Platinum Metals Rev., 1972, 16, (2), 67
NEW PATENTS: April 1972
METALS AND ALLOYS
e. i. du pont de nemours & co. British Patent 1,254,033
The manufacture of Pt powders, for use in metallising compositions and the production of printed circuits, which are relatively coarsegrained and free from N2, is described. Pt is precipitated by Zn from an aqueous PtCl4 solution, HCl is added until no further reaction is observed and the precipitate is filtered off, washed and dried.
Hydride and Carbonyl Triphenylphosphine Derivatives of Ruthenium and Osmium
american cyanamid co. U.S. Patent 3,597,461
Pentacoordinate complexes of Ru and Os have the general formula M(CO)5−n[P(C6H5)3]n, where M is Ru, Os and n is 1,2. They are prepared by reacting the corresponding pentacarbonyls with triphenylphosphine. Dihydride compounds of formula MH2(CO)2[P(C6H5)3]2 (M = Ru, Os) are also described.
ELECTRODEPOSITION AND SURFACE COATINGS
Metal Plating of a Nonconductive Substrate
r.c.a. corp. British Patent 1,253,568
A non-conductive substrate is coated with a film of rubber compounded with benzophenone and elemental. It is then exposed to actinic light in a desired pattern. The article is then sensitised and activated using PdCl2, but the unexposed areas contain free S which poisons the catalyst. This prevents the subsequent deposition of Ni.
Ruthenium Plating Bath
LABORATORY APPARATUS AND TECHNIQUE
bailey meter co. U.S. Patent 3,598,711
An electrochemical cell has a ZrO2 tubular electrolyte with porous Pt electrodes bonded to its inner and outer surfaces. A Pt lead from each electrode transmits the cell emf generated when the inner and outer surfaces of the electrolyte are in contact with gases having different O2 contents.
Alloy for Brazing Powder
consolidation coal co. British Patent 1,251,336
Liquid fuel is obtained by extraction of coal with an organic solvent and hydrogenation of the extract in the presence of a Pt group metal oxide, preferably supported on Al2O3.
universal oil products co. British Patent 1,251,388
Toluene is converted to C6H6 and xylenes by heating it in the presence of H2 and a crystalline aluminosilicate, one of As, Sb, Bi, Se, Te or their compounds and a Group VIII metal, preferably Pt or Pd.
chevron research co. British Patent 1,253,408
A catalyst for reforming of naphtha consists of a porous solid carrier with 0.01−3 wt.% Pt, 0.01−3 wt.% Re and 0.001 to 0.1 wt.% Ir.
olin corp. British Patent 1,254,204
Organic isocyanates are obtained by the reaction of nitro compounds with CO in the presence of a catalyst which includes one halide or oxide of a noble metal, including Ag and Au, but is preferably Pd, Rh, Pt or Ir.
shell internationale research mij. n.v. British Patent 1,255,459
Alkyl/aryl hydrocarbons are isomerised by heating with H2 in the presence of an acidic ceramic oxide and Pd or Pt.
british nuclear design & construction ltd. British Patent 1,255,473
CH4 for use in nuclear reactors is obtained by the reaction of CO2 with pure H2 on Ru/Al2O3.
ruhrchemie a.g. British Patent 1,255,537
Phenylpropanals and phenylpropanols are obtained by reacting styrene with CO and H2 in the presence of Rh catalyst (e.g. Rh2O3).
Hydrocarbon Conversion Catalyst
universal oil products co. British Patent 1,255,544
A hydrocarbon conversion catalyst consists of a carrier material containing Al2O3 and a finely divided crystalline aluminosilicate supporting 0.05−1.0 wt.% of a Pt-group metal and 0.05−1.0 wt.% of Re. See also British Patent 1,256,000.
olin corp. British Patent 1,257,932
Organic isocyanates are obtained by reaction of nitro compounds in the gas phase with CO in the presence of noble metal catalyst particularly Pd, Rh, and their halides and oxides.
standard oil co. British Patent 1,259,297
Phthalic acid is purified by the hydrogenation of impurities in the presence of Pd on C.
british petroleum co. ltd. British Patent 1,259,384
Naphthenes in a petroleum fraction are converted to paraffins in the presence of hydrogenation catalysts, preferably Pt or Pd incorporated with a deionised mordenite.
toray industries inc. British Patent 1,260,529
Toluene is converted to C6H6 and xylene in the presence of a catalyst such as Pd or Pt/Al2O3.
mitsubishi petrochemical co. ltd. British Patent 1,261,458
Olefins are converted to carbonyl compounds by reaction with O2 and water vapour in the presence of a Pd or Rh salt adsorbed on to active C.
e. i. du pont de nemours & co. U.S. Patent 3,597,438
Reductive amination of aldehydes to give secondary amines is catalysed by Rh on Al2O3.
Catalytic Exhaust Purifier
kleen air corp. U.S. Patent 3,598,543
An exhaust purifier consists of a chamber in the exhaust pipe containing alumina spheres which have been impregnated with a Pt salt.
universal oil products co. U.S. Patent 3,600,301
Hydrocarbons are hydroprocessed over a catalytic composite of a porous carrier material, a Re component, a Group VIII noble metal component and a Sn component. A specific example of a hydrocracking catalyst is a composite of a crystalline alumino-silicate, a Pt component, a Re component and a Sn component.
Hydroprocessing of Hydrocarbons
universal oil products co. U.S. Patents 3,607,727 and 3,607,728
The hydroprocessing of hydrocarbons uses a catalytic composite of a porous carrier material, a Group VIII noble metal component and a germanium component. A specific example is a composite of a crystalline alumino-silicate, a Pt component and a Ge component, for use in hydrocracking. U.S. Patent 3,607,728 uses Pb instead of Ge.
Catalytic Purification of Terephthalic Acid
mobil oil corp. U.S. Patent 3,607,921
Crude terephthalic acid is purified at elevated temperatures by contact in the presence of CO with solid particles of an adsorptive agent having substantial CO sorption capacity, e.g. Pd/C.
Catalytic Oxidation of Glucose
johnson, matthey & co. ltd. U.S. Patent 3,607,922
For the oxidation of glucose to gluconic or glucosaccharic acid, an aqueous solution of glucose containing Na or K carbonate or bicarbonate is contacted with an O-containing gas in a trickle column reactor in the presence of a supported Pt group metal catalyst. This corresponds to British Patent 1,208,101.
Production of Hydrogen Peroxide by Anthraquinone Process
f.m.c. corp. U.S. Patent 3,615,207
A catalyst for the production H2O2 by the anthraquinone process contains 0.05−5% Pd dispersed over Al2O3 spheres. The spheres pores are less than 0.06 μ in diameter and have a BET surface area of 20–200 m2/g.
produits chimiques pechiney-st. gobain French Patent 2,052,022
Unsaturated impurities in ethylenic gases are hydrogenated in the presence of a catalyst which is a supported mixture of Pd and V. The selectivity of the catalyst can be varied by altering the Pd : V ratio.
deutsche gold- und silber-scheideanstalt German Offen. 1,767,974
HCN and H2 are produced from NH3 and acrylonitrile at 1100−1400°C in the presence of a Pt catalyst.
shell internationale research mij. n.v. Dutch Appl. 70.08,306
A supported dehydrogenation catalyst is produced by depositing a Group VIII noble metal, e.g. Pt on Al2O3 or another support and then passing an inert gas containing Cd and/or Zn over the support so that elementary metal is deposited.
Activation of Supported Catalysts
shell internationale research mij. n.v. Dutch Appl. 71.04,723
The activity of noble Group VIII metal catalysts on porous supports is increased by treatment in three stages: oxidation, sulphiding and reduction.
Platinum Metal Catalysts
shell internationale research mij. n.v. Dutch Appl. 71.05,986, German Offen. 2,121,765
Hydrocarbon conversion catalysts capable of regeneration are obtained by depositing a Pt metal and a second metal on a pretreated support and calcining the product. In an example an Al2O3 support is pretreated with Sn tartrate and calcined. Pt and additional Sn are then deposited and the product calcined a second time.
Alkyl Aromatic Compound Isomerisation
shell internationale research mij. n.v. Dutch Appl. 71.07,053
The steam isomersiation of alkyl aromatic compounds is catalysed by a hydrogenating/dehydrogenating metal deposited on a refractory metal acidic oxide, e.g. Pt/SiO2-Al2O3.
Palladium Carbonyl Complexes
olin corp. British Patent 1,251,744
The compound PdL(CO)X2, where L is a Lewis base, is prepared by the reaction of (for example) pyridine, quinoline or lutidine with a Pd dihalide and CO. It is a useful catalyst for the conversion of nitro compounds to organic isocyanates. British Patent 1,252,331 uses Pd(py)(SCN)2.
b.p. chemicals ltd British Patent 1,254,776
Acrylonitrile is dimerised in the presence of a Ru compound, preferably the chloride.
british petroleum co. ltd British Patent 1,255,858
Olefins are converted to aldehydes by hydroformylation with a Rh-dicarbonyl-β-diketone.
johnson matthey & co. ltd. British Patent 1,258,045
Hydrogenation, hydroformylation and carbonylation processes using tertiary phosphine complexes with halides on psuedohalides of the Pt group metals may be improved by the use of triphenyl phosphines substituted in the para position with an electron releasing substituent.
maruzen oil co. ltd. British Patent 1,259,145
Butene is oxidised to methyl ethyl ketone in the presence of an aqueous solution containing ferrous sulphate and a Pd compound. The sulphate, nitrate or chloride are preferred.
Production of Cyclic Hydrocarbons
imperial chemical industries ltd. British Patent 1,259,973
A 1,4-cyclohexadiene is combined with a cyclopentadiene at elevated temperature and pressure in the presence of a Rh catalyst such as RhC1L3, where L is a tertiary phosphine, arsine or stibine.
Preparation of Aromatic Isocyanates
olin mathieson chemical corp. U.S. Patent 3,597,466
Organic isocyanates are made by reacting an organic nitro compound with carbon monoxide in the presence of a halide of a noble metal and a cyanamide compound. Preferred cyanamide compounds include alkyl, dialkyl, aryl, diaryl, aralkyl and diaralkyl cyanamides. The noble metal is preferably Pd, Rh, Ir, Re, Pt.
Rhodium Polymerisation Catalyst
u.s. secretary of the army U.S. Patent 3,607,850
Conjugated dienes are polymerised in aqueous emulsion by a water-soluble Rh salt or complex.
institut francais du petrole, des carburants et lubrifiants French Patent 1,603,107
Nitrile polymerisation through the C–N triple bond is catalysed by Group VIII (e.g. Pd) cyanides and unsaturated amines.
Ruthenium Carboxylate Catalysts
johnson, matthey & co. ltd. French Patent 2,055,059
New hydrogenation catalysts are Ru carboxylates of formula Ru2(OCOR)4, where R is alkyl or aryl, and their adducts with arsines, phosphines or stibines, e.g. a Ru(II) acetate-triphenyl phosphate adduct.
Transition Metal Catalysts
FUEL CELLS AND BATTERIES
Fuel Cell Electrodes
united aircraft corp. U.S. Patent 3,615,862
Activated fuel cell electrodes are prepared by electrodeposition of a noble metal catalyst on a solid foil or porous electrode substrate. The electrolyte is an alkali metal hydroxide solution, preferably molten alkali metal hydroxide. Pd black is a preferred noble metal catalyst and Pd or Pd-Ag alloy foils and porous sintered Ni structures are the preferred electrode substrates.
Solderable Stainless Steel
p. r. mallory & co. inc. British Patent 1,256,147
A wet electrolytic capacitor includes a glass-to-metal seal. The metal is stainless steel which is coated first with a layer of Ni, Cr or Co and then with a layer of an alloy of Ag or Cu with one or more of the following: Au, Pd, Pt, Re or Os.
minnesota mining & manufacturing co. British Patent 1,260,722
A photosensitive medium includes a composition which on exposure to light will generate ions of a metal more noble than Ag, preferably Pd.
Flame Resistant Polymer Composition
general electric co. British Patent 1,261,637
A flame-resistant elastomer contains an organo-polysiloxane, a Si hydride, filler and a Pt-containing material to give 0.5–250 parts of Pt per million parts of the organopolysiloxane.
Palladium Photographic Material
eastman kodak co. U.S. Patent 3,597,206
Light sensitive Pd compounds are used in a vinyl alcoholvinyl anthranilate polymer to form a photographic material. The compounds are complexes of Pd salts and carboxylic acids.
Heat Source, Suitable for Use in a Cardiac Pacemaker
commissariat a l’energie atomique U.S. Patent 3,600,586
A heat source consists of an α-emitting material in a leak-tight container. The container consists of an inner sheath of Ta or W and of an outer sheath of Pt.
e. i. du pont de nemours & co. U.S. Patent 3,615,731
Flake Au is made by milling Au powder in a liquid hydrocarbon medium containing 1−20% fatty acid. The flakes are used in metallising and decorative compositions. Harder and brighter flakes are obtained by introducing up to 1% Rh powder into the hydrocarbon media.
Coating for Glass
philips electronic & associated industries ltd. British Patent 1,251,947
A glass article, e.g. the envelope of a Na-vapour discharge lamp, is provided with a transparent heat-reflecting surface film consisting of doped Ir oxide. The dopant is preferably Sn.
Manufacture of Glass Fibres
p.p.g. industries ltd. British Patents 1,259,553 and 1,259,554
Apparatus for melting and homogenising glass and drawing out glass fibres, is described. Channels and pans of Pt are included.
corning glass works U.S. Patent 3,598,635
A material suitable for use in contact with molten glass is obtained by spraying the surface of a refractory with Pt or a Pt alloy in a plasma flame, and heating the coated refractory to 1250°C.
Glass Bushing with High Emissivity Coating
p.p.g. industries inc. U.S. Patent 3,600,146
Pt and Pt alloys such as those used for bushings in the manufacture of glass fibre have relatively low emissivity values. Parts of such bushings are exposed to radiant energy, and to increase the radiant heat exchange a coating of a material having a relatively high emissivity is applied.
ELECTRICAL AND ELECTRONIC ENGINEERING
Ohmic Contacts for Semiconductive Wafers
hewlett-packard co. British Patent 1,253,092
In the manufacture of ohmic contacts, the contact area required on a Si substrate is coated with Pt and the PtSi subcontacts so formed are sputtered with Mo-Au.
philips electronic & associated industries ltd. British Patent 1,254,249
In the manufacture of a switching device, reed contacts of magnetic Ni-Fe alloy are coated with a layer of Au in which is dispersed at least 1 vol.% of C, P, S, Si or metal oxide. A further layer of Ru or Rh is then applied.
Porous Anode Capacitor
general electric co. British Patent 1,254,633
It has been found that Ti- and Ni-case capacitors enhanced with Ru are significantly superior to those enhanced with Pt, Pd or Rh.
badische anilin- & soda-fabrik a. g. British Patent 1,258,619
Pt/Ti or Pt foil on graphite is used as the anode in the production of adiponitrile by electrochemical hydrodimerisation of acrylonitrile.
Ceramic Metallising Compositions
e. i. du pont de nemours & co. British Patent 1,260,023
A brazeable metallising composition consists of 90−99 wt.% of at least one of Pt, Pd, Au, Ag, Rh, Ru, Os and Ir, and 1−10 wt.% of a glass.
e. i. du pont de nemours & co. British Patent 1,260,440
A photopolymerisable composition suitable for forming patterns on inorganic dielectric substrates consists of an organic solvent, and a solid component containing 5−85 wt.% of an organic compound of Ru, Os, Rh, Ir, Pd, Pt, Ag or Au, together with a photopolymerisable aliphatic compound, an organic sensitiser, an organic S compound and flux.
p.p.g. industries inc. British Patent 1,260,645
Anodes which may be used for electrolysis of aqueous alkali metal chloride solutions are coated with an electroconductive oxygen-containing compound which includes a Pt group metal and an alkaline earth or rare earth metal. Examples are Ca or Sr ruthenate or ruthenite.
farbenfabriken a.g. British Patent 1,261,114
Anodes suitable for use in the electrolytic production of olefin oxides from olefins may be made of Pt, Ti coated with one or more Group VIII noble metals (especially Pt with Ir and Rh), Pt/Ta or a Pt-coated inert support.
Electrode for Cardiac Stimulator
medtronic inc. U.S. Patent 3,596,662
A cardiac stimulator electrode has a pair of electrical conductors encapsulated in a flexible nonconductive plastic material, such as silicone rubber. The electrical conductors are Pt alloy coil springs with space coils.
precision electronic components ltd. U.S. Patent 3,607,789
A conductive glaze consists of conductive particles in a Pb germanate glass. A suitable composition contains Au, Pt oxide and Ru oxide.
alpha metals inc. U.S. Patent 3,609,105
A metallising composition for forming electrically conductive areas on dielectric materials is a mixture of 63.7% Au, 32.3% Pd and 4.0% Ag.
Bismuth Titanate Film Capacitor
sylvania electric products inc. U.S. Patent 3,609,482
A film capacitor is made by depositing a base electrode of a Au-Pd alloy on an Al2O3 substrate. A dielectric paste of a mixture of Bi titanate, a Pb borosilicate glass and a resin solution is silk screened on to the base electrode and then baked and fired. An upper electrode of Ag is deposited on the Bi titanate.
t.r.w. semiconductors inc. U.S. Patent 3,609,472
A contact for a semiconductor device capable of withstanding high temperature, chemical attack by silicon etchant and high oxidation atmospheres has a bimetallic layer of an alloy of Pt and Ni on the active regions. The Pt-Ni layer is coated with Pt and this is protected by a covering layer of Rh. A layer of Au is then placed on the Rh.
Brazeable Metallising Compositions
e. i. du pont de nemours & co. U.S. Patent 3,615,734
Brazeable compositions which can be fired below 1400°C consist of 90−99% noble metal(s) and 1−10% of a low-alkali aluminosilicate glass. The noble metals contain at least 50% Pt with a surface of 0.05−5 m2/g.
westinghouse electric corp. U.S. Patent 3,616,408
An oxygen solid-electrolyte cell has two longitudinal holes, the interiors of which are coated with porous Pt. The holes are connected to separate sources of gas to permit flow of different gases over the electrodes within the holes.
p.p.g. industries inc. U.S. Patent 3,616,446
Electrolysis electrodes consist of a Ti or other conducting base coated with an electroconductive oxy-compound of a Pt group metal and either a Group IIA or Group IIIA metal. A typical coating is produced by applying Rh and Mg resinates and heating the resulting film.
Electrode for Formic Acid Combustion
robert bosch g.m.b.h. German Offen. 1,671,418
An electrode for the electrochemical combustion of formic acid consists of a combination of Pt or Pt alloy plus a Group V or VI element on a conducting base.
s. coudrier British Patent 1,251,081
A thermocouple is produced by depositing separated areas of two different metals on to an insulating substrate of suitable geometry. Electric leads are provided from the metal areas to a measuring instrument. The metals used may be Pt and Pt-Rh.