US20090246493A1 - Flexible, high purity expanded graphite sheet, method of producing same, and carbon crucible lining using said sheet - Google Patents
Flexible, high purity expanded graphite sheet, method of producing same, and carbon crucible lining using said sheet Download PDFInfo
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- US20090246493A1 US20090246493A1 US12/478,792 US47879209A US2009246493A1 US 20090246493 A1 US20090246493 A1 US 20090246493A1 US 47879209 A US47879209 A US 47879209A US 2009246493 A1 US2009246493 A1 US 2009246493A1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/536—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite based on expanded graphite or complexed graphite
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B35/00—Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
- B32B2315/02—Ceramics
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/604—Pressing at temperatures other than sintering temperatures
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
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- C—CHEMISTRY; METALLURGY
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/94—Products characterised by their shape
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- C—CHEMISTRY; METALLURGY
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- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
- C04B2237/36—Non-oxidic
- C04B2237/363—Carbon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Definitions
- the present invention relates to a flexible, high-purity expanded graphite sheet, and to a method of producing the same.
- Expanded graphite sheets are generally produced by treating natural graphite, pyrolytic graphite, kish graphite or the like with a mixed solution containing sulfuric acid and nitric acid, for instance, then washing the same with water, drying the same, treating the same for expansion in an expansion oven at about 1,000° C., and firming the same into sheets using a rolling machine, for instance. Expanded graphite sheets are excellent in heat resistance and in gas and liquid in impermeability and therefore are used as packing materials, valve sheets, gaskets, and fuel cell separators, among others.
- Japanese Patent No. 2,620,606 discloses that highly pure expanded graphite sheets having an impurity content of not more than 15 ppm can be obtained by treating such expanded graphite sheets for increased purity in a halogen gas atmosphere at 2,000° C. or above. Such sheets are used in the process of semiconductor production.
- FIG. 1 A sectional view of the main parts of a CZ apparatus is shown in FIG. 1 .
- the CZ apparatus comprises such parts as a carbon crucible 5 supporting a quarts crucible 1 , a heater 2 , an upper ring 6 , and an inner shield 7 , among others.
- polycrystalline silicon placed in the quartz crucible 1 is heated to a high temperature to give a silicon melt 3 , and the tip of a seed crystal held by a seed chuck is brought into contact with the raw material melt 3 and then pulled up while maintaining the contact to thereby pull up a silicon single crystal 4 .
- the carbon crucible 5 made of graphite or a carbon fiber-reinforced carbon composite material (such crucible is hereafter referred to as “carbon crucible”) is in direct contact with the quartz crucible 1 and, therefore, the surface of the carbon crucible 5 is gradually converted to silicon carbide (hereinafter referred to as “SiC”) as a result of the reaction between the quartz crucible 1 and carbon crucible 5 and/or the reaction between vaporized silicon and the graphite crucible.
- SiC silicon carbide
- the difference in coefficient of thermal expansion between carbon and SiC is conducive to cracking of the carbon crucible, for instance.
- the quartz crucible 1 becomes firmly sticking to the carbon crucible 5 , making it difficult to take out the quartz crucible 1 .
- Japanese Patent No. 2,528,285 discloses, as a means for solving such problems, the use of a high-purity expanded graphite sheet as a liner intervening between the quartz crucible 1 and carbon crucible 5 .
- Japanese Patent No. 2,620,606 discloses a method of restoring flexibility which comprises compression molding.
- the method has other problems; the purity of the high-purity expanded graphite sheet is decreased upon compression molding and, when a complicated shape is given to the high-purity expanded graphite sheet insufficient in flexibility restoration by working with a cutter, for instance, the peripheral parts of the sheet are subject to cracking and/or chipping.
- each single crystal production operation consumes one intervening liner and, therefore, it is important to provide a method of producing high-purity expanded graphite sheets which is excellent in mass productivity.
- Another object of the present invention is to provide a high-purity expanded graphite sheet having flexibility and a method of producing the same. Another object of the invention is to provide a method of manufacturing expanded graphite sheets which is suited for mass production as well.
- the invention provides a flexible, high-purity expanded graphite sheet characterized in that it has an impurity content not exceeding 10 ppm and has such a degree of flexibility that a sample thereof can withstand at least 10 times of bending on a testing apparatus such as shown in FIG. 4 .
- the invention provides a flexible, high-purity expanded graphite sheet which has the above characteristics and is further characterized by its bulk density being 0.5 to 1.3 g/cm 3 .
- the invention provides a flexible, high-purity expanded graphite sheet as defined in Claim 1 or 2 which is further characterized by its thickness being 0.2 to 1.0 mm.
- Expanded graphite sheets having a bulk density lower than 0.7 g/cm 3 cannot acquire, even after purification treatment, such a degree of flexibility as to withstand at least 10 times of bending, hence are unfavorable. Expanded graphite sheets having a bulk density exceeding, 1.3 g/cm 3 are also undesirable, since the impurity content therein cannot be reduced to 10 ppm or below even by purification treatment.
- expanded graphite sheets with a bulk density adjusted to 0.8 to 1.3 g/cm 3 , more preferably to 0.9 to 1.3 g/cm 3 are subjected to treatment for attaining high purity.
- the method of purification treatment itself may be any of those known in the art.
- flexible, high-purity expanded graphite sheets having an impurity content of not more than 10 ppm and a degree of flexibility as to withstand at least 10 times of bending can be obtained by heating expanded graphite sheets at 2,000° C. or above in a halogen gas atmosphere to thereby convert metals in the sheets to metal halide compounds showing a high vapor pressure and allow them to vaporize.
- the bulk density and sheet thickness of expanded graphite sheets after purification treatment show little changes and remain almost equal to those before treatment.
- a flexibility measuring apparatus is schematically shown in FIG. 3 .
- a 50-g weight 22 is attached to one end of a 10 mm ⁇ 100 mm sample 21 of a high-purity expanded graphite sheet and subjected to repeated bending by means of bending bodies 24 with a diameter of 6 mm. The number of times of bending until breakage is counted and recorded as the flexibility in the longitudinal direction.
- the invention provides a method of producing flexible, high-purity expanded graphite sheets which comprises forming an expanded graphite sheet having a bulk density of 0.7 to 1.3 g/cm 3 into a desired shape and then subjecting the shaped sheet to purification treatment.
- Expanded graphite sheets having a bulk density less than 0.7 g/cm 3 are undesirable since any purification treatment cannot improve their flexibility to a level of at least 10 times, as mentioned above.
- Expanded graphite sheets having a bulk density exceeding 1.3 g/cm 3 are also unfavorable since their impurity content cannot be reduced to 10 ppm or less by purification treatment.
- the expanded graphite sheet to be treated for purification has a thickness of 0.2 to 1.0 mm.
- the sheet after purification treatment tends to show marked decreases in flexibility and strength, hence are susceptible to cracking, for instance.
- the expanded graphite sheet is thicker than 1.0 mm, the impurity content cannot be reduced to a satisfactory extent by purification treatment.
- the expanded graphite sheet to be subjected to purification treatment has a thickness of 0.3 to 0.9 mm. Most preferably, 0.5 to 0.8-mm-thick expanded graphite sheets are subjected to purification treatment.
- the “desired shape” so referred to herein there may be mentioned, for example, the shape shown in FIG. 2 or FIG. 3 and, further, figures of line symmetry, such as ellipses, stars and the Imperial crest of chrysanthemum, and asymmetric figures.
- the invention provides a modification of the method specified above which modification comprises forming a plurality of expanded graphite sheets each into one and the same desired shape simultaneously in a laminate form, followed by purification treatment.
- modification comprises forming a plurality of expanded graphite sheets each into one and the same desired shape simultaneously in a laminate form, followed by purification treatment.
- This modification is preferred since the mass productivity in manufacturing expanded graphite sheets having one and the same desired, complicated shape can be improved by laying a plurality of expanded graphite sheets one upon another and working them simultaneously in one operation according to the method mentioned above.
- a plurality of expanded graphite sheets each having a thickness of 0.2 to 1.0 mm are laid one upon another. When each expanded graphite sheet is less than 0.2 mm in thickness, the expanded graphite sheet cannot acquire flexibility or strength but becomes susceptible to cracking, for instance.
- the impurity content cannot be reduced to a satisfactory extent by purification treatment; this is unfavorable. It is desirable that the bulk density of expanded graphite sheets prior to purification treatment be 0.7 to 1.3 g/cm 3 .
- the invention provides a method of producing such expanded graphite sheets as mentioned above in which the shaping of expanded graphite sheets is carried out by at least one method selected from among such methods as slitting, punching using a Thomson die, water jet working, and laser working. From the mass productivity viewpoint, however, punching with a Thomson die and water jet working are preferred since they can reduce the working time, are less likely to decrease the purity of expanded graphite sheets and, further, are excellent in mass productivity.
- the purification treatment should preferably be carried out after removing working dust from the worked surface (cut surface) by ultrasonic cleaning in a state immersed in water, alcohol or the like and the subsequent drying for evaporation of the moisture.
- the invention provides the use of the flexible, high-purity expanded graphite sheet as defined in any one of Claims 1 to 3 as a carbon crucible liner.
- a carbon crucible liner When such a high-purity expanded graphite sheet having flexibility and a low impurity content is used as a carbon crucible liner, the stability of the quartz crucible is good and the intrusion of silicon monoxide gas can be prevented, so that the carbon crucible can be inhibited from beg converted to silicon carbide and the life of the expensive carbon crucible can be prolonged.
- FIG. 1 is a schematic sectional view of a single crystal puller.
- FIG. 2 is an illustration of shaping of a high-purity expanded graphite sheet suited for use as an intervening liner in a single crystal pulling apparatus.
- FIG. 3 is an illustration of shaping of another high-purity expanded graphite sheet suited for use as a liner in a single crystal puller.
- FIG. 4 is a schematic representation of a flexibility measuring apparatus.
- the numerical symbols respectively denote the following: 1 —quartz crucible, 2 —heater, 3 —silicon melt, 4 —silicon single crystal, 5 —carbon crucible, 6 —upper ring, 7 —inner shield, 8 —lower ring, 9 —bottom heater, 10 —heat insulator, 11 —spill tray, 21 —sample (of high-purity expanded graphite sheet), 22 —weight, 23 —directions of bending, 24 —benders
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 1. This laminate was formed into the shape shown in FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 3. This laminate was formed into the shape shown in FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 5. This laminate was formed into the shape shown in FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- An expanded graphite sheet made of the same material and having the same size as that used in Example 1 was obtained.
- This sheet was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 1. This laminate was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 . The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-40, thickness: 0.4 mm, bulk density: 1.0 g/cm 3 , ash content: 0.2% by mass) was obtained.
- This sheet was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 5. This laminate was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 . The shaped article was then treated for purification; thus, it was heated to and maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-40, thickness: 0.4 mm, bulk density: 0.7 g/cm 3 , ash content: 0.2% by mass) was obtained.
- This sheet was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 5. This laminate was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 . The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 13. This laminate was formed into the shape shown in FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-20, thickness: 0.2 mm, bulk density: 1.0 g/cm 3 , ash content 0.2% by mass) was obtained.
- This sheet was formed into the shape shown in FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 10 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 15. This laminate was formed into the shape shown in FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-20, thickness: 0.2 mm, bulk density: 0.7 g/cm 3 , ash content: 0.2% by mass) was obtained.
- This sheet was formed into the shape shown in FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 10 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 17. This laminate was formed into the shape shown in FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 19. This laminate was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 . The shaped article was then treated for purification; thus, it was heated to and maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-100, thickness: 1.0 mm, bulk density: 1.0 g/cm 3 , ash content: 0.2% by mass) was obtained.
- This sheet was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 21.
- This laminate was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped article was then treated for purification; thus, it was heated to and maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-100, thickness: 1.0 mm, bulk density: 0.7 g/cm 3 , ash content: 0.2% by mass) was obtained.
- This sheet was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 23.
- This laminate was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped article was then treated for purification; thus, it was heated to and maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 5 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 1. This laminate was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice
- An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-100, thickness: 1.0 mm, bulk density: 1.0 g/cm 3 , ash content: 0.2% by mass) was obtained.
- This sheet was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped articled was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 21.
- This laminate was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an ode diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped article was then treated for purification; thus, it was heated to and maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-100, thickness: 1.0 mm, bulk density: 0.7 g/cm 3 , ash content: 0.2% by mass) was obtained.
- This sheet was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 23.
- This laminate was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped article was then treated for purification; thus, it was heated to and maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 5 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 1. This laminate was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Comparative Example 5. This laminate was formed into the shape shown in FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 5 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 1. This laminate was formed into the shape shown in FIG. 2 by manual working using a cutter. The time required for the shaping was 1 hour. The shaped article was subjected to 3 minutes of ultrasonic cleaning at 43 kHz to thereby remove cut dust derived from the expanded graphite laminate. Then, the shaped article was dried at 100° C. for 30 minutes to evaporate the moisture and then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another 10 expanded graphite sheets made by Toyo Tanso Co. Ltd. (grade name: PF-40, size: 1,000 ⁇ 1,000 ⁇ 0.4 (mm), bulk density: 0.6 g/cm 3 , ash content: 0.2% by mass).
- This laminate was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped article was then treated for purification; thus, it was maintained at; 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made by Toyo Tanso Co. Ltd. (grade name: PF-40, size: 1,000 ⁇ 1,000 ⁇ 0.4 (mm), bulk density: 0.3 g/cm 3 , ash content: 0.2% by mass).
- This laminate was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- a laminate was prepared by laying, one upon another, 10 expanded graphite sheets made by Toyo Tanso Co. Ltd. (grade name: PF-40, size: 1,000 ⁇ 1,000 ⁇ 0.4 (mm), bulk density: 0.2 g/cm 3 , ash content: 0.2% by mass).
- This laminate was formed into the shape shown in FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm 2 .
- the shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed.
- the bulk density of the expanded graphite sheet, the thickness per sheet, the number of sheets in the laminate, the method of shaping, the flexibility in the longitudinal direction, and the purity after purification treatment are summarized in Table 1.
- the expanded graphite sheets after purification treatment showed little changes in bulk density or in sheet thickness and thus were comparable in these respects to the sheets before purification treatment.
- the impurity content of each expanded graphite sheet after purification treatment was determined by weighing at least 15 g of the high-purity expanded graphite sheet in a porcelain crucible, placing the crucible in an electric furnace, heating it at 850° C. for 48 hours, and calculating the impurity content from the mass before heating and the mass after heating.
- Example 1 1.3 0.5 1 Thomson die 12 4 Example 2 1.3 0.5 10 Thomson die 12 4 Example 3 1.0 0.4 1 Thomson die 10 3 Example 4 1.0 0.4 10 Thomson die 10 3 Example 5 0.7 0.4 1 Thomson die 10 2 Example 6 0.7 0.4 10 Thomson die 10 2 Example 7 1.3 0.5 1 Water jet 12 3 Example 8 1.3 0.5 10 Water jet 12 3 Example 9 1.0 0.4 1 Water jet 10 2 Example 10 1.0 0.4 10 Water jet 10 2 Example 11 0.7 0.4 1 Water jet 10 1 Example 12 0.7 0.4 10 Water jet 10 1 Example 13 1.3 0.2 1 Thomson die 20 3 Example 14 1.3 0.2 10 Thomson die 20 3 Example 15 1.0 0.2 1 Thomson die 18 2 Example 16 1.0 0.2 10 Thomson die 18 2 Example 17 0.7 0.2 1 Thomson die 10 1 Example 18 0.7 0.2 10 Thomson die 10 1 Example 19 1.3 1.0 1 Water jet 10 5 Example 20 1.3 0.5 1 Thomson die 12 4 Example 2 1.3 0.5 10 Thomson die 12 4 Example 3 1.0 0.4 1 Thomson die 10 3 Example 5 0.7 0.4 1 Thomson die 10 2 Example
- Example 25 A silicon single crystal growth experiment was carried out using the high-purity expanded graphite sheet obtained in Example 25 and Comparative Example 3 each as an intervening liner in a CZ apparatus.
- the liner produced in Example 25 was used, it was confirmed by the eye that the area of yellowed portions suggesting the formation of silicon carbide was smaller as compared with the case of the liner produced in Comparative Example 3. This resulted from cracking of the high-purity expanded graphite sheet of Comparative Example 3 due to lack of flexibility.
- the products are useful in the semiconductor-related industries as those carbon crucible liners for use in CZ apparatus, CVD ovens and the like which are required to have high purity and flexibility and, in the nuclear industry-related fields, as in-core or in-pile parts required to be flexile and highly pure.
Abstract
The invention provides a flexible, highly pure expanded graphite sheet characterized by having an impurity content of 10 ppm or less and such a degree of flexibility that a sample thereof, 10×100 mm in size can withstand at least 10 times of bending in flexibility test comprising repeatedly bending the sample, with a 50-g weight suspended from one end thereof, by means of bending bodies with a diameter of 6 mm.
Description
- 1. Field of the Invention
- The present invention relates to a flexible, high-purity expanded graphite sheet, and to a method of producing the same.
- 2. Description of the Prior Art
- Expanded graphite sheets are generally produced by treating natural graphite, pyrolytic graphite, kish graphite or the like with a mixed solution containing sulfuric acid and nitric acid, for instance, then washing the same with water, drying the same, treating the same for expansion in an expansion oven at about 1,000° C., and firming the same into sheets using a rolling machine, for instance. Expanded graphite sheets are excellent in heat resistance and in gas and liquid in impermeability and therefore are used as packing materials, valve sheets, gaskets, and fuel cell separators, among others.
- Japanese Patent No. 2,620,606 discloses that highly pure expanded graphite sheets having an impurity content of not more than 15 ppm can be obtained by treating such expanded graphite sheets for increased purity in a halogen gas atmosphere at 2,000° C. or above. Such sheets are used in the process of semiconductor production.
- Hereinafter, a detailed description is given of a high-purity expanded graphite sheet for use in semiconductor production, which is taken as an example. Such a high-purity expanded graphite sheet is also used in the Czochralski (hereinafter referred to as “CZ” for short) process, which is a representative single crystal pulling technique. A sectional view of the main parts of a CZ apparatus is shown in
FIG. 1 . The CZ apparatus comprises such parts as acarbon crucible 5 supporting aquarts crucible 1, aheater 2, anupper ring 6, and aninner shield 7, among others. In the CZ apparatus, polycrystalline silicon placed in thequartz crucible 1 is heated to a high temperature to give asilicon melt 3, and the tip of a seed crystal held by a seed chuck is brought into contact with theraw material melt 3 and then pulled up while maintaining the contact to thereby pull up a silicon single crystal 4. - As shown in
FIG. 1 , thecarbon crucible 5 made of graphite or a carbon fiber-reinforced carbon composite material (such crucible is hereafter referred to as “carbon crucible”) is in direct contact with thequartz crucible 1 and, therefore, the surface of thecarbon crucible 5 is gradually converted to silicon carbide (hereinafter referred to as “SiC”) as a result of the reaction between thequartz crucible 1 andcarbon crucible 5 and/or the reaction between vaporized silicon and the graphite crucible. The difference in coefficient of thermal expansion between carbon and SiC is conducive to cracking of the carbon crucible, for instance. Furthermore, thequartz crucible 1 becomes firmly sticking to thecarbon crucible 5, making it difficult to take out thequartz crucible 1. - Japanese Patent No. 2,528,285 discloses, as a means for solving such problems, the use of a high-purity expanded graphite sheet as a liner intervening between the
quartz crucible 1 andcarbon crucible 5. - When an expanded graphite sheet is treated for improving the purity thereof, the flexibility of the expanded graphite sheet is generally impaired, so that it can no loner be used as a member which is required to have flexibility. Therefore, Japanese Patent No. 2,620,606 discloses a method of restoring flexibility which comprises compression molding. However, the method has other problems; the purity of the high-purity expanded graphite sheet is decreased upon compression molding and, when a complicated shape is given to the high-purity expanded graphite sheet insufficient in flexibility restoration by working with a cutter, for instance, the peripheral parts of the sheet are subject to cracking and/or chipping.
- When the whole inside surface (if the carbon crucible is covered with an expanded graphite sheet, the efficiency of heating of the
quartz crucible 1 decreases. Therefore, in recent years, various complicated liner shapes have been proposed so that the quartz crucible heating efficiency may be improved. Basically, each single crystal production operation consumes one intervening liner and, therefore, it is important to provide a method of producing high-purity expanded graphite sheets which is excellent in mass productivity. - Accordingly, it is an object of the present invention to provide a high-purity expanded graphite sheet having flexibility and a method of producing the same. Another object of the invention is to provide a method of manufacturing expanded graphite sheets which is suited for mass production as well.
- The present inventors made intensive investigations in an attempt to accomplish the above objects and, as a result, found that when an expanded graphite sheet whose bulk density is within a certain specific range is treated for attaining high purity, a high-purity expanded graphite sheet can be obtained without deterioration in flexibility even after the treatment for attaining high purity. This and other findings have now led to completion of the present invention. Thus, in a first aspect (Claim 1), the invention provides a flexible, high-purity expanded graphite sheet characterized in that it has an impurity content not exceeding 10 ppm and has such a degree of flexibility that a sample thereof can withstand at least 10 times of bending on a testing apparatus such as shown in
FIG. 4 . In a second aspect (Claim 2), the invention provides a flexible, high-purity expanded graphite sheet which has the above characteristics and is further characterized by its bulk density being 0.5 to 1.3 g/cm3. In a third aspect (Claim 3), the invention provides a flexible, high-purity expanded graphite sheet as defined inClaim - For obtaining the flexible, high-purity expanded graphite sheet according to
Claim 1, it is necessary to use scaly graphite, kish graphite, pyrolytic graphite or the like as a filler, subject this to oxidation treatment by immersing the same in a mixed acid supplemented with concentrated sulfuric acid, concentrated nitric acid, etc., wash the immersed filler with water and, after drying, treat the same for expansion by heating to give expanded graphite, and adjust the bulk density thereof to about 0.7 to 1.3 g/cm3 by compression molding using a press or rolling machine. Expanded graphite sheets having a bulk density lower than 0.7 g/cm3 cannot acquire, even after purification treatment, such a degree of flexibility as to withstand at least 10 times of bending, hence are unfavorable. Expanded graphite sheets having a bulk density exceeding, 1.3 g/cm3 are also undesirable, since the impurity content therein cannot be reduced to 10 ppm or below even by purification treatment. In a preferred embodiment of the invention, expanded graphite sheets with a bulk density adjusted to 0.8 to 1.3 g/cm3, more preferably to 0.9 to 1.3 g/cm3, are subjected to treatment for attaining high purity. The method of purification treatment itself may be any of those known in the art. For example, flexible, high-purity expanded graphite sheets having an impurity content of not more than 10 ppm and a degree of flexibility as to withstand at least 10 times of bending can be obtained by heating expanded graphite sheets at 2,000° C. or above in a halogen gas atmosphere to thereby convert metals in the sheets to metal halide compounds showing a high vapor pressure and allow them to vaporize. The bulk density and sheet thickness of expanded graphite sheets after purification treatment show little changes and remain almost equal to those before treatment. A flexibility measuring apparatus is schematically shown inFIG. 3 . A 50-g weight 22 is attached to one end of a 10 mm×100mm sample 21 of a high-purity expanded graphite sheet and subjected to repeated bending by means ofbending bodies 24 with a diameter of 6 mm. The number of times of bending until breakage is counted and recorded as the flexibility in the longitudinal direction. - In a fourth aspect (Claim 4), the invention provides a method of producing flexible, high-purity expanded graphite sheets which comprises forming an expanded graphite sheet having a bulk density of 0.7 to 1.3 g/cm3 into a desired shape and then subjecting the shaped sheet to purification treatment. Expanded graphite sheets having a bulk density less than 0.7 g/cm3 are undesirable since any purification treatment cannot improve their flexibility to a level of at least 10 times, as mentioned above. Expanded graphite sheets having a bulk density exceeding 1.3 g/cm3 are also unfavorable since their impurity content cannot be reduced to 10 ppm or less by purification treatment. Preferably, the expanded graphite sheet to be treated for purification has a thickness of 0.2 to 1.0 mm. When the expanded graphite sheet before purification treatment is less than 0.2 mm in thickness, the sheet after purification treatment tends to show marked decreases in flexibility and strength, hence are susceptible to cracking, for instance. When the expanded graphite sheet is thicker than 1.0 mm, the impurity content cannot be reduced to a satisfactory extent by purification treatment. More preferably, the expanded graphite sheet to be subjected to purification treatment has a thickness of 0.3 to 0.9 mm. Most preferably, 0.5 to 0.8-mm-thick expanded graphite sheets are subjected to purification treatment. As the “desired shape” so referred to herein, there may be mentioned, for example, the shape shown in
FIG. 2 orFIG. 3 and, further, figures of line symmetry, such as ellipses, stars and the Imperial crest of chrysanthemum, and asymmetric figures. - In a fifth aspect (Claim 5), the invention provides a modification of the method specified above which modification comprises forming a plurality of expanded graphite sheets each into one and the same desired shape simultaneously in a laminate form, followed by purification treatment. This modification is preferred since the mass productivity in manufacturing expanded graphite sheets having one and the same desired, complicated shape can be improved by laying a plurality of expanded graphite sheets one upon another and working them simultaneously in one operation according to the method mentioned above. Preferably, a plurality of expanded graphite sheets each having a thickness of 0.2 to 1.0 mm are laid one upon another. When each expanded graphite sheet is less than 0.2 mm in thickness, the expanded graphite sheet cannot acquire flexibility or strength but becomes susceptible to cracking, for instance. When each sheet is thicker than 1.0 mm, the impurity content cannot be reduced to a satisfactory extent by purification treatment; this is unfavorable. It is desirable that the bulk density of expanded graphite sheets prior to purification treatment be 0.7 to 1.3 g/cm3.
- In a sixth aspect (Claim 6), the invention provides a method of producing such expanded graphite sheets as mentioned above in which the shaping of expanded graphite sheets is carried out by at least one method selected from among such methods as slitting, punching using a Thomson die, water jet working, and laser working. From the mass productivity viewpoint, however, punching with a Thomson die and water jet working are preferred since they can reduce the working time, are less likely to decrease the purity of expanded graphite sheets and, further, are excellent in mass productivity. It is to be added that when expanded graphite sheets are shaped by punching using a Thomson die, the purification treatment should preferably be carried out after removing working dust from the worked surface (cut surface) by ultrasonic cleaning in a state immersed in water, alcohol or the like and the subsequent drying for evaporation of the moisture.
- In a seventh aspect (Claim 7), the invention provides the use of the flexible, high-purity expanded graphite sheet as defined in any one of
Claims 1 to 3 as a carbon crucible liner. When such a high-purity expanded graphite sheet having flexibility and a low impurity content is used as a carbon crucible liner, the stability of the quartz crucible is good and the intrusion of silicon monoxide gas can be prevented, so that the carbon crucible can be inhibited from beg converted to silicon carbide and the life of the expensive carbon crucible can be prolonged. -
FIG. 1 is a schematic sectional view of a single crystal puller. -
FIG. 2 is an illustration of shaping of a high-purity expanded graphite sheet suited for use as an intervening liner in a single crystal pulling apparatus. -
FIG. 3 is an illustration of shaping of another high-purity expanded graphite sheet suited for use as a liner in a single crystal puller. -
FIG. 4 is a schematic representation of a flexibility measuring apparatus. - In
FIGS. 1 and 4 , the numerical symbols respectively denote the following: 1—quartz crucible, 2—heater, 3—silicon melt, 4—silicon single crystal, 5—carbon crucible, 6—upper ring, 7—inner shield, 8—lower ring, 9—bottom heater, 10—heat insulator, 11—spill tray, 21—sample (of high-purity expanded graphite sheet), 22—weight, 23—directions of bending, 24—benders - The following examples illustrate the present invention more specifically. These examples are, however, by no means limitative of the scope of the present invention.
- An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-50, size: 1,000×1,000×0.5 (mm), bulk density: 1.3 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 10 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 1. This laminate was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made by Toyo Tanso Co. Ltd. grade name: PF-40, thickness 0.4 mm, bulk density: 1.0 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 10 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 3. This laminate was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-40, thickness: 0.4 mm, bulk density: 0.7 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 10 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 5. This laminate was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made of the same material and having the same size as that used in Example 1 was obtained. This sheet was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 1. This laminate was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-40, thickness: 0.4 mm, bulk density: 1.0 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 5. This laminate was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was heated to and maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-40, thickness: 0.4 mm, bulk density: 0.7 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 5. This laminate was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-20, size: 1,000×1,000×0.2 (mm), bulk density: 1.3 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 10 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 13. This laminate was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-20, thickness: 0.2 mm, bulk density: 1.0 g/cm3, ash content 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 10 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 15. This laminate was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-20, thickness: 0.2 mm, bulk density: 0.7 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 10 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 17. This laminate was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-100, size: 1,000×1,000×1.0 (mm), bulk density: 1.3 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 19. This laminate was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was heated to and maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-100, thickness: 1.0 mm, bulk density: 1.0 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 21. This laminate was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was heated to and maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-100, thickness: 1.0 mm, bulk density: 0.7 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 23. This laminate was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was heated to and maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 5 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 1. This laminate was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice - An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-100, thickness: 1.0 mm, bulk density: 1.0 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped articled was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 21. This laminate was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an ode diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was heated to and maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-100, thickness: 1.0 mm, bulk density: 0.7 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 23. This laminate was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was heated to and maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 5 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 1. This laminate was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made by Toyo Tanso Co. Ltd. (grade name: PF-120, size: 1,000×1,000×1.2 (mm), bulk density: 1.3 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 10 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made of the same material and having the same size as the sheet used in Comparative Example 5. This laminate was formed into the shape shown in
FIG. 2 by punching using a hydraulic press and a Thomson die at a pressure of 50 MPa. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 5 expanded graphite sheets made of the same material and having the same size as the sheet used in Example 1. This laminate was formed into the shape shown in
FIG. 2 by manual working using a cutter. The time required for the shaping was 1 hour. The shaped article was subjected to 3 minutes of ultrasonic cleaning at 43 kHz to thereby remove cut dust derived from the expanded graphite laminate. Then, the shaped article was dried at 100° C. for 30 minutes to evaporate the moisture and then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another 10 expanded graphite sheets made by Toyo Tanso Co. Ltd. (grade name: PF-40, size: 1,000×1,000×0.4 (mm), bulk density: 0.6 g/cm3, ash content: 0.2% by mass). This laminate was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was maintained at; 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made by Toyo Tanso Co. Ltd. (grade name: PF-40, size: 1,000×1,000×0.4 (mm), bulk density: 0.3 g/cm3, ash content: 0.2% by mass). This laminate was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - A laminate was prepared by laying, one upon another, 10 expanded graphite sheets made by Toyo Tanso Co. Ltd. (grade name: PF-40, size: 1,000×1,000×0.4 (mm), bulk density: 0.2 g/cm3, ash content: 0.2% by mass). This laminate was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - An expanded graphite sheet made by Toyo Tanso Co. Ltd. grade name: PF-40, size: 1,000×1,000×0.4 (mm), bulk density: 0.6 g/cm3, ash content: 0.2% by mass) was obtained. This sheet was formed into the shape shown in
FIG. 2 by subjecting to water jet working using a nozzle having an orifice diameter of 0.1 mm at a water pressure of 3,000 kg/cm2. The shaped article was then treated for purification; thus, it was maintained at 2,000° C. for 10 hours while gaseous chlorine was fed. - For each of Examples 1 to 25 and Comparative Examples 1 to 11, the bulk density of the expanded graphite sheet, the thickness per sheet, the number of sheets in the laminate, the method of shaping, the flexibility in the longitudinal direction, and the purity after purification treatment are summarized in Table 1. The expanded graphite sheets after purification treatment showed little changes in bulk density or in sheet thickness and thus were comparable in these respects to the sheets before purification treatment.
- The impurity content of each expanded graphite sheet after purification treatment was determined by weighing at least 15 g of the high-purity expanded graphite sheet in a porcelain crucible, placing the crucible in an electric furnace, heating it at 850° C. for 48 hours, and calculating the impurity content from the mass before heating and the mass after heating.
-
TABLE 1 Number Bulk Sheet of sheets Impurity density thickness in Shaping Flexibility content (g/cm3) (mm/sheet) laminate method (times) (ppm) Example 1 1.3 0.5 1 Thomson die 12 4 Example 2 1.3 0.5 10 Thomson die 12 4 Example 3 1.0 0.4 1 Thomson die 10 3 Example 4 1.0 0.4 10 Thomson die 10 3 Example 5 0.7 0.4 1 Thomson die 10 2 Example 6 0.7 0.4 10 Thomson die 10 2 Example 7 1.3 0.5 1 Water jet 12 3 Example 8 1.3 0.5 10 Water jet 12 3 Example 9 1.0 0.4 1 Water jet 10 2 Example 10 1.0 0.4 10 Water jet 10 2 Example 11 0.7 0.4 1 Water jet 10 1 Example 12 0.7 0.4 10 Water jet 10 1 Example 13 1.3 0.2 1 Thomson die 20 3 Example 14 1.3 0.2 10 Thomson die 20 3 Example 15 1.0 0.2 1 Thomson die 18 2 Example 16 1.0 0.2 10 Thomson die 18 2 Example 17 0.7 0.2 1 Thomson die 10 1 Example 18 0.7 0.2 10 Thomson die 10 1 Example 19 1.3 1.0 1 Water jet 10 5 Example 20 1.3 1.0 10 Water jet 10 5 Example 21 1.0 1.0 1 Water jet 10 4 Example 22 1.0 1.0 10 Water jet 10 4 Example 23 0.7 1.0 1 Water jet 10 2 Example 24 0.7 1.0 10 Water jet 10 2 Example 25 1.3 0.5 5 Water jet 12 1 Compar. Ex. 1 1.5 0.5 1 Thomson die 30 50 Compar. Ex. 2 1.5 0.5 10 Thomson die 30 50 Compar. Ex. 3 1.3 0.1 1 Thomson die 1 1 Compar. Ex. 4 1.3 0.1 10 Thomson die 1 1 Compar. Ex. 5 1.3 1.2 1 Thomson die 5 30 Compar. Ex. 6 1.3 1.2 10 Thomson die 5 30 Compar. Ex. 7 1.3 0.5 5 Cutter 12 30 Compar. Ex. 8 0.6 0.4 10 Water jet 1 2 Compar. Ex. 9 0.3 0.4 10 Water jet 1 1 Compar. Ex. 10 0.2 0.4 10 Water jet 1 1 Compar. Ex. 11 0.6 0.4 1 Water jet 1 2 - As is evident from Table 1, those expanded graphite sheets having a bulk density of 0.7 to 1.3 g/cm3 and a thickness of 0.2 to 1.0 mm per sheet showed only slight decreases in flexibility after purification treatment and could be prevented from decreasing in purity.
- A silicon single crystal growth experiment was carried out using the high-purity expanded graphite sheet obtained in Example 25 and Comparative Example 3 each as an intervening liner in a CZ apparatus. When the liner produced in Example 25 was used, it was confirmed by the eye that the area of yellowed portions suggesting the formation of silicon carbide was smaller as compared with the case of the liner produced in Comparative Example 3. This resulted from cracking of the high-purity expanded graphite sheet of Comparative Example 3 due to lack of flexibility.
- When a plurality of expanded graphite sheets having a bulk density of 0.7 to 1.3 g/cm3 and a thickness of 0.2 to 1.0 mm per sheet are formed into a laminate and the late is worked into a desired shape, no impairment in flexibility is found after treatment for attaining high purity. In addition, when the laminate is shaped by water jet working, the working time can be reduced to 1/10 or shorter as compared with that in the prior art and the impurity content can also be reduced to 1/10 or below. Therefore, the products are useful in the semiconductor-related industries as those carbon crucible liners for use in CZ apparatus, CVD ovens and the like which are required to have high purity and flexibility and, in the nuclear industry-related fields, as in-core or in-pile parts required to be flexile and highly pure.
Claims (20)
1. A method of producing flexible, high-purity expanded graphite sheets which comprises forming an expanded graphite sheet having a bulk density of 0.7 to 1.3 g/cm3 into a desired shape and then subjecting the shaped sheet to treatment for attaining high purity.
2. A method of producing flexible, high-purity expanded graphite sheets which comprises forming a plurality of expanded graphite sheets each having a bulk density of 0.7 to 1.3 g/cm3 into one and the same desired shape simultaneously in a laminate form, followed by treatment for attaining high purity.
3. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 1 , wherein the shaping of expanded graphite sheets is carried out by at least one method selected from the group consisting of working on a slitting machine, punching using a Thomson die, water jet working, and laser working.
4. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 2 , wherein the shaping of expanded graphite sheets is carried out by at least one method selected from the group consisting of working on a slitting machine, punching using a Thomson die, water jet working, and laser working.
5. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 1 , wherein the expanded graphite sheet before purification treatment has a thickness of 0.2 to 1.0 mm.
6. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 2 , wherein the expanded graphite sheet before purification treatment has a thickness of 0.2 to 1.0 mm.
7. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 1 , wherein the expanded graphite sheet after purification treatment has an impurity content not exceeding 10 ppm.
8. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 2 , wherein the expanded graphite sheet after purification treatment has an impurity content not exceeding 10 ppm.
9. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 5 , wherein the expanded graphite sheet after purification treatment has an impurity content not exceeding 10 ppm.
10. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 6 , wherein the expanded graphite sheet after purification treatment has an impurity content not exceeding 10 ppm.
11. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 5 , wherein the thickness is 0.3 to 0.9 mm.
12. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 6 , wherein the thickness is 0.3 to 0.9 mm.
13. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 5 , wherein the thickness is 0.5 to 0.8 mm.
14. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 6 , wherein the thickness is 0.5 to 0.8 mm.
15. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 1 , wherein the bulk density is 0.8 to 1.3 g/cm3.
16. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 2 , wherein the bulk density is 0.8 to 1.3 g/cm3.
17. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 1 , wherein the bulk density is 0.9 to 1.3 g/cm3.
18. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 2 , wherein the bulk density is 0.9 to 1.3 g/cm3.
19. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 1 , wherein said purification treatment comprises heating the sheet at 2,000° C. or above in a halogen atmosphere.
20. The method of producing flexible, high-purity expanded graphite sheets as defined in claim 2 , wherein said purification treatment comprises heating the sheet at 2,000° C. or above in a halogen atmosphere.
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US10/462,663 US20040043220A1 (en) | 2002-06-18 | 2003-06-17 | Flexible, high purity expanded graphite sheet, method of producing same, and carbon crucible lining using said sheet |
US12/478,792 US20090246493A1 (en) | 2002-06-18 | 2009-06-05 | Flexible, high purity expanded graphite sheet, method of producing same, and carbon crucible lining using said sheet |
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US10/462,663 Abandoned US20040043220A1 (en) | 2002-06-18 | 2003-06-17 | Flexible, high purity expanded graphite sheet, method of producing same, and carbon crucible lining using said sheet |
US11/124,240 Expired - Lifetime US7914894B2 (en) | 2002-06-18 | 2005-05-09 | Flexible, high purity expanded graphite sheet, method of producing same, and carbon crucible lining using said sheet |
US12/478,792 Abandoned US20090246493A1 (en) | 2002-06-18 | 2009-06-05 | Flexible, high purity expanded graphite sheet, method of producing same, and carbon crucible lining using said sheet |
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US11/124,240 Expired - Lifetime US7914894B2 (en) | 2002-06-18 | 2005-05-09 | Flexible, high purity expanded graphite sheet, method of producing same, and carbon crucible lining using said sheet |
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JP (4) | JP4272248B2 (en) |
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US10988384B2 (en) | 2016-06-07 | 2021-04-27 | Kaneka Corporation | Graphite-sheet processed article and graphite sheet processed article manufacturing method |
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US7914894B2 (en) | 2011-03-29 |
JP2009051730A (en) | 2009-03-12 |
US20050196613A1 (en) | 2005-09-08 |
JP4801101B2 (en) | 2011-10-26 |
TWI248916B (en) | 2006-02-11 |
TW200400155A (en) | 2004-01-01 |
CN1480394A (en) | 2004-03-10 |
JP2008150286A (en) | 2008-07-03 |
JP5004936B2 (en) | 2012-08-22 |
JP2008150287A (en) | 2008-07-03 |
US20040043220A1 (en) | 2004-03-04 |
JP2009133612A (en) | 2009-06-18 |
JP4272248B2 (en) | 2009-06-03 |
JP5210842B2 (en) | 2013-06-12 |
KR100642923B1 (en) | 2006-11-03 |
KR20040002337A (en) | 2004-01-07 |
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