CN101121823B - Method for preparing natural graphite base composite material - Google Patents
Method for preparing natural graphite base composite material Download PDFInfo
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- CN101121823B CN101121823B CN2007100726244A CN200710072624A CN101121823B CN 101121823 B CN101121823 B CN 101121823B CN 2007100726244 A CN2007100726244 A CN 2007100726244A CN 200710072624 A CN200710072624 A CN 200710072624A CN 101121823 B CN101121823 B CN 101121823B
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Abstract
The present invention provides a preparation method of the natural graphite-based composite material. Use the organic solvent to dissolve the asphalt; add the filler; mix well; remove the solvent; smash into the small particles to make the bonding agent mixture. According to the weight percentages of 50 to 70 percent of natural graphite powder, 2 to 20 percent of doped catalytic graphite element, 22 to 35 percent of bonding agent mixture, the raw materials are mixed well to get the mixture; the mixture is used to make the graphite-based composite material of the high strength and high thermal conductivity through the conventional process or the hot pressing process. The advantage of the present invention is: because the raw materials are added with the enhancing filler carbon nanotubem carbon fiber or silicon carbide fiber, the strength of the prepared graphite composite material is significantly enhanced; at the same time, the catalytic graphite element added into the raw materials can improve the graphitization degree of the graphite composite material, so as to further improve the thermal conductivity. Therefore, the natural graphite can be used as the raw material to replace the coke to make the graphite composite material of the high strength and high thermal conductivity; the anti-bending strength is all larger than 30 MPa; the thermal conductivity is larger than 250 W per mK; and the cost is significantly reduced.
Description
(1) technical field
That the present invention relates to is a kind of preparation method of matrix material, specifically is a kind of preparation method of natural graphite base composite material of saying so.
(2) background technology
In microelectronic integrated circuit and power rectifier device, intensive countless minute sized element produces a large amount of heats, because of thermal stress fatigue and heat dispersion that mismatch in coefficient of thermal expansion between chip and the heat sink material causes not good, and then the chip overheating that causes become the main failure forms of microelectronic circuit and device, and the heat radiation of electronic component becomes system for restricting bottleneck of performance problem.
Along with unicircuit develops to high-density, miniaturization, multifunction, more and more harsher to the requirement of electronic package material.As the ideal heat sink material, must satisfy following basic demand: the one, the heat conductivility of material will be got well, and the heat that semi-conductor chip produces when working can be distributed in time; The 2nd, material coefficient of thermal expansion coefficient (CTE) will be complementary with chips such as Si or GaAs, to avoid the thermal stress damage of chip; The 3rd, material will have enough strength and stiffness, chip is played the effect of supporting and protection; The 4th, the cost of material is low as far as possible, to satisfy the requirement of large-scale commercial applications application.Heat sink materials such as traditional metal and alloy more and more have been difficult to adapt to the every requirement of the high speed development of modern advanced integrated circuit technique to encapsulation.
Natural graphite has lightweight, high temperature resistant, corrosion-resistant, heat-conductive characteristic that shaking property of heat resistanceheat resistant is good and good etc., is that other materials is incomparable.Thermal conductivity in the ideal graphite crystal in the layer plane and the thermal conductivity of vertical this in-plane different fully (perpendicular to the thermal conductivity of carbon net plane only be parallel direction 1/400), can reach 2400W/mK near the thermal conductivity of complete crystalline graphite in layer plane, be high-thermal conductive metal materials of aluminum, copper, more than 5～8 times of silver, and its quality only is 1/6～1/2 of a metallic substance, and thermal expansivity is more much lower than metallic substance.This shows that graphite material has huge advantage as scatterer substituted metal and alloy.At present the graphite that adopts mostly is natural graphite or expanded graphite greatly through the bituminous cement moulding.United States Patent (USP) 4,963,414 propose " sandwich " structure scatterers, and promptly middle portion is natural graphite and bituminous thin slice, is up and down sheet metal, with above-mentioned three bonding forming of thin slice, but has the lower problem of the strength of materials by Resins, epoxy.U.S. Pat 3140190 is to mix with a kind of ceramic additive (molybdenum silicide, titanium boride) and liquid carbonaceous binder with Graphite Powder 99 to prepare refractory materials.The strength of materials that with the natural graphite is feedstock production is lower, and for the higher structure graphite material of service requirements intensity, it has been generally acknowledged that should not be with natural graphite as raw material, and adopts refinery coke, pitch coke etc.
(3) summary of the invention
The object of the present invention is to provide a kind ofly to prepare the graphite composite material of high strength, high heat conductance with the natural graphite coke for replacing, technological operation is simple, easy to operate, help preparing the preparation method of a kind of natural graphite base composite material of special high-performance graphite composite material.
The object of the present invention is achieved like this:
(1) with organic solvent pitch is dissolved, add filler, mix, remove and desolvate, be broken into small-particle and make adhesive mixture;
(2) for the ratio of natural graphite powder 50～70%, doping catalyzed graphitization constituent element 2～20%, binder mixtures 22～35% above-mentioned raw materials is mixed equably by weight percentage, obtain mixture;
(3) with mixture compression moulding.
The present invention can also comprise:
1, described filler is the mixture of one or more any ratios of carbon nanotube, carbon fiber and silicon carbide fiber, and add-on is 0.1～60% of a pitch weight.
2, described compression moulding is with mixture at room temperature, pressure is coldmoulding under 10～80MPa, 600～800 ℃ of following charings, impregnation steps 1 described binder mixtures again, and then 600～800 ℃ of following charings, charing-impregnation cycles several times after, 1000～3000 ℃ of following greyings.
3, described compression moulding is that mixture is hot-forming under 1400～3000 ℃ of temperature, 10～80MPa pressure, constant temperature time 10～90min.
4, described doping constituent element is Ti powder, Si powder, Zr powder or ZrO
2The mixture of any ratio of one or more in the powder.
5, described pitch is high softening point bitumen, and softening temperature is 105～200 ℃.
Method of the present invention is compared with existing technology has following advantage:
1, the graphite composite material for preparing high strength, high heat conductance with the natural graphite for the raw material coke for replacing, its bending strength are all greater than 30MPa, and thermal conductivity is greater than 250W/m.K, and cost significantly reduces.
2, owing to added filler carbon nanotube, carbon fiber or the silicon carbide fiber with enhancement in raw material, the intensity of the graphite composite material of feasible preparation significantly improves.
3, owing in raw material, added the catalyzed graphitization constituent element, improve the degree of graphitization of graphite composite material, and then improve its thermal conductivity.
4, prepare graphite composite material with the natural graphite instead of coke, have the excellent characteristic of natural graphite itself: as Heat stability is good, lower resistivity, fugitive constituent and thermal expansivity.
3, technological operation of the present invention is simple, easy to operate, helps preparing the special high-performance graphite composite material.
(4) embodiment
For example the present invention is done in more detail below and describes:
Embodiment 1
With the natural graphite is raw material, and addition is 70%, and binding agent is a coal-tar pitch, and softening temperature is 105 ℃, and adding filler is carbon nanotube, and content is 0.1% of pitch weight, and the addition of binder mixtures is 22%, and the doping constituent element is the Si powder, and addition is 8%.Above-mentioned compound is mixed, and under 2400 ℃, pressure is hot-forming under the 15MPa, constant temperature time 30min.The room-temperature property of the matrix material of preparation is: bending strength is 40MPa, and thermal conductivity is 260W/m.K.
Embodiment 2
With the natural graphite is raw material, and addition is 60%, and binding agent is a coal-tar pitch, and softening temperature is 200 ℃, and adding filler is carbon nanotube, and content is 0.1% of pitch weight, and the addition of binder mixtures is 30%, and the doping constituent element is ZrO
2Powder, addition are 10%.Above-mentioned compound is mixed, and under 2600 ℃, pressure is hot-forming under the 20MPa, constant temperature time 40min.The room-temperature property of the matrix material of preparation is: bending strength is 38MPa, and thermal conductivity is 430W/m.K.
Embodiment 3
With the natural graphite is raw material, and addition is 50%, and binding agent is a coal-tar pitch, and softening temperature is 120 ℃, and adding filler is carbon fiber, and content is 60% of pitch weight, and the addition of binder mixtures is 35%, and the doping constituent element is the Ti powder, and addition is 15%.Above-mentioned compound is mixed, and under 2800 ℃, pressure is hot-forming under the 50MPa, constant temperature time 60min.The room-temperature property of the matrix material of preparation is: bending strength is 60MPa, and thermal conductivity is 350W/m.K.
Embodiment 4
With the natural graphite is raw material, and addition is 70%, and binding agent is a coal-tar pitch, and softening temperature is 106 ℃, and adding filler is carbon nanotube, and content is 2% of pitch weight, and the addition of binder mixtures is 22%, and the doping constituent element is the Si powder, and addition is 8%.Above-mentioned compound is mixed, and moulding process adopts common process, and pressure is coldmoulding under the 40MPa, 800 ℃ of following charings, again through the binder mixtures dipping, and then 800 ℃ of following charings, after charing-impregnation cycles 2 times, 2400 ℃ of following greyings.The room-temperature property of the matrix material of preparation is: bending strength is 36MPa, and thermal conductivity is 250W/m.K.
Embodiment 5
With the natural graphite is raw material, and addition is 58%, and binding agent is a petroleum pitch, and softening temperature is 150 ℃, and adding filler is silicon carbide fiber, and content is 10% of pitch weight, and the addition of binder mixtures is 22%, and the doping constituent element is the Si powder, and addition is 20%.Above-mentioned compound is mixed, and moulding process adopts common process, and pressure is coldmoulding under the 80MPa, 600 ℃ of following charings, again through the binder mixtures dipping, and then 800 ℃ of following charings, after charing-impregnation cycles 4 times, 3000 ℃ of following greyings.The room-temperature property of the matrix material of preparation is: bending strength is 30MPa, and thermal conductivity is 240W/m.K.
Embodiment 6
With the natural graphite is raw material, and addition is 70%, and binding agent is a petroleum pitch, and softening temperature is 180 ℃, and adding filler is carbon nanotube, and content is 30% of pitch weight, and the addition of binder mixtures is 28%, and the doping constituent element is the Ti powder, and addition is 2%.Above-mentioned compound is mixed, and moulding process adopts common process, and pressure is coldmoulding under the 10MPa, 800 ℃ of following charings, again through the binder mixtures dipping, and then 800 ℃ of following charings, after charing-impregnation cycles 2 times, 2400 ℃ of following greyings.The room-temperature property of the matrix material of preparation is: bending strength is 31MPa, and thermal conductivity is 270W/m.K.
Embodiment 7
With the natural graphite is raw material, and addition is 70%, and binding agent is a coal-tar pitch, and softening temperature is 106 ℃, and adding filler is carbon nanotube, and content is 2% of pitch weight, and the addition of binder mixtures is 22%, and the doping constituent element is the Si powder, and addition is 8%.Above-mentioned compound is mixed, and moulding process adopts common process, and pressure is coldmoulding under the 60MPa, 800 ℃ of following charings, again through the binder mixtures dipping, and then 800 ℃ of following charings, after charing-impregnation cycles 5 times, 1000 ℃ of following greyings.The room-temperature property of the matrix material of preparation is: bending strength is 32MPa, and thermal conductivity is 260W/m.K.
Embodiment 8
With the natural graphite is raw material, and addition is 70%, and binding agent is a coal-tar pitch, and softening temperature is 106 ℃, and adding filler is carbon fiber, and content is 40% of pitch weight, and the addition of binder mixtures is 22%, and the doping constituent element is the Ti powder, and addition is 8%.Above-mentioned compound is mixed, and moulding process adopts common process, and pressure is coldmoulding under the 40MPa, 800 ℃ of following charings, again through the binder mixtures dipping, and then 800 ℃ of following charings, after charing-impregnation cycles 2 times, 2600 ℃ of following greyings.The room-temperature property of the matrix material of preparation is: bending strength is 38MPa, and thermal conductivity is 265W/m.K.
Claims (1)
1. the preparation method of a natural graphite base composite material is characterized in that:
(1) with organic solvent pitch is dissolved, add filler, mix, remove and desolvate, be broken into small-particle and make adhesive mixture; Described filler is the mixture of one or more any ratios of carbon nanotube, carbon fiber and silicon carbide fiber, and add-on is 0.1～60% of a pitch weight;
(2) for the ratio of natural graphite powder 50～70%, doping catalyzed graphitization constituent element 2～20%, binder mixtures 22～35% above-mentioned raw materials is mixed equably by weight percentage, obtain mixture; Described doping constituent element is Ti powder, Si powder, Zr powder or ZrO
2The mixture of any ratio of one or more in the powder;
(3) with mixture compression moulding; Described compression moulding is with mixture at room temperature, and pressure is coldmoulding under 10～80MPa, 600～800 ℃ of following charings, impregnation steps 1 described binder mixtures again, and then 600～800 ℃ of following charings, charing-impregnation cycles several times after, 1000～3000 ℃ of following greyings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100726244A CN101121823B (en) | 2007-08-07 | 2007-08-07 | Method for preparing natural graphite base composite material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007100726244A CN101121823B (en) | 2007-08-07 | 2007-08-07 | Method for preparing natural graphite base composite material |
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| CN101121823A CN101121823A (en) | 2008-02-13 |
| CN101121823B true CN101121823B (en) | 2010-09-08 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293772B (en) * | 2008-05-30 | 2011-06-15 | 上海工程技术大学 | Preparation technique for SiC/CNTs composite ceramic |
| CN102050443B (en) * | 2010-11-22 | 2013-12-11 | 中科恒达石墨股份有限公司 | Method for manufacturing doped flexible graphite products |
| CN102417177A (en) * | 2011-08-20 | 2012-04-18 | 山东东昀石墨科技有限公司 | Regulation method of anisotropies of flexible graphite film and board for heat conduction |
| US8568924B2 (en) * | 2011-11-30 | 2013-10-29 | CNano Technology Limited | Modified battery anode with carbon nanotubes |
| CN102531609B (en) * | 2011-12-14 | 2013-06-12 | 太原理工大学 | Carbon nano tube reinforced AlMgB14-TiB2 composite material and preparation method thereof |
| CN102838108B (en) * | 2012-06-16 | 2014-03-12 | 淄博大陆炭素有限责任公司 | Minor-structure high-density graphite product and preparation method thereof |
| CN103450857A (en) * | 2013-09-05 | 2013-12-18 | 中国科学院青岛生物能源与过程研究所 | Composite graphite heat-conducting membrane material with controllable heat conductivity and preparation process thereof |
| CN105609779A (en) * | 2015-10-28 | 2016-05-25 | 江西正拓新能源科技股份有限公司 | Graphite negative electrode material for power lithium ion battery and preparation method therefor |
| CN105489893A (en) * | 2015-10-28 | 2016-04-13 | 江西正拓新能源科技股份有限公司 | Graphite anode material for lithium-ion battery and preparation method of graphite anode material |
| CN105399083B (en) * | 2015-11-19 | 2018-07-10 | 江西宁新新材料股份有限公司 | Aluminum-graphite composite preparation process |
| CN113307646B (en) * | 2021-06-28 | 2023-04-11 | 湖南兴晟新材料科技有限公司 | High-heat-conductivity and high-purity graphite-based composite material and preparation method thereof |
| CN115521160A (en) * | 2022-10-18 | 2022-12-27 | 雅安天蓝新材料科技有限公司 | Regenerated graphite block and preparation method thereof |
| CN116789453B (en) * | 2023-04-19 | 2024-03-19 | 湖北东南佳特碳新材料有限公司 | Graphite crucible and preparation method and application thereof |
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