Platinum Metals Rev., 1987, 31, (2), 108
NEW PATENTS: April 1987
METALS AND ALLOYS
Magneto/Optical Storage Element
sharp k.k. European Appl. 192,256A
The element has a multi-layer structure including a reflective layer of Al-Ni alloy, or an alloy of Al with Pd, Pt, Cr or Mo. These alloys have a lower coefficient of thermal conductivity than Al alone; therefore recording sensitivity and quality of reproduction are maintained.
Reversible Hydrogen Storage
standard oil co. (ohio) European Appl. 198,599A
A reversible H2 storage medium comprises an amorphous metal alloy AnMbM′c where A is one or more of Pd, Pt, Ag, Au and Hg, M is one or more of Ru, Cu, Cr, Zn, etc., and M′ is one or more of C, Mg, Ti, rare earths, etc. A substantial portion of A is disposed on the surface of the material. The composition can be efficiently cycled without embrittlement.
Multi Phase Cermet Compositions
u.s. dept. of energy U.S. Patent 4,605,440
A B carbide-Al cermet has at least four phases and its composition comprises these plus a β carbide-reactive metal component where the reactive metal is chosen from Os, Pd, Pt, Ir, Rh, Ru, Se, Si, Sr, etc. A multiphase microstructure is produced with the ceramic phases homogeneously distributed in the metallic phases and with strong adhesive forces at the ceramic/metal interfaces.
Porous Fine Powder Production
allied corp. U.S. Patent 4,615,736
Salts of Pt, Pd, Ru, Rh, Ag, Au, Hg, Ir, Os, Re, As, and their mixtures are used to produce fine metallic powder by reduction under hypercritical temperature and pressure to form a fluid phase and the metal powder, which is then separated off.
Permanent Magnet Manufacture
toshiba k.k. Japanese Publ. Appl. 61/156,706
A R-Fe-B alloy (where R is at least one of Y and rare-earths and Fe can be substituted by Ru, Rh, Pd, Ir, Os, Re, Co, Cr, Al, etc.) is ground into a grain size of 2–10μ m, moulded in a magnetic field, sintered at 1000−1200°C and cooled to 400°C at 10°C/min; the magnets produced have high magnetic flux density, high coercive force and a variety of uses.
Magnetic Recording Medium
nec corp. Japanese Publ. Appl. 61/204,914
The medium has a magnetic film made from an Fe-Nd alloy containing Pt and optionally Ti. It is prepared by sputtering in Ar on a glass base. The medium has perpendicular magnetic recording properties and good corrosion resistance.
Shape Memory Alloy
tohoku metal ind. ltd. Japanese Publ. Appl. 61/217,544
Actuators operated at high temperatures, such as steam regulation valves use Ti-Ni-Ru.
Soft Palladium Manufacture
CHEMICAL COMPOUNDS
Dibenzalacetone Palladium Complexes
ciba geigy a.g. European Appl. 190,998A
New Pd complexes are copolymerisable with epoxy resin products and heat activated hardeners and/or curing catalysts for use as adhesives for example, but especially in the production of electrically conductive coatings and circuit patterns onto which metals can be deposited electrolessly.
ELECTROCHEMISTRY
Methane Production
gas res. inst. U.S. Patent 4,609,440
CH4 is produced by the electrochemical reduction of CO2 in aqueous solutions, using a Ru cathode. Current efficiencies of up to 30% can be achieved.
Electrolysis of Halide Solutions
standard oil co. U.S. Patent 4,609,442
Halogens are generated from halide containing solutions by using a cell containing an amorphous metal alloy with good electrochemical activity and corrosion resistance. The anode comprises preferably Fe55Ta40Pt5, Ti70Pt30, Zr60Pt40, etc.
Noble Metal Electrode
w. c. heraeus g.m.b.h. German Offen. 3,508,485
The electrode comprises a C particle-impregnated plastic, for example polyethylene, polypropylene, PTFE or PVC, base covered with electrolytically precipitated noble metal, of Ru, Rh, Pd, Ir and/or Pt. The coating has good adhesion to the plastic and the H2-embrittlement problem is overcome.
Electrode Prepation
ELECTRODEPOSITION AND SURFACE COATINGS
Coating for Glass Fibre
toray silicone k.k. European Appl. 192,275A
The coating composition consists of: (a) an organopolysiloxane, (b) a vinylated polysiloxane, (c) and organohydrogenpolysiloxane and (d) a Pt catalyst. The compositions are used for coating optical fibres for long-distance communications, and exhibit high tensile strength.
Ruthenium Chalcogenide Thin Film
cnrs cent. nat. rech. sci. World Patent Appl. 86/5,824A
Doped Ru sulphide, selenide or telluride are formed as a thin film by chemical vapour deposition using organometallic Ru derivatives. Products can be used in the semiconductor industry, especially in hostile environments and for passivation.
Ceramic Metallisation
agency of ind. sci. tech. Japanese Publ. Appl. 61/146,778
Ceramics are metallised by coating with a mixture of Cu salt (CuCO3, CuSO4, CuS, CuO, CuCl2), SiO2 and/or kaolin and at least one of Pd, Pd oxide, or Pt chloride, by heating at 900−1300°C in an oxidising atmosphere, and then reducing. The metallisation layer has adhesive strength and chemical resistance.
Surface Activation of Glass Fibre
nitto boseki k.k. Japanese Publ. Appl. 61/186,250
A glass fibre surface is activated by applying a liquid containing Ti coupling agent and dibenzonitrile Pd chloride, and then reducing the fibre to deposit Pd nuclei to act as a metal plating catalyst. The fibre can be electrolessly coated and has bond strength.
Plastic Antistatic Treatment
hitachi k.k. Japanese Publ. Appl. 61/190,900
Plastic surfaces are rendered antistatic by forming a sputtered film of conductive material, such as Pd, Au, stainless steel, SnO2, etc. Sputtering lowers the electrical resistance of the surface.
Palladium Coatings on Steel
mitsubishi motor corp. Japanese Publ. Appl. 61/201,781
Excess urea is added to PdCl4 to prepare aqueous solutions of pH 2–3, and then clean steel is immersed therein, removed, dried and fixed to coat Pd onto the steel which now has improved heat and oxidation resistance.
Plating Hydraulic Cement
denki kagaku kogyo k.k. Japanese Publ. Appl. 61/210,182
Cement material is surface activated with a platinum group metal compound in a bath to produce a catalytic layer, and is then plated electrolessly with Cu, Ni, Cr, Co, Sn, Ag or Au, etc.
Metal Plating Process
agency of ind. sci. tech. Japanese Publ. Appl. 61/277,175
The process for use with insulation printed circuit boards, magnetic shielding, etc., involves depositing a Pd organosol dispersed in an organic solvent on the article being plated, evaporating the solvent to form a Pd colloid on the article and then plating.
Tinted Coatings
LABORATORY APPARATUS AND TECHNIQUE
Chemical Detector
minnesota mining mfg. co. European Appl. 195,648A
The detector comprises a photoluminescent semiconductor having a metal, preferably Pd, coating on a radiation emitting surface, the height of the Schottky barrier of the diode varying when H2 is absorbed by the metal layer; a source of actinic radiation and a means for detecting changes in the radiation emitted from the surface.
Pressure Transmitting Device
toshiba k.k. Japanese Publ. Appl. 61/194,326
A pressure differential transmitting device includes a diaphragm which consists of a thin sheet of elastic metal to detect the pressure of a fluid. The sheet is an alloy of formula (M–M′)TbY, where M is Fe, Co or Ni, M′ is Pd, Rh, Ir, Pt, Re, W, etc., and Y is Si, B, P, etc. The device is lightweight and has good environmental and corrosion resistance.
Optical Hydrogen Sensor
agency of ind. sci. tech. Japanese Publ. Appl. 61/204,545
The sensor is composed of (a) a substrate with a monolithically embedded optical waveguide, (b) a light-absorbing layer formed on the waveguide area of the substrate and composed of a dielectic substance with dissociated H, part of which may be Ir(OH)n, Rh2O3.xH2O, WO3, MoO3, V2O5, TiO2, heptyl viologen, etc., and (c) an absorbing layer capable of dissociating adsorbed H2, for example Pd or Pt.
Moisture Content Probe
erno raumfahrtech g.m.b.h. German Offen. 3,510,379
A probe for measuring moisture content in a substance has a carrier with a Pt resistance temperature sensor mounted on it. The output signal is dependent upon the thermal conductivity of the substance, and one example of use is for plant-rearing-chamber nutritive media.
Galvanic Gas Humidity Sensor
belorussian lenin univ. Russian Patent 1,223,120
The sensor contains an electrochemical cell with a solid electrolyte and two platinised metal grid electrodes covered in Pt black. Crystal hydrates with or without an anhydrous compound are placed in the cell, and Cr dihydro-tripolyphosphate is used as the solid electrolyte. The sensor determines the relative humidity of a gas from −20 to 100°C.
HETEROGENEOUS CATALYSIS
Optical Fibre Cable
telephone cables ltd. British Appl. 2,172,410A
The cable has H2-trapping powder, such as Pd/C, running longitudinally within the protective cover to catalyse the reaction of H2 and O2 to form H2O, and it is mixed with H2O-sorbent or blocking substance. The powder is supported on a tape to prevent its interference with the movement of the fibres.
Preparation of Oxalic Acid Diester
rohm g.m.b.h. British Appl. 2,173,794A
Diesters of oxalic acid are prepared by oxidative carbonylation of an alcohol at a pressure of 1–700 atm and at 20−250°C in the presence of a catalyst system comprising Pd, at least one metal halide and activated charcoal. High yields are obtained over short times.
Ammonium Nitrate Removal from Waste Water
osaka gas k.k. European Appl. 196,597A
Treatment is effected by contacting waste water with a supported catalyst of Ru, Rh, Pd, Os, Ir, Pt or Au at 100−370°C and pH 3–11.5, in order to oxidise the NH3. The process is especially applicable to waste water from U processing, or reprocessing U fuel.
Ethanol and Propanol Production
bp chemicals ltd. European Appl. 198,681A
The preparation is achieved by vapour phase hydrogenation of acetic or propionic acid over a catalyst comprising a Group VIII metal, preferably Pd or Ru, and Re/C or/SiO2. High long lasting activity and selectivity are attained at 1–150 bar.
Alcohol or Ester Preparation
b.p. chemicals ltd. European Appl. 198,682A
The preparation involves contacting a 2–12C carboxylic acid at increased temperature and pressure with H2 in the presence of a heterogeneous catalyst comprising Mo or W and preferably Pd, Rh or Ru.
Reforming Catalyst
chevron research co. European Appl. 198,721A
The catalyst comprises a large-pore zeolite containing 1 atomic proportion of Pt and at least 0.1 atomic proportions of promotor metal, consisting of at least one of Fe, Co and Ti. The catalyst is highly active and selective for dehydrocyclisation.
Catalytic Combustion of Light Hydrocarbon
nippon shokubai kagaku European Appl. 198,948A
1–4C Hydrocarbon fuels are combusted using a two stage noble metal catalyst system. The first stage catalyst comprises Pd/Pt or Pd/Pt/NiO and effects sufficient combustion to give a temperature high enough to induce secondary combustion with Pt or Pt/Pd. CH4 can be burned without emission of CO, NO2 or hydrocarbons.
One Step Esterification
standard oil co. (ohio) European Appl. 199,530A
The process under mild reaction conditions, involves reaction with O2 in the presence of a Pd based intermetallic catalyst, such as PdTe0.25Zn0.25, supported or unsupported. The aldehyde is preferably (meth)acrolein and the alcohol is preferably methanol.
Deuterated (Meth)acrylic Acid Production
mitsubishi rayon k.k. European Appl. 203,588A
(Meth)acrylic acid is deuterated directly by exchange of H in the presence of a catalyst, preferably Pd, Ru, Ir, Rh or Pt or their compounds at 60−200°C. The resultant acids can be esterified to give deuterated (meth)acrylates for use in the production of low light loss optical fibres.
Hydrogen Production
phillips petroleum co. U.S. Patent 4,602,988
H2 is produced from alkaline aqueous solvents of H2S by irradiation with light at 300–700 nm in the presence of catalytic amounts of ZnO-RuO2, ZnO, ZnS, ZnSe or CuGaS2.
Dehydrogenation Catalyst
uop inc. U.S. Patent 4,608,360
A catalyst for paraffin dehydrogenation comprises Pt, Pd, Ir, Rh, Os, Ru, a co-formed Group IVA metal, such as Ge, Sn, or Pb, and an alkali(ne earth) metal, for example Cs, Rb, K, Na, etc., on an Al2O3 support. The products can be used in the manufacture of detergents, high octane petroleum, pharmaceuticals and plastics.
Propylene Acetoxylation Catalyst
phillips petroleum co. U.S. Patent 4,608,362
The catalyst comprises K, Bi and Pd on a support, together with Rh as a promoter. Acetoxylation of propylene is effected with higher selectivity, conversion and space time yield.
Methane Production
dow chemical co. U.S. Patent 4,609,679
High methane yields from synthesis gas are effected using a supported Ru catalyst along with at least one oxide of Ta, Nb or V. The calcination temperature during support production is such that no crystalline metal oxide is detectable by X-ray diffraction before Ru deposition.
Staging Reforming Catalysts
exxon res. & eng. co. U.S. Patent 4,613,423
The octane quality of a naphtha is improved by reforming in the presence of H2 in a reforming unit comprising several reactors in series, with a Pt or Pt/Re catalyst in each. The catalyst of the last reactor contains Pt and Re and sufficient Ir to increase the 5C + liquid yield.
Hydroisomerisation Catalyst
mobil oil corp. U.S. Patent 4,615,997
The catalyst containing a highly dispersed noble metal, preferably Pt, Pd, Os, Re or Ru and comprising a zeolite of Constraint Index <2, and a binder, is prepared by (a) incorporating noble metal with the zeolite and binder (b) calcining and (c) contacting with a stream of inert gas containing Cl2. The catalyst is used for low pressure isomerisation of paraffin.
Engine Exhaust Filter
toyota jidosha k.k. Japanese Publ. Appl. 61/146,314
A filter for removing C particles from engine exhaust consists of a honeycomb cordierite base with Pd and/or Rh catalysts and alkali metal oxide(s) deposited on it. C particles are trapped and burned at a combustion efficiency of 85%.
I.C.E. Purification Catalyst
nissan chem. ind. k.k. Japanese Publ. Appl. 61,197,038
The catalyst consists of a monolithic support carrying a catalyst of CeO2, Pr6O11, a platinum group metal and activated Al2O3 preliminarily loaded with Ce. It can remove hydrocarbons, CO and NOx simultaneously.
Waste Gas Purification Catalyst
matsushita elec. ind. k.k. Japanese Publ. Appl. 61/230,737
The catalyst consists of a glass fibre sheet whose SiO2 content is increased above 95% by acid- or heat-treatment, and a layer of inorganic oxide, which is mainly γ -Al2O3 where Pt and/or Pd, and TiO2 are supported on the surface. It can be used for clarifying waste gas from domestic petroleum heaters.
Supported Catalyst Preparation
hoechst a.g. German Offen. 3,533,250
The catalyst for exhaust gas purification, hydrogenation and isomerisation reactions is produced by applying Ru, Pd, Rh, Ir or Pt onto a ceramic honeycomb provided with an Al2O3 layer. The honeycomb is soaked in aqueous NH3 solution and at least one noble metal salt, dried and tempered.
Production of Hydroxylamine Sulphate
grodno azot combine Russian Patent 1,214,584
N oxide is reduced with H2 in a 6-vessel cascade reactor using a reaction medium of 18.5−20.0% H2SO4 in the presence of a catalyst of 0.3−0.5% Pt/graphite. Fresh catalyst is added continuously and spent catalyst removed regularly for regeneration and recycling.
HOMOGENEOUS CATALYSIS
Methanol Conversion Catalyst
british petroleum p.l.c. British Appl. 2,171,924A
A catalyst for converting syngas to methanol has formula MaThAbOx (I), where M is at least one of Pd, Pt and Ag, preferably Pd, and A is alkali metal. The production of a precursor to (I) is also claimed.
Pd(II)/PPh3 Containing Catalyst
shell int. res. mij. b.v. European Appl. 194,707A
A catalyst used in the hydrocarboxylation of alkynes with enhanced reaction rates and high selectivity comprises a divalent Pd compound and a tri-organic phosphine (II). The reaction is with CO and carboxylic acid in the liquid phase.
Aldehyde Production
soc. chim. charbonnages World Patent Appl. 86/5,415A
A catalyst system for the production of aldehydes comprises: (a) a Pt complex LPtX2, L is an organic compound containing at least 2 P atoms, X=halogen, (b) a complex combination of Sn and an alkylene carbonate. Aldehydes are produced by the hydroformylation of an ethylenically unsaturated compound with a mixture of CO and H2.
1–4C Alkanol Production
FUEL CELLS
Fuel Cell Electrodes
elec. power res. inst. inc. U.S. Patent 4,610,938
Improved performance with H3PO4 acid electrolyte fuel cells is obtained by coating the Pt/C electrode with a perfluorinated acid-containing addition polymer.
Catalyst for Fuel Cells
united technologies corp. U.S. Patent 4,613,582
A ternary metal alloy catalyst for fuel cell electrodes, and for other uses, which increases the work done by a fuel cell is formed from a finely divided noble metal, preferably Pt/C black, with Co and transition metal compound solutions, followed by reduction in N2.
GLASS TECHNOLOGY
Press-Mould for Glass
matsushita elec. ind. k.k. European Appl. 191,618A
Glass optical elements are press-moulded from softened glass using two moulds made from a high heat resistant base coated with a film of Ir, Ru, an alloy of Ir with Pt, Ru, Os, Rh or Re, or an alloy of Ru with Pt, Ru, Os, Rh or Re.
Optical Glass Mould
ELECTRICAL AND ELECTRONIC ENGINEERING
Electrochromic Element
nippon kogaku k.k. Japanese Publ. Appl. 61/144,630
The element consists of an opaque electrode, a reductively colouring electrochromic layer, a transparent ion-conductive layer and opposite electrode, the latter comprising a dispersed phase of metal or Ir (hydr)oxide and transparent solid electroconductive dispersion medium.
Slide Contact Device
tanaka kikinzoku kogyo Japanese Publ. Appls. 61/156,648–78
The device comprises a brush and commutator or slip ring. The brush is of alloy comprising, in wt.%: 68−72Au, 3−7Pt, 8−12Ag, 12−16Cu and 0.1−2Ni; 20−70Pd and 30−80Ag; or 32−38Pd, 8−12Au, 8−12Pt, 27−33Ag, 12−16Cu and 0.1−2Zn, etc. The device has less wear and a stable, but low contact resistance. Addition of C improves wear resistance.
Platinum Resistance
MEDICAL USES
Platinum Anti-Cancer Complexes
yeda res. & dev. co. ltd. European Appl. 190,464A
Complexes of Pt compounds, such as K2PtCl6, cis-platin, diaquodiammine Pt nitrate and a physiologically acceptable macromolecular carrier, for example a polysaccharide, or a polyamino acid are useful in anti-tumour treatment. Pt is released gradually in vivo thus reducing toxicity. Pt targeting can use anti-tumour antibodies as carriers.
Optical Sensor for Oxygen Monitoring
gould inc. European Appls. 190,829/30A
An extremely small monitoring device, which responds to light, comprises an optical waveguide, an O-sensitive medium preferably including a phenanthroline salt of Ru(II) perchlorate, which fluoresces in response to light, where fluorescence is dependent on O2 partial pressure. The device gives rapid, accurate, precise measurement for remote sensing, for example in arteries, blood vessels or catheters.
The Conjugation of Metallothionine to Bioactive Molecules
du pont de nemours co. European Appl. 196,669A
The production involves conjugating a bioactive molecule, such as an antibody or fragment, steroid, hormone, prostaglandin, etc., to a heterobifunctional crosslinker and then conjugating the product with the metallothionine, the metal of which may be a non-tracer such as Ru, Pt, Bi, Pb, Hg, Au, etc., or at least a part-exchanged tracer, Ru97, Pd103, Hg197, Pb203, Ag111, Au198, etc. The conjugate is useful in diagnosis and radiotherapy.
Preventing Bone Calcium Resorption
sloan-kettering inst. European Appl. 201,804A
The treatment consists of the administration of a suitable metal-containing compound, such as Ga acetate, nitrate or fluoride, diamminedichloro Pt(II), cis-diammine-1,1-cyclobutane dicarboxylate Pt(II), etc.
X-Ray Emitting Implant
nuclear med. inc. World Patent Appl. 86/4,248A
A particle for in vivo tumour-implantation contains Pd enriched in Pd102. This is activated by exposure to neutron flux giving a fraction of X-ray-emitting Pd103. The particle is non-toxic and biocompatible, and facilitates localised exposure.
Implantable Corneal Prosthesis
t. c. white U.S. Patent 4,612,012
An implantable corneal prosthesis comprises a lenticular transparent central portion and a peripheral portion with an outer tissue-contacting surface, preferably such as Pt, Au or polymer. All parts must be biologically compatible.
Malonato Pt (II) Complexes
jerusalem university U.S. Patent 4,614,811
The complexes with anti-tumour activity are of formula L2Pt(II)(OCO)2CH-NH2 where L is a monoor bidentate amine ligand. The complexes are chemically stable and can be injected intravenously.
Blood Gas Sensor
sumitomo elec. ind. k.k. Japanese Publ. Appl. 61/128,945
The sensor has an electrode component made of concentric electrodes comprising a pH electrode, a noble metal electrode, preferably Pt or Au and an Ag/AgCl electrode, which is between the first two. Simultaneous accurate determination of blood O2 and CO2 by skin application is possible.