CN111362686A - 一种六角磁铅石永磁铁氧体材料及其制备方法 - Google Patents
一种六角磁铅石永磁铁氧体材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及铁氧体材料制备技术领域,公开了一种六角磁铅石永磁铁氧体材料及其制备方法,永磁铁氧体材料通式为A1‑x‑yCaxRyFe2n‑ zMzO19,其中:A为Sr或者Sr和Ba,R中包括La,M中包括Co;x为0.15~0.4,y为0.3~0.5,z为0.25~0.45,n为5.3~5.7。制备方法为:配料、预烧、球磨、成型、烧结。本发明以六角Sr铁氧体为基础,采用La3+离子与Ca2+离子共同取代Sr2+的位置,避免了磁体晶体结构的破坏,有效的提高了Co2+离子的代换量,使得制得的永磁铁氧体材料同时获得高的剩磁和内禀矫顽力。
Description
技术领域
本发明涉及铁氧体材料制备技术领域,尤其是涉及一种六角磁铅石永磁铁氧体材料及其制备方法。
背景技术
永磁材料一经磁化即能保持恒定磁性的材料,又称硬磁材料,实际应用中,永磁材料工作于磁滞回线的第二象限退磁部分。常用的永磁材料分为铝镍钴永磁合金、铁氧体永磁、稀土永磁和各种复合永磁材料。
永磁铁氧体磁体是永磁直流电机的关键基础功能材料之一,具有高剩余磁通密度、高矫顽力和高磁能积等特性,能满足强退磁场、低温、高海拔等各种环境下电机的使用要求,具有高的灵敏度和稳定性,可以广泛应用于高功率、高转速、高扭矩的各类电机,如高档汽车电机(ABS电机、启动电机等)、摩托车启动电机、家用电器以及电动工具马达等领域。
最初的永磁铁氧体材料主要是采用具有磁铅石六角结构的锶铁氧体(SrO·6Fe2O3)和钡铁氧体(BaO·6Fe2O3)来制备的。决定烧结永磁铁氧体的磁性能主要有两个参数,即剩余磁通密度(Br)和内禀矫顽力(Hcj)。近年来,随着以La-Co代换为代表的离子代换配方技术的应用,永磁铁氧体性能得到了大幅度的提升,国内外相关科研人员相继开发出剩磁达到4500Gs左右和内禀矫顽力达到5000Oe的永磁铁氧体材料,如中国申请专利200510006196.6、200510118623.X、200510023312.5等。上述三份专利均是以La-Co代换Sr铁氧体为基础(也称为Sr-La-Co铁氧体),大致磁性能在剩磁4200-4500Gs,内禀矫顽力不超过5000Oe。
以Ca作为主要成分的永磁铁氧体(又称Ca铁氧体),只有CaO-Fe2O3和CaO-2Fe2O3是稳定的,类似于典型Sr铁氧体的CaO-6Fe2O3结构上并不稳定。通过La-Co代换,形成的所谓Ca-La-Co铁氧体结构上可以稳定存在,且其磁性能可与普通的Sr-La-Co铁氧体相当。日本公开专利(日本特开2000-223307)公开了一种Ca-La-Co铁氧体,其实施例中显示的较高磁性能可以达到Br为4490Gs,Hcj为4540Oe。
近年来,在Ca-La-Co铁氧体体系上进行其它离子掺杂的研究也比较多,例如中国申请专利201611209131.6通过进一步利用少量F代替O,获得较好磁性能为Br4300Gs,Hcj4450Oe的磁体。中国申请专利201710399787.7通过进一步添加一价碱金属锂、钠或者钾离子进行取代,获得较好磁性能为Br4500Gs左右,Hcj5000Oe左右磁体。
然而无论是单独的Sr-La-Co铁氧体体系,还是目前热门的Ca-La-Co铁氧体体系,都难以同时获得高的剩磁和更高的内禀矫顽力,无法满足越来越高的使用要求。
发明内容
本发明是为了克服现有技术中的永磁铁氧体难以同时获得高的剩磁和更高的内禀矫顽力,无法满足越来越高的使用要求的问题,提供一种六角磁铅石永磁铁氧体材料及其制备方法,以六角Sr铁氧体为基础,采用La3+与Ca2+共同取代Sr2+位置,制得的烧结永磁铁氧体材料的剩磁和内禀矫顽力均比现有技术中的永磁铁氧体有了显著提高。
为了实现上述目的,本发明采用以下技术方案:
一种六角磁铅石永磁铁氧体材料,其特征是,通式为A1-x-yCaxRyFe2n-zMzO19,其中:A为Sr或者Sr和Ba,R中包括La,M中包括Co;x为0.15~0.4,y为0.3~0.5,z为0.25~0.45,n为5.3~5.7。
作为优选,R中还包括Pr、Nd、Bi中的一种或几种。
作为优选,M中还包括Ni和/或Zn。
作为优选,z/y为0.6~1.0。
Sr-La-Co铁氧体磁性能之所以不能得到进一步提高,是因为La-Co代换程度受到限制。众所周知,从Sr铁氧体到Sr-La-Co铁氧体,磁体各项磁性能得到提高,主要是因为Co2+离子部分取代了Fe3+离子,同时为了保持电价平衡,必须利用部分La3+离子取代六角型晶体结构中的Sr2+离子。但是因为La3+的离子半径(0.122nm)比Sr2+离子(0.113nm)稍大,所以随着La-Co取代量的逐步增加,磁体晶体结构会受到影响,容易产生非磁性的LaFeO3,从而影响Sr-La-Co铁氧体磁性能的进一步提高。
因此,本发明中以六角Sr铁氧体为基础,通过添加更多的La-Co来使铁氧体获得更加优良的磁性能,同时为了避免磁体晶体结构的破坏,添加了部分Ca2+,采用La3+离子与Ca2+离子(离子半径0.099nm)共同取代Sr2+的位置,有效的提高了Co2+离子的代换量,使得制得的永磁铁氧体材料同时获得高的剩磁和内禀矫顽力。
本发明还提供了一种上述六角磁铅石永磁铁氧体材料的制备方法,包括如下步骤:
(1)配料:按通式中各元素的摩尔比将含有各元素的原料化合物混合,用湿法混合工艺将混合物粉碎为平均粒度≤0.8μm的混合料浆;
(2)预烧:将混合料浆干燥后在空气中于1150~1280℃下进行预烧得到预烧料;
(3)球磨:向预烧料中加入二次添加物和添加剂,用湿法混合工艺将混合物研磨为平均粒度≤0.65μm的颗粒后得到成型料浆;
(4)成型:调整成型料浆的固含量至65~80wt%后磁场成型得到成型体,成型磁场强度≥13000Gs;
(5)烧结:将成型体先在100~600℃下保温0.5~2h,然后在富氧气氛(即高于空气的含氧量)下进行烧结后得到所述永磁铁氧体材料,烧结温度1100~1300℃,烧结时间0.1~3h。
使用本发明中的方法,可以成功制备出具有上述通式的六角磁铅石永磁铁氧体材料,并且步骤(1)中湿法混合后的混合料浆平均粒度≤0.8μm,避免混合后混合料浆粒度过大,在预烧过程中容易引起预烧不充分,生成M相铁氧体含量过低的情况发生;步骤(2)中将混合料浆干燥后先进行预烧,保证原料化合物可以充分进行固相反应,生成六角晶相,使得得到的预烧料具有良好的质量特性,更好的满足后续工艺的磁性能要求;步骤(3)中成型料浆平均粒度控制在0.65μm以下,避免料浆平均粒度过粗,容易导致烧结后烧结体中晶粒尺寸过粗,影响烧结体的矫顽力;步骤(4)中采用适当的成型磁场强度,防止成型磁场过低造成成型体中磁性颗粒取向度过低,从而影响最终磁体的剩磁;步骤(5)中先在200~400℃下保温0.5~2h,以除去成型料坏中的水分和添加剂,然后在富氧气氛下进行烧结,这将有助于降低烧结体中Fe2+离子的含量,提高烧结体本身的比饱和磁化强度。
因此本发明制备过程中磁性颗粒的取向性好,晶粒尺寸均匀,制得的永磁铁氧体材料同时具有高的剩磁和内禀矫顽力。
作为优选,步骤(1)中所述含有各元素的原料化合物为:Sr、Ba和Ca采用其碳酸盐作为原料化合物;La、Pr和Nd采用其氧化物或者氢氧化物作为原料化合物;Fe、Co、Ni、Zn和Bi采用其氧化物作为原料化合物。采用以上化合物作为原料化合物,各原料化合物中的离子在制备过程中可以有效反应具有本发明中通式的六角磁铅石永磁铁氧体材料。
作为优选,步骤(1)中各原料化合物的平均粒度≤5μm。保证湿法混合后平均粒度可以达到工艺要求。
作为优选,步骤(2)中预烧时间0.1~3h。保证原料化合物可以充分进行固相反应,生成六角晶相,使得得到的预烧料具有良好的质量特性,更好的满足后续工艺的磁性能要求。
作为优选,步骤(3)中所述的二次添加物包括占固含量0.05~2.0wt%的SiO2、0.4~2.0wt%的CaCO3、0~2.0wt%的Al2O3、0~1.5wt%的Cr2O3、0~0.6wt%的ZnO、0.1~1.0wt%的SrCO3及0~0.8wt%的H3BO3,二次添加物的平均粒度≤5μm。添加上述成分和含量的二次添加物,有助于在烧结时抑制晶粒膨胀,增加产品的致密程度,提高磁性颗粒的取向度,从而提高产品的剩磁和内禀矫顽力。
作为优选,步骤(3)中所述的添加剂包括葡萄糖酸钙、聚乙烯醇和山梨糖醇中的一种或几种,添加量为固含量的0.2~1.2wt%。添加上述添加剂可以提高成型料浆的分散性,从而改善磁场成型时的料浆粒子的取向性,提高最终产品的剩磁;添加剂的添加量过大,在后续的烧结过程中容易造成有机物排出不充分,导致烧结体密度下降。成型料浆的平均粒度控制在0.65μm以下,如果料浆平均粒度过粗,容易导致烧结后烧结体中晶粒尺寸过粗,影响烧结体的矫顽力。
因此,本发明的有益效果为:以六角Sr铁氧体为基础,采用La3+离子与Ca2+离子共同取代Sr2+的位置,避免了磁体晶体结构的破坏,有效的提高了Co2+离子的代换量,使得制得的永磁铁氧体材料同时获得高的剩磁和内禀矫顽力。
具体实施方式
下面结合具体实施方式对本发明做进一步的描述。
本发明中各实施例中使用的原料化合物如下:
铁红:其中Fe2O3含量≥99.5wt%,Cl-离子含量≤0.1wt%,颗粒的原始平均粒度为1.6μm;
碳酸锶:其中SrCO3≥98.0wt%,颗粒的原始平均粒度为2.1μm;
碳酸钙:其中CaCO3≥99.0wt%,颗粒的原始平均粒度为4.2μm;
氧化镧:其中La2O3≥99.0wt%,颗粒的原始平均粒度为4.5μm;
三氧化二钴:其中Co2O3≥99.0wt%,颗粒的原始平均粒度为2.5μm;
碳酸钡:其中BaCO3≥98.0wt%,颗粒的原始平均粒度为3.1μm;
氧化镨:其中Pr2O3≥99.0wt%,颗粒的原始平均粒度为4.0μm;
氧化钕:其中Nd2O3≥99.0wt%,颗粒的原始平均粒度为4.0μm;
氧化镍:其中NiO≥99.0wt%,颗粒的原始平均粒度为3.5μm;
氧化锌:其中ZnO≥99.0wt%,颗粒的原始平均粒度为3.5μm。
实施例1:
一种六角磁铅石永磁铁氧体材料,主相式为:Sr0.32Ca0.24La0.44Fe10.87Co0.34O19,其制备方法为:
(1)配料:按主相式中各元素的摩尔比将铁红、碳酸锶、碳酸钙、氧化镧和三氧化二钴放入湿法球磨机中进行混合球磨5h,得到平均粒度为0.8μm的混合料浆;
(2)预烧:将混合料浆在烘箱中进行干燥,然后造球,在空气中1240℃预烧,保温1h,获得颗粒状预烧料;
(3)球磨:称取预烧料450g,添加占固含量0.5wt%的SiO2、0.75wt%的CaCO3,0.4wt%的Cr2O3,再加占固含量0.6wt%的葡萄糖酸钙,然后添加680mL的去离子水作为球磨介质,在高效球磨机中进行24h的湿法粉碎,得到平均粒度为0.64μm的成型料浆;
(4)成型:对成型用料浆进行含水量调整,将料浆的固含量调整为70%,然后成型得到成型体,在压制的同时,在压制方向施加14000Oe的成型磁场,所得成型体是直径为43.2mm、高度为13mm的圆柱体,成型压力为10MPa;
(5)烧结:将成型体先在400℃下保温1h,然后在富氧气氛(即高于空气的含氧量)下进行烧结,升温速度150℃/h,在1220℃保温1.5h,获得所述永磁铁氧体材料。
实施例2:
一种六角磁铅石永磁铁氧体材料,主相式为:Sr0.33Ca0.22La0.35Pr0.10Fe 10.91Co0.34O19,其制备方法为:
(1)配料:按主相式中各元素的摩尔比将铁红、碳酸锶、碳酸钙、氧化镧、氧化镨和三氧化二钴放入湿法球磨机中进行混合球磨5h,得到平均粒度为0.8μm的混合料浆;
(2)预烧:将混合料浆在烘箱中进行干燥,然后造球,在空气中1150℃预烧,保温2h,获得颗粒状预烧料;
(3)球磨:称取预烧料450g,添加占固含量0.5wt%的SiO2、0.75wt%的CaCO3,0.4wt%的Cr2O3,再加占固含量0.6wt%的葡萄糖酸钙,然后添加680mL的去离子水作为球磨介质,在高效球磨机中进行24h的湿法粉碎,得到平均粒度为0.64μm的成型料浆;
(4)成型:对成型用料浆进行含水量调整,将料浆的固含量调整为70%,然后成型得到成型体,在压制的同时,在压制方向施加14000Oe的成型磁场,所得成型体是直径为43.2mm、高度为13mm的圆柱体,成型压力为10MPa;
(5)烧结:将成型体先在400℃下保温1h,然后在富氧气氛(即高于空气的含氧量)下进行烧结,升温速度150℃/h,在1220℃保温1.5h,获得所述永磁铁氧体材料。
实施例3:
一种六角磁铅石永磁铁氧体材料,主相式为:Sr0.34Ca0.25La0.32Nd0.09Fe10.89Co0.35O19,其制备方法为:
(1)配料:按主相式中各元素的摩尔比将铁红、碳酸锶、碳酸钙、氧化镧、氧化钕和三氧化二钴放入湿法球磨机中进行混合球磨5h,得到平均粒度为0.8μm的混合料浆;
(2)预烧:将混合料浆在烘箱中进行干燥,然后造球,在空气中1240℃预烧,保温1h,获得颗粒状预烧料;
(3)球磨:称取预烧料450g,添加占固含量0.5wt%的SiO2、0.75wt%的CaCO3,0.4wt%的Cr2O3,再加占固含量0.6wt%的葡萄糖酸钙,然后添加680mL的去离子水作为球磨介质,在高效球磨机中进行24h的湿法粉碎,得到平均粒度为0.64μm的成型料浆;
(4)成型:对成型用料浆进行含水量调整,将料浆的固含量调整为70%,然后成型得到成型体,在压制的同时,在压制方向施加14000Oe的成型磁场,所得成型体是直径为43.2mm、高度为13mm的圆柱体,成型压力为10MPa;
(5)烧结:将成型体先在400℃下保温1h,然后在富氧气氛(即高于空气的含氧量)下进行烧结,升温速度150℃/h,在1220℃保温1.5h,获得所述永磁铁氧体材料。
实施例4:
一种六角磁铅石永磁铁氧体材料,主相式为:Sr0.35Ca0.23La0.28Pr0.08Nd0.06Fe10.90Co0.3 4O19,其制备方法为:
(1)配料:按主相式中各元素的摩尔比将铁红、碳酸锶、碳酸钙、氧化镧、氧化镨、氧化钕和三氧化二钴放入湿法球磨机中进行混合球磨5h,得到平均粒度为0.8μm的混合料浆;
(2)预烧:将混合料浆在烘箱中进行干燥,然后造球,在空气中1240℃预烧,保温1h,获得颗粒状预烧料;
(3)球磨:称取预烧料450g,添加占固含量0.5wt%的SiO2、0.75wt%的CaCO3,0.4wt%的Cr2O3,再加占固含量0.6wt%的葡萄糖酸钙,然后添加680mL的去离子水作为球磨介质,在高效球磨机中进行24h的湿法粉碎,得到平均粒度为0.64μm的成型料浆;
(4)成型:对成型用料浆进行含水量调整,将料浆的固含量调整为70%,然后成型得到成型体,在压制的同时,在压制方向施加14000Oe的成型磁场,所得成型体是直径为43.2mm、高度为13mm的圆柱体,成型压力为10MPa;
(5)烧结:将成型体先在400℃下保温1h,然后在富氧气氛(即高于空气的含氧量)下进行烧结,升温速度150℃/h,在1220℃保温1.5h,获得所述永磁铁氧体材料。
实施例5:
一种六角磁铅石永磁铁氧体材料,主相式为:Sr0.33Ca0.22La0.45Fe10.91Co0.28Ni0.08O19,其制备方法为:
(1)配料:按主相式中各元素的摩尔比将铁红、碳酸锶、碳酸钙、氧化镧、三氧化二钴和氧化镍放入湿法球磨机中进行混合球磨5h,得到平均粒度为0.8μm的混合料浆;
(2)预烧:将混合料浆在烘箱中进行干燥,然后造球,在空气中1240℃预烧,保温1h,获得颗粒状预烧料;
(3)球磨:称取预烧料450g,添加占固含量0.5wt%的SiO2、0.75wt%的CaCO3,0.4wt%的Cr2O3,再加占固含量0.6wt%的葡萄糖酸钙,然后添加680mL的去离子水作为球磨介质,在高效球磨机中进行24h的湿法粉碎,得到平均粒度为0.64μm的成型料浆;
(4)成型:对成型用料浆进行含水量调整,将料浆的固含量调整为70%,然后成型得到成型体,在压制的同时,在压制方向施加14000Oe的成型磁场,所得成型体是直径为43.2mm、高度为13mm的圆柱体,成型压力为10MPa;
(5)烧结:将成型体先在400℃下保温1h,然后在富氧气氛(即高于空气的含氧量)下进行烧结,升温速度150℃/h,在1220℃保温1.5h,获得所述永磁铁氧体材料。
实施例6:
一种六角磁铅石永磁铁氧体材料,主相式为:Sr0.35Ca0.24La0.41Fe 10.95Co0.25Zn0.09O19,其制备方法为:
(1)配料:按主相式中各元素的摩尔比将铁红、碳酸锶、碳酸钙、氧化镧、三氧化二钴和氧化锌放入湿法球磨机中进行混合球磨5h,得到平均粒度为0.8μm的混合料浆;
(2)预烧:将混合料浆在烘箱中进行干燥,然后造球,在空气中1240℃预烧,保温1h,获得颗粒状预烧料;
(3)球磨:称取预烧料450g,添加占固含量0.5wt%的SiO2、0.75wt%的CaCO3,0.4wt%的Cr2O3,再加占固含量0.6wt%的葡萄糖酸钙,然后添加680mL的去离子水作为球磨介质,在高效球磨机中进行24h的湿法粉碎,得到平均粒度为0.64μm的成型料浆;
(4)成型:对成型用料浆进行含水量调整,将料浆的固含量调整为70%,然后成型得到成型体,在压制的同时,在压制方向施加14000Oe的成型磁场,所得成型体是直径为43.2mm、高度为13mm的圆柱体,成型压力为10MPa;
(5)烧结:将成型体先在400℃下保温1h,然后在富氧气氛(即高于空气的含氧量)下进行烧结,升温速度150℃/h,在1220℃保温1.5h,获得所述永磁铁氧体材料。
实施例7:
一种六角磁铅石永磁铁氧体材料,主相式为:Sr0.34Ca0.23La0.43Fe10.93Co0.24Ni0.06Zn0.0 7O19,其制备方法为:
(1)配料:按主相式中各元素的摩尔比将铁红、碳酸锶、碳酸钙、氧化镧、三氧化二钴、氧化镍和氧化锌放入湿法球磨机中进行混合球磨5h,得到平均粒度为0.8μm的混合料浆;
(2)预烧:将混合料浆在烘箱中进行干燥,然后造球,在空气中1240℃预烧,保温1h,获得颗粒状预烧料;
(3)球磨:称取预烧料450g,添加占固含量0.5wt%的SiO2、0.75wt%的CaCO3,0.4wt%的Cr2O3,再加占固含量0.6wt%的葡萄糖酸钙,然后添加680mL的去离子水作为球磨介质,在高效球磨机中进行24h的湿法粉碎,得到平均粒度为0.64μm的成型料浆;
(4)成型:对成型用料浆进行含水量调整,将料浆的固含量调整为70%,然后成型得到成型体,在压制的同时,在压制方向施加14000Oe的成型磁场,所得成型体是直径为43.2mm、高度为13mm的圆柱体,成型压力为10MPa;
(5)烧结:将成型体先在400℃下保温1h,然后在富氧气氛(即高于空气的含氧量)下进行烧结,升温速度150℃/h,在1220℃保温1.5h,获得所述永磁铁氧体材料。
实施例8:
一种六角磁铅石永磁铁氧体材料,主相式为:Sr0.4Ca0.2La0.4Fe10.3Co0.3O19,其制备方法为:
(1)配料:按主相式中各元素的摩尔比将铁红、碳酸锶、碳酸钙、氧化镧和三氧化二钴放入湿法球磨机中进行混合球磨5h,得到平均粒度为0.8μm的混合料浆;
(2)预烧:将混合料浆在烘箱中进行干燥,然后造球,在空气中1250℃预烧,保温1h,获得颗粒状预烧料;
(3)球磨:称取预烧料450g,添加占固含量0.6wt%的SiO2、0.8wt%的CaCO3,0.3wt%的Cr2O3、0.3wt%的ZnO,再加占固含量0.2wt%的葡萄糖酸钙,然后添加680mL的去离子水作为球磨介质,在高效球磨机中进行22h的湿法粉碎,得到平均粒度为0.62μm的成型料浆;
(4)成型:对成型用料浆进行含水量调整,将料浆的固含量调整为70%,然后成型得到成型体,在压制的同时,在压制方向施加13000Oe的成型磁场,所得成型体是直径为43.2mm、高度为13mm的圆柱体,成型压力为10MPa;
(5)烧结:将成型体先在100℃下保温2h,然后在富氧气氛(即高于空气的含氧量)下进行烧结,升温速度150℃/h,在1100℃保温3h,获得所述永磁铁氧体材料。
实施例9:
一种六角磁铅石永磁铁氧体材料,主相式为:Sr0.4Ca0.2La0.4Fe11.1Co0.3O19,其制备方法为:
(1)配料:按主相式中各元素的摩尔比将铁红、碳酸锶、碳酸钙、氧化镧和三氧化二钴放入湿法球磨机中进行混合球磨5h,得到平均粒度为0.8μm的混合料浆;
(2)预烧:将混合料浆在烘箱中进行干燥,然后造球,在空气中1280℃预烧,保温1h,获得颗粒状预烧料;
(3)球磨:称取预烧料450g,添加占固含量0.6wt%的SiO2、0.8wt%的CaCO3,0.3wt%的Cr2O3,再加占固含量1.2wt%的葡萄糖酸钙,然后添加680mL的去离子水作为球磨介质,在高效球磨机中进行22h的湿法粉碎,得到平均粒度为0.62μm的成型料浆;
(4)成型:对成型用料浆进行含水量调整,将料浆的固含量调整为70%,然后成型得到成型体,在压制的同时,在压制方向施加13000Oe的成型磁场,所得成型体是直径为43.2mm、高度为13mm的圆柱体,成型压力为10MPa;
(5)烧结:将成型体先在400℃下保温0.5h,然后在富氧气氛(即高于空气的含氧量)下进行烧结,升温速度150℃/h,在1210℃保温2h,获得所述永磁铁氧体材料。
实施例10:
一种六角磁铅石永磁铁氧体材料,主相式为:Sr0.19Ba0.16Ca0.23La0.43Fe10.89Co0.35O19,其制备方法为:
(1)配料:按主相式中各元素的摩尔比将铁红、碳酸锶、碳酸钡、碳酸钙、氧化镧和三氧化二钴放入湿法球磨机中进行混合球磨5h,得到平均粒度为0.8μm的混合料浆;
(2)预烧:将混合料浆在烘箱中进行干燥,然后造球,在空气中1150℃预烧,保温3h,获得颗粒状预烧料;
(3)球磨:称取预烧料450g,添加占固含量0.05wt%的SiO2、0.4wt%的CaCO3、2.0wt%的Al2O3、0.6wt%的ZnO、0.1wt%的SrCO3及0.8wt%的H3BO3,再加占固含量1.0wt%的葡萄糖酸钙和0.2wt%的聚乙烯醇,然后添加680mL的去离子水作为球磨介质,在高效球磨机中进行22h的湿法粉碎,得到平均粒度为0.62μm的成型料浆;
(4)成型:对成型用料浆进行含水量调整,将料浆的固含量调整为70%,然后成型得到成型体,在压制的同时,在压制方向施加13000Oe的成型磁场,所得成型体是直径为43.2mm、高度为13mm的圆柱体,成型压力为10MPa;
(5)烧结:将成型体先在600℃下保温2h,然后在富氧气氛(即高于空气的含氧量)下进行烧结,升温速度150℃/h,在1300℃保温0.1h,获得所述永磁铁氧体材料。
实施例11:
一种六角磁铅石永磁铁氧体材料,主相式为:Sr0.3Ca0.4La0.3Fe10.95Co0.25O19,其制备方法为:
(1)配料:按主相式中各元素的摩尔比将铁红、碳酸锶、碳酸钙、氧化镧和三氧化二钴放入湿法球磨机中进行混合球磨5h,得到平均粒度为0.8μm的混合料浆;
(2)预烧:将混合料浆在烘箱中进行干燥,然后造球,在空气中1240℃预烧,保温1h,获得颗粒状预烧料;
(3)球磨:称取预烧料450g,添加占固含量0.5wt%的SiO2、0.75wt%的CaCO3,0.4wt%的Cr2O3,再加占固含量0.6wt%的葡萄糖酸钙,然后添加680mL的去离子水作为球磨介质,在高效球磨机中进行24h的湿法粉碎,得到平均粒度为0.64μm的成型料浆;
(4)成型:对成型用料浆进行含水量调整,将料浆的固含量调整为70%,然后成型得到成型体,在压制的同时,在压制方向施加14000Oe的成型磁场,所得成型体是直径为43.2mm、高度为13mm的圆柱体,成型压力为10MPa;
(5)烧结:将成型体先在400℃下保温1h,然后在富氧气氛(即高于空气的含氧量)下进行烧结,升温速度150℃/h,在1220℃保温1.5h,获得所述永磁铁氧体材料。
实施例12:
一种六角磁铅石永磁铁氧体材料,主相式为:Sr0.35Ca0.15La0.5Fe10.75Co0.45O19,其制备方法为:
(1)配料:按主相式中各元素的摩尔比将铁红、碳酸锶、碳酸钙、氧化镧和三氧化二钴放入湿法球磨机中进行混合球磨5h,得到平均粒度为0.8μm的混合料浆;
(2)预烧:将混合料浆在烘箱中进行干燥,然后造球,在空气中1240℃预烧,保温1h,获得颗粒状预烧料;
(3)球磨:称取预烧料450g,添加占固含量0.5wt%的SiO2、0.75wt%的CaCO3,0.4wt%的Cr2O3,再加占固含量0.6wt%的葡萄糖酸钙,然后添加680mL的去离子水作为球磨介质,在高效球磨机中进行24h的湿法粉碎,得到平均粒度为0.64μm的成型料浆;
(4)成型:对成型用料浆进行含水量调整,将料浆的固含量调整为70%,然后成型得到成型体,在压制的同时,在压制方向施加14000Oe的成型磁场,所得成型体是直径为43.2mm、高度为13mm的圆柱体,成型压力为10MPa;
(5)烧结:将成型体先在400℃下保温1h,然后在富氧气氛(即高于空气的含氧量)下进行烧结,升温速度150℃/h,在1220℃保温1.5h,获得所述永磁铁氧体材料。
对比例1:
对比例1与实施例1的区别在于,对比例1中的Sr全部用Ca替换,即对比例1中永磁铁氧体材料的主相式为:Ca0.56La0.44Fe10.87Co0.34O19,其余均与实施例1中相同。
对比例2:
对比例2与实施例1的区别在于,对比例2中的Ca全部用Sr替换,即对比例2中永磁铁氧体材料的主相式为:Sr0.56La0.44Fe10.87Co0.34O19,其余均与实施例1中相同。
对比例3:
对比例3与实施例8的区别在于,对比例3中n=5.0,即对比例2中六角磁铅石永磁铁氧体材料的主相式为:Sr0.4Ca0.2La0.4Fe9.7Co0.3O19,其余均与实施例8中相同。
对比例4:
对比例4与实施例8的区别在于,对比例4中n=5.8,即对比例3中六角磁铅石永磁铁氧体材料的主相式为:Sr0.4Ca0.2La0.4Fe11.3Co0.3O19,其余均与实施例8中相同。
将上述实施例和对比例中制得的六角磁铅石永磁铁氧体材料的上下表面研磨,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,结果如表1所示。
表1:永磁铁氧体材料磁性能测试结果。
编号 | Br(Gs) | Hcb(Oe) | Hcj(Oe) | (BH)max(MGOe) |
实施例1 | 4720 | 4268 | 5216 | 5.39 |
实施例2 | 4710 | 4055 | 5027 | 5.28 |
实施例3 | 4730 | 4049 | 5079 | 5.32 |
实施例4 | 4700 | 4095 | 5132 | 5.25 |
实施例5 | 4740 | 4102 | 5154 | 5.39 |
实施例6 | 4720 | 4098 | 5012 | 5.30 |
实施例7 | 4710 | 4058 | 5064 | 5.23 |
实施例8 | 4710 | 3975 | 5098 | 5.36 |
实施例9 | 4720 | 4254 | 5085 | 5.45 |
实施例10 | 4760 | 4089 | 5012 | 5.48 |
实施例11 | 4710 | 4194 | 5012 | 5.39 |
实施例12 | 4690 | 3989 | 5140 | 5.25 |
对比例1 | 4480 | 3567 | 4650 | 4.86 |
对比例2 | 4490 | 3624 | 4455 | 4.84 |
对比例3 | 4550 | 3273 | 4676 | 5.08 |
对比例4 | 4580 | 3754 | 4522 | 5.05 |
从表1中可以看出,实施例1~12中采用本发明中的配方比例和方法制备出的永磁铁氧体材料的剩余磁感应强度可以达到4700Gs左右,同时内禀矫顽力可以达到5000Oe以上,具有良好的磁性能。
而对比例1和对比例2中制得的Ca-La-Co铁氧体和Sr-La-Co铁氧体的各项磁性能与实施例1相比均有明显下降;对比例3和对比例4中改变n的取值,使其落在本发明的范围外,制得的永磁铁氧体的磁性能也有明显下降,证明本发明中各元素的比例不是常规选择。
Claims (10)
1.一种六角磁铅石永磁铁氧体材料,其特征是,通式为A1-x-yCaxRyFe2n-zMzO19,其中:A为Sr或者Sr和Ba,R中包括La,M中包括Co;x为0.15~0.4,y为0.3~0.5,z为0.25~0.45,n为5.3~5.7。
2.根据权利要求1所述的一种六角磁铅石永磁铁氧体材料,其特征是,R中还包括Pr、Nd、Bi中的一种或几种。
3.根据权利要求1所述的一种六角磁铅石永磁铁氧体材料,其特征是,M中还包括Ni和/或Zn。
4.根据权利要求1所述的一种六角磁铅石永磁铁氧体材料,其特征是,z/y为0.6~1.0。
5.如权利要求1~4任意所述的一种六角磁铅石永磁铁氧体材料的制备方法,其特征是,包括如下步骤:
(1)配料:按通式中各元素的摩尔比将含有各元素的原料化合物混合,用湿法混合工艺将混合物粉碎为平均粒度≤0.8µm的混合料浆;
(2)预烧:将混合料浆干燥后在空气中于1150~1280℃下进行预烧得到预烧料;
(3)球磨:向预烧料中加入二次添加物和添加剂,用湿法混合工艺将混合物研磨为平均粒度≤0.65µm的颗粒后得到成型料浆;
(4)成型:调整成型料浆的固含量至65~80wt%后磁场成型得到成型体,成型磁场强度≥13000Gs;
(5)烧结:将成型体先在100~600℃下保温0.5~2h,然后在富氧气氛(即高于空气的含氧量)下进行烧结后得到所述永磁铁氧体材料,烧结温度1100~1300℃,烧结时间0.1~3h。
6.根据权利要求5所述的一种六角磁铅石永磁铁氧体材料的制备方法,其特征是,步骤(1)中所述含有各元素的原料化合物为:Sr、Ba和Ca采用其碳酸盐作为原料化合物;La、Pr和Nd采用其氧化物或者氢氧化物作为原料化合物;Fe、Co、Ni、Zn和Bi采用其氧化物作为原料化合物。
7.根据权利要求5或6所述的一种六角磁铅石永磁铁氧体材料的制备方法,其特征是,步骤(1)中各原料化合物的平均粒度≤5µm。
8.根据权利要求5所述的一种六角磁铅石永磁铁氧体材料的制备方法,其特征是,步骤(2)中预烧时间0.1~3h。
9.根据权利要求5所述的一种六角磁铅石永磁铁氧体材料的制备方法,其特征是,步骤(3)中所述的二次添加物包括占固含量0.05~2.0wt%的SiO2、0.4~2.0wt%的CaCO3、0~2.0wt%的Al2O3、0~1.5wt%的Cr2O3、0~0.6wt%的ZnO、0.1~1.0wt%的SrCO3及0~0.8wt%的H3BO3,二次添加物的平均粒度≤5µm。
10.根据权利要求5或9所述的一种六角磁铅石永磁铁氧体材料的制备方法,其特征是,步骤(3)中所述的添加剂包括葡萄糖酸钙、聚乙烯醇和山梨糖醇中的一种或几种,添加量为固含量的0.2~1.2wt%。
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CN109796200A (zh) * | 2019-02-21 | 2019-05-24 | 成都锦钛精工科技有限公司 | 稀土掺杂永磁铁氧体及其制备方法 |
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