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By Pengfu Tan

A thermodynamic model and computer program, CuModel, has been developed to model the distribution behaviors of Cu, Fe, S, O, Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag, copper loss in the slag, and heat balance in copper smelting process, matte converting process and copper con-tinuous smelting process. It can be predicted for any set of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxy-gen-enriched air. This model accounts for physical entrainment between matte and slag phases. It can be used in Isasmelt process, copper flash smelting process, Mitsubishi process, P-S con-verting process and Noranda process. The predictions by the present computer model are com-pared with the known commercial data from Guixi Smelter in China, PASAR Corporation in Philippines, Horne Smelter in Canada, MIM Limited in Australia and Naoshima Smelter in Ja-pan. The agreements between the computer predictions and the commercial data are excellent. In this paper, the applications of CuModel in the copper metallurgical industries have been pre-sented. CuModel has been used by Daye Smelter and Guixi Smelter in China, and by PASAR in Philippines as well.

Jan 1, 2004

By C. A. D' Odorico

The zinc pressure leaching (ZPL) plant at Teck Cominco's Trail Operations was started up in 1981 and represented the world's first commercialization of the technology. From the outset, the process was designed to operate using iron-rich Sullivan Mine zinc concentrate. When the Sullivan Mine reached the end of its life in 2002, the ZPL plant underwent a significant process change with the treatment of 100% Red Dog zinc concentrate. Through careful improvements to existing plant processes, controlled changes to plant operating parameters and a rapid adjustment to the modified process by operations personnel, the plant has been successfully converted to processing a feed of 100% Red Dog zinc concentrate. This paper discusses the challenges faced during the conversion and describes the modifications to plant operating procedures, as well as changes to plant processes.

Jan 1, 2004

The intent of this manual is to provide guidelines for inspectors of drilled shaft construction otherwise referred to as drilled piers, caissons or bored piles. It should also be helpful to train beginning geotechnical engineers with limited first hand experience or for geotechnical engineers who are training inspectors. It is expected that the general guidelines and procedures described here will be supplemented by local geotechnical engineers working in a particular region based on local practice and experience. Since drilled shaft construction procedures vary widely based on local geology and size of project, an all-inclusive manual is not considered practical. This manual focuses on traditional topside inspection for routine drilled shaft construction. Other inspection and evaluation methods that rely on electronic equipment are available, but these methods require extensive training and experience in the interpretation of results. These more sophisticated methods of drilled shaft inspection and evaluation are common in construction, but they are usually provided by specialty subconsultants. The subconsultant will typically submit a report for each shaft, which will be reviewed by the geotechnical engineer. Other manuals are available to describe the electronic methods of drilled shaft inspection.

Jan 1, 2004

By Steve Brace

Electronic detonators have been commercially available to the mining industry worldwide for over ten years. It is estimated that total cumulative global sales will have reached 25 million units by the time of the Conference in February 2004. This is below 0.2% of all detonator types sold during this period. Perhaps 20 million will have been used underground in South African gold, diamond and platinum mines. These will have been produced by South African companies, in South Africa for South African customers. Here efforts have met with greater success and in 2003 fully 5 million, or 3% of local detonators sold, could be of an electronic type. However, it is estimated that about US$7.00 (R50.00) has been expended on R & D, manufacturing facilities and marketing, for each unit so far sold. Large sums of money continue to be spent. Despite the apparent success in South Africa, is it justified? Electronic initiation systems have not produced significant technical benefits to the end-user underground nor corporate profits to the supplier. Some doubt they ever will (even from the large surface operations where the price per unit is much higher). A conclusion might be that they have failed. In 1998 Smit and Pistorius wrote a paper titled “Implications of the Dominant Design in Electronic Initiation Systems in the South African Mining Industry”. This ISEE paper seeks to summarise and review the conclusions of the earlier work. These were: that a dominant design had not yet emerged; the type of connector and the way in which detonators are connected and programmed would be a strong determinant influencing the development of a “winning” product; technical aspects rarely solely determine which becomes the dominant design (marketing, social and economic factors often have a strong influence); electronic initiation systems were an emerging technology for the underground gold mining industry in South Africa and because it was under severe cost pressure the mines would look to them to raise productivity and hence profits; finally, as a dominant design begins to emerge, one could expect a number of players to exit from the industry.

Jan 1, 2004

By A. Vahed

The Goro Nickel Project is situated in the Southern Province of New Caledonia. Inco Limited and Goro Nickel S.A. have developed a process that features the use of pyrohydrolysis to produce nickel oxide. The process treats a blend of laterites by Pressure Acid Leaching followed by solvent extraction of nickel and cobalt using Cyanex 301®. Purified nickel chloride solution is converted to high purity NiO product and 6M hydrochloric acid, which is recycled back to the SX circuit. In co-operation with Andritz AG, spray roaster and fluid-bed pyrohydrolysis technologies were examined for this purpose. Tests were conducted at the Andritz AG pilot plant in Vienna, Austria, and at Goro in larger scale installations. The latter served to establish process engineering design parameters for scale-up. Several process variables were investigated in both technologies and the off-gas characteristics were established. Fluid-bed pyrohydrolysis was selected for the Goro commercial plant, primarily because it produced a granular nickel oxide. The main focus of this paper is to outline the results obtained in pilot plant studies of liquid fueled fluid bed pyrohydrolysis for the Goro Project. Keywords: lnco Goro Nickel, Fluid Bed Pyrohydrolysis, Pilot Plant Tests

Jan 1, 2004

By Ryosuke Matsuoka

Keywords: Tantalum capacitor, Scrap, Recovery, Titanium, Chlorination A recycling process for tantalum from capacitor scraps using an oxidation process followed by mechanical separation and chemical treatment was investigated. This study demonstrates that sintered tantalum electrodes inside the capacitor scraps can be mechanically collected after the oxidation of the scraps in air, and high-purity tantalum oxide powder (Ta2O5) was efficiently recovered after chemical treatment. By reducing the Ta2O5 obtained through magnesiothermic reduction, tantalum powder with 99 mass-% purity was obtained. Using the chlorination for tantalum recovery was also investigated, and the tantalum or tantalum compounds were reacted with chloride wastes such as FeClx. It was found that tantalum was effectively separated and purified when tantalum powder is reacted with FeClx at 1100 K under an argon atmosphere. This recycling process utilizing chloride scrap has now been extended to other reactive metals such as titanium.

Jan 1, 2004

By Yuanbing Ling

Keywords: Calcium sulfate, Sulfuric acid, Phase transformations, Thermodynamic analysis As part of a boarder research project, seeking the development of a cost-effective process for direct production of the high value material, -calcium sulfate hemihydrate, from sulfuric acid at atmospheric as opposed to elevated pressure conditions, the fundamental work presented here has been undertaken. This includes experimental monitoring of phase transformation reactions and thermodynamic analysis of the relationships among the various phases, namely, calcium sulfate dihydrate, hemihydrate and anhydrite in aqueous sulfuric acid solution at temperatures ranging from 20oC to boiling point.

Jan 1, 2004

By Pengfu Tan

NiModel, a thermodynamic model, database and computer program, has been developed to predict the distribution behavior of Ni, Cu, Co, Fe, S, O, As, Sb and Bi, and heat balance in the nickel pyrometallurgical processes such as Outokumpu flash smelting, Outokumpu direct high-grade matte smelting, INCO flash smelting, and Peirce-Smith converting processes. In this model, as much as 16 elements (Ni, Cu, Co, Fe, As, Sb, Bi, S, O, Al, Ca, Mg, Si, N, C and H) are considered. The compositions of matte, slag and gaseous phases, and heat balance are calculated using the thermodynamic data and the activity coefficients of the components derived from the experimental data. The model predictions were compared with the known industrial data from Kalgoorlie Nickel Smelter in Australia, Outokumpu Harjavalta Nickel Smelter in Finland and INCO Metals Company in Canada, and an excellent agreement was obtained. In this paper, the applications of NiModel in the nickel pyrometallurgical industries have been presented. NiModel has been used by Jinchuan Group Limited in China.

Jan 1, 2004

By C. Blawert

The corrosion properties of the skin and the bulk of semi-solid processed and high pressure die cast AZ91 alloy were studied in 5% NaCI solution by (a) analysing the corrosion morphology, (b) measuring electrochemical polarization curves, (c) performing electrochemical impedance spectroscopic measurements, and (d) immersion tests at constant pH-values. Using XRD, LM, SEM and EDX to evaluate the microstructure of skin and bulk specimens, the corrosion results were related to the microstructures of the particular alloys. However, microstructure and corrosion performance were found to be similar for both production processes, and only slight but distinct differences were found. Generally, the skin corrosion properties are inferior to those of the bulk, with the exception of the high pressure die cast AZ91 alloy, where the finer microstructure of the skin layer exhibits a better performance as showed by impedance studies and confirmed in long term immersion tests.

Jan 1, 2004

By M. Pearson, W. Bristowe, A. Hanson

"There's no such thing as quality assurance; only quality control ... by inspection. "(1) A common misunderstanding in the procurement and construction of custom designed, fabricated pressure vessels and piping systems is that quality assurance can be achieved by simply referencing codes, standards, ISO 9002, QMS or other such programs in the contract documents. In the authors' experience, nothing could be further from the truth, not detrimental to the performance of the equipment than the exclusion of inspection activities and reliance upon warranties and "fit-for-purpose" clauses. Likewise, the expectation that fabricators, suppliers, or third party inspectors can provide such assurances is also unrealistic where they have limited knowledge of the process, material selection criteria, or limited technical resources. The development and successful execution of a quality assurance program is a collaborative effort by engineers, designers, material suppliers, equipment fabricators, and field inspectors with the full understanding and support of the end user.This paper presents an outline of the quality control activities undertaken by the authors for several recently completed and on-going hydrometallurgical projects. The activities include: prequalification of fabricators and sub-vendors, shop audits, material validation testing, material source control and verification, positive material identification of weld metal overlay, specialised welding inspection, contamination control for titanium and titanium-clad fabrication, eddy current and mass spectrometer (helium) leak testing of shell-and-tube heat exchangers, hot cycle testing of titanium clad equipment, tolerance verification for refractory lined equipment, final inspection and cleaning.

Jan 1, 2004

By Chuan-Jian Zhong

Gold-based nanoparticles in the size range of a few nm have attracted increasing interests in catalysis, sensors and biomedical applications. The study of the unique catalytic properties of nanosized gold was inspired by the pioneering work of Haruta on the nanogold-catalyzed CO oxidation (1-4). There have been a number of excellent reports discussing both fundamental and application aspects of gold nanoparticles in catalysis (3-8). Our work reported herein is aimed at investigating the preparation and application of gold and its alloy nanoparticles for potential applications in fuel cell catalysis. Fuel cells operating by electrochemical oxidation of hydrogen or methanol fuels at the anode and reduction of oxygen at the cathode are attractive power sources due to their high conversion efficiencies, low pollution, lightweight and high power density. While methanol offers the advantage of easy storage and transportation in comparison with hydrogen fuel cell, its energy density (~2000 Wh/kg) and operating cell voltage (0.4 V) are much lower than the theoretical energy density (~6000 Wh/kg) and the thermodynamic potential (~1.2 V). The poor activity of the anode catalysts and inefficient activity or issue related to "methanol cross-over" at the cathode electrode are associated with the loss of about one-third of the available energy at the cathode and the other one-third at the anode. Extensive studies have been focused on Pt-group metals (Pt+Pd+Rh+Ru+Ir (PGM)) for both anode and cathode catalysts. A major problem is the poisoning of Pt by COlike intermediate species (9,10). Recently, oxide-supported gold nanoparticles in the <10 nm size range have emerged as one of the best catalysts for CO oxidation (1-3,11), and for water gas shift reaction in reforming stage using 5 nm Au on Fe2O3 (6). Gold and its alloy with other metals in the nanosize range present new alternatives (2,12). Whether the unique properties of gold nanoparticles can be exploited for addressing these problems is a focus area of our work. The ability to harness the large surface area-to-volume ratios and the unique surface sites of nanoparticles in <10 nm size range, especially in heterogeneous catalysis, constitutes a major driving force in fundamental research and practical applications of nanoparticle catalysts. It is this size range over which the metal particles undergo a transition from atomic to metallic properties. The understanding of factors controlling the morphological and surface reconstitution associated with such a size range is of fundamental importance to the ultimate exploration of nanostructured catalysts. We have been investigating the interfacial structures and properties of core-shell types of nanoparticles consisting of gold or alloy nanocrystal cores and organic monolayer shells that were prepared by twophase synthesis (13) and processing (14) protocols. Important attributes of such nanoparticles include controllable size monodispersity, processibility, and stability towards size- and composition-tunable catalysis (15-21). Some of these attributes were studied for understanding their electrocatalytic properties in the oxidation of methanol and reduction of oxygen, which are of fundamental interest to fuel cell technology.

Oct 1, 2003

By Philippe V. Scheers

Polycrystalline gold, glassy carbon and gold-activated glassy carbon electrodes were compared for the production of hydrogen peroxide by the cathodic reduction of dissolved oxygen. Gold was deposited on glassy carbon by sputtering with a sputter coater and by electrodeposition from a diluted KAuCl4 solution using short potential steps. The sputtered gold particles were not adherent enough, but there were no adhesion problems with the electrodeposited gold particles. The gold coverage of the glassy carbon surface could be varied by applying a different number of potential steps. The overpotential for the electroreduction of oxygen to hydrogen peroxide decreases with increasing gold coverage of the glassy carbon surface, and for gold coverages exceeding about 16 %, the overpotential is close to that observed on polycrystalline gold.

Oct 1, 2003

By Masayuki Ishikawa

In a radio frequency and optoelectoronic device packaging, Gold-Tin (Au-20 wt% Sn eutectic) solder is used widely due to the excellent electrical and thermal conductivity, high strength, and negligible creep characteristic under repetitive thermal cycling. With the recent lead-free movement, Gold-Tin solder is recognized as an alternative material for high temperature Lead-Tin solder. Generally, Gold-Tin solder is supplied in the forms such as ribbons, pellets, and ring frames. However, these forms must be set-up accurately on the joint area to press chips in bonding, therefore, it is difficult for these forms to satisfy the recent requirements for the down sizing in the connection areas. On the other hand, Au-20 wt% Sn solder paste can be applied flexibly to various supplying methods, such as printing, dispensing system and pin transcript. These methods also make it possible to reduce the production cost. However, in the case of using the solder paste, the void issue is one of the most undesirable problems. The void causes the degradation of the characteristics such as the bond strength, electrical characteristic and thermal conductivity. We have been intensifying the development of the void free paste, and have achieved void reduction by optimizing the powder size, the flux composition and the reflow condition.

Oct 1, 2003

By Mari Yamamoto

Controlled thermolysis of gold(I) complex, [Au(C13H27COO)(PPh3)], at 180 °C for 5 h under an N2 atmosphere affords the new type of monodispersed spherical gold nanoparticles capped by myristate and a small amount of PPh3 ligands (average diameter 23±1.5 nm), in spite of no use of solvent, reducing agent and stabilizer. Much attention has been paid to the preparation and structure determination of transition metal nanoparticles, because of their widespread use in technological applications.1 In general, the chemical reduction of metal salts and organometallic complexes2 by the use of reducing agent is carried out to prepare gold nanoparticles. In some cases, a large amount of solvent and stabilizers such as surfactants,3 polymers4 and ligands5 are used to prevent agglomeration of particles and control the particle size. For instance, Brust et al. reported a two-phase reduction of AuCl4 - by NaBH4 in the presence of dodecanethiol as stabilizer to prepare gold nanoparticles.6 On the other hand, O?Brien et al. recently reported an one-phase preparation of gold nanoparticles by the reduction of AuCl4 - by NaBH4 in the mixture of tri-n-octylphosphine oxide and octadecylamine which act as both solvent and stabilizer, but this procedure also needs reducing agent.7

Oct 1, 2003

By Kenji Koga

In order to derive the population distribution of gold nanoparticle morphologies as a function of size, highresolution electron microscopic (HREM) observations and structural analyses were done for over 4000 particles (3-18 nm) grown by an inert gas aggregation (IGA) source using helium. To obtain structural features threedimensionally and not to skip high-contrast images, twenty photos were taken for each particle by changing tilting angle of a specimen holder in combination with the through-focus procedure. For the reliable structural determinations, HREM images and their tilting sequences were directly compared with multislice-simulation results for icosahedral, decahedral and face-centered cubic morphologies, and finally the population distribution of each morphology was obtained as a function of size. In the present sample, icosahedral particles were dominantly populated over the whole observed size range and decahedral particles with non-spherical truncated bi-pyramid shape were secondly dominant. Even though a large number of sampling has been done, few crystalline particles were observed.

Oct 1, 2003

By Jolanta Olkowska-Oetzel

Reactions of gold?phosphino complexes [(AuX)(PR3)] (X= Cl, Br, I; R = organic rest) with Se(SiMe3)2 lead to the formation of gold complexes with chalcogenide bridges. The reaction of the complex Ph3PAuCl and tBuSe(SiMe3) gives the cluster [Au5Se2(PPh3)4]Cl 1. The in situ preparation of the complex [(AuCl)2dpph] (dpph = Ph2P(CH2)6PPh2) by reaction of dpph with Me2SAuCl, and subsequent reaction with Se(SiMe3)2 leads to the formation of [(Au3Se)2(dpph)3]Cl2 2. Reactions of the gold(I) complex [(AuCl)2dpppe], (dpppe = Ph2P(CH2)5PPh2) with Se(SiMe3)2 and InCl3 in different molar ratios lead to the formation of [Au10Se4(dpppe)4]InCl5 3 and [Au4(SeInCl3)2(dpppe)2] 4. The reaction of [(AuCl)2dpph] with Te(SiMe3)2 and GaCl3 produces the isostructural cluster compound [Au4(TeGaCl3)2(dpph)2] 5. From the reaction of Se(SiMe3)2 with [(AuCl)2dppe] (dppe = Ph2P(CH2)2PPh2) and InCl3 [Au8Se4In(dppe)4](InCl4)3 6 can be isolated. The structures of 1 - 6 were determined by X?ray diffraction.

Oct 1, 2003

By Gaby Steinbach

A novel synthesis is described for the preparation of supported gold catalysts for low-temperature CO oxidation. The novel route is a variation of the inverse co-precipitation method and requires amphoteric metal hydroxides, with zinc and aluminium hydroxides chosen. Catalysts were prepared by inverse co-precipitation (ICPa) and by the novel route (ICPb) and tested for CO oxidation at 60ºC. Preliminary results showed the novel route to be superior to ICPa; the catalysts prepared by ICPb showed higher catalytic activities. The effect on catalytic activity of parameters such as pH, calcination temperature, washing of precursor and calcined catalysts and ageing was investigated. A preparation pH of 9 and a Zn to Al mass ratio of 3 proved to be optimal. It was possible to remove residual chloride by washing thereby enhancing catalyst performance. Ageing and Mg citrate addition were also shown to improve catalyst performance. Characterization of the catalysts revealed that better activities were obtained when the support was more crystalline and had a higher surface area. The presence of carbonate-containing species in the support decreased catalytic activity. 197Au Mössbauer Spectroscopy revealed the presence of Au3+ when catalysts were heat-treated at temperatures of 200ºC and below. Catalysts calcined at 400º had 75% of the gold present as Au0, with the remaining gold present as Au3+.

Oct 1, 2003

By Peter Claus

In the last years, supported gold catalysts with particle sizes smaller than 10 nm have attracted a lot of attention. While gold bulk metal is rather inert in chemical reactions and, thus, is of low interest for catalysis, highly dispersed gold particles supported on oxides as TiO2 or ZrO2 show surprisingly high activities in some reactions important for the chemical industry. The oxidation of carbon monoxide at low temperatures is mainly used as model reaction to study the unusual properties of gold catalysts [1]. On the other hand, to evaluate the catalytic potential of gold, other chemical reactions which allow to control also the selectivity have to be considered. The selective hydrogenation of ???-unsaturated aldehydes to allylic alcohols is of both commercial relevance (e.g. in fine chemical and pharmaceutical intermediate production) and specific scientific interest [2]. Note that thermodynamics favors hydrogenation of the C=C over the C=O group (stronger negative free reaction enthalpy of 35 kJ/mol), and for kinetic reasons the C=C bond is more reactive than the C=O group. Thus, in the presence of most of the conventional hydrogenation catalysts, based on Pt, Rh or Pd, -unsaturated aldehydes such as acrolein and crotonaldehyde are hydrogenated predominantly to the saturated aldehydes and only to a minor extent to unsaturated alcohols. Therefore, it is desirable to find catalysts which are able to control the intramolecular selectivity by hydrogenation preferentially the C=O group while keeping the olefinic double bond intact (Fig. 1).

Oct 1, 2003

By Donka H. Andreeva

Gold catalysts based on different supports, titania, zirconia, ceria and mesoporous titania and zirconia, nonpromoted and promoted by vanadia in the reaction of complete benzene oxidation have been studied. XRD, HRTEM, TPR, Raman and ESR spectroscopy were applied for the characterization of the catalysts. The influence of gold on the reduction behavior, state and structure of vanadia on the surface was studied, as well as the role of supports nature on the properties and catalytic activity. A strong synergistic effect between gold and vanadia was observed for the all studied catalysts with an exception of the catalysts supported on mesoporous zirconia. In the last case the catalysts containing gold and gold-vanadia exhibit high and equal catalytic activity. The catalysts on ceria show highest and stable catalytic activity in the studied reaction among the all studied catalysts.

Oct 1, 2003

By Maria Agostina Cinellu

Some aspects of the reactivity of the two different kinds of gold(III) oxo complexes [Au2(N,N)2(?-O)2][X]2 [N,N = 2,2&apos;-bipyridine (bipy) (1), 6-alkyl-2,2&apos;-bipyridine (bipyR) (2), R = Me a, CH2Me b, CHMe2 c, CMe3 d, CH2CMe3 e] and [Au2(C,N,N)2(?-O)][X]2 [HC,N,N = 6-benzyl-2,2&apos;-bipyridine (bipyR&apos;) (3), R&apos; = CHMeC6H5 a, CMe2C6H5 b] (X = BF4, PF6) have been studied. Treatment with water converts the unsubstituted bipyridine complex [Au2(bipy)2(?-O)2][PF6]2 (1) and the cyclometallated derivatives [Au2(C,N,N)2(?-O)][PF6]2 (3) into the water soluble monomeric hydroxo species [Au(bipy)(OH)2][PF6] (4) and [Au(C,N,N)(OH)][PF6] (5), respectively. These hydroxo species, likely the intermediates in the formation of the oxo complexes, are quantitatively reverted to the latter ones by reflux in anhydrous solvents. Both kinds of oxo complexes react with PPh3 to give OPPh3, the gold(I) complex [Au(PPh3)2][PF6] and the free bipyridine ligands. The reaction of the dioxo complexes [Au2(bipyR)2(?-O)2][PF6]2 (2a, 2b, 2c, 2e) with different alkenes gives the unprecedented alkene complexes [Au(bipyR)(?2-alkene)][PF6]. The styrene adduct [Au(bipyip)(?2- CH2=CHPh)][PF6] (7) (bipyip = 6-iso-propyl-2,2?-bipyridine c) has been characterized, inter alia, by X-ray diffraction analysis. Organic products arising from olefin oxidation are also found in the reaction mixture.

Oct 1, 2003