CN106882962A - 一种高磁能m型钡铁氧体永磁材料及其制备方法 - Google Patents

一种高磁能m型钡铁氧体永磁材料及其制备方法 Download PDF

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CN106882962A
CN106882962A CN201710135253.3A CN201710135253A CN106882962A CN 106882962 A CN106882962 A CN 106882962A CN 201710135253 A CN201710135253 A CN 201710135253A CN 106882962 A CN106882962 A CN 106882962A
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magnetic energy
barium ferrite
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曹庆波
王遵跃
张展胜
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Anhui Dongfang Magnetic Magnet Manufacturing Co Ltd
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Abstract

本发明提出了一种高磁能M型钡铁氧体永磁材料及其制备方法，包括以下摩尔份数组成：铁源35‑60份、硝酸钡4‑5份、聚丙烯酰胺2‑3份、氨基醋酸铜4‑7份、乙酰丙酮钴4‑5份、氨基磺酸镍4‑5份、水合联氨0.5‑1.5份、十六烷基三甲基溴化铵0.5‑2份、硬脂酸金属盐1‑5份、稀土氧化物0‑2.5份、盐卤0‑6份，采用混料、球磨、超声、烧结等步骤制成，通过对钡铁氧体进行铜、钴、镍等掺杂，不仅降低了烧结温度，同时大大提高了磁性能，制得钡铁氧体永磁材料最大磁能积(BH)max为38.5‑40.7kJ/m3，饱和磁化强度MS为344‑361kA/m，剩磁Br为0.495‑0.52T，内禀矫顽力Hcj为435‑447kA/m，居里温度大于390℃。

Description

一种高磁能M型钡铁氧体永磁材料及其制备方法
技术领域
本发明涉及铁氧体磁性材料技术领域，具体涉及一种高磁能M型钡铁氧体永磁材料及其制备方法。
背景技术
铁氧体是一种具有铁磁性的金属氧化物，一般可分为永磁铁氧体、软磁铁氧体和旋磁铁氧体三种，其电阻率比金属、合金磁性材料大得多，而且还有较高的介电性能，同时，铁氧体的磁性能还表现在高频时具有较高的磁导率，因而，铁氧体已成为高频弱电领域用途广泛的非金属磁性材料。由于铁氧体单位体积中储存的磁能较低，饱合磁化强度也较低，因而限制了它在要求较高磁能密度的低频强电和大功率领域的应用。目前，M型永磁铁氧体性能的提升一般是通过离子取代和改进烧结工艺实现的，在离子取代方面，大多通过La3+、Co2+、Al3+、Cu2+、Zn2+等离子取代来提升磁性能，但单种元素离子的取代并不能使铁氧体的性能达到较高的水平；在改进烧结工艺方面，需结合具体的工艺配方，调节合适的烧结温度以形成较好的晶粒提高磁性能。
发明内容
针对上述存在的问题，本发明提出了一种高磁能M型钡铁氧体永磁材料及其制备方法，采用混料、球磨、超声、烧结等步骤制成，通过对钡铁氧体进行铜、钴、镍等掺杂，不仅降低了烧结温度，同时大大提高了磁性能。
为了实现上述的目的，本发明采用以下的技术方案：
一种高磁能M型钡铁氧体永磁材料，包括以下摩尔份数组成：铁源35-60份、硝酸钡4-5份、聚丙烯酰胺2-3份、氨基醋酸铜4-7份、乙酰丙酮钴4-5份、氨基磺酸镍4-5份、水合联氨0.5-1.5份、十六烷基三甲基溴化铵0.5-2份、硬脂酸金属盐1-5份、稀土氧化物0-2.5份、盐卤0-6份。
优选的，高磁能M型钡铁氧体永磁材料包括以下摩尔份数组成：铁源50-60份、硝酸钡4.5-5份、聚丙烯酰胺2.5-3份、氨基醋酸铜5-7份、乙酰丙酮钴4.5-5份、氨基磺酸镍4.5-5份、水合联氨1-1.5份、十六烷基三甲基溴化铵1.5-2份、硬脂酸金属盐4-5份、稀土氧化物1.5-2.5份、盐卤4-6份。
优选的，所述铁源为三氧化二铁或柠檬酸铁和铁精矿的组合物，所述铁精矿添加量为铁源总质量的10-20％。
优选的，所述稀土氧化物为氧化镧、氧化铈中的一种或两者的组合物。
优选的，所述硬脂酸金属盐中金属选自为镁、钡、铜、锌、钙中的一种或多种。
优选的，高磁能M型钡铁氧体永磁材料的制备方法，其特征在于，步骤如下：
1)按重量粉称取原料；
2)将铁源、硝酸钡、硬脂酸金属盐、稀土氧化物、盐卤送入行星球磨机内进行一次球磨至粒径小于15μm，取出后在60℃空气中烘干，然后在供氧条件下进行预烧结，预烧结温度为1100-1150℃，时间为2-3h，然后取出送入球磨机内进行二次球磨至粒径小于3μm，得粗基料；
3)将氨基醋酸铜、乙酰丙酮钴、氨基磺酸镍共混，送入球磨机内在惰性气氛下进行超细球磨10-12h，得混合细粉，再将该混合细粉与聚丙烯酰胺、十六烷基三甲基溴化铵加入100-120倍混合细粉质量的水中，加热搅拌，搅拌条件下向其中滴加水合联氨，待全部滴加完成后，超声分散3-4h，得湿混料；
4)将粗基料与湿混料共混，混匀后置于干燥箱中，调节温度为130-160℃，保温6h，然后降温至45-60℃保温3h，得干混料；
5)将干混料再次送入球磨机中球磨至粒径小于1μm，取出烘干后向其中加入占干混料质量0.2-0.3％的聚乙烯醇，搅拌均匀，然后定型，定型压力为1100MPa，温度为90℃，时间为15min，得成型体；
6)将成型体进行烧结，先在850-900℃保温3-4h，然后以一定速率升温至1050-1100℃保温3-4h，再在700℃回火1-2h，即可。
优选的，步骤2)一次球磨中钢球、原料、水的质量比为3:1:1，二次球磨中钢球、原料、水的质量比为8:1:1.5，步骤3)球磨中钢球、原料、水的质量比为10:1:1.5，步骤5)球磨中钢球、原料、水的质量比为15:1:2。
优选的，步骤3)中加热搅拌具体为温度40℃，搅拌速度为200r/min，超声分散具体为温度35℃，频率25kHz。
优选的，步骤6)中升温速率具体为2℃/min。
由于采用上述的技术方案，本发明的有益效果是：本发明采用混料、球磨、超声、烧结等步骤制成，通过对钡铁氧体进行铜、钴、镍等掺杂、取代，不仅降低了烧结温度，同时大大提高了磁性能。本发明通过合理的原料选择、参数优化、工艺控制等制得钡铁氧体永磁材料最大磁能积(BH)max为38.5-40.7kJ/m3，饱和磁化强度MS为344-361kA/m，剩磁Br为0.495-0.52T，内禀矫顽力Hcj为435-447kA/m，居里温度大于390℃。
在制备过程中先将氨基醋酸铜、乙酰丙酮钴、氨基磺酸镍进行混合，制备Cu-Co-Ni、Cu-Co、Co-Ni、Cu-Ni等联合体，包覆于钡铁氧体表面进行球磨、烧结，大大提高了取代后磁性能的提升，同时添加的低熔点物质不仅有利于低温烧结，也改善了晶粒形貌。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述。基于本发明的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1：
一种高磁能M型钡铁氧体永磁材料，包括以下摩尔份数组成：铁源40份、硝酸钡4份、聚丙烯酰胺3份、氨基醋酸铜4份、乙酰丙酮钴4.3份、氨基磺酸镍4份、水合联氨0.8份、十六烷基三甲基溴化铵0.5份、硬脂酸金属盐4份、稀土氧化物0份、盐卤4份。
其中，铁源为三氧化二铁和铁精矿的组合物，所述铁精矿添加量为铁源总质量的10％，稀土氧化物为氧化镧，硬脂酸金属盐中金属选自为镁、钡、铜。
高磁能M型钡铁氧体永磁材料的制备方法，步骤如下：
1)按重量粉称取原料；
2)将铁源、硝酸钡、硬脂酸金属盐、稀土氧化物、盐卤送入行星球磨机内进行一次球磨至粒径小于15μm，取出后在60℃空气中烘干，然后在供氧条件下进行预烧结，预烧结温度为1130℃，时间为2.5h，然后取出送入球磨机内进行二次球磨至粒径小于3μm，得粗基料；
3)将氨基醋酸铜、乙酰丙酮钴、氨基磺酸镍共混，送入球磨机内在惰性气氛下进行超细球磨11h，得混合细粉，再将该混合细粉与聚丙烯酰胺、十六烷基三甲基溴化铵加入110倍混合细粉质量的水中，加热搅拌，搅拌条件下向其中滴加水合联氨，待全部滴加完成后，超声分散3.5h，得湿混料；
4)将粗基料与湿混料共混，混匀后置于干燥箱中，调节温度为140℃，保温6h，然后降温至60℃保温3h，得干混料；
5)将干混料再次送入球磨机中球磨至粒径小于1μm，取出烘干后向其中加入占干混料质量0.2％的聚乙烯醇，搅拌均匀，然后定型，定型压力为1100MPa，温度为90℃，时间为15min，得成型体；
6)将成型体进行烧结，先在880℃保温3.2h，然后以一定速率升温至1080℃保温3.5h，再在700℃回火1.5h，即可。
实施例2：
一种高磁能M型钡铁氧体永磁材料，包括以下摩尔份数组成：铁源50份、硝酸钡4.8份、聚丙烯酰胺2份、氨基醋酸铜7份、乙酰丙酮钴4.5份、氨基磺酸镍4.5份、水合联氨0.5份、十六烷基三甲基溴化铵2份、硬脂酸金属盐5份、稀土氧化物2.5份、盐卤5份。
其中，铁源为三氧化二铁和铁精矿的组合物，所述铁精矿添加量为铁源总质量的20％，稀土氧化物为氧化铈，硬脂酸金属盐中金属选自为镁、钡、钙。
高磁能M型钡铁氧体永磁材料的制备方法，步骤如下：
1)按重量粉称取原料；
2)将铁源、硝酸钡、硬脂酸金属盐、稀土氧化物、盐卤送入行星球磨机内进行一次球磨至粒径小于15μm，取出后在60℃空气中烘干，然后在供氧条件下进行预烧结，预烧结温度为1150℃，时间为2.8h，然后取出送入球磨机内进行二次球磨至粒径小于3μm，得粗基料；
3)将氨基醋酸铜、乙酰丙酮钴、氨基磺酸镍共混，送入球磨机内在惰性气氛下进行超细球磨11.5h，得混合细粉，再将该混合细粉与聚丙烯酰胺、十六烷基三甲基溴化铵加入120倍混合细粉质量的水中，加热搅拌，搅拌条件下向其中滴加水合联氨，待全部滴加完成后，超声分散3.2h，得湿混料；
4)将粗基料与湿混料共混，混匀后置于干燥箱中，调节温度为150℃，保温6h，然后降温至50℃保温3h，得干混料；
5)将干混料再次送入球磨机中球磨至粒径小于1μm，取出烘干后向其中加入占干混料质量0.2％的聚乙烯醇，搅拌均匀，然后定型，定型压力为1100MPa，温度为90℃，时间为15min，得成型体；
6)将成型体进行烧结，先在850℃保温4h，然后以一定速率升温至1100℃保温4h，再在700℃回火2h，即可。
实施例3：
一种高磁能M型钡铁氧体永磁材料，包括以下摩尔份数组成：铁源60份、硝酸钡5份、聚丙烯酰胺2.5份、氨基醋酸铜6份、乙酰丙酮钴4份、氨基磺酸镍5份、水合联氨1份、十六烷基三甲基溴化铵1.5份、硬脂酸金属盐3份、稀土氧化物1.5份、盐卤3份。
其中，铁源为柠檬酸铁和铁精矿的组合物，所述铁精矿添加量为铁源总质量的20％，稀土氧化物为氧化镧，硬脂酸金属盐中金属选自为镁、钙。
高磁能M型钡铁氧体永磁材料的制备方法，步骤如下：
1)按重量粉称取原料；
2)将铁源、硝酸钡、硬脂酸金属盐、稀土氧化物、盐卤送入行星球磨机内进行一次球磨至粒径小于15μm，取出后在60℃空气中烘干，然后在供氧条件下进行预烧结，预烧结温度为1110℃，时间为2h，然后取出送入球磨机内进行二次球磨至粒径小于3μm，得粗基料；
3)将氨基醋酸铜、乙酰丙酮钴、氨基磺酸镍共混，送入球磨机内在惰性气氛下进行超细球磨12h，得混合细粉，再将该混合细粉与聚丙烯酰胺、十六烷基三甲基溴化铵加入115倍混合细粉质量的水中，加热搅拌，搅拌条件下向其中滴加水合联氨，待全部滴加完成后，超声分散3.5h，得湿混料；
4)将粗基料与湿混料共混，混匀后置于干燥箱中，调节温度为130℃，保温6h，然后降温至55℃保温3h，得干混料；
5)将干混料再次送入球磨机中球磨至粒径小于1μm，取出烘干后向其中加入占干混料质量0.3％的聚乙烯醇，搅拌均匀，然后定型，定型压力为1100MPa，温度为90℃，时间为15min，得成型体；
6)将成型体进行烧结，先在860℃保温3.8h，然后以一定速率升温至1050℃保温4h，再在700℃回火1.8h，即可。
实施例4：
一种高磁能M型钡铁氧体永磁材料，包括以下摩尔份数组成：铁源35份、硝酸钡4.5份、聚丙烯酰胺2.2份、氨基醋酸铜5份、乙酰丙酮钴4.5份、氨基磺酸镍5份、水合联氨1份、十六烷基三甲基溴化铵1份、硬脂酸金属盐2份、稀土氧化物1份、盐卤0份。
其中，铁源为三氧化二铁和铁精矿的组合物，所述铁精矿添加量为铁源总质量的15％，稀土氧化物为氧化镧、氧化铈的组合物，硬脂酸金属盐中金属选自为钡、锌。
高磁能M型钡铁氧体永磁材料的制备方法，步骤如下：
1)按重量粉称取原料；
2)将铁源、硝酸钡、硬脂酸金属盐、稀土氧化物、盐卤送入行星球磨机内进行一次球磨至粒径小于15μm，取出后在60℃空气中烘干，然后在供氧条件下进行预烧结，预烧结温度为1100℃，时间为2.5h，然后取出送入球磨机内进行二次球磨至粒径小于3μm，得粗基料；
3)将氨基醋酸铜、乙酰丙酮钴、氨基磺酸镍共混，送入球磨机内在惰性气氛下进行超细球磨10h，得混合细粉，再将该混合细粉与聚丙烯酰胺、十六烷基三甲基溴化铵加入110倍混合细粉质量的水中，加热搅拌，搅拌条件下向其中滴加水合联氨，待全部滴加完成后，超声分散4h，得湿混料；
4)将粗基料与湿混料共混，混匀后置于干燥箱中，调节温度为130℃，保温6h，然后降温至45℃保温3h，得干混料；
5)将干混料再次送入球磨机中球磨至粒径小于1μm，取出烘干后向其中加入占干混料质量0.3％的聚乙烯醇，搅拌均匀，然后定型，定型压力为1100MPa，温度为90℃，时间为15min，得成型体；
6)将成型体进行烧结，先在900℃保温3h，然后以一定速率升温至1050℃保温3.5h，再在700℃回火1.8h，即可。
实施例5：
一种高磁能M型钡铁氧体永磁材料，包括以下摩尔份数组成：铁源45份、硝酸钡4.5份、聚丙烯酰胺2.8份、氨基醋酸铜6份、乙酰丙酮钴5份、氨基磺酸镍4.5份、水合联氨1.5份、十六烷基三甲基溴化铵1.5份、硬脂酸金属盐1份、稀土氧化物2份、盐卤6份。
其中，铁源为三氧化二铁和铁精矿的组合物，所述铁精矿添加量为铁源总质量的15％，稀土氧化物为氧化镧、氧化铈的组合物，硬脂酸金属盐中金属选自为镁。
高磁能M型钡铁氧体永磁材料的制备方法，步骤如下：
1)按重量粉称取原料；
2)将铁源、硝酸钡、硬脂酸金属盐、稀土氧化物、盐卤送入行星球磨机内进行一次球磨至粒径小于15μm，取出后在60℃空气中烘干，然后在供氧条件下进行预烧结，预烧结温度为1140℃，时间为3h，然后取出送入球磨机内进行二次球磨至粒径小于3μm，得粗基料；
3)将氨基醋酸铜、乙酰丙酮钴、氨基磺酸镍共混，送入球磨机内在惰性气氛下进行超细球磨10.5h，得混合细粉，再将该混合细粉与聚丙烯酰胺、十六烷基三甲基溴化铵加入100倍混合细粉质量的水中，加热搅拌，搅拌条件下向其中滴加水合联氨，待全部滴加完成后，超声分散3h，得湿混料；
4)将粗基料与湿混料共混，混匀后置于干燥箱中，调节温度为160℃，保温6h，然后降温至55℃保温3h，得干混料；
5)将干混料再次送入球磨机中球磨至粒径小于1μm，取出烘干后向其中加入占干混料质量0.2％的聚乙烯醇，搅拌均匀，然后定型，定型压力为1100MPa，温度为90℃，时间为15min，得成型体；
6)将成型体进行烧结，先在860℃保温3.5h，然后以一定速率升温至1080℃保温3h，再在700℃回火1h，即可。
将本发明实施例1-5制得的M型钡铁氧体永磁材料进行磁性能测试：最大磁能积(BH)max为38.5-40.7kJ/m3，饱和磁化强度MS为344-361kA/m，剩磁Br为0.495-0.52T，内禀矫顽力Hcj为435-447kA/m，居里温度为390-406℃。
以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (9)

1.一种高磁能M型钡铁氧体永磁材料，其特征在于，包括以下摩尔份数组成：铁源35-60份、硝酸钡4-5份、聚丙烯酰胺2-3份、氨基醋酸铜4-7份、乙酰丙酮钴4-5份、氨基磺酸镍4-5份、水合联氨0.5-1.5份、十六烷基三甲基溴化铵0.5-2份、硬脂酸金属盐1-5份、稀土氧化物0-2.5份、盐卤0-6份。
2.根据权利要求1所述的高磁能M型钡铁氧体永磁材料，其特征在于，包括以下摩尔份数组成：铁源50-60份、硝酸钡4.5-5份、聚丙烯酰胺2.5-3份、氨基醋酸铜5-7份、乙酰丙酮钴4.5-5份、氨基磺酸镍4.5-5份、水合联氨1-1.5份、十六烷基三甲基溴化铵1.5-2份、硬脂酸金属盐4-5份、稀土氧化物1.5-2.5份、盐卤4-6份。
3.根据权利要求1或2所述的高磁能M型钡铁氧体永磁材料，其特征在于：所述铁源为三氧化二铁或柠檬酸铁和铁精矿的组合物，所述铁精矿添加量为铁源总质量的10-20％。
4.根据权利要求1或2所述的高磁能M型钡铁氧体永磁材料，其特征在于：所述稀土氧化物为氧化镧、氧化铈中的一种或两者的组合物。
5.根据权利要求1或2所述的高磁能M型钡铁氧体永磁材料，其特征在于：所述硬脂酸金属盐中金属选自为镁、钡、铜、锌、钙中的一种或多种。
6.根据权利要求1或2所述的高磁能M型钡铁氧体永磁材料的制备方法，其特征在于，步骤如下：
1)按重量粉称取原料；
2)将铁源、硝酸钡、硬脂酸金属盐、稀土氧化物、盐卤送入行星球磨机内进行一次球磨至粒径小于15μm，取出后在60℃空气中烘干，然后在供氧条件下进行预烧结，预烧结温度为1100-1150℃，时间为2-3h，然后取出送入球磨机内进行二次球磨至粒径小于3μm，得粗基料；
3)将氨基醋酸铜、乙酰丙酮钴、氨基磺酸镍共混，送入球磨机内在惰性气氛下进行超细球磨10-12h，得混合细粉，再将该混合细粉与聚丙烯酰胺、十六烷基三甲基溴化铵加入100-120倍混合细粉质量的水中，加热搅拌，搅拌条件下向其中滴加水合联氨，待全部滴加完成后，超声分散3-4h，得湿混料；
4)将粗基料与湿混料共混，混匀后置于干燥箱中，调节温度为130-160℃，保温6h，然后降温至45-60℃保温3h，得干混料；
5)将干混料再次送入球磨机中球磨至粒径小于1μm，取出烘干后向其中加入占干混料质量0.2-0.3％的聚乙烯醇，搅拌均匀，然后定型，定型压力为1100MPa，温度为90℃，时间为15min，得成型体；
6)将成型体进行烧结，先在850-900℃保温3-4h，然后以一定速率升温至1050-1100℃保温3-4h，再在700℃回火1-2h，即可。
7.根据权利要求6所述的高磁能M型钡铁氧体永磁材料的制备方法，其特征在于：步骤2)一次球磨中钢球、原料、水的质量比为3:1:1，二次球磨中钢球、原料、水的质量比为8:1:1.5，步骤3)球磨中钢球、原料、水的质量比为10:1:1.5，步骤5)球磨中钢球、原料、水的质量比为15:1:2。
8.根据权利要求6所述的高磁能M型钡铁氧体永磁材料的制备方法，其特征在于：步骤3)中加热搅拌具体为温度40℃，搅拌速度为200r/min，超声分散具体为温度35℃，频率25kHz。
9.根据权利要求6所述的高磁能M型钡铁氧体永磁材料的制备方法，其特征在于：步骤6)中升温速率具体为2℃/min。
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