CN107033994A - A kind of Ba-grease containing spitball shape graphene microballoon and preparation method thereof - Google Patents

A kind of Ba-grease containing spitball shape graphene microballoon and preparation method thereof Download PDF

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Publication number
CN107033994A
CN107033994A CN201710302917.0A CN201710302917A CN107033994A CN 107033994 A CN107033994 A CN 107033994A CN 201710302917 A CN201710302917 A CN 201710302917A CN 107033994 A CN107033994 A CN 107033994A
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microballoon
graphene
spitball shape
lubricating grease
parts
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高超
陈琛
韩燚
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Hangzhou Gaoxi Technology Co Ltd
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Hangzhou Gaoxi Technology Co Ltd
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Priority to CN201710302917.0A priority Critical patent/CN107033994A/en
Publication of CN107033994A publication Critical patent/CN107033994A/en
Priority to US16/622,953 priority patent/US11225414B2/en
Priority to KR1020197034665A priority patent/KR102307001B1/en
Priority to PCT/CN2018/077221 priority patent/WO2018196474A1/en
Priority to RU2019138451A priority patent/RU2734476C1/en
Priority to EP18791151.6A priority patent/EP3617141B1/en
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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
    • 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
    • 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
    • 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 Ba-grease containing spitball shape graphene microballoon and preparation method thereof, the lubricating grease is mixed by 70~90 parts of base oils, 5~20 parts of barium base thickening agents, 0.05~5 part of spitball shape graphene microballoon and 1~5 part of other auxiliary agent.By atomization drying, electronation and the step of high-temperature heat treatment three, the group of graphene oxide is removed speed reduction, so as to avoid the fluffy of graphene package assembly in reduction process, obtained the spitball shape graphene microballoon that density is high, specific surface area is low.The wear resistant friction reducing ability of lubricating grease can be effectively improved by being further filled in lubricating grease, the temperature in use of lubricating grease be improved, with excellent heat-resisting quantity, thermal conductivity, extreme-pressure wear-resistant, stability and long-life.

Description

A kind of Ba-grease containing spitball shape graphene microballoon and preparation method thereof
Technical field
The invention belongs to lubricating grease field, it is related to a kind of Ba-grease containing spitball shape graphene microballoon and its preparation Method.
Background technology
Ba-grease is, with aliphatic acid barium soap, to be thickened moderately viscous mineral lubricating oil or synthetic lubricant fluid are made one Kind of lubriation material, with high dropping point, water resistant, resistance to elevated temperatures is good, mechanical stability is good, insoluble in gasoline and alcohol the features such as, often For equipment such as oil pump, water pump, ship propeller, chemical pumps.But the colloid stability of conventional Ba-grease is poor, it is point oily compared with Height, poor thermal conductivity limits it and uses scope.There are many reports that Ba-grease performance is improved on addition auxiliary agent in recent years Road, patent 201510698113.8《A kind of composite barium-base grease composition and preparation method thereof》The middle thickening agent using optimization Proportioning and antioxidant systems, are aided with special refining process, improve colloid stability and the mechanical stability of lubricating grease.In recent years Come, the research to nano material deepens continuously, researchers also attempt to nano-composite material being combined acquisition with lubricating grease more The lubricant of high-quality.
Graphene is a kind of two-dimensional material of atomic thickness, and the specific surface area with superelevation, excellent mechanical property, height are led Heating rate and self lubricity.These characteristics make its application study in terms of lubricating additive attract attention, many researchs in recent years It was found that appropriate graphene can not only reduce coefficient of friction as lubricating additive, and can be by the form of friction clamping film Significantly improve the carrying abrasion resistance of lubricant.But graphene is easily being reunited, and re-forms graphite-structure, and in lubricating grease In dispersiveness it is not good.Although the dispersiveness of graphene can be promoted by adding dispersant and carrying out the method for surface modification With the stacking of reduction graphene, but these sides improve the cost of graphene, and introduce new composition, whole to lubricating grease There may be complicated influence for the performance of body.Patent 201310516349.6《A kind of composite barium-base grease composition and its system Preparation Method》By the way that a part for graphene as thickening agent is added in lubricating grease, greasy property is not only increased, is also shortened Preparation of greases time.
The content of the invention
The purpose of the present invention is that there is provided a kind of barium Ji Run containing spitball shape graphene microballoon for existing technical deficiency Consistent lubricant and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：A kind of barium Ji Run containing spitball shape graphene microballoon Consistent lubricant, is characterised by, in parts by mass including following component：70~90 parts of base oil, 5~20 parts of barium base thickening agent, spitball shape 0.01~5 part of graphene microballoon, 1~5 part of other auxiliary agents.The spitball shape graphene microballoon is 1~200 μm of individual layer by size Graphene film gauffer is formed, and microsphere diameter is 500nm~5 μm, and density is 0.04~0.2g/cm3, carbon-to-oxygen ratio is 10~30.
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 and obtains 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.
Further, other described auxiliary agents include：0.5~2 part of antioxidant, 0~2 part of surfactant, antirust agent 0.5~ 1 part.
Further, the barium base thickening agent is C12-C24Natural acid or synthetic fatty acid and barium hydroxide it is anti- Answer thing
A kind of preparation method of the Ba-grease containing spitball shape graphene microballoon, comprises the following steps：
(1) by spitball shape graphene microballoon, base oil and C12-C24Aliphatic acid is mixed, and is warming up to after 90~110 DEG C, is added Barium hydroxide carries out saponification；
(2) mixture for obtaining step (1) is warming up to 150~180 DEG C, dehydration, then is warming up to 200~220 DEG C of refinings, It is cooled to after 90~120 DEG C and adds other auxiliary agents and remaining base oil, mixed grinding is obtained containing spitball shape graphene microballoon Ba-grease.
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.
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 have Effect absorbs impact, and stability is strong.In addition, spitball shape structure reduces the stacking of graphene, overall stability is improved.Applying Plus graphene microballoon graphene microballoon in the case where rubbing surface carries out rolling friction, extreme pressure can be filled in abrading section in the case of external force Reduction is further worn out, and is remarkably improved the wear resistant friction reducing of lubricating grease.In addition, the graphene of low specific surface area, low porosity Microballoon mechanical property more preferably, is more beneficial for 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 Ba-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 90~110 DEG C, is added barium hydroxide and is carried out Saponification.(5) mixture for obtaining step (4) is warming up to 150~180 DEG C, is dehydrated, then be warming up to 200~220 DEG C of refinings System, is cooled to after 90~120 DEG C and adds other auxiliary agents and remaining base oil, and mixed grinding obtains micro- containing spitball shape graphene The Ba-grease of ball.Other auxiliary agents include：0.5~2 part of antioxidant, 0~2 part of surfactant, 0.5~1 part of antirust agent.
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) 0.1 part of spitball shape graphene microballoon for obtaining step (3), and 54 parts of base oil, 8.9 parts of mixing of stearic acid, It is warming up to after 90 DEG C, adds barium hydroxide and carry out saponification；
(5) mixture for obtaining step (4) is warming up to 160 DEG C, is dehydrated, then is warming up to 210 DEG C of refinings, is cooled to 100 0.6 part of antioxidant, 1.4 parts and 35 parts base oils of antirust agent are added after DEG C, mixed grinding is obtained containing spitball shape graphene microballoon Ba-grease.
Through above step, the Ba-grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon is micro- It is fold microballoon of the diameter at 3~5 μm to see lower, as shown in figure 1, its density is 0.2g/cm3, carbon-to-oxygen ratio is 22.7, specific surface area For 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) 0.1 part of spitball shape graphene microballoon for obtaining step (3), and 54 parts of base oil, 8.9 parts of mixing of stearic acid, It is warming up to after 90 DEG C, adds barium hydroxide and carry out saponification；
(5) mixture for obtaining step (4) is warming up to 160 DEG C, is dehydrated, then is warming up to 210 DEG C of refinings, is cooled to 100 0.6 part of antioxidant, 1.4 parts and 35 parts base oils of antirust agent are added after DEG C, mixed grinding is obtained containing spitball shape graphene microballoon Ba-grease.
Through above step, the Ba-grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon is micro- It is fold microballoon of the diameter at 3~5 μm to see lower, and density is 0.23g/cm3, carbon-to-oxygen ratio is 23.1, and specific surface area is 181m2/g.Institute The performance for obtaining lubricating grease 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) 0.1 part of spitball shape graphene microballoon for obtaining step (3), and 54 parts of base oil, 8.9 parts of mixing of stearic acid, It is warming up to after 90 DEG C, adds barium hydroxide and carry out saponification；
(5) mixture for obtaining step (4) is warming up to 160 DEG C, is dehydrated, then is warming up to 210 DEG C of refinings, is cooled to 100 0.6 part of antioxidant, 1.4 parts and 35 parts base oils of antirust agent are added after DEG C, mixed grinding is obtained containing spitball shape graphene microballoon Ba-grease.
Through above step, the Ba-grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon is micro- It is fold microballoon of the diameter at 3~5 μm to see lower.Its density is 0.25g/cm3, carbon-to-oxygen ratio is 22.9, and specific surface area is 166m2/g。 The performance of gained lubricating grease 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) 0.1 part of spitball shape graphene microballoon for obtaining step (3), and 51 parts of base oil, 12- hydroxy stearic acids 9.8 Part mixing, is warming up to after 100 DEG C, adds barium hydroxide and carries out saponification；
(5) mixture for obtaining step (4) is warming up to 150 DEG C, is dehydrated, then is warming up to 200 DEG C of refinings, is cooled to 120 0.6 part of antioxidant, 1.4 parts of antirust agent, 1 part and 36 parts base oils of surfactant are added after DEG C, mixed grinding is obtained containing paper The Ba-grease of nodular graphite alkene microballoon.
Through above step, the Ba-grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon is micro- It is fold microballoon of the diameter at 3~5 μm to see lower, and 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) 0.1 part of spitball shape graphene microballoon for obtaining step (3), and 52 parts of base oil, 8.9 parts of mixing of stearic acid, It is warming up to after 105 DEG C, adds barium hydroxide and carry out saponification；
(5) mixture for obtaining step (4) is warming up to 155 DEG C, is dehydrated, then is warming up to 215 DEG C of refinings, is cooled to 120 0.6 part of antioxidant, 1.4 parts and 37 parts base oils of antirust agent are added after DEG C, mixed grinding is obtained containing spitball shape graphene microballoon Ba-grease.
Through above step, the Ba-grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon is micro- It is fold microballoon of the diameter at 3~5 μm to see lower, and 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) 0.3 part of spitball shape graphene microballoon for obtaining step (3), and 51 parts of base oil, 12- hydroxy stearic acids 11.6 parts of mixing, are warming up to after 100 DEG C, add barium hydroxide and carry out saponification；
(5) mixture for obtaining step (4) is warming up to 150 DEG C, is dehydrated, then is warming up to 200 DEG C of refinings, is cooled to 120 0.6 part of antioxidant, 1.4 parts of antirust agent, 1 part and 28 parts base oils of surfactant are added after DEG C, mixed grinding is obtained containing paper The Ba-grease of nodular graphite alkene microballoon.
Through above step, the Ba-grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon is micro- It is fold microballoon of the diameter at 3~5 μm to see lower, and 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) 0.05 part of spitball shape graphene microballoon for obtaining step (3), and 48 parts of base oil, 13.1 parts of stearic acid are mixed Close, be warming up to after 100 DEG C, add barium hydroxide and carry out saponification；
(5) mixture for obtaining step (4) is warming up to 150 DEG C, is dehydrated, then is warming up to 200 DEG C of refinings, is cooled to 120 0.6 part of antioxidant, 1.4 parts of antirust agent, 1 part and 28 parts base oils of surfactant are added after DEG C, mixed grinding is obtained containing paper The Ba-grease of nodular graphite alkene microballoon.
Through above step, the Ba-grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon is micro- It is fold microballoon of the diameter at 2~4 μm to see lower, and 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) 0.2 part of spitball shape graphene microballoon for obtaining step (3), and 58 parts of base oil, 17.8 parts of stearic acid are mixed Close, be warming up to after 100 DEG C, add barium hydroxide and carry out saponification；
(5) mixture for obtaining step (4) is warming up to 155 DEG C, is dehydrated, then is warming up to 200 DEG C of refinings, is cooled to 120 0.6 part of antioxidant, 1.4 parts of antirust agent, 1 part and 31 parts base oils of surfactant are added after DEG C, mixed grinding is obtained containing paper The Ba-grease of nodular graphite alkene microballoon.
Through above step, the Ba-grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon is micro- It is diameter in the fold microballoon of 500nm~3 μm to see lower, and 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) 0.1 part of spitball shape graphene microballoon for obtaining step (3), and 41 parts of base oil, 9.4 parts of mixing of stearic acid, It is warming up to after 100 DEG C, adds barium hydroxide and carry out saponification；
(5) mixture for obtaining step (4) is warming up to 155 DEG C, is dehydrated, then is warming up to 210 DEG C of refinings, is cooled to 110 0.6 part of antioxidant, 1.4 parts of antirust agent, 1 part and 35 parts base oils of surfactant are added after DEG C, mixed grinding is obtained containing paper The Ba-grease of nodular graphite alkene microballoon.
Through above step, the Ba-grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon is micro- It is fold microballoon of the diameter at 1~4 μm to see lower, and specific nature is as shown in table 1,2.
Comparative example 1：Method according to embodiment 1 prepares Ba-grease, unlike, without spitball in preparation process 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) 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 put into tube furnace, is continually fed into hydrogen-argon-mixed, temperature 3000 DEG C are risen to, 1h is incubated.
(3) 0.1 part of graphene for obtaining step (2), and 51 parts of base oil, the 8.9 parts of mixing of 12- hydroxy stearic acids, rise After warm to 100 DEG C, add barium hydroxide and carry out saponification；
(4) mixture for obtaining step (3) is warming up to 160 DEG C, is dehydrated, then is warming up to 210 DEG C of refinings, is added after cooling 0.6 part of antioxidant, 1.4 parts and 38 parts base oils of antirust agent, mixed grinding obtain Ba-grease.
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.Gained Ba-grease performance 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) 5 parts of spitball shape graphene microballoon for obtaining step (3), and 58 parts of base oil, 17.8 parts of mixing of stearic acid, It is warming up to after 100 DEG C, adds barium hydroxide and carry out saponification；
(5) mixture for obtaining step (4) is warming up to 155 DEG C, is dehydrated, then is warming up to 200 DEG C of refinings, is cooled to 120 0.6 part of antioxidant, 1.4 parts of antirust agent, 1 part and 31 parts base oils of surfactant are added after DEG C, mixed grinding is obtained containing paper The Ba-grease of nodular graphite alkene microballoon.
Through above step, the Ba-grease containing spitball shape graphene microballoon is obtained.Spitball shape graphene microballoon is micro- It is fold microballoon of the diameter in 500nm~3 μm to see lower, because step (1)~(3) are same as Example 8, therefore graphene microballoon Carbon-to-oxygen ratio, density, specific surface area it is same as Example 8.Specific nature is as shown in table 2.It can be found that improving graphene ball Addition can further lift the properties of lubricating grease.

Claims (10)

1. a kind of Ba-grease containing spitball shape graphene microballoon, it is characterised in that in parts by mass including following component： 70~90 parts of base oil, 5~20 parts of barium base thickening agent, 0.01~5 part of spitball shape graphene microballoon, 1~5 part of other auxiliary agents.Institute Spitball shape graphene microballoon is stated to be formed by single-layer graphene film gauffer, microsphere diameter be 500nm~5 μm, density be 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 higher than 1000 DEG C, obtains spitball Shape graphene 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 0~2 part of face activating agent, 0.5~1 part of antirust agent.
9. lubricating grease according to claim 1, it is characterised in that the barium base thickening agent is C12-C24Natural acid Or the reactant of synthetic fatty acid and barium hydroxide.
10. a kind of preparation method of the Ba-grease containing spitball shape graphene microballoon, it is characterised in that including following step Suddenly：
(1) by spitball shape graphene microballoon, part basis oil and C12-C24Aliphatic acid is mixed, and is warming up to after 90~110 DEG C, is added Barium hydroxide carries out saponification；
(2) mixture for obtaining step (1) is warming up to 150~180 DEG C, is dehydrated, then is warming up to 200~220 DEG C of refinings, cools down Other auxiliary agents and remaining base oil are added after to 90~120 DEG C, mixed grinding obtains the barium base containing spitball shape graphene microballoon Lubricating grease.
CN201710302917.0A 2017-04-28 2017-05-03 A kind of Ba-grease containing spitball shape graphene microballoon and preparation method thereof Pending CN107033994A (en)

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US16/622,953 US11225414B2 (en) 2017-04-28 2018-02-26 Paper ball-like graphene microsphere, composite material thereof, and preparation method therefor
KR1020197034665A KR102307001B1 (en) 2017-04-28 2018-02-26 Paperball-type graphene microspheres and their composite material and manufacturing method
PCT/CN2018/077221 WO2018196474A1 (en) 2017-04-28 2018-02-26 Paper ball-like graphene microsphere, composite material thereof, and preparation method therefor
RU2019138451A RU2734476C1 (en) 2017-04-28 2018-02-26 Graphene microspheres in form of paper lump, composite material of such microspheres and method of making such microspheres
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WO2018196474A1 (en) * 2017-04-28 2018-11-01 杭州高烯科技有限公司 Paper ball-like graphene microsphere, composite material thereof, and preparation method therefor
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Application publication date: 20170811