CN116180006B - TiAlN/CrAlLaBN composite coating, preparation method thereof and cutter - Google Patents
TiAlN/CrAlLaBN composite coating, preparation method thereof and cutter Download PDFInfo
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- CN116180006B CN116180006B CN202310083759.XA CN202310083759A CN116180006B CN 116180006 B CN116180006 B CN 116180006B CN 202310083759 A CN202310083759 A CN 202310083759A CN 116180006 B CN116180006 B CN 116180006B
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- 238000000576 coating method Methods 0.000 title claims abstract description 160
- 239000011248 coating agent Substances 0.000 title claims abstract description 144
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 229910010037 TiAlN Inorganic materials 0.000 title claims abstract 29
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 70
- 230000007704 transition Effects 0.000 claims abstract description 53
- 239000010410 layer Substances 0.000 claims description 166
- 238000000151 deposition Methods 0.000 claims description 93
- 230000008021 deposition Effects 0.000 claims description 57
- 238000005530 etching Methods 0.000 claims description 36
- 229910010038 TiAl Inorganic materials 0.000 claims description 31
- 238000004140 cleaning Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 10
- 238000007740 vapor deposition Methods 0.000 claims description 6
- 238000007733 ion plating Methods 0.000 claims description 4
- 238000005240 physical vapour deposition Methods 0.000 claims description 4
- 229910000997 High-speed steel Inorganic materials 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims 3
- 239000007789 gas Substances 0.000 description 71
- 230000000052 comparative effect Effects 0.000 description 28
- 239000011651 chromium Substances 0.000 description 25
- 238000005498 polishing Methods 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 22
- 239000010936 titanium Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000005520 cutting process Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910003460 diamond Inorganic materials 0.000 description 8
- 239000010432 diamond Substances 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 238000004506 ultrasonic cleaning Methods 0.000 description 8
- 238000001771 vacuum deposition Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000000992 sputter etching Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 230000003139 buffering effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910019590 Cr-N Inorganic materials 0.000 description 1
- 229910019588 Cr—N Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QRRWWGNBSQSBAM-UHFFFAOYSA-N alumane;chromium Chemical compound [AlH3].[Cr] QRRWWGNBSQSBAM-UHFFFAOYSA-N 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
- B23B2228/08—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner applied by physical vapour deposition [PVD]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
- B23B2228/10—Coatings
- B23B2228/105—Coatings with specified thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
- B23B2228/36—Multi-layered
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention provides a TiAlN/CrAlLaBN composite coating, a preparation method thereof and a cutter, and relates to the technical field of coatings. The TiAlN/CrAlLaBN composite coating comprises a TiAlN binding layer, a TiAlN/CrAlLaBN transition layer and a CrAlLaBN top layer which are sequentially arranged on the surface of the substrate from inside to outside; through the combination of the three layers, the prepared composite coating has certain hardness, higher toughness and coating binding force, and excellent comprehensive performance, and can meet the requirement of subsequent severe application scenes. The invention also provides a preparation method of the TiAlN/CrAlLaBN composite coating.
Description
Technical Field
The invention belongs to the technical field of coatings, and relates to a TiAlN/CrAlLaBN composite coating, a preparation method thereof and a cutter.
Background
The cutter coating is deposited on the surface of the cutter, so that the cutting face of the cutter can be effectively protected, the abrasion is reduced, the service cycle of the cutter is prolonged, and meanwhile, the processing quality and the cutting efficiency can be improved. With the continuous progress of material science and manufacturing industry, the requirements of machining on cutting speed and cutting precision are higher and higher, and the cutter coating is also rapidly developed.
The titanium aluminum nitride (TiAlN) coating has the characteristics of low internal stress, high hardness, low heat conductivity, good high-temperature oxidation resistance, good red hardness and the like, and particularly the TiAlN hard coating with high aluminum content has excellent high-temperature oxidation resistance and red hardness, so that the TiAlN hard coating is suitable for high-speed cutting, but the service temperature of the TiAlN coating is generally not higher than 800 ℃, and the application of the TiAlN hard coating is limited to a certain extent. Cr element has a higher melting point and higher oxidation compactness than Ti element, so that Cr is used for replacing Ti to prepare a chromium aluminum nitride (CrAlN) coating, compared with the TiAlN coating, the CrAlN coating has better high-temperature oxidation resistance, smaller friction coefficient during cutting and better capability of removing scraps from a contact surface, but the CrAlN coating has lower toughness than the TiAlN coating and is decomposed at 900 ℃ due to instability of Cr-N bonds, and an intermediate phase Cr 2 N is formed, so that the performance of the coating is reduced, and the gradually severe turning scene is still difficult to meet.
In view of this, the present invention has been made.
Disclosure of Invention
Aiming at the defects and the shortcomings existing in the prior art, the invention aims to provide a TiAlN/CrAlLaBN composite coating, a preparation method thereof and a cutter. The TiAlN/CrAlLaBN composite coating is mainly composed of a TiAlN bonding layer, a TiAlN/CrAlLaBN transition layer and a CrAlLaBN top layer, and the prepared composite coating has certain hardness, higher toughness and coating binding force and excellent comprehensive performance, and can meet the requirement of subsequent severe application scenes.
In order to achieve the above purpose, the following technical scheme is adopted:
The invention provides a TiAlN/CrAlLaBN composite coating, which comprises a TiAlN binding layer, a TiAlN/CrAlLaBN transition layer and a CrAlLaBN top layer which are sequentially arranged on the surface of a substrate from inside to outside.
Furthermore, on the basis of the technical scheme, the TiAlN bonding layer comprises the following elements in percentage by atom: 16-23 at.% of Ti, 20-30 at.% of Al and 50-60 at.% of N;
preferably, the TiAlN bonding layer has a thickness of 0.5-1.5 μm.
Furthermore, on the basis of the technical scheme of the invention, the TiAlN/CrAlLaBN transition layer comprises the following elements in percentage by atom: 6 to 12at.% of Ti, 3 to 9at.% of Cr, 16 to 28at.% of Al, 0.1 to 0.5at.% of La, 0.7 to 3.5at.% of B and 50 to 60at.% of N;
preferably, the thickness of the TiAlN/CrAlLaBN transition layer is 0.2-0.5 mu m.
Furthermore, on the basis of the technical scheme of the invention, the CrAlLaBN top layer comprises the following elements in percentage by atom: 13-21 at.% of Cr, 15-25 at.% of Al, 0.3-1 at.% of La, 1.5-6.5 at.% of B and 50-60 at.% of N;
preferably, the CrAlLaBN top layer has a thickness of 1.5-2.5 μm.
Furthermore, on the basis of the technical scheme of the invention, the materials of the matrix comprise high-speed steel and/or hard alloy.
The invention also provides a preparation method of the TiAlN/CrAlLaBN composite coating, which comprises the following steps:
(a) Vapor depositing a TiAlN bonding layer on the surface of the substrate;
(b) Vapor depositing a TiAlN/CrAlLaBN transition layer on the surface of the TiAlN bonding layer;
(c) And carrying out vapor deposition CrAlLaBN on the surface of the TiAlN/CrAlLaBN transition layer to obtain the TiAlN/CrAlLaBN composite coating.
Further, on the basis of the above technical solution of the present invention, the vapor deposition method in the step (a), the step (b) and the step (c) is a physical vapor deposition method, preferably an arc ion plating method.
Furthermore, on the basis of the technical scheme, in the step (a), the deposition of the TiAlN bonding layer comprises at least the following process parameters: n 2 gas flow is 800-950 sccm, chamber gas pressure is 2-5 Pa, tiAl target current is 100-150A, workpiece support bias voltage is-80 to-120V, and deposition time is 30-90 min;
preferably, in the step (a), before depositing the TiAlN bonding layer, the step of cleaning and etching the substrate is further included.
Furthermore, on the basis of the technical scheme of the invention, in the step (b), the deposition of the TiAlN/CrAlLaBN transition layer comprises at least the following process parameters: n 2 gas flow is 800-950 sccm, chamber gas pressure is 2-5 Pa, tiAl target current is 100-150A, crAlLaB target current is 130-180A, workpiece support bias voltage is-100 to-140V, and deposition time is 5-15 min;
Preferably, crAlLaBN the top layer comprises at least the following process parameters: n 2 gas flow is 800-950 sccm, chamber gas pressure is 2-5 Pa, crAlLaB target current is 130-180A, workpiece support bias voltage is-140 to-180V, and deposition time is 90-150 min.
The invention also provides a cutter, which comprises a cutter substrate and the TiAlN/CrAlLaBN composite coating arranged on the surface of the cutter substrate or the TiAlN/CrAlLaBN composite coating prepared by adopting the preparation method of the TiAlN/CrAlLaBN composite coating.
Compared with the prior art, the technical scheme of the invention has at least the following technical effects:
(1) The invention provides a TiAlN/CrAlLaBN composite coating, which mainly comprises a TiAlN bonding layer, a TiAlN/CrAlLaBN transition layer and a CrAlLaBN top layer; the TiAlN bonding layer has good wettability with the substrate, has certain hardness, can play a supporting role on the top layer coating, has low stress in the TiAlN bonding layer, can improve the toughness of the composite coating, and improves the bonding force of the composite coating; the CrAlLaBN top layer can generate compact-structure (Al, cr) 2O3 on the surface of the coating at high temperature, prevent oxygen elements from diffusing inwards, slow down the oxidation speed of the coating, and B elements can form amorphous compounds at grain boundaries to wrap grains and prevent the grains from growing, so that the grains of the coating are refined, the compactness of the film layer is improved, and the hardness and the wear resistance of the coating are improved. The La element can play a role in solid solution strengthening, the toughness of the coating is synergistically improved while the hardness of the coating is further improved, and a compact oxide film can be formed on the surface of the coating at high temperature by the La element, so that the coating has the effects of improving the thermal stability and high-temperature oxidation resistance of the coating. The TiAlN/CrAlLaBN transition layer can enable the TiAlN bonding layer to be tightly bonded with the CrAlLaBN top layer, reduce residual stress at an interface, improve bonding force of the coating, play a role in buffering when the coating is in service, and improve comprehensive performance of the coating. Through the combination of the three layers, the prepared composite coating has certain hardness, higher toughness and coating binding force, and excellent comprehensive performance, and can meet the requirement of subsequent severe application scenes.
(2) The invention also provides a preparation method of the TiAlN/CrAlLaBN composite coating, and the coating prepared by the preparation method has compact structure, good mechanical property and strong binding force.
(3) The invention also provides a cutter, which comprises a cutter substrate and a TiAlN/CrAlLaBN composite coating arranged on the surface of the cutter substrate. In view of the advantages of the TiAlN/CrAlLaBN composite coating, the cutter comprising the TiAlN/CrAlLaBN composite coating is not easy to wear and has longer service life.
Drawings
FIG. 1 is a schematic illustration of a TiAlN/CrAlLaBN composite coating in one embodiment of the invention;
FIG. 2 is a graph of nose wear length for a tool employing various embodiments of the present invention and comparative coatings.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The process parameters for the specific conditions not noted in the examples below are generally as usual.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically disclosed in the present invention.
According to a first aspect of the invention, there is provided a TiAlN/CrAlLaBN composite coating, comprising a TiAlN binding layer, a TiAlN/CrAlLaBN transition layer and a CrAlLaBN top layer which are sequentially arranged on the surface of a substrate from inside to outside, wherein the specific structure is shown in figure 1.
Specifically, the TiAlN bonding layer is mainly a coating formed by Ti, al and N elements; crAlLaBN a top layer of a coating formed primarily of element Cr, al, la, B, N; located between the TiAlN bonding layer and the CrAlLaBN top layer is a transition layer formed by the TiAlN bonding layer and the CrAlLaBN top layer, namely a TiAlN/CrAlLaBN transition layer.
The TiAlN/CrAlLaBN composite coating mainly comprises a TiAlN bonding layer, a TiAlN/CrAlLaBN transition layer and a CrAlLaBN top layer. The TiAlN bonding layer has good wettability with the substrate, has certain hardness, can play a supporting role on the top layer coating, has low stress in the TiAlN bonding layer, can improve the toughness of the composite coating, and improves the bonding force of the composite coating; the CrAlLaBN top layer can generate compact-structure (Al, cr) 2O3 on the surface of the coating at high temperature, prevent oxygen elements from diffusing inwards, slow down the oxidation speed of the coating, and B elements can form amorphous compounds at grain boundaries to wrap grains and prevent the grains from growing, so that the grains of the coating are refined, the compactness of the coating is improved, and the hardness and the wear resistance of the coating are improved. The La element can play a role in solid solution strengthening, the toughness of the coating is synergistically improved while the hardness of the coating is further improved, and a compact oxide film can be formed on the surface of the coating at high temperature by the La element, so that the coating has the effects of improving the thermal stability and high-temperature oxidation resistance of the coating. The TiAlN/CrAlLaBN transition layer can enable the TiAlN bonding layer to be tightly bonded with the CrAlLaBN top layer, reduce residual stress at an interface, improve bonding force of the coating, play a role in buffering when the coating is in service, and improve comprehensive performance of the coating. Through the combination of the three layers, the prepared composite coating has certain hardness, higher toughness and coating binding force, and excellent comprehensive performance, and can meet the requirement of subsequent severe application scenes.
There is further optimization for the specific composition and thickness of the TiAlN binding layer.
As an alternative embodiment of the present invention, the TiAlN bonding layer comprises the following elements in atomic percentage, based on 100% of the TiAlN bonding layer: 16 to 23at.% of Ti, 20 to 30at.% of Al and 50 to 60at.% of N. Typical but non-limiting atomic percent Ti content is 16at.%, 17at.%, 18at.%, 19at.%, 20at.%, 21at.%, 22at.%, or 23at.%. Typical but non-limiting Al atomic percentage content is 20at.%, 21at.%, 22at.%, 24at.%, 25at.%, 26at.%, 28at.%, or 30at.%. Typical but non-limiting atomic percent amounts of N are 50at.%, 51at.%, 52at.%, 54at.%, 55at.%, 56at.%, 58at.%, or 60at.%.
As an alternative embodiment of the invention, the TiAlN binding layer has a thickness of 0.5-1.5 μm. Typical but non-limiting TiAlN junction layers have a thickness of 0.5 μm, 0.6 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.2 μm, 1.4 μm or 1.5 μm.
As an alternative embodiment of the present invention, the TiAlN/CrAlLaBN transition layer comprises the following elements in atomic percent, based on 100% of the TiAlN/CrAlLaBN transition layer: 6 to 12at.% of Ti, 3 to 9at.% of Cr, 16 to 28at.% of Al, 0.1 to 0.5at.% of La, 0.7 to 3.5at.% of B and 50 to 60at.% of N; typical but non-limiting atomic percent Ti content is 6at.%, 7at.%, 8at.%, 9at.%, 10at.%, 11at.%, or 12at.%. Typical but non-limiting atomic percentage content of Cr is 3at.%, 4at.%, 5at.%, 6at.%, 7at.%, 8at.%, or 9at.%. Typical but non-limiting Al atomic percentage contents are 16at.%, 18at.%, 20at.%, 21at.%, 22at.%, 24at.%, 25at.%, 26at.%, or 28at.%. Typical but non-limiting amounts of La by atomic percent are 0.1at.%, 0.2at.%, 0.3at.%, 0.4at.%, or 0.5at.%. Typical but non-limiting atomic percent content of B is 0.7at.%, 1at.%, 1.5at.%, 1.8at.%, 2.0at.%, 2.5at.%, 3.0at.%, 3.2at.%, or 3.5at.%. Typical but non-limiting atomic percent amounts of N are 50at.%, 51at.%, 52at.%, 54at.%, 55at.%, 56at.%, 58at.%, or 60at.%.
As an alternative embodiment of the invention, the thickness of the TiAlN/CrAlLaBN transition layer is 0.2-0.5 μm. The typical but non-limiting thickness of the TiAlN/CrAlLaBN transition layer is not too thick (the thickness is larger than 0.5 μm), the hardness of the composite coating can be reduced when the thickness is too thick, the service life of the coating is affected, the bonding effect of the TiAlN bonding layer and the CrAlLaBN top layer can be poor when the thickness of the TiAlN/CrAlLaBN transition layer is too thin (the thickness is smaller than 0.2 μm), the residual stress at the interface is high, and the comprehensive performance of the composite coating is affected.
As an alternative embodiment of the invention, the CrAlLaBN top layer comprises the following elements in atomic percent, based on CrAlLaBN top layer taken as 100%: 13-21 at.% of Cr, 15-25 at.% of Al, 0.3-1 at.% of La, 1.5-6.5 at.% of B and 50-60 at.% of N; typical but non-limiting atomic percent Cr content is 13at.%, 14at.%, 15at.%, 16at.%, 17at.%, 18at.%, 20at.%, or 21at.%. Typical but non-limiting Al atomic percentage content is 15at.%, 16at.%, 18at.%, 20at.%, 21at.%, 22at.%, 24at.%, or 25at.%. Typical but non-limiting amounts of La by atomic percent are 0.3at.%, 0.4at.%, 0.5at.%, 0.6at.%, 0.8at.%, 0.9at.%, or 1at.%. Typical but non-limiting atomic percent B content is 1.5at.%, 2.0at.%, 2.5at.%, 3.0at.%, 3.5at.%, 4.0at.%, 4.5at.%, 5.0at.%, 5.5at.%, 6.0at.% or 6.5at.%. Typical but non-limiting atomic percent amounts of N are 50at.%, 51at.%, 52at.%, 54at.%, 55at.%, 56at.%, 58at.%, or 60at.%.
As an alternative embodiment of the invention, crAlLaBN the top layer has a thickness of 1.5 to 2.5 μm. The CrAlLaBN top layer has a typical, but non-limiting, thickness of 1.5 μm, 1.8 μm, 2.0 μm, 2.2 μm, 2.4 μm, or 2.5 μm.
As an alternative embodiment of the invention, the material of the substrate comprises high-speed steel and/or cemented carbide.
According to a second aspect of the present invention, there is also provided a method for preparing the TiAlN/CrAlLaBN composite coating, comprising the steps of:
(a) Vapor depositing a TiAlN bonding layer on the surface of the substrate;
(b) Vapor depositing a TiAlN/CrAlLaBN transition layer on the surface of the TiAlN bonding layer;
(c) And carrying out vapor deposition CrAlLaBN on the surface of the TiAlN/CrAlLaBN transition layer to obtain the TiAlN/CrAlLaBN composite coating.
As an alternative embodiment of the present invention, in step (a), before depositing the TiAlN bonding layer, the step of cleaning and etching the substrate is further included.
And cleaning the substrate to remove impurities and pollutants on the surface, thereby obtaining good cleanliness. As an alternative embodiment of the invention, the surface of the substrate is polished by polishing cloth (matched with 0.5 μm or 1 μm diamond polishing liquid), then the polished substrate is respectively put into absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20-30 min (such as 20min, 22min, 25min, 28min or 30 min), and then is dried for 1-1.5 h at 100-120 ℃ (such as 100 ℃, 110 ℃ or 120 ℃).
After cleaning the substrate, an etching step is also performed. The oxide layer on the surface of the substrate can be removed by etching, so that the surface of the substrate is further cleaned and activated, and the bonding force between the coating and the substrate is improved. As an alternative implementation mode of the invention, a substrate is placed into a vacuum coating machine chamber, the vacuum is firstly pumped to 1X 10 -2～5×10-2 Pa, then heating is started, the temperature of the chamber is increased to 450-500 ℃, the temperature of the chamber is kept for 30-60 min after reaching the set temperature, the vacuum is pumped to 1-5X 10 -3 Pa, ar gas is introduced, the Ar gas flow is 150-220 sccm, the pressure of the chamber is controlled to be 0.3-1 Pa, an etching target (Cr target) is ignited, the etching target current is 90-130A, the bias voltage of a workpiece support is-120-180V, and the etching cleaning time is 80-120 min.
As an alternative embodiment of the present invention, the vapor deposition method in step (a), step (b) and step (c) is physical vapor deposition, and further preferably is an arc ion plating method.
The electric arc ion plating method has high ionization rate and high deposition rate, and the TiAlN/CrAlLaBN composite coating prepared by the method has more compact structure, better mechanical property and stronger binding force.
As an alternative embodiment of the present invention, in the step (a), the deposition of the TiAlN bonding layer includes at least the following process parameters: n 2 air flow is 800-950 sccm, chamber air pressure is 2-5 Pa, tiAl target current is 100-150A, workpiece support bias voltage is-80 to-120V, and deposition time is 30-90 min. Typical but non-limiting N 2 gas flows are 800sccm, 850sccm, 880sccm, 900sccm, 920sccm, or 950sccm, and typical but non-limiting chamber pressures are 2Pa, 3Pa, 4Pa, or 5Pa; typical but non-limiting TiAl target currents are 100A, 110A, 120A, 130A, 140A, or 150A; typical, but non-limiting, workpiece supports are biased at-80V, -90V, -100V, -110V, or-120V. Typical but non-limiting deposition times are 30min, 40min, 50min, 60min, 70min, 80min or 90min.
As an alternative embodiment of the present invention, in the step (b), the deposition of the TiAlN/CrAlLaBN transition layer includes at least the following process parameters: keeping the deposition atmosphere in the step 3 unchanged, wherein the gas flow of N 2 is 800-950 sccm, the chamber gas pressure is 2-5 Pa, the TiAl target current is 100-150A, the CrAlLaB target current is 130-180A, the bias voltage of the workpiece support is-100 to-140V, and the deposition time is 5-15 min. Typical but non-limiting N 2 gas flows are 800sccm, 850sccm, 880sccm, 900sccm, 920sccm, or 950sccm, and typical but non-limiting chamber pressures are 2Pa, 3Pa, 4Pa, or 5Pa; typical but non-limiting TiAl target currents are 100A, 110A, 120A, 130A, 140A, or 150A; typical but non-limiting CrAlLaB target currents are 130A, 140A, 150A, 160A, 170A, or 180A; typical, but non-limiting, workpiece supports are biased at-100V, -110V, -120V, -130V, or-140V. Typical but non-limiting deposition times are 5,7, 8, 10, 11, 13, 14 or 15 minutes.
As an alternative embodiment of the invention, in step (c), the deposition CrAlLaBN of the top layer comprises at least the following process parameters: n 2 gas flow is 800-950 sccm, chamber gas pressure is 2-5 Pa, crAlLaB target current is 130-180A, workpiece support bias voltage is-140 to-180V, and deposition time is 90-150 min. Typical but non-limiting N 2 gas flows are 800sccm, 850sccm, 880sccm, 900sccm, 920sccm, or 950sccm, and typical but non-limiting chamber pressures are 2Pa, 3Pa, 4Pa, or 5Pa; typical but non-limiting CrAlLaB target currents are 130A, 140A, 150A, 160A, 170A, or 180A; typical, but non-limiting, workpiece supports are biased at-140V, -150V, -160V, -170V, or-180V. Typical but non-limiting deposition times are 90min, 100min, 110min, 120min, 130min, 140min, or 150min.
By further limiting the technological parameters of the deposition process in the step (a), the step (b) and the step (c), the prepared composite coating has high hardness, good toughness, excellent comprehensive performance, strong coating binding force and good high-temperature oxidation resistance, can play a good role in protecting a tool nose during turning, and reduces tool nose abrasion.
According to a third aspect of the present invention, there is also provided a tool comprising a tool body and the above TiAlN/CrAlLaBN composite coating provided on the surface of the tool body.
In view of the advantages of the TiAlN/CrAlLaBN composite coating, the cutter comprising the TiAlN/CrAlLaBN composite coating is not easy to wear and has longer service life.
The present invention will be described in further detail with reference to specific examples and comparative examples.
Example 1
The embodiment provides a TiAlN/CrAlLaBN composite coating, which comprises a TiAlN binding layer, a TiAlN/CrAlLaBN transition layer and a CrAlLaBN top layer which are sequentially arranged on the surface of a substrate from inside to outside.
Wherein the TiAlN bonding layer comprises the following elements in atomic percent: ti19.2at.% Al 24.0at.% and N56.8at.% the TiAlN bonding layer has a thickness of 1.2 μm.
The TiAlN/CrAlLaBN transition layer comprises the following elements in atomic percent: ti9.9at.%, cr 8.6at.%, al 22.4at.%, la 0.2at.%, B1.5 at.% and N57.4at.%; the TiAlN/CrAlLaBN transition layer had a thickness of 0.3. Mu.m.
The CrAlLaBN top layer includes elements having the following atomic percent contents: 18.0at.% Cr, 21.3at.% Al, 0.5at.% La, 3.1at.% B, 57.1at.% N; crAlLaBN the top layer had a thickness of 2.2 μm.
The preparation method of the TiAlN/CrAlLaBN composite coating comprises the following steps:
(1) Cleaning a substrate: polishing the surface of a substrate by using polishing cloth (matched with a diamond polishing solution with the thickness of 1 mu m), respectively placing the polished substrate into absolute ethyl alcohol and deionized water for ultrasonic cleaning for 25min, taking out, and drying in an oven at 110 ℃ for 1h;
(2) Argon ion etching and cleaning: placing a substrate into a vacuum coating machine chamber, vacuumizing to 5X 10 -2 Pa, starting heating, heating the chamber to 480 ℃, keeping the temperature for 40min after the temperature of the chamber reaches a set temperature, vacuumizing to 5X 10 -3 Pa, introducing Ar gas, wherein the Ar gas flow is 200sccm, controlling the chamber gas pressure to 0.7Pa, igniting an etching target (Cr target), the etching target current is 100A, the bias voltage of a workpiece rotating frame is-150V, and the etching cleaning time is 100min;
(3) Depositing a TiAlN binding layer: closing Ar gas and an etching target, introducing N 2 gas, controlling the gas flow of N 2 to be 880sccm, controlling the gas pressure of a chamber to be 3Pa, igniting a TiAl (the atomic percentage content is Ti:45 at%, al:55 at%) target, the current of the TiAl target to be 135A, the bias voltage of a workpiece rotating frame to be-90V, and the deposition time to be 70min;
(4) Depositing a TiAlN/CrAlLaBN transition layer: keeping the deposition atmosphere of the step (3) unchanged, simultaneously igniting a TiAl target and a CrAlLaB (Cr: 42 at%, al:51 at%, la:1 at%, B:6 at%) target, depositing a TiAlN/CrAlLaBN transition layer, wherein the TiAl target current is 135A, the CrAlLaB target current is 150A, the workpiece rotating frame bias voltage is-120V, and the deposition time is 10min;
(5) Depositing CrAlLaBN a top layer: keeping the deposition atmosphere of the step (3) unchanged, closing and igniting the TiAl target, depositing CrAlLaBN top layer by using CrAlLaB target, wherein the current of the CrAlLaB target is 150A, the bias voltage of the workpiece support is 160V, the deposition time is 130min, closing CrAlLaB target and bias voltage after the deposition is finished, closing heating, closing N 2 gas, and taking out the substrate when the temperature of the chamber is reduced to room temperature, thus obtaining the TiAlN/CrAlLaBN composite coating.
Example 2
The embodiment provides a TiAlN/CrAlLaBN composite coating, which comprises a TiAlN binding layer, a TiAlN/CrAlLaBN transition layer and a CrAlLaBN top layer which are sequentially arranged on the surface of a substrate from inside to outside.
Wherein the TiAlN bonding layer comprises the following elements in atomic percent: ti16.9at.%, al 27.0at.% and N56.1at.% and the TiAlN bonding layer has a thickness of 0.7 μm.
The TiAlN/CrAlLaBN transition layer comprises the following elements in atomic percent: ti7.9at.%, cr 6.4at.%, al 26.3at.%, la 0.2at.%, B1.1 at.% and N58.1 at.%; the TiAlN/CrAlLaBN transition layer had a thickness of 0.5. Mu.m.
The CrAlLaBN top layer includes elements having the following atomic percent contents: cr14.1at.%, al 24.0at.%, la 0.4at.%, B3.7at.%, N57.8at.%; crAlLaBN the top layer had a thickness of 2.4 μm.
The preparation method of the TiAlN/CrAlLaBN composite coating comprises the following steps:
(1) Cleaning a substrate: polishing the surface of a substrate by using polishing cloth (matched with a diamond polishing solution with the thickness of 1 mu m), respectively placing the polished substrate into absolute ethyl alcohol and deionized water for ultrasonic cleaning for 25min, taking out, and drying in an oven at 110 ℃ for 1h;
(2) Argon ion etching and cleaning: placing a substrate into a vacuum coating machine chamber, vacuumizing to 5X 10 -2 Pa, starting heating, heating the chamber to 480 ℃, keeping the temperature for 40min after the temperature of the chamber reaches a set temperature, vacuumizing to 5X 10 -3 Pa, introducing Ar gas, wherein the Ar gas flow is 200sccm, controlling the chamber gas pressure to 0.7Pa, igniting an etching target (Cr target), the etching target current is 100A, the bias voltage of a workpiece rotating frame is-150V, and the etching cleaning time is 100min;
(3) Depositing a TiAlN binding layer: closing Ar gas and an etching target, introducing N 2 gas, controlling the gas flow of N 2 to be 880sccm, controlling the gas pressure of a chamber to be 3Pa, igniting a TiAl (the atomic percentage content is Ti:40 at%, al:60 at%) target, the current of the TiAl target to be 135A, the bias voltage of a workpiece rotating frame to be-90V, and the deposition time to be 45min;
(4) Depositing a TiAlN/CrAlLaBN transition layer: keeping the deposition atmosphere of the step (3) unchanged, simultaneously igniting a TiAl target and a CrAlLaB (Cr: 35at.%, al:58at.%, la:1at.%, B:6 at.%) target, depositing a TiAlN/CrAlLaBN transition layer, wherein the TiAl target current is 135A, the CrAlLaB target current is 150A, the workpiece rotating frame bias is-120V, and the deposition time is 15min;
(5) Depositing CrAlLaBN a top layer: keeping the deposition atmosphere of the step (3) unchanged, closing and igniting the TiAl target, depositing CrAlLaBN top layer by using CrAlLaB target, wherein the current of the CrAlLaB target is 150A, the bias voltage of the workpiece support is 160V, the deposition time is 140min, closing CrAlLaB target and bias voltage after the deposition is finished, closing heating, closing N 2 gas, and taking out the substrate when the temperature of the chamber is reduced to room temperature, thus obtaining the TiAlN/CrAlLaBN composite coating.
Example 3
The embodiment provides a TiAlN/CrAlLaBN composite coating, which comprises a TiAlN binding layer, a TiAlN/CrAlLaBN transition layer and a CrAlLaBN top layer which are sequentially arranged on the surface of a substrate from inside to outside.
Wherein the TiAlN bonding layer comprises the following elements in atomic percent: ti22.3at.%, al 21.4at.% and N56.3 at.%, the TiAlN bonding layer has a thickness of 1.5 μm.
The TiAlN/CrAlLaBN transition layer comprises the following elements in atomic percent: ti11.2at.%, cr 8.8at.%, al 20.6at.%, la 0.2at.%, B1.4at.% and N57.8at.%; the TiAlN/CrAlLaBN transition layer had a thickness of 0.5. Mu.m.
The CrAlLaBN top layer includes elements having the following atomic percent contents: cr 20.1at.%, al 18.2at.%, la 0.4at.%, B3.9 at.%, N57.4 at.%; crAlLaBN the top layer had a thickness of 1.7 μm.
The preparation method of the TiAlN/CrAlLaBN composite coating comprises the following steps:
(1) Cleaning a substrate: polishing the surface of a substrate by using polishing cloth (matched with a diamond polishing solution with the thickness of 1 mu m), respectively placing the polished substrate into absolute ethyl alcohol and deionized water for ultrasonic cleaning for 25min, taking out, and drying in an oven at 110 ℃ for 1h;
(2) Argon ion etching and cleaning: placing a substrate into a vacuum coating machine chamber, vacuumizing to 5X 10 -2 Pa, starting heating, heating the chamber to 480 ℃, keeping the temperature for 40min after the temperature of the chamber reaches a set temperature, vacuumizing to 5X 10 -3 Pa, introducing Ar gas, wherein the Ar gas flow is 200sccm, controlling the chamber gas pressure to 0.7Pa, igniting an etching target (Cr target), the etching target current is 100A, the bias voltage of a workpiece rotating frame is-150V, and the etching cleaning time is 100min;
(3) Depositing a TiAlN binding layer: closing Ar gas and an etching target, introducing N 2 gas, controlling the gas flow of N 2 to be 880sccm, controlling the gas pressure of a chamber to be 3Pa, igniting a TiAl (atomic percent content is Ti: 50at%, al: 50at%) target, wherein the current of the TiAl target is 135A, the bias voltage of a workpiece rotating frame is-90V, and the deposition time is 90min;
(4) Depositing a TiAlN/CrAlLaBN transition layer: keeping the deposition atmosphere of the step (3) unchanged, simultaneously igniting a TiAl target and a CrAlLaB (Cr: 49 at%, al:44 at%, la:1 at%, B:6 at%) target, depositing a TiAlN/CrAlLaBN transition layer, wherein the TiAl target current is 135A, the CrAlLaB target current is 150A, the workpiece rotating frame bias voltage is-120V, and the deposition time is 15min;
(5) Depositing CrAlLaBN a top layer: keeping the deposition atmosphere of the step (3) unchanged, closing and igniting the TiAl target, depositing CrAlLaBN top layer by using CrAlLaB target, wherein the current of the CrAlLaB target is 150A, the bias voltage of the workpiece support is 160V, the deposition time is 100min, closing CrAlLaB target and bias voltage after the deposition is finished, closing heating, closing N 2 gas, and taking out the substrate when the temperature of the chamber is reduced to room temperature, thus obtaining the TiAlN/CrAlLaBN composite coating.
Comparative example 1
The comparative example provides a TiAlN coating, which is provided on the surface of a substrate.
Wherein the TiAlN coating comprises the following elements in atomic percent: ti19.4at.%, al 24.2at.% and N56.4at.%, tiAlN coating has a thickness of 3.7 μm.
This comparative example provides a TiAlN coating comprising the steps of:
(1) Cleaning a substrate: polishing the surface of a substrate by using polishing cloth (matched with a diamond polishing solution with the thickness of 1 mu m), respectively placing the polished substrate into absolute ethyl alcohol and deionized water for ultrasonic cleaning for 25min, taking out, and drying in an oven at 110 ℃ for 1h;
(2) Argon ion etching and cleaning: placing a substrate into a vacuum coating machine chamber, vacuumizing to 5X 10 -2 Pa, starting heating, heating the chamber to 480 ℃, keeping the temperature for 40min after the temperature of the chamber reaches a set temperature, vacuumizing to 5X 10 -3 Pa, introducing Ar gas, wherein the Ar gas flow is 200sccm, controlling the chamber gas pressure to 0.7Pa, igniting an etching target (Cr target), the etching target current is 100A, the bias voltage of a workpiece rotating frame is-150V, and the etching cleaning time is 100min;
(3) Depositing a TiAlN binding layer: closing Ar gas and an etching target, introducing N 2 gas, controlling the gas flow of N 2 to be 880sccm, controlling the gas flow of a chamber to be 3Pa, igniting a TiAl (the atomic percentage content is Ti:45 at%, al:55 at%) target, wherein the current of the TiAl target is 135A, the bias voltage of a workpiece rotating frame is-90V, the deposition time is 70min, then the bias voltage of the workpiece rotating frame is-120V, the deposition time is 10min, and finally the bias voltage of the workpiece rotating frame is-160V, and the deposition time is 130min;
and after the deposition is finished, closing the TiAl target and the bias voltage, closing the heating, closing the N 2 gas, and taking out the substrate when the temperature of the chamber is reduced to room temperature to obtain the TiAlN coating.
Comparative example 2
This comparative example provides a CrAlLaBN coating with a CrAlLaBN coating disposed on the surface of the substrate.
Wherein CrAlLaBN coating comprises the following elements in atomic percent: cr17.6at.%, al 21.4at.%, la 0.4at.%, B2.7at.%, N57.9 at.%; the CrAlLaBN coating had a thickness of 3.6 μm.
This comparative example provides a CrAlLaBN coating comprising the steps of:
(1) Cleaning a substrate: polishing the surface of a substrate by using polishing cloth (matched with a diamond polishing solution with the thickness of 1 mu m), respectively placing the polished substrate into absolute ethyl alcohol and deionized water for ultrasonic cleaning for 25min, taking out, and drying in an oven at 110 ℃ for 1h;
(2) Argon ion etching and cleaning: placing a substrate into a vacuum coating machine chamber, vacuumizing to 5X 10 -2 Pa, starting heating, heating the chamber to 480 ℃, keeping the temperature for 40min after the temperature of the chamber reaches a set temperature, vacuumizing to 5X 10 -3 Pa, introducing Ar gas, wherein the Ar gas flow is 200sccm, controlling the chamber gas pressure to 0.7Pa, igniting an etching target (Cr target), the etching target current is 100A, the bias voltage of a workpiece rotating frame is-150V, and the etching cleaning time is 100min;
(3) Depositing CrAlLaBN a coating: closing Ar gas and an etching target, introducing N 2 gas, controlling the gas flow of N 2 to be 880sccm, controlling the gas pressure of a chamber to be 3Pa, igniting a CrAlLaB target (the atomic percentage content is Cr:42 at%, al:51 at%, la:1 at%, B:6 at%) and CrAlLaB target current to be 150A, the bias voltage of a workpiece rotating frame to be-90V, the deposition time to be 70min, then adjusting the bias voltage of the workpiece rotating frame to be-120V, the deposition time to be 10min, and finally adjusting the bias voltage of the workpiece rotating frame to be-160V, and the deposition time to be 130min;
And after the deposition is finished, closing CrAlLaB the target and the bias voltage, closing heating, closing N 2 gas, and taking out the substrate when the temperature of the chamber is reduced to room temperature to obtain the CrAlLaBN coating.
Comparative example 3
The comparative example provides a TiAlN/CrAlLaBN composite coating, which comprises a TiAlN binding layer and a CrAlLaBN top layer which are sequentially arranged on the surface of a substrate from inside to outside.
Wherein the TiAlN bonding layer comprises the following elements in atomic percent: ti19.8at.%, al 24.1at.% and N56.1 at.%, the TiAlN bonding layer has a thickness of 1.3 μm.
The CrAlLaBN top layer includes elements having the following atomic percent contents: cr 17.9at.%, al 20.7at.%, la 0.5at.%, B3.3 at.%, N57.6 at.%; crAlLaBN the top layer had a thickness of 2.3 μm.
The preparation method of the TiAlN/CrAlLaBN composite coating of the comparative example comprises the following steps:
(1) Cleaning a substrate: polishing the surface of a substrate by using polishing cloth (matched with a diamond polishing solution with the thickness of 1 mu m), respectively placing the polished substrate into absolute ethyl alcohol and deionized water for ultrasonic cleaning for 25min, taking out, and drying in an oven at 110 ℃ for 1h;
(2) Argon ion etching and cleaning: placing a substrate into a vacuum coating machine chamber, vacuumizing to 5X 10 -2 Pa, starting heating, heating the chamber to 480 ℃, keeping the temperature for 40min after the temperature of the chamber reaches a set temperature, vacuumizing to 5X 10 -3 Pa, introducing Ar gas, wherein the Ar gas flow is 200sccm, controlling the chamber gas pressure to 0.7Pa, igniting an etching target (Cr target), the etching target current is 100A, the bias voltage of a workpiece rotating frame is-150V, and the etching cleaning time is 100min;
(3) Depositing a TiAlN binding layer: closing Ar gas and an etching target, introducing N 2 gas, controlling the gas flow of N 2 to be 880sccm, controlling the gas pressure of a chamber to be 3Pa, igniting a TiAl (the atomic percentage content is Ti:45 at%, al:55 at%) target, the current of the TiAl target to be 135A, the bias voltage of a workpiece rotating frame to be-90V, and the deposition time to be 75min;
(4) Depositing CrAlLaBN a top layer: keeping the deposition atmosphere of the step (3) unchanged, closing and igniting the TiAl target, depositing CrAlLaBN a top layer by using a CrAlLaB target (the atomic percentage content is Cr:42at percent, al:51at percent, la:1at percent, B:6at percent), wherein the current of the CrAlLaB target is 150A, the bias voltage of a workpiece support is-160V, the deposition time is 135min, closing CrAlLaB target and bias voltage after the deposition is finished, closing and heating, closing N 2 gas, and taking out the substrate when the temperature of the chamber is reduced to room temperature, thus obtaining the TiAlN/CrAlLaBN composite coating.
Comparative example 4
The comparative example provides a TiAlN/CrAlN composite coating, which comprises a TiAlN binding layer, a TiAlN/CrAlN transition layer and a CrAlN top layer which are sequentially arranged on the surface of a substrate from inside to outside.
Wherein the TiAlN bonding layer comprises the following elements in atomic percent: ti19.4at.%, al 23.4at.% and N57.2at.% and the TiAlN bonding layer has a thickness of 1.2 μm.
The TiAlN/CrAlN transition layer comprises the following elements in atomic percent: ti10.1at.%, cr 9.9at.%, al 23.5at.% and N56.5at.%; the thickness of the TiAlN/CrAlN transition layer is 0.3 μm.
The CrAlN top layer comprises the following elements in atomic percent: cr 19.8at.%, al23.3at.%, N56.9 at.%; the thickness of the CrAlN top layer was 2.2. Mu.m.
The preparation method of the TiAlN/CrAlN composite coating comprises the following steps:
(1) Cleaning a substrate: polishing the surface of a substrate by using polishing cloth (matched with a diamond polishing solution with the thickness of 1 mu m), respectively placing the polished substrate into absolute ethyl alcohol and deionized water for ultrasonic cleaning for 25min, taking out, and drying in an oven at 110 ℃ for 1h;
(2) Argon ion etching and cleaning: placing a substrate into a vacuum coating machine chamber, vacuumizing to 5X 10 -2 Pa, starting heating, heating the chamber to 480 ℃, keeping the temperature for 40min after the temperature of the chamber reaches a set temperature, vacuumizing to 5X 10 -3 Pa, introducing Ar gas, wherein the Ar gas flow is 200sccm, controlling the chamber gas pressure to 0.7Pa, igniting an etching target (Cr target), the etching target current is 100A, the bias voltage of a workpiece rotating frame is-150V, and the etching cleaning time is 100min;
(3) Depositing a TiAlN binding layer: closing Ar gas and an etching target, introducing N 2 gas, controlling the gas flow of N 2 to be 880sccm, controlling the gas pressure of a chamber to be 3Pa, igniting a TiAl (the atomic percentage content is Ti:45 at%, al:55 at%) target, the current of the TiAl target to be 135A, the bias voltage of a workpiece rotating frame to be-90V, and the deposition time to be 70min;
(4) Depositing a TiAlN/CrAlN transition layer: keeping the deposition atmosphere of the step (3) unchanged, simultaneously igniting a TiAl target and a CrAl (Cr: 45at.%, al:55 at.%) target, depositing a TiAlN/CrAlN transition layer, wherein the TiAl target current is 135A, the CrAl target current is 150A, the workpiece rotating frame bias is-120V, and the deposition time is 10min;
(5) Depositing a CrAlN top layer: keeping the deposition atmosphere of the step (3) unchanged, closing and igniting the TiAl target, depositing a CrAlN top layer by using the CrAl target, wherein the CrAl target current is 150A, the bias voltage of a workpiece support is 160V, the deposition time is 130min, closing the CrAl target and the bias voltage after the deposition is finished, closing and heating, closing N 2 gas, and taking out the substrate when the temperature of the chamber is reduced to room temperature, thus obtaining the TiAlN/CrAlN composite coating.
In order to compare technical effects of the above examples and comparative examples, the following experimental examples were specially set.
Experimental example 1
The hardness, elastic modulus and binding force of the coatings provided in the examples and comparative examples of the present invention were examined. The hardness and the elastic modulus of the coating in each example and comparative example are detected by a nanoindentation instrument, the maximum indentation depth is ensured to be smaller than 1/10 of the thickness of the coating, so that the influence of the hardness of a matrix on the hardness measurement of the coating is avoided, the maximum load is 10mN, the load retention time is 10s, the loading and unloading rates are 20mN/min, and each sample is repeatedly measured for 10 times and then averaged. The ratio H/E of the hardness (H) to the elastic modulus (E) can characterize the toughness of the coating material to a certain extent, the greater the ratio the better the toughness of the coating material.
The binding force of the coating is detected by adopting a large-load scratch instrument, the scratch length is 3mm, the maximum load is 150N, the linear loading rate is 300N/min, the critical load (Lc 2) corresponding to the moment when the coating and the matrix start to peel off is taken as the binding force of the coating, each sample is repeatedly measured for 3 times, and then the average value is taken, and the specific result is shown in Table 1.
TABLE 1
As can be seen from the data in table 1, the hardness of the composite coatings of examples 1 to 3 is high and the toughness is significantly improved as compared to the single-layer coatings of comparative examples 1 and 2. Compared with the coating of comparative example 3, the composite coatings of examples 1-3 have TiAlN/CrAlLaBN transition layers, the hardness of the coating is increased, the elastic modulus is greatly reduced, and the toughness is improved, so that the TiAlN/CrAlLaBN transition layers can play a role in improving the comprehensive performance of the coating. The composite coatings of examples 1 to 3 added La element and B element, and the hardness and toughness of the coating were improved at the same time, compared to the coating of comparative example 4.
In addition, the bonding force of the composite coatings of the examples 1-3 is higher than that of the single-layer coatings of the comparative examples 1 and 2, and meanwhile, the bonding force of the composite coatings of the examples 1-3 is further improved on the basis of the bonding force of the coating of the comparative example 3 due to the improvement effect of the TiAlN/CrAlLaBN transition layer; as can be seen from comparison with the coating of comparative example 4, the addition of La and B elements also improves the coating adhesion.
Experimental example 2
To further examine the effect of the coatings of the examples and comparative examples of the present invention on tool life, the coatings of the above examples and comparative examples were deposited on cemented carbide tools, respectively, a 316L stainless steel bar was dry turned at a cutting speed of 200m/min, a feed rate of 0.3mm/r, a cutting depth of 1.5mm, a cutting time of 30min, and comparative tip wear lengths were observed, with specific results being shown in FIG. 2.
Compared with the cutters deposited with the coatings of the comparative examples 1 and 2, the cutters deposited with the coatings of the examples 1 to 3 have small cutter tip abrasion length, which shows that the TiAlN/CrAlLaBN composite coating provided by the invention has more advantages when being used in a high-speed dry cutting scene than a conventional single-layer coating, and can effectively prolong the service life of the cutters; compared with the cutter for depositing the coating of the comparative example 3, the cutter tip abrasion length of the cutter for depositing the coatings of the examples 1-3 is smaller, which shows that the TiAlN/CrAlLaBN transition layer can play a role in buffering in the use of the cutter, the comprehensive performance of the coating is improved, and the service life of the cutter is further prolonged; as can be seen by comparison with the tool having the coating of comparative example 4 deposited, the addition of La element and B element is effective in reducing wear of the tool nose.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The TiAlN/CrAlLaBN composite coating is characterized by comprising a TiAlN binding layer, a TiAlN/CrAlLaBN transition layer and a CrAlLaBN top layer which are sequentially arranged on the surface of a substrate from inside to outside;
The TiAlN bonding layer comprises the following elements in atomic percent: 16-23 at.% of Ti, 20-28 at.% of Al and 50-60 at.% of N;
The thickness of the TiAlN bonding layer is 0.5-1.5 mu m;
The TiAlN/CrAlLaBN transition layer comprises the following elements in percentage by atom: 6-12 at.% of Ti, 3-9 at.% of Cr, 16-28 at.% of Al, 0.1-0.3 at.% of La, 0.7-3.5 at.% of B and 50-60 at.% of N;
the thickness of the TiAlN/CrAlLaBN transition layer is 0.2-0.5 mu m;
The CrAlLaBN top layer includes elements having the following atomic percent contents: 13-21 at.% of Cr, 15-25 at.% of Al, 0.3-0.6 at.% of La, 1-5 at.% of B, and 51-60 at.% of N;
the thickness of the CrAlLaBN top layer is 1.5-2.5 mu m;
The substrate is made of high-speed steel.
2. The method for preparing the TiAlN/CrAlLaBN composite coating as claimed in claim 1, comprising the steps of:
(a) Vapor depositing a TiAlN bonding layer on the surface of the substrate;
(b) Vapor depositing a TiAlN/CrAlLaBN transition layer on the surface of the TiAlN bonding layer;
(c) And carrying out vapor deposition CrAlLaBN on the surface of the TiAlN/CrAlLaBN transition layer to obtain the TiAlN/CrAlLaBN composite coating.
3. The method of preparing a TiAlN/CrAlLaBN composite coating according to claim 2, wherein the vapor deposition method in step (a), step (b) and step (c) is a physical vapor deposition method.
4. A method of preparing a TiAlN/CrAlLaBN composite coating as claimed in claim 3 wherein the physical vapour deposition method is an arc ion plating method.
5. A method of preparing a TiAlN/CrAlLaBN composite coating as claimed in claim 3 wherein in step (a) the TiAlN bonding layer is deposited by at least the following process parameters: the gas flow of N 2 is 800-950 sccm, the chamber pressure is 2-5 Pa, the TiAl target current is 100-150A, the bias voltage of the workpiece support is-80 to-120V, and the deposition time is 30-90 min.
6. The method of claim 5, wherein in step (a), the step of cleaning and etching the substrate is further included before depositing the TiAlN bonding layer.
7. The method of preparing a TiAlN/CrAlLaBN composite coating according to any one of claims 2 to 6, wherein in step (b), the deposition of the TiAlN/CrAlLaBN transition layer comprises at least the following process parameters: the gas flow of N 2 is 800-950 sccm, the chamber pressure is 2-5 Pa, the TiAl target current is 100-150A, the CrAlLaB target current is 130-180A, the bias voltage of the workpiece support is-100 to-140V, and the deposition time is 5-15 min.
8. The method of claim 7, wherein the deposition of the CrAlLaBN top layer in step (c) comprises at least the following process parameters: the gas flow of N 2 is 800-950 sccm, the chamber pressure is 2-5 Pa, the CrAlLaB target current is 130-180A, the bias voltage of the workpiece support is-140 to-180V, and the deposition time is 90-150 min.
9. A tool comprising a tool substrate and the TiAlN/CrAlLaBN composite coating layer of claim 1 or the TiAlN/CrAlLaBN composite coating layer prepared by the method for preparing the TiAlN/CrAlLaBN composite coating layer of any one of claims 2-8 disposed on the surface of the tool substrate.
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