在Zr(0001)晶面吸附, 氧化后会造成Zr(0001)晶面较大的破坏, 促进氧进入Zr(0001)晶面, 促进疖状腐蚀的发生。     

银-锑-锡三元系合金相圖

银—锑—锡三元系合金的室温固相截面已经用X-射线和金相两种方法测定了出来,而且每一相区的边界都用X-射线方法作了精密确定。相图中主要是由六个单相区,即α,β,γ,β′,纯Sn及纯锑单相区,和七个变相区及两个三相区所构成。没有新相出现,所有的相与银—锑二元系,银—锡二元系和锑—锡二元系所有的相完全符合。     

Localised surface segregation and martensite nucleation in noble metal based ternary alloys

A recent model connecting martensite nucleation with localised surface segregation phenomena is extended to dilute ternary alloys based on -CuZn and -AuCd. Experimental data about composition induced variations of the critical temperature for the onset of martensitic transformation are organised in a coherent fashion by the atomistic Valence Electron Localisation Degree variation model. An analysis of the surface segregation properties of the original and effective alloys involved in micro nucleation events of martensite is performed by a model relying upon charge transfer effects. It is concluded that martensite nucleation may be interpreted in terms of preferential, localised surface segregation events.Preliminary results of the research were presented at the Discussion Meeting on CuZnAl Martensite Shape Memory Alloys, 19–21 June 1984, Leuven, Belgium     

Segregation of Sn and Sb in a ternary Cu(1 0 0)SnSb alloy

Surface segregation studies of Sn and Sb in Cu(1 0 0)-0.14 at.% Sn-0.12 at.% Sb ternary alloy, have been done by making use of Auger Electron Spectroscopy. The method of Linear Temperature Ramp (LTR) was employed, whereby the sample was heated and cooled linearly at a constant rate. The positive heating rate showed both a kinetic segregation profile, as well as a narrow equilibrium segregation region, at higher temperatures. The equilibrium segregation profile was extended by cooling the sample. Sn was first to segregate to the surface due to its higher diffusion coefficient, mainly from a smaller activation energy E_Sn. Sb, due to its higher segregation energy, eventually replaced Sn from the surface. The modified Darken model was used to simulate the profile yielding the following segregation parameters: D_o(Sn) = 6.3 × 10⁻⁶ m²/s, D_o(Sb) = 2.8 × 10⁻⁵ m²/s; E_Sn = 175.4 kJ/mol, E_Sb = 186.3 kJ/mol; , ; Ω_Cu-Sn = 3.4 kJ/mol, Ω_Cu-Sb = 15.9 kJ/mol and Ω_Sn-Sb = −5.4 kJ/mol.     

Surface phase transitions induced by electron mediated adatom-adatom interaction

We propose that the indirect adatom-adatom interaction mediated by the conduction electrons of a metallic surface is responsible for the sqrt[3]xsqrt[3]<==>3x3 structural phase transitions observed in Sn/Ge (111) and Pb/Ge (111). When the indirect interaction overwhelms the local stress field imposed by the substrate registry, the system suffers a phonon instability, resulting in a structural phase transition in the adlayer. Our theory is capable of explaining all the salient features of the sqrt[3]xsqrt[3]<==>3x3 transitions observed in Sn/Ge (111) and Pb/Ge (111), and is in principle applicable to a wide class of systems whose surfaces are metallic before the transition.     

Mössbauer and XRD study of pulse plated Sn-Fe,Sn-Ni and Sn-Ni-Fe electrodeposited alloys

Effect of pulse plating on novel electrodeposited binary and ternary amorphous alloys was studied by ⁵⁷Fe and ¹¹⁹Sn conversion electron Mössbauer spectroscopy and X-ray diffraction. Our results show that by adjusting the parameters of pulse plating a fine tuning of the composition and current efficiency can be achieved within these systems. On the contrary to direct current deposition, where the crystalline FeSn₂ phase dominates, pulse plating technique produces amorphous Sn-Fe alloy phases, of which the ferromagnetic phase is the dominant one. Both, direct current and pulse plated Sn-Ni deposits consist of paramagnetic alloy phases and minor amounts of β-Sn, the occurrence of which correlates with the tin content of the samples. Pulse plated Sn-Ni-Fe coatings are amorphous and in a dominantly ferromagnetic state, however at long on- and off-pulse times and high peak current density the paramagnetic state dominates and β-Sn segregation also occurs.