CN114000106A - Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof - Google Patents

Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof Download PDF

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CN114000106A
CN114000106A CN202111205529.3A CN202111205529A CN114000106A CN 114000106 A CN114000106 A CN 114000106A CN 202111205529 A CN202111205529 A CN 202111205529A CN 114000106 A CN114000106 A CN 114000106A
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solid lubricating
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曹明
赵岚
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Jiujiang University
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/35Sputtering by application of a magnetic field, e.g. magnetron sputtering
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    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58After-treatment
    • C23C14/5806Thermal treatment

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Abstract

The invention discloses a low-friction coefficient MoS2A base composite solid lubricating coating and a preparation method thereof. The low-friction-coefficient composite coating system is metal CuS co-doped MoS2The preparation method comprises the following components in atomic percentage: 0 to 30 at% of metal, 4 to 28 at% of CuS, and MoS2The balance; wherein CuS plays a role in supplementing MoS2Consumption of S and metal doping in the lubricating process play a role in improving MoS2The function of abrasion resistance. Book (I)The invention designs the MoS2The component system combining the solid lubricating material and the metal-CuS dopant solves the problem of MoS2The problems of poor wear resistance, limited service environment service life and the like of the base solid lubricating coating in use prolong the service life of the solid lubricating coating and provide MoS2The base coating is more likely to be used in the field.

Description

Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Technical Field
The invention relates to the technical field of solid lubrication, in particular to a low-friction-coefficient MoS2A base composite solid lubricating coating and a preparation method thereof.
Background
The molybdenum disulfide has good anisotropy and lower friction factor, and the adhesion of S to metal is very strong, so that the molybdenum disulfide can be well attached to the surface of the metal and can always play a lubricating function, and the molybdenum disulfide solid lubricant is a metal sulfide solid lubricant with good performance. However, molybdenum disulfide in the atmospheric environment begins to be gradually oxidized at about 400 ℃, the friction coefficient thereof gradually increases, and the friction coefficient of molybdenum disulfide is increased along with the increase of humidity in the atmosphere due to poor moisture resistance and oxidation resistance.
In order to improve the oxidation resistance and the moisture resistance of molybdenum disulfide, prolong the service life of molybdenum disulfide and expand the application range of molybdenum disulfide, researchers add elementary metals, metal oxides, metal sulfides, metal fluorides and the like to form a two-component or multi-component solid lubricating material with molybdenum disulfide so as to improve the performances of the solid lubricating film such as synergistic lubrication, wear resistance, moisture resistance, oxidation resistance and the like. By supplementing the S element in time, the surfaces of the friction pair are protected from being damaged when performing relative friction motion, and MoS is prolonged2The service life of the base solid lubricating coating is long, and the base solid lubricating coating has important industrial application value.
The lubricating coating with the advantages of good binding force, uniform coating, compactness and the like can be prepared by adopting a physical vapor deposition method, but the problems of increased internal stress between the solid lubricating coating and the substrate and oxidation failure of the solid lubricating coating after repeated use still exist, and MoS can be effectively improved by selecting proper metal co-doping2Mechanical properties of the base lubricating coating. Thus, for MoS2In the problem of short service life, the problems of poor wear resistance and harsh use environment of the molybdenum disulfide-based solid lubricating coating in use are solved by improving a component system combining the molybdenum disulfide solid lubricating coating and the metal additive, so that the purpose of prolonging the service life of the coating is achieved.
Disclosure of Invention
In view of the above, a low friction coefficient MoS is provided2The base composite solid lubricating coating and the preparation method thereof obtain a low-friction and high-wear-resistance solid lubricating product to further prolong MoS2The service life of the base solid lubricating coating under actual industrial conditions.
In order to achieve the purpose, the invention provides the following technical scheme: low-friction-coefficient MoS2Based on a composite solid lubricating coating, the above-mentioned low coefficient of friction MoS2The atomic percentage composition of the base composite solid lubricating coating is as follows: 0 to 30 at% of metal, CuS4 to 28 at% of metal, and MoS2The balance; the metal is a reinforcing phase; the CuS is a synergistic lubricating phase; the metal is selected from any one of Cu, Al and Ti.
Further, the above-mentioned low friction coefficient MoS2The atomic percentage composition of the base composite solid lubricating coating is as follows: cu 0-15 at%, CuS 4-28 at%, MoS2And (4) the balance.
Further, the above-mentioned low friction coefficient MoS2The atomic percentage composition of the base composite solid lubricating coating is as follows: al 0-30 at%, CuS 4-28 at%, MoS2And (4) the balance.
Further, the above-mentioned low friction coefficient MoS2The atomic percentage composition of the base composite solid lubricating coating is as follows: ti 0-5 at%, CuS 4-28 at%, MoS2And (4) the balance.
Another object of the present invention is to provide a low coefficient of friction MoS2The preparation method of the base composite solid lubricating coating comprises the following steps:
step A1, pre-bonding layer sputtering: before magnetron sputtering coating, a magnetron direct-current power supply is adopted, and a Ti bonding layer is pre-deposited on the surface of the substrate for 10-20 min under the condition that the pre-sputtering power is 100W; the bonding layer is pre-deposited before magnetron sputtering coating, so that the internal stress between the coating and the substrate can be reduced, the binding force of the coating is improved, and the service life of the coating is prolonged;
step A2, magnetron sputtering coating: background vacuum degree of 7.5X 10-5~5×10-5Pa, adopting argon as working gas, wherein the working gas pressure is 0.5 Pa-2 Pa, the substrate is not heated, the rotating speed of the sample stage is 3 r/min-5 r/min, and the target base distance is 13 cm-16 cm; setting the sputtering conditions of the metal target: 0W-50W DC sputtering target power supply; setting the sputtering conditions of the CuS target: a 25W-100W radio frequency sputtering target power supply; MoS2Sputtering conditions of the target material: a 100W radio frequency sputtering target power supply; the sputtering time is 2hAbout 3h to obtain low friction coefficient MoS2A base composite solid lubricating coating;
step A3, subjecting the low friction coefficient MoS obtained in step A2 to vacuum conditions2The base composite solid lubricating coating is subjected to heat treatment at 220-420 ℃.
Wherein, metal-CuS-MoS is selected2The solid lubricating coating prepared by co-sputtering the target material can obtain the minimum average friction coefficient of 0.06 after vacuum heat treatment, and the microhardness of the coating is improved due to the densification of a microstructure, so that the overall mechanical property of the composite coating is enhanced, the film-substrate binding force of the coating reaches the HF1 standard of industrial application, and the overall wear resistance is improved; and the oxidation resistance of the composite coating layer doped with metals such as Cu, Al and the like can be further improved after the vacuum heat treatment process.
Further, in step a1, the substrate is: monocrystalline silicon stainless steel with Ra <1nm or surface roughness of 0.1-0.16 μm.
Further, before the step a1, the method further includes the steps of performing acetone and alcohol ultrasonic cleaning, drying and argon plasma cleaning on the substrate.
Further, in the step A1, the thickness of the pre-bonding layer is 35 to 70 nm.
Further, in step A2, the low friction coefficient MoS is2The thickness of the base composite solid lubricating coating is 0.8-2.0 mu m.
The technical scheme can show that the invention has the advantages that:
1. the high-performance solid lubricating coating obtained by the invention has a single-layer compact structure of CuS/MoS2The average friction coefficient of the composite solid lubricating coating is 0.08-0.23, metal is further doped, after vacuum heat treatment, the average friction coefficient is further reduced to 0.06-0.16, and the nano microhardness reaches 1-1.5 GPa; after vacuum heat treatment, the metal-CuS/MoS2The bonding strength of the composite solid lubricating coating can reach HF 1;
2. the invention selects CuS which is easy to decompose at high temperature as the magnetron sputtering to prepare MoS2The main additive component of the base composite solid lubricating coating or the auxiliary composite solid lubricating coatingThe metal of the seed component forms mesophase solid solution, and the prepared coating is subjected to vacuum heat treatment to finally improve MoS2The comprehensive friction performance and mechanical performance of the base solid lubricating coating are realized without complexity, the processing cost is low, the comprehensive use performance of the prepared coating meets the requirement, and the feasibility of industrial application is realized;
3. the invention predeposits the binding layer before magnetron sputtering coating, can reduce the internal stress between the coating and the substrate, and simultaneously, the CuS target material co-sputtering is relative to MoS due to the instability of CuS2The consumption of S in the friction process of the base solid lubricating coating plays a role in supplementing, and the MoS can be better prolonged2The service life of the base lubricant coating;
4. the Cu, Al or Ti metal selected by the invention is used as CuS-MoS2Co-sputtering the target material to develop metal densification MoS2The coating plays roles of strengthening, toughening, resisting oxidation and the like, so that the whole mechanical property of the coating is strengthened, and the overall wear resistance and the moisture resistance of the composite coating are improved;
5. CuS doped MoS of the invention2The preparation method of the base solid lubricating coating can inspire more MoS2Development of solid lubricating composite coating for promoting MoS2The industrial development of the solid lubrication field.
In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention will be described in further detail below.
Drawings
FIG. 1 shows the low coefficient of friction MoS obtained in example 1 of the invention2SEM image of the base composite solid lubricating coating;
FIG. 2 shows the low coefficient of friction MoS obtained in example 1 of the invention2SEM picture of the base composite solid lubricating coating cross-section;
FIG. 3 shows the low coefficient of friction MoS obtained in example 1 of the invention2The wear appearance of the base composite solid lubricating coating after wear;
FIG. 4 shows the low coefficient of friction MoS obtained in example 1 of the invention2Base compositeThe indentation binding force appearance of the solid lubricating coating;
FIG. 5 shows the low coefficient of friction MoS obtained in example 3 of the invention2The indentation bonding force appearance of the base composite solid lubricating coating;
FIG. 6 shows the low coefficient of friction MoS obtained in example 3 of the present invention2A graph of the change of the average friction coefficient of the base composite solid lubricating coating;
FIG. 7 shows the low coefficient of friction MoS obtained in example 3 of the present invention2XRD analysis pattern of the base composite solid lubricating series coating;
FIG. 8 shows the low coefficient of friction MoS obtained in examples 5 to 6 of the present invention2A graph of the change of the average friction coefficient of the base composite solid lubricating coating;
FIG. 9 shows the low coefficient of friction MoS obtained in examples 5 to 6 of the present invention2Raman analysis spectrum of the base composite solid lubricating coating;
FIG. 10 shows the low coefficient of friction MoS obtained in examples 6 to 7 of the present invention2Raman analysis spectrum of the base composite solid lubricating coating;
FIG. 11 shows the low coefficient of friction MoS obtained in examples 6 to 7 of the present invention2The indentation bonding force appearance of the base composite solid lubricating coating;
FIG. 12 shows the low coefficient of friction MoS obtained in examples 6 to 7 of the present invention2A graph of the change of the average friction coefficient of the base composite solid lubricating coating;
FIG. 13 shows the low coefficient of friction MoS obtained in examples 8 to 9 of the present invention2XRD patterns of the base composite solid lubricating coating after treatment at different annealing temperatures;
FIG. 14 shows the low coefficient of friction MoS produced in examples 8 to 9 of the present invention2And (3) a graph of the change of the average friction coefficient of the base composite solid lubricating coating.
Detailed Description
The following detailed description of embodiments of the invention, but the invention can be practiced in many different ways, as defined and covered by the claims.
Example 1
Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Low frictionCoefficient MoS2The base composite solid lubricating coating comprises the following components: CuS27.6 at%, MoS2The balance; the film thickness was 0.8. mu.m.
The coating passes through a CuS target and MoS2The target material co-sputtering comprises the following steps:
(1) carrying out ultrasonic cleaning, drying and argon plasma cleaning on monocrystalline silicon and stainless steel substrates by using acetone and alcohol;
(2) setting technological parameters, the background vacuum degree is 5 multiplied by 10-5Pa, argon is adopted as protective gas, the working pressure is 1Pa, the base temperature is normal temperature, the substrate rotation speed is 3r/min, and the target base distance is 16 cm; both targets adopt a radio frequency power supply, and before formal sputtering, 100W power is set to pre-deposit a Ti pre-bonding layer on the surface of the substrate for 10min, wherein the thickness of the pre-bonding layer is 35 nm;
(3) magnetron sputtering coating: the CuS target adopts a 25W radio frequency sputtering target power supply, MoS2The target adopts a 100W radio frequency sputtering target power supply to sputter for 3h to obtain low friction coefficient MoS2The composite solid lubricating coating is formed.
Example 2
Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Low coefficient of friction MoS2The base composite solid lubricating coating had the same composition as in example 1 and had a coating thickness of 1.5 μm.
The preparation method is the same as that of example 1 except that the CuS target in step (3) adopts a 50W radio frequency sputtering target power supply.
Example 3
Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Low coefficient of friction MoS2The composition and the coating thickness of the base metal composite solid lubricating coating are the same as those of the example 1.
The preparation method obtains the low friction coefficient MoS under the vacuum condition2The base composite solid lubricating coating was heat-treated at 220 ℃, 320 ℃ and 420 ℃ at different temperatures, the other being the same as in example 1.
Experimental example 1
1. Preparation of example 1Low coefficient of friction MoS2Performance testing of the base composite solid lubricating coating
(1) The prepared composite solid lubricating coating has a compact structure and is a mirror surface when observed by naked eyes, the microscopic morphology of the coating is shown in figure 1, and the surface of the coating is granular with the size of about 10-100 nm; the cross-sectional morphology of the prepared coating is shown in fig. 2, the bottom of the cross section is in a compact shape, and the upper part of the cross section shows slightly convex granular shapes.
(2) The friction performance of the composite coating is detected by a high-speed reciprocating friction and wear tester developed by Lanzhou chemical and physical research institute of Chinese academy of sciences. The test conditions were: the room temperature is 22-24 ℃, and the RH is 35-50%. The friction pair material is a steel ball with the diameter of 4mm, and the microhardness tester is used for testing the indentation binding force. The test results are: the average friction coefficient of the composite coating under the load of 10N is 0.17 at the lowest, and the bonding force of the composite coating is HF2 grade.
(3) The composite solid lubricating coating forms obvious scratches in the friction and wear process, and the coating shows a wear mechanism combining adhesive wear and particle wear. The wear appearance and the indentation binding force profile of the coating are shown in figures 3 and 4, the wear resistance is good, and the binding force is low.
2. Low coefficient of friction MoS prepared for example 32Performance testing of the base composite solid lubricating coating
(1) The bonding force and the average friction coefficient of the composite coating after vacuum heat treatment at 220 ℃, 320 ℃ and 420 ℃ in the example 3 are tested, and the test results are shown in fig. 5 and 6, wherein the temperature of CuS25-220 ℃ in the figure indicates that a 25W radio frequency sputtering target power supply is adopted for the CuS target, and the vacuum heat treatment is carried out at 220 ℃; CuS25-320 ℃ represents that the CuS target adopts a 25W radio frequency sputtering target power supply and is subjected to vacuum heat treatment at 320 ℃; CuS25-420 ℃ represents that the CuS target adopts a 25W radio frequency sputtering target power supply and is subjected to vacuum heat treatment at 420 ℃;
(2) low coefficient of friction MoS obtained in example 32Performing X-ray diffraction analysis on the phase of the base composite solid lubricating coating, wherein CuS25-220 ℃ in the figure shows that a 25W vacuum sputtering target power supply is adopted for a CuS target, and vacuum heat treatment is performed at 220 ℃; CuS25-320 ℃ represents that the CuS target adopts a 25W radio frequency sputtering target power supply and is subjected to vacuum heat treatment at 320 ℃; CuS25-420 ℃ meterThe CuS target was heat treated in vacuum at 420 ℃ using a 25W RF sputtering target power supply, and the results are shown in FIG. 7.
The result shows that the CuS target adopts a 25W power radio frequency sputtering power supply and MoS2The composite solid lubricating coating obtained by target co-sputtering is subjected to heat treatment at different temperatures of 220 ℃, 320 ℃ and 420 ℃, the phase is mainly in an amorphous state, and the prepared coating does not generate large grains.
Example 4
Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Low coefficient of friction MoS2The doped metal of the base composite solid lubricating coating is Cu target material, the atomic percentage of Cu is 15 at%, CuS28 at%, and the rest is MoS2The thickness of the composite coating is about 1.5 mu m.
The preparation method comprises the steps of removing 20W direct current sputtering of the Cu target, 25W radio frequency sputtering of the CuS target and MoS2The target material 100W was subjected to RF sputtering, and the rest was the same as in example 1.
Example 5
Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Low coefficient of friction MoS2The composition and coating thickness of the composite solid lubricating coating were the same as in example 4.
The preparation method is to obtain the low friction coefficient MoS under the vacuum condition2The base composite solid lubricating coating was subjected to vacuum heat treatment at different temperatures of 220 deg.C, 320 deg.C and 420 deg.C, and the other steps were the same as in example 4.
Experimental example 2
1. Low coefficient of friction MoS of example 4 without vacuum Heat treatment2Base composite solid lubricating coating identified as Cu20CuS, low coefficient of friction MoS by vacuum heat treatment at different temperatures, example 52The base composite solid lubricating coating is marked as Cu20CuS-220 ℃, Cu20CuS-320 ℃ and Cu20CuS-420 ℃ respectively, and is subjected to average friction coefficient change test and Raman analysis, and the test results are shown in FIGS. 8 and 9.
The results show that the composite coating is more obvious after being annealed at 420 DEG CMoS2Crystallization peak, which shows that the Cu metal doping is beneficial to MoS in the coating during the high-temperature annealing process2Nucleation and nucleation growth, MoS2Corresponding E2g(382cm-1) And A1g(407cm-1) The peaks are very distinct; the corresponding peaks of CuS in the composite coating are not obvious, even the characteristic of the continuous CuS amorphous peak is not obvious, and the Cu doping inhibits the formation of CuS crystals.
In addition, Raman spectra showed that the intensity of Cu was not high2The O peak indicates that Cu is easily oxidized in the coating, which is consistent with the cause of abrasive wear during the rubbing of the composite coating in example 1, although Cu2O has the performance beneficial to the lubrication of the coating under the high-temperature working condition, but does not have the function of remarkably improving the lubricating performance of the coating at normal temperature.
After the coating is annealed at 220 ℃ and 320 ℃, the friction coefficient is obviously reduced, and the average friction coefficient is lower and reaches 0.08 when the coating is annealed at 320 ℃. Thus, annealing at moderate temperatures further improves the Cu-CuS co-doped MoS2The lubricating performance of the base composite coating.
Example 6
Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Low coefficient of friction MoS2The doped metal is Al target material, Al atom percentage is 26 at%, CuS atom percentage is 24 at%, the rest is MoS2The coating thickness was about 1.0. mu.m.
The preparation method adopts 30W direct current sputtering for the metal-doped Al target material, 25W radio frequency sputtering for the CuS target material and MoS2The target material 100W was subjected to RF sputtering, and the rest was the same as in example 4.
Example 7
Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Low coefficient of friction MoS2The composition and coating thickness of the composite solid lubricating coating were the same as in example 6.
The preparation method is to obtain the low friction coefficient MoS under the vacuum condition2The base composite solid lubricating coating was subjected to vacuum heat treatment at different temperatures of 220 deg.C, 320 deg.C and 420 deg.C, and the other steps were the same as in example 6.
Experimental example 3
1. The low friction coefficient MoS prepared in example 6 and not subjected to vacuum heat treatment2The base composite solid lubricating coating was designated Al20CuS, and the low friction coefficient MoS of vacuum heat treatment at 220 deg.C, 320 deg.C and 420 deg.C prepared in example 72The Raman analysis was performed on the base composite solid lubricating coatings, respectively, and the test results are shown in fig. 10. Then, the bonding force and the average friction coefficient change of the composite coating after vacuum heat treatment are tested, and the test results are shown in fig. 11 and 12.
The results show that the increase of Al doping content is beneficial to MoS in the coating2Nucleation and growth. Al metal doped CuS-MoS2The composite coating mainly forms an amorphous structure, and metal atoms are dissolved into MoS2、Cu1.94S crystal lattice, together with which an amorphous structure is formed; the Al doping causes obvious residual stress and microcrack generation, and becomes a source of nucleation in the annealing process of the coating to a certain extent, so that the nucleation and the growth of the coating are promoted in the annealing process. MoS appears on the coating after annealing treatment at 420 DEG C2Phase E1g(285cm-1)、E2g(382cm-1) And A1g(407cm-1) Peaks and weak CuS corresponding peaks. With MoS2The crystals grow, and the corresponding peak of CuS is gradually enhanced and then gradually disappears.
The binding force test result also shows that Al is doped with CuS-MoS2When the coating is compounded, the internal stress of the coating caused by aluminum doping is relatively small or the lattice distortion is less, the binding force of the composite coating is improved after the composite coating is subjected to heat treatment at 420 ℃, the HF1 level is reached, and the toughness of the composite coating is particularly reflected on the toughness of the composite coating after the composite coating is subjected to annealing treatment. The coating has better binding force and is more beneficial to the tribological property and the mechanical property of the coating.
The result shows that the average friction coefficient of the composite coating is gradually reduced after the vacuum heat treatment, the minimum average friction coefficient of the composite coating is 0.064 after the composite coating is annealed at 420 ℃, and the lubricating property of the composite coating is improved.
Example 8
Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Low coefficient of friction MoS2The doped metal is selected from a Ti target material, the atomic percent of Ti is 2.5 at%, the atomic percent of CuS is 20 at%, and the rest is MoS2The coating thickness was about 1.0. mu.m.
In the preparation method, the Ti metal target material adopts 25W direct current sputtering, and the CuS target material adopts 25W radio frequency sputtering and MoS2The target material was subjected to radio frequency sputtering of 100W, and the rest was the same as in example 4.
Example 9
Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Low coefficient of friction MoS2The composition of the base composite solid lubricating coating was the same as in example 8.
The preparation method is to obtain the low friction coefficient MoS under the vacuum condition2The base composite solid lubricating coating was subjected to vacuum heat treatment at different temperatures of 220 deg.C, 320 deg.C and 420 deg.C, and the other steps were the same as in example 8.
Experimental example 4
Low coefficient of friction MoS of example 8 without vacuum Heat treatment2The base composite solid lubricating coating is marked as Ti25CuS, and the low friction coefficient MoS prepared in example 9 by vacuum heat treatment at different temperatures of 220 ℃, 320 ℃ and 420 DEG C2XRD analysis was performed on the base composite solid lubricating coating, and the results are shown in fig. 13, and then the average friction coefficient change of the composite coating after heat treatment is measured, and the results are shown in fig. 14.
The results show that the MoS in the composite coating increases with the temperature of the vacuum heat treatment2The steamed bun peaks are more and more sharp, with MoS at 320 ℃ annealing2The steamed bun peak is sharpest; shows that the doping of Ti is also more beneficial to MoS2And (4) crystallizing.
The average friction coefficient of the composite coating annealed at 420 ℃ is the lowest in the same series and is 0.09, and the nano indentation test result of the composite coating is 1.34GPa, the wear rate of the composite coating is the lowest, namely 40 x 10-7mm3The reason why the mechanical property of the coating is obviously improved is that the coating is more compact after Ti is doped.
Comparative example 1
Pure MoS2The solid lubricating coating has the thickness of 1.0 mu m, and the preparation method comprises the following steps:
(1) carrying out ultrasonic cleaning and drying on the surface of a stainless steel substrate by acetone and alcohol, and carrying out argon plasma cleaning;
(2) setting technological parameters, the background vacuum degree is 5 multiplied by 10-5Pa, argon is adopted as protective gas, the working pressure is 1Pa, the base temperature is normal temperature, the substrate rotation speed is 5r/min, and the target base distance is 16 cm; pre-depositing a Ti bonding layer on the surface of the substrate for 20min by adopting a direct current power supply under the condition that the pre-sputtering power is 100W, wherein the thickness of the pre-bonding layer is 70 nm;
(3) magnetron sputtering coating: MoS2Sputtering the target for 3h by using a 100W radio frequency sputtering target power supply to obtain the target.
Experimental example 5
The pure MoS prepared by the comparative example 1 is compared with a high-speed reciprocating friction and wear tester developed by Lanzhou chemical and physical research institute of Chinese academy of sciences2And (5) carrying out a friction performance test on the solid lubricating film. The test conditions were: room temperature, RH 50%. The friction pair is made of steel balls with the diameter of 4mm, a diamond pressure head with the cone angle of 120 degrees and the tip radius of 0.2mm is adopted in the scratch test, and the reciprocating friction speed is 240 mm/min. The test results showed an average coefficient of friction of 0.175 and a nano-hardness of 0.35 GPa.
Example 10
Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Low coefficient of friction MoS2The base composite solid lubricating coating comprises the following components: CuS4 at%, MoS2The balance; the film thickness was 2.0. mu.m.
The coating passes through a CuS target and MoS2The target material co-sputtering comprises the following steps:
(1) carrying out ultrasonic cleaning, drying and argon plasma cleaning on monocrystalline silicon and stainless steel substrates by using acetone and alcohol;
(2) setting technological parameters, the background vacuum degree is 7.5 multiplied by 10-4Pa, argon is adopted as protective gas, the working pressure is 0.5Pa, the base temperature is normal temperature, the substrate rotation speed is 5r/min, and the target base distance is 13 cm; both targets adopt a radio frequency power supply, before formal sputtering, a direct current power supply with 100W power is set to pre-deposit a Ti pre-bonding layer on the surface of the substrate for 20min, and the thickness of the pre-bonding layer is 70 nm;
(3) magnetron sputtering coating: setting technological parameters, the background vacuum degree is 7.5 multiplied by 10-4Pa, argon is adopted as protective gas, the working pressure is 0.5Pa, the base temperature is normal temperature, the substrate rotation speed is 5r/min, and the target base distance is 13 cm; the CuS target adopts a 100W direct current sputtering target power supply, MoS2The target adopts a 100W radio frequency sputtering target power supply to sputter for 2h, and the low friction coefficient MoS is obtained2The composite solid lubricating coating is formed.
Example 11
Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Low coefficient of friction MoS2The base composite solid lubricating coating comprises the following components: cu7.5at%, CuS28 at%, MoS2The balance; the film thickness was 1.5. mu.m.
The coating passes through a CuS target and MoS2The target material co-sputtering comprises the following steps:
(1) carrying out ultrasonic cleaning, drying and argon plasma cleaning on monocrystalline silicon and stainless steel substrates by using acetone and alcohol;
(2) setting technological parameters and background vacuum degree of 6.5X 10-4Pa, argon is adopted as protective gas, the working pressure is 1.5Pa, the base temperature is normal temperature, the rotating speed of the substrate is 4r/min, and the target base distance is 15 cm; both targets adopt a radio frequency power supply, before formal sputtering, a direct current power supply with 100W power is set to pre-deposit a Ti pre-bonding layer on the surface of the substrate for 15min, and the thickness of the pre-bonding layer is 50 nm;
(3) magnetron sputtering coating: setting technological parameters and background vacuum degree of 6.5X 10-4Pa, argon is adopted as protective gas, the working pressure is 1.5Pa, the base temperature is normal temperature, the rotating speed of the substrate is 4r/min, and the target base distance is 15 cm; sputtering conditions of a Cu target set to 20WA DC sputtering target power supply; CuS target adopts 50W direct current sputtering target power supply, MoS2The target adopts a 100W radio frequency sputtering target power supply to sputter for 2.5h to obtain the low friction coefficient MoS2The composite solid lubricating coating is formed.
Example 12
Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Low coefficient of friction MoS2The base composite solid lubricating coating comprises the following components: 30 at% of Al, 20 at% of CuS and MoS2The balance; the film thickness was 1.2. mu.m.
The coating passes through a CuS target and MoS2The target material co-sputtering comprises the following steps:
(1) carrying out ultrasonic cleaning, drying and argon plasma cleaning on monocrystalline silicon and stainless steel substrates by using acetone and alcohol;
(2) setting technological parameters and background vacuum degree of 6.5X 10-4Pa, argon is adopted as protective gas, the working pressure is 1.5Pa, the base temperature is normal temperature, the rotating speed of the substrate is 4r/min, and the target base distance is 15 cm; both targets adopt a radio frequency power supply, and before formal sputtering, 100W power is set to pre-deposit a Ti pre-bonding layer on the surface of the substrate for 15min, wherein the thickness of the pre-bonding layer is 50 nm;
(3) magnetron sputtering coating: setting technological parameters and background vacuum degree of 6.5X 10-4Pa, argon is adopted as protective gas, the working pressure is 1.5Pa, the base temperature is normal temperature, the rotating speed of the substrate is 4r/min, and the target base distance is 15 cm; setting a 20W direct current sputtering target power supply under the sputtering condition of the Al target material; CuS target adopts 50W direct current sputtering target power supply, MoS2The target adopts a 100W radio frequency sputtering target power supply to sputter for 2.5h to obtain the low friction coefficient MoS2The composite solid lubricating coating is formed.
Example 13
Low-friction-coefficient MoS2Base composite solid lubricating coating and preparation method thereof
Low coefficient of friction MoS2The base composite solid lubricating coating comprises the following components: ti5 at%, CuS25 at%, MoS2The balance; the film thickness was 1.2. mu.m.
The coating passes through a CuS target and MoS2The target material co-sputtering comprises the following steps:
(1) carrying out ultrasonic cleaning, drying and argon plasma cleaning on monocrystalline silicon and stainless steel substrates by using acetone and alcohol;
(2) setting technological parameters, the background vacuum degree is 5 multiplied by 10-4Pa, argon is adopted as protective gas, the working pressure is 2.5Pa, the base temperature is normal temperature, the substrate rotation speed is 4r/min, and the target base distance is 15 cm; both targets adopt a radio frequency power supply, before formal sputtering, a direct current power supply with 100W power is set to pre-deposit a Ti pre-bonding layer on the surface of the substrate for 15min, and the thickness of the pre-bonding layer is 50 nm;
(3) magnetron sputtering coating: setting technological parameters and background vacuum degree of 6.5X 10-4Pa, argon is adopted as protective gas, the working pressure is 1.5Pa, the base temperature is normal temperature, the rotating speed of the substrate is 4r/min, and the target base distance is 15 cm; setting a sputtering condition of a Ti target material, namely a 20W direct-current sputtering target power supply; CuS target adopts 50W direct current sputtering target power supply, MoS2The target adopts a 100W radio frequency sputtering target power supply to sputter for 2.5h to obtain the low friction coefficient MoS2The composite solid lubricating coating is formed.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to 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 (9)

1. Low-friction-coefficient MoS2Based on a composite solid lubricating coating, characterized in that the low friction coefficient MoS2The atomic percentage composition of the base composite solid lubricating coating is as follows: 0 to 30 at% of metal, CuS4 to 28 at% of metal, and MoS2The balance; the metal is a reinforcing phase; the CuS is a synergistic lubricating phase; the metal is selected from any one of Cu, Al and Ti.
2. Low coefficient of friction MoS according to claim 12Based on a composite solid lubricating coating, characterized in that the low friction coefficient MoS2Base composite solid lubricantThe coating comprises the following components in percentage by atom: cu 0-15 at%, CuS 4-28 at%, MoS2And (4) the balance.
3. Low coefficient of friction MoS according to claim 12Based on a composite solid lubricating coating, characterized in that the low friction coefficient MoS2The atomic percentage composition of the base composite solid lubricating coating is as follows: al 0-30 at%, CuS 4-28 at%, MoS2And (4) the balance.
4. Low coefficient of friction MoS according to claim 12Based on a composite solid lubricating coating, characterized in that the low friction coefficient MoS2The atomic percentage composition of the base composite solid lubricating coating is as follows: ti 0-5 at%, CuS 4-28 at%, MoS2And (4) the balance.
5. A low coefficient of friction MoS according to any one of claims 1 to 42The preparation method of the base composite solid lubricating coating is characterized by comprising the following steps:
step A1, pre-bonding layer sputtering: before magnetron sputtering coating, a magnetron direct-current power supply is adopted, and a Ti bonding layer is pre-deposited on the surface of the substrate for 10-20 min under the condition that the pre-sputtering power is 100W;
step A2, magnetron sputtering coating: background vacuum degree of 7.5X 10-5~5×10-5Pa, adopting argon as working gas, wherein the working gas pressure is 0.5 Pa-2 Pa, the substrate is not heated, the rotating speed of the sample stage is 3 r/min-5 r/min, and the target base distance is 13 cm-16 cm; setting the sputtering conditions of the metal target: 0W-50W DC sputtering target power supply; setting the sputtering conditions of the CuS target: a 25W-100W radio frequency sputtering target power supply; MoS2Sputtering conditions of the target material: a 100W radio frequency sputtering target power supply; the sputtering time is 2 h-3 h, and the low friction coefficient MoS is obtained2A base composite solid lubricating coating;
step A3, subjecting the low friction coefficient MoS obtained in step A2 to vacuum conditions2The base composite solid lubricating coating is subjected to vacuum heat treatment at 220-420 ℃.
6. Low coefficient of friction MoS according to claim 52The preparation method of the base composite solid lubricating coating is characterized in that in the step A1, the substrate is as follows: monocrystalline silicon Ra<Stainless steel with the thickness of 1nm or the surface roughness of 0.1-0.16 μm.
7. Low coefficient of friction MoS according to claim 52The preparation method of the base composite solid lubricating coating is characterized by further comprising the steps of carrying out ultrasonic cleaning on the substrate by acetone and absolute ethyl alcohol, drying and argon plasma cleaning before the step A1 is carried out.
8. Low coefficient of friction MoS according to claim 52The preparation method of the base composite solid lubricating coating is characterized in that in the step A1, the thickness of the pre-bonding layer is 35-70 nm.
9. Low coefficient of friction MoS according to claim 52The preparation method of the base composite solid lubricating coating is characterized in that in the step A2, the low friction coefficient MoS2The thickness of the base composite solid lubricating coating is 0.8-2.0 mu m.
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