0.91Pb(Zn1/3Nb2/3)O3-0.09PbTiO3的析晶行为及助溶剂法生长

研究了0.91Pb(znl/3Nb2/3)O3-0.09PbTiO3(PZNT91/9,摩尔分数)在不同组分和配比熔盐中的析晶行为及其对晶体生长的影响。发现B2O3,PbF2等助溶剂不利于钙钛矿相的析出;而BaTiO3-PbO复合体系虽然能够促进钙钛矿相析出,但晶体析出量很少;只有适当比例的。PbO助溶剂比较适合于生长具有铁电性的钙钛矿相PZNT91/9单晶。助溶剂法生长的工艺参数为:溶质与PbO助溶剂的摩尔比为l:l,泡料温度1 150-1 200℃,泡料时间10 h,晶体生长时降温速度0.8-2℃/h,当温度降到900℃时停止生长,以50℃/h快速冷却至室温。所得晶体为琥珀色,最大尺寸达φ30 mm×15 mm,其压电系数和机电偶合系数分别为2000 pc/N和0.92。     

Er3+替代Bi3+对Bi2(Zn1/3Nb2/3)2O7陶瓷烧结温度的影响

研究了Er3 替代Bi3 对Bi2(Zn1/3Nb2/3)2O7系介质材料结构和性能的影响,并借助X射线、扫描电镜、Agilent4284测试仪对其相结构和介电性能进行分析.研究结果表明:经Er3 替代的BZN陶瓷样品烧结温度升高(从960℃升高到1000℃);随着Er3 替代量的增加,Bi2(Zn1/3Nb2/3)2O7系介质材料的晶粒尺寸、介电常数、介电损耗都有所变化;当替代量x=0.1时,介电性能最佳,介电常数为78.7165,介电损耗为0.00134.     

Ba(Mg1/3Nb2/3)O3-Mg4Nb2O9复相陶瓷微波介电性能研究

采用传统固相法制备了(1?x)Ba(Mg1/3Nb2/3)O3?xMg4Nb2O9 [(1?x)BMN?xM4N2,x = 0.003 ~ 0.125] 微波介质陶瓷,研究了相结构、烧结性能与介电性能随 x 的变化规律。结果表明： BMN 与 M4N2 可以两相共存,且二者间存在有限固溶,BMN 的烧结温度及高温稳定性有所降 低。随着 x 的增大,介电常数 εr和谐振频率温度系数 τf逐渐减小,Q × f 值的变化易受到 BMN 有序参数 S 的影响,高度 1:2 有序的 x = 0.026 陶瓷获得了最大 Q × f 值 125000 GHz。综合来看, 在 1320°C 下保温 4 h 烧结的 x = 0.125 样品表现出最佳的微波介电性能：εr = 26.6,Q × f = 111000 GHz,τf = 5 ppm/ºC。     

Pb(Mg1/3Nb2/3)O3-PbZrO3-PbTiO3压电陶瓷的电学性能研究

采用固相烧结法制备了0.40Pb(Mg1/3Nb2/3)O3-(0.6-x)PbZrO3-xPbTiO3压电陶瓷,系统研究了其组分变化对晶体结构、介电和压电性能的影响。研究结果表明,所有样品均属于钙钛矿结构,无第二相产生。随着组分的变化,存在三方相向四方相的转变,并且在x = 0.38附近获得准同型相界组分,呈现出最优的电学性能,最高的压电系数d33 = 520 pC/N,居里温度TC = 238 °C,平面机电耦合系数kp = 0.60,厚度机电耦合系数kt = 0.52,纵向机电耦合系数k33 = 0.73。     

铁系固体超强酸Fe2O3/S2O2-8的制备及丁酸异戊酯的合成

Fe2O3/S2O8^2-超强酸是直接由Fe2O3制备而成。本文研究了焙烧温度对催化活性的影响，探索了催化酯化反应的最佳条件。实验结果表明：Fe2O3/S2O8^2-超强酸催化剂是一种性能良好的酯化催化剂，制备简单，能够循环使用，无三废污染，催化效率高，对丁酸异戊酯酯化率可高达96．02％。     

ZnO-B2O3-SiO2玻璃对Ca[（Li1／3Nb2／3）0.95Zr0.15]O3＋δ微波介电性能的影响陶瓷

研究了ZnO-B2O3-SiO2（ZBS）玻璃对陶瓷的烧结性能及微波介电特性的影响。研究表明ZBS的掺入能有效降低Ca[（Li1／3Nb2／3）0.95Zr0.15]O3＋δ陶瓷体系的烧结温度150-200℃,谐振频率温度系数随ZBS掺入量增加及烧结温度的提高,由负值向正值方向移动。在1000℃,掺入质量分数7wt％的ZBN,陶瓷微波介电性能最佳：εr=31．1,Qf=9550GHz,Tf=-8．9ppm／℃,在960℃烧结4小时,可获得介电性能为：εf=28．6,Qf=641OGHz,Tf=-9．8ppm／℃陶瓷样品。     

Zn3V2O8的电子结构与光学性质的理论研究

采用平面波超软赝势密度泛函理论的方法研究了Zn3V2O8的能带结构、电子态密度和光学特性.能带结果显示Zn3V2O8呈间接带隙的绝缘体型能带,其禁带宽度为2.9 eV.详细的电子态密度结果显示其费米面上的态密度达到20 e/eV,费米能级附近的能级由Zn3p、V3p和O2p电子形成,Zn3d和O2s之间有强的杂化作用.介电性能结果显示在4.4 ～5.7 eV附近有强的吸收峰,在20.6 eV附近有一个次强吸收峰;吸收光谱显示在6.8 eV处有强吸收,在20.7 eV处有一个较弱的吸收峰.     

纳米Ag@ZnO/Zn2Ti3O8的制备及光催化降解油田污水的研究

采用共沉淀法合成银锌钛纳米复合光催化剂,并通过XRD、SEM对其进行了表征.以油田污水中的石油类为降解物,探究其光催化效果.以溴酸钾、EDTA-2Na作为自由基捕获剂,探究银锌钛纳米复合物的光催化机理.XRD结果表明,该催化剂为Ag@ZnO/Zn2Ti3O8.SEM结果表明,其形貌为10～40 nm的纳米球组成的纳米棒...     

Ba缺位和烧结工艺对Ba1-xZn1/3Nb2/3O3陶瓷离子有序度和微波介电性能的影响

利用常规固相法制备了Ba1-xZn1/3Nb2/303(x=O～0.02)陶瓷,研究了Ba缺位对Ba1-xZn1/3Nb2/3O3陶瓷的相成分、B位离子长程有序度(LRO)和微波介电性能的影响规律.X射线衍射(XRD)结果显示,适量的Ba缺位可以提高材料的阳离子有序度,x=0.01时陶瓷具有最大的阳离子有序度;Ba缺位...     

铁电磁体Pb(Fe1/2Nb1/2)O3单晶高温熔液法生长及其结构特征研究

采用高温溶液晶体生长法,选择PbO为助熔剂,以缓慢冷却法获得过饱和度并施以温度振荡,生长出典型尺寸为3 mm×3 mm×3 mm的铁电磁体Pb(Fe1/2Nb1/2)O3单晶.用变温X射线衍射和变温Raman光谱研究了Pb(Fe1/2Nb1/2)O3单晶的结构对称性.结果表明Pb(Fe1/2Nb1/2)O3在实验的最低温度80 K到铁电相变温度383 K之间均为菱面体结构.在反铁磁相变温度Neel点以上,Pb(Fe1/2Nb1/2)O3体对角线逐渐变短,而在该温度以下,其结构没有变化.在测量的温度20～200 K范围内,Raman光谱的峰位不随温度变化,说明其结构在该温度范围内没有明显变化.实验结果将有利于进一步研究铁电磁体的形成机制.     

新型弛豫铁电单晶(1-x)Pb(Zn_(1/3)Nb_(2/3))O_(3-x)PbTiO_3生长的技术创新

(1-x)Pb(Zn_(1/3)Nb_(2/3))O_(3-x)PbTiO_3(PZNT)晶体是弛豫铁电体Pb(Zn_(1/3)Nb_(2/3)O_3与普通铁电体PbTiO_3组成的具有钙钛矿结构的固溶体,其准同型相界成分(x=0.09)附近表现出极其优异的压电性能,在医用超声成像、声纳、微位移器等方面具有广阔的应用前景,分析了PZNT-PbO赝二元系的析晶行为和相关系,总结了PZNT晶体的压电性能,讨论了生长工艺和成分对晶体性能的影响。针对PZNT晶体生长中存在的问题,发展了助熔剂-坩埚下降法、通气诱导成核技术、两步法生长工艺、区熔凝固技术、底部籽晶高温溶液法等多种生长技术,生长出大尺寸的PZNT晶体,并比较了这些生长技术的特点。     

Fabrication of 0.24Pb(In1/2Nb1/2)O3-0.42Pb(Mg1/3Nb2/3)O3-0.34PbTiO3 transparent ceramics by conventional sintering technique

0.24Pb(In_1/2Nb_1/2)O₃-0.42Pb(Mg_1/3Nb_2/3)O₃-0.34PbTiO₃ transparent ceramics were fabricated by a conventional sintering technique. Through optimization of sintering conditions of calcination and sintering temperatures and time, the obtained ceramics showed high optical transmittance of 53% and 71% at light wavelengths of 1300 and 2000 nm, respectively. The ceramics showed a rhombohedral to tetragonal phase transition at ~120°C and a tetragonal to cubic phase transition at 222°C. These transition temperatures were higher than those of 0.67Pb(Mg_1/3Nb_2/3)-0.33PbTiO₃ ceramics. In addition, the ceramics had a ferroelectric hysteresis loop, a large piezoelectric constant d₃₃ of 407 pC/N, and a planar electromechanical coupling factor k_p of 52%. These results suggest that the transparent ceramics may be used as a temperature-stable, linear electro-optic material.     

添加剂对Ba(Zn1/3Nb2/3)O3-Sr(Zn1/3Nb2/3)O3陶瓷介电性能的影响

研究了MnCO3,BaZrO3对0.35Ba(Zn1/3Nb2/3)O3(BZN)-0.65Sr(Zn1/3Nb2/3)O3(SZN)陶瓷介电性能的影响.研究表明:添加MnCO3,BaZrO3时,对陶瓷的烧结均起促进作用,增大介电常数.加入1%(质量分数)的MnCO3可使陶瓷具有较小的介质损耗,同时MnCO3对陶瓷的介电常数温度系数具有正向调整作用.加入BaZrO3后通过生成液相而减少了第二相Ba5Nb4O15,BaNb2O6的生成.所制备的(0.35BZN0.65SZN)+0.1%MnCO3陶瓷的εr≈43.6,αe≈-8×10-6/K,tanδ＝0.6×10-4,且烧结温度低于1 300℃.     

Growth and electrical properties of high-Curie point rhombohedral Mn-Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 thin films

High-quality ternary relaxor ferroelectric (100)-oriented Mn-doped 0.36Pb(In_1/2Nb_1/2)O₃-0.36Pb(Mg_1/3Nb_2/3)O₃-0.28PbTiO₃ (Mn-PIMNT) thin films were grown on SrRuO₃-buffered SrTiO₃ single-crystal substrate in a wide deposition temperature range of 550-620°C using the pulsed laser deposition method. The phase structure, ferroelectric, dielectric, piezoelectric properties, and nanoscale domain evolution were studied. Under the deposition temperature of 620°C, the ferroelectric hysteresis loops and current-voltage curves showed that the film owned significantly enhanced remnant ferroelectric polarization of 34.5 μC/cm² and low leakage current density of 2.7 × 10⁻¹⁰ A/cm². Moreover fingerprint-type nanosized domain patterns with polydomain structures and well-defined macroscopic piezoelectric properties with a high normalized strain constant of 40 pm/V was obtained. Under in situ DC electric field, the domain evolution was investigated and 180° domain reversal was observed through piezoelectric force microscope. These global electrical properties make the current Mn-PIMNT thin films very promising in piezoelectric MEMS applications.     

Structural origin of room temperature poling enhanced piezoelectricity in modified Pb(Mg1/3Nb2/3)O3‐30%PbTiO3 crystals

The piezoelectric properties of [110]‐oriented Mn‐doped Pb(Mg_1/3Nb_2/3)O₃‐30%PbTiO₃ single crystals was found to be enhanced by poling at room temperature, relative to traditional poling on field‐cooling (FC). High‐resolution x‐ray diffraction data revealed a phase transition sequence of cubic→tetragonal→ orthorhombic (O)→monoclinic B‐type (M_B) on field‐cooling with a phase coexistence of single domain O and M_B at 300 K in the FC state; whereas poling at room temperature revealed a M_B single phase. Accordingly, the structural origin of the piezoelectricity enhancement on poling at room temperature is attributed to a pure M_B phase. It is probable, in the FC state, that field‐cooling results in defect dipole migration, which then acts to stabilize regions of the O phase on cooling into the M_B one.     

Enhanced energy storage in temperature stable Bi0.5Na0.5TiO3-modified BaTiO3-Bi(Zn2/3Nb1/3)O3 ceramics

Recently, BaTiO₃-BiMeO₃ ceramics have garnered focused research attention due to their outstanding performance, such as thermal stability, energy efficiency and rapid charge-discharge behavior, however, a lower recoverable energy storage density (W_rec) caused by a relatively low P_max (<30 μC/cm²) mainly hinders practical applications. Herein, the energy density and thermal stability are improved by adding a tertiary component, i.e., Bi_0.5Na_0.5TiO₃, into BaTiO₃-BiMeO₃, resulting in xBi_0.5Na_0.5TiO₃-modified 0.88BaTiO₃-0.12Bi(Zn_2/3Nb_1/3)O₃ ceramics, with x = 0, 0.1, 0.2, 0.3 and 0.4, with superior dielectric properties and eco-friendly impact. Incorporating Bi_0.5Na_0.5TiO₃ with a high saturation polarization and Curie temperature not only significantly enhances P_max of BaTiO₃-Bi(Zn_2/3Nb_1/3)O₃ but also improves Curie temperature of (1-x)[0.88BaTiO₃-0.12Bi(Zn_2/3Nb_1/3)O₃]-xBi_0.5Na_0.5TiO₃ system. Combined with complementary advantages, modified ceramics render a superior energy storage performance (ESP) with a high W_rec of 3.82 J/cm³, efficiency η of 94.4% and prominent temperature tolerance of 25–200 °C at x = 0.3. Moreover, this ceramic exhibit excellent pulse performance, realizing discharge energy storage density W_dis of 2.31 J/cm³ and t_0.9 of 244 ns. Overall, the proposed strategy effectively improved comprehensive properties of BaTiO₃-based ceramics, showing promise in next-generation pulse applications.     

B位掺杂对Pb[(Mn1/3Nb2/3)0.5(Mn1/3Sb2/3)0.5]x(Zr0.825Ti0.175)1-xO3系陶瓷铁电畴反转的影响

用传统陶瓷工艺制备了Pb[(Mn1/3Nb2/3)0.5(Mn1/3Sb2/3)0.5]x(Zr0.825Ti0.175)1-xO3(其中x为B位掺杂的摩尔分数,下同)系铁电陶瓷,研究了室温条件下电滞回线的特性.结果显示:当x≤0.1时,电滞回线出现"束腰";当x=0.2时,"束腰"消失.用X射线光电子能谱、X射线衍射分析手段研究了"束腰"现象,并用氧缺位内偏场理论分析该现象的微观机理.结果表明:过量Mn偏析于晶界,使材料的晶界具有P型导电性,偏析Mn的量越多,晶界p型导电性越强,氧缺位钉扎电畴的能力下降,电畴容易反转,进而导致"束腰"现象消失.另外,随着x增大,剩余极化强度先增大后减小,矫顽场逐渐增大.     

Ferroelectric to Relaxor Transition in BaTiO3–Bi(Zn2/3Nb1/3)O3 Ceramics

The (1?x)BaTiO₃–xBi(Zn_2/3Nb_1/3)O₃ (x = 0.01–0.30) ceramics were synthesized by solid‐state reactions. The solubility limit was determined to be x = 0.20. A systematic structural transition from a tetragonal phase (x ≤ 0.034), to a mixture of tetragonal and rhombohedral phases (0.038 ≤ x ≤ 0.20), and finally to a pseudocubic phase (x ≥ 0.22) at room temperature was identified. Dielectric measurement revealed a ferroelectric (x ≤ 0.04) to relaxor (x ≥ 0.06) transition with permittivity peak broadening and flattening, which was further verified by Raman spectroscopy and differential scanning calorimetry (DSC). Activation energies obtained from the Vogel–Fulcher model displayed an increasing trend from ~0.03 eV for x ~ 0.05, to unusually high values (>0.20 eV) for the compositions with x ≥ 0.15. With the increase in Bi(Zn_2/3Nb_1/3)O₃ content, the polarization hysteresis demonstrated a tendency from high nonlinearity to sublinearity coupled with the reduction in remnant polarization and coervice field. The deconvolution of the irreversible/reversible polarization contribution was enabled by first‐order reversal curve distributions, which indicates that the decreasing polarization nonlinearity with the increase in Bi(Zn_2/3Nb_1/3)O₃ concentration could be related with the change from the ferroelectric domain and domain wall contributions to the weakly coupled relaxor behaviors.