CN113278850B - High-temperature-resistant titanium alloy protective coating and preparation method thereof - Google Patents
High-temperature-resistant titanium alloy protective coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-temperature-resistant titanium alloy protective coating and a preparation method thereof, and relates to the technical field of titanium alloys. The preparation method of the high-temperature resistant titanium alloy protective coating comprises the following steps: (1) plating a high-temperature-resistant metal layer on the surface of the titanium-based alloy; (2) preparing an electrodeposition solution from tetraethoxysilane, 0.05-0.5 mol/L nickel sulfate solution, absolute ethyl alcohol and 0.1-0.5 mol/L potassium nitrate solution; (3) preparing an initial composite film by electrodeposition; (4) putting the titanium-based alloy obtained in the step (3) into a heat treatment furnace at 700-1200 ℃, preserving heat for 4-7 h, and cooling the furnace to obtain the high-temperature resistant titanium alloy protective coating; the thermal expansion coefficient of the high-temperature resistant metal in the step (1) is between that of the titanium-based alloy and that of SiO2In the meantime. The high-temperature resistant titanium alloy protective coating prepared by the method still has good stability and small quality change after being oxidized for 100 hours at 900 ℃.
Description
Technical Field
The invention relates to the technical field of titanium alloy, in particular to a high-temperature resistant titanium alloy protective coating and a preparation method thereof.
Background
The Ti alloy has the characteristics of low density, high specific strength and specific stiffness, good high-temperature creep resistance and oxidation resistance and the like, is a light high-temperature alloy with good comprehensive performance, is widely applied to the aerospace, automobile, chemical industry and medical industry, and is a preferred material for ultrahigh-sound-speed aircrafts and next-generation advanced aircraft engines. Among them, the Ti-Al based intermetallic compound is a popular choice for high temperature structural materials due to its excellent high temperature performance and good environmental stability.
The Ti-Al alloy can be divided into 3 kinds, i.e. Ti3Al, TiAl and TiAl3. Wherein Ti3The high-temperature oxidation resistance of Al is poor, and the use temperature is low (less than or equal to 650 ℃); TiAl3Has the lowest density and the best high temperature oxidation resistance, but has poor room temperature ductility and difficult machining because the solid solution range is too narrow. Titanium-aluminum alloy is brittle at room temperature, lacks sufficient ductility, and has poor deformation workability and wear resistance, and high temperature>800 ℃ C., low oxidation resistance. In order to overcome the defects, domestic and foreign researchers develop a large amount of research, make beneficial attempts, provide measures such as alloy design and surface modification and the like, and obtain a lot of valuable research results.
In view of the problems of high brittleness and poor toughness of Ti-Al alloy, a great deal of research is carried out, the most remarkable of which is in TiAl or Ti3The addition of high-content and high-melting-point transition group elements Nb, Zr, Hf and Ta in Al, particularly the addition of Nb is one of the most effective means for improving the room-temperature plasticity and high-temperature oxidation resistance of TiAl series alloy. The research of Nb-containing titanium-aluminum alloy is firstly developed by the national good professor, and the Nb is usually named as high-Nb titanium-aluminum-based alloy due to the higher addition amount of Nb. The melting point and the ordering temperature of the alloy can be effectively improved by adding the high-melting-point alloying element Nb, so that the titanium-aluminum-based alloy has good oxidation resistance, and simultaneously has the advantages of small density, simple crystal structure and easiness in controlling the microstructure to improve the performance of the titanium-aluminum-based alloy. However, the high-temperature oxidation resistance of the high-niobium TiAl alloy still cannot meet the requirements of people. Nb, Sb, Si, Cr, Y, Mo, Ta, W, Re and the like can effectively improve the high-temperature oxidation resistance of the TiAl alloy, but the mechanical property of the alloy is reduced when the addition amount is too high. The alloying method has its limitations and needs to enhance the high temperature oxidation resistance of the alloy by other methods. Meanwhile, the relationship between the structural performance (strength, toughness and the like) and the environmental performance (wear resistance, corrosion resistance, high temperature resistance and the like) is considered, so that the ideal alloy can be obtained.
Surface modification technology including ion implantation, surface coating, physical vapor deposition, chemical vapor deposition and the like for improving high-temperature oxidation resistance of TiAl alloyMeanwhile, the strength and toughness of the TiAl alloy are not changed, and the research hotspot in the field is formed. Although the ion implantation method has controllable implantation amount and good repeatability, the related equipment is expensive and has low production efficiency, and the change depth of the high niobium TiAl alloy composition is only limited to the range with a shallow surface (the<1 μm). Vapor deposition is to form Al in the oxidation process of aluminum halide which forms vapor phase by halogen effect by utilizing halogen elements such as F, Cl, Br and the like2O3The protective film slows down the oxidation of the substrate. However, the most fatal defect of this method is that it has a high requirement for Al content, and if the Al content is less than 40%, the halogen effect cannot be produced. The silicon-infiltrated layer, the aluminum-infiltrated layer, the silicon-based enamel coating and the like can be used as shielding layers to prevent oxygen from permeating into the matrix, so that the high-temperature oxidation resistance of the coating is improved. However, these coatings generally have inconsistent coefficients of expansion with the substrate, poor adhesion, and high internal stresses within the coating, which makes the coating susceptible to cracking and peeling during service. Therefore, the key point of adopting the protective coating to improve the high-temperature oxidation resistance of the TiAl alloy is to prepare a continuous and compact coating which has good bonding force and oxidation resistance with a substrate.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-temperature resistant titanium alloy protective coating.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a high-temperature resistant titanium alloy protective coating comprises the following steps:
(1) plating a high-temperature-resistant metal layer on the surface of the titanium-based alloy;
(2) preparing an electrodeposition precursor solution: uniformly mixing tetraethoxysilane, 0.05-0.5 mol/L nickel sulfate solution, absolute ethyl alcohol and 0.1-0.5 mol/L potassium nitrate solution according to the volume ratio of 0.1-0.4: 2-8, adjusting the pH value to 3-5, and stirring to obtain a precursor solution;
(3) adding the precursor solution into an electrodeposition tank, and performing electrodeposition by taking the titanium-based alloy plated with the high-temperature-resistant metal layer obtained in the step (1) as a working electrode and platinum or graphite as a counter electrode; the electrode distance is 1-10 cm, and the current density is-0.5 to-2.5 mA/cm2The electrodeposition time is 50-2000 s; after the electrodeposition is finished, washing and drying to obtain the titanium-based alloy with the initial composite film;
(4) putting the titanium-based alloy obtained in the step (3) into a heat treatment furnace at 700-1200 ℃, preserving heat for 4-7 h, and cooling the furnace to obtain the high-temperature resistant titanium alloy protective coating;
the thermal expansion coefficient of the high-temperature resistant metal in the step (1) is between that of the titanium-based alloy and that of SiO2In the meantime.
The invention selects the thermal expansion coefficient between titanium-based alloy and SiO2The high-temperature resistant metal between the titanium-based alloy substrate and the SiO can be weakened as the intermediate layer2The influence of overlarge difference between the thermal expansion coefficients of the coating reduces the thermal stress between the substrate and the coating during heat treatment, and lightens the stripping and cracking tendency of an oxide film. Meanwhile, the high-temperature resistant metal can consume the oxygen diffused in the high-temperature resistant metal, and plays a role in secondary blocking. In addition, SiO2Good thermal stability, low oxygen solubility, environmental protection, rich resources and good high-temperature oxidation resistance. Preparation of SiO containing Ni element by adding nickel sulfate to sol solution2The coating can increase the thermal expansion coefficient of the coating and reduce SiO2The influence caused by the overlarge difference between the thermal expansion coefficients of the coating and the titanium-based alloy can also improve the corrosion resistance of the coating.
Preferably, the titanium-based alloy is an aluminum-containing titanium-based alloy selected from Ti3-Al、Ti-Al、Ti-Al3Any one of Ti-6Al-4V, TiAlNb and Ti-47Al-2Cr-2 Nb.
Preferably, before the step (1), removing the oxide skin on the surface of the titanium-based alloy, cleaning and drying. The titanium-based alloy can be polished by sand paper, and cleaned and deoiled by using organic solvents such as acetone or ethanol.
Preferably, the high-temperature resistant metal is Cr or Ni, and the Cr or the Ni are used as common anti-corrosion metals and have good high-temperature resistance.
Further preferably, the high-temperature resistant metal is Ni, and when Ni is used as the intermediate layer, the high-temperature oxidation resistance of the coating is optimal.
Preferably, said step (2)In the method, the volume ratio of tetraethoxysilane to a nickel sulfate solution to an absolute ethyl alcohol to a potassium nitrate solution is 1: 0.8-1.2: 8-15; wherein the concentration of nickel sulfate in the nickel sulfate solution is 0.05-0.4 mol/L, and the concentration of potassium nitrate in the potassium nitrate solution is 0.15-0.25 mol/L. The applicant of the invention proves through experiments that the components of the electrodeposition solution have great influence on the performance of the prepared high-temperature resistant titanium alloy protective coating, the nickel sulfate concentration is too high to cause silane flocculent precipitation, and the too low concentration can have certain influence on the bonding strength of the surface layer and the middle layer. When the dosage and the concentration of each component are in the range, the mass change of the prepared high-temperature resistant titanium alloy protective coating is less than 0.7mg/cm after being oxidized for 100 hours at 900 DEG C3。
Preferably, graphite is used as the counter electrode in the step (3). Compared with other electrodes, the graphite electrode is easy to process and is suitable for the electrolytic cell of the experiment. In addition, as the anode, the graphite electrode can not be dissolved in the electrolyte in the electrodeposition process, thereby avoiding the influence caused by the introduction of impurities.
Preferably, in the step (3), the current density is controlled to be-1 to-2 mA/cm2The electrodeposition time is controlled to be 50-1000 s.
Preferably, in the step (3), the current density is controlled to be-1.5 to-2 mA/cm2The electrodeposition time is controlled to be 50-500 s.
Preferably, in the step (4), the heat treatment temperature is 700-1000 ℃, and the heat treatment environment is air, argon or vacuum.
Further preferably, in the step (4), the heat treatment temperature is 800-900 ℃.
Meanwhile, the invention also discloses the high-temperature resistant titanium alloy protective coating prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares the high temperature resistant metal layer and the nickel-containing SiO2The titanium alloy protective coating with the layer structure reduces the traditional titanium-based alloy matrix and SiO2The difference of thermal expansion coefficient between the coatings enhances the bonding force between the coatings and the substrate, and in addition, the high-temperature resistant metalThe layer can also secondarily block the diffusion of oxygen, thereby further enhancing the high-temperature resistance of the titanium-based alloy, and the SiO2The Ni in the coating also has certain corrosion resistance.
In addition, the electrodeposition sol-gel method adopted by the invention is simple, convenient to operate, high in efficiency and easy to realize, and can be used for preparing SiO with good bonding force and controllable thickness2And (4) coating.
Drawings
FIG. 1 is a surface SEM image of a bare titanium-aluminum alloy after being oxidized for 100 hours at 900 ℃;
FIG. 2 is a surface SEM image of the high temperature resistant titanium alloy protective coating of example 1 after being oxidized for 100 hours at 900 ℃;
FIG. 3 is a surface SEM image of the refractory titanium alloy protective coating of example 2 after being oxidized for 100h at 900 ℃.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1
According to one embodiment of the high temperature resistant titanium alloy protective coating, the preparation method of the high temperature resistant titanium alloy protective coating comprises the following steps:
(1) matrix pretreatment: firstly, polishing by using sand paper to remove oxide skin on the surface of a titanium-aluminum alloy (the atomic ratio of titanium to aluminum is 1:1), then sequentially ultrasonically cleaning in acetone and ethanol for 10min, and drying for later use;
(2) chemical nickel plating:
preparing a sensitizer: weighing 0.8g of stannous chloride, placing the stannous chloride in a 150mL beaker, measuring 6mL of concentrated hydrochloric acid (12mol/L) by using a 10mL measuring cylinder, dissolving the concentrated hydrochloric acid, then adding 75mL of water, and stirring until the solution is uniform and stable for later use;
preparing an activating agent: weighing 0.03g of palladium chloride, placing the palladium chloride in a 150mL beaker, adding 40mL of absolute ethyl alcohol and 40mL of water, and stirring to form a suspension for later use;
preparing a reducing agent: 60g of sodium hypophosphite is weighed and dissolved in 1L of water, and the mixture is stirred uniformly for standby.
Preparing a plating solution: weighing 2g of sodium citrate, dissolving in 30mL of water, and taking the sodium citrate as a complexing agent; weighing 6g of nickel sulfate, and dissolving in 30mL of water to obtain main salt; weighing 4g of sodium acetate, and dissolving the sodium acetate in 30mL of water to be used as a stabilizer; mixing the three components, stirring uniformly, adding 43.3mL of water, dropwise adding concentrated hydrochloric acid into the solution to adjust the pH value to 4.0-4.5, and then adding 66.6mL of reducing agent.
And (2) sensitizing the sample obtained in the step (1) in a sensitizing agent for 3 minutes, simply cleaning the sample with deionized water, then activating the sample in an activating agent for 2 minutes, simply cleaning the sample with deionized water, and then pre-treating the sample in a reducing agent for 20 seconds. Putting the pretreated sample into a plating solution at 85 ℃ for chemical reaction; and after reacting for 45-60 min, taking out the sample, fully cleaning and blow-drying to obtain the titanium-aluminum alloy with the nickel plated surface.
(3) Electrodeposition of Ni-SiO2Film formation: adding 5mL of tetraethoxysilane and 5mL of 0.1mol/L nickel sulfate solution into 100mL of ethanol potassium nitrate solution, wherein the volume ratio of the ethanol to the potassium nitrate solution is 1:1, the concentration of the potassium nitrate solution is 0.2mol/L, then dropwise adding hydrochloric acid into the solution to adjust the pH value to be 3, and stirring the solution at room temperature for 5 hours for later use. Adopting titanium-aluminum alloy with nickel plated on the surface as a cathode, a graphite electrode as an anode, controlling the electrode distance to be 2cm and controlling the current density to be-2 mA/cm2And the electrodeposition time is 300s, and the film is washed and dried after the deposition is finished to obtain an initial film. And then placing the sample into an argon environment at 800 ℃ for heat treatment for 5h, and cooling the furnace to obtain the high-temperature resistant titanium alloy protective coating.
Performing performance test on the high-temperature resistant titanium alloy protective coating, and measuring the weight gain of a unit area after oxidizing for 100 hours at 900 ℃ so as to evaluate the high-temperature oxidation resistance of the high-temperature resistant titanium alloy protective coating; the anti-stripping performance of the oxide film is tested by a scratch tester, the load range is 5N-200N, the loading speed is 60N/min, the scratch speed is 2mm/min, and the anti-stripping performance of the oxide film is expressed by the vertical load when the coating fails. 3 replicates of each sample were tested and the results are shown in Table 1.
TABLE 1
| Sample (I) | Weight gain (mg/cm)2) | Resistance to peeling |
| Bare titanium-aluminum alloy | 31.20 | 36～41N |
| Example 1 | 0.16 | 153～156N |
As can be seen from table 1, compared with the titanium-aluminum alloy without the coating, the high temperature resistant titanium alloy protective coating prepared in example 1 has good stability, the quality is still not significantly increased after the temperature is maintained at 900 ℃ for 100 hours, and the coating has good anti-stripping performance.
FIG. 1 is a SEM image of the surface of a bare titanium-aluminum alloy after being oxidized for 100h at 900 ℃, and large-particle oxides are formed on the surface of the bare titanium-aluminum alloy; FIG. 2 is an SEM image of the surface of the refractory titanium alloy protective coating of example 1 after being oxidized at 900 ℃ for 100h, and it can be seen that the surface is smooth and no large oxide particles are generated.
Example 2
In an embodiment of the high temperature resistant titanium alloy protective coating of the present invention, a preparation method of the high temperature resistant alloy of the present embodiment includes the following steps:
(1) matrix pretreatment: firstly, polishing by using sand paper to remove oxide skin on the surface of a titanium-aluminum alloy (the atomic ratio of titanium to aluminum is 1:1), then sequentially ultrasonically cleaning in acetone and ethanol for 10min, and drying for later use;
(2) electroplating Cr: weighing 12.5g of chromic anhydride, dissolving in 90mL of water, slowly adding 10mL of 25g/L sulfuric acid, and fully stirring and dissolving until the solution is uniform and stable to obtain electroplating solution; adding the electroplating solution into an electrolytic bath, and adding the pretreated titaniumThe aluminum alloy is vertically placed between two graphite sheets with a spacing of 5cm, connected with electrodes, and controlled in current density of 20A/dm2And electroplating for 1 h. Taking out the sample after the electroplating is finished, and cleaning and blow-drying the sample;
(3) electrodeposition of Ni-SiO2Film formation:
adding 5mL of tetraethoxysilane and 5mL of 0.1mol/L nickel sulfate solution into 100mL of ethanol potassium nitrate solution, wherein the volume ratio of the ethanol to the potassium nitrate solution is 1:1, the concentration of the potassium nitrate solution is 0.2mol/L, then dropwise adding hydrochloric acid into the solution to adjust the pH value to be 3, and stirring the solution at room temperature for 5 hours for later use. Taking the titanium-aluminum alloy with the Cr plated on the surface prepared in the step (2) as a cathode, a graphite electrode as an anode, controlling the electrode distance to be 2cm and controlling the current density to be-2 mA/cm2And the electrodeposition time is 300s, and the film is washed and dried after the deposition is finished to obtain an initial film. And then placing the sample into an argon environment at 800 ℃ for heat treatment for 5h, and cooling the furnace to obtain the high-temperature resistant titanium alloy protective coating.
And (3) carrying out performance test on the high-temperature resistant titanium alloy protective coating, wherein the test method is the same as that of the embodiment 1. The specific test results are shown in table 2.
TABLE 2
| Sample (I) | Weight gain (mg/cm)2) | Resistance to peeling |
| Bare titanium-aluminum alloy | 31.20 | 36～41N |
| Example 2 | 0.22 | 122～127N |
As can be seen from Table 2, compared with the titanium-aluminum alloy without the coating, the high temperature resistant titanium alloy protective coating in example 2 has good stability, and the quality is still not obviously increased after the temperature is maintained at 900 ℃ for 100 hours.
Fig. 3 is a SEM image of the surface of the refractory titanium alloy protective coating of example 2 after being oxidized at 900 ℃ for 100 hours, and it can be seen from the SEM image that no oxide is obviously generated on the surface of the refractory titanium alloy protective coating, which indicates that the refractory titanium alloy protective coating of example 2 has good high temperature oxidation resistance.
Example 3
In the embodiment of the preparation method of the high temperature resistant titanium alloy protective coating, the difference between the preparation method of the embodiment and the embodiment 1 is that the concentrations of nickel sulfate in the step (3) are respectively 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.4mol/L and 0.5mol/L, the performances of different samples are evaluated, the test method is the same as that of the embodiment 1, and the experimental results are shown in Table 3.
TABLE 3
| Concentration of Nickel sulfate (mol/L) | Weight gain (mg/cm)2) | Resistance to peeling |
| 0.05 | 0.55 | 86～89N |
| 0.1 | 0.16 | 153～156N |
| 0.2 | 0.18 | 123～130N |
| 0.4 | 0.35 | 93～106N |
| 0.5 | 1.32 | 65～76N |
As can be seen from Table 3, the concentration of nickel sulfate has a great influence on the performance of the high temperature resistant titanium alloy protective coating, and the high temperature oxidation resistance is enhanced and then weakened with the increase of the concentration. When the concentration of the nickel sulfate is within the range of 0.05-0.4 mol/L, the weight gain of the prepared high-temperature resistant titanium alloy protective coating at high temperature is small, and the high-temperature resistance is excellent.
Example 4
In the embodiment of the preparation method of the high temperature resistant titanium alloy protective coating, the difference between the preparation method of the embodiment and the embodiment 2 is that the concentrations of nickel sulfate in the step (3) are respectively 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.4mol/L and 0.5mol/L, the performances of different samples are evaluated, the test method is the same as that of the embodiment 2, and the experimental results are shown in Table 4.
TABLE 4
| Concentration of Nickel sulfate (mol/L) | Weight gain (mg/cm)2) | Resistance to peeling |
| 0.05 | 0.65 | 76～79N |
| 0.1 | 0.22 | 122～127N |
| 0.2 | 0.23 | 107～111N |
| 0.4 | 0.38 | 92～98N |
| 0.5 | 1.11 | 62～66N |
As can be seen from Table 4, for the titanium-aluminum alloy plated with Cr metal layer, Ni-SiO was further prepared2During coating, the concentration of nickel sulfate is still in the range of 0.05-0.4 mol/L, so that the high-temperature resistant titanium alloy protective coating has the optimal high-temperature resistance.
Example 5
An embodiment of the preparation method of the high temperature resistant titanium alloy protective coating is different from embodiment 1 in that, in the embodiment, the volume ratios of the components in the plating solution used in the step (3) are studied, and the volume ratios of tetraethoxysilane, 0.1mol/L nickel sulfate solution and ethanol potassium nitrate solution (the volume ratio of ethanol to potassium nitrate solution is 1:1, and the concentration of potassium nitrate solution is 0.2mol/L) are respectively 1:1:40, 1:1:30, 1:0.8:16, 1:1:20 and 1:1.2: 24. The properties of the different samples were evaluated in the same manner as in example 1, and the results are shown in Table 5.
TABLE 5
| Volume ratio of | Weight gain (mg/cm)2) | Resistance to peeling |
| 1:1:40 | 0.51 | 93～94N |
| 1:1:30 | 0.24 | 143～145N |
| 1:0.8:16 | 0.21 | 144～145N |
| 1:1:20 | 0.16 | 153～156N |
| 1:1.2:24 | 0.19 | 151～157N |
Example 6
The embodiment of the high temperature resistant titanium alloy protective coating of the invention is different from the embodiment 1 in that the sintering temperature of the step (3) is studied, and the sintering temperatures are 700 ℃, 800 ℃, 1000 ℃ and 1200 ℃. The samples were tested for their properties in the same manner as in example 1, and the results are shown in Table 6.
TABLE 6
Comparative example 1
The preparation method of the high-temperature-resistant titanium alloy protective coating is different from that of the example 1 in that no intermediate Ni layer is arranged, and Ni-SiO is carried out after the pretreatment of a substrate is finished2And (4) depositing a thin film.
Comparative example 2
A high-temperature resistant titanium alloy protective coating is prepared by a method which is different from that of the protective coating in example 1 in that Ni-SiO is not used2And (3) a layer.
Comparative example 3
The preparation method of the high-temperature resistant titanium alloy protective coating is different from that of the embodiment 1 in that a nickel sulfate solution is not added into an electrodeposition plating solution.
The performance of comparative examples 1 to 3 was tested in the same manner as in example 1, and the test results are shown in Table 7.
TABLE 7
| Sample (I) | Weight gain (mg/cm)2) | Resistance to peeling |
| Bare titanium-aluminum alloy | 31.20 | 36～41N |
| Comparative example 1 | 0.28 | 62～65N |
| Comparative example 2 | 1.47 | 133～135N |
| Comparative example 3 | 0.56 | 70～72N |
As can be seen from Table 7, the high temperature resistant titanium alloy protective coating prepared by the comparative example 1 without the intermediate Ni layer and the comparative example 3 without the nickel sulfate in the electrodeposition bath has poor anti-stripping performance, while the comparative example 2 without the surface Ni-SiO2Layers, which are significantly less resistant to thermal oxidation than the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a high-temperature resistant titanium alloy protective coating is characterized by comprising the following steps:
(1) plating a high-temperature-resistant metal layer on the surface of the titanium-based alloy;
(2) preparing an electrodeposition precursor solution: uniformly mixing tetraethoxysilane, 0.05-0.5 mol/L nickel sulfate solution, absolute ethyl alcohol and 0.1-0.5 mol/L potassium nitrate solution according to the volume ratio of 0.1-0.4: 2-8, adjusting the pH value to 3-5, and stirring to obtain a precursor solution;
(3) adding the precursor solution into an electrodeposition tank, and performing electrodeposition by taking the titanium-based alloy plated with the high-temperature-resistant metal layer obtained in the step (1) as a working electrode and platinum or graphite as a counter electrode; the electrode distance is 1-10 cm, and the current density is-0.5 to-2.5 mA/cm2The electrodeposition time is 50-2000 s; after the electrodeposition is finished, washing and drying to obtain the titanium-based alloy with the initial composite film;
(4) putting the titanium-based alloy obtained in the step (3) into a heat treatment furnace at 700-1200 ℃, preserving heat for 4-7 h, and cooling the furnace to obtain the high-temperature resistant titanium alloy protective coating;
the thermal expansion coefficient of the high-temperature resistant metal in the step (1) is between that of the titanium-based alloy and that of SiO2In the meantime.
2. The method of claim 1, wherein the titanium-based alloy is an aluminum-containing titanium-based alloy selected from the group consisting of Ti3-Al、Ti-Al、Ti-Al3Any one of Ti-6Al-4V, TiAlNb and Ti-47Al-2Cr-2 Nb.
3. The method for preparing the high temperature resistant titanium alloy protective coating according to claim 1, wherein before the step (1), the oxide skin on the surface of the titanium-based alloy is removed, cleaned and dried.
4. The method for preparing the high temperature resistant titanium alloy protective coating according to claim 1, wherein the high temperature resistant metal is one of Cr and Ni.
5. The preparation method of the high temperature resistant titanium alloy protective coating according to claim 1, wherein in the step (2), the volume ratio of the tetraethoxysilane to the nickel sulfate solution to the absolute ethyl alcohol to the potassium nitrate solution is 1: 0.8-1.2: 8-15; wherein the concentration of nickel sulfate in the nickel sulfate solution is 0.05-0.4 mol/L, and the concentration of potassium nitrate in the potassium nitrate solution is 0.15-0.25 mol/L.
6. The preparation method of the high temperature resistant titanium alloy protective coating according to claim 5, wherein in the step (2), the concentration of nickel sulfate in the nickel sulfate solution is 0.1-0.2 mol/L.
7. The method for preparing the high temperature resistant titanium alloy protective coating according to claim 1, wherein in the step (3), the current density is controlled to be-1 to-2 mA/cm2The electrodeposition time is controlled to be 50-1000 s.
8. The preparation method of the high temperature resistant titanium alloy protective coating according to claim 1, wherein in the step (4), the heat treatment temperature is 700-1000 ℃, and the heat treatment environment is air, argon or vacuum.
9. The preparation method of the high temperature resistant titanium alloy protective coating according to claim 8, wherein in the step (4), the heat treatment temperature is 800-900 ℃.
10. A high temperature resistant titanium alloy protective coating prepared by the method of any one of claims 1 to 9.
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