Neutron diffraction studies on Ca1−x Ba x Zr4P6O24 solid solutions

Herein we report the results of detailed crystallographic studies of Ca_1−x Ba _x Zr₄P₆O₂₄ compositions from combined Rietveld refinements of powder X-ray and neutron diffraction data. All the studied compositions crystallize in rhombohedral lattice (space group R-3 No. 148). A continuous solid solution is concluded from the systematic variation of unit cell parameters. The variation of unit cell parameters with the composition indicates decreasing trend in a parameter with increasing Ba2+ concentration contrast to an increasing trend in c parameter.      

Bi0·5K0·5TiO3-based lead-free relaxor ferroelectric with high energy storage performances via the grain size and bandgap engineering

Dielectric capacitors with high energy storage performance show a huge competitive advantage for use in vehicles and power electronics. Here, the (1-x) (0.75Bi_0·5K_0·5TiO₃?0.25BiFeO₃) – xSr_0.7Bi_0·2TiO₃ (BKT-BF-xSBT) materials were designed based on the dual optimization strategy of grain size and bandgap. The optimal performance was obtained in the BKT-BF-0.4SBT sample, achieving high energy storage density W_rec of 5.21 J/cm³ and high energy storage efficiency η of 90.87% at 360 kV/cm. The addition of SBT optimized the microstructure and relaxation behavior of BKT-BF ceramic, giving rise to the formation of polar nanoregions (PNRs), small grain size (G), compact grain boundaries, and wide bandgap (E_g) synchronously. Encouragingly, prominent stabilities against temperature, frequency, and cycle numbers, and favorable charge/discharge performance (power density P_D ≈ 64.5 MW/cm³, τ_0.9 ≈ 90 ns) are also accomplished in designed BKT-based ceramics. These findings indicate that the BKT-BF-xSBT ceramic system has excellent potential in the dielectric energy storage field and also provides a viable prospect for engineering design of high-efficiency lead-free dielectrics via bandgap and grain size.     

12CaO·7Al_2O_3∶Ce~(3+)透明陶瓷的制备及其闪烁特性研究

采用高温固相法制备了不同Ce3+掺杂浓度的12Ca O·7Al2O3(C12A7∶x%Ce3+)陶瓷样品。在350 nm紫外光激发下,样品的发射光谱呈现为主峰位于440 nm的宽带,来源于Ce3+的5d1→2F5/2和2F7/2的辐射跃迁。随着Ce3+掺杂浓度的增加,发射强度增大;当Ce3+摩尔分数超过0.7%时,有杂质相出现。为了进一步提高光致发光强度,采用自蔓延燃烧法合成了C12A7∶0.5%Ce3+陶瓷样品。在H2气氛下热处理,通过改变笼中阴离子基团的种类和数目提高了陶瓷闪烁特性(发光强度和衰减时间)。结果表明,C12A7∶Ce3+陶瓷是可应用于闪烁体的潜在材料。     

Co含量对Bi6Fe2-xCoxTi3O18样品多铁性的影响

用固相工艺制备了Bi₆Fe_2-xCo_xTi₃O₁₈ (BFCT-x, x=0, 0.2, 0.6, 0.8, 1.0, 1.2, 1.6, 1.8, 和2.0)多铁陶瓷样品, 样品X射线谱分析发现, 随着Co含量的增加, 样品晶格常数出现了先增大后减小的变化. 室温下, BFCT-0.6样品呈现出相对较高的饱和磁化强度, 2M_s约为4.49 emu/g, BFCT-1.0具有最高的剩余磁化强度, 2M_r约为0.89 emu/g. Co含量在0.2 ≤x≤qslant 1.2范围内, 随着Co含量的增加样品顺磁–铁磁相变温度从752 K降至372 K. 小量的Co改善了样品的铁电性能, 当x=0.6时样品样品的铁电性能最佳, 随着含量增大样品铁电性能下降, 但当x >1.2时样品的铁电性能又得到了改善.     

Crystal structures and phonon modes of Ba(Ca1/2W1/2)O3, Ba(Ca1/2Mo1/2)O3 and Ba(Sr1/2W1/2)O3 complex perovskites investigated by Raman scattering

This work investigates the crystal structures and phonon modes of Ba(Ca_1/2W_1/2)O₃, Ba(Ca_1/2Mo_1/2)O₃ and Ba(Sr_1/2W_1/2)O₃ perovskites by Raman spectroscopy. The samples were produced by conventional solid‐state processing at 1200 °C. X‐ray diffraction showed that single‐phase homogeneous materials were produced, which are cubic or pseudo‐cubic in symmetry. The existing controversies in the literature for these complex perovskites were investigated by comparing experimental Raman data with group‐theory analysis. Ceramics with Ca and W or Mo were found to be cubic, space group Fm3 m. For these materials, four Raman‐active bands were observed and the fitting parameters showed that the Ba(Ca_1/2Mo_1/2)O₃ ceramic presents bands at lower wavenumbers if compared with the Ba(Ca_1/2W_1/2)O₃ sample. For the Ba(Sr_1/2W_1/2)O₃ material, two hypotheses were investigated for monoclinic or triclinic structures. The experimental results showed 12 Raman‐active modes for this ceramic, which is in perfect agreement with the theoretical predictions for a monoclinic (I2/m) structure. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation, characterization and luminescence properties of porous Si3N4 ceramics with Eu2O3 as sintering additive

Porous Si₃N₄ ceramics with photoluminescence properties were prepared by pressureless sintering using α-Si₃N₄ powder as raw material and Eu₂O₃ as sintering additive. Chemical composition, phase formation, microstructure and photoluminescence properties of porous Si₃N₄ ceramics were studied by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence measurements (PL/PLE). The results show that single Eu₂O₃ additive promotes α→β transformation but not significant densification. A broad band emission center at 570 nm assigned to Eu²⁺ is observed, Eu³⁺ in Eu₂O₃ is (partially) converted to Eu²⁺ by reaction with Si₃N₄, which results in a lower β aspect ratio and β-content compared to the other Ln (Ln=lanthanide) oxide additives.     

Fluoride solid electrolytes

Relations between the structure and electrical properties of fluoride systems with different structures are presented. Physical properties of fluorite-structured (MF₂-RF₃, MF₂-AF, MF₂-M′F₂, M = Ba, Pb, R = La-Lu, Sc, Y, A = Li, Na, K, Rb, M′ = Ba, Cd, Mg), orthorhombic (RF₃, R = Tb-Er, Y), tysonite-structured (RF₃-MF₂, R = La-Nd, M = Sr), and monoclinic (BaR₂F₈, R = Ho-Yb, Y) fluoride single crystals or ceramics (ErF₃, MF₂-RF₃, M = Ca, Ba, R = La, Gd, Tb, Y), glasses (ZBLAN, PIBAL) and eutectic composites (LiF-RF₃, R = La-Gd, Y, PbF₂-RF₃, R = Ho, Yb, Y, Sc, PbF₂-AF, A = Li, Na, PbF₂-MgF₂) are compared. Anisotropy of electrical properties is explained. Models of aggregation of defects into clusters are proposed. In fluoritestructured crystals, the highest ionic conductivity was found for PbF₂: 7 mol % ScF₃ (at 500 K, σ₅₀₀ = 0.13 S/cm). In tysonite-structured crystals, the highest ionic conductivity was found for LaF 3: 3 mol % SrF₂ (σ₅₀₀ = 2.4 × 10⁻² S/cm). Different types of coordination polyhedrons and their different linking in orthorhombic and tysonite structures explain a large difference between conductivities in both structures. Published in Russian in Elektrokhimiya, 2009, Vol. 45, No. 6, pp. 668–678. The article is published in the original. Published by report at IX Conference “Fundamental Problems of Solid State Ionics”, Chernogolovka, 2008.     

Development and optimisation of a portable micro-XRF method for in situ multi-element analysis of ancient ceramics

Non-destructive analysis of cultural objects by micro-XRF spectrometry is an advantageous multi-element technique that has rapidly developed during the past few years. Portable instruments contribute significantly to the in situ analysis of valuable cultural objects, which cannot be transported to the laboratory. Ancient ceramics are the most common archaeological findings and they carry a significant historical content. Their analysis often presents certain particularities due to surface irregularities and heterogeneity problems. In the present work, the analytical characteristics (beam spot size, geometry effect and detection limits) of a compact and portable micro-XRF instrument with a monocapillary lens are presented in details. The standard reference materials SARM 69, SRM 620, NCS DC 73332 and the reference materials AWI-1 and PRI-1 were analysed for the determination of the detection limits (DL's) and the evaluation of the accuracy of the micro-XRF. Emphasis is given on the critical parameters, which should be monitored during measurements and influence the final results in the analysis of ancient ceramics. A quantitative analysis of ancient ceramic samples from Abdera (North Greece) is also presented.     

MAS-NMR investigations of the crystallization behaviour of lithium aluminum silicate (LAS) glasses containing P2O5 and TiO2 nucleants

Lithium aluminum silicate (LAS) glass of composition (mol%) 20.4Li₂O-4.0Al₂O₃-68.6SiO₂-3.0K₂O-2.6B₂O₃-0.5P₂O₅-0.9TiO₂ was prepared by melt quenching. The glass was then nucleated and crystallized based on differential thermal analysis (DTA) data and was characterized by ²⁹Si, ³¹P, ¹¹B and ²⁷Al MAS-NMR. XRD and ²⁹Si NMR showed that lithium metasilicate (Li₂SiO₃) is the first phase to c form followed by cristobalite (SiO₂) and lithium disilicate (Li₂Si₂O₅). ²⁹Si MAS-NMR revealed a change in the network structure already for the glasses nucleated at 550 °C. Since crystalline Li₃PO₄, as observed by ³¹P MAS-NMR, forms concurrently with the silicate phases, we conclude that crystalline Li₃PO₄ does not act as a nucleating agent for lithium silicate phases. Moreover, ³¹P NMR indicates the formation of M-PO₄ (M=B, Al or Ti) complexes. The presence of BO₃ and BO₄ structural units in all the glass/glass-ceramic samples is revealed through ¹¹B MAS-NMR. B remains in the residual glass and the crystallization of silicate phases causes a reduction in the number of alkali ions available for charge compensation. As a result, the number of trigonally coordinated B (BO₃) increases at the expense of tetrahedrally coordinated B (BO₄). The ²⁷Al MAS-NMR spectra indicate the presence of tetrahedrally coordinated Al species, which are only slightly perturbed by the crystallization.     

能量色散X射线荧光探针用于古陶瓷的工艺与产地研究

利用能量色散X射线荧光(EDXRF)探针技术,研究了旧县坪遗址出土的一件青瓷样品的制造工艺与产地。从青瓷样品的器壁部,用切割法取下一个断面,用探针进行线性扫描分析。结果表明:在胎釉间存在的白色层状物的化学成分介于胎釉之间,断定其应为在烧制过程中经一系列理化反应而形成的反应层。经对该青瓷样品胎釉化学成分的聚类分析,发现其与宋代河南临汝窑青瓷的胎釉化学成分基本一致。并且,该样品与临汝窑青瓷在釉色和装饰风格上都相近。因此,旧县坪遗址的这件青瓷样品应为临汝窑制品。