CN114196940B - Composite coating cutter and preparation method and application thereof - Google Patents
Composite coating cutter and preparation method and application thereof Download PDFInfo
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- CN114196940B CN114196940B CN202111475991.5A CN202111475991A CN114196940B CN 114196940 B CN114196940 B CN 114196940B CN 202111475991 A CN202111475991 A CN 202111475991A CN 114196940 B CN114196940 B CN 114196940B
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
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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
- 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
- C23C16/029—Graded interfaces
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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
- 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
- C23C16/06—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 metallic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C16/32—Carbides
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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
- 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
Abstract
The invention discloses a composite coating cutter and a preparation method and application thereof, wherein the composite coating cutter comprises a substrate and a composite coating sequentially arranged on the surface of the substrate; the composite coating is prepared by adopting a chemical vapor deposition technology and comprises a first sub-coating and a second sub-coating, wherein a Ti-Al-B-N gradient layer with the boron content changing from low to high is arranged between the first sub-coating and the second sub-coating; the first sub-coating is Ti 1‑x Al x An N layer, the second sub-coating is Ti a Al b B c An N layer; the highest boron content in the gradient layer is not higher than the boron content of the second sub-coating. The invention aims to provide a high-temperature oxidation resistant composite coating cutter, a preparation method thereof and application thereof in high-speed dry cutting.
Description
Technical Field
The invention belongs to the field of machining, and particularly relates to a composite coating cutter, and a preparation method and application thereof.
Background
Materials such as titanium alloy, high-temperature alloy, heat-resistant stainless steel and the like are widely applied to high-end equipment parts in the fields of aerospace, energy and the like, modern cutting processing requires high efficiency and environmental protection, little or no cooling liquid is used, and the high-speed dry cutting demands are increasing. The local temperature of the cutter can reach more than 1000 ℃ during high-speed dry cutting, so that the cutter is required to have good high-temperature oxidation resistance. The titanium alloy, the nickel-based superalloy, the heat-resistant stainless steel and other materials have high strength, the surface of the cutter is easy to generate built-up tumor during cutting processing, and the cutter is seriously bonded and worn. The coating on the surface of the cutting tool can effectively prolong the service life of the tool, and in order to solve the processing problems, the coating of the tool is required to be smooth in surface, low in friction coefficient, high in coating bonding strength and good in wear resistance.
The high-temperature oxidation resistance of the cutter can be obviously improved by adding the aluminum element into the coating, the higher the aluminum content is, the better the oxidation resistance of the coating is, and the friction coefficient of the coating can be reduced by adding the boron and other elements. To ensure a high hardness and wear resistance of the TiAlN coating, it is generally desirable to have a high fcc-AlN content in the TiAlN coating, avoiding the formation of hcp-AlN as much as possible. The TiAlN coating prepared by a Physical Vapor Deposition (PVD) method in the prior art has good high-temperature oxidation resistance and is widely applied to cutting tools, but when the Al content of the TiAlN coating prepared by the PVD method exceeds 67%, hcp-AlN phases with hexagonal structures can be generated, so that the hardness and wear resistance of the coating are reduced.
Furthermore, boron is added to form a TiAlBN coating on the basis of the PVD TiAlN coating, so that the performance of the PVD TiAlN coating (TiAlN coating prepared by using a PVD method) can be changed. Literature studies have shown that when the boron content is 4at.%, the PVD tiabn coating hardness is significantly higher than that of PVD TiAlN coatings, and when the boron content is 9at.%, the PVD tiabn coating hardness is significantly reduced; in addition, after boron is added into TiAlN, the anatase structure a-TiO can be improved 2 Metastable phase-to-rutile structure r-TiO 2 Stabilizing the transition temperature of the phase, promoting a-Al 2 O 3 Therefore, the oxidation resistance of the TiAlN coating can be remarkably improved. In general, PVD TiAlBN coatings have high hardness, and the deposition process is under negative bias, with high coating compressive stress, and often it is difficult to obtain high coating bond strength.
Disclosure of Invention
In view of the above-described drawbacks of the prior art, it is an object of the present invention to provide a high temperature oxidation resistant composite coated cutting tool, a method for its preparation and its use in high speed dry cutting.
This patent scheme provides a composite coating cutter, includes: the coating comprises a substrate and a composite coating layer sequentially arranged on the surface of the substrate; the composite coating is prepared by adopting a chemical vapor deposition technology and comprises a first sub-coating and a second sub-coating, wherein a Ti-Al-B-N gradient layer with the boron content changing from low to high is arranged between the first sub-coating and the second sub-coating; the first sub-coating is Ti 1-x Al x An N layer, the second sub-coating is Ti a Al b B c An N layer; the highest boron content in the gradient layer is not higher than the boron content of the second sub-coating.
Further, the Ti is 1-x Al x In the N layer, x is more than or equal to 0.70 and less than or equal to 0.90; the Ti is a Al b B c In the N layer, a+b+c=1, 0<a≤0.15，0.65≤b≤0.80。
Further, the phase composition of the first sub-coating layer comprises a face-centered cubic structure fcc-TiN, a face-centered cubic structure fcc-AlN and a close-packed hexagonal structure hcp-AlN, and the volume fraction of fcc-AlN is not less than 80%, the fcc-AlN has the following crystal orientation relationship: 0.5<R is less than or equal to 1, wherein: r=i fcc-AlN(111) /(I fcc-AlN(111) +I fcc-AlN(220) )。I fcc-AlN(111) And I fcc-AlN(220) From the utilization of Cu-K α The X-ray diffraction peak areas extracted from the quasi-Voigt peak shape fitting results of the theta-2 theta scan obtained for fcc-AlN (111) and fcc-AlN (220) diffraction peaks were irradiated.
Further, the phase composition of the second sub-coating layer comprises a face-centered cubic structure fcc-TiN, a face-centered cubic structure fcc-AlN, a close-packed hexagonal structure hcp-AlN and an amorphous phase a-BN, and the volume fraction of fcc-AlN is not less than 75% and the volume fraction of a-BN is 5-15%.
Further, the total thickness of the composite coating layer is 5.0 to 25.0 μm, preferably 10.0 to 15.0 μm, the thickness of the first sub-coating layer is 3.0 to 10.0 μm, preferably 5.0 to 8.0 μm, the thickness of the second sub-coating layer is 4.0 to 10.0 μm, preferably 5.0 to 8.0 μm, and the thickness of the gradient layer is 0.50 to 4.0 μm, preferably 2.0 to 3.0 μm.
Further, the composite coating further comprises a bonding layer deposited between the surface of the substrate and the first sub-coating, wherein the bonding layer is one or more of Ti, tiN, tiC, tiCN and the like, preferably TiN, and the thickness of the bonding layer is 0.2-1.5 mu m.
Further, a surface layer is deposited on the surface of the second sub-coating layer, the surface layer is formed by removing the Ti a Al b B c Coating composition outside of N layers.
Further, the surface layer is TiAlN, tiN, tiBN, tiB 2 One or more of TiC, tiCN, tiAlSiN, tiSiN, ti, tiBCN, preferably TiB 2 And the thickness of the surface layer is 0.5 to 3.0 μm, preferably 1.0 to 2.0 μm.
Also provides a preparation method of the composite coating cutter, wherein the composite coating in the composite coating cutter adopts a chemical vapor deposition technology, and H is used under the conditions of 700-1000 ℃ and 4-1000 mbar 2 、TiCl 4 、AlCl 3 、NH 3 、N 2 、BCl 3 Ar is used as a raw material and is deposited on the surface of a matrix in sequence; the composite coating includes a bonding layer, a first subcoat, a gradient layer, and a second subcoat.
Further, the bonding layer is formed by using a chemical vapor deposition technique at 850-950 ℃ and 50-200 mbar to include TiCl 4 、N 2 、H 2 Is obtained by chemical reaction of the raw material on the surface of the substrate.
Further, the first sub-coating is prepared by using chemical vapor deposition technique at 700-900 ℃ and 4-30 mbar to include H 2 、TiCl 4 、AlCl 3 、NH 3 、N 2 Ar is used as a raw material, and the bonding layer is obtained by performing chemical reaction on the surface of the bonding layer.
Further, the gradient layer is prepared by chemical vapor deposition technique at 700-900 ℃ and 4-30 mbar to include H 2 、TiCl 4 、AlCl 3 、BCl 3 、NH 3 、N 2 Ar is used as raw material, and gradually increases BCl 3 Is obtained by a chemical reaction at the surface of the first sub-coating.
Further, the second sub-coating is prepared by chemical vapor deposition technique at 700-900 ℃ and 4-30 mbar to include H 2 、TiCl 4 、AlCl 3 、BCl 3 、NH 3 、N 2 Ar is used as a raw material, and chemical reaction is carried out on the surface of the gradient layer to obtain the high-strength steel.
Further, the composite coating also comprises a surface layer, wherein the surface layer is formed by adopting a chemical vapor deposition technology under the conditions of 750-1000 ℃ and 50-1000 mbar to comprise H 2 、TiCl 4 、BCl 3 Ar is used as a raw material, and chemical reaction is carried out on the surface of the second sub-coating to obtain
Further, the material of the matrix is one of hard alloy, high-speed steel, metal ceramic, polycrystalline diamond and cubic boron nitride.
And the application of the composite coating cutter provided by any one of the above, in particular to the application of high-speed dry cutting of any one of titanium alloy, nickel-based superalloy and heat-resistant stainless steel.
The improvement of this patent brings the following advantage:
(1) Compared with the prior art, the composite coating of the composite coating tool provided by the application is prepared by adopting a Chemical Vapor Deposition (CVD) technology, and when the aluminum content of the TiAlN coating (first sub-coating) in the composite coating reaches 80%, the hcp-AlN phase still cannot appear in the coating. Thus, the CVD TiAlN coating of the present application has a better combination of properties, especially resistance to high temperature oxidation, than PVD TiAlN coatings of the prior art.
(2) Compared with PVD TiAlBN coating, the TiAlBN coating prepared by adopting the CVD method can avoid the formation of hcp-AlN with a hexagonal structure under the condition of higher aluminum content, so that the coating has better high-temperature oxidation resistance and wear resistance. In addition, as an improvement, the ratio of the flow rate of the reaction gas is controlled, namely, BCl is gradually increased when the gradient layer is formed by deposition 3 The content of boron element in the coating can be flexibly adjusted.
(3) The boron content of the gradient layer in the composite coating changes in a gradient manner, which is beneficial to reducing the internal stress of the coating and improving the bonding strength between the coatings. If the boron content of the gradient layer is higher than that of the second sub-coating, more amorphous phases may be formed in the gradient layer, and the hardness and strength of the gradient layer are reduced, so that the supporting effect on the second sub-coating is weakened, plastic deformation easily occurs in the cutting process, and the service life of the cutter is shortened. According to the method, the boron content of the gradient layer is not higher than that of the second sub-coating through ingenious setting of the boron content of the gradient layer, so that the hardness and strength of the gradient layer are improved, and the service life of the cutter is prolonged.
(4) Due to the high hardness of PVD TiAlBN coating, the coating compressive stress is large under the action of negative bias in the deposition process, and high coating bonding strength is often difficult to obtain. The application develops a new method, and forms Ti by using a CVD method by utilizing the characteristics of high deposition temperature of the CVD TiAlBN coating, easy mutual diffusion of elements among the coatings and easy formation of metallurgical bonding among the coatings a Al b B c And the N layer (second sub-coating) enables the second sub-coating to form metallurgical bonding with the adjacent coating, so that higher coating bonding strength is obtained, and the wear resistance of the cutter is further improved.
(5) Because the temperature for preparing the TiAlBN coating by the CVD method is higher, the temperature is generally higher than 700 ℃, the radius of boron atoms is small, and the boron atoms in the TiAlBN coating are easy to diffuse into hard alloy matrixes such as WC-Co groups and the like to form W 3 CoB 3 And the brittleness phase is equal, and the toughness of the cutter is reduced. Therefore, the method can be used for depositing other compact boron-free coating (first sub-coating) before the TiAlBN coating is formed by adopting the CVD method, so that the diffusion of boron element to the substrate can be remarkably reduced.
(6) As an improvement, the present application precisely modulates the second sub-coating (Ti a Al b B c N layer) of Ti, al, B elements. Wherein b represents the content of Al element, and when b is more than or equal to 0.65 and less than or equal to 0.80, the coating has better high-temperature oxidation resistance and high hardness; b>At 0.80, closely packed hexagonal hcp-AlN may be formed, decreasingCoating hardness; and b<At 0.65, the high temperature oxidation resistance of the coating is reduced; a and c respectively represent the contents of Ti and B elements, after the values of a and B are limited, the range of c is limited, the amorphous phase content is too high when the value of c is too high, the hardness of the coating is reduced, and the wear resistance is reduced; the c value is too low, the amorphous phase content is too low, and the effect of grain refinement to improve hardness and wear resistance cannot be achieved, and the best balance can be obtained between the two only when the c value is within the range defined in the present application.
(7) As a modification, the (111) plane is the atomic nearest surface of the face-centered cubic crystal, and there are 12 slip systems. The coating has optimal plastic deformation capability when grown with the preferred orientation of the (111) crystal face, so the coating has better toughness, and the coating has higher hardness when grown with the preferred orientation of the (220) crystal face. The mechanical properties (toughness and hardness) of the coating are regulated by regulating the areas of the diffraction peaks of the (111) crystal faces and the (220) crystal faces.
(8) As an improvement, the volume fraction of the a-BN is 5 to 15 percent; when the volume fraction of a-BN is lower than 5%, the amorphous phase content is too low to realize the effect of grain refinement to improve hardness and wear resistance; above 15%, the amorphous phase content is too high, and the hardness of the coating layer decreases, reducing the wear resistance.
Drawings
FIG. 1 is a schematic cross-sectional view of a composite coated tool according to the present application;
FIG. 2 is a photograph of a fracture electron micrograph of a composite coated tool of the present application;
FIG. 3 is a CVD Ti 0.17 Al 0.83 Fracture electron micrograph of N coating;
FIG. 4 is a CVD TiN/Ti 0.10 Al 0.75 B 0.15 Fracture electron micrograph of N coating;
wherein 100 is a substrate, the composite coatings 200, 201 are bonding layers, 202 are first sub-coatings, 203 are gradient layers, 204 are second sub-coatings, and 205 are surface layers.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Example 1
As shown in fig. 1, a composite coated layer 200 tool includes a substrate 100 and a composite coated layer 200 sequentially disposed on a surface of the substrate 100; the composite coating 200 is prepared by chemical vapor deposition technology, and comprises the following steps from inside to outside: a bonding layer 201, a first sub-coating 202, a gradient layer 203, and a second sub-coating 204 deposited on the surface of the substrate 100. The total thickness of the composite coating 200 is 5.0 to 25.0 μm, preferably 10.0 to 15.0 μm, or 12.0 to 13.0 μm.
The substrate 100 is made of one of cemented carbide, high-speed steel, cermet, and the like. The substrate 100 may be a cutting or forming or stamping tool, or a component or part of a vehicle, or a component or part for the automotive or aerospace industry.
The bonding layer 201 is one or more of Ti, tiN, tiC, tiCN, etc., preferably TiN; the thickness of the bonding layer 201 is 0.2 to 1.5. Mu.m, preferably 0.5 to 0.9. Mu.m, or 1 to 1.3. Mu.m.
The first subcoat 202 is Ti 1-x Al x And an N layer, wherein x is more than or equal to 0.70 and less than or equal to 0.90, and preferably x is more than or equal to 0.75 and less than or equal to 0.85. The thickness is 3.0 to 10.0. Mu.m, preferably 5.0 to 8.0. Mu.m, or 6.0 to 7.0. Mu.m. The phase composition of the first sub-coating 202 comprises face-centered cubic structure fcc-TiN, face-centered cubic structure fcc-AlN and close-packed hexagonal structure hcp-AlN and the volume fraction of fcc-AlN is not less than 80%, the fcc-AlN having the following crystal orientation relationship: 0.5<R.ltoreq.1, preferably 0.7<R is less than or equal to 0.9; wherein: r=i fcc-AlN(111) /(I fcc-AlN(111) +I fcc-AlN(220) )，I fcc-AlN(111) And I fcc-AlN(220) From the utilization of Cu-K α The X-ray diffraction peak areas extracted from the quasi-Voigt peak shape fitting results of the theta-2 theta scan obtained for fcc-AlN (111) and fcc-AlN (220) diffraction peaks were irradiated. (111) The crystal face is the atomic closest face of the face-centered cubic crystal, and has 12 slidesAnd (5) transferring. The coating has optimal plastic deformation capability when grown with the preferred orientation of the (111) crystal face, so the coating has better toughness, and the coating has higher hardness when grown with the preferred orientation of the (220) crystal face. The mechanical properties (toughness and hardness) of the coating are regulated by regulating the areas of the diffraction peaks of the (111) crystal faces and the (220) crystal faces. The face-centered cubic structure refers to a crystal structure in which only the face center, the prism center and the vertex of one unit cell have elements. The close packed hexagonal structure refers to a hexagonal crystal structure having one atom at the center of each bottom surface and three coplanar atoms at the inner half height of the unit cell, except for 12 atoms at the top corner of the hexagonal unit cell, with an axial ratio of approximately 1.633.
The gradient layer 203 is a Ti-Al-B-N layer with the boron content changing from low to high in a gradient manner; the highest boron content in the graded layer 203 is not higher than the boron content of the second sub-coating 204. The thickness is 0.50 to 4.0. Mu.m, preferably 2.0 to 3.0. Mu.m, or 2.5 to 2.8. Mu.m.
The second subcoat 204 is Ti a Al b B c N layers, a+b+c=1, 0<a is more than or equal to 0.15,0.65, b is more than or equal to 0.80; preferably 0<a is more than or equal to 0.1,0.70 and b is more than or equal to 0.75. The thickness is 4.0 to 10.0. Mu.m, preferably 5.0 to 8.0. Mu.m, or 6.0 to 7.0. Mu.m. The phase composition of the second sub-coating 204 comprises face-centered cubic structure fcc-TiN, face-centered cubic structure fcc-AlN, close-packed hexagonal structure hcp-AlN and amorphous phase a-BN, and wherein the volume fraction of fcc-AlN is not less than 75% and the volume fraction of a-BN is 5-15%. The volume fraction of the a-BN is 5 to 15 percent; when the volume fraction of a-BN is lower than 5%, the amorphous phase content is too low to realize the effect of grain refinement to improve hardness and wear resistance; above 15%, the amorphous phase content is too high, and the hardness of the coating layer decreases, reducing the wear resistance. Preferably, the fcc-AlN volume fraction is not less than 85% and the a-BN volume fraction is 8 to 12%.
The composite coating 200 may also include a surface layer 205, the surface layer 205 being made of a different material than the second subcoat 204, i.e., from a material other than Ti a Al b B c Coating compositions other than N layers, e.g. TiAlN, tiN, tiBN, tiB 2 One or more of TiC, tiCN, tiAlSiN, tiSiN, ti, tiBCN, preferably TiB 2 . The thickness of the surface layer 205 is 0.5 to 3.0. Mu.m, preferably 1.0 to 2.0 μm, or 1.3 to 1.8 μm.
Example 2
FIG. 2 is an electron micrograph of a physical fracture of a coating prepared according to the present application, wherein the matrix is WC-Co-based cemented carbide, the bonding layer is TiN, and the first subcoat is Ti 0.17 Al 0.83 The gradient layer is Ti-Al-B-N coating with boron content of 0-15 at%, and the second sub-coating is Ti 0.10 Al 0.75 B 0.15 N. The composite coated cutting tool is prepared by the following steps S1-S4, wherein each coating is prepared by adopting a Chemical Vapor Deposition (CVD) technology.
S1: preparing a bonding layer of TiN, wherein the deposition temperature is 900 ℃, the deposition pressure is 100mbar, and the reaction material comprises TiCl 4 、N 2 、H 2 The purity of each reaction material is more than 99 percent, the deposition time is 60 minutes, and the thickness of the coating is 0.9 mu m;
s2: preparation of first subcoat Ti 0.17 Al 0.83 N, deposition temperature 800 ℃, deposition pressure 10mbar, reaction material including H 2 、TiCl 4 、AlCl 3 、NH 3 、N 2 Ar, the purity of each reaction material is more than 99 percent, the deposition time is 120min, and the thickness of the coating is 4.5 mu m;
s3: preparing a gradient layer Ti-Al-B-N layer, wherein the deposition temperature is 850 ℃, the deposition pressure is 20mbar, and the reaction materials comprise H 2 、TiCl 4 、AlCl 3 、BCl 3 、NH 3 、N 2 Ar, the purity of each reaction material is more than 99 percent, the deposition time is 60 minutes, and the thickness of the coating is 1.2 mu m;
s4: preparation of second subcoat Ti 0.10 Al 0.75 B 0.15 N, deposition temperature 850 ℃, deposition pressure 20mbar, reaction material including H 2 、TiCl 4 、AlCl 3 、BCl 3 、NH 3 、N 2 Ar, the purity of each reaction material is more than 99%, the deposition time is 180min, and the thickness of the coating is 5.0 mu m.
Comparative example 1: FIG. 3 is a CVD Ti 0.17 Al 0.83 An N-coating fracture electron micrograph is prepared as follows:
deposition temperature 800 ℃, deposition pressure 10mbar, reaction gasBody H 2 、TiCl 4 、AlCl 3 、NH 3 、N 2 Ar, the purity of each gas is more than 99.99%, the deposition time is 240min, and the thickness of the coating is 9.5 mu m.
Comparative example 2: FIG. 4 is a CVD TiN/Ti 0.10 Al 0.75 B 0.15 N coating fracture electron micrograph, the preparation method of each layer is as follows:
(1) TiN layer, deposition temperature 900 ℃, deposition pressure 100mbar, reaction gas TiCl 4 、N 2 、H 2 The purity of each gas is more than 99.99 percent, the deposition time is 75 minutes, and the thickness of the coating is 1.5 mu m;
(2)Ti 0.10 Al 0.75 B 0.15 n layer, deposition temperature 850 ℃, deposition pressure 20mbar, reaction gas H 2 、TiCl 4 、AlCl 3 、BCl 3 、NH 3 、N 2 Ar, the purity of each gas is more than 99.99%, the deposition time is 240min, and the thickness of the coating is 8.0 mu m.
Comparative example 3: the PVD TiAlN coating is prepared by the following steps:
(1) Adopting a multi-arc ion plating technology;
(2) Alloy target Al/ti=67/33 (atomic ratio), deposition temperature 550 ℃, deposition pressure 8.0×10 -2 mbar；
(3) The deposition time is 360min, the coating thickness is 9.0 mu m, and the coating component Ti 0.35 Al 0.65 N。
Comparative example 4: PVD TiAlBN coating, its preparation method is as follows:
(1) Adopting a multi-arc ion plating technology;
(2) Alloy target Al/Ti/B=60/30/10 (atomic ratio), deposition temperature 550 ℃, deposition pressure 8.0x10 - 2 mbar；
(3) The deposition time is 360min, the coating thickness is 8.5 mu m, and the coating component Ti 0.34 Al 0.58 B 0.08 N。
Table 1 shows the mechanical properties of example 2 compared with those of comparative examples 1 to 4.
Table 1 mechanical property comparison
The hardness detection method comprises the following steps:
the surface of the substrate is polished to a mirror surface, and after the coating is deposited, a bearing steel ball with the diameter of 20mm is used for facing the surface of the coating for 20 seconds, and diamond grinding agent is added during grinding. Then, the hardness (100 times of amplification) of the coating at the abrasion mark is tested by using a TTX-NHT2 nanoindenter (Austrian An Dongpa company), the pressing needle is a diamond Borschner head (Berkovich), the maximum load is 20mN, the loading rate is 40mN/min, the unloading rate is 40mN/min, the dwell time is 5 seconds, and the pressing depth is less than 1/10 of the total thickness of the coating in order to eliminate the influence of the matrix on the hardness. The hardness of 20 different points was measured in total and averaged as the hardness of the coating.
The method for detecting the bonding strength comprises the following steps:
the bonding strength of the coating to the substrate was measured using a REVETEST scratch tester manufactured by Swiss CSM company. The scratch test method is to slide a hemispherical diamond pressure head with the diameter of about 200 micrometers on the surface of the coating, continuously increasing vertical load L through an automatic loading mechanism in the process, and when L reaches critical load Lc, starting to peel off the coating from a substrate, wherein the interface critical load Lc between the coating and the substrate is the minimum load required by the pressure head to completely scratch the coating and continuously peel off the coating from the substrate; meanwhile, the friction force F between the pressure head and the coating and the substrate correspondingly changes. At this time, the coating generates acoustic emission, the acoustic emission signal, the load variation and the tangential force variation are obtained by the sensor, the acoustic emission signal, the load variation and the tangential force variation are amplified, the amplified acoustic emission signal, the load variation and the tangential force variation are input into a computer to draw the measurement result into a graph through A/D conversion, the acoustic emission peak is correspondingly obtained at the critical load value Lc on the acoustic emission signal-load curve, and the critical load Lc is the criterion of the bonding strength of the coating and the matrix. The test parameters are as follows: and (3) carrying out linear loading, loading 200N, loading speed 99N/min, scratch speed 5mm/min and scratch length 5mm.
The test method for the oxidative weight gain is as follows:
the sample was heated to 1000 ℃ in a muffle furnace under air atmosphere, incubated for 1h, and then taken out of the atmosphere and cooled to room temperature. And weighing the weight of the sample before and after oxidization by adopting a high-precision electronic balance with the precision of 0.1mg, and calculating the oxidization weight gain of the sample.
Coefficient of friction testing is tested against international standard ASTM G99-2017.
Titanium alloy milling comparison:
the processing mode is as follows: milling the surface;
work piece: a square piece;
materials: ti6Al4V;
blade type: SNGX1206ANN-MM4;
cutting conditions: cutting speed 100m/min, feeding 0.2mm/z, cutting depth 1mm, cutting width ae 60mm, and dry cutting;
the measurement results of the wear amount VB (unit mm) of the rear cutter surface of the blade after cutting for different times are shown in Table 2, and the wear amount of the rear cutter surface of the blade is measured by using an OLYMPUS SZ61 optical super-depth-of-field microscope with a graduated scale.
Table 2 comparative wear level of the rear face of a milling titanium alloy Ti6Al4V insert
| Coating layer | 2.2min | 8.8min | 15.4min | 22.2min | 29.8min |
| Example 2 | 0.06 | 0.11 | 0.16 | 0.21 | 0.30 |
| Comparative example 1 | 0.11 | 0.22 | 0.32 | -- | -- |
| Comparative example 2 | 0.08 | 0.15 | 0.20 | 0.31 | -- |
| Comparative example 3 | 0.12 | 0.25 | 0.40 | -- | -- |
| Comparative example 4 | 0.10 | 0.18 | 0.25 | 0.35 | -- |
As can be seen from table 2, the wear resistance of the blade coated with the composite coating of the present application was greatly improved. Superalloy milling comparison:
the processing mode is as follows: milling the surface;
work piece: a square piece;
materials: GH7192;
blade type: SNGX1206ANN-MM4;
cutting conditions: cutting speed is 80m/min, feeding is 0.25mm/z, cutting depth is 1mm, cutting width ae is 60mm, and dry cutting is performed;
the measurement results of the wear amount VB (unit mm) of the rear cutter surface of the blade after cutting for different times are shown in Table 3, and the wear amount of the rear cutter surface of the blade is measured by using an OLYMPUS SZ61 optical super-depth-of-field microscope with a graduated scale.
Table 3 comparative wear on the flank of a milled titanium alloy GH7192 insert
| Coating layer | 3min | 6min | 9min | 12min |
| Example 2 | 0.09 | 0.17 | 0.24 | 0.35 |
| Comparative example 1 | 0.13 | 0.21 | 0.30 | -- |
| Comparative example 2 | 0.12 | 0.19 | 0.26 | 0.50 |
| Comparative example 3 | 0.18 | 0.31 | -- | -- |
| Comparative example 4 | 0.15 | 0.22 | 0.35 | -- |
Compared with the prior art, the service life of the blade coated with the composite coating is greatly prolonged.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (15)
1. A composite coating cutter is characterized by comprising a substrate and a composite coating sequentially arranged on the surface of the substrate; the composite coating is prepared by adopting a chemical vapor deposition technology and comprises a first sub-coating and a second sub-coating, wherein a Ti-Al-B-N gradient layer with the boron content changing from low to high is arranged between the first sub-coating and the second sub-coating; the first sub-coating is Ti 1-x Al x An N layer, the second sub-coating is Ti a Al b B c An N layer; the highest boron content in the gradient layer is not higher than the boron content of the second sub-coating; the Ti is 1-x Al x In the N layer, x is more than or equal to 0.70 and less than or equal to 0.90; the Ti is a Al b B c In the N layer, a+b+c=1, 0<a is more than or equal to 0.15,0.65, b is more than or equal to 0.80; the phase composition of the first sub-coating layer comprises fcc-TiN with a face-centered cubic structure, fcc-AlN with a face-centered cubic structure and hcp-AlN with a close-packed hexagonal structure, and the volume fraction of fcc-AlN is not less than 80%, the fcc-AlN having the following crystal orientation relationship: 0.5<R is less than or equal to 1, wherein: r=i fcc-AlN(111) /(I fcc-AlN(111) +I fcc-AlN(220) ) The method comprises the steps of carrying out a first treatment on the surface of the The phase composition of the second sub-coating comprises fcc-TiN with a face-centered cubic structure, fcc-AlN with a face-centered cubic structure, hcp-AlN with a close-packed hexagonal structure and amorphous phase a-BN, wherein the volume fraction of fcc-AlN is not lower than 75% and the volume fraction of a-BN is 5-15%.
2. The composite coated cutting tool according to claim 1, wherein the total thickness of the composite coating is 5.0-25.0 μm, the thickness of the first sub-coating is 3.0-10.0 μm, the thickness of the second sub-coating is 4.0-10.0 μm, and the thickness of the gradient layer is 0.50-4.0 μm.
3. The composite coated cutting tool according to claim 2, wherein the total thickness of the composite coating is 10.0-15.0 μm, the thickness of the first sub-coating is 5.0-8.0 μm, the thickness of the second sub-coating is 5.0-8.0 μm, and the thickness of the gradient layer is 2.0-3.0 μm.
4. The composite coated cutting tool of claim 1, wherein the composite coating further comprises a bond layer deposited between the substrate surface and the first subcoat, the bond layer being one or more of Ti, tiN, tiC, tiCN, the bond layer having a thickness of 0.2-1.5 μm.
5. The composite coated cutting tool of claim 4, wherein the bonding layer is TiN.
6. A composite coated tool as claimed in claim 1, wherein a surface layer is deposited on the surface of said second sub-coating layer, said surface layer being formed by removing said Ti a Al b B c Coating composition outside of N layers.
7. The composite coated cutting tool of claim 6, wherein the skin layer is TiAlN, tiN, tiBN, tiB 2 One or more of TiC, tiCN, tiAlSiN, tiSiN, ti, tiBCN, and the thickness of the surface layer is 0.5-3.0 μm.
8. The composite coated cutting tool of claim 7, wherein the surface layer is TiB 2 And the thickness of the surface layer is 1.0-2.0 mu m.
9. A method for producing a composite coated cutting tool according to claim 4, wherein the composite coating layer in the composite coated cutting tool is produced by chemical vapor deposition at 700-1000 ℃ and 4-1000 mbar to include H 2 、TiCl 4 、AlCl 3 、NH 3 、N 2 、BCl 3 Ar is used as a raw material and is deposited on the surface of a matrix in sequence; the composite coating comprises a bonding layer, a first sub-coating, a gradient layer and a second sub-coating; the gradient layer is prepared by chemical vapor deposition at 700-900 ℃ and 4-30 mbar to comprise H 2 、TiCl 4 、AlCl 3 、BCl 3 、NH 3 、N 2 Ar is used as raw material, and gradually increases BCl 3 Is obtained by a chemical reaction at the surface of the first sub-coating.
10. The method of claim 9, wherein the bonding layer is formed by chemical vapor deposition at 850-950 ℃ and 50-200 mbar to include TiCl 4 、N 2 、H 2 Is as the originThe material is obtained by carrying out chemical reaction on the surface of the matrix.
11. The method of claim 10, wherein the first sub-coating is prepared by chemical vapor deposition at 700-900 ℃ and 4-30 mbar to include H 2 、TiCl 4 、AlCl 3 、NH 3 、N 2 Ar is used as a raw material, and the bonding layer is obtained by performing chemical reaction on the surface of the bonding layer.
12. The method of claim 11, wherein the second sub-coating is prepared by chemical vapor deposition at 700-900 ℃ and 4-30 mbar to include H 2 、TiCl 4 、AlCl 3 、BCl 3 、NH 3 、N 2 Ar is used as a raw material, and chemical reaction is carried out on the surface of the gradient layer to obtain the high-strength steel.
13. The method of claim 12, wherein the composite coating further comprises a surface layer comprising H by chemical vapor deposition at 750-1000 ℃ and 50-1000 mbar 2 、TiCl 4 、BCl 3 Ar is used as a raw material, and chemical reaction is carried out on the surface of the second sub-coating to obtain the coating.
14. The method for producing a composite coated cutting tool according to any one of claims 9 to 13, wherein the material of the substrate is one of cemented carbide, high-speed steel, polycrystalline diamond, cubic boron nitride.
15. The use of a composite coated tool according to any one of claims 1-8, characterized in that it is a high speed dry cutting of any one of titanium alloy, nickel-based superalloy, heat resistant stainless steel.
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