CN100386288C - 具有改良性能的经济铁氧体型磁体 - Google Patents

具有改良性能的经济铁氧体型磁体 Download PDF

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CN100386288C
CN100386288C CNB028206649A CN02820664A CN100386288C CN 100386288 C CN100386288 C CN 100386288C CN B028206649 A CNB028206649 A CN B028206649A CN 02820664 A CN02820664 A CN 02820664A CN 100386288 C CN100386288 C CN 100386288C
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ferrite
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A·莫雷尔
P·特诺德
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Abstract

本发明涉及包含式为M1-xRxFe12-yTyO19的磁铅石相的铁氧体型磁体，其中：M代表选自Sr，Ba，Ca和Pb的至少一种元素；R代表选自稀土元素和Bi的至少一种元素；T代表选自Co，Mn，Ni，Zn的至少一种元素；0.15＜x＜0.42；0.50＜α＝y/x＜0.90；这样获得一种铁氧体磁体，该磁体同时具有减小的元素T含量和至少580，且优选至少585的综合性能指标GIP＝Br+0.5Hk，Br是以mT表示的剩余磁感应，Hk对应于当B＝0.9Br时的磁场H，以kA/m表示。

Description

具有改良性能的经济铁氧体型磁体
发明背景
本发明与含M磁铅石相的六方晶系铁氧体型磁体的领域相关。
现有技术
包含磁铅石相且具有式MFe12O19的铁氧体型磁体已为人所知，式中M＝Sr，Ba，Ca，Pb等。
还知道具有式(M1-xRx)O·n[(Fe12-yTy)2O3]的这种类型的磁体。
例如欧洲申请EP 0 964 411 A1描述了磁体，该磁体中：
-M是一种选自Sr和/或Ba的元素，
-R是一种属于稀土元素的元素，
-T是一种选自Co，Mn，Ni和Zn的元素，其中：
-x的范围是0.01至0.4，
-y的范围是[x/(2.6n)]至[x/(1.6n)]，
-且n的范围是5至6。
此外，欧洲申请EP 0 905 718 A1描述了具有式M1-xRx(Fe12-yTy)zO19这种类型的磁体，其中：
-M是一种选自Sr，Ba，Ca和Pb的元素，且基本上为Sr，
-R是一种属于稀土元素的元素或Bi，且基本上为La
-T是Co或Co和Zn，其中：
-x的范围是0.04至0.9，
-y的范围是0.04至0.5，同时x/y的范围是0.8至20，和
-z的范围是0.7至1.2。
欧洲专利申请EP 0 758 786 A1，EP 0 884 740和EP 0 940 823 A1，US 6 258 290和EP 1 150 310 A1中也描述了这种类型的磁体。
这种磁体的制造典型地包括以下步骤：
a)或使用湿法形成分散体，或通过干法形成微粒来形成原料的混合物，
b)将或以分散体形式或以微粒形式的所述混合物放入煅烧炉中，在约1250℃煅烧该混合物以形成包含期望的磁铅石相的熟料，
c)湿磨该熟料直到获得一种具有大约1μm颗粒尺寸的微粒的水性分散体，该分散体以浆料的形式且包含约70％的干性提取物(dryextract)，
d)在约1特斯拉的取向磁场和30至50MPa的压力下将该浆料浓缩并压制以获得生坯(green compact)，该生坯是各向异性的且典型地包含87％的干性提取物，
e)干燥并除去残余的水之后，烧结该生坯，
f)最后机械加工以获得预定形状的磁体。
此外还知道如那些在以申请人名义的法国申请N°99 10295和9915093中描述的制造方法。
产生的问题
由现有技术的陈述中的铁氧体型磁体，典型为Sr1-xLaxFe12-yCoyO19型的磁体，产生的问题有两个方面：
第一铁替代元素是一种昂贵的产品，典型为钴，
第二虽然已知的磁体具有高的磁性，磁性典型地使用性能指标IP＝Br+0.5HcJ来测量，其中Br代表剩余磁感应(mT)且HcJ代表矫顽磁场(kA/m)，一些磁体的应用要求磁体具有尽可能为方形的磁化曲线Br＝f(H)，这个方形度典型地通过比值hk＝Hk/HcJ给定，Hk是提供0.90Br的感应的反向磁场。Hk实际上对应于从该磁场起认为磁性损失是不可逆的磁场。
本发明打算获得的铁氧体型磁体，除通常高的磁性之外，该磁体同时是低成本而且其由比值hk＝Hk/HcJ给定的方形度比在相同操作条件下获得的磁体更大，且典型为至少0.95。
已注意到Hk因子最显著的重要性，由此提出一个综合性能指标GIP＝Br+0.5Hk以便考虑到最后的磁性以及磁化与退磁曲线的方形度。本发明打算获得具有至少580的综合性能指标GIP的磁体，优选至少585和甚至至少590。
发明描述
根据本发明，该铁氧体型磁体具有式为M1-xRxFe12-yTyO19的磁铅石相结构(M结构的六方铁氧体)，其中：
M代表选自Sr，Ba，Ca和Pb的至少一种元素，
R代表选自稀土元素和Bi的至少一种元素，
T代表选自Co，Mn，Ni，Zn的至少一种元素，
0.15＜x＜0.42，
0.50＜α＝y/x＜0.90，
这样获得了一种磁体，该磁体同时具有低百分比的元素T和至少580，且优选至少585的综合性能指标GIP＝Br+0.5Hk，Br是以mT表示的剩余磁感应，Hk对应于其中B＝0.9Br时的磁场H，以kA/m表示，Br是剩余磁感应。
除在永磁体领域，且更具体为具有磁铅石或六方铁氧体结构的铁氧体型磁体，基本结构为MFe12O19的永磁体(其中通过其它元素代替M＝Sr，Ba，Pb，Ca且具有化学式M1-xRxFe12-yTyO19，其中R代表元素Bi或稀土元素，而T代表Mn，Co，Ni，Zn的一种元素)领域中的研究以外，本申请人继续其研究并首先考虑改良以性能指标IP＝Br+0.5HcJ描述的磁性能，Br代表以mT表示的剩余磁感应而HcJ是以kA/m表示的矫顽磁场；其次考虑改良永磁体的第二个重要的参数，即通常由hK＝Hk/HcJ(％)表征的退磁曲线的方形度，Hk对应于当B＝0.9Br时的磁场H，以获得至少等于0.95的hK。
实际上，申请人观察到使用许多类型的取代物，例如其中R＝La且T＝Co，方形度hK急剧恶化，这会严重限制这些磁体的应用。
所进行的研究因此打算在不恶化磁体的综合磁性能IP的情况下大大提高方形度hK，以便获得至少等于580且优选至少585和甚至至少590的综合性能指标GIP。
通常，为制造原料的混合物，取铁氧体磁体式的变量“x”等于变量“y”以便遵守磁体的电中性，该磁体的式假定为(其中R＝La且T＝Co)：
Sr1-x 2+Lax 3+Fe12-x 3+Cox 2+O19
测定所获得的这些铁氧体磁体的方形度后，关于取代率x＝y，申请人观察到如图1a中所示的，随着x＝y增加且当至少增加到x＝y＝0.3时，方形度的恶化。
申请人还观察到，如图1b所示，各向异性磁场Ha和矫顽磁场HcJ(kA/m)相对于取代率x＝y发生变化。因此产生如果由各向异性磁场Ha决定的固有磁性随x＝y增加，另一方面由矫顽磁场具体决定的铁氧体的宏观磁性在大约x＝y＝0.2处表现出一个最佳点。
另外，在对以上所得的其中x＝y的磁体进行X-射线衍射分析后，申请人注意到一个尖晶石Co相(CoFe2O4)的异常存在，然而镧似乎完全取代了锶。
申请人首先假定认为部分Co元素可能不参加铁氧体本身的形成，而且这可能导致铁氧体中初始的Fe3+转变为Fe2+。
为验证这个假设，检测了当x＝y范围为0至0.4时所得的铁氧体磁体的电阻率。申请人观察到电阻率的一个快速下降(参见图2)。此外还假定这个减少的电阻率可能涉及离子对Fe2+-Fe3+越来越多的出现，考虑到通过Fe2+和Fe3+离子之间电子跳跃的可能传导。
申请人还假设所述Co尖晶石相的存在可能是所测试铁氧体磁体的方形度hK恶化的原因。
为了解决产生的问题，正是上述假设上的研究工作引导申请人探究铁氧体的领域，该铁氧体：
被弱取代，
其中x与y不同。
在完全不可预料的意义上，申请人发现图3，4a和4b中所示的多边形区域可以解决所产生的问题。
如图5e中所示，所有其它情况相同，使用本发明可以既减少铁氧体磁体中T元素的含量-一种通常昂贵的元素-又提高该铁氧体磁体综合的性能。
附图描述
图1a是表示纵坐标上的方形度hK(％)相对于横坐标上x和y的变化的曲线图，对于具有式Sr1-xLaxFe12-yCoyO19且其中x＝y的铁氧体。
图1b是说明左侧纵坐标上的矫顽磁场HcJ(kA/m)-曲线点为正方形，和右侧纵坐标上的各向异性磁场Ha(kA/m)-曲线点为三角形-相对于横坐标上的x和y变化的曲线图，对于式为Sr1-xLaxFe12-yCoyO19且其中x＝y的铁氧体，。
图2是说明纵坐标(logρ以Ωcm为单位)上的电阻率相对于横坐标上的x和y变化的曲线图，对于式为Sr1-xLaxFe12-yCoyO19且其中x＝y的铁氧体。
图3是横坐标上为x系数且纵坐标上为y系数(铁氧体分子式M1-xRxFe12-yTyO19的系数)来说明本发明的不同区域的曲线图，主要的区域是下列直线限定的区域：
x1＝0.15和x2＝0.42
α1＝0.50和α2＝0.90
其它次级区域通过其它直线限定：
x＝0.17-0.22-0.32
α＝0.60-0.65-0.75-0.80
图3列出了所进行的不同测试，不同系列的测试标记为：A代表x＝0，B代表x＝0.15，C代表x＝0.20，d代表x＝0.30且E代表x＝0.40。
图4a和4b类似于图3且对应于限定的区域：
-图4a中的多边形区域(有阴影线的)由以下直线限定：
x1＝0.17和x2＝0.32
α1＞0.65和α2＜0.90
-图4b中在前述区域之内的多边形区域(有阴影线的)由以下直线限定：
x1＝0.17和x2＝0.22
α1＞0.65和α2＜0.90
一个更受限制的区域(交叉阴影线的)由以下直线限定：
x1＝0.17和x2＝0.22
α1＞0.65和α’2＜0.80
图5a至5e表示所得结果(在纵坐标上)与参数α＝y/x的关系，对于相应在1180℃温度下烧结的磁体的测试B1-1，C1-1，C3-1，C4-1，C5-1和D1-1。
图5a在纵坐标上表示以mT表示的剩余磁感应Br。
图5b在纵坐标上表示对应于其中B＝0.9Br的以kA/m表示的磁场H的Hk，Br是剩余磁感应。
图5c，在纵坐标上，表示以kA/m表示的矫顽磁场HcJ。
图5d，在纵坐标上，表示性能指标IP＝IP＝Br+0.5HcJ。
图5e，在纵坐标上，表示综合性能指标GIP＝Br+0.5Hk。
图6给出退磁曲线的例子，对于测试C1-1为虚线，且对于C3-1为实线。
发明详述
本发明的区域，特别是那些由系数x和α的范围定义的区域，在申请人进行的许多研究和测试之后确定，在示范性实施方案中给出某些这样的区域。
作为一般规则，取系数α不大于0.90以便同时获得元素T含量的显著减少和综合性能GIP的增加，正如出人意料的观察到的。
另一方面，由于综合性能GIP的恶化，申请人观察到α＝0.5的下限。
类似地，关于系数x，其可以根据本发明在0.15至0.42的范围上变化。特别是由于非常高含量的元素T，申请人注意到超出x＝0.2不是有利的。即使可以使用高x获得良好的综合性能，这不是必然有利的，因为只要使用更低的x值能获得相同或更好的性能，并因而能在铁氧体中包含较低浓度的元素T。如以下说明，优选不超过x＝0.32的值。
另一方面，存在系数x(以及y)可能减少的一个下限而且一旦x典型小于0.15，申请人观察到磁性能的极大降低-这种降低不能补偿改良的方形度或成本减少。
根据本发明，具有式M1-xRxFe12-yTyO19的磁体有利的满足以下条件：0.15＜x＜0.32。
本发明的这个次级区域如图3和4a中所示。
另一个最优选的次级区域对应于以下条件：0.17＜x＜0.22。
这个区域如图4b所示。
这些测试表明在所进行的具有x大于0.15且典型大于0.17的测试中获得了最好的结果。
同样，如果使用x＝0.4获得极好的结果，这些结果不会好于那些使用x＝0.3获得的结果。另外，考虑到具有x＝0.4的磁体比那些x＝0.3(对一个相同的系数α)的磁体昂贵很多，优选x不超过0.32。
类似地，由于在具有x＝0.3和x＝0.2的测试之间几乎没有发现性能上的差异，发现允许其中x不超过0.22的磁体是有利的以便获得特别经济的铁氧体磁体。
其它次级区域由系数α＝y/x限定，如图3至4b中所示。
这些测试表现了磁体的优点，该磁体具有关系：0.60＜α＝y/x＜0.90，且优选0.65＜α＝y/x＜0.90，后面的区域如图4a中所示。
一个值得注意的次级区域同样是由关系0.60＜α＝y/x＜0.80定义的区域，且优选由0.65＜α＝y/x＜0.80定义的区域，后面的区域如图4b中所示。
注意到测试C3的特别值得注意，该测试使极低的La含量与高性能相一致，一个其中α＝y/x的范围为0.67至0.77的狭窄区域是特别有利的。在技术和经济上是最重要的区域是通过0.17＜x＜0.22和0.67≤α≤0.77定义的。
使用本发明可以方便的获得具有低T元素含量的铁氧体，其中系数y不超过0.16，甚至不超过0.15，然而仍保持非常高水平的综合性能。
另外注意到可以在一定烧结条件下获得本发明的铁氧体是重要的，特别是在一个相对低的烧结温度下，具体为1220℃或更低，且典型为低于1200℃，从经济的观点上这是有利的。
本发明的所有铁氧体测试是以M＝Sr，R＝La且T＝Co进行的。然而，本发明不限于这种具体的铁氧体。
例如，元素M可以是Sr和Ba的混合物，Sr的原子百分比范围是10％至90％且Ba的原子百分比范围是90％至10％，而且其中R＝La且T＝Co。
在本发明的另一个实施方案中，T所指代的元素的原子浓度满足条件[Co]/([Co]+[Zn]+[Mn]+[Ni])＞30％，优选＞50％且更优选≥70％。在这个实施方案中，也可能选择M＝Sr和R＝La。
本发明的又一个主题是在一个应用中的根据本发明的铁氧体磁体的用途，该应用要求：
-或者磁体同时具有大于590mT的磁性能指标IP和强的退磁曲线方形度，该方形度典型具有至少95％的比值hK＝Hk/HcJ(％)。
-或者具有至少580，且优选至少585的综合性能指标GIP的磁体。
本发明的又一个主题是一种用于制造本发明的磁体的方法，其中：
a)形成元素M，R，T和Fe的前体的混合物，该混合物对应于式M1-xRxFe12-yTyO19的化学计量且符合条件：0.15＜x＜0.42和0.50＜α＝y/x＜0.90，
b)在温度和时间典型为大约1250℃和2小时的条件下煅烧所述混合物以获得熟料，
c)在可选加入添加剂的条件下将所述熟料粉碎，以便获得一种具有小于1μm的平均颗粒尺寸的细颗粒粉末。
d)使所述微粒经受一个典型为1T的取向磁场并在典型为1150至1250℃范围的温度下进行烧结，选择所述温度以便可能获得一种磁体，该磁体：
-或具有典型为至少580，且优选至少585的最大综合性能指标GIP，
-或同时具有典型为至少590mT的性能指标IP＝Br+0.5HcJ，和典型为至少95％的退磁曲线的方形度hK＝Hk/HcJ(％)，Hk对应于当B＝0.9Br时的磁场H。
也可以将以发明者名义的法国申请n°99 10295和99 15093中所描述的制造方法所提供的教导应用到本发明。
下列实施例通过举例说明的方式给出而且不是限制性的。
实施例
对于实验室测试使用前述的方法：
步骤a：
制备对应于组成Sr1-xLaxFe12-yCoyO19的铁氧体的化学计量比的湿混合物，对x和y使用下列值：
  测试标记   X   Y   X/Y＝α(％)
  A0   0   0   -
  A1   0,10   0,10   100
  A2   0,10   0,075   75
  A3   0,10   0,05   50
  B1   0,15   0,15   100
  B2   0,15   0,132   88
  B3   0,15   0,112   75
  B4   0,15   0,1   63
  B5   0,15   0,75   50
  C1   0,2   0,2   100
  C2   0,2   0,176   88
  C3   0,2   0,15   75
  C4   0,2   0,126   63
  C5   0,2   0,1   50
  D1   0,30   0,30   100
  D2   0,30   0,264   88
  D3   0,30   0,225   75
  D4   0,30   0,189   63
  D5   0,30   0,15   50
  E1   0,40   0,40   100
  E2   0,40   0,352   88
  E3   0,40   0,30   75
  E4   0,40   0,252   63
  E5   0,40   0,2   50
使用下列粉料作为原料：
对于元素Sr：SrCO3
对于元素La：以粉末形式且具有1.07m2/g的比表面积(BET方法)和0.93μm平均颗粒直径的La2O3，使用Fisher方法测量其直径，
对于元素Fe：以粉末形式且具有3.65m2/g的比表面积和0.96μm平均颗粒直径的Fe2O3，
对于元素Co：以粉末形式且具有0.96m2/g的比表面积和2.1μm平均颗粒直径的Co3O4。
将该粉料在搅拌器中在水相中混合，然后将该混合物过滤并干燥。使用水作为粘结剂(水分含量为14％重量比)对所得粉料进行球化(pellet)并达到2.5kg/dm3的密度，在煅烧前对将小球进行干燥。
步骤b)：在1250℃下煅烧该粉末混合物2小时。
获得一种具有下列性质的熟料：
  标记   密度＝d(g/cm<sup>3</sup>)   HcJ(kA/m)＝矫顽磁场   Br/d(mT.cm<sup>3</sup>/g)剩余磁感应<sup>＊</sup>
  A0   2,91   301   44,7
  A1   2,87   299   45,1
  A2   2,90   311   44,8
  A3   3,01   306   45,0
  B1   2,85   333   44,6
  B2   3,01   315   44,5
  B3   3,04   313   44,1
  B4   3,03   320   43,9
  B5   3,1   315   43,5
  C1   2,74   355   46,7
  C2   2,97   347   44,1
  C3   2,74   354   45,6
  C4   2,91   364   43,6
  C5   2,87   359   46,3
  D1   2,97   371   43,8
  D2   3,01   374   44,5
  D3   2,85   405   45,3
  D4   2,9   390   44,8
  D5   2,91   361   45,7
  E1   2,81   392   45,2
  E2   2,94   421   44,1
  E3   2,75   436   44,7
  E4   2,80   443   43,9
  E5   2,81   457   43,8
＊相对于煅烧密度的剩余磁感应-与反应产量成比例。
步骤c)：在湿介质中使用下列添加剂粉碎所得熟料，按重量比：
0.52％SiO2(以20％浓度的水溶液形式)
0.86％CaCO3
0.95％SrCO3
所得糊剂的颗粒尺寸：该颗粒具有0.58μm和0.62μm之间的平均直径以及10.3和11.2m2/g之间的BET比表面积，因而最后的磁性能是可比较的。
步骤d)：
粉碎之后，使颗粒经受一个典型为1T的取向磁场，然后在1180℃，1205℃，1220℃或1240℃的温度下烧结。
相对于烧结温度T℃和25分钟烧结时间的结果如下：
  测试标记   T℃   Br(mT)   HcJ(kA/m)   Hk(kA/m)  IP＝Br+HcJ/2   h<sub>K</sub>＝Hk/HcJ(％)   GIP＝Br+Hk/2
  A0-1   1180℃   410   272   267   546   98   543,5
  A1-1   ″   411   328   312   575   95,1   567
  A2-1   ″   418   325   314   581   96,6   575
  A3-1   ″   414   311   296   570   95,2   569
  B1-1   ″   413   360   332   593   92   579
  B2-1   ″   420   347   331   594   95,4   586
  B3-1   ″   417   348   348   591   95,1   583
  B4-1   ″   418   335   319   586   95,2   578
  B5-1   ″   419   321   309   580   96,3   574
  C1-1   ″   413   371   321   599   86   573,5
  C2-1   ″   420   376   350   608   93,1   595
  C3-1   ″   412   369   353   597   96   588,5
  C4-1   ″   411   353   330   588   93   576
  C5-1   ″   411   310   293   566   94   557,5
  D1-1   ″   419   350   278   594   79   558
  D2-1   ″   420   360   296   600   82,2   568
  D3-1   ″   423   368   336   607   91,3   591
  D4-1   ″   413   356   339   591   95,2   583
  D5-1   ″   418   302   278   569   92,1   557
  E1-1   ″   410   277   238   549   86   529
  E2-1   ″   425   333   268   592   80,5   559
  E3-1   ″   417   362   292   598   81   563
  E4-1   ″   418   350   322   593   92   579
  E5-1   ″   415   291   263   561   90   546,5
  A0-2   1205℃   410   265   257   542   94   538,5
  A1-2   ″   425   316   307   583   97,2   579
  A2-2   ″   421   314   307   578   97,8   575
  A3-2   ″   417   302   293   568   97,0   564
  B1-2   ″   417   350   330   592   94   582
  B2-2   ″   413   336   321   581   95,5   574
  B3-2   ″   417   335   325   585   97   580
  B4-2   ″   421   325   316   584   97,2   579
  B5-2   ″   420   306   298   573   97,4   569
  C1-2   ″   421   358   320   600   89   581
  C2-2   ″   419   365   344   602   94,2   591
  C3-2   ″   419   356   344   597   97   591
  C4-2   ″   416   349   340   592   97   586
  C5-2   ″   417   328   319   581   97   576,5
  D1-2   ″   419   350   278   594   79   558
  D2-2   ″   427   355   337   605   94,9   596
  D3-2   ″   427   355   337   605   94,9   596
  D4-2   ″   425   342   333   596   97,4   592
  D5-2   ″   427   316   308   585   97,5   581
  E1-2   ″   426   252   235   552   93   543,5
  E2-2   ″   427   336   272   595   81   563
  E3-2   ″   426   352   293   602   83   572,5
  E4-2   ″   420   345   323   593   94   581
  E5-2   ″   425   311   298   581   96   574
  A1-3   1220℃   423   310   297   578   95,8   572
  A2-3   ″   421   307   295   575   96,1   569
  A3-3   ″   419   296   287   567   97,0   563
  B1-3   ″   420   342   332   600   97   586
  B2-3   ″   424   332   320   590   96,4   578
  B3-3   ″   420   326   316   583   96,9   578
  B4-3   ″   423   317   307   582   96,8   577
  B5-3   ″   424   303   295   576   97,4   572
  C1-3   ″   425   353   321   602   91   585,5
  C2-3   ″   421   358   336   600   93,9   589
  C3-3   ″   424   351   339   600   97   593,5
  C4-3   ″   424   342   332   600   97   586
  C5-3   ″   419   324   315   581   97   576,5
  D1-3   ″   429   320   263   589   82,2   561
  D2-3   ″   429   348   308   603   88,5   583
  D3-3   ″   427   353   335   604   94,9   595
  D4-3   ″   426   337   328   595   97,3   590
  D5-3   ″   427   311   300   585   96,5   579
  E2-3   ″   434   332   271   600   81,6   570
  E3-3   1240℃   431   339   297   601   87,5   580
  E4-3   ″   429   335   322   597   96,1   590
  E5-3   ″   428   308   297   582   96,4   577
结论：如果比较具有减小的元素T含量的测试，所有其它情况相同，即相同的x值和特别是相同的烧结温度(参见实施例对C1-1和C3-1，C1-2和C3-2，C1-3和C3-3)，显然使用本发明可能同时获得：
-价格更低的铁氧体，由于本发明典型地使得30％的Co被铁取代，而且使用相对较低的磁体烧结温度，
-性能全面更好的铁氧体。
具体地，可以注意到在测试C2-2，C3-3和D2-2中获得具有GIP＞590的非常高的性能水平，最经济的铁氧体是对应于测试C3-3的铁氧体。

Claims (4)

1.一种制造包含磁铅石相的铁氧体型磁体的方法，该磁铅石相具有式M1-xRxFe12-yTyO19，其中：
-M代表选自Sr，Ba，Ca和Pb的至少一种元素，
-R代表选自稀土元素和Bi的至少一种元素，
-T代表选自Co，Mn，Ni，Zn的至少一种元素，
所述方法包括下列步骤：
a)形成元素M，R，T和Fe的前体的混合物，该混合物对应于式M1-xRxFe12-yTyO19的化学计量并符合条件：0.17≤x≤0.22和0.67＜α＝y/x＜0.77，
b)煅烧所述混合物以获得熟料，
c)在可选地加入添加剂的条件下对所述熟料进行粉碎，以便获得一种具有小于1μm的平均颗粒尺寸的细颗粒粉末，
d)使所述颗粒经受取向磁场并在1150至1250℃范围的温度下进行烧结，选择所述温度以便获得一种磁体，该磁体：
-或具有至少585的最大综合性能指标GIP，
-或同时具有至少590mT的性能指标IP＝Br+0.5HcJ，和至少95％的退磁曲线的方形度指标hK＝Hk/HcJ(％)，Hk对应于当B＝0.9Br时的场H。
2.权利要求1的方法，其中步骤d)中的烧结温度不超过1220℃。
3.权利要求2的方法，其中步骤d)中的烧结温度小于1200℃。
4.由任意权利要求1-3的方法可以获得的产品。
CNB028206649A 2001-10-19 2002-10-14 具有改良性能的经济铁氧体型磁体 Expired - Fee Related CN100386288C (zh)

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Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MXPA06015044A (es) * 2004-09-10 2007-04-25 Neomax Co Ltd Material magnetico de oxido e iman sinterizado.
DE602006021780D1 (de) * 2005-11-25 2011-06-16 Hitachi Metals Ltd Magnetisches material auf oxidbasis, herstellungsverfahren dafür, gesinterter ferritmagnet und herstellungsverfahren dafür
US7919007B2 (en) * 2005-12-19 2011-04-05 Tdk Corporation Ferrite magnetic material
JP5316737B2 (ja) * 2006-01-11 2013-10-16 Ｔｄｋ株式会社 フェライト磁性材料
HUE029918T2 (en) * 2008-12-18 2017-04-28 Tridelta Hartferrite Gmbh Magnetically hard material
KR101082389B1 (ko) 2011-05-31 2011-11-11 쌍용머티리얼 주식회사 마그네토플럼바이트형 페라이트 자성재료 및 이로부터 유도된 세그멘트형 영구자석
CN103058641B (zh) * 2011-12-14 2014-04-23 南京梅山冶金发展有限公司 一种制备非稀土高磁性永磁铁氧体材料的方法
JP5650270B2 (ja) 2013-03-29 2015-01-07 株式会社リケン マグネトプランバイト型六方晶フェライト及びノイズ抑制シート
CN104003704B (zh) * 2014-02-27 2015-08-19 横店集团东磁股份有限公司 一种无镧钴永磁铁氧体的制备方法
CN104072124A (zh) * 2014-06-30 2014-10-01 中钢天源(马鞍山)通力磁材有限公司 一种直流变频电机用永磁铁氧体磁体的制备方法
CN107324406B (zh) * 2017-07-31 2019-09-24 电子科技大学 一种复合改性的锶铁氧体粉体的制备方法
WO2021010571A1 (ko) * 2019-07-15 2021-01-21 한양대학교 에리카산학협력단 육각판상 형태의 페라이트 구조체 및 그 제조방법
JP2021155317A (ja) * 2020-03-30 2021-10-07 Tdk株式会社 フェライト焼結磁石および回転電気機械
KR20220026315A (ko) * 2020-08-25 2022-03-04 현대자동차주식회사 GHz 대역의 전자파 흡수입자 및 이를 포함하는 전자파 흡수재
KR20220026316A (ko) * 2020-08-25 2022-03-04 현대자동차주식회사 GHz 대역의 전자파 흡수입자 및 이를 포함하는 전자파 흡수재
CN112299836A (zh) * 2020-11-25 2021-02-02 南通冠优达磁业有限公司 一种高频低损耗软磁铁氧体材料及制备方法
CN115849894B (zh) * 2022-11-07 2023-11-10 安徽龙磁科技股份有限公司 一种高磁特性永磁铁氧体材料及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2784498A1 (fr) * 1999-11-30 2000-04-14 Ugimag Sa Procede de fabrication d'aimants du type ferrite
US6258290B1 (en) * 1997-09-19 2001-07-10 Tdk Corporation Magnet powder, sintered magnet, process for producing them, bonded magnet, motor and magnetic recording medium

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2897871B2 (ja) * 1995-08-11 1999-05-31 ティーディーケイ株式会社 磁石粉末、焼結磁石、ボンディッド磁石および磁気記録媒体
WO1998038654A1 (fr) * 1997-02-25 1998-09-03 Tdk Corporation Materiau magnetique a base d'oxyde, particule de ferrite, aimant obtenu par frittage, aimant issu d'une liaison, support d'enregistrement magnetique et moteur
FR2785281B1 (fr) * 1999-07-05 2001-04-27 Ugimag Sa Procede de fabrication de poudres ou biscuits d'hexaferrites de type m
JP2001135512A (ja) * 1999-11-08 2001-05-18 Sumitomo Special Metals Co Ltd フェライト磁石粉末および該磁石粉末を用いた磁石およびそれらの製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6258290B1 (en) * 1997-09-19 2001-07-10 Tdk Corporation Magnet powder, sintered magnet, process for producing them, bonded magnet, motor and magnetic recording medium
FR2784498A1 (fr) * 1999-11-30 2000-04-14 Ugimag Sa Procede de fabrication d'aimants du type ferrite

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