CN113943964A - Titanium alloy surface thermal control wear-resistant coating and preparation method thereof - Google Patents
Titanium alloy surface thermal control wear-resistant coating and preparation method thereof Download PDFInfo
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- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating By Spraying Or Casting (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a titanium alloy surface thermal control wear-resistant coating and a preparation method thereof. The preparation method comprises the following steps: placing the titanium alloy in an electrolyte containing aluminate, and in the plasma electrolytic oxidation process, utilizing direct current pulse current to break down a dielectric film on the surface of the titanium alloy so as to generate plasma micro-arc discharge and grow a thermal control wear-resistant coating on the surface of the titanium alloy in situ; the thermal control wear-resistant coating consists of 40-50wt% of aluminum titanate, 30-40wt% of titanium oxide and 10-30wt% of aluminum oxide.
Description
Technical Field
The invention relates to a titanium alloy surface thermal control wear-resistant coating and a preparation method thereof, in particular to a thermal control wear-resistant coating for the surface of a solar wing titanium alloy movable part of a space station and a preparation method thereof, and belongs to the technical field of thermal control coatings of spacecrafts.
Background
The density of the titanium alloy is about 4.5g/cm3The titanium alloy is only 56 percent of steel, has the strength of 500-1400MPa, is obviously superior to aluminum and magnesium alloy in strength, has superior high-temperature and low-temperature performance, and is widely applied to the fields of aerospace, marine vessels, biology, medicine and the like. With the development of space stations and deep space detection technologies in China, titanium alloys are increasingly widely applied to large structures such as solar wings and antennas.
In the space environment, in order to maintain the normal temperature level of the movable parts of the solar wing of the space station, the surface of the movable parts needs to be added with a thermal control coating material. The thermal control coating is a material for controlling the surface temperature of the solid surface by adjusting the thermal radiation performance of the solid surface, and the solar absorption ratio and the hemispherical emissivity are main performance indexes of the thermal control coating. According to the thermal control design, a thermal control state with a low radiation absorption ratio is required for the surface of an exposed part such as a deployment hinge, a rotary joint, etc. The titanium alloy without surface treatment has the ratio of the solar absorption ratio (as) to the hemispherical emissivity (epsilon H) as high as 5-6, and the surface temperature of the titanium alloy reaches more than 300 ℃ under the condition of solar vertical irradiation, so that the titanium alloy is difficult to meet the use requirement.
The hardness of titanium alloy is usually not more than 350HV, and the titanium alloy is easy to adhere to a grinding part to cause adhesive abrasion, thereby severely limiting the application range. The antenna and the solar wing need to be unfolded on the track for multiple times, and the components of the unfolding mechanism have excellent wear resistance, so that the movable components such as the unfolding mechanism and the like have thermal control and wear resistance.
In order to improve the heat radiation and wear resistance of the surface of the titanium alloy and effectively utilize the excellent mechanical properties of the titanium alloy, a great deal of research work is carried out by domestic and foreign scholars, wherein the most important method is to modify the surface of the titanium alloy by adopting a surface strengthening technology. Currently, surface treatment methods for titanium alloys include electroplating, anodizing, plasma spraying, sputtering, vacuum deposition, and the like. These methods deposit substances on the surface of titanium alloys by physical and chemical methods. The coating with various functions can be obtained by using methods such as plasma spraying, sputtering, vacuum deposition and the like, but the coating is only suitable for coating parts with regular sizes, and the coating of the parts of the spreading mechanism with complicated shapes is difficult to realize. The electroplating, chemical oxidation and anodic oxidation methods are to immerse the titanium alloy in the electrolyte, so that the areas contacted by the electrolyte can be well covered. The metal plating layer obtained by electroplating has high bonding strength with a substrate, and is widely applied to spaceflight, such as titanium alloy gold plating, black nickel electroplating and the like. The titanium alloy is anodized by immersing the titanium alloy in an electrolyte, and a uniform coating can be achieved by the method, but the film layer is thin and dark, and a coating with low solar absorption ratio is difficult to obtain by a coloring method. According to NASA, the solar absorption ratio of the titanium alloy anodic oxidation coating is 0.84-0.86, the hemispherical emissivity is 0.44-0.46, and the ratio of the solar absorption ratio to the hemispherical emissivity is close to 2.
Plasma electrolytic oxidation is similar to anodic oxidation of metals, which is a method of treating titanium alloys by plasma discharge generated in a liquid medium. The coating grows in situ on the substrate, has high bonding strength with the substrate, is not limited by the size and shape of the substrate, and has good covering effect on inner holes and blind holes of parts. Compared with the common anodic oxidation coating, the plasma electrolytic oxidation coating has the advantages of higher compactness, hardness, heat resistance, corrosion resistance and the like. Patent CN106342108B discloses a method for preparing a thermal control coating on the surface of a titanium alloy, which adopts an electrolyte containing silicate to obtain a thermal control coating with low absorption ratio containing silicon oxide, wherein the silicon oxide exists in an amorphous state in the coating, and the coating is loose and has poor hardness and wear resistance.
Disclosure of Invention
The invention provides a titanium alloy surface thermal control wear-resistant coating and a preparation method thereof, aiming at solving the problems, the coating has excellent thermal control performance and wear resistance, and is used for solving the problems of temperature control and wear resistance of the surface of a space expansion part of a spacecraft.
In a first aspect, the invention provides a preparation method of a titanium alloy surface thermal control wear-resistant coating, which comprises the following steps: the titanium alloy is placed in an electrolyte containing aluminate, and in the plasma electrolytic oxidation process, a direct current pulse current is utilized to enable a dielectric film on the surface of the titanium alloy to be broken down so as to generate plasma micro-arc discharge and grow the thermal control wear-resistant coating on the surface of the titanium alloy in situ. The invention adopts the electrolyte containing the aluminate, promotes the generation of the alumina coating through the hydrolysis of the aluminate in the plasma electrolytic oxidation process, and improves the heat radiation performance of the coating.
The coating is composed of aluminum titanate, titanium oxide and aluminum oxide. Wherein, the aluminum titanate is the main crystal phase of the coating. As an example, the thermally controlled wear resistant coating is comprised of 40 to 50 weight percent aluminum titanate, 30 to 40 weight percent titanium oxide, and 10 to 30 weight percent aluminum oxide. Wherein the alumina is preferably 10-20 wt%.
Preferably, the electrolyte comprises: according to the mass to total volume ratio, 1-20g/L aluminate, 1-20g/L auxiliary film forming substance and water as solvent; the auxiliary film-forming substance is one or a combination of carbonate, phosphate, borate, acetate, sulfate and oxalate. By introducing carbonate, phosphate, borate, acetate, sulfate, oxalate and other auxiliary film forming substances into the electrolyte, the deposition of aluminum oxide on the surface of the titanium alloy is promoted, the compactness of the coating is improved, and the hardness and the wear resistance of the coating are improved.
Preferably, the pulse frequency of the direct pulse current is 1 to 500Hz, preferably 50 to 200 Hz. The use of ac pulsed current is not suitable for the present invention because it causes uneven coating color.
Preferably, the forward current density of the plasma electrolytic oxidation is 1-20A/dm2。
Preferably, the forward voltage of the plasma electrolytic oxidation is 450-650V.
Preferably, the treatment time of the plasma electrolytic oxidation is 10-300min, and preferably 30-180 min.
Preferably, the temperature of the plasma electrolytic oxidation is below 60 ℃, preferably 20-40 ℃. Controlling the temperature of the plasma electrolytic oxidation within the above range is advantageous for increasing the hardness of the coating.
Preferably, the thickness of the coating is 10-150 μm.
In a second aspect, the invention further provides the titanium alloy surface thermal control wear-resistant coating obtained by any one of the preparation methods, wherein the solar absorption ratio of the coating is 0.68-0.76, the hemispherical emissivity is greater than 0.85, and the hardness is greater than 1000 HV. The coating can adapt to the processing of the surface of a part with a complex structure, has high bonding strength with a matrix, and has good spatial stability.
Drawings
FIG. 1 is the phase composition of the thermally controlled wear resistant coating on the surface of the titanium alloy of example 1;
FIG. 2 is a surface topography of the thermally controlled wear-resistant coating on the surface of the titanium alloy of example 1;
FIG. 3 is a cross-sectional profile of the surface thermal control wear-resistant coating of the titanium alloy of example 1;
FIG. 4 is the reflectivity curve of the titanium alloy surface thermal control wear-resistant coating in the solar spectrum region of 250-2500nm in example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention.
The thermal control wear-resistant coating on the surface of the titanium alloy is prepared by adopting a plasma electrolytic oxidation method. The method comprises the steps of placing titanium alloy in a liquid-phase medium, and utilizing plasma micro-arc discharge generated by dielectric film breakdown on the surface of the titanium alloy to grow a ceramic coating in situ.
The preparation method of the titanium alloy surface thermal control wear-resistant coating is exemplarily described below.
And (4) pretreatment of the base material. The substrate may be a TC4 titanium alloy. The pretreatment of the titanium alloy substrate comprises an alkali washing process and an acid washing process. The alkali washing process is to adopt an alkaline solution to carry out titanium alloy treatment so as to remove grease on the surface of the titanium alloy. As an example, the alkaline solution consists of sodium silicate, sodium carbonate, sodium phosphate and OP emulsifier. The acid cleaning process is to use acid solution to process titanium alloy, in order to remove the oxide film on the surface of titanium alloy, so as to obtain clean surface. The acidic solution can be 5-20% hydrofluoric acid aqueous solution by mass.
And (4) preparing an electrolyte. The electrolyte contains at least one soluble aluminate. In some embodiments, the electrolyte comprises: according to the mass to total volume ratio, 1-20g/L of aluminate, 1-20g/L of auxiliary film forming substance and water as solvent. And dissolving aluminate and an auxiliary film-forming substance in deionized water to obtain the electrolyte. The pH value of the electrolyte is adjusted by an auxiliary film forming substance, and is generally 10-13.
As a main film forming substance, aluminate is deposited on the surface of the titanium alloy under the action of an electric field force in the oxidation process, is converted into alumina to participate in the generation of a coating, and is partially combined with titanium oxide to generate aluminum titanate, so that the aluminate is used as the main film forming substance. The base material is titanium alloy, the titanium of the base material is converted into titanium oxide in the micro-arc oxidation process, and the aluminum oxide is aluminate in solution and is deposited on the surface of the coating. Under the high-temperature action of plasma discharge, titanium oxide on the surface layer and partial aluminum oxide generate aluminum titanate, and titanium oxide on the bottom layer does not participate in the reaction.
The auxiliary film-forming agent comprises one or more of carbonate, phosphate, borate, acetate, sulfate and oxalate. The auxiliary film-forming substance has the functions of assisting film formation and improving the ion activity in the electrolyte. The auxiliary film forming agent is selected in the invention based on the principle of improving the compactness of the coating and reducing the roughness of the coating.
The plasma electrolytic oxidation power supply can provide a direct current pulse current waveform. The frequency of the current may be 1-500 Hz. Controlling the power supply parameter to be 1-20A/dm of oxidation current density2The treatment time is 10-300min, and the oxidation temperature is less than 60 ℃.
And carrying out plasma electrolytic oxidation on the pretreated titanium alloy. During the plasma electrolytic oxidation process, the coating is generated in a liquid electrolyte. Specifically, the pretreated titanium alloy is used as one electrode to be placed in an electrolyte, the electrolytic bath is made of stainless steel, and the electrolytic bath is used as the other electrode in the plasma electrolytic oxidation process. Stirring by using compressed air to promote mass transfer of the solution, adopting a single-phase pulse current waveform, and forming a layer of inorganic oxide thermal control coating material on the surface of the titanium alloy by controlling current and voltage parameters in the oxidation process.
The titanium alloy surface heat-control wear-resistant coating treated by the process mainly comprises aluminum oxide, and the thickness of the coating is 10-150 mu m.
The invention uses the solar absorption ratio and the hemispherical emissivity to represent the thermal control performance of the coating, and uses the microhardness value to represent the wear resistance of the coating, and the higher the value is, the better the wear resistance of the coating is.
The solar absorptance of the coating was measured using a Varian Carry500 spectrophotometer, usa, and the hemispherical emissivity of the coating was measured by an a-E radiometer. The solar absorption ratio (in the solar radiation region of 250-2500 nm) of the wear-resistant thermal control coating on the surface of the titanium alloy is 0.68-0.76, the hemispherical emissivity is greater than 0.85, the ratio of the solar absorption ratio to the hemispherical emissivity is less than 1, and the microhardness of the coating is greater than 1000 HV.
The titanium alloy surface heat-control wear-resistant coating has high bonding strength with a substrate, and does not have the phenomena of coating separation, peeling and the like after being subjected to cold-hot alternating circulation for 100 times at the temperature of liquid nitrogen (-196 ℃) to +100 ℃. The titanium alloy surface heat control wear-resistant coating can be used for treating complex structural parts and can better protect parts without the coating. The titanium alloy surface thermal control wear-resistant coating has good vacuum-ultraviolet irradiation resistance, the change of the solar absorption ratio after 5000ESH ultraviolet irradiation is less than 0.05, the titanium alloy surface thermal control wear-resistant coating belongs to a high-stability thermal control coating material, and the problems of temperature control and wear resistance of various titanium alloy parts exposed outside a spacecraft can be solved.
The present invention is further illustrated by, but is not limited to, the following examples. In the embodiment, in the plasma electrolytic oxidation treatment process, a titanium alloy part is used as one electrode, a stainless steel plate is used as a counter electrode, a single-phase pulse plasma electrolytic oxidation power supply device is used for carrying out the oxidation process, the whole process comprises the pretreatment of a sample, the plasma electrolytic oxidation, the cleaning and the drying, and the specific treatment process is carried out according to the steps described in the following embodiments.
Example 1
Taking a titanium alloy test piece with the size of 60 multiplied by 60mm, sequentially carrying out alkali washing, acid washing and other procedures, and preparing electrolyte according to the following mass to volume ratio: 3g/L of sodium aluminate, 10g/L of sodium phosphate, 5g/L of sodium carbonate and water as a solvent. And placing the titanium alloy test piece in the electrolyte, connecting the titanium alloy test piece with one electrode of a power supply, and connecting the other electrode of the power supply with the stainless steel plate and placing the titanium alloy test piece in the electrolyte. The power supply has a frequency of 50Hz by adopting a unidirectional pulse current waveform. During the plasma electrolytic oxidation treatment, the voltage is 490V, and the oxidation current density is 2A/dm2Treatment time 120 min. The resulting thermal control coating had a solar absorptance of 0.70, a hemispherical emissivity of 0.86, and a hardness of 1100 HV.
Example 2
Taking a titanium alloy test piece with the size of 60 multiplied by 60mm, sequentially carrying out alkali washing, acid washing and other procedures, and preparing electrolyte according to the following mass to volume ratio: 10g/L of sodium aluminate, 10g/L of sodium tetraborate, 5g/L of sodium acetate and water as a solvent. And placing the titanium alloy test piece in the electrolyte, connecting the titanium alloy test piece with one electrode of a power supply, and connecting the other electrode of the power supply with the stainless steel plate and placing the titanium alloy test piece in the electrolyte. The frequency of the power supply is 100Hz by adopting a unidirectional pulse current waveform. During the plasma electrolytic oxidation treatment, the voltage is 510V, and the oxidation current density is 8A/dm2Treatment time 90 min. The solar absorption ratio of the generated thermal control coating is 0.72, the hemispherical emissivity is 0.87, and the hardness of the coating is 1200 HV.
Example 3
Taking a titanium alloy test piece with the size of 60 multiplied by 60mm, sequentially carrying out alkali washing, acid washing and other procedures, and preparing electrolyte according to the following mass to volume ratio: 15g/L of sodium aluminate, 15g/L of sodium pyrophosphate, 5g/L of sodium sulfate and water as a solvent. Placing the titanium alloy test piece in electrolyte, connecting with one electrode of a power supply, and connecting the other electrode of the power supply with the stainless steel plateConnected and simultaneously placed in the electrolyte. The single-phase pulse current waveform is adopted, and the frequency of the power supply is 200 Hz. During the plasma electrolytic oxidation treatment, the voltage is 520V, and the oxidation current density is 15A/dm2And the treatment time is 60 min. The solar absorption ratio of the generated thermal control coating is 0.73, the hemispherical emissivity is 0.85, and the microhardness of the coating is 1300 HV.
FIG. 1 shows the phase composition analysis results of the thermal control wear-resistant coating on the surface of the titanium alloy. As can be seen in fig. 1, the coating is composed primarily of alumina, titania, and aluminum titanate, wherein the aluminum titanate is the primary crystalline phase of the coating.
FIG. 2 shows the surface topography of a thermally controlled wear resistant coating on the surface of a titanium alloy. As can be seen from fig. 2, the coating surface was granular, and a large number of spark-ignited discharge products were generated, and the size of the discharge products was varied from several micrometers to several tens of micrometers.
FIG. 3 shows the cross-sectional morphology of the thermally controlled wear-resistant coating on the surface of the titanium alloy. As can be seen in fig. 3, the coating thickness was about 20 microns, the coating was denser and dog-tooth bonded to the substrate. In the plasma electrolytic oxidation process, the coating grows in situ on the surface of the matrix, titanium provided by the matrix is converted into titanium oxide, and part of the titanium oxide and aluminate form aluminum titanate.
FIG. 4 shows the reflectivity curve of the titanium alloy surface thermal control wear-resistant coating in the solar spectrum region of 250-2500nm by calculating the solar absorption ratio (alpha) of the coatingS) Is 0.72.
Comparative example 1
Taking a titanium alloy test piece with the size of 60 multiplied by 60mm, sequentially carrying out alkali washing, acid washing and other procedures, and preparing electrolyte according to the following mass to volume ratio: 3g/L of sodium aluminate, 10g/L of sodium phosphate, 5g/L of sodium carbonate and water as a solvent. And placing the titanium alloy test piece in the electrolyte, connecting the titanium alloy test piece with one electrode of a power supply, and connecting the other electrode of the power supply with the stainless steel plate and placing the titanium alloy test piece in the electrolyte. The frequency of the power supply is 100Hz by adopting an alternating current pulse current waveform. The forward current density during the plasma electrolytic oxidation treatment was 8A/dm2Negative current density 4A/dm2Treatment time 120 min. The produced coating has uneven color and high surface roughness.
Comparative example 2
Taking a titanium alloy test piece with the size of 60 multiplied by 60mm, sequentially carrying out alkali washing, acid washing and other procedures, and preparing electrolyte according to the following mass to volume ratio: sodium aluminate 8g/L and water as solvent. And placing the titanium alloy test piece in the electrolyte, connecting the titanium alloy test piece with one electrode of a power supply, and connecting the other electrode of the power supply with the stainless steel plate and placing the titanium alloy test piece in the electrolyte. The frequency of the power supply is 100Hz by adopting a unidirectional pulse current waveform. During the plasma electrolytic oxidation treatment, the forward current density was 8A/dm2, and the treatment time was 60 min. The solar absorption ratio of the generated thermal control coating is 0.65, the hemispherical emissivity is 0.8, and the hardness of the coating is 200 HV.
Comparative example 3
Taking a titanium alloy test piece with the size of 60 multiplied by 60mm, sequentially carrying out alkali washing, acid washing and other procedures, and preparing electrolyte according to the following mass to volume ratio: 8g/L of sodium phosphate, 4g/L of sodium borate and water as a solvent. And placing the titanium alloy test piece in the electrolyte, connecting the titanium alloy test piece with one electrode of a power supply, and connecting the other electrode of the power supply with the stainless steel plate and placing the titanium alloy test piece in the electrolyte. The frequency of the power supply is 100Hz by adopting a unidirectional pulse current waveform. The forward current density during the plasma electrolytic oxidation treatment was 8A/dm2And the treatment time is 60 min. The generated thermal control coating is composed of titanium oxide, the solar absorption ratio of the coating is 0.80, the hemispherical emissivity of the coating is 0.78, and the hardness of the coating is 300 HV.
Claims (9)
1. The preparation method of the titanium alloy surface thermal control wear-resistant coating is characterized by comprising the following steps: placing the titanium alloy in an electrolyte containing aluminate, and in the plasma electrolytic oxidation process, utilizing direct current pulse current to break down a dielectric film on the surface of the titanium alloy so as to generate plasma micro-arc discharge and grow a thermal control wear-resistant coating on the surface of the titanium alloy in situ; the thermal control wear-resistant coating consists of 40-50wt% of aluminum titanate, 30-40wt% of titanium oxide and 10-30wt% of aluminum oxide.
2. The production method according to claim 1, wherein the electrolyte comprises: according to the mass to total volume ratio, 1-20g/L aluminate, 1-20g/L auxiliary film forming substance and water as solvent; the auxiliary film-forming substance is one or a combination of carbonate, phosphate, borate, acetate, sulfate and oxalate.
3. The method of claim 1 or 2, wherein the pulse frequency of the direct pulse current is 1 to 500Hz, preferably 50 to 200 Hz.
4. The production method according to any one of claims 1 to 3, wherein the forward current density of the plasma electrolytic oxidation is 1 to 20A/dm2。
5. The method as claimed in any one of claims 1 to 4, wherein the forward voltage of the plasma electrolytic oxidation is 450-650V.
6. The titanium alloy surface thermal control wear resistant coating according to any one of claims 1 to 5, characterized in that the treatment time of the plasma electrolytic oxidation is 10-300min, preferably 30-180 min.
7. The titanium alloy surface heat control wear resistant coating according to any one of claims 1 to 6, characterized in that the temperature of the plasma electrolytic oxidation is below 60 ℃, preferably 20-40 ℃.
8. The titanium alloy surface heat control wear resistant coating according to any one of claims 1 to 7, characterized in that the thickness of the coating is 10-150 μm.
9. The titanium alloy surface heat-control abrasion-resistant coating obtained by the preparation method according to any one of claims 1 to 8, characterized in that the solar absorption ratio of the coating is 0.68-0.76, the hemispherical emissivity is greater than 0.85, and the hardness is greater than 1000 HV.
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