High-temperature phase relations and thermodynamics in the iron-lead-sulfur system

The PbS activities in FeS-PbS liquid mattes were obtained at 1100 °C and 1200 °C by the dew-point method. Negative deviations were observed, and the liquid-matte solutions were modeled by the Krupkowski formalism. The liquid boundaries of the FeS-PbS phase diagram were derived from the model equations yielding a eutectic temperature of 842 °C atX _Pbs = 0.46. A phase diagram of the pseudobinary FeS-PbS was also verified experimentally by quenching samples equilibrated in evacuated and sealed silica capsules. No terminal solid solution ranges could be found. Within the Fe-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were established at 1200 °C. Activities of Pb were measured by the dew-point technique along the metal-rich boundary of the miscibility gap. Activities of Fe, Pb, and S, along the miscibility gap were also calculated by utilizing the bounding binary thermodynamics, phase equilibria, and tie-lines.     

High-temperature phase relations and thermodynamics in the iron-titanium-oxygen system

Phase equilibria and thermodynamics in the FeO-TiO₂-Ti₂O₃ ternary system were studied at 1500 °C and 1600 °C. In particular, the liquid slag-phase region and its saturation boundary with respect to metallic iron, titania, and lower titanium oxides was investigated. The liquid slag-phase region extends substantially toward an anosovite (Ti₃O₅) composition, and considerable concentrations of divalent iron coexist with trivalent titanium in the liquid-slag phase. This seems to be a consequence of the complete solid solution between ferrous pseudobrookite (FeTi₂O₅) and anosovite (Ti₃O₅), which exists at subsolidus temperatures. The liquid-slag field is significantly enlarged toward the anosovite composition upon increasing the temperature from 1500 °C to 1600 °C. Activities of the components “FeO” and TiO₂ in the liquid-slag region were determined by Gibbs-Duhem integration of the measured oxygen partial pressures at 1500 °C. The FeO shows moderate negative deviation, while titania shows a slight negative deviation in FeO-rich slags and a positive deviation in high-titania slags. The experimentally measured activity values were modeled using regular and biregular solution models, and good agreement was obtained with the biregular solution model.     

Reactions and phase relations in the TiAlO system

Reactions between titanium and alumina were studied experimentally for Al₂O₃ substrates with a titanium-based coating and for planar TiAl₂O₃ diffusion couples in the temperature range between 800 and 1100°C. Isothermal sections through the phase diagram were determined by using these results as well as by investigating equilibrated alloys. These experimental sections agree with those calculated from thermodynamic data. The morphology and layer thickness of the observed reactions zones have been explained on the basis of these phase relations, making use of diffusion data from binary systems TiO and TiAl. The important role of the initial Ti thickness on the type of reaction products has been demonstrated.     

Equilibrium phase relations and thermodynamics of the Cr-0 system in the temperature range of 1500 °C to 1825 °C

Phase relations and thermodynamic properties of the Cr-O system were studied at temperatures from 1500 °C to 1825 °C. In addition to Cr and Cr₂O₂, a third crystalline phase was found to be stable in the temperature range from 1650 °C to 1705 °C. The atomic ratio of oxygen to chromium of this phase, which decomposes upon cooling to form Cr and Cr₂O₃, was determined as 1.33 + 0.02, in good agreement with the formula Cr₃O₄. Temperatures and phase assem blages for invariant equilibria of the Cr-O system were determined as follows: Cr₂O₃ + Cr + Cr₃O₄, 1650 °C ± 2 °C; Cr₃O₄ + Cr + liquid oxide, 1665 °C ± 2 °C; and Cr₃O₄ + Cr₂O₃ + liquid oxide, 1705 °C ± 3 °C. The composition of the liquid oxide phase at the eutectic temperature of 1665 °C was found to be close to CrO. Relations between oxygen pressure and temperature for the univariant equilibria of the Cr-O system were established by equilibrating Cr and/or Cr₂O₃ starting materials in H₂-CO₂ mixtures of known oxygen potentials at temper atures from 1500 ΔC to 1825 °C. From this information, the standard free-energy changes (ΔGΔ) for various reactions were calculated as follows: 2Cr (s) + 3/2O₂ = Cr₂O₃ (s): ΔG ° = -1,092,442 + 237.94T Joules, 1773 to 1923 K; 3Cr (s) + 2O₂ = Cr₂O₄ (s): ΔG ° =-1,355,198 + 264.64T Joules, 1923 to 1938 K; and Cr (s) + l/2O₂ = CrO (1): ΔG ° =-334,218 + 63.81T Joules, 1938 to 2023 K. Formerly Graduate Research Assistant, The Pennsylvania State University Formerly Professor     

High-temperature phase equilibria in the Al-rich corner of the Al-Ti-C system

A thermodynamic analysis of the Al-rich corner in the ternary Al-Ti-C diagram, providing phase relations and regions of phase stability, is presented. An invariant four-phase equilibrium between Al, Al₄C₃, Al₃Ti, and TiC _x takes place at 0.53 at. pct Ti, 7.10⁻⁶ at. pct C, and TiC_0.883 at 966 K. The carbon content of the TiC _x phase, which extends from x=0.48 to 0.98, exerts a significant effect on phase relationships in this ternary system. In particular, it is shown that stoichiometric TiC is not stable in the presence of liquid Al. For example, at 1300 K, a two-phase equilibrium between Al _L and TiC _x exists only in the 0.91<x<0.82 range. Thus, the interaction of Al _L with stoichiometric TiC leads to the formation of the Al₄C₃ aluminum carbide phase, whereas for x<0.82, only the intermetallic compound Al₃Ti can form at this temperature. The results of this analysis were confirmed by X-ray diffraction (XRD) measurements of relevant composites.     

High-temperature phase transitions in rare-earth metals

The study into the relationship between the laws of structure formation in metallic melts and the properties of collective ion vibrations is continuing. The phase-transition temperatures are found from the Lindemann criterion, where the root-nean-square amplitude of ion vibrations about a center of equilibrium is compared to the properties of the distribution of such centers. In a liquid phase, the vibration amplitude can decrease with increasing temperature.     

CaO-SiO2-FeOx-MgO氧化物体系液相区及相关系计算

焚烧垃圾底灰的主要氧化物组分为SiO2、CaO、Al2O3、Fe2O3、Na2O和MgO,该六元体系相关系和热力学性质对于焚烧底灰渣化处理中玻璃相形成以及重金属低浸出具有重要影响.本文运用计算热力学理论及相图计算方法,对CaO-SiO2-FeOx-MgO四元氧化物体系的热力学性质进行了研究,获得了描述该四元系液相吉布斯自由能的模型参数,并依此计算了不同温度及氧分压下SiO2-FeOx-MgO、CaO-SiO2-FeOx和CaO-SiO2-FeOx-MgO体系液相区和高铁区域的相关系.计算结果表明温度及氧分压对上述3个氧化物体系的液相区及高FeOx区域的相平衡关系具有较大影响     

A study of the thermodynamics and phase relationships of the Fe−Co−S−O quaternary system

The oxygen potentials of several three- and two-phase equilibria in the Fe−Co−S−O quaternary system were measured atP _SO2=1, 0.1, and 0.01 atm over wide temperature ranges. The measurements were carried out using a solid oxide electrolyte emf technique. The equilibria measured are sp+ε+δ, s+ε+ξ, sp+ξ+η, and sp+δ. The symbols sp, ε, δ, ξ, and η denote the spinel, monoxide, monosulfide, metal sulfate, and Fe₂O₃ phases, respectively. Compositions for several of the equilibrated phases were measured using electron probe microanalysis. The present results and literature data for the constituent ternary systems were used to obtain thermochemical solution parameters for the sp, ε, δ and ξ solid solution phases. The calculated potential-composition stability diagrams for SO₂ pressures of 1, 0.1, and 0.01 atm at 973, 1023, and 1073 K, respectively, are in good agreement with the experimental results. OMRAN A. MUSBAH, formerly Research Associate at the University of Wisconsin-Madison     

Phase relations in the system Cu-Gd-O

The phase relations in the system Cu-Gd-O have been determined at 1273 K by X-ray diffrac- tion, optical microscopy, and electron microprobe analysis of samples equilibrated in quartz ampules and in pure oxygen. Only one ternary compound, CuGd₂O₄, was found to be stable. The Gibbs free energy of formation of this compound has been measured using the solid-state cell Pt, Cu₂O + CuGd₂O₄ + Gd₂O₃ // (Y₂O₃) ZrO₂ // CuO + Cu₂O, Pt in the temperature range of 900 to 1350 K. For the formation of CuGd₂O₄ from its binary component oxides, CuO (s) + Gd₂O₃ (s) → CuGd₂O₄ (s) ΔG° = 8230 - 11.2T (±50) J mol^-1 Since the formation is endothermic, CuGd₂O₄ becomes thermodynamically unstable with respect to CuO and Gd₂O₃ below 735 K. When the oxygen partial pressure over CuGd₂O₄ is lowered, it decomposes according to the reaction 4CuGd₂O₄ (s) → 4Gd₂O₃ (s) + 2Cu₂O (s) + O₂ (g) for which the equilibrium oxygen potential is given by Δμ_{o 2} = −227,970 + 143.2T (±500) J mol⁻¹ An oxygen potential diagram for the system Cu-Gd-O at 1273 K is presented.     

Phase relations in the system Pb-Sn-Se

Phase equilibria have been determined in the portion of the Pb-Sn-Se system bounded by the compositions Pb-Sn-SnSe-PbSe. The PbSe-SnSe join is quasibinary with only small deviations from stoichiometry. The ternary phase boundaries lie close to the Pb-Sn side of the diagram. Subsolidus relations are shown by a series of isoplethal sections.     

The thermodynamics of the Ni-Co-S ternary system

The thermodynamic properties of the Ni-Co-S ternary system were determined by equilibrating the system with a known sulfur pressure established by using a gas mixture of H₂S/H₂ at 1373, 1473, and 1573 K. The isoactivity contours for Ni and Co were determined by application of the Gibbs-Duhem equation using Schuhmann’s method for ternary systems. For this purpose, a computer program was developed to calculate the activities of nickel and cobalt. The cobalt activity coefficients in dilute solutions of cobalt in the nickel-cobalt-sulfur system were evaluated and found to be 0.33, 0.50, and 0.55 at 1373, 1473, and 1573 K, respectively.     

Ti—Si—C三元体系自蔓延高温合成的反应热力学研究

根据热力学原理对Ti-Si-C三元体系进行了热力学计算分析,计算了Ti3SiC2自蔓延高温合成的绝热温度,绘出了体系各反应产物的反应自由焓ΔG与反应温度T的关系曲线,并测量了Ti3SiC2自蔓延高温合成的实际燃烧温度.研究结果表明:Ti-Si-C三元体系在SHS反应过程中其燃烧波能够自发进行;在SHS反应的高温区域,反应产物的热力学稳定性从高到低依次为Ti3SiC2、SiC、TiC,TiC和SiC有向Ti3SiC2反应转化的趋势;Ti3SiC2的SHS反应实际燃烧温度低于其理论绝热温度,主要原因是实际进行的SHS反应存在热量损失所致.     

Microstructure and phase relations for Ti-Mo-Al alloys

The influence of aluminum additions to a Ti-7 at. pet Mo alloy on the phase equilibria was investigated. The microstructures of the alloys, Ti-7 pct Mo-7 pct Al and Ti-7 pct Mo-16 pct Al, were determined by light and electron microscopy. It was found that with increasing aluminum concentration the formation of the metastable w phase was suppressed. In the Ti-7 pct Mo-16 pct Al alloy the β phase decomposed upon quenching by precipitating coherent, ordered particles having a B2 type of crystal structure (β₂). At low temperatures the equilibrium phases for this alloy were β + α+ β ₂, whereas at high temperature (850° to 950°C) the Ti₃Al phase was in two-phase equilibrium with the β phase. The four-phase equilibrium which exists at a temperature of about 550°C involves the reaction β + Ti₃Al ⇌ α + β₂. G. LUETJERING, formerly Staff Member Materials Research Center, Allied Chemical Corp., Morristown, N. J.,