US3843529A - Metal working lubricant compositions - Google Patents

Metal working lubricant compositions Download PDF

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US3843529A
US3843529A US27960172A US3843529A US 3843529 A US3843529 A US 3843529A US 27960172 A US27960172 A US 27960172A US 3843529 A US3843529 A US 3843529A
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weight percent
percent
lubricant
weight
radical
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R Bertrand
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Dow Silicones Corp
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Dow Corning Corp
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Priority to US27960172 priority Critical patent/US3843529A/en
Priority to CA165,673A priority patent/CA988917A/en
Priority to DE2317708A priority patent/DE2317708C3/en
Priority to SE7306530A priority patent/SE393629B/en
Priority to JP48060746A priority patent/JPS5213275B2/ja
Priority to FR7329044A priority patent/FR2195675B1/fr
Priority to GB3801073A priority patent/GB1407370A/en
Priority to US48709674 priority patent/US3881048A/en
Application granted granted Critical
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    • 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
    • C10M7/00Solid or semi-solid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single solid or semi-solid substances
    • 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
    • C10M2201/04Elements
    • C10M2201/041Carbon; Graphite; Carbon black
    • 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
    • C10M2201/04Elements
    • C10M2201/041Carbon; Graphite; Carbon black
    • C10M2201/042Carbon; Graphite; Carbon black halogenated, i.e. graphite fluoride
    • 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
    • C10M2201/06Metal compounds
    • C10M2201/065Sulfides; Selenides; Tellurides
    • C10M2201/066Molybdenum sulfide
    • 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
    • C10M2201/10Compounds containing silicon
    • C10M2201/102Silicates
    • C10M2201/103Clays; Mica; Zeolites
    • 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
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/12Polysaccharides, e.g. cellulose, biopolymers
    • 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
    • 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
    • C10M2229/00Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04Siloxanes with specific structure
    • C10M2229/05Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C10M2229/052Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/24Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/241Manufacturing joint-less pipes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/242Hot working
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/243Cold working
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
    • C10N2040/245Soft metals, e.g. aluminum
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
    • C10N2040/246Iron or steel
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
    • C10N2040/247Stainless steel
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015Dispersions of solid lubricants
    • C10N2050/02Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/08Solids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10Semi-solids; greasy
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31678Of metal
    • Y10T428/31703Next to cellulosic

Definitions

  • the present invention relates to a water-based lubricant.
  • the invention relates to metal surfaces having a lubricant coating thereon.
  • Lubrication of metals during the working and forming processes is often necessary.
  • the metal working lubricant should lower the friction, improve surface finish and protect new surfaces against atmospheric corrosion.
  • Solid lubricants such as molybdenum disulphide or graphite, are used as metal working lubricants.
  • the use of such lubricants is limited in certain areas of metal working wherein burnishing of the lubricant into the metal surface cannot be tolerated. For example, lubricant con taminated surfaces present difliculties during plating operations.
  • a further object of the invention is to provide metal articles with an adherent corrosion resistant coating.
  • the present invention provides an article comprising a solid metal surface, the surface having coating of a mixture comprising (a) a particulate solid lubricant consisting of a molybdenum disulphide-graphite mixture containing from about to 80 percent by weight molybdenum disulphide and (b) a binder for the lubricant consisting essentially of 40 to weight percent carboxymethylcellulose and 40 to 60 weight percent of an amine-functional silane of the formula (RO) Si ⁇ -CH NHR', hydrolyzates and water soluble partial condensates thereof in which R is an alkyl radical containing from 1 to 4 inclusive carbon atoms; and R is selected from the group consisting of the hydrogen atom, the ⁇ CH NH radical, the
  • the weight ratio of lubricant (a) to binder (b) in the coating being in the range of from 1:1 to 3:1.
  • the invention also provides a lubricant comprising about 50 to weight percent of the molybdenum disulphide-graphite mixture (a) and about 25 to 50 Weight percent of the carboxymethylcellulose-silane binder (b) States Patent 0 ice described above; this being the composition of the coating on the metal article.
  • the use of the molybdenum disulphide-graphite mixture is considered essential in formulating the lubricants of the invention.
  • the defined mixture gives superior performance as compared to formulations utilizing either graphite or molybdenum di sulphide alone.
  • the solid lubricant components are present in the lubricant composition as particles. While the particle size is not critical, for ease in forming coating dispersions, it is preferred that particles in the l to micron diameter size range be utilized.
  • the silane-carboxymethylcellulose components provides a binder system for the lubricant particles in the form of a coating which is adherent to metal surfaces. These components are water-soluble, thus providing easy removal of the coating by washing. The binder system also minimizes burnishing of the metal by the solid lubricants during forming operations.
  • SiOSi water-soluble siloxane
  • silanes such as the gamma-aminopropylsilanes are commercially available.
  • the quaternary salt of the aminoacrylate-functional silane is known and can be prepared by reaction of gamma-chloropropyltrialkoxysilane With 2-(dimethylamino)ethyl methacrylate in the presence of sulfur and methyliodide. Reaction in a solvent at about 100 C. gives good yields of the salt.
  • the hydrochloride salt is also known and is obtained by re acting beta aminoethyl gamma aminopropyltrialkoxysilane with vinylbenzylchloride.
  • the lubricant coating can be applied to any of the solid metals processed by techniques such as extruding, drawing and cold forging.
  • Exemplary of such metals are steel, aluminum, copper, brass, bronze, titanium, tungsten and Monel metal.
  • the described coating provides protection against atmospheric corrosion prior to the metal working.
  • the lubricant coating can be applied as a paste or solvated dispersion by conventional processes such as troweling, dipping, brushing or spraying.
  • Any solvent for carboxymethyl-cellulose can be used in formulating the pastes or dispersions.
  • the solvent should be volatile to the extent that it evaporates at room temperature or slightly above to leave a uniform coating or dry film of lubricant.
  • Suitable solvents include water, methanol, ethanol, isopropanol and the like. For reasons of economy, safety and ease of handling, water is the preferred solvent.
  • a dispersion especially suitable for the dip-coating of metal articles contains about to 30 weight percent of the described molybdenum disulphide-graphite mixture, about 5 to 7.5 weight percent carboxymethylcellulose, about 5 to 7.5 weight percent of an amine-functional silane of the formula (CH O) Si(CH NHtCHfi Nl-l and about 0.5 to 2 weight percent bentonite; the remainder (53 to 74.5 weight percent) being water.
  • the bentonite acts as a stabilizer for the dispersion as well as reducing foaming during mixing of the dispersion.
  • Conventional additives, such as dyes. bactericides, corrosion inhibitors and the like, can also be used in formulating the above-described lubricant composition.
  • Metal articles are coated by dipping or immersing in the aqueous dispersion and allowing the coating to dry at A mixture of grams of molybdenum disulphide powder and 9.2 grams of graphite was added to 105 grams of 4 rusted equally. This demonstrates that all of the coating was removed by washing.
  • the endurance life of the above-described lubricant coating in a sliding steel-on-steel application was determined by use of a Falex test machine run in accordance with ASTM D2625. Endurance life was reported as the time required for failure to occur at 1000 lb. load and at 290 rpm. Test pins dip-coated with the described aqueous lubricant and allowed to dry had an endurance life ranging from 158 to 219 minutes.
  • a lubricant composition containing 34 grams of graphite (instead of the graphite/ molybdenum sulfide mixture) was formulated with the same amounts of the other components described above. Pins coated with this lubricant had a wear life of about five minutes.
  • an Alpha LFW-l test machine (described in US. 3,028,746) was operated at 72 r.p.m. under a load of 630 lbs. using a standard steel ring (R and a standard steel block (R 30).
  • the ring was coated with the lubricant of the invention described above. After 500 Ocycles, the LFW-l wear scar was 1.0 mm. and failure did not occur until after 138,220 cycles.
  • EXAMPLE 2 Lubricant compositions containing various silanes were formulated.
  • the compositions contained 16.5 weight percent molybdenum disulphide, 6.1 weight percent graphite, 1.3 weight percent bentonite, 69.5 weight percent of a 10 percent aqueous solution of carboxymethylcellulose and 6.6 weight percent of the silane.
  • Palex pins were dipped in the aqueous lubricants and the coating was allowed to air dry.
  • the endurance life (as determined by the Falex test) for each of the coatings containing different silanes is listed below:
  • Metal test panels (1" x 3") of aluminum and steel were dipped in the above dispersion and allowed to air-dry for about 4 hours. Uniform adherent, void-free coatings were obtained. Coated steel panels were placed in a Cyclic Environment Tester and subjected to wet conditions for 30 minutes, followed by dry conditions for 15 minutes for a total of three hours. The coated panels showed no evidence of rust. Uncoated steel panels were discolored and beginning to rust after three hours under the same conditions.
  • a portion of steel test panel was coated with the described dispersion and allowed to air dry for 24 hours. The coating was then removed by washing with water. The panel was exposed to atmospheric conditions (average humidity of 80 percent) for one month. The uncoated portion and c ated/Washed portion of the panel were That which is claimed is:
  • a lubricant composition consisting essentially of (a) about 50 to 75 percent by weight of a mixture of solid lubricant particles, the mixture containing from about 50 to weight percent molybdenum disulphide, the remainder being graphite; and
  • the lubricant composition of claim 1 including a solvent for the binder (b).
  • a lubricant composition in accordance with claim 4 consisting essentially of f f g (a) about 15 to 30 weight percent of said mixture of 5 3 )a T 2- T :I I I-@- 2 l solid lubricant particles; (b) about to 7.5 weight percent carboxymethylcellulose; (c) about 5 to 7.5 weight percent of said amine- References Cited i g g g; h b d 10 UNITED STATES PATENTS a out to weig t percent entonite; an about 53 to weight Percent ijiiiiifi 551322 11831255555333: iii-.38 5.
  • a lubricant composition in accordance with claim 4 3,051,586 -8/ 1962 Heath et al. 252-30 wherein the silane is of the formula 15 3,341,454 9/ 1967 Chor et a1 252-22 3,361,666 1/1968 Caddis et a1. 252- (CH)3S CH2CH2CHNH 3,575,858 4/1971 Adair et al. 252 25 6.
  • silane is of the formula E. PI'lmal'y Examiner 7.
  • a lubricant composition in accordance with claim 4 VAUGHN Asslstam Exammer wherein the silane is of the formula U S C1 X R UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 5 ,845 ,529 DATED 1 October 22, 197% INVENTORLSQ ROBERT G.
  • BER'IRAND It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Abstract

RADICAL.

-(CH2)2-NH2(+)-CH2-(1,4-PHENYLENE)-CH=CH2 CL(-)

RADICAL AND THE

THE -(CH2)2-N(+)(-CH3)2-CH2-CH2-OOC-C(-CH3)=CH2 CL(-)

1. A LUBRIANT COMPOSITION CONSISTING ESSENTIALLY OF (A) ABOUT 50 TO 75 PERCENT BY WEIGHT OF A MIXTURE OF SOLID LUBRIANT PARTICLES, THE MIXTURE CONTAINING FROM ABOUT 50 TO 80 WEIGHT PERCENT MOLYBDENUM DISULPHIDE, THE REMAINDER BEING GRAPHITE; AND (B) ABOUT 25 TO 50 PERCENT BY WEIGHT OF A BINDER CONSISTING ESSENTIALLY OF ABOUT 40 TO 60 WEIGHT PERCENT CARBOXYMETHYLCELLULOSE AND ABOUT 40 TO 60 WEIGHT PERCENT OF AN AMINE-FUNCTIONAL SILANE OF THE FORMULA (RO)3SI$CH2$3NHR'', HYDDROLYZATES AND PARTIAL CONDENSATES THEROF IN WHICH R IS AN ALKYL RADICAL CONTAINING FROM 1 TO 4 INCLUSIVE CARBON ATOMS; AND R'' IS SELECTED FROM THE GROUP CONSISTING OF THE HYDROGEN ATOM, THE $CH2$2NH2 RADICAL,

Description

3,843,529 METAL WORKING LUBRICANT COMPOSTTIONS Robert G. Bertrand, Midland, Mich, assignor to Dow Corning Corporation, Midland, Mich. No Drawing. Filed Aug. 10, 1972, Ser. No. 279,601 int. Cl. C1011! 3/0Z, 3/46, 7/50 US. Cl. 252- 8 Claims ABSTRACT OF THE DISCLOSURE A water-dispersible metal working lubricant comprising effective amounts of:
(a) molybdenum disulfide (b) graphite (c) a binder mixture of carboxymethylcellulose and amine-functional silane (d) bentonite SPECIFICATION The present invention relates to a water-based lubricant. In one aspect, the invention relates to metal surfaces having a lubricant coating thereon.
Lubrication of metals during the working and forming processes is often necessary. The metal working lubricant should lower the friction, improve surface finish and protect new surfaces against atmospheric corrosion. Solid lubricants, such as molybdenum disulphide or graphite, are used as metal working lubricants. The use of such lubricants is limited in certain areas of metal working wherein burnishing of the lubricant into the metal surface cannot be tolerated. For example, lubricant con taminated surfaces present difliculties during plating operations.
Thus, it is an object of the present invention to provide metal surfaces with an effective, but easily removed lubricant coating.
It is another object of the invention to provide novel aqueous lubricant compositions.
A further object of the invention is to provide metal articles with an adherent corrosion resistant coating.
These and other objects of the invention will be apparent to one skilled in the art upon reading the disclosure and claims.
The present invention provides an article comprising a solid metal surface, the surface having coating of a mixture comprising (a) a particulate solid lubricant consisting of a molybdenum disulphide-graphite mixture containing from about to 80 percent by weight molybdenum disulphide and (b) a binder for the lubricant consisting essentially of 40 to weight percent carboxymethylcellulose and 40 to 60 weight percent of an amine-functional silane of the formula (RO) Si{-CH NHR', hydrolyzates and water soluble partial condensates thereof in which R is an alkyl radical containing from 1 to 4 inclusive carbon atoms; and R is selected from the group consisting of the hydrogen atom, the {CH NH radical, the
radical and the radical; the weight ratio of lubricant (a) to binder (b) in the coating being in the range of from 1:1 to 3:1.
The invention also provides a lubricant comprising about 50 to weight percent of the molybdenum disulphide-graphite mixture (a) and about 25 to 50 Weight percent of the carboxymethylcellulose-silane binder (b) States Patent 0 ice described above; this being the composition of the coating on the metal article.
The use of the molybdenum disulphide-graphite mixture is considered essential in formulating the lubricants of the invention. When combined with the binder, the defined mixture gives superior performance as compared to formulations utilizing either graphite or molybdenum di sulphide alone. The solid lubricant components are present in the lubricant composition as particles. While the particle size is not critical, for ease in forming coating dispersions, it is preferred that particles in the l to micron diameter size range be utilized.
The silane-carboxymethylcellulose components provides a binder system for the lubricant particles in the form of a coating which is adherent to metal surfaces. These components are water-soluble, thus providing easy removal of the coating by washing. The binder system also minimizes burnishing of the metal by the solid lubricants during forming operations.
Silanes operable in the practice of the invention include When formulated in aqueous lubricant dispersions, the alkoxy substituents hydrolyze to form (HO )Si-=-. It is possible for some of the hydroxyl groups to condense to form a low-molecular weight, water-soluble siloxane (SiOSi) polymer or partial condensate which retains alkoxy and/or hydroxyl-functionality and the defined aminesubstituents. See US. Pat. 3,630,827 concerning these silanes.
Certain of the silanes, such as the gamma-aminopropylsilanes are commercially available. The quaternary salt of the aminoacrylate-functional silane is known and can be prepared by reaction of gamma-chloropropyltrialkoxysilane With 2-(dimethylamino)ethyl methacrylate in the presence of sulfur and methyliodide. Reaction in a solvent at about 100 C. gives good yields of the salt. The hydrochloride salt is also known and is obtained by re acting beta aminoethyl gamma aminopropyltrialkoxysilane with vinylbenzylchloride.
The lubricant coating can be applied to any of the solid metals processed by techniques such as extruding, drawing and cold forging. Exemplary of such metals are steel, aluminum, copper, brass, bronze, titanium, tungsten and Monel metal. In addition to providing surface lubrication during the metal forming operation, the described coating provides protection against atmospheric corrosion prior to the metal working.
The lubricant coating can be applied as a paste or solvated dispersion by conventional processes such as troweling, dipping, brushing or spraying. Any solvent for carboxymethyl-cellulose can be used in formulating the pastes or dispersions. The solvent should be volatile to the extent that it evaporates at room temperature or slightly above to leave a uniform coating or dry film of lubricant. Suitable solvents include water, methanol, ethanol, isopropanol and the like. For reasons of economy, safety and ease of handling, water is the preferred solvent.
A dispersion especially suitable for the dip-coating of metal articles contains about to 30 weight percent of the described molybdenum disulphide-graphite mixture, about 5 to 7.5 weight percent carboxymethylcellulose, about 5 to 7.5 weight percent of an amine-functional silane of the formula (CH O) Si(CH NHtCHfi Nl-l and about 0.5 to 2 weight percent bentonite; the remainder (53 to 74.5 weight percent) being water. The bentonite acts as a stabilizer for the dispersion as well as reducing foaming during mixing of the dispersion. Conventional additives, such as dyes. bactericides, corrosion inhibitors and the like, can also be used in formulating the above-described lubricant composition.
Metal articles are coated by dipping or immersing in the aqueous dispersion and allowing the coating to dry at A mixture of grams of molybdenum disulphide powder and 9.2 grams of graphite was added to 105 grams of 4 rusted equally. This demonstrates that all of the coating was removed by washing.
The endurance life of the above-described lubricant coating in a sliding steel-on-steel application was determined by use of a Falex test machine run in accordance with ASTM D2625. Endurance life was reported as the time required for failure to occur at 1000 lb. load and at 290 rpm. Test pins dip-coated with the described aqueous lubricant and allowed to dry had an endurance life ranging from 158 to 219 minutes.
For purposes of comparison, a lubricant composition containing 34 grams of graphite (instead of the graphite/ molybdenum sulfide mixture) was formulated with the same amounts of the other components described above. Pins coated with this lubricant had a wear life of about five minutes.
In another test, an Alpha LFW-l test machine (described in US. 3,028,746) was operated at 72 r.p.m. under a load of 630 lbs. using a standard steel ring (R and a standard steel block (R 30). The ring was coated with the lubricant of the invention described above. After 500 Ocycles, the LFW-l wear scar was 1.0 mm. and failure did not occur until after 138,220 cycles.
These data demonstrate the excellent lubrication obtained by use of the composition of the invention.
EXAMPLE 2 Lubricant compositions containing various silanes were formulated. The compositions contained 16.5 weight percent molybdenum disulphide, 6.1 weight percent graphite, 1.3 weight percent bentonite, 69.5 weight percent of a 10 percent aqueous solution of carboxymethylcellulose and 6.6 weight percent of the silane. Palex pins were dipped in the aqueous lubricants and the coating was allowed to air dry. The endurance life (as determined by the Falex test) for each of the coatings containing different silanes is listed below:
10 percent aqueous solution of carboxymethylcellulose. During mixing of these components, 10 grams of and 2 grams of bentonite were added. The homogeneous aqueous lubricant contained 22.6 weight percent lubricant particles, 6.9 weight percent carboxymethylcellulose, 6.6 of the described silane, 1.3 weight percent bentonite and 62.6 weight percent water.
Metal test panels (1" x 3") of aluminum and steel were dipped in the above dispersion and allowed to air-dry for about 4 hours. Uniform adherent, void-free coatings were obtained. Coated steel panels were placed in a Cyclic Environment Tester and subjected to wet conditions for 30 minutes, followed by dry conditions for 15 minutes for a total of three hours. The coated panels showed no evidence of rust. Uncoated steel panels were discolored and beginning to rust after three hours under the same conditions.
A portion of steel test panel was coated with the described dispersion and allowed to air dry for 24 hours. The coating was then removed by washing with water. The panel was exposed to atmospheric conditions (average humidity of 80 percent) for one month. The uncoated portion and c ated/Washed portion of the panel were That which is claimed is:
1. A lubricant composition consisting essentially of (a) about 50 to 75 percent by weight of a mixture of solid lubricant particles, the mixture containing from about 50 to weight percent molybdenum disulphide, the remainder being graphite; and
(b) about 25 to 50 percent by Weight of a binder consisting essentially of about 40 to 60 weight percent carboxymethylcellulose and about 40 to 60 weight percent of an amine-functional siiane of the formula (RO) Si{-CH NHR, hydrolyzates and partial condensates thereof in which R is an alkyl radical containing from 1 to 4 inclusive carbon atoms; and R is selected from the group consisting of the hydrogen atom, the (CH NH radical,
3): radical and the I2 radical. 2. The lubricant composition of claim 1 including a solvent for the binder (b).
5 6 3. The lubricant composition of claim 2 wherein the 8. A lubricant composition in accordance with claim 4 solvent is water. wherein the silane is of the formula 4. A lubricant composition in accordance with claim 3 consisting essentially of f f g (a) about 15 to 30 weight percent of said mixture of 5 3 )a T 2- T :I I I-@- 2 l solid lubricant particles; (b) about to 7.5 weight percent carboxymethylcellulose; (c) about 5 to 7.5 weight percent of said amine- References Cited i g g g; h b d 10 UNITED STATES PATENTS a out to weig t percent entonite; an about 53 to weight Percent ijiiiiifi 551322 11831255555333: iii-.38 5. A lubricant composition in accordance with claim 4 3,051,586 -8/ 1962 Heath et al. 252-30 wherein the silane is of the formula 15 3,341,454 9/ 1967 Chor et a1 252-22 3,361,666 1/1968 Caddis et a1. 252- (CH)3S CH2CH2CHNH 3,575,858 4/1971 Adair et al. 252 25 6. A lubricant composition on in accordance with clalm 3,574, 7 1 972 1 et 1 252 .25
4 wherein the silane is of the formula E. PI'lmal'y Examiner 7. A lubricant composition in accordance with claim 4 VAUGHN Asslstam Exammer wherein the silane is of the formula U S C1 X R UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 5 ,845 ,529 DATED 1 October 22, 197% INVENTORLSQ ROBERT G. BER'IRAND It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 5, line 25, that portion of the formula reading GD "(cH o( si4eH NHcH N-crr2cr12 should read (CH O) SiGH NHCH }NCH GI-I gignzd and Scaled this zwenty.seventh Day Of January 1976 [SEAL] i Attest: i i E RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofParents and Trademarks UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,8 5,529 DATED I October 22, 197 INVENTOR(SQ I ROBERT G. BERTRAND It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 5, line 25, that portion of the formula reading (9 "(c11 0( sicH2-) NHoH N- 3H (3H2" should read I (CH3)2 (cH o) si4cH NHcH ;N-crr ctr Signed and Sealed this twenty- Day Of January 1976 [SEAL] Attest:
RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofPatents and Trademarks

Claims (1)

1. A LUBRIANT COMPOSITION CONSISTING ESSENTIALLY OF (A) ABOUT 50 TO 75 PERCENT BY WEIGHT OF A MIXTURE OF SOLID LUBRIANT PARTICLES, THE MIXTURE CONTAINING FROM ABOUT 50 TO 80 WEIGHT PERCENT MOLYBDENUM DISULPHIDE, THE REMAINDER BEING GRAPHITE; AND (B) ABOUT 25 TO 50 PERCENT BY WEIGHT OF A BINDER CONSISTING ESSENTIALLY OF ABOUT 40 TO 60 WEIGHT PERCENT CARBOXYMETHYLCELLULOSE AND ABOUT 40 TO 60 WEIGHT PERCENT OF AN AMINE-FUNCTIONAL SILANE OF THE FORMULA (RO)3SI$CH2$3NHR'', HYDDROLYZATES AND PARTIAL CONDENSATES THEROF IN WHICH R IS AN ALKYL RADICAL CONTAINING FROM 1 TO 4 INCLUSIVE CARBON ATOMS; AND R'' IS SELECTED FROM THE GROUP CONSISTING OF THE HYDROGEN ATOM, THE $CH2$2NH2 RADICAL,
US27960172 1972-08-10 1972-08-10 Metal working lubricant compositions Expired - Lifetime US3843529A (en)

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US27960172 US3843529A (en) 1972-08-10 1972-08-10 Metal working lubricant compositions
CA165,673A CA988917A (en) 1972-08-10 1973-03-09 Metal working lubricant
DE2317708A DE2317708C3 (en) 1972-08-10 1973-04-09 lubricant
SE7306530A SE393629B (en) 1972-08-10 1973-05-09 LUBRICANT COMPOSITION FOR METALWORKING CONTAINING MOLYBDENESULPHID, GRAPHITE, CARBOXIMETHYLELLULOSE AND AN AMINO-FUNCTIONAL SILAN
JP48060746A JPS5213275B2 (en) 1972-08-10 1973-05-30
FR7329044A FR2195675B1 (en) 1972-08-10 1973-08-08
GB3801073A GB1407370A (en) 1972-08-10 1973-08-10 Lubricant compositions
US48709674 US3881048A (en) 1972-08-10 1974-07-10 Metal coated with a lubricant composition

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US3931020A (en) * 1974-08-22 1976-01-06 Gulf & Western Industries, Inc. Smokeless forging lubricant
US4001125A (en) * 1975-06-09 1977-01-04 Grafo Colloids Corporation Lubricant for mandrels, forging dies, molds and the like
US4115282A (en) * 1975-12-02 1978-09-19 Deutsche Texaco Aktiengesellschaft Biodegradable grease composition
US4132656A (en) * 1976-12-20 1979-01-02 Atlantic Richfield Company Solid particles containing lubricating oil composition and method for using same
US4257902A (en) * 1976-08-04 1981-03-24 Singer & Hersch Industrial Development (Pty.) Ltd. Water-based industrial fluids
US4259467A (en) * 1979-12-10 1981-03-31 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains
US4260725A (en) * 1979-12-10 1981-04-07 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes which are thermally bonded to polymerizable groups and which contain hydrophilic sidechains
US4303537A (en) * 1978-11-15 1981-12-01 Dow Corning Gmbh Water based lubricant
US4416132A (en) * 1981-06-24 1983-11-22 E/M Lubricants, Inc. Metal forming lubricant and method of use thereof
US4474669A (en) * 1980-06-02 1984-10-02 United States Steel Corporation Can-making lubricant
US5013466A (en) * 1989-03-23 1991-05-07 Japan Atomic Energy Research Institute Lubricating grease
US5116521A (en) * 1988-07-07 1992-05-26 Nippondenso Co., Ltd. Aqueous lubrication treatment liquid and method of cold plastic working metallic materials
US5297409A (en) * 1992-06-22 1994-03-29 Beaman Danny L Workhardening high-strength steel aircraft components
US5492639A (en) * 1992-02-06 1996-02-20 Lonza Ltd. Mandrel lubricant for the production of seamless tubes
EP0839895A2 (en) * 1996-10-30 1998-05-06 Kawasaki Steel Corporation Lubricant for use in hot work tools
US6136757A (en) * 1996-09-25 2000-10-24 Kelsan Technologies Corporation Solid lubricants and friction modifiers for heavy loads and rail applications
US20070242215A1 (en) * 2006-04-13 2007-10-18 Bausch & Lomb Incorporated Cationic end-capped siloxane prepolymer for reduced cross-link density
US20090143556A1 (en) * 2006-06-30 2009-06-04 Bausch & Lomb Incorporated Polymerizable siloxane-quaternary amine copolymers
US20090235602A1 (en) * 2008-03-21 2009-09-24 Ceccofiglio David H Strengthened shutter system
US20100269558A1 (en) * 2009-04-22 2010-10-28 Gm Global Technology Operations, Inc. Method to Improve Solid Lubricant Film Tribological Performance and Adhesion to Hot Forming Material

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US5476580A (en) * 1993-05-17 1995-12-19 Electrochemicals Inc. Processes for preparing a non-conductive substrate for electroplating
US6303181B1 (en) 1993-05-17 2001-10-16 Electrochemicals Inc. Direct metallization process employing a cationic conditioner and a binder
US5690805A (en) * 1993-05-17 1997-11-25 Electrochemicals Inc. Direct metallization process
US6710259B2 (en) * 1993-05-17 2004-03-23 Electrochemicals, Inc. Printed wiring boards and methods for making them
US5725807A (en) * 1993-05-17 1998-03-10 Electrochemicals Inc. Carbon containing composition for electroplating
US6171468B1 (en) 1993-05-17 2001-01-09 Electrochemicals Inc. Direct metallization process
US5389270A (en) * 1993-05-17 1995-02-14 Electrochemicals, Inc. Composition and process for preparing a non-conductive substrate for electroplating
US5833452A (en) * 1994-12-15 1998-11-10 M-C Power Corporation Coated metal sintering carriers for fuel cell electrodes
FR2803232B1 (en) * 1999-12-29 2002-04-26 Serio Emile Di IMPROVED PROCESS FOR MANUFACTURING LIGHT ALLOY PARTS
US20060029494A1 (en) * 2003-05-27 2006-02-09 General Electric Company High temperature ceramic lubricant
RU2678069C2 (en) * 2014-09-12 2019-01-22 Томас Л. СИДЛЕР Improvements in methods and systems requiring lubrication

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US3051586A (en) * 1958-01-27 1962-08-28 Electrofilm Inc Solid lubricant film resistant to corrosion
US3341454A (en) * 1963-02-25 1967-09-12 Hodson Corp Lubricant composition
US3288710A (en) * 1964-02-21 1966-11-29 Dow Corning Silicones Ltd High load capacity dry film lubricants
US3361666A (en) * 1966-09-09 1968-01-02 Nasa Usa Inorganic solid film lubricants
US3575858A (en) * 1969-05-20 1971-04-20 Us Air Force Lubricating composition consisting of perarylated silanes and solid lubricant powders
US3674690A (en) * 1969-07-08 1972-07-04 Us Air Force Air drying silicone resin bonded dry film lubricant

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3931020A (en) * 1974-08-22 1976-01-06 Gulf & Western Industries, Inc. Smokeless forging lubricant
US4001125A (en) * 1975-06-09 1977-01-04 Grafo Colloids Corporation Lubricant for mandrels, forging dies, molds and the like
US4115282A (en) * 1975-12-02 1978-09-19 Deutsche Texaco Aktiengesellschaft Biodegradable grease composition
US4257902A (en) * 1976-08-04 1981-03-24 Singer & Hersch Industrial Development (Pty.) Ltd. Water-based industrial fluids
USRE33124E (en) * 1976-08-04 1989-12-05 Singer and Hersch Industrial Development (PTY) Ltd. Water-based industrial fluids
US4132656A (en) * 1976-12-20 1979-01-02 Atlantic Richfield Company Solid particles containing lubricating oil composition and method for using same
US4134844A (en) * 1976-12-20 1979-01-16 Atlantic Richfield Company Solid particles containing lubricating oil composition and method for using same
US4303537A (en) * 1978-11-15 1981-12-01 Dow Corning Gmbh Water based lubricant
US4259467A (en) * 1979-12-10 1981-03-31 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains
US4260725A (en) * 1979-12-10 1981-04-07 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes which are thermally bonded to polymerizable groups and which contain hydrophilic sidechains
US4474669A (en) * 1980-06-02 1984-10-02 United States Steel Corporation Can-making lubricant
US4416132A (en) * 1981-06-24 1983-11-22 E/M Lubricants, Inc. Metal forming lubricant and method of use thereof
US5116521A (en) * 1988-07-07 1992-05-26 Nippondenso Co., Ltd. Aqueous lubrication treatment liquid and method of cold plastic working metallic materials
US5013466A (en) * 1989-03-23 1991-05-07 Japan Atomic Energy Research Institute Lubricating grease
US5492639A (en) * 1992-02-06 1996-02-20 Lonza Ltd. Mandrel lubricant for the production of seamless tubes
US5297409A (en) * 1992-06-22 1994-03-29 Beaman Danny L Workhardening high-strength steel aircraft components
US6136757A (en) * 1996-09-25 2000-10-24 Kelsan Technologies Corporation Solid lubricants and friction modifiers for heavy loads and rail applications
EP0839895A2 (en) * 1996-10-30 1998-05-06 Kawasaki Steel Corporation Lubricant for use in hot work tools
EP0839895A3 (en) * 1996-10-30 1998-11-25 Kawasaki Steel Corporation Lubricant for use in hot work tools
CN1070528C (en) * 1996-10-30 2001-09-05 川崎制铁株式会社 Lubricant compsn. for heat working
US20070242215A1 (en) * 2006-04-13 2007-10-18 Bausch & Lomb Incorporated Cationic end-capped siloxane prepolymer for reduced cross-link density
US7960447B2 (en) * 2006-04-13 2011-06-14 Bausch & Lomb Incorporated Cationic end-capped siloxane prepolymer for reduced cross-link density
US20090143556A1 (en) * 2006-06-30 2009-06-04 Bausch & Lomb Incorporated Polymerizable siloxane-quaternary amine copolymers
EP2404951A1 (en) * 2006-06-30 2012-01-11 Bausch & Lomb Incorporated Polymerizable siloxane-quaternary amine copolymers
US20090235602A1 (en) * 2008-03-21 2009-09-24 Ceccofiglio David H Strengthened shutter system
US20100269558A1 (en) * 2009-04-22 2010-10-28 Gm Global Technology Operations, Inc. Method to Improve Solid Lubricant Film Tribological Performance and Adhesion to Hot Forming Material
US8250890B2 (en) * 2009-04-22 2012-08-28 GM Global Technology Operations LLC Method to improve solid lubricant film tribological performance and adhesion to hot forming material

Also Published As

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CA988917A (en) 1976-05-11
FR2195675B1 (en) 1976-11-12
DE2317708B2 (en) 1974-11-21
DE2317708A1 (en) 1974-02-28
GB1407370A (en) 1975-09-24
DE2317708C3 (en) 1975-07-03
US3881048A (en) 1975-04-29
FR2195675A1 (en) 1974-03-08

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