CN114672786B - High-temperature oxidation resistant self-lubricating multilayer coating cutter and preparation method thereof - Google Patents
High-temperature oxidation resistant self-lubricating multilayer coating cutter and preparation method thereof Download PDFInfo
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- CN114672786B CN114672786B CN202210263107.XA CN202210263107A CN114672786B CN 114672786 B CN114672786 B CN 114672786B CN 202210263107 A CN202210263107 A CN 202210263107A CN 114672786 B CN114672786 B CN 114672786B
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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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- 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
- C23C16/308—Oxynitrides
Abstract
The invention provides a high-temperature oxidation resistant self-lubricating multilayer coating cutter and a preparation method thereof, wherein the cutter comprises a substrate and a multilayer coating deposited on the surface of the substrate by adopting a Chemical Vapor Deposition (CVD) method, and the multilayer coating comprises a first subcoat Ti a Al b Si c N(a+b+c＝1，0<a is equal to or less than 0.15,0.65, b is equal to or less than 0.80,0.05, c is equal to or less than 0.20) and a second subcoat Ti h Al i Si j O k N 1‑k (h+i+j＝1，0<h is more than or equal to 0.20,0.50, i is more than or equal to 0.70,0.05, j is more than or equal to 0.20,0.20, k is more than or equal to 0.80), and a gradient layer Ti-Al-Si-O-N having an oxygen content which changes from low to high gradient and being arranged between the first sub-coating layer and the second sub-coating layer, and the highest oxygen content in the gradient layer is not higher than the oxygen content of the second subcoat. The invention aims to provide a coated cutting tool with high-temperature oxidation resistance, self-lubrication, high hardness and high bonding strength and a preparation method thereof.
Description
Technical Field
The invention belongs to the field of cutter preparation, and particularly relates to a high-temperature oxidation resistant self-lubricating multilayer coating cutter and a preparation method thereof.
Background
Modern cutting processing requires high efficiency and environmental protection, little or no cooling liquid, and high-speed dry cutting is increasingly demanded. 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 nickel-based superalloy, the heat-resistant stainless steel and other materials have high strength, the materials are easy to be processed and hardened during cutting, the surfaces of the cutters are easy to generate accumulated chips, and the cutter has serious bonding abrasion. 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 have high self-lubricating property, wear resistance and high-temperature oxidation resistance.
Si element is doped on the basis of Physical Vapor Deposition (PVD) TiAlN coating to form TiAlSiN coating, so that the oxidation resistance and wear resistance of the TiAlN coating can be remarkably improved, and the TiAlSiN coating has been successfully applied to cutting processing of materials such as stainless steel, alloy steel and the like. O element is doped on the basis of PVD TiAlSiN to form a TiAlSiON coating, so that the oxidation resistance and self-lubricity of the TiAlSiN coating can be further improved, but the hardness of the coating is generally reduced, and the wear resistance of the coating is reduced. Therefore, the PVD method for preparing the TiAlSiN and TiAlSiON multilayer coating can exert the synergistic effect of the wear resistance of the TiAlSiN coating and the oxidation resistance and self-lubricating property of the TiAlSiON coating, and the multilayer coating has better comprehensive performance than a single-layer coating.
Existing PVD tiaalsin and tiaalsion coatings tend to have hcp-AlN phases in the coating when the Al content is high (e.g., al >67at.%, ti+al+si=100 at.%), thereby reducing the hardness of the coating. In addition, when the thickness of PVD TiAlSiN and TiAlSiON coatings is large (e.g., >6.0 μm), the internal stress of the coating is large, which easily causes spalling of the coating, and the bonding strength of the coating is low.
Disclosure of Invention
In view of the above-described drawbacks of the prior art, an object of the present invention is to provide a coated cutting tool having high temperature oxidation resistance, capable of self-lubrication, high hardness and high bonding strength, and a method for manufacturing the same.
The application scheme provides a high temperature oxidation resistant self-lubricating multilayer coating cutter, includes: a substrate and a multilayer coating deposited on the surface of the substrate by a Chemical Vapor Deposition (CVD) method, wherein the multilayer coating comprises a first subcoat Ti a Al b Si c N(a+b+c＝1，0<a is equal to or less than 0.15,0.65, b is equal to or less than 0.80,0.05, c is equal to or less than 0.20) and a second subcoat Ti h Al i Si j O k N 1-k (h+i+j＝1，0<h≤0.20，0.50≤i≤0.70，0And a gradient layer Ti-Al-Si-O-N with oxygen content changing from low to high, wherein the highest oxygen content in the gradient layer is not higher than the oxygen content of the second sub-coating.
Further, the first sub-coating is of an amorphous coating nanocrystalline structure, the thickness of an amorphous phase is 6-10nm, and the phase comprises fcc-TiN of a face-centered cubic structure, fcc-AlN of a face-centered cubic structure, hcp-AlN of a close-packed hexagonal structure and a-Si of an amorphous phase x N y The method comprises the steps of carrying out a first treatment on the surface of the The fcc-AlN has a volume fraction of not less than 70% and 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) )。
Further, the second sub-coating layer has a structure of amorphous a-SiO x N y Coating Ti-Al-O-N nanocrystalline, wherein the grain size of the Ti-Al-O-N nanocrystalline is 2-20nm, and the ratio range of the atomic percent of oxygen and nitrogen in the second sub-coating is T=1.0-4.0.
Further, the total thickness of the multi-layer coating is 6.0-20.0 μm, the thickness of the first sub-coating is 2.5-10.0 μm, the thickness of the second sub-coating is 3.0-8.0 μm, and the thickness of the gradient layer is 0.50-2.0 μm.
Further, the multilayer coating further comprises a tie layer deposited between the substrate surface and the first sub-coating; the bonding layer is one or more of Ti, tiN, tiC, tiCN, tiAlN, preferably TiN and TiAlN, and the thickness of the bonding layer is 1.0-2.0 mu m.
Further, the multilayer coating further comprises a Ti-removing layer deposited on the surface of the second sub-coating layer h Al i Si j O k N 1-k An outer surface layer.
Further, the surface layer is one or more of Ti, tiN, tiC, tiCN, tiAlN, tiAlSiN, tiSiN, tiSiCN, preferably TiAlN, and the total thickness of the surface layer is 0.5 to 3.0 μm, preferably 1.0 to 2.0 μm.
Also provided is a method of preparing the above multilayer coated cutting tool, comprising:
adopting chemical vapor deposition technology, under the condition of 700-900 ℃ and 4-30 mbar, using H 2 、TiCl 4 、AlCl 3 、SiCl 4 、NH 3 、N 2 Ar is used as a raw material, and the first sub-coating is obtained through chemical reaction;
adopting chemical vapor deposition technology, under the condition of 700-900 ℃ and 4-30 mbar, using H 2 、TiCl 4 、AlCl 3 、SiCl 4 、CO 2 、NH 3 、N 2 Ar is used as raw material, and gradually increases CO 2 The flow ratio of the first sub-coating layer is subjected to chemical reaction on the surface of the first sub-coating layer to obtain the gradient layer;
adopting chemical vapor deposition technology, under the condition of 700-900 ℃ and 4-30 mbar, using H 2 、TiCl 4 、AlCl 3 、SiCl 4 、CO 2 、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 second sub-coating.
Further, the multilayer coating further comprises a bonding layer formed on the surface of the substrate, wherein the bonding layer comprises a TiN layer and a TiAlN coating; adopting chemical vapor deposition technology, and TiCl is used at the temperature of 850-950 ℃ and the pressure of 50-200 mbar 4 、N 2 、H 2 Depositing the TiN layer on the surface of the matrix for raw materials; by TiCl 4 、AlCl 3 、NH 3 、H 2 、N 2 Ar is used as a raw material, and the TiAlN coating is deposited on the surface of the TiN coating at the temperature of between 750 and 850 ℃ and under the condition of 4 to 20 mbar.
Further, the multilayer coating further comprises a surface layer formed on the surface of the second sub-coating; adopting chemical vapor deposition technology, and TiCl is adopted at the temperature of between 750 and 850 ℃ and under the condition of 4 to 20mbar 4 、AlCl 3 、NH 3 、H 2 、N 2 Ar is used as a raw material, and chemical reaction is carried out on the surface of the second sub-coating to obtain the surface layer.
The improvement of the present application brings the following advantages:
(1) According to the high-temperature oxidation resistant self-lubricating multilayer coating cutter, a Chemical Vapor Deposition (CVD) method is adopted to prepare TiAlSiN (first sub-coating) and TiAlSiON (second sub-coating), and the coating can not generate a low-hardness close-packed hexagonal hcp-AlN phase under the condition that the TiAlSiN and TiAlSiON prepared by the PVD method contain higher Al content.
(2) And because the CVD process deposits the coating at higher temperatures, metallurgical bonds are easily formed between the coating and between the coating and the substrate, and thus still have high bond strength at large coating thicknesses (e.g., >6.0 μm). Therefore, the TiAlSiN and TiAlSiON coatings prepared by the CVD method may possess higher wear resistance, oxidation resistance, and bond strength than PVD TiAlSiN and TiAlSiON coatings.
(3) The multi-layer coating is doped with oxygen element on the basis of CVD TiAlSiN, so that the oxidation resistance and self-lubricity of the coating can be further improved. Compared with PVD TiAlSiN and TiAlSiON multilayer coatings, the TiAlSiN and TiAlSiON multilayer coatings prepared by the CVD method have more excellent wear resistance, oxidation resistance, bonding strength and self-lubricating property.
(4) The atomic weight of each element in the first sub-coating layer and the second sub-coating layer of the multi-layer coating layer is further limited, and the hardness, the high-temperature oxidation resistance and the self-lubricating performance of the coating layer can be further improved within the limited range.
(5) A gradient layer of increasing oxygen content is prepared between the CVD TiAlSiN and TiAlSiON coatings, with the oxygen content increasing progressively from the first subcoat to the second subcoat. The bonding strength between the TiAlSiN and TiAlSiON coatings can be increased in one step. If the oxygen content of the gradient layer is higher than the oxygen content of the second subcoat, the effect of the gradient change to increase the bond strength of the coating will be lost.
(6) Further, a higher volume fraction of fcc-AlN (e.g., > 70%) is beneficial to increasing the hardness of the coating. R >0.5, namely the diffraction peak intensity of fcc-AlN (111) crystal face is larger than fcc-AlN (220 crystal face peak is strong), fcc-AlN has better toughness.
(7) Further, the ratio of atomic percent of oxygen and nitrogen in the second sub-coating ranges from t=1.0 to 4.0, and the oxygen content is set to be higher than the nitrogen content, when the oxygen content is higher (for example, T is equal to or greater than 1), the oxidation resistance and self-lubricity of the coating are better, but when the oxygen content is too high (for example, T is greater than 4), the compactness of the coating is easy to be reduced, and the bonding strength of the coating is low.
(8) When the CVD TiAlSiN coating is directly deposited on the surface of WC-Co-based hard alloy, co element in the matrix is easy to diffuse to the coating, and forms cobalt silicon compound (Co) with Si element in the coating 2 Si、CoSi、CoSi 2 ) The hardness and wear resistance of the coating are reduced. Thus, further, a bonding layer is deposited on the deposited CVD tiaalsin coating to prevent Co in the cemented carbide substrate from diffusing into the coating.
Drawings
FIG. 1 is a schematic diagram of a coating structure of a high temperature oxidation resistant, self-lubricating, multi-layer coated tool according to an embodiment of the present application;
wherein 100 is a substrate, 200 is a multi-layer coating, 201 is a bonding layer, 202 is a first sub-coating, 203 is a gradient layer, 204 is a second sub-coating, and 205 is a surface layer.
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.
As shown in fig. 1, the multi-layer coated cutting tool with high-temperature oxidation resistance and self-lubrication according to the embodiment of the application comprises a substrate 100 and a multi-layer coating 200, wherein the multi-layer coating comprises a first sub-coating 202, a gradient layer 203 and a second sub-coating 204 from inside to outside.
The substrate 100 may be made of one of cemented carbide, high-speed steel, cermet, etc. The substrate is 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 first subcoat may be of the formula Ti a Al b Si c N represents, wherein a+b+c=1, 0<a≤0.15，0.65≤b≤0.80C is more than or equal to 0.05 and less than or equal to 0.20. The first sub-coating layer is of an amorphous coated nanocrystalline structure, and the thickness of the amorphous phase is 6-10nm, preferably 5-8nm. The phase of the first sub-coating comprises fcc-TiN with face-centered cubic structure, fcc-AlN with face-centered cubic structure, hcp-AlN with close-packed hexagonal structure, amorphous phase a-Si x N y . Wherein the volume fraction of fcc-AlN is not less than 70%, preferably not less than 80%, and 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)), in the formula I fcc-AlN(111) And I fcc AlN (220) is formed by using 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. The thickness of the first subcoat is 2.5 to 10.0 μm, preferably 6.0 to 8.0 μm.
The second subcoat may be of the formula Ti h Al i Si j O k N 1-k Represents, where h+i+j=1, 0<h is less than or equal to 0.20,0.50, i is less than or equal to 0.70,0.05, j is less than or equal to 0.20,0.20, and k is less than or equal to 0.80. The second sub-coating is amorphous a-SiO x N y Coating Ti-Al-O-N nanocrystalline structure. Amorphous a-SiO x N y The thickness is 1 to 10nm, preferably 2 to 8nm. The grain size of the Ti-Al-O-N nanocrystalline is 2-20nm, preferably 5-15 nm. The atomic percent of oxygen and nitrogen, i.e. the ratio of O/N, in the second subcoat ranges from t=1.0 to 4.0, preferably t=2.0 to 3.0. The thickness of the second subcoat is 3.0 to 8.0 μm, preferably 4.0 to 6.0 μm.
The gradient layer may be represented by the general formula Ti-Al-Si-O-N, the oxygen content in the gradient layer varies in a gradient from low to high from inside to outside, and the highest oxygen content in the gradient layer is not higher than the oxygen content of the second sub-coating.
As an example, the multilayer coating further comprises a tie layer 201 between the substrate surface and the first sub-coating and an outermost top coating 205. The bonding layer is one or more of Ti, tiN, tiC, tiCN, tiAlN, preferably TiN and TiAlN. The thickness of the bonding layer is 1.0 to 2.0. Mu.m, preferably 1.2 to 1.8. Mu.m. The surface layer is deposited on the surface of the second sub-coating layer, the surface layer is one or more of Ti, tiN, tiC, tiCN, tiAlN, tiAlSiN, tiSiN, tiSiCN, preferably TiAlN, and the total thickness of the surface layer is 0.5-3.0 μm, preferably 1.0-2.0 μm.
The embodiment of the application provides a method for preparing a multi-layer coating cutter, which comprises the following steps:
s2: adopting chemical vapor deposition technology, under the condition of 700-900 ℃ and 4-30 mbar, using H 2 、TiCl 4 、AlCl 3 、SiCl 4 、NH 3 、N 2 Ar is used as a raw material, and a first sub-coating is obtained through chemical reaction;
s3: adopting chemical vapor deposition technology, under the condition of 700-900 ℃ and 4-30 mbar, using H 2 、TiCl 4 、AlCl 3 、SiCl 4 、CO 2 、NH 3 、N 2 Ar is used as raw material, and gradually increases CO 2 And (3) carrying out chemical reaction on the surface of the first sub-coating to obtain a gradient layer.
S4: adopting chemical vapor deposition technology, under the condition of 700-900 ℃ and 4-30 mbar, using H 2 、TiCl 4 、AlCl 3 、SiCl 4 、CO 2 、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 a second sub-coating.
As one embodiment, the multilayer coating further comprises a bonding layer comprising a TiN layer and a TiAlN coating; the method further comprises the following steps of preparing a bonding layer before the step S2:
s1: adopting chemical vapor deposition technology, and TiCl is used at the temperature of 850-950 ℃ and the pressure of 50-200 mbar 4 、N 2 、H 2 Depositing a TiN layer on the surface of the substrate for raw materials; by TiCl 4 、AlCl 3 、NH 3 、H 2 、N 2 Ar is used as a raw material, and a TiAlN coating is deposited on the surface of the TiN coating at the temperature of between 750 and 850 ℃ and under the condition of 4 to 20 mbar.
And the multilayer coating further comprises a surface layer, and the step of preparing the surface layer further comprises the following steps of:
s5: adopting chemical vapor deposition technology, and Ti is adopted at the temperature of between 750 and 850 ℃ and under the condition of 4 to 20mbarCl 4 、AlCl 3 、NH 3 、H 2 、N 2 Ar is used as a raw material, and chemical reaction is carried out on the surface of the second sub-coating to obtain the surface layer.
Example 1
The matrix is WC-Co-based hard alloy, and the bonding layer is TiN+Ti 0.20 Al 0.80 N, the first sub-coating is Ti 0.10 Al 0.75 Si 0.15 The gradient layer is Ti-Al-Si-O-N coating with oxygen content of 0-60 at%, and the second sub-coating is Ti 0.10 Al 0.75 Si 0.15 O 0.75 N 0.25 The surface layer is Ti 0.20 Al 0.80 The preparation method of each layer is as follows:
(1) Bonding layer TiN, deposition temperature 900 ℃, deposition pressure 100mbar, reaction gas TiCl 4 、N 2 、H 2 The purity of each gas is more than 95%, preferably more than 99.99%, the deposition time is 30min, and the thickness of the coating is 0.5 mu m;
(2) Bonding layer Ti 0.20 Al 0.80 N, deposition temperature 800 ℃, deposition pressure 10mbar, reaction gas TiCl 4 、AlCl 3 、NH 3 、N 2 、H 2 The purity of each gas is more than 95%, preferably more than 99.99%, the deposition time is 30min, and the thickness of the coating is 1.0 mu m;
(3) First sub-coating layer Ti 0.10 Al 0.75 Si 0.15 N, deposition temperature 800 ℃, deposition pressure 20mbar, reaction gas H 2 、TiCl 4 、AlCl 3 、SiCl 4 、NH 3 、N 2 Ar, the purity of each gas is more than 95%, preferably more than 99.99%, the deposition time is 240min, and the thickness of the coating is 8.0 μm;
(4) Gradient layer Ti-Al-Si-O-N layer, deposition temperature 800 ℃, deposition pressure 20mbar, reaction gas H 2 、TiCl 4 、AlCl 3 、SiCl 4 、NH 3 、CO 2 、N 2 、Ar，CO 2 The gas proportion of each gas is gradually increased, the purity of each gas is more than 95 percent, preferably more than 99.99 percent, the deposition time is 60 minutes, and the thickness of the coating is 1.5 mu m;
(5) Second sub-coating layer Ti 0.10 Al 0.75 Si 0.15 O 0.75 N 0.25 Deposition temperature 800 ℃, deposition pressure 20mbar, reaction gas H 2 、TiCl 4 、AlCl 3 、SiCl 4 、NH 3 、CO 2 、N 2 Ar, the purity of each gas is greater than 95%, preferably greater than 99.99%, the deposition time is 180min, and the coating thickness is 6.0 μm.
(6) Surface layer Ti 0.20 Al 0.80 N, deposition temperature 800 ℃, deposition pressure 10mbar, reaction gas TiCl 4 、AlCl 3 、NH 3 、N 2 、H 2 The purity of each gas is greater than 95%, preferably greater than 99.99%, the deposition time is 60 minutes, and the coating thickness is 1.5 μm.
Comparative example 1
PVD Ti 0.3 Al 0.6 Si 0.1 N+Ti 0.3 Al 0.6 Si 0.1 O 0.7 N 0.3 The multilayer coating is prepared by adopting a multi-arc ion plating technology, and the specific method is as follows:
(1)Ti 0.3 Al 0.6 Si 0.1 n layer, alloy target Ti/Al/si=25/65/10 (atomic ratio), deposition temperature 550 ℃, deposition pressure 8.0×10 -2 mbar, let in N 2 (purity 99.99%), deposition time was 360min, and coating thickness was 10. Mu.m.
(2)Ti 0.3 Al 0.6 Si 0.1 O 0.7 N 0.3 Layer, alloy target Ti/Al/si=25/65/10 (atomic ratio), deposition temperature 550 ℃, deposition pressure 8.0×10 -2 mbar, gas inlet ratio N 2 /O 2 =1:3 (purity 99.99%), deposition time 180min, coating thickness 5 μm.
Comparative example 2
CVD Ti 0.20 Al 0.80 N/Ti 0.10 Al 0.75 Si 0.15 N multilayer coating, its preparation method is as follows:
(1)Ti 0.20 Al 0.80 n layer, deposition temperature 800 ℃, deposition pressure 10mbar, reaction gas H 2 、TiCl 4 、AlCl 3 、NH 3 、N 2 Ar, purity of each gas is greater than 99.99%, deposition time 270min, coating thickness 10 μm.
(2)Ti 0.10 Al 0.75 Si 0.15 N layer, deposition temperature 800 ℃, deposition pressure 20mbar, reaction gas H 2 、TiCl 4 、AlCl 3 、SiCl 4 、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
CVD TiN/MT-TiCN/TiAlOCN/Al 2 O 3 The preparation method of the multilayer coating comprises the following steps:
(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 60 minutes, and the thickness of the coating is 1.0 mu m;
(2) MT-TiCN layer, deposition temperature 880 ℃, deposition pressure 80mbar, reaction gas H 2 、TiCl 4 、CH 3 CN、N 2 The purity of each gas is more than 99.99 percent, the deposition time is 300 minutes, and the thickness of the coating is 7.5 mu m;
(3) TiAlOCN coating, deposition temperature 950 ℃, deposition pressure 70mbar, reaction gas H 2 、TiCl 4 、AlCl 3 、CH 4 、CO、N 2 The purity of each gas is more than 99.99 percent, the deposition time is 60 minutes, and the thickness of the coating is 1.5 mu m;
(4)Al 2 O 3 coating, deposition temperature 1000 ℃, deposition pressure 60mbar, reaction gas H 2 、AlCl 3 、CO 2 、H 2 S, the purity of each gas is more than 99.99%, the deposition time is 320min, and the thickness of the coating is 8.0 mu m.
Table 1 shows the mechanical properties of example 1, comparative example 2 and comparative example 3.
Table 1 mechanical property comparison
As can be seen from the comparison of the data in Table 1, the multi-layer coated blade prepared by the embodiment of the application is higher than other comparative samples in hardness, bonding strength and friction coefficient, and the multi-layer coated cutting tool provided by the application has more excellent hardness, bonding strength and self-lubricating performance compared with the coated cutting tool in the prior art. And the data of the multilayer coating cutter on the oxidation weight increment is only inferior to that of comparative example 3, which shows that the multilayer coating cutter provided by the application exceeds most of coating cutters in the prior art on the high-temperature-resistant and oxidation-resistant performance.
The hardness test method is as follows
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 is as follows
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 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.
Heat-resistant stainless steel turning comparison
The processing mode is as follows: continuous dry turning
Materials: 347H
Blade type: CNMG120408-MC3
Cutting conditions: cutting speed 120m/min, feeding 0.3mm/z, cutting depth 1.5mm
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 |
| Example 1 | 0.06 | 0.11 | 0.18 | 0.25 |
| Comparative example 1 | 0.12 | 0.23 | 0.30 | -- |
| Comparative example 2 | 0.08 | 0.19 | 0.25 | 0.40 |
| Comparative example 3 | 0.12 | 0.20 | 0.26 | 0.35 |
As can be seen from the comparison of the data in Table 2, the multilayer coated cutting tool prepared by the embodiment of the application has the lowest abrasion loss in all samples no matter in short-time (2.2 min) cutting or long-time (22.2 min) cutting, which indicates that the multilayer coated cutting tool provided by the application has higher and stronger abrasion resistance compared with the coated cutting tool in the prior art.
Superalloy milling comparison
The processing mode is as follows: continuous dry turning
Materials: GH7192
Blade type: CNMG120408-MC3
Cutting conditions: cutting speed 40m/min, feeding 0.2mm/z, cutting depth 1.0mm
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 1 | 0.09 | 0.17 | 0.20 | 0.31 |
| Comparative example 1 | 0.13 | 0.31 | -- | -- |
| Comparative example 2 | 0.12 | 0.19 | 0.28 | 0.40 |
| Comparative example 3 | 0.18 | 0.25 | 0.35 | -- |
As can be seen from the comparison of the data in Table 3, the abrasion loss of the rear tool face of the multi-layer coated tool prepared by the embodiment of the application is smaller than that of other comparison samples. This advantage is more apparent from the comparison of example 1 with comparative example 3 and comparative example 1, the longer the use time. These data fully demonstrate that the multi-layered coated insert provided herein provides a substantial improvement in service life over prior art coated tools.
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 (9)
1. A high temperature oxidation resistant, self-lubricating, multilayer coated cutting tool comprising a substrate and a multilayer coating deposited on the surface of the substrate by a Chemical Vapor Deposition (CVD) process, the multilayer coating comprising:
first sub-coating layer Ti a Al b Si c N, wherein a+b+c=1, 0<a is more than or equal to 0.15,0.65, b is more than or equal to 0.80,0.05, c is more than or equal to 0.20; the first sub-coating is of an amorphous coating nanocrystalline structure, the thickness of an amorphous phase is 6-10nm, and the phase comprises fcc-TiN, fcc-AlN, hcp-AlN and a-Si x N y The method comprises the steps of carrying out a first treatment on the surface of the The fcc-AlN has a volume fraction of not less than 70% and 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) ) The method comprises the steps of carrying out a first treatment on the surface of the And
second sub-coating layer Ti h Al i Si j O k N 1-k Where h+i+j=1, 0<h is less than or equal to 0.20,0.50, i is less than or equal to 0.70,0.05, j is less than or equal to 0.20,0.20, and k is less than or equal to 0.80; the second sub-coating layer has a structure of amorphous a-SiO x N y Coating Ti-Al-O-N nanocrystalline, wherein the grain size of the Ti-Al-O-N nanocrystalline is 2-20nm, and the ratio range T=1.0-4.0 of the atomic percentage of oxygen and nitrogen in the second sub-coating; and
the gradient layer is arranged between the first sub-coating and the second sub-coating, the oxygen content of the gradient layer is changed in a gradient manner from low to high, and the highest oxygen content in the gradient layer is not higher than the oxygen content of the second sub-coating.
2. The multilayer coated tool according to claim 1, wherein the total thickness of the multilayer coating is 6.0-20.0 μm, the thickness of the first subcoat is 2.5-10.0 μm, the thickness of the second subcoat is 3.0-8.0 μm, and the thickness of the gradient layer is 0.50-2.0 μm.
3. The multilayer coated tool of claim 1, wherein the multilayer coating further comprises a tie layer deposited between the substrate surface and the first subcoat; the bonding layer is one or more of Ti, tiN, tiC, tiCN, tiAlN, and the thickness of the bonding layer is 1.0-2.0 mu m.
4. The multilayer coated tool of claim 3, wherein the multilayer coating further comprises Ti-removing deposited on the surface of the second subcoat h Al i Si j O k N 1-k An outer surface layer.
5. The multilayer coated cutting tool according to claim 4, wherein the surface layer is one or more of Ti, tiN, tiC, tiCN, tiAlN, tiAlSiN, tiSiN, tiSiCN and the total thickness of the surface layer is 0.5-3.0 μm.
6. The multilayer coated cutting tool according to claim 5, wherein the surface layer is TiAlN and the total thickness of the surface layer is 1.0-2.0 μm.
7. A method of making the multilayer coated tool of any one of claims 1-6, comprising:
adopting a chemical vapor deposition technology, and under the conditions of 700-900 ℃ and 4-30 mbar, using H 2 、TiCl 4 、AlCl 3 、SiCl 4 、NH 3 、N 2 Ar is used as a raw material, and the first sub-coating is obtained through chemical reaction;
adopting a chemical vapor deposition technology, and under the conditions of 700-900 ℃ and 4-30 mbar, using H 2 、TiCl 4 、AlCl 3 、SiCl 4 、CO 2 、NH 3 、N 2 Ar is used as raw material, and gradually increases CO 2 The flow ratio of the first sub-coating layer is subjected to chemical reaction on the surface of the first sub-coating layer to obtain the gradient layer;
adopting a chemical vapor deposition technology, and under the conditions of 700-900 ℃ and 4-30 mbar, using H 2 、TiCl 4 、AlCl 3 、SiCl 4 、CO 2 、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 second sub-coating.
8. The method of claim 7, wherein the multilayer coating further comprises a bonding layer formed on the surface of the substrate, the bonding layer comprising a TiN layer and a TiAlN coating; adopting chemical vapor deposition technology, and TiCl under the conditions of 850-950 ℃ and 50-200 mbar 4 、N 2 、H 2 Depositing the TiN layer on the surface of the matrix for raw materials; by TiCl 4 、AlCl 3 、NH 3 、H 2 、N 2 Ar is used as a raw material, and the TiAlN coating is deposited on the surface of the TiN coating at the temperature of 750-850 ℃ and under the condition of 4-20 mbar.
9. The method of claim 8, wherein the multilayer coating further comprises a skin layer formed on a surface of the second sub-coating; adopting chemical vapor deposition technology, and TiCl is adopted at the temperature of 750-850 ℃ and the pressure of 4-20 mbar 4 、AlCl 3 、NH 3 、H 2 、N 2 Ar is used as a raw material, and chemical reaction is carried out on the surface of the second sub-coating to obtain the surface layer.
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