CN106866148B - SiC nanowire in-situ reinforced SiCf/SiC composite material and preparation method thereof - Google Patents
SiC nanowire in-situ reinforced SiCf/SiC composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses SiC nanowire in-situ reinforced SiCfThe SiC/SiC composite material comprises a SiC fiber prefabricated part, SiC nanowires and a SiC ceramic matrix, wherein the SiC nanowires grow on the fiber surface of the SiC fiber prefabricated part in situ, and the SiC nanowires are mutually wound to form a net structure; and the SiC ceramic matrix is filled in the pores of the SiC fiber prefabricated part. The preparation method comprises the following steps: (1) surface chemical modification treatment; (2) loading a catalyst; (3) chemical vapor deposition; (4) and (4) dipping and cracking the precursor. The SiC nanowire in-situ reinforced SiCfThe SiC/SiC composite material has the advantages of uniform SiC nanowire distribution, no agglomeration, good combination with SiC fibers, good toughness, high density and the like, the preparation method has simple process, low equipment requirement, environmental protection and good process universality, and the introduced volume fraction of the SiC nanowires is high and controllable.
Description
Technical Field
The invention relates to the field of ceramic matrix composite materials, in particular to SiC nanowire in-situ reinforced SiCfSiC composite materialAnd a method for preparing the same.
Background
Continuous SiC fiber reinforced SiC base (SiC)fthe/SiC) composite material has excellent performances of low density, high specific strength, high specific modulus, low chemical activity and the like, and also has the characteristics of high resistivity, low neutron radiation induction activity and the like, thereby having wide application prospects in the fields of aerospace, nuclear fusion reactors, high-temperature structure wave-absorbing materials and the like.
However, SiCfThe mechanical property of the/SiC composite material applied to high-temperature structural parts needs to be further improved. In particular, the fracture toughness is far from the fracture toughness of high temperature alloys and other materials. SiCfThe low fracture toughness of the/SiC composite material becomes a short plate which restricts the application of the composite material in advanced fields. Since SiCfThe SiC/SiC composite material has wide application prospect in the fields of aerospace and national defense, and develops a large amount of basic research in recent academia for improving the mechanical property of the material. At present, the researches mainly focus on the aspects of improving the fiber performance, optimizing the preparation process of the composite material, improving the performance stability of the composite material and the like, and a more effective reinforcement is selected, particularly, the researches for improving the toughness of the composite material by using a nano material with high mechanical property are not many.
The SiC nanowire becomes a hot point for material research at home and abroad due to the excellent mechanical property and the wide application prospect in composite materials. The maximum bending strength of the SiC nanowire is 53.4 GPa, which is twice that of the micron whisker. In addition, the SiC nanowire has superplasticity at room temperature. The SiC nanowires with proper content are introduced into the composite material, so that the strength, the fracture toughness and the like of the composite material are expected to be improved, and the composite material has a wide application prospect.
SiC nanowire and SiCfthe/SiC composite material has the same chemical composition, so that the problem of physicochemical compatibility between the reinforcement body and the matrix does not exist. Thus, the SiC nanowires are SiCfthe/SiC composite material is an ideal nano reinforcement. But strong van der waals force exists among the nano materials, and the huge specific surface area and the high length-diameter ratio of the one-dimensional nano materials are added, so that the nano materials are easy to form winding conglomeration or agglomeration,greatly reduces the reinforcing effect, and simultaneously is difficult to introduce a one-dimensional nano material reinforcing body with high volume fraction into the composite material. Therefore, the performance of the composite material prepared by the method of directly adding the nano reinforcement is still not satisfactory.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide SiC nanowire in-situ reinforced SiC with uniform SiC nanowire distribution, no agglomeration, good combination with SiC fiber, good toughness and high densityfThe SiC nanowire in-situ reinforced SiC nanowire material is high and controllable in SiC nanowire introduction, simple in process, low in equipment requirement, environment-friendly and good in process universalityfA preparation method of a/SiC composite material.
In order to solve the technical problems, the invention adopts the following technical scheme:
SiC nanowire in-situ reinforced SiCfThe SiC/SiC composite material comprises a SiC fiber prefabricated part, SiC nanowires and a SiC ceramic matrix, wherein the SiC nanowires grow on the fiber surface of the SiC fiber prefabricated part in situ, and the SiC nanowires are mutually wound to form a net structure; and the SiC ceramic matrix is filled in the pores of the SiC fiber prefabricated part.
The SiC nanowire in-situ reinforced SiCfThe SiC/SiC composite material is preferred, and the SiC nanowires occupy SiC enhanced in situ by the SiC nanowiresfThe mass percentage of the/SiC composite material is 2-4.2%.
The SiC nanowire in-situ reinforced SiCfThe SiC ceramic matrix accounts for SiC enhanced in situ of the SiC nanowirefThe mass percentage content of the/SiC composite material is 60-70%.
As a general inventive concept, the present invention also provides SiC nanowires in-situ reinforced SiCfThe preparation method of the/SiC composite material comprises the following steps:
(1) surface chemical modification treatment: dipping the SiC fiber prefabricated part in an organic chemical dipping agent to load organic functional groups on a SiC fiber matrix to obtain a surface chemical modified SiC fiber prefabricated part;
(2) loading a catalyst: dipping the surface chemically modified SiC fiber prefabricated part obtained in the step (1) in a metal ion catalyst precursor solution to enable the organic functional group to adsorb a metal ion catalyst, so as to obtain a catalyst-loaded SiC fiber prefabricated part;
(3) chemical vapor deposition: placing the first SiC ceramic precursor and the SiC fiber prefabricated part loaded with the catalyst obtained in the step (2) in a chemical vapor deposition furnace, and carrying out chemical vapor deposition under the protection of inert gas to grow SiC nanowires in situ on the SiC fiber prefabricated part loaded with the catalyst to obtain a SiC nanowire in-situ reinforced SiC fiber prefabricated part;
(4) dipping and cracking a precursor: placing the SiC nanowire in-situ reinforced SiC fiber prefabricated part obtained in the step (3) in a second SiC ceramic precursor for vacuum impregnation, taking out the SiC fiber prefabricated part for crosslinking and cracking, and repeating the impregnation-crosslinking-cracking process until the weight of the SiC nanowire in-situ reinforced SiC fiber prefabricated part is increased by less than 1% compared with the weight of the SiC nanowire in-situ reinforced SiC fiber prefabricated part obtained in the last impregnation-crosslinking-cracking process to obtain the SiC nanowire in-situ reinforced SiCfa/SiC composite material.
The SiC nanowire in-situ reinforced SiCfPreferably, in the step (1), the organic chemical impregnant is a suspension prepared from ethylenediamine tetraacetic acid and dimethylformamide, and the mass ratio of the ethylenediamine tetraacetic acid to the dimethylformamide is 1: 8-10.
The SiC nanowire in-situ reinforced SiCfPreferably, in the step (2), the metal ion catalyst precursor solution comprises an aqueous solution of a nitrate containing Fe or an aqueous solution of a nitrate containing Ni; in the precursor solution of the metal ion catalyst, the concentration of metal ions is 0.05-2 mol/l.
The SiC nanowire in-situ reinforced SiCfPreferably, in the step (1), the impregnation process conditions are as follows: the dipping temperature is 100-120 ℃, and the dipping time is 5-7 h; the steps areIn the step (2), the technological conditions of the impregnation are as follows: the dipping temperature is 50-70 ℃, and the dipping time is 3-5 h.
The SiC nanowire in-situ reinforced SiCfPreferably, in the step (3), the first SiC ceramic precursor includes polycarbosilane, polysilanesilane, or polymethylsilane, and the deposition temperature of the chemical vapor deposition is 1250 to 1400 ℃ and the deposition time is 1 to 2 hours.
The SiC nanowire in-situ reinforced SiCfPreferably, in the step (4), the second SiC ceramic precursor comprises liquid polycarbosilane containing vinyl; the vacuum impregnation time is 10-12 h, and the vacuum degree is 1000 Pa; the pressure of the crosslinking is 1MPa to 2MPa, the temperature is 300 ℃, and the time is 5h to 8 h; the cracking atmosphere is nitrogen atmosphere, the temperature is 1100 ℃, and the cracking time is 1-2 h.
The SiC nanowire in-situ reinforced SiCfThe preparation method of the/SiC composite material preferably comprises the following step of carrying out surface size removal pretreatment on the SiC fiber matrix before the step (1): and (3) placing the SiC fiber matrix in air, heating to 400-500 ℃, preserving heat for 1-2 h, and then ultrasonically washing in ethanol for 1-2 h.
Compared with the prior art, the invention has the advantages that:
1. SiC nanowire in-situ reinforced SiC of the inventionfThe SiC nanowire grows on the fiber surface of the SiC fiber prefabricated part in situ and is well combined with the SiC fiber; SiC nanowires are mutually wound to form a net structure, are not agglomerated and can be fully filled in pores among fibers, so that the SiC nanowires are uniformly distributed in the SiC fiber prefabricated part, and the formed SiC nanowires are reinforced in situfThe strength and toughness of the/SiC composite material are good, and particularly the fracture toughness is greatly improved; in addition, the SiC ceramic matrix is also filled in the pores of the SiC fiber prefabricated part, so that the density and the strength of the composite material are further improved.
2. SiC nanowire in-situ reinforced SiC of the inventionfSiC composite materialCompared with a mechanical mixing method, the in-situ growth method has obvious advantages and can introduce the SiC nanowires with controllable content and better dispersion into the matrix. In addition, the in-situ growth method is also helpful for improving the bonding strength between the fiber and the SiC nanometer, and is helpful for secondary extraction of the SiC nanometer wire in the process of extracting the fiber, so that more energy is consumed, and the method is very beneficial to improving the fracture toughness of the composite material. The SiC nanowires are introduced into the interface phase of the ceramic matrix composite, and the in-situ grown SiC nanowires improve the combination of the fiber/matrix interface in the SiCf/SiC composite, so that the SiCf/SiC composite is strengthened and toughened. In addition, the method loads organic functional groups on the surface of the SiC fiber matrix for the first time, and then loads the catalyst by utilizing the adsorption effect of the organic functional groups on catalyst ions, compared with a direct catalyst impregnation method, the method can obtain more catalysts which are uniformly distributed on the surface of the SiC fiber, and the loaded catalysts are not easy to remove in the subsequent rinsing process, so that higher SiC nanowires can be introduced through the subsequent chemical vapor deposition, and the weight percent of the SiC nanowires can reach more than 4.2 percent. The subsequent combination with a precursor impregnation conversion process (PIP) can introduce a SiC ceramic matrix to further improve the density of the composite material.
3. SiC nanowire in-situ reinforced SiC of the inventionfThe SiC nanowire content introduced into the SiC fiber prefabricated part is high and controllable, and the appearance and the yield of the SiC nanowire can be controlled by adjusting parameters such as catalyst concentration, CVD process temperature, carrier gas flow ratio and the like.
4. SiC nanowire in-situ reinforced SiC of the inventionfThe preparation method of the/SiC composite material has the advantages of simple process and low equipment requirement, the used process equipment mainly comprises a vacuum impregnation kettle, a resistance furnace, a quartz tube and the like, the process route is simple and easy to implement, and the preparation process has no pollution to the environment.
Drawings
FIG. 1 is a schematic view of a chemical vapor deposition apparatus used in step (4) of example 1 of the present invention.
FIG. 2 is an SEM topography of the SiC fiber three-dimensional fabric loaded with the catalyst in example 1 of the invention.
FIG. 3 shows SiC nanowires in-situ reinforced SiC prepared in example 1 of the present inventionfOptical photographs of the/SiC composite.
FIG. 4 shows SiC nanowires in-situ reinforced SiC prepared in example 1 of the present inventionfSEM topography of the/SiC composite material.
FIG. 5 shows SiC nanowires in-situ reinforced SiC prepared in example 1 of the present inventionfA fracture SEM topography of the/SiC composite material; wherein, the magnification of the diagram c is 20000 times, and the magnification of the diagram d is 50000 times.
FIG. 6 is an SEM topography of a silicon carbide fiber three-dimensional fabric prepared in comparative example 1.
FIG. 7 is an SEM surface topography of a silicon carbide nanowire in-situ reinforced silicon carbide fiber three-dimensional fabric prepared in comparative example 2 of the present invention; wherein, the graph a is magnified 800 times, and the graph b is magnified 5000 times.
FIG. 8 is an SEM topography of a silicon carbide fiber three-dimensional fabric prepared in comparative example 3 of the present invention; wherein, the a picture is magnified 15000 times, and the b picture is magnified 2000 times.
Detailed Description
The invention is further described below with reference to the drawings of the specification and to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available.
Example 1:
the SiC nanowire in-situ reinforced SiC of the inventionfThe SiC/SiC composite material comprises a SiC fiber prefabricated part, SiC nanowires and a SiC ceramic matrix, wherein the SiC nanowires grow on the surface of the fiber matrix of the SiC fiber prefabricated part in situ, and the SiC nanowires are mutually wound to form a net structure; and the SiC ceramic matrix is filled in the pores of the SiC fiber prefabricated part.
In the embodiment, the SiC fiber prefabricated part is a three-dimensional four-way three-dimensional fabric woven by domestic KD-II type SiC fibers, and the mass percentage of the SiC nanowires is 4.2%. The mass percentage of the SiC ceramic matrix is 65 percent.
The SiC nanowire in-situ reinforced SiC of the embodimentfThe preparation method of the/SiC composite material comprises the following steps:
(1) pretreatment: placing the prefabricated three-dimensional four-way three-dimensional fabric of domestic KD-II type SiC fiber in a muffle furnace, heating to 400 ℃ in air, preserving heat for 1h, ultrasonically washing in ethanol for 1h to remove surface glue, and finally drying in air at 60 ℃ to obtain the pretreated three-dimensional fabric of SiC fiber;
(2) surface chemical modification treatment: the ethylene diamine tetraacetic acid (powder) and the dimethyl formamide (liquid) are weighed according to the mass ratio of 1: 10, the two chemicals are mixed to prepare suspension, and the suspension is uniformly stirred by a glass rod. Dipping the pretreated SiC fiber three-dimensional fabric obtained in the step (1) in the suspension at 110 ℃ for 6h to load organic functional groups on the surface of the pretreated SiC fiber three-dimensional fabric, taking the SiC fiber three-dimensional fabric out of the suspension, rinsing the SiC fiber three-dimensional fabric with deionized water, and drying the SiC fiber three-dimensional fabric at 60 ℃ in the air to obtain the surface chemically modified SiC fiber three-dimensional fabric;
(3) loading a catalyst: weighing ferric nitrate, dissolving the ferric nitrate in deionized water to prepare a catalyst precursor aqueous solution with Fe concentration of 0.1mol/l, impregnating the surface chemically modified SiC fiber three-dimensional fabric obtained in the step (2) with the catalyst precursor aqueous solution at 60 ℃, keeping the temperature for 4h, taking out the SiC fiber three-dimensional fabric from the catalyst precursor aqueous solution, rinsing with deionized water, and finally drying in the air at 60 ℃ to obtain the catalyst-loaded SiC fiber three-dimensional fabric;
(4) chemical vapor deposition: as shown in FIG. 1, 5.0g of polycarbosilane 5 (Mw = 2000, Tm = 180 ℃) was weighed and placed in a corundum boat 4, and the corundum boat 4 loaded with polycarbosilane 5 and the catalyst-loaded SiC fiber woven fabric obtained in step (3) were placed together in a cylindrical graphite boat 2, wherein the catalyst-loaded SiC fiber woven fabric was placed above the porous graphite plate 3 of the cylindrical graphite boat 2 (the catalyst-loaded SiC fiber woven fabric was omitted in the figure)Dimensional fabric), the cylindrical graphite boat 2 is placed in a quartz tube 1, and N is continuously introduced2Heating the quartz tube 1 by a heating body 6 to make the SiC fiber three-dimensional fabric loaded with the catalyst in N2Heating to 1300 ℃ under the protection of atmosphere, preserving the heat for 1h, and then cooling to room temperature (N) in nitrogen atmosphere2The gas flow is 10 sccm), namely completing the chemical vapor deposition process, and growing the SiC nanowire on the surface of the SiC fiber three-dimensional fabric loaded with the catalyst in situ to obtain the SiC fiber three-dimensional fabric reinforced by the SiC nanowire in situ.
(5) Dipping and cracking a precursor: and (3) placing the SiC nanowire in-situ reinforced SiC fiber three-dimensional fabric obtained in the step (4) into an impregnation box, then placing the impregnated box into a vacuum impregnation tank, vacuumizing until the pressure in the tank is reduced to 1000Pa, pouring Liquid Polycarbosilane (LPVCS) containing vinyl, enabling the LPVCS to flow into the impregnation box until the SiC nanowire in-situ reinforced SiC fiber three-dimensional fabric is completely immersed, and impregnating for 10 hours under a vacuum condition. And taking out after the impregnation is finished, placing the impregnated product in a graphite mold, adjusting the pressure to be 2MPa in a warm press, and performing crosslinking curing for 6 hours. After the crosslinking and solidification are finished, the mixture is put into a cracking furnace, and N is introduced2Protecting and heating to 1100 ℃ for 1h, and carrying out high-temperature cracking on the LPVCS entering the SiC fiber three-dimensional fabric to generate the SiC ceramic matrix. Repeating the dipping-crosslinking-cracking process until the weight of the SiC nanowire in-situ reinforced SiC fiber three-dimensional fabric is increased by less than 1 percent compared with the weight of the SiC nanowire in-situ reinforced SiC fiber three-dimensional fabric in the last dipping-crosslinking-cracking process, and obtaining the SiC nanowire in-situ reinforced SiCfa/SiC composite material.
The microscopic morphology of the catalyst-loaded SiC fiber three-dimensional fabric obtained after the treatment in steps (2) and (3) of this example is shown in fig. 2, and it can be seen from the figure that after the treatment in steps (2) and (3), the uniformly distributed catalyst is loaded on the surface of the SiC fiber matrix, and the catalyst is connected with the organic functional groups on the surface of the SiC fiber bundle and cannot be removed after the water rinsing.
The macro morphology of the SiC nanowire in-situ reinforced SiC fiber three-dimensional fabric obtained by the treatment of step (4) in this embodiment is shown in fig. 3. As can be seen from the figure, a large amount of white villous substances are covered on the surface of the SiC nanowire in-situ reinforced SiC fiber three-dimensional fabric and between fiber gaps, and the white villous substances are the silicon carbide nanowires. The microscopic morphology of the SiC nanowire in-situ reinforced SiC fiber three-dimensional fabric obtained by the processing of step (4) in this embodiment is shown in fig. 4, which shows that a large number of SiC nanowires are uniformly distributed between the surface of the SiC fiber matrix and the fibers, and the SiC nanowires are intertwined with each other to form a mesh structure. The content of the SiC nanowire reaches 4.2 percent through measurement and calculation.
In the embodiment, the SiC nanowire obtained by the treatment of the step (5) is in-situ reinforced SiCfThe microstructure of the/SiC composite material is shown in FIG. 5, and it can be seen that a large number of SiC nanowires wound into a net structure and bulk SiC ceramic matrixes are distributed among SiC fiber matrixes (i.e., in pores of the SiC fiber three-dimensional fabric).
Comparative example 1:
the comparative example uses substantially the same raw materials and preparation method as example 1, and differs therefrom only in that: this comparative example does not include step (2).
The microstructure of the silicon carbide fiber three-dimensional fabric obtained without surface modification treatment before catalyst impregnation in the comparative example is shown in fig. 6, and it can be seen from fig. 6 that the silicon carbide fiber surface is smooth and has no in-situ grown silicon carbide nanowires. This indicates that the loaded catalyst is rinsed away in the subsequent deionized water rinsing process after the silicon carbide fiber three-dimensional fabric without surface chemical modification treatment is impregnated with the catalyst, and thus, in the subsequent chemical vapor deposition, the silicon carbide nanowires cannot grow due to the absence of the catalyst. In example 1, after the silicon carbide fiber three-dimensional fabric subjected to surface chemical modification is impregnated with the catalyst, the catalyst is uniformly distributed by combining with the surface organic groups, and cannot be removed even by rinsing with deionized water.
Comparative example 2:
the comparative example uses substantially the same raw materials and preparation method as example 1, and differs therefrom only in that: the comparative example does not include step (2), and in the catalyst loading step, the silicon carbide fiber three-dimensional fabric is directly dried in the air at 60 ℃ without being rinsed by deionized water after being taken out from the catalyst precursor aqueous solution.
The microstructure of the silicon carbide fiber three-dimensional fabric obtained by the preparation method of the comparative example is shown in fig. 7, and as can be seen from fig. 7, the silicon carbide nanowires on the surface of the silicon carbide fiber are less in amount and are unevenly distributed and distributed in a needle-punched manner. In example 1, as can be seen from fig. 4, the amount of the silicon carbide nanowires distributed among the fiber matrixes of the silicon carbide fiber three-dimensional fabric is significantly greater and more uniform, and the silicon carbide nanowires are intertwined with each other to form a network structure.
Comparative example 3:
the comparative example uses substantially the same raw materials and preparation method as example 1, and differs therefrom only in that: in step (4) of this comparative example, 5.0g of vinyl-containing Liquid Polycarbosilane (LPVCS) was used as a source material in the CVD process in place of 5.0g of polycarbosilane.
The results of this comparative example are shown in fig. 8, in which a scale-like deposit layer was obtained on the surface of the fiber, and in addition, spherical substances having a diameter of about several micrometers were distributed around the fiber, and the surface of the spherical substances was also scale-like. No SiC nanowire is generated. Such spherical materials are not suitable as SiCfA reinforcing and toughening phase between the/SiC composite material fiber and the matrix.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (7)
1. SiC nanowire in-situ reinforced SiCfThe preparation method of the/SiC composite material is characterized by comprising a SiC fiber prefabricated part, SiC nanowires and a SiC ceramic matrix, wherein the SiC nanowires grow on the fiber surface of the SiC fiber prefabricated part in situ, and the SiC nanowires are mutually wound to form a net structure; the SiC ceramic matrix is filled in the pores of the SiC fiber prefabricated part, and the SiC nanowires occupy the poresSiC nanowire in-situ reinforced SiCfThe mass percentage of the/SiC composite material is 2-4.2%, and the preparation method comprises the following steps:
(1) surface chemical modification treatment: soaking the SiC fiber prefabricated part in an organic chemical impregnant, so that an organic functional group is loaded on a SiC fiber substrate, and obtaining the SiC fiber prefabricated part with the surface chemically modified, wherein the organic chemical impregnant is a suspension prepared from ethylene diamine tetraacetic acid and dimethylformamide, and the mass ratio of the ethylene diamine tetraacetic acid to the dimethylformamide is 1: 8-10;
(2) loading a catalyst: dipping the surface chemically modified SiC fiber prefabricated part obtained in the step (1) in a metal ion catalyst precursor solution to enable the organic functional group to adsorb a metal ion catalyst, then taking out the SiC fiber three-dimensional fabric from the catalyst precursor solution, rinsing the fabric with deionized water, and finally drying the fabric in the air to obtain the catalyst-loaded SiC fiber prefabricated part;
(3) chemical vapor deposition: placing the first SiC ceramic precursor and the SiC fiber prefabricated part loaded with the catalyst obtained in the step (2) in a chemical vapor deposition furnace, and carrying out chemical vapor deposition under the protection of inert gas to grow SiC nanowires in situ on the SiC fiber prefabricated part loaded with the catalyst to obtain a SiC nanowire in-situ reinforced SiC fiber prefabricated part;
(4) dipping and cracking a precursor: placing the SiC nanowire in-situ reinforced SiC fiber prefabricated part obtained in the step (3) in a second SiC ceramic precursor for vacuum impregnation, taking out the SiC fiber prefabricated part for crosslinking and cracking, and repeating the impregnation-crosslinking-cracking process until the weight of the SiC nanowire in-situ reinforced SiC fiber prefabricated part is increased by less than 1% compared with the weight of the SiC nanowire in-situ reinforced SiC fiber prefabricated part obtained in the last impregnation-crosslinking-cracking process to obtain the SiC nanowire in-situ reinforced SiCfa/SiC composite material.
2. The SiC nanowire in situ reinforced SiC of claim 1fThe preparation method of the/SiC composite material is characterized in that the SiC ceramic matrix accounts for SiC of the SiC nanowire in-situ reinforcementfThe mass percentage content of the/SiC composite material is 60-70%.
3. The SiC nanowire in situ reinforced SiC of claim 1fThe preparation method of the/SiC composite material is characterized in that in the step (2), the metal ion catalyst precursor solution comprises an Fe-containing nitrate aqueous solution or an Ni-containing nitrate aqueous solution; in the precursor solution of the metal ion catalyst, the concentration of metal ions is 0.05-2 mol/l.
4. SiC nanowire in-situ reinforced SiC according to any one of claims 1 to 3fThe preparation method of the/SiC composite material is characterized in that in the step (1), the impregnation process conditions are as follows: the dipping temperature is 100-120 ℃, and the dipping time is 5-7 h; in the step (2), the impregnation process conditions are as follows: the dipping temperature is 50-70 ℃, and the dipping time is 3-5 h.
5. SiC nanowire in-situ reinforced SiC according to any one of claims 1 to 3fThe preparation method of the/SiC composite material is characterized in that in the step (3), the first SiC ceramic precursor comprises polycarbosilane, polysilanesilane or polymethylsilane, the deposition temperature of the chemical vapor deposition is 1250-1400 ℃, and the deposition time is 1-2 h.
6. SiC nanowire in-situ reinforced SiC according to any one of claims 1 to 3fThe preparation method of the/SiC composite material is characterized in that in the step (4), the second SiC ceramic precursor comprises liquid polycarbosilane containing vinyl; the vacuum impregnation time is 10-12 h, and the vacuum degree is 1000 Pa; the pressure of the crosslinking is 1MPa to 2MPa, the temperature is 300 ℃, and the time is 5h to 8 h; the cracking atmosphere is nitrogen atmosphere, the temperature is 1100 ℃, and the cracking time is 1-2 h.
7. SiC nanowire in-situ reinforced SiC according to any one of claims 1 to 3fOf composite materials of SiCThe preparation method is characterized by also comprising the following steps of before the step (1), carrying out surface glue removal pretreatment on the SiC fiber matrix: and (3) placing the SiC fiber matrix in air, heating to 400-500 ℃, preserving heat for 1-2 h, and then ultrasonically washing in ethanol for 1-2 h.
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| CN109851362B (en) * | 2018-12-29 | 2021-09-17 | 哈尔滨理工大学 | SiC prepared by 3D formingfMethod for preparing/SiC ceramic composite material |
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| CN111848196B (en) * | 2020-07-24 | 2021-04-09 | 北京航空航天大学 | Preparation method of in-situ silicon carbide nanowire toughened silicon carbide ceramic |
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