CN113024237A - 一种磁性纳米复合材料的制备方法 - Google Patents

一种磁性纳米复合材料的制备方法 Download PDF

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CN113024237A
CN113024237A CN202110265721.5A CN202110265721A CN113024237A CN 113024237 A CN113024237 A CN 113024237A CN 202110265721 A CN202110265721 A CN 202110265721A CN 113024237 A CN113024237 A CN 113024237A
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刘立新
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Shenzhen Xinyi Magnetic Material Co ltd
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Abstract

本发明公开一种磁性纳米复合材料的制备方法，属于磁性材料技术领域。本发明磁性材料包括以下重量份的原料制备而成：三氧化二铁100‑120份、氧化钡10‑20份、氧化钼4‑6份、碳酸钙3‑5份、氧化锰1‑2份、氧化镍5‑7份、氧化铋1‑3份、三氧化钨2‑4份、纳米Si/ZnO0.1‑0.5份。本发明通过加入纳米Si/ZnO，将正硅酸乙酯水解为二氧化硅负载于氧化锌的四氧化三铁的复合物上，同时配合程序升温‑快淬的方法，使得纳米颗粒可以充分的与其他金属氧化物结合，形成紧密结构，有效提升材料的磁性能，所得磁性材料磁积能可以达到59KJ/m3，剩磁可达到629.6mT，磁性能显著提升。

Description

一种磁性纳米复合材料的制备方法
技术领域
本发明属于磁性材料技术领域，具体涉及一种磁性纳米复合材料的制备方法。
背景技术
铁氧体磁性材料是一种复合氧化物烧结体非金属磁性材料，一般分为软磁铁氧体和永磁铁氧体磁性材料。永磁铁氧体磁性材料又包括有钡铁氧体和锶铁氧体，电阻率高，属于半导体类型，故涡流损耗小，矫顽力大，能有效地应用在大气隙的磁路中，特别适于作小型发电机和电动机的永磁体。永磁铁氧体磁性材料的原材料来源丰富，工艺不复杂，成本低，从而具有较高的性价比，被广泛应用于高功率、高转速、高扭矩的各类电机，如高档汽车电机、摩托车启动电机、家用电器以及电动工具马达等领域。目前，为了提高永磁铁氧体的综合磁性能或者提高某些方面的特性性能，主要采用的解决办法是通过改善用来制备永磁铁氧体磁性材料的组分以及相应的比重，或者改良制备永磁铁氧体磁性材料的生产工艺。
中国发明专利201410077393.6(公告日2015年10月14日)公开了一种高磁能永磁铁氧体材料，以重量份数计，包括三氧化二铁100-120份、氧化镧2-4份、二氧化硅16-23份、氧化钡0.5-1.5份、氧化锶0.2-0.8份、碳酸钙15-25份和硬脂酸镁3-9份；以及制备工艺：(1)将三氧化二铁、氧化镧、氧化钡和氧化锶按照比例在空气下进行预烧，预烧温度为1200-1300℃，待原料自然冷却后进行粗破碎；(2)将粗破碎后的原料与二氧化硅、碳酸钙和硬脂酸镁混合后，加入混合物总重1-2倍的水和混合物总重3-6倍的钢球，采用球磨机磨至浆料粒度为0.5-1.0μm；(3)将浆料进行脱水处理，之后在压力为20MPa的条件下压制成型，同时添加5000-8000A/m的取向磁场，得到生坯；(4)将生坯在氧气条件下进行烧结，烧结温度为1200-1300℃，保持2-3h，随后自然降温得到铁氧体材料。制备出的高磁能永磁铁氧体材料，在剩磁、内禀矫顽力及最大磁能积等参数指标明显高于普通的铁氧体材料，提高了整体磁性能。但其制备工艺复杂，成本较高，所制备的永磁铁氧体性能不稳定。因此，改善用来制备永磁铁氧体磁性材料的组分和制备工艺已经成为本领域技术人员的研究热点与难点。
发明内容
本发明针对目前铁氧体永磁材料整体磁性能不佳的问题。本发明提供一种优化的磁性材料配方，实现铁氧体永磁材料综合性能的提升，为实现上述技术目的，本发明所采用的技术方案为：
一种磁性纳米复合材料，包括以下重量份的原料制备而成，三氧化二铁100-120份、氧化钡10-20份、氧化钼4-6份、碳酸钙3-5份、氧化锰1-2份、氧化镍5-7份、氧化铋1-3份、三氧化钨2-4份、纳米Si/ZnO 0.1-0.5份。
优选的，所述纳米Si/ZnO的制备方法为：将5ml正硅酸乙酯滴加到100ml的乙醇溶液中，磁力搅拌，再加入3wt％的氧化锌，再依次加入1.5gFeCl326H2O、4.0g CH3COONa,磁力持续搅拌1h,转移至特氟龙反应釜并于200℃烘箱中反应8h,冷却后转移至离心管,在氮气氛围的手套箱中用去离子水、无水乙醇交替洗涤数次,洗涤后进行固液分离.冷冻干燥48h后研磨即得。
优选的，磁力搅拌的转速为100-300rpm。
一种磁性纳米复合材料的制备方法，包括以下步骤：
1)制备纳米Si/ZnO：将5ml正硅酸乙酯滴加到100ml的乙醇溶液中，磁力搅拌，再加入3wt％的氧化锌，再依次加入1.5gFeCl3· 6H2O、4.0g CH3COONa,磁力持续搅拌1h,转移至特氟龙反应釜并于200℃烘箱中反应8h,冷却后转移至离心管,在氮气氛围的手套箱中用去离子水、无水乙醇交替洗涤数次,洗涤进行固液分离.冷冻干燥48h后研磨即得；
2)按照配方将三氧化二铁100-120份、氧化钡10-20份、氧化钼4-6份、碳酸钙3-5份混合原料后采用硬质氧化锆球为球磨介质球磨12h，烘干后在1300℃下预烧2h；
3)降温后加入氧化锰1-2份、氧化镍5-7份、氧化铋1-3份、三氧化钨2-4份、纳米Si/ZnO0.1-0.5份，进行二次球磨，球磨时间12h，再将混合物置于马弗炉中进行程序升温烧结，后自然冷却降温，得磁性纳米复合材料。
优选的，步骤(2)球磨转速为200r/min。
优选的，步骤(3)程序升温的方式为：5℃/min升温至500℃，保温1h，再以2-3℃/min升温至800℃保温3h，再以1℃/min升温至1000℃烧结1h。
有益效果
本发明针对目前永磁材料结构不均导致的磁性不稳定的问题，通过加入纳米Si/ZnO，将正硅酸乙酯水解为二氧化硅负载于氧化锌的四氧化三铁的复合物上，同时配合程序升温-快淬的方法，使得纳米颗粒可以充分的与其他金属氧化物结合，形成紧密结构，有效提升材料的磁性能，所得磁性材料磁积能可以达到59KJ/m3，剩磁可达到629.6mT，磁性能显著提升。
具体实施方式
下面结合具体实施例对本发明的技术方案做进一步说明，但不限于此。
实施例1
一种磁性纳米复合材料，包括以下重量份的原料制备而成，三氧化二铁100份、氧化钡10份、氧化钼4份、碳酸钙3份、氧化锰1份、氧化镍5份、氧化铋1份、三氧化钨2份、纳米Si/ZnO 0.1份。
所述纳米Si/ZnO的制备方法为：将5ml正硅酸乙酯滴加到100ml的乙醇溶液中，磁力搅拌，再加入3wt％的氧化锌，再依次加入1.5gFeCl3·6H2O、4.0g CH3COONa,磁力持续搅拌1h,转移至特氟龙反应釜并于200℃烘箱中反应8h,冷却后转移至离心管,在氮气氛围的手套箱中用去离子水、无水乙醇交替洗涤数次,洗涤后进行固液分离.冷冻干燥48h后研磨即得。
磁力搅拌的转速为100rpm。
一种磁性纳米复合材料的制备方法，包括以下步骤：
1)制备纳米Si/ZnO：将5ml正硅酸乙酯滴加到100ml的乙醇溶液中，磁力搅拌，再加入3wt％的氧化锌，再依次加入1.5gFeCl3·6H2O、4.0g CH3COONa,磁力持续搅拌1h,转移至特氟龙反应釜并于200℃烘箱中反应8h,冷却后转移至离心管,在氮气氛围的手套箱中用去离子水、无水乙醇交替洗涤数次,洗涤进行固液分离.冷冻干燥48h后研磨即得；
2)按照配方将三氧化二铁100份、氧化钡10份、氧化钼4份、碳酸钙3份混合原料后采用硬质氧化锆球为球磨介质球磨12h，烘干后在1300℃下预烧2h；
3)降温后加入氧化锰1份、氧化镍5份、氧化铋1份、三氧化钨2份、纳米Si/ZnO 0.1份，进行二次球磨，球磨时间12h，再将混合物置于马弗炉中进行程序升温烧结，后自然冷却降温，得磁性纳米复合材料。
步骤(2)球磨转速为200r/min。
步骤(3)程序升温的方式为：5℃/min升温至500℃，保温1h，再以2-3℃/min升温至800℃保温3h，再以1℃/min升温至1000℃烧结1h。
实施例2
一种磁性纳米复合材料，包括以下重量份的原料制备而成，三氧化二铁110份、氧化钡15份、氧化钼5份、碳酸钙4份、氧化锰2份、氧化镍5份、氧化铋2份、三氧化钨4份、纳米Si/ZnO 0.3份。
所述纳米Si/ZnO的制备方法为：将5ml正硅酸乙酯滴加到100ml的乙醇溶液中，磁力搅拌，再加入3wt％的氧化锌，再依次加入1.5gFeCl3·6H2O、4.0g CH3COONa,磁力持续搅拌1h,转移至特氟龙反应釜并于200℃烘箱中反应8h,冷却后转移至离心管,在氮气氛围的手套箱中用去离子水、无水乙醇交替洗涤数次,洗涤后进行固液分离.冷冻干燥48h后研磨即得。
磁力搅拌的转速为300rpm。
一种磁性纳米复合材料的制备方法，包括以下步骤：
1)制备纳米Si/ZnO：将5ml正硅酸乙酯滴加到100ml的乙醇溶液中，磁力搅拌，再加入3wt％的氧化锌，再依次加入1.5gFeCl3·6H2O、4.0g CH3COONa,磁力持续搅拌1h,转移至特氟龙反应釜并于200℃烘箱中反应8h,冷却后转移至离心管,在氮气氛围的手套箱中用去离子水、无水乙醇交替洗涤数次,洗涤进行固液分离.冷冻干燥48h后研磨即得；
2)按照配方将三氧化二铁110份、氧化钡15份、氧化钼5份、碳酸钙4份混合原料后采用硬质氧化锆球为球磨介质球磨12h，烘干后在1300℃下预烧2h；
3)降温后加入氧化锰2份、氧化镍5份、氧化铋2份、三氧化钨4份、纳米Si/ZnO 0.3份，进行二次球磨，球磨时间12h，再将混合物置于马弗炉中进行程序升温烧结，后自然冷却降温，得磁性纳米复合材料。
步骤(2)球磨转速为200r/min。
步骤(3)程序升温的方式为：5℃/min升温至500℃，保温1h，再以2-3℃/min升温至800℃保温3h，再以1℃/min升温至1000℃烧结1h。
实施例3
一种磁性纳米复合材料，包括以下重量份的原料制备而成，三氧化二铁120份、氧化钡20份、氧化钼6份、碳酸钙5份、氧化锰2份、氧化镍7份、氧化铋3份、三氧化钨4份、纳米Si/ZnO 0.5份。
所述纳米Si/ZnO的制备方法为：将5ml正硅酸乙酯滴加到100ml的乙醇溶液中，磁力搅拌，再加入3wt％的氧化锌，再依次加入1.5gFeCl3·6H2O、4.0g CH3COONa,磁力持续搅拌1h,转移至特氟龙反应釜并于200℃烘箱中反应8h,冷却后转移至离心管,在氮气氛围的手套箱中用去离子水、无水乙醇交替洗涤数次,洗涤后进行固液分离.冷冻干燥48h后研磨即得。
磁力搅拌的转速为300rpm。
一种磁性纳米复合材料的制备方法，包括以下步骤：
1)制备纳米Si/ZnO：将5ml正硅酸乙酯滴加到100ml的乙醇溶液中，磁力搅拌，再加入3wt％的氧化锌，再依次加入1.5gFeCl3·6H2O、4.0g CH3COONa,磁力持续搅拌1h,转移至特氟龙反应釜并于200℃烘箱中反应8h,冷却后转移至离心管,在氮气氛围的手套箱中用去离子水、无水乙醇交替洗涤数次,洗涤进行固液分离.冷冻干燥48h后研磨即得；
2)按照配方将三氧化二铁120份、氧化钡20份、氧化钼6份、碳酸钙5份混合原料后采用硬质氧化锆球为球磨介质球磨12h，烘干后在1300℃下预烧2h；
3)降温后加入氧化锰2份、氧化镍7份、氧化铋3份、三氧化钨4份、纳米Si/ZnO 0.5份，进行二次球磨，球磨时间12h，再将混合物置于马弗炉中进行程序升温烧结，后自然冷却降温，得磁性纳米复合材料。
步骤(2)球磨转速为200r/min。
步骤(3)程序升温的方式为：5℃/min升温至500℃，保温1h，再以2-3℃/min升温至800℃保温3h，再以1℃/min升温至1000℃烧结1h。
对比例1
一种磁性纳米复合材料，包括以下重量份的原料制备而成，三氧化二铁120份、氧化钡20份、氧化钼6份、碳酸钙5份、氧化锰2份、氧化镍7份、氧化铋3份、三氧化钨4份、ZnO0.5份。
一种磁性纳米复合材料的制备方法，包括以下步骤：
1)按照配方将三氧化二铁120份、氧化钡20份、氧化钼6份、碳酸钙5份混合原料后采用硬质氧化锆球为球磨介质球磨12h，烘干后在1300℃下预烧2h；
2)降温后加入氧化锰2份、氧化镍7份、氧化铋3份、三氧化钨4份、ZnO 0.5份，进行二次球磨，球磨时间12h，再将混合物置于马弗炉中进行程序升温烧结，后自然冷却降温，得磁性纳米复合材料。
步骤(2)球磨转速为200r/min。
步骤(3)程序升温的方式为：5℃/min升温至500℃，保温1h，再以2-3℃/min升温至800℃保温3h，再以1℃/min升温至1000℃烧结1h。
本对比例除不使用纳米Si/ZnO而使用普通ZnO外，其余均同实施例3。
对比例2
一种磁性纳米复合材料，包括以下重量份的原料制备而成，三氧化二铁120份、氧化钡20份、氧化钼6份、碳酸钙5份、氧化锰2份、氧化镍7份、氧化铋3份、三氧化钨4份、SiO20.5份。
一种磁性纳米复合材料的制备方法，包括以下步骤：
1)按照配方将三氧化二铁120份、氧化钡20份、氧化钼6份、碳酸钙5份混合原料后采用硬质氧化锆球为球磨介质球磨12h，烘干后在1300℃下预烧2h；
2)降温后加入氧化锰2份、氧化镍7份、氧化铋3份、三氧化钨4份、ZnO 0.5份，进行二次球磨，球磨时间12h，再将混合物置于马弗炉中进行程序升温烧结，后自然冷却降温，得磁性纳米复合材料。
步骤(2)球磨转速为200r/min。
步骤(3)程序升温的方式为：5℃/min升温至500℃，保温1h，再以2-3℃/min升温至800℃保温3h，再以1℃/min升温至1000℃烧结1h。
本对比例除不使用纳米Si/ZnO而使用普通SiO2外，其余均同实施例3。
对比例3
一种磁性纳米复合材料，包括以下重量份的原料制备而成，三氧化二铁120份、氧化钡20份、氧化钼6份、碳酸钙5份、氧化锰2份、氧化镍7份、氧化铋3份、三氧化钨4份、纳米Si/ZnO 0.5份。
所述纳米Si/ZnO的制备方法为：将5ml正硅酸乙酯滴加到100ml的乙醇溶液中，磁力搅拌，再加入3wt％的氧化锌，再依次加入1.5gFeCl3·6H2O、4.0g CH3COONa,磁力持续搅拌1h,转移至特氟龙反应釜并于200℃烘箱中反应8h,冷却后转移至离心管,在氮气氛围的手套箱中用去离子水、无水乙醇交替洗涤数次,洗涤后进行固液分离.冷冻干燥48h后研磨即得。
磁力搅拌的转速为300rpm。
一种磁性纳米复合材料的制备方法，包括以下步骤：
1)制备纳米Si/ZnO：将5ml正硅酸乙酯滴加到100ml的乙醇溶液中，磁力搅拌，再加入3wt％的氧化锌，再依次加入1.5gFeCl3·6H2O、4.0g CH3COONa,磁力持续搅拌1h,转移至特氟龙反应釜并于200℃烘箱中反应8h,冷却后转移至离心管,在氮气氛围的手套箱中用去离子水、无水乙醇交替洗涤数次,洗涤进行固液分离.冷冻干燥48h后研磨即得；
2)按照配方将三氧化二铁120份、氧化钡20份、氧化钼6份、碳酸钙5份混合原料后采用硬质氧化锆球为球磨介质球磨12h，烘干后在1300℃下预烧2h；
3)降温后加入氧化锰2份、氧化镍7份、氧化铋3份、三氧化钨4份、纳米Si/ZnO 0.5份，进行二次球磨，球磨时间12h，再将混合物置于马弗炉中进行程序升温烧结，后自然冷却降温，得磁性纳米复合材料。
步骤(2)球磨转速为200r/min。
步骤(3)程序升温的方式为：5℃/min升温至800℃保温3h，再以1℃/min升温至1000℃烧结1h。
本对比例除升温方式与实施例3不同外，其余均同实施例3。
对比例4
本对比例除升温方式与实施例3不同外，其余均同实施例3。
本对比例中步骤(3)程序升温的方式为：5℃/min升温至500℃，保温1h，再以1℃/min升温至1000℃烧结1h。
性能测试
对本发明和对比例所得样品进行测试，具体测试方法为：产品的剩磁Br、磁感矫顽力Hcb、内禀矫顽力Hcj、磁能积BH，采用中国计量科学研究院生产的NIM-500C永磁高温测量仪测量，可输出J-H回线、B-H回线、退磁曲线等，测试环境温度为25℃左右，测试结果的重复性为：Br、Hcb、Hcj均为±0.2％。
表1性能测试结果
磁积能BH(KJ/m3) 内禀矫顽力Hcj(KA/m) 磁感矫顽力Hcb(KA/m) 剩磁Br(mT)
实施例1 55.1 398.5 385.3 623.3
实施例2 57.5 402.6 389.5 625.9
实施例3 59.5 411.8 399.9 629.6
对比例1 51.2 275.1 260.1 612.3
对比例2 50.1 265.2 251.0 613.5
对比例3 52.6 281.8 245.6 616.4
对比例4 53.1 290.2 246.2 617.3
从表中数据我们可以看出，在本发明配方和制备工艺下，所得磁性材料磁积能可以达到59KJ/m3，剩磁可达到629.6mT，磁性能显著提升，而改变了纳米粒子和程序升温工艺的对比例1-4，其磁性能显著下降，这可能是因为，纳米粒子在慢速升温过程中可以有效的控制晶形，充分的与其他金属氧化物结合，形成紧密结构，有效提升材料的磁性能。本发明配方和制备工艺是实现本发明技术效果的关键技术特征，缺一则效弱。
需要说明的是，上述实施例仅仅是实现本发明的优选方式的部分实施例，而非全部实施例。显然，基于本发明的上述实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的其他所有实施例，都应当属于本发明保护的范围。

Claims (6)

1.一种磁性纳米复合材料，其特征在于，包括以下重量份的原料制备而成，三氧化二铁100-120份、氧化钡10-20份、氧化钼4-6份、碳酸钙3-5份、氧化锰1-2份、氧化镍5-7份、氧化铋1-3份、三氧化钨2-4份、纳米Si/ZnO 0.1-0.5份。
2.根据权利要求1所述磁性纳米复合材料，其特征在于，所述纳米Si/ZnO的制备方法为：将5ml正硅酸乙酯滴加到100ml的乙醇溶液中，磁力搅拌，再加入3wt％的氧化锌，再依次加入1.5gFeCl3·6H2O、4.0g CH3COONa,磁力持续搅拌1h,转移至特氟龙反应釜并于200℃烘箱中反应8h,冷却后转移至离心管,在氮气氛围的手套箱中用去离子水、无水乙醇交替洗涤数次,洗涤后进行固液分离.冷冻干燥48h后研磨即得。
3.根据权利要求2所述磁性纳米复合材料，其特征在于，磁力搅拌的转速为100-300rpm。
4.一种权利要求1-3任意一项所述磁性纳米复合材料的制备方法，其特征在于，包括以下步骤：
1)制备纳米Si/ZnO：将5ml正硅酸乙酯滴加到100ml的乙醇溶液中，磁力搅拌，再加入3wt％的氧化锌，再依次加入1.5gFeCl3·6H2O、4.0g CH3COONa,磁力持续搅拌1h,转移至特氟龙反应釜并于200℃烘箱中反应8h,冷却后转移至离心管,在氮气氛围的手套箱中用去离子水、无水乙醇交替洗涤数次,洗涤进行固液分离.冷冻干燥48h后研磨即得；
2)按照配方将三氧化二铁100-120份、氧化钡10-20份、氧化钼4-6份、碳酸钙3-5份混合原料后采用硬质氧化锆球为球磨介质球磨12h，烘干后在1300℃下预烧2h；
3)降温后加入氧化锰1-2份、氧化镍5-7份、氧化铋1-3份、三氧化钨2-4份、纳米Si/ZnO0.1-0.5份，进行二次球磨，球磨时间12h，再将混合物置于马弗炉中进行程序升温烧结，后自然冷却降温，得磁性纳米复合材料。
5.根据权利要求4所述磁性纳米复合材料的制备方法，其特征在于，步骤(2)球磨转速为200r/min。
6.根据权利要求4所述磁性纳米复合材料的制备方法，其特征在于，步骤(3)程序升温的方式为：5℃/min升温至500℃，保温1h，再以2-3℃/min升温至800℃保温3h，再以1℃/min升温至1000℃烧结1h。
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