CN115948742A - Titanium alloy SiOC composite coating and preparation method and application thereof - Google Patents
Titanium alloy SiOC composite coating and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of high-temperature oxidation resistance of metal materials, and particularly relates to a titanium alloy SiOC composite coating, and a preparation method and application thereof. A preparation method of a titanium alloy SiOC composite coating comprises the following steps: s1, removing an oxide skin on the surface of the titanium-based alloy, and cleaning and drying; mixing polydimethylsiloxane and a curing agent for reaction to obtain a precursor solution; s2, immersing the titanium-based alloy treated in the step S1 into a precursor solution for dip-coating and lifting, and curing the dip-coated and lifted titanium-based alloy; and S3, carrying out heat treatment on the titanium-based alloy treated in the step S2, and cooling to obtain the SiOC composite coating on the surface of the titanium-based alloy. The SiOC composite coating has uniform and compact surface, has excellent binding force with a titanium-based alloy matrix, has lower oxidation weight gain at 800-880 ℃, and can remarkably improve the high-temperature oxidation resistance of the titanium-based alloy at the high temperature of 800-880 ℃.
Description
Technical Field
The invention belongs to the field of high-temperature oxidation resistance of metal materials, and particularly relates to a preparation method of a titanium alloy SiOC composite coating.
Background
In recent years, with the continuous development of aerospace, automobile, chemical and other industries, a novel high-temperature structural material with high-temperature corrosion resistance, low density and excellent mechanical properties has attracted extensive attention.
TiAl-based intermetallic compound (TiAl alloy for short) having low density (3.7-4.2 g/cm) 3 Only 50 percent of the current commercial Ni-based alloy), high specific strength and specific stiffness, good high-temperature creep resistance and the like, and the TiAl alloy is widely applied in the fields of aerospace, automobiles, chemical engineering and the like, particularly in the field of aerospace, is commonly used for preparing parts of combustion engines and aeroengines, such as turbine blades or compressor disks, and is considered as an ideal material for replacing the traditional titanium alloy and nickel-based superalloy in the field of high-temperature structural materials. However, when the temperature is higher than 700 ℃, the TiAl alloy surface is formed by TiO 2 And Al 2 O 3 A mixed oxide film of the composition. However, the oxide film has a loose structure and cannot play a role in protection, so that the failure of the TiAl alloy is accelerated.
The prior art discloses a titanium alloy SiOC composite coating, which is prepared by mixing alkoxy silane, absolute ethyl alcohol and potassium nitrate solution, adding metal or metal oxide nano particles and then by an electrodeposition sol-gel method, and can improve the oxidation resistance of a titanium-based alloy at a high temperature of 800 ℃. However, the SiOC coating prepared by the electrodeposition method is thin and has poor multi-deposition effect, so that the protective performance of the SiOC coating is limited, and the titanium alloy SiOC composite coating aims at improving the oxidation resistance of 800 ℃, and does not make relevant improvement on the oxidation resistance of TiAl alloy at the temperature of above 800 ℃, particularly 850 ℃.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of the titanium alloy SiOC composite coating, the prepared SiOC composite coating has excellent binding force with a titanium-based alloy matrix, and the high-temperature oxidation resistance of the titanium-based alloy at the high temperature of 800-850 ℃ can be obviously improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a titanium alloy SiOC composite coating, which comprises the following steps:
s1, removing an oxide skin on the surface of the titanium-based alloy, and cleaning and drying; mixing polydimethylsiloxane and a curing agent for reaction to obtain a precursor solution;
s2, immersing the titanium-based alloy treated in the step S1 into the precursor solution for dip-coating and lifting, and curing the dip-coated and lifted titanium-based alloy;
s3, carrying out heat treatment on the titanium-based alloy treated in the step S2, and cooling to obtain an SiOC composite coating on the surface of the titanium-based alloy;
wherein in the step S1, the mass ratio of the polydimethylsiloxane to the curing agent is 1 (0.05-0.2);
in the step S2, the curing temperature is 25-150 ℃, and the curing time is 1-24 h;
in the step S3, the heat treatment temperature is 700-1100 ℃, and the heat treatment time is 1-5h.
In step S1, polydimethylsiloxane (PDMS) and a curing agent are subjected to a crosslinking reaction to form an organic three-dimensional network, so that a precursor solution is obtained.
In step S2 of the invention, the titanium-based alloy treated in step S1 is immersed in the precursor solution for dip-coating and lifting, and the solvent is evaporated after curing treatment, thereby being beneficial to obtaining the PDMS initial film on the surface of the titanium-based alloy.
In step S3, the titanium-based alloy treated in step S2 is subjected to heat treatment, and after cooling, PDMS can form a stable SiOC network structure after solidification, crosslinking and heat treatment, and the high-temperature-resistant protective performance is achieved.
According to the invention, through preparing a specific precursor solution and a dip-coating and pulling method with a specific process, a thicker titanium alloy SiOC coating can be obtained, the high-temperature oxidation resistance of the titanium alloy SiOC coating is effectively improved, and the oxidation resistance of the TiAl alloy at the temperature of over 800 ℃ is especially improved.
The invention introduces C by a sol-gel method 4- Ionic substitution of O 2- Ions, resulting in an increase in local bond density, enhancing the glass in the coatingA glass network structure. Due to the enrichment of silicon-carbon bonds, various performance characteristics of the coating, such as mechanical performance, chemical stability, creep resistance, thermal shock resistance, oxidation resistance and the like, are gradually improved.
The titanium alloy SiOC composite coating prepared by the invention has the advantages of uniform and compact surface, good chemical stability, high toughness, good wear resistance, excellent binding force with a titanium-based alloy substrate, lower oxidation weight gain at 800-850 ℃, and capability of remarkably improving the high temperature oxidation resistance of the titanium-based alloy at the high temperature of 800-850 ℃.
Moreover, the method is simple, convenient to operate, high in efficiency and easy to implement.
Alternatively, the mass ratio of polydimethylsiloxane to curing agent is 1:0.1 or 1.
Preferably, the polydimethylsiloxane has a viscosity of 20 to 40mpa.s.
Viscosity affects the thickness of the coating and thus the oxidation resistance. The viscosity is increased within a small range, the thickness is increased, the oxidation resistance is improved, but the viscosity is too high, the internal stress of the coating is too large, the coating is easy to peel off, and the oxidation resistance is deteriorated.
More preferably, the viscosity of the polydimethylsiloxane is 23mpa.s.
Alternatively, the polydimethylsiloxane and the curing agent may be mixed and reacted in a solvent.
Preferably, the solvent is one or more of n-hexane, isopropanol or acetone.
More preferably, the solvent is n-hexane.
N-hexane has better compatibility with polydimethylsiloxane.
Alternatively, in step S1, the mixing reaction temperature may be 15 to 25 ℃.
Alternatively, in step S1, the dissolution and reaction rates may be accelerated by stirring to obtain a precursor solution.
Optionally, in step S1, the titanium-based alloy is a titanium-based alloy containing aluminum. The titanium-based alloy includes but is not limited to Ti 3 -Al、Ti-50Al、Ti-Al 3 Ti-6Al-4V, tiAlN and Ti-47Al-2Cr-2Nb. Furthermore, the utility modelFurther, the titanium-based alloy is Ti-50Al.
Alternatively, in step S1, the surface oxide may be removed by sanding the titanium-based alloy substrate.
Optionally, in step S1, the cleaning agent includes, but is not limited to, degreasing liquid and deionized water, and further, the cleaning is performed multiple times by using ultrasound. Furthermore, the cleaning is ultrasonic cleaning in degreasing liquid and deionized water for not less than 10min.
Alternatively, in step S3, the heat treatment may be performed in an air environment, an argon environment, or a vacuum environment.
Preferably, in step S3, the heat treatment is performed in a vacuum environment.
Preferably, in step S3, the heat treatment temperature is 700 ℃ to 1000 ℃. More preferably, in step S3, the heat treatment temperature is 800 ℃ to 900 ℃.
Preferably, the heat treatment time is 1 to 5 hours.
Preferably, in step S1, the precursor solution further includes metal ions, nano metal particles or nano metal oxide particles; in step S1, the mass ratio of the metal ions to the polydimethylsiloxane is (0.05-0.5): 1; in the step S1, the concentration of the nano metal particles or nano metal oxide particles in the precursor solution is 0.01g/100mL-1g/100mL.
The invention can effectively make up the deficiency of SiOC performance by modifying metal ions and doping nano metal particles or nano metal oxide particles, and regulate and control the key performance of the SiOC, such as inorganic SiO 2 、ZrO 2 The nanoparticles have high thermal and chemical stability, and oxygen atoms and metal ions in SiO 2 、ZrO 2 The diffusion speed is very low, the high-temperature protection capability of the coating can be further improved, and the hardness of the coating is increased; al (Al) 2 O 3 The nano-particles have compact crystal form, low oxygen solubility and Al doping 2 O 3 The nano particles can increase the compactness of the coating and prolong the service life of the coating. The doping of the nano metal particles can not only adjust the thermal expansion coefficient of the coating and reduce the thermal expansion of the SiOC coating and the substrateThe difference of the coefficients can also improve the brittleness of the PDMS coating by utilizing the toughness of the metal; meanwhile, the added nano metal particles can be used as a standby protective particle source, and when the SiOC coating generates cracks and other defects, the cracks are compensated by selective oxidation.
According to researches, the composite coating prepared by combining the nano metal particles or nano metal oxide particles with the SiOC has the common advantages of the nano metal particles or nano metal oxide particles and the SiOC, and can finally provide excellent high-temperature oxidation resistance, better wear resistance, toughness and impact resistance for the SiOC coating. And the SiOC coating and the substrate have excellent binding force, and the oxidation resistance and the thermal shock resistance of the titanium-based alloy at the high temperature of 800-850 ℃ can be obviously improved.
The metal ions can react with the SiOC network structure at high temperature to form water glass, improve the microstructure of the coating, improve the structural stability of the coating and play a role in stabilizing the SiOC structure.
Alternatively, the metal ion may be obtained by an organic metal salt.
Alternatively, the mass ratio of organometallic salt to polydimethylsiloxane can be 0.125.
More preferably, the concentration of the nano-metal particles or nano-metal oxide particles in the precursor solution is from 0.05g/100mL to 0.8g/100mL.
Still further preferably, the concentration of the nano metal particles or nano metal oxide particles in the precursor solution is 0.1g/100mL-0.6g/100mL.
Alternatively, an organometallic salt may be added to the precursor solution to introduce metal ions.
Alternatively, in step S1, after the nano metal particles or nano metal oxide particles are added to the precursor solution, the precursor solution may be sufficiently stirred with magnetons to form a suspension, and then dip-coating and drawing may be performed.
Preferably, in step S1, the metal ions include one or more of Al ions, ce ions, or Y ions.
More preferably, the metal ions are Al ions.
PreferablyIn the step S1, the nano metal particles are one or more of Ni nanoparticles, al nanoparticles, zr nanoparticles, or Cr nanoparticles; the nano metal oxide particles are SiO 2 Nanoparticles, al 2 O 3 Nanoparticles or ZrO 2 One or more of the nanoparticles.
More preferably, the nano-metal particles are Ni nanoparticles.
Preferably, in step S1, the mass fraction of the polydimethylsiloxane in the precursor solution is 20wt% to 50wt%.
For example, the mass fraction of polydimethylsiloxane may be 20wt%, 30wt%, 40wt% or 50wt%.
The carbon content in SiOC can be regulated and controlled by configuring different precursor solutions, and the content of two carbon forms, namely carbon and free carbon in a glass grid is changed, so that the performance of the SiOC composite coating in all aspects is regulated. When the carbon in the glass structure is saturated to such an extent that the carbon ions can no longer combine with the glass network, they begin to form the so-called free carbon phase. The free carbon phase can form different graphite structures at different temperatures, and the graphite structures can provide part of freely moving electrons to provide certain conductivity for the coating.
The precursor solution can comprise tetraethoxy siloxane or tetramethoxy silane, the Si content in the tetraethoxy siloxane or tetramethoxy silane is higher, the Si/C ratio can be regulated and controlled, and the protective performance of the coating is further improved.
Preferably, in step S2, the number of dip-coating pulls is 1 to 10.
For example, the number of dip-coating pulls may be 1, 3, 5, 7, or 10.
Preferably, in step S2, the dip coating pull rate is 1.8 to 60mm/min.
For example, the dip pull rate can be 1.8mm/min, 3mm/min, 6mm/min, 30mm/min, or 60mm/min.
The invention also protects the titanium alloy SiOC composite coating prepared by any one of the preparation methods.
Preferably, the thickness of the SiOC composite coating of the titanium alloy is 1-12 μm.
Preferably, the thickness of the titanium alloy SiOC composite coating is 8 μm.
The invention also protects a titanium alloy material which comprises the titanium alloy SiOC composite coating.
The invention also protects the application of the titanium alloy material in the preparation of turbine blades or compressor disks.
Compared with the prior art, the invention has the beneficial effects that: the invention mixes polydimethylsiloxane and curing agent for reaction, and prepares a uniform and compact titanium alloy SiOC composite coating through a sol-gel method and a dip-coating and drawing technology, the SiOC composite coating has good chemical stability, high toughness and good wear resistance, has excellent binding force with a titanium-based alloy matrix, and can remarkably improve the high-temperature oxidation resistance of the titanium-based alloy at the high temperature of 800-850 ℃.
Drawings
FIG. 1 is a scanning electron microscope image of a TiAl alloy specimen of example 3 covered with a SiOC coating having a PDMS concentration of 50wt.% after high temperature oxidation at 850 ℃ for 100 h;
FIG. 2 is a scanning electron microscope image of TiAl alloy specimens of example 3 covered with a SiOC coating having a PDMS concentration of 30wt.% after 100h of high temperature oxidation at 850 ℃;
FIG. 3 is a scanning electron microscope image of TiAl alloy samples covered with the SiOC composite coating doped with Ni nanoparticles of example 5 after being oxidized at 850 ℃ for 100 h.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Polydimethylsiloxane and a matched curing agent, the brand is Dow Corning, and the model is SYLGARD184.
Wherein the polydimethylsiloxane comprises the following specific components: the dimethylsiloxane terminates with dimethylvinylsiloxane (Dimethyl Siloxane, dimethylvinylsiloxane-terminated, > 64.0- < =66.0%, CAS: 68083-19-2), ethylbenzene (Ethylbenzene, > 0.19- < =0.2%, CAS: 100-41-4), dimethylvinylated and trimethylated silica (Dimethylvinylated and trimethylated silica, > 32.0- < =33.0%, CAS: 68988-89-6) in mass percent.
The curing agent comprises the following specific components: dimethylmethylhydrosiloxane and silicone (Siloxanes and Silicones, di-Me, me hydrogen, > < 55.0- < =65.0%, CAS: 68037-59-2), dimethylsiloxane terminated dimethylvinylsiloxane (Dimethyl Siloxane, dimethylvinylsiloxane-terminated, > < 22.0- < =27.0%, CAS: 68083-19-2), dimethylvinylated and trimethylated silica (Dimethylvinylated and trimethylated silica, > < 11.0- < =14.0%, CAS: 68988-89-6), methylvinylcyclosiloxane (dimethylvinylcyclosiloxane, > < 1.0- > 3.0%, CAS: 2554-06-5), in mass percent.
Example 1 Effect of the number of pulls on the preparation of a titanium alloy SiOC composite coating
(1) Firstly, polishing a Ti-50Al alloy pattern by using sand paper, removing surface oxide skin, then sequentially ultrasonically cleaning in degreasing liquid and deionized water for 10min, and finally drying by using hot air for later use;
(2) Adding 4g of polydimethylsiloxane and 0.4 g of curing agent into 16g of n-hexane, and stirring at room temperature until the materials are uniformly mixed to obtain a precursor solution; the mass fraction of the polydimethylsiloxane is 20wt%;
(3) Completely immersing the processed Ti-50Al alloy sample in a PDMS solution, slowly lifting the Ti-50Al alloy sample from the PDMS by using a dip coating and pulling device at the speed of 6mm/min, preserving heat for 2h in air at 120 ℃, respectively repeating the operations for one, three, five and seven times, and finally obtaining three groups of initial films with different layers on the Ti-50Al surface;
(4) And (3) putting the Ti-50Al alloy sample into a vacuum environment at 800 ℃ for heat treatment for 5h, and cooling to room temperature in vacuum to form an SiOC coating on the surface of the TiAl alloy sample.
Subsequently, the Ti-50Al alloy samples covered with different numbers of SiOC coatings were subjected to constant temperature oxidation at 800 ℃ for 100h (using the bare Ti-50Al alloy sample as a control), and the high temperature oxidation resistance was evaluated by the weight gain per unit area, and the experimental results are shown in table 1.
TABLE 1 comparison of the high temperature oxidation resistance at 800 ℃ of bare TiAl alloy and Ti-50Al alloy samples coated with SiOC coatings of different pulling times
| Sample(s) | Number of lifting | Weight gain mg/cm 2 |
| Bare Ti-50Al alloy | - | 1.37 |
| Ti-50Al alloy coated with SiOC coating | 1 | 0.45 |
| Ti-50Al alloy coated with SiOC coating | 3 | 0.093 |
| Ti-50Al alloy coated with SiOC coating | 5 | 0.086 |
| Ti-50Al alloy coated with SiOC coating | 7 | 0.104 |
It can be seen from table 1 that when the surface of the Ti-50Al alloy sample is covered with the SiOC composite coating, the samples pulled three times and five times have better high temperature oxidation resistance, wherein the effect of pulling five times is the best.
Example 2 Effect of the pulling Rate on the preparation of a titanium alloy SiOC composite coating
The specific preparation method is different from that of example 1 in that: the number of pulling times was set to five times, and the pulling rates were changed to 1.8mm/min, 3mm/min, 6mm/min, 30mm/min and 60mm/min, respectively. And finally, evaluating the high-temperature oxidation resistance of the TiAl alloy samples with different pulling rates (by taking the bare TiAl alloy sample as a contrast), wherein the experimental results are shown in Table 2.
TABLE 2 high temperature Oxidation resistance at 850 ℃ of TiAl alloy specimens coated with SiOC coatings of different pull rates
| Sample (I) | The pulling rate is mm/min | Weight gain mg/cm 2 |
| Bare Ti-50Al alloy | - | 3.00 |
| Ti-50Al alloy coated with SiOC coating | 1.8 | 0.31 |
| Ti-50Al alloy coated with SiOC coating | 3 | 0.32 |
| Ti-50Al alloy coated with SiOC coating | 6 | 1.23 |
| Ti-50Al alloy coated with SiOC coating | 30 | 1.21 |
| Ti-50Al alloy coated with SiOC coating | 60 | 1.09 |
As can be seen from Table 2, when the surface of the TiAl alloy sample is covered with the SiOC coating, the high-temperature oxidation resistance effect can be better achieved by 1.8mm/min, 3mm/min, 6mm/min, 30mm/min and 60mm/min, wherein the effects of 1.8mm/min and 3mm/min are the best, and the oxidation weight gain is far lower than that of other samples.
Example 3 Effect of PDMS concentration on titanium alloy SiOC composite coating preparation
The specific preparation method is different from that of example 1 in that: the number of pulls was set to five times, the pull rate was set to 3mm/min, and the mass fraction of PDMS was changed to 20wt.%, 30wt.%, 40wt.%, and 50wt.%, respectively. And finally, evaluating the high-temperature oxidation resistance of TiAl alloy samples with different PDMS concentrations (by taking the naked TiAl alloy sample as a contrast), wherein the experimental results are shown in Table 3. In addition, after the high-temperature oxidation for 100h, the TiAl alloy sample covered with the SiOC composite coating is observed by a scanning electron microscope, and the observation structure is shown in FIG. 1 and FIG. 2.
TABLE 3 high temperature Oxidation resistance at 850 ℃ of TiAl alloy specimens coated with SiOC coatings of different PDMS concentrations
As can be seen from table 3 and fig. 1, when the surface of the TiAl alloy sample is covered with the SiOC coating, 20wt.%, 30wt.%, 40wt.% and 50wt.% of PDMS can achieve better high temperature oxidation resistance, wherein the effect of 50wt.% of PDMS is the best, and after 100 hours, the coating still remains intact and no more oxides appear, which indicates that the higher the concentration is, the better the protective performance of the coating is. However, when the PDMS is doped in a concentration of more than 30wt.%, the coating is subjected to a large thermal stress in a high temperature environment, and cracks may be generated to reduce the service life of the coating, as shown in fig. 2.
Example 4 preparation of Ti-50Al alloy SiOC composite coating by ion modification
(1) Firstly, polishing a Ti-50Al alloy pattern by using sand paper, removing surface oxide skin, then sequentially ultrasonically cleaning in degreasing liquid and deionized water for 10min, and finally drying by using hot air for later use;
(2) Adding 4g of polydimethylsiloxane and 0.4 g of curing agent into 16g of n-hexane, respectively adding 2.0g of polydimethylsiloxane, 1.0g of polydimethylsiloxane and 0.5g of aluminum sec-butoxide, and stirring at room temperature until the materials are uniformly mixed to obtain a precursor solution; the mass fraction of the polydimethylsiloxane is 20wt%;
(3) Completely immersing the processed Ti-50Al alloy sample in a PDMS solution containing secondary aluminum butoxide, slowly extracting the Ti-50Al alloy sample from the PDMS solution containing the secondary aluminum butoxide at the speed of 3mm/min by using a dip-coating pulling device, preserving the temperature for 2h in air at 120 ℃, repeating the operation for five times, and finally obtaining an initial film on the surface of the Ti-50 Al;
(4) And (3) putting the Ti-50Al alloy sample into a vacuum environment at 850 ℃ for heat treatment for 5h, and cooling to room temperature in vacuum to form a SiAlOC composite coating on the surface of the TiAl alloy sample.
Subsequently, the Ti-50Al alloy sample covered with the SiAlOC composite coating was subjected to constant temperature oxidation at 850 ℃ for 100 hours (with the bare Ti-50Al alloy sample as a control), and the high temperature oxidation resistance was evaluated by the weight increase per unit area, and the experimental results are shown in table 4. In addition, after high-temperature oxidation for 100h, the TiAl alloy sample covered with the SiAlOC composite coating is observed by a scanning electron microscope.
TABLE 4 comparison of the high temperature Oxidation resistance at 850 ℃ of bare TiAl alloys and Ti-50Al alloy specimens with SiAlOC coatings of different aluminum sec-butoxide quality
Example 5 preparation of a Ti-50Al alloy SiOC composite coating by means of nanoparticle doping
(1) Firstly, polishing a Ti-50Al alloy pattern by using sand paper, removing surface oxide skin, then sequentially ultrasonically cleaning in degreasing liquid and deionized water for 10min, and finally drying by using hot air for later use;
(2) Adding 7g of polydimethylsiloxane and 0.7 g of curing agent into 9.8g of n-hexane, adding 0.023g of Ni nanoparticles, and performing ultrasonic stirring at room temperature until the mixture is uniformly mixed to obtain a Ni suspension; the concentration in the Ni nanoparticle precursor solution was 0.1g/100mL. The mass fraction of the polydimethylsiloxane is 40wt%;
(3) Completely immersing the processed Ti-50Al alloy sample in a PDMS solution, slowly extracting the Ti-50Al alloy sample from PDMS by using a dip coating and pulling device at the speed of 3mm/min, preserving heat for 2h in air at 120 ℃, repeating the operation for three times, and finally obtaining an initial film on the surface of Ti-50 Al;
(4) And (3) putting the Ti-50Al alloy sample into a vacuum environment at 800 ℃ for heat treatment for 5h, and cooling to room temperature in vacuum to form a Ni-doped SiOC composite coating on the surface of the TiAl alloy sample.
Subsequently, the Ti-50Al alloy sample covered with the Ni-SiOC composite coating is placed at 850 ℃ for constant temperature oxidation for 100h (with the bare Ti-50Al alloy sample and the SiOC coating sample as controls), and the high temperature oxidation resistance is evaluated by the weight increase per unit area, and the specific results are shown in table 5. In addition, after the high-temperature oxidation for 100h, the TiAl alloy sample covered with the SiOC composite coating is observed by a scanning electron microscope, and the specific result is shown in figure 3. It can be seen from fig. 3 that oxidized particles and nickel particles are present on the surface of the intermediate coating after oxidation.
TABLE 5 comparison of the high temperature Oxidation resistance at 850 ℃ of bare TiAl alloys, ti-50Al alloy specimens coated with SiOC coatings and Ni-SiOC coatings
It can be seen from table 4 that the high temperature oxidation resistance of the TiAl alloy specimens can be further improved by doping Ni nanoparticles into the SiOC coating.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The preparation method of the titanium alloy SiOC composite coating is characterized by comprising the following steps:
s1, removing an oxide skin on the surface of the titanium-based alloy, and cleaning and drying the oxide skin; mixing polydimethylsiloxane and a curing agent for reaction to obtain a precursor solution;
s2, immersing the titanium-based alloy treated in the step S1 into the precursor solution for dip-coating and lifting, and curing the dip-coated and lifted titanium-based alloy;
s3, carrying out heat treatment on the titanium-based alloy treated in the step S2, and cooling to obtain an SiOC composite coating on the surface of the titanium-based alloy;
wherein in the step S1, the mass ratio of the polydimethylsiloxane to the curing agent is 1 (0.05-0.2);
in the step S2, the curing temperature is 25-150 ℃, and the curing time is 1-24 h;
in the step S3, the heat treatment temperature is 700-1100 ℃, and the heat treatment time is 1-5h.
2. The method for preparing the titanium alloy SiOC composite coating according to claim 1, wherein in step S1, the precursor solution further comprises metal ions, nano-metal particles or nano-metal oxide particles; in step S1, the mass ratio of the metal ions to the polydimethylsiloxane is (0.05-0.5): 1; in the step S1, the concentration of the nano metal particles or nano metal oxide particles in the precursor solution is 0.01g/100mL-1g/100mL.
3. The method for preparing the titanium alloy SiOC composite coating according to claim 2, wherein in step S1, the metal ions comprise one or more of Al ions, ce ions or Y ions.
4. The method for preparing the SiOC composite coating of the titanium alloy according to the claim 2The preparation method is characterized in that in the step S1, the nano metal particles are one or more of Ni nano particles, al nano particles, zr nano particles or Cr nano particles; the nano metal oxide particles are SiO 2 Nanoparticles, al 2 O 3 Nanoparticles or ZrO 2 One or more of the nanoparticles.
5. The method for preparing the SiOC composite coating of the titanium alloy as claimed in claim 1, wherein in step S1, the polydimethylsiloxane is present in the precursor solution in an amount of 20wt% to 50wt%.
6. The method for preparing the titanium alloy SiOC composite coating according to the claim 1, wherein the dip-coating and drawing times in the step S2 are 1-10 times.
7. The method for preparing the titanium alloy SiOC composite coating according to the claim 1, wherein in the step S2, the dip-coating pulling rate is 1.8-60mm/min.
8. The titanium alloy SiOC composite coating prepared by the preparation method of any one of claims 1 to 7.
9. A titanium alloy material comprising the titanium alloy SiOC composite coating of claim 8.
10. Use of the titanium alloy material according to claim 9 for the production of turbine blades or compressor disks.
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