MgTiO_3-ZnTiO_3-CaTiO_3系统MLCC陶瓷材料及中试生产的研究
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摘要
论文主要研究了MgTiO_3-ZnTiO_3-CaTiO_3(MZC)系介质陶瓷材料高温、中温和低温烧结系列化、MZC系介质陶瓷材料及MLCC研究三方面的问题。
MgTiO_3-ZnTiO_3(MZ)系陶瓷和CaTiO_3系陶瓷的高频介电损耗小，其电容温度系数在-55℃～125℃范围内可以相互补偿。通过调节MZC系的CaTiO_3含量、烧结制度和球磨工艺改变陶瓷的相组成和微观结构，获得高温烧结条件下优异的介电性能。CaTiO_3可以调节系统介电常数和温度系数，还能抑制MZ晶粒的过度生长。球磨时间和球磨介质都对MZC系陶瓷粉料的粒度分布影响大。
分别添加ZnO-H_3BO_3(GD)复合氧化物和Li_2O_3-B_2O_3-SiO_2(G4)复合氧化物可将MZC系陶瓷的烧结温度降低，实现中温和低温烧结。在中温烧结条件下，GD复合氧化物玻璃液相可以促进CaTiO_3晶粒的充分形成，当CaTiO_3晶体已经完全形成时，过剩的玻璃液相则会促进Mg_2TiO_4→MgTiO_3的转化。在低温烧结条件下，随着G4复合氧化物添加量增加时，Mg~（2+）进入ZnTiO_3晶体中取代Zn~(2+),形成(Zn,Mg)TiO_3固溶体,抑制了部分ZnTiO_3六方钛铁矿结构向Zn_2TiO_4立方反尖晶石结构的晶型转变。掺杂G4复合氧化物过多时，玻璃液相抑制了Mg~（2+）进入ZnTiO_3晶体中取代Zn~(2+)，ZnTiO_3不稳定大量转化为Zn2Ti3O8。另外，G4复合氧化物的制备工艺和球磨助剂对系统的相组成也有重要的影响。
通过配方、实验工艺以及介电性能等方面的协调优化，得到了高温、中温和低温烧结条件下性能优良的MZC系陶瓷材料。
(1)高温：添加1.3mol%CaTiO_3的MZC陶瓷在1270℃烧结2h时得到的介电性能较好，介电常数为22.62、介电损耗为1.310-5，和电容温度系数为20.51ppm/℃（-55℃～125℃）。
(2)中温：添加8.25wt%GD玻璃的MZC陶瓷在1110℃烧结2h时得到的介电性能较好，介电常数为22.38、介电损耗为1.710-5，和电容温度系数为20.93ppm/℃（-55℃～125℃）。
(3)低温：添加10.0wt%G4复合氧化物的MZC系陶瓷在900℃烧结8h时得到的介电性能较好，介电常数为20.88、介电损耗为9.510-5和电容温度系数为15ppm/℃（-55℃～125℃）。
对于MZC系陶瓷材料的中试生产和MLCC研究，初试到中试的工艺对MZC陶瓷粉料的粒度分布影响较小，中试样品性能优良。MZC系MLCC的烧结温度低于圆片电容的烧结温度，应合理调节烧结温度。相对圆片电容来说，MLCC介电性能有所下降(介电常数和介电损耗)。
The sintering temperature serialization,pilot production,and MLCC serializationof MgTiO_3-ZnTiO_3-CaTiO_3(MZC) system ceramics were studied.
MgTiO_3-ZnTiO_3(MZ) system and CaTiO_3ceramics with mutual-compensatedtemperature coefficients of capacitance(-55℃～125℃) have low dielectric loss athigh frequency.By addition of appropriate amount of CaTiO_3,sintering system,andmilling technology,the microstructure and phases were altered so that excellentdielectric properties were obtained at high sintering temperature. CaTiO_3not only canadjust the relative dielectric constant (ε_r) and the temperature coefficient ofcapacitance(TCC),but also can inhabit the abnormal growth of MZ grain.The sizedistribution curve of MZC ceramic powder was influenced by milling time andmilling medium significantly.
The addition of ZnO-H_3BO_3(GD) composite oxide and Li_2O_3-B_2O_3-SiO_2(G4)can decrease the sintering temperature of MZC ceramic, so that middle and lowtemperature sintering were obtained. GD composite oxide can form liquid phase atintermediate sintering temperature and promote the formation of CaTiO_3grain.Besides surplus glass phase can promote the transformation from Mg_2TiO_4toMgTiO_3. At low sintering temperature, Zn~(2+)can be replaced by Mg~（2+）by increasingG4composite oxide,which can inhabit the some transformation from ZnTiO_3toZn_2TiO_4.By contrast, a large amount of surplus G4glass phase can promote theformation of Zn2Ti3O8from ZnTiO_3. The morphology of G4and milling medium alsoaffected the phases of system.
By control of formula、process、and dielectric properties, The MZC ceramicswere obtained at high\intermediate\low sintering temperature.
(1) The MZC ceramic doped with1.3mol%CaTiO_3sintered at1270℃for2hhad excellent dielectric properties of=22.62, tan=1.3×10-5, TCC=20.51ppm/℃（-55℃～125℃）.
(2) The MZC ceramic doped with8.25wt%GD glass sintered at1110℃for2hhad excellent dielectric properties of=22.38,=1.7×10-5, TCC=20.93ppm/℃（-55℃～125℃）.
(3) The MZC ceramic doped with10.0wt%G4glass sintered at900℃for8hhad excellent dielectric properties of=20.88,=9.5×10-5, TCC=15ppm/℃（-55℃～125℃）.
For the research of pilot production and MLCC about MZC ceramics, The size distribution curve of MZC ceramic powder were almost not influenced by the processfrom preliminary examination to pilot production.Compared to disk,the sinteringtemperature of MLCC was lower and dielectric properties were decreased to someextent,which was caused by impefect match between ceramics and electrodes.
MgTiO_3-ZnTiO_3(MZ)系陶瓷和CaTiO_3系陶瓷的高频介电损耗小，其电容温度系数在-55℃～125℃范围内可以相互补偿。通过调节MZC系的CaTiO_3含量、烧结制度和球磨工艺改变陶瓷的相组成和微观结构，获得高温烧结条件下优异的介电性能。CaTiO_3可以调节系统介电常数和温度系数，还能抑制MZ晶粒的过度生长。球磨时间和球磨介质都对MZC系陶瓷粉料的粒度分布影响大。
分别添加ZnO-H_3BO_3(GD)复合氧化物和Li_2O_3-B_2O_3-SiO_2(G4)复合氧化物可将MZC系陶瓷的烧结温度降低，实现中温和低温烧结。在中温烧结条件下，GD复合氧化物玻璃液相可以促进CaTiO_3晶粒的充分形成，当CaTiO_3晶体已经完全形成时，过剩的玻璃液相则会促进Mg_2TiO_4→MgTiO_3的转化。在低温烧结条件下，随着G4复合氧化物添加量增加时，Mg~（2+）进入ZnTiO_3晶体中取代Zn~(2+),形成(Zn,Mg)TiO_3固溶体,抑制了部分ZnTiO_3六方钛铁矿结构向Zn_2TiO_4立方反尖晶石结构的晶型转变。掺杂G4复合氧化物过多时，玻璃液相抑制了Mg~（2+）进入ZnTiO_3晶体中取代Zn~(2+)，ZnTiO_3不稳定大量转化为Zn2Ti3O8。另外，G4复合氧化物的制备工艺和球磨助剂对系统的相组成也有重要的影响。
通过配方、实验工艺以及介电性能等方面的协调优化，得到了高温、中温和低温烧结条件下性能优良的MZC系陶瓷材料。
(1)高温：添加1.3mol%CaTiO_3的MZC陶瓷在1270℃烧结2h时得到的介电性能较好，介电常数为22.62、介电损耗为1.310-5，和电容温度系数为20.51ppm/℃（-55℃～125℃）。
(2)中温：添加8.25wt%GD玻璃的MZC陶瓷在1110℃烧结2h时得到的介电性能较好，介电常数为22.38、介电损耗为1.710-5，和电容温度系数为20.93ppm/℃（-55℃～125℃）。
(3)低温：添加10.0wt%G4复合氧化物的MZC系陶瓷在900℃烧结8h时得到的介电性能较好，介电常数为20.88、介电损耗为9.510-5和电容温度系数为15ppm/℃（-55℃～125℃）。
对于MZC系陶瓷材料的中试生产和MLCC研究，初试到中试的工艺对MZC陶瓷粉料的粒度分布影响较小，中试样品性能优良。MZC系MLCC的烧结温度低于圆片电容的烧结温度，应合理调节烧结温度。相对圆片电容来说，MLCC介电性能有所下降(介电常数和介电损耗)。
The sintering temperature serialization,pilot production,and MLCC serializationof MgTiO_3-ZnTiO_3-CaTiO_3(MZC) system ceramics were studied.
MgTiO_3-ZnTiO_3(MZ) system and CaTiO_3ceramics with mutual-compensatedtemperature coefficients of capacitance(-55℃～125℃) have low dielectric loss athigh frequency.By addition of appropriate amount of CaTiO_3,sintering system,andmilling technology,the microstructure and phases were altered so that excellentdielectric properties were obtained at high sintering temperature. CaTiO_3not only canadjust the relative dielectric constant (ε_r) and the temperature coefficient ofcapacitance(TCC),but also can inhabit the abnormal growth of MZ grain.The sizedistribution curve of MZC ceramic powder was influenced by milling time andmilling medium significantly.
The addition of ZnO-H_3BO_3(GD) composite oxide and Li_2O_3-B_2O_3-SiO_2(G4)can decrease the sintering temperature of MZC ceramic, so that middle and lowtemperature sintering were obtained. GD composite oxide can form liquid phase atintermediate sintering temperature and promote the formation of CaTiO_3grain.Besides surplus glass phase can promote the transformation from Mg_2TiO_4toMgTiO_3. At low sintering temperature, Zn~(2+)can be replaced by Mg~（2+）by increasingG4composite oxide,which can inhabit the some transformation from ZnTiO_3toZn_2TiO_4.By contrast, a large amount of surplus G4glass phase can promote theformation of Zn2Ti3O8from ZnTiO_3. The morphology of G4and milling medium alsoaffected the phases of system.
By control of formula、process、and dielectric properties, The MZC ceramicswere obtained at high\intermediate\low sintering temperature.
(1) The MZC ceramic doped with1.3mol%CaTiO_3sintered at1270℃for2hhad excellent dielectric properties of=22.62, tan=1.3×10-5, TCC=20.51ppm/℃（-55℃～125℃）.
(2) The MZC ceramic doped with8.25wt%GD glass sintered at1110℃for2hhad excellent dielectric properties of=22.38,=1.7×10-5, TCC=20.93ppm/℃（-55℃～125℃）.
(3) The MZC ceramic doped with10.0wt%G4glass sintered at900℃for8hhad excellent dielectric properties of=20.88,=9.5×10-5, TCC=15ppm/℃（-55℃～125℃）.
For the research of pilot production and MLCC about MZC ceramics, The size distribution curve of MZC ceramic powder were almost not influenced by the processfrom preliminary examination to pilot production.Compared to disk,the sinteringtemperature of MLCC was lower and dielectric properties were decreased to someextent,which was caused by impefect match between ceramics and electrodes.
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