CN113773892B - Preparation method of lipophilic black phosphorus lubricating oil - Google Patents
Preparation method of lipophilic black phosphorus lubricating oil Download PDFInfo
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- CN113773892B CN113773892B CN202110910356.9A CN202110910356A CN113773892B CN 113773892 B CN113773892 B CN 113773892B CN 202110910356 A CN202110910356 A CN 202110910356A CN 113773892 B CN113773892 B CN 113773892B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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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
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
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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
- C10M2201/04—Elements
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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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- 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
- C10N2030/64—Environmental friendly compositions
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Abstract
The invention belongs to the technical field of novel lubricating materials, and particularly relates to a preparation method of lipophilic black phosphorus lubricating oil. Firstly, grinding black phosphorus crystal powder into fine powder, and drying in vacuum to obtain black phosphorus nanosheet fine powder; modifying the black phosphorus nanosheet by using a lipophilic modifying material to obtain a modified black phosphorus nanosheet; and mixing the modified black phosphorus nanosheet with base lubricating oil to prepare the lipophilic black phosphorus lubricating oil. The lipophilic black phosphorus lubricating oil prepared by the method contains lipophilic functional groups on the surface, has good dispersibility in oil, and has ultralow friction coefficient and relatively higher wear resistance. The lubricating oil disclosed by the invention can reduce the friction coefficient to be below 0.01, has an extremely low friction coefficient, and has excellent anti-wear and anti-compression properties. In addition, the lubricating fluid of the invention takes oil as a reference fluid and can be applied to most engineering manufacturing.
Description
Technical Field
The invention belongs to the technical field of novel lubricating materials, and particularly relates to a preparation method of lipophilic black phosphorus lubricating oil.
Background
With the rapid development of modern industry in China, the contradiction between the energy consumption required by human development and the increasingly deficient and non-renewable resources becomes more and more serious, and the energy consumption caused by unnecessary friction accounts for about 4.5 percent of the total value of national production in China. Therefore, how to reduce the frictional wear will effectively reduce the economic problem caused by the energy loss. In addition, most of the lubricating products in the current market are based on mineral oil or synthetic oil, the lubricating oil pollutes the environment, the friction coefficient is generally about 0.1, the lubricating oil does not have very excellent lubricating performance, and the production process of the lubricating oil is complex and the cost is high. Therefore, the development of a relatively green lubricating oil with ultra-low wear is a problem that needs to be solved urgently.
Disclosure of Invention
The present invention has been made to solve the technical problems of the prior art, and the rapid development of two-dimensional materials has led to its application to semiconductors, electronic devices, bionics, flexible materials, lubricating materials, etc., based on the discovery and recognition of the following problems by the inventors. Among them, two-dimensional materials have been a research focus as lubricant additives. For example: fullerene, graphene, boron nitride, molybdenum disulfide, transition metal carbides, and the like. The edge of the graphene sheet layer contains a large number of functional groups such as hydroxyl groups, carboxyl groups and the like, and the graphene sheet layer has good hydrophilicity. Black phosphorus is three common isohormones of phosphorusOne of the most stable forms of the allotropes (red, white and black phosphorus). Black phosphorus has a natural lamellar structure similar to graphite, consisting of sp 3 The hybridized phosphorus atoms are connected in a honeycomb-like fold pattern, and the layers are connected with weak van der waals force.
The invention aims to provide a preparation method of lipophilic black phosphorus lubricating oil, which aims to overcome the problem of poor dispersibility of the traditional two-dimensional material in an oil-based lubricant and ensure that the prepared lipophilic black phosphorus lubricating oil has good dispersibility
The embodiment of the invention provides a preparation method of lipophilic black phosphorus lubricating oil, which comprises the following steps:
(1) grinding the black phosphorus crystal powder into fine powder, and performing vacuum drying to obtain black phosphorus nanosheet fine powder;
(2) modifying the black phosphorus nanosheet by using a lipophilic modifying material to obtain a modified black phosphorus nanosheet;
(3) and mixing the modified black phosphorus nanosheet with base lubricating oil to prepare the lipophilic black phosphorus lubricating oil.
According to the preparation method of the lipophilic black phosphorus lubricating oil, the lipophilic black phosphorus lubricating oil prepared by the method has the advantages and the technical effects that the surface of the oil-based lubricating liquid contains lipophilic functional groups, the oil-based lubricating liquid has good dispersibility in the lubricating oil, and the oil-based lubricating liquid has an ultralow friction coefficient on bearing steel. Compared with the traditional lubricating liquid (the friction coefficient of a common lubricant is about 0.1), the lipophilic black phosphorus lubricating oil prepared by the embodiment of the invention can reduce the friction coefficient between friction pairs to be below 0.01, and has extremely low friction coefficient and good dispersibility; secondly, the lipophilic black phosphorus lubricating oil prepared by the method of the embodiment of the invention has ultralow friction coefficient and good abrasion resistance, so that the lubricating oil has wide application range, such as: cutting, bearing and the like, and has great practical value. Due to the unique structure of the black phosphorus nanosheet, the lipophilic black phosphorus lubricating oil has good photoelectric conversion efficiency, high electron mobility and excellent biocompatibility, and has good application prospects in the fields of thin film transistors, photoelectric detection, light-operated electronic elements, electroluminescence and biomedicine.
In some embodiments, in step (1), the fine powder has a particle size of 200 to 500 μm.
In some embodiments, in the step (1), the vacuum degree of the vacuum drying is 20 to 30kPa, and the drying time is 4 to 6 hours.
In some embodiments, in the step (2), the lipophilic modifying material contains a lipophilic group, and the lipophilic group contains an alkyl group, a phenyl group, or a cycloalkyl group.
In some embodiments, in step (2), the lipophilic modifying material is a mixed powder formed from n-decylcyclohexane powder and n-decyltriethoxysilane powder.
In some embodiments, in step (2), the modification process is as follows:
(1) forming a first mixed powder by using n-decylcyclohexane powder and n-decyltriethoxysilane powder, wherein the mass ratio of the n-decylcyclohexane powder to the n-decyltriethoxysilane powder in the first mixed powder is as follows: 1(0.5 to 1);
(2) mixing the black phosphorus nanosheet fine powder with the first mixed powder to obtain second mixed powder, wherein the mass ratio of the black phosphorus nanosheet fine powder to the first mixed powder is as follows: (2-7) 1;
(3) mixing the second mixed powder with water, wherein the mass ratio of the second mixed powder to the water is as follows: 20000 (1-4), reacting at 120-150 ℃ for 5-6 hours;
(4) and (3) performing vacuum drying to obtain the modified black phosphorus nanosheet, wherein the vacuum degree of the vacuum drying is 20-30 kPa, and the drying time is 4-6 hours.
In some embodiments, in the step (3), the oil-based lubricating fluid is polyalphaolefin base oil, rapeseed oil, castor oil, or polyether synthetic oil.
In some embodiments, in step (3), the lipophilic black phosphorus lubricating oil is prepared by the following process:
(1) mixing the modified black phosphorus nanosheet with base lubricating oil, wherein the mass ratio of the modified black phosphorus nanosheet to the polyalphaolefin base oil is as follows: (0.01-0.5) 1, heating the obtained mixed solution in a water bath, and stirring to obtain black phosphorus lubricating oil;
(2) and (3) carrying out vibration treatment on the black phosphorus lubricating oil, carrying out centrifugal separation on the black phosphorus lubricating oil after vibration treatment, and obtaining supernatant fluid which is the lipophilic black phosphorus lubricating oil after centrifugal separation.
In some embodiments, the stirring is magnetic stirring, the frequency is 20 to 60Hz, the temperature is 60 to 80 ℃, and the stirring time is 50 to 60 min.
In some embodiments, the vibration treatment is ultrasonic vibration treatment for 6 to 8 hours at a temperature of 30 to 80 ℃.
In some embodiments, the centrifugal separation is performed at a rotation speed of 1000-3000 rpm for 30-60 min.
The embodiment of the invention also provides lipophilic black phosphorus lubricating oil which is prepared by the method of the embodiment of the invention.
According to the lipophilic black phosphorus lubricating oil provided by the embodiment of the invention, the black phosphorus has a graphene-like structure, but atoms in the same layer are not on the same plane, so that a honeycomb-shaped fold structure is formed. The structure has stronger covalent bonds and combines atoms through Van der Waals force, so that the black phosphorus has inherent characteristics of lower shear strength, higher thermodynamic stability and the like.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a graph comparing the friction coefficient versus wear time curves of the lipophilic black phosphorus lubricating oil obtained in example 1 with different liquids.
FIG. 2 is a graph of coefficient of friction versus wear time for the oleophilic black phosphorus lubricating oil obtained in example 2.
FIG. 3 is a graph of the friction coefficient versus differential pressure change for the oleophilic black phosphorus lubricating oil obtained in example 3.
FIG. 4 is a graph of the friction coefficient versus different concentrations of the lipophilic black phosphorus lubricating oil obtained in example 4.
FIG. 5 is a graph of the coefficient of friction versus the different speed profiles for the oleophilic black phosphorus lubricating oil obtained in example 5.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the invention provides a preparation method of lipophilic black phosphorus lubricating oil, which comprises the following steps:
(1) grinding the black phosphorus crystal powder into fine powder, and drying in vacuum to obtain black phosphorus nanosheet fine powder;
(2) modifying the black phosphorus nanosheet by using a lipophilic modifying material to obtain a modified black phosphorus nanosheet;
(3) and mixing the modified black phosphorus nanosheet with base lubricating oil to prepare the lipophilic black phosphorus lubricating oil.
According to the lipophilic black phosphorus lubricating oil prepared by the embodiment of the invention, the surface of the oil-based lubricating liquid contains lipophilic functional groups, and the oil-based lubricating liquid has good dispersibility in the lubricating oil and an ultralow friction coefficient on bearing steel. Compared with the traditional lubricating fluid (the friction coefficient of the common lubricant is about 0.1). The lipophilic black phosphorus lubricating oil prepared by the embodiment of the invention can reduce the friction coefficient between friction pairs to be below 0.01, and has extremely low friction coefficient and good dispersibility. The ultra-low friction coefficient effect and the good abrasion resistance brought by the invention enable the lubricating fluid to have wide application range, such as: cutting, bearing and the like, and has great practical value. Due to the unique structure of the black phosphorus nanosheet, the lipophilic black phosphorus lubricating oil has good photoelectric conversion efficiency, high electron mobility and excellent biocompatibility, and has good application prospects in the fields of thin film transistors, photoelectric detection, light-operated electronic elements, electroluminescence and biomedicine.
The preparation method of the lipophilic black phosphorus lubricating oil comprises the step (1), wherein the granularity of the fine powder is 200-500 microns.
The preparation method of the lipophilic black phosphorus lubricating oil comprises the step (1), wherein the vacuum degree of vacuum drying is 20-30 kPa, and the drying time is 4-6 hours.
According to the preparation method of the lipophilic black phosphorus lubricating oil, in the step (2), the lipophilic modified material contains a lipophilic group, and the lipophilic group contains alkyl, phenyl or cycloalkyl. In some embodiments, the oleophilic-modifying material is a mixed powder formed from n-decylcyclohexane powder and n-decyltriethoxysilane powder.
The application research of black phosphorus in the field of lubrication is relatively less, the friction coefficient of the existing lubrication products is about 0.1 generally, and the black phosphorus is difficult to disperse in the lubricating oil. While n-decylcyclohexane and n-decyltriethoxysilane are specific lipophilic functional groups. Therefore, the black phosphorus nanosheet can be well dispersed in lubricating oil and the lubricating performance can be regulated and controlled by regulating and modifying a cyclic alkyl chain or a silane chain on the surface of the black phosphorus.
The preparation method of the lipophilic black phosphorus lubricating oil provided by the invention is characterized in that in the step (2), the modification process is as follows:
(1) forming a first mixed powder by using n-decylcyclohexane powder and n-decyltriethoxysilane powder, wherein the mass ratio of the n-decylcyclohexane powder to the n-decyltriethoxysilane powder in the first mixed powder is as follows: 1(0.5 to 1);
(2) mixing the black phosphorus nanosheet fine powder with the first mixed powder to obtain second mixed powder, wherein the second mixed powder comprises the black phosphorus nanosheet fine powder and the first mixed powder in a mass ratio of: (2-7) 1;
(3) mixing the second mixed powder with water, wherein the mass ratio of the second mixed powder to the water is as follows: 20000 (1-4), reacting at 120-150 ℃ for 5-6 hours;
(4) and (4) drying in vacuum to obtain the modified black phosphorus nanosheet.
In some embodiments, the vacuum degree of the vacuum drying is 20-30 kPa, and the drying time is 4-6 hours.
In one embodiment, the oil-based lubricating fluid is a polyalphaolefin base oil.
The black phosphorus nanosheet and base oil such as polyalphaolefin base oil form lipophilic black phosphorus nanosheet, wherein the lipophilic black phosphorus nanosheet contains a large number of lipophilic functional groups (such as benzene rings, alkyl groups and the like), and the surface functional groups and the high specific surface area-to-volume ratio enable the black phosphorus as an additive to have better lubricating performance in a lubricating liquid; secondly, the functional groups are beneficial to grafting the lipophilic functional groups on the black phosphorus sheet layer, so that the nano sheet is well dispersed, the agglomeration phenomenon of the black phosphorus nano sheet in oil is avoided, and a good dispersing effect can be achieved without adding any surfactant or dispersant; meanwhile, the black phosphorus functional group strengthens a matrix-filler interface and improves the mechanical property of the lubricating liquid. The degree of oxidation of the nano material can be regulated and controlled by regulating the concentration and the content of the oxidant, namely the quantity of hydrophilic functional groups on the surface of the oxidized nano material is regulated and controlled, so that the performance of the water-based lubricating fluid is regulated and controlled.
In some embodiments, an oleophilic black phosphorus lubricating oil is prepared by the following process:
(1) mixing the modified black phosphorus nanosheet with base lubricating oil, wherein the mass ratio of the modified black phosphorus nanosheet to the base lubricating oil is as follows: (0.01-0.5) 1, heating the obtained mixed solution in a water bath, and stirring to obtain black phosphorus lubricating oil;
the inventors found that when the modified black phosphorus nanosheet is mixed with the base lubricating oil, if the content of the modified black phosphorus nanosheet is too low, the friction coefficient is higher, and if the content of the lipophilic black phosphorus nanosheet is too high, the friction coefficient is also higher, so that the ratio of the modified black phosphorus nanosheet to the base lubricating oil must be within a reasonable range.
(2) And (3) carrying out vibration treatment on the black phosphorus lubricating oil, carrying out centrifugal separation on the black phosphorus lubricating oil after vibration treatment, and obtaining supernatant fluid which is the lipophilic black phosphorus lubricating oil after centrifugal separation.
In some embodiments, the stirring is magnetic stirring, the frequency is 20 to 60Hz, the temperature is 60 to 80 ℃, and the stirring time is 50 to 60 min.
In some embodiments, the vibration treatment is ultrasonic vibration treatment for 6-8 hours at a temperature of 30-80 ℃.
In some embodiments, the centrifugal separation is performed at a rotation speed of 2000-3000 rpm for 50-60 min.
The lipophilic black phosphorus lubricating oil disclosed by the embodiment of the invention contains lipophilic functional groups on the surface, has good dispersibility in oil, and has excellent lubricating property and ultralow friction coefficient. Compared with the traditional lubricating oil (the friction coefficient of the common lubricant is about 0.1), the lubricating oil provided by the embodiment of the invention can reduce the friction coefficient between the friction pairs to be below 0.01, has an extremely low friction coefficient, and the friction pairs are made of bearing steel and the like and are close to actual working conditions. The lubricating oil provided by the embodiment of the invention has an ultralow friction coefficient effect, good wear resistance and good adaptability, so that the lubricating oil can be widely applied to the fields of engines, rail transit, machining and manufacturing, aerospace and the like.
In the examples of the present invention, the specific kind of the base lubricant is not particularly limited, and those skilled in the art can freely select the base lubricant according to actual needs, and as a preferable scheme, the examples of the present invention are more preferably polyalphaolefin base oils.
In the embodiment of the present invention, the specific kind of the lipophilic two-dimensional material is not particularly limited, and may be arbitrarily selected by a person skilled in the art according to actual needs, and as a preferred scheme, the lipophilic two-dimensional material is selected from black phosphorus, graphene, carbon nanotubes, fullerene, transition metal carbide, boron nitride, molybdenum disulfide, and the like; black phosphorus is more preferred.
In the embodiment of the present invention, the kind of the lipophilic group is not particularly limited, and one skilled in the art can freely select the lipophilic group according to actual needs, and as a preferable embodiment, the lipophilic group is selected from the group consisting of alkyl group, phenyl group, cycloalkyl group, etc.; more preferably powders with alkyl and cycloalkyl functionalities.
In the embodiment of the present invention, the specific size of the black phosphorus nanosheet is not particularly limited, and one skilled in the art can optionally select the black phosphorus nanosheet according to actual needs, and as a preferred scheme, the black phosphorus nanosheet has a monolayer thickness of 0.5-0.9nm, a monolayer length of 20-150nm, a monolayer width of 10-180nm, and the number of layers of the black phosphorus nanosheet is 1-10. The inventors found that if the black phosphorus nanosheets are too large in size, wear of the friction pair increases, and if they are too small in size, the production cost increases.
The modified black phosphorus nanosheet with good lipophilicity, which is prepared by the embodiment of the invention, has a large number of oxygen-containing functional groups, hydroxyl groups and the like, and the surface functional groups and the high specific surface area volume ratio enable the lipophilic black phosphorus nanosheet to be used as an additive to have better lubricating property in lubricating oil; secondly, the functional groups are beneficial to good dispersion of the black phosphorus nanosheets, the black phosphorus nanosheets are prevented from agglomerating and precipitating in oil, and a good dispersion effect can be achieved without adding any surfactant or dispersant; meanwhile, the inherent characteristics of the black phosphorus nanosheets enhance the matrix-filler interface and improve the mechanical properties of the lubricating liquid.
According to the embodiment of the invention and the preparation method of the oil-based lubricating fluid, the preparation method is simple and easy to implement, the preparation raw materials are simple and easy to obtain, and the cost is low. The oil-based lubricating fluid prepared by the method has lipophilic functional groups, good dispersibility in most of oil, good stability, ultralow friction coefficient and higher wear resistance. Compared with the traditional lubricating liquid (the friction coefficient of a common lubricant is about 0.1), the lubricating liquid disclosed by the invention can reduce the friction coefficient between friction pairs to be below 0.01, has an extremely low friction coefficient, and has excellent wear resistance and pressure resistance. The ultra-low friction coefficient effect and the good abrasion resistance brought by the invention enable the lubricating fluid to have wide application range, such as: cutting, engine, bearing, etc., and has great practical application value.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to one skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
(1) Weighing 10 parts by weight of black phosphorus crystals with the purity of 99.5%, putting the black phosphorus crystals into a physical grinder, introducing nitrogen into the physical grinder, sealing, and then starting grinding at the speed of 1500rpm for 50min, and drying under the vacuum degree of 20kPa for 5 hours to obtain superfine black phosphorus nanosheet fine powder with the granularity of 400 microns;
(2) mixing n-decylcyclohexane powder and n-decyltriethoxysilane powder in a mass ratio of 1:1 to form first mixed powder, mixing the black phosphorus nanosheet fine powder prepared in the step (1) with the first mixed powder in a mass ratio of 5:1 to obtain second mixed powder, mixing the second mixed powder with water in a mass ratio of 20000:6, reacting at 150 ℃ for 4 hours, and drying at a vacuum degree of 20kPa for 4 hours to obtain the modified black phosphorus nanosheet.
(3) Mixing the modified black phosphorus nanosheet and the polyalphaolefin base oil in the step (2) according to the mass ratio of 0.2:1, placing the obtained mixed solution in a reaction kettle, heating in a water bath, magnetically stirring at the frequency of 30Hz and the temperature of 60 ℃ for 60min to obtain black phosphorus lubricating oil; and (3) carrying out ultrasonic vibration treatment on the black phosphorus lubricating oil for 8 hours at the temperature of 50 ℃, and carrying out centrifugal separation on the black phosphorus lubricating oil after vibration treatment, wherein the rotating speed of the centrifugal separation is 2000rpm, and the separation time is 30 min. The supernatant obtained by centrifugal separation is the lipophilic black phosphorus lubricating oil.
The obtained lipophilic black phosphorus lubricating oil is subjected to friction performance test, the specific test method is to adopt a UMT-5 friction wear tester to carry out the friction performance test, a reciprocating mode is adopted, a friction pair ball is a bearing steel small ball with the length of 4mm, a friction pair is a diamond-like carbon film bearing steel block with the length of 20mm, the width of 20mm and the thickness of 5mm, the load is 3N, and the reciprocating speed frequency range is 6 Hz. The change curve of the friction coefficient of the lipophilic black phosphorus lubricating oil in the plane of the bearing steel ball and the diamond-like carbon film bearing steel block along with time is shown in figure 1. As can be seen from the figure, the coefficient of friction of the lipophilic black phosphorus lubricating oil of the present embodiment gradually decreases with the wear time, and after a short running time and (running and time less than 100 seconds), the coefficient of friction becomes ultra-smooth and relatively stable, and the lowest coefficient of friction is about 0.008. Compared to the coefficient of friction lubricated with the polyalphaolefin base oil of example 1 after addition of the lipophilic modified black phosphorus nanoplates, the stable coefficient of friction when lubricated with only the polyalphaolefin base oil was about 0.1. Therefore, the addition of the lipophilic modified black phosphorus nanosheet in example 1 can effectively reduce the friction coefficient.
Example 2
(1) Weighing 10 parts by weight of black phosphorus crystals with the purity of 99.5 percent, putting the black phosphorus crystals into a physical crusher, introducing nitrogen into the physical crusher, sealing, and then starting crushing at the crushing speed of 1500rpm for 50min, and drying for 5 hours under the vacuum degree of 20kPa to obtain superfine black phosphorus powder with the granularity of 400 microns;
(2) mixing n-decylcyclohexane powder and n-decyltriethoxysilane powder in a ratio of 1:1 to form first mixed powder, mixing the black phosphorus nanosheet fine powder prepared in the step (1) with the first mixed powder in a ratio of 5:1 to obtain second mixed powder, mixing the second mixed powder with water, wherein the mass ratio of the second mixed powder to the water is as follows: 20000:6, reacting at 150 ℃ for 4 hours, and drying under 20kPa vacuum degree for 4 hours to obtain the modified black phosphorus nanosheet.
(3) Mixing the modified black phosphorus nanosheet obtained in the step (2) with poly-alpha-olefin base oil according to the mass ratio of: mixing at a ratio of 0.2:1, placing the obtained mixed solution in a reaction kettle, heating in a water bath, magnetically stirring at a frequency of 30Hz and a temperature of 60 ℃, and stirring for 60min to obtain black phosphorus lubricating oil; and (3) carrying out ultrasonic vibration treatment on the black phosphorus lubricating oil for 8 hours at the temperature of 50 ℃, and carrying out centrifugal separation on the black phosphorus lubricating oil after vibration treatment, wherein the rotating speed of the centrifugal separation is 2000rpm, and the separation time is 30 min. The supernatant obtained by centrifugal separation is the lipophilic black phosphorus lubricating oil.
The prepared lipophilic black phosphorus lubricating oil is subjected to long-time friction performance exploration. The obtained lipophilic black phosphorus lubricating oil is used for friction performance test, the specific test method is to adopt a UMT-5 friction wear tester for friction performance test, a reciprocating mode is adopted, a friction pair ball is a bearing steel small ball with the length of 4mm, a pair grinding pair is a diamond-like thin film bearing steel block with the length of 20mm, the width of 20mm and the thickness of 5mm, the load is 3N, and the reciprocating speed frequency range is 6 Hz. The variation curve of the friction coefficient of the lipophilic black phosphorus oil-based lubricating fluid between the bearing steel ball and the diamond-like carbon film bearing steel block along with time is shown in figure 2. As can be seen from fig. 2, the friction coefficient of the lipophilic black phosphorus lubricating oil tends to decrease first and then to be relatively stable with the increase of time, and the friction coefficient can be kept relatively stable, and the stable time is longer than 3 hours.
Example 3
(1) Weighing 10 parts by weight of black phosphorus crystals with the purity of 99.5 percent, putting the black phosphorus crystals into a physical crusher, introducing nitrogen into the physical crusher, sealing, and then starting crushing at the crushing speed of 1500rpm for 50min, and drying for 5 hours under the vacuum degree of 20kPa to obtain superfine black phosphorus powder with the granularity of 400 microns;
(2) mixing n-decylcyclohexane powder and n-decyltriethoxysilane powder in a ratio of 1:1 to form first mixed powder, mixing the black phosphorus nanosheet fine powder prepared in the step (1) with the first mixed powder in a ratio of 5:1 to obtain second mixed powder, mixing the second mixed powder with water, wherein the mass ratio of the second mixed powder to the water is as follows: 20000:6, reacting at 150 ℃ for 4 hours, and drying under 20kPa vacuum degree for 4 hours to obtain the modified black phosphorus nanosheet.
(3) Mixing the modified black phosphorus nanosheet obtained in the step (2) with polyalphaolefin base oil in a mass ratio of: mixing at a ratio of 0.2:1, placing the obtained mixed solution in a reaction kettle, heating in a water bath, magnetically stirring at a frequency of 30Hz and a temperature of 60 ℃, and stirring for 60min to obtain black phosphorus lubricating oil; and (3) carrying out ultrasonic vibration treatment on the black phosphorus lubricating oil for 8 hours at the temperature of 50 ℃, and carrying out centrifugal separation on the black phosphorus lubricating oil after vibration treatment, wherein the rotating speed of the centrifugal separation is 2000rpm, and the separation time is 30 min. The supernatant obtained by centrifugal separation is the lipophilic black phosphorus lubricating oil.
The friction performance of the prepared lipophilic black phosphorus lubricating oil under different loads is tested by adopting a UMT-5 friction wear tester to test the friction performance, a reciprocating mode is adopted, a friction pair ball is a bearing steel small ball with the diameter of 4mm, a friction pair is a diamond-like thin film bearing steel block with the length of 20mm, the width of 20mm and the thickness of 5mm, the load range is 1-4N, and the reciprocating speed frequency range is 6 Hz. The variation curve of the friction coefficient of the lipophilic black phosphorus oil-based lubricating fluid between the bearing steel ball and the diamond-like carbon film bearing steel block along with time is shown in fig. 3. As can be seen from FIG. 3, there is a load range (1-3N) using the lipophilic black phosphorus lubricating oil such that the coefficient of friction is below 0.01 and is in a super-lubricious condition.
Example 4
(1) Weighing 10 parts by weight of black phosphorus crystals with the purity of 99.5 percent, putting the black phosphorus crystals into a physical crusher, introducing nitrogen into the physical crusher, sealing, and then starting crushing at the crushing speed of 1500rpm for 50min, and drying under the vacuum degree of 20kPa for 5 hours to obtain superfine black phosphorus powder with the granularity of 400 micrometers;
(2) mixing n-decylcyclohexane powder and n-decyltriethoxysilane powder in a ratio of 1:1 to form first mixed powder, mixing the black phosphorus nanosheet fine powder prepared in the step (1) with the first mixed powder in a ratio of 5:1 to obtain second mixed powder, and mixing the second mixed powder with water, wherein the mass ratio of the second mixed powder to the water is as follows: 20000:6, reacting at 150 ℃ for 4 hours, and drying under 20kPa vacuum degree for 4 hours to obtain the modified black phosphorus nanosheet.
(3) Mixing the modified black phosphorus nanosheet obtained in the step (2) with poly-alpha-olefin base oil according to the mass ratio of: mixing at ratio of 0.05-0.5:1, placing the obtained mixed solution in a reaction kettle, heating in water bath, magnetically stirring at 60 deg.C and frequency of 30Hz for 60min to obtain black phosphorus lubricating oil; and (3) carrying out ultrasonic vibration treatment on the black phosphorus lubricating oil for 8 hours at 50 ℃, and carrying out centrifugal separation on the black phosphorus lubricating oil after vibration treatment, wherein the rotating speed of the centrifugal separation is 2000rpm, and the separation time is 30 min. The supernatant obtained by centrifugal separation is the lipophilic black phosphorus lubricating oil.
The obtained lipophilic black phosphorus lubricating oil with different concentrations is subjected to friction performance test, the specific test method is to adopt a UMT-5 friction wear tester to carry out the friction performance test, a reciprocating mode is adopted, a friction pair ball is a bearing steel small ball with the length of 4mm, a friction pair is a diamond-like carbon film bearing steel block with the length of 20mm, the width of 20mm and the thickness of 5mm, the load is 3N, and the reciprocating speed frequency range is 6 Hz. As can be seen from fig. 4, there is a range of concentrations for the coefficient of friction of the oleophilic black phosphorus lubricating oil at different concentrations, and ultra-low wear can be achieved at concentrations ranging from 0.2 to 0.4 wt.%.
Example 5
(1) Weighing 10 parts by weight of black phosphorus crystals with the purity of 99.5 percent, putting the black phosphorus crystals into a physical crusher, introducing nitrogen into the physical crusher, sealing, and then starting crushing at the crushing speed of 1500rpm for 50min, and drying under the vacuum degree of 20kPa for 5 hours to obtain superfine black phosphorus powder with the granularity of 400 micrometers;
(2) mixing n-decylcyclohexane powder and n-decyltriethoxysilane powder in a ratio of 1:1 to form first mixed powder, mixing the black phosphorus nanosheet fine powder prepared in the step (1) with the first mixed powder in a ratio of 5:1 to obtain second mixed powder, and mixing the second mixed powder with water, wherein the mass ratio of the second mixed powder to the water is as follows: 20000:6, reacting at 150 ℃ for 4 hours, and drying under 20kPa vacuum degree for 4 hours to obtain the modified black phosphorus nanosheet.
(3) Mixing the modified black phosphorus nanosheet obtained in the step (2) with polyalphaolefin base oil in a mass ratio of: mixing at a ratio of 0.2:1, placing the obtained mixed solution in a reaction kettle, heating in a water bath, magnetically stirring at a frequency of 30Hz and a temperature of 60 ℃, and stirring for 60min to obtain black phosphorus lubricating oil; and (3) carrying out ultrasonic vibration treatment on the black phosphorus lubricating oil for 8 hours at the temperature of 50 ℃, and carrying out centrifugal separation on the black phosphorus lubricating oil after vibration treatment, wherein the rotating speed of the centrifugal separation is 2000rpm, and the separation time is 30 min. The supernatant obtained by centrifugal separation is the lipophilic black phosphorus lubricating oil.
The friction performance of the obtained lipophilic black phosphorus lubricating oil is tested, and the specific test method is to test the friction performance at different speeds by adopting a UMT-5 friction wear tester, wherein a reciprocating mode is adopted, a friction pair ball is a bearing steel small ball with the diameter of 4mm, a friction pair is a diamond-like thin film bearing steel block with the length of 20mm, the width of 20mm and the thickness of 5mm, the load is 3N, and the reciprocating speed frequency range is 1-9 Hz. As can be seen from FIG. 5, there is a range of reciprocation speed frequencies for the coefficient of friction using the oleophilic black phosphorus lubricant oil, and ultra low wear can be achieved at reciprocation speed frequencies in the range of 6-8 Hz.
In the description of the specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of lipophilic black phosphorus lubricating oil is characterized by comprising the following steps:
(1) grinding the black phosphorus crystal powder into fine powder, and drying in vacuum to obtain black phosphorus nanosheet fine powder;
(2) modifying the black phosphorus nanosheet fine powder by using a lipophilic modifying material to obtain a modified black phosphorus nanosheet;
(3) mixing the modified black phosphorus nanosheet with base lubricating oil to prepare lipophilic black phosphorus lubricating oil,
wherein in the step (1), the black phosphorus crystal powder is ground into fine powder with the granularity of 200-500 microns,
in the step (2), the lipophilic modification material is mixed powder formed by n-decylcyclohexane powder and n-decyltriethoxysilane powder.
2. The method for preparing lipophilic black phosphorus lubricating oil according to claim 1, wherein in the step (1), the vacuum degree of vacuum drying is 20 to 30kPa, and the drying time is 4 to 6 hours.
3. The method for preparing lipophilic black phosphorus lubricating oil according to claim 1, wherein in the step (2), the modification process comprises:
(a) mixing the components in a mass ratio of 1: (0.5-1) forming a first mixed powder from n-decylcyclohexane powder and n-decyltriethoxysilane powder;
(b) mixing the black phosphorus nanosheet fine powder and the first mixed powder in a mass ratio of (2-7) to 1 to obtain second mixed powder;
(c) mixing the second mixed powder with the mass ratio of 20000 (1-4) with water, and reacting for 5-6 hours at the temperature of 120-150 ℃;
(d) and (c) carrying out vacuum drying on the material reacted in the step (c) to obtain the modified black phosphorus nanosheet.
4. The method for preparing lipophilic black phosphorus lubricating oil according to claim 3, wherein in the step (d), the vacuum degree of the vacuum drying is 20 to 30kPa, and the drying time is 4 to 6 hours.
5. The method of preparing a lipophilic black phosphorus lubricating oil according to claim 1 or 4, wherein in step (3), the base lubricating oil is a polyalphaolefin base oil.
6. The method for preparing lipophilic black phosphorus lubricating oil according to claim 1, wherein in the step (3), the process for preparing lipophilic black phosphorus lubricating oil comprises:
(I) mixing the modified black phosphorus nanosheets and the base lubricating oil in a mass ratio of (0.01-0.5): 1, heating the obtained mixed solution in a water bath, and stirring to obtain black phosphorus lubricating oil;
(II) carrying out vibration treatment on the black phosphorus lubricating oil, then carrying out centrifugal separation, and obtaining supernatant fluid which is the lipophilic black phosphorus lubricating oil through centrifugal separation.
7. The method for preparing lipophilic black phosphorus lubricating oil according to claim 6, wherein in the step (I), the stirring is magnetic stirring, the frequency is 20 to 60Hz, the temperature is 60 to 80 ℃, and the stirring time is 50 to 60 min.
8. The method for preparing the lipophilic black phosphorus lubricating oil according to claim 6, wherein in the step (II), the vibration treatment is ultrasonic vibration treatment for 6-8 hours at a temperature of 30-80 ℃.
9. The method for preparing lipophilic black phosphorus lubricating oil according to claim 6, wherein the rotation speed of the centrifugal separation is 1000-3000 rpm, and the separation time is 30-60 min.
10. A lipophilic black phosphorus lubricating oil, characterized by being produced by the method according to any one of claims 1 to 9.
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