Phase equilibria and thermodynamics of binary copper systems with 3d-metals. I. The copper-scandium system

Thermodynamic assessment of the Cu-Sc system was carried out using the CALPHAD method. A set of self-consistent model parameters was obtained with the usage of the information about phases equilibria and thermodynamic. Gibbs energy for the liquid phase was assessed within the framework of the model of ideal associated solution. Optimized model parameters make it possible to reproduce satisfactorily the phase diagram and thermodynamic values. Analysis of the relative thermodynamic stability of supercooled melts and competing crystalline phases let us to predict their glass forming ability by rapid quenching from the liquid state. __________ Translated from Poroshkovaya Metallurgiya, Nos. 3–4(448), pp. 43–55, March–April, 2006.     

Thermodynamics of Liquid Alloys and Metastable Phase Transformations in the Copper - Titanium System

We have used solution calorimetry at temperatures of 1573 K and 1873 K over broad concentration ranges to study the mixing enthalpy of Cu - Ti liquid alloys. The molar mixing enthalpies of the system are significant negative values. We have established the temperature dependence of the molar mixing enthalpies of the system: there is an increase in their exothermicity as the temperature is lowered. The significant negative mixing enthalpies of the system allow us to conclude that the chemical bonds are localized in the studied melts and consequently associates form. We tested this conclusion within ideal associated solution theory, which describes well the results obtained with a set of CuTi and CuTi₂ associates. Using the model obtained, we have calculated the excess thermodynamic functions of mixing (enthalpy, Gibbs free energy, heat capacity) for the liquid alloys. We estimated the Gibbs energies of fcc, bcc, and hcp solutions in the system by the CALPHAD method, using data from the initial sections of the phase diagrams and from the corresponding thermodynamic data. We have calculated the metastable phase equilibria between the limiting solid solutions and the liquid or supercooled liquid phase. It was shown that for the supercooled liquid and the amorphous phase, a broad concentration range of relative thermodynamic stability can be obtained. The concentration range of amorphization of Cu - Ti melts corresponds to the position of the metastable liquidus line and the T₀ line at temperatures close to the temperature range of amorphous solidification. __________ Translated from Poroshkovaya Metallurgiya, Nos. 5–6(443), pp. 67–80, May–June, 2005.     

Phase equilibria in the system HfO2-Y2O3-La2O3 AT 1900°C

We have used x-ray phase analysis, electron-probe microanalysis, petrography, and electron microscopy on annealed specimens to study phase equilibria in the ternary system HfO₂-Y₂O₃-La₂O₃ at 1900 °C over the entire concentration range. We have plotted the isothermal cross section of the phase diagram for this system at the indicated temperature. We found 23 phase regions. A typical feature of the system is formation of solid solutions based on different crystal modifications of the starting components (A-and H-La₂O₃, C-Y₂O₃, T-and F-HfO₂) and also the compounds La₂Hf₂O₇, LaYO₃. We did not observe new phases in the system. The nature of the phase equilibria in the system is consistent with the high relative thermodynamic stability of lanthanum hafnate (ΔH °La₂Hf₂O₇ ≈ 100 kJ/mole) compared with LaYO₃. We established that adding a third component extends the thermal stability region for the ordered phase of LaYO₃ toward higher temperatures. __________ Translated from Poroshkovaya Metallurgiya, Nos. 1–2(447), pp. 73–87, January–February, 2006.     

Phase diagram of the Al2O3-ZrO2-Er2O3 system. III. Solidus surface and phase equilibria in alloy crystallization

The solidus surface for the Al₂O₃-ZrO₂-Er₂O₃ phase is projected for the first time onto the concentration triangle. It consists of five isothermal three-phase fields that correspond to four invariant eutectic equilibria, one invariant transformation equilibrium, and six ruled binary eutectic solidus surfaces. The highest solidus temperature in the system is 2710 °C, which is the melting point of pure ZrO₂, and the lowest is 1720°C, which is the melting point of the ternary eutectic AL + F + Er₃A₅. Neither ternary phases nor visible solid solution areas based on components and binary compounds are found in the system. Based on the data on bounding binary systems, liquidus, and solidus surfaces, the phase equilibrium diagram and reaction scheme for equilibrium crystallization of Al₂O₃-ZrO₂-Er₂O₃ alloys are constructed. __________ Translated from Poroshkovaya Metallurgiya, Vol. 46, No. 5–6 (455), pp. 74–83, 2007.     

Al-Zn(Cu)合金的相变和Al-Zn-Cu系相图

Al-Zn-Cusystemistheimportantbasisfor practicalAlalloysandZnalloys[1].Amiscibility gapofthefccphaseexistsabove277℃inthe Al Znsystem[2].Thealloywhosecompositionis atthetopofthemiscibilitygapiscalledsym metricalalloyAlZn.Thisalloyhasmanytypical properties.Theimportantoneisthatthespi nodaldecompositioneasilytakesplaceinit.In ordertoavoidthedecomposition,Cuhasbeen added,whichiseffective.Additionof2%Cu molefractioncoulddelaythespinodaldecompo sitionfortwogrades[3,4].AlZn 2Cuisanalloy which…     

Phase diagram of the Al2O3-ZrO2-Er2O3 system. II. Phase diagram liqiudus surface

The liquidus surface for the Al₂O₃-ZrO₂-Er₂O₃ phase diagram is projected for the first time onto a concentration triangle. No ternary compounds are found in the system. The liquidus surface is completed by eight primary crystallization fields. Four four-phase nonvariant eutectic equilibria, one four-phase nonvariant transformation equilibrium, and three three-phase nonvariant eutectic equilibria are found in the system. Since ZrO₂ interacts with other phases eutectically, the unique properties of ZrO₂-based T-and F-solid solutions can be combined with the properties of other phases of the ternary system in composite materials. __________ Translated from Poroshkovaya Metallurgiya, Vol. 46, No. 1–2(453), pp. 64–71, 2007.     

Phase diagram of the Al2O3-ZrO2-Sm2O3 system. III. Solidus surface and phase equilibria in alloy crystallization

A projection has been constructed for the solidus surface in the Al₂O₃-ZrO₂-Sm₂O₃ phase diagram on the plane of the concentration triangle, which consists of seven isothermal three-phase fields corresponding to two nonvariant equilibria of eutectic type and five nonvariant equilibria of peritectic type, and also eight lineated surfaces for the end of crystallization of the binary eutectics. The highest temperature on the solidus surface is 2710°C, the melting point of pure ZrO₂, while the lowest is 1680°C, the temperature of the triple eutectic Al + F + SA. No ternary phases or appreciable regions of solid solutions based on the components and the binary compounds are observed. Data on the bounding binary systems, the liquidus and solidus surfaces have been used to construct the phase-equilibrium (melting) diagram together with a reaction scheme for the equilibrium crystallization of alloys in the Al₂O₃-ZrO₂-Sm₂O₃ system. __________ Translated from Poroshkovaya Metallurgiya, Nos. 5–6(449), pp. 56–64, May–June, 2006.     

Phase equilibria calculation of LaI3-MI （M=Na, K, Cs） binary systems

The Gibbs energies of liquid phases in the LaI3-MI (M=Na, K, Cs) systems were described by the modified quasi-chemical model. From the measured phase equilibrium data of these binary systems, a set of thermodynamic functions were optimized by using the CAL-PHAD technique. The enthalpy of mixing and the interaction parameter of the liquid phase were predicted from known data for the LaI3-MI systems.     

Phase diagram of the Al2O3-ZrO2-Sm2O3 system. II. Liquidus surface

A projection has been constructed for the liquidus surface on the plane of the concentration triangle for the Al₂O₃-ZrO₂-Sm₂O₃ phase diagram. There are no ternary compounds, or appreciable regions of solid solutions based on the components and the binary compounds. The liquidus surface is formed by nine fields of primary phase crystallization. There are five four-phase nonvariant peritectic equilibria, as well as two four-phase nonvariant eutectic equilibria, and one three-phase nonvariant eutectic equilibrium. As the ZrO₂ and SmAlO₃ phases interact with other phases by a eutectic mechanism, it is possible to combine the unique properties of the T and F solid solutions based on ZrO₂ with the properties of the other phases in the form of composites. __________ Translated from Poroshkovaya Metallurgiya, Nos. 3–4(448), pp. 28–35, March–April, 2006.     

稀土对Ti0.25V0.34Cr0.2Ni0.2合金相结构和电化学性能的影响

通过XRD, SEM-EDS等方法及电化学测试研究了稀土对Ti0.25V0.34Cr0.2Ni0.2合金的微观结构和电化学性能的影响. 结果表明, Ti0.25V0.34Cr0.2Ni0.2和Ti0.25V0.34Cr0.2Ni0.2RE0.01 (RE分别代表La, Ce, Pr, Nd和混合稀土)合金均由主相为体心立方结构的钒基固溶体相和少量TiNi基第二相组成. 稀土元素加入后, 合金bcc相的晶格参数略有增加; 镧在合金中发生偏析, 形成新相. 添加稀土元素能够加速合金的活化. 303 K温度下基准合金和含Pr合金电极实际测定的理论放电容量大致相等, 约为364 mAh·g-1. 合金的放电容量对温度的变化比较敏感, 高温有利于合金放电. 稀土对合金电极的荷电保持率产生不利影响; 混合稀土的添加能够改善合金的倍率放电性能.     

MgO和MnO对CaO-SiO2-Fe2O3-P2O5渣的物相影响

转炉渣中的磷主要存在于n2CaO·SiO2-3CaO·P2O5（以下简记为nC2S-C3P）固溶体的富磷相中。为了深入理解转炉渣的物相,便于有效富集钢渣中的磷,研究MgO和MnO含量的变化对CaO-SiO2-Fe2O3-P2O5渣中nC2S-C3P固溶体的磷含量及渣结晶物相的影响,并对其进行热力学分析。结果表明：在CaO-SiO2-Fe2O3-P2O5四元渣系中加入少量MgO或MnO,可以在一定程度上提高nC2S-C3P固溶体中的磷含量;继续提高MgO或MnO含量,固溶体中的磷含量不再发生变化。随着MgO或MnO的加入,富铁相增多,有利于钢渣的磁选分离。     

钢中稀土微合金化及其对钒铌沉淀相析出规律的影响

稀土在钢中有一定的固溶量,可达10^-5-10^-4数量级。固溶稀土可以改善与晶界有关的钢的性能,抑制晶粒长大,影响珠光体、马氏体、贝氏体的数量、形态和分布;在奥氏体区能抑制碳氮化钒析出,在铁素体区能促进碳氮化钒析出;稀土对碳化铌形态、大小、分布、数量有影响,可降低碳、铌活度,阻碍碳化铌在奥氏体区的析出。