TW202235640A - 主輔合金系釹鐵硼磁體材料及其製備方法 - Google Patents

主輔合金系釹鐵硼磁體材料及其製備方法 Download PDF

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TW202235640A
TW202235640A TW111107190A TW111107190A TW202235640A TW 202235640 A TW202235640 A TW 202235640A TW 111107190 A TW111107190 A TW 111107190A TW 111107190 A TW111107190 A TW 111107190A TW 202235640 A TW202235640 A TW 202235640A
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韋興
黃佳瑩
湯志輝
黃清芳
蔣志鵬
許德欽
陳大崑
付剛
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大陸商福建省長汀金龍稀土有限公司
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Abstract

本發明公開了一種主輔合金系釹鐵硼磁體材料及其製備方法。本發明的主輔合金系釹鐵硼磁體材料的原料組合物包括主合金原料和輔合金原料,所述輔合金原料在所述主輔合金系釹鐵硼磁體材料的原料組合物中的質量百分比為1.0~15.0mas%。採用該原料組合物製得的主輔合金系釹鐵硼磁體材料在保證高剩磁的同時提高了矯頑力,且其製備方法可以工程化應用。

Description

主輔合金系釹鐵硼磁體材料及其製備方法
本發明係有關一種主輔合金系釹鐵硼磁體材料及其製備方法。
釹鐵硼作為當前常溫磁能積最大的永磁體而備受關注,廣泛應用於曳引電機、伺服電機、新能源汽車主驅電機、磁性元件、風力發電機等領域。但商用磁體的抗退磁能力僅為理論值(約71KOe)的1/4。釹鐵硼的抗退磁能力一般用矯頑力來表徵,矯頑力的大小受釹鐵硼的微觀結構影響大,同時受形核場和釘紮場兩種機制控制,以形核場為主導,形核場提高Hcj的途徑為消除反向疇形核點。從微觀角度,一般有三種提高矯頑力的路徑:
1)提高主相之間的晶界相的去磁耦合能力,具體的做法有通過主相含Nd 6Fe 13X吸收晶界中的Fe,使晶界相向無磁相或反鐵磁相轉變,同時擴寬晶界;或者提高總稀土量,以提高晶界相體積;通過Cu、Ga、Co、Al等晶界元素的添加,改善富釹相的流動性,優化主相顆粒邊界,從而修復主相缺陷,減少反向疇的形成,使Hcj的提高。此類方法提升的Hcj有限,Hcj難以提高至25kOe以上。
2)通過細化晶粒減少主相顆粒的反向疇形核點,越接近單疇尺寸,反向疇越難形成;或通過Nd 6Fe 13X等晶界相的形成消融主相顆粒的銳角,使主相晶界變平滑,減少反向形核點。此類方法對Hcj的提升效果較強,薄膜法製備磁體的Hcj可達29kOe,但難以工程化應用。
3)通過重稀土添加,使主相各向異性場提高,而重稀土資源儲量少、價格高,嚴重制約了釹鐵硼磁體在各行業的應用。通常采雙合金或擴散的方式使重稀土在主相外沿層分佈,提高重稀土的利用率。但是擴散的方式無法應用在厚度較大(>15mm)的磁體,而現有的雙合金法提升的效果有限(大約可將Hcj提高1~1.5kOe)。
本發明為了解決現有技術中雙合金法製備的釹鐵硼磁體矯頑力較低的缺陷,從而提供一種主輔合金系釹鐵硼磁體材料及其製備方法。本發明的主輔合金系釹鐵硼磁體材料在保證高剩磁的同時提高了矯頑力,且其製備方法可以工程化應用。
為了實現上述目的,本發明採用以下技術方案:
本發明提供了一種主輔合金系釹鐵硼磁體材料的原料組合物,其包括主合金原料和輔合金原料;其中,所述主合金原料包括以下組分:輕稀土元素LR,10.0~33.0mas%;LR選自Y、La、Ce、Pr、Nd的一種或多種;重稀土元素HR,0~20.0mas%;HR選自Gd、Dy、Tb和Ho中的一種或多種;M,0.1~5.0mas%;M選自Co、Cu、Al和Ga中的一種或多種;X,0.05~0.7mas%;X選自Zr、Ti和Nb中的一種或多種;B,0.94~1.1mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比;
所述輔合金原料包括以下組分:輕稀土元素LR,0~30.0mas%;LR為Nd和/或Pr;重稀土元素HR,1~80mas%;HR為Dy和/或Tb;M,5.0~20.0mas%;M選自Co、Cu、Al和Ga中的一種或多種;X,3.0~12.0mas%;X選自Ti、Zr、Hf、Nb、W和Ta中的一種或多種;B,0~0.6mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比;
所述輔合金原料在所述主輔合金系釹鐵硼磁體材料的原料組合物中的質量百分比為1.0~15.0mas%。
本發明中,較佳地,所述主合金原料中總稀土含量TRE為26.0~40.0mas%,更佳地為29.0~32.0mas%,例如29.5mas%、30.5mas%或31.5mas%,mas%是指組分在所述主合金原料中的質量百分比。
本發明中,所述主合金原料中,所述LR的含量較佳地為25.0~30.0mas%,例如25.2mas%、29.5mas%或30mas%,mas%是指組分在所述主合金原料中的質量百分比。
本發明中,所述主合金原料中,當所述LR包含Nd時,所述Nd的含量較佳地為18.9~22.5mas%,例如22.125mas%,mas%是指組分在所述主合金原料中的質量百分比。
本發明中,所述主合金原料中,當所述LR包含Pr時,所述Pr的含量較佳地為6.0~7.5mas%,例如6.3mas%或7.375mas%,mas%是指組分在所述主合金原料中的質量百分比。
較佳地,所述主合金原料中,所述LR包含Nd和Pr。更佳地,所述Nd的含量為22.125mas%,所述Pr的含量為7.375mas%;或者,所述Nd的含量為22.5mas%,所述Pr的含量為7.5mas%;或者,所述Nd的含量為18.9mas%,所述Pr的含量為6.3mas%;mas%是指組分在所述主合金原料中的質量百分比。
本發明中,所述主合金原料中,所述HR的含量較佳地為1.0~10.0mas%,例如1.5mas%或5.3mas%,mas%是指組分在所述主合金原料中的質量百分比。
本發明中,所述主合金原料中,當所述HR包含Dy時,所述Dy的含量較佳地為1.0~5.0mas%,例如1.5mas%或4.3mas%。較佳地,所述主合金原料中,所述HR為Dy;所述Dy的含量較佳地為1.5mas%。其中,mas%是指組分在所述主合金原料中的質量百分比。
本發明中,所述主合金原料中,當所述HR包含Ho時,所述Ho的含量較佳地為0.5~2.0mas%,例如1.0mas%,mas%是指組分在所述主合金原料中的質量百分比。
較佳地,所述主合金原料中,所述HR包含Dy和Ho;其中,所述Dy的含量較佳地為4.3mas%,所述Ho的含量較佳地為1.0mas%,mas%是指組分在所述主合金原料中的質量百分比。
本發明中,所述主合金原料中,所述M的含量較佳地為0.5~2.0mas%,例如0.88mas%、1.5mas%或1.65mas%,mas%是指組分在所述主合金原料中的質量百分比。
本發明中,所述主合金原料中,當所述M包含Ga時,所述Ga的含量較佳地為0.2~0.4mas%,例如0.25mas%,mas%是指組分在所述主合金原料中的質量百分比。
本發明中,所述主合金原料中,當所述M包含Al時,所述Al的含量較佳地為0.01~0.1mas%,例如0.03mas%,mas%是指組分在所述主合金原料中的質量百分比。
本發明中,所述主合金原料中,當所述M包含Cu時,所述Cu的含量較佳地為0.1~0.25mas%,例如0.15mas%,mas%是指組分在所述主合金原料中的質量百分比。
本發明中,所述主合金原料中,當所述M包含Co時,所述Co的含量較佳地為0.5~1.0mas%,mas%是指組分在所述主合金原料中的質量百分比。
較佳地,所述主合金原料中,所述M包含Ga、Al、Cu和Co;其中,所述Ga的含量較佳地為0.25mas%,所述Al的含量較佳地為0.03mas%,所述Cu的含量較佳地為0.1mas%,所述Co的含量較佳地為0.5mas%。其中,mas%是指組分在所述主合金原料中的質量百分比。
本發明中,所述主合金原料中,所述X的含量較佳地為0.1~0.35mas%,例如0.11mas%或0.15mas%,mas%是指組分在所述主合金原料中的質量百分比。較佳地,所述主合金原料中,所述X為Zr或Ti。
本發明中,所述主合金原料中,所述B的含量較佳地為0.97~0.99mas%,例如0.98mas%,mas%是指組分在所述主合金原料中的質量百分比。
在一較佳的實施方案中,所述主合金原料包括以下組分:Nd,22.125mas%;Pr,7.375mas%;Ga,0.25mas%;Al,0.03mas%;Cu,0.1mas%;Co,0.5mas%;Zr,0.11mas%;B,0.98mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比。
在一較佳的實施方案中,所述主合金原料包括以下組分:Nd,22.5mas%;Pr,7.5mas%;Dy,1.5mas%;Ga,0.4mas%;Cu,0.25mas%;Co,1.0mas%;Zr,0.35mas%;B,0.97mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比。
在一較佳的實施方案中,所述主合金原料包括以下組分:Nd,18.9mas%;Pr,6.3mas%;Dy,4.3mas%;Ho,1.0mas%;Ga,0.25mas%;Al,0.1mas%;Cu,0.15mas%;Co,1.0mas%;Ti,0.15mas%;B,0.97mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比。
本發明中,所述輔合金原料中總稀土含量TRE較佳地為35.0~50.0mas%,更佳地為40.0~45.0mas%,mas%是指組分在所述輔合金原料中的質量百分比。
本發明中,所述輔合金原料中,所述LR的含量較佳地為20.0~30.0mas%,例如25.0mas%,mas%是指組分在所述輔合金原料中的質量百分比。
本發明中,所述輔合金原料中,當所述LR包含Nd時,所述Nd的含量較佳地為10.0~20.0mas%,例如15.0mas%,mas%是指組分在所述輔合金原料中的質量百分比。
本發明中,所述輔合金原料中,當所述LR包含Pr時,所述Pr的含量較佳地為15.0~25.0mas%,例如20.0mas%,mas%是指組分在所述輔合金原料中的質量百分比。
較佳地,所述輔合金原料中,所述LR為Nd和Pr,所述Nd的含量為15.0mas%,所述Pr的含量為15.0mas%;mas%是指組分在所述輔合金原料中的質量百分比。
本發明中,所述輔合金原料中,所述HR的含量較佳地為15.0~20.0mas%,mas%是指組分在所述輔合金原料中的質量百分比。
較佳地,所述輔合金原料中,所述HR為Tb,所述Tb的含量為15.0mas%,mas%是指組分在所述輔合金原料中的質量百分比。
較佳地,所述輔合金原料中,所述HR為Dy,所述Dy的含量為20.0mas%,mas%是指組分在所述輔合金原料中的質量百分比。
本發明中,所述輔合金原料中,當所述M包含Ga時,所述Ga的含量較佳地為2.0~10.0mas%,例如5.0mas%,mas%是指組分在所述輔合金原料中的質量百分比。
本發明中,所述輔合金原料中,當所述M包含Co時,所述Co的含量較佳地為10.0~20.0mas%,例如15.0mas%,mas%是指組分在所述輔合金原料中的質量百分比。
較佳地,所述輔合金原料中,所述M為Ga和Co;其中,所述Ga的含量較佳地為5.0mas%,所述Co的含量較佳地為15.0mas%,mas%是指組分在所述輔合金原料中的質量百分比。
本發明中,所述輔合金原料中,所述X的含量較佳地為4.0~10.0mas%,例如4.5mas%或5.0mas%,mas%是指組分在所述輔合金原料中的質量百分比。較佳地,所述輔合金原料中,所述X為Zr。
本發明中,所述輔合金原料中,所述B的含量較佳地為0.3~0.6mas%,例如0.4mas%或0.5mas%,mas%是指組分在所述輔合金原料中的質量百分比。
在一較佳的實施方案中,所述輔合金原料包括以下組分:Nd,15.0mas%;Pr,15.0mas%;Tb,15.0mas%;Zr,10.0mas%;B,0.5mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比。
在一較佳的實施方案中,所述輔合金原料包括以下組分:Pr,25.0mas%;Dy,20.0mas%;Zr,4.5mas%;B,0.5mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比。
在一較佳的實施方案中,所述輔合金原料包括以下組分:Pr,20.0mas%;Dy,20.0mas%;Ga,5.0mas%;Co,15.0mas%;Zr,5.0mas%;B,0.4mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比。
本發明中,所述輔合金原料在所述主輔合金系釹鐵硼磁體材料的原料組合物中的質量百分比較佳地為2.0~5.0mas%,例如4.0mas%。
在一更佳的實施方案中,所述主輔合金系釹鐵硼磁體材料的原料組合物,其包括主合金原料和輔合金原料;其中,所述主合金原料包括以下組分:Nd,22.125mas%;Pr,7.375mas%;Ga,0.25mas%;Al,0.03mas%;Cu,0.1mas%;Co,0.5mas%;Zr,0.11mas%;B,0.98mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比;所述輔合金原料包括以下組分:Nd,15.0mas%;Pr,15.0mas%;Tb,15.0mas%;Zr,10.0mas%;B,0.5mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比;所述輔合金原料在所述主輔合金系釹鐵硼磁體材料的原料組合物中的質量百分比為4.0mas%。
在一更佳的實施方案中,所述主輔合金系釹鐵硼磁體材料的原料組合物,其包括主合金原料和輔合金原料;其中,所述主合金原料包括以下組分:Nd,22.5mas%;Pr,7.5mas%;Dy,1.5mas%;Ga,0.4mas%;Cu,0.25mas%;Co,1.0mas%;Zr,0.35mas%;B,0.97mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比;所述輔合金原料包括以下組分:Pr,25.0mas%;Dy,20.0mas%;Zr,4.5mas%;B,0.5mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比;所述輔合金原料在所述主輔合金系釹鐵硼磁體材料的原料組合物中的質量百分比為5.0mas%。
在一更佳的實施方案中,所述主輔合金系釹鐵硼磁體材料的原料組合物,其包括主合金原料和輔合金原料;其中,所述主合金原料包括以下組分:Nd,18.9mas%;Pr,6.3mas%;Dy,4.3mas%;Ho,1.0mas%;Ga,0.25mas%;Al,0.1mas%;Cu,0.15mas%;Co,1.0mas%;Zr,0.2mas%;B,0.97mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比;所述輔合金原料包括以下組分:Pr,20.0mas%;Dy,20.0mas%;Ga,5.0mas%;Co,15.0mas%;Zr,5.0mas%;B,0.4mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比;所述輔合金原料在所述主輔合金系釹鐵硼磁體材料的原料組合物中的質量百分比為4.0mas%。
本發明還提供一種主輔合金系釹鐵硼磁體材料的製備方法,其包括以下步驟:
S1、將所述的主輔合金系釹鐵硼磁體材料的原料組合物中的所述主合金原料和所述輔合金原料分別熔融後鑄造,分別得主合金和輔合金;
S2、將所述主合金和所述輔合金分別氫破碎和微粉碎後混合,進行成型和燒結處理,即得所述主輔合金系釹鐵硼磁體材料。
本發明中,所述熔融、所述鑄造、所述氫破碎、所述微粉碎、所述成型、以及所述燒結均為本領域常規操作方式和條件。
本發明中,所述熔融可按本領域常規的熔融,例如,在熔煉爐中熔煉即可。所述熔煉爐的真空度約為5×10 -2Pa。所述熔煉的溫度可為1300℃~1600℃,較佳地為1500℃~1550℃。
本發明中,所述鑄造的工藝可為本領域常規的鑄造工藝,例如薄帶連鑄法、鑄錠法、離心鑄造法或快淬法。
本發明中,所述氫破碎的工藝可為本領域常規的工藝。所述氫破碎的脫氫溫度可為400℃~650℃,例如500~620℃。
本發明中,所述微粉碎的工藝可為本領域常規的微粉碎工藝。所述微粉碎較佳地在氣流磨中進行。所述微粉碎較佳地在含氧氣氛下進行;所述含氧氣氛中所述氧含量可為80ppm以下,較佳地為50ppm以下。所述微粉碎後的粉末粒徑可為1~20μm。
本發明中,所述成型的條件可為本領域常規,例如在壓機中壓製成為生坯。所述壓機的磁場強度較佳地為0.5T~3.0T,例如1.0~2.0T。所述壓製的壓力可為200~300MPa,例如260MPa。所述壓製的時間可為本領域常規,可為3~30s,例如15s。
本發明中,所述燒結的條件可為本領域常規。所述燒結的溫度可為1000℃~1150℃,較佳地為1060~1090℃。所述燒結的時間可為4~20小時。所述燒結的氣氛較佳地為真空或氬氣氣氛。
本發明還提供一種主輔合金系釹鐵硼磁體材料,其根據所述主輔合金系釹鐵硼磁體材料的製備方法製備得到。
本發明中,所述主輔合金系釹鐵硼磁體材料包括主相和晶界相;其中,所述主相為核殼結構,所述核為LR 2T 14B,所述殼為HR 2T 14B;所述晶界相包括富釹相、XB 2相和R 6T 13M相;
其中,R為LR和/或HR;
LR選自Y、La、Ce、Pr、Nd的一種或多種;
HR選自Gd、Dy、Tb和Ho中的一種或多種;
M選自Cu、Al和Ga中的一種或多種;
X選自Ti、Zr、Hf、Nb、W和Ta中的一種或多種;
T為Fe和/或Co。
較佳地,所述主輔合金系釹鐵硼磁體材料中,LR為Pr和Nd;HR為Tb;M為Cu、Al和Ga;X為Zr;T為Fe和Co。
較佳地,所述主輔合金系釹鐵硼磁體材料中,LR為Pr和Nd;HR為Dy;M為Cu和Ga;X為Zr;T為Fe和Co。
較佳地,所述主輔合金系釹鐵硼磁體材料中,LR為Pr和Nd;HR為Dy和Ho;M為Cu、Al和Ga;X為Ti;T為Fe和Co。
本發明中,所述主合金提供LR 2Fe 14B主相以及一定的富釹相,而輔合金提供HR作為擴散源,在燒結的過程中所述輔合金中的HR通過熔融的富釹相向主相顆粒表層擴散,替代主相顆粒的LR,從而在主相表層形成重稀土殼層HR 2Fe 14B。所述輔合金中低含量的B以固溶體的方式存在,減少HR 2T 14B的存在,使混合過程中HR更易在主相顆粒外沿形成殼層,進而提高了HR的利用效率;同時,低含量B使得輔合金片更易破碎,便於熔煉設備的正常運行,便於下一步的氫破碎。在所述主合金和所述輔合金混合後熱處理,在高溫下富釹相中的X元素與B結合形成沉澱XB 2,原有的R-Fe-X及Fe-X中的Fe被釋放出來,從而提高富釹相的流動性,促進了M元素等形成R 6T 13M相(四方相,無磁相或反磁相),從而在保證高剩磁(Br)的同時提高了磁體的內稟矯頑力(Hcj)。
在符合本領域常識的基礎上,上述各優選條件,可任意組合,即得本發明各較佳實例。
本發明所用試劑和原料均市售可得。
本發明的積極進步效果在於:
本發明通過構建主輔合金搭配的方式,結合特定的原料配比,在釹鐵硼主相顆粒形成重稀土的殼層,同時提高了富釹相的流動性,從而在保證高剩磁的同時提高了磁體的內稟矯頑力。本發明的製備方法簡單易行,可以工程化應用。
下面通過實施例的方式進一步說明本發明,但並不因此將本發明限制在所述的實施例範圍之中。下列實施例中未註明具體條件的實驗方法,按照常規方法和條件,或按照商品說明書選擇。
實施例1~3
(1)鑄造過程:按下表1中實施例1~3所示的配比,將主輔合金系釹鐵硼磁體材料的原料組合物中的主合金原料和輔合金原料分別放入真空熔煉爐在約5×10 -2Pa的真空中以1500~1550℃的溫度分別進行真空熔煉;之後通過薄帶連鑄法將熔煉所得的熔融液分別進行鑄造,製得主合金片和輔合金片。
(2)氫破碎過程:室溫下,分別將步驟(1)中的主合金片和輔合金片進行吸氫,然後在500~620℃下進行真空脫氫處理,即得粗粉碎粉末。
(3)微粉碎處理:在氣流磨中對步驟(2)中的粗粉碎粉末在50ppm以下的氧含量的氣氛下進行微粉碎,即得到平均粒徑為1~20μm的微粉碎粉末。
(4)成型過程:在磁場強度1.0~2.0T壓機中壓製成為生坯,之後在壓力為260MPa的條件下保持15s,即得成型體。
(5)燒結過程:將成型體在1060~1090℃的溫度下燒結,燒結氣氛為真空或氬氣氣氛,即得釹鐵硼永磁材料。
表1主輔合金系釹鐵硼磁體材料的原料組合物的組分和含量(mas%)
Figure 02_image001
其中,“/”表示不含該組分。
效果實施例
(1)透射電子顯微鏡(TEM)測試
取實施例3製得的主輔合金系釹鐵硼磁體材料,利用TEM觀察磁體材料的相結構,結果如圖1所示。圖1顯示了晶界相中富Ti區的元素分佈,可知Ti與B元素緊密相關,結合相圖及熱力學計算,可知此相為TiB 2,而Zr、Ti、Hf等為同族元素,在釹鐵硼的生產中均可生產此相。TiB 2為高溫陶瓷相,在較大的溫區內保持穩定,從而淨化了晶界中的B,使富釹相流動性更好,並為四方相Nd 6Fe 13Ga等相的生成提供有利條件。
(2)磁性能測試
取實施例1~3製得的主輔合金系釹鐵硼磁體材料,使用中國計量院的PFM14.CN型超高矯頑力永磁測量儀進行磁性能檢測。
表2主輔合金系釹鐵硼磁體材料的磁性能
Figure 02_image003
“Br”是指剩磁;永磁材料經過飽和磁化後,撤去外磁場所能保持的磁性,稱為剩磁。磁極化強度矯頑力Hcj(內稟矯頑力)。
(3)FE-EPMA測試:
取實施例1製得的主輔合金系釹鐵硼磁體材料,由FE-EPMA面掃描形成元素分析圖(Tb、Al、Ga、Co、B、CP、Nd、Cu、Zr等),如圖2所示。從圖2可知,Tb等重稀土元素在主相外沿層形成富集殼層,而Zr等高溫元素在晶界相中均勻分佈,使得富釹相的B得到淨化,從而更易生成四方相Nd 6Fe 13Ga等反磁相,兩者共同提升了磁體的矯頑力。
圖1為本發明實施例3的主輔合金系釹鐵硼磁體材料的TEM圖。
圖2為本發明實施例1的主輔合金系釹鐵硼磁體材料的元素分析圖。

Claims (10)

  1. 一種主輔合金系釹鐵硼磁體材料的原料組合物,其包括主合金原料和輔合金原料;其中,所述主合金原料包括以下組分:輕稀土元素LR,10.0~33.0mas%;LR選自Y、La、Ce、Pr、Nd的一種或多種;重稀土元素HR,0~20.0mas%;HR選自Gd、Dy、Tb和Ho中的一種或多種;M,0.1~5.0mas%;M選自Co、Cu、Al和Ga中的一種或多種;X,0.05~0.7mas%;X選自Zr、Ti和Nb中的一種或多種;B,0.94~1.1mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比; 所述輔合金原料包括以下組分:輕稀土元素LR,0~30.0mas%;LR為Nd和/或Pr;重稀土元素HR,1~80mas%;HR為Dy和/或Tb;M,5.0~20.0mas%;M選自Co、Cu、Al和Ga中的一種或多種;X,3.0~12.0mas%;X選自Ti、Zr、Hf、Nb、W和Ta中的一種或多種;B,0~0.6mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比; 所述輔合金原料在所述主輔合金系釹鐵硼磁體材料的原料組合物中的質量百分比為1.0~15.0mas%。
  2. 如請求項1所述的主輔合金系釹鐵硼磁體材料的原料組合物,其特徵在於,所述主合金原料中總稀土含量TRE為26.0~40.0mas%,較佳地為29.0~32.0mas%,例如29.5mas%、30.5mas%或31.5mas%,mas%是指組分在所述主合金原料中的質量百分比; 和/或,所述主合金原料中,所述LR的含量為25.0~30.0mas%,例如25.2mas%、29.5mas%或30mas%,mas%是指組分在所述主合金原料中的質量百分比; 和/或,所述主合金原料中,當所述LR包含Nd時,所述Nd的含量為18.9~22.5mas%,例如22.125mas%;當所述LR包含Pr時,所述Pr的含量為6.0~7.5mas%,例如6.3mas%或7.375mas%;其中,mas%是指組分在所述主合金原料中的質量百分比; 和/或,所述主合金原料中,所述LR包含Nd和Pr;更佳地,所述Nd的含量為22.125mas%,所述Pr的含量為7.375mas%;或者,所述Nd的含量為22.5mas%,所述Pr的含量為7.5mas%;或者,所述Nd的含量為18.9mas%,所述Pr的含量為6.3mas%;其中,mas%是指組分在所述主合金原料中的質量百分比; 和/或,所述主合金原料中,所述HR的含量為1.0~10.0mas%,例如1.5mas%或5.3mas%,mas%是指組分在所述主合金原料中的質量百分比; 和/或,所述主合金原料中,當所述HR包含Dy時,所述Dy的含量為1.0~5.0mas%,例如1.5mas%或4.3mas%;較佳地,所述主合金原料中,所述HR為Dy;所述Dy的含量較佳地為1.5mas%;當所述HR包含Ho時,所述Ho的含量為0.5~2.0mas%,例如1.0mas%;其中,mas%是指組分在所述主合金原料中的質量百分比; 和/或,所述主合金原料中,所述HR包含Dy和Ho;其中,所述Dy的含量較佳地為4.3mas%,所述Ho的含量較佳地為1.0mas%,mas%是指組分在所述主合金原料中的質量百分比; 和/或,所述主合金原料中,所述M的含量為0.5~2.0mas%,例如0.88mas%、1.5mas%或1.65mas%,mas%是指組分在所述主合金原料中的質量百分比; 和/或,所述主合金原料中,當所述M包含Ga時,所述Ga的含量為0.2~0.4mas%,例如0.25mas%;當所述M包含Al時,所述Al的含量為0.01~0.1mas%,例如0.03mas%;當所述M包含Cu時,所述Cu的含量為0.1~0.25mas%,例如0.15mas%;當所述M包含Co時,所述Co的含量為0.5~1.0mas%;其中,mas%是指組分在所述主合金原料中的質量百分比; 和/或,所述主合金原料中,所述M包含Ga、Al、Cu和Co;其中,所述Ga的含量較佳地為0.25mas%,所述Al的含量較佳地為0.03mas%,所述Cu的含量較佳地為0.1mas%,所述Co的含量較佳地為0.5mas%,mas%是指組分在所述主合金原料中的質量百分比; 和/或,所述主合金原料中,所述X的含量為0.1~0.35mas%,例如0.11mas%或0.15mas%,mas%是指組分在所述主合金原料中的質量百分比; 和/或,所述主合金原料中,所述X為Zr或Ti; 和/或,所述主合金原料中,所述B的含量為0.97~0.99mas%,例如0.98mas%,mas%是指組分在所述主合金原料中的質量百分比。
  3. 如請求項1所述的主輔合金系釹鐵硼磁體材料的原料組合物,其特徵在於,所述主合金原料包括以下組分:Nd,22.125mas%;Pr,7.375mas%;Ga,0.25mas%;Al,0.03mas%;Cu,0.1mas%;Co,0.5mas%;Zr,0.11mas%;B,0.98mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比; 或者,所述主合金原料包括以下組分:Nd,22.5mas%;Pr,7.5mas%;Dy,1.5mas%;Ga,0.4mas%;Cu,0.25mas%;Co,1.0mas%;Zr,0.35mas%;B,0.97mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比; 或者,所述主合金原料包括以下組分:Nd,18.9mas%;Pr,6.3mas%;Dy,4.3mas%;Ho,1.0mas%;Ga,0.25mas%;Al,0.1mas%;Cu,0.15mas%;Co,1.0mas%;Ti,0.15mas%;B,0.97mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比。
  4. 如請求項1所述的主輔合金系釹鐵硼磁體材料的原料組合物,其特徵在於,所述輔合金原料中總稀土含量TRE為35.0~50.0mas%,較佳地為40.0~45.0mas%,mas%是指組分在所述輔合金原料中的質量百分比; 和/或,所述輔合金原料中,所述LR的含量為20.0~30.0mas%,例如25.0mas%,mas%是指組分在所述輔合金原料中的質量百分比; 和/或,所述輔合金原料中,當所述LR包含Nd時,所述Nd的含量為10.0~20.0mas%,例如15.0mas%;當所述LR包含Pr時,所述Pr的含量為15.0~25.0mas%,例如20.0mas%;其中,mas%是指組分在所述輔合金原料中的質量百分比; 和/或,所述輔合金原料中,所述LR為Nd和Pr,所述Nd的含量為15.0mas%,所述Pr的含量為15.0mas%;mas%是指組分在所述輔合金原料中的質量百分比; 和/或,所述輔合金原料中,所述HR的含量為15.0~20.0mas%,mas%是指組分在所述輔合金原料中的質量百分比; 和/或,所述輔合金原料中,所述HR為Tb,所述Tb的含量為15.0mas%,mas%是指組分在所述輔合金原料中的質量百分比; 和/或,所述輔合金原料中,所述HR為Dy,所述Dy的含量為20.0mas%,mas%是指組分在所述輔合金原料中的質量百分比; 和/或,所述輔合金原料中,當所述M包含Ga時,所述Ga的含量為2.0~10.0mas%,例如5.0mas%;當所述M包含Co時,所述Co的含量為10.0~20.0mas%,例如15.0mas%;其中,mas%是指組分在所述輔合金原料中的質量百分比; 和/或,所述輔合金原料中,所述M為Ga和Co;其中,所述Ga的含量較佳地為5.0mas%,所述Co的含量較佳地為15.0mas%,mas%是指組分在所述輔合金原料中的質量百分比; 和/或,所述輔合金原料中,所述X的含量為4.0~10.0mas%,例如4.5mas%或5.0mas%,mas%是指組分在所述輔合金原料中的質量百分比;較佳地,所述輔合金原料中,所述X為Zr; 和/或,所述輔合金原料中,所述B的含量為0.3~0.6mas%,例如0.4mas%或0.5mas%,mas%是指組分在所述輔合金原料中的質量百分比; 和/或,所述輔合金原料在所述主輔合金系釹鐵硼磁體材料的原料組合物中的質量百分比為2.0~5.0mas%,例如4.0mas%。
  5. 如請求項1所述的主輔合金系釹鐵硼磁體材料的原料組合物,其特徵在於,所述輔合金原料包括以下組分:Nd,15.0mas%;Pr,15.0mas%;Tb,15.0mas%;Zr,10.0mas%;B,0.5mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比; 或者,所述輔合金原料包括以下組分:Pr,25.0mas%;Dy,20.0mas%;Zr,4.5mas%;B,0.5mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比; 或者,所述輔合金原料包括以下組分:Pr,20.0mas%;Dy,20.0mas%;Ga,5.0mas%;Co,15.0mas%;Zr,5.0mas%;B,0.4mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比。
  6. 如請求項1所述的主輔合金系釹鐵硼磁體材料的原料組合物,其特徵在於,所述主輔合金系釹鐵硼磁體材料的原料組合物包括主合金原料和輔合金原料;其中,所述主合金原料包括以下組分:Nd,22.125mas%;Pr,7.375mas%;Ga,0.25mas%;Al,0.03mas%;Cu,0.1mas%;Co,0.5mas%;Zr,0.11mas%;B,0.98mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比;所述輔合金原料包括以下組分:Nd,15.0mas%;Pr,15.0mas%;Tb,15.0mas%;Zr,10.0mas%;B,0.5mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比;所述輔合金原料在所述主輔合金系釹鐵硼磁體材料的原料組合物中的質量百分比為4.0mas%; 或者,所述主輔合金系釹鐵硼磁體材料的原料組合物包括主合金原料和輔合金原料;其中,所述主合金原料包括以下組分:Nd,22.5mas%;Pr,7.5mas%;Dy,1.5mas%;Ga,0.4mas%;Cu,0.25mas%;Co,1.0mas%;Zr,0.35mas%;B,0.97mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比;所述輔合金原料包括以下組分:Pr,25.0mas%;Dy,20.0mas%;Zr,4.5mas%;B,0.5mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比;所述輔合金原料在所述主輔合金系釹鐵硼磁體材料的原料組合物中的質量百分比為5.0mas%; 或者,所述主輔合金系釹鐵硼磁體材料的原料組合物包括主合金原料和輔合金原料;其中,所述主合金原料包括以下組分:Nd,18.9mas%;Pr,6.3mas%;Dy,4.3mas%;Ho,1.0mas%;Ga,0.25mas%;Al,0.1mas%;Cu,0.15mas%;Co,1.0mas%;Zr,0.2mas%;B,0.97mas%;餘量為Fe;其中,mas%是指組分在所述主合金原料中的質量百分比;所述輔合金原料包括以下組分:Pr,20.0mas%;Dy,20.0mas%;Ga,5.0mas%;Co,15.0mas%;Zr,5.0mas%;B,0.4mas%;餘量為Fe;其中,mas%是指組分在所述輔合金原料中的質量百分比;所述輔合金原料在所述主輔合金系釹鐵硼磁體材料的原料組合物中的質量百分比為4.0mas%。
  7. 一種主輔合金系釹鐵硼磁體材料的製備方法,其包括以下步驟: S1、將如請求項1~6中任一項所述的主輔合金系釹鐵硼磁體材料的原料組合物中的所述主合金原料和所述輔合金原料分別熔融後鑄造,分別得主合金和輔合金; S2、將所述主合金和所述輔合金分別氫破碎和微粉碎後混合,進行成型和燒結處理,即得所述主輔合金系釹鐵硼磁體材料。
  8. 如請求項7所述的主輔合金系釹鐵硼磁體材料的製備方法,其特徵在於,所述熔融在熔煉爐中熔煉,所述熔煉爐的真空度約為5×10 -2Pa,所述熔煉的溫度為1300℃~1600℃,較佳地為1500℃~1550℃; 和/或,所述鑄造的工藝為薄帶連鑄法、鑄錠法、離心鑄造法或快淬法; 和/或,所述氫破碎的脫氫溫度為400℃~650℃,例如500~620℃; 和/或,所述微粉碎在氣流磨中進行; 和/或,所述微粉碎在含氧氣氛下進行;所述含氧氣氛中氧含量較佳地為80ppm以下,更佳地為50ppm以下; 和/或,所述微粉碎後的粉末粒徑為1~20μm; 和/或,所述成型為在壓機中壓製成為生坯;所述壓機的磁場強度較佳地為0.5T~3.0T,例如1.0~2.0T;所述壓製的壓力較佳地為200~300MPa,例如260MPa;所述壓製的時間較佳地為3~30s,例如15s; 和/或,所述燒結的溫度為1000℃~1150℃,較佳地為1060~1090℃; 和/或,所述燒結的時間為4~20小時; 和/或,所述燒結的氣氛為真空或氬氣氣氛。
  9. 一種主輔合金系釹鐵硼磁體材料,其根據請求項7或8所述的主輔合金系釹鐵硼磁體材料的製備方法製備得到。
  10. 如請求項9所述的主輔合金系釹鐵硼磁體材料,其特徵在於,所述主輔合金系釹鐵硼磁體材料包括主相和晶界相;其中,所述主相為核殼結構,所述核為LR 2T 14B,所述殼為HR 2T 14B;所述晶界相包括富釹相、XB 2相和R 6T 13M相;其中,R為LR和/或HR;LR選自Y、La、Ce、Pr、Nd的一種或多種;HR選自Gd、Dy、Tb和Ho中的一種或多種;M選自Cu、Al和Ga中的一種或多種;X選自Ti、Zr、Hf、Nb、W和Ta中的一種或多種;T為Fe和/或Co; 較佳地,所述主輔合金系釹鐵硼磁體材料中,LR為Pr和Nd;HR為Tb;M為Cu、Al和Ga;X為Zr;T為Fe和Co; 較佳地,所述主輔合金系釹鐵硼磁體材料中,LR為Pr和Nd;HR為Dy;M為Cu和Ga;X為Zr;T為Fe和Co; 較佳地,所述主輔合金系釹鐵硼磁體材料中,LR為Pr和Nd;HR為Dy和Ho;M為Cu、Al和Ga;X為Ti;T為Fe和Co。
TW111107190A 2021-03-10 2022-02-25 主輔合金系釹鐵硼磁體材料及其製備方法 TW202235640A (zh)

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