Platinum Metals Rev., 1980, 24, (3), 119
NEW PATENTS: July 1980
METALS AND ALLOYS
Nickel Base Alloy
special metals corp. British Patent 1,565,606
A gamma prime strengthened Ni base alloy contains up to 6% Ru and up to 2% or one or more of the lanthanide metals.
Superplastic Aluminium Alloy
european atomic energy community (euratom) British Patent 1,565,620
An Al alloy containing 17−30% Pd and not more than 1% of impurities possesses superplastic properties. A preferred alloy has a purity of 99.5% + and a Pd content of 23%. The alloy may replace Pd sponge or powder catalysts in hydrogen/deuterium exchange reactions.
Osmium Tetroxide Complexes
johnson matthey & co. ltd. British Patent 1,560,481
Complexes suitable for fixing and staining cells for electron microscopy are obtained from OsO4 and an aromatic tertiary amine, a cycloaliphatic tertiary amine and/or a compound having a heterocyclic ring containing one or two N atoms, such as quinuclidine.
New Iridium Compounds
international nickel co. U.S. Patent 4,174,378
Novel Ir compounds are prepared by refluxing a diammonium hexahalogen salt of Ir and sulphamic acid in an aqueous medium for more than thirty hours. The Ir products are useful in electroplating.
Straight Chain Amine Complexes of Platinum(IV)
Sodium Hypochlorite Production
chlorine engineering corp. ltd. British Patent 1,559,957
Na hypochlorite can be produced efficiently by electrolysis of NaCl in a cell without a diaphragm, if the ratio of anode area to cathode area is at least 1.5:1. Ru oxide/Ti oxide coated electrodes are used in the examples.
Electrolytic Cell Construction
diamond shamrock corp. British Patents 1,561,956/7/8
A monopolar membrane electrolytic cell with an improved flange type of construction may be used for brine electrolysis. The electrodes consist of valve metal bodies coated with platinum group metals or their oxides.
energy development associates inc. U.S. Patent 4,182,662
A cell for the production of H2 by the electrolysis of a halogen acid (HCl or HI acid) has a reaction zone where halogen released by the cell reacts with water, to form additional halogen acid. Ruthenised Ti and platinised Ti catalysts are suitable for the rapid hydrogenation reaction required.
ELECTRODEPOSITION AND SURFACE COATINGS
Noble Metal Ion-Plated Titanium
LABORATORY APPARATUS AND TECHNIQUE
Exhaust Emission Sensor
lucas industries ltd. British Patent 1,562,623
A metal oxide and a temperature sensor located on a ceramic substrate are used to monitor exhaust emissions from an I.C.E. In examples, a sensor containing Ti dioxide, Ta oxide and 1% Pt overprinted with a Pt resistance thermometer is used.
Vapour Heating Apparatus
laporte industries ltd. British Patent 1,564,747
A vapour heater for converting corrosive Ti tetrachloride vapour to TiO2 consists of an Al2O3 casing having an embedded Pt or Pt alloy element. Connections to the element are via flexible Pt, Pt alloy or Ta couplings.
Prevention of Cast Iron Corrosion
hoechst a.g. British Patent 1,564,774
Cast iron boilers used in the treatment of concentrated H2SO4 tend to corrode even when anticorrosion additives of the amine type are present. This corrosion is now avoided by the presence in the system of a noble metal. Pd, Pt and Au are the preferred metals and may be used in the form of wire or chips attached to the cast iron surface.
Temperature Change Detector
united kingdom atomic energy authority British Patent 1,565,901
The temperature inside a nuclear reactor, is monitored by a source which releases radioactive gas at a temperature dependent rate. The radioactive gas is collected by the cooling gas and passed to a trapping system where it is detected. The source may conveniently be Ra-226 deposited on a Pt foil.
Carbon Dioxide Gas Laser
secretary of state for defence British Appl. 2,028,571 A
A Sn oxide-supported Pd or Pt catalyst contained in a porous SiO2 or Al2O3 structure mounted within the envelope of a CO2 gas laser recombines CO and O2 produced during operation of the laser.
robert bosch g.m.b.h. British Appl. 2,029,028 A
A sensor for detecting the presence of soot in diesel exhausts, has an Al2O3 body and two Pt electrodes bridged by a non-conductive layer carrying a catalyst, such as a Pt catalyst. Soot deposits on the bridge and decreases the resistance between the electrodes; and when the gas becomes soot free the catalyst oxidises the soot enabling the resistance to be restored.
matsushita electric industrial co. ltd. European Appl. 9,825
A humidity detector, for detecting steam leaks, includes a humidity-sensitive resistor which is a plate like metal oxide ceramic (Cr oxide, Mg oxide or TiO2) provided with a pair of electrodes (RuO2) and Pt wire leads.
national research development corp. U.S. Patent 4,182,666
A molten electrolyte O2 sensor has a Pt/Pt oxide reference electrode, a Pt counter electrode and a Ag metallised PTFE membrane oxygen diffusion electrode. Metal/metal oxide electrode systems of other noble metals, particularly Au and Ag, may also be used.
national research development corp. U.S. Patent 4,182,667
Ion-sensitive electrodes are formed from a solid mercury amalgam protected by a layer of β -Al2O3. Connections are made to the active amalgam layer by means of Pt disc electrodes. The electrodes may be used for Ag ion measurements, among others.
Hot Cathode for Thermionic Tubes
bbc brown boveri & co. ltd. British Appl. 2,027,263 A
A wire or sheet cathode made by a powder metallurgical/hot swaging process has core and shell portions formed from a carrier metal, Mo, containing small amounts of lanthana, yttria and thoria as activators, greater amounts of the activators being used in core portion. Both portions are joined, carburised and coated with a platinum group metal diffusion promoting additive to form the cathode.
johnson matthey & co. ltd. U.S. Patent 4,183,746
The ceramic (Al2O3) particles of a cermet containing a platinum group metal, Ag or Au as the metallic phase are coated with a second metal (Y, Al, Ti, V, Cr or Ni) to improve the adhesion between the ceramic and metal phase. The cermets are useful as erosion-resistant materials in glass melting.
Hydrogenation of Hydrocarbons
british petroleum co. ltd. British Patent 1,563,168
Lubricating oils of low aromatic content are obtained by hydrogenating hydrocarbon fractions having a distillation end point above 350°C and a S content of 1,000−3,000 ppm over a catalyst which is Pt deposited on a SiO2 Al2O3 support containing SiO2.
Catalytic Waste Heat Recovery
johnson matthey & co. ltd. British Appl. 2,027,609 A
Heat energy may be recovered from waste or effluent gases, such as exhaust gases, containing combustible vapour or droplets by catalytically oxidising the vapour or droplets over a platinum group metal catalyst and removing the heat produced via a heat exchanger.
mobil oil corp. European Appl. 7,734
The efficiency of CO combustion in a regenerator is considerably increased by the periodic addition to the circulating catalyst of a mixture of metal-rich and metal-free particles. The metal-rich particles preferably contain about 50 ppm of Pt, Pd, Ir, Os, Rh, Ru or Re, the total concentration of metal in the mixture being 1−10 ppm. The activity of this mixture is higher than that of a catalyst in which the same amount of metal is evenly distributed among the particles.
dynamit nobel a.g. European Appl. 7,972
Chloro-hydrazobenzenes are obtained by the hydrogenation of the corresponding nitrobenzenes in a turbulent alkaline aqueous-organic medium in the presence of a Pd or Pt catalyst and optionally a naphthoquinone as a co-catalyst.
Oxidation Resistant Coatings
johnson matthey & co. ltd. European Appl. 9,494
An I.C.E. exhaust gas purification catalyst consists of a metal substrate which is not normally oxidation resistant at high temperatures, coated with an oxidation-resistant layer of Al powder in a ceramic binder, a high surface area washcoat and a catalytically active platinum group metal.
e. i. du pont de nemours & co. European Appl. 9,802
A Pd catalyst supported on amorphous SiO2 also contains a small amount of an additive chosen from oxides, hydroxides and carbonates of Zr, Th, Hf, Ce, Ti and Al. The products are useful as hydrogenation catalysts, particularly in a cyclic process for the manufacture of H2O2.
comstock & wescott inc. U.S. Patent 4,171,947
A catalytic combustion apparatus for heating shaving foam dispensed from aerosol cans, which has rapid cold ignition and which is effective when the catalyst is damp, operates on lower alcohol fuel and has a higher catalyst concentration around the fuel inlet. Pellets coated with up to 60% of a platinum metal are used in the inlet areas, whereas the catalytic content of pellets in other areas of the combustor is 2%.
Rhodium Exhaust Gas Purification Catalysts
ford motor co. U.S. Patent 4,172,047
Rh optionally mixed with other catalytic metals, is coated on to a substrate carrying an α -Al2O3 wash coat. Rh is not dissolved into α -Al2O3 when the catalyst is used under the oxidising conditions employed, that is high temperature conditions.
Reactivation of Iridium Catalysts
exxon research & engineering co. U.S. Patent 4,172,817
The time required to reactivate an Ir-containing hydroforming catalyst (deactivated by coke deposition) is reduced by deliberate agglomeration of the Ir prior to sequential reduction/halogenation treatments. Agglomeration may be achieved by a severe coke burn. The method may be used with catalysts containing Pt, Ir and halogen.
Ruthenium Cerium Hydrogenation Catalysts
phillips petroleum co. U.S. Patent 4,172,849
The addition of Ce to a Ru hydrogenation catalyst, particularly catalysts used for the hydrogenation of unsaturated dinitriles, moderates the catalyst degradation and the loss of activity.
Multimetallic Dehydrogenation Catalysts
u.o.p. inc. U.S. Patent 4,172,853
Non-acid catalysts for the preparation of high octane petrols, contain a platinum group metal, a Group IVA metal, a Group IA or IIA metal and a sufficient amount of a lanthanide metal to give a Pt:Ln ratio between 0.01:1 and 1.25:1. Pt-Sn-Nd-Li combinations are used in examples.
High Severity Reforming
cosden technology inc. U.S. Patents 4,174,270/1
Highly aromatic reformates are produced from naphtha feeds by high severity reforming using a reforming catalyst containing a hydrocracking promotor metal, typically a Pt-halogen catalyst containing Ir, Sc, Y or other metals as promotors.
mobil oil corp. U.S. Patent 4,174,272
Non-hydrogenative endothermic cracking of hydrocarbons, at low pressure and high temperature, uses heat supplied by the catalyst as a heat transfer medium. Platinum group metal catalysts, such as Pt or Pd, are heated by burning deposited coke formed during the cracking process.
Oxidation Over Synthetic Amorphous Silicas
mobil oil corp. U.S. Patent 4,176,161
An economical catalyst having shape-selectivity for hydrocarbon conversion is prepared by hydrolysing and polymerising a specified silane, optionally in the presence of a metallic compound, preferably a Pt and/or Pd compound.
Rhodium or Palladium Hydroalkylation Catalyst
phillips petroleum co. U.S. Patent 4,177,165
A catalyst consisting of a Pd or Rh compound supported on a calcined, acidic, Ni and lanthanide metal-exchanged zeolite is effective for hydroalkylation reactions.
Sulphided Platinum-Rhenium Catalyst
u.o.p. inc. U.S. Patent 4,178,268
A selective sulphided catalytic composite for hydrocarbon conversion contains 0.01−2% of a platinum group metal (Pt), 0.01−2% of sulphided Re and 0.1−3.5% of a halogen component supported on a Ziegler Al2O3 carrier.
Steam Cracking of Heavy Feedstocks
institut francais du petrole U.S. Patent 4,180,453
A fresh charge containing aromatic hydrocarbons is hydrotreated mixed with a recycle fraction in the presence of a dual-function catalyst, which preferably contains Pd or another platinum group metal. A portion of the effluent is subjected to steam cracking so that a gas oil recycle fraction may be obtained.
Ruthenium-Containing Perovskite Catalyst
e. i. du pont de nemours & co. U.S. Patent 4,182,694
The B site of a perovskite catalyst of type ABO3 contains up to 10% Ru and up to 20% of another platinum group metal. La and Sr are preferred metals for site A. The catalyst may be used for I.C.E. purification and for HNO3 tail gas decomposition.
Platinum-Catalysed Curable Organo-polysiloxanes
toray silicone co. ltd. U.S. Patent 4,182,824
A composition, based on the Pt-catalysed SiH4 addition to unsaturated groups on Si, contains specified silanes to enhance adhesion of the organo-polysiloxane to substrates.
Palladium and Platinum-Copper Catalysts for Dialkyl-N-Alkylaniline Preparation
ciba-geigy corp. U.S. Patent 4,183,868
Addition of up to 10% Pd or Pt to Cu catalysts used for the preparation of 2,6-dialkyl-N-alkylanilines considerably increases the product yield.
Catalysts for Processing Synthesis Gas
hoechst a.g. German Offen. 2,825,495
Ethanol, acetaldehyde and acetic acid are obtained by the reaction of Co with H2 in the presence of a supported mixture of Rh and Mg.
Metal Fibre Catalysts
w.c. heraeus g.m.b.h. German Offen. 2,829,035
Catalysts which are bundles or webs of Pt, Ag, Rh and/or Pd wires (especially wires of Pt with 5−10% Rh) are used in the oxidation of NH3 or the synthesis of formaldehyde or HCN.
basf a.g. German Offen. 2,830,998
A catalyst for the isomerisation of trans -to cis -2,6-dimethyl morpholine is Al2O3 supporting 5% lanthanide metal oxide and 0.5% Pd.
Selective Hydrogenation of Aldehydes
basf a.g. German Offen. 2,832,699
The selective hydrogenation of olefinic aldehydes to saturated aldehydes is catalysed by 2−90% Pd and 10−98% lanthanide oxide(s) and/or salt(s).
johnson matthey & co. ltd. German Offen. 2,922,755
The solubility of supported Pd, used as a catalyst for the reduction of nitroaromatic compounds with H2, is reduced by maintaining a continued excess of H2 in the reaction medium, with part of the H2 reversibly absorbed on the Pd surface.
johnson matthey & co. ltd. German Offen. 2,924,139
5−12C Hydrocarbons can be obtained from synthesis gas with good selectivity in the presence of a Ru catalyst, especially Al2O3 coated with 0.5% Ru.
Smoke Control for Diesels
johnson matthey & co. ltd. German Offen. 2,927,815
Finely divided particles of C and/or hydrocarbon material in gas streams such as furnace stack gases, are oxidised by mixing with a turbulent stream of O2-containing gas and passing through a catalyst bed. The catalyst consists of a porous ceramic or fine metal wire support, coated with a platinum group metal or its alloy, especially 7.5% Rh-Pt.
kuraray co. ltd. British Appl. 2,026,473 A
The life of a catalyst consisting of Rh, such as a Rh carbonyl phosphine, used in the hydroformylation of olefins may be prolonged by the presence of a phosphine oxide, such as Ph2P(H)O.
ruhrchemie a.g. European Appl. 7,609
Secondary aliphatic aldehydes are obtained by reacting terminal olefins with CO and H2 in the presence of a Rh carboxylate and a tertiary phosphine.
heyl & co. European Appl. 8,407
Catalysts useful in a wide range of organic hydrogenation reactions are polymer-bonded complexes of Group VIII metals, particularly Pd and Pt, such as Pd chloride bonded to polyvinyl alcohol.
Rhodium Hydroformylation Catalysts
bayer a.g. European Appl. 8,763
The hydroformylation of cyclododecatrienes is catalysed by a mixture of dicobalt octacarbonyl and a Rh complex, tris(dibenzyl sulphide) trichloro Rh.
rhone-poulenc industries European Appl. 9,429
Undecadienes containing functional groups, useful intermediates in the manufacture of biodegradable detergents, are obtained by reaction of a diene bearing functional group, such as acetoxy octadiene, with a conjugated diene, such as butadiene, in the presence of a catalyst system consisting of a Rh compound (chloride) and a tertiary phosphine, in the atomic ratio P:Rh preferably 2-6:1.
Palladium Complex Catalyst for Unsaturated Aliphatic Ester Production
texaco development corp. U.S. Patent 4,172,087
A dual function homogeneous Pd complex containing certain organic tertiary nitrogen bases is useful for the selective production of fatty acid derivatives from 1,3-butadiene.
Rhodium Catalyst for Production of Alkane Polyols
Thermally Developable Photographic Material
fuji photo film co. ltd. British Patent 1,560,459
A thermally developable material is based on Ag behenate or another organic Ag salt with Rh or other metal salts to modify its crystal size and shape. Au and platinum group metal sensitisers may be present.
Neutron-Absorbing Silicone Rubber
h.l. zoch U.S. Patent 4,176,093
Pt-catalysed Si-rubber compositions containing a silanol or vinylic diorganopolysiloxane polymer of B carbide and vulcanise at room temperature are useful shielding materials for nuclear plant.
Metal Phosphinate Polymers as Flame Retardants for Polyester Resins
pennwalt corp. U.S. Patent 4,180,495
Poly(metal phosphinates) of Pt, Pd, Rh, Ir, Ru and Ag, among others, may be added to polyesters and polyamides to increase their flame resistance.
Palladium and Platinum Azo Dyes
eastman kodak co. U.S. Patents 4,183,753/4/5
The Pt, Pd and other metal complexes of three types of azo dyestuff for use in photographic elements are disclosed. A suitable dye is, for example, the Pt complex of the reaction product of 3(1-acetyl-6-methyl-1 H-pyrazolo(3,2-c)-s-triazol-3-yl)-4-meth-oxy-aniline and 4(m-chloro-sulphonylbenzene sulph-onamido)1-hydroxy-[4(2,H-di-t-pentylphenoxy)butyl] naphth-2-amide.
ELECTRICAL AND ELECTRONIC ENGINEERING
Growing Single Crystals
philips electronic & associated industries ltd. British Patent 1,561,090
A spherical or ellipsoidal crucible is used to grow single crystals. The crucible can be rotated without setting the liquid in motion, enabling undisturbed growth to be obtained. The crucible is preferably fabricated from Pt and may be used for growing Y oxide containing crystals.
Photovoltaic Generator for Solar Energy Conversion
texas instruments inc. British Patent 1,561,309
Transparent Pt and Pd electrodes are used in a solar energy converter in which a series of semiconductor solar generators are operated directly in communication with, and are wetted by, an electrolyte to force a chemical reaction.
general electric co. British Patent 1,564,335
An igniter electrode for use in gas turbines is made from an alloy consisting of 2-16 vol.% Y, Th or a lanthanide oxide the balance being Ru and/or Ir or alloys based on Ru or Ir. A preferred electrode contains 4-8 vol.% Y2O3 and the balance Ru.
Conductive Pyrochlore Compounds
exxon research & engineering co. British Appl. 2,029,385 A
New pyrochlore conductors for use in oxygen electrodes have the formula A2B2O7−y where y is between 0 and 1, A is Pb and/or Bi and B is Ru and/or Ir. A suitable catalyst is Pb2Ru2O7−y applied to a Au screen.
Non-Aqueous Secondary Cells
western electric co. inc. British Appl. 2,030,352 A
Non-aqueous secondary cells having rutile transition metal oxide positive material and Li negative material are claimed. Ru, Ir and Os oxides rutile materials are used in examples.
xerox corp. European Appl. 7,755
A magnetic thin film with high coercivity and a high squareness B-H hysteresis loop for a high-density magnetic recording medium is obtained by vacuum deposition of a Co-base binary or ternary alloy containing preferably 5-15 at.% Re, Ru and/or Os.
Insulated Gate FETS
international business machines corp. U.S. Patent 4,173,818
Pd silicide-Al metallisation may be used in an improved method of fabricating IGFETS having very short effective channel lengths.
Superconductor Filament Manufacture
u.k. atomic energy authority U.S. Patent 4,177,087
A superconducting fine wire filament of the A3B type is manufactured by forming component filaments in a bronze matrix having specified additives, drawing the compact and reacting the components to form the superconductor. The superconductor is primarily Nb3Sn, although component B metals claimed include Rh, Pd, Os and Ru.
Multi-Refractory Films for Gallium Arsenide Semiconductors
u.s. secretary of the navy U.S. Patent 4,179,533
Individually deposited layers of Ta-Pt-Ta, W-Pt-W or TiW alloy-Pt refractory layers prevent grain boundary migration of electrode Au layers in GaAs semiconductors and produces devices which are thermally stable up to 600°C.
Solid Electrolyte Capacitor
matsushita electric industrial co. ltd. U.S. Patent 4,184,192
Use of Ru, Rh, Pd, Re, Os and/or Ir oxides instead of colloidal C as the cathode collector layer of a solid electrolyte capacitor (such as a MnO2 capacitor) improves the dielectric loss and the frequency-capacitative characteristics of the capacitor.
Platinum Bisamine Complexes
johnson matthey & co. ltd. British Appl. 2,025,938 A
The treatment of tumours or neoplasms may be carried out with complexes of divalent Pt salts and two molecules of the same or different straight chain amines, such as cis -bis(bromoacetato)bis(n-propylamine)Pt (II).
Dental Silicone Compositions
g.–c. shika k.k. British Appl. 2,026,000 A
When using catalysed organovinyl polysiloxanebased compositions for making dental impressions, the moulding may be affected by H2 evolution. A smoother cast is obtained when Pd or Pd alloy powder is present to absorb the H2. The curing catalyst may be a Pt compound.
Platinum Antileukaemia Complexes
united states of america U.S. Patent 4,175,133
1,2-Diaminocyclohexane Pt complexes, such as hydroxymalonato(diaminocyclohexane)Pt, are used for the treatment of L 1210 leukaemia.