CN116715526A - C/C- (Ti, zr, hf, nb, ta) C-SiC composite material and preparation method thereof - Google Patents
C/C- (Ti, zr, hf, nb, ta) C-SiC composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a C/C- (Ti, zr, hf, nb, ta) C-SiC composite material and a preparation method thereof, wherein slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder is immersed into a C/C composite porous blank to obtain a C/C- (Ti, zr, hf, nb, ta) C intermediate, and the C/C- (Ti, zr, hf, nb, ta) C intermediate is subjected to SiC matrix densification through a precursor impregnation cracking process to obtain the C/C- (Ti, zr, hf, nb, ta) C-SiC composite material.
Description
Technical Field
The invention belongs to the technical field of preparation of ultrahigh-temperature ceramic matrix composite materials, and particularly relates to a C/C- (Ti, zr, hf, nb, ta) C-SiC composite material and a preparation method thereof.
Background
The hypersonic aircraft is the leading field of the current aerospace research, the temperature required to be born by the application to aerospace thermal structural components is higher and higher, key thermal components such as rocket nose cones, missile throat liners and the like bear ultrahigh temperature of more than 2000 ℃ and hot airflow scouring, and strict requirements are put on the ablation resistance of the materials.
The C/C composite material is prepared by taking carbon as a matrix, taking carbon fibers as a reinforced framework and adopting a gas phase method or a liquid phase method. The C/C composite material has no melting point, sublimates at 3500 ℃ and has excellent structural stability at high temperature. In addition, the C/C composite material also has excellent ablation resistance, wear resistance and lower density, so that the C/C composite material has good application prospect in the aerospace field. However, the C/C composite material is easy to oxidize at 400 ℃, so that the application of the C/C composite material is severely restricted, and in order to meet the development of the aerospace field, a method for improving the ablation resistance and oxidation resistance of the C/C composite material is required.
The ultra-high temperature ceramic matrix modified C/C composite porous green body can effectively improve the ablation resistance of the C/C composite material, and a reaction infiltration method and a precursor impregnation cracking method are more applied at present. The reaction infiltration method is to infiltrate the metal melt into the C/C blank body under the action of capillary force, so that the molten metal reacts with pyrolytic carbon in the blank body to generate a high-temperature resistant ceramic phase, but the high-temperature resistant ceramic phase damages carbon fibers in the C/C blank body, and the mechanical property is adversely affected. The raw material cost of the precursor dipping cracking method is high, and the porosity of the obtained final material is high, so that the ablation resistance of the material is affected to a certain extent. It can be seen that a single preparation method is difficult to prepare a material with low porosity in a shorter process cycle, and multiple methods should be combined to modify the C/C composite matrix.
The ultrahigh-temperature ceramic matrix modified C/C composite material has better anti-ablation performance, and the anti-ablation performance mainly comes from the self-healing property of a ceramic phase, namely the characteristic of being capable of spontaneously filling cracks in a molten state. At present, siC is a ceramic which is commonly used for modifying a C/C composite porous blank body, because SiC can be oxidized at high temperature to generate SiO with certain fluidity 2 Thereby filling cracks and holes in the composite material and preventing oxygen from penetrating into the matrix to damage the material structure in the ablation process. But by SiO alone 2 The protection of the C/C composite porous green body cannot be well realized because of SiO 2 The fluidity of the material rises with the rise of temperature, and under the continuous flushing of high-temperature hot air flow, siO 2 Will be flushed to the edge by the air flow, resulting in a flushed area of SiO 2 The loss is serious, and part of the C/C blank body can be directly exposed outside, so that the structure is damaged. It is therefore necessary to add some extra-high temperature ceramics to act as a catalyst for SiO 2 By "pinning", i.e. by particle strengthening, of SiO 2 Is flushed by hot gas flow, and in addition, the ultra-high temperature ceramics are oxidized during the ablation process to form other molten oxides, such oxides and SiO 2 Mixing also reduces SiO 2 Is free from SiO 2 Is washed out, and has good oxygen blocking effect.
Most of the students research the low-entropy ceramic modified C/C composite material at present, and the prepared composite material has lower mass ablation rate and well shows the advantage of the ultra-high temperature ceramic matrix modified C/C composite material in the ablation resistance. The high-entropy ceramic not only can inherit the advantages of single-phase ceramic, such as high melting point, high hardness and thermal stability, but also can generate a synergistic effect due to the mutual solid solution of ceramic phases, comprehensively exert the performance advantages of the ceramic phases, and make up for the defects of the single-phase ultrahigh-temperature ceramic. Therefore, the use of high-entropy ceramic matrix to modify C/C composite materials is a trend of future development.
Currently, regarding heightThe entropy ceramic matrix modified C/C composite material and the preparation method thereof have few reports, and the literature is Feiyan Cai, deWeiNi, boWenChen, et al f (Ti, zr, hf, nb, ta) C-SiC high-entropy ceramic matrix composites via precursor infiltration and pyrolysis, journal of the European Ceramic Society,2021, 41:5863-5871.) describes a process for preparing a high entropy ceramic matrix composite. The document utilizes precursor impregnation cracking to respectively introduce a precursor of high-entropy ceramic (Ti, zr, hf, nb, ta) C and a precursor of SiC into a carbon fiber preform, thereby obtaining C f The composite material of the (Ti, zr, hf, nb, ta) C-SiC has better ablation resistance. However, the method has high raw material cost, and the density of the finally obtained material is low, which is 2.40g/cm 3 The porosity is higher, oxygen can easily reach the deep part of the blank through the pores, a certain influence is generated on the ablation resistance of the material, the used raw materials are difficult to prepare, the cost is high, and the defects severely limit the application and popularization of the method.
Disclosure of Invention
Aiming at the problems of overhigh temperature, lower solid solution degree and the like required by the physical preparation of high-entropy ceramic powder in the prior art and the defects of the traditional matrix modification technology that the structural integrity of the C/C composite porous green body is damaged and the porosity of the material is easy to cause by a single preparation method, the first aim of the invention is to provide a preparation method of a C/C- (Ti, zr, hf, nb, ta) C-SiC composite material.
A second object of the present invention is to provide a C/C- (Ti, zr, hf, nb, ta) C-SiC composite material prepared by the above preparation method.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a C/C- (Ti, zr, hf, nb, ta) C-SiC composite material, which is characterized in that slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder is immersed into a C/C composite porous blank to obtain a C/C- (Ti, zr, hf, nb, ta) C intermediate, and the C/C- (Ti, zr, hf, nb, ta) C intermediate is subjected to SiC matrix densification through a precursor dipping cracking process, so that the C/C- (Ti, zr, hf, nb, ta) C-SiC composite material is obtained.
The preparation method of the invention firstly directly adopts the slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder to immerse into the C/C composite porous blank, fills most of pores in the C/C composite porous blank with (Ti, zr, hf, nb, ta) C, then introduces SiC into the intermediate by a precursor dipping cracking method, fills other smaller pores of the intermediate to further densify, and not only shortens the preparation period of preparing the C/C- (Ti, zr, hf, nb, ta) C-SiC composite material by the precursor dipping cracking method alone, but also improves the preparation efficiency, and compared with the preparation of the C/C- (Ti, zr, hf, nb, ta) C-SiC composite material by the precursor dipping cracking method alone, greatly improves the final density, reduces the porosity, obtains a denser ceramic matrix, improves the performance of the composite material and reduces the process cost.
In a preferred scheme, the preparation method of the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder comprises the following steps: tiO is mixed with 2 Powder, zrO 2 Powder, hfO 2 Powder, nb 2 O 5 Powder, ta 2 O 5 Mixing the powder and carbon black powder to obtain mixed powder, adding ethanol, deionized water and polyethylene glycol into the mixed powder, performing first wet ball milling and first drying to obtain powder, pressing the powder to form a blank, performing carbothermic reduction-diffusion reaction on the blank to obtain a high-entropy ceramic block, performing second wet ball milling on the high-entropy ceramic block, and performing second drying to obtain the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder.
In the preparation method of the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder, polyethylene glycol is added as a raw material powder binder, so that on one hand, the forming and densification of oxide raw material powder are facilitated, on the other hand, the increase of the atomic diffusion direction in carbothermic reduction-diffusion reaction is facilitated, the diffusion path is shortened, the uniform distribution among elements is promoted, the guarantee is provided for complete solid solution, the reaction temperature and the requirement on equipment are effectively reduced, and any impurity is not introduced.
Further preferably, the TiO 2 Powder, zrO 2 Powder, hfO 2 Powder, nb 2 O 5 Powder, ta 2 O 5 The particle size of the powder is 0.5-1.5 mu m, the purity is more than or equal to 99.9%, and the particle size of the carbon black powder is 0.04-0.1 mu m.
Further preferably, in the mixed powder, tiO is added in a molar ratio of 2 Powder of ZrO 2 Powder of HfO 2 Powder of Nb 2 O 5 Powder Ta 2 O 5 Powder=17 to 23:17 to 23:8.5 to 11.5:8.5 to 11.5.
Further preferably, the TiO 2 The molar ratio of the powder to the carbon black powder is 1:8-9.
Through the proportion, the atomic number ratio of each of five metal elements in the prepared (Ti, zr, hf, nb, ta) C high-entropy ceramic powder is 17-23%, and the atomic ratio of the metal elements to the carbon elements is 1:1.
Still further preferably, in the mixed powder, tiO is as follows in terms of molar ratio 2 Powder of ZrO 2 Powder of HfO 2 Powder of Nb 2 O 5 Powder Ta 2 O 5 Powder carbon black powder = 2:2:2:1:1:16-17.
Further preferably, the average molecular weight of the polyethylene glycol is 10000 to 20000.
Further preferably, the mass ratio of the polyethylene glycol to the mixed powder is 1:18-22.
Further preferably, the mass ratio of the ethanol to the polyethylene glycol is 9-11:1.
Further preferably, the mass ratio of the ethanol to the deionized water is 9-11:1.
Further preferably, the rotating speed of the first wet ball milling is 160-180 r/min, and the time of the first wet ball milling is 4-9 h.
Further preferably, the temperature of the first drying is 80-110 ℃, and the time of the first drying is 24-36 h.
Further preferably, the pressure of the press molding is 0.5 to 1MPa.
Further preferably, the carbothermic reduction-diffusion reaction is carried out in a vacuum environment, the temperature of the carbothermic reduction-diffusion reaction is 1700-1900 ℃, the carbothermic reduction-diffusion reaction time is 1-2 h, and the heating rate is 10-15 ℃/min.
Polyethylene glycol is added in the invention, and the (Ti, zr, hf, nb, ta) C high-entropy ceramic with complete solid solution and single phase can be obtained at a lower reaction temperature.
Further preferably, absolute ethyl alcohol is used as a ball milling medium for the second wet ball milling, and the mass ratio of the (Ti, zr, hf, nb, ta) C high-entropy ceramic blocks to the absolute ethyl alcohol is 3-6:1.
Further preferably, the ball milling tank is made of hard alloy during the second wet ball milling, the grinding balls are made of hard alloy, the diameter is 1-4 mm, and the mass ratio of the grinding balls to the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder is 2-4:1.
Further preferably, the rotating speed of the second wet ball milling is 220-280 r/min, and the time of the second wet ball milling is 6-12 h.
Still more preferably, the forward and reverse rotation is alternately performed in the second wet ball milling process, the time of any forward rotation is 10-20 min, the time of any reverse rotation is 10-20 min, and the time of interval is 10-20 min.
Further preferably, the temperature of the second drying is 60 to 120 ℃, and the time of the second drying is 16 to 32 hours.
In a preferred embodiment, the particle size of the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder is 600-1500 nm.
The inventors found that the particle size of the (Ti, zr, hf, nb, ta) C high-entropy ceramic powders needs to be controlled within the above range, and if the particle size is smaller than 600nm, the fluidity of the slurry is drastically reduced due to the increase of the surface energy of the powder, which is unfavorable for the introduction of the (Ti, zr, hf, nb, ta) C high-entropy ceramic powders; when the particle size is larger than 1500nm, the bridging effect among the powders is obvious, a large number of holes are formed in the C/C composite porous green body, follow-up introduction of subsequent (Ti, zr, hf, nb, ta) C high-entropy ceramic powders is prevented, and the slurry dipping work is not easy to develop.
Preferably, the slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder is prepared by ball milling (Ti, zr, hf, nb, ta) C high-entropy ceramic powder, deionized water and polyethyleneimine water solution; wherein the volume ratio of the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder to the deionized water is 30-35:65-70, the mass ratio of the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder to the polyethyleneimine aqueous solution is 1:0.035-0.045, and the mass fraction of the polyethyleneimine in the polyethyleneimine aqueous solution is 8-12%.
The (Ti, zr, hf, nb, ta) C high-entropy ceramic powder prepared by the invention can be added with proper deionized water as a solvent and polyethyleneimine as a dispersing agent to obtain slurry with high dispersion and high solid content, and the average molecular weight of the polyethyleneimine used in the invention is 10000-20000.
Further preferably, during ball milling, the ball-material ratio is 1:2-5, the ball milling rotating speed is 100-180 r/min, and the ball milling time is 0.5-1 h.
Further preferably, in the ball milling, the ball milling tank is made of nylon, and the grinding balls are made of ZrO 2 。
Preferably, the density of the C/C composite porous green body is 0.6-1 g/cm 3 。
Further preferably, the C/C composite porous green body is obtained by densifying a carbon fiber preform through chemical vapor deposition, the carbon fiber preform is of a 2.5D needling structure, and the density of the carbon fiber preform is 0.4-0.5 g/cm 3 The carbon fibers in the carbon fiber preform are polyacrylonitrile carbon fibers.
In the preferred scheme, firstly, a dropper is used for dripping slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder on the surface of a C/C composite porous green body, so that the slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder is used for soaking the C/C composite porous green body, then the soaked C/C composite porous green body is soaked in the slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder, and the C/C- (Ti, zr, hf, nb, ta) C intermediate is obtained after drying.
The invention firstly drops the slurry on the upper surface of the C/C composite porous green body by using a rubber head dropper, evenly soaks the slurry into the C/C composite porous green body from top to bottom by the self gravity and capillary force of the slurry, then continuously soaks the soaked material with the slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder until no bubbles appear on the surface of the soaking liquid, and the inventor finds that the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder can enter the C/C composite porous green body in a large amount at one time by the way, and fills most of pores in the C/C composite porous green body and intermediatesDensity of 2.61g/cm 3 And the technical process is greatly shortened.
Further preferably, the drying temperature is 60-120 ℃ and the drying time is 16-24 h.
The precursor dipping and cracking process comprises the steps of dipping a C/C- (Ti, zr, hf, nb, ta) C intermediate in a dipping agent, then solidifying and cracking, and repeating dipping-solidifying-cracking until the precursor is compact;
the impregnant consists of polycarbosilane and n-hexane, and the mass ratio of the polycarbosilane to the n-hexane is 1:1-4.
Further preferably, the dipping is performed by performing the reduced pressure dipping for 5 to 60 seconds at a pressure of 0.3 to 0.7atm, and then performing the pressurized dipping for 3 to 10 minutes at a pressure of 4 to 7 MPa.
Further preferably, the curing temperature is 40-80 ℃, and the curing time is 5-20 h.
Further preferably, the cracking temperature is 1000-1600 ℃, preferably 1200-1400 ℃, the cracking time is 0.5-1.5 h, and the heating rate is 10-15 ℃/min.
In the present invention, repeating the impregnation-curing-pyrolysis until densification in densification means that the mass increase of the prepared composite material is less than 1% of the total mass.
The invention also provides the C/C- (Ti, zr, hf, nb, ta) C-SiC composite material prepared by the preparation method.
The final density of the C/C- (Ti, zr, hf, nb, ta) C-SiC composite material provided by the invention is up to 3.1g/cm 3 。
Principle and advantages
According to the preparation method, slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder is directly immersed into a porous C/C composite blank, the (Ti, zr, hf, nb, ta) C is filled into most of pores in the C/C composite porous blank, siC is introduced into an intermediate through a precursor immersion cracking method, other smaller pores of the intermediate are filled, so that densification is further achieved.
In the preparation method of the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder, polyethylene glycol is added as a raw material powder binder, so that on one hand, the forming and densification of oxide raw material powder are facilitated, on the other hand, the increase of the atomic diffusion direction in carbothermic reduction-diffusion reaction is facilitated, the diffusion path is shortened, the uniform distribution among elements is promoted, the guarantee is provided for complete solid solution, the reaction temperature and the requirement on equipment are effectively reduced, and any impurity is not introduced.
The invention firstly directly introduces self-made (Ti, zr, hf, nb, ta) C high-entropy ceramic powder into a porous C/C composite blank to prepare an intermediate by a slurry impregnation method, reduces raw material and process cost, then introduces SiC into the intermediate by a precursor impregnation cracking method to realize densification, prepares an ablation-resistant C/C- (Ti, zr, hf, nb, ta) C-SiC composite material with higher density, and measures that the density of the intermediate after slurry impregnation is 2.61g/cm 3 The final material density after densification was 3.1g/cm 3 。
Compared with the prior art, the invention has at least the following advantages:
(1) The invention introduces (Ti, zr, hf, nb, ta) C high-entropy ceramic into the porous C/C composite blank to carry out matrix modification through a high solid-phase content slurry dipping process. Compared with the traditional process, the solid phase content of the ceramic in the matrix material is greatly improved, the performance advantage of the ceramic component is better exerted, and the matrix material and the structure are protected from being damaged to the greatest extent because high-temperature reaction is not involved in the slurry dipping process, so that the overall performance of the material is improved. Compared with a brushing method, the slurry dipping can finish the ceramic introduction only by one step.
(2) The invention combines the precursor dipping process, fills the possible pore problem in the slurry dipping process, densifies the matrix material and further improves the overall performance of the material.
(3) The invention adopts ball milling and carbothermal reduction-diffusion reaction to prepare the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder. Compared with the traditional process, the method has the advantages that the crystallinity is improved, the reaction temperature is greatly reduced, and the sintering condition is pressureless sintering, so that the manufacturing cost and the equipment requirement are greatly reduced.
Drawings
FIG. 1 is a flow chart of a method for preparing a C/C- (Ti, zr, hf, nb, ta) -SiC composite material by a high solid phase content slurry impregnation method in combination with a precursor impregnation cracking method.
FIG. 2 is a scanning electron micrograph of a cross-sectional scanning electron microscope of a C/C- (Ti, zr, hf, nb, ta) C-SiC composite material prepared in example 1. The black part in the figure is carbon fiber in the composite material, the gray part is SiC introduced by precursor dipping and cracking, the white part is (Ti, zr, hf, nb, ta) C high-entropy ceramic, the cross section of the material has no obvious holes, the material has higher density, which is beneficial to SiO in the ablation process 2 The rapid filling of the glass tube can realize better oxygen blocking effect.
FIG. 3 shows the composition of example 1 (Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) XRD pattern of high entropy carbide powder. XRD diffraction peaks can be seen to be narrow and strong, indicating that the (Ti, zr, hf, nb, ta) C high-entropy carbide powder prepared according to the method described in the patent has better crystallinity.
FIG. 4 is a phase analysis XRD spectrum of the C/C- (Ti, zr, hf, nb, ta) -SiC composite material provided in example 1. The phases contained in the composite are mainly (Ti, zr, hf, nb, ta) C and SiC.
Detailed Description
The following describes the technical scheme of the present invention in further detail with reference to specific examples and drawings, but the scope and embodiments of the present invention are not limited thereto.
Example 1
The preparation of the C/C- (Ti, zr, hf, nb, ta) -SiC composite material comprises the following steps:
(1) Powder mixing: 6.789g TiO is weighed respectively 2 、10.474gZrO 2 、17.892gHfO 2 、11.297gNb 2 O 5 、18.781gTa 2 O 5 17.136g of carbon black powder was mixed and stirred until uniform. According to the mass of polyethylene glycol, the mass of powder material and the mass of ethanol are respectively equal to 1:21.2, 10:1 and 9:1, 4.318g of deionized water and 38.86g of ethanol are respectively weighed, 3.886g of polyethylene glycol is added after mixing, and after the polyethylene glycol is completely dissolved, the mixed solution is poured into the mixed powder. Ball milling and mixing the obtained mixture for 6 hours at the rotating speed of 180r/min, and putting the mixture into an oven to dry for 36 hours at 80 ℃ to obtain mixed powder.
(2) Compacting and sintering: pressing the powder obtained in the step (1) under 0.5MPa to obtain a blank to be sintered, then placing the blank in a high-temperature sintering furnace to perform carbothermic reduction-diffusion reaction, setting the heat preservation temperature to 1800 ℃, keeping the heat preservation time for 1h, and obtaining the bulk (Ti) with the heating rate of 10 ℃/min 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C high entropy carbide powder.
(3) Ball milling and refining: separately weigh (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) 90g of high-entropy carbide powder, 30g of absolute ethyl alcohol and 360g of tungsten carbide ball mill are placed in a hard alloy ball milling tank. The ball mill pot is put into a planetary ball mill and operated for 12 hours at a rotating speed of 260r/min, and is suspended for 10 minutes every time of 10 minutes, and is reversely rotated for 10 minutes and suspended for 10 minutes. After ball milling is finished, the ball mill is loaded with (Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C, putting the ball milling pot of the high-entropy carbide powder into an oven, setting the temperature to 120 ℃, and drying for 24 hours.
(4) And (3) preparing slurry: respectively weighing 65.1g of high-entropy carbide powder, 11.242g of deionized water, 1.953g of aqueous solution of 10% polyethylenimine by mass fraction and 35g of zirconia ball mill, adding into a nylon ball mill tank, placing into a planetary ball mill for mixing, and continuously rotating at a rotating speed of 160r/min for 1h to obtain (Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C, high-entropy carbide impregnating slurry.
(5) Slurry impregnation: the sizing agent is dripped on the upper surface of the C/C composite porous green body by a rubber head dropper, and the sizing agent is self-containedUniformly soaking the slurry into the C/C blank from top to bottom by gravity and capillary force, then putting the soaked material and the soaking liquid into a plastic bag together for soaking for 5min until no bubbles appear on the surface of the soaking liquid, taking the material out of the soaking liquid, putting the material into an oven, and drying at 110 ℃ for 24h to obtain the material with the density of 2.77g/cm 3 C/C- (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C intermediate.
(6) Precursor impregnation, cracking and densification: repeated precursor impregnation cleavage of the intermediate was performed by reacting polycarbosilane and n-hexane at 1:1, and fully immersing the intermediate into the impregnating solution, pumping the impregnating solution loaded with the intermediate to 0.5atm, and maintaining the pressure for 30s. Then the impregnating solution is put into an autoclave, nitrogen is introduced until the air pressure is 5MPa, and the pressure is maintained for 5min. The material was taken out of the impregnation liquor and dried in an oven at 60 ℃ for 20h. And (3) placing the dried material into a vacuum sintering furnace, heating to 1400 ℃, and keeping the temperature for 1h at a heating rate of 12 ℃/min. The cycle is repeated 14 times until the mass is increased by less than 1%. The final density was 3.13g/cm 3 C/C- (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C-SiC composite material.
Table 1 shows the ablation data for the oxyacetylene flame of example 1 at 2000℃for various times.
TABLE 1
Example 2
The preparation of the C/C- (Ti, zr, hf, nb, ta) -SiC composite material comprises the following steps:
(1) Powder mixing: 6.789g TiO is weighed respectively 2 、10.474gZrO 2 、17.892gHfO 2 、11.297gNb 2 O 5 、18.781gTa 2 O 5 17.136g of carbon black powder was mixed and stirred until uniform. According to the mass of polyethylene glycol, the mass of powder material and the mass of ethanol are respectively 1:18, 10:1 and 10:1, respectivelyIonized water mass=9:1, 5.084g deionized water and 45.576g ethanol are respectively weighed, 4.576g polyethylene glycol is weighed after mixing, and after the polyethylene glycol is completely dissolved, the mixed solution is poured into the mixed powder. Ball-milling and mixing the obtained mixture for 6 hours at the rotating speed of 180r/min, and putting the mixture into an oven to be dried for 24 hours at the temperature of 80 ℃ to obtain mixed powder.
(2) Compacting and sintering: pressing the powder obtained in the step (1) under 0.5MPa to obtain a blank to be sintered, then placing the blank in a high-temperature sintering furnace to perform carbothermic reduction-diffusion reaction, setting the heat preservation temperature to 1700 ℃, the heat preservation time to 1.5h, and the heating rate to 10 ℃/min to obtain a large block (Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C high entropy carbide powder.
(3) Ball milling and refining: separately weigh (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) 120g of high-entropy carbide powder, 40g of absolute ethyl alcohol and 360g of tungsten carbide ball mill are placed in a hard alloy ball milling tank. The ball mill pot was put into a ball mill and was stopped for 5 minutes every 5 minutes at a rotation speed of 260r/min, and the total duration was 12 hours. After ball milling is finished, the ball mill is loaded with (Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C, putting the ball milling pot of the high-entropy carbide powder into an oven, setting the temperature to be 110 ℃, and drying for 24 hours.
(4) And (3) preparing slurry: respectively weighing 35.5g of high-entropy carbide powder, 5.621g of deionized water, 0.977g of aqueous solution of 10% polyethylenimine by mass fraction and 20g of zirconia ball mill, adding into a nylon ball mill tank, placing into a planetary ball mill for mixing, and continuously rotating at a rotating speed of 150r/min for 1h to obtain (Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C, high-entropy carbide impregnating slurry.
(5) Slurry impregnation: dropping the slurry on the upper surface of the C/C composite porous green body by using a rubber head dropper, uniformly soaking the slurry into the C/C green body from top to bottom by means of the self weight and capillary force of the slurry, then soaking the soaked material and the soaking liquid in a plastic bag for 5min until no bubbles appear on the surface of the soaking liquid, taking the material out of the soaking liquid, and putting the material into the plastic bagDrying in an oven at 120deg.C for 21h to obtain a density of 2.75g/cm 3 C/C- (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C intermediate.
(6) Precursor impregnation, cracking and densification: repeated precursor impregnation cleavage of the intermediate was performed by reacting polycarbosilane and n-hexane at 1:2, fully immersing the intermediate into the impregnating solution, pumping the impregnating solution loaded with the intermediate to 0.6atm, and maintaining the pressure for 40s. Then the impregnating solution is put into an autoclave, nitrogen is introduced until the air pressure is 6MPa, and the pressure is maintained for 4min. The material was removed from the impregnation solution and dried in an oven at 50 ℃ for 22h. And (3) placing the dried material into a vacuum sintering furnace, heating to 1400 ℃, and keeping the temperature for 1h at a heating rate of 14 ℃/min. The cycle is repeated 16 times until the mass is increased by less than 1%. The final density was 3.10g/cm 3 C/C- (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C-SiC composite material.
Example 3
The preparation of the C/C- (Ti, zr, hf, nb, ta) -SiC composite material comprises the following steps:
(1) Powder mixing: 6.789g TiO is weighed respectively 2 、10.474gZrO 2 、17.892gHfO 2 、11.297gNb 2 O 5 、18.781gTa 2 O 5 17.136g of carbon black powder was mixed and stirred until uniform. According to the mass of polyethylene glycol, the mass of powder material and the mass of ethanol are respectively equal to 1:20, 10:1 and 9:1, respectively weighing 4.576g of deionized water and 41.18g of ethanol, mixing, weighing 4.118g of polyethylene glycol, and pouring the mixed solution into the mixed powder after the polyethylene glycol is completely dissolved. Ball-milling and mixing the obtained mixture for 9 hours at a rotating speed of 160r/min, and putting the mixture into an oven to be dried for 24 hours at 100 ℃ to obtain mixed powder.
(2) Compacting and sintering: pressing the powder obtained in the step (1) under 1MPa to obtain a blank to be sintered, then placing the blank in a high-temperature sintering furnace to perform carbothermic reduction-diffusion reaction, and setting the heat preservation temperature to be 1800 DEG CThe temperature is kept for 1.5h, the heating rate is 10 ℃/min, and the massive (Ti) is obtained 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C high entropy carbide powder.
(3) Ball milling and refining: separately weigh (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) 120g of high-entropy carbide powder, 40g of absolute ethyl alcohol and 360g of tungsten carbide ball mill are placed in a hard alloy ball milling tank. The ball mill pot was put into a ball mill and was stopped for 5 minutes every 5 minutes at a rotation speed of 260r/min, and the total duration was 12 hours. After ball milling is finished, the ball mill is loaded with (Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C, putting the ball milling pot of the high-entropy carbide powder into an oven, setting the temperature to be 110 ℃, and drying for 24 hours.
(4) And (3) preparing slurry: respectively weighing 65.1g of high-entropy carbide powder, 11.242g of deionized water, 1.953g of aqueous solution of 10% polyethylenimine by mass fraction and 40g of zirconia ball mill, adding into a nylon ball milling tank, placing into a planetary ball mill for mixing, and continuously rotating at a rotating speed of 150r/min for 1h to obtain (Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C, high-entropy carbide impregnating slurry.
(5) Slurry impregnation: dropping the slurry on the upper surface of the C/C composite porous green body by using a rubber head dropper, uniformly soaking the C/C green body from top to bottom by the slurry self weight and capillary force, then putting the soaked material and the soaking liquid into a plastic bag together for soaking for 5min until no bubbles appear on the surface of the soaking liquid, taking the material out of the soaking liquid, putting the material into a baking oven, firstly drying at 80 ℃ for 10h, and then drying at 120 ℃ for 14h to obtain the composite porous green body with the density of 2.75g/cm 3 C/C- (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C intermediate.
(6) Precursor impregnation, cracking and densification: repeated precursor impregnation cleavage of the intermediate was performed by reacting polycarbosilane and n-hexane at 1:1, and fully immersing the intermediate into the impregnating solution, pumping the impregnating solution loaded with the intermediate to 0.5atm, and maintaining the pressure for 40s. Then the impregnating solution is putIntroducing nitrogen into an autoclave until the air pressure is 6MPa, and maintaining the pressure for 4min. The material was removed from the impregnation solution and dried in an oven at 40 ℃ for 20h. And (3) placing the dried material into a vacuum sintering furnace, heating to 1400 ℃, and keeping the temperature for 1h at a heating rate of 10 ℃/min. The cycle is repeated 18 times until the mass is increased by less than 1%. The final density was 3.09g/cm 3 C/C- (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C-SiC composite material.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Comparative example 1
Otherwise, as in example 1, only polyethylene glycol was not added in step (1), and as a result, the high-entropy ceramic powder obtained at the temperature of example 1 exhibited a severe phase separation phenomenon, failing to obtain a high-entropy ceramic powder of a single-phase solid solution.
It is indicated that the sintering temperature must be increased without adding polyethylene glycol, and the sintering time is prolonged, so that the requirements on experimental equipment are increased.
Comparative example 2
Otherwise, as in example 1, only the polyethylene glycol added in step (1) had a mass of 10g, which also resulted in the phase separation of the resulting high-entropy ceramic powder, because the polyethylene glycol was added too much, the average distance between powders increased, and the diffusion path became long. The ratio between polyethylene glycol and powder must be tightly controlled.
Comparative example 3
Otherwise, the conditions are the same as those of example 1, and only the ball milling time rotating speed of the step (3) is less than 200r/min, so that the final particle size is not 600-1500 nm, the powder particle size is larger, ceramic slurry with good fluidity and low viscosity cannot be obtained, ceramic components cannot be introduced into a C/C composite porous blank, and a C/C- (Ti, zr, hf, nb, ta) C intermediate cannot be prepared.
Comparative example 4
Otherwise, the conditions are the same as those in example 1, and only the dispersant added in the step (4) is sodium polyacrylate, so that a stable solid solution ceramic slurry with good fluidity and low viscosity cannot be obtained, and the ceramic powder is easy to separate from deionized water in the slurry impregnation process in the step (3), so that the ceramic powder can only cover the surface of the C/C composite porous green body, but cannot permeate into the C/C composite porous green body.
Comparative example 5
Otherwise, the conditions are the same as in example 1, and only the solid phase volume content in step (4) is set to 42%, because the excessive solid phase content causes too little dispersant, so that some ceramic powder is not fully dispersed, and as a result, a stable solid solution ceramic slurry with good fluidity and low viscosity cannot be obtained, and the ceramic powder is easily separated from deionized water in the slurry impregnation process in step (3), and the impregnation process cannot be completed.
Comparative example 6
Otherwise, the same conditions as in example 1 were adopted, and only the mass of the aqueous solution of 10% by mass of polyethyleneimine added in step (4) was 3g, since excessive dispersant causes that excessive polyethyleneimine is attached to the surface of each powder particle, the increase of the powder particle size is remarkable, and a stable, good-fluidity, low-viscosity solid solution ceramic slurry could not be obtained.
Comparative example 7
Other conditions were the same as in example 1, except that step (5) was repeated 2 times. Since the high-entropy ceramic powder has filled most of the pores during the 1 st slurry impregnation, only a part of the fine pores remain, and since the (Ti, zr, hf, nb, ta) C is bulky and bridging is easily formed between the powders, the 2 nd slurry impregnation process is caused to progress very slowly, resulting in a waste of a large amount of (Ti, zr, hf, nb, ta) C.
Comparative example 8
Other conditions are the same as in example 1, except that the slurry is not added by using a rubber head dropper in step (5), but the C/C composite porous green body is directly soaked in the slurry containing ceramic, and the obtained intermediate has more holes. This is because the slurry is added by using a rubber head dropper not only in the process of introducing ceramic but also in the process of discharging gas from one end; the direct soaking of the green body in the slurry may result in a partial gas being unable to be smoothly discharged.
Claims (10)
1. A preparation method of a C/C- (Ti, zr, hf, nb, ta) C-SiC composite material is characterized by comprising the following steps: immersing the slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder into a C/C composite porous blank to obtain a C/C- (Ti, zr, hf, nb, ta) C intermediate, and densifying the C/C- (Ti, zr, hf, nb, ta) C intermediate into a SiC matrix through a precursor impregnation cracking process to obtain the C/C- (Ti, zr, hf, nb, ta) C-SiC composite material.
2. The method for preparing a C/C- (Ti, zr, hf, nb, ta) C-SiC composite according to claim 1, wherein: the preparation method of the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder comprises the following steps: tiO is mixed with 2 Powder, zrO 2 Powder, hfO 2 Powder, nb 2 O 5 Powder, ta 2 O 5 Mixing the powder and carbon black powder to obtain mixed powder, adding ethanol, deionized water and polyethylene glycol into the mixed powder, performing first wet ball milling and first drying to obtain powder, pressing the powder to form a blank, performing carbothermic reduction-diffusion reaction on the blank to obtain a high-entropy ceramic block, performing second wet ball milling on the high-entropy ceramic block, and performing second drying to obtain the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder.
3. The method for preparing a C/C- (Ti, zr, hf, nb, ta) C-SiC composite according to claim 2, wherein:
the TiO 2 Powder, zrO 2 Powder, hfO 2 Powder, nb 2 O 5 Powder, ta 2 O 5 The particle size of the powder is 0.5-1.5 mu m, the purity is more than or equal to 99.9%, and the particle size of the carbon black powder is 0.04-0.1 mu m;
in the mixed powder, tiO is calculated according to the mole ratio 2 Powder of ZrO 2 Powder of HfO 2 Powder of Nb 2 O 5 Powder Ta 2 O 5 Powder=17 to 23:17 to 23:8.5 to 11.5:8.5 to 11.5;
the TiO 2 The mol ratio of the powder to the carbon black powder is 1:8-9;
the average molecular weight of the polyethylene glycol is 10000-20000;
the mass ratio of the polyethylene glycol to the mixed powder is 1:18-22;
the mass ratio of the ethanol to the polyethylene glycol is 9-11:1;
the mass ratio of the ethanol to the deionized water is 9-11:1;
the rotational speed of the first wet ball milling is 160-180 r/min, and the time of the first wet ball milling is 4-9 h;
the temperature of the first drying is 80-110 ℃, and the time of the first drying is 24-36 h;
the pressure of the compression molding is 0.5-1 MPa;
the carbothermic reduction-diffusion reaction is carried out in a vacuum environment, the temperature of the carbothermic reduction-diffusion reaction is 1700-1900 ℃, the carbothermic reduction-diffusion reaction time is 1-2 h, and the heating rate is 10-15 ℃/min;
the second wet ball milling is carried out by taking absolute ethyl alcohol as a ball milling medium, and the mass ratio of the (Ti, zr, hf, nb, ta) C high-entropy ceramic block to the absolute ethyl alcohol is 3-6:1;
the ball milling tank is made of hard alloy during the second wet ball milling, the grinding balls are made of hard alloy, the diameter is 1-4 mm, and the mass ratio of the grinding balls to the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder is 2-4:1;
the rotational speed of the second wet ball milling is 220-280 r/min, and the time of the second wet ball milling is 6-12 h;
the temperature of the second drying is 60-120 ℃, and the time of the second drying is 16-32 h.
4. A method of preparing a C/C- (Ti, zr, hf, nb, ta) C-SiC composite according to any one of claims 1 to 3, wherein: the grain size of the (Ti, zr, hf, nb, ta) C high-entropy ceramic powder is 600-1500 nm.
5. The method for preparing a C/C- (Ti, zr, hf, nb, ta) C-SiC composite according to claim 1, wherein: the slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder is prepared by ball milling (Ti, zr, hf, nb, ta) C high-entropy ceramic powder, deionized water and polyethyleneimine water solution; wherein the volume ratio of (Ti, zr, hf, nb, ta) C high-entropy ceramic powder to deionized water is 30-35:65-70, the mass ratio of (Ti, zr, hf, nb, ta) C high-entropy ceramic powder to polyethyleneimine aqueous solution is 1:0.035-0.045, and the mass fraction of polyethyleneimine in the polyethyleneimine aqueous solution is 8-12%;
during ball milling, the ball-material ratio is 1:2-5, the ball milling rotating speed is 100-180 r/min, and the ball milling time is 0.5-1 h.
During ball milling, the ball milling tank is made of nylon, and the grinding balls are made of ZrO 2 。
6. The method for preparing a C/C- (Ti, zr, hf, nb, ta) C-SiC composite according to claim 1, wherein: the density of the C/C composite porous green body is 0.6-1 g/cm 3 ；
The C/C composite porous blank is obtained by densifying a carbon fiber preform through chemical vapor deposition, wherein the carbon fiber preform is of a 2.5D needling structure, and the density of the carbon fiber preform is 0.4-0.5 g/cm 3 The carbon fibers in the carbon fiber preform are polyacrylonitrile carbon fibers.
7. The method for preparing a C/C- (Ti, zr, hf, nb, ta) C-SiC composite according to claim 1, wherein: firstly, dripping slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder on the surface of a C/C composite porous green body by using a dropper, soaking the C/C composite porous green body by using the slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder, then soaking the soaked C/C composite porous green body in the slurry containing (Ti, zr, hf, nb, ta) C high-entropy ceramic powder, and drying to obtain the C/C- (Ti, zr, hf, nb, ta) C intermediate.
8. The method for preparing a C/C- (Ti, zr, hf, nb, ta) C-SiC composite according to claim 1, wherein: the precursor dipping and cracking process comprises the steps of dipping a C/C- (Ti, zr, hf, nb, ta) C intermediate in a dipping agent, then solidifying and cracking, and repeating dipping-solidifying-cracking until the precursor is compact;
the impregnant consists of polycarbosilane and n-hexane, and the mass ratio of the polycarbosilane to the n-hexane is 1:1-4.
9. The method for preparing a C/C- (Ti, zr, hf, nb, ta) C-SiC composite according to claim 8, wherein: the dipping process is that the pressure reduction dipping is carried out for 5 to 60 seconds under the air pressure of 0.3 to 0.7atm, and then the pressure pressing dipping is carried out for 3 to 10 minutes under the air pressure of 4 to 7 MPa;
the curing temperature is 40-80 ℃, and the curing time is 5-20 h;
the cracking temperature is 1000-1600 ℃, the cracking time is 0.5-1.5 h, and the heating rate is 10-15 ℃/min.
10. A C/C- (Ti, zr, hf, nb, ta) C-SiC composite material prepared by the method of any one of claims 1 to 9.
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