CN103373720A - Isotropic carbonaceous material and method for producing same - Google Patents
Isotropic carbonaceous material and method for producing same Download PDFInfo
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- CN103373720A CN103373720A CN2012103202379A CN201210320237A CN103373720A CN 103373720 A CN103373720 A CN 103373720A CN 2012103202379 A CN2012103202379 A CN 2012103202379A CN 201210320237 A CN201210320237 A CN 201210320237A CN 103373720 A CN103373720 A CN 103373720A
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- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 238000000034 method Methods 0.000 claims abstract description 51
- 238000012545 processing Methods 0.000 claims description 30
- 238000010298 pulverizing process Methods 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 26
- 238000005087 graphitization Methods 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000010000 carbonizing Methods 0.000 claims description 17
- 230000001681 protective effect Effects 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 12
- 238000009694 cold isostatic pressing Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 238000000462 isostatic pressing Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
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- 238000003825 pressing Methods 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
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Abstract
The invention discloses an isotropic carbonaceous material and a preparation method thereof, wherein mesocarbon microbeads without any binder are crushed and molded into a green body by a cold equal-pressure method, and then the subsequent carbonization treatment time of the green body can be shortened, and the green body is further graphitized to prepare the isotropic carbonaceous material, wherein the surface of the isotropic carbonaceous material is complete and free of defects and has good mechanical, thermal and electrical properties.
Description
Technical field
The invention relates to a kind of isotropy carbonaceous material (isotropic carbonaceous material) and manufacture method thereof, and particularly relevant for a kind of isotropy carbonaceous material and manufacture method thereof of utilizing carbonaceous mesophase spherules but not adding any binding agent.
Background technology
Carbonaceous material mainly is to consist of with carbon, 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, tool oilness, porousness and the performance such as anticorrosive, recently is widely used in each industry such as metallurgy, machinery and semi-conductor.Traditional isotropy graphite processing procedure, normal operation coke (coke) is as raw material, after coal tar pitch (coal tar pitch) mixes, inject extrusion molding in the mould, then under non-oxide condition, be heated to about 1000 ℃, form the pertusate agraphitic carbon of tool (amorphous carbon).Afterwards, through impregnating pitch and again roasting, so carry out repeatedly, to fill up hole again.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 traditional isotropy graphite processing procedure is complicated, and the quality of item Chang Wufa of gained satisfies the demands.Therefore, recently develop carbonaceous mesophase spherules (the mesocarbon microbeads that utilization has self sintering (self-sintering); MCMBs), the steps such as it is need mixing, kneading and pulverizing, also do not need to reach again the roasting supervisor through impregnating pitch again and fill up hole, can make high strength, high-density, highly purified graphite carbon material, not only significantly promote the graphite mechanical properties, also simplified the Production Flow Chart of isotropy graphite complexity.Above-mentioned processing procedure can be consulted relevant front case with the pertinent literature of material, such as United States Patent (USP) notification number US 5,525,276, US 5,547,654, US 5,609, and 800, US4,929,404, and TaiWan, China patent announcement TW 326027, TW 379202, TW424079 etc., at this reference that is listed as this paper.
Yet still there is following problem in the processing procedure of above-mentioned graphite carbon material.For example, above-mentioned processing procedure when follow-up carbonizing treatment, discharges a large amount of volatile components easily when utilizing carbonaceous mesophase spherules to form green compact, and the surface of causing the carbon material of follow-up gained, the problem that produces the crack or break.Secondly, if above-mentioned carbonization processing procedure will carry out at vacuum state (routine TaiWan, China patent described above is contained), when volume production, can cause the significantly lifting of cost.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 be so that the carbonizing treatment time-histories be more tediously long and more power consumption.
Comprehensive speech, the long and power consumption of the fabrication process time of known isotropy graphite carbon material, and there is easily the crack on the surface of the graphite carbon material of gained even breaks, and then limit the scope of its application.
Therefore, need the manufacture method that a kind of isotropy graphite carbon material is provided badly, the problem of crack or defective is arranged with the surface of the graphite carbon material of the known processing procedure gained of effective solution.
Summary of the invention
Therefore, one aspect of the present invention is to provide a kind of manufacture method of isotropy carbonaceous material, it is the carbonaceous mesophase spherules that will not add any binding agent after the isostatic pressing (cold isostatic pressing) such as pulverizing and cold and being molded into green compact, can shorten follow-up carrying out the carbonizing treatment time.
Secondly, another aspect of the present invention is to provide a kind of isotropy carbonaceous material, and it is to utilize aforesaid method obtained, and the surface of the isotropy carbonaceous material of gained is perfectly to fall into and have good machinery, calorifics and an electrical properties.
According to above-mentioned aspect of the present invention, a kind of manufacture method of isotropy carbonaceous material is proposed.In one embodiment, the manufacture method of this isotropy carbonaceous material be pulverize carbonaceous mesophase spherules first and form one pulverize powder after, utilize the cold isostatic pressing that waits to carry out mold pressing the pulverizing powder that does not add any binding agent, to form green compact.Then, green compact are carried out carbonization and graphitization processing, and form the isotropy carbonaceous material.
In the above-described embodiments, aforesaid pulverising step be make carbonaceous mesophase spherules after crushed the median size of the pulverizing powder of gained be 1 μ m to 10 μ m, wherein aforesaid carbonaceous mesophase spherules has toluene insoluble composition (toluene insoluble, TI) and quinoline non-soluble composition (quinoline insoluble, QI), and the difference of TI and QI be that 0.1 weight percent (wt%) is to 2.0wt%.
In the above-described embodiments, aforesaid cold the grade in the isostatic pressing, it is that above-mentioned pulverizing powder is applied 500kg/cm
2To 3000kg/cm
2Larger forming pressure to form green compact.In other example, aforesaid cold isostatic pressing such as grade is that above-mentioned pulverizing powder is applied 800kg/cm
2To 2000kg/cm
2Larger forming pressure.
After making green compact, green compact then under the existence of protective atmosphere, carry out carbonization and graphitization processing, to form the isotropy carbonaceous material.In an illustration, each surface of above-mentioned isotropy carbonaceous material is complete and do not have a crack, this isotropy carbonaceous material in the thermal expansivity of X-axis, Y-axis and Z axis to appoint the difference between the two be less than 10%.
According to one embodiment of the invention, the median size of above-mentioned pulverizing powder is 3 μ m to 8 μ m.
According to one embodiment of the invention, above-mentioned TI and the difference of QI are 0.2wt% to 2.0wt%.
According to one embodiment of the invention, it is nitrogen, argon gas, helium or above-mentioned arbitrary combination that above-mentioned green compact carry out the used protective atmosphere of carbonization and graphitization processing.
According to a further aspect in the invention, propose a kind of isotropy carbonaceous material, it is to utilize the manufacture method of above-mentioned isotropy carbonaceous material obtained, and wherein the isotropy carbonaceous material of gained has 1.75g/cm
3To 1.95g/cm
3Density and 50 to 90 shore hardness.
Use isotropy carbonaceous material of the present invention and manufacture method thereof, it is the carbonaceous mesophase spherules that will not add any binding agent after the isostatic pressing such as pulverizing and cold and being molded into green compact, not only can shorten follow-up carrying out the carbonizing treatment time, and the surface of the isotropy carbonaceous material of gained is that complete, zero defect and isotropy are good, has again good good machinery, calorifics and electrical properties.
Description of drawings
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 according to an embodiment of the invention part schema of the manufacture method of isotropy carbonaceous material;
Wherein, main element nomenclature:
100: method
101: pulverize carbonaceous mesophase spherules to form the step of pulverizing powder
103: will pulverize powder via the cold step that waits isostatic pressing to be molded into green compact
105: green compact are carried out carbonizing treatment, to form the step of char-forming material
107: char-forming material is carried out graphitization processing, to form the step of isotropy carbonaceous material.
Embodiment
Below hash out the embodiment of the invention.Yet, being understandable that embodiment provides many applicable inventive concepts, it may be implemented in the certain content miscellaneous.The specific embodiment of discussing for explanation, is not to limit scope of the present invention only.
The manufacture method of isotropy carbonaceous material of the present invention can utilize following method to make.See also Fig. 1, it is to illustrate the according to an embodiment of the invention part schema of the manufacture method of isotropy carbonaceous material.In one embodiment, at first shown in step 101, utilization for example commercially available ball mill pulverizing equipment, gas is drawn the formula disintegrating apparatus, is sprayed disintegrating apparatus or high pressure homogenizing equipment, pulverizes commercially available carbonaceous mesophase spherules, to form median size (D
50) the pulverizing powder of 1 μ m to 10 μ m.In another example, the median size (D of aforesaid pulverizing powder
50) be 3 μ m to 8 μ m.In another example, also can make the median size (D of aforesaid pulverizing powder
50) be about 5 μ m.
In this explanation is that the median size of pulverizing powder of the present invention is 1 μ m to 10 μ m or 3 μ m to 8 μ m or 5 μ m, helps to form fine and close green compact.If it is excessive to pulverize the median size of powder, formed green compact easily have than macrovoid, and then affect the density of the follow-up isotropy carbonaceous material that makes.If it is too small to pulverize the median size of powder, then increase time and the cost of pulverising step.
Generally speaking, (β-resin), it is had well from sintering characteristic does the green compact moulding through the cold isostatic pressing that waits to the spherome surface of carbonaceous mesophase spherules with an amount of β-resin, after the carbonization of green compact process, the graphitization processing, can prepare high-density isotropy carbonaceous material.Wherein, carbonaceous mesophase spherules has toluene insoluble composition (toluene insoluble, be designated hereinafter simply as TI) and quinoline non-soluble composition (quinoline insoluble, be designated hereinafter simply as QI), and β-resin refers to be insoluble to toluene but the composition that 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 in this explanation be, because the β-resin content of the carbonaceous mesophase spherules that the present invention uses is extremely low, by the pulverizing powder of its gained when follow-up carbonization and the graphitization processing, can avoid discharging a large amount of volatile components, and then the surface that solves the isotropy carbonaceous material of follow-up gained, do not have crack or defective and surperficial incomplete problem.
If β-resin content is lower than 0.1 weight percent (wt%), then aforesaid pulverizing powder is when follow-up carbonizing treatment, and it is not good from sintering (self-sintering) property, is not easy to form complete isotropy carbonaceous material.If β-resin content is greater than 2.0wt%, then aforesaid pulverizing powder when follow-up carbonization and graphitization processing, the problem that the volatile component that carbosphere overflows can cause the isotropy carbonaceous material of follow-up gained the crack to be arranged easily or break.
Then, shown in step 103, utilize the cold isostatic pressing that waits to carry out mold pressing the aforementioned pulverizing powder that does not add any binding agent, to form green compact.In this embodiment, aforesaid cold isostatic pressing such as grade is that the pulverizing powder that is opposite in the rubber mold applies 500kg/cm
2To 3000kg/cm
2Larger forming pressure reach 1 minute to 10 minutes.In another example, the aforesaid cold isostatic pressing that waits is to apply 800kg/cm to pulverizing powder
2To 2000kg/cm
2Larger forming pressure reach 3 minutes to 7 minutes
Then, shown in step 105, in the presence of the first protective atmosphere, aforesaid green compact are carried out carbonizing treatment, and form char-forming material.In an example, aforesaid the first protective atmosphere is nitrogen, argon gas, helium or above-mentioned arbitrary combination.In another example, aforesaid the first protective atmosphere is nitrogen.
In step 105, aforesaid carbonizing treatment be with per hour 5.0 ℃ (℃/hr) to the first average temperature rise rate of 8.0 ℃/hr, aforesaid green compact be heated to 900 ℃ to 1100 ℃ of temperature but do not hold temperature.In other example, aforesaid carbonizing treatment can also 6.0 ℃/the first average temperature rise rate of hr to 7.0 ℃/hr, green compact are heated to 1000 ℃ of temperature but do not hold temperature.
Afterwards, shown in step 107, in the presence of the second protective atmosphere, aforesaid char-forming material is carried out a graphitization processing, form by this isotropy carbonaceous material.In an example, aforesaid the second protective atmosphere is nitrogen, argon gas, helium or above-mentioned arbitrary combination.
In step 107, aforesaid graphitization processing is the second average temperature rise rate with 5.0 ℃/min to 8.0 ℃/min, aforesaid char-forming material is heated to 2500 ℃ to 3000 ℃ of temperature and held temperature 30 minutes to 90 minutes.In another example, aforesaid graphite treatment is the second average temperature rise rate with 6.0 ℃/min to 7.0 ℃/min, aforesaid char-forming material is heated to 2750 ℃ of temperature and held temperature 30 minutes to 90 minutes.
Between aforesaid carbonizing treatment and graphitization processing, or after the graphitization processing, the more alternative cooling step that carries out.Profess it, between aforesaid carbonizing treatment and graphitization processing, alternative was carried out the first natural cooling step, is not using any cooling apparatus, and made the temperature of aforesaid char-forming material be down to 25 ℃ to 40 ℃ in 45 hours to 50 hours.
In addition, after graphitization processing, the more alternative the second nature cooling step that carries out is not using any cooling apparatus to make the temperature of aforesaid isotropy carbonaceous 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 isotropy carbonaceous material of gained finer and close and surperficial perfect sunken.
In this explanation be, above-mentioned alleged " isotropy carbonaceous material " refers to the high-density graphite material that utilizes aforesaid method to make, its surface is complete and does not have defective, and this isotropy carbonaceous material is less than 10% in the difference of appointing the two of the thermal expansivity of X-axis, Y-axis and Z axis, represents it and has better isotropy.Secondly, the density of this isotropy carbonaceous 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 carbonaceous 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 carbonaceous material of the present invention is in the situation that need not add any binding agent, directly will pulverize the pulverizing powder of carbonaceous mesophase spherules gained, utilize the cold isostatic pressing that waits to be molded into green compact, can shorten effectively that green compact are follow-up to carry out the treatment time of carbonization and improve yield, method therefore of the present invention get rid of carry out known dipping, the processing procedure such as roasting to be to mend a split again.
Because the not only environmental protection and energy saving of manufacture method of isotropy carbonaceous material of the present invention, and the isotropy carbonaceous material of gained has better isotropy, its surface is perfect falls into, significantly promote again its machinery, calorifics and electrical properties, and then be applied to enlarge its industry and utilize scope and increase economic worth.For example, the isotropy carbonaceous 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 is not to limit the present invention, and have in the technology of the present invention field and usually know the knowledgeable, without departing from the spirit and scope of the present invention, when being used for a variety of modifications and variations.
Preparation isotropy carbonaceous material
Embodiment 1
At first, (TI is that 99.0%, QI is 98.6%, median size (D with carbonaceous mesophase spherules G
50) be 24 μ m; China Steel Chemical Co., Ltd.; A-1), utilizing gas to draw formula disintegrating apparatus (ALG-2, Ling Guang industrial, Taiwan) pulverizes.Utilize particle size analyzer (Multisizer
TM3, Beckman Coulter, Inc., U.S.A.) analyze the median size (D after carbonaceous mesophase spherules is pulverized
50) be about 5 μ m.Wherein, the basic document of carbonaceous mesophase spherules G is listed in table 1.
Then, with the above-mentioned carbonaceous mesophase spherules through pulverizing of 402 grams, filling is wherein pulverized the pack height of powder in mould and is about 140mm in the cylindric rubber mold (side thickness of die 1.0mm) of internal diameter 76mm.On the mould lid after the serum cap compacting of homogeneity, carry out shrink-wrap (for example, for example utilizing, electric adhesive plaster twines consolidation), avoiding in equal press operation process such as cold grade, fluid under pressure is accidentally invaded in the mould and is polluted.
The above-mentioned mould that contains carbonaceous mesophase spherules places cold grade all to be installed with in standby (CL4.5-22-30, Nikkiso Co., Ltd., Japan), is forced into about Isosorbide-5-Nitrae 00kg/cm
2And under this pressure, kept about 5 minutes.Afterwards, pressure release is taken out the cylindric green compact of compression moulding to normal pressure from rubber mold, and wherein the diameter of these green compact is 60mm, and length is 109mm.
Then, aforementioned green compact are put into general commercially available atmosphere furnace, the first protective atmosphere for example nitrogen in the presence of, with the first average temperature rise rate of 6.55 ℃/hr per hour, aforesaid green compact are heated to 1000 ℃ and do not hold temperature by room temperature (about 30 ℃).Afterwards, carry out the first natural cooling step, not using any cooling apparatus and in about 48 hours, making body of heater naturally be cooled to 25 ℃ to 40 ℃, so carry out the char-forming material of carbonizing treatment gained, its density is 1.62g/cm
3
Then; aforementioned char-forming material is put into high-temperature vacuum furnace (Vacuum Furnace Type 45; Centorr Vacuum Industries; Inc.) in; the second protective atmosphere for example argon gas in the presence of; with the second average temperature rise rate of 6.7 ℃/min, with aforesaid char-forming material by room temperature (about 30 ℃) be heated to 2750 ℃ and hold the temperature 1 hour, to carry out graphitization processing.Afterwards, carry out the second nature cooling step, do not using under any cooling apparatus, make body of heater naturally be cooled to 25 ℃ to 40 ℃, wherein the graphitized material of gained is the isotropy carbonaceous material.The density of the isotropy carbonaceous material of embodiment 1 gained is 1.84g/cm
3, shore hardness is 58, its surface is complete and do not have a defective, and this isotropy carbonaceous material in the thermal expansivity difference therebetween of all directions for (its thermal expansivity in X, Y, Z direction is 6.0 * 10 less than 10%
-6K
-1To 6.1 * 10
-6K
-1).
The isotropy carbonaceous material of embodiment 1 gained further detects its folding strength, ultimate compression strength, heat-conduction coefficient 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 2
Embodiment 2 uses method and the process conditions identical with embodiment 1.Different is that embodiment 2 is that (TI is that 96.9%, QI is 95.0% to use carbonaceous mesophase spherules M, median size (D
50) be 24 μ m; China Steel Chemical Co., Ltd.; A-2) as raw material, its basic document is also listed in table 1.
The density of the char-forming material of embodiment 2 gained is 1.74g/cm
3, and the density of the isotropy carbonaceous material of gained is 1.93g/cm
3, shore hardness is 85, its surface is complete and do not have a defective such as crack, and this isotropy carbonaceous material in the difference of appointing the two of the thermal expansivity of all directions for (its coefficient of expansion hot in nature in X, Y, Z direction is 6.8 * 10 less than 10%
-6K
-1To 7.2 * 10
-6K
-1).
The isotropy carbonaceous material of embodiment 2 gained further detects its folding strength, ultimate compression strength, heat-conduction coefficient and specific resistance, and it detects methods involving, and the details will be described later, and its result is as shown in table 2.
Comparative example 1 is to comparative example 3
Comparative example 1 to comparative example 3 is to use the method identical with embodiment 1 to carry out isostactic pressing, carbonization and the graphitization processing such as cold.Different is, comparative example 1 to comparative example 3 is to use not add any binding agent and (TI is that 99.4%, QI is 98.9%, median size (D without the carbonaceous mesophase spherules B that pulverizes
50) be 21 μ m; China Steel Chemical Co., Ltd.; A-3) as raw material, its basic document is also listed in table 1.
In the cylindric rubber mold (side thickness of die 1.0mm) of internal diameter 71mm, its pack height in mould is about 123mm without the carbonaceous mesophase spherules filling of pulverizing.Green compact after the isostactic pressing such as cold, wherein the diameter of the green compact of comparative example 1 is 59mm, length is 108mm; The diameter of the green compact of comparative example 2 is 58mm, and length is 101mm; The diameter of the green compact of comparative example 3 is 60mm, and length is 105mm.
Secondly, comparative example 1 also is different from embodiment 1 to the isostactic pressing such as cold of comparative example 3, the process conditions of carbonizing treatment, and its process conditions is listed in table 2.
Table 1: the master data of carbonaceous mesophase spherules
The usefulness of assessment isotropy carbonaceous material
1. appearance
Char-forming material and the isotropy carbonaceous material of embodiment 1 to embodiment 2 gained, and comparative example 1 further utilizes its surperficial integrity of visual observations to the char-forming material of comparative example 3 gained, and according to following criterion evaluation, its result is as shown in table 2:
Zero: the surface is complete and do not have defective or a crack
╳: the surface is imperfect and have a multiple tracks crack
╳ ╳: the surface is imperfect and have a serious crack of multiple tracks
Can be learnt by table 2, char-forming material and the isotropy carbonaceous material of embodiment 1 to embodiment 2 gained, its surface is complete and do not have defective or a crack.In comparison, comparative example 1 is to the char-forming material of comparative example 3 gained, and its surface has the crack.In addition, learnt by the actually operating experience that the crannied char-forming material of tool is through the graphitization processing of high temperature more, the crack on the green compact will more shape be serious, so can't make complete isotropy carbonaceous material.
2. physical strength
Secondly, the isotropy carbonaceous material of embodiment 1 to embodiment 2 gained carries out the assessment of physical strength, and 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 Sintech 10/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 testing method and Sintech 10/GL material-testing machine (the MTS Test Systems Co. of ASTM C695, U.S.A.) measure ultimate compression strength, its result is as shown in table 2.
Can be learnt by table 2, char-forming material and the isotropy carbonaceous material of embodiment 1 to embodiment 2 gained, its shore hardness is 58 to 85, and folding strength is 28MPa to 44MPa, and ultimate compression strength is 69MPa to 120MPa.Because comparative example 1 to comparative example 3 can't make complete char-forming material, thus do not carry out graphitization processing, also so measurement character do not arranged.
3. calorifics and electrical properties
Moreover, the isotropy carbonaceous material of embodiment 1 to embodiment 2 gained, carry out the assessment of calorifics and electrical properties, it is to utilize the testing method of ASTM C714 and ASTM E228 to measure heat-conduction coefficient and thermal expansivity, and utilizing the testing method measuring resistance coefficient of ASTM C611, its result is as shown in table 2.
Can be learnt by table 2, char-forming material and the isotropy carbonaceous material of embodiment 1 to embodiment 2 gained, its heat-conduction coefficient is 64W/mK to 40W/mK, thermal expansivity is 6.0 * 10
-6/ K to 7.2 * 10
-6/ K, specific resistance are 7.0 μ Ω m to 10.8 μ Ω m.
Result by table 2 can learn, embodiment 1 to 2 after the isostatic pressing such as pulverizing and cold and being molded into green compact, can shorten the follow-up carbonizing treatment time of carrying out with the carbonaceous mesophase spherules that do not add any binding agent, really can reach purpose of the present invention.
Table 2
Annotate: not test of N.D. representative
Only what this need replenish be, isotropy carbonaceous material of the present invention and manufacture method thereof also can use other carbonaceous mesophase spherules, other carbonizing treatment condition, other graphitization processing conditioned disjunction miscellaneous equipment etc. to carry out only for illustrating in other embodiments.For example, in the technical field of the invention any have know that usually the knowledgeable should understand easily, when green compact size during greater than the cylindric green compact size of the above embodiments of the present invention, above-mentioned carbonization and graphitization processing can be used the average temperature rise rate less than the above embodiment of the present invention, so the char-forming material of gained have complete, fissureless surface with the isotropy carbonaceous material beginning and isotropy good.Therefore, the process conditions of carbonization of the present invention and graphitization processing also visual green compact physical size size or body of heater varies in size, and adjusts to some extent.This by in the technical field of the invention any have know that usually the knowledgeable is known, so do not give unnecessary details in addition.
Comprehensive speech, by the invention described above embodiment as can be known, use isotropy carbonaceous material of the present invention and manufacture method thereof, the carbonaceous mesophase spherules that its advantage is not add any binding agent is after the isostatic pressing such as pulverizing and cold and being molded into green compact, not only can shorten follow-up carrying out carbonization and graphited treatment time, and the surface of the isotropy carbonaceous material of gained is complete, leakless 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 to limit the present invention; the persond having ordinary knowledge in the technical field of the present invention; without departing from the spirit and scope of the present invention; when can being used for a variety of modifications and variations, so protection scope of the present invention is as the criterion when looking accompanying the scope that claims define.
Claims (10)
1. the manufacture method of an isotropy carbonaceous material comprises:
Carbonaceous mesophase spherules is pulverized, pulverized powder to form one of median size 1 μ m to 10 μ m, wherein said carbonaceous mesophase spherules has a toluene insoluble composition TI and a quinoline non-soluble composition QI, and the difference of described TI and QI is 0.1wt% to 2.0wt%;
With described pulverizing powder, carry out mold pressing via a cold isostatic pressing that waits, to form green compact;
In the presence of one first protective atmosphere, described green compact are carried out a carbonizing treatment, and form a char-forming material; And
In the presence of one second protective atmosphere; described char-forming material is carried out a graphitization processing; form by this described isotropy carbonaceous material; arbitrary surface of wherein said isotropy carbonaceous material is perfect falling into, and described isotropy carbonaceous material is less than 10% in the difference of appointing the two of the thermal expansivity of X-axis, Y-axis and Z axis.
2. the manufacture method of isotropy carbonaceous material as claimed in claim 1, wherein said cold to wait isostatic pressing be that described pulverizing powder is applied 500kg/cm
2To 3000kg/cm
2A larger forming pressure to form green compact.
3. the manufacture method of isotropy carbonaceous material as claimed in claim 1, wherein said cold to wait isostatic pressing be that described pulverizing powder is applied 800kg/cm
2To 2000kg/cm
2A larger forming pressure to form green compact.
4. the manufacture method of isotropy carbonaceous material as claimed in claim 1, the median size of wherein said pulverizing powder is 3 μ m to 8 μ m.
5. the manufacture method of isotropy carbonaceous material as claimed in claim 1, the difference of wherein said TI and QI is 0.2wt% to 2.0wt%.
6. the manufacture method of isotropy carbonaceous material as claimed in claim 1, the difference of wherein said TI and QI is 0.4wt% to 2.0wt%.
7. the manufacture method of isotropy carbonaceous material as claimed in claim 1, wherein said the first protective atmosphere is nitrogen, argon gas, helium or above-mentioned arbitrary combination.
8. the manufacture method of isotropy carbonaceous material as claimed in claim 1, wherein said the second protective atmosphere is nitrogen, argon gas, helium or above-mentioned arbitrary combination.
9. isotropy carbonaceous material, it is to use obtainedly such as each described method in the claim 1 to 8, wherein said isotropy carbonaceous material has 1.75g/cm
3To 1.95g/cm
3Density and 50 to 90 shore hardness.
10. isotropy carbonaceous material as claimed in claim 9, wherein said isotropy carbonaceous material has 1.84g/cm
3To 1.93g/cm
3Density and 58 to 85 shore hardness.
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| CN103570008A (en) * | 2012-08-09 | 2014-02-12 | 中国钢铁股份有限公司 | Isotropic graphite material and method for producing same |
| CN106478102A (en) * | 2016-11-02 | 2017-03-08 | 中国科学院上海应用物理研究所 | High-density ultra-fine pore structure graphite production processes |
| CN108610049A (en) * | 2016-12-09 | 2018-10-02 | 中国钢铁股份有限公司 | Isotropic graphite material, manufacturing method and its application |
| CN109355674A (en) * | 2018-10-19 | 2019-02-19 | 核工业第八研究所 | A kind of carbon anode for fluorine production plate preparation method |
| CN117447204A (en) * | 2023-12-22 | 2024-01-26 | 成都中超碳素科技有限公司 | Preparation method of mechanical carbon material |
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| CN110655413B (en) * | 2019-09-18 | 2022-03-04 | 济宁碳素集团有限公司 | Preparation method of isotropic graphite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570008A (en) * | 2012-08-09 | 2014-02-12 | 中国钢铁股份有限公司 | Isotropic graphite material and method for producing same |
| CN103570008B (en) * | 2012-08-09 | 2015-10-28 | 中国钢铁股份有限公司 | Isotropic graphite material and method for producing same |
| CN106478102A (en) * | 2016-11-02 | 2017-03-08 | 中国科学院上海应用物理研究所 | High-density ultra-fine pore structure graphite production processes |
| CN108610049A (en) * | 2016-12-09 | 2018-10-02 | 中国钢铁股份有限公司 | Isotropic graphite material, manufacturing method and its application |
| CN108610049B (en) * | 2016-12-09 | 2021-03-26 | 中国钢铁股份有限公司 | Isotropic graphite material, method for the production thereof and use thereof |
| CN109355674A (en) * | 2018-10-19 | 2019-02-19 | 核工业第八研究所 | A kind of carbon anode for fluorine production plate preparation method |
| CN117447204A (en) * | 2023-12-22 | 2024-01-26 | 成都中超碳素科技有限公司 | Preparation method of mechanical carbon material |
| CN117447204B (en) * | 2023-12-22 | 2024-03-15 | 成都中超碳素科技有限公司 | Preparation method of mechanical carbon material |
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| TW201343547A (en) | 2013-11-01 |
| TWI504563B (en) | 2015-10-21 |
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