JP6023271B2 - 耐火製品 - Google Patents
耐火製品 Download PDFInfo
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- JP6023271B2 JP6023271B2 JP2015116536A JP2015116536A JP6023271B2 JP 6023271 B2 JP6023271 B2 JP 6023271B2 JP 2015116536 A JP2015116536 A JP 2015116536A JP 2015116536 A JP2015116536 A JP 2015116536A JP 6023271 B2 JP6023271 B2 JP 6023271B2
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Description
ジルコン本体は、典型的に、75〜99%ジルコンを含む出発投入物から生成された焼結製品である。この焼結製品は、所望の耐クリープ性および高密度を有する。一実施形態において、組成物は、重量で以下の平均化学組成を有し、重量百分率は酸化物に基づいている:
合計を100%として、
60%≦ZrO2+HfO2≦75%;
27%≦SiO2≦34%;
0%≦TiO2;
0%≦Y2O3≦3.5%;
0%≦Nb2O5+Ta2O5≦5%;および
他の酸化物:≦1.5%
− 酸化物に基づく重量百分率で、Ta2O5>0.00%、好ましくはTa2O5≧0.1%、好ましくはTa2O5≧0.25%である;
− 酸化物に基づく重量百分率で、TiO2<1.5%、好ましくはTiO2<1%、より好ましくはTiO2<0.5%、さらに一層好ましくはTiO2<0.15%、そしてさらにより一層好ましくはTiO2<0.10%である。TiO2はさらには不純物であってもよい;
− 酸化物に基づく重量百分率で、Nb2O5<1%、好ましくはNb2O5≦0.5%、好ましくはNb2O5≦0.3%、Nb2O5≦0.25%さらには、Nb2O5≦0.05%である;
− 組成には、Nb2O5が全く含まれなくてもよい;
− 酸化物Nb2O5およびTa2O5の総含有量、好ましくはこれらの酸化物の少なくとも1つの含有量、詳細にはTa2O5の含有量は、酸化物に基づく重量百分率で0.2%超、0.3%超、好ましくは0.5%超そしてより好ましくは0.8%超である;
− 酸化物Nb2O5およびTa2O5の総含有量、好ましくはこれらの酸化物の少なくとも1つの含有量、そして詳細にはTa2O5の含有量は、酸化物に基づく重量百分率で4%または3%未満、好ましくは2%未満、好ましくは1.7%未満、好ましくは1.5%未満、そしてより好ましくは1%未満である;
− SiO2≧30%;
− ZrO2+HfO2≦72.9%またはZrO2+HfO2≦70%;
− 好ましくは、「他の酸化物」(不純物)の含有量は、酸化物に基づく重量百分率で1.2%未満、好ましくは1%未満、より好ましくは0.7%未満、さらに一層好ましくは0.5%未満、そしてさらにより一層好ましくは0.2%未満である;
− 酸化物に基づく重量百分率で、P2O5<1%、好ましくはP2O5<0.9%、より好ましくはP2O5<0.5%、さらに一層好ましくはP2O5<0.3%、さらにより一層好ましくはP2O5<0.2%である;
− 酸化物に基づく重量百分率で、V2O5<1%、好ましくはV2O5<0.9%、より好ましくはV2O5<0.5%、さらに一層好ましくはV2O5<0.3%、そしてさらにより一層好ましくはV2O5<0.2%である;
− 酸化物に基づく重量で、Al2O3<1%、好ましくはAl2O3<0.6%、より好ましくはAl2O3<0.4%である;
− 酸化物に基づく重量百分率で、CaO<0.1%、好ましくはCaO<0.05%である;
− 酸化物に基づく重量百分率で、Fe2O3<0.2%、好ましくはFe2O3<0.08%である;
− 出発投入量中のジルコン含有量は、酸化物に基づく重量百分率で80%以上、好ましくは90%超、好ましくは95%超である;
− 一実施形態の製品は、80重量%超のジルコン(ZrSiO4)を含む;
− 見かけの気孔率は0.1%超、2%超または4%超である;
− 見かけの気孔率は15%未満、または10%未満さらには8%未満である;
− 本体は、少なくとも1つの寸法、好ましくは全ての寸法が100mm超であるブロックの形をしていてよい。詳細には、ブロックは、正方形または矩形の形状を有していてよい。
a)原料を混合して出発投入物を形成する;
b)前記出発投入物からグリーン部品を成形する;
c)前記グリーン部品を焼結して、前記焼結製品を得る。前記プロセスは、前記製品が一実施形態に係るものとなるような形で出発投入物が決定されるという点で、注目に値する。
一般に、前節に記載のジルコン本体実施形態は、ジルコン結晶粒で構成されており、粒界相はこれらのジルコン結晶粒間に存在する。粒界相は酸化ケイ素を含む。酸化ケイ素は、一般に遊離形態で存在し、これはシリカ(SiO2)が結晶粒のジルコン結晶の一部を成さないことを意味する。本発明者らは、ジルコン本体を一定の処理に付すことにより上述のジルコン本体実施形態の一部の特徴を修正することができる、ということを発見した。このような処理の結果として、予想外の有利な特性を有するジルコン構成要素を生産することができる。
− ジルコン結晶粒間に存在し、酸化ケイ素を含む粒界相と、
を含む構成要素であって、SOOP<0.5SOIPであり、SOIPが外側表面から5000ミクロンの深さのところで測定された内部部分内の酸化ケイ素相の重量パーセントであり、SOOPが100ミクロンの深さで測定された外側部分内の遊離酸化ケイ素相の重量百分率である、構成要素。
− 15%未満、例えば0.05〜10.0%または0.1〜10%の範囲内の見かけの気孔率;
− 3.84〜4.49g/cm3、例えば4.00g/cm3〜4.41g/cm3、または4.00g/cm3〜4.32g/cm3の範囲内の密度;
− 室温での4点試験で60〜190MPa、例えば100〜190MPaのMOR;または
− それらの任意の組合せ、
を含む特性を有する、項目1に記載の構成要素。
− ジルコン結晶粒を含む本体と、ジルコン結晶粒間に存在し酸化ケイ素を含む粒界相とを提供するステップと、
− 本体をハロゲン化物に曝露して、構成要素の外側部分に沿って粒界相を少なくとも部分的に除去するステップと、を含む方法。
Claims (8)
- ジルコン粒を含み、外側部分と内部部分とを有する本体と、
前記ジルコン粒間に存在し、酸化ケイ素を含む粒界相と、
を含む耐火製品であって、SOOP<0.5SOIPであり、SOIPが外側表面から5000ミクロンの深さのところで測定された前記内部部分内の酸化ケイ素相の重量パーセントであり、SOOPが100ミクロンの深さで測定された前記外側部分内の遊離酸化ケイ素相の重量百分率であり、
SO IP が1.0〜5.0wt%の範囲内にある、耐火製品。 - 前記本体が90wt%以上のZrSiO4で構成される、請求項1に記載の耐火製品。
- 前記本体が、
15%未満の見かけの気孔率;
3.84〜4.49g/cm3の範囲内の密度;
室温での4点試験で60〜190MPaのMOR;または、
それらの任意の組合せ、
を含む特性を有する、請求項1に記載の耐火製品。 - ガラス成形器具またはガラス成形器具の構成要素の形をしている、請求項1に記載の耐火製品。
- アイソパイプ、リップ、マンドレル、ブッシングブロック、スパウト、チューブ、プランジャ、オリフィスリング、または撹拌機の形をしている、請求項1に記載の耐火製品。
- 前記粒界相が、前記外側部分から少なくとも部分的に除去されて、前記外側部分が前記内部部分よりも高い気孔率を有するようになる、請求項1に記載の耐火製品。
- 前記外側部分が少なくとも100ミクロンの深さまで延在する、請求項1に記載の耐火製品。
- 前記内部部分と外側部分内の気孔率の間の差が、1vol%以上となるように、前記外側部分が前記内部部分よりも高い気孔率を有する、請求項1に記載の耐火製品。
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