WO2003050332A1 - Preparation de dispersions de nanotubes de carbone stables dans les liquides - Google Patents

Preparation de dispersions de nanotubes de carbone stables dans les liquides Download PDF

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Publication number
WO2003050332A1
WO2003050332A1 PCT/US2002/038643 US0238643W WO03050332A1 WO 2003050332 A1 WO2003050332 A1 WO 2003050332A1 US 0238643 W US0238643 W US 0238643W WO 03050332 A1 WO03050332 A1 WO 03050332A1
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WIPO (PCT)
Prior art keywords
liquid medium
dispersant
carbon nanotube
ofthe
nanotubes
Prior art date
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PCT/US2002/038643
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English (en)
Inventor
Frances E. Lockwood
Zhiqiang Zhang
Original Assignee
Ashland Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US10/021,767 external-priority patent/US6783746B1/en
Application filed by Ashland Inc. filed Critical Ashland Inc.
Priority to BRPI0215135-9A priority Critical patent/BR0215135B1/pt
Priority to MXPA04005761A priority patent/MXPA04005761A/es
Priority to AU2002357065A priority patent/AU2002357065B2/en
Priority to CA2470113A priority patent/CA2470113C/fr
Priority to EP02804723A priority patent/EP1495171A4/fr
Priority to NZ533941A priority patent/NZ533941A/en
Publication of WO2003050332A1 publication Critical patent/WO2003050332A1/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
    • C10M171/00—Lubricating 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
    • C10M171/06—Particles of special shape or size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified

Definitions

  • Carbon nanotubes are a new form ofthe material formed by elemental carbon, which possess different properties than the other forms ofthe carbon materials. They have unique atomic structure, very high aspect ratio, and extraordinary mechanical properties (strength and flexibility), making them ideal reinforcing fibers in composites and other structural materials.
  • Carbon nanotubes are characterized as generally to rigid porous carbon three dimensional structures comprising carbon nanofibers and having high surface area and porosity, low bulk density, low amount of micropores and increased crush strength.
  • the instant process is applicable to nanotubes with or without amorphous carbon.
  • nanotube refers to elongated structures having a cross section (e.g., angular fibers having edges) or diameter (e.g., rounded) less than 1 micron.
  • the structure may be either hollow or solid. Accordingly, the term includes “nanofibrils” and “bucky tubes”.
  • Such structures provide significant surface area when incorporated into a structure because of their size and shape. Moreover, such fibers can be made with high purity and uniformity.
  • the nanotube used in the present invention has a diameter less than 1 micron, preferably less than about 0.5 micron, and even more preferably less than 0.1 micron and most preferably less than 0.05 micron.
  • internal structure refers to the internal structure of an assemblage including the relative orientation ofthe fibers, the diversity of and overall average of fiber orientations, the proximity ofthe fibers to one another, the void space or pores created by the interstices and spaces between the fibers and size, shape, number and orientation ofthe flow channels or paths formed by the connection ofthe void spaces and/or pores.
  • the structure may also include characteristics relating to the size, spacing and orientation of aggregate particles that form the assemblage.
  • relative orientation refers to the orientation of an individual fiber or aggregate with respect to the others (i.e., aligned versus non-aligned).
  • the "diversity of and “overall average” of fiber or aggregate orientations refers to the range of fiber orientations within the structure (alignment and orientation with respect to the external surface ofthe structure).
  • Carbon nanotubes can be used to form a rigid assemblage or be made having diameters in the range of 3.5 to 70 nanometers.
  • the nanotubes, fibrils, bucky tubes and whiskers that are referred to in this application are distinguishable from continuous carbon fibers commercially available as reinforcement materials.
  • continuous carbon fibers In contrast to nanotubes, which have desirably large, but unavoidably finite aspect ratios, continuous carbon fibers have aspect ratios (L D) of at least 10 4 and often 10 6 or more.
  • the diameter of continuous fibers is also far larger than that of nanotubes, being always > 1.0 micron and typically 5 to 7 microns.
  • Continuous carbon fibers are made by the pyrolysis of organic precursor fibers, usually rayon, polyacrylonitrile (PAN) and pitch.
  • they may include heteroatoms within their structure.
  • the graphitic nature of "as made” continuous carbon fibers varies, but they may be subjected to a subsequent graphitization step. Differences in degree of graphitization, orientation and crystallinity of graphite planes, if they are present, the potential presence of heteroatoms and even the absolute difference in substrate diameter make experience with continuous fibers poor predictors of nanofiber chemistry.
  • Carbon nanotubes are typically hollow graphite tubules having a diameter of generally several to several tens nanometers. Carbon nanotubes exist in many forms.
  • the nanofibers can be in the form of discrete fibers or aggregate particles of nanofibers. The former results in a structure having fairly uniform properties. The latter results in a structure having two-tiered architecture comprising an overall macrostructure comprising aggregate particles of nanofibers bonded together to form the porous mass and a microstructure of intertwined nanofibers within the individual aggregate particles.
  • one form of carbon fibrils are characterized by a substantially constant diameter, length greater than about 5 times the diameter, an ordered outer region of catalytically grown, multiple, substantially continuous layers of ordered carbon atoms having an outside diameter between about 3.5 and 70 nanometers, and a distinct inner core region.
  • Each of the layers and the core are disposed substantially concentrically about the cylindrical axis of the fibril.
  • the fibrils are substantially free of pyrolytically deposited thermal carbon with the diameter ofthe fibrils being equal to the outside diameter ofthe ordered outer region.
  • a carbon nanotube suitable for use with the instant process defines a cylindrical carbon fibril characterized by a substantially constant diameter between 3.5 and about 70 nanometers, a length greater than about 5 times the diameter and less than about 5000 times the diameter, an outer region of multiple layers of ordered carbon atoms and a distinct inner core region, each ofthe layers and the core being disposed concentrically about the cylindrical axis ofthe fibril.
  • the entire carbon nanotube is substantially free of thermal carbon overcoat.
  • the term "cylindrical” is used herein in the broad geometrical sense, i.e., the surface traced by a straight line moving parallel to a fixed straight line and intersecting a curve.
  • the inner core region ofthe nanotube may be hollow, or may comprise carbon atoms which are less ordered than the atoms ofthe outer region.
  • Organic carbon atoms as the phrase is used herein means graphitic domains having their c-axes substantially perpendicular to the cylindrical axis ofthe nanotube.
  • the length ofthe nanotube is greater than about 20 times the diameter ofthe nanotube.
  • the nanotube diameter is between about 7 and about 25 nanometers.
  • the inner core region has a diameter greater than about 2 nanometers.
  • the nanotubes tend to aggregate, form agglomerates, and separate from the dispersion.
  • Some industrial applications require a method of preparing a stable dispersion of a selected carbon nanotube in a liquid medium.
  • U.S. Patent 5,523,006 by Strumban teaches the user of a surfactant and an oil medium; however, the particles are Cu-Ni-Sn-Zn alloy particles with the size from 0.01 micron and the suspension is stable for a limited period of time of approximately 30 days.
  • the surfactants don't include the dispersants typically utilized in the lubricant industry.
  • U.S. Patent 5,560,898 by Uchida et al. teaches that a liquid medium is an aqueous medium containing a surfactant; however, the stability of the suspension is of little consequence in that the liquid is centrifuged upon suspension.
  • U.S. Patent 5,853,877 by Sbibuta teaches dispersing disentangled nanotubes in a polar solvent and forming a coating composition with additives such as dispersing agents; however, a method of obtaining a stable dispersion is not taught.
  • U.S. Patent 6,099,965 by Tennent et al. utilizes a kneader teaching mixing a dispersant with other reactants in a liquid medium using a high-torque dispersing tool, yet sustaining the stability ofthe dispersion does not appear to be taught nor suggested. None of the conventional methods taught provide a process for dispersing and maintaining nanotubes in suspension as described and claimed in the instant invention as follows.
  • the present invention provides a method of preparing a stable dispersion of a selected carbon nanotube in a liquid medium, such as water or any water based solution, or oil, with the combined use of surfactants and agitation (e.g. ultrasonication) or other means of agitation.
  • a liquid medium such as water or any water based solution, or oil
  • the carbon nanotube can be either single-walled, or multi-walled, with typical aspect ratio of 500-5000; however, it is contemplated that nanotubes of other configurations can also be utilized with the instant invention. It is contemplated that a mixture containing carbon nanotubes having a length of 1 micron or more and a diameter of 50 nm or less.
  • the raw material may contain carbon nanotubes having a size outside ofthe above ranges.
  • the carbon nanotube is not required to be surface treated providing a hydrophilic surface for dispersion into the aqueous medium, but optionally may be treated.
  • the selected surfactant is soluble or dispers
  • surfactant in the instant invention 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. It is a broad term that covers all materials that have surface activity, including wetting agents, dispersants, emulsifiers, detergents and foaming agents, etc.
  • dispenser 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.
  • the term “dispersant” is general accepted to describe the long chain oil soluble or dispersible compounds which function to disperse the "cold sludge” formed in engines. These two terms are mostly interchangeable in the instant invention; however, in some cases the term “dispersant” is used with the tendency to emphasize, but not restrict to, the ones commonly used in the lubricant industry.
  • the method of making a stable particle-containing dispersions includes physical agitation in combination with chemical treatments .
  • 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.
  • the mixing methods are further aided by electrostatic stabilization by electrolytes, and steric stabilization bypolymeric surfactants (dispersants).
  • the chemical treatment and the use of the claimed surfactants/dispersants are critical to long term stability of the nanotube fluid mixtures.
  • the treatment involves dissolving a selected dispersant into a selected liquid medium.
  • the chemical method includes a two-step approach: dissolving the dispersant into the liquid medium, and then adding the selected carbon nanotube into the dispersant liquid medium mixture with mechanical agitation and/or ultrasonication. These steps can be reversed but may not produce as satisfactory a result.
  • the liquid medium can be water or any water solution, a petroleum distillate, a petroleum oil, synthetic oil, or vegetable oil.
  • the dispersant for the oily liquid medium is a surfactant with low hydrophile-lipophile balance (HLB) value (HLB ⁇ 8) or a polymeric dispersant of the type used in the lubricant industry. It is preferably nonionic, or a mixture of nonionics and ionics.
  • a preferred dispersant for the aqueous liquid medium is of high HLB value (HLB > 10), preferably a nonylphenoxypoly(ethyleneoxy)ethanol-type surfactant. Of course, other alcohol based glycols having a high HLB value can be used as well.
  • the uniform dispersion of nanotubes is obtained with a designed viscosity in the liquid medium.
  • the dispersion of nanotubes may be obtained in the form of a paste, gel or grease, in either a petroleum liquid medium or an aqueous medium.
  • 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.
  • Dl dispersant-detergent
  • the present invention provides a method a dispersing carbon nanotubes into a liquid medium.
  • the nanotubes can be either single-walled, or multi-walled, having a typical nanoscale diameter of 1-500 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 carbon nanotubes, fibers, particles or combination thereof can be utilized as is from the production.
  • the carbon nano particles comprising carbon nanotubes, carbon fibers, carbon particles or combinations thereof can be utilized as a substrate in the present invention' as is' as a commercial product straight from a commercial production process.
  • a preferred embodiment of the instant invention was obtained using a nano particle product having the surface treated chemically to achieve certain level of hydrophilicity by an activated carbon treatment. Moreover, a certain level of hydrophilicity can be achieved by utilizing a vapor disposition process using chemicals such as hydrogen sulfide; and/or by treatment with a strong acid or base.
  • a preferred embodiment utilized a carbon nanotube product obtained from Carbolex at the University of Kentucky which contains amorphous carbon particles and which is believed to utilize an activated carbon treatment to improve the level of hydrophilicity.
  • the Carbolex carbon nanotubes comprise single walled nanotubes, multi- wall nanotubes, and combinations thereof. Moreover, the combination can include small fractions ofthe carboneous materials made up of partially disordered spherical particles and/or short carbon nanotubes.
  • 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 VI (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.
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic oils.
  • 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, ethyleneglycoldiethyleneglycolmonoether, propyleneglycol, 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
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di- hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azealate, dioctylphthalate, 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 monocarboxyHc 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 ' s include the Ethyl-flow series by Ethyl Corporation, "Albermarle Corporation,” including Ethyl-flow 162, 164, 166, 168, and 174, having varying viscosity from about 2 to about 460 centistokes.
  • Emery 3004 polyalphaolefin has a viscosity of 3.86 centistokes (cSt) at 212 °F. (100 °C) and 16.75 cSt at 104 °F (40 °C). It has a viscosity index of 125 and a pour point of -98 °F and it also has a flash point of 432 °F and a fire point of 478 °F.
  • Emery 3006 polyalphaolefin has a viscosity of 5.88 cSt at +212 °F and 31.22 cSt at +104 °F. It has a viscosity index of 135 and a pour point of -87 °F. It also has a flash point of +464 °F and a fire point of +514 °F.
  • polyalphaolefins those sold by Uniroyal Inc. under the brand Synton PAO-40, which is a 40 centistoke polyalphaolefin. Also useful are the Oronite brand polyalphaolefins manufactured by Chevron Chemical Company.
  • Gulf Synfluid 4 cSt PAO commercially available from Gulf Oil Chemicals Company, a subsidiary of Chevron Corporation, which is similar in many respects to Emery 3004 may also be utilized herein.
  • Mobil SHF-41 PAO commercially available from Mobil Chemical Corporation, is also similar in many respects to Emery 3004.
  • the polyalphaolefins will have a viscosity in the range of about 2-40 centistoke at 100°C, with viscosity of 4 and 10 centistoke being particularly preferred.
  • the most preferred synthetic based oil ester additives arepolyolesters 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 polyolester 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 residence 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 ofHenkel 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 centistoke at 100°C.
  • Group III 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 motor oils with no other synthetic oil base 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 III petroleum based stock with a sulfur level less than 0.03, severely hydrotreatd and isodewaxed with saturates greater than or equal to 90 and a viscosity index of greater than or equal to 120 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 ofthe 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 II 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 ASHLAND 325 Neutral defined as a solvent refined neutral having a SABOLT UNIVERSAL viscosity of 325 SUS @ 100°F and ASHLAND 100 Neutral defined as a solvent refined neutral having a SABOLT UNIVERSAL viscosity of 100 SUS @ 100°F, manufactured by the Marathon Ashland Petroleum.
  • Other acceptable petroleum-base fluid compositions include white mineral, paraffinic and MVI 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 andPenreco.
  • 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 MVI naphthenic oils include solvent extracted coastal pale oils available from Exxon Chemical Company, MNI 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.
  • the selected aqueous medium is water, or it can be any water-based solution including alcohol and its derivatives, such as glycols or any water-soluble inorganic salt or organic compound.
  • Dispersants used in the lubricant industry are typically used to disperse the "cold sludge" formed in gasoline and diesel engines, which can be either “ashless dispersants", or containing metal atoms. They can be used in the instant invention since they have been found to be an excellent dispersing agent for soot, an amorphous form of carbon particles generated in the engine crankcase and incorporated with dirt and grease.
  • the ashless dispersants commonly used in the automotive industry contain an lipophilic hydrocarbon group and a polar functional hydrophiHc group.
  • the polar functional group can be of the class of carboxylate, ester, amine, amide, imine, imide, hydroxyl, ether, epoxide, phosphorus, ester carboxyl, anhydride, ornitrile.
  • the lipophilic group can be oligomeric or polymeric in nature, usually from 70 to 200 cabon 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-substitued polyisobutenyl succinimides and succinates, allkylmethacrylate- vinyl pyrrolidinone copolymers, alkyl methacrylate-dialkylaminoethyl 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, Mannichbase and phosphoric acid derivatives.
  • Dl dispersant-detergent
  • LUBRIZOL 9802A is described in the technical brochure (MATERIAL SAFETY DATA SHEET No. 1922959-1232446-3384064) by The Lubrizol Corporation in Wickliffe, OH and is hereby incorporated by reference.
  • LUBRIZOL 9802A is described as a motor oil additive is beheved to contain as an active ingredient a zinc dithiophosphate and/or zinc alkyldithiophosphate.
  • LUBRIZOL 4999 is described in its Technical Brochure (MATERIAL SAFETY DATA SHEET No. 1272553-1192556-3310026) by the Lubrizol Corporation in Wickliffe, OH and is hereby incorporated by reference.
  • LUBRIZOL 9802A is described as a engine oil additive and contains as an active ingredient from 5 to 9.9 percent of a zinc alkyldithiophosphate.
  • OLOA 9061 is described in Technical Brochure "MATERIAL SAFETY DATA SHEET No. 006703 " by Chevron Chemical Company LLC and is hereby incorporated by reference. OLOA 9061 is described as zinc alkyl dithiophosphate compound.
  • IGEPAL CO-630 is described in Technical Brochure "MATERIAL SAFETY DATA SHEET” from Rhodia Inc. and is hereby incorporated by reference. IGEPAL CO-630 is described as a nonylphenoxy poly(ethyleneoxy) ethanol, branched compound.
  • 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 dispersant for the water based carbon nanotube dispersion should be of high HLB value (typically less than or equal to 10), preferable nonylphenoxypoly (ethyleneoxy) ethanol-type surfactants are utilized.
  • the dispersants selected should be soluble or dispersible in the liquid medium.
  • the dispersant can be in a range of up from 0.001 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 1.0 to 8.0 percent, and most preferably in a range of from between 2 to 6 percent.
  • the carbon nanotube can be of any desired weight percentage in a range of from 0.0001 up to 50 percent. For practical application it is usually in a range of from between 0.01 percent to 2 percent, and most preferably in a range of from between 0.05 percent to 0.5 percent.
  • the remainder ofthe formula is the selected oil or water medium.
  • the dispersant functions by adsorbing onto the surface ofthe carbon nanotube.
  • the dispersant contains a hydrophilic segment and a hydrophobic segment which surrounds the carbon particles thereby providing a means for isolating and dispersing the carbon particles.
  • the selection of a dispersant having a particular HLB value is important to determine the dispersant characteristics such as rate and the degree of stabilization over time.
  • 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.
  • 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 polyacryhc 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
  • PVA polyvinyl alcohol
  • PVP polyvinyl pyrrolidone
  • 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 fromRohmax
  • silicates e.g., Acrysol series fromRohmax
  • fillers such as mica, silicas, cellulose, wood flour, clays (including organoclays) andnanoclays, andresinpolymers such as polyvin
  • Plasticizers can also be used in the instant invention and may be selected from the group including phthalate, adipates, sebacate esters, and more particularly: glyceryltri(acetoxystearate) 3 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 dimer acid, distilled dimer acid, polymerized fatty acid trimer, ethyl ester of hydrolyzed collagen, isostearic acid and sorbian oleate and cocoyl hydrolyzed keratin, PPG-12/PEG-65 lanolin oil, dialkyl adipate
  • 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.
  • 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.
  • Ultrasonication is the most preferred physical method in the instant invention since it is less destructive to the carbon nanotube structure than the other methods described. Ultrasonication can be done either in the bath-type ultrasonicator, or by the tip-type ultrasonicator. More typically, tip-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.
  • One dismembrator useful for preparing the instant invention is aModel 550 Sonic dismembrator manufactured by Fisher Scientific Company, located in Pittsburgh Pennsylvania.
  • the instruction manual Publication No. FS-FM-2 published in November of 1996 describing the use ofthe Fisher Scientific Model 550 Sonic Dismembrator is hereby incorporated by reference.
  • the generator power supply converst conventional 50/60 Hz AC line power to 20 kHZ electrical energy which is fed to the converter where it is transformed to mechanical vibration.
  • the heart ofthe convertor is a lead zirconate titanate (Piezoelectric) crystal which, when subjected to an alternating voltage, expands and contracts. The convertor vibrates in the longitudinal direction and transmits this motion to the horn tip immersed in the liquid solution.
  • Cavitation results, in which microscopic vapor bubbles are formed momentarily and implode, causing powerful shock waves to radiate throughout the sample from the tip face.
  • Horns and probes amplify the longitudinal vibration of the convertor; higher amplification (or gain) results in more intense cavitational action and greater disruption.
  • the larger the tip of the probe the larger the volume that can be processed but at lesser intensity.
  • the convertor is tuned to vibrate at a fixed frequency of 20 kHZ. All horns and probes are resonant bodies, and are also tuned to vibrate at 20 kHZ. Of course it is contemplated that other models and competing ultrasonic mixing devices could be utilized in accordance with the present invention.
  • 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 of the instant invention to obtain the concentrate, and the pulverized product may then be dispersed further in a liquid medium with the aid ofthe dispersants described above.
  • pulverization or milling reduces the carbon nanotube average aspect ratio.
  • the instant method of forming a stable suspension of nanotubes in a solution consist of two primary steps. First select the appropriate dispersant for the carbon nanotube and the medium, and dissolve the dispersant into the liquid medium to form a solution, and second add the carbon nanotube into the dispersant containing solution while strongly agitating, ball milling, or ultrasonication ofthe solution.
  • Dispersant LubrizolTM 4999 Liquid Poly(a-olefm), 6 cSt 95.1
  • the dispersions in Examples 1-4 are very uniform, and will remain in a stable dispersion without any sign of separation or aggregation for at least a year.
  • Example 1 up to 4.8 weight percent of a zinc dithiophosphate could be substituted for the LUBRIZOL 9802A since it is the primary active ingredient ofthe product.
  • Example 2 up to 4.8 weight percent of a zinc alkyldithiophosphate could be substituted for the LUBRIZOL 4999 product and be expected to yield similar results since a zinc alkyldithiophosphate is the active ingredient in the LUBRIZOL 4999 product.
  • Example 3 up to 4.8 weight percent a zinc alkyl dithiophosphate compound could be substituted for the OLOA 9061 since the alkyl dithiophosphate compound is the active ingredient in the OLOA 9061 product.
  • FinaUy in Example 4, up to 5.0 weight percent of a nonylphenoxy poly(ethyleneoxy) ethanol, branched compound could be substituted fro the IGEPAL CO- 630 product since the nonylphenoxy poly(ethyleneoxy) ethanol, branched compound is the primary active ingredient in the IGEPAL CO-630 product.
  • the weight percent ofthe carbon nanotube can be up to 10 weight percent, and more preferably up to 1 weight percent and most preferably from .01 to 1 weight percent in the formulations depending upon the preferred viscosity and chemical and physical properties of the resulting products. Accordingly the weight percent ofthe liquid medium can be reduced and the weight percent ofthe dispersant can be increased up to 20 weight percent, more preferably from .01 to 10 weight percent and most preferably from 3 to 6 weight percent.
  • the amount of nanotubes, dispersant, and liquid medium can be varied as long as the desired HBL value is maintained to produce compounds having a gel, grease, or wax type consistency.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

Selon l'invention, l'introduction de nanotubes dans un liquide permet de modifier les propriétés physiques et/ou chimiques de ce liquide. En effet, la dispersion de nanotubes dans des liquides permet de réaliser des améliorations en termes de transfert de chaleur, de propriétés électriques, de viscosité et de pouvoir lubrifiant. Toutefois, les nanotubes réagissent comme des particules hydrophobes et tendent à s'agglomérer dans les liquides. L'invention concerne des procédés destinés à préparer des dispersions stables de nanotubes et consistant à identifier des tensioactifs/dispersants pouvant disperser les nanotubes de carbone dans un milieu liquide aqueux ou à base de pétrole. Un dispersant approprié est choisi pour le nanotube de carbone et le milieu à base d'eau ou d'huile, ce dispersant étant dissous dans le milieu liquide, d'où la formation d'une solution. On ajoute alors le nanotube de carbone au dispersant contenant la solution par agitation, ultrasonication et/ou des combinaisons correspondantes.
PCT/US2002/038643 2001-12-12 2002-12-06 Preparation de dispersions de nanotubes de carbone stables dans les liquides WO2003050332A1 (fr)

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BRPI0215135-9A BR0215135B1 (pt) 2001-12-12 2002-12-06 Método para preparar uma dispersão estável de nanopartículas de carbono em um líquido
MXPA04005761A MXPA04005761A (es) 2001-12-12 2002-12-06 Preparacion de dispersiones de nanotubo de carbono estable en liquidos.
AU2002357065A AU2002357065B2 (en) 2001-12-12 2002-12-06 Preparation of stable carbon nanotube dispersions in liquids
CA2470113A CA2470113C (fr) 2001-12-12 2002-12-06 Preparation de dispersions de nanotubes stables dans des liquides
EP02804723A EP1495171A4 (fr) 2001-12-12 2002-12-06 Preparation de dispersions de nanotubes de carbone stables dans les liquides
NZ533941A NZ533941A (en) 2001-12-12 2002-12-06 Preparation of stable carbon nanotube dispersions in liquids

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US10/021,767 US6783746B1 (en) 2000-12-12 2001-12-12 Preparation of stable nanotube dispersions in liquids
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DE102004021812A1 (de) * 2004-04-30 2005-12-08 KLüBER LUBRICATION MüNCHEN KG Schmierfett, Verfahren zu dessen Herstellung und dessen Verwendung
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EP1751331A2 (fr) * 2004-04-07 2007-02-14 Eikos, Inc. Modificateurs fugitifs de la viscosite et de la stabilite des compositions de nanotubes de carbone
FR2901154A1 (fr) * 2006-05-18 2007-11-23 Arkema France Utilisation de materiaux composites a base de nanotubes de carbone comme agents viscosifiants de solutions aqueuses
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WO2011072228A1 (fr) 2009-12-11 2011-06-16 Massachusetts Institute Of Technology Imagerie spectrale de matériaux photoluminescents
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WO2013019722A1 (fr) 2011-08-01 2013-02-07 Massachusetts Institute Of Technology Capteurs à base de nanostructures photoluminescentes
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EP1509585A4 (fr) * 2002-05-30 2008-04-09 Ashland Inc Amelioration de la conductivite thermique des fluides avec des nanoparticules graphitees et des nanotubes de carbone
EP1509585A1 (fr) * 2002-05-30 2005-03-02 Ashland Inc. Amelioration de la conductivite thermique des fluides avec des nanoparticules graphitees et des nanotubes de carbone
US7052618B2 (en) 2004-01-28 2006-05-30 Agilent Technologies, Inc. Nanostructures and methods of making the same
EP1751331A2 (fr) * 2004-04-07 2007-02-14 Eikos, Inc. Modificateurs fugitifs de la viscosite et de la stabilite des compositions de nanotubes de carbone
EP1751331A4 (fr) * 2004-04-07 2008-11-05 Eikos Inc Modificateurs fugitifs de la viscosite et de la stabilite des compositions de nanotubes de carbone
DE102004021812A1 (de) * 2004-04-30 2005-12-08 KLüBER LUBRICATION MüNCHEN KG Schmierfett, Verfahren zu dessen Herstellung und dessen Verwendung
US8765488B2 (en) 2004-07-22 2014-07-01 The Board Of Trustees Of The University Of Illinois Sensors employing single-walled carbon nanotubes
US10712347B2 (en) 2004-07-22 2020-07-14 The Board Of Trustees Of The University Of Illinois Sensors employing single-walled carbon nanotubes
WO2007011369A3 (fr) * 2004-08-23 2007-03-22 Du Pont Procede d'elaboration de dispersions de nanotube en carbone/polyaniline (cnt/pani)
WO2007011369A2 (fr) * 2004-08-23 2007-01-25 E.I. Dupont De Nemours And Company Procede d'elaboration de dispersions de nanotube en carbone/polyaniline (cnt/pani)
US9023771B2 (en) 2006-01-31 2015-05-05 Nissan Motor Co., Ltd. Nanoparticle-containing lubricating oil compositions
EP1980609A4 (fr) * 2006-01-31 2011-04-13 Nissan Motor Compositions d'huile lubrifiante contenant des nanoparticules
EP1980609A1 (fr) * 2006-01-31 2008-10-15 Nissan Motor Co., Ltd. Compositions d'huile lubrifiante contenant des nanoparticules
KR101213011B1 (ko) 2006-05-18 2012-12-17 상뜨로 나쇼날 드 라 러쉐르쉐 샹띠피크 수용액용 증점제로서의 탄소 나노튜브 기재 복합체 물질의 용도
FR2901154A1 (fr) * 2006-05-18 2007-11-23 Arkema France Utilisation de materiaux composites a base de nanotubes de carbone comme agents viscosifiants de solutions aqueuses
WO2007135323A3 (fr) * 2006-05-18 2008-11-27 Arkema France Utilisation de materiaux composites a base de nanotubes de carbone comme agents viscosifiants de solutions aqueuses
WO2007135323A2 (fr) * 2006-05-18 2007-11-29 Arkema France Utilisation de materiaux composites a base de nanotubes de carbone comme agents viscosifiants de solutions aqueuses
KR100854967B1 (ko) * 2006-08-16 2008-08-28 금호석유화학 주식회사 탄소나노소재 분산액 및 그의 제조방법
US7935767B2 (en) 2006-12-21 2011-05-03 E. I. Du Pont De Nemours And Company Multiblock polymer dispersions of carbon nanotubes
WO2011036411A1 (fr) 2009-09-25 2011-03-31 Arkema France Mélange-maître pour la fabrication de fluide de forage
FR2950628A1 (fr) * 2009-09-25 2011-04-01 Arkema France Melange-maitre pour la fabrication de fluide de forage
US9896611B2 (en) 2009-09-25 2018-02-20 Arkema France Masterbatch for manufacturing a drilling fluid
WO2011072228A1 (fr) 2009-12-11 2011-06-16 Massachusetts Institute Of Technology Imagerie spectrale de matériaux photoluminescents
FR2965274A1 (fr) * 2010-09-28 2012-03-30 Total Raffinage Marketing Composition lubrifiante
WO2012042406A1 (fr) * 2010-09-28 2012-04-05 Total Raffinage Marketing Composition lubrifiante
WO2013019722A1 (fr) 2011-08-01 2013-02-07 Massachusetts Institute Of Technology Capteurs à base de nanostructures photoluminescentes
CN102627727B (zh) * 2012-03-29 2017-05-31 江南大学 一种光敏性聚合物基碳纳米管分散助剂的制备方法和用途
CN102627727A (zh) * 2012-03-29 2012-08-08 江南大学 一种光敏性聚合物基碳纳米管分散助剂的制备方法和用途
WO2013153085A1 (fr) 2012-04-10 2013-10-17 Contitech Ag Mélange de polymères, mélange de type caoutchouc le contenant et procédé de préparation dudit mélange de type caoutchouc
EP2650325A1 (fr) 2012-04-10 2013-10-16 ContiTech AG Mélange de polymères, mélange de caoutchouc comprenant le mélange de polymères et procédé de préparation du mélange de caoutchouc
WO2015191389A2 (fr) 2014-06-13 2015-12-17 Massachusetts Institute Of Tecnology Nanocapteurs optiques sensibles au saccharide

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CA2470113C (fr) 2011-01-25
AU2002357065A1 (en) 2003-06-23
EP1495171A4 (fr) 2008-04-02
CN1617958A (zh) 2005-05-18
EP1495171A1 (fr) 2005-01-12
CN1304657C (zh) 2007-03-14
CA2470113A1 (fr) 2003-06-19
AU2002357065B2 (en) 2008-09-04
MXPA04005761A (es) 2004-11-01
BR0215135A (pt) 2005-01-04
NZ533941A (en) 2006-09-29

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