CN105441890A - High-temperature and low-friction-coefficient hard coating layer and preparation method thereof - Google Patents

High-temperature and low-friction-coefficient hard coating layer and preparation method thereof Download PDF

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CN105441890A
CN105441890A CN201510974804.6A CN201510974804A CN105441890A CN 105441890 A CN105441890 A CN 105441890A CN 201510974804 A CN201510974804 A CN 201510974804A CN 105441890 A CN105441890 A CN 105441890A
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hard coat
friction coefficient
high temperature
temperature low
preparation
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CN105441890B (en
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朱晓东
商琛
李倩叶
邱龙时
徐可为
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Ningbo Yuntu Technology Co Ltd
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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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a high-temperature and low-friction-coefficient hard coating layer and a preparation method thereof. A reactive magnetron sputtering technology is adopted to sputter a metal Mo and B4C composite target on a cathode; the metal Mo and B4C composite target is reacted with N2 in Ar and N2 mixed gas in a vacuum chamber to form a Mo-B-C-N quaternary hard coating layer with proper contents of elements C and B on the surface of a substrate; the Mo-B-C-N quaternary hard coating layer is the high-temperature and low-friction-coefficient hard coating layer; and the contents of B and C in the coating layer are easy to control through adjusting an area of B4C in the composite target. The atomic percentages of elements of C, B, Mo and N in the coating layer are respectively 2-12%, 0.5-8%, 55-42% and 44-38%. The method is simple in process and easy to carry out. The prepared high-temperature and low-friction-coefficient hard coating layer overcomes the defects of performances of a traditional hard plating layer, has the characteristics of high hardness, wear resistance, high temperature and low friction coefficient, and is excellent in promotion and application prospect on a high-speed cutting tool.

Description

A kind of high temperature low-friction coefficient hard coat and preparation method thereof
Technical field
The invention belongs to material surface coating technology field, be specifically related to a kind of high temperature low-friction coefficient hard coat and preparation method thereof.
Background technology
Along with the development of modern mechanical manufacturing industry, at a high speed, a large amount of uses of High Precision Automatic processing units and difficult-to-machine material, high-performance metal-cutting cutter is had higher requirement.Hard coating has higher thermostability and unreactiveness, decreases and cuts heat of friction basad transmission, and coating is from the hardness of height and good wear resistance, ensure that the sharpness that cutting edge is good and cutting ability.But when high speed cutting, the problem that liquid lubricant performance often faces Yin Gaowen and decays, cutting fluid needs to consume ample resources and the energy in production, use, discharge and last handling process, also certain pollution is had to environment, along with industrial discharge standard is more strict, the use of cutting fluid is subject to further restriction.Rubbing factor due to hard coating is general higher, not only makes wearing and tearing aggravate, and a large amount of heat in metal cutting causes coating to produce the phenomenons such as oxidation, thermal fatigue.Therefore, under the prerequisite guaranteeing wear resistance and high-temperature oxidation resistance, reduce the frictional coefficient of coating as far as possible for the wear resistance and the cutting ability better effects if that improve cutter.
The nitride hardness of magnesium-yttrium-transition metal molybdenum can reach 23GPa, close with CrN, TiN etc., and frictional coefficient is lower.Frictional coefficient under high temperature can be lower, but wear resistance sharply declines, and limits its application under harsh machining condition.There is not been reported for the document of current research Mo-B-C-N quaternary coating.
Summary of the invention
The object of the present invention is to provide a kind of high temperature low-friction coefficient hard coat and preparation method thereof, prepare Mo-B-C-N quaternary coating by the method for cosputtering, this coating has both wear-resisting and feature that is high temperature low-friction coefficient.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for high temperature low-friction coefficient hard coat, comprises the following steps:
1) will by metal M o and B 4the composition target that C is formed and substrate are placed in negative electrode in magnetron sputtering equipment vacuum chamber and sample table respectively;
2) to magnetron sputtering equipment vacuum chamber, ar-ion beam sputter clean substrate surface is then used;
3) in magnetron sputtering equipment vacuum chamber, pass into argon gas and nitrogen, magnetron sputtering composition target, and with nitrogen ion beam, auxiliary bombardment is carried out to the coating in deposition in deposition process, obtain high temperature low-friction coefficient hard coat.
Metal M o and B in described composition target 4to be the purity of 20:1 ~ 2:1, Mo be 99.99% for the area ratio of C, B 4the purity of C is 99.9%, and the distance between composition target and substrate is 80 ~ 120mm.
Described substrate is metal base or ceramic bases, and wherein metal base is steel, cast iron or Wimet.
Described step 2) in the vacuum tightness in magnetron sputtering equipment vacuum chamber is extracted into≤5 × 10 -4after Pa, with energy be 800 ~ 1000eV, beam current density is 10 ~ 20 μ A/cm 2ar-ion beam sputter clean substrate surface at least 10min.
Described step 3) in the throughput ratio of the argon gas that passes into and nitrogen be 1:1 ~ 1:10, operating air pressure is 0.1 ~ 2Pa.
Described step 3) in the power of magnetron sputtering be 100 ~ 300W, the time is 120 ~ 240min.
Described step 3) in deposition process with energy be 500eV ~ 2000eV, beam current density is 5 ~ 10 μ A/cm 2nitrogen ion beam auxiliary bombardment is carried out to the coating in deposition.
Described step 3) in after magnetron sputtering terminates, stop pass into argon gas and nitrogen, keep vacuum state, to base reservoir temperature≤60 DEG C.
The high temperature low-friction coefficient hard coat that the preparation method of described high temperature low-friction coefficient hard coat obtains, this high temperature low-friction coefficient hard coat is Mo-B-C-N quaternary coating, wherein the atomic percent of C element is 2 ~ 12%, the atomic percent of B element is 0.5 ~ 8%, the atomic percent of Mo element is 55 ~ 42%, and the atomic percent of N element is 44 ~ 38%.
The hardness of this high temperature low-friction coefficient hard coat is 27 ~ 31GPa, frictional coefficient >=0.23 under normal temperature, frictional coefficient >=0.15 when 600 DEG C.
Relative to prior art, beneficial effect of the present invention is:
The preparation method of high temperature low-friction coefficient hard coat provided by the invention, on the basis of molybdenum nitride, has selected suitable Mo/B 4c composition target and corresponding splash-proofing sputtering process parameter, adopt reaction magnetocontrol sputtering technology cathode sputtering metal Mo and B 4c composition target, and with Ar and N in vacuum chamber 2n in mixed gas 2solid/liquid/gas reactions, defines at substrate surface and obtains the suitable Mo-B-C-N quaternary hard coat of C, B element content, i.e. high temperature low-friction coefficient hard coat, by regulating B in composition target 4the area of C, makes the content of B and C in this coating easily control, and the method technique is simple, easy to implement.
High temperature low-friction coefficient hard coat provided by the invention (Mo-B-C-N quaternary hard coat), wherein the atomic percent of C, B, Mo, N element is respectively 2 ~ 12%, 0.5 ~ 8%, 55 ~ 42%, 44 ~ 38%.This coating overcomes the deficiency of existing hard coating performance, has both the feature of high, the wear-resisting and high temperature low-friction coefficient of hardness, makes it on high speed cutting instrument, have good popularizing application prospect.
Further, found through experiments, the hardness of the high temperature low-friction coefficient hard coat (Mo-B-C-N quaternary hard coat) that the present invention obtains brings up to more than 30GPa by the 23GPa of molybdenum nitride coating, under room temperature, frictional coefficient is reduced to 0.23,600 DEG C of frictional coefficient can be reduced to 0.15, and wear rate is less than 1/20 of molybdenum nitride.
Accompanying drawing explanation
Fig. 1 be the present invention use by metal M o and B 4the structural representation of the composition target that C is formed;
Fig. 2 is the XRD figure of the high temperature low-friction coefficient hard coat that the present invention obtains;
Fig. 3 is the hardness of high temperature low-friction coefficient hard coat that obtains of the present invention and the graph of a relation of C, B content;
Fig. 4 is the average friction coefficient of high temperature low-friction coefficient hard coat and the graph of a relation of C, B content that under normal temperature, the present invention obtains.
Fig. 5 is the wear rate of high temperature low-friction coefficient hard coat and the graph of a relation of C, B content that under normal temperature, the present invention obtains.
Fig. 6 is the average friction coefficient of high temperature low-friction coefficient hard coat and the graph of a relation of C, B content that at 600 DEG C, the present invention obtains.
Fig. 7 is the wear rate of high temperature low-friction coefficient hard coat and the graph of a relation of C, B content that at 600 DEG C, the present invention obtains.
Embodiment
The present invention prepares high temperature low-friction coefficient hard coat (Mo-B-C-N quaternary coating), adopts molybdenum target (purity 99.99%) and B 4composition target made by C target (purity 99.9%), by magnetically controlled DC sputtering, is deposited in the substrate of metal, Wimet or pottery, and assists bombardment to obtain with nitrogen ion beam.The thickness of obtained high temperature low-friction coefficient hard coat (Mo-B-C-N quaternary coating) is 1 ~ 5 μm, and hardness is 27 ~ 31GPa, and the frictional coefficient under normal temperature is minimum is 0.23, and under high temperature, the frictional coefficient of (600 DEG C) is minimum is 0.15.Wherein the atomic percent of C element is 2 ~ 12%, and the atomic percent of B element is the atomic percent of 0.5 ~ 8%, Mo element is 55 ~ 42%, and the atomic percent of N element is 44 ~ 38%.
In conjunction with frictional coefficient under differing temps and wear resistance, show that more excellent scope is the atomic percent 1.5 ~ 6% of the atomic percent 3 ~ 10% of C element, B element.
The concrete steps of the preparation method of high temperature low-friction coefficient hard coat provided by the invention are:
1) with metal (steel, cast iron or Wimet) or pottery for substrate, deoil, after deoxidation compound, hot blast drying on fixing rotatable workpiece frame in a vacuum chamber;
2) by the B of high-purity Mo and some amount 4the composition target of C sheet composition is arranged on controlled sputtering source; Metal M o and B wherein in composition target 4to be the purity of 20:1 ~ 2:1, Mo be 99.99% for the area ratio of C, B 4the purity of C is 99.9%, and the distance between composition target and substrate is 80 ~ 120mm;
3) subsequently vacuum tightness in vacuum chamber is extracted into≤5 × 10 -4pa, passes into the Ar that flow is 20sccm, when gas pressure in vacuum is 0.3Pa, and pre-sputtering Mo/B 4c composition target 5min, the power of pre-sputtering is 150W;
4) ion source passes into 6sccm argon gas subsequently, with ar-ion beam sputter clean substrate surface at least 10min, ion beam ion energy 800 ~ 1000eV, beam current density 10 ~ 20 μ A/cm 2;
5) pass into 4 ~ 10sccm argon gas and 4 ~ 40sccm nitrogen subsequently, form mixed atmosphere, the throughput ratio between argon gas and nitrogen is 1:1 ~ 1:10, and operating air pressure is 0.1 ~ 2Pa.
6) in vacuum chamber inherent argon nitrogen mixed gas atmosphere, with the power of 100 ~ 300W sputtering Mo/B 4c composition target 120 ~ 240min, and with energy 500eV ~ 2000eV, beam current density 5 ~ 10 μ A/cm 2nitrogen ion beam carries out auxiliary bombardment to the coating in deposition, obtained high temperature low-friction coefficient hard coat (Mo-B-C-N quaternary hard coat).
Below in conjunction with drawings and Examples in detail the present invention is described in detail, but the present invention is not limited to following embodiment.
Embodiment 1
1) by molybdenum target in Fig. 1 and 2 pieces of B 4c composition composition target as controlled sputtering source, wherein B 4the area ratio of C and Mo is 1:9, and the distance of composition target and substrate is 10cm;
2) select rapid steel as base material, by its surface derusting polishing, and respectively with acetone, alcohol and deionized water in ultrasonic cleaner after each cleaning 10min, be placed in the sample table in vacuum chamber with hot blast drying;
3) in vacuum chamber vacuum tightness be extracted into≤5 × 10 -4after Pa, with ar-ion beam sputter clean substrate surface 10min, ion energy 800eV, beam current density 10 μ A/cm 2;
4) pass into 4sccm argon gas and 20sccm nitrogen, throughput ratio is 1:5, and operating air pressure is 1Pa, forms mixed atmosphere, adopts magnetron sputtering technique sputtering Mo and B 4c composition target, with energy 2000eV, beam current density 5 μ A/cm in deposition process 2nitrogen ion beam auxiliary bombardment is carried out to the coating in deposition, the power of magnetron sputtering is 200W, time is 180min, after magnetron sputtering terminates, stop passing into argon gas and nitrogen, keep vacuum state, to base reservoir temperature≤60 DEG C, obtained high temperature low-friction coefficient hard coat (Mo-B-C-N quaternary hard coat).In coating, the atomic percentage conc of element is 51.5Mo-44.0N-1.5B-3.0C, and the hardness of coating is 27.6GPa, and thickness is 1.9 μm, and frictional coefficient when normal temperature frictional coefficient is 0.23,600 DEG C is 0.15.
Embodiment 2
1) by molybdenum target in Fig. 1 and 4 pieces of B 4c composition composition target as controlled sputtering source, wherein B 4the area ratio of C and Mo is 1:4.5, and the distance of composition target and substrate is 10cm;
2) select rapid steel as base material, by its surface derusting polishing, and respectively with acetone, alcohol and deionized water in ultrasonic cleaner after each cleaning 10min, be placed in the sample table in vacuum chamber with hot blast drying;
3) in vacuum chamber vacuum tightness be extracted into≤5 × 10 -4after Pa, with ar-ion beam sputter clean substrate surface 10min, ion energy 800eV, beam current density 10 μ A/cm 2;
4) pass into 4sccm argon gas and 20sccm nitrogen, throughput ratio is 1:5, and operating air pressure is 1Pa, forms mixed atmosphere, adopts magnetron sputtering technique sputtering Mo and B 4c composition target, with energy 2000eV, beam current density 5 μ A/cm in deposition process 2nitrogen ion beam auxiliary bombardment is carried out to the coating in deposition, the power of magnetron sputtering is 200W, time is 180min, after magnetron sputtering terminates, stop passing into argon gas and nitrogen, keep vacuum state, to base reservoir temperature≤60 DEG C, obtained high temperature low-friction coefficient hard coat (Mo-B-C-N quaternary hard coat).In coating, the atomic percentage conc of element is 48.5Mo-43.5N-3.0B-5.0C, and the hardness of coating is 29.8GPa, and thickness is 1.7 μm, and frictional coefficient when normal temperature frictional coefficient is 0.28,600 DEG C is 0.16.
Embodiment 3
1) by molybdenum target in Fig. 1 and 6 pieces of B 4c composition composition target as controlled sputtering source, wherein B 4the area ratio of C and Mo is 1:3, and the distance of composition target and substrate is 10cm;
2) select rapid steel as base material, by its surface derusting polishing, and respectively with acetone, alcohol and deionized water in ultrasonic cleaner after each cleaning 10min, be placed in the sample table in vacuum chamber with hot blast drying;
3) in vacuum chamber vacuum tightness be extracted into≤5 × 10 -4after Pa, with ar-ion beam sputter clean substrate surface 10min, ion energy 800eV, beam current density 10 μ A/cm 2;
4) pass into 4sccm argon gas and 40sccm nitrogen, throughput ratio is 1:10, and operating air pressure is 1.5Pa, forms mixed atmosphere, adopts magnetron sputtering technique sputtering Mo and B 4c composition target, with energy 1000eV, beam current density 5 μ A/cm in deposition process 2nitrogen ion beam auxiliary bombardment is carried out to the coating in deposition, the power of magnetron sputtering is 300W, time is 120min, after magnetron sputtering terminates, stop passing into argon gas and nitrogen, keep vacuum state, to base reservoir temperature≤60 DEG C, obtained high temperature low-friction coefficient hard coat (Mo-B-C-N quaternary hard coat).In coating, the atomic percentage conc of element is 42.0Mo-38.0N-8.0B-12.0C, and the hardness of coating is 30.9GPa, and thickness is 1.3 μm, and frictional coefficient when normal temperature frictional coefficient is 0.35,600 DEG C is 0.51.
Embodiment 4
1) by molybdenum target in Fig. 1 and 1 piece of B 4c composition composition target as controlled sputtering source, wherein B 4the area ratio of C and Mo is 1:18, and the distance of composition target and substrate is 10cm;
2) select rapid steel as base material, by its surface derusting polishing, and respectively with acetone, alcohol and deionized water in ultrasonic cleaner after each cleaning 10min, be placed in the sample table in vacuum chamber with hot blast drying;
3) in vacuum chamber vacuum tightness be extracted into≤5 × 10 -4after Pa, with ar-ion beam sputter clean substrate surface 10min, ion energy 800eV, beam current density 10 μ A/cm 2;
4) pass into 4sccm argon gas and 40sccm nitrogen, throughput ratio is 1:10, and operating air pressure is 1.5Pa, forms mixed atmosphere, adopts magnetron sputtering technique sputtering Mo and B 4c composition target, with energy 500eV, beam current density 5 μ A/cm in deposition process 2nitrogen ion beam auxiliary bombardment is carried out to the coating in deposition, the power of magnetron sputtering is 100W, time is 240min, after magnetron sputtering terminates, stop passing into argon gas and nitrogen, keep vacuum state, to base reservoir temperature≤60 DEG C, obtained high temperature low-friction coefficient hard coat (Mo-B-C-N quaternary hard coat).In coating, the atomic percentage conc of element is 55.0Mo-42.5N-0.5B-2.0C, and the hardness of coating is 27.3GPa, and thickness is 2.3 μm, and frictional coefficient when normal temperature frictional coefficient is 0.25,600 DEG C is 0.29.
Embodiment 5
1) by molybdenum target and B 4c composition composition target as controlled sputtering source, wherein B 4the area ratio of C and Mo is 1:2, and the distance of composition target and substrate is 8cm;
2) select cast iron as base material, by its surface derusting polishing, and respectively with acetone, alcohol and deionized water in ultrasonic cleaner after each cleaning 10min, be placed in the sample table in vacuum chamber with hot blast drying;
3) in vacuum chamber vacuum tightness be extracted into≤5 × 10 -4after Pa, with ar-ion beam sputter clean substrate surface 11min, ion energy 1000eV, beam current density 15 μ A/cm 2;
4) pass into 4sccm argon gas and 4sccm nitrogen, throughput ratio is 1:1, and operating air pressure is 0.1Pa, forms mixed atmosphere, adopts magnetron sputtering technique sputtering Mo and B 4c composition target, with energy 1500eV, beam current density 6 μ A/cm in deposition process 2nitrogen ion beam auxiliary bombardment is carried out to the coating in deposition, the power of magnetron sputtering is 150W, time is 160min, after magnetron sputtering terminates, stop passing into argon gas and nitrogen, keep vacuum state, to base reservoir temperature≤60 DEG C, obtained high temperature low-friction coefficient hard coat (Mo-B-C-N quaternary hard coat).
Embodiment 6
1) by molybdenum target and B 4c composition composition target as controlled sputtering source, wherein B 4the area ratio of C and Mo is 1:20, and the distance of composition target and substrate is 9cm;
2) select Wimet as base material, by its surface derusting polishing, and respectively with acetone, alcohol and deionized water in ultrasonic cleaner after each cleaning 10min, be placed in the sample table in vacuum chamber with hot blast drying;
3) in vacuum chamber vacuum tightness be extracted into≤5 × 10 -4after Pa, with ar-ion beam sputter clean substrate surface 12min, ion energy 900eV, beam current density 20 μ A/cm 2;
4) pass into 8sccm argon gas and 32sccm nitrogen, throughput ratio is 1:4, and operating air pressure is 2Pa, forms mixed atmosphere, adopts magnetron sputtering technique sputtering Mo and B 4c composition target, with energy 800eV, beam current density 10 μ A/cm in deposition process 2nitrogen ion beam auxiliary bombardment is carried out to the coating in deposition, the power of magnetron sputtering is 250W, time is 200min, after magnetron sputtering terminates, stop passing into argon gas and nitrogen, keep vacuum state, to base reservoir temperature≤60 DEG C, obtained high temperature low-friction coefficient hard coat (Mo-B-C-N quaternary hard coat).
Embodiment 7
1) by molybdenum target and B 4c composition composition target as controlled sputtering source, wherein B 4the area ratio of C and Mo is 1:12, and the distance of composition target and substrate is 11cm;
2) Ceramics is as base material, by its surface derusting polishing, and respectively with acetone, alcohol and deionized water in ultrasonic cleaner after each cleaning 10min, be placed in the sample table in vacuum chamber with hot blast drying;
3) in vacuum chamber vacuum tightness be extracted into≤5 × 10 -4after Pa, with ar-ion beam sputter clean substrate surface 11min, ion energy 850eV, beam current density 12 μ A/cm 2;
4) pass into 10sccm argon gas and 30sccm nitrogen, throughput ratio is 1:3, and operating air pressure is 1.8Pa, forms mixed atmosphere, adopts magnetron sputtering technique sputtering Mo and B 4c composition target, with energy 1200eV, beam current density 8 μ A/cm in deposition process 2nitrogen ion beam auxiliary bombardment is carried out to the coating in deposition, the power of magnetron sputtering is 180W, time is 220min, after magnetron sputtering terminates, stop passing into argon gas and nitrogen, keep vacuum state, to base reservoir temperature≤60 DEG C, obtained high temperature low-friction coefficient hard coat (Mo-B-C-N quaternary hard coat).
Embodiment 8
1) by molybdenum target and B 4c composition composition target as controlled sputtering source, wherein B 4the area ratio of C and Mo is 1:15, and the distance of composition target and substrate is 12cm;
2) select rapid steel as base material, by its surface derusting polishing, and respectively with acetone, alcohol and deionized water in ultrasonic cleaner after each cleaning 10min, be placed in the sample table in vacuum chamber with hot blast drying;
3) in vacuum chamber vacuum tightness be extracted into≤5 × 10 -4after Pa, with ar-ion beam sputter clean substrate surface 12min, ion energy 950eV, beam current density 18 μ A/cm 2;
4) pass into 6sccm argon gas and 12sccm nitrogen, throughput ratio is 1:2, and operating air pressure is 0.5Pa, forms mixed atmosphere, adopts magnetron sputtering technique sputtering Mo and B 4c composition target, with energy 1800eV, beam current density 7 μ A/cm in deposition process 2nitrogen ion beam auxiliary bombardment is carried out to the coating in deposition, the power of magnetron sputtering is 220W, time is 140min, after magnetron sputtering terminates, stop passing into argon gas and nitrogen, keep vacuum state, to base reservoir temperature≤60 DEG C, obtained high temperature low-friction coefficient hard coat (Mo-B-C-N quaternary hard coat).
Fig. 2 is the XRD figure of the high temperature low-friction coefficient hard coat that the present invention obtains; As can be seen from Figure 2, coating is primarily of MoN phase and a small amount of Mo 2, in Mo-B-C-N quaternary hard coat, also there is a small amount of MoB phase in N phase composite.
Fig. 3 is the hardness of high temperature low-friction coefficient hard coat that obtains of the present invention and the graph of a relation of C, B content, in the coating that wherein embodiment 1 is obtained, the atomic percentage conc of B, C element is respectively 1.5% and 3.0%, in the coating that embodiment 2 is obtained, the atomic percentage conc of B, C element is respectively 3.0% and 5.0%, and in the coating that embodiment 3 is obtained, the atomic percentage conc of B, C element is respectively 8.0% and 12.0%.As can be seen from Figure 3, the hardness of the high temperature low-friction coefficient hard coat add C, forming after B element is all higher than molybdenum nitride coating, and along with the increase of C, B element content, the hardness of high temperature low-friction coefficient hard coat increases gradually.
Fig. 4 is the average friction coefficient of high temperature low-friction coefficient hard coat and the graph of a relation of C, B content that under normal temperature, the present invention obtains, in the coating that wherein embodiment 1 is obtained, the atomic percentage conc of B, C element is respectively 1.5% and 3.0%, in the coating that embodiment 2 is obtained, the atomic percentage conc of B, C element is respectively 3.0% and 5.0%, and in the coating that embodiment 3 is obtained, the atomic percentage conc of B, C element is respectively 8.0% and 12.0%.As can be seen from Figure 4, the average friction coefficient of the high temperature low-friction coefficient hard coat formed after adding C, B element decreases than molybdenum nitride, but along with the increase of C, B element content, the average friction coefficient of high temperature low-friction coefficient hard coat increases gradually.
Fig. 5 is the wear rate of high temperature low-friction coefficient hard coat and the graph of a relation of C, B content that under normal temperature, the present invention obtains, in the coating that wherein embodiment 1 is obtained, the atomic percentage conc of B, C element is respectively 1.5% and 3.0%, in the coating that embodiment 2 is obtained, the atomic percentage conc of B, C element is respectively 3.0% and 5.0%, and in the coating that embodiment 3 is obtained, the atomic percentage conc of B, C element is respectively 8.0% and 12.0%.As can be seen from Figure 5, the wear rate of the high temperature low-friction coefficient hard coat formed after adding C, B element decreases than molybdenum nitride, wear resistance increases than molybdenum nitride, but along with the increase of C, B element content, the wear rate of high temperature low-friction coefficient hard coat increases gradually.
Fig. 6 is the average friction coefficient of high temperature low-friction coefficient hard coat and the graph of a relation of C, B content that at 600 DEG C, the present invention obtains, in the coating that wherein embodiment 1 is obtained, the atomic percentage conc of B, C element is respectively 1.5% and 3.0%, in the coating that embodiment 2 is obtained, the atomic percentage conc of B, C element is respectively 3.0% and 5.0%, and in the coating that embodiment 3 is obtained, the atomic percentage conc of B, C element is respectively 8.0% and 12.0%.As can be seen from Figure 6, the average friction coefficient of the high temperature low-friction coefficient hard coat formed after adding a small amount of C, B element decreases than molybdenum nitride, and the average friction coefficient of the high temperature low-friction coefficient hard coat formed after adding relatively large C, B element is increased significantly than molybdenum nitride, C, B content suitable under high temperature is described can make the frictional coefficient of Mo-B-C-N quaternary hard coat lower than molybdenum nitride.
Fig. 7 is the wear rate of high temperature low-friction coefficient hard coat and the graph of a relation of C, B content that at 600 DEG C, the present invention obtains, in the coating that wherein embodiment 1 is obtained, the atomic percentage conc of B, C element is respectively 1.5% and 3.0%, in the coating that embodiment 2 is obtained, the atomic percentage conc of B, C element is respectively 3.0% and 5.0%, and in the coating that embodiment 3 is obtained, the atomic percentage conc of B, C element is respectively 8.0% and 12.0%.As can be seen from Figure 7, the wear rate of the high temperature low-friction coefficient hard coat formed after adding C, B element is to some extent obviously lower than molybdenum nitride, wear resistance is significantly improved than molybdenum nitride, but along with the increase of C, B element content, the wear rate of high temperature low-friction coefficient hard coat increases gradually.

Claims (10)

1. a preparation method for high temperature low-friction coefficient hard coat, is characterized in that, comprises the following steps:
1) will by metal M o and B 4the composition target that C is formed and substrate are placed in negative electrode in magnetron sputtering equipment vacuum chamber and sample table respectively;
2) to magnetron sputtering equipment vacuum chamber, ar-ion beam sputter clean substrate surface is then used;
3) in magnetron sputtering equipment vacuum chamber, pass into argon gas and nitrogen, magnetron sputtering composition target, and with nitrogen ion beam, auxiliary bombardment is carried out to the coating in deposition in deposition process, obtain high temperature low-friction coefficient hard coat.
2. the preparation method of high temperature low-friction coefficient hard coat according to claim 1, is characterized in that: metal M o and the B in described composition target 4to be the purity of 20:1 ~ 2:1, Mo be 99.99% for the area ratio of C, B 4the purity of C is 99.9%, and the distance between composition target and substrate is 80 ~ 120mm.
3. the preparation method of high temperature low-friction coefficient hard coat according to claim 1, it is characterized in that: described substrate is metal base or ceramic bases, wherein metal base is steel, cast iron or Wimet.
4. the preparation method of high temperature low-friction coefficient hard coat according to claim 1, is characterized in that: described step 2) in the vacuum tightness in magnetron sputtering equipment vacuum chamber is extracted into≤5 × 10 -4after Pa, with energy be 800 ~ 1000eV, beam current density is 10 ~ 20 μ A/cm 2ar-ion beam sputter clean substrate surface at least 10min.
5. the preparation method of high temperature low-friction coefficient hard coat according to claim 1, is characterized in that: described step 3) in the throughput ratio of the argon gas that passes into and nitrogen be 1:1 ~ 1:10, operating air pressure is 0.1 ~ 2Pa.
6. the preparation method of high temperature low-friction coefficient hard coat according to claim 1, is characterized in that: described step 3) in the power of magnetron sputtering be 100 ~ 300W, the time is 120 ~ 240min.
7. the preparation method of high temperature low-friction coefficient hard coat according to claim 1, is characterized in that: described step 3) in deposition process with energy be 500eV ~ 2000eV, beam current density is 5 ~ 10 μ A/cm 2nitrogen ion beam auxiliary bombardment is carried out to the coating in deposition.
8. the preparation method of high temperature low-friction coefficient hard coat according to claim 1, is characterized in that: described step 3) in after magnetron sputtering terminates, stop pass into argon gas and nitrogen, keep vacuum state, to base reservoir temperature≤60 DEG C.
9. the high temperature low-friction coefficient hard coat that the preparation method of the high temperature low-friction coefficient hard coat in claim 1-8 described in any one obtains, it is characterized in that: this high temperature low-friction coefficient hard coat is Mo-B-C-N quaternary coating, wherein the atomic percent of C element is 2 ~ 12%, the atomic percent of B element is 0.5 ~ 8%, the atomic percent of Mo element is 55 ~ 42%, and the atomic percent of N element is 44 ~ 38%.
10. high temperature low-friction coefficient hard coat according to claim 9, is characterized in that: the hardness of this high temperature low-friction coefficient hard coat is 27 ~ 31GPa, frictional coefficient >=0.23 under normal temperature, frictional coefficient >=0.15 when 600 DEG C.
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