Kinetics studies on the dissolution of nitrogen in the CaO-Al2O3-SiO2 and CaO-Al2O3-TiO x melts

The rate of nitrogen dissolution in CaO-Al₂O₃-SiO₂ and CaO-Al₂O₃-TiO _x melts was measured by ¹⁴N–¹⁵N isotope exchange reaction. The rate constant for the CaO-Al₂O₃-SiO₂ melts at the ratio of mass pct CaO/mass pct Al₂O₃ = 1 increases as SiO₂ content increases, whereas the rate constant for the same melts at the ratio of mass pct CaO/mass pct SiO₂ = 1 increases as Al₂O₃ content increases. The rate constant for the CaO-Al₂O₃-TiO _x melts at the ratio of mass pct CaO/mass pct Al₂O₃ = 1 decreases as the TiO _x content increases. The activation energies of nitrogen dissolution in CaO-Al₂O₃-SiO₂ melts are about 1.5 to 3 times larger than that of molten pure iron. Moreover, the rate constant of nitrogen dissolution is independent of the ratio of Ti³⁺/Ti⁴⁺.     

Kinetic studies on the dissolution of nitrogen in CaO-Al2O3, CaO-SiO2, and CaO-CaF2 melts

The rate of nitrogen dissolution in CaO-Al₂O₃, CaO-SiO₂, and CaO-CaF₂ melts was measured by ¹⁴N-¹⁵N isotope exchange reaction. The rate constant of nitrogen dissolution in CaO-based oxide melts, which is defined as first order with respect to nitrogen partial pressure, was found to be much smaller than that in molten iron-based alloys investigated in our previous work. The activation energies for nitrogen dissolution in 40 mass pct CaO-60 Al₂O₃ and 50 CaO-50 SiO₂ melts are 224 and 581 kJ/mol, respectively. For CaO-Al₂O₃ and CaO-SiO₂, dependence of the rate constant on composition is very similar to that of nitride capacities. Moreover, it was confirmed that the rate constant was not affected by oxygen or nitrogen partial pressure.     

温度对CaO-SiO2-Al2O3-MgO高炉渣系Al2O3活度的影响

 Al₂O₃作为熔渣中的主要组元之一,其对熔渣的冶金性能的影响尤为突出。对于高炉炼铁而言,高炉渣中Al₂O₃增加会对炼铁及脱硫造成不利影响。然而,随着中国钢铁工业的不断发展,相对低廉的高Al₂O₃进口铁矿石使用量不断攀升,使得高炉渣中Al₂O₃含量明显增加,高炉渣中Al₂O₃质量分数往往大于15%,更高的甚至大于20%。目前关于高Al₂O₃高炉渣系中Al₂O₃组元的热力学性质(例如采用参考渣法测定Al₂O₃的活度)及其对炉渣冶金性能的影响等研究鲜有报道,而温度是影响冶金熔渣冶金性能的重要热力学因素之一,因此探讨温度对冶金熔渣中Al₂O₃组元活度影响的规律不仅具有重要的研究意义,同时也为现场实践提供坚实的理论依据。采用参考渣法对1 773～1 873 K温度条件下CaO-SiO₂-Al₂O₃-MgO高炉渣系Al₂O₃活度进行测定,并采用Raman光谱对熔渣的结构进行检测。考察了温度对CaO-SiO₂-Al₂O₃-MgO高炉渣系Al₂O₃活度的影响。结果表明,随着温度的增加,熔渣中Al₂O₃的化学势降低,熔渣与铜金属熔液之间的反应向右移动来达到新的平衡,因而Al₂O₃的活度随着温度的增加逐渐降低。温度的增加使熔渣中Al₂O₃与碱性金属氧化物发生反应,使钙铝酸盐(CaO·Al₂O₃和CaO·2Al₂O₃)和镁铝酸盐(MgO·Al₂O₃)等复合物生成量增加,此时熔渣的结构由于O2-的增加而逐渐发生解聚,熔渣中的自由Al₂O₃减少,从而导致Al₂O₃活度逐渐降低。     

Wettability of silicon carbide ceramic by Al2O3/Dy2O3 and Al2O3/Yb2O3 systems

Wettability is an important phenomenon in the liquid phase sintering of silicon carbide (SiC) ceramics. This work involved a study of the wetting of SiC ceramics by two oxide systems, Al₂O₃ /Dy₂O₃ and Al₂O₃ /Yb₂O₃, which have so far not been studied for application in the sintering of SiC ceramics. Five mixtures of each system were prepared, with different compositions close to their respective eutectic ones. Samples of the mixtures were pressed into cylindrical specimens, which were placed on a SiC plate and subjected to temperatures above their melting points using a graphite resistance furnace. The behavior of the melted mixtures on the SiC plate was observed by means of an imaging system using a CCD camera and the sessile drop method was employed to determine the contact angle, the parameter that measures the degree of wettability. The results of variation in the contact angle as a function of temperature were plotted in graphic form which showed that the curves displayed a fast decline and good spreading. All the samples of the two systems presented final contact angles of 40° to 10° indicating their good wetting on SiC in the argon atmosphere. The melted/solidified area and interface between SiC and melted/solidified phase were evaluated by scanning electron microscopy (SEM) and their crystalline phases were identified by X-ray diffraction (DRX). The DRX analysis showed that Al₂O₃ and RE₂O₃ reacted and formed the Dy₃Al₅O₁₂ (DyAg) and Yb₃Al₅O₁₂ (YbAg) phases. The results indicated that the two systems had a promising potential as additives for the sintering of SiC ceramics.     

Solubility and thermodynamic properties of Y2O3 in LiF-YF3 melts

A systematic investigation was undertaken to measure the solubility of Y₂O₃ in several LiF-YF₂ melts, with the YF₃ composition ranging from 20 to 50 mole pct, in the temperature range of 998 to 1273 K. Experimental results showed that the solubility of Y₂O₄ in the melts increased with increase in temperature and also with increased YF₃ content. The activity of Y₂O₃ was calculated using the free energy of fusion of Y₂O₃, . The was deduced from the values of enthalpy, heat of fusion, and melting point of Y₂O₃. From the known values of activity, the activity coefficients of Y₂O₃ as a function of temperature and melt composition were calculated. Considering the ionic nature of the melt, activity coefficients were also calculated using Temkin’s ideal mixing and electrically equivalent fraction methods. The thermodynamic data, such as integral molar enthalpy, entropy, and free energy of formation, were calculated as a function of composition and temperature. The calculated thermodynamic data showed that the melt exhibited a negative deviation from ideal conditions.     

中和结晶过程对Ta2O5粉末粒度特性的影响

采用中和结晶-煅烧法制备Ta2O5粉末,分别考察了中和结晶过程中钽液浓度、钽液起始pH值、结晶温度、氨水浓度、氨水流速和搅拌速度等六个因素对Ta2o5粉末粒度的影响.试验结果表明,在钽液浓度c(Ta2O5)为95g/L,钽液起始pH=1.80,水浴温度60℃,氨水浓度8.0 mol/L,氨水流速1.0 mL/min,搅拌速度40 r/min的条件下,制得的Ta2o5粉末最大平均粒径可达180μm,完全满足生产需求.     

10CrNi2Mo3Cu2V耐热钢的高温析出与脆化机制

摘要：利用光学显微镜、扫描电镜、力学性能测试等方法,分析了10CrNi2Mo3Cu2V耐热钢锻件的脆化原因,并研究了钢在1050～850℃区间的高温析出行为,及其对冲击韧性的影响。结果表明,锻件脆化由粗大的链状M6C相引起,950～850℃温度区间,钢中发生M6C相的高温析出行为,导致冲击韧性恶化。析出温度区间内,降低温度、延长时间均能促进析出相的形核与长大,使M6C相含量增加,尺寸长大,分布更加聚集,逐渐形成链状形貌。Mo元素偏析能够提高M6C相的开始析出温度、增加相含量。锻造温度是影响高温析出行为的关键因素,应控制终锻温度不小于950℃,避免锻后脆化。     

铝锆碳质滑板中SiC晶须形成机理

以铝锆碳滑板基质部分为研究对象,以金属硅粉、石墨和碳黑为原料,混合后在埋碳气氛下,于1 200～1 600℃范围内进行高温处理.通过透射电镜和能谱仪分析,研究发现碳化硅晶须为哑铃状,并且随着热处理温度升高,哑铃状小球慢慢减少,在这个过程中,SiC晶须的生长机理为气-固反应模型.     

炉甘石中ZnCO_3,ZnO,PbCO_3,Fe_2O_3,(CaCO_3+MgCO_3)含量测定的研究

（１）以氨水（１＋４）溶解样品，用ＸＯ作指示剂，ＥＤＴＡ滴定，测定ＺｎＣＯ３含量。（２）以１５％的硫酸铵溶解样品，用ＸＯ作指示剂，ＥＤＴＡ滴定，测定（ＺｎＣＯ３＋ＺｎＯ）含量。（３）以１５％的氯化铵溶液溶解样品，用ＥＢＴ作指示剂，ＥＤＴＡ滴定，测定（ＺｎＣＯ３＋ＺｎＯ＋ＣａＣＯ３＋ＭｇＣＯ３）含量。（４）以１６％的乙酸铵溶液溶解样品，以ＸＯ作指示剂，ＥＤＴＡ滴定，测定（ＰｂＣＯ３＋ＺｎＣＯ３＋ＺｎＯ）含量。（５）以稀盐酸溶解样品，用磺基水杨酸作指示剂，ＥＤＴＡ滴定，测定Ｆｅ２Ｏ３含量。     

Solubility of nitrogen and carbon in CaO-Al2O3 melts in the presence of graphite

CaO-Al₂O₃ slags were melted in graphite crucibles under N₂-CO-Ar gas mixtures at 1600°C. The contents of total nitrogen, cyanide and total carbon of the slags were determined by chemical analyses of quenched samples taken by suction from the melt. The nitrogen is present in the melt as nitride N^3- ion and cyanide CN^-1 ion, and carbon as cyanide and carbide C_2- ion. The equilibrium constants for the respective reactions were evaluated. It is found that the nitride capacity of the melt decreases whereas the cyanide and carbide capacities increase with increasing CaO/Al₂O₃ ratio.     

Solubility of nitrogen and carbon in CaO-Al2O3 melts in the presence of graphite

CaO-Al₂O₃ slags were melted in graphite crucibles under N₂–CO–Ar gas mixtures at 1600°C. The contents of total nitrogen, cyanide and total carbon of the slags were determined by chemical analyses of quenched samples taken by suction from the melt. The nitrogen is present in the melt as nitride N⁻³ ion and cyanide CN⁻¹ ion, and carbon as cyanide and carbide C ₂ ²⁻ ion. The equilibrium constants for the respective reactions were evaluated. It is found that the nitride capacity of the melt decreases whereas the cyanide and carbide capacities increase with increasing CaO/Al₂O₃ ratio.     

CaO-Al2O3基高铝高锰钢保护渣理化性能研究

以L25(65)正交试验为基础配置CaO-Al_2O_3基保护渣,研究了不同组分对高铝高锰钢保护渣理化性能的影响。结果表明,不同组分对CaO-Al_2O_3基连铸保护渣熔化温度的影响均是随其含量的增加,熔化温度降低,对熔化温度影响的主次顺序为Li_2ONa_2OB_2O_3BaOCaF_2MgO;各不同组分在一定含量范围内,对CaO-Al_2O_3基连铸保护渣黏度整体上均有降低的作用;结晶难易程度由难到易的顺序依次为3#、4#、23#、19#、20#及5#保护渣;利用热力学软件计算得到冷却析出物质中,大部分都含Ca_3B_2O_6,而该物质熔点比较低,且玻璃形态好,不易结晶,可以满足部分高铝高锰钢连铸使用要求。     

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.     

The kinetics of the exchange of cobalt(II) ions between NaCl and Na2O-SiO2-Fe2O3 melts in the temperature range 1200 to 1400 K

Studies of the equilibria and kinetics of the Co²⁺ ion exchange in the Na₂O-SiO₂-Fe₂O₃/NaCl system were performed over the 1200 to 1400 K temperature range by measuring the emf of galvanic cells of the following composition: $$( - )Co\left| {\frac{{NaCl - CoCl_2 }}{{Na_2 O - SiO_2 - Fe_2 O3}}} \right.\left| {NaCl - CoCl_2 } \right.\left| {Co( + )} \right.$$ Distribution coefficients α of the Co²⁺ ions between the salt phase and silicate melt are of the l0^?2 order. Differential equations describing the transfer process of the Co²⁺ ions from the salt phase to the silicate phase were solved. The diffusion coefficients D_Co ²⁺ in the Na₂O-SiO₂-Fe₂O₃ melt were determined by substituting the Co²⁺ ion concentration change in fused NaCI into the differential equations. The values of D_Co ²⁺ are about 10^?5 cm²S^?1 and they decrease with decreasing temperature and increasing Fe_?2O_?3 content in slags. The diffusion coefficient of the cobalt (II) ions in slags determined in this way is consistent with that determined by the otating disk method.     

Polythermal description of the oxygen pressures in the melts of the Subsystems Fe-FeOn and FeO-Fe2O3

The phase equilibria in the Subsystem Fe-FeO of the Compound System FeO ranging from mole fractions of x_o = 0 to x_o = 52% are characterised by a wide miscibility gap. Using the van Laar formulation, it is possible, up to mole fractions of x_o = 51%, to describe the liquidus line of the iron, the phase boundaries of the miscibility gap and, with the resultant activities a_Fe and a_FeOn, the oxygen pressures of the liquid phases either side of the miscibility gap, in a manner consistent with the temperature-dependent, experimental data of the relevant literature. In the overlap range (oxygen mole fractions of 50 ? 52%) to the adjacent Subsystem FeO-Fe₂O₃ (oxygen mole fractions of 50 ? 60), a continuous transition is achieved to the experimentally ascertained oxygen pressures in the liquid oxide melts, these being characterised by a tendency towards Compound formation. These -values are very accurately described polythermally by the modified short-range-order model with stipulation of the short ranges 3FeO·Fe₂O₃ and FeO·Fe₂O₃, and also of the dissociation reaction 3(FeO) = (Fe₂O₃) + [Fe] and (Fe₂O₃) = 2(FeO) + [O].     

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.