CN110563479A - Ultrahigh-temperature ceramic matrix composite and preparation method thereof - Google Patents

Ultrahigh-temperature ceramic matrix composite and preparation method thereof Download PDF

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Publication number
CN110563479A
CN110563479A CN201911022737.2A CN201911022737A CN110563479A CN 110563479 A CN110563479 A CN 110563479A CN 201911022737 A CN201911022737 A CN 201911022737A CN 110563479 A CN110563479 A CN 110563479A
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carbon
phenolic resin
temperature
ultrahigh
slurry
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李晓东
陈艳武
陈鑫阳
霍鹏飞
于新民
赵英民
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Aerospace Research Institute of Materials and Processing Technology
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Aerospace Research Institute of Materials and Processing Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • C04B35/83—Carbon fibres in a carbon matrix
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428—Silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5216—Inorganic
    • C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
    • C04B2235/5248—Carbon, e.g. graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/616—Liquid infiltration of green bodies or pre-forms

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Products (AREA)

Abstract

the invention relates to an ultrahigh-temperature ceramic matrix composite and a preparation method thereof. The preparation method comprises the following steps: mixing ceramic powder and thermosetting phenolic resin to prepare slurry; compounding the slurry and the carbon cloth by adopting a hot melt adhesive membrane method to obtain a prepreg; stacking prepreg layers and preparing a molding flat plate; carrying out thermal cracking on the mould pressing flat plate to obtain a carbon/carbon blank; processing the carbon/carbon blank to obtain the carbon/carbon blank with the anti-silicification interface layer; carrying out densification treatment on the carbon/carbon blank with the anti-silicification interface layer by using a PIP (polysilicon-insulator-polysilicon) process to obtain a carbon/carbon matrix; and covering the carbon/carbon matrix with silicon powder, and performing melt siliconizing by adopting a reaction infiltration method to obtain the ultrahigh-temperature ceramic-based composite material. The composite material prepared by the method has excellent mechanical properties and has substantial benefits in the field of aerospace.

Description

ultrahigh-temperature ceramic matrix composite and preparation method thereof
Technical Field
the invention relates to the technical field of ultra-high temperature ceramic matrix composite materials, in particular to an ultra-high temperature ceramic matrix composite material and a preparation method thereof.
Background
The ultrahigh-temperature ceramic matrix composite has a series of excellent performances such as high temperature resistance, ablation resistance and thermal shock resistance, and has a wide application prospect in the field of aerospace aviation. The preparation process of the ultrahigh-temperature ceramic is generally a precursor impregnation-pyrolysis method and a slurry method. The ultrahigh-temperature ceramic matrix composite prepared by the precursor impregnation-pyrolysis method has excellent ablation resistance, but has long preparation period, high cost and high porosity of the composite. The slurry method is to prepare slurry with a certain proportion by adopting ultrahigh-temperature ceramic powder and a precursor, and then prepare the ultrahigh-temperature ceramic matrix composite by adopting a dipping or hot-pressing process. Because the density of the ultrahigh-temperature ceramic powder is higher, the phenomena of closed pores, crusting and the like which influence the impregnation effect are easily formed in the impregnation process, and the material density is lower, so that the mechanical property of the material is influenced.
In recent years, ultra-high temperature ceramic-based composite materials are developed, wherein phenolic resin solution is prepared by adopting ultra-high temperature ceramic powder, then carbon cloth is coated by adopting a coating process, then a composite material flat plate is prepared by adopting a mould pressing process, and melting siliconizing is carried out after the flat plate is cracked. The process has the advantages of short preparation period and the disadvantages of low additive amount of the ultrahigh-temperature ceramic powder and low performance of the composite material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a rapid preparation method of an ultrahigh-temperature ceramic-based composite material and the ultrahigh-temperature ceramic-based composite material.
In order to achieve the purpose, the invention provides the following technical scheme:
1. A preparation method of an ultrahigh-temperature ceramic matrix composite material comprises the following steps:
(1) Mixing ceramic powder and thermosetting phenolic resin to prepare slurry;
(2) Compounding the slurry and the carbon cloth by adopting a hot melt adhesive membrane method to obtain a prepreg;
(3) stacking prepreg layers and preparing a molding flat plate; carrying out thermal cracking on the mould pressing flat plate to obtain a carbon/carbon blank;
(4) processing the carbon/carbon blank to obtain the carbon/carbon blank with the anti-silicification interface layer;
(5) carrying out densification treatment on the carbon/carbon blank with the anti-silicification interface layer by using a PIP (polysilicon-insulator-polysilicon) process to obtain a carbon/carbon matrix;
(6) and covering the carbon/carbon matrix with silicon powder, and performing melt siliconizing by adopting a reaction infiltration method to obtain the ultrahigh-temperature ceramic-based composite material.
2. According to the preparation method of claim 1, in the step (1), the thermosetting phenolic resin is selected from any one or more of boron phenolic resin, barium phenolic resin and ammonia phenolic resin, preferably barium phenolic resin; and/or
The ceramic powder is selected from zirconium carbide powder and/or zirconium boride powder.
3. according to the preparation method of the technical scheme 2, the mass percentage of the ceramic powder in the slurry is 10-70%.
4. According to the preparation method of the technical scheme 1, in the step (2), the slurry accounts for 50-70% of the mass percentage of the prepreg.
5. According to the preparation method of the technical scheme 1, in the step (3), when the mould pressing flat plate is prepared, the volume fraction of the fibre of the mould pressing flat plate is 28-60% through ply numerical control moulding; and/or
The mould pressing flat plate is prepared by adopting a mould pressing process, and the process conditions of the mould pressing process are as follows:
the pressurizing temperature is 100-120 ℃;
The curing temperature is 180-190 ℃;
the heat preservation time is 4-5 h.
6. The preparation method according to claim 1, wherein in step (3), the thermal cracking is performed under an inert atmosphere, and the thermal cracking process conditions are as follows:
The heating rate is 0.5 ℃/min to 1 ℃/min, and the thermal cracking temperature is 600 ℃ to 1000 ℃.
7. According to the preparation method of the technical scheme 1, in the step (4), a chemical vapor infiltration process is adopted to treat the carbon/carbon blank, and the process conditions of the chemical vapor infiltration process are as follows:
The deposition temperature is 900-1050 ℃;
Gas flow rate propane: argon gas 1: 1;
the furnace pressure is controlled to be 2 kPa-10 kPa;
The deposition time is controlled to be 10-60 h each time.
8. The preparation method according to claim 1, wherein in the step (5), the PIP process comprises vacuum impregnation, pressure curing and atmospheric cracking;
Preferably, furfuryl ketone resin is adopted to prepare resin solution for vacuum impregnation and pressure impregnation;
preferably, vacuum impregnation is carried out for 1-2 hours, pressure impregnation is carried out for 1-2 hours, the pressure condition is 3-5 MPa, pressure curing is carried out for 3-4 hours under 1-2 MPa, and normal pressure cracking is carried out for 0.5-4 hours at 800-1200 ℃;
preferably, the repetition frequency of the PIP process is 2-4 times.
9. according to the preparation method of the technical scheme 1, in the step (6), the mass ratio of the silicon powder to the carbon/carbon matrix is 2-5, the infiltration temperature is 1450-1700 ℃, and the heat preservation time is 20 min-2 h.
10. An ultrahigh-temperature ceramic matrix composite material is prepared by the preparation method of any one of technical schemes 1 to 9.
Advantageous effects
The technical scheme of the invention has the following advantages:
(1) the low-density C/C green body is prepared by adopting the ultrahigh-temperature ceramic powder prepreg, the adding amount of the ultrahigh-temperature ceramic powder is controllable, and the adding proportion can be as high as 70%;
(2) according to the invention, the preparation of the anti-silicification interface layer is carried out after the cracking of the mould pressing flat plate, so that the corrosion of silicon to carbon fiber in the infiltration process is effectively reduced, and the mechanical property of the composite material is improved.
Detailed Description
in order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
the invention provides a preparation method of an ultrahigh-temperature ceramic matrix composite, which comprises the following steps:
(1) mixing ceramic powder and thermosetting phenolic resin to prepare slurry;
in some preferred embodiments, the thermosetting phenolic resin is any one or more of boron phenolic resin, barium phenolic resin and ammonia phenolic resin, preferably barium phenolic resin. In some preferred embodiments, the ceramic powder is selected from zirconium carbide powder and/or zirconium boride powder.
the concentration of the slurry (i.e., the mass percentage of the ceramic powder in the slurry) is preferably 10% to 70%, and may be any value (inclusive) within this range, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%. The powder adding proportion is too high, the viscosity of the ceramic powder slurry is too high, and the ceramic powder slurry is not suitable for preparing a glue film; meanwhile, because the content of the powder is higher, the bonding between flat plate layers after mould pressing is poorer, and the layering is easy. The proportion addition is too low to achieve the ceramic powder addition expectations. It can be seen that the maximum addition amount of the ceramic powder in the technical scheme of the invention can reach 70%.
(2) compounding the slurry and the carbon cloth by adopting a hot melt adhesive membrane method to obtain a prepreg;
There are various methods of compounding, such as dipping. The invention adopts a hot melt adhesive film method for compounding to prepare the prepreg. The hot melt adhesive film method specifically comprises the following steps: the sizing agent is made into a glue film, the glue film is compounded on the surface of the carbon cloth, and then the resin is melted by heating and pressurizing and is immersed into the carbon cloth. The process conditions of the hot melt adhesive film method are not specifically limited, and the method belongs to the conventional technology, and can refer to the prior technical scheme. However, the content of the resin paste in the prepreg to be produced is limited in the present invention, and is preferably 50 to 70% (mass percentage content), and may be any value (inclusive) within this range, for example, 50%, 55%, 60%, 65%, 70%.
(3) Stacking prepreg layers and preparing a molding flat plate; carrying out thermal cracking on the mould pressing flat plate to obtain a carbon/carbon blank;
In preparing the molding plate, the fiber volume fraction of the molding plate may be 28% to 60%, for example, 28%, 29%, 30%, 35%, 40%, 45%, 50%, 55%, 60% by ply numerical control molding.
The invention preferably adopts a mould pressing process to prepare the mould pressing flat plate, and the process conditions of the mould pressing process are as follows:
The pressurizing temperature is 100 to 120 ℃, and for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃ and 120 ℃;
the curing temperature is 180 ℃ to 190 ℃, for example, 180 ℃, 185 ℃, 190 ℃;
The holding time is 4 to 5 hours, for example, 4, 4.5, or 5 hours.
For the thermal cracking process, the present invention preferably performs the thermal cracking under an inert atmosphere (preferably nitrogen or argon) under the following process conditions:
the heating rate is 0.5 ℃/min to 1 ℃/min, the heating rate is preferably 0.5 ℃/min to avoid product deformation and cracking, and the thermal cracking temperature is 600 to 1000 ℃ (for example, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃).
(4) processing the carbon/carbon blank to obtain the carbon/carbon blank with the anti-silicification interface layer;
In this step, the present invention preferably uses a chemical vapor infiltration process to treat the carbon/carbon body, wherein the process conditions of the chemical vapor infiltration process are as follows:
The deposition temperature is 900 to 1050 ℃, for example, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃;
Gas flow rate propane: argon gas 1: 1;
the furnace pressure is controlled to be 2kPa to 10kPa, and may be, for example, 2kPa, 3kPa, 4kPa, 5kPa, 6kPa, 7kPa, 8kPa, 9kPa, 10 kPa;
The deposition time is controlled to be 10 h-60 h, for example, 10h, 20h, 30h, 40h, 50h, 60 h.
(5) carrying out densification treatment on the carbon/carbon blank with the anti-silicification interface layer by using a PIP (polysilicon-insulator-polysilicon) process to obtain a carbon/carbon matrix;
For the preparation method provided by the invention, the PIP process comprises vacuum impregnation, pressure curing and atmospheric cracking. When vacuum impregnation and pressure impregnation are carried out, the impregnation glue solution can be a resin glue solution prepared from thermosetting phenolic resin, wherein the thermosetting resin is selected from any one of boron phenolic resin, barium phenolic resin and ammonia phenolic resin. Of course, in the case of impregnation (including vacuum impregnation and pressure impregnation), a phenol resin used in the preparation of the prepreg can be selected as the resin for impregnation. For the process conditions of each step, preferably, vacuum impregnation is carried out for 1-2 hours, pressure impregnation is carried out for 1-2 hours, the pressure condition is 3-5 MPa, pressure curing is carried out for 3-4 hours at 1-2 MPa, and normal pressure cracking is carried out for 0.5-4 hours at 800-1200 ℃. In addition, the repetition frequency of the PIP process is preferably 2-4 times.
(6) and covering the carbon/carbon matrix with silicon powder, and performing melt siliconizing by adopting a reaction infiltration method to obtain the ultrahigh-temperature ceramic-based composite material.
The reactive infiltration can be referred to the prior art, for example, by using a graphite crucible as a reaction vessel and performing a high-temperature treatment using a high-temperature furnace. Preferably, the reaction infiltration treatment is carried out, wherein the mass ratio of the silicon powder to the C/C blank is 2-5 (for example, 2, 3, 4, 5), the infiltration temperature is 1450-1700 ℃ (for example, 1450 ℃, 1500 ℃, 1550 ℃, 1600 ℃, 1650 ℃, 1700 ℃), and the heat preservation time is 20 min-2 h (for example, 20min, 30min, 40min, 50min, 1h, 1.5h, 2 h).
More comprehensively, the preparation method provided by the invention comprises the following steps:
(1) Mixing ceramic powder and thermosetting phenolic resin to prepare slurry;
The thermosetting phenolic resin is any one or more of boron phenolic resin, barium phenolic resin and ammonia phenolic resin. The ceramic powder is zirconium carbide powder and/or zirconium boride powder.
the concentration of the slurry (i.e. the mass percentage of the ceramic powder in the slurry) is preferably 10% to 60%.
(2) compounding the slurry and the carbon cloth by adopting a hot melt adhesive membrane method to obtain a prepreg; in the prepreg, the mass percentage content of the slurry is 50-70%;
(3) stacking prepreg layers and preparing a molding flat plate; carrying out thermal cracking on the mould pressing flat plate to obtain a carbon/carbon blank;
When the mould pressing flat plate is prepared, the volume fraction of the fibre of the mould pressing flat plate can be controlled by a layering numerical control mould to be 28-50 percent; the invention preferably adopts a mould pressing process to prepare the mould pressing flat plate, and the process conditions of the mould pressing process are as follows:
The pressurizing temperature is 100-120 ℃;
The curing temperature is 180-190 ℃;
The heat preservation time is 4-5 h.
For the thermal cracking process, the present invention preferably performs the thermal cracking under an inert atmosphere (preferably nitrogen or argon) under the following process conditions:
The heating rate is 0.5 ℃/min to 1 ℃/min, and the thermal cracking temperature is 600 ℃ to 1000 ℃.
(4) Processing the carbon/carbon blank to obtain the carbon/carbon blank with the anti-silicification interface layer;
In the step, the carbon/carbon blank is processed by adopting a chemical vapor infiltration process, wherein the process conditions of the chemical vapor infiltration process are as follows:
The deposition temperature is 900-1050 ℃;
Gas flow rate propane: argon gas 1: 1;
the furnace pressure is controlled to be 2 kPa-10 kPa;
the deposition time is controlled to be 10-60 h each time.
(5) Carrying out densification treatment on the carbon/carbon blank with the anti-silicification interface layer by using a PIP (polysilicon-insulator-polysilicon) process to obtain a carbon/carbon matrix;
The PIP process includes vacuum impregnation, pressure curing and atmospheric cracking. When vacuum impregnation and pressure impregnation are carried out, the impregnation glue solution is a resin glue solution prepared from thermosetting phenolic resin, wherein the thermosetting resin is selected from any one of boron phenolic resin, barium phenolic resin and ammonia phenolic resin. For the process conditions of each step, vacuum impregnation is carried out for 1-2 hours, pressure impregnation is carried out for 1-2 hours, the pressure condition is 3-5 MPa, pressure curing is carried out for 3-4 hours at 1-2 MPa, and normal pressure cracking is carried out for 0.5-4 hours at 800-1200 ℃. The repetition frequency of the PIP process is 2-4 times.
(6) and covering the carbon/carbon matrix with silicon powder, and performing melt siliconizing by adopting a reaction infiltration method to obtain the ultrahigh-temperature ceramic-based composite material.
When the reaction infiltration treatment is carried out, the mass ratio of the silicon powder to the C/C blank is 2-5, the infiltration temperature is 1450-1700 ℃, and the heat preservation time is 20 min-2 h.
In the preparation method provided by the present invention, the detailed description of the present invention is not given to the known techniques of those skilled in the art.
The invention also provides an ultrahigh-temperature ceramic matrix composite material prepared by the preparation method provided by the invention.
The following are examples of the present invention.
Example 1
(1) preparing slurry: the phenolic resin slurry is prepared by blending barium phenolic resin and ultrahigh-temperature ceramic powder ZrC powder, wherein the ultrahigh-temperature ceramic powder ZrC powder accounts for 20% of the mass of the phenolic resin slurry.
(2) preparing a prepreg: the ultrahigh-temperature ceramic powder prepreg is prepared by compounding phenolic resin slurry with carbon cloth by adopting a hot melt adhesive membrane method, wherein the mass content of the phenolic resin slurry is 60%.
(3) Preparing a low-density carbon/carbon blank: the composite material is prepared by adopting a die pressing process, wherein the volume fraction of the flat plate fiber is controlled to be 40% by the ply number, the pressurizing temperature is controlled to be 120 ℃, the curing temperature is controlled to be 180 ℃, and the heat preservation time is 4 hours.
and carrying out thermal cracking on the mould pressing flat plate, wherein the thermal cracking is carried out in a nitrogen atmosphere, the heating rate is 0.5 ℃/min, and the thermal cracking treatment temperature is 800 ℃.
(4) Preparing an anti-silicification interface layer: preparing an anti-silicification interface layer by adopting a chemical vapor infiltration method, wherein the deposition temperature is 1000 ℃, and the gas flow rate is propane: argon gas 1: 1, controlling the furnace pressure to be 5kPa, and controlling the deposition time to be 20h each time.
(5) Preparation of low density carbon/carbon matrix: the low density carbon/carbon matrix is prepared by a PIP process, which includes vacuum impregnation, pressure curing and atmospheric cracking. When vacuum impregnation and pressure impregnation are carried out, the impregnation glue solution is furfuryl ketone resin solution. For the process conditions of each step, vacuum impregnation is carried out for 2 hours, pressure impregnation is carried out for 2 hours, the pressure condition is 25MPa, pressure curing is carried out for 24 hours at 22MPa, and normal pressure cracking is carried out for 1 hour at 1000 ℃. The PIP process was repeated 2 times.
(6) And (3) molten siliconizing: and (2) placing the low-density carbon/carbon matrix into a graphite crucible, covering the graphite crucible with 99.9% of Si powder, wherein the mass ratio of the silicon powder to the carbon/carbon matrix is 2, placing the graphite crucible into a high-temperature furnace, heating to 1550 ℃, and preserving heat for 1h to obtain the ultrahigh-temperature ceramic-based composite material.
The bending strength of the ultrahigh-temperature ceramic matrix composite material is 240MPa through detection.
example 2
(1) preparing slurry: the phenolic resin slurry is prepared by blending ammonia phenolic resin and ultrahigh-temperature ceramic powder ZrC powder, wherein the mass percentage of the ultrahigh-temperature ceramic powder ZrC powder in the phenolic resin slurry is 40%.
(2) The same as in example 1.
(3) The same as in example 1.
(4) the same as in example 1.
(5) The same as in example 1.
(6) The same as in example 1.
The bending strength of the ultrahigh-temperature ceramic matrix composite material is 215MPa through detection.
Example 3
(1) Preparing slurry: the phenolic resin slurry is prepared by blending ammonia phenolic resin and ultrahigh-temperature ceramic powder ZrC powder, wherein the mass percentage of the ultrahigh-temperature ceramic powder ZrC powder in the phenolic resin slurry is 60%.
(2) The same as in example 1.
(3) The same as in example 1.
(4) the same as in example 1.
(5) the same as in example 1.
(6) The same as in example 1.
The bending strength of the ultrahigh temperature ceramic matrix composite material is 200MPa through detection.
Example 4
(1) Preparing slurry: the phenolic resin slurry is prepared by blending ammonia phenolic resin and ultrahigh-temperature ceramic powder ZrC powder, wherein the ultrahigh-temperature ceramic powder ZrC powder accounts for 80% of the mass of the phenolic resin slurry.
(2) The same as in example 1.
(3) The same as in example 1.
(4) the same as in example 1.
(5) The same as in example 1.
(6) The same as in example 1.
The inventor finds that the powder content is too high, and in the step (3), the mould pressing flat plate is subjected to thermal cracking to generate a layering phenomenon.
example 5
(1) The same as in example 1.
(2) the same as in example 1.
(3) the same as in example 1.
(4) The same as in example 1.
(5) Preparation of low density carbon/carbon matrix: the low density carbon/carbon matrix is prepared by a PIP process, which includes vacuum impregnation, pressure curing and atmospheric cracking. When vacuum impregnation and pressure impregnation are carried out, the impregnation glue solution is ammonia phenolic resin solution. For the process conditions of each step, vacuum impregnation is carried out for 2 hours, pressure impregnation is carried out for 2 hours, the pressure condition is 25MPa, pressure curing is carried out for 24 hours at 22MPa, and normal pressure cracking is carried out for 1 hour at 1500 ℃. The PIP process was repeated 4 times.
(6) The same as in example 1.
the bending strength of the ultrahigh temperature ceramic matrix composite material is 195MPa through detection.
Example 6
(1) The same as in example 1.
(2) preparing a prepreg: the ultrahigh-temperature ceramic powder prepreg is prepared by compounding phenolic resin slurry with carbon cloth by adopting a hot melt adhesive membrane method, wherein the mass content of the phenolic resin slurry is 70%.
(3) the same as in example 1.
(4) The same as in example 1.
(5) The same as in example 1.
(6) the same as in example 1.
The bending strength of the ultrahigh temperature ceramic matrix composite material is 235MPa through detection.
Example 7
(1) The same as in example 1.
(2) preparing a prepreg: the ultrahigh-temperature ceramic powder prepreg is prepared by compounding phenolic resin slurry with carbon cloth by adopting a hot melt adhesive membrane method, wherein the mass content of the phenolic resin slurry is 75%.
(3) The same as in example 1.
(4) The same as in example 1.
(5) The same as in example 1.
(6) The same as in example 1.
the inventors have found that the pulp content is too high and that the fibres are deformed during moulding.
Example 8
(1) the same as in example 1.
(2) preparing a prepreg: the ultrahigh-temperature ceramic powder prepreg is prepared by compounding phenolic resin slurry with carbon cloth by adopting a hot melt adhesive membrane method, wherein the mass content of the phenolic resin slurry is 40%.
(3) The same as in example 1.
(4) The same as in example 1.
(5) The same as in example 1.
(6) The same as in example 1.
The inventor finds that the content of the slurry is too low, the molded flat plate is poor in glue, and the delamination phenomenon occurs after thermal cracking.
Example 9
(1) The same as in example 1.
(2) The same as in example 1.
(3) Preparing a low-density carbon/carbon blank: the composite material is prepared by adopting a die pressing process, the volume fraction of the flat fiber is controlled to be 50% by the ply number, the pressurizing temperature is controlled to be 120 ℃, the curing temperature is controlled to be 180 ℃, and the heat preservation time is 4 hours.
(4) The same as in example 1.
(5) the same as in example 1.
(6) The same as in example 1.
The bending strength of the ultrahigh-temperature ceramic matrix composite material is 220MPa through detection.
Example 10
(1) the same as in example 1.
(2) The same as in example 1.
(3) Preparing a low-density carbon/carbon blank: the composite material is prepared by adopting a die pressing process, the volume fraction of the flat fiber is controlled to be 20% by the ply number, the pressurizing temperature is controlled to be 120 ℃, the curing temperature is controlled to be 180 ℃, and the heat preservation time is 4 hours.
(4) The same as in example 1.
(5) the same as in example 1.
(6) the same as in example 1.
The inventors have found that delamination occurs after thermal cracking of the molded flat plate.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A preparation method of an ultrahigh-temperature ceramic matrix composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) Mixing ceramic powder and thermosetting phenolic resin to prepare slurry;
(2) Compounding the slurry and the carbon cloth by adopting a hot melt adhesive membrane method to obtain a prepreg;
(3) Stacking prepreg layers and preparing a molding flat plate; carrying out thermal cracking on the mould pressing flat plate to obtain a carbon/carbon blank;
(4) processing the carbon/carbon blank to obtain the carbon/carbon blank with the anti-silicification interface layer;
(5) carrying out densification treatment on the carbon/carbon blank with the anti-silicification interface layer by using a PIP (polysilicon-insulator-polysilicon) process to obtain a carbon/carbon matrix;
(6) And covering the carbon/carbon matrix with silicon powder, and performing melt siliconizing by adopting a reaction infiltration method to obtain the ultrahigh-temperature ceramic-based composite material.
2. The method of claim 1, wherein: in the step (1), the thermosetting phenolic resin is selected from any one or more of boron phenolic resin, barium phenolic resin and ammonia phenolic resin, preferably barium phenolic resin; and/or
The ceramic powder is selected from zirconium carbide powder and/or zirconium boride powder.
3. The method of claim 2, wherein: the mass percentage of the ceramic powder in the slurry is 10-70%.
4. the method of claim 1, wherein: in the step (2), the slurry accounts for 50-70% of the mass of the prepreg.
5. The method of claim 1, wherein: in the step (3), when the mould pressing flat plate is prepared, the volume fraction of the fibre of the mould pressing flat plate is 28-60% through ply numerical control moulding; and/or
The mould pressing flat plate is prepared by adopting a mould pressing process, and the process conditions of the mould pressing process are as follows:
The pressurizing temperature is 100-120 ℃;
the curing temperature is 180-190 ℃;
The heat preservation time is 4-5 h.
6. the method of claim 1, wherein: in the step (3), the thermal cracking is carried out under an inert atmosphere, and the process conditions of the thermal cracking are as follows:
The heating rate is 0.5 ℃/min to 1 ℃/min, and the thermal cracking temperature is 600 ℃ to 1000 ℃.
7. The method of claim 1, wherein: in the step (4), a chemical vapor infiltration process is adopted to treat the carbon/carbon blank, wherein the process conditions of the chemical vapor infiltration process are as follows:
The deposition temperature is 900-1050 ℃;
Gas flow rate propane: argon gas 1: 1;
The furnace pressure is controlled to be 2 kPa-10 kPa;
The deposition time is controlled to be 10-60 h each time.
8. The method of claim 1, wherein: in step (5), the PIP process includes vacuum impregnation, pressure curing and atmospheric cracking;
Preferably, hot furfuryl ketone resin is adopted to prepare resin solution for vacuum impregnation and pressure impregnation;
preferably, vacuum impregnation is carried out for 1-2 hours, pressure impregnation is carried out for 1-2 hours, the pressure condition is 3-5 MPa, pressure curing is carried out for 3-4 hours under 1-2 MPa, and normal pressure cracking is carried out for 0.5-4 hours at 800-1200 ℃;
Preferably, the repetition frequency of the PIP process is 2-4 times.
9. The method of claim 1, wherein: in the step (6), the mass ratio of the silicon powder to the carbon/carbon matrix is 2-5, the infiltration temperature is 1450-1700 ℃, and the heat preservation time is 20 min-2 h.
10. An ultra-high temperature ceramic matrix composite characterized in that: prepared by the preparation method of any one of claims 1 to 9.
CN201911022737.2A 2019-10-25 2019-10-25 Ultrahigh-temperature ceramic matrix composite and preparation method thereof Pending CN110563479A (en)

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CN112341228A (en) * 2020-11-09 2021-02-09 航天特种材料及工艺技术研究所 C/ZrC-SiC superhigh temperature ceramic matrix composite and preparation method thereof
CN112409005A (en) * 2020-11-23 2021-02-26 航天特种材料及工艺技术研究所 Preparation method of net-size C/SiC ceramic matrix composite
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CN115975335A (en) * 2022-12-28 2023-04-18 蚌埠凌空科技有限公司 Mould pressing prepreg for high-performance heat-insulation-preventing composite material and preparation method thereof
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CN111233503A (en) * 2020-02-26 2020-06-05 中南大学 Preparation method of fiber-toughened ceramic matrix composite
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CN115975335A (en) * 2022-12-28 2023-04-18 蚌埠凌空科技有限公司 Mould pressing prepreg for high-performance heat-insulation-preventing composite material and preparation method thereof
CN116135820A (en) * 2023-02-13 2023-05-19 航天特种材料及工艺技术研究所 Ultrahigh-temperature ceramic matrix composite material and preparation method thereof
CN116135820B (en) * 2023-02-13 2024-03-08 航天特种材料及工艺技术研究所 Ultrahigh-temperature ceramic matrix composite material and preparation method thereof

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