CN110683852A - Low-cost ceramic-based thermostructural composite material and preparation method thereof - Google Patents
Low-cost ceramic-based thermostructural composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low-cost ceramic matrix composite and a preparation method thereof, belonging to the technical field of composite materials. The ceramic-based thermostructural composite material is formed by impregnating a SiCN ceramic precursor into a carbon fiber braided fabric reinforcement and then compounding the carbon fiber braided fabric reinforcement through curing and cracking processes. According to the preparation method, a SiCN ceramic precursor is used as an impregnation phase, the precursor is introduced into a prefabricated carbon fiber braided fabric through vacuum impregnation, the curing and cracking processes are completed under corresponding temperature and pressure, and the steps are repeated to obtain the compact ceramic matrix composite. The process reduces the preparation cost of the composite material from the three aspects of raw material cost, energy consumption and time, and the composite material can be used for bearing members under the high-temperature condition and has better application prospect.
Description
Technical Field
The invention relates to a ceramic matrix composite material and a preparation method thereof, in particular to a carbon fiber reinforced ceramic matrix thermostructural composite material, and belongs to the technical field of composite materials.
Background
The thermal structure material is a material capable of keeping a certain bearing capacity in a high-temperature aerobic environment, and has wide requirements in the fields of aviation, aerospace and the like. The traditional thermostructural materials mainly comprise metal materials, alloy materials, ceramic materials, resin-based composite materials and the like, the application of the metal materials and the alloy materials is limited to the lower melting point, and the highest service temperature is generally not more than 1100 ℃; the ceramic material has extremely high temperature resistance level and oxidation resistance, but the natural brittle property makes the ceramic material difficult to bear the impact of concentrated force, so that the wide application of the ceramic material is limited; the resin-based composite material adopts an ablation type heat-proof mechanism, has the greatest advantages of small riddle, high strength, capability of keeping the strength in a large heat flow environment, poor oxidation resistance and capability of meeting the short-time use in a specific strong heat flow anaerobic environment.
With the continuous development of the technology in the aerospace field, the performance requirements of the thermostructural materials are increasing day by day, and the carbon fiber reinforced ceramic matrix composite material with higher temperature resistance level and stronger oxidation resistance gradually becomes the first choice of a novel thermostructural material.
The carbon fiber reinforced ceramic matrix composite takes carbon fiber as a reinforcement and ceramic as a matrix, integrates the excellent high-temperature mechanical and physical properties of the carbon fiber and the good chemical and thermal stability of the ceramic matrix, overcomes the defect of brittleness of a single ceramic material, and is a representative of a thermal structure composite which integrates thermal protection, structural bearing and oxidation resistance, and has the characteristics of high fracture toughness, high strength, large specific heat capacity, thermal shock resistance, light specific gravity, excellent oxidation resistance and the like.
In the preparation methods of ceramic matrix composites in the prior art, the liquid Phase Impregnation Pyrolysis (PIP) method and the Chemical Vapor Infiltration (CVI) method are most deeply and commonly researched and applied. The ceramic matrix composite material prepared by the CVI method has high ceramic matrix content and excellent high-temperature oxidation resistance, but the preparation process is limited, the period is too long, the composite material is more used for forming and densifying thin-walled structural parts, and large-size thick-wall complex-shaped components are difficult to obtain. The PIP process is a process for preparing the composite material by impregnating the carbon fiber fabric with the liquid-phase ceramic precursor and then performing pyrolysis, and is an ideal process for preparing the ceramic matrix composite engineering component with large size and complex shape. When the ceramic matrix composite material prepared by the PIP method is used, except for the fiber preform, the ceramic precursor is also an important key raw material, and the mechanical property, the oxidation resistance, the ablation resistance and other comprehensive properties of the composite material are directly influenced by the performance of the ceramic precursor.
At present, the preparation cost of common ceramic-based thermostructural composite materials is high, wherein the ceramic precursor accounts for a large share of the cost of raw materials, for example, the cost of the SiC precursor used by the C/SiC composite material is generally more than 5000 yuan/kg.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a low-cost ceramic-based thermostructural composite material and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a ceramic-based thermostructural composite material is prepared by impregnating a SiCN ceramic precursor with a carbon fiber braided fabric reinforcement and then compounding the reinforcement by curing and cracking processes.
In an alternative embodiment, the carbon fiber woven fabric is in a woven form of at least one of a three-dimensional cross, a fiber cloth lay stitch, a two-dimensional half weave, a three-dimensional wound yarn, or a three-dimensional five-dimensional weave.
In an alternative embodiment, the carbon fiber gauge of the carbon fiber braid is T300 grade, T700 grade, T800 grade, T1000 grade, M40J grade, or M55J grade.
A preparation method of a ceramic-based thermostructural composite material comprises the following steps:
(1) preparing a pyrolytic carbon interface layer on the fiber surface of a carbon fiber braided fabric formed in a certain braided form by adopting a Chemical Vapor Deposition (CVD) method to form a carbon fiber braided fabric reinforcement;
(2) impregnating impregnation liquid formed by preheating a SiCN ceramic precursor into the carbon fiber braided fabric reinforcement formed in the step (1) at a certain temperature and under a certain pressure, and keeping the impregnation time for a certain time to form a carbon fiber braided fabric blank body after the SiCN impregnation;
(3) carrying out high-temperature pressurization curing on the blank formed in the step (2);
(4) carrying out pyrolysis on the solidified blank formed in the step (3);
(5) and (5) repeating the steps (2) to (4) for 5-10 times to obtain the ceramic-based thermostructural composite material.
In an alternative embodiment, the carbon fiber braided fabric in the step (1) is braided in at least one of an orthogonal three-way direction, a fiber cloth layer sewing, a two-dimensional half-braiding, a three-dimensional winding yarn or a three-dimensional five-way direction.
In an alternative embodiment, the carbon fiber specification of the carbon fiber woven fabric in the step (1) is T300 grade, T700 grade, T800 grade, T1000 grade, M40J grade or M55J grade.
In an optional embodiment, the preheating temperature of the SiCN in the step (2) is 60 to 80 ℃.
In an optional embodiment, the temperature in the impregnation process in the step (2) is between room temperature and 90 ℃, the pressure is between-0.1 and 1.0MPa, and the impregnation time is between 2 and 3 hours.
In an alternative embodiment, the curing in step (3): the curing temperature is 180-200 ℃, the curing pressure is 0.3-3 Mpa, and the heat preservation time is 4-8 hours.
In an optional embodiment, the cracking in the step (4) is performed in an inert atmosphere, the temperature is 900-1600 ℃, the heat preservation time is 3-6 hours, and the inert atmosphere can be nitrogen or argon.
Compared with the prior art, the invention has the following beneficial effects:
(1) the SiCN is adopted as the ceramic precursor in the ceramic-based thermostructural composite material provided by the embodiment of the invention, the cost is lower than 1000 yuan/kg, compared with the prior art, the cost of raw materials can be greatly reduced, and the cost performance of the ceramic-based thermostructural composite material is improved.
(2) The ceramic-based thermostructural composite material provided by the embodiment of the invention adopts SiCN as a ceramic precursor, the ceramic yield is up to more than 70%, the curing temperature is lower than 200 ℃, the vacuum impregnation efficiency is higher, and the preparation cost is reduced in various aspects such as time, energy consumption and the like.
(3) The ceramic-based thermostructural composite material provided by the embodiment of the invention takes the carbon fiber braided fabric as a reinforcement and takes SiCN ceramic as a matrix, has excellent mechanical property, higher temperature resistance level and high-temperature oxidation resistance, can be used for bearing members under high-temperature conditions, and has better application prospect.
Drawings
FIG. 1 is an SEM image of the microstructure of a low-cost ceramic thermostructural composite material prepared in example 1;
FIG. 2 is a matrix XRD pattern of the low-cost ceramic matrix thermostructural composite material prepared in example 1;
FIG. 3 is an SEM photograph of a fracture of a tensile test specimen of the low-cost ceramic-based thermostructural composite material prepared in example 2;
FIG. 4 is a graph of density as a function of dip runs for a low cost ceramic matrix thermostructural composite prepared in example 3.
Detailed Description
In order that those skilled in the art will better understand the present invention, the following detailed description of the invention is provided in conjunction with the accompanying drawings and specific embodiments.
The invention designs a preparation method of a low-cost ceramic-based thermostructural composite material, which comprises the steps of utilizing a PIP process, taking a SiCN ceramic precursor as an impregnation phase and a carbon fiber braided fabric as a preform, introducing the precursor into the preform through vacuum impregnation, completing the curing and cracking processes under a proper temperature system, and repeating the steps to obtain the compact ceramic-based composite material.
In the ceramic-based thermostructural composite material of the invention, SiCN used as a ceramic precursor is a liquid polymer with certain flow characteristics, and the preparation method which can be adopted is as follows: the preparation method is characterized by taking methyltrichlorosilane, methylvinyl dichlorosilane and ammonia gas as main raw materials and carrying out ammonolysis polymerization reaction in a toluene solvent, a normal hexane solvent or a tetrahydrofuran solvent at a certain temperature according to a certain proportion.
In the preparation process of the ceramic-based thermostructural composite material, a SiCN ceramic precursor is taken as a dipping phase and is introduced into a carbon fiber braided fabric reinforcement body by a vacuum dipping method. The vacuum impregnation method comprises the following steps: impregnating the carbon fiber fabric with the impregnating solution at a certain temperature (room temperature to 90 ℃) and under a certain pressure (minus 0.1 to 1.0MPa) for 2 to 3 hours to obtain a blank after complete impregnation, and taking out the blank and putting the blank into a curing tank (60 to 90 ℃); curing at a certain temperature (180-200 ℃) and pressure (0.3-3 MPa) for 4-8 hours, and slowly cooling along with a furnace until the impregnation liquid is completely cured.
The embodiment of the invention provides a ceramic matrix thermostructural composite material, which is prepared by impregnating a SiCN ceramic precursor into a carbon fiber braided fabric reinforcement and then compounding the carbon fiber braided fabric reinforcement through curing and cracking processes.
Specifically, in the embodiment of the invention, the carbon fiber braided fabric is in a braided form of at least one of an orthogonal three-way, fiber cloth layer sewing, a two-dimensional half-braiding, a three-dimensional yarn winding or a three-dimensional five-way.
Specifically, in the embodiment of the present invention, the carbon fiber specification of the carbon fiber woven fabric is T300 grade, T700 grade, T800 grade, T1000 grade, M40J grade, or M55J grade.
The embodiment of the invention also provides a preparation method of the ceramic-based thermostructural composite material, which comprises the following steps:
(1) preparing a pyrolytic carbon interface layer on the fiber surface of a carbon fiber braided fabric formed in a certain braided form by adopting a Chemical Vapor Deposition (CVD) method to form a carbon fiber braided fabric reinforcement;
(2) impregnating impregnation liquid formed by preheating a SiCN ceramic precursor into the carbon fiber braided fabric reinforcement formed in the step (1) at a certain temperature and under a certain pressure, and keeping the impregnation time for a certain time to form a carbon fiber braided fabric blank body after the SiCN impregnation;
(3) carrying out high-temperature pressurization curing on the blank formed in the step (2);
(4) carrying out pyrolysis on the solidified blank formed in the step (3);
(5) and (5) repeating the steps (2) to (4) for 5-10 times to obtain the ceramic-based thermostructural composite material.
The following are several specific embodiments of the invention:
example 1
The embodiment of the invention provides a preparation method of a ceramic matrix thermostructural composite material taking a three-way orthogonal structure T300-3k carbon fiber fabric as a reinforcement, which comprises the following steps:
(1) a three-dimensional orthogonal structure T300-3k carbon fiber fabric is used as a reinforcement to prepare a 100mm X100 mm flat sample, and the volume fraction of the fabric fiber is 40%.
(2) Under the protection of nitrogen gas flow, 500g of SiCN precursor is added into a flask, and the temperature is raised and preheated to 60 ℃ while stirring, so that light yellow sticky impregnation liquid is obtained.
(3) Introducing the impregnation liquid in the step (2) into the fabric prepared in the step (1) by a vacuum impregnation method. Keeping the temperature at 60 ℃ and-0.1 MPa for half an hour to ensure that the impregnation liquid is fully impregnated into the fabric; the impregnation was completed at elevated pressure to 0.5MPa for a holding time of 2 hours.
(4) Taking out the impregnated braided fabric obtained in the step (3), and putting the braided fabric into a curing tank (at 60 ℃); curing at 200 deg.C under normal pressure for 8 hr until the precursor is completely cured.
(5) High-temperature cracking: and (3) putting the blank solidified in the step (4) into a high-temperature cracking furnace, and carrying out high-temperature cracking for 3 hours in an inert atmosphere (nitrogen or argon) at 850 ℃ to finish the high-temperature conversion of the SiCN organic polymer precursor into the SiCN ceramic.
(6) And (5) repeating the steps (3) to (5) for 5 times to finally obtain the compact SiCN ceramic matrix composite.
The microstructure of the surface of the low-cost ceramic-based thermostructural composite material prepared by the method is observed by a scanning electron microscope, so that the surface of the material has no obvious holes and the density of the material is good.
Aiming at the density test of the low-cost ceramic-based thermostructural composite material prepared by the method by using a drainage method, the compactness of the material is good, and the density is 1.81g/cm3。
When the low-cost ceramic-based thermostructural composite material prepared by the method is observed by a scanning electron microscope, the fact that no obvious holes exist on the surface of the material can be seen, and the material has good density; the material has obvious fiber extraction phenomenon, which proves that the material has a good toughening mechanism, and the details are shown in figure 1.
The phase analysis of the low-cost ceramic-based thermostructural composite material prepared by the method is carried out by an XRD diffractometer, and the material matrix is mainly composed of Si-C-N ceramic with low crystallinity, which is shown in the attached figure 2 in detail.
The room temperature bending strength of the low-cost ceramic matrix composite material prepared by the method is tested by a three-point bending method, and the room temperature strength of the obtained composite material is 274 MPa.
Example 2
The embodiment of the invention provides a preparation method of a ceramic matrix thermostructural composite material taking a three-way orthogonal structure T300-3k carbon fiber fabric as a reinforcement, which comprises the following steps:
(1) a three-dimensional orthogonal structure T300-3k carbon fiber fabric is used as a reinforcement to prepare a 100mm X100 mm flat sample, and the volume fraction of the fabric fiber is 40%.
(2) Under the protection of nitrogen gas flow, 500g of SiCN precursor is added into a flask, and the temperature is raised and preheated to 80 ℃ while stirring, so that light yellow sticky impregnation liquid is obtained.
(3) Introducing the impregnation liquid in the step (2) into the fabric prepared in the step (1) by a vacuum impregnation method. Keeping the temperature at 80 ℃ and-0.1 MPa for half an hour to ensure that the impregnation liquid is fully impregnated into the fabric; the impregnation was completed at elevated pressure to 0.2MPa for a holding time of 2 hours.
(4) Taking out the impregnated braided fabric obtained in the step (3), and putting the braided fabric into a curing tank (at 80 ℃); and (3) carrying out pressurization curing at the temperature of 200 ℃ and under the pressure of 2.5MPa for 8 hours until the precursor is completely cured.
(5) High-temperature cracking: and (3) putting the blank solidified in the step (4) into a high-temperature cracking furnace, and carrying out high-temperature cracking for 3 hours in an inert atmosphere (nitrogen or argon) at 850 ℃ to finish the high-temperature conversion of the SiCN organic polymer precursor into the SiCN ceramic.
(6) And (5) repeating the steps (3) to (5) for 5 times to finally obtain the compact SiCN ceramic matrix composite.
The fracture of the tensile sample of the low-cost ceramic-based thermostructural composite material prepared by the method is observed by a scanning electron microscope, so that the surface of the material has no obvious holes and the material has good density; the material has obvious fiber extraction phenomenon, which proves that the material has a good toughening mechanism, and the details are shown in figure 3.
The density test of the low-cost ceramic-based thermostructural composite material prepared by the method by using a drainage method proves that the compactness of the material is good, and the density is 1.87g/cm3。
The phase analysis of the low-cost ceramic-based thermostructural composite material prepared by the method is carried out by an XRD diffractometer, and the material matrix is mainly composed of Si-C-N ceramic with low crystallinity.
The low-cost ceramic matrix composite prepared by the method is subjected to 1200 ℃ bending strength test by a three-point bending method, and the high-temperature bending strength of the material is 364 MPa.
Example 3
The embodiment of the invention provides a preparation method of a ceramic matrix thermostructural composite material taking a three-way orthogonal structure T300-1k carbon fiber fabric as a reinforcement, which comprises the following steps:
(1) a three-dimensional orthogonal structure T300-1k carbon fiber fabric is used as a reinforcement to prepare a 100mm X100 mm flat sample, and the volume fraction of the fabric fiber is 40%.
(2) Under the protection of nitrogen gas flow, 500g of SiCN precursor is added into a flask, and the temperature is raised and preheated to 60 ℃ while stirring, so that light yellow sticky impregnation liquid is obtained.
(3) Introducing the impregnation liquid in the step (2) into the fabric prepared in the step (1) by a vacuum impregnation method. Keeping the temperature at 60 ℃ and-0.1 MPa for half an hour to ensure that the impregnation liquid is fully impregnated into the fabric; the impregnation was completed at elevated pressure to 0.5MPa for a holding time of 2 hours.
(4) Taking out the impregnated braided fabric obtained in the step (3), and putting the braided fabric into a curing tank (at 60 ℃); curing at 180 deg.c for 8 hr under normal pressure until the precursor is cured completely.
(5) High-temperature cracking: and (3) putting the blank solidified in the step (4) into a high-temperature cracking furnace, and carrying out high-temperature cracking for 3 hours in an inert atmosphere (nitrogen or argon) at 850 ℃ to finish the high-temperature conversion of the SiCN organic polymer precursor into the SiCN ceramic.
(6) And (5) repeating the steps (3) to (5) for 6 times to finally obtain the compact SiCN ceramic matrix composite.
The microstructure of the surface of the low-cost ceramic-based thermostructural composite material prepared by the method is observed by a scanning electron microscope, so that the surface of the material has no obvious holes and the density of the material is good.
The density test of the low-cost ceramic-based thermostructural composite material prepared by the method by using a drainage method proves that the compactness of the material is good, and the density is 1.86g/cm3. The density change curve of each turn of the composite material is shown in figure 4.
The phase analysis of the low-cost ceramic-based thermostructural composite material prepared by the method is carried out by an XRD diffractometer, and the material matrix is mainly composed of Si-C-N ceramic with low crystallinity.
The room temperature bending strength test is carried out on the low-cost ceramic matrix composite material prepared by the method by using a three-point bending method, and the room temperature strength of the material is 296 MPa.
Example 4
The embodiment of the invention provides a preparation method of a ceramic matrix thermostructural composite material taking a three-way orthogonal structure T300-1k carbon fiber fabric as a reinforcement, which comprises the following steps:
(1) a three-dimensional orthogonal structure T300-1k carbon fiber fabric is used as a reinforcement to prepare a 100mm X100 mm flat sample, and the volume fraction of the fabric fiber is 40%.
(2) Under the protection of nitrogen gas flow, 500g of SiCN precursor is added into a flask, and the temperature is raised and preheated to 80 ℃ while stirring, so that light yellow sticky impregnation liquid is obtained.
(3) Introducing the impregnation liquid in the step (2) into the fabric prepared in the step (1) by a vacuum impregnation method. Keeping the temperature at 80 ℃ and-0.1 MPa for half an hour to ensure that the impregnation liquid is fully impregnated into the fabric; the impregnation was completed at elevated pressure to 0.2MPa for a holding time of 2 hours.
(4) Taking out the impregnated braided fabric obtained in the step (3), and putting the braided fabric into a curing tank (at 80 ℃); and (3) carrying out pressurization curing at the temperature of 200 ℃ and under the pressure of 2.5MPa for 8 hours until the precursor is completely cured.
(5) High-temperature cracking: and (3) putting the blank solidified in the step (4) into a high-temperature cracking furnace, and carrying out high-temperature cracking for 3 hours in an inert atmosphere (nitrogen or argon) at 850 ℃ to finish the high-temperature conversion of the SiCN organic polymer precursor into the SiCN ceramic.
(6) And (5) repeating the steps (3) to (5) for 5 times to finally obtain the compact SiCN ceramic matrix composite.
The microstructure of the surface of the low-cost ceramic-based thermostructural composite material prepared by the method is observed by a scanning electron microscope, so that the surface of the material has no obvious holes and the density of the material is good.
The density test of the low-cost ceramic-based thermostructural composite material prepared by the method by using a drainage method proves that the compactness of the material is good, and the density is 1.92g/cm3。
The phase analysis of the low-cost ceramic-based thermostructural composite material prepared by the method is carried out by an XRD diffractometer, and the material matrix is mainly composed of Si-C-N ceramic with low crystallinity.
The low-cost ceramic matrix composite material prepared by the method is subjected to 1200 ℃ bending strength test by a three-point bending method, and the high-temperature bending strength of the material is 387 MPa.
It should be understood that the specific embodiments described above are merely examples for clarity of description and are not intended to limit the embodiments. Any changes or substitutions that may be easily made by those skilled in the art within the technical scope of the present disclosure are intended to be included within the scope of the present disclosure.
The invention has not been described in detail in part of the common general knowledge of those skilled in the art.
Claims (10)
1. A ceramic-based thermostructural composite material is characterized in that the composite material is prepared by impregnating a SiCN ceramic precursor into a carbon fiber braided fabric reinforcement and then compounding the carbon fiber braided fabric reinforcement by curing and cracking processes.
2. The ceramic matrix thermostructural composite material of claim 1, wherein the carbon fiber braid is in a braided form using at least one of orthorhombic three-way, fiber cloth lay-up stitch, two-dimensional half-braid, three-dimensional wound yarn, or three-dimensional five-way.
3. The ceramic matrix thermostructural composite material according to claim 1, characterized in that the carbon fiber gauge of the carbon fiber braid is a T300 grade, a T700 grade, a T800 grade, a T1000 grade, an M40J grade or an M55J grade.
4. A preparation method of a ceramic-based thermostructural composite material is characterized by comprising the following steps:
(1) preparing a pyrolytic carbon interface layer on the fiber surface of a carbon fiber braided fabric formed in a certain braiding form by adopting a chemical vapor deposition method to form a carbon fiber braided fabric reinforcement;
(2) impregnating impregnation liquid formed by preheating a SiCN ceramic precursor into the carbon fiber braided fabric reinforcement formed in the step (1) at a certain temperature and under a certain pressure, and keeping the impregnation time for a certain time to form a SiCN impregnated blank;
(3) carrying out high-temperature pressurizing and curing on the carbon fiber braided fabric blank formed in the step (2);
(4) carrying out pyrolysis on the solidified blank formed in the step (3);
(5) and (5) repeating the steps (2) to (4) for 5-10 times to prepare the ceramic-based thermostructural composite material.
5. The method for preparing the ceramic thermostructural composite material according to claim 4, wherein the carbon fiber woven fabric in the step (1) is in a woven form using at least one of an orthogonal three-dimensional direction, a fiber cloth layer stitch, a two-dimensional half-woven, a three-dimensional wound yarn, or a three-dimensional five-dimensional direction.
6. The method for preparing a ceramic thermostructural composite material according to claim 4, characterized in that the carbon fiber specification of the carbon fiber braid in step (1) is a T300 grade, a T700 grade, a T800 grade, a T1000 grade, an M40J grade or an M55J grade.
7. The preparation method of the ceramic thermostructural composite material according to claim 4, characterized in that the SiCN preheating temperature in the step (2) is 60-80 ℃.
8. The preparation method of the ceramic thermostructural composite material according to claim 4, characterized in that the temperature in the impregnation process in the step (2) is room temperature to 90 ℃, the pressure is-0.1 to 1.0MPa, and the impregnation time is 2 to 3 hours.
9. The method for preparing a ceramic thermostructural composite material according to claim 4, characterized in that the curing in step (3): the curing temperature is 180-200 ℃, the curing pressure is 0.3-3 Mpa, and the heat preservation time is 4-8 hours.
10. The preparation method of the ceramic thermostructural composite material according to claim 4, characterized in that the cracking in step (4) is carried out in an inert atmosphere, the temperature is 900-1600 ℃, the holding time is 3-6 hours, and the inert atmosphere is nitrogen or argon.
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