CN110453174A - A kind of protective coating and preparation method thereof for titanium alloy substrate surface - Google Patents

A kind of protective coating and preparation method thereof for titanium alloy substrate surface Download PDF

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Publication number
CN110453174A
CN110453174A CN201910506040.6A CN201910506040A CN110453174A CN 110453174 A CN110453174 A CN 110453174A CN 201910506040 A CN201910506040 A CN 201910506040A CN 110453174 A CN110453174 A CN 110453174A
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crn
coating
protective coating
matrix
zrn
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王启民
黄雪丽
张腾飞
李季飞
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Guangdong University of Technology
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Guangdong University of Technology
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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
    • C23C14/0021—Reactive sputtering or evaporation
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation

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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 protective coating and preparation method thereof that the invention discloses a kind of for titanium alloy substrate surface, the protective coating include the interface Cr prime coat, CrN transition zone, CrN/ZrN nano laminated coating and the CrN buffer layer being cascading on matrix surface；The CrN/ZrN nano laminated coating is by CrN nano coating and ZrN nano coating is alternately laminated constitutes.Protective coating provided by the invention has good toughness, high rigidity, high-wearing feature and highly corrosion resistant, with basal body binding force height, greatly extends application range of the titanium matrix under harsh environment and prolongs the service life.In addition, the preparation method of the protective coating prepares protective coating using arc ion plating, stable working performance, repetitive rate is high, and easy to operate, simple process, short preparation period is at low cost, environmentally protective, is convenient for large-scale industrial production.

Description

A kind of protective coating and preparation method thereof for titanium alloy substrate surface
Technical field
The present invention relates to metal material surface protection technology fields, are used for titanium alloy-based body surface more particularly, to one kind The protective coating in face and preparation method thereof.
Background technique
The use failure of industrial application machine components mostly occurs on surface or since surface.According to statistics, surface damage loses Effect accounts for 80% or more all to fail；Loss is as high as hundreds billion of members caused by China is often only because of abrasion.By taking titanium alloy as an example, Titanium alloy has many advantages, such as that density is small, specific strength is high, solderability is good, is mainly used in aerospace and war industry, simultaneously It also has a wide range of applications in many industrial departments such as chemical industry, petroleum, light industry, metallurgy, power generation, sport, medical treatment.But titanium closes Gold wears no resistance, and coefficient of friction is big, Yi Fasheng adhesive wear, and titanium alloy is easy to that fine motion occurs in the junction of vibration component Abrasion and fretting fatigue, the frictional heat and frictional force of interface will aggravate fatigue failure, generate spalling damage, 600 DEG C or more High-temperature oxidation resistance is poor, and unstable in the medium with reproducibility or complexing causes to corrode, and these problems make The application of titanium and its alloy is restricted, therefore also becomes one of the hot spot in investigation of materials field.
Currently, the common Surface hardening treatment technology of titanium alloy has thermal spraying, plating and chemical plating, plasma nitriding, swashs Light cladding, vapor deposition, differential arc oxidation and compound process for treating surface etc., for example, Zhou Dandan et al. (TC4 Alloy by Laser Microstructure and property research [D] the Tianjin Polytechnic University of cladding wear resistant self-lubricating coating, 2017.) select h-BN, Ti3SiC2As Lubricant prepares Ni base self-lubricating wear resistant friction reducing coating on the titanium alloy surface (TC4) by laser melting coating, although to a certain degree On improve wear-corrosion resistance, but ceramic-like cladding coating crackle and spallation problems are serious, and toughness and binding force are insufficient.It adopts Nano-TiO is prepared in titanium alloy surface with anode oxidation process2Although can effectively improve wear-resisting property, anodic oxidation Membrane structure is loose porous, limits the raising to corrosion resisting property.
Therefore, it is necessary to develop while having being used for for good toughness, high-bond, high-wearing feature and highly corrosion resistant The protective coating on titanium alloy substrate surface.
Summary of the invention
The present invention is to overcome the insufficient defect of toughness described in the above-mentioned prior art, binding force, wear resistant corrosion resistant, provides one Kind be used for titanium alloy substrate surface protective coating, the protective coating provided have good toughness, high rigidity, high-wearing feature and Highly corrosion resistant greatly extends application range and extension of the titanium matrix under harsh environment with basal body binding force height Service life.
Another object of the present invention is to provide the preparation method of above-mentioned protective coating, the preparation method provided is using electric arc Ion plating prepares protective coating, and stable working performance, repetitive rate is high, and easy to operate, simple process, short preparation period is at low cost, It is environmentally protective, it is convenient for large-scale industrial production.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of protective coating for titanium alloy substrate surface, including the interface Cr being cascading on matrix surface Prime coat, CrN transition zone, CrN/ZrN nano laminated coating and CrN buffer layer；The CrN/ZrN nano laminated coating is by CrN Nano coating and the alternately laminated composition of ZrN nano coating.
The titanium alloy can be TC4.
Inventor is sequentially depositing the interface Cr prime coat, CrN transition zone, CrN/ZrN nano laminated coating on matrix surface With CrN buffer layer, the protective coating for titanium alloy substrate surface is successfully obtained.In protective coating, the interface Cr prime coat and CrN Transition zone is mainly used for improving the binding force of coating and titanium alloy TC 4 matrix；Modulate the working lining of CrN/ZrN nano laminated coating It can reduce its internal stress, improve its consistency, toughness, hardness and wear-corrosion resistance；Surface C rN transition zone can subtract Slow CrN/ZrN nano laminated coating is destroyed by caused by the fretting wear of external environment and the erosion of corrosive medium etc..
To sum up, protective coating provided by the invention has good toughness, high rigidity, high-wearing feature and highly corrosion resistant, With basal body binding force height, greatly extends application range of the titanium matrix under harsh environment and prolong the service life, such as The protection of the product surfaces such as component of machine, knife mold, operation on the sea.
Preferably, the modulation period of the CrN/ZrN nano laminated coating is 1~500nm, and described CrN/ZrN nanometers more Layer coating with a thickness of 1~500 μm.
It is highly preferred that the modulation period of the CrN/ZrN nano laminated coating is 20~150nm.For example, the CrN/ The modulation period of ZrN nano laminated coating can be 20.6,56 or 144nm.
It is highly preferred that the CrN/ZrN nano laminated coating with a thickness of 1~50 μm.
Preferably, the interface Cr prime coat with a thickness of 1~5000nm.It is highly preferred that the interface Cr prime coat With a thickness of 500nm.
Preferably, the CrN transition zone with a thickness of 1~9000nm.It is highly preferred that the CrN transition zone with a thickness of 2 μm。
Preferably, the CrN buffer layer with a thickness of 1~9000nm.It is highly preferred that the CrN buffer layer with a thickness of 2 μm。
Preferably, the protective coating with a thickness of 1~20nm.
The present invention also protects the preparation method of above-mentioned protective coating, and the preparation method includes the following steps:
S1. by after matrix etching, the interface Cr prime coat is deposited in matrix surface；
S2. CrN transition zone is deposited on the prime coat of the interface Cr；
S3. CrN/ZrN nano laminated coating is deposited on CrN transition zone；
S4. CrN buffer layer is deposited on CrN/ZrN nano laminated coating.
Preferably, the preparation method further includes following steps:
S5. the 2nd CrN/ZrN nano laminated coating is deposited on CrN buffer layer；
S6. the 2nd CrN buffer layer is deposited on the 2nd CrN/ZrN nano laminated coating.
Preferably, the deposition is carried out by arc ion plating.
Preferably, matrix is fixed on bracket when deposition, 1.5~15rpm/min of the bracket rotation, and revolution 0.5~ 5rpm/min。
Preparation method provided by the invention prepares protective coating using arc ion plating, and stable working performance, repetitive rate is high, Easy to operate, simple process, short preparation period is at low cost, environmentally protective, is convenient for large-scale industrial production.
Specifically, step S1. is as follows:
A1 it) cleans matrix: polished treated matrix being sent into supersonic wave cleaning machine, successively with acetone, dehydrated alcohol Carry out ultrasonic cleaning 10min~20min respectively with 15kHz~30kHz, then cleaned with deionized water, then with purity >= 99.5% is dried with nitrogen；
A2 it) vacuumizes and cleans plated film cavity with ion beam etching: the matrix after ultrasonic cleaning is placed in the workpiece of vacuum chamber On bracket, deposition chambers operating temperature is heated to 300 DEG C~500 DEG C, matrix is heated to 300 DEG C~500 DEG C, and extracts deposition Chamber indoor gas；It is evacuated to vacuum degree 5.0 × 10-3Pa or less；
A3) ion beam pulses etch cleaner: when Chamber vacuum degree is 3.0 × 10-3Pa~5.0 × 10-3After Pa, it is passed through gas Body flow is the Ar gas of 200sccm~450sccm, and adjusting deposition chamber environmental pressure is 0.6Pa~1.2Pa, maintains furnace temperature 400 DEG C~500 DEG C, the working time is 5~30min；
A4) electric arc Cr ion etching: opening electric arc Cr target power supply, is passed through the Ar that gas flow is 200sccm~450sccm Gas, adjusting deposition chamber environmental pressure be 0.6Pa~1.2Pa, maintain 400 DEG C~500 DEG C of furnace temperature, the working time be 20~ 60min；
A5 it) deposits the interface Cr prime coat: opening electric arc Cr target power supply, arc ource electric current is 80A~250A, is passed through argon gas 500sccm~1000sccm controls gas pressure in vacuum 0.6Pa~1.2Pa, maintains 400 DEG C~500 DEG C of furnace temperature, sedimentation time 0 ~1h.
Preferably, step a2) used in heating power 3kW~5kW.
Preferably, step a3) used in matrix add back bias voltage -900V~-800V, duty ratio is 50%~70%, is added Thermal power 3kW~5kW.
Preferably, step a4) used in matrix add back bias voltage -900V~-800V, duty ratio is 50%~70%, is added Thermal power 3kW~5kW.
Preferably, step a5) used in matrix add back bias voltage -200V~-100V, duty ratio is 60%~80%, is added Thermal power 1kW~5kW.
Specifically, step S2. is as follows:
A6 it) deposits CrN transition zone: continuing starting electric arc Cr target power supply, arc ource electric current is 80A~250A, is passed through nitrogen 500sccm~950sccm controls gas pressure in vacuum 1.5Pa~4Pa, maintains 400 DEG C~500 DEG C of furnace temperature, sedimentation time 0.5 ~2h.
Preferably, step a6) used in matrix add back bias voltage -200V~-100V, duty ratio is 60%~80%, is added Thermal power 3kW~5kW.
Specifically, step S3. is as follows:
A7 it) deposits CrN/ZrN nano laminated coating: opening electric arc Cr target power supply, and open an electric arc Zr target, be passed through nitrogen Gas 500sccm~950sccm, control 1.5~4Pa of gas pressure in vacuum, maintain 400 DEG C~500 DEG C of furnace temperature, sedimentation time be 1~ 4h。
Preferably, step a6) used in matrix add back bias voltage -200V~-100V, duty ratio is 60%~80%, is added Thermal power 1kW~5kW.
Specifically, step S4. is as follows:
A8 it) deposits CrN buffer layer (repeating a6): continuing starting electric arc Cr target power supply, arc ource electric current is 80A~250A, is led to Enter nitrogen 500sccm~950sccm, control gas pressure in vacuum 1.5Pa~4Pa, matrix adds back bias voltage -200V~-100V, duty Than being 50%~80%, heating power 3kW~5kW maintains 400 DEG C~500 DEG C of furnace temperature, and sedimentation time is 0.5~2h.
Specifically, step S5. is as follows:
A9 it) deposits CrN/ZrN nano laminated coating (repeating a7): opening electric arc Cr target power supply, and open an electric arc Zr Target, is passed through nitrogen 500sccm~950sccm, controls gas pressure in vacuum 1.5Pa~4Pa, matrix add back bias voltage -200V~- 100V, duty ratio be 60%~80%, heating power 3kW~5kW, maintain 400 DEG C~500 DEG C of furnace temperature, sedimentation time be 1~ 4h。
Specifically, step S6. is as follows:
A10 it) deposits CrN buffer layer: continuing starting electric arc Cr target power supply, arc ource electric current is 80A~250A, is passed through nitrogen 500sccm~950sccm controls gas pressure in vacuum 1.5Pa~4Pa, and matrix adds back bias voltage -200V~-100V, and duty ratio is 60%~80%, heating power 3kW~5kW maintain 400 DEG C~500 DEG C of furnace temperature, and sedimentation time is 0.5~2h；
A11) deposition terminates to close power supply, is down to room temperature to vacuum room temperature, opens vacuum chamber and takes out matrix, in matrix table Face forms protective coating.
Compared with prior art, the beneficial effects of the present invention are:
Be sequentially depositing on matrix surface of the present invention the interface Cr prime coat, CrN transition zone, CrN/ZrN nano laminated coating and CrN buffer layer obtains the protective coating for titanium alloy substrate surface, and protective coating obtained has good toughness, height hard Degree, high-wearing feature and highly corrosion resistant greatly extend titanium matrix answering under harsh environment with basal body binding force height With range and prolong the service life, such as the protection of component of machine, knife mold, operation on the sea product surface.
In addition, the preparation method of the protective coating prepares protective coating using arc ion plating, stable working performance is repeated Rate is high, and easy to operate, simple process, short preparation period is at low cost, environmentally protective, is convenient for large-scale industrial production.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the protective coating for titanium alloy substrate surface of the embodiment of the present invention 1.
Fig. 2 is that CrN/ZrN nano laminated coating fills up defect effect schematic diagram in the protective coating of the embodiment of the present invention 1.
Fig. 3 is protective coating, the single layer CrN coating of comparative example 1 and the XRD diagram of matrix of the embodiment of the present invention 1.Matrix is TC4。
Fig. 4 is the SEM shape appearance figure of the protective coating of the embodiment of the present invention 1.Wherein, Fig. 4 (a) is Cross Section Morphology figure；Fig. 4 It (b) is the surface topography map under 10,000 times of amplification.
Fig. 5 is the rockwell indentation figure of the protective coating of the embodiment of the present invention 1.
Fig. 6 is 10,000 circle of the protective coating of the embodiment of the present invention 1, the single layer CrN coating of comparative example 1 and matrix friction operation Coefficient of friction in the process.Relative humidity 45%~60%, range ability 125.6m.
Fig. 7 is 20,000 circle of the protective coating of the embodiment of the present invention 1, the single layer CrN coating of comparative example 1 and matrix friction operation Coefficient of friction in the process.Relative humidity 75%~90%, range ability 351.8m.
Fig. 8 is protective coating, the single layer CrN coating of comparative example 1 and the 3D grinding defect morphology of matrix of the embodiment of the present invention 1. Wherein, Fig. 8 (a) is wear morphology after 10,000 circles；Fig. 8 (b) is wear morphology after 20,000 circles.
Fig. 9 is protective coating, the single layer CrN coating of comparative example 1 and the wear rate column of matrix of the embodiment of the present invention 1 Figure.
Figure 10 is that the corrosion polarization of the protective coating of the embodiment of the present invention 1, the single layer CrN coating of comparative example 1 and matrix is bent Line chart.
Specific embodiment
The present invention is further illustrated With reference to embodiment.
The same or similar label correspond to the same or similar components in the attached drawing of the embodiment of the present invention；It is retouched in of the invention In stating, it is to be understood that if there is the orientation of the instructions such as term " on ", "lower", "left", "right", "top", "bottom", "inner", "outside" Or positional relationship is to be based on the orientation or positional relationship shown in the drawings, and is merely for convenience of description of the present invention and simplification of the description, and It is not that the device of indication or suggestion meaning or element must have a particular orientation, be constructed and operated in a specific orientation, therefore The terms describing the positional relationship in the drawings are only for illustration, should not be understood as the limitation to this patent.
In addition, if there is the terms such as " first ", " second " to be used for description purposes only, be mainly used for distinguishing different devices, Element or component (specific type and construction may identical may also be different), is not intended to show or implies indicated fill It sets, the relative importance and quantity of element or component, and should not be understood as indicating or implying relative importance.
Raw material in embodiment can be by being commercially available；
Unless stated otherwise, the present invention uses reagent, method and apparatus for the art conventional reagent, method and are set It is standby.
Embodiment 1
A kind of protective coating for titanium alloy substrate surface, as shown in Figure 1, including being cascading in matrix surface On the interface Cr prime coat, CrN transition zone, CrN/ZrN nano laminated coating and CrN buffer layer；CrN/ZrN nano laminated coating By CrN nano coating and ZrN nano coating is alternately laminated constitutes, as shown in Figure 2.
This implementation floating coat overall thickness is 17.7um, modulation period 144nm, preparation method is as follows:
Polished treated titanium alloy (TC4) matrix is sent into supersonic wave cleaning machine, successively with acetone, dehydrated alcohol with 30kHz carries out ultrasonic cleaning 10min respectively, is then cleaned with deionized water, then being dried with nitrogen with purity >=99.5%.
Matrix after ultrasonic cleaning is placed on the work support of vacuum chamber, heating power 2kW, deposition chambers is worked warm Degree is heated to 500 DEG C, and extracts deposition chamber gas to vacuum degree 5.0 × 10-3Pa or less.
It is passed through the Ar gas that gas flow is 250sccm, adjusting deposition chamber environmental pressure is 0.9Pa, and matrix adds negative bias Pressure -950V, duty ratio 42%, heating power 2kW maintain 500 DEG C of furnace temperature, carry out the cleaning of pulse aura, the duration is After 7min, electric arc Cr target power supply is opened, is passed through the Ar gas that gas flow is 200sccm, adjusting deposition chamber environmental pressure is 0.8Pa, matrix add back bias voltage -950V, duty ratio 42%, heating power 2kW, 500 DEG C of furnace temperature holding, progress Cr ion etching 30min。
Continue to open electric arc Cr target power supply, arc ource electric current is 180A, is passed through argon gas 200sccm, controls gas pressure in vacuum 0.8Pa, matrix add back bias voltage -80V, duty ratio 70%, and heating power 2kW maintains 400 DEG C of furnace temperature, Cr layers of deposited metal 5min。
It being subsequently passed nitrogen 800sccm, controls gas pressure in vacuum 2Pa, matrix adds back bias voltage -80V, duty ratio 70%, Heating power 1kW maintains 400 DEG C of furnace temperature, deposits CrN coating 1h.
An electric arc Zr target is opened while opening electric arc Cr target power supply, is passed through nitrogen 800sccm, controls gas pressure in vacuum 3Pa, matrix add back bias voltage -80V, duty ratio 70%, and heating power 1kW maintains 400 DEG C of furnace temperature, deposit CrN/ZrN nano junction Structure coating 1.5h.
Electric arc Zr target power supply to be closed, electric arc Cr target power supply is continued starting, arc ource electric current is 180A, it is passed through argon gas 200sccm, Gas pressure in vacuum 0.8Pa is controlled, matrix adds back bias voltage -950V, duty ratio 42%, and heating power 2kW maintains 500 DEG C of furnace temperature, Electric arc chromium ion etches 30min.
Deposition CrN/ZrN nano-structured coating is continued thereafter with, opens electric arc Cr target power supply, and open an electric arc Zr target, It being passed through nitrogen 800sccm, controls gas pressure in vacuum 3Pa, matrix adds back bias voltage -80V, duty ratio 70%, heating power 1kW, 400 DEG C of furnace temperature are maintained, sedimentation time 1.5h.
It is then one layer CrN layers redeposited: to close electric arc Zr target power supply, continue starting electric arc Cr target power supply, arc ource electric current is 180A is passed through nitrogen 800sccm, controls gas pressure in vacuum 2Pa, and matrix adds back bias voltage -80V, duty ratio 70%, heating power 1kW maintains 400 DEG C of furnace temperature, and depositing after sedimentation time 0.5h terminates.
The revolving speed of substrate holder rotation described in coating process is 2rpm/min, and revolution revolving speed is 1rpm/min.Power supply is closed, It is down to room temperature to vacuum room temperature, vacuum chamber is opened and takes out matrix, in the protective coating that matrix surface is formed.
Embodiment 2
The present embodiment is second embodiment of the present invention for the protective coating on titanium alloy substrate surface, not with embodiment 1 With, bracket rotation 4rpm/min, revolution revolving speed is 2rpm/min, coating layer thickness 16.3um, modulation period 56nm.
Embodiment 3
The present embodiment is second embodiment of the present invention for the protective coating on titanium alloy substrate surface, not with embodiment 1 With, bracket rotation 6rpm/min, revolution revolving speed is 3rpm/min, coating layer thickness 15.1um, modulation period 20.6nm.
Comparative example 1
In this comparative example, protective coating is single layer CrN coating；The preparation method is as follows:
It cleans matrix and cleaning process is carried out with embodiment 1 to sample；
Electric arc Cr target power supply is opened, arc ource electric current is 180A, is passed through nitrogen 800sccm, controls gas pressure in vacuum 2Pa, base Body adds back bias voltage -80V, duty ratio 70%, and heating power 1kW maintains 400 DEG C of furnace, and depositing after sedimentation time 8h terminates.It closes Power supply is down to room temperature to vacuum room temperature, opens vacuum chamber and takes out matrix, is CrN single layer in the coating that matrix surface is formed Coating.
Structure and performance test
(1) pattern test
The pattern of protective coating is tested by SEM, instrument is FEI Nova NanoSEM 430, backscatter mode, section Amplify 10,000 times, surface amplifies 20,000 times.
(2) XRD is tested
XRD is tested using Bruker D8ADVANCE, Cu target, acceleration voltage 40kV, electric current 40mA) scanning step is 0.02 °, residence time 0.1s, scanning range be 20~80 °.
(3) hardness and Young's modulus test
Using the hardness and elasticity modulus of nano-hardness tester (Anton Paar TTX-NHT2) measurement coating, load is measured For 5mN, loading speed 10mN/min, duplicate measurements 10 times, compression distance is no more than the 1/10 of coating layer thickness, takes its average value Characterize coating hardness；In addition, the process can measure Young's modulus simultaneously.
(4) binding force is tested
Using rockwell indentation instrument testing coating film-base junction resultant force, the electronic Rockwell apparatus of HR-150DT type, diamond Rockwell Pressure head, pressure are 150kgf (1471N).
(5) wear-resisting property is tested
Using wear-resisting property of the friction and wear tester research coating in the case where different friction circles are several, instrument CSMTHT- 1000 type ball disc type high temperature friction and wear instrument, abrading-ball speed of service 10mm/s, operating radius 2mm, operation circle number 10000, pressure For 5N；3D grinding defect morphology is OLS4100 type laser co-focusing using instrument.
(6) corrosion resistance is tested
Using electrochemical workstation testing coating and the corrosion resistance of matrix, instrument is 1470E electrochemical workstation, is moved Potential polarization curve, scanning range -0.8~0.3V use three-electrode system (Ag/AgCl at room temperature in 3.5%NaCl solution (saturation) makees reference electrode) the corrosion polarization curve of test sample.
Test result
1 hardness of table and Young's modulus test result
H(Gpa) E(Gpa) H/E H3/E2
TC4 4.22 139.57 0.03 0.004
Embodiment 1 21.58 351.10 0.06 0.08
From the figure 3, it may be seen that the protective coating of embodiment 1 is mainly made of CrN, ZrN.As shown in table 1, which can have Effect improves 5 times of surface hardness or more, and according to H/E, H3/E2The raising of value shows the good toughness of coating, that is, has more Good resistance to crack extension ability.Using the pattern of the protective coating of SEM observation embodiment 1, as shown in Figure 4.As shown in Figure 5, prevent Protecting coating and matrix has excellent binding force.By Fig. 6~9 it is found that the protective coating that the embodiment of the present invention 1 provides has friction Coefficient is low, the excellent feature of wear-resisting property, does not cause significant change to the abrasion of coating the extension of frictional distance.By The protective coating corrosion current that Figure 10 can be seen that the offer of embodiment 1 is minimum, has best corrosion resistance, can be right Matrix is effectively protected.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention Protection scope within.

Claims (8)

1. a kind of protective coating for titanium alloy substrate surface, which is characterized in that including being cascading in matrix surface On the interface Cr prime coat, CrN transition zone, CrN/ZrN nano laminated coating and CrN buffer layer；The CrN/ZrN nanometer multilayer Coating is by CrN nano coating and ZrN nano coating is alternately laminated constitutes.
2. protective coating according to claim 1, which is characterized in that the modulation week of the CrN/ZrN nano laminated coating Phase be 1~500nm, the CrN/ZrN nano laminated coating with a thickness of 1~500 μm.
3. protective coating according to claim 1, which is characterized in that the interface Cr prime coat with a thickness of 1~ 5000nm。
4. protective coating according to claim 1, which is characterized in that the CrN transition zone with a thickness of 1~9000nm.
5. protective coating according to claim 1, which is characterized in that the CrN buffer layer with a thickness of 1~9000nm.
6. the preparation method of any one of Claims 1 to 5 protective coating, which comprises the steps of:
S1. by after matrix etching, the interface Cr prime coat is deposited in matrix surface；
S2. CrN transition zone is deposited on the prime coat of the interface Cr；
S3. CrN/ZrN nano laminated coating is deposited on CrN transition zone；
S4. CrN buffer layer is deposited on CrN/ZrN nano laminated coating.
7. preparation method according to claim 6, which is characterized in that the deposition is carried out by arc ion plating.
8. preparation method according to claim 7, which is characterized in that matrix is fixed on bracket when deposition, the bracket 1.5~15rpm/min of rotation, revolve 0.5~5rpm/min.
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