CN104446587B - There is along plane and thickness direction the preparation method of high thermal conductivity coefficient C-base composte material simultaneously - Google Patents
There is along plane and thickness direction the preparation method of high thermal conductivity coefficient C-base composte material simultaneously Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method simultaneously along plane and thickness direction with high thermal conductivity coefficient C-base composte material; Rate of expansion is greater than the expanded graphite of 100, length-to-diameter ratio be less than 1.5 carbon fiber pillar and particle diameter be less than 150 object mesophase pitch and put dispersed with stirring 0.5 ~ 4 hour in a solvent, dry under 60 ~ 150 DEG C of conditions, pulverize; Mixture is being less than pre-molding under 50MPa pressure, then be placed in retort furnace and be warming up to 250 ~ 330 DEG C and be incubated 1 ~ 4 hour, subsequently the idiosome of preoxidation is placed in graphite jig, one is placed in vacuum hotpressing stove and carries out high temperature hot pressing, hot pressing temperature is more than 1300 DEG C, hot pressing pressure is 5 ~ 50MPa, heat-insulation pressure keeping 1 ~ 4 hour.Obtain thermal conductivity and be greater than 140W/ (mK) along in-plane, through-thickness is greater than the high conductive graphite conducting strip of 19W/ (mK).
Description
Technical field
The present invention relates to a kind of preparation method simultaneously along plane and thickness direction with high thermal conductivity coefficient C-base composte material, specifically the preparation method of a kind of expanded graphite and chopped carbon fiber conductive graphite sheet.
Background technology
Along with the fast development of science and technology, efficient heat conduction and heat radiation become the key issue of field of heat management.Such as along with giant-powered computer, notebook computer and the lifting of other electrical installation performances many and the raising of electronic component integration degree, the heat that the thermal value that its unit surface electron device improves constantly makes system produce increases suddenly, if there is no sufficient heat management guarantee, very easily cause related device premature aging or damage.Under microelectronic chip surface temperature must maintain lower temperature, (as silicon device ﹤ 100 DEG C) just can guarantee its high performance operation, many electronic units need could normally to work at the temperature of 40 ~ 60 DEG C, and this proposes more and more higher requirement to thermally conductive material.The limitation such as density is comparatively large owing to existing for traditional metal heat-conducting material (as aluminium, copper etc.), the specific heat conductance ratio of material volume density (thermal conductivity with) is lower, thermal expansivity is higher, oxidizable, have been difficult to meet radiating requirements growing at present.Carbon material has lower density, low thermal coefficient of expansion, excellent mechanical property and higher thermal conductivity, is a class thermally conductive material most with prospects in recent years, thus has broad application prospects in fields such as the energy, communication, electronics.
Expanded graphite is a kind of loose porous vermiform material obtained through graphite intercalation, washing, drying, high-temperature expansion by natural flake graphite.Expanded graphite is owing to having the greying parietal layer of regular bulk, and the obstruction of phonon conduction is less, and heat transfer efficiency is very high, thus utilize expanded graphite to prepare research emphasis that carbon back highly heat-conductive material becomes people, also occurs the mandate or open of similar patent.State Intellectual Property Office of the People's Republic of China's grant number is that the patents of invention such as CN101407322B, CN100368342C, CN101458049A disclose the technology utilizing compression-expansion graphite-made for heat-conducting plate.
Above-described patent of invention disclose only traditional expanded graphite preparation method and pressing process, only obtains the graphite heat conducting material of anisotropic heat conductivity.For graphite flake layer, the vibrations of the lattice of carbon atom are bases of material conducts heat, and therefore in graphite material, phonon transmission can only carry out travel at high speeds along graphite crystal face, and between graphite wafer surface layer due to hypertelorism, have a strong impact on the conduction of phonon.After the process of graphite pressing process, graphite crystal face under hot pressing function along in-plane orientation, thus in graphite heat-conducting fin only along in-plane having high thermal conductivity (being greater than 100W/ (mK)), and through-thickness thermal conductivity is very low, less than 10W/ (mK) (Zhi-HaiFeng, Tong-QiLi, Zi-JunHu, Gao-WenZhao, Jun-ShanWang, Bo-YunHuang, Lowcostpreparationofhighthermalconductivitycarbonblocksw ithultra-highanisotropyfromacommercialgraphitepaper, Carbon, 2012, 50 (10): 3947 – 3948.).The through-thickness thermal conductivity of the graphite heat conduction plate of the announcements such as patent application CN100368342C, CN103539111A of China all at 10W/ (mK) below.Therefore, the through-thickness thermal conductivity that existing published patent of invention obtains far can not meet the requirement to the thermally conductive material capacity of heat transmission such as giant-powered computer, high integrated-optic device, has a kind of highly heat-conductive material simultaneously had along thickness and in-plane is developed on advantage basis seem particularly important at carbon material.
Summary of the invention
The present invention is directed to the defect that graphite heat-conducting fin through-thickness thermal conductivity prepared by existing expanded graphite is too low, provide a kind of along plane and thickness direction graphite heat-conducting fin with high thermal conductivity and preparation method thereof simultaneously.The graphite heat-conducting fin of 140W/ (mK) and 19W/ (mK) is reached respectively, as shown in Figure 1 along plane and thickness direction thermal conductivity.
The present invention is by the following technical solutions:
Have a preparation method for high thermal conductivity coefficient C-base composte material along plane and thickness direction, step is as follows simultaneously:
1) rate of expansion is greater than the expanded graphite of 100, length-to-diameter ratio be less than 1.5 carbon fiber pillar and particle diameter be less than 150 object mesophase pitch and put dispersed with stirring in a solvent, with the rotating speed stirring at normal temperature 0.5 ~ 4 hour of 100 ~ 600r/min, dry under 60 ~ 150 DEG C of conditions, pulverize;
2) above mixture is being less than pre-molding under 50MPa pressure, then be placed in retort furnace and be warming up to 250 ~ 330 DEG C and be incubated 1 ~ 4 hour, subsequently the idiosome of preoxidation is placed in graphite jig, one is placed in vacuum hotpressing stove and carries out high temperature hot pressing, hot pressing temperature is more than 1300 DEG C, hot pressing pressure is 5 ~ 50MPa, heat-insulation pressure keeping 1 ~ 4 hour.
Described solvent is toluene, chloroform, sherwood oil, tetracol phenixin, quinoline or pyridine.
The mass percentage of described expanded graphite, chopped carbon fiber and mesophase pitch is:
Expanded graphite: 45% ~ 80%,
Chopped carbon fiber: 10 ~ 45%;
Mesophase pitch: 8 ~ 35%.
Be described as follows:
(1) preparation of expanded graphite: expansible black lead is expanded at 1000 ~ 1200 DEG C, obtain the expanded graphite that rate of expansion is greater than 100, as shown in Figure 2, be a kind of loose porous structure, rate of expansion refer to expansible black lead expand after with expansion front volume ratio; Also directly commercially available prod can be adopted.
(2) the short of carbon fiber is cut: by short for the carbon fiber small column being switched to length-to-diameter ratio (staple length and diameter ratio) and being less than 1.5;
Because carbon fiber has high thermal conductivity coefficient vertically, and radial thermal conductivity is very low, by its short switch to smaller length after, will trend towards standing vertically in graphite layers in hot pressing subsequently, utilize its high thermal conductivity vertically to realize the transmission of graphite layers hot-fluid, this is very beneficial for the heat conduction of matrix material through-thickness;
By the expanded graphite of above step and the compound of chopped carbon fiber and hot-forming, achieve the expanded graphite that there is high thermal conductivity at in-plane and the compound of carbon fiber vertically with high thermal conductivity, matrix material densification is made through high temperature hot pressing under bituminous cement effect, obtain thermal conductivity and be greater than 140W/ (mK) along in-plane, through-thickness is greater than the high conductive graphite conducting strip of 19W/ (mK).
Beneficial effect of the present invention: matrix material expanded graphite of the present invention is easy to get, the cutting of carbon fiber is simply controlled.In the present invention, microtexture ordering, densification and greying can efficiently complete, the C-base composte material conducting strip with high thermal conductivity coefficient that can obtain, its capacity of heat transmission is far superior to traditional expanded graphite hot pressing coiled material and other expanded graphites and carbon-fibre composite.
Accompanying drawing illustrates:
Fig. 1 is the microcosmic schematic diagram of conducting strip of the present invention, comprises complex form and hot pressing direction;
Fig. 2 is the scanning electron microscopic picture of expanded graphite;
The picture of Fig. 3 after to be that carbon fiber is short cut.
Embodiment
Provide 6 embodiments of the present invention below, be further illustrate of the present invention, instead of limit the scope of the invention.
Embodiment 1
Rate of expansion is selected to be the expanded graphite of 100.The carbon fiber of diameter 30 microns is cut into the chopped carbon fiber (length-to-diameter ratio 1.5) that length is less than 45 microns.Mesophase pitch is ground to 150 orders and stirring and dissolving is dispersed in toluene solution.After expanded graphite (5g), chopped carbon fiber (mass ratio 3g) and pitch toluene solution (asphalt quality is than 2g) are mixed, stir 4 hours with the rotating speed of 100r/min, then dry rapidly at 150 DEG C, pulverize.Above mixture is placed in graphite jig at 50MPa pressure pre-molding, be placed on after taking-up in retort furnace and be slowly warming up to 250 DEG C and be incubated 4 hours, then at the temperature of 1300 DEG C and 50MPa pressure, vacuum hotpressing is carried out, heat-insulation pressure keeping obtained graphite heat-conducting fin after 1 hour, test is 149.2W/ (mK) along in-plane thermal conductivity, and through-thickness thermal conductivity is 19.7W/ (mK).
Embodiment 2
Expanded at 1000 DEG C by expansible black lead, obtaining rate of expansion is the expanded graphite of 200.The carbon fiber of diameter 30 microns is cut into the chopped carbon fiber (length-to-diameter ratio 1) that length is less than 30 microns.Mesophase pitch is ground to 200 orders and stirring and dissolving is dispersed in chloroformic solution.After expanded graphite (4.5g), chopped carbon fiber (mass ratio 2g) and pitch chloroformic solution (asphalt quality is than 3.5g) are mixed, stir 0.5 hour with the rotating speed of 600r/min, then dry rapidly at 60 DEG C, pulverize.Above mixture is placed in graphite jig at 40MPa pressure pre-molding, be placed on after taking-up in retort furnace and be slowly warming up to 330 DEG C and be incubated 1 hour, then at the temperature of 1400 DEG C and 40MPa pressure, vacuum hotpressing is carried out, heat-insulation pressure keeping obtained graphite heat-conducting fin after 4 hours, test is 140.6W/ (mK) along in-plane thermal conductivity, and through-thickness thermal conductivity is 19.4W/ (mK).
Embodiment 3
Expanded at 1050 DEG C by expansible black lead, obtaining rate of expansion is the expanded graphite of 260.The carbon fiber of diameter 40 microns is cut into the chopped carbon fiber that length is less than 60 microns, as shown in Figure 3, chopped carbon fiber diameter 40 microns, length is 60 microns, length-to-diameter ratio 1.5.Mesophase pitch is ground to 200 orders and stirring and dissolving is dispersed in petroleum ether solution.After expanded graphite (8g), chopped carbon fiber (mass ratio 1g) and pitch petroleum ether solution (asphalt quality is than 1g) are mixed, stir 2 hours with the rotating speed of 400r/min, then dry rapidly at 120 DEG C, pulverize.Above mixture is placed in graphite jig at 10MPa pressure pre-molding, be placed on after taking-up in retort furnace and be slowly warming up to 270 DEG C and be incubated 2 hours, then at the temperature of 1500 DEG C and 40MPa pressure, vacuum hotpressing is carried out, heat-insulation pressure keeping obtained graphite heat-conducting fin after 2 hours, test is 163.2W/ (mK) along in-plane thermal conductivity, and through-thickness thermal conductivity is 19.5W/ (mK).
Embodiment 4
Expanded at 1200 DEG C by expansible black lead, obtaining rate of expansion is the expanded graphite of 300.The carbon fiber of diameter 30 microns is cut into the chopped carbon fiber (length-to-diameter ratio 1.3) that length is less than 40 microns.Mesophase pitch is ground to 150 orders and stirring and dissolving is dispersed in carbon tetrachloride solution.After expanded graphite (4.5g), chopped carbon fiber (mass ratio 4.5g) and pitch carbon tetrachloride solution (asphalt quality is than 1g) are mixed, stir 2 hours with the rotating speed of 300r/min, then dry rapidly at 120 DEG C, pulverize.Above mixture is placed in graphite jig at 5MPa pressure pre-molding, be placed on after taking-up in retort furnace and be slowly warming up to 280 DEG C and be incubated 4 hours, then at the temperature of 1500 DEG C and 30MPa pressure, vacuum hotpressing is carried out, heat-insulation pressure keeping obtained graphite heat-conducting fin after 1 hour, test is 145.2W/ (mK) along in-plane thermal conductivity, and through-thickness thermal conductivity is 23.6W/ (mK).
Embodiment 5
Rate of expansion is selected to be the expanded graphite of 200.The carbon fiber of diameter 20 microns is cut into the chopped carbon fiber (length-to-diameter ratio 1.5) that length is less than 30 microns.Mesophase pitch is ground to 200 orders and stirring and dissolving is dispersed in quinoline solution.After expanded graphite (5g), chopped carbon fiber (mass ratio 4.2g) and pitch quinoline solution (asphalt quality is than 0.8g) are mixed, stir 2 hours with the rotating speed of 300r/min, then dry rapidly at 120 DEG C, pulverize.Above mixture is placed in graphite jig at 10MPa pressure pre-molding, be placed on after taking-up in retort furnace and be slowly warming up to 270 DEG C and be incubated 2 hours, then at the temperature of 1600 DEG C and 40MPa pressure, vacuum hotpressing is carried out, heat-insulation pressure keeping obtained graphite heat-conducting fin after 2 hours, test is 146.8W/ (mK) along in-plane thermal conductivity, and through-thickness thermal conductivity is 20.4W/ (mK).
Embodiment 6
Rate of expansion is selected to be the expanded graphite of 300.The carbon fiber of diameter 30 microns is cut into the chopped carbon fiber (length-to-diameter ratio 1.5) that length is less than 45 microns.Mesophase pitch is ground to 200 orders and stirring and dissolving is dispersed in pyridine solution.After expanded graphite (6g), chopped carbon fiber (mass ratio 2g) and pitch pyridine solution (asphalt quality is than 2g) are mixed, be less than the subnormal ambient of 1MPa at pounds per square inch absolute (psia) under, stir 2 hours with the rotating speed of 300r/min, then dry rapidly at 120 DEG C, pulverize.Above mixture is placed in graphite jig at 25MPa pressure pre-molding, be placed on after taking-up in retort furnace and be slowly warming up to 270 DEG C and be incubated 3 hours, then at the temperature of 1800 DEG C and 25MPa pressure, vacuum hotpressing is carried out, heat-insulation pressure keeping obtained graphite heat-conducting fin after 2 hours, test is 163.3W/ (mK) along in-plane thermal conductivity, and through-thickness thermal conductivity is 24.7W/ (mK).
Claims (3)
1. there is along plane and thickness direction a preparation method for high thermal conductivity coefficient C-base composte material simultaneously, it is characterized in that
1) rate of expansion is greater than the expanded graphite of 100, length-to-diameter ratio be less than 1.5 chopped carbon fiber and particle diameter be less than 150 object mesophase pitch and put dispersed with stirring in a solvent, with the rotating speed stirring at normal temperature 0.5 ~ 4 hour of 100 ~ 600r/min, dry under 60 ~ 150 DEG C of conditions, pulverize;
2) above mixture is being less than pre-molding under 50MPa pressure, then be placed in retort furnace and be warming up to 250 ~ 330 DEG C and be incubated 1 ~ 4 hour, subsequently the idiosome of preoxidation is placed in graphite jig, one is placed in vacuum hotpressing stove and carries out high temperature hot pressing, hot pressing temperature is more than 1300 DEG C, hot pressing pressure is 5 ~ 50MPa, heat-insulation pressure keeping 1 ~ 4 hour;
The mass percentage of described expanded graphite, chopped carbon fiber and mesophase pitch is:
Expanded graphite: 45% ~ 80%,
Chopped carbon fiber: 10 ~ 45%;
Mesophase pitch: 8 ~ 35%.
2. the method for claim 1, is characterized in that described solvent is toluene, chloroform, sherwood oil, tetracol phenixin, quinoline or pyridine.
3. the method for claim 1, is characterized in that in the mixing process of raw material being the pickling efficiency of raising pitch in expanded graphite hole, expanded graphite, chopped carbon fiber and mesophase pitch is uniformly mixed under condition of negative pressure.
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