JP2009062203A - Method for producing silicon carbide structure - Google Patents
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本発明は、高温ガスや金属融液のフィルター、高温ガス吸着材、触媒担体、半導体製造装置部材、生体培養坦体材料として、実用化が期待されている炭化ケイ素構造体の製造方法に関するものである。 The present invention relates to a method for producing a silicon carbide structure that is expected to be put to practical use as a high-temperature gas or metal melt filter, a high-temperature gas adsorbent, a catalyst carrier, a semiconductor production apparatus member, and a biological culture carrier material. is there.
炭化ケイ素の多結晶体セラミックスは、高温においても高強度で、耐摩耗性、耐食性に優れた非酸化物半導体で、そのバルク体や多孔体などの構造体は、高温構造部材や半導体製造用部材、発熱体、ディーゼル車の廃ガス浄化用フィルターをはじめとする高温ガスフィルター、溶融金属濾過材、ガス分解浄化反応触媒の坦体などの用途に用いられている。また、炭化ケイ素は、地球の地殻中に豊富に存在する元素で構成されることや、非酸化物セラミックスの中では、表面酸化被膜の形成により耐酸化性も高く、低毒性で長寿命である。 Polycrystalline ceramics of silicon carbide are non-oxide semiconductors that have high strength even at high temperatures, and are excellent in wear resistance and corrosion resistance. Structures such as bulk bodies and porous bodies are high-temperature structural members and semiconductor manufacturing members. It is used in applications such as heating elements, high-temperature gas filters such as diesel exhaust gas purification filters, molten metal filter media, and gas decomposition purification reaction catalyst carriers. Silicon carbide is composed of elements that are abundant in the earth's crust, and among non-oxide ceramics, it has high oxidation resistance due to the formation of a surface oxide film, has low toxicity, and has a long life. .
従来、炭化ケイ素の構造体は、炭化ケイ素粉体の固相および焼結助剤添加による液相焼結技術や加圧焼結技術、有機または無機前駆体の化学反応および熱分解反応を利用した製造技術、各種構造体にシリコンを含む溶液やシリコン融液を含浸させる技術等により合成されてきた。炭化ケイ素の前述の様々な特性を引き出すためには、α型またはβ型の結晶相でなければならず、α型やβ型の結晶相の炭化ケイ素を得るには、不活性雰囲気下で１２００℃から２４００℃におよぶ高温反応や焼成が必要である。高温での製造には時間がかかり効率が悪く、高温条件での処理に対応できる設備が必要となり、製造コストが高いという問題がある。 Conventionally, the structure of silicon carbide has utilized liquid phase sintering technology and pressure sintering technology by adding solid phase and sintering aid of silicon carbide powder, chemical reaction and thermal decomposition reaction of organic or inorganic precursors. It has been synthesized by a manufacturing technique, a technique in which various structures are impregnated with a solution containing silicon or a silicon melt. In order to derive the above-mentioned various characteristics of silicon carbide, it must be in the α-type or β-type crystal phase. To obtain silicon carbide in the α-type or β-type crystal phase, 1200 under an inert atmosphere. A high temperature reaction or calcination ranging from 0 to 2400 ° C. is required. Manufacturing at high temperatures is time consuming and inefficient, and requires equipment that can handle processing under high temperature conditions, resulting in high manufacturing costs.
この長時間の高温製造プロセスを短縮、または省略する製造方法として、非晶質炭素またはフラーレンの粉末とシリコンの粉末とを原料とし、これらの原料の混合体を金型圧縮成型し、ナトリウム蒸気下６００℃から９００℃に加熱することにより、β型結晶構造を有し、混合原料粉末の形態を維持した炭化ケイ素多孔体の合成方法が提案された（非特許文献１参照）。 As a manufacturing method that shortens or omits this long-time high-temperature manufacturing process, amorphous carbon or fullerene powder and silicon powder are used as raw materials, and a mixture of these raw materials is molded by molding, A method for synthesizing a silicon carbide porous body having a β-type crystal structure and maintaining the form of a mixed raw material powder by heating from 600 ° C. to 900 ° C. has been proposed (see Non-Patent Document 1).
しかし、非特許文献１に記載の方法では、炭素とシリコンとの原料粉末を混合成形しなければならず、炭化ケイ素構造体の形態や組織も、混合原料粉末から成形可能な形態に限られてしまうという問題点がある。 However, in the method described in Non-Patent Document 1, the raw material powder of carbon and silicon must be mixed and molded, and the form and structure of the silicon carbide structure are limited to a form that can be formed from the mixed raw material powder. There is a problem that.
本発明の目的は、従来法の原料粉末の混合工程を省き、従来法では実現できなかった主として炭素からなる構造体の形態を保持した炭化ケイ素構造体の製造を、低温で、かつ短時間で行うことことができる炭化ケイ素構造体の製造方法を提供することにある。 The object of the present invention is to eliminate the mixing step of the raw material powder of the conventional method, and to produce a silicon carbide structure that retains the form of the structure mainly composed of carbon, which could not be realized by the conventional method, at a low temperature and in a short time. An object of the present invention is to provide a method for producing a silicon carbide structure that can be performed.
本発明によれば、不活性ガス雰囲気の反応容器中で、シリコンを含むナトリウムの融液を付加した状態で、主として炭素からなる構造体を加熱することを、特徴とする炭化ケイ素構造体の製造方法が得られる。 According to the present invention, a silicon carbide structure characterized by heating a structure mainly composed of carbon in a reaction vessel in an inert gas atmosphere with a silicon-containing sodium melt added thereto. A method is obtained.
また、本発明によれば、前記主として炭素からなる構造体は、天然木材または植物・生体組織を炭化したもの、非晶質炭素、フラーレンまたはカーボンナノチューブを主な構成要素とする素材で人工的に合成された３次元バルク体、布、網、線、繊維、およびそれらが合わさったもののうち、少なくともいずれか一種類であることを、特徴とする炭化ケイ素構造体の製造方法が得られる。 Further, according to the present invention, the structure mainly composed of carbon is artificially made of a material mainly composed of natural wood, carbonized plant / living tissue, amorphous carbon, fullerene, or carbon nanotube. A method for producing a silicon carbide structure characterized in that it is at least one of a synthesized three-dimensional bulk body, cloth, net, wire, fiber, and a combination thereof is obtained.
また、本発明によれば、前記主として炭素からなる構造体を加熱して得られる炭化ケイ素構造体が、前記主として炭素からなる構造体の形態や組織、構造を保持していることを、特徴とする炭化ケイ素構造体の製造方法が得られる。 According to the present invention, the silicon carbide structure obtained by heating the structure mainly composed of carbon retains the form, structure and structure of the structure mainly composed of carbon. A method for producing a silicon carbide structure is obtained.
また、本発明によれば、前記主として炭素からなる構造体を加熱して得られる炭化ケイ素構造体中の主たる炭化ケイ素の結晶構造がβ型であることを、特徴とする炭化ケイ素構造体の製造方法が得られる。 According to the present invention, the silicon carbide structure is characterized in that the main silicon carbide crystal structure in the silicon carbide structure obtained by heating the structure mainly composed of carbon is β-type. A method is obtained.
更に、本発明によれば、前記主として炭素からなる構造体を加熱する温度は、６００℃以上、１２００℃以下であることを、特徴とする炭化ケイ素構造体の製造方法が得られる。 Furthermore, according to the present invention, there is obtained a method for producing a silicon carbide structure characterized in that a temperature for heating the structure mainly composed of carbon is 600 ° C. or more and 1200 ° C. or less.
本発明により、従来よりも簡易に、低温で、かつ短時間で炭化ケイ素構造体を製造することができる炭化ケイ素構造体の製造方法が得られる。これにより、炭化ケイ素構造体を用いた低価格、高性能な高温構造部材や半導体製造用部材、発熱体、廃ガス浄化用フィルター、高温ガスフィルター、溶融金属濾過材、ガス分解浄化反応触媒の坦体、生体培養坦体材料等が得られるという効果が得られる。 By this invention, the manufacturing method of the silicon carbide structure which can manufacture a silicon carbide structure at low temperature and a short time more simply than before is obtained. As a result, low-cost, high-performance high-temperature structural members and semiconductor manufacturing members using silicon carbide structures, heating elements, waste gas purification filters, high-temperature gas filters, molten metal filter media, and gas decomposition purification reaction catalyst carriers The effect that a body, a biological culture carrier material, etc. are obtained is acquired.
以下、本発明の実施の形態について、詳細に説明する。
図１は、合成に使用した反応容器の概略図を示す。まず初めに、木材（バルサと檜材各１０×１０×３０ｍｍ，バルサφ１０ｍｍ×４０ｍｍ）を８０℃の空気中で４時間乾燥後、５５０℃の減圧下（約１００Ｔｏｒｒ）で６時間加熱し、木材を炭化し、植物細胞壁の高次構造を保持した主に炭素からなる構造体とした。次に、得られた植物細胞壁の高次構造を保持した主に炭素からなる構造体である２つの炭化木１（合計２９６．２ｍｇ）を、シリコン３（８１４．６ｍｇ、三津和化学薬品株式会社製、純度９９．９９９％、粒径−２００ｍｅｓｈ）、およびナトリウム２（７９０．７ｍｇ、日本曹達株式会社製、純度９９．９５％）とともに、アルゴンガス雰囲気のグローブボックス中で、焼結窒化ホウ素坩堝４（内径２８ｍｍ、深さ２５ｍｍ、昭和電工株式会社製、純度９９．５％）の中に入れた。さらに、これらをニッケル製ルツボ５に入れた。図２（ａ）は、それぞれの材料をチャージした加熱前の焼結窒化ホウ素坩堝４である。
Hereinafter, embodiments of the present invention will be described in detail.
FIG. 1 shows a schematic diagram of a reaction vessel used for synthesis. First, wood (balsa and bran 10 × 10 × 30 mm, balsa φ10 mm × 40 mm) was dried in air at 80 ° C. for 4 hours and then heated at 550 ° C. under reduced pressure (about 100 Torr) for 6 hours. Was carbonized to obtain a structure mainly composed of carbon retaining the higher-order structure of the plant cell wall. Next, two carbonized woods 1 (total 296.2 mg), which is a structure mainly composed of carbon retaining the higher-order structure of the obtained plant cell wall, were replaced with silicon 3 (814.6 mg, Mitsuwa Chemicals Co., Ltd.). Sintered boron nitride crucible in a glove box in an argon gas atmosphere together with manufactured product, purity 99.999%, particle size -200 mesh), and sodium 2 (790.7 mg, manufactured by Nippon Soda Co., Ltd., purity 99.95%) 4 (inner diameter 28 mm, depth 25 mm, Showa Denko KK, purity 99.5%). Further, these were put in a nickel crucible 5. FIG. 2A shows a sintered boron nitride crucible 4 before heating and charged with each material.
次に、図１に示したように、熱電対８を通したニッケル台６の上にニッケル製ルツボ５を置き、ニッケル製キャップ７で覆った。試料部の雰囲気をＡｒガスで約３ａｔｍに加圧し、ヒーター９により２時間で７００℃まで昇温し、２４時間保持加熱した後、炉冷した。炉冷後、グローブボックス中で焼結窒化ホウ素坩堝４内に入った試料を取り出した。６００℃以下の反応温度では、炭化ケイ素の十分な生成反応が得られず、また、１０００℃では、炭化ケイは合成されるが、ナトリウムの蒸発が激しくなり、１２００℃以上の温度では、図１の装置を用いた合成が困難となる。従って、加熱する温度は、６００℃以上、１２００℃以下、好ましくは９００℃以下の必要がある。 Next, as shown in FIG. 1, a nickel crucible 5 was placed on a nickel base 6 through which a thermocouple 8 was passed and covered with a nickel cap 7. The atmosphere of the sample part was pressurized to about 3 atm with Ar gas, heated to 700 ° C. in 2 hours by the heater 9, held and heated for 24 hours, and then cooled in the furnace. After cooling in the furnace, the sample contained in the sintered boron nitride crucible 4 in the glove box was taken out. At a reaction temperature of 600 ° C. or lower, sufficient formation reaction of silicon carbide cannot be obtained, and at 1000 ° C., silicon carbide is synthesized, but sodium evaporates vigorously, and at a temperature of 1200 ° C. or higher, FIG. It becomes difficult to synthesize using the apparatus. Therefore, the heating temperature needs to be 600 ° C. or higher and 1200 ° C. or lower, preferably 900 ° C. or lower.
図２（ｂ）は、加熱冷却後の焼結窒化ホウ素坩堝４である。図２（ｂ）から明らかに、加熱後の試料は加熱前の形態を維持しており、表面および内部には、固化したナトリウム−シリコン系の金属間化合物を含むナトリウムが付着していることが確認された。この試料に付着したナトリウムやナトリウム−シリコン系の金属間化合物を、イソプロピルアルコールやエタノールと反応させた。その後、この試料を蒸留水で超音波洗浄し、空気中２００℃で乾燥させた。 FIG. 2B shows the sintered boron nitride crucible 4 after heating and cooling. As apparent from FIG. 2 (b), the sample after heating maintains the form before heating, and the surface and the inside are attached with sodium containing solidified sodium-silicon intermetallic compound. confirmed. Sodium or sodium-silicon intermetallic compounds attached to this sample were reacted with isopropyl alcohol or ethanol. Then, this sample was ultrasonically cleaned with distilled water and dried at 200 ° C. in air.
得られた試料をメノウ乳鉢で粉砕し、そのＸ線粉末回折（ＸＲＤ）パターンをＸ線回折装置（株式会社リガク製、製品名「ＲＩＮＴ２２００」：ＣｕＫα線、管電圧４０ｋＶ、管電流４０ｍＡ）を用いて測定した。図３は、バルサを使用して作製した粉砕試料のＸＲＤパターンである。すべてのＸＲＤピークは、立方晶系、格子定数ａ＝０．４３６ｎｍで指数付けされ、さらに各ピークの相対強度から、作製された試料がβ型の結晶構造を有する炭化ケイ素であることが分かる。 The obtained sample was pulverized in an agate mortar, and its X-ray powder diffraction (XRD) pattern was used using an X-ray diffractometer (manufactured by Rigaku Corporation, product name “RINT2200”: CuKα ray, tube voltage 40 kV, tube current 40 mA). Measured. FIG. 3 is an XRD pattern of a ground sample produced using balsa. All XRD peaks are indexed with a cubic system, lattice constant a = 0.436 nm, and the relative intensity of each peak indicates that the prepared sample is silicon carbide having a β-type crystal structure.
洗浄後の試料の形態を、走査型電子顕微鏡：ＳＥＭ（株式会社日立製作所製、製品名「Ｘ−６５０Ｓ」）で観察するとともに、このＳＥＭに搭載されている半導体検出器（ＥＤＡＸ Ｉｎｃ製、製品名「ＮＥＷ ＸＬ３０」）を用いて元素分析を行った。図４は、炭化ケイ素試料のＳＥＭ像である。図４（ａ）は、檜材の炭化木から得られた試料で、図４（ｂ）は、バルサ材の炭化木を用いて得られた試料である。両炭化ケイ素試料に植物特有のセル構造が観察されたことから、ミクロな構造も保持されていることが明らかである。これらの部分のエネルギー分散型Ｘ線分析（ＥＤＸ分析）で、シリコンと炭素とがおおよそ５０ａｔ％づつ含まれており、その他、０．６〜０．７ａｔ％のナトリウム、２〜３ａｔ％の酸素、および０．１ａｔ％の生体由来のカルシウムが検出された。 The morphology of the sample after washing is observed with a scanning electron microscope: SEM (manufactured by Hitachi, Ltd., product name “X-650S”), and a semiconductor detector mounted on this SEM (manufactured by EDAX Inc., product) Elemental analysis was performed using the name “NEW XL30”). FIG. 4 is an SEM image of a silicon carbide sample. FIG. 4A is a sample obtained from a carbonized wood made of firewood, and FIG. 4B is a sample obtained using a carbonized wood made of balsa wood. It is clear that the microscopic structure is also retained from the fact that plant-specific cell structures were observed in both silicon carbide samples. The energy dispersive X-ray analysis (EDX analysis) of these parts contains silicon and carbon in an amount of approximately 50 at%, 0.6 to 0.7 at% sodium, 2-3 at% oxygen, And 0.1 at% of biological calcium was detected.
更に、人工的に合成された炭素構造体として活性炭を使用し、内径２８ｍｍの焼結窒化ホウ素坩堝４内に、粒径６ｍｍの活性炭を３０ｍｇ、ナトリウム２を７３ｍｇ、シリコン３を７１ｍｇ入れ、Ａｒガス雰囲気中、７００℃で２４時間加熱することにより、活性炭の形態を保持したβ型炭化ケイ素が合成された。 Furthermore, using activated carbon as an artificially synthesized carbon structure, 30 mg of activated carbon having a particle diameter of 6 mm, 73 mg of sodium 2 and 71 mg of silicon 3 are placed in a sintered boron nitride crucible 4 having an inner diameter of 28 mm, and Ar gas Β-type silicon carbide retaining the activated carbon form was synthesized by heating at 700 ° C. for 24 hours in an atmosphere.
本実施の形態では、バルサ材と桧材と活性炭とについて説明したが、炭素からなる構造体が得られる天然木材または植物・生体組織を炭化したもの、非晶質炭素、フラーレンまたはカーボンナノチューブなどを主な構成要素とする素材で人工的に合成された３次元バルク体、布、網、線、繊維、およびそれらが合わさったもののうち、少なくともいずれか一種類であれば、同様の反応が得られることは明らかである。 In this embodiment, balsa wood, straw wood, and activated carbon have been described. However, natural wood obtained by obtaining a carbon structure or carbonized plant / biological tissue, amorphous carbon, fullerene, carbon nanotube, etc. The same reaction can be obtained if it is at least one of the three-dimensional bulk material, cloth, net, wire, fiber, and the combination thereof, which are artificially synthesized with the main constituent materials. It is clear.
１ 炭化木
２ ナトリウム
３ シリコン
４ 焼結窒化ホウ素坩堝
５ ニッケル製ルツボ
６ ニッケル台
７ ニッケル製キャップ
８ 熱電対
９ ヒーター
1 Carbide wood 2 Sodium 3 Silicon 4 Sintered boron nitride crucible 5 Nickel crucible 6 Nickel stand 7 Nickel cap 8 Thermocouple 9 Heater
Claims (5)
5. The method for manufacturing a silicon carbide structure according to claim 1, wherein a temperature for heating the structure mainly composed of carbon is 600 ° C. or more and 1200 ° C. or less.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001294413A (en) * | 2000-04-11 | 2001-10-23 | Toyota Motor Corp | METHOD FOR MANUFACTURING CARBON NANOTUBE, METHOD FOR MANUFACTURING POROUS SiC MATERIAL AND POROUS SiC MATERIAL |
| JP2005104752A (en) * | 2003-09-29 | 2005-04-21 | Toto Ltd | Silicon ceramic composite and manufacturing method thereof |
| WO2006070749A1 (en) * | 2004-12-28 | 2006-07-06 | Matsushita Electric Industrial Co., Ltd. | METHOD FOR PRODUCING SILICON CARBIDE (SiC) SINGLE CRYSTAL AND SILICON CARBIDE (SiC) SINGLE CRYSTAL OBTAINED BY SUCH METHOD |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001294413A (en) * | 2000-04-11 | 2001-10-23 | Toyota Motor Corp | METHOD FOR MANUFACTURING CARBON NANOTUBE, METHOD FOR MANUFACTURING POROUS SiC MATERIAL AND POROUS SiC MATERIAL |
| JP2005104752A (en) * | 2003-09-29 | 2005-04-21 | Toto Ltd | Silicon ceramic composite and manufacturing method thereof |
| WO2006070749A1 (en) * | 2004-12-28 | 2006-07-06 | Matsushita Electric Industrial Co., Ltd. | METHOD FOR PRODUCING SILICON CARBIDE (SiC) SINGLE CRYSTAL AND SILICON CARBIDE (SiC) SINGLE CRYSTAL OBTAINED BY SUCH METHOD |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010083732A (en) * | 2008-10-02 | 2010-04-15 | Tohoku Univ | Method for manufacturing silicon crystal and method for manufacturing solar cell film |
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