CN108083801B - Three-dimensional carbon fiber prefabricated part reinforced yttrium oxide-zirconium oxide composite ceramic composite material and preparation method thereof - Google Patents

Three-dimensional carbon fiber prefabricated part reinforced yttrium oxide-zirconium oxide composite ceramic composite material and preparation method thereof Download PDF

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CN108083801B
CN108083801B CN201810008941.8A CN201810008941A CN108083801B CN 108083801 B CN108083801 B CN 108083801B CN 201810008941 A CN201810008941 A CN 201810008941A CN 108083801 B CN108083801 B CN 108083801B
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马青松
曾宽宏
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National University of Defense Technology
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Abstract

The invention discloses a three-dimensional carbon fiber prefabricated part reinforced yttrium oxide-zirconium oxide complex phase ceramic composite material and a preparation method thereof2O3‑ZrO2Multiphase ceramic, Y2O3‑ZrO2In the complex phase ceramics, ZrO2The molar content of (A) is 5-95%, Y2O3‑ZrO2The complex phase ceramic is uniformly filled in the pores of the three-dimensional carbon fiber prefabricated part, and the porosity of the composite material is 8-15%. The preparation method comprises the following steps: (1) preparation of Y2O3‑ZrO2Compounding sol; (2) dipping; (3) drying; (4) heat treatment; (5) and (4) repeating the dipping-drying-heat treatment process of the steps (2) to (4). The composite material has the advantages of low porosity, high density, high temperature resistance, excellent oxidation resistance and mechanical property, and the like, and the preparation method has high preparation efficiency and obviously improves the density and the mechanical property of the prepared composite material.

Description

Three-dimensional carbon fiber prefabricated part reinforced yttrium oxide-zirconium oxide composite ceramic composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of high-temperature-resistant fiber-reinforced ceramic matrix composite materials, and particularly relates to a three-dimensional carbon fiber prefabricated part reinforced yttrium oxide-zirconium oxide (Y)2O3-ZrO2) A complex phase ceramic composite material and a preparation method thereof.
Background
Y2O3-ZrO2Complex phase ceramic with Y function2O3And ZrO2Has the advantages of high temperature resistance, oxidation resistance, creep resistance, corrosion resistance and the like, and simultaneously, Y2O3Can suppress ZrO2The ceramic material is an excellent high-temperature resistant ceramic material, and is widely researched as a thermal barrier coating material. As a monolithic ceramic, Y2O3-ZrO2The fracture toughness of the complex phase ceramic is low, and is 2-4 MPa.m in most cases1/2. Such low fracture toughness results in monomer Y2O3-ZrO2The complex phase ceramics are difficult to be used as structural materials for practical application, especially in the case of impact with large mechanical loadIn the case of thermal shock, toughening treatment is required.
The introduction of fibers in ceramic matrices has proven to be the most effective toughening method capable of significantly improving fracture toughness. Among the reinforcing fibers, carbon fiber is the most widely used reinforcing member because of its advantages such as low cost, high temperature resistance, high tensile strength, and easy weaving and forming into complex shapes. Therefore, if the carbon fiber can be mixed with Y2O3-ZrO2The composite ceramic is compounded together, and the advantages of the composite ceramic and the composite ceramic are combined, so that the fiber reinforced Y with high temperature resistance, oxidation resistance, high strength and high toughness is expected to be obtained theoretically2O3-ZrO2A composite ceramic material.
The fiber preform reinforced composite material can be divided into one-dimensional, two-dimensional and three-dimensional preform reinforced composite materials according to the arrangement mode of fibers in the composite material, namely the structural form of the fiber preform. The one-dimensional composite material is prepared by winding fiber bundles into non-woven cloth through slurry prepared from ceramic matrix powder (the slurry contains a binder for adhering the ceramic powder to fibers), then laying the non-woven cloth in different directions and different angles, or directly winding the non-woven cloth into a required shape in different directions and different angles, and then sintering at high temperature and under no pressure or under hot pressure. The two-dimensional composite material is obtained by adhering a ceramic matrix on the surface of fiber cloth in a manner of coating, dip-coating and the like with slurry prepared from ceramic matrix powder, laminating the fiber cloth, and then sintering at high temperature and under no pressure or under hot pressure. The three-dimensional composite material is obtained by firstly manufacturing fibers into a three-dimensional prefabricated part and then introducing a ceramic matrix into the prefabricated part by means of a gas phase method, a liquid phase method and the like. In comparison, the three-dimensional composite material has better integrity (the in-plane and interlayer performance of the one-dimensional and two-dimensional composite materials is weaker), and the designability of the fiber content and the arrangement directionality is strong, so that the three-dimensional composite material is more suitable for preparing components with complex shapes.
However, densification of three-dimensional composites is difficult to handle in one-dimensional and two-dimensional composite manufacturing processes due to the different preform structures. For the structural features of three-dimensional preforms, two densification methods are currently commonly used: one is to heat the preform as requiredAfter the temperature is reached, gaseous raw materials are introduced, the raw materials are diffused into the prefabricated member and react and deposit under the action of high temperature to obtain a ceramic matrix, pores in the prefabricated member are gradually filled with the ceramic matrix along with the prolonging of the deposition time, and the density is continuously increased, namely a gas phase method; secondly, after the prefabricated member is soaked in the liquid raw material, the prefabricated member is dried to remove the solvent, then the prefabricated member is subjected to heat treatment at high temperature to obtain a ceramic matrix, the soaking, drying and heat treatment are repeated for a plurality of periods, the pores in the prefabricated member are gradually filled with the ceramic matrix, the density is continuously increased, and the method is called as a liquid phase method. In contrast, the liquid phase method has low requirements on equipment, is insensitive to a temperature field and a chemical field in the equipment during compounding, and has more obvious advantages in the preparation of complex shapes and batch components. And for fiber reinforcement Y2O3-ZrO2Complex phase ceramic composites, currently suitable for deposition of Y2O3And ZrO2The gaseous raw material is too little, the deposition characteristic is not ideal enough, the liquid raw material is easy to obtain, and the performance is reliable.
For a liquid phase method, how to rapidly prepare a three-dimensional fiber preform reinforced Y with high density and high mechanical property2O3-ZrO2The complex phase ceramic composite material is a key problem to be solved, and the related key technical points comprise the properties of liquid raw materials, an impregnation process and a heat treatment process. At present, the preparation of three-dimensional carbon fiber prefabricated part reinforced Y by a liquid phase method is not found2O3-ZrO2The research of the composite ceramic material is reported.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a three-dimensional carbon fiber prefabricated part reinforced yttrium oxide-zirconium oxide (Y) with high temperature resistance, oxidation resistance and excellent mechanical property2O3-ZrO2) A complex phase ceramic composite material and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a three-dimensional carbon fiber prefabricated part reinforced yttrium oxide-zirconium oxide complex phase ceramic composite material is characterized by comprising a three-dimensional carbon fiber prefabricated part and Y2O3-ZrO2A complex phase ceramic of said Y2O3-ZrO2In the complex phase ceramics, ZrO2The molar content of Y is 5-95 percent2O3-ZrO2The complex phase ceramic is uniformly filled in the pores of the three-dimensional carbon fiber prefabricated member, and the three-dimensional carbon fiber prefabricated member is reinforced with Y2O3-ZrO2The porosity of the composite ceramic material is 8-15%.
Preferably, the three-dimensional carbon fiber preform is one or more of a three-dimensional carbon fiber preform obtained by laminating and sewing carbon fiber cloth, a three-dimensional carbon fiber preform obtained by alternately laminating and needling carbon fiber cloth and a mesh tire, a three-dimensional carbon fiber preform with a three-dimensional five-direction woven structure, a three-dimensional carbon fiber preform with a two-dimensional semi-woven structure and a three-dimensional carbon fiber preform with a three-dimensional four-direction woven structure; the volume fraction of carbon fibers in the three-dimensional carbon fiber prefabricated part is 25-55%.
As a general inventive concept, the present invention also provides a preparation method of a three-dimensional carbon fiber preform reinforced yttria-zirconia composite ceramic composite material, comprising the following steps:
(1) preparation of Y2O3-ZrO2Compounding sol: will Y2O3Sol and ZrO2Mixing the sol and adding a stabilizer to obtain Y2O3-ZrO2Compounding sol;
(2) dipping: placing the three-dimensional carbon fiber prefabricated part in a container, vacuumizing and sucking Y obtained in the step (1)2O3-ZrO2Compounding sol, vacuum impregnating to make Y2O3-ZrO2Filling the composite sol in the three-dimensional carbon fiber prefabricated part;
(3) and (3) drying: taking out the three-dimensional carbon fiber prefabricated member and drying to remove Y2O3-ZrO2Solvents and stabilizers in the composite sol;
(4) and (3) heat treatment: carrying out heat treatment under the protection of inert atmosphere to obtain the three-dimensional carbon fiber prefabricated partStrong Y2O3-ZrO2A complex phase ceramic composite intermediate;
(5) repeating the dipping-drying-heat treatment process of the steps (2) to (4) until the three-dimensional carbon fiber prefabricated part is reinforced by Y2O3-ZrO2Compared with the previous impregnation-drying-heat treatment process, the weight gain of the intermediate of the composite ceramic material is lower than 1 percent, and the three-dimensional carbon fiber prefabricated part reinforced Y is obtained2O3-ZrO2A composite ceramic material.
Preferably, in the step (1), the stabilizer is strong acid, and the stabilizer and the Y are mixed together2O3The mass ratio of the sol is 2-3: 10.
Preferably, in the preparation method of the three-dimensional carbon fiber preform reinforced yttria-zirconia composite ceramic composite material, the strong acid comprises HNO3HCl or H2SO4。
In the above preparation method of the three-dimensional carbon fiber preform reinforced yttria-zirconia composite ceramic composite material, preferably, in the step (1), Y is2O3-ZrO2In the composite sol, the solid content is 20-40 wt%, and Y is2O3And ZrO2The molar ratio of the composite sol is 95/5-5/95, and the size of the colloidal particles of the composite sol is less than or equal to 30 nm.
Preferably, in the step (3), the drying temperature is 400-700 ℃ and the drying time is 1-6 hours.
Preferably, in the step (2), after vacuum impregnation, air pressure-assisted impregnation is further performed under a set pressure, so that the Y is obtained2O3-ZrO2The composite sol is further filled in the three-dimensional carbon fiber prefabricated member.
Preferably, in the step (2), the vacuum impregnation process conditions include: the vacuum degree is less than or equal to 500Pa, and the dipping time is 4-8 h; the technological conditions of the air pressure auxiliary impregnation are as follows: the set pressure is 2MPa to 10MPa, and the dipping time is 2h to 6 h.
Preferably, in the step (4), the heat treatment process includes: under the protection of inert atmosphere, heating to 1100-1500 ℃ at the speed of 10-20 ℃/min, and keeping the temperature for 0.5-2 h.
Preferably, the preparation method of the three-dimensional carbon fiber preform reinforced yttria-zirconia multiphase ceramic composite material further comprises a three-dimensional carbon fiber preform pretreatment step before the step (2), specifically: and (3) placing the three-dimensional carbon fiber prefabricated part in vacuum or inert atmosphere, heating to 1400-1800 ℃ at the speed of 10-20 ℃/min, and preserving heat for 1-4 h.
Compared with the prior art, the invention has the advantages that:
1. the three-dimensional carbon fiber prefabricated part of the invention reinforces Y2O3-ZrO2A composite ceramic material is prepared from carbon fibres and Y through mixing2O3-ZrO2The advantages of the complex phase ceramic and the three-dimensional prefabricated member are combined together to obtain the high-temperature-resistant and oxidation-resistant three-dimensional carbon fiber prefabricated member reinforced Y with excellent mechanical property2O3-ZrO2A composite ceramic material. The mechanical property of the three-dimensional carbon fiber prefabricated part is utilized to provide excellent mechanical property, particularly high fracture toughness, and the defect of monomer Y is overcome2O3-ZrO2Brittleness of complex phase ceramics; using Y2O3-ZrO2The composite ceramic has excellent oxidation resistance, and carbon fibers are wrapped and protected to provide excellent oxidation resistance of the composite material; utilizing the high temperature resistance of carbon fiber and Y2O3-ZrO2The high melting point of the complex phase ceramic provides the composite material with excellent high temperature resistance.
2. Three-dimensional carbon fiber of the present inventionPrefabricated part reinforced Y2O3-ZrO2The complex phase ceramic composite material has lower porosity (8-15 percent), namely Y2O3-ZrO2The content and the density are high, so that the composite material has excellent mechanical property, high temperature resistance and oxidation resistance.
3. The three-dimensional carbon fiber prefabricated part of the invention reinforces Y2O3-ZrO2Preparation method of composite ceramic material with Y2O3-ZrO2The composite sol is used as a liquid raw material, and a liquid phase method is adopted to prepare a three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2The composite ceramic material has high solid content and nanometer sol to make Y possess high strength2O3-ZrO2The particles are quickly and uniformly filled into the gaps in the prefabricated member, and compared with a technical route starting from a solution, the densification efficiency is high; compared with the technical route of taking the slurry prepared from the ceramic powder as the raw material, Y2O3-ZrO2Good uniformity of particle distribution and generation of Y2O3-ZrO2The complex phase ceramic has low temperature and small damage to fiber.
4. The three-dimensional carbon fiber prefabricated part of the invention reinforces Y2O3-ZrO2A process for preparing composite heterogeneous ceramic material from liquid raw material Y2O3-ZrO2Acid liquor is introduced into the composite sol as a stabilizer, so that Y is solved2O3Sol and ZrO2The sol has poor compatibility due to the obvious difference of hydrolysis speed, and stable Y is obtained2O3-ZrO2The composite sol provides reliable raw material guarantee for the preparation of the composite material. Applicant is preparing Y2O3-ZrO2During compounding of the sol, Y is found2O3Sol and ZrO2The sol is mixed and then precipitated, the precipitation destroys the monodisperse state of nano-sized colloidal particles in the sol, and the obtained particles are in a large-size agglomeration state, cannot be impregnated into pores of a fiber prefabricated member, and cannot be used as a raw material of a technical route of impregnation-drying-heat treatment. In the early days, attempts have been made to add by dilutionChelating agents are added to stabilize Y (principle is to increase steric hindrance and reduce collision probability of colloidal particles)2O3-ZrO2The composite sol has a less ideal stabilizing effect, and the solid content of the composite sol is reduced to a certain extent, so that the preparation efficiency of the composite material is reduced. To better stabilize Y2O3-ZrO2Composite sol, Applicant company's on Y2O3Sol and ZrO2The reason for generating the precipitation after the sol is mixed is deeply researched theoretically and explored practically, and the research result shows that: y is2O3The sol is alkaline, ZrO2The sol is acidic, so when the two are mixed, the pH value is mismatched, the sol is instable and precipitation occurs. The invention reverses thinking according to Y2O3Sol and ZrO2The hydrolysis mechanism in the sol synthesis process is that acid liquid is added to partially peptize hydrolyzed colloidal particles, so that the collision instability probability is reduced, and meanwhile, the pH values of the colloidal particles and the acid liquid are adjusted to the same level, so that the stability of the composite sol is obviously improved, and the solid content and the composite efficiency of the composite sol are not reduced. In addition, the viscosity of the composite sol can be reduced to a certain extent by adding the acid liquor, so that the impregnation into the fiber preform is facilitated. The acid liquid is preferably strong acid, strong acid is against Y2O3-ZrO2The composite sol has a stabilizing effect superior to that of weak acid, wherein nitric acid is used for Y2O3-ZrO2The composite sol has the best stabilizing effect.
5. The three-dimensional carbon fiber prefabricated part of the invention reinforces Y2O3-ZrO2The preparation method of the composite ceramic material is characterized in that Y2O3-ZrO2The composite sol contains a stabilizer, which can remain in the gel in the form of acid radical, and if the composite sol can not be completely removed at a lower temperature, Y at a high temperature can be influenced2O3And ZrO2The reaction and sintering of (2) and also the damage of the carbon fibers. The invention chooses to remove it in the drying stage by raising the drying temperature (400-700 deg.C), in which temperature range the acid radicals will be decomposed, e.g. nitrate radicals can be decomposed to NOxAnd O2To excludeClean, so that Y is not influenced by gas volatilization at high temperature2O3And ZrO2The reaction and sintering shrinkage of the carbon fiber are avoided, and meanwhile, the carbon fiber is not obviously damaged.
6. The three-dimensional carbon fiber prefabricated part of the invention reinforces Y2O3-ZrO2The preparation method of the composite ceramic material further comprises the step of adding Y into the sol used by the invention2O3-ZrO2The composite material is amorphous and nano-scale, has high surface energy, thus having high sintering activity and providing high-quality raw material guarantee for high-temperature heat treatment of the composite material.
7. The three-dimensional carbon fiber prefabricated part of the invention reinforces Y2O3-ZrO2The preparation method of the composite ceramic material further adopts a mode of vacuum impregnation firstly and then air pressure auxiliary impregnation, and the air in the gaps in the prefabrication is firstly removed by vacuum pumping to provide space for the infiltration of the sol, and because the sol is Y with nano-sized single particles uniformly dispersed2O3-ZrO2The composite colloidal particles have good stability, so that the composite colloidal particles can quickly and uniformly enter gaps of the prefabricated member; then, the sol is promoted to further permeate into the interior of the prefabricated member through the action of external air pressure, enters some complex pore spaces of the pore channels, and even can destroy some closed pores to open pores, so that the impregnation efficiency and the filling degree are improved.
8. The three-dimensional carbon fiber prefabricated part of the invention reinforces Y2O3-ZrO2The preparation method of the composite ceramic material further adopts amorphous Y with small and stable grain size2O3-ZrO2On the basis of using the composite sol as a matrix raw material, Y is added2O3-ZrO2The research of sintering shrinkage behavior sets the heat treatment temperature to 1100-1500 ℃, and in the temperature range, Y can be ensured2O3-ZrO2Conversion to Y2O3-ZrO2The composite ceramic can obtain higher density of the matrix (improving the load bearing and load transmission capacity of the matrix), and finally obtain comprehensiveThree-dimensional carbon fiber prefabricated part reinforced Y with excellent performance2O3-ZrO2A composite ceramic material.
In a word, the invention starts from the aspects of liquid raw material characteristics, dipping process, drying process and heat treatment temperature, and obviously improves the three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2The compactness of the composite ceramic material not only enhances the bearing capacity of the matrix, but also enhances the load transfer capacity of the matrix, so that the prepared three-dimensional carbon fiber prefabricated part enhances Y2O3-ZrO2The composite ceramic material has excellent mechanical performance, high temperature resistance and oxidation resistance.
Drawings
FIG. 1 shows a three-dimensional carbon fiber preform reinforcement Y prepared in example 1 of the present invention2O3-ZrO2Macroscopic photograph of the composite ceramic material.
FIG. 2 shows a three-dimensional carbon fiber preform reinforcement Y prepared in example 1 of the present invention2O3-ZrO2Microstructure of the composite ceramic material.
FIG. 3 shows a base material Y of the present invention2O3-ZrO2Composite sol (Y)2O3And ZrO2Molar ratio 1: 1) XRD pattern of the gel powder obtained by drying.
FIG. 4 shows a base material Y of the present invention2O3-ZrO2Composite sol (Y)2O3And ZrO21: 1) the linear shrinkage after heat treatment at different temperatures after pressing into blocks.
FIG. 5 shows a base material Y of the present invention2O3-ZrO2Composite sol (Y)2O3And ZrO2Molar ratio of 1: 1) dried gel powder, XRD pattern after heat treatment at different temperatures.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
Example 1:
the three-dimensional carbon fiber prefabricated part of the invention reinforces Y2O3-ZrO2The composite ceramic material includes three-dimensional carbon fiber prefabricated part and Y2O3-ZrO2A complex phase ceramic wherein Y2O3-ZrO2Multiple-phase ceramic as matrix, three-dimensional carbon fibre prefabricated part as reinforcing phase, Y2O3-ZrO2The complex phase ceramic is uniformly filled in the gaps of the three-dimensional carbon fiber prefabricated part, and Y is2O3-ZrO2In a complex phase ceramic matrix, Y2O3/ZrO2In the present example, the three-dimensional carbon fiber preform reinforced Y2O3-ZrO2The porosity of the composite ceramic material is 12.4%.
In this embodiment, the three-dimensional carbon fiber preform is obtained by sewing a carbon fiber cloth laminate, and the volume fraction of fibers in the three-dimensional carbon fiber preform is 48%.
In this example, the three-dimensional carbon fiber preform is reinforced with Y2O3-ZrO2The bending strength of the composite ceramic material is 234.5MPa, and the fracture toughness is 11.7 MPa.m1/2. After heat treatment for 1h in 1500 ℃ high-temperature inert atmosphere, the strength retention rate is 96.4%; after being oxidized by static air at 1500 ℃ for 0.5h, the strength retention rate is 92.1 percent.
Three-dimensional carbon fiber preform reinforcing Y of above-mentioned this embodiment2O3-ZrO2The preparation method of the complex phase ceramic composite material comprises the following specific process steps:
(1) selecting sol: selecting Y with solid phase content of 30wt%2O3-ZrO2Composite sol as Y2O3-ZrO2Raw material of a complex phase ceramic matrix, wherein Y2O3And ZrO2At a molar ratio of 1: 1, in said Y2O3-ZrO2HNO is added into the composite sol3As stabilizer, HNO3Is added in an amount of Y2O32 by weight of sol5%。
(2) Pre-treating a prefabricated part: selecting a three-dimensional carbon fiber prefabricated part obtained by laminating and sewing carbon fiber cloth as a reinforcing phase, wherein the volume fraction of fibers in the three-dimensional carbon fiber prefabricated part is 48%. And (3) placing the selected three-dimensional carbon fiber prefabricated member in vacuum, heating to 1400 ℃ at the speed of 20 ℃/min, preserving heat for 2 hours, and then cooling along with a furnace to finish the pretreatment of the prefabricated member.
(3) Vacuum impregnation: placing the pretreated three-dimensional carbon fiber prefabricated part in a vacuum tank, vacuumizing until the vacuum degree reaches 300Pa, and sucking Y in the step (1)2O3-ZrO2Compounding the sol with Y2O3-ZrO2And submerging the three-dimensional carbon fiber prefabricated part by the composite sol, and soaking for 6 hours.
(4) Air pressure assisted impregnation: and (4) moving the prefabricated member (still soaked in the sol) to a pressure kettle, inflating to 4MPa, carrying out air pressure assisted impregnation, and keeping for 4 h.
(5) And (3) drying: and taking the three-dimensional carbon fiber preform out of the sol, and drying the three-dimensional carbon fiber preform for 2 hours at 500 ℃ in an inert atmosphere.
(6) And (3) heat treatment: heating the dried three-dimensional carbon fiber prefabricated part to 1300 ℃ at the speed of 15 ℃/min under the protection of high-purity inert gas, preserving heat for 1h, and then cooling along with a furnace to obtain the three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2A complex phase ceramic composite material intermediate.
(7) The process is repeated: repeating the steps (3) to (6) for 27 times, detecting, and finally processing to obtain the three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2Compared with the weight gain of the intermediate of the complex phase ceramic composite material after the last treatment, the weight gain of the intermediate is 0.85 percent, and the three-dimensional carbon fiber prefabricated part reinforced Y is obtained after the compounding process is finished2O3-ZrO2A composite ceramic material.
FIG. 1 shows a three-dimensional carbon fiber preform reinforcement Y prepared in this example2O3-ZrO2Macroscopic photograph of the composite ceramic material. Through detection, the three-dimensional carbon fiber preform reinforced Y obtained in the embodiment2O3-ZrO2Complex phase ceramicThe porosity of the composite material is 12.4%, the bending strength is 234.5MPa, and the fracture toughness is 11.7 MPa.m1/2. After heat treatment for 1h in 1500 ℃ high-temperature inert atmosphere, the strength retention rate is 96.4%; after being oxidized by static air at 1500 ℃ for 0.5h, the strength retention rate is 92.1 percent. FIG. 2 is a schematic view of a three-dimensional carbon fiber preform reinforcement Y prepared in this example2O3-ZrO2The microstructure of the composite ceramic material shows that Y is a microstructure2O3-ZrO2The complex phase ceramic particles are sintered into blocks and are uniformly filled in the fiber bundles, namely gaps among single fibers.
Example 2:
the three-dimensional carbon fiber prefabricated part of the invention reinforces Y2O3-ZrO2The composite ceramic material includes three-dimensional carbon fiber prefabricated part and Y2O3-ZrO2A complex phase ceramic wherein Y2O3-ZrO2Using a heterogeneous ceramic as a matrix, ZrO2The mol content in the multiphase ceramic is 5 percent, the three-dimensional carbon fiber prefabricated part is a reinforcing phase, and Y is2O3-ZrO2The complex phase ceramic is uniformly filled in the gaps of the three-dimensional carbon fiber prefabricated member, in the embodiment, the three-dimensional carbon fiber prefabricated member is reinforced with Y2O3-ZrO2The porosity of the composite ceramic material is 8.8%.
In this embodiment, the three-dimensional carbon fiber preform is a three-dimensional carbon fiber preform having a three-dimensional four-way woven structure, and the volume fraction of fibers in the three-dimensional carbon fiber preform is 53%.
In this example, the three-dimensional carbon fiber preform is reinforced with Y2O3-ZrO2The bending strength of the composite ceramic material is 296.3MPa, and the fracture toughness is 12.9 MPa.m1/2. After heat treatment for 1h in 1500 ℃ high-temperature inert atmosphere, the strength retention rate is 99.2%; after static air oxidation at 1500 ℃ for 0.5h, the strength retention rate is 97.6%.
Three-dimensional carbon fiber preform reinforcing Y of above-mentioned this embodiment2O3-ZrO2The preparation method of the complex phase ceramic composite material comprises the following specific process steps:
(1) selecting sol: selecting Y with the solid phase content of 35wt%2O3-ZrO2Composite sol as Y2O3-ZrO2Raw material of a complex phase ceramic matrix, wherein Y2O3And ZrO2At a molar ratio of 95: 5 in said Y2O3-ZrO2HNO is added into the composite sol3As stabilizer, HNO3The addition amount is Y2O320% by weight of the sol.
(2) Pre-treating a prefabricated part: the three-dimensional carbon fiber prefabricated part with a three-dimensional four-way weaving structure is selected as a reinforcing phase, and the volume fraction of fibers in the three-dimensional carbon fiber prefabricated part is 53%. And (3) placing the selected three-dimensional carbon fiber prefabricated member in a high-purity argon atmosphere, heating to 1800 ℃ at the speed of 20 ℃/min, preserving heat for 1h, and then cooling along with a furnace to finish the pretreatment of the prefabricated member.
(3) Vacuum impregnation: placing the pretreated three-dimensional carbon fiber prefabricated part in a vacuum tank, vacuumizing until the vacuum degree reaches 100Pa, and sucking Y in the step (1)2O3-ZrO2Compounding the sol with Y2O3-ZrO2And submerging the three-dimensional carbon fiber prefabricated part by the composite sol, and soaking for 4 hours.
(4) Air pressure assisted impregnation: and (4) moving the prefabricated member (still soaked in the sol) to a pressure kettle, inflating to 8MPa, carrying out air pressure assisted impregnation, and keeping for 6 hours.
(5) And (3) drying: and taking the three-dimensional carbon fiber preform out of the sol, and drying the three-dimensional carbon fiber preform for 4 hours at 400 ℃ in an inert atmosphere.
(6) And (3) heat treatment: heating the dried three-dimensional carbon fiber prefabricated part to 1500 ℃ at the speed of 15 ℃/min under the protection of high-purity inert gas, preserving heat for 0.5h, and then cooling along with a furnace to obtain the three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2A complex phase ceramic composite material intermediate.
(7) The process is repeated: repeating the steps (3) to (6) for 31 times, detecting, and finally processing to obtain the three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2The weight gain of the intermediate of the complex phase ceramic composite material is as follows compared with the weight gain of the intermediate of the complex phase ceramic composite material after the last treatment0.89 percent, and obtaining the three-dimensional carbon fiber prefabricated part reinforced Y after the compounding process is finished2O3-ZrO2A composite ceramic material.
Through detection, the three-dimensional carbon fiber preform reinforced Y prepared in the embodiment2O3-ZrO2The porosity of the composite ceramic material is 8.8%, the bending strength is 296.3MPa, and the fracture toughness is 12.9 MPa.m1/2. After heat treatment for 1h in 1500 ℃ high-temperature inert atmosphere, the strength retention rate is 99.2%; after static air oxidation at 1500 ℃ for 0.5h, the strength retention rate is 97.6%.
Example 3:
the three-dimensional carbon fiber prefabricated part of the invention reinforces Y2O3-ZrO2The composite ceramic material includes three-dimensional carbon fiber prefabricated part and Y2O3-ZrO2A complex phase ceramic wherein Y2O3-ZrO2Using a heterogeneous ceramic as a matrix, ZrO2The mol content in the multiphase ceramic is 95 percent, the three-dimensional carbon fiber prefabricated part is a reinforcing phase, and Y is2O3-ZrO2The complex phase ceramic is uniformly filled in the gaps of the three-dimensional carbon fiber prefabricated member, in the embodiment, the three-dimensional carbon fiber prefabricated member is reinforced with Y2O3-ZrO2The porosity of the composite ceramic material is 14.3%.
In this example, the three-dimensional carbon fiber preform was a two-dimensional semi-woven structure three-dimensional carbon fiber preform in which the volume fraction of fibers was 46%.
In this example, the three-dimensional carbon fiber preform is reinforced with Y2O3-ZrO2The bending strength of the composite ceramic material is 215.7MPa, and the fracture toughness is 10.4 MPa.m1/2. After heat treatment for 1h in 1500 ℃ high-temperature inert atmosphere, the strength retention rate is 94.2%; after static air oxidation at 1500 ℃ for 0.5h, the strength retention rate is 90.3%.
Three-dimensional carbon fiber preform reinforcing Y of above-mentioned this embodiment2O3-ZrO2The preparation method of the complex phase ceramic composite material comprises the following specific process steps:
(1) selecting sol:selecting Y with solid phase content of 20wt%2O3-ZrO2Composite sol as Y2O3-ZrO2Raw material of a complex phase ceramic matrix, wherein Y2O3And ZrO2At a molar ratio of 5: 95 in said Y2O3-ZrO2HNO is added into the composite sol3As stabilizer, HNO3The addition amount is Y2O320% by weight of the sol.
(2) Pre-treating a prefabricated part: and selecting a three-dimensional carbon fiber prefabricated part with a two-dimensional semi-woven structure as a reinforcing phase, wherein the volume fraction of fibers in the three-dimensional carbon fiber prefabricated part is 46%. And (3) putting the selected three-dimensional carbon fiber prefabricated member in vacuum, heating to 1400 ℃ at the speed of 15 ℃/min, preserving heat for 3 hours, and then cooling along with a furnace to finish the pretreatment of the prefabricated member.
(3) Vacuum impregnation: placing the pretreated three-dimensional carbon fiber prefabricated part in a vacuum tank, vacuumizing until the vacuum degree reaches 200Pa, and sucking Y in the step (1)2O3-ZrO2Compounding the sol with Y2O3-ZrO2And submerging the three-dimensional carbon fiber prefabricated part by the composite sol, and soaking for 8 hours.
(4) Air pressure assisted impregnation: and (4) moving the prefabricated member (still soaked in the sol) to a pressure kettle, inflating to 10MPa, carrying out air pressure assisted impregnation, and keeping for 2 h.
(5) And (3) drying: and taking the three-dimensional carbon fiber preform out of the sol, and drying the three-dimensional carbon fiber preform for 1h at 700 ℃ in an inert atmosphere.
(6) And (3) heat treatment: heating the dried three-dimensional carbon fiber prefabricated part to 1200 ℃ at the speed of 10 ℃/min under the protection of high-purity inert gas, preserving heat for 1.5h, and then cooling along with a furnace to obtain the three-dimensional carbon fiber prefabricated part reinforced Y2O3–ZrO2A complex phase ceramic composite material intermediate.
(7) The process is repeated: repeating the steps (3) to (6) for 25 times, detecting, and finally processing to obtain the three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2The weight gain of the intermediate of the composite ceramic material is 0.81 percent compared with the weight gain of the intermediate of the composite ceramic material after the last treatment, and the composite ceramic material is obtained after the completion of the composite processTo three-dimensional carbon fiber preform reinforcement Y2O3-ZrO2A composite ceramic material.
Through detection, the three-dimensional carbon fiber preform reinforced Y prepared in the embodiment2O3-ZrO2The porosity of the composite ceramic material is 14.3%, the bending strength is 215.7MPa, and the fracture toughness is 10.4 MPa.m1/2. After heat treatment for 1h in 1500 ℃ high-temperature inert atmosphere, the strength retention rate is 94.2%; after static air oxidation at 1500 ℃ for 0.5h, the strength retention rate is 90.3%.
Example 4:
the three-dimensional carbon fiber prefabricated part of the invention reinforces Y2O3-ZrO2The composite ceramic material includes three-dimensional carbon fiber prefabricated part and Y2O3-ZrO2A complex phase ceramic wherein Y2O3-ZrO2Multiple phase ceramic as matrix, Y2O3And ZrO2The molar ratio of the three-dimensional carbon fiber preform to the reinforcing phase is 1: 4, Y is2O3-ZrO2The complex phase ceramic is uniformly filled in the gaps of the three-dimensional carbon fiber prefabricated member, in the embodiment, the three-dimensional carbon fiber prefabricated member is reinforced with Y2O3-ZrO2The porosity of the composite ceramic material is 10.5%.
In this embodiment, the three-dimensional carbon fiber preform is obtained by alternately laminating and needling carbon fiber cloth and a mesh fabric, and the volume fraction of fibers in the three-dimensional carbon fiber preform is 28%.
In this example, the three-dimensional carbon fiber preform is reinforced with Y2O3-ZrO2The bending strength of the composite ceramic material is 112.6MPa, and the fracture toughness is 8.2 MPa.m1/2. After heat treatment for 1h in 1500 ℃ high-temperature inert atmosphere, the strength retention rate is 98.1%; after static air oxidation at 1500 ℃ for 0.5h, the strength retention rate is 92.4%.
Three-dimensional carbon fiber preform reinforcing Y of above-mentioned this embodiment2O3-ZrO2The preparation method of the complex phase ceramic composite material comprises the following specific process steps:
(1) selecting sol:selecting Y with solid phase content of 40wt%2O3-ZrO2Composite sol as Y2O3-ZrO2Raw material of a complex phase ceramic matrix, wherein Y2O3And ZrO2At a molar ratio of 1: 4, in said Y2O3-ZrO2HNO is added into the composite sol3As stabilizer, HNO3The addition amount is Y2O330% by weight of the sol.
(2) Pre-treating a prefabricated part: selecting a three-dimensional carbon fiber prefabricated part obtained by alternately laminating and needling carbon fiber cloth and a net tire as a reinforcing phase, wherein the volume fraction of fibers in the three-dimensional carbon fiber prefabricated part is 28%. And (3) placing the selected three-dimensional carbon fiber prefabricated member in vacuum, heating to 1400 ℃ at the speed of 10 ℃/min, preserving heat for 4 hours, and then cooling along with a furnace to finish the pretreatment of the prefabricated member.
(3) Vacuum impregnation: placing the pretreated three-dimensional carbon fiber prefabricated part in a vacuum tank, vacuumizing until the vacuum degree reaches 500Pa, and sucking Y in the step (1)2O3-ZrO2Compounding the sol with Y2O3-ZrO2And submerging the three-dimensional carbon fiber prefabricated part by the composite sol, and soaking for 8 hours.
(4) Air pressure assisted impregnation: and (4) moving the prefabricated member (still soaked in the sol) to a pressure kettle, inflating to 2MPa, carrying out air pressure assisted impregnation, and keeping for 6 hours.
(5) And (3) drying: and taking the three-dimensional carbon fiber preform out of the sol, and drying for 6 hours at 400 ℃ in an inert atmosphere.
(6) And (3) heat treatment: heating the dried three-dimensional carbon fiber prefabricated part to 1100 ℃ at the speed of 10 ℃/min under the protection of high-purity inert gas, preserving heat for 2 hours, and then cooling along with a furnace to obtain the three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2A complex phase ceramic composite material intermediate.
(7) The process is repeated: repeating the steps (3) to (6) for 36 times, detecting, and finally processing to obtain the three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2Compared with the weight gain of the intermediate of the complex phase ceramic composite material after the last treatment, the weight gain is 0.78 percent, and the complex phase ceramic composite material is compoundedAfter the process is finished, obtaining the three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2A composite ceramic material.
Through detection, the three-dimensional carbon fiber preform reinforced Y obtained in the embodiment2O3-ZrO2The porosity of the composite ceramic material is 10.5%, the bending strength is 112.6MPa, and the fracture toughness is 8.2 MPa.m1/2. After heat treatment for 1h in 1500 ℃ high-temperature inert atmosphere, the strength retention rate is 98.1%; after static air oxidation at 1500 ℃ for 0.5h, the strength retention rate is 92.4%.
Example 5:
the three-dimensional carbon fiber prefabricated part of the invention reinforces Y2O3-ZrO2The composite ceramic material includes three-dimensional carbon fiber prefabricated part and Y2O3-ZrO2A complex phase ceramic wherein Y2O3-ZrO2Multiple phase ceramic as matrix, Y2O3And ZrO2The molar ratio of (A) to (B) is 3: 1, the three-dimensional carbon fiber prefabricated part is a reinforcing phase, and Y is2O3-ZrO2The complex phase ceramic is uniformly filled in the gaps of the three-dimensional carbon fiber prefabricated member, in the embodiment, the three-dimensional carbon fiber prefabricated member is reinforced with Y2O3-ZrO2The porosity of the composite ceramic material is 11.2%.
In this embodiment, the three-dimensional carbon fiber preform is a three-dimensional carbon fiber preform having a three-dimensional five-direction woven structure, and the volume fraction of fibers in the three-dimensional carbon fiber preform is 50%.
In this example, the three-dimensional carbon fiber preform is reinforced with Y2O3-ZrO2The bending strength of the composite ceramic material is 305.6MPa, and the fracture toughness is 13.3 MPa.m1/2. After heat treatment for 1h in 1500 ℃ high-temperature inert atmosphere, the strength retention rate is 99.0 percent; after static air oxidation at 1500 ℃ for 0.5h, the strength retention rate is 97.8%.
Three-dimensional carbon fiber preform reinforcing Y of above-mentioned this embodiment2O3-ZrO2The preparation method of the complex phase ceramic composite material comprises the following specific process steps:
(1) selecting sol: selecting solidY with a phase content of 30wt%2O3-ZrO2Composite sol as Y2O3-ZrO2Raw material of a complex phase ceramic matrix, wherein Y2O3And ZrO2In a molar ratio of 3: 1, in said Y2O3-ZrO2HNO is added into the composite sol3As stabilizer, HNO3The addition amount is Y2O325% by weight of the sol.
(2) Pre-treating a prefabricated part: the three-dimensional carbon fiber prefabricated part with a three-dimensional five-direction woven structure is selected as a reinforcing phase, and the volume fraction of fibers in the three-dimensional carbon fiber prefabricated part is 50%. And (3) placing the selected three-dimensional carbon fiber prefabricated member in a high-purity argon atmosphere, heating to 1600 ℃ at the speed of 15 ℃/min, preserving heat for 2h, and then cooling along with a furnace to finish the pretreatment of the prefabricated member.
(3) Vacuum impregnation: placing the pretreated three-dimensional carbon fiber prefabricated part in a vacuum tank, vacuumizing until the vacuum degree reaches 400Pa, and sucking Y in the step (1)2O3-ZrO2Compounding the sol with Y2O3-ZrO2And submerging the three-dimensional carbon fiber prefabricated part by the composite sol, and soaking for 6 hours.
(4) Air pressure assisted impregnation: and (4) moving the prefabricated member (still soaked in the sol) to a pressure kettle, inflating to 6MPa, carrying out air pressure assisted impregnation, and keeping for 4 hours.
(5) And (3) drying: and taking the three-dimensional carbon fiber preform out of the sol, and drying for 3 hours at 600 ℃ in an inert atmosphere.
(6) And (3) heat treatment: heating the dried three-dimensional carbon fiber prefabricated part to 1400 ℃ at the speed of 20 ℃/min under the protection of high-purity inert gas, preserving heat for 1h, and then cooling along with a furnace to obtain the three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2A complex phase ceramic composite material intermediate.
(7) The process is repeated: repeating the steps (3) to (6) for 28 times, detecting, and finally processing to obtain the three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2Compared with the weight gain of the intermediate of the complex phase ceramic composite material after the last treatment, the weight gain is 0.90 percent, after the compounding process is finished,obtaining a three-dimensional carbon fiber preform reinforcement Y2O3-ZrO2A composite ceramic material.
Through detection, the three-dimensional carbon fiber preform reinforced Y prepared in the embodiment2O3-ZrO2The porosity of the composite ceramic material is 11.2%, the bending strength is 305.6MPa, and the fracture toughness is 13.3 MPa.m1/2. After heat treatment for 1h in 1500 ℃ high-temperature inert atmosphere, the strength retention rate is 99.0 percent; after static air oxidation at 1500 ℃ for 0.5h, the strength retention rate is 97.8%.
From examples 1 to 5, it can be seen that the three-dimensional carbon fiber preform reinforcement Y produced by the production method of the present invention2O3-ZrO2The composite ceramic material has low porosity, high mechanical performance and excellent high temperature oxidation resistance.
In conclusion, the invention is based on Y2O3-ZrO2The characteristics, the current research situation and the existing problems of the complex phase ceramic are combined with the carbon fiber and the Y2O3-ZrO2The three advantages of the complex phase ceramic and the three-dimensional prefabricated member provide the three-dimensional carbon fiber prefabricated member reinforced Y2O3-ZrO2The complex phase ceramic composite material is a novel material system and forms a preparation method capable of obtaining excellent performance.
In the preparation method, HNO is firstly added3As an additive, stable Y is obtained2O3-ZrO2The composite sol provides reliable raw material guarantee for the preparation of the composite material, and then adopts Y with the solid phase content of 20-40 wt%2O3-ZrO2The composite sol (the particle size of the colloid is less than or equal to 30 nm) is used as a matrix raw material, and the prepared material has the porosity of about 11 percent, the bending strength of 305.6MPa and the fracture toughness of 13.3 MPa.m within a limited period (about 30 periods)1/2Three-dimensional five-way carbon fiber reinforced Y2O3-ZrO2A composite ceramic material. Although there is no fully corresponding three-dimensional five-way carbon fiber reinforced Y made by other methods2O3-ZrO2Complex phase ceramic composites can be compared, but are comparable to similar prior art: firstly, AlCl is adopted in the prior art3·6H2O or Al (NO)3)3·9H2Sol prepared from O inorganic salt is used as a matrix raw material, and three-dimensional four-way carbon fiber reinforced Al is prepared by 13 periods of' dipping-drying-1260 ℃ heat treatment2O3The composite material is found that the density is not increased when the subsequent compounding is continued, the porosity is about 30 percent, and the bending strength is only 100MPa to 150 MPa; secondly, preparing Y from organic salt containing Si and organic salt solution containing Y2SiO5The coating needs to remove a large amount of solvent and additive, the preparation efficiency is very low, and a typical parameter is that the thickness is 2 mu m after 20 times of dip-coating heat treatment. Thus, by comparison, it can be seen that a high solid content Y is used2O3-ZrO2Composite sol as Y2O3-ZrO2Compared with the technical route starting from organic or inorganic salt solution, the composite ceramic matrix raw material has the advantages of self-evident preparation efficiency.
In addition, the scanning electron microscope is adopted to observe the reinforced Y of the three-dimensional carbon fiber prefabricated part2O3-ZrO2The microstructure of the composite ceramic material, as shown in FIG. 2, can be seen as Y2O3-ZrO2The multiphase ceramic particles are sintered into blocks and are uniformly filled in the fiber bundles, namely gaps among single fibers, so that the problem of uneven distribution easily caused by slurry raw materials is solved. Thus, Y used in the present invention2O3-ZrO2The composite sol not only maintains the advantages of uniform filling of the inorganic salt or organic salt solution raw material and high-efficiency impregnation of the slurry raw material, but also overcomes the disadvantages of low densification efficiency of the inorganic salt or organic salt solution raw material and non-uniform filling of the slurry raw material.
Then, the invention adopts a mode of vacuum impregnation firstly and then air pressure auxiliary impregnation, firstly, the air in the gap in the prefabrication is removed by vacuum pumping, space is provided for the infiltration of the sol, and because the sol is Y with uniformly dispersed nano-sized single particles2O3-ZrO2The composite colloidal particles have good stability, so that the composite colloidal particles can be rapidly and uniformly dispersedGround into the void of the preform; then, the sol is promoted to further permeate into the interior of the prefabricated member through the action of external air pressure, enters some complex pore spaces of the pore channels, and even can destroy some closed pores to open pores, so that the impregnation efficiency and the filling degree are improved.
Finally, in the sol used according to the invention, Y2O3-ZrO2Is amorphous and nano-scale, has high surface energy and thus high sintering activity. On the basis of the above, by pairing Y2O3-ZrO2The research of sintering shrinkage behavior sets the heat treatment temperature to 1100-1500 ℃, and in the temperature range, Y can be ensured2O3-ZrO2Conversion to Y2O3-ZrO2The composite ceramic can obtain higher density of the matrix (improving the load bearing and load transmission capacity of the matrix), can not cause obvious reaction between the matrix and the carbon fiber (avoiding forming a chemical strong bonding interface and damaging the mechanical property of the carbon fiber), and finally obtains the three-dimensional carbon fiber prefabricated part reinforced Y with excellent comprehensive performance2O3-ZrO2A composite ceramic material.
For Y2O3-ZrO2Carrying out XRD detection on gel powder obtained after the sol is dried:
analysis of the gel powder (Y) by means of an X-ray diffractometer model D8 Advance2O3And ZrO2The molar ratio is 1: 1), the test conditions are CuK α ray, tube current 40mA, tube voltage 40KV, 2 theta = 15-75 degrees and scanning speed 4 DEG/min.
The detection result is shown in FIG. 3, which shows that: the map shows the peak characteristic of the steamed bread, and no sharp Y appears2O3Or ZrO2Characteristic diffraction peak showing Y after drying at 700 deg.C2O3-ZrO2The gel powder is typically in an amorphous state, which has high surface energy and can promote sintering densification.
For Y2O3-ZrO2Drying the sol to obtain gel powder, pressing into blocks, and mixingThe linear shrinkage conditions of the film after heat treatment at different temperatures are detected as follows:
drying the Y2O3-ZrO2Gel powder (Y)2O3And ZrO2Molar ratio 1: 1) into a metal mould with a diameter of 40mm, pressing the powder on a press at 100MPa into round pieces with a diameter of 40mm and a thickness of 5 mm. And (3) putting the round block into a heat treatment furnace, carrying out heat treatment for 1 hour at different temperatures, measuring the change rate of the diameter and the thickness before and after the heat treatment, and measuring 5 points to obtain an average value as a final result.
The detection result is shown in fig. 4, and it can be seen from the figure that: after heat treatment at 1100-1500 ℃, the linear shrinkage rate is gradually increased along with the temperature rise within the range of 12-19%, wherein when the temperature is increased from 1100 ℃ to 1200 ℃, the linear shrinkage rate is obviously increased, and the change from 1200 ℃ to 1500 ℃ is small, which shows that Y is2O3-ZrO2Has better sintering activity. From the data of fig. 4, it is concluded that the line shrinkage is smaller at heat treatment temperatures below 1100 c, and in conjunction with the test results of fig. 5, the present invention selects a heat treatment temperature range of 1100 c to 1500 c.
Y after heat treatment at different temperatures2O3-ZrO2Carrying out XRD detection on the gel powder:
drying the obtained Y2O3-ZrO2Gel powder (Y)2O3And ZrO2The molar ratio is 1: 1), heat treating for 1h at different temperatures, and analyzing the phase composition of the powder by using a D8 advanced X-ray diffractometer under the test conditions of CuK α rays, tube current of 40mA, tube voltage of 40KV, 2 theta = 10-60 degrees and scanning speed of 4 DEG/min.
The detection result is shown in fig. 5, and it can be seen from the figure that: y is formed at 1100 DEG C2O3-ZrO2The crystallization degree of the composite ceramic phase is higher and higher along with the further increase of the temperature, and a weak ZrC phase is generated when the temperature reaches 1500 ℃, which is the activated carbon atmosphere and ZrO in the furnace2The result of the reaction. Although carbon fiber and ZrO2The reaction of (A) is not so active, but the chemical damage to the carbon fiber is minimized while taking into consideration ZrO2The higher the content is, the higher the reaction possibility is, and the heat treatment temperature range is 1100-1500 ℃ in the invention. As can be seen from FIGS. 4 and 5, in this temperature range, the linear shrinkage rate was high without causing the generation of carbon fibers and ZrO2A chemical reaction between them.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.

Claims (13)

1. A three-dimensional carbon fiber prefabricated part reinforced yttrium oxide-zirconium oxide complex phase ceramic composite material is characterized by comprising a three-dimensional carbon fiber prefabricated part and Y2O3-ZrO2A complex phase ceramic of said Y2O3-ZrO2In the complex phase ceramics, ZrO2The molar content of Y is 5-95 percent2O3-ZrO2The complex phase ceramic is uniformly filled in the pores of the three-dimensional carbon fiber prefabricated member, and the three-dimensional carbon fiber prefabricated member is reinforced with Y2O3-ZrO2The porosity of the composite ceramic material is 8-15%; the preparation method comprises the following steps:
(1) preparation of Y2O3-ZrO2Compounding sol: will Y2O3Sol and ZrO2Mixing the sol and adding a stabilizer to obtain Y2O3-ZrO2Compounding sol; the stabilizer is a strong acid comprising HNO3HCl or H2SO4；
(2) Dipping: placing the three-dimensional carbon fiber prefabricated part in a container, vacuumizing and sucking Y obtained in the step (1)2O3-ZrO2Compounding sol, vacuum impregnating to make Y2O3-ZrO2Filling the composite sol in the three-dimensional carbon fiber prefabricated part;
(3) drying: taking out the three-dimensional carbon fiber prefabricated member and drying to remove Y2O3-ZrO2Solvents and stabilizers in the composite sol;
(4) and (3) heat treatment: carrying out heat treatment under the protection of inert atmosphere to obtain the three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2A complex phase ceramic composite intermediate;
(5) repeating the dipping-drying-heat treatment process of the steps (2) to (4) until the three-dimensional carbon fiber prefabricated part is reinforced by Y2O3-ZrO2Compared with the previous impregnation-drying-heat treatment process, the weight gain of the intermediate of the composite ceramic material is lower than 1 percent, and the three-dimensional carbon fiber prefabricated part reinforced Y is obtained2O3-ZrO2A composite ceramic material.
2. The three-dimensional carbon fiber preform-reinforced yttria-zirconia composite ceramic composite material according to claim 1, wherein the three-dimensional carbon fiber preform is one or more of a three-dimensional carbon fiber preform obtained by laminating and sewing carbon fiber cloth, a three-dimensional carbon fiber preform obtained by alternately laminating and needling carbon fiber cloth and a mesh tire, a three-dimensional carbon fiber preform with a three-dimensional five-way woven structure, a three-dimensional carbon fiber preform with a two-dimensional semi-woven structure and a three-dimensional carbon fiber preform with a three-dimensional four-way woven structure; the volume fraction of carbon fibers in the three-dimensional carbon fiber prefabricated part is 25-55%.
3. A preparation method of a three-dimensional carbon fiber prefabricated part reinforced yttrium oxide-zirconium oxide complex phase ceramic composite material comprises the following steps:
(1) preparation of Y2O3-ZrO2Compounding sol: will Y2O3Sol and ZrO2Mixing the sol and adding a stabilizer to obtain Y2O3-ZrO2Compounding sol; the stabilizer is a strong acid comprising HNO3HCl or H2SO4；
(2) Dipping: placing the three-dimensional carbon fiber prefabricated part into a container, vacuumizing and then sucking the three-dimensional carbon fiber prefabricated part obtained in the step (1)Y of (A) is2O3-ZrO2Compounding sol, vacuum impregnating to make Y2O3-ZrO2Filling the composite sol in the three-dimensional carbon fiber prefabricated part;
(3) and (3) drying: taking out the three-dimensional carbon fiber prefabricated member and drying to remove Y2O3-ZrO2Solvents and stabilizers in the composite sol;
(4) and (3) heat treatment: carrying out heat treatment under the protection of inert atmosphere to obtain the three-dimensional carbon fiber prefabricated part reinforced Y2O3-ZrO2A complex phase ceramic composite intermediate;
(5) repeating the dipping-drying-heat treatment process of the steps (2) to (4) until the three-dimensional carbon fiber prefabricated part is reinforced by Y2O3-ZrO2Compared with the previous impregnation-drying-heat treatment process, the weight gain of the intermediate of the composite ceramic material is lower than 1 percent, and the three-dimensional carbon fiber prefabricated part reinforced Y is obtained2O3-ZrO2A composite ceramic material.
4. The method for preparing a three-dimensional carbon fiber preform-reinforced yttria-zirconia composite ceramic composite according to claim 3, wherein in the step (1), the stabilizer is mixed with the Y2O3The mass ratio of the sol is 2-3: 10.
5. The method for preparing the three-dimensional carbon fiber preform reinforced yttria-zirconia composite ceramic material according to any one of claims 3 to 4, wherein in the step (1), Y is2O3-ZrO2In the composite sol, the solid content is 20-40 wt%, and Y is2O3And ZrO2The molar ratio of the composite sol is 95/5-5/95, and the size of the colloidal particles of the composite sol is less than or equal to 30 nm.
6. The preparation method of the three-dimensional carbon fiber preform reinforced yttria-zirconia composite ceramic material according to claim 5, wherein in the step (3), the drying temperature is 400-700 ℃ and the drying time is 1-6 h.
7. The method for preparing the three-dimensional carbon fiber preform-reinforced yttria-zirconia composite ceramic material according to any one of claims 3 to 4, wherein the vacuum impregnation in the step (2) further comprises performing air pressure assisted impregnation under a set pressure to make Y2O3-ZrO2The composite sol is further filled in the three-dimensional carbon fiber prefabricated member.
8. The method for preparing the three-dimensional carbon fiber preform-reinforced yttria-zirconia composite ceramic material according to claim 6, wherein the step (2) further comprises performing air pressure assisted impregnation under a set pressure after vacuum impregnation so that the Y is obtained2O3-ZrO2The composite sol is further filled in the three-dimensional carbon fiber prefabricated member.
9. The method for preparing the three-dimensional carbon fiber preform-reinforced yttria-zirconia composite ceramic composite material according to claim 7, wherein in the step (2), the vacuum impregnation process conditions are as follows: the vacuum degree is less than or equal to 500Pa, and the dipping time is 4-8 h; the technological conditions of the air pressure auxiliary impregnation are as follows: the set pressure is 2MPa to 10MPa, and the dipping time is 2h to 6 h.
10. The method for preparing the three-dimensional carbon fiber preform-reinforced yttria-zirconia composite ceramic composite material according to claim 8, wherein in the step (2), the vacuum impregnation process conditions are as follows: the vacuum degree is less than or equal to 500Pa, and the dipping time is 4-8 h; the technological conditions of the air pressure auxiliary impregnation are as follows: the set pressure is 2MPa to 10MPa, and the dipping time is 2h to 6 h.
11. The preparation method of the three-dimensional carbon fiber preform reinforced yttria-zirconia composite ceramic material according to any one of claims 3 to 4, wherein in the step (4), the heat treatment process comprises: under the protection of inert atmosphere, heating to 1100-1500 ℃ at the speed of 10-20 ℃/min, and keeping the temperature for 0.5-2 h.
12. The method for preparing the three-dimensional carbon fiber preform reinforced yttria-zirconia composite ceramic material according to claim 6, wherein in the step (4), the heat treatment process comprises: under the protection of inert atmosphere, heating to 1100-1500 ℃ at the speed of 10-20 ℃/min, and keeping the temperature for 0.5-2 h.
13. The method for preparing the three-dimensional carbon fiber preform reinforced yttria-zirconia composite ceramic material according to claim 9, wherein in the step (4), the heat treatment process comprises: under the protection of inert atmosphere, heating to 1100-1500 ℃ at the speed of 10-20 ℃/min, and keeping the temperature for 0.5-2 h.
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