CN101049928A - Method for manufacturing high heat conducting foam material of graphite with even apertures - Google Patents
Method for manufacturing high heat conducting foam material of graphite with even apertures Download PDFInfo
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- CN101049928A CN101049928A CN 200610066994 CN200610066994A CN101049928A CN 101049928 A CN101049928 A CN 101049928A CN 200610066994 CN200610066994 CN 200610066994 CN 200610066994 A CN200610066994 A CN 200610066994A CN 101049928 A CN101049928 A CN 101049928A
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- graphite
- foam material
- high heat
- heat conducting
- pitch
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000010439 graphite Substances 0.000 title claims abstract description 44
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 44
- 239000006261 foam material Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title abstract description 18
- 238000004519 manufacturing process Methods 0.000 title description 7
- 239000011302 mesophase pitch Substances 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006260 foam Substances 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000010792 warming Methods 0.000 claims description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000010426 asphalt Substances 0.000 claims description 20
- 239000013543 active substance Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 239000011280 coal tar Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011301 petroleum pitch Substances 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 3
- 239000011294 coal tar pitch Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 3
- 238000013022 venting Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 8
- 239000011295 pitch Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract 6
- 239000011336 carbonized pitch Substances 0.000 abstract 2
- 239000003463 adsorbent Substances 0.000 abstract 1
- 238000010000 carbonizing Methods 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000011800 void material Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- HVUMOYIDDBPOLL-UHFFFAOYSA-N 2-(3,4-Dihydroxyoxolan-2-yl)-2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)C1OCC(O)C1O HVUMOYIDDBPOLL-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001219 Polysorbate 40 Polymers 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 description 1
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 description 1
- 229940101027 polysorbate 40 Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005320 surfactant adsorption Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Images
Abstract
This invention discloses a method for preparing graphite foam material with uniform pore sizes and high heat conductivity. The method comprises: (1) placing mesophase pitch into a high-pressure reactor, adding surfactant, mixing uniformly, vacuumizing, heating to 260-350 deg.C, pressurizing to 2-6.0 MPa, heating to 450-650 deg.C, keeping for 15 min-2 h, cooling, and exhausting to obtain pitch foam; (2) heating the pitch foam at a heating rate not higher than 1 deg.C/min to 950-1100 deg.C, and carbonizing under nitrogen protection to obtain carbonized pitch foam; (3) heating the carbonized pitch foam at a heating rate not higher than 1 deg.C/min to 2500-3000 deg.C under Ar protection, and cooling naturally to obtain graphite foam material with high heat conductivity. The obtained graphite foam material can be widely used in radiators, heat exchangers, brake pads of automobiles and planes, catalyst carriers, and gas adsorbents.
Description
Technical field
The present invention relates to a kind of manufacture method of high heat conducting foam material of graphite, the manufacture method of the uniform high heat conducting foam material of graphite in particularly a kind of aperture.
Background of invention
Carbon foam is applied in high-tech area, and described Application Areas comprises as thermal insulation/lagging material, the conductive filler material that is used for polymkeric substance or plastics, electrode and structured material etc.Having Carbon foam than bigger serface and high porosity has big potentiality and is applied to these fields.
The manufacture method of Carbon foam has, and uses coal or the nitriding of pitch high pressure foaming, or uses raw materials such as coal, pitch, polyethylene by the whipping agent foaming etc., then this porous form is at high temperature solidified, so that obtain Carbon foam.
The thermal conductivity of the Carbon foam that above Carbon foam and preparation method obtain is relatively poor, generally can only be used as lagging material or structured material.People such as U.S. Oak Ridge laboratory James.Klett announced a method for preparing the high graphitization degree Carbon foam in 1997, its principle is to utilize the method for the volatilization of low molecular compound in the mesophase pitch heat-processed from foaming, the aperture average out to 300 μ m of gained Carbon foam, and have the higher specific tenacity and the capacity of heat transmission.People such as Qiu Jieshan of Dalian University of Technology had applied for a kind of method of utilizing coal tar mid-temperature pitch and petroleum pitch to prepare Carbon foam in 2003, and the raw materials used metal-salt that all adopts carries out upgrading.The Yu Ming of Donghua University virtues etc. were applied for a kind of method of utilizing mechanical expressing technique to prepare Carbon foam in 2004, and preparation process need be added whipping agent.The applicant has applied for that an application number is 200510073394.4, and denomination of invention is the application for a patent for invention of high heat conducting foam material of graphite and manufacture method thereof, adopts the special pressure mode of putting to prepare good foams.Above method since raw materials used be pitch, at high temperature cause capillary inhomogeneously owing to polymerization and decomposition, the Carbon foam aperture that makes is not very even, this can influence performances such as the intensity of material and thermal conductivity.
The present patent application is that to utilize mesophase pitch (comprising coal tar mesophase pitch, oil mesophase pitch, synthetic asphalts or their mixture) be raw material, do not carry out upgrading, only add a little tensio-active agent and come the reconciliation statement surface tension, utilize again under the high pressure to prepare high conductive graphite foam from the principle that foams.By adding different tensio-active agents, can make hole bubble homogeneous, hole bubble size and the controlled graphite foam of pore wall thickness, graphite foam product density and porosity ranges are wide, can better adapt to the requirement of different purposes.
Summary of the invention
The preparation method who the purpose of this invention is to provide the uniform high heat conducting foam material of graphite in a kind of aperture, this method can make have large surface area, hole bubble homogeneous, hole bubble size and the controlled graphite foam of pore wall thickness, graphite foam product density and porosity ranges are wide, can better adapt to the requirement of different purposes, physical strength high heat conducting foam material of graphite;
Technical scheme of the present invention is as follows:
The preparation method of the high heat conducting foam material of graphite of uniform pore size provided by the invention, its preparation process is as follows:
(1) mesophase pitch is put into the high-temperature high-voltage reaction device, the interpolation tensio-active agent also mixes, be evacuated to 0.1-0.08MPa, and be warming up to 260-350 ℃ with the temperature rise rate of 1-5 ℃/min, be pressurized to 2-6.0MPa, continuation is warming up to 450-650 ℃ with 1-5 ℃/min temperature rise rate, after constant temperature 15min-2 hour, cools off and venting obtains bituminous froth; The addition of described tensio-active agent is the 0.1%-5% of described mesophase pitch weight; Described tensio-active agent comprises negatively charged ion, positively charged ion or nonionogenic tenside;
(2) the gained bituminous froth is warming up to 950-1100 ℃ with the temperature rise rate that is not more than 1 ℃/min, carries out charing under the omnidistance nitrogen protection, obtain the charing bituminous froth; Gained asphalt foam charcoal body again under argon shield, is warming up to 2500-3000 ℃ with the temperature rise rate that is not more than 1 ℃/min,, just obtains high heat conducting foam material of graphite through naturally cooling.
Described mesophase pitch comprises petroleum asphalt based mesophase pitch, synthetic mesophase asphalt phase, coal tar mesophase pitch or their mixture.Described mesophase pitch is to be the mesophase pitch that raw material obtains through thermal treatment with petroleum pitch, coal-tar pitch or synthetic asphalts.Described tensio-active agent is solid-state or liquid surfactant.
The high heat conducting foam material of graphite of the uniform pore size of the method for the invention preparation, its hole bubble size evenly, pore size distribution is narrow, the aperture is in the 80-800 mu m range, and is and adjustable; Density is 0.25-0.85g/cm
3, void content is 50-85%, thermal conductivity is 50-170W/mk.
High heat conducting foam material of graphite provided by the invention and preparation method thereof has following advantage:
Because used mesophase pitch does not add catalyzer and carries out upgrading; Also need not whipping agent, only need a little tensio-active agent, low cost of manufacture; By adding tensio-active agent reconciliation statement surface tension, realize density and controlled porosity, technology is simple; The foam material of graphite hole bubble structure that finally obtains is even, and performance range is wide, and purposes is wide.
Embodiment
Further describe the present invention below in conjunction with embodiment:
The preparation method of the high heat conducting foam material of graphite of uniform pore size provided by the invention, its preparation process is as follows:
(1) mesophase pitch is put into the high-temperature high-voltage reaction device, the interpolation tensio-active agent also mixes, be evacuated to 0.1-0.08MPa, and be warming up to 260-350 ℃ with the temperature rise rate of 1-5 ℃/min, be pressurized to 2-6.0MPa, continuation is warming up to 350-650 ℃ with 1-5 ℃/min temperature rise rate, after constant temperature 15min-2 hour, cools off and venting obtains bituminous froth; The addition of described tensio-active agent is the 0.1%-5% of described mesophase pitch weight; Described tensio-active agent comprises negatively charged ion, positively charged ion or nonionogenic tenside;
(2) the gained bituminous froth is warming up to 950-1100 ℃ with the temperature rise rate that is not more than 1 ℃/min, carries out charing under the omnidistance nitrogen protection, obtain the charing bituminous froth; Gained asphalt foam charcoal body again under argon shield, is warming up to 2500-3000 ℃ with the temperature rise rate that is not more than 1 ℃/min,, just obtains high heat conducting foam material of graphite through naturally cooling.
Described mesophase pitch comprises petroleum asphalt based mesophase pitch, synthetic mesophase asphalt phase, coal tar mesophase pitch or their mixture.Described mesophase pitch is to be the mesophase pitch that raw material obtains through thermal treatment with petroleum pitch, coal-tar pitch or synthetic asphalts.Described tensio-active agent is solid-state or liquid surfactant.
The high heat conducting foam material of graphite of the uniform pore size of the method for the invention preparation, its hole bubble size evenly, pore size distribution is narrow, the aperture is in the 80-800 mu m range, and is and adjustable; Density is 0.25-0.85g/cm
3, void content is 50-85%, thermal conductivity is 50-170W/mk.
Tensio-active agent has significantly reduced surface tension in the absorption of fluid surface, weakened the trend of liquid contraction surface and foam coalescence, reduced the impellent of the vacuolar membrane of Laplace pressure reduction and therefore generation, thereby be beneficial to the stability of liquid film and relevant dispersion system to the discharge opeing of Plateau border, attenuation.Adopt dissimilar tensio-active agents, since its mechanism of action difference, the bituminous froth performance difference that obtains.
When adopting ionogenic surfactant, the ionogenic surfactant adsorption layer is charged, makes between liquid film two surfaces and produces electric exclusion, and be not easy to approaching.In the adsorption layer of surface active agent between the hydrophobic group of molecule (sometimes between hydrophilic group) have lateral interaction, this makes adsorption layer have certain intensity, makes liquid film can bear suitable external force effect and unlikely breaking.When having adsorption layer, external force makes liquid level local deformaton produce adsorptive capacity and surface pressure uneven distribution, adsorbed molecules will flow direction density little (Marangoni effect) from density general goal band automatically, this is the actual mechanism of repairing liquid film distortion, damage, stable most important to dispersion system.Foam generates and is coated with constantly generation of new surface in the membrane process, and tensio-active agent progressively is adsorbed onto on the surface, reduces surface tension accordingly liquid film is easy to generate; Formed adsorption film can prevent the liquid film contraction and break, make foam stabilization, is evenly distributed.Simultaneously because the mobile rearrangement that promotes the intermediate phase liquid crystal molecule of above-mentioned liquid film makes that the synusia structure of Carbon foam ligament is more regular, cause the thermal conductivity of the finished product that by a relatively large margin raising (can reach 28%) is arranged.
When adopting nonionic surface active agent, the nonionic surface active agent molecule has weakened with the repulsive interaction between the ionogenic surfactant polar group of same electric charge.And polarization may take place and produce further interaction in the polar group of nonionic surface active agent under the electric field action of contiguous surface active agent ion, make the liquid film thickening, under the situation that does not influence material thermal conductivity, improved the compressive strength (can reach 34%) of foam materials greatly.
The gained bituminous froth is warming up to 950-1100 ℃ with the temperature rise rate that is not more than 1 ℃/min, carries out charing under the omnidistance nitrogen protection, obtain the charing bituminous froth; Again with gained charing bituminous froth under argon shield, be warming up to 2500-3000 ℃ with the temperature rise rate that is not more than 1 ℃/min and carry out greying, through naturally cooling, just obtain high heat conducting foam material of graphite.The density of gained high heat conducting foam material of graphite is 0.25-0.85g/cm
3, void content is 50-85%, thermal conductivity is 50-170W/mk.
Embodiment 1
A certain amount of oil mesophase pitch powder is put into the high-temperature high-voltage reaction device, add the aniorfic surfactant Sodium dodecylbenzene sulfonate of oil mesophase pitch powder weight 0.1%, and mix, be evacuated to 0.1MPa, be heated to 260 ℃ with the heat-up rate of 4 ℃/min, be pressurized to 6.0MPa, be warming up to 650 ℃ of temperature with 2 ℃/min again, constant temperature 15min, be cooled to room temperature after, at the uniform velocity bleed off gas to normal pressure, obtain bituminous froth;
The gained bituminous froth is warming up to 950 ℃ with the heat-up rate that is not more than 1 ℃/min, under the omnidistance nitrogen protection, carries out charing and handle, get the charing bituminous froth;
Gained charing bituminous froth again under argon shield, is warming up to 2600 ℃ with the heat-up rate that is not more than 1 ℃/min,, just obtains high heat conducting foam material of graphite as shown in Figure 1 through naturally cooling;
After measured, the prepared high heat conducting foam material of graphite of present embodiment as shown in Figure 1, its density is 0.65g/cm
3, void content is 69%, and thermal conductivity is 170W/mk, and compressive strength is 1.68Kg/cm
2(MPa).
Embodiment 2
Get a certain amount of coal tar mesophase pitch powder and put into the high-temperature high-voltage reaction device, add the nonionic surface active agent span 40 of coal tar mesophase pitch powder weight 5%, and mix, be evacuated to 0.08MPa, temperature rise rate with 5 ℃/min is heated to 350 ℃, be pressurized to 4.0MPa, temperature rise rate with 1 ℃/min is warming up to 450 ℃ again, behind the constant temperature 1h, when being cooled to room temperature with 1-2 ℃/min rate of temperature fall, at the uniform velocity bleeding off gas makes temperature reduce to the softening temperature of raw material (promptly finishing for 300 ℃) up to normal pressure, to obtain bituminous froth;
The gained bituminous froth is warming up to 1050 ℃ with the heat-up rate that is not more than 1 ℃/min, under the omnidistance nitrogen protection, carries out charing and handle, get the charing asphalt foam;
Gained charing bituminous froth again under argon shield, is warming up to 2800 ℃ with the heat-up rate that is not more than 1 ℃/min,, just obtains high heat conducting foam material of graphite as shown in Figure 2 through naturally cooling;
The density of measuring this graphite foam of gained is 0.57g/cm
3, void content is 78%, and thermal conductivity is 120W/mk, and compressive strength is 2.39Kg/cm
2
Embodiment 3
A certain amount of synthetic mesophase asphalt phase powder is put into the high-temperature high-voltage reaction device, add the cationic surfactant hexadecyl front three ammonium chloride of synthetic mesophase asphalt phase powder weight 1.5%, and mix, be evacuated to 0.05MPa, heat-up rate with 1 ℃/min is heated to 290 ℃, be pressurized to 2.0MPa, be warming up to 550 ℃ of temperature with 2 ℃/min again, behind the constant temperature 15min, when being cooled to room temperature with 1-2 ℃/min rate of temperature fall, at the uniform velocity bleed off gas and make temperature reduce to normal temperature, obtain bituminous froth up to normal pressure;
The gained bituminous froth is warming up to 1000 ℃ with the heat-up rate that is not more than 1 ℃/min, under the omnidistance nitrogen protection, carries out charing and handle, get the charing bituminous froth;
Gained charing bituminous froth again under argon shield, is warming up to 3000 ℃ with the heat-up rate that is not more than 1 ℃/min,, just obtains high heat conducting foam material of graphite as shown in Figure 3 through naturally cooling;
After measured, the density of the prepared high heat conducting foam material of graphite of present embodiment is 0.38g/cm
3, void content is 83%, and thermal conductivity is 102W/mk, and compressive strength is 1.79Kg/cm
2(MPa).
Embodiment 4
Get a certain amount of synthetic mesophase asphalt phase powder and put into the high-temperature high-voltage reaction device, the nonionic surface active agent polysorbate40 that adds synthetic mesophase asphalt phase powder weight 2.5% mixes, be evacuated to 0.08MPa, temperature rise rate with 3 ℃/min is heated to 290 ℃, be pressurized to 2.0MPa, temperature rise rate with 1 ℃/min is warming up to 500 ℃ again, behind the constant temperature 2h, when being cooled to room temperature with 1-2 ℃/min rate of temperature fall, at the uniform velocity bleeding off gas makes temperature reduce to the softening temperature of raw material (promptly finishing for 290 ℃) up to normal pressure, to obtain bituminous froth;
The gained bituminous froth is warming up to 1050 ℃ with the heat-up rate that is not more than 1 ℃/min, under the omnidistance nitrogen protection, carries out charing and handle, get the charing asphalt foam,
Gained charing bituminous froth again under argon shield, is warming up to 2800 ℃ with the heat-up rate that is not more than 1 ℃/min,, just obtains high heat conducting foam material of graphite as shown in Figure 4 through naturally cooling;
The density of measuring this graphite foam of gained is 0.59g/cm
3, void content is 74%, and thermal conductivity is 72W/mk, and compressive strength is 3.47Kg/cm
2
Embodiment 5
A certain amount of synthetic mesophase asphalt phase powder is put into the high-temperature high-voltage reaction device, the nonionic surface active agent sorbester p18 that adds synthetic mesophase asphalt phase powder weight 0.5% mixes, be evacuated to 0.08MPa, heat-up rate with 2 ℃/min is heated to 290 ℃, be pressurized to 2.0MPa, be warming up to 550 ℃ of temperature with 2 ℃/min again, behind the constant temperature 0.5h, when being cooled to room temperature with 1-2 ℃/min rate of temperature fall, at the uniform velocity bleed off gas and make temperature reduce to normal temperature, obtain bituminous froth up to normal pressure;
The gained bituminous froth is warming up to 1000 ℃ with the heat-up rate that is not more than 1 ℃/min, under the omnidistance nitrogen protection, carries out charing and handle, get the charing bituminous froth;
Gained charing bituminous froth again under argon shield, is warming up to 2800 ℃ with the heat-up rate that is not more than 1 ℃/min,, just obtains high heat conducting foam material of graphite as shown in Figure 5 through naturally cooling;
After measured, the density of the prepared high heat conducting foam material of graphite of present embodiment is 0.53g/cm
3, void content is 76%, and thermal conductivity is 89W/mk, and compressive strength is 3.48Kg/cm
2(MPa).
Embodiment 6
A certain amount of synthetic mesophase asphalt phase powder is put into the high-temperature high-voltage reaction device, the anionic surfactant so lauryl sulfate of adding synthetic mesophase asphalt phase powder weight 3% mixes, be evacuated to 0.08MPa, heat-up rate with 2 ℃/min is heated to 290 ℃, be pressurized to 2.0MPa, be warming up to 600 ℃ of temperature with 2 ℃/min again, behind the constant temperature 15min, when being cooled to room temperature with 1-2 ℃/min rate of temperature fall, at the uniform velocity bleed off gas and make temperature reduce to normal temperature, obtain bituminous froth up to normal pressure;
The gained bituminous froth is warming up to 1000 ℃ with the heat-up rate that is not more than 1 ℃/min, under the omnidistance nitrogen protection, carries out charing and handle, get the charing bituminous froth;
Gained charing bituminous froth again under argon shield, is warming up to 2800 ℃ with the heat-up rate that is not more than 1 ℃/min,, just obtains high heat conducting foam material of graphite as shown in Figure 6 through naturally cooling;
After measured, the density of the prepared high heat conducting foam material of graphite of present embodiment is 0.42g/cm
3, void content is 81%, and thermal conductivity is 110W/mk, and compressive strength is 1.82Kg/cm
2(MPa).
Embodiment 7
A certain amount of coal tar mesophase pitch powder is put into the high-temperature high-voltage reaction device, the aniorfic surfactant dodecyl sodium sulfonate calcium that adds synthetic mesophase asphalt phase powder weight 5% mixes, be evacuated to 0.08MPa, heat-up rate with 2 ℃/min is heated to 290 ℃, be pressurized to 2.0MPa, be warming up to 600 ℃ of temperature with 2 ℃/min again, behind the constant temperature 15min, when being cooled to room temperature with 1-2 ℃/min rate of temperature fall, at the uniform velocity bleed off gas and make temperature reduce to normal temperature, obtain bituminous froth up to normal pressure;
The gained bituminous froth is warming up to 1000 ℃ with the heat-up rate that is not more than 1 ℃/min, under the omnidistance nitrogen protection, carries out charing and handle, get the charing bituminous froth;
Gained charing bituminous froth again under argon shield, is warming up to 2800 ℃ with the heat-up rate that is not more than 1 ℃/min,, just obtains high heat conducting foam material of graphite shown in Figure 7 through naturally cooling;
After measured, the density of the prepared high heat conducting foam material of graphite of present embodiment is 0.45g/cm
3, void content is 78%, and thermal conductivity is 115W/mk, and compressive strength is 2.01Kg/cm
2(MPa).
Claims (4)
1, a kind of preparation method of high heat conducting foam material of graphite of uniform pore size, its preparation process is as follows:
(1) mesophase pitch is put into the high-temperature high-voltage reaction device, the interpolation tensio-active agent also mixes, be evacuated to 0.1-0.08MPa, and be warming up to 260-350 ℃ with the temperature rise rate of 1-5 ℃/min, be pressurized to 2-6.0MPa, continuation is warming up to 450-650 ℃ with 1-5 ℃/min temperature rise rate, after constant temperature 15min-2 hour, cools off and venting obtains bituminous froth; The addition of described tensio-active agent is the 0.1%-5% of described mesophase pitch weight; Described tensio-active agent comprises negatively charged ion, positively charged ion or nonionogenic tenside;
(2) the gained bituminous froth is warming up to 950-1100 ℃ with the temperature rise rate that is not more than 1 ℃/min, carries out charing under the omnidistance nitrogen protection, obtain the charing bituminous froth; Gained asphalt foam charcoal body again under argon shield, is warming up to 2500-3000 ℃ with the temperature rise rate that is not more than 1 ℃/min,, just obtains high heat conducting foam material of graphite through naturally cooling.
2, by the preparation method of the high heat conducting foam material of graphite of the uniform pore size of claim 1, it is characterized in that described mesophase pitch comprises petroleum asphalt based mesophase pitch, synthetic mesophase asphalt phase, coal tar mesophase pitch or their mixture.
By the preparation method of the high heat conducting foam material of graphite of the described uniform pore size of claim 2, it is characterized in that 3, described mesophase pitch is to be the mesophase pitch that raw material obtains through thermal treatment with petroleum pitch, coal-tar pitch or synthetic asphalts.
4, press the preparation method of the high heat conducting foam material of graphite of claim 1 or 2 described uniform pore sizes, it is characterized in that described tensio-active agent is solid-state or liquid surfactant.
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| CN102219208A (en) * | 2011-03-28 | 2011-10-19 | 航天材料及工艺研究所 | Method for enhancing heat conduction performance of foamy carbon with high aperture ratio |
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| CN105984863A (en) * | 2015-02-26 | 2016-10-05 | 上海宝钢化工有限公司 | Preparing method and application of foam carbon |
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| US6673328B1 (en) * | 2000-03-06 | 2004-01-06 | Ut-Battelle, Llc | Pitch-based carbon foam and composites and uses thereof |
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