WO2016169385A1 - 一种软磁MnZn系功率铁氧体 - Google Patents

一种软磁MnZn系功率铁氧体 Download PDF

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WO2016169385A1
WO2016169385A1 PCT/CN2016/077317 CN2016077317W WO2016169385A1 WO 2016169385 A1 WO2016169385 A1 WO 2016169385A1 CN 2016077317 W CN2016077317 W CN 2016077317W WO 2016169385 A1 WO2016169385 A1 WO 2016169385A1
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mol
soft magnetic
power ferrite
nio
zno
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French (fr)
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赵旭
顾小建
卢飞翔
张雪强
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Hengdian Group DMEGC Magnetics Co Ltd
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Hengdian Group DMEGC Magnetics Co Ltd
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Priority to JP2017555697A priority patent/JP6510072B2/ja
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Definitions

  • the invention relates to the technical field of ferrites, in particular to a soft magnetic MnZn system power ferrite.
  • MnZn ferrite is widely used in the field of electronics and communication as a power transformer material.
  • the parameter that is directly related to the output power of a conventional switching power supply is the saturation flux density of the material.
  • a material with a high saturation magnetic flux density can make the switching power supply more compact and thinner.
  • the power loss of the material affects the conversion efficiency of the electrical energy. The lower the power loss, the higher the conversion efficiency of the device.
  • Chinese invention patents CN102063989, CN101483092, CN101552073, CN102194561 have studied the main components and obtained good performance.
  • a saturation magnetic flux density Bs of 100 ° C above 460 mT there is no way to achieve a saturation magnetic flux density Bs of 100 ° C above 460 mT.
  • the Chinese invention patent CN101290827 achieves a saturation magnetic flux density Bs of 460 mT at 100 ° C, but the process is not a conventional soft ferrite process, and mass production is difficult.
  • China's invention patent publication CN103964832 achieved an achievement of a saturation magnetic flux density Bs of more than 470 mT at 100 °C, but 1-4 mol% of NiO was used in its main component. Since the cost of Ni is very high, its material reduces market competitiveness.
  • the present invention is to overcome the shortcomings of low saturation magnetic flux density and large loss in the prior art, and to provide a soft magnetic MnZn-based power ferrite having high saturation magnetic flux density and low loss.
  • a soft magnetic MnZn-based power ferrite comprising a main component and a subcomponent, the main component comprising Fe 2 O 3 , MnO, ZnO and NiO, calculated as the total amount of the main components, and Fe 2 O 3 is 53.0- 55.0 mol%, ZnO accounts for 3.0-7.0 mol%, NiO accounts for 0-1.0 mol%, and MnO is the balance.
  • the by-components include CoO, SiO 2 , CaCO 3 , Nb 2 O 5 and ZrO 2 .
  • the soft magnetic MnZn-based power ferrite material of the present invention is realized by increasing the content of Fe 2 O 3 and reducing the content of ZnO in order to obtain a high Bs value, and is required to maintain a minimum power consumption of 100 ° C, Fe 2
  • the content of O 3 and ZnO needs to be adjusted together.
  • the content of Fe 2 O 3 and ZnO is within the above range, the requirements of high Bs and low power consumption can be satisfied at the same time.
  • the Bs at 100 ° C will be lower than 460 mT;
  • the content of 2 O 3 is higher than the above range, the Fe 2+ ion content will increase, resulting in a decrease in the resistivity of the material, an increase in the eddy current power loss, and the final 100 ° C power loss cannot satisfy the requirement of less than 320 kW/m 3 .
  • the content of NiO contains 0.
  • the main function of NiO in the main component is: when the addition of NiO causes the temperature at the lowest point of power loss to move to high temperature, in order to ensure the lowest power loss at 100 °C, it is necessary to increase the content of Fe 2 O 3 , so the material after adding NiO The Bs value has increased. At the same time, the addition of NiO will change the temperature coefficient of the anisotropic constant of the material, so the power loss of the material at 25 ° C will be improved, and the power loss at 100 ° C will increase. When the content of NiO exceeds the above range, 100 ° C The power loss will exceed the requirement of less than 320 kW/m 3 .
  • a unique component formulation and a doping element as a subcomponent are mutually blended, obtained by grinding, pressing, and sintering.
  • the main component formula strives to provide a favorable basis for doping more reasonably.
  • the unique doping promotes better liquid phase sintering, finer grain formation, and more uniform and finer growth.
  • the grain distribution while controlling the porosity of the grain boundary, forms a higher sintered density, and finally produces a more reasonable soft magnetic microstructure, thereby obtaining a soft magnetic MnZn-based power ferrite with high saturation magnetic flux density and low loss.
  • the subcomponent includes a first subcomponent and a second subcomponent, and the first subcomponent is CoO, and the content of CoO is 0 to 0.15 wt% based on the total amount of the main components.
  • the content of CoO contains 0.
  • the main role of the first subcomponent CoO is: when CoO is added, the temperature at the lowest point of power loss moves to a low temperature. In order to ensure the lowest power loss at 100 °C, it is necessary to reduce the content of Fe 2 O 3 , so the material after adding CoO The Bs value decreased. When the CoO content exceeded the above range, the Bs value at 100 °C could not meet the requirement of more than 460 mT.
  • the addition of CoO will change the temperature coefficient of the anisotropic constant of the material, so the power loss of the material at 25 ° C will be improved, and the power loss at 100 ° C will increase, but within the above range, the power loss requirements of the material are Meets the requirements of less than 320kW/m 3 .
  • the second subcomponent is SiO 2 , CaCO 3 , Nb 2 O 5 and ZrO 2 , based on the total amount of the main components, SiO 2 is 0.005-0.015 wt%, and CaCO 3 is 0.03-0.15.
  • the wt%, Nb 2 O 5 is 0.05-0.4 wt%, and the ZrO 2 is 0.05-0.4 wt%.
  • the saturation magnetic flux density Bs of the soft magnetic MnZn-based power ferrite is greater than 550 mT at 25 ° C, and the saturation magnetic flux of the soft magnetic MnZn-based power ferrite at 100 ° C
  • the pass density Bs is greater than 460 mT.
  • the soft magnetic MnZn system power ferrite power loss Pcv is less than 750 kW/m 3 at 25 ° C, and the soft magnetic MnZn system power ferrite power is 100 ° C.
  • the loss Pcv is less than 320 kW/m 3 .
  • the beneficial effects of the invention are: the saturation magnetic flux density Bs of 100 ° C is greater than 460 mT, and the core loss Pcv of 100 ° C is less than 320 kW / m 3 ; because of its excellent performance, in the practical application of the product, the device can be further Miniaturization, and due to very low losses, the device's operating efficiency can be further improved.
  • the ratios were calculated in the form of Fe 2 O 3 , MnO, ZnO, and the three raw materials of Fe 2 O 3 , Mn 3 O 4 and ZnO were weighed, and then deionized in the sand mill. The water was mixed and broken for 40 minutes. Spray granulation was carried out after 10 minutes of circulating mixing.
  • the spray was placed in a pre-burning furnace and calcined at 850 ° C for 3 hours.
  • auxiliary components were added to the pre-sintered material: CaCO 3 : 0.08 wt %, SiO 2 : 0.05 wt%, Nb 2 O 5 : 0.02 wt%, and ZrO 2 : 0.02 wt%.
  • CoO and NiO were weighed according to the respective examples and comparative examples. The powder was then placed in a sand mill and deionized water was added for secondary sanding for 90 minutes.
  • the temperature was raised at a certain oxygen and nitrogen ratio, and sintered at a temperature of 1300 ° C for 5 hours.
  • the partial pressure of oxygen during sintering was 5%, and then cooled to room temperature at a certain ratio of oxygen and nitrogen.
  • the sintered sample ring was tested for power consumption Pcv and saturation magnetic flux density Bs using the SY8218 instrument of Japan Iwasaki Corporation.
  • the test conditions were as follows: Pcv was tested at 100 kHz, 200 mT; Bs was tested at 50 Hz, 1194 A/m.
  • the soft magnetic MnZn power ferrite of the present invention has a saturation magnetic flux density Bs of more than 550 mT at 25 ° C and a saturation magnetic at 100 ° C. greater than 460 mT flux density Bs; power-based soft magnetic MnZn ferrite of the present invention, at 100kHz, 200mT test conditions, the power loss Pcv at 25 deg.] C of less than 750kW / m 3, the power loss Pcv at 100 deg.] C of less than 320kW / m 3 . It can be seen that the soft magnetic MnZn-based power ferrite of the present invention has both a high saturation magnetic flux density Bs and a low loss Pcv, and has a very good market prospect.

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Abstract

本发明公开了一种软磁MnZn系功率铁氧体，旨在提供一种饱和磁通密度高、损耗低的软磁MnZn系功率铁氧体。它包括主成分和副成分，所述的主成分包括Fe2O3、MnO、ZnO和NiO，以主成分的总量计算，Fe2O3占53.0-55.0mol％，ZnO占3.0-7.0mol％，NiO占0-1.0mol％，MnO为余量，所述的副成分包括CoO、SiO2、CaCO3、Nb2O5和ZrO2。本发明的有益效果是：100℃的饱和磁通密度Bs大于460mT，100℃的磁芯损耗Pcv小于320kW/m3；因为其具有如此优良的性能，在产品的实际应用上，可以使器件进一步小型化，并且由于非常低的损耗，器件的工作效率还可以进一步提高。

Description

一种软磁MnZn系功率铁氧体 技术领域
本发明涉及铁氧体相关技术领域，尤其是指一种软磁MnZn系功率铁氧体。
背景技术
MnZn铁氧体广泛应用于电子、通讯领域作为电源变压器材料。传统开关电源的输出功率与材料直接相关的参数就是材料的饱和磁通密度。高饱和磁通密度的材料可以使开关电源更加小型化、薄型化。材料的功率损耗会影响电能的转化效率，越低功率损耗，器件的转化效率越高。
近年来，行业对高饱和磁通密度低损耗的铁氧体材料进行了各种研究，如中国发明专利公开CN102063989、CN101483092、CN101552073、CN102194561等对主成分进行了研究，获得了很好的性能，但是其100℃的饱和磁通密度Bs都没有办法做到460mT以上。中国发明专利公开CN101290827达到了100℃饱和磁通密度Bs在460mT，但是其工艺并不是传统的软磁铁氧体工艺，批量生产困难。中国发明专利公开CN103964832获得了100℃饱和磁通密度Bs在470mT以上的成就，但是其主成分中使用了1-4mol％的NiO，由于Ni的成本非常高，其材料降低了市场竞争力。
发明内容
本发明是为了克服现有技术中存在饱和磁通密度低、损耗大的不足，提供了一种饱和磁通密度高、损耗低的软磁MnZn系功率铁氧体。
为了实现上述目的，本发明采用以下技术方案：
一种软磁MnZn系功率铁氧体，包括主成分和副成分，所述的主成分包 括Fe2O3、MnO、ZnO和NiO，以主成分的总量计算，Fe2O3占53.0-55.0mol％，ZnO占3.0-7.0mol％，NiO占0-1.0mol％，MnO为余量，所述的副成分包括CoO、SiO2、CaCO3、Nb2O5和ZrO2。
本发明的软磁MnZn系功率铁氧体材料，为了得到较高的Bs值，通过增加Fe2O3的含量，以及减少ZnO的含量来实现，由于需要保持100℃的功耗最低，Fe2O3和ZnO的含量需要搭配调整来实现。而Fe2O3和ZnO的含量在上述范围内时，可以同时满足高Bs和低功耗的要求，当Fe2O3含量低于上述范围时，100℃的Bs将低于460mT；当Fe2O3的含量高于上述范围时，Fe2+离子含量将增加，导致材料的电阻率下降，涡流功率损耗上升，最终100℃的功率损耗不能满足小于320kW/m3的要求。
其中：NiO的含量范围中包含0。主成分中NiO的主要作用是：当NiO的加入会使功率损耗最低点的温度向高温移动，为了保证100℃的功率损耗最低，需要增加Fe2O3的含量，所以加入了NiO后材料的Bs值有所提高。同时，NiO的加入会改变材料的各向异性常数的温度系数，所以材料25℃的功率损耗会有所改善，而100℃的功率损耗会上升，当NiO的含量超过上述范围时，100℃的功率损耗会超过小于320kW/m3的要求。本发明中，采用特有的组分配方和作为副成分的掺杂元素相互配合，经过研磨、压制、烧结而得。其中，主成分配方力求更合理地为掺杂提供有利的基础，在此基础上，进而以独到的掺杂促进更好地液相烧结、更细化晶粒，生长出更为均匀细化的晶粒分布，同时控制晶界气孔率，形成较高烧结密度，最终生成更为合理的软磁微观结构，从而获得饱和磁通密度高、损耗低的软磁MnZn系功率铁氧体。
作为优选，所述的副成分包括第一副成分和第二副成分，所述的第一副 成分为CoO，以主成分的总量计算为基础，CoO的含量为0-0.15wt％。其中：CoO的含量范围中包含0。第一副成分CoO的主要作用是：当加入CoO会使功率损耗最低点的温度向低温移动，为了保证100℃的功率损耗最低，需要减少Fe2O3的含量，所以加入了CoO后材料的Bs值有所下降，当CoO含量超过上述范围时，100℃的Bs值不能满足大于460mT的要求。另外，CoO的加入会改变材料的各向异性常数的温度系数，所以材料25℃的功率损耗会有所改善，而100℃的功率损耗会上升，但在上述范围内，材料的功率损耗要求都符合了小于320kW/m3的要求。
作为优选，所述的第二副成分为SiO2、CaCO3、Nb2O5和ZrO2，以主成分的总量计算为基础，SiO2为0.005-0.015wt％、CaCO3为0.03-0.15wt％、Nb2O5为0.05-0.4wt％、ZrO2为0.05-0.4wt％。
作为优选，在1194A/m的测试条件下，25℃时所述软磁MnZn系功率铁氧体的饱和磁通密度Bs大于550mT，100℃时所述软磁MnZn系功率铁氧体的饱和磁通密度Bs大于460mT。
作为优选，在100kHz、200mT的测试条件下，25℃时所述的软磁MnZn系功率铁氧体功率损耗Pcv小于750kW/m3，100℃时所述的软磁MnZn系功率铁氧体功率损耗Pcv小于320kW/m3。
本发明的有益效果是：100℃的饱和磁通密度Bs大于460mT，100℃的磁芯损耗Pcv小于320kW/m3；因为其具有如此优良的性能，在产品的实际应用上，可以使器件进一步小型化，并且由于非常低的损耗，器件的工作效率还可以进一步提高。
具体实施方式
下面结合具体实施方式对本发明做进一步的描述。
由于本发明可以使用传统工艺进行批量生产，故以下实施案例均采用统一的生产工艺进行生产，仅配方有所区别，具体制备工艺如下：
1.配料
按照各实施例与对比例配比，分别以Fe2O3、MnO、ZnO形式计算比例，称取Fe2O3、Mn3O4、ZnO三种原料，然后在砂磨机中加入去离子水进行混合和破碎，时间40分钟。循环混合10分钟后进行喷雾造粒。
2.预烧
将喷雾料放入预烧炉中，在850℃下进行预烧，时间3个小时。
3.二次砂磨
在预烧料中加入以下重量百分比的辅助成分：CaCO3：0.08wt％，SiO2：0.05wt％，Nb2O5：0.02wt％，ZrO2：0.02wt％。其中：CoO和NiO按照各实施例与对比例称取。然后将粉料放入砂磨机中加入去离子水进行二次砂磨，砂磨时间90分钟。
4.喷雾造粒和成型
在二次砂磨料中加入约0.08wt％的PVA，以及0.004wt％的消泡剂，然后在喷雾塔中进行喷雾造粒成50-200μm的颗粒。将不同实施例与对比例的颗粒成型成密度为3.00-3.15g/cm3的H25*15*8mm标准样环毛坯。
5.烧结
在一定的氧气和氮气比例下升温，在1300℃的温度条件下烧结5小时，烧结时的氧气分压为5％，然后在一定的氧气和氮气的比例下冷却到室温。
6.测试
将烧结好的样环用日本岩崎公司的SY8218仪器进行功耗Pcv及饱和磁通密度Bs的测试。测试条件分别为：在100kHz，200mT的条件下测试Pcv；在50Hz，1194A/m的条件下测试Bs。
以下是为了更好的说明本发明而列举的实施例，但是本发明并不限于这些实施例。
实施例1
Fe2O3＝54.8mol％、ZnO＝3mol％、MnO＝42.2mol％、NiO＝0.0mol％、CoO＝0.08wt％。
实施例2
Fe2O3＝54.4mol％、ZnO＝4mol％、MnO＝41.6mol％、NiO＝0.0mol％、CoO＝0.08wt％。
实施例3
Fe2O3＝54.0mol％、ZnO＝5mol％、MnO＝41.0mol％、NiO＝0.0mol％、CoO＝0.08wt％。
实施例4
Fe2O3＝53.6mol％、ZnO＝6mol％、MnO＝40.4mol％、NiO＝0.0mol％、CoO＝0.08wt％。
实施例5
Fe2O3＝53.2mol％、ZnO＝7mol％、MnO＝39.8mol％、NiO＝0.0mol％、CoO＝0.08wt％。
对比例1
Fe2O3＝55.2mol％、ZnO＝2mol％、MnO＝42.8mol％、NiO＝0.0mol％、CoO＝0.08wt％。
对比例2
Fe2O3＝52.8mol％、ZnO＝8mol％、MnO＝39.2mol％、NiO＝0.0mol％、CoO＝0.08wt％。
实施例6
Fe2O3＝54.0mol％、ZnO＝6mol％、MnO＝39.5mol％、NiO＝0.5mol％、CoO＝0.08wt％。
实施例7
Fe2O3＝54.0mol％、ZnO＝6mol％、MnO＝39.1mol％、NiO＝0.9mol％、CoO＝0.08wt％。
实施例8
Fe2O3＝54.0mol％、ZnO＝6mol％、MnO＝39.0mol％、NiO＝1.0mol％、CoO＝0.08wt％。
对比例3
Fe2O3＝54.4mol％、ZnO＝6mol％、MnO＝37.6mol％、NiO＝2.0mol％、CoO＝0.08wt％。
实施例9
Fe2O3＝53.8mol％、ZnO＝6mol％、MnO＝40.2mol％、NiO＝0.0mol％、CoO＝0.0wt％。
实施例10
Fe2O3＝53.7mol％、ZnO＝6mol％、MnO＝40.3mol％、NiO＝0.0mol％、CoO＝0.04wt％。
实施例11
Fe2O3＝53.5mol％、ZnO＝6mol％、MnO＝40.5mol％、NiO＝0.0mol％、CoO＝0.12wt％。
实施例12
Fe2O3＝53.4mol％、ZnO＝6mol％、MnO＝40.6mol％、NiO＝0.0mol％、CoO＝0.15wt％。
对比例4
Fe2O3＝53.0mol％、ZnO＝6mol％、MnO＝41.0mol％、NiO＝0.0mol％、CoO＝0.20wt％。
根据以上各实施例与对比例的配方进行制备软磁MnZn系功率铁氧体，并压环烧结测试性能，测试结果见表1。
表1
Figure PCTCN2016077317-appb-000001
从表1中的各项数据分析可得：(1)实施例1-5和对比例1、2相比较，当ZnO的含量低于3mol％时，软磁MnZn系功率铁氧体的功率损耗上升；当ZnO的含量高于7mol％时，软磁MnZn系功率铁氧体的饱和磁通密度降低；(2)实施例4、6、7、8和对比例3相比较，当NiO的含量高于1mol％时，软磁MnZn系功率铁氧体在100℃时的功率损耗上升；(3)实施例4、9、10、11、12和对比例4相比较，当CoO的含量高于0.15wt％时，软磁MnZn系功率铁氧体的饱和磁通密度降低；软磁MnZn系功率铁氧体在100℃时的功率损耗上升。由表1各项性能逐项对比可见：在1194A/m测试条件下，本发明的软磁MnZn系功率铁氧体在25℃时的饱和磁通密度Bs大于550mT，在100℃时的饱和磁通密度Bs大于460mT；本发明的软磁MnZn系功率铁氧体 在100kHz、200mT测试条件下，25℃时的功率损耗Pcv小于750kW/m3，100℃时的功率损耗Pcv小于320kW/m3。由此可见，本发明的软磁MnZn系功率铁氧体同时具备了高饱和磁通密度Bs和低损耗Pcv，具有非常好的市场前景。

Claims (5)

  1. 一种软磁MnZn系功率铁氧体，其特征是，包括主成分和副成分，所述的主成分包括Fe2O3、MnO、ZnO和NiO，以主成分的总量计算，Fe2O3占53.0-55.0mol％，ZnO占3.0-7.0mol％，NiO占0-1.0mol％，MnO为余量，所述的副成分包括CoO、SiO2、CaCO3、Nb2O5和ZrO2。
  2. 根据权利要求1所述的一种软磁MnZn系功率铁氧体，其特征是，所述的副成分包括第一副成分和第二副成分，所述的第一副成分为CoO，以主成分的总量计算为基础，CoO的含量为0-0.15wt％。
  3. 根据权利要求2所述的一种软磁MnZn系功率铁氧体，其特征是，所述的第二副成分为SiO2、CaCO3、Nb2O5和ZrO2，以主成分的总量计算为基础，SiO2为0.005-0.015wt％、CaCO3为0.03-0.15wt％、Nb2O5为0.05-0.4wt％、ZrO2为0.05-0.4wt％。
  4. 根据权利要求1或2或3所述的一种软磁MnZn系功率铁氧体，其特征是，在1194A/m的测试条件下，25℃时所述软磁MnZn系功率铁氧体的饱和磁通密度Bs大于550mT，100℃时所述软磁MnZn系功率铁氧体的饱和磁通密度Bs大于460mT。
  5. 根据权利要求1或2或3所述的一种软磁MnZn系功率铁氧体，其特征是，在100kHz、200mT的测试条件下，25℃时所述的软磁MnZn系功率铁氧体功率损耗Pcv小于750kW/m3，100℃时所述的软磁MnZn系功率铁氧体功率损耗Pcv小于320kW/m3。
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JP6510072B2 (ja) 2019-05-08
EP3288044A1 (en) 2018-02-28
CN104934181A (zh) 2015-09-23
EP3288044A4 (en) 2018-10-31

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