CN106191772B - A kind of high rigidity CrAlN coatings and preparation method thereof containing AlCrN nanometers of insert layers of multiphase - Google Patents

A kind of high rigidity CrAlN coatings and preparation method thereof containing AlCrN nanometers of insert layers of multiphase Download PDF

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CN106191772B
CN106191772B CN201610646873.9A CN201610646873A CN106191772B CN 106191772 B CN106191772 B CN 106191772B CN 201610646873 A CN201610646873 A CN 201610646873A CN 106191772 B CN106191772 B CN 106191772B
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matrix
layer
thickness
craln
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CN106191772A (en
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李伟
刘平
杜浩明
张柯
马凤仓
刘新宽
陈小红
何代华
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University of Shanghai for Science and 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
    • C23C14/22—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
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C28/044—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 coatings specially adapted for cutting tools or wear applications
    • 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
    • C23C28/048—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 with layers graded in composition or physical properties

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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)
  • Inorganic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)

Abstract

A kind of high rigidity CrAlN coatings containing AlCrN nanometers of insert layers of multiphase, by Cr50Al50N layers and Al80Cr20N layers of alternating deposit are on matrix, each layer of Cr50Al50The thickness of N is 4.0 6.0nm, each layer of heterogeneouss Al80Cr20The thickness of N is 0.3~1.4nm, and the overall thickness of coating is 1.5 2.8 μm.The preparation method of above-mentioned coating is additionally provided, first by matrix surface polishing treatment, after ultrasonic cleaning and Ion Cleaning, then uses reactive sputtering alternating sputtering heterogeneouss Al on matrix80Cr20N layers and Cr50Al50N layers.Since the CrAlN coatings of the present invention still can keep high high rigidity, high-wearing feature and high temperature oxidation resistance under high-speed cutting, the protective coating of military service wear-resisting workpiece under high speed cutting tool and other hot conditions can be used as.

Description

A kind of high rigidity CrAlN coatings containing AlCrN nanometers of insert layers of multiphase and its preparation Method
Technical field
The invention belongs to materialogy fields, are related to a kind of hard protective coating, specifically a kind of to contain multiphase AlCrN The high rigidity CrAlN coatings and preparation method thereof of nanometer insert layer.
Background technology
With the progress of society and the development of science and technology, material surface performance requirement is higher and higher, high rigidity, wear-resisting, corrosion resistant Corrosion, various indexs such as high temperature resistance are to weigh the important indicator of current cutting performance.For this purpose, being developed coating knife Tool assigns cutter more that is, by coating one layer of metallic compound haveing excellent performance in tool surface with method chemically or physically Good comprehensive performance.
Cutter coat is developed to Ti, N etc. by initial TiC, TiN as basic element, is formed by the element for being added new Multi-element coating, laminated coating and nanotechnology coating.The TiA1N coatings obtained after Al elements are especially added, relative to biography The TiN coatings of system, performance almost obtain General Promotion.But still there is certain limitation in the such cutter of the extreme occasion of high temperature Property.
Under this background, researcher has found that Cr first has fusing point more higher than Ti, next face-centred cubic structure CrN structure cells can be dissolved more Al compared with TiN structure cells.That therefore develops is applied instead of the AlCrN coatings of Ti with AlTiN with Cr Layer is compared, and high temperature oxidation resisting temperature can significantly improve, friction coefficient smaller, chip removal ability are stronger, although hardness is in a slight decrease, Comprehensive performance is more excellent.Based on this, AlCrN toughness compared with TiA1N is more preferable, more suitable for interrupted cut, it has also become nanometer One of the hot subject of coating research.
Learnt by reading up the literature, AlCrN coatings have successfully been made by a variety of methods at present, obtain it is many it is beneficial at Fruit.By inquiry, the following patent in relation to preparing AlCrN coatings is retrieved：
Application No. is 201410158509.9 patents to relate to a kind of multilayer Al CrN cutting tool coatings and its preparation side Method belongs to machine cut manufacture field.The interfaces Cr implant layer is deposited on the surface of tool matrix, the thickness of the interfaces Cr implant layer Degree is 50~300nm；The thickness of CrN binder courses is 0.1~1 μm, and the thickness of CrN/AlCrN supporting layers is 0.5~3 μm；AlCrN The thickness of functional layer is 1~3 μm；The CrN/AlCrN supporting layers are that CrN and AlCrN modulates nanometer multilayer grading structure, modulation Period is 2~10nm.Aura cleaning is carried out to matrix surface；Open metal Cr targets, the interfaces deposition Cr implant layer, deposition CrN knots Close layer；Cr metals and AlCr alloys targets are opened, CrN/AlCrN supporting layers are deposited；Depositing Al CrN functional layers.With more than 60N's Binding force, the hardness of 40GPa, down to 0.3 friction coefficient, cutter life can be improved 5 times or more.
Application No. is 201210510010.0 patents to relate to a kind of CrAlN/ZrO2Nano coating and preparation method thereof. The coating is by multiple CrAlN layers and ZrO2Layer is constituted, each CrAlN layers and ZrO2Layer alternating deposit is on matrix, and overall thickness is about It is 2.0~4.0 μm.Preparation method by matrix surface polishing treatment, after ultrasonic cleaning and Ion Cleaning, then uses first Reactive sputtering is alternating sputtering CrAlN layers and ZrO on matrix2Layer.The CrAlN/ZrO of the present invention2Nano laminated coating can be simultaneously With high rigidity and high antioxygenic property, highest hardness is up to 47.2GPa, due to ZrO2The insertion of layer hinders Cr, Al original Diffusion of the son to external diffusion and O atom internally, therefore the antioxygenic property of coating is improved, even if adding in air Heat keeps the temperature 30min to 1000 DEG C, and hardness can still keep 36.8GPa.Therefore, which can be used as high speed cutting tool and other The protective coating of military service wear-resisting workpiece under hot conditions, preparation method is with simple for process, deposition velocity is fast, at low cost, knot Close the advantages that intensity is high.
Application No. is the patents of 200910193492.X to relate to a kind of TiN/ (TiN+CrN)/CrAlN nano-composite coatings And preparation method thereof.The nanocomposite laminated coating is in the tool or mould that material is hard alloy, high-speed steel, refractory steel Have on matrix, is by transition zone TIN films, (TiN+CrN) nano composite multiple layer and CrAlN nano composite multiple layer composed structures successively TiN/ (TiN+CrN)/Ti (CN) multiple layer metal nitride ceramics coating.Preparation method is including preheating, surface clean etches, Prepared by transition zone, (TiN+CrN) composite Nano multilayer layer is prepared and the preparation of CrAlN nano composite multiple layers.The invention is logical It crosses coating structure appropriate and designs the binding force for improving CrAlN families of coatings with matrix, maintain the high rigidity of CrAlN coatings And high-temperature behavior.
Application No. is 201410436427.6 patent relate to a kind of self-hardening TiAlN/CrAlN laminated coatings cutter and Preparation method.The laminated coating cutter includes tool matrix and the laminated coating that is deposited on tool matrix, in laminated coating Include an alternating deposit Ti1-xAlxN layers and Cr1-yAlyN layers of multicycle coating, wherein 0.35≤x≤0.67,0.50≤y ≤ 0.70, Ti1-xAlxN layers and Cr1-yAlyThe ratio between N layers thickness >=1.5.Preparation method includes pre-processing tool matrix, Then selective deposition transition zone, then alternating deposit Ti1-xAlxN layers and Cr1-yAlyN layers of multicycle coating, obtains laminated coating Cutter.The laminated coating cutter of the invention have excellent thermal stability and high-temperature oxidation resistance, and can age-hardening, system Preparation Method is simple for process, equipment is conventional, production cost is low.
Application No. is 201010597416.8 patent relate to a kind of high rigidity high elastic modulus CrAlN protective coatings and Preparation method is deposited on matrix, is double-layer structure, and bottom is Cr transition zones, thickness 400-600nm, and outer layer is CrAlN coatings, for fine and close ceramic coating, thickness is 2.2-2.9 μm；The invention also discloses the preparation side of the protective coating Matrix is made surface polishing treatment by method first, is splashed after ultrasonic cleaning and Ion Cleaning, then using direct current or radio frequency reaction Penetrate method priority sputter Cr transition zones and CrAlN coatings on matrix.The invention not only have the up to hardness of 30GPa or so and The elasticity modulus of 350GPa or more, but also there is high oxidation-resistance property and excellent corrosion resistance, preparation method Have many advantages, such as that simple for process, at low cost, bond strength is high.
Application No. is 200610045989.3 patents to relate to a kind of CrN/ of the resistance to high temperature corrosion in wide temperature range CrAlN protective coatings and preparation method, belong to surface engineering technology, prepare CrN/CrAlN coatings in high-temperature alloy surface, use The mode that Cr targets, Al target direct current reactions splash altogether obtains CrN/CrAlN coatings, and substrate temperature is -300 DEG C of room temperature, Ar and N2Using Mass flowmenter controls, and flow is respectively 6-20SCCM (sccm) and 6-20SCCM, operating air pressure are 0.1-0.8Pa.The Al content in coating is controlled by adjusting the power ratio of Cr targets and Al targets, is tied between coating and matrix to improve With joint efforts, apply the substrate negative voltage of 0--150V on matrix.The coating internal layer obtained is CrN layers, and outer layer is Al content in ladder Spend the Cr-Al-N layers of distribution.Coating primarily forms solid solution after being aoxidized in 800-900 DEG C of air have the Cr of Al2O3Film, 1000 DEG C or more oxidation when form rich Al oxidation films.Heat erosion experiment shows that CrN/CrAlN coatings have good hot corrosion resistance.
Application No. is 201010597430.8 patents to relate to a kind of CrAlN/AlON nanometers of high rigidity high elastic modulus Laminated coating material and preparation method thereof is constituted by multiple CrAlN layers and AlON layers, and each CrAlN layers and AlON layers alternately heavy Product forms nanometer scale multilayered structure on matrix, and overall thickness is 1.9~2.5 μm, and every CrAlN layer thickness is 5nm, each AlON layer thickness is 0.3-1.8nm；The invention also discloses the preparation methods of the nano laminated coating material, first by matrix Make surface polishing treatment, replaces sputter CrAlN on matrix after ultrasonic cleaning and Ion Cleaning, then using reactive sputtering Layer and AlON layers.
Application No. is 201010597419.1 patents to relate to a kind of high rigidity high elastic modulus CrAlN/SiO2Nanometer Laminated coating material and preparation method thereof, by multiple CrAlN layers and SiO2Layer is constituted, each CrAlN layers and SiO2Layer alternating deposit Nanometer scale multilayered structure is formed on matrix, overall thickness is 1.9-2.2 μm, and every CrAlN layer thickness is 5nm, each SiO2Layer thickness is 0.6-1.3nm；The invention also discloses the preparation methods of the nano laminated coating material, first by matrix Make surface polishing treatment, replaces sputter CrAlN on matrix after ultrasonic cleaning and Ion Cleaning, then using reactive sputtering Layer and SiO2Layer.
Application No. is 201410253262.9 patents to relate to a kind of CrAlN/ with high rigidity and low-friction coefficient MoS2Laminated coating and preparation method thereof, the CrAlN/MoS2Laminated coating passes through multi-target magnetic control sputtering mode that is, on matrix Alternating sputtering deposits to form CrAlN nanometer layers and MoS2Nanometer layer is CrAlN nanometer layers, top layer MoS close to matrix2Nanometer Layer.CrAlN/MoS22.0-4.5 μm of laminated coating overall thickness, every a CrAlN nanometers of layer thickness 5.0nm, every MoS2Nanometer thickness Spend 0.2~1.4nm.Matrix after cleaning is placed in multi-target magnetic control sputtering instrument, in argon, nitrogen mixed gas atmosphere by preparation method Middle alternating rests on CrAl alloys targets and MoS2Before target, by adjusting CrAl targets and MoS2The power and sedimentation time of target are to control The thickness of each coating is made, it is final to obtain CrAlN/MoS2Laminated coating.
However, above-mentioned existing coating there are still hardness, antioxygenic property, sedimentary condition and deposition efficiencies can not be simultaneous The problem of Gu, cannot meet the performance requirement of high-speed cutting and DRY CUTTING with hardness, high temperature oxidation resistance, production efficiency The shortcomings of.The hardness and antioxygenic property of coating, but excessively high Al can be further increased by improving the Al content in CrAlN coatings Content can cause the crystal structure of coating to change, to make the mechanical property of coating drastically decline.
Invention content
For above-mentioned technical problem in the prior art, the present invention provides one kind containing AlCrN nanometers of insert layers of multiphase High rigidity CrAlN coatings and preparation method thereof, described this high rigidity CrAlN coatings and preparation method thereof will solve existing Hard protective coating in technology is the technical issues of hardness, antioxygenic property, sedimentary condition and deposition efficiency can not be taken into account.
The present invention provides a kind of high rigidity CrAlN coatings containing AlCrN nanometers of insert layers of multiphase, by multiple heterogeneouss Al80Cr20N layers and Cr50Al50N layers of composition, the Al80Cr20N layers and Cr50Al50N layers of alternating deposit are on matrix, the base Body is metal, hard alloy or ceramics, each layer of Cr50Al50The thickness of N is 4.0~6.0 nm, each layer of heterogeneouss Al80Cr20N Thickness be 0.3~1.4nm, the overall thickness of the coating is 1.5-2.8 μm.
Further, Cr50Al50The width of the column crystal of N is between 10~30 nm.
The present invention also provides a kind of systems of above-mentioned high rigidity CrAlN coatings containing AlCrN nanometers of insert layers of multiphase Preparation Method includes the following steps：
1）, a cleaning matrix the step of, will polished treated matrix feeding supersonic wave cleaning machine, respectively in acetone In absolute ethyl alcohol, 5~10min is cleaned successively using 15~30kHz ultrasonic waves；Then Ion Cleaning is carried out, ion is being carried out During cleaning, matrix is put into vacuum chamber, is evacuated down to 6 × 10-4Pa then passes to Ar gas, maintains vacuum degree in 2- 4Pa, with intermediate frequency to matrix into the ion bombardment of 30min when behavior, power 80-100W；
2）, an alternating sputtering Al80Cr20N layers and Cr50Al50N layers of the step of, simultaneously by matrix merging multi-target magnetic control sputtering instrument Alternating rests on Al80Cr20Composition target and Cr50Al50Before composition target, in AlCr composition targets, the atomic ratio of Al and Cr elements is 80:20, in Cr50Al50In composition target, the atomic ratio of Cr and Al elements is 50:50, it is obtained by multiple Al by sputtering80Cr20N layers And Cr50Al50The N layers of nanometer scale laminated coating being alternately superimposed control each layer by adjusting target power output and sedimentation time Cr50Al50The thickness of N is 4.0~6.0 nm, each layer of heterogeneouss Al80Cr20The thickness of N is 0.3~1.4nm, the coating Overall thickness be 1.5-2.8 μm；It is final to obtain high rigidity CrAlN coatings.
Further, step（2）In, the process control parameter by multi-target magnetic control sputtering instrument sputtering process is：
A diameter of 75mm of CrAl composition targets and AlCr composition targets；Ar throughputs：10-50sccm, N2Throughput：5- 20sccm；Cr50Al50N layers of sputtering power direct current 120W, time 12-18s；Al80Cr20N layers of sputtering power radio frequency 80W, time 2- 9s；Target-substrate distance 3-7cm；Total gas pressure range 0.2-0.6Pa.
The present invention is according to the microdeformation mechanism of CrAlN coatings, when CrAlN crystallite dimensions are sufficiently small, especially less than When 10nm, dislocation motion no longer becomes the micromechanism of material deformation, and material deformation depends primarily on CrAlN nanocrystals edge The sliding of crystal boundary.Insert layer in the present invention makes Al due to higher Al content80Cr20There is face-centred cubic structure in N layers CrAlN phases, and there are the AlN phases of hexagonal structure, to make insert layer that heterogeneouss state be presented.The present invention is in Cr50Al50N is applied Layer is inserted into heterogeneouss nanometer layer, limits sliding of the CrAlN nanocrystals along crystal boundary first, therefore is expected to inhibit Cr50Al50N receives The microdeformation of rice coating, makes Cr50Al50N nano coatings are further strengthened.Secondly, the Al of heterogeneouss80Cr20N insert layers make Cr50Al50The column crystal of coherent strengthening attenuates in N coatings, to generate refined crystalline strengthening effect.Finally, by insert layer Method utilizes the Al of heterogeneouss80Cr20N insert layers improve Cr50Al50Whole Al content in N coatings, not reducing, coating is hard Under the premise of degree, the thermal stability of coating is further increased, keeps its friction coefficient smaller, chip removal ability stronger, to obtain more For excellent comprehensive performance.
The preparation method of the present invention is first by matrix surface polishing treatment, after ultrasonic cleaning and Ion Cleaning, then Using reactive sputtering on matrix alternating sputtering heterogeneouss Al80Cr20N layers and Cr50Al50N layers.The present invention's contains multiphase Al80Cr20The Cr of N nanometers of insert layers50Al50N coatings have high rigidity, and highest hardness is up to 39.2GPa, due to heterogeneouss Al80Cr20N nanometer layers are inserted into, and Cr is made50Al50The column crystal of N refines, and generates the effect of refined crystalline strengthening, therefore in nano-multilayer film Outside coherent boundary strengthening mechanism, Cr can be made50Al50N coatings are further strengthened.Simultaneously because CrAlN coatings have well Thermal stability makes it still can keep high high rigidity, high-wearing feature and high temperature oxidation resistance under high-speed cutting.The coating The protective coating of military service wear-resisting workpiece under high speed cutting tool and other hot conditions is can be used as, preparation method has technique letter The advantages that single, at low cost, bond strength is high.The preparation process of the present invention have production efficiency height, less energy consumption, it is at low cost, pair set Standby to require the advantages that relatively low, the present invention can be used as the protection of matrix in the cutter coat and other field of high speed, DRY CUTTING Coating.
The present invention improves Cr by being inserted into the AlCrN insert layers of the high Al content of heterogeneouss50Al50Whole Al in N coatings Content, and so that the crystal column of coherent strengthening in coating is attenuated by the heterogeneouss of insert layer, to generate refined crystalline strengthening effect. Cr50Al50N layers and heterogeneouss Al80Cr20N layers are in coherent strengthening, and film occurs being continuous through multi-layer nano layer, crystallinity good Good column crystal.Al80Cr20N layers and Cr50Al50N layers are in coherent strengthening, and film occurs being continuous through multi-layer nano layer, knot The brilliant good column crystal of degree.
The present invention is compared with prior art, and technological progress is significant.The present invention utilizes heterogeneouss Al80Cr20N nanometers Insert layer is to Cr50Al50N nano-composite coatings carry out refined crystalline strengthening, improve hardness, elasticity modulus and the high temperature resistance of coating comprehensively The effect of oxidation susceptibility makes it can be used as the protective coating of the cutter coat of high-speed dry type cutting and other fields.Applied to dry Formula, cutting tool for high speed cutting surface, to improve the service life of cutter.
Description of the drawings
Fig. 1 is the transmission electron microscope photo of the high rigidity CrAlN coatings containing AlCrN nanometers of insert layers of multiphase（Low power）.
Fig. 2 is the transmission electron microscope photo of the high rigidity CrAlN coatings containing AlCrN nanometers of insert layers of multiphase（High power）.
Specific implementation mode
Below by specific embodiments and the drawings, the present invention is described in further detail, but is not intended to limit the present invention.
Preparation, characterization used in the present invention and measuring instrument：
JGP-450 type magnetic control sputtering systems, Chinese Academy of Sciences Shenyang scientific instrument development center Co., Ltd
D8 Advance type X-ray diffractometers, German Bruker companies
NANO Indenter G200 type nano-hardness testers, Agilent Technologies of the U.S.
Tecnai G2 20 type high resolution transmission electron microscopies, FEI Co. of the U.S.
Quanta FEG450 type scanning electron microscope, FEI Co. of the U.S.
Embodiment 1
Using Cr50Al50（50 atom%:50 atom%）Composition target and Al80Cr20（80 atom%:20 atom%）It is compound Target, a diameter of 75mm；
Ar throughputs：38sccm, N2Throughput：5sccm；Target-substrate distance 3-7cm, total gas pressure range 0.6Pa.
Cr50Al50N layers of sputtering power direct current 120W, time 12s；Heterogeneouss Al80Cr20N layers of sputtering power radio frequency 80W, when Between 2s；
After testing, the Cr obtained50Al50N layer thickness is 4.0nm, heterogeneouss Al80Cr20N layer thickness is 0.3nm, overall thickness It is 1.8 μm, hardness 35.4GPa.
Embodiment 2
Using Cr50Al50（50 atom%:50 atom%）Composition target and Al80Cr20（80 atom%:20 atom%）It is compound Target, a diameter of 75mm；
Ar throughputs are 38sccm, N2Throughput is 5sccm；Target-substrate distance 3-7cm, total gas pressure 0.6Pa;
Cr50Al50N layers of sputtering power direct current 120W, time 15s；Heterogeneouss Al80Cr20N layers of sputtering power radio frequency 80W, when Between 3s.
After testing, the Cr obtained50Al50N layer thickness is 5.0nm, heterogeneouss Al80Cr20N layer thickness is 0.4nm, overall thickness It is 2.1 μm, hardness 36.1GPa.
Embodiment 3
Using Cr50Al50（50 atom%:50 atom%）Composition target and Al80Cr20（80 atom%:20 atom%）It is compound Target, a diameter of 75mm；
Ar throughputs are 38sccm, N2Throughput is 5sccm；Target-substrate distance 3-7cm, total gas pressure 0.6Pa;
Cr50Al50N layers of sputtering power direct current 120W, time 18s；Heterogeneouss Al80Cr20N layers of sputtering power radio frequency 80W, when Between 5s.
After testing, the Cr obtained50Al50N layer thickness is 6.0nm, heterogeneouss Al80Cr20N layer thickness is 0.7nm, overall thickness It it is 2.4 μm, hardness is 36.4 GPa.
Embodiment 4
Using Cr50Al50（50 atom%:50 atom%）Composition target and Al80Cr20（80 atom%:20 atom%）It is compound Target, a diameter of 75mm；
Ar throughputs are 38sccm, N2Throughput is 5sccm；Target-substrate distance 3-7cm, total gas pressure 0.6Pa;
Cr50Al50N layers of sputtering power direct current 120W, time 15s；Heterogeneouss Al80Cr20N layers of sputtering power radio frequency 80W, when Between 6s.
After testing, the Cr obtained50Al50N layer thickness is 5.0nm, heterogeneouss Al80Cr20N layer thickness is 0.9nm, overall thickness It it is 2.8 μm, hardness is 39.2 GPa, and the microstructure of cross section is as depicted in figs. 1 and 2.
Embodiment 5
Using Cr50Al50（50 atom%:50 atom%）Composition target and Al80Cr20（80 atom%:20 atom%）It is compound Target, a diameter of 75mm；
Ar throughputs are 38sccm, N2Qi leel pressure is 5sccm；Target-substrate distance 3-7cm, total gas pressure 0.6Pa;
Cr50Al50N layers of sputtering power direct current 120W, time 12s；Heterogeneouss Al80Cr20N layers of sputtering power radio frequency 80W, when Between 7s.
After testing, the Cr obtained50Al50N layer thickness is 4.0nm, heterogeneouss Al80Cr20N layer thickness is 1.1nm, overall thickness It it is 2.2 μm, hardness is 37. 6GPa.
Embodiment 6
Using Cr50Al50（50 atom%:50 atom%）Composition target and Al80Cr20（80 atom%:20 atom%）It is compound Target, a diameter of 75mm；
Ar throughputs are 38sccm, N2Qi leel pressure is 5sccm；Target-substrate distance 3-7cm, total gas pressure 0.6Pa;
Cr50Al50N layers of sputtering power direct current 120W, time 15s；Heterogeneouss Al80Cr20N layers of sputtering power radio frequency 80W, when Between 8s.
After testing, the Cr obtained50Al50N layer thickness is 5.0nm, heterogeneouss Al80Cr20N layer thickness is 1.2nm, overall thickness It is 2. 4 μm, hardness 36.3GPa.
Embodiment 7
Using Cr50Al50（50 atom%:50 atom%）Composition target and Al80Cr20（80 atom%:20 atom%）It is compound Target, a diameter of 75mm；
Ar throughputs are 38sccm, N2Qi leel pressure is 5sccm；Target-substrate distance 3-7cm, total gas pressure 0.6Pa;
Cr50Al50N layers of sputtering power direct current 120W, time 12s；Heterogeneouss Al80Cr20N layers of sputtering power radio frequency 80W, when Between 9s.
After testing, the Cr obtained50Al50N layer thickness is 4.0nm, heterogeneouss Al80Cr20N layer thickness is 1.4nm, overall thickness It is 2.2 μm, hardness 35.8GPa.

Claims (2)

1. a kind of high rigidity CrAlN coatings containing AlCrN nanometers of insert layers of multiphase, it is characterised in that：By multiple heterogeneouss Al80Cr20N layers and Cr50Al50N layers of composition, the Al80Cr20N layers and Cr50Al50N layers of alternating deposit are on matrix, the base Body is metal, hard alloy or ceramics, each layer of Cr50Al50The thickness of N is 4.0~6.0 nm, each layer of heterogeneouss Al80Cr20N Thickness be 0.3~1.4nm, the overall thickness of the coating is 1.5-2.8 μm, Cr50Al50The width of the column crystal of N 10~ Between 30 nm.
2. a kind of preparation side of the high rigidity CrAlN coatings containing AlCrN nanometers of insert layers of multiphase as described in claim 1 Method, it is characterised in that include the following steps：
1）, a cleaning matrix the step of, will polished treated matrix feeding supersonic wave cleaning machine, respectively in acetone and nothing In water-ethanol, 5~10min is cleaned successively using 15~30kHz ultrasonic waves；Then Ion Cleaning is carried out, Ion Cleaning is being carried out During, matrix is put into vacuum chamber, is evacuated down to 6 × 10-4Pa then passes to Ar gas, maintains vacuum degree in 2-4Pa, uses Intermediate frequency is to matrix into the ion bombardment of 30min when behavior, power 80-100W；
2）, an alternating sputtering Al80Cr20N layers and Cr50Al50Matrix is placed in multi-target magnetic control sputtering instrument and alternating by N layers of the step of Rest on Al80Cr20Composition target and Cr50Al50Before composition target, in Al80Cr20In composition target, the atomic ratio of Al and Cr elements is 80:20, in Cr50Al50In composition target, the atomic ratio of Cr and Al elements is 50:50, it is described to be sputtered by multi-target magnetic control sputtering instrument The process control parameter of process is：
A diameter of 75mm of CrAl composition targets and AlCr composition targets；Ar throughputs：10-50sccm, N2Throughput：5-20sccm； Cr50Al50N layers of sputtering power direct current 120W, time 12-18s；Al80Cr20N layers of sputtering power radio frequency 80W, time 2-9s；Target base Away from 3-7cm；Total gas pressure range 0.2-0.6Pa；
It is obtained by multiple Al by sputtering80Cr20N layers and Cr50Al50The N layers of nanometer scale laminated coating being alternately superimposed, pass through tune Whole target power output and sedimentation time control each layer of Cr50Al50The thickness of N is 4.0~6.0 nm, each layer of heterogeneouss Al80Cr20N Thickness be 0.3~1.4nm, the overall thickness of the coating is 1.5-2.8 μm；It is final to obtain high rigidity CrAlN coatings.
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