CN111500340A - Lubricating additive of hollow graphene oxide, super-lubricating water lubricant, and preparation method and application of super-lubricating water lubricant - Google Patents
Lubricating additive of hollow graphene oxide, super-lubricating water lubricant, and preparation method and application of super-lubricating water lubricant Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/02—Carbon; Graphite
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/14—Inorganic compounds or elements as ingredients in lubricant compositions inorganic compounds surface treated with organic compounds
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a lubricating additive and a super-lubricating water lubricant of hollow graphene oxide, and a preparation method and application thereof. The spherical shell is of a structure with a graphene oxide layer and a polydopamine layer composite layer from inside to outside or a structure with a polydopamine layer, a graphene layer and a polydopamine layer composite layer from inside to outside, the number of layers of the composite layers is single-layer or multi-layer, and the multi-layer structure is formed by repeatedly overlapping a plurality of composite layers. The preparation process firstly obtains graphene oxide/polybamine/Al2O3And (3) repeatedly coating the composite material to obtain a multilayer structure, and then etching to obtain the composite material with the hollow structure. The prepared water lubricant has super-smooth lubrication behavior and abrasion resistance.
Description
Technical Field
The invention belongs to the field of nano materials and the technical field of super-lubricating water lubricants, and particularly relates to a lubricating additive of hollow graphene oxide, a super-lubricating water lubricant, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Mechanical parts are ubiquitous in life and production, and a part of energy is lost due to friction in the process of mechanical operation, especially equipment which runs repeatedly for a long time. Therefore, the method brings great economic loss to the production process of people and causes environmental pollution and resource waste. The lubrication technology of many key parts of motor vehicles, micro-nano mechanical components and the like meets the development bottleneck, and how to know and control the friction and the wear becomes an important solution. Scientists theoretically predict that almost zero friction and abrasion exist between two atomic-level smooth and non-axiality contacted van der waals solid surfaces (such as two-dimensional material surfaces of graphene, molybdenum disulfide and the like), and the friction coefficient defining the ultra-smooth phenomenon is less than 0.01, so that the method has profound significance in the aspects of energy conservation, cost conservation and environmental safety. Despite the development and use of a variety of solid and liquid lubricants, ultra-smooth behavior is rarely achieved on a macroscopic or engineering scale.
Many kinds of lubricants have a certain influence on the environment, and water has attracted attention as a lubricant in the field of tribology as people pay more attention to environmental problems. However, in the boundary lubrication or mixed lubrication state, the pure water has poor lubrication performance, and the water film is easy to break, so that the metal surface is in direct contact, namely solid-solid contact, thereby greatly limiting the application of the pure water in the fields of moving parts and joint fluid lubrication.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a lubricating additive and a super-lubricating water lubricant of hollow graphene oxide, and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in a first aspect, the lubricating additive of the hollow graphene oxide is a spherical hollow structure, the spherical shell is of a structure of a graphene oxide layer and a polydopamine layer composite layer from inside to outside or a structure of a polydopamine layer, a graphene layer and a polydopamine layer composite layer from inside to outside, the number of layers of the composite layers is single layer or multiple layers, and the multiple layers of the structure are formed by repeatedly overlapping a plurality of composite layers.
The invention prepares a lubricating additive, the main components of the lubricating additive are graphene oxide and polydopamine, the lubricating additive has a hollow structure, and the lubricating additive has a lower friction coefficient, and the specific principle is that
The graphene oxide has an ultra-smooth surface, but the existing lubricant prepared by the graphene oxide cannot achieve the ultra-smooth property.
Although it has been recorded that the surface of the graphene oxide solid has zero friction, the ultra-slip performance is rarely achieved on a macroscopic or engineering scale, the graphene or graphene oxide-poly-dopamine composite material prepared in the application achieves ultra-slip, and achieves ultra-slip in an actual mechanical friction process at a macroscopic angle, so that energy consumption is reduced.
The lubricant comprises two lubricant additives, wherein the first lubricant additive is spherical graphene oxide/polydopamine or spherical multilayer graphene oxide/polydopamine; the multi-layer representation may be graphene oxide/polydopamine/graphene oxide/polydopamine, with graphene oxide at the outermost layer and polydopamine at the innermost layer.
The second is graphene oxide spherical polydopamine/graphene/polydopamine or multilayer spherical polydopamine/graphene/polydopamine. The multi-layered representation may be polydopamine/graphene/polydopamine. The graphene oxide is positioned on the outermost layer and the innermost layer.
The polydopamine has reducibility, one surface of the polydopamine, which is wrapped by graphene oxide, can be reduced, and the graphene oxide on the outermost layer does not react with the polydopamine, so that the graphene oxide on the outermost layer in the first lubricating additive is reduced on the inner side and not reduced on the outer side, and the graphene oxide positioned between the two polydopamine layers is actually reduced graphene. The graphene in the second type is located between two poly dopamine layers, so that the graphene is reduced from graphene oxide.
The polydopamine reaction process has reducibility, such as polydopamine/graphene/polydopamine, and both faces of graphene oxide are completely wrapped by polydopamine, which is completely reduced, so that the polydopamine/graphene/polydopamine is written.
For example, graphene oxide/polydopamine/graphene oxide/polydopamine, the structure means that the graphene oxide at the outermost layer does not react with polydopamine and is not reduced; and the surface of the outermost layer of graphene oxide wrapping polydopamine is reduced, so that the graphene oxide is still written as graphene oxide/polydopamine/graphene oxide/polydopamine.
In a second aspect, the preparation method of the lubricating additive of hollow graphene oxide comprises the following specific steps:
mixing a dopamine hydrochloride solution, water and a Tris solution, then adding the HCl solution, then adding a nano alumina colloid aqueous solution, and reacting to obtain a spherical nano alumina composite material containing polydopamine;
adding the obtained polydopamine-coated spherical nano-alumina composite material into a graphene oxide solution, and reacting to obtain graphene oxide/polydopamine/Al2O3A composite material;
mixing graphene oxide/polybara polyamine/Al2O3And mixing the composite material with HCl solution, and etching to obtain the hollow spherical lubricating additive.
And after etching, the nano aluminum oxide in the middle is etched and removed, and the remaining graphene oxide protects the structure of the polydopamine.
The nano alumina ball is used as the carrier ball, one reason is that the shape of the carrier ball is utilized to grow the graphene oxide ball or the graphene ball on the alumina ball, and because the graphene oxide or the graphene cannot form a ball by itself, the alumina ball is easy to prepare and has relatively low price; the prepared nano-alumina sphere contains abundant hydroxyl groups, and polydopamine is easier to graft on the surface of the spherical alumina; the oxygen-containing group or pi-pi bond on the surface of the graphene oxide can be bonded with polydopamine to be polymerized into spherical graphene oxide or graphene. The second reason is that alumina is easily etched by an acid solution with less contamination.
The preparation method of the lubricating additive of the hollow graphene oxide comprises the following specific steps:
mixing a dopamine hydrochloride solution, water and a Tris solution, then adding the HCl solution, then adding a nano alumina colloid aqueous solution, and reacting to obtain a spherical nano alumina composite material containing polydopamine;
adding the obtained polydopamine-coated spherical nano-alumina composite material into a graphene oxide solution, and reacting to obtain graphene oxide/polydopamine/Al2O3A composite material;
the obtained graphene oxide/polybara polyamine/Al2O3Mixing the composite material with dopamine hydrochloride, water and Tris solution, and reacting to obtain polydopamine/graphene/polybamine/Al2O3A composite material;
polydopamine/graphene/polybara polyamine/Al2O3And mixing the composite material with HCl solution, and etching to obtain the hollow spherical lubricating additive.
Graphene oxide/polybara polyamine/Al2O3And mixing the composite material with dopamine hydrochloride, water and a Tris solution, polymerizing the dopamine in the reaction process, combining the dopamine with graphene oxide, and reducing the graphene oxide to obtain the graphene.
In a third aspect, a super-lubricious water lubricant comprises water and the above-described lubricious additive.
In a fourth aspect, the super-lubricant is prepared by mixing the lubricant additive and water in an atmospheric environment.
In a fifth aspect, the use of the ultra-lubricious water lubricant described above in a machine component.
The invention has the beneficial effects that:
1. according to the invention, deionized water is used as a lubricating liquid, and in-situ assembled spherical graphene oxide or graphene composite material is used as a lubricating additive, so that the spherical graphene oxide or graphene can roll on a friction surface, and friction and wear are reduced; the poly-dopamine contains a large amount of hydroxyl groups and amino groups, and is easy to adsorb the surfaces of friction pairs, the poly-dopamine is easy to disperse in water, and the ultra-smooth water lubricant with different additive mass concentrations is prepared under the atmospheric environment condition.
2. The super-lubricating water lubricant can be stored for 6 months to 1 year without obvious precipitation phenomenon, and has long shelf life.
3. Tribology tests show that the water lubricant obtained by the invention has super-smooth lubricating behavior and wear resistance, so that the water lubricant can be used as a super-smooth lubricant material for mechanical moving parts in atmospheric environment.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
Fig. 1 is a flow chart of the preparation of graphene oxide/polydopamine;
fig. 2 is a flow chart of the preparation of polydopamine/graphene/polydopamine;
FIG. 3 is a plot of the friction test of a pure deionized water lubricant on a ball-and-disk of comparative example 1 of the present application.
Fig. 4 is a friction test curve of graphene oxide ball additive water lubricant with a mass concentration of 0.20% on a ball-disk in example 16 of the present application.
Fig. 5 is a friction test curve of graphene ball additive water lubricant with a mass concentration of 0.20% on a ball-disk in example 20 of the present application.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In a first aspect, the lubricating additive of the hollow graphene oxide is a spherical hollow structure, the spherical shell is of a structure of a graphene oxide layer and a polydopamine layer composite layer from inside to outside or a structure of a polydopamine layer, a graphene layer and a polydopamine layer composite layer from inside to outside, the number of layers of the composite layers is single layer or multiple layers, and the multiple layers of the structure are formed by repeatedly overlapping a plurality of composite layers.
In some embodiments of the invention, the spherical hollow structures have a diameter of 50-300 nm.
In a second aspect, the preparation method of the lubricating additive of hollow graphene oxide comprises the following specific steps:
1) mixing a dopamine hydrochloride solution, water and a Tris solution, then adding the HCl solution, then adding a nano alumina colloid aqueous solution, and reacting to obtain a spherical nano alumina composite material containing polydopamine;
2) packaging the obtained polydopamineAdding the wrapped spherical nano-alumina composite material into a graphene oxide solution, and reacting to obtain graphene oxide/polybamine/Al2O3A composite material;
or, 3) the graphene oxide/polybara polyamine/Al obtained in the step 2)2O3The composite material is sequentially and repeatedly subjected to the reaction of mixing dopamine hydrochloride, water, Tris solution and HCl solution in the step 1) and the reaction of graphene oxide in the step 2) to obtain multilayer graphene oxide/polybara polyamine/Al2O3A composite material;
4) the single-layer graphene oxide/polybara polyamine/Al2O3Composite material or multilayer graphene oxide/polybara polyamine/Al2O3And mixing the composite material with HCl solution, and etching to obtain the hollow spherical lubricating additive.
And after etching, the nano aluminum oxide in the middle is etched and removed, and the remaining graphene oxide protects the structure of the polydopamine.
And (3) repeatedly adding a hydrochloric acid solution in the reaction process of mixing the hydrochloric acid solution with the dopamine and Tris solution in the step 1), wherein the hydrochloric acid can react with the Tris solution only after the PH value is adjusted by hydrochloric acid.
In some embodiments of the present invention, the mixture after the reaction in step 3) is separated by centrifugation, the supernatant is removed, and the mixture is freeze-dried to obtain the multilayer graphene oxide/polybamine/Al2O3A composite material.
In some embodiments of the invention, the mixture after the reaction in step 4) is centrifuged to remove the supernatant, and freeze-dried to obtain the lubricant additive.
In some embodiments of the present invention, the volume ratio and the addition amount of the dopamine hydrochloride, the water, the Tris solution and the HCl solution participating in the reaction in step 3) are the same as those in step 1), and the addition amount and the concentration of the graphene oxide solution participating in the reaction are the same as those in step 2).
The other preparation method comprises the following steps:
the preparation method of the lubricating additive of the hollow graphene oxide comprises the following specific steps:
1) mixing a dopamine hydrochloride solution, water and a Tris solution, then adding the HCl solution, then adding a nano alumina colloid aqueous solution, and reacting to obtain a spherical nano alumina composite material containing polydopamine;
2) adding the obtained polydopamine-coated spherical nano-alumina composite material into a graphene oxide solution, and reacting to obtain graphene oxide/polydopamine/Al2O3A composite material;
3) subjecting the graphene oxide/polybara polyamine/Al obtained in the step 2)2O3The composite material is subjected to a reaction of mixing with dopamine hydrochloride, water, a Tris solution and a HCl solution in the step 1) to obtain single-layer polydopamine/graphene/polydopamine/Al2O3A composite material;
or, 4) poly-dopamine/graphene/poly-dopamine/Al obtained in the step 3)2O3The composite material is sequentially and repeatedly subjected to the reaction with graphene oxide in the step 2) and the reaction with dopamine hydrochloride, water, Tris solution and HCl solution in the step 1) to obtain multilayer polydopamine/graphene/polydopamine/Al2O3A composite material;
5) single-layer polydopamine/graphene/polydopamine/Al2O3Composite material or multilayer polydopamine/graphene/polydopamine/Al2O3And mixing the composite material with HCl solution, and etching to obtain the hollow spherical lubricating additive.
Step 1) is to add nano-alumina into a hydrochloric acid-regulated dopamine, water and Tris mixed solution with pH 8.5, and perform polymerization reaction on the surface of the alumina so as to graft the nano-alumina onto the surface.
The surface of the graphene oxide contains abundant hydrophilic groups such as hydroxyl, carboxyl and oxygen-containing groups; the poly-dopamine is bonded with the surface group of the graphene oxide through hydroxyl or pi-pi bonds.
Graphene oxide/polybamine/Al in step 3)2O3And mixing the composite material with dopamine hydrochloride, water, a Tris solution and an HCl solution, polymerizing the dopamine in the reaction process, combining the dopamine with graphene oxide, and reducing the graphene oxide to obtain the graphene.
The step 4) is repeated and orderly to wrap the oxidized graphene and graft the polydopamine, so that the preparation of multilayer polydopamine/graphene/polydopamine/Al is realized2O3A composite material. The number of layers of the composite layer of the polydopamine/graphene is 3-6.
In some embodiments of the invention, dopamine hydrochloride, water, Tris solution, nano-Al in step 1)2O3The ratio of the HCl solution is 0.05-0.15m L: 8-12m L: 2.2-2.7m L: 0.05-0.25g:1m L.
In some embodiments of the invention, the concentration of dopamine hydrochloride in step 1) is 2-5mg/m L, the concentration of Tris solution is 0.05-0.15mol/L solution is 0.05-0.15mol/L, preferably, the concentration of dopamine hydrochloride is 2mg/m L, and the concentration of Tris solution is 0.1mol/L solution is 0.1 mol/L.
In the steps 1), dopamine hydrochloride, water and a Tris solution are mixed, then the HCl solution is used for adjusting the pH value, then nano alumina is added, so that dopamine hydrochloride is polymerized on the surface of the nano alumina, polydopamine is grafted to the surface of the nano alumina, the particle size of the nano alumina is 50-300nm, the nano alumina provides a polydopamine balling carrier, in some embodiments of the invention, in the step 1), nano alumina powder or a nano alumina colloid solution is added, and the concentration of the added nano alumina colloid solution is 0.05-0.15g/m L, preferably 0.1g/m L.
In some embodiments of the present invention, the concentration of the graphene oxide solution in step 2) is 0.5-2.5mg/m L. the grafting process of the polydopamine on the surface of the graphene oxide is performed at normal temperature, the surface of the graphene oxide contains functional groups, such as hydroxyl, carboxyl and oxygen-containing groups, and the polydopamine is in graft connection with the graphene oxide through hydroxyl or pi-pi bonds.
In some embodiments of the present invention, the method for preparing graphene oxide is a Hummer method.
In some embodiments of the invention, the polydopamine is reacted with the alumina for a time period of 10 to 15 hours.
In some embodiments of the invention, the mixture after the reaction in step 1) is subjected to centrifugal separation, supernatant is removed, and freeze drying is performed to obtain the poly-dopamine-coated spherical nano-alumina composite material.
In some embodiments of the present invention, the mixture after the reaction in step 2) is separated by centrifugation, the supernatant is removed, and the mixture is freeze-dried to obtain graphene oxide/polybamine/Al2O3A composite material.
In some embodiments of the present invention, the mixture after the reaction in step 3) is centrifuged to remove the supernatant, and then freeze-dried to obtain monolayer poly-dopamine/graphene/poly-dopamine/Al2O3A composite material.
In some embodiments of the present invention, the mixture after the reaction in step 4) is centrifuged to remove the supernatant, and then freeze-dried to obtain multi-layered polydopamine/graphene/polydopamine/Al2O3A composite material.
In some embodiments of the invention, the solution obtained after etching with HCl in step 5) is centrifuged to remove the supernatant, and freeze-dried to obtain the lubricant additive.
In some embodiments of the present invention, the volume ratio and the addition amount of the dopamine hydrochloride, the water, the Tris solution and the HCl solution participating in the reaction in step 3) or step 4) are the same as those in step 1), and the addition amount and the concentration of the graphene oxide solution participating in the reaction in step 4) are the same as those in step 2).
In a third aspect, a super-lubricious water lubricant comprises water and the above-described lubricious additive.
In some embodiments of the invention, the mass concentration of the lubricant additive in the ultra-lubricious water lubricant is from 0.01% to 0.8%; preferably 0.01-0.5%; further preferably 0.2%. The ultra-lubricious water lubricants in the above mass concentration range have a low coefficient of friction.
In a fourth aspect, the super-lubricant is prepared by mixing the lubricant additive and water in an atmospheric environment.
In a fifth aspect, the use of the ultra-lubricious water lubricant described above in a machine component.
The invention will be further illustrated by the following examples
Example 1
(1) Preparing a graphene oxide solution by using a Hummer improvement method, namely firstly, cooling a 1000m L dry flask in an ice-water bath for 5min, then adding 100m L concentrated sulfuric acid, adding 2g of flake graphite, 1.2g of sodium nitrate and 8.0g of potassium permanganate in the stirring process, controlling the reaction temperature in the ice-water bath to be 5 ℃, carrying out magnetic stirring reaction for 2h, then taking out the flask, placing the flask on a constant-temperature heating magnetic stirrer, carrying out magnetic stirring reaction for 2h at 35 ℃, finally adding 150m L deionized water, raising the reaction temperature to 95 ℃ by using the constant-temperature heating stirrer, continuing to carry out magnetic stirring for 1h to obtain a 50mg/m L graphite oxide solution, adding deionized water to dilute the graphite oxide solution, carrying out ultrasonic oscillation for 2h to obtain a graphene oxide aqueous solution, completely freezing the graphene oxide aqueous solution in a refrigerator, then taking out and placing the graphene oxide solution into a freeze dryer, freezing, vacuumizing and drying to obtain graphene oxide powder.
(2) Adding 20m L deionized water into a 50m L beaker, adding 0.2m L dopamine hydrochloride solution (2.0mg/m L) and 5.0m L Tris solution (0.1 mol/L) into the deionized water, adding 2.0m L prepared HCl solution (0.1 mol/L) into the solution, adjusting the pH value of the solution to 8.5, and adding 100mg nano Al2O3Adding the powder into the solution, and magnetically stirring the whole solution for 12 hours to obtain the poly-dopamine in-situ grafted spherical nano Al2O3A surface; putting the obtained solution into a centrifugal machine, and centrifuging at 10000 rpm for 20 minutes; discarding the supernatant, and wrapping the obtained polydopamine with nano Al2O3And drying the powder, centrifuging and drying to obtain black powder.
(3) Weighing 5mg (2) of black powder, respectively adding the black powder into graphene oxide solution with the concentration of 0.5mg/m L, and then magnetically stirring for 12 hours to obtain monolayer graphene oxide coated polybara polyamine/Al2O3A composite material.
(4) In the obtained graphene oxide/polybara polyamine/Al2O35.0m L is added into the composite material solution to prepare 0.1mol/L HCl solution (hydrochloric acid excess), and the nano Al of the inner core is etched2O3Thereby obtaining a few-layer graphene oxide sphere solution; and putting the obtained solution into a centrifugal machine, centrifuging for 20 minutes at 10000 rpm, discarding supernatant, putting the obtained few-layer graphene oxide spheres into a freeze dryer, freezing and drying to obtain black powder.
As shown in fig. 1, which is a flow chart of graphene oxide/poly-dopamine preparation, a is spherical nano-alumina, b is poly-dopamine/nano-alumina, c is graphene oxide/poly-dopamine/nano-alumina, and d is graphene oxide/poly-dopamine.
Example 2
The difference from example 1 is that the concentration of the graphene oxide solution was 1.0mg/m L.
Example 3
The difference from example 1 is that the concentration of the graphene oxide solution was 1.5mg/m L.
Example 4
Different from example 1, the concentration of the graphene oxide solution was 2.0mg/m L.
Example 5
Different from example 1, the concentration of the graphene oxide solution was 2.5mg/m L.
Example 6
Different from the embodiment 1, the graphene oxide/polybamine/Al2O3Repeating the polydopamine grafting step (3) once to obtain graphene oxide/polybamine/Al2O3The composite material is prepared by mixing dopamine hydrochloride, water, a Tris solution and an HCl solution for reaction in polymerization of polydopamine; wherein the volumes and concentrations of the dopamine hydrochloride, the water, the Tris solution and the HCl solution are the same as those in the step (2).
Example 7
(1) Same as in step (1) of example 1;
(2) same as in step (2) of example 1;
(3) weighing 5mg (2) of black powder, respectively adding the black powder into graphene oxide solution with the concentration of 0.5mg/m L, and then magnetically stirring for 12 hours to obtain monolayer graphene oxide coated polybara polyamine/Al2O3A composite surface;
(4) wrapping the single-layer graphene oxide obtained in the step (3) with polybara polyamine/Al2O3The composite material is mixed with dopamine hydrochloride, water, Tris solution and HCl solution in the step (2) for reaction to obtain polydopamine/graphene/polydopamine/Al2O3A composite material;
(5) the obtained polydopamine/graphene/polydopamine/Al2O35.0m L is added into the composite material solution to prepare 0.1mol/L HCl solution (hydrochloric acid excess), and the nano Al of the inner core is etched2O3Thereby obtaining a few-layer graphene sphere solution; and putting the obtained solution into a centrifugal machine, centrifuging the solution at 10000 rpm for 20 minutes, discarding the supernatant, putting the obtained few-layer graphene spheres into a freeze dryer, freezing and drying to obtain black powder.
As shown in fig. 2, a is spherical nano-alumina, b is poly-dopamine/nano-alumina, c is graphene oxide/poly-dopamine/nano-alumina, d is poly-dopamine/graphene/poly-dopamine/nano-alumina, and e is poly-dopamine/graphene/poly-dopamine.
Example 8
Different from example 7, the concentration of the graphene oxide solution in the step (3) was 1.0mg/m L.
Example 9
Different from example 7, the concentration of the graphene oxide solution in the step (3) was 1.5mg/m L.
Example 10
Except for example 7, the concentration of the graphene oxide solution in the step (3) was 2.0mg/m L.
Example 11
Different from example 7, the concentration of the graphene oxide solution in the step (3) was 2.5mg/m L.
Example 12
The difference from example 7 is: poly-dopamine/graphene/poly-dopamine/Al obtained in the step (4)2O3The composite material is mixed with dopamine hydrochloride, water, Tris solution and HCl solution in the step (3) and the step (2) repeatedlyAnd (3) reacting to obtain the polydopamine/graphene/polydopamine lubricating additive.
Example 13
Adding 1mg of the black powder obtained in the step (4) in the example 1 into a beaker filled with deionized water, sealing the openings of the beaker filled with the black powder and the deionized water in the step (4) at room temperature, and carrying out ultrasonic oscillation for 2 hours to obtain a uniformly mixed solution with the mass concentration of 0.01 percent, thereby obtaining the ultra-smooth water-based lubricant.
Example 14
Different from example 13, the amount of black powder added was 5mg, and a mixed solution having a mass concentration of 0.05% was obtained.
Example 15
Different from example 13, the amount of black powder added was 10mg, and a mixed solution having a mass concentration of 0.1% was obtained.
Example 16
Different from example 13, the amount of the black powder added was 20mg, and a mixed solution having a mass concentration of 0.2% was obtained. The tribology test curve of the super-smooth water lubricant of the multilayer graphene oxide sphere aqueous solution in the atmospheric environment is shown in fig. 4.
Example 17
Different from example 13, the amount of black powder added was 30mg, and a mixed solution having a mass concentration of 0.3% was obtained.
Example 18
Different from example 13, the amount of black powder added was 40mg, and a mixed solution having a mass concentration of 0.4% was obtained.
Example 19
Different from example 13, the amount of black powder added was 50mg, and a mixed solution having a mass concentration of 0.5% was obtained.
Example 20
The difference from example 16 is: the black powder obtained in step (5) of example 7 was added. The tribology test curve of the super-slippery water lubricant of the multilayer graphene sphere aqueous solution in an atmospheric environment is shown in fig. 5.
Example 21
Different from the embodiment 1, the method is characterized in that a nano alumina colloid aqueous solution is added, and the specific operation steps are as follows:
preparing 0.1g/m L nanometer Al in a 100m L beaker2O3Preparing 5.0mg/m L dopamine hydrochloride by colloid water solution, adding 20m L deionized water into a 50m L beaker, adding 0.2m L dopamine hydrochloride solution (2.0mg/m L) and 5m L Tris solution (0.1 mol/L) into deionized water, adding 2.0m L prepared HCl solution (0.1 mol/L) into the solution, adjusting the pH value of the solution to 8.5, and adding 5.0m L nanometer Al2O3The colloidal solution (0.1g/m L) was added to the above prepared solution and the whole solution was magnetically stirred for 12 hours.
The remaining procedure was the same as in example 1. And obtaining the graphene oxide/polydopamine lubricating additive.
Example 21 differs from example 1 in the form of the addition of nano-alumina, i.e. in the method of operation.
Comparative example 1
The water lubricant is deionized water.
Test example 1
The test was carried out in an atmospheric environment using a ball-and-disk reciprocating friction abrasion tester (CETR Co., USA, UMT-3), in which a stainless steel disk was fixed as a lower sample on a flat bottom disk and a steel ball having a diameter of 6.0mm was fixed as a dual ball on an upper sample. The sliding time is 60min, the sliding amplitude is 1mm, the reciprocating frequency is 20Hz, and the load is 1N.
The origin 9.0 software was used to plot the frictional wear curves of fig. 3, 4, and 5 for comparative example 1, example 16, and example 20, respectively, and the results indicated that: compared with pure deionized water, the friction coefficient of the in-situ assembled spherical graphene oxide aqueous solution lubricant is reduced to 0.006, the ultra-slip behavior under a macroscopic atmospheric environment is realized, the wear rate is almost zero, and the in-situ assembled composite material can be further proved to be used as a macroscopic engineering ultra-slip water lubricant additive.
The curves in fig. 4 and fig. 5 are different in trend, which shows that the break-in time required for the poly-dopamine/graphene/poly-dopamine to achieve super-lubricity is shorter than that required for the poly-dopamine/graphene oxide/poly-dopamine in the friction process, and the super-lubricity friction coefficient of the poly-dopamine/graphene oxide/poly-dopamine is more stable.
The friction factors of examples 13 to 20 are shown in table 1:
TABLE 1 Friction factor for different examples
| Examples | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 |
| Coefficient of friction | 0.24 | 0.20 | 0.02 | 0.006 | 0.15 | 0.12 | 0.016 | 0.007 |
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A lubricating additive of hollow graphene oxide is characterized in that: the method comprises the following specific steps: the spherical shell is of a structure with a graphene oxide layer and a polydopamine layer composite layer from inside to outside or a structure with a polydopamine layer, a graphene layer and a polydopamine layer composite layer from inside to outside, the number of layers of the composite layers is single-layer or multi-layer, and the multi-layer structure is formed by repeatedly overlapping a plurality of composite layers.
2. The lubricious additive of hollow graphene oxide of claim 1, wherein: the diameter of the spherical hollow structure is 50-300 nm.
3. The method for preparing a lubricant additive of hollow graphene oxide according to any one of claims 1 to 2, wherein: the method comprises the following specific steps:
1) mixing a dopamine hydrochloride solution, water and a Tris solution, then adding the HCl solution, then adding a nano alumina colloid aqueous solution, and reacting to obtain a spherical nano alumina composite material containing polydopamine;
2) adding the obtained polydopamine-coated spherical nano-alumina composite material into a graphene oxide solution, and reacting to obtain graphene oxide/polydopamine/Al2O3A composite material;
or, 3) the graphene oxide/polybara polyamine/Al obtained in the step 2)2O3The composite material is sequentially and repeatedly subjected to the reaction of mixing dopamine hydrochloride, water, Tris solution and HCl solution in the step 1) and the reaction of graphene oxide in the step 2) to obtain multilayer graphene oxide/polybara polyamine/Al2O3A composite material;
4) the single-layer graphene oxide/polybara polyamine/Al2O3Composite or multilayerGraphene oxide/polybara polyamine/Al2O3Mixing the composite material with HCl solution, and etching to obtain a hollow spherical lubricating additive;
preferably, the mixture after the reaction in step 3) is separated by centrifugation, supernatant is removed, and freeze drying is carried out to obtain the multilayer graphene oxide/polybamine/Al2O3A composite material;
preferably, the mixture after the reaction in the step 4) is subjected to centrifugal separation, supernatant is removed, and the mixture is subjected to freeze drying to obtain the lubricant additive;
preferably, the volume ratio and the addition amount of the dopamine hydrochloride, the water, the Tris solution and the HCl solution participating in the reaction in the step 3) are the same as those in the step 1), and the addition amount and the concentration of the graphene oxide solution participating in the reaction are the same as those in the step 2).
4. The method for preparing a lubricant additive of hollow graphene oxide according to any one of claims 1 to 2, wherein:
1) mixing a dopamine hydrochloride solution, water and a Tris solution, then adding the HCl solution, then adding a nano alumina colloid aqueous solution, and reacting to obtain a spherical nano alumina composite material containing polydopamine;
2) adding the obtained polydopamine-coated spherical nano-alumina composite material into a graphene oxide solution, and reacting to obtain graphene oxide/polydopamine/Al2O3A composite material;
3) subjecting the graphene oxide/polybara polyamine/Al obtained in the step 2)2O3The composite material is subjected to a reaction of mixing with dopamine hydrochloride, water, a Tris solution and a HCl solution in the step 1) to obtain single-layer polydopamine/graphene/polydopamine/Al2O3A composite material;
or, 4) poly-dopamine/graphene/poly-dopamine/Al obtained in the step 3)2O3The composite material is sequentially and repeatedly subjected to the reaction with graphene oxide in the step 2) and the reaction with dopamine hydrochloride, water, Tris solution and HCl solution in the step 1) to obtain multilayer polydopamine/graphene/polydopamine/Al2O3A composite material;
5) single-layer polydopamine/graphene/polydopamine/Al2O3Composite material or multilayer polydopamine/graphene/polydopamine/Al2O3And mixing the composite material with HCl solution, and etching to obtain the hollow spherical lubricating additive.
5. The method for preparing a lubricant additive of hollow graphene oxide according to any one of claims 3 or 4, wherein: dopamine hydrochloride, water, Tris solution and nano Al in step 1)2O3The ratio of the HCl solution is 0.05-0.15m L: 8-12m L: 2.2-2.7m L: 0.05-0.25g:1m L;
or, in the step 1), the concentration of the dopamine hydrochloride is 2-5mg/m L, the concentration of the Tris solution is 0.05-0.15mol/l, the concentration of the HCl solution is 0.05-0.15mol/l, preferably, the concentration of the dopamine hydrochloride is 2mg/m L, the concentration of the Tris solution is 0.1mol/l, and the concentration of the HCl solution is 0.1 mol/l;
or, in the step 1), adding nano alumina powder or nano alumina colloid solution, wherein the concentration of the added nano alumina colloid solution is 0.05-0.15g/m L, preferably 0.1g/m L;
or, the concentration of the graphene oxide solution in the step 2) is 0.5-2.5mg/m L;
or the preparation method of the graphene oxide is a Hummer method.
6. The method for preparing a lubricant additive of hollow graphene oxide according to any one of claims 3 or 4, wherein: the reaction time of the polydopamine and the alumina is 10-15 h;
or, centrifuging the mixture reacted in the step 1), removing supernatant, and freeze-drying to obtain the poly-dopamine-coated spherical nano-alumina composite material;
or, centrifuging the mixture after the reaction in the step 2), removing supernatant, and freeze-drying to obtain the graphene oxide/polybamine/Al2O3A composite material.
7. A method as claimed in claim 4The preparation method of the lubricating additive of the hollow graphene oxide is characterized by comprising the following steps: centrifuging the mixture reacted in the step 3), removing supernatant, and freeze-drying to obtain monolayer poly-dopamine/graphene/poly-dopamine/Al2O3A composite material;
or, centrifuging the mixture reacted in the step 4), removing supernatant, and freeze-drying to obtain multilayer polydopamine/graphene/polydopamine/Al2O3A composite material;
or, carrying out centrifugal separation on the solution obtained by etching by using HCl in the step 5), removing supernatant, and carrying out freeze drying to obtain the lubricating additive;
or, the volume ratio and the adding amount of the dopamine hydrochloride, the water, the Tris solution and the HCl solution participating in the reaction in the step 3) or the step 4) are the same as those in the step 1), and the adding amount and the concentration of the graphene oxide solution participating in the reaction in the step 4) are the same as those in the step 2).
8. An ultra-lubricious water lubricant, comprising: comprising water and the lubricity additive of claim 1;
preferably, the mass concentration of the lubricating additive in the super-lubricating water lubricant is 0.01-0.8%; preferably 0.01-0.5%; further preferably 0.2%.
9. The method of preparing the ultra-lubricious water lubricant of claim 8, wherein: and mixing the lubricating additive and water in an atmospheric environment to obtain the super-lubricating water lubricant.
10. Use of the ultra-lubricious water lubricant of claim 8 in a machine component.
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| CN202010503914.5A CN111500340A (en) | 2020-06-05 | 2020-06-05 | Lubricating additive of hollow graphene oxide, super-lubricating water lubricant, and preparation method and application of super-lubricating water lubricant |
| JP2021535692A JP7224605B2 (en) | 2020-06-05 | 2020-07-21 | Hollow graphene oxide lubricating additives and superlubricating water lubricants, and methods of making and using the same |
| PCT/CN2020/103350 WO2021243825A1 (en) | 2020-06-05 | 2020-07-21 | Hollow graphene oxide lubricating additive, super-lubricating water lubricant, preparation method therefor and use thereof |
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