CN112592170A - 锰锌铁氧体材料及其制备方法和应用 - Google Patents
锰锌铁氧体材料及其制备方法和应用 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 title claims abstract description 32
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 26
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 24
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000292 calcium oxide Substances 0.000 claims abstract description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011787 zinc oxide Substances 0.000 claims abstract description 15
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract 3
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract 3
- 239000002002 slurry Substances 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims 5
- 238000000748 compression moulding Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 abstract description 6
- 230000006698 induction Effects 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 3
- 239000000696 magnetic material Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 230000033228 biological regulation Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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Abstract
本发明提供了一种锰锌铁氧体材料及其制备方法和应用，包括主料成分及添加剂成分，主料包括72.10‑72.70wt％氧化铁、3.2‑4.5wt％氧化锌及余量氧化锰，添加剂包括0.02‑0.2wt％氧化钙、0.01‑0.05wt％纳米二氧化硅、0‑0.06wt％五氧化二铌、0‑0.06wt％氧化锆和0.1‑0.3wt％四氧化三钴；制备方法包括称重、混合、预烧、球磨、砂磨、造粒、成型及烧结等步骤；本发明的材料可以在高频开关电源中应用；本发明的材料具有在高频(1MHz、50mT)条件下25℃及100℃下功率损耗≤250kW/m3的性能，同时具有常温(25℃)、高温(100℃)下的高饱和磁感应强度的特点。
Description
技术领域
本发明属于锰锌软磁铁氧体材料技术领域，具体涉及一种锰锌铁氧体材料及其制备方法，其可用于高频开关电源。
背景技术
随着科学技术的不断进步，电子技术的不断发展，电子设备也向着便携化、智能化和小型化的趋势发展。作为应用于功率转换与传输场合的基础材料锰锌功率铁氧体材料也必须适应这样的趋势，尤其是随着开关电源的高频化、小型轻量化和平面贴装化方向的发展，其对锰锌功率铁氧体材料的要求也越来越高。
锰锌铁氧体材料具有晶粒细小均匀、较低的气孔率、较高的晶界电阻及烧结后的材料内部不残留Fe2O3等要素，才能使材料在高频率下具备低损耗的特性。
发明内容
针对现有技术中的不足，本发明的首要目的是提供一种高频低损耗锰锌铁氧体材料。
本发明的第二个目的是提供一种上述锰锌铁氧体材料的制备方法。
本发明的第三个目的是提供一种上述锰锌铁氧体材料的用途。
为达到上述首要目的，本发明的解决方案是：
一种锰锌铁氧体材料，其包括主料和添加剂；
主料包括如下组分：
氧化铁(Fe2O3) 72.10-72.70wt％，
氧化锌(ZnO) 3.2-4.5wt％，
氧化锰(MnO) 余量；
添加剂以主料为基准，包括如下组分：
优选地，主料中氧化铁的含量为72.4-72.7wt％，氧化锌的含量为3.5-4.2wt％。
优选地，添加剂中氧化钙的含量为0.04-0.12wt％，纳米二氧化硅的含量为0.02-0.04wt％，纳米二氧化硅的粒径≤100nm，四氧化三钴的含量为0.15-0.25wt％，氧化锆的含量为0.02-0.05wt％，五氧化二铌的含量为0.01-0.03wt％。
优选地，添加剂中氧化钙和纳米二氧化硅的比值为1:1-4:1，更优选为2:1-3:1。
为达到上述第二个目的，本发明的解决方案是：
一种上述的锰锌铁氧体材料的制备方法，其包括如下步骤：
(1)、选取Fe2O3、MnO及ZnO原材料，并进行称重；
(2)、将上述三种主料放入球磨机中进行混合，并初步研磨得到混合物；
(3)、将混合物置于马沸炉中在900-950℃，保温1-2h进行预烧；
(4)、预烧后的物料放入球磨机中进行球磨，球磨后的物料放入研磨机中加入纯水和添加剂(CaO、纳米SiO2、Co3O4、ZrO2和Nb2O5)进行砂磨，此阶段主要补正主料的成分及加入添加剂一起磨细，磨细后的料浆粒度不能大于1.5μm；
(5)、将砂磨后的料浆烘干后加入聚乙烯醇(PVA)进行造粒，并将造粒后的料粉压制成型；
(6)、将成型的坯件放入具备气氛调节的烧结炉中，并在氮气保护下进行烧结。
优选地，步骤(4)中，磨细后的料浆粒度不能大于1.2μm。
优选地，步骤(6)中，氮气保护下，烧结的保温温度为1110-1150℃。
优选地，步骤(6)中，烧结时，升温阶段400-500℃至保温温度1110-1150℃，氧含量不大于1.5％。
为达到上述第三个目的，本发明的解决方案是：
一种上述的锰锌铁氧体材料可以在高频开关电源中得以应用。
由于采用上述方案，本发明的有益效果是：
本发明采用特定含量的主料和添加剂制备得到锰锌铁氧体材料，该材料具有在高频(1MHz、50mT)条件下具有更低的功率损耗性能，即25℃及100℃温度下功率损耗均≤250kW/m3，且同时具有常温(25℃)、高温(100℃)下的高饱和磁感应强度特点，故本发明的锰锌铁氧体材料具有高频低损耗的特点。
具体实施方式
本发明提供了一种锰锌铁氧体材料及其制备方法和应用。
<锰锌铁氧体材料>
本发明的锰锌铁氧体材料包括主料和添加剂；其中，主料包括包括如下组分：
Fe2O3 72.10-72.70wt％，
ZnO 3.2-4.5wt％，
MnO 余量；
其中，主料中Fe2O3的添加量优选为72.4-72.7wt％，ZnO的添加量优选为3.5-4.2wt％。
添加剂以主料为基准，包括如下组分：
其中，添加剂中CaO和纳米SiO2(粒径≤100nm)的比值需控制在1:1-4:1之间，更优选为2:1-3:1。
添加剂中CaO的添加量优选为0.04-0.12wt％，纳米SiO2的添加量优选为0.02-0.04wt％，Co3O4的添加量优选为0.15-0.25wt％，ZrO2的添加量优选为0.02-0.05wt％，Nb2O5的添加量优选为0.01-0.03wt％。
<锰锌铁氧体材料的制备方法>
本发明的锰锌铁氧体材料的制备方法包括如下步骤：
(1)、选取Fe2O3、MnO及ZnO原材料，并进行称重；
(2)、将上述三种主料放入球磨机中进行混合，并初步研磨得到混合物；
(3)、将混合物置于马沸炉中在900-950℃，保温1-2h进行预烧；
(4)、预烧后的物料放入球磨机中进行球磨，球磨后的物料放入研磨机中加入纯水和添加剂(CaO、纳米SiO2、Co3O4、ZrO2和Nb2O5)进行砂磨，此阶段主要补正主料的成分及加入添加剂一起磨细，磨细后的料浆D50粒度不能大于1.5μm；
(5)、将砂磨后的料浆烘干后加入PVA进行造粒，并将造粒后的料粉压制成型；
(6)、将成型的坯件放入具备气氛调节的烧结炉中，并在氮气气氛保护下，保温温度为1110-1150℃进行烧结。
其中，在步骤(4)中，磨细后的料浆D50粒度不能大于1.2μm。
在步骤(6)中，氮气气氛保护下，烧结时根据纳米SiO2的加入量调整保温温度，纳米SiO2加入量越大则选择的烧结温度越低，烧结的保温温度优选为1115-1130℃。
在步骤(6)中，烧结气氛在升温阶段400-500℃至保温温度1115-1130℃，氧含量控制在≤1.5％。
进一步地，烧结时，在500℃至保温温度阶段即采取低氧环境下升温，氧含量控制在≤1.0％。
<锰锌铁氧体材料的用途>
本发明的锰锌铁氧体材料可以在高频开关电源中得以应用。
以下结合实施例对本发明作进一步的说明。
实施例1：
本实施例的锰锌铁氧体材料的制备方法包括如下步骤：
(1)、称取72.5wt％Fe2O3、4.0wt％ZnO和余量的MnO原材料，放入球磨机中混合30min，并初步研磨得到混合物；
(2)、将混合物置于马沸炉中900℃，保温1h进行预烧，之后取出冷却；
(3)、预烧后的粉料放入球磨机中球磨30min取出，球磨后的粉料放入研磨机中，同时加入添加剂(CaO添加量为0.04wt％，纳米SiO2添加量为0.02wt％，Co3O4添加量为0.25wt％，ZrO2添加量为0.04wt％，Nb2O5添加量为0.01wt％，并且CaO：纳米SiO2的加入比例为2:1)，并加入纯水湿磨至料浆D50粒径为1.17μm；
(4)、将砂磨后的料浆烘干后加入PVA进行造粒，并压制成型外径为
的样环；
(5)、将样环置于具备气氛调节的烧结炉中，烧结温度根据纳米SiO2添加量设定为1125℃，其中500-1125℃的升温阶段氧含量控制在≤0.1％；对烧结后的样环进行电性能检测，结果如表1所示。
实施例2：
本实施例的锰锌铁氧体材料的制备方法包括如下步骤：
(1)、称取72.6wt％Fe2O3、3.9wt％ZnO和余量的MnO原材料，放入球磨机中混合30min，并初步研磨得到混合物；
(2)、将混合物置于马沸炉中900℃，保温1h进行预烧，之后取出冷却；
(3)、预烧后的粉料放入球磨机中球磨30min取出，球磨后的粉料放入研磨机中，同时加入添加剂(CaO添加量为0.10wt％，纳米SiO2添加量为0.04wt％，Co3O4添加量为0.2wt％，ZrO2添加量为0.04wt％，Nb2O5添加量为0.01wt％，并且CaO：纳米SiO2的加入比例为2.5:1)，并加入纯水湿磨至料浆D50粒径为1.10μm；
(4)、将砂磨后的料浆烘干后加入PVA进行造粒，并压制成型外径为
的样环；
(5)、将样环置于具备气氛调节的烧结炉中，烧结温度根据纳米SiO2添加量设定为1110℃，其中500-1110℃的升温阶段氧含量控制在≤0.1％；对烧结后的样环进行电性能检测，结果如表1所示。
实施例3：
本实施例的锰锌铁氧体材料的制备方法包括如下步骤：
(1)、称取72.7wt％Fe2O3、3.7wt％ZnO和余量的MnO原材料，放入球磨机中混合30min，并初步研磨得到混合物；
(2)、将混合物置于马沸炉中900℃，保温1h进行预烧，之后取出冷却；
(3)、预烧后的粉料放入球磨机中球磨30min取出，球磨后的粉料放入研磨机中，同时加入添加剂(CaO添加量为0.09wt％，纳米SiO2添加量为0.03wt％，Co3O4添加量为0.2wt％，ZrO2添加量为0.03wt％，Nb2O5添加量为0.02wt％，并且CaO：纳米SiO2的加入比例为3:1)，并加入纯水湿磨至料浆D50粒径为1.20μm；
(4)、将砂磨后的料浆烘干后加入PVA进行造粒，并压制成型外径为
的样环；
(5)、将样环置于具备气氛调节的烧结炉中，烧结温度根据纳米SiO2添加量设定为1120℃，其中500-1120℃的升温阶段氧含量控制在≤0.1％；对烧结后的样环进行电性能检测，结果如表1所示。
对比例1：
与实施例1不同之处，烧结温度设定为1160℃，结果如表1所示。
对比例2：
与实施例2不同之处，加入CaO添加量为0.10wt％、纳米SiO2添加量为0.02wt％，CaO：纳米SiO2的加入比例为5:1，结果如表1所示。
对比例3：
与实施例3不同之处，900℃之前的升温阶段在空气中烧结，900-1120℃的升温阶段氧含量控制在≤0.1％，结果如表1所示。
对比例4：
与实施例1不同之处，称取71.80wt％Fe2O3、4.0wt％ZnO和余量的MnO原材料，结果如表1所示。
对比例5：
与实施例1不同之处，称取72.85wt％Fe2O3、4.0wt％ZnO和余量的MnO原材料，结果如表1所示。
对比例6：
与实施例1不同之处，称取72.5wt％Fe2O3、3.0wt％ZnO和余量的MnO原材料，结果如表1所示。
表1各实施例和对比例的性能数据比较
由上述性能测试结果比较可知，采用本发明的配方及制备方法所得的锰锌铁氧体材料在1MHz、50mT条件下具有更低的功率损耗，25℃及100℃温度下均≤250kW/m3，且具有较高的高低温饱和磁感应强度。本发明中因为该材料主要是考核高低温损耗及饱和磁感应强度的整体性能，而不是单一温度的单一性能高低，因此会出现某一条件下数值会更好，但其它条件下则数值不能完全达标的情况。
上述对实施例的描述是为了便于该技术领域的普通技术人员能理解和使用本发明。熟悉本领域技术人员显然可以容易的对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中，而不必经过创造性的劳动。因此，本发明不限于上述实施例。本领域技术人员根据本发明的原理，不脱离本发明的范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
1.一种锰锌铁氧体材料，其特征在于：其包括主料和添加剂；
所述主料包括如下组分：
氧化铁 72.10-72.70wt％，
氧化锌 3.2-4.5wt％，
氧化锰 余量；
所述添加剂以主料为基准，包括如下组分：
2.根据权利要求1所述的锰锌铁氧体材料，其特征在于：所述主料中氧化铁的含量为72.4-72.7wt％，氧化锌的含量为3.5-4.2wt％。
3.根据权利要求1所述的锰锌铁氧体材料，其特征在于：所述添加剂中氧化钙的含量为0.04-0.12wt％，纳米二氧化硅的含量为0.02-0.04wt％，纳米二氧化硅的粒径≤100nm，四氧化三钴的含量为0.15-0.25wt％，氧化锆的含量为0.02-0.05wt％，五氧化二铌的含量为0.01-0.03wt％。
4.根据权利要求1所述的锰锌铁氧体材料，其特征在于：所述添加剂中氧化钙和纳米二氧化硅的比值为1:1-4:1；
优选地，所述添加剂中氧化钙和纳米二氧化硅的比值为2:1-3:1。
5.一种如权利要求1-4任一项所述的锰锌铁氧体材料的制备方法，其特征在于：其包括如下步骤：
(1)、将称重的氧化铁、氧化锰和氧化锌原材料混合，研磨得到混合物；
(2)、将所述混合物预烧，预烧后的物料进行球磨，之后放入研磨机中加入纯水和添加剂进行砂磨，磨细后的料浆粒度不能大于1.5μm；
(3)、将砂磨后的料浆烘干后加入聚乙烯醇进行造粒，压制成型，并在氮气保护下进行烧结；
其中，步骤(2)中，所述添加剂包括氧化钙、纳米二氧化硅、四氧化三钴、氧化锆和五氧化二铌。
6.根据权利要求5所述的制备方法，其特征在于：步骤(2)中，所述预烧的温度为900-950℃，所述预烧时保温的时间为1-2h。
7.根据权利要求5所述的制备方法，其特征在于：步骤(2)中，磨细后的料浆粒度不能大于1.2μm。
8.根据权利要求5所述的制备方法，其特征在于：步骤(3)中，所述氮气保护下，烧结的保温温度为1110-1150℃。
9.根据权利要求5所述的制备方法，其特征在于：步骤(3)中，所述烧结时，升温阶段400-500℃至保温温度1110-1150℃，氧含量不大于1.5％。
10.一种如权利要求1所述的锰锌铁氧体材料在高频开关电源中的应用。
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| CN115196958A (zh) * | 2022-06-02 | 2022-10-18 | 江苏信维感应材料科技有限公司 | 一种高频宽温MnZn铁氧体及其制备方法 |
| CN115448714A (zh) * | 2022-10-12 | 2022-12-09 | 上海宝钢磁业有限公司 | 锰锌铁氧体材料及制备方法和应用 |
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| CN107540363A (zh) * | 2017-09-21 | 2018-01-05 | 郴州市久隆旺高科电子有限公司 | 一种宽温高频低损耗锰锌软磁铁氧体材料及其制备方法 |
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| CN115448714A (zh) * | 2022-10-12 | 2022-12-09 | 上海宝钢磁业有限公司 | 锰锌铁氧体材料及制备方法和应用 |
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