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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 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 Michael Hopp

The beginning of the electroforming technology dates itself on the beginning of the industrial revolution 1800 to 1820 approximately. Basis was the existence of electricity in order to be able to drive the electro-form-process. With the development of the electroforming, big names of the science-history, like Michael Faraday (1791? 1867), Sir Humphry Davy (1778?1829), Max Schlöter (1878?1946), Werner von Siemens (1816?1892), and many others. Already about 1840, the first monograph originated to electroforming (38). While in the first years the electro-forming most extensive only to the coating of art - or other usefulness-objects was used. At the beginning of the 20th century the formation of objects from pure metals became more and more, later also from alloys to application. One of the first bigger electroforming factory, the ?Württembergische Metallwarenfabrik? was working 1894 in Geislingen / Steige, Germany. In the industrial application, the electroforming-technology is to be imagined away for miscellaneous coatingtasks and the form-body-preparation no longer today (18). A little bit confusing is the german name ?galvano-technology?. It based on the Italian physiologist and naturalist Luigi Galvani (1737 ? 1798). This technically seen is however wrong, right, the name is electroforming. The physical bases were founded mainly by Michael Faraday and Sir Humphry Davy.

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 Michael B. Cortie

The young field of nanotechnology has as its objective the design and construction of useful devices made of nanoscale materials. Objects or structures which have at least one important dimension in the range 0.5 to perhaps 50 nm may be considered to be in the nanoscale domain. These sizes lie far below the 200 nm or so that can be resolved with an optical microscope, and are closer in size to the 0.3 nm diameter of individual atoms. Nanotechnology, which is the study and exploitation of these tiny structures, is attracting keen interest at present. The excitement is motivated by the observation that control of matter at the nanoscale holds the promise of faster computing, better medicines, and smarter materials. In this paper, the physical phenomena on which this optimism is based are broadly discussed and explained. Where appropriate, examples of the rather different and curious properties of gold at the nanoscale are used to illustrate the points covered.

Oct 1, 2003

By Daven N. Compton

The optical properties of Au nanoparticles have been known for some time, with both Au colloids and Au nanoparticles embedded in glasses having been extensively studied. In this study, Pt nanoparticles have been incorporated into Au colloids, and the linear and non-linear optical properties investigated. UV-VIS spectrophotometry, fluorescence spectroscopy and the z-scan method have been used to examine the effects of such additions.

Oct 1, 2003

By Hiroaki Sakurai

Using batch reactors equipped with CO and CO2 gas sensor, CO oxidation over Au catalysts in room air has been investigated and compared with Pt catalysts. For both Au and Pt catalysts, the logarithm plot of CO concentration data during initial 10 min are well fitted by straight line, which mean the first order dependence on the CO concentration between 10 and 10,000ppm. The rate constant value (k) over Au and Pt catalyst generally decrease with increasing initial CO concentration above 100ppm. The value decrease especially rapidly between 100ppm and 1,000ppm over Pt catalysts, which should be due to the strong adsorption of CO on Pt. The k value over Au catalyst has become ten times or more as large as the Pt catalysts at 1,000ppm. Already for the initial concentration of 100ppm CO, the strongly adsorbed CO on Pt metal has been clearly observed by FT-IR during the reaction over Pt/Al2O3. A part of the strongly adsorbed CO has been remained on Pt after the disappearance of gas phase CO, and has gradually changed to gas phase CO2. Such strongly adsorbed species on Au has never been observed on Au/TiO2 under the same reaction conditions. These features of Au catalysts are favorable for indoor air purification.

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 Michael B. Cortie

Mesoporous gold sponge has the unique property of being both metallic and highly resistant to oxidation. It has potential application in catalysis, in bio-sensors, in optical coatings, in analytical chemistry and, as we show here, as the basis for a new kind of ultra-capacitor. Due to the cost of gold, the most probable niche for a gold-based ultra-capacitor would be in the high-power/high-energy regime, a region where gold would compete with devices based on RuO2. A high internal resistance limits the power that can be usefully drawn from existing carbon-based ultra-capacitors, and that this problem can potentially be overcome by gold-based devices. A simple proof-of-concept ultra-capacitor based on mesoporous gold is described and its behaviour during charge and discharge cycles examined. In this work a step change in the input or output voltage of the device was used as the controlling parameter. There was also a residual faradaic current resulting from traces of undissolved aluminium left over from the AuAl2 precursor used to make the sponge, and some charge storage due to polarization of the solution. Deconvolution of these three effects was not entirely accomplished, but an ostensible capacitance of about 7 to 14 mF/g Au was demonstrated. Further improvement from these early results seems likely.

Oct 1, 2003

By M. Kinne

Catalyst preparation/ characterization Slightly modified DP (~Schumacher et al. Catal. Lett. 89, 109, 2003) CeO2 HAS 15 from Rhodia calcined in air for~ 2h BET: ~188m2/g, particles size: 5.7nm (TEM, XRD) + HAuCl4 at pH of 6.5-7, (>95% of the Au was deposited) ? Au/CeO2 (2.6wt% Au, ICP-AES) A new conditioning procedure was applied, including heating at low temperature in N2 and H2/N2 mixtures) Patent DE 10205873A1. Very small Au particles <2nm, for CO oxidation catalyst as Au/TiO2, Au/Fe2O3, and Au/Co2O3 Here Au particles size <3.5nm (XRD) Summary ? CO is nearly exclusively adsorbed on the Au particles ? Positive reaction orders of 0.5 are found for CO and H2O ? Ea= 40kJ/mol ? The catalyst is very active and stable ? During WGS reaction huge amounts of formates are formed and cover the surface ? The activity of the catalyst seems to be correlated with the formate species.

Oct 1, 2003

By Michio Okada

Dissociative adsorption of hydrogen (deuterium) on thin gold films grown on Ir{111} surface has been studied with temperature-programmed desorption using a quadrupole mass spectrometer and nuclear reaction analysis. Thin Au{111} films are epitaxially grown on Ir{111}. Surprisingly, H2 (D2) can dissociatively adsorb on these Au{111} films, although it is well known that Au surfaces are noble enough not to dissociate hydrogen molecules [B. Hammer and J.K. Nørskov, Nature 376, (1995) 238]. We attribute this to the sensitivity of hydrogen to changes in the local surface properties, e.g., electron localization (the narrowing of the s-band, the s-band center model), which could explain the upto now unexpected high for the reactivity of a thin Au{111} surface. Moreover, we found that H (D) atoms can be confined into a Au thin film and/or the interface between an Ir surface and the thin Au film. We demonstrate how anomalously reactive thin Au films grown on an Ir surface are, and also compare the Au films with Ag films grown on Ir to test the validity/generality of our proposed s-band center model.

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 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 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 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&apos;s structure and morphology, size and composition of nanoparticles and electrochemical behavior of modified electrodes.

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 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