JP7274590B2 - 高含量のジルコニアを有する耐火性製品 - Google Patents
高含量のジルコニアを有する耐火性製品 Download PDFInfo
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Description
ZrO2: 100%までの残部
HfO 2 : <5%
SiO2: 8.1%~12.0%
B2O3: 0.20%~0.90%
Na2O+K2O: 0.40%~0.80%
Al2O3: 0.3%~2.0%
Y2O3: <2.0%
Fe2O3+TiO2: <0.6%
他の種: <1.5%
を含む、溶融鋳造された耐火性製品を提供する。
該製品の全多孔度が、10%未満、又はさらには5%未満、であること、
好ましくは、該酸化物が、該製品の重量の90%超、95%超、99%超、又はさらには実質的に100%、であること、
ZrO2+HfO2の重量含量が、92.0%未満、若しくはさらには90.0%未満、若しくはさらには89.0%未満、及び/又は83.0%超、若しくはさらには84.0%超、若しくは85.0%超、であること、
SiO2の重量含量が、8.4%超、若しくはさらには8.5%超、若しくはさらには8.6%超、若しくはさらには8.8%超、若しくはさらには9.1%超、及び/又は11.5%未満、若しくはさらには11.0%未満、若しくはさらには10.8%未満、若しくはさらには10.6%未満、であること、
酸化ホウ素B2O3、酸化ナトリウムNa2O及び酸化カリウムK2Oの重量含量の合計が、0.65%超、若しくはさらには0.70%超、若しくはさらには0.75%超、及び/又は1.20%未満、若しくはさらには1.10%未満、若しくはさらには1.00%未満、であること、
酸化ホウ素B2O3の重量含量が、0.25%超、若しくはさらには0.30%超、若しくはさらには0.35%超、若しくはさらには0.40%超、及び/又は0.85%未満、0.80%未満、0.75%未満、0.70%未満、0.60%未満、若しくはさらには0.55%未満、であること、
酸化ナトリウムNa2O及び酸化カリウムK2Oの重量含量の合計が、0.45%超、及び/又は0.75%未満、0.65%未満、であること、
Na2Oの重量含量が、0.40%超、若しくはさらには0.45%超、若しくはさらには0.50%超、及び/又は0.80%未満、若しくはさらには0.70%未満、若しくはさらには0.60%未満、であること、
K2Oが、不純物として存在するか、又はNa2Oを部分的に置き換え、K2Oの重量含量が、0.70%未満、又はさらには0.60%未満、又はさらには0.50%未満、又はさらには0.40%未満、又はさらには0.30%未満、であること、
Al2O3の重量含量が、1.9%未満、若しくはさらには1.8%未満、若しくは1.7%未満、及び/又は0.5%超、若しくはさらには0.6%超、若しくはさらには0.7%超、若しくはさらには0.9%超、1.0%超、若しくはさらには1.1%超、若しくはさらには1.2%超、であること、
Y2O3の重量含量が、0.5%超、若しくはさらには0.7%超、若しくはさらには0.9%超、若しくはさらには1.0%超、若しくはさらには1.1%超、及び/又は1.9%未満、若しくはさらには1.8%未満、若しくはさらには1.7%未満、若しくはさらには1.6%未満、であること、
酸化鉄及び酸化チタンFe2O3+TiO2の重量含量の合計が、0.4%未満、好ましくは0.3%未満、好ましくは0.2%未満、であること、
「他の種」の総重量含量が、1.2%未満、又はさらには1.0%未満、又はさらには0.6%未満、又はさらには0.5%未満、又はさらには0.4%未満、であること、
該「他の種」が、不純物だけからなること、
任意の該「他の種」の重量含量が、0.40%未満、又はさらには0.30%未満、又はさらには0.20%未満、であること、
酸化カルシウムCaO、酸化バリウムBaO、酸化ストロンチウムSrO及び酸化マグネシウムMgOの重量含量の合計が、0.60%未満、0.50%未満、0.40%未満、又はさらには0.30%未満、であること、
CaOの重量含量が、0.60%未満、又はさらには0.40%未満、又はさらには0.30%未満、であること、
BaOの重量含量が、0.60%未満、又はさらには0.40%未満、又はさらには0.30%未満、0.20%未満、0.10%未満、0.05%未満、又は実質的に0、であること、
SrOの重量含量が、0.60%未満、又はさらには0.40%未満、又はさらには0.30%未満、0.20%未満、0.10%未満、0.05%未満、又は実質的に0、であること、
MgOの重量含量が、0.60%未満、又はさらには0.40%未満、又はさらには0.30%未満、であること、
Ta2O5の重量含量が、0.20%未満、0.10%未満、0.05%未満、又は実質的に0、であること、
Nb2O5の重量含量が、0.20%未満、0.10%未満、0.05%未満、又は実質的に0、であること。
SiO2: 8.5%~11.0%
B2O3: 0.30%~0.80%
Na2O+K2O: 0.40%~0.70%
Al2O3: 0.6%~2.0%
を含む、溶融鋳造された耐火性製品を提供する。
SiO2: 8.5%~10.8%
B2O3: 0.30%~0.70%
Na2O+K2O: 0.40%~0.70%
Al2O3: 1.0%~1.8%
を含む、溶融鋳造された耐火性製品を提供する。
SiO2: 9.1%~11.0%
B2O3: 0.30%~0.70%
Na2O+K2O: 0.40%~0.70%
Al2O3: 1.1%~1.8%
を含む、溶融鋳造された耐火性製品を提供する。
a.原材料を混合して、原料を形成すること、
b.融解された材料が得られるまで、上記原料を融解すること、
c.上記融解された材料を鋳造し、冷却によって固化させて、該耐火性製品を得ること
の連続工程を含む方法に関し、
ここで、この方法は、上記耐火性製品が本発明に従うように、上記原材料が選択されるという点で、注目すべきである。
製品は慣用的に、該製品が、融解された材料が得られるまで原料の融解を実行する方法によって得られる場合に、「溶融される」とされ、次に冷却によってこの材料を固化する。
SiO2: 8.5%~10.8%
B2O3: 0.30%~0.70%
Al2O3: 1.0%~1.8%
であり、Na2Oの含量及びK2Oの含量の少なくとも一方は、0.30%超、好ましくは0.35%超、好ましくは0.40%超、である。
a.原材料を混合して、原料を形成すること、
b.融解された材料が得られるまで、上記原料を融解すること、
c.冷却によって上記融解された材料を固化して、本発明に従う耐火性製品を得ること。
下記の非限定的な例は、本発明を例示する目的の為に与えられる。
平均で99%のZrO2+HfO2を含むジルコニアQ1、
平均で33%のSiO2及び66%のZrO2+HfO2を含むジルコンサンド(zircon sand)、
平均で99%のSiO2を含む「Sable BE01 Bedouin」(BE01 Bedouinサンド)シリカ、
平均で98%のB2O3を含む酸化ホウ素、
Na2O源として平均で99.5%のNa2CO3を含む炭酸ナトリウム、
平均で99%のAl2O3を含むAC34タイプのアルミナ、
平均で99%のY2O3を含む酸化イットリウム。
上部構造のブロックが受ける熱機械応力に耐える製品の能力を研究する為に、本発明者等は、MOR/MOE比を熱衝撃耐性につなげるKingeryの理論及び破裂のエネルギーを熱衝撃耐性につなげるHasselmanの理論を使用した。更に、線形弾性力学において、熱機械応力の程度は、破裂弾性率(MOR:modulus of rupture)と弾性率(MOE:modulus of elasticity)との比に関連する。この比は、破裂のエネルギーと同様に、最大化されるべきであり、従って、該製品は、熱機械源の亀裂に対して耐性である。該製品は、1000℃に置かれ、それは、該ブロックのコアにおける温度に実質的に相当する。
破裂弾性率(MOR)は、2つの下方支持体の間の距離を120mmに設定された3点曲げアセンブリに置かれた、150×25×15mm3の寸法を有する試料について、空気中1000℃で測定された最大応力であり、該試料の長さに沿って中間にある上方支持体を提供するパンチの降下速度は、0.5mm/分に等しい。MORの値は、3回の連続測定から生じる平均である。
MOEを測定する為に、MORについて記載されているものと同じアセンブリ、及び試料の偏りの変位をモニタリングし、MOE、すなわち応力とこの応力によって引き起こされた弾性歪みとの比を決定する為の変位センサが使用される。
破裂エネルギーは、2つの下方支持体の間の距離が120mmであり、2つの上方支持体の間の距離が40mmである、4点曲げアセンブリに置かれた、150×25×25mm3の寸法を有し、その中央に60°の角度及び25mmのベースを有する三角形ノッチを有する試料に対して、空気中1000℃で測定される。該上方支持体の降下速度は、20μm/分に等しい。
耐腐食性(CR:corrosion resistance)は、50%のガラスカレット、15%のシリカ、5%のドロマイト及び30%の炭酸ナトリウムからなる粉末を、1450℃の炉内で回転させられる(6rpm)110×100×30mm3の寸法を有する4つの試料にわたって、1時間当たり180グラムの速度で合計20キログラム噴霧することによって測定される。腐食した体積は、3D走査によって測定され、この体積は、初期体積と関連付けられる。
浸出(REx:resistance to exudation)に対する耐性は、空気中、100×100×20mm3の寸法を有する試料において測定される。該試料は、1時間当たり100℃の速度で1550℃にされ、次に1550℃で6時間保持されるサイクルを受ける。RExは、該試料の初期体積に対して、2つのサイクルの後に該試料から抜け出したシリケート相(該試料上に見出される(該試料の体積の増大)、又はるつぼの底部に見出される)の体積パーセンテージである。該試料は、タンクの内部に曝露された該ブロックの表面上の温度に実質的に相当する1550℃に置かれる。
Claims (11)
- 酸化物に基づく重量パーセンテージとして、合計100%に対して、
ZrO2: 100%までの残部
HfO 2 : <5%
SiO2: 8.1%~12.0%
B2O3: 0.20%~0.90%
Na2O+K2O: 0.40%~0.80%
Al2O3: 0.3%~2.0%
Y2O3: <2.0%
Fe2O3+TiO2: <0.6%
他の種: <1.5%
を含む、溶融鋳造された耐火性製品。 - 83.0%<ZrO2+HfO2<92.0%;及び/又は
8.4%<SiO2<11.5%;及び/又は
0.25%<B2O3<0.75%;及び/又は
0.45%<Na2O+K2O<0.75%;及び/又は
0.6%< Al2O3<1.9%;及び/又は
0.5%<Y2O3<1.9%;及び/又は
Fe2O3+TiO2<0.4%;及び/又は
他の種<1.2%
である、請求項1に記載の耐火性製品。 - 84.0%<ZrO2+HfO2<90.0%;及び/又は
8.8%<SiO2<11.0%;及び/又は
0.40%<B2O3<0.70%;及び/又は
Na2O+K2O<0.65%;及び/又は
0.8%< Al2O3<1.7%;及び/又は
0.7%<Y2O3<1.7%;及び/又は
Fe2O3+TiO2<0.3%;及び/又は
他の種<1.0%
である、請求項2に記載の耐火性製品。 - 85.0%<ZrO2+HfO2<90.0%;及び/又は
9.1%<SiO2<10.8%;及び/又は
B2O3<0.60%;及び/又は
0.9%< Al2O3;及び/又は
1.0%<Y2O3<1.6%;及び/又は
Fe2O3+TiO2<0.2%;及び/又は
ZrO2、HfO 2 、SiO2、Y2O3、B2O3、Al2O3、Na2O、K2O、TiO2及びFe2O3以外の他の種<0.5%
である、請求項3に記載の耐火性製品。 - 酸化物に基づく重量パーセンテージとして、
SiO2: 8.5%~11.0%
B2O3: 0.30%~0.80%
Na2O+K2O: 0.40%~0.70%
Al2O3: 0.6%~2.0%
を含む、請求項1~4のいずれか1項に記載の耐火性製品。 - 酸化物に基づく重量パーセンテージとして、
SiO2: 8.5%~10.8%
B2O3: 0.30%~0.70%
Na2O+K2O: 0.40%~0.70%
Al2O3: 1.0%~1.8%
を含む、請求項1~5のいずれか1項に記載の耐火性製品。 - 酸化物に基づく重量パーセンテージとして、
SiO2: 9.1%~11.0%
B2O3: 0.30%~0.70%
Na2O+K2O: 0.40%~0.70%
Al2O3: 1.1%~1.8%
を含む、請求項1~6のいずれか1項に記載の耐火性製品。 - CaO+MgO+BaO+SrO<0.60%である、請求項1~7のいずれか1項に記載の耐火性製品。
- ブロックの形態を有し、ブロックの全ての寸法が10mm超である、請求項1~7のいずれか1項に記載の耐火性製品。
- 請求項1~9のいずれか1項に記載の耐火性製品で作られたブロックを含むガラス融解炉。
- 前記ブロックが上部構造内に配置されている、請求項10に記載のガラス融解炉。
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