201100351 六、發明說明： 【發明所屬之技術領域】 本發明關氧化鋁-碳磚、氧化鋁-碳化矽-碳磚、氧化 鋁-氧化鎂-碳磚等的氧化鋁碳系不燒磚，其係使用於鐵液 輸送或進行脫矽、脫磷、脫硫等的鐵液預備處理之混鐵車 或澆桶的內襯、或滑動噴嘴裝置的板磚、上部噴嘴、下部 噴嘴等。又，關於使用氧化鋁碳系不燒磚之窯爐設備。 Ο 【先前技術】 氧化鋁碳系碍係在以氧化鋁原料與碳原料當作基本構 成的耐火原料配合物中添加有機黏結劑當作黏合劑，進行 混煉、成形後，經由熱處理而製造之具有碳鍵結的氧化銘 系耐火物。特別地，在I 0 0 0 °c以下的溫度進行熱處理的不 燒型，由於可低成本製造且耐用性優異，故現在係成爲鋼 鐵用磚的主流。 〇 於此氧化鋁碳系不燒磚中，除了氧化鋁原料與碳原料 以外’視其用途或使用條件而定’亦使用各式各樣的耐火 原料。例如，於作爲鐵液用的澆桶之內襯所用的磚中使用 氧化鎂（粗粒）或尖晶石（粗粒），於混鐵車的內襯用磚 中使用碳化矽，於滑動噴嘴裝置中所用的板磚中使用氧化 锆高鋁紅柱石或氧化鋁氧化锆等。又，以耐氧化性爲目的 ，亦使用金屬粉、硼化物或玻璃等當作耐火原料。 於此氧化鋁碳系不燒磚中，進一步以對熔渣的耐餓性 提商或使用時的接縫裂開防止爲目的時，有使用氧化鎂或 -5- 201100351 尖晶石的微粉當作耐火原料。此想法爲藉由使用時的熱， 使磚中的MgO或尖晶石中的Mg與氧化鋁原料進行反應而 生成耐熔渣性強的尖晶石，再藉由尖晶石生成時的膨脹而 使組織緻密化，以提高耐蝕性。 然而，氧化鎂係與空氣中的水分反應，有水合及膨脹 的性質（熟化），尤其以粒徑1 ΟΟμηι以下的微粉使用時會 有問題。例如，築爐時，在爐內以加有微粉氧化鎂的氧化 鋁碳系磚當作襯裏，然後進行預熱時，由於在此磚的背面 側所使用的砂漿的水分所產生的水蒸氣，磚中的氧化鎂被 水合而膨脹，會大幅減低磚組織的強度。因此，使用氧化 鎂時，一般組合使用不易熟化的氧化鎂之粗粒與氧化鋁的 微粉或超微粉。因此，利用氧化鎂的尖晶石形成係活性低 ，其耐蝕性提高效果係有限度。再者，以往一般地於耐火 原料之分類中，粗粒係意味粒徑1 mm以上，微粉係意味 ΙΟμιη以上且未達1mm，超微粉係意味粒徑未達ΙΟμιη的 程度。但是，於後述的本發明之尖晶石超微粉中，不受上 述以往的分類所拘束，而是依照本發明的定義。 又，代替氧化鎂，亦有使用含有MgO且不易熟化的 尖晶石。 例如，專利文獻1中記載一種氧化鋁-氧化鎂富化尖 晶石-碳磚，其係配合10〜80質量％的Mg0/Al203之質量 比爲50/50〜95/5且MgO與Al2〇3之合計量爲95質量％以 上的電熔氧化鎂富化尖晶石原料、3〜6 0質量％的碳質原 料及1 〇〜8 5質量％的氧化鋁質原料所成。此氧化鋁-氧化 201100351 鎂富化尖晶石-碳磚，由於不易與熔渣中所含有的CaO成 分等進行反應，而提高耐熔渣性，而且即使尖晶石的含量 爲比較少量，也可得到適度殘存膨脹率的磚。 另外，專利文獻2中記載相對於全配合量而言，添加 0.5〜4 · 0質量％的氧化鎂或氧化鎂富化尖晶石中任一者之 粒徑1 00 μηι以下的微粉當作方鎂石，基質部爲碳鍵結與尖 晶石鍵結的組織的氧化鋁-碳化矽-碳質耐火物。由於此氧 〇 化鎂或氧化鎂富化尖晶石係在1 2 5 0 °c以上與氧化鋁進行反 應，而生成尖晶石’故爲了提高分散性，宜儘可能地微細 (較佳爲粒徑50μπι以下，但作爲耐火物原料係粒徑 1 0 0 μ m 以下）。 又，專利文獻3中記載一種含碳耐火物之製造方法， 其特徵爲將碳系黏合劑加到含有3 0〜9 0質量％的氧化纟呂質· 材料、3〜3 0質量％的碳材料、5〜5 0質量。/〇的粒徑1 m m 以下之Al：2〇3-MgO系尖晶石質材料、〇_ι〜5質量％的外掛 〇之玻璃質材料的配合物中，進行混煉、成形、乾燥。記載 此耐火物係藉由在玻璃質材料的介在下，尖晶石粒彼此結 合’在耐火物使用中的工作面上形成尖晶石交聯層，而可 得到耐蝕性及耐氧化性優異的耐火物。 [先前技術文獻] [專利文獻] [專利文獻1]特開平5-238811號公報 [專利文獻2 ]特開昭5 9 - 3 0 6 9號公報 [專利文獻3]特開平9-25160號公報 201100351 【發明內容】 發明所欲解決的問題 專利文獻1的氧化鋁-氧化鎂富化尖晶石-碳磚’由於 氧化鎂富化尖晶石中的Mg〇含量多’與空氣中的水分進 行反應，而有容易發生自由的MgO之水合反應的問題。 又，於專利文獻1的表2中’記載使用粒徑1 m m以下的 尖晶石，但是於1 mm以下的粒徑之特別規定中，特別是 粒徑大時，其影響顯著出現，由於其使用量，起因於尖晶 石結晶相的高熱膨脹率所致的熱衝撃抵抗性之降低，剪切 應力增大而有破裂、剝離等的問題。 專利文獻2之使用粒徑1 00 μπι以下的氧化鎂富化尖晶 石之氧化鋁碳系磚的情況，雖然確實看到耐蝕性的提高效 果’但是不充分。β卩，於焦爐使用時，依然耐蝕性係成爲 瓶頸壽命，而希望耐蝕性的進一步提高。又，專利文獻2 中亦有發生水合的問題。 於專利文獻3的氧化鋁-尖晶石-碳-玻璃系耐火物之情 況，耐蝕性雖然升高，但因爲係由在高溫將尖晶石粒彼此 的鍵結軟化之玻璃質材料所形成，故熱強度降低，而且因 爲鍵結部分的耐飽性降低，故耐飽性的改善效果係有限。 因此’本發明所欲解決的問題爲在已添加尖晶石的氧 化鋁碳系不燒磚中’抑制水合反應，進一步提高耐飩性。 又’提供使用此氧化鋁碳系不燒磚的窯爐設備。 解決問題的手段 -8 - 201100351 本發明者進行專心一致的硏究，結果發現爲了抑制氧 化鋁碳系不燒碍中的水合反應，提高耐蝕性，必須對於耐 火原料配合物中所配合的尖晶石原料，特別規定（1 )平 均粒徑、（2 ) MgO含有率、（3)耐火物原料配合物中的 含量（配合量）。 即本發明的氧化鋁碳系不燒磚，係以氧化鋁原料與碳 原料當作主原料，且於含有鋁及/或鋁合金以及尖晶石超 〇 微粉的耐火原料配合物中添加有機黏結劑進行混煉、成形 後，在1 000°C以下熱處理而得之氧化鋁碳系不燒磚，其特 徵爲耐火原料配合物中的尖晶石超微粉係粒徑未達150μιη 且平均粒徑爲0.1〜50 μιη、MgO含量爲5〜50質量％而剩 餘部分由ai2o3所構成，耐火原料配合物中的尖晶石超微 粉之含量含2〜20質量％。 當在氧化鋁碳系不燒磚的耐火原料配合物中配合尖晶 石原料時，若如上述專利文獻2不添加鋁及/或鋁合金而 Ο 特別指定粒徑1 ΟΟμπι以下，則二次尖晶石生成反應慢，二 次尖晶石生成所致的耐蝕性提高之效果小。爲了增大二次 尖晶石的生成，有增大尖晶石的配合量，或增大尖晶石中 的MgO含量之手法，但因爲此等手法會導致耐熟化性的 降低，故實用上問題多。相對於此，本發明所使用的尖晶 石超微粉，由於其平均粒徑爲0.1〜50μιη而比表面積大’ 故活性非常高。因此’在磚內部的還原環境下，由於A1 係共存，而尖晶石超微粉容易成爲Mg氣體，於周圍的氧 化鋁原料表面被再氧化，生成二次尖晶石。再者’於磚工 -9 - 201100351 作表面，此Mg氣體與熔渣成分中的Al2〇3或CaO進行反 應，在磚表面上形成連續的尖晶石質保護層。因此可提高 耐蝕性。尙且，尖晶石超微粉所致的上述作用效果’係在 其粒徑未達1 5 0 μηι時能顯著達成。因此’本發明中所言的 尖晶石超微粉係以粒徑未達1 5 0 μηι爲前提’更且以平均粒 徑爲〇. 1〜50μιη當作要件。對於粒徑爲1 50μπι以上的尖 晶石原料，本發明中沒有特別的限定’可連同尖晶石超微 粉一起配合，也可不配合。 此處，於本發明中，所謂的粒子的粒徑未達d ’就是 意味該粒子係通過JIS-Z8 80 1規定的網眼d之篩的粒度’ 所謂的粒子的粒徑爲d以上，就是意味該粒子殘留在相同 篩上的粒度。又，於本發明中，平均粒徑係意味將用雷射 繞射散射式粒度分布計所測定的粒徑與質量比例繪成曲線 圖，累計比例爲50%時的粒徑。 圖1係本發明的氧化鋁碳系不燒碍之熔渣耐蝕性試驗 後的微構造之模型圖，確認在與熔渣3的邊界之磚1表面 上，形成以尖晶石當作主成分的尖晶石質保護層2。本發 明係藉由如此的作用，不大量地使用氧化鎂含量比較少的 尖晶石，而可充分地生成二次尖晶石。 又，已抽掉Mg氣體的尖晶石係含有微細的氣孔，同 時在氧化鋁原料表面上所生成的二次尖晶石之結晶粒間亦 生成空隙，結果超過黏結劑的揮發份而增大氣孔率。結果 氣孔率增加，同時藉由所生成的二次尖晶石之鍵結，而提 高強度，抑制彈性模數的降低，提高耐熱衝撃性。此氣化 -10- 201100351 反應所致的二次尖晶石生成，僅藉由以往粒徑1 00μιη以下 的特定尖晶石原料係難以產生，而藉由平均粒徑爲0.1〜 50μιη的尖晶石超微粉之使用與鋁及/或鋁合金的添加才變 顯著。若平均粒徑未達0.1 μιη，則容易水合，而若超過 5 0 μ m ’則二次尖晶石的生成量變少，故耐蝕性的提高效果 降低。爲了促進二次尖晶石的生成，尖晶石超微粉的平均 粒徑較佳爲小者，更佳爲4〇μπι以下，尤佳爲30μιη以下 ◎ ，最佳爲15μιη以下。 本發明所使用的尖晶石超微粉之化學組成係MgO含 量爲5〜50質量％，而剩餘部分爲Al2〇3 (當然，包含無 可避免的雜質）。尖晶石超微粉的MgO含量若未達5質 量％，則特性接近氧化鋁超微粉，在高溫時超微粉彼此發 生燒結，發生粒徑的增大、二次尖晶石生成反應的停滯。 另一方面，尖晶石超微粉的MgO含量若過50質量％，則 有變容易熟化的問題。 Ο 此尖晶石超微粉係以耐火原料配合物中的尖晶石超微 粉之含量成爲2〜20質量％方式進行配合。若未達2質量 %，則所生成的二次尖晶石之比例少，耐蝕性或熱彎曲強 度的增大效果小。若超過2 0質量％，則M g氣體揮發後的 氣孔率增大，同時磚的熱膨脹變大，發生破裂損傷，有實 用上的問題。 本發明的耐火原料配合物中所配合的鋁及鋁合金，係 具有在磚之使用中將尖晶石中的MgO還原，更生成Mg氣 體的作用。鋁及鋁合金在耐火原料配合物中的合計量較佳 -11 - 201100351 爲0.3〜5質量％。若未達〇 · 3質量％，則二次尖晶石的生 成促進效果變小，而若超過5質量％，則由於所生成的碳 化鋁或氮化鋁而使組織變過度緻密，耐熱衝撃性降低。 此處’本發明的耐火原料配合物之主原料的氧化鋁原 料與碳原料之配合量（耐火原料配合物中的含量）係可爲 氧化鋁原料：6 0〜9 0質量％、碳原料·· 〇 _ 5〜2 〇質量％。而 且’於該主原料中’可配合上述的鋁及/或鋁合金，以使 在耐火原料配合物中的含量成爲〇. 3〜5質量％。 又’於本發明的耐火原料配合物中，除了上述鋁及/ 或鋁合金以及尖晶石超微粉，作爲副原料，亦可配合〇.5 〜40質量％的一般氧化鋁碳系不燒磚之原料所使用的耐火 原料。作爲該副原料’可配合碳化矽原料，以使在耐火原 料配合物中的含量成爲〇 · 5〜1 0質量。/。，同時亦可配合粒 徑爲0. 1 mm以上的氧化鎂原料，以使在耐火原料配合物中 的含量成爲0.5〜25質量。/。。當配合碳化矽及/或氧化鎂原 料時’則成爲適合作爲鐵液鍋或混鐵車之內襯材的氧化鋁 ^ 碳系不燒磚。再者，作爲副原料，藉由配合合計量爲5〜 3 8貞重％的氧化銷局銘紅柱石及氧化銘氧化銷中的1種以 上’可成爲適合作爲滑動噴嘴裝置的板磚或噴嘴之氧化鋁 碳系不燒磚。 於本發明中’硼砂酸玻璃等的玻璃質原料之配合量較 佳爲1 _ 7質量％以下’更佳爲1質量％以下，最佳爲不配合 。玻璃質原料會在所生成的二次尖晶石中生成低熔物，導 致熱強度的降低、耐蝕性的降低。於專利文獻3中，玻璃 -12- 201100351 質材料係用於使尖晶石粒彼此鍵結的必要成分，於使用粒 徑0 · 0 7 5 mm以下的尖晶石原料與鋁或鋁合金的實施例6、 實施例8及比較例2中，配合2〜4質量％ (在本發明所言 的耐火原料配合物中佔有比例爲1 . 8〜3 · 7質量％ )的外掛 之玻璃質原料，與本發明比較下，茲認爲熱強度及耐蝕性 降低。又’由於玻璃質原料進行熔融而被覆尖晶石超微粉 的表面，阻礙Mg氣體的發生，故亦會對二次尖晶石的生 〇 成有不利影響。 又，於本發明中，耐火原料配合物中的Na20、B2〇3 、P2〇5及K2〇之合計量較佳爲0.5質量％以下。本發明中 係如上述地’於磚工作面上形成連續的尖晶石質保護層， 與此保護層內的Α12〇3或Si02等反應而生成低熔點成分的 Na20、B2O3、P2O5及K20之含量係愈少愈佳，Na20、 B2〇3、P2〇5及K2〇之合計量若超過〇·5質量。/。，則在尖晶 石保護層中生成低熔物，保護層的耐蝕性會降低。 Ο 還有，於本發明中，可使用上述氧化鋁碳系不燒磚於 混鐵車或熔鋼鍋等經耐火物內襯的容器，或作爲滑動噴嘴 裝置的板磚或上部噴嘴、下部噴嘴等而使用於窯爐設備。 發明的效果 本發明的氧化銘碳系不燒磚係耐触性、熱強度及耐熟 化性優異。又，由於耐熱衝撃性亦優異，故可抑制破裂剝 離。因此’內襯有本發明的磚之混鐵車或澆桶等的熔融金 屬容器之壽命係升高。又’若使用本發明的磚於滑動噴嘴 -13- 201100351 裝置的板磚、上部噴嘴、下部噴嘴等，則滑動噴嘴裝置的 壽命升筒。 【實施方式】 實施發明的形態 本發明所使用的氧化鋁原料係含有質量％以上的 Al2〇3之耐火原料，可使用耐火物中所—般使用的氧化鋁 原料。例如，可使用電熔氧化鋁、燒結氧化鋁、煅燒氧化 鋁、鋁礬土及礬頁岩中的1種以上。 氧化銘原料係作爲耐蝕性優異的原料，由粗粒到微粉 ’在耐火原料配合物中可使用60〜9〇質量％。丨曰是，從容 易形成一次尖晶石之點來看，更佳爲使用丨5〜4 〇質量％的 粒徑未達ΙΟΟμηι者。 碳原料係用於提高熔渣耐蝕性或耐熱衝撃性，只要是 以往耐火物中所一般使用者’則可沒有問題而使用。較佳 爲使用C含量爲9 0質量％以上的鱗狀石墨、碳黑、無煙 碳及瀝青等中的1種以上。碳原料更佳爲在耐火原料配合 物中配合〇 · 5〜2 0質量％。 本發明所使用的鋁及鋁合金，可沒有問題地使用通常 耐火物中所一般使用者。作爲鋁合金，可使用Al-Si合金 、A1-Mg合金、Al-Si-Mg合金等。鋁及鋁合金較佳爲以粉 末狀且粒徑未達ΙΟΟμιη者在耐火原料配合物中配合〇.3〜 5質量％。 本發明所使用的尖晶石超微粉係狀態圖中存在於普通 -14 - 201100351 尖晶石（Al2〇3 : 71 _7 質量 ％、MgO : 28.3 質量 ％ ) 之固溶體組成，結晶相爲剛玉與尖晶石、尖晶石單 晶石與方鎂石共存者，化學組成係MgO含量爲5, 量％、較佳28〜40質量％且剩餘部分爲Al2〇3者。 無可避免的雜質成分較佳爲未達1質量％。 本發明所使用的尖晶石超微粉係可使用以電熔 結法或濕式合成法等以往製法所製造者。其中，較 〇濕式合成法所製造者，因爲活性非常高，在磚組織 生成二次尖晶石。 作爲濕式合成法，例如已知有於鎂與鋁的混合 中添加鹼劑，以使鎂的化合物與鋁的化合物共沈澱 濕式法’在高溫環境將此混合溶液噴霧以使乾燥之 燥法’或將混合溶液噴霧以使凍結後，進行減壓而 之凍結乾燥法，混合鎂與鋁的醇鹽後，進行水合的 。將以如此的濕式合成法所得之混合物煅燒後，藉 Ο、篩選’可調整至粒徑未達150 μπί且平均粒徑0.1. 。尖晶石超微粉中的MgO與Α12〇3之比例，即使爲 法，也可藉由起始原料的混合比使成爲任意的比例 於本發明中，以氧化鋁原料與碳原料當作主原 用含有鋁及/或鋁合金以及尖晶石超微粉的耐火原 物’但於此等原料以外，作爲副原料，亦可組合使 鎂、碳化矽、氧化銷、高鋁紅柱石、氧化锆高鋁紅 氧化鋁氧化鉻、黏土、碳化硼及玻璃等中的1種以_ 具體的耐火原料配合物之基本構成係含有60〜 之兩側 體或尖 〜50質 再者， 法、燒 佳爲以 中容易 酸性鹽 之化學 噴霧乾 使乾燥 醇鹽等 由粉碎 〜5 0 μπι 任何製 〇 料，使 料配合 用氧化 柱石、 t。 -90質 -15- 201100351 量％的氧化鋁原料、〇 5〜20質量％的碳原料以及0.3〜5 質量％的鋁及/或鋁合金。此耐火原料配合物係可僅爲前述 基本構成’也可爲按照其用途而進一步含有〇·5〜4〇質量 %的副原料之構成。 例如’於作爲鐵液鍋或混鐵車的內襯用磚之用途中， 作爲副原料，可合適地添加0 _ 5〜1 0質量％的碳化矽原料 及/或0_ 5〜25質量％的氧化鎂原料。碳化矽具有提高耐氧 化性的效果，氧化鎂具有防止內襯的磚間之接縫裂開或提 高耐蝕性的效果。其中，氧化鎂原料的粒徑，爲了熟化防 止，較佳爲0.1mm以上。 再者，作爲滑動噴嘴裝置的板磚或噴嘴所使用的氧化 鋁碳系不燒磚用之耐火原料配合物，可添加合計量爲5〜 3 8質量％的氧化锆高鋁紅柱石及氧化鋁氧化銷中的1種以 上當作副原料。藉由添加氧化锆高鋁紅柱石或氧化鋁氧化 鍩，而提高耐熱衝撃性。 於本發明中，由於使用非常高活性的尖晶石超微粉， 若減少形成耐火原料中的低熔點成分之雜質成分，則耐蝕 性更加提高。具體地’耐火原料配合物中的Na20、B2〇3 、P205及K20之合計量較佳爲0.5質量％以下。藉由使耐 火原料配合物中的Na20、Β2〇3、Ρ2〇5及Κ20之合計量成 爲0.5質量。/。以下’可使所得的磚中之Na20、Β2〇3、Ρ205 及Κ20之合計量成爲0.5質量％以下。耐火原料配合物中 的Na20、Β203、Ρ2〇5及Κ2〇之合計量若超過0.5質量％ ，則熔渣耐蝕性、熱彎曲強度等降低。Na2〇、Β2〇3、Ρζ05 -16- 201100351 及κ20亦會由玻璃質原料帶來。因此’玻璃質原料的配合 量較佳爲1 . 7質量％以下’更佳爲1質量％以下’最佳爲不 配合。 於由上述原料所成的耐火原料配合物中添加酚樹脂等 的有機黏結劑進行混煉、成形後’藉由熱處理而得到本發 明的氧化鋁碳系不燒磚。成形係藉由摩擦式壓機或油壓機 等將混煉物塡充於模具而進行。又，熱處理係在1 000°c以 〇 下進行，較佳爲在7〇〇°c以下進行。再者，熱處理由於主 要目的爲使有機黏結劑硬化，故熱處理溫度爲100〜700°c 亦充分。 本發明的氧化鋁碳系不燒磚係藉由使用時的受熱而鋁 或尖晶石超微粉等進行反應，進一步形成結合組織。而且 ’本發明的氧化鋁碳系不燒磚係藉由使用時的受熱而形成 二次尖晶石，成爲耐蝕性極優異的磚，藉由使用作爲鐵液 輸送或進行脫矽、脫磷、脫硫等的鐵液預備處理之混鐵車 〇或澆桶的內襯磚，而混鐵車或澆桶的壽命顯著提高。又， 藉由使用於滑動噴嘴裝置的板磚、上部噴嘴、下部噴嘴等 ’而提高此等構件的耐蝕性，壽命顯著提高。 [實施例] 以下顯示本發明的實施例及比較例。 表1顯示本發明的實施例及比較例所使用的尖晶石超 微粉之特性。表2〜表4顯示實施例及比較例所使用的耐 火原料配合物之組成及試作的氧化鋁碳系不燒磚之特性試 -17- 201100351 驗結果。 於表2〜表4所示的耐火原料配合物中添加酚樹脂進 行混煉，藉由摩擦式壓機成形爲普通形狀後’在2 5 〇 °C進 行熱處理以試作氧化鋁碳系不燒磚。酚樹脂係使用經有機 溶劑稀釋而調整黏性的液狀類型者，其添加量以外掛表示 爲4質量％。 說明表1〜表4所示的各原料。尖晶石原料係將藉由 濕式合成法所製造者煅燒處理後’進行微粉碎，以篩子來 篩選，而調整至表1所示的平均粒徑。再者，表1所示的 尖晶石原料之粒徑皆未達150^m。尖晶石原料的Al2〇3與 MgO之各自含量係如表1所示，使用Na20、B2〇3、p2〇5 及Κ2 Ο (以下稱爲「雜質四種」）之合計量爲0.1質量％ 者。表1中，尖晶石Β〜Η及尖晶石J〜Ν係滿足本發明 之規定的尖晶石超微粉。 電熔氧化鋁係使用A12 〇 3爲9 8質量％而雜質四種的合 計量爲0.2質量°/〇者’氧化鉻高鋁紅柱石係使用ai2〇3爲 55質量％、Zr02爲28質量。/。、3丨02爲16質量％而雜質四 種的合計量爲〇 _ 2質量％者，碳化矽係使用S i C爲9 5質量 %而雜質四種的合計量爲〇. 3質量％者，石墨、無煙碳及碳 黑係使用C爲95質量％而雜質四種的合計量爲〇·2質量％ 者’氧化鎂係使用MgO爲98質量％而雜質四種的合計量 爲0.2質量％者，鋁係使用A1爲99.9質量％者，玻璃係使 用B 2 0 3爲1 5質量％、N a2 〇爲5質量％的硼砂酸玻璃。 其次’說明表2〜4所示的氧化鋁碳系不燒磚之特性 -18- 201100351 試驗結果的項目。 表觀氣孔率係依據】IS R2205進行測定，彈性模數係 以由超音波的傳播速度算出的方法進行測定。 熱彎曲強度係依據J I S R 2 6 5 6在氮氣流通的惰性環境 中，於1400°C進行測定。 耐熱衝撃性係在1 600°C的鐵液中浸漬90秒及取出， 進行3 0秒的水冷後，進行3 0秒的空氣冷卻，重複此操作 〇 直到試驗體（20〇x5〇x4〇mm)的一部分剝落爲止，最高實 施12次爲止。表中顯示發生剝落的試驗次數。 耐蝕性係按照ASTM C8 74-7 7記載的試驗方法，以旋 轉熔渣試驗法來實施。使用鹼度（Ca0/Si02 )爲6的合成 熔渣（高爐熔渣與石灰的混合物），在1 65 0°C進行。將比 較例1的熔損量當作1 00，以指數來表示。此指數愈小， 表示耐蝕性愈良好。 耐熟化性係按照學振法的氧化鎂燒結塊的熟化性試驗 ® 方法，以煤磚的壓縮強度降低率進行評價。 表2顯示與尖晶石原料的平均粒徑及使用量有關的調 査結果。實施例1〜7由於使用平均粒徑在本發明的範圍 內之尖晶石超微粉，故與比較例1比較下，熱彎曲強度、 耐熱衝撃性、耐蝕性皆優異。特別地，於平均粒徑1 5 μιη 以下的實施例5〜7中，耐蝕性的改善係顯著。再者，實 施例2〜7雖然在耐熟化性之點較比較例1還若干差，但 實際使用上沒有問題。 相對於此，於尖晶石原料的MgO含有率爲5〜5〇質 -19- 201100351 量％的範圍內但平均粒徑超過5 0 μ m之情況，如比 所示’由於熱處理後的彈性模數與熱彎曲強度相當 推測受熱時二次尖晶石的生成量少，結果若與實施 比較，則耐熱衝撃性與耐鈾性大幅變低。 實施例8〜實施例1 1係耐火原料配合物中的尖 微粉含量在本發明的範圍內，所有特性皆良好。比 係尖晶石超微粉含量低於本發明的下限，與實施例 熱彎曲強度及耐蝕性降低。又，比較例3係尖晶石 含量超過本發明的上限，耐熱衝撃性與耐熟化性差 若尖晶石超微粉含量過多則磚的熱膨脹變大，故耐 性降低，同亦損害耐熟化性。 比較例4及5係不使用鋁的情況，與實施例2 較下，由於熱彎曲強度低，而且耐蝕性差，故推測 晶石的生成係不充分。比較例6係不使用尖晶石原 況，耐蝕性差。 表3係使用不同化學組成的尖晶石超微粉之例 所示的各實施例係尖晶石超微粉的化學組成在本發 圍內，所有特性皆良好。比較例7由於使用MgO 的尖晶石超微粉’故二次尖晶石的生成係不充分’ 強度及耐蝕性低。比較例8係Mg〇含量過高’耐 不良。由表3可知’尖晶石超微粉的MgO含量愈 熟化性愈低’但若尖晶石超微粉的M g 〇含量爲本 範圍，則得到實用上沒有問題的水平之耐熟化性。 考慮耐蝕性或耐熟化性的平衡’可知尖晶石超微 較例1 低，故 例1〜7 晶石超 較例2 相比， 超微粉 。由於 熱衝撃 及3比 二次尖 料的情 卜表3 明的範 含量低 熱彎曲 熟化性 :多則耐 發明的 又，若 粉中的 -20- 201100351201100351 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to alumina-carbon non-fired bricks such as alumina-carbon brick, alumina-carbonium carbide-carbon brick, alumina-magnesia-carbon brick, etc. The utility model relates to a lining of a mixed iron car or a ladle which is used for iron liquid transportation or iron preparation such as de-purification, dephosphorization and desulfurization, or a slab of a sliding nozzle device, an upper nozzle, a lower nozzle and the like. Further, there is a kiln equipment using alumina carbon-based unfired bricks. Ο 【Prior Art】 Alumina carbon is added to the refractory raw material mixture containing alumina raw materials and carbon raw materials as a basic component, and an organic binder is added as a binder. After kneading and molding, it is produced by heat treatment. Oxidized refractory with carbon bonding. In particular, the non-fired type which is heat-treated at a temperature of I 0 0 ° C or less is currently used as a mainstream of steel for bricks because it can be manufactured at low cost and is excellent in durability.于此 In the alumina carbon-based unfired bricks, various types of refractory raw materials are used in addition to the alumina raw materials and carbon raw materials depending on their use or conditions of use. For example, magnesium oxide (coarse grain) or spinel (coarse grain) is used for the brick used for the lining of the ladle for molten iron, and tantalum carbide is used for the lining brick of the mixed iron car, and the sliding nozzle is used. Zirconium sulphite or alumina zirconia or the like is used for the tile used in the apparatus. Further, for the purpose of oxidation resistance, metal powder, boride or glass is also used as a refractory raw material. In the case of the alumina carbon-based unfired brick, further, in order to prevent the hunger from being hungry or to prevent cracking of the joint during use, there is a fine powder using magnesium oxide or -5-201100351 spinel. As a refractory raw material The idea is to cause MgO in the brick or Mg in the spinel to react with the alumina raw material by heat in use to form a slag-resistant spinel, and then expand by spinel formation. The tissue is densified to improve corrosion resistance. However, magnesium oxide reacts with moisture in the air, and has hydration and swelling properties (aging), and in particular, it is problematic when it is used as a fine powder having a particle diameter of 1 ΟΟμηι or less. For example, when the furnace is built, the alumina carbon brick to which the fine powder of magnesium oxide is added is used as a lining in the furnace, and then the water vapor generated by the moisture of the mortar used on the back side of the brick is preheated. Magnesium oxide in the brick is hydrated and swelled, which greatly reduces the strength of the brick structure. Therefore, when magnesium oxide is used, a coarse powder or an ultrafine powder of alumina which is not easily matured with magnesium oxide is generally used in combination. Therefore, the spinel formation system using magnesium oxide has low activity, and the effect of improving corrosion resistance is limited. Further, conventionally, in the classification of refractory raw materials, coarse particles mean a particle diameter of 1 mm or more, and fine powder means ΙΟμιη or more and less than 1 mm, and ultrafine powder means that the particle diameter does not reach ΙΟμιη. However, the spinel ultrafine powder of the present invention to be described later is not limited by the above-described conventional classification, but is defined in accordance with the present invention. Further, instead of magnesium oxide, a spinel containing MgO and not easily ripened is also used. For example, Patent Document 1 describes an alumina-magnesia-rich spinel-carbon brick which is blended with 10 to 80% by mass of Mg0/Al203 in a mass ratio of 50/50 to 95/5 and MgO and Al2〇. The total amount of 3 is 95% by mass or more of the fused magnesia-rich spinel raw material, 3 to 60% by mass of the carbonaceous raw material, and 1 to 85% by mass of the alumina raw material. The alumina-oxidized 201100351 magnesium-rich spinel-carbon brick has a refractory slag resistance because it is not easily reacted with the CaO component contained in the slag, and even if the content of the spinel is relatively small, A brick with a moderate residual expansion ratio can be obtained. Further, in Patent Document 2, a fine powder having a particle diameter of 100 μm or less of any one of 0.5 to 4.0% by mass of magnesium oxide or magnesium oxide-rich spinel is added as a compound. Magnesia, the matrix portion is an alumina-carbonium carbide-carbonaceous refractory having a carbon-bonded and spinel-bonded structure. Since the magnesium oxysulfide or magnesium oxide-rich spinel system reacts with alumina at a temperature above 1 250 °C to form a spinel, it is preferably as fine as possible in order to improve the dispersibility (preferably The particle size is 50 μm or less, but the particle diameter of the refractory material is 1 0 0 μm or less. Further, Patent Document 3 describes a method for producing a carbon-containing refractory, which is characterized in that a carbon-based adhesive is added to a cerium oxide-containing material containing 30 to 90% by mass, and 3 to 30% by mass of carbon. Material, 5~50 quality. The mixture of Al: 2〇3-MgO-based spinel having a particle diameter of 1 mm or less and 玻璃_ι~5 mass% of the outer glassy material is kneaded, molded, and dried. It is described that the refractory is formed by a combination of a vitreous material and a combination of spinel particles to form a spinel crosslinked layer on a working surface in which the refractory is used, thereby obtaining excellent corrosion resistance and oxidation resistance. Refractory. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. 201100351 [Disclosure] Problems to be Solved by the Invention The alumina-magnesia-rich spinel-carbon brick of Patent Document 1 is subjected to moisture content in the air due to the high content of Mg〇 in the magnesia-rich spinel. The reaction has a problem of hydration reaction of MgO which is liable to occur freely. Further, in Table 2 of Patent Document 1, a spinel having a particle diameter of 1 mm or less is used, but in the case of a special specification of a particle diameter of 1 mm or less, particularly when the particle diameter is large, the influence is remarkably caused by The amount of use is lowered by the high thermal expansion coefficient of the spinel crystal phase, and the shear stress is increased to cause problems such as cracking and peeling. In the case of using the magnesia-rich aluminate brick of the magnesia-rich spinel having a particle diameter of 1 00 μm or less in Patent Document 2, the effect of improving the corrosion resistance is indeed observed, but it is insufficient. When used in a coke oven, the corrosion resistance is still a bottleneck life, and it is desired to further improve the corrosion resistance. Further, Patent Document 2 also has a problem of hydration. In the case of the alumina-spinel-carbon-glass refractory of Patent Document 3, although the corrosion resistance is increased, it is formed of a vitreous material which softens the bonding of the spinel particles to each other at a high temperature. Therefore, the heat strength is lowered, and since the wear resistance of the bonded portion is lowered, the effect of improving the saturability is limited. Therefore, the problem to be solved by the present invention is to suppress the hydration reaction in the alumina-carbon-fired brick to which spinel has been added, and to further improve the tamper resistance. Further, a furnace apparatus using this alumina carbon-based unfired brick is provided. Means for Solving the Problems - 201100351 The present inventors conducted intensive studies and found that in order to suppress the hydration reaction in the alumina carbon-based non-suppression and to improve the corrosion resistance, it is necessary to mix the spines in the refractory raw material complex. As the stone raw material, (1) average particle diameter, (2) MgO content rate, and (3) content (combination amount) in the refractory raw material complex are specified. That is, the alumina carbon-based unfired brick of the present invention uses an alumina raw material and a carbon raw material as main raw materials, and adds an organic binder to a refractory raw material complex containing aluminum and/or aluminum alloy and spinel ultrafine fine powder. After the mixture is kneaded and formed, the alumina carbon-based unfired brick obtained by heat treatment at 1 000 ° C or less is characterized in that the spinel ultrafine powder in the refractory raw material has a particle size of less than 150 μm and an average particle diameter. It is 0.1 to 50 μm, the MgO content is 5 to 50% by mass, and the remainder is composed of ai2o3, and the content of the spinel ultrafine powder in the refractory raw material mixture is 2 to 20% by mass. When the spinel raw material is blended in the refractory raw material mixture of the alumina-carbon-fired brick, if the aluminum and/or the aluminum alloy is not added as in the above-mentioned Patent Document 2, the particle diameter is 1 ΟΟμπι or less, and the secondary tip is The spar formation reaction is slow, and the effect of improving corrosion resistance due to secondary spinel formation is small. In order to increase the formation of secondary spinel, there is a method of increasing the amount of spinel blending or increasing the MgO content in the spinel, but since these methods lead to a decrease in the resistance to ripening, practically, There are many problems. On the other hand, the spinel ultrafine powder used in the present invention has a very high activity because its average particle diameter is 0.1 to 50 μm and the specific surface area is large. Therefore, in the reducing environment inside the brick, since the A1 system coexists, the spinel ultrafine powder easily becomes Mg gas, and is reoxidized on the surface of the surrounding alumina raw material to form a secondary spinel. Furthermore, the surface of the brick -9 - 201100351 reacts with Al2〇3 or CaO in the slag composition to form a continuous spinel protective layer on the surface of the brick. Therefore, corrosion resistance can be improved. Moreover, the above-mentioned effect by the spinel ultrafine powder can be remarkably achieved when the particle diameter is less than 150 μm. Therefore, the spinel ultrafine powder described in the present invention is based on the premise that the particle diameter is less than 150 μm, and the average particle diameter is 〇. 1 to 50 μmη as a requirement. The spinel material having a particle diameter of 1 50 μm or more is not particularly limited in the present invention, and may or may not be blended together with the spinel ultrafine powder. Here, in the present invention, the particle diameter of the so-called particles of less than d ' means that the particle size passes through the sieve of the mesh d defined by JIS-Z8 80 1 'The particle size of the particles is d or more, that is, This means the particle size of the particles remaining on the same sieve. Further, in the present invention, the average particle diameter means that the particle diameter and the mass ratio measured by a laser diffraction scattering type particle size distribution meter are plotted as a graph, and the cumulative ratio is 50%. 1 is a model diagram of a microstructure of an alumina carbon-based non-suppressed slag corrosion resistance test of the present invention, and it is confirmed that spinel is used as a main component on the surface of the brick 1 at the boundary with the slag 3 Spinel protective layer 2. By the action of the present invention, the spinel having a relatively small content of magnesium oxide is not used in a large amount, and the secondary spinel can be sufficiently formed. Further, the spinel in which the Mg gas has been removed contains fine pores, and voids are also formed between the crystal grains of the secondary spinel formed on the surface of the alumina raw material, resulting in an increase over the volatile matter of the binder. Porosity. As a result, the porosity increases, and the strength of the secondary spinel is increased by the bond of the secondary spinel, which suppresses the decrease in the elastic modulus and improves the heat-resistant punchability. The formation of secondary spinel due to the reaction of the gasification-10-201100351 is difficult to produce only by the specific spinel material having a particle diameter of less than 100 μm, and the spinel having an average particle diameter of 0.1 to 50 μm The use of stone ultrafine powder and the addition of aluminum and/or aluminum alloy have become remarkable. When the average particle diameter is less than 0.1 μm, the hydration is easy, and if it exceeds 50 μm, the amount of secondary spinel produced is small, so that the effect of improving corrosion resistance is lowered. In order to promote the formation of the secondary spinel, the average particle diameter of the spinel ultrafine powder is preferably small, more preferably 4 〇μπι or less, still more preferably 30 μιη or less ◎ , and most preferably 15 μιη or less. The chemical composition of the spinel ultrafine powder used in the present invention has a MgO content of 5 to 50% by mass, and the remainder is Al2?3 (of course, containing inevitable impurities). If the MgO content of the spinel ultrafine powder is less than 5% by mass, the characteristics are close to that of the alumina ultrafine powder, and the ultrafine powders are sintered at a high temperature, and the particle size increases and the secondary spinel formation reaction stagnate. On the other hand, if the MgO content of the spinel ultrafine powder exceeds 50% by mass, there is a problem that it becomes easy to mature. Ο The spinel ultrafine powder is blended in such a manner that the content of the spinel ultrafine powder in the refractory raw material mixture is 2 to 20% by mass. If it is less than 2% by mass, the ratio of the generated secondary spinel is small, and the effect of increasing the corrosion resistance or the thermal bending strength is small. When it exceeds 20% by mass, the porosity of the Mg gas after volatilization increases, and the thermal expansion of the brick becomes large, causing cracking damage, which is a practical problem. The aluminum and aluminum alloy to be blended in the refractory raw material composition of the present invention have a function of reducing MgO in the spinel and generating Mg gas in use of the brick. The total amount of aluminum and aluminum alloy in the refractory raw material complex is preferably from 3-1 to 201100351 of from 0.3 to 5% by mass. When the amount is less than 3% by mass, the effect of promoting the formation of the secondary spinel becomes small, and if it exceeds 5% by mass, the structure becomes excessively dense due to the formed aluminum carbide or aluminum nitride, and the heat-resistant squeezing property is obtained. reduce. Here, the blending amount of the alumina raw material and the carbon raw material of the main raw material of the refractory raw material complex of the present invention (the content in the refractory raw material complex) may be an alumina raw material: 60 to 90% by mass, carbon raw material· · 〇 _ 5~2 〇 mass%. Further, the content of the refractory raw material in the refractory raw material is 〇. 3 to 5 mass%, and the above-mentioned aluminum and/or aluminum alloy may be blended in the main raw material. Further, in the refractory raw material composition of the present invention, in addition to the above-mentioned aluminum and/or aluminum alloy and spinel ultrafine powder, as an auxiliary material, it is also possible to blend 〇5 to 40% by mass of general alumina carbon-based unfired bricks. The refractory raw material used for the raw materials. The raw material ' can be blended with the niobium carbide raw material so that the content in the refractory raw material mixture is 〇 5 to 10% by mass. /. At the same time, the magnesium oxide raw material having a particle diameter of 0.1 mm or more may be blended so that the content in the refractory raw material complex is 0.5 to 25 mass. /. . When blended with niobium carbide and/or magnesia raw materials, it becomes an alumina ^ carbon-based non-fired brick suitable as an inner lining for a molten iron pan or a mixed iron car. In addition, as the auxiliary material, one or more of the oxidized pin mullite and the oxidized oxidized pin can be used as a sliding nozzle device by a total amount of 5 to 38% by weight. The alumina carbon system does not burn bricks. In the present invention, the blending amount of the glassy raw material such as borax acid glass is preferably 1 to 7 mass% or less, more preferably 1 mass% or less, and most preferably no compounding. The glassy raw material generates a low-melting substance in the generated secondary spinel, resulting in a decrease in thermal strength and a decrease in corrosion resistance. In Patent Document 3, glass-12-201100351 is a necessary component for bonding spinel particles to each other, and uses a spinel material having a particle diameter of 0·0.75 mm or less and aluminum or aluminum alloy. In Example 6, Example 8 and Comparative Example 2, the external glassy raw material was blended in an amount of 2 to 4% by mass (in the refractory raw material composition of the present invention, the ratio was 1. 8 to 3 · 7 mass%). Compared with the present invention, it is considered that the thermal strength and the corrosion resistance are lowered. Further, since the glassy raw material is melted to coat the surface of the spinel ultrafine powder and hinder the generation of Mg gas, it also adversely affects the growth of the secondary spinel. Further, in the present invention, the total amount of Na20, B2〇3, P2〇5 and K2〇 in the refractory raw material composition is preferably 0.5% by mass or less. In the present invention, as described above, a continuous spinel protective layer is formed on the brick working surface, and reacts with Α12〇3 or SiO2 in the protective layer to form Na20, B2O3, P2O5 and K20 having a low melting point component. The less the content, the better, and the total amount of Na20, B2〇3, P2〇5 and K2〇 exceeds 〇·5 mass. /. , a low-melting substance is formed in the spinel protective layer, and the corrosion resistance of the protective layer is lowered. Further, in the present invention, the alumina-carbon-based non-fired brick may be used in a refractory-lined container such as a mixed iron car or a molten steel pan, or a slab or an upper nozzle or a lower nozzle as a sliding nozzle device. Used in kiln equipment. EFFECT OF THE INVENTION The oxidized carbon-based non-fired brick of the present invention is excellent in contact resistance, heat strength and ripening resistance. Further, since the heat-resistant and squeezing property is also excellent, cracking and peeling can be suppressed. Therefore, the life of the molten metal container in which the mixed iron car or the ladle of the brick of the present invention is lined up is increased. Further, if the brick of the present invention is used for the tile, the upper nozzle, the lower nozzle or the like of the sliding nozzle -13-201100351 device, the life of the nozzle device is lifted. [Embodiment] The present invention is an alumina raw material which contains a mass% or more of refractory raw material of Al2〇3, and an alumina raw material which is generally used in a refractory can be used. For example, one or more of fused alumina, sintered alumina, calcined alumina, bauxite, and shale may be used. The oxidized raw material is used as a raw material having excellent corrosion resistance, and the coarse to fine powder is used in the refractory raw material mixture in an amount of 60 to 9 % by mass. Therefore, from the point of view that it is easy to form a spinel, it is more preferable to use 丨5 to 4 〇% by mass of the particle size which does not reach ΙΟΟμηι. The carbon raw material is used for improving the slag corrosion resistance or the heat-resistant squeegee, and can be used without any problem as long as it is a general user of the conventional refractory. It is preferable to use one or more of scaly graphite, carbon black, smokeless carbon, and pitch, and the like having a C content of 90% by mass or more. More preferably, the carbon raw material is blended with 〇 5 to 20% by mass in the refractory raw material mixture. The aluminum and aluminum alloy used in the present invention can be used as a general user of a general refractory without any problem. As the aluminum alloy, an Al-Si alloy, an A1-Mg alloy, an Al-Si-Mg alloy, or the like can be used. The aluminum and the aluminum alloy are preferably in the form of a powder and have a particle size of less than ΙΟΟμιη, and are blended in the refractory raw material mixture in an amount of 3% to 5% by mass. The spinel ultrafine powder state diagram used in the present invention is composed of a solid solution composed of ordinary -14 - 201100351 spinel (Al2〇3: 71 _7 mass%, MgO: 28.3 mass%), and the crystal phase is corundum. In the case of coexistence with spinel, spinel single crystal and periclite, the chemical composition is MgO content of 5, % by weight, preferably 28 to 40% by mass, and the remainder is Al2〇3. The unavoidable impurity component is preferably less than 1% by mass. The spinel ultrafine powder used in the present invention can be produced by a conventional method such as an electric fusion method or a wet synthesis method. Among them, those produced by the 〇-wet synthesis method have a very high activity, and a secondary spinel is formed in the brick structure. As a wet synthesis method, for example, it is known to add an alkali agent to a mixture of magnesium and aluminum so that a compound of magnesium and a compound of aluminum are coprecipitated by a wet method of spraying the mixed solution in a high temperature environment to dry the drying method. 'Or after the mixed solution is sprayed to freeze, and then subjected to a freeze-drying method under reduced pressure, an alkoxide of magnesium and aluminum is mixed and then hydrated. After the mixture obtained by such a wet synthesis method is calcined, it can be adjusted to have a particle diameter of less than 150 μπί and an average particle diameter of 0.1. The ratio of MgO to Α12〇3 in the spinel ultrafine powder can be made into an arbitrary ratio in the present invention by the mixing ratio of the starting materials, and the alumina raw material and the carbon raw material are used as the main source. Use of refractory originals containing aluminum and/or aluminum alloy and spinel ultrafine powders. However, in addition to these raw materials, it is also possible to combine magnesium, tantalum carbide, oxidized pin, mullite and zirconia as auxiliary materials. One of the aluminum red alumina chrome oxide, clay, boron carbide and glass, etc., the basic composition of the refractory raw material complex contains 60~ both sides or the tip to 50 mass, and the method is Drying the alkoxide or the like with a chemical spray of a medium acid salt to pulverize ~50 μm to any mash, and mix the oxidized column with t. -90 mass -15- 201100351 Amount of alumina raw material, 〇 5 to 20% by mass of carbon raw material, and 0.3 to 5% by mass of aluminum and/or aluminum alloy. The refractory raw material complex may be of the above-mentioned basic constitution or may further comprise a by-product of 5% by mass to 5% by mass in accordance with the use thereof. For example, in the use as a lining brick for a molten iron pan or a mixed iron car, as the auxiliary raw material, 0 to 5 to 10% by mass of the niobium carbide raw material and/or 0 to 5 to 25% by mass may be appropriately added. Magnesium oxide raw material. The niobium carbide has an effect of improving the oxidation resistance, and the magnesia has an effect of preventing the joint between the bricks of the inner liner from cracking or improving the corrosion resistance. Among them, the particle diameter of the magnesium oxide raw material is preferably 0.1 mm or more for aging prevention. Further, as the refractory raw material mixture for alumina carbon-based unfired brick used for the tile or nozzle of the sliding nozzle device, zirconia mullite and alumina in a total amount of 5 to 38% by mass may be added. One or more of the oxidation pins are used as an auxiliary material. The heat-resistant punching property is improved by adding zirconia mullite or alumina yttrium oxide. In the present invention, since the ultra-fine spinel ultrafine powder is used, the corrosion resistance is further improved by reducing the impurity component forming the low-melting component in the refractory raw material. Specifically, the total amount of Na20, B2〇3, P205 and K20 in the refractory raw material composition is preferably 0.5% by mass or less. The total amount of Na20, Β2〇3, Ρ2〇5 and Κ20 in the fire-resistant raw material mixture was measured to be 0.5 mass. /. In the following, the total amount of Na20, Β2〇3, Ρ205, and Κ20 in the obtained bricks may be 0.5% by mass or less. When the total amount of Na20, Β203, Ρ2〇5, and Κ2〇 in the refractory raw material mixture exceeds 0.5% by mass, the slag corrosion resistance, thermal bending strength, and the like are lowered. Na2〇, Β2〇3, Ρζ05 -16- 201100351 and κ20 will also be brought by glassy raw materials. Therefore, the blending amount of the glassy raw material is preferably 1.7 mass% or less, more preferably 1 mass% or less, which is most preferable. An alumina-based unfired brick of the present invention is obtained by heat treatment by adding an organic binder such as a phenol resin to the refractory raw material mixture of the raw material, and kneading and molding. The forming system is carried out by kneading the kneaded material to a mold by a friction press or a hydraulic press. Further, the heat treatment is carried out at 1 000 ° C under 〇, preferably at 7 ° C or lower. Further, since the main purpose of the heat treatment is to harden the organic binder, the heat treatment temperature is also 100 to 700 ° C. The alumina carbon-based unfired brick of the present invention is reacted by aluminum or spinel ultrafine powder or the like by heating at the time of use to further form a bonded structure. Further, the alumina carbon-based unfired brick of the present invention is formed into a secondary spinel by heat during use, and is a brick excellent in corrosion resistance, and is used as a molten iron for transporting or de-phosphorizing or dephosphorization. The iron-lined shovel or the lining brick of the pouring bucket is prepared by the iron liquid preparation such as desulfurization, and the life of the mixed iron car or the ladle is remarkably improved. Further, the corrosion resistance of these members is improved by the use of the tile, the upper nozzle, the lower nozzle or the like of the sliding nozzle device, and the life is remarkably improved. [Examples] Examples and comparative examples of the present invention are shown below. Table 1 shows the characteristics of the spinel ultrafine powder used in the examples and comparative examples of the present invention. Tables 2 to 4 show the compositions of the fire resistant raw material complexes used in the examples and comparative examples and the characteristics of the tested alumina carbon-based unfired bricks -17-201100351. The refractory raw material mixture shown in Tables 2 to 4 is added with a phenol resin, kneaded, and formed into a common shape by a friction press, and then heat-treated at 25 ° C to test for alumina carbon-based unfired bricks. . The phenol resin is a liquid type which is diluted with an organic solvent to adjust the viscosity, and the addition amount is 4% by mass. The respective raw materials shown in Tables 1 to 4 will be described. The spinel raw material was subjected to calcination by a manufacturer of the wet synthesis method, and was finely pulverized, sieved by a sieve, and adjusted to the average particle diameter shown in Table 1. Further, the spinel raw materials shown in Table 1 were all less than 150 μm in particle size. The respective contents of Al2〇3 and MgO of the spinel raw material are as shown in Table 1, and the total amount of Na20, B2〇3, p2〇5, and Κ2 Ο (hereinafter referred to as "four kinds of impurities") is 0.1% by mass. By. In Table 1, spinel Β Η Η and spinel J Ν Ν are spinel ultrafine powders satisfying the requirements of the present invention. The fused alumina system used A12 〇 3 as 98% by mass and the impurity four in a total amount of 0.2 mass%/〇. The chrome oxide mullite system used 55 mass% of ai2〇3 and 28 mass% of Zr02. /. 3 丨 02 is 16% by mass and the total amount of the four impurities is 〇 _ 2% by mass, and the total amount of the four types of impurities is 〇 3% by mass. Graphite, smokeless carbon, and carbon black are used in an amount of 95% by mass of C and a total amount of four kinds of impurities are 〇·2% by mass. The magnesia uses 98% by mass of MgO and 0.2% by mass of the total of impurities. In the case of aluminum, A1 was used as 99.9% by mass, and glass was used as borax acid glass in which B 2 0 3 was 15% by mass and Na 2 〇 was 5% by mass. Next, the characteristics of the alumina carbon-based unfired bricks shown in Tables 2 to 4 are explained -18- 201100351. The apparent porosity was measured in accordance with IS R2205, and the elastic modulus was measured by a method of calculating the propagation velocity of ultrasonic waves. The thermal bending strength was measured at 1400 ° C in an inert atmosphere in which nitrogen gas flowed according to J I S R 2 6 5 6 . The heat-resistant squeegee was immersed in iron liquid at 1 600 ° C for 90 seconds and taken out, and after 30 seconds of water cooling, air cooling was performed for 30 seconds, and this operation was repeated until the test body (20 〇 x 5 〇 x 4 〇 mm) Part of it is peeled off, and it is carried out up to 12 times. The number of tests in which the peeling occurred was shown in the table. The corrosion resistance was carried out in accordance with the test method described in ASTM C8 74-7 7 by the rotary slag test method. A synthetic slag (mixture of blast furnace slag and lime) having a basicity (Ca0/SiO 2 ) of 6 was used at 165 °C. The melt loss amount of Comparative Example 1 was taken as 1 00 and expressed as an index. The smaller the index, the better the corrosion resistance. The ripening resistance was evaluated by the briquetting strength reduction rate of the briquettes according to the maturation test of the magnesia agglomerate of the vibration method. Table 2 shows the results of the investigations relating to the average particle size and amount of the spinel material. In Examples 1 to 7, since the spinel ultrafine powder having an average particle diameter within the range of the present invention was used, it was excellent in thermal bending strength, heat-resistant punching property, and corrosion resistance as compared with Comparative Example 1. In particular, in Examples 5 to 7 having an average particle diameter of 15 μm or less, the improvement in corrosion resistance was remarkable. Further, Examples 2 to 7 were slightly inferior to Comparative Example 1 in terms of resistance to ripening, but there was no problem in practical use. On the other hand, the MgO content in the spinel material is in the range of 5 to 5 〇-19 to 201100 351 %, but the average particle diameter exceeds 50 μm, as shown by the ratio 'by the heat treatment after heat treatment The modulus and the thermal bending strength are estimated to be small when the amount of secondary spinel is generated during heating, and as a result, the heat-resistant and uranium resistance are greatly lowered as compared with the comparison. Example 8 to Example 1 The content of the sharp powder in the refractory raw material mixture was within the scope of the present invention, and all the characteristics were good. The ratio of the ultrafine powder of the spinel is lower than the lower limit of the present invention, and the thermal bending strength and corrosion resistance of the examples are lowered. Further, in Comparative Example 3, the spinel content exceeded the upper limit of the present invention, and the heat-resistant smear resistance and the aging resistance were inferior. If the content of the spinel ultrafine powder was too large, the thermal expansion of the brick became large, so that the resistance was lowered and the ripening resistance was also impaired. In Comparative Examples 4 and 5, when aluminum was not used, compared with Example 2, since the thermal bending strength was low and the corrosion resistance was poor, it was estimated that the spar formation system was insufficient. In Comparative Example 6, the spinel was not used, and the corrosion resistance was poor. Table 3 shows examples of spinel ultrafine powders using different chemical compositions. The chemical compositions of the spinel ultrafine powders of the examples shown in the examples are all good in this range. In Comparative Example 7, since the spinel ultrafine powder of MgO was used, the formation of secondary spinel was insufficient, and the strength and corrosion resistance were low. In Comparative Example 8, the content of Mg 〇 was too high, and the resistance was poor. As is clear from Table 3, the lower the MgO content of the spinel ultrafine powder is, the lower the ripening property is. However, if the M g 〇 content of the spinel ultrafine powder is in the range, the ripening resistance at a level which is practically no problem is obtained. Considering the balance of corrosion resistance or ripening resistance, it is known that the spinel ultrafine is lower than that of the first example, so the examples 1 to 7 spar are superior to those of the example 2, and the ultrafine powder. Due to the thermal flushing and the ratio of the third-order tipping material, Table 3 shows that the fan content is low. Thermal bending. Curing property: Many are resistant to the invention, and if the powder is -20- 201100351
Mg〇含量最佳爲28〜40質量％。 表2及表3的各實施例係在耐火物原料配合物中配合 有氧化鋁、碳化矽、石墨及鋁的氧化鋁-碳化矽-碳磚，表 4中顯示其它成分系的磚。 表4的實施例1 8〜實施例2 3係在氧化鋁-碳化矽-碳 磚中加有其它原料者，具體地實施例18〜實施例21係添 加玻璃者’實施例2 2與23係添加氧化鎂者，實施例2 4 〇 係倂用當作碳原料的石墨與無煙碳者。又，實施例25與 2 6係氧化鋁-氧化鎂-碳磚，實施例27係氧化鋁-碳磚。 此等實施例係與表2及表3之實施例所示的氧化鋁__ 碳化砂-碳磚同樣地，熱彎曲強度高，而且耐飽性優異， 判斷二次尖晶石已生成。又，耐熟化性亦良好。惟，玻璃 質原料的配合量超過1 .7質量％且雜質四種的合計量超過 0.5質量％之實施例2 1係熱彎曲強度或耐蝕性的降低傾向 變大。因此可以說，較佳爲玻璃質原料的配合量係1 . 7質 Ο 量％以下且雜質四種的合計量係〇· 5質量％以下。 另一方面，比較例9係不使用尖晶石原料的氧化鋁_ 氧化鎂-碳磚，比較例1 〇係不使用尖晶石原料的氧化鋁-碳 磚，熱彎曲強度低，而且耐蝕性差。 又，實施例2 8與2 9係使用碳黑當作碳原料、使用氧 化锆高鋁紅柱石當作耐火原料之使用於滑動噴嘴裝置的板 磚等的氧化鋁碳系不燒磚。若與不使用尖晶石原料的比較 例1 1相比，則熱彎曲強度高，而且耐蝕性優異，判斷二 次尖晶石已生成。又，耐熟化性亦良好。 -21 - 201100351 再者’以下顯示對窯爐設備採用本發明的氧化鋁碳系 不燒碍之貫施例。爲了比較’將本發明品實施例6的 Al203-SiC-C質碍與比較例6之習知品的磚鄰接地貼合於 A製鐵所的250T之混鐵車（TPC )之熔渣線’進行1 79ch 實機使用。結果’實施例6的磚的熔損厚度係停留在比較 例6的磚之熔損厚度的40%，得到良好的結果。測定所回 收的磚之物性値，結果表觀氣孔率係實施例6的磚較比較 例6的磚還大，而且熱彎曲強度亦係實施例6的磚較比較 例6的磚高之値，證明如當初設想的機構。 [表1] ΑΙ2〇3(質量 ％) MgO (質量％) 平均粒徑（"m) 尖晶石A 66 33 60 尖晶石B 66 33 50 尖晶石C 66 33 40 尖晶石D 66 33 30 尖晶石E 66 33 20 尖晶石F 66 33 15 尖晶石G 66 33 7 尖晶石Η 66 33 3 尖晶石I 96 3 15 尖晶石J 94 5 15 尖晶石Κ 84 15 15 尖晶石L 71 28 15 尖晶石Μ 59 40 15 尖晶石Ν 49 50 15 尖晶石0 39 60 15 -22- 201100351 Ο ❹ 比較例6 〇 〇 ιο - Csl <0 ο σ> CO r*. s ο 比較例5 〇 Μ ΙΟ ο CM 〇 (O ο ο σ> r*«. s \Λ 比較例4 〇 \η ο CO <0 ο ο 〇> r- U9 比較例3 LO CO s ΙΑ ir» evi 〇J (O 00 00 CM CO CM (O O W 實施例11 ΙΛ c〇 ιη - 〇 csi «0 (Ο «•3 CM in e>i o in β» 實施例10 ΙΟ CO s ΙΑ - ιο CNI U> s s i〇 in C〇 實施例9 1〇 s ΙΟ - m esi (O 二 l〇 CM CJ IO CO 實施例8 » g ΙΛ - C\J eg (O Ο) o 〇> o o CO 比較例2 A g ΙΛ - - eg l〇 00 〇> l〇 o 〇 - 實施例7 〇 g ΙΑ 寸 严 ο esj W 贫 σ> eg CM o in CO 實施例6 〇 s ιη - ο csl U> ο P*» s m GO 實施例5 〇 % ιπ - o Csi to ο r-> CO s CO 實施例4 〇 1/3 - ο Csj in CO l/> in O CO 實施例3 〇 ΙΟ - ο CNI l〇 CSJ c〇 CM e> 00 eo 實施例2 § 另 in - Ο (NJ IA CM o 00 〇0 c〇 Q0 實施例1 § ιη 寸 - 〇 CNI to ο O 03 00 IA 〇> m 比較例1 s U) - 〇 Csj (O ο a> CO r·*- § ιο 平均 粒徑 60// m 50 m 40μ m 30//m| 20^im E 51 U) Ε 卜 ε 3. Ρ〇 電熔氧化鋁(粒徑3〜0.1mm) 電熔氧化鋁(粒徑0.1mm以下） 碳化矽 1 石墨 |鋁(粒徑100//m以下） |尖晶石A (MgO 33質量％) 尖晶石B (MgO 33質量％) 1 1尖晶石C (MgO 33質量％) 1尖晶石D (MgO 33質量％) 1尖晶石E (MgO 33質量％) |尖晶石F (MgO 33質量％) I 1尖晶石G (MgO 33質量％) 1 1尖晶石H (MgO 33質量％) I 〇Λ It ^rf, <ϋ9, P Igo \/ r< 1表觀氣孔率(％) ! |l400t：熱處理後的表觀氣孔率(％) 1 1400Ϊ熱處理後的彈性模數(GPa) 1 |熱彎曲強度(MPa) at 1400°C I耐熱衝擊性(次） 1 l耐触性/«損指數 1 耐熟化性(％) -23- 201100351 比較 例8 〇 S in - O CO m (Ο eg CVJ Si (〇 ο g 實施 例17 〇 g LO - 〇 Ol ιο in 〇> CM CM o s CM 辑 〇 s in 对 - o CsJ to iO σ> CM CM o g 〇> 實施 例15 § s in - O eg l〇 CO 卜 CO CSi g CO 實施 例14 〇 g in - Ο CSi irj CO 卜 (D c〇 in to ΙΛ 揭2 «荜 〇 s in - Ο eg in esi CO 40 CM o 闺2 〇 s in - 〇 40 二 ιο n 〇 in n 〇 g in 对 - 〇 Csl l〇 o c〇 卜 卜 ro 平均 粒徑 15// m I 15/i m 15# m 15/i m| 15# m| 15// m| 15// m 15 // m 1電熔氧化鋁(粒徑3〜0.1mm) |電熔氧化鋁(粒徑0.1mm以下） 1碳化矽 I石墨 |銘(粒徑100 Mm以下） |尖晶石I (MgO 3質量％) 尖晶石J (MgO 5質量％) 尖晶石K (MgO 15質量％) |尖晶石L (MgO 28質量％) |尖晶石F (MgO 33質量％) ! 尖晶石M (MgO 40質量％) |尖晶石N (MgO 50質量％) |尖晶石0 (MgO 60質量％) ΓΟ if B·噸 1¾ Ιο |表觀氣孔率(％) 11400°C熱處理後的表觀氣孔率W 11400°C熱處理後的彈性模數(GPa) 熱彎曲強度(MPa) at 1400°C |耐熱衝撃性(次） I耐蝕性/溶損指數 耐熟化性(％)The Mg〇 content is preferably from 28 to 40% by mass. Each of the examples of Tables 2 and 3 is an alumina-tantalum carbide-carbon brick in which alumina, tantalum carbide, graphite and aluminum are blended in the refractory raw material composition, and bricks of other components are shown in Table 4. Example 1 of Table 4 8 to 2: 3 is added to other materials of alumina-carbonized carbide-carbon brick, and specifically, examples 18 to 21 are glass-added' embodiments 2 2 and 23 For the addition of magnesium oxide, Example 2 4 is used as a carbon raw material for graphite and smokeless carbon. Further, Examples 25 and 26 are alumina-magnesia-carbon bricks, and Example 27 is alumina-carbon bricks. In the same manner as the alumina__carburized sand-carbon bricks shown in the examples of Tables 2 and 3, these examples have high heat bending strength and excellent saturability, and it is judged that secondary spinel has been formed. Moreover, the ripening resistance is also good. In the case where the blending amount of the glassy raw material exceeds 1.7 mass% and the total amount of the four kinds of impurities exceeds 0.5 mass%, the tendency of the thermal bending strength or the corrosion resistance to decrease is increased. Therefore, it is preferable that the blending amount of the vitreous raw material is 1.7 mass% or less and the total amount of four kinds of impurities is 〇·5 mass% or less. On the other hand, Comparative Example 9 is an alumina-magnesia-carbon brick which does not use a spinel material, and Comparative Example 1 is an alumina-carbon brick which does not use a spinel material, has low heat bending strength, and has poor corrosion resistance. . Further, in Examples 28 and 29, alumina carbon-based unfired bricks such as slabs used in a sliding nozzle device using carbon black as a carbon raw material and zirconia mullite as a refractory raw material were used. When compared with Comparative Example 1 1 in which the spinel material was not used, the thermal bending strength was high and the corrosion resistance was excellent, and it was judged that secondary spinel was formed. Moreover, the ripening resistance is also good. -21 - 201100351 Further, the following shows an example of the use of the alumina carbon system of the present invention for the kiln equipment. In order to compare the 'Al203-SiC-C barrier of Example 6 of the present invention with the brick of the conventional product of Comparative Example 6, the slag line ' of the 250T mixed iron vehicle (TPC) of A made iron was attached. 1 79ch is used in real time. As a result, the melt loss thickness of the brick of Example 6 stayed at 40% of the melt loss thickness of the brick of Comparative Example 6, and good results were obtained. The physical properties of the recovered bricks were measured. As a result, the apparent porosity was higher in the brick of Example 6 than in the brick of Comparative Example 6, and the thermal bending strength was also higher than that of the brick of Comparative Example 6 in Comparative Example 6. Prove the institution as originally envisioned. [Table 1] ΑΙ2〇3 (% by mass) MgO (% by mass) Average particle diameter ("m) Spinel A 66 33 60 Spinel B 66 33 50 Spinel C 66 33 40 Spinel D 66 33 30 Spinel E 66 33 20 Spinel F 66 33 15 Spinel G 66 33 7 Spinel Η 66 33 3 Spinel I 96 3 15 Spinel J 94 5 15 Spinel Κ 84 15 15 Spinel L 71 28 15 Spinel Μ 59 40 15 Spinel Ν 49 50 15 Spinel 0 39 60 15 -22- 201100351 Ο ❹ Comparative Example 6 〇〇ιο - Csl <0 ο σ> CO r*. s ο Comparative Example 5 〇Μ ΙΟ ο CM 〇 (O ο ο σ > r*«. s \Λ Comparative Example 4 〇\η ο CO <0 ο ο 〇> r- U9 Comparative Example 3 LO CO s ΙΑ ir» evi 〇 J (O 00 00 CM CO CM (OOW Example 11 ΙΛ c〇ιη - 〇csi «0 (Ο «•3 CM in e> io in β» Example 10 ΙΟ CO s ΙΑ - Ιο CNI U> ssi〇in C〇Example 9 1〇s ΙΟ - m esi (O 2〇CM CJ IO CO Example 8 » g ΙΛ - C\J eg (O Ο) o 〇> oo CO Comparison Example 2 A g ΙΛ - - eg L〇00 〇> l〇o 〇- Example 7 〇g ΙΑ 严 strict esj W lean σ> eg CM o in CO Example 6 〇s ιη - ο csl U> ο P*» sm GO Example 5 〇% ιπ - o Csi to ο r-> CO s CO Example 4 〇1/3 - ο Csj in CO l/> in O CO Example 3 〇ΙΟ - ο CNI l〇CSJ c〇CM e> 00 eo Example 2 § Another in - Ο (NJ IA CM o 00 〇0 c〇Q0 Example 1 § ιη inch - 〇CNI to ο O 03 00 IA 〇> m Comparative Example 1 s U) - 〇Csj ( O ο a> CO r·*- § ιο Average particle size 60// m 50 m 40μ m 30//m| 20^im E 51 U) Ε Bu ε 3. Ρ〇 fused alumina (particle size 3~ 0.1mm) fused alumina (particle size 0.1mm or less) 碳1 graphite|aluminum (particle size 100//m or less) | spinel A (MgO 33% by mass) spinel B (MgO 33% by mass) 1 1 spinel C (MgO 33% by mass) 1 spinel D (MgO 33% by mass) 1 spinel E (MgO 33% by mass) | spinel F (MgO 33% by mass) I 1 spinel G (MgO 33% by mass) 1 1 spinel H (MgO 33% by mass) I 〇Λ It ^rf, <ϋ9, P Igo \/ r< 1 Apparent porosity (%) ! |l400t: Apparent porosity (%) after heat treatment 1 1400ΪElastic modulus after heat treatment (GPa) 1 |Hot bending strength (MPa) at 1400°CI Thermal shock resistance (times) 1 lTear resistance/«loss index 1 Resistance to ripening (%) -23- 201100351 Comparative Example 8 〇S in - O CO m (Ο Eg CVJ Si (〇ο g Example 17 〇g LO - 〇Ol ιο in 〇> CM CM os CM 〇s in pairs - o CsJ to iO σ> CM CM og 〇> Example 15 § s in - O eg l〇CO 卜 CO CSi g CO Example 14 〇g in - Ο CSi irj CO 卜 (D c〇in to 揭 2 2荜〇s in - Ο eg in esi CO 40 CM o 闺2 〇s in - 〇40 二ιο n 〇in n 〇g in 对 - 〇Csl l〇oc〇卜罗 average particle size 15// m I 15/im 15# m 15/im| 15# m| 15// m| 15// m 15 // m 1 fused alumina (particle size 3~0.1mm) | fused alumina (particle size below 0.1mm) 1 碳I graphite|Ming (particle size below 100 Mm) | Stone I (MgO 3% by mass) Spar J (MgO 5% by mass) Spinel K (MgO 15% by mass) | Spinel L (MgO 28% by mass) | Spinel F (MgO 33% by mass) ! Spinel M (MgO 40 mass) %) | Spinel N (MgO 50% by mass) | Spinel 0 (MgO 60% by mass) ΓΟ if B·ton 13⁄4 Ιο | Apparent porosity (%) Apparent porosity of heat treated at 11400 °C W Elastic modulus (GPa) after heat treatment at 11400 °C Thermal bending strength (MPa) at 1400 °C | Thermal shock resistance (times) I Corrosion resistance / dissolution index resistance to ripening (%)
ClCl
-24- 201100351-24- 201100351
ΙΟ CN* S s CM CO CSI d ο CO to ο ο m CM Ο s CM r> ο OJ 10 CO σ> η S 0 s w> IKS iq K Ο s in ο CNi iO CO (Ο CO σ> 0 s 鎰2 in ο - CNi (O 0 ο 00 00 s 0 比較 例9 ΙΟ CM ο 寸 s - OJ CO 0 σ> 00 CO 0 0 實施 例27 in g 寸 - ο CSJ u> CO 卜 r- 0 s ir> 實施 例26 \Λ CM g s - ο Csl to 卜 00 0 s 10 實施 例25 \Γ> CO s ο - ο eg \n €〇 卜 卜 0 s m 實施 例24 in in CM m 卜 卜 - ο CNI 卜 寸 CM 0 If) 實施 例23 m CM LO CM ΙΟ s - ο csl ΙΑ 卜 CO 〇 s m 實施 例22 l〇 CO LO «Μ ΙΟ ο - ο CNJ IO CO 卜 卜 〇 s Ui 實施 例21 n 1/) eg ιο - ο 00 (O (A : 卜 οι CM s u> 實施 例20 CO 3 %Λ CM in - ο 卜 \n 卜 CO esj s lf> 實施 例19 ir> CM m - ο - 40 «Μ (D in CM n in 實施 例18 m l〇 C4 in - ο 1A 〇 CO o \r> CJ <〇 ΐΟ CM m <0 fl 15// m 電熔氧化鋁(粒徑3〜0.1mm) |電熔氧化鋁(粒徑〇_ 1mm以下） 氧化锆高鋁紅柱石(粒徑3〜0.1mm) | 碳化矽 I 石墨 無煙碳 I 碳黑 ! 1氧化鎂(粒徑3〜0.1mm) 1鋁(粒徑100 以下） 1尖晶石F(MgO 33質量％) 1玻璃 m 0¾ cs >-✓ Z_ it 1¾ is lo ® - 表觀氣孔率(％) ! 11400°C熱處理後的表觀氣孔率(％) 11400°C熱處理後的彈性模數(GPa) 1熱彎曲強度(MPa) at 1400°C 1耐熱衝撃性(次） 1耐蝕性/熔損指數 耐熟化性(％) -25- 201100351 【圖式簡單說明】 圖1係本發明的氧化鋁碳系不燒磚之熔渣耐蝕性試驗 後的微構造之模型圖。 【主要元件符號說明】 1 :磚 2 :尖晶石質保護層 3 :熔渣 -26 -ΙΟ CN* S s CM CO CSI d ο CO to ο ο m CM Ο s CM r> ο OJ 10 CO σ> η S 0 s w> IKS iq K Ο s in ο CNi iO CO (Ο CO σ> 0 s镒2 in ο - CNi (O 0 ο 00 00 s 0 Comparative Example 9 CM CM ο s s - OJ CO 0 σ > 00 CO 0 0 Embodiment 27 in g inch - ο CSJ u> CO 卜 r- 0 s ir> Example 26 \Λ CM gs - ο Csl to 00 0 s 10 Example 25 \Γ> CO s ο - ο eg \n €〇卜0 sm Example 24 in in CM m Bub- ο CNI 卜Inch CM 0 If) Example 23 m CM LO CM ΙΟ s - ο csl ΙΑ CO CO 〇 sm Example 22 l〇CO LO «Μ ΙΟ ο - ο CNJ IO CO Bubs s Ui Example 21 n 1/) Eg ιο - ο 00 (O (A: 卜οι CM s u> Example 20 CO 3 %Λ CM in - ο卜\n 卜CO esj s lf> Example 19 ir> CM m - ο - 40 «Μ ( D in CM n in Example 18 ml〇C4 in - ο 1A 〇CO o \r> CJ <〇ΐΟ CM m <0 fl 15// m fused alumina ( Diameter 3~0.1mm) | fused alumina (particle size 〇_1mm or less) zirconia mullite (particle size 3~0.1mm) | bismuth carbide I graphite smokeless carbon I carbon black! 1 magnesium oxide 3~0.1mm) 1 aluminum (particle size below 100) 1 spinel F (MgO 33% by mass) 1 glass m 03⁄4 cs >-✓ Z_ it 13⁄4 is lo ® - apparent porosity (%) ! 11400° Approximate porosity (%) after heat treatment of C. Elastic modulus (GPa) after heat treatment at 11400 °C 1 Thermal bending strength (MPa) at 1400 °C 1 Heat-resistant squeezing property (times) 1 Corrosion resistance/melt loss index resistance to ripening (%) -25- 201100351 [Simplified description of the drawings] Fig. 1 is a model diagram of the microstructure after the slag corrosion resistance test of the alumina carbon-based unfired brick of the present invention. [Main component symbol description] 1 : Brick 2 : Spinel protective layer 3 : Slag -26 -