CN112456993A - 一种可用于铁氧体器件的微波铁氧体材料及制备方法 - Google Patents

一种可用于铁氧体器件的微波铁氧体材料及制备方法 Download PDF

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CN112456993A
CN112456993A CN202011185739.6A CN202011185739A CN112456993A CN 112456993 A CN112456993 A CN 112456993A CN 202011185739 A CN202011185739 A CN 202011185739A CN 112456993 A CN112456993 A CN 112456993A
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ball milling
ferrite material
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microwave ferrite
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赵鑫
彭清华
李心怡
苌群峰
相东
张军傲
张楚贤
郑国龙
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CHINA AEROSPACE TIMES ELECTRONICS CO LTD
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Abstract

本发明公开了一种可用于铁氧体器件的微波铁氧体材料及制备方法。该铁氧体属于锂铁氧体材料，化学成分为LixZnyMnzBiuNiv(Dy,Tb)wFe2.26±γO4±δ，其中：x＝0.35‑0.37，y＝0.27‑0.29，z＝0.045‑0.055，u＝0.004‑0.006，v＝0‑0.03，w＝0‑0.03，γ＝0‑0.0113，δ＝0‑0.02。本发明提出了通过工艺调节饱和磁化强度的方法，可以将制的的微波铁氧体材料的饱和磁化强度控制在4300‑5100Gs范围内。本发明制备的微波铁氧体材料具有高剩磁比(Ms/Mr≥0.9)，低矫顽力(Hc≤2Oe)，低损耗(损耗角正切tanδ≤1×10‑3)等特点。

Description

一种可用于铁氧体器件的微波铁氧体材料及制备方法
技术领域
本发明涉及一种可用于铁氧体器件的微波铁氧体材料及制备方法，属于电子元器件核心材料技术领域。
背景技术
微波铁氧体器件在微波技术中占有重要地位，在航空航天、卫星通信、电子对抗、移动通信及医疗等领域中有着广泛的应用。作为微波铁氧体器件的核心，微波铁氧体材料应用于环行器/隔离器、移相器、铁氧体开关等器件，在微波系统中实现着对微波传输的隔离、通路选择、移相、极化状态控制、开关、调制、倍频、放大等方面的功能。
微波铁氧体是具有亚铁磁性的金属氧化物。当电磁波/场通过微波铁氧体时，由于受到铁磁共振引起的张量磁导率的影响，电磁波/场的场结构产生变化，在输入端口的主模在中心两侧分别是左旋圆极化波和右旋圆极化波。当铁氧体器件工作时，电磁波会受到张量磁导率的影响而发生偏转。利用微波铁氧体材料的旋磁效应可以制造微波铁氧体器件，如：环行器/隔离器、铁氧体开关、铁氧体移相器等。
根据经验公式：(γ×Ms)/f＝p，其中p值取0.6-0.7，γ表示旋磁比，微波铁氧体材料的饱和磁化强度决定了微波铁氧体器件的应用频段。高频段是通信器件重要的发展趋势，因此研究制造高饱和磁化强度的微波铁氧体材料具有重要的现实意义。同时，在材料化学成分配比固定的情况下，通过调节工艺参数来改变饱和磁化强度也为具有重要的实际操作意义。
微波铁氧体材料根据剩磁比(Mr/Ms)的不同可以进一步分为微波旋磁材料和微波矩磁材料，其中微波矩磁材料的剩磁比≥0.85。微波铁氧体材料的剩磁比决定了其应用范围，一般而言，微波旋磁材料应用于环行器/隔离器，微波矩磁铁氧体应用于铁氧体开关。
微波矩磁铁氧体材料的矫顽力决定其切换速度，矫顽力越小，切换越灵敏。微波矩磁铁氧体材料的损耗角正切(介电常数虚部)决定了微波铁氧体器件的损耗，损耗角正切越小，损耗越小。因此，制备低矫顽力、低损耗角正切的微波矩磁铁氧体材料具有重要意义。
发明内容
本发明的技术解决问题是：克服现有技术的不足，提供了一种可用于铁氧体器件的微波铁氧体材料及制备方法，该材料具有本发明制的微波铁氧体材料具有高剩磁比(Ms/Mr≥0.9)，低矫顽力(Hc≤2Oe)，低损耗(损耗角正切tanδ≤1×10-3)等特点。
本发明的技术解决方案是：
一种可用于铁氧体器件的微波铁氧体材料，所述微波铁氧体材料化学成分为：
LixZnyMnzBiuNivDywFe2.26±γO4±δ或者
LixZnyMnzBiuNivTbwFe2.26±γO4±δ，
其中：x＝0.35-0.37，y＝0.27-0.29，z＝0.045-0.055，u＝0.004-0.006，v＝0-0.03，w＝0-0.03，γ＝0-0.0113，δ＝0-0.02。
进一步的，本发明还提出可用于铁氧体器件的微波铁氧体材料的制备方法，步骤如下：
(1)进行配料，根据微波铁氧体材料化学成分，按照化学成分摩尔比换算为质量比进行称量，配料比如下：
Figure BDA0002751342460000021
称量后将粉料充分混合；
进一步的，微波铁氧体材料化学成分为LixZnyMnzBiuNivDywFe2.26±γO4±δ时，配料中选用Dy2O3；微波铁氧体材料化学成分为LixZnyMnzBiuNivTbwFe2.26±γO4±δ时，配料中选用Tb2O3。
(2)预球磨：将称量混合后的粉料、介质溶剂、球磨珠装入球磨罐进行球磨；
进一步的，所用的介质溶剂为非极性溶剂，优选乙醇或正庚烷；粉料、介质溶剂、球磨珠的质量比为1:x:y，其中x＝1.8-2.6，y＝1.8-3.0；球磨罐选用玛瑙罐或不锈钢罐，球磨珠材料与球磨罐相同。
进一步的，预球磨强度为20-60r/min，优选30r/min，球磨时间11-13h；
(3)烘干：将步骤(2)预球磨得到的的配料进行烘干；
烘干温度120-190℃，优选130℃，峰值温度不高于200℃。
(4)一次过筛：将步骤(3)烘干得到的配料过40-80目筛；
(5)预烧结：将步骤(4)一次过筛后得到的配料进行预烧结；
进一步的，预烧结条件为：2小时内均匀升温至355℃，再2小时内由355℃升温至540℃，再3小时内由540℃升温至900℃，900℃保温5小时；断电后随炉冷却。
(6)二次球磨：将步骤(5)预烧结得到的粉料装入球磨罐进行球磨；
二次球磨强度为80-100r/min，优选90r/min，球磨时间29-31h。
(7)烘干：将步骤(6)二次球磨得到的的配料进行烘干；烘干温度120-190℃，优选130℃，峰值温度不高于200℃。
(8)造粒：在步骤(7)烘干得到的粉料中以11-17％的比例加入聚乙烯醇的水溶液，聚乙烯醇的水溶液浓度为质量比8-9％，充分混合研磨后过80目筛；
(9)压型：将步骤(8)造粒得到的粉料放入相应模具中进行压型，得到生坯；压型时，压力范围为：10-35MPa，优选采用20MPa。
(10)二次烧结：将步骤(9)压型得到生坯放入电炉进行烧结。
二次烧结条件为：阶段①：7小时内均匀升温至380℃，再2小时内由380℃升温至580℃，再6小时内580℃升温至1060℃；阶段②：1060℃保温t小时，t＝8-30h，保温时间t后断电后随炉冷却。
改变保温时间t确定铁氧体材料的饱和磁化强度，当t＝8h时，饱和磁化强度为4300Gs，t＝10h时，饱和磁化强度为4400Gs，t＝24h时，饱和磁化强度为4700Gs，t＝28h时，饱和磁化强度为5000Gs，t≥30h时，饱和磁化强度为5100Gs。
本发明与现有技术相比的有益效果是：
(1)本发明制备的微波铁氧体材料具有高剩磁比、低矫顽力、低损耗以及高温度稳定性等特点，可以用于制造高性能的环行器/隔离器、铁氧体开关等微波无源器件。
(2)与传统锂铁铁氧体材料相比，利用本发明得到的微波铁氧体材料主要性能对比如下：
Figure BDA0002751342460000041
具体实施方式
本发明提出了一种可用于铁氧体器件的微波铁氧体材料，所述微波铁氧体材料化学成分为：
LixZnyMnzBiuNivDywFe2.26±γO4±δ或者
LixZnyMnzBiuNivTbwFe2.26±γO4±δ，
其中：x＝0.35-0.37，y＝0.27-0.29，z＝0.045-0.055，u＝0.004-0.006，v＝0-0.03，w＝0-0.03，γ＝0-0.0113，δ＝0-0.02。
进一步的，本发明还提出可用于铁氧体器件的微波铁氧体材料的制备方法，步骤如下：
(1)进行配料，根据微波铁氧体材料化学成分，按照化学成分摩尔比换算为质量比进行称量，配料比如下：
Figure BDA0002751342460000051
称量后将粉料充分混合；
进一步的，微波铁氧体材料化学成分为LixZnyMnzBiuNivDywFe2.26±γO4±δ时，配料中选用Dy2O3；微波铁氧体材料化学成分为LixZnyMnzBiuNivTbwFe2.26±γO4±δ时，配料中选用Tb2O3。
(2)预球磨：将称量混合后的粉料、介质溶剂、球磨珠装入球磨罐进行球磨；
由于在极性溶剂(如：乙醇)中，Li2CO3与其他粉料的溶解度差异较大，会导致混合不充分的情况，因此本发明所用的介质溶剂为非极性溶剂，优选乙醇或正庚烷；粉料、介质溶剂、球磨珠的质量比为1:x:y，其中x＝1.8-2.6，y＝1.8-3.0；球磨罐选用玛瑙罐或不锈钢罐，球磨珠材料与球磨罐相同。
进一步的，预球磨强度为20-60r/min，优选30r/min，球磨时间11-13h；
(3)烘干：将步骤(2)预球磨得到的的配料进行烘干；
烘干温度120-190℃，优选130℃，峰值温度不高于200℃。
(4)一次过筛：将步骤(3)烘干得到的配料过40-80目筛；
(5)预烧结：将步骤(4)一次过筛后得到的配料进行预烧结；
进一步的，预烧结条件为：2小时内均匀升温至355℃，再2小时内由355℃升温至540℃，再3小时内由540℃升温至900℃，900℃保温5小时；断电后随炉冷却。
(6)二次球磨：将步骤(5)预烧结得到的粉料装入球磨罐进行球磨；粉料、介质溶剂、球磨珠的质量比为1:x:y，其中x＝1.8-2.6，y＝1.8-3.0；球磨罐选用玛瑙罐或不锈钢罐，球磨珠材料类型需要与球磨罐相同。二次球磨强度为80-100r/min，优选90r/min，球磨时间29-31h
(7)烘干：将步骤(6)二次球磨得到的的配料进行烘干；烘干温度120-190℃，优选130℃，峰值温度不高于200℃。
(8)造粒：在步骤(7)烘干得到的粉料中以11-17％的比例加入聚乙烯醇的水溶液，聚乙烯醇的水溶液浓度为8-9％(质量比)，充分混合研磨后过80目筛；
(9)压型：将步骤(8)造粒得到的粉料放入相应模具中进行压型，得到生坯；压型时，压力范围为：10-35MPa，优选采用20MPa。
(10)二次烧结：将步骤(9)压型得到生坯放入电炉进行烧结。
二次烧结条件为：阶段①：7小时内均匀升温至380℃，再2小时内由380℃升温至580℃，再6小时内580℃升温至1060℃；阶段②：1060℃保温t小时，t＝8-30h，保温时间t后断电后随炉冷却。
改变保温时间t确定铁氧体材料的饱和磁化强度，当t＝8h时，饱和磁化强度为4300Gs，t＝10h时，饱和磁化强度为4400Gs，t＝24h时，饱和磁化强度为4700Gs，t＝28h时，饱和磁化强度为5000Gs，t≥30h时，饱和磁化强度为5100Gs。
实施例一：
化学成分：Li0.36Zn0.28Mn0.05Bi0.005Fe2.26O4该成分微波铁氧体材料的制备方法如下：
(1)进行配料，根据微波铁氧体材料化学成分，按照化学成分摩尔比换算为质量比进行称量，相关原材料质量如下：
Figure BDA0002751342460000071
称量后将粉料充分混合。
(2)预球磨：将称量混合后的粉料、无水乙醇、不锈钢球磨珠装入不锈钢球磨罐进行球磨，其中：粉料、无水乙醇、球磨珠的质量比为1:2:2.5。预球磨强度(转速)为30r/min，球磨时间12h。
(3)烘干：将步骤(2)预球磨得到的配料在130℃条件下进行烘干。
(4)一次过筛：将步骤(3)烘干得到的配料过70目筛；
(5)预烧结：将步骤(4)一次过筛后得到的配料进行预烧结。预烧结条件为：2小时内均匀升温至355℃，再2小时内由355℃升温至540℃，再3小时内由540℃升温至900℃，900℃保温5小时；断电后随炉冷却。
(6)二次球磨：将步骤(5)预烧结得到的粉料装入不锈钢球磨罐进行球磨；粉料、无水乙醇、不锈钢球磨珠的质量比为1:2:2.5。二次球磨强度(转速)为90r/min，球磨时间30h。
(7)烘干：将步骤(6)二次球磨得到的配料在130℃条件下进行烘干。
(8)造粒：在步骤(7)烘干得到的粉料中以14％的比例加入聚乙烯醇的水溶液，聚乙烯醇的水溶液浓度为8.5％(质量比)，充分混合研磨后过80目筛。
(9)压型：将步骤(8)造粒得到的粉料放入模具中进行压型，所用压力为20MPa，得到生坯。
(10)二次烧结：将步骤(9)压型得到生坯放入电炉进行烧结。
二次烧结条件为：阶段①：7小时内均匀升温至380℃，再2小时内由380℃升温至580℃，再6小时内580℃升温至1060℃；阶段②：将生坯分为两组，分别在1060℃条件下保温24h以及28h。断电后随炉冷却。
得到的微波铁氧体材料性能测试结果如下：
Figure BDA0002751342460000081
实施例二：
化学成分：Li0.36Zn0.28Mn0.05Bi0.005Ni0.001Dy0.002Fe2.26O3.98该成分微波铁氧体材料的制备方法如下：
(1)进行配料，根据微波铁氧体材料化学成分，按照化学成分摩尔比换算为质量比进行称量，相关原材料质量如下：
Figure BDA0002751342460000082
称量后将粉料充分混合。
(2)预球磨：将称量混合后的粉料、无水乙醇、不锈钢球磨珠装入不锈钢球磨罐进行球磨，其中：粉料、无水乙醇、球磨珠的质量比为1:2:2.5。预球磨强度(转速)为30r/min，球磨时间12h。
(3)烘干：将步骤(2)预球磨得到的配料在130℃条件下进行烘干。
(4)一次过筛：将步骤(3)烘干得到的配料过70目筛；
(5)预烧结：将步骤(4)一次过筛后得到的配料进行预烧结。预烧结条件为：2小时内均匀升温至355℃，再2小时内由355℃升温至540℃，再3小时内由540℃升温至900℃，900℃保温5小时；断电后随炉冷却。
(6)二次球磨：将步骤(5)预烧结得到的粉料装入不锈钢球磨罐进行球磨；粉料、无水乙醇、不锈钢球磨珠的质量比为1:2:2.5。二次球磨强度(转速)为90r/min，球磨时间30h。
(7)烘干：将步骤(6)二次球磨得到的配料在130℃条件下进行烘干。
(8)造粒：在步骤(7)烘干得到的粉料中以14％的比例加入聚乙烯醇的水溶液，聚乙烯醇的水溶液浓度为8.5％(质量比)，充分混合研磨后过80目筛。
(9)压型：将步骤(8)造粒得到的粉料放入模具中进行压型，所用压力为20MPa，得到生坯。
(10)二次烧结：将步骤(9)压型得到生坯放入电炉进行烧结。
二次烧结条件为：阶段①：7小时内均匀升温至380℃，再2小时内由380℃升温至580℃，再6小时内580℃升温至1060℃；阶段②：在1060℃条件下保温30h。断电后随炉冷却。
得到的微波铁氧体材料性能测试结果如下：
Figure BDA0002751342460000091
实施例三：
化学成分：Li0.36Zn0.28Mn0.05Bi0.005Ni0.001Tb0.002Fe2.26O3.98该成分微波铁氧体材料的制备方法如下：
(1)进行配料，根据微波铁氧体材料化学成分，按照化学成分摩尔比换算为质量比进行称量，相关原材料质量如下：
Figure BDA0002751342460000101
称量后将粉料充分混合。
(2)预球磨：将称量混合后的粉料、无水乙醇、不锈钢球磨珠装入不锈钢球磨罐进行球磨，其中：粉料、无水乙醇、球磨珠的质量比为1:2:2.5。预球磨强度(转速)为30r/min，球磨时间12h。
(3)烘干：将步骤(2)预球磨得到的配料在130℃条件下进行烘干。
(4)一次过筛：将步骤(3)烘干得到的配料过70目筛；
(5)预烧结：将步骤(4)一次过筛后得到的配料进行预烧结。预烧结条件为：2小时内均匀升温至355℃，再2小时内由355℃升温至540℃，再3小时内由540℃升温至900℃，900℃保温5小时；断电后随炉冷却。
(6)二次球磨：将步骤(5)预烧结得到的粉料装入不锈钢球磨罐进行球磨；粉料、无水乙醇、不锈钢球磨珠的质量比为1:2:2.5。二次球磨强度(转速)为90r/min，球磨时间30h。
(7)烘干：将步骤(6)二次球磨得到的配料在130℃条件下进行烘干。
(8)造粒：在步骤(7)烘干得到的粉料中以14％的比例加入聚乙烯醇的水溶液，聚乙烯醇的水溶液浓度为8.5％(质量比)，充分混合研磨后过80目筛。
(9)压型：将步骤(8)造粒得到的粉料放入模具中进行压型，所用压力为20MPa，得到生坯。
(10)二次烧结：将步骤(9)压型得到生坯放入电炉进行烧结。
二次烧结条件为：阶段①：7小时内均匀升温至380℃，再2小时内由380℃升温至580℃，再6小时内580℃升温至1060℃；阶段②：在1060℃条件下保温30h。断电后随炉冷却。
得到的微波铁氧体材料性能测试结果如下：
Figure BDA0002751342460000111
通过上述实施例可以看出，本发明制备的微波铁氧体材料具有高剩磁比(Ms/Mr≥0.9)，低矫顽力(Hc≤2Oe)，低损耗(损耗角正切tanδ≤1×10-3)等特点。本发明给出了可以用于微波铁氧体器件的高性能微波铁氧体材料。通过控制原材料配比，控制烧结、成相、回火温度，控制晶粒大小、生坯压力参数实现了微波铁氧体材料的晶粒细化与性能优化。成功制造出有高剩磁比、低矫顽力、低损耗以及高温度稳定性的微波铁氧体材料。本发明同时还实现了在微波铁氧体材料化学成分配比固定的情况下，通过调节工艺参数来改变饱和磁化强度的工艺控制，对实际工艺操作具有重要意义。

Claims (10)

1.一种可用于铁氧体器件的微波铁氧体材料，其特征在于，所述微波铁氧体材料化学成分为：
LixZnyMnzBiuNivDywFe2.26±γO4±δ或者
LixZnyMnzBiuNivTbwFe2.26±γO4±δ，
其中：x＝0.35-0.37，y＝0.27-0.29，z＝0.045-0.055，u＝0.004-0.006，
v＝0-0.03，w＝0-0.03，γ＝0-0.0113，δ＝0-0.02。
2.一种如权利要求1所述的可用于铁氧体器件的微波铁氧体材料的制备方法，其特征在于步骤如下：
(1)进行配料，根据微波铁氧体材料化学成分，按照化学成分摩尔比换算为质量比进行称量，配料比如下：
Figure FDA0002751342450000011
称量后将粉料充分混合；
(2)预球磨：将称量混合后的粉料、介质溶剂、球磨珠装入球磨罐进行球磨；
(3)烘干：将步骤(2)预球磨得到的的配料进行烘干；
(4)一次过筛：将步骤(3)烘干得到的配料过40-80目筛；
(5)预烧结：将步骤(4)一次过筛后得到的配料进行预烧结；
(6)二次球磨：将步骤(5)预烧结得到的粉料装入球磨罐进行球磨；
(7)烘干：将步骤(6)二次球磨得到的的配料进行烘干；
(8)造粒：在步骤(7)烘干得到的粉料中以11-17％的比例加入聚乙烯醇的水溶液，聚乙烯醇的水溶液浓度为质量比8-9％，充分混合研磨后过80目筛；
(9)压型：将步骤(8)造粒得到的粉料放入相应模具中进行压型，得到生坯；
(10)二次烧结：将步骤(9)压型得到生坯放入电炉进行烧结。
3.根据权利要求2所述的可用于铁氧体器件的微波铁氧体材料的制备方法，其特征在于：微波铁氧体材料化学成分为LixZnyMnzBiuNivDywFe2.26±γO4±δ时，配料中选用Dy2O3；微波铁氧体材料化学成分为LixZnyMnzBiuNivTbwFe2.26±γO4±δ时，配料中选用Tb2O3。
4.根据权利要求2所述的可用于铁氧体器件的微波铁氧体材料的制备方法，其特征在于：步骤(2)所用的介质溶剂为非极性溶剂，优选乙醇或正庚烷；粉料、介质溶剂、球磨珠的质量比为1:x:y，其中x＝1.8-2.6，y＝1.8-3.0；球磨罐选用玛瑙罐或不锈钢罐，球磨珠材料与球磨罐相同。
5.根据权利要求2所述的可用于铁氧体器件的微波铁氧体材料的制备方法，其特征在于：步骤(2)预球磨强度为20-60r/min，优选30r/min，球磨时间11-13h；步骤(6)二次球磨强度为80-100r/min，优选90r/min，球磨时间29-31h。
6.根据权利要求2所述的可用于铁氧体器件的微波铁氧体材料的制备方法，其特征在于：步骤(3)和步骤(7)进行烘干时，烘干温度120-190℃，优选130℃，峰值温度不高于200℃。
7.根据权利要求2所述的可用于铁氧体器件的微波铁氧体材料的制备方法，其特征在于：步骤(5)预烧结条件为：2小时内均匀升温至355℃，再2小时内由355℃升温至540℃，再3小时内由540℃升温至900℃，900℃保温5小时；断电后随炉冷却。
8.根据权利要求2所述的可用于铁氧体器件的微波铁氧体材料的制备方法，其特征在于：压型时，压力范围为：10-35MPa，优选采用20MPa。
9.根据权利要求2所述的可用于铁氧体器件的微波铁氧体材料的制备方法，其特征在于：步骤(10)二次烧结条件为：阶段①：7小时内均匀升温至380℃，再2小时内由380℃升温至580℃，再6小时内580℃升温至1060℃；阶段②：1060℃保温t小时，t＝8-30h，保温时间t后断电后随炉冷却。
10.根据权利要求9所述的可用于铁氧体器件的微波铁氧体材料的制备方法，其特征在于：改变保温时间t确定铁氧体材料的饱和磁化强度，当t＝8h时，饱和磁化强度为4300Gs，t＝10h时，饱和磁化强度为4400Gs，t＝24h时，饱和磁化强度为4700Gs，t＝28h时，饱和磁化强度为5000Gs，t≥30h时，饱和磁化强度为5100Gs。
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