Search Documents

By T. C. Tseng

Austenitization is a critical stage in heat treatment of steels. The available kinetic data in reference to various initial microstructures are very limited, particularly at high heating rates. In this study, integrated experimental and computational approaches have been conducted to quantify the progress of austenitization and the attained microstructure. In particular, the study is concentrated on cementite and carbide dissolution in two steel grades. Various computational methods are developed to facilitate the study: (l) an algorithm for direct determination of kinetics data as well as progress of transformation from high-rate dilatometer tests; and (2) a suite of mesoscale computational models for particle dissolution, elements diffusion, mechanics, thermodynamic and the resulting kinetics of transfonnation. Critical exprimentation is carried out using advanced techniques in microstructure characterization, chemical analysis, and Gleeble thermal-mechanical simulator on specimens of well-controlled initial microstructures. Keynotes: Cementite, Carbite, Dissolution, Steels, Austenitization

Jan 1, 2003

In low carbon TRIP steels, the formation of carbide-free bainitic ferrite is crucial for the stabilization of austenite. Based on experimental investigations modeling the bainite reaction is examined adopting diffusional and displacive mechanisms, as well as the semi-empirical JMAK approach. Transformation tests were carried out to study the isothermal austenite decomposition into bainitic ferrite for a model steel containing 0.6wt%C, 1.5wt%Mm and 1.5wt%Si which replicates the composition of remaining austenite at the start of the bainite reaction in a classical C-Mn-Si TRIP steel. In the diffusional approach, classical nucleation theory is employed and subsequent growth of bainite plates is modeled using the Zener-Hillert theory. In the displacive approach, the autocatalytic nucleation of bairtite plates is assumed to be rate controlling. The predictive capability of all models is evaluated for temperature ranges where different morphologies of bainitic ferrite have been detected, The shortcomings and inherent challenges associated with either of these modeling approaches will be delineated.

Jan 1, 2003

By A. Cullaj

Several industrial sites suffer from the contamination of soils from heavy metals, which are emitted among others by anthropogenic mining and metallurgical activities. Effective and economic physicochemical technologies for remediation of these sites remain complicated and costly. A new alternative remediation technique is the so-called phytoremediation. This is based on the ability of some plants to accumulate very high concentrations of metals from soils and thus providing the basis for a remediation of the contaminated sites. This technique as an emerging branch of natural biotechnology, has several advantages compared to the sophisticated physicochemical techniques of soil remediation. It is not only environmentally friendly but also its costs are quite low since it is solar driven. Furthermore plants can accumulate metals to such levels that the mineral recovery maybe feasible even in conventional Ni refinery or smelting operations. n this work, the potential of many plants to accumulate nickel has been investigated in order to identify the species which offer the best phytoremedial potential for nickel contaminated soils in Albania. Field surveys have been made in five nickel-containing sites in order to identify the nickel tolerant species that have spontaneously grown in contaminated soils. Atomic Absorption Spectrometry measurements were carried out on 145 different plants collected. 16 of them were identified as having an hyper ability to accumulate nickel since they contained more than 10 000 mg Ni per kg (OW). Seven taxa are of Alyssum genus and one of BornmueIIera genus of Cruciferae. The highest accumulation of nickel was present in aerial parts of Alyssum murale var. chlorocarpum Hausskn (25 500 mg/kg or 2.5%) and Alyssum markgrafii O.E. Schulz (23 700 mg/kg or 2.37%). The seeds germinated are more evidenced at A.m.var. chlorocarpum, about 63%. These plants are suggested as the most promising species to be used for phytoremediation purposes in nickel contaminated soils and phytoextraction of nickel.

Jan 1, 2003

By K. Watling

Vibrational spectra of surface and solution compounds formed during cyclic voltammetry of a gold electrode in a deoxygenated 0.01 mol dm-3 NaCN solution have been examined using surface-enhanced Raman scattering (SERS) spectroscopy. The presence of cyanide at the electrode surface was indicated by Raman bands characteristic of the carbon-nitrogen stretch, CN.. Chemisorption of cyanide on the gold surface was evidenced by the presence of vibrational modes due to gold-carbon stretching, AuC, and gold-carbon-nitrogen bending, AuCN. Prior to the disappearance of the surface cyanide stretch band, a limiting value of the CN was obtained, the same as the value reported for adsorbed cyanide. Effects upon the voltammetry and vibrational modes of surface species due to additions of silver and lead to the gold-cyanide system have been observed.

Jan 1, 2003

By Nobuaki Sato

The electrical conductivity, k, of pure and sodium doped sulfur melts was measured with and without ultrasonic waves at temperatures ranging from 140 to 340° C by the two probe method using an ultra high resistance meter. The II: value of the pure sulfur melt with irradiation jumped at around 170°C by an order of 102 after which it monotonically increased from 10-5 to 10-4 (omega) 1cm-4 with an increase of the temperature. The addition of the sodium metal to the sulfur melt was found to cause a larger jumping in the II: value. The II: value increased with the increase of Na proportion in the melt. For a 10 mol% Na doped sulfur melt it was as high as max. ~30 (omega) 1cm-1 above 180°C under the irradiation of ultrasonics.

Jan 1, 2003

Thallium is a very minor element found in lead ores. It's behaviour during lead smelting has recently become of much greater interest due to the effects it had on the health of waste heat boiler maintenance contractors at a Canadian smelter. In this paper the behaviour of thallium in both traditional and direct lead smelting processes will be examined using computational thermodynamics techniques. Yazawa and his coworkers have made extensive use of computational thermodynamics to examine and illustrate pyrometallurgical processes. It has been shown that thallium behaviour during smelting is strongly influenced by the extent of oxidation of the lead concentrate and by the presence or absence of chlorine in the charge. The condensation behaviour of thallium species in the waste gas handling system was also modelled and it has been confirmed thallium-rich deposits can form at the high temperatures prevailing in waste heat boilers.

Jan 1, 2003

By Sang-Su Lee

This paper shows the application of the porous plug system in the Mitsubishi continuous copper smelting and converting process. This system has already been adopted and utilized in the steel industry to enhance productivity. Recently, some copper smelters have adopted this system but the results have not been satisfactory. The porous plug system was installed at the anode furnace in December 2001 to reduce the oxidation time and decrease the oil consumption. A good effect was that the nitrogen stirring of the melt through porous plugs improved the melt heat transfer. As the result of the enhancing heat transfer the oil consumption and the build-up inside the furnace were actually decreased. But until now the oxidation time has not been sufficiently reduced. In the future, further research and tests are needed in order to increase the productivity and save costs.

Jan 1, 2003

Hazardous waste has often very complicated chemical compositions in a variety of physical forms and is normally processed in rotary kiln incinerators. Due to large variations in waste types and difficulties in feed characterization, the complex transport processes within the incinerator are not well understood, and the incineration process meets challenges in a smooth operation, and expects various uncertainties in the process chemistry and emission control. For better understanding of the incineration process, simulation was carried out by using Computational Fluid-dynamics (CFD) to characterize temperature and species distribution in the incinerator. In order to catch certain aspects of thermal and chemical behavior, a novel approach is proposed to represent approximately the waste streams and the subsequent combustion process. Hazardous waste in various forms from an industrial-rotary-kiln waste incinerator is firstly converted to a hydrocarbon-based virtual fuel mixture with approximately the same HIC molar ratio and calorific value. The simulation of the combustion process of the simplified hazardous waste was proceeded with a combustion model. The distribution of temperature and chemical species especially the remaining CO in the system is preliminarily investigated. Distribution of CO concentration, as a good indicator of emission level for the incineration process, could be used to evaluate the emission control. The predicted temperature distribution has been compared with available measurement data from an operating rotary kiln waste incinerator at A VR-Chieme, in the Netherlands. Reasonable agreement has been reached between the measured and predicted temperature data. [n the next step, measurement of species distribution in the system is planned to further validate the combustion model.

Jan 1, 2003

By Hector Henao

To provide thermodynamic data for converting the nickel matte to liquid nickel, an experimental study was conducted in the phase equilibrium between the Ni-S alloy and the CaO-Al2O3 based slag melted in a MgO crucible at 1873 K under controlled Pso2 of 10.1 kPa and Po2 in a range between 2.5x 10-and 10.1 Pa by using CO-CO2-SO2 gas mixtures. The content of nickel in the slag at Po, of 10.1 Pa, above which solid NiO is expected to precipitate in the equilibrium state, was found to be 4, I mass% and the contents of sulfur and oxygen in the nickel melt were 0.4 and 02 mass%, respectively. ft was clarified that increase in the temperature reduces the solubility of nickel in the slag and the contents of sulfur and oxygen in the alloy, The distribution of minor elements such as gold, silver, copper, cobalt, iron, arsenic and antimony between the Ni-S alloy and the CaO-Al2O3 based slag was also studied. The distribution ratios of iron and cobalt, defined by (%X in slag)/[%X in alloy] where X is the minor element, are larger values than that of nickel, while those of copper, silver and antimony are similar to that of nickel. The distribution ratios of arsenic and gold are lower than that of nickel in the higher range of oxygen partial pressure.

Jan 1, 2003

By F. Kongoli

Viscosity is an important parameter of copper smelting and converting processes. It affects the settling of matte or metal droplets in the slag, distribution of elements etc. Despite this importance, confusion exists on the viscosity of copper smelting slags as a result of disagreements found among the measured viscosity data of several authors especially in the slags of high ferric iron content and close to magnetite precipitation. In this work a critical review of the existing data on the viscosity of copper smelting slags has been first carried out and the effect of oxygen potential on the viscosity of copper smelting slags has been clarified through a coupled quantification of viscosity and liquidus temperature. The confusion in the literature has been clarified and the importance of the relation between the viscosity and the liquidus temperature is discussed.

Jan 1, 2003

By Akira Nishikawa

During the twentieth century the copper smelting industry achieved dramatic expansion corresponding to the vast growth of global economy. This was largely due to innovations in pyro-metallurgical processes, such as autogenous smelting and continuous smelting and converting technologies. However, as copper production capacity increased, its impact on the environment also could not be ignored, and thus with increasing global environmental awareness, many smelting operations either had to renew or rebuild their facilities. In addition to these changes, in places like Japan and Europe, with scarce primary resources, the treatment and recovery of metals from a variety of items such as car shredder dust, used electrical appliances and electronic devices, on top of scraps traditionally treated, is having a profound effect on the reduction of waste and the preservation of primary resources. Thus compared to the days when copper smelting focused on the environmental control in order to break with "Smoke Stack Industry", copper smelting today is making an important contribution to the sustainable development of human society.

Jan 1, 2003

By Takahiro Miki

Soldering material widely used is Sn-Pb alloy, which have low melting point and excellent electrical, strength properties and wettability. However, Pb is one of the toxic elements, which is undesirable due to environmental and safety reasons, thus Pb-free alternative alloy is preferred for new soldering material. Sn-Ag and Sn-Zn based alloys have been viewed as very promising candidates, among many potential substitutes. Addition of third element to these alloys will decrease melting point of the alloys. Hence, Sn-Ag-In and Sn-Zn-Mg alloys are expected to be suitable for replacing Sn-Pb solder alloy. In order to design new Pb-free soldering materials, it is crucial to understand precise thermodynamic properties and phase diagrams of alloy systems. In the present work, ion current ratios of Ag to In and Mg to Zn were measured for Sn-Ag-In and Sn-Zn-Mg alloys by mass spectrometry, respectively. Also, the authors reviewed the thermodynamic properties of terminal binary alloys determined by other researchers and evaluated a thermodynamic functions to express the excess Gibbs free energy of each binary alloy. Thermodynamic functions to express the excess Gibbs free energy of liquid Sn-Ag-In and Sn-Zn-Mg ternary alloys were determined, utilizing the assessed Gibbs free energy of terminal binary alloys with the measured ion current ratios using mass spectrometer.

Jan 1, 2003

By Zhitong Sui

Based on several case studies on the precipitating behavior of valuable nonferrous metal compounds (VNMC) in molten slags a green technology for the recovery of VNMC from molten slags was proposed. This technology involves three steps: (I) The selective enrichment of the dispersed VNMC into the designed mineral phase in the molten slag; (2) The selective coarsening of the designed mineral phase to a critical grain size in the molten slag; (3) The selective separation from tailing of the grown mineral phase in the solidified slag by dressing or hydrometallurgy processes. This is a clean and low cost technique and has a great capacity to deal with a large quantity of slags. The utilization of the recovered VNMC such as Titanium, Boron, Vanadium compounds was summarized as examples of application. It was confirmed by experiments that the precipitating behavior of the designed mineral phases like Perovskite(CaTiO3), Suanite(2MgO*B2O3) and Sincosite(CaOoV2O5*P2O5) in molten slags is obviously affected by operation factors such as temperature, chemical composition, heat-treatment, additives and so on. The precipitating kinetics and mechanism of the VNMC from molten slags during solidification processes were also investigated.

Jan 1, 2003

By Bora Derin

This work deals with the recovery of valuable metals from the ancient copper smelting slags located in Küre-Turkey. In this process, copper and cobalt were recovered in metallic form and/or as their compounds, whereas iron was recovered as magnetic oxide or pigment. Abrasive grit material was produced using reduced final slag. The process stages involved carbothermal reduction in a DC arc furnace, granulation, leaching, chemical precipitation, selective sulfidizing roasting and product preparations. In this paper, the process stages were described as theoretically and experimentally whereas slag and products were characterized in detail.

Jan 1, 2003

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 of this approach, as opposed to releasing the gas to the atmosphere, and the economic benefit of directly utilizing the SO2 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 gamieritic 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 potenrial 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 E. V. Verhoej

The proposed EU directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment promotes the substitution of lead in consumer electronics to reduce emissions from lead in the end of life phase. In this paper, the consequences of substituting lead in solders is assessed using the Eco-Indicator-99 method for the examples. The base metal production system is considered as an interconnected network modeled dynamically in Simulink 4 and Matlab 6 (Mathworks Inc 2000), where the recovery and production of metal components of the assessed product partially overlap. This approach requires global modeling of metal production processes and mass balances and resulting allocation choices. It also reveals the susceptibility of LCA scores to different choices in the modeling and data availability and uncertainty. Besides the comparison between lead-free and lead-containing solders, other side effects are revealed. Lead is carrier material for the recycling and production of many co-elements in the interconnected production and recovery system. Substitution may have adverse effects such as temporary shortages of other connected metals that are often not considered in normal LCA assessments, thus leading to erroneous results. The suggested approach provides directions for including these extemal effects and for further assessment of the environmental effects of substituting lead. This paper shows that in order to assess the environmental aspects of metallurgy, dynamic modeling of the total system is required based on the fundamental thermodynamics in each metallurgical reactor, the basis of this dynamic model. With this the true environmental impact of metallurgy can be explained. In the case of lead free solder, it is shown that the mining of substitutes has a very much larger impact.

Jan 1, 2003

By Supachai Surapunl

The distribution behavior of VA minor elements (As, Sb and Bi) in the smelting stage of the Mitsubishi process were evaluated thermodynamically based on thermodynamic data and operating data. The fractional distributions between the gas, slag and matte phases considered as the degree of vapor saturation of l.0 are as follows: 53.8, 27.2 and 19% for As, 23.6, 56.6 and 19.8% for Sb, and 91.3, l.1 and 7.6% for Bi, respectively. Arsenic is mostly distributed to the gas and slag phases. It is effectively eliminated by volatilizing and slagging. Antimony is mainly in the slag phase, which is suitably removed by slagging. Bismuth is easily vaporized to gas phase. The degree of vapor saturation has a large effect on the distribution behaviors of the three elements between the three phases. The amount of a minor element in the charge has an effect on the distribution of As but no effect on the distributions of Sb and Bi. Increasing matte grade and temperature results in the change of distributions for As and Sb, significantly. The change in the distribution ratio between slag and matte phases also considerably affects the distributions of As and Sb. The distribution behavior of Bi is not significantly changed by the change in matte grade, temperature and distribution ratio.

Jan 1, 2003

By Hiroshi Hashimoto

For the application of sodium carbonate slag treatment to product high purity copper on an industrial scale, the counter-flow batch process that reduces the amount of utilized slag is proposed from the viewpoint of the post-treatment of slag. Based on the distribution ratios of several impurities between the slag and molten copper determined previously, the effectiveness of this process is discussed using a mathematical model and confirmed experimentally. According to the model, the slag consumption to remove Sb to a required level in case of the counter-flow batch process with 3 reactors is calculated to be around 30 % of that in the case of an ordinary batch process, where pure sodium carbonate is used as a slag at every stage.

Jan 1, 2003

By Grigore Matei

The thermodynamic properties of CuzS-FeS system are important not only in the ease of copper smelting but also in the case of general pyro-metallurgy. However there arc not many reported activity data In this study, activities of FeS and CU2S in the Cu2S-FeS system were calculated using the Darken's method from the activity data of the Cu2S-FeS-Sb2S3 systems measured by the transportation method at 1050°C. The activities of Cu2S and FeS in the Cu2S-FeS system showed negative deviation from the ideal behaviour and satisfied the relation of the Gibbs-Duhem equation.

Jan 1, 2003

By Etsuro Shibata

The saturated solubility of chromium oxide and the valence of chromium in the slag are important matters when considering how to effectively utilize chromium-containing slags. The experimental data of various types of slags cited in the literature were arranged according to the optical basicity in order to evaluate the effects of the oxygen potential and the slag composition. The saturated solubility of chromium oxide and the Cr2+/ Cr3+ ratio tend to decrease with the increase of the optical basicity of the slag at an oxygen potential below 10.5 atm. However, at an oxygen potential of 0.21 atm, the saturated solubility and the Cr6+/Cr3+ ratio tend to increase with an increase of the optical basicity. A practical approach was suggested to reduce chromium in the stainless steel slag and simultaneously recover it as a ferroalloy by the direct smelting reduction of chromium oxide in the molten slag using some reductant in a small furnace.

Jan 1, 2003