US3554910A - Organosilane mold lubricants - Google Patents

Organosilane mold lubricants Download PDF

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Publication number
US3554910A
US3554910A US768507A US3554910DA US3554910A US 3554910 A US3554910 A US 3554910A US 768507 A US768507 A US 768507A US 3554910D A US3554910D A US 3554910DA US 3554910 A US3554910 A US 3554910A
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Prior art keywords
mold
organosilane
casting
emulsion
metal
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Expired - Lifetime
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US768507A
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English (en)
Inventor
Milton L Johnson
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Dow Silicones Corp
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Dow Corning Corp
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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M3/00Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C3/00Selection of compositions for coating the surfaces of moulds, cores, or patterns
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02Water
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08Inorganic acids or salts thereof
    • C10M2201/082Inorganic acids or salts thereof containing nitrogen
    • C10M2201/083Inorganic acids or salts thereof containing nitrogen nitrites
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/021Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/221Six-membered rings containing nitrogen and carbon only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/225Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/225Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226Morpholines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/30Heterocyclic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/022Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/04Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having a silicon-to-carbon bond, e.g. organo-silanes

Definitions

  • This invention relates to alkoxysilanes as mold lubricants. In one aspect the invention relates to an improvement in the casting of molten metal.
  • Silicones are known as lubricants and release agents generally. Many organosilicon compounds cannot be used as mold lubricants for molding or casting metal articles because they form a material buildup on the surface of the mold. This material buildup is detrimental because of the close tolerances of certain cast metal part specifications. The buildup also results in the lack of a smooth clean surface on the cast part.
  • silicone release agents and lubricants are not used in many die casting operations because the cast metal article cannot be painted, plated or chemically treated, during the finishing operation. This difiiculty is due to the fact that the metal surfaces contain traces of siloxane which are incompatible with organic constituents in the paint, plating bath compositions and of the like.
  • Another object of the invention is to minimize mold buildup in die casting operations.
  • a method of lubricating molds utilized in the casting of metals comprising applying to the molding surfaces of the mold an organosilane of the general formula R Si(OR') in which R is a lower alkyl radical of not more than 6 carbon atoms, R is a higher alkyl radical containing from 8 to 30 carbon atoms, and a has a value of from 1 to 3.
  • R can be any lower alkyl radical, such as the methyl, ethyl, isopropyl, butyl or hexyl groups.
  • R is a higher alkyl radical, such as the octyl, decyl, dodecyl, tridecyl, octadecyl, C H C H and myricyl groups.
  • R includes the normal and branched chain radicals. It is often convenient to use mixtures of the above silanes, thus R can be the same or different when a is 1 or 2.
  • R substituent is the methyl group. Because of their lower melting point and increased stability when emulsified silanes in which R is an alkyl of 10 to 14 carbon atoms are preferred,
  • the organosilanes utilized in the practice of the invention are the reaction products of R SiCl with a higher alcohol (R'OH), where R, R and a are as defined above.
  • R'OH a higher alcohol
  • the silanes are readily made by known methods.
  • the alkoxysilanes are applied to the mold surfaces in the form of an aqueous emulsion.
  • the emulsion contains from 5 to weight percent of the organosilane and from 1 to 10 weight percent of an emulsifying agent, the rest being water.
  • the emulsions can also contain minor amounts (0.1 to 2 weight percent) of stabilizers, such as freeze-thaw agents, and other additives, such as rust inhibitors.
  • nonionic and anionic emulsifying agents are preferred.
  • Suitable nonionic emulsifying agents are the saponines; condensation products of fatty acids with ethylene oxide such as dodecyl ether of tetraethylene oxide; condensation products of ethylene oxide and sorbitan monolaurate; condensation products of ethylene oxide and sorbitan trioleate and condensation products of phenolic compounds having side chains with ethylene oxide such as condensation products of ethylene oxide with isododecylphenol or nonylphenol; and imine derivatives such as polymerized ethylene imine and N-octadecyl-N,N'-ethylene imide.
  • Suitable anionic emulsifying agents are a kali metal sulforicinates; sulfonated glyceryl esters of fatty acids such as sulfonated monogylcerides of coconut oil acids; salts of sulfonated monovalent alcohol esters such as sodium oleylisothyionate; amides of amino sulfonic acids such as the sodium salt of oleyl methyl tauride; sulfonated products of fatty acid nitriles such as palmitonitrile sulfonate; sulfonated aromatic hydrocarbons such as sodium a-naphthalene monosulfonate; condensation products of naphthalene sulfonic acids with formaldehyde; sodium octahydroanthracene sulfonate and alkylarylsulfonataes having one or several alkyl groups of 8 or less carbon atoms.
  • the organosilanes can also be dissolved in a suitable solvent such as aliphatic hydrocarbons, for example hexane; aromatic hydrocarbons, for example xylene and toluene; or chlorinated hydrocarbons, for example perchloroethylene; and then :be applied to the molding surfaces as a solution.
  • a suitable solvent such as aliphatic hydrocarbons, for example hexane; aromatic hydrocarbons, for example xylene and toluene; or chlorinated hydrocarbons, for example perchloroethylene
  • the organosilanes can be applied to the molding surfaces by conventional techniques, such as brushing, dipping, flooding of the mold, or spraying the material onto the mold.
  • a preferred method utilizes the above-defined emulsions which have been further diluted with from 10 to 300 volumes of water and then sprayed into the interior of the mold prior to each casting cycle.
  • Both ferrous and non-ferrous metals can be casted into the mlods lubricated in accordance with the invention. Alloys of aluminum, zinc, lead, copper, tin and magnesium can be easily cast in the lubricated molds. Gravity casting methods, where the molten metal is poured into a mold, and pressure die casting methods, where the molten metal is forced into the mold, both benefit from the use of the alkoxysilane lubricant. It is conventional to lubricate these molds immediately prior to the casting operation. One measure of the efficiency of the lubricant is the number of molding cycles which can be made using a single mold before the material buildup in that mold necessitates cleaning. By the practice of the invention casting operations can be carried out with little or no down time for mold cleaning. Metal castings made with the lubricated molds do not present problems during painting or plating The following examples are illustrative of the invention which is defined in the claims.
  • EXAMPLE 1 An emulsion containing 35 weight percent 4 weight percent oleic acid, 2.3 weight percent morpholine, and 58.7 weight percent water was dispersed in water to form a lubricant of approximately 50 parts Water to 1 part emulsion. This lubricant was applied to an intricate mold to form aluminum castings by the pressure die casting method. The lubricant was sprayed into the mold prior to each molding cycle. After 1,000 molding cycles, there was no material buildup in the molds.
  • EXAMPLE 2 For purposes of comparison the same type of mold was lubricated with a dispersion of 1 part of a commercially available organosilicone emulsion in 50 parts water. After 100 molding cycles in the aluminum die casting operation, the mold showed a considerable buildup and if critical, it would have been necessary to halt the casting operation to clean the mold.
  • EXAMPLE 4 The emulsion described in Example 2 was diluted with 130 parts of water and utilized to lubricate aluminum valve body molds in a die casting operation. The material proved to be an excellent lubricant.
  • EXAMPLE 5 When the emulsion described in Example 2 was used at an 80 to 1 ratio with water as a lubricant for casting magnesium metal parts, test results were comparable to those obtained in Example 2.
  • a method of lubricating molds utilized in the casting of metal comprising applying to the molding surfaces of said mold an organosilane of the general formula in which R is a lower alkyl radical of not more than 6 carbon atoms;
  • R is a higher alkyl radical of from 8 to 30 carbon atoms
  • a has a value of from 1 to 3.
  • said emulsion consists essentially of 5-60 weight percent of said organosilane; and 1-10 weight percent of an emulsifying agent; the balance being water.
  • organosilane is a mixture Of (CH3)2Si(OC12H25)2 and 6.
  • organosilane is s)2 1s a7)2- 7.
  • R' is an alkyl radical of from 10 to 14 carbon atoms inclusive.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
US768507A 1968-10-17 1968-10-17 Organosilane mold lubricants Expired - Lifetime US3554910A (en)

Applications Claiming Priority (1)

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US76850768A 1968-10-17 1968-10-17

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US3554910A true US3554910A (en) 1971-01-12

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Application Number Title Priority Date Filing Date
US768507A Expired - Lifetime US3554910A (en) 1968-10-17 1968-10-17 Organosilane mold lubricants

Country Status (9)

Country Link
US (1) US3554910A (de)
AT (1) AT297238B (de)
BE (1) BE740355A (de)
CH (1) CH528314A (de)
DE (1) DE1951298A1 (de)
FR (1) FR2020915A1 (de)
GB (1) GB1222903A (de)
NL (1) NL146072B (de)
SE (1) SE341455B (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3941864A (en) * 1973-06-04 1976-03-02 Wacker-Chemie Gmbh Method for manufacturing molded structures and coatings based on inorganic binding agents
US4039143A (en) * 1975-01-06 1977-08-02 General Electric Company Organic hydrocarbon solvent-based green tire lubricant and process
US4043924A (en) * 1973-06-07 1977-08-23 General Electric Company Water based green tire lubricant
US4066560A (en) * 1976-09-20 1978-01-03 General Electric Company Silicone compositions useful as green tire lubricants
US4681714A (en) * 1985-12-27 1987-07-21 Dow Corning Corporation Multiple release mold coating
WO1993011891A1 (en) * 1991-12-16 1993-06-24 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Casting of aluminium-lithium alloys
US5340486A (en) * 1992-08-27 1994-08-23 Acheson Industries, Inc. Lubricant compositions for use in diecasting of metals and process
EP0759348A4 (de) * 1994-05-11 1997-09-24 Daikin Ind Ltd Formverfahren und verdünner für formtrennmittel
WO2003080013A1 (de) * 2002-03-21 2003-10-02 Cognis Deutschland Gmbh & Co. Kg Ölphasen für kosmetische mittel

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3941864A (en) * 1973-06-04 1976-03-02 Wacker-Chemie Gmbh Method for manufacturing molded structures and coatings based on inorganic binding agents
US4043924A (en) * 1973-06-07 1977-08-23 General Electric Company Water based green tire lubricant
US4039143A (en) * 1975-01-06 1977-08-02 General Electric Company Organic hydrocarbon solvent-based green tire lubricant and process
US4066560A (en) * 1976-09-20 1978-01-03 General Electric Company Silicone compositions useful as green tire lubricants
US4681714A (en) * 1985-12-27 1987-07-21 Dow Corning Corporation Multiple release mold coating
WO1993011891A1 (en) * 1991-12-16 1993-06-24 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Casting of aluminium-lithium alloys
US5340486A (en) * 1992-08-27 1994-08-23 Acheson Industries, Inc. Lubricant compositions for use in diecasting of metals and process
EP0759348A4 (de) * 1994-05-11 1997-09-24 Daikin Ind Ltd Formverfahren und verdünner für formtrennmittel
WO2003080013A1 (de) * 2002-03-21 2003-10-02 Cognis Deutschland Gmbh & Co. Kg Ölphasen für kosmetische mittel
US20060008482A1 (en) * 2002-03-21 2006-01-12 Daniela Prinz Oil phases for cosmetic agents

Also Published As

Publication number Publication date
SE341455B (de) 1971-12-27
NL6915665A (de) 1970-04-21
BE740355A (de) 1970-04-16
GB1222903A (en) 1971-02-17
DE1951298A1 (de) 1970-07-16
FR2020915A1 (de) 1970-07-17
NL146072B (nl) 1975-06-16
CH528314A (de) 1972-09-30
AT297238B (de) 1972-03-10

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