钛酸钡基抗还原介质的组成改性及基础工艺研究
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摘要
多层陶瓷电容器(MLCC)是表面组装电路中最重要的电子元件之一。使用贱金属(Ni或Cu)代替昂贵的贵金属Pd或Ag／Pd合金作为内电极，可以极大地降低MLCC的生产成本。为防止Ni(或Cu)金属在空气中烧结时发生氧化，这类使用贱金属内电极的MLCC(BME-MLCC)必须在还原气氛下烧结，从而对MLCC介质材料的性能和应用特性提出了更高的要求。BaTiO_3基抗还原介质陶瓷，作为可以与贱金属内电极共烧的MLCC材料，因而在工业应用和基础研究上都是最具吸引力的发展方向之一。
为满足某些车载用电子系统的对工作温度的苛刻要求，近来满足EIA X8R特性(-55℃～150℃，ΔC／C≤±15％，tanδ_(25℃)≤0.025)的MLCC材料受到了广泛关注。但BaTiO_3本身的居里温度在125℃左右，在此温度以上，材料要满足B特性(ΔC／C≤±15％)非常困难，如何提高BaTiO_3的居里温度以制备X8R材料已经成为目前的研究难点。另一方面，采用亚微米级的超细原料已成为大容量MLCC的工艺基础，而亚微米级的超细原料的使用又对改性掺杂剂的粒径、纯度及掺杂的均匀性提出了更高的要求。为此国内外研究者发展了多种技术以达到在瓷料制备中掺杂剂的粒径控制和均匀分布；然而这些制备超细瓷料的方法都不同程度的存在着设备和操作复杂，原料和辅助材料昂贵等缺陷，导致其在生产实践中受到种种限制。
本论文正是针对上述问题，以BaTiO_3基抗还原陶瓷材料为主要的研究对象，在深入分析BaTiO_3陶瓷的改性机理的基础上，对材料和工艺问题作了创新性和探索性研究。主要内容为：
1．详细研究了稀土元素对BaTiO_3-Mg-R(R=稀土元素La、Pr、Ce、Nd、Sm、Gd、Dy、Ho、Er、Yb)体系的微观结构和介电性能的影响。研究发现，陶瓷晶粒尺寸的变化、壳—芯结构的形成均与稀土元素的固溶度有关。首次发现过量稀土形成的焦绿石相R_2Ti_2O_7可对壳—芯结构的形成起辅助作用。在Dy~(3+)、Ho~(3+)、Er~(3+)和Yb~(3+)掺杂并形成壳—芯结构的样品中，发现居里点随稀土离子的半径减小而升高，首次提出了如下的居里点移动机理：稀土离子取代BaTiO_3的B位将使晶粒壳的BaTiO_3晶胞体积增大，并导致晶粒壳发生相对于晶粒芯的体积膨胀，对晶粒芯产生张应力作用，使晶粒芯的居里点升高；反之，稀土离子的A位取代将使晶粒芯受到压应力作用，导致居里点降低。
2．详细研究了各种掺杂离子对壳—芯结构的BaTiO_3-Mg-R(R=Yb、Ho)系统的介电性能的影响及其改性机理。首次发现，Mg／Yb共掺杂的BaTiO_3陶瓷
Ceramic multilayer capacitors (MLCC) are one of the most important electronic components at the surface mounting of electronic circuits. A substantial cost saving can be achieved by utilizing base metal (Ni or Cu) electrode as internal metallization in MLCC over the more expensive precious metals such as Pd or Ag/Pd. The base-metal-electrode capacitors (BME-MLCC) need to be fired in reducing atmosphere, since the Ni (or Cu) metal is subjective to oxidation during sintering in air. This inevitably results in requirements for high performance non-reducible dielectrics for BME-MLCC. As a result, BaTiO_3-based non-reducible dielectrics, which can be co-fired with BME, have become one of the most attracting fields in both industry and academia.
Nowadays, much attention has been paid to MLCC satisfying EIA X8R specification (-55 to 150℃,ΔC=±15% or less, tan δ_(25℃)≤0.025) for automotive applications, which work under harsh conditions. However, it is very difficult for BaTiO_3-based dielectrics to satisfy the R characteristic (ΔC/C=± 15% or less) when the temperature is higher than 130℃, since the Curie point (T_C) of pure BaTiO_3 is about 125℃. Accordingly, how to shift T_C to higher temperatures has become a key issue in research of BaTiO_3-based X8R materials. Besides, ultrafine starting materials have become the basis of the mass production of MLCC, which inevitably leads to high requirements for particle size, purity, and uniformity of additives. Some technologies have been developed in order to achieve downsizing and uniform distribution of additives. However, most of these techniques suffer from complex equipments, complicated processing procedures and expensive raw materials.
In this thesis, the basic modification mechanisms of BaTiO_3 have been analyzed. Then novel materials and process are explored and investigated for non-reducible dielectrics.
The main results are as follows:
1. The effects of rare earth elements on the microstructure and dielectric properties of BaTiO_3-Mg-R (R=rare earth elementals La, Pr, Ce, Nd, Sm, Gd, Dy, Ho, Er, Yb) system are investigated in detail. The mechanisms governing average grain size and the formation of core-shell structure are discussed in terms of the solubilities of the rare earth elements. Pyrochlore-type R_2Ti_2O_7 is found to be helpful to form core-shell structure. In the cases of Dy~(3+), Ho~(3+), Er~(3+), Yb~(3+)-substituted samples with
为满足某些车载用电子系统的对工作温度的苛刻要求，近来满足EIA X8R特性(-55℃～150℃，ΔC／C≤±15％，tanδ_(25℃)≤0.025)的MLCC材料受到了广泛关注。但BaTiO_3本身的居里温度在125℃左右，在此温度以上，材料要满足B特性(ΔC／C≤±15％)非常困难，如何提高BaTiO_3的居里温度以制备X8R材料已经成为目前的研究难点。另一方面，采用亚微米级的超细原料已成为大容量MLCC的工艺基础，而亚微米级的超细原料的使用又对改性掺杂剂的粒径、纯度及掺杂的均匀性提出了更高的要求。为此国内外研究者发展了多种技术以达到在瓷料制备中掺杂剂的粒径控制和均匀分布；然而这些制备超细瓷料的方法都不同程度的存在着设备和操作复杂，原料和辅助材料昂贵等缺陷，导致其在生产实践中受到种种限制。
本论文正是针对上述问题，以BaTiO_3基抗还原陶瓷材料为主要的研究对象，在深入分析BaTiO_3陶瓷的改性机理的基础上，对材料和工艺问题作了创新性和探索性研究。主要内容为：
1．详细研究了稀土元素对BaTiO_3-Mg-R(R=稀土元素La、Pr、Ce、Nd、Sm、Gd、Dy、Ho、Er、Yb)体系的微观结构和介电性能的影响。研究发现，陶瓷晶粒尺寸的变化、壳—芯结构的形成均与稀土元素的固溶度有关。首次发现过量稀土形成的焦绿石相R_2Ti_2O_7可对壳—芯结构的形成起辅助作用。在Dy~(3+)、Ho~(3+)、Er~(3+)和Yb~(3+)掺杂并形成壳—芯结构的样品中，发现居里点随稀土离子的半径减小而升高，首次提出了如下的居里点移动机理：稀土离子取代BaTiO_3的B位将使晶粒壳的BaTiO_3晶胞体积增大，并导致晶粒壳发生相对于晶粒芯的体积膨胀，对晶粒芯产生张应力作用，使晶粒芯的居里点升高；反之，稀土离子的A位取代将使晶粒芯受到压应力作用，导致居里点降低。
2．详细研究了各种掺杂离子对壳—芯结构的BaTiO_3-Mg-R(R=Yb、Ho)系统的介电性能的影响及其改性机理。首次发现，Mg／Yb共掺杂的BaTiO_3陶瓷
Ceramic multilayer capacitors (MLCC) are one of the most important electronic components at the surface mounting of electronic circuits. A substantial cost saving can be achieved by utilizing base metal (Ni or Cu) electrode as internal metallization in MLCC over the more expensive precious metals such as Pd or Ag/Pd. The base-metal-electrode capacitors (BME-MLCC) need to be fired in reducing atmosphere, since the Ni (or Cu) metal is subjective to oxidation during sintering in air. This inevitably results in requirements for high performance non-reducible dielectrics for BME-MLCC. As a result, BaTiO_3-based non-reducible dielectrics, which can be co-fired with BME, have become one of the most attracting fields in both industry and academia.
Nowadays, much attention has been paid to MLCC satisfying EIA X8R specification (-55 to 150℃,ΔC=±15% or less, tan δ_(25℃)≤0.025) for automotive applications, which work under harsh conditions. However, it is very difficult for BaTiO_3-based dielectrics to satisfy the R characteristic (ΔC/C=± 15% or less) when the temperature is higher than 130℃, since the Curie point (T_C) of pure BaTiO_3 is about 125℃. Accordingly, how to shift T_C to higher temperatures has become a key issue in research of BaTiO_3-based X8R materials. Besides, ultrafine starting materials have become the basis of the mass production of MLCC, which inevitably leads to high requirements for particle size, purity, and uniformity of additives. Some technologies have been developed in order to achieve downsizing and uniform distribution of additives. However, most of these techniques suffer from complex equipments, complicated processing procedures and expensive raw materials.
In this thesis, the basic modification mechanisms of BaTiO_3 have been analyzed. Then novel materials and process are explored and investigated for non-reducible dielectrics.
The main results are as follows:
1. The effects of rare earth elements on the microstructure and dielectric properties of BaTiO_3-Mg-R (R=rare earth elementals La, Pr, Ce, Nd, Sm, Gd, Dy, Ho, Er, Yb) system are investigated in detail. The mechanisms governing average grain size and the formation of core-shell structure are discussed in terms of the solubilities of the rare earth elements. Pyrochlore-type R_2Ti_2O_7 is found to be helpful to form core-shell structure. In the cases of Dy~(3+), Ho~(3+), Er~(3+), Yb~(3+)-substituted samples with
引文
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