CN107287555A - A kind of self-assembled nanometer oxynitride coating and its preparation method and application - Google Patents

A kind of self-assembled nanometer oxynitride coating and its preparation method and application Download PDF

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CN107287555A
CN107287555A CN201710340300.8A CN201710340300A CN107287555A CN 107287555 A CN107287555 A CN 107287555A CN 201710340300 A CN201710340300 A CN 201710340300A CN 107287555 A CN107287555 A CN 107287555A
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self
assembled nanometer
coating
matrix
oxynitride coating
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CN107287555B (en
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王启民
耿东森
代伟
吴正涛
黎海旭
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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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0676—Oxynitrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • C23C14/0084—Producing gradient compositions
    • 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
    • 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
    • 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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Abstract

The present invention discloses a kind of preparation method of self-assembled nanometer oxynitride coating, prepared using traditional PVD technique, according to the phenomenon different with Density Distribution of energy of plasma in the range of target different distance, by adjusting the rotation of sample pivoted frame and revolution speed, change sample in different plasma region residence time, so as to prepare self-assembled nanometer multilayer oxygen nitride coatings.The coating includes oxygen-rich layer and nitrogen-enriched layer, and oxygen-rich layer and nitrogen-enriched layer alternating deposit are on matrix, and coating composition is Al：20~35at.%, Cr:10~25at.%, Si：0~15at.%, O：5~50at.%, N：10~50at.%.The preparation technology of the present invention is simple, and with low cost, adaptability is good, takes into account the advantage of nitride and oxide coating, there is very big application potentiality.

Description

A kind of self-assembled nanometer oxynitride coating and its preparation method and application
Technical field
The invention belongs to material coating field, more particularly, to a kind of self-assembled nanometer oxynitride coating and its system Preparation Method and application.
Background technology
In recent years, metal nitride, oxide, carbon are coated on the products such as tool and mould, component of machine using PVD technique Compound etc. has become a kind of wide variety of process for modifying surface to improve the method for product surface performance and used life, its Middle metal nitride coatings are cutter coat main flows.With the development of process technology, high speed cutting tool and hot-work die are contour Warm application environment, the high-temperature behavior to coating requires more and more higher.The conventional carbon such as TiC, HfC and TiN, CrN, TiCN (nitrogen) compound Coating high-temp oxidation resistance temperature is below 600 DEG C, it is impossible to meet the requirement of high-speed cutting.To improve heat resistance, Al, Cr, Si etc. The rare earth element such as element and Y is protected to add nitride coatings, such as AlTiN, AlCrN, AlTiSiN, AlTiYN improve coating High-temperature behavior, but room for promotion is limited, and the best AlCrN coatings of high-temperature behavior, heat resisting temperature also can only achieve 900-1000 DEG C or so.Further to improve hard coat high-temperature behavior, it is necessary to develop new coating system.Compared with nitride coatings, More preferably, such as aluminum oxide coating layer heat resistance can be to more than 1200 DEG C, but oxide coating fragility for oxide coating thermo-chemical stability High, hardness is low (being less than 20GPa).TiCN/Al2O3The composite coatings such as/TiN improve the high-temperature behavior of coating to a certain extent, lead to (10-400 layers) designs of peroxide/nitride alternate multiple, TiAlN/Al2O3Multilayer cutter coat has nitride hardness concurrently, tough Property good and oxide excellent high temperature chemical stability advantage, in the performance such as high-speed cutting and hot-work die processing aluminium well；By In the high-insulativity of aluminum oxide, the coating need to be using special RF (radio frequency) sputterings and BP-DMS (sputtering of bipolar pulse twin target) Technology, increases equipment cost, and sedimentation rate is relatively low, limits its popularization and application.Therefore, development process simply has oxide concurrently Turn into current urgent problem with the new coating of nitride advantage.
The content of the invention
The invention aims to the defect for overcoming prior art, there is provided a kind of self-assembled nanometer oxynitride coating Preparation method, this method is prepared using conventional arc ion plating and magnetron sputtering, according to plasma in the range of target different distance The physical efficiency amount phenomenon different with Density Distribution, by adjusting the rotation of sample pivoted frame and revolution speed, change sample not on an equal basis from Daughter region residence time, so as to realize the self assembly generation of nanometer multilayer in coating.The preparation technology of coating is simple, cost Cheap, adaptability is good, and takes into account the advantage of nitride and oxide coating, there is very big application potentiality.
It is a further object of the present invention to provide self assembly AlCr (Si) ON nanoscale oxynitride compounds prepared by a kind of above method Coating.
Another object of the present invention is to provide the application of above-mentioned self-assembled nanometer oxynitride coating.
Above-mentioned purpose of the present invention is achieved by the following technical programs：
A kind of preparation method of self-assembled nanometer oxynitride coating, is comprised the following specific steps that：
S1. metallic matrix is cleaned：By matrix polishing, then successively it is cleaned by ultrasonic 10~20min with acetone, alcohol, Load after being dried up again with nitrogen in vacuum chamber；
S2.Ar and metal ion bombardment：Target Cr targets and AlCr (Si) target are installed into equipment, heater is opened and is warming up to 300~500 DEG C, by vacuum chamber to vacuum 1.0~8.0 × 10-3Pa；200~300sccm Ar gas is then passed to, Set work support to bias -800~-1000V, sputter clean, 10~20min of bombardment time are carried out to matrix surface；Again will be inclined Pressure drop lights Cr targets, 60~150A of target current, with high energy Cr Ions Bombardment 3~15min of matrix, activation to -600~-800V Metal base surface is made a concerted effort with improving film-base junction；
S3. nano laminated coating is deposited：It is passed through O2And N2, sample pivoted frame rotational velocity and revolution speed are adjusted, air pressure is controlled In 1.0~3.0Pa, AlCr (Si) target is lighted, 60~150A of target current biases -60~-200V, 0.5~2h of sedimentation time；
S4. arc power is closed, treats that vacuum room temperature is down to room temperature, vacuum chamber is opened and takes out matrix, in matrix surface shape Into coating, as self-assembled nanometer oxynitride coating.
Preferably, rotational velocity described in step S3 is 1~6r/min, and the revolution speed is 0~5r/min.
Preferably, each element atomic percent of AlCrSi targets described in step S3 is Al：55~70at.%, Cr：20~ 35at.%, Si：0~20at.%.
Preferably, O described in step S32Account for O2And N2The 1~25% of cumulative volume.
Preferably, matrix described in step S1-S4 is metal, hard alloy or ceramics.
Self-assembled nanometer oxynitride coating prepared by the above method, the self-assembled nanometer oxynitride coating includes richness Oxygen layer and nitrogen-enriched layer, oxygen-rich layer and the nitrogen-enriched layer alternating deposit is on matrix.
Wherein, the composition of the self-assembled nanometer oxynitride coating is Al：20~35at.%, Cr：10~25at.%, Si：0~15at.%, O：5~50at.%, N：10~50at.%.
Preferably, the gross thickness of the self-assembled nanometer oxynitride coating is 2~10 μm.
Preferably, the thickness in monolayer of the oxygen-rich layer is 2~20nm, and the thickness in monolayer of the nitrogen-enriched layer is 5~100nm.
Preferably, described matrix is metal, hard alloy or ceramics.
Above-mentioned self-assembled nanometer oxynitride coating is in the protection field of component of machine and knife mold product surface Using.
Compared with prior art, the invention has the advantages that：
1. the present invention prepares self-assembled nanometer multilayer oxygen nitride coatings, the coating using arc ion plating and magnetron sputtering The advantage of nitride and oxide coating is taken into account, the difficult shortcoming of oxide coating manufacture is overcome, technique is simple, operable Property it is strong, controllability is good, with low cost, and adaptability is good, it is adaptable to the protection of the product surface such as component of machine, knife mold, has Preferable economic benefit.
2. the present invention is according to the phenomenon different with Density Distribution of energy of plasma in the range of target different distance, by adjusting Whole sample pivoted frame rotation and revolution speed, change sample in different plasma region residence time, prepare it is new from Assemble nanometer multilayer oxygen nitride coatings, go for the working environment under mal-condition.
Brief description of the drawings
Fig. 1 is schematic diagram of the present invention using arc deposited device.
Fig. 2 is SEM the and TEM photos of self-assembled nanometer oxynitride coating prepared by embodiment 1.
Fig. 3 is the structural representation of self-assembled nanometer oxynitride coating.
Embodiment
Present disclosure is further illustrated with reference to specific embodiment, but be should not be construed as limiting the invention. Unless otherwise specified, the conventional meanses that technological means used in embodiment is well known to those skilled in the art.Except non-specifically Illustrate, the reagent of the invention used, method and apparatus is the art conventional reagent, methods and apparatus.
Embodiment 1
A kind of self-assembled nanometer oxynitride coating, including oxygen-rich layer AlCrSiON and nitrogen-enriched layer AlCrSiON.Wherein, it is rich The thickness of oxygen layer is 2nm, and the thickness of nitrogen-enriched layer is that the atom percentage content of each element in 5nm, coating is：Al：20at.%, Cr：10at.%, Si：15at.%, O：50at.%, N：5at.%.
By high speed steel substrate polishing, it is cleaned by ultrasonic 10min through acetone, alcohol, then load vacuum after being dried up with nitrogen It is indoor.Target Cr targets and AlCrSi targets are installed into equipment, heater is opened and is warming up to 300 DEG C, vacuum chamber to vacuum Degree 1.0 × 10-3Below Pa.300sccm Ar gas is passed through, work support bias -1000V is set, matrix surface is sputtered Cleaning, bombardment time 10min.Bias is down to -600V afterwards, Cr targets, target current 150A, with high energy Cr Ions Bombardments is lighted Matrix 15min.Bias is adjusted to -200V, 300sccm N is passed through2Gas and O2, control air pressure is in 3.0Pa, O2/O2+N2Ratio is 25%, light CrAlSi targets, target current 60A, sedimentation time 0.5 hour, its transfer rack revolution speed is 0r/min, from rotating speed Spend for 6r/min.Complete after plated film, treat that vacuum room temperature is down to room temperature, open vacuum chamber and take out matrix, obtain self-assembled nanometer Multilayer oxygen nitride coatings.
Fig. 1 is schematic diagram of the present invention using arc deposited device.Matrix rotates during depositing coating, and matrix is just Energy of plasma and density are higher during to target, react more abundant, nitrogen content is higher, and layer is also thicker；And in matrix away from target Plasma density is relatively low during material, and the oxygen and metal for being easier to reaction generate oxygen-enriched layer, and the nanometer layer is relatively thin, therefore prepared by coating Can self assembly generation nano-multilayered structures in journey.
Fig. 2 is the TEM and SEM photograph of self-assembled nanometer multilayer oxygen nitride coatings.Wherein, Fig. 2 (a) is TEM photos, figure 2 (b) is SEM photograph.As can be seen that coating structure densification fails to substantially distinguish sandwich construction from Fig. 2 (b), and to applying Layer segment finds there are nano-multilayered structures in coating after carrying out TEM test observations, wherein the brighter thinner thickness of color for richness Oxygen layer, and color is thicker compared with deep thickness for nitrogen-enriched layer.
Embodiment 2
A kind of self-assembled nanometer multilayer oxygen nitride coatings, including oxygen-rich layer AlCrSiON and nitrogen-enriched layer AlCrSiON.Its In, the thickness of oxygen-rich layer is 8nm, and the thickness of nitrogen-enriched layer is that the atom percentage content of each element in 30nm, coating is：Al： 25at.%, Cr：15at.%, Si：5at.%, O：5at.%, N：50at.%.
By hard alloy substrate polishing, it is cleaned by ultrasonic 15min through acetone, alcohol, then load true after being dried up with nitrogen In empty room.Target Cr targets and AlCrSi targets are installed into equipment, heater is opened and is warming up to 350 DEG C, vacuum chamber is to true Reciprocal of duty cycle 5.0 × 10-3Below Pa.250sccm Ar gas is passed through, work support bias -800V is set, matrix surface is sputtered Cleaning, bombardment time 20min.Bias is down to -800V afterwards, Cr targets, target current 120A, with high energy Cr Ions Bombardments is lighted Matrix 3min.Bias is adjusted to -150V, 300sccm N is passed through2Gas and O2, control air pressure is in 1.5Pa, O2/O2+N2Ratio is 2%, light CrAlSi targets, target current 80A, sedimentation time 1 hour, its transfer rack revolution speed is 2r/min, rotational velocity For 4r/min.Complete after plated film, treat that vacuum room temperature is down to room temperature, open vacuum chamber and take out matrix, obtain self-assembled nanometer oxygen Nitride coatings.
Embodiment 3
A kind of self-assembled nanometer multilayer oxygen nitride coatings, including oxygen-rich layer AlCrSiON and nitrogen-enriched layer AlCrSiON.Its In, the thickness of oxygen-rich layer is 12nm, and the thickness of nitrogen-enriched layer is that the atom percentage content of each element in 60nm, coating is：Al： 30at.%, Cr：20at.%, Si：10at.%, O：15at.%, N：25at.%.
High speed steel substrate polishing, is cleaned by ultrasonic 15min, then load vacuum chamber after being dried up with nitrogen through acetone, alcohol It is interior.Target Cr targets and AlCrSi targets are installed into equipment, heater is opened and is warming up to 400 DEG C, vacuum chamber to vacuum 5.0×10-3Below Pa.300sccm Ar gas is passed through, work support bias -900V is set, matrix surface is carried out to sputter clearly Wash, bombardment time 15min.Bias is down to -700V afterwards, Cr targets, target current 100A, with high energy Cr Ions Bombardment bases is lighted Body 10min.Bias is adjusted to -120V, 250sccm N is passed through2And O2, control air pressure is in 1.5Pa, O2/O2+N2Ratio is 10%, Light AlCrSi targets, target current 100A, sedimentation time 1.5 hours, its transfer rack revolution speed is 3r/min, and rotational velocity is 3r/min.Complete after plated film, treat that vacuum room temperature is down to room temperature, open vacuum chamber and take out matrix, obtain self-assembled nanometer oxygen nitrogen Compound coating.
Embodiment 4
A kind of self-assembled nanometer multilayer oxygen nitride coatings, including oxygen-rich layer AlCrON and nitrogen-enriched layer AlCrON.Wherein, it is rich The thickness of oxygen layer is 20nm, and the thickness of nitrogen-enriched layer is that the atom percentage content of each element in 100nm, coating is：Al： 35at.%, Cr：25at.%, Si：0at.%, O：30at.%, N：10at.%.
By ceramic matrix polishing, it is cleaned by ultrasonic 20min through acetone, alcohol, then load vacuum chamber after being dried up with nitrogen It is interior.Target Cr targets and AlCr targets are installed into equipment, heater is opened and is warming up to 450 DEG C, vacuum chamber to vacuum 8.0 ×10-3Below Pa.200sccm Ar gas is passed through, sets work support to bias -900~-1000V, matrix surface is sputtered Cleaning, bombardment time 20min.Bias is down to -800V afterwards, Cr targets, target current 60A, with high energy Cr Ions Bombardments is lighted Matrix 15min.Bias is adjusted to -100V, 200sccm N is passed through2Gas, regulation air pressure to 1.0Pa, deposition CrN transition 5min. It is passed through O2, control air pressure is in 3.0Pa, O2/O2+N2Ratio is 1%, lights AlCr targets, target current 150A, bias -150V sink Product time 2 h, its transfer rack revolution speed is 5r/min, and rotational velocity is 1r/min.Complete after plated film, treat vacuum room temperature Room temperature is down to, vacuum chamber is opened and takes out matrix, obtain self-assembled nanometer oxynitride coating.
Fig. 3 is the structural representation of self-assembled nanometer oxynitride coating.It can be seen that self-assembled nanometer oxynitride is applied The structure of layer is made up of oxygen-rich layer and nitrogen-enriched layer, and the coating takes into account the advantage of nitride and oxide coating, overcomes oxidation The difficult shortcoming of thing coating manufacture, in the process of depositing coating, the energy of plasma and close when matrix is turned to just to target Degree is higher, reacts more abundant, nitrogen content is higher, and layer is also thicker；And plasma density is relatively low when matrix is away from target, it is easier to anti- The oxygen and metal answered generate oxygen-enriched layer, and the nanometer layer is relatively thin.Technique is simple, and workable, controllability is good, with low cost, Adaptability is good, it is adaptable to the protection of the product surface such as component of machine, knife mold, with preferable economic benefit.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, is combined and simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (10)

1. a kind of preparation method of self-assembled nanometer oxynitride coating, it is characterised in that comprise the following specific steps that：
S1. metallic matrix is cleaned：By matrix polishing, then successively it is cleaned by ultrasonic 10~20min with acetone, alcohol, then is used Load after nitrogen drying in vacuum chamber；
S2.Ar and metal ion bombardment：Target Cr targets and AlCr (Si) target are installed into equipment, heater is opened and is warming up to 300 ~500 DEG C, by vacuum chamber to vacuum 1.0~8.0 × 10-3Pa；200~300sccm Ar gas is then passed to, is set Work support biases -800~-1000V, and sputter clean, 10~20min of bombardment time are carried out to matrix surface；Bias is dropped again To -600~-800V, Cr targets, 60~150A of target current, with high energy Cr Ions Bombardment 3~15min of matrix, activated metal are lighted Matrix surface is made a concerted effort with improving film-base junction；
S3. nano laminated coating is deposited：It is passed through O2And N2, sample pivoted frame rotational velocity and revolution speed are adjusted, control air pressure exists 1.0~3.0Pa, lights AlCr (Si) target, and 60~150A of target current biases -60~-200V, 0.5~2h of sedimentation time；
S4. arc power is closed, treats that vacuum room temperature is down to room temperature, vacuum chamber is opened and takes out matrix, in matrix surface formation Coating, as self-assembled nanometer oxynitride coating.
2. the preparation method of self-assembled nanometer oxynitride coating according to claim 1, it is characterised in that institute in step S3 Rotational velocity is stated for 1~6r/min, the revolution speed is 0~5r/min.
3. the preparation method of self-assembled nanometer oxynitride coating according to claim 1, it is characterised in that institute in step S3 The each element atomic percent for stating AlCrSi targets is Al：55~70at.%, Cr：20~35at.%, Si：0~20at.%.
4. the preparation method of self-assembled nanometer oxynitride coating according to claim 1, it is characterised in that institute in step S3 State O2Account for O2And N2The 1~25% of cumulative volume.
5. the preparation method of self-assembled nanometer multilayer oxygen nitride coatings according to claim 1, it is characterised in that step Matrix described in S1-S4 is metal, hard alloy or ceramics.
6. the self-assembled nanometer oxynitride coating prepared according to any one of claim 1-5 methods described, it is characterised in that institute Stating self-assembled nanometer oxynitride coating includes oxygen-rich layer and nitrogen-enriched layer, and oxygen-rich layer and the nitrogen-enriched layer alternating deposit is in matrix On.
7. self-assembled nanometer oxynitride coating according to claim 6, it is characterised in that the self-assembled nanometer oxynitriding The composition of thing coating is Al：20~35at.%, Cr：10~25at.%, Si：0~15at.%, O：5~50at.%, N：10~ 50at.%.
8. self-assembled nanometer oxynitride coating according to claim 6, it is characterised in that the self-assembled nanometer oxynitriding The gross thickness of thing coating is 2~10 μm, and the thickness in monolayer of the oxygen-rich layer is 2~20nm, and the thickness in monolayer of the nitrogen-enriched layer is 5 ~100nm.
9. self-assembled nanometer oxynitride coating according to claim 6, it is characterised in that described matrix is metal, hard Alloy or ceramics.
10. the self-assembled nanometer oxynitride coating described in claim any one of 6-9 is in component of machine and knife mold product Application in the protection field on surface.
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Cited By (8)

* Cited by examiner, † Cited by third party
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CN108018528A (en) * 2017-10-31 2018-05-11 广东工业大学 A kind of high-temperature oxidation resistant AlTiYN coatings and preparation method and application
CN108220875A (en) * 2018-01-16 2018-06-29 广东工业大学 A kind of Ti-Al nitride laminated coating cutter and preparation method thereof
CN108330453A (en) * 2018-01-31 2018-07-27 广东工业大学 A kind of AlTiN/AlTiYN nanometer multilayers cutter coat and preparation method thereof
CN108456843A (en) * 2018-01-19 2018-08-28 广东工业大学 A kind of high performance Ti AlSiN nano-composite coatings and its preparation method and application
CN113174562A (en) * 2021-03-17 2021-07-27 广东工业大学 Self-organized nanostructure oxynitride hard coating and preparation method and application thereof
US11560618B2 (en) 2017-11-24 2023-01-24 Oerlikon Surface Solutions Ag, Pfäffikon Al—Cr-based ceramic coatings with increased thermal stability
JP2023026303A (en) * 2021-08-11 2023-02-24 株式会社オンワード技研 AlCr COATING HAVING OXIDATION RESISTANCE AND ABRASION RESISTANCE, AND COATED ARTICLE THEREOF
WO2024060667A1 (en) * 2022-09-20 2024-03-28 株洲钻石切削刀具股份有限公司 Coating cutting tool

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106191791A (en) * 2016-07-06 2016-12-07 广东工业大学 A kind of high temperature low friction Cr AlSiON nano-composite coating and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106191791A (en) * 2016-07-06 2016-12-07 广东工业大学 A kind of high temperature low friction Cr AlSiON nano-composite coating and preparation method thereof

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CN108018528A (en) * 2017-10-31 2018-05-11 广东工业大学 A kind of high-temperature oxidation resistant AlTiYN coatings and preparation method and application
US11560618B2 (en) 2017-11-24 2023-01-24 Oerlikon Surface Solutions Ag, Pfäffikon Al—Cr-based ceramic coatings with increased thermal stability
CN108220875A (en) * 2018-01-16 2018-06-29 广东工业大学 A kind of Ti-Al nitride laminated coating cutter and preparation method thereof
CN108456843A (en) * 2018-01-19 2018-08-28 广东工业大学 A kind of high performance Ti AlSiN nano-composite coatings and its preparation method and application
CN108330453A (en) * 2018-01-31 2018-07-27 广东工业大学 A kind of AlTiN/AlTiYN nanometer multilayers cutter coat and preparation method thereof
CN113174562A (en) * 2021-03-17 2021-07-27 广东工业大学 Self-organized nanostructure oxynitride hard coating and preparation method and application thereof
JP2023026303A (en) * 2021-08-11 2023-02-24 株式会社オンワード技研 AlCr COATING HAVING OXIDATION RESISTANCE AND ABRASION RESISTANCE, AND COATED ARTICLE THEREOF
JP2023026416A (en) * 2021-08-11 2023-02-24 株式会社オンワード技研 AlCr COATING HAVING OXIDATION RESISTANCE AND ABRASION RESISTANCE MADE OF OXYNITRIC SUPERMULTILAYER COATING FILM, COATED ARTICLE THEREOF, AND PRODUCTION METHOD THEREOF
JP7240045B2 (en) 2021-08-11 2023-03-15 株式会社オンワード技研 AlCr oxidation-resistant wear-resistant coating and its coating
JP7240053B2 (en) 2021-08-11 2023-03-15 株式会社オンワード技研 AlCr Oxidation-Resistant and Wear-Resistant Coating Composed of Oxynitride Super Multilayer Coating, Its Coating, and Method for Producing the Same
WO2023199618A1 (en) * 2021-08-11 2023-10-19 株式会社オンワード技研 Alcr oxidation-resistant and wear-resistant coating, and coated object coated by same and method for manufacturing same
WO2024060667A1 (en) * 2022-09-20 2024-03-28 株洲钻石切削刀具股份有限公司 Coating cutting tool

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