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Journal Archive

Platinum Metals Rev., 1984, 28, (2), 91

NEW PATENTS: April 1984



Magnetic Alloy

research institute of electric & magnetic alloys U.S. Patent 4,396,441

A permanent magnet having an ultra-high coercive force and large maximum energy product is made from an alloy of specified crystal structure consisting of 63.76-75.96% Pt, remainder Fe.

Brazing Alloy

general electric co. U.S. Patent 4,396,577

A brazing alloy particularly suitable for use in high temperature gas-turbine engines consists of 25-95% Pd, up to 5% Si, up to 3.5% B, remainder Co.

High Chromium Superalloy

johnson matthey p.l.c. East German Patent 202,310

Ni alloys containing 23-27wt.% Cr of improved mechanical properties and corrosion resistance contain up to 1.7% C, up to 1.5% Ti and/or up to 1.5% Al, 0.3-4% Pt and/or 0.3-8% Ru. The alloy is especially suited for use in contact with molten glass, for example in a centrifugal spinner.


Water Electrolysis

institute of gas technology

U.S. Patent 4,395,316

In a process for producing pure H2 by water electrolysis, the anode is depolarised with a solution of monosaccharides and/or lignins to suppress the evolution of molecular O2. The anode is preferably of Pt coated with a Pb-rich Ru pyrochlore of general formula Pb2(Ru2-xPbx)O7-y where x is 0-1.2.

Film Photoelectrodes

diamond shamrock corp. U.S. Patent 4,396,485

Film photoelectrodes for use particularly in the conversion of solar energy are claimed. They may contain lanthanide and/or platinum group metals.

Cermet Anodes

diamond shamrock corp. U.S. Patent 4,397,729

An improved anode for the electrowinning of a metal especially Al, from a molten salt bath consists of a mixture of a cermet material such as Ni ferrite and Pd, Pt, Ir, Rh, Au or one of their alloys.

Composite Electrolytic Cell Electrodes

c-i-l inc. U.S. Patent 4,401,544

A composite electrode is made by forming a stack of alternate anode plates and cathode plates with a thin plastic film between them. The cathode plates are particularly made of valve metal coated with platinum group metals or their oxides. The composite electrode enables the cell voltage to be reduced.

Palladium Cathode

commissariat a l’energie atomique

French Appl. 2,517,663

An electrolytic process for treating tritium-contaminated aqueous effluents uses a Pd or Pd alloy cathode.


Platinum Metal Paint for Chemical Plating

okuno chemical industry co. ltd.

European Appl. 92,601

A mixture of 0.01-25% Pd or Pd compound in powder form (up to 0.5μ m) and 75-99.99% organic solvent or vehicle is applied to a ceramic or other surface and fired. The resulting film catalyses subsequent chemical plating, for example, Ni, and ensures secure adhesion to the substrate.

White Palladium Electroplating

occidental chemical corp. U.S. Patent 4,392,921

White coating films of Pd are obtained by electrodeposition from a bath containing, per litre, 1–6g Pd as Pd(NH3)2(NO2)2 and 50-100g of an ammonium salt (sulphate or phosphate), buffered to pH 8–10.

Thermochromic Coating Compositions

lgz landis & gyr zug a.g. U.S. Patent 4,394,407

Thermochromic coating compositions, for identity or credit cards, consist essentially of an organic binder, an organic sulphur compound and a compound or complex of a metal which may be Ag, Au, Pd or Pt, among others.

Coating Films for Carbon

j. intrater and g. bertoldo U.S. Patent 4,396,677

Non-dewettable films on surfaces such as graphite, diamond or sapphire are made by applying a mixture of Sn, Pb, In or one of their alloys, and a carbide- or carbonyl-forming metal which may be Ru, Rh, Os or Ir, among others.

Platinum Group Metal Thermal Barriers

johnson matthey & co. ltd. U.S. Patent 4,399,199

Superalloys for use at very high temperatures, in gas turbine engines, are protected by applying a thin film of a platinum group metal (preferably Pt) and a thermal barrier layer of Zr oxide stabilised with another metal oxide, such as Y oxide.

Palladium Electroplating Bath

occidental chemical corp. U.S. Patent 4,401,527

A bath which operates at high current densities and constant plating efficiencies contains Pd ions and excess free nitrite ions (based on the Pd-ions). The bath preferably contains a buffer to hold the pH at 6.5–7.5. In an example the bath contains, per litre, 50g Pd diaminodinitrite, 90g NH4NO3, 10g NaNO2 and 25g ammonium borate.

Rhodium Electroplating

degussa a.g. U.S. Patent 4,402,802

Bright, haze-free Rh coatings of a white-Au colour are obtained from baths containing Rh sulphate and/or phosphate, sulphuric and/or phosphoric acid and also a phenol- or pyridine-sulphonic acid.

Osmium Plating

kharkovskii gosudarstvennyi pedagogichskii institutim. g.s. skovorody Russian Patent 1,014,996

An Os electroplating bath contains per litre 0.19–19g Os ions, 50-300g Na2SO4 and 0.00004-40g NaOH.


Mass Liquid Flow Measurement

lucas industries p.l.c. British Appl. 2,1 19,517A

A fluid being measured flows through a hollow collector electrode assembly which has a central wire electrode of Pt-Rh alloy, Pd-Ru alloy or Pt-plated steel.

Catalytic Combustible Gas Detectors

english electric valve co. ltd. British Appl. 2,121,180A

A combustible gas detector element comprises a heatable wire filament which may be made of Pt or one of its alloys, embedded in a pellet formed overall of an oxidation catalyst, such as Pd or Pt, and a porous non-catalytic inert carrier which comprises colloidal SiO2.

Carbon Monoxide Gas Sensor

honeywell inc. European Appl. 95,844

A CO sensor has an Al2O3 substrate coated with 200-500Å of Rh or Ru which chemisorbs the CO as it passes over the film. The resistance of the film changes in a corresponding way.

Detecting Oxidising and Reducing Agents in Fluids

dow chemical co. European Appl. 96,117

A new detector with an ion exchange membrane has two electrodes with a membrane separating them and also separating the second electrode from the fluid, which contains an oxidising agent or a reducing agent to be detected. This enables the device to stabilise quickly. The first electrode preferably consists of Pt and the second of Pt or Ag. The device is particularly intended for determining Cl2 in air.

Dissolved Hydrogen Concentration Measurement

hitachi ltd. European Appl. 96,417

The H2 dissolved in a water sample is measured by an electrode with a H2-permeable membrane on its surface, preferably made of Pd. A Ag/Ag sulphate reference electrode may be used.

Hydrogen Sensor

netherlands tno European Appl. 97,390

An electrochemical sensor for measuring H activity in metals, for example for testing welds, uses a thin layer of Pd or Pd-Ag alloy as contact and electrode.

Electrochemical Sensor

bayer a.g. U.S. Patent 4,394,239

In a rapid-response sensor for measuring the concentration of CO, H2 or hydrazine in the air, the electrolyte is an aqueous gelatinous polymeric adhesive containing dissolved ionic materials and the measuring electrode is a matrix containing a catalyst. For CO and H2 the matrix is graphite and the catalyst is Pt while for hydrazine the matrix is C coated with Au and the counter electrode is C coated with Pt black.


Autothermal Hydrocarbon Reforming Catalyst

united technologies corp.

British Appl. 2,118,857A

Highly active hydrocarbon steam reforming catalysts, particularly catalysts for autothermal reforming, contain 0.01-6% Rh deposited on an Al2O2 substrate impregnated with 10-35% CaO. These catalysts eliminate the C plugging that occurred with Ni catalysts.

Formaldehyde Production

mitsubishi gas chemical co. inc.

British Appl. 2,121,787A

Formaldehyde is produced by catalytic oxidation-dehydrogenation of methanol with air in the presence of a Ag-Pd catalyst which may contain up to 5% Pd.

Catalytic Alcohol Production

institut francais du petrole

European Appl. 95,408

Alcohols are obtained when carboxylic esters are hydrogenolysed in the presence of a supported mixture of Rh and Ge, Sn and/or Pb. Thus ethanol and butanol are produced by the hydrogenolysis of butyl acetate using a Rh-Sn/SiO2 catalyst.

Iridium Catalyst Pretreatment

mobil oil corp. European Appl. 96,483

A freshly prepared reforming catalyst containing Ir is initially treated with O2 and a hydrogen halide (dry HCl) and then with a reducing agent, also at elevated temperature. A typical catalyst contains 0.3% each of Ir, Pt and Re on a support. The treatment ensures that the Ir is present in its most effective oxidation state.

Heterocatalyst System

university patents inc. European Appl. 98,289

Heterocatalyst systems where a metal complex is reacted with an -OH group which is in a zeolite or molecular sieve cavity are useful for carbonylation, hydrogenation, and Fischer-Tropsch reactions. The metal complex may be of a Group VIII metal, such as Rh, Pd or Pt, as in zeolite-O-Rh(alkyl)2.

Paraffin Dehydrogenation Catalyst

shell internationale research mij. b.v.

European Appl. 98,622

Paraffins containing 2, 3 or 4 C atoms are dehydrogenated in the presence of a known Pt-Sn composition produced in a new way. The Al2O3 is first impregnated with an aqueous Sn compound solution and calcined. The product is then impregnated with an aqueous Pt compound solution, reduced and dehalogenated and finally a Group IA metal compound, such as CsOH is introduced.

Catalytic Engine

johnson matthey & co. ltd. U.S. Patent 4,389,983

A catalytic I.C. engine can be operated on the stratified charge principle. The engine includes one or more precombustion chambers containing a catalyst which is preferably a honeycomb, gauze or corrugated sheet or foil of a platinum group metal and/or alloy (excluding Os).

Catalyst for I.C. Engine Exhaust Systems

w. r. grace & co. U.S. Patent 4,390,456

A catalyst consists of platinum group metal or metals supported on a specified carrier consisting of spheroidal Al2O3 particles of defined properties.

Hydrocarbon Production Catalysts

standard oil co. U.S. Patent 4,390,639

Synthesis gas is converted to a mixture of olefins, alcohols and carboxylic acids over a catalyst which is a mixture of Au and a partly reduced Ru oxide supported on a SiO2-Al2O3 carrier. The products may optionally be further hydrogenated over a mixed oxide catalyst such as RuCoPdZn0.4Ox.

Benzene Hydrogenation Catalyst

stamicarbon b.v. U.S. Patent 4,392,001

The partial hydrogenation of benzene to cyclohexene in the presence of steam is catalysed by metallic Ru.

Hydrocarbon Processing

institut francais du petrole

U.S. Patent 4,392,002

In a process for making petroleum from 4C hydrocarbons, butyl-1-ene is converted to the 2-isomer in the presence of H2 over a catalyst which is an Al2O3 carrier supporting Ni, Co or preferably Pd.

Osmium Tetroxide Catalyst

exxon research & engineering co.

U.S. Patent 4,393,253

The formation of diols by reaction of olefins with water and t-butyl hydroperoxide is catalysed by OsO4 preferably promoted with Na bromide or iodide.

Hydrocarbon Conversion Catalyst

u.s. department of energy U.S. Patent 4,396,539

A catalyst for the conversion of synthesis gas to hydrocarbons consists of a carrier such as Al2O3 supporting Co and Pd or Pt.

Hydrocarbon Dehydrogenation Catalyst

uop inc. U.S. Patent 4,396,540

A catalyst for the dehydrogenation of hydrocarbons consists of a carrier such as Al2O3 impregnated with 0.01-2% Ru formed by pyrolysis of a carbonyl complex, 0.01-2% Pd, Pt, Rh or Ir, 0.01-5% Re and 0.01-5% Group IA or IIA metal.

Immobilised Group VIII Metal Catalysts

mobil oil. co. U.S. Patent 4,400,561

Catalysts for olefin conversion reactions such as dimerisation or hydroformylation consist of a refractory oxide carrier of specified surface properties modified with a functional amine which acts as a bridge to a Group VIII metal. The metal is preferably a platinum group metal, especially rhodium or ruthenium.

Hydrocarbon Reforming Catalyst

ste. francaise des produits pour catalyse

U.S. Patent 4,401,557

Hydrocarbon conversion, especially reforming, is catalysed by a supported mixture of 0.005-1% Pt, 0.005-1% Rh or Os, 0.005-5% Cr, W, Mo, Mn, Re, Ga, In, Tl, Th, Ce, Sm, La, Zn, Cd, Ti or Zr and 0.01-10% halogen.

Hydrocarbon Reforming Mixed Catalyst

standard oil co. (indiana) U.S. Patent 4,401,558

A new catalyst, superior in properties to multimetal supported catalysts, is a mixture of particles of two components, one containing a platinum group metal or metals and the other a Group IVB or VB metal, on halogenated oxide supports. Thus one may contain Pt and Pd and the other V, Ta or Zr.

Reforming Catalysts

exxon research & engineering co.

U.S. Patent 4,404,094

The activity of supported Pt-Ir-halogen reforming catalysts also containing Cu, S or preferably Se is increased by pretreatment with a stream of dry H2 at specified temperature and flow rate for 16 hours or more.

Hydrogenation Catalyst

phillips petroleum co.

U.S. Patent 4,404,124

The selective hydrogenation to ethylene of acetylene in a gas stream composed mainly of ethylene is catalysed by Al2O3 particles impregnated with 0.01-0.025% Pd and at least twice this weight of Ag. The Ag is distributed evenly but the Pd is concentrated at the surface of the particles.

Carbonylation Catalyst

hoechst a.g. German Offen. 3,203,060

An improved catalyst for the synthesis of acetic acid, acetaldehyde and methanol from CO and H2 consists of a SiO2 carrier impregnated with a lanthanide metal chloride and then with Rh chloride.


Crystalline Silicate Catalyst

research association for petroleum alternatives development British Appl. 2,122,591A

Crystalline silicates, useful as catalysts for organic reactions such as polymerisation, alkylation, isomerisation and disproportionation, may include a proportion of La2O3, Ce2O3 and/or M2O3 in which M is Al or at least one trivalent transition metal, such as Rh, Ru, Pd or Ce. The silicates may be impregnated with Ru, Rh, Pd, Pt, La, or Ce. A typical silicate has the formula 0.4Na20.(0.5La2O3. 0.5Ce2O3).80SiO2 and part of the Ce may be replaced by Ru or Nd.

Rhodium Complex Catalysts

imperial chemical industries ltd.

European Appl. 94,748

The formation of aldehydes and acetals from conjugated 4-6C dienes, alcohols, CO and water is catalysed by a system consisting of a Rh complex such as ClRh(CO)(PPh3)2, triphenylphosphine and a strong acid.

Rhodium Complex Catalyst

british petroleum co. p.l.c. European Appl. 94,785

The formation of alkyl formates by reaction of alcohols with CO2 and H2 in THF media, and in the presence of a basic oxide is catalysed by RhCl2(PPh3)3.

Hydroformylation Process

davy mckee (london) ltd.

European Appls. 96,986/88

A new Rh catalyst giving an n-aldehyde : isoaldehyde ratio in the product comparable to a Co catalyst contains Rh, CO and a cyclic phosphite having a bridgehead P atom linked to three O atoms of which at least two form part of an -O-P-O-ring, such as 2,8,9-trioxa-1-phosphatricyclo-[,7]-decane. Similar phosphites are claimed in 96,987.

Mixed Carboxylic Acids Production

shell internationale research mij. b.v. European Appl. 97,978

Mixtures of carboxylic acids, of which one contains a -CH2COOH grouping, are produced by reacting an acid, ketone or ester with CO and H2 in the presence of a Rh catalyst and a source of I and/or Br. The Rh catalyst is preferably complexed with a phosphine, phosphite, etc. Thus propionic acid, acetic acid, butyric acid and isobutyric acid may be produced from methyl acetate in the presence of propionic acid.

Ethanol Production

imperial chemical industries p.l.c.

European Appl. 98,031

Ethanol is produced directly and selectively from CO and H2 using a catalyst mixture of Ru, a Group VII and/or VIII metal and a source of halide in an aprotic amide, imide or heterocyclic compound, such as an alkyl pyrrolidone. Typically the catalyst contains Ru and Co, Fe or Ni carbonyls and KI.

Oil Production from Garbage

johnson matthey p.l.c. U.S. Patent 4,396,786

Cellulosic material is converted to fuel oil by hydrolysing the cellulose, carbonylating the product using a reducing gas, for example H2 and CO in the presence of Cu or a platinum group metal to form a keto acid, heating to polymerise the keto acid and hydrogenating the polymer to form fuel oil. The preferred catalyst is Na ruthenate.

Rhodium Phosphine Hydroformylation Catalysts

toa nenryo k.k. U.S. Patent 4,397,788

New rhodium phosphine compounds isoelectronic with HRh(CO)(PPh3)3 have the structure HRh(CO)(XR3)x(YR3)y, when, X is P, As or Sb, Y is As or Sb; when X is P, Y is P or Sb; when X is As, Y is P, As or Sb; when X is Sb, R is the same or different aryl group, x is 1 or 2 and y is 2 or 1. These compounds, such as HRh(CO)(SbPh3)(AsPh3)2, can be used as hydroformylation catalysts.

Phase Transfer Hydroformylation of Olefins

johnson matthey p.l.c. U.S. Patent 4,399,312

A process for the hydroformylation of olefins which facilitates recovery of noble metal catalysts and which proceeds under mild conditions comprises using as catalyst a water-soluble complex of a platinum group metal, the reaction mixture including aqueous and organic phases and an amphiphilic reagent.

Rhodium Complex Catalysts

union carbide corp. U.S. Patent 4,400,548

In a process for the hydroformylation of olefins to aldehydes using a Rh complex catalyst, the efficiency and thermal stability of the catalyst are improved when the ligand is a bis-t-phosphine monoxide such as bis(diphenylphosphino)ethane P-oxide.

Rhodium Complex Catalysts

f. hoffmann-la roche & co. a.g.

German Offen. 3,302,697

Asymmetric hydrogenation reactions are catalysed by Rh complexes of new chiral phosphines such as 4-(diphenylphosphino)-2-{(diphenylphosphino)methyl}-diphenylphosphinylpyrrolidine or its sulphonate or sulphonamide.


Electrode for a Molten Carbonate Fuel Cell

general electric co. European Appls. 92,765/66

A sintered electrode consists of ceramic particles sintered together through a coating of a 5-95% Ni and 95-5% Cu alloy. The ceramic particles are sensitised with a Sn/Pd chloride solution and then chemically plated with 83% Ni and 17% Cu.

Fuel Cell Reactor Construction

w. r. grace & co. U.S. Patent 4,396,480

The fuel cell reactors consist essentially of stacks of channeled sheets of solid electrolyte, the channels being coated with a catalyst for the formation of O ions, from O2, such as Ag, Au, Pt or Pt-Rh alloy or a catalyst for the oxidation of a reactant ‘fuel’, such as NH3. This catalyst may be Pt, Pt-Rh or Pt-Rh-Pd.


Maximum Photographic Contrast

fuji photo film co. ltd. British Appl. 2,121,554A

Internally fogged emulsions which are sensitised with Ir or Rh salts are used as part of a composite film which yields maximum contrast.

Direct Positive Silver Halide Photographic Material

konishiroku photo industry co. ltd.

European Appl. 93,002

A low speed material which can be handled safely in yellow light uses a fogged emulsion containing a Rh or Ir salt with a hydrophilic layer containing a diazole and a Au compound, such as chloroauric acid.


Cooling Tubes for Fibre Glass Spinning

manville service corp. U.S. Patent 4,397,665

Glass fibres emerging from a spinneret are cooled by hollow tubes made from a base metal such as Cu or Inconel clad with 0.004-0.008 inches of Ag, Au, Pt, Pd, Rh, Ir or their alloys. These are less costly than tubes used at present.

Atomised Platinum

owens–corning fiberglas corp.

U.S. Patent 4,402,885

Atomised metals are formed by forcing streams of molten metal under an applied gas pressure through orifices having openings so small that the surface tension of the molten metal would prevent flow at atmospheric pressure, and impinging the metal streams with streams of pressurised gas or liquid. The process is particularly intended for making atomised Pt for use in glass fibre bushings.


Corrosion Resistant Conductive Glass

international business machines corp.

European Appl. 92,644

Print heads and other precision electrode devices are made from a composite of 1–2 parts RuO2 and 1–6 parts of a SiO2-ZrO2 glass frit.

Schottky Diode

siemens a.g. European Appl. 93,866

A new Schottky diode has an increased breakdown voltage without an extra forward voltage drop. The metal semiconductor barrier is surrounded by a guard ring. The metallisation consists of W or Mo, and Pt, Ni, Au, Ag or Pd and Ag.

Semiconductor Photoelectric Converter

semiconductor research foundation

European Appl. 94,973

Pt and Mo silicide Schottky barriers are used in a high speed, high sensitivity photoelectric converter based on a field effect transistor, static induction transistor or static induction thyristor.

Electrochromic Device for Energy Storage

thomson–csf European Appl. 95,973

Pt anodes may be used in electrochromic devices where the cathode is obtained by the deposition of a polymer obtained electrochemically, from a furan, pyrrole or thiophene.

Optical Recording Material

konishiroku photo industry co. ltd.

European Appl. 98,125

A medium for recording laser beam optical information includes a supported film of physical development nuclei which may be Ag sulphide, Rh sulphide or colloidal Ag, Au or Pd among other materials.

Sparking Plug

ngk spark plug co. U.S. Patent 4,393,324

A sparking plug which requires only a small amount of discharge-tip noble metal is made by sealing a ball of the metal on to the central small bore of a refractory insulator. The metal is Ag and/or Au and/or alloy(s) of them with Pd.

Thick Film Conductor Compositions

e.i. du pont de nemours & co. U.S. Patent 4,394,171

Improved compositions useful for making printed terminations for hermetic ceramic capacitors contain 50-95% of a finely divided mixture of 6-60% Pd and 40-94% Ag and 5-50% of a glass frit consisting essentially of 50-80% Pb3O4 and 10-30% GeO2.

Solar Cells

diamond shamrock corp. U.S. Patent 4,400,451

In solar cells the first electrode is a photoactive true solid/solid solution semiconductor material such as SrTi1-xMxO3, where M is Rh or Ru, and the second transparent electrode may be a Au film or a ternary metal oxide such as La0.01Sr0.99SnO3.

Metallisation Process

r.c.a. corp. U.S. Patent 4,404,235

In an improved process for depositing a metal film on a dielectric surface, the surface is first exposed to a gaseous mixture of H2 and WF6 at 500-650°C to form an adherence layer. The metal is preferably Pt.


Temperature Sensor

welwyn electronics ltd. British Appl. 2,120,453A

A sensor particularly suitable for use in an anemometer has a ceramic substrate, a temperature sensitive resistance element and terminations. The resistance elements are preferably produced by thick film screen printing, by using a Ag/Pd ink.

Radiation Pyrometer

smiths industries p.l.c. British Appl. 2,121,978A

A radiation pyrometer for a gas turbine engine has a sapphire lens to focus the radiation from the turbine blades. The exposed surface of the lens has a vapour deposited Pt alumina layer to catalyse the oxidation of coke deposited on the lens.


Palladium Dental Alloy

j.m. ney corp. British Appl. 2,118,971 A

A new alloy which simulates the appearance of a Pt alloy contains 50-85% Pd, 5-40% Cu and/or Co, 1-15% Ga, up to 5% Ni, Au, In, Ru, and/or Sn, up to 0.5% Re and/or Ir and up to 1% B. The alloy bonds to procelain well and does not discolour. In one example the alloy contains 78.65% Pd, 10% Cu, 9% Ga, 2% Au, 0.25% B and 0.1% Re.

Co-ordination Platinum Compounds

johnson matthey p.l.c. U.S. Patent 4,394,319

The compound dichlorodihydroxydi (isopropylamine) Pt useful for the treatment of cancer or malignant neoplasms is provided in substantially pure form by preparation involving a novel intermediate adduct with dimethylacetamide.

Dental Alloy

w. c. heraeus g.m.b.h U.S. Patent 4,400,350

A dental alloy is claimed which consists of 70-82% Pd, 0.1-10% Au, 5-10% In, 2-5% Cu, 0.5-5% Ga, 0.5-5% Sn, 0.9-2.7% Co, 0.01-0.3% Re and 0.08-0.25% Ru and/or Ir.