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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 Matthew S. Hall

Gold/iron oxide catalysts have been prepared and their catalytic performance evaluated for low temperature CO oxidation. The method and temperature used to dry the sample has a significant effect on their catalytic activity. Analysis by TEM revealed the catalysts contained Au particles, although catalysts with high and low activity did not always differ in their microstructure as evidenced by TEM. Catalysts were characterised using XPS and the difference between the Au(4d) and C(1s) binding energies measured; in general the greater the difference, the higher the catalytic activity of the material.

Oct 1, 2003

By Ayako Iwakoshi

Highly concentrated pastes of gold nanoparticles were successfully produced by use of a special kind of protective polymer and a mild reductant. Solid part of the pastes consists of up to 85wt% of gold nanoparticles, 10~30 nm in diameter, and residual protective polymer. This component can be diluted by any kinds of solvent at arbitrary rates. Electronics, optics, catalysts, colorants and surface metal coatings are possible application fields. 1. Introduction Noble metal nanoparticles are of interest in a variety of fields ? such as colorants, metal coatings, electronics(1), optics(2), and chemical catalysis(3). Especially, in the color field, the gold nanoparticle has been known as an aesthetic red colorant for stained glass and fine glassware, such as Venetian glass. The mechanism of coloring is attributed to surface plasmon absorption of gold nanoparticles(4,5). The gold nanoparticle in stained glass shows very clear red color, which is very durable for hundreds years. On the other hand, the red color of organic pigment in paint films often fades away within several years. We intended to reproduce the elegant and stable coloring of stained glass in paint films. In order to color a very thin, 20~50?m, paint film like stained glass, production of highly concentrated dispersion of gold nanoparticle is necessary. To achieve this, there were two issues to be overcome. One is how to prevent the coagulation of gold nanoparticles in highly concentrated solution. So far, several methods to prepare gold nanoparticles(6,7) were reported. But only a few methods succeeded to stabilize the gold nanoparticle dispersion at higher concentration than ppm order. The other is controlling of the particle size, this is because the color of gold nanoparticles is very sensitive to the particle size. Only when the particle size lies around 10 nm, the suspension exhibits red color like stained glass.

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 Lizelle Glaner

An investigation was carried out by Mintek to investigate the influence of additions of gold to ?Fecraloy?, alloys based on Fe-Cr-Al. The aim was to try and improve the oxidation resistance of the ?Fecraloy? alloys at elevated temperatures over extended periods of time. The ?Fecraloy? alloys are very oxidation resistant alloys already employed in industry as substrates for metallic catalysts in auto-catalyst systems for high performance cars. Since their life and durability is limited by the slow, but steady, oxidation of the substrates, any change in the growth or stability of the oxides could be an improvement.

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 László Guczi1

Nanosize model gold particles with varying size were fabricated by deposition of a 10 nm thick gold film onto SiO2/Si(100) substrate by electron beam evaporation followed by modification using low energy Ar+ ion bombardment. The change in particle size were monitored by the Au 5d valence band states determined by ultraviolet photoelectron spectroscopy (UPS). The gold/iron oxide interface was studied by iron oxide deposition on gold. It was found that the energy profile of Au 5d valence band states are strongly redistributed with decreasing the gold particle size mostly affecting at the lowest and at the highest binding energies. The size effect in the UPS spectra can be interpreted by the energy redistribution rather, than by narrowing the 5d states. The iron oxide deposition increases the catalytic activity in CO oxidation whether it is on gold nanoparticles or on a continuous 80 nm thick gold film. The activity enhancement is significantly larger in case of gold nanoparticles. The interface interaction is operative in enlargement of the catalytic activity even if gold particles are not exposed to the surface, but they are located below the iron oxide layer.

Oct 1, 2003

By Antonio Laguna

During the past few years, synthetic efforts have been addressed to the synthesis of polymeric materials with optical or semiconducting properties or even with capabilities to act as sensors for volatile organic compounds (1). The most recent studies have been concerned with the synthesis of heterometallic systems with short metal-metal interactions and the determination of their optical properties. These complexes are undoubtly interesting from a theoretical viewpoint and include an emerging class of luminescent materials, in which the observed luminescence results mainly from the interactions among the different metal centers, as well as the environments of these atoms. The understanding of the photophysics and photochemistry of these products could permit the design of complexes with appropriate metals and ligands chosen for individual applications. Following a synthetic strategy consisting on reactions between acid heterometal complexes and basic gold precursors we have succeded in synthesizing supramolecular assemblies formed via acid-base stacking, which display tunable luminescence or selective and reversible sensitivity to Vapour Organic Compounds (VOC?s) (2-5). In this sense, in accord with previous Mössbauer studies carried out in the gold precursor complex [AuR2]- (R = C6F5), the basic properties of this and related materials have been employed as building blocks of supramolecular assemblies in their reactions with complexes in wich the metallic centers act as lewis acids as, for instance, Tl(I) or Ag(I) (6). For instance, in the case of silver, by reacting equimolecular quantities of [NBu4][Au(C6F5)2] with AgClO4, in acetone, a solid of stoichiometry [Au2Ag2(C6F5)4(OCMe2)2]n is obtained. The polymeric nature of this material in solid state is confirmed through X-ray analyses (figure 1). It consists of polymeric chains formed by repetition of Au2Ag2 moieties linked through short gold-gold interactions. Nevertheless, in solution, the nature of this polymeric materials was still a matter of controversy and, in this case, the optical properties have been shown as useful tools in order to obtain information. Thus, while dilute acetone solutions of this complex give a emission coming from pentafluorphenyl localized ??* excited states, in accord with the presence of isolated tetranuclear Au2Ag2 units, when the measurements are done at different and higher concentrations, a band that does not obey the Lambert-Beer law appears. This deviation is consistent with molecular aggregation in solution of these units through gold-gold interactions, and a clear correlation between the emssion wavelength and the structure in the solid state and in solution is shown (figure 2). DFT calculations accord with the observed experimental behaviour and show the nature of the orbitals involved in each transition.

Oct 1, 2003

By Jr. Fackler

The ionization potentials of gaseous Group 11elements are similar, with Au(0) being 1.5 eV greater than the next highest member of the group, Cu(0). The ionization potentials are all very much greater than the alkali metals, making these ?coinage? elements rather unreactive to chemical oxidation. Ionization from the first oxidation state shows a different pattern, with Ag(I) being the most difficult of the Group 11 ions to lose an electron. Gold(I) is noble and only normally oxidized in the presence of strongly coordinating ligands such as thiols or cyanide. Gold(I) compounds are 2-, 3- and 4- coordinate, with 3-coordinate species generally showing visible photoluminescence under UV excitation. Dinuclear Au(I) compounds with strongly coordinating S or C ligands can be oxidized to form isolable metal-metal bonded Au(II) compounds which are often readily isolable. Many have been structurally characterized. T he ease with which electrons are lost from closed shell dinuclear sp ecies (with anti-bonding M-M interactions) increases when metalmetal bonded compounds are formed. T his observation was made by our group with oxidative-addition studies of dinuclear gold(I) ylide complexes. It was superbly demonstrated recently by Cotton?s group who reported the isolation and characterization of a dinuclear closed shell transition metal species which is more readily oxidized than cesium. Trinuclear Au(I) pyrazolates, TR(pz), carb eniates, TR(carb), and benzylimidazolates, TR(bz), are well known and undergo electron loss through oxidative addition forming Au(I,III) mixed valence species and ultimately trinuclear Au(III) species. Au(II) species are absent from isolation in these oxidations. These carbeniates and benzylimidazolates also are excellent bases for metals ions such as Tl(I) and Ag(I). The acidic, neutral trinuclear compound [Hg(C6F4)3]3 also interacts with these bases. We have also shown that the neutral organic pi acids C6F6 and TCNQ form stacked pi-acid pi-base products with the trinuclear Au(I) compounds. In this paper, the structure of the octafluoronaphthalene acid-base product will be described. It displays a feature not observed previously in that the product is photoluminescent with a bright yellow emission. The 3.5 ms lifetime is very long and reminiscent of the long lifetimes observed by Balch for the stacked methyl,methoxy Au(carb). The electrochemical oxidation of tetragold(I) clusters, [Au4(form)4] have been studied in 0.1 M Bu4NPF6/CH2Cl2 at Pt working electrode at different scan rates. Three waves are obtained at 0.75, 0.95, and 1.09 V vs Ag/AgCl at scan rate 500 mV/s. The potential of the three reversible waves is independent of the scan rate in the range 50 mV/s to 3 V/s. The current at the third wave is larger than those at the first two waves. These tetranuclear species app ear to be effec tive catalyst precursors for the oxidation in air of CO. Introduction. The electronic structural relationships of the coinage elements and the alkali metals are similar in the sense that each have a [closed shell]ns1 configuration, yet their ionization energies (Table) and chemistries are clearly vastly different. The Group 11coinage elements have an underlying nd10 level immediately below the ns1 level. Unlike the alkali elements, ionization leaves the filled d electron shell the next accessible for further ionization. The coinage elements are all relatively ?noble?, much less reactive to environm ental conditions than the alkali metals. With the coinage elements, oxidation becomes very much dependent upon the types of ligand s availab le to bo nd to the ionized state.

Oct 1, 2003

By Jef M. van der Zel

The idea of veneering rich yellow gold alloys with a low-melting, high expansion porcelain, has been a driving force for metal-ceramic research in dentistry. Since 1990, with the advent of the Carrara System (1), a low firing temperature veneering ceramic allowed the use of gold alloys with a lower content of platinum and palladium than the traditional gold-platinum ceramic alloys and thus a richer yellow color. The earlier high gold-platinum ceramic alloys contained at least 12 percent platinum group metals to allow for dimensional stability when firing the relatively high melting traditional ceramics. This amount of platinum group metals gave the alloys a greyish tinge which made them unattractively steel colored and difficult to present as ?high gold alloys?. In the 90?s the new generation universal low-melting, high expansion gold alloys gained market share at a steady rate, starting in Germany, and have now for a great part replaced the traditional gold-platinum alloys (Fig. 1). The first alloys contained 75 wt-% gold and up to 9 wt-% platinum or palladium. They provided a metal-ceramic system in which a gold alloy having an aesthetic yellow colour is fired on with a dental porcelain tailored thereto. The tailoring is meant in respect of compatible coefficients of thermal expansion, and compatible melting or softening points of metal and porcelain. The major concerns in the beginning were with thermal stability during firing, the thermal expansion coefficient of the alloy against the porcelain (compatibility) and the yellow color. In a later stage, alloys with gold contents in the range of 50-60 wt-% gold were developed in analogy with the pale yellow gold-reduced alloys that were formerly used for crown & bridge work and the white gold-reduced alloys used for metal veneering where gold was substituted in part by palladium.

Oct 1, 2003

By Laura Prati

Gold-on-carbon catalysts resulted very active and selective in liquid phase oxidation [1, 2, 3] and during past studies we established that activity is ruled by two factors: particle dimension and gold exposure on the carbon surface [4]. These two parameters are also connected to the nature of activated carbon where the chemical nature of the surface oxygenated groups probably plays an important role [5]. Our studies, focused on the design of an active gold-on-carbon catalyst for liquid phase application, were aimed, operating a fine tuning of all the parameters involved in determining activity, to optimize gold-on-carbon preparation, keeping in mind that gold particle activity increases with decreasing particle size and increasing gold exposure. Gold sol immobilisation represents a versatile methodology in preparing gold catalysts [6]: throughout this work we used as sol stabilizing agent, the N-dodecil-N,N-dimethyl-3-amino-1-propan sulphonate (SB), that provides both sterical and electrostatic stabilisation, a condition we already demonstrated necessary to preserve particle dimension when carbon is used as the support [6]. We generated different gold sols by varying the relative amount of reagents (HAuCl4, SB, NaBH4), the type of alkali and the temperature of the gold precursor reduction. Moreover, as we had recently evidenced that there is also a carbon effect [5], we employed only one active carbon to immobilize the sols.

Oct 1, 2003

By Oleg G. Tovmachenko

We have studied optical properties of fluorescent nanoparticles. These particles consist of a metal (gold/silver) core, an empty and a dye labelled silica shells. The different dye molecules with moderate quantum yields (about 0.3) has been used. Almost all of types of nanoparticles show fluorescence enhancement. This enhancement is strongly dependent on the degree of the overlap between the surface plasmon band of the metal and the absorption/emission band of the dye molecules. The results are interpreted in terms of competition between local field enhancement and quenching of fluorescence by the metal surface.

Oct 1, 2003

By Eamonn F. Maher

Superconductivity is one of the most remarkable scientific phenomena ever investigated. It is the phenomenon whereby some materials exhibit zero resistance to the passage of an electric current when cooled to low temperatures, and requires a quantum mechanical explanation. Four Nobel prizes in physics have been awarded specifically on the subject of superconductivity, with many more enabled by superconducting technology. For example, particle beams are generated in accelerators and manipulated in ?particle beam lines? in the ?Big Physics? projects around the world eg. at CERN, Geneva, leading to major discoveries in fundamental particle physics. Similarly, at the JET Propulsion laboratory near Oxford, U.K, controlled nuclear fusion has been demonstrated, and magnetic containment of plasmas is key. In the chemical and biological sciences high field NMR spectroscopy has become indispensable for examining organic matter, revealing the mysteries of the workings of cells, genetics, and in the development of new polymers and pharmaceuticals. With all these very advanced uses for superconducting magnets, it is easy to forget that superconductivity is big business, not just a scientific curiosity. MRI (Magnetic Resonance Imaging) superconducting magnets, the key component of high resolution body scanners, use approximately half of the world?s superconducting wire ? the other half being mostly used in accelerator magnets. The MRI market is about 3 billion dollars per annum, and one MRI magnet uses 200km of wire. New applications for superconducting magnets are now appearing including ?Catheter steering?, enabling much shorter timescales for life-saving brain tumour removals and ?Functional MRI?, a whole new area in patient diagnostics. Whilst the use of low temperature superconductors (LTS) is now well established commercially in superconducting magnets and niche electronic applications, the application of LTS in electric power distribution and transport has been very limited to date. It is now more than fifteen years since the so-called High Temperature Superconductor (HTS) materials were discovered: these can be operated at liquid nitrogen temperatures rather than liquid helium temperatures. However, materials processing and scale-up issues have prevented their widespread use, and in particular the required price/performance criteria are only beginning to be reached except in certain niche markets. BSCCO (Bismuth Strontium Calcium Copper Oxide) tapes up to one km long are now readily available, and have been demonstrated in high current cables for power distribution networks, but the general consensus is that 1) it is difficult to reduce the price much further because of the silver matrix required and 2) in applications where coils are required eg. motors, generators, transformers etc the properties of BSCCO are rather poor because of the critical current dependence on magnetic field. Magnetic fields are always associated with coils and windings, and such fields are of course fundamental to the operation of all electrical machines. YBCO (Yttrium Barium Copper Oxide) however, has good characteristics in field and for the last few years there has been intensive research and development costing several tens of millions of dollars worldwide into the scale-up of production of so-called ?coated conductor?. This ?second generation? tape can be produced by any of many different film deposition techniques, with more or less success for short lengths, but as yet it is unavailable in lengths more than a few tens of metres.

Oct 1, 2003

By Fabio Terzi

In this investigation some preliminary results are reported about the electrochemical oxidation of CO using goldbased encapsulated nanoparticles grafted on conducting substrate. The investigation has been planned in four steps: 1. production of Au(111) substrate and modification with self assembled monolayers; 2. synthesis and embedding of nanoparticles; 3. grafting of encapsulated nanoparticles on electrode substrates; 4. investigation of CO electroxidation on the modified electrode. The systems were characterized by means of various techniques (spectroscopic, microscopic, and electrochemical methods), obtaining information about SAM's structure and morphology, size and composition of nanoparticles and electrochemical behavior of modified electrodes.

Oct 1, 2003

By Eiichiro Mizushima

Catalyst systems comprising (Ph3P)AuCH3 and acid co-catalysts were found to be highly efficient for hydration of alkynes to give ketones. Methanol was the best choice of solvents. Introduction Hydration of carbon-carbon unsaturated bonds is one of the environmentally benign routes to the carbon-oxygen bond formation. Hydration of alkynes forming carbonyl compounds, an important variation in this category, is a well known reaction which has been extensively studied. The reaction by acid-catalysis is the most conventional method, while it is applicable only to electron rich acetylenes to obtain satisfactory yields (1,2). The hydration of simple alkynes usually requires another catalyst (co-catalyst), typically a mercury(II) salt (3), which is inconsistent with the guiding principle of Green Chemistry (4).

Oct 1, 2003

By Timothy W. Ellis

Wire Bonding is the dominant IC interconnection process presently used in the semiconductor assembly industry (1). The flexibility, adaptability and cost of wire bonding will continue to keep it as the key process for the interconnection of integrated circuits to substrates. However, wire bonding still has certain technological hurdles to overcome if it is to continue following the semiconductor roadmap (2). Particular issues which need to be addressed include low overall tensile strength, low elastic modulus, low shear per unit area and mechanical loop stability of Gold based micro-alloys. The ability to produce ?Deformation Process Metal-Metal Matrix Composites? (DMMCs) is based upon the deformation nature of immissible metallic systems. For reference, the Gold (Au)-Molybdenum (Mo) phase diagram is shown in Figure 1 (3). By inspection of the diagram, Au has a very low solubility for Mo, while Mo has essentially no solubility for Au. This is the metallurgical analog of oil and water. In the Au-Mo case, this is particularly troublesome when producing precursor ingots of the alloy to be formed into wire products. In Table 1, the melting points and densities are shown for Au and Mo. As shown, the melting point of Mo is significantly higher than Au, and is very close to the boiling point of Au (2856°C). However, Au?s density is higher than that of Mo. As such, conventional casting techniques are not suitable, since solid Mo would float off the surface of an Au melt thus depleting the matrix of its alloy addition. In this work, two-phase composite wires were produced by deformation processing to develop an interconnection wire with elevated tensile strength, modulus and shear to those commonly available in the market (4). This technology has been used previously in the production of high strength electrical conductors particularly for high field pulsed magnets (5).

Oct 1, 2003

By Michele L. Kimble

A fast-flow reactor mass spectrometer has been utilized to investigate the reactions of gas-phase gold cluster anions with CO and oxygen. Addition of CO to Aun - produces species of the form Au(CO)m -, where m = 2-5. However, CO does not bind to Au2 - or Au3 -. With oxygen addition in the cluster source, gold oxide species with both molecular and atomized oxygen are produced. The addition of carbon monoxide to these preoxidized gold cluster anions reveals that select species with 1, 2, and 3 gold atoms participate in the oxidation reaction to produce CO2. Bimolecular rate constants for the reactions between these species and CO are also discussed.

Oct 1, 2003

By S. Ivanova

The results presented in this paper show that the gold solution dilution is a key parameter to control the dispersion of gold on ?-Al2O3 the selected support. The variation of concentration leads to changes in pH which modify the nature of gold complexes from HAuCl4 formed in the solution. These complexes are presented. Some of them (AuCl3(OH)- and AuCl2(OH)2 -) react with the surface of alumina and give interesting interaction. AuCl2(OH)2 complex has been considered as an ideal complex because of the strong anchorage of a bidentate species on the alumina. This complex is formed mainly in a solution of gold with a concentration of 10-4 M giving a pH of 3.5-4.5. The nature of the anchorage and the amount of chlorine, has an influence upon the formation of Au-Cl bridges which modify the dispersion of the gold on alumina of the final catalyst as shown by TEM.

Oct 1, 2003

By John A. Rumball, Martin R. Houchin

Data from autogenous and semi-autogenous tests in a 1.67m diameter mill have been analysed in terms of a new model for rock abrasion. This model defines specific rate as the rate of production of fines (material less than 13mm) per unit mass of rock, where the term “rock” is applied to all ore pieces of ore coarser than the grate size. In most cases, an allowance for preliminary rounding and cleavage was made. A method has been developed to analyse steady-state data, using piecewise fitting to the cumulative size distributions. The model was compared to the well-established models, which are based on the population balance method. The specific rate increased for all rock sizes as the volume of 100mm balls in the mill was increased. Tests using a coarser feed and smaller balls provided further evidence that once rocks are rounded, abrasion is due to localised surface damage, caused by impacts, rather than rotational shear. An allowance for rapid rounding of jagged rocks, followed by less rapid abrasion of rounded pebbles was also tested, but the analysis was not conclusive. The average specific rate is a useful measure of the capacity of a primary mill. The effect of power intensity (kW/t of ore) was also investigated as a means of extrapolating the pilot-plant data to large production mills.

Sep 29, 2003

By Ron H. Derammelaere

"The paper point out of the copper slurry pipelines in South America, providing key statistics, such as throughput, diameter, length, etc. In addition, it will present technical aspects of pipeline design that are unique tomountainous terrain, specifically: choke stations for the control of slack flow, batch hydraulics, automation and training.The pipelines listed in this paper operate successfully at availabilities in excess of 98%. Breaks and plugs can occur due to operator error, but are extremely rare. A review of cross-country slurry pipeline operations worldwide over the last 30 years shows that such a major event occurs, on average, once every five years. Under such a worstcase condition, the downtime rarely exceeds five days. Some pipelines have already been in operation over 30 years, the life span being a function of how well corrosion is kept in check."

Jul 31, 2003