Differential molar heat capacities to test ideal solubility estimations

PURPOSE: Calculation of the ideal solubility of a crystalline solute in a liquid solvent requires knowledge of the difference in the molar heat capacity at constant pressure of the solid and the supercooled liquid forms of the solute, delta Cp. Since this parameter is not usually known, two assumptions have been used to simplify the expression. The first is that delta Cp can be considered equal to zero; the alternate assumption is that the molar entropy of fusion, delta Sf, is an estimate of delta Cp. Reports claiming the superiority of one assumption over the other, on the basis of calculations done using experimentally determined parameters, have appeared in the literature. The validity of the assumptions in predicting the ideal solubility of five structurally unrelated compounds of pharmaceutical interest, with melting points in the range 420 to 470 K, was evaluated in this study. METHODS: Solid and liquid heat capacities of each compound near its melting point were determined using differential scanning calorimetry. Linear equations describing the heat capacities were extrapolated to the melting point to generate the differential molar heat capacity. RESULTS: Linear data were obtained for both crystal and liquid heat capacities of sample and test compounds. For each sample, ideal solubility at 298 K was calculated and compared to the two estimates generated using literature equations based on the differential molar heat capacity assumptions. CONCLUSIONS: For the compounds studied, delta Cp was not negligible and was closer to delta Sf than to zero. However, neither of the two assumptions was valid for accurately estimating the ideal solubility as given by the full equation.     

钢中铝-硅-锰复合脱氧反应的热力学计算

复合脱氧后钢液的最终氧含量优于单独脱氧的效果,同时复合脱氧可产生低熔点、易聚合长大的复合夹杂物,实现最佳的脱氧效果。用热力学方法计算了铝-硅-锰复合脱氧的效果,结果表明,在不同硅锰比下,复合脱氧均比单独用铝脱氧的最终氧含量要低;根据脱氧产物为锰铝榴石的原则得出了合金脱氧剂的组成成分。热态试验验证了理论计算结果。     

Eutectic interface configurations during melting

Experimental studies are presented on the melting of a lamellar eutectic structure in a transparent model alloy system. Steady-state morphologies have been characterized for different dissolution rates. Both coupled and noncoupled melting of eutectic are observed. A diffusive model of coupled eutectic melting has been developed and compared with the experimental results. Because the eutectic spacing is fixed, the system is shown to select the shape so that the average position of the interface for the two phases remains isothermal. A comparison of the predicted shapes with the experimental data shows that the higher melting point phase adjusts its curvature to equate the average temperature of the two phases when the experimental conditions are in the coupled melting regime. The conditions for a coupled melting to be unstable are described for which one of the phases extends further into the liquid. When this extension is significant, a spherodization of the leading phase is observed.     

"活度"质疑

为研究二元系溶液中组元摩尔分数和气相中蒸气压的规律,考察了48个化合物在熔点固液相变的熔化熵变,发现相变时没有发生显著的化合物分解.在假设二元系溶液中存在化合物分子的情况下,组元在全浓度范围符合拉乌尔定律,不存在Lewis定义的“活度”;通过与Mg-Si、In-Sb和Fe-Mn三个二元系实测活度结果对比,证实了计算的平衡摩尔分数即为活度值,二元金属熔体不存在所谓“活度”的观点.推导了在二元系金属熔体存在一个金属间化合物条件下平衡的摩尔分数的通用公式,以及相应的A₂B或AB型金属间化合物的一般公式.将二元系溶液划分为大于纯组元熔点的温度、小于纯组元熔点温度但高于液相线和低于液相线的三个区间,提出了适应不同区间的广义拉乌尔定律的关系式.      

Thermal analysis of the compositional shift in a transient liquid phase during sintering of a ternary Cu-Sn-Bi powder mixture

In this work, differential scanning calorimetry (DSC) and microstructural analysis were used to study the transient-liquid-phase sintering (TLPS) of a Cu-Sn-Bi powder mixture. During sintering, the liquid phase shifts from a Sn-rich (i.e., ∼90 wt pct Sn) to a Bi-rich (i.e., >78 wt pct Bi) composition. In addition, the presence of Bi creates two melting events: a Sn:Bi eutectic reaction at 139 °C and a reaction involving the melting of (Bi) at 191 °C. The Sn:Bi eutectic melting event was fully transient. The melting event at 191 °C was consistent with the formation of a terminal Bi-rich liquid phase. The rate of compositional shift toward this terminal liquid phase at 260 °C was dependent on the rate of the reaction of the Sn with the Cu powder to form intermetallic phases. For mixtures made with medium and fine Cu powder, the terminal Bi-rich composition was reached after isothermal hold times of 20 and 15 minutes, respectively. This resulted in a new melting point for the mixture of 191 °C. For coarse Cu powders, the rate of the compositional shift toward a Bi-rich composition was much slower. The liquid phase remained at a hypoeutectic Sn-Bi composition estimated at 80 wt pct Sn, while the mixture maintained a melting point of 139 °C.     

The surface tensions of indium and cadmium

The surface tensions of 99.9999 pct In and Cd have been measured by the sessile drop method. The surface tension/temperature behavior of liquid indium is nonlinear and within a certainty of 99.5 pct, can be represented by the following quadratic equation:γ _In = 568.0 − 0.04t − 7.08 × 10⁻⁵ t ² ± 5 dyne per cm At its melting point, the surface tension of liquid indium is 560 ± 5 dyne per cm. The slope of the temperature coefficient of the surface tension of liquid cadmium is strongly positive at the melting point, becomes zero about 100°C above the melting temperature (at which point the surface tension is a maximum), and is negative at higher temperatures. At the melting point, the surface tension of cadmium is 590 ± 5 dyne per cm. The surface tension of cadmium is not as readily affected by nonequilibrium thermal conditions as is the surface tension of zinc. The form of the surface tension/temperature curve of indium and cadmium together with similar data for Zn, Cu, Pb, and Sn support a theoretical scheme which generalizes liquid metal surface tension behavior and which, on the basis of calculations, lists liquid metals according to their propensity for surface ordering.     

铁液中Al_2O_3纳米颗粒溶解和熔化的热力学研究

与块体材料相比,纳米材料尺寸小、界面能大,导致其溶解和熔化过程的热力学不同于块体材料.从理论上推导了Al2O3纳米颗粒在铁液中的元素平衡溶度积以及熔化温度与颗粒尺寸之间的关系,结果表明,随颗粒尺寸减小,平衡溶度积逐渐增加,熔化温度逐渐下降,而且粒径越小,平衡溶度积和熔化温度的变化率越大.经计算,1873K铁液中Al2O3的质量分数为0.01%时,半径为0.1nm的Al2O3颗粒比块体Al2O3的平衡溶度积增加了11.71%;半径为1nm的Al2O3颗粒在空气和铁液中的熔化温度分别为1849K和1267K,比块体Al2O3的熔化温度分别下降了454K和1036K.     

CaO-Al2O3基钢液净化剂组成的优化

运用CaO-Al2O3-SiO2三元系的熔点和等αAl2O3相图,分析了CaO-Al2O3渣系净化剂降低钢液中氧化物夹杂的能力与其组成的关系。从热力学角度看,CaO/Al2O3比值高（1.6～2.0）,则αAl2O3低（≤0.02）,有利于钢液中氧化物夹杂的降低;从动力学角度看,CaO/Al2O3低（1.1～1.26）,则熔点低（〈1400℃）,有利于钢液中氧化夹杂的排出。净化剂组成的优化结果表明,适宜的CaO/Al2O3比值为1.41～1.74,净化剂αAl2O3较低（0.02～0.04）,熔点较低（〈1450℃）。工业性试验表明,优化后的净化剂净化钢液效果显著。     

酸溶铝含量对硅镇静钢夹杂物特征及水口堵塞的影响

通过500 g MoSi₂电阻炉熔炼试验考察了酸溶铝Als含量对硅镇静钢中夹杂物形貌、组成、数量及熔点的影响,并对KR铁水预处理-BOF-吹Ar-LF-CC流程现场水口残留物进行微观观察,探讨了夹杂物堵塞水口的机理,提出了硅镇静钢中铝含量的合理控制范围。结果表明,随Als含量增加硅镇静钢的夹杂物熔点升高,夹杂物数量减少;观察水口残留物为低熔点夹杂物镶嵌高熔点夹杂物,高Als钢中固态夹杂物以熔融态夹杂物为粘结剂聚集而粘附水口;钢液中Als含量控制在0.0030%~0.007 5%不会生成皮下气孔、不易水口堵塞。     

Macrosegregation in quiescent melting and liquid-phase sintering

Macrosegregation during melting of alloys can arise if the densities of the alloy components differ. In particular, if the higher-melting component is not present in amounts sufficient to develop an interconnected structure, this component can sink (assuming it is more dense than the liquid) to the crucible bottom during melting. This produces a liquid head consisting of (to a first approximation) the pure lower-melting component. The resulting macrosegregation takes considerable time to eliminate since it exists over a macroscopic distance (that over which the particles sink). Similar considerations apply to liquid-phase sintering, also treated in this article. The tendencies for macrosegregation and the subsequent structure evolution in melted/sintered materials can be summarized in a melting map. Such a map has axes of alloy overall composition and alloy liquidus composition. The development and elimination of macrosegregation proceeds in stages. Following initial particle settling, the liquid in the liquid-plus-solid zone near the crucible bottom, which was generated by the settling, attains its equilibrium composition. Finally, elimination of the long-range liquid concentration gradient takes place. If the material has a composition corresponding to a liquid-phase-sintered alloy, the solid in the liquid-plus-solid zone then attains its equilibrium composition. The times for the various stages can be estimated simply. Melting maps can be refined by placing contours of equilibration time on them.     

Aluminium scrap melting under different liquid aluminium flow conditions: part-II: two phase flow

This experimental research work deals with aluminium (Al) alloy melting in an Al bath. In this liquid metal, nitrogen gas was introduced at specific locations and at different gas flow rates. The samples employed, along with their position in the liquid Al, and the procedure for melting detection, were identical with the ones utilised in Part I. The introduction of gas into liquid Al has different effects on the melting time of the immersed Al 6061 alloy cylinder. For the range of gas flow rates examined, the addition of gas into a stagnant Al bath (i.e. natural convection conditions) produces insignificant changes in melting time. However, when the liquid Al is moving (i.e. forced convection conditions), the gas addition leads to a sizeable reduction in melting time. The melting time reduction ratio is introduced as a way to compare the melting under single and two phase flow liquid Al conditions. It is found that this ratio is affected by the nozzle position and also by the gas flow rate. The concept of an equivalent single phase velocity is also introduced, and defines the single phase velocity of liquid Al which results in the same melting time of the cylinder as under two phase flow conditions. It is found that the equivalent single phase velocity is influenced by both the gas flow rate and the nozzle position. The parameter which most likely contributes to the acceleration of the melting rate in two phase flow is the turbulence intensity, which is expected to increase due to the nitrogen gas injection.     

Determination of the coordination number of liquid metals near the melting point

A plot of the relation between the empty volume fraction and the coordination number as a function of a geometric parameter was constructed. This plot was based on regular crystal structures (fcc, bcc, simple cubic, and diamond cubic) in the solid state. The graphical correlation was used to predict the coordination numbers for liquid metals near the melting point. The coordination numbers of 39 liquid metals were predicted by using Pauling’s univalent ionic radius, the liquid density, and the nearest neighbor separation distance.     

Determination of the coordination number of liquid metals near the melting point

A plot of the relation between the empty volume fraction and the coordination number as a function of a geometric parameter was constructed. This plot was based on regular crystal structures (fcc, bcc, simple cubic, and diamond cubic) in the solid state. The graphical correlation was used to predict the coordination numbers for liquid metals near the melting point. The coordination numbers of 39 liquid metals were predicted by using Pauling’s univalent ionic radius, the liquid density, and the nearest neighbor separation distance.     

新型Al基复合脱氧剂脱氧效果研究

Al作为炼钢脱氧剂单独脱氧时易烧损,导致利用率较低;同时,其脱氧产物Al₂O₃熔点高,形状不规则,不易在脱氧过程中上浮排出,造成水口堵塞,恶化钢材质量.为了提高铝的脱氧效率,同时使脱氧产物Al₂O₃能快速从钢液中上浮排出,本文研究了一种以金属铝为有效脱氧组分,低熔点氧化物渣系为载体的新型复合脱氧剂.实验表明,使用该脱氧剂不仅可以保证钢液中溶解氧的质量分数在10×10-6以下,而且脱氧后钢中Al₂O₃夹杂物与纯Al脱氧相比尺寸更小、数量更少,较显著地提高了钢材的纯净度,具有良好的脱氧效果.      

钙处理技术在钢水精炼中的应用

钢水精炼过程中进行钙处理,对于硅还原的钢种,向钢液中喂入硅钙线,有利于钢水进行深脱氧,去除钢液中残余氧及金属氧化物,提高钢水纯净度;对于硅、铝还原的钢种,向钢液中喂入硅钙线,能够改变高熔点的铝氧化物夹杂的形态,形成低熔点的钙-铝化合物,有利于铝氧化物的去除,提高钢水清洁度,改善钢液的浇铸性能,减轻中间包水口堵塞问题,保证连铸顺利进行,改善钢的质量,提高合金收得率。降低生产成本。     

Direct Observation of Wetting and Spreading of Molten Aluminum on TiB2 in the Presence of a Molten Flux from the Aluminum Melting Point up to 1033?K (760?°C)

The wetting and spreading of molten aluminum on TiB₂ substrates between the aluminum melting point and 1033 K (760 °C) was investigated in the presence of different types of fluxes. The wetting and spreading behavior is observed to depend on the flux, its melting point, its chemistry, and its ability to dissolve alumina. When the flux melting point is higher than the melting point of aluminum, the molten aluminum takes on an initial spherical shape as a result of the thin alumina layer on its surface. After the flux is melted, it dissolves the alumina layer on the liquid aluminum surface causing the aluminum to wet and spread on the substrate. When the flux melts before the aluminum, the alumina layer on the solid aluminum surface is dissolved into the flux. In this case, the aluminum surface in contact with the molten flux is alumina layer free. Thus, the aluminum does not take a spherical shape after melting; it rapidly melts, wets, and spreads on the substrate. The use of a flux allows the wetting behavior of aluminum on TiB₂ to be observed at lower temperatures than previously reported.     

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。     

The founding of EPMA

Abstract

Liquid phase sintering is commonly used in powder metallurgy to improve physical properties through densification enhancement. With the aim of combining the advantages of liquid phase sintering and the use of promising alloying elements such as Mn and Si, liquid promoters with complex compositions were designed to provide a low melting point to form a liquid phase below the common sintering temperatures. The properties of these liquid phases were characterised in terms of contact angle, spreading evolution and infiltration. Using a Krüss drop shape analysis system, both wetting angle experiments and infiltration experiments were performed by changing the substrate characteristics from sintered to green iron specimens respectively. The discussion is based on the different features found for these liquids compared with copper, which is a well known liquid phase former used for improving the properties of low alloy steels. Simulations of the thermodynamic and kinetic processes taking place were performed by combining ThermoCalc and DICTRA software analysis.     

TP2铜管坯水平连铸用石墨结晶器功能失效行为研究

针对TP2铜管坯水平连铸用石墨结晶器进液孔堵塞导致的功能性失效问题,研究了堵塞石墨结晶器进液孔的白色粉末物质的化学成分、来源及形成机理,采用X射线衍射（XRD）、 X射线荧光、差热分析、扫描电子显微镜（SEM）和能谱分析（EDS）等检测手段进行系统性分析。研究结果表明,堵塞石墨结晶器进液孔的白色粉末的组成以SiO2为主,主要来源于炉衬耐火材料。随着铜液中氧含量的增加,铜熔体中的Cu2O和CuO分别与炉衬中的SiO2形成低熔点混合物,后经石墨结晶器冷却析出;低熔点混合物密度小,黏附在结晶器内壁,随着低熔点混合物的累积,最终导致进液孔完全堵塞。根据石墨结晶器的失效机理,对阴极电解铜、木炭和鳞片石墨等原材料及辅料采取烘干等方法,降低其携带的水分,以及加强炉内密封,减少铜液的保温时间等措施,可以降低铜液中的氧含量,减少氧化物粉末的产生,避免结晶器进液孔堵塞,从而防止结晶器功能失效。     

The thermodynamic properties of the masson polymerization models of liquid silicates

The thermodynamic properties of the Masson polymerization models of liquid silicates are examined with specific reference to the orthosilicate composition. The variation of configurational entropy with anion fraction of free oxygen ions in the liquid orthosilicate is shown to be identical for both models. Quantitative relationships between the thermodynamic solution properties of the models and the thermochemical properties of the solid orthosilicate and its component oxides are derived. The models facilitate calculation of the melting temperatures of orthosilicates and afford an explanation of their general melting behavior.