Thermodynamic study of the effect of calcium on removal of phosphorus from silicon by acid leaching treatment

The interaction between calcium and phosphorus in molten silicon was investigated for predicting the removal of phosphorus from silicon by an acid leaching treatment with calcium addition. In the present study, two immiscible liquids of silicon and lead were equilibrated, and the interaction parameter between calcium and phosphorus and the self-interaction parameter of phosphorus in molten silicon at 1723 K were determined.

Boron removal by titanium addition in solidification refining of silicon with Si-Al melt

In order to effectively remove B from Si for its use in solar cells, a process involving B removal by solidification refining of Si using a Si-Al melt with Ti addition was investigated. For clarifying the effect of Ti addition on B removal from the Si-Al melt, TiB₂ solubilities in Si-64.6 at. pct Al melt at 1173 K and Si-60.0 at. pct Al melt at 1273 K were determined by measuring the equilibrium concentrations of B and Ti in the presence of TiB₂ precipitates. The small solubilities of TiB₂ in the Si-Al melt indicate the effective removal of B from the Si-Al melt by Ti addition. Further, solidification experiments of Si-Al alloys containing B by Ti addition were performed, and the effect of Ti addition on the solidification refining of Si with the Si-Al melt was successfully confirmed.     

Equilibrium of calcium vapor with liquid iron and the interaction of third elements

The dissolution equilibrium of calcium vapor in liquid iron was carried out at 1873 K in a two-temperature zone furnace using a vapor-liquid equilibration method. A sealed Mo reaction chamber and a self-made CaO crucible were used in this study. The thermodynamic parameters obtained are as follows. For reaction Ca (g)=[Ca],

Determination of standard gibbs energies of formation of Cr2N and CrN

The standard Gibbs energies of formation of Cr₂N and CrN have been measured by an equilibration technique and by using thermogravimetry and differential thermal analysis (TG-DTA) at temperatures ranging from 1232 to 1523 K. The results are expressed as follows:

Enthalpy of mixing of liquid Ni-Zr and Cu-Ni-Zr alloys

The partial (Δ and the integral (ΔH) enthalpies of mixing of liquid Ni-Zr and Cu-Ni-Zr alloys have been determined by high-temperature isoperibolic calorimetry at 1565 ± 5 K. The heat capacity (C _p) of liquid Ni₂₆Zr₇₄ has been measured by adiabatic calorimetry (C _p=53.5±2.2 J mol⁻¹ K⁻¹ at 1261±15 K). The integral enthalpy of mixing changes with composition from a small positive (Cu-Ni, ΔH (x _Ni=0.50, T=1473 to 1750 K)=2.9 kJ mol⁻¹) to a moderate negative (Cu-Zr; ΔH(x _Zr=0.46, T=1485 K)=−16.2 kJ mol⁻¹) and a high negative value (Ni-Zr; ΔH(x _Zr=0.37, T=1565 K)=−45.8 kJ mol⁻¹). Regression analysis of new data, together with the literature data for liquid Ni-Zr alloys, results in the following relationships in kJ mol⁻¹ (standard states: Cu (1), Ni (1), and Zr (1)):for Ni-Zr (1281≤T≤2270 K),

Determination of gibbs energy of formation of Ni-B-O system by electromotive force measurement using solid electrolyte

The standard Gibbs energies of formation of Ni₃B, Ni₂B, o-Ni₄B₃(Ni_0.586B_0.414), m-Ni₄B₃(Ni_0.564B_0.436), NiB, and Ni₃B₂O₆ of the Ni-B-O system have been determined by measuring electromotive forces of galvanic cells using a Y₂O₃-stabilized ZrO₂ solid oxide electrolyte. The results are as follows:

Thermodynamic properties of aluminum, magnesium, and calcium in molten silicon

The thermodynamic properties of aluminum, magnesium, and calcium in molten silicon were investigated using a chemical equilibration technique at 1723 to 1848 K, 1698 to 1798 K, and 1723 to 1823 K, respectively. The activity coefficient of aluminum in molten silicon was determined by equilibrating molten silicon-aluminum alloys with solid Al₂O₃ and Al₆Si₂O₁₃, that of magnesium was determined by equilibrating molten silicon-magnesium alloys and MgO-SiO₂-Al₂O₃ melts doubly saturated with MgSiO₃ and SiO₂, and that of calcium was determined by equilibrating molten silicon-calcium alloys with SiO₂-saturated CaO-SiO₂ melts. The activity coefficients at infinite dilution relative to the pure liquid state were determined as follows:

Thermodynamic properties and phase equilibria for Pt-Rh alloys

The activity of rhodium in solid Pt-Rh alloys is measured in the temperature range from 900 to 1300 K using the solid-state cell

Determination of gibbs energy of formation of cuspidine (3CaO · 2SiO<Subscript>2</Subscript> · CaF<Subscript>2</Subscript>) from the electromotive force method using CaF<Subscript>2</Subscript> as the solid electrolyte

The standard Gibbs energy change for the following reaction has been directly determined by electromotive force (EMF) measurement using CaF₂ as the solid electrolyte in the temperature range from 1313 to 1329 K.

Phase equilibria in the titanium-oxygen system

Data in the literature on the Magneli oxides of titanium have been critically evaluated and equations have been developed from these data for the standard-state Gibbs energy of formation of the following oxides: Ti₄O₇, Ti₅O₉, Ti₆O₁₁, Ti₈O₁₅, and Ti₉O₁₇. Examination of those data yielded the following:

Determination of Gibbs Energy of Formation of Molybdenum-Boron Binary System by Electromotive Force Measurement Using Solid Electrolyte

The standard Gibbs energies of formation of Mo₂B, ??MoB, Mo₂B₅, and MoB₄ in the molybdenum-boron binary system were determined by measuring electromotive forces of galvanic cells using an Y₂O₃-stabilized ZrO₂ solid oxide electrolyte. The results are as follows: $$ \begin{aligned} \Updelta_{\text{f}} {\text{G}}^\circ \left( {{\text{Mo}}_{2} {\text{B}}} \right)/{\text{J}}\,{\text{mol}}^{ - 1} & = - 193100 + 44.10T \pm 700\left( {1198{\text{ K to }}1323{\text{ K}}\left( {925^\circ {\text{C to }}1050^\circ {\text{C}}} \right)} \right) \\ \Updelta_{\text{f}} {\text{G}}^\circ (\alpha {\text{MoB}})/{\text{J}}\,{\text{mol}}^{ - 1} & = - 164000 + 26.45T \pm 700\left( {1213{\text{ K to }}1328{\text{ K}}\left( {940^\circ {\text{C to }}1055^\circ {\text{C}}} \right)} \right) \\ \Updelta_{\text{f}} {\text{G}}^\circ \left( {{\text{Mo}}_{2} {\text{B}}_{5} } \right)/{\text{J}}\,{\text{mol}}^{ - 1} & = - 622500 + 117.0T \pm 3000\left( {1205{\text{ K to }}1294{\text{ K}}\left( {932^\circ {\text{C to }}1021^\circ {\text{C}}} \right)} \right) \\ \Updelta_{\text{f}} {\text{G}}^\circ \left( {{\text{MoB}}_{4} } \right)/{\text{J}}\,{\text{mol}}^{ - 1} & = - 387300 + 93.53T \pm 3000\left( {959{\text{ K to }}1153{\text{ K}}\left( {686^\circ {\text{C to }}880^\circ {\text{C}}} \right)} \right) \\ \end{aligned} $$ where the standard pressure is 1 bar (100 kPa).     

Kinetic modeling of titania reduction by a methane-hydrogen-argon gas mixture

This article describes kinetic modeling of titania reduction and carburization by methane-containing gas, based on experimental data reported previously by Zhang and Ostrovski. A sequence of titania reduction to titanium oxycarbide,

Electrochemical determination of gibbs energy of formation of NiTiO3 (ilmenite)

Gibbs energy of formation of NiTiO₃ (ilmenite) relative to its component oxides, NiO (rock salt) and TiO₂ (rutile), has been measured employing the solid-state electrochemical cell,

Free energies of formation of WC and W2C,and the thermodynamic properties of carbon in solid tungsten

The activity of carbon in the two-phase regions W + WC and W + W₂C has been obtained from the carbon content of iron rods equilibrated with mixtures of metal plus carbide powders. From this activity data the standard free energies of formation of WC and W₂C have been calculated to be ΔG _f ⁰(WC) = -10,100 + 1.19T ± 100 cal/mole (-42,300 + 4.98T ± 400 J/mole) (1150 to 1575 K) ΔG _f ⁰(W₂C) = - 7300 - 0.56T ± 100 cal/mole (- 30,500 - 2.34T ± 400 J/mole). (1575 to 1660 K) The temperature of the eutectoid reaction W₂C = W + WC was fixed at 1575 ± 5K. Using available data for the solubility of C in solid W, the relative partial molar free energy of C in the dilute solid solution was calculated to be $$\Delta \bar G_C^\alpha {\text{ = 23,000 }} - {\text{ }}[{\text{0}}{\text{.68 }} - R\ln X_C^\alpha ]{\text{ }}T \pm 3000 cal/mole (96,200 - [2.85 - R\ln X_C^\alpha ]{\text{ }}T \pm 12,600 J$$ The heat solution of C in W obtained was \(\Delta \bar H_C^\alpha {\text{ = 23,000 }} \pm {\text{ 5000 cal/mole (96,200 }} \pm {\text{ 20,000 J/mole)}}\) and the excess entropy for the interstitial solid solution, assuming that the carbon atoms are in the octahedral sites, \(\Delta \bar S_C^\alpha {\text{ = (}}xs,i{\text{) }} = - {\text{1}}{\text{.5 }} \pm {\text{ 2 cal/deg - mole (}} - {\text{6}}{\text{.3 }} \pm {\text{ 8 J/deg - mole)}}\) .     

Precipitation of aluminum in the silicon phase contained in W319 and 356 aluminum alloys

Solidification of Al-Si alloys typically yields regions of a eutectic mixture of aluminum and silicon phases. In 319-type and 356 aluminum alloys, we have determined that a small percentage (10 to 25 pct) of the silicon phase contains small (10 to 15 nm) equiaxed precipitates of aluminum as identified by electron diffraction with an orientation relation to the silicon matrix: