TWI697469B - 熱間修補用噴射材 - Google Patents

熱間修補用噴射材 Download PDF

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TWI697469B
TWI697469B TW107145440A TW107145440A TWI697469B TW I697469 B TWI697469 B TW I697469B TW 107145440 A TW107145440 A TW 107145440A TW 107145440 A TW107145440 A TW 107145440A TW I697469 B TWI697469 B TW I697469B
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本田和寬
白曼統一
赤井哲
中道翼
大野洋輔
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日商黑崎播磨股份有限公司
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Abstract

本發明之目的在於提高於熱間修補用噴射材之對經噴射之瞬間被修補面的附著性。本發明之熱間修補用噴射材含有65質量%以上95質量%以下之氧化鎂質原料及0.5質量%以上10質量%以下之酚樹脂，且粒徑未達20μm之氧化鎂質原料含量為5質量%以上30質量%以下，粒徑未達20μm之酚樹脂含量為0.3質量%以上9質量%以下，「前述粒徑未達20μm之氧化鎂質原料含量/前述粒徑未達20μm之酚樹脂含量」為0.6以上30以下。

Description

熱間修補用噴射材
本發明有關於例如轉爐、脫氣爐、鑄鍋、其他窯爐之內鑲材的熱間修補所用之與施工水一起噴射至被修補面之熱間修補用噴射材。 又，本發明中所謂「熱間修補」係指被修補面的溫度處於約600℃以上之狀態下之修補。
例如於轉爐中，對內鑲材之熔損部位係以熱間進行修補。作為熱間修補方法已知有將含有耐火原料及結合劑之噴射材與施工水一起噴射至內鑲材之熔損部位之方法。
以往，該方法所使用之噴射材大多使用於結合劑係使用磷酸鹽或矽酸鹽者，但磷酸鹽或矽酸鹽由於與熔渣一起形成低熔點化合物故有耐用性差的缺點。
因此，近幾年來，基於對噴射施工體賦予耐熔渣浸透性及強度為目的而替代磷酸鹽或矽酸鹽，使用於熱間形成碳鍵之物質，具體為酚樹脂等之碳質樹脂(例如參考專利文獻1)。 [先前技術文獻] [專利文獻]
[專利文獻1] 日本特開2010-235340號公報
[發明欲解決之課題]
專利文獻1中，為了抑制碳質樹脂之軟化延遲，而將碳質樹脂之一部分與被造粒粉體一起形成造粒物之狀態進行調配，但熱不易傳遞至形成造粒物以上的碳質樹脂。因此，碳質樹脂之軟化延遲無法避免，噴射材到達被修補面時會回彈，而有對被修補面之附著性差的問題。
本發明欲解決之課題在於對於熱間修補用噴射材，提高對被修補面之附著性。 [用以解決課題之手段]
本發明人等為了提高對被修補面之附著性(以下簡稱為「附著性」)，認為使用酚樹脂作為碳質樹脂有效。亦即，係因為酚樹脂噴射至被修補面之瞬間凝集而容易發揮適當黏性(接著性)之故。且，本發明人等基於提高耐熔渣浸透性等之耐用性之方面而選擇氧化鎂質原料作為耐火原料。進而，本發明人等為了解決前述課題，著眼於氧化鎂質原料與酚樹脂之調配比例，尤其是超微粉區域之調配比例而積極檢討之結果，終至想到本發明。
亦即，依據本發明之一觀點，提供如下之熱間修補用噴射材。 一種熱間修補用噴射材，其含有65質量%以上95質量%以下之氧化鎂質原料及0.5質量%以上10質量%以下之酚樹脂， 且粒徑未達20μm之氧化鎂質原料含量為5質量%以上30質量%以下，粒徑未達20μm之酚樹脂含量為0.3質量%以上9質量%以下， 「前述粒徑未達20μm之氧化鎂質原料含量/前述粒徑未達20μm之酚樹脂含量」為0.6以上30以下。 [發明效果]
依據本發明，由於粒徑未達20μm之活性非常高的超微粉區域之氧化鎂質原料與酚樹脂之調配比例在特定範圍內，而於超微粉區域中氧化鎂質原料與酚樹脂均衡良好地存在，故形成於噴射瞬間具有適當黏性(接著性)之基質，進而於該基質內形成均一碳鍵。藉此提高附著性。
本發明之熱間修補用噴射材含有65質量%以上95質量%以下之氧化鎂質原料及0.5質量%以上10質量%以下之酚樹脂。 氧化鎂質原料含量未達65質量%時，耐腐蝕性(耐熔渣浸透性)等之耐用性降低。氧化鎂質原料含量超過95質量%時，相對地酚樹脂含量變少而使附著性降低。 又，酚樹脂含量未達0.5質量%時，形成碳鍵之效果減弱，附著性降低。酚樹脂含量超過10質量%時，由於自酚樹脂之揮發較多故噴射施工體之組織成為多孔，使噴射施工體強度降低。
本發明係如前述，限定粒徑未達20μm之超微粉區域之氧化鎂質原料與酚樹脂之調配比例。亦即，粒徑未達20μm之氧化鎂質原料含量為5質量%以上30質量%以下，粒徑未達20μm之酚樹脂含量為0.3質量%以上9質量%以下，其含量比「前述粒徑未達20μm之氧化鎂質原料含量/前述粒徑未達20μm之酚樹脂含量」(以下將該含量比簡稱為「含量比」)為0.6以上30以下。限定如此含量比等之調配比例的理由如下。
粒徑未達20μm之氧化鎂質原料含量未達5質量%時，該超微粉的氧化鎂質原料所具有之凝集效果(凝集所致之附著性保持機能)變弱，附著性降低。粒徑未達20μm之氧化鎂質原料含量超過30質量%時，凝集效果變過大而使黏性變高，故噴射施工時之噴出性變差，其結果附著性亦降低。
粒徑未達20μm之酚樹脂含量未達0.3質量%時，形成碳鍵之反應變慢而使附著性降低。粒徑未達20μm之酚樹脂含量超過9質量%時，噴射施工時因生塵而浮游使附著性降低。再者，由於浮游之超微粉的酚樹脂燃燒，故亦有看不到施工部位之問題。
含量比未達0.6時(超微粉之酚樹脂較多時)，酚樹脂之揮發速度變快而一口氣使噴射施工體收縮，於接著界面噴射施工體會隆起而使接著性降低。而且伴隨附著力降低，因噴射施工體自身重量或噴射壓而產生剝落。另一方面，含量比超過30時(超微粉的酚樹脂較少時)，無法保有附著後之強度而使噴射施工體脫落。該含量比之較佳範圍為0.6以上20以下。
作為本發明使用之氧化鎂質原料及酚樹脂可使用作為熱間修補用噴射材的原料一般使用(市售)者。而且，該等氧化鎂質原料及酚樹脂的粒度構成只要調整為粒徑未達20μm者的含量或含量比為前述之特定範圍內即可。此處，本發明之熱間修補用噴射材中由於氧化鎂質原料之一部分可能成為骨材，故只要於例如粒徑未達4mm之粒度區域，粒度調整為粒徑未達20μm者的含量或含量比為前述之特定範圍內即可。 又，本發明所稱「氧化鎂質原料」係指MgO含量為60質量%以上者，除天然氧化鎂原料以外，亦包含氧化鎂磚或氧化鎂・碳磚之屑。又，本發明所稱之「粒徑」係篩眼，例如所謂粒徑未達20μm係指通過20μm之篩眼者。
本發明之熱間修補用噴射材，除了氧化鎂質原料及酚樹脂以外，可含有0.5質量%以上10質量%以下之瀝青。藉由含有0.5質量%以上10質量%以下之瀝青，可提高噴射施工體強度並提高耐用性。
又，本發明之熱間修補用噴射材除了氧化鎂質原料、酚樹脂及瀝青以外，可適當含有白雲石原料或碳原料等之其他耐火原料、金屬粉、有機纖維等之作為熱間修補用噴射材之原料一般使用者。
本發明之熱間修補用噴射材係與以往之熱間修補用噴射材同樣與施工水一起噴射於被修補面，施工水之添加量等之噴射條件或噴射方法與以往相同。 [實施例]
表1中顯示本發明之實施例及比較例之原料調配與評價結果。實施例及比較例之評價項目與評價方法如以下。又，表1中，所謂「其他原料」係白雲石原料、碳原料及金屬粉。
＜附著性＞ 使用慣用之乾式噴射器，將各例之噴射材噴射至已加熱至約1000℃之氧化鎂碳磚的垂直面(被修補面)，形成噴射施工體。施工水的添加量對於噴射材100質量%以外加計設為20～40質量%。 附著性係以噴射材對被修補面之附著比例予以評價，噴射材對被修補面之附著量相對於使用量之比例為80質量%以上時記為○(良好)，60質量%以上未達80質量%時記為△(可)，未達60質量%時記為×(不可)。
＜耐腐蝕性＞ 將自被噴射施工體切出之特定尺寸的試料，使用旋轉侵蝕試驗機，將C/S=3.4之轉爐爐渣與鋼片作為侵蝕劑，於1650～1700℃侵蝕5小時。測定各例之最大熔損量且求出其倒數，求出將實施例1之其倒數設為100時之相對值。該相對值越大意指耐腐蝕性越優。耐腐蝕性之評價於該相對值為80以上時記為○(良好)，於70以上未達80時記為△(可)，於未達70時記為×(不可)。
＜噴射施工體強度＞ 針對自被噴射施工體切出之特定尺寸的試料，依據JISR2575測定常溫之壓縮強度，求出將實施例1之壓縮強度設為100時之相對值。該相對值越大意指噴射施工體強度越高。噴射施工體強度之評價於該相對值為80以上時記為○(良好)，於70以上未達80時記為△(可)，於未達70時記為×(不可)。
＜噴出性＞ 噴射時目視觀察乾試噴射器之噴嘴前端，於無脈動地噴出時記為○(良好)，有脈動時記為×(不可)。
＜綜合評價＞ 前述各評價項目之評價全部為○時記為○(良好)，△為1～3個其他為○時記為△(可)，任一者為×時記為×(不可)。
Figure 02_image001
如表1所示之在本發明範圍內之實施例1～6係附著性評價為○(良好)或△(可)而為良好，綜合評價亦為良好。
比較例1係氧化鎂質原料的含量較少的例。由於有助於耐腐蝕性(耐熔渣浸透性)提高之氧化鎂質原料較少，故無法獲得充分耐腐蝕性。 比較例2係氧化鎂質原料的含量較多的例。相對地酚樹脂含量變少，無法獲得充分之噴射施工體而附著性降低。因此未取得用以評價耐腐蝕性及噴射施工體強度之試料。
比較例3係粒徑未達20μm之氧化鎂質原料的含量較少的例。粒徑未達20μm之氧化鎂質原料具有之凝集效果變弱，附著性降低。 比較例4係粒徑未達20μm之氧化鎂質原料的含量較多的例。凝集效果變過大，噴射施工時之噴出性惡化，其結果無法獲得充分之噴射施工體，附著性降低。因此未取得用以評價耐腐蝕性及噴射施工體強度之試料。
比較例5係酚樹脂之含量較少，含量比高(粒徑未達20μm之酚樹脂含量較少)之例。由於有助於附著性提高之酚樹脂較少，故無法獲得充分之噴射施工體，附著性降低。因此未取得用以評價耐腐蝕性及噴射施工體強度之試料。 比較例6係酚樹脂之含量較多，含量比低(粒徑未達20μm之酚樹脂含量較多)之例。由於酚樹脂之揮發速度變快，且因粒徑未達20μm之酚樹脂於噴射施工時產塵而浮游，結果附著性降低。

Claims (3)

  1. 一種熱間修補用噴射材，其含有65質量%以上95質量%以下之氧化鎂質原料及0.5質量%以上10質量%以下之酚樹脂， 且粒徑未達20μm之氧化鎂質原料含量為5質量%以上30質量%以下，粒徑未達20μm之酚樹脂含量為0.3質量%以上9質量%以下， 「前述粒徑未達20μm之氧化鎂質原料含量/前述粒徑未達20μm之酚樹脂含量」為0.6以上30以下。
  2. 如請求項1之熱間修補用噴射材，其中含有0.5質量%以上10質量%以下之瀝青。
  3. 如請求項1或2之熱間修補用噴射材，其中「前述粒徑未達20μm之氧化鎂質原料含量/前述粒徑未達20μm之酚樹脂含量」為0.6以上20以下。
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