CN115083707A - 主辅合金系钕铁硼磁体材料及其制备方法 - Google Patents
主辅合金系钕铁硼磁体材料及其制备方法 Download PDFInfo
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- CN115083707A CN115083707A CN202110261268.0A CN202110261268A CN115083707A CN 115083707 A CN115083707 A CN 115083707A CN 202110261268 A CN202110261268 A CN 202110261268A CN 115083707 A CN115083707 A CN 115083707A
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- 239000000956 alloy Substances 0.000 title claims abstract description 285
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 273
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 60
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 44
- 229910052779 Neodymium Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 20
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- 229910052802 copper Inorganic materials 0.000 claims description 16
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
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- 238000002844 melting Methods 0.000 claims description 10
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- AADMRFXTAGXWSE-UHFFFAOYSA-N monoacetoxyscirpenol Natural products CC(=O)OC1C(O)C2OC3(C)C=C(C)CCC3(CO)C1(C)C24CO4 AADMRFXTAGXWSE-UHFFFAOYSA-N 0.000 claims description 10
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
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- 239000002245 particle Substances 0.000 claims description 8
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- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
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- 238000000465 moulding Methods 0.000 claims description 3
- 238000009750 centrifugal casting Methods 0.000 claims description 2
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- 239000011258 core-shell material Substances 0.000 claims description 2
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- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 6
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
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- 238000013467 fragmentation Methods 0.000 description 2
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- 238000003917 TEM image Methods 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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Abstract
本发明公开了一种主辅合金系钕铁硼磁体材料及其制备方法。本发明的主辅合金系钕铁硼磁体材料的原料组合物包括主合金原料和辅合金原料,所述辅合金原料在所述主辅合金系钕铁硼磁体材料的原料组合物中的质量百分比为1.0~15.0mas%。采用该原料组合物制得的主辅合金系钕铁硼磁体材料在保证高剩磁的同时提高了矫顽力,且其制备方法可以工程化应用。
Description
技术领域
本发明涉及一种主辅合金系钕铁硼磁体材料及其制备方法。
背景技术
钕铁硼作为当前常温磁能积最大的永磁体而备受关注,广泛应用于曳引电机、伺服电机、新能源汽车主驱电机、磁性元件、风力发电机等领域。但商用磁体的抗退磁能力仅为理论值(约71KOe)的1/4。钕铁硼的抗退磁能力一般用矫顽力来表征,矫顽力的大小受钕铁硼的微观结构影响大,同时受形核场和钉扎场两种机制控制,以形核场为主导,形核场提高HcJ的途径为消除反向畴形核点。从微观角度,一般有三种提高矫顽力的路径:
1)提高主相之间的晶界相的去磁耦合能力,具体的做法有通过主相含Nd6Fe13X吸收晶界中的Fe,使晶界相向无磁相或反铁磁相转变,同时扩宽晶界;或者提高总稀土量,以提高晶界相体积;通过Cu、Ga、Co、Al等晶界元素的添加,改善富钕相的流动性,优化主相颗粒边界,从而修复主相缺陷,减少反向畴的形成,使HcJ的提高。此类方法提升的HcJ有限,HcJ难以提高至25kOe以上。
2)通过细化晶粒减少主相颗粒的反向畴形核点,越接近单畴尺寸,反向畴越难形成;或通过Nd6Fe13X等晶界相的形成消融主相颗粒的锐角,使主相晶界变平滑,减少反向形核点。此类方法对HcJ的提升效果较强,薄膜法制备磁体的HcJ可达29kOe,但难以工程化应用。
3)通过重稀土添加,使主相各向异性场提高,而重稀土资源储量少、价格高,严重制约了钕铁硼磁体在各行业的应用。通常采双合金或扩散的方式使重稀土在主相外沿层分布,提高重稀土的利用率。但是扩散的方式无法应用在厚度较大(>15mm)的磁体,而现有的双合金法提升的效果有限(大约可将HcJ提高1~1.5kOe)。
发明内容
本发明为了解决现有技术中双合金法制备的钕铁硼磁体矫顽力较低的缺陷,从而提供一种主辅合金系钕铁硼磁体材料及其制备方法。本发明的主辅合金系钕铁硼磁体材料在保证高剩磁的同时提高了矫顽力,且其制备方法可以工程化应用。
为了实现上述目的,本发明采用以下技术方案:
本发明提供了一种主辅合金系钕铁硼磁体材料的原料组合物,其包括主合金原料和辅合金原料;其中,所述主合金原料包括以下组分:轻稀土元素LR,10.0~33.0mas%;LR选自Y、La、Ce、Pr、Nd的一种或多种;重稀土元素HR,0~20.0mas%;HR选自Gd、Dy、Tb和Ho中的一种或多种;M,0.1~5.0mas%;M选自Co、Cu、Al和Ga中的一种或多种;X,0.05~0.7mas%;X选自Zr、Ti和Nb中的一种或多种;B,0.94~1.1mas%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比;
所述辅合金原料包括以下组分:轻稀土元素LR,0~30.0mas%;LR为Nd和/或Pr;重稀土元素HR,1~80mas%;HR为Dy和/或Tb;M,5.0~20.0mas%;M选自Co、Cu、Al和Ga中的一种或多种;X,3.0~12.0mas%;X选自Ti、Zr、Hf、Nb、W和Ta中的一种或多种;B,0~0.6mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比;
所述辅合金原料在所述主辅合金系钕铁硼磁体材料的原料组合物中的质量百分比为1.0~15.0mas%。
本发明中,较佳地,所述主合金原料中总稀土含量TRE为26.0~40.0mas%,更佳地为29.0~32.0mas%,例如29.5mas%、30.5mas%或31.5mas%,mas%是指组分在所述主合金原料中的质量百分比。
本发明中,所述主合金原料中,所述LR的含量较佳地为25.0~30.0mas%,例如25.2mas%、29.5mas%或30mas%,mas%是指组分在所述主合金原料中的质量百分比。
本发明中,所述主合金原料中,当所述LR包含Nd时,所述Nd的含量较佳地为18.9~22.5mas%,例如22.125mas%,mas%是指组分在所述主合金原料中的质量百分比。
本发明中,所述主合金原料中,当所述LR包含Pr时,所述Pr的含量较佳地为6.0~7.5mas%,例如6.3mas%或7.375mas%,mas%是指组分在所述主合金原料中的质量百分比。
较佳地,所述主合金原料中,所述LR包含Nd和Pr。更佳地,所述Nd的含量为22.125mas%,所述Pr的含量为7.375mas%;或者,所述Nd的含量为22.5mas%,所述Pr的含量为7.5mas%;或者,所述Nd的含量为18.9mas%,所述Pr的含量为6.3mas%;mas%是指组分在所述主合金原料中的质量百分比。
本发明中,所述主合金原料中,所述HR的含量较佳地为1.0~10.0mas%,例如1.5mas%或5.3mas%,mas%是指组分在所述主合金原料中的质量百分比。
本发明中,所述主合金原料中,当所述HR包含Dy时,所述Dy的含量较佳地为1.0~5.0mas%,例如1.5mas%或4.3mas%。较佳地,所述主合金原料中,所述HR为Dy;所述Dy的含量较佳地为1.5mas%。其中,mas%是指组分在所述主合金原料中的质量百分比。
本发明中,所述主合金原料中,当所述HR包含Ho时,所述Ho的含量较佳地为0.5~2.0mas%,例如1.0mas%,mas%是指组分在所述主合金原料中的质量百分比。
较佳地,所述主合金原料中,所述HR包含Dy和Ho;其中,所述Dy的含量较佳地为4.3mas%,所述Ho的含量较佳地为1.0mas%,mas%是指组分在所述主合金原料中的质量百分比。
本发明中,所述主合金原料中,所述M的含量较佳地为0.5~2.0mas%,例如0.88mas%、1.5mas%或1.65mas%,mas%是指组分在所述主合金原料中的质量百分比。
本发明中,所述主合金原料中,当所述M包含Ga时,所述Ga的含量较佳地为0.2~0.4mas%,例如0.25mas%,mas%是指组分在所述主合金原料中的质量百分比。
本发明中,所述主合金原料中,当所述M包含Al时,所述Al的含量较佳地为0.01~0.1mas%,例如0.03mas%,mas%是指组分在所述主合金原料中的质量百分比。
本发明中,所述主合金原料中,当所述M包含Cu时,所述Cu的含量较佳地为0.1~0.25mas%,例如0.15mas%,mas%是指组分在所述主合金原料中的质量百分比。
本发明中,所述主合金原料中,当所述M包含Co时,所述Co的含量较佳地为0.5~1.0mas%,mas%是指组分在所述主合金原料中的质量百分比。
较佳地,所述主合金原料中,所述M包含Ga、Al、Cu和Co;其中,所述Ga的含量较佳地为0.25mas%,所述Al的含量较佳地为0.03mas%,所述Cu的含量较佳地为0.1mas%,所述Co的含量较佳地为0.5mas%。其中,mas%是指组分在所述主合金原料中的质量百分比。
本发明中,所述主合金原料中,所述X的含量较佳地为0.1~0.35mas%,例如0.11mas%或0.15mas%,mas%是指组分在所述主合金原料中的质量百分比。较佳地,所述主合金原料中,所述X为Zr或Ti。
本发明中,所述主合金原料中,所述B的含量较佳地为0.97~0.99mas%,例如0.98mas%,mas%是指组分在所述主合金原料中的质量百分比。
在一较佳的实施方案中,所述主合金原料包括以下组分:Nd,22.125mas%;Pr,7.375mas%;Ga,0.25mas%;Al,0.03mas%;Cu,0.1mas%;Co,0.5mas%;Zr,0.11mas%;B,0.98mas%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比。
在一较佳的实施方案中,所述主合金原料包括以下组分:Nd,22.5mas%;Pr,7.5mas%;Dy,1.5mas%;Ga,0.4mas%;Cu,0.25mas%;Co,1.0mas%;Zr,0.35mas%;B,0.97mas%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比。
在一较佳的实施方案中,所述主合金原料包括以下组分: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%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比。
本发明中,所述辅合金原料中总稀土含量TRE较佳地为35.0~50.0mas%,更佳地为40.0~45.0mas%,mas%是指组分在所述辅合金原料中的质量百分比。
本发明中,所述辅合金原料中,所述LR的含量较佳地为20.0~30.0mas%,例如25.0mas%,mas%是指组分在所述辅合金原料中的质量百分比。
本发明中,所述辅合金原料中,当所述LR包含Nd时,所述Nd的含量较佳地为10.0~20.0mas%,例如15.0mas%,mas%是指组分在所述辅合金原料中的质量百分比。
本发明中,所述辅合金原料中,当所述LR包含Pr时,所述Pr的含量较佳地为15.0~25.0mas%,例如20.0mas%,mas%是指组分在所述辅合金原料中的质量百分比。
较佳地,所述辅合金原料中,所述LR为Nd和Pr,所述Nd的含量为15.0mas%,所述Pr的含量为15.0mas%;mas%是指组分在所述辅合金原料中的质量百分比。
本发明中,所述辅合金原料中,所述HR的含量较佳地为15.0~20.0mas%,mas%是指组分在所述辅合金原料中的质量百分比。
较佳地,所述辅合金原料中,所述HR为Tb,所述Tb的含量为15.0mas%,mas%是指组分在所述辅合金原料中的质量百分比。
较佳地,所述辅合金原料中,所述HR为Dy,所述Dy的含量为20.0mas%,mas%是指组分在所述辅合金原料中的质量百分比。
本发明中,所述辅合金原料中,当所述M包含Ga时,所述Ga的含量较佳地为2.0~10.0mas%,例如5.0mas%,mas%是指组分在所述辅合金原料中的质量百分比。
本发明中,所述辅合金原料中,当所述M包含Co时,所述Co的含量较佳地为10.0~20.0mas%,例如15.0mas%,mas%是指组分在所述辅合金原料中的质量百分比。
较佳地,所述辅合金原料中,所述M为Ga和Co;其中,所述Ga的含量较佳地为5.0mas%,所述Co的含量较佳地为15.0mas%,mas%是指组分在所述辅合金原料中的质量百分比。
本发明中,所述辅合金原料中,所述X的含量较佳地为4.0~10.0mas%,例如4.5mas%或5.0mas%,mas%是指组分在所述辅合金原料中的质量百分比。较佳地,所述辅合金原料中,所述X为Zr。
本发明中,所述辅合金原料中,所述B的含量较佳地为0.3~0.6mas%,例如0.4mas%或0.5mas%,mas%是指组分在所述辅合金原料中的质量百分比。
在一较佳的实施方案中,所述辅合金原料包括以下组分:Nd,15.0mas%;Pr,15.0mas%;Tb,15.0mas%;Zr,10.0mas%;B,0.5mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比。
在一较佳的实施方案中,所述辅合金原料包括以下组分:Pr,25.0mas%;Dy,20.0mas%;Zr,4.5mas%;B,0.5mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比。
在一较佳的实施方案中,所述辅合金原料包括以下组分:Pr,20.0mas%;Dy,20.0mas%;Ga,5.0mas%;Co,15.0mas%;Zr,5.0mas%;B,0.4mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比。
本发明中,所述辅合金原料在所述主辅合金系钕铁硼磁体材料的原料组合物中的质量百分比较佳地为2.0~5.0mas%,例如4.0mas%。
在一更佳的实施方案中,所述主辅合金系钕铁硼磁体材料的原料组合物,其包括主合金原料和辅合金原料;其中,所述主合金原料包括以下组分:Nd,22.125mas%;Pr,7.375mas%;Ga,0.25mas%;Al,0.03mas%;Cu,0.1mas%;Co,0.5mas%;Zr,0.11mas%;B,0.98mas%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比;所述辅合金原料包括以下组分:Nd,15.0mas%;Pr,15.0mas%;Tb,15.0mas%;Zr,10.0mas%;B,0.5mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比;所述辅合金原料在所述主辅合金系钕铁硼磁体材料的原料组合物中的质量百分比为4.0mas%。
在一更佳的实施方案中,所述主辅合金系钕铁硼磁体材料的原料组合物,其包括主合金原料和辅合金原料;其中,所述主合金原料包括以下组分:Nd,22.5mas%;Pr,7.5mas%;Dy,1.5mas%;Ga,0.4mas%;Cu,0.25mas%;Co,1.0mas%;Zr,0.35mas%;B,0.97mas%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比;所述辅合金原料包括以下组分:Pr,25.0mas%;Dy,20.0mas%;Zr,4.5mas%;B,0.5mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比;所述辅合金原料在所述主辅合金系钕铁硼磁体材料的原料组合物中的质量百分比为5.0mas%。
在一更佳的实施方案中,所述主辅合金系钕铁硼磁体材料的原料组合物,其包括主合金原料和辅合金原料;其中,所述主合金原料包括以下组分: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%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比;所述辅合金原料包括以下组分:Pr,20.0mas%;Dy,20.0mas%;Ga,5.0mas%;Co,15.0mas%;Zr,5.0mas%;B,0.4mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比;所述辅合金原料在所述主辅合金系钕铁硼磁体材料的原料组合物中的质量百分比为4.0mas%。
本发明还提供一种主辅合金系钕铁硼磁体材料的制备方法,其包括以下步骤:
S1、将所述的主辅合金系钕铁硼磁体材料的原料组合物中的所述主合金原料和所述辅合金原料分别熔融后铸造,分别得主合金和辅合金;
S2、将所述主合金和所述辅合金分别氢破碎和微粉碎后混合,进行成型和烧结处理,即得所述主辅合金系钕铁硼磁体材料。
本发明中,所述熔融、所述铸造、所述氢破碎、所述微粉碎、所述成型、以及所述烧结均为本领域常规操作方式和条件。
本发明中,所述熔融可按本领域常规的熔融,例如,在熔炼炉中熔炼即可。所述熔炼炉的真空度约为5×10-2Pa。所述熔炼的温度可为1300℃~1600℃,较佳地为1500℃~1550℃。
本发明中,所述铸造的工艺可为本领域常规的铸造工艺,例如薄带连铸法、铸锭法、离心铸造法或快淬法。
本发明中,所述氢破碎的工艺可为本领域常规的工艺。所述氢破碎的脱氢温度可为400℃~650℃,例如500~620℃。
本发明中,所述微粉碎的工艺可为本领域常规的微粉碎工艺。所述微粉碎较佳地在气流磨中进行。所述微粉碎较佳地在含氧气氛下进行;所述含氧气氛中所述氧含量可为80ppm以下,较佳地为50ppm以下。所述微粉碎后的粉末粒径可为1~20μm。
本发明中,所述成型的条件可为本领域常规,例如在压机中压制成为生坯。所述压机的磁场强度较佳地为0.5T~3.0T,例如1.0~2.0T。所述压制的压力可为200~300MPa,例如260MPa。所述压制的时间可为本领域常规,可为3~30s,例如15s。
本发明中,所述烧结的条件可为本领域常规。所述烧结的温度可为1000℃~1150℃,较佳地为1060~1090℃。所述烧结的时间可为4~20小时。所述烧结的气氛较佳地为真空或氩气气氛。
本发明还提供一种主辅合金系钕铁硼磁体材料,其根据所述主辅合金系钕铁硼磁体材料的制备方法制备得到。
本发明中,所述主辅合金系钕铁硼磁体材料包括主相和晶界相;其中,所述主相为核壳结构,所述核为LR2T14B,所述壳为HR2T14B;所述晶界相包括富钕相、XB2相和R6T13M相;
其中,R为LR和/或HR;
LR选自Y、La、Ce、Pr、Nd的一种或多种;
HR选自Gd、Dy、Tb和Ho中的一种或多种;
M选自Cu、Al和Ga中的一种或多种;
X选自Ti、Zr、Hf、Nb、W和Ta中的一种或多种;
T为Fe和/或Co。
较佳地,所述主辅合金系钕铁硼磁体材料中,LR为Pr和Nd;HR为Tb;M为Cu、Al和Ga;X为Zr;T为Fe和Co。
较佳地,所述主辅合金系钕铁硼磁体材料中,LR为Pr和Nd;HR为Dy;M为Cu和Ga;X为Zr;T为Fe和Co。
较佳地,所述主辅合金系钕铁硼磁体材料中,LR为Pr和Nd;HR为Dy和Ho;M为Cu、Al和Ga;X为Ti;T为Fe和Co。
本发明中,所述主合金提供LR2Fe14B主相以及一定的富钕相,而辅合金提供HR作为扩散源,在烧结的过程中所述辅合金中的HR通过熔融的富钕相向主相颗粒表层扩散,替代主相颗粒的LR,从而在主相表层形成重稀土壳层HR2Fe14B。所述辅合金中低含量的B以固溶体的方式存在,减少HR2T14B的存在,使混合过程中HR更易在主相颗粒外沿形成壳层,进而提高了HR的利用效率;同时,低含量B使得辅合金片更易破碎,便于熔炼设备的正常运行,便于下一步的氢破碎。在所述主合金和所述辅混合后热处理,在高温下富钕相中的X元素与B结合形成沉淀XB2,原有的R-Fe-X及Fe-X中的Fe被释放出来,从而提高富钕相的流动性,促进了M元素等形成R6T13M相(四方相,无磁相或反磁相),从而在保证高剩磁(Br)的同时提高了磁体的内禀矫顽力(HcJ)。
在符合本领域常识的基础上,上述各优选条件,可任意组合,即得本发明各较佳实例。
本发明所用试剂和原料均市售可得。
本发明的积极进步效果在于:
本发明通过构建主辅合金搭配的方式,结合特定的原料配比,在钕铁硼主相颗粒形成重稀土的壳层,同时提高了富钕相的流动性,从而在保证高剩磁的同时提高了磁体的内禀矫顽力。本发明的制备方法简单易行,可以工程化应用。
附图说明
图1为本发明实施例3的主辅合金系钕铁硼磁体材料的TEM图。
图2为本发明实施例1的主辅合金系钕铁硼磁体材料的元素分析图。
具体实施方式
下面通过实施例的方式进一步说明本发明,但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法,按照常规方法和条件,或按照商品说明书选择。
实施例1~3
(1)铸造过程:按下表1中实施例1~3所示的配比,将主辅合金系钕铁硼磁体材料的原料组合物中的主合金原料和辅合金原料分别放入真空熔炼炉在约5×10-2Pa的真空中以1500~1550℃的温度分别进行真空熔炼;之后通过薄带连铸法将熔炼所得的熔融液分别进行铸造,制得主合金片和辅合金片。
(2)氢破碎过程:室温下,分别将步骤(1)中的主合金片和辅合金片进行吸氢,然后在500~620℃下进行真空脱氢处理,即得粗粉碎粉末。
(3)微粉碎处理:在气流磨中对步骤(2)中的粗粉碎粉末在50ppm以下的氧含量的气氛下进行微粉碎,即得到平均粒径为1~20μm的微粉碎粉末。
(4)成型过程:在磁场强度1.0~2.0T压机中压制成为生坯,之后在压力为260MPa的条件下保持15s,即得成型体。
(5)烧结过程:将成型体在1060~1090℃的温度下烧结,烧结气氛为真空或氩气气氛,即得钕铁硼永磁材料。
表1主辅合金系钕铁硼磁体材料的原料组合物的组分和含量(mas%)
其中,“/”表示不含该组分。
效果实施例
(1)透射电子显微镜(TEM)测试
取实施例3制得的主辅合金系钕铁硼磁体材料,利用TEM观察磁体材料的相结构,结果如图1所示。图1显示了晶界相中富Ti区的元素分布,可知Ti与B元素紧密相关,结合相图及热力学计算,可知此相为TiB2,而Zr、Ti、Hf等为同族元素,在钕铁硼的生产中均可生产此相。TiB2为高温陶瓷相,在较大的温区内保持稳定,从而净化了晶界中的B,使富钕相流动性更好,并为四方相Nd6Fe13Ga等相的生成提供有利条件。
(2)磁性能测试
取实施例1~3制得的主辅合金系钕铁硼磁体材料,使用中国计量院的PFM14.CN型超高矫顽力永磁测量仪进行磁性能检测。
表2主辅合金系钕铁硼磁体材料的磁性能
编号 | 实施例1 | 实施例2 | 实施例3 |
Br(kGs) | 14.3 | 13.1 | 12.2 |
HcJ(kOe) | 18.9 | 24.5 | 30.5 |
“Br”是指剩磁;永磁材料经过饱和磁化后,撤去外磁场所能保持的磁性,称为剩磁。磁极化强度矫顽力HcJ(内禀矫顽力)。
(3)FE-EPMA测试:
取实施例1制得的主辅合金系钕铁硼磁体材料,由FE-EPMA面扫描形成元素分析图(Tb、Al、Ga、Co、B、CP、Nd、Cu、Zr等),如图2所示。从图2可知,Tb等重稀土元素在主相外沿层形成富集壳层,而Zr等高温元素在晶界相中均匀分布,使得富钕相的B得到净化,从而更易生成四方相Nd6Fe13Ga等反磁相,两者共同提升了磁体的矫顽力。
Claims (10)
1.一种主辅合金系钕铁硼磁体材料的原料组合物,其包括主合金原料和辅合金原料;其中,所述主合金原料包括以下组分:轻稀土元素LR,10.0~33.0mas%;LR选自Y、La、Ce、Pr、Nd的一种或多种;重稀土元素HR,0~20.0mas%;HR选自Gd、Dy、Tb和Ho中的一种或多种;M,0.1~5.0mas%;M选自Co、Cu、Al和Ga中的一种或多种;X,0.05~0.7mas%;X选自Zr、Ti和Nb中的一种或多种;B,0.94~1.1mas%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比;
所述辅合金原料包括以下组分:轻稀土元素LR,0~30.0mas%;LR为Nd和/或Pr;重稀土元素HR,1~80mas%;HR为Dy和/或Tb;M,5.0~20.0mas%;M选自Co、Cu、Al和Ga中的一种或多种;X,3.0~12.0mas%;X选自Ti、Zr、Hf、Nb、W和Ta中的一种或多种;B,0~0.6mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比;
所述辅合金原料在所述主辅合金系钕铁硼磁体材料的原料组合物中的质量百分比为1.0~15.0mas%。
2.如权利要求1所述的主辅合金系钕铁硼磁体材料的原料组合物,其特征在于,所述主合金原料中总稀土含量TRE为26.0~40.0mas%,较佳地为29.0~32.0mas%,例如29.5mas%、30.5mas%或31.5mas%,mas%是指组分在所述主合金原料中的质量百分比;
和/或,所述主合金原料中,所述LR的含量为25.0~30.0mas%,例如25.2mas%、29.5mas%或30mas%,mas%是指组分在所述主合金原料中的质量百分比;
和/或,所述主合金原料中,当所述LR包含Nd时,所述Nd的含量为18.9~22.5mas%,例如22.125mas%;当所述LR包含Pr时,所述Pr的含量为6.0~7.5mas%,例如6.3mas%或7.375mas%;其中,mas%是指组分在所述主合金原料中的质量百分比;
和/或,所述主合金原料中,所述LR包含Nd和Pr;更佳地,所述Nd的含量为22.125mas%,所述Pr的含量为7.375mas%;或者,所述Nd的含量为22.5mas%,所述Pr的含量为7.5mas%;或者,所述Nd的含量为18.9mas%,所述Pr的含量为6.3mas%;其中,mas%是指组分在所述主合金原料中的质量百分比;
和/或,所述主合金原料中,所述HR的含量为1.0~10.0mas%,例如1.5mas%或5.3mas%,mas%是指组分在所述主合金原料中的质量百分比;
和/或,所述主合金原料中,当所述HR包含Dy时,所述Dy的含量为1.0~5.0mas%,例如1.5mas%或4.3mas%;较佳地,所述主合金原料中,所述HR为Dy;所述Dy的含量较佳地为1.5mas%;当所述HR包含Ho时,所述Ho的含量为0.5~2.0mas%,例如1.0mas%;其中,mas%是指组分在所述主合金原料中的质量百分比;
和/或,所述主合金原料中,所述HR包含Dy和Ho;其中,所述Dy的含量较佳地为4.3mas%,所述Ho的含量较佳地为1.0mas%,mas%是指组分在所述主合金原料中的质量百分比;
和/或,所述主合金原料中,所述M的含量为0.5~2.0mas%,例如0.88mas%、1.5mas%或1.65mas%,mas%是指组分在所述主合金原料中的质量百分比;
和/或,所述主合金原料中,当所述M包含Ga时,所述Ga的含量为0.2~0.4mas%,例如0.25mas%;当所述M包含Al时,所述Al的含量为0.01~0.1mas%,例如0.03mas%;当所述M包含Cu时,所述Cu的含量为0.1~0.25mas%,例如0.15mas%;当所述M包含Co时,所述Co的含量为0.5~1.0mas%;其中,mas%是指组分在所述主合金原料中的质量百分比;
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的含量较佳地为0.25mas%,所述Al的含量较佳地为0.03mas%,所述Cu的含量较佳地为0.1mas%,所述Co的含量较佳地为0.5mas%,mas%是指组分在所述主合金原料中的质量百分比;
和/或,所述主合金原料中,所述X的含量为0.1~0.35mas%,例如0.11mas%或0.15mas%,mas%是指组分在所述主合金原料中的质量百分比;
和/或,所述主合金原料中,所述X为Zr或Ti;
和/或,所述主合金原料中,所述B的含量为0.97~0.99mas%,例如0.98mas%,mas%是指组分在所述主合金原料中的质量百分比。
3.如权利要求1所述的主辅合金系钕铁硼磁体材料的原料组合物,其特征在于,所述主合金原料包括以下组分:Nd,22.125mas%;Pr,7.375mas%;Ga,0.25mas%;Al,0.03mas%;Cu,0.1mas%;Co,0.5mas%;Zr,0.11mas%;B,0.98mas%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比;
或者,所述主合金原料包括以下组分:Nd,22.5mas%;Pr,7.5mas%;Dy,1.5mas%;Ga,0.4mas%;Cu,0.25mas%;Co,1.0mas%;Zr,0.35mas%;B,0.97mas%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比;
或者,所述主合金原料包括以下组分: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%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比。
4.如权利要求1所述的主辅合金系钕铁硼磁体材料的原料组合物,其特征在于,所述辅合金原料中总稀土含量TRE为35.0~50.0mas%,较佳地为40.0~45.0mas%,mas%是指组分在所述辅合金原料中的质量百分比;
和/或,所述辅合金原料中,所述LR的含量为20.0~30.0mas%,例如25.0mas%,mas%是指组分在所述辅合金原料中的质量百分比;
和/或,所述辅合金原料中,当所述LR包含Nd时,所述Nd的含量为10.0~20.0mas%,例如15.0mas%;当所述LR包含Pr时,所述Pr的含量为15.0~25.0mas%,例如20.0mas%;其中,mas%是指组分在所述辅合金原料中的质量百分比;
和/或,所述辅合金原料中,所述LR为Nd和Pr,所述Nd的含量为15.0mas%,所述Pr的含量为15.0mas%;mas%是指组分在所述辅合金原料中的质量百分比;
和/或,所述辅合金原料中,所述HR的含量为15.0~20.0mas%,mas%是指组分在所述辅合金原料中的质量百分比;
和/或,所述辅合金原料中,所述HR为Tb,所述Tb的含量为15.0mas%,mas%是指组分在所述辅合金原料中的质量百分比;
和/或,所述辅合金原料中,所述HR为Dy,所述Dy的含量为20.0mas%,mas%是指组分在所述辅合金原料中的质量百分比;
和/或,所述辅合金原料中,当所述M包含Ga时,所述Ga的含量为2.0~10.0mas%,例如5.0mas%;当所述M包含Co时,所述Co的含量为10.0~20.0mas%,例如15.0mas%;其中,mas%是指组分在所述辅合金原料中的质量百分比;
和/或,所述辅合金原料中,所述M为Ga和Co;其中,所述Ga的含量较佳地为5.0mas%,所述Co的含量较佳地为15.0mas%,mas%是指组分在所述辅合金原料中的质量百分比;
和/或,所述辅合金原料中,所述X的含量为4.0~10.0mas%,例如4.5mas%或5.0mas%,mas%是指组分在所述辅合金原料中的质量百分比;较佳地,所述辅合金原料中,所述X为Zr;
和/或,所述辅合金原料中,所述B的含量为0.3~0.6mas%,例如0.4mas%或0.5mas%,mas%是指组分在所述辅合金原料中的质量百分比;
和/或,所述辅合金原料在所述主辅合金系钕铁硼磁体材料的原料组合物中的质量百分比为2.0~5.0mas%,例如4.0mas%。
5.如权利要求1所述的主辅合金系钕铁硼磁体材料的原料组合物,其特征在于,所述辅合金原料包括以下组分:Nd,15.0mas%;Pr,15.0mas%;Tb,15.0mas%;Zr,10.0mas%;B,0.5mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比;
或者,所述辅合金原料包括以下组分:Pr,25.0mas%;Dy,20.0mas%;Zr,4.5mas%;B,0.5mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比;
或者,所述辅合金原料包括以下组分:Pr,20.0mas%;Dy,20.0mas%;Ga,5.0mas%;Co,15.0mas%;Zr,5.0mas%;B,0.4mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比。
6.如权利要求1所述的主辅合金系钕铁硼磁体材料的原料组合物,其特征在于,所述主辅合金系钕铁硼磁体材料的原料组合物包括主合金原料和辅合金原料;其中,所述主合金原料包括以下组分:Nd,22.125mas%;Pr,7.375mas%;Ga,0.25mas%;Al,0.03mas%;Cu,0.1mas%;Co,0.5mas%;Zr,0.11mas%;B,0.98mas%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比;所述辅合金原料包括以下组分:Nd,15.0mas%;Pr,15.0mas%;Tb,15.0mas%;Zr,10.0mas%;B,0.5mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比;所述辅合金原料在所述主辅合金系钕铁硼磁体材料的原料组合物中的质量百分比为4.0mas%;
或者,所述主辅合金系钕铁硼磁体材料的原料组合物包括主合金原料和辅合金原料;其中,所述主合金原料包括以下组分:Nd,22.5mas%;Pr,7.5mas%;Dy,1.5mas%;Ga,0.4mas%;Cu,0.25mas%;Co,1.0mas%;Zr,0.35mas%;B,0.97mas%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比;所述辅合金原料包括以下组分:Pr,25.0mas%;Dy,20.0mas%;Zr,4.5mas%;B,0.5mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比;所述辅合金原料在所述主辅合金系钕铁硼磁体材料的原料组合物中的质量百分比为5.0mas%;
或者,所述主辅合金系钕铁硼磁体材料的原料组合物包括主合金原料和辅合金原料;其中,所述主合金原料包括以下组分: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%;余量为Fe;其中,mas%是指组分在所述主合金原料中的质量百分比;所述辅合金原料包括以下组分:Pr,20.0mas%;Dy,20.0mas%;Ga,5.0mas%;Co,15.0mas%;Zr,5.0mas%;B,0.4mas%;余量为Fe;其中,mas%是指组分在所述辅合金原料中的质量百分比;所述辅合金原料在所述主辅合金系钕铁硼磁体材料的原料组合物中的质量百分比为4.0mas%。
7.一种主辅合金系钕铁硼磁体材料的制备方法,其包括以下步骤:
S1、将如权利要求1~6中任一项所述的主辅合金系钕铁硼磁体材料的原料组合物中的所述主合金原料和所述辅合金原料分别熔融后铸造,分别得主合金和辅合金;
S2、将所述主合金和所述辅合金分别氢破碎和微粉碎后混合,进行成型和烧结处理,即得所述主辅合金系钕铁硼磁体材料。
8.如权利要求7所述的主辅合金系钕铁硼磁体材料的制备方法,其特征在于,所述熔融在熔炼炉中熔炼,所述熔炼炉的真空度约为5×10-2Pa,所述熔炼的温度为1300℃~1600℃,较佳地为1500℃~1550℃;
和/或,所述铸造的工艺为薄带连铸法、铸锭法、离心铸造法或快淬法;
和/或,所述氢破碎的脱氢温度为400℃~650℃,例如500~620℃;
和/或,所述微粉碎在气流磨中进行;
和/或,所述微粉碎在含氧气氛下进行;所述含氧气氛中氧含量较佳地为80ppm以下,更佳地为50ppm以下;
和/或,所述微粉碎后的粉末粒径为1~20μm;
和/或,所述成型为在压机中压制成为生坯;所述压机的磁场强度较佳地为0.5T~3.0T,例如1.0~2.0T;所述压制的压力较佳地为200~300MPa,例如260MPa;所述压制的时间较佳地为3~30s,例如15s;
和/或,所述烧结的温度为1000℃~1150℃,较佳地为1060~1090℃;
和/或,所述烧结的时间为4~20小时;
和/或,所述烧结的气氛为真空或氩气气氛。
9.一种主辅合金系钕铁硼磁体材料,其根据权利要求7或8所述的主辅合金系钕铁硼磁体材料的制备方法制备得到。
10.如权利要求9所述的主辅合金系钕铁硼磁体材料,其特征在于,所述主辅合金系钕铁硼磁体材料包括主相和晶界相;其中,所述主相为核壳结构,所述核为LR2T14B,所述壳为HR2T14B;所述晶界相包括富钕相、XB2相和R6T13M相;其中,R为LR和/或HR;LR选自Y、La、Ce、Pr、Nd的一种或多种;HR选自Gd、Dy、Tb和Ho中的一种或多种;M选自Cu、Al和Ga中的一种或多种;X选自Ti、Zr、Hf、Nb、W和Ta中的一种或多种;T为Fe和/或Co;
较佳地,所述主辅合金系钕铁硼磁体材料中,LR为Pr和Nd;HR为Tb;M为Cu、Al和Ga;X为Zr;T为Fe和Co;
较佳地,所述主辅合金系钕铁硼磁体材料中,LR为Pr和Nd;HR为Dy;M为Cu和Ga;X为Zr;T为Fe和Co;
较佳地,所述主辅合金系钕铁硼磁体材料中,LR为Pr和Nd;HR为Dy和Ho;M为Cu、Al和Ga;X为Ti;T为Fe和Co。
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US18/280,725 US20240145137A1 (en) | 2021-03-10 | 2022-01-17 | Main and auxiliary alloy-based neodymium-iron-boron magnet material and preparation method therefor |
PCT/CN2022/072244 WO2022188550A1 (zh) | 2021-03-10 | 2022-01-17 | 主辅合金系钕铁硼磁体材料及其制备方法 |
JP2023544205A JP2024512183A (ja) | 2021-03-10 | 2022-01-17 | 主合金と副合金系ネオジム鉄ホウ素磁石材料及びその製造方法 |
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