CN103373720B - Isotropic carbonaceous material and method for producing same - Google Patents
Isotropic carbonaceous material and method for producing same Download PDFInfo
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- CN103373720B CN103373720B CN201210320237.9A CN201210320237A CN103373720B CN 103373720 B CN103373720 B CN 103373720B CN 201210320237 A CN201210320237 A CN 201210320237A CN 103373720 B CN103373720 B CN 103373720B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 238000000034 method Methods 0.000 claims abstract description 52
- 238000010298 pulverizing process Methods 0.000 claims description 32
- 238000012545 processing Methods 0.000 claims description 30
- 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 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 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
- 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
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 abstract description 14
- 239000011230 binding agent Substances 0.000 abstract description 10
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- 230000000052 comparative effect Effects 0.000 description 17
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- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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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 relate to especially and a kind ofly utilize carbonaceous mesophase spherules but do not add isotropy carbonaceous material and the manufacture method thereof of any binding agent.
Background technology
Carbonaceous material is mainly formed with carbon, by different manufacture method, can obtain unique carbon material of the different qualities such as amorphous carbon, graphite system carbon, thermally decomposed carbon and carbon fibre.Wherein, isotropy graphite (isotropic graphite) material has high temperature resistant, conduction, heat conduction, tool oilness, porousness and the performance such as anticorrosive, is recently widely used in each industries such as metallurgy, machinery and semi-conductor.Traditional isotropy graphite processing procedure, general use coke (coke) is as raw material, after mixing with coal tar pitch (coal tar pitch), inject extrusion molding in mould, then under non-oxide condition, be heated to about 1000 DEG C, form the pertusate agraphitic carbon of tool (amorphous carbon).Afterwards, then through impregnating pitch and roasting again, so carry out repeatedly, to fill up hole.Subsequently, recycling is heat-treated to 2500 DEG C to 3000 DEG C, makes agraphitic carbon form highdensity graphite.
The developing rapidly of energy storage material in recent years, therefore also increases fast for high-density, high strength, high purity and the Isotropic graphite material demand of good processability.But traditional isotropy graphite processing procedure is complicated, and the quality of item Chang Wufa of gained satisfies the demands.Therefore, carbonaceous mesophase spherules (the mesocarbon microbeads that utilization has self sintering (self-sintering) is recently developed; MCMBs), it does not need the steps such as mixing, kneading and pulverizing, also do not need again through impregnating pitch and again roasting supervisor to fill up hole, high strength, high-density, highly purified graphite carbon material can be manufactured, not only significantly improve graphite mechanical properties, also simplify the Production Flow Chart of isotropy graphite complexity.Above-mentioned processing procedure and the pertinent literature of material can consult relevant front case, as U.S. Patent Bulletin US 5,525,276, US 5,547,654, US 5,609,800, US4,929,404, and TaiWan, China patent announcement TW 326027, TW 379202, TW424079 etc., one be listed as reference herein at this.
But still there is following problem in the processing procedure of above-mentioned graphite carbon material.For example, above-mentioned processing procedure, when utilizing carbonaceous mesophase spherules to form green compact, when follow-up carbonizing treatment, easily discharges a large amount of volatile components, and causes the surface of the carbon material of follow-up gained, the problem producing crack or break.Secondly, above-mentioned carbonization processing procedure, to carry out at vacuum state (TaiWan, China patent as escribed above is contained), can cause the significantly lifting of cost when volume production.If in order to avoid the problem of volatile component loss when carbonization and graphitization processing, and slow down the temperature rise rate of carbonizing treatment, carbonizing treatment time-histories will be made more tediously long and more consume energy.
Combine speech, the longer and power consumption of fabrication process time of known isotropy graphite carbon material, and the surface of the graphite carbon material of gained easily there is crack even to break, and then limit its scope applied.
Therefore, need the manufacture method that a kind of isotropy graphite carbon material is provided badly, have the problem of crack or defect with the surface of the graphite carbon material effectively solving known processing procedure gained.
Summary of the invention
Therefore, one aspect of the present invention is the manufacture method providing a kind of isotropy carbonaceous material, its be by the carbonaceous mesophase spherules not adding any binding agent after the isostatic pressing (cold isostatic pressing) such as pulverizing and cold and being molded into green compact, can shorten and follow-uply carry out the carbonizing treatment time.
Secondly, another aspect of the present invention is to provide a kind of isotropy carbonaceous material, and it utilizes obtained by aforesaid method, and the surface of the isotropy carbonaceous material of gained is perfectly fall into and have good machinery, calorifics and 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 first pulverizes carbonaceous mesophase spherules and after forming a pulverizing powder, utilized by the pulverizing powder not adding any binding agent the cold isostatic pressing that waits to carry out mold pressing, to form green compact.Then, green compact are carried out carbonization and graphitization processing, and forms isotropy carbonaceous material.
In the above-described embodiments, aforesaid pulverising step makes the median size of the carbonaceous mesophase spherules pulverizing powder of gained after crushed be 1 μm to 10 μm, wherein aforesaid carbonaceous mesophase spherules has toluene insoluble composition (toluene insoluble, and quinoline non-soluble composition (quinoline insoluble TI), and the difference of TI and QI is that 0.1 weight percent (wt%) is to 2.0wt% QI).
In the above-described embodiments, in aforesaid cold isostatic pressing such as grade, it applies 500kg/cm to above-mentioned pulverizing powder
2to 3000kg/cm
2larger forming pressure to form green compact.In other example, the aforesaid cold isostatic pressing that waits applies 800kg/cm to above-mentioned pulverizing powder
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 isotropy carbonaceous material.In illustrating one, each surface of above-mentioned isotropy carbonaceous material is complete and does not have a crack, this isotropy carbonaceous material in the difference times therebetween of the thermal expansivity of X-axis, Y-axis and Z axis for being less than 10%.
According to one embodiment of the invention, the median size of above-mentioned pulverizing powder is 3 μm to 8 μm.
According to one embodiment of the invention, the difference of above-mentioned TI and QI is 0.2wt% to 2.0wt%.
According to one embodiment of the invention, above-mentioned green compact carry out carbonization and graphitization processing protective atmosphere used is nitrogen, argon gas, helium or above-mentioned arbitrary combination.
According to a further aspect in the invention, a kind of isotropy carbonaceous material is proposed, its be utilize above-mentioned isotropy carbonaceous material manufacture method obtained by, wherein the isotropy carbonaceous material of gained has 1.75g/cm
3to 1.95g/cm
3density and 50 to 90 shore hardness.
Apply isotropy carbonaceous material of the present invention and manufacture method thereof, its be by the carbonaceous mesophase spherules not adding any binding agent after the isostatic pressing such as pulverizing and cold and being molded into green compact, not only can shorten and follow-uply carry out the carbonizing treatment time, and the surface of the isotropy carbonaceous material of gained is complete, zero defect and isotropy is good, there is again good good machinery, calorifics and electrical properties.
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 is the partial process view of the manufacture method illustrating isotropy carbonaceous material according to an embodiment of the invention;
Wherein, main element nomenclature:
100: method
101: pulverize carbonaceous mesophase spherules to form the step pulverizing powder
103: will powder be pulverized via the cold step waiting 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 present invention.But be understandable that, embodiment provides many applicable inventive concepts, and it may be implemented in certain content miscellaneous.The specific embodiment discussed only for illustrating, and is not used to limit scope of the present invention.
The manufacture method of isotropy carbonaceous material of the present invention can utilize following method to obtain.Refer to Fig. 1, it is the partial process view of the manufacture method illustrating isotropy carbonaceous material according to an embodiment of the invention.In one embodiment, first as shown in step 101, utilize such as commercially available ball mill pulverizing equipment, gas to draw formula disintegrating apparatus, spray disintegrating apparatus or high pressure homogenizing equipment, pulverize commercially available carbonaceous mesophase spherules, to form median size (D
50) the pulverizing powder of 1 μm to 10 μm.In another example, the median size (D of aforesaid pulverizing powder
50) be 3 μm to 8 μm.In another example, also can make the median size (D of aforesaid pulverizing powder
50) be about 5 μm.
Described herein, the median size of pulverizing powder of the present invention is 1 μm to 10 μm or 3 μm to 8 μm or 5 μm, contributes to forming finer and close green compact.If the median size pulverizing powder is excessive, the green compact formed easily have comparatively macrovoid, and then affect the density of follow-up obtained isotropy carbonaceous material.If the median size pulverizing powder is too small, then increase time and the cost of pulverising step.
Generally speaking, the spherome surface of carbonaceous mesophase spherules, with appropriate β-resin (β-resin), makes it have good in sintering characteristic, makes green compact shaping through cold isostatic pressing such as grade, green compact, after carbonization, graphitization processing, can prepare high-density isotropy carbonaceous material.Wherein, carbonaceous mesophase spherules has toluene insoluble composition (toluene insoluble, hereinafter referred to as TI) and quinoline non-soluble composition (quinoline insoluble, hereinafter referred to as QI), and β-resin refers to and is insoluble to toluene but the composition being dissolved in quinoline, therefore the content of β-resin is the difference being defined as TI and QI.
β-the resin content being 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, because the β-resin content of the carbonaceous mesophase spherules of the present invention's use is extremely low, by the pulverizing powder of its gained when follow-up carbonization and graphitization processing, can avoid discharging a large amount of volatile components, and then solve the surface of isotropy carbonaceous material of follow-up gained, do not have crack or defect 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 is 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 easily to have crack or break.
Then, as shown in step 103, the cold isostatic pressing that waits is utilized by the aforementioned pulverizing powder not adding any binding agent to carry out mold pressing, to form green compact.In this embodiment, the aforesaid cold isostatic pressing that waits is that the pulverizing powder be opposite in 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 applies 800kg/cm to pulverizing powder
2to 2000kg/cm
2larger forming pressure reach 3 minutes to 7 minutes
Then, as shown, under the existence of the first protective atmosphere, aforesaid green compact are carried out carbonizing treatment, and forms char-forming material.In an example, aforesaid first protective atmosphere is nitrogen, argon gas, helium or above-mentioned arbitrary combination.In another example, aforesaid first protective atmosphere is nitrogen.
In step 105, aforesaid carbonizing treatment be with 5.0 DEG C per hour (DEG C/hr) to first average heating rate of 8.0 DEG C/hr, aforesaid green compact are heated to temperature 900 DEG C to 1100 DEG C and do not hold temperature.In other example, aforesaid carbonizing treatment can also first average heating rate of 6.0 DEG C/hr to 7.0 DEG C/hr, green compact is heated to temperature 1000 DEG C but does not hold temperature.
Afterwards, as shown in step 107, under the existence of the second protective atmosphere, aforesaid char-forming material is carried out a graphitization processing, form isotropy carbonaceous material by this.In an example, aforesaid second protective atmosphere is nitrogen, argon gas, helium or above-mentioned arbitrary combination.
In step 107, aforesaid graphitization processing is with second average heating rate of 5.0 DEG C/min to 8.0 DEG C/min, aforesaid char-forming material is heated to temperature 2500 DEG C to 3000 DEG C and holds temperature 30 minutes to 90 minutes.In another example, aforesaid graphite treatment is with second average heating rate of 6.0 DEG C/min to 7.0 DEG C/min, aforesaid char-forming material is heated to temperature 2750 DEG C and holds temperature 30 minutes to 90 minutes.
Between aforesaid carbonizing treatment and graphitization processing, or after graphitization processing, more alternatively carry out cooling step.Profess it, between aforesaid carbonizing treatment and graphitization processing, alternative carries out the first Temperature fall step, is not using any cooling apparatus, and littlely makes the temperature of aforesaid char-forming material be down to 25 DEG C to 40 DEG C up to 50 hours in 45.
In addition, after graphitization processing, more alternatively carrying out the second nature cooling step, making the temperature of aforesaid isotropy carbonaceous material be down to 25 DEG C to 40 DEG C not using any cooling apparatus.Aforementionedly carry out the first Temperature fall step and/or the second nature cooling step, the isotropy carbonaceous material of gained can be made finer and close and surperficially perfectly to fall into.
Described hereinly be, above-mentioned alleged " isotropy carbonaceous material " refers to the high-density graphite material utilizing aforesaid method obtained, its surface is complete and does not have a defect, and this isotropy carbonaceous material in X-axis, Y-axis and Z axis thermal expansivity appoint the two difference for being less than 10%, represent it and there is preferably 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 when adding any binding agent, directly the pulverizing powder of carbonaceous mesophase spherules gained will be pulverized, the cold isostatic pressing that waits is utilized to be molded into green compact, effectively can shorten that green compact are follow-up to carry out the treatment time of carbonization and improve yield, therefore method of the present invention is got rid of and is carried out the processing procedures such as known dipping, again roasting to mend a split.
Due to the manufacture method not only environmental protection and energy saving of isotropy carbonaceous material of the present invention, and the isotropy carbonaceous material of gained has better isotropy, its surface is perfect sunken, significantly promote again its machinery, calorifics and electrical properties, and then be applied to and expand 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 itself and be not used to limit the present invention, 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.
Prepare isotropy carbonaceous material
Embodiment 1
First, by carbonaceous mesophase spherules G, (TI is 99.0%, QI is 98.6%, median size (D
50) be 24 μm; China Steel Chemical Co., Ltd.; A-1), utilize gas to draw formula disintegrating apparatus (ALG-2, Ling Guang industrial, Taiwan) to pulverize.Utilize particle size analyzer (Multisizer
tM3, Beckman Coulter, Inc., U.S.A.) analyze carbonaceous mesophase spherules pulverize after median size (D
50) be about 5 μm.Wherein, table 1 listed in by the basic document of carbonaceous mesophase spherules G.
Then, by the above-mentioned carbonaceous mesophase spherules through pulverizing of 402 grams, be filled in the cylindric rubber mold (side thickness of die 1.0mm) of internal diameter 76mm, wherein pulverizing the pack height of powder in mould is about 140mm.In mould lid homogeneity serum cap compacting after, carry out shrink-wrap (such as, utilizing such as electrically adhesive plaster to be wound around consolidation), to avoid in equal press operation process such as cold grade, fluid under pressure accidentally invades in mould and pollutes.
The above-mentioned mould containing 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 about Isosorbide-5-Nitrae 00kg/cm
2and under this pressure, maintain about 5 minutes.Afterwards, pressure release, to normal pressure, takes out the cylindric green compact of compression moulding from rubber mold, and wherein the diameter of these green compact is 60mm, and length is 109mm.
Then; aforementioned green compact are put into generally commercially available atmosphere furnace; under the existence of the first protective atmosphere such as nitrogen, with first average heating rate of 6.55 DEG C/hr per hour, aforesaid green compact are heated to 1000 DEG C by room temperature (about 30 DEG C) and are not held temperature.Afterwards, carry out the first Temperature fall step, do not using any cooling apparatus and in about 48 hours, make body of heater Temperature fall to 25 DEG C to 40 DEG C, 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; under the existence of the second protective atmosphere such as argon gas; with second average heating rate of 6.7 DEG C/min, aforesaid char-forming material is heated to 2750 DEG C by room temperature (about 30 DEG C) and holds 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 Temperature fall to 25 DEG C to 40 DEG C, wherein the graphitized material of gained is isotropy carbonaceous material.The density of the isotropy carbonaceous material of embodiment 1 gained is 1.84g/cm
3, shore hardness is 58, and its surface is complete and does not have a defect, and this isotropy carbonaceous material in the thermal expansivity difference therebetween of all directions, in order to be less than 10%, (its thermal expansivity in X, Y, Z-direction is 6.0 × 10
-6k
-1to 6.1 × 10
-6k
-1).
The isotropy carbonaceous material of embodiment 1 gained detects its folding strength, ultimate compression strength, heat-conduction coefficient and specific resistance further, 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 the method identical with embodiment 1 and process conditions.Unlike, embodiment 2 is that (TI is 96.9%, QI is 95.0% to use carbonaceous mesophase spherules M, median size (D
50) be 24 μm; China Steel Chemical Co., Ltd.; A-2) as raw material, its basic document also lists 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, and its surface is complete and does not have defects such as crack, and this isotropy carbonaceous material in the two the difference of appointing of the thermal expansivity of all directions, in order to be less than 10%, (its linear thermal expansion coefficient in X, Y, Z-direction is 6.8 × 10
-6k
-1to 7.2 × 10
-6k
-1).
The isotropy carbonaceous material of embodiment 2 gained detects its folding strength, ultimate compression strength, heat-conduction coefficient and specific resistance further, and it detects methods involving, and the details will be described later, and its result is as shown in table 2.
Comparative example 1 to comparative example 3
Comparative example 1 to comparative example 3 uses the method identical with embodiment 1 to carry out isostactic pressing, carbonization and the graphitization processing such as cold.Use not add any binding agent and (TI is 99.4%, QI is 98.9%, median size (D without the carbonaceous mesophase spherules B pulverized unlike, comparative example 1 to comparative example 3
50) be 21 μm; China Steel Chemical Co., Ltd.; A-3) as raw material, its basic document also lists in table 1.
Be filled in the cylindric rubber mold (side thickness of die 1.0mm) of internal diameter 71mm without the carbonaceous mesophase spherules pulverized, its pack height in mould is about 123mm.Green compact after the isostactic pressing such as cold, wherein the diameter of the green compact of comparative example 1 is 59mm, and 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, the isostactic pressing such as cold of comparative example 1 to comparative example 3, the process conditions of carbonizing treatment are also different from embodiment 1, and its process conditions lists in table 2.
Table 1: the master data of carbonaceous mesophase spherules
The usefulness of assessment isotropy carbonaceous material
1. appearance
The char-forming material of embodiment 1 to embodiment 2 gained and isotropy carbonaceous material, and the char-forming material of comparative example 1 to comparative example 3 gained, utilize the integrity on its surface of visual observations further, and according to following criterion evaluation, its result is as shown in table 2:
Zero: surface is complete and do not have defect or a crack
╳: surface is imperfect and have multiple tracks crack
╳ ╳: surface is imperfect and have the serious crack of multiple tracks
Can be learnt by table 2, the char-forming material of embodiment 1 to embodiment 2 gained and isotropy carbonaceous material, its surface is complete and do not have defect or a crack.In comparison, the char-forming material of comparative example 1 to comparative example 3 gained, its surface has crack.In addition, learnt by actually operating experience, the crannied char-forming material of tool is through graphitization processing at higher temperature, and the crack on green compact will more shape be serious, so cannot obtain 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 utilizes commercially available shore hardness tester (Shore Hardness Tester, Type D, Sato Seiki Co., Japan) measure 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.) folding strength is measured, 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, the char-forming material of embodiment 1 to embodiment 2 gained and isotropy carbonaceous material, 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 cannot obtain complete char-forming material, therefore do not carry out graphitization processing, therefore do not have measurement character yet.
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 utilizes 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, the char-forming material of embodiment 1 to embodiment 2 gained and isotropy carbonaceous material, its heat-conduction coefficient is 64W/mK to 40W/mK, and thermal expansivity is 6.0 × 10
-6/ K to 7.2 × 10
-6/ K, specific resistance is 7.0 μ Ω m to 10.8 μ Ω m.
Can be learnt by the result of table 2, the carbonaceous mesophase spherules not adding any binding agent after the isostatic pressing such as pulverizing and cold and being molded into green compact, can be shortened the follow-up carbonizing treatment time of carrying out, really can reach object of the present invention by embodiment 1 to 2.
Table 2
Note: N.D. representative is not tested
What only need supplement at this is, isotropy carbonaceous material of the present invention and manufacture method thereof are only and illustrate, and other carbonaceous mesophase spherules, other carbonizing treatment condition, other graphitization processing conditioned disjunction miscellaneous equipment etc. also can be used in other embodiments to carry out.For example, in the technical field of the invention any have usually know that the knowledgeable should understand easily, when green compact size is greater than the cylindric green compact size of the above embodiments of the present invention, above-mentioned carbonization and graphitization processing can use the average heating rate less than the above embodiment of the present invention, and the char-forming material of gained like this and isotropy carbonaceous material begin to have complete, fissureless surface and isotropy is 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 in the technical field of the invention any have usually know known by the knowledgeable, therefore separately not repeat.
Comprehensive speech, from the invention described above embodiment, apply isotropy carbonaceous material of the present invention and manufacture method thereof, its advantage is the carbonaceous mesophase spherules not adding any binding agent after the isostatic pressing such as pulverizing and cold and being molded into green compact, not only can shorten and follow-uply carry out carbonization and graphited treatment time, and the surface of the isotropy carbonaceous material of gained is complete, leakless and isotropy is good, more significantly promote its machinery, calorifics and electrical properties, and then increase its industry range of application, improve its economic worth, such as 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 itself and be not used 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, the scope that therefore protection scope of the present invention ought define depending on accompanying claims is as the criterion.
Claims (10)
1. a manufacture method for isotropy carbonaceous material, comprises:
Carbonaceous mesophase spherules is pulverized, powder is pulverized with form median size 1 μm to 10 μm one, wherein said carbonaceous mesophase spherules has an a toluene insoluble composition TI and quinoline non-soluble composition QI, and the difference of described TI and QI is 0.1wt% to 2.0wt%;
By described pulverizing powder, carry out mold pressing, to form green compact via a cold isostatic pressing that waits;
Under the existence of one first protective atmosphere, described green compact are carried out a carbonizing treatment, and forms a char-forming material; And
Under the existence of one second protective atmosphere; described char-forming material is carried out a graphitization processing; form described isotropy carbonaceous material by this; arbitrary surface of wherein said isotropy carbonaceous material is perfect falling into; and described isotropy carbonaceous material in X-axis, Y-axis and Z axis thermal expansivity appoint the two difference for being less than 10%, and the specific resistance of described isotropy carbonaceous material is 7.0 μ Ω m to 10.8 μ Ω m.
2. the manufacture method of isotropy carbonaceous material as claimed in claim 1, the wherein said cold isostatic pressing that waits applies 500kg/cm to described pulverizing powder
2to 3000kg/cm
2a larger forming pressure to form green compact.
3. the manufacture method of isotropy carbonaceous material as claimed in claim 1, the wherein said cold isostatic pressing that waits applies 800kg/cm to described pulverizing powder
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 μm to 8 μm.
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 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 second protective atmosphere is nitrogen, argon gas, helium or above-mentioned arbitrary combination.
9. an isotropy carbonaceous material, it uses obtained by the method according to any one of claim 1 to 8, and 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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| 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 |
| CN110655413B (en) * | 2019-09-18 | 2022-03-04 | 济宁碳素集团有限公司 | Preparation method of isotropic graphite 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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