CN109207923A - A kind of TiN/ZrN nano laminated coating and its preparation method and application - Google Patents
A kind of TiN/ZrN nano laminated coating and its preparation method and application Download PDFInfo
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- CN109207923A CN109207923A CN201811089578.3A CN201811089578A CN109207923A CN 109207923 A CN109207923 A CN 109207923A CN 201811089578 A CN201811089578 A CN 201811089578A CN 109207923 A CN109207923 A CN 109207923A
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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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
- C23C14/0036—Reactive sputtering
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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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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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
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
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Abstract
The invention discloses a kind of TiN/ZrN nano laminated coatings and its preparation method and application.The coating include matrix and alternating deposit TiN layer and ZrN layers, the TiN layer and ZrN layers of the number of plies are respectively 10 ~ 400 layers, and the modulation period of the coating is 4 ~ 40nm, the TiN layer and ZrN layer of thickness in monolayer ratio for 2:1.TiN/ZrN nano laminated coating is prepared using magnetically controlled DC sputtering technology in the present invention, and the hardness of gained coating is up to 28GPa or more, and elasticity modulus is 425 ~ 480GPa, while being also equipped with high-wear resistance and corrosion resistance.Preparation method of the invention is simply controllable, short preparation period, at low cost, gained coating has excellent hardness, toughness, wearability and corrosion resistance, it can be used in harsh environment, be completely suitable in the surfacecti proteon of component of machine, cutter, mold, operation on the sea product.
Description
Technical field
The present invention relates to coating material technical fields, more particularly, to a kind of TiN/ZrN nano laminated coating and its system
Preparation Method and application.
Background technique
Hard films can reduce the friction and wear of workpiece, effectively improve surface hardness, toughness, wearability and the height of product
Temperature stability, increase substantially the service life of coating product, positive adaptation high skill of the modern manufacturing industry to metal cutting tool
Art requirement, in addition, the Travellers on many components, such as frame used in friction environment, the piston ring in internal combustion engine, each
Kind mold etc., hard thin film material can also greatly improve its service life.Therefore hard thin film material can be widely applied to machine
The fields such as tool manufacture, auto industry, textile industry, geological drilling, mould industry, operation on the sea, aerospace.
The research of current most of nitride nano multilayer films is concentrated mainly on the systems such as TiN, TaN, NbN, A1N, CrN,
It is relatively fewer to the research of TiN/ZrN material, only a small number of document reports structure of TiN/ZrN multilayer film, interface roughness and
Mechanical property, such as prior art discloses the more target position vacuum cathode arc ion plating technologies of use in 1Cr17Ni2 stainless steel watch
Face deposits Anti-erosion TiN/ZrN multilayer film, it is found that its anti-anti salt spray corrosion is preferable, but binding force and hardness are poor.Also have
Minority is related to the influence of surface topography of the modulated structure to film, growth behavior of TiN/ZrN multilayer film, but does not have researcher couple
The multiple performances such as wear-resisting and corrosion-resistant of TiN/ZrN nano-multilayer film are studied simultaneously.
Therefore it provides a kind of have the good TiN/ZrN nano laminated coating material of high rigidity, abrasion and corrosion resistance for hair
Exhibition New Rigid thin-film material is of great significance.
Summary of the invention
Primary and foremost purpose of the invention is to overcome above-mentioned the deficiencies in the prior art, provides a kind of TiN/ZrN nano laminated coating.
The coating include alternating deposit TiN layer and ZrN layers, and have higher hardness, high tenacity, higher abrasion resistance and corrosion resistance
Energy.
It is a further object to provide a kind of preparation methods of TiN/ZrN nano laminated coating.
It is yet another object of the invention to provide a kind of TiN/ZrN nano laminated coating component of machine, cutter, mold,
Application in the surfacecti proteon of operation on the sea product.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of TiN/ZrN nano laminated coating, the coating include matrix and alternating deposit TiN layer and ZrN layers, the TiN layer
The number of plies with ZrN layers is respectively 10 ~ 400 layers, and the modulation period of the coating is 4 ~ 40nm, the TiN layer and ZrN layers of single monolayer thick
Degree is than being 2:1.
Compared to signal layer coating, laminated coating has more superior mechanical property, largely parallel with matrix in multilayer film
Inner boundary can play the role of hindering crack propagation, and provide dislocation motion resistance, while increasing toughness, coating
Hardness and strength are also improved.
The coating of physical vapour deposition (PVD) preparation is almost to be embedded in defect, it is impossible to the formation of pin hole is avoided completely, and
When coating is with the growth of column crystal type, column crystal gap also unavoidably becomes the corrosion resistant weak area of coating, works as coating material
When material exposes in aqueous solution, it may occur that local galvanic corrosion causes to accelerate to attack.The present invention can using nano-multilayered structures
So that the forming core again between layers of coating, every layer is filled up upper one layer of defect, forms dense coating structure, is avoided every
The defect of one interlayer, pin hole, column crystal gap.Therefore, coating of the present invention can be reduced and be eliminated using nanostructure and is heavy
The defects of product process, and then improve the corrosion resistance of coating.
The alternating deposit refers to first one layer of TiN layer of deposition, and one layer ZrN layers redeposited, successively alternate cycles form TiN/
ZrN nano laminated coating.
The coating number of plies and thickness determine the overall thickness of coating, and thickness thickens, and crystal grain forms more complete, crystal grain gap cavity
The defects of reduce.But coating layer thickness is thicker, and coating internal stress increases therewith, and excessive internal stress often focuses on coating in coating
At basal body interface, coating is caused to gradually decrease with basal body binding force.
It is highly preferred that every layer of TiN layer be with a thickness of 20nm, every layer ZrN layers with a thickness of 10nm.
It is thick per adjacent two layers of formation, one basic unit for the multilayer film of two kinds of heterogeneities or structure composition
Degree is known as modulation period.Crystalline substance between nano thickness single-layer silicon nitride zirconium under the different modulating period and adjacent nano thickness titanium nitride
Lattice growth conditions are different, and the modulation period is changed and is controlled by adjusting bracket revolution rotational velocity.
Preferably, the TiN layer and ZrN layers of the number of plies are respectively 60 ~ 180 layers.
Preferably, the modulation period of the coating is 4.9 ~ 30nm.
Preferably, described matrix is one of monocrystalline silicon, stainless steel, hard alloy.
A kind of preparation method of TiN/ZrN nano laminated coating, comprising the following steps:
Plated film cavity is first cleaned using ion beam etching, then uses ion beam etching matrix again, uses magnetic control on etching matrix
Alternating deposit TiN layer and ZrN layer are sputtered to get the TiN/ZrN nano laminated coating is arrived, wherein the etching condition are as follows: lose
Carving temperature is 350 ~ 450 DEG C, and etching vacuum degree is 3.0 × 10-3~9×10-3Pa, the condition of the magnetron sputtering alternating deposit
Are as follows: deposition raw material is titanium target and zirconium target, and carrier gas is argon gas and/or Krypton, and reaction gas is nitrogen.
TiN/ZrN nano laminated coating of the present invention is prepared using magnetically controlled DC sputtering technology, is revolved using bracket
Use is transferred to, when sample faces titanium target, titanium target is reacted by the titanium particle of high-speed ion sputter process with nitrogen, in bias effect
Under on matrix deposit one layer of TiN layer.When sample faces column zirconium target, one layer is deposited on matrix with same principle
ZrN layers, successively alternate cycles, finally obtain TiN/ZrN nano laminated coating of the present invention.
The present invention uses ion beam cleaning plated film cavity, the purpose is to take the impurity adhered on cavity, improves and plates
Film layer purity.It is and to make matrix for the gas of the impurity and absorption that further clean on matrix using ion beam etching matrix
Microcosmic roughness is presented in surface atom, and then increases the adhesive force of coating and matrix, simultaneously, moreover it is possible to keep matrix surface living
Property, it is chemisorbed on coating on matrix target surface.
For the present invention using argon gas and/or Krypton as carrier gas, wherein the big bombardment effect of Krypton quality is relatively good, and has higher
Ionization level ionizes argon gas or Krypton under certain vacuum degree and high electric field environment, makes the plasma bombardment cathode generated
Target, by the draw of substrate negative voltage electric field, the target plasma sputtered is reacted with the nitrogen being passed through generates nitrogen
Compound co-deposition is on matrix surface.Carrier gas is not involved in reaction, plays the role of bombarding sputtering target after being ionized.
Preferably, the bracket revolution speed of the magnetron sputtering alternating deposit is 0.5 ~ 5rpm/min.Magnetic of the present invention
Control sputtering alternating deposit in bracket rotation speed can only adjusting bracket revolution speed, and bracket rotational velocity be with bracket public affairs
Rotary speed and become, and bracket rotational velocity is 3 times of revolution speed, it can thus be appreciated that bracket rotational velocity is 1.5 ~ 15 rpm/
min.Bracket rotation speed speed determines the thickness of every layer of TiN layer and ZrN layers, that is, determines the modulation period of nano coating.
It is highly preferred that the bracket revolution speed is 0.5 ~ 1.5 rpm/min.It can thus be appreciated that bracket rotational velocity be 1.5 ~
4.5rpm/min。
Preferably, in the magnetron sputtering alternating deposit substrate bias be -50 ~ -300V, impressed current anode voltage be 50 ~
200V.Substrate bias is back bias voltage, and charged reaction particle guiding growth surface is reduced reaction particle by the introducing of substrate bias
Aerial scattering loss, therefore pile up effect is increased, but substrate bias also increases the kinetic energy and energy of charged particle
Amount, enhances to the sputtering release effect for having formed coating particle.Substrate bias is bigger, plasma sputtering to matrix surface
Shi Nengliang is higher, and bias is bigger, and residual stress is bigger in coating, and bond strength is lower.Bias increases, and projectile energy increases
Greatly, substrate temperature can also increase, and be conducive to deposited particles in the travel motion of matrix surface, be conducive to crystal grain along each crystal face
Growth.With the increase of substrate bias, coating hardness is gradually increased, and finally tends to be saturated.And impressed current anode voltage is anode electricity
Pressure, is placed near matrix, and impressed current anode voltage can attract electronics, increases the collision probability of electronics and gas atom, reaches
The effect for increasing ionization level makes the particle flux for being incident on target material surface have higher energy.
Preferably, the argon flow be 120 ~ 220sccm, Krypton flow be 80 ~ 110sccm, nitrogen flow be 20 ~
100sccm.The present invention is using argon gas and with Krypton as carrier gas, and the flow of carrier gas is bigger, and vacuum degree is lower, and particle encounter is free
Cheng Yue is short, and electronics is reduced by the energy that electric field obtains, and weakens the ability of activation ionization when electronics is reactant gas molecules, target
Sputtering raste reduces, and forms plasma difficulty, causes deposition rate to be lower, coating structure is loose, degradation.It is of the present invention
The uninterrupted of reaction gas nitrogen can influence the combination of the ingredient, structure, defect, surface state, coating and matrix of coating
Power and physical and chemical performance etc..The coating formed under low nitrogen flow contains the alloy of more metallic bond, with basis material phase
Matching, thus binding force is high.When high nitrogen flow, nitrogen is sufficient, and nitride covalent bond ingredient increases in coating, metallic matrix with
Coating bond energy mismatches, and contains biggish misfit strain, there are biggish stress between coating and matrix.With increasing for nitrogen, gold
The respond for belonging to particle and nitrogen that target as sputter comes out enhances, and the collision of plasma and molten drop weakens, big of surface
Grain increases, and the molten drop of formation and cavity can promote stress release in coating, although coating internal stress reduces, due to nitride
Mutually increase, the bonding force of matrix and coating at interface reduces, and causes effect of the coating binding force not as good as molten drop and cavity to coating.
Increase simultaneously with nitrogen flow, the higher Nitride Phase of hardness increases in coating, and coating is finer and close, therefore hardness number also can be with
Increase.
Matrix of the present invention processing polished first, then successively with acetone, dehydrated alcohol under the conditions of 15 ~ 30kHz
10 ~ 20min of ultrasonic cleaning is carried out, then is washed with water, finally being dried with nitrogen with purity >=99.5%.
The specific steps of ion beam etching matrix of the present invention are as follows: when Chamber vacuum reaches background vacuum 5.0 × 10- 3After Pa, it is passed through the argon gas that gas flow is 150sccm, the Krypton of 100sccm, adjusting deposition chamber environmental pressure is 1.0Pa
~ 2.0Pa, matrix add back bias voltage -200V, and Hall ion ource electric current is set as 30A, working time 33min.
Matrix of the present invention is 6 ~ 10cm at a distance from target.Target can control plasma stream at a distance from matrix
Density, and the particle energy of incident matrix surface.Distance is about short, and deposition rate is higher, and projectile energy is bigger, and binding force is got over
Small, structure is finer and close, and residual stress is bigger, and hardness increases.
The working power parameter of alternating sputtering deposition of the present invention are as follows: 6 ~ 7kW of heating power, depositing temperature 350 ~ 420
DEG C, titanium target and zirconium target power output are 5 ~ 7kW.
Alternating sputtering sedimentation time of the present invention is 2 ~ 4h.
Titanium target of the present invention and zirconium target are flat target, and purity is respectively 92.2% and 99.95%.
A kind of surfacecti proteon of TiN/ZrN nano laminated coating in component of machine, cutter, mold, operation on the sea product
In application.TiN/ZrN nano laminated coating produced by the present invention has high rigidity, high-wear resistance and corrosion resistance, system
Preparation Method is simply controllable, short preparation period, at low cost, can apply in harsh environment, is completely suitable for component of machine, knife
Tool, mold, operation on the sea product surfacecti proteon in.
Compared with prior art, the invention has the following beneficial effects:
The present invention provides a kind of TiN/ZrN nano laminated coatings and preparation method thereof, which includes matrix and alternating deposit
TiN layer and ZrN layers, the TiN layer and ZrN layers of the number of plies are respectively 10 ~ 400 layers, modulation period be 4 ~ 40nm, the TiN layer
Thickness in monolayer ratio with ZrN layers is 2:1.The painting of TiN/ZrN nanometer multilayer is prepared using magnetically controlled DC sputtering technology in the present invention
Layer, the hardness of gained coating are up to 28GPa or more, and elasticity modulus is 425 ~ 480GPa, while being also equipped with high-wear resistance and resistance to
Corrosive nature.Preparation method of the invention is simply controllable, and short preparation period is at low cost, and gained coating has excellent hardness, tough
Property, wearability and corrosion resistance, can apply in harsh environment, are completely suitable for component of machine, cutter, mold, sea
In the surfacecti proteon of upper operation product.
Detailed description of the invention
Fig. 1 is the microstructure schematic diagram (a) of the TiN/ZrN nano-multilayered structures coating of the embodiment of the present invention 1 and its fills out
It fills a vacancy and falls into effect schematic diagram (b), 1 is matrix in figure, and 2 be ZrN layers, and 3 be TiN layer, and 4 be bulky grain, and 5 be pin hole, and n is n-layer TiN
Layer and ZrN layers.
Fig. 2 is the SEM shape appearance figure of the TiN/ZrN nano-multilayered structures coating of the embodiment of the present invention 1, wherein (a) is section
Shape appearance figure；(b) amplify the surface topography map under 10,000 times；(c) amplify the surface topography map under 40,000 times.
Fig. 3 is the scratch panoramic imagery figure of the TiN/ZrN nano-multilayered structures coating of the embodiment of the present invention 1.
Fig. 4 is hardness, elasticity modulus, the hardness/bullet of the TiN/ZrN nano-multilayered structures coating of the embodiment of the present invention 1 ~ 6
The comparison diagram of property modulus value.
Fig. 5 is the polishing scratch curve graph of the TiN/ZrN nano-multilayered structures coating of the embodiment of the present invention 1 ~ 6 at room temperature.
Fig. 6 is the wear rate line chart of the TiN/ZrN nano-multilayered structures coating of the embodiment of the present invention 1 ~ 6 at room temperature.
Fig. 7 be the embodiment of the present invention 1 ~ 6 TiN/ZrN nano-multilayered structures coating concentration be 3.5% sodium chloride solution in
Corrosion polarization curve.
Specific embodiment
In order to become apparent from, completely describe technical solution of the present invention, further specifically below by way of specific embodiment
The bright present invention, it should be understood that described herein the specific embodiments are only for explaining the present invention, is not intended to limit the present invention,
Various changes can be carried out in the range of right of the present invention limits.
Embodiment 1
A kind of TiN/ZrN nano laminated coating, the coating include matrix and alternating deposit TiN layer and ZrN layers, wherein described
TiN layer and ZrN layers of the number of plies are respectively 180 layers, and the TiN layer and ZrN layers of thickness in monolayer ratio are 2:1, the matrix of the coating,
Modulation period is shown in Table 1.
The preparation method of above-mentioned TiN/ZrN nano laminated coating, comprising the following steps:
Plated film cavity is first cleaned using ion beam etching, then uses ion beam etching matrix again, uses magnetic control on etching matrix
Alternating deposit TiN layer and ZrN layer are sputtered to get the TiN/ZrN nano laminated coating is arrived, wherein the etching condition are as follows: lose
Carving temperature is 400 DEG C, and etching vacuum degree is 5.0 × 10-3Pa, the condition of the magnetron sputtering alternating deposit are as follows: depositing raw material is
Titanium target and zirconium target, argon flow 160sccm, Krypton flow be 100sccm, nitrogen flow be 60 sccm, substrate bias be-
250V, impressed current anode voltage are 60V, and matrix is 10cm at a distance from target, other concrete operations parameters are shown in Table 1.
Then wherein described matrix processing polished first is successively surpassed under the conditions of 20kHz with acetone, dehydrated alcohol
Sound cleans 15min, then washes with water, finally being dried with nitrogen with purity >=99.5%；
The concrete operation step of ion beam etching matrix are as follows: when Chamber vacuum reaches background vacuum 5.0 × 10-3After Pa, it is passed through
Gas flow is the argon gas of 150sccm, and the Krypton of 100sccm, adjusting deposition chamber environmental pressure is 1.5Pa, and matrix adds negative
Bias -200V, Hall ion ource electric current is set as 30A, working time 33min；
The working power parameter of alternating sputtering deposition are as follows: heating power 6.5kW, 400 DEG C of depositing temperature, titanium target and zirconium target power output are equal
For 6kW.
Embodiment 2 ~ 6
The coating of embodiment 2 ~ 6 is substantially the same manner as Example 1, and difference is, the modulation period of the coating is different, specifically
Operating parameter is shown in Table 1.
The preparation method of the coating of embodiment 2 ~ 6 is substantially the same manner as Example 1, and difference is, the bracket revolution
Speed is different, and concrete operations parameter is shown in Table 1.
Embodiment 7 ~ 8
The coating of embodiment 7 ~ 8 is substantially the same manner as Example 1, and difference is, the matrix of the coating is different, concrete operations
Parameter is shown in Table 1.
The preparation method of the coating of embodiment 7 ~ 8 is same as Example 1.
Table 1
Comparative example 1
A kind of TiN/ZrN nano laminated coating, substantially the same manner as Example 1, difference is that the coating modulation period is
3nm。
Comparative example 2
A kind of TiN/ZrN nano laminated coating, substantially the same manner as Example 1, difference is that the coating modulation period is
100nm。
Performance test and evaluation of result
SEM test is carried out using 430 type scanning electron microscope of Holland FEI Nova Nano to coating made from embodiment 1.
Using electronics beam scanning sample surfaces are focused, secondary electron, back scattering electricity are excited by the interaction of electronics and sample surfaces
The signals such as son simultaneously are imaged to realize observation and analysis to sample surfaces and Cross Section Morphology using these signal modulations.
To coating made from embodiment 1 using Anton Paar company big load scratching instrument (RST-Anton Paar,
Switzreland the observation of scratch panoramic imagery) is carried out.
The performance detections such as hardness are carried out to the coating of embodiment and comparative example of the present invention:
The detection method of coating hardness and elasticity modulus are as follows: use nano-hardness tester raw for CSM instrument limited liability company of Switzerland
The TTX-NHT2 type nano-hardness tester of production is applied by the variation of depth of cup in the indentation of on-line measurement pressure head and uninstall process
The loading-unloading curve of layer, the hardness number and coating elastic mould value of coating are calculated by loading-unloading curve.
The film of coating-base binding ability detection method are as follows: using the big load scratching instrument (RST-Anton of Anton Paar company
Paar, Switzreland) testing coating film-substrate cohesion.Method particularly includes: the diamond penetrator loaded using one is at the uniform velocity
Coating surface is streaked, the loading force on pressure head constantly increases, until coating is peeled off from matrix.Add on pressure head when coating failure
It carries power and is known as critical load Lc, coating failure mainly passes through acoustical signal or micro- sem observation scratch pattern in detection scoring processes
It determines, wherein imaging microscope process is matched with scratching instrument.
The wear-resisting property of coating is tested: using the wear-resisting property of high temperature friction and wear experimental machine testing coating at normal temperature.
Wherein coating abrasion rate W=V/ (P*L)；
In formula, V is abrasion loss, and V=A*2 π γ, and wherein A is polishing scratch area of section, is obtained by optical profilometer；γ is friction
Radius；L is friction total distance, is figured by radius and dead turn；P is the load that is applied.
The corrosion resistance of coating is tested: using electrochemical workstation testing coating and the corrosion resistance of matrix.
To the test result such as table 2 of embodiment of the present invention and comparative example.
Wherein A is the hardness (GPa) of coating, and B is the elasticity modulus (GPa) of coating, and C is the wear rate of coating at room temperature
(× 10-5 m3/ Nm), D is coating in the current density that concentration is in 3.5% sodium chloride solution.
Table 2
Hardness, toughness, wear rate and corrosion resistance are to measure the good and bad relevant criterion of coating quality, the bigger expression of the numerical value of A
Hardness is bigger, and the numerical value of B the big, indicates that the elasticity modulus of coating is bigger, and the numerical value of C is smaller, indicates that wear rate is lower, D value
It is smaller, indicate that current density is lower.The wear rate the big, illustrates that the antifriction performance of coating is poorer.Corrosion current density is lower,
Illustrate that coating is better to the corrosion-resistant protectiveness of matrix, the corrosion resistance of coating is strong.
Fig. 1 is the microstructure schematic diagram (a) of the TiN/ZrN nano laminated coating of the embodiment of the present invention 1 and its fills up scarce
Fall into effect schematic diagram (b), 1 is matrix in figure, and 2 be ZrN layer, and 3 be TiN layer, and 4 be bulky grain, and 5 be pin hole, n be n-layer TiN layer with
ZrN layers.Observation figure (a) is as can be seen that TiN/ZrN nano laminated coating made from embodiment 1 has TiN layer and ZrN conclusion of the business is replaced
The multilayer flat configuration of deposition, from figure (b) as can be seen that the coating obtained in embodiment 1 uses nano-multilayered structures can be with
Make coating forming core, bulky grain 4 and pin hole 5 can be filled up by next layer of progress defect again between layers, form fine and close apply
The defects of layer structure, avoids defect, the pin hole, column crystal gap of each interlayer, it is possible to reduce and eliminate deposition process, into
And improve coating corrosion resistance.
Fig. 2 is the SEM shape appearance figure of the TiN/ZrN nano-multilayered structures coating of the embodiment of the present invention 1, wherein (a) is section
Shape appearance figure；(b) amplify the surface topography map under 10,000 times；(c) amplify the surface topography map under 40,000 times.It can be seen from the figure that
Coating is dense columnar crystal structure, and coating is combined closely with matrix；Surface is more smooth, there is micropore, and crystal grain is thinner.
Fig. 3 shows the scratch panoramic imagery figure of the TiN/ZrN nano-multilayered structures coating of the embodiment of the present invention 1.From Fig. 3
It can be seen that the critical load of TiN/ZrN nano-multilayered structures coating is more than 100N, coating is when loading lotus is 100N, coating
Scratch boundary is clearly demarcated and high-visible, and it is ductility crack mostly caused by scratch that coating, which does not occur continuous rupture situation, this is to apply
What layer was formed in resisting plastic deformation.
The present invention, which depicts the test result of embodiment 1 ~ 6, compares figure, with it is intuitive observation compare bracket rotation speed and
Influence of the modulation period to coating performance.
Fig. 4 shows the hardness of the TiN/ZrN nano-multilayered structures coating of the embodiment of the present invention 1 ~ 6, elasticity modulus, hard
Degree/elasticity modulus comparison diagram.As can be seen from Figure 4: the hardness number of TiN/ZrN nano-multilayered structures coating is relative to matrix
Have and significantly promoted, with the change of revolving speed, the difference of modulation period, hardness number fluctuation is little, the wave within the scope of 29 ~ 33GPa
Dynamic, wherein small coating modulation period, hardness number are bigger.In addition, calculating separately hardness/elastic mould value of coating, hardness/bullet
Property modulus value is generally acknowledged that, the as can be seen from the figure hardness/elasticity modulus of coating related to the toughness of coating and frictional behaviour
It is worth, coating under different modulating period all with higher toughness consistent with the variation tendency that hardness number is presented, wherein modulation week
Phase small TiN/ZrN nano-multilayered structures coating has higher toughness.
Fig. 5 shows the polishing scratch curve of the TiN/ZrN nano-multilayered structures coating of the embodiment of the present invention 1 ~ 6 at room temperature
Figure.As can be seen from Figure 5: Wear track depth when revolving speed is 1.5rmp is most deep, the coating Wear track depth in other ranges of speeds
Equally matched, wearability is all preferable.
Fig. 6 shows the wear rate broken line of the TiN/ZrN nano-multilayered structures coating of the embodiment of the present invention 1 ~ 6 at room temperature
Figure.As can be seen from Figure 6: the wear rate of gained coating is all lower, and wear rate when revolving speed is 1rmp is high compared with other embodiments,
And as the reduction of modulation period, wear rate have downward trend, better wearability is shown.
Fig. 7 shows that the TiN/ZrN nano-multilayered structures coating of the embodiment of the present invention 1 ~ 6 is molten for 3.5% sodium chloride in concentration
Corrosion polarization curve in liquid.As can be seen from Figure 7: matrix corrosion potential is minimum, plated TiN/ZrN nanometer multilayer knot
Structure coating all significantly improves corrosion potential, and the trend of its receiving and losing electrons in etchant solution is made to become more difficult.
TiN/ZrN nano laminated coating corrosion current density substantially also reduces obviously, shows coating to the corrosion-resistant guarantor of matrix
Shield property, comparing each example polarization curve can be seen that the corrosion current density of 1 ~ 3 gained coating of embodiment is lower.
From embodiment and comparative example as can be seen that the hardness of TiN/ZrN nano laminated coating made from embodiment 1 ~ 8 is up to
28GPa or more, elasticity modulus are 425 ~ 480GPa, and wear rate at room temperature is 9.5 × 10-5~21×10-5 m3/ Nm, has
Good wearability, and matrix plates the coating and significantly improves corrosion potential later, illustrates that coating obtained has well
Corrosion resistance.Coating performance made from embodiment 1 ~ 8 is significantly better than comparative example 1 and 2, illustrates modulation period to coating
The performances such as hardness, toughness have great influence.Preparation method of the invention is simply controllable, and short preparation period is at low cost, and gained applies
Layer has excellent hardness, toughness, wearability and corrosion resistance, can be used in harsh environment, can be applied to zero mechanical
Part, cutter, mold, operation on the sea product surfacecti proteon in.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate examples made by the present invention, and is not to this
The restriction of the embodiment of invention.It will be appreciated by those skilled in the art that can also make on the basis of the above description other
Various forms of variations or variation, there is no necessity and possibility to exhaust all the enbodiments.It is all in spirit of the invention
With any modifications, equivalent replacements, and improvements made within principle etc., the protection scope of the claims in the present invention should be included in
Within.
Claims (10)
1. a kind of TiN/ZrN nano laminated coating, which is characterized in that the coating includes the TiN layer and ZrN of matrix and alternating deposit
Layer, the TiN layer and ZrN layer of the number of plies are respectively 10 ~ 400 layers, and the modulation period of the coating is 4 ~ 40nm, the TiN layer with
ZrN layers of thickness in monolayer ratio is 2:1.
2. coating as described in claim 1, which is characterized in that the TiN layer and ZrN layers of the number of plies are respectively 60 ~ 180 layers.
3. coating as described in claim 1, which is characterized in that the modulation period of the coating is 4.9 ~ 30nm.
4. coating as described in claim 1, which is characterized in that described matrix is monocrystalline silicon, stainless steel, one in hard alloy
Kind.
5. such as the preparation method of the claim 1 ~ 4 TiN/ZrN nano laminated coating, which comprises the following steps:
Plated film cavity is first cleaned using ion beam etching, then uses ion beam etching matrix again, uses magnetic control on etching matrix
Alternating deposit TiN layer and ZrN layer are sputtered to get the TiN/ZrN nano laminated coating is arrived, wherein the etching condition are as follows: lose
Carving temperature is 350 ~ 450 DEG C, and etching vacuum degree is 3.0 × 10-3~9×10-3Pa, the condition of the magnetron sputtering alternating deposit
Are as follows: deposition raw material is titanium target and zirconium target, and carrier gas is argon gas and/or Krypton, and reaction gas is nitrogen.
6. preparation method as claimed in claim 5, which is characterized in that the bracket revolution speed of the magnetron sputtering alternating deposit is
0.5~5rpm/min。
7. preparation method as claimed in claim 6, which is characterized in that the bracket revolution speed is 0.5 ~ 1.5rpm/min.
8. preparation method as claimed in claim 5, which is characterized in that substrate bias is -50 in the magnetron sputtering alternating deposit
~ -300V, impressed current anode voltage are 50 ~ 200V.
9. preparation method as claimed in claim 5, which is characterized in that the argon flow is 120 ~ 220sccm, and Krypton flow is
80 ~ 110sccm, nitrogen flow are 20 ~ 100sccm.
10. a kind of TiN/ZrN nano laminated coating component of machine, cutter, mold, operation on the sea product surfacecti proteon in
Application.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110117774A (en) * | 2019-06-17 | 2019-08-13 | 广东工业大学 | A kind of TC4 titanium alloy surface coating and preparation method thereof and TC4 titanium alloy product |
| CN112593188A (en) * | 2021-03-04 | 2021-04-02 | 中南大学湘雅医院 | Composite nano multilayer film, preparation method thereof and medical surgical knife |
| CN113718206A (en) * | 2021-08-23 | 2021-11-30 | 中山市气相科技有限公司 | Preparation method of TaTiN multilayer film with sandwich structure and film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110117774A (en) * | 2019-06-17 | 2019-08-13 | 广东工业大学 | A kind of TC4 titanium alloy surface coating and preparation method thereof and TC4 titanium alloy product |
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| CN112593188B (en) * | 2021-03-04 | 2021-05-14 | 中南大学湘雅医院 | Composite nano multilayer film, preparation method thereof and medical surgical knife |
| CN113718206A (en) * | 2021-08-23 | 2021-11-30 | 中山市气相科技有限公司 | Preparation method of TaTiN multilayer film with sandwich structure and film |
| CN113718206B (en) * | 2021-08-23 | 2023-03-07 | 中山市气相科技有限公司 | Preparation method of TaTiN multilayer film with sandwich structure and film |
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