CN111499369A - 一种Ku波段用高功率旋矩铁氧体材料及其制备方法 - Google Patents

一种Ku波段用高功率旋矩铁氧体材料及其制备方法 Download PDF

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CN111499369A
CN111499369A CN202010379833.9A CN202010379833A CN111499369A CN 111499369 A CN111499369 A CN 111499369A CN 202010379833 A CN202010379833 A CN 202010379833A CN 111499369 A CN111499369 A CN 111499369A
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蒋晓娜
刘小龙
余忠
孙科
邬传健
兰中文
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University of Electronic Science and Technology of China
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Abstract

一种Ku波段用高功率旋矩铁氧体材料及制备方法，属于铁氧体材料制备技术领域。该铁氧体材料包括主料和添加剂，主料Li0.5+0.5x‑ 0.5yTixZnyMn0.06Fe(2.44‑1.5x‑0.5y)(1‑z)O4‑1.5(2.44‑1.5x‑0.5y)z，x＝0.15～0.25，y＝0.04～0.06，z＝0.04～0.06；添加剂按主成分质量百分比，以氧化物计算：0.05～0.20wt％CaCO3，0.20～0.80wt％Bi2O3，0.01～0.10wt％V2O5。本发明旋矩铁氧体材料兼具适宜的饱和磁化强度和自旋波线宽、高居里温度、高剩磁比、低矫顽力和较低铁磁共振线宽和低介电损耗。

Description

一种Ku波段用高功率旋矩铁氧体材料及其制备方法
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Ku波段铁氧体开关和移相器用高功率LiTiZn旋矩铁氧体材料及其制备方法。
背景技术
随着雷达技术的发展，相控阵雷达中开关和移相器等微波/毫米波器件正朝着大功率、高精度、高频化方向发展。Li系铁氧体由于室温下的饱和磁化强度(4πMs)可调范围宽、居里温度(Tc)高和剩磁比(Br/Bm)高而被广泛应用于X波段及以上频段的铁氧体开关或移相器。对于Ku波段高功率铁氧体开关或移相器来说，由于承载功率高，易导致铁氧体材料出现打火现象和发热问题，这就要求铁氧体材料不仅具有适宜的饱和磁化强度、高剩磁比、低矫顽力(Hc)等基本性能，而且要求铁氧体材料具有高自旋波线宽(ΔHk)、低铁磁共线宽(ΔH)、低微波介电损耗(tanδε)和高居里温度，以便提高器件的稳定性。
单元Li铁氧体室温下的饱和磁化强度约3700Gs，居里温度约670℃。为满足Ku波段高功率铁氧体材料性能要求，需将材料的饱和磁化强度降低，通常采用Ti4+、Al3+等非磁性离子取代的手段，这也有利于降低材料的矫顽力和铁磁共振线宽，但这会导致材料居里温度下降，引起材料的温度稳定性下降，这一问题一直未得到很好地解决。
目前，Ti4+、Zn2+离子取代的Li系铁氧体(LiTiZn铁氧体)材料可适用于Ku波段，在国内外均有研究报道。典型代表产品如下，我国西南应用磁学研究所的XL26A型Li系铁氧体材料可适用于Ku波段，其性能指标为：4πMs＝2600±5％Gs，ΔH<250Oe，微波介电常数ε′＝15.5，tanδε<5×10-4，Tc>350℃。美国EMS公司L1201型Li系铁氧体材料的磁性能为：4πMs＝2600Gs，Hc＝0.6Oe，Br/Bm＝0.81，ε′＝17，tanδε<5×10-4，Tc＝325℃，ΔH＝200Oe。俄罗斯Doman公司的SL250型Li系铁氧体材料的性能为：4πMs＝2500Gs，Hc＝1.91Oe，ε′＝15.4，tanδε≤5×10-4，Tc＝550℃，ΔH<500Oe。法国Temex公司的A24型Li系铁氧体材料的性能为：4πMs＝2450GS，ε′＝16.8，tanδε≤5×10-4，Tc＝390℃，ΔH＝250Oe。可见，国内外已经开发出了用于Ku波段铁氧体开关或移相器的材料，且性能各有优势。但针对此类材料，兼具高居里温度(Tc≥480℃)、高剩磁比(Br/Bm≥0.9)、低矫顽力(Hc≤1.5Oe)和较低铁磁共振线宽(ΔH<320Oe)的Li系铁氧体材料还未见报道。
基于上述，本发明提供了一种Ku波段高功率旋矩铁氧体材料及其制备方法。该材料为LiTiZn铁氧体，具有适宜的饱和磁化强度和自旋波线宽、高居里温度、高剩磁比、低矫顽力、较低的铁磁共振线宽和低微波介电损耗。
发明内容
本发明针对Ku波段高功率铁氧体开关或移相器用铁氧体材料，提供了一种高旋矩LiTiZn铁氧体材料及制备方法。该材料由传统氧化物陶瓷工艺制得，性能兼具适宜的饱和磁化强度和自旋波线宽、高居里温度、高剩磁比、低矫顽力和较低铁磁共振线宽和低介电损耗。
本发明所要解决的技术问题是，基于氧化物陶瓷工艺，通过特定的配方、添加剂和制备工艺技术，提供一种Ku波段高功率旋矩铁氧体材料及其制备方法。所制备的Ku波段高功率开关或移相器用铁氧体材料性能参数为：4πMs＝2500±5％Gs、Br/Bm≥0.9、Hc≤1.5Oe、ΔH<320Oe、ΔHk≥3Oe、Tc≥480℃、温度系数α<2.5‰/℃(-55℃～+85℃)、ε′＝15±10％、tanδε<8×10-4。
为解决上述技术问题，本发明采用的技术方案如下：
一种Ku波段用高功率旋矩铁氧体材料，其特征在于，包括主料和添加剂，其中，主料成分按铁氧体分子式Li0.5+0.5x-0.5yTixZnyMn0.06Fe(2.44-1.5x-0.5y)(1-z)O4-1.5(2.44-1.5x-0.5y)z进行计算，x＝0.15～0.25，y＝0.04～0.06，z＝0.04～0.06，所需原料为Li2CO3，TiO2，ZnO，Mn3O4，Fe2O3；添加剂按主成分质量百分比，以氧化物计算为：0.05～0.20wt％CaCO3，0.20～0.80wt％Bi2O3，0.01～0.10wt％V2O5。
一种Ku波段用高功率旋矩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Li2CO3、TiO2、ZnO、Mn3O4、Fe2O3为原料，按照铁氧体分子式Li0.5+0.5x- 0.5yTixZnyMn0.06Fe(2.44-1.5x-0.5y)(1-z)O4-1.5(2.44-1.5x-0.5y)z计算原料质量，并称料，其中x＝0.15～0.25，y＝0.04～0.06，z＝0.04～0.06；
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，时间为1～3h；
步骤3、预烧
将步骤2得到的球磨料烘干，并置于烧结炉内进行预烧，预烧温度为800～900℃，预烧时间为2～4h，完成后，随炉自然降温至室温，得到预烧粉体；
步骤4、二次球磨
在步骤3得到的预烧粉体中加入添加剂，所述添加剂按主成分重量百分比，以氧化物计算为：0.05～0.20wt％CaCO3，0.20～0.80wt％Bi2O3，0.01～0.10wt％V2O5；然后在行星式球磨机中进行二次球磨，时间为2～8h；
步骤5、成型
将步骤4得到的二次球磨料烘干后，加入8～12wt％的聚乙烯醇(PVA)进行造粒，在6～8MPa下压制成环形生坯件；
步骤6、烧结
将步骤5制得的生坯件置于马弗炉内进行烧结，烧结温度为950～1050℃，保温时间为2～5h，升温速率为0.5～2℃/min，完成后，随炉冷却至室温即可得到所述Ku波段用高功率旋矩铁氧体材料。
经过以上工艺制备出的Ku波段高功率旋矩铁氧体材料，显微结构均匀致密。根据相关测试标准对所述材料进行性能测试。
与现有技术相比，本发明的有益效果为：
本发明提供的一种Ku波段用高功率旋矩铁氧体材料，基于氧化物陶瓷工艺，在Li铁氧体基础上，采用非磁性Ti4+、Zn2+离子取代来获得适宜的饱和磁化强度和高剩磁，以满足Ku波段铁氧体材料旋磁性能要求，并确保高居里温度；同时，Ti4+、Zn2+离子还能有效降低磁晶各向异性常数(K1)，进而降低材料的矫顽力和铁磁共振线宽。为获得低剩磁应力敏感性和低介电损耗，在主配方中引入Mn3+离子。利用缺铁技术，进一步降低材料的介电损耗、矫顽力和铁磁共振线宽，并确保高居里温度。通过优化的Bi2O3、CaCO3、V2O5添加剂技术和制备工艺技术严格控制气孔率、晶粒/晶界特性和显微结构，确保材料具有低矫顽力、较低的铁磁共振线宽和适宜的自旋波线宽。本发明所制备的Ku波段高功率开关或移相器用铁氧体材料性能参数为：4πMs＝2500±5％Gs、Br/Bm≥0.9、Hc≤1.5Oe、ΔH<320Oe、ΔHk≥3Oe、Tc≥480℃、温度系数α<2.5‰/℃(-55℃～+85℃)、ε′＝15±10％、tanδε<8×10-4。
附图说明
图1为实施例1得到的高功率旋矩铁氧体材料的扫描电镜照片；
图2为实施例2得到的高功率旋矩铁氧体材料的扫描电镜照片；
图3为实施例3得到的高功率旋矩铁氧体材料的扫描电镜照片；
图4为实施例4得到的高功率旋矩铁氧体材料的扫描电镜照片。
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。
实施例1
一种Ku波段用高功率旋矩铁氧体材料的制备方法，具体包括以下步骤：
步骤1、配料
以Li2CO3、TiO2、ZnO、Mn3O4、Fe2O3为原料，按照铁氧体分子式Li0.5+0.5x- 0.5yTixZnyMn0.06Fe(2.44-1.5x-0.5y)(1-z)O4-1.5(2.44-1.5x-0.5y)z计算原料质量，并称料，其中x＝0.2，y＝0.05，z＝0.04；
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，时间为2h；
步骤3、预烧
将步骤2得到的球磨料烘干，并置于烧结炉内进行预烧，预烧温度为900℃，预烧时间为4h，完成后，随炉自然降温至室温，得到预烧粉体；
步骤4、二次球磨
在步骤3得到的预烧粉体中加入添加剂，所述添加剂按主成分重量百分比，以氧化物计算为：0.10wt％CaCO3，0.40wt％Bi2O3，0.01wt％V2O5；然后在行星式球磨机中进行二次球磨，时间为4h；
步骤5、成型
将步骤4得到的二次球磨料烘干后，加入10wt％的聚乙烯醇(PVA)进行造粒，在8MPa下压制成环形生坯件；
步骤6、烧结
将步骤5制得的生坯件置于马弗炉内进行烧结，烧结温度为1000℃，保温时间为2h，升温速率为1℃/min，完成后，随炉冷却至室温即可得到所述Ku波段用高功率旋矩铁氧体材料。
实施例1制得的Ku波段高功率旋矩铁氧体材料性能见下表：
Figure BDA0002481552320000051
实施例2
一种Ku波段用高功率旋矩铁氧体材料的制备方法，具体包括以下步骤：
步骤1、配料
以Li2CO3、TiO2、ZnO、Mn3O4、Fe2O3为原料，按照铁氧体分子式Li0.5+0.5x- 0.5yTixZnyMn0.06Fe(2.44-1.5x-0.5y)(1-z)O4-1.5(2.44-1.5x-0.5y)z计算原料质量，并称料，其中x＝0.2，y＝0.05，z＝0.05；
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，时间为2h；
步骤3、预烧
将步骤2得到的球磨料烘干，并置于烧结炉内进行预烧，预烧温度为900℃，预烧时间为4h，完成后，随炉自然降温至室温，得到预烧粉体；
步骤4、二次球磨
在步骤3得到的预烧粉体中加入添加剂，所述添加剂按主成分重量百分比，以氧化物计算为：0.15wt％CaCO3，0.50wt％Bi2O3，0.01wt％V2O5；然后在行星式球磨机中进行二次球磨，时间为4h；
步骤5、成型
将步骤4得到的二次球磨料烘干后，加入10wt％的聚乙烯醇(PVA)进行造粒，在8MPa下压制成环形生坯件；
步骤6、烧结
将步骤5制得的生坯件置于马弗炉内进行烧结，烧结温度为1000℃，保温时间为2h，升温速率为1℃/min，完成后，随炉冷却至室温即可得到所述Ku波段用高功率旋矩铁氧体材料。
实施例2制得Ku波段高功率旋矩铁氧体材料性能见下表：
Figure BDA0002481552320000061
实施例3
一种Ku波段用高功率旋矩铁氧体材料的制备方法，具体包括以下步骤：
步骤1、配料
以Li2CO3、TiO2、ZnO、Mn3O4、Fe2O3为原料，按照铁氧体分子式Li0.5+0.5x- 0.5yTixZnyMn0.06Fe(2.44-1.5x-0.5y)(1-z)O4-1.5(2.44-1.5x-0.5y)z计算原料质量，并称料，其中x＝0.225，y＝0.05，z＝0.05；
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，时间为2h；
步骤3、预烧
将步骤2得到的球磨料烘干，并置于烧结炉内进行预烧，预烧温度为900℃，预烧时间为4h，完成后，随炉自然降温至室温，得到预烧粉体；
步骤4、二次球磨
在步骤3得到的预烧粉体中加入添加剂，所述添加剂按主成分重量百分比，以氧化物计算为：0.10wt％CaCO3，0.40wt％Bi2O3，0.01wt％V2O5；然后在行星式球磨机中进行二次球磨，时间为4h；
步骤5、成型
将步骤4得到的二次球磨料烘干后，加入10wt％的聚乙烯醇(PVA)进行造粒，在8MPa下压制成环形生坯件；
步骤6、烧结
将步骤5制得的生坯件置于马弗炉内进行烧结，烧结温度为1000℃，保温时间为3h，升温速率为1℃/min，完成后，随炉冷却至室温即可得到所述Ku波段用高功率旋矩铁氧体材料。
实施例3制得Ku波段高功率旋矩铁氧体材料性能为：
Figure BDA0002481552320000071
实施例4
一种Ku波段用高功率旋矩铁氧体材料的制备方法，具体包括以下步骤：
步骤1、配料
以Li2CO3、TiO2、ZnO、Mn3O4、Fe2O3为原料，按照铁氧体分子式Li0.5+0.5x- 0.5yTixZnyMn0.06Fe(2.44-1.5x-0.5y)(1-z)O4-1.5(2.44-1.5x-0.5y)z计算原料质量，并称料，其中x＝0.225，y＝0.05，z＝0.06；
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，时间为2h；
步骤3、预烧
将步骤2得到的球磨料烘干，并置于烧结炉内进行预烧，预烧温度为900℃，预烧时间为4h，完成后，随炉自然降温至室温，得到预烧粉体；
步骤4、二次球磨
在步骤3得到的预烧粉体中加入添加剂，所述添加剂按主成分重量百分比，以氧化物计算为：0.15wt％CaCO3，0.50wt％Bi2O3，0.01wt％V2O5；然后在行星式球磨机中进行二次球磨，时间为4h；
步骤5、成型
将步骤4得到的二次球磨料烘干后，加入10wt％的聚乙烯醇(PVA)进行造粒，在8MPa下压制成环形生坯件；
步骤6、烧结
将步骤5制得的生坯件置于马弗炉内进行烧结，烧结温度为1020℃，保温时间为2h，升温速率为1℃/min，完成后，随炉冷却至室温即可得到所述Ku波段用高功率旋矩铁氧体材料。
实施例4制得Ku波段高功率旋矩铁氧体材料性能为：
Figure BDA0002481552320000081

Claims (2)

1.一种Ku波段用高功率旋矩铁氧体材料，其特征在于，包括主料和添加剂，其中，主料为Li0.5+0.5x-0.5yTixZnyMn0.06Fe(2.44-1.5x-0.5y)(1-z)O4-1.5(2.44-1.5x-0.5y)z，x＝0.15～0.25，y＝0.04～0.06，z＝0.04～0.06；添加剂按主成分质量百分比，以氧化物计算为：0.05～0.20wt％CaCO3，0.20～0.80wt％Bi2O3，0.01～0.10wt％V2O5。
2.一种Ku波段用高功率旋矩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Li2CO3、TiO2、ZnO、Mn3O4、Fe2O3为原料，按照分子式Li0.5+0.5x- 0.5yTixZnyMn0.06Fe(2.44-1.5x-0.5y)(1-z)O4-1.5(2.44-1.5x-0.5y)z计算原料质量，并称料，其中x＝0.15～0.25，y＝0.04～0.06，z＝0.04～0.06；
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，时间为1～3h；
步骤3、预烧
将步骤2得到的球磨料烘干，并置于烧结炉内进行预烧，预烧温度为800～900℃，预烧时间为2～4h，完成后，随炉自然降温至室温，得到预烧粉体；
步骤4、二次球磨
在步骤3得到的预烧粉体中加入添加剂，所述添加剂按主成分重量百分比，以氧化物计算为：0.05～0.20wt％CaCO3，0.20～0.80wt％Bi2O3，0.01～0.10wt％V2O5；然后进行二次球磨，时间为2～8h；
步骤5、成型
将步骤4得到的二次球磨料烘干，造粒，并压制得到生坯件；
步骤6、烧结
将步骤5制得的生坯件进行烧结处理，烧结温度为950～1050℃，保温时间为2～5h，完成后，随炉冷却至室温即可得到所述Ku波段用高功率旋矩铁氧体材料。
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