CN105838478A - Graphene/onion-like fullerene complex solid lubricant and preparation method thereof - Google Patents
Graphene/onion-like fullerene complex solid lubricant and preparation method thereof Download PDFInfo
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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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
- C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
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- 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
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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Abstract
The invention discloses a graphene/onion-like fullerene complex solid lubricant and its preparation method. Mainly through a chemical method, a polymer grafting agent such as stearic acid and the like is grafted with graphene and then grafted with onion-like fullerene, thus effectively compounding graphene and onion-like fullerene. The solid lubricant not only raises anti-wear and anti-friction properties of lubricating oil and also has good lipophilicity. The product can have good dispersity and stability in lubricating oil and greatly raises overall lubricating property of lubricating oil.
Description
Technical field
The invention belongs to kollag technical field, be specifically related to a kind of kollag by Graphene and onion-like fullerene and preparation method thereof.
Background technology
Fretting wear is prevalent in nature, and friction consumes the biggest energy and resource, it was reported that the energy in the world about l/3 finally consumes in various forms of frictions, and the whole world is annual because the loss that causes of fretting wear is more than a $ 100 billion.Nano-carbon material, owing to because its yardstick is little, light weight, having preferable dispersibility and stability in lubricating oil, has shown the performance of excellence as lube oil additive.And onion-like fullerene (OFLs) is due to its super-strong and super-toughened property, the hexagonal structure of unique graphite-like structure, there is the self-lubricating property of excellence.Due to the Van der Waals force that " nanometer one Bulbus Allii Cepae " interlayer is more weak, make this " nanometer one Bulbus Allii Cepae " easily decomposes, forming one layer of equadag coating between friction pair to be similar to micro-bearing and replace the oil film ruptured to play lubrication, these are that the application of onion-like fullerene self-lubricating property illustrates fine prospect.
Graphene replaces traditional lubricant as lubricant, it is to utilize solid physico-chemical property by temperature, feature that pressure variations influence is less, Graphene is added in lubricating oil, play the distinctive physical and chemical performance of its nano material, playing the effect of pressure-bearing skeleton in lubricating oil, Graphene can partly be seeped into frictional metal surface, changes surface texture, make its hardness change, improve antioxidation, anticorrosive and abrasion resistance.The Graphene not penetrating into metal surface is filled in the concavo-convex place of friction surface, improves the loaded area of rubbing surface, to reduce coefficient of friction, improves bearing capacity.
Summary of the invention
It is an object of the invention to provide a kind of good dispersion, the Graphene that stability is strong/onion-like fullerene composite solid lubricating agent and preparation method thereof, add this additive and not only improve the antiwear and reducing friction performance of lubricating oil, and improve extreme pressure and the bearing capacity of lubricating oil.
Described Graphene/onion-like fullerene composite solid lubricating agent is, by macromolecule scion grafting agent, Graphene and onion-like fullerene are compounded to form kollag；Described Graphene is 1-20:1 with the mass ratio of onion-like fullerene.
Present invention also offers the preparation method of a kind of Graphene/onion-like fullerene composite solid lubricating agent, step is: 1) by polymeric grafting agent and dispersant, join stirring and dissolving in solvent；Adding the graphene oxide powder stirring and evenly mixing being dried and obtain mixture, be heated to reflux by mixture, obtain black solid material, wash, be dried to obtain the graphene oxide powder of macromolecule scion grafting, sample is designated as G1；
2) take G1 and join stirring and evenly mixing in reducing agent, drip strong aqua ammonia；Then it is heated to reflux to reaction completely, washing, to dry, sample is designated as G2；
3) taking in the mixing acid that onion-like fullerene joins concentrated nitric acid and concentrated sulphuric acid, stir under room temperature, washing, to neutral, is dried to obtain the oxidation onion-like fullerene powder body of pretreatment, and sample is designated as G3；
4) mixture of G2 sample and G3 sample is joined in dilute sulfuric acid, stirring reaction under room temperature, product is filtered, washs to neutral, after drying, obtain Graphene/onion-like fullerene composite solid lubricating agent.
Further, described step 1) in polymeric grafting agent be stearic acid, oleic acid or silane coupler；Described dispersant is Span-80, oleic acid, cetyl trimethylammonium bromide or calcium dodecyl benzene sulfonate；Described solvent is hexamethylene；Described stearic acid is 10-0.5:1 with the mass ratio of dispersant, and described stearic acid and the mixture of dispersant are 1:6-10 with the amount ratio of hexamethylene.
Further, described step 1) in the mass ratio of polymeric grafting agent and graphene oxide be 0.5-5:1.
Further, described step 1) in graphene oxide powder prepared by low-temperature oxidation graft process, the specific surface area of described graphene oxide is 200-500m2/ g, sheet footpath is 200-500nm.
Further, described step 1) in the temperature that is heated to reflux of mixture be 60-85 DEG C, the time is 3-6h.
Further, described step 2) in reducing agent be grape extract；G1 is 5-10g/L with the amount ratio of grape extract, and described G1 is 2.5-5g/mL with the amount ratio of strong aqua ammonia.
Further, described step 3) concentrated sulphuric acid is 1-5:1 with the volume ratio of concentrated nitric acid in mixed acid, is chemically pure reagent；Described onion-like fullerene is 1:2-3 with the amount ratio of mixed acid.
Further, described step 3) in onion-like fullerene be that prepared by catalytic decomposition method and purified；The particle diameter of described onion-like fullerene is 30-50nm, and the lamella number of plies is 10-15 layer.
Further, described step 4) in the mass ratio that concentration is 1-3mol/L, mixture and dilute sulfuric acid of dilute sulfuric acid be 1:10-15.
The present invention is compared with prior art, it has the beneficial effect that the Graphene of lamella is got up to form the composite construction in " ball-face " by macromolecule scion grafting agent with onion-like fullerene scion grafting, this appearance structure not only greatly strengthen the antiwear and reducing friction effect of Graphene, and the addition of onion-like fullerene is also greatly enhanced its anti-extreme pressure and bearing capacity.Graphene and the most compound of onion-like fullerene have not only played the lubrication between Graphene " lamella ", and have played the effect of " ball bearing " of onion-like fullerene, serve the superpower effect of collaborative lubrication.With macromolecule scion grafting agent such as stearic acid, the two scion grafting is got up, enhance the adhesion of the two, and for from appearance structure, do not affect respective performance, compared to simply onion-like fullerene and Graphene being combined, in the method for stearic scion grafting relatively simple, need not the highly energy-consumings such as high temperature process, and the lipophile of stearic macromolecular chain effectively reduces counteracting graphene film interlayer Van der Waals force, eliminate the reunion of graphene film interlayer, strengthen compound particle dispersibility in lubricating oil and stability.
Accompanying drawing explanation
Fig. 1 Graphene is schemed with onion-like fullerene compound particle SEM.
Detailed description of the invention
The open a kind of Graphene/onion-like fullerene composite solid lubricating agent of the present invention, mainly by chemical method by macromolecule scion grafting agent scion grafting Graphenes such as stearic acid, scion grafting onion-like fullerene the most again, Graphene is the most compound with onion-like fullerene, and described Graphene is 1-20:1 with the mass ratio of onion-like fullerene.This kollag not only increases antiwear and reducing friction performance and the anti-extreme pressure energy of lubricating oil, and lipophile is fabulous, can have good dispersibility and stability in lubricating oil, and lubricating oil entirety greasy property is greatly improved.
The preparation method of a kind of Graphene of the present invention/onion-like fullerene composite solid lubricating agent is as follows:
A, polymeric grafting agent is uniform with dispersant, joining and add ultrasonic agitation 30-60min in hexamethylene, described polymeric grafting agent is 0.5-10:1 with the mass ratio of dispersant, and described polymeric grafting agent and the mixture of dispersant are 1g:6-10mL with the amount ratio of hexamethylene.
Described dispersant is Span-80, oleic acid, cetyl trimethylammonium bromide or calcium dodecyl benzene sulfonate, and effect is to be dispersed in hexamethylene by stearic acid.
Described polymeric grafting agent is stearic acid, oleic acid, silane coupler (KH550, KH560) etc..
Then adding dry graphene oxide powder and continue ultrasonic agitation 30-60min, described polymeric grafting agent is 0.5-5:1 with the mass ratio of graphene oxide；Described graphene oxide powder is by low-temperature oxidation graft process, and prepared by the Hummers method namely improved, the specific surface area of described graphene oxide is 200-500m2/ g, sheet footpath is 200-500nm.
Then at 60-85 DEG C, the mixture of above-mentioned polymeric grafting agent Yu graphene oxide being heated to reflux 3-6h, be cooled to after room temperature reduce pressure sucking filtration, takes its surface atrament, and with detergent centrifuge washing 5-8 time, described detergent is acetone or petroleum ether.Then being vacuum dried 1-2h at a temperature of 80-100 DEG C and obtain the graphene powder of macromolecule scion grafting, sample is designated as G1.In this step polymeric grafting agent and graphene oxide mixture be heated to reflux temperature, the time can affect the polymeric grafting agent scion grafting graft effect to surface of graphene oxide.
B, takes G1 and joins reducing agent invading the interior stirring 30-60min, drip strong aqua ammonia；Described G1 is 5-10g/L with the amount ratio of reducing agent, and described G1 is 2.5-5g/mL with the amount ratio of strong aqua ammonia；The effect of described strong aqua ammonia is to provide alkaline environment in the solution, makes G1 be easier to be uniformly dispersed.Then 80-90 DEG C is heated to reflux 1-2h, then uses deionized water centrifuge washing 5-8 time, dries, and sample is designated as G2.
Described reducing agent is preferably the red grape extract of self-control, be Fructus Vitis viniferae is squeezed into juice after, be heated to fluidized state and keep 9-10min, then cold filtration 5-8 is all over obtaining.Containing mass concentration in described red grape extract is the ascorbic acid of 0.02-0.04%, the glucose of 2-8%, the resveratrol of 0.01-0.02%, and as reducing agent, effect is that graphene oxide is reduced into Graphene.Reducing agent in red grape extract reacts with G1, and G1 is reduced, and reducing agent content reduces, and red liquid becomes blackish green, and described blackish green is the color of the Graphene that reduction obtains.Therefore the present invention uses red grape extract can play the effect of reducing agent, again can the effect of indicator, Indicator Reaction terminal.
C, takes prepared by catalytic decomposition method and purified onion-like fullerene, joins in the mixing acid of concentrated nitric acid (64%) and concentrated sulphuric acid (98%), and described onion-like fullerene is 1:2-3 with the amount ratio of mixed acid；Stirring 2-6h under room temperature, then with the mixed liquor centrifuge washing of ethanol and deionized water (volume ratio is 2:1) to neutral, then vacuum drying 1-2h obtains the oxidation onion-like fullerene powder body of pretreatment at a temperature of 80-100 DEG C, and sample is designated as G3.
In described mixed acid, concentrated sulphuric acid is 1-5:1 with the volume ratio of concentrated nitric acid, and is chemically pure reagent.The effect of described mixed acid is that onion-like fullerene is carried out oxidation processes, and fullerene surface after oxidation generates oxy radical, and the scion grafting contributing to polymeric grafting agent and fullerene is reacted.
Onion-like fullerene prepared by described catalytic decomposition method particular by ferrum and nickel as catalyst, using acetylene black as carbon source, look unfamiliar on a catalyst at 700-800 DEG C long forming, with low cost compared to additive method, carbon source supply rate high, condition is easy to control.Described onion-like fullerene particle diameter is 30-50nm, and the lamella number of plies is 10-15 layer.
To the purification step of onion-like fullerene it is: be first that dilute hydrochloric acid 80-100 DEG C of the fullerene 1mol/L preparing catalytic decomposition method is heated to reflux 2-3h, after filtration, product is added in the nitration mixture (concentrated sulphuric acid and concentrated nitric acid volume ratio 3-5:1) of concentrated sulphuric acid and concentrated nitric acid 80-100 DEG C and is heated to reflux 2-3h, the product high speed ball milling 5-10h that will filter, obtains onion-like fullerene after purification with deionized water centrifuge washing to neutral the most again.The purity of the onion-like fullerene of described purification be 98% and more than.
The purpose of pretreatment oxidation onion-like fullerene is to remove the foreign particles such as amorphous carbon microgranule therein, amorphous carbon fiber, graphite particulate, improves fullerene purity.
D, is positioned over G2 sample and G3 sample mix in planetary ball mill, and the mass ratio of G2 sample and G3 sample is 1-20:1, high speed ball milling 30-60min under conditions of rotating speed is 2500-3000r/min.Owing to G2 is layer structure, and G3 is 3-D solid structure, and G2 content its lamellar structure high can fold, bend, and increases its contact point, promotes reaction, and the content height of G3 the most easily produces space steric effect, hinders the carrying out of scion grafting reaction.
Then the mixture of G2 sample and G3 sample is joined in dilute sulfuric acid, the concentration of dilute sulfuric acid be the mass ratio of 1-3mol/L, mixture and dilute sulfuric acid be 1:10-15, under room temperature magnetic agitation reaction 24-48h.Described dilute sulfuric acid plays the effect of scion grafting auxiliary agent, promotes the stearic acid on G2 surface and the oxy radical on G3 surface to carry out scion grafting reaction, and the concentration of dilute sulfuric acid and stirring response time are bigger to grafting influential effect.If connecing agent with stearic acid for scion grafting, then using dilute sulfuric acid as scion grafting auxiliary agent, if with oleic acid for scion grafting agent, need to be with octyltri-ethoxysilane for scion grafting auxiliary agent and it needs to high-temperature heating backflow in step d, if with silane coupler for scion grafting agent, then needing with polystyrene is scion grafting auxiliary agent.Sample after filtration hexamethylene washs 5-8 time, the most again with deionized water centrifuge washing to neutral.The sample washed is dried in 50-80 DEG C of baking oven, finally obtains Graphene/onion-like fullerene composite solid lubricating agent.
Embodiment 1
(1) mixture (including 2g stearic acid and 3g Span-80) of 5g stearic acid with Span-80 is joined stirring in 50mL hexamethylene and add ultrasonic 30min, it is subsequently adding the graphene oxide that 2g is dried, continue to stir ultrasonic 30min, 80 DEG C are heated to reflux 3h, reduce pressure after being cooled to room temperature sucking filtration, takes its surface atrament；With detergent acetone centrifuge washing 8 times, being vacuum dried 2h and obtain the graphene powder of stearic acid scion grafting at a temperature of 80 DEG C, sample is designated as G1.
(2) taking 0.5gG1 and join stirring 60min in 100mL redness grape extract, drip the strong aqua ammonia of 200 μ L, then 85 DEG C are heated to reflux 2h, until red liquid becomes blackish green, use deionized water centrifuge washing 8 times after filtration, dry, and sample is designated as G2.
The concrete preparation method of grape extract: after Radix seu Herba Tetrastigmatis Hypoglauci is squeezed into juice, is heated to fluidized state and keeps 10min, and then cold filtration obtains for 8 times.
(3) take 2g through catalytic decomposition method prepare and purified onion-like fullerene join concentrated nitric acid and concentrated sulphuric acid (VHNO3:VH2SO4=1:3) in the nitration mixture that configures, 2h is stirred under room temperature, then with the mixed liquor centrifuge washing of ethanol and deionized water (volume ratio 2:1) to neutral, being then vacuum dried 2h at a temperature of 80 DEG C and obtain the oxidation onion-like fullerene powder body of pretreatment, sample is designated as G3.
Onion-like fullerene preparation and purification step: onion-like fullerene is as catalyst by ferrum and nickel, using acetylene black as carbon source, long forming of looking unfamiliar on a catalyst at 750 DEG C.Followed by purification step, first it is that the dilute hydrochloric acid 85 DEG C that fullerene adds to 1mol/L is heated to reflux 3h, the product of filtration is added in the nitration mixture (concentrated sulphuric acid and concentrated nitric acid volume ratio 3:1) of concentrated sulphuric acid and concentrated nitric acid 90 DEG C and is heated to reflux 2h, the product high speed ball milling 4h that will filter, then obtains onion-like fullerene after purification with deionized water centrifuge washing to neutral.
(4) 4g G2 sample and G3 sample mix (mass ratio G2:G3=5:1) are positioned over planetary ball mill 2500r/min high speed ball milling 30min, then magnetic agitation 24h under (2mol/L) room temperature is added mixture in the dilute sulfuric acid of 40mL, wash 5 times with hexamethylene, with deionized water centrifuge washing to neutral, the sample washed is dried in 80 DEG C of baking ovens, obtains Graphene/onion-like fullerene composite solid lubricating agent.
Embodiment 2
(1) by the mixture (including 1.5g stearic acid and 2g oleic acid) of 3.5g stearic acid with oleic acid, oleic acid is not only a kind of lipophile dispersant can also participate in surface scion grafting reaction, join stirring in 40mL hexamethylene and add ultrasonic 30min, add the graphene oxide powder continuation ultrasonic 30min of stirring that 2g is dried, 80 DEG C are heated to reflux 3h, reduce pressure after being cooled to room temperature sucking filtration, take its surface atrament, with detergent petroleum ether centrifuge washing 8 times, 2h it is vacuum dried at a temperature of 80 DEG C, obtaining the graphene powder of stearic acid scion grafting, sample is designated as G1.
(2) taking 0.7gG1 and join stirring 50min in 100mL redness grape extract, drip the strong aqua ammonia of 179 μ L, 85 DEG C are heated to reflux 2h, until red liquid becomes blackish green, use deionized water centrifuge washing 8 times after filtration, dry, and sample is designated as G2.Grape extract preparation process such as embodiment 1.
(3) take prepared by 2g catalytic decomposition method and purified onion-like fullerene and join concentrated nitric acid and concentrated sulphuric acid (volume ratio VHNO3:VH2SO4=1:4) in the nitration mixture that configures, stir 2h under room temperature, with the mixed liquor centrifuge washing of ethanol and deionized water (volume ratio 2:1) to neutral, be vacuum dried 2h at a temperature of 80 DEG C, obtain the oxidation onion-like fullerene powder body of pretreatment, sample is designated as G3.Onion-like fullerene preparation and purification step such as embodiment 1.
(4) G2 sample and G3 sample mix (mass ratio G2:G3=10:1) are positioned over planetary ball mill 2500r/min high speed ball milling 30min, add mixture to (2mol/L) in the dilute sulfuric acid of 40mL, magnetic agitation 24h under room temperature；Wash 5 times with hexamethylene, with deionized water centrifuge washing to neutral, the sample washed is dried in 80 DEG C of baking ovens, obtains Graphene/onion-like fullerene composite solid lubricating agent.
Embodiment 3
(1) mixture (including 1.5g stearic acid and 2.5g calcium dodecyl benzene sulfonate) of 4g stearic acid with calcium dodecyl benzene sulfonate is joined stirring in 40mL hexamethylene and add ultrasonic 30min, add the homemade graphene oxide powder continuation ultrasonic 30min of stirring that 2g is dried, 80 DEG C are heated to reflux 3h, reduce pressure after being cooled to room temperature sucking filtration, take its surface atrament, with detergent acetone centrifuge washing 8 times, being vacuum dried 2h at a temperature of 80 DEG C and obtain the graphene powder of stearic acid scion grafting, sample is designated as G1.
(2) taking 0.5gG1 and join stirring 60min in the red Sucus Vitis viniferae of 100mL self-control, drip the strong aqua ammonia of 200 μ L, then 85 DEG C are heated to reflux 2h, until red liquid becomes blackish green, use deionized water centrifuge washing 8 times after filtration, dry, and sample is designated as G2.Grape extract preparation process such as embodiment 1.
(3) take prepared by 3g catalytic decomposition method and purified onion-like fullerene and join concentrated nitric acid and concentrated sulphuric acid (volume ratio VHNO3:VH2SO4=1:4) in the nitration mixture that configures, 2h is stirred under room temperature, then with the mixed liquor centrifuge washing of ethanol and deionized water (volume ratio 2:1) to neutral, being then vacuum dried 3h at a temperature of 70 DEG C and obtain the oxidation onion-like fullerene powder body of pretreatment, sample is designated as G3.Onion-like fullerene preparation and purification step such as embodiment 1.
(4) G2 sample and G3 sample mix (mass ratio G1:G2=15:1) are positioned over planetary ball mill 2500r/min high speed ball milling 30min, add mixture in the dilute sulfuric acid of 50mL magnetic agitation 24h under (2mol/L) room temperature, wash 5 times with hexamethylene, with deionized water centrifuge washing to neutral, the sample washed is dried in 80 DEG C of baking ovens, obtains Graphene/onion-like fullerene composite solid lubricating agent.
Embodiment 4
The sample prepared by above-described embodiment 1-3, Graphene, onion-like fullerene respectively take 0.001g and add 10g base oil 4000r/min high-speed stirred 30min to, then its abrasion resistance and bearing capacity are tested, obtain the performance test table of lubricating oil as shown in Figure 1, including embodying the centrefuge experiment of stability, standing experiment, embody the coefficient of friction of abrasion resistance, rub spot diameter, embodies PB, PD value of extreme pressure property.Testing friction performance instruments is MRS-10B four-ball friction and wear test machine, performs GB/T3142-1982 and SH0762-2005 standard.Measurement result is as shown in table 1.
Table 1 lubricating oil sample performance test data table
From table 1 in view of the Friction dates of embodiment 1-3 sample, be used alone the abrasion-resistance of Graphene lubricating oil preferably but anti-extreme pressure energy DeGrain, but and be used alone onion-like fullerene lubricating oil anti-extreme pressure can effective abrasion-resistance effect general.Sample prepared by embodiment 1-3 is compared with being used alone Graphene lubricating oil or be used alone onion-like fullerene lubricating oil, abrasion-resistance and anti-extreme pressure energy effect have lifting, illustrate that Graphene and the most compound of onion-like fullerene have not only been played the lubrication between Graphene " lamella " by the present invention, and played the effect of " ball bearing " of onion-like fullerene, serve the superpower effect of collaborative lubrication.With macromolecule scion grafting agent such as stearic acid, the two scion grafting is got up, enhance the adhesion of the two, respective performance is not affected for from appearance structure, and the lipophile of stearic acid macromolecular chain effectively reduces counteracting graphene film interlayer Van der Waals force, eliminate the reunion of graphene film interlayer, strengthen compound particle dispersibility in lubricating oil and stability.
It can also be seen that from table 1 its comprehensive tribological property is the most excellent when the mass ratio of G2 with G3 is 10:1, and dispersibility and the stabilizing effect in lubricating oil is also the highest, Graphene reaches best with onion-like fullerene synergism.
If accompanying drawing 1 is the SEM picture of kollag.Finding out that from figure onion-like fullerene is dispersed in around surface and the lamella of graphene sheet layer, by the mutual scion grafting of high molecular stearic acid, this shape characteristic greatly strengthen dispersibility and the stability of graphene sheet layer.
Above example is only several in the several preferred implementation of the present invention, it is noted that the invention is not restricted to above-described embodiment；For the person of ordinary skill of the art, still the technical scheme described in previous embodiment can be modified, or wherein portion of techniques feature is carried out equivalent；And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of claimed technical solution of the invention.
Claims (10)
1. Graphene/onion-like fullerene composite solid lubricating agent, it is characterised in that be by macromolecule scion grafting
Graphene and onion-like fullerene are compounded to form kollag by agent；Described Graphene and onion-like fullerene
Mass ratio is 1-20:1.
2. the preparation method of Graphene/onion-like fullerene composite solid lubricating agent, it is characterised in that step is:
1) by polymeric grafting agent and dispersant, stirring and dissolving in solvent is joined；Addition is dried
Graphene oxide powder stirring and evenly mixing obtains mixture, is heated to reflux by mixture, obtains black solid material, wash,
Being dried to obtain the graphene oxide powder of macromolecule scion grafting, sample is designated as G1；
2) take G1 and join stirring and evenly mixing in reducing agent, drip strong aqua ammonia；Then it is heated to reflux to reaction
Completely, washing, to dry, sample is designated as G2；
3) take in the mixing acid that onion-like fullerene joins concentrated nitric acid and concentrated sulphuric acid, stir under room temperature,
Washing, to neutral, is dried to obtain the oxidation onion-like fullerene powder body of pretreatment, and sample is designated as G3；
4) mixture of G2 sample and G3 sample is joined in dilute sulfuric acid, stirring reaction under room temperature, will
Product filters, washing is the most neutral, obtains Graphene/onion-like fullerene composite solid lubricating agent after drying.
The preparation side of a kind of Graphene/onion-like fullerene composite solid lubricating agent the most according to claim 2
Method, it is characterised in that described step 1) in polymeric grafting agent be stearic acid, oleic acid or silane coupler；
Described dispersant is Span-80, oleic acid, cetyl trimethylammonium bromide or calcium dodecyl benzene sulfonate；Institute
Stating solvent is hexamethylene；Described stearic acid is 10-0.5:1 with the mass ratio of dispersant, described stearic acid and dispersion
The mixture of agent and the amount ratio of hexamethylene are 1:6-10.
The preparation side of a kind of Graphene/onion-like fullerene composite solid lubricating agent the most according to claim 2
Method, it is characterised in that described step 1) in the mass ratio of polymeric grafting agent and graphene oxide be 0.5-5:1.
The preparation side of a kind of Graphene/onion-like fullerene composite solid lubricating agent the most according to claim 2
Method, it is characterised in that described step 1) in graphene oxide powder prepared by low-temperature oxidation graft process,
The specific surface area of described graphene oxide is 200-500m2/ g, sheet footpath is 200-500nm.
The preparation side of a kind of Graphene/onion-like fullerene composite solid lubricating agent the most according to claim 2
Method, it is characterised in that described step 1) in the temperature that is heated to reflux of mixture be 60-85 DEG C, the time is 3-6h.
The preparation side of a kind of Graphene/onion-like fullerene composite solid lubricating agent the most according to claim 2
Method, it is characterised in that described step 2) in reducing agent be grape extract；G1 and the use of grape extract
Amount is 2.5-5g/mL than the amount ratio for 5-10g/L, described G1 Yu strong aqua ammonia.
The preparation side of a kind of Graphene/onion-like fullerene composite solid lubricating agent the most according to claim 2
Method, it is characterised in that described step 3) concentrated sulphuric acid is 1-5:1 with the volume ratio of concentrated nitric acid in mixed acid, all
For chemically pure reagent；Described onion-like fullerene is 1:2-3 with the amount ratio of mixed acid.
The preparation side of a kind of Graphene/onion-like fullerene composite solid lubricating agent the most according to claim 2
Method, it is characterised in that described step 3) in onion-like fullerene be prepared by catalytic decomposition method and pass through
Purification；The particle diameter of described onion-like fullerene is 30-50nm, and the lamella number of plies is 10-15 layer.
The preparation side of a kind of Graphene/onion-like fullerene composite solid lubricating agent the most according to claim 2
Method, it is characterised in that described step 4) in the concentration of dilute sulfuric acid be 1-3mol/L, mixture and dilute sulfuric acid
Mass ratio is 1:10-15.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106337578A (en) * | 2016-10-11 | 2017-01-18 | 湖北卓骏自动化工业有限公司 | Parking equipment |
| CN106543478A (en) * | 2016-11-29 | 2017-03-29 | 中国科学院福建物质结构研究所 | A kind of preparation and flame retardance of polymer application of graphene-supported fullerene hybrid |
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| CN117887500A (en) * | 2024-01-11 | 2024-04-16 | 济南一诺润滑油有限公司 | Lubricating oil additive and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101886022A (en) * | 2010-07-08 | 2010-11-17 | 东南大学 | Preparation method of high-efficiency water-based lubricating fluid based on carbon nanotubes |
| CN102585973A (en) * | 2012-02-08 | 2012-07-18 | 哈尔滨工业大学 | Preparation method of graphene oxide-fullerene water-based lubricating additives |
| US20140342955A1 (en) * | 2013-05-16 | 2014-11-20 | Enerage Inc. | Modified Lubricant |
| CN104762122A (en) * | 2015-04-02 | 2015-07-08 | 南京理工大学 | Graphene-fullerene-like molybdenum disulfide compounded lubricating oil additive and preparation method thereof |
-
2016
- 2016-03-23 CN CN201610168920.3A patent/CN105838478B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101886022A (en) * | 2010-07-08 | 2010-11-17 | 东南大学 | Preparation method of high-efficiency water-based lubricating fluid based on carbon nanotubes |
| CN102585973A (en) * | 2012-02-08 | 2012-07-18 | 哈尔滨工业大学 | Preparation method of graphene oxide-fullerene water-based lubricating additives |
| US20140342955A1 (en) * | 2013-05-16 | 2014-11-20 | Enerage Inc. | Modified Lubricant |
| CN104762122A (en) * | 2015-04-02 | 2015-07-08 | 南京理工大学 | Graphene-fullerene-like molybdenum disulfide compounded lubricating oil additive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库 工程科技II辑》 * |
Cited By (13)
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| CN106543478A (en) * | 2016-11-29 | 2017-03-29 | 中国科学院福建物质结构研究所 | A kind of preparation and flame retardance of polymer application of graphene-supported fullerene hybrid |
| CN108198937A (en) * | 2017-12-28 | 2018-06-22 | 厦门大学 | A kind of graphene/fullerene/graphene all-carbon molecular device construction method |
| CN109233983A (en) * | 2018-10-17 | 2019-01-18 | 苏州工业职业技术学院 | It is a kind of to utilize C60The nano-fluid cutting fluid and preparation method of inclusion compound preparation |
| CN109810293B (en) * | 2018-12-29 | 2021-04-02 | 浙江大学宁波理工学院 | Solid lubricant for polymers, method for the production and use thereof |
| CN109810293A (en) * | 2018-12-29 | 2019-05-28 | 浙江大学宁波理工学院 | Solid lubricant for polymer, preparation method and application thereof |
| CN110194985A (en) * | 2019-06-20 | 2019-09-03 | 李祥 | A kind of fullerene fiber lubricating oil and preparation method thereof |
| CN110373278A (en) * | 2019-07-03 | 2019-10-25 | 浙江钱锦气雾剂制品有限公司 | A kind of high-efficiency environment friendly detergent for automobile carburetor |
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