WO2005060648A2 - Lubrifiants a thermoconductivite amelioree contant un nanomateriau - Google Patents

Lubrifiants a thermoconductivite amelioree contant un nanomateriau Download PDF

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Publication number
WO2005060648A2
WO2005060648A2 PCT/US2004/042109 US2004042109W WO2005060648A2 WO 2005060648 A2 WO2005060648 A2 WO 2005060648A2 US 2004042109 W US2004042109 W US 2004042109W WO 2005060648 A2 WO2005060648 A2 WO 2005060648A2
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Prior art keywords
thermal conductivity
graphite
oil
viscosity
fluid
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PCT/US2004/042109
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English (en)
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WO2005060648A3 (fr
Inventor
Zhiqiang Zhang
Gefei Wu
Frances E. Lockwood
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Ashland Inc.
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Publication of WO2005060648A3 publication Critical patent/WO2005060648A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/02—Carbon; Graphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • the invention relates to the field of providing lubricants and functional fluids containing nanomaterial dispersed within automatic transmission fluids, power transmission fluids, and hydraulic steering fluids which exhibit enhanced thermal conductivity as compared to conventional fluids without the nanomaterial dispersions.
  • Lubricants and coolants of various types are used in equipment and in manufacturing processes to remove waste heat, among other functions.
  • water is most preferred for heat removal, however, to expand it's working temperature range, freezing point depressants such as ethylene glycol and/or propylene glycol are added, typically at levels above 10% concentration by volume.
  • freezing point depressants such as ethylene glycol and/or propylene glycol are added, typically at levels above 10% concentration by volume.
  • automotive coolant is typically a mixture of 50-70% ethylene glycol, and the remainder is water.
  • the thermal conductivity of the freezing point depressed fluid is then about two-thirds (2/3) as good as water alone, as illustrated in Table 1.
  • water can not be used for various reasons, such as corrosion, temperature restriction, etc., and then a type of oil, e.g., mineral oil, polyalphaolefin, ester synthetic oil, ethylene oxide/propylene oxide synthetic oil, polyalkylene glycol synthetic oil, etc. is used.
  • the thermal conductivity of these oils is typically 0.12 to 0.16 W/m-K (Watts/meter Kelvin) at room temperature, and thus they are inferior as heat transfer agents to water, since water has a much higher thermal conductivity, 0.61 W/m-K as set forth in Table 1.
  • these oils have many other important functions, and they are carefully formulated to perform to exacting specifications for example for friction and wear performance, low temperature performance, fuel efficiency performance etc.
  • Often designers will desire a fluid with higher thermal conductivity than the conventional oil, but are restricted to oil due to the many other parameters the fluid must meet.
  • graphite in fluids such as lubricants is well known.
  • the graphite is added as a friction reducing agent, which also carries some of the load imposed on the working fluid, and therefore helps to reduce surface damage to working parts.
  • the graphite layered structure In order to be low friction, it is well known that the graphite layered structure must contain some water or other material to create the interlayer spacing and thereby lamellar structure.
  • graphite suspensions e.g., from Acheson Colloid Co., which are specifically intended for use in lubricants.
  • the size of the particles is varied for different dispersions, but the minimum average size for commercially available products is in the submicron range, typically mean as 500-800 nm (nanometers).
  • the thermal advantage of the graphite is not mentioned in the sales literature, nor is the product sold or promoted for its thermal conductivity property.
  • the graphite had some settling tendency in the fluid.
  • Graphite of this size also significantly affects the friction and wear properties of the fluid, and heretofore has been used to reduce friction and improve wear performance of the fluid, e.g. in metalworking fluids.
  • the use of graphite in lubricants for recirculating systems was made unpopular, partly due to evidence that micron size graphite could "pile up" in restricted flow areas in concentrated contacts, thereby leading to lubricant starvation. No recognition ofeffect of graphite particle size on this phenomena was made.
  • Graphite powders can be obtained from UCAR Carbon Company Inc., with thermal conductivity 10-500 W/m-K, and typically > 80 W/m-K, and from Cytec
  • Carbon Fibers LLC with thermal conductivity 400-700 W/m-K. These bulk materials must be reduced to a nanometer-sized powder by various methods for use in the instant invention.
  • Utilization of these inexpensive sources of nanomaterials have not been released in lubrication formulations before and a point of novelty in the instant invention is the ability to reduce the graphite to produce an inexpensive nanomaterial having a particle size suitable for long term dispersion in lubricating compositions and the method of dispersing same.
  • ATF Automatic transmission fluids
  • power transmission fluids and hydraulic steering fluids have stringent requirements for viscosity, stability to oxidation, temperature and shear, low temperature fluidity, and static and dynamic coefficient of friction and their relative levels over many shift cycles. Additionally, the heat transfer requirements in transmissions and pumps are significant. It is generally necessary to use some form of cooling for the transmission fluid, and some designs of transmissions are prevented due to insufficient capability to eliminate waste heat. Because of the friction control requirements, and the relatively large particle size of conventional graphite dispersions, the use of graphite in these fluids is not known.
  • ATF automatic transmission fluids
  • power transmission fluids power transmission fluids
  • hydraulic steering fluids examples and further discussion will focus on automatic transmission fluids; however, the claims are applicable to the power transmission fluids, hydraulic steering fluids, and other types of oil based noncompressible fluids as well.
  • automatic transmission fluids of enhanced thermal conductivity are prepared by dispersing nanometer-sized carbon nanomaterials of thermal conductivity higher than 80 W/m-K into the fluid.
  • carbon nanomaterials used in this invention refers to graphite nanoparticles, carbon nanotubes or fibrils, and other nanoparticles of carbon with graphitic structure. Stable dispersion is achieved by physical and chemical treatments.
  • the instant invention provides a method for making a composition for an automatic transmission fluids that have enhanced thermal conductivity, up to 80% greater than their conventional analogues.
  • One preferred composition contains an effective amount of at least one base oil such as mineral oil, hydrocracked mineral oil with high viscosity index, vegetable derived oils, polyalphaolefins, poly- internal-olefins, polyalkylglycols, polycyclopentadienes, propylene oxide or ethylene oxide based synthetics, silicone oils, phosphate esters or other synthetic esters, or any suitable base oil; an effective amount of at least one type of nanomaterial, preferably graphite nanoparticle or carbon nanotubes, and an effective amount of at least one dispersing agents or surfactants for the purpose of stabilizing the nanoparticles.
  • base oil such as mineral oil, hydrocracked mineral oil with high viscosity index, vegetable derived oils, polyalphaolefins, poly- internal-olefins, polyalkylglycol
  • One preferred nanomaterial is a high thermal conductivity graphite, exceeding 80W/m-K in thermal conductivity, and ground, milled, or naturally prepared with mean particle size less than 500 nm in diameter, and preferably less than 100 nm, and most preferably less than 50 nm.
  • the graphite is dispersed in the fluid by one or more of various methods, including ultrasonication, milling, and chemical dispersion.
  • nanoparticles can be selected from any metal from the Group IV elements, such as carbon materials (carbon nanotubes, fullerenes, graphite, amorphous carbon, carbon particles, carbon fibrils and combinations thereof, etc.), silicone carbide, and clay materials, metal (including transition metals) particles (such as silver, copper, aluminum, etc.), metal oxides, alloy particles, and combinations thereof may be applicable to the instant invention.
  • carbon nanotubes with a graphitic structure are another preferred type of nanomaterial or particles.
  • the thermal conductivity enhancement compared to the fluid without graphite, is proportional to the amount of nanomaterials added.
  • the graphite nanoparticles or nanotubes contribute to the overall fluid viscosity, partly or completely eliminating the need for viscosity index improvers and providing a very high viscosity index.
  • Particle size and dispersing chemistry is controlled to get the desired combination of viscosity and thermal conductivity increase from the base oil while controlling the amount of temporary viscosity loss in shear fields.
  • the resulting fluids have unique properties due to the high thermal conductivity and high viscosity index of the suspended particles, as well as their small size.
  • the present invention provides at a minimum, a fluid of lubricant containing less than 10% by weight graphite nanoparticles.
  • a fluid of lubricant containing less than 10% by weight graphite nanoparticles.
  • aminimumof one or more chemical dispersing agents and/or surfactants is also added to achieve long term stability.
  • dispersant in the instant invention refers to a surfactant added to a medium to promote uniform suspension of extremely fine solid particles, often of colloidal size.
  • dispersant is generally accepted to describe the long chain oil soluble or dispersible compounds which function to disperse the "coldsludge" formed in engines.
  • ITietermsurfactanti einstantinvention refers to any chemical compound that reduces surface tension of a liquid when dissolved into it, or reduces interfacial tension between two liquids or between a liquid and a solid. It is usually, but not exclusively, a long chain molecule comprised of two moieties; a hydrophilic moiety and a lipophilic moiety.
  • hydrophilic and lipophilic moieties refer to the segment in the molecule with affinity for water, and that with affinity for oil, respectively. These two terms, dispersant and surfactant, are mostly used interchangeably in the instant invention for often a surfactant has dispersing characteristics and many dispersants have the ability to reduce interfacial tensions.
  • U.S. Patent 6,783,746 by Zhang et al. teach methods of dispersing nanomaterial in fluids to obtain stable dispersions and is hereby incorporated by reference herein.
  • the particle-containing fluid of the instant invention will have a thermal conductivity higher than the neat fluid, wherein the term 'neat' is defined as the fluid before the particles are added.
  • the fluid can have other chemical agents or other type particles added to it as well to impart other desired properties, e.g. friction reducing agents, antiwear or anticorrosion agents, detergents, antioxidants, dispersants to define a lubricant composition suitable for use in vehicle applications or the like.
  • friction reducing agents e.g. friction reducing agents, antiwear or anticorrosion agents, detergents, antioxidants, dispersants to define a lubricant composition suitable for use in vehicle applications or the like.
  • fluid in the instant invention is broadly defined to include pastes, gels, greases, and liquid crystalline phases in either organic or aqueous media, emulsions and microemulsions.
  • U.S. Patent 4,029,587 by Koch teaches the use of a variety additives for functional fluids applicable to the present invention and is hereby incorporated by reference in its entirety.
  • U.S. Patent 4,116,877 by Outten et al. teaches the use of a variety additives for hydraulic fluids such as automatic transmission fluids and power steering fluids applicable to the present invention and is hereby incorporated by reference in its entirety.
  • the preferred carbon nanomaterials are selected from graphitic carbon structures withbulkthermal conductivity exceeding 80 W/m-K.
  • Apreferred form of carbon nanomaterials is carbon nanotubes.
  • Another preferred form of carbon nanomaterials is high thermal conductivity graphite.
  • a preferred form ofthe high thermal conductivity graphite is POCO FOAM from Poco Graphite.
  • Another preferred form of high thermal conductivity graphite is graphite powders from UCAR Carbon Company Inc.
  • Still another preferred form of high thermal conductivity graphite is graphite powders from Cytec Carbon Fibers LLC.
  • Still another preferred form of graphite is bulk graphite from The Carbide/Graphite Group, Inc.
  • the carbon nanomaterial containing dispersion may also contain a large amount of one or more other chemical compounds, such as polymers, antiwear agents, friction reducing agents, anti-corrosion agents, detergents, metal passivating agents, antioxidants, antifoaming agents, corrosion inhibitors, pour point depressants, and viscosity index improvers that are not for the purpose of dispersing, but to achieve thickening or other desired fluid characteristics.
  • other chemical compounds such as polymers, antiwear agents, friction reducing agents, anti-corrosion agents, detergents, metal passivating agents, antioxidants, antifoaming agents, corrosion inhibitors, pour point depressants, and viscosity index improvers that are not for the purpose of dispersing, but to achieve thickening or other desired fluid characteristics.
  • the carbon nanomaterial dispersion can be pre-sheared, in a turbulent flow, such as a nozzle, or high pressure fuel inj ector, ultrasonic device, or mill in order to achieve a stable viscosity.
  • a turbulent flow such as a nozzle, or high pressure fuel inj ector, ultrasonic device, or mill
  • This may be especially desirable in the case where carbon nanotubes with high aspect ratio are used as the graphite source, since they, even more than spherical particles, will thicken the fluid but loose viscosity when exposed in turbulent flows such as the flow regime in engines.
  • Pre-shearing e.g.
  • a novel method has been developed whereby graphite particles are milled to form a thick pasty liquid of particles with mean size less than 500 nanometers in diameter.
  • the pasty liquid is then used as concentrate to prepare lubricants of various viscosity grades, and can be easily diluted to make a fluid with suitable viscosity for an automatic transmission fluid.
  • a very effective paste can be made by mixing particles in a viscous base fluid in a loading of 5% to 20% by weight and milling for a period of several hours.
  • the base fluid preferably contains from 20% up to 100% ofthe dispersant/surfactant mixture with the remainder being natural, synthetic, or mineral base oil.
  • the final ATF composition should be prepared to give an acceptable lubricant film thickness at the maximum shear rate and temperature of use in the target transmission.
  • the maximum concentration of particles in the final (diluted) automatic transmission fluid is limited by the relationship between viscosity increase of the fluid caused by the particles, and the temporary loss of viscosity (associated with the particles) at maximum temperature and shear rate of fluid use.
  • the heat transfer improvement with the ATF ofthe instant invention will be greater at room temperature than at the highest temperature of use due to the excellent viscosity index ofthe particle- containing fluids, depending on the particle size and their thickening effect.
  • Viscosity index is defined as the relationship of viscosity to the temperature of a fluid.
  • ft is an object ofthe present invention to provide a method of developing a method of forming carbon nanomaterials from inexpensive bulk graphite.
  • the carbon nanomaterial can optionally be surface treated to be hydrophilic at surface for ease of dispersing into the aqueous medium.
  • HLB hydrophile-lipophile balance
  • the dispersants can be the ashless polymeric dispersants used in the lubricant industry.
  • Figure 1 is an atomic force microscopy (AFM) picture of an automatic transmission fluid composition showing the graphite nanoparticles as flakes or plate-like structures with an average diameter of around 50 nm and thickness around 5 nm.
  • AFM atomic force microscopy
  • Figure 2 is a diagram of a hot-wire rig constructed to obtain the absolute measurement ofthe thermal conductivity of electrically conducting liquids by the transient hot-wire method.
  • the present invention provides a graphitic dispersion in fluid medium that gives a high thermal conductivity and improved heat transfer capability compared to conventional fluids ofthe same medium.
  • the fluid medium is targeted in its viscosity, friction, and antioxidant characteristics to perform in modern automatic transmissions.
  • the nanotubes can be cither single- walled, or multi- walled, having a typical nanoscale diameter of 1-200 nanometers. More typically the diameter is around 10-30 nanometers.
  • the length ofthe tube can be in submicron and micron scale, usually from 500 nanometers to 500 microns. More typical length is 1 micron to 100 microns.
  • the aspect ratio ofthe tube can be from hundreds to thousands, more typical 500 to 5000.
  • the surface ofthe nanotube can be treated chemically to achieve certain level of hydrophilicity, or left as is from the production. Unfortunately, the commercial availability ofthe prepared nanotubes is limited making them too expensive for incorporation into commodity type lubricants at this time.
  • graphite is a high-thermal-conductivity graphite commercially available, e.g. POCO FOAM, available from Poco Graphite, Inc., and graphite powders available from UCAR Carbon Company Inc.
  • POCO FOAM is a high thermal conductivity foamed graphite, thermal conductivity typically in the range 100 to 150 W/m-K.
  • a readily commercially available graphite is graphite powders from UCAR Carbon Company Inc., thermal conductivity of 10 to 500 W/m-K , and typically > 80 W/m-K.
  • Still another acceptable form of graphite is the high-thermal-conductivity graphite, Part#875G, from The Carbide/Graphite Group, Inc.
  • graphite are prepared for the instant invention by pulverizing to a fine powder, dispersing chemically and physically in a fluid of choice, and then ball milled or otherwise size reduced until particle, flake, fibril or combinations thereof produce nanomaterial of a size of less than 500 nm mean size is attained.
  • the preferred method is to disperse the graphite by ball milling in a viscous fluid of most additives (detergents, dispersants, etc.) and then diluting the obtained concentrate with base oil and other additives as needed to attain the final viscosity and performance characteristics.
  • the finer the particle size attained upon milling the better the thermal conductivity increase but also the more viscosity thickening effect ofthe pasty concentrate on the final blend.
  • any high thermal conductivity graphite can be used, provided that pulverization, milling and other described chemical and physical methods can be used to reduce the size ofthe final graphite dispersion to below a mean particle size of 500 nm or less.
  • the mechanical process and sequence of adding the components are important in order to fully take advantage ofthe high viscosity index ofthe nanoparticles and to make the final fluid product with exceptionally high viscosity index.
  • High impact mixing is necessary to achieve ) a homogeneous dispersion.
  • Ball mill is one ofthe examples of a high impact mixer.
  • an Eiger Mini Mill (Model: M250-VSE-EXP) is used as the high impact ball mill. It utilizes high wear resistant zirconia beads as the grinding media and circulates the dispersion constantly during milling. To achieve the best milling effect and therefore the best viscosity index improvement, the proper milling procedure has been developed.
  • a 5% to 20% by weight of graphite powders, and more preferably 10% by weight of graphite powders, in base oil dispersion is milled into a paste state. Usually this step takes about 3 to 4 hours.
  • dispersing agent(s) With the addition of dispersing agent(s) the paste changes from paste into liquid almost instantly, and extended milling becomes possible. For most cases the extended milling period is 4 hours. It should be pointed out that if the mixture in the mill turns into a paste, the recirculation of it becomes very difficult and thus a poor milling is resulted. It is also found that if the dispersing agent(s) is(are) added into the mill at the very beginning, the viscosity index ofthe final nanofluids made from the milling process is not as high.
  • Graphite nanomaterials are obtained by pulverizing big graphite chunks weight several pounds or kilograms obtained from The Carbide/Graphite Group.
  • the resulting pulverized material is size-selected through a mesh filter to be less than 75 ⁇ m.
  • Thirty (30) grams of the above pulverized graphite particles and 270 grams of a base oil, DURASYN 162 (a commercial 2 centistokes polyalphaolefin) were added into the Eiger Mini Mill (Model: M250-VSE-EXP). The milling speed was gradually increased to 4000 rpm. In about 4 hours the above mixture turned into thick paste. About 60 grams of this paste was discharged and labeled Paste 'A'.
  • Paste "B" Forty-eight (48) grams of a dispersant package from Lubrizol Inc., LUBRIZOL 9677MX, was added to the rest of the mixture in the mill. The paste became very thin, and successful recirculation was restored. Stopped the mill after another 4 hours of milling and labeled the discharged paste as Paste "B".
  • Paste "C” was obtained by milling a mixture of 30 grams of graphite with diameter less than 75 ⁇ m, 60 grams of LUBRIZOL 9677MX, and 270 grams of DURASYN 162 at 4000 rpm for 8 hours. Note here the dispersing agent LUBRIZOL 9677MX was added into the mill at the very beginning.
  • Example 1 illustrates the 100°C viscosity and viscosity index (VI) ofthe fluids. It was also found that the graphite particle size before milling was an important variable to control the viscosity modification effect as well.
  • a thin Paste D was. obtained.
  • An automatic transmission fluid D was formulation with the same composition as ATF A and result is list in Example 1 as well.
  • the particle size is measured by atomic force microscopy (AFM), and Figure 1 illustrates an AFM picture of ATF B.
  • the graphite nanoparticles appear to be flakes or a plate-like structure, with average diameter of around 50 nm and thickness around 5 nm.
  • the petroleum liquid medium can be any petroleum distillates or synthetic petroleum oils, greases, gels, or oil-soluble polymer composition. More typically, it is the mineral basestocks or synthetic basestocks used in the lube industry, e.g., Group I (solvent refined mineral oils). Group II (hydrocracked mineral oils), Group III (severely hydrocracked oils, sometimes described as synthetic or semi-synthetic oils), Group IV (polyalphaolefins), and Group V (esters, naphthenes, and others). One preferred group includes the polyalphaolefins, synthetic esters, and polyalkylglycols.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene- isobutylene copolymers, chlorinated polybutylenes, poly(l-octenes), poly(l-decenes), etc., and mixtures thereof; alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2- ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.), alkylated diphenyl, ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.
  • Another suitable class of synthetic oils comprises the esters of dicarboxylic acids (e.g., phtalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol diethylene glycol monoether, propylene glycol, etc.).
  • dicarboxylic acids e.g., phtalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, alkenyl malonic acids, etc.
  • alcohols e.g., but
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azealate, dioctyl phthalate, didecyl phthalate, dicicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.
  • Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
  • Other synthetic oils include liquid esters of phosphorus- containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid, etc.), polymeric tetrahydrofurans and the like.
  • Preferred polyalphaolefins include those sold by Mobil Chemical Company as SHF fluids, and those sold by Ethyl Corporation under the name ETHYLFLO, or ALBERMARLE.
  • PAO include the ETHYL-FLOW series by Ethyl Corporation, 'Albermarle Corporation,' including i ETHYL-FLOW 162, 164, 166, 168, and 174, having varying viscosity from about 2 to about 460 centistokes.
  • EMERY 3004 and 3006 provide additional polyalphaolefins basestocks.
  • EMERY 3004 polyalphaolefin has enterprise-to-break at 100°C and 16.75 centistokes at 40°C. It has i a viscosity index of 125 and a pour point of -98°C.
  • EMERY 3006 polyalphaolefin has a viscosity of 5.88 centistokes at 100°C and 31.22 centistokes at 40°C.
  • polyalphaolefins those sold by Uniroyal Inc. under the brand SYNTON PAO-40, which is a 40 centistokes polyalphaolefin. Also useful are the Oronite brand polyalphaolefins manufactured by Chevron Chemical Company.
  • the polyalphaolefins will have a viscosity in the range of about 2-100 centistokes at 100°C , with viscosity of 4 and 10 centistokes being particularly preferred.
  • the most preferred synthetic base oil ester additives are polyolesters and diesters such as di-aliphatic diesters of alkyl carboxylic acids such as di-2-ethylhexylazelate, di-isodecyladipate, and di-tridecyladipate, commercially available under the brand name EMERY 2960 by Emery Chemicals, described in U.S. Patent 4,859,352 to Waynick.
  • Other suitable polyolesters are manufactured by Mobil Oil. Mobil polyolesters P-43, M-045 containing two alcohols, and Hatco Corp. 2939 are particularly preferred.
  • Diesters and other synthetic oils have been used as replacements of mineral oil in fluid lubricants. Diesters have outstanding extreme low temperature flow properties and good resistance to oxidative breakdown.
  • the diester oil may include an aliphatic diester of a dicarboxylic acid, or the diester oil can comprise a dialkyl aliphatic diester of an alkyl dicarboxylic acid, such as di-2-ethyl hexyl azelate, di-isodecyl azelate, di-tridecyl azelate, di-isodecyl adipate, di-tridecyl adipate.
  • Di-2- ethylhexyl azelate is commercially available under the brand name of EMERY 2958 by Emery Chemicals.
  • polyol esters such as EMERY 2935, 2936, and 2939 from Emery Group of Henkel Corporation and Hatco 2352, 2962, 2925, 2938, 2939, 2970, 3178, and 4322 polyol esters from Hatco Corporation, described in U.S. 5,344,579 to Ohtani et al., and Mobil ester P 24 from Mobil Chemical Company.
  • Mobil esters such as made by reacting dicarboxylic acids, glycols, and either monobasic acids or monohydric alcohols like EMERY 2936 synthetic-lubricant basestocks ) from Quantum Chemical Corporation and Mobil P 24 from Mobil Chemical Company can be used.
  • Polyol esters have good oxidation and hydrolytic stability.
  • the polyol ester for use herein preferably has a pour point of about -100°C or lower to -40°C and a viscosity of about 2-460 centistokes at 100°C .
  • Group in oils are often referred to as hydrogenated oil to be used as the sole base oil component ofthe instant invention providing superior performance to conventional ATFs with no other synthetic oilbase or mineral oil base.
  • a hydrogenated oil is a mineral oil subjected to hydrogenation or hydrocracking under special conditions to remove undesirable chemical compositions and impurities resulting in a mineral oil based oil having synthetic oil components and properties.
  • the hydrogenated oil is defined as a Group H petroleum based stock with a sulfur level less than 0.03, severely hydrotieated and isodewaxed with saturates greater than or equal to 90 and a viscosity index of greater than or equal to 120, and may optionally be utilized in amounts up to 90 percent by volume, more preferably from 5.0 to 50 percent by volume and more preferably from 20 to 40 percent by volume when used in combination with a synthetic or mineral oil.
  • the hydrogenated oil my be used as the sole base oil component of the instant invention providing superior performance to conventional motor oils with no other synthetic oil base or mineral oil base.
  • the hydrogenated oil may be present in an amount of up to 95 percent by volume, more preferably from about 10 to 80 percent by volume, more preferably from 20 to 60 percent by volume and most preferably from 10 to 30 percent by volume ofthe base oil composition.
  • a Group I or ⁇ mineral oil basestock may be incorporated in the present invention as a portion ofthe concentrate or a basestock to which the concentrate may be added.
  • Preferred as mineral oil basestocks are the Marathon Ashland Petroleum (MAP) 325 Neutral defined as a solvent refined neutral having a Sabolt Universal viscosity of 325 SUS at 100°C and MAP 100 Neutral defined as a solvent refined neutral having a Sabolt Universal viscosity of 100 SUS at 100°C, both manufactured by the Marathon Ashland Petroleum.
  • MAP Marathon Ashland Petroleum
  • Other acceptable petroleum-base fluid compositions include white mineral, paraffinic and MVT naphthenic oils having the viscosity range of about 20-400 centistokes.
  • Preferred white mineral oils include those available from Witco Corporation, Arco Chemical Company, PSI and Penreco.
  • Preferred paraffinic oils include solvent neutral oils available from Exxon Chemical Company, HVI neutral oils available from Shell Chemical Company, and solvent treated neutral oils available from Arco Chemical Company.
  • Preferred MVT naphthenic oils include solvent extracted coastal pale oils available from Exxon Chemical Company, MVI extracted acid treated oils available from Shell Chemical Company, and naphthenic oils sold under the names HYDROCAL and CALSOL by Calumet, and described in U.S. Patent 5,348,668 to Oldiges.
  • vegetable oils may also be utilizes as the liquid medium in the instant invention.
  • Soybean or rapeseed oil particularly of the high oleic or mid oleic genetically engineered type, commercially available from Archer Daniels Midland Company, are good examples of these oils. Soybean oil is of interest because it has a high thermal conductivity itself.
  • Dispersants used in the lubricant industry are typically used to disperse the "cold sludge” formed in gasoline and diesel engines, which can be cither “ashless dispersants", or containing metal atoms.
  • the ashless dispersants commonly used in the automotive industry contain an lipophilic hydrocarbon group and a polar functional hydrophilic group.
  • the polar functional group can be ofthe
  • the lipophilic group can be oligomeric or polymeric in nature, usually from 70 to 200 carbon atoms to ensure oil solubility.
  • Hydrocarbon polymers treated with various reagents to introduce polar functions include products prepared by treating polyolefins such as polyisobutene first with maleic anhydride, or phosphorus sulfide or chloride, or by thermal treatment, and then with reagents such as polyamine, amine, ethylene oxide, etc.
  • ashless dispersants the ones typically used in the petroleum industry include N- substituted polyisobutenyl succinimides and succinates, alkyl methacrylate- vinyl pyrrolidinone copolymers, alkyl methacrylate-dialkylammoethyl methacrylate copolymers, alkylmethacrylate- polyethylene glycol methacrylate copolymers, and polystearamides.
  • Preferred oil-based dispersants that are most important in the instant application include dispersants from the chemical classes of alkylsuccinimide, succinate esters, high molecular weight amines, Mannich base and phosphoric acid derivatives.
  • polyisobutenyl succinintide-polyethylencpolyamine polyisobutenyl succinic ester
  • polyisobutenyl hydroxybenzyl-polyethylcncpolyamine bis- hydroxypropyl phosphorate.
  • Commercial dispersants suitable for transmission fluid are for example, Lubrizol 890 (an ashless PIB succinimide), Lubrizol 6420 (a high molecular weight PIB succinimide), ETHYL HITEC 646 (a non-boronated PIB succinimide).
  • the dispersant may be combined with other additives used in the lubricant industry to form a ispersant-detergent (DI) additive package for transmission fluids, e.g., LUBRIZOL 9677MX, and the whole DI package can be used as dispersing agent for the nanoparticle dispersions.
  • DI ispersant-detergent
  • a surfactant or a mixture of surfactants with low HLB value typically less than or equal to 8
  • nonionic preferably nonionic
  • a mixture of nonionics and ionics may be used in the instant invention.
  • the dispersants selected should be soluble or dispersible in the liquid medium.
  • the dispersant can be in a range of up from 0.01 to 30 percent, more preferably in a range of from between 0.5 percent to 20 percent, more preferably in a range of from between 1 to 15 percent, and most preferably in a range of from between 2 to 13 percent.
  • the carbon nanomaterials can be of any desired weight percentage in a range of from 0.001 up to 10 percent. For practical application it is usually in a range of from between 0.01 percent to 10 percent, and most preferably in a range of from between 0.1 percent to 5 percent. The remainder ofthe formula is the selected medium. It is believed that in the instant invention the dispersant functions by adsorbing onto the surface ofthe carbon nanomaterials.
  • This dispersion may also contain a large amount of one or more other chemical compounds, preferably polymers, not for the purpose of dispersing, but to achieve thickening or other desired fluid characteristics. These can be added but reduce the amount of particulate that can be used without excessive thickening.
  • the viscosity improvers used in the lubricant industry can be used in the instant invention for the oil medium, which include olefin copolymers (OCP), polymethacrylates (PMA), hydrogenated styrene-diene (STD), and styrene-polyester (STPE) polymers.
  • Olefin copolymers are rubber-like materials prepared from ethylene and propylene mixtures through vanadium-based Ziegler-Natta catalysis.
  • Styrene-diene polymers are produced by anionic polymerization of styrene and butadiene or isoprene.
  • Polymethacrylates are produced by free radical polymerization of alkyl methacrylates.
  • Styrene-polyester polymers are prepared by first co-polymerizing styrene and maleic anhydride and then esterifying the intermediate using a mixture of alcohols.
  • acrylic polymers such as polyacrylic acid and sodium polyacrylate, high-molecular-weight polymers of ethylene oxide such as Polyox WSR from Union Carbide, cellulose compounds such as carboxymethylcellulose, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), xanthan gums and guar gums, polysaccharides, alkanolamides, amine salts of polyamide such as DISPARLON AQ series from King Industries, hydrophobically modified ethylene oxide urethane (e.g., ACRYSOL series from Rohmax), silicates, and fillers such as mica, silicas, cellulose, wood flour, clays (including organoclays) and nanoclays, and resin polymers such as polyvinyl butyral resins, polyurethane resins, acrylic resins and epoxy resins.
  • resin polymers such as polyvinyl butyral resins, polyurethane resins, acrylic resins and epoxy resins.
  • Chemical compounds such as seal swell agents or plasticizers can also be used in the instant invention and may be selected from the group including phthalate, Adipate, sebacate esters, and more particularly: glyceryl tri(acetoxystearate), epoxidized soybean oil, epoxidized linseed oil, N,n-butyl benzene sulfonamide, aliphatic polyurethane, epoxidized soy oil, polyester glutarate, polyester glutarate, triethylene glycol caprate/caprylate, long chain alkyl ether, dialkyl diester glutarate, monomeric, polymer, and epoxy plasticizers, polyester based on adipic acid, hydrogenated dirner acid, distilled dimer acid, polymerized fatty acid trimer, ethyl ester of hydrolyzed collagen, isostearic acid and sorbian oleate and cocoylhydrolyzed keratin, PPG-12/PEG-65 lanolin oil, dial
  • alkyl benzyl phthalate dibutoxy ethoxy ethyl adipate, 2-ethylhexyldiphenyl phosphate, dibutoxy ethoxy ethyl forrnyl, diisopropyl adipate, diisopropyl sebacate, isodecyl oieate, neopentyl glycol dicaprate, neopenty giycol diotanoate, isohexyl neopentanoate, ethoxylated lanolins, polyoxyethylene cholesterol, propoxylated (2 moles) lanolin alcohols, propoxylated lanoline alcohols, acetylated polyoxyethylene derivatives of lanoline, and dimethylpolysiloxane.
  • plasticizers which may be substituted for and/or used with the above plasticizers including glycerine, polyethylene glycol, dibutyl phthalate, and 2,2,4-trimethyl-l,3-pentanediol monoisobutyrate, and diisononyl phthalate all of which are soluble in a solvent carrier.
  • Other seal swelling agents such as Lubrizol 730 can also be used.
  • Antioxidants are an important part of transmission fluids.
  • General classes include zinc dialkyldithiophosphates, alkyl and aryl phenols, alkyl and aryl amines, and sulfurized olefins.
  • Commercial examples are CIBA L57 (phenyl amine) and ETHYL Hl ' l ' EC 1656.
  • Pour point depressants either of polymethyl methacrylate or ethylene propylene olefin copolymer type are useful to decrease the low temperature Brookfield viscosity ofthe ATF. Examples include ROHMAX 3008, ROHMAX 1-333, LUBRIZOL 6662A.
  • Friction Modifiers are used to control friction and torque characteristics of the fluid.
  • Commercial examples include LUBRIZOL 8650 and HITEC 3191.
  • the physical mixing includes high shear mixing, such as with a high speed mixer, homogenizers, microfluidizers, a Kady mill, a colloid mill, etc., high impact mixing, such as ) attritor, ball and pebble mill, etc., and ultrasonication methods or passing through a small orifice such as a fuel injector. Turbulent flows of any type will assist mixing.
  • Ball milling is the most preferred physical method in the instant invention since it is effective at rapidly reducing the graphite particles to very small size while simultaneously dispersing them into a concentrated paste as previously described.
  • the concentrate can then be
  • the raw material mixture may be pulverized by any suitable known dry or wet grinding method.
  • One grinding method includes pulverizing the raw material mixture in the fluid mixture ofthe instant invention to obtain the concentrate, and the pulverized product may then be dispersed further in a liquid medium with the aid of the dispersants described above.
  • pulverization or milling reduces the carbon nanotube average aspect ratio.
  • Ultrasonication is another physical method in the instant invention since it is less destructive to the carbon nanomaterial structure than the other methods described. Ultrasonication can be done either in the bath-type ultrasonicator, or by the horn-type ultrasonicator. More typically, horn-type ultrasonication is applied for higher energy output. Sonication at the medium-high instrumental intensity for up to 30 minutes, and usually in a range of from 10 to 20 minutes is desired to achieve better homogeneity.
  • the instant method of forming a stable dispersion of carbon nanomaterials in a solution consist of three steps. First select the appropriate concentrate of dispersant or mixture of dispersing and other additives for the carbon nanomaterials, and the medium, and dissolve the dispersant into the liquid medium to form a concentrate solution (keeping in mind the final additive concentrations desired following dilution); secondly add a high concentration of the carbon nanomaterials into the dispersant-containing solution, initiate strongly agitating, ball milling, or ultiasonicating, or any combination of physical methods named; following an agitation time of several hours, the resulting paste will be extremely stable and easily dilutable into more base oil and additives to give the final desired concentrations of additives and the desired final viscosity.
  • E is an off-the-shelf regular commercial ATF (MERCON V).
  • Thermal conductivity is measured by a transient hot-wire rig constructed by the inventors in-house according to Nagasaka et al. (Y. Nagasaka and A. Nagashima, Absolute measurement
  • Viscosity 40 (cSt) 28.4 Viscosity 100 (cSt) 7.55 Viscosity Index (VI) 254 (vs. 183 for conventional ATF) Thermal conductivity (W/m-K ) 0.1776 (vs. 0.132 for conventional ATF) RHTEF at 40 1.4 (vs. conventional ATF)
  • Example 3 Components Description Weight percentage Carbon nanomaterial Graphite powder (UCAR) 2.0 Dispersant LUBRIZOL 9677MX 4.0 Base oil DURASYN 166 76.0 Base oil DURASYN 162 18.0
  • Viscosity 40 (cSt) 27.85 Viscosity 100 (cSt) 7.48 Viscosity Index (VI) 257 (vs. 183 for conventional ATF) Thermal conductivity (W/m-K ) 0.1926 (vs. 0.132 for conventional ATF) RHTEF at 40 1.5 (vs. conventional ATF)
  • Example 4 Components Description Weight percentage Carbon nanomaterial POCO Foam Poco Graphite 2.5 Dispersant LUBRIZOL 9677MX 7.5 Base oil SK YUBASE 4 42.5 Base oil SK YUBASE 3L 42.5 Viscosity modifier LUBRIZOL 7720C 5.0 Process Eiger mini mill
  • Viscosity 40 (cSt) 43.12 Viscosity 100 (cSt) 9.55 Viscosity Index (VI) 215 (vs. 183 for conventional ATF) Thermal conductivity (W/m-K ) 0..2092 vs. 0.132 for conventional ATF) RHTEF at 40 1.6 (vs. conventional ATF)
  • Example 5 Components Description Weight percentage Carbon nanomaterial Graphite (The Carbide/Graphite 2.0 Group, Inc.) Dispersant LUBRIZOL 9677MX 5.0 Base oil DURASYN 162 18.0 Base oil HATCO HXL-7156 37.5 Base oil SK YUBASE L3 37.5
  • Viscosity 40 35.18 Viscosity 100 (cSt) 10.48 Viscosity Index (VI) 306 (vs. 183 for conventional ATF) Thermal conductivity (W/m-K ) 0.1889 vs. 0.132 for conventional ATF) ⁇ RHTEF at 40 1.3 (vs.
  • Example 7 Components Description Weight percentage Carbon nanomaterial Multi-walled carbon nanotubes 0.2 Dispersant ORONITE OLOA 9061 4.8 Base oil DURASYN 166 95.0
  • Viscosity 40 (cSt) 46.08 Viscosity 100 (cSt) 9.89 Viscosity Index (VI) 208 (vs. 183 for conventional ATF) Thermal conductivity (W/m-K ) 0.1522 vs. 0.132 for conventional ATF) RHTEF at 40 1.2 (vs. conventional ATF)

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne une composition lubrifiante à thermoconductivité améliorée, jusqu'à 80 % supérieure aux analogues classiques, et des procédés de préparation de ce fluide. Une composition préférée contient une huile de base, un nanomatériau et un agent de dispersion ou un tensioactif destiné à stabiliser ledit nanomatériau. Le nanomatériau préféré est un graphite à thermoconductivité élevée dépassant 80W/m-K. Le graphite est broyé, moulé ou préparé naturellement afin d'obtenir une granulométrie moyenne inférieure à 500 nm (nanomètres) en diamètre, de préférence inférieure à 100 nm, et idéalement inférieure à 50 nm. Ledit graphite est dispersé dans le fluide à l'aide d'un ou de plusieurs procédé(s) comprenant l'ultrasonication, la mouture et la dispersion chimique. Des nanostructures de carbone, telles que des nanotubes, des nanofibres et des nanoparticules, constituent un autre type de structure graphitique utilisée dans l'invention. D'autres matériaux de carbone à thermoconductivité élevée sont également acceptables. Pour conférer une stabilité à long terme, on utilise un ou plusieurs dispersant(s) ou tensioactif(s) chimique(s). L'amélioration de la thermoconductivité par rapport à un fluide sans graphite, est proportionnelle à la quantité de nanomatériaux ajoutée. Ces naomatériaux de carbone contribuent à la viscosité fluidique globale, ce qui supprime partiellement ou complètement le recours à des améliorants d'indice de viscosité et permet d'obtenir un indice de viscosité très élevé. La chimie de granulométrie et de dispersion est commandée afin d'obtenir la combinaison de viscosité et thermoconductivité accrues à partir de l'huile de base tout en régulant la quantité de perte de viscosité temporaire dans des champs de cisaillement. Les fluides résulatant possèdent des propriétés uniques dues à la thermoconductivité et à l'indice de viscosité élevés des particules suspendues ainsi qu'à leur petite taille.
PCT/US2004/042109 2003-12-16 2004-12-16 Lubrifiants a thermoconductivite amelioree contant un nanomateriau WO2005060648A2 (fr)

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WO2011036411A1 (fr) 2009-09-25 2011-03-31 Arkema France Mélange-maître pour la fabrication de fluide de forage
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US10066187B2 (en) 2012-07-02 2018-09-04 Nanomech, Inc. Nanoparticle macro-compositions
US8921286B2 (en) 2012-07-02 2014-12-30 Nanomech, Inc. Textured surfaces to enhance nano-lubrication
WO2014178811A1 (fr) * 2013-04-30 2014-11-06 Boryshchuk Vladislav Additif pour carburants et lubrifiants
US11939548B2 (en) 2019-05-22 2024-03-26 Fuelgems, Inc. Additive for liquid fuels, fuel compositions based on the additive, and methods of manufacture
CN115948193A (zh) * 2022-12-12 2023-04-11 上海纳米技术及应用国家工程研究中心有限公司 一种超润滑水基切削液及其制备方法
CN115948193B (zh) * 2022-12-12 2024-06-11 上海纳米技术及应用国家工程研究中心有限公司 一种超润滑水基切削液及其制备方法

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