CN116121700A - Refractory element doped wear-resistant gradient HfMSiCN ceramic layer and preparation method thereof - Google Patents
Refractory element doped wear-resistant gradient HfMSiCN ceramic layer and preparation method thereof Download PDFInfo
- Publication number
- CN116121700A CN116121700A CN202211740550.8A CN202211740550A CN116121700A CN 116121700 A CN116121700 A CN 116121700A CN 202211740550 A CN202211740550 A CN 202211740550A CN 116121700 A CN116121700 A CN 116121700A
- Authority
- CN
- China
- Prior art keywords
- layer
- hfmsicn
- ceramic layer
- gradient
- wear
- 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.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 50
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000009792 diffusion process Methods 0.000 claims abstract description 28
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 26
- 239000000956 alloy Substances 0.000 claims abstract description 26
- 229910052786 argon Inorganic materials 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 238000000151 deposition Methods 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000012495 reaction gas Substances 0.000 claims abstract description 9
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 118
- 239000013077 target material Substances 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 19
- 238000005498 polishing Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 11
- 238000005299 abrasion Methods 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 7
- 239000002344 surface layer Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000000861 blow drying Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 39
- 239000011248 coating agent Substances 0.000 abstract description 36
- 238000005516 engineering process Methods 0.000 abstract description 20
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000005477 sputtering target Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- 244000137852 Petrea volubilis Species 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 8
- 238000005524 ceramic coating Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- -1 Transition Metal Carbides Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004372 laser cladding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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
- C23C14/0664—Carbonitrides
-
- 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
- C23C14/0036—Reactive sputtering
-
- 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
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
-
- 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
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
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)
Abstract
The invention discloses a refractory element doped wear-resistant gradient HfMSiCN ceramic layer and a preparation method thereof, belonging to the technical field of Ti60 alloy surface modification, wherein a double-layer glow plasma technology is adopted to prepare the HfMSiCN gradient ceramic layer on the surface of a Ti60 sample, the selected refractory doping elements M are Ta, zr, nb, ti respectively, and the types of the refractory doping elements M play a role in determining the high-temperature wear resistance of the gradient HfMSiCN ceramic layer; the method is characterized in that grid-shaped high-purity Hf, si, M, C is used as a sputtering target, the atomic ratio of each element in the target is 5-40%, argon is used as working gas, and nitrogen is used as reaction gas. The HfMSiCN gradient ceramic layer comprises a deposition layer and a diffusion layer, wherein the diffusion layer is connected with the Ti60 matrix, so that the bonding strength between the coating and the matrix can be improved, the mechanical property of the matrix is improved, and the high-temperature friction coefficient and the wear rate are reduced.
Description
Technical Field
The invention belongs to the technical field of Ti60 alloy surface modification, and particularly relates to a refractory element doped wear-resistant gradient HfMSiCN ceramic layer and a preparation method thereof.
Background
With the continuous implementation of the national and manufacturing strategies of the ocean, the development of ocean resources is not separated from the updating of equipment, and the high-temperature components of the marine ship engine face a more serious service environment. The Ti60 alloy has wide application value in key parts of engines of ships and carrier-based aircraft due to high specific strength, excellent corrosion resistance and creep resistance, but the defects of poor wear resistance, easy oxidation and the like at high temperature limit the further application of the Ti60 alloy in the high-temperature parts of the engines. Because the initial end of the high-temperature friction and wear behavior occurs on the surface of the Ti60 alloy, the surface modification technology is adopted to prepare the high-temperature resistant coating on the surface of the Ti60 part, and the surface overcomes the problems while the original excellent performance of the matrix material is maintained.
Transition Metal Carbides (TMC) and nitrides (TMN) have a combination of covalent, ionic and metallic bonds, and are widely used as promising ceramic materials due to their excellent properties, including high hardness and melting point, and excellent thermal stability. Many crystalline TMC and TMN in rock salt structures, due to the stable vacancies, furthermore, transition metal carbonitrides (TMCNs, m=3d, 4d or 5d TM) exhibit superior properties such as high hardness (H), strength and toughness than their corresponding pure carbides and nitrides, such as TaCN, nbCN, crCN and HfCN. Suxuan Du et al, journal Surface&Coatings Technology in volume 328, "N dependent tribochemistry: achieving superhard wear-resistance low-friction TaCxNy films" in which TaC deposited by DC magnetron sputtering is studied x N y A coating in which C and N atoms occupy interstitial sites of the Ta sub-lattice to formNaCl-forming TaC x N y Solid solutions. Compared with TaC coating, taC x N y The coating shows better wear properties, and minimal wear rate. However, the coating deposited by sputtering has poor bonding force with the substrate, further limiting the application range, such as poor high temperature oxidation resistance and easy spalling of the coating under ultra-high temperature abrasion conditions. To further improve the performance of TMCNs coatings. Many researchers have made up for the disadvantages of TMCNs coatings by adding modifying elements (Si, B) to the TMCNs ceramic coating to form a composite ceramic coating, obtaining a composite oxide layer with low oxygen permeability, medium coefficient of thermal expansion, and high viscosity at high temperature wear.
In recent years, various ceramic coatings containing N, B, C and other elements have been widely used, such as "Dependence of characteristics of Hf (M) SiBCN (m=y, ho, ta, mo) thin films on the M choice:ab-initio and experimental study" in journal Acta materials, volume 206, martin Matas et al, herein a Hf (M) SiBCN coating deposited by magnetron sputtering was studied, indicating that a suitable M type and composition was selected to obtain a hard film with good high temperature stability and high conductivity at a relatively low temperature. However, the ceramic layer deposited by magnetron sputtering has poor bonding force with the substrate, and limits the application range.
At present, the preparation method of the ceramic coating mainly comprises a thermal spraying technology, a magnetron sputtering technology and a laser cladding technology. But all suffer from some drawbacks: although the thermal spraying technology is simple to operate, has short preparation period and is not easy to generate deformation and stress, the coating has poor bonding force with the matrix, thin thickness, easy to generate loose porous structure and the like, so that the coating is difficult to meet the use requirement in a high-speed heavy-load environment; the laser cladding technology has the advantages that due to high instantaneous energy, metal liquid drops are easy to splash in the preparation process, small particles are easy to form on the surface of the coating, and the bonding force between the coating and a substrate is poor; the magnetron sputtering technology has wide application in the aspect of coating preparation, but the prepared film has limited thickness and insufficient bonding force with a substrate, and the percentages of all elements in the coating are difficult to be ensured to be equal to those in a target material. Therefore, a preparation method capable of improving the bonding strength of the coating and the substrate and improving the comprehensive performance of the coating and having simple procedures is needed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the refractory element doped wear-resistant gradient Hf (M) SiCN ceramic layer and the preparation method thereof, and the prepared ceramic layer is a gradient ceramic layer with high bonding strength, excellent mechanical property, good high-temperature wear resistance and controllable element types and components.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the refractory element doped wear-resistant gradient HfMSiCN ceramic layer is formed by directly sputtering and depositing a high-purity grid-shaped target material on the surface of Ti60 alloy through a double-glow plasma surface metallurgical technology, wherein the surface layer is a Hf (M) SiCN deposition layer, and the thickness is 10-20 mu M; the middle layer is a diffusion layer with the thickness of 3-10 mu m; the diffusion layer and the Ti60 matrix are mutually diffused, and the content of Hf, M, si, C, N element in the diffusion layer is gradually reduced from the outside to the inside; the refractory doping element M selected each time is Ta, zr, nb or Ti, and the type of the refractory doping element M plays a role in determining the high-temperature wear resistance of the gradient Hf (M) SiCN ceramic layer; argon is the working gas and nitrogen is the reaction gas.
A preparation method of a refractory element doped wear-resistant gradient HfMSiCN ceramic layer comprises the following steps:
step 1, pretreatment of a matrix material
Processing Ti60 alloy into a sample with the size of 15mm multiplied by 5mm by adopting a linear cutting method, polishing by using 80-1000 mesh SiC waterproof abrasive paper, and polishing to form a mirror surface by putting on a polishing machine; finally, placing the mixture into a beaker filled with absolute ethyl alcohol for ultrasonic cleaning and drying for later use;
step 2, cleaning and placing the sample
Polishing the inner wall of a furnace body and the surface of a target material by using fine sand paper before loading the sample, removing surface impurities and oxide films, dipping non-woven fabrics in absolute ethyl alcohol, wiping, putting the pretreated sample and Hf (M) SiC grid-shaped target material into a double-layer glow plasma furnace, arranging the target material composition structure from left to right at equal intervals according to Hf/Si/M/C, adjusting the target base distance to 15-25mm, taking Ti60 alloy as a cathode, taking Hf (M) SiC grid-shaped target material as a source electrode, ar as working gas and N 2 As a means ofThe reaction gas, the grid-shaped high purity Hf, si, M, C is used as a target material, and the atomic ratio of each element is 5% -40%;
step 3, vacuumizing
Closing the double-layer glow plasma furnace body, opening a mechanical pump, and pumping the gas in the furnace to below 2 Pa;
step 4, introducing argon
Opening a gas flowmeter and a valve control switch, and preheating a power supply; opening an argon bottle valve after the furnace reaches the corresponding vacuum degree, and continuously introducing argon for 20 minutes for cleaning;
step 5, starting sputtering
Regulating the air pressure in the double-layer glow plasma furnace body to 25Pa; when starting, the source voltage is regulated to 850V, and the workpiece voltage is 420V;
step 6, preparing the Hf (M) SiCN gradient ceramic layer by using a double-glow plasma metallurgy technology
The gas pressure in the furnace is controlled at 25Pa, the source electrode voltage is 800-900V, the workpiece voltage is 400-450V, the Hf (M) SiCN ceramic layer is prepared by changing the M type and the M content in the Hf (M) SiC grid-shaped target material, reactive nitrogen is introduced, and the flow ratio of the argon to the nitrogen is regulated to 1:3, a step of;
step 7, heat preservation
Preserving heat for 4-7h;
step 8, discharging
And after the heat preservation is finished, cooling to room temperature to obtain the Ti60 alloy with the surface provided with the HfMSiCN gradient ceramic layer.
The beneficial effects are that: the invention provides a refractory element doped wear-resistant gradient HfMSiCN ceramic layer and a preparation method thereof, compared with the prior art, the refractory element doped wear-resistant gradient HfMSiCN ceramic layer has the advantages that:
(1) The invention adopts a double-glow plasma metallurgical technology to prepare the HfMSiCN gradient ceramic layer, takes a high-purity HfMSiC grid-shaped target material as a sputtering target material, can effectively improve the hollow cathode effect and the sputtering rate of the target material, has controllable types and components of the selected refractory doping element M, takes argon as working gas and nitrogen as reaction gas, and can obviously improve the bonding strength between the prepared coating and a substrate due to the existence of a diffusion layer;
(2) The seepage layer prepared by the invention has a certain thickness of 10-40 mu m, forms good metallurgical bonding between the coating and the matrix, improves the mechanical property of the matrix, reduces the high-temperature friction coefficient and the abrasion rate as shown in table 1, can effectively protect the matrix material in a high-temperature friction abrasion environment, and can reduce the abrasion loss of the matrix by 50% under the high-temperature abrasion at 500 ℃;
(3) Compared with the traditional method for relieving the problem of poor film-based bonding by adding a supporting layer, the HfMSiCN ceramic coating can essentially solve the problem of poor film-based bonding by preparing a high-strength and high-toughness coating by adjusting the type and the content of M element in a grid-shaped target;
(4) The preparation method disclosed by the invention is simple to operate, safe and environment-friendly, and low in production cost.
Drawings
FIG. 1 is a schematic view of a target structure used in the present invention;
FIG. 2 is an SEM image of an embodiment 4 of the invention;
FIG. 3 is a schematic illustration of a coating prepared in accordance with the present invention;
in the figure, 1 is a deposition layer, 2 is a diffusion layer, 21 is a coating inward diffusion layer, and 22 is a substrate outward diffusion layer.
Detailed Description
The invention will be described in detail below with reference to the attached drawings and to specific embodiments:
the experimental methods in the following examples are conventional methods unless otherwise specified; the test materials used were purchased from conventional shops unless specified otherwise; the quantitative tests in the following examples were each set up in triplicate, and the data are the average of the triplicate or the standard deviation of the average.
Example 1
The ceramic layer is directly sputtered and deposited on the surface of Ti60 alloy by adopting a high-purity grid-shaped target material through a double-glow plasma surface metallurgical technology, and the surface layer is an HfMSiCN deposition layer with the thickness of 10-20 mu m; the intermediate layer is an HfMSiCN diffusion layer with a thickness of 3-10 μm. The selected refractory doping element M is Ti, and the atomic ratio of each element is 5% -40%. The HfMSiCN ceramic layer comprises a deposition layer 1 and a diffusion layer 2, wherein the coating and the Ti60 matrix form good metallurgical bonding.
The preparation method of the ceramic layer comprises the following steps:
step 1, pretreatment of a matrix material
The Ti60 alloy is processed into a sample with the size of 15mm multiplied by 5mm by adopting a linear cutting method, and then is polished by using 80-1000SiC waterproof sand paper, and then is put on a polishing machine to be polished to a mirror surface. Finally, placing the mixture into a beaker filled with absolute ethyl alcohol for ultrasonic cleaning and drying for later use;
step 2, cleaning and placing the sample
Polishing the inner wall of a furnace body and the surface of a target material by using fine sand paper before loading the sample, removing surface impurities and oxide films, dipping non-woven fabrics in absolute ethyl alcohol, wiping, putting the pretreated sample and HfSiTiC grid-shaped target material into a double-layer glow plasma furnace, arranging target material composition structures from left to right at equal intervals according to Hf/Si/Ti/C, adjusting the target base distance to 18mm, taking Ti60 alloy as a cathode, taking HfSiTiC grid-shaped target material as a source electrode, taking Ar as working gas, and N 2 As a reaction gas;
step 3, vacuumizing: closing the double-layer glow plasma furnace body, opening a mechanical pump, and pumping the gas in the furnace to below 2 Pa;
and 4, introducing argon: opening a gas flowmeter and a valve control switch, and preheating a power supply; opening an argon bottle valve after the furnace reaches the corresponding vacuum degree, and continuously introducing argon for 25 minutes for cleaning;
step 5, starting sputtering: regulating the air pressure in the double-layer glow plasma furnace body to 20Pa; when starting, the source voltage is regulated to 800V, and the workpiece voltage is 400V;
step 6, preparing the HfTiSiCN gradient ceramic layer by a double-glow plasma metallurgical technology: controlling the pressure in the furnace at 25Pa, the source voltage at 850V and the workpiece voltage at 420V, introducing reaction nitrogen, and adjusting the flow ratio of argon to nitrogen to 1:3, a step of;
step 7, heat preservation: preserving heat for 5 hours;
step 8, discharging: after the heat preservation is finished, cooling to room temperature to obtain the Ti60 alloy with the surface provided with the HfTiSiCN gradient ceramic layer, wherein the prepared coating is respectively provided with a HfTiSiCN deposition layer 1 with the thickness of 14.15 mu m, a diffusion layer 2 with the thickness of 2.19 mu m and a Ti60 titanium alloy from the surface to the inside.
Example 2
The ceramic layer is directly sputtered and deposited on the surface of Ti60 alloy by adopting a high-purity grid-shaped target material through a double-glow plasma surface metallurgical technology, and the surface layer is an HfMSiCN deposition layer 1 with the thickness of 10-20 mu m; the intermediate layer is HfMSiCN diffusion layer 2 with thickness of 3-10 μm. The selected refractory doping element M is Ta, and the atomic ratio of each element is 5% -40%. The HfMSiCN ceramic layer comprises a deposition layer and a diffusion layer, wherein the coating and the Ti60 matrix form good metallurgical bonding.
The preparation method comprises the following steps:
step 1, pretreatment of a matrix material
The Ti60 alloy is processed into a sample with the size of 15mm multiplied by 5mm by adopting a linear cutting method, and then is polished by using 80-1000SiC waterproof sand paper, and then is put on a polishing machine to be polished to a mirror surface. Finally, placing the mixture into a beaker filled with absolute ethyl alcohol for ultrasonic cleaning and drying for later use;
step 2, cleaning and placing the sample
Polishing the inner wall of a furnace body and the surface of a target material by using fine sand paper before loading the sample into the furnace, removing surface impurities and oxide films of the target material, then dipping absolute ethyl alcohol by using non-woven fabrics, wiping, putting the pretreated sample and the HfSiTaC grid-shaped target material into a double-layer glow plasma furnace, arranging the target material composition structure from left to right at equal intervals according to Hf/Si/Ta/C, adjusting the target base distance to 18mm, taking Ti60 alloy as a cathode, taking the HfSiTaC grid-shaped target material as a source electrode, taking Ar as a working gas, and N 2 As a reaction gas;
step 3, vacuumizing: closing the double-layer glow plasma furnace body, opening a mechanical pump, and pumping the gas in the furnace to below 2 Pa;
and 4, introducing argon: opening a gas flowmeter and a valve control switch, and preheating a power supply; opening an argon bottle valve after the furnace reaches the corresponding vacuum degree, and continuously introducing argon for 25 minutes for cleaning;
step 5, starting sputtering: regulating the air pressure in the double-layer glow plasma furnace body to 20Pa; when starting, the source voltage is regulated to 800V, and the workpiece voltage is 400V;
step 6, preparing the HfTaSiCN gradient ceramic layer by using a double-glow plasma metallurgical technology: controlling the pressure in the furnace at 25Pa, the source voltage at 850V and the workpiece voltage at 420V, introducing reaction nitrogen, and adjusting the flow ratio of argon to nitrogen to 1:3, a step of;
step 7, heat preservation: preserving heat for 5 hours;
step 8, discharging: after the heat preservation is finished, cooling to room temperature to obtain Ti60 alloy with the surface provided with the HfTaSiCN gradient ceramic layer; the resulting coating was 14.15 μm deposited on the surface and inside of HfTaSiCN, and 2.19 μm thick diffusion layer and Ti60 titanium alloy, respectively.
Example 3
The ceramic layer is directly sputtered and deposited on the surface of Ti60 alloy by adopting a high-purity grid-shaped target material through a double-glow plasma surface metallurgical technology, and the surface layer is an HfMSiCN deposition layer with the thickness of 10-20 mu m; the intermediate layer is an HfMSiCN diffusion layer with a thickness of 3-10 μm. The selected refractory doping element M is Nb, and the type of the refractory doping element M plays a role in determining the high-temperature wear resistance of the gradient HfMSiCN ceramic layer. The HfMSiCN ceramic layer comprises a deposition layer and a diffusion layer, wherein the diffusion layer is connected with the Ti60 matrix.
The preparation method comprises the following steps:
step 1, pretreatment of a matrix material
The Ti60 alloy is processed into a sample with the size of 15mm multiplied by 5mm by adopting a linear cutting method, and then is polished by using 80-1000SiC waterproof sand paper, and then is put on a polishing machine to be polished to a mirror surface. Finally, placing the mixture into a beaker filled with absolute ethyl alcohol for ultrasonic cleaning and drying for later use;
step 2, cleaning and placing the sample
Before loading the sample into furnacePolishing the inner wall of a furnace body and the surface of a target material by fine sand paper, removing surface impurities and oxide films, then dipping absolute ethyl alcohol by using non-woven fabrics, wiping, putting a pretreated sample and an HfSiNbC grid-shaped target material into a double-layer glow plasma furnace, arranging target material composition structures from left to right at equal intervals according to Hf/Si/Nb/C, adjusting the target base distance to 18mm, taking Ti60 alloy as a cathode, taking HfSiNbC grid-shaped target material as a source electrode, taking Ar as working gas and N 2 As a reaction gas;
step 3, vacuumizing: closing the double-layer glow plasma furnace body, opening a mechanical pump, and pumping the gas in the furnace to below 2 Pa;
and 4, introducing argon: opening a gas flowmeter and a valve control switch, and preheating a power supply; opening an argon bottle valve after the furnace reaches the corresponding vacuum degree, and continuously introducing argon for 25 minutes for cleaning;
step 5, starting sputtering: regulating the air pressure in the double-layer glow plasma furnace body to 20Pa; when starting, the source voltage is regulated to 800V, and the workpiece voltage is 400V;
step 6, preparing an HfNbSiCN gradient ceramic layer by a double-glow plasma metallurgical technology: controlling the pressure in the furnace at 25Pa, the source voltage at 850V and the workpiece voltage at 420V, introducing reaction nitrogen, and adjusting the flow ratio of argon to nitrogen to 1:3, a step of;
step 7, heat preservation: preserving heat for 5 hours;
step 8, discharging: after the heat preservation is finished, cooling to room temperature to obtain Ti60 alloy with the surface provided with the HfNbSiCN gradient ceramic layer; the resulting coating was 14.15 μm deposited on the outside and inside of HfNbSiCN, and 2.19 μm thick diffusion layer and Ti60 titanium alloy, respectively.
Example 4
A refractory element doped wear-resistant gradient HfMSiCN ceramic layer and a preparation method thereof are provided, wherein the ceramic layer is directly sputtered and deposited on the surface of Ti60 alloy by adopting a high-purity grid-shaped target material through a double-glow plasma surface metallurgy technology, the surface layer is a Hf (M) SiCN deposition layer, and the thickness is 10-20 mu M; the intermediate layer is an HfMSiCN diffusion layer with a thickness of 3-10 μm. The selected refractory doping element M is Zr, and the type of the refractory doping element M plays a role in determining the high-temperature wear resistance of the gradient HfMSiCN ceramic layer. The HfMSiCN ceramic layer comprises a deposition layer and a diffusion layer, wherein the diffusion layer is connected with the Ti60 matrix.
The preparation method comprises the following steps:
step 1, pretreatment of a matrix material
The Ti60 alloy is processed into a sample with the size of 15mm multiplied by 5mm by adopting a linear cutting method, and then is polished by using 80-1000SiC waterproof sand paper, and then is put on a polishing machine to be polished to a mirror surface. Finally, placing the mixture into a beaker filled with absolute ethyl alcohol for ultrasonic cleaning and drying for later use;
step 2, cleaning and placing the sample
Polishing the inner wall of a furnace body and the surface of a target material by using fine sand paper before loading the sample into the furnace, removing surface impurities and oxide films of the target material, then dipping non-woven fabrics in absolute ethyl alcohol for wiping, putting the pretreated sample and the HfSiZrC grid-shaped target material into a double-layer glow plasma furnace, arranging the target material composition structure from left to right at equal intervals according to Hf/Si/Nb/C, adjusting the target base distance to 18mm, taking Ti60 alloy as a cathode, taking the HfSiZrC grid-shaped target material as a source electrode, taking Ar as a working gas, and N 2 As a reaction gas;
step 3, vacuumizing: closing the double-layer glow plasma furnace body, opening a mechanical pump, and pumping the gas in the furnace to below 2 Pa;
and 4, introducing argon: opening a gas flowmeter and a valve control switch, and preheating a power supply; opening an argon bottle valve after the furnace reaches the corresponding vacuum degree, and continuously introducing argon for 25 minutes for cleaning;
step 5, starting sputtering: regulating the air pressure in the double-layer glow plasma furnace body to 20Pa; when starting, the source voltage is regulated to 800V, and the workpiece voltage is 400V;
step 6, preparing the HfZrSiCN gradient ceramic layer by using a double-glow plasma metallurgical technology: controlling the pressure in the furnace at 25Pa, the source voltage at 850V and the workpiece voltage at 420V, introducing reaction nitrogen, and adjusting the flow ratio of argon to nitrogen to 1:3, a step of;
step 7, heat preservation: preserving heat for 5 hours;
step 8, discharging: after the heat preservation is finished, cooling to room temperature to obtain Ti60 alloy with the surface provided with the HfZrSiCN gradient ceramic layer; the resulting coating was 14.15 μm deposited on the surface and inside of HfZrSiCN, and 2.19 μm thick diffusion layer and Ti60 titanium alloy, respectively.
The coating obtained in examples 1-4 is subjected to a binding force test and a high-temperature friction and wear test, and the results show that the HfTiSiCN, hfTaSiCN, hfNbSiCN and HfZrSiCN gradient ceramic coating has good binding performance with the substrate, and as shown in the following table 2, the binding strength of the HfMSiCN gradient ceramic layer with the substrate is high, and the weight loss of the substrate is obviously larger than that of the coating, so that the coating can effectively improve the wear resistance of the substrate, and has good protection effect on the substrate. Of examples 1 to 4, the coating produced in example 1 had the best overall properties.
TABLE 1 mechanical Property test of coating
| Name of the name | Ti60 | Example 1 | Example 2 | Example 3 | Example 4 |
| Microhardness (HV) | 400.6 | 1203.1 | 890.5 | 1008.6 | 1429.0 |
TABLE 2 bonding strength of coating to substrate and wear weight loss of Ti60 substrate and Hf (M) SiCN coating at different temperatures
It should be noted that the structure of the gradient ceramic layer with HfTiSiCN attached to the surface of Ti60 prepared in example 1 of the present invention is approximately the same as the structure of the gradient ceramic layer with HfMSiCN attached to the surface of Ti60 prepared in examples 2-4, but the mechanical properties and wear resistance are greatly improved, and because the miscibility of the Ti-containing coating and the Ti60 matrix element is higher, a thicker diffusion layer is formed, so that the coating prepared in example 1 has higher bonding force.
The foregoing is merely a preferred embodiment of the present invention, and it will be understood by those skilled in the art that the technical solutions described in the foregoing embodiments may be modified or some or all of the technical features may be replaced by the same modifications or all of the features, and the essence of the corresponding technical solutions should not deviate from the scope of the technical solutions of the embodiments of the present invention, which should be covered in the protection scope of the present invention.
Claims (9)
1. The refractory element doped wear-resistant gradient HfMSiCN ceramic layer is characterized in that the surface layer of the ceramic layer is an HfMSiCN deposition layer, the inner layer is a diffusion layer connected with a substrate, and the diffusion layer and the substrate are mutually diffused; the content of Hf, M, si, C, N element in the diffusion layer is gradually reduced from the outside to the inside; and M is a refractory doping element.
2. Refractory element doped wear resistant gradient HfMSiCN ceramic layer according to claim 1 characterized in that M is Ta, zr, nb or Ti.
3. The refractory element doped wear resistant gradient HfMSiCN ceramic layer according to claim 1, characterized in that the deposited layer thickness is 10-20 μm; the thickness of the diffusion layer is 3-10 mu m.
4. The preparation method of the refractory element doped wear-resistant gradient HfMSiCN ceramic layer is characterized by comprising the following steps of:
step 1: processing the titanium alloy matrix into a proper size according to the requirement, polishing to a mirror surface, cleaning and blow-drying for later use;
step 2: removing impurities and oxide films in a double-layer glow plasma furnace and on the surface layer of a target material, putting the treated target material and a substrate into the double-layer glow plasma furnace, adjusting the target base distance, taking the substrate as a cathode, taking the target material as a source electrode, taking Ar as working gas, and taking N as a working gas 2 As a reaction gas;
step 3: vacuumizing the double-layer glow plasma furnace, and continuously introducing argon for cleaning;
step 4: regulating the air pressure in the double-layer glow plasma furnace body to 25Pa; the glow starting cleans and preheats the double-layer glow plasma furnace;
step 5: controlling the pressure in the furnace at 25Pa, controlling the source voltage at 800-900V, controlling the workpiece voltage at 400-450V, introducing reaction nitrogen, preparing an Hf (M) SiCN ceramic layer by changing the M type and the M content in the Hf (M) SiC grid-shaped target material, and preserving the heat for 4-7h;
step 6: and after the heat preservation is finished, cooling to room temperature to obtain the Ti60 alloy with the surface provided with the Hf (M) SiCN gradient ceramic layer.
5. The method for preparing the refractory element doped abrasion resistant gradient HfMSiCN ceramic layer according to claim 4, wherein the substrate is polished by using 80-1000 mesh SiC waterproof abrasive paper in step 1, and then is polished to a mirror surface by a polishing machine.
6. The method for preparing the refractory element doped abrasion resistant gradient HfMSiCN ceramic layer according to claim 4, wherein the target base distance in the step 2 is 15-25mm, and the targets are equidistantly arranged from left to right according to Hf/Si/M/C.
7. The method for preparing a refractory element doped wear resistant gradient HfMSiCN ceramic layer according to claim 4 or 6, characterized in that the target in step 2 is a grid-like high purity Hf, si, M, C.
8. The method for producing a refractory element doped, wear resistant, gradient HfMSiCN ceramic layer according to claim 4, characterized in that in step 4 the source voltage is adjusted to 850V and the workpiece voltage is 420V at the time of ignition.
9. The method for preparing a refractory element doped wear resistant gradient HfMSiCN ceramic layer according to claim 4, characterized in that in step 5, the flow ratio of argon to nitrogen is adjusted to be 1:3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211740550.8A CN116121700A (en) | 2022-12-30 | 2022-12-30 | Refractory element doped wear-resistant gradient HfMSiCN ceramic layer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211740550.8A CN116121700A (en) | 2022-12-30 | 2022-12-30 | Refractory element doped wear-resistant gradient HfMSiCN ceramic layer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116121700A true CN116121700A (en) | 2023-05-16 |
Family
ID=86293941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211740550.8A Pending CN116121700A (en) | 2022-12-30 | 2022-12-30 | Refractory element doped wear-resistant gradient HfMSiCN ceramic layer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116121700A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116180027A (en) * | 2023-03-01 | 2023-05-30 | 南京航空航天大学 | Heat corrosion resistant CrHfNbTaTiC on Ti60 alloy surface x N y Gradient high-entropy ceramic coating and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0238585A (en) * | 1988-06-14 | 1990-02-07 | Gte Lab Inc | Method for composite coating and adhering on a fire-proof base material |
| US20020170821A1 (en) * | 2001-04-11 | 2002-11-21 | Michael Sandlin | Mechanically alloyed precious metal magnetic sputtering targets fabricated using rapidly solidified alloy powders and elemental Pt metal |
| JP2004090189A (en) * | 2002-09-02 | 2004-03-25 | Kyocera Corp | Cutting tool made from surface coated ti-based cermet |
| CN101096747A (en) * | 2006-06-30 | 2008-01-02 | 株式会社神户制钢所 | Hard film and method for preparing the same |
| US20150225840A1 (en) * | 2012-05-29 | 2015-08-13 | Seco Tools Ab | Method for depositing a coating and a coated cutting tool |
| CN108707871A (en) * | 2018-05-25 | 2018-10-26 | 西安交通大学 | A kind of preparation method of the metal/non-metal laminated film with superhydrophobic characteristic |
| CN114930246A (en) * | 2020-01-16 | 2022-08-19 | Asml荷兰有限公司 | Pellicle membrane for a lithographic apparatus |
-
2022
- 2022-12-30 CN CN202211740550.8A patent/CN116121700A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0238585A (en) * | 1988-06-14 | 1990-02-07 | Gte Lab Inc | Method for composite coating and adhering on a fire-proof base material |
| US20020170821A1 (en) * | 2001-04-11 | 2002-11-21 | Michael Sandlin | Mechanically alloyed precious metal magnetic sputtering targets fabricated using rapidly solidified alloy powders and elemental Pt metal |
| JP2004090189A (en) * | 2002-09-02 | 2004-03-25 | Kyocera Corp | Cutting tool made from surface coated ti-based cermet |
| CN101096747A (en) * | 2006-06-30 | 2008-01-02 | 株式会社神户制钢所 | Hard film and method for preparing the same |
| US20150225840A1 (en) * | 2012-05-29 | 2015-08-13 | Seco Tools Ab | Method for depositing a coating and a coated cutting tool |
| CN108707871A (en) * | 2018-05-25 | 2018-10-26 | 西安交通大学 | A kind of preparation method of the metal/non-metal laminated film with superhydrophobic characteristic |
| CN114930246A (en) * | 2020-01-16 | 2022-08-19 | Asml荷兰有限公司 | Pellicle membrane for a lithographic apparatus |
Non-Patent Citations (3)
| Title |
|---|
| MARTIN MATAS，ET AL.: ""Dependence of characteristics of Hf(M)SiBCN (M=Y, Ho, Ta, Mo)thin films on the M choice:Ab-initio and experimental study"", 《ACTA MATERIALIA》, no. 206, 10 January 2021 (2021-01-10), pages 4 * |
| MENGJUAN YIN, ET AL.: ""Dependence of the M choice on the properties of Hf(M)SiCN (M=Nb, Ta, Ti, Zr) ceramic coatings: ab-initio and experimental study"", 《TRIBOLOGY INTERNATIONAL》, no. 196, 17 April 2024 (2024-04-17) * |
| 郭强强;冯志海;周延春;: "超高温陶瓷的研究进展", 宇航材料工艺, no. 05, 15 October 2015 (2015-10-15) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116180027A (en) * | 2023-03-01 | 2023-05-30 | 南京航空航天大学 | Heat corrosion resistant CrHfNbTaTiC on Ti60 alloy surface x N y Gradient high-entropy ceramic coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108642449A (en) | Superhard tough high-entropy alloy nitride nano composite coating hard alloy blade and preparation method thereof | |
| CN104213075A (en) | AlTiSiN-AlCrSiN nanocrystalline-amorphous multilayer composite superhard toughness coating material and manufacturing method | |
| CN113652659B (en) | Preparation method of high-entropy alloy nitride coating metallurgically bonded with substrate | |
| CN101709470B (en) | Preparation method of composite coating containing in situ generated diffusion barrier | |
| CN111321381B (en) | AlCrNbSiTiBN-based nano composite coating of hard alloy blade and preparation method thereof | |
| CN102560338B (en) | Metal ceramic coating and preparation method thereof | |
| JP2021502564A (en) | Zirconium alloy cladding with improved high temperature oxidation resistance and its manufacturing method | |
| CN109402564A (en) | A kind of AlCrSiN and AlCrSiON double-layer nanometer composite coating and preparation method thereof | |
| CN116121700A (en) | Refractory element doped wear-resistant gradient HfMSiCN ceramic layer and preparation method thereof | |
| CN113235041A (en) | AlCrTiSiWMoN high-entropy alloy nitride coating and preparation method and application thereof | |
| CN114231906A (en) | Thermal barrier coating of high-pressure turbine blade of marine gas turbine and preparation method thereof | |
| CN107034433B (en) | A kind of preparation method of TiCN gradient coating | |
| CN113512710A (en) | 45 steel surface CrN-Cr gradient coating and preparation method and application thereof | |
| CN112941463A (en) | Nano multilayer oxynitride corrosion-resistant protective coating on titanium alloy surface and preparation method and application thereof | |
| CN106467959B (en) | A kind of solid lubrication composite coating of matrix surface and preparation method thereof | |
| CN115198271B (en) | High-heat-matching-property thermal barrier coating and preparation method and application thereof | |
| CN109898056B (en) | PVD (physical vapor deposition) technology-based bulk metal/metal ceramic nanometer gradient material as well as preparation method and application thereof | |
| CN109576662B (en) | PVD (physical vapor deposition) technology-based bulk cermet/metal/cermet bidirectional nano gradient material and preparation method thereof | |
| CN116180027A (en) | Heat corrosion resistant CrHfNbTaTiC on Ti60 alloy surface x N y Gradient high-entropy ceramic coating and preparation method thereof | |
| CN116180014B (en) | Zirconium-titanium self-lubricating wear-resistant coating and preparation method thereof | |
| CN114875360B (en) | High-temperature oxidation resistant NiAl/AlSiON multilayer composite coating and preparation method thereof | |
| CN116219376B (en) | Tantalum surface high-temperature ablation resistant coating and preparation method thereof | |
| CN109652764B (en) | Bulk cermet material based on PVD technology and preparation method and application thereof | |
| CN116162903B (en) | Composite deposited MCrAlY antioxidation coating and preparation process thereof | |
| CN110670020B (en) | Zirconium-aluminum-nitrogen-aluminum oxide multilayer composite coating firmly combined with metal ceramic 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 |