WO2018196474A1 - 一种纸团状石墨烯微球及其复合材料和制备方法 - Google Patents

一种纸团状石墨烯微球及其复合材料和制备方法 Download PDF

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WO2018196474A1
WO2018196474A1 PCT/CN2018/077221 CN2018077221W WO2018196474A1 WO 2018196474 A1 WO2018196474 A1 WO 2018196474A1 CN 2018077221 W CN2018077221 W CN 2018077221W WO 2018196474 A1 WO2018196474 A1 WO 2018196474A1
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Prior art keywords
graphene
parts
microspheres
paper
temperature
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PCT/CN2018/077221
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English (en)
French (fr)
Inventor
高超
陈琛
韩燚
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杭州高烯科技有限公司
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Priority claimed from CN201710294360.0A external-priority patent/CN106966383B/zh
Priority claimed from CN201710293102.0A external-priority patent/CN107090324A/zh
Priority claimed from CN201710294376.1A external-priority patent/CN107090325A/zh
Priority claimed from CN201710302915.1A external-priority patent/CN106987188B/zh
Priority claimed from CN201710302917.0A external-priority patent/CN107033994A/zh
Priority claimed from CN201710302912.8A external-priority patent/CN106977768B/zh
Priority claimed from CN201710302898.1A external-priority patent/CN107057058B/zh
Priority claimed from CN201710302916.6A external-priority patent/CN107022121B/zh
Priority to EP18791151.6A priority Critical patent/EP3617141B1/en
Priority to RU2019138451A priority patent/RU2734476C1/ru
Priority to KR1020197034665A priority patent/KR102307001B1/ko
Priority to US16/622,953 priority patent/US11225414B2/en
Application filed by 杭州高烯科技有限公司 filed Critical 杭州高烯科技有限公司
Publication of WO2018196474A1 publication Critical patent/WO2018196474A1/zh

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    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C10M2201/0413—Carbon; Graphite; Carbon black used as base material
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
    • 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
    • C10M2207/1256—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 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
    • C10M2207/126—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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the field of graphene materials, and relates to a paper-like graphene microsphere, a composite material thereof and a preparation method thereof.
  • graphene As a new type of two-dimensional carbon material, graphene has attracted more and more attention from the world. Due to its superior mechanical properties, electrical properties, thermal properties and unique electromagnetic properties, graphene has shown broad application prospects in many fields and has gradually moved to practical applications. There have been many reports that the combination of graphene and high polymer can significantly improve the tensile strength, Young's modulus and flexural strength of the material. The strengthening mechanism is mainly to utilize the superior mechanical strength of graphene and transfer the stress to graphene. Improve the overall mechanical properties of the composite. Graphene is available in a variety of forms, including graphene films, graphene aerogels, graphene powders, graphene fibers, and the like, which tend to exhibit different reinforcing effects.
  • the combination of graphene aerogel and polymer material can effectively improve the electrical and thermal conductivity of the polymer material.
  • flake graphene has limited enhancement of impact properties, lack of enhancement mechanism, and cannot be used as an effective toughening agent. If graphene is made into a spherical shape, the mechanical strength can be more fully utilized, and it has a unique utilization prospect in terms of improving impact, wear resistance, and elasticity.
  • Patent CN201010593157.1 A method for preparing graphene powder” adopts atomization drying and slow heating treatment to obtain non-expanded graphene powder. The method is simple and can be prepared in large quantities, but there is still gas in direct heat treatment. Release, causing the graphene to partially swell.
  • Patent CN201310131014 A method for preparing graphene material and its use in chemical energy storage and/or conversion” by adding a substance which can react or polymerize or decompose in a graphene oxide dispersion, so that the obtained powder is reduced It has a porous structure and is beneficial to the application in the field of electrochemical energy storage. However, how to obtain a pleated microsphere-like graphene material that does not swell or even shrink is still a major difficulty.
  • Lubricating oil is one of the important means to effectively reduce mechanical energy loss and wear. After adding lubricating oil, it can achieve lubrication, anti-friction, cooling and cooling, cleaning and cleaning, sealing and leakage prevention, anti-rust and anti-corrosion, shock absorption buffer and so on.
  • Conventional lubricating oils are made up of a mixture of base oils and various additives.
  • the base oils are mineral oil, biomass oil and synthetic oil. The additives are used to improve the properties of the base oil.
  • Graphene has an ultra-thin lamellar structure (easy to enter the frictional contact surface), excellent mechanical properties and self-lubricating properties. These properties have attracted attention in the application of lubricating additives.
  • a large number of studies have found that a proper amount of graphene is used as a lubricating additive. Not only can the friction coefficient be reduced, but also the bearing anti-wear performance of the lubricant can be significantly improved by the form of a friction-adsorbing film.
  • graphene is prone to agglomeration in lubricating oils, which affects its dispersion stability in lubricating oils and solvents.
  • the rapid development of the machinery industry has led to the upgrading of the grease industry.
  • the calcium-based grease used in the early stage is used at a lower temperature and is not suitable for use in high-speed applications.
  • the sodium-based grease and sulfhydryl grease developed later are ecologically friendly. And the poor water resistance and other reasons have not made it widely used; later developed lithium-based grease, lithium stearate or 12-hydroxy lithium grease has high use temperature, low friction coefficient, good lubrication performance, resistance
  • the characteristics of water performance and other characteristics make lithium base grease widely used in the automotive industry.
  • high-performance automobiles have put forward more stringent requirements for lithium-based greases, and lithium complex greases have emerged.
  • the composite lithium grease has high dropping point and high temperature resistance; the composite soap has high fiber structure strength, good mechanical stability under high temperature conditions, long service life, and good water repellency resistance.
  • the composite soap has high fiber structure strength, good mechanical stability under high temperature conditions, long service life, and good water repellency resistance.
  • it is difficult to meet the requirements of use due to poor antifriction and anti-wear properties. In order to meet the requirements of demanding conditions, further improvement is required. Its performance.
  • Rubber has unique high elasticity at room temperature, light weight and wide applicability. As an important strategic material, it is widely used in the fields of national economy, high-tech and national defense military. However, the rubber strength is low and the modulus is simple. Low, poor wear resistance, poor fatigue resistance, no practicality, so for most rubbers need to be filled and reinforced.
  • Carbon black (CB) and white carbon black (SiO 2 ) are the main reinforcing agents of traditional rubber. They are widely used in various rubber products, but at the same time as rubber reinforcement, due to the inherent viscoelastic hysteresis loss and rubber of rubber materials. The internal friction between the filler and the macromolecular chain causes a large amount of heat to be generated in the rubber product used in the dynamic environment.
  • Graphene is a two-dimensional carbon material with atomic thickness, which has an ultra-high specific surface area, excellent mechanical properties, high thermal conductivity and self-lubricating properties.
  • many researchers have combined graphene with coatings to improve the performance of waterborne coatings by utilizing the excellent properties of graphene.
  • flake graphene is easily agglomerated to form a stacked graphite structure, on the one hand, the excellent performance of graphene cannot be achieved, and on the other hand, the dispersion stability is lowered.
  • Patent 201510518720.1 High-performance water-based acrylate coating containing graphene and its preparation method and application by adding sulfonated graphene to waterborne acrylate coating, its tensile strength and thermal conductivity are significantly improved.
  • Patent 201610353311.5 A graphene/acrylic conductive electrostatic coating and its preparation method” utilizes a similar method to add graphene to an acrylic coating, so that conductivity and acid mist resistance are improved.
  • Nylon has the largest output, the widest variety and the widest use among the five engineering plastics. It has the advantages of high mechanical strength, high melting point, good wear resistance, oil resistance and heat resistance. It is widely used in automotive, electronic and electrical, machinery and other fields. Due to the higher requirements for the toughness of nylon in many applications, nylon must be toughened to meet these applications.
  • the toughening modification of nylon mainly includes three methods of toughening elastomer, toughening of inorganic rigid particles, and toughening of organic rigid particles. The elastomer can significantly improve the toughness of the nylon material, but at the same time, the material is greatly reduced.
  • Rigidity and strength; inorganic rigid particles and organic rigid particles can be enhanced while toughening, but their toughening range is limited.
  • shape of the rigid particles affects the toughening effect of the matrix.
  • the rigid particles in the flaky, spherical and needle-like structures the rigid particles of the spherical structure have the best toughening effect on the material.
  • the object of the present invention is to provide a paper-like graphene microsphere, a composite material thereof and a preparation method thereof, in view of the deficiencies of the prior art. Contains the following technical solutions:
  • a method for preparing paper-like graphene microspheres comprising the following steps:
  • the reduced graphene oxide microspheres obtained in the step (2) are subjected to high temperature treatment at a temperature higher than 1000 ° C to obtain paper-like graphene microspheres.
  • a reducing agent is contained, and during the atomization process, the graphene oxide sheet is wrinkled, and at the same time, the reducing agent adheres to the surface of the sheet in a molecular form.
  • the reducing agent is hydrogen iodide, hydrogen bromide, hydrazine hydrate, vitamin C, sodium borohydride, etc., and the mass ratio of the reducing agent to the single layer graphene oxide is 0.1-10.
  • the atomization drying temperature is 100 to 200 ° C, so that the reducing agent encapsulated in the pleated structure performs preliminary reduction of graphene oxide.
  • the reducing atmosphere described in the step (2) is one or more of hydrazine hydrate vapor, hydroiodic acid vapor, hydrogen gas, and hydrobromic acid vapor.
  • the reduction conditions are from 60 to 200 ° C for 30 minutes to 48 hours.
  • the high temperature treatment temperature described in the step (3) is 2500 to 3000 ° C, and the atmosphere is one of nitrogen gas, helium gas, hydrogen gas argon gas mixture, and argon gas, and the treatment time is 30 min to 48 h.
  • the present invention firstly prepares graphene oxide microspheres by atomization drying method, and adds a reducing agent to the graphene oxide dispersion liquid before atomization drying, and uniformly mixes the reducing agent in molecular form on the graphene oxide. Sheet surface. Then, during the atomization drying process, part of the reducing agent reacts with the oxygen-containing functional group on the surface of the graphene oxide, the product is released with the evaporation of the solvent, and the remaining reducing agent is attached to the surface of the graphene oxide sheet in a molecular form, and The wrinkles are wrapped up. In the second step, chemical reduction is carried out.
  • the oxygen-containing functional groups inside and on the surface of the graphene oxide microspheres are fully reacted with the reducing agent, and the lower temperature makes the gas generation and release slow, avoiding the direct thermal reduction of the medium group.
  • the mass rapidly removes the gas, causing a sharp expansion of the volume, thus keeping the graphene still tightly bound in the form of pleats without separation.
  • the third step of high-temperature thermal reduction removes a small amount of oxygen-containing functional groups on the one hand, and repairs the defect structure in the graphene oxide sheet, and on the other hand, removes residual moisture, reduction products and unreacted reducing agent in the microspheres. except.
  • the obtained paper-like graphene microspheres have a more dense structure, and the dense paper-like graphene microspheres have good mechanical properties and elasticity at the same time, can effectively absorb impact, and have strong stability, compared with the conventional enhanced filling.
  • the agent has a lower density and a better reinforcing effect.
  • a graphene-based lubricating oil comprising, by mass parts, 100 parts of a base oil, 0.05 to 1 part of paper-like graphene microspheres, and 2 to 14 parts of other auxiliary agents.
  • the paper-like graphene microspheres are formed by folding a single layer of graphene sheets, the diameter of the microspheres is 500 nm to 5 ⁇ m, the density is 0.2 to 0.4 g/cm 3 , the carbon-oxygen ratio is 20 to 60, and the specific surface area is lower than 200m 2 /g.
  • a method for preparing a graphene-based lubricating oil comprising the steps of:
  • auxiliary agents include: 0.5 to 1 part of a dispersing agent, 0.5 to 1.5 parts of an affinity agent, 0.3 to 1 part of a viscosity modifier, 0.2 to 0.5 part of an antifoaming agent, and 0.5 to 10 parts of a preservative.
  • the beneficial effect is that the obtained paper-like graphene microspheres have a more dense structure, and the dense paper-like graphene microspheres have good mechanical properties and elasticity at the same time, can effectively absorb impact, have strong stability, and exert external force.
  • the graphene microspheres under extreme pressure can be filled in the wear part to reduce further wear, which can significantly improve the wear resistance and friction reduction of the lubricating oil.
  • a lithium complex grease containing paper-like graphene microspheres which comprises the following components in parts by mass: 70-90 parts of base oil, 5-20 parts of lithium complex thickener, and paper-like graphene micro
  • the ball is 0.05 to 5 parts
  • the other auxiliary agent is 1 to 5 parts.
  • the paper-like graphene microspheres are formed by folding a single layer of graphene sheets, the diameter of the microspheres is 500 nm to 5 ⁇ m, the density is 0.2 to 0.4 g/cm 3 , the carbon-oxygen ratio is 20 to 60, and the specific surface area is lower than 200m 2 /g.
  • the other auxiliary agent includes 0.5 to 2 parts of an antioxidant, 0 to 2 parts of a surfactant, and 0.5 to 1 part of a rust preventive agent.
  • the complex lithium-based thickener is a complex of a macromolecular acid and a small molecular acid reacted with lithium hydroxide, the macromolecular acid is a C 12 -C 24 fatty acid, and the small molecular acid is a C 1 -C 12 One of a fatty acid or a boric acid, the molar ratio of the macromolecular acid to the small molecular acid is 1:0.1 to 2.
  • a preparation method of a composite lithium-based grease containing paper-like graphene microspheres comprising the following steps:
  • step (2) The mixture obtained in the step (1) is heated to 160 to 180 ° C, dehydrated, and then heated to 190 to 220 ° C for refining. After cooling, other auxiliary agents and remaining base oil are added, and the mixture is ground to obtain paper-like graphite.
  • the amount of the base oil added in the step 1 and the step 2 is determined according to the state of mixing, which ensures uniform mixing and ensures fluidity, and is common knowledge in the art.
  • the obtained paper-like graphene microspheres have good mechanical properties and elasticity, can effectively absorb impact, and have strong stability.
  • the paper-like structure reduces the stacking of graphene and improves the overall stability.
  • the graphene microspheres are subjected to rolling friction on the friction surface, and the graphene microspheres can be filled in the wear portion under extreme pressure to reduce further wear, which can significantly improve the wear resistance and friction reduction of the grease.
  • graphene microspheres with low specific surface area and low void ratio have better mechanical properties and are more conducive to improving lubrication performance.
  • a sulfhydryl grease containing paper-like graphene microspheres which comprises the following components in parts by mass: 70-90 parts of base oil, 5-20 parts of sulfhydryl thickener, and paper-like graphene microspheres 0.01 ⁇ 5 parts, 1 to 5 parts of other additives.
  • the paper-like graphene microspheres are formed by pleating a single-layer graphene sheet having a size of 1 to 200 ⁇ m, the diameter of the microspheres is 500 nm to 5 ⁇ m, the density is 0.04 to 0.2 g/cm 3 , and the carbon-oxygen ratio is 10 ⁇ . 30.
  • the other auxiliary agent comprises: 0.5 to 2 parts of an antioxidant, 0 to 2 parts of a surfactant, and 0.5 to 1 part of a rust preventive.
  • the sulfhydryl thickener is a C 12 -C 24 natural fatty acid or a reaction of a synthetic fatty acid with cesium hydroxide
  • a method for preparing a sulfhydryl grease containing paper-like graphene microspheres comprising the following steps:
  • step (2) The mixture obtained in the step (1) is heated to 150 to 180 ° C, dehydrated, and then heated to 200 to 220 ° C for refining, cooled to 90 to 120 ° C, and then added with other additives and residual base oil, mixed and ground to obtain A sulfhydryl grease containing paper-like graphene microspheres.
  • the amount of the base oil added in the step 1 and the step 2 is determined according to the state of mixing, which ensures uniform mixing and ensures fluidity, and is common knowledge in the art.
  • the invention has the beneficial effects that the obtained paper-like graphene microspheres have good mechanical properties and elasticity, can effectively absorb impact, and have strong stability.
  • the paper-like structure reduces the stacking of graphene and improves the overall stability.
  • the graphene microspheres are subjected to rolling friction on the friction surface, and the graphene microspheres can be filled in the wear portion under extreme pressure to reduce further wear, which can significantly improve the wear resistance and friction reduction of the grease.
  • graphene microspheres with low specific surface area and low void ratio have better mechanical properties and are more conducive to improving lubrication performance.
  • a composite rubber modified by paper-like graphene microspheres comprising the following components in parts by mass: 100 parts of rubber, 0.1 to 10 parts of paper-like graphene microspheres, 0.5 to 5 parts of vulcanizing agent, 3 to 10 parts of vulcanization accelerator and 5-20 parts of other additives.
  • the paper-like graphene microspheres are formed by folding a single layer of graphene sheets, the diameter of the microspheres is 500 nm to 5 ⁇ m, the density is 0.2 to 0.4 g/cm 3 , the carbon-oxygen ratio is 20 to 60, and the specific surface area is lower than 200m 2 /g.
  • the rubber is one or more of natural rubber, nitrile rubber, silicone rubber, butadiene rubber, isoprene rubber, styrene butadiene rubber, ethylene propylene rubber, and neoprene rubber.
  • the other auxiliary agents include: 2 to 5 parts of stearic acid, 0.5 to 2 anti-aging agents, 0.5 to 3 parts of liquid paraffin, and 2 to 10 parts of zinc oxide.
  • the vulcanizing agent is at least one of sulfur, a peroxide, a metal oxide, a resin vulcanizing agent, and a sulfur-containing organic substance.
  • a preparation method of composite rubber modified by paper-like graphene microspheres comprising the following steps:
  • the invention has the beneficial effects that the obtained paper-like graphene microspheres have good mechanical properties and elasticity, can effectively absorb impact, and have strong stability.
  • the paper-like structure reduces the stacking of graphene and improves the overall stability.
  • the paper-like graphene ball can effectively improve the mechanical strength of the rubber, absorb the impact and promote the rebound of the material.
  • the addition of graphene also improves the thermal conductivity and flame retardancy of the material as a whole, making the composite rubber have a higher service life.
  • a graphene-based water-based acrylic paint and a preparation method thereof characterized in that the following components are included in parts by mass: 100 parts of acrylic resin emulsion, 0.1 to 5 parts of paper-like graphene microspheres, 30 to 60 parts of inorganic filler, 0.9 to 12 parts of auxiliary agent, 10 to 20 parts of water.
  • the paper-like graphene microspheres are formed by folding a single layer of graphene sheets, the diameter of the microspheres is 500 nm to 5 ⁇ m, the density is 0.2 to 0.4 g/cm 3 , the carbon-oxygen ratio is 20 to 60, and the specific surface area is lower than 200m 2 /g.
  • the acrylic resin emulsion is one or more of a pure acrylic emulsion, a styrene-acrylic emulsion, and a vinegar-acrylic emulsion.
  • the inorganic filler is one or more of titanium dioxide, silicon dioxide, aluminum oxide, calcium carbonate, and potassium carbonate.
  • the auxiliary agent comprises: 0.1-0.5 parts of dispersing agent, 0.1-0.3 part of preservative, 0.1-0.5 part of film-forming agent, 0.05-0.2 part of leveling agent, 0.5-10 part thickening agent, 0.05-0.5 part elimination Foaming agent.
  • the invention discloses a method for preparing a graphene-based water-based acrylic paint, which comprises: uniformly stirring paper-like graphene microspheres and an acrylic resin emulsion, ultrasonically dispersing, and then sequentially adding water, an auxiliary agent and an inorganic filler, stirring at a high speed, and defoaming. .
  • the invention has the beneficial effects that the obtained paper-like graphene microspheres have good mechanical properties and elasticity, can effectively absorb impact, and have strong stability.
  • the paper-like structure reduces the stacking of graphene and improves the overall stability.
  • the paper-like graphene microspheres After adding the coating, the paper-like graphene microspheres have much lower agglomeration than the flake graphene and the expanded graphite, and can be stably dispersed in the coating for a long time, and the coating film obtained after coating drying has good impact resistance. And due to the corrosion resistance and antibacterial properties of graphene, the related properties of the coating can be further improved.
  • a graphene/cast nylon composite material composed of 0.1 to 5 parts of paper-like graphene microspheres and 100 parts of cast nylon.
  • the paper-like graphene microspheres are formed by folding a single layer of graphene sheets, the diameter of the microspheres is 500 nm to 5 ⁇ m, the density is 0.2 to 0.4 g/cm 3 , the carbon-oxygen ratio is 20 to 60, and the specific surface area is lower than 200m 2 /g.
  • a method for preparing a graphene/cast nylon composite material comprising the steps of:
  • the invention has the beneficial effects that the obtained paper-like graphene microspheres have a more dense structure, and the dense paper-like graphene microspheres have good mechanical properties and elasticity at the same time, can effectively absorb impact and have strong stability.
  • the graphene microspheres can effectively absorb energy and reduce the damage to the cast nylon matrix.
  • the graphene microspheres can roll friction on the friction surface under extreme pressure.
  • the graphene microspheres can be filled in the worn parts to reduce further wear, which can significantly improve the wear-resisting and anti-friction properties of the cast nylon.
  • a method for improving the impact strength of nylon 6 by paper-like graphene which is obtained by using paper-like graphene toughened nylon 6, which is formed by wrinkling a single-layer graphene sheet.
  • the microspheres have a diameter of 500 nm to 5 ⁇ m, a density of 0.2 to 0.4 g/cm 3 , a carbon-oxygen ratio of 20 to 60, and a specific surface area of less than 200 m 2 /g.
  • the weight ratio of nylon 6 to graphene microspheres is 100:0.05 ⁇ 1, premixed in a mixer to obtain a uniformly mixed nylon 6/graphene premix, and nylon 6 and premix before premixing.
  • the graphene microspheres are dried in a vacuum oven at 80-105 ° C for 8 to 12 hours;
  • the premix obtained in the step (1) is melt-blended and extruded by a twin-screw extruder at a processing temperature of 230 to 250 ° C and a rotation speed of 150 to 250 rpm, cooled, and granulated to obtain a nylon 6/graphite. Aene composite.
  • Paper-like graphene microspheres are used as toughening modifiers for nylon 6 materials.
  • the spherical structure of graphene particles is more easily dispersed in the nylon 6 matrix, and the micro-pleated shape and structure on the surface of the graphene microspheres are given.
  • the better flexibility of the graphene particles can further buffer the stress compared with the ordinary sheet filler, similar to the action of the elastic particles, and improve the impact strength of the nylon 6 material.
  • the paper-like graphene toughened nylon 6 composite material is processed by melt blending and extruding.
  • the method has simple operation process, no solvent pollution, high production efficiency and is suitable for large-scale production.
  • graphene not only improves the impact strength of nylon 6 material, but also promotes the 6 crystals of nylon, thereby further improving the rigidity and heat resistance of the material.
  • the comprehensive properties of graphene can also give the material a comprehensive performance of antistatic, ultraviolet aging, flame retardancy and water resistance.
  • Figure 1 is a photograph of a paper-like graphene microsphere prepared by Example 1-1 of the present invention.
  • Example 2 is a microscopic morphology of paper-like graphene microspheres prepared by Example 1-1 of the present invention.
  • Figure 3 is a microscopic morphology of expanded graphene microspheres prepared by Comparative Example 1-1 of the present invention.
  • Figure 5 is a macro photograph of a graphene-based lubricating oil prepared in accordance with Example 2-1 of the present invention.
  • the obtained paper-like graphene microspheres have a black powder appearance as shown in FIG.
  • the pleated microspheres have a diameter of 3 to 5 ⁇ m, as shown in Fig. 2.
  • the density was 0.2 g/cm 3
  • the carbon to oxygen ratio was 22.7
  • the specific surface area was 190 m 2 /g.
  • the obtained paper-like graphene microspheres have a black powder appearance and microscopically are pleated microspheres having a diameter of 3 to 5 ⁇ m.
  • the density was 0.23 g/cm 3
  • the carbon to oxygen ratio was 23.1
  • the specific surface area was 181 m 2 /g.
  • the obtained paper-like graphene microspheres have a black powder appearance and microscopically are pleated microspheres having a diameter of 3 to 5 ⁇ m.
  • the density was 0.25 g/cm 3
  • the carbon to oxygen ratio was 22.9
  • the specific surface area was 166 m 2 /g.
  • the second step of the reduction is mainly to slowly remove the groups on the surface of the graphene oxide.
  • the low reduction temperature or short time may result in insufficient reduction, and the residual groups will continue to be removed during the third high temperature heat treatment.
  • a gas is generated to cause the graphene sheets to expand outward.
  • the carbon-oxygen ratio is mainly affected by the third step reduction, and has little correlation with the second step. Therefore, in summary, the second step of reducing conditions may preferably be a high reduction temperature and a long reduction time.
  • the obtained paper-like graphene microspheres have a black powder appearance and microscopically have pleated microspheres having a diameter of 3 to 5 ⁇ m, and the properties are shown in Table 1-1.
  • the obtained paper-like graphene microspheres have a black powder appearance and microscopically have pleated microspheres having a diameter of 3 to 5 ⁇ m, and the properties are shown in Table 1-1.
  • the obtained paper-like graphene microspheres have a black powder appearance and microscopically have pleated microspheres having a diameter of 3 to 5 ⁇ m, and the properties are shown in Table 1-1.
  • step (3) The reduced graphene oxide microspheres obtained in the step (2) were placed in a tube furnace, nitrogen gas was continuously introduced, the temperature was raised to 2000 ° C, and the temperature was maintained for 1 h to obtain paper-like graphene microspheres.
  • the obtained paper-like graphene microspheres have a black powder appearance and microscopically have pleated microspheres having a diameter of 2 to 4 ⁇ m, and the properties are as shown in Table 1-1.
  • step (3) The reduced graphene oxide microspheres obtained in the step (2) were placed in a tube furnace, nitrogen gas was continuously introduced, the temperature was raised to 3000 ° C, and the temperature was maintained for 1 h to obtain paper-like graphene microspheres.
  • the obtained paper-like graphene microspheres have a black powder appearance and microscopically have pleated microspheres having a diameter of 500 nm to 3 ⁇ m, and the properties are as shown in Table 1-1.
  • step (3) The reduced graphene oxide microspheres obtained in the step (2) were placed in a tube furnace, nitrogen gas was continuously introduced, the temperature was raised to 3000 ° C, and the temperature was maintained for 1 h to obtain paper-like graphene microspheres.
  • the obtained paper-like graphene microspheres have a black powder appearance and microscopically have pleated microspheres having a diameter of 1 to 4 ⁇ m, and the properties are as shown in Table 1-1.
  • the reduced graphene oxide microspheres obtained in the step (1) were placed in a tube furnace, and a hydrogen-argon mixed gas was continuously introduced, the temperature was raised to 2500 ° C, the temperature rising rate was 5 ° C / min, and the temperature was kept for 1 h.
  • the obtained graphene has a black fluffy powder and a microscopic hollow sphere shell having a diameter of 1 to 10 ⁇ m, as shown in FIG.
  • the properties are shown in Table 1-1.
  • the high temperature heat treatment causes the unremoved groups in the reduced graphene oxide microspheres to be detached (the carbon-oxygen ratio is increased), and the generated gas expands the graphene interlayer structure, resulting in an increase in the specific surface area.
  • the graphene microspheres can release less gas in the third step of high-temperature heat treatment, reducing the volume expansion and making the structure more compact. Therefore, in order to obtain graphene microspheres with high density and low specific surface area, it is important to add a reducing agent.
  • microspheres obtained in Examples 1-3, 1-5, 1-8 and Comparative Example 1-1 were compounded with rubber, and the properties were tested as shown in Table 1-2 after mechanical properties test. It has been found that the use of paper-like graphene microspheres having a high density and a low specific surface area can significantly increase the tensile strength and tear strength of the rubber.
  • Steps 1-3 are the same as those in the embodiment 1-1;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), 0.5 parts of the dispersing agent, 0.6 parts of the affinity agent, 0.5 part of the viscosity modifier, 0.3 parts of the anti-foaming agent, and 1 part of the preservative are sequentially added to 100. Stir well in the base oil;
  • Step 5 The mixture obtained in the step (4) is dispersed by ultrasonication and defoamed.
  • a graphene-based lubricating oil is obtained, as shown in Fig. 5, which is a black viscous liquid.
  • the resulting lubricating oil had a coefficient of friction of 0.094.
  • Steps 1-3 are the same as those in the embodiment 1-2;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), 0.5 parts of the dispersing agent, 0.6 parts of the affinity agent, 0.5 part of the viscosity modifier, 0.3 parts of the anti-foaming agent, and 1 part of the preservative are sequentially added to 100. Stir well in the base oil;
  • Step 5 The mixture obtained in the step (4) is dispersed by ultrasonication and defoamed.
  • Steps 1-3 are the same as those in the examples 1-3;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), 0.5 parts of the dispersing agent, 0.6 parts of the affinity agent, 0.5 part of the viscosity modifier, 0.3 parts of the anti-foaming agent, and 1 part of the preservative are sequentially added to 100. Stir well in the base oil;
  • Step 5 The mixture obtained in the step (4) is dispersed by ultrasonication and defoamed.
  • the second step of reducing conditions may preferably be a high reduction temperature and a long reduction time.
  • Steps 1 to 3 are the same as those in the examples 1-4;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), 0.5 parts of the dispersing agent, 0.6 parts of the affinity agent, 0.5 part of the viscosity modifier, 0.3 parts of the anti-foaming agent, and 1 part of the preservative are sequentially added to 100. Stir well in the base oil;
  • Step 5 The mixture obtained in the step (4) is dispersed by ultrasonication and defoamed.
  • Steps 1-3 are the same as those in the examples 1-5;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), 1 part of the dispersing agent, 0.6 parts of the affinity agent, 0.3 parts of the viscosity modifier, 0.3 parts of the anti-foaming agent, and 1 part of the preservative are sequentially added to 100. Stir well in the base oil;
  • Step 5 The mixture obtained in the step (4) is dispersed by ultrasonication and defoamed.
  • Steps 1-3 are the same as Examples 1-6;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), 0.5 parts of the dispersing agent, 1 part of the affinity agent, 0.5 part of the viscosity modifier, 0.5 part of the anti-foaming agent, and 5 parts of the preservative are sequentially added to 100. Stir well in the base oil;
  • Step 5 The mixture obtained in the step (4) is dispersed by ultrasonication and defoamed.
  • Steps 1 to 3 are the same as those in Embodiments 1-7;
  • Step 4 (4) 0.1 parts of the paper-like graphene microspheres obtained in the step (3), 1 part of a dispersing agent, 1.5 parts of an affinity agent, 0.5 part of a viscosity modifier, 0.3 parts of an antifoaming agent, and 8 parts of a preservative Add 100 parts of base oil in turn, and mix well;
  • Step 5 The mixture obtained in the step (4) is dispersed by ultrasonication and defoamed.
  • Steps 1 to 3 are the same as those in Embodiments 1-8;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), 0.8 parts of the dispersing agent, 0.6 parts of the affinity agent, 1 part of the viscosity modifier, 0.5 part of the anti-foaming agent, and 5 parts of the preservative are sequentially added to 100. Stir well in the base oil;
  • Step 5 The mixture obtained in the step (4) is dispersed by ultrasonication and defoamed.
  • Steps 1 to 3 are the same as those in Examples 1-9;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), 1 part of the dispersing agent, 0.7 parts of the affinity agent, 0.5 part of the viscosity modifier, 0.3 parts of the anti-foaming agent, and 10 parts of the preservative are sequentially added to 100. Stir well in the base oil;
  • Step 5 The mixture obtained in the step (4) is dispersed by ultrasonication and defoamed.
  • Comparative Example 2-1 Lubricating oil without graphene.
  • the graphene oxide microspheres obtained in the step (1) are placed in a tube furnace, and a hydrogen-argon mixed gas is continuously introduced, the temperature is raised to 3000 ° C, the heating rate is 5 ° C / min, and the temperature is kept for 1 h;
  • the appearance of the graphene is a black fluffy powder, and the microscopic shape is a hollow spherical shell having a diameter of 1 to 10 ⁇ m.
  • the specific properties of the resulting lubricating oil are shown in Table 2.
  • the more compact ball When combined with lubricating oil, the more compact ball has better friction performance, which can more effectively form protection between the friction surfaces, reducing friction and wear.
  • the graphene microspheres with large specific surface area and large voids are easily deformed after being subjected to pressure, and the friction reducing ability is lowered.
  • step (3) The reduced graphene oxide microspheres obtained in the step (2) are placed in a tube furnace, nitrogen gas is continuously introduced, the temperature is raised to 3000 ° C, and the temperature is maintained for 1 h to obtain paper-like graphene microspheres;
  • a graphene-based lubricating oil is obtained, wherein the paper-like graphene microspheres are microscopically pleated microspheres having a diameter of 500 nm to 3 ⁇ m, and the steps (1) to (3) are the same as those of the embodiment 2-8. Therefore, the carbon-oxygen ratio, density, and specific surface area of the graphene microspheres were the same as in Examples 2-8.
  • the coefficient of friction coefficient is 0.75.
  • step (3) The reduced graphene oxide microspheres obtained in the step (2) are placed in a tube furnace, nitrogen gas is continuously introduced, the temperature is raised to 3000 ° C, and the temperature is maintained for 1 h to obtain paper-like graphene microspheres;
  • a graphene-based lubricating oil is obtained, wherein the paper-like graphene microspheres are microscopically pleated microspheres having a diameter of 500 nm to 3 ⁇ m, and the steps (1) to (3) are the same as those of the embodiment 2-8. Therefore, the carbon-oxygen ratio, density, and specific surface area of the graphene microspheres were the same as in Examples 2-8.
  • the coefficient of friction coefficient is 0.67.
  • Steps 1-3 are the same as those in the embodiment 1-1;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), and 51 parts of the base oil, 8.1 parts of 12-hydroxystearic acid, and 3.8 parts of benzoic acid are mixed, and the temperature is raised to 70 ° C, and then hydroxide is added. Lithium is subjected to a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 160 ° C, dehydrated, and then heated to 190 ° C for refining. After cooling, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent and 35 parts of a base oil are added and mixed and ground to obtain A lithium complex grease containing paper-like graphene microspheres.
  • Steps 1-3 are the same as those in the embodiment 1-2;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), and 51 parts of the base oil, 8.1 parts of 12-hydroxystearic acid, and 3.8 parts of benzoic acid are mixed, and the temperature is raised to 70 ° C, and then hydroxide is added. Lithium is subjected to a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 160 ° C, dehydrated, and then heated to 190 ° C for refining. After cooling, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent and 35 parts of a base oil are added and mixed and ground to obtain A lithium complex grease containing paper-like graphene microspheres.
  • Steps 1-3 are the same as those in the examples 1-3;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), and 51 parts of the base oil, 8.1 parts of 12-hydroxystearic acid, and 3.8 parts of benzoic acid are mixed, and the temperature is raised to 70 ° C, and then hydroxide is added. Lithium is subjected to a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 160 ° C, dehydrated, and then heated to 190 ° C for refining. After cooling, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent and 35 parts of a base oil are added and mixed and ground to obtain A lithium complex grease containing paper-like graphene microspheres.
  • the second step of reducing conditions may preferably be a high reduction temperature and a long reduction time.
  • Steps 1 to 3 are the same as those in the examples 1-4;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), and 47 parts of the base oil, 7.4 parts of 12-hydroxystearic acid, and 4.5 parts of benzoic acid are mixed, and the temperature is raised to 90 ° C, and then hydrogen peroxide is added. Lithium is subjected to a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 170 ° C, dehydrated, and then heated to 200 ° C for refining. After cooling, 0.5 parts of an antioxidant, 1.5 parts of a rust preventive agent and 39 parts of a base oil are added and mixed and ground to obtain A lithium complex grease containing paper-like graphene microspheres.
  • Steps 1-3 are the same as those in the examples 1-5;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), and 63 parts of the base oil, 5.3 parts of 12-hydroxystearic acid, and 6.6 parts of benzoic acid are mixed, and the temperature is raised to 80 ° C, and then hydrogen peroxide is added. Lithium is subjected to a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 165 ° C, dehydrated, and then heated to 200 ° C for refining. After cooling, 0.5 parts of an antioxidant, 1.5 parts of a rust inhibitor and 23 parts of a base oil are added and mixed and ground to obtain A lithium complex grease containing paper-like graphene microspheres.
  • Steps 1-3 are the same as Examples 1-6;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), and 63 parts of the base oil, 5.6 parts of 12-hydroxystearic acid, and 5.3 parts of benzoic acid are mixed, and the temperature is raised to 90 ° C, and then hydrogen peroxide is added. Lithium is subjected to a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 180 ° C, dehydrated, and then heated to 220 ° C for refining. After cooling, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent and 24 parts of a base oil are added and mixed and ground to obtain A lithium complex grease containing paper-like graphene microspheres.
  • Steps 1 to 3 are the same as those in Embodiments 1-7;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), and 63 parts of the base oil, 5.6 parts of 12-hydroxystearic acid, and 5.3 parts of benzoic acid are mixed, and the temperature is raised to 90 ° C, and then hydrogen peroxide is added. Lithium is subjected to a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 180 ° C, dehydrated, and then heated to 220 ° C for refining. After cooling, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent and 24 parts of a base oil are added and mixed and ground to obtain A lithium complex grease containing paper-like graphene microspheres.
  • Steps 1 to 3 are the same as those in Embodiments 1-8;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), 63 parts of the base oil, 5.9 parts of 12-hydroxystearic acid, and 5 parts of p-methylbenzoic acid, and the temperature is raised to 90 ° C. Adding lithium hydroxide to carry out a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 170 ° C, dehydrated, and then heated to 220 ° C for refining. After cooling, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent and 24 parts of a base oil are added and mixed and ground to obtain A lithium complex grease containing paper-like graphene microspheres.
  • Steps 1 to 3 are the same as those in Examples 1-9;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), 61 parts of the base oil, 5.9 parts of 12-hydroxystearic acid, and 4 parts of p-methylbenzoic acid, and the temperature is raised to 90 ° C. Adding lithium hydroxide to carry out a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 170 ° C, dehydrated, and then heated to 220 ° C for refining. After cooling, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent and 27 parts of a base oil are added and mixed and ground to obtain A lithium complex grease containing paper-like graphene microspheres.
  • Comparative Example 3-1 A lithium complex grease was prepared in accordance with the method of Example 3-1, except that no paper-like graphene microspheres were added during the preparation. The performance is shown in Table 3.
  • Comparative Example 3-2 Graphene oxide microspheres were directly thermally reduced without chemical reduction:
  • the appearance of the graphene is a black fluffy powder, and the microscopic shape is a hollow spherical shell having a diameter of 1 to 10 ⁇ m.
  • the properties of the obtained lithium complex grease are shown in Table 3.
  • the density, size and specific surface area of the graphene microspheres have a large effect on the properties of the final composite grease. If the voids increase, the compressive strength, modulus, and resilience of the microspheres decrease, and the effect of lubricating performance when acting on the friction surface is also reduced accordingly. Moreover, the smaller the particles, the easier the dispersion is to achieve stability. Therefore, considering the comprehensive consideration, it is necessary to obtain more dense graphene microspheres.
  • the invention realizes the densification of the graphene microspheres by controlling the reduction parameters at each step, thereby effectively improving the comprehensive performance of the grease.
  • step (3) The reduced graphene oxide microspheres obtained in the step (2) are placed in a tube furnace, nitrogen gas is continuously introduced, the temperature is raised to 3000 ° C, and the temperature is maintained for 1 h to obtain paper-like graphene microspheres;
  • step (4) The mixture obtained in the step (4) is heated to 180 ° C, dehydrated, and then heated to 220 ° C for refining. After cooling, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent and 24 parts of a base oil are added and mixed and ground to obtain A lithium complex grease containing paper-like graphene microspheres.
  • a lithium complex grease containing paper-like graphene microspheres is obtained, and the paper-like graphene microspheres are microscopically pleated microspheres having a diameter of 500 nm to 3 ⁇ m, due to steps (1) to (3).
  • the graphene microspheres had the same carbon-oxygen ratio, density, and specific surface area as in Examples 3-8.
  • the specific properties are shown in Table 3. It has been found that increasing the amount of graphene balls added can further enhance the performance of the grease.
  • Step 1-3 is the same as Embodiment 1-1;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), and 54 parts of the base oil and 8.9 parts of stearic acid are mixed, and the temperature is raised to 90 ° C, and then hydrazine hydroxide is added to carry out a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 160 ° C, dehydrated, and then heated to 210 ° C for refining. After cooling to 100 ° C, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent and 35 parts of a base oil are added and mixed. Grinding to obtain a sulfhydryl grease containing paper-like graphene microspheres.
  • Step 1-3 is the same as Embodiment 1-2;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), and 54 parts of the base oil and 8.9 parts of stearic acid are mixed, and the temperature is raised to 90 ° C, and then hydrazine hydroxide is added to carry out a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 160 ° C, dehydrated, and then heated to 210 ° C for refining. After cooling to 100 ° C, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent and 35 parts of a base oil are added and mixed. Grinding to obtain a sulfhydryl grease containing paper-like graphene microspheres.
  • Step 1-3 is the same as Embodiment 1-3;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), and 54 parts of the base oil and 8.9 parts of stearic acid are mixed, and the temperature is raised to 90 ° C, and then hydrazine hydroxide is added to carry out a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 160 ° C, dehydrated, and then heated to 210 ° C for refining. After cooling to 100 ° C, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent and 35 parts of a base oil are added and mixed. Grinding to obtain a sulfhydryl grease containing paper-like graphene microspheres.
  • the second step of reducing conditions may preferably be a high reduction temperature and a long reduction time.
  • Step 1-3 is the same as Embodiment 1-4;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), and 51 parts of the base oil and 9.8 parts of 12-hydroxystearic acid are mixed, and the temperature is raised to 100 ° C, and then hydrazine hydroxide is added to carry out a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 150 ° C, dehydrated, and then heated to 200 ° C for refining. After cooling to 120 ° C, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent, 1 part of a surfactant, and 36 parts of base oil were mixed and ground to obtain a sulfhydryl grease containing paper-like graphene microspheres.
  • Step 1-3 is the same as Embodiment 1-5;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), 52 parts of the base oil and 8.9 parts of stearic acid are mixed, and the temperature is raised to 105 ° C, and then hydrazine hydroxide is added to carry out a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 155 ° C, dehydrated, and then heated to 215 ° C refining, cooled to 120 ° C, then added 0.6 parts of antioxidant, 1.4 parts of rust inhibitor and 37 parts of base oil, mixed Grinding to obtain a sulfhydryl grease containing paper-like graphene microspheres.
  • Step 1-3 is the same as Embodiment 1-6;
  • Step 4 0.3 parts of the paper-like graphene microspheres obtained in the step (3), and 51 parts of the base oil and 11.6 parts of 12-hydroxystearic acid are mixed, and the temperature is raised to 100 ° C, and then hydrazine hydroxide is added to carry out a saponification reaction;
  • the mixture obtained in the step (4) is heated to 150 ° C, dehydrated, and further heated to 200 ° C for refining, and after cooling to 120 ° C, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent, 1 part of a surfactant, and 28 parts of base oil were mixed and ground to obtain a sulfhydryl grease containing paper-like graphene microspheres.
  • Step 1-3 is the same as Embodiment 1-7;
  • Step 4 0.05 parts of the paper-like graphene microspheres obtained in the step (3), 48 parts of the base oil and 13.1 parts of stearic acid are mixed, and the temperature is raised to 100 ° C, and then hydrazine hydroxide is added to carry out a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 150 ° C, dehydrated, and then heated to 200 ° C for refining. After cooling to 120 ° C, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent, 1 part of a surfactant, and 28 parts of base oil were mixed and ground to obtain a sulfhydryl grease containing paper-like graphene microspheres.
  • Step 1-3 is the same as Embodiments 1-8;
  • Step 4 0.2 parts of the paper-like graphene microspheres obtained in the step (3), and 58 parts of the base oil and 17.8 parts of stearic acid are mixed, and the temperature is raised to 100 ° C, and then hydrazine hydroxide is added to carry out a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 155 ° C, dehydrated, and then heated to 200 ° C for refining. After cooling to 120 ° C, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent, 1 part of a surfactant, and 31 parts of base oil were mixed and ground to obtain a sulfhydryl grease containing paper-like graphene microspheres.
  • Step 1-3 is the same as Embodiments 1-9;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), and 41 parts of the base oil and 9.4 parts of stearic acid are mixed, and the temperature is raised to 100 ° C, and then hydrazine hydroxide is added to carry out a saponification reaction;
  • Step 5 The mixture obtained in the step (4) is heated to 155 ° C, dehydrated, and then heated to 210 ° C for refining. After cooling to 110 ° C, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent, 1 part of a surfactant, and 35 parts of base oil were mixed and ground to obtain a sulfhydryl grease containing paper-like graphene microspheres.
  • Comparative Example 4-1 A sulfhydryl grease was prepared in accordance with the method of Example 4-1 except that no paper-like graphene microspheres were added during the preparation. The performance is shown in Table 4.
  • Comparative Example 4-2 Graphene oxide microspheres were directly thermally reduced without chemical reduction:
  • the appearance of the graphene is a black fluffy powder, and the microscopic shape is a hollow spherical shell having a diameter of 1 to 10 ⁇ m.
  • the properties of the obtained sulfhydryl grease are shown in Table 4.
  • the density, size and specific surface area of the graphene microspheres have a large effect on the properties of the final composite grease. If the voids increase, the compressive strength, modulus, and resilience of the microspheres decrease, and the effect of lubricating performance when acting on the friction surface is also reduced accordingly. Moreover, the smaller the particles, the easier the dispersion is to achieve stability. Therefore, considering the comprehensive consideration, it is necessary to obtain more dense graphene microspheres.
  • the invention realizes the densification of the graphene microspheres by controlling the reduction parameters at each step, thereby effectively improving the comprehensive performance of the grease.
  • step (3) The reduced graphene oxide microspheres obtained in the step (2) are placed in a tube furnace, nitrogen gas is continuously introduced, the temperature is raised to 3000 ° C, and the temperature is maintained for 1 h to obtain paper-like graphene microspheres;
  • the mixture obtained in the step (4) is heated to 155 ° C, dehydrated, and further heated to 200 ° C for refining, and after cooling to 120 ° C, 0.6 parts of an antioxidant, 1.4 parts of a rust preventive agent, 1 part of a surfactant, and 31 parts of base oil were mixed and ground to obtain a sulfhydryl grease containing paper-like graphene microspheres.
  • a sulfhydryl grease containing paper-like graphene microspheres was obtained.
  • the paper-like graphene microspheres are microscopically pleated microspheres having a diameter of 500 nm to 3 ⁇ m. Since steps (1) to (3) are the same as those of Examples 4 to 8, the carbon-oxygen ratio and density of the graphene microspheres are The specific surface area was the same as in Example 8. The specific properties are shown in Table 4. It has been found that increasing the amount of graphene balls added can further enhance the performance of the grease.
  • Steps 1-3 are the same as those in the embodiment 1-1;
  • Step 4 0.2 parts of the paper-like graphene microspheres obtained in the step (3), 100 parts of the butadiene rubber, 5 parts of the vulcanization accelerator TMTD, 2 parts of stearic acid, 1 part of the antioxidant, 2 parts of the liquid paraffin, zinc oxide 4 parts were mixed into the internal mixer for 15 min, the mixing temperature was 70 ° C, and then allowed to stand for 6 h;
  • Step 5 The mixture obtained in the step (4) and 4 parts of sulfur are placed in an open mill at 60 ° C for kneading, finally vulcanized on a flat vulcanizing machine, and vulcanized at 160 ° C for 30 min to obtain a paper-like graphite.
  • a olefinic modified composite rubber A olefinic modified composite rubber.
  • Steps 1-3 are the same as those in the embodiment 1-2;
  • Step 4 0.2 parts of the paper-like graphene microspheres obtained in the step (3), 100 parts of the butadiene rubber, 6 parts of the vulcanization accelerator TMTD, 2 parts of stearic acid, 1 part of the antioxidant, 2 parts of the liquid paraffin, zinc oxide 4 parts were mixed into the internal mixer for 15 min, the mixing temperature was 70 ° C, and then allowed to stand for 6 h;
  • Step 5 The mixture obtained in the step (4) and 3.5 parts of sulfur are placed in an open mill at 60 ° C for kneading, finally vulcanized on a flat vulcanizing machine, and vulcanized at 160 ° C for 30 min to obtain a paper-like graphite.
  • a olefinic modified composite rubber A olefinic modified composite rubber.
  • Steps 1-3 are the same as those in the examples 1-3;
  • Step 4 0.2 parts of the paper-like graphene microspheres obtained in the step (3), 100 parts of the butadiene rubber, 8 parts of the vulcanization accelerator TMTD, 1.5 parts of stearic acid, 1 part of the antioxidant, 2 parts of the liquid paraffin, zinc oxide 4 parts were mixed into the internal mixer for 15 min, the mixing temperature was 70 ° C, and then allowed to stand for 6 h;
  • Step 5 The mixture obtained in the step (4) and 4 parts of sulfur are placed in an open mill at 60 ° C for kneading, finally vulcanized on a flat vulcanizing machine, and vulcanized at 160 ° C for 30 min to obtain a paper-like graphite.
  • a olefinic modified composite rubber A olefinic modified composite rubber.
  • the second step of reducing conditions may preferably be a high reduction temperature and a long reduction time.
  • Steps 1 to 3 are the same as those in the examples 1-4;
  • Step 4 0.1 parts of the paper-like graphene microspheres obtained in the step (3), 100 parts of the butadiene rubber, 4 parts of the vulcanization accelerator TMTD, 2 parts of stearic acid, 1 part of the antioxidant, 1.5 parts of the liquid paraffin, zinc oxide 4 parts were added to the mixer for mixing for 30 min, the mixing temperature was 80 ° C, and then allowed to stand for 5 h;
  • Step 5 The mixture obtained in the step (4) and 3 parts of the vulcanizing agent are placed in an open mill at 80 ° C for kneading, finally vulcanized on a flat vulcanizing machine, and vulcanized at 170 ° C for 20 min to obtain a paper-like dough.
  • Graphene microsphere modified composite rubber
  • Steps 1-3 are the same as those in the examples 1-5;
  • Step 4 0.3 parts of the paper-like graphene microspheres obtained in the step (3), 100 parts of the butadiene rubber, 4 parts of the vulcanization accelerator TMTD, 2 parts of stearic acid, 1 part of the antioxidant, 1.5 parts of the liquid paraffin, zinc oxide 4 parts were added to the mixer for mixing for 30 min, the mixing temperature was 80 ° C, and then allowed to stand for 5 h;
  • Step 5 The mixture obtained in the step (4) and 3 parts of the vulcanizing agent are placed in an open mill at 80 ° C for kneading, finally vulcanized on a flat vulcanizing machine, and vulcanized at 170 ° C for 20 min to obtain a paper-like dough.
  • Graphene microsphere modified composite rubber
  • Steps 1-3 are the same as Examples 1-6;
  • Step 4 0.3 parts of the paper-like graphene microspheres obtained in the step (3), 100 parts of the butadiene rubber, 4 parts of the vulcanization accelerator TMTD, 2 parts of stearic acid, 1 part of the antioxidant, 1.5 parts of the liquid paraffin, zinc oxide 4 parts were added to the mixer for mixing for 30 min, the mixing temperature was 80 ° C, and then allowed to stand for 5 h;
  • Step 5 The mixture obtained in the step (4) and 3 parts of the vulcanizing agent are placed in an open mill at 80 ° C for kneading, finally vulcanized on a flat vulcanizing machine, and vulcanized at 180 ° C for 30 min to obtain a paper-like dough.
  • Graphene microsphere modified composite rubber
  • Steps 1 to 3 are the same as those in Embodiments 1-7;
  • Step 4 0.2 parts of the paper-like graphene microspheres obtained in the step (3), 100 parts of the butadiene rubber, 8 parts of the vulcanization accelerator TMTD, 2 parts of stearic acid, 1 part of the antioxidant, 1.5 parts of the liquid paraffin, zinc oxide 4 parts were added to the mixer for mixing for 30 min, the mixing temperature was 80 ° C, and then allowed to stand for 5 h;
  • Step 5 The mixture obtained in the step (4) and 4 parts of the vulcanizing agent are placed in an open mill at 80 ° C for kneading, finally vulcanized on a flat vulcanizing machine, and vulcanized at 180 ° C for 30 min to obtain a paper-like dough.
  • Graphene microsphere modified composite rubber
  • Steps 1 to 3 are the same as those in Embodiments 1-8;
  • Step 4 0.2 parts of the paper-like graphene microspheres obtained in the step (3), 100 parts of the butadiene rubber, 8 parts of the vulcanization accelerator TMTD, 2 parts of stearic acid, 1 part of the antioxidant, 1.5 parts of the liquid paraffin, zinc oxide 4 parts were added to the mixer for mixing for 30 min, the mixing temperature was 80 ° C, and then allowed to stand for 5 h;
  • Step 5 The mixture obtained in the step (4) and 4 parts of the vulcanizing agent are placed in an open mill at 80 ° C for kneading, finally vulcanized on a flat vulcanizing machine, and vulcanized at 180 ° C for 30 min to obtain a paper-like dough.
  • Graphene microsphere modified composite rubber
  • Steps 1 to 3 are the same as those in Examples 1-9;
  • Step 4 0.2 parts of the paper-like graphene microspheres obtained in the step (3), 100 parts of the butadiene rubber, 7 parts of the vulcanization accelerator TMTD, 1 part of stearic acid, 1 part of the antioxidant, 2.5 parts of the liquid paraffin, zinc oxide 4 parts were added to the mixer for mixing for 30 min, the mixing temperature was 80 ° C, and then allowed to stand for 5 h;
  • Step 5 The mixture obtained in the step (4) and 4 parts of the vulcanizing agent are placed in an open mill at 80 ° C for kneading, finally vulcanized on a flat vulcanizing machine, and vulcanized at 160 ° C for 15 min to obtain a paper-like dough.
  • Graphene microsphere modified composite rubber
  • Comparative Example 5-1 A composite rubber was prepared in the same manner as in Example 5-1 except that no paper-like graphene microspheres were added during the preparation. The performance is shown in Table 5.
  • the graphene oxide microspheres obtained in the step (1) are placed in a tube furnace, and a hydrogen-argon mixed gas is continuously introduced, the temperature is raised to 3000 ° C, the heating rate is 5 ° C / min, and the temperature is kept for 1 h;
  • step (3) 0.2 parts of graphene obtained in step (3), 100 parts of butadiene rubber, 8 parts of vulcanization accelerator TMTD, 2 parts of stearic acid, 1 part of antioxidant, 1.5 parts of liquid paraffin, and 4 parts of zinc oxide are added to the mixture. Mixing in the machine for 30 min, the mixing temperature is 80 ° C, and then standing for 5 h;
  • the appearance of the graphene is a black fluffy powder, and the microscopic shape is a hollow spherical shell having a diameter of 1 to 10 ⁇ m.
  • the performance is shown in Table 5.
  • the performance of graphene reinforced rubber is closely related to the performance of the filler.
  • the invention realizes the densification of the graphene microspheres, the structural integrity and the optimization of the performance by controlling the reduction parameters of each step, thereby effectively improving the comprehensive performance of the composite rubber.
  • step (3) The reduced graphene oxide microspheres obtained in the step (2) are placed in a tube furnace, nitrogen gas is continuously introduced, the temperature is raised to 3000 ° C, and the temperature is maintained for 1 h to obtain paper-like graphene microspheres;
  • a composite rubber modified by paper-like graphene microspheres is obtained.
  • the paper-like graphene microspheres are microscopically pleated microspheres having a diameter of 500 nm to 3 ⁇ m. Since steps (1) to (3) are the same as those of Examples 5 to 8, the carbon-oxygen ratio and density of the graphene microspheres are The specific surface area was the same as in Examples 5-8. The specific properties are shown in Table 5. It can be found that increasing the amount of graphene balls added can further enhance the properties of the rubber.
  • Steps 1-3 are the same as those in the embodiment 1-1;
  • Step 4 0.3 parts of the paper-like graphene microspheres obtained in the step (3), and 100 parts of the pure acrylic emulsion are uniformly stirred, ultrasonically dispersed, and then 15 parts of water, 0.3 parts of a dispersing agent, 0.1 part of a preservative, 0.3 are sequentially added.
  • Steps 1-3 are the same as those in the embodiment 1-2;
  • Step 4 0.3 parts of the paper-like graphene microspheres obtained in the step (3), and 100 parts of the pure acrylic emulsion are uniformly stirred, ultrasonically dispersed, and then 15 parts of water, 0.3 parts of a dispersing agent, 0.1 part of a preservative, 0.3 are sequentially added.
  • Steps 1-3 are the same as those in the examples 1-3;
  • Step 4 0.3 parts of the paper-like graphene microspheres obtained in the step (3), and 100 parts of the pure acrylic emulsion are uniformly stirred, ultrasonically dispersed, and then 15 parts of water, 0.3 parts of a dispersing agent, 0.1 part of a preservative, 0.3 are sequentially added.
  • the second step of reducing conditions may preferably be a high reduction temperature and a long reduction time.
  • Steps 1 to 3 are the same as those in the examples 1-4;
  • Step 4 0.2 parts of the paper-like graphene microspheres obtained in the step (3), and 100 parts of the pure acrylic emulsion are uniformly stirred, ultrasonically dispersed, and then 15 parts of water, 0.3 parts of a dispersing agent, 0.1 part of a preservative, 0.3 are sequentially added.
  • Steps 1-3 are the same as those in the examples 1-5;
  • Step 4 0.4 parts of the paper-like graphene microspheres obtained in the step (3), and 100 parts of the vinegar-acrylic emulsion are uniformly stirred, ultrasonically dispersed, and then 18 parts of water, 0.3 parts of a dispersing agent, 0.1 part of a preservative, 0.3 are sequentially added.
  • Steps 1-3 are the same as Examples 1-6;
  • Step 4 0.4 parts of the paper-like graphene microspheres obtained in the step (3), and 100 parts of the vinegar-acrylic emulsion are uniformly stirred, ultrasonically dispersed, and then 12 parts of water, 0.3 parts of a dispersing agent, 0.1 part of a preservative, 0.3 are sequentially added.
  • Steps 1 to 3 are the same as those in Embodiments 1-7;
  • Step 4 0.5 parts of the paper-like graphene microspheres obtained in the step (3), and 100 parts of the vinegar-acrylic emulsion are uniformly stirred, ultrasonically dispersed, and then 20 parts of water, 0.5 part of a dispersing agent, 0.1 part of a preservative, 0.3 are sequentially added.
  • Steps 1 to 3 are the same as those in Embodiments 1-8;
  • Step 4 0.5 parts of the paper-like graphene microspheres obtained in the step (3), and 100 parts of the vinegar-acrylic emulsion are uniformly stirred, ultrasonically dispersed, and then 18 parts of water, 0.3 parts of a dispersing agent, 0.1 part of a preservative, 0.3 are sequentially added.
  • Steps 1 to 3 are the same as those in Examples 1-9;
  • Step 4 0.5 parts of the paper-like graphene microspheres obtained in the step (3), and 100 parts of the styrene-acrylic emulsion are uniformly stirred, ultrasonically dispersed, and then 14 parts of water, 0.3 parts of a dispersing agent, 0.1 part of a preservative, 0.3 are sequentially added.
  • Comparative Example 6-1 An aqueous acrylic coating was prepared in accordance with the procedure of Example 6-1 except that no paper-like graphene microspheres were added during the preparation. The performance is shown in Table 6.
  • Comparative Example 6-2 Graphene oxide microspheres were directly thermally reduced without chemical reduction:
  • the graphene oxide microspheres obtained in the step (1) are placed in a tube furnace, and a hydrogen-argon mixed gas is continuously introduced, the temperature is raised to 3000 ° C, the heating rate is 5 ° C / min, and the temperature is kept for 1 h;
  • the appearance of the graphene is a black fluffy powder, and the microscopic shape is a hollow spherical shell having a diameter of 1 to 10 ⁇ m, and the properties are shown in Table 6.
  • the mechanical properties of the coating can be improved to some extent after the addition of the coating, the adhesion is decreased due to the presence of the expanded graphene sheet.
  • the hardness, impact strength and wear resistance of the coatings after the addition of the paper-like graphene microspheres are greatly improved, and the density, size and specific surface area of the graphene microspheres are improved to the final composite grease.
  • the performance is more favorable. This is because when the pores of the microspheres are excessive, the compressive strength, modulus, and resilience of the microspheres are lowered, and the performance in the coating film is lowered.
  • the smaller the particles the easier the dispersion is to achieve stability. Therefore, considering the comprehensive consideration, it is necessary to obtain more dense graphene microspheres.
  • the invention realizes the densification of the graphene microspheres by controlling the reduction parameters at each step, thereby effectively improving the comprehensive performance of the coating.
  • step (3) The reduced graphene oxide microspheres obtained in the step (2) are placed in a tube furnace, nitrogen gas is continuously introduced, the temperature is raised to 3000 ° C, and the temperature is maintained for 1 h to obtain paper-like graphene microspheres;
  • a graphene-based aqueous acrylic coating was obtained.
  • the paper-like graphene microspheres are microscopically pleated microspheres having a diameter of 500 nm to 3 ⁇ m. Since steps (1) to (3) are the same as those of Examples 6-8, the carbon-oxygen ratio and density of the graphene microspheres are The specific surface area was the same as in Examples 6-8. The specific properties are shown in Table 6. It can be found that increasing the amount of graphene balls added can further enhance the performance of the coating.
  • Steps 1-3 are the same as those in the embodiment 1-1;
  • Step 4 Add 0.2 parts of paper-like graphene microspheres to 100 parts of molten caprolactam monomer, stir and heat to 120 ° C, remove water by distillation under reduced pressure, add 0.15 parts of sodium hydroxide, and raise the temperature to 140 ° C. After dehydration under reduced pressure for 30 min, the temperature was raised to 155 ° C;
  • Step 5 Add 0.35 parts of cocatalyst 2,4-diisocyanate (TDI) to the mixture obtained in step (4), stir and cast into a mold preheated to 165 ° C, keep warm for 30 min, cool off The mold obtained a graphene/cast nylon composite.
  • TDI cocatalyst 2,4-diisocyanate
  • Steps 1-3 are the same as those in the embodiment 1-2;
  • Step 4 Add 0.2 parts of paper-like graphene microspheres to 100 parts of molten caprolactam monomer, stir and heat to 120 ° C, remove water by distillation under reduced pressure, add 0.15 parts of sodium hydroxide, and raise the temperature to 140 ° C. After dehydration under reduced pressure for 30 min, the temperature was raised to 155 ° C;
  • Step 5 Add 0.35 parts of cocatalyst 2,4-diisocyanate (TDI) to the mixture obtained in step (4), stir and cast into a mold preheated to 165 ° C, keep warm for 30 min, cool off The mold obtained a graphene/cast nylon composite.
  • TDI cocatalyst 2,4-diisocyanate
  • Steps 1-3 are the same as those in the examples 1-3;
  • Step 4 Add 0.2 parts of paper-like graphene microspheres to 100 parts of molten caprolactam monomer, stir and heat to 120 ° C, remove water by distillation under reduced pressure, add 0.15 parts of sodium hydroxide, and raise the temperature to 140 ° C. After dehydration under reduced pressure for 30 min, the temperature was raised to 155 ° C;
  • Step 5 Add 0.35 parts of cocatalyst 2,4-diisocyanate (TDI) to the mixture obtained in step (4), stir and cast into a mold preheated to 165 ° C, keep warm for 30 min, cool off The mold obtained a graphene/cast nylon composite.
  • TDI cocatalyst 2,4-diisocyanate
  • the second step of reducing conditions may preferably be a high reduction temperature and a long reduction time.
  • Steps 1 to 3 are the same as those in the examples 1-4;
  • Step 4 0.3 parts of paper-like graphene microspheres are added to 100 parts of molten caprolactam monomer, stirred and heated to 120 ° C, distilled water to remove water, 0.15 parts of sodium hydroxide is added, and the temperature is raised to 140 ° C. After dehydration under reduced pressure for 30 min, the temperature was raised to 155 ° C;
  • Step 5 Add 0.35 parts of cocatalyst 2,4-diisocyanate (TDI) to the mixture obtained in step (4), stir and cast into a mold preheated to 165 ° C, keep warm for 30 min, cool off The mold obtained a graphene/cast nylon composite.
  • TDI cocatalyst 2,4-diisocyanate
  • Steps 1-3 are the same as those in the examples 1-5;
  • Step 4 0.5 parts of paper-like graphene microspheres are added to 100 parts of molten caprolactam monomer, stirred and heated to 120 ° C, distilled water to remove water, 0.15 parts of sodium hydroxide is added, and the temperature is raised to 140 ° C. After dehydration under reduced pressure for 30 min, the temperature was raised to 155 ° C;
  • Step 5 Add 0.35 parts of cocatalyst 2,4-diisocyanate (TDI) to the mixture obtained in step (4), stir and cast into a mold preheated to 165 ° C, keep warm for 30 min, cool off The mold obtained a graphene/cast nylon composite.
  • TDI cocatalyst 2,4-diisocyanate
  • Steps 1-3 are the same as Examples 1-6;
  • Step 4 Add 0.4 parts of paper-like graphene microspheres to 100 parts of molten caprolactam monomer, stir and raise the temperature to 120 ° C, distill off water under reduced pressure, add 0.15 parts of sodium hydroxide, and raise the temperature to 140 ° C. After dehydration under reduced pressure for 30 min, the temperature was raised to 155 ° C;
  • Step 5 Add 0.35 parts of cocatalyst 2,4-diisocyanate (TDI) to the mixture obtained in step (4), stir and cast into a mold preheated to 165 ° C, keep warm for 30 min, cool off The mold obtained a graphene/cast nylon composite.
  • TDI cocatalyst 2,4-diisocyanate
  • Steps 1 to 3 are the same as those in Embodiments 1-7;
  • Step 4 0.3 parts of paper-like graphene microspheres are added to 100 parts of molten caprolactam monomer, stirred and heated to 120 ° C, distilled water to remove water, 0.15 parts of sodium hydroxide is added, and the temperature is raised to 140 ° C. After dehydration under reduced pressure for 30 min, the temperature was raised to 155 ° C;
  • Step 5 Add 0.35 parts of cocatalyst 2,4-diisocyanate (TDI) to the mixture obtained in step (4), stir and cast into a mold preheated to 165 ° C, keep warm for 30 min, cool off The mold obtained a graphene/cast nylon composite.
  • TDI cocatalyst 2,4-diisocyanate
  • Steps 1 to 3 are the same as those in Embodiments 1-8;
  • Step 4 0.3 parts of paper-like graphene microspheres are added to 100 parts of molten caprolactam monomer, stirred and heated to 120 ° C, distilled water to remove water, 0.15 parts of sodium hydroxide is added, and the temperature is raised to 140 ° C. After dehydration under reduced pressure for 30 min, the temperature was raised to 155 ° C;
  • Step 5 Add 0.35 parts of cocatalyst 2,4-diisocyanate (TDI) to the mixture obtained in step (4), stir and cast into a mold preheated to 165 ° C, keep warm for 30 min, cool off The mold obtained a graphene/cast nylon composite.
  • TDI cocatalyst 2,4-diisocyanate
  • Steps 1 to 3 are the same as those in Examples 1-9;
  • Step 4 0.3 parts of paper-like graphene microspheres are added to 100 parts of molten caprolactam monomer, stirred and heated to 120 ° C, distilled water to remove water, 0.15 parts of sodium hydroxide is added, and the temperature is raised to 140 ° C. After dehydration under reduced pressure for 30 min, the temperature was raised to 155 ° C;
  • Step 5 Add 0.35 parts of cocatalyst 2,4-diisocyanate (TDI) to the mixture obtained in step (4), stir and cast into a mold preheated to 165 ° C, keep warm for 30 min, cool off The mold obtained a graphene/cast nylon composite.
  • TDI cocatalyst 2,4-diisocyanate
  • Comparative Example 7-1 A graphene/cast nylon composite was prepared in accordance with the procedure of Example 7-1 except that no paper-like graphene microspheres were added during the preparation. The performance is shown in Table 7.
  • Comparative Example 7-2 Graphene oxide microspheres were directly thermally reduced without chemical reduction
  • the graphene oxide microspheres obtained in the step (1) are placed in a tube furnace, and a hydrogen-argon mixed gas is continuously introduced, the temperature is raised to 3000 ° C, the heating rate is 5 ° C / min, and the temperature is kept for 1 h;
  • the appearance of the graphene is a black fluffy powder, and the microscopic shape is a hollow spherical shell having a diameter of 1 to 10 ⁇ m.
  • the specific properties of the resulting composite are shown in Table 7.
  • the microspheres with lower specific surface area and higher density have better mechanical strength and shape stability, and have less influence on the process of casting polymerization. Therefore, the first step of spray drying is added to the reducing agent.
  • the second step of chemical reduction and the third step of high temperature heat treatment of compact graphene microspheres have the best effect on casting nylon reinforcement, which can improve the mechanical properties, tribological properties and heat distortion temperature of the material.
  • step (3) The reduced graphene oxide microspheres obtained in the step (2) are placed in a tube furnace, nitrogen gas is continuously supplied, the temperature is raised to 3000 ° C, and the temperature is maintained for 1 h to obtain paper-like graphene microspheres;
  • a graphene/cast nylon composite material is obtained, wherein the paper-like graphene microspheres are microscopically pleated microspheres having a diameter of 500 nm to 3 ⁇ m, due to steps (1) to (3) and examples 7-8.
  • the carbon-oxygen ratio, density, and specific surface area of the graphene microspheres were the same as in Examples 7-8.
  • the specific performance is shown in Table 7.
  • step (3) The reduced graphene oxide microspheres obtained in the step (2) are placed in a tube furnace, nitrogen gas is continuously introduced, the temperature is raised to 3000 ° C, and the temperature is maintained for 1 h to obtain paper-like graphene microspheres;
  • a graphene/cast nylon composite material is obtained, wherein the paper-like graphene microspheres are microscopically pleated microspheres having a diameter of 500 nm to 3 ⁇ m, due to steps (1) to (3) and examples 7-8.
  • the carbon-oxygen ratio, density, and specific surface area of the graphene microspheres were the same as in Examples 7-8.
  • the specific performance is shown in Table 7.
  • Steps 1-3 are the same as those in the embodiment 1-1;
  • Step 4 Nylon 6 and the paper-like graphene microspheres obtained in the step (3) are uniformly mixed in a mixer at a weight ratio of 100:0.2 to obtain a nylon 6/graphene premix, and the nylon 6 is premixed. Drying with graphene microspheres in a vacuum oven at 90 ° C for 12 hours
  • Step 5 The premix obtained in the step (4) was melt-blended and extruded in a twin-screw extruder at a melting temperature of 250 ° C and a screw rotation speed of 200 rpm.
  • the composite material was injection molded into a standard test strip for mechanical properties test.
  • the notched impact strength of the graphene toughened nylon 6 composite material at room temperature cantilever beam was 25.44 KJ/m 2 .
  • Steps 1-3 are the same as those in the embodiment 1-2;
  • Step 4 Nylon 6 and the paper-like graphene microspheres obtained in the step (3) are uniformly mixed in a mixer at a weight ratio of 100:0.2 to obtain a nylon 6/graphene premix, and the nylon 6 is premixed. Drying with graphene microspheres in a vacuum oven at 90 ° C for 12 hours
  • Step 5 The premix obtained in the step (4) was melt-blended and extruded in a twin-screw extruder at a melting temperature of 250 ° C and a screw rotation speed of 200 rpm.
  • the composite material was injection molded into a standard test strip for mechanical performance test.
  • the notched impact strength of the graphene toughened nylon 6 composite material at room temperature cantilever beam was 26.56 KJ/m 2 .
  • Steps 1-3 are the same as those in the examples 1-3;
  • Step 4 Nylon 6 and the paper-like graphene microspheres obtained in the step (3) are uniformly mixed in a mixer at a weight ratio of 100:0.2 to obtain a nylon 6/graphene premix, and the nylon 6 is premixed. Drying with graphene microspheres in a vacuum oven at 90 ° C for 12 hours
  • Step 5 The premix obtained in the step (4) was melt-blended and extruded in a twin-screw extruder at a melting temperature of 250 ° C and a screw rotation speed of 200 rpm.
  • the composite material was injection molded into a standard test strip by an injection molding machine for mechanical property test.
  • the notched impact strength of the graphene toughened nylon 6 composite material at room temperature cantilever beam was 27.15 KJ/m 2 .
  • the second step of reducing conditions may preferably be a high reduction temperature and a long reduction time.
  • Steps 1 to 3 are the same as those in the examples 1-4;
  • Step 4 Nylon 6 and the paper-like graphene microspheres obtained in the step (3) are uniformly mixed in a mixer at a weight ratio of 100:0.2 to obtain a nylon 6/graphene premix, and the nylon 6 is premixed. Drying with graphene microspheres in a vacuum oven at 90 ° C for 12 hours
  • Step 5 The premix obtained in the step (4) was melt-blended and extruded in a twin-screw extruder at a melting temperature of 250 ° C and a screw rotation speed of 200 rpm.
  • the graphene toughened nylon 6 composite material was obtained, and the composite material was injection molded into a standard test sample by an injection molding machine for mechanical property test.
  • the notched impact strength of the graphene toughened nylon 6 composite material at room temperature cantilever beam was 29.80. KJ/m 2 .
  • Steps 1-3 are the same as those in the examples 1-5;
  • Step 4 Nylon 6 and the paper-like graphene microspheres obtained in the step (3) are uniformly mixed in a mixer at a weight ratio of 100:0.2 to obtain a nylon 6/graphene premix, and the nylon 6 is premixed. Drying with graphene microspheres in a vacuum oven at 90 ° C for 12 hours
  • Step 5 The premix obtained in the step (4) was melt-blended and extruded in a twin-screw extruder at a melting temperature of 250 ° C and a screw rotation speed of 200 rpm.
  • the graphene toughened nylon 6 composite material was obtained, and the composite material was injection molded into a standard test strip by an injection molding machine for mechanical performance test.
  • the notched impact strength of the graphene toughened nylon 6 composite material at room temperature cantilever beam was 30.41. KJ/m 2 .
  • Steps 1-3 are the same as Examples 1-6;
  • Step 4 Nylon 6 and the paper-like graphene microspheres obtained in the step (3) are uniformly mixed in a mixer at a weight ratio of 100:0.2 to obtain a nylon 6/graphene premix, and the nylon 6 is premixed. Drying with graphene microspheres in a vacuum oven at 90 ° C for 12 hours
  • Step 5 The premix obtained in the step (4) was melt-blended and extruded in a twin-screw extruder at a melting temperature of 250 ° C and a screw rotation speed of 200 rpm.
  • the graphene toughened nylon 6 composite material was obtained, and the composite material was injection molded into a standard test strip by an injection molding machine for mechanical performance test.
  • the notched impact strength of the graphene toughened nylon 6 composite material at room temperature cantilever beam was 30.87. KJ/m 2 .
  • Steps 1 to 3 are the same as those in Embodiments 1-7;
  • Step 4 Nylon 6 and the paper-like graphene microspheres obtained in the step (3) are uniformly mixed in a mixer at a weight ratio of 100:0.2 to obtain a nylon 6/graphene premix, and the nylon 6 is premixed. Drying with graphene microspheres in a vacuum oven at 90 ° C for 12 hours
  • Step 5 The premix obtained in the step (4) was melt-blended and extruded in a twin-screw extruder at a melting temperature of 250 ° C and a screw rotation speed of 200 rpm.
  • the graphene toughened nylon 6 composite material was obtained, and the composite material was injection molded into a standard test strip for mechanical property test.
  • the notched impact strength of the graphene toughened nylon 6 composite material at room temperature cantilever beam was 31.98. KJ/m 2 .
  • Steps 1 to 3 are the same as those in Embodiments 1-8;
  • Step 4 Nylon 6 and the paper-like graphene microspheres obtained in the step (3) are uniformly mixed in a mixer at a weight ratio of 100:0.2 to obtain a nylon 6/graphene premix, and the nylon 6 is premixed. Drying with graphene microspheres in a vacuum oven at 90 ° C for 12 hours
  • Step 5 The premix obtained in the step (4) was melt-blended and extruded in a twin-screw extruder at a melting temperature of 250 ° C and a screw rotation speed of 200 rpm.
  • the graphene toughened nylon 6 composite material was obtained, and the composite material was injection molded into a standard test strip by an injection molding machine for mechanical performance test.
  • the notched impact strength of the graphene toughened nylon 6 composite material at room temperature cantilever beam was 32.40. KJ/m 2 .
  • Steps 1 to 3 are the same as those in Examples 1-9;
  • Step 4 Nylon 6 and the paper-like graphene microspheres obtained in the step (3) are uniformly mixed in a mixer at a weight ratio of 100:0.2 to obtain a nylon 6/graphene premix, and the nylon 6 is premixed. Drying with graphene microspheres in a vacuum oven at 90 ° C for 12 hours
  • Step 5 The premix obtained in the step (4) was melt-blended and extruded in a twin-screw extruder at a melting temperature of 250 ° C and a screw rotation speed of 200 rpm.
  • the graphene toughened nylon 6 composite material was obtained, and the composite material was injection molded into a standard test sample by an injection molding machine for mechanical performance test.
  • the notched impact strength of the graphene toughened nylon 6 composite material at room temperature cantilever beam was 29.67. KJ/m 2 .
  • Comparative Example 8-1 A nylon 6 material without graphene.
  • the notched impact strength of the obtained graphene toughened nylon 6 composite at room temperature cantilever beam was 11.69 KJ/m 2 .
  • the reduced graphene oxide microspheres obtained in the step (1) are placed in a tube furnace, and a hydrogen-argon mixed gas is continuously introduced, the temperature is raised to 3000 ° C, the heating rate is 5 ° C / min, and the temperature is kept for 1 h;
  • Nylon 6 and the paper-like graphene microspheres obtained in the step (2) are uniformly mixed in a mixer at a weight ratio of 100:0.2 to obtain a nylon 6/graphene premix, and the nylon 6 is premixed.
  • the graphene microspheres were vacuum dried in a vacuum oven at 90 ° C for 12 hours.
  • a graphene toughened nylon 6 composite material is obtained, wherein the appearance of graphene is a black fluffy powder, and the microscopic shape is a hollow spherical shell with a diameter of 1 to 10 ⁇ m, and the composite material is injection molded into a standard test strip by an injection molding machine for mechanical properties.
  • the notched impact strength of the graphene toughened nylon 6 composite at room temperature cantilever beam was 9.55 KJ/m 2 .
  • the composite material prepared by the invention is injection-molded by ASTM standard, and the injection molding machine is injection-molded at 230-260 ° C, and the sample is molded and placed in a standard environment with a temperature of 23 ⁇ 2° C. and a humidity of 50 ⁇ 5% for 88 hours.
  • the test environment has a temperature of 23 ⁇ 2 ° C and a humidity of 50 ⁇ 5%.
  • the large specific surface area can enhance the interfacial adhesion effect between the graphene and the matrix, so that the material absorbs more energy when subjected to impact, and has a better toughening effect.
  • the specific surface area is too large, the graphene powder tends to agglomerate, and the dispersion effect in the matrix is deteriorated, but the stress concentration point is more likely to be formed to lower the material properties.
  • the pleated structure of the paper-like graphene microspheres has very good flexibility, the denser the structure of the microspheres, the less likely the large toughness of the microspheres is damaged by the pressure and the toughness of the material is destroyed.
  • the specific surface area and compactness of the paper-like graphene microspheres can be balanced by the method disclosed in the invention patent, and the graphene toughening agent having the best effect can be prepared for improving the nylon 6 material.
  • Impact strength, at the same time, graphene also gives the material a higher comprehensive heat resistance, aging resistance and antistatic properties, improve water absorption, and expand the application range of nylon 6 material.

Abstract

一种纸团状石墨烯微球及其复合材料和制备方法。这种纸团状石墨烯微球是将氧化石墨烯微球经过化学法进行还原，使氧化石墨烯表面的含氧官能团缓慢脱除，避免了基团快速脱除导致的体积膨胀，因而保持了石墨烯片的紧密结合而不分离；然后通过高温处理，使剩余的少量含氧官能团脱除，并修复氧化石墨烯片中的缺陷结构，在超高温度(2500～3000℃)下石墨结构完美化，使得微球内石墨烯片间的结合能力进一步提高，结构密实化。所得的纸团状石墨烯微球具有良好的力学性能和弹性，能有效吸收冲击，稳定性强，密度高，可被用于增强陶瓷，工程塑料，涂料等领域。

Description

一种纸团状石墨烯微球及其复合材料和制备方法 技术领域
本发明属于石墨烯材料领域，涉及一种纸团状石墨烯微球及其复合材料和制备方法。
背景技术
作为一种新型的二维碳材料，石墨烯越来越受到世人的关注。由于其出众的力学性能，电学性能，热学性能和独特的电磁学性能，石墨烯在许多领域显示出广阔的应用前景，并已逐步走向实际应用。已有许多报道将石墨烯与高聚物复合，可以显著提升材料的拉伸强度、杨氏模量和弯曲强度，增强机理主要是利用石墨烯优越的力学强度，通过将应力转移至石墨烯上来提高复合材料整体的力学性能。石墨烯在使用上有多种形式，包括石墨烯膜、石墨烯气凝胶、石墨烯粉末、石墨烯纤维等等，这些形式往往展现出不同的增强效果。比如，将石墨烯气凝胶与高分子材料复合可以有效提高高分子材料的导电导热率。在常规石墨烯复合材料中，片状石墨烯对冲击性能的增强有限，增强机理缺乏，不能作为一种有效的增韧剂。若将石墨烯制成球形可更加充分地利用其力学强度，在提高冲击、耐磨、弹性等方面具有独特的利用前景。
专利CN201010593157.1《一种制备石墨烯粉体的方法》采用雾化干燥再进行慢速升温热处理的方法得到无膨胀石墨烯粉体，方法简单，可大批量制备，但是仍存在直接热处理时气体释放，导致石墨烯部分膨开。专利CN201310131014《一种制备石墨烯材料的方法及其在化学储能和/或转化中的用途》通过在氧化石墨烯分散液中加入可发生反应或聚合或分解的物质，使得所得粉体在还原后具有多孔结构，有利于电化学储能领域的应用。但是，如何获得不膨胀，甚至收缩的褶皱微球状石墨烯材料仍是一大难点。
摩擦现象广泛存在于机械运动中，造成机器的能量损耗、效率降低、温度升高、使表面磨损、性能下降，以及寿命缩短，由于摩擦中摩擦副导致的磨损，以及摩擦引起的能量损耗和生热，使得机械易于发生故障甚至失效，给人们生活带来经济损失，甚至人身危险。润滑油是有效减缓机械能量损耗和磨损的重要手段之一，加入润滑油后可实现润滑减磨、冷却降温、清洗清洁、密封防漏、防锈防蚀、减震缓冲等功效。常规润滑油是由基础油和多种助剂混合而成，基础油有矿物油、生物质油和合成油三类，助剂则是用于对基础油的性质进行改善。
石墨烯具有超薄的片层结构(易进入摩擦接触面)、优异的力学性能和自润滑性，这些特性使其在润滑添加剂方面的应用研究受到关注，大量研究发现适量的石墨烯作为润滑添加剂不仅可以减少摩擦系数，而且能通过摩擦吸附膜的形式显著提高润滑剂的承载抗磨性能。但石墨烯在润滑油中容易产生团聚现象，从而影响了其在润滑油和溶剂中的分散稳定性。目前，解决石 墨烯在润滑油和水等溶剂中的分散稳定性的方法主要有两种，一种是添加分散剂，利用分散剂的分散作用，使石墨烯均匀稳定地分散在溶剂中，但分散剂有时会影响石墨烯摩擦学性能的发挥；另一种是将石墨烯进行功能化修饰，增加石墨烯在溶剂中的分散稳定性，其关键是功能化分子的选择。但无论是添加分散剂还是进行表面修饰，都额外引入了新的成分，对润滑油整体的性能产生复杂的影响。
机械工业的迅猛发展带动着润滑脂行业的更新换代，早期使用的钙基润滑脂使用温度较低，在高转速的场合中不适合使用；随后研发的钠基脂、钡基脂，由于生态环保和抗水性差等原因并没有使其得到广泛的应用；之后又研发的锂基润滑脂，硬脂酸锂或12-羟锂基润滑脂具有使用温度高、摩擦系数小、润滑性能好、抗水性能好等特点，使锂基脂广泛应用于汽车行业。但随着汽车技术的迅猛发展，高性能汽车对锂基脂提出了更加严苛的要求，复合锂基脂应运而生。复合锂基润滑脂具有高滴点、耐高温性；复合皂的纤维结构强度高，在高温条件下具有良好的机械安定性，有长的使用寿命；有良好的抗水淋特性。普通的复合锂基润滑脂在使用的过程中，虽然较锂基润滑脂具有一定的优势，但是由于减摩抗磨性不佳，难以达到使用要求，为了满足苛刻工况的要求，需要进一步提升其性能。
橡胶在室温下具有独特的高弹性，质量轻，应用性广，作为一种重要的战略性物资被广泛应用于国民经济、高新技术和国防军工等领域.然而，单纯的橡胶强度低、模量低、耐磨差、抗疲劳差，没有实用性，因此对于绝大多数橡胶都需要填充补强。炭黑(CB)和白炭黑(SiO 2)是传统橡胶主要的补强剂，广泛使用于各种橡胶制品中，但是在橡胶补强的同时，由于橡胶材料固有的黏弹滞后损耗和橡胶内部的填料、大分子链之间的相互摩擦，动态环境下使用的橡胶制品会产生大量的热量。而当产生的热量不能及时地传导出去时，橡胶内部会急剧升温，使其性能劣化，此需要提高橡胶制品的导热性来提高其动态使用下的使用性能和使用寿命。此前有许多研究者将纳米填料与橡胶结合来获得更好性能的复合橡胶，如添加富勒烯、蒙脱土、膨胀石墨、碳纳米管等，但是这些材料易于团聚，难以在橡胶这种高粘度体系中分散，并且不能在各种性能中取得平衡，因而应用范围较窄。
水性涂料仍面临涂装性差、手感差、强度低、不耐磨等缺陷，限制了其应用范围。石墨烯是一种原子厚度的二维碳材料，具有超高的比表面积、优异的力学性能、高导热率和自润滑性。近年来许多研究者将石墨烯与涂料相结合，利用石墨烯的优异性能来提高水性涂料的各项指标。然而，片状石墨烯易于团聚，形成堆叠的石墨结构，一方面无法实现石墨烯的优异性能，另一方面降低了其分散的稳定性。专利201510518720.1《含石墨烯的高性能水性丙烯酸酯涂料及其制备方法与应用》通过将磺化石墨烯添加到水性丙烯酸酯涂料中，显著提高了其拉伸强度和导热率。专利201610353311.5《一种石墨烯/丙烯酸导静电涂料及其制备方法》利用了相似 的方法将石墨烯添加到丙烯酸涂料中，使得导电率和耐酸雾性得到提升。
尼龙在五大工程塑料中产量最大、品种最多、用途最广，具有机械强度高、熔点高、耐磨、耐油、耐热性能优良等优点，广泛应用于汽车、电子电气、机械等领域。由于在很多应用领域中对尼龙的韧性有更高的要求，为了满足这些应用，必须对尼龙进行增韧改性。通常情况下，对尼龙的增韧改性主要有弹性体增韧、无机刚性粒子增韧、有机刚性粒子增韧三种方法，弹性体能显著提高尼龙材料的韧性，但同时会大幅度降低材料的刚性和强度；无机刚性粒子和有机刚性粒子在增韧的同时能够增强，但其增韧幅度有限。同时，通过研究发现，刚性粒子的形态会影响基体的增韧效果，在片状、球状、针状结构中的刚性粒子中，球状结构的刚性粒子对材料的增韧效果最好。
发明内容
本发明的目的是针对现有的技术不足，提供一种纸团状石墨烯微球及其复合材料和制备方法。包含以下技术方案：
方案一：
一种纸团状石墨烯微球，所述石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
一种纸团状石墨烯微球的制备方法，包括以下步骤：
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球；
(2)将步骤(1)得到的氧化石墨烯微球，置于还原性气体氛围中进行还原，得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球进行高温处理,温度高于1000℃，得到纸团状石墨烯微球。
进一步地，所述步骤(1)的单层氧化石墨烯分散液中，含有还原剂，在雾化过程中，氧化石墨烯片发生褶皱，同时，还原剂以分子形态附着在片层表面。所述还原剂为碘化氢、溴化氢、水合肼、维生素C、硼氢化钠等，还原剂与单层氧化石墨烯质量比为0.1～10。所述雾化干燥温度为100～200℃，使得包裹在褶皱结构中的还原剂对氧化石墨烯进行初步还原。
进一步地，步骤(2)中所述的还原性气氛为水合肼蒸汽、氢碘酸蒸汽、氢气、氢溴酸蒸汽中的一种或多种。还原条件为60～200℃下还原30min～48h。
进一步地，步骤(3)中所述的高温处理温度为2500～3000℃，气氛为氮气、氦气、氢气氩气混合气、氩气中的一种，处理时间为30min～48h。
有益效果在于：本发明首先通过雾化干燥法制备得到氧化石墨烯微球，在雾化干燥前将还 原剂加入氧化石墨烯分散液中，混合均匀，使还原剂以分子形式负载在氧化石墨烯片表面。之后在雾化干燥的过程中，部分还原剂与氧化石墨烯表面的含氧官能团发生反应，产物随溶剂的挥发而脱出，剩余还原剂则以分子形式附着在氧化石墨烯片表面，并随其皱褶被包裹起来。第二步采用化学还原，在还原性气氛下，氧化石墨烯微球内部和表面的含氧官能团与还原剂充分反应，较低的温度使得气体的产生和释放缓慢，避免了直接热还原中基团快速脱除产生气体，导致体积急剧膨胀的现象，因而保持了石墨烯仍以褶皱片的形式紧密结合而不分离。第三步高温热还原一方面使剩余少量的含氧官能团脱除，并修复氧化石墨烯片中的缺陷结构，另一方面，使微球内残留的水分、还原产物和未反应的还原剂脱除。此外，我们在实验中意外发现，在极高温度下(2500～3000℃)下，石墨烯微球的直径逐渐减小，密度增大，比表面积降低。这可能是由于石墨化温度下，石墨烯片的结构完美化，使得石墨烯褶皱结合力增强，石墨烯片间作用力增大，相互之间的距离缩短，逐步使石墨烯球的结构致密化。
所得纸团状石墨烯微球具有更加致密的结构，这种致密的纸团状石墨烯微球同时具有良好的力学性能和弹性，能有效吸收冲击，稳定性强，相对于常规的增强型填充剂具有更低的密度和更好的增强效果。
方案二：
一种石墨烯基润滑油，按质量份计包括如下组分：基础油100份、纸团状石墨烯微球0.05～1份、其他助剂2～14份。所述纸团状石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
一种石墨烯基润滑油的制备方法，包括以下步骤：
(1)将纸团状石墨烯微球和其他助剂加入基础油中，搅拌均匀。其他助剂包括：分散剂0.5～1份、亲合剂0.5～1.5份、黏度调节剂0.3～1份、抗泡剂0.2～0.5份、防腐剂0.5～10份。
(2)将步骤(1)得到的混合物通过超声分散并脱泡。
有益效果在于：所得纸团状石墨烯微球具有更加致密的结构，这种致密的纸团状石墨烯微球同时具有良好的力学性能和弹性，能有效吸收冲击，稳定性强，在施加外力的情况下石墨烯微球在摩擦面进行滚动摩擦，极压下石墨烯微球可填充于磨损部位降低进一步磨损，可显著提高润滑油的耐磨减摩性。
方案三：
一种含有纸团状石墨烯微球的复合锂基润滑脂，按质量份计包括如下组分：基础油70～90份，复合锂基稠化剂5～20份，纸团状石墨烯微球0.05～5份、其他助剂1～5份。所述纸团状石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
所述其他助剂包括：抗氧剂0.5～2份、表面活性剂0～2份、防锈剂0.5～1份。
进一步地，所述复合锂基稠化剂为大分子酸和小分子酸与氢氧化锂反应的复合物，大分子酸为C 12-C 24的脂肪酸，小分子酸为C 1-C 12的脂肪酸或硼酸的一种，大分子酸和小分子酸的摩尔比为1：0.1～2。
一种含有纸团状石墨烯微球的复合锂基润滑脂的制备方法，包括以下步骤：
(1)将纸团状石墨烯微球、基础油、大分子酸和小分子酸混合，升温至70～100℃后，加入氢氧化锂进行皂化反应；
(2)将步骤(1)得到的混合物升温至160～180℃，脱水，再升温至190～220℃炼制，冷却后加入其它助剂和剩余基础油，混合研磨，得到含有纸团状石墨烯微球的复合锂基润滑脂。
步骤1和步骤2中加的基础油的量根据混合状态确定，既保证混合均匀有保证流动性，为本领域的公知常识。
有益效果在于：所得纸团状石墨烯微球具有良好的力学性能和弹性，能有效吸收冲击，稳定性强。另外，纸团状结构降低了石墨烯的堆叠，提高了整体的稳定性。在施加外力的情况下石墨烯微球在摩擦面进行滚动摩擦，极压下石墨烯微球可填充于磨损部位降低进一步磨损，可显著提高润滑脂的耐磨减摩性。此外，低比表面积、低空隙率的石墨烯微球力学性能更佳，更有利于提高润滑性能。
方案四：
一种含有纸团状石墨烯微球的钡基润滑脂，按质量份计包括如下组分：基础油70～90份，钡基稠化剂5～20份，纸团状石墨烯微球0.01～5份、其他助剂1～5份。所述纸团状石墨烯微球由尺寸为1～200μm的单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.04～0.2g/cm 3，碳氧比为10～30。
进一步地，所述其他助剂包括：抗氧剂0.5～2份、表面活性剂0～2份、防锈剂0.5～1份。所述钡基稠化剂为C 12-C 24的天然脂肪酸或合成脂肪酸与氢氧化钡的反应物
一种含有纸团状石墨烯微球的钡基润滑脂的制备方法，包括以下步骤：
(1)将纸团状石墨烯微球、基础油和C 12-C 24脂肪酸混合，升温至90～110℃后，加入氢氧化钡进行皂化反应；
(2)将步骤(1)得到的混合物升温至150～180℃，脱水，再升温至200～220℃炼制，冷却至90～120℃后加入其它助剂和剩余基础油，混合研磨，得到含有纸团状石墨烯微球的钡基润滑脂。
步骤1和步骤2中加的基础油的量根据混合状态确定，既保证混合均匀有保证流动性，为本领域的公知常识。
本发明的有益效果在于：所得纸团状石墨烯微球具有良好的力学性能和弹性，能有效吸收冲击，稳定性强。另外，纸团状结构降低了石墨烯的堆叠，提高了整体的稳定性。在施加外力的情况下石墨烯微球在摩擦面进行滚动摩擦，极压下石墨烯微球可填充于磨损部位降低进一步磨损，可显著提高润滑脂的耐磨减摩性。此外，低比表面积、低空隙率的石墨烯微球力学性能更佳，更有利于提高润滑性能。
方案五：
一种基于纸团状石墨烯微球改性的复合橡胶，按质量份计包括如下组分：100份橡胶、0.1～10份纸团状石墨烯微球、0.5～5份硫化剂、3～10份硫化促进剂和5～20份其他助剂。所述纸团状石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
所述的橡胶为天然橡胶、丁腈橡胶、硅橡胶、顺丁橡胶、异戊橡胶、丁苯橡胶、乙丙橡胶、氯丁橡胶中的一种或几种。所述其他助剂包括：2～5份硬脂酸、0.5～2防老剂、0.5～3份液体石蜡、2～10份氧化锌。所述的硫化剂为硫磺、过氧化物、金属氧化物、树脂类硫化剂、含硫有机物的中至少一种。
一种基于纸团状石墨烯微球改性的复合橡胶的制备方法，包括以下步骤：
(1)将橡胶、纸团状石墨烯微球、硫化促进剂和其他助剂加入密炼机中混炼10～30min，混炼温度为40～90℃，之后静置5～8h；
(2)将静置后的混料和硫化剂置于40～90℃的开炼机中进行混炼，最后放在平板硫化机上硫化，在150～180℃下硫化10～40min。
本发明的有益效果在于：所得纸团状石墨烯微球具有良好的力学性能和弹性，能有效吸收冲击，稳定性强。另外，纸团状结构降低了石墨烯的堆叠，提高了整体的稳定性。纸团状石墨烯球能有效提升橡胶的力学强度，吸收冲击并促进材料回弹。石墨烯的加入还提高了材料整体的导热性和阻燃性，使得复合橡胶具有更高的使用寿命。
方案六：
一种石墨烯基水性丙烯酸涂料及其制备方法，特征在于，按质量份计包括如下组分：100份丙烯酸树脂乳液、0.1～5份纸团状石墨烯微球、30～60份无机填料、0.9～12份助剂、10～20份水。所述纸团状石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
述的丙烯酸树脂乳液为纯丙乳液、苯丙乳液、醋丙乳液的一种或多种。所述的无机填料为二氧化钛、二氧化硅、氧化铝、碳酸钙、碳酸钾的一种或多种。所述的助剂包括：0.1～0.5份 分散剂、0.1～0.3份防腐剂、0.1～0.5份成膜剂、0.05～0.2份流平剂、0.5～10份增稠剂、0.05～0.5份消泡剂。
一种石墨烯基水性丙烯酸涂料的制备方法，该方法为：将纸团状石墨烯微球和丙烯酸树脂乳液搅拌均匀，超声分散，再依次加入水、助剂和无机填料，高速搅拌，脱泡。
本发明的有益效果在于：所得纸团状石墨烯微球具有良好的力学性能和弹性，能有效吸收冲击，稳定性强。另外，纸团状结构降低了石墨烯的堆叠，提高了整体的稳定性。添加进涂料后，纸团状石墨烯微球相比片状石墨烯和膨胀石墨而言，团聚性大大降低，可在涂料中长期稳定分散，涂覆干燥后所得涂膜具有良好的耐冲击性，并且由于石墨烯的耐腐蚀性和抗菌性，还可进一步提升涂料的相关性能。
方案七：
一种石墨烯/浇铸尼龙复合材料，由0.1～5份纸团状石墨烯微球和100份浇铸尼龙组合而成。所述纸团状石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
一种石墨烯/浇铸尼龙复合材料的制备方法，包括以下步骤：
(1)将0.1～5份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
(2)向步骤(1)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)，搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
本发明的有益效果在于：所得纸团状石墨烯微球具有更加致密的结构，这种致密的纸团状石墨烯微球同时具有良好的力学性能和弹性，能有效吸收冲击，稳定性强，在施加外力的情况下石墨烯微球一方面可有效吸收能量，降低对浇铸尼龙基体的损害，另一方面，当表面发生摩擦时，石墨烯微球可在摩擦面进行滚动摩擦，极压下石墨烯微球可填充于磨损部位降低进一步磨损，可显著提高浇注尼龙的耐磨减摩性。
方案八：
一种纸团状石墨烯提高尼龙6冲击强度的方法，所述方法是利用纸团状石墨烯增韧尼龙6，所述纸团状石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
具体包括以下步骤：
(1)将尼龙6与石墨烯微球重量配比为100:0.05～1，在混合机中进行预混，得到混合均匀的尼龙6/石墨烯预混料，预混前先将尼龙6与石墨烯微球在真空烘箱中80～105℃中烘干 8～12小时；
(2)将步骤(1)得到的预混料用双螺杆挤出机在加工温度230～250℃，转速150～250rpm的条件下熔融共混挤出，冷却，造粒，得尼龙6/石墨烯复合材料。
有益效果在于：
1、纸团状石墨烯微球用于尼龙6材料的增韧改性剂，球状结构的石墨烯粒子更容易分散在尼龙6基体中，石墨烯微球表面的微褶皱形态和结构又赋予了石墨烯粒子更好的柔软性，相对普通片层填料能进一步对应力进行缓冲，类似于弹性粒子作用，提高尼龙6材料的冲击强度。
2、纸团状石墨烯增韧尼龙6复合材料通过熔融共混挤出的方式加工，该方法操作工艺简单，无溶剂污染，生产效率高，适合大规模生产。
3、利用石墨烯对尼龙6材料进行改性，石墨烯不但提高了尼龙6材料的冲击强度，同时也对尼龙6个结晶有促进作用，进而更进一步的提高材料的刚性和耐热性，另由于石墨烯的综合性能也能赋予材料更优良的抗静电性、抗紫外老化性、阻燃性及耐水性等综合性能。
附图说明
图1是经本发明实施例1-1制备的纸团状石墨烯微球的照片。
图2是经本发明实施例1-1制备的纸团状石墨烯微球的微观形貌。
图3是经本发明对比例1-1制备的膨胀石墨烯微球的微观形貌。
图4是经经本发明实施例1-8和对比例1-1制备的石墨烯微球的纳米压痕力学曲线图。
图5是经本发明实施例2-1制备的石墨烯基润滑油宏观照片。
具体实施方式
下面通过实施例对本发明进行具体描述，本实施例只用于对本发明做进一步的说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据上述发明的内容做出一些非本质的改变和调整均属本发明的保护范围。
实施例1-1：
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在60℃下还原1h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至1000℃，保温1h，得到纸团状石墨烯微球。
经以上步骤，得到的纸团状石墨烯微球外观为黑色粉末，如图1所示。微观为直径在3～5μm的褶皱微球，如图2所示。其密度为0.2g/cm 3，碳氧比为22.7，比表面积为190m 2/g。
实施例1-2：
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原1h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至1000℃，保温1h，得到纸团状石墨烯微球。
经以上步骤，得到的纸团状石墨烯微球外观为黑色粉末，微观为直径在3～5μm的褶皱微球。其密度为0.23g/cm 3，碳氧比为23.1，比表面积为181m 2/g。
实施例1-3：
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至1000℃，保温1h，得到纸团状石墨烯微球。
经以上步骤，得到的纸团状石墨烯微球外观为黑色粉末，微观为直径在3～5μm的褶皱微球。其密度为0.25g/cm 3，碳氧比为22.9，比表面积为166m 2/g。
通过对比实施例1-1～1-3可知，通过提高第二步还原温度和时间可以显著降低最终石墨烯微球的比表面积，提高密度，但对碳氧比影响不大。这是由于第二步还原主要是使氧化石墨烯表面的基团进行缓慢脱除，还原温度低或时间短会导致还原不充分，残留的基团在第三部高温热处理时会继续脱除，产生气体而使得石墨烯片向外膨胀。而碳氧比主要受第三步还原影响，与第二步关联不大。因此，综上考虑，第二步还原条件可优选为高还原温度和长还原时间。
实施例1-4：
(1)通过雾化干燥法将含有维生素C的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，维生素C和氧化石墨烯的质量比为0.1，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至1000℃，保温1h，得到纸团状石墨烯微球。
经以上步骤，得到的纸团状石墨烯微球外观为黑色粉末，微观为直径在3～5μm的褶皱微 球，性状如表1-1所示。
实施例1-5：
(1)通过雾化干燥法将含有维生素C的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，维生素C和氧化石墨烯的质量比为1，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至1000℃，保温1h，得到纸团状石墨烯微球。
经以上步骤，得到的纸团状石墨烯微球外观为黑色粉末，微观为直径在3～5μm的褶皱微球，性状如表1-1所示。
实施例1-6：
(1)通过雾化干燥法将含有维生素C的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，维生素C和氧化石墨烯的质量比为5，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至1000℃，保温1h，得到纸团状石墨烯微球。
经以上步骤，得到的纸团状石墨烯微球外观为黑色粉末，微观为直径在3～5μm的褶皱微球，性状如表1-1所示。
实施例1-7：
(1)通过雾化干燥法将含有维生素C的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，维生素C和氧化石墨烯的质量比为1，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至2000℃，保温1h，得到纸团状石墨烯微球。
经以上步骤，得到的纸团状石墨烯微球外观为黑色粉末，微观为直径在2～4μm的褶皱微球，性状如表1-1所示。
实施例1-8：
(1)通过雾化干燥法将含有维生素C的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，维生素C和氧化石墨烯的质量比为1，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至3000℃，保温1h，得到纸团状石墨烯微球。
经以上步骤，得到的纸团状石墨烯微球外观为黑色粉末，微观为直径在500nm～3μm的褶皱微球，性状如表1-1所示。
实施例1-9：
(1)通过雾化干燥法单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至3000℃，保温1h，得到纸团状石墨烯微球。
经以上步骤，得到的纸团状石墨烯微球外观为黑色粉末，微观为直径在1～4μm的褶皱微球，性状如表1-1所示。
对比例1-1：不经过化学还原直接热还原
(1)通过雾化干燥法将Hummers法制备得到的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为130℃；
(2)将步骤(1)得到的还原氧化石墨烯微球放入管式炉中，持续通入氢氩混合气，温度升至2500℃，升温速度为5℃/min，保温1h。
经以上步骤，得到的石墨烯外观为黑色蓬松粉末，微观为直径在1～10μm的空心球壳，如图3所示。性状如表1-1所示。
表1-1 不同实施例得到的产物物性
Figure PCTCN2018077221-appb-000001
对比实施例1-3～1-6可以发现，通过提高雾化干燥前加入的还原剂的量可以有效促进氧化石墨烯微球在第三步处理前的还原程度，这是由于还原剂以分子形式均匀分散在氧化石墨烯表面，在第一步和第二步中与含氧环能团逐步反应，缓慢还原石墨烯，使得碳氧比提升，比表面积降低。而对比第三步还原前后可知，高温热处理导致还原氧化石墨烯微球内部未脱除的基团脱离(碳氧比增大)，产生的气体膨开石墨烯层间结构，导致比表面积上升。但是，通过加入还原剂提高还原性后，石墨烯微球在第三步高温热处理时能更少的释放气体，降低了体积膨胀，使得结构更加密实。因此，为了获得高密度、低比表面积的石墨烯微球，加入还原剂是有重要意义的。
对比实施例1-5,1-7可以发现，在保证前两步还原条件一致的情况下，提高第三步还原温度使得比表面积增大，密度降低，这是由于气体的进一步释放导致片层结构进一步撑开。然而，意想不到的是，当温度升至3000℃后(实施例1-8)，比表面积大幅度降低，可能是温度高于石墨化温度后，石墨烯的大π结构得以修复，片层之间的结合力大大提升，层间距降低，因而使得石墨烯微球向中心“聚集”，更加密实化。
对比实施例1-3,1-9可知，若不加入还原剂，单纯通过3000℃热处理可以显著降低石墨烯微球的比表面积。但是对比实施例8可知，加入还原剂实现热处理前大部分官能团脱除可以得到更加紧实的石墨烯微球。
对比实施例1-8和对比例1-1可知，对比例中直接将氧化石墨烯微球进行高温热处理，还原时大量气体逸出导致体积快速膨胀，比表面积高，密度很低。测试纳米压痕力学曲线后发现，纸团状石墨烯微球的最大压缩应力、模量和回弹率均明显高于膨胀石墨烯球，如图4所示。
实施例1-10
本实施例将实施例1-3、1-5、1-8和对比实施例1-1得到的微球与橡胶复合，经力学性能测试后，性能如表1-2所示。可以发现，使用密度高，比表面积低的纸团状石墨烯微球可显著提升橡胶的拉伸强度和撕裂强度。
表1-2 不同实施例与橡胶复合的拉伸性能
  拉伸强度(MPa) 撕裂强度(kN m -1)
实施例1-3 23.8 25.6
实施例1-5 26.9 28.7
实施例1-8 28.4 31.2
对比例1-1 20.1 19.7
实施例2-1：
步骤1～3同实施例1-1；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和分散剂0.5份、亲合剂0.6份、粘度调节剂0.5份、抗泡剂0.3份、防腐剂1份依次加入100份基础油中，搅拌均匀；
步骤5：将步骤(4)得到的混合物通过超声分散并脱泡。
经以上步骤，得到石墨烯基润滑油，如图5所示，为黑色粘稠液体。所得润滑油的摩擦系数为0.094。
实施例2-2：
步骤1～3同实施例1-2；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和分散剂0.5份、亲合剂0.6份、粘度调节剂0.5份、抗泡剂0.3份、防腐剂1份依次加入100份基础油中，搅拌均匀；
步骤5：将步骤(4)得到的混合物通过超声分散并脱泡。
经以上步骤，得到石墨烯基润滑油，所得润滑油的摩擦系数为0.092。
实施例2-3：
步骤1～3同实施例1-3；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和分散剂0.5份、亲合剂0.6份、粘度调节剂0.5份、抗泡剂0.3份、防腐剂1份依次加入100份基础油中，搅拌均匀；
步骤5：将步骤(4)得到的混合物通过超声分散并脱泡。
经以上步骤，得到石墨烯基润滑油，所得润滑油的摩擦系数为0.089。
纸团状石墨烯微球的比表面积对复合润滑油的减摩性能影响较大，实施例2-3的摩擦系数最低。因此，综上考虑，第二步还原条件可优选为高还原温度和长还原时间。
实施例2-4：
步骤1～3同实施例1-4；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和分散剂0.5份、亲合剂0.6份、粘度调节剂0.5份、抗泡剂0.3份、防腐剂1份依次加入100份基础油中，搅拌均匀；
步骤5：将步骤(4)得到的混合物通过超声分散并脱泡。
经以上步骤，得到石墨烯基润滑油，具体性质如表2所示。
实施例2-5：
步骤1～3同实施例1-5；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和分散剂1份、亲合剂0.6份、粘度调节剂0.3份、抗泡剂0.3份、防腐剂1份依次加入100份基础油中，搅拌均匀；
步骤5：将步骤(4)得到的混合物通过超声分散并脱泡。
经以上步骤，得到石墨烯基润滑油，具体性质如表2所示。
实施例2-6：
步骤1～3同实施例1-6；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和分散剂0.5份、亲合剂1份、粘度调节剂0.5份、抗泡剂0.5份、防腐剂5份依次加入100份基础油中，搅拌均匀；
步骤5：将步骤(4)得到的混合物通过超声分散并脱泡。
经以上步骤，得到石墨烯基润滑油，具体性质如表2所示。
实施例2-7：
步骤1～3同实施例1-7；
步骤4：(4)将步骤(3)得到的纸团状石墨烯微球0.1份，和分散剂1份、亲合剂1.5份、粘度调节剂0.5份、抗泡剂0.3份、防腐剂8份依次加入100份基础油中，搅拌均匀；
步骤5：将步骤(4)得到的混合物通过超声分散并脱泡。
经以上步骤，得到石墨烯基润滑油，具体性质如表2所示。
实施例2-8：
步骤1～3同实施例1-8；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和分散剂0.8份、亲合剂0.6份、粘度调节剂1份、抗泡剂0.5份、防腐剂5份依次加入100份基础油中，搅拌均匀；
步骤5：将步骤(4)得到的混合物通过超声分散并脱泡。
经以上步骤，得到石墨烯基润滑油，具体性质如表2所示。
实施例2-9：
步骤1～3同实施例1-9；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和分散剂1份、亲合剂0.7份、粘度调节剂0.5份、抗泡剂0.3份、防腐剂10份依次加入100份基础油中，搅拌均匀；
步骤5：将步骤(4)得到的混合物通过超声分散并脱泡。
经以上步骤，得到石墨烯基润滑油，具体性质如表2所示。
对比例2-1：不加石墨烯的润滑油。
对比例2-2：不经过化学还原直接热还原
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球放入管式炉中，持续通入氢氩混合气，温度升至3000℃，升温速度为5℃/min，保温1h；
(3)将步骤(2)得到的石墨烯0.1份，和分散剂0.5份、亲合剂0.6份、粘度调节剂0.5份、抗泡剂0.3份、防腐剂1份依次加入100份基础油中，搅拌均匀；
(4)将步骤(3)得到的混合物通过超声分散并脱泡。
经以上步骤，得到的石墨烯外观为黑色蓬松粉末，微观为直径在1～10μm的空心球壳。所得润滑油的具体性质如表2所示。
表2 实施例具体参数与性质
Figure PCTCN2018077221-appb-000002
在与润滑油复合时，更加密实的球具有更好的摩擦性能，能更有效地在摩擦面间形成保护，降低摩擦和磨损。而比表面积大，空洞多的石墨烯微球在受到压力后容易发生形变，减摩能力下降。
实施例2-10：
(1)通过雾化干燥法将含有维生素C的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，维生素C和氧化石墨烯的质量比为1，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至3000℃，保温1h，得到纸团状石墨烯微球；
(4)将步骤(3)得到的纸团状石墨烯微球0.05份，和分散剂0.8份、亲合剂0.6份、粘度调节剂1份、抗泡剂0.5份、防腐剂5份依次加入100份基础油中，搅拌均匀；
(5)将步骤(4)得到的混合物通过超声分散并脱泡。
经以上步骤，得到石墨烯基润滑油，其中纸团状石墨烯微球在微观下为直径在500nm～3μm的褶皱微球，由于步骤(1)～(3)与实施例2-8相同，因此石墨烯微球的碳氧比、密度、比表面积与实施例2-8相同。摩擦系数系数为0.75。
实施例2-11：
(1)通过雾化干燥法将含有维生素C的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，维生素C和氧化石墨烯的质量比为1，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至3000℃，保温1h，得到纸团状石墨烯微球；
(4)将步骤(3)得到的纸团状石墨烯微球1份，和分散剂0.8份、亲合剂0.6份、粘度调节剂1份、抗泡剂0.5份、防腐剂5份依次加入100份基础油中，搅拌均匀；
(5)将步骤(4)得到的混合物通过超声分散并脱泡。
经以上步骤，得到石墨烯基润滑油，其中纸团状石墨烯微球在微观下为直径在500nm～3μm的褶皱微球，由于步骤(1)～(3)与实施例2-8相同，因此石墨烯微球的碳氧比、密度、比表面积与实施例2-8相同。摩擦系数系数为0.67。
对比实施例2-8、2-10、2-11可知，复合润滑油的摩擦系数随纸团状石墨烯微球的加入量增加而降低，体现出石墨烯微球良好的润滑性。
实施例3-1：
步骤1～3同实施例1-1；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油51份、12-羟基硬脂酸8.1份、苯甲酸3.8份混合，升温至70℃后，加入氢氧化锂进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至160℃，脱水，再升温至190℃炼制，冷却后加入抗氧剂0.6份、防锈剂1.4份和35份基础油，混合研磨，得到含有纸团状石墨烯微球的复合锂基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的复合锂基润滑脂。所得润滑脂的性能如表3所示。
实施例3-2：
步骤1～3同实施例1-2；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油51份、12-羟基硬脂酸8.1份、苯甲酸3.8份混合，升温至70℃后，加入氢氧化锂进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至160℃，脱水，再升温至190℃炼制，冷却后加入抗氧剂0.6份、防锈剂1.4份和35份基础油，混合研磨，得到含有纸团状石墨烯微球的复合锂基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的复合锂基润滑脂。所得复合锂基润滑脂的性能如表3所示。
实施例3-3：
步骤1～3同实施例1-3；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油51份、12-羟基硬脂酸8.1份、苯甲酸3.8份混合，升温至70℃后，加入氢氧化锂进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至160℃，脱水，再升温至190℃炼制，冷却后加入抗氧剂0.6份、防锈剂1.4份和35份基础油，混合研磨，得到含有纸团状石墨烯微球的复合锂基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的复合锂基润滑脂。所得复合锂基润滑脂的性能如表3所示。
纸团状石墨烯微球的比表面积越低，密度越高，代表结构越密实，其耐压性和弹性更好，使得复合润滑油的综合性能更佳，如表3所示。因此，综上考虑，第二步还原条件可优选为高还原温度和长还原时间。
实施例3-4：
步骤1～3同实施例1-4；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油47份、12-羟基硬脂酸7.4份、苯甲酸4.5份混合，升温至90℃后，加入氢氧化锂进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至170℃，脱水，再升温至200℃炼制，冷却后加入抗氧剂0.5份、防锈剂1.5份和39份基础油，混合研磨，得到含有纸团状石墨烯微球的复合锂基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的复合锂基润滑脂，具体性质如表3所示。
实施例3-5：
步骤1～3同实施例1-5；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油63份、12-羟基硬脂酸5.3份、苯甲酸6.6份混合，升温至80℃后，加入氢氧化锂进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至165℃，脱水，再升温至200℃炼制，冷却后加入抗氧剂0.5份、防锈剂1.5份和23份基础油，混合研磨，得到含有纸团状石墨烯微球的复合锂基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的复合锂基润滑脂，具体性质如表3所示。
实施例3-6：
步骤1～3同实施例1-6；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油63份、12-羟基硬脂酸5.6份、苯甲酸5.3份混合，升温至90℃后，加入氢氧化锂进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至180℃，脱水，再升温至220℃炼制，冷却后加入抗氧剂0.6份、防锈剂1.4份和24份基础油，混合研磨，得到含有纸团状石墨烯微球的复合锂基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的复合锂基润滑脂，具体性质如表3所示。
实施例3-7：
步骤1～3同实施例1-7；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油63份、12-羟基硬脂酸5.6份、苯甲酸5.3份混合，升温至90℃后，加入氢氧化锂进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至180℃，脱水，再升温至220℃炼制，冷却后加入抗氧剂0.6份、防锈剂1.4份和24份基础油，混合研磨，得到含有纸团状石墨烯微球的复合锂基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的复合锂基润滑脂，具体性质如表3所示。
实施例3-8：
步骤1～3同实施例1-8；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油63份、12-羟基硬脂酸5.9份、对甲基苯甲酸5份混合，升温至90℃后，加入氢氧化锂进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至170℃，脱水，再升温至220℃炼制，冷却后加入抗氧剂0.6份、防锈剂1.4份和24份基础油，混合研磨，得到含有纸团状石墨烯微球的复合锂基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的复合锂基润滑脂，具体性质如表3所示。
实施例3-9：
步骤1～3同实施例1-9；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油61份、12-羟基硬脂酸5.9份、对甲基苯甲酸4份混合，升温至90℃后，加入氢氧化锂进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至170℃，脱水，再升温至220℃炼制，冷却后加入抗氧剂0.6份、防锈剂1.4份和27份基础油，混合研磨，得到含有纸团状石墨烯微球的复合锂基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的复合锂基润滑脂，具体性质如表3所示。
对比例3-1：按照实施例3-1的方法制备复合锂基润滑脂，不同的是，制备过程中不添加纸团状石墨烯微球。性能如表3所示。
对比例3-2：氧化石墨烯微球不经过化学还原直接热还原：
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球放入管式炉中，持续通入氢氩混合气，温度升至3000℃，保温1h。
(3)将步骤(2)得到的石墨烯0.1份，和基础油61份、12-羟基硬脂酸5.9份、对甲基苯甲酸4份混合，升温至90℃后，加入氢氧化锂进行皂化反应；
(4)将步骤(3)得到的混合物升温至170℃，脱水，再升温至220℃炼制，冷却后加入抗氧剂0.6份、防锈剂1.4份和27份基础油，混合研磨，得到复合锂基润滑脂。
经以上步骤，得到的石墨烯外观为黑色蓬松粉末，微观为直径在1～10μm的空心球壳。所得复合锂基润滑脂性能如表3所示。
表3 摩擦性能
Figure PCTCN2018077221-appb-000003
石墨烯微球的密度、尺寸和比表面积对最后复合润滑脂的性能有很大影响。若空隙增多，微球的压缩强度、模量和回弹性下降，在作用于摩擦面时起到润滑性能的作用也相应降低。并且，颗粒越小，分散越容易达到稳定。因而，综合考虑，需要得到更为密实的石墨烯微球。本发明通过控制每一步还原参数，实现了石墨烯微球的密实化，从而有效提升了润滑脂的综合性能。
实施例3-10：
(1)通过雾化干燥法将含有维生素C的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，维生素C和氧化石墨烯的质量比为1，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至3000℃，保温1h，得到纸团状石墨烯微球；
(4)将步骤(3)得到的纸团状石墨烯微球5份，和基础油63份、12-羟基硬脂酸5.6份、苯甲酸5.3份混合，升温至90℃后，加入氢氧化锂进行皂化反应；
(5)将步骤(4)得到的混合物升温至180℃，脱水，再升温至220℃炼制，冷却后加入抗氧剂0.6份、防锈剂1.4份和24份基础油，混合研磨，得到含有纸团状石墨烯微球的复合锂基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的复合锂基润滑脂，纸团状石墨烯微球在微观下为直径在500nm～3μm的褶皱微球，由于步骤(1)～(3)与实施例3-8相同，因此石墨烯微球的碳氧比、密度、比表面积与实施例3-8相同。具体性质如表3所示。可以发现，提高石墨烯球的添加量可进一步提升润滑脂的各项性能。
实施例4-1：
步骤1-3同实施例1-1；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油54份、硬脂酸8.9份混合，升温至90℃后，加入氢氧化钡进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至160℃，脱水，再升温至210℃炼制，冷却至100℃后加入抗氧剂0.6份、防锈剂1.4份和35份基础油，混合研磨，得到含有纸团状石墨烯微球的钡基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的钡基润滑脂。所得润滑脂的性能如表4所示。
实施例4-2：
步骤1-3同实施例1-2；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油54份、硬脂酸8.9份混合，升温至90℃后，加入氢氧化钡进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至160℃，脱水，再升温至210℃炼制，冷却至100℃后加入抗氧剂0.6份、防锈剂1.4份和35份基础油，混合研磨，得到含有纸团状石墨烯微球的钡基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的钡基润滑脂。所得润滑脂的性能如表4所示。
实施例4-3：
步骤1-3同实施例1-3；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油54份、硬脂酸8.9份混合，升温至90℃后，加入氢氧化钡进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至160℃，脱水，再升温至210℃炼制，冷却至100℃后加入抗氧剂0.6份、防锈剂1.4份和35份基础油，混合研磨，得到含有纸团状石墨烯微球的钡基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的钡基润滑脂。所得润滑脂的性能如表4所示。
纸团状石墨烯微球的比表面积越低，密度越高，代表结构越密实，其耐压性和弹性更好，使得复合润滑油的综合性能更佳，如表4所示。因此，综上考虑，第二步还原条件可优选为高还原温度和长还原时间。
实施例4-4：
步骤1-3同实施例1-4；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油51份、12-羟基硬脂酸9.8份混合，升温至100℃后，加入氢氧化钡进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至150℃，脱水，再升温至200℃炼制，冷却至120℃后加入抗氧剂0.6份、防锈剂1.4份、表面活性剂1份和36份基础油，混合研磨，得到含有纸团状石墨烯微球的钡基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的钡基润滑脂。具体性质如表4所示。
实施例4-5：
步骤1-3同实施例1-5；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油52份、硬脂酸8.9份混合，升温至105℃后，加入氢氧化钡进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至155℃，脱水，再升温至215℃炼制，冷却至120℃后加入抗氧剂0.6份、防锈剂1.4份和37份基础油，混合研磨，得到含有纸团状石墨烯微球的钡基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的钡基润滑脂。具体性质如表4所示。
实施例4-6：
步骤1-3同实施例1-6；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.3份，和基础油51份、12-羟基硬脂酸11.6份混合，升温至100℃后，加入氢氧化钡进行皂化反应；
(5)将步骤(4)得到的混合物升温至150℃，脱水，再升温至200℃炼制，冷却至120℃后加入抗氧剂0.6份、防锈剂1.4份、表面活性剂1份和28份基础油，混合研磨，得到含有纸团状石墨烯微球的钡基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的钡基润滑脂。具体性质如表4所示。
实施例4-7：
步骤1-3同实施例1-7；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.05份，和基础油48份、硬脂酸13.1份混合，升温至100℃后，加入氢氧化钡进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至150℃，脱水，再升温至200℃炼制，冷却至120℃后加入抗氧剂0.6份、防锈剂1.4份、表面活性剂1份和28份基础油，混合研磨，得到含有纸团状石墨烯微球的钡基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的钡基润滑脂。具体性质如表4所示。
实施例4-8：
步骤1-3同实施例1-8；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.2份，和基础油58份、硬脂酸17.8份混合，升温至100℃后，加入氢氧化钡进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至155℃，脱水，再升温至200℃炼制，冷却至120℃后加入抗氧剂0.6份、防锈剂1.4份、表面活性剂1份和31份基础油，混合研磨，得到含有纸团状石墨烯微球的钡基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的钡基润滑脂。具体性质如表4所示。
实施例4-9：
步骤1-3同实施例1-9；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，和基础油41份、硬脂酸9.4份混合，升温至100℃后，加入氢氧化钡进行皂化反应；
步骤5：将步骤(4)得到的混合物升温至155℃，脱水，再升温至210℃炼制，冷却至110℃后加入抗氧剂0.6份、防锈剂1.4份、表面活性剂1份和35份基础油，混合研磨，得到含有纸团状石墨烯微球的钡基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的钡基润滑脂。具体性质如表4所示。
对比例4-1：按照实施例4-1的方法制备钡基润滑脂，不同的是，制备过程中不添加纸团状石墨烯微球。性能如表4所示。
对比例4-2：氧化石墨烯微球不经过化学还原直接热还原：
(1)通过雾化干燥法单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球放入管式炉中，持续通入氢氩混合气，温度升至3000℃，保温1h。
(3)将步骤(2)得到的石墨烯0.1份，和基础油51份、12-羟基硬脂酸8.9份混合，升温至100℃后，加入氢氧化钡进行皂化反应；
(4)将步骤(3)得到的混合物升温至160℃，脱水，再升温至210℃炼制，冷却后加入抗氧剂0.6份、防锈剂1.4份和38份基础油，混合研磨，得到钡基润滑脂。
经以上步骤，得到的石墨烯外观为黑色蓬松粉末，微观为直径在1～10μm的空心球壳。所得钡基润滑脂性能如表4所示。
表4 摩擦性能
Figure PCTCN2018077221-appb-000004
石墨烯微球的密度、尺寸和比表面积对最后复合润滑脂的性能有很大影响。若空隙增多，微球的压缩强度、模量和回弹性下降，在作用于摩擦面时起到润滑性能的作用也相应降低。并且，颗粒越小，分散越容易达到稳定。因而，综合考虑，需要得到更为密实的石墨烯微球。本发明通过控制每一步还原参数，实现了石墨烯微球的密实化，从而有效提升了润滑脂的综合性能。
实施例4-10：
(1)通过雾化干燥法将含有维生素C的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，维生素C和氧化石墨烯的质量比为1，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至3000℃，保温1h，得到纸团状石墨烯微球；
(4)将步骤(3)得到的纸团状石墨烯微球5份，和基础油58份、硬脂酸17.8份混合，升温至100℃后，加入氢氧化钡进行皂化反应；
(5)将步骤(4)得到的混合物升温至155℃，脱水，再升温至200℃炼制，冷却至120℃后加入抗氧剂0.6份、防锈剂1.4份、表面活性剂1份和31份基础油，混合研磨，得到含有纸团状石墨烯微球的钡基润滑脂。
经以上步骤，得到含有纸团状石墨烯微球的钡基润滑脂。纸团状石墨烯微球在微观下为直径在500nm～3μm的褶皱微球，由于步骤(1)～(3)与实施例4-8相同，因此石墨烯微球的碳氧比、密度、比表面积与实施例8相同。具体性质如表4所示。可以发现，提高石墨烯球的添加量可进一步提升润滑脂的各项性能。
实施例5-1：
步骤1～3同实施例1-1；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.2份，顺丁橡胶100份、硫化促进剂TMTD5份、硬脂酸2份、防老剂1份、液体石蜡2份、氧化锌4份加入密炼机中混炼15min，混炼温度为70℃，之后静置6h；
步骤5：将步骤(4)得到的混料和4份硫磺置于60℃的开炼机中进行混炼，最后放在平板硫化机上硫化，在160℃下硫化30min，得到基于纸团状石墨烯微球改性的复合橡胶。
经以上步骤，得到基于纸团状石墨烯微球改性的复合橡胶。所得橡胶的性能如表5所示。
实施例5-2：
步骤1～3同实施例1-2；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.2份，顺丁橡胶100份、硫化促进剂TMTD6份、硬脂酸2份、防老剂1份、液体石蜡2份、氧化锌4份加入密炼机中混炼15min，混炼温度为70℃，之后静置6h；
步骤5：将步骤(4)得到的混料和3.5份硫磺置于60℃的开炼机中进行混炼，最后放在平板硫化机上硫化，在160℃下硫化30min，得到基于纸团状石墨烯微球改性的复合橡胶。
经以上步骤，得到基于纸团状石墨烯微球改性的复合橡胶。所得橡胶的性能如表5所示。
实施例5-3：
步骤1～3同实施例1-3；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.2份，顺丁橡胶100份、硫化促进剂TMTD8份、硬脂酸1.5份、防老剂1份、液体石蜡2份、氧化锌4份加入密炼机中混炼15min，混炼温度为70℃，之后静置6h；
步骤5：将步骤(4)得到的混料和4份硫磺置于60℃的开炼机中进行混炼，最后放在平板硫化机上硫化，在160℃下硫化30min，得到基于纸团状石墨烯微球改性的复合橡胶。
经以上步骤，得到基于纸团状石墨烯微球改性的复合橡胶。所得橡胶的性能如表5所示。
纸团状石墨烯微球的比表面积越低，密度越高，代表结构越密实，其耐压性和弹性更好，与橡胶复合后综合性能更好，如表5所示。因此，综上考虑，第二步还原条件可优选为高还原温度和长还原时间。
实施例5-4：
步骤1～3同实施例1-4；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.1份，顺丁橡胶100份、硫化促进剂TMTD4份、硬脂酸2份、防老剂1份、液体石蜡1.5份、氧化锌4份加入密炼机中混炼30min，混炼温度为80℃，之后静置5h；
步骤5：将步骤(4)得到的混料和3份硫化剂置于80℃的开炼机中进行混炼，最后放在平板硫化机上硫化，在170℃下硫化20min，得到基于纸团状石墨烯微球改性的复合橡胶。
经以上步骤，得到基于纸团状石墨烯微球改性的复合橡胶。具体性能如表5所示。
实施例5-5：
步骤1～3同实施例1-5；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.3份，顺丁橡胶100份、硫化促进剂TMTD4份、硬脂酸2份、防老剂1份、液体石蜡1.5份、氧化锌4份加入密炼机中混炼30min，混炼温度为80℃，之后静置5h；
步骤5：将步骤(4)得到的混料和3份硫化剂置于80℃的开炼机中进行混炼，最后放在平板硫化机上硫化，在170℃下硫化20min，得到基于纸团状石墨烯微球改性的复合橡胶。
经以上步骤，得到基于纸团状石墨烯微球改性的复合橡胶。具体性能如表5所示。
实施例5-6：
步骤1～3同实施例1-6；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.3份，顺丁橡胶100份、硫化促进剂TMTD4份、硬脂酸2份、防老剂1份、液体石蜡1.5份、氧化锌4份加入密炼机中混炼30min，混炼温度为80℃，之后静置5h；
步骤5：将步骤(4)得到的混料和3份硫化剂置于80℃的开炼机中进行混炼，最后放在平板硫化机上硫化，在180℃下硫化30min，得到基于纸团状石墨烯微球改性的复合橡胶。
经以上步骤，得到基于纸团状石墨烯微球改性的复合橡胶。具体性能如表5所示。
实施例5-7：
步骤1～3同实施例1-7；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.2份，顺丁橡胶100份、硫化促进剂TMTD8份、硬脂酸2份、防老剂1份、液体石蜡1.5份、氧化锌4份加入密炼机中混炼30min，混炼 温度为80℃，之后静置5h；
步骤5：将步骤(4)得到的混料和4份硫化剂置于80℃的开炼机中进行混炼，最后放在平板硫化机上硫化，在180℃下硫化30min，得到基于纸团状石墨烯微球改性的复合橡胶。
经以上步骤，得到基于纸团状石墨烯微球改性的复合橡胶。具体性能如表5所示。
实施例5-8：
步骤1～3同实施例1-8；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.2份，顺丁橡胶100份、硫化促进剂TMTD8份、硬脂酸2份、防老剂1份、液体石蜡1.5份、氧化锌4份加入密炼机中混炼30min，混炼温度为80℃，之后静置5h；
步骤5：将步骤(4)得到的混料和4份硫化剂置于80℃的开炼机中进行混炼，最后放在平板硫化机上硫化，在180℃下硫化30min，得到基于纸团状石墨烯微球改性的复合橡胶。
经以上步骤，得到基于纸团状石墨烯微球改性的复合橡胶。具体性能如表5所示。
实施例5-9：
步骤1～3同实施例1-9；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.2份，顺丁橡胶100份、硫化促进剂TMTD7份、硬脂酸1份、防老剂1份、液体石蜡2.5份、氧化锌4份加入密炼机中混炼30min，混炼温度为80℃，之后静置5h；
步骤5：将步骤(4)得到的混料和4份硫化剂置于80℃的开炼机中进行混炼，最后放在平板硫化机上硫化，在160℃下硫化15min，得到基于纸团状石墨烯微球改性的复合橡胶。
经以上步骤，得到基于纸团状石墨烯微球改性的复合橡胶。具体性能如表5所示。
对比例5-1：按照实施例5-1的方法制备复合橡胶，不同的是，制备过程中不添加纸团状石墨烯微球。性能如表5所示。
对比例5-2：氧化石墨烯微球不经过化学还原直接热还原：
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球放入管式炉中，持续通入氢氩混合气，温度升至3000℃，升温速度为5℃/min，保温1h；
(4)将步骤(3)得到的石墨烯0.2份，顺丁橡胶100份、硫化促进剂TMTD8份、硬脂酸2份、防老剂1份、液体石蜡1.5份、氧化锌4份加入密炼机中混炼30min，混炼温度为80℃，之后静置5h；
(5)将步骤(4)得到的混料和4份硫化剂置于80℃的开炼机中进行混炼，最后放在平 板硫化机上硫化，在180℃下硫化30min，得到石墨烯改性的复合橡胶。
经以上步骤，得到的石墨烯外观为黑色蓬松粉末，微观为直径在1～10μm的空心球壳。性能如表5所示。
表5 摩擦性能
Figure PCTCN2018077221-appb-000005
石墨烯增强橡胶的性能与填充体的性能密切相关，填充的纸团状石墨烯微球的密度越高，比表面积越大，代表其结构越密实，空隙越少，结构越稳定，在吸收冲击、回弹和耐磨等方面的表现越好。并且，颗粒越小，分散越容易达到稳定。因而，综合考虑，需要得到更为密实的石墨烯微球。本发明通过控制每一步还原参数，实现了石墨烯微球的密实化，结构的完整化和性能的最优化，从而有效提升了复合橡胶的综合性能。
实施例5-10：
(1)通过雾化干燥法将含有维生素C的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，维生素C和氧化石墨烯的质量比为1，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至3000℃，保温1h，得到纸团状石墨烯微球；
(4)将步骤(3)得到的纸团状石墨烯微球0.2份，顺丁橡胶100份、硫化促进剂TMTD8份、硬脂酸2份、防老剂1份、液体石蜡1.5份、氧化锌4份加入密炼机中混炼30min，混炼温度为80℃，之后静置5h；
(5)将步骤(4)得到的混料和4份硫化剂置于80℃的开炼机中进行混炼，最后放在平板硫化机上硫化，在180℃下硫化30min，得到基于纸团状石墨烯微球改性的复合橡胶。
经以上步骤，得到基于纸团状石墨烯微球改性的复合橡胶。纸团状石墨烯微球在微观下为直径在500nm～3μm的褶皱微球，由于步骤(1)～(3)与实施例5-8相同，因此石墨烯微球的碳氧比、密度、比表面积与实施例5-8相同。具体性质如表5所示。可以发现，提高石墨烯球的添加量可进一步提升橡胶的各项性能。
实施例6-1：
步骤1～3同实施例1-1；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.3份，和100份纯丙乳液搅拌均匀，超声分散，再依次加入15份水、0.3份分散剂、0.1份防腐剂、0.3份成膜剂、0.1份流平剂、4份增稠剂、0.3份消泡剂、10份碳酸钙、10份氧化铝、15份二氧化钛，高速搅拌，脱泡。
经以上步骤，得到石墨烯基水性丙烯酸涂料。所得涂料的性能如表6所示。
实施例6-2：
步骤1～3同实施例1-2；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.3份，和100份纯丙乳液搅拌均匀，超声分散，再依次加入15份水、0.3份分散剂、0.1份防腐剂、0.3份成膜剂、0.1份流平剂、4份增稠剂、0.3份消泡剂、10份碳酸钙、10份氧化铝、15份二氧化钛，高速搅拌，脱泡。
经以上步骤，得到石墨烯基水性丙烯酸涂料。所得涂料的性能如表6所示。
实施例6-3：
步骤1～3同实施例1-3；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.3份，和100份纯丙乳液搅拌均匀，超声分散，再依次加入15份水、0.3份分散剂、0.1份防腐剂、0.3份成膜剂、0.1份流平剂、4份增稠剂、0.3份消泡剂、10份碳酸钙、10份氧化铝、15份二氧化钛，高速搅拌，脱泡。
经以上步骤，得到石墨烯基水性丙烯酸涂料。所得涂料的性能如表6所示。
纸团状石墨烯微球的比表面积越低，密度越高，代表结构越密实，其耐压性和弹性更好，使得涂料成膜后的综合性能更佳，如表6所示。因此，综上考虑，第二步还原条件可优选为高还原温度和长还原时间。
实施例6-4：
步骤1～3同实施例1-4；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.2份，和100份纯丙乳液搅拌均匀，超声分散，再依次加入15份水、0.3份分散剂、0.1份防腐剂、0.3份成膜剂、0.1份流平剂、4份增稠剂、0.3份消泡剂、15份碳酸钙、20份二氧化钛，高速搅拌，脱泡。
经以上步骤，得到石墨烯基水性丙烯酸涂料。具体性质如表6所示。
实施例6-5：
步骤1～3同实施例1-5；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.4份，和100份醋丙乳液搅拌均匀，超声分散，再依次加入18份水、0.3份分散剂、0.1份防腐剂、0.3份成膜剂、0.1份流平剂、5份增稠剂、0.1份消泡剂、5份碳酸钙、8份氧化铝、18份二氧化钛，高速搅拌，脱泡。
经以上步骤，得到石墨烯基水性丙烯酸涂料。具体性质如表6所示。
实施例6-6：
步骤1～3同实施例1-6；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.4份，和100份醋丙乳液搅拌均匀，超声分散，再依次加入12份水、0.3份分散剂、0.1份防腐剂、0.3份成膜剂、0.1份流平剂、5份增稠剂、0.1份消泡剂、30份碳酸钙、18份二氧化钛，高速搅拌，脱泡。
经以上步骤，得到石墨烯基水性丙烯酸涂料。具体性质如表6所示。
实施例6-7：
步骤1～3同实施例1-7；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.5份，和100份醋丙乳液搅拌均匀，超声分散，再依次加入20份水、0.5份分散剂、0.1份防腐剂、0.3份成膜剂、0.2份流平剂、10份增稠剂、0.1份消泡剂、30份碳酸钙、10份氧化铝、18份二氧化钛，高速搅拌，脱泡。
经以上步骤，得到石墨烯基水性丙烯酸涂料。具体性质如表6所示。
实施例6-8：
步骤1～3同实施例1-8；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.5份，和100份醋丙乳液搅拌均匀，超声分散，再依次加入18份水、0.3份分散剂、0.1份防腐剂、0.3份成膜剂、0.1份流平剂、5份增稠剂、0.1份消泡剂、25份碳酸钙、8份氧化铝、16份二氧化钛，高速搅拌，脱泡。
经以上步骤，得到石墨烯基水性丙烯酸涂料。具体性质如表6所示。
实施例6-9：
步骤1～3同实施例1-9；
步骤4：将步骤(3)得到的纸团状石墨烯微球0.5份，和100份苯丙乳液搅拌均匀，超声分散，再依次加入14份水、0.3份分散剂、0.1份防腐剂、0.3份成膜剂、0.1份流平剂、5份增稠剂、0.1份消泡剂、20份碳酸钙、8份氧化铝、14份二氧化钛，高速搅拌，脱泡。
对比例6-1：按照实施例6-1的方法制备水性丙烯酸涂料，不同的是，制备过程中不添加纸团状石墨烯微球。性能如表6所示。
对比例6-2：氧化石墨烯微球不经过化学还原直接热还原：
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球放入管式炉中，持续通入氢氩混合气，温度升至3000℃，升温速度为5℃/min，保温1h；
(3)将步骤(2)得到的石墨烯0.3份，和100份纯丙乳液搅拌均匀，超声分散，再依次加入15份水、0.3份分散剂、0.1份防腐剂、0.3份成膜剂、0.1份流平剂、4份增稠剂、0.3份消泡剂、10份碳酸钙、10份氧化铝、15份二氧化钛，高速搅拌，脱泡。
经以上步骤，得到的石墨烯外观为黑色蓬松粉末，微观为直径在1～10μm的空心球壳，性能如表6所示。
表6 摩擦性能
Figure PCTCN2018077221-appb-000006
注：漆膜耐磨性按照GB/T18103-2013《实木复合地板》进行测试，漆膜附着力按照GB/T9286—1998《色漆和清漆介绍漆膜的划格试验》进行测试。
添加入涂料后虽然可以一定程度提升涂料的力学性能，但由于膨胀的石墨烯片存在，附着力下降。从涂料性能的角度来看，加入纸团状石墨烯微球后涂料的硬度、冲击强度、耐磨性得到大幅提高，并且提升石墨烯微球的密度、降低尺寸和比表面积对最后复合润滑脂的性能更为有利。这是由于微球的孔洞过多时，微球的压缩强度、模量和回弹性下降，在涂膜中的表现下降。并且，颗粒越小，分散越容易达到稳定。因而，综合考虑，需要得到更为密实的石墨烯微球。本发明通过控制每一步还原参数，实现了石墨烯微球的密实化，从而有效提升了涂料的综合性能。
实施例6-10：
(1)通过雾化干燥法将含有维生素C的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，维生素C和氧化石墨烯的质量比为1，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至3000℃，保温1h，得到纸团状石墨烯微球；
(4)将步骤(3)得到的纸团状石墨烯微球5份，和100份醋丙乳液搅拌均匀，超声分散，再依次加入18份水、0.3份分散剂、0.1份防腐剂、0.3份成膜剂、0.1份流平剂、5份增稠剂、0.1份消泡剂、25份碳酸钙、8份氧化铝、16份二氧化钛，高速搅拌，脱泡。
经以上步骤，得到石墨烯基水性丙烯酸涂料。纸团状石墨烯微球在微观下为直径在500nm～3μm的褶皱微球，由于步骤(1)～(3)与实施例6-8相同，因此石墨烯微球的碳氧比、密度、比表面积与实施例6-8相同。具体性质如表6所示。可以发现，提高石墨烯球的添加量可进一步提升涂料的各项性能。
实施例7-1：
步骤1～3同实施例1-1；
步骤4：将0.2份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
步骤5：向步骤(4)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)，搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
经以上步骤，得到石墨烯/浇铸尼龙复合材料。所得复合材料的性能如表7所示。
实施例7-2：
步骤1～3同实施例1-2；
步骤4：将0.2份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
步骤5：向步骤(4)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)，搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
经以上步骤，得到石墨烯/浇铸尼龙复合材料，所得复合材料的性能如表7所示。
实施例7-3：
步骤1～3同实施例1-3；
步骤4：将0.2份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
步骤5：向步骤(4)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)，搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
经以上步骤，得到石墨烯/浇铸尼龙复合材料，所得复合材料的性能如表7所示。
纸团状石墨烯微球的比表面积大一方面不利于浇铸聚合的过程，容易产生分相、开裂、粘度过高甚至难聚合的情况，另一方面力学性能弱于更为密实的石墨烯球。因此，综合考虑，第二步还原条件可优选为高还原温度和长还原时间。
实施例7-4：
步骤1～3同实施例1-4；
步骤4：将0.3份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
步骤5：向步骤(4)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)，搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
经以上步骤，得到石墨烯/浇铸尼龙复合材料，具体性质如表7所示。
实施例7-5：
步骤1～3同实施例1-5；
步骤4：将0.5份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
步骤5：向步骤(4)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)，搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
经以上步骤，得到石墨烯/浇铸尼龙复合材料，具体性质如表7所示。
实施例7-6：
步骤1～3同实施例1-6；
步骤4：将0.4份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
步骤5：向步骤(4)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)， 搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
经以上步骤，得到石墨烯/浇铸尼龙复合材料，具体性质如表7所示。
实施例7-7：
步骤1～3同实施例1-7；
步骤4：将0.3份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
步骤5：向步骤(4)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)，搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
经以上步骤，得到石墨烯/浇铸尼龙复合材料，具体性质如表7所示。
实施例7-8：
步骤1～3同实施例1-8；
步骤4：将0.3份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
步骤5：向步骤(4)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)，搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
经以上步骤，得到石墨烯/浇铸尼龙复合材料，具体性质如表7所示。
实施例7-9：
步骤1～3同实施例1-9；
步骤4：将0.3份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
步骤5：向步骤(4)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)，搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
经以上步骤，得到石墨烯/浇铸尼龙复合材料，具体性质如表7所示。
对比例7-1：按照实施例7-1的方法制备石墨烯/浇铸尼龙复合材料，不同的是，制备过程中不添加纸团状石墨烯微球。性能如表7所示。
对比例7-2：氧化石墨烯微球不经过化学还原直接热还原
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球放入管式炉中，持续通入氢氩混合气，温度升至3000℃，升温速度为5℃/min，保温1h；
(4)将0.3份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
(5)向步骤(4)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)，搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
经以上步骤，得到的石墨烯外观为黑色蓬松粉末，微观为直径在1～10μm的空心球壳。所得复合材料的具体性质如表7所示。
在与尼龙6复合时，比表面积更低、密度更大的微球具有更好的力学强度和形状稳定性，并且对浇注聚合的过程影响更小，因此选择第一步喷雾干燥加入还原剂、第二步化学还原、第三步高温热处理得到的紧实石墨烯微球对浇铸尼龙增强来说效果最佳，可对材料的力学性能、摩擦学性能、热变形温度进行提升。
表7 复合材料的综合指标
Figure PCTCN2018077221-appb-000007
实施例7-10：
(1)通过雾化干燥法将含有维生素C的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，维生素C和氧化石墨烯的质量比为1，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至 3000℃，保温1h，得到纸团状石墨烯微球；
(4)将1.5份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
(5)向步骤(4)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)，搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
经以上步骤，得到石墨烯/浇铸尼龙复合材料，其中纸团状石墨烯微球在微观下为直径在500nm～3μm的褶皱微球，由于步骤(1)～(3)与实施例7-8相同，因此石墨烯微球的碳氧比、密度、比表面积与实施例7-8相同。具体性能如表7所示。
实施例7-11：
(1)通过雾化干燥法将含有维生素C的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，维生素C和氧化石墨烯的质量比为1，雾化温度为130℃；
(2)将步骤(1)得到的氧化石墨烯微球，置于水合肼蒸汽中，在90℃下还原24h得到还原氧化石墨烯微球；
(3)将步骤(2)得到的还原氧化石墨烯微球放入管式炉中，持续通入氮气，温度升至3000℃，保温1h，得到纸团状石墨烯微球；
(4)将5份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
(5)向步骤(4)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)，搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
经以上步骤，得到石墨烯/浇铸尼龙复合材料，其中纸团状石墨烯微球在微观下为直径在500nm～3μm的褶皱微球，由于步骤(1)～(3)与实施例7-8相同，因此石墨烯微球的碳氧比、密度、比表面积与实施例7-8相同。具体性能如表7所示。
对比实施例7-8、7-10、7-11可知，复合材料的大多数指标随着纸团状石墨烯微球的添加量上升而提高，说明进一步提高添加量可对性能进一步优化，但断裂伸长率有所降低，因此在实际应用时应进行综合考虑确定合适的添加量。
实施例8-1：
步骤1～3同实施例1-1；
步骤4：将尼龙6与步骤(3)得到的纸团状石墨烯微球按重量比100:0.2，在混合机中混合均匀，得尼龙6/石墨烯预混料，预混前将尼龙6与石墨烯微球在真空烘箱中90℃真空干燥12小时
步骤5：将步骤(4)得到的预混料在双螺杆挤出机中熔融共混挤出，熔融温度为250℃，螺杆转速为200rpm。
将复合材料用注塑机注塑成标准测试样条进行力学性能测试，经测试该石墨烯增韧的尼龙6复合材料的常温悬臂梁缺口冲击强度为25.44KJ/m 2。
实施例8-2：
步骤1～3同实施例1-2；
步骤4：将尼龙6与步骤(3)得到的纸团状石墨烯微球按重量比100:0.2，在混合机中混合均匀，得尼龙6/石墨烯预混料，预混前将尼龙6与石墨烯微球在真空烘箱中90℃真空干燥12小时
步骤5：将步骤(4)得到的预混料在双螺杆挤出机中熔融共混挤出，熔融温度为250℃，螺杆转速为200rpm。
将复合材料用注塑机注塑成标准测试样条进行力学性能测试，经测试该石墨烯增韧的尼龙6复合材料的常温悬臂梁缺口冲击强度为26.56KJ/m 2。
实施例8-3：
步骤1～3同实施例1-3；
步骤4：将尼龙6与步骤(3)得到的纸团状石墨烯微球按重量比100:0.2，在混合机中混合均匀，得尼龙6/石墨烯预混料，预混前将尼龙6与石墨烯微球在真空烘箱中90℃真空干燥12小时
步骤5：将步骤(4)得到的预混料在双螺杆挤出机中熔融共混挤出，熔融温度为250℃，螺杆转速为200rpm。
将复合材料用注塑机注塑成标准测试样条进行力学性能测试经测试该石墨烯增韧的尼龙6复合材料的常温悬臂梁缺口冲击强度为27.15KJ/m 2。
纸团状石墨烯微球的比表面积大时，石墨烯粉末分散效果变差，增韧效果受影响。因此，综上考虑，第二步还原条件可优选为高还原温度和长还原时间。
实施例8-4：
步骤1～3同实施例1-4；
步骤4：将尼龙6与步骤(3)得到的纸团状石墨烯微球按重量比100:0.2，在混合机中混合均匀，得尼龙6/石墨烯预混料，预混前将尼龙6与石墨烯微球在真空烘箱中90℃真空干燥12小时
步骤5：将步骤(4)得到的预混料在双螺杆挤出机中熔融共混挤出，熔融温度为250℃，螺杆转速为200rpm。
经以上步骤得到石墨烯增韧的尼龙6复合材料，将复合材料用注塑机注塑成标准测试样条进行力学性能测试，该石墨烯增韧的尼龙6复合材料的常温悬臂梁缺口冲击强度为29.80KJ/m 2。
实施例8-5：
步骤1～3同实施例1-5；
步骤4：将尼龙6与步骤(3)得到的纸团状石墨烯微球按重量比100:0.2，在混合机中混合均匀，得尼龙6/石墨烯预混料，预混前将尼龙6与石墨烯微球在真空烘箱中90℃真空干燥12小时
步骤5：将步骤(4)得到的预混料在双螺杆挤出机中熔融共混挤出，熔融温度为250℃，螺杆转速为200rpm。
经以上步骤得到石墨烯增韧的尼龙6复合材料，将复合材料用注塑机注塑成标准测试样条进行力学性能测试，该石墨烯增韧的尼龙6复合材料的常温悬臂梁缺口冲击强度为30.41KJ/m 2。
实施例8-6：
步骤1～3同实施例1-6；
步骤4：将尼龙6与步骤(3)得到的纸团状石墨烯微球按重量比100:0.2，在混合机中混合均匀，得尼龙6/石墨烯预混料，预混前将尼龙6与石墨烯微球在真空烘箱中90℃真空干燥12小时
步骤5：将步骤(4)得到的预混料在双螺杆挤出机中熔融共混挤出，熔融温度为250℃，螺杆转速为200rpm。
经以上步骤得到石墨烯增韧的尼龙6复合材料，将复合材料用注塑机注塑成标准测试样条进行力学性能测试，该石墨烯增韧的尼龙6复合材料的常温悬臂梁缺口冲击强度为30.87KJ/m 2。
实施例8-7：
步骤1～3同实施例1-7；
步骤4：将尼龙6与步骤(3)得到的纸团状石墨烯微球按重量比100:0.2，在混合机中混合均匀，得尼龙6/石墨烯预混料，预混前将尼龙6与石墨烯微球在真空烘箱中90℃真空干燥12小时
步骤5：将步骤(4)得到的预混料在双螺杆挤出机中熔融共混挤出，熔融温度为250℃，螺杆转速为200rpm。
经以上步骤得到石墨烯增韧的尼龙6复合材料，将复合材料用注塑机注塑成标准测试样条 进行力学性能测试，该石墨烯增韧的尼龙6复合材料的常温悬臂梁缺口冲击强度为31.98KJ/m 2。
实施例8-8：
步骤1～3同实施例1-8；
步骤4：将尼龙6与步骤(3)得到的纸团状石墨烯微球按重量比100:0.2，在混合机中混合均匀，得尼龙6/石墨烯预混料，预混前将尼龙6与石墨烯微球在真空烘箱中90℃真空干燥12小时
步骤5：将步骤(4)得到的预混料在双螺杆挤出机中熔融共混挤出，熔融温度为250℃，螺杆转速为200rpm。
经以上步骤得到石墨烯增韧的尼龙6复合材料，将复合材料用注塑机注塑成标准测试样条进行力学性能测试，该石墨烯增韧的尼龙6复合材料的常温悬臂梁缺口冲击强度为32.40KJ/m 2。
实施例8-9：
步骤1～3同实施例1-9；
步骤4：将尼龙6与步骤(3)得到的纸团状石墨烯微球按重量比100:0.2，在混合机中混合均匀，得尼龙6/石墨烯预混料，预混前将尼龙6与石墨烯微球在真空烘箱中90℃真空干燥12小时
步骤5：将步骤(4)得到的预混料在双螺杆挤出机中熔融共混挤出，熔融温度为250℃，螺杆转速为200rpm。
经以上步骤得到石墨烯增韧的尼龙6复合材料，将复合材料用注塑机注塑成标准测试样条进行力学性能测试，该石墨烯增韧的尼龙6复合材料的常温悬臂梁缺口冲击强度为29.67KJ/m 2。
对比例8-1：不加石墨烯的尼龙6材料。得到的石墨烯增韧的尼龙6复合材料的常温悬臂梁缺口冲击强度为11.69KJ/m 2。
对比例8-2：不经过化学还原直接热还原
(1)通过雾化干燥法将Hummers法制备得到的单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为130℃；
(2)将步骤(1)得到的还原氧化石墨烯微球放入管式炉中，持续通入氢氩混合气，温度升至3000℃，升温速度为5℃/min，保温1h；
(3)将尼龙6与步骤(2)得到的纸团状石墨烯微球按重量比100:0.2，在混合机中混合均匀，得尼龙6/石墨烯预混料，预混前将尼龙6与石墨烯微球在真空烘箱中90℃真空干燥12 小时。
(4)将步骤(3)得到的预混料在双螺杆挤出机中熔融共混挤出，熔融温度为250℃，螺杆转速为200rpm。
经以上步骤得到石墨烯增韧的尼龙6复合材料，其中石墨烯外观为黑色蓬松粉末，微观为直径在1～10μm的空心球壳，将复合材料用注塑机注塑成标准测试样条进行力学性能测试，该石墨烯增韧的尼龙6复合材料的常温悬臂梁缺口冲击强度为9.55KJ/m 2。
本发明的制备的复合材料采用ASTM标准注塑，注塑机在230～260℃条件下注塑成型，试样成型后在温度为23±2℃，湿度为50±5％的标准环境中放置88h后测试，测试环境为温度为23±2℃，湿度为50±5％。
纸团状石墨烯微球与尼龙6基体复合时，大的比表面积能增强石墨烯与基体的界面粘效果，使得材料受到冲击作用时吸收更多的能量，起到更好的增韧效果，但当比表面积过大时，石墨烯粉体容易团聚，在基体中分散效果变差，反而更容易形成应力集中点降低材料性能。另外，因为纸团状石墨烯微球的褶皱状结构使其自身具有非常好的柔韧性，微球的结构越密实，越不容易因微球受到压力后大的变形而破坏材料的韧性。所以，在实际应用中可以通过该发明专利中公开的方法来平衡纸团状石墨烯微球比表面积与紧实度，制备效果最优的石墨烯增韧剂，用于对提高尼龙6材料的冲击强度，同时，石墨烯还赋予了材料更高的耐热性、耐老化性及抗静电等综合性能，改善吸水性，扩展了尼龙6材料的应用范围。

Claims (30)

  1. 一种纸团状石墨烯微球，其特征在于，所述石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
  2. 一种石墨烯基润滑油，其特征在于，按质量份计包括如下组分：基础油100份、纸团状石墨烯微球0.05～1份、其他助剂2～14份；所述纸团状石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
  3. 根据权利要求2所述的润滑油，其特征在于，其他助剂包括：分散剂0.5～1份、亲合剂0.5～1.5份、黏度调节剂0.3～1份、抗泡剂0.2～0.5份、防腐剂0.5～10份。
  4. 一种石墨烯基润滑油的制备方法，其特征在于，包括以下步骤：
    (1)将纸团状石墨烯微球、分散剂、亲合剂、粘度调节剂、抗泡剂、防腐剂加入基础油中，搅拌均匀；
    (2)将步骤(1)得到的混合物通过超声分散并脱泡。
  5. 一种含有纸团状石墨烯微球的复合锂基润滑脂，其特征在于，按质量份计包括如下组分：基础油70～90份，复合锂基稠化剂5～20份，纸团状石墨烯微球0.05～5份、其他助剂1～5份；所述纸团状石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
  6. 根据权利要求5所述的润滑脂，其特征在于，所述其他助剂包括：抗氧剂0.5～2份、表面活性剂0～2份、防锈剂0.5～1份。
  7. 根据权利要求5所述的润滑脂，其特征在于，所述复合锂基稠化剂为大分子酸和小分子酸与氢氧化锂反应的复合物，大分子酸为C 12-C 24的脂肪酸，小分子酸为C 1-C 12的脂肪酸或硼酸的一种，大分子酸和小分子酸的摩尔比为1：0.1～2。
  8. 一种含有纸团状石墨烯微球的复合锂基润滑脂的制备方法，其特征在于，包括以下步骤：
    (1)将纸团状石墨烯微球、部分基础油、大分子酸和小分子酸混合，升温至70～100℃后，加入氢氧化锂进行皂化反应；
    (2)将步骤(1)得到的混合物升温至160～180℃，脱水，再升温至190～220℃炼制，冷却后加入其它助剂和剩余基础油，混合研磨，得到含有纸团状石墨烯微球的复合锂基润滑脂。
  9. 一种含有纸团状石墨烯微球的钡基润滑脂，其特征在于，按质量份计包括如下组分：基础油70～90份，钡基稠化剂5～20份，纸团状石墨烯微球0.01～5份、其他助剂1～5份；所述纸团状石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
  10. 根据权利要求9所述的润滑脂，其特征在于，所述其他助剂包括：抗氧剂0.5～2份、表面活性剂0～2份、防锈剂0.5～1份。
  11. 根据权利要求9所述的润滑脂，其特征在于，所述钡基稠化剂为C 12-C 24的天然脂肪酸或合成脂肪酸与氢氧化钡的反应物。
  12. 一种含有纸团状石墨烯微球的钡基润滑脂的制备方法，其特征在于，包括以下步骤：
    (1)将纸团状石墨烯微球、部分基础油和C 12-C 24脂肪酸混合，升温至90～110℃后，加入氢氧化钡进行皂化反应；
    (2)将步骤(1)得到的混合物升温至150～180℃，脱水，再升温至200～220℃炼制，冷却至90～120℃后加入其它助剂和剩余基础油，混合研磨，得到含有纸团状石墨烯微球的钡基润滑脂。
  13. 一种基于纸团状石墨烯微球改性的复合橡胶，其特征在于，按质量份计包括如下组分：100份橡胶、0.1～10份纸团状石墨烯微球、0.5～5份硫化剂、3～10份硫化促进剂和5～20份其他助剂；所述纸团状石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
  14. 根据权利要求13所述的复合橡胶，其特征在于，所述橡胶为天然橡胶、丁腈橡胶、硅橡胶、顺丁橡胶、异戊橡胶、丁苯橡胶、乙丙橡胶、氯丁橡胶中的一种或几种。
  15. 根据权利要求13所述的复合橡胶，其特征在于，所述硫化剂为硫磺、过氧化物、金属氧化物、树脂类硫化剂、含硫有机物中的至少一种。
  16. 根据权利要求13所述的复合橡胶，其特征在于，所述其他助剂包括：2～5份硬脂酸、0.5～2防老剂、0.5～3份液体石蜡、2～10份氧化锌。
  17. 一种基于纸团状石墨烯微球改性的复合橡胶的制备方法，其特征在于，包括以下步骤：
    (1)将橡胶、纸团状石墨烯微球、硫化促进剂和其他助剂加入密炼机中混炼10～30min，混炼温度为40～90℃，之后静置5～8h；
    (2)将静置后的混料和硫化剂置于40～90℃的开炼机中进行混炼，最后放在平板硫化机上硫化，在150～180℃下硫化10～40min。
  18. 一种石墨烯基水性丙烯酸涂料，其特征在于，按质量份计包括如下组分：100份丙烯酸树脂乳液、0.1～5份纸团状石墨烯微球、30～60份无机填料、0.9～12份助剂、10～20份水；所述纸团状石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
  19. 根据权利要求18所述的涂料，其特征在于，所述丙烯酸树脂乳液为纯丙乳液、苯丙乳液、醋丙乳液的一种或多种；所述无机填料为二氧化钛、二氧化硅、氧化铝、碳酸钙、碳酸 钾的一种或多种。
  20. 根据权利要求18所述的涂料，其特征在于，所述助剂包括：0.1～0.5份分散剂、0.1～0.3份防腐剂、0.1～0.5份成膜剂、0.05～0.2份流平剂、0.5～10份增稠剂、0.05～0.5份消泡剂。
  21. 一种石墨烯基水性丙烯酸涂料的制备方法，其特征在于，该方法为：将纸团状石墨烯微球和丙烯酸树脂乳液搅拌均匀，超声分散，再依次加入水、助剂和无机填料，搅拌，脱泡。
  22. 一种石墨烯/浇铸尼龙复合材料，其特征在于，由0.1～5份纸团状石墨烯微球和100份浇铸尼龙组成；所述纸团状石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
  23. 一种石墨烯/浇铸尼龙复合材料的制备方法，其特征在于，包括以下步骤：
    (1)将0.1～5份纸团状石墨烯微球加入100份熔融的己内酰胺单体中，搅拌并升温至120℃，减压蒸馏脱除水分，再加入0.15份氢氧化钠，升温至140℃，减压蒸馏脱水30min后升温至155℃；
    (2)向步骤(1)得到的混合物中加入0.35份助催化剂2，4-二异氰酸甲苯酯(TDI)，搅匀后浇注至预热为165℃的模具中，保温30min，冷却脱模得到石墨烯/浇铸尼龙复合材料。
  24. 一种纸团状石墨烯提高尼龙6冲击强度的方法，其特征在于，该方法是利用纸团状石墨烯微球对尼龙材料进行增韧，所述纸团状石墨烯微球由单层石墨烯片皱褶而成，微球直径为500nm～5μm，密度为0.2～0.4g/cm 3，碳氧比为20～60，比表面积低于200m 2/g。
  25. 根据权利要求1所述的方法，其特征在于，其特征在于，步骤如下：
    (1)将尼龙6与石墨烯微球按照重量配比为100:0.05～1，在混合机中进行预混，得到混合均匀的尼龙6/石墨烯预混料，预混前先将尼龙6与石墨烯微球在真空烘箱中80～105℃中烘干8～12小时；
    (2)将步骤(1)得到的预混料用双螺杆挤出机在加工温度230～250℃，转速150～250rpm的条件下熔融共混挤出，冷却，造粒，制得尼龙6/石墨烯复合材料。
  26. 一种纸团状石墨烯微球的制备方法，其特征在于，包括以下步骤：
    (1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球；
    (2)将步骤(1)得到的氧化石墨烯微球，置于还原性气体氛围中进行还原得到还原氧化石墨烯微球；
    (3)将步骤(2)得到的还原氧化石墨烯微球进行高温处理，温度高于1000℃，得到纸团状石墨烯微球。
  27. 根据权利要求2所述的方法，其特征在于，所述步骤(1)的单层氧化石墨烯分散液中，含有还原剂；所述还原剂为碘化氢、溴化氢、水合肼、维生素C、硼氢化钠；还原剂与单 层氧化石墨烯质量比为0.1～10。
  28. 根据权利要求3所述的方法，其特征在于，所述步骤(1)中的雾化干燥温度为100～200℃。
  29. 根据权利要求2所述的方法，其特征在于，所述步骤(2)中的还原性气氛为水合肼蒸汽、氢碘酸蒸汽、氢溴酸蒸汽中的一种或多种；还原条件为60～200℃下还原30min～48h。
  30. 根据权利要求2所述的方法，其特征在于，所述步骤(3)中的高温处理温度为2500～3000℃；高温处理气氛为氮气、氦气、氢气氩气混合气、氩气中的一种，处理时间为30min～48h。
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