201245095 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種鎂碳磚，特別是指—種轉爐用鎂 碳碑。 【先前技術】 煉鋼用轉爐上設置有排出鋼水用的出鋼口，該出鋼口 一般由耐火磚材所砌成。位於出鋼口處的耐火磚材由於需 要與大量的高溫鋼水接觸而常處於溫度急遽變化的環境 下，因此需選用高強度的耐火碑材。 目前廣泛使用具有優良的抗熱衝擊性質的鎂碳磚作為 出鋼口的财火磚材，鎂碳碑係由氧化鎮熟料與精選之石墨 製成。氧化鎖具有極高财火度，但抗熱衝擊性差，而石墨 能在高溫中保持適當強度’具有耐高溫衝擊的優點，因 此結合氧化鎮與石墨而成之鎮碳磚逐漸成為财火碑種之 主流°但轉爐用鎂碳磚面臨著嚴苛的工作環境，破損的情 況依然時常發生，需要修補甚至全面汰換，推究其原因 為：高溫鋼水通過時伴隨的熱衝擊所引起的破損、鋼水通 過時鎂碳磚所承受的應力所引起的破損、出鋼時因鋼水搜 掉所形成的外力而引起的折斷破損等諸多原因。上述問題 的改。’除了需考量鎮碳碑的材質外，也需考量其内徑、 外屯尽度及長度等影響’且隨著轉爐可能使用不同操作溫 度’鎂碳磚材質的改良仍須不斷試驗。 為求轉爐的運轉率提高，迫切需要延長出鋼口之鎂碳 碑的使用壽命，其耐熱衝擊性、耐酸性、耐熔損性、抗磨 201245095 ^、抗剝落性都必須兼顧。其中，抗剝落性被認為是最 〇主意的性質，剝落性損傷會使鎂碳碑的機械性質及厚度 大tw下降，造成使用壽命致命性的降低。 由上述可知，為了製得一種高耐用性之轉爐用鎂碳 碑使了可以在反覆劇烈變化的環境中具有較長的使用壽 命，針對鎂碳磚配方的改良，以提昇鎂碳碑之抗剝落性實 為必要。 【發明内容】 為克服轉爐用鎮碳磚實際工作時所遭遇的問題，本案 發月人，、呈過夕方试驗後，認為基質（matrix)的粒度構成與金 屬粉末的含量比例，是決定耐火磚之耐用度的重要因素， 從而依此尋得一製備鎂碳碑的配方，使鎂碳磚具有較佳抗 剝落性’延長使用壽命。 因此本發明之目的’即在提供一種高耐用性轉爐用鎂 奴磚，藉由調整基質的粒度構成及添加的金屬粉末種類製 得一種具有良好抗剝落性的高耐用性 鎂碳碑。 於是，本發明高耐用性轉爐用鎂碳磚，是藉由將一基 質、一催化劑與一黏結劑進行混合、壓製成型及熱處理所 製成；其中’以該基質之重量為1〇〇 wt%計，該基質包含： 78〜82 Wt%電融氧化鎂；13〜18 wt%鱗狀石墨；0.5〜3.5 wt〇/〇 銘粉；1〜2 wt%矽粉；及0.01〜0.3 wt%碳化硼（B4C)。 透過特定的基質粒度構成，搭配兩相混合的有機黏結 劑與複合種類的金屬粉末所製得的鎂碳磚，各項物性皆合 乎轉爐用鎖碳磚之需求標準，並具有抗剝落的效果。201245095 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a magnesia carbon brick, and more particularly to a magnesium carbon monument for a converter. [Prior Art] The steelmaking converter is provided with a tapping port for discharging molten steel, and the tapping port is generally made of refractory brick. The refractory bricks located at the tapping port are often in a temperature-changing environment due to the need to contact a large amount of high-temperature molten steel, so a high-strength refractory monument is required. At present, magnesia carbon bricks with excellent thermal shock resistance are widely used as the financial bricks for the tapping port, and the magnesia carbon monument is made of oxidized clinker and selected graphite. Oxidation lock has a very high degree of fiscal fire, but the thermal shock resistance is poor, and graphite can maintain the proper strength at high temperature, which has the advantage of high temperature impact resistance. Therefore, the town carbon brick combined with oxidized town and graphite has gradually become a fossil monument. Mainstream ° However, the magnesia carbon brick used in the converter is facing a harsh working environment, and the damage is still happening frequently. It needs to be repaired or even replaced. The reason is: the damage caused by the thermal shock accompanying the passage of high-temperature molten steel, There are many reasons such as the damage caused by the stress of the magnesia carbon brick when the molten steel passes, and the breakage caused by the external force generated by the steel water being found during the steel tapping. The above problems have been changed. In addition to considering the material of the town's carbon monument, it is also necessary to consider the effects of the inner diameter, the outer diameter and the length, and the improvement of the magnesia carbon brick material may continue to be tested as the converter may use different operating temperatures. In order to improve the operation rate of the converter, it is urgent to extend the service life of the magnesium carbide monument of the taphole, and its thermal shock resistance, acid resistance, melt resistance, anti-wear 201245095 ^, and anti-flaking property must be taken into consideration. Among them, the anti-flaking property is considered to be the most unsatisfactory property, and the spalling damage will cause the mechanical properties and thickness of the magnesium carbon monument to decrease, resulting in a fatal reduction in service life. It can be seen from the above that in order to obtain a high durability magnesium carbonate monument for the converter, it is possible to have a long service life in a highly violently changing environment, and to improve the magnesium carbon brick formula to improve the anti-flaking of the magnesium carbon monument. Sex is really necessary. [Summary of the Invention] In order to overcome the problems encountered in the actual work of the town carbon bricks for converters, the person in charge of the case, after the test of the Chinese New Year, considers that the ratio of the size of the matrix to the content of the metal powder is determined. An important factor in the durability of the refractory bricks, thereby finding a formula for preparing the magnesium carbon monument, so that the magnesia carbon brick has better anti-flaking property to prolong the service life. Therefore, the object of the present invention is to provide a high-resistance magnesium brick for a converter, which is obtained by adjusting the particle size composition of the substrate and the type of metal powder added to obtain a high-resistance magnesium carbon sheet having good peeling resistance. Therefore, the magnesia carbon brick for high durability converter of the present invention is prepared by mixing, pressing and heat-treating a substrate, a catalyst and a binder; wherein 'the weight of the substrate is 1% by weight The matrix comprises: 78~82 Wt% fused magnesium oxide; 13~18 wt% scaly graphite; 0.5~3.5 wt〇/〇铭粉; 1~2 wt% 矽 powder; and 0.01~0.3 wt% carbonization Boron (B4C). Through the specific matrix particle size composition, the magnesia carbon brick prepared by mixing the two-phase organic binder and the composite metal powder has the same physical properties as the lock carbon brick for the converter, and has the anti-flaking effect.
S 4 201245095 【實施方式】 本發明高耐用性轉爐用鎂碳磚，是藉由將—基質'一 催化劑與-黏結劑進行混合、壓製成型及熱處理所製成； 其中，以該基質之重量為1〇〇 wt%計，該基質包含^〜Μ wt%電融氡化鎂、13〜18糾％鱗狀石墨、Q 5〜3 $赠。叙粉、 1〜2 Wt%矽粉，及0.01〜0.3 Wt%碳化硼。 刀 [基質] (電融氧化鎂） 較佳地，該電融氧化鎂的純度介於96〜1〇〇%之間。使 1純度96%以上的電融氧化·，可進―步提高鎂碳碑的抗 侵钮性。 較佳地，以5玄基質總重量$ 1〇〇 wt%，該電融氧化鎮包 二粒徑介於3〜5 mm的第—電融氧化鎮1〇〜25、一粒 4介於1〜3 mm的第二電融氧化鎮22〜28、一粒徑介於 〇顧〜U画電融氧化鎂微粉25〜28 wt%及一海水萃取氧化 212〜13 wt%。鎂碳磚之宏、微觀結構對其㈣衝擊性皆有 ^ ’其中粒度與鎂碳碑之熱強度及彈性模數相關。當耐 科所製成之成型品由多種㈣粒徑之氧化鎂組成，1 延：t在的某些細微缺陷，如微氣孔、微裂紋等，有助於 延緩或終止裂紋的擴展。 八^粒徑介於3〜5 mm的第_電融氧化鎂，透過在基質中 3 Ϊ為10〜25 Wt%，可使鎂碳 性。當該第-電融氧⑽含量心^度及南耐熱衝擊 變 、1低於10糾％時，鎂碳磚組織 疏鬆，抗^性不佳’當含量高於25 wt%時，氧化鎂 201245095 易與鋁粉過度反應，使耐熱衝擊性降低。 該電融氧化鎂微粉之粒徑較該等第一及第二電融氧化 鎮小，因此具有較高的活性，較易與在呂粉發生反應，有助 於提升耐熱衝擊性。須注意的是，若電融氧化鎖微粉之用 量高於28 wt%’易與崎過度反應，使磚體組織過度緻密 化，反而不利於抗熱衝擊性。 —該海水萃取氧化鎂係於萃取海水後對所得的氧化鎂進 行一煆燒處理。而處理過之煆燒粉再經不同的處理方式， 會使海水萃取氧化鎂之性質不同，如表面電位、pH值等。 該海水萃取氧化鎮與該等電融氧化鎮相較，兩者純度相 田彳海水萃取氧化鎂之結晶度較小，燒結性較佳，且氧 化鈣及二氧化矽之含量較低。 (鱗狀石墨） "亥典狀石’奚係用於提高炼渣财银性或耐熱衝擊性。當 ,」13 wt/°時，抗剝落和抗熱衝擊效果不佳，易發生 爆裂；當含量高於18糾%時，使熔融鋼對鎂碳磚所造成的 磨耗增加’且彈性模數降低，易產生剝落及高溫抗折強度 下降，使用壽命較短。 (鋁粉及矽粉） ▲本發明使用含有銘粉及石夕粉之複合金屬粉末，使該鎖 奴碑於中溫和南溫環境下的抗氧化效果優於僅用單一種金 屬粉末。金屬粉末可以抑制碳的燃燒，並具有延展性，使 鎮碳碑之抗熱衝擊性能提高，且可以強化材料組織，因此 具有優異的抗侵银效果，使強度和抗氧化性增強。當紹粉 201245095 的:量切L5 wt%時，鎮碳碑的強度不足，容易發 貝年限較短；當铭粉及石夕粉的用量高於5 5心 类’鎂碳磚組織會變得緻密而使彈性上升，抗 差，較易產生破損。 銘粉在鎖碳磚卫作的過程中，因受高溫而氧化為穩定 :、：化物，氧化鋁進一步會與氧化鎂發生反應，最終生成 大晶石(Mgo· Ai2〇3)’再藉由尖晶石生成時的體積膨脹而 使磚體組織緻密化，以提高耐#性及強度，抑制彈性模數 =降低，提高耐熱衝擊性。當紹粉含量小於〇 5咖時，鎮 „化性差’透氣性亦不佳，不利鋼水沖刷，鎂碳磚 谷易朋裂；當鋁粉含量大於3.5 wt%時，效果與3 5㈣相 當而無其它變化。 矽粉具有抗氧化功用，可防止碳被氧化，當矽粉含量 小於1 W%日f，抗氧化性差，造絲碳磚基 質劣化；石夕粉含量大於2 wt%時，高溫強度較差，不利鐵水 沖刷，鎂碳磚基質易流失。較佳地，以該基質之重量計， 該基質包含矽粉1.5 wt%。 (碳化硼） 碳化硼具有抗氧化效果，可避免碳被氧化，有助於提 升鎂碳磚之強度及耐用度。其添加量低於〇〇1糾％時難 以發揮提昇抗氧化性及強度之效果，添加量大於〇 3 wt% 時’會使抗熱衝擊性下降。 為使各組份能均勻分散’較佳地，鱗狀石墨、鋁粉、 梦粉及石厌化侧之粒徑皆小於1 mm。 201245095 較佳地’以該基質總重為100重量份計，該催化劑之 含量為0.1〜0.3重量份’該黏結劑包含酚醛樹脂2〜6重量份 及碳黑0.5~2重量份。添加酚醛樹脂，使該鎂碳磚之各組份 於熱處理時有鍵結生成’強度增加。若該黏結劑之用量過 低’鎂碳磚不易成形。碳黑可對抗使用期間的熔渣穿透。 [黏結劑] 黏結劑於熱處理時會形成鍵結，使該鎂碳磚於低溫至 中溫環境下的強度提升’利於後續搬運及彻築；於高溫高 壓環境時’利用微粉之燒結特性，亦具有足夠強度。適用 於本發明之黏結劑可為盼醒樹脂（nov〇lak resin)、吱β南樹脂 (furan resin)、焦油、瀝青（pitch)，或此等之一組合；其 中’紛酿樹脂較為環保且價格合理，瀝青則具有良好潤濕 性，易與其他粉料結合，有助於提升耐熔損性。 較佳地，該黏結劑包含酚醛樹脂及碳黑。更佳地以 該基質總重為100重量份計，該黏結劑包含酚醛樹脂2〜6 重量份及碳黑0.5〜2重量份。 較佳地，該酚醛樹脂由酚醛樹脂液與酚醛樹脂粉末組 成。該盼醛樹脂液之溶劑可例如但不限於乙二醇、聚乙二 醇，可調整基質之黏度，使電融氧化鎂顆粒及電融氧化鎂 微叔更均勻混合，酚醛樹脂粉末具有增加鎂碳磚成型後之 強度的效果。更佳地，以該基質總重為1〇〇重量份計，該 酚醛樹脂由0.5〜2重量份的酚醛樹脂液及丨〜2重量份的酚醛 樹脂粉末組成。 [催化劑]S 4 201245095 [Embodiment] The magnesium carbide brick for high durability converter of the present invention is prepared by mixing, pressing and heat-treating a substrate-a catalyst with a binder; wherein, the weight of the substrate is 1 〇〇 wt%, the matrix contains ^ ~ Μ wt% electro-magnesium bismuth magnesium, 13 ~ 18 correction% scaly graphite, Q 5 ~ 3 $ gift. Powder, 1~2 Wt% niobium powder, and 0.01~0.3 Wt% boron carbide. Knife [Matrix] (Electrolyzed Magnesium Oxide) Preferably, the electrofused magnesium oxide has a purity of between 96 and 1%. By making the purity of 96% or more of the electrofusion, it is possible to further improve the resistance of the magnesium carbon. Preferably, the total weight of the 5 Xuan matrix is 〇〇1% by weight, and the electro-oxidized oxidized granules have a particle size of 3 to 5 mm, the first electro-oxidation town, 1 〇 25, and 1 4 Å. ~3 mm of the second electro-melting oxidation town 22~28, a particle size between the careless ~U draw electro-magnesium oxide micropowder 25~28 wt% and a seawater extraction oxidation of 212~13 wt%. The macro and microstructure of magnesia-carbon bricks have their impact on (4), where the particle size is related to the thermal strength and elastic modulus of the magnesium carbon. When the molded product made by Nike consists of a variety of (four) particle sizes of magnesium oxide, certain defects such as micropores and microcracks in the extension: help to delay or terminate the crack propagation. The first electro-magnesium oxide with a particle size of 3 to 5 mm is 10 to 25 Wt% in the matrix, and the magnesium can be carbonized. When the content of the first-electrolyzed oxygen (10) is less than 10%, the microstructure of the magnesia carbon brick is loose and the resistance is poor. When the content is higher than 25 wt%, the magnesium oxide 201245095 It is easy to react excessively with aluminum powder to reduce thermal shock resistance. The particle size of the electro-magnesium oxide fine powder is smaller than that of the first and second electro-oxidation oxidized towns, so it has high activity and is easy to react with the powder in the powder, thereby contributing to the improvement of thermal shock resistance. It should be noted that if the amount of the oxidized oxidized lock micropowder is higher than 28 wt%, it is overreacted with the smear, which makes the brick structure excessively densified, which is not conducive to thermal shock resistance. - The seawater extraction of magnesium oxide is carried out by extracting the seawater and then subjecting the obtained magnesium oxide to a calcination treatment. However, the treated sinter powder is subjected to different treatment methods, which will cause different properties of seawater to extract magnesium oxide, such as surface potential and pH. Compared with the electro-oxidation towns, the seawater extraction oxidation town has a smaller crystallinity, better sinterability, and lower content of calcium oxide and cerium oxide. (Scaly graphite) "Haidian-like stone' is used to improve the silver or thermal shock resistance of the slag. When, at 13 wt/°, the anti-flaking and thermal shock resistance is not good, and it is prone to bursting; when the content is higher than 18%, the abrasion caused by the molten steel to the magnesia carbon brick is increased' and the elastic modulus is lowered. It is easy to produce spalling and high temperature flexural strength, and has a short service life. (Aluminum powder and strontium powder) ▲ The invention uses a composite metal powder containing Ming powder and Shishi powder, so that the antioxidant effect of the lock slave in the medium temperature and south temperature environment is better than that of a single metal powder. The metal powder can suppress the combustion of carbon and has ductility, which improves the thermal shock resistance of the carbon monument and can strengthen the material structure, thereby having an excellent anti-intrusion effect and enhancing strength and oxidation resistance. When Shao powder 201245095: the amount cut L5 wt%, the strength of the town carbon monument is not enough, it is easy to send a short period of time; when the amount of Ming powder and Shishi powder is higher than 5 5 heart type 'magnesia carbon brick structure will become It is dense and makes the elasticity rise, and it is easy to produce damage. In the process of locking carbon bricks, Ming powder is oxidized to be stable due to high temperature:::, the alumina will further react with magnesium oxide, and finally form large spar (Mgo·Ai2〇3)' The volume expansion at the time of spinel formation densifies the brick structure to improve the resistance and strength, suppress the elastic modulus = decrease, and improve the thermal shock resistance. When the content of Shao powder is less than 〇5 coffee, the town has poor gas permeability, which is not good for steel scouring, and the magnesium carbon brick is easy to split. When the aluminum powder content is more than 3.5 wt%, the effect is equivalent to 35 (four) without other The powder has anti-oxidation function, which can prevent carbon from being oxidized. When the content of bismuth powder is less than 1 W%, the oxidation resistance is poor, and the carbonized brick matrix is deteriorated. When the content of shifan powder is more than 2 wt%, the high temperature strength is poor. It is unfavorable to wash the molten iron, and the magnesia carbon brick matrix is easily lost. Preferably, the matrix contains 1.5 wt% of niobium powder based on the weight of the matrix. (Boron carbide) Boron carbide has an antioxidant effect and can prevent carbon from being oxidized. It can help to improve the strength and durability of the magnesia carbon brick. It is difficult to exert the effect of improving the oxidation resistance and strength when the amount is less than 〇〇1%, and the heat shock resistance will be improved when the amount is more than 〇3 wt%. In order to allow the components to be uniformly dispersed, preferably, the particle sizes of the scaly graphite, the aluminum powder, the dream powder and the stone anesthesia side are all less than 1 mm. 201245095 Preferably, the total weight of the substrate is 100 weight. The catalyst is contained in an amount of 0.1 to 0.3 parts by weight. The binder comprises 2 to 6 parts by weight of the phenolic resin and 0.5 to 2 parts by weight of the carbon black. The addition of the phenolic resin causes the components of the magnesia carbon brick to bond to form an increase in strength during the heat treatment. If the amount of the binder is excessive Low 'magnesia carbon bricks are not easy to form. Carbon black can resist the penetration of slag during use. [Binder] The binder will form a bond during heat treatment, which will increase the strength of the magnesia carbon brick in low to medium temperature environment. Conducive to the subsequent handling and thorough construction; in the high temperature and high pressure environment 'utilize the sintering characteristics of the micro powder, also has sufficient strength. The adhesive suitable for the present invention can be nov〇lak resin, 吱β南 resin (furan resin) ), tar, pitch, or a combination of these; wherein 'the resin is more environmentally friendly and reasonably priced, the bitumen has good wettability, and it is easy to combine with other powders to help improve the resistance to melting. Preferably, the binder comprises a phenolic resin and carbon black. More preferably, the binder comprises 2 to 6 parts by weight of the phenolic resin and 0.5 to 2 parts by weight of the carbon black based on 100 parts by weight of the total weight of the substrate. Good, the phenolic resin The phenolic resin liquid is composed of a phenolic resin powder, and the solvent of the acetal resin liquid can be, for example, but not limited to, ethylene glycol and polyethylene glycol, and the viscosity of the matrix can be adjusted to make the electro-magnesium oxide particles and the electro-magnesia magnesia Evenly mixed, the phenolic resin powder has an effect of increasing the strength of the magnesia carbon brick after molding. More preferably, the phenolic resin is composed of 0.5 to 2 parts by weight of the phenolic resin liquid and hydrazine based on the total weight of the substrate. ~2 parts by weight of phenolic resin powder composition. [Catalyst]
S 201245095 該催化劑用於促進該黏結劑反應’使該鎂碳碑之硬化 速度提升。 較佳地，以該基質總重為100重量份計，該催化劑之 含量為0.1〜0.3重量份。 較佳地’為配合該黏結劑包含酚醛樹脂，該催化劑為 六甲基四胺，有助於使酚醛樹脂硬化。 本發明轉爐用鎂碳碑的製法是透過將該基質、該催化 劑與該黏結劑進行混合，於1〜2 kg/cm2壓力下屢製成型 後，以22〇〜25〇 °C進行熱處理所製成。 本發明將就以下實施例作進一步說明，但應瞭解的 是，該實施例僅為例示說明之用，而不應被解釋為本發明 實施之限制。 <化學品來源> 3-5mm電熔氧化鎂：產於中國，純度96 %。 鱗狀石墨：產於中目，商品名「895」。含有固定碳％ wt%、灰份3.0〜4.5 wt%、揮發份小於丄wt%，粒度為 0.018 mm，80 0/〇 min。S 201245095 The catalyst is used to promote the reaction of the binder to increase the hardening speed of the magnesium carbon monument. Preferably, the catalyst is contained in an amount of from 0.1 to 0.3 parts by weight based on 100 parts by total of the total mass of the substrate. Preferably, the binder comprises a phenolic resin which is hexamethyltetramine which helps to harden the phenolic resin. The method for preparing magnesium carbonate in the converter of the present invention is prepared by mixing the substrate, the catalyst and the binder, and repeatedly molding at a pressure of 1 to 2 kg/cm 2 , and then heat-treating at 22 〇 to 25 ° C. production. The invention is further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting. <Chemical Source> 3-5 mm fused magnesia: produced in China with a purity of 96%. Scaly graphite: Produced in Zhongmu, the trade name is "895". It contains fixed carbon % wt%, ash content 3.0~4.5 wt%, volatile matter less than 丄wt%, particle size 0.018 mm, 80 0/〇 min.
狀石墨：產於中國，商品名「195」。含有固定碳％ wt/。、灰份3.0〜4.5 wt%及揮發份小於i wt%，粒度為 0.150 min ’ 80 % min 〇 「98HD」，氧化鎂含量 海水萃取氧化鎂：產於日本’商品名 98 wt%。 海水萃取氧化鎂：產於曰本 98 wt%。 商品名「98F」，氧化鎂含量 201245095 碳黑：產於日本，商品名「TGP2000」。 瀝青：產於歐洲’商品名「NP COKE」。 銘粉：含鋁99°/。以上，粒度0.075 mm，95% min以上。 石夕粉：含矽99%以上，粒度0.125 mm，95% min以上。 <實施例> [實施例1J 製造鎂碳碑 1. 混合： 將第一電融氧化鎂22.5 wt%、第二電融氧化鎂22 5 wt%及第三電融氧化鎂23 wt〇/〇依比例加入攪拌器中，均勻 混合1分鐘後，加入酚醛樹脂液2重量份，再攪拌2分鐘 使之均勻混合。於反應槽再加入六曱基四胺〇2重量份， 攪拌2分鐘後再加入鱗狀石墨15 wt%並攪拌4分鐘最後 反應槽中加入已預先混合的氧化鎮微粉1 〇 wt%與盼酿樹脂 粕末2重量份，攪拌30分鐘後出料❶實施例丨之各組份化 學品及用量詳細記載於表i。 2. 壓製成型： 成型係藉由800噸或1300頓摩擦式壓磚機將混煉物填 充於模具而進行。成型碑㈣21G/1G，模具尺寸為2i〇 X 100 X 155 / 145 mm，所用之歷磚機購自於三石深井，型號 為13VCF〇P-iE_B。於2 kg/cm2壓力下，輕壓3〜5下再重 壓6下以上，而後視混煉胚料之狀況調整壓磚之力度及次 數’製得一成型品。 3. 乾燥：Graphite: Produced in China, the trade name is "195". Contains fixed carbon % wt /. , ash content 3.0~4.5 wt% and volatile matter less than i wt%, particle size is 0.150 min ‘ 80 % min 「 “98HD”, magnesium oxide content Seawater extraction magnesia: produced in Japan 'trade name 98 wt%. Seawater extraction of magnesium oxide: produced in 曰本 98 wt%. Product name "98F", magnesium oxide content 201245095 Carbon black: Produced in Japan, trade name "TGP2000". Asphalt: Produced in Europe's trade name "NP COKE". Ming powder: containing aluminum 99 ° /. Above, the particle size is 0.075 mm, 95% min or more. Shi Xi powder: more than 99% bismuth, particle size 0.125 mm, 95% min or more. <Examples> [Example 1J Production of magnesium carbon monument 1. Mixing: 22.5 wt% of the first electro-magnesium oxide, 22 wt% of the second electro-magnesium oxide, and 23 wt% of the third electro-magnesium oxide/ The mixture was added to the stirrer in a ratio, and after uniformly mixing for 1 minute, 2 parts by weight of the phenol resin liquid was added, and the mixture was further stirred for 2 minutes to be uniformly mixed. Add 2 parts by weight of hexamethylenetetramine in the reaction tank, stir for 2 minutes, then add 15 wt% of scaly graphite and stir for 4 minutes. Add the pre-mixed oxidized micropowder 1 〇wt% to the final reaction tank. The resin was added in an amount of 2 parts by weight, and after stirring for 30 minutes, the chemicals and amounts of the components of the examples were detailed in Table i. 2. Press molding: The molding is carried out by filling the kneaded material into a mold by means of an 800-ton or 1300-stroke friction brick press. Forming monument (4) 21G/1G, the mold size is 2i〇 X 100 X 155 / 145 mm, and the calendar machine used is purchased from Sanshi Shenjing, model 13VCF〇P-iE_B. Under the pressure of 2 kg/cm2, press gently for 3~5 times and then press for more than 6 times, and then adjust the strength and number of pressing bricks in the condition of mixing the billet to prepare a molded product. 3. Drying:
S 10 201245095 。將該成型品置於115°C環境中乾燥10小時後，置於220 °c環境中再乾燥24小時，即製成實施例i之鎂碳磚。 性質測試 將實施例1之鎂碳磚採取5x5x5 cm3的樣品，進行下述 各項性質測試，測試結果詳細記載於表2。各項性質之需求 標準依鎂碳磚實際工作需求及所配合之轉爐條件進行調整 及設定。 I成形比重（kg/cm3):成形比重為鎂碳磚成型後之重量除以 其成型後之體積，需求標準為2.9〜3.05 kg/cm3。 2.乾燥比重（kg/cm3):乾燥比重為鎂碳磚乾燥後之重量除以 其乾燥後之體積。 3·乾燥線變（％):乾燥線變為鎂碳磚乾燥前之尺寸除以其乾 燥後之尺寸變化。 4·再熱線變化率（Permanent Linear Charge，簡稱 P.L.C.): 將樣品置於1500°C環境中，依CNS 618 R3 012方法測 量。 5·常溫耐壓強度（Cold Crushing Strength，簡稱 C.C.S.):根 據 ASTM C133-94、JIS R2206 或 CNS 616 R3010 方法（前 述方法均相同）’以萬能試驗機檢測（購自於弘達儀器，型 號HT9501) ’常溫耐壓強度大於3 10 kg/cm2方能合乎需 求標準。 6.尚溫抗折強度（m〇dulus of rupture at medium temperatures，簡稱 HMOR):根據 GB/T 13243-91 方法測 試。 201245095 7·表面氣孔率（Apparent porosity，簡稱AP):根據JIS R2205或ASTM C20方法測量（前述方法為相同）。 8. 體密度（Bulk Density):根據 jis R2205 或 ASTM C20 方 法測量（前述方法均相同），體密度需大於2 84g/cm2方能 合乎需求標準。 9. 咼溫抗氧化測試：秤量該樣品於常溫下之重量。將該樣 品利用向溫爐以5 °C /sec之速率升溫至丨000°c，保持3 小時後，記錄樣品重量，與常溫下重量之重量差計為 l〇〇〇°C消失量，並測量氧化層厚度，該氧化層係因碳鍵 氧化而產生，質地較為脆弱。另取相同來源之樣品予以5 °c/sec之升溫速率加熱至1500t，保持3小時後，記錄 樣品重量並測量氧化層厚度，與常溫下重量之重量差計 為·t：消失量。溫度管理係利用放射溫度計施行。 【實施例2〜9】 製備實施例2〜9之鎮碳磚製法與實施例ι相同，不同 之處在於各組份選用之化合物及含量比例，實施例2〜”斤 用之化學品及詳細用量紀錄於表1。 進行各項性質測試，其採 相同，評價結果詳細記載 將實施例2〜9之鎂碳磚分別 樣方法與測試方式係與實施例1 於表2。 〇 12 201245095 表1 組份 有效 實施 A.I 1 "»Γ 例2 成分 π學品 貧施 實施 *施 實施 實施 實施 --*— 1歹1J丄 例3 例4 例5 例6 例7 J〇mm 22.5 14.7 22.5 14.2 22.5 22.5 22.5 22.5 一例9’ 22.5 氧化 l'3mm 〜·1¾化鎂 22.5 27 22.5 27 22.5 22.5 22.5 22.5 22.5 基質 (wt%) 鎂 〇·Μη 電融氣>| im 卜.# 23 27.5 24.5 27.5 25 25 25 25 25 海水萃取 98F 10 12 12 - - - 12 • - —氧化錯 98HD . - 12.5 12 12 - 12 12 1 1 ΠΠ番 Mg〇嫵今吾 78 81.2 81.5 81.2 82 82 82 82 82 量份） 195 7 7 7 7 7 7 - 15 ΠΛ. 7； Μ 895 17.5 7 7 7 7 7 7 15 - xUl 石墨總含晉 17.5 14 14 14 14 14 14 15 15 鋁粉 0.075 mm 2.7 3 2.7 3 2.2 2.2 2.2 2.2 2.2 矽粉 0.125 mm 1 1 1 1 1 1 1 1 1 碳化 硼 碳化硼 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 黏結劑 (重量 份） 酚醛 酚醛 樹脂液 1-2 1-2 1-2 1-2 1-2 1-2 1-2 1-2 1-2 樹脂 酚醛 樹脂粉末 2 2 2 2 2 2 2 2 2 焦油 焦油 0.5 0.5 _ - - 0.5 - - - 碏黑 TGP2000 • 0.5 0.5 0.5 - 0.5 0.5 0.5 催化劑 (重量 份） 六甲 基 四胺 六甲基四胺 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 -」表示未添加。 13 201245095 表2 性質測試 實施 例1 實施 例2 實施 例3 實施 例4 實施 例5 實施 例6 實施 例7 實施 例8 實施 例9 成形比重(kg/cm3) 2.95 2.92 2.95 2.97 2.98 3.02 2.98 2.98 2.97 乾燥比重(kg/cm3) 2.95 2.92 2.95 2.96 2.98 3.01 2.97 2.96 2.95 乾燥線變(％) 0 0.1 0 0 0.1 0 0.1 0 0 再熱線變化率(％) 0.32 0.41 0.62 0.32 0.41 0.62 0.2 0.58 0.82 常壓耐震強度 (kg/cm2) 445 385 315 549 490 461 429 451 457 高溫抗折強度 (kg/cm2) 121 130 142 128 152 168 126 140 142 表面氣孔率(％) 1.37 1.57 3.09 0.95 0.98 1.27 1.11 1.16 1.64 體密度(g/cm3) 2.98 2.97 2.94 2.93 2.97 2.98 2.96 2.96 2.92 南 溫 抗 氧 化 測 試 1000°C消失量 (%) 1.96 2.88 2.42 1.96 2.88 2.42 3.04 3.85 3.44 1000°C 氧化層厚度 (mm) 誤差 範圍内 誤差 範圍内 誤差 範圍内 誤差 範圍 内 誤差 範圍 内 誤差 範圍 内 誤差 範圍 内 誤差 範圍 内 誤差 範圍 内 1500°C消失量 (%) 3.85 3.2 2.45 3.95 3.38 2.35 3.38 3.65 2.49 1500°C 氧化層厚度 (mm) 0.3 0.2 0.1 0.18 0.15 0.10 0.18 0.24 0.15 s 14 201245095 參見表1及表2，實施例5與實施例6之各組份用量相 同，唯一不同的是黏結劑之種類，實施例5以碳黑為黏結 劑’實施例6則選用焦油。結果顯示，實施例5與實施例6 之樣品，其體密度差小於1%，以碳黑為黏結劑之實施例5 的再熱線^:化率較小’表示在煉鋼製程中該鎮碳磚不會因 溫度的變化而使體積產生大幅的變化，可維持體積的熱穩 定性，因此可有效地降低鎂碳磚之内襯層因溫度變化而造 成的熱衝擊剝落。實施例5亦具有較佳之常壓耐震性質， 但就高溫抗折與1〇〇〇。(：及150(TC的氧化消失量的測試結果 來看，以焦油為黏結劑之鎂碳碑具有較佳的高溫抗折效 果’有利於提升抗鋼水磨蝕性’且高溫抗氧化能力亦較 佳。 實施例5及實施例7之各組份用量相同，唯一不同的 是海水萃取氧化鎂之化學品種類，實施例5選用「98HD」’ 實施例7則選用「98F」。實施例7之再熱線變化率較小， 耐熱衝擊剝落效果較佳。觀察常壓耐震強度、高溫抗折強 度、1000 C消失量及1500°C氧化層厚度之測試結果，實施 例5之鎂碳磚性質較佳，推測選用「98hd」之鎂碳碑，在 高溫環境中具有較佳抗氧化能力。 實施例2與實施例4之各組份用量大致相同，不同之 處在於黏結劑及海水萃取氧化鎂之化學品的種類。實施例2 以焦油為黏結劑，選用海水萃取氧化鎂「98F」，實施例4 則選用碳黑與「98HD丨。砝旲顯千，窨z 」、·〇禾,.、、員不實施例4之再熱線變化 率較小，可減少剝落情況發生’且常壓耐震性質亦較佳， 15 201245095 推測與使用碳黑作為黏結劑有關。 觀察刪及测。c的氧化消失量測試結果，實 4於UMMTC時消失量較少，實施例2於15〇〇β(：時消失 少’推測焦油#「9_」之組合在高溫環境中之抗氧：二 果優於碳黑與「98F」，於前述比較實施例5與實施例6及 比較實施例5及實施例7所推測之結果相同。 實施例8及實施例9之各組份用量相同，唯—不同的 是鱗狀石墨的種類，實施例8選用粒度為〇 〇18爪爪之 「895」，實施例9則選用粒度為〇_15〇爪爪之「195」。結果 顯示，實施例9之高溫抗氧化能力明顯優於實施例^實 施例8之再熱線變化率較小，具有較佳抗剝落效果。 實施例1之基質組成與實施例2〜9稍有不同，實施例工 之鱗狀石墨含量相對較高，氧化鎂含量相對較小。結果顯 示，實施例1之高溫抗折強度及高溫抗氧化能力較差。 综上所述，本發明高耐用性轉爐用鎂碳磚藉由改良配 方以提昇鎂碳磚之耐用度，透過調整基質的原料使用比例 以及氧化鎂的粒度構成，搭配特定黏結劑與催化劑，強化 各組份間的結合強度，進行混合、壓製成型和乾燥後所製 得的鎂碳磚，其各項物性合乎需求，且具有較佳的抗剝落 性’可有效提升轉爐用鎂碳磚的使用壽命。 惟以上所述者’僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明申請專利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍 屬本發明專利涵蓋之範圍内。S 10 201245095. The molded article was dried in an environment of 115 ° C for 10 hours, and then dried in an environment of 220 ° C for another 24 hours to prepare a magnesia carbon brick of Example i. Property test The 5x5x5 cm3 sample of the magnesia carbon brick of Example 1 was subjected to the following property tests, and the test results are detailed in Table 2. The requirements of each nature are adjusted and set according to the actual working requirements of the magnesia carbon bricks and the converter conditions to be matched. I Forming specific gravity (kg/cm3): The specific gravity is the weight after molding of the magnesia carbon brick divided by the volume after molding, and the demand standard is 2.9 to 3.05 kg/cm3. 2. Dry specific gravity (kg/cm3): The dry specific gravity is the weight of the magnesia carbon brick after drying, divided by the volume after drying. 3. Drying line change (%): The drying line is changed to the size of the magnesia carbon brick before drying, divided by the dimensional change after drying. 4. Remanent Linear Charge (P.L.C.): The sample is placed in a 1500 ° C environment and measured according to the CNS 618 R3 012 method. 5. Cold Crushing Strength (CCS): according to ASTM C133-94, JIS R2206 or CNS 616 R3010 (the same method is the same). Tested by universal testing machine (purchased from Hongda Instruments, model HT9501) 'The normal temperature withstand strength is greater than 3 10 kg/cm2 to meet the demand standard. 6. m〇dulus of rupture at medium temperatures (HMOR): tested according to GB/T 13243-91. 201245095 7. Surface porosity (AP): measured according to JIS R2205 or ASTM C20 method (the foregoing method is the same). 8. Bulk Density: Measured according to jis R2205 or ASTM C20 method (the same method is used), the bulk density should be greater than 2 84g/cm2 to meet the demand standard. 9. Anti-oxidation test: Weigh the sample at room temperature. The sample was heated to 丨000 ° C at a rate of 5 ° C / sec in a warm oven, and after holding for 3 hours, the weight of the sample was recorded, and the difference in weight from the weight at normal temperature was calculated as the amount of disappearance of l 〇〇〇 ° C, and The thickness of the oxide layer is measured, and the oxide layer is produced by oxidation of carbon bonds, and the texture is relatively fragile. Another sample of the same source was heated to 1500 t at a heating rate of 5 °c/sec. After 3 hours, the weight of the sample was recorded and the thickness of the oxide layer was measured. The difference in weight from the weight at room temperature was calculated as ·t: disappearance. Temperature management is performed using a radiation thermometer. [Examples 2 to 9] The preparation method of the town carbon bricks of the preparation examples 2 to 9 is the same as that of the example ι, except that the compound and the content ratio of each component are selected, and the chemical of Example 2 to "jin" and the details The dosages are reported in Table 1. The properties were tested in the same manner, and the evaluation results are detailed. The methods and test methods for the magnesia carbon bricks of Examples 2 to 9 are shown in detail in Table 2. Table 12 201245095 1 component effective implementation of AI 1 "» 2 Example 2 π 品 贫 implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation implementation 22.5 22.5 22.5 22.5 Example 9' 22.5 Oxidation l'3mm ~·13⁄4 Magnesium 22.5 27 22.5 27 22.5 22.5 22.5 22.5 22.5 Substrate (wt%) Magnesium 〇·Μη Electric fused gas>| im 卜.# 23 27.5 24.5 27.5 25 25 25 25 25 Seawater extraction 98F 10 12 12 - - - 12 • - - Oxidation error 98HD . - 12.5 12 12 - 12 12 1 1 ΠΠ番Mg〇妩今吾78 81.2 81.5 81.2 82 82 82 82 82 parts) 195 7 7 7 7 7 7 - 15 ΠΛ. 7; Μ 895 17.5 7 7 7 7 7 7 15 - xUl Ink total inclusion 17.5 14 14 14 14 14 14 15 15 Aluminum powder 0.075 mm 2.7 3 2.7 3 2.2 2.2 2.2 2.2 2.2 Tantalum powder 0.125 mm 1 1 1 1 1 1 1 1 1 Boron carbide boron carbide 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Adhesive (parts by weight) Phenolic phenolic resin solution 1-2 1-2 1-2 1-2 1-2 1-2 1-2 1-2 1-2 Resin phenolic resin powder 2 2 2 2 2 2 2 2 2 tar tar 0.5 0.5 _ - - 0.5 - - - 碏 black TGP2000 • 0.5 0.5 0.5 - 0.5 0.5 0.5 catalyst (parts by weight) hexamethyltetramine hexamethyltetramine 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 - Indicates that it was not added. 13 201245095 Table 2 Property Test Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Forming specific gravity (kg/cm3) 2.95 2.92 2.95 2.97 2.98 3.02 2.98 2.98 2.97 Drying Specific gravity (kg/cm3) 2.95 2.92 2.95 2.96 2.98 3.01 2.97 2.96 2.95 Drying line change (%) 0 0.1 0 0 0.1 0 0.1 0 0 Reheat line change rate (%) 0.32 0.41 0.62 0.32 0.41 0.62 0.2 0.58 0.82 Normal pressure and shock resistance (kg/cm2) 445 385 315 549 490 461 429 451 457 High temperature flexural strength (kg/cm2) 121 130 142 128 152 168 126 140 142 Surface porosity (%) 1.37 1.57 3.09 0.95 0.98 1.27 1.11 1.16 1.64 Bulk density ( g/cm3) 2.98 2.97 2.94 2.93 2.97 2.98 2.96 2.96 2.92 South Temperature Antioxidant Test 1000°C Loss (%) 1.96 2.88 2.42 1.96 2.88 2.42 3.04 3.85 3.44 1000°C Oxide Thickness (mm) Within the error range of the error range Within the error range, within the error range, within the error range, within the error range, within the error range, within the error range, within the error range of 1500 °C (%) 3.85 3.2 2.45 3.95 3.38 2.35 3.38 3.65 2.49 15 00°C Oxide layer thickness (mm) 0.3 0.2 0.1 0.18 0.15 0.10 0.18 0.24 0.15 s 14 201245095 Referring to Table 1 and Table 2, the amounts of the components of Example 5 and Example 6 are the same, the only difference is the type of the binder. In Example 5, carbon black was used as a binder. In Example 6, tar was used. The results showed that the samples of Example 5 and Example 6 had a difference in bulk density of less than 1%, and the reheating line of Example 5 with carbon black as the binder was smaller, indicating that the carbon in the steelmaking process was The brick does not change the volume greatly due to the change of temperature, and the thermal stability of the volume can be maintained, so that the thermal shock spalling of the inner liner of the magnesia carbon brick due to temperature change can be effectively reduced. Example 5 also has better atmospheric pressure and shock resistance properties, but is resistant to high temperature and 1 〇〇〇. (: and 150 (TC's oxidation loss test results, the use of tar as a binder of magnesium carbon monument has a better high temperature bending effect 'favors to improve corrosion resistance to molten steel' and high temperature oxidation resistance Preferably, the components of Example 5 and Example 7 are used in the same amount, the only difference being the chemical species of seawater extraction of magnesium oxide, and the use of "98HD" in Example 5 and the "98F" in Example 7. The rate of change of reheat line is small, and the effect of thermal shock resistance is better. Observing the test results of atmospheric shock resistance, high temperature flexural strength, 1000 C disappearance and 1500 ° C oxide thickness, the magnesia carbon brick of Example 5 is better. It is speculated that the "98hd" magnesium carbon monument is used to have better oxidation resistance in high temperature environment. The amounts of the components in Example 2 and Example 4 are about the same, except that the chemical of the binder and seawater extracting magnesium oxide The type of the product. Example 2 Using tar as a binder, seawater is used to extract magnesium oxide "98F", and in example 4, carbon black and "98HD 丨. 砝旲显千, 窨z", 〇禾,,, The staff does not implement the reheat line change of Example 4. The rate is small, which can reduce the occurrence of spalling, and the atmospheric pressure and seismic properties are also better. 15 201245095 It is speculated that it is related to the use of carbon black as a binder. Observed and tested. The oxidation loss test result of c, disappeared in UMMTC The amount is less, and the anti-oxidation in the high temperature environment of the combination of the two 〇〇β(:: disappearing less 'presumably tar# '9_' in Example 2 is better than carbon black and "98F" in the above comparative example. 5 is the same as the results estimated in Example 6 and Comparative Example 5 and Example 7. The components of Example 8 and Example 9 were used in the same amount, except that the type of scaly graphite was different, and the particle size of Example 8 was selected. For the "895" of the 18 claws, the "195" of the jaws having the particle size of 〇_15〇 was selected in Example 9. The results showed that the high-temperature oxidation resistance of Example 9 was significantly better than that of Example 8 The reheat line has a small rate of change and has a better anti-flaking effect. The matrix composition of Example 1 is slightly different from Examples 2 to 9. The scaly graphite content of the embodiment is relatively high, and the magnesium oxide content is relatively small. Shows that the high temperature flexural strength and height of Example 1 The thermal oxidation resistance is poor. In summary, the high durability converter magnesia carbon brick of the present invention improves the durability of the magnesia carbon brick by improving the formulation, adjusting the ratio of the raw materials used of the matrix and the particle size of the magnesium oxide, and matching the specificity. The binder and the catalyst strengthen the bonding strength between the components, and the magnesia carbon brick obtained after mixing, press molding and drying has various physical properties, and has better anti-flaking property, which can effectively improve the converter. The service life of the magnesia carbon bricks is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, it is based on the scope of the invention and the description of the invention. Simple equivalent changes and modifications are still within the scope of the invention.
S 16 201245095 【圖式簡單說明】 201245095 【主要元件符號說明】S 16 201245095 [Simplified illustration] 201245095 [Main component symbol description]