CN106830967B - Heat-resistant high-strength carbon/ceramic fastener and preparation method thereof - Google Patents
Heat-resistant high-strength carbon/ceramic fastener and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 102
- 239000000919 ceramic Substances 0.000 title claims description 26
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 65
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 44
- 239000004917 carbon fiber Substances 0.000 claims abstract description 44
- 239000003292 glue Substances 0.000 claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006229 carbon black Substances 0.000 claims abstract description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 11
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 21
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 15
- 239000005011 phenolic resin Substances 0.000 claims description 15
- 229920001568 phenolic resin Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012466 permeate Substances 0.000 claims description 5
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
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- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 3
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- 238000004519 manufacturing process Methods 0.000 description 8
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
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- 229910016006 MoSi Inorganic materials 0.000 description 1
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- 239000007770 graphite material Substances 0.000 description 1
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- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
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- 238000004321 preservation Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
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- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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Abstract
The invention discloses a heat-resistant high-strength carbon/ceramic material fastener and a preparation method thereof. The carbon/ceramic material comprises the following components: 30-60% of disordered carbon fibers; 10-18% of carbon black; 10-20% of silicon powder; 8-16% of molybdenum powder; 6-12% of silicon carbide; 3-10% of zirconium oxide; 10-25% of glue solution. And firing at high temperature. The invention has excellent high temperature resistance, excellent mechanical property at high temperature, good corrosion resistance and good processing property, and can greatly reduce the preparation and processing cost.
Description
The technical field is as follows:
the invention relates to a high-temperature-resistant and high-strength ceramic material, in particular to a carbon/ceramic fastening piece and a connecting piece for various high-temperature furnaces and a preparation method thereof.
Background art:
an ultra-high temperature (more than 1500 ℃) vacuum furnace is important equipment for industrial production, in particular for the production of new energy materials such as monocrystalline silicon and polycrystalline silicon, or high-performance special ceramics such as BN ceramics and nano ceramics. The equipment relates to a large number of connecting pieces and/or fastening pieces which are in a high-temperature state, the service life of the connecting pieces or fastening pieces made of common metal materials is short in the ultra-high-temperature state, the heat resistance of steel or iron fastening pieces cannot meet the requirement, and in addition, the strength of the conventional fastening pieces made of graphite materials is low, so that the technical requirements of resisting the high temperature of more than 1500 ℃ and the bending strength of more than 100MPa are difficult to achieve. A high temperature resistant fastener made of carbon/carbon (C/C) materials has been developed, which substantially meets the above technical requirements, and the preparation process thereof is as follows: woven carbon fiber preform (density ρ 0.5 g/cm)3) → preform high temperature treatment (> 2000 ℃) → CVD method increasing density (density ρ 1.3 g/cm)3Time 300h) → high temperature treatment (> 2300 ℃) → CVD method increasing density (density ρ of 1.5 g/cm)3Time 500h) - → high temperature treatment (> 2400 ℃) → processing → CVD method of increasing density (density ρ ═ 1.7g/cm3Time 700h) → high temperature treatment (> 2400 ℃) → processing → CVD method of increasing density (density ρ 1.75g/cm ═3And the time is 900h) → high-temperature treatment (> 2400 ℃) → finished products. From the above processes, it can be seen that the raw material of the carbon/carbon material is expensive, the production process is complicated, the production period is very long, the energy consumption is high, the production cost is high, in addition, the product quality is not high, the fastener is easy to fall off, especially, the carbon/carbon material has low oxidation resistance and poor ablation resistance, which results in short product service life, and for the reasons, the fastener problem becomes an important issue for high temperature furnace manufacturingOne of the keys. As the current domestic ultrahigh-temperature vacuum furnace has more than million levels, the using amount of every year of fasteners or connecting pieces exceeds ten million sets of the fasteners or the connecting pieces, if the using life of the fasteners or the connecting pieces is too short, the damage or the replacement of the fasteners or the connecting pieces is a huge loss, and the loss of production interruption, maintenance labor and the like caused by the damage or the replacement is huge. Therefore, the improvement of the performance of the fastener or the connector of the high temperature furnace or equipment has very urgent requirements, and has great economic benefits, which is a problem to be solved urgently.
The invention content is as follows:
the invention aims to disclose a carbon/ceramic material or a fastening piece or a connecting piece prepared from the carbon/ceramic material, which has high mechanical property and can be used in a high-temperature state.
The invention also aims to disclose a preparation method of the carbon/ceramic fastener.
The heat-resistant high-strength carbon/ceramic material comprises the following components: 30-60% of disordered carbon fibers; 10-18% of carbon black; 10-20% of silicon powder; 8-16% of molybdenum powder; 6-12% of silicon carbide; 3-10% of zirconium oxide; 10-25% of glue solution.
The heat-resistant high-strength carbon/ceramic material further comprises the following components: 30-40% of disordered carbon fibers; 10-12% of carbon black; 17-20% of silicon powder; 10-12% of molybdenum powder; 10-12% of silicon carbide; 6-10% of zirconium oxide; 10-15% of glue solution.
The heat-resistant high-strength carbon/ceramic material further comprises the following components: 40-55% of disordered carbon fibers; 16-18% of carbon black; 10-12% of silicon powder; 8-12% of molybdenum powder; 6-8% of silicon carbide; 8-6% of zirconium oxide; 12-25% of glue solution.
The disordered carbon fiber is one of short carbon fiber, waste long carbon fiber and messy carbon fiber or any combination thereof.
The glue solution comprises the following components: 94-98% of phenolic resin; 0.1-2.0% of a coupling agent; 1.0 to 4.0% of ethyl cellulose.
The preparation method of the heat-resistant high-strength carbon/ceramic fastener comprises the following preparation steps:
a. mixing carbon black, silicon powder, molybdenum powder, silicon carbide and zirconia to prepare a mixed intermediate material;
b. soaking the disordered carbon fibers in the glue solution for 12-24 hours;
c. mixing the mixed intermediate material and the glue solution mixed with the disordered carbon fibers to prepare a blank;
d. preserving the heat of the blank at 80-120 ℃ for 10-30 minutes to semi-cure the blank;
e. putting the prepared semi-solidified blank into a mould, pressing at normal temperature, heating and pressurizing, wherein the temperature of the mould is 140-160 ℃, the molding pressure of pressurization is 5-10 Mpa, then heating to 180-220 ℃, and then preserving heat for 1-2 hours to prepare a solidified material;
f. under the protection of nitrogen, the solidified material is sintered at 1400-1800 ℃ to obtain the carbon/ceramic material.
In the step c, the mixed intermediate material is mixed with the glue solution mixed with the disordered carbon fibers, and then kneaded for 4-10 hours by using a kneading machine or mechanically mixed for 4-10 hours.
And c, placing the mixed blank in a sealed state for 10-30 hours to enable the blank to be in a plastic state.
And f, putting the obtained carbon/ceramic material into phenolic resin liquid in an autoclave, and pressurizing to 1.5-2.0 Mpa so as to enable the phenolic resin to permeate into the carbon/ceramic material.
The carbon/ceramic material permeated by the phenolic resin is placed in a high-pressure sintering furnace, and the temperature is increased to 1500-2000 ℃ to prepare the carbon/ceramic material with higher density.
The invention discloses a formula and a proportion of a carbon/ceramic material fastener, and also discloses a preparation method of the carbon/ceramic material. The carbon/ceramic material has higher carbon components, so the carbon/ceramic material has the basic performance of the carbon/carbon material, and simultaneously contains more ceramic components, and the ceramic components generate high-melting-point intermetallic compounds such as MoSi, ZrC, MoZrSi and the like in the high-temperature sintering process to generate a multi-element effect, thereby improving the high-temperature mechanical property of the material and the oxidation resistance and the silicon vapor corrosion resistance of the material. The carbon/ceramic material can be prepared into various mechanical components, in particular fasteners or connecting pieces, and can be applied to ultra-high temperature (> 1500 ℃) vacuum furnaces or various high-temperature equipment. The carbon/ceramic material or the prepared fastener or connecting piece has very excellent high temperature resistance and mechanical property at high temperature, and simultaneously has good corrosion resistance, particularly oxidation resistance, and density far lower than that of metal (such as steel), so that the carbon/ceramic material can be applied to the field of aerospace.
The specific implementation mode is as follows:
the following detailed description will be given of specific embodiments of the present invention, and it should be noted that the specific embodiments of the present invention are to be understood as technical solutions of the present invention, and should not be construed as limiting the scope of the claims of the present invention.
The specific composition (in weight percent) of the first embodiment of the carbon/ceramic material of the invention is: 30-60% of disordered carbon fiber, 10-18% of carbon black, 10-20% of silicon powder, 8-16% of molybdenum powder, 6-12% of silicon carbide, 3-10% of zirconium oxide and 10-25% of glue solution; the above-mentioned components are mixed and then passed through the preparation method given in detail below, and can be fired into the required carbon/ceramic material, and after high-temp. firing, the above-mentioned carbon/ceramic material possesses higher carbon molecule and carbon fibre, so that it possesses the basic property of carbon/carbon (C/C) material, at the same time the above-mentioned material possesses more ceramic components, and the carbon/carbon (C/C) material formed from larger components and ceramic components are mixed and sintered, so that the above-mentioned carbon/ceramic material possesses excellent comprehensive properties, in which the disordered carbon fibre not only can make the carbon/ceramic material possess good isotropy, but also can make the carbon/ceramic material be conveniently die-pressed in the preparation process and possess later-stage mechanical processability.
In order to further improve the oxidation resistance and mechanical properties of the carbon/ceramic material, the specific composition (by weight percent) of the carbon/ceramic material of the second embodiment is as follows: 30-40% of disordered carbon fiber, 10-12% of carbon black, 17-20% of silicon powder, 10-12% of molybdenum powder, 10-12% of silicon carbide, 6-10% of zirconium oxide and 10-15% of glue solution; in the embodiment, the carbon/ceramic material has higher ceramic components, so that the oxidation resistance and the mechanical property of the carbon/ceramic material are further improved, and the stability of the mechanical property of the carbon/ceramic material at high temperature is improved, so that the carbon/ceramic material is more suitable for being used under the aerobic condition.
In order to further improve the high temperature resistance of the carbon/ceramic material, the specific composition (by weight percent) of the carbon/ceramic material of the third embodiment is as follows: 40-55% of disordered carbon fibers, 16-18% of carbon black, 10-12% of silicon powder, 8-12% of molybdenum powder, 6-8% of silicon carbide, 3-6% of zirconium oxide and 12-25% of glue solution; in the embodiment, the carbon fiber composite material has higher percentage of carbon materials and carbon fibers, so that the carbon fiber composite material has the performance of carbon/carbon materials, the brittleness of the material is further reduced, the toughness of the material is improved, and the high-temperature-resistant carbon fiber composite material is more stable against high temperature and high temperature.
The glue solution used in the carbon/ceramic material comprises the following components (by weight percent): 94-98% of phenolic resin (with the trade name of PF-5206, manufactured by Jinan Shengquanwis corporation), 0.1-2.0% of coupling agent (with the trade name of KH-792, manufactured by Tianjin flying materials corporation), 1.0-4.0% of ethyl cellulose (with the trade name of EC, manufactured by Luzhou northern chemical corporation); the glue solution formed by the components is soaked with the disordered carbon fiber and then mixed with the powdery components, the interface combination of the glue solution and the disordered carbon fiber can be ensured, the mixed mixture has good plasticity or moldability, and the uniform mixing of the glue solution and the powdery components also has great benefits on the formation of crystalline phases of carbon, ceramics and both in the carbon/ceramic material.
The disordered carbon fiber is one of short carbon fiber, waste long carbon fiber and messy carbon fiber or any combination thereof. The chopped carbon fibers are favorable for the isotropic performance of the carbon/ceramic material; the waste long carbon fiber is beneficial to improving the strength such as bending strength or tensile strength, and is particularly beneficial to the performance of the final large-size carbon/ceramic material such as a long-size fastening bolt (rod); the carbon fibre has the comprehensive performance of short and long carbon fibres, and can play a role of coupling and enhance the associativity of materials, and particularly, the waste long carbon fibre and the carbon fibre can be waste materials in the production process or the use process of the carbon fibre, so that the influence of the waste fibre on the environment is reduced, the utilization of the waste is improved, and the cost of the invention can be reduced.
The preparation method of the carbon/ceramic material comprises the following steps:
a. mixing carbon black, silicon powder, molybdenum powder, silicon carbide and zirconia to prepare a mixed intermediate material;
b. soaking the disordered carbon fibers in the glue solution for 12-24 hours;
c. mixing the mixed intermediate material and the glue solution mixed with the disordered carbon fibers to prepare a blank;
d. preserving the heat of the blank at 80-120 ℃ for 10-30 minutes to semi-cure the blank;
e. putting the prepared semi-solidified blank into a mould, pressing at normal temperature, heating and pressurizing, wherein the temperature of the mould is 140-160 ℃, the molding pressure of pressurization is 5-10 Mpa, then heating to 180-220 ℃, and then preserving heat for 1-2 hours to prepare a solidified material;
f. under the protection of nitrogen, the solidified material is sintered at 1400-1800 ℃ to obtain the carbon/ceramic material.
In the step a, the carbon black, the silicon powder, the molybdenum powder, the silicon carbide and the zirconium oxide are mixed to prepare a mixed intermediate material for later use, or the mixed intermediate material is put into a ball mill for mixed grinding for 2-4 hours to prepare a mixed intermediate material with uniform granularity and small granularity, so that the specific surface area of each component is increased, the mutual compactness and the mutual permeability of the mixed intermediate material are improved, and the reaction rate and the crystallinity of carbon and ceramic are improved in the sintering process; in the step b, the disordered carbon fibers are soaked in the glue solution for 12-24 hours, the carbon fibers have tiny pores due to the process from the aspect of microstructure, when the carbon fibers are soaked in the glue solution, molecules of the glue solution can enter the tiny pores on the surface and/or in the surface layer of the carbon fibers within a certain time, the entering needs a certain time, the glue solution entering the surface and/or the surface pores of the carbon fibers forms a transition layer after being sintered, the interface effect between the carbon fibers and the carbon/ceramic material structure is increased, and the mechanical strength of the carbon/ceramic material is improved; in the step c, the mixed intermediate material and the glue solution mixed with the disordered carbon fibers are mixed to prepare a blank, in order to further improve the mixing uniformity and enable the glue solution to better and fully permeate into the particle surface layers of the components, the blank is placed into a kneader to be kneaded for 4-10 hours, or the blank is placed into a mixing machine to be mixed for 4-10 hours, the mixed blank is placed in a sealed state for 10-30 hours, preferably 15-24 hours, so that the glue solution, the carbon fibers and the solid particles can fully permeate, wet, diffuse and fuse to enable the blank to be in a plastic state, in the later sintering stage, the combination of the components permeated with the glue solution on the crystallization of the carbon/ceramic material has great benefit, and the blank is prepared into a required plate-shaped blank or a blank in other shapes through a mold; in the step d, after the blank is subjected to heat preservation at the temperature of 80-120 ℃ for 10-30 minutes, semi-solidifying the blank to enable the semi-solidified blank to become a thixotropic blank with certain plasticity; in the step e, the prepared semi-solidified blank is placed in a mould to be pressed at normal temperature, then heated and pressed, the thixotropic blank is placed on a press to be pressed at normal temperature, so that the blank generates plastic deformation, volume contraction, density increase and heat conductivity improvement, the temperature of the blank is ensured to be consistent in the following hot pressing process, then raising the temperature, wherein the mold temperature is 140-160 ℃, the molding pressure of pressurization is 5-10 Mpa, the volatile matter in the blank can be discharged preliminarily, then the temperature is raised to 180-200 ℃ and then the temperature is preserved for 1-2 hours or the temperature is raised to 180-250 ℃ and then the temperature is preserved for 1-3 hours, then naturally cooling, the volatile matter can be basically discharged to solidify the blank to form a solidified material, because the semi-solidified blank has a certain size, volatile substances are discharged at a lower temperature, and chemical reaction can be triggered to enable semi-solidified blanks to become solidified materials while the volatile substances are continuously discharged at a higher temperature; in the step f, the solidified material is sintered at 1400-1800 ℃ under the protection of nitrogen to obtain the carbon/ceramic material, the sintering temperature in the step is higher than the sintering temperature of a common ceramic material, the sintering temperature depends on the components, the formula and the proportion of the carbon/ceramic material, in the sintering process, phenolic resin is carbonized into pyrolytic carbon to increase the total carbon content of the carbon/ceramic material, the sintered carbon/ceramic material has quite high ultrahigh temperature resistance and high strength and can be used as a connecting piece or a fastening piece, and the carbon/ceramic material has good oxidation resistance due to quite high ceramic components, so that the defect that the oxidation resistance of the carbon material or the carbon/ceramic material is not high is overcome.
Because the fine bubbles are difficult to avoid in the sintering process, and the density of the carbon/ceramic material is not optimal, the carbon/ceramic material obtained in the step f is placed into a phenolic resin liquid in an autoclave, and is pressurized to 1.5-2.0 Mpa, so that the phenolic resin permeates into the carbon/ceramic material, and under the pressure, the phenolic resin enters the fine bubbles in the carbon/ceramic material; the carbon/ceramic material permeated by the phenolic resin is placed in a high-pressure sintering furnace, the temperature is raised to 1500-2000 ℃ for sintering, the density of the carbon/ceramic material is further increased after the phenolic resin is carbonized, the high-density carbon/ceramic material has better high-temperature resistance and high mechanical properties such as bending strength and tensile strength, and the carbon/ceramic material can be processed by certain mechanical processing according to requirements to prepare a specific fastener or connecting piece or other structural members.
Compared with fasteners made of carbon/carbon (C/C) materials in the prior art, the carbon/ceramic material prepared by the invention has great advantages, such as saving raw material cost by about 70%, reducing production cycle by about four fifths, improving yield by 15%, reducing production cost by 75%, improving oxidation resistance by one time, improving service life, improving mechanical strength, improving processability due to uniformity of the carbon/ceramic material, producing fasteners of large size and the like.
Claims (9)
1. A heat-resistant high-strength carbon/ceramic fastener is characterized in that the carbon/ceramic fastener comprises the following components:
wherein the glue solution comprises the following components in percentage by weight:
94-98% of phenolic resin;
0.1-2.0% of a coupling agent;
1.0-4.0% of ethyl cellulose.
2. The heat resistant high strength carbon/ceramic fastener of claim 1 wherein the carbon/ceramic composition is:
3. the heat resistant high strength carbon/ceramic fastener of claim 1 wherein the carbon/ceramic composition is:
4. the heat resistant high strength carbon/ceramic fastener as claimed in claim 1, 2 or 3, wherein said random carbon fiber is one of chopped carbon fiber, waste long carbon fiber, and random carbon fiber or any combination thereof.
5. The method for preparing a heat-resistant high-strength carbon/ceramic fastener according to claim 1, 2, 3 or 4, comprising the steps of:
a. mixing carbon black, silicon powder, molybdenum powder, silicon carbide and zirconia to prepare a mixed intermediate material;
b. soaking the disordered carbon fibers in the glue solution for 12-24 hours;
c. mixing the mixed intermediate material and the glue solution mixed with the disordered carbon fibers to prepare a blank;
d. preserving the heat of the blank at 80-120 ℃ for 10-30 minutes to semi-cure the blank;
e. putting the prepared semi-solidified blank into a mould, pressing at normal temperature, heating and pressurizing, wherein the temperature of the mould is 140-160 ℃, the molding pressure of pressurization is 5-10 Mpa, then heating to 180-220 ℃, and then preserving heat for 1-2 hours to prepare a solidified material;
f. under the protection of nitrogen, the solidified material is sintered at 1400-1800 ℃ to obtain the carbon/ceramic material.
6. The method of claim 5, wherein the step c comprises mixing the mixed intermediate material with the glue solution containing the disordered carbon fibers, and kneading the mixture in a kneader for 4 to 10 hours or mechanically mixing the mixture for 4 to 10 hours.
7. The method for preparing a heat-resistant high-strength carbon/ceramic fastener as claimed in claim 6, wherein in the step c, the mixed blank is placed in a sealed state for 10-30 hours to make the blank in a plastic state.
8. The method for preparing a heat-resistant high-strength carbon/ceramic fastener as claimed in claim 5, 6 or 7, wherein after the step f, the obtained carbon/ceramic material is put into a phenolic resin solution in an autoclave and pressurized to 1.5 to 2.0Mpa, so that the phenolic resin permeates into the carbon/ceramic material.
9. The method of claim 8, wherein the carbon/ceramic material infiltrated with phenolic resin is placed in a high pressure sintering furnace and heated to 1500-2000 ℃ to produce a higher density carbon/ceramic material.
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| CN114790121B (en) * | 2022-05-12 | 2023-05-16 | 宁波金鼎紧固件有限公司 | Fastener of heat-resistant high-strength carbon/ceramic material and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251083A (en) * | 1997-03-21 | 2000-04-19 | 戴姆勒-克莱斯勒股份公司 | Fibre-reinforced composite ceramics and method of producing same |
| CN1744974A (en) * | 2002-12-03 | 2006-03-08 | 尤卡碳工业有限公司 | Carbon/carbon composites by hot pressing |
| CN101070395A (en) * | 2007-06-20 | 2007-11-14 | 中南大学 | Method for making braking shoe and piece of charcoal/charcoal-silicon carbonate composite material |
| CN103626512A (en) * | 2013-11-28 | 2014-03-12 | 哈尔滨工业大学 | Carbon/carbon fiber-silicon, boron, carbon and nitrogen ceramic composite material and preparation method thereof |
-
2016
- 2016-12-30 CN CN201611271035.4A patent/CN106830967B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251083A (en) * | 1997-03-21 | 2000-04-19 | 戴姆勒-克莱斯勒股份公司 | Fibre-reinforced composite ceramics and method of producing same |
| CN1744974A (en) * | 2002-12-03 | 2006-03-08 | 尤卡碳工业有限公司 | Carbon/carbon composites by hot pressing |
| CN101070395A (en) * | 2007-06-20 | 2007-11-14 | 中南大学 | Method for making braking shoe and piece of charcoal/charcoal-silicon carbonate composite material |
| CN103626512A (en) * | 2013-11-28 | 2014-03-12 | 哈尔滨工业大学 | Carbon/carbon fiber-silicon, boron, carbon and nitrogen ceramic composite material and preparation method thereof |
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