CN108558383B - NiZn铁氧体材料及制备方法 - Google Patents

NiZn铁氧体材料及制备方法 Download PDF

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CN108558383B
CN108558383B CN201810297827.1A CN201810297827A CN108558383B CN 108558383 B CN108558383 B CN 108558383B CN 201810297827 A CN201810297827 A CN 201810297827A CN 108558383 B CN108558383 B CN 108558383B
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caco
main
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CN108558383A (zh
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孙科
李楷威
余忠
郭荣迪
蒋晓娜
兰中文
陈川
刘昕
孙亮
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State Grid Corp of China SGCC
University of Electronic Science and Technology of China
Global Energy Interconnection Research Institute
State Grid Beijing Electric Power Co Ltd
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State Grid Corp of China SGCC
University of Electronic Science and Technology of China
Global Energy Interconnection Research Institute
State Grid Beijing Electric Power Co Ltd
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Abstract

NiZn铁氧体材料及制备方法，属于铁氧体材料制备技术领域。本发明的铁氧体材料包括主成分和掺杂剂，主成分包括主料和辅料，按摩尔百分比，以氧化物计算，主料包括：47.1～49.6mol％Fe2O3、31.0～35.0mol％ZnO，余量为NiO，以主料的重量为计算基准，辅料包括0.03～0.05wt％的CaO和0.05～0.08wt％的BaTiO3；以主成分的重量为计算基准，掺杂剂包括：0.05～0.40wt％Bi2O3、0.05～0.40wt％Nb2O5、0.01～0.20wt％CaCO3和0.01～0.20wt％BaTiO3，所述CaCO3和BaTiO3的粒径皆为80nm～120nm。本发明的铁氧体材料兼具高阻抗、高磁导率、可应用频率范围宽且具有较高居里温度的特点。

Description

NiZn铁氧体材料及制备方法
技术领域
本发明属于铁氧体材料制备技术领域，特别涉及宽频带高阻抗、高磁导率NiZn铁氧体材料及其制备方法。
背景技术
电力电缆局部放电在线监测系统作为国家智能电网系统的重要一环，其在电网的正常运行和维护、保障国家财产安全、预防危险事故发生方面有着极为重要的意义。我国电力电缆系统监测手段在最近数十年里逐渐由人工巡检向智能电网在线监测过渡，提高了险情处理的响应速度，有效的降低了安全事故的发生率，极大的节约了电力电缆的运营维护成本。局放检测传感器作为电力电缆局放在线监测系统的核心，对作为磁心材料的NiZn铁氧体提出了高饱和磁感应强度、高磁导率、优异的温度稳定性、高电阻率及高阻抗等性能要求。
针对现在的国产电力电缆局放在线监测装置存在的核心部件磁心材料灵敏度低、可靠性差、进口装置价格昂贵等突出问题，亟需研发出一种宽频带高阻抗、高磁导率的NiZn铁氧体材料作为传感器磁心材料，从而大幅提升传感器的灵敏度，提升电力电缆局放在线监测系统的可靠性和准确性，对国家电网的安全监测与维护成本的降低有着重要的意义。
目前已有专利文献报道高磁导率NiZn或NiCuZn铁氧体材料及其制备方法，如已公开的中国专利CN104402428A中公布了一种高频高磁导率高Q值的NiZn铁氧体，其主要组成成分按摩尔比：17.0～19.0mol％NiO，31.0～33.0mol％ZnO，余量为Fe2O3，添加剂为0.2～0.4wt％SnO2，0.002～0.004wt％Dy2O3，该材料在f＞20MHz时，起始磁导率μi>150，Q值大于100；另一公开的专利CN103396113A中的NiZn铁氧体，其主成分按摩尔比计包括：0.2～0.3mol％Nb2O5、44.0～44.5mol％Fe2O3、12.0～12.5mol％ZnO、5.0～5.5mol％NiO、1.2～1.3mol％TaC、0.4～0.5mol％Ga2O3，主成分中添加的改性杂质按照重量计包括：150～180ppm B2O3、330～350ppm La2O3、460～480ppm V2O5、410～430ppm As、250～280ppm Cr、420～450ppm Te、240～260ppm SiO2、450～480ppm Bi2O3、250～280ppm V，在1MHz～10MHz下具有较高的磁导率(μi≈300，f＝1MHz)、高电阻率、低比损耗、低比温度系数等特性，但是制备过程中加入了价格昂贵的TaC、Te等原料，提高了生产成本，且配方复杂，不利于开展大规模工业生产；还有专利CN104030674A中发明的NiCuZn铁氧体，主成份以摩尔百分比为：48.5mol％～49.5mol％Fe2O3，25.0mol％～29.0mol％ZnO，11.5mol％～20.5mol％NiO，，5.0mol％～9.5mol％CuO，掺杂成分质量百分比为：0≤V2O5≤0.12wt％，制备出的NiCuZn铁氧体材料在100kHz～200kHz频率区间内时，起始磁导率μi为950～1000，饱和磁感应强度Bs≥360mT，矫顽力Hc<32A/m，但是其磁导率在MHz频率范围内下降严重，限制了该材料在高频范围内的使用。以上所述专利制备的镍系铁氧体材料，主要存在两类问题：(1)在低频段范围内具有优异的磁导率和饱和磁感应强度等性能的材料，在高频率条件下性能急剧下降，不符合宽频段的使用要求；(2)在高频下具有高磁导率的材料，它的饱和磁感应强度以及居里温度都偏低，若用于制备传感器磁心，会严重影响到传感器的可靠性与灵敏度。因此开发成分简单，成本低廉，性能优良的宽频带高阻抗、高磁导率NiZn铁氧体材料对于满足当前市场的需求有着重要意义。
发明内容
本发明主要针对现有的NiZn铁氧体材料存在的磁导率低、可应用频率范围窄以及居里温度低等不足之处，提出了一种兼具高阻抗、高磁导率、可应用频率范围宽且具有较高居里温度的NiZn铁氧体材料及其制备方法。
本发明解决所述技术问题采用的技术方案是，NiZn铁氧体材料，包括主成分和掺杂剂，其特征在于，主成分包括主料和辅料，
按摩尔百分比，以氧化物计算，主料包括：47.1～49.6mol％Fe2O3、31.0～35.0mol％ZnO，余量为NiO，
以主料的重量为计算基准，辅料包括：0.03～0.05wt％CaO和0.05～0.08wt％BaTiO3；例如，若主料为100g，则CaO为0.03～0.05g。
以主成分的重量为计算基准，掺杂剂包括：0.05～0.40wt％Bi2O3、0.05～0.40wt％Nb2O5、0.01～0.20wt％纳米CaCO3和0.01～0.20wt％纳米BaTiO3，所述CaCO3和BaTiO3的粒径皆为80nm～120nm。
本发明还提供一种NiZn铁氧体材料制备方法，其特征在于，包括以下步骤：
1)配方
以氧化物计算：主料包括：47.1～49.6mol％Fe2O3，31.0～35.0mol％ZnO，余量为NiO，
以主料重量为基准，加入0.03～0.05wt％CaO和0.05～0.08wt％BaTiO3作为辅料；
2)一次球磨
将步骤1)配好的粉料在球磨机内混合均匀，时间2～3小时；
3)预烧
将步骤2)所得球磨料烘干，在800～1000℃炉内预烧2～3小时；
4)掺杂
将步骤3)所得粉料按如下比例掺杂：0.05～0.40wt％Bi2O3、0.05～0.40wt％Nb2O5、0.01～0.20wt％纳米CaCO3、0.01～0.20wt％纳米BaTiO3，所述CaCO3和BaTiO3粒径为80nm～120nm；
5)二次球磨
将步骤4)得到的粉料在球磨机中球磨4～6小时；
6)成型
将步骤5)所得粉料按重量比加入8～12wt％有机粘合剂，混匀，造粒后，在压机上将粒状粉料压制成坯件；
7)烧结
将步骤6)所得生坯置于烧结炉内烧结，在1100℃～1300℃保温4～6小时。
本发明的主成分采用缺铁配方，有效的抑制了Fe2+的生成，提高了NiZn铁氧体的电阻率和阻抗，非磁性Zn2+离子的引入，可显著降低磁晶各向异性常数和磁致伸缩系数，从而降低磁化阻力，同时，非磁性Zn2+离子特喜占据四面体位，适量引入可以提高分子磁矩，从而提升饱和磁化强度，进而提高磁化动力；基于上述磁化动力和阻力的调控，可以获得更高的磁导率。同时，严格控制ZnO的含量，降低非磁性离子Zn2+对居里温度的影响，使得材料具有较高的居里温度。更为重要的是，在一磨过程中，引入适量的CaCO3、BaTiO3添加剂，使之与原材料充分均匀混合，有助于烧结过程中上述杂质更好地富集于晶界处，提高材料的晶界电阻率，提高材料的阻抗。
在掺杂剂的选择上，充分利用Nb2O5、Bi2O3、纳米CaCO3以及纳米BaTiO3等掺杂剂的助熔和阻晶双性作用，实现复合掺杂剂交互作用的控制，一方面提高烧结密度，降低样品的气孔率，有效的提高材料的磁导率，另一方面，控制晶粒尺寸均匀适中，控制材料的晶粒/晶界特性，改善材料的复数磁导率以及阻抗频谱特性；除以上两方面外，基于砖墙模型理论，利用CaCO3和BaTiO3阻抗高，且易在晶界处富集的特点，通过添加这两种具有高电阻、高介电常数的物质，在晶界处形成高阻抗晶界层，可以有效的提高材料的阻抗，改善材料的高频性能，扩展材料的应用频段。
在烧结工艺方面，结合特种高活性亚微米粉体制备工艺，制备高活性亚微米粉体(平均粒径：0.5μm～0.9μm)，借助复合添加剂，实现材料的高密度均匀晶粒烧结，使得晶粒/晶界可控获得均匀的显微结构，进一步减小样品的气孔率。
总的来说，通过适量控制ZnO含量实现对交换作用及磁晶各向异性常数等的控制，从而可以有效调控NiZn铁氧体材料的居里温度及起始磁导率；通过复合掺杂剂的双性作用，有效促进NiZn铁氧体材料的致密化，使得NiZn铁氧体材料具有低的气孔率和高的饱和磁感应强度，同时添加高阻抗物质CaO以及BaTiO3，控制材料的晶粒/晶界特性，进而改变材料的复数阻抗特性；最后通过特种制备工艺，进一步提高材料的致密度。
附图说明
图1为实施例1的复数磁导率曲线图。
图2为实施例2的复数磁导率曲线图。
图3为实施例3的复数磁导率曲线图。
图4为实施例4的复数磁导率曲线图。
图5为实施例1～4的复数阻抗特性曲线对比图。
具体实施方式
针对目前国内外对宽频带、高磁导率NiZn铁氧体材料的研究现状，本发明提出了一种具有宽频带、高磁导率、高居里温度、高阻抗的NiZn铁氧体及其制备方法。其指导思想是：提高材料分子磁矩、调控超交换作用、添加复合掺杂剂改性、特种粉体制备工艺。首先，通过优选的高纯度Fe2O3、NiO、ZnO为原材料，深入分析了NiZn铁氧体的离子占位以及材料中存在的超交换作用、磁化动力、磁化阻力，尤其对于非磁性离子加入可能带来的居里温度下降，制定最优的配方范围；更为重要的是，在一磨过程中，引入适量的CaCO3、BaTiO3等添加剂，使之与原材料充分均匀混合，有助于烧结过程中更好地富集于晶界处，提高材料的晶界电阻率，提高材料的阻抗；其次，深入分析不同掺杂剂对NiZn铁氧体材料显微结构的影响机制，研究了掺杂剂Bi2O3、Nb2O5、BaTiO3、CaCO3等对NiZn铁氧体晶粒/晶界特性的影响，制定最优的掺杂剂含量，有效的提高材料的阻抗，扩展材料的应用频段；接着，选用并按一定比例配好不同直径大小的超硬球磨介质，结合适宜的分散剂球磨粉料至0.5μm～0.9μm，制备了高活性粉体；最后，以制定的配方和掺杂剂及优化的粉体制备工艺为基础，结合高密度均匀晶粒的烧结工艺制备具有宽频带、高阻抗、高磁导率、高居里温度等特点的NiZn铁氧体。
本发明提供一种NiZn铁氧体材料及制备方法，其材料具有高饱和磁感应强度(Bs≥350mT)、高起始磁导率(μi＝1500±15％)、低矫顽力(Hc＜25A/m)、较高的居里温度(Tc≥140℃)及在应用频段内具有较高的复数磁导率实部(μ'≥85，f＝40MHz)等特性。
NiZn铁氧体材料，包括主成分和掺杂剂，主成分由主料和辅料构成。按摩尔百分比，以氧化物计算，主料为：47.1～49.6mol％Fe2O3、31.0～35.0mol％ZnO，余量为NiO，在Fe2O3、ZnO和NiO三种原材料(以重量比计)基础上，加入0.03～0.05wt％的CaO和0.05～0.08wt％的BaTiO3辅料；
掺杂剂按重量百分比：0.05～0.40wt％Bi2O3、0.05～0.40wt％Nb2O5、0.01～0.20wt％纳米CaCO3(粒径80nm～120nm)、0.01～0.20wt％BaTiO3(粒径80nm～120nm)。
本发明的NiZn铁氧体材料的制备方法，包括以下步骤：
1)配方
主料按摩尔百分比，以氧化物计算：47.1～49.6mol％Fe2O3，31.0～35.0mol％ZnO，余量为NiO，在Fe2O3、ZnO和NiO三种原材料(以重量比计)基础上，加入0.03～0.05wt％的CaO和0.05～0.08wt％的BaTiO3辅料；
2)一次球磨
将按照比例配好的粉料在球磨机内混合均匀，时间2～3小时；
3)预烧
将步骤2所得球磨料烘干，在800～1000℃炉内预烧2～3小时；
4)掺杂
将步骤3所得粉料按如下比例掺杂：0.05～0.40wt％Bi2O3、0.05～0.40wt％Nb2O5、0.01～0.20wt％纳米CaCO3(粒径80nm～120nm)、0.01～0.20wt％纳米BaTiO3(粒径80nm～120nm)；
5)二次球磨
在球磨机中按预定比例配好不同直径大小的超硬球磨介质，将步骤4中得到的粉料按照一定球料比例混合，在球磨机中球磨4～6小时；
6)成型
将步骤5所得粉料按重量比加入8～12wt％有机粘合剂，混匀，造粒后，在压机上将粒状粉料压制成坯件；
7)烧结
将步骤6所得生坯置于气氛烧结炉内烧结，在1100℃～1300℃保温4～6小时。
8)测试
将步骤7所得样品进行性能测试。
采用岩崎SY8232B-H分析仪测试材料饱和磁感应强度Bs、剩余磁感应强度Br、矫顽力Hc；
使用HP4291B阻抗分析仪测试材料的复数磁导率及阻抗；
用阿基米德排水法测试材料密度d；
用DX-2700X射线衍射仪测试并分析材料的物相、晶格常数a；
用Netzsch STA409PC热失重分析仪(TGA)测试材料的居里温度；
本发明采用的NiZn铁氧体材料的指标如下：
饱和磁感应强度Bs：≥350mT(H＝1200A/m，f＝1kHz，T＝25℃)；
矫顽力Hc：＜25A/m(H＝1200A/m，f＝1kHz，T＝25℃)；
起始磁导率μi：1500±10％(H＝1A/m，f＝10kHz，T＝25℃)；
不同频率下的复数磁导率μ'：≥1200(f＝1MHz，T＝25℃)，≥250(f＝10MHz，T＝25℃)，≥85(f＝40MHz，T＝25℃)；
居里温度Tc：≥145℃；
阻抗Z(Ω)：≥15(f≥40MHz，T＝25℃)，≥20(f≥80MHz，T＝25℃)。
实施例1～4：NiZn铁氧体材料制备方法，包括以下步骤：
1、配方
主料采用33.5mol％ZnO，49.5mol％Fe2O3，15.5mol％NiO，
在Fe2O3、ZnO和NiO三种原材料(以重量比计)基础上，加入0.04wt％的CaO和0.05wt％的BaTiO3辅料；
2、一次球磨
将按照比例配好的粉料在球磨机内混合均匀，时间3小时；
3、预烧
将步骤2所得球磨料烘干，在900℃炉内预烧2小时；
4、掺杂
将步骤3所得粉料按重量百分比加入以下添加剂：
Figure BDA0001619081050000071
5、二次球磨
在球磨机中按一定比例配好不同直径大小的超硬球磨介质，将步骤4中得到的粉料按照一定球料比例混合，在球磨机中球磨6小时；
6、成型
将步骤5所得粉料按重量比加入12wt％有机粘合剂，混匀、造粒后，在压机上将粒状粉料压制成坯件；
7、烧结
将步骤6所得坯件置于气氛烧结炉内烧结，在1200℃保温6小时；
8、测试结果
经过以上工艺制备出的NiZn铁氧体材料其性能指标如下：
测试结果参见下表及图1～5。
Figure BDA0001619081050000072

Claims (2)

1.NiZn铁氧体材料，包括主成分和掺杂剂，其特征在于，主成分包括主料和辅料，
按摩尔百分比，以氧化物计算，主料包括：33.5mol％ZnO ，49.5mol％Fe2O3 ，15.5mol％NiO ；
以主料的重量为计算基准，辅料包括0.03～0.05wt％的CaO和0.05～0.08wt％的BaTiO3；
以主成分的重量为计算基准，掺杂剂包括：0.05～0.40wt％Bi2O3、0.05～0.40wt％Nb2O5、0.01～0.20wt％CaCO3和0.01～0.20wt％BaTiO3，所述CaCO3和BaTiO3的粒径皆为80nm～120nm；
所述主料为：
在Fe2O3、ZnO和NiO三种原材料基础上以重量比计，加入0.04wt％的 CaO和0.05wt％的BaTiO3辅料；
掺杂剂为：0.05wt％Bi2O3、0.05wt％Nb2O5、0.03wt％CaCO3和0.01wt％BaTiO3，所述CaCO3和BaTiO3的粒径皆为80nm～120nm。
2. NiZn铁氧体材料制备方法，其特征在于，包括以下步骤：
1)配方
以氧化物计算：主料包括：49.5mol％Fe2O3，33.5mol％ZnO， 15.5mol％NiO，
以主料重量为基准，加入0.04wt％的CaO和0.05wt％的BaTiO3作为辅料；
2)一次球磨
将步骤1)配好的粉料在球磨机内混合均匀，时间2～3小时；
3)预烧
将步骤2)所得球磨料烘干，在800～1000℃炉内预烧2～3小时；
4)掺杂
将步骤3)所得粉料按如下比例掺杂：0.05wt％Bi2O3、0.05wt％Nb2O5、0.03wt％纳米CaCO3、0.01wt％纳米BaTiO3，所述CaCO3和BaTiO3粒径为80nm～120nm；
5)二次球磨
将步骤4)得到的粉料在球磨机中球磨4～6小时；
6)成型
将步骤5)所得粉料按重量比加入8～12wt％有机粘合剂，混匀，造粒后，在压机上将粒状粉料压制成坯件；
7)烧结
将步骤6)所得生坯置于烧结炉内烧结，在1100℃～1300℃保温4～6小时。
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CN110767405B (zh) * 2019-09-24 2021-03-30 江西尚朋电子科技有限公司 一种高性能软磁材料及其元件制备方法
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