WO2008018401A1 - SiC-BASED SINTERED PRODUCT, AND METHOD FOR PRODUCTION THEREOF - Google Patents

SiC-BASED SINTERED PRODUCT, AND METHOD FOR PRODUCTION THEREOF Download PDF

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Publication number
WO2008018401A1
WO2008018401A1 PCT/JP2007/065343 JP2007065343W WO2008018401A1 WO 2008018401 A1 WO2008018401 A1 WO 2008018401A1 JP 2007065343 W JP2007065343 W JP 2007065343W WO 2008018401 A1 WO2008018401 A1 WO 2008018401A1
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Prior art keywords
sic
sintered body
porosity
weight
sintered product
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PCT/JP2007/065343
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English (en)
French (fr)
Inventor
Tomoo Nagatome
Kazuhiko Kawaguchi
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Mitsui Kinzoku Co Ltd
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Mitsui Mining and Smelting Co Ltd
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Priority to JP2008528807A priority Critical patent/JP5199091B2/ja
Publication of WO2008018401A1 publication Critical patent/WO2008018401A1/ja
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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
    • C04B35/56—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 carbides or oxycarbides
    • C04B35/565—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 carbides or oxycarbides based on silicon carbide
    • C04B35/575—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 carbides or oxycarbides based on silicon carbide obtained by pressure sintering
    • C04B35/5755—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 carbides or oxycarbides based on silicon carbide obtained by pressure sintering obtained by gas pressure sintering
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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
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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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
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    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
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    • C04B2235/963—Surface properties, e.g. surface roughness

Definitions

  • the present invention relates to a SiC-based sintered body used for firing an object to be fired, such as ceramics, tiles, and electronic parts, and a method for producing the same.
  • Si-SiC sintered body also referred to as SiC-based sintered body
  • SiC-based sintered body containing SiC and Si as constituents
  • SiC and Si as constituents
  • the Si-SiC sintered body is mainly made by adding carbon (C) fine powder and an organic binder to SiC particles, forming them by casting, extrusion molding, press molding, etc., and then firing them in a Si atmosphere. Manufactured.
  • press molding is optimal for mass production and industrialization, but there is a problem that layer peeling occurs at the time of molding, and damage is also caused during handling due to low retention. was there.
  • Patent Document 1 Japanese Patent No. 2968882
  • the present invention is to provide an SiC sintered body that is excellent in debinding of a fired product and can obtain a fired product having a uniform composition, and a method for producing the same. Means for solving the problem
  • the SiC sintered body of the present invention includes at least SiC and Si containing SiC and Si as constituent components.
  • the average surface roughness of the sintered body is 5 Hm to 100 ⁇ m. By setting the surface roughness, it becomes easy to remove the binder of the fired product placed on the sintered body, so that it is excellent in debinding, and the ability to obtain a fired product of uniform composition S It will be that monkey.
  • the present invention provides a SiC sintered body containing at least SiC and Si as constituent components, wherein the sintered body has a surface porosity of 0.3% or more. You can also.
  • This surface porosity also makes it easy to remove the binder of the object to be fired placed on the sintered body, so that it is excellent in debinding, and the object to be fired has a uniform composition. It can be obtained.
  • the present invention combines the above characteristics, and the average surface roughness of the sintered body is from 5 Hm to 100 ⁇ m, and the surface porosity of the sintered body is 0.3% or more. It can also be a SiC sintered body.
  • the surface porosity is preferably larger than the internal porosity, and the ratio of the surface porosity to the internal porosity (surface porosity / internal porosity) is 1.3. The above is more preferable.
  • the sintered body preferably has a silicon nitride crystal on the surface.
  • a molding raw material containing SiC powder, graphite powder, an organic binder and water is molded, sintered, and then cooled. It is a manufacturing method that mentions a manufacturing method in which nitrogen gas is introduced into at least one of the sintering process and the cooling process.
  • the nitrogen gas can remove Si from the surface of the sintered body, so that the surface can be appropriately roughened.
  • the pressure of the nitrogen gas is 0. IMPa to; 1. OMPa, the firing temperature is 1500 ° C to 2500 ° C, the firing temperature holding time is 8 hours or more, and the rate of temperature rise is 120 ° C / hr or more is preferable.
  • the surface porosity referred to in the present invention is a depth having a depth from both surfaces of about 30% of the thickness.
  • Porosity refers to porosity
  • internal porosity refers to the porosity of the other central part.
  • the surface porosity is a porosity of 3 mm depth from both surfaces
  • the internal porosity is a porosity of 3 mm to 7 mm from the surface.
  • the surface of a SiC sintered body containing SiC and Si as constituents is roughened, the average surface roughness is 5 m to 100 m, and the surface porosity is 0.3% or more. Do this.
  • a SiC sintered body satisfying both the range of the average surface roughness and the surface porosity is acceptable.
  • the SiC sintered body of the present invention can be manufactured by molding a molding raw material in which SiC powder, graphite powder, an organic binder, and water or an organic solvent are mixed and then sintering.
  • SiC powder 3 ⁇ fine particles having an average particle diameter of 30 111 to 85 111, preferably 55 m to 75 m can be used. Moreover, you may mix and use what differs in a particle size. When particles having different particle sizes are used, SiC fine particles having an average particle size of 1 am to 10 m, preferably 2 am to 8 am can be used as the SiC fine particles.
  • the graphite powder having an average particle size of 3.0 ⁇ m to 8.5 ⁇ 111, preferably 5.5 ⁇ m to 7.5 ⁇ m can be used.
  • the graphite powder is contained in an amount of 1% by weight to 15% by weight, preferably 3% by weight to 10% by weight, based on the SiC powder.
  • organic binder a lignin sulfonic acid organic binder, a polysaccharide organic binder, or an acrylic organic binder can be used, and 1 wt% to 5 wt%, preferably 2 wt% with respect to the SiC powder. ⁇ 2.5% by weight is contained.
  • SiC powder SiC powder, graphite powder, an organic binder, water or an organic solvent, and mix them to obtain a forming raw material.
  • Mixing can be carried out using a grinder such as a ball mill or a fret mill.
  • the degree of crushing is determined by placing an appropriate amount of raw material before crushing into a 20 mm x 20 mm mold, measuring the number of graphite agglomerated powder on the press surface with a magnifying glass when press forming, Similarly, numbers can be measured and their ratio can be calculated.
  • Examples of the molding method include casting (intrusion) molding, extrusion molding, press molding, and the like, and a molded body can be produced using these. Of these, hydraulic presses and vibration presses that are preferred for press molding are good! /.
  • Firing is performed at a firing temperature of 1500 in a metal silicon atmosphere and an argon (Ar) gas atmosphere.
  • C, preferred ⁇ is 1800. C ⁇ ; 1950.
  • the metal silicon atmosphere means, for example, a situation in which metal silicon is stored in a firing furnace, and the molten metal silicon is absorbed into the formed body by capillary action! /, Let's do it! After that, nitrogen) gas is introduced at the time of firing at 1400 ° C or higher, which is the melting point of silicon, or at the time of cooling.
  • SiN whiskers are formed immediately after firing, it is preferable to remove them by sandblasting.
  • the pressure of the nitrogen (N) gas is preferably 0 ⁇ IMPa ⁇ ;! ⁇ OMPa
  • the pressure is 0.4 MPa to 0.9 MPa.
  • the molded body has a substantially rectangular plate shape, it is preferable that the molded body is erected, that is, fired with one of the side end surfaces as the lower surface from the viewpoint of warpage prevention. At this time, the interval between the compacts
  • the thickness should be 2 mm or more, preferably 5 mm or more. This prevents the formations from adhering to each other due to Si leaching.
  • the surface porosity should be larger than the internal porosity!
  • the ratio of surface porosity to internal porosity is 1.3 or more. Is more preferably 2.0 or more, still more preferably 5.0 or more. This results in a SiC sintered body with excellent reactivity of the object to be fired.
  • the SiC sintered body of the present invention has an average surface roughness of 5 111 to 100 111 or a surface porosity of 0.
  • the surface has an appropriate roughness of 3% or more, the binder of the fired product placed on the sintered body is easily removed, and the fired product is not fused to the sintered body. Also
  • the object to be fired has a uniform structure with the binder sufficiently removed.
  • the average surface roughness was measured at five points according to JIS-B0601, and the average was obtained.
  • the surface porosity or internal porosity was measured at four points by changing the location according to the boiling method described in JIS-R1634, and the average was obtained.
  • the obtained molded body was put into a firing furnace having a silicon reservoir at the bottom, and from Ar to room temperature (804. lkPa (8.2 kg / cm 2 )) from room temperature to 700 ° C for 3.5 hours
  • the temperature is raised at a heating rate of about 200 ° C / hr, held at 700 ° C for 1 hour, and then heated from 700 ° C to 1880 ° C for 8 hours (a heating rate of about 150 ° C).
  • the firing temperature of 1880 ° C was maintained for 11.5 hours.
  • nitrogen gas was introduced and fired at 1800 ° C. for 0.5 hours under a nitrogen gas atmosphere (804 lkPa (8.2 kg / cm 2 )) to obtain a SiC sintered body.
  • the physical properties of the obtained sintered body were an average surface roughness of 9.8 ⁇ ⁇ and a surface porosity of 0.5%.
  • the ratio (surface porosity / internal porosity) was 5.5.
  • the bending strength, which is an index of strength, was 185 MPa.
  • Example 2 For 100 parts by weight of powder consisting of 79% by weight of SiC fine particles with an average particle size of 55 ⁇ m, 19% by weight of SiC fine particles with an average particle size of 3 ⁇ m, and 2% by weight of graphite powder with an average particle size of 6 am Then, 1.2 parts by weight of an acrylic organic binder and 17 parts by weight of water were blended and wet-ground with a ball mill to obtain a molding raw material. This forming raw material was poured with a plaster mold to obtain a molded body of 250 mm XI 20 mm X 6 mm.
  • the obtained molded body was put into a firing furnace having a silicon reservoir at the bottom, and from Ar to room temperature (804. lkPa (8.2 kg / cm 2 )) from room temperature to 700 ° C for 3.5 hours
  • the temperature is raised at a heating rate of about 200 ° C / hr, held at 700 ° C for 1 hour, and then heated from 700 ° C to 1880 ° C for 8 hours (a heating rate of about 150 ° C).
  • the firing temperature of 1880 ° C was maintained for 11.5 hours.
  • nitrogen gas was introduced and fired at 1800 ° C. for 0.5 hours under a nitrogen gas atmosphere (804 lkPa (8.2 kg / cm 2 )) to obtain a SiC sintered body.
  • the obtained sintered compact had an average surface roughness of 6.9111 and a surface porosity of 0.4%.
  • the ratio (surface porosity / internal porosity) was 2.0.
  • the bending strength, which is an index of strength, was 250 MPa.
  • Graphite powder with an average particle size of 0.1 111 is 100 parts by weight of powder consisting of 50% by weight of SiC fines with an average particle size of 1.011 m and 50% by weight of SiC fine particles with an average particle size of 25 ⁇ m.
  • 0 parts by weight, 0.1 part by weight of organic binder (methylcellulose) and 3.0 parts by weight of water were blended and pulverized with a ball mill to obtain a raw material for molding.
  • This raw material for molding was put into a mold and hydraulically pressed at 300 kg / cm 2 to obtain an expanded body of 200 mm ⁇ 30 mm ⁇ 10 mm.
  • the obtained compact was obtained in the same manner as in Example 1 except that nitrogen gas was not introduced during firing to obtain a SiC sintered body.
  • the obtained sintered compact had an average surface roughness of 3.7 111 and a surface porosity of 0.15%.
  • the ratio (surface porosity / internal porosity) was 0.83.
  • a material to be fired made of kaolin is applied to the SiC sintered body of Examples 1 and 2 or Comparative Example 1. Then, it was baked at 1200 ° C for 12 hours, and it was confirmed that the material to be fired was fused to the sintered SiC.

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Description

明 細 書
SiC質焼結体及びその製造方法
技術分野
[0001] 本発明は、陶磁器、タイル、電子部品等の被焼成物を焼成するために用いる SiC 質焼結体及びその製造方法に関する。
背景技術
[0002] SiCと Siを構成成分として含む Si— SiC焼結体（SiC質焼結体ともいう。 )は、工業 的に優れた耐熱性及び耐火度を備えており、陶磁器、タイル、電子部品等の被焼成 物の焼成用棚板などとして用いるものである。
Si— SiC焼結体は、主に、 SiC粒子にカーボン（C)微粉末と有機バインダーとを添 加し、これを流し込み成形、押出成形、プレス成形等により成形した後、 Si雰囲気中 で焼成して製造される。
[0003] 前記製造方法の内、プレス成形は、量産化、工業化には最適なものであるが、成形 時に層状の剥離が生じやすぐまた、保形成が低いため取扱い時に破損が生じると いう問題があった。
この問題を解決するために、下記特許文献 1に記載されている SiC質焼結体が開 発されている。
[0004] 特許文献 1：特許第 2968882号公報
発明の開示
発明が解決しょうとする課題
[0005] しかし、上記特許文献 1に記載の SiC質焼結体は、プレス成形した際、表面にプレ ス圧力が集中して平滑となり、被焼成物の脱バインダーが十分に行うことができず、 均一組成の被焼成物を得ることができないという問題があった。
[0006] 本発明は、上記課題に鑑み、被焼成物の脱バインダーに優れ、均一組成の被焼成 物を得ることができる SiC質焼結体及びその製造方法を提供せんとするものである。 課題を解決するための手段
[0007] 本発明の SiC質焼結体は、少なくとも SiCと Siとを構成成分として含む SiC質焼結 体であって、前記焼結体の平均面粗さが 5 H m〜100 μ mであることを特徴とする。 この表面粗さとすることにより、前記焼結体上に載せた被焼成物のバインダーが抜 けやすくなるため、脱バインダーに優れたものとなり、また、均一組成の被焼成物を得 ること力 Sでさるあのとなる。
[0008] 本発明は、少なくとも SiCと Siとを構成成分として含む SiC質焼結体であって、前記 焼結体の表面気孔率が 0. 3%以上である SiC質焼結体とすることもできる。
この表面気孔率とすることによつても、前記焼結体上に載せた被焼成物のバインダ 一が抜けやすくなるため、脱バインダーに優れたものとなり、また、均一組成の被焼 成物を得ることができるものとなる。
[0009] 本発明は、上記特徴を合わせて、前記焼結体の平均面粗さが 5 H m〜； 100 μ mで あり、かつ、前記焼結体の表面気孔率が 0. 3%以上である SiC質焼結体とすることも できる。
[0010] 上記焼結体において、表面気孔率は、内部気孔率よりも大であるのが好ましぐ表 面気孔率と内部気孔率の比率 (表面気孔率/内部気効率）が 1. 3以上であるのがよ り好ましい。
このようにすることにより、内部に巣のない焼結体となり、強度的に優れたものとなる
〇
[0011] また、上記焼結体において、表面に窒化ケィ素結晶を有するのが好ましい。
[0012] 上記焼結体の製造方法としては、 SiC粉体、黒鉛粉、有機バインダー及び水を含 有してなる成形用原料を成形した後、焼結し、冷却する SiC質焼結体の製造方法で あって、少なくとも焼結工程、冷却工程のどちらか一方に窒素ガスを導入する製造方 法を挙げること力 Sでさる。
成形後に窒素ガスを導入して焼結或いは冷却することにより、窒素ガスは、焼結体 の表面から Siを取り去ることができるため、表面を適度な粗さにすることができる。
[0013] 上記製造方法において、窒素ガスの圧力は 0. IMPa〜； 1. OMPaとし、焼成温度 は 1500°C〜2500°C、焼成温度保持時間は 8時間以上とし、昇温速度は 120°C/h r以上とするのが好ましい。
[0014] なお、本発明でいう表面気孔率は、厚さに対して約 30%の両表面からの深さの気 孔率をいい、内部気孔率は、それ以外の中心部の気孔率をいう。例えば、厚さを 10 mmとした場合、表面気孔率は、両表面から 3mm深さまでの気孔率であり、内部気 孔率は、表面から 3mm〜7mmまでの深さの気孔率である。
発明を実施するための最良の形態
[0015] 以下、本発明の好適な実施形態を説明する。
本発明は、 SiCと Siとを構成成分として含む SiC質焼結体の表面を粗くしたもので あり、平均面粗さでは 5 m〜； 100 m、表面気孔率では 0· 3%以上となるようにす る。もちろん、これら平均面粗さと表面気孔率との両方の範囲を満たす SiC質焼結体 としてあよい。
本発明の SiC質焼結体は、 SiC粉末と、黒鉛粉と、有機バインダーと、水又は有機 溶剤とを混合した成形用原料を成形した後、焼結して製造することができる。
[0016] SiC粉末は、 3^微粒として平均粒径30 111〜85 111、好ましくは 55 m〜75 mのものを用いることができる。また、粒径の異なるものを混合して用いてもよい。粒 径の異なるものを使用する場合には、 SiC微粒に平均粒径が 1 a m〜； 10 m、好ま しくは 2 a m〜8 a mの SiC微粉を用いることができる。
[0017] 黒鉛粉は、平均粒径 3.0 ^ m〜8.5 ^ 111、好ましくは 5.5 ^ m〜7.5 ^ mのものを用 いること力 Sできる。黒鉛粉は、 SiC粉末に対して 1重量％〜； 15重量％、好ましくは 3重 量％〜10重量％含有させる。
[0018] 水又は有機溶剤は、後述するプレス成形の場合には、 SiC粉末に対して 1重量％
〜6重量％含有させるのが好ましぐまた、後述する铸込み成形の場合には、 SiC粉 末に対して 10重量％〜20重量％含有させるのが好ましい。
[0019] 有機バインダーは、リグニンスルホン酸系有機バインダーや多糖類系有機バインダ 一、アクリル系有機バインダーを用いることができ、 SiC粉末に対して 1重量％〜5重 量％、好ましくは 2重量％〜2. 5重量％含有させる。
[0020] SiC粉末と、黒鉛粉と、有機バインダーと、水又は有機溶剤とを配合し、これを混合 して成形用原料とすること力できる。混合は、ボールミル、フレットミル等の粉砕機を用 いて fiうことができる。
この際、黒鉛の凝集粒子の 90重量％以上が解砕されるまで解砕する。なお、ここで 解砕度は、解砕前の原料を 20mm X 20mmの成形型に適量入れ、プレス成形したと きにプレス面にある黒鉛凝集粉の数を拡大鏡で測定し、また解砕後の原料も同様に 数を測定し、これらの比を求めて計算することができる。
[0021] 成形方法としては、流し込み（铸込み）成形、押出成形、プレス成形などがあり、こ れらを用いて成形体を作成することができる。なかでも、プレス成形が好ましぐ油圧 プレスや振動プレスがよ!/、。
[0022] 上記成形体を以下のように焼成することにより、本発明の SiC質焼結体を製造する こと力 Sでさる。
[0023] 焼成は、金属シリコン雰囲気、かつ、アルゴン (Ar)ガス雰囲気下において、焼成温 度 1500。C〜2500。C、好まし <は 1800。C〜； 1950。Cで行う。なお、ここで金属シリコ ン雰囲気とは、例えば、焼成炉内に金属シリコン貯まりを有し、溶融した該金属シリコ ンが毛細管現象により成形体に吸収されるような状況を形成して!/、ることを!/、う。 その後、窒素 ）ガスを、シリコンの融点である 1400°C以上での焼成時又は冷却 時に導入する。これにより、 SiC質焼結体表面に SiN (窒化ケィ素）の針状結晶による 凹凸を形成することができ、安全性に優れ、電子部品等の被焼成物の脱バインダー 性に優れた SiC質焼結体を得ることができる。窒素ガスの導入は、 SiC質焼結体への 金属シリコンの吸収を妨げないため、焼成工程の最後又は冷却工程に行うのが好ま しい。
焼成直後に SiNのゥイスカーが多く生成している場合、サンドブラストで除去するの が好ましい。
この焼成の際、窒素（N )ガスの圧力は、 0· IMPa〜； ! · OMPaとするのが好ましく
、より好ましくは 0. 4MPa〜0. 9MPaとする。
[0024] 成形体を略矩形板状とした場合は、成形体を立てて、つまりいずれかの側端面を 下面として焼成するのが、反り防止の観点から好ましい。この際、各成形体の間隔を
2mm以上、好ましくは 5mm以上とするのがよぐこれにより Siの浸み出しによる各成 形体同士の付着を防止できる。
[0025] 上記焼結体にお!/、て、表面気孔率は、内部気孔率よりも大であるのがよ!/、。特に表 面気孔率と内部気孔率との比率 (表面気孔率/内部気孔率）は、 1. 3以上であるの がよぐより好ましくは 2. 0以上、さらに好ましくは 5. 0以上である。これにより、被焼成 物の反応性に優れた SiC質焼結体となる。
[0026] 本発明の SiC質焼結体は、平均面粗さを5 111〜100 111、或いは表面気孔率を 0
. 3%以上として表面に適度の粗さを有するため、前記焼結体上に載せた被焼成物 のバインダーが抜けやすくなり、被焼成物が前記焼結体に融着することがない。また
、被焼成物は、バインダーが充分に抜け、均一な組織となる。
[0027] 以下、本発明の実施例を説明する。ただし、本発明はこれに限定されるものではな い。
なお、下記実施例及び比較例において、平均面粗さは、 JIS— B0601に従い、場 所を変更して 5点測定し、その平均を求めた。また、表面気孔率又は内部気孔率は、 JIS— R1634に記載の煮沸法に従い、場所を変更して 4点測定し、その平均を求め た。
[0028] (実施例 1)
平均粒径 70 ,1 mの SiC微粒 97重量％と、平均粒径 6 μ mの黒鉛粉 3重量％とから なる粉体 100重量部に対して、リグニンスルホン酸系有機バインダー 2重量部、多糖 類系有機バインダー 2. 5重量部及び水 4. 5重量部を配合し、成形用原料とした。こ の成形用原料を、金型に入れ、振動プレスし、 350mm X 300mm X 6mmの成形体 を得た。
得られた成形体を、下部にシリコン貯まりを有する焼成炉の中に入れ、 Arガス雰囲 気下（804. lkPa (8. 2kg/cm2) )で室温から 700°Cまで 3. 5時間（昇温速度約 20 0°C/hr)で昇温し、 700°Cで 1時間保持した後、 700°Cから 1880°Cまで 8時間（昇 温速度約 150°C)で昇温し、 1880°Cの焼成温度を 11. 5時間保持した。その後、窒 素ガスを導入し、窒素ガス雰囲気下（804· lkPa (8. 2kg/cm2) )で 0· 5時間、 188 0°Cで焼成し、 SiC質焼結体を得た。
得られた焼結体の物性は、平均面粗さ 9. 8 μ ΐη^表面気孔率 0. 5%であった。ま た、比率 (表面気孔率/内部気孔率）は 5. 5であった。強度の指標である曲げ強さは 185MPaであった。
[0029] (実施例 2) 平均粒径 55 μ mの SiC微粒 79重量％と、平均粒径 3 μ mの SiC微粉 19重量％と、 平均粒径 6 a mの黒鉛粉 2重量％とからなる粉体 100重量部に対して、アクリル系有 機バインダー 1. 2重量部及び水 17重量部を配合し、これをボールミルで湿式粉砕し て成形用原料を得た。この成形用原料を、石膏型で铸込み、 250mm X I 20mm X 6mmの成形体を得た。
得られた成形体を、下部にシリコン貯まりを有する焼成炉の中に入れ、 Arガス雰囲 気下（804. lkPa (8. 2kg/cm2) )で室温から 700°Cまで 3. 5時間（昇温速度約 20 0°C/hr)で昇温し、 700°Cで 1時間保持した後、 700°Cから 1880°Cまで 8時間（昇 温速度約 150°C)で昇温し、 1880°Cの焼成温度を 11. 5時間保持した。その後、窒 素ガスを導入し、窒素ガス雰囲気下（804· lkPa (8. 2kg/cm2) )で 0· 5時間、 188 0°Cで焼成し、 SiC質焼結体を得た。
得られた焼結体の物性は、平均面粗さ 6. 9 111、表面気孔率 0. 4%であった。ま た、比率 (表面気孔率/内部気孔率）は 2. 0であった。強度の指標である曲げ強さは 250MPaであった。
[0030] (比較例 1)
平均粒径 1. 011 mの SiC微粉 50重量％と、平均粒径 25 μ mの SiC微粒 50重量％ とからなる粉体 100重量部に対し、平均粒径 0. 1 111の黒鉛粉1. 0重量部、有機バ インダー（メチルセルロース） 0. 1重量部及び水 3. 0重量部で配合し、これをボール ミルで粉砕して成形用原料を得た。この成形用原料を、金型に入れ、 300kg/cm2 で油圧プレスし、 200mm X 30mm X 10mmの成开乡体を得た。
得られた成形体を、焼成時に窒素ガスを導入しない以外は、実施例 1と同様にし、 SiC質焼結体を得た。
得られた焼結体の物性は、平均面粗さ 3. 7 111、表面気孔率 0. 15%であった。ま た、比率（表面気孔率/内部気孔率）は 0. 83であった。
[0031] (評価）
上記実施例 1 , 2及び比較例 1を用いて、下記融着性を評価した。
[0032] (融着性）
材質カオリンからなる被焼成物を、実施例 1 , 2又は比較例 1の SiC質焼結体上に 置き、 1200°Cで 12時間焼成し、被焼成物が SiC質焼結体に融着している力、を確認 した。
[0033] (結果）
上記実施例 1 , 2及び比較例 1の SiC質焼結体を、各 6枚用いて上記評価を行った 。〇は「融着なし」、△は「少し融着あり」、 Xは「融着しており、取り出せない、或いは 被焼成物が破損」として評価した。
その結果を表 1に示す。
[0034] [表 1]
〇 Δ X
実施例 1 4枚 2枚 なし
実施例 2 3枚 3枚 なし
比較例 1 なし 6枚 なし

Claims

請求の範囲
[1] 少なくとも SiCと Siとを構成成分として含む SiC質焼結体であって、前記焼結体の 平均面粗さが 5 m〜； 100 mである SiC質焼結体。
[2] 少なくとも SiCと Siとを構成成分として含む SiC質焼結体であって、前記焼結体の 表面気孔率が 0. 3%以上である SiC質焼結体。
[3] 少なくとも SiCと Siとを構成成分として含む SiC質焼結体であって、前記焼結体の 平均面粗さが 5 m〜； 100 mであり、かつ、前記焼結体の表面気孔率が 0. 3%以 上である SiC質焼結体。
[4] 表面気孔率は、内部気孔率よりも大である請求項 2又は 3に記載の SiC質焼結体。
[5] 表面気孔率と内部気孔率の比率 (表面気孔率/内部気孔率）が 1. 3以上である請 求項 4に記載の SiC質焼結体。
[6] 表面に窒化ケィ素結晶を有する請求項;!〜 5のいずれかに記載の SiC質焼結体。
[7] SiC粉体、黒鉛粉、有機バインダー及び水を含有してなる成形用原料を成形した 後、焼結し、冷却する SiC質焼結体の製造方法であって、少なくとも焼結工程、冷却 工程のどちらか一方に窒素ガスを導入する SiC質焼結体の製造方法。
[8] 窒素ガスの圧力が 0. IMPa〜； 1. OMPaである請求項 7に記載の SiC質焼結体の 製造方法。
PCT/JP2007/065343 2006-08-09 2007-08-06 SiC-BASED SINTERED PRODUCT, AND METHOD FOR PRODUCTION THEREOF Ceased WO2008018401A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6036372A (ja) * 1983-07-29 1985-02-25 ヘキスト・セラムテック・アクチェンゲゼルシャフト ケイ素浸透され、反応結合された炭化ケイ素から成る成形体の製法
JPH06157141A (ja) * 1992-11-19 1994-06-03 Ngk Insulators Ltd 耐スポーリング性焼結体
JP2002274946A (ja) * 2001-03-22 2002-09-25 Ngk Insulators Ltd ＳｉＣ質熱処理用治具

Family Cites Families (2)

* Cited by examiner, † Cited by third party
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US20050084717A1 (en) * 2001-10-22 2005-04-21 Eiji Tani Silicon carbide based porous structure and method for manufacturing thereof
JP4155940B2 (ja) * 2004-04-16 2008-09-24 日本碍子株式会社 セラミックス複合材の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6036372A (ja) * 1983-07-29 1985-02-25 ヘキスト・セラムテック・アクチェンゲゼルシャフト ケイ素浸透され、反応結合された炭化ケイ素から成る成形体の製法
JPH06157141A (ja) * 1992-11-19 1994-06-03 Ngk Insulators Ltd 耐スポーリング性焼結体
JP2002274946A (ja) * 2001-03-22 2002-09-25 Ngk Insulators Ltd ＳｉＣ質熱処理用治具

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