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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 Olaf Andersen

Crucible melt extraction yields short metal fibers with eqivalent diameters as low as 50 µm from almost arbitrary metals and alloys. Highly porous components can be made from such fibers by suitable deposition and sintering methods. This technology is being developed at the Dresden based Department of Powder Metallurgy and Composite Materials of the Fraunhofer Institute for Manufacturing and Advanced Materials (IFAM) and has been applied to gold alloys and iron-base alloys containing small additions of precious metals. From the manufactured gold fibers, sintered structures were made for decorative applications. Additionally, it was found that due to rapid solidification during the fiber formation, precious metals can be finely dispersed in ironchromium- aluminum (FeCrAl) and FeAl20 alloys. Good catalytic activity at elevated temperatures was found in compositions containing 3 wt.-% Ce and 0.5 wt.-% Pt.

Oct 1, 2003

By Andreea Catalina Gluhoi

Oxidation and reduction reactions of N-containing molecules have been studied over different types of gold-based catalysts, Au/MOx/Al2O3 and Au/MIOx/MIIOx/Al2O3 (M, MI, MII=Li, Rb, Mg, Ce, Zr, Mn, Cu) prepared by deposition precipitation with urea. In general, all the catalysts were already active at low temperatures. NH3 oxidation was effectively catalyzed by Au/CuO/Al2O3, a catalyst which also gives the highest yield in N2. NO reduction by H2 performed over gold-based catalysts produced N2O, N2 and NH3 and N2O reduction resulted in the formation of dinitrogen. For all the reactions, large synergistic effects have been obtained by addition of different kind of additives.

Oct 1, 2003

By Masaru Kato

The plated gold being used by the electronics industry can be broadly classified into two categories: soft gold and hard gold. Soft gold is used for circuit metallization and for bonding semiconductor chips, while hard gold is indispensable as the contact material on electrical connectors, electromechanical relays, and printed circuit boards. The traditional baths from which to plate soft gold as well as hard gold contain the cyanide complex, [Au(CN)2]-, as the source of gold, which liberates free cyanide ions during the plating. The free cyanide is not only highly toxic but also attacks photoresists used to delineate circuit patterns and bonding pads. For these reasons, non-cyanide baths are in use to plate soft gold, whereas hard gold can be plated only from cyanide baths at present. In this presentation, the current status of both electrolytic and electroless non-cyanide processes for plating soft gold will be reviewed.

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 Jörg Fischer-Bühner

Conventional 22ct Au jewellery alloys are comparably soft in the as-cast and soft-annealed state and hardening by cold-working is the only way of giving strength to the jewellery. The paper first focuses on hardening of 22ct jewellery alloys by conventional means, i.e. solid solution hardening with base metals (aiming particularly at an increased as-cast hardness) as well as precipitation hardening by alloying with base metals beyond the solubility limits and subsequent age-hardening heat treatment. Co-additions of ~2% turned out to result in most pronounced solid solution hardening up to ~100 HV1 in an investment cast & quenched state. Subsequent heat treatments, consisting of solution annealing at 850°C for 1h followed by water quenching and ageing at 300°C ? 400°C for ~ 1h lead to pronounced age-hardening with a peak hardness of ~ 260 HV1. In contrast, 22ct Au alloyed with Ni, Fe or Sb display no age-hardening effect within the same range of heat treatment parameters. The 2nd part of the paper reports on some preliminary trials to enhance the hardening effect of the base metals by additions of suitable elements, which possess a strong tendency to phase formation with the added base metal during ageing treatments. It is shown, that the age-hardening behavior of 22ct and 990/995 Au alloyed with Co or Ni can be remarkably influenced by additions of Sb. A total of only 10wt%0 of CoSb or NiSb-additions lead to a peak hardness of ~ 150 HV1 for a 22ct Au and ~ 100-120 HV1 for 990 Au , which is obtained already after very short ageing times (20-40min) at 300-400°C after solution annealing at 700°C / 1h / water quenching. It is suggested that the age-hardening mechanism in these alloys consists in precipitation of intermetallic CoSb- and NiSb-phases.

Oct 1, 2003

By Timothy W. Ellis

Gold-based materials have been a mainstay of the electronics and semiconductor industry since the physics was just a laboratory curiosity. Gold is the workhorse material in wire bond, flip chip and off wafer interconnections due to its corrosion resistance, ability to form metallurgical bonds by soldering or cold welding, and ease of fabrication. As the electronics and semiconductor industries grew, so did the use, of Gold in spite of the feature size reduction so elegantly demonstrated in Moore?s law. However, several revolutions in the Silicon miracle are threatening Gold?s place as the material of choice. Although cost is always an issue, the limitations are associated with the chemistry of Gold based alloys. Will Gold remain? Emerging requirements of bioelectronics, photonics and power requirements in conventional device represent new opportunities for Gold to shine. Additionally, as the world market demand for electronic, semiconducting, bio-electronic and photonic technology increases, given the right technology, Gold still can provide value proposition.

Oct 1, 2003

By Franz Simon

Conventional fine gold electrolytes for barrel applications working electrolytically actually permit significant precious metal savings by corresponding optimizations but the most gold is still deposited on areas of the components where it is not absolutely essential for the desired bonding and soldering applications, i.e. in high current density areas. Therefore an electrolyte working electrolessly has been developed which inevitably leads to a much more uniform thickness distribution since in an electroless process there are no areas favoured by metal deposition and current distribution. The new electrolyte will be presented and its performance will be compared with conventional electrolytes as regards thickness distribution. The potential gold savings will be discussed.

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 Benedetto Corain

The production and dispersion of metal nanoclusters onto inorganic supports and amorphous carbon rest on well consolidated technologies belonging to the realm of industrial catalysis and of basic catalysis research (1). In spite of the existence of a variety of specific synthetic strategies, their very rationale relies on three main approaches i. e.: A: precursors of both the metal nanoparticles and of the relevant supports (or the support itself) are intimately mixed (even let to react) at ambient conditions and then thermo-reduced according to very controlled protocols (2); B: precursors of metal nanoclusters are let to be adsorbed onto suitable supports from the gas or liquid phase and subsequently thermally decomposed (3); C: metastable size-controlled metal nanoclusters are previously generated in a liquid medium and subsequently transferred onto pre-formed support particles (4). The production and dispersion of metal nanoclusters onto organic soluble supports is also a rather well documented academic praxis (5, 6, 7, 8) able to provide e.g. size-controlled Au0 nanoclusters of 4.4±1.7 nm (5). Our group started in 1997 developing (9) an innovative approach to the synthesis of metal nanoclusters dispersed inside insoluble, albeit accessible (see below) mechanically robust gel-type resins (10), which procedure was tested so far on palladium metal. Metal ions are previously dispersed upon ion-exchange inside of the polymer framework, followed by chemical reduction and by the aggregation of born metal atoms into nanoclusters, the size of which is templated (11, 12) by the three-dimensional intercommunicating meshes that build up the overall polymer framework (Figure 1).

Oct 1, 2003

By Yongbao Zhu

The Ag2O-mediated reactions of cycloaurated compounds with a general formula Au(L)Cl2 (L = bi-dentate C?N ligand) with thiosalicylic acid, N-acetyl cysteine or 1,2-benzenedithiol in DMF proceeds via ligand substitution of the Au?Cl bonds to afford the S-O and S?S adducts all in good yields. The reactivity of the dichloro, S-O and S-S adducts towards thiols were examined by reacting with cysteine in an aqueous medium, revealing that all of Au-Cl, Au-O and Au-N are labile for thiol displacement. The measurement of the inhibitive activities of these compounds against human cathepsins B and K showed that the dichloro and S-O adducts are effective inhibitors with IC50 values ranging from 0.1 to 2.6 -M, and that the S-S adducts are inactive.

Oct 1, 2003

By Daniel B. Leznoff

The cyanoaurate anions [Au(CN)2]- and [Au(CN)4]- are shown to be useful building blocks for synthesizing supramolecular coordination polymers. For the gold(I) unit, aurophilic interactions often increase the structural dimensionality of the system and can impart increased thermal stability to the metal-polymers produced. A series of polymers of the form M[Au(CN)2]2(Ligand)x have also been prepared and show large colour changes upon changing the ligand, thus illustrating a sensor-type application. Both building blocks can mediate significant antiferromagnetic and ferromagnetic interactions between transition-metal centres in the polymers. For the gold(III) unit, no metal-metal interactions are observed, although weak Au-N(cyano) interactions control the intermolecular packing. Several structural examples of cyanoaurate-based coordination polymers are presented, including 2-D and 3-D arrays and a supramolecular square.

Oct 1, 2003

By Ana Adé

The use of gold compounds in homogeneous catalysed organic reactions has been undervalued for many years due to the preconceived opinion that gold is an expensive and extremely chemically inert metal. However, recent reports have changed this assessment and gold salts in small amounts are known to display high catalytic activity.[1] Thus, it has been reported recently that anhydrous AuCl3 catalyses the formation of C-C and C-O bonds (usually mediated by hydrochloric and other protonic and Lewis acids).[2] Some examples include Michael type additions, selective cross cycloisomerisation/dimerisation of propargyl or allenyl ketones, benzannulation between o-alkynylbenzaldehides and alkynes or cyclisation of alkenyl furans. It is noteworthy that some of these reactions[2a] can be also catalysed by silver salts but with much lower yields. The 1,3-dipolar cycloaddition of nitrones to alkenes is a powerful synthetic method that has found numerous applications in the synthesis of a variety of carbon frameworks.[3] Several laboratories have focused on the development of Lewis acidic reagents to modulate the selectivity of the reaction.[4] Despite the extensive study performed, there are not many examples in which a metallic complex catalyses the dipolar cycloaddition. Most of these reactions require the presence of a metallic complex and nitrone in a 1:1 molar ratio. Recently, we have carried out stoichiometric reactions of the N-benzil-C(2-pyridil)nitrone, 1, with different dipolarophiles in the presence of zinc and silver compounds.[5] Apart from an increase of the reaction rate and the selective formation of one of the possible isomers, we have shown the formation of zinc and silver-nitrone complexes during the reaction, which behave as the intermediates in the cycloaddition process. As suggested by the results obtained with silver complexes, we decided to test gold derivatives (in the oxidation states of I and III). Interestingly, we have found that they can be used not only as stoichiometric reagents but they can also mediate these cycloadditions in catalytic amounts (5 to 10 mol % respect to the nitrone). Here we present the results on the 1,3-dipolar cycloaddition reaction of the N-benzil-C(2-pyridil)nitrone (2-PyBN), 1, and methylacrilate, 2, (Eq. 1) catalysed by gold(III) derivatives.

Oct 1, 2003

By Shamil Shaikhutdinov

CO adsorption on gold particles deposited on well-ordered alumina and various iron oxide films has been studied with temperature programmed desorption (TPD) and infrared reflection adsorption spectroscopy (IRAS). Structural characterization has been performed with scanning tunneling microscopy. Data show that the CO adsorption exhibits a size effect in that small particles adsorb CO more strongly. The effect generally vanishes after annealing to 500 K. For annealed samples, CO TPD and IRAS spectra are nearly independent of the particle size and supports studied. The results indicate that the CO interaction with gold surfaces is essentially similar and involves low coordinated atoms.

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 Christopher W. N. Anderson

Induced hyperaccumulation of gold by plants was first reported in 1998 by researchers from Massey University in New Zealand who proposed the idea of mining gold using plants (phytomining). Since that time research has been conducted to understand the conditions under which plants can be made to take up economic amounts of the metal. One key focus has been on the geochemistry of gold-rich soils, leading to a diagnostic test that can predict how suitable a particular soil might be to gold phytomining. Field trials have been conducted at several locations around the world in collaboration with industry partners. A Decision Support System has been developed to assist in the design and management of phytomining operations, and economic modeling has been carried out to set targets levels for phytomining technology. Novel studies are now examining the form of gold in plants. Research suggests that plants may store gold as discrete metallic nanoparticles in leaf and stem tissues, an observation that may lead to new ways to recover the metal from harvested biomass.

Oct 1, 2003

By Hannu J. Häkkinen

Metal clusters exhibit unique size-dependent physical and chemical properties that differ from those of bulk materials or large particles. Here we discuss recent theoretical investigations of the catalytic properties of free and MgO-supported gold clusters. The catalytic activity of gold clusters depends sensitively on the environment, charge state, and chemical composition of the catalyst. Relativistic bonding effects stabilize large planar structures for gas-phase gold clusters, and non-compact ?quasiplanar? structures are present as important isomers also for surface-supported clusters. The hybridization of the atomic 5d and 6s states is significantly enhanced by the relativistic effects, and large spatial variations in the nature of the local electronic structure make the low-coordinated gold atoms preferable adsorption sites for oxygen molecules. The adsorbed oxygen molecules are activated to superoxo- and peroxo-states via charge-transfer from gold, and Eley-Rideal and Langmuir-Hinshelwood reactions with CO proceed via low-barrier formation of intermediates, which do not require O-O dissociation as precursors. This facilitates the low-temperature (below 300 K) activity of gold nanocatalysts in CO oxidation. Other gold nanostructures, such as mono-atomic gold nanowires, may also become important prototype systems in chemical sensing and nanocatalysis; here we show that they are active promoters of hydrogen dissociation.

Oct 1, 2003

By Jeremy D. Glennon

A number of exciting challenges, opportunities and unanswered questions remain concerning the chemistry, geochemistry, medical, industrial and analytical applications of gold and its compounds.1 Among the challenges presented is the need for extraction methods for gold, at process and indeed analytical scales, that avoid the use of organic solvents or hazardous reagents. Extensive environmental contamination has occurred in the Brazilian Amazon from the mercury-gold amalgamation process. Major problems with the cyanidation process are the relatively slow dissolution kinetics and the health and environmental problems associated with it. With innovation and technical changes, a cleaner way for solubilising and extracting this versatile precious metal can be found. This cleaner future may lie in supercritical fluid science. Interestingly, geochemical studies of gold solubility and speciation in hydrothermal solutions have highlighted the importance of supercritical conditions and sulphur species in the deposition of gold in natural environments. Gold solubility in supercritical brines is far higher than previously supposed while interest in the high content of carbon dioxide in the mineralizing fluids is growing. 2,3 In recent years, also, there has been a tremendous amount of attention paid in analytical chemistry and in industry, to the area of supercritical fluid extraction (SFE) of organic and metallic species. 4 This interest has been fuelled by the introduction of more stringent environmental control and the subsequent need for cleaner solvents and processes to replace established ones. Carbon dioxide is the substance of choice for SFE because of its moderate critical parameters (Tc = 31oC, Pc = 73atm), inertness and availability in pure form. It is an excellent extraction medium for non-polar and moderately polar species, and with careful ligand design, it can be used for analytical and process scale metal extraction from solution and solid phases. In general, the dissolution of a metal in supercritical CO2 (sc-CO2) requires that the charge on the metal ion be neutralised on complexation by the ligand or through a form of ion pairing (analogous to the situation where metal ions are extracted into organic solvents, such as methyl isobutyl ketone or toluene). In this way, then, many chelating agents such as dithiocarbamates and hydroxamic acids have been utilised to extract metal ions such as Cu and Fe into sc- CO2, the process greatly enhanced by the use of fluorinated ligand derivatives. 5-7 In this review paper, we show that supercritical conditions and complexation with sulphur donor atoms, important in the natural deposition of gold, can form the basis of a clean, eco-friendly chemistry for gold extraction. Analytical scale extractions of gold from a variety of matrices can be conveniently used to assess the efficiency of any new proposed ligand.

Oct 1, 2003

By Donald S. Cameron

By dispersing gold in high surface area form supported on metal oxides, its inert character can be transformed to make economical, effective catalysts. Gold has already been demonstrated in a number of fuel cell applications such as gas phase catalysts, electro-catalysts, and electrical connectors. In this paper, the various types of fuel cell systems are reviewed, and several opportunities for gold identified. Low temperature fuel cells, including alkaline and solid polymer electrolyte types rely on high surface area platinum group metal catalysts which are highly susceptible to poisoning by low concentrations of carbon monoxide in the fuel supply. Hydrogen is frequently obtained by steam reforming hydrocarbons, followed by the water gas shift (WGS) reaction. A promising initial use for supported gold catalysts is in catalysing this WGS reaction. Research has shown that gold supported on iron oxide (Au/a-Fe2O3 ) WGS catalysts are more active than the current commercial copper oxide / zinc oxide catalysts, and effective at temperatures as low as 120oC. Products from reformer/ water gas shift reactors can be further purified by removing traces of carbon monoxide. If a small proportion of oxygen is introduced into the fuel gas stream, carbon monoxide can be preferentially oxidized to carbon dioxide even in the presence of hydrogen. Gold nanoparticle catalysts on iron oxide support (Au/a-Fe2O3 ) have exhibited higher activity than commercially available platinum on alumina (Pt/?- Al2O3 ) preferential oxidation catalysts. The low temperature of this reaction may make it feasible to incorporate these catalysts within the fuel cell itself. Proton exchange fuel cells provide several possible applications for catalytically active gold and its alloys. Carbon supported platinum group metals would benefit greatly from improved electrical conductivity if gold replaced some or all of the carbon support material. As electrode current densities are raised, electrical resistance constitutes an increasing proportion of voltage losses within the fuel cell. Dramatic reductions in cell stack voltage losses have already been demonstrated by reducing inter-cell contact resistance using gold plating. The low temperature oxidation properties of gold catalysts have been investigated in controlling gaseous emissions from direct methanol fuel cells, and gold also provides essential catalysis in building direct borohydride oxidation fuel cells. The prospect of a range of other applications for gold in fuel cells to contribute useful improvements in corrosion resistance and conductivity is assessed. Globally, fuel cells have been developed for a wide range of applications including stationary generators, cars and buses, industrial vehicles and small portable power supplies, each of which represents a substantial market. Hence there are likely to be many and varied opportunities for gold catalysts to contribute to the performance and economics of the systems being commercialized.

Oct 1, 2003