CN107287012A - A kind of composite sodium-based lubricating grease containing spitball shape graphene microballoon and preparation method thereof - Google Patents

A kind of composite sodium-based lubricating grease containing spitball shape graphene microballoon and preparation method thereof Download PDF

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Publication number
CN107287012A
CN107287012A CN201710475096.0A CN201710475096A CN107287012A CN 107287012 A CN107287012 A CN 107287012A CN 201710475096 A CN201710475096 A CN 201710475096A CN 107287012 A CN107287012 A CN 107287012A
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microballoon
lubricating grease
spitball shape
graphene
sodium
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高超
申瑜
陈琛
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Changxin De Technology Co Ltd
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Changxin De Technology Co Ltd
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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/02—Carbon; Graphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2207/1265—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 used as thickening agent
    • 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
    • C10M2207/127—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 polycarboxylic
    • C10M2207/1276—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 polycarboxylic used as thickening agent
    • 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
    • C10M2207/128—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 containing hydroxy groups; Ethers thereof
    • C10M2207/1285—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 containing hydroxy groups; Ethers thereof used as thickening agents
    • 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
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/141—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
    • C10M2207/1415—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic used as thickening agent
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

The invention discloses a kind of composite sodium-based lubricating grease containing spitball shape graphene microballoon and preparation method thereof, the lubricating grease is mixed by base oil, composite sodium-based thickening agent, spitball shape graphene microballoon and other auxiliary agents, wherein 0.1~5 part in parts by mass of spitball shape graphene microballoon.Spitball shape graphene microballoon has good mechanical property and elasticity, can effectively absorb impact, and stability is strong.On the one hand spitball shape structure reduces the stacking of graphene, added in lubricating grease after can be with fine dispersion, on the other hand effectively reduction working face friction, and fill up and prevent further expand in abrading section.The composite sodium-based lubricating grease containing spitball shape graphene microballoon of the present invention has excellent heat-resisting quantity, extreme-pressure wear-resistant, water-resistance, anti-corrosive properties and long-life.

Description

A kind of composite sodium-based lubricating grease containing spitball shape graphene microballoon and preparation method thereof
Technical field
The invention belongs to lubricating grease field, be related to a kind of composite sodium-based lubricating grease containing spitball shape graphene microballoon and its Preparation method.
Background technology
Friction phenomenon is widely present in mechanical movement, causes energy loss, efficiency reduction, the temperature of machine to raise, make Surface abrasion, hydraulic performance decline, and the lost of life, due to being worn and torn caused by friction pair in friction, and energy caused by friction Loss and heat so that machinery is prone to failure or even failure, gives people life and brings economic loss, or even Personal Risk. The use of lubricating oil and lubricating grease is that people's daily life reduces the important means of friction and wear, for lubricating oil, profit Consistent lubricant operating temperature range is wider, it is adaptable to than the environment of lubricating oil low speed, can have good close for a long time without additional maintenance Sealing property, can prevent pollutant from invading equipment, and energy noise-decreasing and vibrations, it is adaptable to harsh operating condition.But profit Consistent lubricant also has many shortcomings, and such as viscosity is strong, and poor fluidity, thermal diffusivity is bad, for fat, changes fat inconvenience, is adjusted for fat amount hardly possible, Impurity can not be removed from lubricated surface.
Graphene is a kind of two-dimensional material of atomic thickness, the specific surface area with superelevation, excellent mechanical property and from Lubricity.These characteristics make its application study in terms of lubricating additive attract attention, and many researchs in recent years find appropriate Graphene as lubricating additive can not only reduce coefficient of friction, and can be significantly improved by the form of friction clamping film The carrying abrasion resistance of lubricant.But graphene is easily being reunited, graphite-structure is re-formed, and it is scattered in lubricating grease Property is not good.Although the dispersiveness and reduction stone of graphene can be promoted by adding dispersant and carrying out the method for surface modification The stacking of black alkene, but these sides improve the cost of graphene, and new composition is introduced, to the performance that lubricating grease is overall There may be complicated influence.
The content of the invention
The purpose of the present invention is that there is provided a kind of compound sodium containing spitball shape graphene microballoon for existing technical deficiency Base grease and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：A kind of compound sodium containing spitball shape graphene microballoon Base grease, is characterised by, in parts by mass including following component：70~90 parts of base oil, composite sodium-based thickening agent 5~30 Part, 0.1~5 part of spitball shape graphene microballoon, 1~5 part of other auxiliary agents.The spitball shape graphene microballoon is by single-layer graphene film Gauffer is formed, and microsphere diameter is 500nm~5 μm, and density is 0.2~0.4g/cm3, carbon-to-oxygen ratio is 20~60, and specific surface area is less than 200m2/g。
The spitball shape graphene microballoon is prepared by following steps：
(1) the single-layer graphene oxide dispersion liquid for being prepared Hummers methods by atomization drying method is dried, and obtains oxygen Graphite alkene microballoon；
(2) the graphene oxide microballoon for obtaining step (1), is placed in reducibility gas atmosphere, at 60~200 DEG C also Former 30min~48h obtains redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) carries out high-temperature process, temperature is not less than 1000 DEG C, obtains To spitball shape graphene microballoon.
Further, in the single-layer graphene oxide dispersion liquid of the step (1), reducing agent can also be contained.In atomization During, fold occurs for graphene oxide sheet, meanwhile, reducing agent is attached to sheet surfaces with molecular conformation.The reducing agent is Hydrogen iodide, hydrogen bromide, hydrazine hydrate, vitamin C, sodium borohydride etc..Reducing agent and single-layer graphene oxide mass ratio be 0.1~ 10.Atomization drying temperature in the step (1) is 100~200 DEG C so that be wrapped in the reducing agent in pleated structure to oxidation Graphene is tentatively reduced.
Further, the reducing atmosphere described in step (2) is hydrazine hydrate steam, hydroiodic acid steam, hydrogen, hydrobromic acid One or more in steam.Reducing condition is：30min~48h or so is reduced at 60~200 DEG C.
Further, the high-temperature process temperature described in step (3) be 2500~3000 DEG C, processing time be 30min~ 48h, atmosphere is one kind in nitrogen, helium, hydrogen argon gas gaseous mixture, argon gas.
A kind of composite sodium-based preparation of greases method containing spitball shape graphene microballoon, comprises the following steps：
(1) by spitball shape graphene microballoon, base oil, other auxiliary agents and C12-C24Aliphatic acid is mixed, and is warming up to 80~110 After DEG C, add sodium hydroxide and carry out saponification, then add C1-C22Aliphatic acid is combined, and is warming up to 200~210 DEG C；
(2) mixture for obtaining step (1) is mixed with remaining base oil, is cooled to 90~130 DEG C, dehydration, after cooling Grinding, obtains the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
The amount of the base oil added in step 1 and step 2 is determined according to admixture, has both ensured to be well mixed guaranteed flowing Property, it is the common knowledge of this area.
Further, other auxiliary agents described in step (1) include：0.5~2 part of antioxidant, 0~2 part of surfactant, 0.5~1 part of antirust agent.The composite sodium-based thickening agent is by C12-C24Sodium soap and C1-C22Sodium soap is constituted, C12-C24Fat Fat acid sodium and C1-C22The mol ratio of sodium soap is 1:0.1~2.
The beneficial effects of the present invention are：The present invention prepares graphene oxide microballoon by atomization drying method first, Reducing agent is added in graphene oxide dispersion before atomization drying, is well mixed, reducing agent is supported on molecular forms Graphene oxide sheet surface.Afterwards during atomization drying, the oxygen-containing function of partial reduction agent and surface of graphene oxide Group reacts, and product is deviate from the volatilization of solvent, and remaining reducing agent is then attached to graphene oxide sheet table with molecular forms Face, and be wrapped with its gauffer.Second step uses electronation, under reducing atmosphere, inside graphene oxide microballoon Fully reacted with reducing agent with the oxygen-containing functional group on surface, relatively low temperature make it that the generation and release of gas are slow, it is to avoid Group fast eliminating produces gas, the phenomenon for causing volume drastically to expand in direct thermal reduction, thus maintain graphene still with The form of fold piece is combined closely without separating.On the one hand 3rd step high temperature thermal reduction takes off remaining a small amount of oxygen-containing functional group Remove, and repair the defect sturcture in graphene oxide sheet, on the other hand, make the moisture of residual in microballoon, reduzate and not anti- The reducing agent removing answered.In addition, we have been surprisingly found that in an experiment, and at extreme temperatures under (2500~3000 DEG C), graphene The diameter of microballoon is gradually reduced, density increase, specific surface area reduction.This be probably due under graphitization temperature, graphene film Perfect structure so that graphene fold adhesion strengthens, the increase of graphene film intermolecular forces, Distance Shortened each other, Progressively make the compact structure of graphene ball.
Gained spitball shape graphene microballoon has good mechanical property and elasticity, can effectively absorb impact, stability is strong. In addition, spitball shape structure reduces the stacking of graphene, overall stability is improved.The graphene in the case where applying external force Microballoon graphene microballoon in the case where rubbing surface carries out rolling friction, extreme pressure can be filled in abrading section reduction and be further worn out, and can show Write the wear resistant friction reducing for improving lubricating grease.In addition, the graphene microballoon mechanical property of low specific surface area, low porosity is more preferably, more Be conducive to improving greasy property.
Brief description of the drawings
Fig. 1 is the microscopic appearance of the spitball shape graphene microballoon prepared through the embodiment of the present invention 1.
Fig. 2 is the microscopic appearance of the expanded graphite alkene ball prepared through present invention contrast 2.
Embodiment
The method for preparing the composite sodium-based lubricating grease containing spitball shape graphene microballoon comprises the following steps：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon.The list It can also contain reducing agent in layer graphene oxide dispersion.Reducing agent is hydrogen iodide, hydrogen bromide, hydrazine hydrate, vitamin C, boron Sodium hydride etc..Reducing agent is 0.1~10 with single-layer graphene oxide mass ratio.Atomization drying temperature is 100~200 DEG C；(2) will The graphene oxide microballoon that step (1) is obtained, is placed in reducibility gas atmosphere, and 30min~48h is reduced at 60~200 DEG C Obtain redox graphene microballoon；Described reducing atmosphere is in hydrazine hydrate steam, hydroiodic acid steam, hydrobromic acid steam It is one or more；(3) the redox graphene microballoon for obtaining step (2) carries out high-temperature process, and temperature is higher than 1000 DEG C, obtained To spitball shape graphene microballoon；Atmosphere is one kind in nitrogen, helium, hydrogen argon gas gaseous mixture, argon gas, and processing time is 30min~48h.Further, the temperature treatment temperature is 2500~3000 DEG C.(4) the paper nodular graphite for obtaining step (3) Alkene microballoon and base oil, other auxiliary agents and C12-C24Aliphatic acid is mixed, and is warming up to after 80~110 DEG C, is added sodium hydroxide and is carried out Saponification, then adds C1-C22Aliphatic acid is combined, and is warming up to 200~210 DEG C.Other auxiliary agents include：Antioxidant 0.5 ~2 parts, 0~2 part of surfactant, 0.5~2 part of antirust agent.(5) mixture for obtaining step (4) is mixed with remaining base oil Close, be cooled to 90~130 DEG C, dehydration is ground after cooling, obtains the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
The present invention is specifically described below by embodiment, the present embodiment is served only for doing further the present invention Bright, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art makes one according to the content of foregoing invention A little nonessential changes and adjustment belong to protection scope of the present invention.
Embodiment 1：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature Spend for 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and 1h is reduced at 60 DEG C and is obtained Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.5 part of spitball shape graphene microballoon for obtaining step (3), and 61 parts of base oil, 12- hydroxy stearic acids 7.4 Part, 0.6 part of antioxidant, 1.4 parts of mixing of antirust agent, are warming up to after 90 DEG C, add sodium hydroxide and carry out saponification, then add 5.5 parts of benzoic acid are combined, and are warming up to 200 DEG C；
(5) mixture for obtaining step (4) is mixed with 24 parts of base oils, is cooled to 90 DEG C, dehydration is ground after cooling, Obtain the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
Through above step, the composite sodium-based lubricating grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon It is fold microballoon of the diameter at 3~5 μm under microcosmic, as shown in Figure 1.Its density is 0.2g/cm3, carbon-to-oxygen ratio is 22.7, compares table Area is 190m2/g.The performance of gained lubricating grease is as shown in table 2.
Embodiment 2：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature Spend for 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and 1h is reduced at 90 DEG C and is obtained Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.5 part of spitball shape graphene microballoon for obtaining step (3), and 61 parts of base oil, 12- hydroxy stearic acids 7.4 Part, 0.6 part of antioxidant, 1.4 parts of mixing of antirust agent, are warming up to after 90 DEG C, add sodium hydroxide and carry out saponification, then add 5.5 parts of benzoic acid are combined, and are warming up to 210 DEG C；
(5) mixture for obtaining step (4) is mixed with 24 parts of base oils, is cooled to 90 DEG C, dehydration is ground after cooling, Obtain the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
Through above step, the composite sodium-based lubricating grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon Microcosmic lower for fold microballoon of the diameter at 3~5 μm.Its density is 0.23g/cm3, carbon-to-oxygen ratio is 23.1, and specific surface area is 181m2/g.The performance of the composite sodium-based lubricating grease of gained is as shown in table 2.
Embodiment 3：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature Spend for 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.5 part of spitball shape graphene microballoon for obtaining step (3), and 61 parts of base oil, 12- hydroxy stearic acids 7.4 Part, 0.6 part of antioxidant, 1.4 parts of mixing of antirust agent, are warming up to after 90 DEG C, add sodium hydroxide and carry out saponification, then add 5.5 parts of benzoic acid are combined, and are warming up to 210 DEG C；
(5) mixture for obtaining step (4) is mixed with 24 parts of base oils, is cooled to 90 DEG C, dehydration is ground after cooling, Obtain the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
Through above step, the composite sodium-based lubricating grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon Microcosmic lower for fold microballoon of the diameter at 3~5 μm.Its density is 0.25g/cm3, carbon-to-oxygen ratio is 22.9, and specific surface area is 166m2/g.The performance of the composite sodium-based lubricating grease of gained is as shown in table 2.
By comparative example 1~3, final stone can be significantly reduced by improving second step reduction temperature and time The specific surface area of black alkene microballoon, improves density, but influence little to carbon-to-oxygen ratio.This is due to that second step reduction mainly makes oxidation The group of graphenic surface is slowly removed, reduction temperature is low or the time it is short can cause that reduction is insufficient, the group of residual exists Removing is may proceed to during the 3rd high-temperature heat treatment, gas is produced and graphene film is outwards expanded.And spitball shape graphene is micro- The specific surface area of ball is lower, and density is higher, and representative structure is more closely knit, and its resistance to pressure and elasticity are more preferable so that compounded lubricating oil Combination property more preferably, as shown in table 2.Therefore, to sum up consider, second step reducing condition is preferably high reduction temperature and long reduction Time.
Embodiment 4：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide The mass ratio of alkene microballoon, vitamin C and graphene oxide is 0.1, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.7 part of spitball shape graphene microballoon for obtaining step (3), and 63 parts of base oil, 6.8 parts of stearic acid, antioxygen 0.6 part of agent, 1.4 parts of mixing of antirust agent, are warming up to after 110 DEG C, add sodium hydroxide and carry out saponification, then add 4.1 parts Benzoic acid is combined, and is warming up to 200 DEG C；
(5) mixture for obtaining step (4) is mixed with 24 parts of base oils, is cooled to 130 DEG C, dehydration is ground after cooling, Obtain the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
Through above step, the composite sodium-based lubricating grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon Microcosmic lower for fold microballoon of the diameter at 3~5 μm.Specific nature is as shown in table 1,2.
Embodiment 5：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide The mass ratio of alkene microballoon, vitamin C and graphene oxide is 1, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.6 part of spitball shape graphene microballoon for obtaining step (3), and 63 parts of base oil, 6.8 parts of stearic acid, antioxygen 0.6 part of agent, 1.4 parts of mixing of antirust agent, are warming up to after 110 DEG C, add sodium hydroxide and carry out saponification, then add 4.1 parts Benzoic acid is combined, and is warming up to 200 DEG C；
(5) mixture for obtaining step (4) is mixed with 24 parts of base oils, is cooled to 130 DEG C, dehydration is ground after cooling, Obtain the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
Through above step, the composite sodium-based lubricating grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon Microcosmic lower for fold microballoon of the diameter at 3~5 μm.Specific nature is as shown in table 1,2.
Embodiment 6：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide The mass ratio of alkene microballoon, vitamin C and graphene oxide is 5, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 1 part of spitball shape graphene microballoon for obtaining step (3), and 63 parts of base oil, 6.8 parts of stearic acid, antioxidant 0.6 part, 1 part of surfactant, the mixing of 1.4 parts of antirust agent, be warming up to after 100 DEG C, add sodium hydroxide and carry out saponification, so 4.1 parts of benzoic acid are added afterwards to be combined, and are warming up to 200 DEG C；
(5) mixture for obtaining step (4) is mixed with 24 parts of base oils, is cooled to 110 DEG C, dehydration is ground after cooling, Obtain the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
Through above step, the composite sodium-based lubricating grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon Microcosmic lower for fold microballoon of the diameter at 3~5 μm.Specific nature is as shown in table 1,2.
Embodiment 7：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide The mass ratio of alkene microballoon, vitamin C and graphene oxide is 1, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter To 2000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.8 part of spitball shape graphene microballoon for obtaining step (3), and 58 parts of base oil, 12- hydroxy stearic acids 5.8 Part, 0.6 part of antioxidant, 1.4 parts of mixing of antirust agent, are warming up to after 80~110 DEG C, add sodium hydroxide and carry out saponification, so 4 parts of decanedioic acid are added afterwards to be combined, and are warming up to 200~210 DEG C；
(5) mixture for obtaining step (4) is mixed with 30 parts of base oils, is cooled to 90~130 DEG C, dehydration, after cooling Grinding, obtains the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
Through above step, the composite sodium-based lubricating grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon Microcosmic lower for fold microballoon of the diameter at 2~4 μm.Specific nature is as shown in table 1,2.
Embodiment 8：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide The mass ratio of alkene microballoon, vitamin C and graphene oxide is 1, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter To 3000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.6 part of spitball shape graphene microballoon for obtaining step (3), and it is 52 parts of base oil, 10.1 parts of stearic acid, anti- 0.6 part of oxygen agent, 1.4 parts of mixing of antirust agent, are warming up to after 80~110 DEG C, add sodium hydroxide and carry out saponification, then add 7.8 parts of decanedioic acid are combined, and are warming up to 200~210 DEG C；
(5) mixture for obtaining step (4) is mixed with 28 parts of base oils, is cooled to 90~130 DEG C, dehydration, after cooling Grinding, obtains the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
Through above step, the composite sodium-based lubricating grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon It is fold microballoon of the diameter in 500nm~3 μm under microcosmic.Specific nature is as shown in table 1,2.
Embodiment 9：
(1) dried by atomization drying method single-layer graphene oxide dispersion liquid, obtain graphene oxide microballoon, atomization temperature For 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter To 3000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.6 part of spitball shape graphene microballoon for obtaining step (3), and it is 52 parts of base oil, 10.1 parts of stearic acid, anti- 0.6 part of oxygen agent, 1.4 parts of mixing of antirust agent, are warming up to after 80~110 DEG C, add sodium hydroxide and carry out saponification, then add 7.8 parts of decanedioic acid are combined, and are warming up to 200~210 DEG C；
(5) mixture for obtaining step (4) is mixed with 28 parts of base oils, is cooled to 90~130 DEG C, dehydration, after cooling Grinding, obtains the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
Through above step, the composite sodium-based lubricating grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon Microcosmic lower for fold microballoon of the diameter at 1~4 μm.Specific nature is as shown in table 1,2.
Comparative example 1：Method according to embodiment 1 prepares composite sodium-based lubricating grease, unlike, in preparation process without Spitball shape graphene microballoon.Performance is as shown in table 1,2.
Comparative example 2：Graphene oxide microballoon is without the direct thermal reduction of electronation：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature Spend for 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1) is put into tube furnace, is continually fed into hydrogen-argon-mixed, temperature 3000 DEG C are risen to, 1h is incubated.
(4) 0.6 part of spitball shape graphene microballoon for obtaining step (3), and it is 52 parts of base oil, 10.1 parts of stearic acid, anti- 0.6 part of oxygen agent, 1.4 parts of mixing of antirust agent, are warming up to after 80~110 DEG C, add sodium hydroxide and carry out saponification, then add 7.8 parts of decanedioic acid are combined, and are warming up to 200~210 DEG C；
(5) mixture for obtaining step (4) is mixed with 28 parts of base oils, is cooled to 90~130 DEG C, dehydration, after cooling Grinding, obtains the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
Through above step, obtained graphene outward appearance is black fluffy powder, and microcosmic is hollow ball of the diameter at 1~10 μm Shell, as shown in Figure 2.The composite sodium-based PERFORMANCE OF GREASES of gained is as shown in table 1,2.
The embodiment design parameter of table 1 and property
The frictional behaviour of table 2
Comparative example 3~6 is it can be found that the amount of the reducing agent added by improving before atomization drying can be effectively facilitated Reducing degree of the graphene oxide microballoon before three step process, this is due to that reducing agent is dispersed in oxidation with molecular forms Graphenic surface, can roll into a ball step-reaction, slow reduced graphene so that carbon-to-oxygen ratio is put forward in the first step and second step with ether ring Rise, specific surface area reduction.And contrast knowable to before and after the reduction of the 3rd step, high-temperature heat treatment causes inside redox graphene microballoon The group not removed departs from (carbon-to-oxygen ratio increase), and the swelling graphene interlayer structure of gas of generation causes specific surface area to rise.But It is to be improved by adding reducing agent after reproducibility, the release gas that graphene microballoon can be less in the 3rd step high-temperature heat treatment, Reduce volumetric expansion so that structure is more closely knit.Therefore, in order to obtain high density, low specific surface area graphene microballoon, plus It is significant to enter reducing agent.
Comparative example 5,7 is it can be found that in the case where ensureing that first two steps reducing condition is consistent, improve the reduction of the 3rd step Temperature causes specific surface area to increase, density reduction, and this is due to that the further release of gas causes lamellar structure further to strut. However, surprisingly, after temperature rises to 3000 DEG C (embodiment 8), specific surface area is greatly lowered, it may be possible to which temperature is high In after graphitization temperature, the big π structures of graphene are repaired, and the adhesion between lamella is greatly promoted, interlamellar spacing reduction, because And cause graphene microballoon to center " aggregation ", more densification.
Comparative example 3,9 is understood, if being added without reducing agent, can significantly reduce graphite by 3000 DEG C of heat treatments merely The specific surface area of alkene microballoon.But comparative example 8 is understood, add reducing agent and realize that most of functional group's removing can before heat treatment To obtain the graphene microballoon of more consolidation.
Comparative example 8 and comparative example 1 are understood, graphene oxide microballoon directly is carried out into high-temperature heat treatment in comparative example, A large amount of gas effusions cause volume rapid expanding during reduction, and specific surface area is high, and density is very low.
Density, size and the specific surface area of graphene microballoon have a significant impact to the performance of last complex grease.If empty Gap increases, and compressive strength, modulus and the resilience of microballoon decline, and play a part of greasy property also phase when acting on rubbing surface It should reduce.It is scattered more easily to reach stabilization also, particle is smaller.Thus, consider, it is necessary to obtain more densely cross-linked graphite Alkene microballoon.The present invention realizes the densification of graphene microballoon, so as to effectively improve profit by controlling each step Reduction parameter The combination property of consistent lubricant.
Embodiment 10：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide The mass ratio of alkene microballoon, vitamin C and graphene oxide is 1, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter To 3000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) 0.6 part of spitball shape graphene microballoon for obtaining step (3), and it is 52 parts of base oil, 10.1 parts of stearic acid, anti- 0.6 part of oxygen agent, 1.4 parts of mixing of antirust agent, are warming up to after 80~110 DEG C, add sodium hydroxide and carry out saponification, then add 7.8 parts of decanedioic acid are combined, and are warming up to 200~210 DEG C；
(5) mixture for obtaining step (4) is mixed with 28 parts of base oils, is cooled to 90~130 DEG C, dehydration, after cooling Grinding, obtains the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
Through above step, the composite sodium-based lubricating grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon It is fold microballoon of the diameter in 500nm~3 μm under microcosmic, because step (1)~(3) are same as Example 8, therefore graphene Carbon-to-oxygen ratio, density, the specific surface area of microballoon are same as Example 8.Specific nature is as shown in table 2.It can be found that improving graphene The addition of ball can further lift the properties of lubricating grease.

Claims (10)

1. a kind of composite sodium-based lubricating grease containing spitball shape graphene microballoon, it is characterised in that in parts by mass including as follows Component：70~90 parts of base oil, composite sodium-based 5~30 parts of thickening agent, 0.1~5 part of spitball shape graphene microballoon, other auxiliary agents 1 ~5 parts.The spitball shape graphene microballoon is formed by single-layer graphene film gauffer, and microsphere diameter is 500nm~5 μm, and density is 0.2~0.4g/cm3, carbon-to-oxygen ratio is 20~60, and specific surface area is less than 200m2/g。
2. lubricating grease according to claim 1, it is characterised in that the spitball shape graphene microballoon is prepared by following steps Obtain：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon；
(2) the graphene oxide microballoon for obtaining step (1), is placed in reducibility gas atmosphere and is reduced, obtain oxygen reduction Graphite alkene microballoon；
(3) the redox graphene microballoon for obtaining step (2) carries out high-temperature process, and temperature is not less than 1000 DEG C, obtains paper Nodular graphite alkene microballoon.
3. lubricating grease according to claim 2, it is characterised in that the single-layer graphene oxide dispersion liquid of the step (1) In, reducing agent can also be contained.The reducing agent is hydrogen iodide, hydrogen bromide, hydrazine hydrate, vitamin C, sodium borohydride etc..Reduction Agent is 0.1~10 with single-layer graphene oxide mass ratio.
4. lubricating grease according to claim 2, it is characterised in that atomization drying temperature in the step (1) for 100~ 200℃。
5. lubricating grease according to claim 2, it is characterised in that the reducing atmosphere in the step (2) is hydrazine hydrate One or more in steam, hydroiodic acid steam, hydrobromic acid steam.Reducing condition is：At 60~200 DEG C reduce 30min~ 48h or so.
6. lubricating grease according to claim 2, it is characterised in that the high-temperature process temperature in the step (3) is 2500 ~3000 DEG C.
7. lubricating grease according to claim 2, it is characterised in that the high-temperature process atmosphere in the step (3) is nitrogen, One kind in helium, hydrogen argon gas gaseous mixture, argon gas, processing time is 30min~48h.
8. lubricating grease according to claim 1, it is characterised in that other described auxiliary agents include：0.5~2 part of antioxidant, table Face activating agent 0~2 parts of composite sodium-based lubricating grease, 0.5~2 part of antirust agent.
9. lubricating grease according to claim 1, it is characterised in that the composite sodium-based thickening agent is by C12-C24Sodium soap And C1-C22Sodium soap is constituted, C12-C24Sodium soap and C1-C22The mol ratio of sodium soap is 1:0.1~2.
10. a kind of composite sodium-based preparation of greases method containing spitball shape graphene microballoon, it is characterised in that including following Step：
(1) by spitball shape graphene microballoon, part basis oil, other auxiliary agents and C12-C24Aliphatic acid is mixed, and is warming up to 80~110 After DEG C, add sodium hydroxide and carry out saponification, then add C1-C22Aliphatic acid is combined, and is warming up to 200~210 DEG C；
(2) mixture for obtaining step (1) is mixed with remaining base oil, is cooled to 90~130 DEG C, dehydration is ground after cooling, Obtain the composite sodium-based lubricating grease containing spitball shape graphene microballoon.
CN201710475096.0A 2017-06-21 2017-06-21 A kind of composite sodium-based lubricating grease containing spitball shape graphene microballoon and preparation method thereof Pending CN107287012A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104560315A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Composite sodium-based lubricating grease and preparation method thereof
CN106185904A (en) * 2016-07-15 2016-12-07 浙江大学 A kind of high fold graphene paper

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104560315A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Composite sodium-based lubricating grease and preparation method thereof
CN106185904A (en) * 2016-07-15 2016-12-07 浙江大学 A kind of high fold graphene paper

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Application publication date: 20171024