CN117383923A - 一种钙钡锶永磁铁氧体及其制备方法 - Google Patents

一种钙钡锶永磁铁氧体及其制备方法 Download PDF

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CN117383923A
CN117383923A CN202210816841.4A CN202210816841A CN117383923A CN 117383923 A CN117383923 A CN 117383923A CN 202210816841 A CN202210816841 A CN 202210816841A CN 117383923 A CN117383923 A CN 117383923A
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magnetic ferrite
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邓志刚
黄家林
刘力
白枭
龙国俊
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Zigong Joint Mag Magnetic Materials Co ltd
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Abstract

一种钙钡锶永磁铁氧体的制备方法，其特征在于，包括以下步骤：(1)配料；按CaxBaySr(1‑x‑y)Fe2nO19计算出铁红、碳酸钙、碳酸锶、碳酸钡的质量，并添加二氧化硅、分散剂及其他添加剂，得到混合料A；(2)混料；将混合料A和水加入球磨机内进行球磨得到料浆，(3)一次预烧结；将步骤(2)所得料浆进行一次预烧结得到预烧料块；(4)磨料；将步骤(3)中所得预烧料块粉碎磨粉并过筛；(5)二次球磨，将步骤(4)中得到的预烧粗粉加入添加剂和水进行球磨得到二次料浆；(6)成型；二次料浆压制成型得到生坯；(7)二次烧结，生坯放入烧结炉中烧结得到熟坯；(8)磨加工检测，将熟坯进行磨加工，并检测数值。

Description

一种钙钡锶永磁铁氧体及其制备方法
技术领域
本发明涉及磁性材料领域，尤其涉及一种钙钡锶永磁铁氧体及其制备方法。
背景技术
永磁铁氧体又称硬磁铁氧体，因其具有高的矫顽力，且只需从外部提供一次充磁能量，就能产生恒定的磁场，因此其广泛用于汽车、家电、电动玩具等行业。
永磁铁氧体包括锶铁氧体、钡铁氧体、钴铁氧体、钙铁氧体等，应用最广泛的是锶铁氧体，其次是钡铁氧体，两者均属磁铅石型，晶体为六角晶系，易磁化轴在C轴，其分子式为MO.6Fe2O3或MFe12O19(M＝Sr、Ba,Pb等)，简称M型。
现有主流技术方案是锶铁氧体和钡铁氧体分开生产，锶铁氧体磁性能远高于钡铁氧体的磁性能，锶铁氧体用于汽车、家电等高端产品，钡铁氧体用于喇叭磁等低端产品，同时因碳酸锶的价格约为碳酸钡价格的3.5-5倍，因此锶铁氧体的市场价格远高于钡铁氧体的市场价格。
锶铁氧体的成本高，所使用的碳酸锶的价格约为碳酸钡价格的3.5-5倍；钡铁氧体的磁性能很低，只能用于极少数的低端产品，中华人民共和国电子行业标准SJ/T10412-2016《永磁铁氧体料粉》的常规钡铁氧体预烧料YF25和锶铁氧YF30/YF30H性能标准对比如下表2。
表2:常规钡铁氧体预烧料YF25和锶铁氧YF30/YF30H性能标准
对应的中华人民共和国电子行业标准SJ/T104110-2002《永磁铁氧体材料》的常规钡铁氧体材料Y25和锶铁氧Y30H-1性能标准对比如下表3，与上述永磁铁氧体料粉性能相一致。
表3:常规钡铁氧体材料Y25和锶铁氧Y30H-1性能标准
从以上可以看出，钡铁氧体的磁性能远低于锶铁氧体的磁性能。
发明内容
为解决上述问题，本发明提供以下方案：
一种钙钡锶永磁铁氧体的制备方法，包括以下步骤：
(1)配料；按CaxBaySr(1-x-y)Fe2nO19计算出铁红、碳酸钙、碳酸锶、碳酸钡的质量，并添加二氧化硅、分散剂及其他添加剂，得到混合料A；
(2)混料；将混合料A和水加入球磨机内进行球磨得到料浆，混合料：水：球的重量比为，1：(1.1-1.5)：(1.5-4)；
(3)一次预烧结；将步骤(2)所得料浆平摊并烘干，再将烘干后的料浆轻敲成块状进行一次预烧结得到预烧料块；
(4)磨料；将步骤(3)中所得预烧料块经过粉碎机进行粉碎磨粉并过筛得到预烧粗粉；
(5)二次球磨，将步骤(4)中得到的预烧粗粉投入球磨机并加入添加剂和水进行球磨得到二次料浆；
(6)成型；将步骤(5)中得到的二次料浆加(注)入模具并压制成型得到生坯；
(7)二次烧结，将步骤(6)中得到的生坯放入烧结炉中烧结得到熟坯；
(8)磨加工检测，将步骤(7)中得到的熟坯进行磨加工，得到钙钡锶永磁铁氧体磁体，并检测磁性能。
进一步地，CaxBaySr(1-x-y)Fe2nO19中，0.005≤x≤0.25，0.05≤y≤0.80，5.5≤n≤6.3.
进一步地，所述铁红可以替换为铁鳞(Fe3O4)或替换为铁红与铁鳞的组合。
进一步地，所述碳酸钙、碳酸锶、碳酸钡还可由氧化钙、氧化锶、氧化钡替换。
进一步地，所述二氧化硅占混合料A重量的0.01％-0.4％，分散剂占混合料A重量的0.05％-0.4％。
进一步地，所述其他添加剂包括但不限于硼酸、氧化铋、氧化铝、氧化铬、高岭土；其用量配比为硼酸占混合料A重量的0.01％-0.5％，氧化铋占混合料A重量的0.01％-0.4％，氧化铝占混合料A重量的0.01％-1.0％，氧化铬占混合料A重量的0.01％-0.8％，高岭土占混合料A重量的0.01％-1.0％。
进一步地，步骤(3)中料浆平摊为2-8mm的料层，并烘干至含水率小于5％；将料层轻敲为3-13mm的块状。
进一步地，所述步骤(3)中一次预烧结的温度曲线如表1所示。
进一步地，所述步骤(4)中，将预烧料块粉碎磨粉的时间为2-6分钟，粉碎磨粉后过40-120目筛网，得到的预烧粗粉粒度在3-6um。
进一步地，所述步骤(5)中，添加剂包括碳酸钙、二氧化硅、硼酸、氧化铝、氧化铬、高岭土、分散剂中的至少两种配料；所述配料用量与预烧粗料重量占比分别为，碳酸钙0.1％-1.5％，二氧化硅0.01％-0.5％，硼酸0.01％-0.4％，氧化铝0.01％-1.5％，氧化铬0.01％-1.5％，高岭土0.01％-1.5％，分散剂0.05％-0.5％，所述分散剂可以使用葡萄糖酸钙、山梨糖醇或其他分散剂
进一步地，所述步骤(2)与步骤(5)中混料和磨料所用的钢球直径为4-6.5mm的合金钢球或轴承钢球；合金钢球的含铬量为5％-15％。
进一步地，所述步骤(5)中二次球磨进行6-13小时，二次料浆的平均颗粒度为0.85-1.1um。
进一步地，所述生坯直径34.1mm，高度16.5-17.5cm，压制压力为380-420KG/cm2。
本发明的有益效果为：
1.通过添加分散剂，减少颗粒的团聚，粒度分布更加均匀，混和料浆的流动性更好，出料更快、更干净，减少了球磨内混和料浆的残留量，在连续生产时，减少了残留量对下一机料的粒径均匀度的影响。
2.添加不同的添加剂促进烧结，有效控制晶粒的生长和晶粒形貌，提高烧结磁体的单畴颗粒比例，添加剂在形成高密度提高剩余磁化强度Br的同时，极大的提高铁氧体的内禀矫顽力HcJ，即使在有较高比例钡存在的情况下，也能获得远远高于传统钡铁氧体的磁性能，尤其是能获得优异HcJ，比钡永磁铁氧体的HcJ高达78％。
3.与传统的锶永磁铁氧体相比，本发明的钙钡锶永磁铁氧体根据不同的钙与钡取代锶的量，将不同程度的降低铁氧体材料的成本，且在一定的取代范围内，获得高于传统的锶永磁铁氧体的磁性能。
4.本发明混料使用φ4－φ6.5mm，钢球量只使用传统量的30％左右料浆即可混和均匀，因钢球磨损少材料的成份更准确，更能获得优秀的磁性能，将极大的降低混料时球磨机的用电量和钢球的损耗量，同时降低钢球对球磨机的磨损。
5.烧结中采用特殊的温度曲线，一次预烧结曲线在1200℃前以2-4℃/M的升温速度快速升温，在1200℃到烧结温度(如烧结温度1250℃，保温1.5-4小时)段，将升温速度调整到0.33-1.33℃/M，形成一段次高温区，与传统的在烧结温度前一直以2-5℃/M快速升温相比，因在1200℃时氧化铁红与氧化钡、氧化锶等铁氧体化的反应已经到达高峰阶段，在1200℃明显降低升温速度，增加了在此段的反应时间，因此段温度比最高烧结温度低，生成的铁氧体晶粒细小而均匀，同时因增加了一段次高温区，高温区的烧结温度可以比传统的烧结温度降低20-80℃，在节约能源的同时，使得村料的铁氧体化一直在较低温度下进行反应，加上加入的添加剂二氧化硅SiO2有控制晶粒生长和控制晶粒形貌的作用，铁氧体材料的晶粒细小而均匀，因此在有钡存在的情况下，仍然能获得远远高于现有钡铁氧体的HcJ。
6.二次球磨料浆的平均粒度控制较粗，即便在平均粒度达到0.85-1.10um的情况下，也能获高的磁性能，料浆的排水性和成型性优秀，球磨和成型效率高、成本低。
7、本发明的钙钡锶永磁铁氧体生产工艺简单、易控制，用现有的大生产设备即可实现工业化量产，也容易实现自动化控制。
附图说明
图1为一次预烧结温度曲线图；
图2为本发明工艺流程图；
图3为传统锶永磁铁氧体混合料浆SEM照片；
图4为本发明的钙钡锶永磁铁氧体混合料浆SEM照片。
图5：传统的锶永磁铁氧体预烧料粗粉SEM照片。
图6：本发明的钙钡锶永磁铁氧体预烧料粗粉SEM照片。
具体实施方式
实施例1：
按本发明的组成CaxBaySr(1-x-y)Fe2nO19取x＝0.05，y＝0.15，n＝5.90，即Ca0.05Ba0.15Sr0.8Fe11.8O19，按此分子式计算准确称量CaCO3、BaCO3、SrCO3和Fe2O3，并加入此4种原料总量0.2％的SiO2和0.15％的分散剂葡萄糖酸钙，配料总量为为1.5KG,加入水1.8KG，钢球为φ4.8mm的合金钢球4.5KG，混料2小时。
混和料浆在滤布中摊平到3.5mm烘干到含水率小于5％，成片状在箱式炉中按表1和图1所示的一次烧结温度曲线升降温，在1250℃保温2.5小时得到块状预烧料，块状预烧料破碎过100目筛，检测铁氧体预烧料粗粉的平均粒度为4.3um，取1KG预烧料粗粉，加入0.8％的碳酸钙，0.2％的二氧化硅,0.2％的硼酸和0.2％葡萄糖酸钙(分散剂)，加入水1.6KG，φ4.8mm的合金钢球12KG,开机磨12小时(平均粒度0.90um)，料浆滤水到含水率32％，将料浆在8000GS的磁场中压成φ34.1mm，高度16.5mm的生坯。图4为钙钡锶永磁铁氧体混合料浆SEM照片，图3为传统的锶永磁铁氧体混合料浆SEM照片，通过两者对比，本发明的钙钡锶永磁铁氧体预烧料粗粉晶粒细小均匀，形貌完整。
将生坯在箱式炉1210℃保温1小时烧结得到熟坯，将熟坯的上下表面磨加工得到铁氧体磁体，检测磁体的性能如表4所示。
实施例2:
按传统的钡永磁铁氧体的组分BaFe11.8O19制备钡永磁铁氧体，参照实施例1的制备工艺，所不同的是，除配比成份不同外，一次预烧料配比只加入0.2％的SiO2，不加入分散剂葡萄糖酸钙，配料总量为1.5KG,混和钢球采用φ12.7mm(占比50％)、φ10mm(占比30％)和φ8mm(占比20％)的混合合金钢球8.0KG，混和2小时，混和料浆烘干在箱式炉中以3.3℃/M的升温速度升温到1290℃保温2.5H,二次球磨用φ8mm的合金钢球磨料，其他工艺同实施例1的制备工艺，检测磁体的磁性能见表4。
实施例3:
按传统的锶永磁铁氧体的组分SrFe11.8O19制备锶永磁铁氧体，除配比成份不同外，其他工艺同对比实施例2，检测磁体的性能见表4。
以上实施例1和对比实施例2、对比实施例3的磁体检测性能见如下表4。
磁性能 Br(mT) HcB(KA/m) HcJ(KA/m) (BH)max(KJ/m3) 备注
实施例1 406.3 285.7 299.7 32.6 本发明永磁铁氧体
实施例1 405.8 287.2 302.2 32.3 本发明永磁铁氧体
实施例2 386.3 163.7 170 26.1 钡永磁铁氧体
实施例2 388.4 163 168.2 26.4 钡永磁铁氧体
实施例3 400.2 272.6 285.4 31.2 锶永磁铁氧体
实施例3 401.7 272.0 284.6 31.5 锶永磁铁氧体
表4:实施例1和对比实施例2/3的磁性能对比
从以上实施例1和对比实施例2、对比实施例3来看，本发明的实施例1的钙钡锶永磁铁氧体获得了远高于传统钡铁氧体的磁性能，Br高约5.0％，HcJ高约78％，本发明的实施例1的钙钡锶永磁铁氧体与实施例3传统的锶永磁铁氧体相比，按投料时的碳酸盐重量百分比计算，在钙和钡取代锶占比22.7％降低成本的同时，获得了高于传统锶永磁铁氧体的磁性能，Br高约1.3％，HcJ高约5.6％。
实施例4：
按本发明的组成CaxBaySr(1-x-y)Fe2nO19取x＝0.05，y＝0.40，n＝6.05，即Ca0.05Ba0.40Sr0.55Fe12.1O19，与实施例1相比，增加了钡的占比，n由5.9提高到6.05，按投料时的碳酸盐重量百分比计算，钙和钡取代锶占比达到了51.3％，超过了一半，其他工艺按实施例1的制备方法，磁体的磁性能如下表5：
实施例5
按本发明的组成CaxBaySr(1-x-y)Fe2nO19取x＝0.08，y＝0.30，n＝6.1，即Ca0.08Ba0.30Sr0.62Fe12.1O19，与实施例1相比，增加了钙和钡的占比，n由5.9提高到6.1，按投料时的碳酸盐重量百分比计算，钙和钡取代锶占比达到了42.3％(钙的取代比例由0.46％增加到了0.71％)，其他工艺按实施例1的制备方法。
实施例4、实施例5的磁体磁性能如表5所示。
磁性能 Br(mT) HcB(KA/m) HcJ(KA/m) (BH)max(KJ/m3) 备注
实施例4 402.6 275 287.2 31.8 增加了钡的取代量
实施例4 401.8 276.3 288.2 31.7 增加了钡的取代量
实施例5 402.3 277 289 31.8 增加了钙和钡的取代量
实施例5 402.1 278 290.4 31.8 增加了钙和钡的取代量
表5:实施例4、实施例5磁体磁性能表
从以上实施例4和实施例5来看，本发明的实施例4和实施例5均在钙和钡取代锶的重量占比分别达到51.3％和42.3％的高比例取代量的情况下，获得了较优秀的磁性能，其磁性能远高于传统钡铁氧体的磁性能，Br高约3.9％，HcJ高约71％，本发明的实施例4和实施例5的钙钡锶永磁铁氧体与实施例3传统的锶永磁铁氧体相比，在大幅度低成本的同时，获得了和传统锶永磁铁氧体相当的磁性能。
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 (10)

1.一种钙钡锶永磁铁氧体的制备方法，其特征在于，包括以下步骤：
(1)配料；按CaxBaySr(1-x-y)Fe2nO19计算出铁红、碳酸钙、碳酸锶、碳酸钡的质量，并添加二氧化硅、分散剂及其他添加剂，得到混合料A；
(2)混料；将混合料A和水加入球磨机内进行球磨得到料浆，混合料：水：球的重量比为，1：(1.1-1.5)：(1.5-4)；
(3)一次预烧结；将步骤(2)所得料浆平摊并烘干，再将烘干后的干料块轻敲成块状进行一次预烧结得到预烧料块；
(4)磨料；将步骤(3)中所得预烧料块经过粉碎机进行粉碎磨粉并过筛得到预烧粗粉；
(5)二次球磨，将步骤(4)中得到的预烧粗粉投入球磨机并加入添加剂和水进行球磨得到二次料浆；
(6)成型；将步骤(5)中得到的二次料浆加入模具并压制成型得到生坯；
(7)二次烧结，将步骤(6)中得到的生坯放入烧结炉中烧结得到熟坯；
(8)磨加工检测，将步骤(7)中得到的熟坯进行磨加工，并检测数值。
2.如权利要求1中所述一种钙钡锶永磁铁氧体的制备方法，其特征在于：所述二氧化硅占混合料A重量的0.01％-0.4％，分散剂占混合料A重量的0.05％-0.4％。
3.如权利要求1中所述一种钙钡锶永磁铁氧体的制备方法，其特征在于：所述其他添加剂包括但不限于硼酸、氧化铋、氧化铝、氧化铬、高岭土；其用量配比为硼酸占混合料A重量的0.01％-0.5％，氧化铋占混合料A重量的0.01％-0.4％，氧化铝占混合料A重量的0.01％-1.0％，氧化铬占混合料A重量的0.01％-0.8％，高岭土占混合料A重量的0.01％-1.0％。
4.如权利要求1中所述一种钙钡锶永磁铁氧体的制备方法，其特征在于：步骤(3)中料浆平摊为2-8mm的料层，并烘干至含水率小于5％；将料层轻敲为3-13mm的块状，但不限于此方法，如亦可将料浆烘干到含水率5-10％加工成3-10mm的料球。
5.如权利要求1中所述一种钙钡锶永磁铁氧体的制备方法，其特征在于：所述步骤(3)中一次预烧结的温度曲线如下表1：
表1：一次预烧结温度曲线
6.如权利要求1中所述一种钙钡锶永磁铁氧体的制备方法，其特征在于：所述步骤(4)中，将预烧料块粉碎磨粉的时间为2-6分钟，粉碎磨粉后过40-120目筛网，得到的预烧粗粉的平均粒度在3-6um。
7.如权利要求1中所述一种钙钡锶永磁铁氧体的制备方法，其特征在于：所述步骤(5)中，添加剂包括碳酸钙、二氧化硅、硼酸、氧化铝、氧化铬、高岭土、分散剂中的至少两种配料；所述配料用量与预烧粗料重量占比分别为，碳酸钙0.1％-1.5％，二氧化硅0.01％-0.5％，硼酸0.01％-0.4％，氧化铝0.01％-1.5％，氧化铬0.01％-1.5％，高岭土0.01％-1.5％，分散剂0.05％-0.5％。
8.如权利要求1中所述一种钙钡锶永磁铁氧体的制备方法，其特征在于：所述步骤(2)与步骤(5)中混料和磨料所用的钢球为直径4-6.5mm的合金钢球或轴承钢球；合金钢球的含铬量为5％-15％。
9.如权利要求1中所述一种钙钡锶永磁铁氧体的制备方法，其特征在于：所述步骤(5)中二次球磨进行6-13小时，二次料浆的平均颗粒度为0.85-1.1um。
10.一种钙钡锶永磁铁氧体，其特征在于，所述钙钡锶永磁铁氧体由权利要求1-9任一一项所述方法制备所得。
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