CN113943160B - Preparation method of silicon carbide ceramic matrix composite with self-repairing function - Google Patents
Preparation method of silicon carbide ceramic matrix composite with self-repairing function Download PDFInfo
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Abstract
The invention belongs to the technical field of ceramic matrix composite preparation, and particularly relates to a preparation method of a silicon carbide ceramic matrix composite with a self-repairing function. The method comprises the steps of carrying out surface treatment on micro-nano particles with a self-healing function by utilizing a chemical vapor deposition process, depositing a uniform BN coating layer on the surfaces of the micro-nano particles to obtain surface modified self-healing particles with a core-shell structure, preparing the particles, high carbon residue resin, an organic solvent and a dispersing agent into slurry, preparing the slurry and fibers into prepreg, and carrying out curing, carbonization and liquid Si infiltration to obtain the modified silicon carbide ceramic-based composite material. On one hand, the method utilizes a core layer with a self-repairing functional component in a core-shell structure to generate glass phase sealing and filling pores and cracks at high temperature; on the other hand, since the shell layer is BN having a layered structure, when a crack propagates to the surface of the core-shell structure, the shell layer having a weak interface characteristic extends the propagation path of the crack through an energy absorption mechanism such as interlayer slip, crack deflection, and the like.
Description
Technical Field
The invention belongs to the technical field of ceramic matrix composite preparation, and particularly relates to a preparation method of a silicon carbide ceramic matrix composite with a self-repairing function.
Background
Ceramic Matrix Composites (CMCs) generally refer to composites in which a ceramic matrix is loaded with a reinforcement material to form a dispersed phase of the loaded reinforcement material and a continuous phase of the ceramic matrix, wherein the dispersed phase may be continuous fibers, particles, or whiskers. Currently, much research in the aerospace field is mainly carried out on continuous fiber reinforced ceramic matrix composites, in particular on silicon carbide fiber reinforced silicon carbideBase composite material (SiC for short) f a/SiC composite). The ceramic matrix composite material retains the advantages of high temperature resistance, oxidation resistance, abrasion resistance, corrosion resistance and the like of the ceramic material, and can fully play the reinforcing and toughening role of the ceramic fiber, thereby becoming the best high temperature resistant material for preparing the hot end component of the aircraft engine.
At present, the self-repairing modes of the composite material are mainly divided into two modes, wherein one mode is an embedded self-repairing composite material; the other is an in-situ self-healing composite. In the former, self-repairing components are directly embedded in a matrix material, and once the material generates defects such as cracks and the like, the embedded self-repairing components generate a glass-state oxide with fluidity in an oxidation environment, and the oxide can flow to a damaged surface to play a role in healing the cracks. The latter refers to a special composite material which can perform self-repair under certain conditions under the condition that no repair medium is additionally added into the matrix material. Wherein the research of the embedded self-repairing composite material is more extensive.
At present, the typical self-healing component used for modifying the ceramic matrix composite material is mainly boron-containing ceramic, such as simple substance boron, a B-C system, a Si-B-C system, silicon boron glass and the like. The self-healing mechanism is that the boron-containing component is oxidized into a glass state mobile phase at high temperature to seal and fill the cracks of the matrix to play a role in sealing and healing, and the material is prevented from being further oxidized. However, this modification means only imparts a single self-healing function to the material. Meanwhile, the introduction of other phases can influence the mechanical properties of the material to a certain extent, so that the strength and toughness of the material cannot meet the use requirements.
Disclosure of Invention
The invention provides a preparation method of a silicon carbide ceramic matrix composite material with a self-repairing function. The method aims to introduce micro-nano particles with a core-shell structure into a silicon carbide substrate, so that on one hand, a shell layer with weak interface characteristics prolongs the crack diffusion path through energy absorption mechanisms such as interlayer slippage, crack deflection and the like, and plays a toughening role; on the other hand, under the oxidation condition, the self-healing component of the nuclear layer generates a mobile glass phase due to oxidation to play a role in sealing, so that the interior of the material is protected from being invaded by an oxidizing medium. Not only can enhance the mechanical property of the material, but also can endow the material with the capability of active healing. The technical solution of the invention comprises the following steps:
a preparation method of a silicon carbide ceramic matrix composite material with a self-repairing function comprises the following steps:
step 1: placing the micro-nano particles with self-healing function into a graphite crucible with an opening at the bottom, placing the graphite crucible into an effective heating zone of a chemical vapor deposition furnace, and performing BCl 3 Is a source of boron, NH 3 As a nitrogen source, H 2 Depositing a BN coating on the surface of the particles as carrier gas, setting the deposition pressure to be 200 Pa-1000 Pa, the deposition temperature to be 800-1200 ℃, and keeping the temperature for 30-100 min;
step 2: mixing the micro-nano particles coated with the BN coating prepared in the step 1 with a dispersing agent, high carbon residue resin and an organic solvent, and dispersing by using a ball mill to prepare mixed slurry;
and step 3: coating the mixed slurry prepared in the step (2) on a silicon carbide fiber fabric, and removing the organic solvent by reduced pressure evaporation to prepare a prepreg;
and 4, step 4: placing the prepreg obtained in the step 3 in a mould, and curing and molding by using a hot press, wherein the curing temperature is set to be 200-300 ℃, the pressure is set to be 0.2-10 MPa, and the time is set to be 1-5 h, so that a prefabricated body is obtained;
and 5: carbonizing the preform obtained in the step (4) at 700-1000 ℃ in an inert atmosphere for 30-120 min to obtain a porous body;
step 6: putting silicon powder on the surface of a porous body, putting the porous body into a graphite crucible, and reacting for 5-30 min under the vacuum condition at the infiltration temperature of 1380-1500 ℃ to obtain the modified SiCf/SiC composite material. The mass ratio of the silicon powder to the porous body is 2-5: 1.
BCl in the step 1 3 、NH 3 、H 2 The volume fraction ratio of (A) is as follows: 10-15: 20-35: 70-50.
The ball milling conditions in the step 3 are that the rotating speed is 200 r/min-600 r/min, the ball milling time is 4 h-10 h, the grinding balls are zirconia balls, and the ball-to-material ratio is 1-3: 1.
the mixed slurry in the step 3 comprises the following micro-nano particles coated with the BN coating, high carbon residue resin and organic solvent in a mass ratio: 5-20: 50-60: 150 to 200 parts; the mass ratio of the dispersing agent to the micro-nano particles is 0.5-2: 1.
The ball mill adopts a planetary ball mill.
The organic solvent is one of ethanol, methanol, isopropanol, acetone, toluene, xylene, butyl acetate or ethyl acetate.
The micro-nano particles with the self-healing function comprise B 4 C、SiB 4 、SiB 6 Elemental boron, borosilicate glass, Ti 3 AlC 2 、Ti 2 AlC。
The particle size range of the micro-nano particles is 10-50 mu m, and the purity is not less than 99.9%.
The purity of the silicon powder is not less than 99.99%.
The high carbon residue resin is one of phenolic resin and derivatives thereof, furan resin and derivatives thereof.
The invention has the advantages and beneficial effects that: carrying out surface treatment on micro-nano particles with a self-healing function by utilizing a chemical vapor deposition process, and depositing a layer of uniform BN coating layer on the surfaces of the particles to obtain surface modified self-healing particles with a core-shell structure, wherein the modified self-healing component with the core-shell structure is cracked when a base material generates micro cracks, and core layer substances of the modified self-healing component with the core-shell structure generate glassy state oxides under oxidation, reach crack surfaces through capillary siphonage, and are polymerized with a catalyst dispersed in the base body to achieve the purpose of repairing the cracks, so that the material is endowed with the capability of active repair; secondly, as the shell layer is BN with a layered structure, when the crack is expanded to the surface of the core-shell structure, the shell layer with weak interface characteristic prolongs the diffusion path of the crack through energy absorption mechanisms such as interlayer slippage, crack deflection and the like; and the crack path is prolonged, so that the diffusion path of the environmental medium is prolonged, the oxidation resistance of the composite material is improved, and the composite material has double functions of repairing and toughening.
Detailed Description
The technical scheme of the invention is described in detail by combining the specific examples as follows:
a preparation method of a silicon carbide ceramic matrix composite with a self-repairing function comprises the following steps:
step 1: placing the micro-nano particles with self-healing function into a graphite crucible with an opening at the bottom, placing the graphite crucible into an effective heating zone of a chemical vapor deposition furnace, and performing BCl 3 Is a source of boron, NH 3 As a nitrogen source, H 2 Depositing a BN coating on the surface of the particles as carrier gas, setting the deposition pressure to be 200 Pa-1000 Pa, the deposition temperature to be 800-1200 ℃, and keeping the temperature for 30-100 min; BCl 3 、NH 3 、H 2 The volume fraction ratio of (A) is as follows: 10-15: 20-35: 70-50. The micro-nano particles with the self-healing function comprise B 4 C、SiB 4 、SiB 6 Elemental boron, borosilicate glass, Ti 3 AlC 2 、Ti 2 And (4) AlC. The particle size range of the micro-nano particles is 10-50 mu m, and the purity is not less than 99.9%.
Step 2: mixing the micro-nano particles coated with the BN coating prepared in the step 1 with a dispersing agent, high carbon residue resin and an organic solvent, and dispersing by a planetary ball mill to prepare mixed slurry; the organic solvent is one of ethanol, methanol, isopropanol, acetone, toluene, xylene, butyl acetate or ethyl acetate. The high carbon residue resin is one of phenolic resin and derivatives thereof, furan resin and derivatives thereof. The dispersing agent is one of PVA and PVB.
And step 3: coating the mixed slurry prepared in the step (2) on a silicon carbide fiber fabric, and removing the organic solvent by reduced pressure evaporation to prepare a prepreg; the ball milling conditions are that the rotating speed is 200 r/min-600 r/min, the ball milling time is 4 h-10 h, the grinding balls are zirconia balls, and the ball-to-material ratio is 1-3: 1.
the mixed slurry comprises the following micro-nano particles coated with a BN coating, high carbon residue resin and an organic solvent in a mass ratio: 5-20: 50-60: 150 to 200 parts; the mass ratio of the dispersing agent to the micro-nano particles is 0.5-2: 1.
And 4, step 4: placing the prepreg obtained in the step 3 in a mould, and curing and molding by using a hot press, wherein the curing temperature is set to be 200-300 ℃, the pressure is set to be 0.2-10 MPa, and the time is set to be 1-5 h, so that a prefabricated body is obtained;
and 5: carbonizing the preform obtained in the step (4) at 700-1000 ℃ in an inert atmosphere for 30-120 min to obtain a porous body;
step 6: putting silicon powder on the surface of a porous body, putting the porous body into a graphite crucible, and reacting for 5-30 min under the vacuum condition at the infiltration temperature of 1380-1500 ℃ to obtain the modified SiCf/SiC composite material. The mass ratio of the silicon powder to the porous body is 2-5: 1. The purity of the silicon powder is not less than 99.99%.
Example 1:
step 1: SiB6 particles with the particle size of 10 μm and the purity of 99.99 percent are put into a graphite crucible with an opening at the bottom and are placed in an effective heating zone of a chemical vapor deposition furnace. BCl3 is used as a boron source, NH3 is used as a nitrogen source, H2 is used as a carrier gas, and a BN coating is deposited on the surface of SiB6 particles. Setting deposition pressure at 200Pa, deposition temperature at 1000 deg.C, and holding time for 30 min. Wherein the volume fraction ratio of BCl3, NH3 and H2 is as follows: 12: 28: 60, adding a solvent to the mixture;
step 2: mixing 5g of SiB6 particles coated with a BN coating with 1g of dispersing agent PVB, 50g of phenolic resin and 150g of absolute ethyl alcohol, and dispersing by using a ball mill, wherein the ball milling condition is that the rotating speed is 600r/min, the ball milling time is 4 hours, the grinding balls are zirconia balls, and the ball-to-material ratio is 2:1, preparing mixed slurry.
And step 3: coating the mixed slurry prepared in the step (2) on a silicon carbide fiber fabric, and removing the organic solvent by reduced pressure evaporation to prepare a prepreg;
and 4, step 4: placing the prepreg obtained in the step 3 in a mould, and curing and molding by using a hot press, wherein the curing temperature is set to be 200 ℃, the pressure is set to be 0.2MPa, and the time is set to be 1h, so that a prefabricated body is obtained;
and 5: carbonizing the preform obtained in the step (4) at 700 ℃ in an inert atmosphere for 120min to obtain a porous body;
step 6: placing silicon powder (with the purity of 99.99%) which is 2:1 in mass ratio with the porous body on the surface of the porous body, placing the silicon powder into a graphite crucible, and reacting for 30min under the vacuum condition at the infiltration temperature of 1380 ℃ to obtain the modified SiCf/SiC composite material.
Example 2:
step 1: particles of B4C, 50 μm in size and 99.9% pure, were placed in a graphite crucible with an opening in the bottom and placed in the active heating zone of a chemical vapor deposition furnace. BCl3 is used as a boron source, NH3 is used as a nitrogen source, H2 is used as a carrier gas, and a BN coating is deposited on the surface of the B4C particles. Setting deposition pressure at 500Pa, deposition temperature at 800 deg.C, and holding time at 40 min. Wherein the volume fraction ratio of BCl3, NH3 and H2 is as follows: 15: 35: 50;
step 2: mixing 15g of B4C particles coated with a BN coating with 22.5g of dispersing agent PVA, 60g of furan resin and 180g of butyl acetate, and dispersing by using a ball mill, wherein the ball milling condition is a rotating speed of 400r/min, the ball milling time is 5 hours, the grinding balls are zirconia balls, and the ball-to-material ratio is 3:1, preparing mixed slurry.
And step 3: coating the mixed slurry prepared in the step (2) on a silicon carbide fiber fabric, and removing the organic solvent by reduced pressure evaporation to prepare a prepreg;
and 4, step 4: placing the prepreg obtained in the step 3 in a mould, and curing and molding by using a hot press, wherein the curing temperature is set to 230 ℃, the pressure is set to 4MPa, and the time is set to 2h to obtain a prefabricated body;
and 5: carbonizing the preform obtained in the step (4) at 800 ℃ in an inert atmosphere for 60min to obtain a porous body;
step 6: placing silicon powder (with the purity of 99.99%) which is in a mass ratio of 3:1 with the porous body on the surface of the porous body, placing the silicon powder into a graphite crucible, and reacting for 20min at the infiltration temperature of 1450 ℃ under the vacuum condition to obtain the modified SiCf/SiC composite material.
Example 3:
step 1: ti3AlC2 particles with a particle size of 30 μm and a purity of 99.95% were placed in a graphite crucible with an opening at the bottom and placed in an effective heating zone of a chemical vapor deposition furnace. BCl3 is used as a boron source, NH3 is used as a nitrogen source, H2 is used as a carrier gas, and a BN coating is deposited on the surfaces of Ti3AlC2 particles. Setting deposition pressure at 1000Pa, deposition temperature at 1100 deg.C, and holding time for 100 min. Wherein the volume fraction ratio of BCl3, NH3 and H2 is as follows: 10: 20: 70;
step 2: mixing 20g of Ti3AlC2 particles coated with a BN coating with 40g of dispersing agent PVB, 55g of phenolic resin derivative and 200g of butyl acetate, and dispersing by using a ball mill, wherein the ball milling condition is that the rotating speed is 200r/min, the ball milling time is 10 hours, the grinding balls are zirconia balls, and the ball-to-material ratio is 2.5: 1, preparing mixed slurry.
And step 3: coating the mixed slurry prepared in the step (2) on a silicon carbide fiber fabric, and removing the organic solvent by reduced pressure evaporation to prepare a prepreg;
and 4, step 4: placing the prepreg obtained in the step 3 in a mould, and curing and molding by using a hot press, wherein the curing temperature is set to be 300 ℃, the pressure is set to be 10MPa, and the time is set to be 5 hours to obtain a prefabricated body;
and 5: carbonizing the preform obtained in the step (4) at 1000 ℃ in an inert atmosphere for 100min to obtain a porous body;
step 6: placing silicon powder (with the purity of 99.99%) which is 5:1 in mass ratio with the porous body on the surface of the porous body, placing the silicon powder into a graphite crucible, and reacting for 5min under the vacuum condition at the infiltration temperature of 1500 ℃ to obtain the modified SiCf/SiC composite material.
Claims (10)
1. A preparation method of a silicon carbide ceramic matrix composite with a self-repairing function is characterized by comprising the following steps:
step 1: placing the micro-nano particles with self-healing function into a graphite crucible with an opening at the bottom, placing the graphite crucible into an effective heating zone of a chemical vapor deposition furnace, and performing BCl 3 Is a source of boron, NH 3 As a nitrogen source, H 2 Depositing a BN coating on the surface of the particles as carrier gas, setting the deposition pressure to be 200 Pa-1000 Pa, the deposition temperature to be 800-1200 ℃, and keeping the temperature for 30-100 min;
step 2: mixing the micro-nano particles coated with the BN coating prepared in the step 1 with a dispersing agent, high carbon residue resin and an organic solvent, and dispersing by using a ball mill to prepare mixed slurry;
and step 3: coating the mixed slurry prepared in the step (2) on a silicon carbide fiber fabric, and removing the organic solvent by reduced pressure evaporation to prepare a prepreg;
and 4, step 4: placing the prepreg obtained in the step 3 in a mould, and curing and molding by using a hot press, wherein the curing temperature is set to be 200-300 ℃, the pressure is set to be 0.2-10 MPa, and the time is set to be 1-5 h, so that a prefabricated body is obtained;
and 5: carbonizing the preform obtained in the step (4) at 700-1000 ℃ in an inert atmosphere for 30-120 min to obtain a porous body;
step 6: putting silicon powder on the surface of a porous body, putting the porous body into a graphite crucible, and reacting for 5-30 min under the vacuum condition at the infiltration temperature of 1380-1500 ℃ to obtain the modified SiCf/SiC composite material, wherein the mass ratio of the silicon powder to the porous body is 2-5: 1.
2. The method for preparing a silicon carbide ceramic matrix composite material with self-repairing function as claimed in claim 1, wherein: BCl in the step 1 3 、NH 3 、H 2 The volume fraction ratio of (A) is as follows: 10-15: 20-35: 70-50.
3. The method for preparing a silicon carbide ceramic matrix composite material with self-repairing function as claimed in claim 1, wherein: the ball milling conditions in the step 2 are that the rotating speed is 200 r/min-600 r/min, the ball milling time is 4 h-10 h, the grinding balls are zirconia balls, and the ball-to-material ratio is 1-3: 1.
4. the method for preparing a silicon carbide ceramic matrix composite material with self-repairing function as claimed in claim 1, wherein: the mixed slurry in the step 2 comprises the following micro-nano particles coated with the BN coating, high carbon residue resin and organic solvent in a mass ratio: 5-20: 50-60: 150 to 200 parts; the mass ratio of the dispersing agent to the micro-nano particles is 0.5-2: 1.
5. The method for preparing a silicon carbide ceramic matrix composite material with self-repairing function as claimed in claim 1, wherein: the ball mill adopts a planetary ball mill.
6. The method for preparing a silicon carbide ceramic matrix composite material with self-repairing function as claimed in claim 1, wherein: the organic solvent is one of ethanol, methanol, isopropanol, acetone, toluene, xylene, butyl acetate or ethyl acetate.
7. The method for preparing a silicon carbide ceramic matrix composite material with self-repairing function as claimed in claim 1, wherein: the micro-nano particles with the self-healing function comprise B 4 C、SiB 4 、SiB 6 Elemental boron, borosilicate glass, Ti 3 AlC 2 、Ti 2 AlC。
8. The method for preparing a silicon carbide ceramic matrix composite material with self-repairing function as claimed in claim 1, wherein: the particle size range of the micro-nano particles is 10-50 mu m, and the purity is not less than 99.9%.
9. The method for preparing a silicon carbide ceramic matrix composite material with self-repairing function as claimed in claim 1, wherein: the purity of the silicon powder is not less than 99.99%.
10. The method for preparing a silicon carbide ceramic matrix composite material with self-repairing function as claimed in claim 1, wherein: the high carbon residue resin is one of phenolic resin and derivatives thereof, furan resin and derivatives thereof.
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