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By Katsumi Ogi, Hiroto Uchida, Masamitsu Sato, Atsushi Itsuki

"(BTMSE)Ag(hfac) (BTMSE = trans-bis(trimethylsilyl)ethene) was chosen as a suitable precursor for the XeCl laser (308nm) MOCVD of Ag. Iso-propanol solution of (BTMSE)Ag(hfac) was used as a liquid source for the liquid delivery method, high deposition rate 9nm/min at substrate temperatures of 100°C and 120°C were obtained at the vaporizer temperature of 90°C. This deposition rate is three times faster than by conventional bubbling method and life of the source and reproducibility of the deposition were also improved. Electric resistivities of the laser deposited film shows significantly low resistivity of 10-6Q-cm compared to 1 o-3Q-cm of thermal MOCVD film. These results indicates that the laser MOCVD is one of the effective method for the preparation of the high quality silver film.IntroductionSilver films are a potentially important metallization material in electronic and photonic devises due to their lowest resistivity (1.6µ0-cm) among the metals, high optical reflectance and chemical stability. The MOCVD technique has advantages to sputtering or evaporation in the point of conformal growth and better coverage on sharp steps and narrow gaps[l-2]. For MOCVD application, silver precursors must have sufficient vapor pressure without decomposition at their evaporation temperature. To achieve stable precursor gas supply, liquid delivery of precursor material is promising[3-4] especially for materials that have not enough heat stability and high vapor pressure like silver complexes[S-10]. Several new silver complexes for MOCVD and UV irradiation effect to their MOCVD silver film quality were reported by same authors[5]. In this paper new solvent system for liquid delivery system of silver MOCVD were investigated to suite XeCl(308nm) laser MOCVD application."

Jan 1, 1998

By Yuan Zeping

This paper describes the distribution and removal of the main impurities in the pyrometallurgical process ?at the Guixi Smelter. The paper discusses in detail our converting schedule?of3S-SB and injecting deeply a mixture ofNa2CO) and CaO flux into the converters to enhance impurity removal.

Jan 1, 1998

By Yoji Imai, Akio Watanabe, Masakazu Mukaida

"To clarify the feasibility of alkoxides and acetylacetonates as precursors for laser CVD of metal oxides, vapors of tantalum or titanium alkoxides and zirconium acetylacetonate were irradiated by KrF excimer laser and deposits were characterized by XRD and XPS measurements. As for tantalum and titanium, non-stoichiometric crystalline oxides grew nearly phototropically, however, zirconium oxides deposited showed only halo-pattern by XRD measurements. Electric conductivity measurements of tantalum oxides implied the improvement of the insulating properties by the addition of activated oxygen to the ambient.IntroductionThere has been renewed increasing attention to the metallic oxide thin films because ofits promising usefulness in many applications, such as high-Tc superconductors and ferroelectric devices. A variety of thin film preparation techniques have been studied such as sputtering, chemical liquid deposition (sol-gel and metalorganic decomposition), pulsed laser deposition and chemical vapor deposition (CVD). Among them, we think CVD is the most promising method because it offers a high controllability of morphology and good step coverage at relatively high growth rate. Preparation of oxide films by CVD can be achieved using a precursor containing metallic element and oxygen containing gas such as N20 at the same time. However, metalorganic (MO) compounds which contain both metallic element and oxygen, directly bonded to metallic element, seems to be more favorable because some of MO has a good properties for CVD such as a rather high vapor pressure, stability in ambient and low toxicity."

Jan 1, 1998

By Steven I. Baskin

Cyanides are utilized in many industrial applications including preparation of chemical intermediates, electroplating, and' mining, Cyanide has been utilized in chemical warfare operations as well Cyanide is also synthesized and found in plants and animals including man where it is thought to perform multiple functions. A variety of enzymes are known to detoxify cyanide under different conditions. These include rhodanese, 3-mercaptopyruvate-sulfur transferase, thiosulfate reductase, cystathionaseand albumin. Cyanide appears tQ exert its toxic effect primarily by inhibiting cytochrome oxidase? although other enzymes are also inhibited. Therapeutic antagonist categories to treat cyanide include methemoglobin formers such as nitrite, sulfane-sulfur donors such as thiosulfate, metal salts or complexes such as cobalt and cyanohydrin-forming compounds such as dihydroxyacetone or alpha keto-glutaric acid. Advantages and disadvantages of each category will be discussed. Newer compounds under development have been found that may allow for prophylactic therapy for cyanide poisoning with minimal side effects; In addition, portable co-oximetry devices may provide real-time measurement of cyanide in field units.

Jan 1, 1998

By I. Kim, J. C. Choi, W. D. Cho

"The effect of yttrium addition on the oxidation behavior of Fe3Al intermetallic compound was investigated in the range of temperature 800 to 1100 °C in 0.2 atm 02 in terms of oxidation rate and oxide adhesion. The oxidation rate of alloys, Fe-14.3 wt% Al and Fe-14.1 wt% Al-0.3 wt% Y, was nearly identical and the parabolic rate constant calculated as a function of temperature is Kp=5128 exp[-39506(cal/mol)/RT] mg2/cm4 hr.Rapid cooling and ultrasonic stress tests were carried out to test adhesion of scale formed on the alloys. While the oxide layer formed on the Fe-Al alloy without Y was found to be fragile and detached easily during the tests, the oxide layer formed on the Fe-Al alloy containing Y was protective, dense, and adhesive. The following two mechanisms were proposed to explain the adhesion improvement of Ah03 formed on the Fe3Al containing yttrium : (1) the addition of yttrium decrease generation of growth stress in alumina scale because the preferential diffusion of yttrium through grain boundary in alumina scale prevent internal oxidation of Al, one of main causes of growth stress, and (2) the second phase formed on the oxide scales prevents crack propagation through the scales, leading to better mechanical stability of the oxide scales.IntroductionIron aluminides have attracted the attention of many researchers as a candidate for use at high temperature because of their excellent oxidation resistance due to the formation of protective alumina scale. In order to resist aggressive environments at elevated temperatures, oxide scale formed on iron-uluminum alloy must satisfy the following three requirements : (1) thermodynamic stability (2) slow growth rate (3) adherence on substrate. According to Wallwork and Hed [l], the most suitable alloys for high temperature application are Fe, Ni, and Co alloys with the protection of Si02, Cr203, and Ah03 scales. While chromium oxide can vaporize as Cr03 above 1000 °C and silicon oxide may form low melting silicate [2,3], Alz03 has a high melting point and is the most stable among the three oxides thermodynamically [6]. In this respect, iron aluminides forming alumina seem to be most suitable for use at high temperature. However, alumina scale formed on the iron aluminum alloys tends to be easily spalled during oxidation due to the combination of growth stress and thermal stress."

Jan 1, 1998

By S. Ozbilen

"Al-Li binary alloys with nominal Li contents of0.15, 1.1and2.8 (in wt%) were aged naturally at room temperature for two months, aged at low temperatures ( 65 and 1 OOEC) for up to 2 months and aged artificially at 190EC for 4 days after water quenching to 25EC following solutionizing at 530EC for 20 minutes. Ageing behavior of these binary alloys were studied by Vicker's Hardness measurements and DSC thermal analysis. Thermal analysis results indicate the formation of GP zones of Al-Li system in Al-2.8wt%Li binary alloy. In the same alloy, rapid quenching from one phase region (a) gives rise to precipitation of small o' particles in a matrix (a) with still high supersaturation. During ageing of this alloy below lOOEC an additional transformation, i.e., GP zone formation occurs proceeding at a very high rate which is described on the basis of the theoretical analysis for the quenched Al-Li system proposed by Khachaturyan et al [6]. Ageing at temperatures below 11 OEC takes place slowly by the formation of small d' particles of lower thermal stability than the quenched-in d precipitates in addition to GP zones resulting in an increase in hardness compared to water quenched samples. During artificial ageing, GP zones transform by dissolution to d' precipitates while d' particles already in the microstructure coarsen during under aged condition at which hardness increases with time till peak aged condition.IntroductionIn binary Al-Li alloys the d' (Al3Li) fully coherent internally ordered inetastable phase of Li2 structure with a=0.4038d [1-5] forms homogeneously between 120 and 190EC before the formation of stable d' (A!Li) phase and cause the superior mechanical properties. This is due to an appreciable age hardening effect resulting because of the d' precipitation during ageing [1]. The response of d' to decomposition and its formation kinetics have been studied previously and it is believed that the decomposition of the a-supersaturated solid solution occurs in a two stage process; i.e., a 6 d' (Al3Li) 6 d(A!Li). Khachturyan et al [6] theoretically investigated precipitation of the d' phase and gave an interpretation of the transformation paths of the quenched Al-Li alloys. They predict that the disordered supersaturated solid solution congruently orders, and then the uniformly ordered solution decomposes into ordered regions that differ in Li-content. Finally, ordered d' phase forms in the disordered matrix."

Jan 1, 1998

By Yuri Gelfgat

"The report presents the results of theoretical and experimental investigations of the MHD method used for production of composite materials from immiscible melts, e.g., Al-Pb, Zn-Pb, Bi-Ga and others, which, when solidified, can be presumed as ""frozen emulsions""IntroductionThe searching of the methods for controlling the phase distribution in various liquid heterogeneous media is one of urgent tasks in modem material science. The studies [1-3] have revealed that in case of electrically conducting media the influence of electromagnetic body forces on the liquid can be a rather effective mean of such a control. The current paper investigates some physical conformities governing the behaviour of binary liquid metal systems with a immiscibility region under electromagnetic processing designated to produce ingots with homogeneous structure.The main idea of the proposed method rests upon a concept that the electromagnetic forces in the melt are similar to gravity forces due to buoyancy effects in space and have a selective ability to influence the melt components dependent on their conductivity. In crossed electric E and magnetic B fields (fig.I) each component of the medium is influence by the force density f = jXB, where the current density j is determined by the conductivity a of the component j = -oE. When this force is directed parallel or non-parallel to the gravity vector, the buoyancy of suspended particles can be controlled accordingly.This phenomenon allows one to create a situation in binary system, when the sums of all mass forces (gravity and electromagnetic) affecting every component are equal, and two components are under conditions of equilibrium with respect to each other. These conditions are called quasiweightlessness, which is generated in the melt by the electromagnetic forces."

Jan 1, 1998

By Rey B. Marquez

This paper introduces and outlines the implementation of Reliability Centered Maintenance (RCM) at Phelps Dodge Hidalgo Inc. By using a disciplined approach to the everyday maintenance functions, a proactive strategy is being developed which "raises the bar" for plant maintenance. The main objectives are: integration of Operations and Maintenance partnerships, transformation of maintenance practices from a reactive to proactive mode through the introduction of a progressive Predictive/Preventive Maintenance program (PDM/PM) paradigm changes, increased management support of maintenance functions, introduction of new indices and root cause analysis, updated; training, and definition of RCM components. RCM is the vehicle being utilized to reach the higher level of equipment availability and utilization. However, the ultimate goal is to venture beyond RCM and into the new frontier of Total Maintenance Management (TMM).

Jan 1, 1998

By Antti Roine

HSC Chemistry is a widely-used therniochemical tool in the chemical and metallurgical industries and in universities. The main reasons for it's popularity is the easy user interface and the large integrated thermochemical database. This paper summarizes the main properties of the new HSC Chemistry version 3.0, and gives a short review of the new features: Some metallurgical applications with the new features are also presented. HSC Chemistry 3:0 contains seven calculation modules and a thermochemical database with more than 11 ,000 chemical compounds. The new spreadsheet type table editor gives more control to the user, the new graphics routines have fewer limitations and more formatting properties. The capability and speed of calculation routines have also been improved.

Jan 1, 1998

By Rolando Campos

In August 1993, the operation of Refimet Chile's copper custom smelter commenced at La Negra, near Antofagasta in northern Chile. Design smelter throughput corresponded to 235 000 tonnes of concentrate, calcines and copper cements arising from suppliers in the north of the country to produce 90 000 t/y of blister copper. Refimet had initially gained experienced in building and operating leaching, roasting and a blast furnace facility at Rungue, near Santiago, followed by Roasting at La Negra. The initial smelter project was based on conventional reverb- smelting and Peirce-Smith converting and the majority of equipment was 'purchased second-hand and rehabilitated or modified. After only 3 years in production, the treatment capacity was significantly improved by introduction of technical improvements to the original plant operating scheme. Recently, the plant was further expanded to an annual smelting capacity in excess of 400 000 t/y feed, corresponding to around 160 000 t/y copper production. This expansion, referred to as Phase 2, was achieved by modification of the reverb to oxy-fuel firing, addition of a further (second-hand) acid plant, fire refining and anode casting facilities. Parallel development of concentrate injection into enlarged converters-also took place. Following successful commissioning of Phase 2 expansion, initial engineering studies for a third expansion phase have been completed. This aims to use leading technology based on bath smelting of bone-dry concentrates in a Continuous Reactor. This paper provides an overview of the relatively short plant history, its development and improvements together with operating indices achieved.

Jan 1, 1998

By Stephen C. Britten

An in-situ amperometric slag sensor for measuring the concentration of easily dissociable oxides in slags at temperatures between 1200-1600°C is being developed. The sensor provides the same information as potentiometric sensors while also providing data on the concentration of the transition metal species and the diffision kinetics within the slag. The electrochemical technique utilized in the sensor is similar to methods utilized in aqueous voltammetry.

Jan 1, 1998

By D. Neuschiltz, M. Witthaut, R. Cremer

"Metastable (Ti,Al)N coatings with fee structure have been shown to exhibit superior performance as compared to TiN under conditions of wear at elevated temperatures due to their better oxidation resistance and hardness. The oxidation resistance of these coatings increases significantly with increasing Al-content. However, the deposition of (Ti,Al)N films with Ti/ Al ratios below about 30/70 leads to a hexagonal structure which is not suitable for tribological coatings. Only little is known about the location of the cubic to hexagonal phase transition and hence about the optimum composition of (Ti,Al)N hard coatings.To determine the position of this transition, Tii-xAlxN films with different Ti/Al ratios were deposited on high speed steel at substrate temperatures between 100 and 700 °C by means of reactive MSIP. The composition of the films was determined by electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS), the crystallographic structure by thin film X-ray diffraction (XRD).It could be shown that in case of deposition temperatures of 300-700 °C a two-phase region exists in the metastable TiN-AlN phase diagram, which expands with increasing temperature, wheras at 100 °C substrate temperature no two-phase region was observed. But in opposition to the phase diagram known from literature, which is based on thermodynamic estimations, the detected two-phase region is narrow for typical PVD temperatures, thus allowing the deposition of cubic single-phase Al-rich (Ti,Al)N hardcoatings for tribological applications. Based on these results, a new Ti1-xAlxN film with x = 0.62 has been developed, which showed an increase of oxidation resistance by a factor of 4."

Jan 1, 1998

By Y. Maeda

Kosaka Smelter is a copper smelter located at the nothern part of Japan? and has been treating. complex sulfide concentrates using flash smelting technology for a long time. The flash smelting technology has an advantage in the point of controllability of matte grade and heat balance in the reaction shaft. But the disadvantage of this process, is that the dust generation ratio is high compared with other smelting process such as injection smelting technology. This reason why is that the flash smelting process is the oxidation process for the fine sulfide concentrates applying flash reaction in the oxygen enriched stream In addition of this disadvantage, the sulfide concentrates contains much volatile impurities is resulted the dust; eneration ratio more. This paper outlines the recent improvement of the flash reaction in the furnace and the behavior of impurities in Kosaka Smelter.

Jan 1, 1998

By Takeshi Ohgai, Hisaaki Fukushima, Tetsuya Akiyama, Joon-Seo Ki

"Recently, an intensive attention has been paid to the electrodeposition of Zn-Cr alloy in the field of the production of super-highly corrosion-resistant alloy plated steel sheets for the next generation. In this study the electrodeposition of Zn-Cr alloys from the sulfate baths was conducted to investigate the codeposition mechanism of Cr with Zn. As a result, Cr was codeposited with Zn at higher current densities in both polyethyleneglycol(PEG)-free and PEG- containing baths. However, PEG made it possible to reduce Cr+ to the metallic state and Cr existed in the form of Cr(III) hydroxide in the deposits obtained from PEG-free bath. The measurements of the partial polarization curve of Zn and the pH in the cathode layer revealed that PEG acted as a polarizer to shift the cathode potential to the reduction potential of the composited hydroxides of Zn and Cr formed due to the pH rise in the cathode layer.1. IntroductionRecently, much attention has been paid to the electrodeposition of Zn-Cr alloys because of its application to the production of super-highly corrosion-resistant alloy plated steel sheets for the next generation1Hl_ Some researches have already tried to commercialize this type of steel sheet. High corrosion-resistance of this steel sheet is brought about by codeposited Cr in the alloys. According to Piontelli's classification5l concerned with metal deposition from aqueous solution, Cr belong; to an inert metal and its deposition is associated with a large amount of hydrogen evolution. Therefore the current efficiency for Cr deposition is extremely poor. It has been also reported that Cr is unable to codeposit in the electrodeposited Zn film in the absence of a certain additive in the solution. 0-compounds group colloids7l, ether group organic compounds8), 9>, peptide based compounds10l, etc., have been found to be effective additives to induce the codeposition of Cr with Zn. However, few studies have been made on the codeposition mechanism of Cr with Zn. In this research, the fundamental electrodeposition behavior of Zn-Cr alloys from sulfate baths was investigated to clarify the codeposition mechanism."

Jan 1, 1998

By Vadim J. Jabotinski

This paper describes several areas of application for electron beam processing of materials. The technology and use of electron beam systems in gas phase synthesis reactions are described. Gas phase reactions may be used to generate ultra- fine metal or ceramic powder that are very pure and crystalline. Among the examples presented are: the generation of nanometer sized metal powders and the gas phase synthesis of silicon carbide for silica and methane. The experimental system is described and future theoretical and experimental objectives are identified.

Jan 1, 1998

By Patricio Barrios

In February 1996, ATLANTIC, COPPER completed the construction of a Project for Expansion and Environmental Improvements in its Smelter and Electrolytic Refinery located in Huelva. Following the expansion, the new operating concept is based on the simultaneous blowing of two converters, while increasing throughput in the Flash Furnace up to the level required to deliver matte to both converters. While the production level planned with the Project.(270,000 MTPY of copper from concentrates) was reached the following June, work since then has been carried out to optimize the new equipment .and to develop a new operating shedule. This paper describes operational experiences from the start up of the Expansion Project, difficulties encountered and operating improvements introduced, which have allow an increase of production levels up to 300,000 MTPY of copper.

Jan 1, 1998

By Vladimir Mindin

This paper presents results of thermodynamic investigations and experimental' studies of some essential for pyrometallurgy of sulfide concentrates topics. Among them: 1. Thermodynamic simulation and experimental investigations of roasting process, 2. Thermodynamic investigations of sulfur dioxide off-gases treatment technologies. 3. Investigations on "Mind in -Kiknadze" effect of suppression of sulfur dioxide formation during sulfide concentrates roasting in the vapor containing atmosphere. 4. Thermodynamic simulation and experimental investigations of sulfide concentrates and manganese containing materials co-roasting processes. Some essential aspects of thermodynamic simulation techniques are also discussed.

Jan 1, 1998

By Michael J. Nicol

Growing environmental and occupational safety concerns about the use of cyanide in gold processing has increased the interest in more acceptable alternatives. The most likely of these is thiosulfate. However, the thiosulfate process lacks a proven in-pulp method of recovering the dissolved gold, because activated carbon is not effective for the absorption of the gold thiosulfate complex .. Anion exchange resins do offer a possible route for in-pulp recovery. This paper describes work aimed at the evaluation of the effectiveness of commercially available anion exchange resins for the recovery of gold from thiosulfate leach liquors? and pulps. It has been found that strong-base resins are superior to weak-base resins in that they have a larger capacity, which assists in reducing the competition from other anions within a leach solution. Further studies with a selected commercial strong-base resin have shown that competing polythionateanions (particularly tri-and tetrathionate). Lower the maximum possible gold loading but that gold is selectively recovered over other base metal anions in solution. Kinetic experiments found that while? competilig anibns did not affect the initial rate? of gold loading it was important to minimise the contact time of the resin in solution so to prevent displacement of loaded gold by competing anions over longer times. A small-scale resin-in-pulp plant investigation showed gold can be recovered from a leach pulp by a strong-base resin to yield gold loadings of 3000 mg/L, barren pulp containing less than 0.05 mg/L of dissolved gold and. copper loadings of 500 mg/L. Loaded copper was displaced gold and at a loading of 2000 mg/L gold the copper loading was minimal «500 mg/L). The resin was found to recover gold adsorbed on the solids that would, otherwise have. reported to tails if a solid/liquid separation method were used. A patented two-step elution process in which copper and then gold are separately eluted from the resin is also discussed.

Jan 1, 1998

By Sungdon Kim, Chuljoo Kim, Joonsoo Kim, Hosung Yoon

"This study was performed to establish the optimum leaching condition through the experiments for the oxidized roasting followed by leaching of fluorocarbonate rare earth mineral (bastnasite) using sulfuric acid, and to establish the optimum condition for the recovery of cerium by ion- sieve method from the leached solution of bastnasite. The optimum conditions for the sulfuric acid leaching by the oxidizing roasting of bastnasite concentrates are that the roasting temperature is 550 -600 °C, the roasting time is 2 hrs, the concentration of sulfuric acid is 6N, the leaching temperature is S0°C and the leaching time is 3 hrs. At this time, the leaching yield of total rare earth oxides in the leaching of bastnasite concentrates is about 91%. When cerium is recovered by ion-sieve method from the solution obtained by the sulfuric acid leaching of the roasted bastnasite, the optimum conditions are that the TREO(total rare earth oxide) of leached solution is below 70 g/l, the flow rate of leached solution is 9.6 ml/min and the ratio of height to diameter of resin packed in column is above 9. In these conditions, the recovery of cerium of yield 85% and purity 96% is possible.IntroductionThe rare earths are generally called to Lanthanides, which are totally 17 elements including Scandium of atomic number 21 and Yttrium of atomic number 39 in addition to 1 S elements from Lanthanum of atomic number 57 to Lutetium of atomic number 71. Since the separation to each element is very difficult because of their similar chemical properties, the rare earths were used as the mixed rare earths and the mischmetal without separating to each element. However, the high purity rare earths are recently produced commercially to each element so that they are used as the materials for high tech. industry such as electric and electronic materials, catalysts, optical materials, special alloy and 8Uperconductive materials, and their consumption is rapidly increasing. Therefore, the purpose of this study is firstly to prepare leached solution by using the series of process of the oxidation-roasting and leaching by sulfuric acid. Next, second purpose is the separation and recovery of cerium by ion-sieve method."

Jan 1, 1998

By William E. Torres

The Southern Peru Limited smelter, in Ilo, operates two reverberatory furnaces, seven Peirce-Smith converters, one Teniente Converter, two casting wheels and a single contact acid plant. The Teniente Converter was commissioned in August 1995 and was designed to smelt 744 dry metric tons (820 dry short tons) of concentrate per day. The process off-gas is collected in a water-cooled hood, cooled in a spray chamber, and cleaned in a Joy electrostatic precipitator for further treatment in the Acid Plant. This paper presents the current Teniente Converter operating practices and control philosophy. Relevant improvements and modifications to achieve a 379 day campaign without tuyere replacement and a daily average smelting rate of 862 dry metric tons (940 dry short tons) of concentrate are discussed.

Jan 1, 1998