CN110283639B - Functional lubricating oil additive and preparation method and application thereof - Google Patents

Functional lubricating oil additive and preparation method and application thereof Download PDF

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CN110283639B
CN110283639B CN201910650989.3A CN201910650989A CN110283639B CN 110283639 B CN110283639 B CN 110283639B CN 201910650989 A CN201910650989 A CN 201910650989A CN 110283639 B CN110283639 B CN 110283639B
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lubricating oil
boron nitride
graphene oxide
oil additive
coupling agent
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CN110283639A (en
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郝青丽
杨锐
雷武
夏锡锋
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Nanjing University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00Lubricating compositions characterised by the additive being an inorganic material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10Compounds containing silicon
    • C10M2201/102Silicates
    • C10M2201/103Clays; Mica; Zeolites
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/14Inorganic compounds or elements as ingredients in lubricant compositions inorganic compounds surface treated with organic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40Low content or no content compositions
    • C10N2030/41Chlorine free or low chlorine content compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40Low content or no content compositions
    • C10N2030/42Phosphor free or low phosphor content compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40Low content or no content compositions
    • C10N2030/43Sulfur free or low sulfur content compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64Environmental friendly compositions

Abstract

The invention discloses a functional lubricating oil additive and a preparation method and application thereof. The composite material and the lubricating oil are mixed according to a certain proportion, extremely excellent friction reduction and wear resistance can be obtained with a very small addition amount, a layer of self-repairing film is formed on the surface of a friction pair in the friction and wear process, the hardness of the surface of the friction pair is effectively enhanced, the wear resistance of a wear surface is effectively improved, and therefore the service life of a grinding piece is prolonged.

Description

Functional lubricating oil additive and preparation method and application thereof
Technical Field
The invention relates to a functional graphene/modified boron nitride/montmorillonite ternary composite material lubricating oil additive, a preparation method and application thereof, and belongs to the technical field of lubricating oil.
Background
Chinese patent CN201711383769 discloses a lubricating oil additive of functionalized graphene loaded montmorillonite, a preparation method and an application thereof, and although the lubricating oil additive has extremely excellent dispersion performance in lubricating oil and certain antifriction and repair capacity, the friction coefficient is not low enough to reduce.
The boron nitride sheet layer has good high temperature resistance, excellent corrosion resistance, higher thermal conductivity, lower thermal expansion coefficient, insulation, wave transmission and other properties, is a novel functional material with great application value, and has important application in the fields of heat conduction, lubrication, hydrogen storage, battery diaphragm materials, high-temperature oxidation resistant coatings, catalysis and the like. Guo Qiliang researches the antifriction ability of boron nitride as an additive in lubricating oil and lubricating grease, and compared with molybdenum disulfide and graphite, the boron nitride lubricating grease has more excellent performance. China mechanical engineering, 1995(02):57-58+79 ], but the boron nitride directly used as a lubricating oil additive has poor dispersion stability in oil products and is easy to agglomerate, and the boron nitride material has no report of having the capability of repairing a wear surface.
Disclosure of Invention
The invention aims to provide a functional graphene/modified boron nitride/montmorillonite ternary composite material lubricating oil additive, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: a functional graphene/modified boron nitride/montmorillonite ternary composite material lubricating oil additive is formed by mixing functional graphene oxide, modified boron nitride and montmorillonite in a mass ratio of 4:1-16: 2-32.
The lubricating oil additive is prepared by the following steps:
(1) preparing a dispersion liquid of graphene oxide by using graphene oxide prepared by an improved Hummers method as a raw material, adding a silane coupling agent, reacting at 25-100 ℃ for 1-6h, separating and cleaning to obtain functional graphene oxide;
(2) adding a silane coupling agent into the boron nitride dispersion liquid, reacting for 1-8h at 25-100 ℃, centrifuging, and cleaning to obtain modified boron nitride;
(3) mixing and stirring the modified boron nitride, the montmorillonite and the dispersion liquid of the functional graphene oxide for 0.5-2h, reacting for 1-5h at the temperature of 100-180 ℃, centrifuging and cleaning to obtain the lubricating oil additive.
Preferably, in the step (1) and the step (2), the silane coupling agent is any one of A-1100, A-1110, A-1120 and KBM-602.
Preferably, in the step (1), the mass ratio of the graphene oxide to the silane coupling agent is 1: 24-200.
Preferably, in the step (2), the mass ratio of the boron nitride to the silane coupling agent is 1: 50-200.
Preferably, the mass ratio of the graphene oxide to the boron nitride to the montmorillonite is 4:1-16: 2-32.
Preferably, in the step (1) to (3), the dispersion liquid of graphene oxide, the dispersion liquid of boron nitride, and the dispersion liquid of functional graphene oxide are the same in dispersion liquid, and each dispersion liquid includes ethanol or water.
Preferably, in steps (1) to (3), the heating mode is reflux heating or autoclave heating reaction.
The functional graphene/modified boron nitride/montmorillonite ternary composite material lubricating oil additive is applied, and the concentration of the additive in the lubricating oil is 0.011-0.089 wt%; the lubricating oil can be any brand of lubricating oil, such as Kunlun Scorpio F5000, SF15W-40 type lubricating oil and great wall SJ10W-40 lubricating oil, and can also be base oil such as mineral base oil or synthetic base oil.
By means of the technical scheme, the functional graphene/modified boron nitride/montmorillonite ternary composite lubricating oil additive prepared by the invention has the following advantages:
1) the preparation method disclosed by the invention is simple in preparation process, the raw materials are easy to obtain, the prepared additive does not contain sulfur, phosphorus, chlorine and other elements, and the preparation process is green and environment-friendly.
2) The composite material lubricating oil additive prepared by the invention has excellent antifriction and antiwear performances and is obviously superior to other single materials.
Drawings
FIG. 1 is a flow diagram of the preparation of a functional graphene/modified boron nitride/montmorillonite ternary composite lubricating oil additive.
Detailed Description
The invention is described in detail below with reference to the drawings and the embodiments, but the embodiments do not limit the invention in any way.
Referring to FIG. 1, the preparation of the ternary composite lubricating oil additive of the present invention is illustrated by the following examples.
Example one
(1) Graphene oxide prepared by a modified Hummers method was used as a raw material to prepare 160g of an aqueous dispersion of 0.025 wt% graphene oxide. Then, 6mL of the silane coupling agent (A-1100) was added, and the mixture was stirred at room temperature for 1 hour. Finally, the mixture was transferred to a flask and reacted at 80 ℃ for 2 hours. And standing, cooling, performing centrifugal separation, washing with water, and adding a proper amount of deionized water to obtain the aqueous dispersion of the functional graphene oxide.
(2) 0.04g of boron nitride is weighed, added with water and stirred uniformly to obtain an aqueous dispersion of the boron nitride, 6mL of silane coupling agent (A-1100) is added at room temperature and stirred for 1h, the mixture is heated and reacted for 2h at 80 ℃, and the modified boron nitride is obtained by centrifugation and water washing.
(3) Mixing and stirring the modified boron nitride, 0.16g of montmorillonite and the aqueous dispersion of the functional graphene oxide for 1 hour; transferring the mixture to a reaction kettle for hydrothermal reaction at 120 ℃ for 4 hours, standing and cooling; and (4) performing centrifugal separation, washing with water and ethanol respectively, and drying to obtain the functional graphene/modified boron nitride/montmorillonite ternary composite material lubricating oil additive.
(4) Evaluation of tribological Properties
The prepared functional graphene/modified boron nitride/montmorillonite ternary composite material lubricating oil additive is mixed with Kunlun Scorpio SF15W-40 lubricating oil in different proportions. A friction and wear test is carried out by using an MRS-10G four-ball friction and wear testing machine, and a GCr steel ball with the hardness of 770HV and the diameter of 12.7mm is used for testing. And (3) testing conditions are as follows: load 197N, speed 600rpm, test time 3600 s. The friction coefficient and the wear-scar diameter of the composite lubricant additive at different concentrations in the example are shown in table 1, and the test results of the simple graphene oxide, montmorillonite and boron nitride at a concentration of 0.044 wt% are shown for comparison, so that the composite lubricant additive prepared by the single-component material has excellent lubricating performance, the friction coefficient can be reduced by about 73.67% and the wear-scar diameter can be reduced by about 18.18% compared with the simple lubricant. Meanwhile, microhardness test is carried out on the grinding spot surface, and the test result is shown in table 2, so that the use of the composite material lubricating oil additive can be seen, and the hardness of the grinding spot surface is improved by 18.70 percent compared with that of the steel ball.
Example two
(1) Graphene oxide prepared by a modified Hummers method was used as a raw material to prepare 160g of an aqueous dispersion of 0.025 wt% graphene oxide. Then, 1mL of a silane coupling agent (A-1110) was added and the reaction was carried out at 25 ℃ for 5 hours. And standing, cooling, performing centrifugal separation, washing with water, and adding a proper amount of deionized water to obtain the aqueous dispersion of the functional graphene oxide.
(2) 0.01g of boron nitride is weighed, added with water, stirred and dispersed evenly to obtain an aqueous dispersion of the boron nitride, 0.5mL of silane coupling agent (A-1110) is added to react for 8h at room temperature, and the modified boron nitride is obtained after centrifugation and water washing.
(3) Mixing and stirring the modified boron nitride, 0.02g of montmorillonite and the aqueous dispersion of the functional graphene oxide for 0.5 h; transferring the mixture to a reaction kettle for hydrothermal reaction at 200 ℃ for 1h, standing and cooling; and (4) performing centrifugal separation, washing with water and ethanol respectively, and drying to obtain the functional graphene/modified boron nitride/montmorillonite ternary composite material lubricating oil additive.
(4) Evaluation of tribological Properties
The prepared functional graphene/modified boron nitride/montmorillonite ternary composite material lubricating oil additive is mixed with 0.044 wt% of Kunlun scorpion SF15W-40 lubricating oil. A friction and wear test is carried out by using an MRS-10G four-ball friction and wear testing machine, and a GCr steel ball with the hardness of 770HV and the diameter of 12.7mm is used for testing. And (3) testing conditions are as follows: load 197N, speed 600rpm, time 3600 s. The test results are given in table 1.
EXAMPLE III
(1) Graphene oxide prepared by a modified Hummers method was used as a raw material to prepare 160g of an ethanol dispersion of graphene oxide having a concentration of 0.025 wt%. Then, 8mL of a silane coupling agent (A-1120) was added, and the reaction was refluxed at 80 ℃ for 1 hour. Washing with water and ethanol, and adding a proper amount of ethanol to obtain an ethanol dispersion liquid of the functional graphene oxide.
(2) 0.16g of boron nitride is weighed, added with ethanol, stirred and dispersed evenly to obtain ethanol dispersion liquid of the boron nitride, added with 16mL of silane coupling agent (A-1120), refluxed and reacted for 3h at the temperature of 60 ℃, centrifuged and washed to obtain the modified boron nitride.
(3) Mixing and stirring the modified boron nitride, 0.32g of montmorillonite and the ethanol dispersion liquid of the functional graphene oxide for 2 hours; transferring the mixture into a reaction kettle for reflux reaction at 100 ℃ for 5 hours, standing and cooling; and (4) performing centrifugal separation, washing with water and ethanol respectively, and drying to obtain the functional graphene/modified boron nitride/montmorillonite ternary composite material lubricating oil additive.
(4) Evaluation of tribological Properties
The prepared functional graphene/modified boron nitride/montmorillonite ternary composite material lubricating oil additive is mixed with 0.044 wt% of Kunlun scorpion SF15W-40 lubricating oil. A friction and wear test is carried out by using an MRS-10G four-ball friction and wear testing machine, and a GCr steel ball with the hardness of 770HV and the diameter of 12.7mm is used for testing. And (3) testing conditions are as follows: load 197N, speed 600rpm, time 3600 s. The test results are given in table 1.
Example four
(1) Graphene oxide prepared by a modified Hummers method was used as a raw material to prepare 160g of an ethanol dispersion of graphene oxide having a concentration of 0.025 wt%. Then, 3mL of a silane coupling agent (KBM-602) was added thereto, and the mixture was transferred to a reaction vessel and reacted at 95 ℃ for 4 hours. Washing with water and ethanol, and adding a proper amount of ethanol to obtain an ethanol dispersion liquid of the functional graphene oxide.
(2) 0.08g of boron nitride is weighed, added with ethanol, stirred and dispersed to obtain ethanol dispersion liquid of the boron nitride, added with 16mL of silane coupling agent (KBM-602) and transferred to a reaction kettle to react for 1h at 100 ℃, and then the modified boron nitride is obtained after centrifugation and water washing.
(3) Mixing and stirring the modified boron nitride, 0.24g of montmorillonite and the ethanol dispersion liquid of the functional graphene oxide for 2 hours; transferring to a reaction kettle for reaction at 150 ℃ for 5h, standing and cooling; and (4) performing centrifugal separation, washing with water and ethanol respectively, and drying to obtain the functional graphene/modified boron nitride/montmorillonite ternary composite material lubricating oil additive.
(4) Evaluation of tribological Properties
The prepared functional graphene/modified boron nitride/montmorillonite ternary composite material lubricating oil additive is mixed with 0.044 wt% of Kunlun scorpion SF15W-40 lubricating oil. A friction and wear test is carried out by using an MRS-10G four-ball friction and wear testing machine, and a GCr steel ball with the hardness of 770HV and the diameter of 12.7mm is used for testing. And (3) testing conditions are as follows: load 197N, speed 600rpm, time 3600 s. The test results are given in table 1.
TABLE 1 Friction coefficient and wear scar diameter for different oil samples
Figure BDA0002135225550000051
TABLE 2 micro-hardness test results for the abraded surfaces
Figure BDA0002135225550000052

Claims (8)

1. A functional lubricating oil additive is prepared by mixing functional graphene oxide, modified boron nitride and montmorillonite in a mass ratio of 4:1-16: 2-32;
the preparation method comprises the following steps:
(1) preparing a dispersion liquid of graphene oxide by using graphene oxide prepared by an improved Hummers method as a raw material, adding a silane coupling agent, reacting at 25-100 ℃ for 1-6h, separating and cleaning to obtain functional graphene oxide;
(2) adding a silane coupling agent into the boron nitride dispersion liquid, reacting for 1-8h at 25-100 ℃, centrifuging, and cleaning to obtain modified boron nitride;
(3) mixing and stirring the modified boron nitride, the montmorillonite and the dispersion liquid of the functional graphene oxide for 0.5-2h, reacting for 1-5h at the temperature of 100-180 ℃, centrifuging, and cleaning to obtain the lubricating oil additive.
2. The lubricating oil additive according to claim 1, wherein in the step (1) and the step (2), the silane coupling agent is any one of A-1100, A-1110, A-1120, and KBM-602.
3. The lubricating oil additive according to claim 1, wherein in the step (1), the mass ratio of the graphene oxide to the silane coupling agent is 1:24 to 200.
4. The lubricating oil additive according to claim 1, wherein in the step (2), the mass ratio of the boron nitride to the silane coupling agent is 1:50 to 200.
5. The lubricating oil additive according to claim 1, wherein the dispersant used in each of the dispersions in the steps (1) to (3) is the same and is selected from any one of ethanol and water.
6. The method of preparing the lubricating oil additive of claim 1, comprising the steps of:
(1) preparing a dispersion liquid of graphene oxide by using graphene oxide prepared by an improved Hummers method as a raw material, adding a silane coupling agent, reacting at 25-100 ℃ for 1-6h, separating and cleaning to obtain functional graphene oxide;
(2) adding a silane coupling agent into the boron nitride dispersion liquid, reacting for 1-8h at 25-100 ℃, centrifuging, and cleaning to obtain modified boron nitride;
(3) mixing and stirring the modified boron nitride, the montmorillonite and the dispersion liquid of the functional graphene oxide for 0.5-2h, reacting for 1-5h at the temperature of 100-180 ℃, centrifuging, and cleaning to obtain the lubricating oil additive.
7. Use of the lubricating oil additive according to any of claims 1 to 5, wherein the additive is present in the lubricating oil at a concentration of 0.011 to 0.089 wt.%.
8. Use according to claim 7, wherein the lubricating oil comprises Kunlun Scorpio F5000 lubricating oil, SF15W-40 lubricating oil and great wall SJ10W-40 lubricating oil, or mineral base oil, synthetic base oil.
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