CN114409393B - 一种高矫顽力低损耗复合六角铁氧体材料及其制备方法 - Google Patents
一种高矫顽力低损耗复合六角铁氧体材料及其制备方法 Download PDFInfo
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Abstract
一种高矫顽力低损耗复合六角铁氧体材料及其制备方法，属于铁氧体材料制备技术领域。所述复合六角铁氧体材料包括主配方和掺杂剂，主配方包括：BaCO3、ZnO、CoO和Fe2O3；添加剂包括：Bi2O3、H3BO3、SiO2。本发明通过一步合成具有交换耦合作用的W型和M型复合六角铁氧体，大幅度提高复合六角铁氧体的矫顽力，有利于实现微波器件的准平面特性；对添加剂配比及工艺优化，得到了兼具低铁磁共振线宽特征的W型和M型复合六角铁氧体，有利于降低准平面化器件的插入损耗，实现工程化应用。因此，本发明六角铁氧体材料兼具高而可调的磁晶各向异性场、高的剩磁比、高的矫顽力以及较低的铁磁共振线宽特性。
Description
技术领域
本发明属于铁氧体材料制备技术领域，具体涉及一种高矫顽力低损耗复合六角铁氧体材料及其制备方法。
背景技术
随着微波技术的快速发展，环行器正朝着小型轻量化、集成化和低损耗的方向发展。传统X波段环行器所采用的铁氧体材料主要为尖晶石型和石榴石型两种类型，受器件原理以及材料性能的限制，基于上述两种铁氧体材料制作的环行器工作时需要外加永磁体提供偏置磁场。并且永磁体的尺寸会随器件工作频率的提高而增大，这大大增加了整机系统的体积和质量，与微波器件小型轻量化和平面化的发展趋势相悖。因此，探究一种具有“自建內场”特性的自偏置材料是十分重要的。为了实现这一目标，磁性材料必须具有高而可调的磁晶各向异性场和高的剩磁比才能建立其内置磁场。c轴织构的六角铁氧体因其具有高而可调的磁晶各向异性场(Ha)、高剩磁比(Mr/Ms)、高矫顽力(Hc)以及高居里温度(Tc)而成为极具前景的自偏置材料。利用上述六角铁氧体材料独有优势能够为环行器工作时提供自偏置场，完全摆脱外加磁钢束缚，使得环行器能够以准平面化状态工作，大大降低了器件的体积和质量。
六角铁氧体按晶体结构分为M型、W型、U型、X型、Y型以及Z型六角铁氧体。由于U型和X型六角铁氧体的结构复杂，制备比较困难，而Y型和Z型六角铁氧体又不具有c轴织构，因此广泛研究的自偏置材料是W型和M型六角铁氧体。然而，M型六角铁氧体拥有着高的Ha(16.9kOe)，仅适用于Ka波段及以上的频率。同样是c轴织构的W型六角铁氧体，具有低的Ha(12.5kOe)，是应用于X波段环行器的不错选择。针对W型六角铁氧体，伊斯兰堡通信卫星大学(Ceram.Int.，2019，45：24202)表明Ni2+取代可提高Ba0.5Sr0.5NixZn2-xFe16O27的矫顽力，矫顽力从142Oe提升到187Oe。杭州电子科技大学(J.Sol-Gel Sci.Technol.，2020，96：604)研究表明纯相的BaZn2Fe16O27铁氧体的矫顽力低于250Oe。安徽大学(J.Ceram.Process.Res.，2020，21：378)研究表明Pr2+取代将Sr1-xPrx Zn0.8Co1.2Fe16O27的矫顽力从139Oe提升到249Oe。电子科技大学(Ceram.Int.，2019，45：12205)对Gd3+取代Sr1-xGdxNi2Fe16O27的磁性能进行了研究，表明Gd3+取代Sr2+能提高矫顽力，但样品的矫顽力均低于650Oe。巴哈德因·扎卡利亚大学(Ceram.Int.，2011，37：3691)研究表明La3+取代可提升BaZn2LaxFe16-xO27的矫顽力，但矫顽力仍低于850Oe。专利CN107792889A采用水热法制备了SrxCoyFezO27铁氧体，虽然其比饱和磁化强度最高约为78～80emu/g，但矫顽力较低，约为200～700Oe。上述研究表明，W型六角铁氧体的矫顽力相对较低，很难突破1000Oe。
基于上述，目前W型六角铁氧体材料仍无法实现高矫顽力的特性，因此本发明提供一种高矫顽力低损耗复合六角铁氧体材料及其制备方法。
发明内容
本发明的目的在于，针对背景技术存在的W型六角铁氧体材料矫顽力低的问题，提出了一种高矫顽力低损耗复合六角铁氧体材料及其制备方法。
为实现上述目的，本发明采用的技术方案如下：
一种高矫顽力低损耗复合六角铁氧体材料，其特征在于，所述复合六角铁氧体材料包括主配方和掺杂剂，所述主配方包括：3.51～3.83mol％BaCO3、5.60～6.07mol％ZnO、0.29～0.32mol％CoO、90.10～90.27mol％Fe2O3；
添加剂占主配方重量百分比为：1.5～5.0wt％Bi2O3、1.5～5.0wt％H3BO3、0.4～0.8wt％SiO2。
一种高矫顽力低损耗复合六角铁氧体材料的制备方法，其特征在于，包括以下步骤：
步骤1、配料：
以BaCO3、ZnO、CoO、Fe2O3作为原料，按照“3.51～3.83mol％BaCO3、5.60～6.07mol％ZnO、0.29～0.32mol％CoO、90.10～90.27mol％Fe2O3”的比例称料，混料，配制得到初始粉体；
步骤2、一次球磨：
将步骤1得到的初始粉体在球磨机内混合均匀，球磨时间为9～15h；
步骤3、预烧：
将步骤2得到的一次球磨料烘干，以5～8℃/min升温至1250～1350℃进行预烧，预烧时间为6～10h，形成W型六角铁氧体，随后以2～8℃/min降温至1000～1200℃进行预烧，预烧时间为6～10h，形成M型六角铁氧体，即可得到W型和M型复合六角铁氧体预烧粉体；
步骤4.掺杂：
在步骤3得到的预烧粉体中加入添加剂，所述添加剂占主配方重量百分比为1.5～5.0wt％Bi2O3、1.5～5.0wt％H3BO3、0.4～0.8wt％SiO2；
步骤5、二次球磨：
将步骤4得到的混合粉料在球磨机中球磨9～24h，粉料粒度控制在0.6～0.9μm之间；
步骤6：脱水：
将步骤5得到的球磨浆料脱水，脱水后料浆含水量控制在15～35wt％之间；
步骤7、成型：
将步骤6得到的脱水浆料在磁场成型机下压制成型，成型磁场强度为1.2～1.4T，成型压力为80～120MPa；
步骤8、烧结：
将步骤7压制得到的坯件置于烧结炉内烧结，烧结温度为900～1100℃，时间为10min～60min，得到所述复合六角铁氧体材料。
对步骤8得到的复合六角铁氧体样品进行磁性能测试：材料的饱和磁化强度4πMs、剩余磁化强度4πMr、剩磁比Mr/Ms、矫顽力Hc采用美国LakeShore 8604型VSM测试，铁磁共振线宽(ΔH)采用美国Agilent N5227A矢量网络分析仪测试。
本发明制备的高矫顽力低损耗复合六角铁氧体材料最终的技术指标如下：
饱和磁化强度4πMs：≥3.3kGs；
剩余磁化强度4πMr：≥2.5kOe；
剩磁比Mr/Ms：≥0.77；
矫顽力Hc：≥1196Oe；
线宽ΔH：≤530Oe。
本发明的原理如下：
本发明提供的一种高矫顽力低损耗复合六角铁氧体材料，主配方采用W型和M型六角铁氧体，采用高低温分段预烧法，使原料充分反应形成W型和M型六角铁氧体，从而一步合成具有W型和M型结构的复合六角铁氧体；根据交换耦合理论，短距离接触的两种磁性颗粒之间存在交换耦合作用，磁矩易于向易轴平行排列，各向异性增强，可大幅度提高复合六角铁氧体的矫顽力；采用低熔点的H3BO3和Bi2O3，形成致密化片状晶粒，提高密度，降低线宽；湿压磁场成型时，粉料沿磁场取向，形成c轴取向。
与现有技术相比，本发明的有益效果为：
本发明提供的一种高矫顽力低损耗复合六角铁氧体材料及其制备方法，一步合成具有交换耦合作用的W型和M型复合六角铁氧体，大幅度提高复合六角铁氧体的矫顽力，有利于实现微波器件的准平面特性；对添加剂配比及工艺优化，得到了兼具低铁磁共振线宽特征的W型和M型复合六角铁氧体，有利于降低准平面化器件的插入损耗，实现工程化应用。因此，本发明六角铁氧体材料兼具高而可调的磁晶各向异性场、高的剩磁比、高的矫顽力以及较低的铁磁共振线宽特性。
附图说明
图1为实施例2得到的复合六角铁氧体材料的磁滞回线；
图2为实施例2得到的复合六角铁氧体材料的铁磁共振。
具体实施方式
下面结合附图和实施例，详述本发明的技术方案。
针对X波段微波器件小型轻量化的应用需求，本发明提供一种高矫顽力低损耗复合六角铁氧体材料及其制备方法。首先通过优选高纯度的BaCO3、ZnO、CoO、Fe2O3为原材料，深入分析了复合六角铁氧体材料的离子占位情况和各向异性起源，以实现高而可调的磁晶各向异性Ha、高的剩磁比Mr/Ms、高的矫顽力Hc以及较低的铁磁共振线宽ΔH为指导思想，确定最优的配方范围；其次根据不同种类添加剂对复合六角铁氧体材料助熔/阻晶交互作用机制，选用Bi2O3、H3BO3、SiO2等添加剂调控复合六角铁氧体材料晶界/晶粒特性，确定最优的添加剂配方；最后在上述配方、添加剂及粉体制备工艺优化的前提下，结合高密度均匀晶粒的烧结工艺，最终制备出兼具高而可调的磁晶各向异性场、高的剩磁比、高的矫顽力以及较低的铁磁共振线宽特征的复合六角铁氧体材料。
实施例
一种高矫顽力低损耗复合六角铁氧体材料的制备方法，具体包括以下步骤：
步骤1、配料
实施例1～2
主配方见下表：
步骤2、一次球磨：
将步骤1得到的初始粉体在球磨机内混合均匀，球磨时间为12h；
步骤3、预烧：
将步骤2得到的一次球磨料烘干，以6℃/min升温至1250℃进行预烧，预烧时间为6h，形成W型六角铁氧体，随后以2℃/min降温至1125℃进行预烧，预烧时间为6h，形成M型六角铁氧体，即可得到W型和M型复合六角铁氧体预烧粉体；
步骤4.掺杂：
在步骤3得到的预烧粉体中加入添加剂，所述添加剂占主配方重量百分比为4.0wt％Bi2O3、4.0wt％H3BO3、0.6wt％SiO2；
步骤5、二次球磨：
将步骤4得到的混合粉料在球磨机中球磨18h，粉料粒度控制在0.6～0.9μm之间；
步骤6：脱水：
将步骤5得到的球磨浆料脱水，脱水后料浆含水量控制在25wt％左右；
步骤7、成型：
将步骤6得到的脱水浆料在磁场成型机下压制成型，成型磁场强度为1.4T，成型压力为120MPa；
步骤8、烧结：
将步骤7压制得到的坯件置于烧结炉内烧结，烧结温度为980℃，时间为30min，得到所述复合六角铁氧体材料。
对实施例步骤8得到的复合六角铁氧体样品进行磁性能测试：材料的饱和磁化强度4πMs、剩余磁化强度4πMr、剩磁比Mr/Ms、矫顽力Hc采用美国LakeShore8604型VSM测试，铁磁共振线宽(ΔH)采用美国Agilent N5227A矢量网络分析仪测试。
实施例得到的复合六角铁氧体材料，其性能指标如下：
实施例1～2、对比例1～2测试结果如下：
Claims (1)
1.一种高矫顽力低损耗复合六角铁氧体材料的制备方法，其特征在于，包括以下步骤：
步骤1、配料：
以BaCO3、ZnO、CoO、Fe2O3作为原料，按照“3.51~3.83mol%BaCO3、5.60~6.07mol%ZnO、0.29~0.32mol%CoO、90.10~90.27mol%Fe2O3” 的比例称料，混料，配制得到初始粉体；
步骤2、一次球磨：
将步骤1得到的初始粉体在球磨机内混合均匀，球磨时间为9~15 h；
步骤3、预烧：
将步骤2得到的一次球磨料烘干，以5~8℃/min升温至1250～1350℃进行预烧，预烧时间为6～10h，形成W型六角铁氧体，随后以2~8℃/min降温至1000～1200℃进行预烧，预烧时间为6～10h，形成M型六角铁氧体，即可得到W型和M型复合六角铁氧体预烧粉体；
步骤4.掺杂：
在步骤3得到的预烧粉体中加入添加剂，所述添加剂占主配方重量百分比为1.5~5.0wt%Bi2O3、1.5~5.0wt%H3BO3、0.4~0.8wt%SiO2；
步骤5、二次球磨：
将步骤4得到的混合粉料在球磨机中球磨9~24h，粉料粒度控制在0.6~0.9μm之间；
步骤6：脱水：
将步骤5得到的球磨浆料脱水，脱水后料浆含水量控制在15~35 wt%之间；
步骤7、成型：
将步骤6得到的脱水浆料在磁场成型机下压制成型，成型磁场强度为1.2~1.4T，成型压力为80~120MPa；
步骤8、烧结：
将步骤7压制得到的坯件置于烧结炉内烧结，烧结温度为900~1100℃，时间为10min~60min，得到所述复合六角铁氧体材料。
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