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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 J. C. Gathje

Newmont acquired the Phoenix Project through the acquisition of Battle Mountain Gold in 2000. Shortly after the acquisition, Newmont Metallurgical Services (NMS) and Nevada Operations began development work on a process to Pressure Oxidize (PDX) precious metal rich copper concentrates from Phoenix using the Lone Tree PDX facilities at Valmy, Nevada. The high precious metals content of the Phoenix concentrate - Au up to -300 g/t and especially Ag, up to -1700 g/t - led Newmont to the development of a High Temperature PDX process that achieves high cyanide leach recovery of Au and Ag, from the PDX solids, without the requirement for a messy and expensive "lime boil" or sulphate destruction process. Base metals content in Phoenix concentrates range from: 15-25 % for Cu, 1-10 % for Zn and 0-2 % for Pb. Excellent solution extraction of Cu and Zn is achieved while Pb is precipitated in the PDX residue. In addition to achieving high Au and Ag recovery this process produces very clean PDX discharge liquors that require minimum effort to remove contaminant metals and PDX solids that have superior settling and filtration characteristics. All of these factors contribute to lower capital and operating costs for the overall process. This paper describes the laboratory and PDX pilot plant developments for this process.

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 S. Nagamatsu

Alumina supported gold catalyst prepared by spray reaction method (spr) provides gold particle with about 20 nm of diameter. The gold particle size is larger than conventional gold catalysts. However, the spr catalyst shows higher catalytic activity for NO-CO reaction. In the present paper, we have discussed the local structures of spr-Au/Al2O3 catalyst by using Au L3-edge XANES spectra. In order to investigate the local structures of Au-sites, multiple scattering approach to XANES analysis was applied. Calculated Au L3-edge XANES spectra for fcc-Au and Au2O3 were in good agreement with the observed spectra. XANES spectra for spr-Au/Al2O3 were characterized by 4 types of Au sites (bulk, interface, surface and peripheral). In this case, almost all gold sites (> 90 %) are bulk site. The other sites are less than 10 % of gold particle. However, the experimental and the calculated results of Au L3-edge XANES spectra for spr-Au/Al2O3 require about 30 % of gold oxide or hydroxide. Bulk of Al2O3 contains a certain number of gold nano-particles, which was incorporated in the bulk Al2O3 support. In the interface area, gold oxide forms a few layers. This result was also supported by DV-Xa electronic structure calculations. The comparison of the catalytic activities of the spray catalysts and the impregnation catalyst for the NO-CO reactions imply synergy effects between gold nano-particles and alumina support.

Oct 1, 2003

By Paul J. Cascone

This paper will discuss the science behind the development of a unique gold alloy for dental prosthetic applications. The alloy (GOLDTECH BIO2000) contains 99.7% gold providing unquestioned biocompatibility and unsurpassed esthetics. The topics discussed are: (1) How the alloy meets the functional requirements of a porcelain-fused-to-metal dental alloy. (2) How the alloy color affects the esthetics of the restoration and why the color of gold is best. (3) Overcoming the intrinsic malleability of gold when grinding the alloy surface. (4) Preventing the oxide color from interfering with the alloy esthetics. (5) Attaining excellent porcelain adhesion. (6) How the design of the restoration allows for the production of single and multiple unit restorations. Gold 2003

Oct 1, 2003

By Christina Graf

A synthesis of colloidal gold shell particles with a silica core is described. Small gold nanoclusters were attached to the functionalized surface of colloidal silica particles. Reductive growth and coalescence of these clusters lead to the formation of a closed gold layer. By variation of the thickness of this gold layer and the radius of the shell it is possible to adjust the plasmon resonance of the gold shell particles over the whole visible and infrared region of the spectrum. The optical properties of the particles made are in good agreement with theoretical calculations for coreshell particles. Due to their low polydispersity these gold shell particles form in solution large crystals with submicron lattice constants. It is also possible to produce hollow gold shells by dissolution of the silica core. A new method to coat the silica core gold shell particles with an additional outer silica shell is also presented. This allows due to a reduction in the Van-der-Waals forces to make more permanent dried crystals and facilitates functionalization of the particles for use in various photonic applications.

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 Christopher W. Corti

A major aim of the GOLD 2003 conference, is to promote new gold related science and technology with a view to developing new useful industrial applications for gold. Current industrial uses have provided a steady annual industrial demand for gold of around 350-400 tonnes in recent years, the bulk of which is centred on electronics applications, with dental uses constituting the second largest application. However, there is good reason to believe that whilst gold will continue to play a major role in these sectors in the future, substantial growth of demand is not anticipated. Increased industrial demand for gold is only likely to come through the emergence of new applications, probably most significantly in five broad market sectors: ? Pollution and emission control technologies, including fuel cells. ? New uses for gold in advanced electronics, electrical systems and devices. ? Chemical processing of a range of bulk and speciality chemicals, using gold based catalysts ? Advanced coatings exploiting the novel properties of gold, particularly in nanoparticulate form. ? New biomedical uses for gold including medical treatments, drugs, implants, sensors and devices. There is cause for optimism that many new applications for gold could emerge in these sectors over the next decade and that this will lead to a substantial growth in demand for gold. It is clear that many of these new opportunities will be based on a chemical approach to synthesis of useful products rather than what has historically been a materials or mechanical approach. To turn this expectation into reality requires sustained support of R & D and a determination to exploit this new science and technology into viable commercial applications.

Oct 1, 2003

By Rodolfo Zanella

Au/TiO2 catalysts prepared by deposition-precipitation with NaOH (DPN) (~3 wt%) and urea (DPU) (~8 wt%) were tested in crotonaldehyde hydrogenation at atmospheric pressure. There is no differences in activity (mole.gAu -1 s-1) and selectivity between both DPU and DPN samples for a given activation treatment. This is due to the fact that DPU and DPN samples exhibit similar gold particle size distribution, although the gold loading in DPU is much higher that in DPN. The DPU samples were reduced under H2 at different temperatures (120-500 °C) or under air at 300 °C with various flow rates, to vary the average particle size within a large range, 1.7 to 8.7 nm. The selectivity to crotyl alcohol (selective hydrogenation of the carbonyl bond) is high, 60-70 %, and almost constant as a function of the particle size. The selectivity to crotyl alcohol is also constant for conversions between 10 and 50%. These results suggest that the adsorption mode of crotonaldehyde is of ?3 or ?4-type. In contrast, the TOF depends on the gold particle size, it drastically increases when the gold particle size is ~2 nm. Our results are in agreement with former studies that suggest that the gold atoms involved in the hydrogenation process are those of low coordination.

Oct 1, 2003

By Stephen J. Roberts

Gold catalysts were prepared on co-precipitated, calcined copper oxide - zinc oxide support by an inverse deposition-precipitation method. These catalysts were characterised by X-ray diffraction (XRD) and temperature-programmed reduction (TPR) and studied for CO oxidation activity at various catalyst calcination temperatures. TPR studies of the support material exhibited a double peak and shift to lower temperatures for the reduction of Cux+ to metallic copper, as opposed to the single reduction peak for pure CuO. This phenomenon is possibly caused by an interaction with the zinc oxide. The addition of gold to the support CuOZnO led to a further shift in copper reducibility to lower temperatures. Gold present in the initial uncalcined catalyst as Au3+ was auto-reduced to Au0 under various calcination temperatures. The Au3+ reduction peak was observed to shift to lower temperatures with increasing calcination temperature. The catalytic activity was found to pass through a minimum value with respect to calcination temperature. Catalysts with both gold in entirely the 3+ or metallic oxidation state were found to exhibit high activity. Furthermore, the catalysts were found to decrease in activity with decreasing Au3+ content up to an intermediate calcination temperature, afterwhich the activity increased sharply. Possibly at higher temperatures, a stronger Au-support interaction is formed, leading to a new active site.

Oct 1, 2003

By Susumu Tsubota

Three types of reference gold catalysts, i.e., 3wt%Au/TiO2 (Au-Ti: Type A), and 0.3wt%Au/Fe2O3 on alumina beads (AUS: Type B), and 5wt%Au/Fe2O3 (Au-Fe: Type C), were produced in a test plant scale by Sud-Chemie Catalysts Japan, INC. under the licensing of AIST. To evaluate the validity of the preparation methods and conditions used for the reference samples, elemental analyses by ICP, particle size measurements by TEM, and catalytic activity measurements for the oxidation of CO and H2 over these catalysts were made. Gold catalysts can be prepared in a large scale of ca 400g for the Au-Ti and Au-Fe catalysts, 5 kg for the AUS catalyst with good reproducibility. It was confirmed that they were available for useful as the reference gold catalysts of World Gold Council.

Oct 1, 2003

By Laurence D. Burke

The electrocatalytic behaviour of gold in aqueous media is surprisingly complex and a novel view of gold electrode surfaces is proposed to explain the observed electrochemical responses. The metal surface is considered as a chemically (or redox) modified electrode, with equilibrated, low energy, surface gold atoms functioning as a relatively inert support and low coverage, high energy, protruding gold atoms (or minute clusters of same) functioning as electrocatalytic redox mediators. The protruding atoms are viewed as surface active sites and the complex electrocatalytic behaviour is attributed to the basic instability of the mediators, the diversity (and poor control) of same, and the acid/base (or hydrolysis) behaviour of the oxidized states of the mediators. It is assumed that major advances in the application of gold in the heterogeneous catalysis of gas phase reactions will be accompanied by similar advances in the use of gold in the electrocatalysis area; however, this will require considerable work of both a practical and theoretical nature.

Oct 1, 2003

By Golaleh Riahi

An original method is used to obtain stable nanoparticles of gold-based mono- and bimetallic systems supported on an acidic zeolite. This approach has been applied to PtHY (1wt% Pt) and to bimetallic Pt-AuHY containing 1% of platinum to which is added the amount of gold required to give Au/Pt molar ratios of 20,40,60 and 80%. Metal clusters of Au or Pt-AuHY are formed inside the supercages of the zeolite framework by the thermal reduction of cations by the ligands (en = H2N-CH2-CH2-NH2) under inert gas flow at a temperature depending on the metal. The use of acidic zeolites favours the dispersion of the metal and the thermal stability of the particles. This stability is explained by chemical anchoring of metal clusters by the Brønsted sites of the support. Several techniques have proved that for a molar ratio of 20% metal particles of Pt-AuHY are bimetallic. The segregation of Pt and Au starts for molar ratio =?40%. The catalysts tested on the methylcyclopentane hydroconversion reaction reveal that the addition of gold to platinum leads to an increase in the activity and an improvement in the selectivity for isomerization of the skeleton (cyclohexane and benzene) to the detriment of hydrogenolysis. Similar results were obtained for the dodecane isomerisation to isododecane. These catalysts were also tested in CO, propene and propane oxidation. The activity of fresh catalysts is rather low. It increases after their pretreatment in oxygen or hydrogen atmosphere. In propene oxidation in the reaction mixture O2 ? H2, beside total oxidation of propene to CO2, also propene hydrogenation was observed, particularly at low temperatures. The presence of Au enhances the hydrogenation properties: high selectivities (> 90%) to propane and high propane yields on PtAu HY are observed up to ~150oC, whereas for Pt HY catalyst the selectivity and yield to C3H8 decreases rapidly with the temperature beginning from ~100oC.

Oct 1, 2003

By Masami Nakamoto

Controlled thermolysis of gold(I) thiolate complex, [C14H29(CH3)3N][Au(SC12H25)2], at 180 °C for 5 h under an N2 atmosphere produces novel gold nanoparticles passivated by alkyl groups derived from the precursor complex, the TEM photograph of which shows spherical particles with average diameter 26 nm. Since Brust et al. reported the two-phase reduction of AuCl4 - by NaBH4 to afford monodispersed gold nanoparticles passivated by alkanethiolate ligands (1), plenty of preparative investigations on gold nanoparticles (2,3) and its surface modification (3,4) have appeared, because of their potential applications in microelectronics (5). However, those preparative methods generally involve the reduction of AuCl4 - by reducing agent NaBH4 in the presence of suitable organic stabilizers such as alkanethiol (1-4), phosphane (5), quarternary ammonium salts (6), surfactants (7) or polymers (8). On the other hand, O?Brien et al. recently reported the preparation of organically capped gold nanoparticles at 190 °C, where tri-n-octylphosphine oxide and/or n-octadecylamine are used both as a reaction medium and as a passivating ligand (6), but this procedure also needs NaBH4 as reducing agent. Our strategy of novel preparative method of gold nanoparticles is the combination of reductive elimination of thiolate ligands and simultaneous attachment of organic moiety on the growing nuclei. Gold(I) thiolate complexes with ammonium cations were useful for our preparative method. We now report the controlled thermolysis of gold(I) thiolate complexes, [R(CH3)3N][Au(SC12H25)2] and [R(CH3)3N][Au(SC6H4-p-R?)2] (R= C14H29, C12H25; R?= C8H17, CH3), under an N2 atmosphere, where the powder of gold(I) thiolate complexes completely melts to afford the precursor liquid and then the liquid gradually decomposes. In spite of no use of reducing agent and solvent, reduction reaction is thermochemically induced to afford novel gold nanoparticles passivated by alkyl groups rather than by alkanethiolate ligands. Figure 1a shows a typical transmission electron microscopy (TEM) image of gold nanoparticles prepared by thermolysis of [C14H29(CH3)3N][Au(SC12H25)2] at 180 °C for 5 h, indicating a controlled growth of spherical gold nanoparticles. As shown in Fig. 1b, these spherical gold nanoparticles display the size distribution ranging from 5 to 50 nm. Although the particle size is larger than that of thiol-derivatized gold nanoparticles (less than 5 nm) prepared by NaBH4 reduction (1-3), the aggregation of gold nuclei is smoothly regulated and the growth of core gold is limited to be 26 nm in average diameter in spite of thermal procedure.

Oct 1, 2003

By Toshiharu Teranishi

When we apply the Au nanoparticle superlattices to the future nanooptical and nanoelectronic devices, the control of not only the particle size but also the interparticle spacing and symmetry of superlattice are the essential problems to be overcome. First, we developed a novel synthetic procedure to precisely control the particle size of alkanethiol-protected Au nanoparticles in the range from 1.5 to 9.7 nm by the heat-treatment of the small Au nanoparticles in the solid state. Absorption and nonlinear optical properties of alkanethiol-protected Au nanoparticle superlattices were then elucidated. On the other hand, the hexagonal close-packed (hcp) 2D superlattices of small Au nanoparticles with the interparticle spacings from 1.9 to 3.6 nm were successfully prepared by using newly-synthesized ligand for single electron tunneling devices. Finally, various symmetric superlattices, such as chain (2-fold), quasi-honeycomb (3-fold), square (4-fold), etc., of Au nanoparticles could be produced by making use of interligand interactions or some templates.

Oct 1, 2003

By Elma van der Lingen

Gold is considered the most inert of all metallic elements, but the metal can show catalytic activity when prepared by specific techniques. Preparation techniques being used to prepare gold catalysts systems mainly involve precipitation methods incorporating gold compounds or complexes. This paper introduces a totally different method for the preparation of gold-based heterogeneous catalysts that can be used for oxidation and reduction reactions, as well as electrocatalysts. The method involves alloying of gold with a less noble metal, such as aluminium, to form a gold-containing intermetallic precursor. AuAl2 was produced by melting gold and aluminium together in a vacuum arc furnace under a protective atmosphere. The aluminium is then dissolved from the AuAl2 precursor by means of NaOH to produce a highly porous gold structure. The paper also reports on a method of incorporating transition metal oxide(s) with the porous gold to form an active heterogeneous catalyst. Promoter elements can also be melted with AuAl2 to improve catalytic activity. Alloying has the advantage that the promoter element can be in contact on atomic level with the gold. In-situ xray photoelectron spectroscopy (XPS) studies have also been done on the porous gold catalysts to further clarify the CO oxidation mechanism on gold-based catalysts.

Oct 1, 2003

By Ronald L. Bruening

IBC has developed a cost effective MRT process for the selective extraction and recovery of gold, copper, and a mixture of other base metals from mine leach cyanide solutions. This is a two-stage system in which the gold is first recovered selectively as a high purity salt. The copper is then recovered separately as a sulfate salt. The other base metals are then collected as a cyano anion concentrate. Three different SuperLig® materials are used. The first stage can be used alone on gold leach solutions where copper and other base metals are not a problem. The two or three stage system is used when the base metals build up in the leach solution, resulting in increased costs. The cyanide or cyanide/cyano anion concentrate can be recycled back to the leach solution until the build-up of other salts, etc. becomes too high, or this too can be controlled with a percentage bleed stream.

Oct 1, 2003