CN116770227B - High strength and toughness low internal stress thick TiNi & TiAl (Ni) NXTiAlN composite hard coating and preparation method thereof - Google Patents
High strength and toughness low internal stress thick TiNi & TiAl (Ni) NXTiAlN composite hard coating and preparation method thereof Download PDFInfo
- Publication number
- CN116770227B CN116770227B CN202310751182.5A CN202310751182A CN116770227B CN 116770227 B CN116770227 B CN 116770227B CN 202310751182 A CN202310751182 A CN 202310751182A CN 116770227 B CN116770227 B CN 116770227B
- Authority
- CN
- China
- Prior art keywords
- tini
- tialn
- tial
- target
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910010380 TiNi Inorganic materials 0.000 title claims abstract description 144
- 238000000576 coating method Methods 0.000 title claims abstract description 138
- 239000011248 coating agent Substances 0.000 title claims abstract description 133
- 229910010038 TiAl Inorganic materials 0.000 title claims abstract description 114
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 144
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 135
- 239000010410 layer Substances 0.000 claims abstract description 121
- 229910010037 TiAlN Inorganic materials 0.000 claims abstract description 110
- 239000010936 titanium Substances 0.000 claims abstract description 48
- 239000011159 matrix material Substances 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 238000007733 ion plating Methods 0.000 claims abstract description 19
- 239000002346 layers by function Substances 0.000 claims abstract description 18
- 230000007704 transition Effects 0.000 claims abstract description 15
- 238000005516 engineering process Methods 0.000 claims abstract description 13
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 5
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001256 stainless steel alloy Inorganic materials 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 70
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 62
- 238000000151 deposition Methods 0.000 claims description 48
- 229910004349 Ti-Al Inorganic materials 0.000 claims description 43
- 229910004692 Ti—Al Inorganic materials 0.000 claims description 43
- 229910052757 nitrogen Inorganic materials 0.000 claims description 39
- 229910004337 Ti-Ni Inorganic materials 0.000 claims description 34
- 229910011209 Ti—Ni Inorganic materials 0.000 claims description 34
- 229910052786 argon Inorganic materials 0.000 claims description 34
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 claims description 34
- 230000001105 regulatory effect Effects 0.000 claims description 34
- 230000008021 deposition Effects 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 230000001276 controlling effect Effects 0.000 claims description 16
- 239000013077 target material Substances 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 8
- -1 argon ions Chemical class 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000009434 installation Methods 0.000 claims description 6
- 239000002923 metal particle Substances 0.000 claims description 6
- 238000013461 design Methods 0.000 claims description 5
- 238000010884 ion-beam technique Methods 0.000 claims description 5
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000005520 cutting process Methods 0.000 abstract description 2
- 239000011253 protective coating Substances 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 19
- 229910052710 silicon Inorganic materials 0.000 description 19
- 239000010703 silicon Substances 0.000 description 19
- 235000012431 wafers Nutrition 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000010963 304 stainless steel Substances 0.000 description 8
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 8
- 150000004767 nitrides Chemical class 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011153 ceramic matrix composite Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 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
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- 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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- 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
- C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
The invention relates to a high-strength and high-toughness low-internal-stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating and a preparation method thereof, belonging to the technical field of protective coatings. The coating takes an alloy matrix as a substrate, is prepared by adopting a multi-arc ion plating multi-target codeposition technology, and comprises a Ti bonding layer, a TiAlN transition layer and a TiNi & TiAl (Ni) N X/TiAlN functional layer from inside to outside. The total thickness of the coating prepared by the invention is 5-30 mu m, and the microhardness is more than 2000 Hv. The coating has excellent bonding performance with a matrix, has the characteristics of high toughness, high hardness, low internal stress, excellent crack extension resistance, high-temperature oxidation resistance and the like, and can be suitable for wear-resistant protection of materials such as hard alloy cutting tools, stainless steel alloys, titanium aluminum alloys and the like.
Description
Technical Field
The invention relates to the technical field of protective coatings, in particular to a high-strength and high-toughness low-internal-stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating and a preparation method thereof.
Background
The transition metal nitride has the characteristics of high hardness, excellent wear resistance, higher chemical inertness and the like, and has been widely used as a wear-resistant coating, including various high-speed steels, hard alloy cutters, aircraft engine blades, and the like. However, the brittleness of the nitride coating is high and the internal stress is high, so that the bonding performance of the coating and the substrate is reduced with the increase of the thickness (the tendency of peeling of the single-layer nitride coating when the thickness exceeds 6-7 μm is obviously increased), and the reliability and the application range of the application of the single-layer nitride coating are limited.
The preparation of the thick hard coating with high performance (such as low internal stress, high hardness, high toughness, good wear resistance, corrosion resistance and the like) can be realized by reasonably optimizing the nitride coating structure, such as designing a multi-element composite nitride/metal alternating layer or superlattice nitride/metal gradient layer and the like, and through sub-layer screening, interface control, structure parameter regulation and the like. For example, in literature ①(Shuai J,Zuo X,Wang Z,et al.Erosion behavior and failure mechanism of Ti/TiAlN multilayer coatings eroded by silica sand and glass beads.Journal of Materials Science&Technology 21(2021)179-190), tiAlN/Ti multilayer coatings prepared using arc ion plating techniques; in the patent of the issued publication number CN105862004B, tiAlCrN & MoS 2/Ti/Al/Cr multi-element composite hard coating prepared by adopting an intermediate frequency magnetron sputtering technology; the method for embedding the ductile phase into the ceramic substrate to form the ceramic matrix composite hard coating is also a method for effectively inhibiting crack formation and expansion, improving the toughness of the coating and reducing the internal stress of the coating by referring to the design principle of the particle toughening ceramic matrix composite. For example, zrN/Cu coatings prepared in literature ②(Musil J,Zeman P.Structure and microhardness of magnetron sputtered ZrCu and ZrCu-N films-ScienceDirect.Vacuum 52(1999)269-275) using medium frequency magnetron sputtering techniques; in addition, other common coating toughening methods also include phase change toughening, compressive stress toughening and the like.
Disclosure of Invention
The invention aims to provide a high-strength and high-toughness low-internal-stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating and a preparation method thereof, wherein the coating has excellent combination property with a matrix, and the coating has the characteristics of high toughness, high hardness, low internal stress, excellent crack expansion resistance, high-temperature oxidation resistance and the like, and can greatly improve the application reliability and service life of the hard coating.
The technical scheme of the invention is as follows:
The TiNi & TiAl (Ni) N X/TiAlN composite hard coating with high strength and toughness and low internal stress is formed by sequentially and circularly superposing a TiNi & TiAl (Ni) N X low internal stress hard layer and a TiAlN high internal stress strong hard layer with the layer thickness ratio r being 1:1 or more and 1:5 from inside to outside, wherein the TiNi & TiAl (Ni) N X/TiAlN composite hard coating comprises a Ti bonding layer, a TiAlN transition layer and a TiNi & TiAl (Ni) N X/TiAlN functional layer; the total number of layers N of TiNi & TiAl (Ni) N X/TiAlN functional layers is adjustable within the range of 2-20, and the total number of layers N is an even number.
The high-strength and high-toughness low-internal-stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating is characterized in that the thickness of a Ti bonding layer in the TiNi & TiAl (Ni) N X/TiAlN composite hard coating is 0.2-1.0 mu m, the thickness of a TiAlN transition layer is 0.2-3.0 mu m, and the total thickness of the composite hard coating is 5.0-30.0 mu m.
The TiNi & TiAl (Ni) N X/TiAlN composite hard coating with high strength and toughness and low internal stress is characterized in that the TiNi & TiAl (Ni) N X/TiAlN composite hard coating with high strength and toughness and low internal stress is a TiNi metal particle toughened TiNi (Ni) N X composite hard coating regulated and controlled by pulse bias; the atomic proportion relation of each element in TiAl (Ni) N X phase is as follows: al/(ti+al+ni) =0 to 0.5, ni/(ti+al+ni) =0.05 to 0.3, x=n/(n+ti+al+ni) =0.35 to 0.5; the atomic proportion relation of each element in TiNi phase is as follows: ti/(ti+ni+n) =0.40 to 0.55, and Ni/(ti+ni+n) =0.40 to 0.5.
The high-strength and high-toughness low-internal-stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating has the microhardness of more than 2000 Hv.
The preparation method of the TiNi & TiAl (Ni) N X/TiAlN composite hard coating with high strength and toughness and low internal stress comprises the step of preparing the TiNi & TiAl (Ni) N X/TiAlN composite hard coating by adopting a multi-arc ion plating technology and adopting a multi-target co-deposition technology.
The preparation method of the high-strength and high-toughness low-internal stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating comprises the following specific steps:
Step 1, grinding and polishing an alloy matrix to ensure that the surface roughness Ra of the alloy matrix is lower than 0.2 mu m;
step 2, immersing the alloy matrix in a mixed solvent of absolute ethyl alcohol and acetone for 10-15 min, ultrasonically cleaning, removing oil stains, and drying for later use;
step 3, installing 1 pure Ti target, 1 Ti-Al alloy target and 1 Ti-Ni alloy target in a chamber of multi-arc ion plating equipment, wherein the connecting line of the target centers of the Ti-Al alloy target and the Ti-Ni alloy target is vertical to a base, the Ti-Al alloy target is positioned at the upper end, the Ti-Ni alloy target is positioned at the lower end, and the distance between the double target centers of the Ti-Al alloy target and the Ti-Ni alloy target is in the range of 25-30 cm; the horizontal positions of the pure Ti target and the Ti-Al alloy target are kept basically consistent, and the installation positions of the pure Ti target and the Ti-Al alloy target are opposite to the Ti-Al alloy target;
Step 4, hanging an alloy matrix at a position between a Ti-Al alloy target and a Ti-Ni alloy target bullion on a rotating frame in a cavity, wherein the specific position is determined by the designed layer thickness ratio of TiNi & TiAl (Ni) N X/TiAlN functional layer, plating bias parameters and Ni content required by TiAl (Ni) N X phase in the TiNi & TiAl (Ni) N X low internal stress tough layer;
Step 5, revolving the revolving frame to a position opposite to the target center of the pure Ti, closing a chamber door, after the temperature of the chamber is raised to 200 ℃ and the air pressure in the chamber is pumped to be less than or equal to 7.0 multiplied by 10 -3 Pa, starting the revolving frame to rotate, introducing argon, keeping the air pressure between 3.0 Pa and 4.0Pa, starting a bias power supply, setting pulse bias to be-700V to-900V, setting the duty ratio to be 30-40%, cleaning for 3-10 minutes by using argon ions, and closing the bias power supply;
Step 6, maintaining self-transmission of the rotating frame, adjusting an argon flow meter, and maintaining the air pressure in the cavity to be 1.5-2.0 Pa; starting a bias power supply, setting pulse bias voltage to-850 to-1000V, and setting duty ratio to 5-10%; starting a pure Ti target arc power supply, and regulating the arc current to 70-80A; bombarding for 3-5 min by using a high-energy ion beam to remove surface dirt and oxide skin;
step 7, regulating pulse bias voltage to-200V to-400V, duty ratio to 15-20%, arc current to 70-80A, depositing Ti bonding layer, and controlling coating thickness by changing deposition time;
Step 8, maintaining self-transmission of a rotating frame, opening a nitrogen flow valve, regulating a nitrogen flow meter and an argon flow meter, controlling the flow ratio of the nitrogen flow meter and the argon flow meter to be in a range of 7:1-15:1, maintaining the air pressure in a cavity to be 1.5-2.0 Pa, starting an arc power supply of a Ti-Al alloy target, regulating pulse bias to be-100V to-300V, and regulating the arc current to be 70-100A with a duty ratio of 10-20%; opening the revolving frame to revolve to a position opposite to the connecting line of the Ti-Al alloy target and the target center of the Ti-Ni alloy target, closing the revolving frame to revolve, and opening the revolving frame to rotate; closing a pure Ti target arc power supply, depositing a TiAlN transition layer, and controlling the thickness of the coating by changing the deposition time;
Step 9, regulating a nitrogen flow meter, maintaining the air pressure in a cavity to 2.0-3.0 Pa, regulating pulse bias to-200V to-500V, switching on a Ti-Ni alloy target arc power supply with a duty ratio of 15-20%, regulating arc current to 70-85A, depositing a TiNi & TiAl (Ni) N X low internal stress tough layer, and controlling the thickness of the coating by changing deposition time;
Step 10, regulating a nitrogen flow meter, and maintaining the air pressure in the cavity to be 1.5-2.0 Pa; adjusting pulse bias to-100V to-300V, switching off a Ti-Ni alloy target arc power supply, depositing a TiAlN high internal stress hard layer, and controlling the thickness of the coating by changing deposition time;
Step 11, continuously depositing a TiNi & TiAl (Ni) N X low internal stress tough layer according to the step 9 and continuously depositing a TiAlN high internal stress hard layer according to the step 10 after the deposition of the TiAlN high internal stress hard layer is finished until the total number N of TiNi & TiAl (Ni) N X/TiAlN functional layers reaches the design requirement of the number of layers; after the coating deposition is finished, the arc power supply and the bias power supply are turned off, the nitrogen flow valve and the argon flow valve are turned off, and the rotating frame self-transmission is turned off;
And 12, maintaining the air pressure in the cavity to be less than or equal to 7.0 multiplied by 10 -3 Pa, and taking out the alloy matrix after the temperature of the cavity is cooled to be lower than 100 ℃ to finish the preparation of the TiNi & TiAl (Ni) N X/TiAlN composite hard coating.
In the preparation method of the high-strength and high-toughness low-internal-stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating, in the step 1, the alloy matrix is a hard alloy material, a stainless steel alloy material, a titanium alloy material or a titanium aluminum alloy material.
In the preparation method of the high-strength and high-toughness low-internal stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating, in the step 3, the purity of a pure Ti target material is more than or equal to 99.9wt.%; in the Ti-Al alloy target, the Al content is 30at percent to 50at percent, and the alloy purity is more than or equal to 99.9wt percent; in the Ti-Ni alloy target material, the Ti content is 50at percent, the Ni content is 50at percent, and the alloy purity is more than or equal to 99.9 wt%.
The design idea of the invention is as follows:
The invention uses TiAlN ceramic coating as base, and adopts multi-arc ion plating to prepare TiNi & TiAl (Ni) N X/TiAlN composite hard coating by multi-target co-deposition technology. The Ti bonding layer and the TiAlN transition layer are designed to improve the bonding performance between the coating and the substrate. Meanwhile, the TiNi & TiAl (Ni) N X low internal stress tough layer designed by the invention adopts a synergistic effect mode of TiNi metal particle toughening and Ni solid solution toughening, so that the TiNi & TiAl (Ni) N X low internal stress tough layer has the characteristics of low internal stress, high hardness, high toughness and the like. By taking the titanium alloy as an intermediate layer and alternately depositing the titanium alloy and the TiAlN high internal stress hard layer, the internal stress of the whole TiNi & TiAl (Ni) N X/TiAlN composite hard coating can be effectively reduced, and the toughness of the coating is greatly improved. Meanwhile, the coating has the characteristics of high hardness, excellent crack extension resistance, high-temperature oxidation resistance and the like, and can be suitable for wear-resistant protection of hard alloy cutting tools, stainless steel alloy, titanium aluminum alloy and other materials.
Compared with the prior art, the invention has the following advantages:
1. The invention adopts a multi-target codeposition technology, takes a TiNi metal particle toughened TiNi & TiAl (Ni) N X low internal stress tough layer regulated by pulse bias as an intermediate layer, alternately deposits with a TiAlN high internal stress hard layer, combines the structural design of a Ti bonding layer and a TiAlN transition layer, can effectively reduce the internal stress of the whole coating, prepares a composite hard coating with the thickness exceeding 10 mu m and excellent combination property, and can greatly improve the application reliability and service life of the hard coating.
2. The TiNi & TiAl (Ni) N X/TiAlN composite hard coating designed by the invention adopts a synergistic effect mode of TiNi metal particle toughening, ni element solid solution toughening and multilayer coating structure toughening, and can effectively improve the toughness of the coating on the premise of not losing the hardness of the coating, so that the coating has the characteristics of high toughness, high hardness, excellent crack expansion resistance, high-temperature oxidation resistance and the like.
3. The TiNi & TiAl (Ni) N X/TiAlN composite hard coating designed by the invention is prepared at one time by adopting a multi-arc ion plating technology, and the preparation process of the coating is simple and easy to implement, and has no use and release of harmful substances in the preparation process, thereby being environment-friendly.
Drawings
FIG. 1 is a schematic diagram of a high strength and toughness low internal stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating. Reference numerals in the drawings: 1. a base; 2. a Ti bonding layer; 3. a TiAlN transition layer; 4. TiNi & TiAl (Ni) N X/TiAlN functional layer; 5. TiNi & TiAl (Ni) N X low internal stress tough layer; 6. TiAlN high internal stress hard layer.
Fig. 2 is a schematic diagram of the working principle of the multi-arc ion plating apparatus used in the present invention. Reference numerals in the drawings: the vacuum furnace comprises a first target arc power supply, a second target arc power supply, a third target arc power supply, a 13 base, a 14 pulse bias power supply and a 15 vacuumizing port, wherein the first target arc power supply, the second target arc power supply, the 3 cavity, the 4 air inlet, the 5 rotating frame, the 6 top seat, the 7 sample, the 8 heating device, the 9 second target arc power supply, the 10 second target arc power supply, the 11 third target arc power supply, the 12 third target arc power supply, the 13 base, the 14 pulse bias power supply and the 15 vacuumizing port.
FIG. 3 is an SEM cross-sectional morphology of TiNi & TiAl (Ni) N X/TiAlN composite hard coating of example 1.
Fig. 4 is an SEM cross-sectional morphology of the TiNi & TiAl (Ni) N X low internal stress toughness layer of example 1.
FIG. 5 is an XRD pattern of TiNi & TiAl (Ni) N X low internal stress toughness layer of example 1. In the figure, the abscissa 2θ represents the diffraction angle (devie), and the ordinate Intensity represents the relative Intensity (a.u.).
FIG. 6 is an SEM cross-sectional morphology of TiNi & TiAl (Ni) N X/TiAlN composite hard coating of example 2.
Detailed Description
As shown in fig. 1, the high-strength and high-toughness low-internal-stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating structure designed by the invention is prepared by adopting a multi-arc ion plating multi-target codeposition technology by taking a matrix 1 as a substrate, and mainly comprises a Ti bonding layer 2, a TiAlN transition layer 3 and a TiNi & TiAl (Ni) N X/TiAlN functional layer 4 from inside to outside; the TiNi & TiAl (Ni) N X/TiAlN functional layer 4 is formed by sequentially and circularly superposing a TiNi & TiAl (Ni) N X low-internal-stress tough layer 5 and a TiAlN high-internal-stress hard layer 6 with the layer thickness ratio r being 1:1 or more and r being 1:5 or less; wherein the total layer number N of TiNi & TiAl (Ni) N X/TiAlN functional layer 4 is adjustable within the range of 2-20, and the total layer number N is an even number.
As shown in fig. 2, the multi-arc ion plating apparatus used in the present invention mainly includes a first target arc power supply 1, a first target 2, a chamber 3, an air inlet 4, a rotating frame 5, a top seat 6, a heating device 8, a second target 9, a second target arc power supply 10, a third target 11, a third target arc power supply 12, a base 13, a pulse bias power supply 14, and a vacuum pumping port 15, and has the following specific structure:
The two sides of the upper part in the cavity 3 are oppositely provided with a first target 2 and a second target 9 corresponding to the sample 7, one side of the lower part in the cavity 3 is provided with a third target 11 corresponding to the sample 7, the first target 2 is arranged on the first target arc power supply 1, the second target 9 is arranged on the second target arc power supply 10, the third target 11 is arranged on the third target arc power supply 12, the first target 2 is a pure Ti target, the second target 9 is a Ti-Al alloy target, and the third target 11 is a Ti-Ni alloy target. The lower end parts of the two sides of the cavity 3 are respectively provided with an air inlet 4 and a vacuumizing port 15, working or reaction gas enters the cavity 3 from the air inlet 4, and the vacuum maintaining system vacuumizes the cavity 3 through the vacuumizing ports 15.
A top seat 6, a heating device 8, a base 13 and a pulse bias power supply 14 are sequentially arranged in the cavity 3 from top to bottom along the central axis direction; the rotating frame 5 capable of rotating is arranged between opposite surfaces on the horizontal top seat 6 and the horizontal base 13, the samples 7 are arranged up and down on the rotating frame 5, the selectable sample hanging positions are respectively S1, S2 and S3 … … Sn (N is more than or equal to 1) from top to bottom, and the specific sample hanging positions are determined by the designed layer thickness ratio of TiNi & TiAl (Ni) N X/TiAlN functional layers, coating bias parameters and the required Ni content of the TiNi (Ni) N X phase in the TiNi & TiAl (Ni) N X low internal stress tough layer.
For a further understanding of the present invention, reference should be made to the following description of the invention taken in conjunction with the accompanying drawings, which are included to provide a further understanding of the nature and advantages of the invention, and not to the limit of the claims.
Example 1
In the embodiment, ti6Al4V alloy, 304 stainless steel alloy and silicon wafers with the sizes of 50.0mm multiplied by 5.0mm multiplied by 0.2mm are used as matrix materials, and a multi-arc ion plating technology is adopted to respectively prepare a TiNi & TiAl (Ni) N X/TiAlN composite hard coating and a TiNi & TiAl (Ni) N X low-internal stress tough layer.
(1) Preparing an alloy target: the pure Ti target, ti-Al alloy target and Ti-Ni alloy target prepared by adopting a vacuum melting method are used as cathode targets. Wherein the purity of the pure Ti target material is more than or equal to 99.9 wt%; the Ti-Al alloy target material comprises Ti-30Al (at.%) and the purity of the alloy is more than or equal to 99.9wt.%; the Ti-Ni alloy target material comprises Ti-50Ni (at%) and the alloy purity is greater than or equal to 99.9 wt%.
(2) Alloy target installation: 1 pure Ti target, 1 Ti-Al alloy target and 1 Ti-Ni alloy target were installed in a chamber of a multi-arc ion plating apparatus. Wherein, the wiring between the Ti-Al alloy target and the target center of the Ti-Ni alloy target is vertical to the base, the Ti-Al alloy target is positioned at the upper end, the Ti-Ni alloy target is positioned at the lower end, and the distance between the target centers of the two targets is 30cm; the horizontal positions of the pure Ti target and the Ti-Al alloy target are kept basically consistent, and the installation positions of the pure Ti target and the Ti-Al alloy target are opposite to the Ti-Al alloy target.
(3) Pretreatment of a matrix sample: after grinding and polishing the Ti6Al4V alloy and 304 stainless steel alloy matrix (with the size of 15mm multiplied by 20mm multiplied by 2.5 mm) by SiC sand paper, controlling the surface roughness Ra of the alloy matrix to be 0.05 mu m, and putting alcohol and acetone into the alloy matrix according to the volume ratio of 1:1, ultrasonic cleaning for 10min in the mixed solution, and drying for later use. The silicon wafer is fixed on a clamp, and the clamp is used for shielding one of two surfaces of the silicon wafer so as to realize single-sided deposition of a TiNi & TiAl (Ni) N X low-internal-stress tough layer on the silicon wafer.
(4) Coating: and coating a TiNi & TiAl (Ni) N X/TiAlN composite hard coating on the surface of the Ti6Al4V alloy by adopting multi-arc ion plating equipment. The coating steps are as follows:
① Sample hanging position selection: and (3) hanging the Ti6Al4V alloy matrix on a rotating frame in the cavity, so that the Ti6Al4V alloy matrix is opposite to the target center of the Ti-Al alloy target.
② And (5) revolving the revolving frame to a position opposite to the target center of the pure Ti, and closing the chamber door. After the temperature of the chamber is raised to 200 ℃ and the air pressure in the chamber is pumped to 5.0 multiplied by 10 -3 Pa, starting the rotating frame to rotate, introducing argon, keeping the air pressure at about 4.0Pa, starting a bias power supply, setting pulse bias to-850V, setting the duty ratio to be 40%, cleaning a substrate sample by using argon ions for 5min, and closing the bias power supply.
③ Maintaining the self-transmission of the rotating frame, adjusting an argon flow meter, maintaining the air pressure in the cavity to 2.0Pa, starting a bias power supply, and starting a pure Ti target arc power supply. The specific process parameters are as follows: the pulse bias is-900V, duty cycle 10%, arc current 70A. And bombarding the matrix sample by using a high-energy ion beam for 3min, and removing dirt and oxide scale on the surface of the matrix sample.
④ The pulse bias voltage is regulated to-200V, the duty ratio is 20%, the arc current is 70A, the Ti bonding layer is deposited, and the deposition time is 5min.
⑤ Maintaining self-transmission of the rotating frame, opening a nitrogen flow valve, adjusting nitrogen and argon flow meters, controlling the flow ratio of the nitrogen to the argon to be 10:1, maintaining the air pressure in the cavity to 2.0Pa, starting an arc power supply of the Ti-Al alloy target, adjusting pulse bias to-100V, adjusting arc current to 70A, and controlling the duty ratio to be 20%. And (3) closing the rotation of the rotating frame, opening the revolution of the rotating frame to enable the rotating frame to revolve to a position opposite to the connecting line of the target centers of the Ti-Al alloy target and the Ti-Ni alloy target, closing the revolution of the rotating frame, and opening the rotation of the rotating frame. And (3) switching off the arc power supply of the pure Ti target material, and depositing a TiAlN transition layer for 22min.
⑥ Regulating a nitrogen flow meter, maintaining the air pressure in a cavity to 2.5Pa, regulating pulse bias to-200V, turning on a Ti-Ni alloy target arc power supply, regulating arc current to 70A, and depositing a TiNi & TiAl (Ni) N X low-internal stress tough layer for 20min.
⑦ Regulating a nitrogen flow meter, maintaining the air pressure in the cavity to 2.0Pa, regulating the pulse bias to-100V, closing the arc power supply of the Ti-Ni alloy target material, and depositing the TiAlN high internal stress hard layer for 65min. After the coating deposition is finished, the arc power supply and the bias power supply of the Ti-Al alloy target material are turned off, the flow valves of nitrogen and argon are turned off, and the rotating frame rotates.
⑧ And (3) keeping the air pressure in the cavity at 6.0 multiplied by 10 -3 Pa, taking out the Ti6Al4V alloy sample after the temperature of the cavity is cooled to below 100 ℃, and finishing the preparation of the TiNi & TiAl (Ni) N X/TiAlN composite hard coating.
In addition, a 304 stainless steel alloy and a silicon wafer with the size of 50.0mm multiplied by 5.0mm multiplied by 0.2mm are used as matrix materials, and TiNi & TiAl (Ni) N X low internal stress tough layer coating process is respectively deposited on the 304 stainless steel alloy surface and the silicon wafer single face according to the TiNi & TiAl (Ni) N X low internal stress tough layer coating process in the coating and plating process of the step (4). Wherein, a TiNi & TiAl (Ni) N X low internal stress tough layer is deposited on one side of the silicon wafer and used for measuring the residual stress of the coating. The specific coating steps are as follows:
① Sample hanging position selection: the sample hanging positions of the 304 stainless steel alloy matrix and the silicon chip on the rotating frame are consistent with the sample hanging positions of the Ti6Al4V alloy matrix.
② The rotating frame is arranged at a position opposite to the connecting line of the Ti-Al alloy target and the target center of the Ti-Ni alloy target, and the chamber door is closed. After the temperature of the chamber is raised to 200 ℃ and the air pressure in the chamber is pumped to 6.0X10 -3 Pa, starting the rotating frame to rotate, introducing argon, keeping the air pressure at about 4.0Pa, starting a bias power supply, setting pulse bias to-850V, setting the duty ratio to be 40%, cleaning the substrate sample for 3min by using argon ions, and closing the bias power supply.
③ Maintaining self-transmission of the rotating frame, opening a nitrogen flow valve, adjusting nitrogen and argon flow meters, controlling the flow ratio of the nitrogen to the argon to be 10:1, maintaining the air pressure in the cavity to 2.0Pa, starting a bias power supply, and starting a Ti-Al alloy target arc power supply. The specific process parameters are as follows: arc current 70A, pulse bias is set to-950V, duty cycle 10%. And bombarding the matrix sample by using a high-energy ion beam for 3min, and removing dirt and oxide scale on the surface of the matrix sample.
④ Adjusting a nitrogen flow meter, maintaining the air pressure in the cavity to 2.5Pa, adjusting pulse bias to-200V, turning on a Ti-Ni alloy target arc power supply, and depositing a TiNi & TiAl (Ni) N X low-internal-stress tough layer. The specific process parameters are as follows: the arc current of the Ti-Al alloy target material is 70A; and the arc current 70A of the Ti-Ni alloy target material. The deposition time of the TiNi & TiAl (Ni) N X low-internal-stress tough layer on the surface of the 304 stainless steel alloy substrate is 60min, the deposition time of the TiNi & TiAl (Ni) N X low-internal-stress tough layer on the surface of the silicon wafer is 7min, after the coating deposition is finished, a Ti-Al alloy target arc power supply, a Ti-Ni alloy target arc power supply and a bias power supply are turned off, a nitrogen and argon flow valve is turned off, and the rotating frame autorotation is turned off.
⑤ And (3) keeping the air pressure in the cavity at 5.0 multiplied by 10 -3 Pa, and respectively taking out 304 stainless steel alloy and silicon wafer samples after the temperature of the cavity is cooled to below 100 ℃ to finish the preparation of the TiNi & TiAl (Ni) N X low-internal stress tough layer.
(5) Coating structure characterization and performance testing
As shown in FIG. 3, the TiNi & TiAl (Ni) N X/TiAlN composite hard coating deposited on the surface of the Ti6Al4V alloy matrix in the embodiment is complete and compact, and is well combined with the alloy matrix. In the composite hard coating, the thickness of the Ti bonding layer is about 0.5 mu m, and the thickness of the TiAlN transition layer is about 2.1 mu m; the layer thickness ratio r of TiNi & TiAl (Ni) N X/TiAlN functional layer is about 1:3, 2 layers (namely TiNi & TiAl (Ni) N X and 1 layer each of TiAlN) are provided, the thickness of the TiNi & TiAl (Ni) N X low internal stress tough layer is about 1.9 μm, the thickness of the TiAlN high internal stress hard layer is about 6.0 μm, and the total thickness of the composite hard coating is about 10.5 μm. EDS detection results show that the atomic percentage content of each element in the TiNi & TiAl (Ni) N X low-internal stress tough layer TiAl (Ni) N X matrix phase is as follows: ti:42.57%, al:14.37%, ni:4.43%, N:38.66 percent, and a small amount of white strip-shaped second phase particles (TiNi toughening particles) are uniformly distributed in the TiNi & TiAl (Ni) N X low-internal stress tough layer. The micro-hardness value of TiNi & TiAl (Ni) N X/TiAlN composite hard coating obtained in the embodiment is about 2254.9HV.
As shown in FIG. 4, the TiNi & TiAl (Ni) N X low internal stress toughness layer deposited on the surface of the 304 stainless steel alloy substrate in the embodiment is complete and compact, and is well combined with the alloy substrate, and the total thickness is about 6.1 mu m. EDS detection shows that the atomic percentage content of each element in the matrix phase of the TiAl (Ni) N X in the gray region in the low-internal stress tough layer is as follows: ti:39.66%, al:16.44%, ni:3.98%, N:39.92%. In the low-internal-stress tough layer, the atomic percentage content of each element in the white strip-shaped second phase particles (TiNi toughening particles) pointed by the arrow is as follows in sequence: ti:53.67%, ni:43.40%, N:2.93 percent belongs to a micro-nitrogen TiNi metal soft tough phase, and because Ni element belongs to a metal element which does not form nitride, the nitrogen content in the TiNi metal soft tough phase is lower, so that a nitride hard phase is avoided. In the low internal stress tough layer, the soft tough phase of the embedded TiNi metal may be related to the tissue structure, the melting point (TiNi alloy melting point is about 1240-1310 ℃, the TiAl alloy melting point is higher than 1400 ℃, and the pure Ti metal melting point is about 1668 ℃) and the heat conducting property of the TiNi alloy target, and the factors can cause obvious differences in sputtering yield, target temperature and sputtering metal ion energy in the evaporation sputtering process of the TiNi alloy target, so that a large number of metal droplets are easily generated in the evaporation sputtering process of the TiNi alloy target. by adjusting the pulse bias voltage value and the nitrogen gas pressure value, the injection energy of the incident plasma is improved, and the size and the quantity of TiNi metal phases can be reduced. When the TiNi metal soft tough phase is uniformly embedded in the TiAl (Ni) N X matrix phase, the internal stress of the whole TiNi & TiAl (Ni) N X low internal stress tough layer can be effectively reduced, and the toughness of the coating is improved. As shown in fig. 5, diffraction peaks of TiN were detected in the XRD pattern, and diffraction peaks of crystalline Ni or Ni-containing phase were not detected, which indicates that Ni element in the matrix phase of TiAl (Ni) N X was solid-dissolved in the Ti (Al) N coating lattice in the gray region in the low internal stress tough layer of TiNi & TiAl (Ni) N X. Through detection, the hardness value of the TiNi & TiAl (Ni) N X low-internal stress tough layer obtained by the embodiment is 1911.4HV.
Residual stress of the deposited TiNi & TiAl (Ni) N X low internal stress tough layer was measured and calculated using a substrate deformation method and Stoney formula (below). The specific test and calculation method is as follows: after a TiNi & TiAl (Ni) N X low internal stress tough layer is deposited on a silicon wafer according to the steps on one side, the Si wafer is bent towards the side not coated with the coating, and the residual stress in the coating is compressive stress. The curvature radius of the silicon wafer is measured by a contact surface profiler, the thickness and the section morphology of the coating are measured and observed by a scanning electron microscope, the thickness and the section morphology are substituted into Stoney formula, the residual stress of the coating is calculated, when the residual stress is calculated, the Young modulus of the silicon wafer is 130.9GPa, the Poisson ratio of the silicon wafer is 0.28, and the thickness of the silicon wafer is 200 mu m.
E s: young's modulus of the substrate;
v s: poisson's ratio of the substrate;
t s: the thickness of the substrate;
t f: the thickness of the coating;
r: radius of curvature of substrate bending caused by the full thickness residual stress of the coating.
The radius of curvature of the substrate (Si sheet) bending caused by the full thickness residual stress of the coating was measured and calculated to be about 0.9042 x10 6～1.1145×106 μm, and the thickness of the coating was about 0.6 to 0.75 μm, i.e., the residual stress was about-1.795±0.0148gpa (-No. stands for compressive stress) in the TiNi & TiAl (Ni) N X low internal stress tough layer deposited on the Si sheet surface.
Example 2
In the embodiment, ti6Al4V alloy is used as a matrix material, and a multi-arc ion plating technology is adopted to prepare the TiNi & TiAl (Ni) N X/TiAlN composite hard coating.
(1) The preparation and installation of the alloy target, the pretreatment of the matrix sample, the selection of the sample hanging position and the like are the same as those of the preparation of the TiNi & TiAl (Ni) N X/TiAlN composite hard coating in the embodiment 1.
(2) Coating: a TiNi & TiAl (Ni) N X/TiAlN composite hard coating is deposited by using a multi-arc ion plating device.
The coating steps are as follows:
① And (5) revolving the revolving frame to a position opposite to the target center of the pure Ti, and closing the chamber door. After the temperature of the chamber is raised to 200 ℃ and the air pressure in the chamber is pumped to 5.0 multiplied by 10 -3 Pa, starting the rotating frame to rotate, introducing argon, keeping the air pressure at about 4.0Pa, starting a bias power supply, setting pulse bias to-800V, setting the duty ratio to be 40%, cleaning a substrate sample by using argon ions for 3min, and closing the bias power supply;
② Maintaining the self-transmission of the rotating frame, adjusting an argon flow meter, maintaining the air pressure in the cavity to 2.0Pa, starting a bias power supply, and starting a pure Ti target arc power supply. The specific process parameters are as follows: the pulse bias is-950V, duty cycle 10%, arc current 70A. And bombarding the matrix sample by using a high-energy ion beam for 3min, and removing dirt and oxide scale on the surface of the matrix sample.
③ The pulse bias voltage is regulated to-200V, the duty ratio is 20%, the arc current is 70A, the Ti bonding layer is deposited, and the deposition time is 5.5min.
④ Maintaining self-transmission of the rotating frame, opening a nitrogen flow valve, adjusting nitrogen and argon flow meters, controlling the flow ratio of the nitrogen to the argon to be in a range of 8:1, maintaining the air pressure in the cavity to 2.0Pa, adjusting pulse bias to-100V, adjusting the duty ratio to 20%, starting a Ti-Al alloy target arc power supply, and adjusting the arc current to 70A. And opening the revolving frame to revolve to a position opposite to the connecting line of the Ti-Al alloy target and the target center of the Ti-Ni alloy target, closing the revolving frame to revolve, and opening the revolving frame to rotate. And (3) switching off the arc power supply of the pure Ti target material, and depositing a TiAlN transition layer for 21min.
⑤ Regulating a nitrogen flow meter, maintaining the air pressure in a cavity to 2.5Pa, regulating pulse bias to-200V, turning on a Ti-Ni alloy target arc power supply, regulating arc current to 70A, and depositing a TiNi & TiAl (Ni) N X low-internal stress tough layer for 12min.
⑥ Regulating a nitrogen flow meter, maintaining the air pressure in the cavity to 2.0Pa, regulating the pulse bias to-100V, closing the arc power supply of the Ti-Ni alloy target material, and depositing the TiAlN high internal stress hard layer for 33min.
⑦ And after the TiAlN coating is deposited, continuously depositing a TiNi & TiAl (Ni) N X low-internal-stress tough layer according to the step 5 and depositing a TiAlN high-internal-stress hard layer according to the step 6 until the total number of TiNi & TiAl (Ni) N X/TiAlN functional layers is n=6. After the coating deposition is finished, the arc power supply and the bias power supply are turned off, the nitrogen valve and the argon valve are turned off, and the rotating frame self-transmission is turned off.
⑧ And (3) keeping the air pressure in the cavity at 4.0 multiplied by 10 -3 Pa, taking out the Ti6Al4V alloy sample after the temperature of the cavity is cooled to below 100 ℃, and finishing the preparation of the TiNi & TiAl (Ni) N X/TiAlN composite hard coating.
(3) Coating structure characterization and performance testing
As shown in FIG. 6, the TiNi & TiAl (Ni) N X/TiAlN composite hard coating deposited on the surface of the Ti6Al4V alloy matrix in the embodiment is complete and compact, and is well combined with the alloy matrix. In the composite hard coating, the thickness of the Ti bonding layer is about 0.55 mu m, and the thickness of the TiAlN transition layer is about 2.20 mu m; the layer thickness ratio of TiNi & TiAl (Ni) N X/TiAlN functional layers is about 1:3, 6 layers (namely TiNi & TiAl (Ni) N X and 3 layers of TiAlN each), the TiNi & TiAl (Ni) N X low internal stress toughness layer has a thickness of about 1.15 μm, the TiAlN high internal stress hard layer has a thickness of about 3.30 μm, and the composite hard coating has a total thickness of about 16.1 μm. A small amount of white strip-shaped TiNi phase toughening particles are distributed in the TiNi & TiAl (Ni) N X low-internal-stress toughening layer, and EDS detection results show that the atomic percentage content of each element in the TiNi (Ni) N X matrix phase in the toughening layer is as follows: ti:40.78%, al:13.64%, ni:4.66%, N:40.92%. The hardness value of the TiNi & TiAl (Ni) N X/TiAlN composite hard coating obtained in the embodiment is 2096.6HV.
Comparative example 1
A TiAlN hard coating is prepared by taking a silicon wafer with the size of 50.0mm multiplied by 5.0mm multiplied by 0.2mm as a matrix material and adopting a multi-arc ion plating method.
(1) Preparing an alloy target: the Ti-30Al (at%) alloy target material prepared by adopting a vacuum smelting method is used as a cathode target, and the purity of the alloy is more than or equal to 99.9 wt%.
(2) Alloy target installation: the Ti-30Al (at.%) alloy target is installed in a multi-arc ion plating device.
(3) The pretreatment of the base test piece was the same as in example 1.
(4) Coating: and depositing the TiAlN hard coating by using a multi-arc ion plating device. The coating steps are as follows:
① Fixing the silicon wafer on a clamp to shield one of two surfaces of the silicon wafer; and hanging a clamp for fixing the silicon wafer on a rotating frame opposite to the Ti-Al target, closing a chamber door, after the temperature of the chamber is raised to 200 ℃, vacuumizing the chamber to 5.0 multiplied by 10 -3 Pa, starting the rotating frame to rotate, introducing argon, keeping the air pressure between 4.0Pa, starting a bias power supply, setting pulse bias to-850V, setting the duty ratio to be 40%, cleaning the sample for 3min by using argon ions, and closing the bias power supply.
② Maintaining the rotating frame to rotate, opening a nitrogen flow valve, adjusting nitrogen and argon flow meters, controlling the flow ratio of the nitrogen to the argon to be 7:1, maintaining the air pressure in the cavity to 2.0Pa, starting a bias power supply, and starting a Ti-Al alloy target arc power supply. The specific process parameters are as follows: arc current 70A, pulse bias-900V, duty cycle 10%. Bombarding the matrix sample for 3min by using target ions, and removing dirt and oxide scale on the surface of the matrix sample.
③ The pulse bias was adjusted to-100V, duty cycle 20%, and the TiAlN coating was deposited. The specific process parameters are as follows: the arc current of the Ti-Al alloy target material is 70A, and the deposition time is 10min. After the coating deposition is finished, the arc power supply and the bias power supply are turned off, the nitrogen valve and the argon valve are turned off, and the rotating frame is turned off.
④ And (3) keeping the air pressure in the cavity at 4.0 multiplied by 10 -3 Pa, taking out the Si sheet sample after the temperature of the cavity is cooled to below 100 ℃, and finishing the preparation of the TiAlN hard coating.
(5) Coating structure characterization and performance testing
The same stress test method as in example 1 was used, and the curvature radius of the bending of the substrate (Si sheet) caused by the residual stress of the full thickness of the coating layer was measured and calculated to be about 0.3362×10 6～0.3376×106 μm, and the thickness of the coating layer was about 0.81 μm, namely, the residual stress was about-4.442.+ -. 0.0094GPa (-number stands for compressive stress) in the TiAlN hard coating layer deposited on the surface of the Si sheet. The measurement result is 2.5 times of the measurement result of residual stress in the TiNi & TiAl (Ni) N X low internal stress tough layer in the example 1.
The results of the examples and the comparative examples show that by adopting the preparation process in the invention, the TiNi metal particles toughened TiNi & TiAl (Ni) N X low internal stress tough layer regulated by pulse bias is used as an intermediate layer and is deposited alternately with the TiAlN high internal stress hard layer, so that the internal stress of the TiNi & TiAl (Ni) N X/TiAlN composite hard coating can be reduced, the toughness of the composite coating can be improved, the preparation of the composite hard coating with the thickness of more than 10 mu m and excellent bonding performance can be realized, and the application reliability and the service life of the hard coating can be greatly improved.
Claims (7)
1. A high-strength and high-toughness low-internal-stress thick TiNi & TiNi (Ni) N X/TiAlN composite hard coating is characterized in that an alloy matrix is taken as a substrate, the TiNi & TiNi (Ni) N X/TiAlN composite hard coating comprises a Ti bonding layer, a TiAlN transition layer and a TiNi & TiNi (Ni) N X/TiAlN functional layer from inside to outside, and the TiNi & TiNi (Ni) N X/TiAlN functional layer is formed by sequentially and circularly superposing a TiNi & TiNi (Ni) N X low-internal-stress tough layer and a TiAlN high-internal-stress hard layer with the layer thickness ratio r being 1:1 or less than or equal to 1:5; the total number of layers N of TiNi & TiAl (Ni) N X/TiAlN functional layers is adjustable within the range of 2-20, and the total number of layers N is an even number;
In the TiNi & TiNi (Ni) N X/TiAlN composite hard coating, the TiNi & TiNi (Ni) N X low internal stress tough layer is a TiNi metal particle toughened TiNi (Ni) N X composite hard coating regulated by pulse bias; the atomic proportion relation of each element in TiAl (Ni) N X phase is as follows: al/(ti+al+ni) =0 to 0.5, ni/(ti+al+ni) =0.05 to 0.3, x=n/(n+ti+al+ni) =0.35 to 0.5; the atomic proportion relation of each element in TiNi phase is as follows: ti/(ti+ni+n) =0.40 to 0.55, and Ni/(ti+ni+n) =0.40 to 0.5.
2. The high-strength, high-toughness, low-internal stress and thick TiNi (Ni) N X/TiAlN composite hard coating according to claim 1, wherein the Ti bonding layer is 0.2-1.0 μm in thickness, the TiAlN transition layer is 0.2-3.0 μm in thickness, and the total thickness of the composite hard coating is 5.0-30.0 μm.
3. The high strength and toughness low internal stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating according to claim 1, wherein the microhardness of the TiNi & TiAl (Ni) N X/TiAlN composite hard coating is more than 2000 Hv.
4. A method for preparing a high-strength low-internal stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating according to any one of claims 1 to 3, wherein the TiNi & TiAl (Ni) N X/TiAlN composite hard coating is prepared by a multi-target co-deposition technology by adopting a multi-arc ion plating technology.
5. The method for preparing the high-strength and high-toughness low-internal stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating, according to claim 4, is characterized by comprising the following specific steps:
Step 1, grinding and polishing an alloy matrix to ensure that the surface roughness Ra of the alloy matrix is lower than 0.2 mu m;
step 2, immersing the alloy matrix in a mixed solvent of absolute ethyl alcohol and acetone for 10-15 min, ultrasonically cleaning, removing oil stains, and drying for later use;
step 3, installing 1 pure Ti target, 1 Ti-Al alloy target and 1 Ti-Ni alloy target in a chamber of multi-arc ion plating equipment, wherein the connecting line of the target centers of the Ti-Al alloy target and the Ti-Ni alloy target is vertical to a base, the Ti-Al alloy target is positioned at the upper end, the Ti-Ni alloy target is positioned at the lower end, and the distance between the double target centers of the Ti-Al alloy target and the Ti-Ni alloy target is in the range of 25-30 cm; the horizontal positions of the pure Ti target and the Ti-Al alloy target are kept basically consistent, and the installation positions of the pure Ti target and the Ti-Al alloy target are opposite to the Ti-Al alloy target;
Step 4, hanging an alloy matrix at a position between a Ti-Al alloy target and a Ti-Ni alloy target bullion on a rotating frame in a cavity, wherein the specific position is determined by a designed layer thickness ratio of TiNi & TiAl (Ni) N X/TiAlN functional layer, plating bias parameters and Ni content required by TiAl (Ni) N X phase in a TiNi & TiAl (Ni) N X low-internal stress tough layer;
Step 5, revolving the revolving frame to a position opposite to the target center of the pure Ti, closing a chamber door, after the temperature of the chamber is raised to 200 ℃ and the air pressure in the chamber is pumped to be less than or equal to 7.0 multiplied by 10 -3 Pa, starting the revolving frame to rotate, introducing argon, keeping the air pressure between 3.0 Pa and 4.0Pa, starting a bias power supply, setting pulse bias to be-700V to-900V, setting the duty ratio to be 30-40%, cleaning for 3-10 minutes by using argon ions, and closing the bias power supply;
Step 6, maintaining the rotation of the rotating frame, adjusting an argon flow meter, and maintaining the air pressure in the cavity to be 1.5-2.0 Pa; starting a bias power supply, setting pulse bias voltage to-850 to-1000V, and setting duty ratio to 5-10%; starting a pure Ti target arc power supply, and regulating the arc current to 70-80A; bombarding for 3-5 min by using a high-energy ion beam to remove surface dirt and oxide skin;
Step 7, regulating pulse bias voltage to-200V to-400V, duty ratio to 15-20%, arc current to 70-80A, depositing Ti bonding layer, and controlling coating thickness by changing deposition time;
Step 8, maintaining the rotation of the rotating frame, opening a nitrogen flow valve, regulating a nitrogen flow meter and an argon flow meter, controlling the flow ratio of the nitrogen flow meter and the argon flow meter to be in a range of 7:1-15:1, maintaining the air pressure in the cavity to be 1.5-2.0 Pa, starting a Ti-Al alloy target arc power supply, regulating pulse bias to-100V to-300V, and regulating the arc current to 70-100A with a duty ratio of 10-20%; opening the revolving frame to revolve to a position opposite to the connecting line of the Ti-Al alloy target and the target center of the Ti-Ni alloy target, closing the revolving frame to revolve, and opening the revolving frame to rotate; closing a pure Ti target arc power supply, depositing a TiAlN transition layer, and controlling the thickness of the coating by changing the deposition time;
Step 9, regulating a nitrogen flow meter, maintaining the air pressure in a cavity to 2.0-3.0 Pa, regulating pulse bias to-200V to-500V, switching on a Ti-Ni alloy target arc power supply with a duty ratio of 15-20%, regulating arc current to 70-85A, depositing a TiNi & TiAl (Ni) N X low internal stress tough layer, and controlling the thickness of the coating by changing deposition time;
Step 10, regulating a nitrogen flow meter, and maintaining the air pressure in the cavity to be 1.5-2.0 Pa; adjusting pulse bias to-100V to-300V, switching off a Ti-Ni alloy target arc power supply, depositing a TiAlN high internal stress hard layer, and controlling the thickness of the coating by changing deposition time;
Step 11, continuously depositing a TiNi & TiAl (Ni) N X low-internal-stress tough layer according to the step 9 and continuously depositing a TiAlN high-internal-stress hard layer according to the step 10 after the deposition of the TiAlN high-internal-stress hard layer is finished until the total number N of TiNi & TiAl (Ni) N X/TiAlN functional layers reaches the design requirement of the number of layers; after the coating deposition is finished, the arc power supply and the bias power supply are turned off, the nitrogen flow valve and the argon flow valve are turned off, and the rotating frame is turned off for autorotation;
And 12, maintaining the air pressure in the cavity to be less than or equal to 7.0 multiplied by 10 -3 Pa, and taking out the alloy matrix after the temperature of the cavity is cooled to be lower than 100 ℃ to finish the preparation of the TiNi & TiAl (Ni) N X/TiAlN composite hard coating.
6. The method for preparing the high-strength and high-toughness low-internal stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating according to claim 5, wherein in the step 1, the alloy substrate is a hard alloy material, a stainless steel alloy material, a titanium alloy material or a titanium aluminum alloy material.
7. The method for preparing the high-strength and high-toughness low-internal stress thick TiNi & TiAl (Ni) N X/TiAlN composite hard coating, which is characterized in that in the step 3, the purity of a pure Ti target material is more than or equal to 99.9wt.%; in the Ti-Al alloy target, the Al content is 30at percent to 50at percent, and the alloy purity is more than or equal to 99.9wt percent; in the Ti-Ni alloy target material, the Ti content is 50at percent, the Ni content is 50at percent, and the alloy purity is more than or equal to 99.9 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310751182.5A CN116770227B (en) | 2023-06-25 | 2023-06-25 | High strength and toughness low internal stress thick TiNi & TiAl (Ni) NXTiAlN composite hard coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310751182.5A CN116770227B (en) | 2023-06-25 | 2023-06-25 | High strength and toughness low internal stress thick TiNi & TiAl (Ni) NXTiAlN composite hard coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116770227A CN116770227A (en) | 2023-09-19 |
| CN116770227B true CN116770227B (en) | 2024-06-28 |
Family
ID=87990912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310751182.5A Active CN116770227B (en) | 2023-06-25 | 2023-06-25 | High strength and toughness low internal stress thick TiNi & TiAl (Ni) NXTiAlN composite hard coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116770227B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116334536A (en) * | 2023-03-29 | 2023-06-27 | 东北大学 | High-toughness transition metal nitride TiAl (Ni) N X Hard coating and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4555862B2 (en) * | 2005-09-01 | 2010-10-06 | オーエスジー株式会社 | Hard laminate coating and hard laminate coating tool |
| CN101318394A (en) * | 2007-06-06 | 2008-12-10 | 厦门金鹭特种合金有限公司 | Novel TiA1N composite multiple coating applied for cutting tool |
| CN102345091A (en) * | 2010-07-29 | 2012-02-08 | 鸿富锦精密工业（深圳）有限公司 | Coating, part having the coating, and preparation method of the part |
| CN104260440B (en) * | 2014-09-25 | 2016-06-15 | 温岭市温峤友德工具厂 | A kind of nano-composite coating cutter containing aluminum titanium silicon yttrium nitrogen and preparation method thereof |
| CN110004415B (en) * | 2019-04-09 | 2021-03-12 | 河南科技学院 | High-toughness and high-hardness thick Ti/TiAlN multilayer coating and preparation method thereof |
| EP4059637A1 (en) * | 2021-03-17 | 2022-09-21 | Seco Tools Ab | Cutting tool |
-
2023
- 2023-06-25 CN CN202310751182.5A patent/CN116770227B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116334536A (en) * | 2023-03-29 | 2023-06-27 | 东北大学 | High-toughness transition metal nitride TiAl (Ni) N X Hard coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116770227A (en) | 2023-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Microstructure, hardness and corrosion behaviour of Ti/TiN multilayer coatings produced by plasma activated EB-PVD | |
| CN106893986B (en) | A kind of high rigidity AlCrN nano-composite coating and its preparation process | |
| CN111005002B (en) | Preparation method of erosion-resistant and corrosion-resistant self-cleaning coating for compressor blade | |
| CN105887012B (en) | A kind of Zr-B-N nano-composite coatings preparation process | |
| CN112981321B (en) | Single-phase structure (CrZrVTiAl) N high-entropy ceramic coating and preparation method thereof | |
| RU2678492C1 (en) | Device for producing a composite film of multi-element alloy | |
| CN106987816A (en) | Preparation process of high-aluminum-content ultra-compact Al-Cr-Si-N coating | |
| CN113652659B (en) | Preparation method of high-entropy alloy nitride coating metallurgically bonded with substrate | |
| CN101698933B (en) | Multi-element Ti-Al-N nanometer composite laminated coating and preparation method thereof | |
| CN108251797B (en) | TiAlN/CrN multilayer coating for titanium alloy cutting tool and preparation method thereof | |
| CN103409722A (en) | Method for preparing anti-erosion coating on surface of aero engine air compressor blade | |
| CN111647851B (en) | Zr-B-N nano composite coating with high hardness and high toughness and preparation method thereof | |
| CN107338409B (en) | Process method for preparing nitrogen-based hard coating by adjustable magnetic field arc ion plating | |
| CN109402564A (en) | A kind of AlCrSiN and AlCrSiON double-layer nanometer composite coating and preparation method thereof | |
| CN104480443A (en) | Hard and tough nano composite ZrAlCuN coating and preparation method thereof | |
| CN109778119A (en) | A kind of Ni-CrSiN wear-and corrosion-resistant coating and preparation method thereof | |
| CN109735799A (en) | A kind of cutting tool surface multi-layer step high temperature wear-resistant coating and preparation method thereof | |
| CN101294284A (en) | Ablation-resistant fatigue-resistant plasma surface recombination reinforcing method | |
| CN102766846A (en) | AN/Cr1-xAlxN/Cr30(Al, Y)70N hard gradient coating and its prepn | |
| CA2600097A1 (en) | Physical vapour deposition process for depositing erosion resistant coatings on a substrate | |
| CN106893991A (en) | Preparation process of Zr-B-O-N nano composite coating | |
| CN116334536B (en) | High-toughness transition metal nitride TiAl (Ni) NXHard coating and preparation method thereof | |
| CN102912302B (en) | Method for preparing yttrium/silicon nitride compound coating material on surface of magnesium alloy | |
| CN116770227B (en) | High strength and toughness low internal stress thick TiNi & TiAl (Ni) NXTiAlN composite hard coating and preparation method thereof | |
| CN103045998A (en) | Product containing CrNiTiAlN quinary coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |