CN103172376B - 一种白钨矿型微波介质陶瓷材料及其制备方法 - Google Patents

一种白钨矿型微波介质陶瓷材料及其制备方法 Download PDF

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CN103172376B
CN103172376B CN201310091579.2A CN201310091579A CN103172376B CN 103172376 B CN103172376 B CN 103172376B CN 201310091579 A CN201310091579 A CN 201310091579A CN 103172376 B CN103172376 B CN 103172376B
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dielectric ceramic
microwave dielectric
ceramic materials
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CN103172376A (zh
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李金艳
梁英
周迪
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Huawei Technologies Co Ltd
Xian Jiaotong University
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Huawei Technologies Co Ltd
Xian Jiaotong University
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Abstract

本发明实施例提供了一种白钨矿型微波介质陶瓷材料，微波介电常数高（εr为70～75），微波性能良好（Q×f=9230GHz～10110GHz），谐振频率温度系数可调（τf为-210ppm/°C～+135ppm/°C），以及，该白钨矿型微波介质陶瓷材料不需添加任何助烧剂就可以低温烧结制得，化学组成及制备工艺简单，物相单一。本发明实施例还提供了一种白钨矿型微波介质陶瓷材料的制备方法。

Description

一种白钨矿型微波介质陶瓷材料及其制备方法
技术领域
本发明涉及电子陶瓷及其制备领域，特别是涉及一种白钨矿型微波介质陶瓷材料及其制备。
背景技术
微波介质陶瓷是近三十年来迅速发展起来的新型功能电子陶瓷材料，它具有损耗低、频率温度系数小、介电常数高等特点。用这种微波陶瓷材料可以制成介质谐振器、介质滤波器、双工器、微波介质天线、介质稳频振荡器、介质波导传输线等器件，这些器件广泛应用于移动通信、卫星电视广播通信、雷达、卫星定位导航系统等等众多领域。
应用于现代通讯技术的微波介质陶瓷材料在性能上应满足以下要求：1，系列化的介电常数εr，以满足不同器件对不同频率段的要求；2，尽可能小的介质损耗tanδ或高的品质因子Q值（Q=1/tanδ，常用Q×f来表示，f为工作频率或谐振频率，具有实用价值的材料的Q值至少应该在1000以上，Q×f>5000GHz。例如Al2O3基材料，其Q×f可高达上百万），以保证优良的选频特性；3，趋于零的谐振频率温度系数TCF（τf）（对大部分介质材料来说，其τf取决于介电常数温度系数），从而保证器件良好的温度稳定性；4，低成本环保材料。
为了满足器件小型化以及集成化的发展需要，寻找、制备与研究高介电常数（εr>45，高K值）、低损耗（Q×f>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）的新型微波介质陶瓷始终是当前研究的热点与重点。
发明内容
有鉴于此，本发明实施例第一方面提供了一种白钨矿型微波介质陶瓷材料，微波介电常数高，微波性能良好，谐振频率温度系数可调，以及，该白钨矿型微波介质陶瓷材料不需添加任何助烧剂就可以低温烧结制得，化学组成及制备工艺简单，物相单一。本发明实施例第二方面提供了一种白钨矿型微波介质陶瓷材料的制备方法。
第一方面，本发明实施例提供了一种白钨矿型微波介质陶瓷材料，分子式为：Bi(V1-xInx/3Mo2x/3)MoO4,0.06≤x≤0.12。
其中，一种白钨矿型微波介质陶瓷材料以ABO4这种典型的白钨矿组成为基础，Bi+3离子占据A位，V5+、In3+、Mo6+离子联合占据B位。
优选地，0.08≤x≤0.10。
优选地，所述白钨矿型微波介质陶瓷材料的微波介电常数εr为70～75，品质因数Q×f值为9230GHz～10110GHz，谐振频率温度系数τf为-210ppm/℃～+135ppm/℃。
本发明实施例第一方面提供的白钨矿型微波介质陶瓷材料的微波介电常数高，微波性能良好，谐振频率温度系数可调，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、低温共烧陶瓷系统（LTCC）、陶瓷天线、多芯片组件（MCM）等介质材料使用。
第二方面，本发明实施例提供了一种白钨矿型微波介质陶瓷材料的制备方法，包括以下步骤：
1）将原料V2O5、In2O3、MoO3和Bi2O3按通式Bi(V1-xInx/3Mo2x/3)MoO4中的化学计量比进行配料，0.06≤x≤0.12；
2）将步骤1）中的配料混合，球磨3～6个小时，在100℃～200℃下烘干，过筛后压制得块状体；
3）将块状体经650℃～750℃预烧，并保温4～6小时，制得样品烧块；
4）将样品烧块粉碎，并经过5～6个小时的二次球磨，在100℃～200℃下烘干、造粒，造粒后过筛，制得瓷料粉末；
5）将瓷料粉末压制成型，在780℃～840℃下烧结2～3个小时成瓷，制得白钨矿型微波介质陶瓷材料。
其中，以低熔点氧化物MoO3、Bi2O3以及V2O5作为主元，以ABO4这种典型的白钨矿组成为基础，通过Bi+3离子占据A位，V5+、In3+、Mo6+离子联合占据B位，通过固相反应烧结的方法实现了在没有添加任何烧结助剂的前提下780℃～840℃低温烧结制得白钨矿型微波介质陶瓷材料。
优选地，0.08≤x≤0.10。
优选地，所述白钨矿型微波介质陶瓷材料的微波介电常数εr为70～75，品质因数Q×f值为9230GHz～10110GHz，谐振频率温度系数τf为-210ppm/℃～+135ppm/℃。
优选地，步骤2）中过筛200目后压制得块状体。
优选地，步骤4）中造粒后经60目与120目筛网双层过筛。
本发明实施例第二方面提供的白钨矿型微波介质陶瓷材料的制备方法中不需添加任何助烧剂，烧结温度低，制备工艺简单，物相单一。
本发明实施例的优点将会在下面的说明书中部分阐明，一部分根据说明书是显而易见的，或者可以通过本发明实施例的实施而获知。
具体实施方式
下面分多个实施例对本发明实施例进行进一步的说明。其中，本发明实施例不限定于以下的具体实施例。在不变主权利的范围内，可以适当的进行变更实施。
本发明实施例第一方面提供了一种白钨矿型微波介质陶瓷材料，微波介电常数高，微波性能良好，谐振频率温度系数可调，以及，该白钨矿型微波介质陶瓷材料不需添加任何助烧剂就可以低温烧结制得，化学组成及制备工艺简单，物相单一。本发明实施例第二方面提供了一种白钨矿型微波介质陶瓷材料的制备方法。
第一方面，本发明实施例提供了一种白钨矿型微波介质陶瓷材料，分子式为：Bi(V1-xInx/3Mo2x/3)MoO4,0.06≤x≤0.12。
其中，一种白钨矿型微波介质陶瓷材料以ABO4这种典型的白钨矿组成为基础，Bi+3离子占据A位，V5+、In3+、Mo6+离子联合占据B位。
0.08≤x≤0.10。
所述白钨矿型微波介质陶瓷材料的微波介电常数εr为70～75，品质因数Q×f值为9230GHz～10110GHz，谐振频率温度系数τf为-210ppm/℃～+135ppm/℃。
本发明实施例第一方面提供的白钨矿型微波介质陶瓷材料的微波介电常数高，微波性能良好，谐振频率温度系数可调，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、低温共烧陶瓷系统（LTCC）、陶瓷天线、多芯片组件（MCM）等介质材料使用。
第二方面，本发明实施例提供了一种白钨矿型微波介质陶瓷材料的制备方法，包括以下步骤：
1）将原料V2O5、In2O3、MoO3和Bi2O3按通式Bi(V1-xInx/3Mo2x/3)MoO4中的化学计量比进行配料，0.06≤x≤0.12；
2）将步骤1）中的配料混合，球磨3～6个小时，在100℃～200℃下烘干，过筛200目后压制得块状体；
3）将块状体经650℃～750℃预烧，并保温4～6小时，制得样品烧块；
4）将样品烧块粉碎，并经过5～6个小时的二次球磨，在100℃～200℃下烘干、造粒，造粒后经60目与120目筛网双层过筛，制得瓷料粉末；
5）将瓷料粉末压制成型，在780℃～840℃下烧结2～3个小时成瓷，制得白钨矿型微波介质陶瓷材料。
其中，以低熔点氧化物MoO3、Bi2O3以及V2O5作为主元，以ABO4这种典型的白钨矿组成为基础，通过Bi+3离子占据A位，V5+、In3+、Mo6+离子联合占据B位，通过固相反应烧结的方法实现了在没有添加任何烧结助剂的前提下780℃～840℃低温烧结制得白钨矿型微波介质陶瓷材料。首先是选取合适比例的配方，选取合适的初始氧化物以及合适的取代物，通过一次球磨使得氧化物混合均匀，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。
0.08≤x≤0.10。
所述白钨矿型微波介质陶瓷材料的微波介电常数εr为70～75，品质因数Q×f值为9230GHz～10110GHz，谐振频率温度系数τf为-210ppm/℃～+135ppm/℃。
步骤2）中过筛200目后压制得块状体。
步骤4）中造粒后经60目与120目筛网双层过筛。
本发明实施例第二方面提供的白钨矿型微波介质陶瓷材料的制备方法中不需添加任何助烧剂，烧结温度低，制备工艺简单，物相单一。
实施例1：
将分析纯度的原料V2O5、In2O3、MoO3和Bi2O3按通式Bi(V0.94In0.02Mo0.04)MoO4中的化学计量比进行配料。配制后充分混合球磨4个小时，然后烘干、过筛、压块，经700℃预烧4个小时，然后将预烧后的块状样品粉碎后再进行二次球磨5小时，磨细烘干后造粒，经60目与120目筛网双层过筛，即可得到所需瓷料。将瓷料按需要压制成型（片状或者柱状），然后在780℃～840℃空气下烧结2h成瓷，即可得到白钨矿型微波介质陶瓷材料。
该白钨矿型微波介质陶瓷材料的性能达到如下指标：
780℃～840℃空气中烧结成瓷，微波下的介电性能εr=73（4.84GHz），品质因子Q=2,050，Qf=9,920GHz，微波下的谐振频率温度系数TCF=-210ppm/℃（25℃～85℃）。
实施例2：
将分析纯度的原料V2O5、In2O3、MoO3和Bi2O3按通式Bi(V0.92In0.02667Mo0.05333)MoO4中的化学计量比进行配料。配制后充分混合球磨4个小时，然后烘干、过筛、压块，经700℃预烧4个小时，然后将预烧后的块状样品粉碎后再进行二次球磨5小时，磨细烘干后造粒，经60目与120目筛网双层过筛，即可得到所需瓷料。将瓷料按需要压制成型（片状或者柱状），然后在780℃～840℃空气下烧结2～3h成瓷，即可得到白钨矿型高k值微波介质陶瓷材料。
该白钨矿型微波介质陶瓷材料的性能达到如下指标：
780℃～840℃空气中烧结成瓷，微波下的介电性能εr=75（4.77GHz），品质因子Q=2,120，Qf=10,110GHz，微波下的谐振频率温度系数TCF=-154ppm/℃（25℃～85℃）。
实施例3：
将分析纯度的原料V2O5、In2O3、MoO3和Bi2O3按通式Bi(V0.9In0.03333Mo0.06667)MoO4中的化学计量比进行配料。配制后充分混合球磨4个小时，然后烘干、过筛、压块，经700℃预烧4个小时，然后将预烧后的块状样品粉碎后再进行二次球磨5小时，磨细烘干后造粒，经60目与120目筛网双层过筛，即可得到所需瓷料。将瓷料按需要压制成型（片状或者柱状），然后在780℃～840℃空气下烧结2～3h成瓷，即可得到白钨矿型高k值微波介质陶瓷材料。
该白钨矿型微波介质陶瓷材料的性能达到如下指标：
780℃～840℃空气中烧结成瓷，微波下的介电性能εr=74（4.91GHz），品质因子Q=1,910，Qf=9,380GHz，微波下的谐振频率温度系数TCF=+65ppm/℃（25℃～85℃）。
实施例4：
将分析纯度的原料V2O5、In2O3、MoO3和Bi2O3按通式Bi(V0.88In0.04Mo0.08)MoO4中的化学计量比进行配料。配制后充分混合球磨4个小时，然后烘干、过筛、压块，经700℃预烧4个小时，然后将预烧后的块状样品粉碎后再进行二次球磨5小时，磨细烘干后造粒，经60目与120目筛网双层过筛，即可得到所需瓷料。将瓷料按需要压制成型（片状或者柱状），然后在780℃～840℃空气下烧结2～3h成瓷，即可得到白钨矿型高k值微波介质陶瓷材料。
该白钨矿型微波介质陶瓷材料的性能达到如下指标：
780℃～840℃空气中烧结成瓷，微波下的介电性能εr=70（5.13GHz），品质因子Q=1,800，Qf=9,230GHz，微波下的谐振频率温度系数TCF=+135ppm/℃（25℃～85℃）。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施方式仅限于此，对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单的推演或替换，都应当视为属于本发明由所提交的权利要求书确定专利保护范围。

Claims (8)

1.一种白钨矿型微波介质陶瓷材料，其特征在于，所述白钨矿型微波介质陶瓷材料的分子式为：Bi(V1-xInx/3Mo2x/3)MoO4,0.06≤x≤0.12。
2.如权利要求1所述的一种白钨矿型微波介质陶瓷材料，其特征在于，所述0.08≤x≤0.10。
3.如权利要求1所述的一种白钨矿型微波介质陶瓷材料，其特征在于，所述白钨矿型微波介质陶瓷材料的微波介电常数εr为70～75，品质因数Q×f值为9230GHz～10110GHz，谐振频率温度系数τf为-210ppm/℃～+135ppm/℃。
4.一种白钨矿型微波介质陶瓷材料的制备方法，其特征在于，包括以下步骤：
1）将原料V2O5、In2O3、MoO3和Bi2O3按通式Bi(V1-xInx/3Mo2x/3)MoO4中的化学计量比进行配料，0.06≤x≤0.12；
2）将步骤1）中的配料混合，球磨3～6个小时，在100℃～200℃下烘干，过筛后压制得块状体；
3）将块状体经650℃～750℃预烧，并保温4～6小时，制得样品烧块；
4）将样品烧块粉碎，并经过5～6个小时的二次球磨，在100℃～200℃下烘干、造粒，造粒后过筛，制得瓷料粉末；
5）将瓷料粉末压制成型，在780℃～840℃下烧结2～3个小时成瓷，制得白钨矿型微波介质陶瓷材料。
5.如权利要求4所述的白钨矿型微波介质陶瓷材料的制备方法，其特征在于，所述0.08≤x≤0.10。
6.如权利要求4所述的白钨矿型微波介质陶瓷材料的制备方法，其特征在于，所述白钨矿型微波介质陶瓷材料的微波介电常数εr为70～75，品质因数Q×f值为9230GHz～10110GHz，谐振频率温度系数τf为-210ppm/℃～+135ppm/℃。
7.如权利要求4所述的白钨矿型微波介质陶瓷材料的制备方法，其特征在于，所述步骤2）中过筛200目后压制得块状体。
8.如权利要求4所述的白钨矿型微波介质陶瓷材料的制备方法，其特征在于，所述步骤4）中造粒后经60目与120目筛网双层过筛。
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