On differential thermal analyzer curves for the melting and freezing of alloys

Using a heat-flow model of a differential thermal analyzer and thermal characteristics obtained by fitting experimental results for a pure metal, the response of the differential thermal analyzer is modeled for the melting and solidification of alloys. The enthalpy-temperature relation used for the alloy simulations is obtained by two different methods: (1) equilibrium and Scheil considerations derived solely from thermodynamic information and (2) solute-diffusion micromodels coupled to the differential thermal analysis (DTA) heat-flow equations. During the consideration of pure material melting, simple expressions are obtained for the effect of sample size and heating rate on the DTA melting onset temperature, peak temperature, and peak height, which assist in the proper calibration of a differential thermal analyzer. For alloys, the smearing effect of the DTA heat flow at different heating and cooling rates is demonstrated for various solidification-path features. In particular, the DTA peak temperature during melting, which is often selected as the liquidus temperature experimentally, is shown to be significantly higher than the liquidus temperature for small-freezing-range alloys and/or for alloys with slow solid diffusion. The DTA curves calculated for freezing with dendritic growth due to supercooling, quantify the errors associated with the determination of the liquidus temperature on cooling.     

Modifying ability of titanium-based pelleted master alloys

The problem of enhancing the quality of pressed titanium master alloys is discussed to increase the rate and degree of dissolution of their components and to ensure the formation of a fine-grained structure in aluminum alloys. A technology of producing a pelleted titanium master alloy for effective correction of the chemical composition of an aluminum alloy in casting is developed and tested. Incoming inspection of the component composition and the flux distribution in the volume of pressed pellets of various manufacturers is performed. The rate of dissolution of pressed powder master alloys in the aluminum melt is studied, and their modifying ability is estimated after studying the microstructures of cast blanks. Molasses is used as a binder in a pelleted master alloy. As a result, we achieved a uniform flux distribution over the pellet volume and the formation of uniform pores after annealing as compared pelleted master alloys of other manufacturers. The fabricated alloying briquettes have higher strength characteristics and their dissolution rate in the aluminum melt is higher than those of analogs by 15–20%.     

Reoxidation of Ni‐ and Ni‐Fe‐Alloys by Al2O3‐SiO2 Refractory Materials

Reactions at the refractory/melt interface during ingot casting of Ni‐ and Ni‐Fe‐alloys were studied. The casts were performed using different alumino‐silicate bricks as refractory materials. Samples taken from the casting channel before and after casting were investigated using light and scanning electron microscopy with XPS. Thermodynamic calculations were performed with FactSage and the results were compared with the results from industrial tests. After the melt has infiltrated the surface layer of the bricks, refractory corrosion starts with an attack of Mn and Mg of the melt on SiO₂ and Fe₂O₃ of the refractory bonding matrix. Despite the presence of elements with higher oxygen affinity in the melt, low‐melting alumino‐silicate phases are predominantly built by the reaction with Mn and Mg. In a second step this liquid phase either traps non‐metallic inclusions from the melt or, at higher contents of Zr, Ti, Mg, Y etc. in the melt, causes massive reoxidation and inclusion formation. The refractory materials investigated show an increasing trend for reoxidation with an increasing amount of SiO₂ in glassy phases of the refractory bonding matrix. By the use of a refractory material with higher mullite content in the bonding matrix or by use of alumina bricks a strong reoxidation of the melt and intense inclusion formation can be avoided. These observations are also valid for other alloys with higher contents of elements with high affinity to oxygen.     

Development of a new method to produce melts suitable for the production of amorphous Fe−Si−B materials

Research work was performed on the development of a new reduction process for the melting and refining of boron containing alloys used in the production of amorphous material for transformer cores. Based on fundamental thermodynamics principles, a reduction refining process was developed which employs conventional steelmaking vessels for using steel scrap, ferro alloys, and boron ores to produce an Fe−Si−B alloy. The process can eliminate the need for ferro boron alloy, high purity iron, and remelt stock to produce the Fe−Si−B alloy. Process variables were established which show the effects of mixing time, reductant alloy additions, slag chemistry, and temperature on the reduction kinetics. Final melt chemistries have lower levels of sulfur, nitrogen, and other tramp elements than conventional methods for producing the Fe−Si−B melt.     

The use of controlled solidifcation and melting experiments to determine liquidus and solidus boundaries

Theoretical steady-state solute profiles at melting and solidifying interfaces predict that the solid-liquid interface temperature should correspond to the liquidus temperature upon melting and the solidus temperature upon freezing. Experiments have been carried out with Sn−Bi and Sn−Sb alloys which show that it is experimentally possible to achieve the predicted steady-state profiles on melting and freezing in concentrated alloys. A technique was developed to measure solid-liquid interface temperatures and the solidus and liquidus phase boundaries were determined in these two systems. The results are compared to literature values.     

Melting of secondary-phase particles in Al-Mg-Si alloys

The melting of secondary-phase particles—or, more precisely, the melting of such particles together with the surrounding matrix—in two ternary Al-Mg-Si alloys has been studied. In the quasi-binary Al-Mg₂Si alloy, one melting reaction is found. In the alloy with an Si content in excess of that necessary to form Mg₂Si, three different melting reactions are observed. At upquenching temperatures above the eutectic temperature, the reaction rates are very high, and it is assumed that they are controlled by diffusion of the alloying elements in the liquid. Melting is also observed after prolonged annealing at temperatures below the eutectic temperature in these alloys, which is explained by the different diffusion rates of Mg and Si. The rate of the melting reaction is in this case assumed to be controlled by diffusion of the alloying elements in the solid α-Al phase. It is shown that calculation of the particle/matrix interface composition, which determines when melting is possible, cannot be made solely on the basis of the phase diagram, but must also include the rate of diffusion of Mg and Si. The melting temperatures observed differ somewhat from the accepted eutectic temperatures for these alloys. On prolonged annealing, the liquid droplets formed dissolve into the surrounding matrix and their chemical composition is found to change during dissolution. The resulting eutectic structure after quenching of a droplet is explained by the phase diagram and the different diffusion rates of Mg and Si as well as by the nucleation conditions of the constituents involved.     

Melting of secondary-phase particles in Al-Mg-Si alloys

The melting of secondary-phase particles—or, more precisely, the melting of such particles together with the surrounding matrix—in two ternary Al-Mg-Si alloys has been studied. In the quasi-binary Al-Mg₂Si alloy, one melting reaction is found. In the alloy with an Si content in excess of that necessary to form Mg₂Si, three different melting reactions are observed. At upquenching temperatures above the eutectic temperature, the reaction rates are very high, and it is assumed that they are controlled by diffusion of the alloying elements in the liquid. Melting is also observed after prolonged annealing at temperatures below the eutectic temperature in these alloys, which is explained by the different diffusion rates of Mg and Si. The rate of the melting reaction is in this case assumed to be controlled by diffusion of the alloying elements in the solid α-Al phase. It is shown that calculation of the particle/matrix interface composition, which determines when melting is possible, cannot be made solely on the basis of the phase diagram, but must also include the rate of diffusion of Mg and Si. The melting temperatures observed differ somewhat from the accepted eutectic temperatures for these alloys. On prolonged annealing, the liquid droplets formed dissolve into the surrounding matrix and their chemical composition is found to change during dissolution. The resulting eutectic structure after quenching of a droplet is explained by the phase diagram and the different diffusion rates of Mg and Si as well as by the nucleation conditions of the constituents involved.     

Ultrasonic-Assisted Soldering of 5056 Aluminum Alloy Using Quasi-Melting Zn-Sn Alloy

To obtain sound butt-joints of 5056 aluminum alloy rods, ultrasonic-assisted soldering was conducted using Zn-18Sn and Zn-60Sn alloys. Each solder foil was inserted between rods of 5056 aluminum alloy. Ultrasonic vibration was propagated to faying surfaces at soldering temperatures below the liquidus temperature of the solder alloys, and then the samples were air cooled to room temperature. The optimum vibration time at the soldering temperature must be more than 2 seconds to have complete wetting and less than 4 seconds to avoid excessive dissolution of the 5056 alloy. The 5056 alloy joints soldered using quasi-melting. Zn-Sn alloys showed greater strength than the joints soldered at the temperatures over its respective liquidus temperature. As the soldering temperature was increased, the increased formation of the intermetallic compound Mg₂Sn or phases containing Mg generated by dissolution of 5056 into the solder layer decreased the joint strength. Ultrasonic-assisted soldering at an optimum temperature between solidus and liquidus of the Zn-Sn alloys is an important consideration for producing sound joints with sufficient strength.     

Effect of the solidification time on the median particle size of powders produced by water atomisation

Present empirical correlations to predict the median particle size of water atomised powders have a validity restricted to a particular atomiser and alloy family. This work proposes a mathematical function that takes into account the influence of the heat transfer coefficient and, therefore, of the solidification time on the median particle size. This equation is applied in combination with previously proposed empirical correlations to extend their validity to a broader range of alloys. Experiments were conducted with alloys of different melting point (Fe base, Cu base and Sn). Quantitative measurements of the median particle size, tap density and several shape factors, and qualitative observations of the particle shape confirmed the importance of the heat transfer rate. It is shown that the inclusion of the solidification time effect results in a better agreement between calculated and experimental data when both low and high melting temperature alloys are taken together.     

Thermodynamic behaviour of zinc in Fe‐C and CaO‐FeO‐CaF2 slag at high temperatures

The distribution ratio of zinc between Ag‐Zn and Fe‐Zn alloys was measured to clarify the thermodynamic behaviour of zinc in Fe‐C melt at high temperatures. Also, the distribution ratio between Ag‐Zn alloy and CaO‐FeO‐CaF₂ slag was measured to understand the dissolution mechanism of zinc in molten slags. The activity coefficient of zinc in Ag‐Zn alloy was preliminarily measured as a fundamental thermodynamic data for the activity of zinc in Fe‐C melt. From the dependence of the activity coefficient of zinc in Fe‐C melts on temperature and carbon content, the following equation could be obtained at 1473 ‐ 1623 K: The distribution ratio of zinc between Ag‐Zn alloy and CaO‐FeO‐CaF₂ slag increased by increasing both the oxygen potential and slag basicity. The stoichiometric coefficients of the dissolution reaction were obtained by considering the relationship between zinc distribution ratio and slag basicity or oxygen partial pressure, when one of these two independent variables was fixed. The dissolution reaction of zinc into the slags could be described as follows:      

The columnar to equiaxed transition in tin-lead alloys

Tin-lead alloys were solidified directionally and the position of the columnar to equiaxed transition determined on vertical sections of the ingots. The columnar length was found to increase with decreasing lead concentration and increasing heat transfer coefficient. A mathematical model of the heat flow in the system was used to determine local temperatures, temperature gradients, and velocities in the solidifying alloy. Comparing the position of the columnar to equiaxed transition and local thermal conditions, it was found that the transition occurred when the temperature gradient in the melt at the liquidus temperature was 0.11°C/mm for Sn 10 wt pct Pb, 0.10°C/mm for Sn 5 wt pct Pb, and 0.13°C/mm for Sn 15 wt pct Pb. The position of the transformation was found to be independent of melt superheat for the conditions considered.     

Anodic dissolution of Pb-Sb alloys in an equimolar mixture of potassium and lead chlorides

The effect of temperature and antimony concentration on the anodic dissolution of Pb-Sb alloys in an equimolar KCl-PbCl₂ melt is investigated. It is shown that, up to the specific values of the current densities, the main process is lead dissolution, which starts at near-equilibrium potentials. The theoretical anode polarization curve for the dissolution of Pb-Sb alloys is calculated. It is established that the limiting stage is the mass transfer from the alloy side.     

Dissolution of iron intermetallics in Al-Si Alloys through nonequilibrium heat treatment

Conventional heat treatment techniques in Al-Si alloys to achieve optimum mechanical properties are limited to precipitation strengthening processes due to the presence of second-phase particles and spheroidization of silicon particles. The iron intermetallic compounds present in the microstructure of these alloys are reported to be stable, and they do not dissolve during conventional (equilibrium) heat treatments. The dissolution behavior of iron intermetallics on nonequilibrium heat treatment has been investigated by means of microstructure and mechanical property studies. The dissolution of iron intermetallics improves with increasing solution temperature. The addition of manganese to the alloy hinders the dissolution of iron intermetallics. Nonequilibrium heat treatment increases the strength properties of high iron alloys until a critical solution temperature is exceeded. Above this temperature, a large amount of liquid phase is formed as a result of interdendritic and grain boundary melting. The optimum solution treatment temperature for Al-6Si-3.5Cu-0.3Mg-lFe alloys is found to be between 515 °C and 520 °C.     

Phase-Field Simulation of Fusion Interface Events during Solidification of Dissimilar Welds: Effect of Composition Inhomogeneity

We investigate the events near the fusion interfaces of dissimilar welds using a phase-field model developed for single-phase solidification of binary alloys. The parameters used here correspond to the dissimilar welding of a Ni/Cu couple. The events at the Ni and the Cu interface are very different, which illustrate the importance of the phase diagram through the slope of the liquidus curves. In the Ni side, where the liquidus temperature decreases with increasing alloying, solutal melting of the base metal takes place; the resolidification, with continuously increasing solid composition, is very sluggish until the interface encounters a homogeneous melt composition. The growth difficulty of the base metal increases with increasing initial melt composition, which is equivalent to a steeper slope of the liquidus curve. In the Cu side, the initial conditions result in a deeply undercooled melt and contributions from both constrained and unconstrained modes of growth are observed. The simulations bring out the possibility of nucleation of a concentrated solid phase from the melt, and a secondary melting of the substrate due to the associated recalescence event. The results for the Ni and Cu interfaces can be used to understand more complex dissimilar weld interfaces involving multiphase solidification. This article is based on a presentation given in the symposium entitled “Materials Behavior: Far from Equilibrium” as part of the Golden Jubilee Celebration of Bhabha Atomic Research Centre, which occurred December 15–16, 2006 in Mumbai, India.     

硅热法镁冶炼料球导热系数研究

针对硅热法镁冶炼还原反应计算分析中存在的料球密度、比热容、导热系数等基础物性参数给定不准确的问题,采用同步热分析仪和激光导热分析仪测试了镁冶炼原料的基本物性参数,探究了温度、成型压力、配硅比等因素对原料各物性参数的影响。结果表明,煅白球团与料球的导热系数随温度的升高而减小、随成型压力增大而明显增大。     

The melting and dissolution of low-carbon steels in iron-carbon melts

Direct experimental proof is presented in the paper for the role played by the mass transfer of carbon in accelerating or facilitating the melting and dissolution of pure iron specimens in iron-carbon melts. It is shown that pure iron may readily melt in iron-carbon melts even under conditions where the temperature of the molten phase is considerably below the melting point of the pure iron or low-carbon specimen. A mathematical interpretation is developed for these experimental results that includes the mass transfer of carbon and the unsteady state heat transfer within a moving boundary system. The results of the analysis were found to agree with the experimental data thus providing a basis for further calculations aimed at predicting the melting of scrap in the basic oxygen furnace. These calculations show that scrap melting, facilitated by carbon diffusion from the melt to the scrap surface, begins very early during the process and that melting is retarded and even terminated during the blow when the bath has insufficient superheat to provide the necessary sensible and latent heat required for melting. It follows therefore that the rate of scrap melting in steelmaking processes is accelerated if the removal of carbon in the bath is retarded or if the temperature of the bath is increased rapidly in order to maintain a high level of superheat during the refining process.     

Liquidus temperatures and phase equilibria in the BaCl<Subscript>2</Subscript>–MCl–BaO systems

The liquidus temperatures of the BaO–BaCl₂–MCl systems (with M = alkali metal) are determined by thermal analysis. The caloric effects observed during melting of the barium-containing chloride eutectic with barium oxide additions are studied. A chemical mechanism of barium oxide dissolution in the melts is confirmed. X-ray diffraction patterns taken for the melt solidified after experiment indicate the presence of barium oxychloride Ba₄OCl₆ in the solid phase. It is shown that the significant increase in the liquidus temperature in adding the barium oxide to barium-containing chloride molten mixtures is related to substantial changes in their composition and structure.     

EAF Smelting Trials of Waste‐Carbon Briquettes at Avesta Works of Outokumpu Stainless AB for Recycling Oily Mill Scale Sludge from Stainless Steel Production

The EAF steel plant of Avesta Works, Outokumpu Stainless AB, has been used to perform smelting reduction trials of briquettes consisting of oily mill scale sludge, carbon and other wastes. A total of 7 briquette smelting trials were performed. The heats were processed smoothly smelting 3 t of briquettes or 3.4 mass‐% of metal charges. The quantities of FeSi powder and O₂ gas injected and electric energy supplied were increased to smelt briquettes of 6 t. No impacts were found on the analyses of the crude stainless steel tapped from the EAF during the trials. The results of the briquette smelting have been evaluated by referring to the data from the reference heats and results from earlier laboratory tests. The recovery of Cr, Ni and Fe elements from the briquettes was nearly complete and was found to occur mainly through carbon reduction. The slag masses were not increased in three trials as compared with the reference heats. There were moderate increases in the slag masses in four trial heats. The increases were, nevertheless, lower by 52‐69% than the slag masses generated by Sireduction of the briquette oxides. Afterwards, by referring results from the present trials, waste‐carbon briquettes amounting to 1‐3 t were smelted very smoothly in many of the EAF heats at Avesta Works to recycle the oily mill scale sludge and other wastes from stainless steel production.     

Evolution of Globular Microstructure in New Rheocasting and Super Rheocasting Semi‐Solid Slurries

Based on the solidification theory for metal alloys, a simple recipe for the controlled processing of globular microstructures without external stirring is presented: Firstly, small solidification nuclei must be distributed homogeneously throughout a melt. In New Rheocasting (NRC) these nuclei are formed by forced homogeneous nucleation due to partial quenching of the melt, while in Super Rheocasting (SRC) the nuclei are “second phase particles” in specially designed alloys, which are grown in a controlled fashion in a certain temperature range. Potential alloy compositions for SRC are provided. Secondly, given these melts with small particles in them, globular growth can be assured by utilizing the Gibbs‐Thomson “self healing effect” and slow further cooling to allow diffusion in the melt and to suppress constitutional supercooling. This simple recipe is applicable to various ferrous and non‐ferrous alloys. If an SRC alloy is cooled more rapidly than necessary for globular growth of the primary phase, but is held sufficiently long in the SRC range for dispersoid formation, these dispersoids can act as potent grain refiners and possibly enhance elevated temperature properties. A combination of both processes by using SRC alloys in the NRC equipment may lead to pressure tight castings with low porosity and finer grain structure than can be achieved with NRC on its own, and consequently, better mechanical properties.     

Determination of interface heat transfer coefficient between aluminum casting and graphite mold

To produce castings of titanium, nickel, copper, aluminum, and zinc alloys, graphite molds can be used, which makes it possible to provide a high cooling rate. No die coating and lubricant are required in this case. Computer simulation of casting into graphite molds requires knowledge of the thermal properties of the poured alloy and graphite. In addition, in order to attain adequate simulation results, a series of boundary conditions such as heat transfer coefficients should be determined. The most important ones are the interface heat transfer coefficient between the casting and the mold, the heat transfer coefficient between the mold parts, and the interface heat transfer coefficient into the environment. In this study, the interface heat transfer coefficient h between the cylindrical aluminum (99.99%) casting and the mold made of block graphite of the GMZ (low ash graphite) grade was determined. The mold was produced by milling using a CNC milling machine. The interface heat transfer coefficient was found by minimizing the error function reflecting the difference between the experimental and simulated temperatures in a mold and in a casting during pouring, solidification, and cooling of the casting. The dependences of the interface heat transfer coefficient between aluminum and graphite on the casting surface temperature and time passed from the beginning of pouring are obtained. It is established that, at temperatures of the metal surface contacting with a mold of 1000, 660, 619, and 190°C, the h is 1100, 4700, 700, and 100 W/(m² K), respectively; i.e., when cooling the melt from 1000°C (pouring temperature) to 660°C (aluminum melting point), the h rises from 1100 to 4700 W/(m² K), and after forming the metal solid skin on the mold surface and decreasing its temperature, the h decreases. In our opinion, a decrease in the interface heat transfer coefficient at casting surface temperatures lower than 660°C is associated with the air gap formation between the surfaces of the mold and the casting because of the linear shrinkage of the latter. The heat transfer coefficient between mold parts (graphite–graphite) is constant, being 1000 W/(m² K). The heat transfer coefficient of graphite into air is 12 W/(m² K) at a mold surface temperature up to 600°C.