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1.
Subsolidus phase relations have been determined for the Bi2O3-Fe2O3-Nb2O5 system in air (900-1075 °C). Three new ternary phases were observed—Bi3Fe0.5Nb1.5O9 with an Aurivillius-type structure, and two phases with approximate stoichiometries Bi17Fe2Nb31O106 and Bi17Fe3Nb30O105 that appear to be structurally related to Bi8Nb18O57. The fourth ternary phase found in this system is pyrochlore (A2B2O6O′), which forms an extensive solid solution region at Bi-deficient stoichiometries (relative to Bi2FeNbO7) suggesting that ≈4-15% of the A-sites are occupied by Fe3+. X-ray powder diffraction data confirmed that all Bi-Fe-Nb-O pyrochlores form with positional displacements, as found for analogous pyrochlores with Zn, Mn, or Co instead of Fe. A structural refinement of the pyrochlore 0.4400:0.2700:0.2900 Bi2O3:Fe2O3:Nb2O5 using neutron powder diffraction data is reported with the A cations displaced (0.43 Å) to 96g sites and O′ displaced (0.29 Å) to 32e sites (Bi1.721Fe0.190(Fe0.866Nb1.134)O7, Fdm (#227), ). This displacive model is somewhat different from that reported for Bi1.5Zn0.92Nb1.5O6.92, which exhibits twice the concentration of small B-type cations on the A-sites as the Fe system. Bi-Fe-Nb-O pyrochlores exhibited overall paramagnetic behavior with large negative Curie-Weiss temperature intercepts, slight superparamagnetic effects, and depressed observed moments compared to high-spin, spin-only values. The single-phase pyrochlore with composition Bi1.657Fe1.092Nb1.150O7 exhibited low-temperature dielectric relaxation similar to that observed for Bi1.5Zn0.92Nb1.5O6.92; at 1 MHz and 200 K the relative permittivity was 125, and above 350 K conductive effects were observed.  相似文献   

2.
X-ray photoelectron spectroscopy (XPS) measurements were carried out on a strontium pyroniobate (Sr2Nb2O7) powder sample, which was synthesized using standard solid-state method. The binding energy (BE) differences between the O 1s and cation core levels, Δ(O-Nb)=BE(O 1s)-BE(Nb 3d5/2) and Δ(O-Sr)=BE(O 1s)-BE(Sr 3d5/2), were used to characterize the valence electron transfer on the formation of the Nb-O and Sr-O bonds. The chemical bonding effects were considered on the basis of our XPS results for Sr2Nb2O7 and earlier published structural and XPS data for other Sr- or Nb-containing oxide compounds. The new data point for Sr2Nb2O7 is consistent with the previously derived relationship for a set of Nb5+-niobates that Δ(O-Nb) increases with increasing mean Nb-O bond distance, L(Nb-O). A new empirical relationship between Δ(O-Sr) and L(Sr-O) was also obtained. Interestingly, the correlation between Δ(O-Sr) and L(Sr-O) was found to differ from that between Δ(O-Nb) and L(Nb-O). Possible cause for the difference is discussed.  相似文献   

3.
Subsolidus phase relations in the CuOx-TiO2-Nb2O5 system were determined at 935 °C. The phase diagram contains one new phase, Cu3.21Ti1.16Nb2.63O12 (CTNO) and one rutile-structured solid solution series, Ti1−3xCuxNb2xO2: 0<x<0.2335 (35). The crystal structure of CTNO is similar to that of CaCu3Ti4O12 (CCTO) with square planar Cu2+ but with A site vacancies and a disordered mixture of Cu+, Ti4+ and Nb5+ on the octahedral sites. It is a modest semiconductor with relative permittivity ∼63 and displays non-Arrhenius conductivity behavior that is essentially temperature-independent at the lowest temperatures.  相似文献   

4.
Garnet-structure related metal oxides with the nominal chemical composition of Li5La3Nb2O12, In-substituted Li5.5La3Nb1.75In0.25O12 and K-substituted Li5.5La2.75K0.25Nb2O12 were prepared by solid-state reactions at 900, 950, and 1000 °C using appropriate amounts of corresponding metal oxides, nitrates and carbonates. The powder XRD data reveal that the In- and K-doped compounds are isostructural with the parent compound Li5La3Nb2O12. The variation in the cubic lattice parameter was found to change with the size of the dopant ions, for example, substitution of larger In3+(rCN6: 0.79 Å) for smaller Nb5+ (rCN6: 0.64 Å) shows an increase in the lattice parameter from 12.8005(9) to 12.826(1) Å at 1000 °C. Samples prepared at higher temperatures (950, 1000 °C) show mainly bulk lithium ion conductivity in contrast to those synthesized at lower temperatures (900 °C). The activation energies for the ionic conductivities are comparable for all samples. Partial substitution of K+ for La3+ and In3+ for Nb5+ in Li5La3Nb2O12 exhibits slightly higher ionic conductivity than that of the parent compound over the investigated temperature regime 25-300 °C. Among the compounds investigated, the In-substituted Li5.5La3Nb1.75In0.25O12 exhibits the highest bulk lithium ion conductivity of 1.8×10−4 S/cm at 50 °C with an activation energy of 0.51 eV. The diffusivity (“component diffusion coefficient”) obtained from the AC conductivity and powder XRD data falls in the range 10−10-10−7 cm2/s over the temperature regime 50-200 °C, which is extraordinarily high and comparable with liquids. Substitution of Al, Co, and Ni for Nb in Li5La3Nb2O12 was found to be unsuccessful under the investigated conditions.  相似文献   

5.
A crystal structural model for the orthorhombic compound V2.38Nb10.7O32.7, which is known as “V2Nb9O27.5”, was developed by means of selected area electron diffraction (SAED), Rietveld refinement and high resolution electron microscopy (HREM). The metastable compound is obtained by thermal decomposition of freeze-dried precursors as chain-like agglomerated nanoparticles or by reaction of V2O5 with fresh-precipitated Nb2O5 as more compact micro-scaled crystals. With the latter, it was possible to identify its structure for the first time (space group Cmmm). The tetragonal tungsten bronze (TTB)-type structure shows high potential for ionic intercalation, since easily reducible [V5+2O2−] units are implemented in the tunnels of a rigid niobium oxide framework.  相似文献   

6.
Phase transitions in MgAl2O4 were examined at 21-27 GPa and 1400-2500 °C using a multianvil apparatus. A mixture of MgO and Al2O3 corundum that are high-pressure dissociation products of MgAl2O4 spinel combines into calcium-ferrite type MgAl2O4 at 26-27 GPa and 1400-2000 °C. At temperature above 2000 °C at pressure below 25.5 GPa, a mixture of Al2O3 corundum and a new phase with Mg2Al2O5 composition is stable. The transition boundary between the two fields has a strongly negative pressure-temperature slope. Structure analysis and Rietveld refinement on the basis of the powder X-ray diffraction profile of the Mg2Al2O5 phase indicated that the phase represented a new structure type with orthorhombic symmetry (Pbam), and the lattice parameters were determined as a=9.3710(6) Å, b=12.1952(6) Å, c=2.7916(2) Å, V=319.03(3) Å3, Z=4. The structure consists of edge-sharing and corner-sharing (Mg, Al)O6 octahedra, and contains chains of edge-sharing octahedra running along the c-axis. A part of Mg atoms are accommodated in six-coordinated trigonal prism sites in tunnels surrounded by the chains of edge-sharing (Mg, Al)O6 octahedra. The structure is related with that of ludwigite (Mg, Fe2+)2(Fe3+, Al)(BO3)O2. The molar volume of the Mg2Al2O5 phase is smaller by 0.18% than sum of molar volumes of 2MgO and Al2O3 corundum. High-pressure dissociation to the mixture of corundum-type phase and the phase with ludwigite-related structure has been found only in MgAl2O4 among various A2+B3+2O4 compounds.  相似文献   

7.
The structures of NaRu2O4 and Na2.7Ru4O9 are refined using neutron diffraction. NaRu2O4 is a stoichiometric compound consisting of double chains of edge sharing RuO6 octahedra. Na2.7Ru4O9 is a non-stoichiometric compound with partial occupancy of the Na sublattice. The structure is a mixture of single, double and triple chains of edge-shared RuO6 octahedra. NaRu2O4 displays temperature independent paramagnetism with . Na2.7Ru4O9 is paramagnetic, χ0= with and a Curie constant of 0.0119 emu/mol Oe K. Specific heat measurements reveal a small upturn at low temperatures, similar to the upturn observed in La4Ru6O19. The electronic contribution to the specific heat (γ) for Na2.7Ru4O9 was determined to be15 mJ/moleRu K2.  相似文献   

8.
Orthorhombic Al2O3-rich aluminoborate is an important ceramic material for which two slightly different compositions have been assumed: Al5BO9 (5Al2O3:B2O3) and Al18B4O33 (9Al2O3:2B2O3). The formula Al18B4O33 (=Al4.91B1.09O9) was derived from results of chemical analyses when crystal structure data were not yet available. Subsequent structural investigations indicated Al5BO9 composition. Nevertheless, Al18B4O33 was still accepted as the correct stoichiometry assuming that additional B replaces 9% Al.Powder samples of both compositions and ones with excess boron were prepared by solid state reactions between α-Al2O3 and B2O3/H3BO3 at temperatures above 1100 °C and single-crystals were grown from flux at 1100 and 1550 °C. Products were investigated by single-crystal and powder XRD, 11B and 27Al solid-state MAS-NMR, Raman and FTIR spectroscopy as well as Laser-ablation ICP-MS. No indication of the predicted 9% B→Al substitution was found. LA ICP-MS indicated 12.36(27) wt% B2O3 corresponding to Al4.97B1.03O9. Hence, the suggested Al18B4O33 stoichiometry can be excluded for all synthesized samples. A very low amount of Al vacancies at a five-fold coordinated site are likely, charge balanced by an additional nearby three-fold coordinated B site. All evidences indicate that the title compound should be reported as Al5−xB1+xO9 with x<0.038(6), which is close to Al5BO9.  相似文献   

9.
MgAl2O4 spinel doping into cathode materials LiMn2O4 was used to improve the cyclic performance of the cathode. X-ray analysis results showed, when MgAl2O4 precursors were mixed with LiMn2O4 and sintered at 770 ℃ for 12 hour, MgAl2O4-LiMn2O4 mulriple spinel with the same physical characteristics as pure LiMn2O4 were synthesized. The electro-chemical performance testing showed, comparing with pure LiMn2O4, the first charge-discharge capacity of doping materials somewhat reduced, but the cyclic performance improved. The mechanism for doping material was also discussed.  相似文献   

10.
通过调节B2O3‐Bi2O3‐ZnO‐Al2O3(BBZA)玻璃的添加量研究其对钛酸钡(BaTiO3)陶瓷烧结条件、晶体结构和介电性能的影响。结果表明:添加适量的BBZA玻璃能够有效地将BaTiO3陶瓷烧结温度由1350℃降至950℃,并使其致密化。同时,添加BBZA玻璃后,BaTiO3的晶体结构随着烧结温度的升高而发生转变(立方相→四方相)。另外,BBZA玻璃的引入使BaTiO3陶瓷的居里峰得到了有效的抑制和拓宽。陶瓷微观形貌显示,玻璃相均匀分布在BaTiO3晶粒表面。优化的BaTiO3陶瓷制备条件如下:BBZA添加量(质量分数)为2.0%,烧结温度为950℃。在该条件下制备的BaTiO3陶瓷介电常数达到1364,介电损耗低至1.2%。  相似文献   

11.
Phase equilibria studies of the CaO:TiO2:Nb2O5 system confirmed the formation of six ternary phases: pyrochlore (A2B2O6O′), and five members of the (110) perovskite-slab series Can(Ti,Nb)nO3n+2, with n=4.5, 5, 6, 7, and 8. Relations in the quasibinary Ca2Nb2O7−CaTiO3 system, which contains the Can(Ti,Nb)nO3n+2 phases, were determined in detail. CaTiO3 forms solid solutions with Ca2Nb2O7 as well as CaNb2O6, resulting in a triangular single-phase perovskite region with corners CaTiO3-70Ca2Ti2O6:30Ca2Nb2O7-80CaTiO3:20CaNb2O6. A pyrochlore solid solution forms approximately along a line from 42.7:42.7:14.6 to 42.2:40.8:17.0 CaO:TiO2:Nb2O5, suggesting formulas ranging from Ca1.48Ti1.48Nb1.02O7 to Ca1.41Ti1.37Nb1.14O7 (assuming filled oxygen sites), respectively. Several compositions in the CaO:TiO2:Ta2O5 system were equilibrated to check its similarity to the niobia system in the pyrochlore region, which was confirmed. Structural refinements of the pyrochlores Ca1.46Ti1.38Nb1.11O7 and Ca1.51Ti1.32V0.04Ta1.10O7 using single-crystal X-ray diffraction data are reported (Fd3m (#227), a=10.2301(2) Å (Nb), a=10.2383(2) Å (Ta)), with Ti mixing on the A-type Ca sites as well as the octahedral B-type sites. Identical displacive disorder was found for the niobate and tantalate pyrochlores: Ca occupies the ideal 16d position, but Ti is displaced 0.7 Å to partially occupy a ring of six 96g sites, thereby reducing its coordination number from eight to five (distorted trigonal bipyramidal). The O′ oxygens in both pyrochlores were displaced 0.48 Å from the ideal 8b position to a tetrahedral cluster of 32e sites. The refinement results also suggested that some of the Ti in the A-type positions may occupy distorted tetrahedra, as observed in some zirconolite-type phases. The Ca-Ti-(Nb,Ta)-O pyrochlores both exhibited dielectric relaxation similar to that observed for some Bi-containing pyrochlores, which also exhibit displacively disordered crystal structures. Observation of dielectric relaxation in the Ca-Ti-(Nb,Ta)-O pyrochlores suggests that it arises from the displacive disorder and not from the presence of polarizable lone-pair cations such as Bi3+.  相似文献   

12.
In this work we report about a new rare-earth oxoborate β-Dy2B4O9 synthesized under high-pressure/high-temperature conditions from Dy2O3 and boron oxide B2O3 in a B2O3/Na2O2 flux with a walker-type multianvil apparatus at 8 GPa and 1000°C. Single crystal X-ray structure determination of β-Dy2B4O9 revealed: , a=616.2(1) pm, b=642.8(1) pm, c=748.5(1) pm, α=102.54(1)°, β=97.08(1)°, γ=102.45(1)°, Z=2, R1=0.0151, wR2=0.0475 (all data). The compound exhibits a new structure type which is built up from bands of linked BO3- (Δ) and tetrahedral BO4-groups (□). The Dy3+-cations are positioned in the voids between the bands. According to the conception of fundamental building blocks β-Dy2B4O9 can be classified with the notation 2Δ6□:Δ3□=4□=3□Δ. Furthermore we report about temperature-resolved in situ powder diffraction measurements and IR-spectroscopic investigations on β-Dy2B4O9.  相似文献   

13.
通过调节B2O3-Bi2O3-ZnO-Al2O3(BBZA)玻璃的添加量研究其对钛酸钡(BaTiO3)陶瓷烧结条件、晶体结构和介电性能的影响。结果表明:添加适量的BBZA玻璃能够有效地将BaTiO3陶瓷烧结温度由1 350℃降至950℃,并使其致密化。同时,添加BBZA玻璃后,BaTiO3的晶体结构随着烧结温度的升高而发生转变(立方相→四方相)。另外,BBZA玻璃的引入使BaTiO3陶瓷的居里峰得到了有效的抑制和拓宽。陶瓷微观形貌显示,玻璃相均匀分布在BaTiO3晶粒表面。优化的BaTiO3陶瓷制备条件如下:BBZA添加量(质量分数)为2.0%,烧结温度为950℃。在该条件下制备的BaTiO3陶瓷介电常数达到1 364,介电损耗低至1.2%。  相似文献   

14.
A new borate, Cs2Al2B2O7, was synthesized by solid-state reaction. It crystallizes in the monoclinic space group P21/c with a=6.719(1) Å, b=7.121(1) Å, c=9.626(3) Å, β=115.3(1)°, and Z=2. In the structure, two AlO4 tetrahedra and two BO3 planar triangles are connected alternately by corner-sharing to from nearly planar [Al2B2O10] rings, which are further linked via common O1 atom to generate layers in the bc plane. These layers then share the O3 atoms lying on a center of inversion to form a three-dimensional framework with Cs atoms residing in the channels. The IR spectrum confirms the presence of both BO3 and AlO4 groups and the UV-vis-IR diffuse reflectance spectrum indicates a band gap of about 4.13(2) eV.  相似文献   

15.
Magnetic diphase nanostructures of ZnFe2O4/γ-Fe2O3 were synthesized by a solvothermal method. The formation reactions were optimized by tuning the initial molar ratios of Fe/Zn. All samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and Raman spectra. It is found that when the initial molar ratio of Fe/Zn is larger than 2, a diphase magnetic nanostructure of ZnFe2O4/γ-Fe2O3 was formed, in which the presence of ZnFe2O4 enhanced the thermal stability of γ-Fe2O3. Further increasing the initial molar ratio of Fe/Zn larger than 6 destabilized the diphase nanostructure and yielded traces of secondary phase α-Fe2O3. The grain surfaces of diphase nanostructure exhibited a spin-glass-like structure. At room temperature, all diphase nanostructures are superparamagnetic with saturation magnetization being increased with γ-Fe2O3 content.  相似文献   

16.
采用水热合成法制备了Co3O4及复合Ag/Co3O4、CuO/Co3O4一维纳米产品。用XRD,FE-SEM和TEM手段对产品进行了表征。采用循环伏安法研究了合成产品修饰的玻碳电极在碱性溶液中对对硝基苯酚的电催化还原性能。与裸玻碳电极相比,1mmol·L-1的对硝基苯酚在用Co3O4、特别是CuO/Co3O4修饰的玻碳电极上还原的峰电流明显增大,用Ag/Co3O4(Ag/Co原子比分别为1∶5和2∶5)修饰的玻碳电极催化还原对硝基苯酚时,尽管还原峰电流增大不是太大,但其峰电位明显降低(分别降低0.265和0.371V)。  相似文献   

17.
The crystal structures of K2S2O7, KNaS2O7 and Na2S2O7 have been solved and/or refined from X-ray synchrotron powder diffraction data and conventional single-crystal data. K2S2O7: From powder diffraction data, monoclinic C2/c, Z=4, a=12.3653(2), b=7.3122(1), , β=93.0792(7)°, RBragg=0.096. KNaS2O7: From powder diffraction data; triclinic , Z=2, a=5.90476(9), b=7.2008(1), , α=101.7074(9), β=90.6960(7), γ=94.2403(9)°, RBragg=0.075. Na2S2O7: From single-crystal data; triclinic , Z=2, a=6.7702(9), b=6.7975(10), , α=116.779(2), β=96.089(3), γ=84.000(3)°, RF=0.033. The disulphate anions are essentially eclipsed. All three structures can be described as dichromate-like, where the alkali cations coordinate oxygens of the isolated disulphate groups in three-dimensional networks. The K-O and Na-O coordinations were determined from electron density topology and coordination geometry. The three structures have a cation-disulphate chain in common. In K2S2O7 and Na2S2O7 the neighbouring chains are antiparallel, while in KNaS2O7 the chains are parallel. The differences between the K2S2O7 and Na2S2O7 structures, with double-, respectively single-sided chain connections and straight, respectively, corrugated structural layers can be understood in terms of the differences in size and coordinating ability of the cations.  相似文献   

18.
Two novel noncentrosymmetric borates oxides, MBi2B2O7 or MBi2O(BO3)2 (MCa, Sr), have been synthesized by solid-state reactions in air at temperatures in the 600-700 °C range. Their crystal structures have been determined ab initio and refined using powder neutron diffraction data. CaBi2B2O7 crystallizes in the orthorhombic Pna21 space group with a=8.9371(5) Å, b=5.4771(3) Å, c=12.5912(7) Å, Z=4, Rwp=0.118, χ2=2.30. SrBi2B2O7 crystallizes in the hexagonal P63 space group with a=9.1404(4) Å, c=13.0808(6) Å, Z=6, Rwp=0.115, χ2=4.15. Large displacement parameters suggest the presence of disorder in SrBi2B2O7 as also revealed by diffuse 2×a superstructure reflections in electron diffraction patterns. Both structures are built of identical (001) neutral layers of corner-sharing BO3 triangles and MO6 trigonal prisms forming six-membered rings in which Bi2O groups are located. Adjacent layers are stacked in a staggered configuration and connected through weak Bi-O bonds. A moderate efficiency for second harmonic generation (SHG) has been measured for a powder sample of CaBi2B2O7 (deff=2deff(KDP)).  相似文献   

19.
A new structural state 25L-Ta2O5, obtained from sintering and annealing treatments of a Ta2O5 powder, is identified both by electron diffraction and high resolution imaging on a transmission electron microscope (TEM). According to general rules for the different L-Ta2O5 structures proposed by Grey et al. (J. Solid State Chem. 178 (2005) 3308), a structural model is derived from their crystallographic data on 19L-Ta2O5. This model yields simulated images in agreement with high resolution TEM observations of the structure oriented along its [001] zone axis, but only for a very thin crystal thickness of less than 1.2 nm. Such a limitation is shown to be due to a modulation of the structure along its [001] axis. Actually, from an analysis of a diffuse scattering and of its evolution into satellites reflections as a function of the cooling rate, a second order incommensurate phase transition can be assumed to occur in this compound. The property of single phase samples observed by TEM is also verified by X-ray powder diffraction. In a discussion about studies performed by different authors on incommensurate structures in the system Ta2O5-WO3, it is noticed that TEM results, similar to ours, indicate that phase transitions could be expected in these structures.  相似文献   

20.
采用溶胶-凝胶与固相反应相结合的方法制备了xNiFe2O4/(1-x)BaTiO3(x=0.1,0.2,0.3,0.4,0.5,0.6)系列复合多铁材料.X射线衍射(XRD)结果表明,复合材料中只含有钙钛矿结构的BaTiO3和尖晶石结构的NiFe2O4,说明共烧过程中两者未发生明显的化学反应,铁电相与铁磁相共存.扫描电子显微镜(SEM)观测结果表明材料内部是异质结构的,高分辨透射电子显微镜(HRTEM)观测结果进一步说明了NiFe2 O4和BaTiO3共存,并且在两种物质的接触处能够看到清晰的界面.这种由BaTiO3和NiFe2 O4组成的复合材料对外同时表现出铁电性和铁磁性.电滞回线结果表明,该复合材料具有铁电性,但存在着一定的漏电.介电频谱表明材料的介电常数随着频率的升高而下降,在低频下达到定值,并且铁磁相的含量对材料的介电性有影响.磁性能测试结果表明材料的磁性源于NiFe2O4,并且磁性随着NiFe2O4含量的增加而增强.  相似文献   

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