TW493185B - High performance iron-rare earth-boron-refractory-cobalt nanocomposites - Google Patents

High performance iron-rare earth-boron-refractory-cobalt nanocomposites Download PDF

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TW493185B
TW493185B TW088111739A TW88111739A TW493185B TW 493185 B TW493185 B TW 493185B TW 088111739 A TW088111739 A TW 088111739A TW 88111739 A TW88111739 A TW 88111739A TW 493185 B TW493185 B TW 493185B
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Wen-Cheng Jang
Bao-Min Ma
Qun Chen
Charles O Bounds
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Santoku Inc
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Description

493185 A7 _ B7 五、發明説明（i ) 本發明镅域 本發明有關磁性材料，尤其有關包括鐵、稀土元素、 硼、耐火金屬及鈷之磁性超微複合物材料，具有有利之磁 性而適合製作黏結磁鐵〇 背景眘訊 含有鈸、鐵及硼之磁性合金由於其等之有利磁性，故 曾經廣泛硏究供用於燒結及黏合磁鐵〇 Nd2 Fe: 4 B相已經確 認爲一種表現特佳磁性之硬磁相。
Koon 之美國專利 4,402,770 號、4,409,043 號及 Re. 34, 322號（其等係以指述方式納入本文）揭示各種磁性合 金，包含在指定範圍內之鑭及其他稀土元素、過渡金屬如 鐵及鈷、以及硼〇雖然所揭示之合金已經發現具有良好之 磁性，但此等合金不具有最佳之性質，故未變成具有商業 活力。 本發明提供有利之磁性而適合於商業上生產黏合磁鐵 〇 本發明綜沭 本發明提供一種具有控制組成之超微複合物磁性材料 ，表現增進之磁性且易加工〇本發明之一目的爲提供一種 超微複合物磁性材料，包含在指定範圍內之鐵、稀土元素 (尤其鑭、鐯及钕）、硼、耐火金屬及鈷0 本發明組合物可爲（Ndi- y Lay ) v Fe: 〇 〇 - Y - w - X - z Cow Mz Bx 通式，式中M爲至少一由鈦、锆、給、釩、鈮、钽、鉻、 鉬及鎢中選出之耐火金屬；v約爲5至15; w大於或等於 本紙張尺度適用中國國家標準（CNS )八4规格（2丨0X297公釐） ----_--‘I裝-- (請先^讀背复) 、ατ 經濟部智M財產局’㈣工消費合作社印製 493185 A7 _____ B7 五、發明説明（2 ) 5 約爲9至30;y約爲〇· 〇5至0·5 ;而冗約爲0.1至 5 〇 Μ較佳爲鉻。 本發明尙有一目的爲提供一種超微複合物磁性材料， 包括一硬磁相、一軟磁相、及一較佳爲耐火金屬硼化物之 沉澱相〇硬磁相較佳爲Nd2Fe14B，而軟磁相較佳爲包含α - Fe 、Fe3B或其組合形式。該材料最佳爲包含aL(Fe,Co) 及 R2 (Fe,Co)14B 等相。 本發明提供一種製作超微複合物磁性材料之方法〇該 方法包括提供一包含鐵、稀土元素（較佳爲钕及鑭）、硼 、至少一耐火金屬（較佳爲鉻）及鈷之熔融組合物，迅速 將該組合物固化以形成實質無定形之材料，以及熱處理該 材料〇 簡要圖說 圖1 :於旋壓態（Vs = 25米/秒）中及最佳熱處理後 (Nd〇 . 9 5 La。. 〇 5 )9 . δ Fe7 8 Cr2 Β: 〇 . 5 條帶磁性能。圖 2 :以 Vs = 25 米 / 秒淬火之（Nd().95La〇.〇5)9.5Fe78Cr2Bi().5 條 帶熔融液X光繞射圖案。圖3 :於最佳熱處理後”^.95_ La〇 . 〇 5 )9 . 5 Fe7 8 - x Cox Cr2 Β!。. 5 (x = 〇-l〇)條帶磁性能。圖 4 : (Nd〇.95La〇.〇5)9.5Fe78-xC〇xCr2Bi〇.5 (X=0-10)條 帶於最佳處理後去磁化曲線0圖5 : TMA掃描經熱處理之 (Nd〇.95La〇.〇5)9.5Fe78-xC〇xCr2Bi〇.5 (x=0_10) ’ （a) x = 0、（b) χ = 2·5、（c) x = 5、（d) χ = 7·5而（e) x = 10，顯示 存在二磁相，亦即2 : 14 : 1及a -Fe ，且Tc在二者相位中增 加。圖 6 : (^〇.951^().。5)9.5?678-\(^(^281().5條帶於 本紙張尺度適用中國國家標準（CNS ) Λ4规格（210X 297公釐） —5 — (請先閱讀背而之注意事項再
I 經濟部智慈財產局貨工消费合作社印製 493185 A7 ---— _B7___ 、 五、發明説明（3 ) 最佳熱處理後X光繞射圖案，其中（a) x = 0、（b) χ = 2·5、 (c) x = 5、（d) χ = 7·5、而（e) χ = 1〇〇 圖 7 :具最佳磁性之 (Nd〇 . 9 5 La。. 〇 δ ) 9 δ Fe7 8 - x Cox Cr2 Β! 〇 . 5 條帶之 ΤΕΜ 顯微組 織，其中（a) x = 〇、（b) x = 5、而（c) x = 10o 圖 8 :各種合 金條帶（Nd〇.95La〇.{)5)9 5Fe78-xCc)xCr2Bi〇.5 (x = 〇- l〇) 之外加磁場之δ Μ變化ο : 較佳具體形式詳沭 超微複合物由於其等之潛在高殘留性（Br)及最大能量 積（BHmax)，已就黏合磁鐵予密集硏究。在NdFeB系統中 ，曾開發二類型之超微磁鐵，亦即a -Fe/Nd2 Fei 4 B [ 1 ]及 Fe3B/Nd2Fe14B [2,3] 〇此等超微複合物之Br可因個別相 位之化學組成及平均晶粒尺寸、α-Fe與Nd2Fe14B [1]或 Fe3 B與Nd2 Fei 4 B [2，3]之體積分量及分布而强烈受到影響 〇此外，及（BH)max可藉增加軟磁相（a-Fe)及/或硬 磁相（2 : 14 : 1相）之飽和磁化作用進一步增進。同樣，固 有矯頑性（i He )及垂直度强烈受到元素置換作用及顯微組 織[4 , 5 , 6 ]影響〇不管製作或元素置換/添加方法爲何， 習用NdFeB型三元超微複合物通常顯現小於9 KOe之iHc 〇 雖然 Nd8Fe87B5 &Nd8Fe87.5B4.5 之交換電偶式 a-Fe/ Nd2Fe14B型超微複合物曾經報導顯現極高之(12.5 kG) 及（BH)max (23·3 MGOe) [7]，但低 iHe (5·3 KOe)可能 仍將其等之應_用限制於某些領域內譬如微馬達〇 本發明之組合物可爲通式： (REl-yL^y)vFei〇〇-v-w-x-zC〇wMzBx 本纸張尺度適用中國國家標準（CNS ) Λ4規格（210X 297公釐）~^ —6- (請先閱讀背而之注意事項再本页 丁 、\'ύ 經濟部智慧財產局Μ工消費合作社印製 493185 A7 B7 五、發明説明（4) 式中RE爲至少一非鑭之稀土元素；Μ爲至少一由鈦、锆、 給、釩、鈮、鉅、鉻、鉬及鎢中選出之耐火金屬；ν約爲 5至15;w大於或等於5 ;χ約爲9至30;y約爲〇·〇5至 0.5 ;而2約爲0·1至5 〇 合宜之稀土元素包括鑭、鋪、鐯、鈒、鉅、釤、銪、 金L、紘、鏑、纟火、銷、錢、鏡及鐘。本發明之總稀土含量 在本文中稱爲nTRE” 〇本文所用”RE”一詞意指鑭以外之所 有合宜稀土元素。較佳之RE元素爲钕、鐯、鏑、絨及其等 之混合物，而最佳爲鈸、鐯及其等之混合物〇合宜之耐火 金屬包括週期表中IVb 、Vb及VIb族之元素，例如鈦、銷 、給、釩、鈮、鉅、鉻、鉬及鎢〇本發明組合物之耐火金 屬含量在本文中稱爲π Μ ” ◦ Μ較佳爲至少一由鈦、釩、鈮 、鉻及鉬中選出之耐火金屬更佳爲至少一由鈦、鈮及 鉻中選出之耐火金屬〇 Μ最佳爲鉻或鈦或其組合〇將鈷添 加於本發明超微複合物材料之利益一般始於約1 %至40% ，雖然本發明特佳組合物包含約等於或大於5 %鈷〇下表 列出TRE 、硼、耐火金屬及銘之典型、較佳及更佳範圍〇 ---------r^丨β--- (請先間讀背而之注*事項孙^^^4頁) 訂 經濟部智总財走局Μ工消赀合作社印製 概約範圍 TRE 硼 耐火金屬 鈷 鐵 典型 5-15 9-30 0 • 1 -5 5-40 餘量 較佳 9-12 9-12 0 .5-4 5-20 餘量 更佳 9.5-11.5 10-12 0 .5-3 6-15 餘量 最佳 9.5-11.5 10.5-11.5 1 -2 . 5 7-12 餘量 本發明之磁性材料較隹爲以- 一迅速固化及熱處理程序 本纸張尺度適用中國國家標準（CNS ) Λ4規格（2丨0〕<297公楚) -7- 493185 A7 _ B7 五、發明説明（5 ) 產生〇迅速固化之獲致係藉譬如熔融液旋壓、噴澆、熔融 液榨出、霧化及噴塗細片冷卻等技術將組合物自熔化狀態 迅速冷卻。通常採用約每秒鐘104至107 °c之冷卻速率， 較佳爲約1〇5至1〇6 °c〇經迅速固化之材料較佳爲實質上 無定形0在迅速固化之後，可將材料硏磨、硏磨並熱處理 、或者直接熱處理。 ： 經濟部智£財產局員工消赀合作社印製 本發明之組合物經發現具有增進之可加工性，而容許 使用較慢之迅速固化速率〇舉例言之，在熔融液旋壓程序 期間，可使用較緩慢之轉輪速度及/或可處理較大體積之 材料。使用較緩慢熔融液轉輪速度之能力爲屬重要，因與 轉輪接觸之熔化合金直澆口窩在輪速度減小時實質爲更穩 定0此外，處理較大材料體積之能力容許生產成本降低〇 在該組合物迅速固化成實質上爲無定形狀態之後，其 較佳爲予熱處理以誘生自發性結晶作用。本文中所用A自 發性結晶作用〃一詞意指細微晶體晶粒之迅速及實質同質 形成作用〇自發性結晶作用較佳爲藉由加熱該材料至一指 定溫度達一經控制之時段而獲致，此造成晶體晶粒成核作 用，致無實質之後績晶粒生長0合宜溫度約爲4〇〇至800 °C，較佳爲約600至750 °c，更佳爲約645至700 °c，最 佳爲6 4 5至6 5 5 °C 〇加熱時間較佳爲約〇 · 〇 〇 1秒鐘至2小 時，更佳爲約0.01秒鐘至15分鐘。該材料可於任何合宜之 裝置譬如爐內加熱◦可採用連續及/或批式加熱方法0該 材料較佳爲加熱至其結晶溫度，並在出現實質晶粒生長之 前將熱源移去。 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X 297公釐） —8 ~ 493185 經濟部智惡財產局員工消費合作社印製 A7 B7 五、發明説明（6) 本發明粉末形式之超微複合物磁性材料適用於形成具 有良好磁性之黏合磁鐵。任何習用以製備黏合磁鐵之方法 均可利用〇粉末超微複合物式磁性材料較佳爲與黏合劑混 合，並予固化。黏合劑較佳約佔黏合磁鐵重量之〇 . 5至4 % 〇 經發現，超微複合物之添加提供各種於約加鴒至180 °0且保持約15分鐘時不可逆感應損失（之量）約小於-4% ，較佳爲約小於-3.5% 〇 實驗 以下實例例示本發明之各種不同情況’且無意限制其 範疇〇 表 I : (Nd〇.95La〇.〇5)9.5Fe78Cr2Bi〇.5 條帶在旋壓態及 在650、675及700 °c — 10分鐘熱處理後之1、iHc 及（BH)… 條帶狀況 Br(kG) i He ( kOe ) BHm a x (MGOe) 旋壓態（25米/秒）7·6 9·9 8·5 650 °C 分鐘 8·4 10.3 14.0 675 °C -1〇 分鐘 8·2 9·8 12·5 700°C-l〇 分鐘 8.2 9 · 5 12.8 表 II : (Nd0.95La0.05)9.5Fe78-xCoxCi:2B10.5 (χ = 0-1〇) 條帶在最佳處理後L、iHe及（BH)max之比較 鈷含量 x= Br ( kG) i He ( kOe ) BHmax(k0e) 0 8 . 4 l〇·3 14·0 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210 X 297公釐） (請先間讀背而之注意事項洱本頁)
一 9 一 493185 A7 B7 五、發明説明（ .4 8 . 10 10 10 10 10.4 14 14 15 19 經濟部智慧財產局Μ工消Φ合作社印製 表 DI : ( N d 〇 . 9 5 L a 〇 . 〇 5 ) 9 · 5 F e 7 8 - X c 0 - c r 2 B 工 〇 . 5 ( k = 0 - 1 0 ) 條帶在最佳處理後之i L 、不可逆感應損失及可逆 感應溫度係數（習知爲α)之比較 1 鈷含量 X = 0 2.5 5.0 7.5 10 對照組（商用） 藉眞空感應熔化製備具有（Ndo.HLao.osh.sFeH-x-CoxCi^Bio.s (χ=0-10) 組成之合金鑄錠 。將約 3 克 之鑄錠 塊壓碎成小塊，以適應熔融液旋壓用坩堝之尺寸0將一孔 徑約0.7-0.8毫米之石英噴嘴用於熔融液旋壓。用約15至 25米/秒之輪速（Vs )產生條帶。利用具有Cii-K α射線之X-光粉末繞射測定條帶之晶性。以熱重力分析儀（TGA )併同 5 0e之外加磁場（習知爲熱磁分析（TMA))測定各磁相及 i Hc 不可逆感應 α (kOe ) 損失（％ ) % ( °C 10.3 -3 . 5 -0.184 10.2 -2.7 -0.144 10.2 -3 . 0 -0.131 10.3 -3.2 -0.118 9.5 -3.4 -0.105 9.2 -4.5 -0.105 本紙張尺度適用中國國家標準（CNS ) Λ4規格（2丨〇 X 公釐） -10- (請先閱讀背而之注意事項再 493185 A7 B7 五、發明説明（8) 相應居里點（Tc)〇以約650至700艺熱處理部份爲無定形 之選定條帶分鐘，以引致結晶並增進磁性。用約50 KOe 之脈衝場將淬火態且經熱處理之條帶磁化，並以外加磁場 爲12 KOe之振動試樣磁力計（VSM)測量各帶之磁性。開放 電路特性亦即不可逆感應損失之測定方法爲將一尺寸約爲 4毫米χ_2·5毫米X 50毫米之全磁化帶置於零外:加磁場下 之VSM內，以約2至18(k/C爲週期〇Wohlfarth之殘留分 析[8 , 9 ]予採用以測定部份鈷置換鐵對所得材料之交換電 偶式交作强度之衝擊〇 圖1中顯亦（以(1。.951^().()5)9.51^78(^281().5條帶在 熔融液旋壓態（Vs = 25米/秒）以及分別在約以650、675 與700 °C對熱處理約10分鐘後之Br、iHe及（BH)max 〇爲 便利計，將此等試樣之Br、iHe及（BH)max列於表I供參 考。旋壓態條帶之Br、iHe及（BH)max在無任何熱處理時 較低：分別爲7.6 kG、9.9 kOe及8.5 MGOe，故可歸因於 條帶之不完全結晶作用，如由圖2中無定形前質合金寬尖 峰之疊合及2:14:1及α-Fe尖峰所證明。在適當退火後， Br及（BH)max二者顯著增進〇在6 50 °〇厂分鐘熱處理後獲 得 8·4 kG之 Br、10.3 kOe 之 iHe 及14 MG^e 之（BH) m a x 〇 當以較高溫度亦即約67 5或約7 00 °C處理時，可觀察到Br 及（BH) m a x急劇減小，指示可能已出現細微之晶粒生長或 相轉變。不同於Br及（BH) „ a x ，i He在任何熱處理後均較 恆定保持於9.5至9.9 kOe 〇所有數値均暗示，約650 °C 達約1〇分鐘之處理對本發明材料可爲較佳之熱處理0 本紙張尺度適用中國國家標準（CNS ) Λ4規格（21 OX 297公釐） -11- (請先間讀背而之注意事項再1^本页) .批衣-- I HI- HI i 經濟部智慈財產局段工消費合作社印製 493185 經濟部智葸財產局段工消费合作社印製 A7 ____B7五、發明説明（9 ) 圖3中所顯爲熱處理時，Br、iHe及（BH)raax隨鈷在 (Nd。. 95La〇 . )9 · sFe78 · 5_xCoxCr2Bi〇 . 5 合金系列中含量 之變化。初期，及（BH)max在低鈷濃度亦即χ = 2·5及5 時幾乎保持恆定，然後在X增加大於7·5時增大。在X爲 7.5及10之各試樣上獲得多於9·1 kG及15.8 MGOe之1及 (BH)m a x 〇此等高Br値暗示磁硬相及軟相間存在實質之交 換電偶交作。以鈷置換鐵明顯不實質衝撃i 〇在各實驗 組成內iHe範圍爲9·5至10.3 kOeo在x = 10之條帶上獲得 10·4 kG 之Br、9.5 kOe 之iHe 及19.8 MGOe 之（BH)max 〇該高i He與鈷置換鐵可能弱化硬磁相之各向異性常數並 績導致超微複合物上所得i He減小〇高鈷含量合金之顯微 結構改變可能在解釋所保存高i He値時扮演關鍵之角色〇 理論上，在有鉻存在時添加鈷可能改變前質合金用於熔融 液旋壓之液體特性，並修正超微複合物之顯微結構〇爲便 利計，將此合金系列之Br、iHe列於表II供比 較。圖 4 顯不（Nd〇.95La〇.〇5)9.5Fe78-xC〇xCr2Bi〇.5 (X= 0-10)條帶之第二象限去磁作用曲線。該去磁作用曲線之 iHe及垂直度似乎對鈷置換量不敏感。可推論（BH)max隨 鈷含量之變化依照Br之相同趨勢〇 爲了解導致Br及（BHhu隨鈷置換量改變之機制，檢 驗磁相轉變作爲溫度範圍約25至°c之鈷含量之結果。 圖 5(a)、（b)、（c)、（d)及（e)中所示爲 χ = 0、2·5、5.0 、7·5 及 10 之（^1(1().951^〇.()5)9.5?678-»(^(^(]12 131().5最佳 處理條帶之個別ΤΜΑ掃描〇在對照組試樣4 = 0)中僅發現 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210Χ297公釐) 一 12- (請先閲讀背而之注念事項再1^本页) i· 裝· I I--Ψ !丨I 、···τ 線ί 493185 A7 B7___ 五、發明説明（1〇) 二磁相，亦即R2Fe14B及α-Fe 〇經發現，在鈷含量由x = 0增加至10時，2 : 14 ·· 1相之Tc經約289 °C增高至3 93 °C 〇 此暗示可假設鈷進入Nd2 ( Fe，Co ) : 4 B相之晶體結構內。亦 發現，當X由〇增加至10時，α-Fe之Tc由約712 °C增加 至860 *〇 〇又，此Tc改變亦意味鈷亦可能形成a - (Fe , Co ) 固溶體〇 1 經最佳處理條帶之平均晶粒尺寸亦藉X-光繞射（XRD) 及傳輸電子顯微術（TEM)加以比較。圖6( a)、（b)、（ c )、 (d)及（e)中所示爲實驗條帶之XRD圖案〇所有受硏究試 樣之類似尖峰寬度指示對a - ( F e，C 〇 )及2 : 1 4 : 1相而言，此 等試樣之平均晶粒尺寸大約相同。圖7(a)、（b)及（c)中 所示爲 x = 〇、5之（Nd〇.95LaQ.〇5)9.5Fe78-xGoxCr2BiG.52 TEM分析。在5 %含鈷合金中多少出現更多之晶粒生長（ 參閱圖7(a)及（b) )〇平均晶粒尺寸之差異在X由5增加 至10時變成較不顯著，如圖7(b)及（c )中所示。然而，晶 粒周邊似乎變成較不明確，甚至在X增加至時被一沾汚 之第二相（未顯示）包圍。顯微結構之此一改變可解釋爲 何iHc對鈷含量不敏感〇 圖8中所示爲δ M (=md (H)-( l-2mr (H))之作圖，其中 md爲減小之去磁化作用而mr爲減小之殘留性[8，9 ]，均相 對於（Nd〇 .95La〇 .〇5 )9 .5Fe78-xCoxCr2Bi〇 ·δ (χ = 0、2·5、 5、7. 5及10)條帶之五個受硏究組成之外加磁場而言。此 等作圖中之正5Μ尖峰高度指示在磁硬相與軟相間存在交 換電偶交作。將x = 7. 5及10 (晶粒粗化現象及顯微結構改 本紙張尺度適用中國國家標準（CNS ) Λ4規格（2丨0:< 297公釐） n _ : —In an— mu I -- - -- I 1-: s 士· 儿？先間讀背而之注念事項再^^本頁) 、；o 經濟部智总財產.¾¾工消費合作社印t -13- 493185 經濟部智慧財產局’貨工消赀合作社印製 A7 B7 五、發明説明（η) 變）中所發現之高Br相結合，可得結論爲此等試樣之Br及 (BH)max之增加可能因鈷置換而由a-(Fe,C〇)及2:14:1二 者相位之飽和去磁化作用之增加引起。此外，此亦可能暗 示需要使細微平均晶粒所强化之交換電偶交作與晶粒粗化 及顯微結構改變間折衷，以於高鈷濃度材料（5<x<10) 上獲致最高心及（BH)max 〇如上述，鈷之置換鐵便2··14··1 相之Tc增加，而此對高操作溫度應用亦可能具有吸引力〇 表HI中所示爲i He 、不可逆感應損失及可逆感應溫度 係數α、隨所硏究材料之鈷濃度之變化。對於x = 〇 ，不可 逆損失及α分別爲-3.5%及- 0.184% / °C 〇鈷之置換鐵在 X由0變化至10時將α由-〇·184%/1減小至-0.105%/ °C 〇 α量之減小可直接與TC之增加相關，如於燒結Nd(Fe, Co) B磁鐵[10]中所觀察到者。然而，在各組成中，該不可 逆損失似由-2.7%變化至3.5 %，而與鈷含量不相關〇對 於x = 10,所得不可逆損失爲-3.4%而《爲-0.105%/°C 9 此等數値匹擬供黏合磁鐵應用之市售NdFeB粉末（不可逆 損失爲- 4·5% 而 α 爲-〇.l〇5%/°C) 〇 在本發明最佳處理磁性材料中僅存在二磁相，亦即α - Fe 及 R2Fei4B ，包括較佳之（Nd〇.95La〇.()5)9.5Fe78-x -CoxCr2B1Q.5 (x = 0-10)條帶。鈷之置換鐵（即例如χ = 2·5 至1〇之較佳範圍）使a - (Fe,Co)及112卩％(；〇)146二者相位 之居里點（Tc)〇各試樣中之Br及（BH)max亦隨高鈷含量增 加〇在磁硬相及軟相間可觀察到交換電偶作用。以TEM分 析在稀薄鈷置換（x = 2.5及5 )之最佳加工條帶中發現晶 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X 297公釐） T! (請先閱讀背而之注意事項再本ϊ-rc )
-14- 493185 A7 B7 五、發明説明（12) 粒粗化現象0晶粒粗化在x增加至6或更高時變成較不明 顯〇舉例言之，在X = l〇時觀察到一包圍主要相之沾汚之晶 粒周邊相位（未顯示）。在譬如具有（Nd〇 . 9 5 La。. 〇 δ )9 . δ-^680〇1()02：61().5通式之較佳組成上獲得10·4 kG之ΒΓ、 9.5 kOe 之 iHe 及 19.8 MGOe 之（BH)max 〇 此外，完全處 理材料之可逆感應溫度係數大小經發現隨鈷含量增加而減 小〇 總之，熔融液旋壓超微複合物如"^.^!^。.^)^^-Fe7 8 - x Cox Cr2 Β! Q . δ (χ = 0-10)之相轉變及磁性證實二磁相 亦即 a-(Fe,Co)及 R2(Fe，Co)14B〇 鈷之置換鐵（如 χ = 2.5 至10)以每％之鈷置換量約爲20°C之速率使a-(Fe,Co)及 R2(Fe，Co)14B二者相位之居里點（Tc)增加〇在含有低鈷含 量（例如x = 5 )之最佳加工條帶上觀察到小量之晶粒粗化 現象〇鈷含量之進一步增加對所得平均晶粒尺寸無效應〇 反之，有一不明之晶粒周邊相位圍繞例如x = 10之條帶上之 主要相位〇此顯微結構改變之一理由可能爲鈷含量增加時 iHc保持大於9.5 kOe 〇於所有試樣中均發現在磁硬相與 軟相間有交換電偶作用。殘留性1及最大能量積（BH)max 在χ = 7·5及10時急劇增進，此可能因α - (Fe,Co)及R2(Fe, C〇 ) : 4 B飽和磁化作用以及其間交換電偶作用之增加而引起 〇 在（Nd〇.95La〇.()5)9.5Fe68C〇i〇Cr2Bi〇.5 h 獲致 1 〇 . 4 k G 之Br、9.5 kOe 之iHe 及19·8 MGOe 之（BH)max 〇 此外， 最佳加工材料之可逆感應溫度係數經發現隨鈷濃度增加而 減小〇 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 一 15- 請先間讀背而之注意事項再
經濟部智慧財產局g(工消費合作社印製 • mu n 1 -» mu βι^ϋ· 493185 A7 B7^__ 五、發明説明（13) 參考文獻 [1] A. Manaf, R. A. Buckley, H. A. Davies and M. Leonowicz, J. Magn. Magn. Mater” 101，360 (1991)· [2] R. Coehoom, D. B. de Mooji, J. P. W. B. Duchateau, and K. H. J. Buschow, J. Phys· 49, C8, 669 (1988).
[3] E. F. Kneller and R. Hawig, IEEE Trans. Magn., 27,3588 (1991). i [4] A. Manaf, P. Z. Zhang, I. Ahmed, H. A. Davies and R. A. Buckley, IEEE Trans. Mag., 29 (1993) 2866.
[5] A. Manaf, M. Al-Khafaji, P. Z. Zhang, H. A. Davies, R. A. Buckley and W. Rainforth, J. Magn. Magn. Mater. 128 (1993) 307.
[6] W· C· Chang, D· M. Hsing，B. M. Ma and C. 0· Bounds，IEEE Trans, Magn· 32 (1996)，4425· [7] J. Bauer, M. Seeger, A. Zem, and H. Kronmuller, J. Appl. Phys. 80 (1996) 1667.
[8] F. Vajda and E. D. Torre, J. Appl. Phys. 75 (1994) 5689.
[9] P. E. Kelly, K. O' Grady, P. I. Mayo and R. W. Cantrell, IEEE Trans. Magn., MAG-25 (1989) 388.
[10] B.M. Ma, W. L. Liu, Y.L. Liang, D.W. Scoot, and C.O. Bounds, J. Appl, Phys., 75 (1994) 6628. (請先間讀背而之注念市項#
I 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Λ4規格（2丨OX 297公釐) -16-

Claims (1)

  1. 493185 Λ8 R8 C8 D8
    六、申請專利範圍 1 · 一種超微複合物磁性材料，具有通式： (REj.yLcly )vFGi〇〇-v-W-X-iC〇wMxBx 式中RE爲至少一由鈽、鍇、钕、鉅、釤、銪、釓、鉞、鏑 、鈥、餌、铥、鏡及錙所組成集團中選出之稀土元素；Μ 爲至少一由鈦、锆、給、釩、鈮、鉅、鉻、鉬及鎢所組成 集圃中選出之耐火金屬；ν約爲5至15; w大於或等於5 ;x約爲9至30;y約爲0·05至0·5 ;而2約爲0·1至5 〇 2 ·如申請專利範園第1項之超微複合^^料，其中w 大於或等於6 〇 3 ·如申請專利範圍第1項之超微複合，其中RE 爲至少一由鈒、錯、鏑及铽所組成集圆中選出之元素。 4 ·如申請專利範圍第1項之超微複合料，其中RE 爲至少一由鈒及鐯所組成集團中選出之元素。 5 ·如申請專利範圍第3項之超微複合料，其中Μ 爲至少一由汰、釩、鈮、鉻及鉬所組成集團中選出之耐火 金屬；ν約爲9至12;w約爲6至20;χ約爲9至12; y 約爲〇 · 〇 5至〇 · 1 ;而z約爲〇 . 5至4 〇 6 ·如申請靱利範園笫3项之超微複合^?料，其中Μ 爲至少一由汰、鈮或鉻所組成集團中選出之耐火金屬；ν 約爲9.5至11.5; w約爲6至15; X約爲10至12; y約爲 0·05 至 0.07;而 z 約爲 〇·5 至 3 〇 ‘ 1 性 / 7 ·如申請專利範圍第3項之超微複合料，其中Μ 爲鉻；ν約爲9.5至11·5; w約爲7至12; X約爲10·5至 本紙张尺度適川1丨，四四家楳準（CNS)A‘l规格（m〇 公:¾ ) -17- 請 先 間 背 經濟部t/ii財產Λ7诗工消货合作社印奴 之 注 t 事 項
    1/ 493185 A8 B8 C8 D8 六、申請專利範圍 11 ;y約爲0.05至0.07;而Z約爲1至2.5 Ο 8 ·如申請專利範圍第3項之超微複合料，其中 Μ 爲钛； 11 約爲9 · 5至11 · 5 ; w約爲7至12 ; X約爲1〇 · 5至 ’ ；y約爲0 · 05至0 . 07 ;而ζ約爲1至2 . 5 〇身1生， 9 ·如申請專利範圍第3項之超微複合料，其中χ 約大於或等於9.5 〇 t磁^生， 10·如申請專利範圍第3項之超微複合痴^料 約大於或等於10〇 I衡V生 11 ·如申請專利範圍第3項之超微複合 約大於或等於10.5ο L磁性/ 1 2 ·如申請專利範圍第：i項之超微複合^料 的爲10.5至30 〇 13·—種黏合磁鐵，包含： 一超微複合物磁性材料，具有通式： (Klijl_yL/3.y )vFG100-V-W-X-zC〇wM2Bx 式中re爲至少一由鈾、鍇、鈸、鉅、釤、銪、釓 其中X 其中X 其中X 铽、鏑 -----κ-------¾ (請先閱讀背面之注意事項再填寫本頁) • ϋ n 訂--------線I 經濟部智慈財產局員工消f合作社印被 、鈥、餌、铥、鏡及餾所組成集團中選出之稀土元素；Μ 爲至少一由鈦、錯、給、釩、鈮、鉅、鉻、鉬及鎢所組成 集團中選出之耐火金屬；ν約爲5至15; w大於或等於5 ;X約爲9至30; y約爲0·05至0.5 ;而2約爲0.1至5 ;以及 一黏合劑。 1 4 ·如申請專利範圍第1 3項之黏合磁鐵，其中該黏合劑 約佔該黏合磁鐵之0.5至4重量％ 〇 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -18- 493185 Λ8 B8 C8 _ D8 六、申請專利範圍 15·—種製作黏合磁鐵之方法，包含： 提供一粉狀超微複合物磁性材料，具有通式： (Rtjl - yL3.y )yFGi Ο Ο _χ - % C〇wMz Βχ 式中RE爲至少一由鈽、鐯、钕、鉅、釤、銪、釓、鉞、鏑 、狄、餌、铥、鏡及餾所組成集團中選出之稀土元素；Μ 爲至少一由鈦、锆、給、釩、鈮、鉅、鉻、鉬及_所組成 集團中選出之耐火金屬；ν約爲5至15; w大於或等於5 ;x約爲9至30;y約爲0.05至0.5 ;而？約爲0.1至5 f 將該粉狀超微複合物磁性材料與一黏合劑混合；以 及 使該黏合劑固化以形成黏合磁鐵〇 1 6 .如申請專利範圍第1項之超微複合$^料，其中不 可逆感應損失之量在加熱至1 8 〇 °C約達1 5分鐘時小於-4 % 〇 (請先閱讀背面之注意事項本頁) 經濟部智慧財產局員工消货合作社印製 本紙張尺度適用中0國家標準（CNS)A‘l规格（210 X 297公兗） -19-
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