CN104480443A - Hard and tough nano composite ZrAlCuN coating and preparation method thereof - Google Patents
Hard and tough nano composite ZrAlCuN coating and preparation method thereof Download PDFInfo
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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
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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
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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
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
Abstract
The invention discloses a hard and tough nano composite ZrAlCuN coating and a preparation method thereof, and relates to a nano composite coating and a preparation method thereof. A hard and tough coating with thickness of several microns is generated on the surface of a metal matrix to improve the wearing resistance of the matrix under action of impact load, and can be used as a tool and mould surface coating as well as an erosion-resistant protective coating. The coating is a composite coating consisting of a transition layer and a working layer, wherein the transition layer is used for improving bonding strength. The working layer is a nano composite coating consisting of nitrides and metal single substances which are immiscible with one another. The preparation method of the hard and tough nano composite ZrAlCuN coating comprises the following steps: sputtering Zr, Al and Cu elements by adopting a magnetron sputtering technology, and performing co-deposition by taking N2 as a working gas to form the nano composite structure coating. The coating not only has high hardness, but also has high toughness, and can be firmly bonded with the matrix.
Description
Technical field
The present invention relates to nano-composite coating and preparation method thereof, particularly relate to zirconium aluminum bronze nitrogen (hereinafter referred to as the ZrAlCuN) nano-composite coating and preparation method thereof with high rigidity, high tenacity.
Background technology
Adopt the method for magnetron sputtering, metallic matrix deposits one deck hard nitride coatings, the hardness of matrix and wear-resistant, corrosion resistant performance can be significantly improved.This method is widely used.As deposited one deck TiN coating at cutter or die surface, because TiN belongs to nitride ceramics, it is high a lot of that its hardness compares metal, and the life-span of cutter or mould therefore can be made to improve several times.The nitride that magnesium-yttrium-transition metal Ti, Zr, Ta etc. are formed is current modal hard nitride coatings.
From raising wear resistance, the coating hardness of preparation is higher, and its wear resistance is stronger.Therefore, the developing direction of hard nitride coatings improves its hardness.The method of main employing has two kinds, and a kind of is the composition changing coating, and a kind of is the heterogeneous microstructure changing coating.With regard to first method, in practice, constantly there is new coating system, in TiN, such as add alloy element Al form TiAlN coating.Due to Al be solidly soluted in TiN lattice time, the atom size of Al and the atom of Ti vary in size, and cause lattice distortion thus, thus produce solid solution strengthening effect, its hardness can reach 20 ~ 30GPa, thus improves abrasion resistance properties.Second method, nano composite structure is the main method improving coating hardness.As TiN/ZrN nano-composite coating is compounded to form by TiN crystal grain and ZrN, its hardness comparatively TiN coating improves a lot.These hard coats are applied in anti abrasive occasion.
But for the metallic substance of the load that withstands shocks, not only require that the hardness of hard coat is high, also will have high toughness simultaneously.Such as, in aircraft engine, titanium alloy blade mainly bears erosion effect, and the hardness of titanium alloy is lower, therefore in the urgent need at its surface deposition one deck hard protection coatings.Erosion particle impacts body material from each different angles, the effect of existing cutting, have again the effect of dynamic impulsion, therefore not only require that matrix surface protective coating has high hardness to resist cutting, and the function demand coating of continuous dynamic impact loads has high toughness.Therefore, emphasize merely that TiN, TiAlN of hardness are that the hard coat of representative can not meet the demands.For cutter, mould coating, under impact loading, the coating of poor toughness can lose efficacy very soon, there is same problem.
Therefore, the novel super-hard coating simultaneously with high rigidity and high tenacity is only the following coated material system having engineer applied most and be worth.Obtain while maintenance higher hardness, obtain good toughness, the military service performance of hard coat under moving load can be ensured.
With regard to current hard protection coatings, also do not occur that there is high hardness and high flexible coating simultaneously.
Summary of the invention
The present invention, in order to solve the problem of metallic substrate surface hard nanometer compound coating opposing impact loading, provides one and possesses hard, tough performance ZrAlCuN nano-composite coating and preparation method thereof simultaneously.
For this reason, the present invention adopts following technical scheme:
A kind of ZrAlCuN nano-composite coating, is characterized in that: sputtered transition layer and working lining successively at matrix surface.Transition layer is metal level, is made up of zirconium (Zr), aluminium (Al), copper (Cu); Working lining is nitride ZrAlCuN ceramic layer.Said matrix refers to titanium alloy or hard alloy metal material.
Namely transition layer can be the metal level that Zr, Al, Cu codeposition is formed, and also can be first deposit Zr, Al, then deposit Zr, the metal level that Al, Cu are formed.The thickness of transition layer is between 100 ~ 300nm.
Working lining is ZrAlCuN nitride ceramics layer, because Cu and ZrAlN does not dissolve each other, therefore can form ZrAlN nanocrystalline with Ni metal nano composite structure.The thickness of working lining is between 1um ~ 4um.
In working lining ZrAlCuN, the atomic percent 20% ~ 40% of Al, coating is with ZrN crystalline structure for base, and the content of Al is no more than its solid solubility in ZrN, namely forms ZrAlN sosoloid, and does not occur AlN phase.Otherwise cause the hardness of coating to reduce, degraded toughness.
In working lining ZrAlCuN, the atomic percent 2% ~ 5% (if the atomic percent of Cu is greater than 5%, coating hardness can be caused to reduce) of Cu.
In working lining ZrAlCuN, the nanocrystalline size of ZrAlN is less than 20nm, and Cu can be solidly soluted in ZrAlN lattice, also can the form Dispersed precipitate of metal simple-substance on ZrAlN crystal particle crystal boundary.Adopt XRD to test the phase composite of ZrAlCuN coating, can't detect the existence of Cu simple substance phase.
The hardness of working lining ZrAlCuN is greater than 35GPa, when adopting Vickers indenter to be less than 4.9N load press-in ZrAlCuN coat inside, ZrAlCuN coating can not with matrix stripping, and impression diagonal lines crackle can not be produced; When 4.9N is pressed into coat inside, the radial cracking of generation is no more than impression catercorner length; When adopting 9.8N to be pressed into coat inside, coating can not produce phenomenon of bursting apart.
The preparation method of said ZrAlCuN nano-composite coating, is characterized in that:
(1) metal base cleaning;
(2) argon ion sputtering cleaning in vacuum chamber: be heated to 200 ?after 400 DEG C of temperature, in vacuum chamber, pass into argon gas, open grid bias power supply, argon gas discharging produces plasma body, under the effect of bias voltage, bombard matrix.
(3) ion source cleaning.Pass into argon gas, open ion source generation glow discharge and clean.
(4) transition layer is prepared.Open sputtering target, sputtering Zr, Al, Cu metal forms metal level at matrix surface.Wherein, Al atomic percent 20% ~ 40%, Cu atomic percent 2% ~ 5%.
(5) preparation work layer.Pass into nitrogen (N
2), use gas meter to control the flow of reactant gases.On intermediate metal, deposition obtains ZrAlCuN ceramic layer.
(6) cool and come out of the stove: in order to prevent coatingsurface oxidized, allowing workpiece be cooled to less than 100 DEG C under vacuo after plated film, cool to room temperature with the furnace afterwards, and then take out sample.
(7) described sputtering target, namely can be ZrAlCu alloys target, also can be Zr, Al, Cu elemental metals target, can also be ZrAl alloys target and Cu elemental metals target.
Further, the atomic percent of described ZrAlCu alloys target, Al is no more than 20%, Cu and is no more than 2%.
Further, in vacuum chamber argon ion sputtering cleaning time, vacuum tightness between 1 ~ 3Pa, between grid bias power supply 1000V ~ 1200V.
Further, when ion source sputter clean, vacuum tightness between 0.3 ~ 0.6Pa, between ion source power 200W ~ 400W.
In the process depositing ZrAlCu transition layer and ZrAlCuN working lining, controlled sputtering source strobe pulse power supply, pulsed voltage 200 ~ 1000V, pulse-repetition 100Hz ~ 300Hz.
When depositing ZrAlCu transition layer, time 5 ~ 15min.
When depositing ZrAlCuN working lining, vacuum tightness is between 0.5 ~ 0.8Pa.
When depositing ZrAlCuN working lining, negative bias is between 200V ~ 500V.
When depositing ZrAlCuN working lining, between ion source power 200W ~ 300W.
When depositing ZrAlCuN working lining, depositing time 60 ~ 180min.
In sum, the present invention utilizes magnetron sputtering technique, by regulation and control coated component, Optimizing Process Parameters, deposition obtains the nano combined hard tough coating of ZrAlCuN, and compared with the hard magnesium-yttrium-transition metal nitride coatings prepared with existing magnetron sputtering technique, tool has the following advantages:
(1) hardness of coating improves further.The coating hardness of magnesium-yttrium-transition metal nitride TiN, ZrN etc. two constituent element is higher, as TiAlN, ZrAlN, utilizes solid solution strengthening effect can improve the hardness of coating by adding more multicomponent.These elements added are generally nitride forming elements, so formation is single phase structure, do not form the nano composite structure of unnecessary two phase composites.And the present invention adds Cu element does not dissolve each other with nitride, Cu can be gathered in around crystal boundary, define nano composite structure, the effect brought not only serves solid solution strengthening effect, and due to Cu refinement nitride grains, make use of the principle of refined crystalline strengthening, further increase the hardness of coating, can more than 35GPa.
(2) coating toughness be improved significantly.The nitride grains due to Cu refinement, the ZrAlN uniform small grains of formation, its toughness and general hard coat TiN, TiAlN and TiN/ZrN compares, and tool increases significantly.
This possess high hardness and the coating of toughness simultaneously, can significantly improve the effect of matrix opposing shock load.
Accompanying drawing explanation
Fig. 1 a is the hardness curve preparing ZrAlCuN nano-composite coating in specific embodiment one.
Fig. 1 b is the toughness test vickers indentation preparing ZrAlCuN nano-composite coating in specific embodiment one.
Fig. 2 a is the hardness curve preparing ZrAlCuN nano-composite coating in specific embodiment two.
Fig. 2 b is the toughness test vickers indentation preparing ZrAlCuN nano-composite coating in specific embodiment two.
Embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment one:
In the present embodiment, take titanium alloy ti6al4v as matrix, adopt magnetron sputtering technique deposition ZrAlCuN coating, to improve the erosion resistant performance of titanium alloy.Concrete preparation process is as follows:
(1) the preliminary cleaning of titanium alloy: use tap water, the then rinsing in deionized water after 15 minutes of metal cleaner ultrasonic cleaning sample, putting into mass percent concentration is afterwards 0.5% rare H
3pO
4middle surface active 2 minutes, ultrasonic cleaning 15 minutes in acetone after rinsing, puts into vacuum chamber after oven dry again.
(2) vacuum chamber argon sputter cleaning: after being heated to 200 DEG C, pass into argon gas (volume percent >99.99%) in vacuum chamber, make vacuum chamber internal gas pressure rise to 1.0Pa.Now opening grid bias power supply, is under the effect of 1200V in negative bias, and argon gas discharging produces plasma body, bombards matrix, Bombardment and cleaning 15 minutes under the effect of bias voltage.
(3) ion source cleaning: pass into argon gas to vacuum tightness 0.3Pa, open ion source power 300W, negative bias 500V, cleans 15 minutes.
(4) deposit ZrAlCu transition layer: pass into argon gas to vacuum tightness 0.5Pa, open ZrAlCu (atomic ratio 85:13:2.Because the sputtering raste of Zr, Al and Cu tri-kinds of elements is different, cause target composition and film composition variant.) alloy sputtering targets, sputtering sedimentation ZrAlCu metal level 5 minutes.Substrate negative voltage 200V, sputtering current 2A, pulsed voltage 300V, pulse-repetition 100Hz, ion source power 200W.
(5) ZrAlCuN working lining is deposited: pass into argon gas and nitrogen (volume percent >99.99%), partial pressure of ar gas 0.5Pa, nitrogen partial pressure 0.01Pa, opens ZrAlCu alloy sputtering targets, deposition ZrAlCuN nano-composite coating.Substrate negative voltage 200V, sputtering current 3A, pulsed voltage 480V, pulse-repetition 100Hz, ion source power 200W, 60 minutes time.
(6) cool and come out of the stove: in order to prevent coatingsurface oxidized, allowing workpiece in vacuum chamber, be cooled to less than 100 DEG C after plated film, cool to room temperature with the furnace afterwards, and then take out sample.
(7) composition of the ZrAlCuN coating prepared by is Zr
0.77al
0.20cu
0.03n (atoms metal and atom N ratio are close to 1:1), transition region thickness 100nm, working lining thickness 1 μm.Performance test is carried out to prepared ZrAlCuN nano-composite coating:
Nanometer press fit instrument is adopted to measure nanometer penetration hardness.Fig. 1 a is nanometer press-in curve, and obtaining this nano-composite coating hardness is thus 40.1GPa.
Adopt Vickers' hardness Vickers indenter testing coating toughness.Fig. 1 b is the vickers indentation under 4.9N load, can see that coating and matrix are peeled off, and coating is for producing brittle failure, and impression diagonal lines radial cracking is less than catercorner length.Show that the toughness of this coating is fine.
Embodiment two:
In the present embodiment, take rapid steel as matrix, adopt magnetron sputtering technique deposition ZrAlCuN coating, to improve the performance of Hardness of High Speed Steel and shock-resistant load.Concrete preparation process is as follows:
(1) the preliminary cleaning of titanium alloy: use metal cleaner ultrasonic cleaning sample tap water after 15 minutes, then rinsing in deionized water, putting into mass percent concentration is afterwards 1% rare HCl surface active 2 minutes, ultrasonic cleaning 15 minutes in acetone after rinsing, puts into vacuum chamber after oven dry again.
(2) vacuum chamber argon sputter cleaning: after being heated to 400 DEG C, pass into argon gas (volume percent >99.99%) in vacuum chamber, make vacuum chamber internal gas pressure rise to 3.0Pa.Now opening grid bias power supply, is under the effect of 1000V in negative bias, and argon gas discharging produces plasma body, bombards matrix, Bombardment and cleaning 15 minutes under the effect of bias voltage.
(3) ion source cleaning: pass into argon gas to vacuum tightness 0.6Pa, open ion source power 400W, negative bias 500V, cleans 15 minutes.
(4) deposit ZrAlCu transition layer: pass into argon gas to vacuum tightness 0.5Pa, open Zr, Al, Cu elemental metals (atomic percent >99.9%) sputtering target, sputtering sedimentation ZrAlCu metal level 15 minutes.Substrate negative voltage 200V.Sputtering target is pulsed sputter target, Zr target pulsed voltage 200V, sputtering current 2A, pulse-repetition 100Hz; Al target sputtering current 1A, pulsed voltage 200V, pulse-repetition 100Hz; Cu target sputtering current 0.5A, pulsed voltage 200V, pulse-repetition 50Hz.Ion source power 400W.Depositing time 15min.
(5) ZrAlCuN working lining is deposited: pass into argon gas and nitrogen (volume percent >99.99%), partial pressure of ar gas 0.5Pa, nitrogen partial pressure 0.01Pa, opens Zr, Al, Cu sputtering target, deposition ZrAlCuN nano-composite coating.Substrate negative voltage 300V, Zr target pulsed voltage 200V, sputtering current 2A, pulse-repetition 100Hz; Al target sputtering current 1A, pulsed voltage 100V, pulse-repetition 300Hz; Cu target sputtering current 0.5A, pulsed voltage 200V, pulse-repetition 100Hz.Ion source power 400W.Depositing time 180 minutes.
(6) cool and come out of the stove: in order to prevent coatingsurface oxidized, being cooled to less than 100 DEG C under allowing workpiece after plated film in vacuum chamber, cooling to room temperature with the furnace afterwards, and then taking out sample.
(7) composition of the ZrAlCuN coating prepared by is Zr
0.69al
0.29cu
0.02n (atoms metal and atom N ratio are close to 1:1), transition region thickness 300nm, working lining thickness 4 μm.Performance test is carried out to prepared ZrAlCuN nano-composite coating:
Nanometer press fit instrument is adopted to measure nanometer penetration hardness.Fig. 2 a is nanometer press-in curve, and obtaining this nano-composite coating hardness is thus 41GPa.
Adopt Vickers' hardness Vickers indenter testing coating toughness.Fig. 2 b is the vickers indentation under 4.9N load, and can see that coating and matrix are peeled off, coating does not produce brittle failure, and remarkable radial cracking does not appear in impression diagonal lines.Show that the toughness of this coating is fine.
Embodiment three:
In the present embodiment, take rapid steel as matrix, adopt magnetron sputtering technique deposition ZrAlCuN coating, to improve the performance of Hardness of High Speed Steel and shock-resistant load.Concrete preparation process is as follows:
(1) the preliminary cleaning of rapid steel: use metal cleaner ultrasonic cleaning sample tap water after 15 minutes, then rinsing in deionized water, putting into mass percent concentration is afterwards 0.8% rare HCl surface active 2 minutes, ultrasonic cleaning 15 minutes in acetone after rinsing, puts into vacuum chamber after oven dry again.
(2) vacuum chamber argon sputter cleaning: after being heated to 300 DEG C, pass into argon gas (volume percent >99.99%) in vacuum chamber, make vacuum chamber internal gas pressure rise to 2.0Pa.Now opening grid bias power supply, is under the effect of 1000V in negative bias, and argon gas discharging produces plasma body, bombards matrix, Bombardment and cleaning 15 minutes under the effect of bias voltage.
(3) ion source cleaning: pass into argon gas to vacuum tightness 0.5Pa, open ion source power 300W, negative bias 500V, cleans 15 minutes.
(4) ZrAlCu transition layer is deposited: pass into argon gas to vacuum tightness 0.5Pa, open ZrAl alloy (atomic ratio 85:15) target, metal refining ZrAl about 5 minutes, then Cu elemental metals (atomic percent >99.9%) sputtering target is opened, sputtering sedimentation ZrAlCu metal level 10 minutes.Substrate negative voltage 200V.Sputtering target is pulsed sputter target, ZrAl target pulsed voltage 200V, sputtering current 2A, pulse-repetition 100Hz; Cu target sputtering current 0.5A, pulsed voltage 100V, pulse-repetition 100Hz.Ion source power 300W.
(5) deposit ZrAlCuN working lining: pass into argon gas and nitrogen, partial pressure of ar gas 0.79Pa, nitrogen partial pressure 0.01Pa, open ZrAl, Cu sputtering target, deposition ZrAlCuN nano-composite coating.Substrate negative voltage 500V, ZrAl target pulsed voltage 500V, sputtering current 2A, pulse-repetition 100Hz; Cu target sputtering current 0.5A, pulsed voltage 200V, pulse-repetition 300Hz.Ion source power 300W.Depositing time 120 minutes.
(6) cool and come out of the stove: in order to prevent coatingsurface oxidized, being cooled to less than 100 DEG C under allowing workpiece after plated film in vacuum chamber, cooling to room temperature with the furnace afterwards, and then taking out sample.
(7) composition of the ZrAlCuN coating prepared by is Zr
0.55al
0.40cu
0.05n (atoms metal and atom N ratio are close to 1:1), transition region thickness 260nm, working lining thickness 2.5 μm.Performance test is carried out to prepared ZrAlCuN nano-composite coating:
Nanometer press fit instrument is adopted to measure nanometer penetration hardness.This nano-composite coating hardness is 35GPa.
Adopt Vickers' hardness Vickers indenter testing coating toughness.Coating and matrix are peeled off, and remarkable radial cracking does not appear in impression diagonal lines.
Claims (9)
1. a hard tough nano combined ZrAlCuN coating, is characterized in that: sputtered transition layer and working lining successively at matrix surface; Transition layer is metal level, is made up of zirconium, aluminium, copper; Working lining is nitride ZrAlCuN ceramic layer; Said matrix refers to titanium alloy or hard alloy metal material.
2. the hard tough nano combined ZrAlCuN coating of one according to claim 1, is characterized in that:
Transition layer is the metal level that Zr, Al, Cu codeposition is formed, or first deposits Zr, Al, then deposits Zr, the metal level that Al, Cu are formed.
3. the hard tough nano combined ZrAlCuN coating of one according to claim 1, is characterized in that:
The thickness of working lining is between 1 μm ~ 4 μm, and the thickness of transition layer is between 100 ~ 300nm.
4. the hard tough nano combined ZrAlCuN coating of one according to claim 1, is characterized in that:
In working lining ZrAlCuN, the atomic percent 2% ~ 5% of the atomic percent 20% ~ 40%, Cu of Al.
5. the hard tough nano combined ZrAlCuN coating of one according to claim 1, is characterized in that:
In transition layer, Al atomic percent 20% ~ 40%, Cu atomic percent 2% ~ 5%.
6. prepare claim 1 ?the method of a kind of hard tough nano combined ZrAlCuN coating of 5 any one, it is characterized in that step is as follows:
(1) metal base cleaning;
(2) argon ion sputtering cleaning in vacuum chamber: be heated to 200 ?after 400 DEG C of temperature, in vacuum chamber, pass into argon gas, open grid bias power supply, argon gas discharging produces plasma body, under the effect of bias voltage, bombard matrix;
(3) ion source cleaning; Pass into argon gas, open ion source generation glow discharge and clean;
(4) transition layer is prepared; Open sputtering target, sputtering Zr, Al, Cu metal forms metal level at matrix surface;
(5) preparation work layer; Pass into nitrogen, use gas meter to control the flow of reactant gases; On intermediate metal, deposition obtains ZrAlCuN ceramic layer;
(6) cool and come out of the stove: allowing workpiece be cooled to less than 100 DEG C under vacuo after plated film, cool to room temperature with the furnace afterwards, and then take out sample;
Described sputtering target is ZrAlCu alloys target, or Zr, Al, Cu elemental metals target, or ZrAl alloys target and Cu elemental metals target;
In the process preparing ZrAlCu transition layer and ZrAlCuN working lining, controlled sputtering source strobe pulse power supply, pulsed voltage 200 ~ 1000V, pulse-repetition 100Hz ~ 300Hz;
When depositing ZrAlCu transition layer, time 5 ~ 15min;
Deposit ZrAlCuN working lining time, vacuum tightness between 0.5 ~ 0.8Pa, negative bias between 200V ~ 500V, between ion source power 200W ~ 400W, depositing time 60 ~ 180min.
7. method according to claim 6, is characterized in that:
The atomic percent of described ZrAlCu alloys target, Al is no more than 20%, Cu and is no more than 2%.
8. method according to claim 6, is characterized in that:
In vacuum chamber argon ion sputtering cleaning time, vacuum tightness between 1 ~ 3Pa, between grid bias power supply 1000V ~ 1200V.
9. method according to claim 6, is characterized in that:
When ion source sputter clean, vacuum tightness between 0.3 ~ 0.6Pa, between ion source power 200W ~ 400W.
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| CN109023283A (en) * | 2018-09-29 | 2018-12-18 | 中国科学院宁波材料技术与工程研究所 | A kind of quaternary solid-ceramic coating with corrosion resistance and preparation method thereof and device |
| CN109023279A (en) * | 2018-09-17 | 2018-12-18 | 南京航空航天大学 | A kind of Cu-CrBN nano-composite coating and preparation method thereof |
| CN109112481A (en) * | 2018-09-29 | 2019-01-01 | 中国科学院宁波材料技术与工程研究所 | A kind of solid-ceramic coating and preparation method thereof with antibacterial and corrosion resistance |
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| CN106167419B (en) * | 2016-07-12 | 2019-01-04 | 平定莹玉陶瓷有限公司 | Heat-stable ceramic casserole and preparation method with metal magnetic conducting film |
| CN107723645A (en) * | 2017-10-18 | 2018-02-23 | 北京天宜上佳新材料股份有限公司 | A kind of repeatable lightweight brake disc utilized and preparation method thereof |
| CN109023279A (en) * | 2018-09-17 | 2018-12-18 | 南京航空航天大学 | A kind of Cu-CrBN nano-composite coating and preparation method thereof |
| CN109023283A (en) * | 2018-09-29 | 2018-12-18 | 中国科学院宁波材料技术与工程研究所 | A kind of quaternary solid-ceramic coating with corrosion resistance and preparation method thereof and device |
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| CN109023283B (en) * | 2018-09-29 | 2020-05-12 | 中国科学院宁波材料技术与工程研究所 | Quaternary hard ceramic coating with corrosion resistance, and preparation method and device thereof |
| CN114000118A (en) * | 2021-10-25 | 2022-02-01 | 哈尔滨工程大学 | Preparation method of nitride layer with adjustable titanium alloy surface hardness gradient distribution layer thickness |
| CN114000118B (en) * | 2021-10-25 | 2024-03-22 | 哈尔滨工程大学 | Preparation method of titanium alloy surface hardness gradient distribution layer thickness adjustable nitride layer |
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