CN104031716A - Lubricants containing graphene - Google Patents
Lubricants containing graphene Download PDFInfo
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- CN104031716A CN104031716A CN201310070711.1A CN201310070711A CN104031716A CN 104031716 A CN104031716 A CN 104031716A CN 201310070711 A CN201310070711 A CN 201310070711A CN 104031716 A CN104031716 A CN 104031716A
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- lubricating oil
- oil containing
- functional group
- containing graphene
- graphene
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 88
- 239000000314 lubricant Substances 0.000 title 1
- 239000000843 powder Substances 0.000 claims abstract description 54
- 239000010687 lubricating oil Substances 0.000 claims abstract description 49
- 125000000524 functional group Chemical group 0.000 claims abstract description 36
- 239000003607 modifier Substances 0.000 claims abstract description 16
- 230000001050 lubricating effect Effects 0.000 claims abstract description 15
- 239000004519 grease Substances 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
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- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- -1 methacryloxy, acryloxy Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
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- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 claims 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims 1
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- BHQCQFFYRZLCQQ-UHFFFAOYSA-N (3alpha,5alpha,7alpha,12alpha)-3,7,12-trihydroxy-cholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004380 Cholic acid Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
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- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 2
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- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 2
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 2
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- 238000009736 wetting Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Lubricants (AREA)
Abstract
A lubricating oil containing graphene comprises a lubricating grease and a plurality of modified graphene powders, wherein the modified graphene powders account for 0.001wt% to 10wt% of the lubricating grease, are uniformly dispersed in the lubricating grease, each modified graphene powder comprises at least one surface modification layer, each surface modification layer comprises a surface modifier, each surface modifier comprises at least two functional groups, the two functional groups are respectively positioned at two ends of each surface modifier, one functional group of each functional group and an organic functional group on the surface of the corresponding graphene powder generate chemical bonding, the other functional group of each functional group forms the surface characteristic of the corresponding modified graphene powder, and the surface modification layer can provide good affinity between the modified graphene powder and the lubricating oil.
Description
Technical field
The present invention relates to a kind of lubricating oil, espespecially a kind of lubricating oil that includes Graphene.
Background technology
Mono-layer graphite, be called again Graphene (graphene), be a kind of by monolayer carbon atom the crystalline network with the tightly packed one-tenth bi-dimensional cellular of graphite key (sp2) shape, therefore only there is the thickness of a carbon atom, graphite key is the compound keys of covalent linkage and metallic bond, can say the heaven-made match of isolator and electrical conductor.The Andre Geim of Univ Manchester UK in 2004 and Konstantin Novoselov successfully utilize the mode of tape stripping graphite, and confirmation can obtain the Graphene of individual layer, and obtains the Nobel prize for physics of 2010.
Graphene be at present the thinnest be in the world also the hardest material, thermal conductivity is higher than carbon nanotube and diamond, under normal temperature, its electronic mobility is also than carbon nanotube or silicon wafer height, resistivity is lower than copper or silver, it is the current material of resistivity minimum in the world, these unique electric charge mechanical propertiess make to add the matrix material greater functionality of Graphene, not only show excellent mechanics and electric property, also there is good processing characteristics, for matrix material provides more wide Application Areas.But the Graphene of structural integrity is the two dimensional crystal by the benzene six-ring containing any labile bond does not combine, chemical stability is high, its surface is inert condition, a little less than interacting with other medium (as solvent etc.), and between the sheet of Graphene and sheet, there is stronger Fan get Wa Li, easily produce and reunite, make it be insoluble in water and other conventional organic solvent, more difficult and other material blending forms matrix material, thereby greatly limited further research and the application of Graphene, the past is applied as matrix material mainly with other graphite-like or carbon class material.
US Patent No. 201000204072 is passed through expanded graphite again ball milling control particle diameter after the processing such as microwave expansion, a small amount of 0.01wt%～2wt% that adds is at machining oil or other lubricating oil, strengthens lubricating oil Yin Gaowen and evaporate lost oilness in the course of processing.Expanded graphite is a vermiform material, and length reaches the spectrum of hundreds of microns conventionally, is not suitable for high-accuracy power lubrication purposes.
US Patent No. 20070158609 mixes to strengthen the character such as oilness, the capacity of heat transmission, viscosity with lubricating grease with lubricating oil with carbon nanotube (CNT), optimum addition is 0.1wt%～3wt%, but CNT has the quantification of being difficult for and the high problem of unit price, has limited the business-like potentiality of its related products.
US Patent No. 8349774B2 is added in lubricating oil and strengthens its lubricating quality with graphite and silver-colored composite nano rice corpuscles, and best adding proportion is all individually 0.1vol%～1vol%, but Ag is a kind of precious metal, also will limit its business-like application on cost.
Summary of the invention
Main purpose of the present invention is to provide a kind of lubricating oil that contains Graphene, this lubrication pockets that contains Graphene is containing lubricating grease and multiple upgrading graphene powder, it is 0.001wt% to 10wt% that described upgrading graphene powder accounts for weight ratio, be dispersed evenly in this lubricating grease, and respectively this upgrading graphene powder comprises at least one surfaction layer, this at least one surfaction layer comprises a surface modifier, comprise at least two functional groups, lay respectively at two ends of this surface modifier, this at least two functional group's a functional group and the organic functional base on this graphene powder surface produce chemical bonded refractory, another functional group of this at least two functional group forms the surface property of this upgrading graphene powder, and this surfaction layer can provide upgrading graphene powder and the good affinity of lubricating oil.
In the lubricating oil that the present invention contains Graphene, surface modifier accounts between the weight percent 0.1-10.0wt% of each this upgrading graphene powder weight, and the lubricating oil that contains Graphene has following physical properties, the planar dimension of upgrading graphene powder is greater than 1um and thickness is less than 10nm, and the plane length of described upgrading graphene powder and the ratio of thickness are greater than 100, this lubricating oil that contains Graphene makes the mutual frictional coefficient of operand be less than 0.1, and the heat-conduction coefficient of this lubricating oil that contains Graphene is greater than 0.2W/mK.
The surface modifier of surfaction layer comprise coupler, lipid acid and resin at least one of them, the structure of this this coupler is M
x(R)
y(R ')
z, wherein M is a metallic element, R is a wetting ability functional group, R ' is a lipophilicity functional group, wherein 0≤x≤6, 1≤y≤20, and 1≤z≤20, wherein M is selected from aluminium, titanium, one of them of zirconium and silicon, R is selected from alkoxyl group, carbonyl, carboxyl, acyloxy, amido, stretch alkoxyl group and stretch one of them of alcoxyl carboxyl, and R ' is selected from vinyl, cycloaliphatic ring oxyalkyl, styryl, methacryloxy, acryloxy, fatty group amido, chloropropane base, fatty group thiohydroxy, fatty group sulfonium ion base, isocyanato, fatty group Urea-based, fatty group carboxyl, fatty group hydroxyl, cyclohexyl, phenyl, fatty group formyl radical, one of them of ethanoyl and benzoyl.This lipid acid is selected from one of them of stearic acid and oleic acid; This resin is selected from one of them of epoxy resin, polyurethane resin, silicone resin, phenol resins and alkyd resin.
Further, the lubricating oil that the present invention contains Graphene also comprises at least one dispersion agent, this dispersion agent has two ends, one of them end of this two end have a long carbochain and a phenyl at least one of them, the other end wherein of this two end have monosulfonic acid root functional group, a cholic acid root functional group and a carboxyl at least one of them.
By this, because graphene powder contained in the present invention is by surfaction, and make graphene powder and the good affinity of lubricating oil, promote significantly the applicability of Graphene, and the advantage of numerous Graphenes can be applied in actual product, and improve the variety of issue facing in prior art.
Embodiment
Below embodiments of the present invention are done to more detailed description, make those of ordinary skill in the art study carefully after this specification sheets and can implement according to this.
The lubricating oil that contains Graphene that invention provides, comprise lubricating grease and multiple upgrading graphene powder, it is 0.001wt% to 10wt% that described upgrading graphene powder accounts for weight ratio, be dispersed evenly in this lubricating grease, and respectively this upgrading graphene powder comprises at least one surfaction layer, this at least one surfaction layer comprises a surface modifier, comprise at least two functional groups, lay respectively at two ends of this surface modifier, this at least two functional group's a functional group and the organic functional base on this graphene powder surface produce chemical bonded refractory, another functional group of this at least two functional group forms the surface property of this upgrading graphene powder, and this surfaction layer can provide upgrading graphene powder and the good affinity of lubricating oil.
In the lubricating oil that the present invention contains Graphene, surface modifier accounts between the weight percent 0.1-10.0wt% of each this upgrading graphene powder weight, and the lubricating oil that contains Graphene has following physical properties, the planar dimension of upgrading graphene powder is greater than 1um and thickness is less than 10nm, and the plane length of described upgrading graphene powder and the ratio of thickness are greater than 100, this lubricating oil that contains Graphene makes the mutual frictional coefficient of operand be less than 0.1, and the heat-conduction coefficient of this lubricating oil that contains Graphene is greater than 0.2W/mK.
The surface modifier of surfaction layer comprise coupler, lipid acid and resin at least one of them, the structure of this this coupler is M
x(R)
y(R ')
z, wherein M is a metallic element, R is a wetting ability functional group, R ' is a lipophilicity functional group, wherein 0≤x≤6, 1≤y≤20, and 1≤z≤20, wherein M is selected from aluminium, titanium, one of them of zirconium and silicon, R is selected from alkoxyl group, carbonyl, carboxyl, acyloxy, amido, stretch alkoxyl group and stretch one of them of alcoxyl carboxyl, and R ' is selected from vinyl, cycloaliphatic ring oxyalkyl, styryl, methacryloxy, acryloxy, fatty group amido, chloropropane base, fatty group thiohydroxy, fatty group sulfonium ion base, isocyanato, fatty group Urea-based, fatty group carboxyl, fatty group hydroxyl, cyclohexyl, phenyl, fatty group formyl radical, one of them of ethanoyl and benzoyl.Common coupler has silicane, metatitanic acid lipid, zirconic acid lipid, aluminium zirconic acid lipid, aluminic acid lipid, chromic acid lipid, wherein common with silicane.
Surface modifier of the present invention can be selected the lipid acid of high-carbon number, it also possesses two functional groups that have relative two ends, one functional group can react with graphene powder surface, another functional group forms the surface property that is different from pure graphene powder simultaneously, be easy to produce affinity between lubricating oil, this high carbon number lipid acid is selected from one of them of stearic acid and oleic acid.This resin is selected from one of them of epoxy resin, polyurethane resin, silicone resin, phenol resins and alkyd resin.
Further, the lubricating oil that the present invention contains Graphene also comprises at least one dispersion agent, this dispersion agent has two ends, one of them end of this two end have a long carbochain and a phenyl at least one of them, the other end wherein of this two end have monosulfonic acid root functional group, a cholic acid root functional group and a carboxyl at least one of them.
With actual experiment, as explanation, first, prepare graphene powder below, the mode of preparation comprises oxidation step, peels off and prereduction step, reduction and heat treatment step and mechanical mill and reduction step.Oxidation step graphite material oxidation forms graphite oxide, graphite material can be selected from natural graphite (graphite), expansible black lead (expandable graphite), electrographite (artificial graphite), graphite fibre (graphite fiber), carbon nanotube (carbon nano-tube) and carbonaceous mesophase spherules (mesophase carbon micro-bead) at least one of them.The mode of oxidation is Han Mosi (Hummers) method, but is not limited to this.Peel off with prereduction step system this graphite oxide contact to thermal source, to form the how graphite oxide of meter structure of individual layer.Reduction and heat treatment step by individual layer how the graphite oxide of rice structure be positioned in reducing atmosphere, by individual layer how the oxygen-content reduction of the graphite oxide of rice structure to 1wt%.Finally, by mechanical mill and reduction step, by individual layer how the graphite oxide of rice structure be separated into mono-layer graphite completely, adopt basic solution as abrasive solvents simultaneously, the mode of wherein grinding can be ultrasonic vibrating (ultrasonication), planetary grinding (planetary ball mill), ball milling (ball mill) and pneumatic type grinding (jet mill) at least one of them.Be ammoniacal liquor (ammonia as the basic solution of abrasive solvents, NH4OH), lithium hydroxide (lithium hydroxide, LiOH), sodium hydroxide (sodium hydroxide, NaOH) and potassium hydroxide (potassium hydroxide, KOH) at least one of them.
Then, adopt coupler aminosiloxane (3-Aminopropyl triethoxysilane) as surface modifier, the graphene powder of previously having prepared is made as to upgrading graphene powder, the structure of this coupler is Si (C3H6N) (C2H5O) 3, embodiment is for to add surface modifier in the mixing solutions of one ethanol and water, add again graphene powder to carry out mix and blend, last air exhaust filtering take out powder and in baking oven heat drying, can obtain upgrading graphene powder.
The lubricating oil that includes Graphene is made in example 1-5 upgrading graphene powder and lubricating grease blending, making method adds upgrading graphene powder respectively in lubricating grease according to different ratios, mix via mechanical-physical, as high pressure homogenizer, stirrer, ultrasonic vibrating machine make graphene uniform be scattered in lubricating oil after processing, then measure frictional coefficient by four-ball tester.Wherein the content of different upgrading graphene powders arranges in table 1 the frictional coefficient impact of lubricating oil.Relatively learnt by frictional coefficient, only need to add the oilness that can significantly promote lubricating oil less than the upgrading graphene powder of 0.002wt%, too much upgrading graphene powder makes an addition in lubricating grease, cause on the contrary frictional coefficient to rise, again by the thermal conduction instrument sample test heat-conduction value with example 2 for example 1 respectively, be respectively 0.14W/mK and W/mK, add upgrading graphene powder contributes to the thermal conduction of lubricating oil to promote simultaneously, temperature can effectively reduce workpiece operation time, the life-span of prolongation workpiece.Therefore add upgrading graphene powder and not only contribute to promote its performance in lubricating oil, more because addition is low, limited on holistic cost impact.
Form 1
Example 6-10 illustrates and further adds the performance performance of dispersion agent in the lubricating oil that contains Graphene again, wherein this dispersion agent is selected oleic acid, respectively upgrading graphene powder and dispersion agent are added in lubricating grease, mix through mechanical-physical again, as extremely completely even after high pressure homogenizer, stirrer, the processing of ultrasonic vibrating machine, then by four-ball tester measurement frictional coefficient.The result of table 2 shows further adds after dispersion agent, because the dispersiveness of upgrading graphene powder is better, frictional coefficient more declines, and the addition of upgrading graphene powder can further reduce, and shows that upgrading graphene powder affects the performance of frictional coefficient in the degree of scatter of lubricating oil.
Form 2
By this, because graphene powder contained in the present invention is by surfaction, and make graphene powder and lubricating oil there is good affinity, promote the applicability of Graphene, more can be by the characteristic of Graphene, make lubricating oil there is better heat conductivity, lower frictional coefficient, reduced friction, can also further promote the stability of viscosity.
The foregoing is only to explain preferred embodiment of the present invention; not attempt is done any pro forma restriction to the present invention according to this; there are any modification or the change of the relevant the present invention that does under identical invention spirit therefore all, all must be included in the category that the invention is intended to protection.
Claims (12)
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