CN115196987A - Carbon nano tube/fiber multi-scale reinforced ceramic matrix composite material and preparation method thereof - Google Patents
Carbon nano tube/fiber multi-scale reinforced ceramic matrix composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon nano tube/fiber multi-scale reinforced ceramic matrix composite and a preparation method thereof. The preparation method is simple in preparation process, the process of supplying the reduction gas and the carbon source gas by the polycarbosilane precursor is safe and controllable, and the preparation method has remarkable advantages in the aspect of rapid and safe preparation.
Description
Technical Field
The invention relates to a preparation method of a ceramic matrix composite, in particular to a carbon nano tube/fiber multi-scale reinforced ceramic matrix composite and a rapid preparation method thereof, belonging to the technical field of ceramic matrix composites.
Background
For continuous fiber reinforced ceramic matrix composites, the bonding interface between the fiber and the matrix has a significant impact on the mechanical properties of the material, especially the toughness of the composite. At present, modifying the surface of the fiber, regulating and controlling the interface bonding strength of the fiber and the matrix, and improving the mechanical properties of the composite material have become one of the hot research directions. In order to improve the interfacial bonding of the composite material and improve the toughness of the material, it is common practice to prepare one or more interfacial coatings on the surface of the fiber. Although the coatings have better effect of improving the interface bonding of the fiber and the matrix, the reinforcing effect on the composite material is not obvious. Therefore, new interface structures are gradually designed, namely, the improvement of the structural performance of the composite material and the increase of the heat conductivity coefficient are realized by introducing a low-dimensional nano material modified interface with excellent mechanical property and high heat conductivity. Wherein the low-dimensional nano material mainly comprises single-wall/multi-wall carbon nano tubes or nano wires, silicon carbide nano wires and the like. The in-situ growth of the low-dimensional nano material can play a role of bridging between two fibers and between two bundles of fibers, and the two reinforcements are combined to form a natural micron-nano mixed reinforced structure. In addition, the surface roughness of the low-dimensional nano material modified continuous fiber is obviously increased, which is beneficial to increasing the effective contact area between the fiber surface and the matrix, thereby relieving the stress concentration at the fiber defect. Meanwhile, the mechanical engaging force between the fibers and the matrix is enhanced, the interface bonding strength of the composite material is improved, more fibers are pulled out in the failure process, the crack propagation direction and path are changed, and a certain amount of fracture energy is absorbed. The multi-scale hybrid composite material composed of the low-dimensional nano material, the traditional continuous fiber and the matrix has excellent fiber-leading mechanical property and good matrix-leading mechanical property, and is more suitable for a load environment with more frequent interlaminar load and impact than the traditional ceramic matrix composite material. Therefore, the multi-scale hybrid composite material modified based on the low-dimensional nano material has become a leading focus in the field of new material research. The currently common preparation process is chemical vapor deposition (CVI), in which hydrogen is used as a reducing gas to reduce the catalyst, thereby improving the growth efficiency of the carbon nanotubes. However, hydrogen itself has flammable and explosive characteristics, and the preparation of carbon nanotubes has high technical requirements on deposition equipment. In order to reduce the difficulty and cost of carbon nanotube preparation, it is highly desirable to develop a rapid and safe preparation process without preparing a hydrogen gas source.
Disclosure of Invention
The invention aims to overcome the defects and provides a carbon nano tube/fiber multi-scale reinforced ceramic matrix composite and a preparation method thereof. The preparation method is simple in preparation process, the process of providing the reduction gas and the carbon source gas by the polycarbosilane precursor is safe and controllable, and the method has remarkable advantages in the aspect of rapid and safe preparation.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a carbon nano tube/fiber multi-scale reinforced ceramic matrix composite material comprises the following steps:
s1, preparing a catalyst solution;
s2, soaking the fiber satin cloth in a catalyst solution, standing, taking out and airing to obtain the fiber satin cloth loaded with the catalyst; manufacturing the fiber satin cloth loaded with the catalyst into a fiber fabric with a preset thickness by adopting a layer-spreading sewing process;
s3, placing the fiber fabric in a container with polycarbosilane at the bottom, wherein the fiber fabric is positioned above the polycarbosilane precursor and is not contacted with the polycarbosilane;
s4, heating the container, decomposing polycarbosilane in the container to generate reducing gas and carbon source gas, and growing the carbon nano tubes in the fiber fabric under the action of the reducing gas and the carbon source gas to obtain a carbon nano tube/fiber reinforcement fabric;
and S5, adopting a precursor impregnation cracking process to densify the carbon nanotube/fiber reinforcement fabric to obtain the carbon nanotube/fiber reinforcement ceramic matrix composite.
Further, the specific method for preparing the catalyst solution in the step S1 is to dissolve the catalyst in deionized water by using an ultrasonic dispersion process at room temperature, wherein the catalyst is one or more of cobalt acetate, nickel nitrate or ferrocene;
the mass fraction of the catalyst solution is 0.5-3%.
Further, the fiber satin cloth in the step S2 comprises one or a combination of two of carbon fiber satin cloth and silicon carbide fiber satin cloth;
before the fiber satin cloth is soaked in the catalyst solution, the fiber satin cloth is subjected to degumming treatment at the temperature of 800-1200 ℃ for 1-4 hours.
Further, in the step S3, the container is a graphite box, the bottom of the graphite box is filled with the solidified polycarbosilane, a graphite column is arranged in the graphite box, the fiber fabric is supported above the polycarbosilane precursor through the graphite column, and the distance between the fiber fabric and the polycarbosilane is 2-5 cm;
heating the container in inert atmosphere at 900-1500 deg.c for 1-5 hr.
Further, in the step S4, the reducing gas generated after the polycarbosilane is decomposed includes hydrogen, and the carbon source gas includes methane;
the mass of the carbon nano tubes in the carbon nano tube/fiber reinforcement fabric accounts for 1-8% of the mass of the fiber fabric;
in the carbon nanotube/fiber reinforcement fabric, the carbon nanotubes are in a nanometer scale, and the fibers in the fiber fabric are in a micrometer scale or higher.
Further, the specific method for densifying the carbon nanotube/fiber reinforcement fabric by using the precursor impregnation cracking process in the step S5 is to circularly perform the pressure impregnation-curing-cracking process on the carbon nanotube/fiber reinforcement fabric until the density of the carbon nanotube/fiber reinforcement ceramic matrix composite material meets the predetermined requirement.
Further, the precursor solution used for pressure impregnation in the step S5 comprises solid PCS and liquid PCS, and the mass ratio of the solid PCS to the liquid PCS is 0.5-2; the dipping pressure is 1-5MPa, the dipping time is 2-6 hours, and the dipping temperature is 60-130 ℃;
the curing temperature is 160-500 ℃, and the curing time is 1-5 hours;
the cracking temperature is 950-1500 ℃, and the cracking time is 1-3 hours.
Further, in step S2, the fiber satin is soaked in the catalyst solution at normal temperature for 30-60 min, and after standing, the fiber satin is taken out and dried to obtain the fiber satin loaded with the catalyst.
The carbon nanotube/fiber multi-scale reinforced ceramic matrix composite material prepared by the preparation method has the density of 1.8-2.2g/cm 3 。
Compared with the prior art, the invention has the following beneficial effects:
(1) In the preparation method of the carbon nano tube/fiber multi-scale reinforced ceramic matrix composite material, the small molecular gas released by polycarbosilane in the high-temperature cracking process is used for reducing the catalyst on the surface of the fiber and growing the carbon nano tube in situ.
(2) According to the invention, by introducing the carbon nano tube, the combination of the fiber and the matrix can be effectively improved, so that the purpose of secondary toughening is further achieved on the composite material, and the bending strength and the fracture toughness of the composite material with the carbon nano tube are remarkably improved.
(3) The invention designs a reaction vessel, and the carbon nano tube can stably grow under the action of micromolecular gas generated by decomposing polycarbosilane precursor by matching with proper heating conditions.
(4) The invention adopts the vacuum impregnation process to pour the catalyst solution into the fiber fabric, realizes the uniform dispersion of the catalyst in the fiber fabric, and provides a foundation for the uniform growth of the carbon nano tube in the fiber fabric.
(5) The invention adopts the cured Precursor (PCS) as the carbon source required by the preparation of the carbon nano tube, and reduces the influence of water molecules and the like released by the PCS precursor in the low-temperature stage on the preparation of the carbon nano tube.
Drawings
FIG. 1 is a schematic diagram of the release of gas species from Polycarbosilane (PCS) according to the present invention under different temperature conditions;
FIG. 2 is a schematic diagram of the present invention for in-situ preparation of carbon nanotubes using Polycarbosilane (PCS) after thermal curing;
FIG. 3 is a graph showing the morphology of carbon nanotubes/carbon fiber reinforcement prepared by the present invention at different heating times; wherein (a) is 0h, (b) is 0.5h, (c) is 1h, and (d) is 3h.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The invention provides a preparation method for carrying out catalyst reduction and carbon nanotube in-situ growth on the surface of a fiber by using small molecular gas (H2 or CH4 and the like) released by solidified Polycarbosilane (PCS) in a high-temperature cracking process, aiming at solving the problems of long preparation period, high equipment requirement, long preparation period, high cost and the like of a carbon nanotube on the surface of the fiber, wherein the types of the gas released in the heating process of the polycarbosilane are shown in figure 1. And then regulating and controlling the content, the length-diameter ratio and the like of the carbon nano tubes on the surface of the fiber by changing the cracking temperature of the solidified polycarbosilane, and finally performing matrix densification on the carbon nano tube/fiber multi-scale reinforcement fabric by adopting a precursor impregnation cracking process. The method comprises the following specific steps:
1) Preparation of catalyst solution: preferably, cobalt acetate, nickel nitrate or ferrocene and the like are used as catalysts, deionized water is used for dissolving the catalysts, an ultrasonic auxiliary process is adopted for fully dissolving the catalysts at room temperature, and a catalyst solution with the mass fraction of 0.5% -3% is prepared, wherein in the step, the ultrasonic temperature is 25-40 ℃, and the ultrasonic time is 5-20min.
2) Preparing a carbon nano tube/fiber multi-scale reinforcement fabric: introducing a catalyst on the surface of the carbon fiber or silicon carbide fiber satin cloth by adopting a catalyst solution impregnation method, and carrying out catalyst reduction on the surface of the fiber by utilizing micromolecular gas released by a polycarbosilane precursor in a high-temperature cracking process to realize in-situ growth of the carbon nano tube on the surface of the fiber.
The method comprises the following specific steps: soaking carbon fiber or silicon carbide fiber satin cloth with a certain size after glue discharging in the catalyst solution prepared in the step 1) for standing, wherein the fiber is coated with some organic glue in the preparation process to form a bundle, and the glue discharging aims at removing organic impurities such as sizing agent and the like on the surface of the fiber; then taking out and naturally airing, and preparing the fiber fabric with the thickness required by the design by adopting a layer-laying sewing process; finally, the fiber fabric was placed in a graphite box with polycarbosilane precursor at the bottom. The graphite box was filled with a graphite column supporting the fabric, and the fibrous fabric was placed over the cured Polycarbosilane (PCS) to keep a distance from the polycarbosilane precursor, ensuring that the fabric did not contact the polycarbosilane precursor, as shown in fig. 2. Finally, the whole is in inert gas Ar or N 2 High-temperature heating is carried out in the atmosphere to prepare the carbon nano tube/fiber multi-scale reinforcement fabric, wherein the precursor is heated along with the temperature increase, polycarbosilane decomposes hydrogen, methane and other gases which can be respectively used as a reducing gas and a carbon source gas for preparing the carbon nano tube, and micromolecule gas released by the polycarbosilane precursor in the high-temperature cracking process carries out catalyst reduction on the surface of the fiber and realizes the carbon nano tubeGrowing in situ on the surface of the fiber to obtain the carbon nano tube/fiber multi-scale reinforcement fabric, wherein the multi-scale means that the carbon nano tube is in a nano scale, and the fiber is in a micron or higher scale.
Preferably, the fiber degumming treatment temperature in the step 2) is as follows: the glue discharging treatment time is as follows at 800-1200 deg.C: 1-4 hours, and the high-temperature heating temperature is as follows: 900-1500 ℃, and the high-temperature heating time is as follows: the distance between the fabric and the precursor is 2-5 cm after 1-5 hours, and the reduction gas and the carbon source gas can be ensured to fully contact the catalyst on the surface of the fiber fabric. Wherein, the weight gain ratio of the carbon nano tube in the fiber fabric is as follows: 1 to 8 percent. The morphology of carbon nanotube/carbon fiber reinforcement prepared by different heating times is shown in FIG. 3, wherein (a): 0h, (b): 0.5h, (c): 1h and (d): 3h, and the growth process of carbon nanotubes on the fiber surface is clearly shown in FIG. 3.
3) And (3) densifying the matrix: densifying the carbon nanotube/fiber multi-scale reinforcement fabric prepared in the step 2) by adopting a precursor impregnation cracking process (PIP) to prepare the carbon nanotube/fiber multi-scale reinforcement ceramic matrix composite.
Preferably, the step of the impregnation cracking process in the step 3) is as follows: pressure dipping the carbon nano tube/fiber multi-scale reinforcement fabric obtained in the step 2), and then, carrying out Ar or N inert gas 2 And (4) carrying out curing and pyrolysis in the gas atmosphere, and finally circulating the impregnation and pyrolysis process until the density requirement is met. Wherein the precursor solution for impregnation comprises solid PCS and liquid PCS, and the mass ratio of the solid PCS to the liquid PCS is 0.5-2; the dipping pressure is 1-5MPa, the dipping time is 2-6 hours, and the dipping temperature is 60-130 ℃. The curing temperature is 160-500 ℃, and the curing time is 1-5 hours; the cracking temperature is 950-1500 deg.C, and the cracking time is 1-3 hr.
Example 1
A preparation method of a carbon nano tube/fiber multi-scale reinforcement ceramic matrix composite material comprises the following steps:
1) Using continuous carbon fiber as raw material, firstly weaving into satin cloth, then placing in inert gas Ar or N 2 And performing high-temperature glue discharging treatment in the atmosphere. The rubber discharge process conditions are as follows: the glue discharging temperature is 900 DEGThe rubber discharge time is 1.5 hours.
2) Cobalt acetate is used as a catalyst, and deionized water is used for dissolving to prepare a catalyst solution.
And then placing the catalyst solution in an ultrasonic cleaning machine for ultrasonic-assisted dissolution, and finally preparing the fully dissolved catalyst solution. Wherein the concentration (mass fraction) of the catalyst solution is 1.5%, the ultrasonic temperature is 28 ℃, and the ultrasonic time is 15min.
3) Standing and soaking the carbon fiber satin cloth subjected to rubber discharge in the catalyst solution prepared in the step 2), taking out and drying the carbon fiber satin cloth, and preparing the fiber fabric by adopting a layer-spreading sewing process. Finally, the fiber fabric is placed on the polycarbosilane precursor and is wholly filled with inert gas Ar or N 2 And (3) heating at high temperature in the atmosphere to prepare the carbon nano tube/fiber multi-scale reinforcement fabric. The distance between the fabric and the polycarbosilane precursor is 4cm, and the high-temperature heating temperature is as follows: the temperature is 900 ℃, and the heat preservation time is as follows: for 1 hour.
4) Adopting a PIP process to densify the carbon nanotube/fiber multi-scale reinforcement fabric prepared in the step 3). Wherein the mass ratio of solid PCS to liquid PCS in the impregnation phase is 1; the dipping pressure is 1.5MPa, the dipping time is 2 hours, and the dipping temperature is 60 ℃. The curing temperature is 200 ℃, and the curing time is 2 hours; the cracking temperature is 1050 ℃, and the holding time is 3 hours. The final density obtained was 2.03g/cm 3 The bending strength of the carbon nanotube/fiber multi-scale reinforced ceramic matrix composite material is 411MPa, which is obviously higher than that of the carbon nanotube composite material (325 MPa) without introduction.
Example 2
A preparation method of a carbon nano tube/fiber multi-scale reinforcement ceramic matrix composite material comprises the following steps:
1) Using continuous silicon carbide fiber as raw material, firstly weaving into satin cloth, then placing in inert gas Ar or N 2 And performing high-temperature glue discharging treatment in the atmosphere. The rubber discharge process conditions are as follows: the rubber discharging temperature is 800 ℃, and the rubber discharging time is 1 hour.
2) Nickel nitrate is used as a catalyst, and deionized water is used for dissolving to prepare a catalyst solution. And then placing the catalyst solution in an ultrasonic cleaning machine for ultrasonic-assisted dissolution, and finally preparing the fully dissolved catalyst solution. Wherein the concentration of the catalyst solution is 2%, the ultrasonic temperature is 30 ℃, and the ultrasonic time is 10min.
3) Standing and soaking the silicon carbide fiber satin cloth subjected to binder removal in the catalyst solution prepared in the step 2), taking out and drying the silicon carbide fiber satin cloth, and preparing the fiber fabric by adopting a layer-spreading sewing process. Finally, the fiber fabric is placed on the polycarbosilane precursor and is wholly filled with inert gas Ar or N 2 And (3) heating at high temperature in the atmosphere to prepare the carbon nano tube/fiber multi-scale reinforcement fabric. The distance between the fabric and the polycarbosilane precursor is 5cm, and the high-temperature heating temperature is as follows: the heat preservation time is as follows at 1000℃: for 1 hour.
4) Adopting a PIP process to densify the carbon nano tube/fiber multi-scale reinforcement fabric prepared in the step 3). Wherein the mass ratio of the solid PCS to the liquid PCS in the impregnation phase is 1.2; the impregnation pressure was 2.5MPa, the impregnation time was 2 hours, and the impregnation temperature was 65 ℃. The curing temperature is 210 ℃, and the curing time is 1 hour; the cracking temperature is 1000 ℃, and the holding time is 2 hours. The final density was 2.05g/cm 3 The carbon nano tube/fiber multi-scale reinforced ceramic matrix composite has the bending strength of 397MPa, which is obviously higher than that of the composite without the carbon nano tube (325 MPa).
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to limit the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the embodiments and implementations of the invention without departing from the spirit and scope of the invention, and are within the scope of the invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.
Claims (10)
1. A preparation method of a carbon nano tube/fiber multi-scale reinforced ceramic matrix composite material is characterized by comprising the following steps:
preparing a catalyst solution;
soaking the fiber satin cloth in a catalyst solution, standing, taking out and airing to obtain the fiber satin cloth loaded with the catalyst; manufacturing the fiber satin cloth loaded with the catalyst into a fiber fabric with a preset thickness by adopting a layer-spreading sewing process;
placing the fiber fabric in a container with polycarbosilane at the bottom, wherein the fiber fabric is positioned above the polycarbosilane precursor and is not contacted with the polycarbosilane;
heating the container, decomposing polycarbosilane in the container to generate reducing gas and carbon source gas, and growing carbon nanotubes in the fiber fabric under the action of the reducing gas and the carbon source gas to obtain a carbon nanotube/fiber reinforcement fabric;
and adopting a precursor impregnation cracking process to densify the carbon nanotube/fiber reinforcement fabric to obtain the carbon nanotube/fiber reinforcement ceramic matrix composite.
2. The method for preparing the carbon nanotube/fiber multi-scale reinforced ceramic matrix composite according to claim 1, wherein the specific method for preparing the catalyst solution comprises dissolving the catalyst in deionized water by an ultrasonic dispersion process at room temperature, wherein the catalyst is one or more of cobalt acetate, nickel nitrate or ferrocene;
the mass fraction of the catalyst solution is 0.5-3%.
3. The method according to claim 1, wherein the fiber satin comprises one or a combination of two of a carbon fiber satin or a silicon carbide fiber satin;
before the fiber satin cloth is soaked in the catalyst solution, the fiber satin cloth is subjected to glue discharging, the glue discharging treatment temperature is 800-1200 ℃, and the glue discharging treatment time is 1-4 hours.
4. The method for preparing the carbon nanotube/fiber multi-scale reinforced ceramic matrix composite according to claim 1, wherein the container is a graphite box, the bottom of the graphite box is filled with the cured polycarbosilane, a graphite column is arranged in the graphite box, the fiber fabric is supported above the polycarbosilane precursor through the graphite column, and the distance between the fiber fabric and the polycarbosilane is 2-5 cm;
heating the container in inert atmosphere at 900-1500 deg.c for 1-5 hr.
5. The method according to claim 1, wherein the reducing gas generated by decomposition of polycarbosilane comprises hydrogen, and the carbon source gas comprises methane;
the mass of the carbon nano tubes in the carbon nano tube/fiber reinforcement fabric accounts for 1-8% of the mass of the fiber fabric;
in the carbon nanotube/fiber reinforcement fabric, the carbon nanotubes are in a nanometer scale, and the fibers in the fiber fabric are in a micrometer scale or higher.
6. The method of claim 1, wherein the step of densifying the carbon nanotube/fiber reinforced ceramic matrix composite using a precursor impregnation and pyrolysis process includes performing a pressure impregnation-curing-pyrolysis process on the carbon nanotube/fiber reinforced ceramic matrix composite in a cyclic manner until the density of the carbon nanotube/fiber reinforced ceramic matrix composite meets a predetermined requirement.
7. The method for preparing the carbon nanotube/fiber multi-scale reinforced ceramic matrix composite material according to claim 6, wherein the precursor solution for pressure impregnation comprises solid PCS and liquid PCS, and the mass ratio of the solid PCS to the liquid PCS is 0.5-2; the dipping pressure is 1-5MPa, the dipping time is 2-6 hours, and the dipping temperature is 60-130 ℃;
the curing temperature is 160-500 ℃, and the curing time is 1-5 hours;
the cracking temperature is 950-1500 ℃, and the cracking time is 1-3 hours.
8. The method for preparing the carbon nanotube/fiber multi-scale reinforced ceramic matrix composite according to claim 1, wherein the fiber satin cloth is soaked in the catalyst solution at normal temperature for 30-60 min, and is taken out after standing and dried to obtain the catalyst-loaded fiber satin cloth.
9. A carbon nanotube/fiber multi-scale reinforced ceramic matrix composite material obtained by the preparation method according to any one of claims 1 to 8.
10. The carbon nanotube/fiber multi-scale reinforced ceramic matrix composite according to claim 9, wherein the carbon nanotube/fiber multi-scale reinforced ceramic matrix composite has a density of 1.8-2.2g/cm 3 。
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