WO2008069936A1 - Composition anti-grippage avec nanoparticules solides lubrifiantes - Google Patents

Composition anti-grippage avec nanoparticules solides lubrifiantes Download PDF

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Publication number
WO2008069936A1
WO2008069936A1 PCT/US2007/024481 US2007024481W WO2008069936A1 WO 2008069936 A1 WO2008069936 A1 WO 2008069936A1 US 2007024481 W US2007024481 W US 2007024481W WO 2008069936 A1 WO2008069936 A1 WO 2008069936A1
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Prior art keywords
composition
lubricating
nano
sized
solid particles
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PCT/US2007/024481
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English (en)
Inventor
Prakash S. Patel
Shabbir Attarwala
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Henkel Corporation
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Publication of WO2008069936A1 publication Critical patent/WO2008069936A1/fr
Priority to US12/469,961 priority Critical patent/US8258086B2/en

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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
    • C10M171/00Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/06Particles of special shape or size
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    • 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
    • C10M2201/0413Carbon; Graphite; Carbon black used as base material
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    • 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
    • C10M2201/0416Carbon; Graphite; Carbon black used as thickening agents
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    • 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
    • C10M2201/05Metals; Alloys
    • C10M2201/053Metals; Alloys used as base material
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    • 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
    • C10M2201/062Oxides; Hydroxides; Carbonates or bicarbonates
    • C10M2201/0623Oxides; Hydroxides; Carbonates or bicarbonates used as base material
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    • 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
    • C10M2201/0653Sulfides; Selenides; Tellurides used as base material
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    • 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
    • C10M2201/0663Molybdenum sulfide used as base material
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10Compounds containing silicon
    • C10M2201/102Silicates
    • C10M2201/103Clays; Mica; Zeolites
    • C10M2201/1036Clays; Mica; Zeolites used as thickening agents
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    • 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
    • C10M2201/105Silica
    • C10M2201/1056Silica used as thickening agents
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026Butene
    • C10M2205/0265Butene used as base material
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    • 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
    • C10M2217/04Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/044Polyamides
    • C10M2217/0446Polyamides used as thickening agents
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    • 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
    • C10M2229/02Unspecified siloxanes; Silicones
    • C10M2229/025Unspecified siloxanes; Silicones used as base material
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/02Groups 1 or 11
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    • C10N2010/00Metal present as such or in compounds
    • C10N2010/04Groups 2 or 12
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    • C10N2010/00Metal present as such or in compounds
    • C10N2010/06Groups 3 or 13
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    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/08Groups 4 or 14
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2010/00Metal present as such or in compounds
    • C10N2010/12Groups 6 or 16
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    • C10N2010/00Metal present as such or in compounds
    • C10N2010/14Group 7
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/16Groups 8, 9, or 10
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    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/055Particles related characteristics
    • C10N2020/06Particles of special shape or size
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    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/56Boundary lubrication or thin film lubrication
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    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/04Aerosols
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    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10Semi-solids; greasy

Definitions

  • the present invention relates to anti-seize and /or lubricant compositions, particularly compositions including nano-sized particles.
  • An anti-seize composition is typically used to prevent metal-to-metal joints from seizing, galling or cold-welding. Seizing may occur when metal-to-metal joints are placed under fairly high loads and then subjected to reciprocal, relatively small-displacement movements.
  • a lubricating composition is typically used to reduce the coefficient of friction between two sliding parts, thereby facilitating relatively large sliding movements between the parts.
  • An anti- seize /lubricating composition depending upon the specific application, may be used as an anti-seize composition, as a lubricating composition, or in both capacities. For example, an anti-seize/ lubricating composition may act as a lubricating composition for a lightly loaded roller bearing.
  • An anti- seize /lubricating composition may acts as an anti-seize composition with applied to a highly loaded threaded fastener subjected to load reversals.
  • An anti- seize /lubricating composition may act in both capacities when parts, for example, gears, need to slide relative to one another when rotating and to transmit high loads when stationary.
  • Anti-seize /lubricating compositions are available as liquids, pastes, solids and aerosols.
  • Anti-seize /lubricating compositions may be expected to operate under a variety of conditions, including, for instance, high loads, extreme temperatures, dirty and /or corrosive operating environments, etc.
  • anti- seize /lubricating compositions may be expected to survive, for example, by not wearing off or by not breaking down, for relatively extended periods of time.
  • anti-seize /lubricating compositions may be expected to operate without contaminating adjacent parts cause by, for example, simple physical transference or outgassing of volatile components.
  • Anti-seize /lubricating compositions may also be expected to protect the surface of the individual parts, for example, by inhibiting or preventing corrosion.
  • anti- seize/ lubricating compositions may be expected to have other, more esoteric characteristics, such as facilitating heat transfer, being non-toxic, working under extreme humidity conditions, etc.
  • C5-A Copper Anti-Seize is a suspension of copper and graphite in a high-quality grease, which protects metal parts from rust, corrosion, galling, and seizing at temperatures to 1800°F (982°C), and tested to MIL(PRF)- A- 907-E.
  • Nickel Anti-Seize is a copper-free product, recommended for stainless steel and other metal fittings to prevent corrosion, seizing, and galling in harsh, chemical environments, and temperatures to 2400°F (1315°C).
  • MoIy Paste is a low friction product, which lubricates press fits, protects during break-in and under high static loads up to 750°F (400°C).
  • Silver Grade Anti-Seize is a temperature-resistant, petroleum-based inert lubricant compound fortified with graphite and metallic flake, which will not evaporate or harden in extreme cold or heat and is for use in assemblies up to 1600°F (871°C).
  • Heavy Duty Anti-Seize is a metal free product, which provides excellent lubricity, outstanding lubrication to all metals including stainless steel, aluminum, and soft metals up to 2400°F (1315°C).
  • Marine Grade Anti-Seize is formulated to protect assemblies exposed directly or indirectly to fresh and salt water.
  • Marine Grade Anti-Seize works well in high humidity conditions, and has excellent lubricity, superior water wash-out and water spray resistance, and prevents galvanic corrosion, protects in temperatures from -29°C to 1315°C (-20 0 F to 2400°F).
  • Gra ⁇ hite-50 Anti-Seize is an electrically conductive, non-metallic product, which is temperature resistant up to 900°F (482°C).
  • Moly-50 Anti-Seize is a thread lubricant, which is temperature resistant to 750°F (400°C) and provides excellent lubricity.
  • Zinc Anti-Seize protects aluminum and ferrous surfaces from seizure and corrosion up to 750°F (400°C).
  • N-1000 High Purity Anti-Seize is a copper-based product, which is suitable for long-term, stainless steel applications and high-nickel, alloy bolting.
  • N-5000 High Purity Anti-Seize is a nickel-based product, is recommended for highly corrosive environments to 2400°F (1315°C).
  • High Performance N-5000 High Purity Anti-Seize, a nickel-based product is temperature resistant to 2400°F (1315°C).
  • N-7000 High Purity Anti- Seize is a metal-free product, which provides high levels of purity.
  • White Hi- Temp Anti-Seize is a non-metallic product which protects against high temperature seizing and galling of mated metal parts, up to 2000°F (1093°C), while demonstrating excellent lubricity and use on various metals, such as copper, brass, cast iron, steel and all alloys including stainless steel.
  • Nano-sized lubricating solid particles are a microscopic particle whose size is measure in nanometers (nm), generally with at least one dimension being less than 500 nm. Nano-sized particles typically exhibit properties different from the properties of the bulk material or the material in a particle size larger than nano-size.
  • One explanation for this is that as particles decrease in size surface characteristics of the material begin to dominate, possibly because the percentage of atoms at the surface becomes significant.
  • Nano-sized particles may be made from a wide variety of materials, including, by way of non-limiting example, carbon, metals, and ceramics.
  • Carbon black is an example of a nano-sized particle that has been used for many years.
  • Nanotubes made of carbon, boron and nitrogen are known.
  • Pure metal nano- sized particles, such as silver or platinum find used as catalysts.
  • Ceramics may include metal oxides, such as titanium, zinc, aluminum and iron oxides, or silicates or silicon oxides, such as clay.
  • nano-sized particles may be formed of one or more materials.
  • nano-sized particles may be coated or chemically modified to make them more or less hydrophilic, or nano- sized particles may be doped, i.e., a dopant element such as boron, phosphorous, and arsenic, to name a few, may be incorporated into the base material.
  • a dopant element such as boron, phosphorous, and arsenic, to name a few
  • Nano-sized particles may be formed using a wide variety of techniques, including, by way of non-limiting examples, chemical or physical vapor deposition, physical vapor synthesis, reactive sputtering, electro-deposition, laser pyrolysis, laser ablation, spray conversion, mechanical alloying, sol gel techniques, supercritical fluid precipitation and solid-state processes such as grinding or milling.
  • Nano-sized particles may come in a wide variety of forms, including, by way of non-limiting example, powders, crystals, flakes, nanotubes, nanowires, nanospheres. Nano-sized particles may be nano-sized in all three dimensions, in two dimensions, or only in one dimension. Thus, for example, metal oxide ceramic nano-sized powders may be roughly the same size (ranging from 2-3 nm up to 200-300 nm) in all three dimensions. Silicate nano-sized particles may form flakes having a thickness on the order of lnm and width dimensions on the order of 100-1000 nm. And carbon nanotubes, multi-walled or single walled, may have diameters on the order of 0.5-50 nm, but with lengths ranging from a few hundred nanometers to a micron or more.
  • Conventional lubricants typically have relatively low percentages of lubricating solids (on the order of 5-10%). Under extreme pressure conditions, the lubricating solids may squeeze out from between the working parts, allowing detrimental metal-to-metal contact. Alternatively, at elevated temperatures (on the order of 300-600°F), the oil or grease may burn off, leaving only the lubricating solids to act as a barrier between the working parts. Under these conditions, lubricants having relatively low percentages of lubricating solids may also allow detrimental metal-to-metal contact.
  • an anti-seize composition that includes lubricating solids and at least one of a material selected from a grease and an oil.
  • the lubricating solids include at least 15 weight percent of nano-sized lubricating solid particles, desirably at least 20 weight percent of nano-sized particles.
  • the nano-sized lubricating solid particles each have at least one dimension, on average, of less than 500 ran.
  • the nano-sized lubricating solid particles may each have at least one dimension, on average, of less than 100 nm, desirably less than 50 nm.
  • the nano-sized lubricating solid particles may include metallic particles.
  • the metallic particles may include at least one of a material selected from copper, aluminum, nickel and alloys and combinations thereof.
  • the nano-sized lubricating solid particles may include at least one of a material selected from graphite, molybdenum disulfide, tungsten disulfide, zirconium oxide, cerium oxide, tin oxide, magnesium oxide, calcium oxide and combinations thereof.
  • the nano-sized lubricating solid particles may include amorphous nanoparticles, nanopowders, nanotubes, nanocrystals, and combinations thereof, which may be constructed of non- metallic materials, such as polytretrafluoroethylene and mica.
  • the grease may include a mineral oil thickened with at least one of a material selected from sodium, aluminum, calcium, lithium and combinations thereof.
  • the grease may include an oil thickened with at least one of a material selected from a bentonite clay, a silica, a polymer and combinations thereof.
  • the grease may include a synthetic oil thickened with at least one of a material selected from a silica, a polymer, a metallic soap and combinations thereof.
  • the oil may include at least one of a material selected from a mineral oil, a synthetic oil and combinations thereof.
  • the synthetic oil may include at least one material selected from a silicone, an ester, an olefin, a glycol, a polybutene and combinations thereof.
  • the anti-seize composition may include at least one polymeric thickener, such as a polyamide.
  • the inventive composition may be in liquid form; the composition may be in aerosol form; the composition may be in paste, or the composition may be in stick form.
  • the composition may include at least one suspending agent.
  • the suspending agent may include a silica.
  • the anti-seize composition may include at least one additive selected from the group consisting of an anti- corrosion additive, an extreme pressure additive, and an antioxidant additive.
  • the composition may have a Mil-907-E breakaway torque ranging from 50 to 200 foot-pounds.
  • a method of preparing a composition useful for anti-seize and /or lubricating purposes includes selecting a lubricating solid having at least 15 weight percent of nano-sized lubricating solid particles, wherein the nano-sized lubricating solid particles each have at least one dimension, on average, of less than 500 nm.
  • the method further includes selecting at least one grease or an oil and mixing the lubricating solid with the at least one of a grease or an oil.
  • a method of using a composition useful for anti-seize and /or lubricating purposes includes obtaining an anti-seize /lubricating composition including lubricating solids and at least one of a material selected from the group consisting of a grease and an oil, wherein the lubricating solids include at least 15 weight percent of nano-sized lubricating solid particles, and where the nano-sized lubricating solid particles each have at least one dimension, on average, of less than 500 nm.
  • the method further includes applying a portion of the anti- seize /lubricating composition onto a surface and matingly engaging the surface with a complementary surface.
  • the present invention is directed to anti-seize/ lubricating compositions and to methods of preparing and using a composition useful for anti-seize and /or lubricating purposes.
  • the anti-seize /lubricating composition of the present invention includes lubricating solids that incorporate nano-sized lubricating solid particles. It is expected that utilizing nano-sized lubricating solid particles in lubricating solids will lend improved properties to the anti-seize /lubricating compositions, such as superior lubricity and superior torque tension controlling properties, which may result in more uniform clamping loads on assembly joints. This may prove to be particularly useful in critical boiling applications such as nuclear power plants, fossil fuel plants, aerospace applications and refineries.
  • a nano-sized particle is defined as a particle with at least one dimension being less than 500 nm.
  • the present invention also encompasses agglomerates of nano-sized particles, i.e. clumps of one or more nano-sized particles, as long as most of the surface area of the individual nano-sized particles is maintained.
  • Average particle dimension of the nano-sized particles may range from 0 to 500 nm. It is expected that average particle dimensions may typically range from 10 to 200 nm, and more typically, from 20 to 100 nm.
  • An anti-seize/ lubricating composition of the present invention includes lubricating solids.
  • a lubricating solid may be any particulate matter that decreases the coefficient of friction between sliding parts.
  • lubricating solids may not provide as low a friction coefficient as can be obtained with fluid films, in general, lubricating solids are relatively independent of the relative speed of the sliding parts.
  • lubricating solids can be effectively used for relatively slow sliding speeds of the parts, for reciprocating motion of the sliding parts and when relatively heavy loads are applied to the sliding parts.
  • Lubricating solids also typically remain more effective at elevated temperatures than do liquid lubricants.
  • Lubricating solids Unlike liquid lubricants, which may burn off at elevated temperatures thereby leaving the sliding parts without lubrication or with greatly reduced lubrication, lubricating solids remain in place and continue to provide lubrication at these elevated temperatures. Lubricating solids also generally provide excellent boundary lubrication, as compared to liquid lubricants, staying in place and not migrating or being squeezed out from between the sliding parts.
  • Lubricating solids may be metallic or non-metallic lubricants, and may be provided in a powder, particulate or flake form. Typically, it is desirable that these lubricating solids having high melting points.
  • Typical lubricating solids may include, by way of non-limiting examples, copper, aluminum, nickel, graphite, molybdenum, molybdenum disulfide, tungsten disulfide, zirconium oxide, cerium oxide, boron nitride, polytetrafluoroethylene, mica, calcium oxide, calcium fluoride, zinc oxide, tin oxide, magnesium oxide, and /or any combination of the above.
  • the selection of the specific lubricating solid(s) will depend upon the desired end properties of the anti-seize/ lubricating composition.
  • lubricating solids Properties that may influence the selection of lubricating solids include, by way of non-limiting examples, desired temperature resistance, thermal conductivity, lubricity, chemical reactivity, and chemical resistance of the composition, the material properties of the working parts and cost.
  • copper as a lubricating solid would typically not be desired when there is the possibility that the anti-seize /lubricating composition would be exposed to ammonia, as in some chemical processing plants, or to platinum catalysts, as in some refinery operations.
  • nickel, graphite and /or calcium oxide as the lubricating solid(s) may be preferred.
  • nickel or calcium oxide may be used for extreme high-temperature applications (up to 2400 0 F); while molybdenum disulfide may be more appropriate for less extreme high- temperature applications (up to about 750 0 F).
  • not all solids in flake, particulate or powder form may be considered to be lubricating solids.
  • certain fillers used in known grease formulations may have relatively poor lubricating properties.
  • silica gels, carbon black and bentonite clay have poor lubricity, but are provided in some grease formulations as thickeners and, possibly, to provide higher temperature resistance. Carbon black may also be provided to improve the conductivity of the grease.
  • These known grease thickeners i.e. silica gels, carbon black and bentonite clay
  • An anti-seize/ lubricating composition of the present invention includes a material selected from the group consisting of a grease and an oil.
  • the composition may include a grease.
  • Greases are semi-fluid, semi-solid materials typically used to deliver a lubricant.
  • Grease generally consists of a thickener and a liquid lubricant dispersed within the thickener.
  • the manufacture of grease typically involves a chemical reaction.
  • a soap-based grease may be a mixture of a fluid lubricant, usually a petroleum oil or a synthetic oil, dispersed in a soap thickener. Soap thickeners may be formed by reacting, i.e.
  • a complex soap is formed by the reaction of an alkali with a high-molecular-weight fat or fatty acid to form soap, and the simultaneous reaction of the alkali with a short-chain organic or inorganic acid to form a metallic salt (the complexing agent).
  • Complexing agents usually increase the dropping point of grease.
  • Lithium, calcium, and aluminum greases are common alkalis in complex-soap greases.
  • Non-soap thickeners such as clays, silica gels, carbon black, and various synthetic organic materials may also be used in grease manufacture. Any of various liquid lubricants or base oils may be dispersed within the thickener. Commonly, a mineral oil, a synthetic oil, or a vegetable oil is used depending upon the application.
  • Consistency or penetration of grease is a measure of the consistency of grease, utilizing a penetrometer. Penetration is reported as the tenths of a millimeter (penetration number) that a standard cone, acting under the influence of gravity, will penetrate the grease sample under test conditions prescribed by test method ASTM D 217. Standard test temperature is 25 0 C (77 0 F). The higher the penetration number, the softer the grease. Undisturbed penetration is the penetration of a grease sample as originally received in its container. Unworked penetration is the penetration of a grease sample that has received only minimal handling in transfer from its original container to the test apparatus.
  • Worked penetration is the penetration of a sample immediately after it has been subjected to 60 double strokes in a standard grease worker; other penetration measurements may utilize more than 60 strokes.
  • Block penetration is the penetration of block grease (grease sufficiently hard to hold its shape without a container).
  • additives may be added to greases to improve or modify their characteristics.
  • additives may be used to provide or improve dropping point, thermal stability, shear stability, resistance to water washout, antioxidant or oxidation stability, corrosion resistance, and anti-wear properties.
  • lubricating solids are incorporated into some standard grease formulations.
  • a food grade grease may contain around 5 weight percent or less of zinc oxide.
  • an extreme pressure (EP) grease may contain around 5 weight percent or less of molybdenum sulfide.
  • both the zinc oxide and the molybdenum sulfide act as lubricating solids.
  • Greases useful in forming the anti-seize/ lubricating composition of the present invention may include, by way of non-limiting examples, at least a mineral oil and /or a synthetic oil.
  • a mineral oil is an oil that is manufactured from crude oil that has undergone a variety of complex separation processes.
  • a synthetic oil is an oil created by the chemical reaction of several ingredients, for example, esters and synthetic hydrocarbons.
  • Synthetic oils include semi-synthetic oils, which are mixtures of synthetic oils and non-synthetic oils.
  • Greases useful in forming the anti-seize /lubricating composition of the present invention may also include, by way of non-limiting examples, an oil thickened with a bentonite clay, a silica and /or a polymer.
  • Bentonite clay is a chemically (amine) treated clay.
  • a Silicas refer to fumed silica.
  • Typical polymers used for thickening grease include polyurea, fluorocarbon and polybutene.
  • Greases useful in forming the anti-seize/ lubricating composition of the present invention may further include, by way of non-limiting examples, one or more mineral oils thickened with sodium, aluminum, calcium and /or lithium. Such metal-thickened mineral oils typically have minimum oil separation, higher dropping properties, good water resistance, oxidation stability and corrosion resistance, among other properties.
  • Other greases useful in forming the anti-seize/ lubricating composition of the present invention may include, by way of non-limiting examples, one or more synthetic oils thickened with a silica, a polymer and /or a metallic soap.
  • a metallic soap is formed by the neutralization of a weak fatty acid by a strong base, in a processes known as saponification.
  • Metallic soap thickened, synthetic oil greases are particularly useful for low- as well as high-temperature resistance applications.
  • Polymer thickened, synthetic oil-based greases include polyurea greases, which are particularly useful as ball bearing greases.
  • other greases as may be suitable for a specific application, may be used without departing form the spirit of the invention.
  • the anti-seize/ lubricating composition of the present invention may include an oil.
  • the oil serves to control, in part, the spreadability of the composition.
  • Useful oils include petroleum oils, mineral oils, and synthetic oils, such as silicone oils, ester-based oils, olefin-based oils, glycol oils, polybutene- based oils, and the like.
  • Various additives may be added to the oils to improve or modify their characteristics. As with the greases described above, additives may be used to provide or improve antioxidant, anti corrosion, and anti-wear properties, among other properties.
  • Oils useful in forming the anti-seize /lubricating composition of the present invention may further include, by way of non-limiting examples, a synthetic oil which includes one or more silicones, esters, olefins, glycols and /or polybutene.
  • Silicon-based synthetic oils generally have excellent oxidation and viscosity stability.
  • Ester-based synthetic oils generally have good fire resistance.
  • Olefin-based synthetic oils generally have good lubricity.
  • Glycol-based synthetic oils are generally have no effect on rubber gaskets.
  • Polybutene-based synthetic oils are generally clean burning without residue.
  • other oils may be used without departing form the spirit of the invention.
  • the lubricating solids of the present invention include nano-sized lubricating solid particles.
  • Nano-sized particles or nanoparticles are characterized as particles having at least one dimension of less than 500 nm. Notably, it appears that novel properties differentiating nanoparticles from bulk material develop at this critical length scale.
  • the measured dimension corresponds to a structural feature such as a width, length, height, thickness, diameter, etc. of the particle.
  • These characteristic dimensions of nano-sized particles may be measured using any suitable method, including for example, dynamic light scattering (DLS), photon correlation spectroscopy (PCS), quasi-elastic light scattering (QELS) or X- Ray Diffraction (XRD).
  • DLS dynamic light scattering
  • PCS photon correlation spectroscopy
  • QELS quasi-elastic light scattering
  • XRD X- Ray Diffraction
  • scanning probe microscopes including atomic force microscopes (AFM) may be used to determine the average dimensions of the nano-sized particles.
  • An AFM can easily measure particle dimensions of greater than 100 nm, and can measure particle dimension of from 1 to lOOnm with special considerations.
  • the lubricating solids of the inventive anti-seize/ lubricating compositions include nano-sized lubricating solid particles in an amount greater than 15 weight percent based on the total weight of the lubricating solids.
  • the weight of the lubricating solids does not include the weight of the grease and /or oil, themselves, or any non-lubricating additives to the grease and /or oil.
  • grease thickeners such as carbon black or silica gels, which may include solid particles, are not included in the weight of the lubricating solids.
  • lubricating solids such as the zinc oxide lubricating solid discussed above with respect to certain food grade greases and the molybdenum sulfide lubricating solid discussed above with respect to certain extreme pressure greases, these pre-mixed lubricating solids are included in the total weight of the lubricating solids.
  • nano-sized lubricating solid particles in the lubricating solids When the amount of nano-sized lubricating solid particles in the lubricating solids is at or above about 15 weight percent of the lubricating solids, it is expected that the characteristics of the lubricating solids, will begin to be influenced by the characteristics of the nano-sized particles. At or above about a 20 weight percent of nano-sized particles in the lubricating solids, it is expected that the effects of the nano-sized lubricating solid particles will be even more pronounced. When nano-sized lubricating solid particles comprise from 30 to 40 weight percent of the lubricating solids, given the present costs associated with nano-sized particles, it is expected that the maximum cost benefit of including nano-sized lubricating solid particles in the lubricating solids will have been exceeded.
  • the remaining weight percent of the lubricating solids may be made up of conventional particles or other solid materials, without limitation. In the limiting case, for special applications, up to 100 weight percent of the lubricating solids may be comprised of nano-sized lubricating solid particles.
  • the nano-sized lubricating solid particles of the lubricating solids may include metallic or non-metallic particles.
  • nano-sized metallic particles include copper, aluminum, and nickel.
  • Other useful nano-sized lubricating solid particles may include graphite, molybdenum, molybdenum disulfide, tungsten disulphide, zirconium oxide, cerium oxide, tin oxide, magnesium oxide, calcium oxide, mica, and combinations thereof.
  • the nano-sized lubricating solid particles may be of any form, including, nanopowders, nanotubes, nanocrystals, and combinations thereof.
  • Nanopowders as used herein, are powders composed of nano-sized particles having an average diameter below 50nm. The individual particles of nanopowders are generally free to move in relationship with each other and, accordingly, when not in liquid suspension resemble smoke particles.
  • Nanotubes can be multi-walled generally cylindrical particles or single-walled generally cylindrical particles. They typically have a diameter-to-length ratio from about 5 to 20, although they are not limited to these ratios.
  • a nanocrystal is a crystalline material, as opposed to amorphous, with dimensions measured in nanometers.
  • Nanocrystals can be inorganic, for example, composed of germanium, or organic, for example, composed of DAST (trans-4-[4-(dimethylamino)]stilbezolium-p- toluenesulfonate).
  • Organic nanocrystals are basically an aggregate of organic molecules that are orderly arranged in alignment.
  • the average characterizing dimension of the nano-sized particles may be considerably less than 500 run.
  • the nano-sized particles may have at least one dimension, on average, of less than 100 nm. It may also be desirable to have even smaller nano-sized particles.
  • the nano-sized particles may have at least one dimension, on average, of less than 50 nm. The smaller the average minimum dimension, the more surface area per unit volume of nano-sized particles, and thus the more likely that the nano-particles will exhibit properties dependent upon surface characteristics.
  • the present invention may also include certain additives, including but not limited to anti-corrosion, extreme pressure (EP), and antioxidant additives.
  • additives including but not limited to anti-corrosion, extreme pressure (EP), and antioxidant additives.
  • examples of commercially available additives include the anticorrosion additive: Vanlube® RI-BA, the extreme pressure additive: Molyvan® L, and the antioxidant additive: Vanlube® AZ, all supplied by R.T. Vanderbilt Co., Inc. of Norwalk, CT.
  • the anti-seize/ lubricating composition may include a polymeric thickener, which may include a polyamide, such as those commercially available as a non-reactive free flowing powder under the trade name DISPARLON® 6200, 6100 and 6500 from King Industries Specialties Company of Norwalk, CT.
  • the recommended use in accordance with commercially available data sheets for DISPARLON® 6200 is for epoxy adhesive and potting compounds in amounts of about 0.5% to about 3% by weight; the recommended use in accordance with commercially available data sheets for DISPARLON® 6500 is for epoxy adhesive and potting compounds in amounts of about 0.5% to about 3% by weight.
  • the inventive compositions include the polymeric thickener in amounts of about 2.5% to about 20%, for instance about 5% to about 15%, such as about 7% to about 10%, by weight of the total composition.
  • the non-flowability characteristics of a composition can be obtained with minimal undesirable effects, such as loss of substantial tensile properties or sealing characteristics.
  • these materials can be added directly in solid form, such as in powder or particulate form, without pre-melting of the particles or even heating of the polymerizable compounds. It is often practical, however, to slightly heat the polymerizable compounds before or after incorporating the polymeric thickener for the sake of expediency. This is not necessary to obtain the non-flowable characteristics but is used as a practical and expedient processing measure.
  • the polyamide materials of the present invention desirably have a particle size less than about 15 microns, although other particle sizes are useful.
  • the melting or softening point of the polymeric thickener ranges from about 200 0 F (93°C) to about 500°F (260 0 C).
  • a polyamide having a melting point of about 250°F-270°F (121°C- 132°C) and desirably about 260 0 F (127°C) is employed.
  • the polymeric thickener may further include polyamides, polyacrylamides, polyimides, and polyhydroxyalkylacrylates.
  • a more particular description of a urea-urethane includes a combination of an alkali metal cation and the reaction product of (a) a polyfunctional isocyanate and an hydroxy and an amine; or (b) a phosgene or phosgene derivative, and a compound having 3 to 7 polyethylene ether units terminated at one end with an ether group and at the other end with a reactive functional group selected from an amine, an amide, a thiol or an alcohol; or (c) a monohydroxy compound, a diisocyanate and a polyamine.
  • reaction product described in (c) When the reaction product described in (c) is employed it is generally formed by first reacting a monohydroxy compound with a diisocyanate to form a mono-isocyanate adduct, and subsequently reacting the mono-isocyanate reaction product with a polyamine in the presence of an alkali metal salt and aprotic solvent, as described in U.S. Patent No. 4,314,924, the disclosure of which is hereby expressly incorporated herein by reference.
  • a commercially available version of the reaction product described in (c) is believed to be BYK®-410, from BYK-Chemie, of Wallingford, CT. BYK-Chemie describes this reaction product as a urea-urethane.
  • Useful isocyanates for forming the reaction product(s) of the additive include polyisocyanates such as phenyl diisocyanate, toluene diisocyanate, 4,4'- diphenyl diisocyanate, 4,4'-diphenylene methane diisocyanate, dianisidine diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenyl ether diisocyanate, p- phenylene diisocyanate, 4,4'-dicydo-hexylmethane diisocyanate, 1,3-bis- (isocyanatomethyl) cydohexane, cyclohexylene diisocyanate, tetrachlorophenylene diisocyanate, 2,6-diethyl-p-phenylenediisocyanate, and 3,5- diethyl-4,4'-diisocyanatodiphenylmethane.
  • polyisocyanates that may be used are polyisocyanates obtained by reacting polyamines containing terminal, primary and secondary amine groups or polyhydric alcohols, for example, the alkane, cycloalkane, alkene and cydoalkane polyols such as glycerol, ethylene glycol, bisphenol-A, 4,4'-dihydroxy-phenyldimethylmethane-substituted bisphenol-A, and the like, with an excess of any of the above-described isocyanates.
  • polyamines containing terminal, primary and secondary amine groups or polyhydric alcohols for example, the alkane, cycloalkane, alkene and cydoalkane polyols such as glycerol, ethylene glycol, bisphenol-A, 4,4'-dihydroxy-phenyldimethylmethane-substituted bisphenol-A, and the like, with an excess of any of the above-described isocyanates.
  • Useful alcohols for reacting with the polyisocyanates also indude polyethyl glycol ethers having 3-7 ethylene oxide repeating units and one end terminated with an ether or an ester, polyether alcohols, polyester alcohols, as well as alcohols based on polybutadiene.
  • the spedfic type of alcohol chosen and the molecular weight range can be varied to achieve the desired effect.
  • monohydroxy compounds, straight or branched chain aliphatic or cyclic primary or secondary alcohols containing C 5-25 , and alkoxylated derivatives of these monohydroxy compounds are useful.
  • Phosgene and phosgene derivatives such as bischloroformates, may be used to make the reaction product of the additive (c). These compounds are reacted with a nitrogen-containing compound, such as an amine, an amide or a thiol to form the adduct. Phosgenes and phosgene derivatives may also be reacted with an alcohol to form the reaction product.
  • a nitrogen-containing compound such as an amine, an amide or a thiol
  • the alkali metal cations are usually provided in the form of a halide salt.
  • a halide salt for example, sodium, potassium and lithium halide salts are useful.
  • sodium chloride, sodium iodide, sodium bromide, potassium chloride, potassium iodide, potassium bromide, lithium chloride, lithium iodide, lithium bromide and combinations thereof may be employed.
  • the reaction products of additive (c) of the present invention are usually present in and added to the composition with an alkali metal salt, in a solvent carrier.
  • the solvents are desirably polar aprotic solvents in which the reaction to form the reaction product was carried out.
  • N-methyl pyrrolidone, dimethylsulfoxide, hexamethylphosphoric acid triamide, N, N- dimethylformamide, N,N,N',N'-tetramethylurea, N,N-dimethylacetamide, N- butylpyrrolidone, tetrahydrofuran and diethylether may be employed.
  • One particularly desirable additive is the combination of a lithium salt and a reaction product which is formed by reacting a monohydroxy compound with a diisocyanate compound to form a mono-isocyanate first adduct, which is subsequently reacted with a polyamine in the presence of lithium chloride and 1- methy-2-pyrrolidone to form a second adduct.
  • a commercially available additive of this sort is sold by BYK-Chemie, of Wallingford, CT under the tradename BYK® 410. This commercially available additive is described by BYK-Chemie product literature as being a urea urethane having a minor amount of lithium chloride present in a l-methyl-2 pyrrolidone solvent.
  • Amines which can be reacted with phosgene or phosgene derivatives to make the reaction product include those which conform to the general formula R ⁇ -NH 2 , where R 11 is aliphatic or aromatic.
  • Desirable aliphatic amines include polyethylene glycol ether amines.
  • Desirable aromatic amines include those having polyethylene glycol ether substitution on the aromatic ring.
  • JEFF AMINE® commercially available amines sold under the tradename JEFF AMINE® by Huntsman Corporation of Houston, TX, may be employed. Examples indude JEFF AMINE® D-230, JEFF AMINE® D-400, JEFF AMINE® D- 2000, JEFF AMINE® T-403, JEFF AMINE® ED-600, JEFF AMINE® ED-900, JEFF AMINE® ED-2001, JEFF AMINE® EDR-148, JEFF AMINE® XTJ-509, JEFF AMINE® T-3000, JEFF AMINE® T-5000, and combinations thereof.
  • the JEFF AMINE® D series are diamine based products and may be represented by:
  • the JEFF AMINE® T series are trifunctional amine products based on propylene oxide and may be represented by:
  • the JEFF AMINE® T-403 product is a trifunctional amine and may be represented by:
  • the JEFF AMINE® ED series are polyether diamine-based products and may be represented by:
  • Amides useful for reacting with the phosgene or phosgene derivatives include those which correspond to the following formula:
  • R 12 may be an aliphatic or aromatic, substituted or unsubstituted, hydrocarbon or heterohydrocarbon, substituted or unsubstituted, having C 1-36 .
  • Alcohols useful in forming the reaction product with the phosgene or phosgene derivatives include those described above.
  • Another polymeric thickener useful herein includes hydroxyl-, amine- or amide-modified aliphatic hydrocarbons and polyester-amide based rheological additives.
  • Hydroxy-, amine- or amide-modified aliphatic hydrocarbons include THIXCIN® R, THIXCIN® GR, THIXATROL® ST and THIXATROL® GST, each of which available from Rheox Inc. of Hightstown, NJ.
  • These modified aliphatic hydrocarbons are castor oil based materials.
  • the hydroxyl modified aliphatic hydrocarbons are partially dehydrated castor oil or partially dehydrated glycerides of 12-hydrostearic acid. These hydrocarbons may be further modified with polyamides to form polyamides of hydroxyl stearic acid, and are described as being useful polyamides.
  • Polyester-amide based rheolgical additives include THIXATROL® TSR, THIXATROL® SR and THIXATROL® VF rheological additives available from Rheox Inc., Hightstown, NJ. These rheological additives are described to be reaction products polycarboxylic acids, polyamines, alkoxylated polyols and capping agents. Useful polycaboxylic acids include sebadc add, poly(butadiene) dioic adds, dodecane dicarboxylic add and the like. Suitable polyamines indude diamine adkyls. Capping agents are described as being monocarboxylic adds having aliphatic unsaturation.
  • the anti-seize composition may indude at least one suspending agent, which may indude silica.
  • the silica may be a fumed silica.
  • An example of a fumed silica is Cab-O-Sil® M-5 by Cabot Corp. of Boston, MA.
  • the anti-seize /lubricating composition of the present invention may be manufactured in liquid, aerosol, paste, or stick form.
  • the liquid formulation may, for example, be formed by mixing petroleum or synthetic oil with the lubricating solids, which indude nano-sized partides.
  • the aerosol formulation may, for example, be formed by diluting anti-seize paste having lubricating solids, which indude nano-sized partides, with faster drying solvent and a propellant.
  • the paste formulation may, for example, be formed by mixing grease and oil with lubricating solids, which include nano-sized partides.
  • the stick formulation may, for example, be formed by mixing grease and oil with a polymeric thickener and with lubricating solids, which indude nano-sized partides.
  • the anti-seize /lubricating composition may optionally have a Mil-907-E breakaway torque ranging form 50 to 200 foot-pounds.
  • One method for preparing the composition of the present invention could include the steps of (1) selecting a lubricating solid having at least 15 weight percent of nano-sized lubricating solid particles having least one dimension, on average, of less than 500 nm; (2) selecting a grease and/ or an oil; (2) and mixing the lubricating solid with the oil and/ or grease.
  • One method for using the composition of the present invention could include the steps of (1) selecting an anti-seize/ lubricating composition having a grease and /or oil and lubricating solids, wherein the lubricating solids include at least 15 weight percent of nano-sized lubricating solid particles having at least one dimension of at least one structural feature of less than 500 nm, and (2) applying a portion of the anti-seize lubricating composition onto a surface and matingly engaging the surface with a complementary surface.
  • the surface may be a threaded surface.

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  • Lubricants (AREA)

Abstract

Composition anti-grippage contenant des solides lubrifiants et au moins l'un des matériaux choisis parmi une graisse et une huile. Les solides lubrifiants comprennent au moins 15 pour cent de nanoparticules solides lubrifiantes. Lesdites nanoparticules solides lubrifiantes ont chacune au moins une dimension, en moyenne, inférieure à 500 nm.
PCT/US2007/024481 2006-12-01 2007-11-28 Composition anti-grippage avec nanoparticules solides lubrifiantes WO2008069936A1 (fr)

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CN113025289A (zh) * 2019-12-09 2021-06-25 中国石油化工股份有限公司 一种钻井液润滑剂及其制备方法
CN114276864A (zh) * 2021-12-30 2022-04-05 二重(德阳)重型装备有限公司 水性不锈钢紧固件防卡咬剂及其制备方法
CN114423850A (zh) * 2019-09-18 2022-04-29 株式会社捷太格特 润滑脂组合物和滚动轴承
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WO2010097778A1 (fr) 2009-02-27 2010-09-02 Total Raffinage Marketing Composition de graisse
CN101974361A (zh) * 2010-08-20 2011-02-16 泰安天健应用技术推广中心 一种多功能纳米复合材料抗磨剂
CN101967418A (zh) * 2010-10-19 2011-02-09 陈玉祥 一种油性纳米超硬粉体悬浮液及其制备方法
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