CN108424134B - 一种石榴石型固溶体磁介电功能介质陶瓷材料及制备方法 - Google Patents
一种石榴石型固溶体磁介电功能介质陶瓷材料及制备方法 Download PDFInfo
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Abstract
本发明公开了一种石榴石型固溶体磁介电功能介质陶瓷材料及制备方法，以石榴石型铁氧体陶瓷Y3Fe5O12和石榴石型微波介质陶瓷Ca3LiMgV3O12为原料，通过调节铁氧体‑微波介质陶瓷的原料配比一次性合成固溶体，并得到了一系列兼具磁性、优良介电性能以及微波性能的磁介电功能介质陶瓷材料，其具体结构表达通式为：xY3Fe5O12‑(1‑x)Ca3LiMgV3O12，其中0.01≤x≤0.99。而且本发明陶瓷材料的烧结温度为1000～1450℃，化学组成及制备工艺简单，物相单一。
Description
技术领域
本发明属于电子陶瓷技术领域，具体涉及一种石榴石型固溶体磁介电功能介质陶瓷材料及制备方法。
背景技术
信息产业的迅猛发展要求通信、雷达、导航、电子对抗等电子装备具有多功能、小型化、高机动性能等特性，这就要求相关的电子材料具有多功能性，如磁电性能、磁光性能、柔性压电等，其中磁电特性备受关注。众所周知，在介质材料中传输的电磁波的波长与介质的介电常数和磁导率的乘积之平方根成反比，因此采用具有较高介电常数和较高磁导率的磁电复合材料可以在不改变器件和天线设计的情况下，极大地减小器件和天线的尺寸。此外，低损耗磁介电复合材料可以应用于制作LC振荡器、滤波器、变频器等器件，具有磁电耦合效应的磁电复合材料还可应用于换能器、执行器和传感器等方面。
微波介质陶瓷主要用于制作谐振器、滤波器、介质天线、介质导波回路等微波元器件，可用于移动通讯、卫星通讯和雷达等方面。随着科学技术日新月异的发展，通信信息量的迅猛增加，以及人们对无线通信的要求，使用卫星通讯和卫星直播电视等微波通信系统己成为当前通信技术发展的必然趋势。随着电子信息技术不断向高频化和数字化方向发展，对元器件的小型化，集成化以至模块化的要求也越来越迫切。
同时具有较高介电常数和较高磁导率的单相材料非常稀少，传统的单相铁氧体陶瓷，如镍锌、锰锌铁氧体，虽然在低频下具有较高的介电常数和磁导率，但是低频介电损耗也非常大，并且在微波频率范围内，它们的介电损耗仍然较高，难以在宽频范围内得到广泛的应用。如今备受关注的磁电复合材料绝大部分是将磁性材料和非磁性介电材料进行两相或多相复合，以获得具有磁介电功能的复合材料。
对于陶瓷基两相共烧材料而言，它们通常能在低频下表现出较高的介电常数和较高的磁导率，但是这类材料的高损耗特点限制了它在高频范围下的应用。对于聚合物基两相复合材料而言，由于受到样品机械强度、加工工艺等条件的制约，磁性相铁氧体陶瓷粉末的体积分数通常比较低(不超过50％)，从而造成这种复合材料的低磁导率和低介电常数的特点。此外，聚合物基复合材料由于受到低熔点聚合物基体材料的限制，使用温度通常在200℃以内。
综上所述，随着多功能介质材料广泛应用于LC振荡器、谐振器、滤波器、变频器等器件以及介质波导、介质基板、介质超材料等领域，为了满足器件小型化以及集成化的发展需要，低损耗磁介电功能介质材料以其独特的性能优势，逐渐成为器件开发制造的关注热点。
相对于复相材料而言，单相材料的制备工艺较为简单，避免了两相共烧匹配的要求。目前尚无一种兼具低频高介电常数和高磁导率以及微波小损耗的磁介电功能介质陶瓷材料，以满足信息和通讯技术高频化和小型化发展的需求。因此，寻找、制备与研究中高介电常数(εr>10)、较高的磁导率(μr>5)、低损耗(Qf>5000GHz)、近零谐振频率温度系数(TCF＝0ppm/℃)、低成本(不含或者含有少量贵重金属)、环保(至少无铅，尽量不含或者含有较少有毒原材料)的新型磁介电功能介质陶瓷材料成为了当前研究的热门方向。
发明内容
本发明的一个目的是提供一种石榴石型固溶体磁介电功能介质陶瓷材料，解决现有磁介电功能介质陶瓷材料无法兼具低频高介电常数和高磁导率以及微波小损耗的问题。
本发明的另一个目的是提供一种石榴石型固溶体磁介电功能介质陶瓷材料的制备方法。
本发明所采用的一个技术方案是，一种石榴石型固溶体磁介电功能介质陶瓷材料，结构表达通式为：xY3Fe5O12-(1-x)Ca3LiMgV3O12，其中0.01≤x≤0.99。
本发明以石榴石型高磁导率铁氧体材料Y3Fe5O12和石榴石型微波介质材料Ca3LiMgV3O12作为主元，使得二者生成以任意比例互溶的固溶体，同时保留了铁氧体的磁学性能以及微波介质材料的微波介电性能。本发明根据晶体化学原理和电介质理论，以A3B5O12这种典型的石榴石组成为基础，使用Y3+、Ca2+中的一种或几种离子的组合来占据A位，使用Fe3+、Mg2+，Li+，V5+中的一种或几种离子占据B位，在没有添加任何烧结助剂的前提下，可以在1000℃～1400℃的温度范围内烧结出致密的且同时具有较高的磁导率、较高介电常数以及优良微波介电性能的新型功能陶瓷。
上述石榴石型固溶体磁介电功能介质陶瓷材料的制备方法，采用固相反应烧结的方法来制备上述陶瓷材料。首先按照配方选取初始氧化物以及取代物(碳酸盐)，然后通过一次球磨使得氧化物混合均匀，接着通过预烧结过程使得氧化物进行初步的反应，再通过二次球磨细化反应物的颗粒尺寸，最后通过烧结过程得到所需要的陶瓷样品。
具体包括以下步骤：
1)将原料Y2O3、Fe2O3、CaO、MgO、Li2CO3、V2O5按通式xY3Fe5O12-(1-x)Ca3LiMgV3O12配制，其中0.01≤x≤0.99；
2)将配制后的原料混合，加入溶剂后球磨，然后烘干、压块、预烧；
3)预烧后进行二次球磨，球磨后烘干，加入粘结剂后造粒，得瓷料，将瓷料压制成型后烧结，得到所述陶瓷材料。
其特点还在于：
步骤2)中预烧温度为800～1100℃，预烧的保温时间为4～6小时。
步骤3)中烧结温度为1100～1150℃，烧结时间为2～4小时。
步骤2)中球磨后过200目筛后，用过筛的粉体压块；步骤3)中造粒后过依次60目与120目筛，以过筛的粉体作为瓷料。
步骤2)中溶剂为无水乙醇或去离子水，其添加量等于原料总质量的80-120％。
步骤3)中粘结剂为5％聚乙烯醇水溶液，其添加量为二次球磨粉体总质量的8～15％。
步骤2)中球磨4～8小时，步骤3)球磨5～6小时。
本发明的另一个技术方案是，一种石榴石型固溶体磁介电功能介质陶瓷材料的制备方法，其特征在于，包括以下步骤：将原料粉末按陶瓷材料通式配制，将配制后的原料混合，加入溶剂后球磨，然后烘干、压块、预烧；预烧后进行二次球磨，球磨后烘干，加入粘结剂后造粒，得瓷料，将瓷料压制成型后烧结，得到所述陶瓷材料。
将本发明的xY3Fe5O12-(1-x)Ca3LiMgV3O12介质陶瓷材料与传统的磁介电功能材料进行比较。传统磁介电功能材料大多是通过固相法工艺，将具有磁性与介电性能的不同材料进行复合烧结而成。以文献《Low-Temperature Sintering Li2MoO4/Ni0.5Zn0.5Fe2O4Magneto-Dielectric Composites for High-Frequency Application》(L.He,Zhou D.,Yang H.,Niu Y.,Xiang F.,Wang H.Journal of the American CeramicSociety 97,2552-2556(2014))中记载的xLi2MoO4-(1-x)Ni0.5Zn0.5Fe2O4磁介电复合材料为例。该材料选择微波介质陶瓷Li2MoO4和铁氧体Ni0.5Zn0.5Fe2O4复合共烧，其方法主要考虑两种功能相材料烧结中的物相共存即可，复合后的材料兼具原功能相材料的磁性与介电性能，但是受到第二相影响，复合材料的性能衰减较严重，尤其是磁介电损耗难以控制。该材料中x＝0.5为性能最优样品，在10MHz-1GHz范围内，介电常数7.14-6.84，介电损耗0.09-0.02，磁导率5.23-3.30，磁损耗0.06-0.65。与本发明陶瓷材料相比，本发明陶瓷材料低频相对磁导率为5～40(≤100MHz)，低频介电常数为10～20(≤100MHz)，具有较低的低频介电损耗(tanδ<10-2，100MHz)，微波介电常数为10～20(7GHz)，拥有良好的微波性能，品质因数Qf＝1000～20000GHz，明显优于传统材料。而且，尽管该文献中微波介质陶瓷Li2MoO4本身性能优异，其体积分数也高达50％，但是复合后该材料的介电损耗仍然较高，其微波介电性能无法测出。Ni0.5Zn0.5Fe2O4磁导率可达200左右，但是复合材料的磁导率只有5。
本发明所制备的石榴石型固溶体磁介电功能介质陶瓷材料具有以下有益效果：具有更高的介电常数、更高的磁导率以及更低的磁电损耗。另外该陶瓷材料的烧结温度为1000～1450℃，化学组成及制备工艺简单，物相单一，可以作为射频多层陶瓷电容器、片式微波介质谐振器或滤波器、陶瓷天线、多芯片组件(MCM)等介质材料使用。
附图说明
图1是本发明中实施例1材料样品的微观结构测试图片；
图2是本发明中实施例1材料样品的EDS能谱测试图片；
图3是本发明中实施例1材料样品的XRD测试结果；
图4是本发明中实施例1材料样品的不同温度-密度烧结曲线测试结果。
具体实施方式
下面结合附图和具体实施方式对本发明作进一步的详细说明，但本发明并不限于这些实施方式。
实施例1
制备0.5Y3Fe5O12-0.5Ca3LiMgV3O12磁介电功能介质陶瓷材料。
将分析纯的原料Y2O3、Fe2O3、CaO、MgO、Li2CO3、V2O5，按配方0.5Y3Fe5O12-0.5Ca3LiMgV3O12配制。将配制后的化学原料混合，然后放入尼龙罐中，向尼龙罐中加入与原料等重量的无水乙醇，球磨4小时，充分混合磨细，球磨后取出，然后于100～200℃快速烘干，烘干后过200目筛，然后预压成块体；将块体预烧后得到样品烧块，预烧的条件为1100℃保温4小时；将样品烧块粉碎后球磨5～6小时，充分混合磨细，球磨后于100～200℃烘干，烘干后加入粉体总质量15％的粘合剂，粘合剂采用5％聚乙烯醇水溶液，然后造粒，再依次用60目与120目筛网双层过筛，得到造粒瓷料粉末。将造粒瓷料粉末按需要压制成型，即通过液压机(YE-600济南试验机厂)压制成块体，所用压力大小为150Mpa/m2，然后在1100℃下烧结2小时成瓷，即可得到即可得到0.5Y3Fe5O12-0.5Ca3LiMgV3O12磁介电功能介质陶瓷材料。
该组陶瓷材料的微观结构如图1所示，经过1100℃/2小时烧结后，陶瓷微观结构致密，晶粒大小均匀，图2能谱分析显示，配方组分中所包含的相关元素在陶瓷材料内均匀分布，且元素比例与配方设计比例一致。
该组陶瓷材料的XRD测试数据如图3所示，结果显示，石榴石相Y3Fe5O12与Ca3LiMgV3O12完美固溶，生成的固溶体0.5Y3Fe5O12-0.5Ca3LiMgV3O12材料物相单一，且与Y3Fe5O12和Ca3LiMgV3O12具有相同的晶体结构，属于la-3d点群。图4为该材料的烧结温度-密度测试曲线，可以看出1125℃陶瓷密度达最大值，由于烧结温度对微波介电性能影响较大，因此为了保证材料的微波介电性能，烧结温度取1100℃。
该组陶瓷材料的性能达到如下指标：在1MHz～100MHz频率范围内具有：相对磁导率μr＝10，相对介电常数εr＝15，介电损耗tanδ＝0.31～0.02，室温饱和磁化强度Ms＝10(emu/g)，微波下的介电性能εr＝11.6(7.0GHz)，品质因子Q＝303，Qf＝2820GHz。
实施例2
制备0.35Y3Fe5O12-0.65Ca3LiMgV3O12磁介电功能介质陶瓷材料。
将分析纯的原料Y2O3、Fe2O3、CaO、MgO、Li2CO3、V2O5，按配方0.35Y3Fe5O12-0.65Ca3LiMgV3O12配制。将配制后的化学原料混合，然后放入尼龙罐中，向尼龙罐中加入原料重量80％的去离子水，球磨4小时，充分混合磨细，球磨后取出，然后于100～200℃快速烘干，烘干后过200目筛，然后预压成块体；将块体预烧后得到样品烧块，预烧的条件为800℃保温6小时；将样品烧块粉碎后球磨5～6小时，充分混合磨细，球磨后于100～200℃烘干，烘干后加入粉体总质量15％的粘合剂，粘合剂采用5％聚乙烯醇水溶液，然后造粒，再依次用60目与120目筛网双层过筛，得到造粒瓷料粉末。将造粒瓷料粉末按需要压制成型，即通过液压机(YE-600济南试验机厂)压制成块体，所用压力大小为180Mpa/m2，然后在1100℃下烧结4小时成瓷，即可得到即可得到0.35Y3Fe5O12-0.65Ca3LiMgV3O12磁介电功能介质陶瓷材料。
该组陶瓷材料的性能达到如下指标：在1MHz～300MHz频率范围内具有：相对磁导率μr＝6，相对介电常数εr＝11.2，介电损耗tanδ＝0.23～0.008，室温饱和磁化强度Ms＝5(emu/g)，微波下的介电性能εr＝9.3(8.0GHz)，品质因子Q＝2315，Qf＝18520GHz。
实施例3
制备0.7Y3Fe5O12-0.3Ca3LiMgV3O12磁介电功能介质陶瓷材料。
将分析纯的原料Y2O3、Fe2O3、CaO、MgO、Li2CO3、V2O5，按配方0.7Y3Fe5O12-0.3Ca3LiMgV3O12配制。将配制后的化学原料混合，然后放入尼龙罐中，向尼龙罐中加入与原料重量120％的去离子水，球磨4小时，充分混合磨细，球磨后取出，然后于100～200℃快速烘干，烘干后过200目筛，然后预压成块体；将块体预烧后得到样品烧块，预烧的条件为1000℃保温4小时；将样品烧块粉碎后球磨5～6小时，充分混合磨细，球磨后于100～200℃烘干，烘干后加入粉体总质量12％的粘合剂，粘合剂采用5％聚乙烯醇水溶液，然后造粒，再依次用60目与120目筛网双层过筛，得到造粒瓷料粉末。将造粒瓷料粉末按需要压制成型，即通过液压机(YE-600济南试验机厂)压制成块体，所用压力大小为160Mpa/m2，然后在1150℃下烧结3小时成瓷，即可得到即可得到0.7Y3Fe5O12-0.3Ca3LiMgV3O12磁介电功能介质陶瓷材料。
该组陶瓷材料的性能达到如下指标：在1MHz～100MHz频率范围内具有：相对磁导率μr＝15，相对介电常数εr＝12.2，介电损耗tanδ＝0.44～0.09，室温饱和磁化强度Ms＝20(emu/g)，微波下的介电性能εr＝9.3(7.4GHz)，品质因子Q＝231，Qf＝1710GHz。
Claims (8)
1.一种石榴石型固溶体磁介电功能介质陶瓷材料，其特征在于，结构表达通式为：xY3Fe5O12-(1-x)Ca3LiMgV3O12，其中0.01≤x≤0.99。
2.根据权利要求1所述的石榴石型固溶体磁介电功能介质陶瓷材料，其特征在于，采用固相反应烧结法制备得到，制备方法包括以下步骤：
1)由原料Y2O3、Fe2O3、CaO、MgO、Li2CO3、V2O5按通式xY3Fe5O12-(1-x)Ca3LiMgV3O12配制，其中0.01≤x≤0.99；
2)将配制后的原料混合，加入溶剂后球磨，然后烘干、压块、预烧；
3)预烧后进行二次球磨，球磨后烘干，加入粘结剂后造粒，得瓷料，将瓷料压制成型后烧结，得到所述陶瓷材料。
3.根据权利要求2所述的石榴石型固溶体磁介电功能介质陶瓷材料，其特征在于，步骤2)中所述预烧温度为800～1100℃，预烧的保温时间为4～6小时。
4.根据权利要求2所述的石榴石型固溶体磁介电功能介质陶瓷材料，其特征在于，步骤3)中所述烧结温度为1100～1150℃，烧结时间为2～4小时。
5.根据权利要求2所述的石榴石型固溶体磁介电功能介质陶瓷材料，其特征在于，步骤2)中所述球磨后过200目筛后，用过筛的粉体压块；步骤3)中造粒后过依次60目与120目筛，以过筛的粉体作为瓷料。
6.根据权利要求2所述的石榴石型固溶体磁介电功能介质陶瓷材料，其特征在于，步骤2)中所述溶剂为无水乙醇或去离子水，其添加量等于原料总质量的80-120％。
7.根据权利要求2所述的石榴石型固溶体磁介电功能介质陶瓷材料，其特征在于，步骤3)中所述粘结剂为5％聚乙烯醇水溶液，其添加量为二次球磨粉体总质量的8～15％。
8.根据权利要求2所述的石榴石型固溶体磁介电功能介质陶瓷材料，其特征在于，步骤2)中所述球磨4～8小时，步骤3)球磨5～6小时。
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