CN111825441B - 高介电常数、高饱和磁化强度石榴石铁氧体材料、其制备方法及应用 - Google Patents

高介电常数、高饱和磁化强度石榴石铁氧体材料、其制备方法及应用 Download PDF

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CN111825441B
CN111825441B CN202010730001.7A CN202010730001A CN111825441B CN 111825441 B CN111825441 B CN 111825441B CN 202010730001 A CN202010730001 A CN 202010730001A CN 111825441 B CN111825441 B CN 111825441B
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dielectric constant
saturation magnetization
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鲜聪
杨菲
刘运桃
廖杨
任仕晶
蒋运石
孔伟
袁红兰
陈建杰
冯涛
罗建成
高春燕
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CETC 9 Research Institute
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Abstract

本发明公开了一种高介电常数、高饱和磁化强度石榴石铁氧体材料，属于微波铁氧体材料领域，其化学式组成为：BiaCabGdcY3‑a‑b‑ cFe5‑d‑e‑f‑g‑δHfdZreVfSngO12，其中1.0≤a≤1.7，0≤b≤1，0≤c≤0.3，0≤d≤0.6，0≤e≤0.5，0≤f≤0.3，0≤g≤0.3，δ为缺铁量，本发明还公开了、其制备方法及应用，本发明的铁氧体材料的介电常数为32～33，且同时具有较高的饱和磁化强度、较低的铁磁共振线宽，这些优点不仅可以有效的降低器件的尺寸，还可以增加器件的带宽，降低器件的插入损耗，可以用于小型化的微波器件中，尤其适用于雷达、5G通信等领域，另外，本发明的制备方法合理，便于推广应用。

Description

高介电常数、高饱和磁化强度石榴石铁氧体材料、其制备方法 及应用
技术领域
本发明涉及微波铁氧体材料领域，尤其涉及一种高介电常数、高饱和磁化强度石榴石铁氧体材料、其制备方法及应用。
背景技术
高介电常数钇铁石榴石铁氧体材料的研制目的，是为了解决铁氧体器件小型化困难的问题。传统钇铁石榴石铁氧体材料的介电常数为13～15，根据铁氧体器件理论，想要实现铁氧体器件进一步的小型化，在不增加材料介电常数的前提下，难度极大。
在上世纪就有文章报道在钇铁石榴石中掺入高极化离子可以有效的增大钇铁石榴石的介电常数。并且近些年来也有一些专利报道了高介电常数钇铁石榴石材料的制备方法，如专利公开号为CN107417266A、名称为“一种无稀土石榴石铁氧体材料及其制备方法”、公开号为CN104478425A、专利名称为“用于通信微波隔离器和环形器的铁氧体及制备方法”、公开号为CN107034517A、专利名称为“改性的石榴石结构和射频系统”等，这些铁氧体材料，虽然相对于传统的材料，能在一定程度上提高介电常数，比如CN107417266A的介电常数能提高到21左右，CN104478425A的介电常数能提高到28左右，CN107034517A的介电常数能提高到19-31；
但是，现有的这些铁氧体材料都存在一些问题：比如相比于传统钇铁石榴石材料，高介电常数钇铁石榴石材料铁磁共振线宽较大，这会导致器件的损耗较大；高介电常数钇铁石榴石材料的居里温度较低，这直接影响材料的工程化应用；为了提高材料的介电常数，掺杂高极化离子，导致饱和磁化强度降低，影响器件的带宽和使用频率。
也就是说，目前的高介电常数石榴石材料的铁磁共振线宽、饱和磁化强度、居里温度等性能指标还无法满足器件使用要求。
发明内容
本发明的目的之一，就在于提供一种高介电常数、高饱和磁化强度石榴石铁氧体材料，以解决上述问题。
为了实现上述目的，本发明采用的技术方案是这样的：一种高介电常数、高饱和磁化强度石榴石铁氧体材料，其化学式组成为：BiaCabGdcY3-a-b-cFe5-d-e-f-g-δHfdZreVfSngO12，其中1.0≤a≤1.7，0≤b≤1，0≤c≤0.3，0≤d≤0.6，0≤e≤0.5，0≤f≤0.3，0≤g≤0.3，δ为缺铁量。
本发明通过掺杂Zr4+、Sn4+、V5+、Hf4+等离子联合、部分替代Fe3+，降低材料的铁磁共振线宽△H并调控材料的饱和磁化强度；采用Bi3+、Ca2+、Gd3+部分取代Y3+，调整饱和磁化强度，尤其是其中的Bi3+，是高极化离子，起到增加介电常数的作用。
本发明的目的之二，在于提供上述的高介电常数、高饱和磁化强度石榴石铁氧体材料的制备方法，采用的技术方案为：
(a)一次料的制备：按组成化学式BiaCabGdcY3-a-b-cFe5-d-e-f-g-δHfdZreVfSngO12称取原材料进行球磨，球料比例为4:1～1.5，料与溶剂比例为1:1～1.2，球磨4～8h，然后过滤烘干过筛，在700～1000℃进行预烧处理，然后自然冷却，得到一次料；
(b)二次料的制备：将步骤(a)处理好的一次料敲碎，按料与溶剂的比例1:0.8～1进行球磨4～8h，然后过滤烘干，即得到二次料；
(c)造粒：将制备的二次料加入胶合剂，进行造粒过筛；
(d)成型：造粒好的细粉放入模具进行压制，压制压强为50MPa～250MPa，得到材料生坯
(e)烧结；将生坯装入空气气氛或氧化气氛炉中进行烧结，即得。
作为优选的技术方案：步骤(a)中的原材料为分析纯，其化学式分别为Fe2O3、Bi2O3、Gd2O3、CaCO3、ZrO2、HfO2、V2O5、SnO2、Y2O3。
作为优选的技术方案：步骤(a)中，球磨比为4:1，球磨时间为4h。
作为优选的技术方案：步骤(a)中，所述球为氧化锆或钢球，所述溶剂为去离子水或酒精。
作为优选的技术方案：步骤(b)中，料与溶剂的比例为1:0.8，球磨时间为4h。
步骤(a)、(c)中过筛时筛规格大小为20目～60目。
作为优选的技术方案：步骤(c)中，所述胶合剂为聚乙烯醇水溶液，浓度为5wt％～12wt％。
作为优选的技术方案：步骤(e)中，烧结温度为900℃～1100℃，保温6小时以上。
本发明的目的之三，在于提供上述的高介电常数、高饱和磁化强度石榴石铁氧体材料的应用，可以用于小型化的微波器件中，尤其适用于雷达、5G通信等领域。
与现有技术相比，本发明的优点在于：本发明的铁氧体材料的介电常数为32～33，且同时具有较高的饱和磁化强度、较低的铁磁共振线宽，这些优点不仅可以有效的降低器件的尺寸，还可以增加器件的带宽，降低器件的插入损耗，可以用于小型化的微波器件中，尤其适用于雷达、5G通信等领域，另外，本发明的制备方法合理，便于推广应用。
附图说明
图1为高介电常数石榴石旋磁基片和普通石榴石旋磁基片；
图2为用高介电常数石榴石旋磁基片设计的环行器和用普通石榴石旋磁基片设计的环行器；
图3为高介电常数石榴石旋磁基片设计的环行器插入损耗、隔离度的仿真结果；
图4为高介电常数石榴石旋磁基片设计的环行器驻波比的仿真结果；
图5为普通石榴石旋磁基片设计的环行器插入损耗、隔离度的仿真结果；
图6为普通石榴石旋磁基片设计的环行器驻波比的仿真结果。
具体实施方式
下面将结合附图对本发明作进一步说明。
实施例1：按组成化学式BiaCabGdcY3-a-b-cFe5-d-e-f-g-δHfdZreVfSngO12称取Fe2O3、Bi2O3、Gd2O3、CaCO3、ZrO2、HfO2、V2O5、SnO2、Y2O3,其中a＝1.5，b＝0.45，c＝0，d＝0.48，e＝0.07，f＝0，g＝0，δ＝0.05。
实施例2：按组成化学式BiaCabGdcY3-a-b-cFe5-d-e-f-g-δHfdZreVfSngO12称取Fe2O3、Bi2O3、Gd2O3、CaCO3、ZrO2、HfO2、V2O5、SnO2、Y2O3,其中a＝1.5，b＝0.45，c＝0，d＝0.43，e＝0.12，f＝0，g＝0，δ＝0.05。
实施例3：按组成化学式BiaCabGdcY3-a-b-cFe5-d-e-f-g-δHfdZreVfSngO12称取Fe2O3、Bi2O3、Gd2O3、CaCO3、ZrO2、HfO2、V2O5、SnO2、Y2O3,其中a＝1.5，b＝0.45，c＝0，d＝0.38，e＝0.17，f＝0，g＝0，δ＝0.05。
实施例4：按组成化学式BiaCabGdcY3-a-b-cFe5-d-e-f-g-δHfdZreVfSngO12称取Fe2O3、Bi2O3、Gd2O3、CaCO3、ZrO2、HfO2、V2O5、SnO2、Y2O3,其中a＝1.5，b＝0.45，c＝0，d＝0.33，e＝0.22，f＝0，g＝0，δ＝0.05。
实施例5：按组成化学式BiaCabGdcY3-a-b-cFe5-d-e-f-g-δHfdZreVfSngO12称取Fe2O3、Bi2O3、Gd2O3、CaCO3、ZrO2、HfO2、V2O5、SnO2、Y2O3,其中a＝1.5，b＝0.45，c＝0.1，d＝0.38，e＝0.17，f＝0，g＝0，δ＝0.05。
实施例6：按组成化学式BiaCabGdcY3-a-b-cFe5-d-e-f-g-δHfdZreVfSngO12称取Fe2O3、Bi2O3、Gd2O3、CaCO3、ZrO2、HfO2、V2O5、SnO2、Y2O3,其中a＝1.5，b＝0.45，c＝0，d＝0.38，e＝0.17，f＝0.1，g＝0，δ＝0.05。
实施例7：按组成化学式BiaCabGdcY3-a-b-cFe5-d-e-f-g-δHfdZreVfSngO12称取Fe2O3、Bi2O3、Gd2O3、CaCO3、ZrO2、HfO2、V2O5、SnO2、Y2O3,其中a＝1.5，b＝0.45，c＝0，d＝0.38，e＝0.17，f＝0，g＝0.1，δ＝0.05。
制备方法：按照实施例1～7称取原材料，原材料都为分析纯；
一次料的制备：将称取好的原材料进行湿法球磨，球：料：稀释剂的比例为4:1:1,(球为氧化锆或钢球,稀释剂为去离子水或酒精)，湿法球磨4h，然后过滤烘干过筛，在700～1000℃进行预烧处理，然后自然冷却；
二次料的制备：将制备好的一次敲碎，倒入球磨罐中，进行二次球磨，球：料：稀释剂的比例为4:1:0.8，湿法球磨4h，然后过滤烘干；
造粒：将二次料加入浓度为9wt％的聚乙烯醇水溶液，充分混合后过筛；
成型：将造粒后的颗粒放入模具进行压制，压制压力为100MPa，得到材料生坯；
烧结：将生坯装入空气气氛炉中进行烧结，烧结温度为900℃～1100℃，保温时间8小时后，自然冷却；
测试：将烧结出的样品进行密度、饱和磁化强度、铁磁共振线宽和介电常数的测试，测试结果如表1所示；
表1:实施例1-7的铁氧体的性能
Figure BDA0002602778580000061
Figure BDA0002602778580000071
上述性能数据，与现有的报道相比：
与“改性的石榴石结构和射频系统”相比，该专利的表2中，介电常数达到31.15，铁磁共振线宽52Oe，饱和磁化强度1857，本专利的介电常数更高，可以达到32以上，而且铁磁共振线宽的最优值更低，从而能够实现尺寸更小的低损耗铁氧体器件，且制备过程中无退火处理，工艺更简单。
铁氧体基片的制备：根据器件的设计要求，将烧结出的样品机械加工成不同尺寸的铁氧体基片，如果是微带器件还需进行基片两面抛光处理，如果是带线器件设计还需对基片进行单面焙银，上述的两面抛光处理和单面焙银均是现有技术。
实施例8：将采用实施例4的材料制得的旋磁基片、普通石榴石旋磁基片(Y3Fe5O12)(介电常数14，饱和磁化强度1850Gs，铁磁共振线宽15Oe)建立环行器三维电磁场模型，设计5G波段(2.5～2.7GHz)的环行器，基片尺寸对比如图1所示，环行器尺寸对比如图2所示，环行器的仿真性能对比如图3～6所示；
从图2中可以看出，采用本发明材料设计的器件其体积尺寸减少约30％，有效解决了器件小型化设计的难题；
从图3～6可以看出：本发明的高介电常数石榴石旋磁基片设计的环行器尺寸比普通旋磁基片设计的环行器尺寸小约30％；隔离度相近，都大于20dB；驻波比相近，都小于1.2；本发明的高介电常数石榴石旋磁基片设计的环行器插入损耗为0.2dB，虽然略大于普通旋磁基片设计环行器的0.1dB，但能够满足器件的设计使用要求。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (9)

1.一种高介电常数、高饱和磁化强度石榴石铁氧体材料，其特征在于：其化学式组成为：BiaCabGdcY3-a-b-cFe5-d-e-f-g-δHfdZreVfSngO12，其中a=1.5，b=0.45，c=0，d=0.33，e=0.22，f=0，g=0，δ为缺铁量,δ=0.05。
2.权利要求1所述的高介电常数、高饱和磁化强度石榴石铁氧体材料的制备方法，其特征在于：
（a）一次料的制备：按组成化学式 BiaCabGdcY3-a-b-cFe5-d-e-f-g-δHfdZreVfSngO12称取原材料进行球磨，球料比例为4:1～1 .5，料与溶剂比例为1: 1～1 .2，球磨4～8 h，然后过滤烘干过筛，在700～1000℃进行预烧处理，然后自然冷却，得到一次料；
（b）二次料的制备：将步骤（a）处理好的一次料敲碎，按料与溶剂的比例1:0 .8～1进行球磨4～8h，然后过滤烘干，即得到二次料；
（c）造粒：将制备的二次料加入胶合剂，进行造粒过筛；
（d）成型：造粒好的细粉放入模具进行压制，压制压强为50MPa～250MPa，得到材料生坯
（e）烧结；将生坯装入空气气氛或氧化气氛炉中进行烧结，即得。
3.根据权利要求2所述的制备方法，其特征在于：步骤（a）中，球磨比为4:1，球磨时间为4h。
4.根据权利要求2所述的制备方法，其特征在于：步骤（a）和/或步骤（c）中，所述球为氧化锆或钢球，所述溶剂为去离子水或酒精。
5.根据权利要求2所述的制备方法，其特征在于：步骤（b）中，料与溶剂的比例为1:0.8，球磨时间为4h。
6.根据权利要求2所述的制备方法，其特征在于：步骤(a)、(c)中过筛时筛规格大小为20目～60目。
7.根据权利要求2所述的制备方法，其特征在于：步骤(c)中，所述胶合剂为聚乙烯醇水溶液，浓度为5wt％～12wt％。
8.根据权利要求2所述的制备方法，其特征在于：步骤(e)中，烧结温度为900℃～1100℃，保温6小时以上。
9.权利要求1所述的高介电常数、高饱和磁化强度石榴石铁氧体材料的应用，其特征在于：用于雷达、5G通信铁氧体器件。
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