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By RIINA SALMIMIES, Paula Vehmaanperä, Antti Häkkinen

The dissolution of iron oxides in mixtures of acids is fairly uncommon but can result in a more efficient dissolution process. The objective in this work was to investigate the dissolution of synthetic hematite powder in mixtures of oxalic and sulfuric acid. Experiments were done at different acid ratios and temperatures. An increase in temperature from 15 to 35 °C increased solubility, whereas an increase from 35 to 50 °C did not change the solubility but had a profound effect on the kinetics. An important finding was that oxalic acid advanced the dissolution process since increasing the amount of oxalic acid in the system resulted in faster kinetics and higher solubilities. The dissolution kinetics were well described with the Kabai model, which was the only studied model able to describe the whole reaction time. However, the solid specific constant a varied for the different acid ratios and this is argued to be a result of changes in the solid phase. The changes in the constant a were not in line with the original study of Kabai, which indicates that a cannot be the solid specific constant but it can be the constant connected to dissolving media describing the changes in the dissolution mechanism.

Sep 23, 2020

By RIINA SALMIMIES, ANTTI HAKKINEN, PAULA VEHMAANPERA

Better understanding of the mechanisms and kinetics of dissolution can benefit several industrial processes. For example, iron can be leached from clays, which can be further used as a raw material in the ceramic industry. Another important application is the regeneration of ceramic filter media, which are used in the dewatering of iron ores. Dissolution of iron oxides in mixtures of acids is fairly uncommon and a less well-understood phenomenon, but it can result in a more efficient process. This work also shows that the determination of dissolution mechanisms and kinetics is not straightforward in different acid systems.

By Víctor Vázquez, Guillermo Tiburcio, Martin Encinas, Jesús L. Valenzuela, Erick Montaño, Alejandro Valenzuela, José Parga

Merrill-Crowe is the primary process used for the concentration and purification of silver in a cyanide solution. The Langmuir Adsorption model for silver recovery in a cyanide solution was used for the study. The maximum adsorption capacity was 6.19 mmol/g for silver. This model properly adjusts the experimental results of the adsorption equilibrium with high correlation coefficients, which also favors the formation of a single layer of molecules adsorbed for the silver in the electrocoagulation- generated species. The thermodynamic parameters ΔG, ΔH, and ΔS were estimated, and it was found that the adsorption process is exothermic and spontaneous. For the kinetic study, the Lagergren second-order equation was used to study the adsorption speed. To characterize the solids coming from the electrocoagulation, X-ray diffraction (XRD), and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDX) were used; the results of this study suggest that silver is present in aluminite, hydroniumjarosite, and alunogen.

Oct 30, 2021

By A. R. Farkoosh, K. Korgiopoulos, McGill University, O. Rodop, L. A. Villegas Armenta

"New generation of Al-Mg-Si alloys with thermally stable dispersoids that prevent recrystallization and grain growth during hot deformation are currently used in automotive components requiring good formability. Alloy chemistry controls the phase formation especially age-hardening precipitates, dispersoids, and primary intermetallic which have pronounced effect on grain structure, strength and formability. In this work, thermodynamic calculations have been used to predict the effects of varying levels of Si (0.5-1.5wt%), Mg (0.5-1.5wt%) and Mn (0.1-2.5wt%) on phase selection. Thermodynamic calculations have been performed in equilibrium and non-equilibrium conditions via the FactSage™ software using the FTlite database. Selected compositions have been cast, heat treated, extruded and characterized through scanning electron microscopy with energy dispersive spectroscopy and electron channeling contrast imaging techniques. The calculations showed that at the hot deformation temperature of ~540 oC, exceeding certain Mg and Si levels would lead to retained *-Mg2Si intermetallics and Si particles at the grain boundaries in addition to a-Al-(Mn,Fe)-Si. It was found that retained *-Mg2Si phase which adversely affects formability can be avoided for Si+2Mg levels lower than 2.3wt%. FactSage calculations also showed that increasing Mn from 0.5wt% to 1wt% leads to an increase in the amount of dispersoids (from 1wt% to 2wt%) that can potentially slow down recrystallization and grain growth during hot deformation and improve formability. Calculations at room temperature also show that for an alloy with 0.7wt% Mg, excess Si beyond 0.7 wt% promotes the precipitation of Si clusters in the Al matrix that accelerate natural age-hardening. Results were confirmed by experimental investigation.INTRODUCTIONAluminum alloy 6082 (Al-Mg-Si) is used in the automotive industry because of its high strength, and good weldability (I. J. Polmear, 2006). The alloy is age-hardenable through the precipitation of ß-Mg2Si and its precursors, and the recrystallization is usually inhibited by Mn- and Cr-containing dispersoids formed through high temperature heat treatments (I. Polmear & Couper, 1988). However, it is known that minor changes in alloy chemistry (Mg/Si ratio) can have significant influences on the ductility and formability of these alloys by altering phase selection and the resultant microstructure (Gupta, Lloyd, & Court, 2001; McQueen & Celliers, 1997; Zajac, Hutchinson, Johansson, & Gullman, 1994). For automotive applications where wrought alloys (usually extrusions) are cold-formed to produce suspension components, the chemistry of the alloys and the extruded structure are of crucial importance as they determine the formability at room temperature (Asensio-Lozano, Suárez-Peña, & Vander Voort, 2014). In this study, thermodynamic calculations along with experimental investigations were carried out on the Al-Mg-Si system to understand their phase formation and precipitation hardening as a function of alloy composition."

Jan 1, 2016

The published liquidus data on the Pb-PbS system have been correlated on the basis of one-coefficient Margules equations. Thermodynamic properties of the components of this system have been obtained, and it has also been found that the calculated miscibility gap of this system exists over a very narrow range of temperature (1041 to 1058°C).

Jan 1, 1972

By M. Nagamori, A. J. Plumpton

"Commercial HCl-leaching of magnesite and serpentine yields highly concentrated aqueous solutions containing 25 mass % to 33 mass % MgCl2. The partial molar enthalpies and heat capacities, the ionic activities of Mg2+ and Cl–, and the Raoultian activity of H2O have been assessed for the concentrated MgCl2-H2O solutions at temperatures of 348 to 373 K. These thermodynamic data are used to calculate the pH of aqueous MgCl2 solutions saturated with a Mg-bearing mineral such as magnesite, serpentine, brucite, forsterite, enstatite or talc. On the basis of these thermodynamic data, technico-economic aspects are discussed as to neutralization with pulverized MgCO3, water evaporation from the MgCl2 solutions, and ore composition including such minor constituents as CaCO3, FeCO3 and Fe3O4. IntroductionA major magnesium electrolytic reduction plant operates in Quebec, where another will begin its production in the year 2000. One uses imported magnesite ore as raw material, while the other will utilize local asbestos tailings (serpentine). Both processes produce a concentrated salt solution of 25 mass % to 33 mass % MgCl2 by leaching the ore with concentrated hydrochloric acid. Thus, the two processes differ mainly in the HCl-leach and related operations. After the HCl-leach of the ore, the serpentine process yields about 25 times more wet cake to filter and wash than the magnesite counterpart. A comparative cost-engineering study with respect to slurry filtration and cake washing has been published elsewhere (Blackburn and Nagamori, 1994). By contrast, the present study considers the thermodynamics and technicoeconomics of the HCl-leach itself for both ores."

Jan 1, 1999

By S. R. Steinacker, H. Schnideritsch, J. Antrekowitsch

Primary copper industry flue dust plays an increasingly important role in the creation of matte and slag. From a thermodynamic point of view, the chemically formed section of fine particles play a techno-logically interesting role in comparison to the mechanical carry-over. Here, the volatilization and the sub-sequent condensation in the off gas system lead to a characteristic distribution of the contained elements which are represented by various compounds of desired metals like zinc and lead. On the contrary, certain undesired components such as arsenic, bismuth and cadmium accumulate within the product as well. This paper describes existing models and theories concerning the formation of flue dust in the copper smelting process and presents a thorough investigation of the physico-chemical fundamentals by verifying assump-tions with thermodynamic calculations. By fully understanding the formation patterns at different stages and temperatures within the process, better knowledge for flue dust in the first step of the pyrometallurgi-cal copper smelting can be obtained - hence leading to new ideas and incentives for the following stages in the copper production cycle.

Jan 1, 2015

By C. Caballero, A. Warczok, K. Itagaki, A. Moyano, J. Font

The Codelco Norte Smelter process 2,500 tpd of arsenic-bearing concentrates with an arsenic content of up to 1.5% in one of its two main smelting units, the Teniente Converter. The product, 1,100 tpd high-grade matte or white metal, is traditionally fed to the PS converters, while the 1,700 tpd of slag is fed to the slag cleaning electric furnace for copper recovery. This is achieved in a very reductive environment which reduces the viscosity of the slag and enhances the sedimentation of the high-grade matte droplets. The behavior of arsenic in this non-oxidative environment was studied at lab-scale and fundamental thermodynamic data were obtained. Based on these data a thermodynamicbase model to assess the arsenic behavior in reductive environment was developed. It is based on a mass balance for the reduction and sedimentation stages performed in an electric furnace which allows the recovery of high-grade matte droplets after decreasing the viscosity of the slag. This model can be a very suitable tool for predicting fractional distribution of arsenic in the slag cleaning electric furnace, when the distribution ratio, vapor saturation degree, temperature, y As and pO2 are given.

Jan 1, 2007

By William E. Frazier

The presence of minute amounts of sulfur (10ppm) in nickel-base superalloys has been associated with reduced oxidation resistance and the premature spallation of protective coatings. Removal of sulfur by annealing these alloys in a hydrogen atmosphere has been successfully attempted by several researchers. This paper examines the fundamental thermodynamics and kinetics governing hydrogen desulfurization of elemental nickel. Limiting conditions for successful desulfurization are delineated. Assuming that the diffusion of sulfur is the rate limiting process of desulfurization, the effectiveness as well as time associated with hydrogen desulfurization is explored.

Jan 1, 1994

By R. C. Reed, L. T. Wu, H. C. Harada, K. Kawagish, R. T. Wu

Oxidation of pure metals is a chemical reaction in which the metal loses one or more electrons, such that the atom of the metal changes from the neutral state to a positively charge ion and reacts with oxygen to form an oxide of the metal. The oxide can form as a protective and adherent scale that slows down further oxidation, or may spall off repeatedly, exposing fresh metal surface to react with oxygen. In multi-component alloy systems such as typical high temperature NiCrAlY bond coats, more than one oxidation mechanism may take place at once and thus, complicates the study of oxidation. To better understand the competition between formations of oxides of different compositions, a thermodynamic assessment is carried out to study the oxidation mechanism of a Ni-27Cr-9Al (at %) ternary alloy. Based on the assessment, it is demonstrated that the layering of different oxides can be determined, with the most stable oxide (alumina) existing directly above the metal-oxide interface and the least stable oxide (nickel oxide) locating on the outer most layer. A comparison between the calculated results and previously published experimental observations shows excellent agreement.

Jan 1, 2010

By Shilai Yuan, Huimin Lu, Zhijiang Gao, Panpan Wang

"Solvent refining of silicon through using Si-Al melts is a valid method to remove the impurities from metallurgical grade silicon (MG-Si) melt. The thermodynamic behavior of impurities Fe, Al, Ca, Ti, Cu, C, B and P in MG-Si during the solidification of MG-Si was studied based on the available thermodynamic parameters and experimental data. The morphology of inclusions was investigated by Scanning Electron Microscope (SEM). The chemical composition of inclusions in MG-Si and Al-Si melt was analyzed by EPMA. It is found that the amount of white inclusion reduces and most impurities are solved into the Al-Si melts. After solidification of Si–Al alloy using induction heating and acid leaching, impurities can be effectively removed. The solidification of silicon from the Si–Al melt is found to be more effective for purification than general silicon solidification.IntroductionPhotovoltaic energy is one of promising energy resources in a sustainable society because of its inexhaustibility and cleanliness. Although the production and installation of solar cells have increased significantly during the last decade, the cost of solar cell installation is still high. Multicrystalline silicon has now become the main material in the photovoltaic market because of its low production cost and because of the relative high conversion efficiency of solar cells made from this material, which has been studied for a long time [1-3].Electronic grade (EG) silicon (99.9999999% Si) is commonly used as the raw material to produce SOG-Si (99.9999% Si). Silicon produced from the chemical routes restricts the development of solar cells due to environment threaten, high energy consumption and low productivity. Purification of metallurgical grade silicon (MG-Si) is a low cost, environment friendly method. Although several metallurgical processes such as directional solidification, vacuum refining and electron beam melting [4], have been developed, the cost reduction and refining efficiencies for manufacturing silicon is still have to be further optimized.In the purification process, it is difficult to remove boron and phosphorus by the conventional metal refining method. The refining efficiency depends on the segregation behavior of different elements in solid silicon and the liquid phase. The segregation ratios of all investigated impurities were found to be much smaller than the segregation coefficients between solid and liquid Al-Si melts [5]. For instance, the segregation coefficient of B in Si is 0.8 at the silicon melting point (1687K), whereas it is around 0.2 when silicon is solidified from Si-Al melt at 1273K. For phosphorus the segregation coefficient is 0.06 when silicon is solidified from Si-Al melt at 973K°C, which is much less than 0.35 for recrystallization from liquid silicon. Since the segregation coefficient of boron in silicon is 0.8, it cannot be removed by directional solidification."

Jan 1, 2014

By Xueqin Li, Xuewei Lv, Yu Zhang, Wenchao He

In order to make full use of the chromium-bearing vanadium titanium magnetite with chromium, a new process of “direct reduction-electric furnace smelting separation” has been developed for recovering the iron, vanadium, titanium and chromium in recent years. In this paper, FactSage, one of the most frequently-used thermodynamic calculation software, was used to calculate the reduction degree of Fe, V and Cr with different n C/nO (mole ratio of carbon and oxygen). It was found that the suitable operating conditions of direct reduction process were n C/nO > 1.07 and T > 1473 K. In addition, the direct reduction experiment of Hongge vanadium titanium magnetite was carried out and the obtained samples after direct reduction were analyzed by XRD and chemical composition. The result shows that the metallization rate of carbon-containing pellet is nearly 90%.

Mar 1, 2018

By P. Piga, O. Sammarco

There is a markedly increasing tendency to design deeper and deeper mines, to use larger amounts of explosive per round, to increase the advance rate of the excavations and so the natural ventilation tends to be more intense in the new mines. For this reason, the mines that make use of powerful mechanical ventilation should also take into account such factors as natural ventilation pressures, especially in the case of mines excavated in high-temperature rocks for which natural ventilation is particularly intense. The results of the studies reported here refer to a very hot mine excavated in an area with a high geothermal flow (the Boccheggiano - Campiano mine, southern Tuscany). At various external temperatures, experimental measurements and analyses have been made of the trend of the thermodynamic characteristics of the ventilation air and of the trends of the air/rock heat exchange along the downcast shaft and along the upcast shaft. These data were then used to work out approximate values of the corresponding natural ventilation pressures. After having identified the most conspicuous variations of the thermodynamic parameters of the ventilation air and the factors causing them, an assessment was made of the repercussions they have on the air flow rates and, above all, on the climatic conditions of the underground excavation sites. The natural ventilation pressures were found not to be constant in time; indeed they change continously and it is difficult to predict the changes. Moreover, it was found that their influence on the ventilation of a section of the mine network is greater if the effect of mechanical ventilation on that section is weaker. In the mine section where the measurements were carried out, some portions were found where the ventilation could become insufficient as a result of the effects of natural ventilation pressures. Finally, some guidelines to be followed in designing hot mines have been put forward which ensure efficient ventilation throughout the network at times with the aid of the natural ventilation pressures, which in certain circumstances may reach very high values in mines of this type.

Jan 1, 1987

By Nourreddine Menad

Plastic materials have been associated with electric and electronic applications since the early days of the electrical industry. Plastics can amount to 30 percents of the scrap mass. Generally, they are treated with flame retardants such as halogenated ones and they can result in different toxic chemical compounds. These plastics can be used as combustibles in the recovery of copper and precious metals. However, during their combustion, halogenated flame retardants can produce dibenzo-p-dioxins and dibenzo-furans. The estimated thermodynamic data of several organic compounds resulting from combustion of electric and electronic scrap, have been used in conjunction with the program HSC to calculate the conditions for dioxin and furan formation. The results show that the formation of the dioxins is dependent on the quantities of carbon, hydrogen, chlorine and oxygen reacting in a given system, as well as on parameters such as temperature and pressure.

Jan 1, 1998

By Eric Klaffenbach

Valorization of slag from metallurgical industrial processes becomes ever more important as this may help optimizing and reducing the use of natural resources such as rock and sand. In view of this objective, metallurgical processes have to be analyzed in order to modify the slag composition so that it will meet the expected requirements of potential users of these resources. This paper gives the results of a thermodynamic analysis of the flash smelting process to understand the impact of operational parameters on slag chemistry and elemental partitioning in the process. It is shown that an increase of the matte grade and temperature leads to higher deportment of Pb, Zn and As to the slag. With increasing matte grade the volatilization of these elements decreases. Furthermore, the results indicate an increasing solubility of Cu and S in slag at higher temperatures.

By Motohiro Horiguchi, Kazuo Ichii, Toshio Oishi

"As a fundamental study to prepare copper-based alloys with rare earths (RE: La, Gd, Nd, Ce and Y) without any inclusions, the solubility of rare earth in liquid copper was experimentally determined. Liquid copper alloys were equilibrated with carbon and rare earth carbide in a graphite crucible in an argon atmosphere at 1523-1873 K.Solubilities of rare earth in liquid copper were determined by approaching the equilibrium values from both the lower and the ·higher concentrations than those expected· in the preliminary experiments. They were expressed as a function of temperature. Carbon in Cu-RE alloy was also analyzed and thermodynamically discussed.IntroductionOver the past several years, the demand for highly conductive and high strength copper-based alloys, such as Cu-Cr, Cu-Zr and Cu-Cr-Zr for use in electronic materials has increased.1 -7 These alloying elements are very reactive and easily oxidized to form oxide inclusions during melting. To avoid the oxide inclusions, it may be effective to utilize the strong reducing power of carbon in conditions under which no carbides form.In this study, to provide fundamental data for producing Cu-RE( rare earth) alloys without any inclusions, the solubility of rare earth in liquid copper in equilibrium with .carbon .was determined and discussed on the basis of the experimental results and the thermodynamic data.ExperimentalSample preparation for equilibrium experimentsOxygen-free copper (99.99%), lanthanum (99.9%), gadolinium (99.9%), neodymium (99.9%), cerium (99.9%) and yttrium (99.9%), and their oxides were used as starting materials.Each rare earth carbide was prepared by mixing rare earth oxide with carbon, which is a little more than the stoichiometric composition, pressing it into a tablet form and sintering at about 2000.K for 20 ks in a vacuum furnace using a graphite crucible. Powder X-ray analysis showed that only the carbon and rare earth carbide (REC2) was present in each sample.Cu-RE mother alloys (5-20 mass % RE) were prepared beforehand by mixing metallic rare earth with oxygen-free copper, and melting in an electric arc furnace."

Jan 1, 2000

By Animesh Jha

Univariant diagrams are constructed for the reduction of nickel and cobalt oxide and sulphide minerals. The results from the carbothermic and hydrogen reduction of sulphide minerals are compared. The importance role of lime and calcium sulphate in controlling the emission of sulphurous- gases during reduction reaction is also explained. The mechanism of carbothermic reduction of nickel sulphide is explained by examining the sulphur exchange and reduction reactions. The phase equilibrium relationships that determine the formation of multicomponent liquid are characterised. Also the governing equilibria for inert atmosphere calcination- roasting of nickel and cobalt sulphide minerals are also described for the metallization of nickel and cobalt.

Jan 1, 1993

By Miao Tian

Large quantities of copper complex resources are produced globally and urgent to be cleanly processed. This article presents a thermodynamic analysis of mixed smelting process including low-grade polymetallic copper sulfide concentrates, high copper content sulfide concentrates, metallurgical by-products (copper removal slag from lead metallurgy), and copper powder from electronic waste. A top blown smelting reactor to simulate mixed smelting process is developed using a metallurgical process simulator, METSIM. Reactor parameters, heat loss and phase distributions are estimated from actual plant data. The proper proportion between complicated primary and secondary copper resources is determined by analyzing the influence of the feed rates of various resources, oxygen, silica flux and revert on the smelting performance. Autogenous smelting process is built by optimized matching materials of copper complex resources, in terms of the reactor temperature, copper content in matte and slag, and the percentage of magnetite in slag.

By A. D. Davis

Limestone-based material is effective for reducing arsenic concentrations below the current limit of 10 parts per billion for drinking water, typically resulting in final concentrations of about 4 to 6 ppb. However, in laboratory and field testing, further reductions to the 1 ppb range are difficult to achieve with limestone unless other material such as iron is added. The removal mechanism with untreated limestone appears to be the formation of a low-solubility precipitate of hydrated calcium arsenate, in the form of arsenate-apatite. Likely reactions and thermodynamic data indicate a theoretical removal limit of about 2 to 4 ppb for arsenic using raw limestone. Limestone also can reduce concentrations of cadmium and lead below 1 ppb in water, resulting in >99% removal efficiency. Thermodynamic constraints appear to be favorable for reactions involving the formation of otavite during cadmium removal and the formation of hydrocerussite during lead removal.

Feb 27, 2013

By L. B. Pankratz

Thermodynamic data on the elements, oxides, sulfides, halides, and selected hydrides, carbides, nitrides, carbonates, sulfates, silicates, and miscellaneous compounds were reviewed, evaluated, and compiled at the Bureau of Mines. Values for CP°, S°, H° -H°298, ?Hf°, and ?Gf° are given in tabular form. A brief thermodynamic background and a number of examples and applications are presented.

Jan 1, 1984