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By F. Ajersch, P: Tsantrizos, K: Shanker

"TiN films have been deposited on various substrates by a novel reactive plasma technology. In this process, a nitrogen source (NH3 or N2) and TiCl4 are reacted in the jet of a plasma torch, and are deposited onto a substrate forming TiN films at a high growth rate ( > 2µm/min). It was found that the process parameters strongly affect the microstructure, thickness, density, and growth rate of the TiN films. These parameters include source of nitrogen (NH3 or N2, N/Ti ratio, temperature of substrate, and spray distance. In general, it was found that thick and dense coatings were deposited when the N:Ti ratio was kept low, and the substrate temperature was high. Also, for the series of conditions investigated, NH3 was found to give much better results than N2•. The limitations and advantages of this technique are also discussed in this paper.IntroductionTiN is an extremely hard material and is used in many wear applications, particularly as a protective coating on cutting tools to extend their Iife(1.2). Owing to its excellent chemical stability, TiN is also frequently used as a diffusion barrier in the electronics industry for sub-micron Al/TiN/Si ohmic contact systems (3) or as a coating on high-temperature resistant alloys in gas turbine applications (4), based on its good resistance to oxidation. Other applications include decorative coatings in the jewelry industry, and specialized applications such as solar energy absorbers and transparent heat mirrors(5).TiN films can be deposited/formed using various techniques. The main techniques of deposition are CVD (Chemical Vapour Deposition) and PVD (Physical Vapour Deposition). Each of these techniques can have many variations in equipment characteristics, reactants as well as a range of process parameters (pressure and temperature). In the CVD process, TiN is generally deposited onto a heated substrate where a chemical reaction takes place. The reaction can be one of reduction(6) (e.g.: TiCI4 + 0.5N2 + 2H2 --> TiN + 4HCI), of thermal decomposition(7) (e.g. decomposition of titanium dialkylamide), or of displacement (e.g. TiCI4 + NH3 --> TiN + 3HCI + 0.5CI2)' The displacement and reduction reactions are the most common."

Jan 1, 1994

By T. DebRoy

In recent years rapid technological advances have been achieved in the application of high energy density heat sources such as lasers and electron beams in diverse metals processing operations such as metal refining, fabrication, coating, surface modification and alloying. However, our phenomenological understanding of these new and emerging processes has not kept pace with the technological achievements. Inadequate understanding of plasma-metal interactions, the complexity of the component physical processes, and the scarcity of thermophysical data at temperatures much higher than the melting points of metals are the main difficulties in the comprehensive analysis of these processes. Several unique contemporary issues related to metals processing with high energy density beams such as rapid evaporation of alloying elements during processing and the role of plasma in influencing vaporization rate interfacial tension and species solubility in metals are discussed in this paper.

Jan 1, 1993

By B. Madelin

Over the last ten years, Minemet Recherche and Metaleurop have used an approach in order to investigate and improve the operation of its Smelting furnace and its lead blast furnaces. This approach gives importance- to three complementary means of investigation : - Probing campains in the industrial furnace (temperature and gas analysis profiles), - Chemical and physical modeling (coke combustion, sinter reduction modes, flows patterns, ?.) , - Staged mass and heat balances or kinetic model. This allows to define the limits of operation of each blast furnace and to predict the influence of operating parameters on the furnace performances. For the zinc Imperial smelting furnace, the probing results show the existence- of both an Isothermal reserve zone at 1015ºc and a chemical equilibrium between ZnO and gas which makes possible the use of a practical model for heat and material balances. In particular, very good prediction on the influences of operating parameters can be made. On the contrary, for lead blast furnaces, the probing results show that the thermal and chemical equilibria are not reached. Consequently, classical models for staged heat and mass balances are not sufficient. The use of the other means allows then to characterize the specific influences of operating parameters on the thermal instabilities of these furnaces and their allowed limits.

Jan 1, 1990

By Susumu Okabe, Etsuji Kimura

"The Mitsubishi Continuous Copper Smelting and Converting Process is the typical applications of injection metallurgy to nonferrous metallurgical operation, where the top blowing multiple lance system is employed for the continuous feeding of the raw materials and reaction gases into the molten bath. This results in an effective dispersion of the reactants into a strongly agitated bath. These are considered as the major advantage of the process with respect to the high production efficiency. On the other hand, however, the strong agitation may cause a considerable amount of refractory wear, and the melt splash generated by the lancing may also have negative effects on the productivity, i.e. the increase in the refractory wear, the metal loss, the heat loss, and the accretion growth, etc. Therefore, the optimization of the blowing condition as wen as furnace design is very important to achieve a stable and efficient operation, and fundamental understanding of the injection, agitation, and splashing is badly needed.In this paper, fundamental aspects of the Mitsubishi Process regarding injection, especially splashing phenomena, are discussed. The splashing on a vertical plane caused by the top blowing gas injection onto liquid surface was investigated through physical model study. As a result of the study, the splashing rate on the furnace wan was wen correlated with the physical properties of the bath materials, gas velocity, cavity shape, lance/wall distance and ceiling position. Obtained equations were compiled in a computer program and have been successfully applied to the evaluation of the furnace design. IntroductionInjection metallurgy is an application of gas/solid-in-liquid dispersing operation to the metallurgical processing, and has been widely adopted in various fields in order to improve their efficiency or productivity. The dispersed small particles of gas or solid materials in the liquid phase result in increased interface area, and injected momentum causes an agitation and enhanced heat and materiel transfer. Typical examples of injection metallurgy are LD converter for steel making, PS converter, Noranda process, Isasme1t for copper making, and Mitsubishi Material's continuous copper smelting and converting process, and so on."

Jan 1, 1996

By T. T. Chen

A mineralogical study of copper anodes and copper anode slimes was carried out to elucidate the silver phases present and the behaviour of silver during copper electrorefining. Most of the silver in the anodes is in metastable solid solution in the copper metal. As the copper dissolves, silver also dissolves, but is rapidly removed from solution by a variety of reactions. Some of the silver is precipitated as Ag by cuprous ions and some is precipitated as a complex CU-Ag-Pb-As-Se oxidate phase. Much of the silver, however, reacts with copper selenides to form, progressively, (CU,Ag) 2se, AgCuSe and Ag2se. The reaction commences at the periphery of the selenide grains and progresses inward; the result is commonly a silver-rich species on the outside of a silver-deficient core. Slimes collected periodically throughout the electrorefining cycle show a progressive silver enrichment of the selenides. Traces of Ag2Te also may be present, but the telluride seems to J:ie a rare constituent of most raw anode slimes.

Jan 1, 1989

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

By Akira Yazawa

The similarities and differences in copper, nickel and lead smelting processes are discussed based on the sulfur-oxygen chemical potential diagrams and the free energy minimization assessments using a thermodynamic software. The prominent features of copper smelting are ascribable to the fact that copper has a strong affinity for sulfur but weak for oxygen and the liquid phase immiscibility between Cu and Cu2S. During the oxidation of sulfides, nickel metal is not stable except at temperatures higher than 1500°C, well miscible with its sulfide, and is oxidized more easily than copper. Metallic lead looks as stable as copper during the oxidation of the concentrate but Pb and PbS. are much more miscible with each other and the vaporization loss is considerable. In the reductive smelting of oxides, the effects of oxygen potential and temperature on the copper contents in slag are not significant due to the monovalent character of copper and the reduction of copper content in slag is not easy in practice. The effect of the slag compositions on the oxidic metal contents of slag is much more significant for lead than either copper or nickel. Due to the immiscible nature between Pb and Fe, high grade lead bullion is easily obtained and lead is more tolerant to impurities.

Jan 1, 1998

By Kimiaki Utsunomiya, Yasumasa Hattori, Yoshiaki Mori, Toyokazu Okubo

"The effect of various operating conditions on splashing behavior in a Peirce-Smith converter has been investigated with a 1/5.7 scale cold model. Dynamic similarity between the model and a commercial converter was attained by setting the modified Froude number in the model experiments in· the range for normal converter operation. It is known that for a given modified Froude number the dimensionless penetration length of gas into the liquid phase increases as the liquid density decreases. Moreover, penetration· length has a large effect on splashing behavior. Therefore, a heavy liquid, a mixture of water and lead concentrate was used as the liquid phase. It was concluded that the amount of splash dramatically decreases with a reduction in the buoyancy energy per, unit liquid mass and an increase in the horizontal distance between the tuyere tip and the edge of the mouth.IntroductionSubmerged gas injection is widely used in practice in ferrous and nonferrous pyrometallurgical operations to achieve large gas-liquid contact areas and good agitation of liquid for rapid chemical reaction. The common application in ·nonferrous industry is the Peirce-Smith converter with multi-tuyere for copper and nickel matte converting. This process has been used for over 100 years because of its effectiveness in mixing of the molten bath, as well as its merits of the engineering simplicity. However, the mechanisms which · determine the blowing performance is poorly understood, and the design and operating conditions of the Peirce-Smith converter varies widely from plant to plant, such as by diameter, length, mouth angle, tuyere position and level of molten matte. Smelters have continuously made an effort to increase converter productivity, implying maximum tuyere blowing rate. Above a certain critical blowing rate, splash of molten matte from the converter mouth becomes unacceptable because of dangerous ejection and accretion buildup around the converter mouth, which results in interference with effective hood sealing. In fact, a 1993 converter survey[!] reported that splash was a major limiting factor for blowing rate and 54% of responding plants from around the world regard it as a limiting condition[2]. In order to increase tuyere blowing rate a study of the effect of various operating conditions on splashing behavior is expected."

Jan 1, 2000

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 J. J. Talja

An investigation of oxidation of various nickel concentrates was carried out using differential scanning calorimetry (DSC). The aim of this study was to determine the ignition temperature and investigate other oxidation behavior of various sulfide-based nickel concentrates. Variables in the experiments were mineralogy, particle size and partial pressure of oxygen with temperature increasing linearly at 25 K/min from 323 to 1023 K (50-750 °C). The igni¬tion temperature was determined to represent the starting point of rapid oxidation. The reac¬tion enthalpies of the concentrates were determined and the amount of heat generated up to various time were used to calculate the extent of reaction. Mineralogical changes at various stages of oxidation were also investigated. For this purpose a second set of DSC-experiments were carried out in which each experiment was interrupted at a desired temperature between 673-873 K. From these tests the weight loss of samples were determined and changes in the individual constituent of sulfide minerals were analyzed. For pentlandite-based Ni-concentrates the ignition temperature was 705-710 K (approximately 435 °C). Pyrite was the first sulfide to oxidize. Reactivity of the violarite-based concentrate was greater than those of the pentlandite-based concentrates. The stoi-chiometry of pentlandite changed before ignition because of preferential oxidation of iron. Rapid oxidation of the pentlandite mineral occurred at about 823 K (550 °C). By 900 K about 90 % of the iron in pentlandite was converted to hematite, and NiS containing some iron was formed.

Jan 1, 1994

By Anja Pfennig, Thomas Böllinghaus, Marcus Wolf

During CCS components are exposed to a corrosive environment and mechanical stress which results in corrosion fatigue and is inevitably followed by the lifetime reduction of these components. The lifetime reduction of the cyclically loaded high alloyed stainless injectionpipe steel AISI 420C (X46Cr13, 1.4034) constantly exposed to highly corrosive CO2- saturated hot thermal water is demonstrated in in-situ-laboratory experiments (T = 60 °C, brine: Stuttgart Aquifer, flow rate: 30 l/h, CO2) in an environment similar to the on-shore CCS-site in the Northern German Bassin. In-situ tension-compression experiments were established simultaneously along with electrochemical measurements using a newly designed corrosion chamber in a resonant testing machine at a frequency as low as 30 – 40 Hz. In addition technical CO2 was introduced into the closed system at a rate close to 9 L/h. S-N plots, micrographic analysis and surface analysis of the fracture surface are demonstrated. X46Cr13 (surface roughness Rz = 4) reached the maximum number of cycles (12.5 x 106) at stress amplitude of 173 MPa producing a low scatter range of 1:3.5. Hydroxide and siderite layers were found on pits and crack surfaces. No typical fatigue limit exists. Pit corrosion prior to crack initiation may be identified as failure cause.

Jan 1, 2016

By D. J. Murdock

Cominco Ltd. has developed a number of innovative technologies for electrowinning. The paper discusses the application of these technologies to the copper industry. Tankhouse and cell design will be discussed in addition to anode cleaning and cathode handling. Specific examples of the application of this technology to the copper industry are cited.

Jan 1, 1987

By B. C. Jena

Activities of carbon, cobalt and nickel were evaluated in the ternary systems iron-carbon-cobalt and iron-carbon-nickel for the temperature range 1300-1600°C for cobalt and 1300-1700°C for nickel. The carbon activities were determined from the knowledge of activities (1) in the binary system iron-carbon, (2) in the dilute ternary systems and (3) from the knowledge of carbon saturation data. The activities were mathematically expressed with the Taylor series expansion of Wagner's interaction parameter formalism modified to suit concentrated solutions. The cobalt and nickel activities were determined from the knowledge of carbon activities by applying the Gibbs-Schuhmann integration and from cobalt and nickel activities in the binary systems iron-cobalt and iron-nickel. Partial molar enthalpies of mixing were determined based on the temperature behaviour of the activity coefficients.

Jan 1, 1992

By J. E. Dutrizac

The behaviour of the lanthanide elements during the precipitation of sodium and potassium jarosites at 98oC from sulphate media was systematically investigated. The lower atomic weight lanthanide elements (La to Gd) are characterized by the limited solubility of their alkali-lanthanide sulphates, such as NaNd(SO4)2?H2O, which commonly contaminate the jarosite precipitates. Hence, single phase jarosite-type compounds were precipitated only from solutions containing <0.4 g/L of the La to Sm lanthanides. The sulphates of the heavier atomic weight lanthanide elements (Tb to Lu) have significantly higher solubilities such that solutions containing up to 10 g/L of the individual lanthanides could be investigated without the precipitation of alkali-lanthanide sulphate species. Even at the highest lanthanide concentrations, however, none of the jarosite precipitates incorporated more than 0.3 wt% of any of the lanthanide elements. Comparable levels of lanthanide incorporation were noted in both Na-jarosite and K-jarosite. Although the mass of the jarosite precipitate increased with increasing ferric sulphate concentration or with increasing pH, the extent of lanthanide incorporation was not significantly affected. Clearly, the trivalent lanthanide elements do not substitute extensively for trivalent iron in the jarosite structure. This behaviour likely reflects the significantly lower hydrolyzability and larger size of the trivalent lanthanide ions relative to ferric ions.

Jan 1, 2003

By Arpad E. Tonna

Recycling of materials from lithium-oxyhalide batteries is a complex task, since the dismantling of batteries is associated with many hazards. The electrolyte and the lithium anode metal are extremely reactive in the presence of water or water vapor. Therefore, the dismantling process is a complex task. In this process, the lithium battery is electrically discharged, then frozen in liquid argon, and cut into small size pieces. These are fed into an incinerator, where the unreacted portion of lithium metal, thionyl chloride, plastic separators and carbon paste are decomposed and burned to gaseous products. The aluminum, iron (steel) and nickel pieces are recovered as saleable scrap metals. The off-gases are scrubbed with an alkaline sodium carbonate containing solution. The clean gases are released to the environment. The particulate mater recovered from the scrub-suspension would be available as additive to the cement industry . The recycling of battery decomposition products improves the economic viability of the disposal processes. Work is in progress to develop safe handling, processing and recycling large size lithium batteries.

Jan 1, 1995

By A. Kar

A mathematical model is presented for pure titaqium deposition from titanium tetrabromide on a stainless-steel (SS 304) substrate. Five three-dimensional, transient, and nonlinear partial differential equations are used to account for the diffusion of various species inside the deposition chamber and the thermal decomposition of titanium tetrabromide, titanium dibromide, and titanium monobromide at the surface of the substrate in order to determine the thickness of the titanium film deposited on the substrate. The effects of various process parameters on the deposition and shape of titanium films are examined, and under certain conditions, the deposited titanium films are found to have volcanic profiles.

Jan 1, 1992

By L. M. Abrantes, A. P. Paiva

"A brief review of some innovative methods for the direct recovery of metals from loaded organic phases is presented; emphasis is given to electroreductive stripping and cementation, which are described and illustrated by examples: of current research. The recovery of silver using a two-phase electrolysis - by direct application of an electrical potential to a mixture of a metal loaded organic phase· containing Cyanex 471X, obtained by solvent extraction, and a stabilized sodium thiosulfate solution - is more extensively discussed. The overall efficiencies are analyzed and compared with data obtained by conventional stripping procedures. Some preliminary results achieved for the recovery of the precious metal using galvanic stripping, applied directly to similar organic solutions and involving zinc and iron powders as reducing agents, are also evaluated.Introductory ReviewThe application of hydrometallurgical methods to the recovery of metal values from ores and concentrates has been receiving a growing interest, either from researchers or from the mining industry [1].For the concentration / purification of the relatively low concentrated metallic solutions resulting from the leaching of those raw materials, solvent extraction (SX) is a well established technique [2]; the loaded organic solvent is then conventionally contacted with a suitable aqueous solution, the metal in its final form being usually recovered from this solution by electrowinning.As an efficient and / or selective stripping is sometimes difficult to achieve, depending on the specific characteristics of the system under consideration, some alternative procedures have been analyzed in order to overcome this problem. One of the chosen routes, mainly developed by Hirai and Komasawa, is to promote the reduction of the desired metal species in the organic phase, in such a way that the stripping stage becomes feasible; for the selective stripping of vanadium from a solvent containing a mixture of vanadium and molybdenum, the authors successfully used reductive [3], electro-reductive [4,5] and photo-reductive [6] techniques. The two latter methodologies have also been applied to the recovery of europium from a solvent containing europium, samarium and gadolinium [7,8].However, further processing is necessary to recover the metal in its solid state; therefore, methods causing the direct reduction of the metal species in the organic phase to their fmal metallic form would be of interest, as an intermediate step would be avoided"

Jan 1, 1997

By Richard D. Hagni

Microscopic examination of selected, representative, unweathered samples of Birmingham, Alabama, Silurian, sedimentary iron ores has fully revealed the nature of the phosphorous-bearing mineral grains. The grains are composed of carbonate-fluorapatite (collophane), range in size from 1 um to 2.25 mm, and exhibit varied types of intergrowth with hematite. Modal analyses conducted under cathodolumi-nescence have provided quantitative data on the a3undance of each of 15 types of phosphorous-bearing mineral grains and made it possible to assess the potential phosphorous liberation from four types of iron ore. The results indicate that 27% of the total phosphorous contained in the iron ores in the western part of the Birmingham district can be expected to be liberated by fine grinding; 60% for ores in the eastern part of the district.

Jan 1, 1982

By Timothy W. Ellis

This paper presents the basic theory of operation, physical chemistry and phase equilibria which allow the development of liquid-liquid extraction circuits based on metallic solvents. The incorporation of reduction and reduction/diffusion processes into the process &apos;scheme is discussed and a detailed description of ,several liquid-liquid extraction schemes are developed. A synopsis of experimental results obtained using this: method to separate rare earth and other metal based materials will be given.

Jan 1, 1996

By Hojat Naderi

In this research assisted leaching of chalcopyrite using sodium peroxodisulfate was studied. Electrochemical techniques such as Tafel analysis and electrochemical impedance spectroscopy (EIS) were used to investigate the surface reactions of a chalcopyrite electrode in the presence and absence of Na2S2O8. According to the results, addition of sodium peroxodisulfate increases the current exchange of the corrosion process and prevents the formation of a passive layer on the surface of the electrode. EIS tests show the trans-passive dissolution of the passive layer on the chalcopyrite electrode in presence of Na2S2O8. Equivalent electrochemical circuits were modeled for Na2S2O8-free and -containing solutions and the model parameters were compared to determine the effect of S2O8 2− on chalcopyrite dissolution. Copper dissolution from pure chalcopyrite mineral and chalcopyrite concentrate was carried out using 15 g/L sulfuric acid solution with and without Na2S2O8. Simultaneous presence of 10 g/L ferric ion and 40 g/L peroxodisulfate salt results in about 40 and 18% of Cu extraction from chalcopyrite concentrate and pure chalcopyrite mineral, after 96 h, respectively.