CN110923707A - Titanium alloy surface high-temperature-resistant composite coating material based on laser cladding - Google Patents

Titanium alloy surface high-temperature-resistant composite coating material based on laser cladding Download PDF

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CN110923707A
CN110923707A CN202010024032.0A CN202010024032A CN110923707A CN 110923707 A CN110923707 A CN 110923707A CN 202010024032 A CN202010024032 A CN 202010024032A CN 110923707 A CN110923707 A CN 110923707A
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powder
titanium alloy
temperature
cladding
composite coating
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李玉新
聂金浩
杨宜鑫
白培康
赵占勇
魏守征
关庆丰
蔡杰
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North University of China
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North University of China
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C24/00Coating starting from inorganic powder
    • C23C24/08Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/04Alloys 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 carbonitrides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-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
    • C22C32/0089Non-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 other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass

Abstract

The invention relates to a laser cladding-based titanium alloy surface high-temperature-resistant composite coating material which is prepared by mixing the following powder raw materials in percentage by mass: 30-60% of Ni-based alloy powder, 30-50% of TiBCN powder and 10-30% of Nb powder. The high-temperature resistant composite coating material on the surface of the titanium alloy is laser-cladded on the surface of the titanium alloy, so that a high-temperature resistant cladding coating which is free of air holes and cracks, compact in structure and fine in grains can be formed, the high-temperature wear resistance and the high-temperature oxidation resistance of the cladding coating can be obviously improved, and the surface hardness and the corrosion resistance of the cladding coating are also greatly improved compared with those of other coatings.

Description

Titanium alloy surface high-temperature-resistant composite coating material based on laser cladding
Technical Field
The invention belongs to the technical field of preparation of metal surface coating materials, and relates to a metal-ceramic composite coating material, in particular to a high-temperature-resistant composite coating material for laser cladding and strengthening the surface of a titanium alloy.
Background
The titanium alloy material has high specific strength and good high-temperature mechanical property, and is a preferable structural and functional material in the industries of aerospace, weaponry, chemical engineering, medical treatment and the like. However, titanium alloy materials have disadvantages of low hardness, wear resistance, and poor oxidation resistance in high temperature environments, which limit their use in friction members.
Laser cladding is an advanced surface modification technology, and belongs to a rapid solidification process. The laser cladding process is a dynamic melting process, and in the process of cladding various traditional oxide ceramic powder, carbide composite powder and metal-ceramic powder, due to the inconsistent element density of each component in a molten pool and other physical property differences, bubbles are easily generated in the cladding process, so that the defects of cracks, air holes and the like exist in the finally formed cladding layer.
CN 106835126A discloses a ceramic composite material for laser cladding of titanium alloy surface, which is prepared from 20-65 wt% of Ti powder, 25-75 wt% of TiBCN ceramic powder and 2-10 wt% of B4And C, mixing the powder C. The ceramic composite material can form a composite ceramic cladding coating metallurgically combined with a titanium alloy matrix on the surface of a titanium alloy through a laser cladding technology, the hardness of the coating can reach 3.5-4.5 times of that of the titanium alloy matrix, the wear resistance of the coating is obviously improved, the wear rate of a test sample is only 1/3-1/4 of that of the titanium alloy matrix, and the wear rate is obviously reduced compared with that of the matrix. The composite ceramic cladding coating adopts a Ti + TiBCN powder system to blend B4C, the coating combines the advantages of the ceramic coating and the in-situ authigenic ceramic coating, and not only has the hardness and the durability of the cladding coatingThe grindability is improved, and the thermal expansion of the coating is reduced, reducing the residual stress. However, the problems of the air holes and the crack defects of the composite ceramic cladding coating are not fundamentally solved.
CN 108707893A discloses a ZrO based ceramic material2The doped laser cladding metal-ceramic coating material is prepared from 5-20 wt% of Ti powder, 70-92 wt% of TiBCN ceramic powder and 3-10 wt% of ZrO2Mixing the powders. The coating material is cladded on the surface of the titanium alloy substrate by utilizing a laser cladding technology, so that the strain energy of the residual thermal stress of laser cladding can be absorbed, the generation and extension of cracks caused by stress concentration are reduced, the fracture toughness of the cladding coating is improved, and the strength and the corrosion resistance of the cladding coating are improved, thereby forming the toughened metal-ceramic cladding coating. Doped ZrO thereof2Under the rapid heating of laser, the particles generate phase change from a tetragonal phase to a monoclinic phase, thereby absorbing the strain energy of the residual thermal stress of laser cladding, improving the fracture toughness of the cladding coating and achieving the expansion control of the coating microcrack source. However, ZrO2The toughening of (2) has certain timeliness and cannot be used in a high-temperature environment.
Song Bo Han (influence of Nb on the structure and performance of laser cladding nickel-based alloy [ D ]. Shijiazhuang railway university, 2016.) prepares Ni60 laser cladding layer and Nb + Ni60 laser cladding layer on the surface of No. 45 steel respectively, although the wear resistance is improved, the wear resistance is not improved substantially.
Disclosure of Invention
The invention aims to provide a laser cladding-based titanium alloy surface high-temperature-resistant composite coating material, which is laser cladded on the titanium alloy surface, can improve the high-temperature wear resistance of the titanium alloy surface, obtain a cladding coating without holes and cracks and with fine grains, and further improve the high-temperature oxidation resistance of the cladding layer.
The laser cladding-based titanium alloy surface high-temperature-resistant composite coating material is prepared by mixing the following powder raw materials in percentage by mass: 30-60% of Ni-based alloy powder, 30-50% of TiBCN powder and 10-30% of Nb powder.
The Ni-based alloy powder may be any conventional Ni-based alloy powder containing a Cr element or an Al element, for example, FGH97 alloy powder, Ni60 alloy powder, Ni45 alloy powder, and the like.
In the laser cladding-based titanium alloy surface high-temperature-resistant composite coating material, the particle sizes of the Ni-based alloy powder, the TiBCN powder and the Nb powder are preferably 100-300 meshes.
The titanium alloy surface high-temperature-resistant composite coating material is obtained by fully mixing various powder raw materials in a ball mill. Preferably, the mixing time should be not less than 2 hours.
Further, the titanium alloy surface high-temperature-resistant composite coating material obtained by mixing is dried and then used. The specific drying condition is that the composite coating material is heated to 80-100 ℃, dried in vacuum for 1-2 hours and then naturally cooled.
The titanium alloy surface high-temperature-resistant composite coating material provided by the invention is suitable for cladding on the titanium alloy surface by adopting a laser cladding technology to form a high-temperature-resistant cladding coating.
Specifically, the high-temperature resistant composite coating material on the surface of the titanium alloy is uniformly paved on the surface of a titanium alloy substrate, and under the protection of inert gas, the composite coating material is scanned by laser irradiation and is cladded on the surface of the titanium alloy substrate to form a high-temperature resistant cladding coating.
Preferably, the invention adopts a coaxial powder feeding method to uniformly spread the composite coating material on the surface of the titanium alloy matrix for laser cladding. The preferable powder feeding speed in the spreading process is 4-6 g/min.
More preferably, the laser power of the laser cladding process is set to be 1200-1600W, the diameter of a laser spot is 4mm, laser cladding scanning is carried out at the laser scanning speed of 5-9 mm/s, and the scanning overlap ratio is 45-55%.
Furthermore, before laser cladding, the surface of the titanium alloy substrate is pretreated, including the surface is polished to remove an oxide layer and impurities on the surface, and is cleaned and dried by alcohol or acetone.
According to the invention, the niobium powder is added into the nickel-based alloy powder and the TiBCN ceramic powder to obtain the titanium alloy surface high-temperature-resistant composite coating material, and the titanium alloy surface high-temperature-resistant composite coating material is subjected to laser cladding on the surface of a titanium alloy substrate, so that a high-temperature-resistant cladding coating which is free of holes and cracks, compact in structure and fine in grains can be formed, the high-temperature wear resistance and the high-temperature oxidation resistance of the cladding coating can be obviously improved, and the surface hardness and the corrosion resistance of the cladding coating are greatly improved compared with those of other coatings.
In the laser cladding process, Nb element in the composite coating material occupies crystal boundaries, so that the binding force between the coating crystal boundaries is enhanced; meanwhile, part of the TiBCN is decomposed, NbC formed by C and part of Nb is firstly subjected to eutectic precipitation to form heterogeneous nuclei, and the nucleation rate in the solidification and crystallization process is improved. The factors refine the structure of the cladding coating, thereby effectively controlling the generation of pores and cracks.
The reason for improving the cladding coating performance is very complicated, and besides the TiBCN factor, the coating mainly comprises TiC, TiN and TiB2And Ti (CN), Ni3B and other hard phases, and NbAl formed by Al in the matrix entering a molten pool in the processes of fine grain strengthening, solid solution strengthening and laser cladding3Intermetallic compounds, etc. The TiBCN powder can precipitate new strengthening phase in the heating process and promote the interface reaction around the strengthening phase, so as to provide elements for the generation of other ceramic phases. A series of ceramic phases, intermetallic compound phases and solid solution phases are generated in the cladding process, so that the high-temperature wear resistance of the cladding coating is further improved, the cladding coating which is free of pore cracks, compact in structure and fine in grains is obtained, and the high-temperature oxidation resistance of the surface of the titanium alloy matrix is improved.
On the other hand, the compact tissue structure and low porosity are also important factors for improving the high-temperature oxidation resistance of the coating. Secondly, besides the high temperature resistance of the Ni-based alloy powder, Cr or Al elements in the powder form Cr under the high temperature environment2O3Or Al2O3The protective film also effectively prevents the defect that the oxidation rate of Nb is increased after the temperature exceeds 600 ℃.
Drawings
Fig. 1 is a graph comparing wear rates of cladding coatings prepared in examples and comparative examples.
FIG. 2 is a scanning electron micrograph of a cross section of the cladding layer of example 1(A) and comparative example 1 (B).
Detailed Description
In order that the objects, features and effects of the invention may be more fully realized and more readily understood, the invention will now be further described with reference to the following specific examples. The examples are only for illustrating the technical solutions of the present invention more clearly, and are not intended to limit the present invention in any way. The invention is susceptible to various modifications and alternative forms. It will be understood by those skilled in the art that various changes, modifications, equivalents, and improvements may be made to the embodiments without departing from the spirit and scope of the invention.
Example 1.
Weighing 40g of FGH97 alloy powder with the granularity of 200 meshes, 40g of TiBCN powder and 20g of Nb powder, adding the materials into a ball mill, mixing for 2h, taking out, and drying for 1 h in a vacuum environment at the temperature of 80 ℃ to obtain the titanium alloy surface high-temperature-resistant composite coating material.
Taking a titanium alloy sample with the specification of 20 multiplied by 20mm, carrying out coarse grinding treatment on the surface of the titanium alloy sample by 180-mesh metallographic abrasive paper, cleaning the titanium alloy sample by using acetone to remove oil stains, wiping the titanium alloy sample clean, wiping the titanium alloy sample by using alcohol, and drying the titanium alloy sample by blowing to obtain the pretreated titanium alloy base material.
Placing the titanium alloy sample subjected to surface treatment on a laser cladding workbench, and adjusting laser cladding technological parameters as follows: the laser power is 1400W, the spot diameter is 4mm, the scanning speed is 7mm/s, the powder feeding rate is 80mg/s, the lap joint rate is 50%, and the alloy powder carrier gas pressure is 0.8 MPa. The method is characterized in that a laser cladding mode of coaxial powder feeding is adopted, a high-temperature resistant composite coating material on the surface of the titanium alloy is filled into a powder cavity of a laser cladding device and is paved on the surface of a titanium alloy sample, and a cladding coating which is metallurgically bonded with a matrix is generated on the surface of the titanium alloy under the irradiation of laser energy.
Example 2.
Weighing 45g of Ni60 alloy powder with the granularity of 200 meshes, 45g of TiBCN powder and 10g of Nb powder, adding the materials into a ball mill, mixing for 2h, taking out, and drying for 1 h in a vacuum environment at the temperature of 80 ℃ to obtain the high-temperature-resistant composite coating material on the surface of the titanium alloy.
The titanium alloy sample is pretreated according to the method of the embodiment 1 and then placed on a laser cladding workbench. Adjusting laser cladding process parameters: the laser power is 1600W, the diameter of a light spot is 4mm, the scanning speed is 7mm/s, the powder feeding rate is 65mg/s, the lap joint rate is 50 percent, and the carrier gas pressure of the alloy powder is 0.8 MPa. The method is characterized in that a laser cladding mode of coaxial powder feeding is adopted, a high-temperature resistant composite coating material on the surface of the titanium alloy is filled into a powder cavity of a laser cladding device and is paved on the surface of a titanium alloy sample, and a cladding coating which is metallurgically bonded with a matrix is generated on the surface of the titanium alloy under the irradiation of laser energy.
Example 3.
Weighing 45g of Ni45 alloy powder with the granularity of 200 meshes, 40g of TiBCN powder and 15g of Nb powder, adding the materials into a ball mill, mixing for 2h, taking out, and drying for 1 h in a vacuum environment at the temperature of 80 ℃ to obtain the high-temperature-resistant composite coating material on the surface of the titanium alloy.
The titanium alloy sample is pretreated according to the method of the embodiment 1 and then placed on a laser cladding workbench. Adjusting laser cladding process parameters: the laser power is 1200W, the spot diameter is 4mm, the scanning speed is 5mm/s, the powder feeding rate is 65mg/s, the lap joint rate is 50 percent, and the alloy powder carrier gas pressure is 0.8 MPa. The method is characterized in that a laser cladding mode of coaxial powder feeding is adopted, a high-temperature resistant composite coating material on the surface of the titanium alloy is filled into a powder cavity of a laser cladding device and is paved on the surface of a titanium alloy sample, and a cladding coating which is metallurgically bonded with a matrix is generated on the surface of the titanium alloy under the irradiation of laser energy.
Comparative example 1.
Taking the pretreated titanium alloy base material in the example 1, and cladding mixed powder consisting of 50wt% of FGH97 alloy powder and 50wt% of TiBCN on the surface of the base material according to the laser cladding parameter conditions of the example 1 to form a cladding coating.
Comparative example 2.
Taking the pretreated titanium alloy matrix material in the embodiment 1, and cladding mixed powder consisting of 50wt% of Nb powder and 50wt% of TiBCN on the surface of the matrix according to the laser cladding parameter conditions of the embodiment 2 to form a cladding coating.
Comparative example 3.
Taking the pretreated titanium alloy base material in the embodiment 1, and cladding mixed powder consisting of 50wt% of Ni45 alloy powder and 50wt% of Nb powder on the surface of the base material according to the laser cladding parameter conditions of the embodiment 3 to form a cladding coating.
The high-temperature wear resistance and the high-temperature oxidation resistance of the cladding coatings obtained in the above examples 1 to 3 and comparative examples 1 to 3 were respectively tested.
The high-temperature friction and wear test is carried out on a HT-1000 type high-temperature friction and wear testing machine. Selection of Si for test3N4The ceramic ball is used as a friction pair, the rotating speed of the motor is 500r/min, the abrasion time is 30min, the test load is 5N, the test temperature is 800 ℃, and the friction radius is 1 mm.
The upper and lower planes of the sample to be abraded are smooth and parallel, and are cleaned by ultrasonic waves. After the experiment, the wear rate was measured using an MT-500 type probe material surface wear scar measuring instrument, and the wear rate results are shown in fig. 1.
The smaller the wear rate is, the better the high-temperature wear resistance of the cladding coating is. According to fig. 1, the wear rates of examples 1 to 3 were 0.215, 0.229 and 0.234, respectively, and the wear rates of comparative examples 1 to 3 were 0.493, 0.514 and 0.927, respectively, and the high-temperature wear resistance of each comparative example was significantly inferior to that of the corresponding example.
Among them, comparative examples 1 and 2 are significantly inferior to examples 1 and 2 in high-temperature wear resistance because Nb powder and Ni-based alloy powder are not used, respectively. In contrast, in comparative example 3, the high temperature wear resistance was significantly reduced due to the lack of strengthening effect of the ceramic phase, as compared with example 3.
The high-temperature oxidation resistance test is carried out in static state, normal pressure and atmospheric atmosphere according to the HB 5258-2000 aviation industry standard, and the test equipment adopts a box type resistance furnace.
The samples prepared in examples 1 to 3 and comparative examples 1 to 3 and the titanium alloy substrate sample without any cladding coating formed by laser cladding are heated to 800 ℃ and oxidized for 100 hours, air-cooled and weighed, and the oxidation weight increase of the cladding coating of the sample per unit area is calculated, and specific test results are listed in table 1. The less the oxidation weight gain of the cladding coating, the stronger the oxidation resistance and the longer the service life.
Among them, the high-temperature oxidation resistance of comparative example 1 is significantly inferior to that of example 1. In comparative example 2, the addition of Nb element improves the compactness of the cladding coating and reduces the generation of pores and cracks, but Nb is easily oxidized at a high temperature of 800 ℃, so that the high-temperature oxidation resistance of the cladding coating is reduced compared with example 2, and is reduced more than that of example 1. Also, the high temperature oxidation resistance of comparative example 3 is inferior to that of example 3 due to the lack of strengthening effect of the ceramic phase.
The SEM topographies of the cross sections of the coatings of example 1 and comparative example 1 are shown in FIG. 2, respectively, and it is clear that the cross section of the coating of example 1 is dense, and has no pores and no cracks.

Claims (10)

1. A laser cladding-based titanium alloy surface high-temperature-resistant composite coating material is prepared by mixing the following powder raw materials in percentage by mass: 30-60% of Ni-based alloy powder, 30-50% of TiBCN powder and 10-30% of Nb powder.
2. The titanium alloy surface refractory composite coating material as defined in claim 1, wherein said Ni-based alloy powder is a Ni-based alloy powder containing Cr element or Al element.
3. The titanium alloy surface refractory composite coating material as defined in claim 1 or 2, wherein said Ni-based alloy powder is any one of FGH97 alloy powder, Ni60 alloy powder and Ni45 alloy powder.
4. The titanium alloy surface high-temperature-resistant composite coating material as claimed in claim 1 or 2, wherein the particle size of the Ni-based alloy powder, the TiBCN powder and the Nb powder is 100-300 meshes.
5. The titanium alloy surface high temperature resistant composite coating material according to claim 1 or 2, wherein the powder raw materials are mixed in a ball mill for not less than 2 hours.
6. The titanium alloy surface high-temperature-resistant composite coating material as claimed in claim 1 or 2, wherein the titanium alloy surface high-temperature-resistant composite coating material obtained by mixing is heated to 80-100 ℃ and dried in vacuum for 1-2 hours.
7. The method for forming the cladding coating on the surface of the titanium alloy matrix by using the high-temperature-resistant composite coating material for the titanium alloy surface as claimed in claim 1 through laser cladding comprises the steps of uniformly paving the high-temperature-resistant composite coating material for the titanium alloy surface on the surface of the titanium alloy matrix, and scanning the composite coating material through laser irradiation under the protection of inert gas to enable the composite coating material to be cladded on the surface of the titanium alloy matrix to form the high-temperature-resistant cladding coating.
8. The method as claimed in claim 7, wherein the composite coating material is uniformly spread on the surface of the titanium alloy substrate by a coaxial powder feeding method at a powder feeding speed of 4-6 g/min for laser cladding.
9. The method of claim 7, wherein the laser power of the laser cladding process is 1200-1600W, the diameter of the laser spot is 4mm, and the laser cladding scanning is performed at a laser scanning speed of 5-9 mm/s.
10. The method of claim 7, wherein the laser scanning has an overlap ratio of 45-55%.
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CN102943267A (en) * 2012-12-12 2013-02-27 江苏新亚特钢锻造有限公司 High abrasion-proof laser cladding nickel-base alloy powder and preparation method thereof
CN106835126A (en) * 2017-03-20 2017-06-13 中北大学 A kind of Laser Cladding on Titanium Alloy ceramic composite
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