Activities, concentration fluctuations and complexing in liquid Ca-Al alloys

Détermination de l'activité du calcium par la méthode d'effusion de Knudsen. Calcul, à partir de la distribution mesurée pour l'aluminium entre l'alliage et du fer pur, de l'activité de l'aluminium dans des alliages riches en calcium. Détermination en combinant les deux méthodes, des activités des deux composants et de l'énergie de Gibbs de mélange pour tout le domaine de composition. Calcul et analyse du facteur de structure concentration-concentration

Volume effects and associations in liquid alloys

The regular associated solution model for binary systems has been modified by incorporating the size of the complex as an explicit variable. The thermodynamic properties of the liquid alloy and the interactions between theA ?B type of complex and the unassociated atoms in anA-B binary have been evaluated as a function of relative size of the complex using the activity coefficients at infinite dilution and activity data at one other composition in the binary. The computational procedure adopted for determining the concentration of clusters and interaction energies in the associated liquid is similar to that proposed by Lele and Rao. The analysis has been applied to the thermodynamic mixing functions of liquid Al-Ca alloys believed to contain Al2Ca associates. It is found that the size of the cluster significantly affects the interaction energies between the complex and the unassociated atoms, while the equilibrium constant and enthalpy change for the association reaction exhibit only minor variation, when the equations are fitted to experimental data. The interaction energy between unassociated free atoms remains virtually unaltered as the size of the complex is varied between extreme values. Accurate data on free energy, enthalpy, and volume of mixing at the same temperature on alloy systems with compound forming tendency would permit a rigorous test of the proposed model.

Synthesis of nanodispersed phases during rapid solidification and crystallization of glasses in Ti75Ni25 alloys

The formation of the metallic glass and crystalline phases and related microstructures and the decomposition behavior of rapidly solidified Ti75Ni25 alloys obtained under different processing conditions have been investigated in detail. The competition between glass transition and nucleation of beta-Ti during rapid solidification leads to the possibility of synthesizing the nanocomposites of beta-Ti and glass. Additionally, it is shown that the presence of a small amount of Si also promotes simultaneous nucleation of fine Ti2Ni intermetallic compound. Thermodynamic calculation of the metastable phase diagram indicates the presence of a metastable eutectic reaction between alpha-Ti and Ti2Ni. Evidence of this reaction at lower cooling rates has been presented. On heating, the glass decomposes through this reaction. Finally, on the basis of understanding of the microstructural evolution during decomposition, a new approach has been adopted to synthesize a nanodispersed composite of alpha-Ti in the crystalline Ti2Ni matrix with a narrow size distribution by controlling the devitrification heat treatment of the metallic glass.

Assessing formability of sheet metals through advanced tensile and LASER speckle analysis

The ability of a metal to resist strain localisation and hence reduction in local thickness, is a most important forming property upon stretching. The uniform strain represents in this regard a critical factor to describe stretching ability - especially when the material under consideration exhibits negative strain rate sensitivity and dynamic strain ageing (DSA). A newly developed Laser Speckle Technique (LST), e.g. see [1], was used in-situ during tensile testing with two extensometers. The applied technique facilitates quantitative information on the propagating plasticity (i.e. the so-called PLC bands) known to take place during deformation where DSA is active. The band velocity (V-band), and the bandwidth (W-band) were monitored upon increasing accumulated strain. The knowledge obtained with the LST was useful for understanding the underlying mechanisms for the formability limit when DSA and negative strain rate sensitivity operate. The goal was to understand the relationship between PLC/DSA phenomena and the formability limit physically manifested as shear band formation. Two principally different alloys were used to discover alloying effects.

Solubility and activity of oxygen in liquid gallium and gallium copper alloys

The solubility of oxygen in liquid gallium in the temperature range 775 –1125 °C and in liquid gallium-copper alloys at 1100 °C, in equilibrium with β-Ga2O3, has been measured by an isopiestic equilibrium technique. The solubility of oxygen in pure gallium is given by the equation log (at.% O) = −7380/T + 4.264 (±0.03) Using recently measured values for the standard free energy of formation of β-Ga2O3 and assuming that oxygen obeys Sievert's law up to the saturation limit, the standard free energy of solution of oxygen in liquid gallium may be calculated : View the MathML sourceΔ°298 = −52 680 + 6.53T (±200) cal where the standard state for dissolved oxygen is an infinitely dilute solution in which the activity is equal to atomic per cent. The effect of copper on the activity of oxygen dissolved in liquid gallium is found to be in good agreement with that predicted by a recent quasichemical model in which it was assumed that each oxygen is interstitially coordinated to four metal atoms and that the nearest neighbour metal atoms lose approximately half their metallic cohesive energies.

Solubility and activity of oxygen in liquid indium and copper indium alloys

The solubility of oxygen in liquid indium in the temperature range 650–820 °C and in liquid copper-indium alloys at 1100 °C in equilibrium with indium sesquioxide has been measured by a phase equilibration technique. The solubility of oxygen in pure indium is given by the relation log(at.% O) = −4726/T + 3.73 (±0.08) Using the recently measured values for the standard free energy of formation of In2O3 and assuming that oxygen obeys Sievert's law up to saturation, the standard free energy of solution of molecular oxygen in liquid indium is calculated as View the MathML sourceΔG°= −51 440 + 8.07 T (±500) cal where the standard state for dissolved oxygen is an infinitely dilute solution in which activity is equal to atomic per cent. The effect of indium additions on the activity coefficient of oxygen dissolved in liquid copper was measured by a solid oxide galvanic cell. The interaction parameter ϵ0In is given by View the MathML source The experimentally determined variation of the activity coefficient of oxygen in dilute solution in Cu-In alloys is in fair agreement with that predicted by a quasichemical model in which each oxygen atom is assumed to be interstitially coordinated to four metal atoms and the nearest neighbour metal atoms are assumed to lose approximately half their metallic cohesive energies.

A new matched thermochemical diagram for vacuum refining of nickel and cupronickel alloys

Sulfur and oxygen dissolved in nickel and cupronickel melts can be remwed as gaseous oxides of sulfur by a vacuum treatment. Presented in this paper is a new matched thermcxhemical disgran~ that permit.. direct evaluation of the equilibrium partial pressure of SO, as a function of temperature wer an alloy of specified compition. The matched thermochemical diagram consists of a central plot which shows the integral Gibbs' energy of mixing for the binary system SO, at different temperatures. The central plot is flanked on either side by terminal plots of the chemical potentials of oxygen and sulfur, as functions of temperature, for different alloy compositions. By projecting the chemical wtentials of oxygen and sulfur from the terminal lots on to the central diagram, ihe equilibrium partial pressure of S0,can be directly ;cad on the nomograms on the central plot at different temperatures. The matched therrnochemical diagrams are useful in assuring the efficiency of vacuum refining.

On the Structural Stability of Melt Spun Ribbons of Fe95-x Zr (x) B4Cu1 (x=7 and 9) Alloys and Correlation with Their Magnetic Properties

Melt spun ribbons of Fe95-x Zr (x) B4Cu1 with x = 7 (Z7B4) and 9 (Z9B4) alloys have been prepared, and their structure and magnetic properties have been evaluated using XRD, DSC, TEM, VSM, and Mossbauer spectroscopy. The glass forming ability (GFA) of both alloys has been calculated theoretically using thermodynamical parameters, and Z9B4 alloy is found to possess higher GFA than that of Z7B4 alloy which is validated by XRD results. On annealing, the amorphous Z7B4 ribbon crystallizes into nanocrystalline alpha-Fe, whereas amorphous Z9B4 ribbon shows two-stage crystallization process, first partially to bcc solid solution which is then transformed to nanocrystalline alpha-Fe and Fe2Zr phases exhibiting bimodal distribution. A detailed phase analysis using Mossbauer spectroscopy through hyperfine field distribution of phases has been carried out to understand the crystallization behavior of Z7B4 and Z9B4 alloy ribbons. In order to understand the phase transformation behavior of Z7B4 and Z9B4 ribbons, molar Gibbs free energies of amorphous, alpha-Fe, and Fe2Zr phases have been evaluated. It is found that in case of Z7B4, alpha-Fe is always a stable phase, whereas Fe2Zr is stable at higher temperature for Z9B4. (C) The Minerals, Metals & Materials Society and ASM International 2015

Undercooling and Rapid Solidification of Nb-Si Eutectic Alloys Studied by Long Drop Tube

Niobium-silicide alloys have great potential for high temperature turbine applications. The two-phase Nb/Nb5Si3 in situ composites exhibit a good balance in mechanical properties. Using the 52 in drop tube, the effect of undercooling and rapid solidification on the solidification process and micro-structural characterization of Nb-Si eutectic alloy was studied. The microstructures of the Nb-Si composites were investigated by optics microscope (OM), X-ray diffraction (XRD) and scanning electron microscope (SEM) equipped with X-ray energy dispersive spectrometry (EDS). Up to 480 K, deep undercooling of the Nb-Si eutectic samples was successfully obtained, which corresponds to 25% of the liquidus temperature. Contrasting to the conventional microstructure usually found in the Nb-Si eutectic alloy, the microstructure of the undercooled sample is divided into the fine and coarse regions. The most commonly observed microstructure is Nb+Nb5Si3, and the Nb3Si phase is not be found. The change of coarseness of microstructure is due to different cooling rates during and after recalescence. The large undercooling is sufficient to completely bypass the high temperature phase field.

Conduction-electron localized-moment interaction in palladium-silicon base amorphous alloys containing transition metals

The electrical and magnetic properties of amorphous alloys obtained by rapid quenching from the liquid state have been studied. The composition of these alloys corresponds to the general formula M_xPd_80-xSi₂₀, in which M stands for a metal of the first transition series between chromium and nickel and x is its atomic concentration. The concentration ranges within which an amorphous structure could be obtained were: from 0 to 7 for Cr, Mn and Fe, from 0 to 11 for Co and from 0 to 15 for Ni. A well-defined minimum in the resistivity vs temperature curve was observed for all alloys except those containing nickel. The alloys for which a resistivity minimum was observed had a negative magnetoresistivity approximately proportional to the square of the magnetization and their susceptibility obeyed the Curie-Weiss law in a wide temperature range. For concentrated Fe and Co alloys the resistivity minimum was found to coexist with ferromagnetism. These observations lead to the conclusion that the present results are due to a s-d exchange interaction. The unusually high resistivity minimum temperature observed in the Cr alloys is interpreted as a result of a high Kondo temperature and a large s-d exchange integral. A low Fermi energy of the amorphous alloys (3.5 eV) is also responsible for the anomalies due to the s-d exchange interaction.

Electrical resistance and thermoelectric power of the metastable phases in tellurium-base alloys

By using techniques of rapid quenching from the melt, metastable phases have been obtained in ternary alloys which contain tellurium as a major component and two of the three noble metals (Cu, Ag, Au) as minor components. The metastable phases found in this investigation are either simple cubic or amorphous. The formation of the simple cubic phase is discussed. The electrical resistance and the thermoelectric power of the simple cubic alloy (Au₃₀Te₇₀) have been measured and interpreted in terms of atomic bondings. The semiconducting properties of a metastable amorphous alloy (Au₅Cu₂₅Te₇₀) have been measured. The experimental results are discussed in connection with a theoretical consideration of the validity of band theory in an amorphous solid. The existence of extrinsic conduction in an amorphous semiconductor is suggested by the result of electrical resistance and thermoelectric power measurements.

New parameters of many-body potentials: studying the thermal and mechanical properties of noble metals

New parameters of nearest-neighbor EAM (1N-EAM), n-th neighbor EAM (NN-EAM), and the second-moment approximation to the tight-binding (TB-SMA) potentials are obtained by fitting experimental data at different temperatures. In comparison with the available many-body potentials, our results suggest that the 1N-EAM potential with the new parameters is the best description of atomic interactions in studying the thermal expansion of noble metals. For mechanical properties, it is suggested that the elastic constants should be calculated in the experimental zero-stress states for all three potentials. Furthermore, for NNEAM and TB-SMA potentials, the calculated results approach the experimental data as the range of the atomic interaction increases from the first-neighbor to the sixth-neighbor distance.

Crystallographic and electrochemical characteristics of melt-spun Ti-Zr-Ni-Cu alloys

Ti44Zr32Ni22Cu2 and Ti41Zr29Ni28Cu2 alloys were prepared by the melt-spinning method. The phase structure was analyzed by X-ray diffraction, and the electrochemical performances of the melt-spun alloys were investigated. The results indicated that the Ti44Zr32Ni22Cu2 alloy was composed of the icosahedral quasicrystals and amorphous phases, and the Ti41Zr29Ni28Cu2 alloy comprised icosahedral quasicrystals, amorphous, and Laves phases. The maximum discharge capacity was 141 mAh/g for the Ti44Zr32Ni22Cu2 alloy and 181 mAh/g for the Ti41Zr29Ni28Cu2 alloy, respectively. The Ti41Zr29Ni28Cu2 alloy also showed a better high-rate dischargeabifity and cycling stability. The better electrochemical properties should be ascribed to the high content of Ni, which was beneficial to the electrochemical kinetic properties and made the alloy more resistant to oxidation, as well as to the Laves phase in the Ti41Zr29Ni28Cu2 alloy, which could work as the electro-catalyst and the micro-current collector.