CN116409988A - 高介电中等饱和磁化强度石榴石铁氧体材料及制备方法 - Google Patents
高介电中等饱和磁化强度石榴石铁氧体材料及制备方法 Download PDFInfo
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Abstract
高介电中等饱和磁化强度石榴石铁氧体材料及制备方法,涉及材料技术。本发明的石榴石铁氧体材料化学式为BiaCabYcZrdVeFe5‑d‑e‑δO12,其中,0≤a≤1.2,0≤b≤1.46,0.34≤c≤1.8,0≤d≤0.45,0≤e≤0.505,0≤δ≤0.3,δ为缺铁量。本发明的石榴石铁氧体材料的介电常数为23~25,且同时具有中等的饱和磁化强度、铁磁共振线宽可低至30Oe、介电损耗低至2.0×10‑4、居里温度高达205℃,未使用除钇以外的其他稀土元素。该材料不仅可以有效降低微波铁氧体器件的尺寸,还可以降低器件的插入损耗,增加器件带宽,且成本低。
Description
技术领域
本发明涉及材料技术,特别涉及一种无镧系元素的高介电常数、中等饱和磁化强度石榴石铁氧体材料及其制备方法,特别是应用于雷达、5G通信系统中铁氧体器件,属于微波铁氧体材料领域。
背景技术
随着近年来微波技术的迅猛发展,系统对于元器件小型轻量化和高性能提出了更高要求。作为5G、雷达等通讯系统重要部件的微波铁氧体环行器,其发展方向已转向小型轻量化、低损耗和大带宽,并且这种要求越来越高,甚至达到苛刻的程度,因此,发展该类型环行器/隔离器已迫在眉睫。与其它种类的铁氧体相比,多晶石榴石铁氧体具有低损耗的显著优势,其铁磁共振线宽可小于30Oe,已成为X波段以下铁氧体环行器的首选材料。根据铁氧体器件设计理论,铁氧体材料的介电常数越大,越有利于铁氧体器件实现小型轻量化。另外,将铁氧体材料嵌入电介质材料中制成环行器基板,不仅能够有效降低环行器的插入损耗,而且能够拓宽环行器的带宽。但常规石榴石铁氧体材料的微波介电常数约14左右,已不能满足人们对环行器铁氧体材料的新要求。因此,开发出高介电常数、低损耗的石榴石铁氧体材料已成为实现微波铁氧体器件小型轻量化和大带宽的关键途径。
目前针对高介电低损耗YIG的研究,主要集中于对Y3+和Fe3+的取代。中国专利公开号为CN109563640A的《温度不敏感介电常数石榴石》专利,采用氧化物陶瓷工艺制备的Bi1.4Caa+2bZraVbFe5.03-a-bO11.97铁氧体。当a=0.4,b=0.6时,4πMs=1046Gs,ΔH=48Oe,ε′=25.94,tanδε=8.4×10-4,Tc=196.16℃。但该材料的介电损耗相对偏大,居里温度相对较低,不利于提高环行器带宽。当a=0.6,b=0.5时,4πMs=1120Gs,ΔH=31Oe,ε′=27.52,tanδε=5.7×10-4,Tc=145.5℃。该材料铁磁共振线宽和介电损耗低,但居里温度相对较低,器件的工作温度范围相对较窄。
中国专利公开号为CN112456998A,公开的《一种高介电常数的石榴石铁氧体材料及其制备方法》,公开了一种化学式为Y3-a-b-(2c+d+e)GdaBibCa2c+d+eVcZrdSneMnfAlgFe5-c-d-e-f-g-δO12,0≤a≤1.2,0.6≤b≤1.5,0≤c≤0.6,0≤d≤0.7,0≤e≤0.7,0≤f≤0.15,0≤g≤0.5,0≤δ≤0.3,δ为工艺缺铁量。制备出4πMs=1055Gs,ΔH=45Oe,ε′=26.5,tanδε=4.3×10-4,Tc=171℃的石榴石材料。该专利制备得到的石榴石铁氧体材料,饱和磁化强度中等,介电常数较大,但居里温度相对较低,相对应的微波铁氧体器件能应用于C波段,但工作温度范围较窄不利于实际应用。
美国专利公开号为US20200027632A1,公开的《MagneticmaterialswithhighCurietemperaturesanddielectricconstants》,公开了一种GdBiZrV取代的无Y配方石榴石铁氧体。其中化学式为Bi1.46Gd0.18Ca1.36Zr0.36V0.5Fe4.12O11.97的材料具备如下性能:4πMs=1179Gs,ΔH=29Oe,ε′=27.57,Tc=221.5℃。另外一款铁氧体材料配方为Bi1.4Gd0.24Ca1.36Zr0.36V0. 5Fe4.12O11.97,材料性能为:4πMs=1130Gs,ΔH=39Oe,ε′=26.92,Tc=222.4℃。该材料的居里温度、介电常数较高,但配方中使用了大量的Bi元素(Bi≥1.4)、镧系稀土元素,成本较高。
从上述所公开的专利申请或授权的专利文件可知该种材料存在如下问题:一是通过Bi3+等高极化离子提高石榴石铁氧体的介电常数,但由于引入的Bi3+过多,又会导致材料的ΔH较大,从而使得微波铁氧体的损耗过高;二是高介电中等饱和磁化强度的石榴石铁氧体由于离子取代的量比较多,通常都具有较低的居里温度(Tc<200℃),为了提升居里温度,通常会在十二面体位增加镧系稀土元素,使成本增加。
发明内容
本发明所要解决的技术问题是,针对石榴石铁氧体器件小型轻量化和大带宽问题,提供一种无镧系元素的高介电常数、中等饱和磁化强度石榴石铁氧体材料及其制备方法,着重提高石榴石铁氧体材料的介电常数,降低铁磁共振线宽,同时,提高居里温度,以满足C波段以下铁氧体环行器/隔离器小型轻量化和大带宽需求,且成本低。
本发明解决所述技术问题采用的技术方案是,高介电中等饱和磁化强度石榴石铁氧体材料,其特征在于,化学式为BiaCabYcZrdVeFe5-d-e-δO12,其中,0≤a≤1.2,0≤b≤1.46,0.34≤c≤1.8,0≤d≤0.45,0≤e≤0.505,0≤δ≤0.3,δ为缺铁量。
本发明还提供一种高介电中等饱和磁化强度石榴石铁氧体材料的制备方法,包括以下步骤:
(1)配料:按化学式BiaCabYcZrdVeFe5-d-e-δO12,0≤a≤1.2,0≤b≤1.46,0.34≤c≤1.8,0≤d≤0.45,0≤e≤0.505,0≤δ≤0.3,δ为缺铁量,计算并称取原料,所述原料为Bi2O3、CaCO3、Y2O3、ZrO2、V2O5、Fe2O3;
(2)一次球磨:各原料球磨后烘干;
(3)预烧:将步骤2)所得的粉料在830~900℃进行预烧,然后破碎;
(4)二次球磨:将步骤3)所得预烧料后烘干;
(5)造粒:将二次球磨所得粉料造粒;
(6)成型:造粒料压制成型;
(7)烧结:将成型的生坯件进行烧结。
所述步骤(7)为:将成型的生坯件置于空气气氛烧结炉中采用多步烧结法进行烧结,包括三个加热工序:第一个加热工序为850~900℃,保温时间为1~5小时;第二个加热工序为910~960℃,保温时间为1~5小时;第三个加热工序为970~1020℃,保温时间为20~30小时。
所述步骤(2)为:将步骤1)各原料与氧化锆球、去离子水混匀,球:料:水质量比为4:1:1.5,球磨时间为5~8小时,经烘干后进行过80目筛。
所述步骤(3)为:将步骤2)所得的粉料在830~900℃进行预烧,保温时间为1~5h,预烧后进行破碎、过筛。
所述步骤(4)为:将步骤3)所得预烧料在行星式球磨机中进行二次球磨,球:料:水质量比为4:1:1.5,球磨6~8小时,然后烘干、过80目筛。
所述步骤(5)为:将二次球磨所得粉料按重量百分比加入12wt%的聚乙烯醇(PVA)水溶液进行造粒,过筛,取80~200目间造粒料;
所述步骤(6)为:造粒料置入模具进行压制成型,压制压强为150~200MPa。
与现有技术相比,本发明的优点在于:本发明的高介电中等饱和磁化强度石榴石铁氧体材料的介电常数为23~25,且同时具有中等的饱和磁化强度、铁磁共振线宽可低至30Oe、介电损耗低至2.0×10-4、居里温度高达205℃,未使用除钇以外的其他稀土元素。该材料不仅可以有效降低微波铁氧体器件的尺寸,还可以降低器件的插入损耗,增加器件带宽,且成本低。
附图说明
图1为实施例1石榴石铁氧体材料的扫描电镜照片。
图2为实施例2石榴石铁氧体材料的扫描电镜照片。
图3为实施例3石榴石铁氧体材料的扫描电镜照片。
具体实施方式
本发明针对C波段以下铁氧体环行器/隔离器用铁氧体基板,提供一种无镧系元素的石榴石铁氧体材料及其制备方法。其具有以下特点:中等饱和磁化强度(4πMs=1050~1250Gs)、高介电常数(ε′≥23)、低铁磁共振线宽(ΔH≤30Oe)、低介电损耗(tanδε≤2×10-4)和高居里温度(Tc≥205℃)的特点,可有效降低微波环行器/隔离器中心结区尺寸,可满足该类型器件小型轻量化和大带宽设计需求。
作为一个实施方式,高介电中等饱和磁化强度石榴石铁氧体材料的制备方法,包括以下步骤:
1)配料:按化学式BiaCabYcZrdVeFe5-d-e-δO12,0≤a≤1.2,0≤b≤1.46,0.34≤c≤1.8,0≤d≤0.45,0≤e≤0.505,0≤δ≤0.3,δ为缺铁量,计算并称取原料,所述原料为
Bi2O3、CaCO3、Y2O3、ZrO2、V2O5、Fe2O3,纯度为分析纯;
2)一次球磨:将步骤1)各原料与氧化锆球、去离子水在行星式球磨机中进行混匀,球:料:水质量比为4:1:1.5,球磨时间为5~8小时,经烘干后进行过80
目筛;
3)预烧:将步骤2)所得的粉料在830~900℃进行预烧,保温时间为1~5h,预烧后进行破碎、过筛;
4)二次球磨:将步骤3)所得预烧料在行星式球磨机中进行二次球磨,球:料:
水质量比为4:1:1.5,球磨6~8小时,然后烘干、过80目筛;
5)造粒:将二次球磨所得粉料按重量百分比加入12wt%的聚乙烯醇(PVA)水溶液进行造粒,过筛,取80~200目间造粒料;
6)成型:造粒料置入模具进行压制成型,压制压强为150~200MPa;
7)烧结:将成型的生坯件置于空气气氛烧结炉中采用多步烧结法进行烧结,包括三个加热工序。其中第一个加热工序为850~900℃,保温时间为1~5小时;第二个加热工序为910~960℃,保温时间为1~5小时;第三个加热工序为970~1020℃,保温时间为20~30小时。
以下通过具体实施例进一步说明。
实施例1:
配料:根据化学式BiaCabYcZrdVeFe5-d-e-δO12,a=1.2,b=1.245,c=0.555,d=0.415,e=0.415,δ=0,δ为工艺缺铁量,分别计算并称取原料,所述原料分析纯的Y2O3、Bi2O3、CaCO3、ZrO2、V2O5、Fe2O3,称出相应重量的原材料。
一次球磨:将原材料装入球磨罐中,并按料:球:水=1:4:1.5的比例加入氧化锆球和去离子水,一次球磨5~8小时后出料。球磨罐用不锈钢制成,以减少球磨过程中磨损的Fe进入料中,浆料经烘干后80目筛,装入专用的刚玉坩埚中。
预烧:将装有粉料的刚玉坩埚放入空气气氛的箱式炉中进行预烧,预烧温度为830~900℃,保温1~5小时。
二次球磨:将预烧料在行星式球磨机中进行二次球磨,球:料:水质量比为4:1:1.5,球磨6~8小时,然后烘干、过80目筛;
造粒:将二次球磨所得的二次料烘干后,按重量百分比加入12wt%的PVA溶液后进行造粒过筛;
成型:造粒好的细粉放入模具进行压制,压制压强为150~200Mpa;
烧结:将成型的生坯件置于空气气氛烧结炉中采用多步烧结法进行烧结,包括三个加热工序。其中第一个加热工序为850~900℃,保温时间为1~5小时;第二个加热工序为910~960℃,保温时间为1~5小时;第三个加热工序为970~1010℃,保温时间为20~30小时。。
实施例2:
配料:根据化学式BiaCabYcZrdVeFe5-d-e-δO12,1.0≤a≤1.2,1.2≤b≤1.46,0.34≤c≤0.8,0.4≤d≤0.45,0.4≤e≤0.505,0≤δ≤0.3,δ为缺铁量,分别计算并称取原料,所述原料为分析纯的Y2O3、Bi2O3、CaCO3、ZrO2、V2O5、Fe2O3,称出相应重量的原材料。
一次球磨:将原材料装入球磨罐中,并按料:球:水=1:4:1.5的比例加入氧化锆球和去离子水,一次球磨5~8小时后出料。球磨罐用不锈钢制成,以减少球磨过程中磨损的Fe进入料中,浆料经烘干后80目筛,装入专用的刚玉坩埚中。
预烧:将装有粉料的刚玉坩埚放入空气气氛的箱式炉中进行预烧,预烧温度为880℃,保温时间为1~5h。
二次球磨:将预烧料在行星式球磨机中进行二次球磨,球:料:水质量比为4:1:1.5,球磨6~8小时,然后烘干、过80目筛;
造粒:将二次球磨所得的二次料烘干后,按重量百分比加入12wt%的PVA溶液后进行造粒过筛;
成型:造粒好的细粉放入模具进行压制,压制压强为150~200Mpa;
烧结:将成型的生坯件置于空气气氛烧结炉中采用多步烧结法进行烧结,包括三个加热工序。其中第一个加热工序为870℃,保温时间为1~5小时;第二个加热工序为930℃,保温时间为1~5小时;第三个加热工序为990℃,保温时间为20~30小时。
实施例3:
配料:根据化学式BiaCabYcZrdVeFe5-d-e-δO12,1.0≤a≤1.2,1.2≤b≤1.46,0.34≤c≤0.8,0.4≤d≤0.45,0.4≤e≤0.505,0≤δ≤0.3,δ为缺铁量,分别计算并称取原料,所述原料为分析纯的Y2O3、Bi2O3、CaCO3、ZrO2、V2O5、Fe2O3,称出相应重量的原材料。
一次球磨:将原材料装入球磨罐中,并按料:球:水=1:4:1.5的比例加入氧化锆球和去离子水,一次球磨8小时后出料。球磨罐用不锈钢制成,以减少球磨过程中磨损的Fe进入料中,浆料经烘干后80目筛,装入专用的刚玉坩埚中。
预烧:将装有粉料的刚玉坩埚放入空气气氛的箱式炉中进行预烧,预烧温度为830~900℃,保温2小时。
二次球磨:将预烧料在行星式球磨机中进行二次球磨,球:料:水质量比为4:1:1.5,球磨6小时,然后烘干、过80目筛;
造粒:将二次球磨所得的二次料烘干后,按重量百分比加入12wt%的PVA溶液后进行造粒过筛;
成型:造粒好的细粉放入模具进行压制,压制压强为200Mpa;
烧结:将成型的生坯件置于空气气氛烧结炉中采用多步烧结法进行烧结,包括三个加热工序。其中第一个加热工序为850~900℃,保温时间为3小时;第二个加热工序为910~960℃,保温时间为3小时;第三个加热工序为970~1020℃,保温时间为20小时。
由图1~图3的照片可知,本发明的铁氧体材料平均晶粒尺寸均在1.5μm~2.5μm之间,基本保持多面体结构,气孔较少,致密性比较好。
实验与数据
三种实施例样品基本性能见下表:
Claims (7)
1.高介电中等饱和磁化强度石榴石铁氧体材料,其特征在于,化学式为BiaCabYcZrdVeFe5-d-e-δO12,其中,0≤a≤1.2,0≤b≤1.46,0.34≤c≤1.8,0≤d≤0.45,0≤e≤0.505,0≤δ≤0.3。
2.高介电中等饱和磁化强度石榴石铁氧体材料的制备方法,其特征在于,包括以下步骤:
(1)配料:按化学式BiaCabYcZrdVeFe5-d-e-δO12,0≤a≤1.2,0≤b≤1.46,0.34≤c≤1.8,0≤d≤0.45,0≤e≤0.505,0≤δ≤0.3,δ为缺铁量,计算并称取原料,所述原料为Bi2O3、CaCO3、Y2O3、ZrO2、V2O5、Fe2O3;
(2)一次球磨:各原料球磨后烘干;
(3)预烧:将步骤2)所得的粉料在830~900℃进行预烧,然后破碎;
(4)二次球磨:将步骤3)所得预烧料后烘干;
(5)造粒:将二次球磨所得粉料造粒;
(6)成型:造粒料压制成型;
(7)烧结:将成型的生坯件进行烧结。
3.如权利要求2所述的高介电中等饱和磁化强度石榴石铁氧体材料的制备方法,其特征在于,所述步骤(7)为:将成型的生坯件置于空气气氛烧结炉中采用多步烧结法进行烧结,包括三个加热工序:第一个加热工序为850~900℃,保温时间为1~5小时;第二个加热工序为910~960℃,保温时间为1~5小时;第三个加热工序为970~1020℃,保温时间为20~30小时。
4.如权利要求2所述的高介电中等饱和磁化强度石榴石铁氧体材料的制备方法,其特征在于,所述步骤(2)为:将步骤1)各原料与氧化锆球、去离子水混匀,球:料:水质量比为4:1:1.5,球磨时间为5~8小时,经烘干后进行过80目筛。
5.如权利要求2所述的高介电中等饱和磁化强度石榴石铁氧体材料的制备方法,其特征在于,所述步骤(3)为:将步骤2)所得的粉料在830~900℃进行预烧,保温时间为1~5h,预烧后进行破碎、过筛。
6.如权利要求2所述的高介电中等饱和磁化强度石榴石铁氧体材料的制备方法,其特征在于,所述步骤(4)为:将步骤3)所得预烧料在行星式球磨机中进行二次球磨,球:料:水质量比为4:1:1.5,球磨6~8小时,然后烘干、过80目筛。
7.如权利要求2所述的高介电中等饱和磁化强度石榴石铁氧体材料的制备方法,其特征在于,所述步骤(5)为:将二次球磨所得粉料按重量百分比加入12wt%的聚乙烯醇(PVA)水溶液进行造粒,过筛,取80~200目间造粒料;
所述步骤(6)为:造粒料置入模具进行压制成型,压制压强为150~200MPa。
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CN116854460A (zh) * | 2023-07-31 | 2023-10-10 | 东阳富仕特磁业有限公司 | 一种高介电常数高居里温度低损耗微波铁氧体材料及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120133452A1 (en) * | 2010-11-30 | 2012-05-31 | Skyworks Solutions, Inc. | Effective substitutions for rare earth metals in compositions and materials for electronic applications |
CN111662079A (zh) * | 2020-06-28 | 2020-09-15 | 中国电子科技集团公司第九研究所 | 一种介电常数可调的小线宽低损耗微波石榴石材料及制备方法 |
CN114436637A (zh) * | 2022-03-07 | 2022-05-06 | 西南应用磁学研究所(中国电子科技集团公司第九研究所) | 一种高介电常数高功率微波铁氧体材料及其制备方法 |
CN114477995A (zh) * | 2022-02-23 | 2022-05-13 | 西南应用磁学研究所(中国电子科技集团公司第九研究所) | 一种中饱和磁化强度功率型高介电常数石榴石材料及其制备方法 |
CN115340371A (zh) * | 2022-07-26 | 2022-11-15 | 深圳顺络电子股份有限公司 | 一种铁氧体材料、制备方法及微波通信器件 |
-
2023
- 2023-04-12 CN CN202310388195.0A patent/CN116409988A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120133452A1 (en) * | 2010-11-30 | 2012-05-31 | Skyworks Solutions, Inc. | Effective substitutions for rare earth metals in compositions and materials for electronic applications |
CN111662079A (zh) * | 2020-06-28 | 2020-09-15 | 中国电子科技集团公司第九研究所 | 一种介电常数可调的小线宽低损耗微波石榴石材料及制备方法 |
CN114477995A (zh) * | 2022-02-23 | 2022-05-13 | 西南应用磁学研究所(中国电子科技集团公司第九研究所) | 一种中饱和磁化强度功率型高介电常数石榴石材料及其制备方法 |
CN114436637A (zh) * | 2022-03-07 | 2022-05-06 | 西南应用磁学研究所(中国电子科技集团公司第九研究所) | 一种高介电常数高功率微波铁氧体材料及其制备方法 |
CN115340371A (zh) * | 2022-07-26 | 2022-11-15 | 深圳顺络电子股份有限公司 | 一种铁氧体材料、制备方法及微波通信器件 |
Non-Patent Citations (1)
Title |
---|
Y.J. WU ET AL.: "Magnetic and magnetodielectric properties of Bi-substituted yttrium iron garnet ceramics", 《JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS》, vol. 324, pages 3334 - 3337, XP028504725, DOI: 10.1016/j.jmmm.2012.05.045 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116854460A (zh) * | 2023-07-31 | 2023-10-10 | 东阳富仕特磁业有限公司 | 一种高介电常数高居里温度低损耗微波铁氧体材料及其制备方法 |
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