CN103030135B - Preparation method of antioxidant high-heat-conductivity foamy carbon material - Google Patents
Preparation method of antioxidant high-heat-conductivity foamy carbon material Download PDFInfo
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- CN103030135B CN103030135B CN201310002629.5A CN201310002629A CN103030135B CN 103030135 B CN103030135 B CN 103030135B CN 201310002629 A CN201310002629 A CN 201310002629A CN 103030135 B CN103030135 B CN 103030135B
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Abstract
The invention relates to a preparation method of an antioxidant high-heat-conductivity foamy carbon material, which belongs to the field of inorganic functional materials for heat management and is mainly applied to oxidation protection of foamy carbon. The preparation method comprises the following steps: with high-heat-conductivity foamy carbon as a framework, performing carbon coating treatment on a foam pore wall; and promoting reaction of the carbon coating and a silicon-containing active component to form a silicon carbide antioxidant coating. Compared with the pure foamy carbon material, the antioxidant high-heat-conductivity foamy carbon material prepared by the preparation method has the advantages as follows: the antioxidant performance at 800 DEG C is lower than or equal to 3*10-3 g/(s.cm<3>), the compressive strength is improved by more than twice, the volume heat conductivity is improved by more than 20%, and the aperture ratio is reduced by at most 20%.
Description
Technical field
The present invention relates to a kind of preparation method of anti-oxidant type high heat conducting foam carbon material, this invention belongs to heat management and uses inorganic functional material field, is mainly used in the oxidation protection of foamy carbon.
Background technology
High heat conducting foam carbon is the porous thermal management materials being prepared through technological processs such as foaming, carbonization, greyings by mesophase pitch, the open-celled structure that it is good and good heat-conductive characteristic make it have extraordinary Filled Dielectrics, pass through and exchange capability of heat, are the Novel hot management materials that using value is very high.High heat conducting foam carbon, because specific heat conductance is very high, is particularly suitable for applying in the heat management system in the fields such as space flight, space flight, boats and ships, and heat management system in some field need to be on active service in high temperature aerobic environment.Foamy carbon material, owing to being just very easy to oxidation in surpassing the well-oxygenated environment of 300 ℃, causes the consumption of material.High heat conducting foam carbon material is formed by connecting by very thin hole wall, and while being on active service in well-oxygenated environment, hole wall oxidation very easily occurs and causes thermal conduction path fracture, greatly reduces heat conductivility and the mechanical property of material.Therefore for the high heat conducting foam carbon material using in high temperature aerobic environment, it is carried out to antioxidation treatment and be very important.
The antioxidation treatment that document adopts for foamy carbon material mainly comprises matrix modification and two kinds of methods of face coat.For the former, mainly by add anti-oxidant constituent element in foamy carbon precursor, then form the foamy carbon material with anti-oxidant constituent element.This method is for heat insulation effective with foamy carbon material, and unfavorable for high heat conducting foam carbon material because anti-oxidant constituent element add the orientation that membership affects foamy carbon hole wall carbon-coating, thereby greatly reduce the thermal conductivity of foamy carbon, affect its heat conveyance performance.The top coat anti-oxidation method for foamy carbon material adopting in document has mainly adopted the slurry cladding process with anti-oxidant constituent element to prepare oxidation resistant coating on foamy carbon top layer, realizes the anti-oxidant of foamy carbon.The method can realize anti-oxidant for the foamy carbon with closed pores structure, and can not realize the completely anti-oxidant of material for the high heat conducting foam carbon material this method with high opening rate: oxidation resistant coating exists only in foamy carbon surface, and the oxygen in environment also can enter the oxidation that internal foam carbon is caused in inside by perforate.If slurry filling pore is formed to the continuous oxidation resistant coating in top layer, will lose Filled Dielectrics and the handling capacity of foamy carbon under arms time, thereby lose heat management function.If adopting slurry method fills, promote the foamy carbon in internal void to form coating, hole that will filled and process carbon, cause declining to a great extent of porosity and percentage of open area, and can in forming coating procedure, corrode foamy carbon hole wall, cause declining to a great extent of foamy carbon mechanical property and heat-conductive characteristic.Therefore the anti-oxidation treatment method that document provides all can not provide effective antioxidant defense for high heat conducting foam carbon.
The technology of the present invention method overcomes art methods deficiency, provides a kind of high heat conducting foam carbon of can effectively protecting not oxidized in high temperature aerobic environment, and the anti-oxidation method that significantly improves of the over-all properties of material.
Summary of the invention
The present invention is directed to that oxidation occurs high heat conducting foam carbon material in high temperature aerobic environment and the mechanics of materials strength degradation that causes and complement heat conduction performance reduce problem, overcome the deficiency of art methods, provide a kind of in the harmless method that forms oxidation resistant coating of foamy carbon hole wall, realize the military service of high heat conducting foam carbon material in high temperature aerobic environment.
Take high heat conducting foam carbon as skeleton, foam cell walls is carried out to the processing of carbon coating, then promote carbon coating and silicon-containing active component reaction to form silicon carbide oxidation resistant coating, concrete technical scheme is as follows:
1) cleaning of high heat conducting foam carbon: high heat conducting foam carbon material is carried out to clean, and the impurity in scumming carbon surface and hole, opens pore channel;
2) high heat conducting foam carbon hole wall carbon coating: can adopt chemical vapor infiltration method, also can adopt vacuum impregnation carbon source precursor (resin, pitch)/carbonizing treatment method to form carbon-coating at foamy carbon hole wall, then thermal treatment >=0.1h at >=1500 ℃, forming thickness is the carbon coating of 0.5 μ m～100 μ m;
Can repeating step 2 in order to form continuous carbon coating);
3) silicon carbide oxidation resistant coating preparation: reaction mass is placed in to crucible bottom, in the middle part of crucible, place step 2) the high heat conducting foam carbon that obtains, high heat conducting foam carbon does not contact with reaction mass, then crucible is placed in to high-temperature vacuum furnace is warming up to reaction mass and can forms the temperature containing silicon vapor, insulation, makes by foamy carbon hole and with the carbon coating on hole wall, to react formation silicon carbide containing silicon vapor;
Described reaction mass can produce containing silicon vapor, and reaction mass is a kind of or its mixture in elemental silicon, silicon-dioxide, silane, silane derivative;
The temperature of high-temperature vacuum furnace is relevant with the raw-material character that can form siliceous source of the gas with soaking time, but temperature should be within the scope of 1200 ℃～2000 ℃, with guarantee to form containing silicon vapor can with foamy carbon hole wall on the reaction of carbon coating form silicon carbide, but can transient response do not cause the corrosion of foamy carbon skeleton; That the selection of soaking time need to guarantee to form is continuous, have certain thickness coat of silicon carbide, and the soaking time of optimization is 0.1h～10h.In formation coating procedure, high-temperature vacuum furnace vacuumizes continuously or remains under certain vacuum tightness and carries out, further to promote containing the formation of silicon vapor with containing the circulation of silicon vapor in foamy carbon hole.
In order further to improve the antioxidant effect of oxidation resistant coating, can continue other coatings of preparation or seal glaze and process on the coat of silicon carbide surface obtaining.
Beneficial effect
The anti-oxidant type high heat conducting foam carbon material that method of the present invention obtains is compared with pure foam carbon material, 800 ℃ of antioxidant property≤3 * 10
-3g/ (s.cm
3), ultimate compression strength improves more than 2 times, and bulk thermal conductivity improves more than 20%, and percentage of open area declines and is no more than 20%.
Accompanying drawing explanation
Fig. 1 has provided vapor phase process and has prepared silicon carbide oxidation resistant coating schematic diagram.In figure, 1 for forming the reaction mass of the siliceous steam of gas phase; 2 is the siliceous steam forming in coating preparation process; 3 for having passed through the high heat conducting foam carbon material that carbon coating is processed; 4 is the crucible body of splendid attire reaction system; 5 is crucible cover.
Embodiment
As shown in Figure 1, Fig. 1 is the schematic diagram that vapor phase process is prepared silicon carbide oxidation resistant coating, wherein, at the bottom of crucible placing response material 1, in the middle part of crucible, place high heat conducting foam material 3, between reaction mass 1 and high heat conducting foam material 3, for reaction mass, produce containing silicon vapor 2, the crucible body 4 of crucible and crucible cover 5 are by a seal cavity of crucible formation, on crucible cover 5, there is hole, the gas in crucible can be discharged.
Embodiment 1
1) adopting volume density is 0.30g/cm
3, percentage of open area is 92%, thermal conductivity is that the foamy carbon that 42W/ (m K), ultimate compression strength are 0.3MPa is enhancing object.Adopt ultrasonic cleaning process high opening rate foamy carbon to be carried out to clean, the chip in scumming carbon hole;
2) adopt chemical vapor infiltration to prepare carbon coating, detailed process is as follows: carbon source is that propane, temperature are 1000 ℃, and depositing time is 50 hours, and the volume density of the coating foamy carbon material of acquisition is 0.40g/cm
3; By this material pyroprocessing 1h at 1800 ℃, obtain the high heat conducting foam carbon material of carbon coating, its volume density is 0.39 g/cm
3.
3) usining the mixed powder (volume ratio is 1:1) of silicon and silicon-dioxide, as silicon source, is placed on crucible bottom, then the foamy carbon of carbon coating is placed in to crucible bottom, after cover lid, is placed in high-temperature vacuum furnace.First High Temperature Furnaces Heating Apparatus is vacuumized, to gauge pressure, stop vacuumizing after lower than 0.1atm, be then filled with rare gas element (argon gas) and keep flowing of rare gas element to normal pressure.High Temperature Furnaces Heating Apparatus is heated to 1600 ℃, and naturally cooling after constant temperature 1.5h, obtains the anti-oxidant type high heat conducting foam carbon material with coat of silicon carbide.
After tested, the volume density of anti-oxidant type high heat conducting foam carbon material is 0.5 g/cm
3, thermal conductivity is 55 W/ (m K), and ultimate compression strength is 1.8MPa, and 800 ℃ of antioxidant properties are 2.2 * 10
-3g/ (s.cm
3), percentage of open area is 85%.
Embodiment 2
1) adopting volume density is 0.50g/cm
3, percentage of open area is 85%, thermal conductivity is that the foamy carbon that 80W/ (m K), ultimate compression strength are 1.2MPa is enhancing object.Adopt ultrasonic cleaning process high opening rate foamy carbon to be carried out to clean, the chip in scumming carbon hole;
2) adopt chemical vapor infiltration to prepare carbon coating, detailed process is as follows: carbon source is that propane, temperature are 1000 ℃, and depositing time is 50 hours, and the volume density of the coating foamy carbon material of acquisition is 0.62g/cm
3; By this material pyroprocessing 1h at 1800 ℃, obtain the high heat conducting foam carbon material of carbon coating, its volume density is 0.60 g/cm
3.
3) using silica flour as silicon source, be placed on crucible bottom, then the foamy carbon of carbon coating is placed in to crucible bottom, after cover lid, be placed in high-temperature vacuum furnace.First High Temperature Furnaces Heating Apparatus is vacuumized, to gauge pressure, stop vacuumizing after lower than 0.1atm, be then filled with rare gas element (argon gas) and keep vacuum state to 0.6atm.High Temperature Furnaces Heating Apparatus is heated to 1700 ℃, and naturally cooling after constant temperature 1h, obtains the anti-oxidant type high heat conducting foam carbon material with coat of silicon carbide.Then the silicon sol of take carries out vacuum impregnation packing as packing agent to the coat of silicon carbide forming, and forms the anti-oxidant type high heat conducting foam carbon material of silicon-dioxide packing coat of silicon carbide.
After tested, the volume density of the anti-oxidant type high heat conducting foam carbon material of silicon-dioxide packing is 0.75 g/cm
3, thermal conductivity is 100 W/ (m K), and ultimate compression strength is 5.2MPa, and 800 ℃ of antioxidant property antioxidant properties are 0.8 * 10
-3g/ (s.cm
3), percentage of open area is 76%.
Embodiment 3
1) adopting volume density is 0.50g/cm
3, percentage of open area is 85%, thermal conductivity is that the foamy carbon that 80W/ (m K), ultimate compression strength are 1.2MPa is enhancing object.Adopt ultrasonic cleaning process high opening rate foamy carbon to be carried out to clean, the chip in scumming carbon hole;
2) adopting mid-temperature pitch is that precursor adopts vacuum impregnation/carborization to prepare carbon coating, detailed process is as follows: the medium temperature coal pitch that the softening temperature of take is 78 ℃ is precursor, (foamy carbon is suppressed with graphite cake pitch to be injected to the container of splendid attire foamy carbon when 120 ℃ of molten states, prevent that it is floating in pitch), after liquid level is higher than the enough height in foamy carbon surface, this system is carried out to heating, vacuum dipping, vacuum tightness is 0.1atm, and the hold-time is 3h.After vacuum impregnation completes, foamy carbon is taken out, then carry out unsettled heating (120 ℃), the unnecessary pitch melting in hole is flowed out.Again foamy carbon is heated to 3h in the loft drier of 150 ℃, afterwards in carbide furnace at 1000 ℃ thermal treatment 1h, then take out in High Temperature Furnaces Heating Apparatus pyroprocessing 1h at 1800 ℃, obtain the high heat conducting foam carbon material of carbon coating, its volume density is 0.54 g/cm
3.The high heat conducting foam carbon material that repeats to obtain after a said process carbon coating, volume density is 0.58 g/cm
3.
3) usining Polycarbosilane, silica flour and silicon-dioxide compound (weight ratio is 1:2:2), as silicon source, is placed on crucible bottom, then the foamy carbon of carbon coating is placed in to crucible bottom, after cover lid, is placed in high-temperature vacuum furnace.First High Temperature Furnaces Heating Apparatus is vacuumized, to gauge pressure, stop vacuumizing after lower than 0.1atm, be then filled with rare gas element (argon gas) and keep vacuum state to 0.6atm.High Temperature Furnaces Heating Apparatus is first heated to 1000 ℃, 1 hour post-heating to 1600 ℃ of constant temperature, naturally cooling after constant temperature 1h, obtains the anti-oxidant type high heat conducting foam carbon material with coat of silicon carbide.Then the silicon sol of take carries out vacuum impregnation packing as packing agent to the coat of silicon carbide forming, and forms the anti-oxidant type high heat conducting foam carbon material of silicon-dioxide packing coat of silicon carbide.
After tested, the volume density of the anti-oxidant type high heat conducting foam carbon material of silicon-dioxide packing is 0.71 g/cm
3, thermal conductivity is 97 W/ (m K), and ultimate compression strength is 3.8MPa, and 800 ℃ of antioxidant property antioxidant properties are 1.5 * 10
-3g/ (s.cm
3), percentage of open area is 78%.
Claims (4)
1. a preparation method for anti-oxidant type high heat conducting foam carbon material, is characterized in that step comprises:
1) cleaning of high heat conducting foam carbon: high heat conducting foam carbon material is carried out to clean;
2) high heat conducting foam carbon hole wall carbon coating: adopt vacuum impregnation carbon source presoma/carbonizing treatment method to form carbon-coating at foamy carbon hole wall, thermal treatment >=0.1h at >=1500 ℃ then, forming thickness is the carbon coating of 0.5 μ m～100 μ m;
3) silicon carbide oxidation resistant coating preparation: reaction mass is placed in to crucible bottom, in the middle part of crucible, place step 2) the high heat conducting foam carbon that obtains, high heat conducting foam carbon does not contact with reaction mass, then crucible is placed in to high-temperature vacuum furnace is warming up to reaction mass and can forms the temperature containing silicon vapor, insulation, make by foamy carbon hole and with the carbon coating on hole wall, to react formation silicon carbide containing silicon vapor, obtain anti-oxidant type high heat conducting foam carbon material;
Described reaction mass can produce containing silicon vapor; Described presoma is resin or pitch.
2. a preparation method for anti-oxidant type high heat conducting foam carbon material, is characterized in that step is:
1) cleaning of high heat conducting foam carbon: high heat conducting foam carbon material is carried out to clean;
2) high heat conducting foam carbon hole wall carbon coating: adopt chemical vapor infiltration method to form carbon-coating at foamy carbon hole wall, thermal treatment >=0.1h at >=1500 ℃ then, forming thickness is the carbon coating of 0.5 μ m～100 μ m;
3) silicon carbide oxidation resistant coating preparation: reaction mass is placed in to crucible bottom, in the middle part of crucible, place step 2) the high heat conducting foam carbon that obtains, high heat conducting foam carbon does not contact with reaction mass, then crucible is placed in to high-temperature vacuum furnace is warming up to reaction mass and can forms the temperature containing silicon vapor, insulation, make by foamy carbon hole and with the carbon coating on hole wall, to react formation silicon carbide containing silicon vapor, obtain anti-oxidant type high heat conducting foam carbon material;
Described reaction mass can produce containing silicon vapor.
3. the preparation method of a kind of anti-oxidant type high heat conducting foam carbon material according to claim 1, is characterized in that: step 3) in reaction mass be a kind of or its mixture in elemental silicon, silicon-dioxide, silane, silane derivative.
4. the preparation method of a kind of anti-oxidant type high heat conducting foam carbon material according to claim 1, is characterized in that: on the coat of silicon carbide surface obtaining, continue other coatings of preparation or seal glaze and process.
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| CN104250107B (en) * | 2013-06-28 | 2017-12-08 | 中国地质大学（北京） | A kind of Carbon foam surface in situ synthesizes Si3N4The method of coating |
| CN104651789A (en) * | 2014-05-20 | 2015-05-27 | 鞠云 | Preparation process of novel C/Si film |
| CN107504325A (en) * | 2017-07-29 | 2017-12-22 | 南京航空航天大学 | A kind of preparation method of high temperature VIP composites |
| CN114249314B (en) * | 2020-09-23 | 2023-10-10 | 中国科学院金属研究所 | High-porosity three-dimensional communication structure foam carbon and preparation method thereof |
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| CN1275850C (en) * | 2003-11-25 | 2006-09-20 | 复旦大学 | Preparation method of carbon material with highly ordered nanometer hole of graphite hole wall structure |
| CN101104893A (en) * | 2006-07-14 | 2008-01-16 | 中国科学院金属研究所 | Metal/carbonyl composite foaming material and preparation method thereof |
| CN101224988A (en) * | 2008-01-29 | 2008-07-23 | 中国人民解放军国防科学技术大学 | Low-temperature preparation method of C/SiC ceramic matrix composite material |
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Patent Citations (5)
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| CN1275850C (en) * | 2003-11-25 | 2006-09-20 | 复旦大学 | Preparation method of carbon material with highly ordered nanometer hole of graphite hole wall structure |
| CN101104893A (en) * | 2006-07-14 | 2008-01-16 | 中国科学院金属研究所 | Metal/carbonyl composite foaming material and preparation method thereof |
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