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By Michael Zinigrad

The quality of metallic materials depends on their composition and structure and these are determined by various physico-chemical and technological factors. To effectively prepare materials with required composition, structure and properties it is necessary to carry out a research in two parallel directions: Comprehensive analysis of thennodynamics, kineties and mechanisms of the processes taking place at the solid-liquid-gaseous phase interface during welding processes and development of mathematical models of the specific welding technologies. We have developed unique method of mathematical modeling of phase interaction at high temperatures. This method allows us to build models taking into account the thennodynamic characteristics of the processes, the influence of the initial composition and temperature on the equilibrium state of the reactions, the kinetics of heterogeneous processes, the influence of the temperature, composition, hydrodynamic and thennal factors on the velocity of the chemical and diffusion processes. The model can be implemented in the optimization of various technological processes in welding, surfacing, casting as well as in manufacturing of steels and non-ferrous alloys, materials refining, alloying with special additives, removing of non-metallic inclusions.

Jan 1, 2003

By U .. C. Rojas, J .. C. Gomez

"Fire Refined Copper (EI Teniente Three Stars) has been produced at Caletones Smelter of Codelco Chile since almost the beginning of its operations.Due to changing features of the copper market, together with the targets on technical efficiency and productivity, it has become more and more relevant for copper industry to reach both, good final product quality and a proper environmental control.At present, copper refining process at Caletones Smelter takes place in two cylindrical tilting furnaces, where solid fluxes are injected through horizontal tuyeres into the molten bath. (Fig. N2 1)Solid reagents are pneumatically conveyed and injected into the liquid copper bath attaining excellent solid - liquid contact, so the impurities removal efficiencies are found to be high. Same injection tuyeres are used to introduce both oxidising agent (normal air) and reducing agent (reformed gas) into the molten bath. Air or nitrogen is used as conveying gas for solid reagents, depending on the process stage.This pap~r gives a fundamental description of the process and industrial results related to the injection of blend of sodium and calcium carbonates to remove arsenic and antimony, silica and granulated reverberatory slag to remove lead and a mixture of calcium carbonate and mineral coal to reduce the selenium content of the fire refined copper."

Jan 1, 1996

By J. Brent Hiskey

Recently basic concepts of semiconductor electrochemistry and solid-state electronic structure theory have been applied to the dissolution of mineral electrodes. In this paper, fundamental aspects of semiconductor electro- chemistry and interfacial charge-transfer processes are reviewed. Information regarding the electronic and semiconductor properties of chalcopyrite is summarized. The electrochemical response of chalcopyrite in acidic solution is analyzed in terms of initial dissolution processes. The initial charge- transfer reaction involves the consumption of holes. It has been shorn that Fermi level pinning is consistent with observed electrochemical and dissolution behavior. Semiconductor electrochemistry has proved helpful in explaining the formation of intermediate surface films produced during the initial stages of chalcopyrite dissolution

Jan 1, 1993

By Veena Sahajwalla

The cupola furnace is a coke-fueled shaft furnace used as a primary melting unit in iron foundries. Control of chemical composition of the iron tapped from the cupola is a key factor in productivity and quality control. In an effort to develop a control model for the cupola, a fundamental approach based on physical and chemical principles has been taken to describe the melting process. The behavior of oxidation of the solid charge in the stack of the cupola has been studied. Sulfidation of the charge materials by sulfur-bearing components released to the furnace gases from the coke has been described. Carburization of metal droplets of iron and of steel in separate molten streams has been characterized. Finally, reactions with alloying elements in the hearth (well) of the furnace have been defined. These reactions have been described in a computer-implemented model developed to predict the composition of the iron tapped from the cupola. The model has utilized the thermodynamics and kinetics of the oxidation, sulfidation, and carburization reactions, including temperature and physical aspects, in the various zones of the melting unit. The model predictions have been compared favorably with operating results.

Jan 1, 1992

By René Winand

Due to chemical and electrochemical behavior of the most common additives in copper electrorefining i.e. gelatine, thiourea and chloride ions, it is essential to simulate as far as possible true industrial practice while performing laboratory experiments. The three additives must be studied simultaneously, and added continuously to the electrorefining cell. Ratio electrolyte volume to cathode area; ratio bleed flow to cathode area; hydrodynamic conditions; residence time of electrolyte in the cell; current density; electrolyte and soluble anode must be as near as possible to industrial ones. Experiments performed in the author's laboratory show that under these conditions, reproducible results can be obtained at normal industrial current density and at high current density as well. Problems are however still encountered when developing a sensor for additives monitoring, due to electrolyte redox potential and to substrate influenced thin layer deposition.

Jan 1, 1995

By Filippos Patsiogiannis

Laboratory size (5 kg) aluminum killed low carbon steel melts were desulfurized with synthetic fluxes in zirconia crucibles. The sulfur, oxygen, aluminum, silicon, and manganese contents in the melt were determined as a function of refining time and temperature. With a good argon shield and synthetic flux cover, melt reoxidation was not observed. Sulfur removal followed first order reaction kinetics. The effectiveness of calcia saturated calcium-aluminate (12CaO.7Al2O3) based fluxes in desulfurizing the steel melts was evaluated. The effects of initial sulfur level of the melt, weight of the flux (slag), and additions of tellurium, fluorspar, and barium oxide to the melt on the kinetics of desulfurization were also studied.

Jan 1, 1993

By Esperidiana A. B. Moura, Célio H. Wataya, Roberta A. Lima, Rene R. Oliveira

The purpose of this study was to investigate the mechanical, morphological and thermal properties of biodegradable composites based on aliphatic-aromatic copolyester/polylatic acid blends (PBAT/PLA blends) reinforced by açaí seed fibers, an abundant byproduct of the açaí fruit agro industry. The biodegradable polymeric composites were prepared by melting extrusion process using a twin-screw extruder machine. The fibers removed from the açaí seed were used as the reinforcement and PBAT/PLA blends as the matrix. The influence of the açaí seed fibers addition on properties of composites was investigated by tensile and impact tests, SEM, DSC, and XRD analysis. Correlation between properties was discussed. In addition, açaí seed fibers characterization by SEM, XRD and WDXRF have also been carried out. The addition of açaí seed fibers on biodegradable PBAT/PLA blends showed that it is possible to get interesting property gains in biodegradable polymer by using waste from renewable sources.

Jan 1, 2015

By V. P. Bystrov

Vanyukov process has been developed and investigated in Russia over the last 25 years. It has been established that various kind of material could be treated in Vanyukov process. The results of the pilot plant trials as well as industrial experience are presented in this paper.

Jan 1, 1993

By B. Mishra, W. A. Averill

"The application of various hydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, ego metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been investigated and suggested for dealing with some of these wastes and scrap material.The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EM] and decontamination and decommissioning [D&D].IntroductionThe high temperature carbothermic or metallothermic smelting reduction methods for metal production are associated with the generation of significant quantity of waste as slags, flue dusts, sludges, residues, effluent salts etc. Certain hydrometallurgical processes also generate lots of aqueous waste due to the inherent nature of the technique. Also, the gas-based reduction processes are not applicable to many stable metal compounds, such as alumina, titania, beryllia, lanthanide and actinide oxides, etc. due to thermodynamic considerations. All these methods cause substantial environmental hazard. There is a need to develop alternative processes which have low waste or ideally a ""zero-waste"" generation.Pyrochemical processes using molten salts provide a unique opportunity for the extraction and refining of many reactive and valuable metals either directly from the beneficiated ore (aluminum, beryllium, neodymium, plutonium, uranium, etc.) or from other process effluent that contain reactive metal compounds. The processes reduce metal compounds electrolytically (A12O 3 and BeCI2) on a carbon anode or by calciothermic reduction (Po, Nd). The by-product, in the latter case, is a calcium oxide saturated halide salt. The waste-treatment to recycle the halide has to be done as a separate step or stored as a contaminated waste. A successful separation technology can provide a new insight to the waste minimization strategy for the nuclear industry."

Jan 1, 1996

By D. Papazoglou

This work was undertaken to investigate the thermodynamic and kinetic feasibility of using hot sulfur dioxide bearing gases from smelting processes to selectively sulfate the nickel in nickel laterite ores for subsequent extraction in water. The environmental benefits ofthis approach, as opposed to releasing the gas to the atmosphere, and the economic benefit of directly utilizing the S02 rather than converting it to sulfuric acid are strong drivers for such a process. A thermodynamic analysis indicated that selective sulfation of the nickel could be feasible under appropriate conditions and these were explored through a series of laboratory scale experiments. Laterite samples were reacted at temperatures between 500 and 800°C with an equilibrated mixture of sulfur dioxide, oxygen and nitrogen in a fixed bed reactor. Tests were conducted on saprolitic ore from Bulong, Western Australia, limonitic ore from New Caledonia and garnieritic ore from Indonesia. Nickel extractions were highest from the limonite and relatively low from the other ores. The maximum selective extraction of nickel from the limonite in a single stage sulfation was 73%. Sulfation of other elements present in the laterites was also examined. A two-stage process was also identified which involved sulfation using a strong sulfation potential followed by weaker sulfation potential to attempt to convert ferric sulfate formed in the first stage to ferric oxide. This increased the extraction for the limonite ore to around 84% Ni, 95% Co and 2% Fe. Direct sulfation of laterite could be feasible in locations where sulfide smelting or roasting operations are relatively close to laterite deposits.

Jan 1, 2003

By Lauri Holappa

Copper converting is mostly performed in Peirce-Smith converters. The process is still very similar to the original one developed in the early 20th century. It is a batch process in a horizontal cylindrical reactor with air blowing via tuyeres along the length of the reactor side. The Peirce-Smith converter has its roots in Bessemer's inventions in the 1850's as he tested both horizontal and vertical vessels for steel converting. However, for steel making a vertical pear-shaped converter with air bottom-blowing was established. In the course of time, there was a distinct necessity for oxygen usage instead of air due to harmful effects of nitrogen to steel properties and its cooling effect. In-bath blowing of oxygen did not succeed, however, and top-blown oxygen converter with oxygen lance (LD or BOF) was first developed in he 1950's and emerged rapidly to a dominating position. Somewhat later oxygen bottom-blowing via special shrouded tuyeres was developed (OBM or Q-BOP) but has attained only fractional share. Bottom-blowing technique had, however, impact on the current combined blown converters which adopted the benefits of both top and bottom blowing. In copper converting Peirce-Smith type converters have kept their position until today although new processes have been introduced and at least few of them seem to be emerging. In one respect copper converting has a clear leading position i.e. in the progress of continuous converting processes (Mitsubishi, Ausmelt). These processes utilise top-blowing lances instead of in-bath blowing tuyeres. A different principle for continuous converting is flash converting by Kennecott Outokumpu, which makes smelting and converting independent of each others. Solid ground matte is used as a feed for flash converting in a reactor shaft similar to Outokumpu matte flash smelting. A comparable process has been presented by Inco too. The paper discusses principal physico-chemical and process technical similarities and differences in copper and steel converting. Although these processes are metallurgically quite different it seems that during the modem history of ferrous and non-ferrous metallurgy, starting from the 1850's, the exchange of knowledge between these disciplines has been quite intensive. In long-term perspective, many similarities in the development can be found but also divergences due to different ambient circumstances.

Jan 1, 2003

By P. Chris Pistorius

An example is presented to illustrate the joint effect of local reaction equilibria and mass transfer limitations, for reactions during ladle refining of steel. The example relies on some of the kinetic principles that David Robertson has employed to quantify many metallurgical processes. In calcium treatment of alumina inclusions in aluminum-killed steels, solid CaS forms as an intermediate reaction product. During subsequent reaction, CaS disappears and calcium aluminate forms; at the same time, aluminum and sulfur dissolve in the steel. Kinetic analysis shows that the rate of this reaction is not limited by mass transfer of dissolved aluminum and sulfur away from the reacting inclusions. The reaction rate is likely limited by transport of dissolved calcium. This example also illustrates the use of FactSage macros for kinetic modeling.

Jan 1, 2014

By A. V. Reddy, C. Beckermann

"The DC continuous casting of a grain refined AI-4.5%Cu round ingot with realistic boundary conditions is numerically simulated. Of particular interest are the effects of the transport of free solid in the form of equiaxed grains on the macro segregation patterns and the final grain size distribution. The study uses a previously developed two-phase model that incorporates descriptions of heat transfer, solute redistribution, melt convection, and solid transport on the system scale with microscopic models of solutal undercooling, microsegregation and grain impingement. The numerical results indicate that grain transport inhibits the formation of inverse segregation in the ingot shell and promotes negative centerline segregation. This is explained by the reduction in the solid coherency next to the mold and the advection of solute-lean grains towards the centerline. Comparisons with the experiments of Finn et al. [5] illustrate the need for considerable improvements in the model. IntroductionMacrosegregation continues to be one of the concerns in DC continuous casting of aluminum ingots. The variation in composition over the ingot cross section results in the need to adjust alloy composition in order to meet mechanical property specifications in finished products. The extent of macrosegregation is greatly affected by the casting conditions, such as casting speed, superheat, cooling rate, mold size, alloy composition, and grain refining practices. Thus, it is of great interest to develop a comprehensive mathematical model to simulate the casting process, enabling the selection of conditions that minimize macrosegregation while maintaining a high productivity."

Jan 1, 1994

By James P. Bennett

EAF slag chemistry and its control have been recognized as important in producing quality steel at a low price for a number of decades_ EAF steel producers make lime and dolomite additions to furnaces, controlling the CIS ratios and sulfur pickup from the steel. Existing phase diagram data at 1600°C for CaO, MgO, FeO, SiO2, and Al2O3 was used to write a computer model optimizing slag chemistry for slag foaming and reduced refractory wear. The model, its development, and its use in an industrial steelmaking environment will be discussed along with how the model can improve energy efficiency. The importance of EAF mass balance to account for critical materials like Si in scrap and refractory wear using the model will also be emphasized_

Jan 1, 2003

By T. T. Chen

Hydrometallurgical products are difficult to characterize because of their fine grain sizes, heterogeneity, often amorphous structures and water soluble or hydrated constituents. Such products are advantageously studied using complementary mineralogical techniques including >50, ore microscopy, SEM-EDX, electron microprobe analysis, selective leaching and wet chemical analysis to determine the phases and their morphologies, to identify specific element carriers, and to elucidate the chemical reactions occurring during the metallurgical process. Sample preparation is an important consideration for these materials. For extremely fine-grained particles, or soft and brittle products such as elemental sulphur, the study of loose powder mounts provides information not available from the examination of polished sections. To demonstrate the application of the various mineralogical techniques, commercial zinc roaster calcines and leach residues, copper refinery anodes and anode slimes, and laboratory bornite leach residues were examined in detail. The various sample preparation and mineralogical methods are presented, and the use of these complementary and practical mineralogical techniques to improve the understanding of a particular hydrometallurgical system is discussed.

Jan 1, 1989

By Satu Jyrkönen

A single-particle laminar-flow technique was used to study reactions of sulfidic nickel particles. The studied materials were three natural nickel concentrates and four synthesised nickel mattes. The variables of the experiments were the gas preheating temperature (500 - 1300°C), the composition of the reaction gas (N2 + 0 - 75 vol-% 02) and the ,particle size of the feed. Chemical analysis of the particles was used to determine the oxidation degree of the materials, and optical and scanning electron microscopy were used to detect alteration in their morphology, internal composition and structure. General reactivity of the materials was monitored by the extent of sulfur removal. The reaction mechanism of the studied materials was found to depend primarily on the materials composition as well as oxygen content of the reaction gas.

Jan 1, 1998

By D. Lui, B. G. Thomas, B. Ho

"Results from mathematical models and plant experiments are combined to quantify the effect of transverse depressions and oscillation marks on heat transfer in the continuous casting mold. A heat transfer model has been developed to calculate transient heat conduction within the solidifying steel, coupled with the steady-state heat conduction with the continuous casting mold wall. The model features a detailed treatment of the interfacial gap between the shell and mold, including mass and momentum balances on the solid and liquid powder layers. The model predicts the solidified shell thickness down the mold, temperature in the mold and shell, thickness of the resolidified and liquid powder layers, heat flux distribution down the mold, mold water temperature rise, ideal taper of the mold walls, and other related phenomena. The important effect of non-uniform distribution of superheat is incorporated using the results from previous 3-D turbulent fluid flow calculations within the liquid cavity. Results from plant experiments confirm that transverse surface depressions and oscillation marks form at the meniscus and move down the mold. Measurements of mold thermocouple temperatures and breakout shell thickness were used to calibrate the models. The results indicate that the surface depressions and oscillation marks are filled with mold flux, but still have a significant effect on decreasing heat transfer. The predicted mold temperature fluctuations are consistent with measurements. If the depressions become filled with air, their effect is greatly increased. These results should be useful in the difficult task of interpreting transient mold thermocouple signals for on-line quality monitoring.IntroductionMany different types of intermittent surface defects on steel slabs arise during initial solidification in the mold of the. continuous casting machine. These defects include deep oscillation marks, surface depressions, and cracks. They may lead to quality problems, such as slivers, in the final rolled product. In severe cases, breakouts may occur, where liquid steel bursts through a thin section of the shell and drains over the casting machine below the mold."

Jan 1, 1997

By V. P. Keran

The lead and copper smelting processes employed by Mount Isa Mines Limited, Mount Isa, Australia, are used to illustrate an operating viewpoint of some problems and solutions encountered in existing commercial sulphide smelters. The smelting processes discussed; include updraught sintering, blast furnace and reverberatory smelting, and converting. Selected examples are given of methods implemented, and options available, to improve the productivity and efficiency of conventional smelting processes.

Jan 1, 1983

The cleaning of copper containing fayalite slag using a CuFe alloy was studied under an oxygen pressure ranging from 10-7 to 5 X 10-11 atm at 1200º c. The reduction of copper from fayalite slags by Cu-Fe alloys was found to be very effective. For example, at a P 02 of 10-7 atm, the copper content in the slag was reduced from 4.1 to 0.402 wt. percent after 90 min. of reaction time using a Cu- 5.27 wt. percent Fe alloy. The copper reduction rates were found to be independent of P02 in the gas phase when using Cu-Fe alloys which exhibit an iron activity of greater than 0.4. A mechanism for slag c1eaning is proposed based on the concept that the Cu-Fe alloy lowers the oxygen potential of the slag according to Eq.1 1, fol1owed by the reduction of cuprous oxide by wustite as shown in Eq.2. Here X represents element X in the alloy phase while (X) represents the element in the slag phase. The copper and iron transfer behaviour obtained in this study are explained by a ?Stepwise equilibrium model.

Jan 1, 1985

By S. R. Reddy

Thennodynamic properties of several quaternary systems are calculated using our recently modified Margules equations. The modified Margules equations are expressed up to infinite order in the vicinity of solvent. Quaternary system of one solvent and three,solute partials are derived. First order interaction coefficients of binary, ternary and cross -interaction parameters of quaternary system are used to'evaluate the partial functions. In the original fonn of Margules equations,derived partial functions are convergent and same 'as Unified ,Interaction Parameter Fonnalism. But considering up to infinite order of the Margules coefficients, the functions are divergent, in order to overcome this restriction, Margules equations are modified to get consistent equations. Derived partial functions are thennodynamica Hy consistent with Maxwell and Gibbs Duhem relations. The derived logarithmic activity coefficient of the solvent and solutes are consistent with the ternary systems. The calculated data, ie., activity coefficient values of nitrogen and interaction coefficients are in good agreement with the data of Fe-Cr-V -N. Fe-Ni-V -N, Fe-Cr-Ta-N and Fe-Ni-Ta-N systems.

Jan 1, 1999