CN110642634A - C/SiC-ZrB2Composite material and preparation method thereof - Google Patents
C/SiC-ZrB2Composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to C/SiC-ZrB2Composite materials and methods for making the same. The preparation method comprises the following steps: solidifying and cracking the precursor to obtain the nanometer ZrB2The SiC complex phase ultra-high temperature ceramic powder; mixing the ultra-high temperature ceramic powder with the precursor to prepare ultra-high temperature ceramic powder slurry; taking the slurry as a steeping liquor, and carrying out early-stage densification treatment on the C/C composite material; taking a precursor as a dipping solution, and carrying out later-stage densification treatment on the composite material subjected to the earlier-stage densification treatment to obtain the C/SiC-ZrB2A composite material. The wetting quality of the precursor, the carbon fiber and the matrix is good, and the penetration depth is improved; the early densification adopts slurry as impregnating solution, and the later densification adopts precursorThe body is directly impregnated, and the uniformity and the densification degree of the composite material are improved on the basis of ensuring the impregnation efficiency and the impregnation depth.
Description
Technical Field
The invention relates to the technical field of C/SiC composite materials, in particular to C/SiC-ZrB2Composite material and preparation method thereof
Background
The C/SiC composite material has a series of excellent performances of low density, high temperature resistance, high specific modulus, high specific strength, thermal shock resistance and the like, and is widely applied to the field of aerospace. However, the long-term oxidation resistance use temperature of the C/SiC composite material does not exceed 1650 ℃. Since the aerospace craft needs to be normally used under the severe conditions of high speed and ultrahigh temperature, and also needs to have excellent performances of high reliability and long service life, the aerospace material is required to have more excellent and stable performances and a corresponding preparation process. In order to improve the high-temperature oxidation and ablation resistance of the C/SiC composite material, an effective method is to introduce ultrahigh-temperature ceramic components into a SiC matrix to modify the matrix. Zirconium boride (ZrB)2) As an excellent ultrahigh-temperature ceramic material, the material has extremely high melting point, high thermal conductivity, low thermal expansion coefficient and good thermal shock resistance, can maintain strength and stability in a high-temperature environment, and can well meet the use requirements in the ultrahigh-temperature environment.
At present, the process for introducing the zirconium boride, an ultra-high temperature ceramic component, into the composite material is mainly a PIP process: a precursor containing a zirconium source and a boron source is used as an impregnating material, and a precursor impregnating pyrolysis method is used for densifying the C/C composite material, so that zirconium boride is introduced into a matrix. The inventor finds in research that the composite material prepared by the process has the following problems: the impregnation period is longer: the times of PIP process are generally more than 10 times, which leads to a great increase of impregnation period; the impregnation difficulty is large: the impregnation is completed by auxiliary means such as vacuum pumping and the like so as to ensure that the impregnated material can better enter the carbon fiber matrix; the concentration of the impregnating material is large: in order to ensure the densification effect, the impregnation liquid with higher concentration is adopted, and the problems of smaller impregnation depth, higher impregnation difficulty, uneven impregnation and the like are caused. Besides the problems in the impregnation stage, the currently used preparation process also has the problems of low densification efficiency, poor densification effect, uneven distribution of zirconium boride in a matrix and the like in the densification effect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides C/SiC-ZrB2Composite materials and methods for making the same.
In order to solve the technical problems, the invention provides the following technical scheme:
C/SiC-ZrB2A method of preparing a composite material, the method comprising the steps of:
(1) solidifying and cracking the precursor to obtain the nanometer ZrB2The SiC complex phase ultra-high temperature ceramic powder; the precursor is polyborosilazane-polyzirconyl-oxoalkane copolymer;
(2) mixing the ultrahigh-temperature ceramic powder obtained in the step (1) with a precursor to prepare ultrahigh-temperature ceramic powder slurry;
(3) taking the slurry obtained in the step (2) as an impregnating solution, and carrying out early-stage densification treatment on the C/C composite material; and
(4) taking a precursor as a dipping solution, and carrying out later-stage densification treatment on the composite material subjected to the earlier-stage densification treatment to obtain the C/SiC-ZrB2A composite material.
Preferably, the precursor is solidified at the temperature of 220-260 ℃ and then cracked at the temperature of 1600-1800 ℃ in the argon atmosphere to obtain the nano ZrB with the particle size of 200-400nm2The SiC complex phase superhigh temperature ceramic powder.
Preferably, when preparing the ultrahigh-temperature ceramic powder slurry, the mass percentage of the ultrahigh-temperature ceramic powder in the slurry is controlled to be less than 30 wt%, preferably 10-30 wt%, and more preferably 10-20 wt%.
Preferably, a precursor impregnation cracking method is adopted for carrying out the early densification treatment and the later densification treatment.
Preferably, when the precursor impregnation cracking method is adopted for carrying out early densification treatment, the cycle times are 2-5 times; and/or
When the precursor impregnation cracking method is adopted for the post densification treatment, the density increase of the composite material is controlled to be less than or equal to 1 percent.
Preferably, when the early densification treatment is performed, the process conditions of the precursor impregnation cracking method are as follows: the impregnation mode is vacuum impregnation or normal pressure impregnation, the curing temperature is 200-300 ℃, and the cracking temperature is 1600-1800 ℃; and/or
When the later densification treatment is carried out, the process conditions of the precursor impregnation cracking method are as follows: the impregnation method is vacuum impregnation or normal pressure impregnation, the curing temperature is 200-300 ℃, and the cracking temperature is 1600-1800 ℃.
Preferably, a pyrolytic carbon interface layer is deposited on the carbon fiber preform by using a chemical vapor deposition method to obtain the C/C composite material used in the step (3).
Preferably, the density of the C/C composite material is 0.8-1.0g/cm3。
Preferably, the carbon fiber preform is any one of a carbon fiber needle punched structure, a carbon cloth laminated sewing structure and a fine weaving and puncturing structure.
C/SiC-ZrB2The composite material is prepared by the preparation method provided by the invention.
Advantageous effects
The technical scheme of the invention has the following advantages:
the densification efficiency is improved: the invention adopts nano ZrB2the/SiC ceramic powder and the precursor are mixed to prepare slurry, and the slurry is adopted for densification, so that the densification efficiency of the matrix is improved.
Nanoscale SiC-ZrB2Phase uniform dispersion: the slurry has small viscosity, so that the dipping depth is larger and uniform, and in addition, the powder used by the slurry is the same as the precursor cracking product, thereby the carbon/SiC-ZrB2Uniformly dispersed nano SiC-ZrB is formed in the composite material2And (4) phase(s).
The degree of densification is increased: the precursor, the carbon fiber and the matrix adopted by the invention have good wettability, and the penetration depth of the precursor is favorably improved, so that the prepared C/SiC-ZrB2The density of the composite material is higher; the invention adopts SiC/ZrB in the early densification treatment stage2Preparing ultrahigh-temperature ceramic powder slurry from the ultrahigh-temperature ceramic powder and a precursor as impregnation liquid, and adopting the method in the later densification treatment stageThe precursor is directly impregnated, and the uniformity and the densification degree of the composite material are improved on the basis of ensuring the impregnation efficiency and the impregnation depth.
ZrB is introduced into a matrix by the preparation method provided by the invention2Component preparation of C/SiC-ZrB2The composite material fully utilizes the advantages of each ceramic component in the matrix, namely SiC and ZrB2The oxidation forms an oxidation protection layer which can effectively prevent oxygen from diffusing into the material, so the oxidation resistance and ablation resistance of the material under severe environment can be improved through the synergistic effect of ceramic matrix components, and the service temperature is over 1600 ℃.
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, in a first aspect, a C/SiC-ZrB2A method for preparing a composite material. Compared with the prior technical scheme of introducing zirconium boride, namely an ultrahigh-temperature ceramic component, into the C/SiC composite material, the preparation method provided by the invention adopts the precursor to carry out curing and cracking to obtain nanoscale SiC/ZrB2Ultra-high temperature ceramic powder prepared by mixing SiC/ZrB2And preparing ultrahigh-temperature ceramic powder slurry from the ultrahigh-temperature ceramic powder and the precursor as impregnation liquid to perform early-stage densification on the C/C composite material. In one aspect, the nano ZrB used in the invention2The SiC complex phase ultra-high temperature ceramic powder can directly introduce the ultra-high temperature ceramic component into the C/C composite material, so that the invention can obtain higher densification effect without repeating the dipping procedure for many times, thereby greatly reducing the production period; the impregnation liquid with higher concentration is not needed, so that the problems of increased impregnation difficulty, smaller impregnation depth, uneven impregnation and the like caused by the use of the impregnation liquid with higher concentration are solved. On the other hand, of nanometric dimensionsZrB2The introduction of SiC superhigh temperature ceramic powder also reduces the viscosity of the slurry for dipping, and then the nanometer ZrB2The SiC superhigh temperature ceramic powder has small size and good dispersibility in the precursor, so the impregnation liquid used by the invention has large impregnation depth and SiC-ZrB2The phase distribution is uniform, thereby improving the densification effect. Secondly, cracking products of the precursor in the dipping solution and the nanometer ZrB2The SiC superhigh temperature ceramic powder is the same, so the invention adopts the powder containing SiC/ZrB2After being impregnated by the ultrahigh-temperature ceramic powder and the precursor impregnation liquid, the uniformly dispersed nano SiC-ZrB can be formed in the composite material2Phase, thereby obtaining dense and uniform C/SiC-ZrB2A composite material.
In addition, the precursor adopted by the preparation method provided by the invention has good wettability with carbon fiber and matrix, and is beneficial to improving the penetration depth of the precursor, so that the prepared C/SiC-ZrB can be improved to a certain extent2And (5) compactness of the composite material.
According to the invention, the precursor is directly impregnated in the later densification treatment stage, the material pore size is larger in the earlier stage, and the impregnation efficiency is high by adopting slurry, but if slurry is always adopted for impregnation, the surface layer of the composite material is easy to seal holes, so that the density gradient is caused. And with the repeated impregnation, the densification degree of the composite material is gradually improved, the pores are gradually reduced, and the impregnation depth can be increased by directly impregnating the composite material with a precursor with lower viscosity at the later stage, so that the uniformity and the densification degree of the material are improved.
Specifically, the preparation method provided by the invention comprises the following steps:
(1) solidifying and cracking the precursor to obtain the nanometer ZrB2The SiC complex phase ultra-high temperature ceramic powder; the precursor is polyborosilazane-polyzirconyloxyalkane copolymer, and the precursor material used in the invention is the existing material and is obtained by purchase;
(2) mixing the ultrahigh-temperature ceramic powder obtained in the step (1) with a precursor to prepare ultrahigh-temperature ceramic powder slurry;
(3) taking the slurry obtained in the step (2) as an impregnating solution, and carrying out early-stage densification treatment on the C/C composite material; and
(4) taking a precursor as a dipping solution, and carrying out later-stage densification treatment on the composite material subjected to the earlier-stage densification treatment to obtain the C/SiC-ZrB2A composite material.
In some preferred embodiments, the precursors are cured at 260 deg.C (e.g., 220 deg.C, 225 deg.C, 230 deg.C, 235 deg.C, 240 deg.C, 245 deg.C, 250 deg.C, 255 deg.C, 260 deg.C) and then cracked at 1800 deg.C (e.g., 1600 deg.C, 1650 deg.C, 1700 deg.C, 1750 deg.C, 1800 deg.C) in an argon atmosphere, preferably at 1700 deg.C. The nanometer ZrB with the grain diameter of 200-400nm can be obtained by adopting the solidification and cracking process2The composite superhigh temperature ceramic powder with the grain size characteristic may be used in soaking carbon fiber composite material to obtain excellent soaking depth and homogeneous dispersion in the precursor, so as to obtain high densifying effect. If the particle size is too small, the viscosity of the slurry is higher, and the impregnation difficulty is increased; if the particle size is too large, impregnation difficulty may be increased because the particle size is large, and uniformity of dispersion may be deteriorated.
In some preferred embodiments, when preparing the ultra-high temperature ceramic powder slurry, the invention controls the mass percentage of the ultra-high temperature ceramic powder in the slurry to be less than 30 wt%, that is, the nano ZrB in the invention2The mass percentage of the/SiC complex phase ultrahigh temperature ceramic powder in the slurry is more than 0 but less than or equal to 30 wt%, for example, 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, preferably 10-30 wt%, more preferably 10-20 wt%, most preferably 15 wt%.
In some preferred embodiments, the present invention employs a precursor dip pyrolysis process for both pre-densification and post-densification.
A Precursor Impregnation Pyrolysis (PIP) method is a prior art, and the process comprises the following steps: impregnating the fiber preform with an impregnating material (such as an impregnating solution), curing and molding, then performing pyrolysis, and repeating the impregnation-curing-pyrolysis process for a plurality of cycles to obtain a compact composite material. In the present invention, when the preliminary densification treatment is performed, the precursor impregnation and cracking process is preferably performed under the following process conditions: the impregnation method is vacuum impregnation or atmospheric impregnation, the curing temperature is 200-. In addition, in the present invention, when the precursor impregnation cracking method is used for the preliminary densification treatment, the number of cycles is preferably 2 to 5, and may be, for example, 2, 3, 4, or 5.
In some preferred embodiments, the process conditions of the precursor impregnation cracking method in the post densification treatment of the present invention are preferably as follows: the impregnation method is vacuum impregnation or atmospheric impregnation, the curing temperature is 200-. In some preferred embodiments, the composite material density is preferably controlled to increase by less than or equal to 1% during the post densification treatment by the precursor impregnation pyrolysis method.
In some preferred embodiments, the density of the C/C composite material used in step (3) of the present invention is from 0.8 to 1.0g/cm3The obtained composite material can be ensured to have better mechanical property.
In some preferred embodiments, the present invention may utilize a chemical vapor deposition process to deposit a pyrolytic carbon interface layer on a carbon fiber preform to obtain the C/C composite used in step (3). The chemical vapor deposition method is the prior art, the process steps are not detailed in the invention, and the density of 0.9-1.0g/cm can be obtained by adjusting the process conditions according to the prior technical scheme3The composite material of (1). When the C/C composite material is prepared, the used carbon fiber preform can be any one of a carbon fiber needling structure, a carbon cloth lamination sewing structure and a fine weaving puncturing structure.
More fully, the preparation method provided by the invention comprises the following steps:
(1) curing the precursor at the temperature of 250-300 ℃, and then cracking the precursor at the temperature of 1600-1800 ℃ in an argon atmosphere to obtain the nano ZrB with the particle size of 200-400nm2The SiC complex phase ultra-high temperature ceramic powder; the precursor is polyborosilazane-polyzirconyl-oxoalkane copolymer;
(2) mixing the ultrahigh-temperature ceramic powder obtained in the step (1) with a precursor to prepare ultrahigh-temperature ceramic powder slurry; controlling the mass percentage of the ultrahigh-temperature ceramic powder in the slurry to be below 30 wt%, preferably 10-30 wt%;
(3) taking the slurry obtained in the step (2) as an impregnating solution, and carrying out early-stage densification treatment on the C/C composite material; and
(4) taking a precursor as a dipping solution, and carrying out later-stage densification treatment on the composite material subjected to the earlier-stage densification treatment to obtain the C/SiC-ZrB2A composite material;
in the step (4), the precursor is polyborosilazane-polyzirconyl-oxoalkane copolymer; carrying out early densification treatment and later densification treatment by adopting a precursor impregnation cracking method; when a precursor impregnation cracking method is adopted for carrying out early densification treatment, the cycle times are 2-5 times; when a precursor impregnation cracking method is adopted for carrying out later-stage densification treatment, the density of the composite material is controlled to increase by less than or equal to 1 percent; when the early densification treatment is carried out, the process conditions of the precursor impregnation cracking method are as follows: the impregnation mode is vacuum impregnation or normal pressure impregnation, the curing temperature is 200-300 ℃, and the cracking temperature is 1600-1800 ℃; when the later densification treatment is carried out, the process conditions of the precursor impregnation cracking method are as follows: the impregnation mode is vacuum impregnation or normal pressure impregnation, the curing temperature is 200-300 ℃, and the cracking temperature is 1600-1800 ℃;
depositing a pyrolytic carbon interface layer on the carbon fiber preform by using a chemical vapor deposition method to obtain the C/C composite material used in the step (3); the density of the C/C composite material is 0.8-1.0g/cm3(ii) a The carbon fiber prefabricated body is any one of a carbon fiber needling structure, a carbon cloth lamination sewing structure and a fine weaving puncturing structure.
The present invention is provided in a second aspectProvide a C/SiC-ZrB2A composite material produced by any one of the production methods provided in the first aspect of the present invention, wherein ZrB is introduced into a matrix2Component preparation of C/SiC-ZrB2The composite material fully utilizes the advantages of each ceramic component in the matrix, namely SiC and ZrB2The oxidation forms an oxidation protection layer which can effectively prevent oxygen from diffusing into the material, so the oxidation resistance and ablation resistance of the material under severe environment can be improved through the synergistic effect of ceramic matrix components, and the service temperature is over 1600 ℃.
The following are examples of the present invention.
Details which are not described in detail in the following examples are known to a person skilled in the art.
Example 1
S1, adopting a carbon cloth laminated and stitched structure carbon fiber preform, forming a pyC interface layer on the carbon fiber preform by utilizing a chemical vapor deposition (CVI) process, and preparing the carbon fiber preform with the density of 0.95g/cm3The low density C/C composite of (1).
S2, solidifying the precursor material of polyborosilazane-polyzirconyl oxoalkane copolymer at 250 ℃, then cracking for 2h at 1700 ℃ in Ar atmosphere to obtain nano ZrB with the particle size of 200-400nm2/SiC superhigh temperature ceramic powder.
S3, mixing nanometer ZrB2The SiC superhigh temperature ceramic powder and the precursor (the component is same as S2) are mixed to prepare superhigh temperature ceramic powder slurry, and the superhigh temperature ceramic powder accounts for 20 wt% of the slurry.
And S4, using the ultrahigh-temperature ceramic powder slurry as a steeping liquor, and performing matrix densification on the C/C composite material by using a PIP process, wherein the steeping mode is normal-pressure steeping, the curing temperature is 250 ℃, the cracking temperature is 1700 ℃, and the cycle number of the PIP process is 3.
And S5, taking a precursor (the same as S2) as impregnation liquid, and performing matrix densification on the composite material obtained by densifying the S4 by a PIP process again, wherein the impregnation mode is normal-pressure impregnation, the curing temperature is 250 ℃, the cracking temperature is 1700 ℃, and the density of the composite material is increased by less than or equal to 1%.
Compared with the preparation of C/SiC by a PIP process only using a precursor as a dipping solution-ZrB2Compared with the composite material, the period is shortened by 30 days (in the case of obtaining the composite material with the same density), the density is improved by 10 percent, and the tensile strength is improved by 30 percent.
Example 2 to example 3
Examples 2 and 3 were prepared substantially identically to example 1, except that: in S4, the number of times of PIP processes of example 2 and example 3 is 2 times and 5 times, respectively.
Examples 4 to 8
Example 4 and example 8 were prepared essentially identically to example 1, except that: in S3, the mass percentages of the ultra-high temperature ceramic powders in examples 4 and 8 in the slurry are 5 wt%, 10 wt%, 15 wt%, 30 wt% and 35 wt%, respectively.
Examples 9 to 11
Example 9 and example 11 were prepared essentially identically to example 1, except that: in S1, each of examples 9 and 11 was prepared to have a density of 0.8g/cm by adjusting the process parameters of the CVD process3、1.0g/cm3、1.5g/cm3The C/C composite material of (1).
Example 12
S1, adopting a carbon cloth laminated and stitched structure carbon fiber preform, forming a pyC interface layer on the carbon fiber preform by utilizing a chemical vapor deposition (CVI) process, and preparing the carbon fiber preform with the density of 0.95g/cm3The low density C/C composite of (1).
S2, solidifying the precursor material of polyborosilazane-polyzirconyl oxoalkane copolymer at 250 ℃, then cracking for 2h at 1700 ℃ in Ar atmosphere to obtain nano ZrB with the particle size of 200-400nm2/SiC superhigh temperature ceramic powder.
S3, mixing nanometer ZrB2The SiC superhigh temperature ceramic powder and the precursor (the component is same as S2) are mixed to prepare superhigh temperature ceramic powder slurry, and the superhigh temperature ceramic powder accounts for 5 wt% of the slurry.
And S4, taking the ultrahigh-temperature ceramic powder slurry as a steeping liquor, and performing matrix densification on the C/C composite material by using a PIP process for 3 times.
And S5, continuously taking the ultrahigh-temperature ceramic powder slurry as a steeping liquor, and performing matrix densification on the composite material subjected to densification by the S4 by using a PIP process until the density of the composite material is increased by less than or equal to 1%.
Example 13
S1, adopting a carbon cloth laminated and stitched structure carbon fiber preform, forming a pyC interface layer on the carbon fiber preform by utilizing a chemical vapor deposition (CVI) process, and preparing the carbon fiber preform with the density of 0.95g/cm3The low density C/C composite of (1).
And S2, taking the polyborosilazane-polyzirconyl oxoalkane copolymer precursor as an impregnation liquid, and performing matrix densification on the C/C composite material by using a PIP process for 3 times.
And S3, continuing to use the precursor as impregnation liquid, and performing matrix densification on the composite material subjected to the densification of the S2 by adopting a PIP (PIP) process until the density of the composite material is increased by less than or equal to 1%.
The properties of the composites obtained in examples 1 to 13 were characterized, including the following aspects:
density: GJB/T8133.14 test method for physical and chemical properties of electric carbon products part 14, volume density;
tensile strength: GJB6475-2008 about test method for tensile property of continuous fiber reinforced ceramic matrix composite at normal temperature.
The results are shown in Table 1.
The PIP cycle numbers in embodiments 1 to 3 are different, with the least PIP cycle number in embodiment 2 and the most PIP cycle number in embodiment 3. From the detection results, as the number of PIP cycles increases, the density of the finally prepared composite material becomes obviously higher and then becomes obviously lower, and the tensile strength is also the same. Therefore, the inventor proposes to control the repetition times of the PIP process in the early stage of densification treatment to be 2 to 5 times according to the variation trend reflected by the detection results of examples 1 to 3, so as to achieve a better densification treatment effect, and the excessive impregnation times easily cause surface sealing, so that the performance is not necessarily high, but the impregnation period is increased. Most preferably, the PIP process of the early densification treatment stage is repeated 3 times.
Examples 4 to 8 the ultra-high temperature ceramic powder in the impregnation liquid used in the previous densification process was different in mass percentage from the slurry, and in addition to example 1, the ultra-high temperature ceramic powder was 5 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, 35 wt% in the slurry. From the detection results, as the proportion of the ultrahigh-temperature ceramic powder is increased, the density and the tensile strength of the composite material are both increased, but when the proportion exceeds 15 wt%, the density and the tensile strength of the composite material are decreased as the proportion is increased. Based on the discovery, the mass percentage of the ultrahigh-temperature ceramic powder in the slurry is preferably controlled to be 10-30 wt%, more preferably 10-20 wt%, and most preferably 15 wt% in the early densification treatment stage.
The density of the C/C composites used in examples 9 to 11 was different, plus that of example 1, the density of the C/C composite was 0.8g/cm3、0.95g/cm3、1.0g/cm3、1.5g/cm3. From part of the test results, as the density of the used C/C composite material increases, the density of the composite material tends to become larger, and the tensile strength is also improved. However, from the results of the test in example 11, the density of the C/C composite material is not as high as possible. Based on this, the density of the C/C composite material used in the invention is controlled to be 0.8-1.0g/cm3。
Example 12 slurry containing ultra high temperature ceramic powder was used as the impregnation solution in both the early and late densification stages. From the comparison results of example 12 and example 4, although example 12 employs ultra-high temperature ceramic powder in both the early and late densification stages, the properties of the final composite material prepared in example 12 are not as good as example 4, especially the density is significantly lower than example 4. Although the proportion of the ultrahigh-temperature ceramic powder in the preparation process of example 12 is only 5 wt%, if the composite material is impregnated with the slurry containing this component all the time, the surface layer of the composite material is easily sealed, resulting in a density gradient. And along with the repeated impregnation, the densification degree of the composite material is gradually improved, the pores are gradually reduced, and the impregnation difficulty at the later stage is increased, so that the performance of the composite material is improved, the performance of the composite material is not obviously improved, and the performance of the composite material is reduced.
Example 13 only the precursor was used as the impregnation solution in both the early and late densification treatment stages. From the results of the tests in example 13, the density of the composite material obtained by this process is significantly lower than that of the present invention, and the tensile strength is inferior to that of the present invention. This further demonstrates the nano-ZrB incorporated in the present invention2The benefits of the/SiC double-phase ceramic powder.
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. C/SiC-ZrB2The preparation method of the composite material is characterized by comprising the following steps:
(1) solidifying and cracking the precursor to obtain the nanometer ZrB2The SiC complex phase ultra-high temperature ceramic powder; the precursor is polyborosilazane-polyzirconyl-oxoalkane copolymer;
(2) mixing the ultrahigh-temperature ceramic powder obtained in the step (1) with a precursor to prepare ultrahigh-temperature ceramic powder slurry;
(3) taking the slurry obtained in the step (2) as an impregnating solution, and carrying out early-stage densification treatment on the C/C composite material; and
(4) taking the precursor as a dipping solution, and carrying out early-stage densification treatment on the precursorThe composite material is subjected to post densification treatment to obtain the C/SiC-ZrB2A composite material.
2. The production method according to claim 1,
curing the precursor at the temperature of 220-260 ℃, and then cracking the precursor at the temperature of 1600-1800 ℃ in an argon atmosphere to obtain the nano ZrB with the particle size of 200-400nm2The SiC complex phase superhigh temperature ceramic powder.
3. The production method according to claim 1 or 2,
when preparing the ultrahigh-temperature ceramic powder slurry, the mass percentage of the ultrahigh-temperature ceramic powder in the slurry is controlled to be less than 30 wt%, preferably 10-30 wt%, and more preferably 10-20 wt%.
4. The production method according to any one of claims 1 to 3,
and performing early densification treatment and later densification treatment by adopting a precursor impregnation cracking method.
5. The production method according to claim 4,
when a precursor impregnation cracking method is adopted for carrying out early densification treatment, the cycle times are 2-5 times; and/or
When the precursor impregnation cracking method is adopted for the post densification treatment, the density increase of the composite material is controlled to be less than or equal to 1 percent.
6. The production method according to claim 5,
when the early densification treatment is carried out, the process conditions of the precursor impregnation cracking method are as follows: the impregnation mode is vacuum impregnation or normal pressure impregnation, the curing temperature is 200-300 ℃, and the cracking temperature is 1600-1800 ℃; and/or
When the later densification treatment is carried out, the process conditions of the precursor impregnation cracking method are as follows: the impregnation method is vacuum impregnation or normal pressure impregnation, the curing temperature is 200-300 ℃, and the cracking temperature is 1600-1800 ℃.
7. The production method according to any one of claims 1 to 6,
and (3) depositing a pyrolytic carbon interface layer on the carbon fiber preform by using a chemical vapor deposition method to obtain the C/C composite material used in the step (3).
8. The production method according to claim 7,
the density of the C/C composite material is 0.8-1.0g/cm3。
9. The production method according to claim 7,
the carbon fiber prefabricated body is any one of a carbon fiber needling structure, a carbon cloth lamination sewing structure and a fine weaving puncturing structure.
10. C/SiC-ZrB2Composite material, characterized in that it is obtained by the process according to any one of claims 1 to 9.
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