CN111233503A - Preparation method of fiber-toughened ceramic matrix composite - Google Patents
Preparation method of fiber-toughened ceramic matrix composite Download PDFInfo
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C2948/00—Indexing scheme relating to extrusion moulding
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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Abstract
The invention discloses a preparation method of a fiber toughened ceramic matrix composite material, which comprises the following steps: s1, preparing a carbon fiber toughening polymer: the method comprises the following steps of taking carbon fibers, resin, a curing agent and a lubricant as raw materials, uniformly stirring the raw materials, placing the raw materials in an extruder for granulation, placing the raw materials in an injection molding machine, injecting the raw materials into a mold under the pressure of 80-100 Mpa, demolding after curing, carrying out heat treatment at 250-300 ℃ for 2-10 hours, and cooling to obtain the CFRP part; s2, preparing the carbon fiber toughened carbon-based porous body: carrying out high-temperature carbonization treatment on the CFRP part obtained in the step S1 to obtain a carbon fiber toughened carbon-based porous body; s3, preparing a SiC ceramic matrix: and (4) performing high-temperature infiltration treatment on the carbon fiber toughened carbon-based porous body obtained in the step S2 to obtain the fiber toughened ceramic-based composite material. Compared with the prior art, the technical scheme of the invention has high efficiency and low cost, is not limited by geometric dimensions, is particularly suitable for producing small parts, can realize near-size forming and manufacturing of special-shaped parts according to actual requirements, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of preparation of fiber toughened ceramic matrix composite materials, and particularly relates to a preparation method of a fiber toughened ceramic matrix composite material.
Background
The carbon fiber toughened SiC-based (C/C-SiC) composite material has the advantages of light weight, high specific modulus, high specific strength, high temperature resistance, corrosion resistance and the like, and shows wide application prospects in the fields of aerospace thermal structure parts, high-speed/high-energy-load equipment braking systems and the like.
At present, the process for preparing the C/C-SiC composite material mainly comprises the following steps:
(1) preparing a carbon fiber toughened carbon-based porous body;
(2) and preparing the SiC matrix.
The preparation method of the SiC matrix mainly comprises the following steps: chemical Vapor Infiltration (CVI), Polymer Impregnation Pyrolysis (PIP) and reactive infiltration (LSI), of which the reactive infiltration (LSI) is receiving attention at low cost and high efficiency. The carbon fiber toughened carbon-based porous body for preparing the SiC matrix is directly related to the microstructure and the performance of the C/C-SiC composite material.
At present, the preparation process of the carbon fiber toughened carbon-based porous body mainly relates to two key aspects of construction of a carbon fiber toughened body and preparation of matrix carbon, and the main methods comprise ① construction of a fiber prefabricated body, impregnation and cracking of a chemical gas phase and/or a precursor to prepare a carbon matrix, ② mixing of fibers and resin, compression molding, high-temperature carbonization, and ③ preparation of the carbon matrix by adding the chemical gas phase and/or the impregnation and cracking of the precursor on the basis of ②.
The preparation methods of the three carbon fiber toughened carbon-based porous bodies are mainly applied to the application fields with low production cost such as aerospace, high-energy-load brake systems and other high-end equipment, and mainly have the following problems: the method has the advantages of high cost, low generation efficiency, long generation period, unsuitability for large-scale batch production, limitation by geometric size and shape, unsuitability for production of parts with different sizes and shapes, and difficulty in meeting the requirement of the civil market on the low-cost carbon fiber toughened SiC-based composite material.
Disclosure of Invention
The invention aims to solve the technical problem in the prior art and provides a preparation method of a fiber toughened ceramic matrix composite material, which is efficient, low in cost, free from the limitation of geometric size and shape and suitable for large-scale industrial production.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of a fiber toughened ceramic matrix composite material, which comprises the following specific steps:
s1, preparation of carbon fiber toughening polymer
S11, granulating
(1) The granulation process comprises the following raw materials:
carbon fiber: preferably, polyacrylonitrile-based carbon fibers are adopted, and the length of the carbon fibers is further preferably 0.1mm to 1 mm;
resin: varnish-type phenol resins are preferably used;
curing agent: preferably, hexamethylenetetramine (more than or equal to 99 percent) is adopted;
lubricant: preferably, magnesium stearate is used, and further preferably, the magnesium content therein is 4.59%;
wherein: the volume fraction of the carbon fiber is 20-50%; the resin, the curing agent and the lubricant are mixed according to the volume fraction ratio of 80-90: 5-10: 5-10, configuring;
in order to further inhibit the volume shrinkage of the carbon fiber reinforced resin composite material (CFRP) during the carbonization process, in step S1, 2 to 10wt% of nano-sized or micro-sized ceramic particles or carbon particles are added to the resin. The inventive introduction of carbon particles or ceramic particles can regulate the size and distribution rule of pores in the matrix after CFRP carbonization.
Preferably, the ceramic particles comprise B4C、SiC、TiC、ZrC、ZrB2、TiB2、BN、Si3N4、Ti3SiC2At least one of the isoparticulates; the carbon particles include at least one of carbon black and pyrolytic carbon powder.
(2) The granulation process of the invention comprises the following specific process flows:
as one of preferable modes, in order to prepare the compound, the invention uses a screw extruder in the granulation process;
preference is further given to using a co-rotating twin-screw extruder ZSC 25 from Noris plastics GmbH & Co.
The screw extruder is provided with a processing unit, and the processing unit sequentially comprises a feeding zone, a plasticizing zone, a homogenizing zone and a nozzle.
According to a preferable scheme, firstly, the resin, the curing agent and the lubricant are stored according to a volume fraction ratio of 80-90: 5-10: 5-10, mixing and stirring to obtain a mixture, storing the mixture in a funnel, and introducing the mixture into a feeding area of a processing unit;
further preferably, a screw feeder is adopted for material guiding;
to ensure a precise and continuous supply of the components, the carbon fibers are preferably introduced directly into the plasticizing zone and mixed with the above-mentioned mixture coming from the feed zone, the volume fraction of the carbon fibers being controlled here to be 20 to 50%.
The carbon fiber and the mixture are uniformly mixed and then are placed in a plasticizing area, and the temperature of the plasticizing area is controlled to be 50 ℃;
and the materials enter a homogenizing zone for processing after passing through a plasticizing zone, and the processed materials are discharged through a circular die with the diameter of 5-10 mm.
Preferably, the temperature in the feeding zone is controlled to be 50-60 ℃; controlling the temperature in the plasticizing zone to be 50-60 ℃; controlling the temperature in the homogenization zone to be 90-100 ℃; the temperature of the nozzle area is controlled to be 90-100 ℃.
Preferably, after the granulation process treatment, the material strip is cooled to room temperature in a standard atmosphere and cut into small compound blocks with the thickness of 2-5 mm.
S12, injection molding-curing
The injection molding process is completed through an injection molding machine, and the adjustable clamping force of the injection molding machine is preferably 150 kN-1000 kN.
Preferably, a processing unit is arranged in the injection molding machine, and the processing unit sequentially comprises a feeding area, a plasticizing area and a nozzle.
The injection molding process comprises the following specific steps:
and placing small compound blocks with the thickness of 2-5 mm obtained in the granulation process in a feeding area, and then drawing the small compound blocks into a plasticizing area by the rotation of a screw in an injection molding machine. During the drawing into the plasticizing zone, the compound pieces become molten due to the shear stress and the thermal radiation of the cylinder. And then, in the axial movement process of the screw, injecting the molten material into a mold with the temperature of 175-200 ℃ through a nozzle under the pressure of 80-100 Mpa. And finally, keeping the temperature in the mold for 90-100 seconds, and after the curing process is finished, opening the mold and ejecting the final CFRP part.
Preferably, the temperature of the barrel is set to 50 to 75 ℃ in the feed zone and to 70 to 85 ℃ in the temperature plasticizing zone and the nozzle. Further preferably, the temperature in the feeding zone is controlled to be 70 ℃ and the temperature in the plasticizing zone and at the nozzle is controlled to be 85 ℃.
S13, heat treatment
After the CFRP part is obtained, the CFRP part is placed in a heating furnace, the temperature is slowly increased to 250-300 ℃ at the temperature increasing speed of 5-10 ℃/min, and the CFRP part is cooled to the room temperature along with the furnace after being kept warm for 2-10 hours.
S2, preparation of carbon fiber toughened carbon-based porous body
Carrying out high-temperature carbonization treatment on the CFRP part obtained in the step S1 at the temperature of 600-1000 ℃ to obtain a carbon fiber toughened carbon-based porous body;
preferably, the high-temperature carbonization treatment specifically comprises:
and (4) heating the CFRP part obtained in the step (S1) in a vacuum environment to 600-800 ℃, preserving heat for 1-3 h, continuously heating to 800-1000 ℃, preserving heat for 1-5 h, and cooling to room temperature to obtain the carbon fiber toughened carbon-based porous body.
Further preferably, the high-temperature carbonization treatment specifically comprises:
and (4) placing the CFRP part obtained in the step (S1) in a vacuum carbon tube furnace, vacuumizing, heating to 600-800 ℃ at a heating rate of 0.1-1.0 ℃/min, preserving heat for 1-3 h, continuously heating to 800-1000 ℃ and preserving heat for 1-5 h, and finally cooling to room temperature along with the furnace.
S3. preparation of SiC ceramic matrix
The carbon fiber toughened carbon-based porous body obtained in the step S2 is subjected to high-temperature infiltration treatment at the temperature of 1000-1800 ℃ to obtain the fiber toughened ceramic-based composite material.
Preferably, the high-temperature infiltration treatment specifically comprises:
placing the carbon fiber toughened carbon-based porous body obtained in the step S2 in a vacuum environment, filling nitrogen or argon to a micro positive pressure, heating to 1000-1200 ℃, and preserving heat for 1-2 hours; heating to 1300-1350 ℃, and vacuumizing; heating to 1600-1800 ℃, preserving the heat for 0.5-1.5 h, and cooling to room temperature.
Further preferably, the high-temperature infiltration treatment specifically comprises:
and (4) placing the carbon fiber toughened carbon-based porous body obtained in the step (S2) in a vacuum carbon tube furnace, vacuumizing, filling nitrogen to a micro positive pressure, heating to 1000-1200 ℃ at a heating rate of 2-10 ℃/min, preserving heat for 1h, continuing to heat to 1300-1350 ℃ at a heating rate of 2-5 ℃/min, vacuumizing, continuing to heat to 1600-1800 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 0.5-1.5 h, and finally cooling to room temperature along with the furnace.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, 2-10 wt% of nano-scale or micron-scale ceramic particles or carbon particles are creatively added into resin powder, so that not only can the volume shrinkage of a carbon fiber reinforced resin composite material (CFRP) in the carbonization process be inhibited, but also the size and the distribution rule of pores in a matrix after the CFRP is carbonized can be further regulated; moreover, the addition of the ceramic particles or the carbon particles is more beneficial to the preparation process of granulation → injection molding → solidification → heat treatment → carbonization → high-temperature infiltration, so that the process flow can efficiently, quickly and massively produce products and simultaneously ensure the performance and quality of the produced products.
The injection molding is creatively set to be completed in a high-temperature cavity through high-pressure injection molding, the heat preservation is completed after the injection molding, namely, the solidification is completed, the solidification and the demolding are performed, then the heating is carried out to 250-300 ℃ for heat treatment, and the cracking in the CFRP high-temperature carbonization process is further relieved.
The invention creatively provides a process method for extrusion forming of carbon fiber toughened polymer, which has high efficiency and low cost, is not limited by geometric dimension, is especially suitable for producing small parts, can realize near-dimension forming and manufacturing of special-shaped parts according to actual requirements, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a bending stress-strain curve of the C/C-SiC composite material obtained in examples 7 and 8.
FIG. 2 is an electron micrograph of the C/C-SiC composite obtained in example 7.
FIG. 3 is an electron micrograph of the C/C-SiC composite material obtained in example 8.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
It should be noted that: in the granulation process of the embodiment of the invention, a homodromous twin-screw extruder ZSC 25 from Noris Plastic GmbH & Co.KG is used, and the screw extruder is provided with a processing unit which sequentially comprises a feeding zone, a plasticizing zone, a homogenizing zone and a nozzle.
The injection molding process of the embodiment of the invention uses an injection molding machine, the adjustable clamping force of the injection molding machine is 150 kN-1000 kN, the injection molding machine is provided with a processing unit, and the processing unit sequentially comprises a feeding area, a plasticizing area and a nozzle.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
The embodiment provides a preparation method of a fiber toughened ceramic matrix composite material, which comprises the following specific steps:
s1, preparation of carbon fiber toughening polymer
S11, granulating
Selecting carbon fibers: polyacrylonitrile-based carbon fiber with length of 0.1mm
Selecting resin: a varnish-type phenolic resin (Bakelite phenolic resin, Germany) added with 2 wt% of BN nano-scale particles with the particle size of 20-50 nanometers
The curing agent is selected from: hexamethylene tetramine (more than or equal to 99 percent)
The lubricant is selected from: magnesium stearate (magnesium content 4.59%)
Storing the resin, the curing agent and the lubricant according to a volume fraction ratio of 90: 5: 5 mixing and stirring, then storing in a funnel, and then introducing them into a feeding area of a screw extruder processing unit through a screw feeder, wherein the temperature of the feeding area is set to be 50 ℃; controlling the volume fraction of the carbon fiber at 30%, and directly introducing the carbon fiber into a plasticizing zone to be mixed with the powder from the feeding zone; after the carbon fibers and the powder are mixed, the mixture enters a plasticizing area, and the temperature of the plasticizing area is set to be 50 ℃; then entering a homogenizing zone and a nozzle zone, wherein the temperatures of the homogenizing zone and the nozzle zone are both set to be 90 ℃, and the nozzle is a circular die in the embodiment; after the material passes through the plasticizing zone, discharging the material processed in the homogenizing zone through a circular die with the diameter of 10 mm; subsequently, the strip was cooled to room temperature in a standard atmosphere and cut into composite pieces having a thickness of 5 mm.
S12, injection molding-curing
The compound pellets obtained in step S11 were placed in the feed zone of an injection molding machine and then pulled into the plasticizing zone by the rotation of the screw in the injection molding machine. During the drawing into the plasticizing zone, the compound pieces become molten due to the shear stress and the thermal radiation of the cylinder. Then, during the axial movement of the screw, the molten material was injected through a nozzle into a mold at a temperature of 200 ℃ under a pressure of 80Mpa, held in the above mold for 90 seconds, and after completion of the solidification process, the mold was opened and the final CFRP part was ejected.
S13, heat treatment
And (5) placing the CFRP part obtained in the step (S12) in a heating furnace, slowly heating to 300 ℃ at the heating speed of 5-10 ℃/min, preserving the heat for 5h, and then cooling to room temperature along with the furnace to obtain the heat-treated CFRP part.
S2, preparation of carbon fiber toughened carbon-based porous body
And (4) placing the CFRP part subjected to heat treatment obtained in the step S1 in a vacuum carbon tube furnace, vacuumizing, heating to 600 ℃ at a heating rate of 0.1-1.0 ℃/min, preserving heat for 2 hours, continuously heating to 800 ℃ and preserving heat for 3 hours, and finally cooling to room temperature along with the furnace.
S3. preparation of SiC ceramic matrix
And (4) placing the carbon fiber toughened carbon-based porous body obtained in the step (S2) in a vacuum carbon tube furnace, vacuumizing, filling nitrogen to a micro positive pressure, heating to 1200 ℃ at a heating rate of 2-10 ℃/min, preserving heat for 1h, continuing to heat to 1350 ℃ at a heating rate of 2-5 ℃/min, vacuumizing, continuing to heat to 1600 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1h, and finally cooling to room temperature along with the furnace to obtain the fiber toughened ceramic-based composite material.
Example 2
This example provides a method for preparing a fiber-toughened ceramic matrix composite, which is substantially the same as example 1 except that:
S1：
s11, adding 3 wt% of SiC nano-particles into resin, wherein the particle size is 50-100 nanometers;
s12, injecting the molten material into the die through a nozzle, wherein the extrusion pressure is 100 Mpa.
Example 3
This example provides a method for preparing a fiber-toughened ceramic matrix composite, which is substantially the same as example 1 except that:
S1：
s11, the length of the carbon fiber is 0.2 mm; 5 wt% of TiC nano-scale particles are added into the resin, and the particle size is 100-300 nanometers; the resin, the curing agent and the lubricant are stored according to the volume fraction ratio of 80: 5: 10, adding; the volume fraction of the carbon fibers was controlled at 40%.
Example 4
This example provides a method for preparing a fiber-toughened ceramic matrix composite, which is substantially the same as example 1 except that:
S1：
s11, the length of the carbon fiber is 0.2 mm; the resin is added with 5 wt% of Ti3SiC2Nano-scale ceramic particles with the particle size of 100-500 nanometers; controlling the volume fraction of the carbon fiber at 40%;
s12, injecting a molten material into a mold through a nozzle, wherein the extrusion pressure is 100 Mpa;
S2：
heating to 600 ℃ at a heating rate of 0.1-1.0 ℃/min, preserving heat for 2h, continuously heating to 1000 ℃ and preserving heat for 2h, and finally cooling to room temperature along with the furnace.
Example 5
This example provides a method for preparing a fiber-toughened ceramic matrix composite, which is substantially the same as example 1 except that:
S1：
s11, the length of the carbon fiber is 0.2 mm; 5 wt% of carbon particles are added into the resin, and the particle size is 10-100 micrometers; the resin, the curing agent and the lubricant are stored according to the volume fraction ratio of 80: 5: 10, adding; the volume fraction of the carbon fibers was controlled at 40%.
Example 6
This example provides a method for preparing a fiber-toughened ceramic matrix composite, which is substantially the same as example 1 except that:
S1：
s11, the length of the carbon fiber is 0.5 mm; the resin is added with 5 wt% of ZrC micron-sized ceramic particles, and the particle size is 20-100 microns; the resin, the curing agent and the lubricant are stored according to the volume fraction ratio of 80: 5: 10, adding; controlling the volume fraction of the carbon fiber at 30%;
s12, injecting a molten material into a mold through a nozzle, wherein the extrusion pressure is 100 Mpa;
S3：
and (4) placing the carbon fiber toughened carbon-based porous body obtained in the step (S2) in a vacuum carbon tube furnace, vacuumizing, filling nitrogen to a micro positive pressure, heating to 1200 ℃ at a heating rate of 2-10 ℃/min, preserving heat for 1h, continuing to heat to 1350 ℃ at a heating rate of 2-5 ℃/min, vacuumizing, continuing to heat to 1800 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1h, and finally cooling to room temperature along with the furnace to obtain the fiber toughened ceramic-based composite material.
Example 7
This example provides a method for preparing a fiber-toughened ceramic matrix composite, which is substantially the same as example 1 except that:
S1：
s11, the length of the carbon fiber is 0.5 mm; the resin was added with 5 wt% of B4C nano-scale ceramic particles with the particle size of 100-300 nanometers; the resin, the curing agent and the lubricant are stored according to the volume fraction ratio of 80: 5: 10, adding; (ii) a Controlling the volume fraction of the carbon fiber at 50%;
s12, injecting a molten material into a mold through a nozzle, wherein the extrusion pressure is 100 Mpa;
S3：
and (4) placing the carbon fiber toughened carbon-based porous body obtained in the step (S2) in a vacuum carbon tube furnace, vacuumizing, filling nitrogen to a micro positive pressure, heating to 1200 ℃ at a heating rate of 2-10 ℃/min, preserving heat for 1h, continuing to heat to 1350 ℃ at a heating rate of 2-5 ℃/min, vacuumizing, continuing to heat to 1800 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1h, and finally cooling to room temperature along with the furnace to obtain the fiber toughened ceramic-based composite material.
Example 8
This example provides a method for preparing a fiber-toughened ceramic matrix composite, which is substantially the same as example 1 except that:
S1：
s11, the length of the carbon fiber is 0.5 mm; the resin was added with 7 wt% of B4C micron-sized particles with the particle size of 50-100 microns; the resin, the curing agent and the lubricant are stored according to the volume fraction ratio of 80: 5: 10, adding; controlling the volume fraction of the carbon fiber at 40%;
S3：
and (4) placing the carbon fiber toughened carbon-based porous body obtained in the step (S2) in a vacuum carbon tube furnace, vacuumizing, filling nitrogen to a micro positive pressure, heating to 1200 ℃ at a heating rate of 2-10 ℃/min, preserving heat for 1h, continuing to heat to 1350 ℃ at a heating rate of 2-5 ℃/min, vacuumizing, continuing to heat to 1800 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1h, and finally cooling to room temperature along with the furnace to obtain the fiber toughened ceramic-based composite material.
Example 9
This example provides a method for preparing a fiber-toughened ceramic matrix composite, which is substantially the same as example 1 except that:
S1：
s11, the length of the carbon fiber is 1.0 mm; the resin was added with 4 wt% of Si3N4The nano-scale ceramic particles have the particle size of 100-300 nanometers; the resin, the curing agent and the lubricant are stored according to the volume fraction ratio of 80: 5: 10, adding; controlling the volume fraction of the carbon fiber to be 20%;
s12, injecting a molten material into a mold through a nozzle, wherein the extrusion pressure is 100 Mpa;
S3：
and (4) placing the carbon fiber toughened carbon-based porous body obtained in the step (S2) in a vacuum carbon tube furnace, vacuumizing, filling nitrogen to a micro positive pressure, heating to 1200 ℃ at a heating rate of 2-10 ℃/min, preserving heat for 1h, continuing to heat to 1350 ℃ at a heating rate of 2-5 ℃/min, vacuumizing, continuing to heat to 1800 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1h, and finally cooling to room temperature along with the furnace to obtain the fiber toughened ceramic-based composite material.
As shown in Table 1, the performance of the fiber-toughened ceramic matrix composite materials obtained in examples 1 to 9 was tested; as shown in fig. 1, the bending stress-strain curves of the C/C-SiC composite materials obtained in examples 7 and 8 show that examples 7 and 8 show better mechanical properties and fracture behavior, indicating that the process features of the invention have better application prospects; as shown in fig. 2, which is an electron micrograph of the C/C-SiC composite material obtained in example 7, it can be seen that the prepared material has no obvious preferred orientation of fiber distribution, higher density and fewer pores; as shown in FIG. 3, which is an electron micrograph of the C/C-SiC composite material obtained in example 8, it can be seen that the prepared material has no obvious preferred orientation of fiber distribution, higher density and fewer pores.
TABLE 1 testing of the Properties of fiber-toughened ceramic matrix composites
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the fiber toughened ceramic matrix composite material is characterized by comprising the following steps of:
s1, preparation of carbon fiber toughening polymer
Carbon fibers, resin, a curing agent and a lubricant are used as raw materials, the raw materials are uniformly stirred and then placed in an extruder for granulation, and material particles are obtained; placing the material particles in an injection molding machine, injecting the material particles into a mold with the temperature of 175-200 ℃ under the pressure of 80-100 Mpa, keeping the pressure for 90-100 s, demolding, carrying out heat treatment at 250-300 ℃ for 2-10 h, and cooling to obtain a CFRP part;
s2, preparation of carbon fiber toughened carbon-based porous body
Carrying out high-temperature carbonization treatment on the CFRP part obtained in the step S1 at the temperature of 600-1000 ℃ to obtain a carbon fiber toughened carbon-based porous body;
s3. preparation of SiC ceramic matrix
Carrying out high-temperature infiltration treatment on the carbon fiber toughened carbon-based porous body obtained in the step S2 at the temperature of 1000-1800 ℃ to obtain a fiber toughened ceramic-based composite material;
wherein: in the step S1, the volume fraction of the carbon fiber is 20-50%; the resin, the curing agent and the lubricant are mixed according to the volume fraction ratio of 80-90: 5-10: 5-10, configuring; 2-10 wt% of nano-scale or micro-scale ceramic particles or carbon particles are added into the resin.
2. The method for preparing a fiber toughened ceramic matrix composite according to claim 1, wherein in step S1, said ceramic particles include B4C、SiC、TiC、ZrC、ZrB2、TiB2、BN、Si3N4、Ti3SiC2At least one of the isoparticulates; the carbon particles include at least one of carbon black and pyrolytic carbon powder.
3. The method for preparing a fiber-toughened ceramic-based composite material according to claim 1, wherein in step S1, the carbon fibers are polyacrylonitrile-based carbon fibers, and preferably, the length of the carbon fibers is 0.1mm to 1 mm.
4. The method for preparing a fiber toughened ceramic matrix composite according to claim 1, wherein in step S1, the resin is a phenolic resin.
5. The method for preparing a fiber-toughened ceramic-based composite material according to claim 1, wherein in step S1, the curing agent is hexamethylenetetramine; preferably, in step S1, the lubricant is magnesium stearate.
6. The method for preparing a fiber toughened ceramic matrix composite according to any one of claims 1 to 5, wherein in step S1, the granulation process performed in the extruder is specifically as follows:
s11, arranging a processing unit on the extruder, wherein the processing unit sequentially comprises a feeding area, a plasticizing area, a homogenizing area and a nozzle area, mixing resin, a curing agent, a lubricant storage and carbon fibers, sequentially passing through the feeding area, the plasticizing area and the homogenizing area, and finally discharging through a nozzle;
wherein the temperature in the feeding zone is controlled to be 50-60 ℃; controlling the temperature in the plasticizing zone to be 50-60 ℃; controlling the temperature in the homogenization zone to be 90-100 ℃; the temperature of the nozzle area is controlled to be 90-100 ℃.
7. The method for preparing a fiber-toughened ceramic-based composite material according to any one of claims 1 to 5, wherein in step S1, the injection molding-curing process in the injection molding machine and the mold is specifically as follows:
s12, arranging a processing unit in the injection molding machine, wherein the processing unit sequentially comprises a feeding area, a plasticizing area and a nozzle, the material particles enter from the feeding area after granulation, after the plasticizing area is in a molten state, the molten material is injected into a mold with the temperature of 175-200 ℃ through the nozzle under the pressure of 80-100 Mpa, the mold is kept for 90-100 seconds, and a CFRP part is obtained after demolding;
wherein the temperature of the feeding zone is controlled to be 50-75 ℃, and the temperature of the plasticizing zone and the temperature of the nozzle are controlled to be 70-85 ℃.
8. The method for preparing a fiber-toughened ceramic-based composite material according to any one of claims 1 to 5, wherein in step S1, the heat treatment process specifically comprises:
s13, placing the demoulded CFRP part in a heating furnace, slowly heating to 250-300 ℃ at a heating speed of 5-10 ℃/min, preserving heat for 2-10 h, and cooling to room temperature along with the furnace.
9. The method for preparing a fiber-toughened ceramic-based composite material according to claim 1, wherein the step S2 specifically comprises: and (4) heating the CFRP part obtained in the step (S1) in a vacuum environment to 600-800 ℃, preserving heat for 1-3 h, continuously heating to 800-1000 ℃, preserving heat for 1-5 h, and cooling to room temperature to obtain the carbon fiber toughened carbon-based porous body.
10. The method for preparing a fiber-toughened ceramic-based composite material according to claim 1, wherein the step S3 specifically comprises: placing the carbon fiber toughened carbon-based porous body obtained in the step S2 in a vacuum environment, filling nitrogen or argon to a micro positive pressure, heating to 1000-1200 ℃, and preserving heat for 1-2 hours; heating to 1300-1350 ℃, and vacuumizing; heating to 1600-1800 ℃, preserving the heat for 0.5-1.5 h, and cooling to room temperature.
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