CN111876732B - Molybdenum boride/molybdenum sulfide nano composite coating and preparation method thereof - Google Patents

Molybdenum boride/molybdenum sulfide nano composite coating and preparation method thereof Download PDF

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CN111876732B
CN111876732B CN202010555201.3A CN202010555201A CN111876732B CN 111876732 B CN111876732 B CN 111876732B CN 202010555201 A CN202010555201 A CN 202010555201A CN 111876732 B CN111876732 B CN 111876732B
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molybdenum
coating
magnetron sputtering
molybdenum sulfide
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CN111876732A (en
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朱晓东
王大伟
李倩叶
李雁淮
宋忠孝
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Xian Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3435—Applying energy to the substrate during sputtering
    • C23C14/345—Applying energy to the substrate during sputtering using substrate bias
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract

The invention discloses a boron nitrideMolybdenum/molybdenum sulfide nano composite coating and preparation method thereof, and metal Mo and B are sputtered by adopting reactive magnetron sputtering technology as cathode 4 C、MoS 2 A composite target and Ar and N in a vacuum chamber 2 N in the mixed gas 2 The Mo-B-S-C-N five-membered hard coating, namely the boron molybdenum nitride/molybdenum sulfide nano composite coating, is obtained on the surface of the substrate through gas reaction, and B in the composite target is regulated 4 C and MoS 2 The area of (c) allows the content of B and S in the coating to be easily controlled. The atomic percentage of B, C, S, mo, N element in the coating is 0.5-12%, 2-14%, 0.5-10%, 55-40% and 42-24%. The method has simple process and easy implementation. The invention overcomes the defects of the friction performance of the existing hard coating, has the characteristics of high hardness, wear resistance and low friction coefficient from room temperature to high temperature, and has good application prospect and popularization value on high-speed or dry cutting tools.

Description

Molybdenum boride/molybdenum sulfide nano composite coating and preparation method thereof
Technical Field
The invention belongs to the technical field of material surface coatings, and particularly relates to a boron molybdenum nitride/molybdenum sulfide nano composite coating and a preparation method thereof.
Background
With the development of cutting technology, particularly in certain high-speed cutting and other specific machining conditions, such as deep hole machining and complex machining environments, the performance requirement on the cutter material is higher when the cutting fluid cannot be sufficiently lubricated and cooled. When the high-speed cutting condition or the partial lubrication and cooling are not enough, a large amount of cutting heat is generated due to friction, so that the cutter is gradually worn out in a binding way to fail, and the processing quality of a workpiece is reduced. This means that the cutter itself needs to have the characteristics of high hardness, good wear resistance, stable chemical properties, heat resistance, oxidation resistance, low friction coefficient, and the like. The low friction coefficient hard coating with wear resistance and abrasion resistance not only can reduce friction and abrasion of a workpiece and reduce or replace liquid lubrication and cooling, save equipment investment, but also can avoid environmental pollution caused by cutting fluid and realize clean production, so that the low friction coefficient hard coating is an efficient and clean green cutting tool and has quite wide application prospect in the modern cutting and machining industry.
The metal molybdenum nitride has higher hardness, and the friction coefficient is far lower than that of other transition group metal nitrides such as TiN. Although the molybdenum nitride coating has a low coefficient of friction at high temperatures, it is susceptible to oxidation resulting in reduced strength hardness and insufficient wear resistance. The oxidation resistance and hardness of the molybdenum nitride coating are improved through an alloying method, the friction coefficient of the coating is further reduced, and the application field and the use condition of the molybdenum nitride coating can be expanded. At present, the literature for researching the Mo-B-S-C-N quinary coating is not reported yet.
Disclosure of Invention
The invention aims to provide a boron molybdenum nitride/molybdenum sulfide nano composite coating and a preparation method thereof, wherein the Mo-B-S-C-N quinary coating is prepared by a co-sputtering method, and the coating has the characteristics of wear resistance and low friction coefficient at room temperature and high temperature.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the boron molybdenum nitride/molybdenum sulfide nano composite coating comprises the following steps:
1) Will be composed of metal Mo and B 4 C and MoS 2 The composite target and the substrate are respectively arranged on a cathode and a sample table in a vacuum chamber of the magnetron sputtering equipment;
2) Vacuumizing a vacuum chamber of the magnetron sputtering equipment, and then sputtering and cleaning the surface of the substrate by using argon ions;
3) Argon and nitrogen are introduced into a vacuum chamber of the magnetron sputtering equipment, the magnetron sputtering composite target is subjected to auxiliary bombardment on the coating in deposition by nitrogen ions in the deposition process, and the boron-molybdenum nitride/molybdenum sulfide nano composite coating is obtained.
Metal Mo and (B) in the composite target 4 C and MoS 2 ) The area ratio of (B) is 10:1-7:3, wherein B is as follows 4 C and MoS 2 The area ratio is 5:1-1:5, the purity of Mo is 99.99%, and B is 4 C and MoS 2 The purity of the composite target is 99.9%, and the distance between the composite target and the substrate is 80-120 mm.
The substrate is a metal substrate or a ceramic substrate, wherein the metal substrate is steel, cast iron or hard alloy.
In the step 2), the vacuum degree in the vacuum chamber of the magnetron sputtering equipment is pumped to be less than or equal to 5 multiplied by 10 -4 And after Pa, applying negative bias voltage to the substrate by 400-800V, and cleaning the surface of the substrate by utilizing argon ion sputtering for at least 10min.
The flow ratio of the argon to the nitrogen introduced in the step 3) is 1:1-1:10, and the working air pressure is 0.1-2 Pa.
The power of the magnetron sputtering in the step 3) is 100-300W, and the time is 120-240 min.
And in the step 3), the substrate is negatively biased for 40V-120V in the deposition process, and nitrogen ions and argon ions are utilized to carry out auxiliary bombardment on the coating in the deposition process.
And 3) stopping introducing argon and nitrogen after the magnetron sputtering is finished, and keeping the vacuum state until the substrate temperature is less than or equal to 60 ℃.
The boron nitride/molybdenum sulfide nano composite coating is a Mo-B-S-C-N five-membered coating, wherein the atomic percentage of Mo element is 55-40%, the atomic percentage of N element is 42-24%, the atomic percentage of B element is 0.5-12%, the atomic percentage of C element is 2-14%, and the atomic percentage of S element is 0.5-10%.
The hardness of the boron molybdenum nitride/molybdenum sulfide nano composite coating is 19-27 GPa, the friction coefficient at normal temperature is more than or equal to 0.19, and the friction coefficient at 600 ℃ is more than or equal to 0.15.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the boron molybdenum nitride/molybdenum sulfide nano composite coating selects proper metals Mo and B on the basis of the molybdenum nitride coating 4 C and MoS 2 Composite target and corresponding sputtering technological parameters, and the metal Mo and B are sputtered by cathode through reactive magnetron sputtering technology 4 C and MoS 2 A composite target and Ar and N in a vacuum chamber 2 N in the mixed gas 2 The gas reaction forms a Mo-B-S-C-N five-membered hard coating with proper B, C, S element content on the surface of the substrate, namely a boron molybdenum nitride/molybdenum sulfide nano composite coating, and the preparation method comprises the following steps ofB in composite target 4 C and MoS 2 The area occupied by the target ensures that the contents of B and S in the coating are easy to control, and the method has simple process and easy implementation.
The invention provides a boron molybdenum nitride/molybdenum sulfide nano composite coating (Mo-B-S-C-N five-membered hard coating), wherein the atomic percentage of B, C, S, mo, N element is 0.5-12%, 2-14%, 0.5-10%, 55-40% and 42-24% respectively. The coating overcomes the defects of the existing hard coating in the aspect of performance and tribological performance, has the characteristics of high hardness, wear resistance and low friction coefficient at room temperature and high temperature, and has good popularization and application prospects on high-speed cutting or dry cutting tools.
Further, experiments show that the hardness of the boron molybdenum nitride/molybdenum sulfide nano composite coating (Mo-B-S-C-N five-membered hard coating) prepared by the invention can reach 27GPa, the friction coefficient at room temperature is as low as 0.19, the friction coefficient at 600 ℃ can be as low as 0.15, and the wear rate is less than 1/80 of that of the molybdenum nitride coating.
Drawings
FIG. 1 shows the metallic Mo and B used in the present invention 4 C and MoS 2 Schematic structural diagram of the composite target;
FIG. 2 is an XRD pattern of a molybdenum boride/molybdenum sulfide nanocomposite coating produced in accordance with the present invention;
FIG. 3 is a graph showing the relationship between the hardness and B, S content of the boron molybdenum nitride/molybdenum sulfide nanocomposite coating produced by the present invention;
FIG. 4 is a graph showing the relationship between the average friction coefficient and B, S content of the boron-molybdenum nitride/molybdenum sulfide nanocomposite coating prepared by the present invention at room temperature.
FIG. 5 is a graph showing the relationship between the wear rate and B, S content of the boron-molybdenum nitride/molybdenum sulfide nanocomposite coating prepared by the present invention at room temperature.
FIG. 6 is a graph of average coefficient of friction versus B, S content for a molybdenum boride/sulfide nanocomposite coating made in accordance with the present invention at 600 ℃.
FIG. 7 is a graph of wear rate versus B, S content for a molybdenum boride/sulfide nanocomposite coating made in accordance with the present invention at 600 ℃.
Detailed Description
The invention prepares the boron nitride molybdenum/molybdenum sulfide nano composite coating (Mo-B-S-C-N five-membered coating) by adopting a molybdenum target (purity is 99.99%) and B 4 C target (purity 99.9%) and MoS 2 The target (purity 99.9%) is made into a composite target, deposited on a metal, hard alloy or ceramic substrate by direct current magnetron sputtering, and bombarded with nitrogen ions and argon ions under the negative bias of the substrate. The thickness of the prepared boron molybdenum nitride/molybdenum sulfide nano composite coating (Mo-B-S-C-N quinary coating) is 1-5 mu m, the hardness is 17-27 GPa, the friction coefficient at normal temperature is at least 0.19, and the friction coefficient at high temperature (600 ℃) is at least 0.15. Wherein the atomic percentage of the element C is 2-14%, the atomic percentage of the element B is 0.5-12%, the atomic percentage of the element S is 0.5-10%, the atomic percentage of the element Mo is 55-40%, and the atomic percentage of the element N is 44-24%.
The friction coefficient and the wear resistance at different temperatures are combined to obtain the more optimal range of 3-6% of the atomic percentage of the S element and 4-12% of the atomic percentage of the B element.
The preparation method of the boron molybdenum nitride/molybdenum sulfide nano composite coating provided by the invention comprises the following specific steps:
1) Taking metal (steel, cast iron or hard alloy) or ceramic as a substrate, degreasing, deoxidizing and drying by hot air, and fixing on a rotatable workpiece frame in a vacuum chamber;
2) High-purity Mo and a certain amount of B 4 C and MoS 2 The composite target formed by the target pieces is arranged on a magnetron sputtering source; metallic Mo and (B) in composite targets 4 C and MoS 2 ) The area ratio of (B) is 10:1-7:3, wherein B is as follows 4 C and MoS 2 The area ratio is 5:1-1:5, the purity of Mo is 99.99%, and B is 4 C and MoS 2 The purity of the composite target is 99.9%, and the distance between the composite target and the substrate is 80-120 mm;
3) Then the vacuum degree in the vacuum chamber is pumped to be less than or equal to 5 multiplied by 10 -4 Pa, introducing Ar with the flow of 20sccm, and pre-sputtering Mo/B when the pressure of the vacuum chamber is 0.3Pa 4 C, compounding the target for 5min, wherein the pre-sputtering power is 150W;
4) Then introducing argon with the concentration of 6sccm into the ion source, applying negative bias voltage to the substrate for 400-800V, and sputtering and cleaning the surface of the substrate by argon ions generated by glow discharge for at least 10min;
5) Then 4-10 sccm argon and 4-40 sccm nitrogen are introduced to form a mixed atmosphere, the flow ratio of the argon to the nitrogen is 1:1-1:10, and the working pressure is 0.1-2 Pa.
6) Sputtering Mo/B in a vacuum chamber in an argon-nitrogen mixed atmosphere at a power of 100-300W 4 And C the composite target is 120-240 min, and a negative bias voltage of 40 eV-120V is applied to the substrate, and nitrogen ions and argon ions are utilized to carry out auxiliary bombardment on the coating in deposition, so that the boron-molybdenum nitride/molybdenum sulfide nano composite coating (Mo-B-S-C-N five-membered hard coating) is prepared.
The present invention is described in detail below with reference to the drawings and examples, but the present invention is not limited to the following examples.
Example 1
1) Molybdenum target and 2 blocks B in FIG. 1 4 C and 2 MoS blocks 2 A composite target consisting of B as a magnetron sputtering source 4 C and MoS 2 And the area ratio of Mo is 1:1:8, and the distance between the composite target and the substrate is 10cm;
2) Selecting high-speed steel as a base material, derusting and polishing the surface of the base material, respectively cleaning the base material for 10min in an ultrasonic cleaner by using acetone, alcohol and deionized water, drying the base material by using hot air, and placing the base material on a sample table in a vacuum chamber;
3) The vacuum degree in the vacuum chamber is pumped to be less than or equal to 5 multiplied by 10 -4 After Pa, the substrate is negatively biased at 800V, and argon ions generated by glow discharge are used for sputtering and cleaning the surface of the substrate for 10min;
4) Introducing 4sccm argon and 20sccm nitrogen at a flow ratio of 1:5 and working pressure of 0.8Pa to form a mixed atmosphere, and sputtering Mo and (B) by using a magnetron sputtering technology 4 C and MoS 2 ) And (3) adding negative bias voltage to the substrate for 100eV in the deposition process of the composite target, performing auxiliary bombardment on the deposited coating by utilizing nitrogen ions, wherein the power of magnetron sputtering is 200W, the time is 200min, and after the magnetron sputtering is finished, stopping introducing argon and nitrogen, and keeping the vacuum state until the temperature of the substrate is less than or equal to 60 ℃, thereby preparing the boron-molybdenum nitride/molybdenum sulfide nano composite coating (Mo-B-S-C-N five-element hard coating). The atomic percentage of the elements in the coating is 48.0Mo-31.0N-5.5B-11.0C-45S, the hardness of the coating is 23.5GPa, the thickness is 2.0 mu m, the friction coefficient at normal temperature is 0.19, and the friction coefficient at 600 ℃ is 0.34.
Example 2
1) Molybdenum target and 2 blocks B in FIG. 1 4 C and 1 MoS 2 A composite target consisting of B as a magnetron sputtering source 4 C and MoS 2 And the area ratio of Mo is 2:1:17, and the distance between the composite target and the substrate is 10cm;
2) Selecting high-speed steel as a base material, derusting and polishing the surface of the base material, respectively cleaning the base material for 10min in an ultrasonic cleaner by using acetone, alcohol and deionized water, drying the base material by using hot air, and placing the base material on a sample table in a vacuum chamber;
3) The vacuum degree in the vacuum chamber is pumped to be less than or equal to 5 multiplied by 10 -4 After Pa, the substrate is negatively biased at 800V, and argon ions generated by glow discharge are used for sputtering and cleaning the surface of the substrate for 10min;
4) Introducing 4sccm argon and 20sccm nitrogen at a flow ratio of 1:5 and working pressure of 0.8Pa to form a mixed atmosphere, and sputtering Mo and (B) by using a magnetron sputtering technology 4 C and MoS 2 ) And (3) adding negative bias voltage to the substrate for 100eV in the deposition process of the composite target, performing auxiliary bombardment on the deposited coating by utilizing nitrogen ions, wherein the power of magnetron sputtering is 190W, the time is 180min, and after the magnetron sputtering is finished, stopping introducing argon and nitrogen, and keeping the vacuum state until the temperature of the substrate is less than or equal to 60 ℃, thereby preparing the boron-molybdenum nitride/molybdenum sulfide nano composite coating (Mo-B-S-C-N five-element hard coating). The atomic percentage of the elements in the coating is 52.0Mo-31.0N-4.5B-9.5C-3.0S, the hardness of the coating is 23.2GPa, the thickness is 2.1 mu m, the normal temperature friction coefficient is 0.27, and the friction coefficient at 600 ℃ is 0.26.
Example 3
1) Molybdenum target and 4 blocks B in FIG. 1 4 C and 2 MoS blocks 2 A composite target consisting of B as a magnetron sputtering source 4 C and MoS 2 And the area ratio of Mo is 2:1:7, and the distance between the composite target and the substrate is 10cm;
2) Selecting high-speed steel as a base material, derusting and polishing the surface of the base material, respectively cleaning the base material for 10min in an ultrasonic cleaner by using acetone, alcohol and deionized water, drying the base material by using hot air, and placing the base material on a sample table in a vacuum chamber;
3) The vacuum degree in the vacuum chamber is pumped to be less than or equal to 5 multiplied by 10 -4 After Pa, the substrate is negatively biased at 800V, and argon ions generated by glow discharge are used for sputtering and cleaning the surface of the substrate for 10min;
4) Introducing 4sccm argon and 40sccm nitrogen, wherein the flow ratio is 1:10, the working pressure is 1.2Pa, forming a mixed atmosphere, and sputtering Mo and B by adopting a magnetron sputtering technology 4 And (3) adding negative bias voltage to the substrate for 100eV in the deposition process of the C composite target, carrying out auxiliary bombardment on the deposited coating by utilizing nitrogen ions, wherein the power of magnetron sputtering is 180W, the time is 120min, and after the magnetron sputtering is finished, stopping introducing argon and nitrogen, and keeping the vacuum state until the temperature of the substrate is less than or equal to 60 ℃, thereby preparing the boron-molybdenum nitride/molybdenum sulfide nano composite coating (Mo-B-S-C-N five-element hard coating). The atomic percentage of elements in the coating is 42.0Mo-32.0N-9.5B-12.5C-4.0S, the hardness of the coating is 26.8GPa, the thickness is 1.5 mu m, the normal temperature friction coefficient is 0.24, and the friction coefficient at 600 ℃ is 0.15.
Example 4
1) Molybdenum target and 5 blocks B in FIG. 1 4 C and 1 MoS 2 A composite target consisting of B as a magnetron sputtering source 4 C and MoS 2 And the area ratio of Mo is 5:1:14, and the distance between the composite target and the substrate is 10cm;
2) Selecting high-speed steel as a base material, derusting and polishing the surface of the base material, respectively cleaning the base material for 10min in an ultrasonic cleaner by using acetone, alcohol and deionized water, drying the base material by using hot air, and placing the base material on a sample table in a vacuum chamber;
3) The vacuum degree in the vacuum chamber is pumped to be less than or equal to 5 multiplied by 10 -4 After Pa, the substrate is negatively biased at 800V, and argon ions generated by glow discharge are used for sputtering and cleaning the surface of the substrate for 10min;
4) Introducing 4sccm argon and 40sccm nitrogen, wherein the flow ratio is 1:10, the working pressure is 1.2Pa, forming a mixed atmosphere, and sputtering Mo and B by adopting a magnetron sputtering technology 4 The C composite target is characterized in that a substrate is negatively biased for 90eV in the deposition process, nitrogen ions are utilized to carry out auxiliary bombardment on a coating in the deposition, the power of magnetron sputtering is 180W, the time is 240min, and after the magnetron sputtering is finished, argon and nitrogen are stopped being introduced, and the vacuum state is maintained untilThe temperature of the substrate is less than or equal to 60 ℃, and the boron molybdenum nitride/molybdenum sulfide nano composite coating (Mo-B-S-C-N five-membered hard coating) is prepared. The atomic percentage of the elements in the coating is 40.0Mo-33.5N-12.B-14.0C-0.5S, the hardness of the coating is 27.5GPa, the thickness is 1.7 mu m, the normal temperature friction coefficient is 0.32, and the friction coefficient at 600 ℃ is 0.20.
Example 5
1) Molybdenum target and B 4 C and MoS 2 A composite target consisting of B as a magnetron sputtering source 4 C and MoS 2 And the area ratio of Mo is 1:1:20, and the distance between the composite target and the substrate is 8cm;
2) Selecting hard alloy as a substrate material, polishing the surface of the substrate material, respectively cleaning the substrate material with acetone, alcohol and deionized water in an ultrasonic cleaner for 10min, drying the substrate material with hot air, and placing the substrate material on a sample table in a vacuum chamber;
3) The vacuum degree in the vacuum chamber is pumped to be less than or equal to 5 multiplied by 10 -4 After Pa, the substrate is negatively biased at 800V, and argon ions generated by glow discharge are used for sputtering and cleaning the surface of the substrate for 12min;
4) Introducing 4sccm argon and 4sccm nitrogen, wherein the flow ratio is 1:1, the working pressure is 0.1Pa, forming a mixed atmosphere, and sputtering Mo and B by adopting a magnetron sputtering technology 4 And (3) adding negative bias voltage to the substrate for 120eV in the deposition process of the C composite target, performing auxiliary bombardment on the deposited coating by utilizing nitrogen ions, wherein the power of magnetron sputtering is 300W, the time is 160min, and after the magnetron sputtering is finished, stopping introducing argon and nitrogen, and keeping the vacuum state until the temperature of the substrate is less than or equal to 60 ℃, thereby preparing the boron-molybdenum nitride/molybdenum sulfide nano composite coating (Mo-B-S-C-N five-element hard coating).
Example 6
1) Molybdenum target and B 4 C and MoS 2 A composite target consisting of B as a magnetron sputtering source 4 C and MoS 2 And the area ratio of Mo is 1:2:7, and the distance between the composite target and the substrate is 9cm;
2) Cast iron is selected as a base material, the surface of the base material is derusted and polished, and is respectively cleaned for 10 minutes in an ultrasonic cleaner by acetone, alcohol and deionized water, and then is dried by hot air and is placed on a sample table in a vacuum chamber;
3) True senseThe vacuum degree in the air chamber is pumped to be less than or equal to 5 multiplied by 10 -4 After Pa, the substrate is negatively biased at 800V, and argon ions generated by glow discharge are used for sputtering and cleaning the surface of the substrate for 15min;
4) Introducing 8sccm argon and 32sccm nitrogen, wherein the flow ratio is 5:1, the working pressure is 2Pa, forming a mixed atmosphere, and sputtering Mo and B by adopting a magnetron sputtering technology 4 And (3) adding negative bias voltage to the substrate for 40eV in the deposition process of the C composite target, performing auxiliary bombardment on the deposited coating by utilizing nitrogen ions, wherein the power of magnetron sputtering is 140W, the time is 200min, and after the magnetron sputtering is finished, stopping introducing argon and nitrogen, and keeping the vacuum state until the temperature of the substrate is less than or equal to 60 ℃, thereby preparing the boron-molybdenum nitride/molybdenum sulfide nano composite coating (Mo-B-S-C-N five-element hard coating).
Example 7
1) Molybdenum target and B 4 C and MoS 2 A composite target consisting of B as a magnetron sputtering source 4 C and MoS 2 And the area ratio of Mo is 1:5:14, and the distance between the composite target and the substrate is 11cm;
2) Selecting alumina ceramic as a base material, polishing the surface of the base material, respectively cleaning the base material for 10min in an ultrasonic cleaner by using acetone, alcohol and deionized water, drying the base material by using hot air, and placing the base material on a sample table in a vacuum chamber;
3) The vacuum degree in the vacuum chamber is pumped to be less than or equal to 5 multiplied by 10 -4 After Pa, the substrate is negatively biased at 800V, and argon ions generated by glow discharge are used for sputtering and cleaning the surface of the substrate for 20min;
4) Introducing 10sccm argon and 30sccm nitrogen, wherein the flow ratio is 3:1, the working pressure is 1.6Pa, forming a mixed atmosphere, and sputtering Mo and B by adopting a magnetron sputtering technology 4 And (3) adding negative bias voltage to the substrate for 60eV in the deposition process of the C composite target, carrying out auxiliary bombardment on the deposited coating by utilizing nitrogen ions, wherein the power of magnetron sputtering is 280W, the time is 220min, and after the magnetron sputtering is finished, stopping introducing argon and nitrogen, and keeping the vacuum state until the temperature of the substrate is less than or equal to 60 ℃, thereby preparing the boron-molybdenum nitride/molybdenum sulfide nano composite coating (Mo-B-S-C-N five-element hard coating).
Example 8
1) Molybdenum target and B 4 C composite target is used as a magnetron sputtering source, wherein B 4 The area ratio of C to Mo is 1:15, and the distance between the composite target and the substrate is 12cm;
2) Selecting high-speed steel as a base material, derusting and polishing the surface of the base material, respectively cleaning the base material for 10min in an ultrasonic cleaner by using acetone, alcohol and deionized water, drying the base material by using hot air, and placing the base material on a sample table in a vacuum chamber;
3) The vacuum degree in the vacuum chamber is pumped to be less than or equal to 5 multiplied by 10 -4 After Pa, the substrate is negatively biased at 700V, and argon ions generated by glow discharge are used for sputtering and cleaning the surface of the substrate for 10min;
4) Introducing 6sccm argon and 12sccm nitrogen, wherein the flow ratio is 1:2, the working pressure is 0.4Pa, forming a mixed atmosphere, and sputtering Mo and B by adopting a magnetron sputtering technology 4 And (3) adding negative bias voltage to the substrate for 80eV in the deposition process, performing auxiliary bombardment on the deposited coating by utilizing nitrogen ions, wherein the power of magnetron sputtering is 100W, the time is 140min, and after the magnetron sputtering is finished, stopping introducing argon and nitrogen, and keeping the vacuum state until the temperature of the substrate is less than or equal to 60 ℃, thereby preparing the boron-molybdenum nitride/molybdenum sulfide nano composite coating (Mo-B-S-C-N five-membered hard coating).
FIG. 2 is an XRD pattern of a molybdenum boride/molybdenum sulfide nanocomposite coating produced in accordance with the present invention; as can be seen from FIG. 2, the Mo-B-S-C-N quinary hard coating consists essentially of MoN phase and Mo 2 N phase composition, small amounts of MoB and MoS are also present in the coating 2 And (3) phase (C).
FIG. 3 is a graph showing the relationship between the hardness and B, S content of the boron-molybdenum nitride/molybdenum sulfide nanocomposite coating produced in accordance with the present invention, wherein the content of B, S element in the coating produced in example 1 is 5.5% and 4.5% by atom, the content of B, S element in the coating produced in example 2 is 4.5% and 3.0% by atom, the content of B, S element in the coating produced in example 3 is 9.5% and 4.0% by atom, and the content of B, S element in the coating produced in example 4 is 12.0% and 0.5% by atom, respectively. As can be seen from FIG. 3, the hardness of the boron molybdenum nitride/molybdenum sulfide nano composite coating formed after B, S element is added is high, the content of B element is increased, the hardness of the boron molybdenum nitride/molybdenum sulfide nano composite coating is increased, and the hardness of the coating is reduced after S element is added.
FIG. 4 is a graph showing the relationship between the average friction coefficient and the content of B, S element in the boron-molybdenum nitride/molybdenum sulfide nanocomposite coating prepared according to the present invention at room temperature, wherein the content of B, S element in the coating prepared in example 1 is 5.5% and the content of B, S element in the coating prepared in example 2 is 4.5% and 3.0% respectively, the content of B, S element in the coating prepared in example 3 is 9.5% and 4.0% respectively, and the content of B, S element in the coating prepared in example 4 is 12.0% and 0.5% respectively. As can be seen from fig. 4, the average friction coefficient of the boron nitride/molybdenum sulfide nanocomposite coating formed after adding B, S element is lower than 0.32, and the S element content is increased, and the average friction coefficient of the boron nitride/molybdenum sulfide nanocomposite coating is reduced.
FIG. 5 is a graph showing the relationship between the abrasion rate and C, B content of the boron-molybdenum nitride/molybdenum sulfide nanocomposite coating produced by the present invention at room temperature, wherein the content of B, S element in the coating produced in example 1 is 5.5% and 4.5% by atom, the content of B, S element in the coating produced in example 2 is 4.5% and 3.0% by atom, the content of B, S element in the coating produced in example 3 is 9.5% and 4.0% by atom, and the content of B, S element in the coating produced in example 4 is 12.0% and 0.5% by atom, respectively. As can be seen from FIG. 5, the wear rate of the boron molybdenum nitride/molybdenum sulfide nano composite coating formed after B, S element is lower and is 10 -16 m 3 (N·m) -1 The abrasion rate of the boron molybdenum nitride/molybdenum sulfide nanocomposite coating decreases with increasing element B, S content.
FIG. 6 is a graph showing the relationship between the average friction coefficient and C, B content of the molybdenum boride/molybdenum sulfide nanocomposite coating produced by the present invention at 600deg.C, wherein the content of B, S element in the coating produced in example 1 was 5.5% and 4.5% by atom, the content of B, S element in the coating produced in example 2 was 4.5% and 3.0% by atom, the content of B, S element in the coating produced in example 3 was 9.5% and 4.0% by atom, and the content of B, S element in the coating produced in example 4 was 12.0% and 0.5% by atom, respectively. As can be seen from fig. 6, the average friction coefficient of the molybdenum boride/molybdenum sulfide nanocomposite coating formed after adding B, S element is lower than 0.4, while the average friction coefficient of the molybdenum boride/molybdenum sulfide nanocomposite coating formed after adding B, S element is lower, which indicates that the appropriate C, B content at high temperature is more beneficial to reducing the friction coefficient of the Mo-B-S-C-N five-membered hard coating.
FIG. 7 is a graph showing the relationship between the abrasion rate and C, B content of the molybdenum boride/molybdenum sulfide nanocomposite coating of the present invention at 600deg.C, wherein the content of B, S element in the coating of example 1 was 5.5% and 4.5% by atom, the content of B, S element in the coating of example 2 was 4.5% and 3.0% by atom, the content of B, S element in the coating of example 3 was 9.5% and 4.0% by atom, and the content of B, S element in the coating of example 4 was 12.0% and 0.5% by atom, respectively. As can be seen from fig. 7, the wear rate of the boron molybdenum nitride/molybdenum sulfide nanocomposite coating formed after adding B, S element is significantly lower than that of molybdenum nitride, but with increasing B, S element content, the wear rate of the boron molybdenum nitride/molybdenum sulfide nanocomposite coating is reduced, and the wear rate is only 1/80 of MoN when the B, S element ratio is appropriate.

Claims (8)

1. A molybdenum boride/molybdenum sulfide nanocomposite coating, characterized by: the boron molybdenum nitride/molybdenum sulfide nano composite coating is a Mo-B-S-C-N five-membered coating, wherein the atomic percentage of Mo element is 55-40%, the atomic percentage of N element is 42-24%, the atomic percentage of B element is 9.5-12%, the atomic percentage of C element is 2-14%, and the atomic percentage of S element is 0.5-10%;
the boron nitride molybdenum sulfide nano composite coating is prepared according to the following steps:
1) Will be composed of metal Mo and B 4 C and MoS 2 The composite target and the substrate are respectively arranged on a cathode and a sample table in a vacuum chamber of the magnetron sputtering equipment; metallic Mo and (B) 4 C and MoS 2 ) The area ratio is 10:1-7:3, wherein B is as follows 4 C and MoS 2 The area ratio is 5:1-1:5, the purity of Mo is 99.99%, and B is 4 C and MoS 2 The purity of (2) is 99.9%, and the composite targetThe distance between the substrate and the substrate is 80-120 mm;
2) Vacuumizing a vacuum chamber of the magnetron sputtering equipment, then introducing argon and performing glow discharge, and applying negative bias to a substrate for sputtering cleaning;
3) Argon and nitrogen are introduced into a vacuum chamber of the magnetron sputtering equipment, the magnetron sputtering composite target is subjected to negative bias on a substrate in the deposition process, and nitrogen ions are used for bombardment, so that the boron molybdenum nitride/molybdenum sulfide nano composite coating is obtained, the flow ratio of the argon to the nitrogen is 5:1-1:10, and the working pressure is 0.1-2 Pa.
2. The molybdenum boride/molybdenum sulfide nanocomposite coating according to claim 1, characterized in that: the hardness of the boron molybdenum nitride/molybdenum sulfide nano composite coating is 19-27 GPa, the friction coefficient at normal temperature is more than or equal to 0.19, and the friction coefficient at 600 ℃ is more than or equal to 0.15.
3. A method for preparing a boron molybdenum nitride/molybdenum sulfide nano composite coating according to claim 1, comprising the steps of:
1) Will be composed of metal Mo and B 4 C and MoS 2 The composite target and the substrate are respectively arranged on a cathode and a sample table in a vacuum chamber of the magnetron sputtering equipment; metallic Mo and (B) 4 C and MoS 2 ) The area ratio is 10:1-7:3, wherein B is as follows 4 C and MoS 2 The area ratio is 5:1-1:5, the purity of Mo is 99.99%, and B is 4 C and MoS 2 The purity of the composite target is 99.9%, and the distance between the composite target and the substrate is 80-120 mm;
2) Vacuumizing a vacuum chamber of the magnetron sputtering equipment, then introducing argon and performing glow discharge, and applying negative bias to a substrate for sputtering cleaning;
3) Argon and nitrogen are introduced into a vacuum chamber of the magnetron sputtering equipment, the magnetron sputtering composite target is subjected to negative bias on a substrate in the deposition process, and nitrogen ions are used for bombardment, so that the boron molybdenum nitride/molybdenum sulfide nano composite coating is obtained, the flow ratio of the argon to the nitrogen is 5:1-1:10, and the working pressure is 0.1-2 Pa.
4. A method for preparing a molybdenum boride/molybdenum sulfide nanocomposite coating according to claim 3, characterized in that: the substrate is a metal substrate or a ceramic substrate, wherein the metal substrate is steel, cast iron or hard alloy.
5. A method for preparing a molybdenum boride/molybdenum sulfide nanocomposite coating according to claim 3, characterized in that: in the step 2), the vacuum degree in the vacuum chamber of the magnetron sputtering equipment is pumped to be less than or equal to 5 multiplied by 10 -4 And after Pa, applying negative bias voltage to the substrate by 400-800V, and cleaning the surface of the substrate by utilizing argon ion sputtering for at least 10min.
6. A method for preparing a molybdenum boride/molybdenum sulfide nanocomposite coating according to claim 3, characterized in that: the power of the magnetron sputtering in the step 3) is 100-300W, and the time is 120-240 min.
7. A method for preparing a molybdenum boride/molybdenum sulfide nanocomposite coating according to claim 3, characterized in that: in the step 3), the substrate is negatively biased to 40V-120V in the deposition process, and nitrogen ions are utilized to carry out auxiliary bombardment on the coating in the deposition process.
8. A method for preparing a molybdenum boride/molybdenum sulfide nanocomposite coating according to claim 3, characterized in that: and 3) stopping introducing argon and nitrogen after the magnetron sputtering is finished, and keeping the vacuum state until the substrate temperature is less than or equal to 60 ℃.
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JPS61120897A (en) * 1984-11-19 1986-06-07 Nippon Telegr & Teleph Corp <Ntt> Preparation of solid lubricant film
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CN105441890A (en) * 2015-12-22 2016-03-30 西安交通大学 High-temperature and low-friction-coefficient hard coating layer and preparation method thereof
CN105887025A (en) * 2016-06-15 2016-08-24 济宁学院 ZrTiN/MoS2 composite antifriction wear-resistant coated tool and preparation process thereof
CN110735120A (en) * 2019-10-31 2020-01-31 江苏科技大学 NbN/MoSN/MoS2Hard self-lubricating nano-structure composite film and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61120897A (en) * 1984-11-19 1986-06-07 Nippon Telegr & Teleph Corp <Ntt> Preparation of solid lubricant film
US5135808A (en) * 1990-09-27 1992-08-04 Diamonex, Incorporated Abrasion wear resistant coated substrate product
CN105441890A (en) * 2015-12-22 2016-03-30 西安交通大学 High-temperature and low-friction-coefficient hard coating layer and preparation method thereof
CN105887025A (en) * 2016-06-15 2016-08-24 济宁学院 ZrTiN/MoS2 composite antifriction wear-resistant coated tool and preparation process thereof
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