CN103221998A - 磁交换耦合的核-壳纳米磁体 - Google Patents
磁交换耦合的核-壳纳米磁体 Download PDFInfo
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Abstract
永久性磁体(12)被制造成具有由薄软磁性壳(15)包围的硬磁性核(14)。所述硬磁性核可提供相对高的矫顽力(Hci),并且所述软磁性壳可提供相对高的磁通密度(B)。由于所述核和壳之间的磁交换耦合,可在宽温度范围内,包括高于150℃的温度,实现相对高的最大磁能积(BH)max。此外,无需使用稀土金属或者贵重金属即可实现该效果,这有助于使磁体的制造成本保持为较低。为了允许在所述核和壳之间进行充分的磁交换耦合,所述壳的宽度小于约40纳米,并且控制整体尺寸,以使所述壳的宽度小于所述核的布洛赫畴壁厚度的两倍。
Description
相关申请的交叉引用
本申请要求2010年11月15日申请的、题为“磁交换耦合的核-壳纳米磁体(Magnetic Exchange Coupled Core-Shell Nanomagnets)”的美国临时专利申请61/413,869的优先权,通过引用的方式将其合并于此。
背景技术
当前,永久磁体广泛应用于各种应用领域,包括诸如电动车和风力发电机的电动机应用。不幸的是,很多永久性磁体的性能在高温时会降低,这使得它们不适合于某些应用中,例如,温度经常超过150摄氏度(℃)的电动机应用。此外,很多永久性磁体由昂贵的材料制成,例如,贵重金属或者稀土金属,这使永久性磁体具有有限的可用性。
作为例子,一些包括Nd2Fe14B、镝掺杂的Nd2Fe14B、SmCo和Sm2Fe17N3的稀土磁体已经用于或者考虑用于混合电动机和电动车。这种磁体中的Nd2Fe14B通常可提供最高的最大磁能积(BH)max。然而,该磁体的工作温度限制在大约150℃,这归因于大约为310到400℃的低居里温度。此外,磁化强度随着温度降低,并且通常会在居里温度附近消失。为了提高工作温度,可在磁体中加入镝,但是,在磁体中加入镝会提高矫顽力,并降低磁化强度。因此,替代效果相对的不明显。
因此,本领域需要一种至今尚未解决的能够在高温下有效的工作的廉价永磁体。
附图说明
参考附图能够更好的理解本发明。附图中的元件并没有按照彼此之间的实际尺寸来绘制,而将重点放在了清楚地示出本发明的原理上。此外,在一些附图中,相同的参考标记表示相应的部件。
图1示出了具有由软磁性壳包围的硬磁性核的纳米磁性颗粒的示例性实施方式。
图2是具有由软磁性壳(坡莫合金)包围的硬磁性核(MnAl)的纳米磁体颗粒的最大磁能积(BH)max的图。
图3是具有由软磁性壳包围的硬磁性核(τ-MnAl)的纳米磁体颗粒在300开尔文(K)处的、基于硬磁相的(BH)max的体积分数(fh)图,其中,Mr/Ms=1,并且软壳的饱和磁化在1.3到2.2T的范围之间。
图4是具有由软磁性壳包围的硬磁性核(τ-MnAl)的纳米磁体颗粒在300开尔文(K)处的、基于硬磁相的(BH)max的体积分数(fh)图,其中,Mr/Ms=0.7,并且软壳的饱和磁化在1.3到2.2T的范围之间。
图5是具有由软磁性壳包围的硬磁性核(τ-MnAl)的纳米磁体颗粒在450开尔文(K)处的、基于硬磁相的(BH)max的体积分数(fh)图,其中,Mr/Ms=1,并且软壳的饱和磁化在1.3到2.2T的范围之间。
图6是具有由软磁性壳包围的硬磁性核(τ-MnAl)的纳米磁体颗粒在450开尔文(K)处的、基于硬磁相的(BH)max的体积分数(fh)图,其中,Mr/Ms=0.7,并且软壳的饱和磁化在1.3到2.2T的范围之间。
图7是具有由软磁性壳包围的硬磁性核(MnBi)的纳米磁体颗粒在300开尔文(K)处的、基于硬磁相的(BH)max的体积分数(fh)图,其中,Mr/Ms=1,并且软壳的饱和磁化在1.3到2.2T的范围之间。
图8是具有由软磁性壳包围的硬磁性核(MnBi)的纳米磁体颗粒在450开尔文(K)处的、基于硬磁相的(BH)max的体积分数(fh)图,其中,Mr/Ms=1,并且软壳的饱和磁化在1.3到2.2T的范围之间。
图9是具有由软磁性壳包围的硬磁性核(BaM)的纳米磁体颗粒在300开尔文(K)处的、基于硬磁相的(BH)max的体积分数(fh)图,其中,Mr/Ms=1,并且软壳的饱和磁化在1.3到2.2T的范围之间。
图10是具有由软磁性壳包围的硬磁性核(BaM)的纳米磁体颗粒在450开尔文(K)处的、基于硬磁相的(BH)max的体积分数(fh)图,其中,Mr/Ms=1,并且软壳的饱和磁化在1.3到2.2T的范围之间。
具体实施方式
本发明总体上涉及磁交换耦合的核-壳纳米磁体。在一个示例性的实施方式中,永久性磁体被制造成具有由薄软磁性壳包围的硬磁性核。所述硬磁性核可提供相对高的矫顽力(Hci),并且所述软磁性壳可提供相对高的磁通密度(B)。由于核和壳之间的磁交换耦合,可在宽温度范围内(包括高于150℃的温度)实现相对高的最大磁能积(BH)max。此外,无需使用稀土金属或者贵重金属即可实现该效果,这有助于使磁体的制造成本保持为较低。为了允许在核和壳之间进行充分的磁交换耦合,而控制整个壳的厚度,以使壳的宽度小于核的布洛赫(Bloch)畴壁厚度的两倍。
图1示出了示例性的核-壳纳米磁性颗粒,所述核-壳纳米磁性颗粒12被制造成具有由硬磁性材料组成的核14和由软磁性材料组成的壳15。在一个示例性的实施方式中,核14的材料包括锰、铝、铋、锶、铅、铁或氧(至少有一个硬磁性元素,但更优选的是具有至少两个硬磁元素),壳的材料包括铁,钴,镍,铝,硅,氮或氧(至少有一个软磁性元素,但更优选的是具有至少两个软磁性元素)。作为例子,硬磁性核14可由铝化锰(MnAl)、M型六角铁氧体(BaFe12O19)或锰铋(MnBi)组成,软磁性壳15可以由Fe65Co35,坡莫合金(Fe20Ni80)或铁硅铝磁合金(FeAlSi)组成。然而,在其它实施方式中,其它元素和/或元素的组合也是可能的。
如同核14一样,核-壳颗粒12的形状通常是球形,然而,在其他实施方式中,它还可以具有其他形状,例如,针状或者六角形。此外,壳15形成了环绕并包围核14的中空的球体,并且核14填充在所述中空球体的空间内。在一个实施方式中,其他形状(例如,圆柱形、立方体形、或者六角形)的壳15也是可能的。在一个示例性的实施方式中,壳15的厚度(δs)大约为20nm到40nm之间,该厚度小于核14的布洛赫(Bloch)畴壁厚度的两倍。此外,围绕着核14的壳15的厚度是均匀的。然而,应该强调的是,在其他实施方式中,核-壳颗粒12的其他形状和配置也是可能的。
核-壳颗粒12的(BH)max可由以下公式表示(假设Mr=Ms):
(1)Mr=fhMh+fsMs,当Ms=Mr时,→等式(6),R.Skomski
第3591页,E.Kneller
(2) →等式(8),R.Skomski
Mr:硬磁相+软磁相的剩磁
Ms:软磁相的饱和磁化
Mh:硬磁相的饱和磁化
Kh:硬磁相的磁各向异性能量
Ks:软磁相的磁各向异性能量
fh:硬磁相的体积分数
fs:软磁相的体积分数
μ0:4π×10-7N/A2
[参考文献1]R.Skomski和J.M.D.Coey,”Giant energy product innanostructured two-phase magnets”,phys.Rev.B,48,21(1993)
[参考文献2]E.F.Kneller和R.Hawig,”The exchange-spring magnet:Anew material principle for permanent magnets”,IEEE Trans,Magn.27,pp.3588-3600,(1991)
假设Mr=0.7Ms,Br=μ0Mr,那么,Br=0.7μ0Ms,Br=0.7Bs
(5)
当 时
(6)
当 时
(7)
Bs_soft:软磁相的Bs[T]
Bh_hard:硬磁相的Bs[T]
图2示出了τ相MnAl-坡莫合金核-壳纳米磁体的(BH)max根据硬核的体积分数(fh)的变化。其中使用了硬磁性τ-MnAl核(饱和磁化=0.7T;磁性各向异性常数Kh=1MJ/m3)和软磁性坡莫合金壳(饱和磁化=1T;磁性各向异性常数Ks=0.01MJ/m3)。
使用等式(6)和(7)来分别在和时计算MnAl-坡莫合金核-壳纳米磁体的(BH)max。需要指出的是,在Hn=Mr/2和fh=8%处,(BH)max大约为12MGOe,而纯(fh=100%)MnAl纳米磁体的(BH)max大约为7MGOe。
τ相MnAl核-软壳纳米磁体(即,纳米磁体具有形成硬磁性核14的τ相MnAl)用于使用等式(6)和(7)来根据饱和磁化(Ms)和壳的厚度(δs)计算(BH)max,其中,壳15由软磁性合金组成。然而,通常希望壳的厚度(δs)小于核14的布洛赫(Bloch)畴壁厚度的两倍,以允许在核14和壳15之间进行有效的磁交换耦合。这是因为当壳的厚度增加到大于布洛赫(Bloch)畴壁厚度时,磁交换耦合会变得较弱。τ相MnAl的布洛赫(Bloch)畴壁厚度大约为15nm[G.G.Korznikova,J.of Microscopy,第239,239,2010卷]。因此,壳的厚度最好小于30nm。图3示出了当存在交换耦合时,MnAl-CoFe(2.2T)核-壳纳米磁体的(BH)max变成大约55MGOe。这种高(BH)max归因于交换耦合。
在另外一个实施方式中,钡铁氧体(BaM:BaFe12O19)-Fe65Co35核-壳纳米磁体用于计算(BH)max。图9示出了这种磁体的(BH)max作为硬BaM核的体积分数(fh)的函数。当fh等于55%时,(BH)max估计为大约22.5MGOe。由于钡铁氧体的布洛赫(Bloch)畴壁厚度大约为14nm,因此希望用于100nm的钡铁氧体颗粒的壳的厚度大约为11nm,以提供约22.5MGOe[M.Zises和M.j.Thornton,Spin Electronics,第220页,2001年春]。
图4-10示出了各种核-壳纳米磁体在不同温度下的(BH)max估计。特别的,图3示出了当Mr/Ms=1时,使用了τ-MnAl的核14在300K处的(BH)max的图,图4示出了当Mr/Ms=0.7时,使用了τ-MnAl的核14在300K处的(BH)max的图,图5示出了当Mr/Ms=1时,使用了τ-MnAl的核14在450K处的(BH)max的图,图6示出了当Mr/Ms=0.7时,使用了τ-MnAl的核14在450K处的(BH)max的图,图7示出了当Mr/Ms=1时,使用了MnBi的核14在300K处的(BH)max的图,图8示出了当Mr/Ms=1时,使用了MnBi的核14在450K处的(BH)max的图,图9示出了当Mr/Ms=1时,使用了BaM的核14在300K处的(BH)max的图,以及图10示出了当Mr/Ms=1时,使用了BaM的核14在450K处的(BH)max的图。
需要指出的是,能够使用各种技术来制造纳米磁体,如在此所描述的,包括化学镀、化学和物理综合以及在聚合物基体中嵌入核-壳纳米磁体。
在一个示例性的实施方式中,在蒸馏水中混合M型六角铁氧体纳米颗粒和阴离子表面活性剂,同时进行带有氩气吹扫的机械搅拌,并随后利用去离子水进行清洗。所述阴离子表面活性剂使得Fe2+和Co2+阳离子能够附着到核六角铁氧体颗粒上。当阴离子表面活性剂分散在水中时,亲水头可能会亲水,而疏水尾则会憎水。可供选择的阴离子表面活性剂可以是十二烷基硫酸钠(SDS)、十二烷基硫酸钠(sodium laurilsulfate或sodium laurylsulfate)(SLS),当然其他阴离子表面活性剂也是可能的。SDS的水溶液已经常用于分散或者悬浮磁铁矿(Fe3O4)颗粒。需要指出的是,M型六角铁氧体核颗粒已经是氧化物。因此,六角铁氧体不是Fe和Co,其化学性质稳定。在将FeCl2·4H2O和CoCl2·6H2O这两种初始的壳材料添加到该溶液中之前,可通过氩气吹扫来对含有阴离子表面活性剂的溶液进行脱气。优选的持续进行该吹扫,直到涂层过程结束。以期望的流动速率将还原剂NdBH4滴入到该溶液中,过渡金属离子从而达到它们的金属状态。对涂敷有Co-Fe的M型六角铁氧体进行过滤,并在大约80℃的烘箱中进行干燥。该相同的过程也适用于在惰性气体环境下制造MnAl和MnBi核-壳纳米颗粒。在其它实施方式中,其他的技术可用于制造纳米磁性颗粒。
Claims (3)
1.一种核-壳纳米磁体颗粒(12),包括:
硬磁性材料的核(14)和
用于包围所述核的软磁性材料的壳(15),
其中,所述壳的厚度小于40纳米,并且小于所述核的布洛赫畴壁厚度的两倍。
2.根据权利要求1所述的核-壳纳米磁体颗粒,其中,围绕着所述核的所述壳的厚度是均匀的。
3.根据权利要求1所述的核-壳纳米磁体颗粒,其中,所述核不包括稀土元素。
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