CN116426914A - Titanium alloy surface ceramic reinforced titanium-based wear-resistant coating and preparation method thereof - Google Patents
Titanium alloy surface ceramic reinforced titanium-based wear-resistant coating and preparation method thereof Download PDFInfo
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- CN116426914A CN116426914A CN202310520411.2A CN202310520411A CN116426914A CN 116426914 A CN116426914 A CN 116426914A CN 202310520411 A CN202310520411 A CN 202310520411A CN 116426914 A CN116426914 A CN 116426914A
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- 238000000576 coating method Methods 0.000 title claims abstract description 39
- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 239000010936 titanium Substances 0.000 title claims abstract description 34
- 239000000919 ceramic Substances 0.000 title claims abstract description 30
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 42
- 239000011159 matrix material Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000010288 cold spraying Methods 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 238000005507 spraying Methods 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000005488 sandblasting Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 13
- 238000005516 engineering process Methods 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000004372 laser cladding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Mechanical Engineering (AREA)
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- Other Surface Treatments For Metallic Materials (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
The invention discloses a titanium alloy surface ceramic reinforced titanium-based wear-resistant coating and a preparation method thereof, wherein (1) the surface of a TC4 titanium alloy matrix is subjected to sand blasting treatment; (2) WC ceramic powder with specific granularity and pure Ti powder are selected, and mixed powder of WC and Ti is prepared and dried. (3) And spraying mixed powder on the surface of the pretreated matrix through a high-pressure cold spraying process, so that the mixed powder is deposited on the surface of the matrix to form the high-wear-resistance composite coating. The high-density WC ceramic particles are adopted as the reinforcing phase, and the prepared titanium-based composite coating has excellent compactness and wear resistance, and compared with a titanium alloy matrix, the wear rate of the titanium-based composite coating is reduced by 3 orders of magnitude, so that the problem of poor wear resistance of the common titanium alloy matrix is effectively solved.
Description
Technical Field
Belongs to the field of surface engineering, and in particular relates to a titanium alloy surface ceramic reinforced titanium-based wear-resistant coating and a preparation method thereof.
Background
The titanium alloy is an important light metal material, has high specific strength, corrosion resistance and good comprehensive mechanical property, and is widely applied to the fields of aerospace, ocean engineering, oil gas exploitation, medical appliances and the like. However, titanium alloy has the problems of large friction coefficient and poor wear resistance, so that the titanium alloy is easy to wear and lose efficacy in the use process, and the application of the titanium alloy in various fields is limited. Surface protective coating preparation is generally an effective way to improve wear resistance. Various surface technologies are adopted by scholars at home and abroad to improve, such as ion implantation, vapor deposition, micro-arc oxidation, thermal spraying, laser cladding technology and the like, which are effective means for modifying the surface of the titanium alloy, but the problems of low efficiency, insufficient carrying capacity of a thin layer, poor combination, harmful phase change and oxidation, high residual tensile stress and the like still exist.
In recent years, metal matrix composite coatings have been of interest for having a unique combination of hardness and toughness, with outstanding characteristics in aggressive wear environments. Compared with the traditional thermal spraying technology, the low-temperature characteristic of the cold spraying technology can effectively avoid high-temperature phase transformation, oxidation, residual stress, brittle phase interface cracking and the like. Moreover, research shows that the tamping effect and the work hardening effect of the ceramic particles can effectively increase the plastic deformation of the cold spraying particles, and the ceramic particles which are dispersed and reserved in the metal matrix increase the bearing capacity of the coating, so that the wear resistance of the coating is greatly improved. However, the related reports are mainly focused on metals such as Al, ni, cu, and the like, and alloys thereof. Some small amounts of titanium-based composite coating patents focus on how to improve inter-particle bonding in combination with post-treatment techniques or are limited by the large number of poor interfaces introduced by the increased content of ceramic particles, which are only shot-blasted particles, and which are not largely retained in the coating.
In view of the foregoing, there is a need for developing a composite coating material system applied to the surface of titanium alloy by cold spray technology, so as to fully retain ceramic particles in the coating and improve inter-particle bonding, and finally obtain excellent wear resistance.
Disclosure of Invention
The invention provides a titanium alloy surface ceramic reinforced titanium-based wear-resistant coating and a preparation method thereof. According to the method, WC ceramic powder and pure Ti powder are mixed according to a certain proportion to obtain original cold spraying powder, and the high-density WC/Ti composite coating is prepared by utilizing the tamping effect of high-density WC ceramic particles in the spraying process. And (3) controlling a cold spraying process: and the high-density high-wear-resistance composite coating is rapidly formed on the surface of the titanium alloy matrix by parameters such as gas temperature, gas pressure, spraying distance and the like. The powder is polygonal pure Ti powder (particle size of 100-400 meshes) and polygonal WC ceramic powder (particle size of 100-300 meshes) manufactured by a crushing method.
The invention is realized by the following technical scheme:
the preparation method of the ceramic reinforced titanium-based wear-resistant coating on the surface of the titanium alloy comprises the following steps:
(1) According to the volume fraction, 40-80% WC ceramic powder and the balance Ti powder are taken, uniformly mixed and dried;
(2) Performing sand blasting pretreatment on the surface of a titanium alloy matrix material to remove oxide films and impurities on the surface of the matrix, and obtaining enough surface roughness;
(3) And (3) depositing the mixed powder on the surface of the titanium alloy matrix treated in the step (2) by using a high-pressure cold spraying technology to prepare the composite coating with the thickness of more than 2 mm.
According to the preparation method, the WC ceramic powder is polygonal WC powder with the particle size of 100-300 meshes, and the pure Ti powder is polygonal Ti powder with the particle size of 100-400 meshes.
In the preparation method, in the step (1), the drying temperature is 80 ℃, and the heat preservation is carried out for 2 hours.
In the preparation method, in the step (3), the technological parameters of cold spraying are as follows: gas temperature: 400-600 ℃, gas pressure 2-4 MPa, spraying distance: 25-45 mm, and the moving speed of the mechanical arm is 50-100 mm/s.
In the preparation method, in the step (3), the working temperature of carrier gas is 600 ℃, the pressure of working gas is 3MPa, and the pressure of powder feeding gas is 3.2MPa; the powder feeding speed of the powder feeder was set at 2.5rpm, and the powder feeding air flow rate was set at 200L/min.
The titanium alloy surface ceramic reinforced titanium-based wear-resistant coating prepared according to any one of the preparation methods.
Advantageous effects
The WC ceramic adopted by the invention has high hardness, good chemical stability and excellent wear resistance. In the spraying process, high momentum is obtained by the high-density WC ceramic particles, and a tamping effect and a work hardening effect are generated on the metallic titanium matrix. The sand blasting effect introduced by the ceramic particles increases the roughness of the deposition surface, promotes the occurrence of mechanical occlusion, and finally obtains a compact WC-Ti composite coating. Meanwhile, the impact broken WC ceramic fragments are wedged into the titanium matrix, and the evenly dispersed ceramic particles improve the plastic shearing resistance of the coating. The WC-Ti composite coating has excellent wear resistance under the combined action of the reinforced metal base and the ceramic particles in the coating.
In addition, the invention provides a method for rapidly depositing the coating, which comprises the following steps: the high-pressure cold spraying technology is adopted for rapid additive manufacturing, and the method has the characteristics of low cost, high efficiency, breakthrough of thickness dimension limitation, compressive residual stress, good combination and the like.
Drawings
Fig. 1: the cross-section SEM image of the cold spray WC-Ti composite coating provided by the invention;
fig. 2: the invention provides a sample abrasion surface image;
Detailed Description
The present invention will be described in detail with reference to specific examples.
The preparation method of the titanium alloy surface wear-resistant coating mainly comprises the following two steps:
step A: according to the volume ratio of 40-80% of WC ceramic, the balance of pure Ti is prepared into powder, evenly mixed, and placed in a drying oven to be heated to 80 ℃, and then kept for 2 hours, so that the fluidity of the powder is ensured. And placing the pretreated mixed powder into a powder feeder, wherein the powder feeding speed of the powder feeder is set to be 1.5-2.5 rpm, and the powder feeding air flow is 150-200L/min.
And (B) step (B): performing sand blasting pretreatment on the surface of a TC4 titanium alloy matrix material to remove impurities such as oxide films and the like on the surface of the matrix, and obtaining enough surface roughness; fixing the TC4 titanium alloy substrate after sand blasting on a vertical mechanical arm, enabling a cold spraying spray gun to be vertical to the surface of the substrate, adjusting the spraying distance to be 25-45 mm, and setting a mechanical arm movement scanning path. And C, regulating the preheating temperature of the mixed powder in the step A through a heater, regulating the air pressure at two stages of preheating and spraying through a pressure reducing valve connected with a high-pressure nitrogen cylinder, and carrying out cold spraying on the surface of the substrate by using cold spraying equipment, and ending heating and air supply after the composite coating which is compact in combination and excellent in performance is obtained.
In the step A, the average grain size of the pure Ti powder is 33 μm, and the average grain size of the WC ceramic powder is 42 μm.
The moving speed of the manipulator in the cold spraying process is 50-100 mm/s.
Example 1
The invention takes TC4 as a matrix (the components are shown in table 1), and the specific process steps for preparing the cold spraying wear-resistant coating are as follows:
table 1TC4 substrate composition table (wt.%)
Step one: and carrying out sand blasting treatment on the TC4 titanium alloy substrate with the length of 100mm and the width of 50mm, and removing peeling layers, pollutants, oxide layers, fatigue layers and scratches on the outer surface of the substrate to the surface of the exposed metal, so that the surface of the substrate is rough, and good bonding is formed.
Step two: the Ti powder with the average grain diameter of 33 mu m and WC with the average grain diameter of 42 mu m are weighed according to 80vol.% of WC and 20vol.% of Ti, 35g and 465g are respectively weighed and uniformly mixed, and are placed in a vacuum drying oven to be heated to 80 ℃, kept for 2 hours, cooled to normal temperature and sieved once again, so that the fluidity of the powder is ensured.
Step three: and (3) fixing the titanium alloy substrate processed in the step (A) on a vertical mechanical arm, and enabling a cold spraying spray gun to be vertical to the surface of the substrate, wherein the adjustment distance is 25mm. And (3) preparing the composite coating by using cold spraying equipment, wherein the working temperature of carrier gas is 600 ℃, the pressure of working gas is 3MPa, and the pressure of powder feeding gas is 3.2MPa. The powder feeding speed of the powder feeder was set at 2.5rpm, and the powder feeding air flow rate was set at 200L/min. The obtained coating has the cross-sectional morphology shown in figure 1, the thickness exceeding 2mm and the hardness reaching 480HV0.3.
In this example, rapid deposition of the composite wear resistant coating was achieved using a high pressure cold spray apparatus. The low working temperature avoids high-temperature oxidation of the titanium material, and the residual compressive stress characteristic of the titanium material realizes good combination of the thick wear-resistant coating and the matrix. Under the same dry friction condition, the wear-resistant test results of the titanium alloy and the composite coating show that compared with a TC4 alloy matrix, the wear rate of the wear-resistant coating prepared by the invention is reduced by 3 orders of magnitude, and the appearance of the wear surface of the coating is shown in figure 2.
It will be understood that modifications and variations will be apparent to those skilled in the art from the foregoing description, and it is intended that all such modifications and variations be included within the scope of the following claims.
Claims (6)
1. The preparation method of the ceramic reinforced titanium-based wear-resistant coating on the surface of the titanium alloy is characterized by comprising the following steps of: (1) According to the volume fraction, 40-80% WC ceramic powder and the balance Ti powder are taken, uniformly mixed and dried;
(2) Performing sand blasting pretreatment on the surface of a titanium alloy matrix material to remove oxide films and impurities on the surface of the matrix, and obtaining enough surface roughness;
(3) And (3) depositing the mixed powder on the surface of the titanium alloy matrix treated in the step (2) by using a high-pressure cold spraying technology to prepare the composite coating with the thickness of more than 2 mm.
2. The method of claim 1, wherein the WC ceramic powder is a polygonal WC powder having a particle size of 100-300 mesh and the pure Ti powder is a polygonal Ti powder having a particle size of 100-400 mesh.
3. The method according to claim 1, wherein in the step (1), the drying temperature is 80℃and the temperature is kept for 2 hours.
4. The method of claim 1, wherein in step (3), the process parameters of the cold spray are as follows: gas temperature: 400-600 ℃, gas pressure 2-4 MPa, spraying distance: 25-45 mm, and the moving speed of the mechanical arm is 50-100 mm/s.
5. The method according to claim 1, wherein in the step (3), the carrier gas has a working temperature of 600 ℃, a working gas pressure of 3MPa, and a powder feeding gas pressure of 3.2MPa; the powder feeding speed of the powder feeder was set at 2.5rpm, and the powder feeding air flow rate was set at 200L/min.
6. The titanium alloy surface ceramic reinforced titanium-based wear-resistant coating prepared by the preparation method according to any one of claims 1-5.
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| CN202310520411.2A CN116426914A (en) | 2023-05-10 | 2023-05-10 | Titanium alloy surface ceramic reinforced titanium-based wear-resistant coating and preparation method thereof |
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| CN202310520411.2A CN116426914A (en) | 2023-05-10 | 2023-05-10 | Titanium alloy surface ceramic reinforced titanium-based wear-resistant coating and preparation method thereof |
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