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By Dilek Kirgöz, Onuralp Yücel, Murat Alkan

"In this study, Mo containing Fe-based alloys, such as Fe-Ni-Cr-Mo, were synthesized using a mixture of Fe203-NiO-Cr203-Mo03 powders reducing with Al powders by metallothermic process which is a high energy efficient, fast and low-cost production technique for synthesis of cast alloys and advanced ceramics. Detailed thermochemical studies were simulated by using FactSage 6.2 Thermochemical software in order to calculate adiabatic temperature of the reactions and effects of initial molar composition on the final products. In the metallothermic processes, effects of stoichiometric Al addition and addition of the oxide powders (Alz03, Si02, CaO, MgO) on the metal recovery and compositions of final alloys were carried out. Final products were characterized by using chemical analysis (AAS), XRD, XRF and SEM/EDS techniques.IntroductionSelf Propagating High Temperature Synthesis (SHS) has significant advantages compared to the high technology furnace applications, such as very short processing time, simple operation, low energy requirement and low cost [l, 2]. In a SHS process, the ignition starts the combustion and propagates throughout the reactant mixture yielding the desired product. However, the disadvantages of the process such as inhomogeneous or unreacted products due to undesirable reaction rates needs to be overcome by changing some parameters such as ignition temperature, particle size, additive, atmosphere etc. [3, 4]. This work aims to establish a scientific and engineering background in the production of some cast Fe based alloys (Fe-Ni-Cr-Mo) which are used as surface coatings, wear-corrosion-oxidation resistive applications via SHS (Self Propagating High Temperature Synthesis) metallurgy which is attractive process technique regarding fast and low-cost production ability of cast alloys."

Jan 1, 2013

By Versiane Albis Leão

This work aims at the selection of an appropriate eluant for cyanide recycling using ion exchange resins. Based on a literature review as well as on experimental results, the elution of resins loaded with copper and minor amounts of iron and nickel is discussed. The resins Imac HP 555s, Amberlite IRA 900 (Rohm&Hass) and Purolite A860S (Purolite Co) were eluted using either NaCI, zinc and nickel cyanides, hydrochloric acid, sulfuric acid or acid thiourea solutions. The results indicate that saline solutions are effective only with polyacrylic resins (Purolite A860S), failing to desorb the metals, specially the nickel cyanocomplex, loaded on polystyrene-based resins. Cyanide solutions of both zinc and nickel are capable of eluting over 90% of the loaded metals. In contact with pure acid' solutions, iron precipitates onto the resin beads, as Cu(II) ferrous cyanideCu2Fe(CN)6.xH20. Thiourea is able to elute all the three metal cyanocomplexes owing to the increased solubility of copper cyanocomplexes in the presence of this complexing agent. The results demonstrate that a universal eluant is not available and the selection of the most appropriate resin-elution procedure should be based on the specific features of the system under consideration

Jan 1, 1998

By Pengfu Tan

In order to understand and control the formation of dioxins and furans in iron ore sinter plants and to possibly avoid expensive end-of-pipe removal stages, thermodynamic calculations on the stability of PCDD/Fs have been combined with sinter process modeling by means of kinetic simulations and computational fluid dynamics. Three thermodynamic databases of PCDD/Fs, derived using the Group Additivity approach and two computational molecular modeling methods, MNDO and PM3, respectively, combined with the SGTE database have been used to model the PCDDIF formation and the PCDD/F isomer distributions in iron ore sintering. The results show very similar conditions for the PCDD/F formation using the different databases. Concerning the isomer distributions of toxic PCDD/Fs, the calculated data derived from the MNDO method showed optimum agreement with measured values from industrial furnaces. The thermodynamic calculations also proved that the isomer distributions found in combustion processes are equilibrium values, while the concentration ratio of PCDDs and PCDFs in the wind boxes does not represent an equilibrium state. A CFD model of iron ore sintering was developed including the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. On the basis of these information and experimental observations reported in the literature possible pathways for the PCDD/F formation in sinter plants have been identified: PCDD/Fs are formed in the critical temperature region of 250 to 450°C below the combustion zone, are then carried downwards with the gas and condensed close to the bottom of the sinter bed. Transported to the discharge end with the solid mixture, they are again released into the gas phase when the flame front approaches the bottom. PCDD/Fs are also formed in the last wind boxes when the hot off-gases cool down and reach the critical temperature range. Consequently, methods to reduce the dioxin formation reactions are proposed including inhibitor addition to the sinter feed and off-gas quenching.

Jan 1, 2003

A novel process is being developed for metal recovery from waste electrical and electronic equipment involving a leach reactor coupled to an electrochemical reactor. Metals such as Ag, Au, Cu, Pb, Pd, Sn etc. are dissolved from shredded electronic scrap in an acidic aqueous chloride electrolyte by oxidising them with aqueous dissolved chlorine species. In the electrochemical reactor: (i) chlorine is generated at the anode for use as the oxidant in the leach reactor, and, simultaneously, (ii) at the cathode, the dissolved metals are electrodeposited from the leach solution. The extended Butler-Volmer equation was used to provide predictions of the electrode potential dependences of partial current densities and, hence, total current densities, current efficiencies and alloy compositions for acidic aqueous chloride electrolytes containing Ag(I), Au(III), Cu(II), Pb(II), Pd(IV) and Sn(IV) species, together with dissolved chlorine. With judicious choice of kinetic parameters, the predicted total current density ? electrode potential behaviour of such solutions was in good agreement with experimental data for a rotating Pt disc electrode. Reduction of dissolved chlorine at a Pt rotating disc electrode exhibited mass transport controlled behaviour, in agreement with Levich?s equation over the potential range 0.3-0.9 V (SHE). This could form the basis of a linear sensor, possibly using a microelectrode for measurement and control of the dissolved chlorine concentration in the efflux of leach reactors and inlet to electrowinning reactors in the envisaged process.

Jan 1, 2003

By T. T. Chen

Raw anode slimes consisting primarily of PbSO4, AgCuSe, Cu3Se2, Cu2-x Se, Cu2O, CuSO4.5H2O, Sn arsenate and Sb-Bi-As oxide are batch-leached with electrolyte-O2 to dissolve Cu. During this process, Cu2O and CuSO4.5H2O are solubilized and the Cu in the selenides is leached with the formation of Ag2Se and Se. A small amount of Cu remains in the Ag2Se, Sn arsenate and Sb-Bi-As oxide. The decopperized slimes are repulped in Na2CO3 solution to convert most of the PbSO4 to NaPb2(CO3)2(OH). The Sn arsenate and Sb-Bi-As oxide partly react, but the Ag2Se is not significantly affected by the Na2CO3 solution. The NaPb2(CO3)2(OH) intermediate phase is dissolved in acetic acid to leave a final product consisting of Ag2Se, Se, Sn arsenate and Sb-Bi-As oxide, together with small amounts of PbSO4, NaPb2(CO3)2(OH) and various gangue constituents.

Jan 1, 1993

By Y. A. Chang

The objective of the present study is to evaluate and compile the relevant phase equilibria and thermodynamic data reported in the literature for the ternary system Cu-Fe-S. It is hoped that the results presented here will be useful to practising engineers and scientists in industry who are attempting to improve continually the existing processes of copper extraction and refining. At the same time, the present work will undoubtedly reveal the lack of some basic data which are important for the improvement of our existing extractive processes. Lastly, this work will also show that the development of theoretical models for the alloy phases in the Cu-Fe-S system is essential before complete consistency between the phase equilibria and the thermodynamic data can be achieved.

Jan 1, 1976

By E. vanHuyssteen

A method of establishing the relationship between the mineralogy of a sinter and its subsequent processing behaviour in a lead blast furnace is demonstrated. It involves: 1) analyzing the Zn-spinels, hardystonite, larsenite, Pb-silicates, Pb-arsenates, Pb-(Ca)-sulphates and other femtes with an electron microprobe; 2) determining the extent of elemental substitutions in various mineral structures; 3) establishing a sequence in which the various phases formed during sintering. In this manner the relationship between the bulk chemistry of a sinter formulation and the speciation of elements into various phases in the sinter can be established. Specifically, the-substitution of Mg for Zn in hardystonite significantly influences sinter production. Mg substitution releases Zn into the surrounding matrix. This Zn reacts with the Pb-silicate to form larsenite thereby reducing the amount of Pb-silicate available for anhydrite digestion. Excessive amounts of residual anhydrite thus result if the sinter formulation is based solely on the CaO/Si& ratio.

Jan 1, 1993

By W. G. Davenport

Chapter 13 evaluated the %02 in blast, industrial oxygen and oil requirements for smelting FeSrCuFeS2 concentrates~ This chapter examines high eu grade CU2S-CuFeS2 concentrates the same way.

Jan 1, 2001

By J. R. Donald

Surface and interfacial phenomena play a significant role in refractory performance. For example, the wettability of the refractory material with slag, matte, and metal influences infiltration and interfacial reactions. Yet, very little fundamental information regarding the surface properties of refractory materials and slag is available. Thus, in the present work, the sessile drop technique incorporating a high temperature furnace equipped with X-ray fluorescope was employed to investigate the surface and interfacial phenomena of fayalite-type slags on solid alumina at 1200?C. The iron to silica (Fe/SiO,) ratios employed were 1.4 and 2.0, and the oxygen potentials used were log p02 =-11 and log p02=-9 atmospheres. The contact angle between the fayalite-type slags and the alumina were determined to be relatively low, at about 16.9 to 19.6 degrees under the experimental conditions. The surface tension of fayalite slag (Fe/SiO2=1.4) at an oxygen potential of log -11 was 0.298, which agreed with the work of previous researchers. The surface tension of the fayalite was observed to increase with time. The spinel FeAl2O4. was determined to be the product of the interfacial reaction, and 8.8 to 15.8 mass percent alumina was dissolved into the slag after 40 minutes.

Jan 1, 1996

By Michael L. Sorokin

The behaviour of cobalt during processing of nickel raw material is analysed within the Ni-Co-Fe-S-O-SiO2 system using the computer model. For this purpose the thermodynamic parameters for "three-suffix" Margules's equations in Co-Fe-S and Co-Fe¬Ni-O-S1O2 systems were computed! Phase and iso-activity diagrams for Co-Fe-S system, and phase diagrams for the systems Co-O, Co-Fe-O, Co-Ni-O, C-oO=SiO2 and Co-Fe-O¬SiO2 are calculated using the developed computer programs and identified parameters. The diagrams are used to analyze cobalt behaviour at smelting and converting.

Jan 1, 1995

By T. Wang, R. G. Reddy, D. Mantha

"A new eutectic LiN03-NaN03-KN03-KN02 quaternary molten salt system was calculated using thermodynamic modeling. The eutectic temperature was predicted to be 100°C. The melting point and heat capacity of the salt eutectic composition were determined using DSC. The experimentally determined melting point is in excellent agreement with the predicted value. The melting point is more than 124°C lower than that of the KN03-NaN03 solar salt. The density of the molten salt was experimentally determined as function of temperature. Using the density, heat capacity and the melting point, thermal energy storage density and gravimetric storage density of the quaternary molten salt were calculated and compared with that of solar salt. The larger storage density value of this molten salt indicates that this salt has a better energy storage capacity for solar power generation systems.IntroductionMolten salts have been used as thermal energy storage media for solar energy applications. Nitrates are being used in the solar energy applications for their low melting point, low unit cost, high heat capacity, high thermal stability, negligible vapor pressure and high energy storage density [l]. Solar salt (NaN03/KN03: 60/40) is the most popular thermal energy storage medium which is currently being used with the freezing point of 221 ·c [2]; another ternary system HITEC® which contains NaN03, KN03 and NaN02 has freezing point of 141°C [3]. Newer nitrate salt mixtures are being studied and projected as potential candidates for thermal energy storage (TES) and heat transfer (HT) applications. Based on these favorable features, molten salt can work directly as the energy storage medium below 500°C [l]. Development and synthesis of newer molten salt mixtures with freezing point lower than those currently used for thermal energy storage applications is necessary for sustained utilization of solar energy. The approach to develop lower freezing point molten salt mixtures is by the prediction of new eutectic mixtures and also by the development of new nitrate compounds."

Jan 1, 2012

By Gavin K. W. Freeman

The efficient separation of cobalt from nickel is a fundamental objective in the refining of cobalt. Based on recent experience at the Corefco refinery in Fort Saskatchewan, the identification of a novel process for the selective precipitation of cobalt from aqueous ammonia leach liquors is described. The addition of calcium sulphate, CaSO4.2H2O (gypsum), to an aqueous solution containing cobalt(III) hexammine sulphate, [Co(NH3)6]2(SO4)3, will result in the precipitation of a sparingly soluble double salt having the stoichiometry, [Co(NH3)6]2(SO4)3.2CaSO4.xH2O, where x = 4 or 6. Leach residues, which may contain a significant quantity of cobalt associated with the cobalt calcium double salt, can be washed with process solutions that contain ammonium carbonate. After contact with ammonium carbonate, the cobalt is recovered into solution, while the calcium is re-precipitated as the insoluble carbonate. The simplicity of this elemental separation and its high selectivity for cobalt, as well as the demonstrated usefulness in improving cobalt recoveries, are the basis for the potential applications of this process.

Jan 1, 2003

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, PSo, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of O2 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By Peter Koh

The velocity solid charge attains when dropping down concentrate chutes is an important boundary condition when developing mathematical models of flash furnace burners and reaction shafts. In this work an experimental rig was developed to measure the velocity attained when nickel concentrate and sand were dropped down a vertical pipe 3m long. The velocity measurements showed that the nickel concentrate did not fall as individual particles. The measured values of the velocity approached, but did not attain, those calculated for solid bodies, the disparity being attributed to friction at the pipe wall and fluid drag losses. After falling 2 m velocities between 5-6 m/s were attained. The analysis was extended and applied to understanding the intermittent problem of puffing which sometimes occurs from the top of the concentrate chute. The pressure at the bottom of the chute is the net result of two opposing pressures, namely that developed by (a)the process air entering through the velocity control device, and (b) the solids falling down the concentrate chute. Flow back up the chute occurs when the former exceeds the latter. The process air pressures in the burner were obtained from CFD simulations of a full burner. Variables considered included air speed through the velocity control device, drop height and furnace draft. The analysis was useful in highlighting the operating conditions which were conducive to puffing and in establishing procedures to minimise its occurrence.

Jan 1, 2006

By Jiayan Li, Yi Tan, Yao Liu, Yaqiong Li, Shenrui Wu

"A metallurgical grade silicon (MG-Si) refining concept process was presented. Under vacuum conditions, silicon was selectively oxidized by high purity silicon dioxide to form gaseous silicon monoxide while impurities with low vapor pressure in MG-Si were rejected in residue; Then high purity silicon was obtained from the disproportionation of condensed silicon monoxide; and by-produced silicon dioxide was recycled for the oxidation step. Thermodynamics on boron rejection during the oxidation were studied in this work. In the temperature range of 1200-1800K, the saturated vapor pressure of boron, and the Gibbs free energy changes, the equilibrium partial pressures of silicon monoxide and boron oxides of potential reactions were calculated. And the effect of boron activity in MG-Si was also discussed. The results indicated that boron in MG-Si can be rejected during the oxidation and it showed the potential for the further development of the new refining process.IntroductionAs global energy consumption growing dramatically, higher prices of energy and global warming problem have attracted more and more attention [1]. As a clean and renewable energy industry, the photovoltaic (PV) industry converts solar energy to electricity using solar cell device and has a growth rate of about 30% in recent years. It has caused a shortage of silicon feedstock due to that about 90% of solar cells are made of crystalline silicon. And high energy consumption during the production of silicon material, i.e. solar grade silicon (SoG-Si), is main obstacle for its mass production."

Jan 1, 2012

By R. K. F. Lam

Unacceptable levels of impurity were noted in high purity chromium melting. Analysis of recent melting data determined that oxygen content in chromium is the critical parameter. Thermodynamics studies identify zirconia to be the most stable oxide in the presence of liquid chromium, followed by alumina and silica. Iron oxide reacts readily with liquid Cr. A certain degree of chemical reaction between liquid chromium and oxides does occur, contamination by the crucible is therefore unavoidable. Equilibrium constants indicate that a chromium oxide addition decreases 'ceramic dissolution and reduces impurity contamination. Safe operating conditions with oxygen content between 1190 ppm and 2500 ppm were identified. Additions of chromium oxide (Cr2O3) of 161 grams and 264 grams to liquid chromium yielded acceptable levels of impurity, and oxygen content was respectively increased to 1624 ppm and 2 179 ppm. A new process of melting high purity chromium with chromium oxide addition for controlling the activity of Cr2O3 is recommended.

Jan 1, 1997

By R. W. McCallum, B. Jensen, K. W. Dennis

"There are substantial challenges in the exploration of magnetic materials in the R-TM-X system (R =rare earth, TM= transition metal, X =stabilizing element) where Xis an element which has high vapor pressure, high reactivity, toxicity, or a refractory nature. This research focuses on discovering new phases with high anisotropy and high magnetization through closed diffusion couples inside high purity Fe crucibles. Either vapor-solid reactions or powder metallurgy techniques are then employed to isolate a stoichiometric sample based on a potentially magnetic phase found in the diffusion couple. For this research, X = F, Ca, Sr, Se, Zn, Bi or Cd, TM= Fe, and R = Nd. New ternary phases have been discovered with WDS and EDS, and magnetic transition temperatures have been measured with a SQUID magnetometer and VSM.IntroductionSince the discovery of the RCo5 compounds in the 1960s, rare earth- transition metal (R-TM) magnets have been the main focus of permanent magnetic research over the last five decades. Iron-based magnetic materials were studied next in attempts to avoid the unstable price of cobalt as well as the high price of Sm, the top performer in the RCos and RzC011 series. This hunt eventually led to the discovery of Nd2Fe14B with a theoretical BHmax of 64 MGOe, nearly double that of the previous samarium based magnets. The next few decades were devoted to enhancing the magnetic properties ofNd2Fe14B by the improvement of processing techniques and the additions of alloying elements. The only complete elemental substitution discovered in this system was R1Fe14C, which did not improve magnetic properties. It is probably safe to say that most ternary R-TM-X systems, where Xis any element that may stabilize a ternary phase, have been investigated if they may be prepared by conventional processes such as arc or induction melting. The present study offers a systematic approach to developing a novel diffusion couple technique in which the volatile, reactive or toxic alloying elements are laser welded inside a high purity Fe crucible. This experimental setup will prevent the oxidation of the rare earth element, as well as contain the volatile X element. As the goal of the research was to find new rare earth permanent magnets, only phases which contained greater than 60 wt% Fe were investigated. 247"

Jan 1, 2012

By Salustio s. Guzman

The standard .free energies of formation of tin chlorides were estimated with reviewed and estimated basic thermodynamic data, and measured reversible potentials for the disproportionation of tin dichloride into metallic tin and tin tetrachloride. Values for cºp, Sº, Hº?-Hº 298, -(Gº - Hº298) /T,.Hºf, Gºf, and log Kp are given in tabular form, these estimations are compared with estimations reported in the literature.

Jan 1, 1985

By Lauri E. K. Holappa

The aim of the metallurgical process development is, nowadays, to search for the shortest, most economical, more environmentally friendly and sustainable route to convert raw materials to finished products. Recent progress in steelmaking processes ? BOF and EAF - has also motivated to search for more advanced casting technologies to shorten process route. Continuous casting, which became industrially feasible in the 1960s, is now a mainstream technology with over 90% share of the world steel casting. After the 1980s, the increase in steel production and consumption, particularly from automobile, construction and home appliances industries, required steel manufacturers to accelerate production with more concise procedures, so that near-net-shape casting took the trend of development in order to bypass and simplify the downstream processes, e.g. cold/hot rolling mill or extrusion mill, to directly obtain finished products with required geometries. Progress in flat and long products changed the industrial operation pattern, strengthened steel production efficiency, and formed the operation concepts of the integrated steelworks and mini-mills, respectively. Thin slab casting and strip casting have represented the most important progress and promise, in the recent years, of such innovations furthermore strengthening the production efficiency and, concurrently, coinciding with the demands of environmental protection and sustainability. This paper reviews the most recent progresses in near-net-shape casting and prospects the impacts to steel industries as well as the development trends of steel production, in general.

Jan 1, 2006

By J. K. S. Tee

Using a novel method, zinc has been selectively removed from galvanized steel scrap on a laboratory scale. The separation is based on thermodynamic principles: during chlorination in air-chlorine (10:l) mixtures at 800 OC, zinc forms a volatile product (zinc chloride) while iron does not chlorinate as its oxides are more stable than the respective chlorides. As much as 92 % of zinc is removed from the surface of steel within 10 minutes. This process overcomes tedious and costly preparatory stages associated with leaching - electrowinning methods.

Jan 1, 1999