CN107337447A - 一种低成本永磁铁氧体及其制备方法 - Google Patents

一种低成本永磁铁氧体及其制备方法 Download PDF

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CN107337447A
CN107337447A CN201710548213.1A CN201710548213A CN107337447A CN 107337447 A CN107337447 A CN 107337447A CN 201710548213 A CN201710548213 A CN 201710548213A CN 107337447 A CN107337447 A CN 107337447A
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magnet ferrite
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CN107337447B (zh
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丁伯明
胡良权
叶华
吕舒宏
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Hengdian Group DMEGC Magnetics Co Ltd
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Abstract

本发明属于磁性材料及其制备技术领域。本发明公开了一种低成本永磁铁氧体,其主相为A1‑xRxFe2n‑yTyO19;本发明还公开了一种低成本永磁铁氧体的制备方法,在永磁铁氧体的制备过程中,在预烧料中添加了一定含量的红料。本发明中的永磁铁氧体具有更高的磁性能,能够适应当下电子元器件小型化、高磁学性能等趋势;本发明中的制备方法,在预烧料中添加了一定量的红料,可以起到增加产品致密度并起到细化晶粒的作用,能够在较大程度上提高材料的磁性能。

Description

一种低成本永磁铁氧体及其制备方法
技术领域
本发明涉及磁性材料及其制备技术领域,尤其是涉及一种低成本永磁铁氧体及其制备方法。
背景技术
作为由氧化物形成的永磁材料,熟知的有六方晶系的M型(磁铅石型)Sr铁氧体或Ba铁氧体。由这些铁氧体形成的铁氧体磁性材料,是以永磁铁氧体烧结体或粘结永磁体形式而得到供应的。近年,随着电子零部件朝小型化、高性能化发展,对于永磁铁氧体材料,也要求其小型化且具备高的磁性能。一般来说,永磁铁氧体的磁性指标多使用剩余磁感应强度(Br)及内禀矫顽力(Hcj),并且将这两个指标高的认为其磁性能高。如何提高永磁铁的Br及Hcj出发,技术人员进行过改变成分的相关研究,如通过离子置换,调整摩尔比等进行大量的研究。
中国专利公布号CN102436899A,专利公布日为2012年5月2日,公开了一种铁氧体磁性材料及其制造方法,其通过在常规铁氧体球磨过程中添加碳酸锶和微量的La元素,提高Co在铁氧体中的固溶量,进而提高铁氧体的磁性能,生产成本较低。但是通过这种方法制备而的铁氧体磁性能的提高有限,仍然无法满足当下社会对磁性材料小型化高性能化的要求,虽然调整了其原料组分,但是其磁性能,如剩余磁感应强度Br(约为4000Gs)、内禀娇顽力Hcj(约为4000Oe)等磁性能参数仍旧无法满足现有的需求。
发明内容
为解决上述问题,本发明提供了一种具有较高磁性能能够满足器件小型化要求并具有较低生产成本的用词铁氧体。
本发明还相应地提供了一种低成本永磁铁氧体的制备方法。
为实现上述目的,本发明采用的技术方案如下:
一种低成本永磁铁氧体,其主相为A1-xRxFe2n-yTyO19,其中A为Sr或Ba,R为稀土元素中的至少一种且必须含有La,T为Co、Mn或Zn中的至少一种且必须含有Co;同时,0.05≤x≤0.5,0.02≤y≤0.5,5.3≤n≤6.1。
作为优选,R为La和Pr,其中La和Pr的化学计量比为(0.9:0.1)~(0.5:0.5)。
作为优选,T为Co和Mn,其中Co和Mn的化学计量比为0.9:0.1。
作为优选,T为Co和Zn,其中Co和Zn的化学计量比为0.9:0.1。
一种低成本永磁铁氧体的制备方法,包括以下步骤:
a)备料:按A1-xRxFe2n-yTyO19中各元素的化学计量比称取原料;
b)粉碎:将上述原料湿混球磨,使得球磨后原料的中值粒径D50为0.70~0.80微米,球磨后干燥制得配混粉料;
c)预烧:将配混粉料在8~12Mpa压力下预压处理,并在1200~1300℃下保温1~4小时,获得块状预烧料,将块状预烧料粉碎后制得预烧细粉料;
d)配料:先向预烧细粉料中加入红料,使得红料的重量百分含量为0.15~10wt%,余量为预烧细粉料;再向其中加入无机添加剂和有机添加剂制得混合料,以预烧细粉料和红料的总重量计,无机添加剂的添加量为1.4~2.4wt%,有机添加剂的添加量为0.5~1.0wt%;
e)湿磨:向混合料中加入混合料重量1.4~1.5倍的水,球磨18~22小时;
f)离心调浆:将由球磨后制得的浆料离心脱水并调整浆料浓度制得料浆;
g)成型:将料浆压制成型制得成型体;
h)烧结:将成型体在1200~1260℃空气氛围下烧结60~100分钟制得低成本永磁铁氧体。
作为优选,红料为常温红料或煅烧红料。
作为优选,常温红料由按A1-xRxFe2n-yTyO19中各元素的化学计量比称取原料,然后将原料球磨湿混并烘干后制得。
作为优选,煅烧红料由按A1-xRxFe2n-yTyO19中各元素的化学计量比称取原料,然后将原料混合并湿磨烘干,接着在900℃下热处理2小时制得。
作为优选,无机添加剂为氧化硅和氧化钙的混合物,其中氧化硅与氧化钙的重量比1:1.2~4,有机添加剂为山梨糖醇或葡萄糖酸钙中的一种。
无机添加剂和有机添加剂的添加更主要的是为了改善粉体的成型性能,使得粉料的成型更加的容易,也可以保证成型后材料外形的完整。
作为优选,步骤a中的原料为各元素相应的氧化物或碳酸盐。
采用元素相应的氧化物和碳酸盐作为原料,经高温处理后,可以避免除相应元素和氧元素之外的杂质元素的进入,而且碳酸盐在高温添加下分解生成的氧化物具有更高的活性,能够加快原料之间的反应,也能促进原料之间反应的程度。
作为优选,步骤c中,预烧细粉料的中值粒径D50为3~4.0微米。
作为优选,步骤e中,球磨后浆料的中值粒径为0.70~0.75微米。
作为优选,步骤f中,离心脱水后料浆中的固含量为60~70wt%。
作为优选,步骤g中,料浆压制在14000~15000Oe的磁场下进行,磁场方向为压制方向;压制压力4.5~5.5Mpa。
作为优选,步骤h中,烧结保温前先在100~600℃保温1~2小时。
烧结保温前在较低温度进行热处理以彻底除去成型体中的有机组分。
作为优选,步骤h中,烧结时的升温速率为150℃/h。
本发明与现有技术最大的不同是,通过添加未经过或未经过充分固相反应的“红料”来提高磁性能,现有技术中也有添加所谓红料的技术手段,但是现有技术中的红料一般指由碳酸锶、氧化铁、氧化镧和氧化钴按一定摩尔比配合而成的料,或者是指将按前述原料配合而成的粉料经低温如900摄氏度煅烧而成的粉料,这种方法可以在一定的程度上对材料的磁性能有些改善,但是由于其红料的配比与往往与原组分存在一定的差异,其改善程度有限,甚至在某一些配方中,这些配比不同的红料反而会造成材料磁性能的降低。本发明中采用与基体材料配比相同的未反应或为充分固相反应的红料,可以避免因组分配比的差异造成磁性能的下降,可以更好的提高材料的磁性能。添加红料之所以可以使材料磁性能得到改善的原因是,红料添加后在烧结过程中发生吞并作用,生料粒度较小,填在熟料孔隙中是坯件的密度增大,且加入的生料后产品的收缩率也增大,从而增加了产品密度,有利于剩余磁感应强度Br的提高,同时由于生熟料粒度的差异,在烧结过程中,晶粒将产生非连续性生长,且晶粒很难充分长大,客观上起着细化晶粒的作用,有利于内禀娇顽力Hcj的提高。
因此,本发明具有以下有益效果:
(1)本发明中的永磁铁氧体具有更高的磁性能,能够适应当下电子元器件小型化、高磁学性能等趋势;
(2)本发明中的制备方法,在预烧细粉料中添加了一定量的红料,可以起到增加产品致密度并起到细化晶粒的作用,能够在较大程度上提高材料的磁性能。
具体实施方式
下面结合具体实施方式对本发明的技术方案作进一步的说明。
显然,所描述的实施例仅是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
一种低成本永磁铁氧体,其主相为Sr0.95La0.05Fe10.58Co0.02O19
一种低成本永磁铁氧体的制备方法,包括以下步骤:
a)备料:按Sr0.95La0.05Fe10.58Co0.02O19中各元素的化学计量比称取原料;
b)粉碎:将上述原料湿混球磨,使得球磨后原料的中值粒径D50为0.70微米,球磨后干燥制得配混粉料;
c)预烧:将配混粉料在8Mpa压力下预压处理,并在1200℃下保温1小时,获得块状预烧料,将块状预烧料粉碎至中值粒径D50为3.0微米,制得预烧细粉料;
d)配料:以预烧细粉料与红料的总重量为500g计,先向499.25g预烧细粉料中加入0.75g红料,再向其中加入7.5g无机添加剂和2.5g山梨糖醇制得混合料;红料为常温红料,常温红料由按Sr0.95La0.05Fe10.58Co0.02O19中各元素的化学计量比称取原料,然后将原料球磨湿混并烘干后制得;无机添加剂为氧化硅和氧化钙的混合物,其中氧化硅与氧化钙的重量比1:2.5;
e)湿磨:向混合料中加入混合料重量1.4倍的水,球磨18小时,球磨后浆料的中值粒径为0.70微米;
f)离心调浆:将由球磨后制得的浆料离心脱水并调整浆料中固含量为60wt%,制得料浆;
g)成型:在磁场强度为14000Oe、磁场方向为压制方向的磁场并且压制压力4.5Mpa条件下,将料浆压制成型制得成型体;所得成型体是直径为43.2mm、高度为13mm的圆柱体;
h)烧结:将成型体在1200℃空气氛围下烧结80分钟制得低成本永磁铁氧体;烧结时的升温速率为150℃/h,烧结保温前先在100℃保温2小时。
实施例2
一种低成本永磁铁氧体,其主相为Sr0.75(La0.9Pr0.1)0.25Fe11.75(Co0.9Zn0.1)0.25O19
一种低成本永磁铁氧体的制备方法,包括以下步骤:
a)备料:按Sr0.75(La0.9Pr0.1)0.25Fe11.75(Co0.9Zn0.1)0.25O19中各元素的化学计量比称取原料;b)粉碎:将上述原料湿混球磨,使得球磨后原料的中值粒径D50为0.75微米,球磨后干燥制得配混粉料;
c)预烧:将配混粉料在10Mpa压力下预压处理,并在1250℃下保温3小时,获得块状预烧料,将块状预烧料粉碎至中值粒径D50为3.5微米,制得预烧细粉料;
d)配料:以预烧细粉料与红料的总重量为500g计,先向475g预烧细粉料中加入25g红料,再向其中加入10g无机添加剂和3.75g山梨糖醇制得混合料;红料为常温红料,常温红料由按Sr0.75(La0.9Pr0.1)0.25Fe11.75(Co0.9Zn0.1)0.25O19中各元素的化学计量比称取原料,然后将原料球磨湿混并烘干后制得;无机添加剂为氧化硅和氧化钙的混合物,其中氧化硅与氧化钙的重量比1:3.0;
e)湿磨:向混合料中加入混合料重量1.45倍的水,球磨20小时,球磨后浆料的中值粒径为0.725微米;
f)离心调浆:将由球磨后制得的浆料离心脱水并调整浆料中固含量为65wt%,制得料浆;
g)成型:在磁场强度为14500Oe、磁场方向为压制方向的磁场并且压制压力4.75Mpa条件下,将料浆压制成型制得成型体;所得成型体是直径为43.2mm、高度为13mm的圆柱体;
h)烧结:将成型体在1250℃空气氛围下烧结90分钟制得低成本永磁铁氧体;烧结时的升温速率为150℃/h,烧结保温前先在350℃保温1.5小时。
实施例3
一种低成本永磁铁氧体,其主相为Sr0.5(La0.5Pr0.5)0.5Fe11.7(Co0.9Zn0.1)0.5O19
一种低成本永磁铁氧体的制备方法,包括以下步骤:
a)备料:按Sr0.5(La0.5Pr0.5)0.5Fe11.7(Co0.9Zn0.1)0.5O19中各元素的化学计量比称取原料;
b)粉碎:将上述原料湿混球磨,使得球磨后原料的中值粒径D50为0.80微米,球磨后干燥制得配混粉料;
c)预烧:将配混粉料在12Mpa压力下预压处理,并在1300℃下保温4小时,获得块状预烧料,将块状预烧料粉碎至中值粒径D50为3~4.0微米,制得预烧细粉料;
d)配料:以预烧细粉料与红料的总重量为500g计,先向450g预烧细粉料中加入50g红料,再向其中加入12g无机添加剂和5g葡萄糖酸钙制得混合料;红料为煅烧红料,煅烧红料由按Sr0.5(La0.5Pr0.5)0.5Fe11.7(Co0.9Zn0.1)0.5O19中各元素的化学计量比称取原料,然后将原料混合并湿磨烘干,接着在900℃下热处理2小时制得;无机添加剂为氧化硅和氧化钙的混合物,其中氧化硅与氧化钙的重量比1:4;
e)湿磨:向混合料中加入混合料重量1.5倍的水,球磨22小时,球磨后浆料的中值粒径为0.75微米;
f)离心调浆:将由球磨后制得的浆料离心脱水并调整浆料中固含量为70wt%,制得料浆;
g)成型:在磁场强度为15000Oe、磁场方向为压制方向的磁场并且压制压力5.5Mpa条件下,将料浆压制成型制得成型体;所得成型体是直径为43.2mm、高度为13mm的圆柱体;
h)烧结:将成型体在1260℃空气氛围下烧结100分钟制得低成本永磁铁氧体;烧结时的升温速率为150℃/h,烧结保温前先在600℃保温1小时。
实施例4
一种低成本永磁铁氧体,其主相为Sr0.75La0.25Fe11.8Co0.2O19
一种低成本永磁铁氧体的制备方法,包括以下步骤:
a)备料:按Sr0.75La0.25Fe11.8Co0.2O19中各元素的化学计量比称取原料;
b)粉碎:将上述原料湿混球磨,使得球磨后原料的中值粒径D50为0.75微米,球磨后干燥制得配混粉料;
c)预烧:将配混粉料在10Mpa压力下预压处理,并在1260℃下保温3小时,获得块状预烧料,将块状预烧料粉碎至中值粒径D50为3.5微米,制得预烧细粉料;
d)配料:以预烧细粉料与红料的总重量为500g计,先向480g预烧细粉料中加入20g红料,再向其中加入2.5g氧化硅、9.25g碳酸钙和3.0山梨糖醇制得混合料;红料为常温红料,常温红料由按Sr0.75La0.25Fe11.8Co0.2O19中各元素的化学计量比称取原料,然后将原料球磨湿混并烘干后制得;
e)湿磨:向混合料中加入720g水,球磨20小时,球磨后浆料的中值粒径为0.73微米;
f)离心调浆:将由球磨后制得的浆料离心脱水并调整浆料中固含量为65wt%,制得料浆;
g)成型:在磁场强度为14500Oe、磁场方向为压制方向的磁场并且压制压力5Mpa条件下,将料浆压制成型制得成型体;所得成型体是直径为43.2mm、高度为13mm的圆柱体;
h)烧结:将成型体在1210℃空气氛围下烧结90分钟制得低成本永磁铁氧体;烧结时的升温速率为150℃/h,烧结保温前先在550℃保温1.5小时。
实施例5
一种低成本永磁铁氧体,其主相为Sr0.75La0.25Fe11.8Co0.2O19
一种低成本永磁铁氧体的制备方法,包括以下步骤:
a)备料:按Sr0.75La0.25Fe11.8Co0.2O19中各元素的化学计量比称取原料;
b)粉碎:将上述原料湿混球磨,使得球磨后原料的中值粒径D50为0.75微米,球磨后干燥制得配混粉料;
c)预烧:将配混粉料在10Mpa压力下预压处理,并在1260℃下保温3小时,获得块状预烧料,将块状预烧料粉碎至中值粒径D50为3.5微米,制得预烧细粉料;
d)配料:以预烧细粉料与红料的总重量为500g计,先向480g预烧细粉料中加入20g红料;再向其中加入2.5g氧化硅、9.25g碳酸钙和3.0山梨糖醇制得混合料;红料为煅烧红料,煅烧红料由按Sr0.75La0.25Fe11.8Co0.2O19中各元素的化学计量比称取原料,然后将原料混合并湿磨烘干,接着在900℃下热处理2小时制得;
e)湿磨:向混合料中加入720g水,球磨20小时,球磨后浆料的中值粒径为0.73微米;
f)离心调浆:将由球磨后制得的浆料离心脱水并调整浆料中固含量为65wt%,制得料浆;
g)成型:在磁场强度为14500Oe、磁场方向为压制方向的磁场并且压制压力5Mpa条件下,将料浆压制成型制得成型体;
h)烧结:将成型体在1210℃空气氛围下烧结90分钟制得低成本永磁铁氧体;烧结时的升温速率为150℃/h,烧结保温前先在550℃保温1.5小时。
实施例6
一种低成本永磁铁氧体,其主相为Sr0.8La0.2Fe11.8Co0.2O19
一种低成本永磁铁氧体的制备方法,包括以下步骤:
a)备料:按Sr0.8La0.2Fe11.8Co0.2O19中各元素的化学计量比称取原料;
b)粉碎:将上述原料湿混球磨,使得球磨后原料的中值粒径D50为0.72微米,球磨后干燥制得配混粉料;
c)预烧:将配混粉料在10Mpa压力下预压处理,并在1210℃下保温1小时,获得块状预烧料,将块状预烧料粉碎至中值粒径D50为3.5微米,制得预烧细粉料;
d)配料:以预烧细粉料与红料的总重量为500g计,先向450g预烧细粉料中加入50g红料,再向其中加入2.0g氧化硅、5.2g碳酸钙和3.0g葡萄糖酸钙制得混合料;红料为常温红料,常温红料由按Sr0.8La0.2Fe11.8Co0.2O19中各元素的化学计量比称取原料,然后将原料球磨湿混并烘干后制得;
e)湿磨:向混合料中加入720g水,球磨20小时,球磨后浆料的中值粒径为0.73微米;
f)离心调浆:将由球磨后制得的浆料离心脱水并调整浆料中固含量为65wt%,制得料浆;
g)成型:在磁场强度为14000Oe、磁场方向为压制方向的磁场并且压制压力4.5~5.5Mpa条件下,将料浆压制成型制得成型体;
h)烧结:将成型体在1205℃空气氛围下烧结60分钟制得低成本永磁铁氧体;烧结时的升温速率为150℃/h,烧结保温前先在550℃保温1.5小时。
上述实施例的原料中,Fe2O3为纯度≥99.3wt%,Mn-≤0.25wt%,Cl-≤0.1wt%,颗粒的原始平均粒度≤1.5μm;La2O3为纯度≥99.3wt%,颗粒的原始平均粒度≤5um;Co2O3为Co含量≥72.5wt%,颗粒的原始平均粒度≤3um;SrCO3为纯度≥97wt%,颗粒的原始平均粒度≤1.5um;
磁性能试验:
对比例1:对比例中除不添加红料外,其他设置同实施例4;即称取500g预烧料按照实施例4所记载的制备方法进行永磁铁氧体的制备;
试验方法:将由上述实施例1~6及对比例1中制得的永磁铁氧体的上下表面研磨,然后测量其剩余磁感应强度(Br)、矫顽力(Hcb)、内禀矫顽力(Hcj)、最大磁能积(BH)max。
磁性能试验结果:
对上述实施例1~6及对比例1所得的永磁铁氧体按上述方法进行磁性能测试,所得的磁性能如下表:
序号 Br(Gs) Hcb(Oe) Hcj(Oe) (BH)max
实施例1 4293 4050 4312 4.58
实施例2 4442 3960 4742 4.56
实施例3 4425 3987 4864 4.76
实施例4 4430 4120 4683 4.72
实施例5 4420 3981 4754 4.58
实施例6 4430 4023 4851 4.75
对比例1 4410 3850 4510 4.51
由上述表格经比较可以得知,与对比相比,在预烧料中添加红料之后,制得的永磁铁氧体的磁性能有了一定的提高;同时与背景技术中所记载专利中制得的永磁铁氧体相比较,磁性能有了巨大的提高。
应当理解的是,对于本领域普通技术人员来说,可以根据上述说明加以改进或变换,而所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (9)

1.一种低成本永磁铁氧体,其特征在于:其主相为A1-xRxFe2n-yTyO19,其中A为Sr或Ba,R为稀土元素中的至少一种且必须含有La,T为Co、Mn或Zn中的至少一种且必须含有Co;同时,0.05≤x≤0.5,0.02≤y≤0.5,5.3≤n≤6.1。
2.根据权利要求1所述的一种低成本永磁铁氧体,其特征在于:
所述的R为La和Pr,其中La和Pr的化学计量比为(0.9:0.1)~(0.5:0.5)。
3.根据权利要求1所述的一种低成本永磁铁氧体,其特征在于:
所述的T为Co和Mn,其中Co和Mn的化学计量比为0.9:0.1。
4.根据权利要求1所述的一种低成本永磁铁氧体,其特征在于:
所述的T为Co和Zn,其中Co和Zn的化学计量比为0.9:0.1。
5.一种根据权利要求1~4所述的低成本永磁铁氧体的制备方法,其特征在于包括以下步骤:
a)备料:按A1-xRxFe2n-yTyO19中各元素的化学计量比称取原料;
b)粉碎:将上述原料湿混球磨,使得球磨后原料的中值粒径D50为0.70~0.80微米,球磨后干燥制得配混粉料;
c)预烧:将配混粉料在8~12Mpa压力下预压处理,并在1200~1300℃下保温1~4小时,获得块状预烧料,将块状预烧料粉碎后制得预烧细粉料;
d)配料:先向预烧细粉料中加入红料,使得红料的重量百分含量为0.15~10wt%,余量为预烧细粉料;再向其中加入无机添加剂和有机添加剂制得混合料,以预烧细粉料和红料的总重量计,无机添加剂的添加量为1.4~2.4wt%,有机添加剂的添加量为0.5~1.0wt%;
e)湿磨:向混合料中加入混合料重量1.4~1.5倍的水,球磨18~22小时;
f)离心调浆:将由球磨后制得的浆料离心脱水并调整浆料浓度制得料浆;
g)成型:将料浆压制成型制得成型体;
h)烧结:将成型体在1200~1260℃空气氛围下烧结60~100分钟制得低成本永磁铁氧体。
6.根据权利要求5所述的一种低成本永磁铁氧体的制备方法,其特征在于:
所述的红料为常温红料或煅烧红料。
7.根据权利要求6所述的一种低成本永磁铁氧体的制备方法,其特征在于:
所述的常温红料由按A1-xRxFe2n-yTyO19中各元素的化学计量比称取原料,然后将原料球磨湿混并烘干后制得。
8.根据权利要求6所述的一种低成本永磁铁氧体的制备方法,其特征在于:
所述的煅烧红料由按A1-xRxFe2n-yTyO19中各元素的化学计量比称取原料,然后将原料混合并湿磨烘干,接着在900℃下热处理2小时制得。
9.根据权利要求5所述的一种低成本永磁铁氧体的制备方法,其特征在于:
所述的无机添加剂为氧化硅和氧化钙的混合物,其中氧化硅与氧化钙的重量比1:1.2~4,所述的有机添加剂为山梨糖醇或葡萄糖酸钙中的一种。
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