CN118771889A - HfC (great Voltage channel)xNySiC modified C/C composite material and preparation method thereof - Google Patents
HfC (great Voltage channel)xNySiC modified C/C composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 89
- 238000001764 infiltration Methods 0.000 claims abstract description 77
- 230000008595 infiltration Effects 0.000 claims abstract description 77
- 238000001035 drying Methods 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000004140 cleaning Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 25
- 238000007789 sealing Methods 0.000 claims abstract description 24
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- 230000004048 modification Effects 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims description 26
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- 230000008901 benefit Effects 0.000 abstract description 3
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- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 40
- 229910010271 silicon carbide Inorganic materials 0.000 description 35
- 229910002804 graphite Inorganic materials 0.000 description 28
- 239000010439 graphite Substances 0.000 description 28
- 238000007664 blowing Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 239000010431 corundum Substances 0.000 description 14
- 229910052593 corundum Inorganic materials 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
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- 229910052799 carbon Inorganic materials 0.000 description 12
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- 238000004506 ultrasonic cleaning Methods 0.000 description 8
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- 229910052735 hafnium Inorganic materials 0.000 description 5
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Abstract
The invention discloses an HfC xNy -SiC modified C/C composite material and a preparation method thereof, comprising the following steps: pretreating the C/C composite material to obtain a C/C preform for infiltration; mixing HfSi 2 with Si 3N4 powder, and drying to obtain powder for infiltration; placing the C/C preform for infiltration in parallel on the upper layer of the powder for infiltration, continuously adding the powder for infiltration until the powder for infiltration completely covers the upper surface of the C/C preform for infiltration and is higher than the upper surface of the C/C preform for infiltration, sealing, and then carrying out modification treatment at high temperature through a reaction infiltration process to obtain the C/C-HfC xNy -SiC composite material; polishing, cleaning and drying the C/C-HfC xNy -SiC composite material to obtain the HfC xNy -SiC modified C/C composite material. The composite material prepared by adopting the reaction infiltration process has the advantages of strong interface bonding, excellent ablation resistance and strong anti-scouring performance.
Description
Technical Field
The invention belongs to the technical field of C/C composite material modification, and relates to an HfC xNy -SiC modified C/C composite material and a preparation method thereof.
Background
Since 1958, carbon/carbon composite materials have been found to be widely used in aerospace field hot end components such as solid rocket engine nozzles, nose cones and leading edges of aircraft, turbine engine blades, and the like due to their low density, high thermal conductivity, high specific strength, high specific modulus, low coefficient of thermal expansion, and the characteristic that mechanical strength does not rise back with temperature rise. However, the carbon/carbon composite material has higher oxidation activity, and the oxidation weight loss greatly reduces the strength of the material. Poor ablation resistance in high enthalpy combustion environments and poor oxidation stability under oxygen-containing heat flows greatly limit the application of carbon/carbon composites.
The melting point of the superhigh temperature ceramic (UHTCs) exceeds 3000 ℃, the melting point of the oxide is above 1800 ℃, and the superhigh temperature ceramic is a heat protection material which can keep the physical and chemical properties relatively stable under the high temperature environment (> 2000 ℃) and the plasma reaction atmosphere and can be repeatedly used above 1650 ℃, and is considered to be an ideal introduction material for improving the performance of the C/C composite material. Research shows that the hafnium carbonitride (HfC xNy) superhigh temperature ceramic has higher melting point, more excellent hardness, toughness and ductility than HfC (3890 ℃), and can better meet the requirements of the service environment of a new generation hypersonic aircraft on the material performance. However, few studies on HfC xNy are currently carried out, and the existing reports are mainly focused on some theoretical calculations and preparation of HfC xNy ceramics and performances of the ceramics, and few students take HfC xNy as a matrix modification component to study the influence of the HfC xNy on the performances of the C/C composite materials.
The literature "Zhang,J.et al.Ablation behavior of a novel carbonitrides HfC0.68N0.32 coating for C/C composites in laser and oxyacetylene environment.Journal of the European Ceramic Society 44,3049-3057." adopts an HfCl 4-CH4-N2-H2 -Ar system, an HfC 0.68 N0.32 coating is deposited on a SiC coating prefabricated on the surface of a C/C composite material through a CVD process, and the material shows good anti-ablation performance under laser and oxyacetylene atmosphere. However, the coating prepared by CVD has poor bonding force with the substrate, and the coating is easy to peel off in the high-temperature long-term ablation process.
Disclosure of Invention
The invention aims to provide an HfC xNy -SiC modified C/C composite material and a preparation method thereof, and solves the problem of poor interface binding force in the prior art.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
A preparation method of an HfC xNy -SiC modified C/C composite material comprises the following steps:
pretreating the C/C composite material to obtain a C/C preform for infiltration;
Mixing HfSi 2 with Si 3N4 powder, and drying to obtain powder for infiltration;
Placing the C/C preform for infiltration in parallel on the upper layer of the powder for infiltration, continuously adding the powder for infiltration until the powder for infiltration completely covers the upper surface of the C/C preform for infiltration and is higher than the upper surface of the C/C preform for infiltration, sealing, and then carrying out modification treatment at high temperature through a reaction infiltration process to obtain the C/C-HfC xNy -SiC composite material;
Polishing, cleaning and drying the C/C-HfC xNy -SiC composite material to obtain the HfC xNy -SiC modified C/C composite material.
Further, the pretreatment includes polishing treatment, cleaning treatment, boiling treatment, and drying treatment.
Further, the boiling treatment temperature is 100-350 ℃ and the treatment time is 1-6 h.
Further, the drying treatment temperature is 70 ℃, and the treatment time is 6-10 h.
Further, the molar ratio of HfSi 2 to Si 3N4 powder is 1-4:1-4.
Further, the HfSi 2 and the Si 3N4 powder are mixed by ball milling, wherein in the ball milling process, the ball-material ratio is 2:1, the rotating speed is 200-500 rpm, and the ball milling time is 4-6 h.
Further, the drying temperature of the powder for infiltration is 60-100 ℃ and the drying time is 8-12 h.
Further, the conditions of the modification treatment are as follows: under the protection environment of Ar or N 2 inert atmosphere or the vacuum environment with the vacuum degree of 1-100 Pa, the temperature is 1600-2100 ℃, the temperature rising rate is 4-10 ℃/min, and the heat preservation time is 0.5-3 h.
Further, the drying temperature of the HfC xNy -SiC modified C/C composite material is 60-100 ℃ and the time is 6-12 h.
The HfC xNy -SiC modified C/C composite material prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of an HfC xNy -SiC modified C/C composite material, which takes mixed powder of HfSi 2 and Si 3N4 as an infiltration agent, and uses HfC xNy with ultra-high melting point, strong hardness, certain toughness and ductility for modifying the C/C composite material, wherein Si 3N4 provides a nitrogen source, and the interface bonding of the composite material prepared by adopting a reaction infiltration process is strong. In addition, the introduction of SiC makes Hf (C, N) -based composites attractive for different high temperature applications, and the relative content of HfC xNy component and SiC is regulated by varying the HfSi 2 to Si 3N4 molar ratio, making the tissue composition easy to control. The invention has simple process and low requirement on equipment, and compared with hafnium carbide, the melting point of the hafnium carbonitride is higher, and the hafnium carbonitride ceramic matrix composite material has excellent ablation resistance under the high-temperature oxygen-containing environment. And hafnium carbonitride has higher hardness, certain toughness and ductility, and has strong anti-scouring performance in extreme aerodynamic heat and high-speed particle erosion environments compared with other ultra-high temperature ceramic matrixes. The service life of the material in the high heat flux, high pressure air flow and high speed particle erosion environment can be better improved, the endurance of the high speed aircraft is prolonged, and the method has great space strategic significance. Meanwhile, on the basis of the invention, the preparation and performance improvement scheme of the HfC xNy modified carbon/carbon composite material can be designed more widely, so that the development prospect of the invention is quite considerable, and the economic benefit and the social benefit are quite outstanding.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a method for preparing a HfC xNy -SiC modified C/C composite material of the present invention.
FIG. 2 is an XRD pattern of the HfC xNy -SiC modified C/C composite prepared in example 1 of the present invention.
FIG. 3 is an SEM image of a HfC xNy -SiC modified C/C composite made according to example 1 of the present invention.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features such as values, amounts, and concentrations that are defined herein in the numerical or percent ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise indicated, the terms "comprising," including, "" containing, "" having, "or the like are intended to cover the meanings of" consisting of … … "and" consisting essentially of … …, "e.g.," a includes a "is intended to cover" a includes a and the other "and" a includes a only.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The following examples use instrumentation conventional in the art. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The following examples used various starting materials, unless otherwise indicated, were conventional commercial products, the specifications of which are conventional in the art. In the description of the present invention and the following examples, "%" means weight percent, and "parts" means parts by weight, and ratios means weight ratio, unless otherwise specified.
The invention is described in further detail below with reference to the attached drawing figures:
Referring to fig. 1, the invention provides a preparation method of an HfC xNy -SiC modified C/C composite material, comprising the following steps:
Step 1: 2.5D C/C composite material is selected, and is processed into a block sample with the size of 10mm multiplied by 10mm, and silicon carbide sand paper with the size of 50 meshes, 800 meshes and 3000 meshes is sequentially used for polishing treatment, so that the sample is ensured to have no obvious defect when being impregnated with a reaction melt, and the surface is in a regular light clean state. And (3) ultrasonically cleaning the polished sample by using deionized water for 3-5 times, wherein the cleaning time is 30-60 min each time, then boiling the blocky sample at 100-350 ℃ for 1-6 h until no bubbles emerge from the surface of the sample, ensuring that the open holes in the sample are completely opened, and then drying the sample in an electrothermal blowing drying oven at 70 ℃ for 6-10 h to obtain the C/C preform for infiltration.
Step 2: mixing HfSi 2 with Si 3N4 powder according to a molar ratio of 1-4:1-4, placing the powder mixture and zirconia grinding balls into a corundum ball milling tank, wherein the ball material ratio is 2:1, sealing the corundum ball milling tank, ball milling with a planetary ball mill at a rotating speed of 200-500 rpm for 4-6 hours, taking out powder, and then placing the powder in an electrothermal blowing drying oven at 60-100 ℃ for drying for 8-12 hours to obtain evenly mixed powder for infiltration.
Step 3: the method comprises the steps of adopting a reaction infiltration process to carry out modification treatment on a C/C composite material, paving 3-5 layers of graphite paper on the inner wall of a graphite crucible, paving 4-10 mm thick infiltration powder on the bottom of the crucible, placing a C/C preform for infiltration on the upper layer of the powder for infiltration in parallel, continuously adding the powder for infiltration until the powder for infiltration completely covers the C/C preform for infiltration and is 5-10 mm higher than the upper surface of the C/C preform for infiltration, ensuring that the powder for infiltration is in a loose state in the powder adding process for infiltration, and after the powder for infiltration is added, sequentially carrying out sealing treatment by using the graphite paper and a carbon felt, and then carrying out sealing treatment on the crucible.
Step 4: the sealed crucible is placed in a graphite furnace for high-temperature treatment, and the high-temperature treatment conditions are as follows: the temperature is 1600-2100 ℃, the vacuum degree in the furnace is 1-100 Pa, or the temperature rising rate is 4-10 ℃/min and the heat preservation time is 0.5-3 h under the protection of Ar or N 2 inert atmosphere, then the power-off cooling is carried out, and the C/C-HfC xNy -SiC composite material is obtained after the sample is cooled to the room temperature along with the furnace.
Step 5: and (3) polishing the C/C-HfC xNy -SiC composite material obtained after reaction infiltration by using diamond grinding discs of 50 meshes, 800 meshes and 3000 meshes in sequence, so as to ensure that no obvious protrusion exists on the surface. And then carrying out ultrasonic cleaning on the sample by using deionized water for 3-5 times, wherein each cleaning time is 30-60 min, and then placing the sample into an electrothermal blowing drying oven to be dried for 6-12 h at 60-100 ℃ to obtain the HfC xNy -SiC modified C/C composite material.
The invention is described in further detail below in connection with specific examples:
embodiment one:
Step 1: 2.5D C/C composite material with the density of 1.1g/cm 3 is selected and processed into a block sample with the density of 10mm multiplied by 10mm, and silicon carbide sand paper with the density of 50 meshes, 800 meshes and 3000 meshes is sequentially used for polishing treatment, so that no obvious defect is caused when the sample is subjected to reaction melt infiltration, and the surface is in a regular light clean state. And (3) carrying out ultrasonic cleaning on the polished sample by using deionized water for 5 times, wherein the cleaning time is 30min each time, then, carrying out boiling treatment on the blocky sample at 300 ℃ for 3h until no bubble emerges on the surface of the sample, ensuring that an opening in the sample is completely opened, and then, placing the sample in an electrothermal blowing drying oven at 70 ℃ for 8h for standby.
Step 2: mixing HfSi 2 and Si 3N4 powder according to a molar ratio of 4:1, placing the powder mixture and zirconia grinding balls into a corundum ball milling tank, wherein the ball material ratio is 2:1, sealing the corundum ball milling tank, ball milling for 6 hours by using a planetary ball mill under the condition of 400rpm, sieving, and then placing in an electrothermal blowing drying oven at 70 ℃ for drying for 8 hours to obtain a uniformly mixed powder mixture, and taking the uniformly mixed powder mixture as powder for infiltration.
Step 3: the method comprises the steps of adopting a reaction infiltration process to carry out modification treatment on a C/C composite material, paving 5 layers of graphite paper on the inner wall of a graphite crucible, paving 10mm thick powder for infiltration on the bottom of the crucible, placing the porous C/C composite material on the upper layer of the powder for infiltration in parallel, continuously adding the powder to completely cover a sample and be 10mm higher than the upper surface of the sample, ensuring that the powder is in a loose state in the powder adding process, sealing the crucible by using the graphite paper and a carbon felt in sequence after the powder is added, and then sealing the crucible.
Step 4: the sealed crucible is placed in a graphite furnace for high-temperature treatment, and the high-temperature treatment conditions are as follows: the temperature is 1700 ℃, the furnace pressure is 10Pa, the heating rate is 5 ℃/min, the heat preservation time is 3h, then the power-off cooling is carried out, and the sample is taken out after being cooled to the room temperature along with the furnace.
Step 5: and (3) polishing the composite material obtained after the reaction infiltration by using diamond grinding discs of 50 meshes, 800 meshes and 3000 meshes in sequence, so as to ensure that no obvious protrusions exist on the surface of the sample. And then carrying out ultrasonic cleaning on the sample by using deionized water for 5 times, wherein the cleaning time is 60 minutes each time, and then putting the sample into an electrothermal blowing drying oven to be dried for 10 hours at 80 ℃ to obtain the HfC xNy -SiC modified C/C composite material.
X-ray diffraction analysis is carried out on the prepared composite material, and as shown in figure 2, the high-melting-point hafnium carbonitride is generated in the infiltration process. Analysis of SEM images of the composite material prepared, as shown in fig. 3, it can be seen from fig. 3 that the sample surface formed a white HfC xNy phase with a grey SiC phase. It can thus be determined that the present example obtained a HfC xNy -SiC modified C/C composite.
Embodiment two:
Step 1: C/C composite material with density of 1.7g/cm 3 is selected, and is processed into cubic block-shaped samples with size of 10mm, and silicon carbide sand paper with 50 meshes, 800 meshes and 3000 meshes is sequentially used for polishing treatment, so that the samples are ensured to have no obvious defects when being impregnated with reaction melt, and the surfaces are in a regular light clean state. And (3) ultrasonically cleaning the polished sample by using deionized water for 3 times, wherein the cleaning time is 60 minutes each time, then, boiling the blocky sample for 3 hours at 350 ℃ until no bubble appears on the surface of the sample, ensuring that the open pores in the sample are completely opened, and then, putting the sample in an electrothermal blowing drying box at 70 ℃ for 6 hours for later use.
Step 2: mixing HfSi 2 and Si 3N4 powder according to a molar ratio of 4:1, placing the powder mixture and zirconia grinding balls into a corundum ball milling tank, wherein the ball material ratio is 2:1, sealing the corundum ball milling tank, ball milling for 6 hours by using a planetary ball mill under the condition of 400rpm, sieving, and then placing in an electrothermal blowing drying oven at 70 ℃ for drying for 8 hours to obtain a uniformly mixed powder mixture, and taking the uniformly mixed powder mixture as powder for infiltration.
Step 3: the preparation method comprises the steps of carrying out modification treatment on a C/C composite material by adopting a reaction infiltration process, paving 4 layers of graphite paper on the inner wall of a graphite crucible, paving 10mm thick powder for infiltration on the bottom of the crucible, placing the porous C/C composite material on the upper layer of the powder for infiltration in parallel, continuously adding the powder to completely cover a sample and be 10mm higher than the upper surface of the sample, ensuring that the powder is in a loose state in the powder adding process, sealing the crucible by using the graphite paper and a carbon felt in sequence after the powder is added, and then sealing the crucible.
Step 4: the sealed crucible is placed in a graphite furnace for high-temperature treatment, and the high-temperature treatment conditions are as follows: the temperature is 1700 ℃, the furnace pressure is 10Pa, the heating rate is 5 ℃/min, the heat preservation time is 3h, then the power-off cooling is carried out, and the sample is taken out after being cooled to the room temperature along with the furnace, thus obtaining the modified carbon-carbon composite material.
Step 5: and (3) polishing the composite material obtained after the reaction infiltration by using diamond grinding discs of 50 meshes, 800 meshes and 3000 meshes in sequence, so as to ensure that no obvious protrusions exist on the surface of the sample. And then carrying out ultrasonic cleaning on the sample by using deionized water for 5 times, wherein the cleaning time is 30min each time, and then putting the sample into an electrothermal blowing drying oven to be dried for 12h at 80 ℃ to obtain the HfC xNy -SiC modified C/C composite material.
Embodiment III:
Step 1: 2.5D C/C composite material with the density of 1.2g/cm 3 is selected and processed into a block sample with the density of 10mm multiplied by 10mm, and silicon carbide sand paper with the density of 50 meshes, 800 meshes and 3000 meshes is sequentially used for polishing treatment, so that no obvious defect is caused when the sample is subjected to reaction melt infiltration, and the surface is in a regular light clean state. And (3) ultrasonically cleaning the polished sample by using deionized water for 3 times, wherein the cleaning time is 60 minutes each time, then boiling the blocky sample for 4 hours at 200 ℃ until no bubbles emerge from the surface of the sample, ensuring that the open holes in the sample are completely opened, and then placing the sample in an electrothermal blowing drying box at 70 ℃ for 6 hours for later use.
Step 2: mixing HfSi 2 and Si 3N4 powder according to a molar ratio of 4:1, placing the powder mixture and zirconia grinding balls into a corundum ball milling tank, wherein the ball material ratio is 2:1, sealing the corundum ball milling tank, ball milling for 4 hours by using a planetary ball mill under the condition of 400rpm, sieving, and then placing in an electrothermal blowing drying oven at 70 ℃ for drying for 8 hours to obtain a uniformly mixed powder mixture, and taking the uniformly mixed powder mixture as powder for infiltration.
Step 3: the preparation method comprises the steps of carrying out matrix modification on a C/C composite material by adopting a reaction infiltration process, paving 5 layers of graphite paper on the inner wall of a graphite crucible, paving 6mm thick powder for infiltration on the bottom of the crucible, placing the porous C/C composite material on the upper layer of the powder for infiltration in parallel, continuously adding the powder until the powder completely covers a sample and is 8mm higher than the upper surface of the sample, ensuring that the powder is in a loose state in the powder adding process, sealing the crucible by using the graphite paper and a carbon felt in sequence after the powder is added, and then sealing the crucible.
Step 4: the sealed crucible is placed in a graphite furnace for high-temperature treatment, and the high-temperature treatment conditions are as follows: and (3) introducing Ar gas atmosphere into the furnace at the temperature of 1900 ℃, heating at the rate of 10 ℃/min, keeping the temperature for 2 hours, then powering off and cooling, and taking out the sample after the sample is cooled to room temperature along with the furnace.
Step 5: and (3) polishing the composite material obtained after the reaction infiltration by using diamond grinding discs of 50 meshes, 800 meshes and 3000 meshes in sequence, so as to ensure that no obvious protrusions exist on the surface of the sample. And then carrying out ultrasonic cleaning on the sample by using deionized water for 5 times, wherein the cleaning time is 30min each time, and then putting the sample into an electrothermal blowing drying oven to be dried for 12h at 80 ℃ to obtain the HfC xNy -SiC modified C/C composite material.
Embodiment four:
Step 1: 2.5D C/C composite material with the density of 1.7g/cm 3 is selected and processed into a block sample with the density of 10mm multiplied by 10mm, and silicon carbide sand paper with the density of 50 meshes, 800 meshes and 3000 meshes is sequentially used for polishing treatment, so that no obvious defect is caused when the sample is subjected to reaction melt infiltration, and the surface is in a regular light clean state. And (3) ultrasonically cleaning the polished sample by using deionized water for 3 times, wherein the cleaning time is 30min each time, then boiling the blocky sample for 3h at 350 ℃ until no bubbles emerge from the surface of the sample, ensuring that the open holes in the sample are completely opened, and then placing the sample in an electrothermal blowing drying oven at 70 ℃ for 8h for later use.
Step 2: mixing HfSi 2 and Si 3N4 powder according to a molar ratio of 4:1, placing the powder mixture and zirconia grinding balls into a corundum ball milling tank, wherein the ball material ratio is 2:1, sealing the corundum ball milling tank, ball milling for 4 hours by using a planetary ball mill under the condition of 300rpm, sieving, and then placing in an electrothermal blowing drying oven at 70 ℃ for drying for 10 hours to obtain a uniformly mixed powder mixture, and taking the uniformly mixed powder mixture as powder for infiltration.
Step 3: the preparation method comprises the steps of carrying out matrix modification on a C/C composite material by adopting a reaction infiltration process, paving 5 layers of graphite paper on the inner wall of a graphite crucible, paving 6mm thick powder for infiltration on the bottom of the crucible, placing the porous C/C composite material on the upper layer of the powder for infiltration in parallel, continuously adding the powder to completely cover a sample and be 8mm higher than the upper surface of the sample, ensuring that the powder is in a loose state in the powder adding process, sealing the crucible by using the graphite paper and carbon powder in sequence after the powder is added, and then sealing the crucible.
Step 4: the sealed crucible is placed in a graphite furnace for high-temperature treatment, and the high-temperature treatment conditions are as follows: and (3) introducing Ar gas atmosphere into the furnace at the temperature of 1900 ℃, maintaining the atmospheric pressure, heating at the speed of 4 ℃/min, keeping the temperature for 1h, then powering off and cooling, and taking out the sample after the sample is cooled to the room temperature along with the furnace.
Step 5: and (3) polishing the composite material obtained after the reaction infiltration by using diamond grinding discs of 50 meshes, 800 meshes and 3000 meshes in sequence, so as to ensure that no obvious protrusions exist on the surface of the sample. And then carrying out ultrasonic cleaning on the sample by using deionized water for 5 times, wherein the cleaning time is 40min each time, and then putting the sample into an electrothermal blowing drying oven to be dried for 12h at 80 ℃ to obtain the HfC xNy -SiC modified C/C composite material.
Fifth embodiment:
Step 1: 2.5D C/C composite material with the density of 1.1g/cm 3 is selected and processed into a block sample with the density of 10mm multiplied by 10mm, and silicon carbide sand paper with the density of 50 meshes, 800 meshes and 3000 meshes is sequentially used for polishing treatment, so that no obvious defect is caused when the sample is subjected to reaction melt infiltration, and the surface is in a regular light clean state. And (3) ultrasonically cleaning the polished sample by using deionized water for 5 times, wherein the cleaning time is 30min each time, then, boiling the blocky sample for 3 hours at 350 ℃ until no bubble appears on the surface of the sample, ensuring that the open pores in the sample are completely opened, and then, putting the sample in an electrothermal blowing drying box at 80 ℃ for 8 hours for standby.
Step 2: mixing HfSi 2 and Si 3N4 powder according to a molar ratio of 4:1, placing the powder mixture and zirconia grinding balls into a corundum ball milling tank, wherein the ball material ratio is 2:1, sealing the corundum ball milling tank, ball milling for 6 hours by using a planetary ball mill under the condition of 300rpm, sieving, and then placing in an electrothermal blowing drying oven at 70 ℃ for drying for 10 hours to obtain a uniformly mixed powder mixture, and taking the uniformly mixed powder mixture as powder for infiltration.
Step 3: the preparation method comprises the steps of carrying out matrix modification on a C/C composite material by adopting a reaction infiltration process, paving 5 layers of graphite paper on the inner wall of a graphite crucible, paving 6mm thick powder for infiltration on the bottom of the crucible, placing the porous C/C composite material on the upper layer of the powder for infiltration in parallel, continuously adding the powder until the powder completely covers a sample and is 8mm higher than the upper surface of the sample, ensuring that the powder is in a loose state in the powder adding process, sealing the crucible by using the graphite paper and a carbon felt in sequence after the powder is added, and then sealing the crucible.
Step 4: the sealed crucible is placed in a graphite furnace for high-temperature treatment, and the high-temperature treatment conditions are as follows: and (3) introducing Ar gas atmosphere into the furnace at 2100 ℃, heating at a rate of 5 ℃/min, maintaining for 1h, then powering off and cooling, and taking out the sample after the sample is cooled to room temperature along with the furnace.
Step 5: and (3) polishing the composite material obtained after the reaction infiltration by using diamond grinding discs of 50 meshes, 800 meshes and 3000 meshes in sequence, so as to ensure that no obvious protrusions exist on the surface of the sample. And then carrying out ultrasonic cleaning on the sample by using deionized water for 5 times, wherein the cleaning time is 30min each time, and then putting the sample into an electrothermal blowing drying oven to be dried for 12h at 80 ℃ to obtain the HfC xNy -SiC modified C/C composite material.
Example six:
Step 1: 2.5D C/C composite material with the density of 1.7g/cm 3 is selected and processed into a block sample with the density of 10mm multiplied by 10mm, and silicon carbide sand paper with the density of 50 meshes, 800 meshes and 3000 meshes is sequentially used for polishing treatment, so that no obvious defect is caused when the sample is subjected to reaction melt infiltration, and the surface is in a regular light clean state. And (3) ultrasonically cleaning the polished sample by using deionized water for 3 times, wherein the cleaning time is 60 minutes each time, then boiling the blocky sample for 3 hours at 300 ℃ until no bubbles emerge from the surface of the sample, ensuring that the open holes in the sample are completely opened, and then placing the sample in an electrothermal blowing drying box at 80 ℃ for drying for 8 hours for later use.
Step 2: mixing HfSi 2 and Si 3N4 powder according to a molar ratio of 1:1, placing the powder mixture and zirconia grinding balls into a corundum ball milling tank, wherein the ball material ratio is 2:1, sealing the corundum ball milling tank, ball milling for 4 hours by using a planetary ball mill under the condition of 400rpm, sieving, and then placing in an electrothermal blowing drying oven at 70 ℃ for drying for 10 hours to obtain a uniformly mixed powder mixture, and taking the uniformly mixed powder mixture as powder for infiltration.
Step 3: the preparation method comprises the steps of carrying out matrix modification on a C/C composite material by adopting a reaction infiltration process, paving 5 layers of graphite paper on the inner wall of a graphite crucible, paving 4mm thick powder for infiltration on the bottom of the crucible, placing the porous C/C composite material on the upper layer of the powder for infiltration in parallel, continuously adding the powder until the powder completely covers a sample and is 8mm higher than the upper surface of the sample, ensuring that the powder is in a loose state in the powder adding process, sealing the crucible by using the graphite paper and a carbon felt in sequence after the powder is added, and then sealing the crucible.
Step 4: the sealed crucible is placed in a graphite furnace for high-temperature treatment, and the high-temperature treatment conditions are as follows: and (3) introducing Ar gas atmosphere into the furnace at 2100 ℃, heating at a rate of 5 ℃/min, maintaining for 1h, then powering off and cooling, and taking out the sample after the sample is cooled to room temperature along with the furnace.
Step 5: and (3) polishing the composite material obtained after the reaction infiltration by using diamond grinding discs of 50 meshes, 800 meshes and 3000 meshes in sequence, so as to ensure that no obvious protrusions exist on the surface of the sample. And then carrying out ultrasonic cleaning on the sample by using deionized water for 3 times, wherein the cleaning time is 60 minutes each time, and then putting the sample into an electrothermal blowing drying oven to be dried for 12 hours at 80 ℃ to obtain the HfC xNy -SiC modified C/C composite material.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing an HfC xNy -SiC modified C/C composite, comprising:
pretreating the C/C composite material to obtain a C/C preform for infiltration;
Mixing HfSi 2 with Si 3N4 powder, and drying to obtain powder for infiltration;
Placing the C/C preform for infiltration in parallel on the upper layer of the powder for infiltration, continuously adding the powder for infiltration until the powder for infiltration completely covers the upper surface of the C/C preform for infiltration and is higher than the upper surface of the C/C preform for infiltration, sealing, and then carrying out modification treatment at high temperature through a reaction infiltration process to obtain the C/C-HfC xNy -SiC composite material;
Polishing, cleaning and drying the C/C-HfC xNy -SiC composite material to obtain the HfC xNy -SiC modified C/C composite material.
2. The method for preparing an HfC xNy -SiC modified C/C composite according to claim 1, wherein said pretreatment comprises a polishing treatment, a cleaning treatment, a boiling treatment and a drying treatment.
3. The method for preparing the HfC xNy -SiC modified C/C composite material according to claim 2, wherein the boiling treatment temperature is 100-350 ℃ and the treatment time is 1-6 h.
4. The method for preparing the HfC xNy -SiC modified C/C composite material according to claim 2, wherein the drying treatment temperature is 70 ℃ and the treatment time is 6-10 h.
5. The method for preparing the HfC xNy -SiC modified C/C composite material according to claim 1, wherein the molar ratio of HfSi 2 to Si 3N4 powder is (1-4): 1-4.
6. The preparation method of the HfC xNy -SiC modified C/C composite material according to claim 1, wherein the HfSi 2 and Si 3N4 powder are mixed by ball milling, the ball-material ratio is 2:1, the rotating speed is 200-500 rpm, and the ball milling time is 4-6 h.
7. The method for preparing the HfC xNy -SiC modified C/C composite material according to claim 1, wherein the drying temperature of the infiltration powder is 60-100 ℃ and the drying time is 8-12 h.
8. The method for preparing the HfC xNy -SiC modified C/C composite material according to claim 1, wherein the modification treatment conditions are as follows: under the protection environment of Ar or N 2 inert atmosphere or the vacuum environment with the vacuum degree of 1-100 Pa, the temperature is 1600-2100 ℃, the temperature rising rate is 4-10 ℃/min, and the heat preservation time is 0.5-3 h.
9. The method for preparing the HfC xNy -SiC modified C/C composite material according to claim 1, wherein the drying temperature of the HfC xNy -SiC modified C/C composite material is 60-100 ℃ and the time is 6-12 h.
10. A HfC xNy -SiC modified C/C composite produced by the method of any one of claims 1 to 9.
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