CN114804847B - 一种永磁铁氧体及其制备方法 - Google Patents

一种永磁铁氧体及其制备方法 Download PDF

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CN114804847B
CN114804847B CN202110081783.0A CN202110081783A CN114804847B CN 114804847 B CN114804847 B CN 114804847B CN 202110081783 A CN202110081783 A CN 202110081783A CN 114804847 B CN114804847 B CN 114804847B
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ball mill
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CN114804847A (zh
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邓志刚
王怡伟
刘力
丁仁宇
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Zigong Joint Mag Magnetic Materials Co ltd
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Abstract

一种永磁铁氧体的制备方法，包括以下步骤(1)混料，将氧化物和碳酸盐粉末进行预混合成为预混料，然后使用滚动球磨粉机混合得到混合料；(2)预烧，混合料过滤烘干去除水分后，烧结得到无稀土掺杂永磁铁氧体预烧料；(3)制粉，预烧料进行粗破碎，得到平均粒径在2‑6μm的粗破碎预烧粉末；添加表面活性剂及添加剂；破碎混合，得到平均粒径在0.6‑1.0μm的料浆；(4)压制生坯：将料浆过滤水分，压制成生坯；(5)烧结，将生坯烧结，得到烧结磁体；(6)打磨与测量，将烧结磁体冷却至室温后，进行表面磨削加工，得到标准块。

Description

一种永磁铁氧体及其制备方法
技术领域
本发明涉及永磁铁氧体领域，尤其涉及一种永磁铁氧体及其制备方法。
背景技术
铁氧体材料由于性能稳定，价格较低的优势，在市场中一直占有很大的比例。随着电子器件的集成小型化，要求铁氧体材料具有更高的磁性能，而目前市场上使用的高性能永磁铁氧体都是通过稀土元素及贵重金属钴掺杂来提高铁氧体磁性能的；由于稀土元素及一些贵金属的资源有限。因此，对无稀土及贵金属掺杂永磁铁氧体改性的研究具有重要意义。
目前，第一类钡锶铁氧体，由于性能不足，难以完全满足市场发展需求。而第二类稀土镧及钴改性铁氧体及第三类钙系镧钴掺杂铁氧体，虽然磁性能较高，但需要大量使用稀土元素及贵重金属元素钴，生产成本高，性价比低，对稀土资源及贵金属的节约使用不利。
发明内容
为解决上述问题，本发明提供以下方案：
一种永磁铁氧体的制备方法，包括以下步骤：
(1)混料，按化学结构式R1-xCaxFe2n-y-zMyZnzO19的组分要求，将氧化物和碳酸盐粉末进行预混合成为预混料，然后使用滚动球磨粉机混合得到混合料；
(2)预烧，将步骤(1)中所得的混合料，过滤烘干去除水分后，平铺于辊道窑的烧结钵中，在1100-1300℃之间预烧0.5-4小时，得到无稀土及贵金属掺杂永磁铁氧体预烧料；
(3)制粉，将步骤(2)中得到的无稀土及贵金属掺杂永磁铁氧体预烧料，在振动破碎机进行粗破碎，得到平均粒径在2-6μm的粗破碎预烧粉末；添加表面活性剂及添加剂；然后使用滚筒球磨机破碎混合，得到平均粒径在0.6-1.0μm的料浆；
(4)压制生坯：将步骤(3)中得到的料浆过滤水分，使其含水量为在35％-45％，采用湿压磁场取向压制成直径为34.1mm，高度为14-16mm的生坯，压制压力为7-9MPa，脉冲磁场为6-10Koe；
(5)烧结，将步骤(4)得到的生坯在辊道窑中950-1300℃下保温0.5-3h烧结，得到烧结磁体，烧结气氛为空气氧化性气氛，升温速率为20-400℃/h；烧结后的磁体降温速率为20-45℃/h。
(6)打磨与测量，将烧结磁体冷却至室温后，进行表面磨削加工，得到可测量标准块，按照GB/T3217-92国家标准进行检验测量。
进一步的，所述氧化物原料为Cr2O3、TiO2、Al2O3、CaO、Fe2O3、PbO、ZnO；碳酸盐粉末原料为CaCO3、BaCO3、SrCO3；所述的表面活性剂包含葡萄糖、葡萄糖酸钙、山梨糖醇、石墨烯、聚乙二醇、抗坏血酸、油酸中的一种或一种以上混合体。
进一步的：所述表面活性剂组分为葡萄糖、葡萄糖酸钙、山梨糖醇、石墨烯、聚乙二醇、抗坏血酸、油酸中的一种或一种以上混合体。
进一步的，表面活性剂的添加量为0.1-4％。
进一步的，所述添加剂的添加量为0.1-10％
进一步的，所述添加剂至少包括CaCO3、SiO2、Al2O3、H3BO3、SrCO3、BaCO3、Cr2O3中的三种，各添加剂占R1-xCaxFe2n-y-zMyZnzO19重量百分比为，0.2％≤CaCO3≤2％，0.1％≤SiO2≤2％，0.1％≤Al2O3≤2％，0％≤H3BO3≤2％，0％≤SrCO3≤2％，0％≤BaCO3≤2％，0％≤Cr2O3≤2％。
进一步的，所述球磨机粉碎时料、水、球的质量比为1：1.5：12.5。
进一步的，所述滚筒球磨机的滚筒内直径为350mm，球磨机转速为85r/min，钢球直径为5mm。混料时间优选5-10小时，制粉的二次细破碎时间15-20小时。
一种永磁铁氧体，所述永磁铁氧体使用以上所述制备方法制备而成。
进一步的，所述永磁铁氧体为六角晶系结构，其化学结构式为R1-xCaxFe2n-y- zMyZnzO19，其中0.1≤x≤0.7，0≤y≤0.5,0≤z≤0.3,5.2≤n≤6.5，R为Ba、Sr、Pb中的一种或一种以上,M为Cr、Al、Ti中的一种或一种以上。
本发明的有益效果为：
在不掺杂任何稀土及贵金属元素的情况下，采用掺杂至少包含Cr3+、Zn2+、Ca2+、Al3 +、Ti4+中的一种或两种离子来提高永磁锶铁氧体的磁性能，通过调整离子替换量及改善制备工艺可以制备出：剩磁Br：415-425mT，内禀矫顽力Hcj：300-380KA/m，最大磁能积BH(max)：32-35KJ/m3的高性价比永磁铁氧体磁体。
具体实施方式
以下结合具体实施例对本发明作进一步详细说明。
实施例1：
按照化学式Sr0.8Ca0.2Fe11.5Cr0.1Zn0.05O19进行主成分配比称量SrCO3：120g、Cr2O3：7.6g、CaCO3：20g、Fe2O3：920g、ZnO：4g。将原料粉末按料：水：球＝1:1.5:12.5重量比投入到滚筒球磨机中球磨5小时，球磨机转速85r/min，得到悬浮颗粒的平均粒径在0.8um的混合料。滤干烘干后在辊道窑中烧结，烧结温度为1280℃，保温时间为0.5小时。
在振动破碎机中粗破碎后，过120目筛，获得预烧料粗粉。
随后加入添加剂，添加剂含量占一次预烧料重量比为：山梨糖醇：1.0％、CaCO3：0.6％、SiO2：0.3％、H3BO3：0.2％、SrCO3：0.4％、Cr2O3：0.2％，按料：水：球＝1:1.5:12.5重量比投入到滚筒球磨机中球磨14小时，球磨机转速85r/min，得到平均粒度为0.8um的料浆。
在湿压磁场成型压机压制生坯，磁场强度6KOe，成型压力8MPa。
生坯在辊道窑空气气氛中烧结，烧结温度为1184℃，保温时间为1小时，随炉自然空冷至室温，得到剩磁Br：416mT，内禀矫顽力Hcj：363KA/m，最大磁能积BH(max)：33.4KJ/m3的高性价比无稀土永磁铁氧体。
实施例2：
按照化学式Sr0.7Ca0.3Fe11Cr0.1Al0.1Zn0.1O19进行主成分配比称量SrCO3：105g、Cr2O3：7.6g、Al2O3:5.1g、CaCO3：30g、Fe2O3：880g、ZnO：8g。将原料粉末按料：水：球＝1:1.5:12.5重量比投入到滚筒球磨机中球磨3小时，球磨机转速85r/min，得到悬浮颗粒的平均粒径在1.12um的混合料。滤干烘干后在辊道窑中烧结，烧结温度为1265℃，保温时间为1小时。
在振动破碎机中粗破碎后，过120目筛，获得粗破碎预烧料粗粉。
随后加入添加剂，添加剂含量占一次预烧料重量比为：山梨糖醇：0.3％、油酸：0.3％、CaCO3：1.0％、SiO2：0.5％、H3BO3：0.4％、BaCO3：0.4％、Cr2O3：0.1％，按料：水：球＝1:1.5:12.5重量比投入到滚筒球磨机中球磨13小时，球磨机转速85r/min，得到平均粒度为0.85um的料浆。
在湿压磁场成型压机压制生坯，磁场强度8KOe，成型压力7.5MPa。
生坯在辊道窑空气气氛中烧结，烧结温度为1195℃，保温时间为1.5小时，随炉自然空冷至室温，得到剩磁Br：418mT，内禀矫顽力Hcj：372KA/m，最大磁能积BH(max)：34.1KJ/m3的高性价比无稀土永磁铁氧体。
实施例3：
按照化学式Sr0.6Ca0.4Fe10.4Cr0.1Al0.1Ti0.1Zn0.15O19进行主成分配比称量SrCO3：90g、Cr2O3：7.6g、Al2O3:5.1g、TiO2:8g、CaCO3：40g、Fe2O3：832g、ZnO：12g。将原料粉末按料：水：球＝1:1.5:12.5重量比投入到滚筒球磨机中球磨6小时，球磨机转速85r/min，得到悬浮颗粒的平均粒径在0.81um的混合料。滤干烘干后在辊道窑中烧结，烧结温度为1255℃，保温时间为2小时。
在振动破碎机中粗破碎后，过120目筛，获得粗破碎预烧料粗粉。
随后加入添加剂，添加剂含量占一次预烧料重量比为：葡萄糖酸钙：0.4％、石墨烯：0.1％、CaCO3：1.2％、SiO2：0.6％、H3BO3：0.4％、SrCO3：0.4％、BaCO3：1.2％，按料：水：球＝1:1.5:12.5重量比投入到滚筒球磨机中球磨16小时，球磨机转速85r/min，得到平均粒度为0.78um的料浆。
在湿压磁场成型压机压制生坯，磁场强度9KOe，成型压力7.5MPa。
生坯在辊道窑空气气氛中烧结，烧结温度为1185℃，保温时间为2小时，随炉自然空冷至室温，得到剩磁Br：422mT，内禀矫顽力Hcj：376KA/m，最大磁能积BH(max)：34.8KJ/m3的高性价比无稀土永磁铁氧体。
实施例4：
按照化学式Sr0.5Ca0.5Fe10.8Cr0.2Al0.1Ti0.1Zn0.2O19进行主成分配比称量SrCO3：75g、Cr2O3：15.2g、Al2O3:5.1g、TiO2:8g、CaCO3：50g、Fe2O3：864g、ZnO：16g。将原料粉末按料：水：球＝1:1.5:12.5重量比投入到滚筒球磨机中球磨8小时，球磨机转速85r/min，得到悬浮颗粒的平均粒径在0.77um的混合料。滤干烘干后在辊道窑中烧结，烧结温度为1160℃，保温时间为4小时。
在振动破碎机中粗破碎后，过120目筛，获得粗破碎预烧料粗粉。
随后加入添加剂，添加剂含量占一次预烧料重量比为：山梨糖醇：0.6％、抗坏血酸：0.4％、CaCO3：0.4％、SiO2：0.2％、Al2O3：0.4％、SrCO3：0.4％、Cr2O3：0.5％，按料：水：球＝1:1.5:12.5重量比投入到滚筒球磨机中球磨18小时，球磨机转速85r/min，得到平均粒度为0.67um的料浆。
在湿压磁场成型压机压制生坯，磁场强度9KOe，成型压力7.5MPa。
生坯在辊道窑空气气氛中烧结，烧结温度为1235℃，保温时间为0.5小时，随炉自然空冷至室温，得到剩磁Br：425mT，内禀矫顽力Hcj：336KA/m，最大磁能积BH(max)：33.4KJ/m3的高性价比无稀土永磁铁氧体。
实施例5：
按照化学式Sr0.4Ca0.6Fe10.8Al0.3Ti0.2Zn0.25O19进行主成分配比称量SrCO3：60g、Al2O3:15.3g、TiO2:16g、CaCO3：60g、Fe2O3：864g、ZnO：20g。将原料粉末按料：水：球＝1:1.5:12.5重量比投入到滚筒球磨机中球磨10小时，球磨机转速85r/min，得到悬浮颗粒的平均粒径在0.74um的混合料。滤干烘干后在辊道窑中烧结，烧结温度为1200℃，保温时间为4小时。
在振动破碎机中粗破碎后，过120目筛，获得粗破碎预烧料粗粉。
随后加入添加剂，添加剂含量占一次预烧料重量比为：山梨糖醇：0.6％、聚乙二醇：0.4％、CaCO3：0.4％、SiO2：0.2％、Al2O3：0.3％、SrCO3：0.4％，按料：水：球＝1:1.5:12.5重量比投入到滚筒球磨机中球磨15小时，球磨机转速85r/min，得到平均粒度为0.81um的料浆。
在湿压磁场成型压机压制生坯，磁场强度10KOe，成型压力9MPa。
生坯在辊道窑空气气氛中烧结，烧结温度为1225℃，保温时间为1小时，随炉自然空冷至室温，得到剩磁Br：421mT，内禀矫顽力Hcj：306KA/m，最大磁能积BH(max)：32.7KJ/m3的高性价比无稀土永磁铁氧体。
最后，需要注意的是，以上列举的仅是本发明的具体实施例。显然，本发明不限于以上实施例，还可以有很多变形。本领域的普通技术人员能从本发明公开的内容中直接导出或联想到的所有变形，均应认为是本发明的保护范围。

Claims (9)

1.一种永磁铁氧体的制备方法，其特征在于：包括以下步骤：
（1）混料，按化学结构式R1-xCaxFe2n-y-zMyZnzO19的组分要求，将氧化物和碳酸盐粉末进行预混合成为预混料，然后使用滚动球磨粉机混合得到混合料，其中0.1≤x≤0.7，0＜y≤0.5, 0＜z≤0.3,5.2≤n≤6.5，R为Sr、Pb中的一种或一种以上,M为Cr、Al、Ti中的一种或一种以上；
（2）预烧，将步骤（1）中所得的混合料，过滤烘干去除水分后，平铺于辊道窑的烧结钵中，在1100-1300℃之间预烧0.5-4小时，得到无稀土掺杂永磁铁氧体预烧料；
（3）制粉，将步骤（2）中得到的无稀土掺杂永磁铁氧体预烧料，在振动破碎机进行粗破碎，得到平均粒径在2-6μm的粗破碎预烧粉末；添加表面活性剂及添加剂；然后使用滚筒球磨机破碎混合，得到平均粒径在0.6-1.0μm的料浆；
（4）压制生坯：将步骤（3）中得到的料浆过滤水分，使其含水量为35%-45%，采用湿压磁场取向压制成直径为34.1mm，高度为14-16mm的生坯，压制压力为7-9MPa，脉冲磁场为6-10KOe；
（5）烧结，将步骤（4）得到的生坯在辊道窑中950-1300℃下保温0.5-3h烧结，得到烧结磁体，烧结气氛为空气氧化性气氛，升温速率为20-400℃/h；
（6）打磨与测量，将烧结磁体冷却至室温后，进行表面磨削加工，得到可测量标准块，按照GB/T3217-92国家标准进行检验测量。
2.如权利要求1中所述一种永磁铁氧体的制备方法，其特征在于：所述氧化物原料为Cr2O3、TiO2、Al2O3、CaO、Fe2O3、PbO、ZnO；碳酸盐粉末原料为CaCO3、SrCO3；所述的表面活性剂包含葡萄糖、葡萄糖酸钙、山梨糖醇、石墨烯、聚乙二醇、抗坏血酸、油酸中的一种或一种以上混合体。
3.如权利要求1中所述一种永磁铁氧体的制备方法，其特征在于：所述表面活性剂组分为葡萄糖、葡萄糖酸钙、山梨糖醇、石墨烯、聚乙二醇、抗坏血酸、油酸中的一种或一种以上混合体。
4.如权利要求1中所述一种永磁铁氧体的制备方法，其特征在于：表面活性剂的添加量为0.1-4%。
5.如权利要求1中所述一种永磁铁氧体的制备方法，其特征在于：所述添加剂的添加量为0.1-10%。
6.如权利要求1中所述一种永磁铁氧体的制备方法，其特征在于：所述添加剂至少包括CaCO3、SiO2、Al2O3、H3BO3、SrCO3、Cr2O3中的三种，各添加剂占R1-xCaxFe2n-y-zMyZnzO19重量百分比为，0.2%≤CaCO3≤2%，0.1%≤SiO2≤2%，0.1%≤Al2O3≤2%，0%≤H3BO3≤2%，0%≤SrCO3≤2%，0%≤Cr2O3≤2%。
7.如权利要求1中所述一种永磁铁氧体的制备方法，其特征在于：所述球磨机粉碎时料、水、球的质量比为1：1.5：12.5。
8.如权利要求1中所述一种永磁铁氧体的制备方法，其特征在于：所述滚筒球磨机的滚筒内直径为350mm，球磨机转速为85r/min，钢球直径为5mm。
9.一种永磁铁氧体，其特征在于：所述永磁铁氧体使用权利要求1-8任一项所述制备方法制备而成。
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