中温烧结BaTiO_3基热稳定陶瓷铁电机理与中试生产研究
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摘要
多层陶瓷电容器（MLCC）是电子信息技术的重要基础器件。由于电子系统的发展要求，MLCC向宽温、大容量和低成本方向发展。以BaTiO_3为基铁电陶瓷材料是MLCC的重要材料。本文从分析钛酸钡的晶体结构入手，以提高温度稳定性、提高介电常数、降低烧结温度为目标，对温度稳定型中温烧结瓷料进行研究。并运用XRD、SEM等现代微观分析手段，对其内在机理进行研究。
1、分别讨论了Nb_2O_5、MgO、CoCO_3、CeO_2以及Bi_2O_3等对钛酸钡系统的介电性能的影响，并成功制备处所需的X8R陶瓷材料，性能参数如下：室温介电常数ε25oC>2500,介电损耗tanδ<2.0%,-55oC到150oC范围内最大电容量变化率不超过±15%
2、Pb(Ti_(0.55)Sn_(0.45))O_3掺杂能有效提高BaTiO_3基陶瓷居里点到150℃以上。从结构上看，Pb~(2+)离子的引入进行A位取代，Sn~(2+)离子的引入进行B位取代，引起成分起伏相变扩散，造成居里点向高温移动。通过TEM、XRD分析可知，Pb(Ti_(0.55)Sn_(0.45))O_3与BaTiO_3可形成部分固溶体并形成核－壳结构。核－壳两相相互制约及叠加作用使钛酸钡陶瓷呈现温度稳定性。当在BaTiO_3基陶瓷中添加2wt%Pb(Ti_(0.55)Sn_(0.45))O_3时，样品呈现很好的介电温度特性：ε25oC>1750,介电损耗tanδ<2.0%,-55oC到150oC范围内最大电容量变化率不超过±10%，满足EIAX9R标准。3、球磨中，磨球直径小，球磨时间长，最终粉体粒度会变小而比表面积
变大，这能有效地抑制在烧结时BaTiO_3晶粒生长并产生细晶效应。掺杂元素对BaTiO_3颗粒进行均匀的包裹形成更多的壳-芯晶粒，即铁电相BaTiO_3晶核的比例减小，而顺电相晶壳的体积比增大，使得BaTiO_3基陶瓷居里峰压平展宽，介电常数温度变化率趋于平缓。烧结温度对晶粒的生长、空洞的密度、杂质离子的扩散分布、晶相的组成等有着重要的作用，并对介质陶瓷最终的介电性能产生重要影响。4、将钛酸铋钠(Bi_(0.5)Na_(0.5)TiO_3，BNT)引入BaTiO_3陶瓷中以取代上述配方中
Pb(Ti_(0.55)Sn_(0.45))O_3的使用，BNT与BaTiO_3合成BTBNT，BTBNT具有更高的居里温度（170℃）。再通过Nb_2O_5调节BTBNT的介电温度变化率，Nb~(5+)能够占据Ti~(4+)的位置，并形成富Ti的非铁电相区。而这些第二相的存在使得BTBNT陶瓷的居里峰发生扩散，使得介电温度曲线更加平坦。在合适的配方时，可获得无铅化的X9R陶瓷：ε≈1660、tanδ=0.0194、ΔC/C25℃≤±15%。最后又研究了烧结温度和球磨时间对BTBNT-基陶瓷介电性能的影响。
Multilayer ceramic capacitors (MLCC) are important fundamental components of electronic information technology. To meet the requirements of electronic system, MLCC are developing towards wide temperature, large capacitance and low cost. BaTiO3based ferroelectric ceramics are one of the important materials of MLCC. The preparation of temperature-stable ceramics sintered at medium temperature were researched in this dissertation, of which the principles and micromechanism was researched by modern methods such as XRD, SEM on the basis of crystal structure.
1、The effects of Nb2O5, CoCO3, MgO, CeO2, Bi2O3to the dielectric properties of the system was discussed too. A X8R system with the following parameters was gained:ε>2500at1KHz, tanδ≤1.5%,|△ε/ε|<15%in the region of-55～150℃.
2、The Pb(Tio.55Sno.45)O3additives can shift the Curie temperature of BaTiO3to150℃. Pb2+substitutes for A-site and Sn4+substitutes for B-site in ABO3structure, causing the constituent phase transition diffusion, so the Curie temperature was shifted to higher temperature. Pb(Ti0.55Sn0.45)O3and BaTiO3can form partial solid solution, and core-shell structure was observed, so the temperature characteristics of the capacitance of the system was improved. When2wt%Pb(Tio.55Sno.45)O3was added,the sample showed super dielectric properties that the dielectric constant was>1750at25℃, dielectric loss was lower than2.0%and TCC was≤±10%from-55℃to200℃.Therefore the materials satisfied EIA X9R specifications.
3、When the mixed materials were milling, the smaller milling balls and the longer milling time resulted in smaller particle size of the materials and bigger specific surface area,and the growth of BaTiO3grain can be more effectively restricted with smaller specific surface area and smaller powder size,and fine-grain effect can be produced. More shell-core grain can be formed with the doping elements distributing into BaTiO3particles greatly, and the volume of ferroelectric phase core is increased while the volume of shell decreased. The dielectric property of doping BaTiO3is enhanced with the Curie peak flat and a slowing rate of dielectric constant. The physical and electrical properties of ceramics are greatly influenced by sintering process, and the growth of grain、density of holes、the distribution of doping elements and the crystal phase are affected by the sintering temperature, which also determine the final dielectric properties.
4、In order to environmental protection, Bi0.sNao.sTiO3,(BNT) was doped to substitute for Pb(Ti0.55Sn0.45)O3.BTBNT has higher Curie temperature (170℃)which was generated by calcining the mixture of BaTiO3and BNT. As additives,Nb2O5can accommodate the temperature coefficient of capacitance (TCC)cures of the ceramics based on BTBNT.Nb5+mainly enters the Ti-sites as a donor and the secondary phases are identified as Ti-rich phases.the existence of the secondary phases can flatting the TCC.Suitable Nb2O5-doped BTBNT ceramic material is able to satisfy the EIA X9R specification with a dielectric constant of1660and a dielectric loss of0.0194, AC/C25℃≤15%. At last, the influence of milling time and sintering temperature on the dielectric properties of BTBNT ceramics was investigated.
1、分别讨论了Nb_2O_5、MgO、CoCO_3、CeO_2以及Bi_2O_3等对钛酸钡系统的介电性能的影响，并成功制备处所需的X8R陶瓷材料，性能参数如下：室温介电常数ε25oC>2500,介电损耗tanδ<2.0%,-55oC到150oC范围内最大电容量变化率不超过±15%
2、Pb(Ti_(0.55)Sn_(0.45))O_3掺杂能有效提高BaTiO_3基陶瓷居里点到150℃以上。从结构上看，Pb~(2+)离子的引入进行A位取代，Sn~(2+)离子的引入进行B位取代，引起成分起伏相变扩散，造成居里点向高温移动。通过TEM、XRD分析可知，Pb(Ti_(0.55)Sn_(0.45))O_3与BaTiO_3可形成部分固溶体并形成核－壳结构。核－壳两相相互制约及叠加作用使钛酸钡陶瓷呈现温度稳定性。当在BaTiO_3基陶瓷中添加2wt%Pb(Ti_(0.55)Sn_(0.45))O_3时，样品呈现很好的介电温度特性：ε25oC>1750,介电损耗tanδ<2.0%,-55oC到150oC范围内最大电容量变化率不超过±10%，满足EIAX9R标准。3、球磨中，磨球直径小，球磨时间长，最终粉体粒度会变小而比表面积
变大，这能有效地抑制在烧结时BaTiO_3晶粒生长并产生细晶效应。掺杂元素对BaTiO_3颗粒进行均匀的包裹形成更多的壳-芯晶粒，即铁电相BaTiO_3晶核的比例减小，而顺电相晶壳的体积比增大，使得BaTiO_3基陶瓷居里峰压平展宽，介电常数温度变化率趋于平缓。烧结温度对晶粒的生长、空洞的密度、杂质离子的扩散分布、晶相的组成等有着重要的作用，并对介质陶瓷最终的介电性能产生重要影响。4、将钛酸铋钠(Bi_(0.5)Na_(0.5)TiO_3，BNT)引入BaTiO_3陶瓷中以取代上述配方中
Pb(Ti_(0.55)Sn_(0.45))O_3的使用，BNT与BaTiO_3合成BTBNT，BTBNT具有更高的居里温度（170℃）。再通过Nb_2O_5调节BTBNT的介电温度变化率，Nb~(5+)能够占据Ti~(4+)的位置，并形成富Ti的非铁电相区。而这些第二相的存在使得BTBNT陶瓷的居里峰发生扩散，使得介电温度曲线更加平坦。在合适的配方时，可获得无铅化的X9R陶瓷：ε≈1660、tanδ=0.0194、ΔC/C25℃≤±15%。最后又研究了烧结温度和球磨时间对BTBNT-基陶瓷介电性能的影响。
Multilayer ceramic capacitors (MLCC) are important fundamental components of electronic information technology. To meet the requirements of electronic system, MLCC are developing towards wide temperature, large capacitance and low cost. BaTiO3based ferroelectric ceramics are one of the important materials of MLCC. The preparation of temperature-stable ceramics sintered at medium temperature were researched in this dissertation, of which the principles and micromechanism was researched by modern methods such as XRD, SEM on the basis of crystal structure.
1、The effects of Nb2O5, CoCO3, MgO, CeO2, Bi2O3to the dielectric properties of the system was discussed too. A X8R system with the following parameters was gained:ε>2500at1KHz, tanδ≤1.5%,|△ε/ε|<15%in the region of-55～150℃.
2、The Pb(Tio.55Sno.45)O3additives can shift the Curie temperature of BaTiO3to150℃. Pb2+substitutes for A-site and Sn4+substitutes for B-site in ABO3structure, causing the constituent phase transition diffusion, so the Curie temperature was shifted to higher temperature. Pb(Ti0.55Sn0.45)O3and BaTiO3can form partial solid solution, and core-shell structure was observed, so the temperature characteristics of the capacitance of the system was improved. When2wt%Pb(Tio.55Sno.45)O3was added,the sample showed super dielectric properties that the dielectric constant was>1750at25℃, dielectric loss was lower than2.0%and TCC was≤±10%from-55℃to200℃.Therefore the materials satisfied EIA X9R specifications.
3、When the mixed materials were milling, the smaller milling balls and the longer milling time resulted in smaller particle size of the materials and bigger specific surface area,and the growth of BaTiO3grain can be more effectively restricted with smaller specific surface area and smaller powder size,and fine-grain effect can be produced. More shell-core grain can be formed with the doping elements distributing into BaTiO3particles greatly, and the volume of ferroelectric phase core is increased while the volume of shell decreased. The dielectric property of doping BaTiO3is enhanced with the Curie peak flat and a slowing rate of dielectric constant. The physical and electrical properties of ceramics are greatly influenced by sintering process, and the growth of grain、density of holes、the distribution of doping elements and the crystal phase are affected by the sintering temperature, which also determine the final dielectric properties.
4、In order to environmental protection, Bi0.sNao.sTiO3,(BNT) was doped to substitute for Pb(Ti0.55Sn0.45)O3.BTBNT has higher Curie temperature (170℃)which was generated by calcining the mixture of BaTiO3and BNT. As additives,Nb2O5can accommodate the temperature coefficient of capacitance (TCC)cures of the ceramics based on BTBNT.Nb5+mainly enters the Ti-sites as a donor and the secondary phases are identified as Ti-rich phases.the existence of the secondary phases can flatting the TCC.Suitable Nb2O5-doped BTBNT ceramic material is able to satisfy the EIA X9R specification with a dielectric constant of1660and a dielectric loss of0.0194, AC/C25℃≤15%. At last, the influence of milling time and sintering temperature on the dielectric properties of BTBNT ceramics was investigated.
引文
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