La2O3/γ-Al2O3复合产物的浸渍-燃烧法制备及表征

采用浸渍-燃烧法制备了La2O3/γ-Al2O3复合产物,原料为La(NO3)3.6H2O(A.R)、一水合柠檬酸和工业级的拟薄水铝石.以六水合硝酸镧和一水合柠檬酸分别为镧源和燃烧剂,柠檬酸与六水硝酸镧的摩尔比为5∶6左右.将拟薄水铝石研磨成粉末并溶于柠檬酸和镧的配合物溶液中,搅拌至凝胶状,110℃干燥2h,再放入马弗炉中焙烧2 h得到产物.采用XRD、BET、XPS进行分析和表征,结果表明La3+的加入提高了γ-Al2O3的热稳定性,随着样品焙烧温度升高,比表面积下降,孔容、孔径变大.随着La3+的量的增加,样品的比表面积增大,孔径尺寸分布变宽.通过控制La3+加入的量以及焙烧温度,可调控多孔γ-Al2O3粉体的比表面积、孔容、孔径大小及孔径分布.     

MnO2对Ba(Mg1/3Nb2/3)O3微观结构和微波介电性能的影响

研究了MnO2助烧剂对Ba(Mg1/3Nb2/3)O3陶瓷的微观结构和微波介电性能.MnO2可以有效地使Ba(Mg1/3Nb2/3)O3陶瓷的致密化温度由1550℃降低到1400℃左右.随MnO2掺量的增加,Ba(Mg1/3Nb2/3)O3陶瓷的12超晶格衍射峰的强度减弱,但是没有第二相出现.1400℃烧结4h陶瓷的晶粒尺寸在1.5μm左右.MnO2的掺入改善了Ba(Mg1/3Nb2/3)O3陶瓷的微波介电性能,MnO2掺量为1%mol的Ba(Mg1/3Nb2/3)O3陶瓷具有最好的微波介电性能εr≈31.5,Qf=68000,τf=3.11×10-5/℃,这可归功于陶瓷具有相当高的相对密度.     

SiO2/TiO2复合气凝胶的孔道结构研究

为了在常压干燥下制备高比表面积且具有多级孔道结构的SiO2/TiO2复合气凝胶,以正硅酸乙酯、钛酸丁酯为原料,利用低聚体聚合将分相平行引入到溶胶凝胶过程中,获得SiO2/TiO2醇凝胶,并通过溶剂替换技术实现气凝胶的常压干燥制备.不同硅钛比气凝胶的内部结构研究表明:合成的气凝胶是由纳米SiO2和TiO2颗粒分散复合而成的介孔块体,其中Ti—O—Ti、Si—O—Si和Ti—O—Si键相互交织.气凝胶的结构变化是分相与溶胶凝胶过程相互竞争的结果.Si含量能显著改善气凝胶的结构,当n(Ti)∶n(Si)为3∶1时,比表面积高达712.2 m2/g,平均孔径为3.36 nm;当n(Ti)∶n(Si)为1.5∶1时,复合气凝胶具有明显双连续孔道,比表面积高,同时孔状结构清晰.     

液相包裹法制备Pb(Mg1/3Nb2/3)O3-CoFe2O4磁电耦合材料

以无机盐Nb2O5、Mg(NO3)2、Pb(NO3)4、Co(NO3)2、Fe2(NO3)3为原料,柠檬酸和EDTA为络合剂,分别制备了Nb5+、Mg2+、Pb2+、Co2+、Fe3+等离子的络合溶液。采用络合法制备了铌酸镁-铁酸钴先驱体(MgNb2O6-CoFe2O4,简称MN-CFO)。此先驱体在1000℃煅烧1h后,得到纯净的MgNb2O6-CoFe2O4固溶体。采用液相包裹法制备了铌镁酸铅-铁酸钴(Pb(Mg1/3Nb2/3)O3-CoFe2O4)先驱体,在1000℃煅烧1h,Pb(Mg1/3Nb2/3)O3-CoFe2O4先驱体分解为具有铁电相Pb(Mg1/3Nb2/3)O3和铁磁相CoFe2O4的复相组织。研究了10%过量的PbO对煅烧过程中烧绿石相向铁电相的转变作用,并在700℃煅烧5h条件下制备了不含烧绿石相的Pb(Mg1/3Nb2/3)O3-CoFe2O4固溶体。     

层状锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的共沉淀法合成

以Ni(NO3)2·6H2O,Co(NO3)2·6H2O,Mn(CH3COO)2·4H2O,LiOH·H2O为原料,采用NaOH-Na2CO3共沉淀的方法,在空气中合成了三元层状锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2.采用XRD研究了所合成材料的结构.考查了不同烧结温度对材料电化学性能的影响.结果表明,所合成的材料具有典型的α-NaFeO2层状结构特征,900℃下合成的材料具有最优的循环性能,初始放电容量为169.4mAh/g,初次库仑效率为83.2%,且20次循环后,容量保持率达到96.3%.     

Ag/Bi3.25La0.75Ti3O12/Bi4Ti3O12/Si结构铁电薄膜制备及其铁电性能的研究

利用溶胶-凝胶(sol-gel)方法,在硅基底上制备了Bi3.25La0.75Ti3O12/Bi4Ti3O12/Si铁电薄膜,其中Bi4Ti3O12作为缓冲层.用XRD方法分析了该结构铁电薄膜的物相结构;用扫描电镜对薄膜样品进行表面形貌观察;并且对该结构的铁电性能进行了研究.     

(1-x)Pb(Fe2/3W1/3)O3-xPb(Mg1/2W1/2)O3多铁性材料的有序结构及磁性能

以无机盐为前驱体,利用溶胶-凝胶法固溶合成了(1-x)Pb(Fe2/3W1/3)O3-xPb(Mg1/2W1/2)O3多铁性固溶体.XRD分析表明,在0≤x≤1.0的掺杂范围内,700℃煅烧所得产物都具有钙钛矿结构;x=0时得到的纯Pb(Fe2/3W1/3)O3为长程无序结构,x=1.0时可获得完全有序的纯Pb(Mg1/2W1/2)O3相,其单胞为Pb(Fe2/3W1/3)O3单胞的2倍;当0相似文献   

制备方法对Cu/La2O3催化剂上醇转移脱氢性能的影响

采用沉积-沉淀法(DP)、共沉淀法(CP)和浸渍法(IMP)制备了Cu/La2O3催化剂,并用ICP-AES、BET、XRD、H2-TPR及TEM等对催化剂进行了表征,以1-辛醇转移脱氢制备1-辛醛的反应为探针反应研究了不同的制备方法对Cu/La2O3催化剂性能的影响。结果表明,与采用共沉淀法(CP)和浸渍法(IMP)制备的催化剂相比,沉积-沉淀法(DP)制备的Cu/La2O3催化剂具有更大的比表面积和更高分散度的Cu物种,使得Cu/La2O3催化剂在1-辛醇液相转移脱氢制1-辛醛的反应中具有更好的转移脱氢活性。     

碳热还原协同溶胶-凝胶法合成纳米ZrB2粉末

利用ZrO2-B2O3-C反应体系碳热还原的基本原理,分别使用正丙醇锆(Zr(OC3H7)4)、硼酸(H3BO3)和蔗糖(C12H22O11)为原料,采用溶胶-凝胶-碳热还原法合成了二硼化锆(ZrB2)纳米粉末。我们首先使用络合剂醋酸(AcOH)修饰Zr(OC3H7)4,以防止Zr(OC3H7)4的快速水解;其次,选用蔗糖作为碳源,是考虑到蔗糖热解时可以完全分解为碳,这样可以准确计算热解过程碳的生成量。此外,研究了凝胶温度对ZrB2纳米粉末形貌的影响。结果表明:当起始原料B/Zr(mol.)=2.3、热解温度为1 550℃时,通过碳热还原协同溶胶-凝胶法成功合成了单相ZrB2纳米粉末;当凝胶温度分别为65、75和85℃时,ZrB2纳米粉末形貌从球状演变为链状,最后生长为棒状,生长机理为定向吸附。     

(1-x)(Mg0.7Zn0.3)TiO3-xCa0.61La0.26TiO3系陶瓷的微波介电性能研究（英文）

本实验研究了(1-x)(Mg0.7Zn0.3)TiO3-x(Ca0.61La0.26)TiO3(MZT-CLT)系陶瓷的微观结构和微波介电性能,通过(Ca0.61La0.26)TiO3来协调(Mg0.7Zn0.3)TiO3陶瓷的谐振频率温度系数.MZT-CLT陶瓷的主晶相为(Mg0.7Zn0.3)TiO3,第二相为Ca0.61La0.26TiO3和(Mg0.7Zn0.3)Ti2O5.烧结温度和陶瓷组成对微波介电性能影响显著,当烧结温度为1275℃时,可以获得良好的致密度,当烧结温度超过1300℃时,Zn的蒸发导致陶瓷致密度和介电性能下降.随着(Ca0.61La0.26)TiO3含量的增大,材料的介电常数增大,品质因数减小.当x=0.13,烧结温度为1275℃保温4h,(MZT-CLT)陶瓷具有优良微波介电性能,εr=26,Q.f=86000 GHz,τf=-6×10-6/℃.     

Structure transformations and dielectric properties of PbY1/2Nb1/2O3 and PbHo1/2Nb1/2O3 compounds

The metastable pseudomonoclinic perovskite phases, PbY_1/2Nb_1/2O₃ and PbHo_1/2Nb_1/2O₃ were prepared under conditions of high pressures and temperatures. Investigations of structural parameters, thermal stability and some dielectric properties were carried out. The data were analyzed by comparison with corresponding data of other representatives of the PbB_1/2³⁺Nb_1/2O₃ series. The dependence of unit cell parameters on the B³⁺ rare earth cation radius for the PbB_1/2³⁺Nb_1/2O₃ perovskites was correlated with a change of electronic structure of the rare earth elements, in particular, with the 4f-shell filling.     

Structure and ferroelectric properties of Bi(Zn1/2Ti1/2)O3-(Bi1/2K1/2)TiO3 perovskite solid solutions

Lead-free piezoelectric ceramics based on χBi(Zn_1/2Ti_1/2)O₃-(1-χ)(Bi_1/2K_1/2)TiO₃ were obtained via solid state processing techniques. A single perovskite phase with tetragonal symmetry was obtained for Bi(Zn_1/2Ti_1/2)O₃ (BZT) substitutions up to 20 mol%. The maximum density was 97.1% at the composition of χ = 0.1. The dielectric measurement indicated that the transition temperature decreased linearly with increasing BZT content. The P-E loops revealed an increase in remanent polarization (P_r) with the addition of BZT. The maximum planar coupling coefficient, κ_r, for the χ = 0.1 composition was 21.6 and the piezoelectric coefficient, d₃₃, for χ = 0, χ = 0.05, and χ = 0.1 was 108, 185, and 235 pm/V, respectively. Overall, the dielectric and piezoelectric properties showed significant improvement when BZT was added.     

Neutron powder diffraction and magnetic study of perovskites Pb(Mn1/2Nb1/2)O3 and Pb(Mn1/4Fe1/4Nb1/2)O3

The structural and magnetic properties of the complex metal oxides Pb(Mn_1/2Nb_1/2)O₃ (PMNO) and Pb(Mn_1/4Fe_1/4Nb_1/2)O₃ (PMFNO), which belong to a class of disordered perovskites have been studied. The magnetic susceptibilities of PMNO showed hysteresis between field cooled and zero-field cooled conditions below the transition of 15 K, suggesting that the material has a spin-glass feature. Neutron diffraction patterns of PMNO showed no evidence of a long-range magnetic ordering at 1.5 K, which is consistent with spin-glass behavior. Rietveld refinements of neutron powder diffraction data collected at different temperatures between 1.5 and 700 K have been carried out in order to extract structural information. The crystal structure of this compound is cubic (space group Pmm) within the whole temperature interval. The Mn and Nb ions were found to be disordered over the perovskite B-sites. The main feature of this structure is the positional disorder at the Pb site, the importance of which in connection with the ferroic transitions is briefly discussed. The Pb cations show a positional disorder shifting from their high-symmetry positions along the [1 1 1] direction. The effect of Fe-doping on PMNO has been studied. The substitution of Fe at the Mn site in PMFNO results in a small changes of the magnetic properties without significant differences in the crystal structures. The factors governing the observed structural and magnetic properties of PMNO and PMFNO are discussed and compared with those of other quaternary Mn-containing perovskites. For the PbB³⁺_1/2Nb_1/2O₃ series with the isomorphous substitution B³⁺, graphs of average lattice parameters of the perovskite phase and the temperatures of ferroelectric and magnetic phase transitions as functions of the B³⁺ cation radius were constructed and are discussed. Influence of A-cation sublattice on magnetic properties is also considered.     

Depolarization temperature and piezoelectric properties of Na1/2Bi1/2TiO3-Na1/2Bi1/2(Zn1/3Nb2/3)O3 ceramics by two-stage calcination method

A new group of NBT-based lead-free piezoelectric ceramics, Na_1/2Bi_1/2TiO₃-Na_1/2Bi_1/2(Zn_1/3Nb_2/3)O₃, was synthesized using the two-stage calcination method and depolarization temperatures and piezoelectric properties were also investigated. The XRD analysis showed that the ceramics system had a morphotropic phase boundary (MPB) between the rhombohedral and the tetragonal structure. The highest piezoelectric properties of d ₃₃ = 97 pC/N and k _t = 0·46 were obtained near MPB compositions. Furthermore, the depolarization temperatures near MPB compositions were slightly decreased and the lowest T _d was maintained at 210°C.     

Phase developments in the Pb(Zn1/2W1/2)O3-Pb(Zn1/3Ta2/3)O3-Pb(Zn1/3Nb2/3)O3 pseudo-ternary system

The phase stability ranges in the B-site precursor (Zn_1/2W_1/2)O₂-(Zn_1/3Ta_2/3)O₂-(Zn_1/3Nb_2/3)O₂ were determined by X-ray diffraction (XRD), where wolframite, tri-αPbO₂, and columbite phases were identified. Next attempts were carried out (with the addition of PbO) for the system Pb(Zn_1/2W_1/2)O₃-Pb(Zn_1/3Ta_2/3)O₃-Pb(Zn_1/3Nb_2/3)O₃, where the perovskite phase did not develop in the entire compositions investigated. Instead, only the Pb₂WO₅ and pyrochlore phases (along with ZnO) resulted.     

K2(Rb2,Cs2,Tl2)TeBr6(I6) and Rb3(Cs3)Sb2(Bi2)Br9(I9) perovskite compounds

We systematize available experimental data on the crystal structure of the ternary halides K₂(Rb₂,Cs₂,Tl₂)TeBr₆(I₆) and Rb₃(Cs₃)Sb₂(Bi₂)Br₉(I₉), analyze the general trends in the properties of their single crystals, and examine the key features of the physicochemical interaction in related systems.     

The investigation of the hydrothermal crystallization in Nd2O31bGeO21bNaOH1bH2O system

The hydrothermal crystallization in Nd₂O₃1bGeO₂1bNaOH1bH₂O system is investigated. The single crystals of NaNd₃[GeO₄]₂(OH)₂, Na_4,67[GeO₄]₃O, NaNd₃Ge₄O₁₃, Nd₂GeO₅, Nd₂Ge₂O₇, Nd(OH)₃, Na₄Ge₉O₂₀,Na₂GeO₃·H₂O are obtained. The phase diagram of the crystallization fields in the system under consideration is built. The germanates synthesized are stadied by X-Ray analysis and IR-spectroscopy.     

Crystallization of CaHf1? x Zr x Ti2O7 (0?≤ x ≤?1) zirconolite in SiO2–Al2O3–CaO–Na2O–TiO2–HfO2–ZrO2–Nd2O3 glasses

Glass-ceramics containing (Hf,Zr)-zirconolite crystals (nominally CaHf_1−x Zr _x Ti₂O₇ with 0 ≤ x ≤ 1) were envisaged to immobilize minor actinides and plutonium. Such materials were prepared in this study by controlled crystallization of glasses belonging to the SiO₂–Al₂O₃–CaO–Na₂O–TiO₂–HfO₂–ZrO₂–Nd₂O₃ system. Neodymium was used as trivalent actinides surrogate. The effect of total or partial substitution of ZrO₂ by HfO₂ (neutron poison for fission reactions) on glass crystallization in the bulk and near the surface is presented. It appeared that Hf/Zr substitution had not significant effect on nature, structure, and composition of crystals formed both on glass surface (titanite + anorthite) and in the bulk (zirconolite). This result can be explained by the close properties of Zr⁴⁺ and Hf⁴⁺ ions and by their similar structural role in glass structure. However, strong differences were observed between the nucleation rate I_Z of zirconolite crystals in glasses containing only HfO₂ and in glasses containing only ZrO₂. Hf-zirconolite (CaHfTi₂O₇) crystals were shown to nucleate only very slowly in comparison with Zr-zirconolite (CaZrTi₂O₇) crystals. Composition changes - by increasing either HfO₂ or Al₂O₃ concentration or by introducing ZrO₂ in parent glass - were performed to increase I_Z in hafnium-rich glasses. The proportion of Nd³⁺ ions incorporated in the zirconolite phase was estimated using ESR.     

Synthesis and structural characterization of (Bi2O3)1?x (Y2O3)x and (Bi2O3)1?x (Gd2O3)x solid solutions

Solid solution series, (Bi₂O₃)_1−x (Y₂O₃)_x and (Bi₂O₃)_1−x (Gd₂O₃)_x, forx = 0.10, 0.20, 0.30 and 0.40 were synthesized by standard ceramic technique. The structural phase characterization was carried out using X-ray powder diffraction technique. It was found that the solid solution containing 20–40 mole% of Y₂O₃ had face-centred cubic structure. All samples of the solid solution series, (Bi₂O₃)_1−x (Gd₂O₃)_x, had rhombohedral single phase in the concentration range 0.10 ≤x ≤ 0.40. Lattice parameters offcc phase of Y₂O₃ doped samples were calculated from the X-ray diffraction data. The lattice constant ‘a’ gradually decreases with increasing content of dopant concentration (x) for the Y₂O₃ doped system and obeys Vegard’s rule. The unit cell parameters for the (Bi₂O₃)_1−x (Gd₂O₃)_x doped samples showing rhombohedral phase were obtained on hexagonal setting.     

Piezoelectric shear-mode properties of Pb(Yb1/2Nb1/2)O3-PbTiO3 ceramics

A Pb(Yb_1/2Nb_1/2)O₃-PbTiO₃ [PYNT] solid solution was synthesized and characterized for its potential use. The shear-mode dielectric and piezoelectric behaviors of PYNT with a morphotropic phase boundary (MPB) composition were studied as a function of temperature. Dielectric permittivity K₁₁^T and loss were found to be 2310 and 2.5%, respectively, at room temperature. Piezoelectric coefficient d₁₅ and electromechanical coupling factor k₁₅ were calculated to be 710 pC/N and 0.70, respectively, maintaining nearly constant up to 300 °C, resistivity and RC time constant were observed to be 2.4 × 10⁹ Ω cm and 1.07 s, respectively, at 350 °C. These good piezoelectric properties, together with the high Curie temperature (T_c ∼ 370 °C), indicate that PYNT is a promising candidate for high temperature-shear sensor and inkjet actuator applications.