CN107916402A - A kind of AlCrTiSiCN coating structures and preparation method thereof - Google Patents

A kind of AlCrTiSiCN coating structures and preparation method thereof Download PDF

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CN107916402A
CN107916402A CN201711166990.6A CN201711166990A CN107916402A CN 107916402 A CN107916402 A CN 107916402A CN 201711166990 A CN201711166990 A CN 201711166990A CN 107916402 A CN107916402 A CN 107916402A
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alcrtisicn
coatings
coating
targets
matrix
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CN107916402B (en
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王铁钢
郭玉垚
刘艳梅
侯翔
林伟
戚厚军
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Tianjin University of Technology
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24Vacuum evaporation
    • C23C14/32Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325Electric arc evaporation
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021Reactive sputtering or evaporation
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02Pretreatment of the material to be coated
    • C23C14/021Cleaning or etching treatments
    • C23C14/022Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02Pretreatment of the material to be coated
    • C23C14/024Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025Metallic sublayers
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0664Carbonitrides

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)

Abstract

The invention discloses a kind of AlCrTiSiCN coating structures and preparation method thereof, it includes matrix, Al Cr Ti alloy transitions layers and AlCrTiSiCN coatings, Al Cr Ti alloy transition layers are combined with matrix, AlCrTiSiCN coatings are combined with Al Cr Ti alloy transition layers, and the AlCrTiSiCN coatings are formd with amorphous phase Si3N4It is wrapped in AlN, TiN, CrN, Al8SiC7、Cr2N0.39C0.16Etc. the nano composite structure coating of nanometer crystalline phase.Nano combined AlCrTiSiCN coatings stable chemical performance, does not react with common chemical attack medium.Amorphous phase can effectively stop the germinating and extension of micro-crack in coating, drastically increase coating toughness.AlCrTiSiCN coatings have higher hardness and toughness, and wear-resisting property is good.AlCrTiSiCN uniform coating thickness and compact structure, have good bond strength with matrix.

Description

A kind of AlCrTiSiCN coating structures and preparation method thereof
Technical field
The invention belongs to material surface engineering technolog field, and in particular to a kind of AlCrTiSiCN coating structures and its preparation Method.
Background technology
With the high finishing of modern efficient and difficult-to-machine material use it is increasing to cutter high temperature hardness, wearability and heat The requirement of the performances such as chemical stability becomes further harsh.Currently used TiN coating hardness is low, wears no resistance, especially hot steady Qualitative difference, limits the application in cutting tool.TiN coatings, shape are arrived by introducing alloying element (such as Al, Zr, Cr, V) The multi-element coating system (such as TiAlN) of Cheng Xin, can improve coating hardness, improve the abrasion resistance and heat endurance of coating, still The oxidation resistance temperature of coating only has 800 DEG C, is not met by temperature when cutting.Therefore, some simple binary or ternary Coating cannot gradually meet severe machining condition.In recent years, in order to further improve the high temperature hardness of cutter coat and Antioxygenic property, improves the bond strength of coating and matrix, coated cutting tool is more suitable for the severe processing conditions such as cutting, research Emphasis focused on nano composite structure coating system.
Nano composite structure coating is to be embedded in very thin amorphous layer (such as a- by isolated nanocrystalline (such as nc-TiN) Si3N4) in a kind of composite structure coating for being formed, nanocrystalline hardness is higher, and amorphous phase plasticity is good, and two-phase interface cohesive energy is high, brilliant Body phase and amorphous phase are in thermodynamically separation trend;In addition, it is tiny it is nanocrystalline in can not form dislocation, it is intercrystalline thin non- Crystal layer can effectively stop Grain Boundary Sliding, and substantial amounts of two-phase interface adds micro-crack extension resistance.Therefore, this cutter coat tool Have high rigidity (>40GPa), high tenacity, excellent wear-resisting property and high high-temp stability, are suitable for high-speed cutting, dry processing Etc. operating mode.
The present invention is prepared for CrAlTiSiCN nanometers again using arc ion plating (aip) in 304 stainless steels and single crystalline Si on piece Close coating.The coating has higher hardness, high temperature oxidation resistance and wearability.The coating is particularly suitable for modern high Rapid-curing cutback machining field, further improves the usage service life of cutter, reduces the use of cutting fluid, realize green manufacturing.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of AlCrTiSiCN coating structures and its preparation Method.
The present invention is achieved by the following technical solutions:
A kind of AlCrTiSiCN coating structures, it includes matrix, Al-Cr-Ti alloy transitions layer and AlCrTiSiCN coatings, Al-Cr-Ti alloy transition layers are combined with matrix, and AlCrTiSiCN coatings are combined with Al-Cr-Ti alloy transition layers, described AlCrTiSiCN coatings are formd with amorphous phase Si3N4It is wrapped in AlN, TiN, CrN, Al8SiC7、Cr2N0.39C0.16Etc. nanocrystalline The nano composite structure coating of phase.
The preparation method of the AlCrTiSiCN coating structures is:
The base vacuum of vacuum chamber is first evacuated to 4.0 × 10-3Pa, and 500 DEG C are preheated to, then application -800V direct currents are inclined Pressure, it is 150sccm that argon flow amount is passed through into vacuum chamber, carries out Glow Discharge Cleaning to matrix surface, operating pressure is maintained at 2.4Pa, Discharge Cleaning 10min;
Argon flow amount is turned down afterwards to 70sccm, and operating pressure is reduced to 0.8Pa, while opens AlCr targets and AlTi targets electricity Source, target becomes Cr30Al70, Ti30Al70, and (the Cr atoms in atomic ratio, i.e. AlCr targets account for 30%, Al atoms and account for 70%; Ti atoms in AlTi targets account for 30%, Al atoms and account for 70%), and AlCr targets and AlTi targets average output power and target current are 1.0kW and 75A, then with icon bombardment cleaning 5min;Then reduce and be biased into -50V, depositing Al-Cr-Ti alloy transition layers 10min, two target material surfaces are 290mm apart from substrate, 500 DEG C of depositing temperature;
It is subsequently passed reacting gas N2And C2H2, by the flow of argon gas, nitrogen and acetylene be adjusted to respectively 40sccm, 220sccm, 40sccm, are then turned on Si targets, and Si targets output power and target current are respectively 0.9kW, 65A, adjust operating pressure dimension Hold in 1.2Pa, depositing temperature is maintained as 500 DEG C, starts depositing Al-Cr-Ti-Si-C-N coatings.
The advantages of the present invention are:
Nano combined AlCrTiSiCN coatings stable chemical performance, does not react with common chemical attack medium.In coating Amorphous phase can effectively stop the germinating and extension of micro-crack, drastically increase coating toughness.
AlCrTiSiCN coatings have higher hardness and toughness, and wear-resisting property is good.
AlCrTiSiCN uniform coating thickness and compact structure, have good bond strength with matrix.
N is introduced when preparing AlCrTiSiCN coatings2And C2H2, especially C2H2Introducing (introducing carbon atom), one Aspect part carbon atom is dissolved into nitride crystalline lattice, plays the role of solution strengthening, can strengthen the hardness and wearability of coating Can, on the other hand, the doping of carbon adds the species of nanometer crystalline phase, forms Al8SiC7、Cr2N0.39C0.16Etc. nanocrystalline Phase, and these carbide or the nanocrystalline hardness and strength compared to AlN, TiN, CrN with higher of carbonitride, so that again into one Step improves the mechanical property of coating.
AlCrTiSiCN preparation technology of coating is reproducible, and compared with multilayer film, the former application range is wider, and practicality is more By force, the component surface of complexity is applied especially to, there is unique advantage.
Brief description of the drawings
Fig. 1 is the XRD spectrum of AlCrTiSiCN coatings,
The surface topography map of Fig. 2A lCrTiSiCN coatings,
The Cross Section Morphology figure of Fig. 3 AlCrTiSiCN coatings,
Fig. 4 be the aluminium oxide ceramic ball of AlCrTiSiCN coatings and a diameter of 5.99mm to the grinding defect morphology figure after mill,
Fig. 5 is AlCrTiSiCN coating average friction coefficient figures.
Embodiment
Technical scheme is further illustrated with reference to specific embodiment.
The base vacuum of vacuum chamber is first evacuated to 4.0 × 10-3Pa, and 500 DEG C are preheated to, then application -800V direct currents are inclined Pressure, it is 150sccm that argon flow amount is passed through into vacuum chamber, carries out Glow Discharge Cleaning to matrix surface, operating pressure is maintained at 2.4Pa, Discharge Cleaning 10min;
Argon flow amount is turned down afterwards to 70sccm, operating pressure be reduced to 0.8Pa (because when transition zone too high pressure make from Son can produce reverse sputtering, and ion is not easy to deposit, and 0.8pa is deposition pressure best when depositing transition zone), while open AlCr Target and AlTi target power supplies, (the Cr atoms in atomic ratio, i.e. AlCr targets account for 30%, Al originals by target material composition Ti30Al70, Cr30Al70 Son accounts for 70%;Ti atoms in AlTi targets account for 30%, Al atoms and account for 70%), AlCr targets and AlTi targets average output power and target Electric current is 1.0kW and 75A, then with icon bombardment cleaning 5min;Then reduce and be biased into -50V, depositing Al-Cr-Ti alloy mistakes Cross a layer 10min, two target material surfaces are 290mm apart from substrate, 500 DEG C of depositing temperature;
It is subsequently passed reacting gas N2And C2H2(purity is 99.999%), the flow of argon gas, nitrogen and acetylene is distinguished 40sccm, 220sccm, 40sccm are adjusted to, is then turned on Si targets (Si targets be polycrystalline Si target, purity 99.999%), the output of Si targets Power and target current are respectively 0.9kW, 65A, adjust operating pressure maintain 1.2Pa (it is different from the pressure of transition zone because High Voltage can increase ion motion speed during depositing coating, ion is quickly deposited on matrix, the deposition effect reached Fruit), depositing temperature is maintained as 500 DEG C, starts depositing Al-Cr-Ti-Si-C-N coatings;Sample sedimentation time is 3h.
Fig. 1 is the XRD spectrum of AlCrTiSiCN coatings.As can be seen from Fig., which is in polycrystalline state, comprising AlN, TiN, CrN、Al8SiC7And Cr2N0.39C0.16,Etc. nanometer crystalline phase and amorphous phase Si3N4, based on AlN, TiN and CrN, it is all crystalline phase Face-centred cubic structure;This structure formed by isolated Nanocrystals Embedded in very thin amorphous layer is typical nano combined Structure.This structure coating has high rigidity, high tenacity, excellent wear-resisting property and high high-temp stability, is suitable for cutting Cutter, mould and component of machine surface.(200) crystallographic plane diffraction peak intensity is of a relatively high, illustrates the coating along (200) Crystal face preferential growth, this growth pattern improve the hardness of coating, coating is had more preferable mechanical property.Divide more than Analysis can, AlCrTiSiCN coatings are formd with amorphous phase Si3N4It is nanocrystalline and a small amount of to be wrapped in a large amount of AlN, TiN, CrN Al8SiC7、Cr2N0.39C0.16Nanocrystalline nano composite structure coating, makes coating have more preferable mechanical property and high warm surely It is qualitative.
The surface topography and section SEM patterns of AlCrTiSiCN coatings are as shown in Figures 2 and 3.Fig. 2 and Fig. 3 is respectively the painting The surface topography and Cross Section Morphology of layer.Figure it is seen that coating shows as typical electric arc ion coating plating feature, knot of tissue Structure dense uniform, surface have a small amount of bulky grain and micropore to produce.Testing coating surface composition composition for 2.76%Cr, 14.05%Al, 17.77%Ti, 17.01%C, 3.1%Si and 45.3%N.From figure 3, it can be seen that coating is made of two parts, One be 198nm AlCrTi alloy transition layers, another is exactly deposited AlCrTiSiCN coatings, and whole coating layer thickness is 3.47μm.Coating structure dense uniform, is presented some tiny column crystals, and interface is well combined between coating/transition zone/matrix.
Fig. 4 is the aluminium oxide ceramic ball of AlCrTiSiCN coatings and a diameter of 5.99mm to the grinding defect morphology after mill, its method It is 2N to load, is using rotate-stationary mode, sliding speed 10.47cm/s, sliding distance 62.83m, polishing scratch orbit radius 5mm.As shown in Figure 4, which has substantial amounts of ditch dug with a plow, and wear mechanism shows as abrasive wear, and polishing scratch plane compares It is smooth, do not change much, Wear track depth is shallower, and the average wear rate through calculating AlCrTiSiCN coatings is 1.25 × 10- 14m3.N-1.m-1Show excellent wear-resisting property.
Fig. 5 is the average friction coefficient of AlCrTiSiCN coatings, from figure 5 it can be seen that after 30s running-in periods, The friction coefficient of AlCrTiSiCN coatings maintains 0.65 or so, and in 320s, friction coefficient is climbed to higher stabilization Phase, friction coefficient is 0.75 or so at this time.Friction coefficient is relatively large, brilliant since AlCrTiSiCN coating surfaces are relatively rough Particle size is big, and big crystal grain plays inhibition in friction testing, so as to add the friction coefficient of coating.
In addition, AlCrTiSiCN coatings have big hardness, about 40.7Gpa, big hardness causes tight to the secondary abrasion of friction Weight, adds the contact area with coating, frictional force is bigger, that is, adds the friction coefficient of AlCrTiSiCN coatings.
Conclusion
Nano combined AlCrTiSiCN coatings stable chemical performance, does not react with common chemical attack medium.In coating Amorphous phase can effectively stop the germinating and extension of micro-crack, drastically increase coating toughness.
AlCrTiSiCN coatings have higher hardness and toughness, and wear-resisting property is good.
AlCrTiSiCN uniform coating thickness and compact structure, have good bond strength with matrix.
AlCrTiSiCN preparation technology of coating is reproducible.Compared with multilayer film, the former application range is wider, and practicality is more By force, the component surface of complexity is applied especially to, there is unique advantage.
Exemplary description has been done to the present invention above, it should explanation, in the situation for the core for not departing from the present invention Under, any simple deformation, modification or other skilled in the art can not spend the equivalent substitution of creative work equal Fall into protection scope of the present invention.

Claims (2)

1. a kind of AlCrTiSiCN coating structures, including matrix, Al-Cr-Ti alloy transitions layer and AlCrTiSiCN coatings.Al- Cr-Ti alloy transition layers are combined with matrix, and AlCrTiSiCN coatings are combined with Al-Cr-Ti alloy transition layers, described AlCrTiSiCN coatings are formd with amorphous phase Si3N4It is wrapped in AlN, TiN, CrN, Al8SiC7、Cr2N0.39C0.16Etc. nanocrystalline The nano composite structure coating of phase.
2. the preparation method of AlCrTiSiCN coating structures according to claim 1, it is characterised in that:
The base vacuum of vacuum chamber is first evacuated to 4.0 × 10-3Pa, is preheated to 500 DEG C, application -800V Dc biases, to vacuum chamber It is 150sccm to be inside passed through argon flow amount, and Glow Discharge Cleaning is carried out to matrix surface, and operating pressure is maintained at 2.4Pa, and electric discharge is clear Wash 10min.
Argon flow amount is turned down afterwards to 70sccm, operating pressure is reduced to 0.8Pa, while opens AlCr targets and AlTi target power supplies, Cr atoms in AlCr targets account for 30%, Al atoms and account for 70%;Ti atoms in AlTi targets account for 30%, Al atoms and account for 70%, AlCr Target and AlTi targets average output power and target current are 1.0kW and 75A, then with icon bombardment cleaning 5min;Then reduce inclined It is depressed into -50V, depositing Al-Cr-Ti alloy transition layer 10min, two target material surfaces are 290mm apart from substrate, depositing temperature 500 ℃;
It is subsequently passed reacting gas N2And C2H2, by the flow of argon gas, nitrogen and acetylene be adjusted to respectively 40sccm, 220sccm, 40sccm, is then turned on Si targets, and Si targets output power and target current are respectively 0.9kW, 65A, adjust operating pressure and maintain 1.2Pa, depositing temperature are maintained as 500 DEG C, start depositing Al-Cr-Ti-Si-C-N coatings.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109161848A (en) * 2018-09-18 2019-01-08 岭南师范学院 A kind of CrAlBCN coating, the nano combined CrAlBCN coating of low friction seawater corrosion resistance and preparation method thereof
CN112941470A (en) * 2021-02-04 2021-06-11 上海应用技术大学 TiAlSiCN micro-nano coating and preparation method thereof
CN112962059A (en) * 2021-02-04 2021-06-15 上海应用技术大学 CrAlTiSiCN nano composite coating and preparation method thereof
CN113025979A (en) * 2021-02-26 2021-06-25 沈阳三聚凯特催化剂有限公司 Nanocrystalline amorphous composite coating and preparation method thereof
CN114517286A (en) * 2021-12-27 2022-05-20 河南镀邦光电股份有限公司 Superhard conductive film sputtering coating method for detecting ECG
CN114632910A (en) * 2022-01-17 2022-06-17 温州瑞明工业股份有限公司 Preparation method of nano-composite multi-element oxycarbide coating on surface of die-casting aluminum die
CN115261803A (en) * 2022-07-11 2022-11-01 武汉汇九厨具科技有限公司 Amorphous nano composite material film and preparation method and application thereof
CN117467937A (en) * 2023-12-04 2024-01-30 苏州六九新材料科技有限公司 AlCrVTiSiCN coating, preparation method thereof and cutter
CN117568747A (en) * 2023-12-04 2024-02-20 苏州六九新材料科技有限公司 AlCrVTiSiCN/AlCrN multilayer composite coating, preparation method thereof and cutter

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109161848A (en) * 2018-09-18 2019-01-08 岭南师范学院 A kind of CrAlBCN coating, the nano combined CrAlBCN coating of low friction seawater corrosion resistance and preparation method thereof
CN112941470A (en) * 2021-02-04 2021-06-11 上海应用技术大学 TiAlSiCN micro-nano coating and preparation method thereof
CN112962059A (en) * 2021-02-04 2021-06-15 上海应用技术大学 CrAlTiSiCN nano composite coating and preparation method thereof
CN113025979A (en) * 2021-02-26 2021-06-25 沈阳三聚凯特催化剂有限公司 Nanocrystalline amorphous composite coating and preparation method thereof
CN113025979B (en) * 2021-02-26 2022-06-03 沈阳三聚凯特催化剂有限公司 Nanocrystalline amorphous composite coating and preparation method thereof
CN114517286A (en) * 2021-12-27 2022-05-20 河南镀邦光电股份有限公司 Superhard conductive film sputtering coating method for detecting ECG
CN114632910A (en) * 2022-01-17 2022-06-17 温州瑞明工业股份有限公司 Preparation method of nano-composite multi-element oxycarbide coating on surface of die-casting aluminum die
CN115261803A (en) * 2022-07-11 2022-11-01 武汉汇九厨具科技有限公司 Amorphous nano composite material film and preparation method and application thereof
CN117467937A (en) * 2023-12-04 2024-01-30 苏州六九新材料科技有限公司 AlCrVTiSiCN coating, preparation method thereof and cutter
CN117568747A (en) * 2023-12-04 2024-02-20 苏州六九新材料科技有限公司 AlCrVTiSiCN/AlCrN multilayer composite coating, preparation method thereof and cutter
CN117467937B (en) * 2023-12-04 2024-09-10 苏州六九新材料科技有限公司 ALCRVTISICN coating, preparation method thereof and cutter
CN117568747B (en) * 2023-12-04 2024-10-11 苏州六九新材料科技有限公司 ALCRVTISICN/AlCrN/CrN multilayer composite coating, preparation method thereof and cutter

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