CN112341160B - 一种宽频高q低温度系数钡镁钙铌钽系复合陶瓷及其制备方法 - Google Patents

一种宽频高q低温度系数钡镁钙铌钽系复合陶瓷及其制备方法 Download PDF

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CN112341160B
CN112341160B CN202011227024.2A CN202011227024A CN112341160B CN 112341160 B CN112341160 B CN 112341160B CN 202011227024 A CN202011227024 A CN 202011227024A CN 112341160 B CN112341160 B CN 112341160B
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magnesium
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周洪庆
单怡婷
陆阳
罗现福
钱磊
罗会安
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Nanjing Tech University
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Abstract

本发明提供了一种宽频高Q低温度系数钡镁钙铌钽系复合陶瓷及其制备方法。其特征是由钡镁钙铌钽系复合钙钛矿型陶瓷组分及相应的陶瓷助烧剂所组成；使用高纯度的原料为主成分，按特定化学计量比配料，以适当的比例在球磨机中混合研磨，经预烧得到大部分的目标物相，再经球磨得到所需的精细陶瓷粉体。然后通过干压或注塑成型，在空气气氛中排胶、烧结致密化，最后对烧成的瓷件进行后处理。该陶瓷料具有相对介电常数20到32之间连续可调、介质损耗低、体积小、耐温高等特点，而且对温度条件不敏感，具有良好的环境适应性，完全满足大规模相控阵雷达、各类机载星载、5G微基站与终端等电子设备对体积制约、可靠性的苛刻要求。

Description

一种宽频高Q低温度系数钡镁钙铌钽系复合陶瓷及其制备 方法
技术领域
本发明涉及一种适合高灵敏性宽频滤波器用多元复合陶瓷及其制备方法，尤其涉及一种一种宽频高Q低温度系数钡镁钙铌钽系复合陶瓷及其制备方法，属于无机复合材料领域。
背景技术
射频微波技术是当今人类社会文明发展的重要标志，也是国家安全与经济发展的支柱，人类为了更好地利用宽频微波资源一直在不懈努力。在移动通信领域，微波电磁场发挥着必不可少的媒介作用。由于其频率高，波长短，可携带的信息容量大，具备极强的方向性和抗干扰能力，能获得较高的通信质量；具有穿透电离层能力，可用于卫星通信。因此，微波已成为炙手可热的高端信息的重要资源，广泛应用于雷达天线、移动基站、北斗系统、空天飞行器、汽车电子等领域。随着5G互联网+以及北斗卫星导航系统组网实用，新一代的通信技术将在数据传输的稳定性、高速性及便携性上进行更深入的研究优化。
基于移动通讯的快速发展，宽频微波元器件正在不断向小型化、高效能、低损耗、低成本方向演进，基于微波介质陶瓷的功能器件正在快速升级优化，伴随着5G网络、北斗导航系统发展及国内大量芯片依靠进口的现实，高Q低损耗低温度系数微波介质陶瓷新材料将在未来相当长的时间，支撑高端信息的应用与发展。
发明内容
本发明的目的是为了改进现有技术的不足而提供一种宽频高Q低温度系数钡镁钙铌钽系复合陶瓷，本发明的另一目的是提供上述宽频高Q低温度系数钡镁钙铌钽系复合陶瓷的制备方法。
本发明的技术方案为：一种宽频高Q低温度系数钡镁钙铌钽系复合陶瓷，其特征是由钡镁钙铌钽系复合钙钛矿型陶瓷组分及相应的陶瓷助烧剂所组成；其中：钡镁钙铌钽系复合钙钛矿型陶瓷组分的重量百分量为83～90％；陶瓷助烧剂的重量百分量为10～17％。
优选上述钡镁钙铌钽系复合钙钛矿型陶瓷组分和各组分占钡镁铌钽钙钛矿型系陶瓷总量的重量百分量分别为：
BaCO3 25-45％；MgCO3 10-20％；CaCO3 5-15％；Nb2O5 15-23％；Ta2O5 15-23％。
优选上述的陶瓷助烧剂由氧化镁、氧化锌、氧化铝、氧化硅和钨酸五种成分组成，各成分占钡镁钙铌钽系氧化物与助烧剂总量的重量百分含量分别为：
MgO 3-8％；ZnO 2-5％；Al2O3 1.5-3.5％；SiO2 2-5％；H2WO3 0.5-2.5％。
本发明还提供了一种制备上述的宽频高Q低温度系数钡镁铌钽复合陶瓷的方法，其具体步骤如下：
(1)按钡镁钙铌钽系复合钙钛矿型陶瓷组分配方，分别称取BaCO3、MgCO2、CaCO3、Nb2O5和Ta2O5，混合6～12h；
(2)将混合均匀的原料过150目筛，然后在马弗炉中，进行特定物相合成预烧，1050-1250℃，保温1-5h；
(3)将合成预烧料取出后，破碎成细粉并过筛100目筛，按主料与助烧剂的配比，精确称取适量的预烧合成料、添加适量的助烧剂，置于球磨罐中，加入料球质量比1:(4-5)的比例的直径8-10mm球磨石，以及料和蒸馏水质量比为1:(4-5)的比例，在行星磨高速球磨15-45h；
(4)将球磨细度达到要求的陶瓷浆料，倒出烘干，细碎过200目筛，粒度均匀、中位径控制在1.0-2.0um之间；
(5)在粒径与粒度分布合理的瓷粉中，按照干压或注塑两种方式成型；
(6)将干压或注塑成型的陶瓷生坯体，置于电热炉内，以0.25-0.5℃/min升温至500-550℃，缓慢排胶、脱蜡分段保温1-3h，达到500-550℃之后，以2-3℃/min升温至1000-1100℃，再以0.5-1.5℃/min升温至1450℃-1580℃设定温度，保温5-20h，再以0.5-1℃/min降温200-600℃保温2-5h，过程中氧气分压159.2-170mmHg，600℃以后随炉冷却，得到宽频高Q低温度系数钡镁钙铌钽系复合陶瓷。
其中步骤(5)中所述的干压成型为：在干压粉料中，加入质量浓度为6-8％的PVA粘结剂，按照瓷粉总质量的12-17％造粒，在500-800MPa压力范围成型，压制成Ф13mm×(8～12)mm的陶瓷生坯；所述的注塑成型为：在注塑粉料中，加入瓷粉总质量为8-12％的石蜡，同时加入瓷粉总质量6-12％的聚丙烯粘结剂，混练均匀，在120-180℃、5-30MPa压力范围注塑成型。
本发明宽频高Q低温度系数钡镁铌钽复合陶瓷材料的特点：
(1)所制坯体表面平整、光滑；
(2)烧成收缩率16～20％(X、Y轴)、16～19％(Z轴)；
(3)烧结瓷体介电性能：在宽频3--20G范围，介电常数稳定，且介电常数在20-32之间连续可调，Qf≥85000，介电损耗≤6.5×10﹣5；
(4)陶瓷烧结体结构致密、多晶相稳定、晶粒适中、大小均匀，近零气孔率。
附图说明
图1为本发明钡镁钙铌钽复合陶瓷干压与注塑成型与致密化烧结样品照片；
图2本发明1550℃保温18h烧成钡镁钙铌钽复合陶瓷微观结构SEM照片。
具体实施方式
表1为本发明具体实施钡镁钙铌钽复合陶瓷预烧用各组分碳酸盐和氧化物含量。按表1所示分别称取各组分，经8h混匀后，在马弗炉中预烧，1220℃保温3h，使碳酸盐分解，消除部分晶型转化造成的内应力与少量有机杂质，合成多种晶相，经湿法球磨得到平均粒径为1.43μm钡镁钙铌钽复合陶瓷粉料。按表2的配方进行混合造粒，在65MPa干压、28MPa注塑成型，分别制备坯体。将生坯置于电热炉内，以0.5℃/min升温至500℃，缓慢排胶、脱蜡分段保温1-3h，达到550℃之后，以2-3℃/min升温至1000℃，再以1℃/min升温至1550℃设定温度，保温18h，再以1℃/min降温200-600℃保温5h，然后随炉冷却，得到本发明的高Q低温度系数多元复合陶瓷，图1所示。对烧结体性能测试如表3所示。本发明钡镁钙铌钽复合陶瓷的微观结构SEM照片，如图2所示。
表1本发明中钡镁钙铌钽复合陶瓷主体系各组分含量(wt％)
组分 BaCO<sub>3</sub> MgCO<sub>3</sub> CaCO<sub>3</sub> Nb<sub>2</sub>O<sub>5</sub> Ta<sub>2</sub>O<sub>5</sub>
No.1 27.8 17.4 11.3 21.2 22.3
No.2 35.7 15.2 7.4 19.9 21.8
No.3 43.2 13.6 5.8 18.1 19.3
表2钡镁钙铌钽复合陶瓷加助烧剂各组分的含量(wt％)
Figure BDA0002763908090000041
表3钡镁铌钽复合陶瓷材料烧结收缩与介电性能
Figure BDA0002763908090000051

Claims (3)

1.一种宽频高Q低温度系数钡镁钙铌钽系复合陶瓷，其特征是由钡镁钙铌钽系复合钙钛矿型陶瓷组分及相应的陶瓷助烧剂所组成；其中：钡镁钙铌钽系复合钙钛矿型陶瓷组分的重量百分量为83~90%； 陶瓷助烧剂的重量百分量为 10~17%；钡镁钙铌钽系复合钙钛矿型陶瓷组分和各组分占钡镁铌钽钙钛矿型系陶瓷总量的重量百分量分别为：BaCO3 25-45%； MgCO3 10-20% ； CaCO3 5-15% ； Nb2O5 15-23%；Ta2O5 15-23%；陶瓷助烧剂由氧化镁、氧化锌、氧化铝、氧化硅和钨酸五种成分组成，各成分占钡镁钙铌钽系氧化物与助烧剂总量的重量百分含量分别为：MgO 3-8%；ZnO 2-5%；Al2O3 1.5-3.5%；SiO2 2-5%；H2WO3 0.5-2.5%。
2.一种制备如权利要求1所述的宽频高Q低温度系数钡镁铌钽复合陶瓷的方法，其具体步骤如下：
(1) 按钡镁钙铌钽系复合钙钛矿型陶瓷组分配方，分别称取BaCO3、MgCO2、CaCO3、Nb2O5和Ta2O5，混合6~12h；
(2) 将混合均匀的原料过150目筛，然后在马弗炉中，进行特定物相合成预烧，1050-1250℃，保温1-5h；
(3) 将合成预烧料取出后，破碎成细粉并过筛100目筛，按主料与助烧剂的配比，精确称取适量的预烧合成料、添加适量的助烧剂，置于球磨罐中，加入料球质量比1:（4-5）的比例的直径8-10mm球磨石，以及料和蒸馏水质量比为1:（4-5）的比例，在行星磨高速球磨15-45 h；
(4)将球磨细度达到要求的陶瓷浆料，倒出烘干，细碎过200目筛，粒度均匀、中位径控制在1.0-2.0um之间；
(5)在粒径与粒度分布合理的瓷粉中，按照干压或注塑两种方式成型；
(6) 将干压或注塑成型的陶瓷生坯体，置于电热炉内，以0.25-0.5℃/min升温至500-550℃，排胶、脱蜡分段保温1-3h，达到500-550℃之后，以2-3℃/min升温至1000-1100℃，再以0.5-1.5℃/min升温至1450℃-1580℃设定温度，保温5-20 h，再以0.5-1℃/min降温200-600℃保温2-5h，过程中氧气分压159.2-170mmHg，600℃以后随炉冷却，得到宽频高Q低温度系数钡镁钙铌钽系复合陶瓷。
3.根据权利要求2所述的方法，其特征在于步骤（5）中所述的干压成型为：在干压粉料中，加入质量浓度为6-8%的PVA粘结剂，按照瓷粉总质量的12-17%造粒，在500-800MPa压力范围成型，压制成Ф13mm×(8~12)mm 的陶瓷生坯；所述的注塑成型为：在注塑粉料中，加入瓷粉总质量为8-12%的石蜡，同时加入瓷粉总质量6-12%的聚丙烯粘结剂，混练均匀，在120-180℃、5-30MPa压力范围注塑成型。
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