Processing mediated enhancement of ferroelectric and electrocaloric properties in Ba(Ti0.8Zr0.2)O3–(Ba0.7Ca0.3)TiO3 lead-free piezoelectrics

High-performance Ba(Ti_0.8Zr_0.2)O₃–(Ba_0.7Ca_0.3)TiO₃ (BCZT) fiber crystals were grown using laser-heated pedestal growth (LHPG) for a systematic investigation of processing effects on structure and physical properties. By changing the growth rate (200−5 mm/h), fiber crystals with varying stoichiometry were realized: controlled composition, Ba_0.872Ca_0.128Ti_0.925Zr_0.075O_3-δ, for the optimized crystal (5 mm/h), relative to the ceramic sample (SS) synthesized by the ceramic method. SS and optimized fibers exhibited larger energy storage densities of 700 and 868 mJ/cm³, respectively. Electrocaloric (EC) measurements by direct and indirect methods yielded ΔT of 1.3 K & 0.95 K and EC responsivity (ΔT/ΔE) of 0.3 and 0.43 K mm/kV for SS and 5 mm/h respectively, at 30 kV/cm, at least two-folds higher compared to 200 mm/h fiber. The EC responsivity of our samples is comparable to that of Pb(Mg,Nb)O₃ crystals. These results demonstrate that BCZT has potential application as EC elements when the composition is controlled by fine-tuning of growth parameters.     

Structure and physical properties of Ba(PO3)2–AlF3–BaSO4 fluoro-sulfo-phosphate glasses

Alkali-earth-metaphosphate-based fluoro-sulfo-phosphate M(PO₃)₂–AlF₃–MSO₄ (MPFS, M = Ca, Sr, Ba) glasses have been developed via simultaneously incorporating fluoride and sulfate into metaphosphate glass. Their glass-forming regions were efficiently determined under the guidance of thermodynamic calculation method. The physical and structural properties of BaPFS glass were investigated in detail. Furthermore, near-infrared spectroscopic properties of Er³⁺-doped BaPFS (Er–BaPFS) glass were studied. Physical parameters, such as Abbe's number ν_d (55-75) and nonlinear refractive index n₂ (1.17-1.86 × 10⁻¹³ esu), of BaPFS glass are strongly depended on P/F/S ratio. The structure of BaPFS glass gradually depolymerizes and tends to become multianionic when Ba(PO₃)₂ is substituted by AlF₃ and BaSO₄. Anion-substitution strategy effectively modulates the property and structure of glass, providing a scheme to derive glass materials. In addition, enhanced emission at ~1.5 μm has been observed from Er–BaPFS glass along with large emission cross section (5.0-5.5 × 10⁻²¹ cm²) and long lifetime (6.7-7.3 ms), resulting in large figure of merit (3.46-3.84 × 10⁻²³ cm²·s), which is a promising candidate for solid-state laser.     

Aging effect in Er3+-doped 0.5Ba(Zr0.2Ti0.8)O3–0.5(Ba0.7Ca0.3)TiO3 ceramics

Usually, aging in poled ferroelectrics leads to degradation of certain physical properties. In this study, we found a remarkable aging effect in tetragonal Er³⁺-doped 0.5Ba(Zr_0.2Ti_0.8)O₃–0.5(Ba_0.7Ca_0.3)TiO₃ (BZT-BCT) ceramics after poling. It is observed that the domains can spontaneously rotate to keep their spontaneous polarization direction similar to that of the poling electric field during aging for the poled ceramics. Furthermore, compared with freshly poled ceramics, the thermally stimulated current (TSC) peak of the aged ones shifts toward a higher temperature (10°C). And the temperature of the TSC peak in the aged ceramics is exactly equal to their Curie temperature. Such features indicate that aging for the poled ceramics could stabilize the alignment of ordered ferroelectric domains. Additionally, a downward TSC peak above Curie temperature is obtained in both poled and aged ceramics, demonstrating that poling and aging can lead to ordered alignment of defect dipoles. The aging mechanism of poled Er³⁺-doped BZT-BCT ceramics has proposed and discussed in this article.     

Origin of superior dielectric and piezoelectric properties in 0.4Ba(Zr0.2Ti0.8)O3–0.6(Ba0.7Ca0.3)TiO3 at intermediate grain sizes

Grain size effect is one of the most important issues to develop next-generation multilayer microdevices. In this work, the tetragonal 0.4Ba(Zr_0.2Ti_0.8)O₃–0.6(Ba_0.7Ca_0.3)TiO₃ (BZT–60BCT) ceramics with a wide grain size from 2.1 to 24 μm were successfully prepared by using ultrafine nano powder and two-step sintering. The results demonstrate that critical/intermediate grain size of dielectric constant ε_r and piezoelectric constant d₃₃ appears at ∼12.9 μm. It was found that the presence of large lattice tetragonality, and enhanced domain wall motion induced by domain coexistence between submicron and nano size in sample with a grain size of ∼12.9 μm, resulting in the superior dielectric and piezoelectric properties. These findings and analyses of the origin of superior dielectric and piezoelectric properties at intermediate grain size have important practical implications in the design of high-performance piezoelectric ceramics.     

Effects of microstructure on the microwave dielectric properties of Ba(Co1/3Nb2/3)O3 and (1−x)Ba(Co1/3Nb2/3)O3–xBa(Zn1/3Nb2/3)O3 ceramics

Ba(Co_1/3Nb_2/3)O₃(BCN) has a 1:2 ordered hexagonal structure. A large amount of the liquid phase, which contains high concentrations of Ba and Nb ions was found in the BCN ceramics. Q-values of BCN increased with increasing sintering temperature; however, it significantly decreased when the sintering temperature exceeded 1400 °C. The presence of a large amount of liquid phase could be responsible for the decrease of the Q-value. For (1−x)Ba(Co_1/3Nb_2/3)O₃–xBa(Zn_1/3Nb_2/3)O₃ [(1−x)BCN–xBZN] ceramics, the 1:2 ordered hexagonal structure was observed in the specimens with x⩽0.3 and the BaNb₆O₁₆ second phase was found in the specimens with x⩾0.6. Grain growth, which is related to the BaNb₆O₁₆ second phase occurred in the specimens with x⩾0.5. In this work, the excellent microwave dielectric properties of τ_f=0.0 ppm/°C, ε_r=34.5 and Q×f=97,000 GHz were obtained for the 0.7BCN–0.3BZN ceramics sintered at 1400 °C for 20 h.     

Ba3Tb(BO3)3:Eu3+的制备与发光性质

采用高温固相法合成了Ba3Tb(BO3)3:Eu3+红色荧光粉,并研究了Ba3Tb(BO3)3:Eu3+的发光特性。Ba3Tb(BO3)3:Eu3+的激发光谱包含250nm～330nm和350nm～400nm的2个宽带,最大峰值位于383nm,可以被紫外-近紫外发光二极管(light-emitting diodes,LED)有效激发。Ba3Tb(BO3)3:Eu3+的发射谱显示出4组发射峰,其主发射峰位于620nm,对应Eu3+的5D0→7F2跃迁;Eu3+掺杂摩尔分数为2%时,Ba3Tb(BO3)3:Eu3+发光亮度最高。经分析发现Ba3Tb(BO3)3:Eu3+存在Tb3+→Eu3+的能量传递。     

水热法合成Ba(Ti_(0.8)Zr_(0.2))O_3纳米粉体

钛酸钡(BaTiO_3)系列电子材料是一类重要的功能材料,正逐渐向小体积、功能化、大容量方向发展,常采用掺杂改性的方式提高其介电常数及稳定性。本次实验主要以TiCl_4、BaCl_2·2H_2O、ZrOCl_2、NaOH为原料,采用水热合成法制备锆钛酸钡[Ba(Ti_(0.8)Zr_(0.2))O_3,BZT]纳米粉体,并探讨反应温度、Ba/(Ti+Zr)摩尔比以及pH对BZT粉体合成的影响。实验结果表明,在反应温度为220℃,反应时间为4h,Ba/(Ti+Zr)=1.4,且pH为14时制备的BZT粉体物相单一,分散性较好,粒径较小。当提高pH及前驱物的Ba/(Ti+Zr)摩尔比及升高反应温度时,均有利于BZT晶体形成,而且粉体粒径减小。     

中温烧结(Ba、Sr)TiO3电容器陶瓷

采用常规电容器陶瓷制备工艺 ,借助正交设计实验法研究了在配方对中温烧结 (12 0 0℃ ) (Ba,Sr)TiO3 (BST)基陶瓷介电性能的影响 ,得到了影响BST基陶瓷介电性能的主次因素以及各因素水平影响其性能的趋势 ,同时得到介电常数最大的配方和介质损耗最小的配方 ,得到了综合性能最佳的适合单片电容器和独石电容器的中温烧结 (12 0 0℃ )BST基陶瓷基方 ,它具有中介 (ε≥ 2 195 )、低损耗 (tanδ≤ 0 .0 15 5 )和高耐压 (大于 4 .5Mv/m)。探讨了各组分对BST基陶瓷介电性能的影响机理 ,为研制中温烧结单片电容器和独石电容器陶瓷提供了依据     

(1-x)Ba(Mg1/3Nb2/3)O3-xBaSnO3陶瓷的微波介电性能

用传统陶瓷制备方法制备了(1-x)Ba(Mg1/3Nb2/3)O3-xBaSnO3[0.0≤x≤0.3,(1-x)BMN-xBS]体系微波介质陶瓷,研究了该陶瓷的微观结构和微波介电性能.用X射线衍射仪研究陶瓷的晶体结构.用扫描电镜观察陶瓷的显微结构.用网络分析仪测试陶瓷的微波介电性能.结果表明:晶格常数c和a均随x值的增加而增加;晶格常数比(c/a)随x值的增加而减小.当x≥0.1时,1∶2有序衍射峰消失.陶瓷的平均晶粒尺寸在0.7～2 μm之间.随x值的增加,陶瓷的相对介电常数(εr)和谐振频率温度系数(τr)呈线性减小;品质因数与谐振频率的乘积(Qf)呈非线性变化.当x=0.15时,Qf达到最大值,为86 200 GHz.当x=0.3时,在此体系中可以获得τf接近零的微波介质陶瓷Ba(Sn0.3Mg0.233Nb0.467)O3,其微波介电性能如下:εr=26.1;Qf=42 500GHz;τr=4.3×10-6/℃.     

Ball milling–based piezocatalysis using .5Ba(Zr0.2Ti0.8)O3–.5(Ba0.7Sr0.3)TiO3 ceramics

One of the newly light on processes utilized in applications for cleaning water is piezocatalysis. Mechanical vibrations generated through ultrasonication are generally used to separate out the charges in ferroelectric ceramics. The current research presents a novel prospective methodology of ball milling, where it is used as a facile and green technique for water remediation. The movement of the planetary ball mill imparts enough force such that reactive species are produced which are responsible for organic dye degradation. One of the results in the parametric analysis showed that by using 0.30 g of the 0.5Ba(Zr_0.2Ti_0.8)O₃–0.5(Ba_0.7Sr_0.3)TiO₃ (BST–BZT) powder, 62% of the methylene blue (MB) dye was degraded in 60 minutes.     

共沉淀法制备(Ba、Sr)TiO_3粉体的研究

以无机盐为原料 ,用共沉淀法制备了电子陶瓷 ( Ba、Sr) Ti O3系列粉体材料 ,确定了前驱体最佳锻烧工艺条件为温度 1 1 50℃ ,时间为 2 h,并用热分析研究了前驱体在锻烧过程中的质能变化情况 ,讨论了 ( Ba、Sr)Ti O3粉体的生成机理 ,并用 X- ray衍射分析对 ( Ba、Sr) Ti O3进行了表征 ,表明 ( Ba、Sr) Ti O3为一新的均相化合物 ,用图解外推法计算了系列产品的晶胞常数。     

共沉淀法制备(Ba、Sr)TiO3粉体的研究

以无机盐为原料 ,用共沉淀法制备了电子陶瓷 ( Ba、Sr) Ti O3系列粉体材料 ,确定了前驱体最佳锻烧工艺条件为温度 1 1 50℃ ,时间为 2 h,并用热分析研究了前驱体在锻烧过程中的质能变化情况 ,讨论了 ( Ba、Sr)Ti O3粉体的生成机理 ,并用 X- ray衍射分析对 ( Ba、Sr) Ti O3进行了表征 ,表明 ( Ba、Sr) Ti O3为一新的均相化合物 ,用图解外推法计算了系列产品的晶胞常数。     

Synthesis and Characterization of Lead-Free Ferroelectric 0.5[Ba(Zr0.2Ti0.8)O3]–0.5[(Ba0.7Ca0.3)TiO3]—Polyvinylidene Difluoride 0–3 Composites

0.5[Ba(Zr_0.2Ti_0.8)O₃]–0.5[(Ba_0.7Ca_0.3)TiO₃]/[BZT–BCT]–polyvinylidene difluoride/[PVDF] 0–3 composites were prepared by uniaxial hot-press method for different volume fractions of BZT–BCT ceramic powder in a PVDF polymer matrix. The structural, microstructural and dielectric properties were investigated and discussed. There was an increase in relative permittivity (ε_r) and dielectric loss (tan δ) of the composites with increase in the volume fraction of the ceramics. At room temperature and at 1 kHz frequency, 0.25[BZT–BCT]–0.75[PVDF] composite showed a highest relative permittivity (ε_r) ~41.     

Preparation and properties of (Ba0·7Sr0·3)TiO3 powders and thin films using precursor solutions formed from alkoxide-hydroxide

(Ba_0·7Sr_0·3)TiO₃ powders and thin films were prepared using alkoxide-hydroxide route. Solutions of Ba and Sr hydroxides dissolved in methanol were reacted with Ti-isopropoxide under conditions of stirring at room temperature for 15 h, and then dried under reduced pressure at ≦40°C to prepare precursors of (Ba_0·7Sr_0·3)TiO₃ powder. The amorphous precursors were hydrolyzed at 100°C by introducing nitrogen gas containing water vapor. The hydrolyzed products were crystalline nanosize powders of (Ba_0·7Sr_0·3)TiO₃. As-hydrolyzed (Ba_0·7Sr_0·3)TiO₃ powders showed a good crystallinity with cubic phase. (Ba_0·7Sr_0·3)TiO₃ thin films were also successfully prepared at 650°C on Pt/Ti/SiO₂/Si substrates from precursor solutions obtained by the reaction of alkoxide with hydroxides. The (Ba_0·7Sr_0·3)TiO₃ thin films exhibited the microstructure with fine grains as small as 20–60 nm. The dielectric constants of the thin films ranged from 600 to 800 at room temperature.     

Microwave-assisted sintering and improved dielectric,ferroelectric properties of 0.5[(Ba0.7Ca0.3)TiO3]–0.5[Ba(Zr0.2Ti0.8)O3] lead-free ceramics

0.5[(Ba_0.7Ca_0.3)TiO₃]–0.5[Ba(Zr_0.2Ti_0.8)O₃] lead-free ceramics were synthesised by coprecipitation method and sintered by fast microwave sintering (MWS) and by conventional sintering (CS) at 1200°C. After being sintered with the two different methods, the materials were characterised for structural, microstructural, frequency and temperature-dependent dielectric properties, Raman spectroscopy, and ferroelectric measurements. Results are compared and discussed in the present paper. X-ray diffraction confirms the presence of the tetragonal and rhombohedral phases in the composites sintered by both methods. The ferroelectric to paraelectric transition temperature (Tc) is increased in microwave-sintered composite. Diffuse constant (γ) values show BCT–BZT ceramics to be neither normal ferroelectrics nor relaxor ferroelectrics. Raman spectra confirm phase transition in the ceramic samples. Saturation polarisation (Ps) values are 7.62 and 4.28?µC?cm^?2 and nearly equal remanant polarisation (Pr) values were observed for BCT–BZT composite sintered with MWS and CS, respectively.     

Bi_4Ti_3O_(12)掺杂(Ba,Sr)TiO_3基电容器陶瓷介电性能研究

采用传统固相法制备了Bi_4Ti_3O_(12)掺杂(Ba_(0.71),Sr_(0.29))TiO_3(BST)陶瓷。研究了Bi_4Ti_3O_(12)掺杂量对BST电容器陶瓷介电性能、物相组成和微观结构的影响。结果表明:随着Bi_4Ti_3O_(12)掺杂的增加,BST陶瓷的相对介电常数逐渐减小,介电损耗先减小然后增大,Bi_4Ti_3O_(12)掺杂后的BST陶瓷仍为钙钛矿结构。当Bi_4Ti_3O_(12)掺杂量为1.6 wt%时,BST陶瓷的综合介电性能最好,εr为3744,tanδ为0.0068,ΔC/C为+1.70%,-44.61%,容温特性符合Y5V特性。     

Structural,dielectric and ferroelectric properties of Ba1−x(Bi0.5Na0.5)xTiO3 ceramics

Lead free Ba_1?x(Bi_0.5Na_0.5)_xTiO₃ (x=0, 0.02, 0.04, 0.06, 0.08, 0.1) ferroelectric ceramics were synthesized by conventional solid state reaction technique. Sintering was done at 1200 °C for 2 h in air atmosphere. The final products have tetragonal symmetry with decreasing c/a ratio confirmed by X-ray diffraction analysis. The grain size varies between 300 nm to 1000 nm for x=0 to 0.1. With increase in Bi_0.5Na_0.5TiO₃ [BNT] content, the room temperature permittivity decreases whereas the Curie temperature (T_c) increases and its highest value was found to be 155 °C for 10 mol% of BNT addition. The ceramics show stable and low dielectric loss characteristics. The remnant polarization (P_r) and the coercive field (E_c) increases monotonously with increase in BNT content. The highest value of 2P_r (=17 μC/cm²) and 2E_c (=22 Kv/cm) was obtained for x=10 mol% BNT addition.     

Dielectric properties and diffuse phase transition behavior of CuO-doped lead-free Ba(ZrxTi1−x)O3 ceramics

CuO-doped lead-free Ba(Zr_0.2Ti_0.8)O₃ (BZT20) ceramics were prepared through a solid state processing technique, and the effects of CuO on microstructure, dielectric properties and diffuse phase transition behavior were investigated. The average grain sizes were increased by CuO doping. The temperature and frequency dependences of the dielectric constant revealed that CuO-doped BZT20 ceramics exhibited broad diffuse phase transition behavior. The dielectric constant increased with increasing CuO concentration. The value of T_m and degree of diffusion (γ) changed regularly in the studied compositional ranges. The BZT20 samples with 1.0 mol% CuO doping, sintered at 1310 °C, showed excellent dielectric property and lower diffusivity with ε_m=21,371 and γ=1.87. These results can be explained by the disordered distribution of Cu ions in the B sites and the weakened bonding force with oxygen ions in Cu substituted BZT20 structure.     

异质界面个数对PbZr_(0.52)Ti_(0.48)O_3/Ba(Mg_(1/3)Ta_(2/3))O_3薄膜铁电性能的影响

采用溶胶-凝胶法制备PbZr_(0.52)Ti_(0.48)O_3(PZT)薄膜前驱体溶液,采用水溶液凝胶法制备Ba(Mg_1/_3Ta_2/_3)O_3(BMT)薄膜前驱体溶液。研究了异质界面个数对PZT/BMT薄膜微观形貌、铁电性能的影响。在PZT/BMT薄膜中,PZT薄膜没有裂纹、结晶良好,界面个数的增加有利于PZT薄膜结构的致密。界面个数的增加可降低PZT/BMT薄膜剩余极化值和矫顽场。PZT/BMT薄膜在适当偏置电场下存在一个介电峰值,且正负偏置电场下的介电峰值不同,介电偏压特性曲线呈现不对称分布。采用二极管等效界面势垒和对薄膜电滞回线求导可有效解释介电偏压特性曲线不对称和介电峰值的差异。     

Design and characterization of novel manganite perovskites Ba1-xBixTi1-xMnxO3 (0≤x≤0.2)

Polycrystalline manganite powders of Ba_1-xBi_xTi_1-xMn_xO₃ (x = 0, x = 0.1 and x = 0.2) were synthesized by the conventional solid-state reaction process. Their crystal structure, morphological, optical, dielectric and electrical properties were investigated. X-ray diffraction of the prepared samples was made at room temperature and confirmed the formation of a perovskite phase. Structural refinement, using the Rietveld method, revealed a tetragonal P4mm phase of pure BTO and a tetragonal P4/mmm phase with the presence of vacancies for both doped samples (x = 0.1 and x = 0.2). Scanning electron microscopy indicated that the perovskite samples had a grain size smaller than 1 μm. From UV–vis–NIR spectra, we found that the band gap reduces from 3.29 eV to 1.48 eV with the increase of Bi and Mn amounts, resulting in a shift of the absorption wavelength region toward the visible range. Dielectric analysis was conducted in a wide range of temperatures at different frequencies. Phase transitions were identified from thermal dielectric results, showing that the samples exhibited a non-relaxor behavior. The structural transformation from tetragonal to cubic structure corresponding to the transition from ferroelectric phase to paraelectric phase was observed in the dielectric properties investigation. The complex impedance spectroscopy indicated the presence of grain and grain boundary effects in the conduction mechanism. Electrical analysis showed that doping with Bi and Mn enhanced the DC conductivity. Furthermore, the DC conductivity temperature dependence confirmed that the studied samples present a semiconductor behavior. The activation energies of grain and grain boundaries depended on the amount of incorporated Bi and Mn. The activation energy of grain varied between 0.54 and 0.87 eV suggesting that the DC electrical conductivity is governed by ionized oxygen vacancies. The activation energy of grain boundaries varied between 0.85 and 0.58 eV.