經濟部智慧財產局員工消費合作社印製 490333 Α7 Β7 五、發明說明（1 ) 本發明係有關可有效控制於含有鋁之鋁鎭靜鋼等連續 鑄造中熔鋼通過之噴嘴內孔狹窄，甚至閉塞者之連續鑄造 用噴嘴。 先行技術中，熔鋼之連續鑄造用噴嘴係爲如下目的使 用之。 熔鋼之連續鑄造中連續鑄造用噴嘴具有由tun cHcer 注模具注入熔鋼之功能，惟此乃爲藉由此時與熔鋼之空氣 接觸之氧化之防止，或防止熔鋼之飛散，更爲防止往非金 屬介在物及模具面浮遊物之鑄片內卷曲而使注入熱水整流 化等目的下被使用者。 先行技術熔鋼之連續鑄造用噴嘴材質主要由石墨、鋁 氧粉、二氧化矽、矽氧化物等所組成者，惟，鑄造鋁鎭靜 鋼時將出現以下問題點。 鋁鎭靜鋼等，與做爲脫氧劑所添加之鋁存在於熔鋼中 之氧相互反應後，產生α -鋁氧粉等之非金屬介在物。又 ，熔鋼通過噴嘴時與大氣中之氧相互反應後，更產生鋁氧 粉。因此，鑄造鋁鎭靜鋼等時，於連續鑄造用噴嘴之內孔 表面上附著上述之鋁氧粉等之非金屬介在物後，堆積之後 ，其結果使得內孔變狹窄，最差情況使內孔閉塞而無法安 定鑄造。或此附著堆積後之α -鋁氧粉等非金屬介在物剝 離或脫落後卷入鑄片，導致鑄片之品質降低。 爲防止因上述α -鋁氧粉等非金屬介在物之內孔狹窄 及閉塞、由形成內孔之連續鑄造用噴嘴內面往通過上述內 孔流動熔鋼噴射不活性氣體後，防止存在於熔鋼中之^ - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -4 - ---------------.----訂---------線 (請先閱讀背面之注意事項再填寫本頁) 490333 A7 B7 五、發明說明（2) 鋁氧粉等之非金屬介在物附著堆積於連續鑄造用噴嘴內孔 面之方法被廣泛使用之（如特公平6 - 5 9 3 3號公報） 〇 惟，由上述熔鋼連續鑄造用噴嘴之內面噴出不活性氣 體之方法將出現如下之問題。 亦即，所噴出之不活性氣體量太多則藉由不活性氣體 產生之氣泡卷入鑄片中之氣孔，而產生缺陷。反之，所噴 出之不活性氣體量太少則α -鋁氧粉等之非金屬介在物附 著於連續鑄造用噴嘴之內孔面，堆積後，內孔狹窄，甚至 最壞情況致使噴嘴塞閉。 又，由連續鑄造用噴嘴內面往通過該內孔之流動熔鋼 均勻噴入不活性氣體有結構上之困難，且，長時間鑄造時 ，連續鑄造用噴嘴材質之組織劣化及伴隨結構劣化，造成 所噴出之不活性氣體之調節不安定。其結果造成α —鋁氧 粉等之非金屬介在物附著於連續鑄造用噴嘴之內孔面，進 而堆積使得內孔狹窄，甚至閉塞。 藉由非金屬介在物產生噴嘴閉塞，特別是鋁氧粉（ A 1 2 0 3 )介在物之噴嘴閉塞，將出現如下問題。亦即， (1 )鋼中之鋁藉由通過耐火物之接合部及耐火物組 織卷入空氣後氧化，且，含碳之耐火物中二氧化砂還原後 產生之S i〇供與氧後，生成鋁氧粉。 (2 )此鋁氧粉擴散、凝聚後形成鋁氧粉介在物。 (3 )又，噴嘴之內孔面中，石墨、碳消失後，內孔 表面成凹凸狀，易造成鋁氧粉介在物之堆積。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 0 .丨訂---------線· 經濟部智慧財產局員工消費合作社印製 -5 - 經濟部智慧財產局員工消費合作社印製 490333 A7 ______ B7 五、發明說明（3 ) 另外’做爲材質面之對策，由與鋁氧化物之反應性降 低使非氧化物原料（S i c，S 1 3 N 3、B N、Z r B 2 、Sialon等）添加於鋁氧粉石墨質，或由其自體所成之噴 嘴被提出（如：特公昭61 - 38152號公報）。 惟’添加上述原料於一般使用之鋁氧粉石墨質上時， 若太多量則無防止附著效果，由耐蝕性、劣化性之面觀之 均不實用。 另外，以非氧化物系之原料作成噴嘴時，其效果雖可 期待’而原料、製造面之成本卻高、極不實用。 更且’含Ca〇之氧化物原料（Ca〇、 Zr〇2、 Ca〇· Si〇2、 2Ca〇· Si〇2等）藉由Ca〇與 A 1 2〇3反應後易由熔鋼分離，產生低融點物質，因此亦 被提出由含石墨- C a〇之氧化物原料所成之噴嘴（如： 特公昭6 2 — 5 6 1〇1號公報）。 惟’藉由鑄造時之熔鋼溫度條件後，C a〇與 A i 2〇3反應性易受影響，因此，不產生低融點物質，且 ，於鋼中含多量A 1 2 0 3介在物時，其耐分裂性及耐蝕性 等面無法有效確保C a〇量。又，由耐火物於熔鋼所流出 之骨材內Z r〇2量其比重太高，因此，不易於熔鋼中浮出 ，不易由熔鋼浮出分離之。 本發明係於使用中噴嘴內孔面形成玻璃層後，防止卷 入通過耐火物之空氣，防止產生鋁氧粉，且，藉由使噴嘴 內孔面組織之平滑化後，控制於噴嘴內孔面鋁氧粉介在物 之堆積與附著，防止內孔狹窄，更可防止閉塞，提供可安 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -6- ----------------*--/1 l· I ---------^ IAWI (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印制衣 490333 A7 ______ B7 五、發明說明（4 ) 定鑄造之連續鑄造用噴嘴。 第1發明係其與連續鑄造用噴嘴熔鋼接觸之內孔表層 部以A 1 2〇3或A 1 2〇3做爲主成份，其融點爲1 8 0 0 °C以上之骨材爲1 5〜6 〇重量％，殘餘部份爲壽山石所 成之組成物者爲特徵之熔鋼連續鑄造用噴嘴者。 第2發明係其與連續鑄造用噴嘴熔鋼接觸之內孔表層 部爲銘氧粉（A 1 2〇3 )或以銘氧粉（A 1 2〇3 )做爲主 成份’其融點爲1 8 〇 (^艽以上之骨材爲1 5〜6 〇重量 % ’殘餘部份爲壽山石所成之組成物中，添加結合材·混 煉後成形’以非氧化氣中進行燒成者爲特徵之熔鋼連續鑄 造用噴嘴者。 第3發明係該壽山石爲使粒徑2 5 0 # m以下爲總壽 山石配合比量之6 0重量％以下者爲特徵之熔鋼連續鑄造 用噴嘴者。 第4發明係該壽山石以葉蠘石（A 1 2〇3· 4 S 1 0 2 · Η 2〇）做爲主成份者爲特徵之熔鋼連續鑄造 用噴嘴者。 第5發明係該壽山石爲8 0 0 °C以上煅燒後，結晶水 消失者爲特徵之熔鋼連續鑄造用噴嘴者。 第6發明係該結合材爲熱硬化性樹脂者爲特徵之熔鋼 連續鑄造用噴嘴者。 〔圖面之簡單說明〕 圖1係接觸於熔鋼之噴嘴內孔表層部中本發明所具備 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） ------------41^-----Γ U— t---------^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 490333 A7 B7 五、發明說明（5) 之耐火物之噴嘴縱切面圖者。 圖2係噴嘴內孔表層部及噴嘴下部（浸漬於熔鋼部份 )中本發明所具備耐火物之噴嘴切面圖者。 圖3係本發明與比較例中其配合組成·物理特性做爲 表1所代表之圖者。 主要元件對照表 10 連續鑄造用噴嘴 3 表層部以外之部份 2 表層部 1 內孔 〔發明之最佳實施形態〕 本發明中最被注視之面係以壽山石做爲噴嘴耐火物之 主成份使用之，同時，不配合先行技術之噴嘴所配合之石 墨者。石墨係於噴嘴使用時，與含於耐火物中之二氧化矽 之如下反應。Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 490333 Α7 Β7 V. Description of the invention (1) The present invention is related to the narrow inner hole of the nozzle through which the molten steel can be effectively controlled in continuous casting such as aluminum and static steel containing aluminum. Nozzle for continuous casting. In the prior art, the nozzle for continuous casting of molten steel is used for the following purposes. In the continuous casting of molten steel, the nozzle for continuous casting has the function of injecting molten steel from the tun cHcer injection mold, but this is to prevent oxidation by contact with the air of the molten steel at this time, or to prevent the scattering of the molten steel, and more Prevent the user from being curled into the casting slab of the non-metallic intermediary and floating on the mold surface to rectify the injected hot water. The material used for the continuous casting nozzle of the prior art molten steel is mainly composed of graphite, aluminum oxide powder, silicon dioxide, silicon oxide, etc. However, the following problems will occur when casting aluminum and static steel. Al-alloy steel and the like react with oxygen added to the molten steel as deoxidizer to produce non-metallic intermediaries such as α-aluminum oxide powder. In addition, when the molten steel passes through the nozzle and reacts with oxygen in the atmosphere, it produces aluminum oxide powder. Therefore, when casting aluminum and static steel, etc., the above-mentioned non-metallic intermediaries such as alumina oxide powder are adhered to the surface of the inner hole of the continuous casting nozzle, and after the accumulation, the inner hole becomes narrower. In the worst case, the inner hole is narrowed. The hole is closed and cannot be stably cast. Or the non-metallic intermediaries such as α-aluminum oxide powder after the adhesion and accumulation are peeled off or fall off, and they are rolled into the slab, which causes the quality of the slab to decrease. In order to prevent the narrowness and occlusion of the inner holes of non-metallic intermediaries such as α-aluminum oxide, the inert gas is sprayed from the inner surface of the continuous casting nozzle for forming the inner holes to the molten steel flowing through the inner holes to prevent the ^ In steel-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -4----------------.---- Order- ------- Line (Please read the precautions on the back before filling this page) 490333 A7 B7 V. Description of the invention (2) Non-metallic intermediaries such as aluminum oxide powder are deposited on the inner hole surface of the continuous casting nozzle This method is widely used (such as Japanese Patent Publication No. 6-5933). However, the method of injecting inert gas from the inner surface of the above-mentioned nozzle for continuous casting of molten steel will cause the following problems. That is, if too much inert gas is ejected, bubbles generated by the inert gas are entangled with pores in the slab, resulting in defects. Conversely, if the amount of the inactive gas ejected is too small, non-metallic intervening substances such as α-aluminum oxide powder adhere to the inner hole surface of the nozzle for continuous casting. After the accumulation, the inner hole is narrow, and even the worst case causes the nozzle to be blocked. In addition, it is structurally difficult to uniformly inject an inactive gas from the inner surface of the continuous casting nozzle to the flowing molten steel passing through the inner hole, and when the casting is performed for a long time, the structure of the material of the continuous casting nozzle is deteriorated and the accompanying structure is deteriorated. Causes unstable adjustment of the discharged inactive gas. As a result, non-metallic interfering substances such as α-aluminum oxide powder are adhered to the inner hole surface of the nozzle for continuous casting, and the inner hole is narrowed or even blocked due to accumulation. The nozzle occlusion caused by non-metallic intervening substances, especially the nozzle occlusion of the aluminum oxide powder (A 1 2 0 3) intervening substances, will cause the following problems. That is, (1) aluminum in steel is oxidized by being entangled in the air through the joints of the refractory and the refractory structure, and Si i0 generated after the reduction of the sand dioxide in the carbon-containing refractory is supplied with oxygen To generate aluminum oxide powder. (2) The aluminum oxide powder is diffused and agglomerated to form an aluminum oxide powder intermediate. (3) In addition, in the inner hole surface of the nozzle, after the disappearance of graphite and carbon, the inner hole surface becomes uneven, which is likely to cause the accumulation of aluminum oxide powder. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) 0. 丨 Order --------- Line · Ministry of Economy Wisdom Printed by the Consumer Cooperative of the Property Bureau-5-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 490333 A7 ______ B7 V. Description of the Invention (3) In addition, as a countermeasure for the material, the reaction with aluminum oxide is reduced Non-oxide raw materials (S ic, S 1 3 N 3, BN, Z r B 2, Sialon, etc.) are added to the aluminum oxide powder graphite, or the nozzles formed by them are proposed (such as: Teko Zhao 61- 38152). However, when the above-mentioned raw materials are added to alumite powder graphite which is generally used, if the amount is too large, there is no effect of preventing adhesion, and it is not practical from the aspects of corrosion resistance and deterioration. In addition, when a nozzle is made of a non-oxide-based raw material, the effect is expected, but the cost of the raw material and the manufacturing surface is high and extremely impractical. Furthermore, 'Ca〇-containing oxide raw materials (Ca〇, Zr〇2, Ca〇 · SiO2, 2Ca〇 · SiO2, etc.) are easily separated from the molten steel after Ca 0 reacts with A 1 203. It produces low melting point materials, so it has also been proposed as a nozzle made of graphite-C a0-containing oxide raw materials (eg, Japanese Patent Publication No. 6 2-5 6 1101). However, after the temperature conditions of the molten steel during casting, the reactivity of C a0 and A i 2 0 3 is easily affected. Therefore, no low melting point material is generated, and a large amount of A 1 2 0 3 is contained in the steel. In the case of solids, the surface of its split resistance and corrosion resistance cannot effectively ensure the C a0 content. In addition, the amount of ZrO2 in the aggregate flowing out of the molten steel from the refractory material is too high, so it is not easy to float out of the molten steel, and it is not easy to separate it from the molten steel. The invention is that after the glass layer is formed on the inner hole surface of the nozzle during use, the air passing through the refractory is prevented to prevent the generation of alumina powder, and the inner surface of the nozzle is smoothed and then controlled in the inner hole of the nozzle The surface aluminum oxide powder accumulates and adheres to the material, preventing the inner hole from narrowing and preventing occlusion. It also provides safe paper. The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -6- ---- ------------ *-/ 1 l · I --------- ^ IAWI (Please read the notes on the back before filling out this page) Employees of the Bureau of Intellectual Property, Ministry of Economic Affairs Consumption cooperative printing clothing 490333 A7 ______ B7 V. Description of the invention (4) Nozzle for continuous casting of fixed casting. The first invention is that the surface layer of the inner hole in contact with the molten steel of the continuous casting nozzle is composed of A 1 2 0 3 or A 1 2 0 3 as a main component, and the bone material whose melting point is 1 800 ° C or more is 15 to 60% by weight, and a nozzle for molten steel continuous casting characterized by a composition made of shoushan stone. The second invention is that the surface layer portion of the inner hole in contact with the molten steel of the continuous casting nozzle is Ming oxygen powder (A 1 2 0 3) or uses Ming oxygen powder (A 1 2 0 3) as the main component. Its melting point is 1 8 〇 (^ 艽 or more of the aggregate is 15 ~ 60 ％ by weight 'The remainder is a composition made of Shoushan stone, the binding material is added and formed after kneading', and the firing is performed in a non-oxidizing gas. Characteristics of nozzles for continuous casting of molten steel. The third invention is the nozzles for continuous casting of molten steel characterized in that the Shoushan stone has a particle size of 250 # m or less as 60% by weight of the total Shoushan stone mixing ratio. The fourth invention is the nozzle for molten steel continuous casting, which is characterized by the main component of chertite (A 1203 · 4 S 10 2 · Η 20). The fifth invention is that the shoushan stone is The nozzle for molten steel continuous casting is characterized by the disappearance of crystal water after calcination above 800 ° C. The sixth invention is the nozzle for molten steel continuous casting characterized by the bonding material being a thermosetting resin. [Picture Brief description of the surface] Fig. 1 is the paper size provided by the present invention in the surface layer portion of the inner hole of the nozzle that contacts the molten steel National Standard (CNS) A4 Specification (210 X 297 Public Love) ------------ 41 ^ ----- Γ U— t --------- ^ (Please Read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 490333 A7 B7 V. Description of the invention (5) Nozzle longitudinal section of the refractory nozzle. Sectional view of the nozzle of the refractory provided by the present invention in the lower part of the nozzle (immersed in the molten steel part). Fig. 3 shows the combination composition and physical characteristics of the present invention and the comparative example as shown in Table 1. Main components Table 10 Nozzle for continuous casting 3 Parts other than the surface layer part 2 Surface layer part 1 Inner hole [the best embodiment of the invention] The most watched surface in the present invention is the use of shoushan stone as the main component of the nozzle refractory, At the same time, graphite that is not matched with the nozzle of the prior art is used. The graphite reacts with the silica contained in the refractory as follows when the nozzle is used.
Si〇2(S) + C(S) = SiO(g) + CO(g)Si〇2 (S) + C (S) = SiO (g) + CO (g)
3SiO(g) + 2Al-Ah〇3(S) + 3Si 3C〇（g) + 2Al = Al2〇3(S) + 3C 藉由以上之反應後，二氧化矽分解後生成3 i 0 (g )及C〇（g )，成爲鋼中之氧供給源，與鋼中A 1反應 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) ^ ---------------·—11U— ---------^ —Awl (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 490333 A7 B7 五、發明說明（ό) 後生成A 1 2〇3。惟，壽山石時，與熔鋼中之碳共存下仍 未分解壽山石之粒子之壽山石之主鑛物之葉鱲石（ A 1 2 0 3 · 4 s 1 0 2 · 1"12〇）等之3丨〇2爲安定者。 此點可由壽山石與樹脂粉末及碳微粉所成之造粒進行作成 後，於透氣裝置內埋入1 5 0 0 °C X 2 4 h r熱處理後之 顯微鏡觀察下無粒子之崩散，氣泡產生者可證明。 又，先行技術之石墨添加1 0重量％之材質中，其熱 傳導率爲9 . 8 (kc. a l/m/hr/°C)相對的本發 明未添加石墨之材質中爲2 · 4 (kca 1/m/hr/ °C )較低者，且具優異之斷熱性、不易附著生金、及不易 析出α - A 1 2〇3等之非金屬介在物。 更且，含有先行技術之石墨之噴嘴中其石墨氧化時’ 內孔表面之平滑度降低，流於噴嘴內孔之熔鋼呈亂流因此 ，a - A 1 2〇3等之非金屬介在物被堆積之。而，未添加 石墨者其平滑度不會降低，因此不會於噴嘴內孔面產生凹 凸，不會堆積α - A 1 2〇3等之非金屬介在物。 壽山石之半熔鋼溫度爲1 5 0 0 °C左右者，與熔鋼接 觸之作動面中熔鋼後，玻璃皮膜成形後，平滑其作動面之 組織，且，藉由玻璃皮膜後可控制卷入通過耐火物組織之 空氣。 此點可由氧化氣中添加1 5 0 0 °C X 1 h r熱處理後 之石墨之材質透氣率爲6 · 5X10— 4 darcy相對的’相 同於其他條件未添加石墨之材質中1 5 0 0 °C X 1 h r熱 處理後透氣率爲1·〇ΧΐΟ-4 darcy較小者’透氣率降 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -9- --------------------^---------^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 490333 A7 B7 五、發明說明（7 ) 低點可判定之。 做爲連續鑄造用噴嘴使用時，於內孔面積極生成玻璃 皮膜，且，維持耐分裂性，因此，壽山石之配合重量比率 以4 0重量％以上者宜，當8 6重量％以上時其軟化變形 極大，且，對於熔鋼之耐蝕性不良，因此，以8 5重量％ 以下者宜。另外，此配合量爲其他成份之殘餘部份者。 本發明噴嘴係以A 1 2〇3或以A 1 2〇3爲主成份者做 爲骨材，其融點爲1 8 0 0 °C以上之骨材配合1 5〜6 0 重量％者’以A 1 2〇3爲主成份’做爲骨材之尖晶石 M g 0 * Al2〇3、八12〇3，431〇2係具有可賦予 成形體之噴嘴具有強度與耐蝕性之作用者。 做爲壽山石之種類者可使用葉蠟石質壽山石、陶土質 壽山石、絹雲母質壽山石三種中任一種，惟，考慮使用時 ，與熔鋼接觸之內孔面呈半熔融化後，玻璃層之形成與熔 鋼之耐熔損性後，以耐火度S K 2 9〜3 2之葉蠟石質壽 山石爲較理想者。陶土質壽山石其耐火度爲S K 3 3〜 3 6爲較高者，反之，絹雲母質壽山石其耐火度則爲 SK 2 6〜2 9之較低者，因此，均不適合。 做爲壽山石者使用於8 0 0 °C以上進行煅燒後，結晶 水消失之壽山石之理由係若配合未煅燒之壽山石後’所形 成之噴嘴燒成後，其壽山石中之結晶水將於5 0 0〜 8〇0 °C下被釋放，此時熱膨脹率呈異常變大，此乃成形 體內龜裂所致。 壽山石之粒度若平均粒徑2 5 0 Mm以下爲壽山石配 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -TO- ---------------Γ u I l· I ^---------線 (請先閱讀背面之注意事項再填寫本頁) 490333 A7 B7 五、發明說明（8) 合重量比之6 0 %以上時，易產生成形時之層壓塑料等組 織缺陷，且，做爲連續鑄造用噴嘴使用時，易產生壽山石 粒子之軟化變形，因此，以6 0 %以下者宜。 由主成份葉蠟石（A 12〇3· 4 S i 0 2 · H2〇）之 壽山石6 5〜9 0重量％之殘餘部份，主成份A 1 2〇3或 A 1 2〇3之骨材1 5〜6 0重量％所成之耐火物組成無壽 山石粒之分解，不致如S 1〇2之做爲鋼中之供氧源者。且 ，壽山石之半熔融溫度爲1 5 0 Ot左右，接近熔鋼之鑄 造溫度，與熔鋼接觸之作動面中形成玻璃皮膜層後，使作 動面組織呈平滑後，控制卷入通過耐火物組織之空氣後， 具有抑制A 1 2〇3及金屬之附著效果。 爲使該壽山石與骨材所配合之組成物於噴嘴成形，以 熱硬化性樹脂如：苯酚樹脂、呋喃樹脂等5〜1 5重量做 爲結合材配合後，噴嘴之形狀被成形後，燒成之。此成形 方法係其C I P ( Cold isostatic pressing )壓縮呈均勻成 形體者宜。又，燒成溫度以1000〜1300 °c者宜。 另外，做爲燒成氣體者還原性氣體。亦即非氧化性氣體者 比氧化性氣體者所配合之樹脂較不會氧化較爲理想者。 以下，參考本發明連續鑄造用噴嘴圖面之同時進行說 明。圖1係代表本發明之連續鑄造用浸漬噴嘴之垂直切面 之1例者。此連續鑄造用噴嘴1 0係配置於tun dicer與 模具之間，將熔鋼由tun dicer往模具注入做爲浸漬噴嘴使 用之。如圖1所示，連續鑄造用噴嘴1 0之熔鋼之流動內 孔1之表層部2係藉由具有上述化學成份組成之耐火物所 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ---------訂---------線· 經濟部智慧財產局員工消費合作社印製 -11 - 經濟部智慧財產局員工消費合作社印製 490333 A7 B7 五、發明說明（9) 形成者。表層部以外之部份3爲先行技術之鋁氧粉石墨質 者。 另外’此連續鑄造噴嘴之尺寸如：全長約爲1 m、內 孔直徑約爲6 c m、外直徑爲1 6 c m者、厚度約爲5 c m者。本發明耐火物之厚度爲2〜1 5mm者。又，此 尺寸僅爲1例，本發明並非僅限於此，可依所鑄造之鑄片 尺寸進行變更。 又，圖2係代表全部浸漬於鑄模內熔鋼之部份以本發 明耐火物所製成之噴嘴形態。任何狀態下，一般閉塞噴嘴 內孔之鋁氧粉集聚於噴嘴下部之內孔。本發明浸漬噴嘴於 內孔表層部2中抑制附著，堆積存在於熔鋼中之鋁氧粉等 非金屬介在物。以下，藉由實施例說明本發明。 實施例. 於不同成份之9個混合物中添加5〜1 0重量％之粉 末及溶液之苯酚樹脂後，此等經混合、混煉後取得之組成 物於1 0 0 0〜1 2 〇 〇。(：下進行燒成之。由此9個組成 物調製成如下之成形體。 第1成形體（以下稱成形體1 )係針對鋁氧粉等之非 金屬介在物之附著量及熔鋼進行耐蝕性之試驗，爲具有 3〇mmx 3〇mmx 2 3〇mm尺寸之成形體者。 第2成形體（以下稱成形體2 )係爲測定透氣率之具 有5 OcDmmx 2 Omm尺寸之成形體者，第3成形體（ 以下稱成形體3 )係爲試驗耐分裂性之具有外徑1 〇〇 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -IT- ------------4!^--------訂---------線"^^丨 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 490333 A7 B7 五、發明說明（10) mm、內徑6Omm及長度25Omm尺寸之成形體者。 分別取得之成形體於1 0 0 0〜1 2 0 0 °C溫度下燒成後 ，調整採樣1〜9。 上述分別之採樣1至5 (以下稱本發明之採樣）及採 樣6至9 (以下稱比較用採樣）中，表1顯示其物理特性 値（氣孔率及容積比重）。將本發明分別之成形體3之採 樣1至5及比較用採樣6至9於電爐上以1 5 0 0 t之溫 度下進行加熱3 0分鐘後，藉由水進行急冷後進行檢測其 耐分裂性。其結果以表1代表圖3示之。 將上述本發明分別成形體1之採樣1至5及比較用採 樣6至9浸漬於含有0.02至0·05重量％之鋁之 1 5 2 0 °C溫度之熔鋼中浸漬1 8 0分鐘後，檢測其熔損 率（％ )及附著鋁氧粉等之非金屬介在物之量。其結果以 表1代表圖3示之。 又，分別將本發明成形體2之採樣1至5及比較用採 樣6至9於電爐上以1 5 0 0 °C溫度進行加熱6 0分鐘後 ，測定其冷卻後之透氣率。該試驗結果，以表1代表圖1 示之。由表.1可淸楚發現，本發明之採樣具有優異之耐分 裂性，不但熔損率極低，且，不附著鋁氧粉等非金屬介在 物，因此，可有效控制熔鋼連續鑄造用噴嘴內孔之狹窄， 更可有效抑制閉塞。 又，本發明之採樣由於透氣率小，實用上可抑制通過 耐火物卷入之空氣。 另外，比較用之採樣6中，由於壽山石含量過多，鋁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -1T- -----------------^------------^ ^^1 (請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 490333 A7 B7 五、發明說明（11) 氧粉附著量雖少，耐分裂性卻明顯低劣，同時’對於溶鋼 之耐蝕性亦明顯不良。 又’比較用採樣7中，取代壽山石因含A 1 2〇3與 S 1〇2之單體故S i〇2分解之後，供入氧於鋼中，導致 鋁氧粉附著量明顯增大。另外，比較用採樣8中，取代壽 山石者未含S i〇2 ’僅含A 1 2〇3因此儘管去除供於鋼 中氧之鑛物，其耐分裂性仍明顯低劣、透氣率高、鋁氧粉 等之非金屬介在物之附著量亦多。 另外，比較用採樣9中，雖由石墨、壽山石與 A 1 2〇3所組成者，惟，由於含有石墨，因此’當熔鋼溫 度爲極低之1 5 2 0 ± 1 〇°C時，鋁氧粉附著量稍多，且 ，生金附著量亦多。 〔產業上可利用性〕 如以上之說明，本發明熔鋼連續鑄造用噴嘴不會產生 耐火物組織之劣化，可有效控制因鋁氧粉等非金屬介在物 所導致鋁鎭靜鋼之內孔狹窄、甚至閉塞、可安定鑄造之。 又，使用本發明之噴嘴後，將1進料3 0 0噸之低碳 鋁鎭靜鋼以2絞合線之切片連續鑄造機鑄造後，可使5至 7進料鑄造無閉塞之噴嘴。又，先行技術之噴嘴進行鑄造 後，2至4進料鑄造後則產生噴嘴閉塞進而造成鑄造中斷 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -14- -----------------------------^ (請先閱讀背面之注意事項再填寫本頁) 490333 A7 B7 五、發明說明（12 ) 經濟部智慧財產局員工消費合作社印製 〇 Z © Ο Ο 〇 —> CO ^ 〇〇 〇〇 \〇 ㈠〜’乂 cjn ^ CSI οο ο as Ό 無龜裂 m ❺ Ο Ο 〇 CNI > — 13.4 2.43 8.7 2.8 CN wo ί'·"Ή 龜裂出現 Ξ ^ 比較用 Θ Ο m to -~' 12.9 2.46 8.0 2.4 Ο OQ 無龜裂 r—* r—Η ο ο r—t 12.8 2.50 8.4 2.0 Csl 無龜裂 CO r—l 本發明樣品Ν 〇 . Ο Ο Ο m -~~' 13.3 2.47 9.7 4.1 Ό un CNI 無龜裂 ^ UO Ο Ο .11· .11. @ Ο Ο Ο CO ι~1 13.3 2.48 9.9 4.0 OQ 無龜裂 ο ο .11· .11· © 5 ^ - 13.7 2.44 9.0 3.7 CNl 無龜裂 ο ο •ΙΓ .11· Θ S ^ - 13.5 2.45 9.0 3.6 oo o C<1 無龜裂 ο ο .11· .11. ㊀ 0 10 W οο — ^ 13.2 2.47 9.2 2.9 o υη r—* 無龜裂 ο ο .11· _ΙΙ. ο < ^ .. ^ ^ 9 〇 〇 W Ε < s 03 s - S _賊條· a m m ξ i£ « it s 嫉娣觳癒芒 熔損率（％) (熔鋼溫度1500°C ) 透氣率氧化氣分 (10'4 X darcy) 145CTC lhr處理後 耐分裂性 ε ^ w Ξ ο 5 ^ _ _ 二 £ # ^ S ^ J ^ ^ ； W 配合組成 (重量％ ) 物理特性 -lb - ------------41^--------1---------^ (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）3SiO (g) + 2Al-Ah〇3 (S) + 3Si 3C〇 (g) + 2Al = Al2〇3 (S) + 3C After the above reaction, the silicon dioxide is decomposed to generate 3 i 0 (g) And C0 (g), become the oxygen supply source in steel, and react with A1 in steel. The paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) ^ -------- ------- · —11U— --------- ^ —Awl (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 490333 A7 B7 5 After the invention description (ό), A 1 2 03 is generated. However, in the case of Shoushan stone, coexisting with the carbon in the molten steel has not yet decomposed the particles of Shoushan stone. The main mineral of the Shoushan stone is a vermiculite (A 1 2 0 3 · 4 s 1 0 2 · 1 " 12〇), etc. 3 丨〇2 is a stable person. This point can be made from pellets made of shoushan stone, resin powder and carbon fine powder, and embedded in a ventilating device after heat treatment at 15 0 ° CX 2 4 hr without microscopic observation of the particles. prove. In addition, in the prior art graphite-added material with a weight of 10%, its thermal conductivity is 9.8 (kc. Al / m / hr / ° C). In contrast, in the present invention, the graphite-free material is 2. 4 (kca 1 / m / hr / ° C), and has excellent thermal insulation, hard to adhere to gold, and difficult to precipitate non-metallic intermediaries such as α-A 1 2 03. In addition, in the nozzle containing graphite of the prior art, when the graphite is oxidized, the smoothness of the inner hole surface is reduced, and the molten steel flowing in the inner hole of the nozzle is turbulent. Therefore, non-metallic intermediaries such as a-A 1 2 03 Be stacked. On the other hand, if graphite is not added, the smoothness will not be lowered, so there will be no unevenness on the inner hole surface of the nozzle, and non-metallic intervening materials such as α-A 1 2 03 will not be deposited. The temperature of Shoushan Stone's semi-fused steel is about 15 0 ° C. After the molten steel is in the active surface that is in contact with the molten steel, the glass film is formed to smooth the structure of the active surface, and the volume can be controlled by the glass film. Into the air passing through the refractory structure. This point can be added to the oxidizing gas at 15 0 0 ° CX 1 hr after the heat treatment of the graphite material. The air permeability is 6 · 5X10— 4 darcy relative 'same as the other conditions without the addition of graphite 1 5 0 0 ° CX 1 After hr heat treatment, the air permeability is 1 · 〇χΐΟ-4 darcy, whichever is smaller, the air permeability is reduced. The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -9- -------- ------------ ^ --------- ^ (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 490333 A7 B7 5 2. Description of the invention (7) The low point can be judged. When used as a nozzle for continuous casting, a glass film is actively formed on the inner hole surface and maintains crack resistance. Therefore, the blending weight ratio of Shoushan Stone is preferably 40% by weight or more, and it will soften when it is 86% by weight or more. The deformation is extremely large and the corrosion resistance to molten steel is poor, so it is preferably 85% by weight or less. In addition, this blending amount is the remainder of other ingredients. The nozzle of the present invention is made of A 1 2 0 3 or A 1 2 0 3 as the main component, and the melting point of the bone material above 18 0 ° C is 15-60% by weight. A 1 2 03 is the main component of spinel Mg 0 * Al 2 0 3, 8 12 3, 4 30 2 as the bone material, which has the effect of giving the formed body nozzle strength and corrosion resistance. . As the type of shoushan stone, you can use any one of the pyrophyllite shoushan stone, the clay shoushan stone, and the sericite shoushan stone. However, when considering the use, the inner hole surface in contact with the molten steel is semi-melted. After forming the melting loss resistance with molten steel, a pyrophyllite shoushanite with a fire resistance of SK 2 9 ~ 32 is preferred. The clay-type Shoushan stone has a higher fire resistance of S K 3 3 ~ 36, and conversely, the sericite-type Shoushan stone has a lower fire resistance of SK 2 6 ~ 29, so it is not suitable. As a Shoushan stone, the reason for using Shoushan stone whose crystal water disappears after being calcined at more than 80 ° C is that if the nozzle formed by the uncalcined Shoushan stone is burned, the crystal water in the Shoushan stone will be 50%. Released at 0 ~ 80 ° C, at this time the thermal expansion rate becomes abnormally large, which is caused by cracks in the forming body. If the average particle size of Shoushan stone is less than 2 50 Mm, the paper size of Shoushan stone is compatible with Chinese National Standard (CNS) A4 (210 X 297 mm) -TO- -------------- -Γ u I l · I ^ --------- line (please read the precautions on the back before filling this page) 490333 A7 B7 V. Description of the invention (8) When the total weight ratio is more than 60% It is easy to produce structural defects such as laminated plastics during molding, and when used as a nozzle for continuous casting, it is easy to cause softening and deformation of shoushanite particles. Therefore, it is preferable that it is less than 60%. Residual part of Shoushan stone 65-90% by weight of the main component pyrophyllite (A 12〇3 · 4 S i 0 2 · H2〇), the bone of the main ingredient A 1 2 03 or A 1 2 03 The 15-50% by weight of the refractory formed by the material constitutes no decomposition of the Shoushan stone, and it is not as good as the source of oxygen in steel as S 102. In addition, the semi-melting temperature of Shoushan Stone is about 150 Ot, which is close to the casting temperature of molten steel. After the glass film layer is formed on the moving surface in contact with the molten steel, the structure of the moving surface is smoothed, and the structure is controlled to pass through the refractory structure. After air, it has the effect of suppressing the adhesion of A 1 203 and metal. In order to form the composition composed of the shoushanite and the bone material in the nozzle, 5 to 15 weights of thermosetting resins such as phenol resin and furan resin are used as the binding material. After the shape of the nozzle is formed, it is fired. Of it. This forming method is preferably one in which C I P (Cold Isostatic Pressing) is compressed to form a uniform body. The firing temperature is preferably 1000 to 1300 ° C. In addition, it is a reducing gas as a firing gas. That is, the non-oxidizing gas is more ideal than the resin compounded with the oxidizing gas. Hereinafter, the description will be made while referring to the drawing surface of the continuous casting nozzle of the present invention. Fig. 1 shows an example of a vertical section of a dipping nozzle for continuous casting according to the present invention. This continuous casting nozzle 10 is arranged between the tun dicer and the mold, and the molten steel is injected from the tun dicer into the mold as an immersion nozzle. As shown in Figure 1, the surface layer 2 of the flowing inner hole 1 of the molten steel nozzle 10 for continuous casting is made of refractory materials with the above-mentioned chemical composition. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page) --------- Order --------- Line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs- 11-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 490333 A7 B7 V. Description of Invention (9) The creator. Part 3 other than the surface layer part is a prior art alumina powder graphite. In addition, the dimensions of this continuous casting nozzle are, for example, those having a total length of approximately 1 m, an inner hole diameter of approximately 6 cm, an outer diameter of 16 cm, and a thickness of approximately 5 cm. The thickness of the refractory of the present invention is 2 to 15 mm. In addition, this size is only an example, and the present invention is not limited to this, and can be changed according to the size of the cast slab. Fig. 2 shows the form of a nozzle made of the refractory material of the present invention in which all the molten steel is immersed in a mold. In any state, the aluminum oxide powder that normally closes the inner hole of the nozzle is collected in the inner hole at the lower part of the nozzle. The immersion nozzle of the present invention suppresses adhesion in the inner-hole surface layer portion 2 and accumulates non-metallic intermediaries such as alumina powder in the molten steel. Hereinafter, the present invention will be described by way of examples. Example: After adding 5 to 10% by weight of powder and a solution of phenol resin to 9 mixtures of different ingredients, the composition obtained after mixing and kneading is in the range of 1000 to 12,000. (: Firing is carried out below. From these 9 compositions, the following formed bodies are prepared. The first formed body (hereinafter referred to as formed body 1) is for the amount of non-metallic substances such as alumina oxide powder and the amount of molten steel. The corrosion resistance test is a molded body having a size of 30 mmx 30 mm x 2 30 mm. The second molded body (hereinafter referred to as a molded body 2) is a molded body having a size of 5 OcDmmx 2 Omm for measuring the air permeability. The third formed body (hereinafter referred to as formed body 3) is an outer diameter of 100 for testing the resistance to splitting. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -IT- --- --------- 4! ^ -------- Order --------- line " ^^ 丨 (Please read the precautions on the back before filling this page) Economy Printed by the Ministry of Intellectual Property Bureau's Consumer Cooperatives 490333 A7 B7 V. Description of the invention (10) mm, shaped body with a diameter of 60 mm and a length of 25 mm. The shaped bodies were obtained at 1 00 0 to 1 2 0 0 ° C After firing at the temperature, adjust the samples 1 to 9. Among the above-mentioned samples 1 to 5 (hereinafter referred to as the sampling of the present invention) and samples 6 to 9 (hereinafter referred to as the comparative sampling), Table 1 shows the physical Property 气 (porosity and volume specific gravity). Samples 1 to 5 and comparative samples 6 to 9 of the molded body 3 of the present invention are heated on an electric furnace at a temperature of 15 0 t for 30 minutes, and then borrowed. After being quenched with water, the split resistance was tested. The results are shown in Table 1 and shown in Figure 3. Samples 1 to 5 and comparative samples 6 to 9 of the molded body 1 of the present invention were immersed in 0.02 to 0 · After being immersed in molten steel at a temperature of 1520 ° C of 05 wt% aluminum for 180 minutes, the melt loss rate (%) and the amount of non-metallic intervening substances such as aluminum oxide powder were measured. The results are shown in the table. 1 represents that shown in Fig. 3. In addition, samples 1 to 5 and comparative samples 6 to 9 of the molded body 2 of the present invention were heated on an electric furnace at 150 ° C for 60 minutes, and then measured for cooling. The test results are shown in Table 1 as shown in Figure 1. From Table. 1, it can be clearly found that the sample of the present invention has excellent split resistance, not only the melt loss rate is extremely low, but also no aluminum oxide is attached. Non-metallic intermediaries such as powder can effectively control the narrowness of the inner hole of the nozzle for continuous casting of molten steel, and can effectively suppress the closing In addition, because the sample of the present invention has a small air permeability, it can practically suppress the air entrained by the refractory. In addition, in the sample 6 for comparison, due to the excessive content of shoushanite, the aluminum paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -1T- ----------------- ^ ------------ ^ ^^ 1 (Please read first Note on the back? Matters need to be completed on this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 490333 A7 B7 V. Description of the invention (11) Although the amount of oxygen powder is small, the split resistance is significantly inferior. Corrosion resistance is also significantly poor. In 'Sampling 7 for comparison', the replacement of Shoushan Stone due to the monomers containing A 1 2 03 and S 1 02 resulted in the decomposition of S 102 and supply of oxygen to the steel, resulting in a significant increase in the amount of aluminum oxide powder adhered. In addition, in Comparative Sampling 8, those who replaced Shoushan Stone did not contain S i0 2 'and contained only A 1 2 03. Therefore, despite the removal of the minerals that supply oxygen in steel, its split resistance is still significantly inferior, the air permeability is high, and aluminum oxide There is also a large amount of adhesion of non-metallic intermediaries such as powder. In addition, in comparison sample 9, although it is composed of graphite, shoushanite, and A 1 2 03, because it contains graphite, 'when the molten steel temperature is extremely low 1520 ± 10 ° C, The amount of aluminum oxide powder attached is slightly more, and the amount of gold deposit is also large. [Industrial Applicability] As described above, the nozzle for continuous casting of the molten steel of the present invention does not cause deterioration of the refractory structure, and can effectively control the inner holes of aluminum-alloyed steel caused by non-metallic intermediaries such as aluminum oxide powder. Narrow, even occluded, stable to cast. In addition, after using the nozzle of the present invention, 300 tons of low-carbon aluminum alloy static steel with 1 feed is casted by a 2-strand continuous die casting machine, and 5 to 7 feeds can be used to cast the nozzle without occlusion. In addition, after the nozzles of the prior art are cast, the nozzles will be blocked after 2 to 4 feeds and the casting will be interrupted. This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -14- --- -------------------------- ^ (Please read the notes on the back before filling out this page) 490333 A7 B7 V. 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Ο < ^ .. ^ ^ 9 〇〇W Ε < s 03 s-S _ thieves · amm ξ i £ «it s Melting loss rate (%) (melting steel temperature 1500 ° C) Air permeability Oxidation gas content (10'4 X darcy) 145CTC lhr Split resistance after treatment ^ w Ξ ο 5 ^ _ _ 2 £ # ^ S ^ J ^ ^; W compound composition (% by weight) Physical properties -lb------------- 41 ^ -------- 1 ------- -^ (Please read the notes on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)