CN112759409B - Carbon/carbon composite material vapor deposition process - Google Patents
Carbon/carbon composite material vapor deposition process Download PDFInfo
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Abstract
The invention discloses a carbon/carbon composite material vapor deposition process, and relates to the technical field of carbon material preparation. The preparation method comprises the steps of preparing a carbon fiber woven piece, dipping treatment and vapor deposition. Before vapor deposition, pretreatment is carried out by using nano particles and nano fibers, and during vapor deposition, the temperature in a furnace is set to be 800-950 ℃, a carbon source is a mixed gas of methane, butylene and acetylene, and deposition is carried out for 50-150 hours; then setting the temperature in the furnace to be 1000-1200 ℃, using methane as a carbon source, and depositing for 50-100h to ensure that the density of the carbon/carbon composite material crucible reaches more than 1.8g/cm 3. The invention can effectively improve the deposition speed of carbon atoms in the material of the woven piece during vapor deposition of the woven piece, realize rapid densification and simultaneously obtain good mechanical properties.
Description
Technical Field
The invention relates to the technical field of carbon material preparation, in particular to a carbon/carbon composite material vapor deposition process.
Background
The carbon/carbon composite material is a novel high-performance structural function composite material which is formed by taking multidimensional braided carbon fibers as a reinforcing phase and taking pyrolytic carbon formed by chemical vapor infiltration or liquid phase impregnation cracking as a matrix, has the advantages of low density, high elastic modulus, large specific strength, low coefficient of thermal expansion, good corrosion resistance and high-temperature performance and the like, and has good application prospect in the fields of aerospace, chemical engineering, metallurgy, nuclear energy and the like.
In recent years, with the popularization and application of carbon/carbon composite materials in the aspect of civil equipment, many companies adopt carbon/carbon composite material crucibles to replace isostatic graphite crucibles, the carbon/carbon composite material crucibles are crucible preforms woven by taking carbon fibers as raw materials, and then matrix carbon reinforced fiber structures are obtained by adopting methods such as a chemical vapor deposition process, a chemical vapor infiltration process, an impregnation process and the like. However, in the conventional CVI method such as the isothermal CVI method, the deposition rate is generally between 2.78 and 6.94 multiplied by 10 to 5 mu m/s because the deposition process is controlled by diffusion and transmission of carbon source gases, so that the densification period of the carbon/carbon composite material is as long as hundreds of hours, the efficiency is low, the cost is high, and the popularization and application of the carbon/carbon composite material are seriously restricted.
Chinese patent application 201410799205.0 discloses a method for rapid vapor deposition densification of carbon/carbon composite material, comprising the following steps: (1) the density is 1.2-1.5g/cm3The surface of the carbon/carbon composite material woven piece is processed to be smooth, and oil stains on the surface are cleaned for later use; (2) placing the carbon/carbon composite material woven piece into a cylindrical vapor deposition tool, and enabling a laser beam to pass through a central circular hole of an upper cover of the vapor deposition tool and focus on the surface of the carbon/carbon composite material woven piece; (3) high-power laser is adopted, the laser wavelength is controlled to be 10.6 mu m, the output power is 3-4.5kW, carbon atoms are rapidly heated and gasified and are deposited in a carbon/carbon composite material weaving piece, and the rapid vapor deposition densification of the carbon/carbon composite material is realized. The invention adopts high-power laser to promote the vapor deposition process of the carbon/carbon composite material, so that the deposition rate of pyrolytic carbon reaches 10-15 mu m/s, and the specific temperature is equal to that of an isothermal CVI (chemical vapor infiltration) methodThe method is improved by 5 orders of magnitude. However, the method uses high-power laser, has higher requirements on technology and equipment, and is difficult to realize large-scale production.
Chinese patent application 201210166266.4 discloses a preparation process of a carbon/carbon composite material crucible for a monocrystalline silicon furnace, which adopts a prefabricated body woven by polyacrylonitrile-based carbon fibers, takes mixed gas of natural gas, propylene and petroleum liquefied gas as a carbon source and nitrogen or argon as carrier gas, regularly switches upper air inlet and lower air inlet of a pipeline in a uniform temperature thermal field formed by a vertical tank type deposition furnace, realizes the combination of a uniform temperature method, a differential pressure method and a forced airflow method by utilizing the pressure difference of the air inside and outside the crucible, realizes the integral rapid densification of a crucible woven part, and the density of the crucible can reach 1.6g/cm after 300 to 350 hours3Compared with the traditional free deposition process, the method greatly shortens the deposition time and reduces the production cost. After the crucible is mechanically processed, the crucible is used in a thermal field of a monocrystalline silicon furnace, the service life of the carbon/carbon composite material crucible is prolonged by 3 to 5 times compared with a hot isostatic pressing graphite crucible, the cost performance is obviously superior to that of the graphite crucible, and the production cost and labor intensity of monocrystalline silicon are greatly reduced. This method is still time consuming.
In view of this, the present application provides a vapor deposition process for carbon/carbon composite material, which improves the structure of the material of the woven piece, increases the deposition rate of carbon atoms in the material of the woven piece, realizes rapid densification, and obtains good mechanical properties at the same time.
Disclosure of Invention
The invention aims to provide a carbon/carbon composite material vapor deposition process, which is characterized in that a nano material layer is added into a woven piece material, then a solution containing nano particles is used for presoaking, and meanwhile, the vapor deposition process conditions are controlled, so that the deposition speed of carbon atoms on the woven piece material can be effectively increased during vapor deposition of the woven piece, rapid densification is realized, and good mechanical properties are obtained.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a carbon/carbon composite material vapor deposition process comprises the following steps:
(1) preparing a carbon fiber woven piece: is divided intoWeaving net blank and carbon cloth with carbon fiber material, weaving sandwich cloth with nanometer fiber and carbon fiber, arranging the sandwich between the net blank and the carbon cloth, needling to obtain felt, winding the felt on a crucible mold, and overlapping and winding the needled carbon cloth and the net blank until the density reaches 0.4-0.7g/cm3Obtaining a carbon fiber woven piece;
(2) dipping treatment: and (2) completely soaking the carbon fiber woven piece obtained in the step (1) in a soaking solution, and performing ultrasonic-assisted treatment, wherein the soaking solution comprises a solvent, nano particles and epoxy resin, the soaking temperature is 50-95 ℃, and the soaking time is 30-150 min.
(3) Vapor deposition: drying the impregnated carbon fiber woven piece, inversely placing the carbon fiber woven piece on a support floor in a deposition furnace, covering an air mask on the support floor in the carbon fiber woven piece, setting the furnace pressure to be 3-8KPa, firstly setting the temperature in the furnace to be 800-plus-one 950 ℃, setting a carbon source to be mixed gas of methane, butylene and acetylene, and depositing for 50-150 h; then setting the temperature in the furnace to 1000-1200 ℃, taking methane as a carbon source, and depositing for 50-100h to ensure that the density of the carbon/carbon composite material crucible reaches 1.8g/cm3The above.
Preferably, in the step (1), the mass ratio of the nanofibers to the carbon fibers in the sandwich cloth is 1:40-80, and more preferably 1: 50.
Preferably, in the step (1), the preparation method of the sandwich cloth comprises the following steps: weaving the carbon fiber into a cloth piece, soaking the cloth piece into the dispersed nanofiber solution, filtering to remove the solvent to enable the nanofiber to be left on the cloth piece, taking out and drying to obtain the carbon fiber nano-fabric.
Further preferably, the sandwich fabric can be prepared by using a paper sheet former, specifically: pouring the nanofiber into a standard paper sheet former, adding water, stirring for 3-10min to obtain nanofiber solution, stirring the cloth piece in the standard paper sheet former for 1-5min, opening, filtering, taking out, and drying to obtain the nanofiber fabric.
The nanofiber solution has a mass concentration of 0.1 to 1%, preferably 0.4%.
Preferably, in the felt in the step (1), the mass ratio of the total mass of the net tire and the carbon cloth to the sandwich cloth is 4-10: 1.
Preferably, in the step (2), the mass ratio of the carbon fiber woven piece to the impregnating solution is 1: 5-20.
Preferably, in the step (2), the mass ratio of the solvent, the nanoparticles and the epoxy resin in the impregnation liquid is 20:1-2:1-2, and more preferably 20:1.6: 1.2.
Wherein the solvent is at least one selected from ethyl acetate, ethanol and acetone.
The nano particles are at least one of nano titanium dioxide and nano silicon dioxide, and the particle size is not more than 60 nm.
Preferably, in the step (2), the impregnation temperature is 68 ℃, and the impregnation time is 60 min.
Preferably, in the step (3), the drying includes, but is not limited to, natural airing, blow drying, drying and the like, and further preferably drying at 105 ℃.
Preferably, in the step (3), the volume ratio of methane, butene and acetylene in the mixed gas is 1.8-2.2:3.8-4.2:0.8-1.2, and is further preferably 2:4: 1.
Preferably, in the step (3), the carrier gas for vapor deposition is nitrogen, and the volume ratio of the carrier gas to the carbon source is 2: 1.
Preferably, in the step (3), the mixed gas introducing amount is controlled to be 6m3H, methane inlet of 4m3/h。
Preferably, in the step (3), the pressure difference between the inside and the outside of the crucible is controlled to be 650 KPa.
The invention has the following beneficial effects:
(1) the deposition speed of carbon atoms on the material of the woven piece can be effectively improved during the vapor deposition of the woven piece, the rapid densification is realized, and the vapor deposition treatment time is shortened;
(2) the defect of mechanical property reduction caused by rapid densification is avoided, and the process disclosed by the invention can obtain good mechanical property.
Drawings
Fig. 1 is a schematic structural view of a carbon fiber woven member of the present application.
Detailed Description
The present invention will be further explained with reference to specific examples in order to make the technical means, the technical features, the technical objectives and the effects of the present invention easier to understand, but the following examples are only preferred embodiments of the present invention, and not all embodiments of the present invention. In the interest of clarity, not all features of an actual implementation are described. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail. It will of course be appreciated that in the development of any such actual embodiment, numerous implementation-specific details must be set forth in order to achieve the developer's specific goals. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention.
The experimental methods in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the embodiment described below, it is preferred that,
the nano titanium dioxide is purchased from titanium Tang nanotechnology, and the particle size is 5 nm;
the nano silicon dioxide is purchased from Jiangsu Tianxing New Material Co., Ltd, model TSP-H10, and has the particle size of 20 nm;
the epoxy resin is Dow DER 671;
the nano-fiber is purchased from nano-new material science and technology, article number 9112.
Basic embodiment
(1) Preparing a carbon fiber woven piece: pouring the nano-fibers into a standard paper sheet former, adding water, stirring for 5min to obtain a nano-fiber solution with the mass concentration of 0.1-1%, wherein the mass ratio of the nano-fibers to the carbon fibers is 1:40-80, stirring the cloth piece in the standard paper sheet former up and down for 3min, opening the water filter, filtering out water, taking out and drying to obtain the sandwich cloth;
respectively weaving a mesh tire and carbon cloth by using carbon fiber raw materials, arranging an interlayer between the mesh tire and the carbon cloth, and compounding into a felt by needling, wherein the mass ratio of the total mass of the mesh tire and the carbon cloth to the mass of the interlayer cloth is 4-10: 1; winding the felt on a crucible mold, and overlapping and winding the needled carbon cloth and the net body until the density reaches 0.4-0.7g/cm3Obtaining a carbon fiber woven piece;
(2) dipping treatment: completely soaking the carbon fiber woven piece obtained in the step (1) in an impregnation liquid, wherein the mass ratio of the carbon fiber woven piece to the impregnation liquid is 1: 5-20, ultrasonic auxiliary treatment (ultrasonic power 1000W), wherein the impregnation liquid comprises a solvent, nano particles and epoxy resin, the impregnation temperature is 50-95 ℃, and the impregnation time is 30-150 min.
(3) Vapor deposition: drying the impregnated carbon fiber woven piece in an oven at 105 ℃ for 60min, inversely placing the dried carbon fiber woven piece on a support floor in a deposition furnace, covering an air mask on the support floor in the carbon fiber woven piece, and pressing the furnace at 3-8 KPa;
firstly setting the temperature in the furnace to 800-950 ℃, wherein the carbon source is the mixed gas of methane, butylene and acetylene, and the introduction amount of the mixed gas is 6m3Depositing for 50-150h, wherein the carrier gas is nitrogen, the volume ratio of the carrier gas to the carbon source is 2: 1;
then setting the temperature in the furnace to 1000-1200 ℃, using methane as a carbon source and 4m of methane introduction amount3The carrier gas is nitrogen, the volume ratio of the carrier gas to the carbon source is 2:1, the deposition is carried out for 50-100h, the pressure difference between the inside and the outside of the crucible is controlled at 650KPa, and the density of the obtained carbon/carbon composite material crucible reaches 1.75g/cm3The above.
In the step (2), the mass ratio of the solvent, the nanoparticles and the epoxy resin in the impregnation liquid is 20:1-2:1-2, and more preferably 20:1.6: 1.2.
In the step (3), the volume ratio of methane, butylene and acetylene in the mixed gas is 1.8-2.2:3.8-4.2: 0.8-1.2.
Example 1
(1) Preparing a carbon fiber woven piece: weaving carbon fibers into a cloth piece, pouring the nanofibers into a standard paper sheet former, adding water and stirring for 5min to obtain a nanofiber solution with the mass concentration of 0.4%, wherein the mass ratio of the nanofibers to the carbon fibers is 1:50, vertically stirring the cloth piece in the standard paper sheet former for 3min, starting to filter water, filtering out water, taking out, and drying in an oven at 75 ℃ for 60min to obtain the sandwich cloth;
respectively weaving a mesh tire and carbon cloth by using carbon fiber raw materials, arranging an interlayer between the mesh tire and the carbon cloth, and compounding into a felt by needling, wherein the mass ratio of the total mass of the mesh tire and the carbon cloth to the mass of the interlayer cloth is 6: 1; winding the felt on a crucible mold, and then overlapping and winding the needled carbon cloth and the net bodyThe density reaches 0.39g/cm3Obtaining a carbon fiber woven piece;
(2) dipping treatment: completely soaking the carbon fiber woven piece obtained in the step (1) in an impregnation liquid, wherein the mass ratio of the carbon fiber woven piece to the impregnation liquid is 1: 10, carrying out ultrasonic auxiliary treatment (ultrasonic power is 1000W), and uniformly mixing and stirring the ethyl acetate, the nano titanium dioxide and the epoxy resin to obtain the impregnation liquid, wherein the mass ratio of the ethyl acetate to the nano titanium dioxide to the epoxy resin is 20:1.6:1.2, the impregnation temperature is 68 ℃, and the impregnation time is 60 min. And recovering the residual nanoparticles.
(3) Drying the impregnated carbon fiber woven piece in an oven at 105 ℃ for 60min to obtain a crucible prefabricated piece, inversely placing the crucible prefabricated piece on a supporting floor in a deposition furnace, covering an air mask on the supporting floor in the carbon fiber woven piece, and pressing the furnace at 5 KPa;
firstly, setting the temperature in a furnace to be 850 ℃, using a carbon source of a mixed gas of methane, butylene and acetylene, wherein the volume ratio of the methane to the butylene to the acetylene in the mixed gas is 2:4:1, and the introduction amount of the mixed gas is 6m3Depositing for 80 hours, wherein the carrier gas is nitrogen, the volume ratio of the carrier gas to the carbon source is 2: 1;
then setting the temperature in the furnace to 1100 ℃, taking methane as a carbon source and 4m of methane as an inlet amount3And/h, the carrier gas is nitrogen, the volume ratio of the carrier gas to the carbon source is 2:1, the deposition is carried out for 50h, and the pressure difference between the inside and the outside of the crucible is controlled at 650 KPa.
Example 2
(1) Preparing a carbon fiber woven piece: weaving carbon fibers into a cloth piece, pouring the nanofibers into a standard paper sheet former, adding water and stirring for 5min to obtain a nanofiber solution with the mass concentration of 0.1%, wherein the mass ratio of the nanofibers to the carbon fibers is 1:40, vertically stirring the cloth piece in the standard paper sheet former for 3min, starting to filter water, filtering out water, taking out, and drying in an oven at 75 ℃ for 60min to obtain the sandwich cloth;
respectively weaving a mesh tire and carbon cloth by using carbon fiber raw materials, arranging an interlayer between the mesh tire and the carbon cloth, and compounding into a felt by needling, wherein the mass ratio of the total mass of the mesh tire and the carbon cloth to the mass of the interlayer cloth is 4: 1; winding the felt on a crucible mold, and overlapping and winding the needled carbon cloth and the net body until the density reaches 0.24g/cm3Obtaining a carbon fiber woven piece;
(2) dipping treatment: completely soaking the carbon fiber woven piece obtained in the step (1) in an impregnation liquid, wherein the mass ratio of the carbon fiber woven piece to the impregnation liquid is 1:5, carrying out ultrasonic auxiliary treatment (ultrasonic power is 1000W), wherein the impregnation liquid is prepared by uniformly mixing and stirring ethanol, nano titanium dioxide and epoxy resin, the mass ratio of the ethanol to the nano titanium dioxide to the epoxy resin is 20:1:1, the impregnation temperature is 68 ℃, and the impregnation time is 60 min. And recovering the residual nanoparticles.
(3) Drying the impregnated carbon fiber woven piece in an oven at 105 ℃ for 60min to obtain a crucible prefabricated piece, inversely placing the crucible prefabricated piece on a supporting floor in a deposition furnace, covering an air mask on the supporting floor in the carbon fiber woven piece, and pressing the furnace at 5 KPa;
firstly, setting the temperature in a furnace to be 850 ℃, using a carbon source of a mixed gas of methane, butylene and acetylene, wherein the volume ratio of the methane to the butylene to the acetylene in the mixed gas is 2:4:1, and the introduction amount of the mixed gas is 6m3Depositing for 80 hours, wherein the carrier gas is nitrogen, the volume ratio of the carrier gas to the carbon source is 2: 1;
then setting the temperature in the furnace to 1100 ℃, taking methane as a carbon source and 4m of methane as an inlet amount3And/h, the carrier gas is nitrogen, the volume ratio of the carrier gas to the carbon source is 2:1, the deposition is carried out for 50h, and the pressure difference between the inside and the outside of the crucible is controlled at 650 KPa.
Example 3
(1) Preparing a carbon fiber woven piece: weaving carbon fibers into a cloth piece, pouring the nanofibers into a standard paper sheet former, adding water and stirring for 5min to obtain a nanofiber solution with the mass concentration of 1%, wherein the mass ratio of the nanofibers to the carbon fibers is 1:80, vertically stirring the cloth piece in the standard paper sheet former for 5min, starting to filter water, filtering out water, taking out, and drying in an oven at 75 ℃ for 60min to obtain the sandwich cloth;
respectively weaving a mesh tire and carbon cloth by using carbon fiber raw materials, arranging an interlayer between the mesh tire and the carbon cloth, and compounding into a felt by needling, wherein the mass ratio of the total mass of the mesh tire and the carbon cloth to the mass of the interlayer cloth is 10: 1; winding the felt on a crucible mold, and then overlapping and winding the needled carbon cloth and the net body to achieve the density of 0.57g/cm3Obtaining a carbon fiber woven piece;
(2) dipping treatment: completely soaking the carbon fiber woven piece obtained in the step (1) in an impregnation liquid, wherein the mass ratio of the carbon fiber woven piece to the impregnation liquid is 1:20, performing ultrasonic-assisted treatment (ultrasonic power is 1000W), and the impregnation liquid is prepared by uniformly mixing and stirring acetone, nano silicon dioxide and epoxy resin, wherein the mass ratio of the acetone, the nano silicon dioxide and the epoxy resin is 20:2:2, the impregnation temperature is 68 ℃, and the impregnation time is 60 min. And recovering the residual nanoparticles.
(3) Drying the impregnated carbon fiber woven piece in an oven at 105 ℃ for 60min to obtain a crucible prefabricated piece, inversely placing the crucible prefabricated piece on a supporting floor in a deposition furnace, covering an air mask on the supporting floor in the carbon fiber woven piece, and pressing the furnace at 5 KPa;
firstly, setting the temperature in a furnace to be 850 ℃, using a carbon source of a mixed gas of methane, butylene and acetylene, wherein the volume ratio of the methane to the butylene to the acetylene in the mixed gas is 2:4:1, and the introduction amount of the mixed gas is 6m3Depositing for 80 hours, wherein the carrier gas is nitrogen, the volume ratio of the carrier gas to the carbon source is 2: 1;
then setting the temperature in the furnace to 1100 ℃, taking methane as a carbon source and 4m of methane as an inlet amount3And/h, the carrier gas is nitrogen, the volume ratio of the carrier gas to the carbon source is 2:1, the deposition is carried out for 50h, and the pressure difference between the inside and the outside of the crucible is controlled at 650 KPa.
Example 4
The steps (1) and (2) are the same as the embodiment 1, and the step (3) is as follows:
drying the impregnated carbon fiber woven piece in an oven at 105 ℃ for 60min to obtain a crucible prefabricated piece, inversely placing the crucible prefabricated piece on a supporting floor in a deposition furnace, covering an air mask on the supporting floor in the carbon fiber woven piece, and pressing the furnace at 5 KPa;
firstly setting the temperature in a furnace to be 800 ℃, setting a carbon source to be a mixed gas of methane, butylene and acetylene, wherein the volume ratio of the methane to the butylene to the acetylene in the mixed gas is 1.8:4.2:0.8, and the introduction amount of the mixed gas is 6m3Depositing for 50 hours, wherein the carrier gas is nitrogen, the volume ratio of the carrier gas to the carbon source is 2: 1;
then setting the temperature in the furnace to 1000 ℃, taking methane as a carbon source and 4m of methane input3And/h, the carrier gas is nitrogen, the volume ratio of the carrier gas to the carbon source is 2:1, the deposition is carried out for 80h, and the pressure difference between the inside and the outside of the crucible is controlled to be 650 KPa.
Example 5
The steps (1) and (2) are the same as the embodiment 1, and the step (3) is as follows:
drying the impregnated carbon fiber woven piece in an oven at 105 ℃ for 60min to obtain a crucible prefabricated piece, inversely placing the crucible prefabricated piece on a supporting floor in a deposition furnace, covering an air mask on the supporting floor in the carbon fiber woven piece, and pressing the furnace at 5 KPa;
firstly, setting the temperature in a furnace to 950 ℃, using a carbon source of a mixed gas of methane, butene and acetylene, wherein the volume ratio of the methane to the butene to the acetylene in the mixed gas is 2.2:3.8:1.2, and the introduction amount of the mixed gas is 6m3Depositing for 150 hours, wherein the carrier gas is nitrogen, the volume ratio of the carrier gas to the carbon source is 2: 1;
then setting the temperature in the furnace to 1200 ℃, taking methane as a carbon source and 4m of methane input3And/h, the carrier gas is nitrogen, the volume ratio of the carrier gas to the carbon source is 2:1, the deposition is carried out for 100h, and the pressure difference between the inside and the outside of the crucible is controlled at 650 KPa.
Comparative example 1
Unlike example 1, comparative example 1 was not subjected to the impregnation treatment, i.e., the woven fabric of step (1) was prepared, and had a density of 0.41g/cm3。
Comparative example 2
In contrast to example 1, comparative example 2 had no sandwich cloth added and the knit density was 0.40g/cm3。
Comparative example 3
Different from the embodiment 1, the mass ratio of the total mass of the net tire and the carbon cloth to the sandwich cloth is 12:1, and the density of the weaving piece is 0.68g/cm3。
Comparative example 4
In contrast to example 1, the knit density was 0.46g/cm3Epoxy resin was not added to the impregnation solution.
Comparative example 5
In contrast to example 1, the knit density was 0.43g/cm3No nanoparticles were added to the impregnation solution.
Comparative example 6
In contrast to example 1, the knit density was 0.42g/cm3And the mass ratio of the ethyl acetate, the nano titanium dioxide and the epoxy resin in the impregnation liquid is 20:2.5: 0.5.
Comparative example 7
In contrast to example 1, the knit density was 0.83g/cm3。
Comparative example 8
The steps (1) and (2) are the same as the embodiment 1, and the step (3) is as follows:
drying the impregnated carbon fiber woven piece in an oven at 105 ℃ for 60min to obtain a crucible prefabricated piece, inversely placing the crucible prefabricated piece on a supporting floor in a deposition furnace, covering an air mask on the supporting floor in the carbon fiber woven piece, and pressing the furnace at 5 KPa;
setting the temperature in the furnace to 1000 ℃, taking methane as a carbon source and 6m of mixed gas introduction quantity3And/h, the carrier gas is nitrogen, the volume ratio of the carrier gas to the carbon source is 2:1, the deposition is carried out for 200h, and the pressure difference between the inside and the outside of the crucible is controlled at 650 KPa.
Comparative example 9
Unlike example 1, in step (3), the volume ratio of methane, butene and acetylene in the mixed gas was 1:1: 1.
Results testing
1. Vapor deposition rate detection
Density change after vapor deposition completion is as in table 1:
table 1.
| Density g/cm of knitted fabric3 | Density g/cm after CVD3 | |
| Example 1 | 0.39 | 1.92 |
| Example 2 | 0.24 | 1.75 |
| Example 3 | 0.57 | 1.84 |
| Example 4 | 0.40 | 1.87 |
| Example 5 | 0.39 | 2.21 |
| Comparative example 1 | 0.41 | 1.33 |
| Comparative example 2 | 0.40 | 1.67 |
| Comparative example 3 | 0.68 | 1.80 |
| Comparative example 4 | 0.46 | 1.85 |
| Comparative example 5 | 0.43 | 1.38 |
| Comparative example 6 | 0.42 | 1.71 |
| Comparative example 7 | 0.83 | 1.72 |
| Comparative example 8 | 0.39 | 1.63 |
| Comparative example 9 | 0.39 | 1.82 |
2. The crucible preforms prepared in examples 1 to 3 and comparative examples 1 to 7 were subjected to T-peel strength test according to a unified method, and the results are shown in Table 2:
table 2.
3. The crucible preforms after vapor deposition of the embodiment and comparative example were shaped at 1800 ℃ according to a uniform method, turned, shaped, ground and polished to obtain the finished crucible, and the tensile strength was measured, the results are shown in table 3:
table 3.
| Tensile strength Mpa | |
| Example 1 | 78 |
| Example 2 | 80 |
| Example 3 | 77 |
| Example 4 | 82 |
| Example 5 | 78 |
| Comparative example 1 | 76 |
| Comparative example 2 | 72 |
| Comparative example 3 | 68 |
| Comparative example 4 | 71 |
| Comparative example 5 | 76 |
| Comparative example 6 | 75 |
| Comparative example 7 | 79 |
| Comparative example 8 | 81 |
| Comparative example 9 | 76 |
It can be seen that the density of the vapor-deposited alloy reaches more than 1.75g/cm3, the deposition time is shortened by improving the braided part and the vapor deposition process, and the alloy has better strength performance.
The present invention is not limited to the above-described preferred embodiments, but rather, the present invention is to be construed broadly and cover all modifications, equivalents, and improvements falling within the spirit and scope of the present invention.
Claims (8)
1. A carbon/carbon composite material vapor deposition process is characterized by comprising the following steps:
(1) preparing a carbon fiber woven piece: respectively weaving net body and carbon cloth with carbon fiber raw materials, weaving sandwich cloth with nano fiber and carbon fiber, arranging the sandwich between the net body and the carbon cloth, compounding into felt by needling, winding the felt on a crucible mold, and overlapping and winding the needled carbon cloth and the net body until the density reaches 0.4-0.7g/cm3Obtaining a carbon fiber woven piece;
(2) dipping treatment: completely soaking the carbon fiber woven piece obtained in the step (1) in a soaking solution, and performing ultrasonic-assisted treatment, wherein the soaking solution comprises a solvent, nano particles and epoxy resin, the soaking temperature is 50-95 ℃, and the soaking time is 30-150 min; in the impregnation liquid, the mass ratio of the solvent to the nano particles to the epoxy resin is 20:1-2: 1-2; the nano particles are selected from at least one of nano titanium dioxide and nano silicon dioxide, and the particle size is not more than 60 nm;
(3) vapor deposition: drying the impregnated carbon fiber woven piece, inversely placing the carbon fiber woven piece on a support floor in a deposition furnace, covering an air mask on the support floor in the carbon fiber woven piece, setting the furnace pressure to be 3-8KPa, firstly setting the temperature in the furnace to be 800-950 ℃, and setting the carbon source to be methane, butylene and acetyleneDepositing the mixed gas for 50-150 h; then setting the temperature in the furnace to 1000-1200 ℃, taking methane as a carbon source, and depositing for 50-100h to ensure that the density of the carbon/carbon composite material crucible reaches 1.8g/cm3The above; the volume ratio of methane, butylene and acetylene in the mixed gas is 1.8-2.2:3.8-4.2: 0.8-1.2.
2. The vapor deposition process according to claim 1, wherein in step (1), the mass ratio of the nanofibers and the carbon fibers in the sandwich fabric is 1: 40-80.
3. The vapor deposition process according to claim 2, wherein in step (1), the mass ratio of nanofibers to carbon fibers in the sandwich cloth is 1: 50.
4. The vapor deposition process according to claim 1, wherein in step (1), the mass ratio of the total mass of the mesh body and the carbon cloth to the sandwich cloth in the felt is 4-10: 1.
5. The vapor deposition process of claim 1, wherein in step (2), the mass ratio of the solvent, the nanoparticles, and the epoxy resin in the impregnating solution is 20:1.6: 1.2.
6. A vapour deposition process according to claim 1, wherein the solvent is selected from at least one of ethyl acetate, ethanol, acetone.
7. The vapor deposition process according to claim 1, wherein in the step (2), the mass ratio of the carbon fiber woven piece to the impregnating solution is 1: 5-20.
8. The vapor deposition process according to claim 1, wherein in the step (3), the mixed gas is introduced in an amount of 6m3H, methane inlet of 4m3/h。
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