CN114149270A - Ablation-resistant composite material and preparation method and application thereof - Google Patents
Ablation-resistant composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an ablation-resistant composite material and a preparation method and application thereof, wherein the method comprises the following steps: uniformly mixing zirconium acetate, yttrium nitrate hexahydrate, ethyl orthosilicate and deionized water, heating, raising the temperature, and concentrating the obtained solution to obtain zirconium sol; uniformly mixing magnesium oxide fibers, zirconium boride fibers and deionized water to obtain raw material slurry; carrying out vacuum filtration on the obtained raw material slurry to obtain a magnesium oxide fiber preform; soaking the obtained magnesium oxide fiber preform with the zirconium sol obtained in the step 1), and performing hot press molding to obtain a block body; carrying out heat treatment on the obtained block, and naturally cooling to room temperature to obtain a magnesium oxide composite plate body; and depositing a silicon carbide layer on the surface of the obtained magnesium oxide composite plate body to obtain the ablation-resistant composite material. The ablation-resistant composite material disclosed by the invention keeps the characteristics of low heat conduction and high temperature resistance and simultaneously improves the strength and ablation resistance.
Description
Technical Field
The invention belongs to the technical field of high-temperature-resistant heat insulation materials, and particularly relates to an ablation-resistant composite material and a preparation method and application thereof.
Background
The hypersonic flight vehicle is an important field for the exploration of aerospace science and technology, and is a popular field developed in advanced aerospace countries in recent years. The device is necessary for testing the thermal performance of the hypersonic aircraft, and in the conventional device for testing the thermal performance of the hypersonic aircraft, flame heats a sample to be tested, and strong air current scouring is accompanied in the heating process. Aiming at a sample to be detected with a large size, flame flow can be dispersed after the surface of the sample is washed, and the washing below the sample can not be caused. Aiming at a sample to be detected with a small size, the diameter of the flame flow is larger than the size of the sample, and the flame flow can scour the lower part of the sample. In the thermal test process, a high-temperature-resistant heat-insulating material is used below the sample to be separated from a metal table top of the test equipment, the sample is usually made of a ceramic matrix composite material, an aluminum oxide plate and a zirconium oxide plate are common, the temperature resistance can reach more than 2000 ℃, and after the ablation temperature is continuously increased, the plate can be melted and failed.
Disclosure of Invention
In view of the above, the present invention aims to provide an ablation-resistant composite material, and a preparation method and an application thereof, and aims to solve the technical problem of being capable of resisting temperature of more than 2300 ℃ and having high strength on the premise of maintaining heat insulation capability.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The preparation method of the ablation-resistant composite material provided by the invention comprises the following steps:
1) preparing zirconium sol: uniformly mixing zirconium acetate, yttrium nitrate hexahydrate, ethyl orthosilicate and deionized water, heating, raising the temperature, and concentrating the obtained solution to obtain zirconium sol;
2) mixing materials: uniformly mixing magnesium oxide fibers, zirconium boride fibers and deionized water to obtain raw material slurry;
3) preparing a prefabricated body: carrying out vacuum filtration on the raw material slurry obtained in the step 2) to obtain a magnesium oxide fiber preform;
4) hot-press molding: soaking the magnesium oxide fiber preform obtained in the step 3) with the zirconium sol obtained in the step 1), and performing hot press molding to obtain a block body;
5) and (3) heat treatment: carrying out heat treatment on the block obtained in the step 4), and naturally cooling to room temperature to obtain a magnesium oxide composite plate body;
6) forming a silicon carbide coating: depositing a silicon carbide layer on the surface of the magnesium oxide composite plate body obtained in the step 5) to obtain the ablation-resistant composite material.
Preferably, in the preparation method of the ablation-resistant composite material, in step 1), the amount of the zirconium acetate is 900-.
Preferably, in the preparation method of the ablation-resistant composite material, in the step 1), the reaction temperature is 40-100 ℃ and the reaction time is 0.5-3 h.
Preferably, in the preparation method of the ablation-resistant composite material, in the step 2), the magnesium oxide fiber is a chopped fiber, the diameter is 1-20 μm, and the length is 1-20 mm; the zirconium boride fiber is chopped fiber with the diameter of 1-20 μm and the length of 1-20 mm.
Preferably, in the preparation method of the ablation-resistant composite material, in the step 2), the amount of the magnesium oxide fiber is 90-110 parts by weight, the amount of the zirconium boride fiber is 180-220 parts by weight, and the amount of the deionized water is 600-2000 parts by weight.
Preferably, in the preparation method of the ablation-resistant composite material, in the step 3), the vacuum degree of the vacuum filtration is-0.05 to-0.95 MPa; the vacuum filtration time is 10s-3 min.
Preferably, in the preparation method of the ablation-resistant composite material, in the step 4), the pressure of the hot press molding is 0.1-100MPa, the pressure maintaining time is 0.1-2h, the heating temperature of the hot press molding is 100-300 ℃, and the heating time is 1-8 h.
Preferably, in the preparation method of the ablation-resistant composite material, in the step 5), the heat treatment temperature is 1200-1800 ℃, and the heat treatment time is 10-20 h.
Preferably, in the preparation method of the ablation-resistant composite material, in the step (6), the deposition mode is CVD vapor deposition; the CVD vapor deposition temperature is 900-1300 ℃, the time is 20-30h, the introduced gas is trichloromethylsilane, hydrogen and argon, and the volume ratio of the trichloromethylsilane to the hydrogen to the argon is 1: (5-20): (5-20).
The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. According to the ablation-resistant composite material provided by the invention, the 5% compressive strength of the ablation-resistant composite material is 20.9-23.1MPa, the 10% compressive strength is 35.1-45.2MPa, the heat conductivity coefficient is 3.7-5.7W/mK, the mass ablation rate is 0.02-0.03g/s, no melting occurs under ablation at 2300 ℃, and the weight loss is 0.83-1.03%.
Preferably, the ablation-resistant composite described above, wherein said ablation-resistant composite is made by the method described above.
The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. According to the sample pad plate provided by the invention, the sample pad plate is made of the ablation-resistant composite material.
The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme. According to the invention, the thermal performance testing device comprises the sample pad.
By the technical scheme, the invention at least has the following advantages:
the ablation-resistant composite material prepared by the invention keeps the characteristics of low heat conduction and high temperature resistance and improves the strength and ablation resistance.
The ablation-resistant composite material has the 5% compressive strength of 20.9-23.1MPa, the 10% compressive strength of 35.1-45.2MPa, the heat conductivity coefficient of 3.7-5.7W/mK and the mass ablation rate of 0.02-0.03 g/s.
The ablation-resistant composite material can be used in the thermal test of a hypersonic aircraft and used as a sample backing plate, and has no melting at 2300 ℃ and weight loss less than or equal to 2%.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to the specific embodiments, structures, characteristics and effects of the ablation-resistant composite material, the preparation method and the application thereof according to the present invention, in combination with the preferred embodiments.
Unless otherwise specified, the following materials, reagents and the like are commercially available products well known to those skilled in the art; unless otherwise specified, all methods are well known in the art. Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The following procedures or conditions, which are not specifically mentioned, may be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the art.
The magnesium oxide fiber has low thermal conductivity and poor strength; the zirconium boride fiber has high heat conductivity coefficient and high strength, and has the problem of oxidation. The applicant unexpectedly finds that the problem of the two fibers can be solved after mixing by blending the proportion of the two fibers, so that the strength is improved, the heat conductivity coefficient is reduced, and the oxidation of the zirconium boride fiber is reduced; in addition, after CVD vapor deposition of silicon carbide, the problem of zirconium boride fiber oxidation is further solved, and the thermal weight loss and the mass ablation rate are reduced.
According to an embodiment of the present invention, there is provided a method for preparing an ablation-resistant composite material, including the steps of:
1) preparing zirconium sol: uniformly mixing zirconium acetate, yttrium nitrate hexahydrate, ethyl orthosilicate and deionized water, heating, raising the temperature, and then carrying out reduced pressure concentration on the obtained solution to obtain zirconium sol;
2) mixing materials: uniformly mixing magnesium oxide fibers, zirconium boride fibers and deionized water to obtain raw material slurry;
3) preparing a prefabricated body: carrying out vacuum filtration on the raw material slurry obtained in the step 2) to obtain a magnesium oxide fiber preform;
4) hot-press molding: soaking the magnesium oxide fiber preform obtained in the step 3) with the zirconium sol obtained in the step 1), and performing hot press molding to obtain a block body;
5) and (3) heat treatment: carrying out heat treatment on the block obtained in the step 4), and naturally cooling to room temperature to obtain a magnesium oxide composite plate body;
6) forming a silicon carbide coating: depositing a silicon carbide layer on the surface of the magnesium oxide composite plate body obtained in the step 5) to obtain the ablation-resistant composite material.
According to some embodiments of the present invention, in step 1), the amount of zirconium acetate may be 900-. Zirconium acetate is used as a raw material, poly-zirconium acetate is formed through a polycondensation reaction, yttrium nitrate hexahydrate serves as a phase stabilizer, deionized water serves as a reaction solvent, and tetraethoxysilane serves as a fiber flexibility regulator. The key is the proportion of zirconium acetate and yttrium nitrate hexahydrate, if the weight proportion of zirconium acetate and yttrium nitrate hexahydrate is less than (900-: (90-110), the performance of the curing agent is influenced and the strength is reduced due to too low zirconium acetate; if the weight ratio of the zirconium acetate to the yttrium nitrate hexahydrate is greater than (900-: (90-110), when the yttrium nitrate hexahydrate is too low, phase transformation can occur after heat treatment, and the strength is also influenced. Deionized water is used as a reaction solvent, and both too low and too high can affect the performance of the curing agent. The same applies to tetraethoxysilane, which is too low or too high, resulting in a decrease in strength. For this reason, the amount of the zirconium acetate is preferably 950-; the using amount of the yttrium nitrate hexahydrate is preferably 95-105 parts by weight, the using amount of the deionized water is preferably 950-1050 parts by weight, and the using amount of the ethyl orthosilicate is preferably 45-55 parts by weight.
According to some embodiments of the present invention, wherein in step 1), the viscosity of the selected zirconium sol is 800-.
According to some embodiments of the present invention, in step 1), the yttrium nitrate hexahydrate may be analytically pure or guaranteed reagent, the zirconium acetate may be analytically pure or guaranteed reagent, and the ethyl orthosilicate may be analytically pure or guaranteed reagent. In consideration of cost, the above raw materials are generally selected only to be analytically pure.
According to some embodiments of the present invention, wherein in the step 1), the reaction temperature may be set to 40 to 100 ℃ and the reaction time may be set to 0.5 to 3 hours. If the reaction temperature is lower than 40 ℃, the raw materials do not react with each other; if the temperature is higher than 100 ℃, the viscosity of the produced zirconium sol is high, which affects impregnation. If the reaction time is less than 0.5h, the reaction is insufficient, and the curing effect is reduced; if the reaction time is longer than 3 hours, energy consumption is wasted. Therefore, the reaction temperature is preferably 50 to 80 ℃; the reaction time is preferably 0.5 to 1 hour.
According to some embodiments of the invention, wherein in step 2), the magnesium oxide fibers are selected to be chopped fibers with a diameter of 1-20 μm and a length of 1-20 mm; the zirconium boride fiber is selected to be chopped fiber, the diameter is 1-20 μm, and the length is 1-20 mm. The diameter and length of the fibers primarily affect the thermal insulation and dispersion properties. The above length and diameter of the magnesia fiber and zirconium boride fiber are selected taking into account existing fiber practices. If the lengths of the two fibers are longer than the above-mentioned 1-20mm, the materials in the step 2) may be mixed with difficulty. In view of the above, the diameter of the magnesium oxide fiber is preferably 1 to 10 μm, and the length is preferably 2 to 5 mm; the zirconium boride fiber preferably has a diameter of 1 to 10 μm and a length of 2 to 10 mm.
According to some embodiments of the present invention, in step 2), the amount of the magnesium oxide fiber may be 90-110 parts by weight, the amount of the zirconium boride fiber may be 180-220 parts by weight, and the amount of the deionized water may be 600-2000 parts by weight. The weight ratio of the magnesium oxide fiber and the zirconium boride fiber influences the compression strength, the heat conductivity coefficient, the thermal weight loss and the mass ablation rate of a final product, the higher the ratio of the magnesium oxide fiber and the zirconium boride fiber is, the poorer the strength is, the lower the ratio is, the higher the heat conductivity coefficient is, the higher the thermal weight loss is, the higher the mass ablation rate is, and further the thermal ablation performance is poorer. The increase of the magnesium oxide fiber can lead to the enhancement of ablation resistance, the reduction of strength and temperature resistance, and the reduction of the magnesium oxide fiber can lead to the reduction of oxidation resistance of a sample; the increase of the zirconium boride fiber can increase the heat conductivity coefficient, reduce the oxidation resistance and reduce the temperature resistance; deionized water is the space that the fibre dispersed mixes, and the reduction can lead to the material to mix inhomogeneous, and the increase can cause the waste. In consideration of the above factors, the amount of the magnesium oxide fiber is preferably 95 to 105 parts by weight; the amount of the zirconium boride fiber is preferably 190-210 parts by weight; the amount of deionized water is preferably 1000-1600 parts by weight.
According to some embodiments of the invention, in the step 3), the vacuum degree of the vacuum filtration is-0.05 to-0.95 MPa; the vacuum filtration time is 10s-3 min. The vacuum degree and time of suction filtration mainly affect the preparation of the preform. If the vacuum degree is lower than-0.95 MPa or the time is lower than 10s, the forming of the prefabricated body is influenced; if the vacuum degree is higher than-0.05 MPa and the time is higher than 3min, unnecessary energy consumption is increased.
According to some embodiments of the invention, wherein in step 4), the pressure, temperature and time are controlled to ensure the block is shaped. The pressure of the hot-press molding is 0.1-100MPa, the pressure maintaining time is 0.1-2h, the heating temperature of the hot-press molding is 100-300 ℃, and the heating time is 1-8 h. In order to better shape the block, the pressure of the hot press forming is preferably 10-50MPa, the dwell time is preferably 0.5-1h, the heating temperature of the hot press forming is preferably 150-250 ℃, and the heating time is preferably 3-6 h. The soaking time of the zirconium sol can be 5-20s, and the magnesium oxide fiber preform can be completely soaked after being placed.
According to some embodiments of the invention, wherein step 5), the heat treatment is to allow the zirconium sol to completely solidify. The heat treatment temperature can be set to 1200-1800 ℃, and the heat treatment time can be set to 10-20 h. If the temperature of the heat treatment is lower than 1200 ℃, the curing is not completely carried out, and the purpose of the heat treatment cannot be achieved; if the temperature of the heat treatment is higher than 1800 c, unnecessary energy consumption is increased. The heat treatment temperature is preferably 1400 ℃ to 1800 ℃ and the heat treatment time is preferably 12 to 18 hours, in view of the complete solidification of the zirconium sol. The above-mentioned solidification refers to a process of converting the zirconium sol into zirconium oxide. Whereas more than 1200 zirconia sols will be converted to zirconia.
According to some embodiments of the invention, wherein in step 6), the deposition is by CVD vapor deposition; the temperature of the CVD vapor deposition is 900-1300 ℃, preferably 1000-1200 ℃, and the time is 20-30h, preferably 20-25 h; the introduced gas can be trichloromethylsilane, hydrogen and argon, and the volume ratio of the trichloromethylsilane to the argon is 1: (5-20): (5-20). The thickness of the formed silicon carbide layer is 0.1-0.2 mm.
The embodiment of the invention also provides an ablation-resistant composite material, wherein the 5% compressive strength of the ablation-resistant composite material is 20.9-23.1MPa, the 10% compressive strength of the ablation-resistant composite material is 35.1-45.2MPa, the thermal conductivity of the ablation-resistant composite material is 3.7-5.7W/mK, the mass ablation rate of the ablation-resistant composite material is 0.02-0.03g/s, no melting occurs under ablation at 2300 ℃, and the weight loss of the ablation-resistant composite material is 0.83-1.03%.
There is also provided, in accordance with an embodiment of the present invention, a sample pad made of the ablation-resistant composite described above. Specifically, the sample backing plate is cut from the ablation-resistant composite material according to the required size.
According to an embodiment of the present invention, there is further provided a thermal performance testing apparatus, including the sample pad, a heating system and a temperature testing system, where the heating system and the temperature testing system are selected from the prior art, and the specific structure and connection relationship thereof are not described herein again.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with certain insubstantial modifications and adaptations of the invention based on the teachings of the invention set forth herein.
Example 1
Mixing 1000g of zirconium acetate, 100g of yttrium nitrate hexahydrate, 1000g of deionized water and 50g of tetraethoxysilane, placing the mixture in a glass reaction kettle, reacting for 0.5h at 60 ℃, and concentrating the obtained solution in a reduced pressure evaporation device for 30min to obtain zirconium sol with the viscosity of 1000 mPas; uniformly mixing 100g of magnesium oxide fiber (the diameter is 1-10 mu m, the length is 2-5mm), 200g of zirconium boride fiber (the diameter is 1-10 mu m, the length is 2-10mm) and 1300g of deionized water to obtain raw material slurry; carrying out suction filtration on the raw material slurry for 1min under the vacuum degree of-0.5 MPa to obtain a magnesium oxide fiber preform; soaking the magnesium oxide fiber preform with 1000g of zirconium sol for 10s, and putting the magnesium oxide fiber preform into a pressing mold of 100mm x 100mm for hot press molding, wherein the pressure is 10MPa, the pressure maintaining time is 1h, and the temperature is 150 ℃, so as to obtain a block body; and (3) carrying out heat treatment on the block body at 1600 ℃ for 12h, and naturally cooling to room temperature to obtain the magnesium oxide composite plate body. Depositing the surface of the magnesium oxide composite plate body for 25h at 1200 ℃ by using a CVD (chemical vapor deposition) method, introducing gases of trichloromethylsilane, hydrogen and argon, wherein the volume ratio of the trichloromethylsilane to the hydrogen to the argon is 1: 10: and 10, the introduction rate of trichloromethylsilane is 50ml/min, the introduction rates of hydrogen and argon are both 500ml/min, and a silicon carbide coating with the thickness of 0.2mm is formed on the surface of the magnesium oxide composite plate body to obtain the ablation-resistant composite material. The ablation-resistant composite material can be used for preparing a sample base plate in a thermal performance testing device.
Example 2
Mixing 1100g of zirconium acetate, 110g of yttrium nitrate hexahydrate, 1000g of deionized water and 50g of tetraethoxysilane, placing the mixture in a glass reaction kettle, reacting for 1 hour at 70 ℃, and concentrating the obtained solution in a reduced pressure evaporation device for 30 minutes to obtain zirconium sol with the viscosity of 1000 mPas; uniformly mixing 100g of magnesium oxide fiber (the diameter is 1-10 mu m, the length is 2-5mm), 180g of zirconium boride fiber (the diameter is 1-10 mu m, the length is 2-10mm) and 1000g of deionized water to obtain raw material slurry; carrying out suction filtration on the raw material slurry for 1min at a vacuum degree of-0.5 MPa to obtain a magnesium oxide fiber preform; soaking the magnesium oxide fiber preform with 1000g of zirconium sol for 10s, and putting the magnesium oxide fiber preform into a pressing mold of 100mm x 100mm for hot press molding, wherein the pressure is 8MPa, the pressure maintaining time is 1h, and the temperature is 160 ℃, so as to obtain a block body; and (3) carrying out heat treatment on the block body at 1600 ℃ for 10h, and naturally cooling to room temperature to obtain the magnesium oxide composite plate body. Depositing the surface of the magnesium oxide composite plate body for 20 hours at 1100 ℃ by using a CVD (chemical vapor deposition) method, introducing gases of trichloromethylsilane, hydrogen and argon, wherein the volume ratio of the trichloromethylsilane to the hydrogen to the argon is 1: 10: and 10, the introduction rate of trichloromethylsilane is 50ml/min, the introduction rate of hydrogen and argon is 500ml/min, a silicon carbide coating with the thickness of 0.2mm is formed, and a silicon carbide coating with the thickness of 0.1mm is formed on the surface of the magnesium oxide composite plate body, so that the ablation-resistant composite material is obtained. The ablation-resistant composite material can be used for preparing a sample base plate in a thermal performance testing device.
Example 3
Mixing 900g of zirconium acetate, 100g of yttrium nitrate hexahydrate, 1000g of deionized water and 40g of tetraethoxysilane, placing the mixture in a glass reaction kettle, reacting for 1 hour at 65 ℃, and concentrating the obtained solution in a reduced pressure evaporation device for 30 minutes to obtain zirconium sol with the viscosity of 1000 mPas; uniformly mixing 90g of magnesium oxide fiber (the diameter is 1-10 mu m, the length is 2-5mm), 200g of zirconium boride fiber (the diameter is 1-10 mu m, the length is 2-10mm) and 1000g of deionized water to obtain raw material slurry; carrying out suction filtration on the raw material slurry for 1min at a vacuum degree of-0.5 MPa to obtain a magnesium oxide fiber preform; soaking the magnesium oxide fiber preform with 1000g of zirconium sol for 10s, and putting the magnesium oxide fiber preform into a pressing mold of 100mm x 100mm for hot press molding, wherein the pressure is 8MPa, the pressure maintaining time is 0.5h, and the temperature is 140 ℃, so as to obtain a block body; and (3) carrying out heat treatment on the block body at 1600 ℃ for 12h, and naturally cooling to room temperature to obtain the magnesium oxide composite plate body. Depositing the surface of the magnesium oxide composite plate body for 20 hours at 1200 ℃ by using a CVD (chemical vapor deposition) method, introducing gases of trichloromethylsilane, hydrogen and argon, wherein the volume ratio of the trichloromethylsilane to the hydrogen to the argon is 1: 10: and 10, introducing trichloromethylsilane at a rate of 50ml/min and introducing hydrogen and argon at a rate of 500ml/min to form a silicon carbide coating with the thickness of 0.2mm, and forming a silicon carbide coating with the thickness of 0.1mm on the surface of the magnesium oxide composite plate body to obtain the ablation-resistant composite material. The ablation-resistant composite material can be used for preparing a sample base plate in a thermal performance testing device.
Example 4
This example differs from example 1 in that the amount of the magnesium oxide fiber used was 90 g. The ablation-resistant composite material can be used for preparing a sample base plate in a thermal performance testing device.
Example 5
This example differs from example 1 in that the amount of the magnesium oxide fiber used was 95 g. The ablation-resistant composite material can be used for preparing a sample base plate in a thermal performance testing device.
Example 6
This example differs from example 1 in that the amount of magnesium oxide fibers used was 105 g. The ablation-resistant composite material can be used for preparing a sample base plate in a thermal performance testing device.
Example 7
This example differs from example 1 in that the amount of the magnesium oxide fiber used was 110 g. The ablation-resistant composite material can be used for preparing a sample base plate in a thermal performance testing device.
Example 8
This example differs from example 1 in that the amount of the zirconium boride fiber used was 180 g. The ablation-resistant composite material can be used for preparing a sample base plate in a thermal performance testing device.
Example 9
This example differs from example 1 in that the amount of zirconium boride fibres used was 190 g. The ablation-resistant composite material can be used for preparing a sample base plate in a thermal performance testing device.
Example 10
This example differs from example 1 in that the amount of the zirconium boride fiber used was 210 g. The ablation-resistant composite material can be used for preparing a sample base plate in a thermal performance testing device.
Example 11
This example differs from example 1 in that the amount of the zirconium boride fiber used was 220 g. The ablation-resistant composite material can be used for preparing a sample base plate in a thermal performance testing device.
Comparative example 1
This comparative example differs from example 1 in that the comparative example was not subjected to a CVD vapor deposition treatment.
Comparative example 2
This comparative example differs from example 1 in that no magnesium oxide fiber is included.
Comparative example 3
This comparative example differs from example 1 in that no zirconium boride fibers are included.
Comparative example 4
This comparative example is different from example 1 in that the magnesium oxide fiber was used in an amount of 70 g.
Comparative example 5
This comparative example differs from example 1 in that the amount of the magnesium oxide fiber used was 130 g.
Comparative example 6
This comparative example differs from example 1 in that the amount of the zirconium boride fiber used was 160 g.
Comparative example 7
This comparative example differs from example 1 in that the amount of the zirconium boride fiber used was 240 g.
Test example
The weight loss on heating of the ablation-resistant composite materials prepared in examples 1-11 of the invention and the composite materials of comparative examples 1-7 was tested according to the standard GBT27761-2011, the mass ablation rate was tested according to the standard GJB323a-96, the thermal conductivity was tested according to the standard GBT5990-1986, the compressive strength was tested according to the standard GBT8489-1987, and the state of ablation at 2300 ℃ without melting was directly observed according to the conventional naked eye in the art.
The performance of the ablation-resistant composites prepared in examples 1-11 above and the composites of comparative examples 1-7 were tested as follows, and the results are shown in Table 1.
TABLE 1
As can be seen from the test data in Table 1, the ablation-resistant composite materials of examples 1-11 of the present invention have a 5% compressive strength of 20.9MPa-23.1MPa, a 10% compressive strength of 35.1MPa-45.2MPa, a thermal conductivity of 3.7-5.7W/mK, a mass ablation rate of 0.02-0.03g/s, no melting under ablation at 2300 ℃, and a weight loss of 0.83-1.03%.
The test data of comparative examples 1-3 show that the reasonable proportions of the components can enable the final ablation-resistant composite material to meet the requirements, wherein the properties of example 1 are optimal.
Comparing the test data of examples 4-7 with example 1, it can be seen that the magnesium oxide fiber component primarily affects the strength, thermal conductivity of the final ablation resistant composite. The thermal conductivity coefficient is continuously increased along with the reduction of the proportion of the magnesium oxide fibers; the strength is continuously reduced with the increase of the proportion of the magnesium oxide fiber.
Comparing the test data of examples 8-11 with example 1, it can be seen that the zirconium boride fiber component primarily affects the strength, thermal conductivity of the final ablation resistant composite. The strength is continuously reduced along with the reduction of the proportion of the zirconium boride fibers; with the increase of the proportion of the zirconium boride fiber, the heat conductivity coefficient is continuously increased.
Comparing the test data of example 1 with that of comparative example 1, it can be seen that the absence of the silicon carbide coating of comparative example 1 can cause the zirconium boride fiber to be oxidized, and the melting occurs at 2300 ℃, so that the use requirement of the thermal performance test cannot be met.
Comparing the test data of example 1 with comparative examples 2 and 4-5, it can be seen that comparative example 2 contains no magnesia fiber, and the proportion of the magnesia fiber of comparative example 4 is too low, resulting in too high thermal conductivity, too high thermal weight loss, and too high mass ablation rate of the final material, i.e. poor ablation resistance; whereas the magnesium oxide fiber ratio of comparative example 5 is too high, resulting in insufficient strength of the final material.
Comparing the test data of example 1 with comparative examples 3, 6-7, it can be seen that comparative example 3 contains no zirconium boride fibers and comparative example 6 has too low a proportion of zirconium boride fibers, resulting in a low strength of the final material; whereas too high a proportion of the zirconium boride fiber of comparative example 7 results in too high a thermal conductivity of the final material and poor ablation resistance.
The sample backing plate prepared from the ablation-resistant composite material of the embodiment 1-11 is used for a thermal performance testing device of a hypersonic aircraft, can meet the requirement of performing a thermal ablation experiment at 2300 ℃ in the thermal ablation experiment, is used as the sample backing plate, and is not melted at 2300 ℃, so that the related experiment can be normally performed.
In the description of the present invention, numerous specific details are set forth. It is understood, however, that embodiments of the invention may be practiced without these specific details. In some embodiments, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the ablation-resistant composite material is characterized by comprising the following steps of:
1) preparing zirconium sol: uniformly mixing zirconium acetate, yttrium nitrate hexahydrate, ethyl orthosilicate and deionized water, heating, raising the temperature, and concentrating the obtained solution to obtain zirconium sol;
2) mixing materials: uniformly mixing magnesium oxide fibers, zirconium boride fibers and deionized water to obtain raw material slurry;
3) preparing a prefabricated body: carrying out vacuum filtration on the raw material slurry obtained in the step 2) to obtain a magnesium oxide fiber preform;
4) hot-press molding: soaking the magnesium oxide fiber preform obtained in the step 3) with the zirconium sol obtained in the step 1), and performing hot press molding to obtain a block body;
5) and (3) heat treatment: carrying out heat treatment on the block obtained in the step 4), and naturally cooling to room temperature to obtain a magnesium oxide composite plate body;
6) forming a silicon carbide coating: depositing a silicon carbide layer on the surface of the magnesium oxide composite plate body obtained in the step 5) to obtain the ablation-resistant composite material.
2. The method for preparing the ablation-resistant composite material as recited in claim 1, wherein in the step 1), the amount of the zirconium acetate is 900-1100 parts by weight, the amount of the yttrium nitrate hexahydrate is 90-110 parts by weight, the amount of the ethyl orthosilicate is 40-60 parts by weight, and the amount of the deionized water is 900-1100 parts by weight; the reaction temperature is 40-100 ℃, and the reaction time is 0.5-3 h.
3. The method of preparing an ablation-resistant composite material according to claim 1, wherein in step 2), the magnesium oxide fiber is a chopped fiber having a diameter of 1 to 20 μm and a length of 1 to 20 mm; the zirconium boride fiber is chopped fiber, the diameter is 1-20 mu m, and the length is 1-20 mm; the dosage of the magnesium oxide fiber is 90-110 parts by weight, the dosage of the zirconium boride fiber is 180-220 parts by weight, and the dosage of the deionized water is 600-2000 parts by weight.
4. The method for preparing the ablation-resistant composite material according to the claim 1, wherein in the step 3), the vacuum degree of the vacuum filtration is-0.05 to-0.95 MPa; the vacuum filtration time is 10s-3 min.
5. The method for preparing the ablation-resistant composite material as claimed in claim 1, wherein in the step 4), the pressure of the hot press forming is 0.1-100MPa, the pressure maintaining time is 0.1-2h, the heating temperature of the hot press forming is 100-300 ℃, and the heating time is 1-8 h; in the step 5), the heat treatment temperature is 1200-1800 ℃, and the heat treatment time is 10-20 h.
6. The method for preparing an ablation-resistant composite material according to claim 1, wherein in step 6), the deposition is performed by CVD vapor deposition; the CVD vapor deposition temperature is 900-1300 ℃, the time is 20-30h, the introduced gas is trichloromethylsilane, hydrogen and argon, and the volume ratio of the trichloromethylsilane to the hydrogen to the argon is 1: (5-20): (5-20).
7. The ablation-resistant composite material is characterized in that the 5% compressive strength of the ablation-resistant composite material is 20.9-23.1MPa, the 10% compressive strength of the ablation-resistant composite material is 35.1-45.2MPa, the heat conductivity coefficient of the ablation-resistant composite material is 3.7-5.7W/mK, the mass ablation rate is 0.02-0.03g/s, no melting occurs under ablation at 2300 ℃, and the weight loss is 0.83-1.03%.
8. The ablation-resistant composite of claim 7, wherein the ablation-resistant composite is made by the method of any of claims 1-6.
9. A sample pad, characterized in that it is made of the ablation-resistant composite material according to claim 7 or 8.
10. A thermal performance testing apparatus comprising the sample pad of claim 9.
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