TW200800839A - High-electric resistivity, high-zirconia fused cast refractories - Google Patents

Abstract

This invention provides a high zirconia cast refractory having a stable high electric resistance with less change in aging at a high temperature and a heat cycle stability with difficulty in being peeled off in raising a temperature. The high zirconia cast refractory whose property relating to the viscosity of a glass phase at a temperature of around 1,000 DEG C and residual stress at the surface of the refractory are controlled contains ZrO2 of 87-96 wt.%, Al2O3 of ≥ 0.1 and < 0.8 wt.%, SiO2 of 3-10 wt.%, Na2O of < 0.05 wt.%, K2O of 0.01-0.2 wt.%, B2O3 of 0.1-1.0 wt.%, BaO of 0.1-0.5 wt.%, SrO of < 0.05 wt.%, CaO of 0.01-0.15 wt.%, Y2O3 of 0.05-0.4 wt.%, MgO of ≤ 0.1 wt.%, and Fe2O3 and TiO2 in total of ≤ 0.3 wt.%, but substantially does not contain P2O5 and CuO. Its electric resistance after being kept at 1,500 DEG C for 12 h is 200 Ωcm or above.

Description

200800839 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種適於玻璃熔融爐之高氧化鍅鑄造耐火 物’係關於一種在升温時尤其於500〇C附近不會產生剝 離’而穩定、尤其熱循環穩定性優良、且高溫下之電阻特 性得到顯著提高的高氧化鍅鑄造耐火物。 【先前技術】200800839 IX. Description of the Invention: [Technical Field] The present invention relates to a high cerium oxide cast refractory suitable for a glass melting furnace, which is stable with respect to a kind which does not peel off at a temperature rise, especially near 500 〇C. A high cerium oxide cast refractory which is excellent in thermal cycle stability and which has remarkably improved electric resistance characteristics at high temperatures. [Prior Art]

先則以來’較多的是使用大量含有Zrc&gt;2 (氧化鍅或二氧 化鍅）之鑄造耐火物作為玻璃熔融爐用耐火物。其理由在 於，Zr〇2係對於熔融玻璃而言耐蝕性特別大之金屬氧化 物。例如，使用含有80重量％以上的Zr〇2之高氧化鍅鑄造 耐火物作為如此之鑄造耐火物。 —高氧化锆鑄造耐火物中，Zr〇2之含量較高，且組織緻 密，故而相對於所有_類之炫融玻璃肖具有車交大之耐姓 性。進而，其具有下述優良特徵，即，由於其具有不會在 與溶融玻璃之界面處生成反應層之性質，因此不會使炫融 玻璃中產生結石或結筋等缺陷。因此，高氧化結鑄造耐火 物係尤其適於製造高品質玻璃之耐火物。 高氧化錯鑄造耐火物之礦物組織係以下述形態而構成 的，即：單斜晶系氧化結結晶占其大部分，少量之玻璃相 填充該氧化錯結晶之晶粒邊界。 11 5 0 C附近會隨著急劇的 晶系之可逆轉變。藉由玻 &lt;轉變所引起的體積變化 另一方面，已知氧化锆結晶在 體積變化而引起單斜晶系與正方 璃相之流動來緩和由於該氧化鍅 117809.doc 200800839 而產生之應力，藉此可以生產等級製造出在製造時不會產 生破裂之高氧化锆鑄造耐火物。 然而，在高氧化锆鑄造耐火物中玻璃相所占之量較少， 但根據構成玻璃相之成分之種類或量，高氧化錯禱造耐火 物之特性會受到非常大之影響。 又’可知存在下述情形：若高氧化錯鑄造耐火物經受熱 歷程，則玻璃相之二氧化石夕與氧化錐會產生反應，結晶成 锆英石。為抑制如此之玻璃相結晶化等使之成為穩定之玻 璃相，而添加有Na2〇、Ba0等驗金屬氧化物或驗土類氧化 物。 近來:就液晶面板玻璃（LCD，Liquid Crystai此㈣， 液，顯示器）等無驗玻璃而言，為提高其特性，採用了電 = :::則之組成之玻璃。因此’亦要求作為該玻璃之融 解‘、、、之爐内材料的高氧化鍅鑄造耐火物為高電阻產品。 刻前之高電阻產品之電阻係升溫至特定溫度之時 特疋溫度下經過數小時 』于俊之，則疋值，可明確，數值 思疋性或持續性存在問題。 言亦^當保持時間變長時，電阻會增加之情形。具體而 後之♦比較剛升溫至⑽代後與保持12小時 之⑽％。1則保持12小時後之電阻增加至剛升溫後之電阻 著笋英石“原因在於，錯英石析出至玻璃相甲，電阻隨 者^央石之析出而增加。In the first place, a large amount of cast refractory containing Zrc&gt;2 (yttria or yttrium oxide) was used as a refractory for a glass melting furnace. The reason for this is that Zr〇2 is a metal oxide having a particularly high corrosion resistance to molten glass. For example, a high cerium oxide cast refractory containing 80% by weight or more of Zr 〇 2 is used as such a cast refractory. - In the high zirconia cast refractory, the content of Zr〇2 is high and the structure is dense, so that it has a high resistance to the name of the glazed glass. Further, it has an excellent feature that it does not cause defects such as stones or ribs in the glazing glass because it has a property of not forming a reaction layer at the interface with the molten glass. Therefore, high oxidation knot cast refractory systems are particularly suitable for the manufacture of high quality glass refractories. The mineral structure of the high-oxidation-staggered cast refractory is constituted by a monoclinic oxide crystal which accounts for a large part of the crystal, and a small amount of the glass phase fills the grain boundary of the oxidized crystal. The reversible transformation of the crystal system will occur near 11 5 0 C. Volume change caused by glass transition On the other hand, it is known that zirconia crystals change in volume to cause the flow of monoclinic and square glass phases to alleviate the stress generated by the yttrium oxide 117809.doc 200800839, Thereby, it is possible to produce a high zirconia cast refractory which does not cause cracking at the time of manufacture. However, the amount of the glass phase in the high zirconia cast refractory is small, but depending on the kind or amount of the components constituting the glass phase, the characteristics of the highly oxidized refractory refractory are greatly affected. Further, it can be seen that if the high oxidation fault casting refractory is subjected to a heat history, the silica phase of the glass phase reacts with the oxidation cone to crystallize into zircon. In order to suppress such a glass phase crystallization and the like, a stable glass phase is added, and a metal oxide such as Na2〇 or Ba0 or a soil-based oxide is added. Recently, in the case of non-existing glass such as liquid crystal panel glass (LCD, Liquid Crystai, liquid, display), in order to improve its characteristics, a glass of electric =:: is used. Therefore, it is also required that the high yttria-cast refractory which is the material of the melting of the glass, is a high-resistance product. When the resistance of the high-resistance product before engraving is raised to a specific temperature, it takes several hours at a special temperature. 』Yu Junzhi, the value of depreciation is clear, and the value of thinking or persistence is problematic. Words also ^ When the retention time becomes longer, the resistance will increase. Specifically, the ratio is just raised to (10)% after the (10) generation and maintained for 12 hours. 1 After 12 hours, the resistance increased to the resistance immediately after the temperature rise. The reason is that the wrong stone precipitated to the glass phase, and the resistance increased with the precipitation of the central stone.

%此，錯英；^ k I 述之熱循環挪試：：阻方面係有利的’然而，於後 1 s成為龜裂或粉化之原因，故其對於高 117809.doc 200800839 氧化鍅縳造耐火物而言並不理想。 因此’需要可於高溫下維持穩定之高電阻特性的高氧化 鍅轉造耐火物。%本,错英;^ k I The thermal cycle test: The resistance is favorable. However, it is the cause of cracking or chalking after 1 s, so it is high for 117809.doc 200800839 It is not ideal for refractory. Therefore, there is a need for a high yttria conversion refractory which can maintain stable high resistance characteristics at high temperatures.

又’於使用高氧化料造耐火物築造玻㈣㈣之产开， 時，有時亦會引起下述事故：於築爐後之升温過程中二氧 化鍅鑄造耐火物之邊角部破裂飛出，或者用作爐内面^ 氧化錯鑄造敎物之-部分表面成為貝殼狀剝離。&quot; 於引起了如此之高氧化錯鑄造耐火物之破損時，已破損 之部分對於熔融玻璃之侵蝕性變得非常弱。因此，存在於 熔融玻璃中會產生結石或結筋等缺陷之問題。 、 關於該升溫時之剝離，已知其會受到製品表面之殘餘應 2之較大影響。殘餘應力有2種，對於製品而言，於製作 日作為殘餘應力，存在殘餘拉伸應力之情形、以及殘餘 壓，應力之情形。所謂壓縮應力，是指假設耐火物之某二 占0守，集中於該一點之方向上施加力之情形。又，所謂拉 伸應力，是指於自該一點向外側發散之方向上施加力之情 形0 士一般而言，於對耐火物進行加熱之情形時，由於表面會 恥脹，故會新產生與之相反的力即壓縮應力。因此，當高 氧化锆鑄造耐火物表面之殘餘應力為壓縮應力之情形時， 口加熱而產生之壓縮應力與作為殘餘應力之壓縮應力的合 力曰作用於尚氧化錯鑄造耐火物之表面。由此，即便殘餘 &amp;力相對較小，亦容易在升溫時產生破裂或剝離。較好的 疋殘餘應力較小，且殘餘應力為壓縮應力而不是拉伸應 117809.doc 200800839 力。In addition, when the production of glass (4) (4) is made by using a high-oxidation refractory, the following accidents may occur: the corners of the cerium oxide cast refractory rupture and fly out during the heating process after the furnace is built, Or used as the inside of the furnace ^ Oxidation of the wrong castings - part of the surface becomes a shell-like peel. &quot; When such a high oxidation fault casting refractory is damaged, the damaged portion becomes very weak to the molten glass. Therefore, there is a problem that defects such as stones or ribs are generated in the molten glass. Regarding the peeling at the time of temperature rise, it is known that it is greatly affected by the residual amount 2 of the surface of the product. There are two kinds of residual stresses, and in the case of a product, as a residual stress on the production day, there are cases of residual tensile stress, and residual pressure and stress. The so-called compressive stress refers to a situation in which it is assumed that some of the refractory is occupied by the refractory, and the force is applied in the direction of the point. Further, the term "tensile stress" refers to a situation in which a force is applied in a direction in which it is diverged outward from the point. In general, when the refractory is heated, since the surface is swollen, a new generation occurs. The opposite force is the compressive stress. Therefore, when the residual stress on the surface of the high zirconia cast refractory is a compressive stress, the resultant of the compressive stress generated by the mouth heating and the compressive stress as the residual stress acts on the surface of the oxidized cast refractory. Thereby, even if the residual &amp; force is relatively small, it is easy to cause cracking or peeling at the time of temperature rise. The better residual stress is less, and the residual stress is compressive stress rather than tensile.

於曰本專利特開平8-48573號公報中揭示有下述者··若 表面之殘餘應力為80 MPa以下之拉伸應力、或50 MPa以下 之壓縮應力，則可防止升溫時之剝離。然而，對於多數製 品而言，在製造時，於模具内灌注熔融液進行鑄造時所產 生之小孔狀缺陷存在於表面附近。與其他緻密部分相比 較’於強度較弱之小孔狀缺陷附近，即便是在上述殘餘應 力之範圍内，亦無法完全防止升溫時之剝離。因此，必須 研究殘餘應力之更適當之範圍。 進而，就使用咼氧化錯鑄造财火物之玻璃溶解爐而言， 較多的是燃燒器燃燒式之加熱爐。而且’每隔數十分鐘進 仃燃燒器之切換，每次切換時鑄造耐火物表面之溫度會上 下波動故而，大夕使用數年之鑄造耐火物將受到非常多 次數之加熱循環。因此’需要對於熱循環較穩定之高氧化 錯每造财火物。 就對於熱循環之穩定性而言，重要 _ ^ ^ ^ 紝 °里旻的疋，可吸收氧化兹 〜曰曰在附近之急劇體積變化的麵相，即便受到* 循環亦不會產生變化。若# … 右錯夬石析出至玻璃相中，則存名 下迷h形，無法吸收氧化昝 Θ + Μ 之體積變化，熱循環測試後戈 歹欠存體積膨脹率變大，產 ^^ 生龜衣。而且，熱循環測試後4 欠存體積膨脹率與玻璃相 L疋丨生之間存在下述關係。 於釔央石等之結晶析出至玻 Μ你+戌— 内邻γ之^形時，熱循環沒 坟存體積膨脹率超過1〇%。 定η士 力 万面’玻璃相較未 寸之汉存體積膨脹率為j 〇% ’ 下。因此，可藉由測定歹丨 117809.doc 200800839 存^積膨脹率，而推斷玻璃相之穩定性。 具有间電阻之耐火物於日本專利特開昭03-285 173號公 報、日本專利特開平4_193766號公報、日本專利特開平 48573號公報、日本專利特開平8_277162號公報、日本專 利特開平10-59768號公報、w〇 2005/068393號中有所揭 示0 熱循環穩g於日本專利特開平4_193766號公報、日本 _ 專利特開平8_48573號公報、日本專利特開平8·277162號公 報中有所揭示。 防止升%之表面剝離於曰本專利特開平8_48573號公 報、日本專利特開平8_277162號公報中有所揭示。 曰本專利特開昭63-285 173號公報揭示有下述高電阻高 氧化鍅鑄造耐火物：其特徵在於，不含有離子半徑較小之 Li2〇、Na2〇、CaO、Cu0、Mg0、p2〇5，而含 w 5 重量 0/〇 以下之K2〇、Sr0、Ba0、CS2〇中的丨種以上。然而，於該 • 曰本專利特開昭63_285173號公報之揭示中，雖電阻較 高，但不含有玻璃相之穩定化所必需之。〇。又，由於不 含有CaO,故存在張力較大，而在單面加熱時出現破裂之 、 缺點。 於日本專利特開平4-193766號公報中，揭示有下述具有 高電阻且對於熱循環較穩定之高氧化錘電鑄耐火物：其特 欲在於含有1〜3重1。/。之Al2〇3 ’不含有Na2〇、κ2〇，含有 0.3〜3重量％之6&amp;0、81.0、€3〇中的1種以上，含有〇〜15重 量％之ΖηΟ。 117809.doc -10- 200800839 然而，於该日本專利特開平4-193766號公報之揭示中， Ah〇3之含量較高，電，阻並不充分，且不含·有Na2〇、Κ2〇 中之任一者，故熱循環穩定性並不充分。 於曰本專利特開平8-48573號公報中，揭示有下述高氧 化锆電鑄耐火物：其含有〇.05重量％以上之Na2〇，、 SrO、MgO之總量為0.05至3重量％，且對於反覆加熱之熱 循環較穩定，進而表面剝離較少且具有高電阻。然而，由 • 於含有0.05重量％以上之Na2〇，故雖玻璃相變得穩定但電 阻並不充分。又，雖含有Ba0等驗土類氧化物，然而其含 量上限過多，為3重量％。因此，於過量含有時，殘存膨 脹率變大’熱循環穩定性出現問題。 進而，於曰本專利特開平8_48573號公報中，提出有拉 伸應力為80 MPa以下及壓縮應力為5〇Mpa&amp;下作為殘餘應 力之適當範圍’然而應力之範圍過寬，則存在下述情形： #於耐火物表面部分存在小孔狀缺陷，則即便是在範圍内 _ 亦會導致升溫時之剝離。 曰本專利特開平訌277162號公報中，揭示有下述高氧化 锆電鑄耐火物··其含有0.〇5重量％以上之Na20，且仙20與 K2〇之口。十含里為0·1至〇·65重量％，BaO、SrO、及MgO之 總量為1·1至2·8重量％，含有〇·2重量％以下之p2〇5。該高 氧化鍅電鑄而才火物對於反覆加熱之熱循環較穩定，進而， 表面剝離較少且具有高電阻。然而，由於含有0.05重量％ 、上之Na2〇，故雖玻璃相變得穩定但電阻並不充分。 於曰本專利特開平1〇乃9768號公報中，揭示有下述具有 117809.doc -11 - 200800839 高電阻且對於熱循環較穩定之高氧化錯電鑄敎物：其含 有〇.〇5重量％以上之Na2〇及K2〇，不含有㈣等驗土類 氧化物〇 胃 然而，於日本專利特開平1G_59768號公報之揭示中，由 於不含有鹼土類金屬氧化物’故而為使玻璃穩定化，必須 使他2〇之含量為〇.〇5重量％以上。目此，導致電阻不充 分。 於w〇 2005/068393號中，揭示有下述具有高電阻之高氧 化锆電鑄耐火物：其含有0·8重量％以上之Ale3，含有小 於0.04重量％之他2〇’含有小於〇4重量％之。〇。然而： 由於該耐火物中，八丨2〇3之含量為〇8重量％以上，故而電 阻不充分。 進而，CaO係使玻璃穩定化之成分，然而若過度添加， 則會助長锯英石之生成，故而必須更精細地限制含量。 【發明内容】 本發明之目的在於，提供一種具有於高溫下經時變化較 少而穩定之高電阻特性，升溫時難以剝離，且具有熱循環 穩定性之高氧化鍅鑄造耐火物。 若例示本發明之高氧化锆鑄造耐火物，則其係如請求項 1〜7之南氧化錯禱造耐火物。 本發明之高氧化鍅鑄造耐火物，於1500它下保持12小時 後之電阻為200 Ώ cm以上，於升溫過程中不會產生剝離， 且對於熱循環之穩定性優良。 尤其，若將本發明之高氧化锆鑄造耐火物甩於玻璃之溶 117809.doc -12- 200800839 融爐，則升溫時不會產生剝離，且具有高電阻特性。因 此，由該熔融爐所生產之玻璃製品無缺陷，可長期使用， 在產業上非常有益。 本發明者等人專心研究的結果為，提供一種與玻璃相之 1 〇〇〇 C附近之黏度相關的特性及耐火物表面之殘餘應力得 到控制的高氧化錘鑄造耐火物，藉由將高氧化鍅鑄造耐火 物中所含之各成分限制為下述範圍，即，Zr02為87重量％ 以上、96重量％以下，Si〇2為3重量❶/。以上、1〇重量％以 下，Al2〇3為〇.1重量％以上、小於〇 8重量％，Na2〇為小於 〇·〇5重量％，K20為0.01重量％以上、〇.2重量％以下，b2〇3 為〇.1重量％以上、1.0重量％以下，Ba〇為〇 ；!重量％以上、 〇·5重量％以下，SrO為小於〇·〇5重量％，Ca0為〇.〇1重量％ 以上、0.15重量％以下，Y2〇3為0·05重量％以上、〇 4重量 %以下’ MgO為0.1重量％以下，Fe2〇3 + Ti〇2為小於〇·3重量 %，實質上不含有CuO及Ρ2〇5 (為〇.〇1重量％以下），可獲得 於15 0 0 C下保持12小時後之電阻為200 Ώ cm以上，於升溫 時不會剝離，且對於熱循環較穩定之高氧化鍅鑄造耐火 物。 進而較好的是，一種與玻璃相之1000°C附近之黏度相關 的特性及耐火物表面之殘餘應力得到控制的高氧化鍅鑄造 耐火物，藉由將高氧化錯鑄造耐火物中所含之各成分限制 為下述範圍，即，Zr02為88重量％以上、96重量％以下， 8102為3重量％以上、9重量％以下，A1203為〇·1重量％以 上、小於0.8重量％，Na20為小於0.04重量％，Κ20為0.01 117809.doc -13- 200800839 重量％以上、0·15重量％以下，32〇3為〇1重量％以上、〇·7 重里/〇以下，BaO為〇.1重量％以上、〇 5重量％以下，Sr〇 為小於0.05重量％，Ca0為0.01重量％以上、〇15重量％以 下，Y2〇3為0.05重量％以上、〇.2重量％以下，Mg〇為〇 〇5 重置％以下，FeWdTiO2為小於〇.3重量％，實質上不含有 CuO及P2〇5 (〇 〇1重置％以下），從而可獲得於Μ⑽。◦下保持 12小時後之電阻為2〇〇 n.cm以上，於升溫時不會剝離，且 對於熱循環較穩定之高氧化鍅鑄造耐火物。 本發明者等人，為同時滿足高氧化锆鑄造耐火物於高溫 下長妗間穩定之高電阻特性、作為對於反覆升溫及降溫之 %疋性之麥數的熱循環穩定性、以及防止升溫時之剝離， 就鹼金屬氧化物、鹼土類氧化物、氧化鋁等廣範圍之氧化 物之含量進行了詳細研究的結果，獲得下述見解。 雖尚氧化鍅鑄造耐火物中所占之玻璃相之含量較少，但 構成玻璃相之成分之種類或量會相互影響，從而導致玻璃 相對咼氧化鍅鑄造耐火物之特性具有非常大之影響。 即於焉氧化錯鑄造耐火物中，為提高在高溫下之電 阻，必須使離子半徑較小之Na的氧化物即Na2〇顯著少於 先則。然而，若僅減少Na2〇，則無法滿足熱循環穩定性、 及防止升溫時之剝離。因此，可發現，尤其就Al2〇3、 〇 〜〇、Ca〇而言，藉由在適當之範圍内添加該 等成分’可同時滿足於高溫下之長時間穩定之高電阻、熱 循％穩定性、及防止升溫時之剝離。 方面’於南氣化鍅禱造耐火物之製品表面，殘餘應 117809.doc -14- 200800839 力會於製造步驟之鑄造、逐漸冷卻之過程中產生。因此 殘餘應力會根據所使用之鑄模之種類或逐漸冷卻速声而心 到較大的影響。 又 然而’若僅調整鑄造或逐漸冷卻之條件，則無法精確地 控制殘餘應力之種類或大小。即，即便鑄造條件或逐漸冷 部條件相同，若組成不同，則仍會存在殘餘壓縮應力作為 殘餘應力、及殘餘拉伸應力作為殘餘應力之情形。Japanese Patent Publication No. 8-48573 discloses that if the residual stress of the surface is a tensile stress of 80 MPa or less or a compressive stress of 50 MPa or less, peeling at the time of temperature rise can be prevented. However, for most of the products, small hole-like defects generated during the casting of the molten metal in the mold for casting are present near the surface at the time of manufacture. Compared with other dense portions, in the vicinity of the small-pore defects having weaker strength, even in the range of the above-mentioned residual stress, peeling at the time of temperature rise cannot be completely prevented. Therefore, a more appropriate range of residual stress must be studied. Further, in the case of a glass melting furnace using a ruthenium-oxidized mis-casting property, a burner-type heating furnace is often used. Moreover, the switching of the burners every tens of minutes, the temperature of the surface of the cast refractory will fluctuate every time it is switched, and the cast refractory used for several years will be subjected to a very many heating cycles. Therefore, it is necessary to make a high oxidation fault for the thermal cycle. As far as the stability of the thermal cycle is concerned, the 疋 in the important _ ^ ^ ^ 纴 ° can absorb the surface of the abrupt volume change in the vicinity of the oxidation, and does not change even if it is subjected to the * cycle. If #... right-handed vermiculite is precipitated into the glass phase, the name is h-shaped, and the volume change of yttrium oxide + Μ cannot be absorbed. After the thermal cycle test, the volume expansion ratio of the sputum is increased, and the yield is increased. Turtle clothes. Moreover, the following relationship exists between the underfill volume expansion ratio and the glass phase L after the thermal cycle test. When the crystals of the 钇 钇 石 析 析 析 至 至 至 Μ Μ Μ Μ 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内 内The η 士 士 万 ’ ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” Therefore, the stability of the glass phase can be inferred by measuring the expansion ratio of 歹丨 117809.doc 200800839. A refractory having a mutual resistance is disclosed in Japanese Laid-Open Patent Publication No. Hei 03-285 173, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. It is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The surface which is prevented from being increased by % is disclosed in Japanese Laid-Open Patent Publication No. Hei 8-48573, and Japanese Patent Application Laid-Open No. Hei 08-277162. Japanese Patent Publication No. Sho 63-285-173 discloses a high-resistance high-yttria-cast refractory characterized by not containing Li2〇, Na2〇, CaO, Cu0, Mg0, p2〇 having a small ionic radius. 5, and contains more than 丨 of K2〇, Sr0, Ba0, CS2〇 of w 5 weight 0/〇 or less. However, in the disclosure of Japanese Laid-Open Patent Publication No. SHO63-285173, the electric resistance is high, but it is not necessary for the stabilization of the glass phase. Hey. Further, since CaO is not contained, there is a disadvantage that the tension is large and cracking occurs upon heating on one side. Japanese Patent Publication No. Hei 4-193766 discloses a high-oxidation hammer electroformed refractory having high electrical resistance and stable to thermal cycling, which is characterized in that it contains 1 to 3 weights. /. Al2〇3' does not contain Na2〇, κ2〇, and contains 0.3 to 3% by weight of one or more of 6&amp;0, 81.0, and €3, and contains 〇~15% by weight of ΖηΟ. 117809.doc -10- 200800839 However, in the disclosure of Japanese Patent Laid-Open No. Hei 4-193766, the content of Ah〇3 is high, the electric resistance is not sufficient, and it does not contain Na2〇, Κ2〇. Either of them, the thermal cycle stability is not sufficient. Japanese Laid-Open Patent Publication No. Hei 8-48573 discloses a high-zirconia electroformed refractory having a content of 0.05% by weight or more of Na2〇, and a total amount of SrO and MgO of 0.05 to 3% by weight. And the thermal cycle for repeated heating is relatively stable, and thus the surface peeling is less and has high resistance. However, since the content of Na2〇 is 0.05% by weight or more, the glass phase becomes stable but the resistance is not sufficient. Further, although a soil-based oxide such as Ba0 is contained, the upper limit of the content is too large and is 3% by weight. Therefore, when it is excessively contained, the residual expansion ratio becomes large, and there is a problem in thermal cycle stability. Further, in Japanese Laid-Open Patent Publication No. Hei 8-48573, it is proposed that the tensile stress is 80 MPa or less and the compressive stress is 5 〇Mpa &amp; and the appropriate range of residual stress is used. However, the range of the stress is too wide, and the following case exists. : #There is a small hole-like defect on the surface of the refractory, and even if it is within the range, it will cause peeling at the time of temperature rise. Japanese Laid-Open Patent Publication No. 277162 discloses a high-zirconia electroformed refractory having a content of 0.5% by weight or more of Na20 and a mouth of 20 and K2. The total content of BaO, SrO, and MgO is from 1.1 to 2.8 wt%, and contains p2〇5 of 〇·2 wt% or less. The high cerium oxide electroforming is stable for the thermal cycle of the reverse heating, and further, the surface peeling is small and the electrical resistance is high. However, since it contains 0.05% by weight of Na2〇, the glass phase becomes stable but the resistance is not sufficient. In Japanese Patent Laid-Open Publication No. Hei 9768, the following high-oxidation casting compound having high resistance of 117809.doc -11 - 200800839 and stable to thermal cycle is disclosed: it contains 〇.〇5 weight %2 or more of Na2〇 and K2〇 do not contain (4), etc., and the earth-type oxides are smothered. However, in the disclosure of Japanese Laid-Open Patent Publication No. Hei 1G_59768, the glass is stabilized because it does not contain an alkaline earth metal oxide. The content of 2 〇 must be 〇 〇 5% by weight or more. For this reason, the resistance is not sufficient. In WO 2005/068393, there is disclosed a high-zirconia high-zirconia electroformed refractory having a high electrical resistance of more than 0.8% by weight of Ale3, containing less than 0.04% by weight of its 2〇' containing less than 〇4 % by weight. Hey. However, since the content of the barium oxide in the refractory is 8% by weight or more, the electric resistance is insufficient. Further, CaO is a component which stabilizes the glass. However, if it is excessively added, it promotes the formation of sawing stone, and therefore it is necessary to more restrict the content. DISCLOSURE OF THE INVENTION An object of the present invention is to provide a high cerium oxide cast refractory having high resistance characteristics which are less stable over time at a high temperature and which is stable, which is difficult to peel off at the time of temperature rise and which has thermal cycle stability. If the high zirconia cast refractory of the present invention is exemplified, it is a refractory refractory made according to claims 1 to 7. The high cerium oxide cast refractory of the present invention has a resistance of 200 Ώ cm or more after being kept at 1500 for 12 hours, does not cause peeling during heating, and is excellent in stability against thermal cycling. In particular, when the high zirconia cast refractory of the present invention is melted in a glass 117809.doc -12-200800839 melting furnace, peeling does not occur at the time of temperature rise, and high resistance characteristics are obtained. Therefore, the glass product produced by the melting furnace has no defects and can be used for a long period of time, which is very advantageous in the industry. As a result of intensive research by the present inventors, a highly oxidized hammer cast refractory having a viscosity-related property in the vicinity of the glass phase and a residual stress on the surface of the refractory is controlled by high oxidation. Each component contained in the ruthenium cast refractory is limited to a range of 87% by weight or more and 96% by weight or less of ZrO 2 and 3 parts by weight of Si 〇 2 . The above, 1% by weight or less, Al2〇3 is 1.1% by weight or more, less than 〇8% by weight, Na2〇 is less than 〇·〇5重量%, and K20 is 0.01% by weight or more and 〇.2% by weight or less. B2〇3 is 11% by weight or more and 1.0% by weight or less, and Ba〇 is 〇; !% by weight or more, 〇·5% by weight or less, SrO is less than 〇·〇5重量%, and Ca0 is 〇.〇1 by weight % or more, 0.15% by weight or less, Y2〇3 is 0.05 wt% or more, 〇4 wt% or less 'MgO is 0.1% by weight or less, and Fe2〇3 + Ti〇2 is less than 〇·3 wt%, substantially not Containing CuO and Ρ2〇5 (for 〇.〇1% by weight or less), the resistance after holding for 12 hours at 1500 °C is 200 Ώ cm or more, does not peel off at the time of temperature rise, and is stable for thermal cycling. High yttrium oxide cast refractory. Further preferably, a high cerium oxide cast refractory which is controlled in accordance with the viscosity of the glass phase in the vicinity of 1000 ° C and the residual stress of the refractory surface is controlled by the high oxidation fault casting refractory. Each component is limited to a range of 88% by weight or more and 96% by weight or less, 8102 is 3% by weight or more and 9% by weight or less, and A1203 is 〇·1% by weight or more and less than 0.8% by weight, and Na20 is Less than 0.04% by weight, Κ20 is 0.01 117809.doc -13- 200800839% by weight or more, 0. 15% by weight or less, 32〇3 is 〇1% by weight or more, 〇·7 is less than 〇, and BaO is 〇.1 by weight. % or more, 〇 5% by weight or less, Sr 〇 is less than 0.05% by weight, Ca0 is 0.01% by weight or more, 〇 15% by weight or less, Y2 〇 3 is 0.05% by weight or more, 〇. 2% by weight or less, and Mg 〇 is 〇 〇5 Resetting % or less, FeWdTiO2 is less than 0.3% by weight, and substantially does not contain CuO and P2〇5 (〇〇1 is less than or equal to %), so that it can be obtained in Μ(10). After 12 hours of holding under the armpit, the electric resistance is 2 〇〇 n.cm or more, and it does not peel off at the time of temperature rise, and the refractory is casted for high yttria which is stable in thermal cycle. The inventors of the present invention are in order to simultaneously satisfy the high-resistance characteristics of the high zirconia cast refractory at a high temperature and the long-twisting temperature, the thermal cycle stability as the number of enthalpy for the temperature rise and the temperature drop, and the prevention of temperature rise. The results of detailed investigations on the content of a wide range of oxides such as alkali metal oxides, alkaline earth oxides, and aluminum oxides were obtained, and the following findings were obtained. Although the content of the glass phase in the yttria-cast refractory is small, the kind or amount of the components constituting the glass phase affect each other, and the glass has a very large influence on the characteristics of the ruthenium oxide ruthenium cast refractory. That is, in the ruthenium-casting refractory refractory, in order to increase the resistance at a high temperature, it is necessary to make the oxide of Na having a small ionic radius, that is, Na2 〇, significantly less than the first. However, if only Na2〇 is reduced, the thermal cycle stability and the peeling at the time of temperature rise cannot be satisfied. Therefore, it has been found that, in particular, in the case of Al2〇3, 〇~〇, Ca〇, by adding these components within an appropriate range, it is possible to simultaneously satisfy the high resistance at a high temperature for a long period of time, and the heat cycle is stable. Sex, and prevent peeling when warming up. On the surface of the product of the refractory in the gasification of the south, the residue should be produced during the casting and gradual cooling of the manufacturing steps. Therefore, the residual stress will have a large influence depending on the type of mold used or the gradual cooling of the speed. However, if only the conditions of casting or gradual cooling are adjusted, the type or size of the residual stress cannot be accurately controlled. That is, even if the casting conditions or the gradual cooling conditions are the same, if the composition is different, there are cases where residual compressive stress is used as residual stress and residual tensile stress is used as residual stress.

而且，著眼於殘餘應力及高氧化錯鑄造耐火物之玻璃相 之熱特性而進行專心研究之結果可發現，測定高氧化鍅鑄 造耐火物之熱彎曲強度時之破壞狀態下的變化溫度（〗卜及 與高氧化鍅鑄造耐火物之玻璃相組成相同的玻璃之玻璃轉 移點（Tg)(2)，與殘餘應力有密切之關係，藉由控制該等 ⑴或(2) ’可製造出於升溫時不會引起剝離之高氧化鍅鑄 造耐火物。 對於高氧化錯鑄造耐火物而言，在熱彎曲強度測定中， :相強度與室溫下大致相等之低溫區域、及彎曲強度極 端下降之高溫區域中’破壞形態不同。於低溫區域内，脆 性破壞顯[形成平滑之斷面；於高溫區域内，由於晶粒 邊界之玻璃相之軟化或流動，破壞變成伴著塑性變形之破 壞形態，從而呈現出起毛邊之斷面。而且，在玻璃相之玻 璃轉移點以上時，u η , 因伴者塑性形之破壞而導致強度急劇 下降。 【實施方式】 實施例 】17809.doc 200800839 圖1表示本發明之範圍内的實施例4(表1 )及本發明之範 圍外的比較例4(表2)之熱彎曲強度。實施例4之自脆性破壞 至伴著塑性變形之破壞之變化點為’彎曲強度6〇 Mpa、變 化溫度875°C，包含在本發明之範圍内。該樣本之6〇〇它以 下之低溫區域之強度為122x1(T2 MPa，1300。(：以上之高溫 區域之強度為2χΐ(Γ2 MPa。該等之中間強度為（122-2)—2 =60 MPa，與該彎曲強度相應之溫度為87vc，與實測值大 致相等。 又’比較例4之彎曲強度之變化溫度為8〇(rc，在本發明 之範圍外。 與比較例4之中間強度即（107-7»5〇 MPa相應之溫度 為81 0°C，大致與實測之變化溫度相等。 如此，熱彎曲強度之破壞形態之變化溫度大致等於與彎 曲強度之低溫部分下的值及高温部分下的值之中間強度相 應之溫度，從而亦可自強度測定值推斷出破壞形態之變化 溫度。 進而，利用 ΕΡΜΑ (Electron Probe X-ray MicroAnalyzer， x射線微量分析器），實施圖i所示之樣本之玻璃相的定量 分析。調配試劑以獲得組成與所獲得之分析值相同的玻 璃，於鉑坩鍋中使該調配物加熱熔融，製成玻璃狀固化 物。使用熱膨脹測定計，測定該玻璃之玻璃轉移點（Tg)。 其、、、σ果為，貫施例4之Tg為890°c，比較例4之Tg為810°C。 玻璃轉移點（Tg)下之玻璃之黏度為i〇u〜1〇】5泊左右，於 較玻璃轉移點（Tg)更高的溫度下，黏度隨溫度之上升而下 117809.doc -16- 200800839 降，從而玻璃會具有，流動性。 因此，玻璃轉移點(Tg)較高，意味著即便於高溫下玻璃 之黏性亦較高。 又’於南氧化錯鑄造耐火物中所含有之氧化物中，最使 si〇2玻璃之玻璃轉移點下降者為Ν^〇。因此，根據^^2〇之 含置’亦可在某種程度上推斷出玻璃轉移點。 於南氧化錯鑄造耐火物之自鑄造至冷卻為止的過程中，Moreover, focusing on the thermal characteristics of the residual stress and the glass phase of the high-oxidation-staggered cast refractory, it was found that the temperature at the time of the failure of the high yttrium-cast refractory was determined. And the glass transition point (Tg) (2) of the same glass composition as the high yttria-cast refractory glass phase, which is closely related to the residual stress, can be manufactured by controlling the (1) or (2) ' High yttria cast refractory does not cause peeling. For high oxidation fault cast refractories, in the measurement of hot bending strength, the low temperature region where the phase strength is approximately equal to room temperature and the high temperature at which the bending strength is extremely lowered In the region, the shape of the failure is different. In the low temperature region, the brittle failure is obvious [forms a smooth section; in the high temperature region, due to the softening or flow of the glass phase of the grain boundary, the failure becomes a failure mode accompanied by plastic deformation, thereby The cross section of the burr is present. Moreover, when it is above the glass transition point of the glass phase, u η causes a sharp drop in strength due to the destruction of the plastic form of the companion. [Embodiment] Example] 17809.doc 200800839 Fig. 1 shows the thermal bending strength of Example 4 (Table 1) within the scope of the present invention and Comparative Example 4 (Table 2) outside the scope of the present invention. The change point from brittle failure to failure with plastic deformation is 'bending strength 6 〇 Mpa, change temperature 875 ° C, and is included in the scope of the present invention. The strength of the sample below 6 〇〇 below the low temperature region is 122 x 1 (T2 MPa, 1300. (: The strength of the above high temperature region is 2 χΐ (Γ2 MPa. The intermediate strength is (122-2) - 2 = 60 MPa, and the temperature corresponding to the bending strength is 87 vc, and the measured value Further, the change temperature of the bending strength of Comparative Example 4 is 8 〇 (rc, which is outside the range of the present invention. The intermediate strength of Comparative Example 4 is (107-7»5 MPa, and the temperature is 81 0°). C, which is approximately equal to the measured temperature of change. Thus, the temperature of the deformation of the thermal bending strength is approximately equal to the temperature corresponding to the value of the low temperature portion of the bending strength and the intermediate strength of the value under the high temperature portion, and thus the self strength Determining the damage form Further, quantitative analysis of the glass phase of the sample shown in Fig. i was carried out by using an Electron Probe X-ray MicroAnalyzer (x-ray microanalyzer). The reagent was formulated to obtain a glass having the same composition as the obtained analytical value. The composition was heated and melted in a platinum crucible to obtain a glassy cured product. The glass transition point (Tg) of the glass was measured using a thermal expansion meter. The σ fruit was the Tg of Example 4. For 890 ° C, the Tg of Comparative Example 4 is 810 ° C. The viscosity of the glass under the glass transfer point (Tg) is i〇u~1〇] about 5 poises, at a higher temperature than the glass transition point (Tg). Underneath, the viscosity rises with the temperature down 117809.doc -16- 200800839, so the glass will have, fluidity. Therefore, the glass transition point (Tg) is high, meaning that the viscosity of the glass is high even at high temperatures. Further, among the oxides contained in the oxidized cast refractory, the glass transition point of the si〇2 glass is most reduced. Therefore, the glass transition point can be inferred to some extent according to the inclusion of ^^2〇. During the process from casting to cooling of the south oxidized cast refractory,

所產生之殘餘應力與玻璃相之關係可如下所述而推定。 考慮下述情形，即，高氧化鍅鑄造耐火物之外層凝固結 束後，其内層自此開始凝固。於冷卻過程中之氧化鍅结晶 之形態變化溫度（約100(TC)附近，玻璃相之黏度較低而具 有充分之流動性之情形時，因氧化鍅結晶之形態變化而產 生之應力藉由玻璃之流動而得到緩和。因此，因氧化錯結 晶之形態變化而產生之應力不會影響到鑄塊之殘餘應力。 於此情形日夺，進一步進行冷卻，自内層喪失流動性之後開 始積蓄基於外層與内層之溫度差的熱應力，藉此產生殘餘 應力。其結果為，高氧化鍅鑄造耐火物表面之殘餘應力成 為S縮應力。 另一方面 附近，玻璃 氧化錐結晶 ，於冷卻過程中之氧化錯結晶之形態變化溫度 相之黏度較高而無充分之流動性之情形時，因 之形態變化而產生之應力未得到充分缓和，從 —^ — ,τ艰刀。於此情形 時，進-步進行冷卻，基於内層與外層之 力、與前輯粒氧化録晶之形g變化時所產生之應; 117809.doc -17- 200800839 之合計成為殘餘應力。其結果為，高氧化锆鑄造耐火物表 2之殘餘應力，成為較破璃相之黏性較低之情形更小的屢 縮應力或拉伸應力。 即’若熱彎曲強度測定中之破壞形態之變化溫度與破璃 轉移點⑽分別為⑼代、81代左右，則高氧化料造耐 A物之玻璃相於⑽代附近之黏度較低，製品表面之殘餘 應力為塵縮應力’成為本發明之適#範圍外之殘餘應力。 另方面’若熱彎曲強度測定中之破壞形態之變化溫度 與玻璃轉移點师別為叫崎左右^由下述表 2亦可表明’咼氧化锆鑄造耐火物中之玻璃相於1〇〇〇。。 附近之黏度較南’製品表面之殘餘應力為拉伸應力，成為 本發明之適當範圍内之殘餘應力。 如此，藉由控制與玻璃相之黏度（尤其係⑽旳附近之 玻璃相之黏度）相關之特性’可控制高氧化結鑄造耐火物 之殘餘應力。 兮於本發明中’著眼於熱彎曲強度測定中之破壞形態產生 又化之溫度及玻璃轉移點’然而’著眼於其他熱特性之指 標’例^應變點等之情形，亦包含於本發明之範圍内。 又，高氧化錯鑄造耐火物係氧化鍅結晶與玻璃相之混合 物。而且’氧化锆之電阻顯著低於作為玻璃相主成分的二 氧化秒。 一 ^此，為將尚氧化錯鑄造耐火物之電阻提高，必須增加 南氧化鍅鑄造耐火物中之玻璃相之量，或者使玻璃相之組 成接近作為高電阻之高純度二氧化矽玻璃。 H7809.doc 200800839 玻璃相之量鱼%. AU A4. Θ t 一乳化鍅夏相反，就耐侵蝕性方面而言，The relationship between the residual stress generated and the glass phase can be estimated as follows. Consider the case where the inner layer of the high cerium oxide cast refractory is solidified after the solidification of the outer layer. The morphological change temperature of cerium oxide crystal during cooling (about 100 (TC), when the viscosity of the glass phase is low and there is sufficient fluidity, the stress caused by the morphological change of cerium oxide crystals is caused by the glass. The flow is relieved. Therefore, the stress generated by the morphological change of the oxidized staggered crystal does not affect the residual stress of the ingot. In this case, further cooling is performed, and the fluidity is lost from the inner layer and then accumulated based on the outer layer. The thermal stress of the temperature difference of the inner layer, thereby generating residual stress. As a result, the residual stress on the surface of the high yttria cast refractory becomes the S-shrinkage stress. On the other hand, the glass oxide cone crystallizes, and the oxidation error during the cooling process When the morphological change of the crystallization is high and the viscosity of the phase is high and there is no sufficient fluidity, the stress caused by the morphological change is not sufficiently alleviated, from -^ to τ, in this case, the step is further advanced. Cooling, based on the force of the inner and outer layers, and the shape of the granules of the former granules; 117809.doc -17- 200800839 It becomes a residual stress. As a result, the residual stress of Table 2 of the high zirconia cast refractory becomes a contraction stress or tensile stress which is smaller than the case where the viscosity of the glass phase is low. The change temperature of the failure mode and the break point of the glass break (10) are (9) and 81 generations respectively. The glass phase of the high-oxidation material resistant to the A material has a lower viscosity near the (10) generation, and the residual stress on the surface of the product is dust reduction. The stress 'is the residual stress outside the range of the present invention. On the other hand, if the temperature of the failure mode in the measurement of the thermal bending strength is changed, the temperature and the glass transition point are different from that of the Sasaki. The glass phase of the zirconia cast refractory is 1 〇〇〇. The residual stress near the surface of the product is tensile stress, which is the residual stress in the proper range of the present invention. Thus, by control and glass The viscosity of the phase (especially the viscosity of the glass phase near (10) 旳) can control the residual stress of the high oxidation knot casting refractory. In the present invention, the focus is on the determination of the thermal bending strength. The case where the temperature and the glass transition point of the bad form are generated 'however' is focused on other thermal characteristics, such as the strain point, etc., are also included in the scope of the present invention. Further, the high oxidation fault casting refractory is cerium oxide. a mixture of crystallization and a glass phase. Moreover, the resistance of zirconia is significantly lower than that of the oxidized second as the main component of the glass phase. In order to increase the electrical resistance of the oxidized cast refractory, it is necessary to increase the ruthenium ruthenium cast refractory. The amount of the glass phase in the middle, or the composition of the glass phase is close to the high-purity high-purity ceria glass. H7809.doc 200800839 The amount of glass phase fish. AU A4. Θ t Sexually speaking,

Si〇2之上限限制為1 〇重量％。 又’為使玻璃相高電阻化，僅可能減少離子半徑較小之 驗離子」尤其是Na2〇e其結果為，输之玻璃轉移點 (Tg)增高，電阻亦增加。 例如，。仏2〇與Si〇2之莫耳比為丨：2之玻璃即Na2Si2〇5之 Tg為732 C ’然而不含有Na2〇(Si〇2的Tg為1463。〇，電阻 亦顯著增加。 然而，僅單純減少Ν&amp;2〇時，雖玻璃轉移點Tg及電阻增 加但無法同B寸滿足用以防止下述狀況之殘餘應力的合適 性，即：製造製品時之龜裂、或因熱循環測試後錯英石之 生成而引起的殘存體積膨脹率之增力”或升溫時所產生之 龜裂。 曰因此，藉由將對電阻影響較大之N&amp;0之含量限制為最低 ΐ，且專心研究並查明防止製造時之龜裂所必需之或 對於玻璃穩定化而言重要的Al2〇3、以〇、Ca〇、ΙΑ、 SrO等之含量的適當範圍，可實現高電阻化。 圖2表示表1之實施例4及表2之比較例9之於15〇〇艺保持 時之電阻的經時變化。 於圖2中，實施例4之電阻較穩定，而比較例9之電阻隨 時間之經過而增加。 圖3係實施例4之於150(rc下保持12小時後之顯微鏡相 片。於粒狀之氧化锆結晶之晶粒邊界觀察玻璃相。顏色較 濃且看上去細長的部分係玻璃相。 117809.doc -19- 200800839 圖4係比較例9之於朦c下保持12小時後之顯微鏡相 :知’於粒狀氧化錯結晶之晶粒邊界之玻璃相中散佈 有錯英石之較小粒狀結晶。 於實施例4中，名H 。广ΠΓ # 4士，1 朴 在15〇〇C下保持12小時後亦不會生成結 央石，故電阻值較穩定。The upper limit of Si〇2 is limited to 1% by weight. Further, in order to increase the resistance of the glass phase, it is only possible to reduce the detection ion having a small ionic radius, especially Na2〇e. As a result, the glass transition point (Tg) of the glass is increased and the electric resistance is also increased. E.g,. The molar ratio of 仏2〇 to Si〇2 is 丨: the glass of 2, that is, the Tg of Na2Si2〇5 is 732 C', but does not contain Na2〇 (the Tg of Si〇2 is 1463. 〇, the electrical resistance also increases significantly. However, When only Ν&amp;2〇 is simply reduced, although the glass transition point Tg and the resistance increase, but the same as B, the suitability for preventing residual stress in the following conditions, that is, cracking during manufacturing of the product, or heat cycle test The increase in the residual volume expansion rate caused by the formation of the wrong stone or the crack generated during the temperature rise. Therefore, by limiting the content of N&amp;0 which has a large influence on the resistance to the lowest level, and focusing on It is possible to achieve high resistance by studying and ascertaining the appropriate range of the content of Al2〇3, which is necessary for the prevention of cracking during manufacture or for glass stabilization, and the content of ruthenium, Ca〇, ΙΑ, SrO, etc. The change of the resistance of the comparative example 9 of Table 1 and the comparative example 9 of Table 2 at the time of 15 〇〇 is maintained. In Fig. 2, the electric resistance of the embodiment 4 is relatively stable, and the electric resistance of the comparative example 9 with time Figure 3 is a microscope of Example 4 at 150 (12 hours after rc) The glass phase is observed at the grain boundary of the granular zirconia crystal. The thicker and more elongated portion is the glass phase. 117809.doc -19- 200800839 Figure 4 is a comparison of Example 9 under 朦c to maintain 12 Microscopic phase after hours: It is known that the smaller phase of the phenocrytic stone is dispersed in the glass phase of the grain boundary of the granular oxidized crystal. In Example 4, the name H. 广ΠΓ # 4士, 1 Park will not form a knot stone after 12 hours at 15 ° C, so the resistance value is relatively stable.

然而，於比較例9中，由於Si〇2含量較多’故升溫至 1· C時之電阻較高’隨時間之經過會自玻璃相生成錯英 故電阻進一步增加。於比較例9中，雖電阻較高，但 谷易生成鍅英石，於熱循環測試後樣本出現粉化。 於實施例4中’電阻具有穩定性，在熱循環測試後，殘 存體積膨脹率亦較小，且亦未生成錯英石。 繼而’就本發明之高氧化錯鑄造耐火物之各成分加以說 明。 /r〇2之含量為87重量％以上、％重量％以下。更好的 是，Zr〇2之含量為88重量％以上、％重量％以下。若 少於87重量％ ’則财蝕性較差’若多於％重量％，則與其2 他成分失衡，容易於耐火物中產生龜裂。However, in Comparative Example 9, since the content of Si〇2 was large, the electric resistance when the temperature was raised to 1·C was high, and the resistance was further increased from the glass phase due to the passage of time. In Comparative Example 9, although the electric resistance was high, the valley was liable to form bismuth, and the sample was powdered after the heat cycle test. In Example 4, the electric resistance was stable, and after the thermal cycle test, the residual volume expansion ratio was also small, and no smectite was generated. Next, the components of the high oxidation fault casting refractory of the present invention will be described. The content of /r〇2 is 87% by weight or more and % by weight or less. More preferably, the content of Zr〇2 is 88% by weight or more and % by weight or less. If it is less than 87% by weight, the financial property is poor. If it is more than 5% by weight, it is unbalanced with the other components, and cracks are likely to occur in the refractory.

Si〇2之含量為3重量％以上、1G重量％以下。更好的是， Si〇2之含量為3重量％以上、9重量％以下。 若Si〇2之含量少於3重量％，則難以於耐火物中形成充分 之玻璃相。雖二氧化矽越多越可提高電阻，但若多於丨❹重 量％，則耐火物對於熔融玻璃之耐蝕性會變差，且於高溫 下玻璃相自耐火物之滲出會增加。 B2〇3之含量為〇.1重量％以上、1〇重量％以下。更好的 I17809.doc *20- 200800839 是’ B2〇3之含量為(^重量％以上、〇 7重量。/。以下。若B 乂於0.1重里％ ’貝,j製成製品時無法防止撕裂型龜裂之 生。若多w.o重量％，則熱循環測試後之殘存體積膨Μ 接近20%，並且拉伸應力變大，於使用 \ 齡则_之高氧化錯鑄造_火物之_行加_ 單面加熱測試中會出現破裂。The content of Si〇2 is 3% by weight or more and 1% by weight or less. More preferably, the content of Si〇2 is 3% by weight or more and 9% by weight or less. If the content of Si〇2 is less than 3% by weight, it is difficult to form a sufficient glass phase in the refractory. Although the electric resistance is increased as the amount of cerium oxide is increased, the corrosion resistance of the refractory to the molten glass is deteriorated, and the leaching of the glass phase from the refractory is increased at a high temperature. The content of B2〇3 is 〇1% by weight or more and 1% by weight or less. Better I17809.doc *20- 200800839 is the content of 'B2〇3 is (^% by weight or more, 〇7 weight. /. below. If B 乂 is 0.1% by weight), it cannot be prevented when it is made into a product. If the weight is more than %, the residual volume expansion after the thermal cycle test is close to 20%, and the tensile stress becomes large, and the use of \ age is high oxidized wrong casting _ fire goods _ Line _ rupture occurs in the one-sided heating test.

Ah〇3之含量為（^重量％以上、小於〇8重量％。具 有下述效果’ gP ’使添加成分之溶融物之流動性提高而容 2進行鑄造，並騎㈣火物中之ZK)2_於麵相中， 從而不會使玻璃中生成鍅英石。 若Α12〇3之含量少於〇.〗重量％，則熱循環測試後之殘存 體積膨脹率變為3G%左右，π火物之熱循環敎性變差。 右A12 〇 3之含里為0 · 8重着' %P ，目丨丨S奋 里里/〇以上，則雖可提高熱循環穩定 性，但電阻顯著下降。 又，A!2〇3具有使高氧化鍅鑄造耐火物表面之壓縮應力 增加的效果。The content of Ah〇3 is (% by weight or more and less than 8% by weight. It has the following effect 'gP' to improve the fluidity of the melt of the added component and to carry out casting, and ride (4) ZK in the fire) 2_ in the face, so that no bismuth is formed in the glass. If the content of Α12〇3 is less than 〇. 重量%, the residual volume expansion ratio after the thermal cycle test becomes about 3G%, and the thermal cycle π of the π fire material deteriorates. The right A12 〇 3 contains 0 · 8 with '%P, and the target S Furi / 〇 above, although the thermal cycle stability can be improved, but the resistance is significantly reduced. Further, A!2〇3 has an effect of increasing the compressive stress on the surface of the high cerium oxide cast refractory.

NhO之含量為小於〇.〇5重量％。更好的是ν&amp;2〇之含量為 小於0.04重篁％。若Na2〇之含量為Q 〇5重量％以上，則对 火物之電阻急劇下降。又，Na2〇具有使玻璃相之玻璃轉移 點溫度(Tg)急劇降低之效果，並且具有使耐火物之壓縮應 力增加之效果。 κ20之含量為0.01重量％以上、〇·2重量％以下。更好的 是，ΚΑ之含量為0.01重量％以上、〇15重量％以下。κ2〇 在Na20之含里叉到限制之本發明之情形時為必需成分。若 117809.doc -21 - 200800839 Κ20少於〇·〇!重量％(即實質上不含有），則熱循環測試後之 t火物之反存體積膨脹率非常大，熱循環穩定性變差。若 多於0·2重量％，則耐火物之電阻變得不充分。 又，尺2〇亦與Na2〇同樣具有使耐火物之壓縮應力增加之 效果。The content of NhO is less than 〇.〇5 wt%. More preferably, the content of ν &amp; 2 为 is less than 0.04% by weight. When the content of Na2〇 is Q 〇 5% by weight or more, the resistance to the fire is sharply lowered. Further, Na2〇 has an effect of rapidly lowering the glass transition point temperature (Tg) of the glass phase, and has an effect of increasing the compressive stress of the refractory. The content of κ20 is 0.01% by weight or more and 〇·2% by weight or less. More preferably, the content of cerium is 0.01% by weight or more and 〇 15% by weight or less. Κ2〇 is an essential component in the case of the present invention in which the Na20 is forked to the limit. If 117809.doc -21 - 200800839 Κ20 is less than 〇·〇!% by weight (that is, it is not substantially contained), the anti-storage volume expansion rate of the t-fire after the thermal cycle test is very large, and the thermal cycle stability is deteriorated. If it is more than 0.2% by weight, the electrical resistance of the refractory becomes insufficient. Further, the ruler 2 has an effect of increasing the compressive stress of the refractory material as well as Na2〇.

BaO係使破璃相穩定之成分，故於本發明中為必需成 分。 • Ba〇之含量為0.1重量％以上、0.5重量％以下。若Ba〇之 含量少於0.1重量％，則耐火物之熱循環後的殘存體積膨服 率較大，熱循環穩定性變差。若Ba〇之含量超過0.5重量 /〇則電阻下降，並且熱循環後之殘存體積膨脹率亦增 加，熱循環穩定性變差。BaO is a component which stabilizes the glass frit phase, and is therefore an essential component in the present invention. • The content of Ba〇 is 0.1% by weight or more and 0.5% by weight or less. If the content of Ba〇 is less than 0.1% by weight, the residual volume expansion rate after the thermal cycle of the refractory is large, and the thermal cycle stability is deteriorated. If the content of Ba〇 exceeds 0.5 wt/〇, the electric resistance decreases, and the residual volume expansion ratio after the heat cycle also increases, and the thermal cycle stability deteriorates.

SrO之含量為小於〇 〇5重量％。對於Sr〇而言，其防止對 耐火物鑽孔時之龜裂之效果較大，然而若為〇 〇5重量％以 上，則耐火物之電阻將變得不充分。 _ CaO之含量為0.01重量％以上、〇 15重量％以下。“ο與The content of SrO is less than 〇 5% by weight. In the case of Sr〇, the effect of preventing cracking when drilling a refractory is large, but if it is 5% by weight or more, the electrical resistance of the refractory becomes insufficient. The content of CaO is 0.01% by weight or more and 〇 15% by weight or less. "ο and

Ba〇同樣，可使玻璃相變得穩定。Ca〇在氧化鍅原料中作 為雜質存在，於本發明中係必要成分。 於不含有CaO之情形時，拉伸應力變大，在單面加熱時 會產生剝離。然而，若耐火物中所含之Ca〇多於〇·丨5重量 % ’則耐火物之熱循環加熱後的殘存體積膨脹率變大，極 端之情形下耐火物會粉化。 Y2〇3之含量為0.05重量％以上、04重量％以下。進而， 較好的是，Υ2〇3之含量為〇 〇5重量％以上、〇·2重量％以 117809.doc -22- 200800839 下。Y 2 〇 3於氧化錯原料中係作為雜質而存在。然而，若超 過0.4重量％ ’則耐火物之熱循 。 “、、俊的殘存體積膨脹率 、交，…、循環穩定性較差並且電阻亦會下降。Similarly, Ba〇 can stabilize the glass phase. Ca 存在 exists as an impurity in the cerium oxide raw material, and is an essential component in the present invention. When CaO is not contained, the tensile stress becomes large, and peeling occurs upon heating on one side. However, if the Ca 含 contained in the refractory is more than 5% by weight of 〇·丨, the residual volume expansion ratio of the refractory after the heat cycle heating is increased, and the refractory is pulverized at the extreme end. The content of Y2〇3 is 0.05% by weight or more and 04% by weight or less. Further, it is preferred that the content of Υ2〇3 is 〇5% by weight or more and 〇·2% by weight is 117809.doc -22-200800839. Y 2 〇 3 is present as an impurity in the oxidizing material. However, if it exceeds 0.4% by weight, the heat of the refractory is followed. ",, Jun's residual volume expansion rate, intersection, ..., cycle stability is poor and the resistance will also drop.

MgO之含量為〇1重量 入旦丛 里乂卜進而，較好的是，Mg〇之 二 重量％以下。Mg0作為氧化錯原料中之雜質而 二在。右超過(M重量％，則耐火物之熱循環測試後的殘存 體積膨脹率變大，熱循環穩定性較差。 及Ti〇2之合計含量狀3重量％以下。以敲叫 、’广中係作為雜質而存在，但由於其會影響到製作時之 破裂’因此較好的是〇·3重量％以下。 於本發明中實質上不含有⑽及⑽。於⑽及⑽與 ⑽共存之情形時，形成低融點玻璃，具有使化學耐久性 ::下降之性質。χ，P2〇5會使耐火物對熱循環之穩定性 顯者下降。又，該等原料之吸濕性較大，於在原料中加以 使用之h形時，具有難以製成緻密之耐火物的性質。 =〇在減少耐火物之破裂方面係有效的，然而由於其會 使烙嘁破璃著色，故而較理想的是實質上不含有Cu〇。 於本發明中，實質上不含有係指，雖藉由分析法、分析 儀益之精度，仍小於0.01重量％。 #剛文所述之各實施例及比較例之高氧化鍅鑄造耐火物係 藉由通常之方法而製成的。 &quot;、 ^ 於使鍅英砂脫石夕而獲得之氧化鍅原料中，以特A 丨《λ 寸疋比 入Si〇2、ai2〇3、Na20、Β2〇3、及其他粉末原料 兮蓉、、©人 &quot;、/ντ ’將 〜寸此β後，以電弧電爐進行熔融，並於已準備之鑄模中 I17809.doc •23· 200800839 進行鑄造’將其埋入氧化鋁粉末中逐漸冷卻至室溫為止。 對於鑄模’使用黑省製、製品部分之尺寸為 iooxsooxsso mm、且於其上部一體連接有内尺寸為 140x235x35 0 mm之冒口部分者。 冷部後，自氧化鋁粉末中取出製品，將製品部分自冒口 口P刀切離’獲得所期望之高氧化錯禱造耐火物。此時，讀 g忍外觀上有無龜裂。 特：實：例1至實施例10之高氧化錯鑄造耐火物之組成及 特性不於表1。The content of MgO is 〇1 by weight. Further, it is preferably 5% by weight or less of Mg 〇. Mg0 acts as an impurity in the oxidizing faulty material. When the right amount exceeds (M% by weight, the residual volume expansion ratio after the thermal cycle test of the refractory becomes large, and the thermal cycle stability is poor. The total content of Ti〇2 is 3% by weight or less. To knock, 'Guangzhong system It exists as an impurity, but it affects the rupture at the time of manufacture. Therefore, it is preferable that it is 3% by weight or less. In the present invention, substantially no (10) and (10) are contained. When (10) and (10) and (10) coexist. Forming a low-melting point glass, which has the property of reducing chemical durability:: χ, P2〇5 will significantly reduce the stability of the refractory to the thermal cycle. Moreover, the hygroscopicity of the raw materials is greater. When the h-shape is used in the raw material, it has a property that it is difficult to form a dense refractory. = 〇 is effective in reducing the rupture of the refractory, but since it causes the enamel to be colored, it is preferable It does not substantially contain Cu 〇. In the present invention, substantially no such finger is contained, and although the precision of the analytical method and the analytical instrument is still less than 0.01% by weight, the respective examples and comparative examples described in the text are High cerium oxide cast refractory by the usual Made by the method. &quot;, ^ In the cerium oxide raw material obtained by removing the sputum from the stone, the special A λ λ 疋 疋 〇 〇 〇 ai ai ai ai ai ai ai ai ai ai ai ai 、 、 、 、 、 、 、 、 、 、 、 、 、 And other powder raw materials Cistanche, and © people &quot;, / ντ ' will be melted in an electric arc furnace after the β, and will be cast in the prepared mold I17809.doc •23· 200800839 The alumina powder is gradually cooled to room temperature. For the mold, the black product is used, the size of the product part is iooxsooxsso mm, and the riser portion having the inner dimension of 140x235x35 0 mm is integrally connected to the upper portion. The product is taken out from the alumina powder, and the part of the product is cut away from the mouth of the mouth P to obtain the desired high oxidation fault-making refractory. At this time, there is no crack in the appearance of reading g. The composition and characteristics of the high oxidation fault cast refractory to Example 10 are not shown in Table 1.

117809.doc 24- 200800839117809.doc 24- 200800839

ο r—ί 6.60 0.55 0-01 0.50 0.03 0.08 0.10 0.20 0,02 0.15 0.10 &lt;0.01 I &lt;0.01 碌 850 ! 850 T—( 1 碟 1 〇 〇6 250 Os 91.5 6.10 0.55 0.02 0.50 0.06 0.40 0.15 0.20 &lt;0.01 0.35 0.03 &lt;0.01 &lt;0.01 〇〇 〇〇 们 r—^ 1 碟 〇 〇\ 220 〇〇 92.0 6.10 0.55 0.03 0.50 0.05 0.08 0.10 0.20 | 0.04 0.18 0.01 &lt;0.01 &lt;0.01 碟 〇〇 〇〇 ο r-H t 碟 碟 10.0 250 卜 95.2 3.09 0,60 0.01 0.30 0.02 0.10 0.10 0.23 0,02 | 0.18 &lt;0.01 1 &lt;0.01 1 &lt;0.0! 碟 JQ 〇〇 〇 00 碟 〇 〇6 200 VO 93.6 4.10 0.50 &lt;0.01 0.50 0.10 0.50 0.09 0.20 | 0.03 0.20 0.04 &lt;0.01 1 &lt;0.01 〇〇 0 ON 0 碟 10.0 230 92.2 6.65 0.10 &lt;0.01 0.50 0.09 0.08 0.01 0.12 &lt;0.01 0.05 &lt;0.01 &lt;0.01 &lt;0.01 碟 〇 &lt;N 〇\ 0 冢 to t—H 碟 碟 od 600 寸 91.6 6.40 0.60 &lt;0.01 0.45 0，10 0.20 0.09 0.23 0.02 0.15 &lt;0.01 &lt;0.01 &lt;0.01 碟 〇〇 δ 卜 0 rn m 92.5 4.70 0.60 0.01 0.95 0.20 0.40 0.09 0.20 0.02 0.15 0.03 &lt;0.01 &lt;0.01 g 00 ο 冢 (N 10.0 250 (N 91.5 6.65 0.65 0,04 0.15 0.01 0.40 0.15 0.20 &lt;0.01 0.14 0.01 &lt;0.01 &lt;0.01 萄 § 00 ο ON 0 r-H 碟 碟 0 00 220 r ( ON oo 8.80 0.75 &lt;0.01 0.50 0.04 0.20 0-10 0.25 0.02 0.10 0.02 &lt;0.01 &lt;0.01 0 t On 0 ON 碟 0 m 實施例 Zr02 GO ai2o3 Na20 B2〇3 o BaO CaO Fe2〇3+Ti02 i SrO Y2〇3 MgO CuO p205 製造時之龜裂 玻璃轉移點Tg(°c) 熱彎曲強度之變化溫度(°c) 殘餘應力(Mpa) 單面加熱測試 熱循環測試龜裂、粉化之有無 殘存體積膨脹率(％) 電阻(Ω-cm) 成分 (重量°/〇) -25- 壊w :碱舰。$鳄奪4:碱τ 117809.doc 200800839 又，將比較例1至1 5之高氧化錯鑄造耐火物之組成及特 性示於表2。ο r—ί 6.60 0.55 0-01 0.50 0.03 0.08 0.10 0.20 0,02 0.15 0.10 &lt;0.01 I &lt;0.01 850 850 ! 850 T—( 1 dish 1 〇〇 6 250 Os 91.5 6.10 0.55 0.02 0.50 0.06 0.40 0.15 0.20 &lt;0.01 0.35 0.03 &lt;0.01 &lt;0.01 rr-^ 1 〇〇 〇〇 \ 220 〇〇92.0 6.10 0.55 0.03 0.50 0.05 0.08 0.10 0.20 | 0.04 0.18 0.01 &lt;0.01 &lt;0.01 〇ο rH t Disc 10.0 250 Bu 95.2 3.09 0,60 0.01 0.30 0.02 0.10 0.10 0.23 0,02 | 0.18 &lt;0.01 1 &lt;0.01 1 &lt;0.0! Disc JQ 〇〇〇00 Disc 〇〇6 200 VO 93.6 4.10 0.50 &lt;0.01 0.50 0.10 0.50 0.09 0.20 | 0.03 0.20 0.04 &lt;0.01 1 &lt;0.01 〇〇0 ON 0 Disc 10.0 230 92.2 6.65 0.10 &lt;0.01 0.50 0.09 0.08 0.01 0.12 &lt;0.01 0.05 &lt;0.01 &lt;0.01 &lt;0.01 disc 〇&lt;N 〇\ 0 冢to t-H disc od 600 inch 91.6 6.40 0.60 &lt;0.01 0.45 0,10 0.20 0.09 0.23 0.02 0.15 &lt;0.01 &lt;0.01 &lt;0.01 Disc 〇〇δ 0 rn m 92.5 4.70 0.60 0.01 0.95 0.20 0.40 0.09 0.20 0.02 0.15 0.03 &lt;0.01 &lt;0.01 g 00 ο 冢 (N 10.0 250 (N 91.5 6.65 0.65 0,04 0.15 0.01 0.40 0.15 0.20 &lt;0.01 0.14 0.01 &lt;0.01 &lt;0.01 §§ 00 ο ON 0 rH Disc 0 00 220 r ( ON oo 8.80 0.75 &lt;0.01 0.50 0.04 0.20 0-10 0.25 0.02 0.10 0.02 &lt;0.01 &lt;0.01 0 t On 0 ON Disc 0 m Example Zr02 GO ai2o3 Na20 B2〇3 o BaO CaO Fe2〇3+Ti02 i SrO Y2〇3 MgO CuO p205 Turtle at the time of manufacture Cracked glass transfer point Tg(°c) Change in thermal bending strength Temperature (°c) Residual stress (Mpa) One-sided heating test Thermal cycle test Cracking, chalking presence or absence of residual volume expansion ratio (%) Resistance (Ω-cm ) Ingredients (weight ° / 〇) -25- 壊w : Alkali ship. $ crocodile 4: base τ 117809.doc 200800839 Further, the composition and characteristics of the high oxidation fault casting refractories of Comparative Examples 1 to 15 are shown in Table 2.

117809.doc 26-117809.doc 26-

to .92.9.j 丨 5-40 1 0.60 0.09 ο 1 0.05 1 &lt;0.01 &lt;0.01 (Nj d &lt;0.01 1 0.12 &lt;0.01 | &lt;0.01 &lt;0.01 綠 820 800 m i—f r^H 寸 ϊ—ί 92.3 4.45 ο ι &lt; &lt;0.01 ο &lt;0.01 ο r i CN o f-H d (N d 0.15 &lt;0.01 &lt;0.01 &lt;0.01 880 900 s 碟 ο m 〇 m ? '&lt; 92.0 5.88 0.10 &lt;0.01 ο 0.25 0.25 &lt;0.01 0.23 &lt;0.01 1 LahJ 1 &lt;0.01 | &lt;0.01 &lt;0.01 碟 910 o m rn 290 (N 92.9 4.10 0.50 I &lt;0.01 ο 0.25 0.25 0.30 0.40 | &lt;0.01 [ο·” 1 1 &lt;0.011 I &lt;0.011 &lt;0.011 瑞 〇 oo 碟 沄 r-H f rn On 4.00 0.72 0.07 cn ο 0,07 1.00 0.13 0.23 0,03 0.18 0.01 1 &lt;0.01 | ! &lt;0.01 碟 820 800 t—1 1 碟 oo τ—^ 〇 y&quot;H 92.4 4,57 0.55 0.07 0.50 0.06 0.70 0,10 0.30 0.20 0.15 0.20 &lt;0.01 0.10 碟 820 800 oo r—H 1 碟 〇 On 86.5 11.15 0.65 &lt;0.01 0.50 0.02 I 0.20 0.09 1 0.20 &lt;0.01 | 0.15 I | 0.03 1 I &lt;0.011 丨 0.40 〇 CN On o CTs (N 〇 m oo oo 92.5 5.40 0.55 0.04 0.50 0.05 &lt;0.01 0.10 1 0.20 0.08 0.45 0.01 &lt;0.01 &lt;0.01 〇 m oo o § 1 t 1 碟 沄 r-H 卜 92.5 6.06 0.45 &lt;0.01 0.20 &lt;0.0! 0.20 0.10 0.23 0.01 0,16 0.01 &lt;0.01 co.oi | 無(變形)1 g oo o 冢 1 V 250 v〇 93.0 4.00 0.50 0.02 0.50 0,10 1 0.09 | 0.20 0.03 0.17 0.04 I &lt;0.011 &lt;0.01 830 1 o oo oo 1-( 1 碟 »r» (N ο 93.7 4.14 0.55 0.04 0.50 0.40 0.08 0.10 0.20 &lt;0.01 j 0.18 0.01 &lt;0.01 &lt;0.01 800 卜 wn (N τ—Η 寸 91.0 6.10 0.62 ο 1.20 0.10 0.20 0.11 | 0.23 0.02 0.13 0.01 &lt;0.01 &lt;0.01 o r-H CO ο oo CN m 92.7 4.70 1.20 m Ο &lt;0.01 0.05 0.40 0.12 0.20 0.02 0.16 0.03 I &lt;0.011 &lt;0.01 810 ο 00 1 1 4： (N &lt;N 91.6 7·10 0.05 0-01 0.050 0.03 0.40 | 0.18 1 0.20 &lt;0.01 0.18 0.01 &lt;0.01 &lt;0.01 s oo 850 1 1 350 92.7 5.10 0.90 0.02 0.50 &lt;0.01 &lt;0.01 0.18 0.25 &lt;0.01 0.15 | 0.02 I &lt;0.01 &lt;0.01 890 oo 1 ί g r-H 比較例 Zr02 Si02 Α!2〇3 Na20 Β2〇3 BaO CaO |Fe2〇3+Ti〇2 J SrO Y2〇3 MgO CuO P2〇5 製造時之龜裂 玻璃轉移點Tg(°c) 熱彎曲強度之變化溫度(°c) 殘餘應力(Mpa) 單面加熱測試 熱循環測試龜裂、粉化之有無 殘存體積膨脹率(％) 電阻(Ωχηα) 成分 (重量％) 117809.doc -27- 笮W塄_ :碱I -笮鹚奪4:碱4 sw¥ 200800839 表1及表2中之各成分係以重置％单位而計。各成分之分 析’對於K2〇、Na2〇係利用炎光法，對於j&gt;2〇5係利用吸光 法’對於其他成分係利用ICP而進行。然而，本發明並不 限定於該等分析法，亦可利用其他分析法而實施。 玻璃轉移點之測定係，首先，使用EPMA進行高氧化鍅 鑄造耐火物之玻璃相之分析。繼而，於鉑坩鍋中融解並冷 卻而製成相同組成之玻璃。對該玻璃塊進行加工，製作直 徑為8 mm、長度為20 mm之樣本◊繼而，對樣本施加$ # 之荷重，並以每分鐘5t之升溫速度升溫至n〇(rc為止， 測定膨脹率之變化點作為Tg。 熱彎曲強度係，將高氧化錘鑄造耐火物切成厚度10x寬 度20X長度100 _，於碳化石夕發熱體之電爐中以每分鐘5艺 之升溫速度升溫’到達設定溫度後保持10分鐘以上，其後 測定彎曲強度。樣本數各為3塊。 殘餘應力之敎係’藉由使用有應變計之穿孔法而測定 100x300x300 mm之樣本表面的啵測定點之殘餘應力。 於該測定法係根據米谷茂所著之「殘餘應力之產生及對 朿」（養賢堂發行）中所記載之s〇ET，vancr〇m贿_ =進行。首先’對樣本之赚3 00賴之！面，自表面研 磨？3咖。觀察研磨過之面’於會對黏接應變計造成障礙 之：孔内填充環氧樹脂，使之成為平滑之面。 矣k而’於該平滑面 &amp; 展氧樹脂於一處測定點上黏附 3個應變計（共和電隼 古 “ I ain gauge)。應變計，係使用與 间羊^造耐火物之熱膨脹率相符之自身溫度保證型應 117809.doc -28- 200800839To .92.9.j 丨5-40 1 0.60 0.09 ο 1 0.05 1 &lt;0.01 &lt;0.01 (Nj d &lt;0.01 1 0.12 &lt;0.01 | &lt;0.01 &lt;0.01 Green 820 800 mi—fr^H ϊ —ί 92.3 4.45 ο ι &lt;&lt;0.01 ο &lt;0.01 ο ri CN o fH d (N d 0.15 &lt;0.01 &lt;0.01 &lt;0.01 880 900 s discο m 〇m ? '&lt; 92.0 5.88 0.10 &lt;; 0.01 ο 0.25 0.25 &lt; 0.01 0.23 &lt; 0.01 1 LahJ 1 &lt;0.01 | &lt;0.01 &lt;0.01 Disc 910 om rn 290 (N 92.9 4.10 0.50 I &lt;0.01 ο 0.25 0.25 0.30 0.40 | &lt;0.01 [ο ·" 1 1 &lt;0.011 I &lt;0.011 &lt;0.011 〇 〇 沄 沄rH f rn On 4.00 0.72 0.07 cn ο 0,07 1.00 0.13 0.23 0,03 0.18 0.01 1 &lt;0.01 | ! &lt;0.01 Disc 820 800 t—1 1 dish oo τ—^ 〇y&quot;H 92.4 4,57 0.55 0.07 0.50 0.06 0.70 0,10 0.30 0.20 0.15 0.20 &lt;0.01 0.10 dish 820 800 oo r—H 1 dish 〇On 86.5 11.15 0.65 &lt; 0.01 0.50 0.02 I 0.20 0.09 1 0.20 &lt;0.01 | 0.15 I | 0.03 1 I &lt;0.011 丨0.40 〇CN On o CTs (N 〇m oo oo 92.5 5.40 0.55 0.04 0.50 0.05 &lt;0.01 0.10 1 0.20 0.08 0.45 0.01 &lt;;0.0 1 &lt;0.01 〇m oo o § 1 t 1 Disc 沄rH Bu 92.5 6.06 0.45 &lt;0.01 0.20 &lt;0.0! 0.20 0.10 0.23 0.01 0,16 0.01 &lt;0.01 co.oi | No (deformation) 1 g oo o冢1 V 250 v〇93.0 4.00 0.50 0.02 0.50 0,10 1 0.09 | 0.20 0.03 0.17 0.04 I &lt;0.011 &lt;0.01 830 1 o oo oo 1-( 1 dish »r» (N ο 93.7 4.14 0.55 0.04 0.50 0.40 0.08 0.10 0.20 &lt;0.01 j 0.18 0.01 &lt;0.01 &lt;0.01 800 wn (N τ - Η inch 91.0 6.10 0.62 ο 1.20 0.10 0.20 0.11 | 0.23 0.02 0.13 0.01 &lt;0.01 &lt;0.01 o rH CO ο oo CN m 92.7 4.70 1.20 m Ο &lt;0.01 0.05 0.40 0.12 0.20 0.02 0.16 0.03 I &lt;0.011 &lt;0.01 810 ο 00 1 1 4: (N &lt;N 91.6 7·10 0.05 0-01 0.050 0.03 0.40 | 0.18 1 0.20 &lt;;0.01 0.18 0.01 &lt;0.01 &lt;0.01 s oo 850 1 1 350 92.7 5.10 0.90 0.02 0.50 &lt;0.01 &lt;0.01 0.18 0.25 &lt;0.01 0.15 | 0.02 I &lt;0.01 &lt;0.01 890 oo 1 ί g rH Comparative Example Zr02 Si02 Α!2〇3 Na20 Β2〇3 BaO CaO |Fe2〇3+Ti〇2 J SrO Y2〇3 MgO CuO P2〇5 Cracked glass transfer point Tg(°c) heat during manufacture Temperature change temperature (°c) Residual stress (Mpa) One-sided heating test Thermal cycle test Crack, powder presence or absence of residual volume expansion ratio (%) Resistance (Ωχηα) Composition (% by weight) 117809.doc -27-笮W塄_: base I - 笮鹚 4: base 4 sw¥ 200800839 Each component in Tables 1 and 2 is based on the % unit of reset. The analysis of each component was carried out by using ICP for the K2〇 and Na2〇 systems by the illuminating method, and for the j&gt;2〇5 system by the absorbing method. However, the present invention is not limited to the analysis methods, and may be carried out by other analysis methods. The glass transition point was determined by first analyzing the glass phase of the high cerium oxide cast refractory using EPMA. Then, it is melted in a platinum crucible and cooled to form a glass of the same composition. The glass block was processed to prepare a sample having a diameter of 8 mm and a length of 20 mm, and then a load of $# was applied to the sample, and the temperature was raised to n〇 (rc until the temperature of 5 t per minute, and the expansion ratio was measured. The change point is Tg. The thermal bending strength system cuts the high oxide hammer cast refractory into a thickness of 10x width and 20X length of 100 _, and heats up at a heating rate of 5 art per minute in an electric furnace of a carbonized stone heater. The tensile strength was measured for 10 minutes or more, and the bending strength was measured. The number of samples was 3 pieces. The residual stress was determined by measuring the residual stress of the 啵 measurement point of the sample surface of 100×300×300 mm by using a perforation method with a strain gauge. The measurement method is based on the s〇ET, vancr〇m bribes written in the “Residual Stress Generation and Confrontation” (promulgation of Yangxiantang) by Mi Gumao. First of all, the profit of the sample is 30,000. Face, self-surface grinding? 3 coffee. Observing the ground surface' will cause obstacles to the adhesion strain gauge: the hole is filled with epoxy resin to make it a smooth surface. 矣k and 'the smooth surface &amp; Oxygen resin in one Three strain gauges are attached to the measuring point (Iain gauge). The strain gauges are self-temperature-guaranteed in accordance with the thermal expansion rate of the refractory made by the sheep. 117809.doc -28- 200800839

變计，亚利甩3線式接線法與測定器相接。自身溫度保證 型應變計，可減少因測定樣品之溫度變化而導致的表觀應 變，因此可減少測定誤差。又，3線式接線法與先前所使 用之2線式接、線法相比，彳去除因導線之溫度變化而導致 的表觀應變，故而較好。該應變計為長方形，並以其長度 方向之中心線相互成12〇度之角.度的方式而黏附。繼而， 於該中心線相交之位置上，利用測定器（共和電業製 =CAM-20A)測定因_出直徑為25咖之貫通孔而產生的應 又使口亥值藉由三向應變分析而計$出殘餘應力。殘餘 應力為拉伸應力時以正數表示，為壓縮應力時以負數表 不。為負數時，數字越大則壓縮應力越大。 單面力…、測忒係，將1〇〇x3〇〇x3〇〇 mm之樣本設置於電 爐内’ U使300x300 mm之面在爐内，而相反側與外部空 氣相接觸。使樣本卩每分鐘1〇〇，c之升溫速度升溫至 1000°C為止，測定升溫時有無龜裂。 熱循環穩定性係，自100x300x300 mm之樣本之底部切 出50 50 mm之樣本。將樣本***電爐内，以每分鐘 3 C之升/jHL速度升溫至8G(rc為止並保持！小時。此後，以 母分鐘3°C之升溫速度升溫至12⑽。c為止並保持！小時。此 後’以母分鐘3’C之冷卻速度冷卻至8〇〇〇c為止。此後，反 覆進行該刚1與12()代之熱循環45次，逐漸冷卻後，觀 察有無龜裂或粉化。進而’測定熱循環測 化，計算出殘存體積膨脹率。 &lt; 又，若熱循環測試中殘存體積膨脹率超過ι〇%，則會生 I17809.doc -29- 200800839 成錯英石。並且，殘在 I鉑夕 存體積杉脹率越大，則銼英石之生成 里越多。於熱循 Λ 昝 、’、0中殘存體積膨脹率超過10%而生成 鉛央石之表2之比較例中 樣隨時間婵加…測定值與圖2之比較例9同 1 wn變化之穩定性較差。 龟阻係精由基於 JISR1650·2之四端子法而測定的。採用 19 mm徑之岩芯，自 山 ，本刀』出長度30 mm之樣本。於距 離兩金而部5 mm部分之矣而、杜/ *The meter, the Alibaba 3-wire wiring method is connected to the measuring device. The self-temperature-guaranteed strain gage reduces the apparent strain caused by the temperature change of the measured sample, thus reducing the measurement error. Further, the 3-wire type wiring method is preferable to the 2-wire type connection and line method previously used, since the 表 is removed by the apparent strain caused by the temperature change of the wire. The strain gauges are rectangular and adhered in such a manner that their center lines in the longitudinal direction are at an angle of 12 degrees to each other. Then, at the position where the center line intersects, the measuring device (Kyowa Electric Co., Ltd. = CAM-20A) is used to measure the through hole of the diameter of 25 coffee, and the value of the mouth is analyzed by the three-direction strain. And the residual stress is calculated. The residual stress is expressed as a positive number for tensile stress and negative for compressive stress. When it is negative, the larger the number, the greater the compressive stress. Single-sided force..., measuring system, set a sample of 1〇〇x3〇〇x3〇〇 mm in the furnace' U so that the surface of 300x300 mm is in the furnace, and the opposite side is in contact with the external air. The sample 卩 was set to 1 Torr per minute, and the temperature increase rate of c was raised to 1000 ° C, and the presence or absence of cracking at the time of temperature rise was measured. Thermal cycling stability was performed by cutting a 50 50 mm sample from the bottom of a 100 x 300 x 300 mm sample. Insert the sample into the electric furnace and raise the temperature to 8G (rc until rc!) at a rate of 3 C/jHL per minute. After that, the temperature is raised to 12 (10) at the temperature rise rate of 3 °C at the mother's minute. 'Cooling to 8 〇〇〇c at a cooling rate of 3'C at the mother's minute. Thereafter, the heat cycle of the first 1 and 12 () was repeated 45 times, and after cooling, the presence or absence of cracking or chalking was observed. 'Measure the thermal cycle measurement and calculate the residual volume expansion rate. · Also, if the residual volume expansion rate in the thermal cycle test exceeds ι〇%, I17809.doc -29- 200800839 will be born into the wrong stone. In the case of I platinum, the larger the volume expansion rate, the more the formation of strontium stone. The comparison example of Table 2 in which the residual volume expansion ratio of heat cycle ', ', 0 exceeds 10% to produce lead shale. The sample was added over time... The measured value was inferior to the comparison of Example 9 in Figure 2. The stability of the same wn change was determined by the four-terminal method based on JISR1650·2. The core of 19 mm diameter was used. From the mountain, the knife is a sample with a length of 30 mm. It is 5 mm away from the two gold parts. Du / *

丨刀之表面進行溝槽加工後，進行超聲波清 山”利用乾燥機乾燥。乾燥後，將鉑板設置於樣本之兩 ::於溝：部分纏繞鉑線作為端子，藉由交流Μ Hz之函 文波產生盗產生固定電壓，測定施加於樣本以及電阻設定 為與樣本相同程度之標準電阻的電壓，自所獲得之電廢值 求出樣本之電阻值。敎係以每分鐘代之升溫速度升溫After the surface of the file is grooved, the ultrasonic cleaning is carried out by a dryer. After drying, the platinum plate is placed in the sample two: in the groove: a part of the platinum wire is wound as a terminal, and the letter of AC Μ Hz is used. The wave generates a fixed voltage, measures the voltage applied to the sample and the resistance is set to the same standard resistance as the sample, and the resistance value of the sample is obtained from the obtained electric waste value. The temperature is increased by the rate of temperature increase per minute.

j15〇(rc為止後，保持12小時而進行的。測定到達150(TC 日可之電阻值’進而’確認保将12小時後之電阻值為穩定 值。繼而，求出保持12小時後之電阻測定值，作為15〇〇。〇 之電阻值。 表1所示之貝知例丨至貫施例1 〇處於本發明之範圍内。 表2所示之比較例！，與前文所述之w〇 2⑽68393號所 揭示之發明之實施例相對應。通常，於氧化錯原斜中，含 有1重里A左右之丫2〇3作為雜質。於WO 2005/068393號 中，對於BaO及K2〇之揭示並不明確，但若考慮到w〇 2005/068393號中實施例之分析值之總量及Υ2〇3含量，則 可明確’於該等製品中不含有尺2〇或^〇。 於比較例1中，NaaO較少，然而A12〇3較多，因此電阻不 117809.doc -30- 200800839 充分。 又’知2〇較少且不含有K2〇及㈣，因此，熱循環測試 &lt;之殘存體積膨脹率較大，缺乏對熱循環之穩定性。 比車父例2係a12〇3、32〇3較少之干办丨 裂。 不例。於製造時產生了龜. 電阻較高’但熱循環測試後產生龜裂而粉化。 時r:i2°3、叫〇較多而β2〇3較少之情形。於製造 低。 裂°又，雖具有熱循環测試穩定性，但電阻較 比較例4係Na2〇、β2〇3較多之愔 面加熱測試後，產生列 〆。塾縮應力較大，單 衣痕。熱循環測試後之殘存體積膨 脹率亦較大，電阻亦較低。 ^ &quot; 比較例5係K2〇較吝夕一点丨 _ 殘存μ— _ ° tFw低’熱«測試後之 歹欠存體積膨脹率較大，缺乏«循環之穩定性。 比車乂例ό係Ba〇較多之示例。電阻 之=積膨脹率較大，缺乏對熱循二Γ測試後 “乂例7係K2〇、Na2〇較少之 高，製品成為凹陷之形狀。隨，公時黏性較 之殘存體積膨脹率亦較大而粉環測試後 性。 、乏對熱循環之穩定 比較例8係知〇較少、心0及Y2〇5較多 低，缺乏對熱循環之穩定性。 ’、例。電阻較 比較例9係Zr〇2、Si〇2較多且含有Μ之 較高，但缺乏經時穩定 5下列。雖電阻 熱循環測試後之殘存體藉 117809.doc 200800839 膨脹率較大而粉化。 比較例10係Na20、MgO、SrO較多且含右公^ ^ ^ , h〇5，相當於 則文所述之日本專利特開平8_277162號公 / ϊ 心只施例的干 歹*。電阻較低，熱循環測試後之殘存體積膨 “ 乏對.熱循環之穩定性。 缺 比較例11係Na20、Ba0較多，相當於 剎4主P目Τ η 引乂所迷之曰本專 利特開平8-48573號公報之實施例的示例。 寻 電阻較低。 比較例12係CaO、Fe2〇3+Ti〇2較多之示例。 熱循環測試後之殘存體藉p 交 乂 S* ’ 定性。 殘存體積祕杨大，缺乏fm循環之穩 比較例η係不含有Na2〇,相當於前文所述 開昭63-285173获八相 ^ 本專利特 唬A報之貫施例的示例。雖電阻較古^ 拉伸應力較大，而认抑 电,罕乂问’但 而於早面加熱時產生了龜裂。 後之殘在舻接阶昨* 熱循核測試 绞存體積膨脹率亦較大而粉化。 比較例14係Al2〇3、Ba〇、夕 之示例，且較多且不含有ν~〇、κ2〇 號公報之實施㈣_文所权日本專料開平4 i 9 3 7 6 6 定性。 电,力罕乂低缺乏對熱猶環之穩 比較例1 5係NhO較吝日丁人士上人 乂夕且不含有鹼土類氧化物之示例，且 馮相虽於前文所述之日士宙心&amp; 且 施例的亍存丨Φ 日I專利特開平10-59768號公報 時產生了龜列。敎t 應力較大而於單面加熱 衣，、、、# %測試後之殘存體積膨脹率亦較大， 缺乏對熱循環之穩定性。 叙大 117809.doc -32- 200800839 【圖式簡單說明】 圖1係表不高氧化錯鱗造耐火物之熱彎曲強度測定結果 的圖。多數&gt; + 之而疋溫度（25〜14〇〇。〇下之彎曲強度係將比勤 例4與本發明進行對比而表示。 圖2 4系表示丄卜 圖。 ’、呵氧化錯禱造耐火物之電阻之經時變化的J15〇 (after rc, it was kept for 12 hours. The measurement reached 150 (the resistance value of TC day) and then confirmed that the resistance value after 12 hours was stable. Then, the resistance after 12 hours was obtained. The measured value is taken as the resistance value of 15 〇〇. The examples shown in Table 1 are within the scope of the present invention. The comparative example shown in Table 2, and the above-mentioned w Corresponding to the embodiment of the invention disclosed in No. 2 (10) No. 68,393. Generally, in the oblique direction of the oxidation, a ruthenium 2 〇 3 containing about 1 aliquot of A is used as an impurity. In WO 2005/068393, the disclosure of BaO and K2 〇 is disclosed. It is not clear, but considering the total amount of analytical values and the Υ2〇3 content of the examples in WO〇2005/068393, it can be clarified that 'these products do not contain the ruler 2〇 or ^〇. In 1 case, NaaO is less, but A12〇3 is more, so the resistance is not sufficient 117809.doc -30- 200800839. Also know that 2〇 is less and does not contain K2〇 and (4), therefore, the thermal cycle test &lt; The volume expansion ratio is large, and the stability to the thermal cycle is lacking. It is less than the car parent's case 2 a12〇3, 32〇3. It is produced by a crack. It is produced at the time of manufacture. The resistance is high. But after the thermal cycle test, cracks are formed and powdered. When r: i2°3, there are more sputum and β2〇3 is less. In the case of low manufacturing, the crack has a thermal cycle test stability, but the resistance is higher than that of the comparative example 4, Na2〇, β2〇3, and the tantalum heating test produces a tantalum. The contraction stress is large. Single clothing marks. The residual volume expansion rate after thermal cycle test is also large, and the resistance is also low. ^ &quot; Comparative Example 5 is K2〇 吝 丨 丨 _ Remaining μ _ ° tFw low 'hot« after test The volume expansion ratio of the under-reserved volume is large, and the stability of the cycle is lacking. The example of the 〇 〇 比 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻K2〇 and Na2〇 are less high, and the product becomes a shape of a depression. The public viscosity is larger than that of the residual volume and the powder ring is tested. The stability of the fatigue cycle is compared with the case of the thermal cycle. Less 、, heart 0 and Y2 〇 5 are much lower, lacking stability to thermal cycling. ', Example. Resistance is better than Comparative Example 9 Zr 〇 2 Si〇2 is more and contains higher yttrium, but lacks stability over time. 5 Although the residual body after resistance thermal cycling test is 117809.doc 200800839, the expansion ratio is larger and pulverized. Comparative Example 10 is Na20, MgO SrO is more and contains right ^ ^ ^ , h 〇 5 , which is equivalent to the Japanese patent special opening 8_277162 / ϊ 只 only the dry 歹 *. The resistance is low, the residual after the thermal cycle test The expansion of the volume is "lack of stability. The stability of the thermal cycle. The lack of Comparative Example 11 is more than Na20, Ba0, which is equivalent to the brake of the main P-type Τ 乂 乂 曰 实施 实施 实施 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 Example. The sourcing resistance is low. Comparative Example 12 is an example in which CaO and Fe2〇3+Ti〇2 are many. The residual body after the thermal cycle test is characterized by p 交 S* ’. The residual volume is large, and the stability of the fm cycle is lacking. The comparative example η does not contain Na2〇, which is equivalent to the example of the above-mentioned example of the application of the eight-phase patent. Although the resistance is relatively large, the tensile stress is large, and the electric resistance is suppressed. However, cracks are generated when heating on the early surface. After the residual in the 阶 昨 yesterday * hot nuclear test swell volume expansion rate is also large and powdered. Comparative Example 14 is an example of Al2〇3, Ba〇, and Xi'an, and many of them are not included in the implementation of the publication of ν~〇, κ2〇 (4) _ Wenquan Japanese special material Kaiping 4 i 9 3 7 6 6 Qualitative. Electricity, the strength is low, and the lack of heat is relatively stable. Example 1 The 5 series NhO is an example of a Japanese person who does not contain alkaline earth oxides, and Feng Xiang is a Japanese scholar as described above. The heart &amp; and the application of the 丨 丨 日 I Japanese Patent Laid-Open No. 10-59768 issued a turtle column.敎t The stress is large and the residual volume expansion rate after the single-sided heating coat, ,, #% test is also large, and the stability to the thermal cycle is lacking. SYDa 117809.doc -32- 200800839 [Simple description of the drawing] Fig. 1 is a graph showing the results of measurement of the thermal bending strength of a refractory which is not highly oxidized. Most of the temperature is (25~14〇〇. The bending strength of the underarm is compared with the present invention in comparison with the present invention. Fig. 2 is a diagram showing the 丄 图. Refractory resistance change over time

圖3係表示實 圖4係表示實 施例4之電阻測定後 施例9之電阻測定後 之顯微鏡相片的圖 之顯微鏡相片的圖Fig. 3 is a view showing a micrograph of a micrograph of the electric resistance measurement after the electric resistance measurement of the embodiment 9 after the electric resistance measurement of the fourth embodiment.

117809.doc 33-117809.doc 33-

Claims (1)

200800839 十、申請專利範圍： 1 · 一種咼氧化鍅鑄造耐火物，其特徵在於：其係與玻，璃相 之1000。(：附近之黏度相關的特性及耐火物表面之殘餘應 力得到控制者，其化學成分為：Zr〇2為87重量％以上、 96重量％以下，Al2〇3為〇]重量％以上、小於〇 8重量％， Si〇2為3重量％以上、1〇重量％以下，化2〇為小於0 05重 量°/〇 ’ K2〇為〇,〇1重量％以上、〇·2重量％以下，為 _ 〇·1重量％以上、1.0重量％以下，BaO為0·1重量％以上、 〇.5重量％以下，St〇為小於〇.05重量％，〜〇為〇 〇1重量 %以上、〇·15重量％以下，Y2〇3為0·05重量％以上、〇 4重 量％以下，MgO為0·1重量％以下，Fe203與Ti02之總量為 0·3重1%以下’實質上不含有pas及Cu〇(小於〇〇1重量 %)’且該高氧化錯鑄造耐火物於1 5 00 °C下保持1 2小時後 的電阻為200 Ω cm以上。 2 · 種n乳化錯麵造耐火物’其特徵在於：其係與玻璃相 • 之1 0 0 0 °C附近之黏度相關的特性及耐火物表面之殘餘廯 力得到控制者，其化學成分為：Zr02a 88重量％以上、 96重里％以下’八丨2〇3為〇.1重量％以上、小於〇.8重量％， • Si〇2為3重量％以上、9重量％以下，NaW為小於〇·〇4重量 %，K2〇為〇.〇1重量％以上、〇.15重量％以下，B2〇3g 〇 j 重量％以上、0.7重量％以下，BaO為0.1重量％以上、〇 5 重量。/〇以下，SrO為小於〇·〇5重量％，CaO為〇·〇ι重量％以 上、0.15重量％以下，Y2〇3為〇·〇5重量％以上、〇·2重量％ J 以下，MgO為0·05重量％以下，Fe203與Ti02之總量為〇 3 117809.doc 200800839 重量％以下，實質上不含有ho〗及Cu〇(小於〇〇1重量 °/〇) ’且該高氧化鍅鑄造耐火物於1 5 〇〇它下保持丨2小時後 的電阻為200 Ω cm以上。 3·如請求項1或2之高氧化鍅鑄造耐火物，其表面上之殘餘 應力為30 MPa以下之拉伸應力、2〇 MPa以下之壓縮應 力。 4·如請求項1至3中任一項之高氧化錯鑄造耐火物，其於熱 彎試驗中，自脆性破壞變化至伴有塑性變形之破壞的溫 度為 850°C 至 950。(：。 5·如請求項1至4中任一項之高氧化锆鑄造耐火物，其中高 氧化錯鑄造耐火物中玻璃相之玻璃轉移點（Tg)為85〇〇c至 950〇C 〇 6·如請求項1至5中任一項之高氧化鍅鑄造耐火物，其熱循 環測試後之殘存體積膨脹率為1 0%以下。 7·如請求項1至6中任一項之高氧化錯鑄造耐火物，其於 1500 C下保持12小時後的電阻為250 Ω cm以上。 117809.doc200800839 X. Patent application scope: 1 · A bismuth oxide ruthenium cast refractory, characterized in that it is 1000 with glass and glass. (The viscosity-related characteristics in the vicinity and the residual stress on the surface of the refractory are controlled, and the chemical composition is: Zr〇2 is 87% by weight or more and 96% by weight or less, and Al2〇3 is 〇]% by weight or more and less than 〇 8 wt%, Si〇2 is 3% by weight or more and 1% by weight or less, and 2 〇 is less than 0 0 weight 〇 / 〇 ' K2 〇 is 〇, 〇 1% by weight or more, 〇 · 2% by weight or less, _ 〇·1% by weight or more and 1.0% by weight or less, BaO is 0.1% by weight or more, 〇.5% by weight or less, St〇 is less than 〇0.55% by weight, and 〇 is 〇〇1% by weight or more, 〇 15% by weight or less, Y2〇3 is 0.055% by weight or more, 〇4% by weight or less, MgO is 0.1% by weight or less, and the total amount of Fe203 and TiO2 is 0·3 and 1% or less. Containing pas and Cu〇 (less than 〇〇1% by weight)' and the resistance of the high-oxidation casting refractory after holding at 150 ° C for 12 hours is 200 Ω cm or more. 2 · n emulsified surface The refractory is characterized in that it is related to the viscosity of the glass phase at around 1000 ° C and the residual force of the refractory surface. The chemical composition of the product is: Zr02a 88% by weight or more, 96% by weight or less 'Eight 丨 2 〇 3 is 1. 1% by weight or more, less than 8 8% by weight, • Si 〇 2 is 3% by weight or more, 9 The weight % or less, NaW is less than 〇·〇4% by weight, K2〇 is 〇.〇1% by weight or more, 〇15% by weight or less, B2〇3g 〇j% by weight or more, 0.7% by weight or less, and BaO is 0.1% by weight. % or more and 〇5 by weight. /〇, SrO is less than 〇·〇5 wt%, CaO is 〇·〇ι wt% or more, 0.15 wt% or less, and Y2〇3 is 〇·〇5 wt% or more, 〇· 2% by weight or less, MgO is 0. 5% by weight or less, and the total amount of Fe203 and TiO 2 is 〇3 117809.doc 200800839% by weight or less, and substantially does not contain ho and Cu 〇 (less than 〇〇1 weight ° / 〇 'And the resistance of the high cerium oxide cast refractory after holding it for 15 hours under 15 〇〇 is 200 Ω cm or more. 3. The high cerium oxide cast refractory according to claim 1 or 2, on the surface thereof The residual stress is a tensile stress of 30 MPa or less and a compressive stress of 2 〇 MPa or less. 4. According to any one of claims 1 to 3 Oxidation mis-cast refractory, in the hot bending test, the temperature from the brittle failure to the destruction with plastic deformation is 850 ° C to 950. (: 5. The high of any one of claims 1 to 4 A zirconia cast refractory wherein the glass transition point (Tg) of the glass phase in the high oxidation fault cast refractory is from 85 〇〇c to 950 〇C 〇6. The high yttria casting according to any one of claims 1 to 5 The refractory has a residual volume expansion ratio of 10% or less after the heat cycle test. The high-oxidation-staggered cast refractory according to any one of claims 1 to 6, which has a resistance of 250 Ω cm or more after being held at 1500 C for 12 hours. 117809.doc