CN105568235A - High-hardness CrBCN nanometer composite structure protective coating and preparation method thereof - Google Patents

High-hardness CrBCN nanometer composite structure protective coating and preparation method thereof Download PDF

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CN105568235A
CN105568235A CN201610130605.1A CN201610130605A CN105568235A CN 105568235 A CN105568235 A CN 105568235A CN 201610130605 A CN201610130605 A CN 201610130605A CN 105568235 A CN105568235 A CN 105568235A
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protective coating
crbcn
composite structure
layer
nano composite
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CN105568235B (en
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周溯源
韩滨
付德君
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Yichang Houhuang Vacuum Technology Co., Ltd.
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SUZHOU INSTITUTE OF WUHAN 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
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates

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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)
  • Inorganic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention provides a high-hardness CrBCN nanometer composite structure protective coating depositing on and covering a substrate. A transition layer is arranged between the protective coating and the substrate and divided into an upper layer and a lower layer. The lower layer making contact with the substrate is a metal combined layer made of Cr. The upper layer making contact with the protective coating is made of CrN. The thickness of the transition layer is 200-400 nm. The protective coating is of a nanometer composite structure with CrN nanometer equiaxed grains wrapped with the amorphous BCN interface phase and is 2-5 microns thick. The CrBCN nanometer composite protective coating has the advantages of high hardness and high abrasion resistance, and can serve as a coating for parts such as a high-speed cutting tool and a die and as a protective coating for equipment in other fields. A preparation method of the high-hardness CrBCN nanometer composite structure protective coating has the advantages of being high in production efficiency, low in energy consumption, simple in process, free of pollution, low in requirement for equipment and the like.

Description

A kind of high rigidity CrBCN nano composite structure protective coating and preparation method thereof
Technical field
The present invention relates to a kind of New Rigid supercoat; in particular to a kind of high rigidity CrBCN nano composite structure protective coating and preparation method thereof; be applied to cutter, mould etc. and bear the load parts such as wear-resisting, impact as protective coating, belong to material surface modifying technology field.
Background technology
Along with the development of society and the progress of science and technology, more and more higher requirement is proposed to the surface property of material, require that material is while the certain toughness of maintenance, also requires that material surface has higher hardness, wear-resisting, corrosion-resistant and resistance to elevated temperatures.Applying certain thickness coating at material surface is improve a kind of effective way of material surface performance, its development has adapted to the hi-tech requirement of modern society to material military service performance, has been widely used in the fields such as machinofacture, automotive industry, geological drilling, mould industry.Nanometer hard coat is a kind of effective process for modifying surface.Superhard coating is the coated material that hardness is greater than 40GPa, Wimet superhard coating cutter is integrated with intensity, toughness and hardness advantage, can significantly improve machining efficiency and quality, meet the new demand of high-speed and high-efficiency numerical control cutting processing, become the representative of high-grade cutter of new generation.Exploitation superhard coating coating, to raising China Computerized Numerical Control processing technology application level, promotes China's basis manufacturing capacity and has important practical significance.Along with going from bad to worse of material military service environment; higher requirement be it is also proposed to the performance of protective coating material; traditional protective coating, as TiN, TiC, TiCN, CrN, TiAlN etc. binary and ternary coating can not meet the demands that main drawback is its hardness gradually, film/base bonding force, wear resisting property and resistance toheat can not meet cutting requirement under extremely mal-condition.
Nanocrystalline and amorphous compound coating is the high-performance novel coating developed rapidly in recent years, the nanocrystalline of this material coating is wrapped up by amorphous phase, there is the performances such as good hardness, wear resistance, solidity to corrosion, coated cutting tool can be made to have higher cutting ability and longer work-ing life.In recent years, owing to having the high temperature resistant property of high rigidity, high-modulus, high-wearing feature and excellence, in nanocrystalline and amorphous composite superhard coating, the high rigidity of coating has relation primarily of the structure of the crystallization phases in coating and amorphous phase, and the size of crystallization phases particle directly determines the hardness of coating.Nanocomposite superhard material, with the performance of its excellence, as ultrahigh hardness, high tenacity and low frictional coefficient etc., causes the great interest of global researcher.Become the developing direction that advanced protective coating field is important, the requirement of high speed cutting and DRY CUTTING can have been met.
At present, known by inquiry document, nano composite structure coating is successfully obtained by different physical gas-phase deposite methods, by update search to the Patents preparing nano composite structure coating as follows:
Application number be 201210011554 Chinese patent relate to a kind of V-Al-N hard coat of nano composite structure, composition is expressed as (V 1-xal x) N, wherein, 1-x is 0.41 ~ 0.6, x is 0.4 ~ 0.59, while guarantee is compared with low-friction coefficient, can ensures to have higher hardness, be particularly suitable as cutter coat.This invention also discloses the preparation method of V-Al-N hard coat, comprises the following steps: matrix cleans; Deposited coatings: in a vacuum chamber, be arranged on by Al target on intermediate frequency negative electrode, V target is arranged on DC cathode, passes into Ar gas and N 2gas, by the power of adjustment Al target and the power of V target, under 250 DEG C ~ 500 DEG C and 0.3Pa ~ 1.0Pa condition, to the V-Al-N hard coat of matrix sputtering sedimentation nano composite structure.
Application number be 201010176236 Chinese patent relate to a kind of nano composite titanium-chromium-aluminum-silicon nitride cutter coating and preparation method thereof, tool matrix is WC/Co Wimet, coating includes the nano composite titanium-chromium-aluminum-silicon nitride coating of transition layer, wherein containing titanium, chromium, aluminium, silicon and nitrogen element, grain size at 5 ~ 15nm, coat-thickness 1 ~ 4 μm, coating microhardness 30GPa, high-temperature stability reaches more than 1022 DEG C, is applicable to the glass hard steel material machining under high-speed condition.
In above-mentioned existing nano-structured coating and technology of preparing thereof, do not seen the ultrahigh hardness coating that can reach more than 40GPa, and Young's modulus is also lower; In addition, existing technology of preparing energy consumption in preparation process is comparatively large, and efficiency is lower, and the equipment used also has a series of defects such as cost is high, production process is complicated, is difficult to realize large-scale industrial production.
Summary of the invention
Instant invention overcomes the deficiencies in the prior art; provide a kind of nano combined protective coating of CrBCN with high rigidity, high-wearing feature; can be used as the supercoat of the coating of the part such as high speed cutting tool, mould and other field equipment, and its preparation method has that production efficiency is high, energy consumption is low, technique is simple, pollution-free, to advantages such as equipment requirements are lower.
Realizing the technical scheme that above-mentioned purpose of the present invention adopts is:
A kind of high rigidity CrBCN nano composite structure protective coating; deposition is covered on matrix; transition layer is provided with between described protective coating and matrix; described transition layer is divided into two-layer up and down; the lower floor contacted with matrix phase is metal bonding layer Cr, and the upper strata contacted with protective coating is CrN, and the thickness of transition layer is 200 ~ 400nm; described protective coating is the nano composite structure of amorphous BCN interfacial phase parcel CrN nanometer equi-axed crystal, and its thickness is 2 ~ 5 μm.
The grain-size of described CrN nanometer equi-axed crystal is 5 ~ 10nm.
Described matrix is Wimet, stainless steel, rapid steel, carbon steel, die steel or pottery.
The preparation method of described high rigidity CrBCN nano composite structure protective coating comprises the following steps:
(1), the selecting of target: select purity to be two chromium targets of 99.99% and the array mode of two boron chromium targets, four targets are mutually 90 degree of placements, and centre is heating rod;
(2), substrate pretreated technique: routine is deoiled, decontamination process to be used by matrix surface washing composition to carry out, and then carries out polished finish, finally uses acetone and ethanol to carry out ultrasonic cleaning respectively, loads vacuum chamber, then carry out Ion Cleaning after oven dry;
(3), transition layer is deposited: by the matrix after Ion Cleaning at 200 DEG C ~ 400 DEG C, vacuum tightness 1x10 -3deposit Metal Cr layer under the condition of Pa, bias voltage-800V, then under 1.0Pa nitrogen environment, chromium target by radio frequency cathodic control, under bias voltage-150 ~-200 laid shoot part, deposition 10 ~ 20min, obtain CrN layer, the total thickness of Cr layer and CrN layer is 200 ~ 400nm;
(4), CrBCN layer preparation: utilize boron chromium target to carry out deposition CrBCN layer in vacuum chamber, the background vacuum of vacuum chamber is better than 5 × 10 -3pa, boron chromium target is by radio frequency cathodic control, and sputtering atmosphere adopts Ar and N 2and acetylene C 2h 2mixed gas, deposition pressure is 0.8 ~ 2Pa, substrate temperature 200 DEG C ~ 400 DEG C; sputtering power is 280 ~ 400W; sputtering time is 90 ~ 120min, and target-substrate distance is 5cm, obtains 2 ~ 5 μm of thick CrBCN nano composite structure protective coatings at the deposited on silicon of transition layer.
Ion Cleaning described in step (2) is specially: described matrix is put into vacuum chamber, open Ar gas after vacuumizing, Ar airshed is 20 ~ 50sccm, maintains vacuum tightness at 2 ~ 4Pa, adopt radio-frequency power supply described matrix to be carried out to the ion bombardment of 30min, power is 80 ~ 100W; The arc current of boron chromium target controls to be 70 amperes, and the arc current of chromium target controls to be 70 amperes, and bombardment bias voltage control is-350 volts.
In step (2), the frequency of Ultrasonic Cleaners is 15 ~ 30kHz.
In described step (4), Ar airshed is 20 ~ 50sccm, N 2airshed is 100 ~ 120sccm, acetylene C 2h 2gas flow is 30 ~ 60sccm.
In step (3) and (4), the temperature range of matrix is 200 DEG C ~ 400 DEG C.
The CrBCN supercoat adopting processing method of the present invention to obtain is by nanometer CrN matrix phase and the phase composite of amorphous BCN interfacial phase two; and form nano composite structure at coat inside; the i.e. crystallite-cladded CrN nanometer equi-axed crystal being of a size of 5 ~ 10nm of BCN interfacial phase, utilizes the dispersion effect of BCN amorphous phase to reduce the internal stress of CrN.Utilize BCN coating amorphous characteristic to limit the grain growing of CrN coating, obtain the CrN of nanocrystalline state, make CrN coating have good toughness.Under this nano composite structure, dislocation motion is difficult to carry out.Adding due to chromium nitride transition layer simultaneously; this invention is made to improve bonding force between film and matrix and resistance toheat; especially hardness and the wear resisting property of film is improved; therefore; described CrBCN protective coating not only has the high rigidity more than 40GPa; and there is excellent high temperature oxidation resistance and corrosion resistance, the film/base bonding force of film is up to more than 200N.The present invention can be used as the protective coating of the high-load equipments such as the coating of the parts such as high-speed dry type cutting cutter, mould and the impact of other field taking up wear.And preparation method of the present invention has the features such as technique is simple, sedimentation velocity is fast, cost is low, production efficiency is high, energy consumption is low, lower to equipment requirements.
Accompanying drawing explanation
Fig. 1 is the structural representation of multi-target magnetic control sputtering instrument used in the present invention;
The CrBCN compound coating Cross Section Morphology figure of Fig. 2 prepared by the present invention;
The CrBCN compound coating of Fig. 3 prepared by the present invention surface topography map.
Embodiment
High rigidity CrBCN nano composite structure protective coating prepared in following examples of the present invention, deposition is covered on matrix, and described matrix is Wimet, stainless steel, rapid steel, carbon steel, die steel or pottery.Transition layer is provided with between described protective coating and matrix; described transition layer is divided into two-layer up and down; the lower floor contacted with matrix phase is metal bonding layer Cr; the upper strata contacted with protective coating is CrN; the thickness of transition layer is 200 ~ 400nm; described protective coating is the nano composite structure of amorphous BCN interfacial phase parcel CrN nanometer equi-axed crystal, and its thickness is 2 ~ 5 μm.The grain-size of described CrN nanometer equi-axed crystal is 5 ~ 10nm.
The instrument preparing high rigidity CrBCN nano composite structure protective coating of the present invention used is respectively: JGP-450 type multi-target magnetic control sputtering instrument and M308457 Ultrasonic Cleaners.
The present invention for the instrument tested is: EDAX energy spectrometer (EDS) analysis ingredient; JEOLJEM2010 type Flied emission transmission electron microscope (HRTEM) observes microscopic appearance; D/MAX2550VB/PC type X-ray diffractometer (XRD) measures thing phase composite; NANOIndenterG200 type nano-hardness tester measures consistency and elasticity modulus.
As shown in Figure 1, its vacuum chamber is surrounded by furnace wall the structure of wherein said multi-target magnetic control sputtering instrument, and vacuum chamber height is 50cm, and volume is 50x50x50cm 3.Vacuum chamber side is provided with fire door, to facilitate the handling of workpiece.Vacuum chamber is provided with vacuum orifice, vacuumizes unit and is vacuumized vacuum chamber by vacuum orifice, and vacuumize unit and be made up of mechanical pump and molecular pump, highest attainable vacuum can reach 10 -4pa.Hollow cathode ion source installed by fire door, and in order to improve the ionization level of acetylene gas, vacuum chamber both sides are mounted alternately with two electric arc Cr targets and two electric arc CrB 2target, the diameter of circular electric arc target is 100mm, electric arc target is equipped with epistasis magnet for fettering the shape of target arc.In burner hearth, well heater is installed, the temperature in vacuum chamber can be regulated easily.Specimen holder is positioned at the central position of burner hearth, and sample hangs on specimen holder, can carry out revolving round the sun and rotation, and specimen holder rotating speed is adjustable.Such layout can make plasma density in vacuum chamber increase considerably, and the complete submergence of workpiece in the plasma.Coating deposition rate, hardness, sticking power are greatly improved.Owing to being optimized target structure, Distribution of Magnetic Field evenly, make electric arc homogenous combustion on target surface, improve the homogeneity of coating and reduce the consumption of target.
The concrete preparation method of high rigidity CrBCN nano composite structure protective coating provided by the present invention is as shown in the following example:
Embodiment 1
Select purity to be two chromium targets of 99.99% and the array mode of two boron chromium targets, four targets are mutually 90 degree of placements, and centre is heating rod.Routine is deoiled, decontamination process to be used by matrix surface washing composition to carry out, then carry out polished finish, finally use acetone and ethanol to carry out ultrasonic cleaning respectively, the frequency of Ultrasonic Cleaners is 15 ~ 30kHz, load vacuum chamber after oven dry, then carry out Ion Cleaning; Ion Cleaning is specially: described matrix is put into vacuum chamber, and open Ar gas after vacuumizing, Ar airshed is 30sccm, maintains vacuum tightness at 2 ~ 4Pa, and adopt radio-frequency power supply described matrix to be carried out to the ion bombardment of 30min, power is 80 ~ 100W; The arc current of boron chromium target controls to be 70 amperes, and the arc current of chromium target controls to be 70 amperes, and bombardment bias voltage control is-350 volts.
By the matrix after Ion Cleaning at 350 DEG C, vacuum tightness 1x10 -3the Metal Cr layer of 50 nanometer thickness is deposited under the condition of Pa, bias voltage-800V, then under 1.0Pa nitrogen environment, chromium target by radio frequency cathodic control, under bias voltage-150 ~-200 laid shoot part, deposition 10 ~ 20min, obtain the CrN layer of 150 nanometer thickness, the total thickness of Cr layer and CrN layer is 200nm;
Finally utilize boron chromium target to carry out deposition CrBCN layer in vacuum chamber, the background vacuum of vacuum chamber is better than 5 × 10 -3pa, boron chromium target is by radio frequency cathodic control, and sputtering atmosphere adopts Ar and N 2and acetylene C 2h 2mixed gas, deposition pressure is 1.2Pa, and sputtering power is 360W, substrate temperature 350 DEG C, and sputtering time is 90 ~ 120min, and target-substrate distance is 5cm, obtains 5 μm of thick CrBCN nano composite structure protective coatings at the deposited on silicon of transition layer.In mixed gas, Ar airshed is 30sccm, N 2airshed is 100sccm, acetylene C 2h 2gas flow is 30sccm.
After tested, the hardness of the nano composite structure protective coating obtained in the present embodiment is 40.7GPa.Through X-ray material phase analysis, coating is face-centred cubic structure, and preferred orientation is (200), in nanocrystalline growth.Frictional coefficient is lower than 0.40.Preparation terminates rear naturally cooling, obtains the nanocrystalline super-hard self-lubricating nano-composite coating of CrBCN.C in compound coating 3n 4, CrN, CrB 2crystal grain is nanocrystalline, and grain-size is 5nm.
Fig. 2 is CrBCN compound coating Cross Section Morphology figure prepared by the present embodiment, as can be seen from the figure, coating is transitioned into CrN layer from pure metal Cr layer, crossfade into CrBCN layer subsequently, finally arrive CrBCN compound coating, coated component has gradual change, hardness also has gradual change simultaneously, rational design makes the internal stress of coating little, strong adhesion.
Fig. 3 is the surface topography map of the CrBCN compound coating that the present embodiment obtains, and as can be seen from the figure, coatingsurface has a small amount of small-particle, and this is a small amount of pollution caused in arc discharge process, the mainly molten drop of Cr.
Embodiment 2
In the present embodiment, preparation process is substantially identical with embodiment 1, and difference is that substrate temperature is 300 DEG C, sputtering power 320W in the present embodiment when depositing transition layer and CrBCN layer.In mixed gas, Ar airshed is 40sccm, N 2airshed is 100sccm; Acetylene gas flow is 30sccm.After tested, the hardness of the nano composite structure protective coating obtained in the present embodiment is 36.7GPa.Through X-ray material phase analysis, coating is face-centred cubic structure, and preferred orientation is (200), in nanocrystalline growth.
Embodiment 3
In the present embodiment, preparation process is substantially identical with embodiment 1, and difference is that substrate temperature is 300 DEG C, sputtering power 400W in the present embodiment when depositing transition layer and CrBCN layer.In mixed gas, Ar airshed is 30sccm, N 2airshed is 100sccm; Acetylene gas flow is 30sccm.After tested, the hardness of the nano composite structure protective coating obtained in the present embodiment is 35.8GPa.Through X-ray material phase analysis, coating is face-centred cubic structure, and preferred orientation is (200), in nanocrystalline growth.

Claims (7)

1. a high rigidity CrBCN nano composite structure protective coating; deposition is covered on matrix; it is characterized in that: between described protective coating and matrix, be provided with transition layer; described transition layer is divided into two-layer up and down; the lower floor contacted with matrix phase is metal bonding layer Cr, and the upper strata contacted with protective coating is CrN, and the thickness of transition layer is 200 ~ 400nm; described protective coating is the nano composite structure of amorphous BCN interfacial phase parcel CrN nanometer equi-axed crystal, and its thickness is 2 ~ 5 μm.
2. high rigidity CrBCN nano composite structure protective coating according to claim 1, is characterized in that: the grain-size of described CrN nanometer equi-axed crystal is 5 ~ 10nm.
3. high rigidity CrBCN nano composite structure protective coating according to claim 1, is characterized in that: described matrix is Wimet, stainless steel, rapid steel, carbon steel, die steel or pottery.
4. a preparation method for high rigidity CrBCN nano composite structure protective coating according to claim 1, is characterized in that comprising the following steps:
(1), the selecting of target: select purity to be two chromium targets of 99.99% and the array mode of two boron chromium targets, four targets are mutually 90 degree of placements, and centre is heating rod;
(2), substrate pretreated technique: routine is deoiled, decontamination process to be used by matrix surface washing composition to carry out, and then carries out polished finish, finally uses acetone and ethanol to carry out ultrasonic cleaning respectively, loads vacuum chamber, then carry out Ion Cleaning after oven dry;
(3), transition layer is deposited: by the matrix after Ion Cleaning at 200 DEG C ~ 400 DEG C, vacuum tightness 1x10 -3deposit Metal Cr layer under the condition of Pa, bias voltage-800V, then under 1.0Pa nitrogen environment, chromium target by radio frequency cathodic control, under bias voltage-150 ~-200 laid shoot part, deposition 10 ~ 20min, obtain CrN layer, the total thickness of Cr layer and CrN layer is 200 ~ 400nm;
(4), CrBCN layer preparation: utilize boron chromium target to carry out deposition CrBCN layer in vacuum chamber, the background vacuum of vacuum chamber is better than 5 × 10 -3pa, boron chromium target is by radio frequency cathodic control, and sputtering atmosphere adopts Ar and N 2and acetylene C 2h 2mixed gas, deposition pressure is 0.8 ~ 2Pa, substrate temperature 200 DEG C ~ 400 DEG C; sputtering power is 280 ~ 400W; sputtering time is 90 ~ 120min, and target-substrate distance is 5cm, obtains 2 ~ 5 μm of thick CrBCN nano composite structure protective coatings at the deposited on silicon of transition layer.
5. the preparation method of high rigidity CrBCN nano composite structure protective coating according to claim 4, it is characterized in that: the Ion Cleaning described in step (2) is specially: described matrix is put into vacuum chamber, Ar gas is opened after vacuumizing, Ar airshed is 20 ~ 50sccm, maintain vacuum tightness at 2 ~ 4Pa, adopt radio-frequency power supply described matrix to be carried out to the ion bombardment of 30min, power is 80 ~ 100W; The arc current of boron chromium target controls to be 70 amperes, and the arc current of chromium target controls to be 70 amperes, and bombardment bias voltage control is-350 volts.
6. the preparation method of high rigidity CrBCN nano composite structure protective coating according to claim 4, is characterized in that: in step (2), the frequency of Ultrasonic Cleaners is 15 ~ 30kHz.
7. the preparation method of high rigidity CrBCN nano composite structure protective coating according to claim 4, it is characterized in that: in described step (4), Ar airshed is 20 ~ 50sccm, N 2airshed is 100 ~ 120sccm, acetylene C 2h 2gas flow is 30 ~ 60sccm.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109161848A (en) * 2018-09-18 2019-01-08 岭南师范学院 A kind of CrAlBCN coating, the nano combined CrAlBCN coating of low friction seawater corrosion resistance and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103343326A (en) * 2013-07-08 2013-10-09 武汉大学 Nanocrystalline ultrahard composite coating and preparation method thereof
CN103567374A (en) * 2012-08-07 2014-02-12 现代自动车株式会社 Coating material for aluminum die casting mold and method of manufacturing the coating material
CN103572289A (en) * 2012-08-07 2014-02-12 现代自动车株式会社 Multi-layer mold coating
CN104152857A (en) * 2014-08-13 2014-11-19 徐州力泰钢结构有限公司 High-hardness TiAlZrN/CrN nano multi-layer coating and preparation method thereof
CN104213075A (en) * 2014-09-22 2014-12-17 武汉大学 AlTiSiN-AlCrSiN nanocrystalline-amorphous multilayer composite superhard toughness coating material and manufacturing method
CN104805408A (en) * 2015-05-19 2015-07-29 上海井研精密工具有限公司 High-hardness TiSiBN nano-composite structure protective coating and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103567374A (en) * 2012-08-07 2014-02-12 现代自动车株式会社 Coating material for aluminum die casting mold and method of manufacturing the coating material
CN103572289A (en) * 2012-08-07 2014-02-12 现代自动车株式会社 Multi-layer mold coating
CN103343326A (en) * 2013-07-08 2013-10-09 武汉大学 Nanocrystalline ultrahard composite coating and preparation method thereof
CN104152857A (en) * 2014-08-13 2014-11-19 徐州力泰钢结构有限公司 High-hardness TiAlZrN/CrN nano multi-layer coating and preparation method thereof
CN104213075A (en) * 2014-09-22 2014-12-17 武汉大学 AlTiSiN-AlCrSiN nanocrystalline-amorphous multilayer composite superhard toughness coating material and manufacturing method
CN104805408A (en) * 2015-05-19 2015-07-29 上海井研精密工具有限公司 High-hardness TiSiBN nano-composite structure protective coating and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
K. YAMAMOTO等: "Nano-multilayered CrN/BCN coating for anti-wear and low friction applications", 《SURFACE & COATING TECHNOLOGY》 *
KENJI YAMAMOTO等: "Properties of nano-multilayered hard coatings deposited by a new hybrid coating process: Combined cathodic arc and unbanlanced magnetron sputtering", 《SURFACE & COATING TECHNOLOGY》 *
P. PESCH等: "New multifunctional PVD-coating in the material system Cr-BCN-Si for steel sheet forming", 《SURFACE & COATING TECHNOLOGY》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109161848A (en) * 2018-09-18 2019-01-08 岭南师范学院 A kind of CrAlBCN coating, the nano combined CrAlBCN coating of low friction seawater corrosion resistance and preparation method thereof
CN109161848B (en) * 2018-09-18 2021-07-13 岭南师范学院 CrAlBCN coating, low-friction seawater corrosion-resistant nano composite CrAlBCN coating and preparation method thereof

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