CN106747397B - Yig铁氧体材料及制备方法 - Google Patents

Yig铁氧体材料及制备方法 Download PDF

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CN106747397B
CN106747397B CN201710137283.8A CN201710137283A CN106747397B CN 106747397 B CN106747397 B CN 106747397B CN 201710137283 A CN201710137283 A CN 201710137283A CN 106747397 B CN106747397 B CN 106747397B
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ball milling
sintering
yig ferrite
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孙科
郭启广
余忠
蒋晓娜
兰中文
郭荣迪
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University of Electronic Science and Technology of China
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Abstract

YIG铁氧体材料及制备方法，属于铁氧体材料制备技术领域，本发明的YIG铁氧体材料包括主料和掺杂剂，其特征在于，主料包括47.8～61.1mol％Fe2O3、26.1～36.4mol％Y2O3、1.2～13.0mol％SnO2，余量为CaCO3；按重量百分比，以氧化物计算，掺杂剂包括：0.05～0.40wt％Bi2O3、0.05～0.10wt％Nb2O5、0.05～0.20wt％Ta2O5、0.50～0.60wt％纳米BaTiO3。本发明兼具小线宽、低损耗且原材料廉价易得的特性。

Description

YIG铁氧体材料及制备方法
技术领域
本技术属于铁氧体材料制备技术领域，特别涉及小线宽、低损耗的YIG铁氧体材料及其制备方法。
背景技术
铁氧体微波器件(如电调谐滤波器、限幅器、移相器、环行器等)具有承载功率高、损耗低等优点，长期以来在相控阵雷达、电子对抗以及高能物理粒子加速器、移动通信、人造卫星、电视等军用和民用方面发挥着重要作用。随着铁氧体微波器件向高频化、轻型化等方向发展，对应用于其中的铁氧体提出了更多新要求，如饱和磁化强度符合特定要求、微波介电损耗tanδε小、铁磁共振线宽ΔH小、温度稳定性高等，以获得更好的通信质量和更低廉的生产成本。因此小线宽、低损耗的微波铁氧体材料具有非常广阔的应用前景。
目前已有专利文献报道石榴石YIG铁氧体材料及其制备方法，如已公开的中国专利CN 101591168A中公开了一种石榴石铁氧体，其化学式为：Y3-2xCa2xVxInyMnzFe5-x-y-zO12或Y3-xCaxGexInyMnzFe5-x-y-zO12，饱和磁化强度为80kA/m时，铁磁共振线宽ΔH为0.5kA/m，居里温度为235℃；专利CN 105347782A中提出石榴石铁氧体材料化学式为SmxY3-x-y-2z-p-q-q′Ca2x+z+p+qVzGepInq″SnqTiq′AlwMnw′Fe5-z-p-q-q′-q″-w-w′-δO12，饱和磁化强度为127kA/m，居里温度为240℃，铁磁共振线宽ΔH为3.2kA/m，介电常数14.4，介电损耗tanδε为0.4×10-4；专利CN102976740A中发明的石榴石铁氧体化学式为Y3-x′-2x-z-p-qBix′Ca2x+z+p+qVxGezInySnpTiqMnwAlw′Fe5-x-y-z-p-q-w-w′-δO12，通过采用Ge4+、In3+、Sn4+等离子联合取代及缺铁配方，提高了材料的介电常数，饱和磁化强度为128kA/m，居里温度为230℃，铁磁共振线宽为0.8kA/m，介电常数15.0，介电损耗tanδε为0.7×10-4。上述专利的材料组成成分复杂，同时在材料制备过程中选用了价格昂贵的原材料如In2O3、GeO2等，而当前In2O3市价约2000元/kg、GeO2市价约7000元/kg。因此开发成分简单、成本低廉、性能优良的YIG铁氧体材料对于满足当前市场的需求具有广阔前景。
发明内容
本发明所要解决的技术问题是，针对现有的YIG铁氧体材料存在的线宽大、损耗高或线宽虽小但原材料价格昂贵等不足，提出一种兼具小线宽、低损耗且原材料廉价易得的微波铁氧体材料及其制备方法。
本发明解决所述技术问题采用的技术方案是，YIG铁氧体材料，其组分包括：
47.8～61.1mol％Fe2O3，26.1～36.4mol％Y2O3，1.2～13.0mol％SnO2，余量为CaCO3；
掺杂剂按重量百分比，以氧化物计算：0.05～0.40wt％Bi2O3、0.05～0.10wt％Nb2O5、0.05～0.20wt％Ta2O5、0.50～0.60wt％纳米BaTiO3。即，在YIG材料(包含主料和掺杂剂)中，Bi2O3的比例为0.05～0.40wt％，Nb2O5为0.05～0.10wt％，Ta2O5为0.05～0.20wt％，纳米BaTiO3为0.50～0.60wt％。其中，“纳米BaTiO3”表示BaTiO3的粒径为纳米级，粒径≤100纳米。
本发明还提供YIG铁氧体的制备方法，其特征在于，包括下述步骤：
1)配方
以Fe2O3、Y2O3、SnO2、CaCO3为原料，按照分子式Y3-xCaxFe5-xSnxO12确定原料比例，0.05≤x≤0.60；
2)一次球磨
将按照比例配好的粉料在球磨机内混合均匀；
3)预烧
将步骤2所得球磨料烘干，在800～1100℃炉内预烧1～3小时；
4)掺杂
将步骤3所得料粉按如下比例掺杂：0.05～0.40wt％Bi2O3、0.05～0.10wt％Nb2O5、0.05～0.20wt％Ta2O5、0.50～0.60wt％纳米BaTiO3；
5)二次球磨
将步骤4)得到的粉料在球磨机中球磨；
6)成型
将步骤5)所得料粉按重量比加入8～12wt％有机粘合剂，混匀，造粒后，在压机上将粒状粉料压制成坯件；
7)烧结
将步骤6)所得坯件置于气氛烧结炉内烧结，在1300℃～1400℃保温4～6小时。
8)测试
将步骤7)所得样品进行性能测试。
材料比饱和磁化强度ζs用美国Quantum Design SQUID VSM测试；
材料密度d用阿基米德排水法测试，饱和磁化强度由Ms＝ζsd计算；
材料的物相、晶格常数a用DX-2700X射线衍射仪测试并分析；
材料的居里温度用Netzsch STA409PC热失重分析仪(TGA)测试；
按IEC标准在9.3GHz下测量样品的铁磁共振线宽ΔH、介电常数ε′和介电损耗tanδε。
本发明采用的YIG铁氧体材料的指标如下：
饱和磁化强度Ms：≥147kA/m(25℃)；
气孔率P：＜0.9％；
铁磁共振线宽ΔH(9.3GHz)：＜2.3kA/m(25℃)；
介电常数ε′(9.3GHz)：＝14.8±5％
介电损耗tanδε(9.3GHz)：≤1.05×10-4
居里温度Tc：187～273℃
本发明提出的离子取代的YIG铁氧体线宽分离计算方法解决如下三个问题：其一，通过离子取代减小磁晶各向异性常数K1，降低磁晶各向异性线宽ΔHa；其二，通过离子取代减弱材料晶格间的超交换作用以调控材料的居里温度；其三，通过掺杂高活性纳米BaTiO3有效降低材料的微波介电损耗，对降低微波器件的损耗有重要意义。
具体实施方式
针对目前国内外对小线宽、低损耗YIG铁氧体材料的研究，本发明提出了了一种具有小线宽、低损耗、高介电常数的YIG铁氧体及其制备方法。其指导思想是：降低磁晶各向异性、调控超交换作用、添加高活性纳米掺杂剂、特种粉体制备工艺。首先，通过优选的高纯度Fe2O3、Y2O3、SnO2、CaCO3为原材料，深入分析了YIG铁氧体的离子占位以及材料中存在的超交换作用、磁化动力、磁化阻力，尤其对降低铁磁共振线宽和微波介电损耗，制定最优的配方范围；其次，深入分析不同掺杂剂对YIG铁氧体材料显微结构的影响机制，研究了掺杂剂Bi2O3、Nb2O5、Ta2O5、高活性纳米BaTiO3等对YIG铁氧体晶粒/晶界特性的影响，制定最优的掺杂剂含量；接着，选用并按一定比例配好不同直径大小的超硬球磨介质，结合适宜的分散剂球磨粉料至0.5～0.9μm，制备了高活性粉体；最后，以制定的配方和掺杂剂为基础及优化的粉体制备工艺，结合高密度均匀晶粒的烧结工艺制备具有小线宽、低损耗、低介电损耗等特点的YIG铁氧体。
本发明的核心思想是：在配方上，采用Sn4+-Ca2+联合取代，Ca2+取代Y3+使得材料的制备成本降低，非磁性Sn4+取代八面体16a位的Fe3+使得晶格中的磁性离子数量发生变化，控制材料的交换作用，从而调控材料的居里温度。另一方面，Sn4+取代可以减小材料的磁晶各向异性常数K1，有利于减小材料的磁晶各向异性线宽ΔHa，且Sn4+取代使得在较低的烧结温度下材料的致密化程度增加、气孔率P降低，进而减小材料的气孔致宽ΔHp。
在掺杂剂的选取上，采用Bi2O3、Nb2O5、Ta2O5、高活性纳米BaTiO3等掺杂剂的助熔和阻晶双性作用，实现复合掺杂剂交互作用的控制，一方面提高烧结密度，降低样品的气孔率，有效地降低YIG铁氧体材料的气孔致宽ΔHp；另一方面，控制晶粒尺寸均匀适中，控制材料的晶粒/晶界特性，降低材料损耗；除以上两方面外，通过具有高介电常数的高活性纳米BaTiO3掺杂剂富集于晶界处及高价离子对Fe2+形成的抑制作用，可以有效的提高材料的电阻率，降低YIG铁氧体的微波介电损耗。
在烧结工艺方面，结合特种高活性亚微米粉体制备工艺，制备高活性亚微米粉体，借助复合添加剂双性作用，在烧结过程中应用二次还原工艺，实现材料的高密度均匀晶粒烧结。复合添加剂的双性作用和二次还原烧结技术使得材料的晶粒/晶界特性可控，获得均匀的显微结构，进一步减小样品的气孔率，降低气孔致宽从而减小损耗。
总的来说，通过对磁晶各向异性和分子场交换作用的控制，实现调控YIG铁氧体材料的居里温度和降低磁晶各向异性线宽ΔHa；通过低熔点、高介电常数掺杂剂的引入，控制材料的晶粒/晶界特性，有效促进YIG铁氧体材料的致密化生长，使得YIG铁氧体材料具有低的气孔线宽ΔHp和低的微波介电损耗；最后通过特种制备工艺，进一步减小材料损耗。
本发明材料具有适当的饱和磁化强度(Ms≥147KA/m)、小线宽(ΔH＜2.3kA/m)、居里温度可调(187～273℃)、介电常数高(ε′(9.3GHz)＝14.8±5％)、低介电损耗(tanδε(9.3GHz)≤1.05×10-4)及低气孔率(p＜0.9％)等特性。
本发明提出的YIG铁氧体材料主成分按摩尔百分比计算，转换成分子式为Y3- xCaxFe5-xSnxO12(0.05≤x≤0.60)，x表示取代量，掺杂剂成分按重量百分比，以氧化物计算。
本发明具体包括以下步骤：
1、配方
采用47.8～61.1mol％Fe2O3，26.1～36.4mol％Y2O3，1.2～13.0mol％SnO2，余量为CaCO3；
2、一次球磨
将按照比例配好的粉料在球磨机内混合均匀，时间4～6小时；
3、预烧
将步骤2所得球磨料烘干，并在800～1100℃炉内预烧1～3小时；
4、掺杂
将步骤3所得料粉按如下比例掺杂：0.05～0.40wt％Bi2O3、0.05～0.10wt％Nb2O5、0.05～0.20wt％Ta2O5、0.50～0.60wt％纳米BaTiO3；
本发明中，采用“～”表示范围的，皆包含端值本数，例如“47.8～61.1mol％Fe2O3”的数值范围中，包含47.8与61.1两个数值。
掺杂剂的含量是以主料和掺杂剂的整体质量为计算基准，例如0.05～0.40wt％Bi2O3是指以所有主料和所有掺杂剂的质量和为基准，Bi2O3的含量为0.05～0.40wt％。
5、二次球磨
在球磨机中按一定比例配好不同直径大小的超硬球磨介质，将步骤4中得到的粉料按照一定球料比例混合，在球磨机中球磨4～8小时；
6、成型
将步骤5所得料粉按重量比加入8～12wt％有机粘合剂，混匀，造粒后，在压机上将粒状粉料压制成坯件；
7、烧结
将步骤6所得坯件置于气氛烧结炉内烧结，在1300℃～1400℃保温4～6小时；
8、测试
将步骤7所得样品进行性能测试。
材料比饱和磁化强度ζs用美国Quantum Design SQUID VSM测试；
材料密度d用阿基米德排水法测试；饱和磁化强度由Ms＝ζsd计算；
材料的物相、晶格常数a用DX-2700X射线衍射仪测试并分析；
材料的居里温度用Netzsch STA409PC热失重分析仪(TGA)测试；
按IEC标准在9.3GHz下测量样品的铁磁共振线宽ΔH、介电常数ε′和介电损耗tanδε。
具体实施例：
实施例1～5：一种YIG铁氧体材料的制备方法包括以下步骤：
1、配方
实施例1～5(x表示分子式Y3-xCaxFe5-xSnxO12中Sn离子取代量)主配方及纳米BaTiO3掺杂量见下表：
Figure BDA0001241749390000061
2、一次球磨
将按照比例配好的粉料在球磨机内混合均匀，时间6小时；
3、预烧
将步骤2所得球磨料烘干，在1100℃炉内预烧2小时；
4、掺杂
将步骤3所得料粉按以下重量百分比掺杂：0.20wt％Bi2O3、0.05wt％Nb2O5、0.10wt％Ta2O5、0.50wt％纳米BaTiO3；
5、二次球磨
在球磨机中按一定比例配好不同直径大小的超硬球磨介质，将步骤4中得到的粉料按照一定球料比例混合，在球磨机中球磨6小时；
6、成型
将步骤5所得料粉按重量比加入12wt％有机粘合剂，混匀，造粒后，在压机上将粒状粉料压制成坯件；
7、烧结
将步骤6所得坯件置于气氛烧结炉内烧结，在1380℃保温6小时；
8、测试结果
经过以上工艺制备出的离子取代YIG铁氧体材料其性能指标如下：
实施例1～5测试及计算结果如下：
Figure BDA0001241749390000071

Claims (2)

1.YIG铁氧体材料的制备方法，其特征在于，
所述YIG铁氧体材料的原料包括主料和掺杂剂，主料包括47.8~61.1mol% Fe2O3、26.1~36.4mol% Y2O3、1.2~13.0mol% SnO2，余量为CaCO3；
按重量百分比，以氧化物计算，掺杂剂包括：0.05~0.40wt%Bi2O3、0.05~0.10wt%Nb2O5、0.05~0.20wt%Ta2O5、0.50~0.60wt%纳米BaTiO3；
制备方法包括下述步骤：
1)配方
以Fe2O3、 Y2O3、SnO2、CaCO3为原料，按照分子式Y3-x Ca x Fe5-x Sn x O12确定原料比例，0.05≤x≤0.60；
2)一次球磨
将按照比例配好的原料在球磨机内混合均匀；
3)预烧
将步骤2）所得球磨料烘干，在800~1100℃炉内预烧1~3小时；
4)掺杂
将步骤3）所得料粉按如下重量百分比掺杂：0.05~0.40wt%Bi2O3、0.05~0.10wt%Nb2O5、0.05~0.20wt%Ta2O5、0.50~0.60wt%纳米BaTiO3；
5)二次球磨
将步骤4）得到的粉料在球磨机中球磨；
6)成型
将步骤5）所得料粉按重量比加入8~12wt％有机粘合剂，混匀，造粒后，在压机上将粒状粉料压制成坯件；
7)烧结
将步骤6）所得坯件置于气氛烧结炉内烧结，在1300℃~1400℃保温4~6小时。
2.根据权利要求1所述YIG铁氧体材料的制备方法，其特征在于：
所述一次球磨步骤中，球磨时间为4~6h；
所述纳米BaTiO3的粒径≤100纳米；
所述二次球磨步骤中，球磨时间为4~8h。
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