CN115385680B - 一种高介低线宽微波旋磁铁氧体材料及其制备方法 - Google Patents

一种高介低线宽微波旋磁铁氧体材料及其制备方法 Download PDF

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CN115385680B
CN115385680B CN202211117935.9A CN202211117935A CN115385680B CN 115385680 B CN115385680 B CN 115385680B CN 202211117935 A CN202211117935 A CN 202211117935A CN 115385680 B CN115385680 B CN 115385680B
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苏桦
梁吉
杨钊
荆玉兰
李元勋
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Abstract

本发明属于电子材料技术领域，具体涉及一种高介低线宽微波旋磁铁氧体材料及其制备方法。本发明通过严格控制Bi离子在YIG旋磁铁氧体中的替代量在12.5～13.5之间，再通过Gd、V、Ca、Zr等离子的复合替代，以及二次球磨时的H3BO3和WO3微量掺杂，并在工艺上引入了热等静压的工艺，最终制备出4πMs为1838～1850Gs，介电常数27～31，铁磁共振线宽≤20Oe的高介低线宽旋磁铁氧体材料。本发明让旋磁铁氧体材料高介电常数和低铁磁共振线宽的兼具成为可能，为微波铁氧体器件的进一步小型化提供了基础。

Description

一种高介低线宽微波旋磁铁氧体材料及其制备方法
技术领域
本发明属于电子材料技术领域，具体涉及一种兼具高介电常数和低铁磁共振线宽的微波旋磁铁氧体材料及其制备方法。
背景技术
微波铁氧体器件在微波技术中占有非常重要的地位，在航空航天、卫星通信、电子对抗以及移动通信等领域都有着非常广泛的应用。微波旋磁铁氧体材料作为微波铁氧体器件的核心，在环行器、隔离器、移相器、变极化器等微波铁氧体器件中实现着对微波传输信号进行隔离、移相、调制、倍频、放大、通路选择以及极化状态控制等作用，其性能的优劣直接决定了微波铁氧体器件综合性能的好坏。近年来，随着国防及民用无线通信技术的快速发展，小型化、宽频带和多功能的发展趋势在各种通信电子产品中体现得越来越明显。雷达、基站、手机等无线通信电子系统的体积越做越小，但功能却越来越强大，这就对其中采用的各种微波铁氧体器件小型化和集成度提出了越来越高的要求。
由于电磁波在介质中传播的波长与介电常数的平方根成反比，因而提高旋磁铁氧体材料的介电常数就成为了实现微波铁氧体器件小型化的重要手段。如在带线型中心结环行器中旋磁铁氧体圆盘半径R有如下近似计算公式：
Figure BDA0003846139390000011
其中k为有效波数，ω为工作角频率，c为光速，ε为铁氧体介电常数，μeff为铁氧体有效磁导率。可见，旋磁铁氧体圆盘半径大小与铁氧体介电常数的平方根成反比。目前，实践研究也很好的证明了这一点。因此提高旋磁铁氧体材料的介电常数是减小微波铁氧体器件尺寸的有效突破口。但是，提高旋磁铁氧体的介电常数往往与降低其铁磁共振线宽相互矛盾，此外，还需要兼顾好Ms(饱和磁化强度)、居里温度等材料参数，研发难度很大；目前对于旋磁铁氧体材料的性能优化改良均是在材料配方上进行调整。
譬如美国transtech公司最早于2016年申报的美国专利(US 9,263,175 B2)，提出采用适量Bi替代Y的方式，可以有效提升旋磁YIG材料的介电常数，但其报道的高介旋磁YIG铁磁共振线宽还比较高(超过50Oe)，居里温度也较低(低于200℃)。深圳顺络电子2018年申请的专利(CN 111285673 A)，采用Bi、Ca、Zr、Al和Mn等离子共替代的方式来提升材料的介电常数，但同样材料的铁磁共振线宽也较大(超过45Oe)。2021年横店东磁也申请了发明专利(CN 113896521 A)，其采取了Bi、Gd、Ca、Nb、V等10种元素共替代的方式，实现了一款铁磁共振线宽约20Oe，介电常数25～28的低线宽高介旋磁铁氧体材料，但材料饱和磁化强度较低，大概在1200Gs左右。该技术虽然材料铁磁共振线宽较低，但不太适合目前应用最广泛的高场旋磁器件对材料4πMs要求在1850±50Gs的应用需求。
发明内容
针对上述存在问题或不足，为解决现有高场旋磁器件对旋磁铁氧体材料高介低线宽的应用需求，本发明提供了一种高介低线宽微波旋磁铁氧体材料及其制备方法，该高介低线宽旋磁YIG铁氧体材料在4πMs为1838～1850Gs，介电常数介于27～31，铁磁共振线宽≤20Oe，可替代目前通用的4πMs在1850Gs左右的低线宽YIG材料，以显著缩小环行器和隔离器的体积，进而缩小整个通信系统的质量和体积，具有很好的应用前景。
一种高介低线宽微波旋磁铁氧体材料，分子式为BixY2.9-x-y-2zGd0.1Ca2z+yZryVzFe5-y-zO12，4πMs为1838～1850Gs，介电常数27～31，铁磁共振线宽≤20Oe。通过将原料组分配料后经一次球磨烘干于750℃～850℃预烧，再掺杂预烧料0.03～0.06wt％的H3BO3和0.03～0.06wt％的WO3经二次球磨烘干后，加入PVA溶液造粒成型，然后再通过热等静压工艺进一步提升生胚致密度，最后于960～990℃烧结制备。
上述高介低线宽微波旋磁铁氧体材料的制备方法，包括以下步骤：
步骤1：以Bi2O3、Y2O3、Gd2O3、CaCO3、V2O5、ZrO2和Fe2O3为初始原料，按照旋磁铁氧体材料的分子式BixY2.9-x-y-2zGd0.1Ca2z+y ZryVzFe5-y-zO12进行配料，其中x＝1.25～1.35，y＝0.45～0.55，z＝0.1～0.15；然后在球磨机中进行混料、一次球磨后烘干。
步骤2：将步骤1所得烘干料过筛后压实打孔，升温至750℃～850℃进行预烧，保温6～8小时，随炉冷却到室温得到预烧料。
步骤3：将步骤2所得预烧料进行粗粉粹后，同时加入预烧料重量百分比0.03～0.06wt％的H3BO3和0.03～0.06wt％的WO3进行微量掺杂；然后在球磨机中进行二次球磨至粉料平均粒度在1微米以下，再烘干。
步骤4：在步骤3得到的二次球磨烘干料中加入占其重量8％～10％的PVA溶液造粒，并压制成型，得生胚。
步骤5：将步骤4所得生胚进行热等静压：等静压机液体温度升温至65～80℃，保温10～20分钟后，于22～26MPa保压10～20分钟，进一步提升生胚的致密度。
步骤6：将步骤5热等静压后所得的生胚于960～990℃烧结。
首先以2～3℃/分的升温速率升温至150～200℃保温1～2小时排水，然后以2～3℃/分的升温速率升温至500～600℃保温2～4小时排胶，再以2～3℃/分的升温速率升温至960～990℃保温6～12小时，最后随炉冷却至室温即得高介低线宽微波旋磁铁氧体材料，该材料可根据应用目标的要求，切割成需要的基片厚度。
本发明创新点主要体现在：
(1)首先严格控制了Bi离子在YIG旋磁铁氧体中的替代量，再结合掺杂和热等静压工艺途径来进一步提升材料介电常数，以更好的兼顾高介和低线宽的综合要求。根据相关研究报道，Bi离子替代确实可以显著提升旋磁铁氧体材料的介电常数，但也会导致铁磁共振线宽的大幅上升，特别是Bi替代量达到和超过1.4以后，损耗会大幅度的上升。因此本发明先严格限制了Bi替代量为12.5～13.5之间，能最好的兼顾提升介电常数和控制铁磁共振线宽的综合要求。
(2)其次，通过Gd、V、Ca、Zr等离子的复合替代，更好的兼顾了提升材料的致密度和降低材料铁磁共振线宽的综合要求，同时对Ms也不造成明显影响，仍然能够维持在1850Gs左右。
(3)通过在二次球磨时同时掺杂微量的H3BO3和WO3，优化铁氧体材料的微观形貌以提升烧结样品的致密化程度，利于降低铁磁共振线宽和提升介电常数。
(4)最后，在传统压制成型的基础上，引入了热等静压的工艺，以确保生胚样品在不开裂变形的前提上，进一步提升生胚密度，达到单纯机械压制达不到的成型效果，进而有利于进一步的提高材料烧结密度和介电常数，并降低铁磁共振线宽。
综上所述，本发明提供了4πMs为1838～1850Gs，介电常数27～31，铁磁共振线宽≤20Oe的高介低线宽旋磁铁氧体材料。让旋磁铁氧体材料高介电常数和低铁磁共振线宽的兼具成为可能，为微波铁氧体器件的进一步小型化提供了基础，非常利于小型化环行器和隔离器的研发和生产。
附图说明
图1为本发明高介低线宽旋磁铁氧体材料的制备方法流程图。
具体实施方式
下面结合附图和实施例及其测试结果，以对本发明做进一步的详细说明。
以下实施例均固定工艺条件为：
按3℃/分的升温速率至800℃预烧，保温6小时；二次球磨时均掺杂0.04wt％的H3BO3和0.04wt％的WO3；造粒时PVA溶液添加量为10％；热等静压70度保温15分钟后，于24MPa保压15分钟；烧结时以2℃/分的升温速率升温至200℃保温2小时排水，然后再以2℃/分的升温速率升温至600℃保温3小时排胶，然后再以2.5℃/分的升温速率升温至960～990℃保温8小时。
以高纯的Bi2O3、Y2O3、Gd2O3、CaCO3、V2O5、ZrO2和Fe2O3为初始原料，通过改变材料BixY2.9-x-y-2zGd0.1Ca2z+y ZryVzFe5-y-zO12配方(x，y，z的取值)来获得不同的实测对照结果。
Figure BDA0003846139390000041
通过以上实施例可见，本发明通过严格控制Bi离子在YIG旋磁铁氧体中的替代量在12.5～13.5之间，再通过Gd、V、Ca、Zr等离子的复合替代，以及二次球磨时的H3BO3和WO3微量掺杂，并在工艺上引入了热等静压的工艺，最终制备出4πMs为1838～1850Gs，介电常数27～31，铁磁共振线宽≤20Oe的高介低线宽旋磁铁氧体材料。为微波铁氧体器件的进一步小型化提供了基础。

Claims (7)

1.一种高介低线宽微波旋磁铁氧体材料，其特征在于：
分子式为BixY2.9-x-y-2zGd0.1Ca2z+y ZryVzFe5-y-zO12，4πMs为1838～1850Gs，介电常数27～31，铁磁共振线宽≤20Oe；其中x＝1.25～1.35，y＝0.45～0.55，z＝0.1～0.15；
将原料组分配料后经一次球磨烘干于750℃～850℃预烧，再掺杂预烧料0.03～0.06wt％的H3BO3和0.03～0.06wt％的WO3经二次球磨烘干后，加入PVA溶液造粒成型，然后进行热等静压，最后于960～990℃烧结制备。
2.如权利要求1所述高介低线宽微波旋磁铁氧体材料的制备方法，其特征在于，包括以下步骤：
步骤1、按照旋磁铁氧体材料分子式BixY2.9-x-y-2zGd0.1Ca2z+y ZryVzFe5-y-zO12以Bi2O3、Y2O3、Gd2O3、CaCO3、V2O5、ZrO2和Fe2O3为原料进行配料，其中x＝1.25～1.35，y＝0.45～0.55，z＝0.1～0.15；然后在球磨机中进行混料、一次球磨后烘干；
步骤2、将步骤1所得烘干料过筛后压实打孔，升温至750℃～850℃进行预烧，并保温6～8小时，随炉冷却至室温得预烧料；
步骤3、将步骤2所得预烧料粗粉粹后，同时加入预烧料重量百分比0.03～0.06wt％的H3BO3和0.03～0.06wt％的WO3掺杂；然后在球磨机中进行二次球磨至粉料平均粒度在1微米以下，再烘干；
步骤4、在步骤3得到的二次球磨烘干料中加入占其重量8％～10％的PVA溶液造粒，并压制成型，得生胚；
步骤5、将步骤4所得生胚进行热等静压，等静压机液体温度升温至65～80℃并保温10～20分钟后，于22～26MPa保压10～20分钟；
步骤6、将步骤5热等静压后所得生胚于960～990℃烧结：
首先以2～3℃/分的升温速率升温至150～200℃保温1～2小时排水，然后以2～3℃/分的升温速率升温至500～600℃保温2～4小时排胶，再以2～3℃/分的升温速率升温至960～990℃保温6～12小时，最后随炉冷却至室温即得高介低线宽微波旋磁铁氧体材料。
3.如权利要求2所述高介低线宽微波旋磁铁氧体材料的制备方法，其特征在于：所述步骤2按3℃/分的升温速率至800℃预烧，保温6小时。
4.如权利要求2所述高介低线宽微波旋磁铁氧体材料的制备方法，其特征在于：所述步骤3二次球磨时掺杂0.04wt％的H3BO3和0.04wt％的WO3。
5.如权利要求2所述高介低线宽微波旋磁铁氧体材料的制备方法，其特征在于：所述步骤4造粒时PVA溶液添加量为10％。
6.如权利要求2所述高介低线宽微波旋磁铁氧体材料的制备方法，其特征在于：所述步骤5热等静压为70℃保温15分钟后，于24MPa保压15分钟。
7.如权利要求2所述高介低线宽微波旋磁铁氧体材料的制备方法，其特征在于：所述步骤6烧结时以2℃/分的升温速率升温至200℃保温2小时排水，再以2℃/分的升温速率升温至600℃保温3小时排胶，然后以2.5℃/分的升温速率升温至960～990℃保温8小时。
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