JP2649220B2 - Silicon nitride / silicon carbide composite powder, composite compact, method for producing them, and method for producing silicon nitride / silicon carbide composite sintered body - Google Patents
Silicon nitride / silicon carbide composite powder, composite compact, method for producing them, and method for producing silicon nitride / silicon carbide composite sintered bodyInfo
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- JP2649220B2 JP2649220B2 JP7319737A JP31973795A JP2649220B2 JP 2649220 B2 JP2649220 B2 JP 2649220B2 JP 7319737 A JP7319737 A JP 7319737A JP 31973795 A JP31973795 A JP 31973795A JP 2649220 B2 JP2649220 B2 JP 2649220B2
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- silicon nitride
- silicon carbide
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は窒化珪素／炭化珪素
複合粉末及び複合成形体並びにそれらの製造方法及び窒
化珪素／炭化珪素複合焼結体の製造方法に関し、特に優
れた強度、硬度、靱性、耐熱衝撃性、耐摩耗性等を有す
る窒化珪素／炭化珪素ナノコンポジットを製造するのに
適する複合粉末、複合成形体並びにそれらの製造方法及
び複合焼結体の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon nitride / silicon carbide composite powder and a composite molded body, a method for producing the same, and a method for producing a silicon nitride / silicon carbide composite sintered body. The present invention relates to a composite powder suitable for producing a silicon nitride / silicon carbide nanocomposite having thermal shock resistance, abrasion resistance and the like, a composite molded body, a method for producing them, and a method for producing a composite sintered body.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】窒化珪
素系セラミックス焼結体は、高強度、高耐熱性、高耐熱
衝撃性、高耐摩耗性などの点から、高温での使用条件が
苛酷な構造用セラミックスとしての利用が期待されてい
る。また、その物性を向上する目的で、種々の成分が添
加されている。中でも、炭化珪素は良好な耐酸化性、高
温強度及び機械的強度を発揮し得るセラミックス成分で
あり、窒化珪素に炭化珪素を配合したセラミックス焼結
体が提案されている。しかし、単に窒化珪素粉末と炭化
珪素粉末とを混合して得た焼結体では、ナノコンポジッ
ト構造を有することがなく、炭化珪素粉末（ミクロンオ
ーダの大きさ）は窒化珪素の粒界に存在するにとどま
る。そのため、窒化珪素中に炭化珪素が微細に分散した
ナノコンポジット構造を有する焼結体を得るために、種
々の方法が提案されている。2. Description of the Related Art Sintered silicon nitride ceramics have severe operating conditions at high temperatures in terms of high strength, high heat resistance, high thermal shock resistance, and high wear resistance. It is expected to be used as a simple structural ceramic. Also, various components are added for the purpose of improving the physical properties. Among them, silicon carbide is a ceramic component capable of exhibiting good oxidation resistance, high-temperature strength, and mechanical strength, and a ceramic sintered body in which silicon nitride is mixed with silicon carbide has been proposed. However, a sintered body obtained by simply mixing a silicon nitride powder and a silicon carbide powder does not have a nanocomposite structure, and the silicon carbide powder (on the order of microns) exists at a grain boundary of silicon nitride. Stay in. Therefore, various methods have been proposed to obtain a sintered body having a nanocomposite structure in which silicon carbide is finely dispersed in silicon nitride.
【０００３】特開平2-160669号は、平均粒径１μｍ以下
の炭化珪素が粒界に分散し、かつ数ナノメータから数百
ナノメータの大きさの炭化珪素の微細粒子が窒化珪素粒
子内に分散した微細構造を有する窒化珪素−炭化珪素複
合焼結体を開示している。この複合焼結体は、液相焼結
系において平均粒径が0.5 μｍ以下の微細な炭化珪素を
生成する非晶質窒化珪素−炭化珪素複合粉末又は窒化珪
素−炭化珪素混合粉末を使用し、焼結助剤の存在下で15
00〜2300℃の温度で焼結することにより製造される。し
かし、非晶質窒化珪素−炭化珪素複合粉末は、有機珪素
化合物の気相反応法により得られるもので、非常にコス
ト高であり、かつ量産性に劣る。また、非晶質粉末は成
形性に劣るという問題がある。また、窒化珪素−炭化珪
素混合粉末として具体的に開示されているものは、上記
と同様な処方により得られた非晶質窒化珪素粉末と炭化
珪素粉末との混合粉末であり、やはり同じ問題がある。
さらに、開示されているものはすべて成形の必要がない
ホットプレスによる焼成である。Japanese Patent Application Laid-Open No. Hei 2-160669 discloses that silicon carbide having an average particle size of 1 μm or less is dispersed in grain boundaries, and fine particles of silicon carbide having a size of several nanometers to several hundred nanometers are dispersed in silicon nitride particles. A composite silicon nitride-silicon carbide sintered body having a microstructure is disclosed. This composite sintered body uses an amorphous silicon nitride-silicon carbide composite powder or a silicon nitride-silicon carbide mixed powder that generates fine silicon carbide having an average particle diameter of 0.5 μm or less in a liquid phase sintering system, 15 in the presence of sintering aids
It is manufactured by sintering at a temperature of 00-2300 ° C. However, the amorphous silicon nitride-silicon carbide composite powder is obtained by a gas phase reaction method of an organic silicon compound, and is very expensive and inferior in mass productivity. Further, there is a problem that the amorphous powder is inferior in moldability. What is specifically disclosed as a silicon nitride-silicon carbide mixed powder is a mixed powder of an amorphous silicon nitride powder and a silicon carbide powder obtained by the same formulation as described above, and the same problem still remains. is there.
In addition, all that is disclosed is firing by hot pressing which does not require molding.
【０００４】また特開平3-261611号は、窒化珪素／炭化
珪素複合焼結体を製造するための窒化珪素複合粉末を製
造する方法であって、金属珪素粉末と炭素質粉末とを混
合し、得られた混合物を窒素含有不活性ガス雰囲気中、
1400℃以下の温度で加熱して、金属珪素粉末の炭化反応
と窒化反応とを同時に行うことを特徴とする方法を開示
している。しかし、この複合粉末は出発材料中に焼結助
剤を含まないため、熱処理により生成する窒化珪素はβ
型になりやすく、複合粉末中のα型窒化珪素含有率を高
めるのが困難であった。また、β型の窒化珪素は針状に
粒成長するので、得られる粉末は粒径が大きく、粉砕も
困難であった。窒化珪素原料粉末には焼結性向上の観点
から、α型窒化珪素含有率が高く微粒子であることが求
められるが、開示されている方法ではこれらの条件を満
たすことができず、焼結性に劣るという問題がある。Japanese Patent Application Laid-Open No. Hei 3-261611 discloses a method for producing a silicon nitride composite powder for producing a silicon nitride / silicon carbide composite sintered body, comprising mixing a metal silicon powder and a carbonaceous powder, The resulting mixture in a nitrogen-containing inert gas atmosphere,
A method is disclosed in which a carbonization reaction and a nitridation reaction of metal silicon powder are simultaneously performed by heating at a temperature of 1400 ° C. or less. However, since this composite powder does not contain a sintering aid in the starting material, the silicon nitride generated by the heat treatment has β
It was difficult to form a mold, and it was difficult to increase the α-type silicon nitride content in the composite powder. In addition, since the β-type silicon nitride grows in a needle-like shape, the resulting powder has a large particle size and is difficult to pulverize. From the viewpoint of improving the sinterability, the silicon nitride raw material powder is required to have a high α-type silicon nitride content and to be fine particles, but the disclosed method cannot satisfy these conditions, and There is a problem that it is inferior.
【０００５】なお、β型窒化珪素原料粉末を焼成して高
い特性を持つ焼結体を得る方法が報告されているが（Ｆ
Ｃレポート、1994(5) 、pp.130〜133 ）、この方法では
β型窒化珪素粉末の粒度分布の制御を行い、微細粉末化
かつ均一な粒径とすることが必要であり、またガス圧焼
結法による高温焼成が必要であることから、工程が複雑
になることが予想される。またこの報告からβ型窒化珪
素粉末が焼結性の低い粉末であることが確認された。[0005] A method of firing a β-type silicon nitride raw material powder to obtain a sintered body having high characteristics has been reported (F.
C report, 1994 (5), pp. 130-133), in this method, it is necessary to control the particle size distribution of the β-type silicon nitride powder, to make the powder finer and to have a uniform particle size, Since high-temperature sintering by a sintering method is required, the process is expected to be complicated. From this report, it was confirmed that the β-type silicon nitride powder was a powder having low sinterability.
【０００６】したがって本発明の目的は、良好な焼結性
を有し、高強度の焼結体を形成できる窒化珪素／炭化珪
素複合粉末及び複合成形体並びにそれらの製造方法及び
窒化珪素／炭化珪素複合焼結体の製造方法を提供するこ
とである。Accordingly, an object of the present invention is to provide a silicon nitride / silicon carbide composite powder and a composite compact having good sinterability and capable of forming a high-strength sintered body, a method for producing the same, and silicon nitride / silicon carbide. An object of the present invention is to provide a method for manufacturing a composite sintered body.
【０００７】[0007]
【課題を解決するための手段】以上の目的に鑑み鋭意研
究の結果、本発明者等は、出発材料として珪素粉末と炭
素質粉末及び焼結助剤を使用し、特定の条件で熱処理す
れば、α型窒化珪素含有率の高い窒化珪素／炭化珪素複
合粉末又は複合成形体が得られ、それによって高い焼結
性を有する複合粉末又は複合成形体となることを発見
し、本発明を完成した。Means for Solving the Problems As a result of intensive studies in view of the above objects, the present inventors have found that using silicon powder, carbonaceous powder and a sintering aid as starting materials and subjecting them to heat treatment under specific conditions. To obtain a silicon nitride / silicon carbide composite powder or composite molded body having a high α-type silicon nitride content, and thereby to obtain a composite powder or composite molded body having high sinterability, and completed the present invention. .
【０００８】すなわち、本発明の窒化珪素／炭化珪素複
合粉末は、珪素粉末に炭素質粉末と焼結助剤とを混合
し、得られた混合粉末を窒素ガス含有雰囲気下において
熱処理して、珪素の窒化と炭化とを起こして得られるも
ので、前記複合粉末中のα型窒化珪素の含有量が全窒化
珪素の３０％以上であることを特徴とする。第一の実施
例では、前記焼結助剤の含有量は前記複合粉末の全量を
１００重量％として５〜２０重量％であり、第二の実施
例では、前記焼結助剤は（ａ）周期律表３Ａ族元素及び
４Ａ族元素の酸化物からなる群より選ばれた一種以上の
化合物、又は（ｂ）窒化アルミニウムと前記（ａ）の化
合物との混合物である。 That is, the silicon nitride / silicon carbide composite powder of the present invention is obtained by mixing a carbonaceous powder with a silicon powder and a sintering aid, and subjecting the resulting mixed powder to heat treatment in a nitrogen gas-containing atmosphere. , Wherein the content of α-type silicon nitride in the composite powder is 30% or more of the total silicon nitride. First implementation
In an example, the content of the sintering aid is the total amount of the composite powder.
5 to 20% by weight as 100% by weight, the second implementation
In an example, the sintering aid comprises (a) a Group 3A element of the periodic table and
At least one selected from the group consisting of oxides of Group 4A elements
Compound or (b) aluminum nitride and compound of (a)
It is a mixture with the compound.
【０００９】また、本発明の窒化珪素／炭化珪素複合成
形体は、珪素粉末に炭素質粉末と焼結助剤とを混合し、
得られた混合粉末から形成した成形体を窒素ガス含有雰
囲気下において熱処理して、珪素の窒化と炭化とを起こ
して得られるもので、前記複合成形体中のα型窒化珪素
の含有量が全窒化珪素の３０％以上であることを特徴と
する。第一の実施例では、前記焼結助剤の含有量は前記
複合成形体の全量を１００重量％として５〜２０重量％
であり、第二の実施例では、前記焼結助剤は（ａ）周期
律表３Ａ族元素及び４Ａ族元素の酸化物からなる群より
選ばれた一種以上の化合物、又は（ｂ）窒化アルミニウ
ムと前記（ａ）の化合物との混合物である。 Further, the silicon nitride / silicon carbide composite molded article of the present invention is obtained by mixing a carbonaceous powder and a sintering aid with a silicon powder,
A molded body formed from the obtained mixed powder is obtained by heat-treating in a nitrogen gas-containing atmosphere to cause nitridation and carbonization of silicon, and the content of α-type silicon nitride in the composite molded body is entirely It is characterized by being 30% or more of silicon nitride. In the first embodiment, the content of the sintering aid is
5 to 20% by weight based on 100% by weight of the total amount of the composite molded body
In the second embodiment, the sintering aid comprises (a)
From the group consisting of oxides of Group 3A and Group 4A elements
One or more selected compounds, or (b) aluminum nitride
And a mixture of the compound (a).
【００１０】本発明のα型窒化珪素の含有量が全窒化珪
素の３０％以上である窒化珪素／炭化珪素複合粉末を製
造する方法は、珪素粉末に炭素質粉末と焼結助剤とを混
合し、得られた混合粉末を窒素ガス含有雰囲気下におい
て熱処理して、珪素の窒化と炭化とを起こし、その際窒
化炭化反応を1000℃〜1450℃の温度で行い、かつ少なく
とも反応開始前の温度から保持温度に到達するまでの昇
温速度を２℃／分未満にすることを特徴とする。The method of the present invention for producing a silicon nitride / silicon carbide composite powder having an α-type silicon nitride content of 30% or more of the total silicon nitride comprises mixing a silicon powder with a carbonaceous powder and a sintering aid. Then, the obtained mixed powder is heat-treated in an atmosphere containing nitrogen gas to cause nitridation and carbonization of silicon, in which case the nitriding and carbonizing reaction is performed at a temperature of 1000 ° C to 1450 ° C, and at least the temperature before the start of the reaction. The rate of temperature rise until the temperature reaches the holding temperature is set to less than 2 ° C./min.
【００１１】本発明のα型窒化珪素の含有量が全窒化珪
素の３０％以上である窒化珪素／炭化珪素複合成形体を
製造する方法は、珪素粉末に炭素質粉末と焼結助剤とを
混合し、得られた混合粉末から成形体を形成し、前記成
形体を窒素ガス含有雰囲気下において熱処理して、珪素
の窒化と炭化とを起こし、その際窒化炭化反応を1000℃
〜1450℃の温度で行い、かつ少なくとも反応開始前の温
度から保持温度に到達するまでの昇温速度を２℃／分未
満にすることを特徴とする。[0011] The method of the present invention for producing a silicon nitride / silicon carbide composite molded article in which the content of α-type silicon nitride is 30% or more of the total silicon nitride is as follows. After mixing, a compact is formed from the obtained mixed powder, and the compact is heat-treated in an atmosphere containing nitrogen gas to cause nitridation and carbonization of silicon.
The process is carried out at a temperature of 11450 ° C., and the rate of temperature rise from at least the temperature before the start of the reaction to the holding temperature is set to less than 2 ° C./min.
【００１２】窒化珪素／炭化珪素複合焼結体を製造する
本発明の第一の方法は、上記窒化珪素／炭化珪素複合粉
末から成形体を形成し、前記成形体を窒素ガス含有雰囲
気中において1600℃〜2200℃で焼結することを特徴とす
る。In a first method of the present invention for producing a silicon nitride / silicon carbide composite sintered body, a molded body is formed from the above silicon nitride / silicon carbide composite powder, and the molded body is heated to 1600 in a nitrogen gas-containing atmosphere. It is characterized by sintering at 2200C.
【００１３】窒化珪素／炭化珪素複合焼結体を製造する
本発明の第二の方法は、上記窒化珪素／炭化珪素複合成
形体を窒素ガス含有雰囲気中において1600℃〜2200℃で
焼結することを特徴とする。[0013] A second method of the present invention for producing a silicon nitride / silicon carbide composite sintered body comprises sintering the silicon nitride / silicon carbide composite molded body at 1600 ° C to 2200 ° C in an atmosphere containing nitrogen gas. It is characterized by.
【００１４】[0014]
【発明の実施の形態】以下、本発明を詳細に説明する。 〔１〕出発原料 (a) 珪素粉末 本発明に使用する珪素粉末は、平均粒径が0.2 〜20μ
ｍ、特に0.3 〜10μｍであるのが好ましい。平均粒径が
0.2 μｍより小さいと、粉末表面の酸化が大であり、ま
た20μｍより大きいと均一な分散が困難となるとともに
反応性に乏しくなる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [1] Starting Materials (a) Silicon Powder The silicon powder used in the present invention has an average particle size of 0.2 to 20 μm.
m, particularly preferably 0.3 to 10 μm. Average particle size
If it is smaller than 0.2 μm, the oxidation of the powder surface is large, and if it is larger than 20 μm, uniform dispersion becomes difficult and reactivity becomes poor.
【００１５】なお、珪素粉末としては、JIS G 2312 に
規定されているような比較的低純度で安価なものから、
半導体のシリコンウェーハの破材を粉砕したような高純
度のものまで、広い範囲のものを使用することができ
る。また高純度の珪素粉末を使用した場合、Fe、Cr、Co
等の化合物あるいは単体を添加し、反応を促進すること
もできる。The silicon powder may be selected from relatively low-purity and inexpensive materials as defined in JIS G 2312.
A wide range of materials can be used, including high-purity materials obtained by pulverizing broken materials of semiconductor silicon wafers. When high-purity silicon powder is used, Fe, Cr, Co
The reaction can be promoted by adding a compound such as described above or a simple substance.
【００１６】出発原料中の珪素粉末と炭素質粉末の合計
量を100 重量％としたとき、珪素粉末の含有量は、81.2
〜97.6重量％が好ましく、84.2〜93.2重量％がより好ま
しい。珪素粉末が81.2重量％より少ないと焼結体が緻密
化しずらくなり、所望の複合焼結体が得られない。また
97.6重量％より多いと炭化珪素の複合効果が十分でなく
なる。When the total amount of the silicon powder and the carbonaceous powder in the starting material is 100% by weight, the content of the silicon powder is 81.2%.
997.6% by weight is preferred, and 84.2-93.2% by weight is more preferred. If the silicon powder is less than 81.2% by weight, the sintered body is hard to be densified, and a desired composite sintered body cannot be obtained. Also
If it exceeds 97.6% by weight, the combined effect of silicon carbide will not be sufficient.
【００１７】(b) 炭素質粉末 本発明に使用する炭素質粉末は、微細であれば特に限定
されないが、グラファイト粉末もしくはアセチレンブラ
ック、ケッチェンブラック等のカーボンブラック粉末が
好ましい。炭素質粉末は、平均粒径が20μｍ以下、特に
10μｍ以下であるのが好ましい。平均粒径が20μｍより
大きいと均一な分散が困難となる。(B) Carbonaceous powder The carbonaceous powder used in the present invention is not particularly limited as long as it is fine, but graphite powder or carbon black powder such as acetylene black or Ketjen black is preferred. The carbonaceous powder has an average particle size of 20 μm or less, particularly
It is preferably 10 μm or less. If the average particle size is larger than 20 μm, uniform dispersion becomes difficult.
【００１８】出発原料中の珪素粉末と炭素質粉末の合計
量を100 重量％としたとき、炭素質粉末の含有量は、2.
4 〜18.8重量％が好ましく、6.8 〜15.8重量％がより好
ましい。炭素質粉末が2.4 重量％より少ないと複合効果
が得られず、また18.8重量％より多いと焼結体が緻密化
しない。When the total amount of the silicon powder and the carbonaceous powder in the starting material is 100% by weight, the content of the carbonaceous powder is 2.
It is preferably from 4 to 18.8% by weight, more preferably from 6.8 to 15.8% by weight. If the carbonaceous powder is less than 2.4% by weight, the composite effect cannot be obtained, and if it is more than 18.8% by weight, the sintered body will not be densified.
【００１９】(c) 窒化珪素粉末 混合粉末の成形性を良くするとともに、窒化珪素生成の
核とするために、0.1〜５μｍ、好ましくは0.1 〜３μ
ｍの平均粒径を有する窒化珪素粉末を添加してもよい。
窒化珪素粉末の添加量は、熱処理により生成する窒化珪
素と添加する窒化珪素の合計を100 重量％として、０〜
10重量％とするのが好ましく、より好ましくは０〜５重
量％とする。窒化珪素粉末の添加量が多すぎると（珪素
粉末に対する窒化珪素粉末の割合が高すぎると）、Ｓｉ
の反応焼結が不十分であり、複合効果が得られない。(C) Silicon nitride powder In order to improve the moldability of the mixed powder and to use it as a nucleus for silicon nitride formation, 0.1 to 5 μm, preferably 0.1 to 3 μm.
A silicon nitride powder having an average particle size of m may be added.
The addition amount of the silicon nitride powder is 0 to 100% by weight of the total of the silicon nitride formed by the heat treatment and the added silicon nitride.
The content is preferably 10% by weight, more preferably 0 to 5% by weight. If the addition amount of the silicon nitride powder is too large (if the ratio of the silicon nitride powder to the silicon powder is too high), Si
Is insufficient in reaction sintering, and a combined effect cannot be obtained.
【００２０】(d) 炭化珪素粉末 炭化珪素粉末は、窒化珪素粉末と同様の目的、つまり珪
素粉末混合粉末の成形性を良くするとともにして炭化珪
素生成の核とするために少量添加してもよい。好ましい
炭化珪素粉末の添加量は、熱処理により生成する炭化珪
素と添加する炭化珪素との合計量を100 重量％として、
０〜10重量％であり、より好ましくは０〜５重量％であ
る。炭化珪素の添加量が多すぎると珪素の反応焼結が不
十分となり、複合効果が得られない。(D) Silicon Carbide Powder Silicon carbide powder may be added in a small amount for the same purpose as silicon nitride powder, that is, to improve the moldability of the silicon powder mixed powder and to serve as a nucleus for silicon carbide formation. Good. The preferable addition amount of silicon carbide powder is as follows: the total amount of silicon carbide formed by heat treatment and silicon carbide to be added is 100% by weight.
It is 0 to 10% by weight, more preferably 0 to 5% by weight. If the addition amount of silicon carbide is too large, the reaction sintering of silicon becomes insufficient, and a combined effect cannot be obtained.
【００２１】(e) 焼結助剤粉末 複合粉末製造時の焼結助剤粉末が（ａ）周期律表３Ａ族
元素及び４Ａ族元素の酸化物からなる群より選ばれた１
種以上の化合物、又は前記（ａ）と、（ｂ）窒化アルミ
ニウムとからなる。中でも、（ａ）Ｙ2 Ｏ3 、Ｌｕ2 Ｏ
3 、Ｙｂ2 Ｏ3、ＨｆＯ2 からなる群より選ばれた少な
くとも１種の化合物が好ましく、Ｙ2 Ｏ3 単独が特に好
ましい。(E) Sintering aid powder The sintering aid powder used in producing the composite powder is selected from the group consisting of (a) oxides of Group 3A and Group 4A elements of the periodic table.
At least one kind of compound, or (a) and (b) aluminum nitride. Among them, (a) Y 2 O 3 and Lu 2 O
3, Yb 2 O 3, at least one compound selected from the group consisting of HfO 2 are preferred, Y 2 O 3 alone is particularly preferred.
【００２２】複合成形体製造時の焼結助剤粉末が（ａ）
周期律表３Ａ族元素及び４Ａ族元素の酸化物からなる群
より選ばれた１種以上の化合物、又は（ｂ）窒化アルミ
ニウム及び／又は酸化珪素と、前記（ａ）とからなる。
中でも、（ａ）Ｙ2 Ｏ3 、Ｌｕ2 Ｏ3 、Ｙｂ2 Ｏ3 、Ｈ
ｆＯ2 からなる群より選ばれた少なくとも１種の化合
物、又は前記（ａ）と酸化珪素とが好ましく、Ｙ2 Ｏ3
単独、又はＹ2 Ｏ3 と酸化珪素とが特に好ましい。[0022] The sintering aid powder during the production of the composite molded body is (a)
It comprises one or more compounds selected from the group consisting of oxides of Group 3A and Group 4A elements of the periodic table, or (b) aluminum nitride and / or silicon oxide, and (a).
Among them, (a) Y 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , H
At least one compound selected from the group consisting of fO 2 , or (a) and silicon oxide are preferable, and Y 2 O 3
Alone, or Y 2 O 3 and silicon oxide are particularly preferred.
【００２３】焼結助剤粉末の含有量は、熱処理により生
成した複合粉末又は複合成形体の全量を100 重量％とし
て、５〜20重量％とするのが好ましく、より好ましくは
７〜15重量％とする。焼結助剤粉末が５重量％より少な
いと得られる複合粉末の焼結性が不十分であり、また20
重量％より多いと焼結体の高温強度が低くなる。The content of the sintering aid powder is preferably from 5 to 20% by weight, more preferably from 7 to 15% by weight, based on 100% by weight of the total amount of the composite powder or composite compact produced by the heat treatment. And If the amount of the sintering aid powder is less than 5% by weight, the sinterability of the obtained composite powder is insufficient, and
If it is more than 10% by weight, the high-temperature strength of the sintered body decreases.
【００２４】焼結助剤は、珪素粉末、炭素質粉末と一緒
に混合して窒化／炭化処理を行う。最初から焼結助剤を
添加することにより、複合粉末又は複合成形体中におけ
るα型窒化珪素の含有量が大きくなるとともに、焼結助
剤の分散状態が良くなり、焼結体特性が向上する。The sintering aid is mixed with silicon powder and carbonaceous powder to perform nitriding / carbonizing treatment. By adding the sintering aid from the beginning, the content of α-type silicon nitride in the composite powder or composite molded body increases, the dispersion state of the sintering aid improves, and the characteristics of the sintered body improve. .
【００２５】〔２〕複合粉末の製造方法 (1) 混合粉末の作製 まず、各成分を上記配合比となるように配合し、ボール
ミル、ニーダー等で十分に混合する。混合は乾式でも湿
式でも良い。湿式混合の場合には、粉末混合物に水、エ
タノール、ブタノール等の分散媒体を加える。また、適
当な有機又は無機バインダーを添加することができる。
有機バインダーとしては、例えばエチルシリケート、ポ
リエチレングリコール、ポリビニルアルコール（ＰＶ
Ａ）、アクリルエマルジョン、ポリウレタンエマルジョ
ン等が挙げられる。また、無機バインダーも添加するこ
とができる。[2] Production Method of Composite Powder (1) Preparation of Mixed Powder First, the respective components are blended so as to have the above-mentioned blending ratio, and are sufficiently mixed by a ball mill, a kneader or the like. Mixing may be dry or wet. In the case of wet mixing, a dispersion medium such as water, ethanol, or butanol is added to the powder mixture. Also, an appropriate organic or inorganic binder can be added.
As the organic binder, for example, ethyl silicate, polyethylene glycol, polyvinyl alcohol (PV
A), an acrylic emulsion, a polyurethane emulsion and the like. Also, an inorganic binder can be added.
【００２６】(2) 窒化／炭化処理 次に、混合粉末を窒素含有雰囲気下で加熱し、混合粉末
中の珪素粉末を窒化すると同時に炭化する。窒化率と炭
化率は出発原料中のＣの添加量により決まる。すなわ
ち、実質的に全てのＣは珪素と結合して炭化珪素となる
ので、未反応の珪素が実質的に全て窒化珪素に転化する
ことになる。例えば、ＳｉとＣとが100 ：７のモル比で
混合されているとすると、窒化珪素と炭化珪素とのモル
比は31：７となる。(2) Nitriding / Carburizing Treatment Next, the mixed powder is heated in a nitrogen-containing atmosphere to nitride and carbonize the silicon powder in the mixed powder. The nitridation rate and carbonization rate are determined by the amount of C in the starting material. That is, since substantially all of C is combined with silicon to form silicon carbide, substantially all unreacted silicon is converted to silicon nitride. For example, if Si and C are mixed at a molar ratio of 100: 7, the molar ratio of silicon nitride to silicon carbide is 31: 7.
【００２７】窒化／炭化処理の諸条件は、混合粉末の組
成等により多少変更する必要があるが、温度は1450℃以
下とする。1450℃を超える温度に加熱すると、珪素が溶
出したり、珪素の気化が起こったりするので好ましくな
い。窒化／炭化処理温度の下限は1000℃とするのが好ま
しい。1000℃未満であると、窒化／炭化反応が起こらな
いか、起こっても反応速度が低すぎる。より好ましい反
応温度は1100〜1380℃である。The conditions of the nitriding / carbonizing treatment need to be slightly changed depending on the composition of the mixed powder, but the temperature is set to 1450 ° C. or less. Heating to a temperature exceeding 1450 ° C. is not preferable because silicon elutes or silicon evaporates. The lower limit of the nitriding / carbonizing treatment temperature is preferably set to 1000 ° C. If the temperature is lower than 1000 ° C., the nitriding / carbonization reaction does not occur, or the reaction rate is too low even if it occurs. A more preferred reaction temperature is 1100-1380 ° C.
【００２８】本発明では、窒化反応の反応温度（保持温
度）付近での昇温速度を小さくする。具体的には、雰囲
気温度が900 〜1300℃以上になると、昇温速度を２℃／
分未満とし、好ましくは 0.5℃／分以下とする。昇温速
度が２℃／分以上になると、窒化反応が激しくなり、生
成される複合粉末内におけるα型窒化珪素の含有率が減
少し、複合粉末の焼結性が低下するので好ましくない。
好ましいα型窒化珪素の含有率は、複合粉末中の全窒化
珪素に対して30％以上、特に好ましくは40％以上とす
る。In the present invention, the rate of temperature rise near the reaction temperature (holding temperature) of the nitriding reaction is reduced. Specifically, when the ambient temperature is 900 to 1300 ° C or higher, the temperature increasing rate is 2 ° C /
Min, preferably 0.5 ° C / min or less. When the rate of temperature rise is 2 ° C./min or more, the nitridation reaction becomes violent, the content of α-type silicon nitride in the produced composite powder decreases, and the sinterability of the composite powder decreases.
The preferred content of α-type silicon nitride is at least 30%, particularly preferably at least 40%, based on the total silicon nitride in the composite powder.
【００２９】窒素含有雰囲気の圧力は１kgf ／cm2 以上
とするのが好ましく、より好ましくは５〜2000kgf ／cm
2 とする。窒素含有雰囲気の圧力が１kgf ／cm2 未満で
あると窒化が良好に進まない。窒化／炭化処理の反応時
間は、処理温度等により多少変化するが、一般に１〜10
時間程度とするのが好ましい。なお、窒素含有雰囲気と
は窒素含有ガスの雰囲気で、窒素含有ガスとしては窒素
ガス、窒素と水素の混合ガスあるいは窒素とアンモニア
の混合ガス等が挙げられる。The pressure of the nitrogen-containing atmosphere is preferably 1 kgf / cm 2 or more, more preferably 5 to 2000 kgf / cm 2.
Assume 2 . If the pressure of the nitrogen-containing atmosphere is less than 1 kgf / cm 2 , nitriding does not proceed well. The reaction time of the nitriding / carbonizing treatment varies slightly depending on the treatment temperature and the like, but is generally 1 to 10
It is preferable to set it to about an hour. Note that the nitrogen-containing atmosphere is an atmosphere of a nitrogen-containing gas, and examples of the nitrogen-containing gas include a nitrogen gas, a mixed gas of nitrogen and hydrogen, or a mixed gas of nitrogen and ammonia.
【００３０】(3) 粉末の粉砕 得られた窒化珪素／炭化珪素複合物を粉砕して、複合粉
末とする。粉砕はボールミル、ジェットミル、アトリシ
ョンミル等を用いて行うことができる。粉砕によって得
られる複合粉末の平均粒径は0.1 〜５μｍであるのが好
ましく、0.3 〜３μｍであるのがより好ましい。(3) Pulverization of Powder The obtained silicon nitride / silicon carbide composite is pulverized into a composite powder. The pulverization can be performed using a ball mill, a jet mill, an attrition mill or the like. The average particle size of the composite powder obtained by pulverization is preferably from 0.1 to 5 μm, more preferably from 0.3 to 3 μm.
【００３１】以上の条件で窒化／炭化処理を行うと、混
合粉末中の珪素粒子は炭素と反応して出発原料の珪素粒
子及び炭素粒子よりも微細な炭化珪素の微細粒子を生成
するとともに、窒化されて出発原料の珪素粒子よりも微
細なα−窒化珪素を高割合で含む窒化珪素が生成され
る。When the nitriding / carbonizing treatment is carried out under the above conditions, the silicon particles in the mixed powder react with carbon to form fine particles of silicon carbide and finer silicon carbide than the starting material silicon particles and carbon particles. As a result, silicon nitride containing α-silicon nitride, which is finer than the silicon particles of the starting material, in a high ratio is generated.
【００３２】〔３〕複合成形体の製造方法 (1) 成形体の作製 まず、各成分を上記〔２〕(1) の欄に記載したのと同じ
方法で配合し、混合する。得られた混合粉末を所望の形
状に成形するが、成形方法としてはプレス成形、スリッ
プキャスティング成形、射出成形等を使用することがで
きる。[3] Production method of composite molded article (1) Production of molded article First, each component is blended and mixed by the same method as described in the above section [2] (1). The obtained mixed powder is molded into a desired shape. As a molding method, press molding, slip casting molding, injection molding or the like can be used.
【００３３】プレス成形の場合には、分散媒体を除去後
に所望のプレス型を用いて成形を行う。スリップキャス
ティング成形の場合には、分散媒体とともに吸湿性の型
に流し込む。射出成形の場合には適当な有機又は無機バ
インダーを添加して、型内に射出する。有機バインダー
としては、例えばエチルシリケート、ポリエチレングリ
コール、ポリビニルアルコール（ＰＶＡ）、アクリルエ
マルジョン、ポリウレタンエマルジョン等が挙げられ
る。また無機バインダーも添加することができる。複雑
な形状の成形体を作製するにはスリップキャスティング
成形や射出成形が好ましい。In the case of press molding, molding is performed using a desired press mold after removing the dispersion medium. In the case of slip casting, it is poured into a hygroscopic mold together with the dispersion medium. In the case of injection molding, an appropriate organic or inorganic binder is added and the mixture is injected into a mold. Examples of the organic binder include ethyl silicate, polyethylene glycol, polyvinyl alcohol (PVA), acrylic emulsion, and polyurethane emulsion. An inorganic binder can also be added. To produce a molded article having a complicated shape, slip casting or injection molding is preferred.
【００３４】(2) 窒化／炭化処理 窒化／炭化処理の条件は上記[2] (2) の欄に記載したの
とほぼ同じでよいが、成形体の厚さ、出発原料粉末の粒
径等により多少変更する必要があり、温度は1450℃以下
とする。1450℃を超える温度に加熱すると、珪素が溶出
するので好ましくない。窒化／炭化処理温度の下限は10
00℃とするのが好ましい。1000℃未満であると、窒化／
炭化反応が起こらないか、起こっても反応速度が低すぎ
る。より好ましい反応温度は1200〜1400℃である。(2) Nitriding / Carburizing Treatment The conditions of the nitriding / carbonizing treatment may be almost the same as those described in the above section [2] (2), but the thickness of the compact, the particle size of the starting material powder, etc. Therefore, it is necessary to change the temperature slightly, and the temperature should be 1450 ° C or less. Heating to a temperature exceeding 1450 ° C. is not preferable because silicon elutes. The lower limit of nitriding / carbonizing treatment temperature is 10
It is preferably set to 00 ° C. If the temperature is lower than 1000 ° C, nitriding /
The carbonization reaction does not occur, or if it does, the reaction rate is too low. A more preferred reaction temperature is 1200-1400 ° C.
【００３５】本発明では、窒化反応の反応温度（保持温
度）付近での昇温速度を小さくする。具体的には、雰囲
気温度が900 〜1300℃以上になると、昇温速度を２℃／
分未満とし、好ましくは 0.5℃／分以下とする。昇温速
度が２℃／分以上になると、窒化反応が激しくなり、生
成される複合成形体内におけるα型窒化珪素の含有率が
減少し、複合成形体の焼結性が低下するので好ましくな
い。好ましいα型窒化珪素の含有率は、複合成形体中の
全窒化珪素に対して30％以上、特に好ましくは40％以上
とする。In the present invention, the rate of temperature rise near the reaction temperature (holding temperature) of the nitriding reaction is reduced. Specifically, when the ambient temperature is 900 to 1300 ° C or higher, the temperature increasing rate is 2 ° C /
Min, preferably 0.5 ° C / min or less. If the rate of temperature rise is 2 ° C./min or more, the nitridation reaction becomes violent, the content of α-type silicon nitride in the formed composite decreases, and the sinterability of the composite decreases. The preferred content of α-type silicon nitride is at least 30%, particularly preferably at least 40%, based on the total silicon nitride in the composite molded body.
【００３６】以上の条件で窒化／炭化処理を行うと、成
形体中の珪素粒子は炭素と反応して出発原料の珪素粒子
及び炭素粒子よりも微細な炭化珪素粒子を生成するとと
もに、窒化されて出発原料の珪素粒子よりも微細なα−
窒化珪素を含む窒化珪素が生成される。When the nitriding / carburizing treatment is performed under the above conditions, the silicon particles in the molded body react with carbon to form silicon carbide particles that are finer than the starting material silicon particles and carbon particles, and are also nitrided. Α- finer than the starting silicon particles
Silicon nitride containing silicon nitride is generated.
【００３７】〔４〕複合焼結体の製造方法 (1) 窒化珪素／炭化珪素複合焼結体を製造する本発明の
第一の方法は、まず上記〔２〕の欄に記載した窒化珪素
／炭化珪素複合粉末を上記〔３〕(1) の欄に記載したも
のと同じ方法で成形する。成形体を1600〜2200℃の温度
で、好ましくは1800〜2000℃の温度で焼結する。焼結温
度が1600℃未満であると、焼結体の緻密化が不十分にな
り、所望の特性が得られない。また焼結温度が2200℃を
超えると窒化珪素の分解が始まるので好ましくない。焼
結は非酸化性雰囲気下、好ましくは窒素ガス雰囲気下で
行う。このとき、雰囲気ガス圧は５〜2000kgf ／cm2 程
度とするのが好ましい。また、焼結温度保持時間は１〜
５時間程度とするのが好ましい。良好な焼結体密度を達
成するためにはホットプレス又はＨＩＰが好ましい。特
にＨＩＰで焼成する場合は、複雑な形状の焼結体も製造
できる。[4] Method for Manufacturing Composite Sintered Body (1) The first method of the present invention for manufacturing a silicon nitride / silicon carbide composite sintered body is as follows. The silicon carbide composite powder is formed by the same method as described in the above section [3] (1). The compact is sintered at a temperature of 1600-2200 ° C, preferably at a temperature of 1800-2000 ° C. If the sintering temperature is lower than 1600 ° C., the densification of the sintered body becomes insufficient, and desired characteristics cannot be obtained. If the sintering temperature exceeds 2200 ° C., decomposition of silicon nitride starts, which is not preferable. Sintering is performed in a non-oxidizing atmosphere, preferably in a nitrogen gas atmosphere. At this time, the atmospheric gas pressure is preferably set to about 5 to 2000 kgf / cm 2 . Also, the sintering temperature holding time is 1 to
Preferably, it is about 5 hours. Hot pressing or HIP is preferred in order to achieve a good sintered body density. In particular, when firing by HIP, a sintered body having a complicated shape can be manufactured.
【００３８】(2) 窒化珪素／炭化珪素複合焼結体を製造
する本発明の第二の方法は、上記〔３〕の欄に記載した
窒化珪素／炭化珪素複合成形体を上記〔４〕(1) の欄に
記載したものと同じ方法で焼結する。なお、焼結する前
に、窒化珪素／炭化珪素複合成形体を酸化性雰囲気中に
おいて熱処理してもよい。この熱処理により窒化珪素／
炭化珪素複合成形体を構成する窒化珪素及び炭化珪素の
表面が酸化され、酸化珪素の皮膜が形成される。この皮
膜により酸化珪素を焼結助剤として添加した場合と同様
に、酸化珪素と焼結助剤が反応して焼結が促進される。
熱処理の温度は1300℃未満が好ましい。(2) In the second method of the present invention for producing a silicon nitride / silicon carbide composite sintered body, the silicon nitride / silicon carbide composite molded article described in the above section [3] is prepared by the above [4] ( Sinter in the same manner as described in 1). Before sintering, the silicon nitride / silicon carbide composite molded body may be heat-treated in an oxidizing atmosphere. The silicon nitride /
The surfaces of silicon nitride and silicon carbide constituting the silicon carbide composite molded body are oxidized to form a silicon oxide film. As with the case where silicon oxide is added as a sintering aid, this film reacts with silicon oxide and the sintering aid to promote sintering.
The temperature of the heat treatment is preferably less than 1300 ° C.
【００３９】(3) 窒化珪素／炭化珪素複合焼結体 上記方法で得られた窒化珪素／炭化珪素複合焼結体は、
窒化珪素粒子内に微細な炭化珪素粒子が分散したいわゆ
るナノコンポジット構造を有する。炭化珪素粒子は窒化
珪素粒子より熱膨張率が大きいため、窒化珪素粒子に残
留応力が働くと考えられる。また窒化珪素の粒界に分散
した微細な炭化珪素粒子は、窒化珪素の粒界すべりを抑
制するくさびのような作用をすると考えられる。(3) Silicon nitride / silicon carbide composite sintered body The silicon nitride / silicon carbide composite sintered body obtained by the above method is:
It has a so-called nanocomposite structure in which fine silicon carbide particles are dispersed in silicon nitride particles. Since silicon carbide particles have a larger coefficient of thermal expansion than silicon nitride particles, it is considered that residual stress acts on the silicon nitride particles. It is also considered that fine silicon carbide particles dispersed in the silicon nitride grain boundaries act like a wedge that suppresses grain boundary sliding of silicon nitride.
【００４０】従って、炭化珪素／窒化珪素の比が小さい
場合、上記効果が十分に得られない。一方、炭化珪素／
窒化珪素の比が大きすぎると、分散する炭化珪素粒子が
多すぎて窒化珪素の粒成長が抑制されてしまい、焼結体
密度が十分に増大しない。以上の点から炭化珪素／窒化
珪素の重量比は５／95〜50／50が好ましく、15／85〜40
／60がより好ましい。Therefore, when the ratio of silicon carbide / silicon nitride is small, the above effects cannot be sufficiently obtained. On the other hand, silicon carbide /
If the ratio of silicon nitride is too large, too many silicon carbide particles are dispersed, so that grain growth of silicon nitride is suppressed, and the density of the sintered body does not sufficiently increase. From the above points, the weight ratio of silicon carbide / silicon nitride is preferably 5/95 to 50/50, and 15/85 to 40/50.
/ 60 is more preferred.
【００４１】[0041]
【実施例】以下、本発明を具体的実施例によりさらに詳
細に説明するが、本発明はこれに限定されるものではな
い。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited thereto.
【００４２】実施例１ (1) 複合粉末の作製 平均粒径が0.5 μｍの珪素粉末（JIS MSi 1 ）と、炭素
質として粒径が５μｍ以下のカーボン粉末と、平均粒径
が0.1 μｍの窒化珪素粉末と、平均粒径が0.2μｍの炭
化珪素粉末と、平均粒径が1.4 μｍのＹ2 Ｏ3 粉末と、
平均粒径が２μｍのＡｌＮ粉末とを、表１に示す割合で
（ただし、珪素粉末及び炭素質であるカーボン粉末の配
合比は、生成した複合粉末における窒化珪素、炭化珪素
及び焼結助剤の割合が表１０に示した目的配合比となる
ように、窒化珪素及び炭化珪素が生成する反応式に従っ
て計算した値である。）秤量し、ボールミルにより200
重量部のエタノールを溶媒として８０重量部のボールと
ともに18時間混合し、乾燥した。 Example 1 (1) Preparation of Composite Powder A silicon powder (JIS MSi 1) having an average particle size of 0.5 μm, a carbon powder having a particle size of 5 μm or less as carbonaceous material, and a nitride having an average particle size of 0.1 μm Silicon powder, silicon carbide powder having an average particle size of 0.2 μm, Y 2 O 3 powder having an average particle size of 1.4 μm,
An AlN powder having an average particle diameter of 2 μm was mixed at a ratio shown in Table 1 (however, the mixing ratio of the silicon powder and the carbonaceous carbon powder was determined based on the proportion of silicon nitride, silicon carbide, and sintering aid in the produced composite powder). It is a value calculated according to a reaction formula for producing silicon nitride and silicon carbide so that the ratio becomes the target compounding ratio shown in Table 10.)
The mixture was mixed with 80 parts by weight of a ball using 18 parts by weight of ethanol as a solvent for 18 hours and dried.
【００４３】得られた原料粉末を反応容器に入れ、1300
℃からの昇温速度を0.5 ℃／分として1380℃まで昇温し
た後、60分間保持した。雰囲気は窒素ガス雰囲気として
９kgf ／cm2 のガス圧下で窒化／炭化反応を起こさせた
後、200 重量部のアルコール及び200 重量部の窒化珪素
ボールとともに２リットルのポリエチレンポットに入れ
て、ボールミルで７日間粉砕し、複合粉末を調製した。The obtained raw material powder was placed in a reaction vessel, and 1300
The temperature was raised to 1380 ° C. at a rate of 0.5 ° C./min from the temperature and then maintained for 60 minutes. After nitriding / carbonizing reaction was caused under a gas pressure of 9 kgf / cm 2 as a nitrogen gas atmosphere, the mixture was put into a 2 liter polyethylene pot together with 200 parts by weight of alcohol and 200 parts by weight of silicon nitride balls, and then ball milled. The mixture was ground for a day to prepare a composite powder.
【００４４】得られた複合粉末のＸ線回折を測定し、α
型窒化珪素とβ型窒化珪素の結晶相を同定し、全窒化珪
素中のα型窒化珪素の含有率を下式で求めた。 α型窒化珪素の含有率（％）＝100 ×(102) 面と(210)
面の合計回折強度（α型窒化珪素）／（(102) 面と(21
0) 面の合計回折強度（α型窒化珪素）＋(101) 面と(21
0) 面の合計回折強度（β型窒化珪素））結果はまとめ
て表７に示す。X-ray diffraction of the obtained composite powder was measured, and α
The crystal phases of silicon nitride of the type and silicon of the type β were identified, and the content of α-type silicon nitride in the total silicon nitride was determined by the following equation. α-type silicon nitride content (%) = 100 × (102) plane and (210)
Total diffraction intensity of plane (α-type silicon nitride) / ((102) plane and (21)
0) plane total diffraction intensity (α-type silicon nitride) + (101) plane and (21) plane
Table 7 summarizes the results of the (0) plane total diffraction intensity (β-type silicon nitride).
【００４５】 表１ 原料粉末組成 重量（ｇ） 配合比（重量％） 珪素粉末 270.7 69.9 カーボン粉末 43.7 11.3 窒化珪素粉末 14.9 3.9 炭化珪素粉末 7.7 2.0 Ｙ2 Ｏ3 粉末 35.0 9.0 ＡｌＮ粉末 15.0 3.9 Table 1 Raw material powder composition Weight (g) Mixing ratio (% by weight) Silicon powder 270.7 69.9 Carbon powder 43.7 11.3 Silicon nitride powder 14.9 3.9 Silicon carbide powder 7.7 2.0 Y 2 O 3 powder 35.0 9.0 AlN powder 15.0 3.9
【００４６】(2) 複合焼結体の作製 (1) で得た複合粉末を55×35×６ｍｍの形状に圧力200k
gf／cm2 の金型プレスで予備成形した後、ＣＩＰで４ト
ン／平方センチの等方圧を加えた。次いで最高保持温度
1850℃、最高窒素ガス圧力1000kgf ／cm2 の条件でＨＩ
Ｐ焼結を行い、窒化珪素／炭化珪素複合焼結体を得た。
得られた焼結体の組織を電子顕微鏡で観察したところ、
ナノコンポジット構造を有することが分かった。(2) Preparation of Composite Sintered Body The composite powder obtained in (1) was formed into a shape of 55 × 35 × 6 mm at a pressure of 200 kPa.
After preforming with a gf / cm 2 mold press, an isotropic pressure of 4 ton / square cm was applied by CIP. Then the maximum holding temperature
HI at 1850 ° C, maximum nitrogen gas pressure 1000kgf / cm 2
P sintering was performed to obtain a silicon nitride / silicon carbide composite sintered body.
When the structure of the obtained sintered body was observed with an electron microscope,
It was found to have a nanocomposite structure.
【００４７】(3) 複合焼結体の物性 得られた焼結体の密度をアルキメデス法で測定した。JI
S R-1601に従って、焼結体を３ｍｍ×４ｍｍ×40ｍｍの
大きさに切断して試験片とし、３点曲げ強度試験（室温
及び1400℃）、及び破壊靭性値Ｋ1 c の測定を以下の条
件で行った結果を表７に示す。 (i) ３点曲げ強度試験：室温の場合にはスパン30ｍｍ及
びクロスヘッドスピード0.5 ｍｍ／分の条件で行い、ま
た。1400℃の場合には1400℃に昇温し１時間保持した後
上記条件で行った。 (ii)破壊靭性値：ＳＥＮＢ法（Single Edge Notched Be
am Method ）に従って求めた。(3) Physical Properties of Composite Sintered Body The density of the obtained sintered body was measured by the Archimedes method. JI
According to SR-1601, the sintered body was cut into a size of 3 mm × 4 mm × 40 mm to obtain a test piece, and a three-point bending strength test (room temperature and 1400 ° C.) and a measurement of a fracture toughness value K 1 c were performed as follows. Table 7 shows the results obtained under the conditions. (i) Three-point bending strength test: At room temperature, the test was performed under the conditions of a span of 30 mm and a crosshead speed of 0.5 mm / min. In the case of 1400 ° C., the temperature was raised to 1400 ° C. and the temperature was maintained for 1 hour, and then the above conditions were used. (ii) Fracture toughness: SENB method (Single Edge Notched Be
am Method).
【００４８】実施例２ 実施例１で得た窒化珪素／炭化珪素複合粉末を用いて、
実施例１と同条件で成形し、実施例１と同条件でＨＩＰ
処理を経た後さらに窒素ガス雰囲気下、1500℃で２時間
保持する常圧焼結を行い、焼結体を得た。実施例１と同
様に焼結体の強度試験を行い、結果を表７に示す。 Example 2 Using the silicon nitride / silicon carbide composite powder obtained in Example 1,
Molded under the same conditions as in Example 1 and HIP under the same conditions as in Example 1.
After the treatment, normal pressure sintering was performed at 1500 ° C. for 2 hours under a nitrogen gas atmosphere to obtain a sintered body. A strength test was performed on the sintered body in the same manner as in Example 1, and the results are shown in Table 7.
【００４９】実施例３ (1) 複合粉末の作製 平均粒径が0.5 μｍの珪素粉末（JIS MSi 1 ）と、炭素
質として平均粒径が500 オングストロームのアセチレン
ブラック粉末と、平均粒径が0.1 μｍの窒化珪素粉末
と、平均粒径が0.2 μｍの炭化珪素粉末と、平均粒径が
1.4 μｍのＹ2 Ｏ3 粉末とを、表２に示す割合で（ただ
し、実施例１と同様に表１０に示した目的配合比より計
算した値である。）秤量し、ボールミルにより200 重量
部のエタノールを溶媒として80重量部のボールとともに
18時間混合し、乾燥した。 Example 3 (1) Preparation of Composite Powder A silicon powder (JIS MSi 1) having an average particle size of 0.5 μm, an acetylene black powder having an average particle size of 500 Å as carbonaceous material, and an average particle size of 0.1 μm Silicon nitride powder, silicon carbide powder having an average particle size of 0.2 μm,
1.4 μm of Y 2 O 3 powder was weighed in the ratio shown in Table 2 (however, calculated from the target compounding ratio shown in Table 10 in the same manner as in Example 1), and 200 parts by weight by a ball mill. With 80 parts by weight of ethanol as solvent
Mix for 18 hours and dry.
【００５０】 表２ 原料粉末組成 重量（ｇ） 配合比（重量％） 珪素粉末 274.9 72.9 アセチレンブラック粉末 39.4 10.4 窒化珪素粉末 16.1 4.3 炭化珪素粉末 6.9 1.8 Ｙ2 Ｏ3 粉末 40.0 10.6 Table 2 Raw material powder composition Weight (g) Compounding ratio (% by weight) Silicon powder 274.9 72.9 Acetylene black powder 39.4 10.4 Silicon nitride powder 16.1 4.3 Silicon carbide powder 6.9 1.8 Y 2 O 3 powder 40.0 10.6
【００５１】得られた原料粉末を反応容器に入れ、1300
℃からの昇温速度を0.5 ℃／分として1380℃まで昇温し
た後、1380℃で保持せず処理を終了した。雰囲気は窒素
ガス雰囲気として９kgf ／cm2 のガス圧下で窒化／炭化
反応を起こさせた後、200 重量部のアルコール及び200
重量部の窒化珪素ボールとともに２リットルのポリエチ
レンポットに入れて、ボールミルで７日間粉砕し、複合
粉末を調製した。得られた複合粉末のα型窒化珪素の含
有率を実施例１と同様に求めた。結果を表７に示す。The obtained raw material powder was placed in a reaction vessel, and 1300
After the temperature was raised to 1380 ° C. at a rate of 0.5 ° C./min from the temperature, the treatment was terminated without maintaining the temperature at 1380 ° C. The nitriding / carbonization reaction was performed under a gas pressure of 9 kgf / cm 2 in a nitrogen gas atmosphere, and then 200 parts by weight of alcohol and 200 parts by weight
The mixture was placed in a 2 liter polyethylene pot together with parts by weight of silicon nitride balls and pulverized by a ball mill for 7 days to prepare a composite powder. The α-type silicon nitride content of the obtained composite powder was determined in the same manner as in Example 1. Table 7 shows the results.
【００５２】(2) 複合焼結体の作製 (1) で得た複合粉末を直径42ｍｍの黒鉛ダイスに充填
し、９kgf ／cm2 の窒素ガス雰囲気中で、4.8 トンの荷
重で最高1850℃まで昇温して、ホットプレス焼結を行
い、窒化珪素／炭化珪素複合焼結体を得た。得られた焼
結体の組織を電子顕微鏡で観察したところ、ナノコンポ
ジット構造を有することが分かった。得られた複合焼結
体の物性を実施例１と同様に求めた。結果を表７に示
す。(2) Preparation of Composite Sintered Body The composite powder obtained in (1) was filled in a graphite die having a diameter of 42 mm and heated to a maximum of 1850 ° C. under a nitrogen gas atmosphere of 9 kgf / cm 2 at a load of 4.8 tons and a load of 4.8 tons. The temperature was raised and hot press sintering was performed to obtain a silicon nitride / silicon carbide composite sintered body. Observation of the structure of the obtained sintered body with an electron microscope revealed that the structure had a nanocomposite structure. The physical properties of the obtained composite sintered body were determined in the same manner as in Example 1. Table 7 shows the results.
【００５３】実施例４ 平均粒径が3.4 μｍである珪素粉末（JIS MSi 1 ）を使
用した以外は実施例３と同様にして、窒化珪素／炭化珪
素複合粉末及び焼結体を得た。得られた粉末のα型窒化
珪素の含有率を実施例１と同様に求め、結果を表７に示
す。得られた複合焼結体の物性を実施例１と同様に求め
た。結果を表７に示す。 Example 4 A silicon nitride / silicon carbide composite powder and a sintered body were obtained in the same manner as in Example 3 except that silicon powder (JIS MSi 1) having an average particle size of 3.4 μm was used. The content of α-type silicon nitride in the obtained powder was determined in the same manner as in Example 1, and the results are shown in Table 7. The physical properties of the obtained composite sintered body were determined in the same manner as in Example 1. Table 7 shows the results.
【００５４】比較例１ 実施例１と同じ原料粉末を用い、1300℃からの昇温速度
を２℃／分とした以外は実施例１と同様の熱処理条件及
び窒素雰囲気下で窒化／炭化反応を起こさせた。熱処理
した後実施例１と同様にボールミルで７日間粉砕した。 Comparative Example 1 The same raw material powder as in Example 1 was used, and the nitriding / carbonization reaction was carried out under the same heat treatment conditions and nitrogen atmosphere as in Example 1 except that the heating rate from 1300 ° C. was changed to 2 ° C./min. Awakened. After the heat treatment, the mixture was ground in a ball mill for 7 days in the same manner as in Example 1.
【００５５】得られた窒化珪素／炭化珪素複合粉末を用
いて、実施例１と同条件で成形し、実施例１と同条件で
ＨＩＰ焼結を行い、焼結体を得た。実施例１と同様に焼
結体の強度試験及びＫ1 c の測定を行った。結果を表７
に示す。Using the obtained silicon nitride / silicon carbide composite powder, molding was performed under the same conditions as in Example 1, and HIP sintering was performed under the same conditions as in Example 1 to obtain a sintered body. A strength test of the sintered body and measurement of K 1 c were performed in the same manner as in Example 1. Table 7 shows the results
Shown in
【００５６】比較例２ 炭素質粉末としてアセチレンブラック粉末を用いた以外
は、実施例１と同じ原料粉末を用い、比較例１と同様の
熱処理条件で窒化／炭化反応を起こさせた。熱処理した
後実施例１と同様にボールミルで７日間粉砕し、複合粉
末を調製した。 Comparative Example 2 The same raw material powder as in Example 1 was used except that acetylene black powder was used as the carbonaceous powder, and a nitriding / carbonization reaction was caused under the same heat treatment conditions as in Comparative Example 1. After the heat treatment, the mixture was pulverized in a ball mill for 7 days in the same manner as in Example 1 to prepare a composite powder.
【００５７】得られた窒化珪素／炭化珪素複合粉末を用
いて、実施例１と同条件で成形し、実施例１と同条件で
ＨＩＰ焼結を行い、焼結体を得た。実施例１と同様に焼
結体の強度試験を行い、結果を表７に示す。Using the obtained silicon nitride / silicon carbide composite powder, molding was performed under the same conditions as in Example 1, and HIP sintering was performed under the same conditions as in Example 1 to obtain a sintered body. A strength test was performed on the sintered body in the same manner as in Example 1, and the results are shown in Table 7.
【００５８】比較例３ 比較例２で得た窒化珪素／炭化珪素複合粉末を用いて、
実施例１と同条件で成形し、実施例１と同条件でＨＩＰ
処理を経た後さらに実施例２と同条件で常圧焼結を行
い、焼結体を得た。実施例１と同様に焼結体の強度試験
及び破壊靭性値Ｋ1 c の測定を行い、結果を表７に示
す。 Comparative Example 3 Using the silicon nitride / silicon carbide composite powder obtained in Comparative Example 2,
Molded under the same conditions as in Example 1 and HIP under the same conditions as in Example 1.
After the treatment, normal pressure sintering was performed under the same conditions as in Example 2 to obtain a sintered body. The strength test and the fracture toughness value K 1 c of the sintered body were measured in the same manner as in Example 1, and the results are shown in Table 7.
【００５９】比較例４ Ｙ2 Ｏ3 粉末とＡｌＮ粉末を添加しない以外は、実施例
１と同様の粉末を表３に示す割合で秤量し、ボールミル
により実施例１と同じ条件で混合し、乾燥した。 Comparative Example 4 The same powder as in Example 1 was weighed at the ratio shown in Table 3 except that the Y 2 O 3 powder and the AlN powder were not added, mixed by a ball mill under the same conditions as in Example 1, and dried. did.
【００６０】 表３ 原料粉末組成 重量（ｇ） 配合比（重量％） 珪素粉末 300.6 80.4 カーボン粉末 48.5 13.0 窒化珪素粉末 16.5 4.4 炭化珪素粉末 8.5 2.3 Table 3 Raw material powder composition Weight (g) Mixing ratio (% by weight) Silicon powder 300.6 80.4 Carbon powder 48.5 13.0 Silicon nitride powder 16.5 4.4 Silicon carbide powder 8.5 2.3
【００６１】得られた原料粉末を反応容器に入れ、実施
例１と同じ条件で窒化／炭化反応を起こさせた。熱処理
した後の複合粉末を90重量％として、平均粒径が1.4 μ
ｍのＹ2 Ｏ3 粉末７重量％と、平均粒径が２μｍのＡｌ
Ｎ粉末３重量％とを、200 重量％のアルコール及び200
重量％の窒化珪素ボールとともに、２リットルのポリエ
チレンポットに入れて、ボールミルで７日間混合粉砕
し、実施例１と同組成となる複合粉末を調製した。得ら
れた複合粉末のα型窒化珪素の含有率を実施例１と同様
にして求めた。結果はまとめて表７に示す。The obtained raw material powder was placed in a reaction vessel, and a nitriding / carbonization reaction was caused under the same conditions as in Example 1. Assuming that the composite powder after heat treatment is 90% by weight, the average particle size is 1.4μ
7% by weight of Y 2 O 3 powder and Al having an average particle size of 2 μm
3% by weight of N powder and 200% by weight of alcohol and 200% by weight.
The resulting mixture was placed in a 2 liter polyethylene pot together with the silicon nitride ball at a weight ratio of 7% and mixed and ground by a ball mill for 7 days to prepare a composite powder having the same composition as in Example 1. The α-type silicon nitride content of the obtained composite powder was determined in the same manner as in Example 1. The results are summarized in Table 7.
【００６２】得られた窒化珪素／炭化珪素複合粉末を用
い、実施例１と同条件で成形し、実施例１と同条件でＨ
ＩＰ焼結を行い、窒化珪素／炭化珪素複合焼結体を得
た。得られた焼結体の強度試験を行い、結果を表７に示
す。Using the obtained silicon nitride / silicon carbide composite powder, molding was performed under the same conditions as in Example 1, and H was formed under the same conditions as in Example 1.
IP sintering was performed to obtain a silicon nitride / silicon carbide composite sintered body. A strength test was performed on the obtained sintered body, and the results are shown in Table 7.
【００６３】実施例５ (1) 複合粉末の作製 平均粒径が0.7 μｍの珪素粉末（JIS MSi 1 ）と、炭素
質として粒径が５μｍ以下のカーボン粉末と、平均粒径
が１μｍのＬｕ2 Ｏ3 粉末とを、表４に示す割合で（た
だし、実施例１と同様に表１０に示した目的配合比より
計算した値である。）秤量し、ボールミルにより200 重
量部のエタノールを溶媒として100 重量部のボールとと
もに18時間混合し、乾燥した。 Example 5 (1) Preparation of Composite Powder Silicon powder (JIS MSi 1) having an average particle diameter of 0.7 μm, carbon powder having a particle diameter of 5 μm or less as carbonaceous material, and Lu 2 having an average particle diameter of 1 μm The O 3 powder was weighed at the ratio shown in Table 4 (however, calculated from the target compounding ratio shown in Table 10 in the same manner as in Example 1), and 200 parts by weight of ethanol was used as a solvent by a ball mill. Blended with 100 parts by weight of ball for 18 hours and dried.
【００６４】 表４ 原料粉末組成 重量（ｇ） 配合比（重量％） 珪素粉末 270.1 71.2 カーボン粉末 38.7 10.2 Ｌｕ2 Ｏ3 粉末 70.5 18.6 Table 4 Raw material powder composition Weight (g) Mixing ratio (% by weight) Silicon powder 270.1 71.2 Carbon powder 38.7 10.2 Lu 2 O 3 powder 70.5 18.6
【００６５】得られた原料粉末を反応容器に入れ、1150
℃からの昇温速度を0.5 ℃／分として1230℃まで昇温し
た後、60分間保持した。雰囲気は窒素ガス雰囲気として
９kgf ／cm2 のガス圧下で窒化／炭化反応を起こさせた
後、200 重量部のアルコール及び200 重量部の窒化珪素
ボールとともに２リットルのポリエチレンポットに入れ
て、ボールミルで７日間粉砕し、複合粉末を調製した。
得られた複合粉末のα型窒化珪素の含有率を実施例１と
同様に求めた。結果を表７に示す。The obtained raw material powder was placed in a reaction vessel, and 1150
After the temperature was raised to 1230 ° C. at a rate of 0.5 ° C./min from the temperature, the temperature was maintained for 60 minutes. After nitriding / carbonizing reaction was caused under a gas pressure of 9 kgf / cm 2 as a nitrogen gas atmosphere, the mixture was put into a 2 liter polyethylene pot together with 200 parts by weight of alcohol and 200 parts by weight of silicon nitride balls, and then ball milled. The mixture was ground for a day to prepare a composite powder.
The α-type silicon nitride content of the obtained composite powder was determined in the same manner as in Example 1. Table 7 shows the results.
【００６６】(2) 複合焼結体の作製 (1) で得た複合粉末を用いて、実施例１と同じ条件で成
形した。この成形体を９kgf ／cm2 の窒素ガス雰囲気
中、2000℃で４時間常圧焼結し、ついで1000kgf／cm2
の窒素ガス雰囲気中、1850℃て１時間ＨＩＰ焼結した。
実施例１と同様に得られた複合焼結体の強度試験を行
い、結果を表７に示す。(2) Preparation of Composite Sintered Body The composite powder obtained in (1) was molded under the same conditions as in Example 1. This compact was sintered under a normal pressure at 2000 ° C. for 4 hours in a nitrogen gas atmosphere of 9 kgf / cm 2 , and then 1000 kgf / cm 2.
HIP sintering was performed at 1850 ° C. for 1 hour in a nitrogen gas atmosphere.
A strength test was performed on the composite sintered body obtained in the same manner as in Example 1, and the results are shown in Table 7.
【００６７】実施例６ (1) 複合粉末の作製 平均粒径が0.7 μｍの珪素粉末（JIS MSi 1 ）と、炭素
質として粒径が５μｍ以下のカーボン粉末と、平均粒径
が１μｍのＬｕ2 Ｏ3 粉末と、平均粒径が２μｍのＡｌ
Ｎ粉末とを、表５に示す割合で（ただし、実施例１と同
様に表１０に示した目的配合比より計算した値であ
る。）秤量し、ボールミルにより200 重量部のエタノー
ルを溶媒として100 重量部のボールとともに18時間混合
し、乾燥した。 Example 6 (1) Preparation of Composite Powder A silicon powder (JIS MSi 1) having an average particle size of 0.7 μm, a carbon powder having a particle size of 5 μm or less as carbonaceous material, and Lu 2 having an average particle size of 1 μm O 3 powder and Al with an average particle size of 2 μm
N powder was weighed at the ratio shown in Table 5 (however, the value was calculated from the target compounding ratio shown in Table 10 in the same manner as in Example 1), and 100 parts by weight of ethanol was used as a solvent in a ball mill using 200 parts by weight of ethanol. Blended with 18 parts by weight of ball and dried.
【００６８】 表５ 原料粉末組成 重量（ｇ） 配合比（重量％） 珪素粉末 266.3 69.9 カーボン粉末 38.1 10.0 Ｌｕ2 Ｏ3 粉末 61.7 16.2 ＡｌＮ粉末 15.0 3.9 Table 5 Raw material powder composition Weight (g) Mixing ratio (% by weight) Silicon powder 266.3 69.9 Carbon powder 38.1 10.0 Lu 2 O 3 powder 61.7 16.2 AlN powder 15.0 3.9
【００６９】得られた原料粉末を実施例５と同じ方法で
窒化／炭化反応を起こさせた後、200 重量部のアルコー
ル及び200 重量部の窒化珪素ボールとともに２リットル
のポリエチレンポットに入れて、ボールミルで７日間粉
砕し、複合粉末を調製した。得られた複合粉末のα型窒
化珪素の含有率を実施例１と同様に求めた。結果を表７
に示す。The obtained raw material powder was subjected to a nitriding / carbonization reaction in the same manner as in Example 5, and then put into a 2-liter polyethylene pot together with 200 parts by weight of alcohol and 200 parts by weight of silicon nitride balls. For 7 days to prepare a composite powder. The α-type silicon nitride content of the obtained composite powder was determined in the same manner as in Example 1. Table 7 shows the results
Shown in
【００７０】(2) 複合焼結体の作製 (1) で得た複合粉末を用いて、実施例１と同じ条件で成
形した後、実施例５と同じ方法で常圧焼結及びＨＩＰ焼
結を行った。実施例１と同様に得られた複合焼結体の強
度試験を行い、結果を表７に示す。(2) Preparation of Composite Sintered Body The composite powder obtained in (1) was molded under the same conditions as in Example 1 and then subjected to normal pressure sintering and HIP sintering in the same manner as in Example 5. Was done. A strength test was performed on the composite sintered body obtained in the same manner as in Example 1, and the results are shown in Table 7.
【００７１】比較例５ 焼結助剤としてＬｕ2 Ｏ3 粉末に替えて平均粒径１μｍ
のＩｎ2 Ｏ3 粉末を用いた以外は、実施例６と同じ原料
粉末を表６に示す割合で（ただし、実施例１と同様に表
１０に示した目的配合比より計算した値である。）秤量
し、ボールミルにより200 重量部のエタノールを溶媒と
して100 重量部のボールとともに18時間混合し、乾燥し
た。 Comparative Example 5 An average particle size of 1 μm was used instead of Lu 2 O 3 powder as a sintering aid.
Except for using In 2 O 3 powder, the same raw material powders as in Example 6 in the proportions indicated in Table 6 (provided that the value calculated from the object compounding ratio shown in the same manner as Table 10 in Example 1. ) Weighed and mixed with 200 parts by weight of ethanol as a solvent together with 100 parts by weight of a ball by a ball mill for 18 hours and dried.
【００７２】 表６ 原料粉末組成 重量（ｇ） 配合比（重量％） 珪素粉末 278.0 74.0 カーボン粉末 39.8 10.6 Ｉｎ2 Ｏ3 粉末 43.0 11.4 ＡｌＮ粉末 15.0 4.0 Table 6 Raw material powder composition Weight (g) Mixing ratio (% by weight) Silicon powder 278.0 74.0 Carbon powder 39.8 10.6 In 2 O 3 powder 43.0 11.4 AlN powder 15.0 4.0
【００７３】得られた原料粉末を実施例５と同じ方法で
窒化／炭化反応を起こさせた後、200 重量部のアルコー
ル及び200 重量部の窒化珪素ボールとともに２リットル
のポリエチレンポットに入れて、ボールミルで７日間粉
砕し、複合粉末を調製した。得られた複合粉末のα型窒
化珪素の含有率を実施例１と同様に求めた。結果を表７
に示す。The obtained raw material powder was subjected to a nitriding / carbonization reaction in the same manner as in Example 5, then put into a 2 liter polyethylene pot together with 200 parts by weight of alcohol and 200 parts by weight of silicon nitride balls, and then ball milled. For 7 days to prepare a composite powder. The α-type silicon nitride content of the obtained composite powder was determined in the same manner as in Example 1. Table 7 shows the results
Shown in
【００７４】得られた複合粉末を用いて、実施例１と同
じ条件で成形した後、実施例５と同じ方法で常圧焼結及
びＨＩＰ焼結を行った。実施例１と同様に得られた複合
焼結体の強度試験を行い、結果を表７に示す。After molding the obtained composite powder under the same conditions as in Example 1, normal pressure sintering and HIP sintering were performed in the same manner as in Example 5. A strength test was performed on the composite sintered body obtained in the same manner as in Example 1, and the results are shown in Table 7.
【００７５】[0075]
【表７】 [Table 7]
【００７６】表７から分かるように、窒化／炭化反応時
の昇温速度を２℃／分にした比較例１〜３の複合粉末で
は、昇温速度を0.5 ℃／分にした実施例１〜４に比べα
型窒化珪素の含有率が大きく低下した。また、焼結助剤
を含んでいない比較例４及び焼結助剤としてＩｎ2 Ｏ3
粉末を用いた比較例５では、実施例１及び実施例５、６
に比べてα型窒化珪素の含有率が大きく低下した。As can be seen from Table 7, in the composite powders of Comparative Examples 1 to 3 in which the heating rate during the nitriding / carbonization reaction was 2 ° C./min, Examples 1 to 3 in which the heating rate was 0.5 ° C./min. Α compared to 4
The content of the silicon nitride was greatly reduced. Further, Comparative Example 4 containing no sintering aid and In 2 O 3
In Comparative Example 5 using powder, Examples 1 and 5 and 6 were used.
, The content of α-type silicon nitride was greatly reduced.
【００７７】実施例７ (1) 複合成形体の作製 平均粒径が0.5 μｍの珪素粉末（JIS MSi 1 ）と、炭素
質として粒径が５μｍ以下のカーボン粉末と、平均粒径
が0.1 μｍの窒化珪素粉末と、平均粒径が0.2μｍの炭
化珪素粉末と、平均粒径が1.4 μｍのＹ2 Ｏ3 粉末と
を、表８に示す割合で（ただし、実施例１と同様に表１
０に示した目的配合比より計算した値である。）秤量
し、ボールミルにより200 重量部のエタノールを溶媒と
して100 重量部のボールとともに18時間混合し、乾燥し
た。 Example 7 (1) Preparation of Composite Molded Product A silicon powder (JIS MSi 1) having an average particle size of 0.5 μm, a carbon powder having a particle size of 5 μm or less as carbonaceous material, and a carbon powder having an average particle size of 0.1 μm A silicon nitride powder, a silicon carbide powder having an average particle diameter of 0.2 μm, and a Y 2 O 3 powder having an average particle diameter of 1.4 μm were mixed at the ratio shown in Table 8 (however, Table 1 was used in the same manner as in Example 1).
This is a value calculated from the target compounding ratio shown in FIG. ) Weighed and mixed with 200 parts by weight of ethanol as a solvent together with 100 parts by weight of a ball by a ball mill for 18 hours and dried.
【００７８】 表８ 原料粉末組成 重量（ｇ） 配合比（重量％） 珪素粉末 274.9 72.9 カーボン粉末 39.4 10.4 窒化珪素粉末 16.1 4.3 炭化珪素粉末 6.9 1.8 Ｙ2 Ｏ3 粉末 40.0 10.6 Table 8 Raw material powder composition Weight (g) Mixing ratio (% by weight) Silicon powder 274.9 72.9 Carbon powder 39.4 10.4 Silicon nitride powder 16.1 4.3 Silicon carbide powder 6.9 1.8 Y 2 O 3 powder 40.0 10.6
【００７９】得られた原料粉末を55×35×６mmの形状に
予備成形した後、ＣＩＰ装置で４トン／平方センチメー
トルの等方圧を加えた。得られた成形体を反応容器に入
れ、1200℃からの昇温速度を0.5 ℃／分として1450℃ま
で昇温した後、30分間保持した。雰囲気は20容量％の水
素ガスと80容量％の窒素ガスとの混合ガス雰囲気とし
て、９kgf ／cm2 のガス圧下で窒化／炭化反応を起こさ
せ、複合成形体を調製した。得られた複合成形体のα型
窒化珪素の含有率を実施例１と同様に求めた。結果を表
１１に示す。After the obtained raw material powder was preformed into a shape of 55 × 35 × 6 mm, an isotropic pressure of 4 tons / cm 2 was applied by a CIP device. The obtained molded body was placed in a reaction vessel, heated to 1450 ° C. at a rate of 0.5 ° C./min from 1200 ° C., and held for 30 minutes. The atmosphere was a mixed gas atmosphere of 20% by volume of hydrogen gas and 80% by volume of nitrogen gas, and a nitriding / carbonization reaction was caused under a gas pressure of 9 kgf / cm 2 to prepare a composite molded body. The α-type silicon nitride content of the obtained composite molded body was determined in the same manner as in Example 1. Table 11 shows the results.
【００８０】(2) 複合焼結体の作製 (1) で得た複合成形体を、９kgf ／cm2 の窒素ガス雰囲
気中、2050℃で４時間常圧焼結し、ついで1000kgf ／cm
2 の窒素ガス雰囲気中、1900℃て１時間ＨＩＰ焼結し
た。得られた焼結体の組織を電子顕微鏡で観察したとこ
ろ、ナノコンポジット構造を有することが分かった。実
施例１と同様に得られた複合焼結体の強度試験を行い、
結果を表１１に示す。(2) Production of Composite Sintered Body The composite molded body obtained in (1) was sintered at 2050 ° C. for 4 hours under a nitrogen gas atmosphere of 9 kgf / cm 2 at normal pressure, and then 1000 kgf / cm 2
HIP sintering was performed at 1900 ° C. for 1 hour in a nitrogen gas atmosphere of No. 2 . Observation of the structure of the obtained sintered body with an electron microscope revealed that the structure had a nanocomposite structure. A strength test was performed on the composite sintered body obtained in the same manner as in Example 1,
Table 11 shows the results.
【００８１】実施例８ (1) 複合成形体の作製 実施例７で得た原料粉末を用いて、実施例７と同じ条件
で成形し、実施例７と同じ条件で窒化／炭化反応を起こ
させ、複合成形体を調製した。得られた複合成形体のα
型窒化珪素の含有率を実施例１と同様に求めた。結果を
表１１に示す。 Example 8 (1) Preparation of Composite Molded Article The raw material powder obtained in Example 7 was molded under the same conditions as in Example 7, and a nitriding / carbonization reaction was caused under the same conditions as in Example 7. A composite molded article was prepared. Α of the obtained composite molded body
The content of the silicon nitride was determined in the same manner as in Example 1. Table 11 shows the results.
【００８２】(2) 複合焼結体の作製 (1) で得た複合成形体を700 ℃の酸化雰囲気下で24時間
処理した後、実施例７と同じ条件で常圧焼結及びＨＩＰ
焼結を行った。実施例１と同様に得られた複合焼結体の
強度試験を行い、結果を表１１に示す。(2) Preparation of Composite Sintered Body After the composite molded body obtained in (1) was treated in an oxidizing atmosphere at 700 ° C. for 24 hours, normal pressure sintering and HIP were performed under the same conditions as in Example 7.
Sintering was performed. The composite sintered body obtained in the same manner as in Example 1 was subjected to a strength test, and the results are shown in Table 11.
【００８３】実施例９ (1) 複合成形体の作製 実施例７で使用した原料粉末と、平均粒径が１μｍのＳ
ｉＯ2 粉末とを、表９に示す割合で（ただし、実施例１
と同様に表１０に示した目的配合比より計算した値であ
る。）秤量し、実施例７と同じ条件で混合、乾燥した。
得られた原料粉末を実施例７と同じように成形体とし、
実施例７と同じ条件で窒化／炭化反応を起こさせ、複合
成形体を調製した。得られた複合成形体のα型窒化珪素
の含有率を実施例１と同様に求めた。結果を表１１に示
す。 Example 9 (1) Production of Composite Molded Product The raw material powder used in Example 7 was mixed with S having an average particle size of 1 μm.
iO 2 powder at a ratio shown in Table 9 (however,
It is a value calculated from the target compounding ratio shown in Table 10 in the same manner as in. ) Weighed, mixed and dried under the same conditions as in Example 7.
The obtained raw material powder was formed into a compact in the same manner as in Example 7,
Under the same conditions as in Example 7, a nitriding / carbonization reaction was caused to prepare a composite molded body. The α-type silicon nitride content of the obtained composite molded body was determined in the same manner as in Example 1. Table 11 shows the results.
【００８４】 表９ 原料粉末組成 重量（ｇ） 配合比（重量％） 珪素粉末 164.6 72.7 カーボン粉末 23.6 10.4 窒化珪素粉末 9.7 4.3 炭化珪素粉末 4.1 1.8 Ｙ2 Ｏ3 粉末 24.0 10.6 ＳｉＯ2 粉末 0.4 0.2 Table 9 Raw material powder composition Weight (g) Mixing ratio (% by weight) Silicon powder 164.6 72.7 Carbon powder 23.6 10.4 Silicon nitride powder 9.7 4.3 Silicon carbide powder 4.1 1.8 Y 2 O 3 powder 24.0 10.6 SiO 2 powder 0.4 0.2
【００８５】(2) 複合焼結体の作製 (1) で得た複合成形体を実施例７と同じ条件で常圧焼結
及びＨＩＰ焼結を行った。実施例１と同様に得られた複
合焼結体の強度試験を行い、結果を表１１に示す。(2) Production of composite sintered body The composite molded body obtained in (1) was subjected to normal pressure sintering and HIP sintering under the same conditions as in Example 7. The composite sintered body obtained in the same manner as in Example 1 was subjected to a strength test, and the results are shown in Table 11.
【００８６】比較例６ (1) 複合成形体の作製 実施例７で得た原料粉末を用いて、実施例７と同じ条件
で成形し、実施例７と同じ条件で窒化／炭化反応を起こ
させ、複合成形体を調製した。得られた複合成形体のα
型窒化珪素の含有率を実施例１と同様に求めた。結果を
表１１に示す。 Comparative Example 6 (1) Preparation of Composite Molded Article The raw material powder obtained in Example 7 was molded under the same conditions as in Example 7, and a nitriding / carbonization reaction was caused under the same conditions as in Example 7. A composite molded article was prepared. Α of the obtained composite molded body
The content of the silicon nitride was determined in the same manner as in Example 1. Table 11 shows the results.
【００８７】(2) 複合焼結体の作製 (1) で得た複合成形体を1300℃の酸化雰囲気下で24時間
処理した後、実施例７と同じ条件で常圧焼結を行った
が、焼結体は分解して密度測定も困難な状態になったた
め、実験は中止した。(2) Preparation of Composite Sintered Body After the composite molded body obtained in (1) was treated in an oxidizing atmosphere at 1300 ° C. for 24 hours, normal-pressure sintering was performed under the same conditions as in Example 7. The experiment was stopped because the sintered body was decomposed and the density measurement became difficult.
【００８８】 表１０ 生成した複合粉末又は複合成形体の目的配合比 焼結助剤 ： 母材(SiCN) 窒化珪素：炭化珪素 実施例１ ７重量％Ｙ2 Ｏ3 90重量％ 66重量％ 34重量％(1) ３重量％ＡｌＮ 実施例２ ７重量％Ｙ2 Ｏ3 90重量％ 66重量％ 34重量％(1) ３重量％ＡｌＮ 実施例３ ８重量％Ｙ2 Ｏ3 92重量％ 70重量％ 30重量％(1) 実施例４ ８重量％Ｙ2 Ｏ3 92重量％ 70重量％ 30重量％(1) 実施例５ 14.1重量％Ｌｕ2 Ｏ3 85.9重量％ 70重量％ 30重量％ 実施例６ 12.34 重量％Ｌｕ2 Ｏ3 84.66 重量％ 70重量％ 30重量％ ３重量％ＡｌＮ 実施例７ ８重量％Ｙ2 Ｏ3 92重量％ 70重量％ 30重量％(1) 実施例８ ８重量％Ｙ2 Ｏ3 92重量％ 70重量％ 30重量％(1) 実施例９ ８重量％Ｙ2 Ｏ3 91.86 重量％ 70重量％ 30重量％(1) 0.14重量％ＳｉＯ2 比較例１ ７重量％Ｙ2 Ｏ3 90重量％ 66重量％ 34重量％(1) ３重量％ＡｌＮ 比較例２ ７重量％Ｙ2 Ｏ3 90重量％ 66重量％ 34重量％(1) ３重量％ＡｌＮ 比較例３ ７重量％Ｙ2 Ｏ3 90重量％ 66重量％ 34重量％(1) ３重量％ＡｌＮ 比較例４ − 100 重量％ 66重量％ 34重量％(1) 比較例５ 8.61重量％Ｉｎ2 Ｏ3 88.39 重量％ 70重量％ 30重量％ ３重量％ＡｌＮ比較例６ ８重量％Ｙ2 Ｏ3 92重量％ 70重量％ 30重量％(1) 注（１）：原料粉末に種晶として５重量％づつ加えた窒化珪素及び炭化珪素を 含む。Table 10 Target Compounding Ratio of the Generated Composite Powder or Composite Molding Sintering Aid: Base Material (SiCN) Silicon Nitride: Silicon Carbide Example 1 7% by weight Y 2 O 3 90% by weight 66% by weight 34% by weight % (1) 3% by weight AlN Example 2 7% by weight Y 2 O 3 90% by weight 66% by weight 34% by weight (1) 3% by weight AlN Example 3 8% by weight Y 2 O 3 92% by weight 70% by weight 30% by weight (1) Example 4 8% by weight Y 2 O 3 92% by weight 70% by weight 30% by weight (1) Example 5 14.1% by weight Lu 2 O 3 85.9% by weight 70% by weight 30% by weight Example 6 12.34 wt% Lu 2 O 3 84.66 wt% 70 wt% 30 wt% 3 wt% AlN Example 7 8 wt% Y 2 O 3 92 wt% 70 wt% 30 wt% (1) Example 8 8 wt% Y 2 O 3 92 wt% 70 wt% 30 wt% (1) Example 9 8 wt% Y 2 O 3 91.86 wt% 70 wt% 30 wt% (1) 0.14 wt% SiO 2 Comparative Example 1 7 wt% Y 2 O 3 90% by weight 66% by weight 34% by weight (1) 3% by weight AlN Comparative Example 2 7% by weight Y 2 O 3 90% by weight 66% by weight 34% by weight (1) 3% by weight AlN Comparative Example 3 7% by weight Y 2 O 3 90% by weight 66 wt% 34 wt% (1) 3% by weight AlN Comparative example 4 - 100 wt% 66 wt% 34 wt% (1) Comparative example 5 8.61 wt% an In 2 O 3 88.39 wt% 70 wt% 30 wt% 3 wt% AlN Comparative example 6 8 wt% Y 2 O 3 92 wt% 70 wt% 30 wt% (1) Note (1): containing 5 wt% increments added silicon nitride and silicon carbide as seed crystals to the raw material powder.
【００８９】 表１１ 実施例７ 実施例８ 実施例９ 比較例６ 複合成形体のα型窒化珪素 含有率（％）(1) 100 100 100 100 ３点曲げ強度（ＭＰａ） 室温曲げ強度 575.1 730.3 563.6 − 1400℃曲げ強度 491.2 606.6 629.8 − 焼結体密度（ｇ／ｃｍ3 ） 3.27 3.29 3.30 （未測定） 注（１）： α型窒化珪素の含有率（％）＝100 ×(102) 面と(210) 面の合計 回折強度（α型窒化珪素）／（(102) 面と(210) 面の合計回折強度（α型窒化珪 素）＋(101) 面と(210) 面の合計回折強度（β型窒化珪素））Table 11 Example 7 Example 8 Example 9 Comparative Example 6 α-type silicon nitride content of composite molded body (%) (1) 100 100 100 100 Three-point bending strength (MPa) Room temperature bending strength 575.1 730.3 563.6 − 1400 ° C bending strength 491.2 606.6 629.8 − Sintered body density (g / cm 3 ) 3.27 3.29 3.30 (not measured) Note (1): α-type silicon nitride content (%) = 100 × (102) Total diffraction intensity of (210) plane (α-type silicon nitride) / total diffraction intensity of ((102) plane and (210) plane (α-type silicon nitride) + total diffraction intensity of (101) plane and (210) plane ( β-type silicon nitride))
【００９０】以上の通り、実施例７〜９の複合成形体が
高いα型窒化珪素含有率を示し、またそれからなる複合
焼結体が高い曲げ強度と焼結密度を示した。As described above, the composite compacts of Examples 7 to 9 exhibited a high α-type silicon nitride content, and the composite sintered compacts thereof exhibited high bending strength and sintered density.
【００９１】[0091]
【発明の効果】以上詳述したように、本発明によれば、
珪素粉末と炭素質粉末と焼結助剤とを含有する混合粉末
を出発材料として用い、窒素ガス含有雰囲気中及び特定
の昇温速度で熱処理により珪素の窒化と炭化とを起こさ
せることにより、高いα型窒化珪素含有率を有する複合
粉末及び複合成形体が得られる。このため、本発明の方
法により得られた複合粉末又は複合成形体からなる複合
焼結体は優れた高温強度、耐静疲労特性、耐摩耗性及び
硬度を有する。このような特性を有する窒化珪素／炭化
珪素複合焼結体は、高温下で使用される構造部材等に好
適である。As described in detail above, according to the present invention,
Using a mixed powder containing a silicon powder, a carbonaceous powder, and a sintering aid as a starting material, and causing nitridation and carbonization of silicon by heat treatment in a nitrogen gas-containing atmosphere and at a specific temperature increasing rate, A composite powder and a composite compact having an α-type silicon nitride content are obtained. Therefore, the composite sintered body composed of the composite powder or composite molded body obtained by the method of the present invention has excellent high-temperature strength, static fatigue resistance, wear resistance, and hardness. The silicon nitride / silicon carbide composite sintered body having such characteristics is suitable for a structural member or the like used at a high temperature.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０４Ｂ 35/591 Ｃ０４Ｂ 35/58 １０２Ｆ 35/626 １０２Ｑ １０２Ｖ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical indication location C04B 35/591 C04B 35/58 102F 35/626 102Q 102V
Claims (15)
合し、得られた混合粉末を窒素ガス含有雰囲気下におい
て熱処理して、珪素の窒化と炭化とを起こして得られる
窒化珪素と炭化珪素との複合粉末において、前記焼結助
剤の含有量が前記複合粉末の全量を１００重量％として
５〜２０重量％であり、かつ前記複合粉末中のα型窒化
珪素の含有量が全窒化珪素の３０％以上であることを特
徴とする窒化珪素／炭化珪素複合粉末。1. A silicon nitride obtained by mixing a carbonaceous powder and a sintering aid into a silicon powder and subjecting the obtained mixed powder to a heat treatment in an atmosphere containing nitrogen gas to cause nitridation and carbonization of silicon. in the composite powder of silicon carbide, the sintered Yuisuke
The content of the agent is 100% by weight based on the total amount of the composite powder.
A silicon nitride / silicon carbide composite powder, characterized in that the content is 5 to 20% by weight and the content of α-type silicon nitride in the composite powder is 30% or more of the total silicon nitride.
合し、得られた混合粉末を窒素ガス含有雰囲気下におい
て熱処理して、珪素の窒化と炭化とを起こして得られる
窒化珪素と炭化珪素との複合粉末において、前記焼結助
剤が（ａ）周期律表３Ａ族元素及び４Ａ族元素の酸化物
からなる群より選ばれた一種以上の化合物、又は（ｂ）
窒化アルミニウムと前記（ａ）の化合物との混合物であ
ることを特徴とする窒化珪素／炭化珪素複合粉末。2. A mixture of silicon powder with carbonaceous powder and a sintering aid.
And place the resulting mixed powder under an atmosphere containing nitrogen gas.
Heat treatment to cause nitridation and carbonization of silicon.
In a composite powder of silicon nitride and silicon carbide, the sintering aid is (a) at least one compound selected from the group consisting of oxides of Group 3A and Group 4A elements of the periodic table, or (b)
A mixture of aluminum nitride and the compound of (a).
Silicon nitride / silicon carbide composite powder wherein a that.
合粉末において、前記化合物（ａ）がＹ ２ Ｏ ３ 、Ｌｕ ２
Ｏ ３ 、Ｙｂ ２ Ｏ ３ 及びＨｆＯ ２ からなる群から選ばれた
少なくとも１種であることを特徴とする窒化珪素／炭化
珪素複合粉末。3. The silicon nitride / silicon carbide composite powder according to claim 2 , wherein said compound (a) is Y 2 O 3 , Lu 2
Selected from the group consisting of O 3 , Yb 2 O 3 and HfO 2
A silicon nitride / silicon carbide composite powder, which is at least one kind .
素／炭化珪素複合粉末において、前記混合粉末は、珪素
粉末と、炭素質粉末と、焼結助剤粉末と、窒化珪素粉末
及び／又は炭化珪素粉末とを混合してなることを特徴と
する窒化珪素／炭化珪素複合粉末。4. The silicon nitride / silicon carbide composite powder according to claim 1, wherein the mixed powder comprises silicon powder, carbonaceous powder, sintering aid powder, and silicon nitride powder. and / or a silicon carbide powder mixed with silicon carbide powder.
素／炭化珪素複合粉末において、炭化珪素／窒化珪素の
重量比が５／９５〜５０／５０であることを特徴とする
窒化珪素／炭化珪素複合粉末。5. The silicon nitride / silicon carbide composite powder according to claim 1, wherein the weight ratio of silicon carbide / silicon nitride is 5/95 to 50/50. / Silicon carbide composite powder.
合し、得られた混合粉末から形成した成形体を窒素ガス
含有雰囲気下において熱処理して、珪素の窒化と炭化と
を起こして得られる窒化珪素と炭化珪素との複合成形体
において、前記焼結助剤の含有量が前記複合成形体の全
量を１００重量％として５〜２０重量％であり、かつ前
記複合成形体中のα型窒化珪素の含有量が全窒化珪素の
３０％以上であることを特徴とする窒化珪素／炭化珪素
複合成形体。6. A silicon powder mixed with a carbonaceous powder and a sintering aid, and a molded body formed from the obtained mixed powder is heat-treated in an atmosphere containing nitrogen gas to cause nitridation and carbonization of silicon. In the composite molded body of silicon nitride and silicon carbide obtained by the above, the content of the sintering aid is the total of the composite molded body.
Silicon nitride, characterized in that the amount of α-type silicon nitride in the composite molded body is 30% or more of the total silicon nitride, the content being 5 to 20% by weight based on 100% by weight. / Silicon carbide composite molded body.
合し、得られた混合粉末から形成した成形体を窒素ガス
含有雰囲気下において熱処理して、珪素の窒化と炭化と
を起こして得られる窒化珪素と炭化珪素との複合成形体
において、前記焼結助剤が（ａ）周期律表３Ａ族元素及
び４Ａ族元素の酸化物からなる群より選ばれた一種以上
の化合物、又は（ｂ）窒化アルミニウムと前記（ａ）の
化合物との混合物であることを特徴とする窒化珪素／炭
化珪素複合成形体。7. A silicon powder mixed with a carbonaceous powder and a sintering aid.
The molded body formed from the mixed powder obtained was mixed with nitrogen gas.
Heat treatment in an atmosphere containing silicon to nitride and carbonize silicon.
In a composite molded body of silicon nitride and silicon carbide obtained by causing the above, the sintering aid is (a) one or more compounds selected from the group consisting of oxides of Group 3A and Group 4A elements of the periodic table. or (b) aluminum nitride and said (a)
A silicon nitride / silicon carbide composite molded product, which is a mixture with a compound .
合成形体において、前記化合物（ａ）がＹ ２ Ｏ ３ 、ＬＵ
２ Ｏ ３ 、Ｙｂ ２ Ｏ ３ 及びＨｆＯ ２ からなる群から選ばれ
た少なくとも１種であることを特徴とする窒化珪素／炭
化珪素複合成形体。8. The silicon nitride / silicon carbide composite molded article according to claim 7 , wherein said compound (a) is Y 2 O 3 , LU.
Selected from the group consisting of 2 O 3 , Yb 2 O 3 and HfO 2
And a silicon nitride / silicon carbide composite molded body characterized in that it is at least one kind .
素／炭化珪素複合成形体において、前記混合粉末は、珪
素粉末と、炭素質粉末と、焼結助剤粉末と、窒化珪素粉
末及び／又は炭化珪素粉末とを混合してなることを特徴
とする窒化珪素／炭化珪素複合成形体。9. The silicon nitride / silicon carbide composite compact according to claim 6, wherein the mixed powder is a silicon powder, a carbonaceous powder, a sintering aid powder, and a silicon nitride powder. And / or a silicon carbide powder .
珪素／炭化珪素複合成形体において、炭化珪素／窒化珪
素の重量比が５／９５〜５０／５０であることを特徴と
する窒化珪素／炭化珪素複合成形体。10. The silicon nitride / silicon carbide composite molded article according to claim 6, wherein the weight ratio of silicon carbide / silicon nitride is 5/95 to 50/50. Silicon / silicon carbide composite molded body.
３０％以上である窒化珪素／炭化珪素複合粉末の製造方
法において、珪素粉末に炭素質粉末と焼結助剤とを混合
し、得られた混合粉末を窒素ガス含有雰囲気下において
熱処理して、珪素の窒化と炭化とを起こし、その際窒化
炭化反応を１０００℃〜１４５０℃の温度で行い、かつ
少なくとも反応開始前の温度から保持温度に到達するま
での昇温速度を２℃／分未満にすることを特徴とする方
法。11. A method for producing a silicon nitride / silicon carbide composite powder in which the content of α-type silicon nitride is 30% or more of the total silicon nitride, wherein a carbonaceous powder and a sintering aid are mixed with the silicon powder, The obtained mixed powder is heat-treated in an atmosphere containing nitrogen gas to cause nitridation and carbonization of silicon. At this time, the nitriding and carbonizing reaction is performed at a temperature of 1000 ° C to 1450 ° C, and is maintained at least from the temperature before the start of the reaction. A method wherein the rate of temperature rise until the temperature is reached is less than 2 ° C./min.
３０％以上である窒化珪素／炭化珪素複合成形体の製造
方法において、珪素粉末に炭素質粉末と焼結助剤とを混
合し、得られた混合粉末から成形体を形成し、前記成形
体を窒素ガス含有雰囲気下において熱処理して、珪素の
窒化と炭化とを起こし、その際窒化炭化反応を１０００
℃〜１４５０℃の温度で行い、かつ少なくとも反応開始
前の温度から保持温度に到達するまでの昇温速度を２℃
／分末満にすることを特徴とする方法。12. A method for producing a silicon nitride / silicon carbide composite molded article in which the content of α-type silicon nitride is 30% or more of the total silicon nitride, wherein carbon powder and sintering aid are mixed with silicon powder. A molded body is formed from the obtained mixed powder, and the molded body is heat-treated in an atmosphere containing nitrogen gas to cause nitridation and carbonization of silicon.
C. to 1450 ° C., and at least a temperature increase rate from a temperature before the start of the reaction to a holding temperature of 2 ° C.
/ A method characterized by being full.
する方法において、請求項１〜５のいずれかに記載の窒
化珪素／炭化珪素複合粉末から成形体を形成し、前記成
形体を窒素ガス含有雰囲気中において１６００℃〜２２
００℃で焼結することを特徴とする方法。13. A method for producing a silicon nitride / silicon carbide composite sintered body, to form a molded body of silicon nitride / silicon carbide composite powder according to any one of claims 1 to 5, Nitrogen said molded body 1600 ° C. to 22 in a gas-containing atmosphere
A method characterized by sintering at 00 ° C.
する方法において、請求項６〜１０のいずれかに記載の
窒化珪素／炭化珪素複合成形体を窒素ガス含有雰囲気中
において１６００℃〜２２０００℃で焼結することを特
徴とする方法。14. A method for producing a silicon nitride / silicon carbide composite sintered body, wherein the silicon nitride / silicon carbide composite molded body according to claim 6 is heated to 1600 ° C. to 22000 in an atmosphere containing nitrogen gas. A method characterized by sintering at ℃.
素複合焼結体を製造する方法において、前記窒化珪素／
炭化珪素複合成形体を酸化性雰囲気中において１３００
℃末満で熱処理した後、窒素ガス含有雰囲気中において
１６００℃〜２２００℃で焼結することを特徴とする方
法。15. The method for producing a silicon nitride / silicon carbide composite sintered body according to claim 14, wherein
The silicon carbide composite molded body is placed in an oxidizing atmosphere at 1300.
A method comprising heat-treating at a temperature below ℃ and sintering at 1600 ° C to 2200 ° C in an atmosphere containing nitrogen gas.
Priority Applications (2)
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|---|---|---|---|
| JP7319737A JP2649220B2 (en) | 1994-11-29 | 1995-11-14 | Silicon nitride / silicon carbide composite powder, composite compact, method for producing them, and method for producing silicon nitride / silicon carbide composite sintered body |
| US08/625,043 US5767025A (en) | 1994-03-30 | 1996-03-29 | Composite powder comprising silicon nitride and silicon carbide |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-319037 | 1994-11-29 | ||
| JP31903794 | 1994-11-29 | ||
| JP7319737A JP2649220B2 (en) | 1994-11-29 | 1995-11-14 | Silicon nitride / silicon carbide composite powder, composite compact, method for producing them, and method for producing silicon nitride / silicon carbide composite sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08225311A JPH08225311A (en) | 1996-09-03 |
| JP2649220B2 true JP2649220B2 (en) | 1997-09-03 |
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| JP5440977B2 (en) * | 2009-09-03 | 2014-03-12 | 電気化学工業株式会社 | Method for producing high-purity silicon nitride fine powder |
| US9793461B2 (en) * | 2014-09-05 | 2017-10-17 | Mossey Creek Technologies, Inc. | Nano-structured porous thermoelectric generators |
| CN114262230B (en) * | 2021-12-17 | 2022-12-13 | 中国科学院上海硅酸盐研究所 | Silicon nitride-silicon carbide porous ceramic wave-absorbing material and preparation method thereof |
| CN114956829B (en) * | 2022-06-18 | 2023-06-02 | 江苏诺明高温材料股份有限公司 | Silicon nitride combined silicon carbide brick for dry quenching chute and preparation method thereof |
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| US5187129A (en) * | 1987-12-21 | 1993-02-16 | Eaton Corporation | Process for making silicon nitride and powders and articles made therefrom |
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