Preparation and Dielectric Properties of Mn-Doped Ba0.6Sr0.4TiO3-MgTiO3 Composite Ceramics

Barium strontium titanate (Ba_0.6Sr_0.4TiO₃, BST) nano-powders were prepared using Ba(NO₃)₂, Sr(NO₃)₂, oxalic acid dehydrate, and tetrabutyl titanate (Ti(OC4H9)4) as precursors by the chemical co-precipitation method. The product was characterized by thermogravimetry-differential scanning calorimetry (TG-DSC) thermal analyses, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The experimental results indicated that the resulting Ba_0.6Sr_0.4TiO₃ nano-powders were homogeneous with agglomerated nature. The Ba_0.6Sr_0.4TiO₃-MgTiO₃ (BST-MT) bulk composite ceramics doped by Mn were obtained by the traditional solid phase method. The XRD patterns demonstrated that Mn-doped BST was unable to change the perovskite crystalline structure of BST materials. SEM photographs revealed that the crystalline grains became larger with increasing the content of doping Mn (<1.5% (x, molar fraction)) and then the size of grains decreased after the Mn content exceeded 1.5% in the BST ceramics, suggesting the effect of Mn doping on the morphologies of BST-MT composites. The dielectric properties of BST-MT composite ceramics doped with 0.1%-2.0% (x) Mn were investigated systematically. Two effects of Mn doping on the dielectric properties of the BST-MT composite ceramics were observed. At low Mn doping concentrations (<1.5%), Mn mainly acted as an acceptor dopant to replace Ti at the B site of ABO3 perovskite structure, leading to a diffused phase transition. It was also observed that the grain size increased drastically as the Mn content increased and thus caused the decrease of dielectric loss. At higher Mn doping concentrations (>1.5%), the grain size decreased and the suppression of permittivity and the drastic increase of the dielectric losses were observed, which indicated a “composite” mixing effect.     

锰掺杂Ba0.6Sr0．4TiO3-MgTiO3复相陶瓷的制备和介电性能

以分析纯的Ba(NO3)2、Sr(NO3)2、草酸和钛酸丁酯为原料,采用草酸盐共沉淀法制备了钛酸锶钡(Ba0.6Sr0.4tiO3,BST)纳米粉体.XRD和SEM分析结果表明,该方法制备出立方相的Ba0.6Sr0.4TiO3粉体,平均粒径小于100 nm,具有较高的烧结活性.用传统固相法制备了锰掺杂钛酸锶钡.钛酸镁(Ba0.6Sr0.4TiO3-MgTiO3,BST-MT)复相陶瓷,系统研究了掺杂0.1%-2.0%(x,摩尔分数,下同)锰对钛酸锶钡-钛酸镁复相陶瓷微观形貌和介电性能的影响机理.结果表明,当锰的掺杂量小于1.5%时,Mn作为受主掺杂取代占据钙钛矿ABO3的B位,因此导致居里点略微向高温偏移和相变扩散的发生,锰的掺杂导致晶格畸变,促进了晶粒生长,使晶界相比例下降,因此介电损耗随着锰掺杂量的增大而减小;当锰的掺杂量为1.5%时,介电损耗达到最小值,继续增大掺杂量,介电常数下降,介电损耗上升.     

Bi4(Ti1/3Sn2/3)3O12掺杂BaTiO3基X8R陶瓷微观结构与介电性能

研究了Bi4(Ti1/3Sn2/3)3O12掺杂对钛酸钡基陶瓷微观结构和介电性能影响。结果表明,掺杂Bi4(Ti1/3Sn2/3)3O12后钛酸钡基陶瓷晶粒明显长大,同时烧结温度可由1 280℃降低至1 180℃。系统的介电性能和Bi4(Ti1/3Sn2/3)3O12的掺杂量有密切关系。当Bi4(Ti1/3Sn2/3)3O12的掺杂量从0.5mol%增加到2mol%,体系的居里峰被明显压低和展宽,当掺杂量为2mol%时居里峰变得不明显。当Bi4(Ti1/3Sn2/3)3O12的掺杂量从0.5mol%增加到2mol%,系统的居里温度由131℃升高至139℃。当Bi4(Ti1/3Sn2/3)3O12的掺杂量为1mol%时,钛酸钡基陶瓷介电常数为1 930,介电常数温度变化率为5%(-55℃),13%(134℃),-8%(150℃),满足X8R标准。     

Diffusion of Sr and Zr in BaTiO3 single crystals

The diffusion of strontium and zirconium in single crystal BaTiO₃ was investigated in air at temperatures between 1000 °C and 1250 °C. Thin films of SrTiO₃, deposited by spin coating a precursor solution and thin films of zirconium, deposited onto the sample surfaces by sputtering, were used as diffusion sources. The diffusion profiles were measured by SIMS depth profiling on a time-of-flight secondary ion mass spectrometer (ToF-SIMS). The diffusion coefficients of strontium and zirconium were given by D_Sr = 3.6 × 10^2.0±4.4 exp[−(543 ± 117) kJ mol⁻¹/(RT)] cm² s⁻¹ and D_Zr = 1.1 × 10^1.0±2.1 exp[−(489 ± 56) kJ mol⁻¹/(RT)] cm² s⁻¹. The results are discussed in terms of different diffusion mechanisms in the perovskite structure of BaTiO₃.     

Structure and infrared emissivity of silicon-containing polyimide/BaTiO3 nanocomposite films

Silicon-containing polyimide/BaTiO₃ nanocomposite films were prepared by the direct mixing of silicon-containing polyamic acid and BaTiO₃ nanoparticles under ultrasonic wave irradiation, followed with thermal imidization. Structure and thermal properties were measured with FTIR, XPS, SEM, DSC and TGA. The results showed that the compatibility of BaTiO₃ and a polyimide might be improved by the introduction of dimethylsilylene groups into the backbone of a polyimide; and BaTiO₃ nanoparticles in the nanocomposites tended to form clusters. The clusters coalesced into a more uniform structure at a higher BaTiO₃ filling than at a lower one.The interfacial interaction between BaTiO₃ and the silicon-containing polyimide resulted in the increase of the glass transition and the thermal decomposition temperature. It was found that the nanocomposites exhibited lower infrared emissivity value than the pure polyimide and the magnitude of infrared emissivity value was related to the content of BaTiO₃ in the nanocomposites.     

Nd2O3添加量对BaTiO3陶瓷介电性能的影响

BaTiO₃ ceramics doped with Nd₂O₃(the additive content was respectively 0.001,0.002,0.003,0.005,0.01,0.03mol)were prepared by Sol-Gel method. Effects of Nd₂O₃ contents on the dielectric constant (ε), the dielectric loss (tanδ) ,the Curie-temperature (T_C) and the resistivity (ρ) of BaTiO₃ ceramic were studied. When Nd₂O₃ content was 0.001mol and 0.002mol, the dielectric constant was increased obviously, but the dielectric loss was also increased. When Nd₂O₃ content was 0.003mol, the dielectric constant was increased, and the dielectric loss was decreased, which was suitable for application in condenser. The resistivity was decreased obviously with the increasing of Nd₂O₃ contents, the resistivity was the smallest when Nd₂O₃ content was 0.001mol. The Curie-temperature was also decreased with the increasing of Nd₂O₃ contents.     

铁和铈对光还原分离铕的影响

镧系元素的f→d跃迁和荷移跃迁带用相应波长的光激发会导致相应元素发生光氧化和光还原。在能形成高价的元素中,Ce~(3+)最易发生光氧化。     

Dye-sensitized solar cells made from BaTiO3-coated TiO2 nanoporous electrodes

We reported on the preparation of a thin BaTiO₃-coated layer (2.27 nm) on the surface of TiO₂ and its further application in the dye-sensitized solar cells (DSCs). The as-prepared BaTiO₃–TiO₂ films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscope (TEM). The performances of the DSCs with and without BaTiO₃ coating were analyzed by cyclic voltammograms (CVs), electrochemical impedance spectroscopy (EIS), and current–voltage measurements. It was found that the BaTiO₃–TiO₂ films with about 12 μm thickness increased the dye adsorption, resulting in increased J_sc. In the meantime, the BaTiO₃ modification on the TiO₂ surface is beneficial to the formation of an energy barrier against the electron transfer from TiO₂ to I₃⁻, providing the increase of V_oc due to the increased electron density in the TiO₂ that is caused by the increased electron lifetime.     

锰掺杂Ba0.6Sr0.4TiO3-MgTiO3复相陶瓷的制备和介电性能

以分析纯的Ba(NO3)2、Sr(NO3)2、草酸和钛酸丁酯为原料, 采用草酸盐共沉淀法制备了钛酸锶钡（Ba0.6Sr0.4TiO3, BST）纳米粉体. XRD和SEM分析结果表明, 该方法制备出立方相的Ba0.6Sr0.4TiO3粉体, 平均粒径小于100 nm, 具有较高的烧结活性. 用传统固相法制备了锰掺杂钛酸锶钡-钛酸镁(Ba0.6Sr0.4TiO3-MgTiO3, BST-MT)复相陶瓷, 系统研究了掺杂0.1%-2.0%(x, 摩尔分数, 下同)锰对钛酸锶钡-钛酸镁复相陶瓷微观形貌和介电性能的影响机理. 结果表明, 当锰的掺杂量小于1.5%时, Mn作为受主掺杂取代占据钙钛矿ABO3的B位, 因此导致居里点略微向高温偏移和相变扩散的发生, 锰的掺杂导致晶格畸变, 促进了晶粒生长, 使晶界相比例下降, 因此介电损耗随着锰掺杂量的增大而减小; 当锰的掺杂量为1.5%时, 介电损耗达到最小值, 继续增大掺杂量, 介电常数下降, 介电损耗上升.     

掺镁钛酸钡纳米棒的水热合成和光催化性能

用水热法制备掺镁钛酸钡(Ba1-xMgxTiO3(x=0,0.10,0.20,0.30,0.40),BMT)纳米粉体。运用X射线衍射仪(XRD)、场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM)、紫外可见漫反射光谱技术(DRS)等手段对样品进行了表征,并在可见光照射下于溶液中考察了其光催化降解甲基橙反应活性。结果表明,通过控制氢氧根浓度可以得到不同形貌的纳米粉体。基于不同条件下制备的样品的微结构分析,提出了这些不同形貌的形成机制。制备出的BMT材料的带隙能约为2.61 eV。光催化反应结果表明BMT的光催化活性比掺氮TiO2高得多。OH-浓度为8 mol·L-1时制备的BMT纳米棒光催化效率最高,经可见光照射360 min,浓度为0.01 mmol·L-1甲基橙溶液的降解率可达到93.0%,且循环使用4次后,其光催化活性并没有明显降低,表明BMT是一种稳定有效的可见光催化剂.     

The effect of glass additives on the microwave dielectric properties of Ba(Mg1/3Ta2/3)O3 ceramics

The effect of glass additives on the densification, phase evolution, microstructure and microwave dielectric properties of Ba(Mg_1/3Ta_2/3)O₃ (BMT) was investigated. Different weight percentages of quenched glass such as B₂O₃, SiO₂, B₂O₃-SiO₂, ZnO-B₂O₃, 5ZnO-2B₂O₃, Al₂O₃-SiO₂, Na₂O-2B₂O₃·10H₂O, BaO-B₂O₃-SiO₂, MgO-B₂O₃-SiO₂, PbO-B₂O₃-SiO₂, ZnO-B₂O₃-SiO₂ and 2MgO-Al₂O₃-5SiO₂ were added to calcined BMT precursor. The sintering temperature of the glass-added BMT samples were lowered down to 1300 °C compared to solid-state sintering where the temperature was 1650 °C. The formation of high temperature satellite phases such as Ba₅Ta₄O₁₅ and Ba₇Ta₆O₂₂ were found to be suppressed by the glass addition. Addition of glass systems such as B₂O₃, ZnO-B₂O₃, 5ZnO-2B₂O₃ and ZnO-B₂O₃-SiO₂ improved the densification and microwave dielectric properties. Other glasses were found to react with BMT to form low-Q phases which prevented densification. The microwave dielectric properties of undoped BMT with a densification of 93.1% of the theoretical density were ε_r=24.8, and Q_u×f=80,000. The BMT doped with 1.0 wt% of B₂O₃ has Q_u×f=124,700, ε_r=24.2, and . The unloaded Q factor of 0.2 wt% ZnO-B₂O₃-doped BMT was 136,500 GHz while that of 1.0 wt% of 5ZnO-2B₂O₃ added ceramic was Q_u×f=141,800 GHz. The best microwave quality factor was observed for ZnO-B₂O₃-SiO₂ (ZBS) glass-added ceramics which can act as a perfect liquid-phase medium for the sintering of BMT. The microwave dielectric properties of 0.2 wt% ZBS-added BMT dielectric was Q_u×f=152,800 GHz, ε_r=25.5, and .     

Bi掺杂对La0.1Sr0.9TiO3陶瓷热电性能的影响

在5% H₂+95% N₂（V/V）还原气氛中1 500℃烧结4 h制备La_0.1Bi_xSr_0.9-xTiO₃（x=0、0.05、0.075、0.1）陶瓷,并对其组成、显微结构和热电性能进行研究。结果表明：掺Bi试样的主晶相均为SrTiO₃,当Bi掺杂量大于0.075时,样品中出现少量Bi₂O₃杂相;掺Bi试样的晶粒发育完全,形状规则,结合紧密,显示出Bi₂O₃良好的助烧效果。另外,Bi元素掺入使La_0.1Sr_0.9TiO₃陶瓷的电导率和Seebeck系数绝对值显著增加,说明Bi元素的掺入可有效提高材料的载流子浓度和载流子迁移率。其中,x=0.075时试样的功率因子最大,在400℃时为692 μW·m^-1·K^-2。虽然其热导率比未掺杂Bi试样有所提高,x=0.075时试样的ZT值在500℃时仍可达0.172,比未掺杂Bi试样提高了130%。     

Bi掺杂对La_(0.1)Sr_(0.9)TiO_3陶瓷热电性能的影响

在5%H_2+95%N_2(V/V)还原气氛中1 500℃烧结4 h制备La_(0.1)Bi_xSr_(0.9-x)TiO_3(x=0、0.05、0.075、0.1)陶瓷,并对其组成、显微结构和热电性能进行研究。结果表明:掺Bi试样的主晶相均为Sr Ti O3,当Bi掺杂量大于0.075时,样品中出现少量Bi_2O_3杂相;掺Bi试样的晶粒发育完全,形状规则,结合紧密,显示出Bi_2O_3良好的助烧效果。另外,Bi元素掺入使La_(0.1)Sr_(0.9)TiO_3陶瓷的电导率和Seebeck系数绝对值显著增加,说明Bi元素的掺入可有效提高材料的载流子浓度和载流子迁移率。其中,x=0.075时试样的功率因子最大,在400℃时为692μW·m~(-1)·K~(-2)。虽然其热导率比未掺杂Bi试样有所提高,x=0.075时试样的ZT值在500℃时仍可达0.172,比未掺杂Bi试样提高了130%。     

Bi2O3掺杂对Ag(Nb0.8Ta0.2)O3陶瓷结构和介电性能的影响

本文研究了Bi₂O₃掺杂对Ag(Nb_0.8Ta_0.2)O₃陶瓷的结构和介电性能的影响。X射线衍射(XRD)结果表明,Bi₂O₃的掺杂可以使陶瓷中Ag⁺被还原并析出,且银析出的量随Bi₂O₃掺杂量的增加而不断增加,这可能源自于Bi³⁺对Ag⁺的取代。在一定范围内增大Bi₂O₃掺杂量可提高Ag(Nb_0.8Ta_0.2)O₃陶瓷的室温介电常数,降低介电损耗,并使温度系数向负值方向移动。当Bi₂O₃的掺杂量约为3.5wt%时,样品具有较大的介电常数(ε=672)和较小的介电损耗(tanδ=7.3×10^-4)。     

Bi_2O_3掺杂对Ag(Nb_(0.8)Ta_(0.2))O_3陶瓷结构和介电性能的影响(英文)

本文研究了Bi2O3掺杂对Ag(Nb0.8Ta0.2)O3陶瓷的结构和介电性能的影响。X射线衍射(XRD)结果表明,Bi2O3的掺杂可以使陶瓷中Ag+被还原并析出,且银析出的量随Bi2O3掺杂量的增加而不断增加,这可能源自于Bi3+对Ag+的取代。在一定范围内增大Bi2O3掺杂量可提高Ag(Nb0.8Ta0.2)O3陶瓷的室温介电常数,降低介电损耗,并使温度系数向负值方向移动。当Bi2O3的掺杂量约为3.5wt%时,样品具有较大的介电常数(ε=672)和较小的介电损耗(tanδ=7.3×10-4)。     

Preparation and catalytic performance of superfine Ni/BaTiO3 catalyst

Superfine Ni/BaTiO₃ catalysts were prepared by impregnation method and used successfully for CO₂ reforming CH₄ to syngas. The effects of preparation method and the temperatures of calcination, reduction and reaction on the catalytic activity of the Ni/BaTiO₃ system were investigated. This revised version was published online in June 2006 with corrections to the Cover Date.     

BaPbO3与BaTiO3多晶态陶瓷缺陷结构对比

BaPbO，是具有类金属导电特性的钙钛矿结构导电陶瓷，其晶体结构由Ba2＋和O^2-离子紧密堆积形成，pb^4＋离子占据由O^2-离子形成的八面体空隙。BaTiO3同为钙钛矿结构的陶瓷材料，由Ba^2＋和O^2-离子紧密堆积形成，Ti^4＋离子占据由O^2-离子形成的八面体空隙。BaPbO3和BaTiO3的A位离子相同,B位离子都为可变价离子。     

Fabrication of highly refractive BaTiO3 nanocomposite films using heat resistant polymer as matrix

Highly refractive, heat-resistant BaTiO₃ nanocomposite films were fabricated via in situ polymerization to homogeneously disperse barium titanate (BT) nanoparticles into polyimide (PI) matrix. BT nanoparticles surface-modified with O-phosphorylethanol phthalimide (PPHI) were employed to the in situ polymerization in which condensation reactions of a diphthalic anhydride and a diamine were conducted to form the prepolymer of poly(amic acid) (PAA) that was thermally imidized in the following step. The nanoparticles surface-modified were added to PAA solution at different times in the polymerization to examine the effect of PAA molecular weight on the refractive index (RI) of the nanocomposite films, which indicated that relatively low molecular weights (<10,000) of PAA formed at the point of nanoparticle addition was appropriate for enhancement of nanocomposite RI. An additional treatment of chemical imidization using acetic acid anhydride and pyridine, which was followed by the thermal imidization, was performed to examine the effect of polyimide structure on RI of nanocomposite films. The RI of nanocomposite films with excellent thermal stability could be successfully enhanced to n = 1.88 by the chemical imidization.     

新钽酸盐Ba3TiTa4O15的结构与介电性能

在BaO Ta2O5系统通过掺Ti4＋合成了新钽酸盐Ba3TiTa4O15,用粉晶XRD对其结构进行了分析,并测试了其烧结体的介电特性.结果表明:Ba3TiTa4O15在室温下属于填满型四方钨青铜结构,晶胞参数a=1.256 27(6)nm, c=0.395 86(4)nm; Ba3TiTa4O15在－35 ℃从铁电相转变为顺电相.     

铌酸盐Ba3NaBiNb10O30的结构与介电特性

一些铁电铌酸盐具有优良的电光性能和非线性光学性能,因此该类化合物的人工合成,结果与性能的研究受到了人们的重视,其中钨青铜结构的系列晶体（例如SBN,KNSBN,SCNN）在材料制备和器件设计方面都取得了很大进展,它们在实时全息存储,集成光学与光信号处理等领域具有广泛的应用前景[1-4],Ba2NaNb5O145(BNN)是目前认为最好的一种倍频晶体,Geusic[5,6]等人报导了在BNN晶体能实现最优位相匹配,可将1．06um红外光以100％的效率转换为0．53um绿光,我们在BaO-Na2O-Nb2O5体系中通过掺杂Bi3 合成了铌酸盐Ba3NaBiNb10O30,并采用粉晶X射线衍射（XRD）对其结构进行了分析,测试了其烧结体的介电特性。