TW201313656A - 不定形耐火材料 - Google Patents
不定形耐火材料 Download PDFInfo
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- TW201313656A TW201313656A TW101126814A TW101126814A TW201313656A TW 201313656 A TW201313656 A TW 201313656A TW 101126814 A TW101126814 A TW 101126814A TW 101126814 A TW101126814 A TW 101126814A TW 201313656 A TW201313656 A TW 201313656A
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- Prior art keywords
- olivine
- mass
- refractory material
- organic binder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
- B22D41/02—Linings
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/013—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics containing carbon
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- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/20—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in magnesium oxide, e.g. forsterite
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- Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
[課題]本發明之課題為提供一種不管是否在結合劑上使用有機結合劑,例如超過1000℃的高溫域下不易產生強度下降之不定形耐火材料。[解決手段]解決課題之技術手段為提供一種本發明之不定形耐火材料,其係包含粒徑1mm以上之粗粒域及粒徑未滿1mm之微粒域所構成之耐火性粉體、以及有機結合劑,混合燒成橄欖石於微粒域上,且前述有機結合劑之使用量相對於前述耐火性粉體100質量%其為1質量%以上20%質量以下。
Description
本發明,係關於用有機結合劑於結合劑上之不定形耐火材料。
以下,沒有制限的意味,作為不定形耐火材料,列舉餵槽(tundish)塗佈層之形成上所使用之塗佈材料為例子進行說明。
在鋼的連續鑄造所使用之餵槽(tundish),其係在鐵皮的內側上,具有設置耐火材料內襯之構造。再來,其耐火材料內襯的表面上,因為殘鋼處理的容易化或耐火材料內襯的保護等目的,有時會形成塗佈層。塗佈層,為經由塗佈材料所構成之不定形耐火材料。
如專利文獻1所指示,各自瞭解到塗佈材料,與其他的不定形耐火材料一樣,係包含粒徑1mm以上之粗粒域及粒徑未滿1mm之微粒域所構成之耐火性粉體、以及結合劑。在耐火性粉體上,一般是使用鎂砂質原料。作為結合劑,其為矽酸鈉等之無機結合劑、及酚樹脂等之有機結合劑。
[專利文獻1]日本特開2006-7317號公報
[專利文獻2]日本特開2000-176612號公報
[專利文獻3]日本特開平4-130066號公報
[專利文獻4]日本專利第4273099號公報
餵槽(tundish)使用時,來自溶鋼的受熱使塗佈層達到超過1000℃的溫度。
無機結合劑,例如在600℃~1000℃之中間溫度域上所賦予強度為有效,因為為低熔點物質,在超過1000℃之高溫域,成為使強度及耐腐蝕性下降的因素。
有機結合劑,伴隨其所含揮發成份之逸散至1000℃時形成碳鍵。碳鍵,不易浸潤於爐渣,因為不是低熔點物質,與無機結合劑相比,在超過1000℃之高溫域勝過其強度及耐腐蝕性之賦予效果。
但是,即使是碳鍵,在超過1000℃之高溫域其強度的安定性並不令人滿意。碳鍵在高溫域容易經由氧化產生劣化。
在高溫域碳鍵劣化的課題,不限於塗佈材料,一般適用於使用有機結合劑於結合劑之不定形耐火材料。
特別在氧化環境下容易產生碳鍵的劣化,即使在非氧化環境下,碳鍵在高溫域可能發生分解或逸散。因此,無論氧化環境、非氧化環境,期望在高溫域強度安定性優異
之不定形耐火材料。
本案發明者們,研究的結果,發現在有機結合劑的使用下,在耐火性粉體上粒徑未滿1mm之微粒域上,混合燒成橄欖石,在高溫域提高強度之安定性。此為粒徑未滿1mm之燒成橄欖石,因為粒徑細小容易燒結,碳鍵易受損傷所以適度地在高溫域燒結,被認為是有助於賦予強度。
一直以來,橄欖石在耐火材料之技術領域上,被稱為耐火性粉體。但是,粒徑未滿1mm時,而且已預先燒成之橄欖石,與有機結合劑組合使用之例子到目前為止沒有看過。以下,進行具體地說明。
專利文獻2,揭示作為塗佈材料之不定形耐火材料上,使用橄欖石之例子(參照專利文獻2之表1)。但是,在專利文獻2並不限於橄欖石預先燒成者。假使此為預先燒成者,因為橄欖石只用在粒徑1mm以上之粗粒域,所以橄欖石不容易燒結,在高溫域幾乎不能賦予強度。
專利文獻3,揭示用於澆注熔融金屬容器施工之不定形耐火材料上,混合粒徑未滿1mm之橄欖石之例子。但是,在專利文獻3,橄欖石必須是未燒成的。未燒成橄欖石,在耐火材料使用中,經由體積膨脹使組織上形成裂紋,且伴隨結晶水之釋放(參照專利文獻3之3頁左上欄2行~同頁右上欄5行)。因此,寧可抑制耐火材料之強度表現。經由橄欖石之燒結之強度表現,橄欖石只有為預先燒成者時才能奏效。
專利文獻4,揭示用於製鋼用電氣爐之噴塗補修之不定形耐火材料上,使用粒徑未滿1mm之燒成橄欖石之例子(參照專利文獻4之表2及3)。但是,在專利文獻4,結合劑之全部為無機結合劑所構成。因此,自然與無機結合劑之絕對使用量一多時,那在高溫域來自無機結合劑之低熔點物質就變成多量存在,經由燒成橄欖石之燒結產生強度表現之效果完全沒有發揮。
本發明之目的,為提供不管是否在結合劑上使用有機結合劑,例如超過1000℃之高溫域不易發生強度下降之不定形耐火材料。
根據本發明之一個觀點,其係提供一種不定形耐火材料,其係包含:由粒徑1mm以上之粗粒域及粒徑未滿1mm之微粒域所構成之耐火性粉體、以及有機結合劑,混合燒成橄欖石於微粒域上,且前述有機結合劑之使用量相對於前述耐火性粉體100質量%其為1質量%以上20%質量以下。
在來自有機結合劑之碳鍵容易劣化之高溫域,粒徑未滿1mm之燒成橄欖石經由燒結具提高本體結構之強度。因此,不管是否使用有機結合劑,可以在高溫域不易發生強度之下降。
以下,經由實施形態對於不定形耐火材料做具體地說明。不定形耐火材料為耐火性粉體上至少加上有機結合劑。
耐火性粉體,其係粒徑1mm以上之粗粒域、及粒徑未滿1mm之微粒域所組成。粗粒域與微粒域之質量比並沒有特別規定,從粒度構成接近最密堆積結構、得到可實用之耐腐蝕性等之觀點來看,經由該領域具備通常技術者之技術常識可自行確定。通常情況下,以耐火性粉體為100質量%時,以其粗粒域為:25~65質量%、與微粒域為:35~75質量%所組成者為佳。
在本說明書,若粒子之粒徑為d以上時,係意味著粒子殘留在JIS-Z8801上所規定篩目為d之篩上為其粒度,當粒子之粒徑未滿d時,係意味著粒子通過同篩時為其粒度。
在微粒域上,混合燒成橄欖石為必要。
在本說明書上,所謂燒成橄欖石其係天然物之橄欖岩,在800℃以上所燒成者。橄欖岩,為以橄欖石為主體之複合物,伴隨一部份之蛇紋石化者。
橄欖岩,主要礦物相為矽酸鎂石(2MgO.SiO2)、頑火輝石(MgO.SiO2)、鐵橄欖石(2FeO.SiO2)、及蛇紋石(3MgO.2SiO2.H2O)等。
橄欖岩,從約800℃開始例如以下(1)、(2)式所
示之分解反應。
2FeO.SiO2+O2 → Fe2O3、Fe3O4+SiO2………(1)
3MgO.2SiO2.2H2O → Mg2SiO4+SiO2+H2O………(2)
上述(2)式,表示結晶水的釋放。暫時,此結晶水的釋放,產生在耐火材料使用中時,耐火材料之強度表現被抑制。另一方面,橄欖岩預先在800℃以上所燒成之燒成橄欖石,結晶水釋放已經終了,所以實質上並不含結晶水,或至少比原本的橄欖岩之結晶水含量更少。因此,結晶水之釋放並不會招致強度低下。
在表1,表示燒成橄欖石化學成分構成之一具體實例。還有,在表1,其Igloss以灼熱減量表示。
如同表1所示,燒成橄欖石的大部分為MgO。MgO之熔點高達2850℃。但是,燒成橄欖石,因為經由燒成上述(1)及(2)式所表示之分解反應已經終了,所以殘餘上以自由的形態包含SiO2或Fe2O3。此結果,燒成橄欖石的熔點,成為各成分的共熔點,比MgO之熔點要低得多。燒成橄欖石的熔點為例如1600~1800℃。
從確實化去除橄欖岩中之結晶水之目的,及確實化上述自由之SiO2或Fe2O3之形成之目的來看,橄欖岩之燒
成溫度,以1000℃以上為佳、1200℃以上為更佳。
混合在微粒域之燒成橄欖石,粒徑未滿1mm時因為細容易燒結。所謂燒結,係在比熔點更低的溫度下,在沒有液相干預之下經由固相反應,這些粒子彼此結合的一種現象。若有粒徑未滿1mm之燒成橄欖石,例如1000~1200℃程度、或是在其以下之溫度產生燒結,其燒結狀態,至少維持到燒成橄欖石之熔點。
因此,未滿粒徑1mm之燒成橄欖石,至少,從1000~1200℃程度至1600~1800℃之溫度範圍內,經由燒結具提高本體結構強度之效果。因此,此溫度範圍,為來自有機結合劑之碳鍵容易劣化之溫度範圍。
亦即,經由本不定形耐火材料時,不管是否使用有機結合劑,由於至少在上述溫度範圍經由燒成橄欖石之燒結補償強度,可以不會因為碳鍵的劣化而造成強度的下降。
還有,磷酸鈉或玻璃料(frit)等之無機結合劑,熔點太低,在1000℃已經為液相狀態,在靠近1000℃賦予強度的效果難以奏效。又,鎂砂質原料、氧化鋁質原料、及二氧化矽質原料等之耐火性粉體,熔點太高,假使在微粒域混合也難以在靠近1000℃下產生燒結。在上述溫度範圍下剛好容易引起碳鍵劣化之燒結,為燒成橄欖石使用於微粒域時所特有的效果。
燒成橄欖石佔據在微粒域上的比率下限沒有特別限定。但是,為了提高燒成橄欖石賦予強度效果的確實性,燒成橄欖石佔據微粒域之4質量%以上為佳。
燒成橄欖石佔據在微粒域上的比率上限也沒有特別限定,由燒成橄欖石構成微粒域的全部亦可,於微粒域上含有燒成橄欖石以外之耐火性粉體亦可。唯,將燒成橄欖石的比率抑制在佔微粒域53質量%以下時,可抑制燒成橄欖石之過燒結,並保持耐熱的剝落性良好。
在微粒域上含有燒成橄欖石以外之耐火性粉體時,其材種沒有特別限定,例如,可使用鎂氧結塊或電熔鎂砂等之鎂砂質原料、白雲石熟料(Dolomite clinker)等之白雲石質原料、氧化鈣熟料等之氧化鈣質原料、電熔氧化鋁、鋁礬土等之氧化鋁質原料、尖晶石熟料等之尖晶石質原料、其他氧化物原料、碳黑等之碳質原料、碳化矽質原料、氮化矽質原料、其他非氧化物原料、以及以此等中至少一種作為其主要成分之選自使用完了之耐火材料廢料中一種以上。
在微粒域上含有燒成橄欖石以外之耐火性粉體時,燒成橄欖石以外之殘餘,由比燒成橄欖石更高熔點之原料所構成者為佳。藉由此,抑制經由微粒域所成基質部之過燒結,可以達到提高耐熱的剝落性。慣用之耐火性粉體,至少如上所示之各原料,也比燒成橄欖石熔點高。其中鎂砂質原料,不僅具有高的熔點,與燒成橄欖石一樣,因為以MgO為主成分,有助於提高經由微粒域所構成之基質部組織的整體性或是連續性、強度和耐腐蝕性的改善。
構成粗粒域之原料沒有特別限定,例如,與微粒域的情況相同,可使用以上所例示之各原料。
但是,在粗粒域上混合燒成橄欖石為佳。藉由此,實現耐腐蝕性的改善。此燒成橄欖石為藉由SiO2成分之溶出提高爐渣的黏性,於本耐火材料的表面上形成黏稠的保護膜,達到防止爐渣的滲透的效果。又,因為在微粒域混合燒成橄欖石,在粗粒域上也藉由混合燒成橄欖石,以提高粗粒域與微粒域和組織的整體性或連續性,有助於強度及耐腐蝕性之提高。
為了增加這樣效果的確實性,在粗粒域上由35質量%以上之燒成橄欖石所構成為佳。粗粒域,粗超過粒徑1mm以上時,因為比微粒域更難燒結,在粗粒域即使多量使用燒成橄欖石,也不會發生過度燒結的問題。
粗粒域,以含有粒徑3mm以上之粒子為佳。即使暫時在此耐火材料有裂紋,可以阻止顆粒上的傳播。粗粒域之最大粒徑並沒有特別限定,例如,以10mm以下為佳,以8mm以下為更佳。
有機結合劑之使用量,相對於外掛耐火性粉體100質量%,以1質量%以上20質量%以下為必要。當此未滿1質量%時,無法確保作為本體結構最低限度之強度。又,當超過20質量%時其容積安定性惡化,最後會產生龜裂。還有,對於耐火性粉體100質量%與有機結合劑之比率以2質量%以上10質量%以下為佳,又,如為3質量%以上6質量%以下的話,為更佳。
作為有機結合劑,在熱間形成碳鍵之物質,例如可選自樹脂、糖類、瀝青、焦油、其他瀝青之一種以上來使用
。作為樹脂,可列舉酚樹脂、呋喃樹脂、環氧樹脂、三聚氰胺樹脂、萜烯樹脂。可與樹脂共同併用六亞甲基芳香四胺等之硬化劑,此情況硬化劑也包含有機結合劑之概念者。作為糖類,可列舉葡萄糖、果糖、半乳糖、及甘露糖等之單糖類或、蔗糖、麥芽糖、乳糖、纖維乙醣、及海藻糖等之二糖類。瀝青和焦油,石油系及煤系之任一種皆可。亦可與樹脂或瀝青共同使用含有例如多元醇等之溶劑,此情況溶劑也包含有機結合劑之概念者。瀝青與樹脂併用時,以具雙方相溶性之溶劑為佳。
亦可與有機結合劑共同併用無機結合劑。作為無機結合劑,例如可選自矽酸鹽、磷酸鹽、硼酸、硼酸鹽、硼砂、玻璃料(frit)、及水泥之一種以上來使用。作為矽酸鹽,可列舉矽酸鈉、矽酸鉀、矽酸鈣。作為磷酸鹽,可列舉六偏磷酸鈉、焦磷酸鈉、四聚磷酸鈉、三聚磷酸鈉、超磷酸鈉、磷酸鉀、磷酸鋰、磷酸鈣、磷酸鎂、磷酸鋁。作為水泥,可列舉氧化鋁水泥、鎂砂水泥、波特蘭水泥。所謂玻璃料(frit),其係可選自含有矽酸鹽、磷酸鹽、碳酸鋰、氟化鈉、及硼酸鹽中之一種以上之出發原料進行熔融、急冷且粉碎所得到之玻璃粉末、例如可列舉硼矽酸系玻璃或鋯石系玻璃。
無機結合劑之熔點,未滿1000℃,通常為300~900℃,當其單獨置於超過1000℃之高溫域,因為不能維持鍵結形態,所以幾乎沒有強度賦予的效果。
但是,在本實施形態,無機結合劑不是以形成鍵為目
的,係以促進燒成橄欖石之燒結為目的來使用。亦即,藉由使用無機結合劑,經由微粒域之燒成橄欖石的粒子界面能量低下,在低溫度,具體而言變成例如從700~800℃程度開始進行燒結。因此,經由微粒域之燒成橄欖石賦予強度而擴大溫度範圍。例如,在氧化環境下使用本耐火材料之情況等時,即使碳鍵之劣化從1000℃以下就能夠開始,也可以抑制強度之下降。
以促進燒成橄欖石之燒結為目的而使用無機結合劑時,該使用量,佔結合劑之比率以50%質量%以下就足夠。有此添加量的話,伴隨低熔點物質之生成亦可忽視耐腐蝕性之低下。
本不定形耐火材料,可只由耐火性粉體及結合劑所構成,進而含有其他添加物亦可。
作為其他添加物,例如可列舉選自有機纖維、金屬纖維、金屬粉、黏性調整劑、及分散劑中之一種以上。作為有機纖維,可列舉維尼綸纖維、聚乙烯纖維、聚丙烯纖維、紙漿纖維,其具提高作業性、斷熱化、及熱間之應力緩和效果。作為金屬纖維,可列舉不銹鋼纖維、Fe纖維、Cu纖維、Al纖維、Ni纖維。作為金屬粉,可列舉Fe粉、Cu粉、Al粉、金屬Si粉、Fe-Si合金粉。作為黏性調整劑,可列舉煤油、重油、雜酚油、蒽油等之煤或石油系之油、植物油、動物油、醚、己內醯胺等之內醯胺類、乙醯苯胺或乙醯乙酸苯胺等之乙醯苯胺類、丁基酚等之烷基酚類。黏性調整劑,具防止灰塵或促進流動之效果。從黏
性調整劑之概念,即用於上述結合劑之溶劑為被去除者。作為分散劑,例如可列舉陰離子系改性木質素木質素磺酸鹽、或β-萘磺酸鹽。
以下,對將上述不定形耐火材料作為塗佈材料使用之餵槽(tundish)乾式塗佈法進行說明。
圖1(a)~(d),為餵槽(tundish)之示意性的局部剖面圖。餵槽(tundish),具有在鐵皮1之內側設置耐火材料內襯2之構造。
如同圖1(a)所示,首先,在餵槽(tundish)的底面上,將不定形耐火材料4,在其上不添加水使保持粉末狀並鋪平,且整平後,在餵槽(tundish)內***中子3。中子3,為已取得具有相對應在餵槽(tundish)的內面形狀上之外面形狀的中空容器狀,例如,以鐵板等之金屬板所構成。
如同圖1(b)所示,接著,在餵槽(tundish)之側面與中子3之間的間隙上,將不定形耐火材料4,在其上不添加水使保持粉末狀進行填充。於不定形耐火材料4進行填充之際,為了減低空隙密實地進行填充,在不定形耐火材料4上賦予振動為佳。
由以上,與***餵槽(tundish)之中子3,與餵槽(tundish)之耐火材料內襯2之間、不定形耐火材料不伴隨水的添加維持粉末狀完成已填充狀態之準備。
還有,只在餵槽(tundish)之側面上形成塗佈層時,圖1(a)所示對餵槽(tundish)底面的不定形耐火材料
之平鋪是不必要的。
如同圖1(c)所示,接著,通過中子3,從中子3之內側將不定形耐火材料4於100~400℃進行加熱。加熱用例如燃燒器或溫風機。加熱時間為例如2~20分鐘。藉由此加熱,使不定形耐火材料4中有機結合劑軟化,發現其保形性。
如同圖1(d)所示,接著,將中子3從餵槽(tundish)中取出。藉由此得到塗佈層5。
其次,供為餵槽(tundish)使用。使用餵槽(tundish)時,從溶鋼來的受熱使塗佈層5的溫度達到超過1000℃溫度。因此,使塗佈層5內之有機結合劑碳鍵化,賦予強度於塗佈層5。
但是,碳鍵在超過1000℃之高溫域經由氧化容易產生劣化。塗佈層5,因為其厚度薄到為5~100mm程度,在塗佈層5上,謀求強度的安定化特為重要。這點,於塗佈層5中之粒徑未滿1mm之燒成橄欖石,在容易引起碳鍵的氧化的溫度域燒結,經由賦予強度於塗佈層5,可謀取塗佈層5強度的安定化。
接著,藉由繼續使用餵槽(tundish)使塗佈層5損耗時,會再次重新形成塗佈層。因此,首先,在停止餵槽(tundish)的使用之後,從耐火材料內襯2的表面,去除殘鋼與上次形成塗佈層5之殘留物,再次依上述之順序進行重複進行。
還有,將本不定形耐火材料施工於餵槽(tundish)的
耐火材料內襯上之方法,並不特別限於以上說明之乾式塗佈法。在本不定形耐火材料上添加水,可在耐火材料內襯進行噴灑或抹平。
但是,在塗佈層的用途上,在施工用水時,施工時本不定形耐火材料與耐火材料內襯太過密著,容易變成對耐火材料內襯之本不定形耐火材料之過多燒附。本不定形耐火材料,因為包含容易燒結之粒徑未滿1mm之燒成橄欖石,燒附往往會更加過度。
塗佈層,從其去除作業之容易觀點來看,與燒附補修材等之一般的補修用不定形耐火材料不同的是,會要求對底層亦即耐火材料內襯之燒附小到一定程度。本不定形耐火材料用於塗佈層之形成時,採用乾式塗佈法,因為可防止在施工時本不定形耐火材料與耐火材料內襯之密著度過高,無論是否含有容易燒結之粒徑未滿1mm之燒成橄欖石,可以使耐火材料內襯2不易產生過剩地燒附。
在表2~4上,展示經由實施例及比較例其不定形耐火材料之構成與評價結果。在表2~4,在微粒域及粗粒域的燒成橄欖石,使用表1所示者。
以下,對於表2~4的評價項目進行說明。
熱間強度:內尺寸為30×30×120mm的框架上填充不定形耐火材料,在200℃使其乾燥。之後,對解除框架所得到之不定形耐火材料進行評價。具體而言,在1200℃
之熱間狀態測定跨距於100mm的彎曲強度,藉由此熱間彎曲強度,以◎、○、△、×之4段階進行相對評價。在4段階的相對評價上,以◎、○、△、×之順序表示優異之評價結果。
耐熱的剝落性:將不定形耐火材料填充在框架上,於1000℃加熱10分鐘使其固化附在試料上,重複進行浸漬於1500℃之溶鋼並放置在室溫,測定直到試料崩潰為止重複進行次數。藉由重複次數,以◎、○、△、×4段階進行相對評價。在4段階的相對評價上,以◎、○、△、×之順序表示優異之評價結果。
耐腐蝕性:將不定形耐火材料填充在框架上,於1000℃加熱10分鐘使其固化附在試料上,使用高頻感應電爐進行侵蝕試驗。在侵蝕劑,使用轉爐爐渣與鋼片以質量比1:1組合者,在1500℃進行侵蝕3小時後,測定平均熔損尺寸。藉由平均熔損尺寸,以◎、○、△、×4段階進行相對評價。4段階的相對評價上,以◎、○、△、×之順序表示優異之評價結果。
表2,表示佔微粒域上其燒成橄欖石變更種種比率之結果。
例1為在微粒域上沒有混合燒成橄欖石之比較例。如同例2所示,佔微粒域之燒成橄欖石的比率僅為4質量%的微量,但與例1相比較時,可看到在1200℃其熱間強度之改善效果。如例3~例6所示,佔微粒域之燒成橄欖石的比率為18質量%以上時,在1200℃的熱間強度改善效果變為顯著。
又,佔微粒域之燒成橄欖石的比率為18質量%以上時,與佔微粒域之燒成橄欖石的比率為0質量%及4質量%時相比較,耐腐蝕性也被改善。此為燒成橄欖石經由SiO2的溶出提高侵蝕劑之黏性,在本耐火材料之表面上形成黏稠性保護膜,被認為係因為顯示了防止侵蝕劑之浸透的效果。
但是,如例6所示,佔微粒域之燒成橄欖石的比率超過53質量%時,會使耐熱的剝落性下降。這被認為係因為經由微粒域之燒成橄欖石使燒結變成過剩。綜合以上的結果進行判斷時,佔微粒域之燒成橄欖石的比率以4質量%以上53質量%以下為佳。
表3,以表2的例3為基礎,表示在結合劑上有機結合劑與無機結合劑變更種種使用量之結果。
如例7所示,有機結合劑相對於外掛耐火性粉體100質量%時未滿1質量%時,碳鍵的形成量過少,在1200℃之熱間強度下降的同時,耐熱的剝落性及耐腐蝕性也下降。
進而,例7為了將結合劑的全部作為無機結合劑,無論在微粒域是否含有燒成橄欖石,在1200℃上完全沒有看到熱間強度之改善效果。此係因為無機結合劑的相對使用量過多,使熱間來自低熔點物質之液相多量生成,認為係因為燒成橄欖石經由燒結其強度表現的效果完全無法發揮。
又,例19為相對於外掛耐火性粉體100質量%含有25質量%之有機結合劑之不定形耐火材料。此時,因為比相對於外掛耐火性粉體100質量%含有20質量%以下之有機結合劑其有機結合劑的量相對地變多,經由碳化或分解時的收縮或膨脹,使容積安定性惡化,最後產生龜裂。
以上,經由表3的結果,有機結合劑相對於外掛耐火性粉體100質量%為1質量%以上20質量%以下是必要的。當其未滿1質量%時,無法確保作為本體結構的最低限強度。又,超過20質量%時其容積安定性惡化,最後產生龜裂。還有,對於耐火性粉體100質量%其有機結合劑之比率以2質量%以上10質量%以下為佳,又,如果
為3質量%以上6質量%以下則更佳。
表4,以表3之例11作為基礎,表示佔粗粒域之燒成橄欖石變更種種比率的結果。
粗粒域由35質量%以上之燒成橄欖石所構成時,可看到耐腐蝕性更加改善的效果。此為粗粒域之燒成橄欖石經由SiO2之溶出,形成黏性的高矽酸鹽皮膜,被認為經
由此顯示具抑制此基質部之侵蝕劑浸透的效果。
以上,對於本發明之具體實例進行說明,但本發明並不限於此。例如,各種組合及改良其可能性對該領域具備通常技術者將是顯而易見。
本發明之不定形耐火材料,不限於餵槽(tundish),例如,可被廣泛利用在轉爐、AOD爐、VOD爐、RH式或DH式等之真空脫氣爐、其他精鍊爐、電氣爐、澆桶、鐵壺、出鋼槽(tapping trogh)、其他之熔融金屬容器的內襯之形成或補修。
本發明之不定形耐火材料之施工後的使用環境,可在氧化環境亦可在非氧化環境。特別是在氧化環境下因為容易產生碳鍵之劣化,本發明,適合使用於氧化環境下其意義特別大。
本發明之不定形耐火材料,在溫間施工及熱間施工之任一種皆可利用。在本說明書上,所謂熱間施工以施工對象面的溫度為600℃以上時為宜,溫間施工其係施工對象面的溫度在常溫~600℃未滿時。
作為溫間施工法特有之例子,其係具有於***熔融金屬容器上之中子與熔融金屬容器的耐火材料內襯之間,不伴隨水的添加直接以粉末狀所填充的狀態準備不定形耐火材料之步驟、與通過中子加熱不定形耐火材料之後,從熔融金屬容器取出去除中子之步驟之乾式塗佈法。此外,作
為溫間施工法特有的例子,也可列舉抹平、沖壓、搗打等方法。
作為熱間施工法特有的例子,可列舉將本不定形耐火材料收集在集裝袋(FIBC)或乙烯袋等之可燃性袋上並投擲到施工對象部位上之方法。
作為熱間施工及溫間施工之任一種皆適用的例子,其係將本不定形耐火材料以氣流運輸送入中空管內,噴灑在施工對象面上之噴灑施工法。在噴灑施工法,亦可在接續中空管內及/或中空管先端上之噴嘴內添加水在本不定形耐火材料上。即使在用水施工的情況,水不包括在本不定形耐火材料之構成要件上。又,作為本不定形耐火材料之構成要件的無機結合劑,亦可添加在接續中空管內及/或中空管先端之噴嘴內上。
本不定形耐火材料之性狀,並沒有特別限制。結合劑上粉末狀之物,例如,可使用粉末酚樹脂使本不定形耐火材料成為粉末狀。又,例如或只在部份的結合劑上使用液狀物,或微量併用黏性調整劑,可使本不定形耐火材料,在可氣流運輸的程度時成為濕潤性狀。又,或使用液狀物在結合劑上,或結合劑即使為粉末狀,併用黏性調整劑,可使本不定形耐火材料變成泥漿狀或夯土狀。可以應用施工法來調整本不定形耐火材料之性狀,對該領域具備通常技術者將是顯而易見。
1‧‧‧鐵皮
2‧‧‧耐火材料內襯
3‧‧‧中子
4‧‧‧不定形耐火材料
5‧‧‧塗佈層
[圖1]餵槽(tundish)模式的局部剖面圖。
Claims (3)
- 一種不定形耐火材料,其係包含:由粒徑1mm以上之粗粒域及粒徑未滿1mm之微粒域所構成之耐火性粉體、以及有機結合劑,混合燒成橄欖石於前述微粒域上,且前述有機結合劑之使用量相對於外掛前述耐火性粉體100質量%其為1質量%以上20%質量以下。
- 如申請專利範圍第1項之不定形耐火材料,其中在前述粗粒域也混合燒成橄欖石,該粗粒域之35質量%以上為由燒成橄欖石所構成。
- 一種餵槽(tundish),其係將如申請專利範圍第1項或第2項之不定形耐火材料藉由乾式塗佈法形成於塗佈層而成者。
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- 2012-07-25 TW TW101126814A patent/TW201313656A/zh unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI504452B (zh) * | 2014-01-28 | 2015-10-21 | ||
TWI632126B (zh) * | 2014-02-28 | 2018-08-11 | 黑崎播磨股份有限公司 | 鋼的鑄造用耐火物,和滑動噴嘴裝置用板,以及鋼的鑄造用耐火物之製造方法 |
Also Published As
Publication number | Publication date |
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JP2013032247A (ja) | 2013-02-14 |
CN103687828B (zh) | 2015-07-29 |
WO2013018476A1 (ja) | 2013-02-07 |
JP5419231B2 (ja) | 2014-02-19 |
CN103687828A (zh) | 2014-03-26 |
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