A7 -436^7 ' 五、發明説明（1 ) 本發明係關於陶瓷組合物，其在高熔解溫度之金屬譬如 鐵或鋼之處理與鑄造上特別有價值。 關於製造被使用在熔融金屬譬如鋼之處理與鱗造上之物 件之一般實施，係來自碳結合之陶瓷材料（亦稱爲黑色耐 火材料）。此種物件之實例係爲供含有熔融金屬之容器用 之傾倒喷嘴，該容器譬如盛桶或澆鑄用漏斗，及圍繞著從 一個容器流至另一個容器之金屬液流之套筒。此等碳結合 之陶瓷材料係製自一種混合物，其包含石墨，一或多種氧 化物譬如氧化銘、氧化鎂及氧化錯，及黏合劑譬如盼樹脂 或瀝青，其將分解而產生破鍵。 上述碳結合之陶瓷材料遭遇到許多缺點。其具有不良熱 振抵抗性及易於龜裂，以致其必須以某種方式方處理譬如 喷嘴與套筒之物件，以在物件被迅速加熱至高溫時，使所 產生之熱振降至最低。此材料亦具有低氧化作用抵抗性， 因其含有相對較高比例之碳，主要是呈石墨形式。此材料 在特定應用上亦壤遇到其他缺點。例如，當铸造銘淨靜辆 時，噴嘴之外部表面容易受到存在於噴嘴所浸没之熔融金 屬表面上之溶渣攻擊（稱爲熔澄管線攻擊），以及嘴嘴孔易 在使用時由於氧化鋁之積聚而變得阻塞。 目前已發現一種碳結合之陶瓷材料，其包含氮化硼、二 硼化鲒及至少一種其他耐火材料之混合物，其特別可作爲 習用含石墨之碳結合陶瓷材料之替代物使用，以用於製造 供熔融金屬譬如鋼之處理與鑄造上使用之物件。 根據本發明之第一個特徵，係提供一種陶瓷組合物，其 -q - |乂::.一丄 (CNS ) A4規格（210X297公羞） ^^1 ^^1 ^^1 ^^1 ^^1 ^^1 ^ΙΛ!/ ^^1 1^1 ^^1 m. ^~W (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 4 3 647 1 A7 ________B7 五、發明説明（2 ) 包含氮化硼、二硼化锆及至少一種其他耐火材料粒子之混 合物，藉有機黏合劑之分解所產生之碳結合在一起。 該其他耐火材料可爲例如耐火金屬、氧化物、碳化物、 棚化物或I化物。 耐火金屬可爲例如硼。 適當耐火氧化物之實例，包括氧化鋁、氧化锆、氧化鎂 、氧化虹、氧化與、氧化鉻及氧化砂。可使用超過一種氧 化物，且氧化物可爲混合耐火氧化物，譬如富銘紅柱石。 適當碳化物之實例，包括碳化矽、碳化硼、碳化鋁及碳 化锆。可使用超過一種碳化物。 適當硼化物之實例，包括二硼化鈦與六硼化鈣，及適當 氮化物之實例，包括氮化矽、氮化鋁、氮化鈦、氮化锆及 赛而隆（sialon)。可使用超過一種硼化物及超過一種氮化 物。 經濟部中央標準局貝工消費合作社印製 -------------；----:-訂 (請先閲讀背面之注意事項再填寫本頁) 根據本發明之一項較佳具體實施例，陶瓷組合物係包含 氪化硼、二硼化锆及氧化锆之混合物，且此陶瓷組合物較 佳係含有5-70重量％氮化硼，更佳爲15_5〇重量％，5-60 重量％二硼化锆，更佳爲15-50重量％，及5-80重量％氧 化锆，更佳爲10-60重量％。 根據本發明之另一項較佳具體實施例，陶瓷組合物係包 含敗化棚、一棚化錯及氧化銘之混合物，且此陶资組合物 較佳係含有5-70重量％氮化硼，更佳爲15-50重量％，5-60重量％二硼化锆，更佳爲15-50重量％，及10-70重量％ 氧化鋁，更佳爲15-60重量％。 .： • 4 _ 冲埋. __ Μ 本紙張尺度制巾麵家縣（c叫Α4規格（2iGX297公澄) ~— 436471 A7 ___ B7__ 五、發明説明（3) 在上述較佳具體實施例中，陶瓷组合物中各成份之比例 ，係以重量百分比表示，以陶瓷組合物之總重量爲基準， 排除碳鍵° 會分解而產生碳鍵之有機黏合劑，可爲例如酚曱醛樹脂 ，譬如酚醛清漆或可溶酚-甲醛樹脂、尿素-曱醛樹脂、三 聚氰胺-甲醛樹脂、環氧樹脂、呋喃樹脂或瀝青。 有機黏合劑較佳爲酚-甲醛樹脂，且此樹脂較佳係以液 體形式使用。可使用粉狀酚樹脂，但必須溶解此樹脂在適 當溶劑中，譬如在糠醛中，以使樹脂與其他成份混合並產 生陶瓷組合物。液體酴樹脂之用量通常爲5-25重量％，較 佳爲10-15重量％，以全部其他成份爲基準，並於陶瓷組 合物產生後，此組合物通常將含有2-12重量％，較佳爲5 重量％之譜之藉由樹脂分解所產生之碳，以陶瓷組合物之 總重量爲基準。 經濟部中央標準局員工消費合作社印製 本發明之陶瓷組合物可以下述方式製成，首先將氮化硼 、二棚化锆及其他耐火材料之粒子混合在一起，然後添加 液體樹脂並混合，直到粒子與樹脂之混合物均勾爲止。可 能必須加熱混合物以降低樹脂之液體含量，以使得此混合 物適合用以成形。然後，使混合物形成所要之形狀，較佳 係在適當模具中藉由混合物之冷等力壓製。於成形後，將 此型料加熱以使樹脂熟化與交聯，例如在约150 - 300°C下 約1小時，然後在約700-1200°C下加熱，以使樹脂熱解並 產生碳鍵。 雖然本發明之陶瓷組合物可用於其他應用，例如在玻璃A7 -436 ^ 7 'V. Description of the invention (1) The present invention relates to ceramic compositions, which are particularly valuable in the treatment and casting of metals with high melting temperatures such as iron or steel. The general implementation of the manufacturing and processing of molten metal such as steel is based on carbon-bonded ceramic materials (also known as black refractory materials). Examples of such articles are pouring nozzles for containers containing molten metal, such as kegs or casting funnels, and sleeves surrounding a stream of metal flowing from one container to another. These carbon-bonded ceramic materials are made from a mixture containing graphite, one or more oxides such as oxide oxide, magnesium oxide, and oxide, and binders such as resin or asphalt, which will decompose to produce broken bonds. The carbon-bonded ceramic materials described above suffer from many disadvantages. It has poor thermal shock resistance and is prone to cracking, so that it must handle objects such as nozzles and sleeves in a way that minimizes the thermal vibration generated when the object is rapidly heated to high temperatures. This material also has low resistance to oxidation because it contains a relatively high proportion of carbon, mainly in the form of graphite. This material also suffers from other disadvantages in certain applications. For example, when casting a clean car, the external surface of the nozzle is vulnerable to slag attack (known as a melt line attack) existing on the surface of the molten metal submerged by the nozzle, and the mouth of the nozzle is easily affected by alumina during use. Accumulate and become blocked. A carbon-bonded ceramic material has been discovered that includes a mixture of boron nitride, hafnium diboride, and at least one other refractory material, which is particularly useful as a substitute for conventional graphite-containing carbon-bonded ceramic materials for use in manufacturing Articles for the processing and casting of molten metals such as steel. According to a first feature of the present invention, a ceramic composition is provided, which has -q-| 乂 ::. 一 丄 (CNS) A4 size (210X297 male shame) ^^ 1 ^^ 1 ^^ 1 ^^ 1 ^ ^ 1 ^^ 1 ^ ΙΛ! / ^^ 1 1 ^ 1 ^^ 1 m. ^ ~ W (Please read the precautions on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 3 647 1 A7 ________B7 V. Description of the Invention (2) A mixture containing boron nitride, zirconium diboride, and at least one other refractory particle, which are combined by carbon generated by the decomposition of an organic binder. The other refractory materials may be, for example, refractory metals, oxides, carbides, sintered compounds, or Iides. The refractory metal may be, for example, boron. Examples of suitable refractory oxides include alumina, zirconia, magnesia, rainbow oxide, oxidized oxide, chromium oxide, and sand oxide. More than one oxide can be used, and the oxide can be a mixed refractory oxide, such as Fuming Andalusite. Examples of suitable carbides include silicon carbide, boron carbide, aluminum carbide, and zirconium carbide. More than one carbide can be used. Examples of suitable borides include titanium diboride and calcium hexaboride, and examples of suitable nitrides include silicon nitride, aluminum nitride, titanium nitride, zirconium nitride, and sialon. More than one boride and more than one nitride can be used. Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -------------; ----:-Order (please read the precautions on the back before filling this page) According to one of the inventions In a preferred embodiment, the ceramic composition comprises a mixture of boron halide, zirconium diboride, and zirconia, and the ceramic composition preferably contains 5-70% by weight of boron nitride, and more preferably 15-50% by weight. %, 5-60% by weight of zirconium diboride, more preferably 15-50% by weight, and 5-80% by weight of zirconia, more preferably 10-60% by weight. According to another preferred embodiment of the present invention, the ceramic composition comprises a mixture of a degraded shed, a shed, and an oxide, and the ceramic composition preferably contains 5-70% by weight of boron nitride. , More preferably 15-50% by weight, 5-60% by weight zirconium diboride, more preferably 15-50% by weight, and 10-70% by weight alumina, more preferably 15-60% by weight. .: • 4 _ flushing. __ Μ Towel Noodle Home County (c called A4 size (2iGX297 Gongcheng) ~ 436471 A7 ___ B7__ 5. Description of the invention (3) In the above-mentioned preferred embodiments, The proportion of each component in the ceramic composition is expressed by weight percentage, based on the total weight of the ceramic composition, excluding carbon bonds ° Organic binders that will decompose to produce carbon bonds, can be, for example, phenolic resin, such as phenolic Varnish or soluble phenol-formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin, epoxy resin, furan resin or asphalt. The organic binder is preferably a phenol-formaldehyde resin, and the resin is preferably used in a liquid form. .Powder phenol resin can be used, but the resin must be dissolved in a suitable solvent, such as furfural, to mix the resin with other ingredients and produce a ceramic composition. The amount of liquid resin is usually 5-25% by weight, It is preferably 10-15% by weight, based on all other ingredients, and after the ceramic composition is produced, the composition will usually contain 2-12% by weight, preferably 5% by weight, produced by resin decomposition. The carbon is based on the total weight of the ceramic composition. The ceramic composition of the present invention printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs can be made in the following way. First, boron nitride, zirconium zirconia, and other refractory materials The particles are mixed together, and then the liquid resin is added and mixed until the particles and resin mixture are hooked. It may be necessary to heat the mixture to reduce the resin's liquid content so that the mixture is suitable for forming. Then, the mixture is formed into the desired The shape is preferably pressed in a suitable mold by cold isostatic pressing of the mixture. After forming, the molding is heated to mature and crosslink the resin, for example, at about 150-300 ° C for about 1 hour, and then Heating at about 700-1200 ° C to pyrolyze the resin and produce carbon bonds. Although the ceramic composition of the present invention can be used in other applications, such as in glass
本紙張尺度適用中國國家4票率（CNS )八4規格（21〇X297公幻 (請先鬩讀背面之注項再填寫本頁) ^ 4 3 6471 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（4 ) 之熔解與處理上，或在相對較低熔解溫度之金屬譬如銘及 其合金之熔解、處理及鋒造上，但此組合物特別可用於^ 熔解溫度之金屬譬如鐵或鋼之處理與鑄造上。 當使用於金屬譬如鋼之處理與鋒造上時，本發明陶资組 合物中三種成份之每一種，係對組合物賦予特定性質。I 化硼使得組合物於熔融態鋼或熔融態熔渣存在下不會潤濕 ，因此當使用於例如用以鋒造噴嘴之組合物中時，將防止 喷嘴由於氧化鋁積聚所致之阻塞。此外，氮化硼使得此等 組合物對熱振具有抵抗性，且幫助保護組合物免於氧化。 二硼化銼賦予耐浸蝕性，在比氮化硼更高之溫度（高達约 1250°C )下賦予保護作用使免於氧化，及改良組合物尉於 被熔融態熔渣攻擊之抵抗性。在此等較隹具體實施例中， 氡化鋁與氧化錶均會改良組合物對於被熔融態鋼攻擊之抵 抗性。 爲増加組合物在較高溫度例如高達約1400°C下之氧化作 用抵抗性，一般期望在組合物中，以組合物之重量爲基準 ，包含某一比例，例如5-20重量％之碳>((;矽及/或二硼化 鈦，作爲第三種耐火材料之至少一部份。 關於本發明之陶瓷組合物在鋼之處理與鑄造應用上之實 例，係爲襯料，及噴嘴與套筒，譬如在連續鑄造上所使用 者。上述含氧化锆組合物係特別適合用以形成於使用時在 熔融態鋼之表面與位於鋼頂部上之熔融態熔渣兩者間之邊 界之噴嘴部份。上述含氧化銘組合物係特別適合用以形成 噴嘴之内部，因其可容易地與用以形成噴嘴其餘部份之氧 本紙張尺度適用中國國家標率（CNS ) A4規格（21〇χ297公襲） (請先鬩讀背面之注意事項再填寫本頁} 訂' 43 64 7 1 A7 B7 五、發明説明（5 ) 化鋁-石墨材料共壓製，且其會防止氧化鋁積聚及噴嘴阻 塞。雖然若需要時此等組合物可用以形成整個噴嘴，但較 佳係僅使用彼等以形成如上述之喷嘴部份。然後，噴嘴之 其餘部份可製自習用碳結合之陶瓷材料，譬如碳結合之氧 化鋁與石墨混合物。 下述實例係用以説明本發明： 實例1 按下表1製備一系列組合物。各耐火成份之量係以重量 百分比表示，以整體爲基準，及液體樹脂之量係以整體耐 火成份之重量百分比表示。 表1 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 組合物 編號 BN ZrB2 Α1 2〇3 Zr02 SiC 樹脂 1 20 45 35 - - 10 2 25 40 35 - 13 3 30 35 35 - 15 4 20 35 45 - - 10 5 30 35 30 - 5 15 6 15 35 - 50 - 7 7 15 25 - 60 — 7 8 50 35 - 15 - 20 根據本發明之陶瓷組合物係以下述方式製成，首先將微 本紙張尺度適用中國國家摞华（CNS ) A4規格（2〗0X297公釐） 436471 A7 B7 五、發明説明（6 ) 粒子氮化硼、微粒子二硼化锆，及若存在時之微粒子氧化 銘、氧化锆及碳化矽在強力混合機中混合在一起，然後添 加液體酚甲醛樹脂，及混合直到粒子與樹脂之混合物均勻 爲止。 氮化硼爲耐火級，其含有至高7重量％氧，並具有粒度 小於10微米，及二硼化锆具有粒度小於45微米。氧化鋁與 氧化锆均爲50/50 w/w之小於500微米粒子與小於53微米粒 子。碳化矽具有粒度小於150微米。 樹脂爲液體酚醛清漆酚甲醛樹脂，其具有60重量％之固 含量。 將粒子與液體樹脂之混合物加熱，以降低樹脂之液體含 量’以使得混合物適合用於成形。然後，將混合物製成待 測試樣，其方式是混合物在模具中之冷等力壓製，於成形 後，將試樣剝離模具並於200。〇下加熱1小時，以使樹脂熟 化與交聯。最後將待測試樣在9〇〇°C下加熱，以使樹脂熱 解並產生碳鍵。 實例2 經濟部中央標準局員工消費合作杜印製 測試得自實例1之組合物卜2、3及4，以評估其對於熔 融態鋼之抵抗性，並與習用碳結合之氧化鋁-石墨材料比 較，其方式是度量當其浸沒在1650°C下之熔融態鋼中時之 腐蝕速率。 使用實例1中所述之方法，藉等力壓製以製成5〇亳米直 徑及300毫米長度之棒狀物，且精確地度量其直徑。然後 ，將此棒狀物保持在央具中，並在置於感應爐内之熔融態 本紙張尺度適用中國國家榇準（CNS ) A4規格（210x297公釐） 迤.1 (請先聞讀背面之注意事項再填寫本頁) ^ 4 3 64 7 1 A7 B7 五、發明説明（7 ) 鋼中浸没一小時。在試驗結束時，再度量棒狀物之直徑。 所得之結果係表列於下表2中。 表2 組合物編號 腐蝕速率（亳米/小時） 1 0.3 2 0.2 3 0.1 4 0.6 氧化鋁/石墨 2 眚例3 測試得自實例1之組合物6、7及8，以評估其對於熔融態 熔渣之抵抗性，並與破結合之氧化锆石墨材料比較，其方 式是度量當其浸没在1580°C下之熔融態熔渣中時之腐蚀速 率。 經濟部中央標準局桌工消費合作社印製 使用實例1中所述之方法，製成與實例1具有相同尺寸之 棒狀物，並精確地度量其直徑。將硼矽酸鹽玻璃撒在置於 感應爐中之熔融態鋼之表面上，並使其熔解以形成熔渣。 然後’將棒狀物保持在央具中，並浸沒在熔融態鋼中一小 時。於試驗結束時，在已經與熔融態熔渣接觸之區域中， 再度量棒狀物之直徑。 所獲得之結果係示於下表3中。This paper size applies to China's national 4 vote rate (CNS) and 8 4 specifications (21 × 297 public fantasy (please read the notes on the back before filling out this page) ^ 4 3 6471 A7 B7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Preparation 5. Description of the invention (4) for melting and processing, or for melting, processing, and forming of metals with relatively low melting temperatures such as Ming and its alloys, but this composition is particularly useful for metals with melting temperatures such as Treatment and casting of iron or steel. When used in the treatment and forging of metals such as steel, each of the three ingredients in the ceramic composition of the present invention imparts specific properties to the composition. Boron I makes the composition It does not wet in the presence of molten steel or molten slag, so when used in, for example, a composition used to sharpen a nozzle, it will prevent nozzle clogging due to alumina buildup. In addition, boron nitride makes These compositions are resistant to thermal shock and help protect the composition from oxidation. Diboride files impart erosion resistance and provide protection at temperatures higher than boron nitride (up to about 1250 ° C). Free from oxidation And improve the resistance of the composition to attack by molten slag. In these more specific embodiments, aluminized aluminum and oxide scale will improve the resistance of the composition to attack by molten steel. Resistance to oxidation at higher temperatures, such as up to about 1400 ° C, it is generally desirable to include a certain proportion, such as 5-20% by weight of carbon, in the composition based on the weight of the composition > (( Silicon and / or titanium diboride as at least part of the third refractory material. Examples of the ceramic composition of the present invention in steel processing and casting applications are linings, nozzles and sleeves For example, it is used in continuous casting. The above zirconia-containing composition is particularly suitable for forming the nozzle portion at the boundary between the surface of the molten steel and the molten slag on the top of the steel during use. The above-mentioned oxide-containing composition is particularly suitable for forming the inside of the nozzle, because it can easily be used with the oxygen used to form the rest of the nozzle. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇χ297 Strike) ( Please read the notes on the back before filling out this page} Order '43 64 7 1 A7 B7 V. Description of the invention (5) Aluminum-graphite material is co-pressed, and it will prevent alumina accumulation and nozzle blockage. These compositions can be used to form the entire nozzle, but it is preferred to use only them to form the nozzle portion as described above. Then, the rest of the nozzle can be made from carbon-bonded ceramic materials, such as carbon-bonded oxidation. A mixture of aluminum and graphite. The following examples are used to illustrate the present invention: Example 1 A series of compositions were prepared according to the following Table 1. The amount of each refractory component is expressed in weight percent, based on the whole, and the amount of liquid resin is based on The weight percentage of the overall refractory ingredients is shown in Table 1. (Please read the precautions on the back before filling this page) Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Composition Number BN ZrB2 Α1 2〇3 Zr02 SiC Resin 1 20 45 35- -10 2 25 40 35-13 3 30 35 35-15 4 20 35 45--10 5 30 35 30-5 15 6 15 35-50-7 7 15 25-60 — 7 8 50 35-15-20 according to Ceramic combination of the present invention It is made in the following way. First, the micro paper size is applied to the Chinese National Huahua (CNS) A4 specification (2〗 0X297 mm). 436471 A7 B7 V. Description of the invention (6) Particle boron nitride and fine zirconium diboride , And if present, the fine particles of oxide, zirconia and silicon carbide are mixed together in a powerful mixer, and then liquid phenol formaldehyde resin is added, and mixed until the mixture of particles and resin is uniform. Boron nitride is a refractory grade that contains up to 7% by weight of oxygen and has a particle size of less than 10 microns, and zirconium diboride has a particle size of less than 45 microns. Both alumina and zirconia are 50/50 w / w particles smaller than 500 microns and particles smaller than 53 microns. Silicon carbide has a particle size of less than 150 microns. The resin was a liquid novolac novolac resin having a solid content of 60% by weight. The mixture of particles and liquid resin is heated to reduce the liquid content of the resin 'so that the mixture is suitable for molding. Then, the mixture was made into a test sample by cold isostatic pressing of the mixture in a mold, and after forming, the sample was peeled from the mold and placed at 200 ° C. It was heated at 0 ° C for 1 hour to mature and crosslink the resin. Finally, the sample to be tested is heated at 900 ° C to pyrolyze the resin and generate carbon bonds. Example 2 The consumer cooperation of the Central Bureau of Standards, Ministry of Economic Affairs, Du printed the composition obtained from Example 1, Bu 3, 4, and 4 to evaluate its resistance to molten steel and to combine it with conventional carbon alumina-graphite materials For comparison, the way is to measure the corrosion rate when immersed in molten steel at 1650 ° C. Using the method described in Example 1, a rod having a diameter of 50 mm and a length of 300 mm was pressed by isostatic pressing, and its diameter was accurately measured. Then, keep this rod in the central appliance and put it in the molten state in an induction furnace. The paper size is applicable to China National Standard (CNS) A4 (210x297 mm) 迤 .1 (Please read the back first Please note this page before filling in this page) ^ 4 3 64 7 1 A7 B7 V. Description of the invention (7) Immersion in steel for one hour. At the end of the test, the diameter of the rod is measured again. The results obtained are tabulated in Table 2 below. Table 2 Composition number Corrosion rate (亳 m / h) 1 0.3 2 0.2 3 0.1 4 0.6 Alumina / graphite 2 眚 Example 3 Compositions 6, 7 and 8 obtained from Example 1 were tested to evaluate their ability to melt in the molten state. The resistance of the slag is compared with the broken bonded zirconia graphite material by measuring the corrosion rate when it is immersed in molten slag at 1580 ° C. Printed by the Table Workers Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Using the method described in Example 1, a rod having the same size as that of Example 1 was made, and its diameter was accurately measured. Borosilicate glass is sprinkled on the surface of molten steel placed in an induction furnace and allowed to melt to form slag. The rod is then held in the fixture and immersed in molten steel for one hour. At the end of the test, the diameter of the rod was remeasured in the area already in contact with the molten slag. The results obtained are shown in Table 3 below.
-------.--' J恭----；----riT (請先閱讀背面之注意事項再填寫本頁) $張纽適$中國國“準（c叫A4规格（210 43647 1 at B7 五、發明説明（8 ) 表3 組合物編號 腐蝕速率（毫米/小時） 6 2 7 2.5 8 0.5 氧化锆/石墨 4 眚例4 測試得自實例1之全部八種組合物，以評估其對氧化作 用之抵抗性，其方式是度量其在1200°C下，於不同時間間 隔下之氧化速率。 藉實例1中所述之方法，製成30毫米直徑及10毫米高之 圓盤形試樣。將試樣稱重並置於電烘箱中，歷經不同時間 ，然後移除、冷卻及再稱重。 其結果係示於下表4中，其係以試樣之重量改變表示， 毫克/平方公分/小時。 fn· ^^^^1 ^^^^1 —Bn vn^i —^^1 vt» i^i ^^^^1 1 {請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標率（CNS ) A4規格（2〗OX2.97公釐） 436471 五、發明説明（ A7 B7 轰4 組合物編號 2小時 26小時 130小時 1 0.97 -0.14 0.0001 2 2.77 -0.37 -0.00005 3 1.74 -0.60 -0.00002 4 5.54 2.97 -0.0015 5 0.63 0.20 0.00001 6 15.10 1.89 0.00025 7 10.73 1.69 0.00008 8 0.54 0.29 0.00003 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 正如表4中之結果顧示，氳化速率係f晳上隨著時間降 低，於130小時後抵逵f際上露。這可解蘇爲組合物所固 有的被動氣化現象。 實例 測試組合物1與3，並與習用碳結合之氧化鋁-石墨材料 比較，以評估當用以形成噴嘴之内部表面，而熔融態鋼係 經過其間進行鑄造時，其壓抑由於氧化鋁積聚所造成阻塞 作用之能力。 使用實例1中所述之方法製成管狀噴嘴，其具有外徑50 毫米、内徑15毫米及長度300米。將噴嘴浸沒在具有鋁含 量0.2重量％之鋁淨靜鋼中。在喷嘴浸沒後，使氧氣泡進 入鋼中，並將喷嘴連續擾拌以分佈氧。於30分鐘後結束試 -η - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標隼局貝工消費合作社印製 43 647 1 at __B7___ 五、發明説明（10) 驗，並移除噴嘴。然後將喷嘴切片並檢查，以評估氧化鋁 之積聚。 氧化鋁-石墨材料變成不良地阻塞。組合物3未顯示阻 塞，而组合物1確實顯示有些阻塞，此材料頗優於氧化鋁-石墨材科。 實例6 使用實例1中所述之方法，按下表5製備四種組合物。 所使用之氮化硼、二硼化錯、氧化鋁及氧化锆均與實例1 中所使用者相同。二硼化鈦、硼及六硼化鈣係爲粒度小於 50微米之粉末。氧化鎂具有粒度53至500微米。各成份之 量係以如實例1之相同方式表示。 表5 成份 組合物 9 組合物 10 组合物 11 組合物 12 BN 40 20 10 40 ZrB2 35 30 35 30 TiB2 15 15 10 15 B 10 10 - - A1 2〇3 - 20 10 - Zr02 - - 15 CaB6 5 - — MgO 1 - — 35 - 樹脂 18 15 15 20 本紙張尺度適用中國國家標率（CNS ) A4規格（210X297公釐）-------.-- 'J Christine ----; ---- riT (Please read the precautions on the back before filling this page) $ 张 纽 宜 $ 中国 国 "准 （c called A4 specification (210 43647 1 at B7 V. Description of the invention (8) Table 3 Composition number Corrosion rate (mm / hr) 6 2 7 2.5 8 0.5 Zirconia / graphite 4 Example 4 All eight compositions obtained from Example 1 were tested In order to evaluate its resistance to oxidation, the way is to measure its oxidation rate at different time intervals at 1200 ° C. Using the method described in Example 1, make a 30 mm diameter and 10 mm height Disk-shaped sample. The sample is weighed and placed in an electric oven, and then removed, cooled, and re-weighed. The results are shown in Table 4 below, which is expressed by the change in sample weight , Mg / cm² / h. Fn · ^^^^ 1 ^^^^ 1 —Bn vn ^ i — ^^ 1 vt »i ^ i ^^^^ 1 1 {Please read the notes on the back before filling (This page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. The paper size is applicable to China National Standards (CNS) A4 specifications (2〗 OX2.97 mm). 436471 5. Description of the invention (A7 B7) 4 Composition number 2 hours 26 hours 130 hours 1 0.97 -0.14 0.0001 2 2.77 -0.37 -0.00005 3 1.74 -0.60 -0.00002 4 5.54 2.97 -0.0015 5 0.63 0.20 0.00001 6 15.10 1.89 0.00025 7 10.73 1.69 0.00008 8 0.54 0.29 0.00003 (please first (Please read the notes on the back and fill in this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. As shown in the results in Table 4, the rate of conversion has clearly decreased with time, reaching 130% after 130 hours. This can solve the phenomenon of passive gasification inherent in the composition. Examples test compositions 1 and 3 and compare them with conventional carbon-bonded alumina-graphite materials to evaluate when used to form the inner surface of a nozzle, and The molten steel is capable of suppressing the blocking effect due to the accumulation of alumina when casting through it. The tubular nozzle is made using the method described in Example 1 and has an outer diameter of 50 mm, an inner diameter of 15 mm, and a length of 300. M. The nozzle is immersed in an aluminum static steel with an aluminum content of 0.2% by weight. After the nozzle is immersed, oxygen bubbles are allowed to enter the steel, and the nozzle is continuously stirred to distribute oxygen End the test after 30 minutes -η-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 43 647 1 at __B7___ V. Description of the invention (10 ) Check and remove the nozzle. The nozzles were then sectioned and inspected to assess alumina accumulation. The alumina-graphite material becomes poorly blocked. Composition 3 did not show blockage, while Composition 1 did show some blockage, which is a material superior to the alumina-graphite family. Example 6 Using the method described in Example 1, four compositions were prepared according to Table 5. The boron nitride, diboride, alumina, and zirconia used were the same as those used in Example 1. Titanium diboride, boron and calcium hexaboride are powders with a particle size of less than 50 microns. Magnesium oxide has a particle size of 53 to 500 microns. The amount of each component is expressed in the same manner as in Example 1. Table 5 Ingredient composition 9 composition 10 composition 11 composition 12 BN 40 20 10 40 ZrB2 35 30 35 30 TiB2 15 15 10 15 B 10 10--A1 2 03-20 10-Zr02--15 CaB6 5- — MgO 1-— 35-Resin 18 15 15 20 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm)
(請先聞讀背面之注意事項再填寫本頁)(Please read the notes on the back before filling this page)
4 3 6 4-7 1 A7 B7 五、發明説明) .〆 使用實例3中所述之方法測試此等組合物，以評估其對 於溶融態熔渣之抵抗性，及使用實例4中所述之方法測試 之，以評估其對氧化作用之抵抗性。 所得之結果係示於下表6中。氧化作用抵抗性試驗之結 果，係以試樣之重量改變表示，毫克/平方公分/小時。 表6 組合物編號 腐蝕速率 (毫米/小時） 2小時 26小時 130小時 9 0.4 0.3 0.2 0 10 0.8 0.4 0.3 0 11 0.7 20 4 0.01 12 1 0.4 0.2 0 宥例7 製備一種混合物，其具有下列組成，以重量計：- 氮化硼 20% 二硼化锆 20% 二氧化锆 55% 碳化碎 5% (讀先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 四種成份之每一種均如實例1中所述。 將陶瓷成份之混合物與6.5重量％如實例1中所述之具有 固含量60重量％之液體酚醛清漆酚甲醛樹脂混合，以此四 種陶瓷成份之總重量爲基準。 然後，使用實例1中所述之程序，製成呈4公分直徑與 -13 - 障埋丨 本紙張尺度適用中國國家標準（CNS ) A4规格（2[0X297公釐） 經濟部中央標準局員工消費合作社印製 43647 1 at _ B7 五、發明説明（12) 30公分長度之棒狀物形式之陶瓷待測試樣，並精確地度量 棒狀物之直徑。 將含有7重量％氟化物之熔渣，熔解在置於250公斤容 量之高頻感應加熱爐中而保持在165(TC下之熔融態鋼頂部 上0 接著將棒狀物保持在夾具中，並藉由將其浸沒在熔融態 鋼中兩小時造行測試，以評估其對於熱振之抵抗性，熔融 態鋼與熔渣之浸透程度，及在熔渣/金屬界.面處之腐蝕速 率。將製自碳結合之氧化錐-石墨材料之類似棒狀物，以 類似方式進行測試。兩種型式之棒狀物均具有適當熱振抵 抗性及對浸透之抵抗性，但製自根據本發明組合物之棒狀 物，以其在熔逢/金屬界面處之腐蝕速率觀之，係爲優越 的。碳結合之氧化锆-石墨棒狀物在熔渣管線上具有腐触 速率爲每小時3.05毫米，而製自根據本發明組合物之棒狀 物則具有腐蝕速率僅爲每小時0.95亳米。 實例8 製備一種混合物，其具有下列組成，以重量計：- 氮化硼 25% 二硼化錯 20% 氧化鋁 55% 三種成份之每一 種均如實例1中所述。 將陶资成份之混合物與7.5重量％如實例1中所述之具有 固含量60重量％之液體粉路清漆紛甲醒樹脂混舍’以此二 種陶瓷成份之總重量爲基準。 本紙張尺度適用中國國家標準（CNS ) A4規格（加/297公缝） (請先聞請背面之注意事項再填寫本頁)4 3 6 4-7 1 A7 B7 V. Description of the Invention) 〆 These compositions were tested using the method described in Example 3 to evaluate their resistance to molten slag, and using the methods described in Example 4 The method was tested to assess its resistance to oxidation. The results obtained are shown in Table 6 below. The results of the oxidation resistance test are expressed as the weight change of the sample, mg / cm² / h. Table 6 Composition number Corrosion rate (mm / h) 2 hours 26 hours 130 hours 9 0.4 0.3 0.2 0 10 0.8 0.4 0.3 0 11 0.7 20 4 0.01 12 1 0.4 0.2 0 7 Example 7 A mixture was prepared having the following composition, By weight:-Boron Nitride 20% Zirconium Diboride 20% Zirconium Dioxide 55% Carbonized Broken 5% (Read the precautions on the back before filling out this page) The Central Consumers Bureau of the Ministry of Economy Staff Consumer Cooperatives printed four Each of the ingredients is as described in Example 1. The mixture of ceramic components was mixed with 6.5% by weight of a liquid novolac phenol-formaldehyde resin having a solid content of 60% by weight as described in Example 1, based on the total weight of the four ceramic components. Then, using the procedure described in Example 1, it was made into a diameter of 4 cm and -13-burying. 丨 This paper size applies the Chinese National Standard (CNS) A4 specification (2 [0X297 mm). Printed by the cooperative 43647 1 at _ B7 V. Description of the invention (12) A ceramic sample to be tested in the form of a rod with a length of 30 cm, and accurately measure the diameter of the rod. The molten slag containing 7% by weight of fluoride is melted and placed in a high-frequency induction heating furnace with a capacity of 250 kg and kept at the top of a molten steel at TC 0 (TC). Then, the rod is held in a jig, and The test was performed by immersing it in molten steel for two hours to evaluate its resistance to thermal vibration, the degree of penetration of molten steel and slag, and the corrosion rate at the slag / metal interface. Similar rods made from a carbon-bonded oxide cone-graphite material were tested in a similar manner. Both types of rods have appropriate thermal shock resistance and resistance to penetration, but are made according to the invention The rod of the composition is superior in terms of its corrosion rate at the melting / metal interface. The carbon-bonded zirconia-graphite rod has a corrosion contact rate of 3.05 per hour on the slag pipeline. Millimeters, while rods made from the composition according to the invention have a corrosion rate of only 0.95 mm per hour. Example 8 A mixture was prepared having the following composition by weight:-boron nitride 25% diboride 20% wrong alumina 55% three Each of the ingredients is as described in Example 1. A mixture of ceramic materials and 7.5% by weight of a liquid powder varnish with a solid content of 60% by weight as described in Example 1 are mixed. The total weight of various ceramic ingredients is the basis. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (plus 297 stitches) (please read the precautions on the back before filling this page)
43647 1 at B7 五、發明説明（13 ) 然後，使用實例1中所述之程序，製成呈4公分直徑與 30公分長度之棒狀物形式之陶瓷待測試樣。 接著將棒狀物保持在夹具中，並浸沒在含有0.05至0.1 重量％鋁之鋁淨靜鋼中，置於250公斤容量之高頻感應加 熱爐内。將熔融態鋼之表面覆蓋一層米殼，且爲防止試驗 期間鋼之過度氧化，亦使用氬氣以保護鋼之表面。熔融態 鋼之溫度爲1570至1580°C，且浸沒時間爲2小時。製自碳 結合之氧化鋁-石墨材料之類似棒狀物，係以類似方式進 行測試。於試驗結束時，製自根據本發明組合物之棒狀物 ，比製自碳結合之氧化鋁-石墨材料之棒狀物，具有可感 知地較少之氧化銘積聚在其表面上。 (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 1543647 1 at B7 V. Description of the invention (13) Then, using the procedure described in Example 1, a ceramic test sample in the form of a rod with a diameter of 4 cm and a length of 30 cm was made. The rod is then held in a jig and immersed in an aluminum pure static steel containing 0.05 to 0.1% by weight of aluminum and placed in a high frequency induction heating furnace having a capacity of 250 kg. The surface of the molten steel was covered with a layer of rice shell. To prevent excessive oxidation of the steel during the test, argon was also used to protect the surface of the steel. The temperature of molten steel is 1570 to 1580 ° C, and the immersion time is 2 hours. Similar rods made from carbon-bonded alumina-graphite materials were tested in a similar manner. At the end of the test, rods made from the composition according to the present invention had sensibly less oxidized deposits accumulated on their surfaces than rods made from carbon-bonded alumina-graphite materials. (Please read the notes on the back before filling out this page) Order Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 15
本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐）This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)