TW201835005A - 含石墨耐火物及含石墨耐火物之製造方法 - Google Patents

含石墨耐火物及含石墨耐火物之製造方法 Download PDF

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TW201835005A
TW201835005A TW107104966A TW107104966A TW201835005A TW 201835005 A TW201835005 A TW 201835005A TW 107104966 A TW107104966 A TW 107104966A TW 107104966 A TW107104966 A TW 107104966A TW 201835005 A TW201835005 A TW 201835005A
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graphite
containing refractory
refractory
mass
carbon fiber
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TWI691473B (zh
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吉田圭佑
松永久宏
濱洋一郎
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日商Jfe鋼鐵股份有限公司
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Abstract

本發明係提供較先前之耐火物更高的抗彎強度及破壞能的含石墨耐火物及該耐火物之製造方法。   本發明係一種石墨之含量為1質量%以上、80質量%以下之範圍內的含石墨耐火物,將纖維直徑為1μm/條以上、45μm/條以下之範圍內的碳纖維在1000條以上、300000條以下之範圍內捆紮,長度100mm以上之碳纖維束被配置於內部。

Description

含石墨耐火物及含石墨耐火物之製造方法
本發明係關於在內部配置碳纖維束的含石墨耐火物及含石墨耐火物之製造方法。
在煉鐵廠中煉鐵步驟或製鋼步驟所使用的設備(精鍊容器、搬送容器等)係以在高溫下可耐長期間之使用之方式內襯施工耐火物。在精煉步驟使用的轉爐係使用氧化鎂.碳質耐火物,在熔鐵預備處理步驟使用的熔鐵鍋(torpedo)或高爐鍋之內襯係使用氧化鋁.碳化矽.碳質耐火物。此等之耐火物係在藉由裝入物所致的機械上的衝擊、藉由溶鋼及熔融爐渣之攪拌所致的磨耗、藉由熔融爐渣所致的爐渣侵蝕及作業中之劇烈的溫度變化等非常嚴酷的條件下使用。因此,為了進行安定的作業,使用可耐嚴酷的條件的耐用性高的耐火物亦為理想。
作為提昇耐火物之耐用性的技術,在專利文獻1係開示將棒狀或網狀之高強度纖維束以合成樹脂等固化,不破壞高強度纖維束之形狀而配置於內部的耐火物。記載有用如此之方式,以不破壞高強度纖維束之形狀而配置於耐火物的內部,提昇耐火物之機械上的強度及耐裂開性。在專利文獻2係開示有藉由耐熱性之接著劑,由拉伸強度高的纖維所構成的單方向之束、撚繩或織物被接著於表面之一部分或全體的耐火物。記載有用如此之方式,以於表面之一部分或全體將由拉伸強度高的纖維所構成的單方向之束、撚繩或織物接著於耐火物,而改善拉伸強度,抑制龜裂產生或破壞,藉由此而可提昇耐火物之壽命。 [先前技術文獻] [專利文獻]
專利文獻1:日本特開2005-320196號公報   專利文獻2:日本特開2007-106618號公報
[發明所欲解決之課題]
配置於專利文獻1及專利文獻2所開示的耐火物的碳纖維之長度為90mm以下,作為使用在曝露於嚴酷的條件的轉爐等的耐火物係有強度不充分的課題。本發明係鑑於上述課題而為者,該目的係提供相較於先前之耐火物而抗彎強度更高及用以破壞耐火物所需要的能量(之後,記載為「破壞能」)更高的含石墨耐火物以及含石墨耐火物之製造方法。 [用以解決課題之手段]
解決如此的課題的本發明之特徵係依照以下所述。   (1) 一種含石墨耐火物,其係石墨之含量為1質量%以上、80質量%以下之範圍內的含石墨耐火物,其特徵為:將長度為100mm以上之碳纖維束被配置於內部,前述碳纖維束係纖維直徑為1μm/條以上、45μm/條以下之範圍內的碳纖維在1000條以上、300000條以下之範圍內捆紮而形成。   (2) 如(1)之含石墨耐火物,其中,前述碳纖維係在1000條以上、60000條以下之範圍內被捆紮。   (3) 如(1)或(2)之含石墨耐火物,其中,前述含石墨耐火物係在20質量%以上、99質量%以下之範圍內包含氧化鎂原料。   (4) 如(1)或(2)之含石墨耐火物,其中,前述含石墨耐火物係在10質量%以上、95質量%以下之範圍內包含氧化鋁原料,包含1質量%以上碳化矽原料。   (5) 如(4)之含石墨耐火物,其中,前述含石墨耐火物係進而在1質量%以上、50質量%以下之範圍內包含二氧化矽原料。   (6) 如(1)或(2)之含石墨耐火物,其中,前述含石墨耐火物係將已粉碎使用完畢之耐火物的耐火物屑,以10質量%以上、90質量%以下之範圍內包含。   (7) 如(1)至(6)中任一項之含石墨耐火物,其中,前述碳纖維束係使用由酚樹脂、氧化鋁溶膠、二氧化矽溶膠、瀝青和焦油中所選定的1種以上之接著劑而接著。   (8) 如(1)至(6)中任一項之含石墨耐火物,其中,前述碳纖維束係由酚樹脂、環氧樹脂、三聚氰胺樹脂、尿素樹脂、醇酸樹脂、不飽和聚酯樹脂、聚胺基甲酸酯、熱硬化性聚醯亞胺、氧化鋁溶膠、二氧化矽溶膠、氧化鋯溶膠、氧化鉻溶膠、氧化鈦溶膠、氧化鎂溶膠、氧化鈣溶膠、氧化釔溶膠、瀝青、焦油及澱粉糊中選定的1種以上之接著劑而接著。   (9) 如(1)至(8)中任一項之含石墨耐火物,其中,前述含石墨耐火物係在對於前述含石墨耐火物而外加為0.10質量%以上、10質量%以下之範圍內,更包含纖維直徑為1μm/條以上、45μm/條以下,纖維長度為1mm以下,對於纖維直徑的纖維長度之比率(纖維長度/纖維直徑)為2以上、1000以下的短碳纖維。   (10) 一種含石墨耐火物之製造方法,其係在1質量%以上、80質量%以下之範圍內含有石墨,於內部配置碳纖維束的含石墨耐火物之製造方法,其特徵為:具有捆紮碳纖維而作為前述碳纖維束的束化步驟、與調配石墨於耐火物原料而作為含石墨耐火物原料的調配步驟、與將已配置前述碳纖維束的前述含石墨耐火物原料成形而作為成形體的成形步驟、與乾燥前述成形體的乾燥步驟;在前述束化步驟係將纖維直徑為1μm/條以上、45μm/條以下之範圍內的前述碳纖維,在1000條以上、300000條以下之範圍內捆紮,設為長度100mm以上之碳纖維束。   (11) 如(10)之含石墨耐火物之製造方法,其中,在前述束化步驟係將前述碳纖維在1000條以上、60000條以下之範圍內捆紮。   (12) 如(10)或(11)之含石墨耐火物之製造方法,其中,前述耐火物原料係氧化鎂原料,在前述調配步驟係在20質量%以上、99質量%以下之範圍內調配前述氧化鎂原料。   (13) 如(10)或(11)之含石墨耐火物之製造方法,其中,前述耐火物原料係氧化鋁原料及碳化矽原料,在前述調配步驟係在10質量%以上、95質量%以下之範圍內調配前述氧化鋁原料,調配1質量%以上前述碳化矽原料。   (14) 如(13)之含石墨耐火物之製造方法,其中,前述耐火物原料係氧化鋁原料、碳化矽原料及二氧化矽原料,在前述調配步驟係在10質量%以上、95質量%以下之範圍內調配氧化鋁原料,調配1質量%以上前述碳化矽原料,在1質量%以上、50質量%以下之範圍內調配前述二氧化矽原料。   (15) 如(10)或(11)之含石墨耐火物之製造方法,其中,前述耐火物原料係已粉碎使用完畢之耐火物的耐火物屑,在前述調配步驟係在10質量%以上、90質量%以下之範圍內調配前述耐火物屑。   (16) 如(10)至(15)中任一項之含石墨耐火物之製造方法,其中,在前述束化步驟係使用由酚樹脂、氧化鋁溶膠、二氧化矽溶膠、瀝青及焦油中所選定的1種以上之接著劑而接著前述碳纖維。   (17) 如(10)至(15)中任一項之含石墨耐火物之製造方法,其中,在前述束化步驟係使用由酚樹脂、環氧樹脂、三聚氰胺樹脂、尿素樹脂、醇酸樹脂、不飽和聚酯樹脂、聚胺基甲酸酯、熱硬化性聚醯亞胺、氧化鋁溶膠、二氧化矽溶膠、氧化鋯溶膠、氧化鉻溶膠、氧化鈦溶膠、氧化鎂溶膠、氧化鈣溶膠、氧化釔溶膠、瀝青、焦油及澱粉糊中所選定的1種以上之接著劑而接著前述碳纖維。   (18) 如(10)至(17)中任一項之含石墨耐火物之製造方法,其中,在前述成形步驟之前,更具有混練前述含石墨耐火物原料的混練步驟、與於成形前述含石墨耐火物原料的模框,填充已混練的含石墨耐火物原料與前述碳纖維束的填充步驟。   (19) 如(18)之含石墨耐火物之製造方法,其中,在前述填充步驟係對於前述模框之容積而填充5容積%以上之前述含石墨耐火物原料後,以相互間距離成為3mm以上之方式,重複並排前述碳纖維束而配置,於前述模框填充前述含石墨耐火物原料與前述碳纖維束。   (20) 如(10)至(17)中任一項之含石墨耐火物之製造方法,其中,在前述成形步驟之前,更具有混練前述含石墨耐火物原料的混練步驟、與於成形前述含石墨耐火物原料的成形容器,填充已混練的含石墨耐火物原料與前述碳纖維束的填充步驟;在前述成形步驟係介由壓力媒體而施加壓力於前述成形容器而成形成形體。   (21) 如(10)至(20)中任一項之含石墨耐火物之製造方法,其中,在前述調配步驟係將纖維直徑為1μm以上、45μm以下、纖維長度為1mm以下、對於纖維直徑的纖維長度之比率(纖維長度/纖維直徑)為2以上、1000以下之範圍內的短碳纖維,在對於前述含石墨耐火物原料而外加為0.10質量%以上、10質量%以下之範圍內調配。    [發明之效果]
藉由將具有100mm以上之長度的碳纖維束配置於內部,可製造高於先前之抗彎強度及破壞能的含石墨耐火物。將如此地已提升抗彎強度及破壞能的含石墨耐火物,例如,以使用於轉爐耐火物而可實現安定的轉爐作業,可延長含石墨耐火物之壽命。
使用於轉爐之內襯的氧化鎂.碳質耐火物係在藉由裝入物所致的機械上的衝擊、藉由溶鋼及熔融爐渣之攪拌所致的磨耗、藉由熔融爐渣所致的爐渣侵蝕及轉爐作業中之劇烈的溫度變化等非常嚴酷的條件下使用。因此,於進行安定的作業係使用可耐如此的嚴酷的條件的耐用性高的氧化鎂.碳質耐火物為理想。同樣地,因為使用於熔鐵鍋(torpedo)或高爐鍋等之熔鐵預備處理容器之內襯的氧化鋁.碳化矽.碳質耐火物亦在非常嚴酷的條件下使用,所以使用可耐此等之條件的耐用性高的氧化鋁.碳化矽.碳質耐火物為理想。
本發明者等係發現將纖維直徑為1μm/條以上、45μm/條以下之碳纖維以1000條以上、300000條以下之範圍內捆紮,將長度100mm以上之碳纖維束配置於耐火物之內部,成為高於先前含石墨耐火物之抗彎強度及破壞能而完成本發明。以下,作為本發明之實施形態使用氧化鎂.碳質耐火物之例而說明本發明。
第1圖係表示關於本實施形態的氧化鎂.碳質耐火物10之一例的立體圖和側視圖。第1(a)圖係氧化鎂.碳質耐火物10之立體圖,第1(b)圖係氧化鎂.碳質耐火物10之側視圖。在關於本實施形態的氧化鎂.碳質耐火物10係於已調配氧化鎂原料於石墨的氧化鎂.碳質原料12之內部,沿著長邊方向配置複數之碳纖維束14。由此,提昇氧化鎂.碳質耐火物10之抗彎強度及破壞能。
在關於本實施形態的氧化鎂.碳質耐火物10係以1質量%以上、80質量%以下之範圍內包含石墨,在20質量%以上、99質量%以下之範圍內包含氧化鎂原料。由此,可抑制因熱剝落所致的耐火物之破裂,且可提昇對於轉爐爐渣的耐熔損性。另一方面,若將石墨之含量設為未達1質量%,則無法抑制因熱剝落所致的耐火物之破裂,耐破裂性大幅地降低。若氧化鎂原料之含量設為未達20質量%,則對於轉爐爐渣的耐熔損性降低,熔損量增大。
第2圖為碳纖維束14之立體圖。碳纖維束14係捆紮複數之碳纖維而形成。碳纖維束14之長度L1係100mm以上,設為沿著在已配置碳纖維束14的氧化鎂.碳質耐火物10的碳纖維束14之長邊方向的長度以下。碳纖維束14係以端面之寬L2為1.0mm以上、20.0mm以下,厚度L3為0.001mm以上、6.0mm以下,以L2之長度成為長於L3之方式,以纖維直徑為1μm/條以上、45μm/條以下之範圍內之碳纖維為1000條以上、300000條以下之範圍內捆紮。
以如此之方式,在本實施形態,碳纖維束14係將纖維直徑為1μm/條以上、45μm/條以下之範圍內之碳纖維,以1000條以上、300000條以下之範圍內捆紮而形成。藉由此,顯現於已配置碳纖維束14的部位抑制因碳纖維束14所致的龜裂之進展的效果,氧化鎂.碳質耐火物10之抗彎強度及破壞能提高。另一方面,若設為碳纖維之纖維直徑為未達1μm/條且條數未達1000條之碳纖維束,則因為碳纖維束過細,所以無法抑制碳纖維束龜裂之進展,無法提昇抗彎強度及破壞能。若設為碳纖維之纖維直徑為超過45μm/條且條數超過300000條之碳纖維束,則因為碳纖維束過粗所以碳纖維束與耐火物原料之纏繞惡化,於成形時產生回彈,成形變為困難。碳纖維束14係亦可將碳纖維在1000條以上、60000條以下之範圍內捆紮而形成。
碳纖維束14係將上述碳纖維之束以由酚樹脂、環氧樹脂、三聚氰胺樹脂、尿素樹脂、醇酸樹脂、不飽和聚酯樹脂、聚胺基甲酸酯、熱硬化性聚醯亞胺、氧化鋁溶膠、二氧化矽溶膠、氧化鋯溶膠、氧化鉻溶膠、氧化鈦溶膠、氧化鎂溶膠、氧化鈣溶膠、氧化釔溶膠、瀝青、焦油及澱粉糊中所選定的1種以上之接著劑而接著為理想。以接著碳纖維之束,因為碳纖維間之密著性及碳纖維束與耐火物原料之密著性提昇而可更緻密化成形體,所以氧化鎂.碳質耐火物10之抗彎強度及破壞能提高。
碳纖維束14之端面之寬L2之長度係長於端面之厚度L3。以如此之方式,以設為碳纖維束14之端面之寬L2之長度為長於端面之厚度L3的扁平形狀,可對碳纖維束14賦予抗彎強度之向異性。而且,以如此之方式排列已賦予抗彎強度之向異性的碳纖維束14之方向而配置於耐火物之內部,而氧化鎂.碳質耐火物10亦成為具有抗彎強度之向異性。
關於本實施形態的氧化鎂.碳質耐火物10係由與成形面16成為垂直的方向壓製而成形製造的耐火物。如第1圖所示,碳纖維束14係碳纖維束14之端面之長邊方向之方向被排列於同一方向,以成形面16與端面之長邊方向之角度θ1成為90°之方式配置。在第1(b)圖,虛線18係為了表示成形面16與碳纖維束14之端面之長邊方向之角度θ1而記載的平行於成形面16的線。   如此,以端面之長邊方向與成形面16之角度θ1成為90°之方式,藉由將碳纖維束14之端面之寬度方向之方向排列於同一方向而配置,於成形之壓製時氧化鎂.碳質原料12變得容易進入碳纖維束14之周圍,提昇氧化鎂.碳質耐火物10之成形性。進而,以將長邊方向之方向排列於同一方向而配置,而成為氧化鎂.碳質耐火物10亦具有抗彎強度之向異性,以長邊方向與成形面16之角度θ1成為90°之方式配置碳纖維束14,藉由成為氧化鎂.碳質耐火物10之碳纖維束14之端面之短邊方向的方向之抗彎強度,可提高成為碳纖維束14之端面之長邊方向的方向之抗彎強度。長邊方向與成形面16之角度θ1係設為90°為理想,但施工上之精度係可容許90±45°程度之誤差。
第3圖係表示將氧化鎂.碳質耐火物10作為轉爐耐火物使用的一例的概略立體圖。如第3圖所示,在轉爐已使用氧化鎂.碳質耐火物10的情況,氧化鎂.碳質耐火物10係以成形面16朝向轉爐之圓周方向(第3圖中,箭頭20)之方式設置。在此情況,氧化鎂.碳質耐火物10係因轉爐作業中之劇烈的溫度變化所致重覆膨脹和收縮,因此於圓周方向,亦即於成為垂直於成形面16的方向產生應力。
如上述,關於本實施形態的氧化鎂.碳質耐火物10係具有抗彎強度之向異性,對於成為平行於成形面16的方向之抗彎強度而言成為垂直於成形面16的方向之抗彎強度較高。因此,將氧化鎂.碳質耐火物10之成形面16,以在轉爐中朝向應力產生的圓周方向而配置,成為對於在轉爐產生的應力可顯現高抗彎強度的氧化鎂.碳質耐火物10。如此,將關於具有抗彎強度之向異性的本實施形態的氧化鎂.碳質耐火物10,以將抗彎強度高的方向朝向在轉爐產生應力的方向而配置,可提昇氧化鎂.碳質耐火物10之耐用性。
關於本實施形態的氧化鎂.碳質耐火物10係如第1圖所示,以成為垂直於氧化鎂.碳質耐火物10之成形面16的方向與沿著碳纖維束14之長度L1的方向之角度θ2成為90°之方式配置。如此,以配置碳纖維束14,相較於以成為垂直於成形面16的方向與沿著碳纖維束14之長度L1的方向成為平行之方式配置的情況,對於成為垂直於成形面16的方向之力的氧化鎂.碳質耐火物10之抗彎強度及破壞能變高。
第4圖係表示成為垂直於氧化鎂.碳質耐火物10之成形面16的方向與沿著碳纖維束14之長度L1的方向之角度θ2為45°的氧化鎂.碳質耐火物10的立體圖和側視圖。第5圖係表示成為垂直於氧化鎂.碳質耐火物10之成形面16的方向與沿著碳纖維束14之長度L1的方向之角度θ2為135°的氧化鎂.碳質耐火物10的立體圖和側視圖。如第4圖及第5圖所示之方式,以成為垂直於氧化鎂.碳質耐火物10之成形面16的方向與沿著碳纖維束14之長度L1的方向之角度θ2成為45°以上、135°以下之範圍內之方式,配置碳纖維束14為理想。藉由此,相較於在成為垂直於氧化鎂.碳質耐火物10之成形面16的方向與沿著碳纖維束14之長度L1的方向成為平行之方式配置碳纖維束14的情況,可提高氧化鎂.碳質耐火物10之抗彎強度及破壞能。在第4圖、第5圖係表示將各碳纖維束14設為平行,對於面AEHD而言平行地配置的例子,但如角度θ1與θ2為各自在45°以上、135°以下之範圍內,則即使各自之碳纖維束14不平行亦可提高氧化鎂.碳質耐火物10抗彎強度及破壞能。
關於本實施形態的氧化鎂.碳質耐火物10係亦可進而將纖維直徑為1μm/條以上、45μm/條以下,纖維長度為1mm以下,對於纖維直徑的纖維長度之比率(纖維長度/纖維直徑)為2以上、1000以下之範圍內的短碳纖維,在對於氧化鎂.碳質原料12而外加為0.10質量%以上、10質量%以下之範圍內包含。以包含短碳纖維,該短碳纖維抑制氧化鎂.碳質耐火物10之龜裂之進展,由此,氧化鎂.碳質耐火物10之抗彎強度及破壞能變高。
第6圖係表示關於本實施形態的氧化鎂.碳質耐火物10之製造流程之一例的圖。使用第6圖而說明氧化鎂.碳質耐火物10之製造方法。氧化鎂.碳質耐火物10係藉由碳纖維之束化步驟、與氧化鎂.碳質原料12之調配步驟、與氧化鎂.碳質原料12之混練步驟、與填充步驟、與成形步驟、與乾燥步驟而製造。
在碳纖維之束化步驟(S101)係首先,例如解開碳纖維之纖維直徑為1μm/條以上、45μm以下的市售之布狀之碳纖維,取出長度為100mm以上之絲狀之碳纖維。作為市售之碳纖維係有纖維絲狀、纖維束狀、交叉狀等各式各樣之形狀之碳纖維,但任一均可適宜地使用。接著,將已取出的絲狀之碳纖維以1000條以上、300000條以下之範圍內捆紮,設為長度為100mm以上之碳纖維束。接著,使碳纖維束浸漬於酚樹脂等之接著劑1~2分鐘左右。將碳纖維束由酚樹脂等之接著劑取出,自然乾燥24小時以上。
在氧化鎂.碳質原料12之調配步驟(S102)係以石墨之含量為對於氧化鎂.碳質原料12而言成為1質量%以上、80質量%以下,氧化鎂原料之含量為對於氧化鎂.碳質原料12而言成為20質量%以上、99質量%以下之方式調配而設為氧化鎂.碳質原料12。更進一步,在調配步驟係硬化劑及黏著劑為外加而添加特定量。
在調配步驟係除了石墨以外,亦可進而將纖維直徑為1μm以上、45μm以下,纖維長度為1mm以下,對於纖維直徑的纖維長度之比率(纖維長度/纖維直徑)為2以上、1000以下之範圍內的短碳纖維調配於氧化鎂.碳質原料12。
在氧化鎂.碳質原料12之混練步驟(S103)係將氧化鎂.碳質原料12使用混練裝置而混練。在填充步驟(S104)係填充對於耐火物之模框之容積而言為5容積%以上之已混練的氧化鎂.碳質原料12,之後,以碳纖維束14之相互間距離成為3mm以上之方式,排列碳纖維束14而配置。接著,填充對於模框之容積而言為5容積%以上之已混練的氧化鎂.碳質原料12,之後,以碳纖維束14之相互間距離成為3mm以上之方式,排列碳纖維束14而配置。重複實施此氧化鎂.碳質原料12之填充、與碳纖維束14之配置,於模框填充氧化鎂.碳質原料12、與碳纖維束14。
如此,以碳纖維束14之相互間距離成為3mm以上之方式,排列碳纖維束14而配置,同時交互地重複氧化鎂.碳質原料12之填充與碳纖維束之配置,於橫方向及高度方向使碳纖維分散而配置,可增加氧化鎂.碳質原料12與碳纖維束之接觸面積,由此,提高氧化鎂.碳質耐火物之抗彎強度及破壞能。另一方面,在不使碳纖維束分散於橫方向及高度方向而配置的情況係無法增加氧化鎂.碳質原料12與碳纖維束之接觸面積,無法提高氧化鎂.碳質耐火物10之抗彎強度及破壞能。碳纖維束14之相互間距離係以成為100mm以下之方式配置為理想。若將碳纖維束14之相互間距離設為超過100mm,則碳纖維束14變少而提高抗彎強度及破壞能的效果變小。
在混練步驟實施氧化鎂.碳質原料12之混練後,以填充步驟於已混練的氧化鎂.碳質原料12配置碳纖維束14為理想。在配置碳纖維束14後實施混練步驟,藉由已設置於混練機的攪拌葉片而切斷碳纖維束14,因為提高氧化鎂.碳質耐火物之抗彎強度及破壞能的效果變小所以不理想。
在成形步驟(S105)係由成為垂直於成形面16的方向加壓,使模框之內部形狀轉印於已填充於耐火物之模框內的氧化鎂.碳質原料12,成形成形體。作為模框係可使用金屬、木材、合成樹脂、橡膠等之材質之模框。成形體係在乾燥步驟(S106)以230℃乾燥18小時,製造碳纖維束14已被配置於內部的氧化鎂.碳質耐火物10。
在本實施形態係表示作為耐火物原料使用氧化鎂原料的例子,但不限於此,取代氧化鎂原料,亦可使用氧化鋁原料及碳化矽原料,亦可使用氧化鋁原料、碳化矽原料及二氧化矽原料。在使用氧化鋁原料及碳化矽原料的情況係將氧化鋁原料,對於含石墨耐火物原料而言在10質量%以上、95質量%以下之範圍內調配,將碳化矽原料,對於含石墨耐火物原料而言調配1質量%以上即可。在使用氧化鋁原料、碳化矽原料及二氧化矽原料的情況係將氧化鋁原料,對於含石墨耐火物原料而言在10質量%以上、95質量%以下之範圍內調配,將碳化矽原料,對於含石墨耐火物原料而言調配1質量%以上,將二氧化矽原料,對於含石墨耐火物原料而言在1質量%以上、50質量%以下之範圍內調配即可。
以將氧化鋁原料之調配量作為10質量%以上、95質量%以下,可提昇對於熔鐵預備處理爐渣的耐熔損性,同時亦可抑制因熱剝落所致的破裂。另一方面,若將氧化鋁原料之調配量作為未達10質量%,則因為對於熔鐵預備處理爐渣的耐熔損性降低所以不理想。若將氧化鋁原料之調配量設為超過95質量%,則無法抑制因熱剝落所致的龜裂之產生,因為耐破裂性降低所以不理想。
以將碳化矽原料之調配量作為1質量%以上,則因為可抑制在大氣環境下的石墨之氧化,所以可維持含石墨耐火物之高耐破裂性。另一方面,若將碳化矽原料之調配量作為未達1質量%,則無法抑止在大氣環境下的石墨之氧化,因為含石墨耐火物之耐破裂性降低所以不理想。
以將二氧化矽原料之調配量作為1質量%以上、50質量%以下,可作成併存高耐破裂性和高耐熔損性的含石墨耐火物。另一方面,若將二氧化矽原料之調配量作為未達1質量%,則因為膨脹量少且微細龜裂不生成,所以抗熱衝擊破壞性無法變大,因為耐破裂性降低所以不理想。若將二氧化矽原料之調配量作為超過50質量%,則因為耐熔損性大幅降低所以不理想。
如此於石墨以上述之方式調配氧化鋁原料及碳化矽原料、或是氧化鋁原料、碳化矽原料及二氧化矽原料,可提昇含石墨耐火物之對於熔鐵預備處理爐渣的耐熔損性,且,可提高含石墨耐火物之抗彎強度及破壞能。因此,該耐火物係可合適地使用作為熔鐵鍋(torpedo)或高爐鍋等之熔鐵預備處理容器之內襯耐火物。
在本實施形態係表示作為耐火物原料使用氧化鎂原料的例子,但不限於此,亦可取代氧化鎂原料,使用氧化鋁原料及氧化鋯原料以對於包含氧化鋁原料、氧化鋯原料及石墨的平板耐火物亦配置關於本實施形態的碳纖維束,可提高該平板耐火物之抗彎強度及破壞能。
在本實施形態係表示作為耐火物原料使用了氧化鎂原料的例子,但不限於此,亦可取代氧化鎂原料,運用粉碎使用完畢之氧化鋁.碳化矽.碳質耐火物而得到的耐火物屑。在使用耐火物屑的情況係將耐火物屑,對於含石墨耐火物原料而言在10質量%以上、90質量%以下之範圍內調配即可。由此,可實現與僅使用未經使用的未用原料的情況之含石墨耐火物相同程度之耐破裂性及耐熔損性。
使用了耐火物屑的耐火物屑原料係相較於未用原料而純度低,但以於耐火物屑調配10質量%以上未用原料,可抑制耐火物原料具有的Al2 O3 成分具有的耐熔損性之大幅的降低。另一方面,若耐火物屑原料之調配量超過90質量%,則未用原料之調配量過少,無法抑制耐火物屑原料中具有的Al2 O3 成分具有的耐熔損性之大幅的降低。若耐火物屑原料之調配量未達10質量%,則因為耐火物屑之再利用率過低,所以作為產業廢棄物之耐火物屑之處理費用大幅地上昇。
在本實施形態係表示於模框填充含石墨耐火物原料和碳纖維束14,成形成形體的例子,但不限定於此。例如,亦可藉由使用如第7圖所示的成形容器的CIP成形而成形成形體。第7圖係說明藉由CIP成形所致的成形方法的圖,第7(a)圖係表示於成形容器36填充氧化鎂.碳質原料12和碳纖維束14的狀態,第7(b)圖係表示將成形容器36裝入已裝滿壓力媒體40的CIP裝置38的狀態。
首先,說明關於於成形容器36填充氧化鎂.碳質原料12和碳纖維束14的方法。在具有金屬芯棒32、與上支撐盤34、與下支撐盤35的支撐構件30,以成為與金屬芯棒32平行之方式,於上支撐盤34及下支撐盤35拉伸複數之碳纖維束14而配置。將已拉伸碳纖維束14的支撐構件30配置於橡膠製之成形容器36內。於以支撐構件30和成形容器36所形成的空間區域填充氧化鎂.碳質原料12,關閉成形容器36之開口而密閉。將已密封的成形容器36,裝入例如以水或油等之壓力媒體40裝滿的CIP裝置38,對壓力媒體40施加49MPa以上、490MPa以下之壓力。藉由此,介由壓力媒體40而可施加均等的壓力於成形容器36,可成形成形體。CIP成形係使用於大的鼓風口耐火物之成形為理想,金屬芯棒32之長度、金屬芯棒32之直徑、上支撐盤34、下支撐盤35之大小、成形容器36之大小係配合所期望之鼓風口耐火物之鼓風口徑等之大小而適宜地制定為佳。在進行CIP成形的情況,成形容器36之材質係使用橡膠為理想。 實施例
接著,關於實施例進行說明。將使用於轉爐的將氧化鎂.碳質原料作為骨材的含石墨耐火物,用以下所示的方法評估。首先,為了研討氧化鎂原料及石墨之含量,按照表1,改變氧化鎂原料之含量、和石墨之含量,按照第6圖之流程,製作含石墨耐火物後,評估耐熔損性及耐破裂性。
關於耐熔損性係使用第8圖所示的高頻感應爐的內襯分別法而測定。   第8圖係說明使用高頻感應爐50的熔損試驗的剖面模式圖。   如第8圖所示,具備感應線圈52的高頻感應爐50之底板54上筒狀地設置含石墨耐火物60,以試驗溫度1500℃、將溫度保持時間設為4小時,將熔鐵56或表2所示的組成之合成爐渣58投入1小時左右,於冷卻後測定熔損量。表1之耐熔損性係以將實施調配例1-3之熔損量設為100的熔損指數進行評估。亦即,在熔損指數為未達100之情況係意味著相較於實施調配例1-3而言熔損量較少,在熔損指數超過100之情況係意味著相較於實施調配例1-3而言熔損量較多。
關於耐破裂性係將40×40×200mm之試料之長邊方向之動彈性率E0 按照JIS(日本工業規格) R 1605所規定的超音波脈衝法而測定。將以1500℃加熱10分鐘,水冷5分鐘,大氣冷卻10分鐘設為1循環的剝落試驗重複實施3次,之後,再次測定動彈性率E3 ,算出在試驗前後之動彈性率之變化率E3 /E0 ,以該值評估耐破裂性。此動彈性率之變化率E3 /E0 小係意味著耐破裂性低。
如表1所示,將石墨之含量作為1質量%以上、80質量%以下,氧化鎂原料之含量作為20質量%以上、99質量的實施調配例1-2~1-8係耐熔損性、耐破裂性為一定,但將石墨之含量設為0.5質量%的實施調配例1-1係耐破裂性大幅地降低,將氧化鎂原料之含量作為10.0質量%的實施調配例1-9係耐熔損性大幅地降低。由此等之結果,確認在使用氧化鎂原料作為耐火物原料的情況,以將石墨含量作為1質量%以上、80質量%以下,將氧化鎂原料之含量作為20質量%以上、99質量%以下,可併存含石墨耐火物之耐熔損性與耐破裂性。
接著,說明關於碳纖維束之長度對含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性帶來影響之情事。將已評估的含石墨耐火物之製造條件及評估結果表示於表3。
如表3所示,將纖維直徑為0.8~7μm/條之碳纖維以碳纖維束14之端面成為扁平形狀之方式捆紮990~12000條後,碳纖維束14之端面之寬度尺寸係收在1.0mm以上、20.0mm以下之範圍內,厚度係收在0.001mm以上、10.0mm以下之範圍內。碳纖維係使用解開東麗公司製TORAYCA(登錄商標)型號CK6261C者。將此碳纖維束各自切出90mm、100mm、200mm、400mm、600mm、800mm、1000mm之長度,為了使碳纖維間之密著性及碳纖維束與氧化鎂.碳質原料之密著性提昇,所以使碳纖維束浸漬1分鐘於酚樹脂而使其密著後,用以下之方法填充此等之碳纖維束和氧化鎂.碳質原料。
對於耐火物之大小為長邊方向1000mm、短邊方向300mm、高度90mm的模框之模框容積,填充10容積%之氧化鎂.碳質原料於模框之底部,成為垂直於成形面的方向與沿著碳纖維束之長度L1的方向之角度θ2成為90°,以碳纖維束之相互間距離成為5mm之方式配置。已填充於模框的氧化鎂.碳質原料係表示於表1的實施調配例1-5之氧化鎂.碳質原料。
以重複此氧化鎂.碳質原料之填充與碳纖維束之配置,將氧化鎂.碳質原料與碳纖維束填充於模框。填充結束後,按照第6圖之流程,進行成形、乾燥而製作實施例2-1~2-7及比較例2-1之含石墨耐火物。測定此含石墨耐火物之抗彎強度、破壞能、耐熔損性及耐破裂性。
含石墨耐火物之抗彎強度係將試驗片尺寸設為40×40×140mm,中心間距離設為100mm,荷重施加速度設為0.5mm/min,依據JIS(日本工業規格)R 2213所記載的3點彎曲試驗方法而進行。
第9圖係表示藉由3點彎曲試驗方法而得到的荷重–變位曲線之一例。破壞能係使用以3點彎曲試驗方法所得到的荷重–變位曲線而可算出。在荷重–變位曲線上,將表示第1最大值的變位作為基準位置,將距該基準位置之變位成為1mm的範圍之面積作為破壞能算出。
如表3所示,裝入長度為100mm以上之碳纖維束的實施例2-1~2-7之含石墨耐火物係抗彎強度及破壞能顯著地提高。另一方面,使用長度為未達100mm之碳纖維束的比較例2-1之含石墨耐火物係相較於實施例2-1~2-7之含石墨耐火物而言抗彎強度及破壞能較低。作為此原因係可認為因為比較例2-1之含石墨耐火物係碳纖維束之長度為短,所以不發揮藉由碳纖維束所致的抑制耐火物之龜裂進展效果之故。由此等之結果,確認提高含石墨耐火物之抗彎強度及破壞能係將碳纖維之長度作為100mm以上即可。
接著,說明關於碳纖維直徑及碳纖維束之條數對於含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性帶來影響之情事。將已評估的含石墨耐火物之製造條件及評估結果表示於表4。
如表4所示,實施例3-1~3-5及比較例3-1、3-2之含石墨耐火物係長度為600mm,將纖維直徑為1μm/條、7μm/條、23μm/條、45μm/條、50μm/條的碳纖維之捆紮條數設為900條、1000條、10000條、12000條、30000條、60000條、300000條、400000條的的碳纖維束配置於含石墨耐火物的含石墨耐火物。此等含石墨耐火物之原料成分係與實施調配例1-5相同,含石墨耐火物之大小係與實施例2-1相同。測定實施例3-1~3-5及比較例3-1、3-2之含石墨耐火物之抗彎強度、破壞能、耐熔損性及耐破裂性。
如表4所示,使用將纖維直徑為1μm/條以上、45μm/條以下之範圍內之碳纖維在1000條以上、300000條以下之範圍內之條數捆紮的碳纖維束的實施例3-1~3-5及實施例2-5之含石墨耐火物係抗彎強度及破壞能高。另一方面,使用纖維直徑為未達1μm/條且碳纖維之條數為未達1000條的碳纖維束的比較例3-1之含石墨耐火物係相較於實施例2-5及實施例3-1~3-5之含石墨耐火物而言抗彎強度及破壞能較低。使用將纖維直徑為超過45μm/條的50μm/條之碳纖維捆紮超過300000條的400000條的碳纖維束的比較例3-2之含石墨耐火物係於成形時產生層合,碳纖維束由耐火物之側面凸出而成形為困難。作為此原因係被認為是碳纖維束變得過粗,碳纖維束與氧化鎂.碳質原料不纏繞,於成形時因碳纖維束所致的回彈產生為其原因。由此等之結果,於提高含石墨耐火物之抗彎強度及破壞能係使用將纖維直徑為1μm/條以上、45μm/條以下之範圍內之碳纖維捆紮1000條以上、300000條以下之範圍內之條數的碳纖維束即可。
接著,說明關於碳纖維束之接著之有無對於含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性帶來影響之情事。將已評估的含石墨耐火物之製造條件及評估結果表示於表5。
如表5所示,實施例4-1~4-11之含石墨耐火物係配置將長度為600mm,直徑為7μm/條之碳纖維捆紮12000條,作為接著劑使用酚樹脂、氧化鋁溶膠、二氧化矽溶膠、瀝青、焦油及澱粉糊而已接著的碳纖維束及未接著的碳纖維束的含石墨耐火物。此等之含石墨耐火物之原料成分係與實施調配例1-5相同,大小係與實施例2-1相同,製造方法係與表3之說明所記載的方法相同。測定實施例4-1~4-11之含石墨耐火物之抗彎強度、破壞能、耐熔損性及耐破裂性。
如表5所示,使用採用酚樹脂、氧化鋁溶膠、二氧化矽溶膠、瀝青、焦油、澱粉糊而已接著的碳纖維束的實施例2-5、4-1~4-5之含石墨耐火物係抗彎強度及破壞能高。使用採用酚樹脂和氧化鋁溶膠、酚樹脂和二氧化矽溶膠、酚樹脂和瀝青、酚樹脂和焦油、酚樹脂和澱粉糊而接著的碳纖維束的實施例4-6~4-10之含石墨耐火物係抗彎強度及破壞能高。
另一方面,使用未接著的碳纖維束的實施例4-11之含石墨耐火物係相較於實施例2-5及實施例4-1~4-10之含石墨耐火物而言抗彎強度及破壞能較低。作為此原因係被認為是因接著碳纖維束,而碳纖維間之密著性及碳纖維束與氧化鎂.碳質原料之密著性更提昇之故。由此等之結果,確認於提高含石墨耐火物之抗彎強度及破壞能係使用由酚樹脂、氧化鋁溶膠、二氧化矽溶膠、瀝青、焦油及澱粉糊中選定的1種以上之接著劑而接著碳纖維,設為碳纖維束為理想。又,可認為使用像上述接著劑的環氧樹脂、三聚氰胺樹脂、尿素樹脂、醇酸樹脂、不飽和聚酯樹脂、聚胺基甲酸酯、熱硬化性聚醯亞胺、氧化鋯溶膠、氧化鉻溶膠、氧化鈦溶膠、氧化鎂溶膠、氧化鈣溶膠及氧化釔溶膠亦可得到同樣之效果。
接著,說明關於碳纖維束之傾斜度對於含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性帶來影響之情事。將已評估的含石墨耐火物之製造條件及評估結果表示於表6。
如表6所示,實施例5-1~5-3之含石墨耐火物係將長度為600mm,直徑為7μm/條之碳纖維捆紮12000條的碳纖維束與耐火物之短邊方向之角度θ2以成為0°、45°、90°、135°之方式配置的含石墨耐火物。此等含石墨耐火物之原料成分係與實施調配例1-5相同,含石墨耐火物之大小係與實施例2-1相同,製造方法係與表3之說明所記載的方法相同。
所謂以碳纖維束與耐火物之短邊方向之角度θ2成為90°之方式配置的含石墨耐火物係如第1圖所示的含石墨耐火物,以該角度θ2成為45°之方式配置的含石墨耐火物係如第4圖所示的含石墨耐火物,以該角度θ2成為135°之方式配置的含石墨耐火物係如第5圖所示的含石墨耐火物。測定實施例5-1~5-3之含石墨耐火物之抗彎強度、破壞能、耐熔損性及耐破裂性。
如表6所示,以碳纖維束與短邊方向之角度θ2成為90°之方式配置的實施例2-5之含石墨耐火物、以與短邊方向之角度θ2成為45°之方式配置碳纖維束的實施例5-1之含石墨耐火物及與短邊方向之角度θ2成為135°之方式配置碳纖維束的實施例5-2之含石墨耐火物係抗彎強度及破壞能高。另一方面,以碳纖維束與短邊方向之角度θ2成為0°之方式配置的實施例5-3之含石墨耐火物係相較於實施例2-5及實施例5-1、5-2之含石墨耐火物而言抗彎強度及破壞能較低。由此等之結果,可確認於提高含石墨耐火物之抗彎強度及破壞能係以與含石墨耐火物之短邊方向之角度θ2成為45°以上、135°以下之方式,配置碳纖維束為理想。
接著,說明關於碳纖維束之間隔對於含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性帶來影響之情事。將已評估的含石墨耐火物之製造條件及評估結果表示於表7。
如表7所示,實施例6-1~6-4之含石墨耐火物係將長度為600mm,直徑為7μm/條之碳纖維捆紮12000條的碳纖維束為以碳纖維束之相互間距離成為1mm、3mm、30mm、100mm之方式配置的含石墨耐火物。此等含石墨耐火物之原料成分係與實施調配例1-5相同,含石墨耐火物之大小係與實施例2-1相同,製造方法係與表3之說明所記載的方法相同。測定實施例6-1~6-4之含石墨耐火物之抗彎強度、破壞能、耐熔損性及耐破裂性。
如表7所示,以碳纖維束之相互間距離成為3mm、30mm之方式配置碳纖維束的實施例6-1、6-2之含石墨耐火物之抗彎強度及破壞能係略高於以碳纖維束之相互間距離成為100mm之方式配置的實施例6-3之含石墨耐火物之抗彎強度及破壞能。將碳纖維束之相互間距離作為1mm而配置的實施例6-4之含石墨耐火物係碳纖維束之間隔過窄,於成形時變得容易產生層合。因此,實施例6-4之含石墨耐火物之抗彎強度及破壞能降低,耐熔損性和耐裂開性亦降低。將碳纖維束之相互間距離設為100mm的情況之抗彎強度及破壞能係相較於碳纖維束之相互間距離設為3mm以上、30mm以下的情況而言若干降低者幾乎不改變。由此等之結果,可確認提高含石墨耐火物之抗彎強度及破壞能係將碳纖維束之相互間距離作為3mm以上、100mm以下為理想,將碳纖維束之相互間距離作為3mm以上、30mm以下為較理想。
接著,說明關於成形方向之碳纖維束之間隔對於含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性帶來影響之情事。將已評估的含石墨耐火物之製造條件及評估結果表示於表8。
如表8所示,實施例7-1之含石墨耐火物係不實施重複氧化鎂.碳質原料之填充和碳纖維束之配置,更加配置將長度為600mm,直徑為7μm/條之碳纖維捆紮12000條的碳纖維束的含石墨耐火物。此含石墨耐火物之原料成分係與實施調配例1-5相同,含石墨耐火物之大小係與實施例2-1相同。測定此含石墨耐火物之抗彎強度、破壞能、耐熔損性及耐破裂性。
如表8所示,將碳纖維束配置為層狀的實施例2-5之含石墨耐火物係抗彎強度及破壞能高。另一方面,更加配置碳纖維束的實施例7-1之含石墨耐火物係抗彎強度及破壞能低。由此結果,確認提高含石墨耐火物之抗彎強度及破壞能係重複氧化鎂.碳質原料之填充和碳纖維束之配置而層狀地配置碳纖維束為理想。
接著,說明關於碳纖維束之配置時機對於含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性帶來影響之情事。將已評估的含石墨耐火物之製造條件及評估結果表示於表9。
如表9所示,實施例8-1之含石墨耐火物係將長度為1200mm,直徑為7μm/條之碳纖維捆紮24000條的碳纖維束配置於已混練後之氧化鎂.碳質原料而製作的含石墨耐火物。實施例8-2之含石墨耐火物係將相同碳纖維束配置於混練前之氧化鎂.碳質原料,於之後混練而製作的含石墨耐火物。此等含石墨耐火物之原料成分係與實施調配例1-5相同,含石墨耐火物之大小係與實施例2-1相同。測定實施例8-1、8-2之含石墨耐火物之抗彎強度、破壞能、耐熔損性及耐破裂性。
如表9所示,於混練後之氧化鎂.碳質原料配置碳纖維束的實施例8-1之含石墨耐火物係抗彎強度及破壞能高。另一方面,於混練前調配碳纖維束,之後混練的實施例8-2之含石墨耐火物係相較於實施例8-1之含石墨耐火物而言抗彎強度及破壞能較低。作為此原因係被認為是若將碳纖維束於配置後進行混練,則於該混練中因攪拌葉片而切斷碳纖維束,使纖維長度變短,結果碳纖維束之抑制龜裂進展效果變少。由此等之結果,確認於提高含石墨耐火物之抗彎強度及破壞能係在混練耐火物原料後,在實施成形步驟前將碳纖維束配置於耐火物原料為理想。
接著,說明關於相對碳纖維束之短邊方向而言的角度對於在CIP成形製造的含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性帶來影響之情事。將已評估的含石墨耐火物之製造條件及評估結果表示於表10。
第10圖係表示實施例9-1~9-3之碳纖維束之裝入角度的剖面模式圖。如表10及第10(a)、(b)、(c)圖之方式,於上支撐盤34與下支撐盤35之間將纖維長度800mm、直徑7μm/條之碳纖維捆紮2400條,以與表3之說明所記載的接著方法相同之方法接著的碳纖維束,碳纖維束之長邊方向與含石墨耐火物之短邊方向所構成的角度θ3成為45°(第10(b)圖)、90°(第10(a)圖)、135°(第10(c)圖)及5°,且,以碳纖維束之相互間距離成為5mm之方式配置支撐構件30。將已配置碳纖維束14的支撐構件30放入成形容器36之中,於以支撐構件30與成形容器36形成的空間填充氧化鎂.碳質原料12後,關閉開口而密閉。
第11圖係表示以CIP裝置成形的狀態的剖面模式圖。如第11圖所示,於裝滿壓力媒體40的CIP裝置38裝入已密閉的成形容器36,介由壓力媒體40而加壓成形容器36。施加特定時間壓力後,由成形容器36取出成形體而製作實施例9-1~9-4之含石墨耐火物。此等含石墨耐火物之原料成分係與實施調配例1-5相同,含石墨耐火物之大小係與實施例2-1相同。測定實施例9-1~9-4之含石墨耐火物之抗彎強度、破壞能、耐熔損性及耐破裂性。
如表10所示,將相對含石墨耐火物之短邊方向的角度θ3作為45°、90°、135°的實施例9-1~9-3之含石墨耐火物係對於短邊方向之應力的抗彎強度及破壞能高。另一方面,將相對含石墨耐火物之短邊方向的角度θ3作為5°的實施例9-4之含石墨耐火物係相較於實施例9-1~9-3之含石墨耐火物而言,對於短邊方向之應力的抗彎強度及破壞能較低。由此等之結果,確認於提高含石墨耐火物之抗彎強度及破壞能係在以CIP成形而成形的含石墨耐火物,亦以相對含石墨耐火物之短邊方向的角度θ3成為45°以上、135°以下之方式配置碳纖維束為理想。
說明關於對於第10圖所示的含石墨耐火物而將碳纖維束之配置方向沿著含石墨耐火物之長邊方向的方向改變而相對碳纖維束之長邊方向的角度對於以CIP成形製造的含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性帶來影響之情事。將已評估的含石墨耐火物之製造條件及評估結果表示於表11。
第12圖係表示實施例10-1~10-3之碳纖維束之裝入角度的剖面模式圖。使用長邊方向1500mm、短邊方向150mm、高度150mm之成形容器,以表11及第12(a)、(b)、(c)圖所示之方式,於上支撐盤34與下支撐盤35之間將纖維長度1200mm、直徑7μm/條之碳纖維捆紮24000條,將以同於記載在表3之說明的接著方法之方法接著的碳纖維束,碳纖維束之長邊方向與含石墨耐火物之長邊方向所形成的角度θ4成為45°(第12(b)圖)、90°(第12(a)圖)、135°(第12(c)圖)及5°,且以碳纖維束之相互間距離成為5mm之方式配置。如此以使配置碳纖維束14的支撐構件30旋轉90°的狀態放入成形容器36之中,在以支撐構件30與成形容器36形成的空間填充氧化鎂.碳質原料12後,關閉開口而密閉。
第13圖為表示以CIP裝置成形的狀態的剖面模式圖。如第13圖所示,於裝滿壓力媒體40的CIP裝置38裝入已密閉的成形容器36,介由壓力媒體40而加壓成形容器36。施加特定時間壓力後,由成形容器36取出成形體而製作實施例10-1~10-4之含石墨耐火物。此等含石墨耐火物之原料成分係與實施調配例1-5相同,含石墨耐火物之大小係與實施例2-1相同。測定實施例10-1~10-4之抗彎強度、破壞能、耐熔損性及耐破裂性。
如表11所示,將相對含石墨耐火物之長邊方向的角度θ4作為45°、90°、135°的實施例10-1~10-3之含石墨耐火物係對於長邊方向之應力的抗彎強度及破壞能高。另一方面,將相對含石墨耐火物之長邊方向的角度θ4作為5°的實施例10-4之含石墨耐火物係相較於實施例10-1~10-3之含石墨耐火物而言,對於長邊方向之應力的抗彎強度及破壞能較低。由此等之結果,確認於提高含石墨耐火物之抗彎強度及破壞能係以相對含石墨耐火物之長邊方向的角度θ4成為45°以上、135°以下之方式配置碳纖維束14為理想。
接著,說明關於使用於熔鐵預備處理容器之內襯耐火物的氧化鋁原料、碳化矽原料及二氧化矽原料之調配量對於含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性帶來影響之情事。將已評估的含石墨耐火物之製造條件及評估結果表示於表12。
如表12所示,實施例11-1~11-11之含石墨耐火物係使用改變氧化鋁原料、碳化矽原料、二氧化矽原料及石墨之調配量的含石墨耐火物原料,配置將長度為600mm,直徑為7μm/條之碳纖維捆紮12000條的碳纖維束的含石墨耐火物。此等含石墨耐火物之大小係與實施例2-1相同,製造方法係與表3之說明所記載的方法相同。測定實施例11-1~11-11之含石墨耐火物之抗彎強度、破壞能、耐熔損性及耐破裂性。
如表12所示,將氧化鋁原料之調配量作為10質量%以上、95質量%以下之範圍內,將二氧化矽原料之調配量作為1質量%以上、50質量%以下之範圍內,將碳化矽原料之調配量作為1質量%以上的實施例11-3~11-5及實施例11-7~11-10之含石墨耐火物係破壞能高,可併存高耐破裂性和高耐熔損性。另一方面,將氧化鋁原料之調配量作為9.0質量%,將二氧化矽原料之調配量作為0.6質量%的實施例11-1之含石墨耐火物係抗彎強度及耐熔損性降低。將二氧化矽原料之調配量作為0.6質量%的實施例11-2之含石墨耐火物係耐熔損性降低。將二氧化矽原料之調配量作為55.0質量%的實施例11-6之含石墨耐火物,耐熔損性亦降低。進而,將氧化鋁原料之調配量作為99.0質量%的實施例11-11之含石墨耐火物係抗彎強度及破壞能降低。由此等之結果,確認作為含石墨耐火物原料,在使用氧化鋁原料、碳化矽原料、二氧化矽原料及石墨的情況提高含石墨耐火物之抗彎強度及破壞能係將氧化鋁原料之調配量設為10質量%以上、95質量%以下之範圍內,將碳化矽原料之調配量設為1質量%以上,將二氧化矽原料之調配量設為1質量%以上、50質量%以下之範圍內為理想。
接著,說明關於將被使用於熔鐵預備處理容器之內襯耐火物的使用完畢之氧化鋁.碳化矽.碳質耐火物屑加以粉碎而得到的耐火物屑之調配量對於含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性帶來影響之情事。將已評估的含石墨耐火物之製造條件及評估結果表示於表13。
如表13所示,實施例12-1~12-4之含石墨耐火物係使用改變耐火物屑、氧化鋁原料、碳化矽原料、二氧化矽原料及石墨之調配量的含石墨耐火物原料,配置長度為600mm,直徑為7μm/條之碳纖維捆紮12000條的碳纖維束的含石墨耐火物。此等含石墨耐火物之大小係與實施例2-1相同,製造方法係與表3之說明所記載的方法相同。測定實施例12-1~12-4之含石墨耐火物之抗彎強度、破壞能、耐熔損性及耐破裂性。
如表13所示,確認將耐火物屑之調配量作為10質量%以上、90質量%以下之範圍內的實施例12-1~12-3之含石墨耐火物係具有與僅使用未用原料的含石墨耐火物同程度之耐破裂性及耐熔損性。另一方面,將耐火物屑之調配量作為95.0質量%的實施例12-4之含石墨耐火物係耐熔損性降低。由此等之結果,可確認在作為含石墨耐火物原料,使用將使用完畢之氧化鋁.碳化矽.碳質耐火物屑加以粉碎而得到的耐火物屑的情況提高含石墨耐火物之抗彎強度及破壞能係將耐火物屑之調配量作為10質量%以上、90質量%以下之範圍內為理想。
接下來,說明關於在氧化鋁.碳質系之含石墨耐火物的氧化鋁原料及碳化矽原料之調配量對於含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性帶來影響之情事。將已評估的含石墨耐火物之製造條件及評估結果表示於表14。
如表14所示,實施例13-1~13-6之含石墨耐火物係使用改變氧化鋁原料、碳化矽原料及石墨之調配量的含石墨耐火物原料,配置長度為600mm,直徑為7μm/條之碳纖維捆紮12000條的碳纖維束的含石墨耐火物。此等含石墨耐火物之大小係與實施例2-1相同,製造方法係與表3之說明所記載的方法相同。測定實施例13-1~13-6之含石墨耐火物之抗彎強度、破壞能、耐熔損性及耐破裂性。
如表14所示,可確認將氧化鋁原料之調配量作為10質量%以上、95質量%以下之範圍內的實施例13-2~13-5之含石墨耐火物係可高度地維持抗彎強度及破壞能,進而,可併存高耐破裂性及耐熔損性。另一方面,將氧化鋁原料之調配量作為6.0質量%的實施例13-1之含石墨耐火物係抗彎強度及破壞能降低。將氧化鋁原料之調配量作為98質量%的實施例13-6之含石墨耐火物係無法抑制因熱剝落所致的龜裂之產生,耐破裂性降低,耐熔損性亦降低。由此等之結果,可確認在使用了氧化鋁.碳質系之含石墨耐火物的情況提高含石墨耐火物之抗彎強度及破壞能係將氧化鋁原料之調配量作為10質量%以上、95質量%以下之範圍內,將碳化矽原料之調配量作為1質量%以上為理想。
接著,說明關於在二氧化矽.碳質系之含石墨耐火物的二氧化矽原料及碳化矽原料之調配量對於含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性所帶來的影響。將已評估的含石墨耐火物之製造條件及評估結果表示於表15。
如表15所示,實施例14-1~14-4、比較例14-1之含石墨耐火物係使用改變二氧化矽原料、碳化矽原料及石墨之調配量的含石墨耐火物原料,配置長度為600mm,直徑為7μm/條之碳纖維捆紮12000條的碳纖維束的含石墨耐火物。此等含石墨耐火物之大小係與實施例2-1相同,製造方法係與表3之說明所記載的方法相同。測定實施例14-1~14-4、比較例14-1之含石墨耐火物之抗彎強度、破壞能、耐熔損性及耐破裂性。
如表15所示,可確認將二氧化矽原料之調配量作為1質量%以上、50質量%以下之範圍內的實施例14-2~14-3之含石墨耐火物係可高度地維持抗彎強度及破壞能,進而,可併存高耐破裂性及耐熔損性。另一方面,將二氧化矽原料之調配量作為未達1質量%的實施例14-1之含石墨耐火物係二氧化矽原料之調配量少,石墨之調配量多達99.0質量%,所以耐熔損性大幅地降低。將二氧化矽原料之調配量作為98.0質量%的實施例14-4之含石墨耐火物係無法抑制因熱剝落所致的龜裂之產生,耐破裂性降低,破壞能亦降低。由此等之結果,可確認在使用了二氧化矽.碳質系之含石墨耐火物的情況提高含石墨耐火物之抗彎強度及破壞能係將二氧化矽原料之調配量設為1質量%以上、50質量%以下之範圍內為理想。
接著,說明關於短碳纖維對於已調配短碳纖維的含石墨耐火物之抗彎強度、破壞強度、耐熔損性及耐破裂性所帶來的影響。將已評估的含石墨耐火物之製造條件及評估結果表示於表16。
如表16所示,實施例15-1~15-9之含石墨耐火物係使用將改變纖維直徑及纖維長度的短碳纖維以不同的調配量調配的含石墨耐火物原料,配置長度為600mm,直徑為7μm/條之碳纖維捆紮12000條的碳纖維束的含石墨耐火物。此等含石墨耐火物之大小係與實施例2-1相同,製造方法係與表3之說明所記載的方法相同。測定實施例15-1~15-9之含石墨耐火物之抗彎強度、破壞能、耐熔損性及耐破裂性。
如表16所示,纖維直徑為1μm/條~25μm/條,纖維長度為2μm~1000μm,對於纖維直徑的纖維長度之比率為2~40的短碳纖維,對於含石墨耐火物原料而外加為0.10質量%以上、10質量%以下之範圍內調配的實施例15-1~15-4之含石墨耐火物係抗彎強度及破壞能高。已調配纖維直徑為超過45μm/條的50μm/條之短碳纖維的實施例15-5之含石墨耐火物係短碳纖維之纖維直徑粗,於成形時產生層合。因此,實施例15-5之含石墨耐火物係相較於實施例15-1~15-4之含石墨耐火物而言抗彎強度及破壞能較低。
已調配纖維長度為超過1000μm(1mm)的2000μm(2mm)之短碳纖維的實施例15-6之含石墨耐火物係碳纖維和耐火物原料之纏繞差,已成形時產生層合。因此,實施例15-6之含石墨耐火物係相較於實施例15-1~15-4之含石墨耐火物而言抗彎強度及破壞能較低。
已調配對於纖維直徑的纖維長度之比率為未達2的1之短碳纖維的實施例15-7之含石墨耐火物係碳纖維和耐火物原料之纏繞差,因此,實施例15-7之含石墨耐火物係相較於實施例15-1~15-4之含石墨耐火物而言抗彎強度及破壞能較低。
以成為未達0.10質量%的0.05質量%之方式調配的短碳纖維的實施例15-8之含石墨耐火物係碳纖維之調配量過少而無法得到藉由短碳纖維所致的抑制龜裂進展效果。因此,實施例15-8之含石墨耐火物係相較於實施例15-1~15-4之含石墨耐火物而言抗彎強度及破壞能較低。
以成為超過10質量%的15質量%之方式調配的短碳纖維的實施例15-9之含石墨耐火物係碳纖維和耐火物原料全部不纏繞,在已成形時產生層合。因此,實施例15-9之含石墨耐火物係相較於實施例15-1~15-4之含石墨耐火物而言抗彎強度及破壞能較低。
由此等之結果,可確認於提高含石墨耐火物之抗彎強度及破壞能係將纖維直徑為1μm/條~25μm/條,纖維長度為2μm~1000μm,纖維直徑與纖維長度之比率為2~40的短碳纖維,對於含石墨耐火物原料而外加為0.10質量%以上、10質量%以下之範圍內調配為理想。
10‧‧‧氧化鎂.碳質耐火物
12‧‧‧氧化鎂.碳質原料
14‧‧‧碳纖維束
16‧‧‧成形面
18‧‧‧虛線
20‧‧‧箭頭
30‧‧‧支撐構件
32‧‧‧金屬芯棒
34‧‧‧上支撐盤
35‧‧‧下支撐盤
36‧‧‧成形容器
38‧‧‧CIP裝置
40‧‧‧壓力媒體
50‧‧‧高頻感應爐
52‧‧‧感應線圈
54‧‧‧底板
56‧‧‧熔鐵
58‧‧‧合成爐渣
60‧‧‧含石墨耐火物
[第1圖]第1圖係表示關於本實施形態的氧化鎂.碳質耐火物10之一例的立體圖和側視圖。   [第2圖]第2圖為碳纖維束14之立體圖。   [第3圖]第3圖係表示將氧化鎂.碳質耐火物10作為轉爐耐火物使用的一例的概略立體圖。   [第4圖]第4圖係表示短邊方向與碳纖維束14之角度θ2為45°的氧化鎂.碳質耐火物10的立體圖和側視圖。   [第5圖]第5圖係表示短邊方向與碳纖維束14之角度θ2為135°的氧化鎂.碳質耐火物10的立體圖和側視圖。   [第6圖]第6圖係表示關於本實施形態的氧化鎂.碳質耐火物10之製造流程之一例的圖。   [第7圖]第7圖係說明藉由CIP成形所致的成形方法的圖。   [第8圖]第8圖係說明使用高頻感應爐50的熔損試驗的剖面模式圖。   [第9圖]第9圖係表示藉由3點彎曲試驗方法而得的荷重–變位曲線之一例。   [第10圖]第10圖係表示實施例9-1~9-3之碳纖維束之裝入角度的剖面模式圖。   [第11圖]第11圖係表示以CIP裝置成形的狀態的剖面模式圖。   [第12圖]第12圖係表示實施例10-1~10-3之碳纖維束之裝入角度的剖面模式圖。   [第13圖]第13圖係表示以CIP裝置成形的狀態的剖面模式圖。

Claims (21)

  1. 一種含石墨耐火物,其係石墨之含量為1質量%以上、80質量%以下之範圍內的含石墨耐火物,其特徵為:   將長度為100mm以上之碳纖維束被配置於內部,   前述碳纖維束係纖維直徑為1μm/條以上、45μm/條以下之範圍內的碳纖維在1000條以上、300000條以下之範圍內捆紮而形成。
  2. 如請求項1之含石墨耐火物,其中,前述碳纖維係在1000條以上、60000條以下之範圍內被捆紮。
  3. 如請求項1或請求項2之含石墨耐火物,其中,前述含石墨耐火物係在20質量%以上、99質量%以下之範圍內包含氧化鎂原料。
  4. 如請求項1或請求項2之含石墨耐火物,其中,前述含石墨耐火物係在10質量%以上、95質量%以下之範圍內包含氧化鋁原料,包含1質量%以上碳化矽原料。
  5. 如請求項4之含石墨耐火物,其中,前述含石墨耐火物係進而在1質量%以上、50質量%以下之範圍內包含二氧化矽原料。
  6. 如請求項1或請求項2之含石墨耐火物,其中,前述含石墨耐火物係將已粉碎使用完畢之耐火物的耐火物屑,以10質量%以上、90質量%以下之範圍內包含。
  7. 如請求項1至請求項6中任一項之含石墨耐火物,其中,前述碳纖維束係使用由酚樹脂、氧化鋁溶膠、二氧化矽溶膠、瀝青和焦油中所選定的1種以上之接著劑而接著。
  8. 如請求項1至請求項6中任一項之含石墨耐火物,其中,前述碳纖維束係由酚樹脂、環氧樹脂、三聚氰胺樹脂、尿素樹脂、醇酸樹脂、不飽和聚酯樹脂、聚胺基甲酸酯、熱硬化性聚醯亞胺、氧化鋁溶膠、二氧化矽溶膠、氧化鋯溶膠、氧化鉻溶膠、氧化鈦溶膠、氧化鎂溶膠、氧化鈣溶膠、氧化釔溶膠、瀝青、焦油及澱粉糊中選定的1種以上之接著劑而接著。
  9. 如請求項1至請求項8中任一項之含石墨耐火物,其中,前述含石墨耐火物係在對於前述含石墨耐火物而外加為0.10質量%以上、10質量%以下之範圍內,更包含纖維直徑為1μm/條以上、45μm/條以下,纖維長度為1mm以下,對於纖維直徑的纖維長度之比率(纖維長度/纖維直徑)為2以上、1000以下的短碳纖維。
  10. 一種含石墨耐火物之製造方法,其係在1質量%以上、80質量%以下之範圍內含有石墨,於內部配置碳纖維束的含石墨耐火物之製造方法,其特徵為:   具有   捆紮碳纖維而作為前述碳纖維束的束化步驟、與   調配石墨於耐火物原料而作為含石墨耐火物原料的調配步驟、與   將已配置前述碳纖維束的前述含石墨耐火物原料成形而作為成形體的成形步驟、與   乾燥前述成形體的乾燥步驟;   在前述束化步驟係將纖維直徑為1μm/條以上、45μm/條以下之範圍內的前述碳纖維,在1000條以上、300000條以下之範圍內捆紮,設為長度100mm以上之碳纖維束。
  11. 如請求項10之含石墨耐火物之製造方法,其中,在前述束化步驟係將前述碳纖維在1000條以上、60000條以下之範圍內捆紮。
  12. 如請求項10或請求項11之含石墨耐火物之製造方法,其中,前述耐火物原料係氧化鎂原料,   在前述調配步驟係在20質量%以上、99質量%以下之範圍內調配前述氧化鎂原料。
  13. 如請求項10或請求項11之含石墨耐火物之製造方法,其中,前述耐火物原料係氧化鋁原料及碳化矽原料,   在前述調配步驟係在10質量%以上、95質量%以下之範圍內調配前述氧化鋁原料,   調配1質量%以上前述碳化矽原料。
  14. 如請求項13之含石墨耐火物之製造方法,其中,前述耐火物原料係氧化鋁原料、碳化矽原料及二氧化矽原料,   在前述調配步驟係在10質量%以上、95質量%以下之範圍內調配氧化鋁原料,   調配1質量%以上前述碳化矽原料,   在1質量%以上、50質量%以下之範圍內調配前述二氧化矽原料。
  15. 如請求項10或請求項11之含石墨耐火物之製造方法,其中,前述耐火物原料係已粉碎使用完畢之耐火物的耐火物屑,   在前述調配步驟係在10質量%以上、90質量%以下之範圍內調配前述耐火物屑。
  16. 如請求項10至請求項15中任一項之含石墨耐火物之製造方法,其中,在前述束化步驟係使用由酚樹脂、氧化鋁溶膠、二氧化矽溶膠、瀝青及焦油中所選定的1種以上之接著劑而接著前述碳纖維。
  17. 如請求項10至請求項15中任一項之含石墨耐火物之製造方法,其中,在前述束化步驟係使用由酚樹脂、環氧樹脂、三聚氰胺樹脂、尿素樹脂、醇酸樹脂、不飽和聚酯樹脂、聚胺基甲酸酯、熱硬化性聚醯亞胺、氧化鋁溶膠、二氧化矽溶膠、氧化鋯溶膠、氧化鉻溶膠、氧化鈦溶膠、氧化鎂溶膠、氧化鈣溶膠、氧化釔溶膠、瀝青、焦油及澱粉糊中所選定的1種以上之接著劑而接著前述碳纖維。
  18. 如請求項10至請求項17中任一項之含石墨耐火物之製造方法,其中,在前述成形步驟之前,更具有   混練前述含石墨耐火物原料的混練步驟、與   於成形前述含石墨耐火物原料的模框,填充已混練的含石墨耐火物原料與前述碳纖維束的填充步驟。
  19. 如請求項18之含石墨耐火物之製造方法,其中,在前述填充步驟係對於前述模框之容積而填充5容積%以上之前述含石墨耐火物原料後,以相互間距離成為3mm以上之方式,重複並排前述碳纖維束而配置,於前述模框填充前述含石墨耐火物原料與前述碳纖維束。
  20. 如請求項10至請求項17中任一項之含石墨耐火物之製造方法,其中,在前述成形步驟之前,更具有   混練前述含石墨耐火物原料的混練步驟、與   於成形前述含石墨耐火物原料的成形容器,填充已混練的含石墨耐火物原料與前述碳纖維束的填充步驟;   在前述成形步驟係介由壓力媒體而施加壓力於前述成形容器而成形成形體。
  21. 如請求項10至請求項20中任一項之含石墨耐火物之製造方法,其中,在前述調配步驟係將纖維直徑為1μm以上、45μm以下、纖維長度為1mm以下、對於纖維直徑的纖維長度之比率(纖維長度/纖維直徑)為2以上、1000以下之範圍內的短碳纖維,在對於前述含石墨耐火物原料而外加為0.10質量%以上、10質量%以下之範圍內調配。
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WO2018155118A1 (ja) 2018-08-30
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TWI691473B (zh) 2020-04-21
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