JPWO2005019133A1 - 窒化珪素質焼結体およびその製造方法、並びにそれを用いた耐溶融金属用部材、耐摩耗用部材 - Google Patents
窒化珪素質焼結体およびその製造方法、並びにそれを用いた耐溶融金属用部材、耐摩耗用部材 Download PDFInfo
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Abstract
Description
特に、機械的特性を向上させる目的で窒化珪素質焼結体の粒界層(grain boundary layer)にFe、W、Cr、Mo等の金属珪化物を析出させた窒化珪素質焼結体が提案されている(特許文献1〜4参照)
第1金属珪化物:Fe、Cr、MnおよびCuのうち少なくとも1つの第1の金属元素からなる金属珪化物
第2金属珪化物:W、Moのうち少なくとも1つの第2の金属元素からなる金属珪化物
第3金属珪化物:第1の金属元素と第2の金属元素を含む複数金属成分からなる金属珪化物
前記隣接相は、第1金属珪化物が第2金属珪化物または第3金属珪化物を取り囲むように形成されていることが好ましい。
前記窒化珪素の結晶の平均粒径が15μm以下であることが好ましい。
また、前記第1の金属元素を計0.2〜10質量%、前記第2の金属元素を計0.1〜3質量%の範囲とし、前記第1の金属元素を第2の金属元素より多く含有することが好ましい。
前記窒化珪素質燒結体は、Si粉末、もしくはSi粉末と窒化珪素粉末の混合粉末と、平均粒径が0.5〜20μmの前記第1の金属元素の化合物からなる粉末と、平均粒径が0.1〜5μmの前記第2の金属元素の化合物からなる粉末とを含む粉体を成形、焼成して得たものであることが好ましい。
前記隣接相は、第2金属珪化物が第1金属珪化物または第3金属珪化物を取り囲むように形成されていることも好ましい。
前記第1の金属元素を計0.01〜2質量%、前記第2の金属元素を計0.2〜10質量%の範囲とし、前記第2の金属元素を第1の金属元素より多く含有することが好ましい。
前記窒化珪素質燒結体は、Si粉末、もしくはSi粉末と窒化珪素粉末の混合粉末と、平均粒径が0.1〜5μmの前記第1の金属元素の化合物からなる粉末と、平均粒径が1〜30μmの前記第2の金属元素の化合物からなる粉末とを含む粉体を成形、焼成して得たものであることも好ましい。
前記原料粉末と有機結合剤とからなる成形体を作製する成形工程と、
実質的に窒素ガス、アルゴンガス、またはこれらの混合ガスからなる雰囲気中で前記有機結合材を脱脂して脱脂体を作製する脱脂工程と、
前記脱脂体を実質的に窒素ガス雰囲気中で窒化体に変換する窒化工程と、
前記窒化体を窒素ガスを含有する非酸化性雰囲気中で焼成して焼結体を作製する焼成工程とを有することを特徴とする。
前記焼成工程における降温速度が50℃/時間以上であることが好ましい。
前記予備混合粉末として平均粒径が0.1〜5μmの前記第1の金属元素の化合物と、平均粒径が1〜30μmの前記第2の金属元素の化合物とを用い、前記第1の金属元素を計0.01〜2質量%、前記第2の金属元素を計0.2〜10質量%の範囲とし、前記第2の金属元素を前記第1の金属元素よりも多く窒化珪素質焼結体中に含有させることが好ましい。
また、本発明の耐摩耗用部材は、上記窒化珪素質焼結体を用いたことを特徴とする。
12:窒化珪素の結晶
14:隣接相
16、16a、16b、16c:第1金属珪化物
18、18a、18b、18c:第2金属珪化物
20:粒界層
22:第3金属珪化物
本発明の窒化珪素質焼結体は、窒化珪素の結晶と、以下の第1〜第3金属珪化物のうち少なくとも2つを含む粒界層とを有した窒化珪素質焼結体であって、粒界層は第1〜第3金属珪化物のうち少なくとも2つが互いに接する隣接相を有する窒化珪素質焼結体である。
先ず、窒化珪素質焼結体の好ましい実施形態(第1の実施形態)では、第1金属珪化物が第2金属珪化物または第3金属珪化物を取り囲むようにして隣接相を形成している。第2金属珪化物または第3金属珪化物よりも第1の金属珪化物の破壊靱性が高い傾向があるので、大きな機械的応力がかかった場合、窒化珪素質焼結体に割れが生じたり、クラックが入ったりすることが抑制され、機械的特性を向上させることができる。
本実施の形態では、上述の隣接相の構成とは逆、即ち、第2金属珪化物が第1金属珪化物または第3金属珪化物を取り囲むように形成されている。第2金属珪化物は第1金属珪化物または第3金属珪化物よりも熱膨張係数が小さい傾向にある。このため、第1金属珪化物または第3金属珪化物の熱膨張によって発生する熱応力を、隣接した第2金属珪化物が緩和し、耐熱衝撃性をさらに向上するものと考えられる
Si粉末、もしくはSi粉末と窒化珪素粉末の混合粉末に、予め平均粒径0.1〜20μmのFe、Cr、MnおよびCuのうち少なくとも1つの第1の金属元素の化合物に、平均粒径0.1〜30μmのW、Moのうち少なくとも1つの第2の金属元素の化合物を湿式混合、乾燥して得られた予備混合粉末を混合して原料粉末を作製する原料作製工程と、
前記原料粉末と有機結合剤とからなる成形体を作製する成形工程と、
実質的に窒素ガス、アルゴンガス、またはこれらの混合ガスからなる雰囲気中で前記有機結合材を脱脂して脱脂体を作製する脱脂工程と、
脱脂体を実質的に窒素ガス雰囲気中で窒化体に変換する窒化工程と、
窒化体を窒素ガスを含有する非酸化性雰囲気中で焼成して焼結体を作製する焼成工程とを有する。
まず、上述のような湿式混合によって、第1、第2の金属元素の化合物が偏在することなく予備混合粉末中に均一分散させ、乾燥によって第1、第2の金属元素の化合物からなる粒子を互いに固着させた予備粉末を作成する。その結果、予備混合粉末は、第1、第2の金属元素の化合物がそれぞれ均一分散すると共に、互いの粒子が固着したものとなる。なお、この均一分散と固着を達成するために、湿式混合に用いる溶媒としては水、イソプロピルアルコール、エタノール、メタノールのうち少なくとも1つが好適である。溶媒中に水を含有させると、第1、第2の金属元素の化合物の粒子を、乾燥過程で互いに強固に固着させることができるのでさらに好ましい。
この製造方法によって、窒化工程で、第1金属珪化物前駆体が、第2金属珪化物前駆体または第3金属珪化物前駆体を取り囲むように形成された隣接相前駆体が生成される。なお、第1、第2の金属元素が製造過程で不純物として混入する場合は、その不純物を除去するなどして第1、第2の金属元素の含有量を制御してもよい。具体的には、例えば、粉末混合工程において使用する機械の摩耗によって金属のFe成分が原料粉末中に混入する場合、粉末混合工程の後、この粉末に磁場を印加してFe成分を吸着し、除去することにより、最終的に窒化珪素質焼結体に含まれるFeの含有量を制御することができる。
さらに、脱脂工程、窒化工程、前記焼成工程を同一の炉内で連続して実施することが、窒化珪素質焼結体の製造コストを特に低減するので好ましい。
その結果、表2に示したように、本発明の試料No.1〜15は隣接相が観察され、強度、破壊靭性値が高く、熱衝撃試験で割れまたはクラックが発生しなかった。また、隣接相を0.1〜5体積%含有していた。
例えば、アルミニウム低圧鋳造用のストーク、バーナーチューブ、ヒーターチューブ、TC保護管、ダイカスト用のダイカストスリーブ、バーナーチューブ、ヒーターチューブ、熱電対保護管、ラドル、鋳込み型、ホットチャンバー用のピストン、スリーブ、ノズル、ピストン保持部品等のアルミニウム溶湯用部材として好適に用いることができる。
Claims (15)
- 窒化珪素の結晶と、以下の第1〜第3金属珪化物のうち少なくとも2つを含む粒界層とを有した窒化珪素質焼結体であって、
前記粒界層は、第1〜第3金属珪化物のうち少なくとも2つが互いに接する隣接相を有することを特徴とする窒化珪素質焼結体。
第1金属珪化物:Fe、Cr、MnおよびCuから成る群から選択された少なくとも1つの第1の金属元素からなる金属珪化物
第2金属珪化物:W、Moのうち少なくとも1つの第2の金属元素からなる金属珪化物
第3金属珪化物:第1の金属元素と第2の金属元素を含む複数金属成分からなる金属珪化物 - 前記第1の金属元素がFe、前記第2の金属元素がWであることを特徴とする請求項1に記載の窒化珪素質焼結体。
- 前記隣接相では、第1金属珪化物が、第2金属珪化物または第3金属珪化物を取り囲むように形成されていることを特徴とする請求項1または2のいずれかに記載の窒化珪素質焼結体。
- 前記窒化珪素の結晶粒子の平均粒径が15μm以下であることを特徴とする請求項3に記載の窒化珪素質焼結体。
- 窒化珪素質焼結体中における前記第1の金属元素の含有量を計0.2〜10質量%、前記第2の金属元素の含有量を計0.1〜3質量%の範囲とし、前記第1の金属元素を第2の金属元素より多く含有したことを特徴とする請求項3または4に記載の窒化珪素質焼結体。
- Si粉末、もしくはSi粉末と窒化珪素粉末の混合粉末と、平均粒径が0.5〜20μmの前記第1の金属元素の化合物からなる粉末と、平均粒径が0.1〜5μmの前記第2の金属元素の化合物からなる粉末とを含む粉体を成形、焼成して得られることを特徴とする請求項4または5に記載の窒化珪素質焼結体。
- 前記隣接相では、第2金属珪化物が、第1金属珪化物または第3金属珪化物を取り囲むように形成されていることを特徴とする請求項1または2のいずれかに記載の窒化珪素質焼結体。
- 窒化珪素質焼結体中における前記第1の金属元素の含有量を計0.01〜2質量%、前記第2の金属元素の含有量を計0.2〜10質量%の範囲とし、前記第2の金属元素を第1の金属元素より多く含有したことを特徴とする請求項7に記載の窒化珪素質焼結体。
- Si粉末、もしくはSi粉末と窒化珪素粉末の混合粉末と、平均粒径が0.1〜5μmの前記第1の金属元素の化合物からなる粉末と、平均粒径が1〜30μmの前記第2の金属元素の化合物からなる粉末とを含む粉体を成形、焼成して得られることを特徴とする請求項7または8に記載の窒化珪素質焼結体。
- Si粉末、もしくはSi粉末と窒化珪素粉末の混合粉末に、予め平均粒径0.1〜20μmのFe、Cr、MnおよびCuのうち少なくとも1つの第1の金属元素の化合物に、平均粒径0.1〜30μmのW、Moのうち少なくとも1つの第2の金属元素の化合物を湿式混合、乾燥して得られた予備混合粉末を混合して原料粉末を作製する原料作製工程と、
前記原料粉末と有機結合剤とからなる成形体を作製する成形工程と、
実質的に窒素ガス、アルゴンガス、またはこれらの混合ガスからなる雰囲気中で前記有機結合材を脱脂して脱脂体を作製する脱脂工程と、
前記脱脂体を実質的に窒素ガス雰囲気中で窒化体に変換する窒化工程と、
前記窒化体を窒素ガスを含有する非酸化性雰囲気中で焼成して焼結体を作製する焼成工程とを有することを特徴とする窒化珪素質焼結体の製造方法。 - 前記予備混合粉末として平均粒径が0.5〜20μmの前記第1の金属元素の化合物と、平均粒径が0.1〜5μmの前記第2の金属元素の化合物とを用い、
窒化珪素質焼結体中における前記第1の金属元素の含有量が計0.2〜10質量%、前記第2の金属元素の含有量が計0.1〜3質量%の範囲となり、前記第1の金属元素が前記第2の金属元素よりも多く窒化珪素質焼結体中に含有されるよう製造することを特徴とする請求項10に記載の窒化珪素質焼結体の製造方法。 - 前記焼成工程における降温速度が50℃/時間以上であることを特徴とする請求項10または11に記載の窒化珪素質焼結体の製造方法。
- 前記予備混合粉末として平均粒径が0.1〜5μmの前記第1の金属元素の化合物と、平均粒径が1〜30μmの前記第2の金属元素の化合物とを用い、
窒化珪素質焼結体中における前記第1の金属元素の含有量が計0.01〜2質量%、前記第2の金属元素の含有量が計0.2〜10質量%の範囲となり、前記第2の金属元素が前記第1の金属元素よりも多く窒化珪素質焼結体中に含有されるよう製造することを特徴とする請求項10に記載の窒化珪素質焼結体の製造方法。 - 請求項3〜6のいずれかに記載の窒化珪素質焼結体を用いたことを特徴とする耐溶融金属用部材。
- 請求項7〜9のいずれかに記載の窒化珪素質焼結体を用いたことを特徴とする耐摩耗用部材。
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