CN115074731A - Porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating and preparation method and application thereof - Google Patents
Porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating and preparation method and application thereof Download PDFInfo
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- CN115074731A CN115074731A CN202210504888.7A CN202210504888A CN115074731A CN 115074731 A CN115074731 A CN 115074731A CN 202210504888 A CN202210504888 A CN 202210504888A CN 115074731 A CN115074731 A CN 115074731A
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- 238000000576 coating method Methods 0.000 title claims abstract description 88
- 239000011248 coating agent Substances 0.000 title claims abstract description 86
- 230000003647 oxidation Effects 0.000 title claims abstract description 51
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000151 deposition Methods 0.000 claims abstract description 58
- 230000008021 deposition Effects 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005520 cutting process Methods 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 229910052786 argon Inorganic materials 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 59
- 239000007789 gas Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000005530 etching Methods 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000002346 layers by function Substances 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 230000003064 anti-oxidating effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000013077 target material Substances 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 238000005240 physical vapour deposition Methods 0.000 abstract description 6
- 238000007740 vapor deposition Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 238000010891 electric arc Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000003754 machining Methods 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000007733 ion plating Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 229910010038 TiAl Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 102100032047 Alsin Human genes 0.000 description 1
- 101710187109 Alsin Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910010037 TiAlN Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- 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
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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- 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
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- C23C14/0664—Carbonitrides
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- 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
- C23C14/3435—Applying energy to the substrate during sputtering
- C23C14/345—Applying energy to the substrate during sputtering using substrate bias
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- 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
- C23C14/3485—Sputtering using pulsed power to the target
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- 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
- C23C14/54—Controlling or regulating the coating process
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/36—Carbonitrides
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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Abstract
The invention discloses a porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating, a preparation method and application thereof, wherein the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating is an integral body consisting of a TiN bonding layer, a TiCN porous wear-resistant layer and a TiAlXN-based wear-resistant and oxidation-resistant layer, the three sub-layers are arranged from inside to outside, and the total thickness of the coating is 7-10 mu m. The composite coating prepared by the high-temperature vapor deposition, cathodic arc and HiPIMS technology has the advantages of chemical physical vapor deposition, fully utilizes the advantages of electric arc and magnetic control, and deposits a TiAlXN layer on the surface of a substrate by controlling the flow of nitrogen and argon, the pulse peak current, the deposition time and the like; the multi-layer composite coating organically combined by the different functional sublayers has high toughness, wear resistance, oxidation resistance and impact resistance, is very suitable for machining in an intermittent cutting mode and scenes of wear resistance, oxidation resistance and vibration resistance, has a simple preparation process, and is convenient for industrial production.
Description
Technical Field
The invention relates to the technical field of surface coatings, in particular to a porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating as well as a preparation method and application thereof.
Background
In recent years, a method of coating metal nitrides on products such as tools, dies, mechanical parts, etc. to improve the surface properties and the service life of the products has become a widely used surface modification technology. With the continuous development of coating technology, the new high oxidation resistance and the like meet the requirements of modern manufacturing industry on high hardness, high toughness, high wear resistance and high temperature performance of the coating.
The nitride coating is a coating material widely used for cutting tools such as milling cutters, turning tools and the like, such as TiAlN, TiAlCrN, Ti AlSiN and the like, and has high hardness and good wear resistance. However, nitride coatings also have disadvantages: the brittleness is large, the bonding strength with the substrate is not high enough, the thermal stability under the high temperature condition is not enough, and the shock resistance is poor. In order to exert the performance advantages of each coating, the multilayer oxide/(carbon) nitride composite coating prepared by the chemical vapor deposition method has very excellent comprehensive performance and is widely applied to cutting tools. However, due to the high process temperature of the chemical vapor deposition method, the base material of the cutting tool is easy to have the actions of element diffusion, chemical reaction and the like in the coating deposition process. The physical vapor deposition method has the characteristics of low deposition temperature, small influence on the properties of the substrate material, good surface quality, flexible process and the like, and is a more promising method for preparing the composite coating with the complex structure.
At present, the application of arc ion plating and magnetron sputtering in Physical Vapor Deposition (PVD) is the most widely. Among them, arc ion plating has higher ionization rate than magnetron sputtering, stronger wear resistance and better film-substrate bonding force, and is the mainstream choice of hard coating cutters. However, the surface of the film deposited by the traditional cathodic arc ion plating inevitably has large particles and rough surface, so that the coating cutter has large friction force during cutting, generates more heat and is easier to wear. By adopting the preparation method of high-temperature vapor deposition, cathodic arc and HiPIMS, plasma with higher density can be generated, the ionization rate is higher, and the deposition rate is faster. The prepared thick film has obviously reduced large particles on the surface, the wear-resistant layer is organized into a porous structure, has better impact resistance and tipping resistance effects, the friction coefficient is obviously reduced at high temperature, and the film-substrate binding force is higher.
The method for preparing the porous TiCN/TiAlXN wear-resistant coating by using the high-temperature vapor deposition, cathodic arc and HiPIMS methods is not reported, and the hard alloy cutter deposited with the porous TiCN/TiAlXN wear-resistant composite coating is one of the important development directions for improving the impact resistance, oxidation resistance and wear resistance of the hard film cutter at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating, a preparation method and application thereof, so that the overall impact resistance, wear resistance, low stress and high bonding strength of the coating are ensured, and the problems in the background art are solved.
In order to achieve the purpose, the invention provides the following technical scheme: a porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating is composed of 3 sublayers, wherein the sublayers sequentially comprise a TiN bonding layer, a TiCN porous wear-resistant layer and a TiAlXN-based wear-resistant and oxidation-resistant layer from inside to outside; the total thickness of the TiCN/TiAlXN wear-resistant and oxidation-resistant coating is 7-10 mu m, the thickness of the TiN bonding layer is 0.05-0.1 mu m, the thickness of the TiCN porous wear-resistant layer is 5-7 mu m, and the thickness of the TiAlXN-based wear-resistant and oxidation-resistant layer is 2-3 mu m.
Preferably, the atomic percentage content of each element in the TiAlXN-based wear-resistant and oxidation-resistant layer is Ti: 30-50 at.%, Al: 30-70 at.%, N: 10-50 at.%, X: 0-20 at.%; wherein X is C, Si, Zr, Mo, V, Cr and rare earth elements.
In addition, in order to achieve the purpose, the invention also provides the following technical scheme: a preparation method of a porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating comprises the following steps:
s1, polishing the surface of the substrate, and then putting the substrate into a solution in a hot water bath at 35 ℃ for ultrasonic cleaning; spraying fine gravel for 3-5 times, wherein each time of spraying is 2-5 seconds, and the sand spraying pressure is 0.8-1.3Kg/cm 2 Cleaning in hot water bath solution for 30min, and baking in oven;
s2, clamping the sample obtained in the step S1 into a furnace, vacuumizing, heating and starting to deposit to prepare a TiN bonding layer;
s3, starting to deposit and prepare a TiCN porous wear-resistant layer on the basis of the step S2;
s4, taking out the sample in the step S3, and repeating the step S1;
s5, charging the sample obtained in the step S4 into a furnace, performing medium-frequency pulse etching at 300-500 ℃, and pumping the vacuum chamber to 3.0-10.0 x10 -3 Pa, introducing Ar gas 350-550sccm, setting the workpiece bias voltage to-600-1000V, the frequency to 20-250 k Hz, the rotating speed to 1.5-5.5 r/min, performing pulse etching on the surface of the sample for 10-15 min, and then using H 2 Cleaning the furnace chamber;
s6, introducing Ar gas of 350-550sccm, adjusting the bias voltage to-100-200V, setting the ion source current to 10-15A and the rotating speed to 1.5-5.5 r/min, performing gas ion source direct current etching on the sample obtained in the step S5 for 20-25 min, and then using H 2 Cleaning the furnace chamber;
and S7, depositing the TiAlXN-based wear-resistant and oxidation-resistant functional layer on the sample obtained in the step S6 by adopting a cathodic arc combined HiPIMS high-energy pulse magnetron sputtering technology and controlling the flow of nitrogen and argon, the pulse peak current and the deposition time parameters.
Preferably, the solution in step S1 is acetone or alcohol; the fine granular gravel is corundum, zirconia or carborundum; the baking is specifically baking at 60 ℃ for 20 min.
Preferably, in the step S2 of preparing the TiN bonding layer by deposition, the deposition temperature is 850-900 ℃, the deposition pressure is 95-101KPa, and the used gas comprises TiCl 4 ，H 2 ，N 2 And Ar, wherein, TiCl 4 From H 2 Carried into a reaction furnace, TiCl 4 The temperature of the water bath is 45-48 ℃.
Preferably, in the step S3 of preparing the TiCN porous wear-resistant layer by deposition, the deposition temperature is 1000-1050 ℃, the deposition pressure is 6-50KPa, and the used gas comprises TiCl 4 ，H 2 ，CH 4 ，N 2 And Ar, mainly used for controlling gas concentration and chemical equilibrium, wherein, TiCl 4 Brought into the reaction furnace by H, TiCl 4 The temperature of the water bath is 45-48 ℃.
Preferably, the CH 4 The gas flow percentage is 3.5 percent to 4 percent, TiCl 4 The gas flow percentage is 1.5% -3%.
Preferably, in step S7, a cathodic arc is combined with a HiPIMS high-energy pulse magnetron sputtering technique, and the flow rate of nitrogen and argon, the pulse peak current, and the deposition time are controlled, specifically: adjusting the bias voltage to-100 to-250V, and introducing N of 400 to 750sccm 2 Igniting at least 2 Ti with Ar gas of 400-750 sccm a Al b X c Rectangular magnetron target, at least 4 Ti a Al b X c Cylindrical arc target, regulation N 2 The pressure is 0.5-3.5 Pa, the Ar pressure is adjusted to 0.5-3.5 Pa, the deposition temperature is 450-550 ℃, the deposition pressure is 9800-10500Mpa, the rotating speed is 1.5-5.5 r/min, the waveform of a pulse arc power supply is rectangular wave, the average current is 70-120A, and the bias voltage is as follows: -30 to-500V, frequency: 20-250 KHz, duty cycle: 5% -75%, the output current of the arc source electromagnetic coil: 0.3-5.2A, depositing the TiAlXN layer for 100-300 min.
Preferably, the Ti is a Al b X c The atomic percentage of Ti in the target material is 10-50 at.%, and Al: 30 to 67 at.%,x is C, Si, Zr, Mo, V or Cr; a + b + c is 100 at.%.
In addition, in order to achieve the purpose, the invention also provides the following technical scheme: an application of a porous composite TiCN/TiAlXN wear-resistant anti-oxidation coating in the field of surface protection of mechanical parts and cutting dies.
The invention has the beneficial effects that:
1) the porous wear-resistant composite coating provided by the invention is composed of three sublayers with different functions and components, and firstly, compared with the traditional Cr and Ti pure metal bonding layer, the nano TiN bonding layer has higher obdurability, can play a good bonding role between a cutter substrate material and a surface coating material, and enables the coating to be firmly combined with the substrate; secondly, when the coating is prepared at 850-900 ℃, the bonding strength of the coating can be ensured, and the diffusion of barrier elements is avoided to form a brittle layer; providing coherent growth conditions for nucleation growth of the porous wear-resistant layer again, and avoiding overlarge residual stress caused by lattice distortion; finally, after the porous wear-resistant layer is prepared, the stress of the coating is reduced by adopting sand blasting, a support foundation is provided for the subsequent preparation of the wear-resistant and oxidation-resistant layer, and the integral impact resistance, wear resistance, low stress and high bonding strength of the coating are ensured.
2) The composite coating prepared by the high-temperature vapor deposition, cathodic arc and HiPIMS technology has the advantages of chemical physical vapor deposition (coherent growth and formation of porous equiaxed crystals are formed by the high-temperature vapor deposition, the impact and energy absorption resisting effect of the coating is ensured, fibrous crystals are formed by the physical vapor deposition, the hardness, wear resistance and oxidation resistance of the coating are ensured), the advantages of electric arc and magnetic control are fully utilized, and the TiAlXN layer is deposited on the surface of a substrate by controlling the flow of nitrogen and argon, the pulse peak current, the deposition time and the like. Compared with the traditional arc ion plating, the pulse arc ion plating can generate plasma with higher density, has faster deposition rate, lower residual stress and higher coating hardness and is more wear-resistant.
Drawings
FIG. 1 is a schematic view of a porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating;
FIG. 2 is a friction curve of the porous wear-resistant and oxidation-resistant coating prepared in example 1;
FIG. 3 is a friction curve of the porous wear-resistant and oxidation-resistant coating prepared in example 2;
fig. 4 is a friction curve of the porous wear-resistant oxidation-resistant coating prepared in example 3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the present invention provides a technical solution: a porous composite TiCN/TiAlXN wear-resistant and anti-oxidation coating is composed of 3 sub-layers, as shown in figure 1, a TiN bonding layer, a TiCN porous wear-resistant layer and a TiAlXN-based wear-resistant and anti-oxidation layer are sequentially arranged on the sub-layers from inside to outside; the total thickness of the TiCN/TiAlXN wear-resistant and oxidation-resistant coating is 7-10 mu m, the thickness of the TiN bonding layer is 0.05-0.1 mu m, the thickness of the TiCN porous wear-resistant layer is 5-7 mu m, and the thickness of the TiAlXN-based wear-resistant and oxidation-resistant layer is 2-3 mu m.
Further, the atomic percentage content of each element in the TiAlXN-based wear-resistant oxidation-resistant layer is Ti: 30-50 at.%, Al: 30-70 at.%, N: 10-50 at.%, X: 0-20 at.%; wherein X is C, Si, Zr, Mo, V, Cr and rare earth elements.
A preparation method of a porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating comprises the following specific steps:
s1, depositing a bonding layer: polishing the surface of the substrate to mirror surface (Ra is 0.2 μm), cleaning in hot water bath at 35 deg.C for 30min under ultrasonic wave, spraying fine corundum for three times (2-5 s each time) at 0.8-1.3Kg/cm 2 Cleaning in hot water bath acetone solution for 30min, baking in oven at 60 deg.C for 20min, clamping, charging into furnace, vacuumizing, and heatingStarting to prepare the bonding layer, the deposition temperature is 850-900 ℃, the deposition pressure is 95-101KPa, and the gas including TiCl is used 4 ，H 2 ，N 2 And Ar, wherein TiCl 4 From H 2 Carried into a reaction furnace, TiCl 4 The temperature of the water bath is 45-48 ℃, and the thickness of the coating is 0.05-0.1 mu m.
S2, a TiCN porous wear-resistant layer: starting to prepare a porous wear-resistant layer on the basis of the step S1, wherein the deposition temperature is 1000-1050 ℃, the deposition pressure is 6-50KPa, and the gas comprises TiCl 4 ，H 2 ，CH 4 ，N 2 And Ar, wherein TiCl 4 From H 2 Carried into a reaction furnace, TiCl 4 The temperature of the water bath of (1) is 45-48 ℃, wherein the thickness of the coating is 5-7 μm. Where the temperature and gas ratio are critical for the formation of a porous, wear-resistant layer, CH 4 The gas flow percentage is 3.5 to 4 percent, and TiCl 4 The percentage of gas flow is 1.5% -3%.
S3 TiAlXN-based functional coating: cleaning the sample prepared by S2 in an acetone solution with a hot water bath at 35 ℃ for 30min in ultrasonic waves, baking the sample in an oven at 50 ℃ for 20min, clamping the sample in a cathodic arc and HiPIMS vacuum system to prepare a TiAlXN-based coating, and depositing a TiAlXN-based functional layer: adjusting the bias voltage to-100 to-250V, and introducing N of 400 to 750sccm 2 Igniting at least 2 Ti with Ar gas of 400-750 sccm a Al b X c Rectangular magnetron target, at least 4 Ti a Al b X c Cylindrical arc target (target material Ti) a Al b X c The atomic percentage of Ti is 10-50 at.%, Al: 30-67 at.%, X can be C, Si, Zr, Mo, V, Cr and rare earth metal element, a + b + C is 100 at.%), regulating N 2 The pressure is 0.5-3.5 Pa, the Ar pressure is adjusted to 0.5-3.5 Pa, the deposition temperature is 450-550 ℃, the deposition pressure is 9800-10500MPa, the rotating speed is 1.5-5.5 r/min, the waveform of the pulse arc power supply is rectangular wave, the average current is 70-120A, and the bias voltage is as follows: -30 to-500V, frequency: 20-250 KHz, duty cycle: 5% -75%, the output current of the arc source electromagnetic coil: 0.3-5.2A, depositing a TiAlXN functional layer for 100-300 min to prepare a high-performance TiAlXN nano composite coating, wherein the thickness of the coating is 2-3 mu m, and the atomic percent of each element in the TiAlXN-based coating isThe content of Ti: 30-50 at.%, Al: 30-70 at.%, N: 10-50 at.%, X: 0 to 20 at.%.
An application of a porous composite TiCN/TiAlXN wear-resistant anti-oxidation coating in the field of surface protection of mechanical parts and cutting dies.
Example 1
The porous wear-resistant oxidation-resistant coating is deposited on a TiCN-WC-MoC-Ni-Co metal ceramic matrix
S1, polishing the metal ceramic cutter substrate to remove an oxide layer on the surface, and putting the metal ceramic cutter substrate into a solution in a hot water bath at 35 ℃ for ultrasonic cleaning for 30 min; spraying with fine grit for 5 times (5 s each time) under a pressure of 1.3Kg/cm 2 Cleaning in hot water bath solution for 30min, and baking in oven at 60 deg.C for 20 min;
s2, clamping the sample obtained in the step S1 into a furnace, vacuumizing and heating to start preparing the bonding layer, wherein the deposition temperature is 900 ℃, the deposition pressure is 101KPa, and the used gas comprises TiCl 4 ，H 2 ，N 2 And Ar, wherein TiCl 4 From H 2 Carried into a reaction furnace, TiCl 4 The temperature of the water bath of (2) was 48 ℃ and the thickness of the coating was 0.1. mu.m;
s3, preparing a porous wear-resistant layer on the basis of the step S2, wherein the deposition temperature is 1050 ℃, the deposition pressure is 50KPa, and the gas used comprises TiCl 4 ，H 2 ，CH 4 ，N 2 And Ar, wherein, TiCl 4 From H 2 Carried into a reaction furnace, TiCl 4 The temperature of the water bath was 48 ℃ and the thickness of the coating was 7 μm, wherein the temperature and gas ratio are critical for the formation of a porous wear layer, CH 4 Gas flow percentage of 4%, TiCl 4 The gas flow percentage was 3%.
S4, taking out the sample in the step S3, and repeating the step S1.
S5, charging the sample in the step S4 into a furnace, performing medium-frequency pulse etching at 500 ℃, and pumping the vacuum chamber to 10.0x10 -3 Pa, introducing Ar gas of 550sccm, setting the bias voltage of a workpiece to 1000V, the frequency of 250k Hz and the rotating speed of 5.5 r/min, performing pulse etching on the surface of the sample for 15min, and then using H 2 Cleaning the furnace chamber;
s6, DC direct current etching: introducing Ar gas of 550sccm, adjusting bias voltage to-200V, setting ion source current to 15A and rotation speed to 5.5 r/min, performing gas ion source direct current etching on the sample obtained in the step S5 for 25min, and then using H 2 The oven cavity is cleaned.
S7, depositing a TiAlMoN functional layer: the bias voltage is adjusted to-250V, and 750sccm of N is introduced 2 Gas 750sccm Ar gas, igniting at least 2 Ti a Al b Mo c Rectangular magnetron target, at least 4 Ti a Al b Mo c A cylindrical arc target. Such as: 3 of Ti a Al b Mo c Rectangular magnetic control target, 6 Ti a Al b Mo c A cylindrical arc target. (target Ti) a Al b Mo c The atomic percentage of Ti is 10-50 at.%, Al: 30-67 at.%, and a + b + c is 100 at.%), adjusting N 2 Regulating Ar pressure to 3.5Pa, regulating the temperature to 550 ℃, regulating the rotating speed to 5.5 r/min, and regulating the waveform of a pulse arc power supply to be rectangular wave, the average current to be 120A and the bias voltage to be: -500V, frequency: 250KHz, duty cycle: 70%, arc source electromagnetic coil output current: and 5.2A, depositing a TiAl MoN functional layer for 100min to prepare a high-performance TiAl MoN nano composite coating with the thickness of 3 mu m, wherein the atomic percent of each element in the TiAl MoN-based coating is Ti: 30-50 at.%, Al: 30-70 at.%, N: 10-50 at.%, Mo: 0 to 20 at.%.
The porous TiCN/TiAlMoN wear-resistant and oxidation-resistant coating prepared by the embodiment has the hardness of 45GPa, the residual stress of-0.3 GPa, the surface roughness of 90nm, the average friction coefficient of 0.36 and the friction curve as shown in FIG. 2.
Example 2:
depositing the porous wear-resistant oxidation-resistant coating on a WC-Co hard alloy substrate
S1, polishing the hard alloy matrix to remove an oxide layer on the surface, and putting the hard alloy matrix into a solution in a hot water bath at 35 ℃ for ultrasonic cleaning for 30 min; spraying with fine grit for 3 times (2 s each time) under 0.8Kg/cm 2 Cleaning in hot water bath solution for 30min, and baking in oven at 60 deg.C for 20 min;
s2, obtaining the step S1The sample is clamped into a furnace, the bonding layer is prepared by vacuumizing and heating, the deposition temperature is 850 ℃, the deposition pressure is 95KPa, and the used gas comprises TiCl 4 ，H 2 ，N 2 And Ar, wherein TiCl 4 From H 2 Carried into a reaction furnace, TiCl 4 The temperature of the water bath of (1) was 45 ℃ and the thickness of the coating was 0.05. mu.m;
s3, preparing the porous wear-resistant layer on the basis of the step S2, wherein the deposition temperature is 1000 ℃, the deposition pressure is 6KPa, and the gas used comprises TiCl 4 ，H 2 ，CH 4 ，N 2 And Ar, wherein TiCl 4 From H 2 Carried into a reaction furnace, TiCl 4 The temperature of the water bath of (1) was 45 ℃ and the thickness of the coating was 5 μm, wherein the temperature and gas ratio are critical for the formation of a porous wear layer, CH 4 Gas flow percentage of 3.5%, TiCl 4 The gas flow percentage was 1.5%.
S4, taking out the sample in S3, and repeating S1.
S5, charging the S4 sample into a furnace, performing medium-frequency pulse etching at 300 ℃, and pumping the vacuum chamber to 3.0x10 -3 Pa, introducing Ar gas of 350sccm, setting the bias voltage of the workpiece to 600V, the frequency to 20k Hz, the rotating speed to 1.5 r/min, performing pulse etching on the surface of the sample for 10min, and then using H 2 Cleaning the furnace chamber;
s6, DC direct current etching: introducing Ar gas of 350sccm, adjusting bias voltage to-100, setting ion source current to 10A and rotation speed to 1.5 r/min, performing gas ion source direct current etching on S5 sample for 20min, and then using H 2 The oven cavity is cleaned.
S7, depositing a TiAlVN functional layer: the bias voltage is adjusted to-100V, and N of 400sccm is introduced 2 Gas, 400sccm Ar gas, igniting at least 2 Ti a Al b V c Rectangular magnetron target, at least 4 Ti a Al b V c Cylindrical arc target (target material Ti) a Al b V c The atomic percentage of Ti is 23 at.%, Al: 67 at.%, a + b + c 100 at.%), adjusting N 2 The air pressure is adjusted to 0.5Pa, the Ar air pressure is adjusted to 3Pa, the temperature is 450 ℃, the rotating speed is 1.5 r/min, the waveform of the pulse arc power supply is rectangular wave, the average current is 70A, and the bias voltage is as follows: -30V, frequency: 20KHz, duty cycle: 25Percent, the current output by the arc source electromagnetic coil: 0.3A, depositing a TiAlVN functional layer for 300min to prepare a high-performance TiAlVN nano composite coating, wherein the thickness of the coating is 2-3 mu m, and the atomic percentages of elements in the TiAlVN-based coating are Ti: 30-50 at.%, Al: 30-70 at.%, N: 10-50 at.%, V: 0 to 20 at.%.
The hardness of the porous TiCN/TiAlVN wear-resistant oxidation-resistant coating prepared by the embodiment is 46GPa, the residual stress is-0.32 GPa, the surface roughness is 85nm, the average friction coefficient is 0.342, and the friction curve is shown in figure 3.
Example 3:
the porous wear-resistant oxidation-resistant coating is deposited on a WC-TiC-Co hard alloy matrix
S1, polishing the hard alloy cutter substrate to remove an oxide layer on the surface, and putting the hard alloy cutter substrate into a solution in a hot water bath at 35 ℃ for ultrasonic cleaning for 30 min; spraying with fine grit for 3 times (each for 3 s) under a pressure of 1.2Kg/cm 2 Cleaning in hot water bath solution for 30min, and baking in oven at 60 deg.C for 20 min;
s2, clamping the sample obtained in the step S1 into a furnace, vacuumizing and heating to start preparing the bonding layer, wherein the deposition temperature is 850 ℃, the deposition pressure is 95KPa, and the used gas comprises TiCl 4 ，H 2 ，N 2 And Ar, wherein TiCl 4 From H 2 Carried into a reaction furnace, TiCl 4 The temperature of the water bath of (1) was 45 ℃ and the thickness of the coating was 0.06. mu.m;
s3, preparing a porous wear-resistant layer on the basis of the step S2, wherein the deposition temperature is 1000 ℃, the deposition pressure is 20KPa, and the gas used comprises TiCl 4 ，H 2 ，CH 4 ，N 2 And Ar, wherein TiCl 4 From H 2 Carried into a reaction furnace, TiCl 4 The temperature of the water bath of (1) was 45 ℃ and the thickness of the coating was 5.3 μm, wherein the temperature and gas ratio are critical for the formation of a porous wear layer, CH 4 Gas flow percentage of 3.5%, TiCl 4 The gas flow percentage was 2%.
S4, taking out the sample in S3, and repeating S1.
S5, charging the S4 sample into a furnace, and carrying out intermediate frequency treatment at 400 DEG CPulse etching, the vacuum chamber is pumped to 5.0x10 -3 Pa, introducing Ar gas of 450sccm, setting workpiece bias voltage of-800V, frequency of 50k Hz, rotation speed of 5 r/min, performing pulse etching on the surface of the sample for 12min, and then using H 2 Cleaning the furnace chamber;
s6, DC direct current etching: introducing Ar gas of 450sccm, adjusting bias voltage to-120V, setting ion source current to 12A and rotation speed to 5 r/min, performing gas ion source direct current etching on the S5 sample for 22min, and then using H 2 The oven cavity is cleaned.
S7, deposition of a TiAlYN functional layer: the bias voltage is adjusted to-200V, and N of 450sccm is introduced 2 Gas 450sccm of Ar gas, igniting at least 2 Ti a Al b Y c Rectangular magnetron target, at least 4 Ti a Al b Y c Cylindrical arc target (target material Ti) a Al b Y c The atomic percentage of Ti is 25 at.%, Al: 67 at.%, a + b + c 100 at.%), adjusting N 2 The air pressure is adjusted to 1Pa, the Ar air pressure is adjusted to 3Pa, the temperature is 480 ℃, the rotating speed is 5 r/min, the waveform of the pulse arc power supply is rectangular wave, the average current is 90A, and the bias voltage is as follows: 100V, frequency: 100KHz, duty cycle: 50%, arc source electromagnetic coil output current: 1.2A, depositing a TiAlYN functional layer for 150min to prepare a high-performance TiAlYN nano composite coating, wherein the thickness of the coating is 2 mu m, and the atomic percent of each element in the TiAlYN-based coating is Ti: 30-50 at.%, Al: 30-70 at.%, N: 10-50 at.%, Y: 0 to 20 at.%.
The hardness of the porous TiCN/TiAlYN wear-resistant oxidation-resistant coating prepared in the embodiment is 50GPa, the residual stress is-0.22 GPa, the surface roughness is 80nm, the average friction coefficient is 0.325, and the friction curve is shown in figure 4.
The multilayer composite coating organically combined by different functional sublayers has the advantages of high toughness, wear resistance, oxidation resistance and impact resistance, is very suitable for machining in an intermittent cutting mode and scenes of wear resistance, oxidation resistance and vibration resistance, and is simple in preparation process and convenient for industrial production.
The invention adopts the preparation method of high-temperature vapor deposition, cathodic arc and HiPIMS, can generate plasma with higher density, and has higher ionization rate and higher deposition rate. The prepared thick film has obviously reduced large particles on the surface, the wear-resistant layer is organized into a porous structure, has better impact resistance and tipping resistance effects, the friction coefficient is obviously reduced at high temperature, and the film-substrate binding force is higher.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (10)
1. The porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating is characterized by comprising 3 sublayers, wherein the sublayers sequentially comprise a TiN bonding layer, a TiCN porous wear-resistant layer and a TiAlXN-based wear-resistant and oxidation-resistant layer from inside to outside; the total thickness of the TiCN/TiAlXN wear-resistant and oxidation-resistant coating is 7-10 mu m, the thickness of the TiN bonding layer is 0.05-0.1 mu m, the thickness of the TiCN porous wear-resistant layer is 5-7 mu m, and the thickness of the TiAlXN-based wear-resistant and oxidation-resistant layer is 2-3 mu m.
2. The porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating of claim 1, wherein: the TiAlXN-based wear-resistant anti-oxidation layer comprises the following elements in atomic percent: 30-50 at.%, Al: 30-70 at.%, N: 10-50 at.%, X: 0-20 at.%; wherein X is C, Si, Zr, Mo, V or Cr.
3. A preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to claims 1-2 is characterized in that: the method comprises the following steps:
s1, polishing the surface of the substrate, and then putting the substrate into a solution in a hot water bath at 35 ℃ for ultrasonic cleaning; spraying fine gravel for 3-5 times, wherein each time of spraying is 2-5 seconds, and the sand spraying pressure is 0.8-1.3Kg/cm 2 Cleaning in hot water bath solution for 30min, and baking in oven;
s2, clamping the sample obtained in the step S1 into a furnace, vacuumizing, heating and starting to deposit to prepare a TiN bonding layer;
s3, starting to deposit and prepare a TiCN porous wear-resistant layer on the basis of the step S2;
s4, taking out the sample in the step S3, and repeating the step S1;
s5, charging the sample obtained in the step S4 into a furnace, performing medium-frequency pulse etching at 300-500 ℃, and pumping the vacuum chamber to 3.0-10.0 x10 -3 Pa, introducing Ar gas 350-550sccm, setting the workpiece bias voltage to-600-1000V, the frequency to 20-250 k Hz, the rotating speed to 1.5-5.5 r/min, performing pulse etching on the surface of the sample for 10-15 min, and then using H 2 Cleaning the furnace chamber;
s6, introducing Ar gas of 350-550sccm, adjusting the bias voltage to-100-200V, setting the ion source current to 10-15A and the rotation speed to 1.5-5.5 rpm, performing gas ion source direct current etching on the sample obtained in the step S5 for 20-25 min, and then using H 2 Cleaning the furnace chamber;
and S7, depositing the TiAlXN-based wear-resistant and oxidation-resistant functional layer on the sample obtained in the step S6 by adopting a cathodic arc combined HiPIMS high-energy pulse magnetron sputtering technology and controlling the flow of nitrogen and argon, the pulse peak current and the deposition time parameters.
4. The preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to claim 3, characterized in that: the solution in the step S1 is acetone or alcohol; the fine granular gravel is corundum, zirconia or carborundum; the baking is specifically baking at 60 ℃ for 20 min.
5. The preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to claim 3, characterized by comprising the following steps: in the step S2 of preparing the TiN bonding layer by deposition, the deposition temperature is 850-900 ℃, the deposition pressure is 95-101KPa, and the used gas comprises TiCl 4 ，H 2 ，N 2 And Ar, wherein, TiCl 4 From H 2 Carried into a reaction furnace, TiCl 4 The temperature of the water bath is 45-48 ℃.
6. According to the claimsThe preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating is characterized by comprising the following steps: in the step S3 of preparing the TiCN porous wear-resistant layer by deposition, the deposition temperature is 1000-1050 ℃, the deposition pressure is 6-50KPa, and the used gas comprises TiCl 4 ，H 2 ，CH 4 ，N 2 And Ar, wherein, TiCl 4 From H 2 Carried into a reaction furnace, TiCl 4 The temperature of the water bath is 45-48 ℃.
7. The preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to claim 6, characterized in that: the CH 4 The gas flow percentage is 3.5 percent to 4 percent, TiCl 4 The gas flow percentage is 1.5% -3%.
8. The preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to claim 3, characterized in that: in the step S7, a cathodic arc and HiPIMS high-energy pulse magnetron sputtering technology is adopted, and the flow rate of nitrogen and argon, the pulse peak current and the deposition time are controlled, specifically: adjusting the bias voltage to-100 to-250V, and introducing N of 400 to 750sccm 2 Igniting at least 2 Ti with Ar gas of 400-750 sccm a Al b X c Rectangular magnetron target, at least 4 Ti a Al b X c Cylindrical arc target, regulation N 2 The pressure is 0.5-3.5 Pa, the Ar pressure is adjusted to 0.5-3.5 Pa, the deposition temperature is 450-550 ℃, the deposition pressure is 9800-10500Mpa, the rotating speed is 1.5-5.5 r/min, the waveform of a pulse arc power supply is rectangular wave, the average current is 70-120A, and the bias voltage is as follows: -30 to-500V, frequency: 20-250 KHz, duty cycle: 5% -75%, the output current of the arc source electromagnetic coil: 0.3-5.2A, depositing the TiAlXN layer for 100-300 min.
9. The preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to claim 8, characterized in that: the Ti a Al b X c The atomic percentage of Ti in the target material is 10-50 at.%, and Al: 30-67 at.%, X is C, Si, Zr, Mo, V or Cr; a + b + c is 100at.％。
10. The application of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to any one of claims 1-2 or the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating prepared by the preparation method according to any one of claims 3-9 in the field of surface protection of mechanical parts and cutting tools and dies.
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| CN107075692A (en) * | 2014-11-05 | 2017-08-18 | 瓦尔特公开股份有限公司 | Include the cutting element of multilayer PVD coatings |
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| CN105316629A (en) * | 2015-11-19 | 2016-02-10 | 上海应用技术学院 | Super-hard nano-micron multilayer composite coating and preparation method thereof |
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