CN115196987B - 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 disclosed by the invention is simple in preparation process, and the process of providing the reducing gas and the carbon source gas by the polycarbosilane precursor is safe and controllable, so that 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 of the fiber and the matrix has an important 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 become one of hot research directions. In order to improve the interfacial bonding of the composite material and to increase the toughness of the material, it is common practice to prepare one or more interfacial coatings on the surface of the fibers. Although these coatings have a better effect of improving the interface bonding between the fibers and the matrix, the reinforcing effect on the composite is less pronounced. Therefore, the novel interface structure is gradually designed, namely, the structural performance of the composite material is improved and the heat conductivity coefficient is increased by introducing a low-dimensional nano material modified interface with excellent mechanical property and high heat conductivity. Wherein the low-dimensional nanomaterial mainly comprises single-wall/multi-wall carbon nanotubes or nanowires, silicon carbide nanowires, and the like. The in-situ growth 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 surface of the fiber and the matrix, thereby relieving the stress concentration at the defect of the fiber. Meanwhile, the mechanical meshing force between the fiber and the matrix is enhanced, the interface bonding strength of the composite material is improved, more fiber is 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 fibers and the matrix has excellent fiber dominant mechanical properties and good matrix dominant mechanical properties, and is more suitable for a load environment which is subjected to interlayer load and more frequent impact than the traditional ceramic matrix composite material. Therefore, multi-scale hybrid composite materials based on low-dimensional nanomaterial modification have now become leading-edge hot spots in the new material research field. At present, a common preparation process is chemical vapor deposition (CVI), wherein hydrogen is required to be used as a reducing gas to reduce a catalyst, so that the growth efficiency of the carbon nano tube is improved. However, hydrogen gas has inflammable and explosive characteristics, and the technical requirement for deposition equipment is high for preparing the carbon nano tube. In order to reduce the difficulty and cost of carbon nanotube preparation, development of a rapid and safe preparation process without preparing a hydrogen gas source is needed.
Disclosure of Invention
The invention aims to overcome the defects and provide a carbon nano tube/fiber multi-scale reinforced ceramic matrix composite and a preparation method thereof, wherein a catalyst is uniformly loaded on the surface of a fiber by adopting an impregnation method, and then a polycarbosilane precursor is subjected to high-temperature pyrolysis to generate reducing gas and carbon source gas required by the growth of the carbon nano tube, so that the growth of the carbon nano tube in a fiber fabric is completed to obtain the carbon nano tube/fiber reinforced fabric, and the carbon nano tube/fiber reinforced ceramic matrix composite can be obtained after densification treatment is carried out on the carbon nano tube/fiber reinforced fabric. The preparation method disclosed by the invention is simple in preparation process, and the process of providing the reducing gas and the carbon source gas by the polycarbosilane precursor is safe and controllable, so that the preparation method has remarkable advantages in the aspect of rapid and safe preparation.
In order to achieve the above purpose, the present invention provides the following technical solutions:
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; preparing fiber satin cloth loaded with a catalyst into fiber fabric with a preset thickness by adopting a layering stitching 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 a 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 S5, densifying the carbon nano tube/fiber reinforcement fabric by adopting a precursor impregnation cracking process to obtain the carbon nano tube/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 adopting an ultrasonic dispersion process under the condition of room temperature, wherein the catalyst is one or a combination of more than one of cobalt acetate, nickel nitrate or ferrocene;
the mass fraction of the catalyst solution is 0.5% -3%.
Further, the fiber satin fabric in the step S2 includes one or a combination of two of carbon fiber satin fabric and silicon carbide fiber satin fabric;
before the fiber satin is soaked in the catalyst solution, the fiber satin is subjected to glue removal, the glue removal treatment temperature is 800-1200 ℃, and the glue removal treatment time is 1-4 hours.
Further, in the step S3, the container is a graphite box, the bottom of the graphite box is provided with 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.
Further, in the step S4, the reducing gas generated after the decomposition of the polycarbosilane includes hydrogen, and the carbon source gas includes methane;
the mass of the carbon nano tube 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 nano-sized, and the fibers in the fiber fabric are micro-sized or higher.
Further, the specific method for densification of the carbon nanotube/fiber reinforcement fabric by using the precursor impregnation and pyrolysis process in step S5 is to circularly perform the pressure impregnation-curing-pyrolysis process on the carbon nanotube/fiber reinforcement fabric until the density of the carbon nanotube/fiber reinforcement ceramic matrix composite 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 the step S2, the fiber satin cloth is soaked in the catalyst solution for 30-60 min at normal temperature, and is taken out for airing after standing, so that the fiber satin cloth loaded with the catalyst is obtained.
The carbon nano tube/fiber multi-scale reinforced ceramic matrix composite material is obtained by the preparation method, and the density of the carbon nano tube/fiber multi-scale reinforced ceramic matrix composite material is 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 catalyst and the in-situ growth carbon nano tube on the fiber surface are reduced by using the micromolecular gas released by the polycarbosilane in the high-temperature cracking process, the preparation method has the advantages of simple process, short preparation period, convenient regulation and control, and the preparation method solves the technical defects of high equipment requirement, high risk caused by the need of being provided with a hydrogen gas source and the like in the traditional chemical vapor deposition process, and has remarkable advantages in the aspect of rapid and safe preparation.
(2) According to the invention, the combination of the fiber and the matrix can be effectively improved by introducing the carbon nano tube, so that the composite material is secondarily toughened, and the bending strength and the fracture toughness of the composite material with the carbon nano tube are obviously improved.
(3) The invention designs a reaction container, and is matched with proper heating conditions, so that the carbon nano tube can stably grow under the action of small molecular gas generated by the decomposition of the polycarbosilane precursor.
(4) The invention adopts the vacuum impregnation technology 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 method adopts the cured Precursor (PCS) as a carbon source required by the preparation of the carbon nano tube, and reduces the influence of releasing water molecules and the like 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 at different temperature conditions for Polycarbosilane (PCS) of the present invention;
FIG. 2 is a schematic diagram of in situ preparation of carbon nanotubes using heat cured Polycarbosilane (PCS) in accordance with the present invention;
FIG. 3 is a graph showing the morphology of the carbon nanotube/carbon fiber reinforcement prepared at different heating times according to the present invention; 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 clear from the following detailed description of the invention.
The word "exemplary" is used 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. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The invention provides a preparation method for reducing a catalyst and growing carbon nanotubes in situ on the surface of a fiber by using micromolecular gases (H2 or CH4 and the like) released by cured 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 the carbon nanotubes on the surface of the fiber, wherein the types of the released gases 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 tube on the surface of the fiber by changing the cracking temperature of the cured polycarbosilane, and finally densifying the matrix of the carbon nano tube/fiber multi-scale reinforcement fabric by adopting a precursor dipping and cracking process. The method comprises the following specific steps:
1) Preparation of the 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 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 to the surface of 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 small molecular gas released by a polycarbosilane precursor in a high-temperature cracking process so as 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 certain size after glue discharge in the catalyst solution prepared in the step 1), standing, and coating organic glue on the fiber in the preparation process to form a bundle silk, wherein the glue discharge aims at removing organic impurities such as sizing agent and the like on the surface of the fiber; taking out, naturally airing, and preparing the fiber fabric with the thickness required by design by adopting a layering and sewing process; finally, the fiber web was placed in a graphite box with polycarbosilane precursor at the bottom. The graphite column in the graphite box supports the fabric, and the fiber fabric is placed over the cured Polycarbosilane (PCS) to maintain a distance from the polycarbosilane precursor to ensure that the fabric does not contact the polycarbosilane precursor, as shown in fig. 2. Finally, the whole is treated by inert gas Ar or N 2 High-temperature heating is carried out in the gas atmosphere to prepare the carbon nano tube/fiber multi-scale reinforcement fabric, wherein the precursor is polymerized with the increase of temperature in the heating processThe silane decomposes hydrogen, methane and other gases which can be respectively used as reducing gas and carbon source gas for preparing the carbon nano tube, the micromolecular gas released by the polycarbosilane precursor in the high-temperature cracking process reduces the catalyst on the fiber surface and realizes the in-situ growth of the carbon nano tube on the fiber surface to obtain the carbon nano tube/fiber multi-scale reinforcement fabric, wherein the multi-scale refers to the nano-scale carbon nano tube and the micron and higher fiber.
Preferably, the temperature of the fiber glue discharging treatment in the step 2) is as follows: the glue discharging treatment time is 800-1200 ℃, and the glue discharging treatment time is as follows: the high-temperature heating temperature is 1-4 hours: 900-1500 ℃, and the high-temperature heating time is as follows: the distance between the fabric and the precursor is 2-5 cm within 1-5 hours, so that the reducing 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 rate of the carbon nano tube in the fiber fabric is as follows: 1% -8%. The morphology of the carbon nanotube/carbon fiber reinforcement prepared at different heating times is shown in fig. 3, wherein (a) 0h, (b) 0.5h, (c) 1h and (d) 3h, and the growth process of the carbon nanotubes on the fiber surface is clearly shown in fig. 3.
3) Densification of the matrix: and (3) densifying the carbon nano tube/fiber multi-scale reinforcement fabric prepared in the step (2) by adopting a precursor impregnation cracking process (PIP) to prepare the carbon nano tube/fiber multi-scale reinforcement ceramic matrix composite.
Preferably, the steps of the impregnation pyrolysis process in the step 3) are as follows: pressure impregnating the carbon nano tube/fiber multi-scale reinforcement fabric obtained in the step 2) and then carrying out inert gas Ar or N 2 And (3) curing and high-temperature pyrolysis are carried out in the gas atmosphere, and finally the soaking pyrolysis process is circulated 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 ℃ and the time is 1-3 hours.
Example 1
The preparation method of the carbon nano tube/fiber multi-scale reinforcement ceramic matrix composite material comprises the following steps:
1) The continuous carbon fiber is used as raw material, firstly woven into satin cloth, then is treated with inert gas Ar or N 2 And (5) performing high-temperature glue discharging treatment in the atmosphere. The process conditions for discharging the adhesive are as follows: the glue discharging temperature is 900 ℃ and the glue discharging 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 cleaner for ultrasonic auxiliary 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) And (3) standing and soaking the carbon fiber satin cloth subjected to glue removal in the catalyst solution prepared in the step (2), taking out and drying, and preparing the fiber fabric by adopting a layering and stitching process. Finally, the fiber fabric is placed over the polycarbosilane precursor and is integrally exposed to inert gas Ar or N 2 And (3) heating at high temperature in the air 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: and 1 hour.
4) And (3) densifying the carbon nano tube/fiber multi-scale reinforcement fabric prepared in the step (3) by adopting a PIP process. Wherein the mass ratio of the solid PCS to the liquid PCS in the impregnation phase is 1; the impregnation pressure was 1.5MPa, the impregnation time was 2 hours and the impregnation temperature was 60 ℃. The curing temperature is 200 ℃ and the curing time is 2 hours; the cleavage temperature was 1050℃and the incubation time was 3 hours. The final density was 2.03g/cm 3 The bending strength of the carbon nano tube/fiber multi-scale reinforced ceramic matrix composite is 411MPa, which is obviously higher than that of the composite without introducing the carbon nano tube (325 MPa).
Example 2
The preparation method of the carbon nano tube/fiber multi-scale reinforcement ceramic matrix composite material comprises the following steps:
1) The continuous silicon carbide fiber is used as raw material, firstly woven into satin cloth, then the satin cloth is woven with inert gasAr or N 2 And (5) performing high-temperature glue discharging treatment in the atmosphere. The process conditions for discharging the adhesive are as follows: the glue discharging temperature is 800 ℃, and the glue discharging time is 1 hour.
2) The 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 cleaner for ultrasonic auxiliary 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) And (3) standing and soaking the silicon carbide fiber satin cloth subjected to glue removal in the catalyst solution prepared in the step (2), and then taking out and drying the silicon carbide fiber satin cloth to prepare the fiber fabric by adopting a layering and stitching process. Finally, the fiber fabric is placed over the polycarbosilane precursor and is integrally exposed to inert gas Ar or N 2 And (3) heating at high temperature in the air 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 1000 ℃ as follows: and 1 hour.
4) And (3) densifying the carbon nano tube/fiber multi-scale reinforcement fabric prepared in the step (3) by adopting a PIP process. 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 cleavage temperature was 1000℃and the incubation time was 2 hours. The final density was 2.05g/cm 3 The bending strength of the carbon nano tube/fiber multi-scale reinforced ceramic matrix composite is 397MPa, which is obviously higher than that of the composite (325 MPa) without introducing the carbon nano tube.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
What is not described in detail in the present specification is a well known technology to those skilled in the art.
Claims (10)
1. The preparation method of the carbon nano tube/fiber multi-scale reinforced ceramic matrix composite material is characterized by comprising the following steps of:
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; preparing fiber satin cloth loaded with a catalyst into fiber fabric with a preset thickness by adopting a layering stitching process;
placing a 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 a 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;
densification is carried out on the carbon nano tube/fiber reinforcement fabric by adopting a precursor dipping and cracking process, so as to obtain the carbon nano tube/fiber reinforcement ceramic matrix composite;
the container is a graphite box, the cured polycarbosilane is arranged at the bottom of the graphite box, 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.
2. The preparation method of the carbon nano tube/fiber multi-scale reinforced ceramic matrix composite material is characterized in that the specific method for preparing the catalyst solution is that the catalyst is dissolved in deionized water by adopting an ultrasonic dispersion process under the room temperature condition, and the catalyst is one or a combination of more than one of cobalt acetate, nickel nitrate or ferrocene;
the mass fraction of the catalyst solution is 0.5% -3%.
3. The method of preparing a carbon nanotube/fiber multiscale-reinforced ceramic matrix composite according to claim 1, wherein the fiber satin comprises one or a combination of two of carbon fiber satin or silicon carbide fiber satin;
before the fiber satin is soaked in the catalyst solution, the fiber satin is subjected to glue removal, the glue removal treatment temperature is 800-1200 ℃, and the glue removal treatment time is 1-4 hours.
4. The method for preparing a carbon nanotube/fiber multiscale reinforced ceramic matrix composite according to claim 1, wherein the vessel is heated in an inert atmosphere at 900-1500 ℃ for 1-5 hours.
5. The method for preparing a carbon nanotube/fiber multiscale reinforced ceramic matrix composite according to claim 1, wherein the reducing gas generated after decomposition of polycarbosilane comprises hydrogen and the carbon source gas comprises methane;
the mass of the carbon nano tube 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 nano-sized, and the fibers in the fiber fabric are micro-sized or higher.
6. The method for preparing the carbon nanotube/fiber multiscale reinforced ceramic matrix composite according to claim 1, wherein the specific method for densifying the carbon nanotube/fiber reinforcement fabric by using the precursor impregnation and cracking process 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 meets the predetermined requirement.
7. The method for preparing the carbon nanotube/fiber multiscale reinforced ceramic matrix composite material according to claim 6, wherein the precursor solution used 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 nano tube/fiber multi-scale reinforced ceramic matrix composite material according to claim 1, wherein the fiber satin is soaked in a catalyst solution for 30-60 min at normal temperature, and is taken out and dried after standing, so that the fiber satin loaded with the catalyst is obtained.
9. A carbon nanotube/fiber multiscale reinforced ceramic matrix composite obtained according to the preparation method of any one of claims 1 to 8.
10. The carbon nanotube/fiber multiscale reinforced ceramic matrix composite of claim 9, wherein the carbon nanotube/fiber multiscale reinforced ceramic matrix composite has a density of 1.8 to 2.2g/cm 3 。
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