【作者】 马家峰；

【导师】 刘心宇；

【作者基本信息】 中南大学 ， 电子信息材料与器件， 2013， 博士

【摘要】 摘要：基于(Ba0.85Ca0.15)(Ti0.90Zr0.1)O3(BCTZ)钙钛矿型无铅压电陶瓷具有压电常数高、介电常数大、损耗小、制备与废弃处理对环境污染低等优点,并根据其目前存在烧结温度高、居里温度低等问题。本文首先采用Ag2O, MnO2掺杂改性BCTZ基体,研究对陶瓷烧结特性的影响；其次采用In2O3, Ga2O3, Sb2O3掺杂改性BCTZ基体,研究对陶瓷的晶粒生长规律的影响；之后采用BiAlO3, BiYbO3, Ba(Cu0.5W0.5)O3复合取代BCTZ基体,研究对陶瓷居里温度的影响规律；根据前面的研究结果,采用In2O3, Ga2O3, Ba(Cu0.5W0.5)O3掺杂(复合)(Ba0.85Ca0.15)(Ti0.90Zr0.1)O3(BCTZ99)基体,研究对陶瓷的晶粒及居里温度的影响规律；最后对比分析了In2O3, Ga2O3, Ba(Cu0.5W0.5)O3对BCTZ和BCTZ99基体的影响和作用机理。本文研究的主要内容如下：系统研究了BCTZ-Ag, BCTZ-Mn体系陶瓷的组成与相结构、显微组织、密度及电性能的影响关系,并对比分析了Ag2O, MnO2对BCTZ陶瓷的影响规律。XRD表明：BCTZ-Ag陶瓷的MPB在x=0.1附近；BCTZ-Mn陶瓷的MPB在0.06≤x≤0.10内。陶瓷的最佳性能为：BCTZ-Ag陶瓷x=0.08时,d33=616pC/N,kp=58.1%, r=5.6Ω, tan δ=0.63%; BCTZ-Mn陶瓷x=0.08时,d33=495pC/N,kp=49.6%, tan δ=1.58%, Pr=10.9μC/cm2。对比发现：BCTZ-0.08%Ag陶瓷的晶粒尺寸为50-90μm,远大于BCTZ-0.08%Mn陶瓷的30-40μm。系统研究了BCTZ-In, BCTZ-Ga, BCTZ-Sb体系陶瓷的组成与相结构、显微晶相组织、密度及电性能的影响关系,探讨陶瓷相变与铁电温谱的关系,并对比分析了In2O3, Ga2O3, Sb2O3对BCTZ陶瓷晶粒生长的影响规律。SEM表明：BCTZ-In陶瓷呈现小晶粒长大数量逐渐增多；BCTZ-Ga陶瓷的晶粒逐渐长大；BCTZ-Sb陶瓷的晶粒均匀长大。陶瓷的最佳性能为：BCTZ-In陶瓷x=0.08时,d33=605pC/N, kp=57.7%, r=6.8Ω, tanδ=1.56%, Pr=11.1μC/cm2; BCTZ-Ga陶瓷x=0.10时,d33=705pC/N,kp=61%, r=5.2Ω, tan δ=1.75%, Pr=11.3μC/cm2; BCTZ-Sb陶瓷x=0.1时,d33=556pC/N,kp=52%, r=5.2Ω, tan δ=1.3%, Pr=12.6μC/cm2。铁电温谱表明：BCTZ-0.1%Ga陶瓷的TR-T相变在25-40℃内；BCTZ-0.1%Sb陶瓷在-60-20℃内Pr达到饱和为15μC/cm2,TR-T相变在20-40℃内。比较BCTZ-In, BCTZ-Ga, BCTZ-Sb, BCTZ陶瓷发现,最大晶粒尺寸分别80μm,50μm,15μm,5μm。系统研究了BCTZ-BA, BCTZ-BY, BCTZ-BCW体系陶瓷的组成与相结构、显微组织及电性能的影响关系,探讨陶瓷相变与铁电温谱的关系,并对比分析了BiAlO3, BiYbO3, Ba(Cu0.5W0.5)O3对BCTZ陶瓷居里温度的影响规律。结果表明：BCTZ-BA和BCTZ-BY陶瓷的Tc向低温移动；BCTZ-BCW陶瓷的Tc向高温推移,并在0.05%≤<x≤0.30%内存在MPB；陶瓷的最佳性能为：BCTZ-BA陶瓷x=0.1%时,d33=536pC/N, kp=55.6%, tan δ=1.26%,Pr=10.8μC/cm2; BCTZ-BY陶瓷x=0.1%时,d33=580pC/N, kp=56.4%, r=10.9Ω, tan δ=1.12%, Pr=12.18μC/cm2; BCTZ-BCW陶瓷x=0.1%时,d33=555pC/N, kp=55.3%, r=8.6Ω, tan δ=1.2%, Pr=11.0μC/cm2。铁电温谱表明：BCTZ-0.1%BA陶瓷在-50℃时Pr达到饱和,TRT相变在30-40℃内；BCTZ-0.1%BY陶瓷在-60-20℃内Pr呈线性下降,TR-T相变在20-40℃内；BCTZ-0.1%BA, BCTZ-0.1%BY, BCTZ-0.1%BCW陶瓷的Tc变化依次为：Tc-BCW>Tc-BY＞Tc-BA。系统研究了BCTZ99-Ga, BCTZ99-In, BCTZ99-BCW体系陶瓷的组成与相结构、显微组织及电性能的影响关系,探讨陶瓷相变与铁电温谱的关系。结果表明：BCTZ99-In陶瓷的PPT相变在0.04≤x≤0.06内,晶粒均匀长大,Tc稍微降低；BCTZ99-Ga陶瓷的晶粒长大,Tc向高温推移；BCTZ99-BCW陶瓷的MPB在0.05%≤x≤0.20%内,晶粒均匀长大,Tc提高到127℃。陶瓷的最佳性能为：BCTZ99-In陶瓷x=0.06时,d33=507pC/N, kp=49.8%, tan δ=1.35%, Pr=14.9μC/cm2; BCTZ99-Ga陶瓷x=0.08时,d33=440pC/N, kp=56%, r=7.6Ω, Pr=15.3μC/cm2; BCTZ99-BCW陶瓷x=0.1%时,d33=300pC/N,kp=30%, tanδ=1.6%, Pr=14.8μC/cm2。铁电温谱表明：BCTZ99-0.08%Ga陶瓷的To-T相变在20-40℃内。对比研究了BCTZ与BCTZ99, BCTZ-0.08%In与BCTZ99-0.06%In, BCTZ-0.1%Ga与BCTZ99-0.08%Ga, BCTZ-0.1%BCW与BCTZ99-0.1%BCW陶瓷的εr-f关系, tan δ-f关系,θ-f关系,Z-f关系,介电弥散相变和压电性能的退极化规律。结果表明：BCTZ-0.08%In和BCTZ99-0.06%In陶瓷在40-10M Hz内均呈现低的tan δ,均属于硬性掺杂,增强并稳定了压电性能；BCTZ99-0.06%In陶瓷呈现弥散相变特征。BCTZ-0.1%Ga和BCTZ99-0.08%Ga陶瓷在40-10M Hz内均呈现低的tanδ和较高的εr,且均属于硬性掺杂,增强并稳定了压电性能；BCTZ99-0.08%Ga陶瓷呈现弥散相变特征。BCTZ99-0.1%BCW陶瓷主要表现出硬性掺杂,增强了温度稳定性,但压电性能降低；BCTZ-0.1%BCW陶瓷主要表现出软性掺杂,降低了压电性能和温度稳定性；BCTZ-0.1%BCW和BCTZ99-0.1%BCW陶瓷均呈现弥散相变特征。更多还原

【Abstract】 Abstract:Based on the fact that perovskite type of (Ba0.85Ca0.15)(Ti0.90Zr0.1)O3lead-free piezoelectric material have high piezoelectric properties, big dielectric constant, low dielectric loss, the less pollution of preparation and waste disposal, and according to the problems of high sintering temperature and the low Curie temperature. First, Ag2O and MnO2were added into BCTZ system ceramics respective, the sintering characteristics of the BCTZ system ceramics were studied. Secondly, In2O3, Ga2O3and Sb2O3were added into BCTZ system ceramics respective, the orderliness of crystal growth of the BCTZ system ceramics was studied. Third, BiAlO3, BiYbO3and Ba(Cu0.5W0.5)O3were compounded into BCTZ system ceramics respective, the orderliness of Curie temperature of the BCTZ system ceramics were studied. According to the previous results, In2O3, Ga2O3and Ba(Cu0.5Wo.5)03were added into BCTZ system ceramics respective, the orderliness of Curie temperature and crystal growth of the BCTZ system ceramics were studied. Last, the influence and mechanisms of In2O3, Ga2O3and Ba(Cu0.5W0.5)O3in the BCTZ and BCTZ99ceramics were studied by contrast. Several important conclusions can be summarized as follows:The relation between composition and crystalline structure, microstructure, density, electric properties of BCTZ-Ag and BCTZ-Mn new systems ceramics were systemically investigated. The influence of Ag2O, MnO2in the BCTZ and BCTZ99ceramics were studied by contrast. It was found that the Morphotropic Phase Boundary (MPB) for the BCTZ-Mn ceramic lies in the range of0.06≤x≤0.10; the Morphotropic Phase Boundary (MPB) for the BCTZ-Ag ceramic lies in the range of x=0.1. The best piezoelectric properties ofd33=616pC/N, kp=58.1%, r=5.6Ω, tan δ=0.63%for the BCTZ-Ag ceramic at x=0.08; d33=495pC/N,kp=49.6%, tan δ=1.58%,Pr=10.9μC/cm2for the BCTZ-Mn ceramic at x=0.08. The grain size of the BCTZ-0.08%Ag ceramic (50-90μm) is bigger than the BCTZ-0.08%Mn ceramic (30-40μm) by contrast. The relation between composition and crystalline structure, microstructure, density, electric properties of BCTZ-In, BCTZ-Ga and BCTZ-Sb new systems ceramics were systemically investigated. The relation between the ferroelectric properties as a function of temperature and the phase transformation for the ceramics were studied, and the influences on crystal growth of In2O3, Ga2O3and Sb2O3in the BCTZ ceramics were studied by contrast. It was found that the big grains of the BCTZ-In ceramics were increased gradually; the grains of BCTZ-Ga and BCTZ-Sb ceramics were grown up averagely. The best piezoelectric properties of d33=605pC/N, kp=51.1%, r=6.8Ω, tan δ=1.56%, Pr=11.1μC/cm2for the BCTZ-In ceramic at x=0.08; d33=705pC/N, kp=61%, r=5.2Ω, tan δ=1.75%, Pr=11.3μC/cm2for the BCTZ-Ga ceramic at x=0.10; d33=556pC/N,kp=52%, tan δ=1.3%, Pr=12.6μC/cm2for the BCTZ-Sb ceramic at x=0.10. It was found that TR-T of the BCTZ-0.1%Ga ceramic lies in the range of25-40℃; TR-T of the BCTZ-0.1%Sb ceramic lies in the range of20-40℃; Pr of BCTZ-0.1%Sb ceramic was reach the maximum value15μC/cm2in the range of-60-20℃by the ferroelectric properties as a function of temperature. The grain size of BCTZ-0.08%In, BCTZ-0.1%Ga, BCTZ-0.1%Sb and BCTZ ceramics were80μm,50μm,15μm and5μm by contrast.The relation between composition and crystalline structure, microstructure, density, electric properties of BCTZ-BA, BCTZ-BY and BCTZ-BCW systems ceramics were systemically investigated. The relation between the ferroelectric properties as a function of temperature and the phase transformation for the ceramics were studied, and the influences on the Curie temperature of BiAlO3, BiYbO3and Ba(Cu0.5W0.5)O3in the BCTZ ceramics were studied by contrast. It was found that Tc of the BCTZ-BA and BCTZ-BY ceramics were shifted to a lower temperature; Tc of the BCTZ-BCW ceramics were shifted to a higher temperature, and the Morphotropic Phase Boundary (MPB) lies in the range of0.05%≤x≤0.30%. The best piezoelectric properties of d33=536pC/N,kp=55.6%, tan δ=1.26%, Pr=10.8μC/cm2for the BCTZ-BA ceramic at x=0.1%; d33=580pC/N,kp=56.4%, r=10.9Ω, tan δ=1.12%, Pr=12.18μC/cm2for the BCTZ-BY ceramic at x=0.1%;d33=555pC/N, kp=55.3%, r=8.6Ω, tan δ=1.2%, Pr=11.0μC/cm2for the BCTZ-BCW ceramic at x=0.1%. It was found that Pr of BCTZ-0.1%Sb ceramic was reach the maximum value15μC/cm2at-50℃, and TR-T lies in the range of30-40℃; Pr of BCTZ-0.1%BY ceramic was linear decrease in the range of-60-20℃, and TR-T lies in the range of20-40℃by the ferroelectric properties as a function of temperature. The Curie temperature Tc of BCTZ-0.1%BA, BCTZ-0.1%BY and BCTZ-0.1%BCW ceramics were Tc-BCW>Tc-BY> Tc-BA by contrast.The relation between composition and crystalline structure, microstructure, density, electric properties of BCTZ99-Ga, BCTZ99-In and BCTZ99-BCW systems ceramics were systemically investigated, and the relation between the ferroelectric properties as a function of temperature and the phase transformation for the ceramics were studied. It was found that the Polymorphic Phase Transition (PPT) for the BCTZ99-In ceramic lies in the range of0.04<x<0.06, the grains of the ceramics were grown up averagely, Tc of the ceramics was shifted to a low temperature; the grains of the BCTZ99-Ga ceramics were grown up, and Tc was shifted to a high temperature; the Morphotropic Phase Boundary (MPB) for the BCTZ99-BCW ceramics lies in the range of0.05%≤x≤0.20%, the grains were grown up averagely, Tc of the ceramics was shifted to127℃. The best piezoelectric properties of d33=507pC/N, kp=49.8%, tan δ=1.35%, Pr=14.9μC/cm2for the BCTZ99-In ceramic at x=0.06; d33=440pC/N, kp=56%, r=7.6Ω, Pr=15.3μC/cm2for the BCTZ99-Ga ceramic at x=0.08; d33=300pC/N, kp=30%, tanδ=1.6%, Pr=14.8μC/cm2for the BCTZ-BCW ceramic at x=0.1%. TO-T of BCTZ99-0.08%Ga ceramics lies in the range of20-40℃by the ferroelectric properties as a function of temperature.Studied on comparing the relaxor characteristics and depolarization temperature, and the frequency dependence of the dielectric properties, impedance and phase angle of BCTZ and BCTZ99, BCTZ-0.08%In and BCTZ99-0.06%In, BCTZ-0.1%Ga and BCTZ99-0.08%Ga, BCTZ-0.1%BCW and BCTZ99-0.1%BCW ceramics. The results showed that tan δ of BCTZ-0.08%In and BCTZ99-0.06%In ceramics were all lower than the based ceramics in the range of40-10M Hz, the BCTZ-0.08%In and BCTZ99-0.06%In ceramics showed "hard" characteristics and have enhanced piezoelectric properties; The BCTZ99-0.06%In ceramic showed the relaxor characteristics. Tan δ of BCTZ-0.1%Ga and BCTZ99-0.08%Ga ceramics showed a low values, but εr of the ceramics showed a high values. The BCTZ-0.1%Ga and BCTZ99-0.08%Ga ceramics showed "hard" characteristics and have enhanced piezoelectric properties. The BCTZ99-0.08%Ga ceramic showed the relaxor characteristics. The BCTZ99-0.1%BCW ceramic clear showed "hard" characteristics, and had enhanced temperature stability, but reduced the piezoelectric properties of the ceramic. The BCTZ-0.1%BCW ceramic clear showed "soft" characteristics, and reduced the piezoelectric properties and temperature stability. The BCTZ-0.1%BCW and BCTZ99-0.1%BCW ceramics showed the relaxor characteristics.更多还原