CN113718202A - Preparation method and application of graphite alkyne lubricating film - Google Patents

Preparation method and application of graphite alkyne lubricating film Download PDF

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CN113718202A
CN113718202A CN202111045436.9A CN202111045436A CN113718202A CN 113718202 A CN113718202 A CN 113718202A CN 202111045436 A CN202111045436 A CN 202111045436A CN 113718202 A CN113718202 A CN 113718202A
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graphite alkyne
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CN113718202B (en
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公培伟
李娟�
刘哲
赵凯
刘建喜
徐书生
刘维民
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Qufu Normal University
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    • C—CHEMISTRY; METALLURGY
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    • F16N—LUBRICATING
    • F16N15/00—Lubrication with substances other than oil or grease; Lubrication characterised by the use of particular lubricants in particular apparatus or conditions
    • F16N15/02—Lubrication with substances other than oil or grease; Lubrication characterised by the use of particular lubricants in particular apparatus or conditions with graphite or graphite-containing compositions

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Abstract

The invention discloses a preparation method and application of a graphite alkyne lubricating film, wherein the method comprises the following steps: (1) using monocrystalline silicon as a substrate, depositing a copper nano film on the surface of the monocrystalline silicon by using a physical vapor deposition method, wherein the deposition temperature is not lower than 110 ℃, and immediately and rapidly cooling the copper nano film after the deposition is finished to obtain the substrate deposited with the copper nano film for later use; (2) and (2) carrying out coupling reaction on hexaalkynyl benzene in a solvent, and generating a graphite alkyne film on the surface of the copper nano film of the substrate obtained in the step (1). The graphite alkyne film prepared by the method has a good lubricating effect, particularly keeps excellent lubricating property under long-term abrasion, has stable lubricating property, and ensures that the graphite alkyne film prepared by the method has a good application prospect in the field of mechanical engineering.

Description

Preparation method and application of graphite alkyne lubricating film
Technical Field
The invention relates to the technical field of preparation of solid lubricating materials, in particular to a preparation method and application of a graphite alkyne lubricating film.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
As is well known, friction and wear are prevalent in industrial production and nature, and this process results in a great deal of energy dissipation and material waste. The lubrication technology has been considered as the most effective method for reducing mechanical wear and prolonging the service life of equipment, and among various lubrication technologies and materials, the solid lubricant can be used for special working conditions such as high vacuum, strong radiation, high and low temperature, and has the advantages of small volume, no need of sealing, long service life and the like. In particular solid lubricants based on carbon materials, by changing sp, sp2And SP3The carbon-based composite material is formed by periodic bonding motif in a network formed by hybridized carbon atoms, has a two-dimensional layered structure, has weak van der Waals force among molecules, is easy to slide among layers, has the advantages of large specific surface area, high strength, light weight, good flexibility, various preparation methods and the like, and can effectively improve the wear-resistant and anti-friction properties of the material.
At present, solid lubricating materials such as carbon nanotubes, graphite, fullerene, graphene and the like are widely applied to the field of friction to improve the wear resistance and wear resistance of a friction pair. In particular, a thin film lubricant such as graphene has been widely used because of its special structure, excellent mechanical properties, stable chemical properties, good thermal conductivity, good electron fluidity, and the like. The graphene film material with the nano thickness has good self-lubricating property and strong binding force, and can be applied to precise instruments and equipment, so that the carbon-based lubricating film has great research value and application prospect.
The graphdine as a novel carbon material has excellent performances such as a highly conjugated 2D structure, remarkable electronic properties, high carrier mobility, good stability and the like. Theoretical calculations show that, compared with other carbon materials known at present, the existence of acetylene bonds has a remarkable influence on the mechanical properties of graphite, and the acetylene bonds in the graphathpane endow the graphathpane with better flexibility, so that the breaking strain of the graphathpane is correspondingly improved. The graphite alkyne has extremely high mechanical strength, low shear strength and high surface area, so that the graphite alkyne has a huge application prospect in the fields of tribology and lubrication. In recent years, great progress is made in the preparation of graphite alkyne block materials, and the preparation is mainly divided into a dry chemical method and a wet chemical method. The dry chemical synthesis method mainly comprises a scanning tunnel microscope, surface synthesis in a chemical vapor deposition system, an explosion method and a top-down method, and the wet chemical synthesis method mainly comprises copper surface mediated synthesis, interface assisted synthesis and solid phase Van der Waals epitaxy. Wet chemistry methods provide a more efficient method for preparing large area graphdine materials suitable for practical use than dry chemistry methods. However, the above-mentioned techniques cannot effectively synthesize a solid lubricating film, and are mainly due to the problems of poor binding property with a substrate, uneven growth, rough surface, poor lubricating property, and the like of the graphite alkyne film synthesized by the above-mentioned methods.
The prior art discloses a graphite alkyne film and a preparation method and application thereof, wherein a copper sheet or a substrate with any surface covered with a copper film layer is used as a substrate, and hexaalkynyl benzene is subjected to coupling reaction under the catalysis of copper to obtain the graphite alkyne film. However, the inventor finds that the surface of the graphite alkyne film prepared by the method is rough, the film grows unevenly, the lubricating property is poor when the graphite alkyne film is used as a lubricating film, and the excellent lubricating potential of the graphite alkyne as a lubricating material is not exerted. Therefore, the inventor believes that an effective method and technology for preparing a graphite alkyne film with a uniform surface and enabling the film material to have good lubricating property are still lacking.
Disclosure of Invention
In order to solve the problems, the invention researches and discovers that: when the graphite alkyne film is deposited on a copper sheet or a substrate with any surface covered with the copper film layer, the appearance of the copper film layer has great influence on the surface appearance of the graphite alkyne film, and further influences the lubricating property of the graphite alkyne film. On the basis, the invention provides a preparation method of the graphite alkyne lubricating film, which can effectively overcome the problems, and the prepared graphite alkyne film can obtain good lubricity when being used as a solid lubricating material.
Specifically, to achieve the above object, the technical solution of the present invention is as follows:
in a first aspect of the present invention, a method for preparing a graphite alkyne lubricating film is disclosed, comprising:
(1) using monocrystalline silicon as a substrate, depositing a copper nano film on the surface of the monocrystalline silicon by using a Physical Vapor Deposition (PVD) method, wherein the deposition temperature is not lower than 110 ℃, and immediately and rapidly cooling the copper nano film after the deposition is finished to obtain the substrate deposited with the copper nano film for later use.
(2) And (2) carrying out coupling reaction on hexaalkynyl benzene (HEB) in a solvent, depositing the hexaalkynyl benzene (HEB) on the surface of the copper nano film of the substrate obtained in the step (1), and drying the graphite alkyne film deposited on the surface of the copper nano film to obtain the graphene nano film.
Further, in step (1), the method for rapid cooling comprises: and (5) placing the substrate deposited with the copper nano film in a cooling device for cooling to obtain the copper nano film. The copper atoms can be pinned in a short time through rapid cooling, and the copper atoms are prevented from agglomerating on the surface of the monocrystalline silicon substrate.
Further, in the step (1), the deposition temperature is controlled to be between 110 and 150 ℃, and more preferably, between 110 and 135 ℃.
Further, in the step (1), the power in the physical vapor deposition is 18-25W, and the deposition time is kept at 4-5.5 min. Compared with other methods, the physical vapor deposition technology can effectively avoid the problem that the copper nano film is not uniformly distributed on the surface of the substrate, and further ensures that the synthesized graphite alkyne film has good integrity and uniformity.
Further, in the step (1), before deposition, the deposition surface of the monocrystalline silicon is cleaned by ethanol and ether respectively, and then bombarded in argon plasma to remove impurities, oxide layers and the like on the surface of the monocrystalline silicon, so as to obtain a clean substrate.
Further, in the step (2), the substrate deposited with the copper nano-film is placed in pyridine, and then hexaalkynyl benzene is added to perform a coupling reaction under the catalysis of the copper nano-film, so that the hexaalkynyl benzene reacts to generate the graphite alkyne film deposited on the surface of the copper nano-film.
Further, in the step (2), the coupling reaction is performed in an oxygen-free and light-shielded environment in the whole process, because (hexaalkynyl benzene) is unstable in chemical property, is easily decomposed by light, and is easily oxidized in oxygen.
Further, in the step (2), the mass volume ratio of the hexaalkynyl benzene to the pyridine is 0.008-0.009 g: 20-25 mL.
Further, in the step (2), the coupling reaction is carried out under heating conditions, optionally, the heating temperature is controlled between 60 ℃ and 65 ℃, and the reaction time is 5 to 9 days.
Further, in the step (2), the graphite alkyne film deposited on the surface of the copper nano film is taken down, repeatedly washed by nitrogen-nitrogen Dimethylformamide (DMF) and ethanol, and then dried, so that the graphite alkyne film is obtained.
Further, in the step (2), the method for preparing hexaalkynyl benzene comprises the following steps: dissolving hexa (trimethylsilyl ethynyl) benzene (HEB-TMS) in tetrahydrofuran, adding tetrabutylammonium fluoride (TBAF) solution after reaction, reacting under anaerobic and dark conditions (preferably at-8-0 ℃), diluting the reaction solution with ethyl acetate, washing with saturated salt solution, extracting an organic phase, drying with anhydrous magnesium sulfate, and carrying out freeze drying treatment to obtain the graphite alkyne monomer: hexaalkynyl benzene.
In a second aspect of the invention, the application of the graphite alkyne lubricating film as a solid lubricating material in the fields of friction, lubrication and the like is disclosed.
Compared with the prior art, the invention has the following beneficial effects:
in order to overcome the adverse effect of a common substrate on the surface appearance of the graphite alkyne film, the invention carries out technical optimization and improvement on the following aspects. Secondly, the invention adopts the PVD technology to deposit the copper nano-film on the surface of the monocrystalline silicon, thereby effectively avoiding the problem that the copper nano-film is not uniformly distributed on the surface of the substrate and ensuring that the synthesized graphite alkyne film has good integrity and uniformity. Thirdly, the invention adopts the technology of rapidly cooling the nano copper film immediately after high-temperature deposition at the temperature of 110 ℃ and above, so that copper atoms are pinned on the surface of the monocrystalline silicon substrate in a short time, and the copper atoms are prevented from agglomerating on the surface of the monocrystalline silicon substrate, because the copper atoms under the nanoscale have good migration capacity at high temperature, and if the nano copper atoms are not rapidly cooled, the agglomeration phenomenon easily occurs under the short-time high-temperature condition after the deposition is finished, and the problem that the surface of the obtained nano copper film is uneven, uneven and even incomplete is caused. These defects, in turn, significantly affect the lubricity of the resulting graphite alkyne film. After the technology provided by the invention is adopted, the prepared graphite alkyne film has a good lubricating effect (the friction coefficient is about 0.1), particularly still keeps excellent lubricating performance (the friction coefficient is about 0.12) under long-time abrasion, has high stable lubricating performance, and ensures that the graphite alkyne film prepared by the invention has a good application prospect in the field of mechanical engineering.
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 exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is a diagram illustrating the effect of the graphite alkyne film prepared in the first embodiment of the present invention.
Fig. 2 is a raman bopp diagram of the graphone thin film prepared in the first embodiment of the present invention.
FIG. 3 is a transmission electron micrograph of a graphdine thin film prepared according to the first embodiment of the present invention.
Fig. 4 is a graph of friction data of the graphite acetylene lubricating film prepared in the first example and the single crystal silicon substrate used in the preparation thereof.
Fig. 5 is a graph showing friction data of the graphite acetylene lubrication film produced in each of the first and fourth examples and the single-crystal silicon substrate used in the production thereof.
Fig. 6 is a graph showing friction data of the graphite acetylene lubricating film produced in each of the first, fifth, and sixth examples and the single-crystal silicon substrate used in the production of the film in the first example.
Fig. 7 is an SEM image of the graphite acetylene lubrication film prepared in the first example after a friction test.
Fig. 8 is a graph of friction data of the graphite acetylene lubrication film prepared in the first example and the single crystal silicon substrate used in the preparation thereof under different load conditions.
Detailed Description
In the following description, further specific details of the invention are set forth in order to provide a thorough understanding of the invention. The terminology used in the description of the invention herein is for the purpose of describing particular advantages and features of the invention only and is not intended to be limiting of the invention.
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. Unless otherwise indicated, the drugs or agents used in the present invention are used according to the instructions of the product or by the conventional methods in the art. The technical solution of the present invention will be further explained with reference to the drawings and the detailed description of the specification.
First embodiment
The preparation method of the graphite alkyne lubricating film comprises the following steps:
(1) synthesis of graphyne monomer (HEB): dissolving 50mg of HEB-TMS in 17mL of tetrahydrofuran, reacting in an ice-water bath, adding 0.5mL of tetrabutylammonium fluoride solution, reacting for 30 minutes under oxygen-free and dark conditions, diluting the reaction solution with ethyl acetate, washing with saturated saline, extracting an organic phase, drying with anhydrous magnesium sulfate, performing rotary evaporation at 45 ℃ for spin-drying, and performing freeze-drying treatment to obtain HEB for later use. It should be noted that the HEB can also be prepared by other methods, and is not limited to the method mentioned in this example.
(2) Preparation of a specific graphyne substrate:
before deposition, cleaning the surface of a monocrystalline silicon wafer by using ethanol and diethyl ether, and then bombarding the monocrystalline silicon wafer in argon plasma to remove impurities, an oxide layer and the like on the surface of the monocrystalline silicon to obtain a clean substrate for later use;
at 1X 2 cm2The single crystal silicon wafer is deposited with copper by using a PVD (physical vapor deposition) technology, the pre-deposition treatment is firstly carried out in the whole argon flow state under the basic pressure in the deposition process so as to remove an oxide layer on the copper target and impurities thereof, and then the deposition of elemental copper is carried out on the single crystal silicon wafer.
The deposition process is finished at the high temperature of 115 +/-5 ℃ to achieve the effect of activating the surface of the monocrystalline silicon, the pre-deposition time is 5 minutes, the actual deposition time is five minutes, the power is 20W, the deposition mode is uninterrupted deposition, the monocrystalline silicon wafer after the deposition is finished is directly placed on a device containing condensed water to be cooled, the monocrystalline silicon wafer deposited with the nano copper film is taken out after being cooled to the constant temperature, and is dried for 5 minutes in plasma containing argon after being washed in ether and acetone, and the dried monocrystalline silicon wafer deposited with the nano copper film is obtained.
(3) Preparing a graphite alkyne lubricating film: and (3) placing the dried monocrystalline silicon wafer deposited with the nano copper film obtained in the step (2) into a three-neck flask containing 50mL of pyridine, dissolving HEB obtained in the step (1) into 25mL of pyridine, slowly dropwise adding the pyridine into the three-neck flask, wherein the dropwise adding process is sectional dropwise adding without continuous dropwise adding to achieve the effect of full reaction, heating the three-neck flask to 60 ℃ while dropwise adding, reacting under the conditions of oxygen-free protection (nitrogen atmosphere), light shielding and slow stirring, uniformly distributing the dropwise added medicines, and reacting for 7 days to obtain the graphite alkyne lubricating film.
(4) Surface treatment of a graphite alkyne lubricating film: and taking the synthesized graphite alkyne lubrication film out of the three-neck flask, sequentially washing the film for multiple times by using nitrogen-nitrogen Dimethylformamide (DMF) and ethanol, and drying the film by vacuum heating at 60 ℃ for about 60min to obtain the graphite alkyne lubrication film with a dry surface.
Second embodiment
The preparation method of the graphite alkyne lubricating film comprises the following steps:
(1) synthesis of graphyne monomer (HEB) was the same as in the first example.
(2) Preparation of a specific graphyne substrate:
before deposition, cleaning the surface of a monocrystalline silicon wafer by using ethanol and diethyl ether, and then bombarding the monocrystalline silicon wafer in argon plasma to remove impurities, an oxide layer and the like on the surface of the monocrystalline silicon to obtain a clean substrate for later use;
at 1X 2 cm2The single crystal silicon wafer is deposited with copper by using a PVD (physical vapor deposition) technology, the pre-deposition treatment is firstly carried out in the whole argon flow state under the basic pressure in the deposition process so as to remove an oxide layer on the copper target and impurities thereof, and then the deposition of elemental copper is carried out on the single crystal silicon wafer.
The deposition process is finished at a high temperature of 130 +/-5 ℃ to achieve the effect of activating the surface of the monocrystalline silicon, the pre-deposition time is 5 minutes, the actual deposition time is five minutes, the power is 20W, the deposition mode is uninterrupted deposition, the monocrystalline silicon wafer after the deposition is finished is directly placed on a device containing condensed water to be cooled, the monocrystalline silicon wafer deposited with the nano copper film is taken out after being cooled to a constant temperature, and is dried in plasma containing argon for 5 minutes after being washed in ether and acetone, and the dried monocrystalline silicon wafer deposited with the nano copper film is obtained.
(3) Preparing a graphite alkyne lubricating film: and (3) placing the dried monocrystalline silicon wafer deposited with the nano copper film obtained in the step (2) into a three-neck flask containing 50mL of pyridine, dissolving HEB obtained in the step (1) into 25mL of pyridine, slowly dropwise adding the pyridine into the three-neck flask, wherein the dropwise adding process is sectional dropwise adding without continuous dropwise adding to achieve the effect of full reaction, heating the three-neck flask to 60 ℃ while dropwise adding, reacting under the conditions of oxygen-free protection (nitrogen atmosphere), light shielding and slow stirring, uniformly distributing the dropwise added medicine, and reacting for 5 days to obtain the graphite alkyne lubricating film.
(4) Surface treatment of a graphite alkyne lubricating film: as in the first embodiment.
Third embodiment
The preparation method of the graphite alkyne lubricating film comprises the following steps:
(1) synthesis of graphyne monomer (HEB) was the same as in the first example.
(2) Preparation of a specific graphyne substrate:
before deposition, cleaning the surface of a monocrystalline silicon wafer by using ethanol and diethyl ether, and then bombarding the monocrystalline silicon wafer in argon plasma to remove impurities, an oxide layer and the like on the surface of the monocrystalline silicon to obtain a clean substrate for later use;
at 1X 2 cm2The single crystal silicon wafer is deposited with copper by using a PVD (physical vapor deposition) technology, the pre-deposition treatment is firstly carried out in the whole argon flow state under the basic pressure in the deposition process so as to remove an oxide layer on the copper target and impurities thereof, and then the deposition of elemental copper is carried out on the single crystal silicon wafer.
The deposition process is finished at a high temperature of 120 +/-5 ℃ to achieve the effect of activating the surface of the monocrystalline silicon, the pre-deposition time is 5 minutes, the actual deposition time is five minutes, the power is 20W, the deposition mode is uninterrupted deposition, the monocrystalline silicon wafer after the deposition is finished is directly placed on a device containing condensed water to be cooled, the monocrystalline silicon wafer deposited with the nano copper film is taken out after being cooled to a constant temperature, and is dried for 5 minutes in plasma containing argon after being washed in ether and acetone, and the dried monocrystalline silicon wafer deposited with the nano copper film is obtained.
(3) Preparing a graphite alkyne lubricating film: and (3) placing the dried monocrystalline silicon wafer deposited with the nano copper film obtained in the step (2) into a three-neck flask containing 50mL of pyridine, dissolving HEB obtained in the step (1) into 25mL of pyridine, slowly dropwise adding the pyridine into the three-neck flask, wherein the dropwise adding process is sectional dropwise adding without continuous dropwise adding to achieve the effect of full reaction, heating the three-neck flask to 60 ℃ while dropwise adding, reacting under the conditions of oxygen-free protection (nitrogen atmosphere), light shielding and slow stirring, uniformly distributing the dropwise added medicines, and reacting for 9 days to obtain the graphite alkyne lubricating film.
(4) Surface treatment of a graphite alkyne lubricating film: as in the first embodiment.
Fourth embodiment
The preparation method of the graphite alkyne lubricating film comprises the following steps:
(1) synthesis of graphyne monomer (HEB) was the same as in the first example.
(2) Preparation of a specific graphyne substrate:
before deposition, cleaning the surface of a monocrystalline silicon wafer by using ethanol and diethyl ether, and then bombarding the monocrystalline silicon wafer in argon plasma to remove impurities, an oxide layer and the like on the surface of the monocrystalline silicon to obtain a clean substrate for later use;
at 1X 2 cm2The single crystal silicon wafer is deposited with copper by using a PVD (physical vapor deposition) technology, the pre-deposition treatment is firstly carried out in the whole argon flow state under the basic pressure in the deposition process so as to remove an oxide layer on the copper target and impurities thereof, and then the deposition of elemental copper is carried out on the single crystal silicon wafer.
The deposition process is finished at the low temperature of 80 +/-5 ℃, the pre-deposition time is 5 minutes, the actual deposition time is five minutes, the power is 20W, the deposition mode is uninterrupted deposition, the deposited monocrystalline silicon piece is cooled on a device containing condensed water for rapid cooling, the monocrystalline silicon deposited with the nano copper film is taken out after being cooled to the constant temperature, and the monocrystalline silicon is dried in plasma containing argon for 5 minutes after being washed in ether and acetone, so that the dried monocrystalline silicon deposited with the nano copper film is obtained.
(3) Preparing a graphite alkyne lubricating film: and (3) placing the dried monocrystalline silicon wafer deposited with the nano copper film obtained in the step (2) into a three-neck flask containing 50mL of pyridine, dissolving HEB obtained in the step (1) into 25mL of pyridine, slowly dropwise adding the pyridine into the three-neck flask, wherein the dropwise adding process is sectional dropwise adding without continuous dropwise adding to achieve the effect of full reaction, heating the three-neck flask to 60 ℃ while dropwise adding, reacting under the conditions of oxygen-free protection (nitrogen atmosphere), light shielding and slow stirring, uniformly distributing the dropwise added medicines, and reacting for 7 days to obtain the graphite alkyne lubricating film.
(4) Surface treatment of a graphite alkyne lubricating film: as in the first embodiment.
Fifth embodiment
The preparation method of the graphite alkyne lubricating film comprises the following steps:
(1) synthesis of graphyne monomer (HEB) was the same as in the first example.
(2) Preparation of the substrate: before deposition, the copper sheet is subjected to surface cleaning treatment by using ethanol and diethyl ether, and then bombarded in argon plasma to remove impurities, oxide layers and the like on the surface of the copper sheet, so that a clean copper sheet substrate is obtained for later use.
(3) Preparing a graphite alkyne lubricating film: and (3) placing the copper sheet substrate obtained in the step (2) into a three-neck flask containing 50mL of pyridine, dissolving HEB obtained in the step (1) into 25mL of pyridine, slowly dropwise adding the HEB into the three-neck flask, wherein the dropwise adding process is segmented dropwise adding and does not need continuous dropwise adding to achieve the effect of full reaction, heating the three-neck flask to 60 ℃ while dropwise adding, reacting under the conditions of oxygen-free protection (nitrogen atmosphere), light shielding and slow stirring, uniformly distributing the dropwise added medicines, and reacting for 7 days to obtain the graphite alkyne lubricating film.
(4) Surface treatment of a graphite alkyne lubricating film: as in the first embodiment.
Sixth embodiment
The preparation method of the graphite alkyne lubricating film comprises the following steps:
(1) synthesis of graphyne monomer (HEB) was the same as in the first example.
(2) Preparation of a specific graphyne substrate:
before deposition, cleaning the surface of a glass sheet by using ethanol and diethyl ether, and then bombarding the glass sheet in argon plasma to remove impurities, an oxide layer and the like on the surface of the glass to obtain a clean substrate for later use;
at 1X 2 cm2The glass sheet is deposited with copper by using a PVD (physical vapor deposition) technology, the pre-deposition treatment is firstly carried out in the whole argon flow state under the basic pressure in the deposition process so as to remove an oxide layer on the copper target and impurities thereof, and then the deposition of elemental copper is carried out on the glass sheet.
The deposition process is finished at the high temperature of 115 +/-5 ℃, the predeposition time is 5 minutes, the actual deposition time is five minutes, the power is 20W, the deposition mode is uninterrupted deposition, the deposited glass sheet is directly placed on a device containing condensed water for cooling without cooling treatment, the glass sheet deposited with the nano copper film is taken out after being cooled to the constant temperature, and the glass sheet is dried for 5 minutes in plasma containing argon after being washed in ether and acetone, so that the dried glass sheet deposited with the nano copper film is obtained.
(3) Preparing a graphite alkyne lubricating film: and (3) placing the dried glass sheet deposited with the nano copper film obtained in the step (2) into a three-neck flask filled with 50mL of pyridine, dissolving HEB obtained in the step (1) into 25mL of pyridine, slowly dropwise adding the HEB into the three-neck flask, wherein the dropwise adding process is segmented dropwise adding without continuous dropwise adding to achieve the effect of full reaction, heating the three-neck flask to 60 ℃ while dropwise adding, reacting under the conditions of oxygen-free protection (nitrogen atmosphere), light shielding and slow stirring, uniformly distributing the dropwise added medicine, and reacting for 7 days to obtain the graphite alkyne lubricating film.
(4) Surface treatment of a graphite alkyne lubricating film: as in the first embodiment.
Performance characterization and testing
Fig. 1 is a diagram showing the effects of the graphite alkyne lubrication film prepared in the first embodiment, and it can be seen that the obtained graphite alkyne lubrication film has a regular and flat surface.
FIG. 2 is a Raman spectrum of the graphdine material prepared in the first example, and it can be seen that the peak position of the carbon material is 1306cm-1、1668cm-1The peak position of the alkyne bond in graphyne is 2238cm-1On the other hand, the first example is explained to successfully synthesize a thin film of a graphdine component.
FIG. 3 is a transmission electron microscope image of the graphite alkyne lubricating film synthesized in the first example; it can be seen that the synthesized graphdine sample is a thin, transparent two-dimensional lamellar structure with a width of about 207 nm.
Fig. 4 is a friction data graph of the graphite alkyne lubrication film prepared in the first embodiment and the monocrystalline silicon substrate used in the preparation process and under the conditions of 1N, 1Hz and 30min, and it can be seen that the graphite alkyne lubrication film has a friction coefficient of about 0.1 and a good lubrication effect.
Fig. 5 is a friction data graph of the graphite alkyne lubrication film prepared in each of the first and fourth examples and the monocrystalline silicon substrate used in the preparation of the same, and it can be seen that the lubrication performance of the graphite alkyne lubrication film prepared in each of the two examples is improved (by about 3 times) compared with that of the monocrystalline silicon substrate. However, the friction performance of the graphite alkyne lubrication film of the first embodiment is significantly superior to that of the fourth embodiment because the first embodiment employs a technique of rapidly cooling the nano-copper film immediately after high-temperature deposition at a temperature of 110 ℃ or more. The fourth embodiment adopts a low-temperature slow cooling post-treatment mode, which is not beneficial to the structure of the monocrystalline silicon substrate nano copper film.
FIG. 6 is a graph showing friction data of the graphite acetylene lubricating film prepared in each of the first, fifth and sixth examples and the single crystal silicon substrate used in the film preparation of the first example (friction test conditions: 1N, 1Hz, 30 min). The graphite alkyne lubricating film with more uniform surface appearance is obtained because the monocrystalline silicon has a regular surface structure and a single component when being used as a substrate, and copper atoms are favorably and more uniformly spread on the surface of the monocrystalline silicon, while the other two types of substrates do not have the functions.
FIG. 7 is an SEM image of the graphite acetylene lubricating film prepared in the first example after a friction test (friction test conditions: 1N, 1Hz, 30min, room temperature 25 ℃ C.) showing that scratches on the film surface are shallow, indicating that excellent lubricating properties are maintained during continuous friction for a long period of time.
Fig. 8 is a graph of friction data of the graphite acetylene lubrication film prepared in the first embodiment and the monocrystalline silicon substrate adopted in the preparation process under different test conditions (the load is 0.5N, 1N and 2N respectively, the frequency is 3Hz, and the test time is 30 min), and it can be seen that the lubrication film still has good lubrication performance after the load is doubled.
The above description is only illustrative of several embodiments of the present invention and should not be taken as limiting the scope of the invention. It should be noted that other persons skilled in the art can make modifications, substitutions, improvements and the like without departing from the spirit and scope of the present invention, and all of them belong to the protection scope of the present invention. Therefore, the scope of the invention should be determined from the description and claims.

Claims (10)

1. A preparation method of a graphite alkyne lubricating film is characterized by comprising the following steps:
(1) using monocrystalline silicon as a substrate, depositing a copper nano film on the surface of the monocrystalline silicon by using a physical vapor deposition method, wherein the deposition temperature is not lower than 110 ℃, and immediately and rapidly cooling the copper nano film after the deposition is finished to obtain the substrate deposited with the copper nano film for later use;
(2) and (2) carrying out coupling reaction on hexaalkynyl benzene in a solvent, and generating a graphite alkyne film on the surface of the copper nano film of the substrate obtained in the step (1).
2. The method for preparing a graphite alkyne lubricating film as claimed in claim 1, wherein the rapid cooling method in step (1) comprises the following steps: and (5) placing the substrate deposited with the copper nano film in a cooling device for cooling to obtain the copper nano film.
3. The method for preparing a graphite alkyne lubricating film as claimed in claim 1, wherein in the step (1), the power of the physical vapor deposition is 18-25W, and the deposition time is kept at 4-5.5 min.
4. The method for preparing a graphite alkyne lubricating film as claimed in claim 1, wherein in the step (1), before deposition, the deposition surface of the monocrystalline silicon is respectively cleaned by ethanol and diethyl ether, and then is bombarded in argon plasma to obtain a clean substrate.
5. The method for preparing a graphite alkyne lubricating film as claimed in claim 1, wherein in the step (2), the substrate deposited with the copper nano film is placed in pyridine, and then hexaalkynyl benzene is added to perform a coupling reaction under the catalysis of the copper nano film, so that the hexaalkynyl benzene generates the graphite alkyne film on the surface of the copper nano film.
6. The method for preparing a graphite alkyne lubricating film as claimed in claim 5, wherein in the step (2), the ratio of the mass of the hexaalkynyl benzene to the volume of the pyridine is 0.008-0.009 g: 20-25 mL.
7. The method for preparing a graphite alkyne lubricating film as claimed in claim 1, wherein in the step (2), the coupling reaction is carried out in an oxygen-free and light-proof environment;
preferably, in the step (2), the coupling reaction is carried out under heating; more preferably, the heating temperature is controlled to be 60-65 ℃, and the reaction time is 5-9 days.
8. The method for preparing a graphite alkyne lubricating film according to claim 1, wherein in the step (2), the graphite alkyne film deposited on the surface of the copper nano film is repeatedly washed by nitrogen-nitrogen dimethylformamide and ethanol, and then is dried in vacuum to obtain the graphite alkyne film.
9. The method for preparing a graphite alkyne lubricating film as recited in claim 1, wherein in the step (2), the method for preparing the hexaalkynyl benzene comprises the steps of: dissolving hexa (trimethylsilyl ethynyl) benzene in tetrahydrofuran, adding tetrabutylammonium fluoride solution after reaction, reacting under anaerobic and dark conditions (preferably at-8-0 ℃), diluting the reaction solution with ethyl acetate, washing with saturated saline solution, extracting an organic phase, drying with anhydrous magnesium sulfate, and carrying out freeze drying treatment to obtain the graphite alkyne monomer: hexaalkynyl benzene.
10. The application of the graphite alkyne lubrication film obtained by the preparation method of any one of claims 1 to 9 as a solid lubrication material in the fields of friction and lubrication.
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