3D hierarchical Zn3(OH)2V2O7·2H2O and Zn3(VO4)2 microspheres: Synthesis,characterization and photoluminescence

Via a simple glycine-assisted hydrothermal route, large-scale 3D hierarchical Zn₃(OH)₂V₂O₇·2H₂O microspheres have been fabricated. Their purity, crystalline phase, morphologies and thermal stability were characterized by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), Fourier transform IR (FTIR), scanning electron microscopy (SEM) and thermogravimetry-differential scanning calorimetry (TG-DSC). The SEM results indicate that the microspheres are self-assembled by numerous nanoflakes with mean thickness of 100 nm. Some factors influencing the morphologies of the Zn₃(OH)₂V₂O₇·2H₂O micro-/nanostructures have been systematically investigated, as well as quantity of glycine and the reaction time. The possible mechanism of the crystal growth and assembled procedure were also proposed. The as-prepared Zn₃(OH)₂V₂O₇·2H₂O can be transformed into Zn₃(VO₄)₂ with the similar morphologies by calcination in air at 600 °C. Furthermore, the photoluminescent properties of both Zn₃(OH)₂V₂O₇·2H₂O and Zn₃(VO₄)₂ were studied and exhibited different spectra.     

Pb(Zn1/3Nb2/3)O3-Ba(Zn1/3Nb2/3)O3铁电陶瓷结构与性能的研究

采用固相反应的方法系统地研究了BZN稳定PZN基陶瓷的相结构与介电性能.随着BZN含量的增加,PZN-BZN陶瓷中钙钛矿相的稳定性增强,居里温度近似呈线性下降,室温介电常数和介质损耗随也显著降低,最小值分别为380和0.002.为获得100%钙钛矿结构的PZN基陶瓷所需BZN的最小用量为8mol%～10mol%,当BZN的mol%超过15mol%时,PZN基陶瓷中钙钛矿相所占的百分比不再受烧结工艺的影响,基本保持100%.1kHz时Pb0.9Ba0.1Zn1/3Nb2/3O3陶瓷的最大介电常数Kmax=8680,tgδ=0.02,相应的居里温度Tm为24℃.     

Dehydration/amine intercalation in Zn(O3PR)–H2O phosphonates: the missing link,X-ray structure of Zn(O3PCH3)

The hydrothermal synthesis of colorless crystals of Zn(O₃PCH₃) was achieved using a solution of zinc nitrate and methylphosphonic acid (1:1) in water, in the presence of thiourea. The structure was determined by single crystal X-ray diffraction [monoclinic, space group P2₁/c (No. 14), a=8.7226(9) Å, b=5.2156(7) Å, c=10.847(1) Å, V=389.48(9) ų, Z=2]. From this result, the mechanism of the structure modification taking place during the dehydration of Zn(O₃PR)–H₂O phosphonates was clearly demonstrated.     

Microwave dielectric properties and applications of Ba(Zn1/3Nb2/3)O3–Ca(Zn1/3Nb2/3)O3 composite ceramics by one-step synthesis method

(1 ? x) Ca(Zn_1/3Nb_2/3) O₃ ? xBa(Zn_1/3Nb_2/3)O₃ (short for CZN/BZN, x = 0–1.0) ceramics were prepared and investigated through the “one-step synthesis method” method. The structure of the system was analyzed using X-ray diffraction. The microstructure of the sintered pellet was analyzed using scanning electron microscopy. Dielectric constant (ε_r), temperature coefficient of resonant frequency (τ_f) and the unloaded quality factor (Q × f) were measured in the microwave frequency region. Two dielectric properties were firstly in the rising tendency and then decreasing with the increased x. On the other hand, a good combination of microwave dielectric properties (ε_r = 24, Q × f = 23,510 GHz τ_f = ?9 ppm/°C) were obtained at x = 0.1. The compositions have excellent microwave dielectric properties and hence are suitable for ceramic capacitors or dielectric resonators applications.     

Low-temperature sintering and piezoelectric properties of Pb(Fe2/3W1/3)O3–added Pb(Zn1/3Nb2/3)O3–Pb(Ni1/3Nb2/3)O3–Pb(Zr,Ti)O3 ceramics

Low-temperature sintering of (a–x)Pb(Zr_0.48Ti_0.52)O₃–bPb(Ni_1/3Nb_2/3) O₃–cPb(Zn_1/3Nb_2/3)O₃–xPb(Fe_2/3W_1/3)O₃ (a + b + c + x = 1, 0.06 ≤ x ≤ 0.10) ceramics were prepared through two-step synthesis process using perovskites-structured ferroelectric materials Pb(Fe_2/3W_1/3)O₃ (PFW) as a sintering aid. The effects of PFW content on the densification, microstructure, phase structure, dielectric and piezoelectric properties of the ceramics were investigated. The sintering temperature was reduced from 1,180 °C (without PFW addition) to 940 °C when the material was PFW-doped. PFW-doping increased the sintered density and the average grain size of PFW–PNN–PZN–lead zirconate titanate ceramics. The ceramics sintered at 940 °C for 4 h with x = 0.08 exhibited favorable properties, which were listed as follows: d₃₃ = 496pC/N, εT 33/ε₀ = 3,119, tanδ = 2.1 % and Curie temperature = 242 °C. These values indicated that the newly developed composition might be suitable for multilayer piezoelectric devices application.     

Ferroelectric properties of (1 − x)Bi(Zn1/2Ti1/2)O3–xPbZrO3 ceramics

The (1 − x)Bi(Zn_1/2Ti_1/2)O₃–xPbZrO₃ solid solution ceramics were prepared by using solid-state reaction method, and their ferroelectric properties were investigated. It was found that the perovskite structure is stable for compositions with x ≥ 0.900. Within this composition range, the crystal structure of the solid solution preserves the orthorhombic symmetry of PbZrO₃ (PZ). The Curie point of the ceramics was found to decrease with increasing Bi(Zn_1/2Ti_1/2)O₃ (BZT) content. The intermediate ferroelectric phase of PZ was stabilized by BZT addition and exists within a much wider temperature range in the solid solution.     

Chemical Bath Co-deposited ZnS Film Prepared from Different Zinc Salts: ZnSO_4—Zn(CH_3COO)_2, Zn(NO_3)_2—Zn(CH_3COO)_2,or ZnSO_4—Zn(NO_3)_2

ZnSO_4—Zn(CH_3COO)_2, Zn(NO_3)_2—Zn(CH_3COO)_2, ZnSO_4—Zn(NO_3)_2, ZnSO_4, Zn(NO_3)_2 or Zn(CH_3COO)_2 have been used as zinc sources to prepare ZnS thin films by chemical bath deposition and co-deposition methods.Zn(NO_3)_2 or/and Zn(CH_3COO)_2 is/are favorable for cluster by cluster deposition process while ZnSO_4 favors ion by ion deposition process regardless of concentration ratios of ZnSO_4. However, Zn(NO_3)_2 affects the nucleation density of Zn S nuclei on the substrate. Zn S thin films deposited from ZnSO_4—Zn(CH_3COO)_2 are not only more homogeneous and compact, but also have higher growth rate and adhesion on to the glass substrate. The cubic ZnS films are obtained after only single deposition. The average transmission of films from S6, S7, S8, S9 and S1 for 2 and 2.5 h is greater than 85% in visible region. Compared with the film from S6(112 nm), the film from S7 is not only thicker(125 nm), but also more transparent. The band gaps of the films deposited from S6, S7, S8, S9 and S1 for 2 and 2.5 h range from 3.88 to 3.98 e V.The effects of anions from different zinc salts are discussed in detail.     

Complexes with substituted 2,5-dihydroxy-p-benzoquinones: The inclusion compounds [Y(H2O)3]2 (C6Cl2O4)3·6.6H2O and [Y(H2O)3]2 (C6Br2O4)3·6H2O

Single crystal of [Y(H₂O)₃]₂ (C₆Br₂O₄)₃·6H₂O and [Y(H₂O)₃]₂ (C₆Cl₂O₄)₃·6.6H₂O were grown in aqueous silicagel. The compounds are in principle isostructural. In Y chloranilate one additional water site is occupied as verified by X-ray single crystal structure analysis. Y³⁺ is nine-coordinated by three water molecules and six oxygen atoms of the bischelating (C₆X₂O₄)²⁻ ions (XCl, Br). The coordination polyhedron is an only slightly distorted tri-capped trigonal prism. The connection of Y³⁺ with the dianions leads to infinite, corrugated layers. The layer stacking yields cage-like cavities in which water molecules are accomodated. Hydrogen bonds interlink adjacent layers. Further hydrogen bonds involve the entrapped water molecules. DSC measurements indicated a complicated dehydration process which caused right at the start destruction of the single crystals.     

Zn—Al2O3和Zn—SiO2复合镀层的研制

详细叙述了Ｚｎ－Ａｌ２Ｏ３和Ｚｎ－ＳｉＯ２复合镀层的制做方法，提出了复合镀液中所用微粒子和净化处理方法。对复合镀层的耐腐蚀性和结合力进行了测定，得出了耐腐蚀性和结合力均较好的Ｚｎ－Ａｌ２Ｏ３和Ｚｎ－ＳｉＯ２复合镀层中粒子的含量范围等有用的数据。     

Electromechanical properties of Pb(In(1∕2)Nb(1∕2))O(3)-Pb(Mg(1∕3)Nb(2∕3))O(3)-PbTiO(3) single crystals

The Pb(In(1∕2)Nb(1∕2))O(3)-Pb(Mg(1∕3)Nb(2∕3))O(3)-PbTiO(3) (PIN-PMN-PT) crystals were studied as function of phase and orientation. The properties, including the Curie temperature T(C), ferroelectric-ferroelectric phase transition temperature T(R∕O-T), coercive field, and piezoelectric∕dielectric responses, were systematically investigated with respect to the composition of PIN-PMN-PT crystals. The Curie temperature T(C) was found to increase from 160 to 220 °C with ferroelectric-ferroelectric phase transition temperature T(R-T) and T(O-T) being in the range of 120-105 °C and105-50 °C, respectively. The piezoelectric activity of PIN-PMN-PT crystals was analyzed by Rayleigh approach. The ultrahigh piezoelectric response for domain engineered [001] (1600-2200 pC∕N) and [011] (830-1550 pC∕N) crystals was believed to be mainly from the intrinsic contribution, whereas the enhanced level of piezoelectric and dielectric losses at the compositions around morphotropic phase boundaries (MPBs) was attributed to the phase boundaries motion.     

Dielectric properties of BaTiO3–Bi(Zn1/2Ti1/2)O3–NaNbO3 solid solutions

In order to develop dielectric ceramics with temperature-stable permittivity characteristics, perovskite BaTiO₃–Bi(Zn_1/2Ti_1/2)O₃–NaNbO₃ ceramic solid solutions were investigated with a particular focus on effects of BaTiO₃ and NaNbO₃ contents on the dielectric properties of ternary compounds. Keeping the ratios of the other two constituents constant, decreasing the BaTiO₃ content leads to a broadening of the temperature-dependent permittivity maximum and a decrease in the overall permittivity. For compositions of constant BaTiO₃ content, replacing Bi(Zn_1/2Ti_1/2)O₃ with NaNbO₃ shifts the temperature of the maximum permittivity to lower temperatures (e.g., to ?103 °C for a composition of 70BT–5BZT–25NN) while maintaining a broad permittivity peak with temperature, which for the 50BT–25BZT–25NN composition also satisfies the X9R standard. Thus, the investigation of BT–BZT–NN compounds resulted in promising dielectric properties with broad temperature ranges of high permittivity, which is of interest for advanced capacitor applications.     

Domain size engineering in tetragonal Pb(In(1∕2)Nb(1∕2))O(3)-Pb(Mg(1∕3)Nb(2∕3))O(3)-PbTiO(3) crystals

The effect of domain size on the dielectric and piezoelectric properties of [111]-oriented tetragonal Pb(In(1∕2)Nb(1∕2))O(3)-Pb(Mg(1∕3)Nb(2∕3))O(3)-PbTiO(3) crystals was investigated. The dielectric permittivity (?(33?) (T)∕?(0)) and piezoelectric coefficient (d(33)) were found to be on the order of 13 800 and 1630 pC∕N, respectively, for samples with domain size of ～500?nm, a 3-fold increase to crystals with domain size of ～50?μm. Rayleigh analysis revealed that the extrinsic contribution to the piezoelectric response increased from ～8% to 30% with decreasing domain size, due to the increased domain wall density and associated irreversible domain wall motion. The enhanced properties were thought to relate to the fine domain structures, however, showing a poor electric field and temperature stabilities with domain size of 500?nm. Of particular significance is that samples with domain size being on the order of 5?μm exhibit field and temperature stabilities, with yet high piezoelectric properties, make it potential for transducer applications.     

Reaction of Cd(NO3)2·4H2O with 4,4'–bipyridine (bpy) in MeOH solvent: synthesis and characterization of T-shaped [Cd(bpy)1.5(NO3)2]·3H2O,square grid [Cd(bpy)2(H2O)2](NO3)2·4H2O and linear polymeric [Cd(bpy)(H2O)2(NO3)2]

The influence of concentration of water and metal salt in the reaction between Cd(NO₃)₂·4H₂O and 4,4′–bipyridine in MeOH has been studied and three compounds namely, T-shaped [Cd(bpy)_1.5(NO₃)₂]·3H₂O, 1 square grid [Cd(bpy)₂(H₂O)₂](NO₃)₂ 4H₂O, 2 and one dimensional linear polymer, [Cd(bpy)(H₂O)₂(NO₃)₂], 3 were isolated quantitatively in this process. Compound 1 forms in MeOH at high dilution of the metal salt (5.0 mg/mL or less) and for the metal-to-ligand ratio 1:(1.5–2.0). Compound 2 forms exclusively in the concentration range, 17–33% for water in MeOH by volume and 12–28 mg/mL for the metal salt of the solution. Outside these limits, mixtures of 2 and 3 were isolated. For 1:1 ratio of metal salt to bpy, the linear polymer, 3 was obtained in major quantity and its formation was found to be independent of concentration of water or the metal salt. Compounds 1 and 2 have been characterized by X-ray crystallography. On heating all the compounds decompose through a common intermediate [Cd(bpy)(NO₃)₂] and finally to CdO as monitored by TG.     

Synthesis and structure of actinide(VII) compounds Rb3NpO4(OH)2·3H2O and Rb3PuO4(OH)2·3H2O

Actinide(VII) salts Rb₃[NpO₄(OH)₂]·3H₂O (I) and Rb₃[PuO₄(OH)₂]·3H₂O (II) were prepared as single crystals and examined by X-ray diffraction. The compounds are isostructural and crystallize in the monoclinic system, space group C2/c, Z = 4; unit cell parameters: a = 12.1544(3), b = 10.9942(2), c = 7.789(2) ?, ?? = 91.0930(11)° for I and a = 12.1254(3), b = 10.9506(2), c = 7.7699(2) ?, ?? = 90.8253(12)° for II. The main structural elements of I and II are centrosymmetrical anions [AnO₄(OH)₂]^3? forming together with water molecules, owing to strong hydrogen bonding, chains oriented along [101]. In [AnO₄(OH)₂]^3? anions, the central An(VII) atom has a tetragonal-bipyramidal oxygen surrounding. The An-O(OH) interatomic distances decrease in going from I to II owing to actinide contraction by a factor of ??2 more strongly than the An-O bond lengths in the equatorial planes of the bipyramids. The previously studied structure of Cs₃[NpO₄(OH)₂]·3H₂O (III) was refined.     

Microwave dielectric properties of flexible silicone rubber – Ba(Zn1/3Ta2/3)O3 composite substrates

Silicone rubber composites filled with Ba(Zn_1/3Ta_2/3)O₃ (BZT) were prepared by hot pressing and the effect of filler content on the microwave dielectric, mechanical and thermal properties as well as on moisture absorption were investigated. The observed relative permittivity (ɛ_r) was compared with different theoretical models. Among the different theoretical models Jayasundere Smith and Modified Lichtenecker were in good agreement with experimental values of ɛ_r. The study of the mechanical property showed that the silicone rubber – BZT composites were flexible and stretchable. The coefficient of thermal expansion and specific heat capacity decreased whereas thermal conductivity, thermal diffusivity and the moisture absorption increased with increase in filler loading.     

Investigation of single and multidomain Pb(In(0.5)Nb(0.5))O(3)-Pb(Mg(1∕3)Nb(2∕3))O(3)-PbTiO(3) crystals with mm2 symmetry

The piezoelectric properties of Pb(In(0.5)Nb(0.5))O(3)-Pb(Mg(1∕3)Nb(2∕3))O(3)-PbTiO(3) crystals with various engineered domain configurations were investigated. Rhombohedral and monoclinic∕orthorhombic crystals poled along their crystallographic [011] directions were found to possess macroscopic mm2 symmetry, with "2R" and "1O" domain, respectively. Crystals with the "2R" domain configuration were found to exhibit high extensional piezoelectric coefficients d(33) (～1300 pC∕N) and d(32) (～-1680 pC∕N), while crystals with the "1O" configuration possessed high shear coefficients d(15) (～3500 pC∕N) and d(24) (～2070 pC∕N), with relatively low extensional piezoelectric coefficients d(33) (～340 pC∕N) and d(32) (～-260 pC∕N). The observed results were explained by "polarization rotation" model, as related to their respective domain configurations.     

(Y2O3,Yb2O3)复合掺杂ZrO2材料的中低温电导率

采用交流复阻抗体技术对（Y2O3，Yb2O3)复合掺杂ZrO2材料在573－873K这一温度范围的离子电导率随组成的变化关系进行了研究，发现在ZrO2-Y2O3系统加入Yb2O3会使得材料在中低温区域电导率降低。用经典的Arrhenius公式对实验数据进行的分析表明，导导率降低的原因在于Yb^3＋与结构中氧空位之间的缔合比Y^3 与氧空位之间的缔合更甚，阻碍了氧空位在中低温下的定向迁移。     

Effect of sintering parameters on the microstructure and microwave dielectric properties of Ba(Zn1/3Nb2/3)O3–ZnNb2O6 Ceramics

Ba(Zn_1/3Nb_2/3)O₃–ZnNb₂O₆(BZNZ) composite ceramics were fabricated by conventional solid solution processing. After optimizing the composition, the effects of the sintering parameters, such as the heating rate, the soaking time, and the cooling rate on densities, microstructure, and microwave dielectric properties were investigated using orthogonal experimental design method. The results show that with increasing the content of Ba(Zn_1/3Nb_2/3)O₃, the ε _r increases, while the Q × f value increases first, then decreases, and τ _f shifts to the negative value. The BZNZ ceramics with composition of 0.3Ba(Zn_1/3Nb_2/3)O₃–0.7ZnNb₂O₆ show the optimal dielectric properties. The results of orthogonal experimental design show that sintering parameters play an important role in the microstructure and dielectric properties. The ceramics show obvious duplex-grain structure. The importance sequence of the sintering parameters is: cooling rate > heating rate > soaking time. The sintering parameters were optimized, with 0.3Ba(Zn_1/3Nb_2/3)O₃–0.7ZnNb₂O₆ ceramic sintered at a heating rate of 2 °C/min, soaking time of 8 h, and cooling in the air. Samples have the excellent dielectric properties: ε_r = 32.75, Q × f = 34,100, and τ _f  = ?10.2 ppm/°C.     

Microwave dielectric properties and low-temperature sintering of (Zn0.8Mg0.2)2SiO4–TiO2 ceramics with Li2O–B2O3

Effects of Li₂O–B₂O₃ on the sintering behavior and the microwave dielectric properties of (Zn_0.8Mg_0.2)₂SiO₄–TiO₂ ceramics were investigated as a function of Li₂O–B₂O₃ content and sintering temperature. The Li₂O–B₂O₃ combined additives successfully reduced the sintering temperature of (Zn_0.8Mg_0.2)₂SiO₄–TiO₂ ceramics from 1,250 °C to 900 °C. With the increase of Li₂O–B₂O₃ content, the TiO₂ phase decreased and the unknown second phase increased, which led to the dielectric constant (ε _r ) and the maximum Q × f value decrease, and the temperature coefficient of resonant frequency (τ _f ) shift to a negative value. The specimens with 3 wt%Li₂O–B₂O₃ sintered at 900 °C for 2 h showed ε _r of 8.84, Q × f value of 15,500 GHz, and τ _f of 17.8 ppm/°C. And the material was compatible with Ag electrodes, which made it a promising ceramic for low temperature co-fired ceramics technology application.