CN107056336B - Long-time ablation-resistant composite coating on surface of carbon/carbon composite material and preparation method thereof - Google Patents

Long-time ablation-resistant composite coating on surface of carbon/carbon composite material and preparation method thereof Download PDF

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CN107056336B
CN107056336B CN201710204416.9A CN201710204416A CN107056336B CN 107056336 B CN107056336 B CN 107056336B CN 201710204416 A CN201710204416 A CN 201710204416A CN 107056336 B CN107056336 B CN 107056336B
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李贺军
贾瑜军
付前刚
姚西媛
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Northwestern Polytechnical University
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Abstract

The invention relates to a long-time ablation-resistant composite coating on the surface of a carbon/carbon composite material and a preparation method thereof2O3Complex phase ceramic coating. The prepared composite coating can effectively protect the C/C composite material for at least 700s in an ultrahigh-temperature environment. The invention has the beneficial effects that: by introducing rare earth La into ZrC coating2O3Using La2O3The low-volatility composite oxide formed by the zirconia at the ultrahigh temperature heals the pores and cracks in the ultrahigh-temperature ceramic coating at the high temperature, so that the ablation protection time of the ultrahigh-temperature ceramic coating is prolonged.

Description

Long-time ablation-resistant composite coating on surface of carbon/carbon composite material and preparation method thereof
Technical Field
The invention belongs to a preparation technology of a carbon/carbon composite material, and relates to a long-time ablation-resistant composite coating on the surface of the carbon/carbon composite material and a preparation method thereof.
Background
The C/C composite material is an ideal thermal structure material due to the excellent performances of low density, high specific strength, high specific modulus, high temperature resistance, ablation resistance and the like, and has very wide application prospect in the field of aerospace. However, the easy oxidation at high temperature is always a key problem which restricts the practical application of the C/C composite material. Surface coating techniques are an effective means to solve this problem. To date, oxidation protection technology for C/C composites below 1600 ℃ has achieved satisfactory results.
Document 1 "Oxidation protection of ultra-high temperature ceramic ZrxTa1- xB2-SiC/SiC coating prepared by in-situ reaction method for carbon/carbon composites, Xuanru Ren, Hejun Li, Kezhi Li, Qiangang Fu. journal of the European ceramic Society 2015, (35): 897. 907. "reported Zr prepared by in-situ reaction method on the surface of C/C compositexTa1-xB2the-SiC/SiC composite coating can protect the C/C composite material for 1412 hours under the static oxidation condition of 1500 ℃, and the oxidation weight loss rate is only 0.1 wt.%.
Document 2 "TaxHf1-xB2-SiC Multiphase oxidation protective coating for SiC-coated carbon/carbon composites, Xuanru Ren, Hejun Li, Qiangang Fu, Kezhili Corrosion Science2014, (87): 479) 488, "Ta prepared by in situ reaction on the surface of C/C compositesxHf1-xB2the-SiC multiphase coating can protect the C/C composite material for 1480h under the static oxidation condition of 1500 ℃.
The ultra-long oxidation protection time shows that the research on the oxidation protection coating of the C/C composite material below 1700 ℃ is relatively mature, the coating systems mainly take silicon-based coatings as main materials, and borosilicate glass generated by the oxidation of the coatings at high temperature is utilized to prevent the permeation of oxygen. At temperatures above 1700 c, however, the protective properties of the coating are greatly reduced by the severe volatilization of the silicon element in the silicon-based coating at very high temperatures, sometimes even leading to severe damage of the coating system due to reactive oxidation of the silicon-based compound. Therefore, the oxidation resistance and ablation resistance protection at the temperature of more than 1700 ℃ mainly adopts ultra-high temperature ceramics (mainly refer to carbides, borides and the like of zirconium and hafnium) or modified ultra-high temperature ceramics. However, the ablation protection of these coatings is also short-lived.
Document 3 "Xiaohong Shi, Junhao Huo, Junliang Zhu, Lei Liu, Hejun Li, Xiaojunhu, Mengyan Li, Lingjun Guo, Qiangang Fu. approximation resistance of SiC-ZrC coating predicted by a simple two-step method on carbon fiber reinforced composites, correction Science2014, (88) 49-55", although the reported SiC-ZrC coatings can be in 2.4MW/m2The coating can resist ablation and protect the C/C composite material 45s under the heat flow, but the main component of the coating is mainly silicon-based material, the loss of the coating is serious after the coating is oxidized under the ultrahigh-temperature ablation environment, and the service life of the coating is difficult to prolong.
Document 4 "approximation Resistance of ZrB2-SiC Coating Prepared by SupersonicAtmperene Plasma Spraying for SiC-Coated Carbon/Carbon Composites, Yulei Zhang, Zhixiong Hu, Hejun Li, Jincui ren. ceramics International 2014, (40) 14749-2Coating of-SiC at 2.4MW/m2The ablated 60s coating is destroyed mainly due to insufficient viscosity of the generated oxide layerAre susceptible to degradation at high temperatures.
Document 5 "approximation resistance of HfC-SiC coating prepared by hybridization plating for SiC-coated C/C compositions, Yang Yang, Kezhi Li, Zhurigang Zhao, Hejun Li. ceramics International 2016, (42) 4768-" reported HfC-SiC coatings although at 2.4MW/m2The C/C composite material is protected for 60s by ablation resistance under the heat flow, however, the effective protection time is shorter because silicon-based phase modification is adopted.
As mentioned above, these ultra-high temperature ceramic coating systems contain a silicon-based phase, which is oxidized to form SiO2Or borosilicate glass has insufficient viscosity at ultrahigh temperature and SiC is likely to be subjected to active oxidation, so that the anti-ablation performance of the coating is deteriorated, and the oxidation protection time of the coating is short, so that the long-time oxidation resistance or anti-ablation protection at the temperature of more than 1700 ℃ becomes a bottleneck which is difficult to break through in the application of the C/C composite material.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a long-time ablation-resistant composite coating on the surface of a carbon/carbon composite material and a preparation method thereof, and provides long-time ablation protection for the C/C composite material in an ultrahigh-temperature environment of over 1700 ℃.
Technical scheme
A long-time ablation-resistant composite coating on the surface of a carbon/carbon composite material is characterized in that: the inner coating is SiC coating, and the outer coating is ZrC-La2O3Complex phase ceramic coating.
A method for preparing the long-time ablation-resistant composite coating on the surface of the carbon/carbon composite material is characterized by comprising the following steps:
step 1: burying the pretreated C/C composite material in the mixed powder in a graphite crucible, putting the graphite crucible into a hot-pressing vacuum reaction furnace using graphite as a heating element, performing vacuum treatment on the vacuum furnace to ensure that the vacuum degree reaches-0.09 MPa, introducing Ar gas to the normal pressure, raising the furnace temperature from room temperature to 1800-2100 ℃ at the temperature rise speed of 5-10 ℃/min, and preserving the temperature for 1-3 hours; turning off a power supply, naturally cooling to room temperature, and introducing Ar gas for protection in the whole process to obtain the C/C composite material with the SiC inner coating on the surface;
the mixed powder comprises the following components: mixing Si powder, C powder and Al2O3Mixing 65-85 wt%, 10-25 wt% and 5-10 wt% of the powder in a resin ball milling tank, and mixing for 2-4 hr to obtain mixed powder;
step 2, preparing powder for spraying by adopting a spray drying method:
1) mixing 10 vol.% to 25 vol.% La2O3Uniformly stirring and mixing the powder and ZrC powder in a corundum mortar;
2) preparing a polyvinyl alcohol solution with the concentration of 3 wt.% as a binder, and mixing and stirring for 30min according to the proportion of 40-50 wt.% of distilled water, 2-5 wt.% of the binder and 40-50 wt.% of ceramic mixed powder to form feed slurry; then, granulating by adopting a spray drying method;
step 3, preparing ZrC-La2O3Complex phase ceramic coating:
placing the C/C composite material with the surface containing the SiC inner coating obtained in the step 1 into a clamp, filling the spraying powder prepared in the step 2 into a powder feeder, and spraying the powder onto the C/C composite material embedded with the SiC coating according to the following process parameters to prepare ZrC-La2O3A complex phase ceramic coating;
plasma spraying process parameters: spraying direct current: 380-450A; spraying direct-current voltage: 115-140V; main gas flow: 75-85L/min; auxiliary gas flow rate: 4.5-5.5L/min; powder feeding rate: 20-40 g/min; spraying distance: 80-140 mm; the spraying process is 8-15 times of spraying.
The pretreatment of the C/C composite material is as follows: and polishing the C/C composite material, ultrasonically cleaning, and drying in an oven.
When the spray drying method is used for granulation: the inlet temperature of the dryer is 300-330 ℃, the outlet temperature is 110-150 ℃, the rotating speed of the spray head is 30-40 rpm, and the feeding speed is 65-85 ml/min.
Advantageous effects
The invention provides a long-time ablation-resistant composite coating on the surface of a carbon/carbon composite material and a preparation method thereof, and a bag is adoptedThe SiC coating and ZrC-La are prepared by a two-step method of burying method and supersonic plasma spraying (SAPS for short)2O3Complex phase ceramic coating. The prepared composite coating can effectively protect the C/C composite material for at least 700s in an ultrahigh-temperature environment. The invention has the beneficial effects that: by introducing rare earth La into ZrC coating2O3Using La2O3The low-volatility composite oxide formed by the zirconia at the ultrahigh temperature heals the pores and cracks in the ultrahigh-temperature ceramic coating at the high temperature, so that the ablation protection time of the ultrahigh-temperature ceramic coating is prolonged.
Drawings
FIG. 1 is ZrC-La prepared in example 32O3And (3) carrying out secondary electronic pictures on the cross section back scattering and the surface of the/SiC composite coating.
FIG. 2 is ZrC-La prepared in example 32O3the/SiC composite coating is ablated at the heat flow of 2.4MW/m2Surface secondary electron pictures after ablation for 200s in oxyacetylene environment.
Fig. 3 is a magnified photograph and spectral analysis of the different regions in fig. 2. (a) Magnified photograph of area a (B) magnified photograph of area B.
FIG. 4 ZrC-La prepared in example 32O3the/SiC composite coating is ablated at the heat flow of 2.4MW/m2A macroscopic photograph after 700s of ablation in an oxyacetylene environment.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the technical scheme adopted by the invention for solving the technical problem comprises the following steps:
step 1: preparation of SiC undercoating
1) Polishing the C/C composite material, ultrasonically cleaning, and drying in a drying oven;
2) mixing Si powder, C powder and Al2O3Mixing 65-85 wt%, 10-25 wt% and 5-10 wt% of the powder in a resin ball milling tank for 2-4 hr to mix the powder evenly;
3) placing the mixed powder into a graphite crucible, burying the C/C composite material in the mixed powder, placing the graphite crucible into a hot-pressing vacuum reaction furnace with graphite as a heating element, vacuumizing to enable the vacuum degree to reach-0.09 MPa, introducing Ar gas to normal pressure, heating the furnace temperature from room temperature to 1800-2100 ℃ at the heating speed of 5-10 ℃/min, and preserving the heat for 1-3 hours; turning off a power supply, naturally cooling to room temperature, and introducing Ar gas for protection in the whole process to obtain the C/C composite material with the SiC coating on the surface;
step 2: spray drying method for preparing powder for spraying
1) Adding 15% of La by volume2O3Uniformly stirring and mixing the powder and ZrC powder in a corundum mortar;
2) preparing a polyvinyl alcohol solution with the concentration of 3 wt.% as a binder, and mixing and stirring the polyvinyl alcohol solution and the ceramic mixed powder according to the proportion of 40-50 wt.% of distilled water, 2-5 wt.% of the binder and 40-50 wt.% of the ceramic mixed powder to form feed slurry. Then granulating by a spray drying method. The inlet temperature of the dryer is 300-330 ℃, the outlet temperature is 110-150 ℃, the rotating speed of the spray head is 30-40 rpm, and the feeding speed is 65-85 ml/min.
And step 3: preparation of ZrC-La2O3Complex phase ceramic coating
Placing the C/C composite material with the surface containing the SiC inner coating obtained in the step 1 into a sample clamp, filling the spraying powder prepared in the step 2 into a powder feeder, opening the SAPS equipment, and spraying the powder onto the C/C composite material embedded with the SiC coating according to the following process parameters to prepare ZrC-La2O3Complex phase ceramic coating.
The plasma spraying process parameters are as follows:
spraying direct current: 380-450A; spraying direct-current voltage: 115-140V; main gas flow: 75-85L/min; auxiliary gas flow rate: 4.5-5.5L/min; powder feeding rate: 20-40 g/min; spraying distance: 80-140 mm; the spraying process is 8-15 times of spraying.
The specific embodiment is as follows:
example 1:
step 1: and preparing a SiC inner coating. The specific process is as follows:
1) and sequentially polishing the C/C composite material by using No. 400 and No. 800 sandpaper, cleaning by using absolute ethyl alcohol, and drying for 24 hours in an oven at the temperature of 80 ℃ for later use.
2) 100g of Si powder, 18g of C powder and Al powder were weighed out separately2O3And 8g of powder, placing the powder in a rosin ball milling tank, adding different amounts of agate balls with different diameters, and carrying out ball milling and mixing treatment for 2 hours. The obtained mixed powder is used as an embedding material.
3) And putting half of the mixed powder into a graphite crucible, then putting the cleaned C/C composite material on the mixed powder, and then putting the other half of the embedded powder to completely cover the sample.
And (3) putting the graphite crucible filled with the embedded powder and the C/C composite material into a hot-pressing vacuum reaction furnace using graphite as a heating body. And vacuumizing the reaction furnace to ensure that the vacuum degree reaches-0.09 MPa, and then keeping the vacuum for 40 minutes. Then argon was introduced to normal pressure. This process was repeated twice for the scrubbing treatment. The furnace temperature was then raised to 2050 ℃ at a ramp rate of 10 ℃/min and held for 2.5 hours. And finally, powering off, naturally cooling to room temperature, and introducing argon for protection in the whole process. And after the heat treatment is finished, taking out the crucible, taking out the C/C composite material sample, and cleaning the embedded powder on the surface of the coated sample to obtain the SiC-coated C/C composite material.
Step 2: the powder for spraying is prepared by a spray drying method. The specific process is as follows:
1) adding 15% of La by volume2O3Uniformly stirring and mixing the powder and ZrC powder in a corundum mortar;
2) polyvinyl alcohol solution with the concentration of 3 wt.% is prepared as a binder, and the polyvinyl alcohol solution and the binder are mixed and stirred for 30min according to the proportion of 47 wt.% of distilled water, 3 wt.% of binder and 50 wt.% of ceramic mixed powder to form feed slurry. The inlet temperature of the dryer was raised to 320 c, the outlet temperature to 120 c, the nozzle speed was adjusted to 37rpm, and the prepared slurry was fed through the feed apparatus of the granulator at a feed rate of 65 ml/min. And after all slurry feeding is finished, collecting dry powder at a discharge port to be used as powder for spraying.
And step 3: preparation of ZrC-La2O3Complex phase ceramic coating
Fixing the C/C composite material with the SiC inner coating prepared in the step 1 by using a sample clamp, loading the spraying powder prepared in the step 2 into a powder feeder, opening SAPS equipment, and checking whether the equipment leaks water and gas. After the equipment is confirmed to be intact, spraying the spraying powder on the C/C composite material sample coated with the SiC coating according to the following spraying parameters to obtain ZrC-La2O3The C/C composite material is coated by the/SiC composite coating.
The specific SAPS process parameters are as follows:
spraying direct current: 390A; spraying direct-current voltage: 130V; main gas flow: 75L/min; auxiliary gas flow rate: 4.5L/min; powder feeding rate: 20 g/min; spraying distance: 100 mm; spraying was performed 12 times.
Example 2:
step 1: and preparing a SiC inner coating. The specific process is as follows:
1) and sequentially polishing the C/C composite material by using No. 400 and No. 800 sandpaper, cleaning by using absolute ethyl alcohol, and drying for 24 hours in an oven at the temperature of 80 ℃ for later use.
2) 100g of Si powder, 18g of C powder and Al powder were weighed out separately2O3And 8g of powder, placing the powder in a rosin ball milling tank, adding different amounts of agate balls with different diameters, and carrying out ball milling and mixing treatment for 2 hours. The obtained mixed powder is used as an embedding material.
3) And putting half of the mixed powder into a graphite crucible, then putting the cleaned C/C composite material on the mixed powder, and then putting the other half of the embedded powder to completely cover the sample.
And (3) putting the graphite crucible filled with the embedded powder and the C/C composite material into a hot-pressing vacuum reaction furnace using graphite as a heating body. And vacuumizing the reaction furnace to ensure that the vacuum degree reaches-0.09 MPa, and then keeping the vacuum for 40 minutes. Then argon was introduced to normal pressure. This process was repeated twice for the scrubbing treatment. The furnace temperature was then raised to 2000 ℃ at a ramp rate of 10 ℃/min and held for 2.5 hours. And finally, powering off, naturally cooling to room temperature, and introducing argon for protection in the whole process. And after the heat treatment is finished, taking out the crucible, taking out the C/C composite material sample, and cleaning the embedded powder on the surface of the coated sample to obtain the SiC-coated C/C composite material.
Step 2: the powder for spraying is prepared by a spray drying method. The specific process is as follows:
1) adding 15% of La by volume2O3Uniformly stirring and mixing the powder and ZrC powder in a corundum mortar;
2) polyvinyl alcohol solution with the concentration of 3 wt.% is prepared as a binder, and the polyvinyl alcohol solution is mixed and stirred for 30min according to the proportion of 49 wt.% of distilled water, 2 wt.% of binder and 49 wt.% of ceramic mixed powder to form feed slurry. The inlet temperature of the dryer was raised to 310 c, the outlet temperature to 125 c, the nozzle speed was adjusted to 40rpm, and the prepared slurry was fed through the feed apparatus of the granulator at a feed rate of 65 ml/min. And after all slurry feeding is finished, collecting dry powder at a discharge port to be used as powder for spraying.
And step 3: preparation of ZrC-La2O3Complex phase ceramic coating
Fixing the C/C composite material with the SiC inner coating prepared in the step 1 by using a sample clamp, loading the spraying powder prepared in the step 2 into a powder feeder, opening SAPS equipment, and checking whether the equipment leaks water and gas. After the equipment is confirmed to be intact, spraying the spraying powder on the C/C composite material sample coated with the SiC coating according to the following spraying parameters to obtain ZrC-La2O3The C/C composite material is coated by the/SiC composite coating.
The specific SAPS process parameters are as follows:
spraying direct current: 400A; spraying direct-current voltage: 128V; main gas flow: 75L/min; auxiliary gas flow rate: 4.5L/min; powder feeding rate: 22 g/min; spraying distance: 100 mm; spraying was performed 12 times.
Example 3:
step 1: and preparing a SiC inner coating. The specific process is as follows:
1) and sequentially polishing the C/C composite material by using No. 400 and No. 800 sandpaper, cleaning by using absolute ethyl alcohol, and drying in an oven at 80 ℃ for later use.
2) 100g of Si powder, 18g of C powder and Al powder were weighed out separately2O38g of powder, placing the powder in a rosin ball milling tank, and adding different quantities of agate balls with different diametersBall milling and mixing for 2 hours. The obtained mixed powder is used as an embedding material.
3) And putting half of the mixed powder into a graphite crucible, then putting the cleaned C/C composite material on the mixed powder, and then putting the other half of the embedded powder to completely cover the sample.
And (3) putting the graphite crucible filled with the embedded powder and the C/C composite material into a hot-pressing vacuum reaction furnace using graphite as a heating body. And vacuumizing the reaction furnace to ensure that the vacuum degree reaches-0.09 MPa, and then keeping the vacuum for 40 minutes. Then argon was introduced to normal pressure. This process was repeated twice for the scrubbing treatment. The furnace temperature was then raised to 2050 ℃ at a ramp rate of 10 ℃/min and held for 2.5 hours. And finally, powering off, naturally cooling to room temperature, and introducing argon for protection in the whole process. And after the heat treatment is finished, taking out the crucible, taking out the C/C composite material sample, and cleaning the embedded powder on the surface of the coated sample to obtain the SiC-coated C/C composite material.
Step 2: the powder for spraying is prepared by a spray drying method. The specific process is as follows:
1) adding 15% of La by volume2O3Uniformly stirring and mixing the powder and ZrC powder in a corundum mortar;
2) polyvinyl alcohol solution with the concentration of 3 wt.% is prepared as a binder, and the polyvinyl alcohol solution is mixed and stirred for 30min according to the proportion of 48 wt.% of distilled water, 3 wt.% of binder and 49 wt.% of ceramic mixed powder to form feed slurry. The inlet temperature of the dryer was raised to 315 deg.C, the outlet temperature was raised to 115 deg.C, the rotational speed of the spray head was adjusted to 38rpm, and the prepared slurry was then fed through the feed apparatus of the granulator at a feed rate of 75 ml/min. And after all slurry feeding is finished, collecting dry powder at a discharge port to be used as powder for spraying.
And step 3: preparation of ZrC-La2O3Complex phase ceramic coating
Fixing the C/C composite material with the SiC inner coating prepared in the step 1 by using a sample clamp, loading the spraying powder prepared in the step 2 into a powder feeder, opening SAPS equipment, and checking whether the equipment leaks water and gas. After the equipment is confirmed to be intact, spraying the spraying powder according to the following spraying parametersObtaining ZrC-La on a C/C composite material sample coated with SiC2O3The C/C composite material is coated by the/SiC composite coating.
The specific SAPS process parameters are as follows:
spraying direct current: 400A; spraying direct-current voltage: 125V; main gas flow: 75L/min; auxiliary gas flow rate: 4.5L/min; powder feeding rate: 25 g/min; spraying distance: 100 mm; spraying was performed 12 times.
In all examples, the Si powder had a purity of 99.5% and a particle size of 300 mesh, the C powder had a purity of 99% and a particle size of 300 mesh, and Al was added2O3The powder is analytically pure (the mass percentage content is more than or equal to 99.8 percent), the granularity is 300 meshes, the purity of ZrC powder is 99 percent, the granularity is 400 meshes, and La powder2O3The purity of the powder was 99% and the particle size was 325 mesh.
FIG. 1 is ZrC-La prepared in example 32O3And (3) carrying out secondary electronic pictures on the cross section back scattering and the surface of the/SiC composite coating. As can be seen from the figure, the prepared coating has a double-layer structure, and ZrC-La is externally added2O3The coating and embedded SiC coating interfaces were jagged, indicating that the two bond well. The surface appearance shows that the prepared coating has compact structure and does not have large holes and defects.
FIG. 2 is ZrC-La prepared in example 32O3the/SiC composite coating is ablated at the heat flow of 2.4MW/m2Surface secondary electron pictures after ablation for 200s in oxyacetylene environment. As can be seen, the surface of the coating is dense after ablation, and the surface of the coating is composed of cells and flat areas.
Fig. 3 is a magnified photograph and spectral analysis of the different regions in fig. 2. As can be seen from the figure, the oxidized surface is denser regardless of the cellular and flat areas. The flat regions consist of a structure in which a melt phase and particles are mixed, and the energy spectrum shows that these regions all contain La. The cells are composed of a few large grains, and the spectrum shows that the La content at the grain boundaries is greater than the La content within the grains. The La-containing oxide can effectively fill the defects of cracks, pores and the like in the coating, thereby improving the thermal protection capability of the coating.
FIG. 4 ZrC-La prepared in example 32O3the/SiC composite coating is ablated at the heat flow of 2.4MW/m2A macroscopic photograph after 700s of ablation in an oxyacetylene environment. As can be seen, the coating can protect the C/C composite material for at least 700 seconds.

Claims (3)

1. A preparation method of a long-time ablation-resistant composite coating on the surface of a carbon/carbon composite material is characterized by comprising the following steps: the inner coating of the composite coating is a SiC coating, and the outer coating is ZrC-La2O3A complex phase ceramic coating;
the method comprises the following specific steps:
step 1: burying the pretreated C/C composite material in the mixed powder in a graphite crucible, putting the graphite crucible into a hot-pressing vacuum reaction furnace using graphite as a heating element, performing vacuum treatment on the vacuum furnace to ensure that the vacuum degree reaches-0.09 MPa, introducing Ar gas to the normal pressure, raising the furnace temperature from room temperature to 1800-2100 ℃ at the temperature rise speed of 5-10 ℃/min, and preserving the temperature for 1-3 hours; turning off a power supply, naturally cooling to room temperature, and introducing Ar gas for protection in the whole process to obtain the C/C composite material with the SiC inner coating on the surface;
the mixed powder comprises the following components: mixing Si powder, C powder and Al2O3Mixing 65-85 wt%, 10-25 wt% and 5-10 wt% of the powder in a resin ball milling tank, and mixing for 2-4 hr to obtain mixed powder;
step 2, preparing powder for spraying by adopting a spray drying method:
1) mixing 10 vol.% to 25 vol.% La2O3Uniformly stirring and mixing the powder and ZrC powder in a corundum mortar;
2) preparing a polyvinyl alcohol solution with the concentration of 3 wt.% as a binder, and mixing and stirring for 30min according to the proportion of 40-50 wt.% of distilled water, 2-5 wt.% of the binder and 40-50 wt.% of ceramic mixed powder to form feed slurry; then, granulating by adopting a spray drying method;
step 3, preparing ZrC-La2O3Complex phase ceramic coating:
placing the C/C composite material with the surface containing the SiC inner coating obtained in the step 1 into a clamp, and filling the spraying powder prepared in the step 2 into powder feedingSpraying powder on the C/C composite material embedded with the SiC coating according to the following process parameters to prepare ZrC-La2O3A complex phase ceramic coating;
plasma spraying process parameters: spraying direct current: 380-450A; spraying direct-current voltage: 115-140V; main gas flow: 75-85L/min; auxiliary gas flow rate: 4.5-5.5L/min; powder feeding rate: 20-40 g/min; spraying distance: 80-140 mm; the spraying process is 8-15 times of spraying.
2. The method for preparing the long-time ablation-resistant composite coating on the surface of the carbon/carbon composite material according to claim 1, wherein the method comprises the following steps: the pretreatment of the C/C composite material is as follows: and polishing the C/C composite material, ultrasonically cleaning, and drying in an oven.
3. The method for preparing the long-time ablation-resistant composite coating on the surface of the carbon/carbon composite material according to claim 1, wherein the method comprises the following steps: when the spray drying method is used for granulation: the inlet temperature of the dryer is 300-330 ℃, the outlet temperature is 110-150 ℃, the rotating speed of the spray head is 30-40 rpm, and the feeding speed is 65-85 ml/min.
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