TW201406651A - Isotropic graphite material and method of producing the same - Google Patents
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本發明是有關於一種等方向性石墨材料及其製造方法，且特別是有關於一種利用中間相碳微球但不添加任何黏結劑之等方向性石墨材料及其製造方法。 The present invention relates to an isotropic graphite material and a method of producing the same, and more particularly to an isotropic graphite material utilizing mesophase carbon microspheres without the addition of any binder and a method of making the same.
石墨材料是碳元素所構成的，藉由不同製造方法，可得到非晶系碳、石墨系碳、熱分解碳及碳纖等不同特性的獨特碳材。其中，等方向性石墨(isotropic graphite)材料具有耐高溫、導電、導熱、潤滑、多孔性、可塑和抗腐蝕等性能，近來廣泛應用於冶金、機械及半導體等各產業。傳統的石墨製程，一般使用焦碳(coke)作為原料，與煤焦瀝青(coal tar pitch)混合後，注入模內擠壓，接著在非氧化的條件下加熱至約1000℃，形成具有孔洞的無定型碳(amorphous carbon)。之後，再經過浸漬瀝青及再燒焙，如此進行多次，以填補孔洞。隨後，再利用熱處理至2500℃至3000℃，使無定型碳形成高密度的石墨。 The graphite material is composed of carbon elements, and different carbon materials, such as amorphous carbon, graphite-based carbon, thermal decomposition carbon, and carbon fiber, can be obtained by different manufacturing methods. Among them, isotropic graphite materials have high temperature resistance, electrical conductivity, thermal conductivity, lubrication, porosity, plasticity and corrosion resistance, and have recently been widely used in various industries such as metallurgy, machinery and semiconductors. Conventional graphite processes generally use coke as a raw material, mixed with coal tar pitch, injected into an in-mold, and then heated to about 1000 ° C under non-oxidizing conditions to form pores. Amorphous carbon. After that, the asphalt is impregnated and re-baked, and this is done several times to fill the holes. Subsequently, heat treatment is further applied to 2500 ° C to 3000 ° C to form amorphous carbon to form high density graphite.
近年來儲能材料的迅速發展，因此對於高密度、高強度、高純度且加工性能好之等方向性石墨材料需求亦快速增加。然而，傳統石墨製程複雜、且所得之製品品質無法滿足需求。因此，近來開發出利用自燒結式(self-sintering)之中間相碳微球(mesocarbon microbeads；MCMBs)，其係不需混合、揉捏及粉碎步驟，亦不需再經過浸漬瀝青及再燒結等程序來填補孔洞，即可製造高強度、高密度、高純 度的石墨碳材，不僅大幅提升了石墨機械性質，亦簡化了等方向性石墨材料複雜的生產流程。上述製程與材料的相關文獻可參閱相關前案，如美國專利公告號US 5,525,276、US 5,547,654、US 5,609,800、US 4,929,404，以及台灣專利公告號TW 326027、TW 379202、TW424079等，在此一併列為本文之參考文獻。 In recent years, the rapid development of energy storage materials has led to a rapid increase in demand for directional graphite materials with high density, high strength, high purity and good processing properties. However, the conventional graphite process is complicated and the quality of the obtained product cannot meet the demand. Therefore, mesocarbon microbeads (MCMBs) using self-sintering have recently been developed, which do not require mixing, kneading, and pulverizing steps, and do not require impregnation of asphalt and re-sintering. Program to fill holes, you can create high strength, high density, high purity The graphite carbon material not only greatly improves the mechanical properties of graphite, but also simplifies the complicated production process of isotropic graphite materials. The above-mentioned processes and materials can be found in related documents, such as U.S. Patent Nos. 5,525,276, 5,547,654, 5,609,800, 4,929,404, and Taiwan Patent Publication Nos. TW 326027, TW 379202, TW424079, etc. References.
然而上述石墨材料之製程仍存在以下問題。舉例而言，上述製程在利用中間相碳微球形成生坯時，在後續碳化與石墨化處理時，容易釋放出大量的揮發性成分，而造成後續所得之石墨碳材的表面，產生裂縫或缺陷而表面不完整的問題。其次，上述製程若需要在真空狀態進行碳化處理(例如上述之台灣專利所載)，在量產時會造成本的大幅提升。倘若，為了避免碳化與石墨化處理時揮發性成分逸散的問題，而放慢碳化處理的升溫速率，將會使得碳化處理時程更加冗長且更耗能。 However, the above process of the graphite material still has the following problems. For example, when the above process is used to form a green body by using mesocarbon microbeads, in the subsequent carbonization and graphitization treatment, a large amount of volatile components are easily released, resulting in the surface of the subsequently obtained graphite carbon material, causing cracks or Defects and incomplete surface problems. Secondly, if the above process needs to be carbonized in a vacuum state (for example, as described in the above-mentioned Taiwan patent), it will cause a substantial increase in mass production. If, in order to avoid the problem of the escape of volatile components during carbonization and graphitization, the rate of temperature increase of the carbonization process is slowed down, which will make the carbonization process longer and more energy-intensive.
綜言之，習知等方向性石墨材料之製程處理時間較長且耗能，而所得之石墨材料的表面容易有裂縫、甚至破裂，進而限制其應用之範圍。 In summary, conventional directional graphite materials have a long processing time and energy consumption, and the surface of the obtained graphite material is prone to cracks or even cracks, thereby limiting the range of application thereof.
因此，亟需提供一種等方向性石墨材料之製造方法，以徹底解決習知製程所得之石墨材料的表面有裂縫或缺陷，而限制其應用之範圍等問題。 Therefore, there is a need to provide a method for producing an isotropic graphite material to completely solve the problem that the surface of the graphite material obtained by the conventional process has cracks or defects, and limits the scope of application thereof.
因此，本發明之一態樣是在提供一種等方向性石墨材料的製造方法，其係將經或未經前處理之中間相碳微球， 經冷等均壓法模壓成生坯後，利用多階段碳化處理，以縮短碳化處理的時間，繼而進行石墨化處理，而形成等方向性碳質材料。 Accordingly, one aspect of the present invention provides a method of producing an isotropic graphite material which is a mesocarbon microbead with or without pretreatment. After being molded into a green body by a cold equalizing method, the multi-stage carbonization treatment is used to shorten the carbonization treatment time, followed by graphitization treatment to form an isotropic carbonaceous material.
其次，本發明之另一態樣是在提供一種等方向性石墨材料，其係利用上述方法所製得，且所得之等方向性石墨材料之表面為完整無裂紋缺陷且具有良好的機械、熱學與電學性質。 Secondly, another aspect of the present invention provides an isotropic graphite material which is obtained by the above method, and the surface of the obtained isotropic graphite material is a complete crack-free defect and has good mechanical and thermal properties. And electrical properties.
根據本發明之上述態樣，提出一種等方向性石墨材料的製造方法。在一實施例中，此等方向性石墨材料的製造方法係將經或未經前處理之中間相碳微球，利用冷等均壓法進行模壓，以形成一生坯。接著，將生坯進行多階段碳化與石墨化處理，而形成等方向性石墨材料。 According to the above aspect of the invention, a method of producing an isotropic graphite material is proposed. In one embodiment, the method of making the directional graphite material is to mold the mesocarbon microbeads with or without pretreatment by cold equalization to form a green body. Next, the green body is subjected to multi-stage carbonization and graphitization to form an isotropic graphite material.
在上述實施例中，未經前處理的中間相碳微球之平均粒徑為20μm至30μm，其中前述之中間相碳微球具有甲苯不溶(toluene insoluble)成分(TI)以及喹啉不溶(quinoline insoluble)成分(QI)，且TI與QI之差值為0.1重量百分比(wt%)至2.0 wt%。 In the above embodiment, the mesocarbon microbeads which have not been pretreated have an average particle diameter of from 20 μm to 30 μm, wherein the mesophase carbon microspheres have a toluene insoluble component (TI) and a quinoline insoluble (quinoline). Insoluble) component (QI), and the difference between TI and QI is 0.1 weight percent (wt%) to 2.0 wt%.
在上述實施例中，前述之冷等均壓法中，其係對經或未經前處理的中間相碳微球施加500 kg/cm2至3000 kg/cm2之壓力，以形成生坯。 In the above embodiment, in the cold equalizing method described above, a pressure of 500 kg/cm 2 to 3000 kg/cm 2 is applied to the mesocarbon microbeads which are or are not pretreated to form a green body.
在製成生坯後，生坯接著於第一保護氣氛之存在下，進行多階段碳化處理，以利用複數種升溫速率將生坯由室溫(約10℃至40℃)升溫至1000℃，而形成一碳化材料，其中當生坯之溫度為300℃至1000℃時，生坯之升溫速率為隨製程處理時間遞增之單調遞增函數。 After the green body is formed, the green body is then subjected to a multi-stage carbonization treatment in the presence of a first protective atmosphere to raise the green body from room temperature (about 10 ° C to 40 ° C) to 1000 ° C using a plurality of heating rates. A carbonized material is formed, wherein when the temperature of the green body is from 300 ° C to 1000 ° C, the heating rate of the green body is a monotonically increasing function that increases with the processing time.
在多階段碳化處理後，接著將前述之碳化材料進行石墨化處理，藉此形成等方向性石墨材料。在一例示中，上述之等方向性石墨材料之一表面為完整且不具裂紋缺陷，該等方向性石墨材料於X軸、Y軸與Z軸之熱膨脹係數之任二者的差異度為小於10%。 After the multi-stage carbonization treatment, the aforementioned carbonized material is then subjected to graphitization treatment, thereby forming an isotropic graphite material. In one example, the surface of one of the above-mentioned isotropic graphite materials is intact and has no crack defects, and the difference of the thermal expansion coefficients of the X-axis, the Y-axis and the Z-axis of the directional graphite material is less than 10 %.
依據本發明一實施例，上述之多階段碳化處理之多個升溫速率更包含由室溫(約10℃至40℃)升溫至300℃之第一升溫速率、由300℃升溫至500℃之第二升溫速率、由500℃升溫至800℃之第三升溫速率以及由800℃升溫至1000℃之第四升溫速率。在此實施例中，第一升溫速率係等於或大於第二升溫速率，第三升溫速率大於第二升溫速率，且第四升溫速率大於第三升溫速率。 According to an embodiment of the invention, the plurality of temperature rising rates of the multi-stage carbonization treatment further includes a first temperature increase rate from room temperature (about 10 ° C to 40 ° C) to 300 ° C, and a temperature increase from 300 ° C to 500 ° C. The second rate of temperature rise, a third rate of temperature increase from 500 ° C to 800 ° C, and a fourth rate of temperature increase from 800 ° C to 1000 ° C. In this embodiment, the first heating rate is equal to or greater than the second heating rate, the third heating rate is greater than the second heating rate, and the fourth heating rate is greater than the third heating rate.
依據本發明一實施例，當生坯之溫度為300℃至1000℃時，上述之第三升溫速率可為第二升溫速率之2.5倍至3.5倍，而第四升溫速率可為第二升溫速率之7倍至8倍。 According to an embodiment of the invention, when the temperature of the green body is from 300 ° C to 1000 ° C, the third heating rate may be 2.5 times to 3.5 times the second heating rate, and the fourth heating rate may be the second heating rate. 7 to 8 times.
根據本發明之另一態樣，提出一種等方向性石墨材料，其係利用上述之等方向性石墨材料的製造方法所製得，其中所得之等方向性石墨材料具有1.75g/cm3至1.95g/cm3之密度以及50至90之蕭氏硬度。 According to another aspect of the present invention, an isotropic graphite material is produced which is produced by the above-described method for producing an isotropic graphite material, wherein the obtained isotropic graphite material has a range of 1.75 g/cm 3 to 1.95. The density of g/cm 3 and the hardness of 50 to 90.
應用本發明之等方向性石墨材料及其方法，其係將經或未經前處理之中間相碳微球，經冷等均壓法模壓成生坯後，利用多階段碳化處理，可縮短整體製程時間，且由此所得之等方向性石墨材料具有較佳的等方向性、表面完整無裂紋缺陷又具有良好的機械、熱學與電學性質。 The use of the isotropic graphite material of the present invention and the method thereof, wherein the intermediate phase carbon microspheres with or without pretreatment are molded into a green body by cold equal equalization method, and the multi-stage carbonization treatment can shorten the whole The process time, and the resulting directional graphite material has better isotropicity, surface integrity and crack-free defects, and good mechanical, thermal and electrical properties.
承前所述，本發明提供一種等方向性石墨材料及其製造方法，其係將經或未經前處理之中間相碳微球，經冷等均壓法模壓成生坯後，利用多階段碳化處理，可獲得等方向性較佳且表面完整無裂紋缺陷之等方向性石墨材料，並縮短整體製程時間。 As described above, the present invention provides an isotropic graphite material and a method for producing the same, which comprises using a multi-stage carbonization of a mesocarbon microbead with or without pretreatment after being molded into a green body by cold isostatic pressing. The treatment can obtain a directional graphite material with equal directionality and complete surface without crack defects, and shorten the overall process time.
申言之，本發明之等方向性石墨材料的製造方法可利用下述方法製得。請參閱第1圖，其係繪示根據本發明一實施例之等方向性石墨材料的製造方法之部分流程圖。在一實施例中，此方法100可先如步驟101之所示，將前述經或未經前處理之中間相碳微球，經冷等均壓法進行模壓，以形成生坯，其中前述之冷等均壓法係對上述經或未經前處理之中間相碳微球施加500 kg/cm2至3000 kg/cm2之壓力達1分鐘至10分鐘，其中前述壓力係指最大成型壓力。在其他例子中，前述之冷等均壓法係對上述經或未經前處理之中間相碳微球施加1000 kg/cm2至2000 kg/cm2之壓力。 In other words, the method for producing an isotropic graphite material of the present invention can be obtained by the following method. Please refer to FIG. 1 , which is a partial flow chart showing a method of manufacturing an isotropic graphite material according to an embodiment of the invention. In one embodiment, the method 100 may first mold the intermediate or non-pretreated mesocarbon microbeads by cold equalization as shown in step 101 to form a green body, wherein the foregoing The cold equal pressure equalization method applies a pressure of 500 kg/cm 2 to 3000 kg/cm 2 to the above-mentioned or untreated mesocarbon microbeads for 1 minute to 10 minutes, wherein the aforementioned pressure means the maximum molding pressure. In other examples, the aforementioned cold iso-pressure equalization method applies a pressure of from 1000 kg/cm 2 to 2000 kg/cm 2 to the above-described or pre-treated mesocarbon microbeads.
在此實施例中，前述未經前處理之中間相碳微球之粉體原料的平均粒徑(D50)為20μm至30μm，而經前處理之中間相碳微球之粉體原料的平均粒徑為1μm至10μm。一般而言，中間相碳微球之球體表面吸附適量之β-樹脂(β-resin)，使其具有良好自燒結特性，經過冷等均壓法成型、碳化、石墨化處理後，可製備高密度等方向性石墨材料。其中，中間相碳微球具有甲苯不溶(toluene insoluble)成分(以下簡稱為TI)以及喹啉不溶(quinoline insoluble)成 分(以下簡稱為QI)，而β-樹脂是指不溶於甲苯但溶於喹啉的成分，因此β-樹脂的含量係界定為TI與QI之差值。適用於本發明之中間相碳微球的β-樹脂含量極低，在一例子中，TI與QI之差值為0.1重量百分比(wt%)至2.0 wt%。在另一例子中，TI與QI之差值為0.2 wt%至2.0 wt%。在又一例子中，TI與QI之差值為0.4 wt%至2.0 wt%。 In this embodiment, the average particle diameter (D 50 ) of the powder raw material of the aforementioned untreated mesocarbon microbeads is 20 μm to 30 μm, and the average of the powder raw materials of the pretreated mesocarbon microbeads is 20 μm to 30 μm. The particle diameter is from 1 μm to 10 μm. In general, the surface of the sphere of the mesophase carbon microspheres adsorbs an appropriate amount of β-resin (β-resin), so that it has good self-sintering characteristics, and can be prepared after being subjected to cold equalization, carbonization, and graphitization. Density and other directional graphite materials. The mesophase carbon microspheres have a toluene insoluble component (hereinafter abbreviated as TI) and a quinoline insoluble component (hereinafter referred to as QI), and the β-resin refers to insoluble in toluene but soluble in quinine. The composition of the porphyrin, and thus the content of the β-resin is defined as the difference between TI and QI. The β-resin content of the mesocarbon microbeads suitable for use in the present invention is extremely low. In one example, the difference between TI and QI is from 0.1 weight percent (wt%) to 2.0 wt%. In another example, the difference between TI and QI is from 0.2 wt% to 2.0 wt%. In yet another example, the difference between TI and QI is from 0.4 wt% to 2.0 wt%.
惟在此說明的是，倘若β-樹脂含量低於0.1重量百分比(wt%)，則中間相碳微球在後續碳化與石墨化處理時，其自燒結(self-sintering)性不佳，不容易形成表面完整的等方向性石墨材料。倘若β-樹脂含量大於2.0 wt%，則在後續碳化與石墨化處理時，碳微球內部溢出的揮發性成分會造成後續所得之等方向性石墨材料的表面，容易有裂縫或破裂問題。 However, it is stated here that if the β-resin content is less than 0.1% by weight (wt%), the mesocarbon microbeads have poor self-sintering properties in subsequent carbonization and graphitization treatments, It is easy to form a surface-complete isotropic graphite material. If the β-resin content is more than 2.0 wt%, the volatile components that overflow inside the carbon microspheres may cause the surface of the subsequently obtained isotropic graphite material to be susceptible to cracking or cracking during subsequent carbonization and graphitization.
然後，如步驟103所示，在第一保護氣氛之存在下，將前述之生坯進行多階段碳化處理，其係利用複數種升溫速率將生坯由室溫(約10℃至40℃)升溫至1000℃，而形成碳化材料。在一例子中，前述之第一保護氣氛為氮氣、氬氣、氦氣以及上述之任意組合。在另一例子中，前述之第一保護氣氛為氮氣。 Then, as shown in step 103, the green body is subjected to a multi-stage carbonization treatment in the presence of a first protective atmosphere, wherein the green body is heated from room temperature (about 10 ° C to 40 ° C) by a plurality of heating rates. To 1000 ° C, a carbonized material is formed. In one example, the first protective atmosphere described above is nitrogen, argon, helium, and any combination thereof. In another example, the aforementioned first protective atmosphere is nitrogen.
根據本發明之一實施例，當步驟103之生坯的溫度為300℃至1000℃時，生坯之升溫速率可定義為隨製程處理時間遞增之單調遞增函數。申言之，在一例式中，步驟103之多階段碳化處理可包括但不限於由室溫(約10℃至40℃)升溫至300℃之第一升溫速率、由300℃升溫至500℃之第二升溫速率、由500℃升溫至800℃之第三升溫速率以及由 800℃升溫至1000℃之第四升溫速率，其中第一升溫速率係等於或大於第二升溫速率，第三升溫速率大於第二升溫速率，且第四升溫速率大於第三升溫速率。 According to an embodiment of the present invention, when the temperature of the green body of step 103 is from 300 ° C to 1000 ° C, the heating rate of the green body can be defined as a monotonically increasing function that increases with the processing time. In one example, the multi-stage carbonization treatment of step 103 may include, but is not limited to, a first temperature increase rate from room temperature (about 10 ° C to 40 ° C) to 300 ° C, and a temperature increase from 300 ° C to 500 ° C. a second heating rate, a third heating rate from 500 ° C to 800 ° C, and The temperature rises from 800 ° C to a fourth temperature increase rate of 1000 ° C, wherein the first temperature increase rate is equal to or greater than the second temperature increase rate, the third temperature increase rate is greater than the second temperature increase rate, and the fourth temperature increase rate is greater than the third temperature increase rate.
上述第二升溫速率至第四升溫速率為逐步或連續變化且為隨製程處理時間遞增之單調遞增函數。多階段碳化處理由300℃升溫至1000℃時，溫度相對於製程處理時間之導數即為升溫速率，此升溫速率以不超過10℃/min為較佳。換言之，第二升溫速率、第三升溫速率以及第四升溫速率可保持恆定或隨時程而增加，其中，自第二升溫速率起，多階段碳化處理之溫度以不再下降為較佳。 The second to fourth heating rate is a stepwise or continuous change and is a monotonically increasing function that increases with process time. When the multi-stage carbonization treatment is carried out from 300 ° C to 1000 ° C, the derivative of the temperature with respect to the process time is the temperature increase rate, and the temperature increase rate is preferably not more than 10 ° C / min. In other words, the second heating rate, the third heating rate, and the fourth heating rate may be kept constant or increased over time, wherein the temperature of the multi-stage carbonization treatment is no longer decreased from the second heating rate.
舉例而言，當生坯之溫度為300℃至1000℃時，第三升溫速率可為第二升溫速率之2.5倍至3.5倍，而第四升溫速率可為第二升溫速率之7倍至8倍。由此所得之等方向性石墨材料具有較佳的等方向性且表面完整無裂紋缺陷。 For example, when the temperature of the green body is 300 ° C to 1000 ° C, the third heating rate may be 2.5 times to 3.5 times the second heating rate, and the fourth heating rate may be 7 times to 8 times of the second heating rate. Times. The isotropic graphite material thus obtained has a preferred isotropic property and a surface intact without crack defects.
在一例示中，第二升溫速率可為每分鐘0.02℃(℃/min)至1.0℃/min。在另一例示中，第二升溫速率可為0.02℃/min至0.7℃/min。在又一例示中，第二升溫速率可為0.02℃/min至0.05℃/min。 In one example, the second rate of temperature increase can be from 0.02 ° C (° C/min) to 1.0 ° C/min per minute. In another illustration, the second rate of temperature increase can be from 0.02 °C/min to 0.7 °C/min. In yet another illustration, the second rate of temperature increase can be from 0.02 °C/min to 0.05 °C/min.
在此需說明的是，在其他實施例中，上述多個升溫速率更可各自進一步在溫度範圍更小之區間中，進行升溫速率調控。舉例而言，由500℃升溫至800℃之第三升溫速率可進一步區分為由500℃升溫至600℃之第三(1)升溫速率以及由600℃升溫至800℃之第三(2)升溫速率，其中第三(2)升溫速率可等於或大於第三(1)升溫速率。惟本發明之升溫速率調控的方式並不限於此處所舉，其他溫度範圍之區間 亦可自由地在溫度範圍更小之區間中進行升溫速率調控。 It should be noted that, in other embodiments, the plurality of heating rates may be further adjusted in the temperature range of the temperature range. For example, the third temperature increase rate from 500 ° C to 800 ° C can be further divided into a third (1) temperature increase rate from 500 ° C to 600 ° C and a third (2) temperature increase from 600 ° C to 800 ° C. The rate, wherein the third (2) temperature increase rate may be equal to or greater than the third (1) temperature increase rate. However, the method of temperature regulation of the present invention is not limited to the ones mentioned herein, and the ranges of other temperature ranges are not limited. It is also free to adjust the heating rate in a smaller temperature range.
之後，如步驟105所示，在第二保護氣氛之存在下，將前述之碳化材料進行一石墨化處理，藉此形成等方向性石墨材料。在一例子中，前述之第二保護氣氛為氮氣、氬氣、氦氣以及上述之任意組合。在另一例子中，前述之第二保護氣氛為氬氣。 Thereafter, as shown in step 105, the carbonized material described above is subjected to a graphitization treatment in the presence of a second protective atmosphere, thereby forming an isotropic graphite material. In one example, the aforementioned second protective atmosphere is nitrogen, argon, helium, and any combination thereof. In another example, the aforementioned second protective atmosphere is argon.
在步驟105中，前述之石墨化處理係以5.0℃/min至8.0℃/min之第五升溫速率，將前述之碳化材料加熱至溫度2500℃至3000℃並持溫30分鐘至90分鐘。在另一例子中，前述之石墨處理係以6.0℃/min至7.0℃/min之第五升溫速率，將前述之碳化材料加熱至溫度2750℃並持溫30分鐘至90分鐘。 In step 105, the foregoing graphitization treatment heats the aforementioned carbonized material to a temperature of 2500 ° C to 3000 ° C at a fifth heating rate of 5.0 ° C / min to 8.0 ° C / min and holds the temperature for 30 minutes to 90 minutes. In another example, the foregoing graphite treatment heats the aforementioned carbonized material to a temperature of 2750 ° C and a temperature of 30 minutes to 90 minutes at a fifth heating rate of 6.0 ° C / min to 7.0 ° C / min.
在前述之碳化處理與石墨化處理之間，或石墨化處理之後，更可選擇性進行降溫步驟。申言之，在前述之碳化處理與石墨化處理之間，可選擇性進行第一自然降溫步驟，在不使用任何冷卻設備且於45小時至50小時，使前述之碳化材料之溫度降至25℃至40℃。 After the carbonization treatment and the graphitization treatment described above, or after the graphitization treatment, the temperature reduction step is more selectively performed. It is stated that, between the foregoing carbonization treatment and graphitization treatment, the first natural temperature lowering step can be selectively performed, and the temperature of the aforementioned carbonized material is lowered to 25 without using any cooling equipment and from 45 hours to 50 hours. °C to 40 °C.
另外，在石墨化處理之後，更可選擇性進行第二自然降溫步驟，在不使用任何冷卻設備使前述之等方向性石墨材料之溫度降至25℃至40℃。前述進行第一自然降溫步驟及/或第二自然降溫步驟，可使所得之等方向性石墨材料更加緻密且表面完整無裂紋缺陷。 In addition, after the graphitization treatment, the second natural temperature lowering step can be selectively performed to lower the temperature of the aforementioned directional graphite material to 25 ° C to 40 ° C without using any cooling equipment. The first natural cooling step and/or the second natural cooling step are performed to make the obtained isotropic graphite material more dense and surface intact without crack defects.
在此說明的是，上述所稱之「等方向性石墨材料」係指利用上述方法製得之高密度石墨材料，其表面為完整且不具裂紋缺陷，且此等方向性石墨材料於X軸、Y軸與Z 軸之熱膨脹係數之任二者的差異度為小於10%，代表其具有較佳的等方向性。其次，此等方向性石墨材料之密度為1.75 g/cm3至1.95 g/cm3，且其蕭氏硬度為50至90。在其他例子中，此等方向性石墨材料之密度為1.84 g/cm3至1.93 g/cm3，且其蕭氏硬度為58至85。 It is to be noted that the term "isotropic graphite material" as used herein refers to a high-density graphite material obtained by the above method, the surface of which is intact and free of crack defects, and the directional graphite material is on the X-axis, The difference between the thermal expansion coefficients of the Y-axis and the Z-axis is less than 10%, which means that it has a better isotropic property. Second, these directional graphite materials have a density of 1.75 g/cm 3 to 1.95 g/cm 3 and a Shore hardness of 50 to 90. In other examples, the directional graphite material has a density of 1.84 g/cm 3 to 1.93 g/cm 3 and a Shore hardness of 58 to 85.
值得一提的是，本發明之等方向性石墨材料的製造方法，是直接將經或未經前處理之中間相碳微球，經冷等均壓法模壓成生坯後，再利用多階段碳化處理，可縮短生坯進行碳化的處理時間並提高良率，因此本發明之方法排除進行習知之浸漬、再燒結等製程以修補裂縫。 It is worth mentioning that the method for producing the isotropic graphite material of the present invention directly uses the intermediate phase carbon microspheres with or without pretreatment, and then is molded into a green body by cold equal equalization method, and then uses multiple stages. The carbonization treatment can shorten the treatment time for carbonization of the green body and improve the yield. Therefore, the method of the present invention eliminates the conventional impregnation, re-sintering, and the like to repair cracks.
由於本發明之等方向性石墨材料的製造方法不僅環保節能，且所得之等方向性石墨材料具有較佳等方向性、其表面完整無裂紋缺陷，又大幅提升其機械、熱學以及電學性質，進而應用於擴大其產業利用範圍並增加經濟價值。舉例而言，前述所得之等方向性石墨材料可應用於電火花加工、連續鑄造、單晶矽長晶爐等。 Since the method for manufacturing an isotropic graphite material of the present invention is not only environmentally friendly and energy-saving, and the obtained isotropic graphite material has better equi-directionality, the surface is completely free of crack defects, and the mechanical, thermal and electrical properties thereof are greatly improved, and further It is used to expand the scope of its industrial use and increase its economic value. For example, the isotactic graphite material obtained as described above can be applied to electric discharge machining, continuous casting, single crystal enamel crystal growth furnace, and the like.
以下利用實施例以說明本發明之應用，然其並非用以限定本發明，本發明技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾。 The following examples are provided to illustrate the application of the present invention, and are not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention.
實施例1至實施例4使用中間相碳微球B為原料，其中中間相碳微球B之基本資料係列於第1表(其TI為99.4%，QI為98.9%，平均粒徑(D50)為21μm；中鋼碳素化 學股份有限公司)。 Example 1 to Example 4 use mesocarbon microbeads B as raw materials, wherein the basic data series of mesocarbon microbeads B is in Table 1 (the TI is 99.4%, the QI is 98.9%, and the average particle diameter (D 50) ) is 21 μm; Sinosteel Carbon Chemical Co., Ltd.).
將約55克之上述未經前處理的中間相碳微球B，充填於內徑約25 mm的圓筒狀橡膠模具(模壁厚度1.0 mm)內，其中中間相碳微球於模具內之充填高度為約140 mm。模具蓋上同質的橡膠蓋壓實後，進行簡易包裝(例如，利用例如電氣膠布纏繞緊實)，以避免在冷等均壓操作過程中，加壓液體不慎侵入模具內而造成污染。 About 55 g of the above-mentioned unpretreated mesocarbon microbeads B were filled in a cylindrical rubber mold (having a wall thickness of 1.0 mm) having an inner diameter of about 25 mm, wherein the mesocarbon microbeads were filled in the mold. The height is approximately 140 mm. After the homogenous rubber cover on the mold cover is compacted, it is simply packaged (for example, tightly wound with an electrical tape) to avoid contamination of the pressurized liquid into the mold during cold equalizing operation.
上述含有中間相碳微球之模具置於冷等均壓設備(CL4.5-22-30，Nikkiso Co.,Ltd.,Japan)中，加壓至約1,800 kg/cm2並於此壓力下維持至少約5分鐘。之後，洩壓至常壓，從橡膠模具中取出壓製成型的圓柱狀生坯，並將其對切為生坯樣品。此種生坯的直徑為約21 mm，長度為約55 mm。 The above mold containing mesocarbon microbeads was placed in a cold equalizing apparatus (CL4.5-22-30, Nikkiso Co., Ltd., Japan), and pressurized to about 1,800 kg/cm 2 under this pressure. Maintain at least about 5 minutes. Thereafter, the pressure was released to normal pressure, and the press-formed cylindrical green body was taken out from the rubber mold, and the pair was cut into a green sample. Such green bodies have a diameter of about 21 mm and a length of about 55 mm.
接著，將前述生坯放入一般市售之管型氣氛爐中，例如三區溫控管型爐(堯富精密公司，台灣)，在第一保護氣氛例如氮氣之存在下，進行多階段碳化處理，其係根據第1表所列之多階段升溫條件，將前述之生坯由室溫(約10℃至40℃)加熱至1000℃，以進行碳化處理，而形成碳化材料。之後，進行第一自然降溫步驟，在不使用任何冷卻設備且於第一保護氣氛之存在下，使爐體自然降溫至低於100℃。 Next, the green body is placed in a generally commercially available tubular atmosphere furnace, for example, a three-zone temperature-controlled tubular furnace (Yufu Precision Co., Ltd., Taiwan), and multi-stage carbonization is carried out in the presence of a first protective atmosphere such as nitrogen. The treatment is carried out by heating the above-mentioned green body to room temperature (about 10 ° C to 40 ° C) to 1000 ° C according to the multi-stage temperature rising conditions listed in Table 1, to carry out carbonization treatment to form a carbonized material. Thereafter, a first natural cooling step is performed to naturally cool the furnace body to below 100 ° C without using any cooling equipment and in the presence of a first protective atmosphere.
實施例1至實施例4所得之碳化材料的密度為1.58 g/cm3至1.63 g/cm3，蕭氏硬度為93至101，其表面為完整且不具裂紋缺陷。 The carbonized materials obtained in Examples 1 to 4 had a density of 1.58 g/cm 3 to 1.63 g/cm 3 and a Shore hardness of 93 to 101, and the surface was intact and free from crack defects.
實施例5使用中間相碳微球G為原料，其中中間相碳微球G之基本資料係列於第1表(其TI為99.0%，QI為98.6%，平均粒徑(D50)為24μm；中鋼碳素化學股份有限公司)。 Example 5 uses mesocarbon microbeads G as a raw material, wherein the basic data series of mesocarbon microbeads G is in Table 1 (the TI is 99.0%, the QI is 98.6%, and the average particle diameter (D 50 ) is 24 μm; Sinosteel Carbon Chemical Co., Ltd.).
在通氮氣作保護的情況下，將中間相碳微球G置於200℃至500℃溫度範圍內，進行6小時的熱處理。其後，利用氣引式粉碎設備(ALG-2，凌廣工業公司，台灣)進行粉碎。之後，利用粒徑分析儀(MultisizerTM 3，Beckman Coulter,Inc.,U.S.A.)分析此中間相碳微球經粉碎後之粉體原料，其平均粒徑(D50)為約7 μm。 In the case of protection with nitrogen gas, the mesocarbon microbeads G were placed in a temperature range of 200 ° C to 500 ° C for heat treatment for 6 hours. Thereafter, the pulverization was carried out using a gas-injection pulverizing apparatus (ALG-2, Lingguang Industrial Co., Ltd., Taiwan). Thereafter, after the analysis of mesophase carbon microbeads comminuted raw powder using a particle size analyzer (Multisizer TM 3, Beckman Coulter, Inc., USA), having an average particle diameter (D 50) of about 7 μm.
接著，將約860克之上述經前處理的粉體，充填於內徑100 mm的圓筒狀橡膠模具(模壁厚度4.0 mm)內，其中粉碎粉體於模具內之充填高度為約160 mm。模具蓋上同質的橡膠蓋並壓實後，進行簡易包裝(例如，利用例如電氣膠布纏繞緊實)，以避免在冷等均壓操作過程中，加壓液體不慎侵入模具內而造成污染。 Next, about 860 g of the above pretreated powder was filled in a cylindrical rubber mold (molar wall thickness: 4.0 mm) having an inner diameter of 100 mm, and the filling height of the pulverized powder in the mold was about 160 mm. After the mold is covered with a homogenous rubber cover and compacted, it is simply packaged (for example, tightly wound with an electrical tape) to avoid contamination of the pressurized liquid in the mold during cold equalizing operation.
上述充填經前處理之中間相碳微球的模具，置於冷等均壓設備(井豐油壓公司製之濕式冷均壓機，成型室直徑130 mm、高度400 mm，最大成型壓力2500 kg/cm2)中，加壓至約1,400 kg/cm2並於此壓力下維持約5分鐘。之後，洩壓至常壓，從橡膠模具中取出壓製成型的圓柱狀生坯。如此，所製得生坯的直徑為79 mm，長度為134 mm。 The above mold for filling the pretreated intermediate phase carbon microspheres is placed in a cold equalizing device (wet cold equalizing machine manufactured by Jingfeng Hydraulic Co., Ltd., the molding chamber has a diameter of 130 mm, a height of 400 mm, and a maximum molding pressure of 2,500. In kg/cm 2 ), it was pressurized to about 1,400 kg/cm 2 and maintained at this pressure for about 5 minutes. Thereafter, the pressure was released to normal pressure, and the press-formed cylindrical green body was taken out from the rubber mold. Thus, the green body produced has a diameter of 79 mm and a length of 134 mm.
接著，將前述生坯放入一般市售之氣氛爐中，在第一保護氣氛例如氮氣之存在下，進行多階段碳化處理，其係 根據第1表所列之多階段升溫條件，將前述之生坯由室溫(約10℃至40℃)加熱至1000℃，以進行碳化處理，而形成碳化材料。之後，進行第一自然降溫步驟，在不使用任何冷卻設備且於約48小時內，使爐體自然降溫至室溫(約10℃至40℃)，如此進行碳化處理所得之碳化材料，其表面完整、無裂紋缺陷，經測其密度為1.67 g/cm3。 Next, the green body is placed in a generally commercially available atmosphere furnace, and a multi-stage carbonization treatment is carried out in the presence of a first protective atmosphere such as nitrogen, which is based on the multi-stage temperature rising conditions listed in Table 1, The green body is heated from room temperature (about 10 ° C to 40 ° C) to 1000 ° C for carbonization to form a carbonized material. Thereafter, the first natural cooling step is performed, and the furnace body is naturally cooled to room temperature (about 10 ° C to 40 ° C) in about 48 hours without using any cooling equipment, and the carbonized material obtained by the carbonization treatment is surfaced. Complete, crack-free defects, measured to have a density of 1.67 g/cm 3 .
然後，將前述碳化材料放入真空高溫爐(Vacuum Furnace Type 45，Centorr Vacuum Industries,Inc.)中，在第二保護氣氛例如氬氣之存在下，以平均6.7℃/min之第五升溫速率，將前述之碳化材料由室溫(約10℃至40℃，或約30℃)加熱至2750℃並持溫1小時，以進行石墨化處理。之後，進行第二自然降溫步驟，在不使用任何冷卻設備下，使爐體自然降溫至室溫(約10℃至40℃)附近，其中所得之石墨材料即為等方向性石墨材料。實施例5所得之等方向性石墨材料的密度為1.85 g/cm3，蕭氏硬度為58，其表面為完整且不具裂縫缺陷，且此等方向性石墨材料於各方向之熱膨脹係數其間的差異度為小於10%(其於X、Y、Z方向的熱膨脹係數均為5.7×10-6K-1至6.0×10-6K-1)。 Then, the foregoing carbonized material is placed in a vacuum high temperature furnace (Vacuum Furnace Type 45, Centorr Vacuum Industries, Inc.) at a fifth heating rate of 6.7 ° C/min in the presence of a second protective atmosphere such as argon. The foregoing carbonized material was heated from room temperature (about 10 ° C to 40 ° C, or about 30 ° C) to 2750 ° C and held at a temperature for 1 hour for graphitization. Thereafter, a second natural cooling step is performed to naturally cool the furnace body to near room temperature (about 10 ° C to 40 ° C) without using any cooling equipment, wherein the graphite material obtained is an isotropic graphite material. Example 5 obtained from the density and the like graphite material directivity embodiment of 1.85 g / cm 3, Shore hardness of 58, a surface having cracks is incomplete and defects, and a graphite material such directivity in all directions of the thermal expansion coefficient difference therebetween The degree is less than 10% (the coefficient of thermal expansion in the X, Y, and Z directions is 5.7 × 10 -6 K -1 to 6.0 × 10 -6 K -1 ).
實施例5所得之等方向性石墨材料進一步檢測其抗折強度、抗壓強度以及電阻係數，其檢測相關方法詳如後述，其結果如第2表所示。 The isotropic graphite material obtained in Example 5 was further tested for its flexural strength, compressive strength, and electrical resistivity. The method for detecting the details is as described later, and the results are shown in Table 2.
實施例6使用中間相碳微球M為原料，其中中間相碳微球M之基本資料係列於第1表(其TI為96.9%，QI為 95.0%，平均粒徑(D50)為24μm；中鋼碳素化學股份有限公司)。 Example 6 uses mesocarbon microbeads M as a raw material, wherein the basic data series of mesocarbon microbeads M is in Table 1 (its TI is 96.9%, QI is 95.0%, and average particle diameter (D 50 ) is 24 μm; Sinosteel Carbon Chemical Co., Ltd.).
中間相碳微球M在使用前，先利用氣引式粉碎設備(同於實施例5所用者)進行粉碎；使用粒徑分析儀(同於實施例5者)分析此中間相碳微球經粉碎後之平均粒徑(D50)為約5 μm。 The mesocarbon microbeads M were first pulverized by a gas-injection pulverizing apparatus (as used in Example 5) before use; the mesophase carbon microspheres were analyzed using a particle size analyzer (same as in Example 5). The average particle diameter (D 50 ) after pulverization was about 5 μm.
接著，將約250克之上述經前處理的粉體，充填於內徑71 mm的圓筒狀橡膠模具(模壁厚度1.0 mm)內，其中粉碎粉體於模具內之充填高度為約118 mm。 Next, about 250 g of the above pretreated powder was filled in a cylindrical rubber mold having an inner diameter of 71 mm (mold wall thickness: 1.0 mm), and the filling height of the pulverized powder in the mold was about 118 mm.
上述充填經粉碎前處理之中間相碳微球的模具，置於冷等均壓設備(CL4.5-22-30，Nikkiso Co.,Ltd.,Japan)中中，加壓至約1,400 kg/cm2進行生坯成型。如此，所製得生坯的直徑為52 mm，長度為92 mm。 The above-mentioned mold filled with the mesocarbon microbeads before the pulverization was placed in a cold equalizing apparatus (CL4.5-22-30, Nikkiso Co., Ltd., Japan) and pressurized to about 1,400 kg/ Cm 2 is used for green molding. Thus, the resulting green body has a diameter of 52 mm and a length of 92 mm.
接著，將前述生坯如實施例5一般，在氣氛爐中進行多階段碳化處理，而多階段升溫條件其係根據第1表所列。如此進行碳化處理所得之碳化材料，其表面完整、無裂縫，經測其密度為1.74 g/cm3。 Next, the green body described above was subjected to a multi-stage carbonization treatment in an atmosphere furnace as in Example 5, and the multi-stage temperature rising conditions were listed in Table 1. The carbonized material obtained by the carbonization treatment has a complete surface and no crack, and the density thereof is 1.74 g/cm 3 .
然後，將前述碳化材料進行石墨化處理，其方法及條件則是完全同於實施例5者。如此，所製得之等方向性石墨材料，其密度為1.93 g/cm3，蕭氏硬度為85，其表面為完整且不具裂縫缺陷，且此等方向性石墨材料於各方向之熱膨脹係數其間的差異度為小於10%(其於X、Y、Z方向的熱膨脹係數均為6.8×10-6K-1至7.2×10-6K-1)。 Then, the carbonized material was subjected to graphitization treatment, and the method and conditions were the same as those in Example 5. Thus, the obtained isotropic graphite material has a density of 1.93 g/cm 3 and a Shore hardness of 85, and the surface thereof is intact and has no crack defects, and the thermal expansion coefficients of the directional graphite materials in all directions are between The degree of difference is less than 10% (the coefficient of thermal expansion in the X, Y, and Z directions is 6.8 × 10 -6 K -1 to 7.2 × 10 -6 K -1 ).
實施例6所得之等方向性石墨材料進一步檢測其抗折強度、抗壓強度、熱傳導係數以及電阻係數，其結果如第 2表所示。 The isotropic graphite material obtained in Example 6 was further tested for its flexural strength, compressive strength, heat transfer coefficient and electrical resistivity, and the results were as follows. 2 table shown.
比較例1至比較例2係使用與實施例1相同之方法進行冷等均壓成型、碳化及石墨化處理。不同的是，比較例1至比較例2之碳化處理的製程條件不同於實施例1，其製程條件係列於第2表。 In Comparative Example 1 to Comparative Example 2, cold isostatic pressing, carbonization, and graphitization were carried out in the same manner as in Example 1. The difference was that the process conditions of the carbonization treatment of Comparative Example 1 to Comparative Example 2 were different from those of Example 1, and the process conditions were serialized in Table 2.
實施例1至實施例6所得之碳化材料與實施例5至實施例6所得之石墨材料，以及比較例1至比較例2所得之碳化材料，進一步利用目測觀察其表面之完整性，並依下列標準評估，其結果如第2表所示：○：表面完整且不具裂紋缺陷 The carbonized materials obtained in Examples 1 to 6 and the graphite materials obtained in Examples 5 to 6 and the carbonized materials obtained in Comparative Examples 1 to 2 were further visually observed for the surface integrity, and the following Standard evaluation, the results are shown in Table 2: ○: Surface integrity and no crack defects
×：表面不完整，且具有嚴重裂紋。 ×: The surface is incomplete and has a severe crack.
由第2表可得知，實施例1至實施例6所得之碳化材料與實施例5至實施例6所得之石墨材料，其表面完整且 不具裂紋缺陷或裂縫。相較之下，比較例1至比較例2所得之碳化材料與石墨材料，其表面不完整且具有裂縫；由於所製之碳化材料破裂、不完整，無法進一步進行石墨化以製出完整的等方向性石墨材料。 As can be seen from the second table, the carbonized materials obtained in Examples 1 to 6 and the graphite materials obtained in Examples 5 to 6 have a surface intact and No cracks or cracks. In comparison, the carbonized material and the graphite material obtained in Comparative Example 1 to Comparative Example 2 have incomplete surface and cracks; since the carbonized material is broken and incomplete, further graphitization cannot be performed to produce a complete product. Directional graphite material.
其次，實施例1至實施例6所得之碳化材料與實施例5至實施例6所得之石墨材料進行機械強度之評估，其係利用市售之蕭氏硬度試驗機(Shore Hardness Tester,Type D,Sato Seiki Co.,Japan)測量蕭氏硬度(Shore硬度；Hs)，利用ASTM(American Society for Testing and Materials)C651之測試方法與Sintech 10/GL材料試驗機(MTS Test Systems Co.,U.S.A.)測量抗折強度，並利用ASTM C695之測試方法與Sintech 10/GL材料試驗機測量抗壓強度，其結果如第2表所示。 Next, the carbonized materials obtained in Examples 1 to 6 and the graphite materials obtained in Examples 5 to 6 were evaluated for mechanical strength using a commercially available Shore Hardness Tester (Type D, Sato Seiki Co., Japan) measured Shore hardness (Shore hardness; Hs) using ASTM (American Society for Testing and Materials) C651 test method and Sintech 10/GL material testing machine (MTS Test Systems Co., USA) The flexural strength was measured and the compressive strength was measured using a test method of ASTM C695 and a Sintech 10/GL material testing machine. The results are shown in Table 2.
由第2表可得知，實施例5至實施例6所得之等方向性石墨材料，其蕭氏硬度為58至85，抗折強度為32 MPa至44 MPa，抗壓強度為68 MPa至120 MPa As can be seen from the second table, the isotropic graphite materials obtained in Examples 5 to 6 have a Shore hardness of 58 to 85, a flexural strength of 32 MPa to 44 MPa, and a compressive strength of 68 MPa to 120. MPa
依照這些比較例之製程條件進行碳化處理後，所製出之碳化材料坯體表面皆有嚴重裂縫，亦即無法製出完整的碳化材料；也因而無法進一步以石墨化處理製出完整的等方向性石墨材料。與實施例1至實施例4作比較，比較例1至比較例2無法製得完整的石墨材料的原因，是在碳化處理時某些溫度區段的加溫速率太快。 After the carbonization treatment according to the process conditions of these comparative examples, the surface of the carbonized material body produced has serious cracks, that is, a complete carbonized material cannot be produced; and thus it is impossible to further form a complete isotropic direction by graphitization. Graphite material. In comparison with Examples 1 to 4, the reason why Comparative Example 1 to Comparative Example 2 could not produce a complete graphite material was that the heating rate of some temperature sections was too fast at the time of carbonization treatment.
再者，實施例5與實施例6所得之等方向性石墨材料進行熱學與電學性質之評估，其係利用ASTM C714與ASTM E228之測試方法測量熱傳導係數以及熱膨脹係數，並利用ASTM C611之測試方法測量電阻係數，其結果如第2表所示。 Furthermore, the isotactic graphite materials obtained in Example 5 and Example 6 were evaluated for thermal and electrical properties, and the thermal conductivity and thermal expansion coefficient were measured by ASTM C714 and ASTM E228, and the test method of ASTM C611 was used. The resistivity was measured, and the results are shown in Table 2.
由第2表可得知，實施例5與實施例6所得之等方向性石墨材料，其熱傳導係數在40 W/mK附近，熱膨脹係數為5.7×10-6/K至7.2×10-6/K，電阻係數為6.6 μ Ω m至10.8 μ Ω m。 As can be seen from the second table, the isotropic graphite materials obtained in Example 5 and Example 6 have a heat transfer coefficient of around 40 W/mK and a coefficient of thermal expansion of from 5.7 × 10 -6 /K to 7.2 × 10 -6 / K, the resistivity is 6.6 μ Ω m to 10.8 μ Ω m.
其次，由第2表之結果可得知，實施例1至6將未經或經前處理之中間相碳微球，經冷等均壓法進行模壓，以形成生坯後，利用多階段碳化處理，可縮短進行碳化及石墨化的處理時間，並進而製出表面完整且不具裂紋缺陷之碳化材料以及等方向性石墨材料，而且等方向性石墨材料的性質良好，因此確實可達到本發明之目的。 Next, as can be seen from the results of Table 2, Examples 1 to 6 used the intermediate phase carbon microspheres which were not or pretreated, were molded by cold equalization to form a green body, and then used multi-stage carbonization. The treatment can shorten the treatment time for carbonization and graphitization, and further produce a carbonized material having an intact surface and no crack defects, and an isotropic graphite material, and the properties of the isotropic graphite material are good, so that the present invention can be achieved. purpose.
惟在此需補充的是，本發明之等方向性石墨材料及其製造方法亦可使用其他中間相碳微球或其他反應條件等進行，此為本發明所屬技術領域中任何具有通常知識者所熟知，故不另贅述。 However, it should be added here that the isotropic graphite material of the present invention and the method for producing the same can also be carried out using other mesocarbon microbeads or other reaction conditions, etc., which is any one of ordinary skill in the art to which the present invention pertains. Well known, so I will not repeat them.
綜言之，由上述本發明實施方式可知，應用本發明之等方向性石墨材料及其製造方法，其優點在於將經或未經前處理之中間相碳微球，經冷等均壓法模壓成生坯後，利用多階段碳化處理，可縮短碳化處理時間，且所得之等方向性石墨材料的表面為完整、無裂紋缺陷且等方向性佳， 更大幅提升其機械、熱學以及電學性質，進而增加其產業應用範圍，提高其經濟價值，例如可應用於電火花加工、連續鑄造、單晶矽長晶爐等。 In summary, it can be seen from the above embodiments of the present invention that the use of the isotropic graphite material of the present invention and the method for producing the same have the advantages that the intermediate phase carbon microspheres with or without pretreatment are molded by cold equalization method. After the green body is formed, the carbonization treatment time can be shortened by multi-stage carbonization treatment, and the surface of the obtained isotropic graphite material is complete, has no crack defects and has good isotropic property. It will greatly enhance its mechanical, thermal and electrical properties, thereby increasing its industrial application range and increasing its economic value. For example, it can be applied to EDM, continuous casting, single crystal enamel crystal furnaces, etc.
雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，本發明所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 The present invention has been disclosed in the above embodiments, and is not intended to limit the scope of the present invention, and it is possible to make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.
100‧‧‧方法 100‧‧‧ method
101‧‧‧將經或未經前處理的中間相碳微球，經由冷等均壓法模壓成生坯之步驟 101‧‧‧Steps of molding mesocarbon microbeads with or without pretreatment into a green body by cold isostatic pressing
103‧‧‧將生坯進行多階段碳化處理，以形成碳化材料之步驟 103‧‧‧Steps for multi-stage carbonization of green bodies to form carbonized materials
105‧‧‧將碳化材料進行石墨化處理，以形成等方向性石墨材料之步驟 105‧‧‧Steps for graphitizing carbonized materials to form isotropic graphite materials
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之說明如下：第1圖係繪示根據本發明一實施例之等方向性石墨材料的製造方法的部分流程圖。 The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Part of the flow chart of the method.
100‧‧‧方法 100‧‧‧ method
101‧‧‧將經或未經前處理的中間相碳微球，經由冷等均壓法模壓成生坯之步驟 101‧‧‧Steps of molding mesocarbon microbeads with or without pretreatment into a green body by cold isostatic pressing
103‧‧‧將生坯進行多階段碳化處理，以形成碳化材料之步驟 103‧‧‧Steps for multi-stage carbonization of green bodies to form carbonized materials
105‧‧‧將碳化材料進行石墨化處理，以形成等方向性石墨材料之步驟 105‧‧‧Steps for graphitizing carbonized materials to form isotropic graphite materials
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