CN102627993A - Preparation method of water-soluble graphene oxide-carbon nanotube extreme-pressure lubrication additive - Google Patents
Preparation method of water-soluble graphene oxide-carbon nanotube extreme-pressure lubrication additive Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 124
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 124
- 238000005461 lubrication Methods 0.000 title claims abstract description 56
- 239000000654 additive Substances 0.000 title claims abstract description 53
- 230000000996 additive effect Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 40
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- HJPOKQICBCJGHE-UHFFFAOYSA-J [C+4].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound [C+4].[Cl-].[Cl-].[Cl-].[Cl-] HJPOKQICBCJGHE-UHFFFAOYSA-J 0.000 claims description 19
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 238000009987 spinning Methods 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 239000002071 nanotube Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 abstract description 8
- 230000001050 lubricating effect Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000005097 cold rolling Methods 0.000 abstract description 2
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- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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Abstract
The invention relates to a preparation method of a water-soluble extreme-pressure lubrication additive and concretely relates to a preparation method of a water-soluble graphene oxide-carbon nanotube extreme-pressure lubrication additive to solve technical problems of high cost, bad stability, bad lubricating property and the like of present emulsified water-soluble lubricants. The preparation method of the invention comprises the following steps: 1, carboxylated carbon nanotube preparation; 2, chloridizated carbon nanotube preparation; 3, water-soluble polymer modified carbon nanotube preparation; and 4, graphene oxide-carbon nanotube extreme-pressure lubrication additive preparation. Water-soluble lubricants prepared by adopting the extreme-pressure lubrication additive of the invention have the advantages of environmental pollution reduction, production cost reduction, use stability improvement, and extreme-pressure lubrication performance possessing. The extreme-pressure lubrication additive of the invention can be applied to fields of aqueous cold rolling liquids, micro mechanical lubrication and the like.
Description
Technical field
The present invention relates to the preparation method of water-soluble extreme boundary lubrication additive.
Background technology
The energy of worldwide production has 1/3-1/2 to consume in frictional wear, and the damage of various machine parts about 80% is owing to multi-form wearing and tearing cause, this shows friction, the financial loss that caused of wearing and tearing is inestimable.Along with the development of petroleum industry, the oil lubricant technology reaches its maturity, and is widely used in each industrial sector.The whole world is required to be about 40,000,000 tons in its consumption MO every year, accounts for 2% of oil production rate.In the later stage sixties in last century,, as lubricant medium, cause people's very big concern with water base fluid proxy-mineral oil along with the world energy sources crisis.And in the last thirty years in the global range to the pay attention to day by day of environment protection, make people be more prone to this low pollution medium of water base fluid.For oil, not only petroleum resources can be practiced thrift with water, and environmental pollution and production cost can be reduced.
Domestic and international widely used water-based lubricating liquid belongs to oil-in-water type mostly at present; Has remarkable advantages although compare with oil lubricant; But the oil-in-water type lubricating fluid still has problems, and what application was the widest at present is anionic emulsifier, and their emulsifying properties are good; Certain cleaning and lubricity are arranged, but stability---resistance to hard water is poor; And nonionic emulsifier is not afraid of hard water, but price is higher again; The two has the common shortcoming again simultaneously---be difficult to metal is realized evenly lubricated effectively.
Summary of the invention
The present invention is the technical problem that will solve existing oil-in-water type water-based lubricating liquid cost height, poor stability, lubricity difference, and the preparation method of water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive is provided.
The preparation method of the water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive among the present invention carries out according to the following steps:
One, the preparation of carboxylic carbon nano-tube: carbon nanotube is joined stirring and reflux 12～48h in the mixed acid solution under agitation condition; After the cooling with mixed solution spinning 15～45min under the rotating speed of 3500～4500rpm; Isolated throw out water is washed till and is neutral; Adopt the millipore filtration of 0.20～0.25 μ m to carry out suction filtration then, filter cake at 60～90 ℃ of following vacuum dryings, is obtained carboxylic carbon nano-tube; Wherein, mixed acid solution is the HNO of 14～15mol/L by concentration
3With concentration be the H of 18～19mol/L
2SO
4Be 1: 2～4 to mix by volume, the ratio of carbon nanotube quality and mixed acid solution volume is 1g: 20～200mL;
Two, the preparation of chloride carbon nanotube: the carboxylic carbon nano-tube that obtains in the step 1 is added in the mixed solution of thionyl chloride and toluene also ultra-sonic dispersion 15～60min; Then under nitrogen protection; Spinning, abandoning supernatant are carried out in intensification degree to 50～100 ℃ backflow 1～5 day then; Precipitated product at 70～100 ℃ of following vacuum-drying 12～48h, is obtained the chloride nanotube; Wherein, the ratio of carboxylic carbon nano-tube quality and mixeding liquid volume is 1g: 600～1000mL, and the volume ratio of thionyl chloride and toluene is 1～2: 1 in the mixed solution;
Three, the preparation of the carbon nanotube of water-soluble polymer modification: chloride carbon nanotube that obtains in the step 2 and water-soluble high-molecular compound are joined in the solvent, and ultra-sonic dispersion 1～3h reacted 1～3 day under 60～120 ℃ of conditions then; Solvent evaporated is scattered in desciccate and obtains the aqueous solution in the deionized water, the aqueous solution is splashed in the ethanol precipitate again, places 60～90 ℃ vacuum drying oven to be drying to obtain the carbon nanotube that water-soluble polymer is modified then; Wherein, the ratio of solvent volume and chloride carbon nanotube quality is 1～5L: 1g, and the mass ratio of water-soluble high-molecular compound and chloride carbon nanotube is 50～200: 1; The ratio of desciccate quality and deionized water volume is 10～100g: 1L in the said aqueous solution; The volume ratio of ethanol and deionized water is 8～10: 1; Described solvent is N; Dinethylformamide, said water-soluble high-molecular compound are any one in Z 150PH, polyoxyethylene glycol and the hydro-polyacrylamide;
Four, the preparation of graphene oxide-carbon nanotube extreme boundary lubrication additive: adopt the Hummers legal system to be equipped with graphite oxide; The carbon nanotube that resulting water-soluble polymer in this graphite oxide and the step 3 is modified joins in the deionized water; Behind ultra-sonic dispersion 10～60min; The room temperature lucifuge stirred 12 hours; Spinning 10～30min under the rotating speed of 15000～17000rpm places 60～90 ℃ the dry 12～48h of vacuum drying oven with the resulting throw out of spinning again, promptly gets graphene oxide-carbon nanotube extreme boundary lubrication additive; Wherein, the carbon nanotube that water-soluble polymer is modified and the mass ratio of graphene oxide are 1～2: 1, and the ratio of graphene oxide quality and deionized water volume is 1g: 1～5L.
Mechanism of the present invention: because graphite has good lubrication, overstable physical property, nontoxic excellent properties such as inexpensive and high temperature resistant; Be acknowledged as the ideal solid lubricant; Yet; The non-wetting ability of graphite has greatly limited its research and application in the water based lubrication additive, and the application of graphite in the water based lubrication additive that appear as of graphene oxide provides opportunity.Because the mechanism of graphite lubrication is the relatively sliding of its interlayer, can further improve its lubricity if adopt nanotechnology that sliding friction is become rolling resistance.Carbon nanotube is a kind of typical nanoparticle.The explanation of carbon nanotube antifriction antiwear mechanism is mainly based on the pebbles model in the boundary lubrication theory; Think that promptly the carbon nanotube size is less; Can think approximate bar-shaped, between friction pair, can freely roll, play support loading and make the wear resistance raising of lubricant film as pebbles.Adopt graphene oxide-carbon nanotube extreme boundary lubrication additive to replace traditional oil lubricant and oil-in-water type lubricating fluid, can reduce environmental pollution, reduce cost, improve stability in use, have multiple efficacies such as extreme boundary lubrication, cooling, antirust inhibition simultaneously.
The present invention adopts the Hummers method and is aided with ultra-sonic dispersion and prepares graphene oxide, and this graphene oxide has good dispersiveness in the aqueous solution.It is carbon nano-tube modified to prepare water-soluble polymer then, and wherein water-soluble polymer and carbon nanotube link together through the chemically bonded effect, makes carbon nanotube have good wetting ability.Graphene oxide and carbon nanotube interact through pi-pi bond and realize assembling.
Water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive among the present invention has following characteristics: (1) raw material graphite itself has good lubrication; Chemical property is stable; The occurring in nature reserves are big; Cheap, adopt graphite to prepare water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive, production cost is low; (2) have the polymer flexibility molecular chain in the carbon nanotube structure, can improve the anti-attrition performance of slip additive, lubricity is good; (3) the firm carbon nanotube constituent element that is dispersed in the graphene oxide interlayer can strengthen its supporting capacity; (4) the prepared additive of the present invention has good dispersiveness in water, can form uniform and stable solution, and viscosity is little, free settling not, and life cycle is long.
A plurality of fields such as water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive of the present invention can be applicable to the cold rolling liquid of water-based, and micromechanics is lubricated.
Description of drawings
Fig. 1 is the ir spectra of the polyethyleneglycol modified carbon nanotube of step 2 synthetic in the experiment one; Fig. 2 is the transmission electron microscope picture of step 3 synthetic water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive in the experiment one; Fig. 3 tests synthetic graphene oxide in-carbon nanotube extreme boundary lubrication additive wear scar diameter and extreme pressure value and its concentration relationship curve, wherein-■-be the relation curve of wear scar diameter and concentration;--be the relation curve of extreme pressure value and concentration.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive carries out according to the following steps in this embodiment:
One, the preparation of carboxylic carbon nano-tube: carbon nanotube is joined stirring and reflux 12～48h in the mixed acid solution under agitation condition; After the cooling with mixed solution spinning 15～45min under the rotating speed of 3500～4500rpm; Isolated throw out water is washed till and is neutral; Adopt the millipore filtration of 0.20～0.25 μ m to carry out suction filtration then, filter cake at 60～90 ℃ of following vacuum dryings, is obtained carboxylic carbon nano-tube; Wherein, mixed acid solution is the HNO of 14～15mol/L by concentration
3With concentration be the H of 18～19mol/L
2SO
4Be 1: 2～4 to mix by volume, the ratio of carbon nanotube quality and mixed acid solution volume is 1g: 20～200mL;
Two, the preparation of chloride carbon nanotube: the carboxylic carbon nano-tube that obtains in the step 1 is added in the mixed solution of thionyl chloride and toluene also ultra-sonic dispersion 15～60min; Then under nitrogen protection; Spinning, abandoning supernatant are carried out in intensification degree to 50～100 ℃ backflow 1～5 day then; Precipitated product at 70～100 ℃ of following vacuum-drying 12～48h, is obtained the chloride nanotube; Wherein, the ratio of carboxylic carbon nano-tube quality and mixeding liquid volume is 1g: 600～1000mL, and the volume ratio of thionyl chloride and toluene is 1～2: 1 in the mixed solution;
Three, the preparation of the carbon nanotube of water-soluble polymer modification: chloride carbon nanotube that obtains in the step 2 and water-soluble high-molecular compound are joined in the solvent, and ultra-sonic dispersion 1～3h reacted 1～3 day under 60～120 ℃ of conditions then; Solvent evaporated is scattered in desciccate and obtains the aqueous solution in the deionized water, the aqueous solution is splashed in the ethanol precipitate again, places 60～90 ℃ vacuum drying oven to be drying to obtain the carbon nanotube that water-soluble polymer is modified then; Wherein, the ratio of solvent volume and chloride carbon nanotube quality is 1～5L: 1g, and the mass ratio of water-soluble high-molecular compound and chloride carbon nanotube is 50～200: 1; The ratio of desciccate quality and deionized water volume is 10～100g: 1L in the said aqueous solution; The volume ratio of ethanol and deionized water is 8～10: 1; Described solvent is N; Dinethylformamide, said water-soluble high-molecular compound are any one in Z 150PH, polyoxyethylene glycol and the hydro-polyacrylamide;
Four, the preparation of graphene oxide-carbon nanotube extreme boundary lubrication additive: adopt the Hummers legal system to be equipped with graphite oxide; The carbon nanotube that resulting water-soluble polymer in this graphite oxide and the step 3 is modified joins in the deionized water; Behind ultra-sonic dispersion 10～60min; The room temperature lucifuge stirred 12 hours; Spinning 10～30min under the rotating speed of 15000～17000rpm places 60～90 ℃ the dry 12～48h of vacuum drying oven with the resulting throw out of spinning again, promptly gets graphene oxide-carbon nanotube extreme boundary lubrication additive; Wherein, the carbon nanotube that water-soluble polymer is modified and the mass ratio of graphene oxide are 1～2: 1, and the ratio of graphene oxide quality and deionized water volume is 1g: 1～5L.
The present invention adopts the Hummers method and is aided with ultra-sonic dispersion and prepares graphene oxide, and this graphene oxide has good dispersiveness in the aqueous solution.It is carbon nano-tube modified to prepare water-soluble polymer then, and wherein water-soluble polymer and carbon nanotube link together through the chemically bonded effect, makes carbon nanotube have good wetting ability.Graphene oxide and carbon nanotube interact through pi-pi bond and realize assembling.
Water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive among the present invention has following characteristics: (1) raw material graphite itself has good lubrication; Chemical property is stable; The occurring in nature reserves are big; Cheap, adopt graphite to prepare water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive, production cost is low; (2) have the polymer flexibility molecular chain in the carbon nanotube structure, can improve the anti-attrition performance of slip additive, lubricity is good; (3) the firm carbon nanotube constituent element that is dispersed in the graphene oxide interlayer can strengthen its supporting capacity; (4) the prepared additive of the present invention has good dispersiveness in water, can form uniform and stable solution, and viscosity is little, free settling not, and life cycle is long.
Embodiment two: what this embodiment and embodiment one were different is: the ratio of carbon nanotube quality and mixed acid solution volume is 1g: 60～160mL in the step 1.Other step is identical with embodiment one with parameter.
Embodiment three: what this embodiment and embodiment one were different is: the ratio of carbon nanotube quality and mixed acid solution volume is 1g: 110mL in the step 1.Other step is identical with embodiment one with parameter.
Embodiment four: what this embodiment was different with one of embodiment one to three is: the ratio of carboxylic carbon nano-tube quality and mixeding liquid volume is 1g: 700～900mL in the step 2.Other step is identical with one of embodiment one to three with parameter.
Embodiment five: what this embodiment was different with one of embodiment one to four is: in the step 2 in the mixed solution volume ratio of thionyl chloride and toluene be 1.4～1.6: 1.Other step is identical with one of embodiment one to four with parameter.
Embodiment six: what this embodiment was different with one of embodiment one to five is: the mass ratio of water-soluble high-molecular compound and chloride carbon nanotube is 100～150: 1 in the step 3.Other step is identical with one of embodiment one to five with parameter.
Embodiment seven: what this embodiment was different with one of embodiment one to six is: N in the step 3, the ratio of dinethylformamide volume and chloride carbon nanotube quality is 2～4L: 1g.Other step is identical with one of embodiment one to six with parameter.
Embodiment eight: what this embodiment was different with one of embodiment one to seven is: described in the step 3 in the aqueous solution ratio of desciccate quality and deionized water volume be 40～70g: 1L.Other step is identical with one of embodiment one to seven with parameter.
Embodiment nine: what this embodiment was different with one of embodiment one to eight is: the carbon nanotube that water-soluble polymer is modified in the step 4 and the mass ratio of graphene oxide are 1.4～1.6: 1.Other step is identical with one of embodiment one to eight with parameter.
Embodiment ten: what this embodiment was different with one of embodiment one to nine is: the ratio of graphene oxide quality and deionized water volume is 1g: 2～4L in the step 4.Other step is identical with one of embodiment one to nine with parameter.
For verifying that beneficial effect of the present invention has carried out following experiment:
Experiment one: the preparation method of the water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive of this experiment carries out according to the following steps:
One, the preparation of carboxylic carbon nano-tube: the 5g carbon nanotube is joined stirring and reflux 24h in the mixed acid solution under agitation condition; After the cooling with mixed solution spinning 30min under the rotating speed of 4000rpm; Isolated throw out water is washed till and is neutral; Adopt the millipore filtration of 0.22 μ m to carry out suction filtration then, gained carboxylic carbon nano-tube filter cake is vacuum drying under 70 ℃ of conditions, and wherein mixing acid is the HNO of 14.5mol/L by 40mL concentration
3With 120mL concentration be the H of 18.4mol/L
2SO
4Be to mix at 1: 3 by volume;
Two, the preparation of chloride carbon nanotube: the carboxylic carbon nano-tube that obtains in the 1g step 1 is added in the mixed solution of 350mL thionyl chloride and 350mL toluene also ultra-sonic dispersion 25min; Then temperature be 75 ℃ with the nitrogen protection condition under; Reflux and carried out spinning in 2 days afterwards; Abandoning supernatant at 80 ℃ of following vacuum-drying 24h, obtains the chloride carbon nanotube with precipitated product;
Three, the preparation of the carbon nanotube modified of water-soluble polymer: with the N that the 1g chloride carbon nanotube and the 100g polyoxyethylene glycol of step 1 preparation joins 2L, in the dinethylformamide, ultra-sonic dispersion 1h reacted 2 days under 100 ℃ of conditions then; Solvent evaporated is scattered in the 20g desciccate in the 500mL deionized water and obtains the aqueous solution, the aqueous solution is splashed in the 5L ethanol precipitate again, places 80 ℃ vacuum drying oven to be drying to obtain polyethyleneglycol modified carbon nanotube then; The ir spectra of the polyethyleneglycol modified carbon nanotube of this step preparation is as shown in Figure 1, and the characteristic infrared that has demonstrated carbon nanotube and polyoxyethylene glycol among Fig. 1 absorbs, at 846cm
-1With 950cm
-1The charateristic avsorption band that the place occurs is the stretching vibration peak of acyl chlorides, at 1720cm
-1The place demonstrates intensive ester group characteristic peak, proves that carbon nanotube and polyoxyethylene glycol link together through ester group;
Four, the preparation of graphene oxide-carbon nanotube extreme boundary lubrication additive: adopt the Hummers legal system to be equipped with graphite oxide; The carbon nanotube that resulting water-soluble polymer in this graphite oxide of 0.5g and the 0.5g step 2 is modified joins in the 1L deionized water; Ultra-sonic dispersion 45min; The room temperature lucifuge stirred 12 hours; Spinning 30min under the rotating speed of 16000rpm places 80 ℃ the dry 24h of vacuum drying oven with the resulting throw out of spinning, promptly gets graphene oxide-carbon nanotube extreme boundary lubrication additive.Experiment one prepared graphene oxide-carbon nanotube extreme boundary lubrication additive is added in the entry; Process lubricating fluid; Utilize transmission electron microscope observing; Fig. 2 shows the transmission electron microscope picture of above-mentioned slip additive, and the result shows that graphene oxide and carbon nanotube all have good dispersiveness in water, and realizes the assembling of graphene oxide and carbon nanotube through the pi-pi bond interaction.
Water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive to preparation in the above-mentioned experiment one carries out the frictional behaviour test.Adopt four ball frictional testing machines testing friction performances, speed of mainshaft 1450rpm, 20 ℃ of test temperatures, test uses the steel ball material to be GCr15, and hardness is HRC64-66, and surfaceness is Ra=0.012 μ m.The present invention is that 2% the trolamine aqueous solution is basal liquid with mass percent, adds graphene oxide of the present invention-carbon nanotube extreme boundary lubrication additive.Extreme pressure value (PB) is tested with reference to GB3142-82; Wear scar diameter (WSD) is 200N in load, and the test duration is 30 minutes, investigates the influence of graphene oxide-carbon nanotube extreme boundary lubrication additive to WSD.Fig. 3 shown concentration and the wear scar diameter and the extreme pressure value of graphene oxide-carbon nanotube extreme boundary lubrication additive relation curve (among the figure-■-the be relation curve of wear scar diameter and concentration;--be extreme pressure value with the relation curve of concentration).Presentation of results; With mass percent is that 2% the trolamine aqueous solution is that basal liquid carries out wear scar diameter and extreme pressure value that tribology experiments obtains and is respectively 0.86mm and 98.5N; In basal liquid, add a certain amount of graphene oxide-carbon nanotube extreme boundary lubrication additive and can significantly improve the frictional behaviour of basal liquid, improve simultaneously effect its mass percent be 0.5% o'clock best.Add 0.5% graphene oxide-carbon nanotube extreme boundary lubrication additive and make the wear scar diameter of basal liquid reduce 27.9%, make the extreme pressure value increase 270.6%.
Claims (10)
1. the preparation method of water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive is characterized in that the preparation method of water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive carries out according to the following steps:
One, the preparation of carboxylic carbon nano-tube: carbon nanotube is joined stirring and reflux 12～48h in the mixed acid solution under agitation condition; After the cooling with mixed solution spinning 15～45min under the rotating speed of 3500～4500rpm; Isolated throw out water is washed till and is neutral; Adopt the millipore filtration of 0.20～0.25 μ m to carry out suction filtration then, filter cake at 60～90 ℃ of following vacuum dryings, is obtained carboxylic carbon nano-tube; Wherein, mixed acid solution is the HNO of 14～15mol/L by concentration
3With concentration be the H of 18～19mol/L
2SO
4Be 1: 2～4 to mix by volume, the ratio of carbon nanotube quality and mixed acid solution volume is 1g: 20～200mL;
Two, the preparation of chloride carbon nanotube: the carboxylic carbon nano-tube that obtains in the step 1 is added in the mixed solution of thionyl chloride and toluene also ultra-sonic dispersion 15～60min; Then under nitrogen protection; Spinning, abandoning supernatant are carried out in intensification degree to 50～100 ℃ backflow 1～5 day then; Precipitated product at 70～100 ℃ of following vacuum-drying 12～48h, is obtained the chloride nanotube; Wherein, the ratio of carboxylic carbon nano-tube quality and mixeding liquid volume is 1g: 600～1000mL, and the volume ratio of thionyl chloride and toluene is 1～2: 1 in the mixed solution;
Three, the preparation of the carbon nanotube of water-soluble polymer modification: chloride carbon nanotube that obtains in the step 2 and water-soluble high-molecular compound are joined in the solvent, and ultra-sonic dispersion 1～3h reacted 1～3 day under 60～120 ℃ of conditions then; Solvent evaporated is scattered in desciccate and obtains the aqueous solution in the deionized water, the aqueous solution is splashed in the ethanol precipitate again, places 60～90 ℃ vacuum drying oven to be drying to obtain the carbon nanotube that water-soluble polymer is modified then; Wherein, the ratio of solvent volume and chloride carbon nanotube quality is 1～5L: 1g, and the mass ratio of water-soluble high-molecular compound and chloride carbon nanotube is 50～200: 1; The ratio of desciccate quality and deionized water volume is 10～100g: 1L in the said aqueous solution; The volume ratio of ethanol and deionized water is 8～10: 1; Described solvent is N; Dinethylformamide, said water-soluble high-molecular compound are any one in Z 150PH, polyoxyethylene glycol and the hydro-polyacrylamide;
Four, the preparation of graphene oxide-carbon nanotube extreme boundary lubrication additive: adopt the Hummers legal system to be equipped with graphite oxide; The carbon nanotube that resulting water-soluble polymer in this graphite oxide and the step 3 is modified joins in the deionized water; Behind ultra-sonic dispersion 10～60min; The room temperature lucifuge stirred 12 hours; Spinning 10～30min under the rotating speed of 15000～17000rpm places 60～90 ℃ the dry 12～48h of vacuum drying oven with the resulting throw out of spinning again, promptly gets graphene oxide-carbon nanotube extreme boundary lubrication additive; Wherein, the carbon nanotube that water-soluble polymer is modified and the mass ratio of graphene oxide are 1～2: 1, and the ratio of graphene oxide quality and deionized water volume is 1g: 1～5L.
2. according to the preparation method of the said water soluble oxidized graphene-carbon nano tube of claim 1 extreme boundary lubrication additive, it is characterized in that the ratio of carbon nanotube quality and mixed acid solution volume is 1g: 60～160mL in the step 1.
3. according to the preparation method of the said water soluble oxidized graphene-carbon nano tube of claim 1 extreme boundary lubrication additive, it is characterized in that the ratio of carbon nanotube quality and mixed acid solution volume is 1g: 110mL in the step 1.
4. according to the preparation method of claim 2 or 3 said water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additives, it is characterized in that in the step 2 that the ratio of carboxylic carbon nano-tube quality and mixeding liquid volume is 1g: 700～900mL.
5. according to the preparation method of the said water soluble oxidized graphene-carbon nano tube of claim 4 extreme boundary lubrication additive, it is characterized in that in the step 2 that the volume ratio of thionyl chloride and toluene is 1.4～1.6: 1 in the mixed solution.
6. according to the preparation method of the said water soluble oxidized graphene-carbon nano tube of claim 5 extreme boundary lubrication additive, it is characterized in that in the step 3 that the mass ratio of water-soluble high-molecular compound and chloride carbon nanotube is 100～150: 1.
7. according to the preparation method of the said water soluble oxidized graphene-carbon nano tube of claim 6 extreme boundary lubrication additive, it is characterized in that in the step 3, N, the ratio of dinethylformamide volume and chloride carbon nanotube quality is 2～4L: 1g.
8. according to the preparation method of the said water soluble oxidized graphene-carbon nano tube of claim 7 extreme boundary lubrication additive, it is characterized in that in the step 3 that the ratio of desciccate quality and deionized water volume is 40～70g: 1L in the said aqueous solution.
9. the preparation method of said according to Claim 8 water soluble oxidized graphene-carbon nano tube extreme boundary lubrication additive is characterized in that in the step 4, and the carbon nanotube that water-soluble polymer is modified and the mass ratio of graphene oxide are 1.4～1.6: 1.
10. according to the preparation method of the said water soluble oxidized graphene-carbon nano tube of claim 9 extreme boundary lubrication additive, it is characterized in that in the step 4 that the ratio of graphene oxide quality and deionized water volume is 1g: 2～4L.
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