CN113929485A - A kind of preparation method of TiC-Ti3SiC2 double modified C/C-SiC composite material - Google Patents
A kind of preparation method of TiC-Ti3SiC2 double modified C/C-SiC composite material Download PDFInfo
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- CN113929485A CN113929485A CN202111338636.3A CN202111338636A CN113929485A CN 113929485 A CN113929485 A CN 113929485A CN 202111338636 A CN202111338636 A CN 202111338636A CN 113929485 A CN113929485 A CN 113929485A
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Abstract
The invention provides TiC-Ti3SiC2The preparation method of the double modified C/C-SiC composite material comprises the steps of depositing a pyrolytic carbon coating and a SiC coating on the surface of the pretreated carbon fiber in sequence; uniformly mixing phenolic resin, alcohol and TiC particles to obtain impregnation slurry; putting the prefabricated body after interface modification into the prepared dipping slurry, and carrying out in-situ crosslinking and curing after vacuum dipping; then placing the prefabricated body in a high-temperature cracking furnace for high-temperature cracking, making once impregnation and cracking into a technological cycle, and making several times of cycles to obtain intermediate denseThe degree is 1.0-1.6g/cm3(ii) a Carrying out high-temperature heat treatment on the impregnated intermediate; carrying out ultrasonic cleaning and drying treatment on the intermediate subjected to high-temperature heat treatment; then, the Si or Si-Al alloy is infiltrated through an infiltration process to obtain TiC-Ti3SiC2A double modified C/SiC composite material.
Description
Technical Field
The invention relates to the technical field of design and preparation of composite materials, in particular to TiC-Ti3SiC2A preparation method of a double modified C/C-SiC composite material.
Background
The C/C-SiC composite material appears as a thermal structure material in the 80 th century at the earliest, is a composite material taking carbon fibers as a reinforcement and carbon and silicon carbide as matrixes, integrates the excellent mechanical property of the carbon fiber reinforcement and the good chemical and thermal stability of a ceramic matrix, has a series of excellent properties such as high specific strength, high specific modulus, excellent high-temperature mechanical property, high thermal conductivity, low thermal expansion coefficient and the like of the C/C composite material, has the properties which are not possessed by a series of C/C composite materials such as high densification degree, long service life, strong environmental adaptability and the like, particularly outstanding oxidation resistance, overcomes the defect that the C/C composite material can be oxidized at 370 ℃ in the air to cause serious damage to the material, and is a thermal protection material, The structural bearing and the anti-oxidation are combined into a whole, and the material is applied to high and new fields, such as a heat-proof structure of a world shuttle transportation system, long-life anti-oxidation parts of solid and liquid engines, a brake pad of an aviation aircraft and the like.
Matrix modification is an effective means for further improving the performance of the C/C-SiC composite material. In order to meet the use requirements of higher temperature, a high melting point phase is generally required to be introduced into the C/C-SiC composite material so as to improve the ablation resistance of the C/C-SiC composite material, such as introduction of ultrahigh temperature carbide or boride ceramic. Among them, titanium carbide ceramics are typical transition metal carbides, and have excellent characteristics such as a high melting point, high hardness, and wear resistance. Application number CN 201510025732.0 discloses a preparation method of a ZrC-TiC modified C/C-SiC composite material, which specifically comprises the steps of preparing a low-density C/C intermediate by adopting a chemical vapor infiltration method, then melting and infiltrating mixed powder of Si, Zr and Ti into the C/C intermediate, and generating a ceramic phase in situ through a high-temperature reaction to obtain the ZrC-TiC modified C/C-SiC composite material. The preparation temperature of the method is too high, the requirement on equipment is high, and the carbon fiber can be damaged to a certain extent.
In order to enhance the ability to resist crack propagation and improve damage tolerance, it is usually necessary to introduce a toughening phase into the C/C-SiC composite, such as MAX phase ceramic (Mn +1AXn phase, where n is 1, 2 or 3; M is a transition group metal element, a is a group IIIA or group IVA element, and X is a carbon or nitrogen element): on one hand, the special structure of the MAX phase ceramic enables the MAX phase ceramic to be plastically deformed like metal, and high damage tolerance is shown, the MAX phase ceramic is introduced into the compact matrix, so that the damage tolerance of the MAX phase ceramic is certainly improved, and a toughening mechanism of the compact matrix is enriched, so that the crack propagation resistance of the MAX phase ceramic is enhanced; on the other hand, the MAX phase ceramic has good oxidation resistance and mechanical property, and can be used as a high-temperature structural material. To date, Ti3SiC2Is a MAX phase ceramic which has been most widely studied so far, and Ti3SiC2Has good thermophysical/chemical compatibility with SiC. If Ti is mixed with3SiC2Distributed in a brittle matrix, then Ti3SiC2The crack of the matrix can be slipped, pinned, deflected and bridged when stressed, and the expansion of the crack is inhibited through the self microscopic deformation, so that the damage tolerance of the matrix can be further improved through the complex process of multiple deflection of the crack in the matrix, and the aim of strengthening and toughening the C/C-SiC is expected to be fulfilled. Application number CN201810193507.1 discloses in-situ generation of Ti3SiC2A process for preparing phase-toughened silicon carbide ceramic-base composite material includes such steps as preparing slurry from TiC powder, adhesive resin and organic solvent, preparing prepreg with fibres, hot pressing, charring to obtain fibre/C-TiC porous body, wrapping Si powder on the surface of porous body, and in-situ generating Ti by high-temp smelting silicon osmosis3SiC2. The method needs hot-press molding equipment, and has great limitation on the shape and the size of the prepared sample. In addition, in the prior art, Ti3SiC2In the preparation method of the modified SiC-based composite material, high-melting-point phases such as TiC and the like can not be consolidated in the fiber bundles,therefore, a protective layer can not be formed in the RMI process to protect the fibers, and the composite material can not be subjected to in-bundle toughening.
Disclosure of Invention
The invention aims to provide TiC-Ti3SiC2The invention discloses a preparation method of a double-modified C/C-SiC composite material, which aims to solve the technical problems in the prior art. According to the invention, fine TiC powder is introduced by adopting resin slurry with good viscosity, TiC particles are uniformly distributed in fiber bundles and between bundles in the prefabricated member through uniform permeation of resin, and stable consolidation of the TiC particles is ensured through in-situ crosslinking and solidification of the resin. After the steps, the residual pore space in the fiber bundle is small, and an enough infiltration channel cannot be provided, so that most TiC particles in the bundle can be retained in the subsequent RMI process. The C/C-TiC intermediate prepared based on the scheme can directly realize TiC-Ti at relatively low temperature by utilizing Si or Si-Al alloy infiltration3SiC2Preparation of a double modified C/C-SiC composite, in which the TiC matrix is mainly in the form of particles within the fibre bundle and the Ti is3SiC2The matrix is distributed in the beam and among the beams. The modified C/C-SiC composite material realizes the cooperative enhancement and toughening of TiC particles and MAX phases in and among beams, the ablation resistance is greatly improved compared with the unmodified C/C-SiC composite material, and simultaneously, the high-toughness phase Ti is used for improving the ablation resistance3SiC2The modified composite material also has excellent mechanical property and frictional wear property.
In order to achieve the purpose, the invention provides TiC-Ti3SiC2The preparation method of the double modified C/C-SiC composite material comprises the following steps:
depositing a pyrolytic carbon coating and a SiC coating on the surface of the pretreated carbon fiber in sequence by adopting a chemical vapor deposition method to obtain a prefabricated part;
step two, uniformly mixing phenolic resin, alcohol and TiC particles to obtain impregnation slurry;
step three, putting the prefabricated body prepared in the step one into the dipping slurry prepared in the step two, and carrying out vacuum dippingAfter 140min at 140 ℃ and 140 ℃, drying and curing in situ for 140min at 140 ℃ and 160 ℃; then placing the prefabricated body in a high-temperature cracking furnace, heating to 800-3；
Step four, carrying out high-temperature heat treatment on the dipped prefabricated body, wherein the heat treatment temperature is 1600 ℃ and 1800 ℃, and the treatment time is 0.5-2 h;
fifthly, performing ultrasonic cleaning and drying treatment on the prefabricated body subjected to high-temperature heat treatment;
step six, embedding the prefabricated body obtained in the step five by adopting Si or Si-Al alloy powder, wherein the infiltration temperature is 1300-1600 ℃, and preserving the heat for 60-300min in a vacuum furnace to obtain TiC-Ti3SiC2A double modified C/SiC composite material.
Further, the carbon fiber is a carbon fiber three-dimensional needled felt, and the volume fraction of the carbon fiber is 20-35 vol.%.
Further, in the first step, the pretreatment process of the carbon fiber is as follows: the carbon fiber braided fabric is subjected to heat treatment and glue removal under the vacuum condition, the heat treatment temperature is 1000-1400 ℃, and the treatment time is 0.5-1.5 h.
Further, in the step one, the specific process of depositing the pyrolytic carbon coating on the surface of the pretreated carbon fiber by using a chemical vapor deposition method comprises the following steps: propylene or methane is used as a carbon source, argon or nitrogen is used as a diluent gas, the pressure is 200-2000Pa, and the deposition temperature is 800-1200 ℃.
Further, in the step one, the specific process of depositing the SiC coating on the carbon fiber on which the pyrolytic carbon coating is deposited by using a chemical vapor deposition method is as follows: trichloromethylsilane and hydrogen are introduced into a deposition chamber by a bubbling method by taking trichloromethylsilane as a gas source, hydrogen as a carrier gas and argon as a diluent gas, wherein the molar mixing ratio of the trichloromethylsilane to the hydrogen is 1:10, the temperature of the deposition chamber is 960-1200 ℃, the pressure is 200-2000Pa, and the density range of the obtained blank is 0.7-1.0g/cm3。
Furthermore, the thickness of the pyrolytic carbon coating deposited on the surface of the carbon fiber is 50-500nm, and the thickness of the SiC coating is 0.2-1 μm.
Furthermore, in the second step, the grain diameter of TiC particles is 0.5-5 μm, and the addition amount of the TiC particles is 8-18 wt% of the total weight of the impregnating slurry.
Further, in the second step, the mass ratio of the phenolic resin to the alcohol is 3-4: 5.
And further, in the third step, the prefabricated body is immersed in the dipping slurry to be heated together, and the solidification and the cracking are carried out in an in-situ mode.
Further, in the fifth step, the ultrasonic cleaning and drying treatment of the preform subjected to the high-temperature heat treatment specifically comprises: and (3) placing the prefabricated body after high-temperature heat treatment in an ultrasonic cleaning machine, cleaning for 10-30min, taking out the prefabricated body, and drying for 2-3h in an oven at the temperature of 100-.
According to the invention, TiC particles are introduced into the preform by adopting a slurry impregnation method, the mixed solution of phenolic aldehyde and alcohol is used as impregnation slurry, the slurry has certain viscosity, the TiC particles can be uniformly mixed by simple mechanical stirring without ball milling mixing, adverse effects of a ball milling process on the powder are avoided, the impregnation effect of the TiC powder is improved due to moderate viscosity, the powder cannot fall off, a sample cannot be affected by steps such as cleaning, the impregnation process is carried out under a vacuum condition, the TiC particles can be introduced into the preform without pressurization in the process, and the operation is simple.
The carbon fiber surface coating is prepared by adopting a chemical vapor deposition process, the thickness of the PyC coating is 50-500nm, the thickness of the SiC coating is 0.2-1 mu m, the coating within the thickness range can effectively protect the carbon fiber, reduce the damage caused by the subsequent process, ensure the bonding strength of the fiber and the matrix to be moderate and play a toughening effect of interfacial crack deflection, and in addition, the coating within the thickness range can also ensure that enough space is still left in the fiber bundle, thereby facilitating the mass introduction of the subsequent TiC-containing particle slurry.
The mass ratio of the impregnated slurry phenolic resin to the alcohol is 3: 5-4: 5, and the ratio can ensure that the slurry has moderate viscosity, has a good dispersion effect on TiC particles, obtains enough carbon source after cracking, and can ensure enough fluidity, so that the slurry has a good impregnation effect on the intermediate.
The grain diameter of the TiC particles is 0.5-5 mu m, the grain diameter range can ensure that the TiC particles are stably dispersed in the slurry, and a large amount of TiC particles can permeate into the fiber bundle along with the slurry in the dipping process.
In the impregnating slurry, TiC particles are uniformly dispersed, the dispersing effect is stable, the content of TiC introduced into the composite material can be regulated and controlled by changing the adding proportion of TiC, the adding amount of the TiC particles is controlled to be 8-18 wt.%, a large amount of TiC can be introduced into the composite material, and the stable solidification of the TiC particles in a fiber bundle can be further ensured by resin in-situ crosslinking and curing.
After the prefabricated body is subjected to dipping pyrolysis, TiC particles exist among the fiber bundles and are distributed in the fiber bundles, so that the ablation resistance of the composite material is greatly improved. The high-melting-point TiC phase in the fiber bundle can also play a role in protecting fibers in infiltration and play a role in toughening particles in the bundle during loading. In addition, part of TiC particles among fiber bundles are converted into Ti in situ in RMI process3SiC2And obtaining the double modified C/C-SiC composite material. Inter-fiber bundle Ti3SiC2The material has the functions of deflecting cracks and preventing the cracks from expanding, the damage tolerance of the brittle matrix is improved, and the frictional wear performance of the material is improved.
The density of the prefabricated body prepared by the dipping pyrolysis process is 1.0-1.6g/cm3The prefabricated body in the range contains more TiC phases, and the composite material obtained after the RMI process has better service performance.
The high-temperature heat treatment process for the preform is beneficial to opening closed pores formed in the preform in the impregnation pyrolysis process, and provides infiltration channels for the RMI process, so that the reaction is more sufficient. The high-temperature treatment time is 1-3h, and the damage to the fiber caused by long-time high-temperature reaction is avoided while the closed pores are fully opened.
The ultrasonic cleaning process can remove redundant powder on the surface layer of the prefabricated body, and the treatment process can avoid the crusting phenomenon on the surface of the prefabricated body in the RMI process, thereby being beneficial to full reaction in the technological process.
The RMIThe process takes silicon or aluminum-silicon alloy powder as raw materials, the aluminum-silicon alloy powder as the raw materials can reduce the infiltration temperature in the RMI process, reduce the damage of high temperature to fibers, and simultaneously Al can enter Ti through solid solution3SiC2In the crystal lattice of (A), Ti having higher oxidation resistance is generated3Si(Al)C2And (4) phase(s).
The invention has the following beneficial effects:
the TiC is introduced in a phenolic resin impregnation mode, on one hand, the slurry is moderate in viscosity and has a good filling effect on pores in a fiber bundle, TiC particles can be solidified in an area in the bundle after cracking and carbonization to form a high-melting-point TiC 'layer', and a certain protection effect on fibers is achieved in a subsequent high-temperature RMI process; on the other hand, the slurry components are controllable, the content of TiC can be regulated and controlled by changing the proportion of the slurry components, the generated C/C-TiC porous body has good stability, TiC is not easy to peel off, operations such as cleaning and processing can be carried out, the technological process is simple and convenient to operate and wide in applicability, and TiC uniformly distributed is converted into Ti3SiC2The powder is uniformly distributed, and can form a large amount of phase interfaces with the ceramic matrix.
According to the invention, the low-temperature preparation of the TiC modified C/C-SiC composite material is realized by combining slurry impregnation with reaction infiltration, the anti-ablation performance of the C/C-SiC composite material is greatly improved by introducing the high-melting-point TiC phase, and Ti generated by the reaction of the interbeam TiC and Si3SiC2And the mechanical property of the composite material is improved, and the composite material has excellent frictional wear property. By TiC and Ti3SiC2The content adjustment shows that the composite material prepared by the invention can support the application of the C/C-SiC composite material in the fields of thermal structure/protection, friction braking and the like.
In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention will be described in further detail below with reference to the drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1a is TiC-Ti prepared in the preferred embodiment 1 of the present invention3SiC2A microstructure diagram of a double modified C/C-SiC composite material;
FIG. 1b is TiC-Ti prepared in the preferred embodiment 1 of the present invention3SiC2A microstructure diagram of crack deflection caused by TiC particles in the beam during bending loading of the double modified C/C-SiC composite material;
FIG. 1c is a spectral scan corresponding to the location of region 1 in FIG. 1 a;
FIG. 2a is TiC-Ti prepared by the method of the preferred embodiment 23SiC2A comparison graph of the shapes of the double-modified C/C-SiC composite material and the unmodified C/C-SiC composite material prepared in the comparative example 2 after ablation;
FIG. 2b is an enlarged TiO illustration of area 1 of FIG. 2a2A topography map;
FIG. 2c is a diagram of TiC-Ti prepared in the preferred embodiment 2 of the present invention3SiC2Performing surface scanning on the energy spectrum of the ablation pit region of the double-modified C/C-SiC composite material;
FIG. 3a is TiC-Ti prepared by the method of the preferred embodiment 23SiC2The appearance diagram of the friction surface of the double modified C/C-SiC composite material after the dynamic and static ring friction test;
FIG. 3b is TiC-Ti prepared in the preferred embodiment 2 of the present invention3SiC2Typical friction curves for the double modified C/C-SiC composites.
Detailed Description
Embodiments of the invention will be described in detail below with reference to the drawings, but the invention can be implemented in many different ways, which are defined and covered by the claims.
The invention provides TiC-Ti3SiC2The preparation method of the double-modified C/C-SiC composite material specifically comprises the following steps:
1) taking the carbon fiber three-dimensional needled felt as a prefabricated body, carrying out heat treatment and glue removal on the carbon fiber braided fabric under the vacuum condition at the heat treatment temperature of 1000-1400 ℃ for 0.5-1.5h, wherein the volume fraction of the carbon fiber is 20-35 vol.%.
2) And depositing a pyrolytic carbon coating on the surface of the carbon fiber by chemical vapor deposition. Propylene or methane is used as a carbon source, argon or nitrogen is used as a diluent gas, the pressure is 200-2000Pa, the deposition temperature is 800-1200 ℃, and the thickness of the pyrolytic carbon coating prepared on the surface of the fiber is controlled to be 50-500 nm.
3) And depositing a SiC coating on the surface of the carbon fiber by adopting chemical vapor deposition. Trichloromethylsilane as gas source, hydrogen as carrier gas and argon as diluent gas are introduced into a deposition chamber by a bubbling method, wherein the molar mixing ratio of the trichloromethylsilane to the hydrogen is 1:10, the temperature of the deposition chamber is 960-1200 ℃, the pressure is 200-2000Pa, and the density range of the obtained blank is controlled to be 0.7-1.0g/cm3。
4) And preparing the impregnation slurry. Taking phenolic resin as a precursor, taking alcohol as a solvent, mixing a certain amount of TiC particles (the particle size is 0.5-5 mu m), and mechanically stirring and uniformly mixing to obtain impregnation slurry, wherein the mass ratio of the phenolic resin to the alcohol is 3-4:5, and the addition amount of the TiC particles is 8-18 wt%;
5) the impregnation process is carried out under the vacuum condition, the prefabricated body is firstly arranged in a self-made stone ink box, the impregnation slurry is added into the stone ink box until the upper surface of the prefabricated body is completely submerged, then the graphite box is arranged in a closed container, the vacuum is continuously pumped for 140min, the graphite box is taken out, the heat preservation is carried out in an oven at the temperature of 140 ℃ for 140min, the in-situ drying and solidification are carried out, the prefabricated body is arranged in a high-temperature pyrolysis furnace, the temperature is increased to 800 ℃ for 1000 ℃ at the temperature rising speed of 10-15 ℃/min, the high-temperature pyrolysis is carried out under the protection of argon for 40-80min, the temperature is reduced to the room temperature along with the furnace, the one-time impregnation heating and cracking is carried out into a process cycle, and the density of the composite material obtained through multiple cycles is 1.0-1.6g/cm3；
6) And carrying out high-temperature heat treatment on the prefabricated body, wherein the heat treatment temperature is 1600-1800 ℃, and the treatment time is 0.5-2 h.
7) And (3) placing the preform in an ultrasonic cleaning machine, cleaning for 10-30min, taking out the preform, and drying for 2h in an oven at 100 ℃.
8) Obtaining the C/C-SiC composite material by the RMI process of the prefabricated body, and enabling partial TiC to generate Ti in situ3SiC2. By Si or Si-Al alloy powder is used as a raw material, the infiltration temperature is 1300-1600 ℃, the heat preservation is carried out for 60-300min in a vacuum furnace, and finally the TiC-Ti is obtained3SiC2A double modified C/SiC composite material.
Firstly, preparing PyC and SiC interface layers on the surfaces of prefabricated fibers by a chemical vapor deposition process, and controlling the total thickness of the interface layers to ensure that enough pores are still reserved in fiber bundles; dissolving phenolic resin and TiC micron powder in alcohol according to a certain proportion to prepare slurry, carrying out vacuum infiltration on the prefabricated body, and carrying out multiple times of infiltration, in-situ crosslinking curing and cracking to obtain a C/C porous body with TiC particles distributed in the beam and among the beams; finally, the infiltration process is carried out to infiltrate Si or Si-Al alloy to obtain TiC-Ti3SiC2A double modified C/C-SiC composite material. The invention realizes the cooperative reinforcement and toughening of the C/C-SiC composite material in and among bundles, wherein the TiC matrix with high melting point is mainly positioned in the fiber bundles, and the Ti with high toughness3SiC2The matrix is distributed in the beam and among the beams. The preparation method has wide applicability, and the modified composite material has greatly improved ablation resistance compared with the C/C-SiC composite material, and simultaneously has good mechanical property and frictional wear property.
The present invention is explained below with reference to specific examples.
Example 1:
selecting a carbon fiber three-dimensional needled felt with the size of 120mm multiplied by 30mm (needling direction) multiplied by 120mm as a prefabricated body, wherein the fiber volume fraction is 25 vol.%, and preparing the final composite material by the following steps:
1. the felt body is firstly subjected to heat treatment at 1400 ℃ to remove glue, and then is cleaned and dried. And sequentially preparing a PyC coating and a SiC coating on the surface of the carbon fiber by adopting a chemical vapor deposition process for later use, wherein the thickness of the PyC coating is 0.2 mu m, and the thickness of the SiC coating is 0.5 mu m.
2. 450g of phenolic aldehyde and 600g of alcohol are mixed, 150g of TiC micro powder with the particle size of 1-5 mu m is added, and mechanical stirring is carried out for 30min to obtain the dipping slurry. Adopting vacuum impregnation process, placing the preform in a graphite box with proper size, adding impregnation slurry until the preform is completely submerged, placing the graphite box in a closed container, and continuously vacuumizing for 120min(ii) a Putting the graphite box into an oven, setting the temperature of the oven to be 150 ℃, and drying for 120 min; and then putting the graphite box into a vacuum high-temperature furnace, and cracking under the protection of argon atmosphere at the temperature of 1000 ℃ for 60 min. Repeating the above steps, and vacuum impregnating and cracking for 4 times to obtain intermediate with density of 1.5g/cm3。
3. Carry out high temperature heat treatment to the preform in high temperature furnace, heat treatment temperature 1800 ℃, processing time 1h, this process is favorable to reducing the inside obturator of preform, promotes later stage infiltration effect.
4. Placing the prefabricated body in an ultrasonic cleaning machine for cleaning for 20min, taking out the prefabricated body, placing the prefabricated body in an oven for drying for 2h at the temperature of 100 ℃, embedding the prefabricated body subjected to high-temperature treatment by adopting aluminum-silicon alloy particles, and selecting silicon in the aluminum-silicon alloy: the Al atomic ratio is 9: 1, infiltrating for 300min under the conditions that the pressure is 1000Pa and the temperature is 1400 ℃ to prepare TiC-Ti3SiC2A double modified C/SiC composite material.
Comparative example 1:
the only difference between comparative example 1 and example 1 is that no TiC micropowder is added to the slurry in step 2, otherwise the same as example 1.
The density of the composite material is measured by a drainage method, the bending strength of the composite material is measured by a three-point bending method, the size of a test sample strip is 4.5mm x 3mm x 50mm, the span is 30mm, and the loading speed is 0.5 mm/min. The test results are shown in table 1, the average bending strength of the matrix-modified composite material is 171.5MPa, and the performance is improved by 68.8% compared with the unmodified composite material (average bending strength is 101.6 MPa).
TABLE 1C/C-SiC composites with TiC-Ti3SiC2Mechanical property comparison of composite material after double modification
Observing the microstructure by adopting an SEM scanning electron microscope, wherein the voltage is 20 kV; the elemental composition was analyzed by EDS spectroscopy. FIG. 1a is TiC-Ti3SiC2Dual modified C/C-SiC composite material microstructure, wherein the inter-bundle pores are mainly filled by SiC matrix, and more Ti generated by reaction is in the matrix3SiC2The phases are present, with a large amount of TiC phases distributed within the fiber bundle and still present in the form of micron-sized particles, whose deflecting effect on cracks is observed after loading (fig. 1 b). FIG. 1c is a plot of the spectral scan at region 1 of FIG. 1a, showing that the predominant component is Ti3SiC2Or Ti3Si(Al)C2Form of MAX phase and TiSi2And (4) phase(s).
Example 2:
example 2 the preparation process differs from example 1 as follows: 1) the thickness of the PyC coating was 0.4 μm and the thickness of the SiC coating was 1.0 μm; 2) the slurry is soaked for 3 times, and the density of the intermediate before siliconizing is 1.30g/cm3(ii) a 3) Si particles are adopted instead of Si-Al alloy particles during infiltration; the rest is the same as example 1.
Comparative example 2:
the only difference between comparative example 2 and example 2 is that no TiC micropowder is added to the step 2 slurry, otherwise the same as example 2.
The prepared composite material is subjected to ablation resistance test by using oxyacetylene ablation, the flow ratio of oxygen to acetylene is 1.38:1, and the heat flow density is about 4200kW/m2Ablation time 30s, ablation direction is perpendicular to the needle punching direction. The ablation test sample size was 45mm × 30mm (needle punching direction) × 7mm, and 5 samples of each group were measured to calculate the average line ablation rate and mass ablation rate. FIG. 2a is TiC-Ti prepared by the method of the preferred embodiment 23SiC2A comparison graph of the shapes of the double-modified C/C-SiC composite material and the unmodified C/C-SiC composite material prepared in the comparative example 2 after ablation; FIG. 2b is an enlarged TiO illustration of area 1 of FIG. 2a2Topography showing ablated TiO2The shape of a continuous oxide layer is presented, the function of an isolation layer is achieved, and the ablation resistance of the modified material is effectively improved; FIG. 2c is a diagram of TiC-Ti prepared in the preferred embodiment 2 of the present invention3SiC2The spectral surface scanning results of the ablation pit area of the double modified C/C-SiC composite material further confirm the existence of a large amount of oxides.
As can be seen from FIG. 2a, modified in example 2The size of the ablation pit of the C/C-SiC composite material is small, and a high-magnification electron micrograph shows that a compact TiO is formed on the ablation surface2-SiO2The oxide layer has the linear ablation rate of 7.75 mu m/s and the mass ablation rate of 2.89mg/s, and the ablation resistance of the oxide layer is greatly improved compared with that of the unmodified C/C-SiC composite material in the comparative example 2; while the unmodified C/C-SiC composite material obtained in comparative example 2 had a wire ablation rate of 15.85 μm/s and a mass ablation rate of 5.44 mg/s).
In addition to the ablation resistance, the modified C/C-SiC composite material is subjected to dual friction and wear test. The sizes of the dynamic test ring and the static test ring are 75mm of outer diameter, 53mm of inner diameter and 15mm of thickness. And (3) testing conditions are as follows: moment of inertia J0.32 kg · m2Pressure P is 0.87MPa, speed n is 7000rpm, and energy-carrying capacity E is 0.11 x 106J. Photographs of the test ring after the rubbing test and typical rubbing curves are shown in fig. 3a and 3b, and the curves appear as typical "saddle" shapes. The modified composite material has excellent friction resistance, the average friction coefficient of 10 times is 0.33, the linear wear rate of a moving ring is 4.45 mu m/time, and the mass wear rate is 40.63 mg/time; the linear wear rate of the static ring is 1.25 mu m/time, and the mass wear rate is 20.08 mg/time.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by 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 protection scope of the present invention.
Claims (10)
1. TiC-Ti3SiC2The preparation method of the double modified C/C-SiC composite material comprises the following steps:
depositing a pyrolytic carbon coating and a SiC coating on the surface of the pretreated carbon fiber in sequence by adopting a chemical vapor deposition method to obtain a prefabricated part;
step two, uniformly mixing phenolic resin, alcohol and TiC particles to obtain impregnation slurry;
step three, placing the prefabricated body prepared in the step one into the dipping slurry prepared in the step two, vacuum dipping for 140min, and drying and solidifying in situ at the temperature of 140-Dissolving for 100-; then placing the prefabricated body in a high-temperature cracking furnace, heating to 800-3；
Step four, carrying out high-temperature heat treatment on the dipped prefabricated body, wherein the heat treatment temperature is 1600 ℃ and 1800 ℃, and the treatment time is 0.5-2 h;
fifthly, performing ultrasonic cleaning and drying treatment on the prefabricated body subjected to high-temperature heat treatment;
step six, embedding the prefabricated body obtained in the step five by adopting Si or Si-Al alloy powder, wherein the infiltration temperature is 1300-1600 ℃, and preserving the heat for 60-300min in a vacuum furnace to obtain TiC-Ti3SiC2A double modified C/SiC composite material.
2. TiC-Ti of claim 13SiC2The preparation method of the double-modified C/C-SiC composite material is characterized in that the carbon fiber is a carbon fiber three-dimensional needled felt, and the volume fraction of the carbon fiber is 20-35 vol.%.
3. TiC-Ti of claim 13SiC2The preparation method of the double-modified C/C-SiC composite material is characterized in that in the first step, the pretreatment process of the carbon fiber is as follows: the carbon fiber braided fabric is subjected to heat treatment and glue removal under the vacuum condition, the heat treatment temperature is 1000-1400 ℃, and the treatment time is 0.5-1.5 h.
4. TiC-Ti of claim 13SiC2The preparation method of the double-modified C/C-SiC composite material is characterized in that in the step one, the specific process of depositing the pyrolytic carbon coating on the surface of the pretreated carbon fiber by adopting a chemical vapor deposition method comprises the following steps: propylene or methane is used as a carbon source, argon or nitrogen is used as a diluent gas, the pressure is 200-2000Pa, and the deposition temperature is 800-1200 ℃.
5. TiC-Ti of claim 43SiC2The preparation method of the double-modified C/C-SiC composite material is characterized in that in the step one, the specific process of depositing the SiC coating on the carbon fiber after the pyrolytic carbon coating is deposited by adopting a chemical vapor deposition method comprises the following steps: trichloromethylsilane and hydrogen are introduced into a deposition chamber by a bubbling method by taking trichloromethylsilane as a gas source, hydrogen as a carrier gas and argon as a diluent gas, wherein the molar mixing ratio of the trichloromethylsilane to the hydrogen is 1:10, the temperature of the deposition chamber is 960-1200 ℃, the pressure is 200-2000Pa, and the density range of the obtained blank is 0.7-1.0g/cm3。
6. TiC-Ti of claim 13SiC2The preparation method of the double-modified C/C-SiC composite material is characterized in that the thickness of a pyrolytic carbon coating deposited on the surface of carbon fibers is 50-500nm, and the thickness of a SiC coating is 0.2-1 mu m.
7. TiC-Ti of claim 13SiC2The preparation method of the double-modified C/C-SiC composite material is characterized in that in the second step, the grain size of TiC particles is 0.5-5 mu m, and the addition amount of the TiC particles is 8-18 wt% of the total weight of the impregnating slurry.
8. TiC-Ti of claim 13SiC2The preparation method of the double-modified C/C-SiC composite material is characterized in that in the second step, the mass ratio of the phenolic resin to the alcohol is 3-4: 5.
9. TiC-Ti of claim 13SiC2The preparation method of the double-modified C/C-SiC composite material is characterized in that in the third step, the prefabricated body is immersed in the dipping slurry to be heated together, and the solidification and the cracking are carried out in an in-situ mode.
10. TiC-Ti of claim 13SiC2A preparation method of a double modified C/C-SiC composite material,the method is characterized in that in the fifth step, the ultrasonic cleaning and drying treatment of the prefabricated body after the high-temperature heat treatment are specifically as follows: and (3) placing the prefabricated body after high-temperature heat treatment in an ultrasonic cleaning machine, cleaning for 10-30min, taking out the prefabricated body, and drying for 2-3h in an oven at the temperature of 100-.
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