Thermodynamic description of the Sn–Ag–Au ternary system

Gibbs energy of hcp_A3 phase in the Ag–Sn binary system has been reassessed using compatible lattice stability. Combined with previous assessments of the Ag–Au and Au–Sn binary systems, the Sn–Ag–Au ternary system has been thermodynamically optimized using the CALPHAD method on the basis of available experimental information. The solution phases including liquid, fcc_A1, hcp_A3 and bct_A5, are modeled as substitutional solutions, while the intermediate compound Ag₃Sn is treated using a 2-sublattice model because Au can be dissolved to a certain degree. The solubility of Ag in the Au–Sn intermediate phases, D0₂₄, Au₅Sn, AuSn, AuSn₂ and AuSn₄, is not taken into account. Thermodynamic properties of liquid alloys, liquidus projection and several vertical and isothermal sections of this ternary system have been calculated, which are in reasonable agreement with the reported experimental data.     

Thermodynamic assessment of the Au–Ni system

The phase diagram and thermodynamic properties of the Au–Ni system have been assessed from experimental thermodynamic and phase diagram data by means of the CALPHAD method. A consistent set of thermodynamic parameters for each phase was obtained. Good agreement is reached between the calculated and experimental results. The calculated congruent point is 1214.3 K and 42.6 at.% Ni and the critical point of the miscibility gap is 1089.5 K and 73.0 at.% Ni.     

An optimal method to calculate the viscosity of simple liquid ternary alloys from the measured binary data

An optimal method to calculate the viscosity of simple liquid ternary alloys from the measured binary data is investigated in this paper. In order to find a relationship which describes the ternary viscosity data from binary data most adequately, a comparison was made between three different approaches tested on the example of the Au–Ag–Cu system. The optimal method turned out to be the extension of the Redlich–Kister polynomial to excess viscosity without any ternary term. This optimal method was applied further on the Fe–Ni–Co system. The estimation of viscosities for liquid Fe–Ni–Co alloys was done in different sections with molar ratio of two components equal to 1:1, 1:3 and 3:1. A diagram showing iso-viscosity lines was constructed at the investigated temperature of 1873 K.     

The experimental study of the Bi–Sn, Bi–Zn and Bi–Sn–Zn systems

The binary Bi–Sn was studied by means of SEM (Scanning Electron Microscopy)/EDS (Energy-Dispersive solid state Spectrometry), DTA (Differential Thermal Analysis)/DSC (Differential Scanning Calorimetry) and RT-XRD (Room Temperature X-Ray Diffraction) in order to clarify discrepancies concerning the Bi reported solubility in (Sn). It was found that (Sn) dissolves approximately 10 wt% of Bi at the eutectic temperature.

The experimental effort for the Bi–Zn system was limited to the investigation of the discrepancies concerning the solubility limit of Zn in (Bi) and the solubility of Bi in (Zn). Results indicate that the solubility of both elements in the respective solid solution is approximately 0.3 wt% at 200 C.

Three different features were studied within the Bi–Sn–Zn system. Although there are enough data to establish the liquid miscibility gap occurring in the phase diagram of binary Bi–Zn, no data could be found for the ternary. Samples belonging to the isopleths with w(Bi) 10% and w(Sn) 5%, 13% and 19% were measured by DTA/DSC. The aim was to characterize the miscibility gap in the liquid phase. Samples belonging to the isopleths with w(Sn) 40%, 58%, 77/81% and w(Zn) 12% were also measured by DTA/DSC to complement the study of Bi–Sn–Zn. Solubilities in the solid terminal solutions were determined by SEM/EDS. Samples were also analyzed by RT-XRD and HT-XRD (High Temperature X-Ray Diffraction) confirming the DTA/DSC results for solid state phase equilibria.     

Experimental investigation and thermodynamic calculation of the Fe–Si–Bi system

Phase relationship of the Fe–Si–Bi ternary system was established by optical microscope, scanning electron microscope in combination with energy dispersive spectroscopy and X–ray diffraction. Isothermal sections of the Fe–Si–Bi system at 973 and 1173 K consist of 3 and 4 three–phase equilibrium regions, respectively. The liquid phase is in equilibrium with all the Fe–Si phases. No ternary compound is found and Bi is almost insoluble in the Fe–Si phases. Combining the reliable thermodynamic data from literature with the current experimental work, phase relationship of the Fe–Si–Bi system have been thermodynamically extrapolated. The calculated results are in good agreement with the experimental results.     

A critical thermodynamic assessment of the Mg–Ni, Ni–Y binary and Mg–Ni–Y ternary systems

A thorough review and critical evaluation of phase equilibria and thermodynamic data for the phases in the Mg–Ni–Y ternary system have been carried out over the entire composition range from room temperature to above the liquidus. This system is being modeled for the first time using the modified quasichemical model which considers the presence of short range ordering in the liquid. The Gibbs energies of the different phases have been modeled, and optimized model parameters that reproduce all the experimental data simultaneously within experimental error limits have been obtained. For the liquid phases, the modified quasichemical model is applied. A sublattice model within the compound-energy formalism is used to take proper account of the structures of the binary intermediate solid solutions. The Mg–Ni and Ni–Y binary systems have been re-optimized based on the experimental phase equilibrium and thermodynamic data available in the literature. The optimized thermodynamic parameters for the Mg–Y system are taken from the previous thermodynamic assessment of the Mg–Cu–Y system by the same authors. The constructed database has been used to calculate liquidus projection, isothermal and vertical sections which are compared with the available experimental information on this system. The current calculations are in a good agreement with the experimental data reported in the literature.     

Layer-by-layer construction of an active multilayer enzyme electrode applicable for direct amperometric determination of cholesterol

A biosensor for direct amperometric determination of cholesterol was constructed by a layer-by-layer nanothin film formation using cholesterol oxidase (COx) and poly(styrenesulfonate) on a monolayer of microperoxidase covalently-immobilized on Au–alkanethiolate electrodes. Cyclic voltammograms (CVs) of microperoxidase covalently-immobilized on mercaptopropionic acid- and aminoethanethiol-monolayer electrodes showed a redox wave with the formal potential of 0.40 V (versus Ag | AgCl | NaCl (sat.)). The formal potential and the apparent heterogeneous electron-transfer rate of immobilized microperoxidase were not specific with the inner Au–alkanethiolate layer. The biosensor shows a linear current response for cholesterol at the applied potential of 0 V in the concentration range of 0.2–3.0 mM with a correlation coefficient of 0.969. The current response of the biosensor for cholesterol was very rapid (response time <20 s) and was highly reproducible; sample standard deviation of the current response at the concentration of 1.5 mM in five individual determinations was 0.09. The magnitude of the amperometric response for cholesterol was 0.13 μA cm⁻² at the concentration of 1.5 mM. The inertness and stability of the biosensor towards the potential electrical interferents, -ascorbic acid, pyruvic acid and uric acid, was tested, and it was found that the biosensor rapidly responses to the addition of cholesterol even in the presence of these interferents.     

Thermodynamic modeling of Fe–Ti–Bi system assisted with key experiments

Phase equilibria of Fe–Ti–Bi ternary system have been studied in this work. Firstly, by using alloy sampling, the isothermal section of Fe–Ti–Bi ternary system at 773 K was determined, where the existence of a ternary phase Bi₂FeTi₄ was confirmed. Meanwhile, formation enthalpies of the intermediate phases BiTi₂, Bi₉Ti₈ and Bi₂FeTi₄, were obtained with first-principles calculations. Based on experimental data of phase equilibria and thermodynamic properties in literatures along with the calculated formation enthalpies in this work, thermodynamic modeling of Ti–Bi binary system and Fe–Ti–Bi ternary system were carried out with the CALPHAD approach. A set of self-consistent thermodynamic parameters to describe the Gibbs energy for various phases in Fe–Ti–Bi ternary system was finally obtained, with which solidification processes of two typical Fe–Ti–Bi alloys could be reasonably explained.     

Thermodynamic modeling of the Mg–Bi and Mg–Sb binary systems and short-range-ordering behavior of the liquid solutions

In order to investigate the short range ordering behavior of liquid Mg–Bi and Mg–Sb solutions, thermodynamic modeling of the Mg–Bi and Mg-Sb binary systems has been performed. All available thermodynamic and phase diagram data of the Mg–Bi and Mg–Sb binary systems have been critically evaluated and all reliable data have been simultaneously optimized to obtain one set of model parameters for the Gibbs energies of the liquid and all solid phases as functions of composition and temperature. In particular, the Modified Quasichemical Model, which accounts for short-range-ordering of nearest-neighbor atoms in the liquid, was used for the liquid solutions. A comparative evaluation of both systems was helpful to resolve inconsistencies of the experimental data. The thermodynamic modeling shows the strong ordering behavior in the liquid Mg–Bi and Mg–Sb solutions at Mg₃Bi₂ and Mg₃Sb₂ compositions, respectively, and predicts the metastable liquid miscibility gaps at sub-solidus temperatures. All calculations were performed using the FactSage thermochemical software.     

Thermodynamic and ab initio investigation of the Al–H–Mg system

A coupled ab initio and thermodynamic study of the Al–H–Mg system has been carried out and a self-consistent thermodynamic database has been obtained. Magnesium alanate Mg(AlH₄)₂, a candidate material for hydrogen storage, has been included into the database. According to Density Functional first principles calculations, the alanate is an insulator and its thermodynamic properties have been obtained at room temperature. This compound has been found metastable at 298.15 K and 1 bar. The alanate has been found thermodynamically stable only at high pressure when the formation of the binary β-MgH₂ phase is neglected. A reassessment of thermodynamic parameters of the liquid phase in the binary Mg–H system has also been carried out in order to be consistent with the Al–H system. The present results can reproduce reasonably well the available experimental data.     

Thermodynamic and ab initio investigation of the Cu–Dy system

A combined ab initio and thermodynamic study of the Cu–Dy system has been performed and a self-consistent thermodynamic database has been obtained. Density functional theory has been applied by using the VASP code in order to obtain the enthalpy of formation at 0 K of intermetallic compounds. Experimental information on the Cu–Dy phase diagram and thermodynamic properties of its alloys have been collected. Using these data, optimized parameters have been obtained by applying the CALPHAD approach. The present results reproduce the experimental data available reasonably well, although some features of the Cu–Dy system need to be further clarified.     

Experimental investigation and modeling of vapor-liquid equilibria for Bi–Zn and Bi–Sn–Zn systems at 10 Pa

For the Bi–Zn and Bi–Sn–Zn systems, vacuum distillation experiments were carried out at 10 Pa. The results show that the content of Zn for the Bi–Zn system in the vapor phase could reach more than 0.999 mol fraction in vacuum distillation. The VLE (vapor-liquid equilibrium) data were correlated using the Tsuboka-Katayama's modification of the Wilson equation (T-K-Wilson). The correlation showed good agreement with experimental data. Thermodynamic consistency tests of experimental data for the binary and ternary systems were presented by the Van Ness method. The results demonstrate that VLE phase diagram is reliable for predicting the process of vacuum distillation for the systems. It provides an efficient way to guide the separation and purification of crude Zn in vacuum metallurgy     

A thermodynamic description of the Al–Ca–Zn ternary system

A comprehensive thermodynamic database of the Al–Ca–Zn ternary system is presented for the first time. Critical assessment of the experimental data and re-optimization of the binary Al–Zn and Al–Ca systems have been performed. The optimized model parameters of the third binary system, Ca–Zn, are taken from the previous assessment of the Mg–Ca–Zn system by the same authors. All available as well as reliable experimental data both for the thermodynamic properties and phase boundaries are reproduced within experimental error limits. In the present assessment, the modified quasichemical model in the pair approximation is used for the liquid phase and Al_FCC phase of the Al–Zn system to account for the presence of the short-range ordering properly. Two ternary compounds reported by most of the research works are considered in the present calculation. The liquidus projections and vertical sections of the ternary systems are also calculated, and the invariant reaction points are predicted using the constructed database.     

Thermodynamic evaluation of the phase equilibria and glass-forming ability of the Fe–Si–B system

A thermodynamic study has been carried out on the Fe–Si–B ternary system, which is important in the development of transformer core materials and Ni-based filler metals. A regular solution approximation based on the sublattice model was adopted to describe the Gibbs energy for the individual phases in the binary and ternary systems. Thermodynamic parameters for each phase were evaluated by combining the experimental results from differential scanning calorimetry with literature data. The evaluated parameters enabled us to obtain reproducible calculations of the isothermal and vertical section diagrams. Furthermore, the glass-forming ability of this ternary alloy was evaluated by introducing thermodynamic quantities obtained from the phase diagram calculations into Davies–Uhlmann kinetic formulations. In this evaluation, the time–temperature-transformation (TTT) curves were obtained, which are a measure of the time required to transform to the minimum detectable mass of crystal as a function of temperature. The critical cooling rates calculated on the basis of the TTT curves enabled us to evaluate the glass-forming ability of this ternary alloy. The results show good agreement with the experimental data in the compositional amorphization range.     

Statistical Translation of Text and Speech: First Results with the RWTH System

In this paper, we describe a first version of a system for statisticaltranslation and present experimental results. The statistical translationapproach uses two types of information: a translation model and a languagemodel. The language model used is a standard bigram model. The translationmodel is decomposed into lexical and alignment models. After presenting the details of the alignment model, we describe the search problem and present a dynamic programming-based solution for the special case of monotone alignments.So far, the system has been tested on two limited-domain tasks for which abilingual corpus is available: the EuTrans traveller task (Spanish–English,500-word vocabulary) and the Verbmobil task (German–English, 3000-wordvocabulary). We present experimental results on these tasks. In addition to the translation of text input, we also address the problem of speech translation and suitable integration of the acoustic recognition process and the translation process.     

Thermodynamic optimization of the Ni–Sn binary system

Through the CALPHAD method and based on experimental data of thermodynamic properties and phase boundaries, the phase diagram of the Ni–Sn binary system has been reassessed. The liquid and fcc_A1 (terminal rich nickel solid solution) phases were described by using a simple substitutional model, the excess Gibbs energy being formulated with a Redlich–Kister expression. The other intermediate phases (Ni₃Sn_HT, Ni₃Sn₂_HT, Ni₃Sn₂_LT, Ni₃Sn₄), were described with a several sublattice model with different formula; the Gibbs energy of the reference compounds was assumed to be linear, and the binary interaction terms on the sub-lattices to be constant. Ni₃Sn_LT was treated as a stoichiometric compound. The solubility of Ni in the terminal phase bct_A5(Sn) was neglected because it is very small. Finally a set of self-consistent thermodynamic parameters for all condensed phases in the Ni–Sn binary system was obtained, which can reproduce most of the experimental data.