CN103570008A - Isotropic graphite material and method for producing same - Google Patents
Isotropic graphite material and method for producing same Download PDFInfo
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- CN103570008A CN103570008A CN201210333064.4A CN201210333064A CN103570008A CN 103570008 A CN103570008 A CN 103570008A CN 201210333064 A CN201210333064 A CN 201210333064A CN 103570008 A CN103570008 A CN 103570008A
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- 239000007770 graphite material Substances 0.000 title claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 238000000034 method Methods 0.000 claims abstract description 66
- 230000007547 defect Effects 0.000 claims abstract description 20
- 238000010000 carbonizing Methods 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 32
- 238000002203 pretreatment Methods 0.000 claims description 29
- 238000012545 processing Methods 0.000 claims description 28
- 238000005087 graphitization Methods 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 19
- 230000001681 protective effect Effects 0.000 claims description 15
- 238000009694 cold isostatic pressing Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 238000007669 thermal treatment Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 238000003763 carbonization Methods 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 239000004005 microsphere Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 10
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Abstract
The invention discloses a method for preparing an isotropic graphite material, which is characterized in that after intermediate phase carbon microspheres which are optionally pretreated are molded into a green body by a cold equal-pressure method, the overall process time can be effectively shortened by utilizing multi-stage carbonization treatment, and the obtained isotropic graphite material has better isotropy, complete surface, no crack defect and good mechanical, thermal and electrical properties.
Description
Technical field
The invention relates to a kind of isotropy graphite material and manufacture method thereof, and particularly relevant for a kind of isotropy graphite material and manufacture method thereof of utilizing carbonaceous mesophase spherules but not adding any binding agent.
Background technology
Graphite material is that carbon forms, and by different manufacture method, can obtain amorphous carbon, graphite is unique carbon material of the different qualities such as carbon, thermally decomposed carbon and carbon fibre.Wherein, that isotropy graphite (isotropic graphite) material has is high temperature resistant, conduction, heat conduction, lubricated, porousness, the performance such as plastic and anticorrosive, is recently widely used in each industries such as metallurgy, machinery and semi-conductor.Traditional graphite processing procedure, the general coke (coke) that uses is as raw material, after mixing with coal tar pitch (coal tar pitch), inject extruding in mould, then under non-oxide condition, be heated to approximately 1000 ℃, form the pertusate agraphitic carbon of tool (amorphous carbon).Afterwards, then pass through impregnating pitch and bake again, so carrying out repeatedly, to fill up hole.Subsequently, recycling is heat-treated to 2500 ℃ to 3000 ℃, makes agraphitic carbon form highdensity graphite.
Developing rapidly of energy storage material in recent years, therefore the isotropy graphite material demand for high-density, high strength, high purity and good processability also increases fast.Yet conventional graphite processing procedure quality of item complicated and gained cannot satisfy the demands.Therefore, recently develop carbonaceous mesophase spherules (the mesocarbon microbeads utilizing from sintered type (self-sintering); MCMBs), it is not need mixing, kneading and pulverising step, also do not need through impregnating pitch and the knot supervisor that reburns, to fill up hole again, can manufacture high strength, high-density, highly purified graphite carbon material, not only significantly promote graphite mechanical properties, also simplified the Production Flow Chart of isotropy graphite material complexity.Above-mentioned processing procedure can be consulted relevant front case to the pertinent literature of material, as U.S. Patent Bulletin US5,525,276, US5,547,654, US5,609,800, US4,929,404, and TaiWan, China patent announcement TW326027, TW379202, TW424079 etc., at this, one be listed as reference herein.
Yet still there is following problem in the processing procedure of above-mentioned graphite material.For example, above-mentioned processing procedure, when utilizing carbonaceous mesophase spherules to form green compact, when follow-up carbonization and graphitization processing, easily discharges a large amount of volatile components, and the surface of causing the graphite carbon material of follow-up gained produces crack or defect and surperficial incomplete problem.Secondly, above-mentioned processing procedure if desired carries out carbonizing treatment (routine TaiWan, China patent described above is contained) at vacuum state, can cause this significantly lifting when volume production.If the problem of volatile component loss during for fear of carbonization and graphitization processing, and slow down the temperature rise rate of carbonizing treatment, will make the more tediously long and more power consumption of carbonizing treatment time-histories.
Comprehensive speech, the fabrication process time of known isotropy graphite material is length and power consumption, and easily there is crack on the surface of the graphite material of gained, even breaks, and then limit the scope of its application.
Therefore, need the manufacture method that a kind of isotropy graphite material is provided badly, thoroughly to solve the surface of the graphite material of known processing procedure gained, have crack or defect, and limit the problems such as scope of its application.
Summary of the invention
Therefore, one aspect of the present invention is to provide a kind of manufacture method of isotropy graphite material, its be by through or without the carbonaceous mesophase spherules of pre-treatment, through the cold isostatic pressing that waits, be molded into after green compact, utilize multistage carbonizing treatment, to shorten the time of carbonizing treatment, then carry out graphitization processing, and form isotropy carbonaceous material.
Secondly, another aspect of the present invention is to provide a kind of isotropy graphite material, and it is to utilize aforesaid method obtained, and the surface of the isotropy graphite material of gained is complete flawless defect and has good machinery, calorifics and electrical properties.
According to above-mentioned aspect of the present invention, a kind of manufacture method of isotropy graphite material is proposed.In one embodiment, the manufacture method of this isotropy graphite material be by through or without the carbonaceous mesophase spherules of pre-treatment, utilize the cold isostatic pressing that waits to carry out mold pressing, to form green compact.Then, green compact are carried out to multistage carbonization and graphitization processing, and form isotropy graphite material.
In the above-described embodiments, median size without the carbonaceous mesophase spherules of pre-treatment is 20 μ m to 30 μ m, wherein aforesaid carbonaceous mesophase spherules has toluene insoluble (toluene insoluble) composition (TI) and quinoline non-soluble (quinoline insoluble) composition (QI), and the difference of TI and QI is that 0.1 weight percent (wt%) is to 2.0wt%.
In the above-described embodiments, aforesaid cold grade in isostatic pressing, its be to through or without the carbonaceous mesophase spherules of pre-treatment, apply 500kg/cm
2to 3000kg/cm
2pressure, to form green compact.
After making green compact; green compact are then under the existence of the first protective atmosphere; carry out multistage carbonizing treatment; to utilize multiple temperature rise rate that green compact are warming up to 1000 ℃ by room temperature (approximately 10 ℃ to 40 ℃); and form a char-forming material; wherein, when the temperature of green compact is 300 ℃ to 1000 ℃, the temperature rise rate of green compact is the monotone increasing function increasing progressively with the fabrication process time.
After multistage carbonizing treatment, then aforesaid char-forming material is carried out to graphitization processing, form by this isotropy graphite material.In an illustration, a surface of above-mentioned isotropy graphite material is complete and do not have a crack defect, this isotropy graphite material in the diversity factor of appointing the two of the thermal expansivity of X-axis, Y-axis and Z axis for being less than 10%.
According to one embodiment of the invention, a plurality of temperature rise rates of above-mentioned multistage carbonizing treatment more comprise by room temperature (approximately 10 ℃ to 40 ℃) and are warming up to first temperature rise rate of 300 ℃, by 300 ℃, are warming up to second temperature rise rate of 500 ℃, by 500 ℃, are warming up to the 3rd temperature rise rate of 800 ℃ and by 800 ℃ of the 4th temperature rise rates that are warming up to 1000 ℃.In this embodiment, the first temperature rise rate is to be equal to or greater than the second temperature rise rate, and the 3rd temperature rise rate is greater than the second temperature rise rate, and the 4th temperature rise rate is greater than the 3rd temperature rise rate.
According to one embodiment of the invention, when the temperature of green compact is 300 ℃ to 1000 ℃, the 3rd above-mentioned temperature rise rate can be 2.5 times to 3.5 times of the second temperature rise rate, and the 4th temperature rise rate can be 7 times to 8 times of the second temperature rise rate.
According to a further aspect in the invention, propose a kind of isotropy graphite material, it is to utilize the manufacture method of above-mentioned isotropy graphite material obtained, and wherein the isotropy graphite material of gained has 1.75g/cm
3to 1.95g/cm
3density and 50 to 90 shore hardness.
Apply isotropy graphite material of the present invention and method thereof, its be by through or without the carbonaceous mesophase spherules of pre-treatment, through the cold isostatic pressing that waits, be molded into after green compact, utilize multistage carbonizing treatment, can shorten the overall process time, and the isotropy graphite material of gained have preferably isotropy, surperficial complete flawless defect and have again good machinery, calorifics and electrical properties thus.
Accompanying drawing explanation
For above and other objects of the present invention, feature, advantage and embodiment can be become apparent, appended the description of the drawings is as follows:
Fig. 1 illustrates the part schema of the manufacture method of isotropy graphite material according to an embodiment of the invention;
Wherein, main element nomenclature:
100: method;
101: by through or without the carbonaceous mesophase spherules of pre-treatment, via the cold step that waits isostatic pressing to be molded into green compact;
103: green compact are carried out to multistage carbonizing treatment, to form the step of char-forming material;
105: char-forming material is carried out to graphitization processing, to form the step of isotropy graphite material.
Embodiment
Described in brought forward, the invention provides a kind of isotropy graphite material and manufacture method thereof, its be by through or without the carbonaceous mesophase spherules of pre-treatment, through the cold isostatic pressing that waits, be molded into after green compact, utilize multistage carbonizing treatment, can obtain the isotropy graphite material of the better and surperficial complete flawless defect of isotropy, and shorten the overall process time.
Profess it, the manufacture method of isotropy graphite material of the present invention can utilize following method to make.Refer to Fig. 1, it is to illustrate the part schema of the manufacture method of isotropy graphite material according to an embodiment of the invention.In one embodiment, this method 100 can be first as shown in step 101, by aforementioned warp or without the carbonaceous mesophase spherules of pre-treatment, through the cold isostatic pressing that waits, carries out mold pressing, to form green compact, wherein the aforesaid cold isostatic pressing that waits is to apply 500kg/cm to above-mentioned warp or without the carbonaceous mesophase spherules of pre-treatment
2to 3000kg/cm
2pressure reach 1 minute to 10 minutes, wherein aforementioned pressure refers to maximum forming pressure.In other example, the aforesaid cold isostatic pressing that waits is to apply 1000kg/cm to above-mentioned warp or without the carbonaceous mesophase spherules of pre-treatment
2to 2000kg/cm
2pressure.
In one embodiment, pre-treatment can be a pulverization process.In another embodiment, pre-treatment can be before pulverization process, more at least comprised a thermal treatment.
In this embodiment, the median size (D of the powder raw material of the aforementioned carbonaceous mesophase spherules without pre-treatment
50) be 20 μ m to 30 μ m, and be 1 μ m to 10 μ m through the median size of the powder raw material of the carbonaceous mesophase spherules of pre-treatment.Generally speaking, the spherome surface of carbonaceous mesophase spherules adsorbs appropriate β-resin (β-resin), makes it have well from sintering characteristic, through cold, waits after isostatic pressing moulding, carbonization, graphitization processing, can prepare high-density isotropy graphite material.Wherein, carbonaceous mesophase spherules has toluene insoluble (toluene insoluble) composition (being designated hereinafter simply as TI) and quinoline non-soluble (quinoline insoluble) composition (being designated hereinafter simply as QI), and β-resin refers to the composition that is insoluble to toluene but is dissolved in quinoline, so the content of β-resin is the difference that is defined as TI and QI.β-the resin content that is applicable to carbonaceous mesophase spherules of the present invention is extremely low, and in an example, the difference of TI and QI is that 0.1 weight percent (wt%) is to 2.0wt%.In another example, the difference of TI and QI is 0.2wt% to 2.0wt%.In another example, the difference of TI and QI is 0.4wt% to 2.0wt%.
Only described hereinly be, if β-resin content is lower than 0.1 weight percent (wt%), carbonaceous mesophase spherules is when follow-up carbonization and graphitization processing, and it is not good from sintering (self-sintering) property, is not easy to form the complete isotropy graphite material in surface.If β-resin content is greater than 2.0wt%,, when follow-up carbonization and graphitization processing, the volatile component that overflow carbosphere inside can cause the surface of the isotropy graphite material of follow-up gained, easily has crack or splintering problem.
Then, as shown in step 103, under the existence of the first protective atmosphere, aforesaid green compact are carried out to multistage carbonizing treatment, it is to utilize multiple temperature rise rate that green compact are warming up to 1000 ℃ by room temperature (approximately 10 ℃ to 40 ℃), and forms char-forming material.In an example, aforesaid the first protective atmosphere is nitrogen, argon gas, helium and above-mentioned arbitrary combination.In another example, aforesaid the first protective atmosphere is nitrogen.
According to one embodiment of the invention, when the temperature of the green compact of step 103 is 300 ℃ to 1000 ℃, the temperature rise rate of green compact may be defined as the monotone increasing function increasing progressively with the fabrication process time.Profess it, in a routine formula, the multistage carbonizing treatment of step 103 can include but not limited to be warming up to first temperature rise rate of 300 ℃, by 300 ℃, be warming up to second temperature rise rate of 500 ℃, by 500 ℃, be warming up to the 3rd temperature rise rate of 800 ℃ and by 800 ℃ of the 4th temperature rise rates that are warming up to 1000 ℃ by room temperature (approximately 10 ℃ to 40 ℃), wherein the first temperature rise rate is to be equal to or greater than the second temperature rise rate, the 3rd temperature rise rate is greater than the second temperature rise rate, and the 4th temperature rise rate is greater than the 3rd temperature rise rate.
Above-mentioned the second temperature rise rate to the four temperature rise rates are for progressively or continuously changing and being the monotone increasing function increasing progressively with the fabrication process time.When multistage carbonizing treatment is warming up to 1000 ℃ by 300 ℃, temperature is temperature rise rate with respect to the derivative of fabrication process time, and this temperature rise rate is to be no more than 10 ℃/min for better.In other words, the second temperature rise rate, the 3rd temperature rise rate and the 4th temperature rise rate can keep constant or increase with time-histories, and wherein, from the second temperature rise rate, the temperature of multistage carbonizing treatment is better no longer to drop to.
For example, when the temperature of green compact is 300 ℃ to 1000 ℃, the 3rd temperature rise rate can be 2.5 times to 3.5 times of the second temperature rise rate, and the 4th temperature rise rate can be 7 times to 8 times of the second temperature rise rate.The isotropy graphite material of gained has preferably isotropy and surperficial complete flawless defect thus.
In an illustration, the second temperature rise rate can be 0.02 ℃ of per minute (℃/min) to 1.0 ℃/min.In another illustration, the second temperature rise rate can be 0.02 ℃/min to 0.7 ℃/min.In another illustration, the second temperature rise rate can be 0.02 ℃/min to 0.05 ℃/min.
At this, it should be noted that, in other embodiments, above-mentioned a plurality of temperature rise rates more can be separately further in the less interval of temperature range, carry out temperature rise rate regulation and control.For example, by 500 ℃, being warming up to the 3rd temperature rise rate of 800 ℃ can further divide into by 500 ℃ and be warming up to the 3rd (1) temperature rise rate of 600 ℃ and by 600 ℃ of the 3rd (2) temperature rise rates that are warming up to 800 ℃, wherein the 3rd (2) temperature rise rate can be equal to or greater than the 3rd (1) temperature rise rate.Only the mode of temperature rise rate regulation and control of the present invention is not limited to this place act, and temperature rise rate regulation and control also can freely be carried out in the interval of other temperature range in the less interval of temperature range.
Afterwards, as shown in step 105, under the existence of the second protective atmosphere, aforesaid char-forming material is carried out to a graphitization processing, form by this isotropy graphite material.In an example, aforesaid the second protective atmosphere is nitrogen, argon gas, helium and above-mentioned arbitrary combination.In another example, aforesaid the second protective atmosphere is argon gas.
In step 105, aforesaid graphitization processing is the 5th temperature rise rate with 5.0 ℃/min to 8.0 ℃/min, aforesaid char-forming material is heated to 2500 ℃ to 3000 ℃ of temperature and holds temperature 30 minutes to 90 minutes.In another example, aforesaid graphite treatment is the 5th temperature rise rate with 6.0 ℃/min to 7.0 ℃/min, aforesaid char-forming material is heated to 2750 ℃ of temperature and holds temperature 30 minutes to 90 minutes.
Between aforesaid carbonizing treatment and graphitization processing, or after graphitization processing, the more alternative cooling step that carries out.Profess it, between aforesaid carbonizing treatment and graphitization processing, alternative is carried out the first natural cooling step, is not using any cooling apparatus and in 45 hours to 50 hours, is making the temperature of aforesaid char-forming material be down to 25 ℃ to 40 ℃.
In addition, after graphitization processing, the more alternative the second nature cooling step that carries out, is not being used any cooling apparatus to make the temperature of aforesaid isotropy graphite material be down to 25 ℃ to 40 ℃.Aforementioned the first natural cooling step and/or the second nature cooling step of carrying out, can make the finer and close and surperficial complete flawless defect of the isotropy graphite material of gained.
Described hereinly be, above-mentioned alleged " isotropy graphite material " refers to the high-density graphite material that utilizes aforesaid method to make, its surface is complete and does not have crack defect, and this isotropy graphite material for being less than 10%, represents that it has preferably isotropy in the diversity factor of appointing the two of the thermal expansivity of X-axis, Y-axis and Z axis.Secondly, the density of this isotropy graphite material is 1.75g/cm
3to 1.95g/cm
3, and its shore hardness is 50 to 90.In other example, the density of this isotropy graphite material is 1.84g/cm
3to 1.93g/cm
3, and its shore hardness is 58 to 85.
It is worth mentioning that, the manufacture method of isotropy graphite material of the present invention, be directly by through or without the carbonaceous mesophase spherules of pre-treatment, through the cold isostatic pressing that waits, be molded into after green compact, recycling multistage carbonizing treatment, can shorten green compact and carry out the treatment time of carbonization and improve yield, therefore method of the present invention get rid of carry out known dipping, the processing procedures such as knot that reburn to be to mend a split.
Not only environmental protection and energy saving of manufacture method due to isotropy graphite material of the present invention, and the isotropy graphite material of gained has better isotropy, its surperficial complete flawless defect, significantly promote again its machinery, calorifics and electrical properties, and then be applied to expand its industry and utilize scope and increase economic worth.For example, the isotropy graphite material of aforementioned gained can be applicable to electrospark machining, continuous casting, the long brilliant stove of silicon single crystal etc.
Below utilize embodiment so that application of the present invention to be described, so it,, not in order to limit the present invention, has and conventionally knows the knowledgeable in the technology of the present invention field, without departing from the spirit and scope of the present invention, and when being used for a variety of modifications and variations.
Prepare isotropy graphite material
Embodiment 1 to embodiment 4
It is raw material that embodiment 1 to embodiment 4 is used carbonaceous mesophase spherules B, and wherein the basic document of carbonaceous mesophase spherules B is to list in table 1 (its TI is that 99.4%, QI is 98.9%, median size (D
50) be 21 μ m; China Steel Chemical Co., Ltd.).
By the above-mentioned carbonaceous mesophase spherules B without pre-treatment of approximately 55 grams, filling is in the cylindric rubber mold (side thickness of die 1.0mm) of the about 25mm of internal diameter, and wherein the pack height of carbonaceous mesophase spherules in mould is about 140mm.In mould lid after the serum cap compacting of homogeneity, carry out shrink-wrap (for example, utilizing for example electric adhesive plaster to be wound around consolidation), to avoid in equal press operation process such as cold grade, fluid under pressure is accidentally invaded in mould and is polluted.
The above-mentioned mould that contains carbonaceous mesophase spherules is placed in cold grade and is all installed with in standby (CL4.5-22-30, Nikkiso Co., Ltd., Japan), is forced into approximately 1,800kg/cm
2and maintain at least about 5 minutes under this pressure.Afterwards, pressure release, to normal pressure, is taken out the cylindric green compact of compression moulding from rubber mold, and by it to being cut to green compact sample.The diameter of this kind of green compact is about 21mm, and length is about 55mm.
Then; aforementioned green compact are put into general commercially available cast atmosphere furnace; three district's temperature control cast stove (Yao Fu Micronics Inc. for example; Taiwan), at the first protective atmosphere, for example under the existence of nitrogen, carry out multistage carbonizing treatment; it is the multistage Elevated Temperature Conditions listed according to table 1; aforesaid green compact are heated to 1000 ℃ by room temperature (approximately 10 ℃ to 40 ℃), to carry out carbonizing treatment, and form char-forming material.Afterwards, carry out the first natural cooling step, do not using any cooling apparatus and under the existence of the first protective atmosphere, body of heater is being cooled to naturally lower than 100 ℃.
The density of the char-forming material of embodiment 1 to embodiment 4 gained is 1.58g/cm
3to 1.63g/cm
3, shore hardness is 93 to 101, its surface is complete and does not have crack defect.
Embodiment 5
It is raw material that embodiment 5 is used carbonaceous mesophase spherules G, and wherein the basic document of carbonaceous mesophase spherules G is to list in table 1 (its TI is that 99.0%, QI is 98.6%, median size (D
50) be 24 μ m; China Steel Chemical Co., Ltd.).
In the situation that logical nitrogen is protected, carbonaceous mesophase spherules G is placed in 200 ℃ to 500 ℃ temperature ranges, carry out the thermal treatment of 6 hours.Thereafter, utilizing gas to draw formula disintegrating apparatus (ALG-2 ，Ling Guang industrial, Taiwan) pulverizes.Afterwards, utilize particle size analyzer (Multisizer
tM3, Beckman Coulter, Inc., U.S.A.) analyze this carbonaceous mesophase spherules powder raw material after crushed, its median size (D
50) be approximately 7 μ m.
Then, by the above-mentioned powder through pre-treatment of approximately 860 grams, filling is in the cylindric rubber mold (side thickness of die 4.0mm) of internal diameter 100mm, and wherein pulverizing the pack height of powder in mould is about 160mm.In mould lid after the serum cap compacting of homogeneity, carry out shrink-wrap (for example, utilizing for example electric adhesive plaster to be wound around consolidation), to avoid in equal press operation process such as cold grade, fluid under pressure is accidentally invaded in mould and is polluted.
Above-mentioned filling, through the mould of the carbonaceous mesophase spherules of pre-treatment, is placed in cold grade and is all installed with standby (the cold balancer of wet type of Jing Feng oil pressure company system, the diameter 130mm of forming room, height 400mm, maximum forming pressure 2500kg/cm
2) in, be forced into about Isosorbide-5-Nitrae 00kg/cm
2and under this pressure, maintain approximately 5 minutes.Afterwards, pressure release, to normal pressure, is taken out the cylindric green compact of compression moulding from rubber mold.So, the diameter of obtained green compact is 79mm, and length is 134mm.
Then; aforementioned green compact are put into general commercially available atmosphere furnace; at the first protective atmosphere for example under the existence of nitrogen; carry out multistage carbonizing treatment; it is the multistage Elevated Temperature Conditions listed according to table 1; aforesaid green compact are heated to 1000 ℃ by room temperature (approximately 10 ℃ to 40 ℃), to carry out carbonizing treatment, and form char-forming material.Afterwards, carry out the first natural cooling step, do not using any cooling apparatus and in approximately 48 hours, make body of heater naturally be cooled to room temperature (approximately 10 ℃ to 40 ℃), so carry out the char-forming material of carbonizing treatment gained, its surface is complete, flawless defect, through surveying its density, is 1.67g/cm
3.
Then; aforementioned char-forming material is put into high-temperature vacuum furnace (Vacuum Furnace Type45; Centorr Vacuum Industries; Inc.) in; at the second protective atmosphere for example under the existence of argon gas, with the 5th temperature rise rate of average 6.7 ℃/min, by aforesaid char-forming material by (approximately 10 ℃ to 40 ℃ of room temperatures; or approximately 30 ℃) be heated to 2750 ℃ and hold temperature 1 hour, to carry out graphitization processing.Afterwards, carry out the second nature cooling step, do not using under any cooling apparatus, body of heater is cooled near room temperature (approximately 10 ℃ to 40 ℃) naturally, wherein the graphite material of gained is isotropy graphite material.The density of the isotropy graphite material of embodiment 5 gained is 1.85g/cm
3, shore hardness is 58, its surface is complete and do not have a rift defect, and this isotropy graphite material in the thermal expansivity of all directions diversity factor therebetween, in order to be less than 10%, (its thermal expansivity in X, Y, Z direction is 5.7 * 10
-6k
-1to 6.0 * 10
-6k
-1).
The isotropy graphite material of embodiment 5 gained further detects its folding strength, ultimate compression strength and specific resistance, and it detects methods involving, and the details will be described later, and its result is as shown in table 2.
Embodiment 6
It is raw material that embodiment 6 is used carbonaceous mesophase spherules M, and wherein the basic document of carbonaceous mesophase spherules M is to list in table 1 (its TI is that 96.9%, QI is 95.0%, median size (D
50) be 24 μ m; China Steel Chemical Co., Ltd.).
Carbonaceous mesophase spherules M before use, first utilizes gas to draw formula disintegrating apparatus (being same as embodiment 5 employees) and pulverizes; Use particle size analyzer (being same as embodiment) to analyze this carbonaceous mesophase spherules median size (D after crushed
50) be approximately 5 μ m.
Then, by the above-mentioned powder through pre-treatment of approximately 250 grams, filling is in the cylindric rubber mold (side thickness of die 1.0mm) of internal diameter 71mm, and wherein pulverizing the pack height of powder in mould is about 118mm.
Above-mentioned filling is through pulverizing the mould of the carbonaceous mesophase spherules of pre-treatment, is placed in during cold grade is all installed with in standby (CL4.5-22-30, Nikkiso Co., Ltd., Japan), is forced into about Isosorbide-5-Nitrae 00kg/cm
2carry out green compact moulding.So, the diameter of obtained green compact is 52mm, and length is 92mm.
Then, aforementioned green compact, as embodiment 5, are carried out to multistage carbonizing treatment in atmosphere furnace, and multistage Elevated Temperature Conditions its be listed according to table 1.So carry out the char-forming material of carbonizing treatment gained, its surface is complete, leakless, through surveying its density, is 1.74g/cm
3.
Then, aforementioned char-forming material is carried out to graphitization processing, its method and condition are to be same as embodiment completely.So, prepared isotropy graphite material, its density is 1.93g/cm
3, shore hardness is 85, its surface is complete and do not have a rift defect, and this isotropy graphite material in the thermal expansivity of all directions diversity factor therebetween, in order to be less than 10%, (its thermal expansivity in X, Y, Z direction is 6.8 * 10
-6k
-1to 7.2 * 10
-6k
-1).
The isotropy graphite material of embodiment 6 gained further detects its folding strength, ultimate compression strength, heat-conduction coefficient and specific resistance, and its result is as shown in table 2.
Comparative example 1 is to comparative example 2
Comparative example 1 to comparative example 2 is to use the method identical with embodiment 1 to carry out isostactic pressing, carbonization and the graphitization processing such as cold.Different, comparative example 1 is different from embodiment 1 to the process conditions of the carbonizing treatment of comparative example 2, and its process conditions is to list in table 2.
The basic document of table 1, carbonaceous mesophase spherules
The usefulness of assessment char-forming material and isotropy graphite material
1. appearance
The graphite material of the char-forming material of embodiment 1 to embodiment 6 gained and embodiment 5 to embodiment 6 gained, and comparative example 1 is to the char-forming material of comparative example 2 gained, further utilize its surperficial integrity of visual observations, and according to following criterion evaluation, its result is as shown in table 2:
Zero: surface is complete and do not have a crack defect
*: surface is imperfect, and has severe crack.
By table 2, can be learnt, the graphite material of the char-forming material of embodiment 1 to embodiment 6 gained and embodiment 5 to embodiment 6 gained, its surface is complete and do not have crack defect or a crack.In comparison, comparative example 1 is to char-forming material and the graphite material of comparative example 2 gained, and its surface is imperfect and have a crack; Due to made char-forming material break, imperfect, cannot further carry out greying to make complete isotropy graphite material.
2. physical strength
Secondly, the graphite material of the char-forming material of embodiment 1 to embodiment 6 gained and embodiment 5 to embodiment 6 gained carries out the assessment of physical strength, it is to utilize commercially available shore hardness tester (Shore Hardness Tester, Type D, Sato Seiki Co., Japan) measurement shore hardness (Shore hardness; Hs), utilize testing method and Sintech10/GL material-testing machine (the MTS Test Systems Co. of ASTM (American Society for Testing and Materials) C651, U.S.A.) measure folding strength, and utilize the testing method of ASTM C695 and Sintech10/GL material-testing machine to measure ultimate compression strength, its result is as shown in table 2.
By table 2, can be learnt, the isotropy graphite material of embodiment 5 to embodiment 6 gained, its shore hardness is 58 to 85, and folding strength is 32MPa to 44MPa, and ultimate compression strength is 68MPa to 120MPa
According to the process conditions of these comparative examples, carry out after carbonizing treatment, the char-forming material billet surface of making all has serious crack, that is cannot make complete char-forming material; Also thereby cannot further with graphitization processing, make complete isotropy graphite material.Make comparisons with embodiment 1 to embodiment 4, comparative example 1 cannot make the reason of complete graphite material to comparative example 2, is that the speed of heating of some temperature section is too fast when carbonizing treatment.
3. calorifics and electrical properties
Moreover, embodiment 5 carries out the assessment of calorifics and electrical properties with the isotropy graphite material of embodiment 6 gained, it is to utilize the testing method of ASTM C714 and ASTM E228 to measure heat-conduction coefficient and thermal expansivity, and utilize the testing method measuring resistance coefficient of ASTM C611, its result is as shown in table 2.
By table 2, can be learnt, the isotropy graphite material of embodiment 5 and embodiment 6 gained, its heat-conduction coefficient is near 40W/mK, and thermal expansivity is 5.7 * 10
-6/ K to 7.2 * 10
-6/ K, specific resistance is 6.6 μ Ω m to 10.8 μ Ω m.
Secondly, result by table 2 can be learnt, embodiment 1 to 6 by without or through the carbonaceous mesophase spherules of pre-treatment, through the cold isostatic pressing that waits, carry out mold pressing, to form after green compact, utilize multistage carbonizing treatment, can shorten and carry out carbonization and graphited treatment time, and and then to make surface complete and do not have char-forming material and an isotropy graphite material of crack defect, and isotropy graphite material is well-behaved, therefore really can reach object of the present invention.
Only at this, need supplement, isotropy graphite material of the present invention and manufacture method thereof also can be used other carbonaceous mesophase spherules or other reaction conditions etc. to carry out, this by the technical field of the invention any have conventionally know that the knowledgeable is known, therefore separately do not repeat.
Comprehensive speech, from the invention described above embodiment, apply isotropy graphite material of the present invention and manufacture method thereof, its advantage be by through or without the carbonaceous mesophase spherules of pre-treatment, through the cold isostatic pressing that waits, be molded into after green compact, utilize multistage carbonizing treatment, can shorten the carbonizing treatment time, and the surface of the isotropy graphite material of gained is complete, flawless defect and isotropy are good, more significantly promote its machinery, calorifics and electrical properties, and then increase its industry range of application, improve its economic worth, for example can be applicable to electrospark machining, continuous casting, the long brilliant stove of silicon single crystal etc.
Although the present invention discloses as above with embodiment; so it is not in order to limit the present invention; persond having ordinary knowledge in the technical field of the present invention; without departing from the spirit and scope of the present invention; when being used for a variety of modifications and variations, so the scope that protection scope of the present invention ought define depending on accompanying claims is as the criterion.
Table 2
Note: N.D. represents not test maybe and cannot test.
Claims (12)
1. a manufacture method for isotropy graphite material, comprises:
By through or without the carbonaceous mesophase spherules of a pre-treatment, via a cold isostatic pressing that waits, carry out mold pressing, to form green compact, wherein the TI of carbonaceous mesophase spherules and the difference of QI without described pre-treatment is 0.1wt% to 2.0wt%;
Under the existence of one first protective atmosphere, described green compact are carried out to a multistage carbonizing treatment, to utilize multiple temperature rise rate that described green compact are warming up to 1000 ℃ by 10 ℃ to 40 ℃ of room temperatures, and form a char-forming material, wherein, when the temperature of described green compact is 300 ℃ to 1000 ℃, the temperature rise rate of described green compact is the monotone increasing function increasing progressively with the fabrication process time; And
Under the existence of one second protective atmosphere; described char-forming material is carried out to a graphitization processing; form by this described isotropy graphite material; the surface of wherein said isotropy graphite material is complete flawless defect, and described isotropy graphite material in the diversity factor of appointing the two of the thermal expansivity of X-axis, Y-axis and Z axis for being less than 10%.
2. the manufacture method of isotropy graphite material as claimed in claim 1, the wherein said cold isostatic pressing that waits is to apply 500kg/cm to described warp or without the carbonaceous mesophase spherules of a pre-treatment
2to 3000kg/cm
2pressure to form green compact.
3. the manufacture method of isotropy graphite material as claimed in claim 1, the wherein said cold isostatic pressing that waits is to apply 1000kg/cm to described warp or without the carbonaceous mesophase spherules of a pre-treatment
2to 2000kg/cm
2pressure to form green compact.
4. the manufacture method of isotropy graphite material as claimed in claim 1, wherein said pre-treatment is a pulverization process.
5. the manufacture method of isotropy graphite material as claimed in claim 4, wherein said pre-treatment, before pulverization process, also at least comprises a thermal treatment.
6. the manufacture method of isotropy graphite material as claimed in claim 4, wherein the median size through the carbonaceous mesophase spherules of described pre-treatment is 1 μ m to 10 μ m.
7. the manufacture method of isotropy graphite material as claimed in claim 1, wherein said the first protective atmosphere is nitrogen, argon gas, helium and above-mentioned arbitrary combination.
8. the manufacture method of isotropy graphite material as claimed in claim 1, the temperature rise rate of wherein said multistage carbonizing treatment comprises by room temperature and is warming up to first temperature rise rate of 300 ℃, by 300 ℃, is warming up to second temperature rise rate of 500 ℃, by 500 ℃, is warming up to the 3rd temperature rise rate of 800 ℃ and by 800 ℃ of the 4th temperature rise rates that are warming up to 1000 ℃, described the first temperature rise rate is to be equal to or greater than described the second temperature rise rate, described the 3rd temperature rise rate is greater than described the second temperature rise rate, and described the 4th temperature rise rate is greater than described the 3rd temperature rise rate.
9. the manufacture method of isotropy graphite material as claimed in claim 8, wherein when the temperature of described green compact is 300 ℃ to 1000 ℃, described the 3rd temperature rise rate is 2.5 times to 3.5 times of described the second temperature rise rate, and described the 4th temperature rise rate is 7 times to 8 times of described the second temperature rise rate.
10. the manufacture method of isotropy graphite material as claimed in claim 1, wherein said the second protective atmosphere is nitrogen, argon gas, helium and above-mentioned arbitrary combination.
11. 1 kinds of isotropy graphite materials, it is to utilize the manufacture method of the isotropy graphite material as described in claim 1 to 10 any one obtained, wherein said isotropy graphite material has 1.75g/cm
3to 1.95g/cm
3density and 50 to 90 shore hardness.
12. isotropy graphite materials as claimed in claim 12, wherein said isotropy graphite material has 1.85g/cm
3to 1.93g/cm
3density and 58 to 85 shore hardness.
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| CN105645397A (en) * | 2016-03-03 | 2016-06-08 | 湖南省长宇新型炭材料有限公司 | Superfine-structure graphite for EDM (electrical discharge machining) and preparation method of superfine-structure graphite for EDM |
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| TWI610887B (en) * | 2016-10-27 | 2018-01-11 | 中國鋼鐵股份有限公司 | Isotropic graphite material, method of producing the same and application thereof |
| TWI628064B (en) * | 2017-09-18 | 2018-07-01 | 中國鋼鐵股份有限公司 | Method of manufacturing graphite molds, graphite molds manufactured by the method, and use thereof |
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| US20080044656A1 (en) * | 2006-08-16 | 2008-02-21 | Feng Chia University | Carbonaceous composite particles and uses and preparation of the same |
| CN101654239A (en) * | 2009-08-27 | 2010-02-24 | 清华大学 | Isotropic graphite product and preparation method thereof |
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| US20080044656A1 (en) * | 2006-08-16 | 2008-02-21 | Feng Chia University | Carbonaceous composite particles and uses and preparation of the same |
| CN101654239A (en) * | 2009-08-27 | 2010-02-24 | 清华大学 | Isotropic graphite product and preparation method thereof |
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