TW446690B - Refractories for casting a rare-earth alloy, their production method, and method for casting an rare-earth alloy - Google Patents

Refractories for casting a rare-earth alloy, their production method, and method for casting an rare-earth alloy Download PDF

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Publication number
TW446690B
TW446690B TW088110340A TW88110340A TW446690B TW 446690 B TW446690 B TW 446690B TW 088110340 A TW088110340 A TW 088110340A TW 88110340 A TW88110340 A TW 88110340A TW 446690 B TW446690 B TW 446690B
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Taiwan
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oxide
weight
rare earth
funnel
refractory
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TW088110340A
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English (en)
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Hiroshi Hasegawa
Nobuhiko Kawamura
Shiro Sasaki
Yoichi Hirose
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Showa Denko Kk
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
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A7 446690 B7____ 五、發明說明(1 ) [技術領域] 本發明係有關製造如R-Fe-B系磁鐵用合金,R-Ni系氫 吸留合金,Sm-Co系磁鐵用合金等之含有稀土類元素(R ) 做為其主成分之一之稀土類合金之时火物及其製造方法, 以及稀土類合金之鑄造方法。 [技術背景] 最近’活用稀土類合金之優異的磁氣特性之稀土類燒 結磁鐵或稀土類結合磁鐵逐漸受到重視。尤其是R_Fe-B系 磁鐵,正在進行提高磁氣特性之開發。在R-Fe-B系磁鐵方 面,除了擔當磁性之強磁性相R2FeI4B相之外,還存在著 液相燒結之擔當者且對特性之提昇之R Rich相(Nd等之稀 土類元素之濃度高之非磁性之相)大有助益。 惟為必須提高強磁性相之R2Fe14B相之體積比至高特 性磁鐵之程度’ RV 7千相之體積比一定會減少。因此以 先前方法鑄時,R U 7千相分散不良,一部分發生R 9 7 千相不足而往往得不到充分之特性》 另一方面,越是R2Fe14B相之體積比高的组成之磁鐵 用合金,在合金中越容易產生α-Fe»此種a -Fe顯著傷害 磁鐵用合金之粉碎性而成為粉碎時之組成變動之原因,會 引起磁氣特性之降低與增加分散(dispersion)。 為此,有人提出帶胜連铸法(strip casting)(特開平5-' 222488號公報’特開平5-595490號公報)以做為解決上述 有關高特性磁鐵之問題。在該方法中,因可以以比先前之 金屬鑄模鑄造法更高之冷卻速度凝固,故可以製造組織精 本紙張尺度適用中國國家標4 <CNS)A4規格(210 X 297公釐) --------------裝--------訂---------線 (請先s?讀f-面t注音?事項再填寫本頁) - - 經濟部智慧財產局員工消費合作社印製 4 經濟部智慧財產局員工消費合作社印製 A7 B7__ 五、發明說明(2 ) 細化’ R 4 7千相精細地分散而不容易產生α -Fe之合金。 特開平5-222488號中記載在凝固稀土類金-鐵-硼系合 金熔融物以製造永久磁鐵用合金銕塊時,使合金熔融物之 冷卻速度在丨0至500°C/秒,過冷度10至500。(:之冷卻條件 下均勻凝固以帶胚連鑄法製得塊〇_〇5至15mm範圍之厚度 之鑄塊。具體的鑄造法是將熔液由漏斗(Tundish)倒落於 旋轉輥上。 特開平5-295490號例示了製造鱗片狀合金之旋轉盤法 以及製造薄帶或薄片狀合金之雙輥法。 另一方面,最近,做為用於二次電池之電極材料,有 一種氫吸留特性優異的R-Ni系氩吸留合金受到注意。為了 提昇其氫吸留特性或其他之材料特性,在該合金中添加了 鈷、錳、鋁等之元素。因此,以先前之金屬鑄模鑄造法製 造時’容易發生添加元素之顯微偏折(micr〇segregati〇n), 為使用結晶組成均質化’必須做長時間之熱處理。 t又,在氫吸留合金之捣碎工程中,通常可以搗碎至數 十公忽(//)’但利用金屬缚模鑄造法製得之合金時,不容 易搗碎,粒徑大而含有富於添加元素之相,所以搗碎後之 粉末粒度分佈不均,對氫吸留特性有不良影響,最後所得 之氫吸留合金粉末之氣吸留特性不充分為其缺點。 因此,做為鮮決此問題之方法,有人提出帶胚連鑄法 ‘(特開平5-320?则號公報)m可以比先前之金屬禱 模鎮造法更高之冷钟溫度凝固’因此可以製得具有均勻性 優異之組成及組織之合金.利用此種合金,可以製得具有 --------I-----裝--------訂---------線 {請先閱讀背面之注意事項再填寫本頁) A7 446690 五、發明說明(3 ) 起始充電速度大’電池壽命長,且電氣容量大等特性之二 次電池。第1圖為表示帶胚連鑄法之圖式,在可傾倒之提 鍋Ϊ中注入由溶解爐(未圏示)流出之熔液2於漏斗3,由該 盤以一定的供應速度至水冷銅輥(單輥)4 ^隨著輥的旋轉 ,溶液2在水冷銅輥4上面鑄造成形為薄板5形狀’然後薄 板5由輥脫離’被槌子(未圖示)敲碎成薄片6而儲存於金屬 承散Ί。 如上所述,在帶胚連鑄法中,通常是將熔液一點n供 應給輥,以便合金之厚度變成lmm以下。因此,必須保持 由坩鍋引導熔液到冷卻輥之漏斗等不會吸收熔液的熱以致 於凝固。 通常在耐火物氧化鋁、富鋁紅柱石、氧化鋁富鋁紅柱 石' 氧化鎂、氧化鍅、氧化鈣製作之漏斗少量通過熔液時 ,熔液的熱即被漏斗吸收而凝固以致於無法鑄造。此時, 如將漏上弄薄,吸收熱量變少,熔液之流動性即保持良好 ,惟那種薄型漏斗不易製造且容易破裂,所以處理困難。 在使用上述之一般的耐火物所製成的漏斗時,為不發 生上述問題,至少必須將漏斗之表面溫度加熱至與炫液之 溫度大致相同之溫度。但是該等漏斗之加熱有下列的問題 , 丨.熔液溫度約為1200至boot ,可加熱到該温度之加 ( 熱器很昂貴。 2·要對整個漏斗加熱,其裝置之構造複雜。 3.視熔解爐内之真空度,加熱器有時會放電,安全上 本紙張尺度適用中國國家標準(CNS)A4規格(21G X 297公爱) -------------------lit---------^ {請讀^-面之注奪¥項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(4 ) 有問題。 此外’本申請人在歐洲公開公報EP0784350AI中揭示 將氩吸留合金之熔液注入旋轉中之圓筒狀鑄模内之急冷離 心鑄造之方法,注入之熔液與鑄模旋轉一周之間,熔液表 面即凝固,並該凝固面上依次注入熔液鑄造之方法,以及 對鑄模裡面供應熔液由鑄模内兩處以上之噴嘴來進行之方 法。實施該方法的裝置如第2圖所示。 在第2圖中’ 1〇為真空室’其中裝設可傾倒之熔解爐^ ,一次固定漏斗139,2次來回運動漏斗13b,以及旋轉圓 筒鑄模14a。旋轉圊筒鑄模14a係藉由旋轉機構16來旋轉。 炫液由熔解爐12流到一次固定漏料13a,二次來回運 動漏斗13b,再注入旋轉圓筒鑄模14a,並在旋圓筒鑄裡面 缚造鍵料15。此外,插入圓筒鑄模内設置有數個喷嘴,可 使漏斗來回運動。 本發明人曾對帶連鑄法中穩定供應稀土類合金熔液之 耐火物材質加以檢討。另外,也對離心鑄造法中減少熔液 之供應量以供應熔液給旋轉鑄模之耐火物材質,以及單輥 急冷法中由細噴嘴供應熔液之耐火物材質之外,熔液供應 量多時能減少溫降之耐火材質加以檢討。其結果是,發現 通常做為電爐之耐熱材料使用之氧化鋁—氧化矽系或氧化 锆系與熔液毫無反應,且在鑄造時也不需要預熱,終於達 ' 成本發明。 [發明之啟示] 亦即,有關鑄造鑄造本發明第1之稀土類合金之用之 本纸張尺,ti®用争理园家標单(CNSM4規格(2]0 X 297公釐) ----------------------訂--------I <請先閱讀背面之注意事項再填寫本頁) 4 466 9 0 A7 經濟部智慧財產局員工消費合作社印製 本紙張尺度適 B7 五、發明說明(5 ) 耐火物具有下列(1)至(3)之特徵: (1) 氧化鋁及氧化矽之含量 本第1發明之耐火物為氧化鋁—氧化矽系,對於含有 黏合劑等之全部成分重量之氧化鋁之含量為70重量%以上 ,而氧化矽之含量為30重量%以下。 構成耐火物之氧化鋁之含量越多越可以提高耐熱性, 所以為使耐火物在1200至l50〇t之溫度範圍内具有充分之 耐熱性,氧化鋁之含量必須為70重量%。此外,氧化矽之 含量越多’而ί火物成形後之加工性越高,冑於缚造時之熱 衝擊,耐火物不容易破裂。但是氧化矽含量越多,氧化鋁 之含量相對減少,耐火物之耐熱溫度變低。因此氧化矽之 含量必須為30重量%以下。理想的含量為氧化紹為8〇重量 %以上,而氧化矽為20重量%以下。 本第1發明之耐火物中,氧化銘與氧化發宜為整體的9〇 重量%以上,而其他部份為雜質或伴隨元素。 (2) 鬆密度與熱傳導率: 為不使稀土類合金熔液之熱被耐火物吸收,而在鑄造 途中熔液呈現顯著之溫度下降,極端時呈現完全凝固或半 凝固狀態,耐火物應盡量呈多孔狀,使熱傳導率降低:尤 其是,在稀土類全金之鑄造時之代表的熔液溫度範圍12〇〇 至140〇t之熱傳導率最重要,故將耐火物之鬆密度定為 U/cm3以下,在溫度範圍120〇至1400。(:之熱傳導率定為 〇.5kcal/(mh°C)以下,耐火物之鬆密度以約〇5g/cm3以下為 佳。 ^ 用中國國家標準(CNS)A4規格(210 X 297公粲 -------------裝--------訂-----· I ---線 <規先1«.讀^面41-注意事項再填寫本夏> 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(6 ) 為使耐火物之熱傳導率盡量減少,與其含有缴密充填 之氧化鋁粉末’不如含有氧化鋁纖維(真密度為 3.87g/Cm3)70重量%為佳。尤其是將氧化鋁纖維之方向不 必整齊而隨便排列,纖維宜互相交叉排列。同樣地也可以 將氧化鋁纖維與富鋁紅柱石纖維(真密度3丨6g/cm3) 一共含 有70重量%以上以降低熱傳導率。 此外,除了氧化石夕被包含耐火物中成為富鋁紅柱石纖 維之外,也成為膠態氧化矽,或膠態富鋁紅柱石包含其中 〇 (3)灼熱減量 通木1而ί火物疋利用樹脂等有機黏合劑或水玻璃等之 無機黏合劑來成形,但使時並不法除此等黏合劑。因此, 如直接使用该对火物,則由於溶液的熱,有機黏合劑使分 解成氮氣,一氧化碳及二氧碳等之有機氣體與水,同時與 熔液反應而使熔液之流性惡化。另外由易分解無機化合物 所放出之結合水,碳酸氣等也有同樣的影響。熔液之流動 性過分惡化時,熔液會在漏斗中凝固。因此,事先由耐火 物儘2:元全去除點合劑是極其重要的事。從而在本發明中 ,以1400°C,1小時之加熱條件下之灼熱減量率定為ο」重 量%以下為其特徵。此外’如滿足上述鬆密度,熱傳導率 ,灼熱減量率,即可將氧化鋁之一部分置換為氧化鍅、氧 化欽、氧化妈、氧化鎂,而此等成分之理想上限為合計5 重量%。另外還可以包含不超過5重量%之範圍内之氧化 鐵、二氧化一鐵、四氧化三鐵、氧化鈉、氧化鉀及其他不 本虼張尸、度遶用办國國家標垄(.CNS)A.i規格(2〗0 X 297公釐) --------------裝--------訂---------線 {锖先W讀背面之注項再填寫本頁) 446 6 9 0 A7 B7 經濟部智慧財產局員工消費合作社印 五、發明說明( 可避免之雜質做為雜質β 其次,有關本第2發明之稀土類合金缚造用对火物具 有下述(4)至(6)項之特徵。 ⑷氧化错及氧她、三氧化二錦、氧化#、氧化铭 、氧化鈦或氧化;5夕之含量: 本第2發明之耐火物為氧化錯系,其特徵為對於含有 黏合劑等之全部成分重量,氧化錯之含量為7〇重量%以上 、氧化紀、三氧化二鈽 '氧化妈、氣化鎂、氧化紹、氧化 鈦或氧化矽之中之一種以上之含量為3〇重量%以下 '纯粹 之氧化锆在至,显至1170C止為斜晶構造,而在117〇至237〇 □c止為扭曲之四方晶,而237〇t以上為螢石構造之立方形 。冷卻時,由〗not之四方晶轉移至單斜晶構造時,發生 4%之體積蟛脹,如係純碎之氧化锆時就會發生龜裂終至 破壞(例如,κ中島、s島田所著「固態離子學」,第1〇1至 1〇3冊、第131至135頁,年)。因此,為防止破而做為 沒有體積膨脹之等軸晶系之構造,以使用在氧化錯中添氧 化釔、三氧化二鋪、氧化約或氧化錢之一種以上而被置換 固溶之穩定化氧化銼為佳。另外,為改善耐熱’物理上持 續性,以添加氧化鋁、氧化鈦或氧化矽之中之—種以上為 有效。之所以將該等之添加量限定於3〇重量%以下之理由 是添加30重量%以下即有防止破壞之效果,此等添加物對 氧化锆之固溶量有限制,氧化釔與三氧化二鈽償格昂貴, 如添量之氧化鈣、氧化錳,以及三氧化二鋁、氧化鈦、、 氧化矽時,容易與熔液反應之各點。利用這些添加量之較 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) - --------——I* ------ — I 訂--------- {锖先閱讀^面之注意事項再填窝本頁》 A7 B7 五、發明說明(8 佳添加範圍為1至1 5重量% 再者,氧化石夕實際上與氧化錘結合成氧切錯而存在 。在本第2發明之_火物中,氧化錯與氧化紀、三氧化_ 鈽、氧化辦、氧化猛、氧仙 '氧化銳或氧切之中之= 種以上之合計宜為整體之85重量%以上,_ 質與伴隨元素等。 雜 (5) 鬆密度與熱傳導率 與第一發明相同’故省略其說明。 (6) 灼熱減量 除了另外做為雜質可以包含不超過5重量%之範圍之 氧化鐵 '三氧化二鐵、四氧化三鐵、氧化鈉、氧化鉀、氧 化給、碳及其他不可避免之雜質這—點以外與上述⑺相 同。 耐火物之製造方法: 至於本第1發明有關之耐火物之製造方法係將氧化鋁 纖維富鋁紅柱石纖維及氧化矽纖維之中選出一種以上, 以及無機黏合劑及有機黏合劑之一種以上之黏合劑混合而 成之混合物成形,乾燥,固化後,再以lOOOt至140(TC加 熱處理’使耐火物中之氧化鋁成為7〇重量。/。以上,且氧化 石夕成為3 0重量%以下。 本發明有關的方法係首先將選自氡化鋁纖維,富鋁紅 柱石織維及氧化矽纖維之中之一種以上加以配合。例如, 氣化纖與氧化;e夕纖維之組合,氧化鋁纖維與富鋁組柱石 纖維之組合皆可。另外成形混合有機與無機黏合劑之一種 -----— — — It — I I- . I I (靖先閲讀背面之注意事項再填寫本頁) 言 經濟部智慧財產局員工消費合作社印製 11 A7 446690 ______B7_____ 五、發明說明(9 ) 以上的黏合劑之混合物。混合物中之各成分之配合量必須 使耐火物中之氧化鋁為70重量%以上,且氧化矽成為3〇重 量%以下;如使用水玻璃等之含氧化矽黏合劑時,來自黏 合劑與織維之氧化矽之總量必須為一定量。 無機黏合劑可以使用例如水玻璃、膠態氧化石夕等β另 外有機黏合劑可以使用例如矽酸乙酯,乙基纖維素,三乙 二醇等。上述二種黏合劑也可以並用,此時,可以提昇成 形體之乾燥強度與高溫結合強度。同時對於纖維重量 分黏合劑要以1至30重量分為佳,另外,黏合劑中之比例 是以全體為100重量分’有機黏合劑以50至100重量分為佳 〇 其次,將纖維與黏合劑之混合物利用壓床、壓印成為 漏斗、導管、喷管等形狀。為了在加熱處理後容易加工成 為漏斗、導管、喷嘴等,也可以形成如板狀,圓柱狀或圓 筒狀之單純形狀。然後使其充分地自然乾燥使其具有以後 處理上堅固程度之後,藉由加熱處理使成形物内部之有機 物分解而產生多孔構造以促進黏合劑之結合。因為有機物 在400°C至800。(:左右會分解,所以藉此溫度之熱處理即可 獲得多孔構造’但是為了充分去除有機黏合劑,成形物必 須以1000°c至1400-C加熱處理。加溫度不超過i〇0(rc時, 有機黏合劑之去除變成不完全’成為熔液流動性惡化之原 因。另外加熱溫度超過1400°C時’成形物燒結而變脆,不 易處理。另外對於流通熔液時之熱衝擊脆弱,容易破裂。 至於本發明之第二發明有關之耐火物之製造方法係將 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) I n n n n n D I n n I n D n n i n n 一8,< * I iff n n I n n I . H « _ (請先w讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 12 A7 經濟部智慧財產局員工消費合作社印枭 五、發明說明(10) 選自氧化錯纖维、氧化錯鬚晶之令之一種以上,以混合無 機黏合劑及/或有機點合劑而成之混合物成形,俾时火物 中之氧化鍅成為70重量%以上’且氧化釔、三氧化二鈽' 氧化鈣、氧化鎂、氧化鋁、氧化鈦或氧化矽之一種以上之 口。十成為30重量%以下’乾燥固化後再以1〇〇〇至!彻。c加 熱處理。 在本發明有關之方法中,首先將選自氧化錯纖維,氧 化銼鬚晶’穩定化氧化錯纖維’穩定化氧化锆鬚晶之中之 一種以上加以配合。例如,穩定化氧化錯單獨,氧化結纖 維及穩定化氣化錯纖維之組合皆可H將混合有機及 無機黏合劑之一種以上之混合物加以成形。混合物中之各 成分之配合量應為耐火物中之氧化錯為70重量%以上且氧 化釔、二氧化二鈽'氧化鈣、氧化鎂、氧化鋁、氧化鈦或 氡化石夕之-種以上之合計成為3()重量%以下。如果使用水 玻璃等之含氧化㈣合劑時,則來自黏合劑、纖維、鬚晶 之氧化矽總量應為一定量。 其他事項與第一發明相同。 藉由將用於鑄造稀土類合金熔液之本第1及第2發明有 關之耐火物之材質如上所述,從組成鬆密度、熱傳導率及 灼熱減量之面加以特定即可以滿足耐熱性;溶液流動性, 耐破損性及耐熱衝擊性。 本發明有關之稀土類合金之鑄造法之特徵在於藉由將 稀土類合金之熔液由第丨或第2發明之耐火物所加工之漏斗 家標巫(CNSU4 規格 mo 297 公-- • 13 - 裝--------訂---------線 (請先閱讀背面之注項再填寫本頁) 4466 9 Ο Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明說明(11 '導管、喷嘴等灌注於旋轉單輥表面,旋轉雙輥表面以製 造較佳厚度為0.1至lmm之薄板、薄帶、薄片、壓片等。 另外之特徵為藉由注入熔液於旋轉園筒裡面以製造較佳厚 度為1至20mm之筒狀材料。稀土類合金係指稀土類磁鐵用 合金,尤其是R-Fe-B系磁鐵用合金;R-Ni系氫吸留合金、 Sm-Co系磁石用合金等β做為R-Fe-B系磁鐵用合金可轉造 例如23.0°/。之敍、6_0%之镨、1.0°/。之鎮、1.0%之蝴、0.9% 之鈷' 0.1°/。之銅、0.3%之鋁,其他為鐵之組成者。做為R_Ni 系氫吸留合金*可以鑄造例8.7%之鑭、17.1%之鈽、2.0% 之鐯、5,7之敍、1.3%之姑、5.3%之猛、1_9%之鋁,其他 為錄之組合者。做為Sm-Co系磁鐵用合金,可以_造25.〇% 之釤、18.0%之鐵、5.0%之銅、3.0%锆,其他為鈷之組成 者。但是本發明並不限定於此等组成β 上述之漏斗係指由溶解爐或提銷接受稀土類合金溶液 之容器’其具有灌液口以調整薄的鋒造物所必需之灌液速 度。在離心鑄造法或帶胚連鑄法中,因為流經漏斗之熔液 量少,所以會發明上述之熔液吸熱之問題。導管是在離心 鎊造法或帶胚連鑄法中熔解爐與漏斗離開過遠時,用於將 溶液引導至漏斗内部之漏斗之一種形態。所謂喷嘴是指設 置於漏斗或導管之灌液口。尤其是用於離心鑄造之漏斗, 嘴嘴是用於控制熔液對圓旋轉圓筒裡面之體積速度者D此 外,在帶胚連鑄法所用之漏斗時,噴嘴是用於熔液成為層 流’且以一定速度灌入單輥或雙輥。利用本發明之耐火物 做為漏斗鑄造時,熔液流動性良好,因此薄片等之厚度分 t紙張尺度賴巾ϋ國家標準(CNS)A4規格⑵〇 X 297公爱) i H ϋ n I n BE n I .^1 n I - «I a— n I n « n n n ' -' - -(锖先閲讀背面之注意事項再填寫本頁) 14 - 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(12) 佈均勻,組織亦然。此外,將薄片粉碎為磁鐵用合金粉末 時,粉末粒度固定,最終產品之磁鐵特性會穩定化是可以 期待的。另外,由於熔液之速度得到控制,例如在帶胚連 鑄法時,容易將薄片之厚度控制於〇 3 mm以下。此時,稀 土類合金之凝固速度變快,可以形成精細組織。 至於鑄造法中之較佳條件,對漏斗等之灌液溫度,在 上述例示組成之R-Fe-B系磁鐵用合金為135〇至15〇〇。匚’在 上述例示組成之R-Ni氫吸留合金為1350至1500。(:,而在上 述例示組成之Sm-Co系磁鐵用合金為135〇至丨500°C ,另外 在帶胚連鑄法中由漏斗等到單輥之出液溫度,在上述例示 組成之R-Fe-B系磁鐵用合金為13 00至145(TC ,在上述例示 組成之R-Ni氫吸留合金為1300至145(rc,而在上述例示組 成之Sm-Co系磁鐵用合金為;[300至1450°C。 灌液量係由輥或旋轉筒之面積,其旋轉速度及企望之 鑄造厚度來決定。 在本發明中,雖然灌液速度很低速,也不必將漏斗, 導管等預熱即可鑄造稀土類合金熔液,又在鑄造中不必對 它們保溫即可實現良好的液流。從而,在先前之鑄造法中 ,在預熱等之準備作業需要相當的時間與注意,另外在鑄 造中為保持良好之鑄造條件必須依賴有經驗之漏斗之保溫 ,如考慮及此,可以說本發明之鑄造法在操作上及穩定性
I 方面實屬非常進步之方法。 圖式之簡單說明 第1圖為說明帶胚連鑄法之圖式。 本紙狀 ® ^ ^^TcKS)M ^(2]〇xV97 -------— III — — *------ I · I I I I--1 1 (請先閱讀背面之注意事項再填寫本頁) Α7 446 6 9 Ο Β7___ 五、發明說明(13) 第2圖為說明先前之離心鱗造法之圖式。 第3圖為在實施例及比較例中所使用之漏斗圖式。 實施發明之最佳形態: [第1發明之實施例及比較例] 以下利用實施例再詳細說明本發明。 在下面要說明之實施例1至4及比較例1至9所使用之耐 火物之構成成分具有下列之特性: 氧化紹纖維平均直徑5以m,平均長度0.5mm。 富紹紅柱石纖維:平均直徑5 # m,平均長度0.5mm。 膠態氧化矽:平均直徑3至4仁m » 耀態富铭紅柱石:平均直徑3至4 y m。 氧化紹粒子:平均直徑3至4 μ m d 至於黏合劑則使用具有代表性之矽酸乙酯之矽酸乙酯4〇。 實施例1 為達成第1表所記載之耐火物構成,將氧化鋁、富鋁 紅柱石及氧化矽混合,對此纖維混合物1〇〇重量分配合黏 合劑15重量分’將該纖維混合物1〇〇重量分配合黏合劑15 重量分’將該纖維混合物與黏合劑充分混合之淤漿狀混合 物以壓機成形為管狀漏斗材料,利用自然乾燥固化以後, 以第1表所示之加熱處理溫度進行加熱處理。漏斗1具有第 3圖所示之形狀’各部分之尺寸為寬(w)36〇rnrn,高
I (h)125mm ’長⑴900m,而導流部深度(hi)為100mm,上部 寬度〇1)為31〇111111,底部寬(%)為3 0〇111111〇 第1表表示氧化鋁及氧化矽之化學分析結果,鬆密度 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---------裝 — II 訂·--I-----線 (請先閲讀背面之注$項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 16 A7 B7 五、發明說明(I4) 及们2。0至14峨之熱傳導率之最高值。另外.,由漏中 才木取式驗片,在14GG C烘烤1小時,測^減量之結果如第j 表所示。 經由調整供液量俾使正要開始鑄造之前之溫度(拙液 溫度)為145〇t之NdFeB系合金由漏斗3之—端之㈣2之 厚度變成〇.5mm流出,由另—端在帶胚連禱親上鎮造合計 100 A斤肖’炼液正常流出並未在漏斗上凝固,也沒有另 行漏斗之預熱。矯造完畢後’檢查漏斗之狀態,但沒有發 見表示與熔液之反應的變色或異物等。 再者,經由下面公式所定義之流動係數表示熔液之容 易流動性的結果為0.67。 訂 流動係數’留於漏斗内之—定排出壓(head㈣厲) 之溶液要由噴嘴流出時之實際流速除以相同狀態之炫液由 喷嘴流出時之用伯努利定理(B〇rn〇u出s 丁^職)計算出來 之理論流速。 線 再者,此公式所記載之理論流速v在設定重力加速度 經 濟 部 智 慧 財 產 局 員 工 消 費 合 社 印 為g,滯留於漏斗之熔液之厚度為^^夺,可利用下式計算: V=,(2gh) a 實施例2 利用與實施例丨相同之耐火物所構成之漏斗以實施 例相同之帶胚連鑄法缚造錦鑭稀土合金(mish _叫㈣ 恥系合金(出液溫度145〇t.),熔液並未在漏斗上凝固,但 正t流動。此時之流動係數為〇.67。 鑄造完畢後,檢查3漏斗之狀態,並未發見與熔液之 甲國國家標準(CNS)..\4規格(2l(! x 297公爱 ]7 A7 4 466 9 0 B7__ 五、發明說明(15) 反應® 實施例3 使用與實施例相同之耐火物製成的漏斗,並以實施例 1相同的帶胚連鑄法鑄造Sm-Co系合金(出液溫度1450°c )之 結果’溶液並未在漏斗上凝固而正常流動,此時之流動係 數 0.71 » 鎊造完畢後,檢査3漏斗之狀態,並未發見與熔液之 反應。 比較例1 利用第1表記載之耐火物所製成之漏斗,以實施例1相 同之方法’以帶胚連鑄法鑄造NdFeB系合金。但是在鑄造 途中,熔液之流動性漸趨惡化,終於凝固起來。熔液在勉 強流動之間之流動係數為0.26。 再者,此耐火物之加熱處理條件為800 ΐτι小時,在 1400eC之灼熱減量比為4·〇重量% » 比較例2 將與實施例1相同組成的耐火物與實施例】同樣地加入 成漏斗。此時之耐火物之加熱條件是15〇〇它下1小時加 工當中耐火物破裂好多次。 實施例4 , 以實施例1相同之方法製作,第1表記載之耐火物所構 成之漏斗,並以實施例丨相同之帶胚連鑄法鑄造了 NdFeB 系合金之結果,熔液未在漏斗凝固而正常流出。正要鑄造 之前之溶液溫度(出液溫度)為145代。此時之流動係數為 本紙張尺度適用中國國家標準<CNS)A4規格(210 X 297公爱) ----------裝·--ill 訂--— — — — —--線 - * C - (請先閲讀背面之注項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 18 A7
五、發明說明(l6) 0.77。此外,並未實施漏斗之預熱。 鑄造完畢後,檢查了漏斗之狀態,未發見與熔液之反 應。 fc.較例3 利用在第1表比較例3所記載耐火物所構成而以第!表 之方法所製成之漏斗,以實施例1相同之方法,用帶胚連 鑄法鑄造NdFeB系合金》但是在鑄造當中熔液之流動性逐 漸惡化,終至凝固。熔液在勉強流動之間之流動係數為〇 Μ 〇 再者,該耐火物之加熱處理條件為8〇〇»C 1小時,在丨4〇〇 °C之灼熱減量比為4.0重量%。 比較例4 將第1表比較例所記載之組成之耐火物以實施例1同的 方法加工為漏斗。此時之耐火物的加熱條件為1500°c I小 時’加工過程中’耐火物多次破裂。 比較例5 利用在第1表比較例5所記載耐火物所構成之漏斗,以 實施例1相同的方法,以帶胚連鑄法鑄造^肝化系合金之 結果。溶液未在漏斗上凝固而流動,但在铸造過程中發生 了由漏斗底面之漏液。補正漏液部分之流動係為〇 45。 缚造完畢後,檢查了漏斗之狀態的結果,漏斗穿孔, 該孔周圍之大範圍内變色。另外剖開漏斗觀察穿孔表面之 結果禮認了縱使未穿孔部分,接觸到熔液之絕大部分有變 色係在每遣日ΐ ^液與漏斗之反應所致。由此推論當溶液 木紙張反度述用由國圉家標準(CN:S)A.l規格(2i!j X 297公¥ ; -n I n n ϋ ϋ ϋ ϋ I * 1« 1 }· n n tt Ε.』6J* I n In t n ! n I (請先閱讀背面之注§項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 19 經濟部智慧財產局員工消費合作社印製 446 6 9 0 a7 _____B7__ 五、發明說明(17 ) 流動係數低於實施例1之情形之原因在於熔液與巧斗反應 以致引起熔液之流動性惡化。 比較例6 將第2表比較例7所記載之耐火物(該耐火物係由氧化物纖 維,富鋁紅柱石纖維,膠態富鋁紅柱石及一般的耐火物之 氧化鋁耐火搗碎之顆粒所構成)以實施例1相同的方法加工 為漏斗。並以實施例1相同的方法,利用帶胚連鑄法鋒造 NdFeB系合金之結果,一開始炫液之流動性即惡化,尚未 鑄造完成時即告凝固。在熔液勉強流動之間的流動係數為 0.24。 比較例8 將第3表比較例8所記載之一般的耐火物以實施例1 一 樣地加工,並以實施例相同的方法帶胚連鑄法擬製造 NdFeB系合金。可是,熔液開始流入漏斗時立刻凝固以致 無法铸造。 另外,鑄造完畢後,去除殘留於漏斗内之合金以調查 漏斗之狀態,並未看到與溶液之反應。 比較例9 將第3表比較例9所記載之一般的耐火物以實施例一樣 地加工成漏斗,並利用與實施例相同的方法帶胚連鑄法擬 製造NdFeB系合金。可是熔液開始流入漏斗時立刻凝固以 致無法鑄造。 另外,鑄造完畢後,去除殘留於漏斗内之合金,剖開 漏斗以觀察穿孔表面之結果,確認了漏斗内部也變色,與 本紙張尺度適用中國國家標準(CNSMd規格(210 X 297公釐) — — — 11 — 1 — · — - I I ! I 1 訂 I ---1-^^ , ' - - - (請先閱讀背面之注意#-項再填寫本頁) 20 A7
五、發明說明(18) 熔液有反應之事實。 第1表耐火物之構成主要成分及特性 構成Γ 主要成分 鬆密 度 g/cm3 熱傳 導率 kcal/ (mh °C) 加熱處理 灼熱減 量率Wt% 氣化 鋁織 維含 量 wi% 富鋁 红柱 石纖 維含 量 wt% 膠態 氧化 矽含 量 wt。/。 膠態 富鋁 紅柱 石含 董 wt% Α120 3含董 wt% Si02 含量 wt% 實施例 卜3 83 — 15 - 83 15 0.3 0.41 1200°C1 時間 <0.1以下 比較例1 «3 一 15 一 83 \\5 0.3 0.4] 800°C】時間 4.0 比較例2 83 一 15 — 83 15 0.3 0.41 150(TCi 時間 <0_1以下 實施例4 82 10 一 5 93 4 0.3 0.40 1200°C1 時間 < 0.1 jITt* 比較例3 82 10 — 93 4 0.3 0.40 800ΐ I時瓦 广4.0 比較例4 82 10 — 5 93 4 0.3 0,40 I500°C1時間 < 0.〗以下 比較例5 93 — ~ 97 26 0.3 0.48 ]200°C1 畤間 <0.1以下 第2表耐火物之構成主要成分及特性 成構 主要成分 鋁柱織含 富紅石維 量 % wt 態鋁柱含 膠富红石 量咖一 氧化 is含 量 wt% A120 3含量 wt%
Si〇2 含量 wt% 鬆密 度 g/cm3 熱傳 導牟 kcal/( mh^C) 加熱處理 灼熱減 量率wt% --------I-----裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 比較例6 50 10 35 92 比較例7 30 20 10 35 87 1.6 2.3 ]200t 1時間 1.6 2.4 】200°C 1時間 <0.1以下 <0.1以下 經濟部智慧財產局員工消費合作社印製 第3表耐火物之構成主要成分及特性 構成 主要成分 鬆密 度 g/cm3 熱傳 導率 kcal/(m h°C) 加熱處理 灼熱減 量準wt% 比ΐ交例「 比叙例9 氧化鋁 纖維含 量Wt% 富雜紅 柱石纖 維含量 wt% A1203 含量 wt% 恥2含 量wt% 98 Ί — 98 2.8 4,1 「無 <0,1以下 95 68 26 2.1 3.8 無 <0.1以下 本氣張尺度適用中國國家標準(〇:S)A4蜆格(210x29了公餐 2! 經濟部智慧財產局員工消費合作杜印製 446 6 9 0 A7 ____B7____ 五、發明說明(I9) [第2發明之實施例及比較例] 以下要說明之實施例5至26及比較例10至29中所使用 之耐火物之構成成分具有下列之特性: 氧化鍅纖維:平均直徑5em,平均長度丨5mm。 氧化锆鬚白:平均直徑5仁m,平均長度5〇〇mm。 穩疋化氧化錯纖維,平均直徑5#^,平均長度i,5 mm 0 穩疋化氧化錯鬚白:平均直役5/zm,平均長度500# m *黏合劑是使用具有矽酸乙酯代表性之矽酸乙酯4 〇。 實施例5 將氧化錯' 氧化釔、氧化矽混合使其成為第4表所記 載之耐火物之構成,對此纖維混合物1〇〇重量分配合以黏 合劑15重量分,再將此纖维混合物與黏合劑充分混合之齡 漿狀混合物以壓機成形使其成為管狀漏斗材料,並利用自 然乾燥固化後,在第4表所示之加熱處理溫度進行加熱處 理。漏斗3具有第3圖所示之形狀,各部分之尺寸與第玉發 明之實施例與比較例相同。 在第4表中表示有氧化錯、氧化紀、氧化矽之化學分 析結果,鬆密度及在12〇〇至〗400°C之熱傳導率最高值。另 外也表示由漏斗採集試樣於1400°C烘烤1小時後測定原料 之結果。 i 將正要缚造前之溫度(出液溫度)為145(TC之NdFeB系 合金由漏斗1之一端將供液量調整為熔液2之厚度成為 0.5mm流出’並由另—端在帶胚連鎮輥上鎮造總計i〇〇公 本紙張尺度適用中國國豕標準(CNS)A4規格(2]〇 X 297公愛) I-------- -----------I 1^ <請先閲讀背面之注意事項再填寫本頁) 22 經濟部智慧財產局員工消費合作社印製 A7 ____B7__ 五、發明說明(20 ) 斤之結果,熔液並未在漏斗上凝固而正常地流動。此外, 並未實施漏斗之預熱《鑄造完畢後,檢查了漏斗之狀態, 惟未發現表示與熔液反應之變色,異物等。 再者’以實施例1所定義之流動係數表示熔液之易流 動性時為0.71。 實施例6 利用與實施例5相同之耐火物所構成之漏斗,以實施 例5相同用帶胚連鑄法鑄造鈽鍊稀土合金(Misch Metai)Ni 系合金(出液溫度145(TC )之結果,溶液並未在漏斗上凝固 而正常流動。此時之流動係數為0.71。鑄造完畢後,檢查 漏斗之狀態,惟未發見與熔液之反應。 實施例7 利用與實施例5相同之耐火物構成之漏斗以實施例相 同之帶胚連鑄法鑄造SmCo系合金(液溫度145〇。(:)之結果 ’炼液並未在漏斗上凝固而正常流出。此時之流動係數為 0.77。鑄造完畢後檢查了漏斗’惟未發見與熔液之反應。 將第4表所記載之耐火物所構成之漏斗以實施例5相同 之方法製作,並以實施例相同之帶胚連鑄法鑄造NdFeB系 合金之結果,無論何種材質之漏斗上皆未凝固熔液而正常 流出(出液溫度1450°C)。該等鑄造時之熔液之流動係數如 第4表所記載。再者,並未在漏斗之預熱。鑄造完畢後, h查了漏斗之狀態’惟未發見與溶液之反應D 實施例1 0至1 7 ..... ^^1 ei < ^^1 - f— HI ^ί— I -1 I ^ 4 - - - -i -- 1 n an —i I (請先w讀背面之注$項再填寫本頁) 23 446 6 9 Ο Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明說明(21 擬利用第5表所記載之耐火物所構成之漏斗4實施例5 相同之方法即帶胚連铸法鋒造NdFeB系合金,但是無論何 種漏斗在鑄造過程中熔液之流動性即逐漸惡化,終致凝固 。熔液勉強流動之間之流動係數為0.27至0_30。 另外,該耐火物之加熱處理條件為800°C下1小時,在 1400°C之灼熱減量率所有漏斗皆為4.0重量%。 實施例18至25 將第5表所組成之耐火物與實施例5 —樣地加工成漏斗 。此時耐火物之加熱條件為1 500°C下1小時,在加過程中 所有之漏斗之耐火物多次破裂。 實施例26 利用第5表比較例26記載之耐火物製成的漏斗,以實 施例5相同的方法即帶胚連鑄法鑄造NdFeB系合金之結果 ’溶液固然無問題地流動,惟缚造過程中由漏斗之底面發 生液漏。補正液漏部分之流動係數為0.43。 鑄造完畢後’檢查漏斗之狀態之結果,漏斗有破洞, 該洞之周圍廣冷地變色。又剖開漏斗檢查破洞表面之結果 ’沒有破洞的部分接觸到溶液之絕大部分皆變色,確認了 鑄造時與漏斗發生了反應。由此事實推定熔液之流動係數 會比實施例5之情形低的原因是熔液與漏斗反應以致熔液 之流動性惡化之故》 實施例27至28 將第6表之比較例2 7至2 8所記載之一般之咐火物以實 施例5相同之方法加工成漏斗,並擬以實施例相同之方法 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公楚) I I I 1 I--— — — ——— ' II I 1 I--^ «— — III— — — (請4?閲讀"面之注意事項再填寫本頁) -24 A7 B7__ 五、發明說明(22) ,即帶胚連鑄法鑄造NdFeB系合金’但是熔液在正開始流 入漏斗時即告凝圍,以致無法缚造。 此外’於鑄造完畢後去除殘留於漏斗内之合金並檢查 漏斗之狀態’惟未發見與熔液之反應。 實施例29 將第6表比較例2 9記載之一般耐火物以實施5 一樣加工
為漏斗,並擬以實施例5相同之方法帶胚連鑄法鑄造NdFeB 系合金。但是熔液正要流入漏斗時即告凝固,以致無法鑄 造。 ’“、 [產業上可利用性] 根據本發明’利用稀土類磁鐵用原料不需使用複雜之 工程與裝置即可穩定製造最合適之合金,極為實用。除了 此合金以外,在鋒造各種稀土類合金時之镇造條件的品質 管理也容易。 ---------------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製
本紙張尺度逹用中國國家揉準(CN.S)/VJ规格(2W ο 9 6 6 4 4
7 7 A B 五、發明說明(23 ) 經濟部智慧財產局員工消費合作社印製 |實施挪6| 實齡C5 I實施令_ I實施畑1 I實施筆1 tmm\ 實施卿 丨實施例19 丨實施例18 實施例17 |實施例16| 丨實施例15| |實施例14| |實施例13| 丨實赫㈣ 丨實施例li 1 丨實施例l〇| I實施#J91 丨實施例8 1 1實施w 1 丨實施例6 1 丨實施例5 1 ΟΊ 1 1 1 1 s 1 I 1 1 i 1 1 l 1 1~* f 1 1 1 氣化 纖 維 ;wt% 寐 [ 1 ί 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ! 氧化 m 白 wt% s s 1 s S 1——· s 8 h—4 8 s 8 8 8 8 (—4 8 δ s 8 8 s 8 穩定化 氡德 纖維 wt% Η—1 1 1 1-^ 8 1~« 1 1 1 1 1 1 1 1 ] 1 1 1 1 1 ! 1 穩定化 氧碰 鬚白 wt% Ό to VD NJ Ό VD o VO 00 to v〇 00 〇\ 'O 私 為 'Ο Ο ο 私 00 〇\ Ό π 氧化1 鍅 wt% 主要成分 OO OO OO OO <1 00 〇〇 00 1 1 1 1 \ LTi 二 OO 00 OO 氧化 ί乙 wt% 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 OO 1 1 1 1 1 1 三氧1 化二 剑ΐ wt% 1 1 1 1 1 1 1 1 1 1 [ 1 1 1 I 1 1 1 1 1 1 氧化 鈣 wt% 1 1 1 1 1 1 1 1 1 1 1 1 1 Lh 1 I 1 1 1 1 1 氧化 錳 wt% 1 1 ] 1 ! 1 1 1 1 ,-J\ 1 1 i 1 1 1 i 1 I 氣化 鋁 wt% 1 1 1 1 1 1 1 1 1 1 1 1 ί 1 I 1 1 1 1 1 1 氧化 鈦 wt% 〇 k) o NJ o io 〇 N> o ΪΟ o k) <^Ί o io o io 1 〇 to o to o to Ο Κί 〇 to ο N> o io o *K> o to o k> o •to 氧化 矽 wt% 0.48( 0.48 0.48 0.48 0.48] 0.48 0.48 1~1 1—* 0.48 0.48| 0.48 0.48 0.48 0.48 0.48 j 0.48 1 0.48 0.48 0.48 鬆密 度 g^cm3 0.16 0.16 0.16 0.16 0.16 0.16 0.16 1 0.44 0.25 0.16] ! 0.16 0.16 j 0l6l 0.16] 0.16 0.16] 0.16 ; 0.16 0.16 0.16 0.16 0.16 熱傳 導率 kcal/ (mh°C) D00°ci小時 1300°CI 小時 1300°C1 小時 1300°C1 小時 1300°C1 小時 1300〇C1 小時 1 1300°C1 小時 1300°C1 小時 1300°C1 小時 B00°C1小時 ll300°Cl 小時 1300°C1 小時 1300〇C1 小時 1 丨1300。(:1小時| [1300。。1 小時 1 |1300。。1小時| 1300°C1 小時 丨1300。。1小兩 luotrci 小時 | 1300°C1 小時 1300°C1 小時 1300°C1 小時 加熱處理 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <〇^ <0.1 <0.1 <0.1 <0.1 <0.1 :<0」 <0.1 1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 NdFeB NdFeB NdFeB NdFeB NdFeB NdFeB NdFeB NdFeB NdFeB z P- "T3 Π» CO ;NdFeB | NdFeB | | NdFeB 1 NdFeB [NdFeB」 NdFeB I NdFeB ί 1 NdFeB NdFeB SmCo Mi-Ni NdFeB 鑄造 合金 0.71 0-71 0.71 0.71 0.71 0.71 | 0.59 0.66 0.67 j 0.62 I 0.63 I I 0.64 I 0.63 I 0.65 I 0.66 0.71 0.71 L〇.?i 0.71 0.71 0.71 0.71 溶湯之 流動係 數 本紙張尺度適用中國國家標準(CNS)A-l規格(2Ιϋ X 297公釐) --------------裝 i ί (請^"lsf面之江意事項再填寫本頁) 訂 -结 26 經濟部智慧时產局員工消費合泎社^;'" A7 __B7 五、發明說明(24 ) |實施例26| 1實施例25| 1實施例24| 1實施例23| 1實施例22| |實施例21| |實施例2〇j |實施例19| |實施例181 |實施例17 |實施例16 |實施例15 「實施例14 1實施例13 實施例12 I實施例11 實施例10 L^i 1^1 1 1 ! 1~1 1 Ln 1 ί 1 ^―* I 1雜素f 1 1 1 ο I 1 1 1 s 1 i 1 ah 8 g 8 1 s S Nvk S g S 1 8 S 8 1—* s 穩定 化氧 化錯 纖維 wt% i _1 Ο 1 8 >—1 〇 ί 1~1 1 8 1~> \ 1 j 穩定 化氧 化錯 鬚白 wt% ^Τ\ Ο iS ^―· 〇 <—1 Ό t—1 IS 00 to Ι-— Η-· ss ?s 1— 式雜㈣ 主要成分 <1 -Ο 0〇 〇〇 00 <x 00 <1 <1 00 00 00 <ϊ 00 ί 1 1 1 1 ί 1 1 1 1 i 1 1 1 i 1 1 1 ! 1 1 1 1 1 I 1 1 I 1 1 1 i 1 1 1 1 1 ! ! 1 1 I ! 1 1 ^ 1¾ CT ^ 1 Ui 1 1 1 L/i 1 ! 1 1 1 LTi 1 1 1 I 1 1 1 1 1 ! 1 1 1 ! 1 1 S Ui δ S g LTi S δ ΐ-Λ 〇 to 〇 Κ3 〇 k) s |冬斤梦 〇 O 尝 ο 4¾ oo 〇 00 〇 ο 态 〇 00 Ο 尝 〇 ο 00 Ο oo ο 垚 〇 〇 〇 h Ο oo 〇 t?、s Ο o 5; ο ο 5; 〇 ο Sn o Ο 5: 〇 ο 5; ο 〇\ ο 〇 1—* 〇> 〇 t—t· σ\ ο 5; o 5; o k 熱傳 導率 kcal/ (mh D〇 8 η° 1500°C1 小時 i5(xrci 小時 1500。(21 小時 1500°ci 小時 1500°ci 小時 1500°C1 小時 1500。(:1 小時 1500°ci 小時 1 800°C1小時 800°ci小時 sootn小時 800〇C1小時 800〇ci 小時 1 1 800°C1 小時 1 | 800°CH、時丨 | 800〇CH、時 加熱處理 Λ p Λ p Λ ρ Λ ρ Λ ρ »—1 Λ ρ Λ ρ Λ ρ Λ ρ 〇 ο Ο 〇 〇 灼熱 減 量率 wt% NdFeBj 1 1 1 1 NdFeB NdFeB: !NdFeB NdFeB NdFeB NdFeB NdFeB NdFeB If 〇 1 ί 1 1 ί s s Ο 〇 ίο Ο ίο 1 δ o NJ 溶湯 之流 動係 數 ί Hh 1 加工時耐火物破損 加工日fiS彳火物破損 加工時耐火物破損 加工時耐火物破損 加工日树火物破損 加工日秦耐火物破損 加工時耐火物破損 加工時对火物破損 #造途中溶液;疑固 中溶液;疑固 鎮造途中溶液凝固 _造途中溶液凝:固 #造途中溶液凝固 丨鋒造途中溶液凝固| | #造it中溶液凝固 i#造途中溶液凝固 斗 丨 i (請先閱-背面之土意事項再填寫本頁) -蟑 ^ ^ 'i vC\>;A-i ΐ·Κ.: X ^97 27 ο 9 6 6 4 4 A7B7 五、發明說明(25) 經濟部智慧財產局員工消費合作社印製 |實施例29| 1實施例28| 1實施例27| iS ι^ιι 雜 1 00 1 1 1 穩定 化氡 化錯 纖維 wt% ! 穩定 化氧 德 鬏白 wt% 1 1 1 s $擗左梦 主要成分 1 ί 1 1 1 1 ^ ^ ^ jst |u 1 1 1 1 1 1 式玄綷$衅 1 1 1 1 1 1 ^ p 1 1 1 |喀安抻 Ui L〇 Κ) κ> 鬆密 度 g/cm1 ON U) u> 熱傳 導率 kcal/ (mh °C) 新 m 加熱處理 Λ ρ Λ ρ Λ ρ 4 Η« 拉 S |NdFeB] NdFeB 1 j NdFeB 1 a> ^ 1 1 1 ^ S11; 缚造開始後,即凝固 轉造開始後,即凝固 鍀造開始後,即凝固1 備考 郝6戽冷婪八雜洚奸啦洚今知恭谇 -------------- I I <^先閱讀背面之注意事項再填寫本頁) 訂: 線· 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 28

Claims (1)

  1. d46 6 9 l告本· A8 B8 C8 D8 經濟部中央標準局員工消費合作社印製 申請專利範^~~ L 一種稀土類合金鑄造用对火物,其特徵為:實質上由70 重量%以上之氧化鋁及30重要%以下之氧化矽所構成, 鬆密度為lg/cm3以下,在1200至1400°C之溫度範圍之 熱傳導率為〇.5kcal/(mh°C)以下,1400°C與1小時之加 熱條件下之灼熱減量率為〇.5重量%以下。 2. 如申請專利範圍第1項之稀土類合金鑄造用耐火物,其 中含有氧化鋁纖維70重量%以上。 3. 如申請專利範圍第1項之稀土類合金鑄造用耐火物,其 中含有氧化鋁纖維與富鋁紅柱石共計70重量%以上。 4‘一種稀土類合金缚造用财火物,其特徵為實質上由7〇 重量。/。以上之氧化錘及30重量。/〇以下之氧化釔、三氧化 二鈽、氧化鈣、氧化猛、氧化鋁、氧化鈦之1種以上所 成’鬆密度為2g/cm3以下在1200至1400°C之溫度範圍 之熱傳導率為O.Skcal/imht:)以下,在1400X:及1小時 之加熱條件下之灼熱減量率為〇.5重量%以下。 5. 如申請專利範圍第4項之稀土類合金鑄造用耐火物,其 中氧化鍅纖維、氧化锫鬆白、穩定化氧化鍅纖維,穩 定化氧化鍅鬆白之任一種以上之含量為7〇重量%以上 〇 6. —種稀土類合金鑄造用耐火物之製造方法,其特徵為 將氧化鋁纖維,富鋁紅柱石纖維及氧化矽纖雉之中所 出之一種以上,以及無機黏合劑及有機黏合劑之一種 以上混合而成之混合物加以成形,並於乾燥固化後再 以lOOOt至丨40〇r進行熱處理,俾耐火物中之氧化鋁成 表紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ^、·ιτ^ (ifJfc閲#-圯面<,注1^項再填窝本頁) , 29 8 8 8 8 ABCD 經濟部中央標準局員工消穿合作社印製 力、申請專利範圍 為70重量0/〇以上而氧化石夕成為30重量%以下。 7_ -種稀土類合讀造料火物之製造方法,其特徵為 將氧化銘纖維’氧化錯鬆白,穩定化氧化錯氧化锆纖 維,穩定化氧化結鬆白之中選出一種以上以及與無 機黏合劑及有機黏合劑之一種以上之黏合劑混合而成 之混合物加以成形,並於乾燥固化後再以1〇〇〇t至〗4〇〇 C進行熱處理俾耐火物中之氧化锆成為7〇重量%以上 ,且氧化釔、三氧化鈽、氧化鈣、氧化錳,氧化鋁 氧化鈦或氧化矽之中之—種以上之合計為3〇重量%以 下。 8. —種稀土類合金之鑄造方法,係將稀土類合金之熔液 由漏斗’導管或喷嘴灌注於旋轉單輥之表面,旋轉雙 輥之表面或旋轉圓筒之内面,其特徵為: 上述漏斗’導管或噴嘴之耐火物實質上由7〇重量 %以上之氧化鋁及3 〇重量%以下之氧化矽所構成,鬆 密度為lg/cm3,在1200至l4〇〇°C之溫度範圍之熱傳導 率為0.5kcal/(mh°C)以下,在1400°C及1小時之加熱條 件之灼熱減量率為〇·5重量%以下。 9. 一種稀土類合金之鑄造方法,係將稀土類合金之熔液 由漏斗’導管或喷嘴灌注於旋轉單輥之表面,旋轉雙 輥之表面或旋轉圓筒之内面,其特徵為: 上述漏斗,導管或喷嘴之耐火物實質上由70重量 %以上之氧化鋁及3 〇重量%以下之氧化釔、三氧化二 鈽、氧化鈣、氧化錳、氧化鋁、氧化鈦或氧化矽之!種 本紙張尺庋適用中國國家樣準(CNS ) Λ4規格(2】0X297公釐;1 ----------梦-------:'sj------♦ (請先閱讀背面之注意事項再填"本頁} 30 ABCD 446690 六、申請專利範圍 以上所構成’鬆密度為2g/cm3,在〗2〇〇至i4〇〇ec之溫 度範圍之熱傳導率為〇 5〇kcai/(mh°c )以下,在1400〇C 及1小時之加熱條件之灼熱減董率為〇 5重量%以下之 耐火物。 10. 如申請專利範圍第8或9項之稀土類合金鑄造方法,其 中上述稀土類合金被鑄造成厚度為01至1111111之薄板、 薄片、薄帶或壓片。 11. 如申請專利範圍第8或9項之稀土類合金之鑄造方法, 其中上述稀土類合金係鑄造成厚度之圓筒材 料。 12·如申請專利ίΕ圍㈣項之稀土類合金_造方法,其中 上述漏斗,$管或喷嘴不必預熱可灌注稀土類合金之 溶液。 13·如申請專職圍第叫之稀土類合㈣造方法,其中 上述漏斗,導管或喷嘴不必預熱可灌注稀土類合金之 熔液。 ^------1T------^ (請先S9-讀f面‘之注ί項再填寫本瓦) · . 經濟部中央標準局負工消費合作社印裝 31
TW088110340A 1998-06-22 1999-06-21 Refractories for casting a rare-earth alloy, their production method, and method for casting an rare-earth alloy TW446690B (en)

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