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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 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 Serena Biella

Gold has received a growing interest as a catalyst for the selective oxidation of organic molecules using oxygen under mild conditions1. In the liquid phase application small gold particles (2.5-7 nm) deposited over different solid supports can be used but, like many other noble metals, their catalytic activity depends upon the nature of the support and the preparation metod2-5. In particular, gold on carbon is the preferred catalyst for the oxidation of the alcoholic 2-7 and the aldehydic7-9 groups and one of the best preparation method is the immobilisation of colloidal particles2-5,8,9. Suggested application of gold catalysis in fine chemicals production, tested on laboratory scale preparations, is reported in table 110. In order to produce more efficient catalysts for the liquid phase oxidation and to derive new insights into the reaction mechanism, we have made a comparison among catalytic systems based on different metals. The first effort was to test the activity, if present, of naked metal particles and then to study the influence of various materials commonly used as a support.

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 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&apos;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