Thermodynamic analysis of alloys Ti–Al, Ti–V, Al–V and Ti–Al–V

Thermodynamic analysis of three binary Ti-based alloys: Ti–Al, Ti–V, and Al–V, as well as ternary alloy Ti–Al–V, is shown in this paper. Thermodynamic analysis involved thermodynamic determination of activities, coefficient of activities, partial and integral values for enthalpies and Gibbs energies of mixing and excess energies at four different temperatures: 2000, 2073, 2200 and 2273 K, as well as calculated phase diagrams for the investigated binary and ternary systems. The FactSage is used for all thermodynamic calculations.     

Ti-Al合金熔体与氧化物陶瓷界面反应的热力学分析(英文)

研究CaO、MgO、Al2O3和Y2O3与熔融Ti及Ti合金之间的界面反应热力学。根据氧化物在Ti合金熔体中的溶解反应机制建立热力学模型,通过热力学分析预测各氧化物相对于Ti-Al(0≤x(Al)≤0.5)合金的热力学稳定性。根据氧化物坩埚熔炼实验结果来研究氧化物与Ti-xAl合金熔体的界面反应,对熔炼效果进行定量分析,发现随着合金中Al含量的提高和熔体温度的降低,合金中杂质元素含量成比例的减少,这与氧化物稳定性计算结果一致。     

Thermodynamics of Selected Ti-Al and Ti-Al-Cr Alloys

Two alloys in the Ti-Al system (Ti-45 a/o Al,Ti-62Al) and three alloys in the Ti-Al-Cr system(Ti-47Al-2Cr, Ti-47Al-13Cr, Ti-51Al-12Cr) were selectedfor a thermodynamic study because of interest in their high-temperature oxidation behavior. Activitiesof Al and Ti were measured using a twin Knudsen-cellassembly with one cell acting as an internal standard.For the Ti-45Al alloy, Al activity was also measured with an EMF technique. The Ti-Al-Cr data wereconsistent with the Al and Ti activities expected fromthe adjacent binary Ti-Al phase fields. Implications ofthis work on oxidation properties arediscussed.     

Anodic passivity of some titanium base alloys in aggressive environments

The passivity of titanium, binary Ti‐15Mo and ternary Ti‐15Mo‐5Al alloys in hydrochloric acid solutions was studied by potentiostatic, potentiodynamic, linear polarization and electrochemical impedance spectroscopy (EIS) techniques. The anodic passivity of binary Ti‐15Mo and ternary Ti‐15Mo‐5Al titanium alloys differs from that of the base metal in hydrochloric acid solutions. The corrosion potentials of both alloys are nobler than of the titanium because the beneficial effect of molybdenum. The critical passivation current density for binary Ti‐15Mo alloy is higher than of titanium; this fact can be explained by the instability of the constituent phases in hydrochloric acid solutions. Ternary Ti‐15Mo‐5Al alloy exhibits two critical passivation current densities (i_cr1 and i_cr2) with higher values than of the base metal and two critical passivation potentials (E_cr1 and E_cr2); at the first critical passivation potential (E_cr1) the porous titanium trioxide (Ti₃O₅) is formed and at the second critical passivation potential (E_cr2) this oxide is converted to a still higher valence oxide, the compact and protective titanium dioxide (TiO₂). The dissolution current densities in the passive range of alloys are higher than of the base metal due the dissolution of the alloying elements in this potential range. The alloys are more resistant than titanium presenting lower corrosion rates. A three time constants equivalent circuit was fitted: one time constant is for the double layer capacity (C_dl) and for the passive film (R_p); another time constant is for the charge transfer reactions visualised by a constant phase element (CPE) and a resistance (R₁); the third time constant is for diffusion processes through the passive film represented by a resistance (R₂) and a Warburg element (W).     

One component metal oxide sintering additive for β-SiC based on thermodynamic calculation and experimental observations

This paper examines a range of metal oxides, including those containing relatively safe elements under neutron irradiation, such as Cr, Fe, Ta, Ti, V and W, as well as widely used oxides, Al₂O₃, MgO and Y₂O₃, as a sintering additive for β-SiC theoretically and experimentally. After selecting the most probable SiC oxidation reaction at 1973–2123 K, the condition where the metal oxide additive does not decompose SiC was calculated based on the standard Gibbs formation free energies. Thermodynamic calculations revealed that Al₂O₃, MgO and Y₂O₃ could be an effective sintering additive without decomposing SiC under hot pressing conditions, which was demonstrated experimentally. On the other hand, no one component metal oxide that contains a safe element for nuclear reactor applications was found to be an effective sintering additive due to the formation of metal carbides and/or silicides. Overall, the simulation based on thermodynamic calculations was found to be quite useful for selecting effective metal oxide additives.     

基于Miedema模型和Toop模型的Al-Si-Er合金热力学参数计算

运用Miedema混合焓模型计算了Al-Er、Si-Er和Al-Si二元合金的部分热力学性质,选择Er为非对称性组元,在此基础上结合Toop模型计算出Al-Si-Er三元合金的混合焓、过剩熵与过剩自由能。结果表明,Al-Si-Er三元合金的混合焓、过剩熵与过剩自由能在整个浓度范围内均为负值,在富Er和贫Er区域各热力学参数变化趋势较大。通过计算Al、Si和Er 3种组元的偏摩尔过剩自由能得到Al-Si-Er三元合金各组元的等活度值曲线。曲线显示各组元随着摩尔分数的减少其活度值都急剧减小,在三元系成分三角形的中心部分Al、Si和Er的活度值都很小,这表明Al、Si和Er 3种组元之间存在很强的相互作用,易形成三元金属间化合物,这一结论与Al-Si-Er三元相图的实际情况相符合。     

U基二元熔体的热力学计算

采用Miedema半经验模型计算了U-Nb、U-Ti及U-Zr二元熔体的混合热、过剩熵及过剩自由能等热力学性质,并根据热力学原理计算了组元U在不同温度的二元熔体中的活度值.结果表明,U-Nb,U-Ti和U-Zr熔体相对于拉乌尔定律均呈负偏差,U-Ti和U-Zr合金较U.Nb合金更易于形成中间化合物.计算结果与实验相图符合较好.     

Thermodynamic Assessment of Zn-Fe-Nb Ternary System

The Nb-Zn binary system has been thermodynamically assessed using CALPHAD approach by combining available experimental data and the data from ab initio calculations of the formation enthalpies for NbZn₂, NbZn₃ and NbZn₁₅. Solution phases including Liquid, Bcc, Hcp were modeled as substitutional phases, of which the excess Gibbs energies being formulated with the Redlich-Kister polynomial function. All the binary compounds were treated as stoichiometric phases. Incorporated with the reported thermodynamic parameters of Fe-Zn and Fe-Nb binary systems, two isothermal sections at 723 and 873 K of Zn-Fe-Nb ternary system were thermodynamically optimized where one stoichiometric ternary phase (τ) and the ternary solubility in intermetallic compound (ε) were taken into consideration. Furthermore, liquidus projection was predicted accordingly.     

Thermodynamic Assessment of the Ti-Ir System

The thermodynamic assessment of the binary system Ti-Ir has been carried out by modeling the Gibbs energy of all individual phases using the calculation of phase diagrams approach based on the available literature data including the phase equilibria and thermodynamic properties. The Gibbs free energies of the liquid, bcc, fcc and hcp phases were described by the subregular solution model with Redlich-Kister formula, and those of the intermetallic compounds (Ti₃Ir, γTiIr, βTiIr and TiIr₃) in the Ti-Ir binary system were described by the two-sublattice model. The calculations are in good agreement with the literature data on both phase equilibria and thermodynamic properties in the Ti-Ir system.     

Isothermal section of Al–Ti–Zr ternary system at 1073 K

Through alloy sampling combined with diffusion triple technique, phase equilibria in Al–Ti–Zr ternary system at 1073 K were experimentally determined with electron probe microanalysis (EPMA). Experimental results show that there is a solid solution β(Ti,Zr) which dissolves Al up to 16.3% (mole fraction). Ti and Zr can substitute each other in most Ti–Al and Al–Zr binary intermediate phases to a certain degree while the maximum solubility of Zr in Ti₃Al and TiAl reaches up to 17.9% and 4.0% (mole fraction), respectively. The isothermal section consists of 16 single-phased regions, 27 two-phased regions and 14 three-phased regions. No ternary phase was detected.     

ACTIVITY OF In IN LIQUID In-Bi-Tl ALLOYS

The activities of In in two pseudo-binary systems of fixed molar fraction ratio N_(Bi)/N_(Ti) have been measured by means of EMF method using zirconia solid electrolyte gal- vanic cells over the temperature range of 973—1223 K.The excess free energies were deter- mined based on the experimental data.The experimentally determined thermodynamic prop- erties of the ternary alloys agree well with the values caleulated from the author's equations using related binary data.The excess free energies are negative in almost all compositions ex- cept those near the In-Tl side and become negatively larger as the compositions approach the Bi-Tl side.     

Local structure of calcium silicate melts from classical molecular dynamics simulation and a newly constructed thermodynamic model

The distributions of local structural units of calcium silicate melts were quantified by means of classical molecular dynamics simulation and a newly constructed structural thermodynamic model. The distribution of five kinds of Si-O tetrahedra Q_i from these two methods was compared with each other and also with the experimental Raman spectra, an excellent agreement was achieved. These not only displayed the panorama distribution of microstructural units in the whole composition range, but also proved that the thermodynamic model is suitable for the utilization as the subsequent application model of spectral experiments for the thermodynamic calculation. Meanwhile, the five refined regions mastered by different disproportionating reactions were obtained. Finally, the distributions of two kinds of connections between Q_i were obtained, denoted as Q_i-Ca-Q_j and Q_i-[O_b]-Q_j, from the thermodynamic model, and a theoretical verification was given that the dominant connections for any composition are equivalent connections.     

A generalized thermodynamic treatment of phase equilibria in coherent multilayers

We present a generalized way of treating phase equilibria in coherent planar multilayers. A correct recognition of elastic stress and strain components as thermodynamic potentials or densities is crucial for the use of the criteria for intrinsic stability as well as for the applicability of the conventional method of common tangent construction and the Gibbs phase rule. It is shown that a method analogous to the conventional common tangent construction exists in thermodynamic density subspaces for which some of density variables are held constant. In a thermodynamic density subspace withm _s density variables fixed, a common tangent construction can be made between the extremized free energies for systems of (m_s+l)-phase coexistence in order to satisfy the thermodynamic equilibrium conditions of systems with more thanm _s+1 coexisting phases. This method is applied to a coherent binary system configured as plane-parallel plates to demonstrate that equilibrium states with more than two coexisting phases cannot be thermodynamically stable in the binary multilayer system under certain mechanical loading conditions.     

Evaporation loss of components during induction skull melting of Ti—13Al—29Nb—2·5Mo

Saturated vapour pressures of the Al, Ti and Nb components in Ti—13Al—29Nb—2·5Mo (wt-%) melts were calculated at arbitrary temperatures. The calculated values at 2150 K for Ti, Al and Nb were 2·0, 30·7 and 0·17 Pa, respectively. From the thermodynamic point of view, the principal evaporation loss is of the Al component. Based on the saturated vapour pressure, the mass transport coefficient of the Al component, evaporation loss rates of the Ti, Al and Nb components and the evaporation loss of the Al component were calculated. When the melt temperature is 2100 K, the evaporation control changes from the double control mode to the single interface volatilisation control mode with increasing chamber pressure at a transition pressure of about 4 Pa. The rates of evaporation loss of the components are N_Al≈15N_Ti≈46N^Nb. A critical chamber pressure of about 13·33 Pa exists during induction skull melting of the Ti—13Al—29Nb—2·5Mo alloy. In order to prevent the evaporation loss of Al, the chamber pressure should be kept above 13·33 Pa. The theoretical calculation of the evaporation loss of the Al component is in good agreement with experimental values. IJCMR/432     

System Ho-Rh-O: Phase Equilibria, Chemical Potentials and Gibbs Energy of Formation of HoRhO3

The thermodynamic properties of the HoRhO₃ were determined in the temperature range from 900 to 1300?K by using a solid-state electrochemical cell incorporating calcia-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of orthorhombic perovskite HoRhO₃, from Ho₂O₃ with C-rare earth structure and Rh₂O₃ with orthorhombic structure, can be expressed by the equation; $$ \Updelta G_{{{\text{f}}({\text{ox}})}}^{ \circ } \left( { \pm 78} \right)/({\text{J}}/{\text{mol}}) = - 50535 + 3.85\left( {T/{\text{K}}} \right) $$ Using the thermodynamic data of HoRhO₃ and auxiliary data for binary oxides from the literature, the phase relations in the Ho-Rh-O system were computed at 1273?K. Thermodynamic data for intermetallic phases in the binary Ho-Rh were estimated from experimental enthalpy of formation for three compositions from the literature and Miedema??s model, consistent with the phase diagram. The oxygen potential-composition diagram and three-dimensional chemical potential diagram at 1273?K, and temperature-composition diagrams at constant oxygen partial pressures were computed for the system Ho-Rh-O. The decomposition temperature of HoRhO₃ is 1717(±2)?K in pure O₂ and 1610(±2)?K in air at a total pressure p ^o?=?0.1?MPa.