TW201641469A - 碳化矽質耐火塊 - Google Patents

碳化矽質耐火塊 Download PDF

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TW201641469A
TW201641469A TW105106433A TW105106433A TW201641469A TW 201641469 A TW201641469 A TW 201641469A TW 105106433 A TW105106433 A TW 105106433A TW 105106433 A TW105106433 A TW 105106433A TW 201641469 A TW201641469 A TW 201641469A
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Kenji Yanagi
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Abstract

本發明課題為提供一種耐蝕性提高的碳化矽質耐火塊。 解決課題的手段為一種耐火塊，其係具有：由具有既定形狀的碳化矽質耐火物所構成之耐火性塊本體1；以及將該塊本體1的外表面部分在氧氣環境下加熱，使至少一部分的碳化矽氧化而形成為氧化矽的燒成被膜層2。燒成被膜層2以氧化矽的形式燒結，耐蝕性會提高。

Description

碳化矽質耐火塊
本發明關於一種碳化矽質耐火塊。
一直以來，碳化矽質耐火塊被廣泛利用在各種產業用途，尤其是高爐等的工業用爐材。這些耐火塊會預先成形為既定形狀，因此具有能夠以零件的方式搬運、或將塊體彼此積層而製成較大的構造物之優點。關於碳化矽質耐火塊的耐久性，從耐熔損性(耐浸蝕性)、耐剝落性(耐熱衝撃性)或耐潮解性等的觀點來考量，已有各種改良。例如，專利文獻1揭示了一種可鑄性耐火物，其係藉由將燒成而形成了耐氧化被膜的氮化矽鍵結SiC耐火物粉碎，並將所得到的粉碎顆粒製成SiC原料，而具備了耐剝落性。
[先前技術文獻] [專利文獻]
[專利文獻1]日本特開2010-275120號公報
目前產業上正需要較容易使用或高耐久性等 之更良好的耐火塊。
本發明人發現藉由將碳化矽質耐火塊在氧化性環境下加熱，可獲得利用表面部分的層來提高耐蝕性的耐火塊，而完成了本發明。
本發明之碳化矽質耐火塊，其特徵為，具有：由具有既定形狀的碳化矽質耐火物所構成之耐火性塊本體；以及將該塊本體的外表面部分在氧化性環境下加熱，使至少一部分的碳化矽氧化而形成為氧化矽的燒成被膜層。
本發明之碳化矽質耐火塊是由塊本體與燒成被膜層所構成。碳化矽質耐火塊可因應使用目的而具有既定形狀。例如，以模框成形的耐火塊會具有既定形狀。此外，將剖面為一定的長尺狀物體以既定間隔切斷而成的耐火塊，也會具有既定形狀。塊本體為碳化矽質耐火物。此處，廣義地來說，碳化矽質包括了碳化矽。燒成被膜層是碳化矽氧化燒成而形成，因此若燒成前的塊本體所含有的碳化矽少，則難以形成燒成被膜層。所以，在將耐火塊的總成分定為100重量%(以下，%意指重量%)時，碳化矽質宜為含有5%以上的碳化矽的物體。甚至，較佳為含有50%以上的碳化矽。
塊本體所含有的碳化矽以外的成分，可列舉矽、鋁、鈣等的氧化物、碳化物等。另外還可含有金屬矽等的金屬。這些碳化矽以外的成分及摻合比例可因應用途來運用。此外，各成分為顆粒或粒狀。可因應用途 適當地選擇粒度及粒度分布。
塊本體的種類可為使鑄料流進模具中而成形的既定形狀可鑄性塊、在模具內按壓成形所製成的既定形狀按壓成形塊、將既定形狀的成形體燒成而得的燒成塊之任一者。此處，可鑄性塊亦被稱為預鑄塊，並且是將顆粒、粒狀耐火物等以水等製成泥漿狀，使其流進模具內並且固化成既定形狀而成的物體。按壓成形塊是將粉末、顆粒、粒狀耐火物在模具內按壓使其緻密化而成的物體。通常，與可鑄性塊相比，按壓成形塊是呈填充的狀態，氣孔率較低。燒成塊是將可鑄性塊或按壓成形塊等的成形而得到的塊體加熱，使其燒結而成的塊體。
碳化矽質耐火物的碳化矽會與氧發生反應而成為氧化矽，因此通常是在非氧化性環境中燒結。另外，為了促進燒結，也有使用金屬矽或金屬氧化物等的燒結助劑的情形。
本發明之燒成被膜層，是將由具有既定形狀的碳化矽質耐火物所構成之耐火性塊本體的表面部分在氧的存在下燒成，使表面部分所含有的碳化矽成分氧化而形成為氧化矽，以進行表面部分的燒結。
燒成被膜層的厚度係以定在0.5mm以上為佳。
在耐火塊本體上形成燒成被膜層的情況下，原本的耐火塊本體的機械強度愈低，形成燒成被膜層所產生的耐蝕性提升的效果愈高。所以，與氣孔率低的按壓成形塊相比，在氣孔率高的可鑄性塊上形成燒成被膜層較為有效。但是，即使在按壓成形塊上形成燒成被膜層，也 會有耐蝕性提升的效果。此外，將可鑄性塊或按壓成形塊在非氧氣體環境下燒成，並將所得的燒成塊進一步在氧氣體環境下燒成而形成燒成被膜層也是有效的。
本發明之碳化矽質耐火塊，與不具有燒成被膜層而且相同的組成的碳化矽質耐火塊相比，在以鑄料將塊彼此接合的情況下，親和性較良好，耐蝕性提高。此外，本發明的碳化矽質耐火塊，對於高爐渣的耐熔損性及耐剝落性高。因此，具有作為高爐熔鋼用耐火塊的高耐久性。
1‧‧‧塊本體
2‧‧‧燒成被膜層
第1圖為本發明實施例之燒成可鑄性耐火塊的一部分的放大剖面圖。
第2圖表示本發明實施例之燒成可鑄性耐火塊的一部分剖面的矽分布之矽元素分析圖。
第3圖表示與第2圖相同部分剖面的氧分布之氧元素分析圖。
以下，揭示本發明的合適的實施形態。
將本發明之燒成可鑄性耐火塊的一部分的放大剖面圖表示於第1圖。此燒成可鑄性耐火塊是由具有500mm×500mm×300mm的形狀，由碳化矽質耐火物所構成之耐火性塊本體1，以及將該塊本體1的外表面部分在氧氣環境中加熱，使至少一部分的碳化矽氧化而形成為氧化矽的 燒成被膜層2所構成。
此燒成可鑄性耐火塊可藉由以下方法獲得。首先，調製出以Al2O3為3%、SiO2為4%、SiC為86%的化學成分比率(重量%)而含有的碳化矽質鑄料。使用該碳化矽質鑄料，成形為500mm×500mm×300mm的可鑄性耐火塊，然後，在110℃下乾燥24小時，製成可鑄性耐火塊。將該可鑄性耐火塊在大氣中以1400℃以上的高溫加熱數小時，在表面形成約1mm的燒成被膜層2，製成本實施形態的燒成可鑄性耐火塊。
將該燒成可鑄性耐火塊切斷，調查含有燒成被膜層2的塊本體1一部分剖面的矽及氧的元素分布。將矽分布圖表示於第2圖，氧分布圖表示於第3圖。另外，在第2圖及第3圖中，燒成被膜層2的表面邊界以及與塊本體1的交界皆劃上粗黑線。所以，第2圖及第3圖之中，左右延伸的2條黑線之間為燒成被膜層2，下面的一條黑線的下方部分對應於塊本體1的部分。由第3圖可知，氧存在的部分呈黑色，燒成被膜層2的部分比塊本體1的部分還黑，代表氧比較多。此外還可知，第2圖的燒成被膜層2的黑色部分表示矽較多，因此燒成被膜層1的黑色部分為氧化矽。另外還可看出第2圖的白色部分為空隙。
此燒成可鑄性耐火塊的氣孔率為10.1%、總體比重為2.63%。另外，燒成可鑄性耐火塊的壓縮強度(強度)為81MPa、彎曲強度為39MPa。熔損測試是使用在高爐渣(鹼度C/S=1.0)中添加軋鋼鱗片(mill scale)10%的物體，根據感應爐DIP法，在測試溫度1500~1550℃、熔損 時間6小時的條件下進行。在熔損測試之中，爐渣線(SL)部的熔損深度為1.7mm。耐剝落性測試是依據感應爐DIP法，在測試溫度1450~1550℃、1循環的浸漬時間15分鐘、空氣冷卻時間15分鐘的條件下進行。在耐剝落性測試之中，至破裂造成脫落為止的循環數為7次。
為了進行比較，針對並未形成燒成被膜層的可鑄性耐火塊進行同樣的測試。並未形成燒成被膜層的可鑄性耐火塊的氣孔率為14.8%、總體比重為2.42%。另外，並未形成燒成被膜層的可鑄性耐火塊的壓縮強度為12MPa、彎曲強度為3MPa。在熔損測試之中，SL部的熔損深度為5.1mm。在耐剝落性測試之中，至破裂造成脫落為止的循環數為7次。
本發明之碳化矽質耐火塊，尤其是燒成可鑄性耐火塊，其壓縮強度為81MPa、彎曲強度為39MP，與通常的可鑄性耐火塊的壓縮強度為12MPa、彎曲強度為3MPa相比，極高。關於耐熔損性，熔損深度從5.1mm大幅減少至1.7mm。另外，能夠維持住耐剝落性。
像這樣，本發明之碳化矽質耐火塊，藉由表面部分的層提高了作為耐火塊的耐蝕性。
1‧‧‧塊本體
2‧‧‧燒成被膜層

Claims (3)

  1. 一種碳化矽質耐火塊，其特徵為，具有：由具有既定形狀的碳化矽質耐火物所構成之耐火性塊本體；以及將該塊本體的外表面部分加熱，使至少一部分的碳化矽氧化而形成為氧化矽的燒成被膜層。
  2. 如請求項1之碳化矽質耐火塊，其中前述塊本體為使鑄料流進模具中而成形的既定形狀可鑄性塊、在模具內按壓成形所製成的既定形狀按壓成形塊、將既定形狀的成形體燒成而得的燒成塊之任一者。
  3. 如請求項1或2之碳化矽質耐火塊，其中前述碳化矽質耐火物，在將全體定為100重量%時，碳化矽為5%以上。
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