CN103159496A - Method for preparing carbon/carbon composite material - Google Patents
Method for preparing carbon/carbon composite material Download PDFInfo
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- CN103159496A CN103159496A CN2013100952486A CN201310095248A CN103159496A CN 103159496 A CN103159496 A CN 103159496A CN 2013100952486 A CN2013100952486 A CN 2013100952486A CN 201310095248 A CN201310095248 A CN 201310095248A CN 103159496 A CN103159496 A CN 103159496A
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- carbon
- composite material
- carbon composite
- carbon cloth
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Abstract
The invention provides a method for preparing a carbon/carbon composite material. An electrochemical plating method is adopted to support a nickel catalyst on a carbon fiber cloth, so that the small granularity and distribution uniformity of the catalyst are ensured, and the usage of raw materials is reduced; and when the carbon/carbon composite material is prepared by adopting a chemical vapor deposition method, the nickel catalyst is adopted to accelerate an aromatization process of a source gas, so that the conversion rate of the source gas is increased, a deposition process is accelerated, the preparation period of the carbon/carbon composite material is shortened, and the preparation cost of the carbon/carbon composite material is lowered. The method comprises the following steps of: by utilizing a nickel sheet as an anode and a carbon cloth as a cathode, plating nickel on carbon fibers; drying, laminating and puncturing the carbon fibers to form a prefabricate body; and putting the prefabricate body in a chemical vapor deposition furnace, and preparing the carbon/carbon composite material by utilizing a narrow slit deposition method. The nickel catalyst is adopted to accelerate the aromatization process of the source gas, so that the conversion rate of the source gas is increased, pyrolytic carbon can be obtained through quick deposition, the preparation period of the carbon/carbon composite material is shortened, thus the preparation cost of the carbon/carbon composite material is lowered.
Description
Technical field
The invention belongs to relate to a kind of chemical materials the preparation method, be specifically related to a kind of preparation method of carbon/carbon composite.
Background technology
Carbon/carbon composite is present unique high-temperature structural material that can be used for more than 1650 ℃, performance with many excellences, raise and rising etc. have broad application prospects at aerospace, military affairs, medical science and many civil areas as high specific strength, high ratio modulus, high-fracture toughness, low density and intensity temperature.But the problems such as carbon/carbon composite complex manufacturing technology, preparation cycle length, starting material low conversion rate and densification are inhomogeneous cause its production cost high, have seriously restricted the further application and development of this material.Catalyzer is the material of energy accelerated reaction process.According to the formation mechanism of RESEARCH OF PYROCARBON, select the aromatization process of suitable catalyzer acceleration source gas, transformation efficiency and the fast deposition that can improve source gas obtain matrix carbon, thereby shorten the preparation cycle of carbon/carbon composite, reduce production costs.At present, the investigator to have developed multiple Ni catalyst based in order to solve the problem that exists in the carbon/carbon composite preparation process.But catalyzer exists the larger retardance gas channel of particle, skewness and solution to waste the problems such as serious.
Document 1 " nickel catalytic Preparation of Carbon/Carbon Composites, Shi Xiaohong, Li Hejun, Wang Yinwei, Li Kezhi.Carbon technique, 2004(03) " a kind of method of catalytic Preparation of Carbon/Carbon Composites is disclosed, the method by be immersed in load liquid phase Ni salt on precast body after heat reduction obtain Ni simple substance, improved the sedimentation rate of RESEARCH OF PYROCARBON.But the liquid impregnation method that this research is adopted waste is larger, and the heap(ed) capacity of catalyzer should not be controlled, and needs the nickel oxide that obtains after heat treated is used H again
2Just can obtain nickel simple substance with Ar reduction, complex process and have potential safety hazard.
Document 2 " research of nickel catalytic Preparation of Carbon/Carbon Composites, Zhou Zhenzhong, Li Tiehu, Li Caixia, Song Faju.The material Leader, 2007(09) " disclose a kind of method of catalytic Preparation of Carbon/Carbon Composites, the method has adopted Ni/SiO
2, Ni/Al2O
3, the Ni/ZSM-5 loaded catalyst, improved the sedimentation rate of RESEARCH OF PYROCARBON.But the catalyzer that adopts due to this research is pulverous, can not guarantee the homogeneity in the spreading process, and granules of catalyst is larger, easily blocks gas channel.Therefore, can not guarantee the homogeneity of densification.
Summary of the invention
The technical problem that solves
The problems such as for fear of the deficiencies in the prior art part, the present invention proposes a kind of preparation method of carbon/carbon composite, exists in prior art to overcome, and granules of catalyst larger retardance gas channel, skewness and solution waste are serious.
Technical scheme
A kind of preparation method of carbon/carbon composite is characterized in that step is as follows:
Step 1, respectively carbon cloth and nickel plate are carried out surface treatment, detailed process is:
The carbon cloth of making is soaked 30min～1h carry out surface degreasing in dehydrated alcohol, put into the baking oven dry for standby after distilled water flushing;
B. with nickel plate supersound process 10min in dehydrated alcohol, the distilled water flushing post-drying is standby;
Step 2: take the nickel plate as anode, carbon cloth is negative electrode, carries out nickel plating on carbon cloth; Described electroplate liquid is: every preparation 1L electroplate liquid takes the NiSO of 100～350g
46H
2The NiCl of O, 30～80g
26H
2The H of O, 15～40g
3BO
3MgSO with 20～25g
4Be dissolved in and make the 1L electroplate liquid in distilled water;
Step 3, preparation precast body, detailed process is:
A. after plating is completed, the carbon cloth that takes off is placed in baking oven with distilled water flushing, is incubated 1～10 hour post-drying under 70～120 ℃;
B. with the carbon cloth of oven dry with 5～10 layers of laying, utilize carbon fiber line puncture wherein, make precast body;
Step 4, chemical Vapor deposition process prepare RESEARCH OF PYROCARBON, and detailed process is:
A. the mould of precast body being packed into is placed in chemical vapor deposition stove, vacuumize make vacuum tightness reach-0.1～-0.01Mpa, pass into argon gas and again vacuumize to normal pressure, repeat this process 3 times;
B. be warming up to 500～1100 ℃ under argon shield, heat-up rate is controlled at 5～10 ℃/min;
C. pass into methane or propylene gas deposition RESEARCH OF PYROCARBON under argon shield, insulation is until the density of precast body reaches 1.0～2.5g/cm under 500～1100 ℃
3
D. turn off that the speed with 5～20 ℃/min is cooled to 300～200 ℃ after methane or propylene gas valve, after turning off power supply and naturally being down to room temperature, sample is taken out in blow-on, obtains carbon/carbon composite.
Beneficial effect
The preparation method of a kind of carbon/carbon composite that the present invention proposes, electronickelling simple substance catalytic Preparation of Carbon/Carbon Composites on carbon cloth.Electrochemical plating add that nickel-loaded catalyst easily operates, coating is evenly distributed and plating solution can repeatedly utilize, and can reduce production costs.At present, have example at graphite flake and carbon fiber electrically nickel plating and catalysis Formed nanotube.Therefore, electronickelling as catalyzer, under suitable process conditions, can obtain to have the carbon/carbon composite of desired density on the precast body of carbon.
The present invention is a kind of method that catalytic deposition prepares carbon/carbon composite.Utilize electrochemical plating to add nickel-loaded catalyst on carbon cloth, guaranteed small grain size and the distributing homogeneity of catalyzer, reduced raw-material consumption; When adopting chemical vapor deposition method for preparing carbon/carbon/carbon composite, aromatization process by nickel catalyzator acceleration source gas, the transformation efficiency of raising source gas also accelerates deposition process, shortens the fabrication cycle of carbon/carbon composite, reduces the preparation cost of carbon/carbon composite.
Embodiment
Now the invention will be further described in conjunction with the embodiments:
Embodiment 1:
The present embodiment is a kind of quick method for preparing carbon/carbon composite, comprises two master operations of loading catalyst and chemical vapour deposition, and its detailed process is:
Step 1, the carbon cloth that will make soak 40min and carry out surface degreasing in dehydrated alcohol, put into the baking oven dry for standby after distilled water flushing; With nickel plate supersound process 10min in dehydrated alcohol, the distilled water flushing post-drying is standby.
Step 2, take 200gNiSO respectively
46H
2O, 60gNiCl
26H
2O, 30gH
3BO
3And 15gMgSO
4Be dissolved in and make the 1L electroplate liquid in appropriate distilled water; Junction circuit is take the nickel plate as anode, carbon cloth is negative electrode, opens power supply, regulates electric current to 40mA, nickel plating 20min on carbon cloth.
Step 3, plating are placed on appropriate distilled water flushing the carbon cloth that takes off in baking oven after completing, 80 ℃ of insulations oven dry in 2 hours; With 5 layers of laying of carbon cloth of oven dry, utilize the carbon fiber line puncture wherein, make precast body.
Step 4, the precast body mould of packing into is placed in chemical vapor deposition stove, vacuumizes vacuum tightness is reached-0.09Mpa, pass into argon gas and again vacuumize to normal pressure, repeat this process 3 times; Be warming up to 700 ℃ under argon shield, heat-up rate is controlled at 5 ℃/min; Pass into methane or propylene gas deposition RESEARCH OF PYROCARBON under argon shield, insulation for some time is until the density of precast body reaches 1.5g/cm under 700 ℃
3, turn off that the speed with 10 ℃/min is cooled to 200 ℃ after the propylene valve, after turning off power supply and naturally being down to room temperature, sample is taken out in blow-on.
Through above-mentioned institute in steps, prepared the carbon/carbon composite sample.The manufacture craft of this method is relatively simple, preparation cycle is shorter, the starting material transformation efficiency is high and densification is relatively even.
Embodiment 2:
The present embodiment is a kind of quick method for preparing carbon/carbon composite, comprises two master operations of loading catalyst and chemical vapour deposition, and its detailed process is:
Step 1, the carbon cloth that will make soak 40min and carry out surface degreasing in dehydrated alcohol, put into the baking oven dry for standby after distilled water flushing; With nickel plate supersound process 10min in dehydrated alcohol, the distilled water flushing post-drying is standby.
Step 2, take 250gNiSO respectively
46H
2O, 60gNiCl
26H
2O, 30gH
3BO
3And 20gMgSO
4Be dissolved in and make the 1L electroplate liquid in appropriate distilled water; Junction circuit is take the nickel plate as anode, carbon cloth is negative electrode, opens power supply, regulates electric current to 100mA, nickel plating 15min on carbon cloth.
Step 3, plating are placed on appropriate distilled water flushing the carbon cloth that takes off in baking oven after completing, 80 ℃ of insulations oven dry in 2 hours; With 5 layers of laying of carbon cloth of oven dry, utilize the carbon fiber line puncture wherein, make precast body.
Step 4, the precast body mould of packing into is placed in chemical vapor deposition stove, vacuumizes vacuum tightness is reached-0.09Mpa, pass into argon gas and again vacuumize to normal pressure, repeat this process 3 times; Be warming up to 900 ℃ under argon shield, heat-up rate is controlled at 5 ℃/min; Pass into methane or propylene gas deposition RESEARCH OF PYROCARBON under argon shield, insulation for some time is until the density of precast body reaches 1.5g/cm under 900 ℃
3, turn off that the speed with 10 ℃/min is cooled to 200 ℃ after the propylene valve, after turning off power supply and naturally being down to room temperature, sample is taken out in blow-on.
Through above-mentioned institute in steps, prepared the carbon/carbon composite sample.The manufacture craft of this method is relatively simple, preparation cycle is shorter, the starting material transformation efficiency is high and densification is relatively even.
Embodiment 3:
The present embodiment is a kind of quick method for preparing carbon/carbon composite, comprises two master operations of loading catalyst and chemical vapour deposition, and its detailed process is:
Step 1, the carbon cloth that will make soak 40min and carry out surface degreasing in dehydrated alcohol, put into the baking oven dry for standby after distilled water flushing; With nickel plate supersound process 10min in dehydrated alcohol, the distilled water flushing post-drying is standby.
Step 2, take 200gNiSO respectively
46H
2O, 60gNiCl
26H
2O, 30gH
3BO
3And 30gMgSO
4Be dissolved in and make the 1L electroplate liquid in appropriate distilled water; Junction circuit is take the nickel plate as anode, carbon cloth is negative electrode, opens power supply, regulates electric current to 200mA, nickel plating 6min on carbon cloth.
Step 3, plating are placed on appropriate distilled water flushing the carbon cloth that takes off in baking oven after completing, 80 ℃ of insulations oven dry in 2 hours; With 5 layers of laying of carbon cloth of oven dry, utilize the carbon fiber line puncture wherein, make precast body.
Step 4, the precast body mould of packing into is placed in chemical vapor deposition stove, vacuumizes vacuum tightness is reached-0.09Mpa, pass into argon gas and again vacuumize to normal pressure, repeat this process 3 times; Be warming up to 1000 ℃ under argon shield, heat-up rate is controlled at 8 ℃/min; Pass into methane or propylene gas deposition RESEARCH OF PYROCARBON under argon shield, insulation for some time is until the density of precast body reaches 1.5g/cm under 1000 ℃
3, turn off that the speed with 15 ℃/min is cooled to 200 ℃ after the propylene valve, after turning off power supply and naturally being down to room temperature, sample is taken out in blow-on.
Through above-mentioned institute in steps, prepared the carbon/carbon composite sample.The manufacture craft of this method is relatively simple, preparation cycle is shorter, the starting material transformation efficiency is high and densification is relatively even.
Embodiment 4:
The present embodiment is a kind of quick method for preparing carbon/carbon composite, comprises two master operations of loading catalyst and chemical vapour deposition, and its detailed process is:
Step 1, the carbon cloth that will make soak 40min and carry out surface degreasing in dehydrated alcohol, put into the baking oven dry for standby after distilled water flushing; With nickel plate supersound process 10min in dehydrated alcohol, the distilled water flushing post-drying is standby.
Step 2, take 200gNiSO respectively
46H
2O, 60gNiCl
26H
2O, 30gH
3BO
3And 20gMgSO
4Be dissolved in and make the 1L electroplate liquid in appropriate distilled water; Junction circuit is take the nickel plate as anode, carbon cloth is negative electrode, opens power supply, regulates electric current to 200mA, nickel plating 8min on carbon cloth.
Step 3, plating are placed on appropriate distilled water flushing the carbon cloth that takes off in baking oven after completing, 80 ℃ of insulations oven dry in 2 hours; With 5 layers of laying of carbon cloth of oven dry, utilize the carbon fiber line puncture wherein, make precast body.
Step 4, the precast body mould of packing into is placed in chemical vapor deposition stove, vacuumizes vacuum tightness is reached-0.09Mpa, pass into argon gas and again vacuumize to normal pressure, repeat this process 3 times; Be warming up to 1000 ℃ under argon shield, heat-up rate is controlled at 10 ℃/min; Pass into methane or propylene gas deposition RESEARCH OF PYROCARBON under argon shield, insulation for some time is until the density of precast body reaches 1.8g/cm under 1000 ℃
3, turn off that the speed with 18 ℃/min is cooled to 200 ℃ after the propylene valve, after turning off power supply and naturally being down to room temperature, sample is taken out in blow-on.
Through above-mentioned institute in steps, prepared the carbon/carbon composite sample.The manufacture craft of this method is relatively simple, preparation cycle is shorter, the starting material transformation efficiency is high and densification is relatively even.
Claims (1)
1. the preparation method of a carbon/carbon composite is characterized in that step is as follows:
Step 1, respectively carbon cloth and nickel plate are carried out surface treatment, detailed process is:
The carbon cloth of making is soaked 30min～1h carry out surface degreasing in dehydrated alcohol, put into the baking oven dry for standby after distilled water flushing;
B. with nickel plate supersound process 10min in dehydrated alcohol, the distilled water flushing post-drying is standby;
Step 2: take the nickel plate as anode, carbon cloth is negative electrode, carries out nickel plating on carbon cloth; Described electroplate liquid is: every preparation 1L electroplate liquid takes the NiSO of 100～350g
46H
2The NiCl of O, 30～80g
26H
2The H of O, 15～40g
3BO
3MgSO with 20～25g
4Be dissolved in and make the 1L electroplate liquid in distilled water;
Step 3: the preparation precast body, detailed process is:
A. after plating is completed, the carbon cloth that takes off is placed in baking oven with distilled water flushing, is incubated 1～10 hour post-drying under 70～120 ℃;
B. with the carbon cloth of oven dry with 5～10 layers of laying, utilize carbon fiber line puncture wherein, make precast body;
Step 4, chemical Vapor deposition process prepare RESEARCH OF PYROCARBON, and detailed process is:
A. the mould of precast body being packed into is placed in chemical vapor deposition stove, vacuumize make vacuum tightness reach-0.1～-0.01Mpa, pass into argon gas and again vacuumize to normal pressure, repeat this process 3 times;
B. be warming up to 500～1100 ℃ under argon shield, heat-up rate is controlled at 5～10 ℃/min;
C. pass into methane or propylene gas deposition RESEARCH OF PYROCARBON under argon shield, insulation is until the density of precast body reaches 1.0～2.5g/cm under 500～1100 ℃
3
D. turn off that the speed with 5～20 ℃/min is cooled to 300～200 ℃ after methane or propylene gas valve, after turning off power supply and naturally being down to room temperature, sample is taken out in blow-on, obtains carbon/carbon composite.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038110A (en) * | 2015-07-06 | 2015-11-11 | 陕西科技大学 | Electrochemically modified carbon cloth reinforced friction material and preparation method thereof |
| CN114232329A (en) * | 2021-10-25 | 2022-03-25 | 西安航空学院 | B4Preparation method of C @ CNT nanowire composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077773A (en) * | 2007-06-15 | 2007-11-28 | 清华大学 | Method for preparing carbon nano-tube array on the basis of chemical vapour deposition |
| CN101659564A (en) * | 2009-09-22 | 2010-03-03 | 西北工业大学 | Method for generating carbon matrix of carbon/carbon composite materials with catalysis |
| CN101659563A (en) * | 2009-09-22 | 2010-03-03 | 西北工业大学 | Preparation method of carbon/carbon complex material dually enhanced by carbon whisker and carbon fiber |
| CN102276281A (en) * | 2011-05-19 | 2011-12-14 | 中南大学 | Method for preparing nano-SiC fiber reinforced carbon-carbon composite material |
-
2013
- 2013-03-22 CN CN2013100952486A patent/CN103159496A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077773A (en) * | 2007-06-15 | 2007-11-28 | 清华大学 | Method for preparing carbon nano-tube array on the basis of chemical vapour deposition |
| CN101659564A (en) * | 2009-09-22 | 2010-03-03 | 西北工业大学 | Method for generating carbon matrix of carbon/carbon composite materials with catalysis |
| CN101659563A (en) * | 2009-09-22 | 2010-03-03 | 西北工业大学 | Preparation method of carbon/carbon complex material dually enhanced by carbon whisker and carbon fiber |
| CN102276281A (en) * | 2011-05-19 | 2011-12-14 | 中南大学 | Method for preparing nano-SiC fiber reinforced carbon-carbon composite material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038110A (en) * | 2015-07-06 | 2015-11-11 | 陕西科技大学 | Electrochemically modified carbon cloth reinforced friction material and preparation method thereof |
| CN114232329A (en) * | 2021-10-25 | 2022-03-25 | 西安航空学院 | B4Preparation method of C @ CNT nanowire composite material |
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Application publication date: 20130619 |