CN114196940A - 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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- CN114196940A CN114196940A CN202111475991.5A CN202111475991A CN114196940A CN 114196940 A CN114196940 A CN 114196940A CN 202111475991 A CN202111475991 A CN 202111475991A CN 114196940 A CN114196940 A CN 114196940A
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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
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- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
The invention discloses a composite coating cutter and a preparation method and application thereof, and the composite coating cutter comprises a substrate and composite coatings 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, and a Ti-Al-B-N gradient layer with the boron content changing from low to high in a gradient manner is arranged between the first sub-coating and the second sub-coating; the first sub-coating is Ti1‑xAlxN layers, the second sub-coating layer isTiaAlbBcN layers; the highest boron content in the gradient layer is not higher than the boron content of the second subcoating. The invention aims to provide a composite coating cutter resistant to high-temperature oxidation, 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 as well as 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 demand is increasing day by day. The local temperature of the cutter can reach over 1000 ℃ during high-speed dry cutting, so that the cutter is required to have good high-temperature oxidation resistance. Titanium alloy, nickel-based high-temperature alloy, heat-resistant stainless steel and other materials have high strength, and the surface of the cutter is easy to generate built-up edges during cutting processing, so that the cutter is seriously bonded and abraded. The surface coating of the cutting tool can effectively prolong the service life of the tool, and in order to solve the processing problems, the surface of the tool coating is required to be smooth, the friction coefficient is low, the bonding strength of the coating is high, and the wear resistance is good.
The aluminum element is added into the coating, so that the high-temperature oxidation resistance of the cutter can be obviously improved, 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 elements such as boron and the like. To ensure that the TiAlN coating has a high hardness and wear resistance, it is generally desirable to have a high content of fcc-AlN in the TiAlN coating, avoiding the formation of hcp-AlN as much as possible. In the prior art, a TiAlN coating prepared by a Physical Vapor Deposition (PVD) method generally 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 percent, hcp-AlN phase with a hexagonal structure is generated, so that the hardness and the wear resistance of the coating are reduced.
Moreover, boron element is added on the basis of the PVD TiAlN coating to form a TiAlN coatingLayer, the properties of PVD TiAlN coatings (TiAlN coatings prepared using PVD methods) can be altered. Literature research shows that when the boron content is 4 at.%, the hardness of the PVD TiAlN coating is obviously higher than that of the PVD TiAlN coating, and when the boron content is 9 at.%, the hardness of the PVD TiAlN coating is obviously reduced; in addition, after the boron element is added into TiAlN, the anatase structure a-TiO can be improved2Metastable opposite rutile structure r-TiO2Stabilizing the transition temperature of the phase and promoting a-Al2O3Thereby remarkably improving the oxidation resistance of the TiAlN coating. Generally, the PVD TiAlBN coating has high hardness, and the coating has large compressive stress under the action of negative bias in the deposition process, so that high coating bonding strength is difficult to obtain.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a composite coated cutting tool resistant to high temperature oxidation, as well as a method for its preparation and use in high speed dry cutting.
This patent scheme provides a composite coating cutter, includes: the composite coating comprises a substrate and composite coatings 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, and a Ti-Al-B-N gradient layer with the boron content changing from low to high in a gradient manner is arranged between the first sub-coating and the second sub-coating; the first sub-coating is Ti1-xAlxN layer, the second sub-coating is TiaAlbBcN layers; the highest boron content in the gradient layer is not higher than the boron content of the second subcoating.
Further, the Ti1-xAlxIn the N layer, x is more than or equal to 0.70 and less than or equal to 0.90; the TiaAlbBcIn the N layers, a + b + c is 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 the 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 is ═ Ifcc-AlN(111)/(Ifcc-AlN(111)+Ifcc-AlN(220))。Ifcc-AlN(111)And Ifcc-AlN(220)Respectively from utilizing Cu-KαIrradiating an X-ray diffraction peak area extracted from a quasi-Voigt peak shape fitting result of a theta-2 theta scan obtained for fcc-AlN (111) and fcc-AlN (220) diffraction peaks.
Further, the phase composition of the second sub-coating layer comprises fcc-TiN in a face-centered cubic structure, fcc-AlN in a face-centered cubic structure, hcp-AlN in a close-packed hexagonal structure and amorphous a-BN, and the volume fraction of the fcc-AlN is not less than 75% and the volume fraction of the a-BN is 5-15%.
Further, the total thickness of the composite coating is 5.0-25.0 μm, preferably 10.0-15.0 μm, the thickness of the first sub-coating is 3.0-10.0 μm, preferably 5.0-8.0 μm, the thickness of the second sub-coating is 4.0-10.0 μm, preferably 5.0-8.0 μm, and the thickness of the gradient layer is 0.50-4.0 μm, preferably 2.0-3.0 μm.
Further, the composite coating further comprises a bonding layer deposited between the surface of the substrate and the first sub-coating, 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 microns.
Further, a surface layer is deposited on the surface of the second sub-coat layer, the surface layer being formed by removing the TiaAlbBcCoating composition except N layers.
Further, the surface layer is TiAlN, TiN, TiBN, TiB2One or more of TiC, TiCN, TiAlSiN, TiSiN, Ti and TiBCN, preferably TiB2And the thickness of the surface layer is 0.5 to 3.0 μm, preferably 1.0 to 2.0 μm.
The composite coating in the composite coating cutter is prepared by adopting a chemical vapor deposition technology and using H under the conditions of 700-1000 ℃ and 4-1000 mbar2、TiCl4、AlCl3、NH3、N2、BCl3Ar is used as a raw material and is formed by sequentially depositing on the surface of a substrate; the composite coating includes a bonding layer, a first subcoat, a gradient layer, and a second subcoat.
Further, the bonding layer is formed by chemical vapor deposition to include TiCl at 850-950 ℃ under 50-200 mbar4、N2、H2Is obtained by chemical reaction on the surface of a substrate.
Further, the first sub-coating is formed by adopting a chemical vapor deposition technology under the conditions of 700-900 ℃ and 4-30 mbar and comprises H2、TiCl4、AlCl3、NH3、N2Ar is a raw material and is obtained by a chemical reaction on the surface of the bonding layer.
Further, the gradient layer is formed by chemical vapor deposition technology under the conditions of 700-900 ℃ and 4-30 mbar and comprises H2、TiCl4、AlCl3、BCl3、NH3、N2Ar as raw material and gradually increasing BCl3Is obtained by chemical reaction at the surface of the first sub-coating.
Further, the second sub-coating is formed by chemical vapor deposition technology under the conditions of 700-900 ℃ and 4-30 mbar and comprises H2、TiCl4、AlCl3、BCl3、NH3、N2Ar is a raw material and is obtained by chemical reaction on the surface of the gradient layer.
Further, the composite coating further comprises a surface layer, wherein the surface layer is prepared by adopting a chemical vapor deposition technology under the conditions of 750-1000 ℃ and 50-1000 mbar and comprises H2、TiCl4、BCl3Ar is used as a raw material and is obtained by chemical reaction on the surface of the second sub-coating
Further, the material of the substrate is one of hard alloy, high-speed steel, metal ceramic, polycrystalline diamond and cubic boron nitride.
The composite coating cutter is applied to high-speed dry cutting of any one of titanium alloy, nickel-based high-temperature alloy and heat-resistant stainless steel.
The improvement of this patent brings the following advantage:
(1) compared with the prior art, the composite coating cutter is prepared by adopting a Chemical Vapor Deposition (CVD) technology, and when the content of aluminum in a TiAlN coating (a first sub-coating) in the composite coating reaches 80%, an hcp-AlN phase still cannot appear in the coating. Therefore, the CVD TiAlN coating has better comprehensive performance, especially high-temperature oxidation resistance, than the PVD TiAlN coating in the prior art.
(2) Compared with a PVD TiAlN coating, the TiAlN coating prepared by the CVD method can avoid the formation of hcp-AlN with a hexagonal structure under the condition of higher aluminum content, so that the TiAlN coating has better high-temperature oxidation resistance and wear resistance. In addition, as an improvement, when a gradient layer is formed by deposition, the flow ratio of the reaction gas is controlled, namely BCl is gradually increased3The proportion of (A) can flexibly adjust the content of the boron element in the coating.
(3) The boron content of the gradient layer in the composite coating is in gradient change, which is beneficial to reducing the internal stress of the coating and improving the bonding strength between the coatings. And if the boron content of the gradient layer is higher than that of the second sub-coating, more amorphous phases are likely to be formed in the gradient layer, and the hardness and the strength of the gradient layer are reduced, so that the supporting effect on the second sub-coating is weakened, plastic deformation is likely to occur in the cutting process, and the service life of the cutter is shortened. This application is through the ingenious setting to gradient layer boron content, lets the boron content on gradient layer not higher than the boron content of second subcoating, has improved the hardness and the intensity on gradient layer, has strengthened the life of cutter.
(4) Because the PVD TiAlBN coating has high hardness, the coating has larger compressive stress under the action of negative bias in the deposition process, and high coating bonding strength is difficult to obtain. The method develops a new method, and Ti is deposited and formed 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 metallurgical bonding among the coatingsaAlbBcN layers (second sub-coatings) are formed, and the second sub-coatings and the adjacent coatings form metallurgical bonding, so that higher coating bonding strength is obtained, and the wear resistance of the cutter is further improved.
(5) Due to CVDThe TiAlN coating prepared by the method has higher temperature which is usually more than 700 ℃, the radius of boron atoms is small, and the boron atoms in the TiAlN coating are easy to diffuse into WC-Co base and other hard alloy matrixes to form W3CoB3And the toughness of the cutter is reduced due to the equal brittleness phase. Therefore, according to the method, before the TiAlBN coating is deposited and formed by adopting the CVD method, other dense boron-free coatings (first sub-coatings) are deposited and formed, and the diffusion of boron elements to a substrate can be remarkably reduced.
(6) As an improvement, the present application precisely conditions the second subcoat (Ti)aAlbBcN layer) of Ti, Al, B elements. In the formula, 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>When the thickness is 0.80, hcp-AlN with a close-packed hexagonal structure can be formed, so that the hardness of the coating is reduced; and b<At 0.65, the high-temperature oxidation resistance of the coating is reduced; a and c respectively represent the content of Ti and B elements, after the values of a and B are limited, the range of the value of c is limited, and when the value of c is too high, the content of amorphous phase 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, the effect of improving the hardness and the wear resistance by grain refinement cannot be realized, and the optimal balance between the c value and the wear resistance can be obtained only when the c value is within the range defined by the application.
(7) As an improvement, the (111) crystal face is the atomic closest arrangement face of the face-centered cubic crystal and has 12 slip systems. The coating has the best plastic deformation capability when the coating grows in the preferred orientation of the (111) crystal plane, so that the coating has better toughness, and the coating has higher hardness when the coating grows in the preferred orientation of the (220) crystal plane. The mechanical properties (toughness and hardness) of the coating are adjusted by regulating and controlling the areas of (111) and (220) crystal plane diffraction peaks.
(8) As an improvement, the volume fraction of the a-BN is 5-15%; when the volume fraction of the a-BN is less than 5%, the content of the amorphous phase is too low, and the effect of improving the hardness and the wear resistance by grain refinement cannot be realized; above 15%, the amorphous phase content is too high, and the hardness of the coating is reduced, reducing the wear resistance.
Drawings
FIG. 1 is a schematic cross-sectional view of a composite coated cutting tool according to the present application;
FIG. 2 is a fracture electron micrograph of a composite coated cutting tool according to the present application;
FIG. 3 is CVD Ti0.17Al0.83Fracture electron micrographs of the N coating;
FIG. 4 shows CVD TiN/Ti0.10Al0.75B0.15Fracture electron micrographs of the N coating;
wherein 100 is a substrate, 200, 201 are bonding layers, 202 is a first subcoat, 203 is a gradient layer, 204 is a second subcoat, and 205 is a surface layer.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
As shown in fig. 1, a composite coating 200 cutting tool includes a substrate 100 and a composite coating 200 sequentially disposed on the surface of the substrate 100; the composite coating 200 is prepared by a chemical vapor deposition technology and sequentially comprises the following components 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 5.0-25.0 μm, preferably 10.0-15.0 μm, or 12.0-13.0 μm.
The base 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 part or part of a vehicle, or a part or part for the automotive industry or aerospace industry.
The bonding layer 201 is one or more of Ti, TiN, TiC, TiCN and the like, and TiN is preferred; the bonding layer 201 has a thickness of 0.2 to 1.5 μm, preferably 0.5 to 0.9 μm, or 1 to 1.3 μm.
The first sub-coating 202 is Ti1-xAlxN layer, 0.70-0.90, preferably 0.75-0.85. The thickness is 3.0 to 10.0 μm, preferably 5.0 to 8.0 μm, or 6.0 to 7.0 μm. The phase composition of the first sub-coating 202 includes a face-centered cubic structure fcc-TiN, a face-centered cubic structure fcc-AlN, and a close-packed hexagonal structure hcp-AlN, and a volume fraction of the 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 is ═ Ifcc-AlN(111)/(Ifcc-AlN(111)+Ifcc-AlN(220))，Ifcc-AlN(111)And Ifcc-AlN(220)Respectively from utilizing Cu-KαIrradiating an X-ray diffraction peak area extracted from a quasi-Voigt peak shape fitting result of a theta-2 theta scan obtained for fcc-AlN (111) and fcc-AlN (220) diffraction peaks. (111) The crystal plane is the atomic closest arrangement plane of the face-centered cubic crystal and has 12 slip systems. The coating has the best plastic deformation capability when the coating grows in the preferred orientation of the (111) crystal plane, so that the coating has better toughness, and the coating has higher hardness when the coating grows in the preferred orientation of the (220) crystal plane. The mechanical properties (toughness and hardness) of the coating are adjusted by regulating and controlling the areas of (111) and (220) crystal plane diffraction peaks. The face-centered cubic structure is a crystal structure in which only elements are present in the face center, the edge center, and the apex of one unit cell. A hexagonal close packed structure refers to a hexagonal crystal structure with one atom at the center of each base, and three coplanar atoms at the half height inside the cell, except 12 atoms at the apex of the hexagonal 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 μm, preferably 2.0 to 3.0 μm, or 2.5 to 2.8 μm.
The second sub-coating 204 is TiaAlbBcN layers, a + b + c being 1, 0<a is less than or equal to 0.15, b is less than or equal to 0.65 and less than or equal to 0.80; preferably 0<a is less than or equal to 0.1, and b is less than or equal to 0.75 and more than or equal to 0.70. The thickness is 4.0 to 10.0 μm, preferably 5.0 to 8.0 μm, or 6.0 to 7.0 μm. The phase composition of the second sub-coating 204 comprises face-centered cubic fcc-TiN, face-centered cubic fcc-AlN, hexagonal close-packed hcp-AlN, and amorphous a-BN, and wherein the volume fraction of fcc-AlNNot less than 75 percent and the volume fraction of the alpha-BN is 5-15 percent. The volume fraction of the a-BN is 5-15%; when the volume fraction of the a-BN is less than 5%, the content of the amorphous phase is too low, and the effect of improving the hardness and the wear resistance by grain refinement cannot be realized; above 15%, the amorphous phase content is too high, and the hardness of the coating is reduced, reducing the wear resistance. Preferably, the volume fraction of fcc-AlN is not less than 85% and the volume fraction of a-BN is 8-12%.
The composite coating 200 may further comprise a surface layer 205, the surface layer 205 being made of a different material than the second sub-coating 204, i.e. made of other than TiaAlbBcCoating compositions other than N-layers, e.g. TiAlN, TiN, TiBN, TiB2One or more of TiC, TiCN, TiAlSiN, TiSiN, Ti and TiBCN, preferably TiB2. The surface layer 205 has a thickness of 0.5 to 3.0 μm, preferably 1.0 to 2.0 μm, or 1.3 to 1.8 μm.
Example 2
FIG. 2 is an electron micrograph of a coating real object fracture prepared according to the present application, wherein the substrate is WC-Co based cemented carbide, the bonding layer is TiN, and the first sub-coating is Ti0.17Al0.83N, the gradient layer is a Ti-Al-B-N coating with the boron content of 0-15 at.%, and the second sub-coating is Ti0.10Al0.75B0.15And N is added. The composite coated cutting tool is manufactured through the following steps S1-S4, and each of the following coatings is manufactured by Chemical Vapor Deposition (CVD).
S1: preparing a bonding layer TiN, the deposition temperature is 900 ℃, the deposition pressure is 100mbar, and the reaction material comprises TiCl4、N2、H2The purity of each reaction material is more than 99 percent, the deposition time is 60min, and the thickness of the coating is 0.9 mu m;
s2: preparation of the first subcoat Ti0.17Al0.83N, deposition temperature 800 ℃, deposition pressure 10mbar, reaction material comprising H2、TiCl4、AlCl3、NH3、N2Ar, 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 Ti-Al-B-N layer at 850 deg.C under 20mbar of reaction material including H2、TiCl4、AlCl3、BCl3、NH3、N2Ar, the purity of each reaction material is more than 99 percent, the deposition time is 60min, and the thickness of the coating is 1.2 mu m;
s4: preparation of the second subcoat Ti0.10Al0.75B0.15N, deposition temperature 850 ℃, deposition pressure 20mbar, reaction material comprising H2、TiCl4、AlCl3、BCl3、NH3、N2Ar, the purity of each reaction material is more than 99 percent, the deposition time is 180min, and the thickness of the coating is 5.0 mu m.
Comparative example 1: FIG. 3 is CVD Ti0.17Al0.83The preparation method of the electron micrograph of the fracture of the N coating is as follows:
deposition temperature 800 deg.C, deposition pressure 10mbar, reaction gas H2、TiCl4、AlCl3、NH3、N2Ar, the purity of each gas is more than 99.99 percent, the deposition time is 240min, and the thickness of the coating is 9.5 mu m.
Comparative example 2: FIG. 4 shows CVD TiN/Ti0.10Al0.75B0.15The fracture electron micrograph of the N coating layer comprises the following preparation methods of the layers:
(1) TiN layer, deposition temperature is 900 ℃, deposition pressure is 100mbar, and reaction gas TiCl4、N2、H2The purity of each gas is more than 99.99 percent, the deposition time is 75min, and the thickness of the coating is 1.5 mu m;
(2)Ti0.10Al0.75B0.15n layers, deposition temperature 850 ℃, deposition pressure 20mbar, reaction gas H2、TiCl4、AlCl3、BCl3、NH3、N2Ar, the purity of each gas is more than 99.99 percent, the deposition time is 240min, and the thickness of the coating is 8.0 mu m.
Comparative example 3: the PVD TiAlN coating comprises the following preparation method:
(1) adopting multi-arc ion plating technology;
(2) the Al/Ti alloy target material is 67/33 (atomic ratio), the deposition temperature is 550 ℃, and the deposition pressure is 8.0 multiplied by 10-2mbar；
(3) The deposition time is 360min, and the coating thickness is 9.0 μmCoating composition Ti0.35Al0.65N。
Comparative example 4: the PVD TiAlBN coating is prepared by the following steps:
(1) adopting multi-arc ion plating technology;
(2) the alloy target Al/Ti/B is 60/30/10 (atomic ratio), the deposition temperature is 550 ℃, and the deposition pressure is 8.0 multiplied by 10- 2mbar；
(3) The deposition time is 360min, the coating thickness is 8.5 mu m, and the coating component is Ti0.34Al0.58B0.08N。
Table 1 shows the mechanical properties of example 2 compared with comparative examples 1 to 4.
TABLE 1 comparison of mechanical properties
The hardness detection method comprises the following steps:
polishing the surface of the substrate into a mirror surface, performing opposite grinding on the surface of the coating for 20 seconds by using a bearing steel ball with the diameter of 20mm after the coating is deposited, and adding a diamond grinding agent during grinding. The hardness of the coating at the grinding mark was then tested (amplified by 100 times) using a nano indenter model TTX-NHT2 (austria anappe), the indenter was a diamond Berkovich indenter (Berkovich), the maximum load was 20mN, the loading rate was 40mN/min, the unloading rate was 40mN/min, the dwell time was 5 seconds, and in order to eliminate the influence of the matrix on the hardness, the penetration depth was 1/10 which was less than the total thickness of the coating. The hardness was measured at 20 different points in total and the average was taken as the hardness of the coating.
The detection method of the binding strength is as follows:
the bond strength of the coating to the substrate was measured using a REVETEST scratch tester manufactured by CSM of Switzerland. The scratch test method is to slide a hemispherical diamond indenter with a diameter of about 200 microns on the surface of the coating, continuously increasing the vertical load L through an automatic loading mechanism in the process, when L reaches its critical load Lc, the coating and the substrate begin to peel off, the critical load Lc of the interface between the coating and the substrate, i.e. the minimum load required for the indenter to completely scratch through the coating and continuously peel it off from the substrate; meanwhile, the friction force F between the pressure head and the coating and the substrate correspondingly changes. At the moment, the coating can generate acoustic emission, an acoustic emission signal, the load variation and the tangential force variation during scratching are obtained through a sensor, the acoustic emission signal, the load variation and the tangential force variation are amplified and input into a computer, a measurement result is drawn into a graph through A/D conversion, an acoustic emission peak is correspondingly obtained at a critical load value Lc on an acoustic emission signal-load curve, and the critical load Lc is a criterion of the bonding strength of the coating and the matrix. The test parameters are: linear loading, loading load 200N, loading rate 99N/min, scratch speed 5mm/min, scratch length 5 mm.
The test method for oxidative weight gain was as follows:
the sample is placed in a muffle furnace and heated to 1000 ℃ under the air atmosphere, the temperature is kept for 1h, and then the sample is taken out and cooled to room temperature in the air. And weighing the weight of the sample before and after oxidation by adopting a high-precision electronic balance with the precision of 0.1mg, and calculating the oxidation weight gain of the sample.
The coefficient of friction test was carried out with reference to the international standard ASTM G99-2017.
Milling comparison of titanium alloy:
the processing mode is as follows: surface milling;
workpiece: a block member;
materials: ti6Al 4V;
blade type: SNGX1206ANN-MM 4;
cutting conditions are as follows: cutting at 100m/min, feeding at 0.2mm/z, cutting at 1mm depth and 60mm cutting width ae, and dry cutting;
the measurement results of the wear VB (unit mm) of the flank face of the blade after cutting for different time are shown in Table 2, and the wear of the flank face of the blade is measured by an OLYMPUS SZ61 optical super depth of field microscope with a scale.
TABLE 2 comparison of flank wear for 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 insert coated with the composite coating of the present application was greatly improved. High-temperature alloy milling comparison:
the processing mode is as follows: surface milling;
workpiece: a block member;
materials: GH 7192;
blade type: SNGX1206ANN-MM 4;
cutting conditions are as follows: cutting at a speed of 80m/min, feeding at 0.25mm/z, cutting at a depth of 1mm and a cutting width ae of 60mm, and performing dry cutting;
the measurement results of the wear VB (unit mm) of the flank face of the blade after cutting for different time are shown in Table 3, and the wear of the flank face of the blade is measured by an OLYMPUS SZ61 optical super depth of field microscope with a scale.
TABLE 3 comparison of flank wear of milling 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 above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (16)
1. A composite coating cutter is characterized by comprising a substrate and composite coatings 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, and a Ti-Al-B-N gradient layer with the boron content changing from low to high in a gradient manner is arranged between the first sub-coating and the second sub-coating; the first sub-coating is Ti1-xAlxN layer, the second sub-coating is TiaAlbBcN layers; the highest boron content in the gradient layer is not higher than the boron content of the second subcoating.
2. The composite coated cutting tool according to claim 1, wherein the Ti is1-xAlxIn the N layer, x is more than or equal to 0.70 and less than or equal to 0.90; the TiaAlbBcIn the N layers, a + b + c is 1, 0<a≤0.15，0.65≤b≤0.80。
3. A composite coated cutting tool according to claim 1, wherein the phase composition of the first sub-coating comprises face centered cubic fcc-TiN, face centered cubic fcc-AlN and close packed hexagonal hcp-AlN with a volume fraction of fcc-AlN of not less than 80%, said fcc-AlN having the following crystal orientation relationship: 0.5<R is less than or equal to 1, wherein: r is ═ Ifcc-AlN(111)/(Ifcc-AlN(111)+Ifcc-AlN(220))。
4. The composite coated cutting tool according to claim 1, wherein the phase composition of the second sub-coating comprises fcc-TiN, fcc-AlN, hcp-AlN and a non-crystalline a-BN, and wherein the volume fraction of fcc-AlN is not less than 75% and the volume fraction of a-BN is 5 to 15%.
5. The composite coated cutting tool according to claim 1, wherein the total thickness of the composite coating is 5.0 to 25.0 μm, preferably 10.0 to 15.0 μm, the thickness of the first sub-coating is 3.0 to 10.0 μm, preferably 5.0 to 8.0 μm, the thickness of the second sub-coating 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.
6. The composite coated cutting tool according to claim 1, wherein the composite coating further comprises a bonding layer deposited between the substrate surface and the first sub-coating, the bonding layer being one or more of Ti, TiN, TiC, TiCN, preferably TiN, the bonding layer having a thickness of 0.2-1.5 μm.
7. The composite coated cutting tool of claim 1 wherein a surface layer is deposited on the surface of said second subcoat, said surface layer being formed by removing said TiaAlbBcCoating composition except N layers.
8. A composite coated tool according to claim 1, characterized in that the surface layer is TiAlN, TiN, TiBN, TiB2One or more of TiC, TiCN, TiAlSiN, TiSiN, Ti and TiBCN, preferably TiB2And the thickness of the surface layer is 0.5 to 3.0 μm, preferably 1.0 to 2.0 μm.
9. The preparation method of the composite coating cutter is characterized in that the composite coating in the composite coating cutter comprises H through adopting a chemical vapor deposition technology under the conditions of 700-1000 ℃ and 4-1000 mbar2、TiCl4、AlCl3、NH3、N2、BCl3Ar is used as a raw material and is formed by sequentially depositing on the surface of a substrate; the composite coating includes a bonding layer, a first subcoat, a gradient layer, and a second subcoat.
10. The method as claimed in claim 9, wherein the bonding layer is formed by chemical vapor deposition to include TiCl at 850-950 ℃ and 50-200 mbar4、N2、H2Is obtained by chemical reaction on the surface of the substrate.
11. The method for preparing a composite coated cutting tool according to claim 10, wherein the first sub-coating is formed by chemical vapor deposition at 700-900 ℃ and 4-30 mbar to include H2、TiCl4、AlCl3、NH3、N2Ar is a raw material and is obtained by a chemical reaction on the surface of the bonding layer.
12. The method of claim 11, wherein the gradient layer is formed by chemical vapor deposition at 700-900 ℃ under 4-30 mbar to include H2、TiCl4、AlCl3、BCl3、NH3、N2Ar as raw material and gradually increasing BCl3Is obtained by chemical reaction at the surface of the first sub-coating.
13. The method for preparing a composite coated cutting tool according to claim 12, wherein the second sub-coating is formed by chemical vapor deposition to include H at 700-900 ℃ under 4-30 mbar2、TiCl4、AlCl3、BCl3、NH3、N2Ar is a raw material and is obtained by chemical reaction on the surface of the gradient layer.
14. The method of claim 13, wherein the composite coating further comprises a surface layer formed by chemical vapor deposition at 750-1000 deg.CUnder the condition of 50-1000 mbar, to include H2、TiCl4、BCl3Ar is used as a raw material and is obtained by chemical reaction on the surface of the second sub-coating.
15. A method of making a composite coated cutting tool as claimed in any one of claims 8 to 14, wherein the material of the substrate is one of cemented carbide, high speed steel, cermet, polycrystalline diamond, cubic boron nitride.
16. Use of a composite coated tool according to any of claims 1-8 for high speed dry cutting of any of titanium alloys, nickel based superalloys, heat resistant stainless steels.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100119315A1 (en) * | 2007-04-02 | 2010-05-13 | Ceratizit Austria Gesellschaft M.B.H. | Multilayer cvd coating |
| CN101952482A (en) * | 2008-02-21 | 2011-01-19 | 山高刀具公司 | Multilayered coated cutting tool |
| WO2017136969A1 (en) * | 2016-02-11 | 2017-08-17 | 广东工业大学 | Boron nitride composite coating, graded structure ultrafine hard alloy cutting tool with the composite coating, and method for manufacturing same |
| CN107974670A (en) * | 2017-11-10 | 2018-05-01 | 苏州苏硬表面技术有限公司 | A kind of process for the processing of tool surface coating |
| CN110158046A (en) * | 2019-07-02 | 2019-08-23 | 富耐克超硬材料股份有限公司 | Composite coating, self-lubricating composite coating cutter and preparation method thereof |
-
2021
- 2021-12-06 CN CN202111475991.5A patent/CN114196940B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100119315A1 (en) * | 2007-04-02 | 2010-05-13 | Ceratizit Austria Gesellschaft M.B.H. | Multilayer cvd coating |
| CN101952482A (en) * | 2008-02-21 | 2011-01-19 | 山高刀具公司 | Multilayered coated cutting tool |
| WO2017136969A1 (en) * | 2016-02-11 | 2017-08-17 | 广东工业大学 | Boron nitride composite coating, graded structure ultrafine hard alloy cutting tool with the composite coating, and method for manufacturing same |
| CN107974670A (en) * | 2017-11-10 | 2018-05-01 | 苏州苏硬表面技术有限公司 | A kind of process for the processing of tool surface coating |
| CN110158046A (en) * | 2019-07-02 | 2019-08-23 | 富耐克超硬材料股份有限公司 | Composite coating, self-lubricating composite coating cutter and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 孙丽丽;杨会生;成浩;汪爱英;: "占空比对中频磁控溅射(Al,Ti)N周期性多层膜组织与性能的影响" * |
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| CN114836754A (en) * | 2022-04-27 | 2022-08-02 | 赣州澳克泰工具技术有限公司 | Coated cutting tool and preparation method thereof |
| CN114836754B (en) * | 2022-04-27 | 2023-04-28 | 赣州澳克泰工具技术有限公司 | Coated cutting tool and preparation method thereof |
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