CN108147796A - Three-dimensional silicon carbide fiber reinforced silicon oxide-zirconium oxide composite ceramic composite material and preparation method thereof - Google Patents

Three-dimensional silicon carbide fiber reinforced silicon oxide-zirconium oxide composite ceramic composite material and preparation method thereof Download PDF

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CN108147796A
CN108147796A CN201810008319.7A CN201810008319A CN108147796A CN 108147796 A CN108147796 A CN 108147796A CN 201810008319 A CN201810008319 A CN 201810008319A CN 108147796 A CN108147796 A CN 108147796A
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silicon carbide
carbide fiber
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dimensional silicon
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CN108147796B (en
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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 preparation method of a three-dimensional silicon carbide fiber reinforced silicon oxide-zirconium oxide complex phase ceramic composite material, which comprises the following steps: (1) to SiO2‑ZrO2Stabilizing the composite sol; (2) dipping the three-dimensional silicon carbide fiber prefabricated member in the stabilized SiO2‑ZrO2In the composite sol; (3) drying the impregnated three-dimensional silicon carbide fiber prefabricated member; (4) heat treatment; (5) and (4) repeating the dipping-drying-heat treatment processes in the steps (2) to (4) until the weight of the three-dimensional silicon carbide fiber reinforced silicon oxide-zirconium oxide complex phase ceramic composite intermediate is increased by less than 1% compared with the previous dipping-drying-heat treatment process, so as to obtain the three-dimensional silicon carbide fiber reinforced silicon oxide-zirconium oxide complex phase ceramic composite. The three-dimensional silicon carbide fiber reinforced silicon oxide-zirconium oxide composite ceramic composite material prepared by the invention has the advantages of high temperature resistance, oxidation resistance, excellent mechanical property and the like.

Description

Three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material and its Preparation method
Technical field
The invention belongs to heat safe fiber reinforced ceramic matrix composites and its preparing technical field more particularly to one kind Three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material and preparation method thereof.
Background technology
Silica-zirconia complex phase ceramic is SiO2And ZrO2React the solid solution structure compound to be formed, and has both SiO2And ZrO2High temperature resistant, it is anti-oxidant, corrosion-resistant the advantages that, be a kind of excellent high temperature ceramic material, in high temperature catalyst Carrier, the refractory material of glass and steel-making kiln, antioxidant coating etc. are with the obvious advantage, have a extensive future.As monomer Ceramics, the fracture toughness of silica-zirconia complex phase ceramic is relatively low, is in most cases 2~3MPam1/2.It has been reported that, i.e., It is nanocrystalline silica-zirconia complex phase ceramic that Fast Sintering obtains to make, and fracture toughness also only has 4.13MPam1/2.Such as This low fracture toughness causes monomeric silicon oxide-zirconium oxide complex phase ceramic to be difficult to obtain practical application as structural material, especially It is in the occasion with the impact of larger mechanical load, thermal shock, it is necessary to carry out toughening processing.
Fiber is introduced in ceramic matrix, has proven to significantly improve the maximally efficient toughening of fracture toughness Method.Silicon carbide fibre high temperature resistant, anti-oxidant, tensile strength and modulus are high, the enhancing as high-performance ceramic based composites It is mutually increasingly taken seriously, is especially applied to long-life oxidation resistant occasion.It therefore, if can be by silicon carbide fibre and SiO2– ZrO2Complex phase ceramic is combined with each other, with reference to the advantage of the two, be theoretically expected to obtain have both high temperature resistant, anti-oxidant, high intensity, The fiber reinforcement silica-zirconia complex phase ceramic composite material of high tenacity.
According to the arrangement mode of fiber in the composite, the i.e. structure type of fiber preform, can be divided into it is one-dimensional, two Dimension, three-dimensional prefab enhancing composite material.One-dimensional composite material refers to the mud for being configured to fibre bundle by ceramic matrix powder Slurry（There is bonding agent that ceramic powders are adhered on fiber in slurry）Be wound in laminated cloth, then by laminated cloth by different directions, no Either directly required shape is wound in angle laying by different directions, different angle then to burn through high temperature pressure-free or hot pressing Tie obtained composite material.The modes such as Two-dimensional Composites refer to by brushing, the mud that dip-coating ceramic matrix powder is configured to The ceramic matrix in fiber cloth surface adhesion, after fiber cloth lamination, the composite wood that is obtained through high temperature pressure-free or hot pressed sintering Material.Three-dimensional composite material refers to first be fabricated to fiber the prefabricated component of 3 D stereo, then passes through the means such as vapor phase method, liquid phase method Ceramic matrix is introduced into obtained composite material in prefabricated component.In comparison, the globality of three-dimensional composite material is more excellent（One In the face of peacekeeping Two-dimensional Composites, interlayer performance it is weaker）, the designability of fiber content and arragement direction is strong, more suitable For the preparation of complex shaped components.
However, due to the difference of preform structure, the densification of three-dimensional composite material is difficult to indiscriminately imitate one-dimensional, two-dimentional composite wood The preparation process of material.For the design feature of three-dimensional prefab, two kinds of densifying methods of generally use at present：First, by prefabricated component After being heated to required temperature, it is passed through gaseous feed, raw material diffuses in prefabricated component that reactive deposition obtains ceramics under high temperature action Matrix, with deposition time increases, hole is gradually filled by ceramic matrix in prefabricated component, and consistency is continuously increased, referred to as gas Xiang Fa；Second is that after prefabricated component is impregnated liquid material, then dry removal solvent is thermally treated resulting in ceramic matrix at high temperature, " dipping-drying-heat treatment " several periods are repeated, hole is gradually filled by ceramic matrix in prefabricated component, and consistency is continuous Increase, referred to as liquid phase method.In contrast, requirement of the liquid phase method to equipment is low, in compound tense equipment temperature field, chemical fields Insensitive, the advantage when prepared by complicated shape and batch component is more obvious.And for fiber reinforcement silica-zirconia For complex phase ceramic composite material, it is suitable for depositing SiO at present2And ZrO2Gaseous feed it is very little, deposition characteristics are also not enough managed Think, liquid material is then easier to obtain, dependable performance.
For liquid phase method, the three-dimensional fiber prefabricated component enhancing of high-compactness, strong mechanical performance how is quickly prepared Silica-zirconia complex phase ceramic composite material, is a critical issue for needing to solve, and involved key technology point includes Liquid material property, impregnation technology, heat treatment process.It does not find also to prepare three-dimensional silicon carbide fibre preforms by liquid phase method at present The research report of part enhancing silica-zirconia complex phase ceramic composite material.
Invention content
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide a kind of high temperature resistant, anti-oxidant and power Learn three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material of function admirable and preparation method thereof.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of preparation method of three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material, including following step Suddenly：
（1）Prepare SiO2-ZrO2Complex sol：By SiO2Colloidal sol and ZrO2Colloidal sol mixes, and adds in stabilizer, obtains SiO2-ZrO2 Complex sol；
（2）Dipping：Three-dimensional silicon carbide fiber preform is placed in container, step is sucked after vacuumizing（1）The SiO of gained2- ZrO2Complex sol carries out vacuum impregnation, makes the SiO2-ZrO2Complex sol is filled in three-dimensional silicon carbide fiber preform；
（3）It is dry：Three-dimensional silicon carbide fiber preform is taken out into drying, to remove SiO2-ZrO2Solvent in complex sol and Stabilizer；
（4）Heat treatment：It is heat-treated under inert atmosphere protection, obtains three-dimensional silicon carbide fiber reinforcement silica-zirconia Complex phase ceramic composite material intermediate；
（5）Repeat step（2）~（4）Dipping-drying-heat treatment process, until three-dimensional silicon carbide fiber reinforcement silica-oxygen Change zirconium complex phase ceramic composite material intermediate compared to last dipping-drying-heat treatment process weightening less than 1%, obtain three-dimensional Silicon carbide fibre enhances silica-zirconia complex phase ceramic composite material.
The preparation method of above-mentioned three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material, preferably , the step（1）In, the stabilizer includes HNO3, HCl or H2SO4In it is one or more.
The preparation method of above-mentioned three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material, preferably , the stabilizer and the SiO2The mass ratio of colloidal sol is 2~3: 10.
The preparation method of above-mentioned three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material, preferably , the step（1）In, the SiO2-ZrO2In complex sol, solid content is 20wt%~40wt%, SiO2With ZrO2Mole Than being 95/5~5/95, colloid size≤30nm of complex sol.
The preparation method of above-mentioned three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material, preferably , the step（3）In, drying temperature is 400 DEG C~700 DEG C, and drying time is 1h~6h.
The preparation method of above-mentioned three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material, preferably , the step（2）In, the vacuum-impregnated process conditions are：Vacuum degree≤500Pa, dip time are 4h~8h.
The preparation method of above-mentioned three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material, preferably , the step（2）In, it is additionally included in after vacuum impregnation under setting pressure and carries out air pressure assistant soakage, make the SiO2-ZrO2 Complex sol is further filled in three-dimensional silicon carbide fiber preform；The process conditions of the air pressure assistant soakage are：It is described Pressure is set as 2MPa~10MPa, dip time is 2h~6h.
The preparation method of above-mentioned three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material, preferably , the step（4）In, the process of thermal treatment process is：Under inert atmosphere protection, with 10 DEG C/min~20 DEG C/min Rate be warming up to 1100 DEG C~1500 DEG C, keep the temperature 0.5h~2h.
The preparation method of above-mentioned three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material, preferably , three-dimensional silicon carbide fiber preform that the three-dimensional silicon carbide fiber preform is sutured for silicon carbide fibre cloth lamination, Three-dimensional silicon carbide fiber preform that silicon carbide fibre cloth and net tire alternative stacked needle pierce, the three of three-dimensional five-way braiding structure Tie up silicon carbide fibre prefabricated component, the three-dimensional silicon carbide fiber preform of two-dimentional half braiding structure, three-dimensional four-way braiding structure three It ties up one or more in silicon carbide fibre prefabricated component；The volume point of silicon carbide fibre in the three-dimensional silicon carbide fiber preform Number is 20%~55%.
The preparation method of above-mentioned three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material, preferably , in the step（2）Three-dimensional silicon carbide fiber preform pre-treatment step is further included before, specially：By the three-dimensional carbon SiClx fiber preform is placed under vacuum or inert atmosphere, and 600 DEG C~1200 are warming up to the rate of 5 DEG C/min~15 DEG C/min DEG C and keep the temperature 1h~4h.
The inventive concept total as one, the present invention also provides silicon carbide three-dimensional made from a kind of above-mentioned preparation method is fine Dimension enhancing silica-zirconia complex phase ceramic composite material, including three-dimensional silicon carbide fiber preform and SiO2-ZrO2Complex phase is made pottery Porcelain, the SiO2-ZrO2In complex phase ceramic, ZrO2The molar content of ceramics is 5%~95%, the SiO2-ZrO2Complex phase ceramic is equal It is even to be filled in the hole of the three-dimensional silicon carbide fiber preform, the three-dimensional silicon carbide fiber reinforcement silica-zirconia The porosity of complex phase ceramic composite material is 8%~15%.
Compared with prior art, the advantage of the invention is that：
1st, the present invention is with SiO2-ZrO2Complex sol is liquid material, and three-dimensional silicon carbide fiber preform is prepared using liquid phase method Enhance silica-zirconia complex phase ceramic composite material, high solids content, nanoscale colloidal sol can make SiO2-ZrO2Particle is fast Speed is filled uniformly in gap in prefabricated component, and compared to the technology path from solution, efficiency of densification is high；It compares In the technology path using the mud that ceramic powders are configured to as raw material, SiO2-ZrO2The distributing homogeneity of particle is good, and generates SiO2-ZrO2The temperature of complex phase ceramic is low, small to the damage of fiber.
The present invention during three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material is prepared, Acid solution is introduced in liquid material silica-zirconia complex sol as stabilizer, solves SiO2Colloidal sol and ZrO2Colloidal sol because Caused by hydrolysis rate is significantly different the problem of poor compatibility, stable SiO is obtained2-ZrO2Complex sol is composite wood The preparation of material provides reliable raw material guarantee.Applicant is preparing SiO2-ZrO2It is found during complex sol, SiO2It is molten Glue and ZrO2It is precipitated after colloidal sol mixing, precipitation destroys the monodisperse status of nano-scale colloidal particle in colloidal sol, obtains Be large scale aggregating state particle, can not be impregnated into the hole of fiber preform, it is impossible to as " dipping-drying-heat The raw material of processing " technology path.Early period was once attempted by diluting, adding the modes such as chelating agent（Principle is increases steric hindrance, drop The collision probability of low colloidal particle）To stablize SiO2-ZrO2Complex sol, but one is that stabilization effect is not too much preferable, second is that meeting The solid content of complex sol is reduced to a certain extent, so as to reduce the preparation efficiency of composite material.In order to preferably stablize SiO2-ZrO2Complex sol, applicant is to SiO2Colloidal sol and ZrO2The reason of generating precipitation after colloidal sol mixing has carried out deep Theoretical research and practical exploration, result of study show：SiO2Colloidal sol is alkaline, ZrO2Colloidal sol is acidity, thus during the two mixing, PH value mismatch, colloidal sol unstability, is precipitated.Reverse thinking of the present invention, according to SiO2Colloidal sol and ZrO2Water in colloidal sol building-up process Mechanism is solved, the colloidal particle part peptization hydrolyzed by adding acid solution collides unstability probability, simultaneously so as to reduce The pH value of the two is adjusted to same level, hence it is evident that improve the stability of complex sol, consolidating for complex sol will not be reduced Content and combined efficiency.In addition, addition acid solution can also reduce the viscosity of complex sol to a certain extent, so as to be conducive to fibre Tie up the dipping in prefabricated component.
Acid solution is preferably strong acid, and strong acid is to SiO2-ZrO2The stablizing effect of complex sol is better than weak acid, wherein, nitric acid pair SiO2-ZrO2The stablizing effect of complex sol is best.
2nd, due to SiO2-ZrO2Contain stabilizer in complex sol, it can be remained in the form of acid group in gel, if not It can be excluded totally, SiO under high temperature can be influenced at a lower temperature2And ZrO2Reaction and sintering, while can also damage carbonization Silica fibre.Present invention selection is in drying stage by improving drying temperature（400 DEG C~700 DEG C）It removes it, in this temperature In the range of, acid group will be decomposed, as nitrate anion can resolve into NOxAnd O2And exclude totally, it so at high temperature would not be because having Gaseous volatilization and influence SiO2And ZrO2Reaction and sintering shrinkage, while be unlikely to that silicon carbide fibre is caused significantly to damage again Wound.
3rd, it is preferred, in colloidal sol used in the present invention, SiO2-ZrO2It is amorphous state, and for nanoscale, surface energy It is very high, thus with high sintering activity, the high-temperature heat treatment for composite material provides good raw material guarantee.
4th, preferred, the present invention using first vacuum impregnation and then air pressure assistant soakage mode, is first vacuumized in impregnation stage The air in prefabricated hollow gap is excluded, the infiltration for colloidal sol provides space, and the individual particle due in colloidal sol being nano-scale is equal The SiO of even dispersion2-ZrO2Composite colloid particle has good stability, it is thus possible to rapidly, evenly into prefabricated component In gap；Then it is acted on by external pressure, colloidal sol is promoted further to be penetrated into prefabricated component inside, complicated into some ducts In gap or even can destroy some closed pores makes it become trepanning, so as to improve pickling efficiency and filling extent.
5th, preferably, the present invention is using the small and stable SiO of amorphous state, grain size2-ZrO2Complex sol is as matrix On the basis of raw material, by SiO2-ZrO2The research of sintering shrinkage behavior, the present invention are 1100 DEG C treatment temperature set ~1500 DEG C, in this temperature range, it both can ensure that SiO2-ZrO2It is converted to SiO2-ZrO2Complex phase ceramic, but can obtain compared with High base densities degree（Matrix is improved to bear load and transmit the ability of load）, the final three-dimensional carbon for obtaining high comprehensive performance SiClx fiber reinforcement silica-zirconia complex phase ceramic composite material.
In short, the present invention sets about in terms of liquid material characteristic, impregnation technology, drying process, heat treatment temperature four, significantly Improve three-dimensional silicon carbide fiber preform enhancing SiO2-ZrO2The compactness extent of complex phase ceramic composite material, both enhances matrix The bearing capacity of itself, and the ability that matrix transmits load is enhanced, thus prepared three-dimensional silicon carbide fiber reinforcement aoxidizes Silicon-zirconium oxide complex phase ceramic composite material shows excellent mechanical property, high temperature resistance and antioxygenic property.
6th, three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material prepared by the present invention for the first time will Silicon carbide fibre, SiO2-ZrO2Complex phase ceramic, three-dimensional prefab three advantage be combined together, obtaining a kind of has excellent power Learn the high temperature resistant of performance, oxidation resistant three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material.Utilize three The mechanical characteristic for tieing up silicon carbide fibre prefabricated component provides excellent mechanical property, is provided in particular in high fracture toughness, overcomes Monomer SiO2-ZrO2The brittleness of complex phase ceramic；Utilize SiO2-ZrO2Complex phase ceramic and the excellent anti-oxidation characteristics of silicon carbide fibre, There is provided composite material excellent antioxygenic property；Utilize the high-temperature stability and SiO of silicon carbide fibre2-ZrO2The height of complex phase ceramic Fusing point provides composite material excellent heat-resisting ability.Also, the composite material porosity is relatively low（8%~15%）Namely SiO2-ZrO2Content and consistency are high, thus the composite material has excellent mechanical property, high temperature resistance and inoxidizability Energy.
Description of the drawings
Fig. 1 is the three-dimensional silicon carbide fiber reinforcement SiO prepared by the embodiment of the present invention 12-ZrO2Complex phase ceramic composite material Photomacrograph.
Fig. 2 is the three-dimensional silicon carbide fiber reinforcement SiO prepared by the embodiment of the present invention 12-ZrO2Complex phase ceramic composite material Micro-structure diagram.
Fig. 3 is the matrix material SiO of the present invention2-ZrO2Complex sol（SiO2With ZrO2Molar ratio be 1: 1）Through drying The XRD spectrum of gained gel powder.
Fig. 4 is the matrix material SiO of the present invention2-ZrO2Complex sol（SiO2With ZrO2Molar ratio be 1: 1）Through drying Gel powder afterwards, it is repressed it is blocking after, at different temperatures be heat-treated after linear shrinkage situation.
Fig. 5 is the matrix material SiO of the present invention2-ZrO2Complex sol（SiO2With ZrO2Molar ratio be 1: 1）Through drying Gel powder afterwards, the XRD spectrum after different temperatures heat treatment.
Specific embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and It limits the scope of the invention.
Embodiment 1：
A kind of preparation method of the three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material of the present invention, packet Include processing step in detail below：
（1）Colloidal sol is chosen：Choose the SiO that solid concentration is 40wt%2-ZrO2Complex sol is as SiO2-ZrO2Complex phase ceramic base The raw material of body, wherein SiO2With ZrO2Molar ratio for 1: 1, in above-mentioned SiO2-ZrO2HNO is added in complex sol3As stabilization Agent, HNO3Addition is SiO2The 30% of sol weight.
（2）Prefabricated component pre-processes：Choose the three-dimensional silicon carbide fibre that silicon carbide fibre cloth is pierced with net tire alternative stacked needle Dimension prefabricated component is reinforced phase, and the volume fraction of fiber is 24% in three-dimensional silicon carbide fiber preform.By the three-dimensional silicon carbide of selection Fiber preform is placed under vacuum, is warming up to 600 DEG C with the rate of 5 DEG C/min and is kept the temperature 4h, then cools down with stove, is completed prefabricated The pretreatment of part.
（3）Vacuum impregnation：Pretreated three-dimensional silicon carbide fiber preform is placed in vacuum tank, is evacuated to vacuum When degree reaches 500Pa, step is sucked（1）SiO2-ZrO2Complex sol makes SiO2-ZrO2Complex sol floods three-dimensional silicon carbide Fiber preform impregnates 8h.
（4）Air pressure assistant soakage：By prefabricated component（Still it is immersed in colloidal sol）It moves in autoclave pressure, is inflated to 2MPa, carry out Air pressure assistant soakage keeps 6h.
（5）It is dry：Three-dimensional silicon carbide fiber preform is taken out from colloidal sol, in an inert atmosphere dry 6h at 400 DEG C.
（6）Heat treatment：By dried three-dimensional silicon carbide fiber preform under high purity inert gas protection, with 10 DEG C/ The rate of min is warming up to 1100 DEG C, and keeps the temperature 2h, then cools down with stove, obtains three-dimensional silicon carbide fiber reinforcement silica-oxidation Zirconium complex phase ceramic composite material intermediate.
（7）Repetitive process：Repeat step（3）~（6）, totally 28 times, after testing, after last time is handled, three-dimensional silicon carbide Treated that rate of body weight gain is 0.89% compared to last for fiber reinforcement silica-zirconia complex phase ceramic composite material intermediate, Recombination process finishes, and obtains three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material.
Fig. 1 is the three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite wood that the present embodiment is prepared The photomacrograph of material.After testing, the three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic that the present embodiment obtains is compound The porosity of material is 9.6%, bending strength 117.0MPa, fracture toughness 7.1MPam1/2.Through 1500 DEG C of high temperature inerts After 1h being heat-treated in atmosphere, strength retention ratio 97.3%；After 1500 DEG C of still airs aoxidize 0.5h, strength retention ratio 98.6%.
Fig. 2 is the three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite wood that the present embodiment is prepared The micro-structure diagram of material, it can be seen that it, which is formed, includes three-dimensional silicon carbide fiber preform and SiO2-ZrO2Complex phase ceramic, In, SiO2-ZrO2Complex phase ceramic is matrix, SiO2With ZrO2Molar ratio for 1: 1, three-dimensional silicon carbide fiber preform is enhancing Phase, SiO2-ZrO2Into bulk after complex phase ceramic particles sintering, it is uniformly filled in the gap between fibre bundle inside i.e. fiber.
Embodiment 2：
A kind of preparation method of the three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material of the present invention, packet Include processing step in detail below：
（1）Colloidal sol is chosen：Choose the SiO that solid concentration is 30wt%2-ZrO2Complex sol is as SiO2-ZrO2Complex phase ceramic base The raw material of body, wherein SiO2With ZrO2Molar ratio is 95: 5, in above-mentioned SiO2-ZrO2HNO is added in complex sol3As stabilization Agent, HNO3Addition be SiO2The 25% of sol weight.
（2）Prefabricated component pre-processes：Choosing the three-dimensional silicon carbide fiber preform that silicon carbide fibre cloth lamination sutures is Reinforced phase, the volume fraction of fiber is 46% in three-dimensional silicon carbide fiber preform.By the three-dimensional silicon carbide fiber preform of selection It is placed under vacuum, 1000 DEG C are warming up to the rate of 10 DEG C/min and keep the temperature 2h, then cool down with stove, complete the pre- place of prefabricated component Reason.
（3）Vacuum impregnation：Pretreated three-dimensional silicon carbide fiber preform is placed in vacuum tank, is evacuated to vacuum When degree reaches 300Pa, step is sucked（1）SiO2-ZrO2Complex sol makes SiO2-ZrO2Complex sol floods three-dimensional silicon carbide Fiber preform impregnates 6h.
（4）Air pressure assistant soakage：By prefabricated component（Still it is immersed in colloidal sol）It moves in autoclave pressure, is inflated to 4MPa, carry out Air pressure assistant soakage keeps 4h.
（5）It is dry：Three-dimensional silicon carbide fiber preform is taken out from colloidal sol, in an inert atmosphere dry 2h at 500 DEG C.
（6）Heat treatment：By dried three-dimensional silicon carbide fiber preform under high purity inert gas protection, with 15 DEG C/ The rate of min is warming up to 1200 DEG C, and keeps the temperature 1.5h, then cools down with stove, obtains three-dimensional silicon carbide fiber reinforcement silica-oxygen Change zirconium complex phase ceramic composite material intermediate.
（7）Repetitive process：Repeat step（3）~（6）, totally 24 times, after testing, after last time is handled, three-dimensional silicon carbide Treated that rate of body weight gain is 0.88% compared to last for fiber reinforcement silica-zirconia complex phase ceramic composite material intermediate, Recombination process finishes, and obtains three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material.
After testing, the three-dimensional silicon carbide fiber preform enhancing SiO that the present embodiment obtains2-ZrO2Complex phase ceramic composite material Porosity for 14.4%, bending strength 202.5MPa, fracture toughness 11.7MPam1/2.Through 1500 DEG C of high temperature inert gas After 1h being heat-treated in atmosphere, strength retention ratio 92.1%；After 1500 DEG C of still airs aoxidize 0.5h, strength retention ratio 96.7%.Its Composition includes three-dimensional silicon carbide fiber preform and SiO2-ZrO2Complex phase ceramic, wherein, SiO2-ZrO2Complex phase ceramic is matrix, SiO2With ZrO2Molar ratio for 95: 5, three-dimensional silicon carbide fiber preform is reinforced phase, SiO2-ZrO2Complex phase ceramic is uniformly filled out It fills in the gap of three-dimensional silicon carbide fiber preform.
Embodiment 3：
A kind of preparation method of the three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material of the present invention, packet Include processing step in detail below：
（1）Colloidal sol is chosen：Choose the SiO that solid concentration is 35wt%2-ZrO2Complex sol is as SiO2-ZrO2Complex phase ceramic base The raw material of body, wherein SiO2With ZrO2Molar ratio is 5: 95, in above-mentioned SiO2-ZrO2HNO is added in complex sol3As stabilization Agent, HNO3Addition is SiO2The 20% of sol weight.
（2）Prefabricated component pre-processes：The three-dimensional silicon carbide fiber preform for choosing three-dimensional four-way braiding structure is reinforced phase, three The volume fraction for tieing up fiber in silicon carbide fibre prefabricated component is 51%.The three-dimensional silicon carbide fiber preform of selection is placed in high-purity It in argon gas atmosphere, is warming up to 1200 DEG C with the rate of 15 DEG C/min and keeps the temperature 1h, then cool down with stove, complete the pre- place of prefabricated component Reason.
（3）Vacuum impregnation：Pretreated three-dimensional silicon carbide fiber preform is placed in vacuum tank, is evacuated to vacuum When degree reaches 100Pa, step is sucked（1）SiO2-ZrO2Complex sol makes SiO2-ZrO2Complex sol floods three-dimensional silicon carbide Fiber preform impregnates 4h.
（4）Air pressure assistant soakage：By prefabricated component（Still it is immersed in colloidal sol）It moves in autoclave pressure, is inflated to 8MPa, carry out Air pressure assistant soakage keeps 6h.
（5）It is dry：Three-dimensional silicon carbide fiber preform is taken out from colloidal sol, in an inert atmosphere dry 4h at 400 DEG C.
（6）Heat treatment：By dried three-dimensional silicon carbide fiber preform under high purity inert gas protection, with 15 DEG C/ The rate of min is warming up to 1500 DEG C, and keeps the temperature 0.5h, then cools down with stove, obtains three-dimensional silicon carbide fiber reinforcement silica-oxygen Change zirconium complex phase ceramic composite material intermediate.
（7）Repetitive process：Repeat step（3）~（6）, totally 30 times, after testing, after last time is handled, three-dimensional silicon carbide Treated that rate of body weight gain is 0.90% compared to last for fiber reinforcement silica-zirconia complex phase ceramic composite material intermediate, Recombination process finishes, and obtains three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material.
After testing, the three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic that the present embodiment is prepared is compound The porosity of material is 8.6%, bending strength 286.4MPa, fracture toughness 13.5MPam1/2.Through 1500 DEG C of high temperature inerts After 1h being heat-treated in atmosphere, strength retention ratio 97.7%；After 1500 DEG C of still airs aoxidize 0.5h, strength retention ratio 98.1%. It, which is formed, includes three-dimensional silicon carbide fiber preform and SiO2-ZrO2Complex phase ceramic, wherein, SiO2-ZrO2Complex phase ceramic is base Body, ZrO2Molar content in complex phase ceramic is 95%, and three-dimensional silicon carbide fiber preform is reinforced phase, SiO2-ZrO2Complex phase Ceramics are uniformly filled in the gap of three-dimensional silicon carbide fiber preform.
Embodiment 4：
A kind of preparation method of the three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material of the present invention, packet Include processing step in detail below：
（1）Colloidal sol is chosen：Choose the SiO that solid concentration is 20wt%2-ZrO2Complex sol is as SiO2-ZrO2Complex phase ceramic base The raw material of body, wherein SiO2With ZrO2Molar ratio for 3: 1, in above-mentioned SiO2-ZrO2HNO is added in complex sol3As stabilization Agent, HNO3Addition is SiO2The 20% of sol weight.
（2）Prefabricated component pre-processes：The three-dimensional silicon carbide fiber preform for choosing two-dimentional half braiding structure is reinforced phase, three-dimensional The volume fraction of fiber is 43% in silicon carbide fibre prefabricated component.The three-dimensional silicon carbide fiber preform of selection is placed under vacuum, 800 DEG C are warming up to the rate of 10 DEG C/min and keeps the temperature 3h, is then cooled down with stove, complete the pretreatment of prefabricated component.
（3）Vacuum impregnation：Pretreated three-dimensional silicon carbide fiber preform is placed in vacuum tank, is evacuated to vacuum When degree reaches 200Pa, step is sucked（1）SiO2-ZrO2Complex sol makes SiO2-ZrO2Complex sol floods three-dimensional silicon carbide Fiber preform impregnates 8h.
（4）Air pressure assistant soakage：By prefabricated component（Still it is immersed in colloidal sol）It moves in autoclave pressure, is inflated to 10MPa, carry out Air pressure assistant soakage keeps 2h.
（5）It is dry：Three-dimensional silicon carbide fiber preform is taken out from colloidal sol, in an inert atmosphere dry 1h at 700 DEG C.
（6）Heat treatment：By dried three-dimensional silicon carbide fiber preform under high purity inert gas protection, with 10 DEG C/ The rate of min is warming up to 1300 DEG C, and keeps the temperature 1h, then cools down with stove, obtains three-dimensional silicon carbide fiber reinforcement silica-oxidation Zirconium complex phase ceramic composite material intermediate.
（7）Repetitive process：Repeat step（3）~（6）, totally 26 times, after testing, after last time is handled, three-dimensional silicon carbide Treated that rate of body weight gain is 0.78% compared to last for fiber reinforcement silica-zirconia complex phase ceramic composite material intermediate, Recombination process finishes, and obtains three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material.
After testing, the three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic that the present embodiment is prepared is compound The porosity of material is 12.5%, bending strength 231.2MPa, fracture toughness 11.2MPam1/2.It is lazy through 1500 DEG C of high temperature Property atmosphere in heat treatment 1h after, strength retention ratio 95.4%；After 1500 DEG C of still airs aoxidize 0.5h, strength retention ratio 97.6%.It, which is formed, includes three-dimensional silicon carbide fiber preform and SiO2–ZrO2Complex phase ceramic, wherein, SiO2-ZrO2Complex phase ceramic For matrix, SiO2With ZrO2Molar ratio for 3: 1, three-dimensional silicon carbide fiber preform is reinforced phase, SiO2-ZrO2Complex phase ceramic It is uniformly filled in the gap of three-dimensional silicon carbide fiber preform.
Embodiment 5：
A kind of preparation method of the three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material of the present invention, packet Include processing step in detail below：
（1）Colloidal sol is chosen：Choose the SiO that solid concentration is 30wt%2-ZrO2Complex sol is as SiO2-ZrO2Complex phase ceramic base The raw material of body, wherein SiO2With ZrO2Molar ratio for 1: 3, in above-mentioned SiO2-ZrO2HNO is added in complex sol3As stabilization Agent, HNO3Addition is SiO2The 25% of sol weight.
（2）Prefabricated component pre-processes：The three-dimensional silicon carbide fiber preform for choosing three-dimensional five-way braiding structure is reinforced phase, three The volume fraction for tieing up fiber in silicon carbide fibre prefabricated component is 50%.The three-dimensional silicon carbide fiber preform of selection is placed in high-purity It in argon gas atmosphere, is warming up to 1000 DEG C with the rate of 10 DEG C/min and keeps the temperature 2h, then cool down with stove, complete the pre- place of prefabricated component Reason.
（3）Vacuum impregnation：Pretreated three-dimensional silicon carbide fiber preform is placed in vacuum tank, is evacuated to vacuum When degree reaches 400Pa, step is sucked（1）SiO2-ZrO2Complex sol makes SiO2-ZrO2Complex sol floods three-dimensional silicon carbide Fiber preform impregnates 6h.
（4）Air pressure assistant soakage：By prefabricated component（Still it is immersed in colloidal sol）It moves in autoclave pressure, is inflated to 6MPa, carry out Air pressure assistant soakage keeps 4h.
（5）It is dry：Three-dimensional silicon carbide fiber preform is taken out from colloidal sol, in an inert atmosphere dry 3h at 600 DEG C.
（6）Heat treatment：By dried three-dimensional silicon carbide fiber preform under high purity inert gas protection, with 20 DEG C/ The rate of min is warming up to 1400 DEG C, and keeps the temperature 1h, then cools down with stove, obtains three-dimensional silicon carbide fiber reinforcement silica-oxidation Zirconium complex phase ceramic composite material intermediate.
（7）Repetitive process：Repeat step（3）~（6）, totally 27 times, after testing, after last time is handled, three-dimensional silicon carbide Treated that rate of body weight gain is 0.95% compared to last for fiber reinforcement silica-zirconia complex phase ceramic composite material intermediate, Recombination process finishes, and obtains three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material.
After testing, the three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic that the present embodiment is prepared is compound The porosity of material is 11.3%, bending strength 312.4MPa, fracture toughness 13.2MPam1/2.It is lazy through 1500 DEG C of high temperature Property atmosphere in heat treatment 1h after, strength retention ratio 97.1%；After 1500 DEG C of still airs aoxidize 0.5h, strength retention ratio 97.6%.It, which is formed, includes three-dimensional silicon carbide fiber preform and SiO2-ZrO2Complex phase ceramic, wherein, SiO2-ZrO2Complex phase ceramic For matrix, SiO2With ZrO2Molar ratio for 1: 3, three-dimensional silicon carbide fiber preform is reinforced phase, SiO2-ZrO2Complex phase ceramic It is uniformly filled in the gap of three-dimensional silicon carbide fiber preform.
By embodiment 1 to 5 it is found that the present invention preparation method be prepared three-dimensional silicon carbide fiber reinforcement silica- Zirconium oxide complex phase ceramic composite material has low porosity, strong mechanical performance and excellent high temperature oxidation resistance.
In conclusion the present invention bases oneself upon SiO2-ZrO2The characteristics of complex phase ceramic, present Research with there are the problem of, with reference to carbon SiClx fiber, SiO2-ZrO2Complex phase ceramic, the advantage of three-dimensional prefab three provide three-dimensional silicon carbide fiber reinforcement SiO2- ZrO2This new material system of complex phase ceramic composite material, and form the preparation method that can obtain excellent performance.
In preparation method, first by adding HNO3For additive, stable SiO is obtained2-ZrO2Complex sol is Composite material preparation provides reliable raw material guarantee, then uses SiO of the solid concentration for 20wt%~40wt%2-ZrO2It is multiple Close colloidal sol（Colloidal particle size≤30nm）For matrix material, in limit cycle（Nearly 30 periods）Only have with regard to porosity can be prepared 11% or so, bending strength up to 312.4MPa, fracture toughness up to 13.2MPam1/2Three-dimensional five-way silicon carbide fibre enhancing SiO2-ZrO2Complex phase ceramic composite material.Although the three-dimensional five-way silicon carbide fibre prepared without completely corresponding other methods increases Strong SiO2-ZrO2Complex phase ceramic composite material can compare, but can be compared with the similar prior art：First, existing skill AlCl is used in art3·6H2O or Al (NO3)3·9H2The colloidal sol that O inorganic salts are configured to is matrix material, passes through 13 periods " dipping--1260 DEG C of drying heat treatment " prepares three-dimensional four-way fibre reinforced Al2O3Composite material finds follow-up continuation compound tense Density no longer increases, and porosity 30% or so, bending strength is only 100MPa~150MPa；Second is that contain Si organic salts with having containing Y Machine salting liquid prepares Y2SiO5Coating needs removing to fall a large amount of solvents and additive, and preparation efficiency is very low, and a canonical parameter is 20 Best-Effort request heat treatment, just 2 μm of thickness are done.Therefore, by comparing it can be found that using high solid loading SiO2-ZrO2 Complex sol is as SiO2-ZrO2Complex phase ceramic matrix material, compared to the technology road of the solution from organic or inorganic salt Line, the advantage on preparation efficiency are self-evident.
In addition, the three-dimensional silicon carbide fiber reinforcement SiO using the scanning electronic microscope observation present invention2-ZrO2Complex phase is made pottery The microstructure of porcelain composite material, as shown in Figure 2, it can be seen that, SiO2-ZrO2Into bulk after complex phase ceramic particles sintering, uniformly Be filled in inside fibre bundle the gap between i.e. fiber, avoid that mud raw material is susceptible to the problem of being unevenly distributed.Cause This, the SiO that the present invention uses2-ZrO2Complex sol, had both maintained inorganic salts or organic slat solution raw material can fill uniformly The advantages of advantage and mud raw material high efficiency impregnate, and overcome inorganic salts or organic slat solution raw material efficiency of densification is inclined The shortcomings that low and mud raw material fill non-uniform shortcoming.
Next, the present invention using first vacuum impregnation and then air pressure assistant soakage mode, first vacuumize exclude it is prefabricated in Air in gap, the infiltration for colloidal sol provide space, due to being SiO that the individual particle of nano-scale uniformly disperses in colloidal sol2- ZrO2Composite colloid particle has good stability, it is thus possible to rapidly, evenly into the gap of prefabricated component；Then It is acted on by external pressure, colloidal sol is promoted further to be penetrated into prefabricated component inside, into the gap of some ducts complexity, even Some closed pores, which can be destroyed, makes it become trepanning, so as to improve pickling efficiency and filling extent.
Finally, in colloidal sol used in the present invention, SiO2-ZrO2It is amorphous state, and is nanoscale, surface can be very high, Thus with high sintering activity.On this basis, by SiO2-ZrO2The research of sintering shrinkage behavior, the present invention is at heat Reason temperature is set as 1100 DEG C~1500 DEG C, in this temperature range, both can ensure that SiO2-ZrO2It is converted to SiO2-ZrO2It is multiple Phase ceramics, and higher base densities degree can be obtained（Matrix is improved to bear load and transmit the ability of load）, while will not Lead to reacting between matrix and silicon carbide fibre（It avoids the formation of chemical strong combination interface and damages the mechanical property of silicon carbide fibre Energy）, the final three-dimensional silicon carbide fiber reinforcement SiO for obtaining high comprehensive performance2-ZrO2Complex phase ceramic composite material.
To SiO2-ZrO2The gel powder obtained after drying sol carries out XRD detections：
Gel powder is analyzed using D8 Advance types X-ray diffractometer（SiO2With ZrO2Molar ratio be 1: 1）Phase composition. Test condition is：CuK alpha rays, tube current 40mA, tube voltage 40KV, 2 θ=10~60 °, 4 °/min of sweep speed.
Testing result is referring to Fig. 3, as seen from the figure：" steamed bun " peak feature is presented in collection of illustrative plates, sharp SiO does not occur2Or ZrO2 Characteristic diffraction peak shows through 700 DEG C of dried SiO2-ZrO2Gel powder be typical amorphous state, unbodied state With high surface energy, can be densified with acceleration of sintering.
To SiO2-ZrO2The gel powder obtained after drying sol, it is repressed it is blocking after, it is hot at different temperatures to it Treated, and linear shrinkage situation is detected：
By dried SiO2-ZrO2Gel powder（SiO2With ZrO2Molar ratio be 1: 1）It is put into the metal die of diameter 40mm In, powder is pressed into the round block of diameter 40mm, thickness 5mm on press under 100MPa.Round block is put into heat-treatment furnace, After being heat-treated 1h at different temperatures, the change rate of diameter, thickness before and after being heat-treated is measured, it is final to survey 5 points and be averaged As a result.
Testing result is referring to Fig. 4, as seen from the figure：After 1100 DEG C~1500 DEG C heat treatment, linear shrinkage ratio is in 9%~14% model It increases with temperature in enclosing and gradually increases, wherein, when temperature is from when being increased to 1300 DEG C for 1200 DEG C, linear shrinkage ratio increase is unknown It is aobvious, illustrate SiO2-ZrO2With preferable sintering activity.According to Fig. 4 data it can be extrapolated that being heat-treated at less than 1100 DEG C, linear shrinkage Rate can further decline, and be unfavorable for densified sintering product, so the present invention selects heat treatment temperature lower limit as 1100 DEG C.
SiO after being heat-treated to different temperatures2-ZrO2Gel powder carries out XRD detections：
The SiO that will be obtained after drying2-ZrO2Gel powder（SiO2With ZrO2Molar ratio be 1: 1）It is placed under different temperatures at heat 1h is managed, then using the phase composition of D8 Advance type X-ray diffractometer analysed for powder.Test condition is：CuK alpha rays, pipe electricity Flow 40mA, tube voltage 40KV, 2 θ=10~60 °, 4 °/min of sweep speed.
Testing result is referring to Fig. 5, as seen from the figure：At 1100 DEG C~1300 DEG C, SiO2-ZrO2With ZrO in complex phase ceramic2 Based on crystalline phase, SiO2There is no crystallize or crystallize it is faint and by ZrO2It masks, 1400 DEG C of whens start to generate zircon （ZrSiO4）Phase, the crystallization degree of zircon increased at 1500 DEG C.According to the literature, after more than 1600 DEG C, zircon Mutually SiO can be resolved into again2And ZrO2, and SiO at this time2And ZrO2It is easy to react with silicon carbide fibre, to Compound Material Engineering It can be unfavorable.Therefore, the present invention selects the heat treatment temperature upper limit as 1500 DEG C.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned implementation Example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that for the art Those of ordinary skill for, improvements and modifications without departing from the principle of the present invention, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

1. a kind of preparation method of three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material, including following Step：
（1）Prepare SiO2-ZrO2Complex sol：By SiO2Colloidal sol and ZrO2Colloidal sol mixes, and adds in stabilizer, obtains SiO2-ZrO2 Complex sol；
（2）Dipping：Three-dimensional silicon carbide fiber preform is placed in container, step is sucked after vacuumizing（1）The SiO of gained2- ZrO2Complex sol carries out vacuum impregnation, makes the SiO2-ZrO2Complex sol is filled in three-dimensional silicon carbide fiber preform；
（3）It is dry：Three-dimensional silicon carbide fiber preform is taken out into drying, to remove SiO2-ZrO2Solvent in complex sol and steady Determine agent；
（4）Heat treatment：It is heat-treated under inert atmosphere protection, obtains three-dimensional silicon carbide fiber reinforcement silica-zirconia Complex phase ceramic composite material intermediate；
（5）Repeat step（2）~（4）Dipping-drying-heat treatment process, until three-dimensional silicon carbide fiber reinforcement silica-oxygen Change zirconium complex phase ceramic composite material intermediate compared to last dipping-drying-heat treatment process weightening less than 1%, obtain three-dimensional Silicon carbide fibre enhances silica-zirconia complex phase ceramic composite material.
2. the system of three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material according to claim 1 Preparation Method, which is characterized in that the step（1）In, the stabilizer includes HNO3, HCl or H2SO4In it is one or more.
3. the system of three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material according to claim 2 Preparation Method, which is characterized in that the stabilizer and the SiO2The mass ratio of colloidal sol is 2~3: 10.
4. the system of three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material according to claim 3 Preparation Method, which is characterized in that the step（1）In, the SiO2-ZrO2In complex sol, solid content is 20wt%~40wt%, SiO2With ZrO2Molar ratio for 95/5~5/95, colloid size≤30nm of complex sol.
It is 5. compound according to Claims 1 to 4 any one of them three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic The preparation method of material, which is characterized in that the step（3）In, drying temperature be 400 DEG C~700 DEG C, drying time for 1h~ 6h。
6. the system of three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material according to claim 5 Preparation Method, which is characterized in that the step（2）In, the vacuum-impregnated process conditions are：Vacuum degree≤500Pa, during dipping Between be 4h~8h.
7. the system of three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material according to claim 6 Preparation Method, which is characterized in that the step（2）In, it is additionally included in after vacuum impregnation under setting pressure and carries out air pressure assistant soakage, Make the SiO2-ZrO2Complex sol is further filled in three-dimensional silicon carbide fiber preform；The work of the air pressure assistant soakage Skill condition is：For the pressure that sets as 2MPa~10MPa, dip time is 2h~6h.
8. three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material described according to claim 6 or 7 Preparation method, which is characterized in that the step（4）In, the process of thermal treatment process is：Under inert atmosphere protection, with The rate of 10 DEG C/min~20 DEG C/min is warming up to 1100 DEG C~1500 DEG C, keeps the temperature 0.5h~2h.
9. the system of three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase ceramic composite material according to claim 8 Preparation Method, which is characterized in that the three-dimensional silicon carbide fiber preform is the three-dimensional carbon that silicon carbide fibre cloth lamination sutures Three-dimensional silicon carbide fiber preform that SiClx fiber preform, silicon carbide fibre cloth and net tire alternative stacked needle pierce, three-dimensional The three-dimensional silicon carbide fiber preform of five-way braiding structure, the three-dimensional silicon carbide fiber preform of two-dimentional half braiding structure, three-dimensional It is one or more in the three-dimensional silicon carbide fiber preform of four-way braiding structure；Carbon in the three-dimensional silicon carbide fiber preform The volume fraction of SiClx fiber is 20%~55%.
10. one kind three-dimensional silicon carbide fiber reinforcement silica as made from claim 1~9 any one of them preparation method- Zirconium oxide complex phase ceramic composite material, which is characterized in that including three-dimensional silicon carbide fiber preform and SiO2-ZrO2Complex phase ceramic, The SiO2-ZrO2In complex phase ceramic, ZrO2The molar content of ceramics is 5%~95%, the SiO2-ZrO2Complex phase ceramic is uniformly filled out It fills in the hole of the three-dimensional silicon carbide fiber preform, the three-dimensional silicon carbide fiber reinforcement silica-zirconia complex phase The porosity of ceramic composite is 8%~15%.
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CN108658616A (en) * 2018-07-09 2018-10-16 中国人民解放军国防科技大学 ZrO (ZrO)2-SiO2Low-temperature rapid preparation method of base composite material
CN112745143A (en) * 2021-01-05 2021-05-04 北京化工大学 ZrO preparation by adopting sol-gel method2-SiO2Method for coating C/C composite material with-SiC
CN114085089A (en) * 2021-11-03 2022-02-25 福建立亚新材有限公司 Preparation method of waste continuous silicon carbide fiber reinforced silicate ceramic

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