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1.
Five series of perovskite-type compounds in the system La1−xCaxCr1−yTiyO3 with the nominal compositions y=0, x=0-0.5; y=0.2, x=0.2-0.8; y=0.5, x=0.5-1.0; y=0.8, x=0.6-1.0 and y=1, x=0.8-1 were synthesized by a ceramic technique in air (final heating 1350 °C). On the basis of the X-ray analysis of the samples with (Ca/Ti)?1, the phase diagram of the CaTiO3-LaCrIIIO3-CaCrIVO3 quasi-ternary system was constructed. Extended solid solution with a wide homogeneity range is formed in the quasi-ternary system CaCrIVO3-CaTiO3-LaCrIIIO3. The solid solution La(1−x′−y)Ca(x′+y)CrIVxCrIII(1−x′−y)TiyO3 exists by up to 0.6-0.7 mol fractions of CaCrIVO3 (x<0.6-0.7) at the experimental conditions. The crystal structure of the compounds is orthorhombic in the space group Pbnm at room temperature. The lattice parameters and the average interatomic distances of the samples within the solid solution ranges decrease uniformly with increasing Ca content. Outside the quasi-ternary system, the nominal compositions La0.1Ca0.9TiO3, La0.2Ca0.8TiO3, La0.4Ca0.6Cr0.2Ti0.8O3 and La0.3Ca0.7Cr0.2Ti0.8O3 in the system La1−xCaxCr1−yTiyO3 were found as single phases with an orthorhombic structure. In the temperature range between 850 and 1000 °C, the synthesized single-phase compositions are stable at pO2=6×10−16-0.21×105 Pa. Oxygen stoichiometry and electrical conductivity of the separate compounds were investigated as functions of temperature and oxygen partial pressure. The chemical stability of these oxides with respect to oxygen release during thermal dissociation decreases with increasing Ca-content. At 900 °C and oxygen partial pressure 1×10−15-0.21×105 Pa, the compounds with x>y (acceptor doped) are p-type semiconductors and those with x<y (donor doped) and x=y are n-type semiconductors. The type and level of electrical conductivity are functions of the concentration ratios of cations occupying the B-sites of the perovskite structures: [Cr3+]/[Cr4+] and [Ti4+]/[Ti3+]. The maximum electrical conductivity at 900 °C and pO2=10−15 Pa was found for the composition La0.1Ca0.9TiO3 (near 50 S/cm) and in air at 900 °C for La0.5Ca0.5CrO3 (close to 100 S/cm).  相似文献   

2.
A tin(II) squarate Sn2O(C4O4)(H2O) was synthesized by hydrothermal technique. It crystallizes in the monoclinic system, space group C2/m (no. 12) with lattice parameters a=12.7380(9) Å, b=7.9000(3) Å, c=8.3490(5) Å, β=121.975(3)°, V=712.69(7) Å3, Z=4. The crystal structure determined with an R=0.042 factor, consists of [(Sn4O10)(H2O)2] units connected from one another in the [101] and [010] directions via squarate groups to form layers separated by Sn(II) lone pairs. This compound presents the same remarkable structural arrangement as observed in the tin-oxo-fluoride Sn2[Sn2O2F4] inorganic compound with Sn(II) lone pairs E(1) and E(2) concentrated in large rectangular-shape tunnels running along [001] direction.  相似文献   

3.
4.
Eu3+-doped Ca2SnO4 (solid solutions of Ca2−xEu2xSn1−xO4, 0?x?0.3) and Eu3+ and Y3+-codoped Ca2SnO4 (Ca1.8Y0.2Eu0.2Sn0.8O4) were prepared by solid-state reaction at 1400 °C in air. Rietveld analysis of the X-ray powder diffraction patterns revealed that Eu3+ replaced Ca2+ and Sn4+ in Eu3+-doped Ca2SnO4, and that Eu3+ replaced Ca2+ and Y3+ replaced Sn4+ in Ca1.8Y0.2Eu0.2Sn0.8O4. Red luminescence at 616 nm due to the electric dipole transition 5Do7F2 was observed in the photoluminescence (PL) spectra of Ca2−xEu2xSn1−xO4 and Ca1.8Y0.2Eu0.2Sn0.8O4 at room temperature. The maximum PL intensity in the solid solutions of Ca2−xEu2xSn1−xO4 was obtained for x=0.1. The PL intensity of Ca1.8Y0.2Eu0.2Sn0.8O4 was 1.26 times greater than that of Ca2−xEu2xSn1−xO4 with x=0.1.  相似文献   

5.
Blue photoluminescence properties of Ti-doped alkaline-earth stannates, A2(Sn1−xTix)O4 (A=Ca, Sr, Ba) (x=0.005-0.15), were examined at room temperature. These stannates showed intense broad emission bands peaking at 445 nm for Ca2SnO4, at 410 nm for Sr2SnO4, and at 425 nm for Ba2SnO4 under UV excitation. Emission intensities were relatively insensitive to Ti concentration and no sharp concentration quenching was observed. Mixing alkaline-earth ions in the crystal structures did not increase the emission intensities in the A2(Sn1−xTix)O4 system. The excitation spectra of these stannates exhibited broad bands just below the fundamental absorption edges, implying that luminescence centers do not consist of the component elements in the host materials. It was suggested that the isolated TiO6 complexes are possible luminescence centers in these materials, as previously proposed in other Ti-doped stannates such as Mg2SnO4 and Y2Sn2O7.  相似文献   

6.
The hydration behaviour of Ca3Al2O6, Ca12Al14O33 and CaAl2O4 with added amorphous silica at 40, 65 and 90 °C has been studied for periods ranging from 1 to 31 days. In hydrated samples crystalline phases like katoite (Ca3Al2(SiO4)3−x(OH)4x) and gibbsite, Al(OH)3, were identified, likewise amorphous phases like Al(OH)x, calcium silicate hydrates, C-S-H, and calcium aluminosilicate hydrates, C-S-A-H, were identified. The stoichiometry of Ca3Al2(SiO4)3−x(OH)4x (0?3−x?0.334), which was the main crystalline product, was established by Rietveld refinement of X-ray and neutron diffraction data and by transmission electron microscopy.  相似文献   

7.
Over 100 samples were prepared as (Ga,In)4(Sn,Ti)n−4O2n−2, n=6, 7, and 9 by solid-state reaction at 1400 °C and characterized by X-ray diffraction. Nominally phase-pure beta-gallia-rutile intergrowths were observed in samples prepared with n=9 (0.17?x?0.35 and 0?y?0.4) as well as in a few samples prepared with n=6 and 7. Rietveld analysis of neutron time-of-flight powder diffraction data were conducted for three phase-pure samples. The n=6 phase Ga3.24In0.76Sn1.6Ti0.4O10 is monoclinic, P2/m, with Z=2 and a=11.5934(3) Å, b=3.12529(9) Å, c=10.6549(3) Å, β=99.146(1)°. The n=7 phase Ga3.24In0.76Sn2.4Ti0.6O12 is monoclinic, C2/m, with Z=2 and a=14.2644(1) Å, b=3.12751(2) Å, c=10.6251(8) Å, β=108.405(1)°. The n=9 phase Ga3.16In0.84Sn4TiO16 is monoclinic, C2/m, with Z=2 a=18.1754(2) Å, b=3.13388(3) Å, c=10.60671(9) Å, β=102.657(1)°. All of the structures are similar in that they possess distorted hexagonal tunnels parallel to the [010] vector.  相似文献   

8.
Zn2TixSn1−xO4 (0?x?1) solid solutions with an inverse spinel structure (Fd3m) were synthesized by solid-state reactions at 1300°C of the stoichiometric mixtures of ZnO, TiO2 and SnO2. X-ray diffraction, thermogravimetric and differential thermal analyses, scanning electron microscopy, transmission electron microscopy and BET specific surface area measurements were used to gain insights into the solid-state reactions and phase transformation of the system. Optical absorption property of the Zn2TixSn1−xO4 (0?x?1) solid solutions was studied with the ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS). The Zn2TixSn1−xO4 (0?x?1) solid solutions showed optical absorptions of the semiconductors in the near ultraviolet region; the adsorption band shifts with the composition of the solid solution.  相似文献   

9.
Composite solid electrolytes in the system (1 − x)LiNO3-xAl2O3, with x = 0.0-0.5 were synthesized by sol-gel method. The synthesis carried out at low temperature resulted in voluminous and fluffy products. The obtained materials were characterized by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy/energy dispersive X-ray, Fourier transform infrared spectroscopy and AC impedance spectroscopy. Structural analysis of the samples showed base centred cell type of point lattice of LiNO3 for the composite samples with x = 0.1-0.2 and body centred cell for the sample with x = 0.3. A trace amount of α-LiAlO2 crystal phase was also present in these composite samples. The thermal analysis showed that the samples were in a stable phase between 48 °C and 230-260 °C. Morphological analysis indicated the presence of amorphous phase and particles with sizes ranging from micro to nanometre scale for the composite sample with x = 0.1. The conductivities of the composites were in the order of 10−3 and 10−2 S cm−1 at room temperature and 150 °C, respectively.  相似文献   

10.
A novel red light-emitting material, Ca3Al2O6:Eu3+, which is the first example found in the Ca3Al2O6 host, was prepared by calcination of a layered double hydroxide precursor at 1350 °C. The precursor, [Ca2.9−xAl2Eux(OH)9.8](NO3)2+x·2.5H2O, was prepared by coprecipitation of metal nitrates with sodium hydroxide. The material is a loose powder composed of irregular particles formed from aggregation of particles of a few nanometers, as shown in scanning electron microscope (SEM) images. It was found that the photoluminescence intensity reached the maximum when the calcination temperature was 1350 °C and the concentration of Eu3+ was 1.0%. The material emits bright red emission at 614 nm under a radiation of λ=250 nm.  相似文献   

11.
Polyoxoniobate chemistry, both in the solid state and in solution is dominated by [Nb6O19]8−, the Lindquist ion. Recently, we have expanded this chemistry through use of hydrothermal synthesis. The current publication illustrates how use of heteroatoms is another means of diversifying polyoxoniobate chemistry. Here we report the synthesis of Na8[Nb8Ti2O28]·34H2O and its structural characterization from single-crystal X-ray data. This salt crystallizes in the P-1 space group (a=11.829(4) Å, b=12.205(4) Å, c=12.532(4) Å, α=97.666(5)°, β=113.840(4)°, γ=110.809(4)°), and the decameric anionic cluster [Nb8Ti2O28]8− has the same cluster geometry as the previously reported [Nb10O28]6− and [V10O28]6−. Molecular modeling studies of [Nb10O28]6− and all possible isomers of [Nb8Ti2O28]8− suggest that this cluster geometry is stabilized by incorporating the Ti4+ into cluster positions in which edge-sharing is maximized. In this manner, the overall repulsion between edge-sharing octahedra within the cluster is minimized, as Ti4+ is both slightly smaller and of lower charge than Nb5+. Synthetic studies also show that while the [Nb10O28]6− cluster is difficult to obtain, the [Nb8Ti2O28]8− cluster can be synthesized reproducibly and is stable in neutral to basic solutions, as well.  相似文献   

12.
New titanyl phosphate Ti2O(H2O)(PO4)2 has been prepared and characterized by X-ray and neutron diffraction, nuclear magnetic resonance, infrared and Raman spectroscopies and thermogravimetric analysis. The crystal structure has been solved from neutron powder diffraction data at 300 K by Rietveld method in P21 space group. The refinement led to satisfactory profile factors (Rp=2.7%, Rwp=3.2%) and crystal structure model indicators (RB=5.8%, RF=3.2%). The cell is monoclinic with a=7.3735 Å, b=7.0405 Å, c=7.6609 Å and β=121.48°, Z=4. The structure can be described as a three-dimensional framework built up by chains of [TiO5(OH2)] octahedra with alternative short bonds [Ti(1)-O(12); Ti(2)-O(12), 1.88-1.84 Å] and long ones [Ti(1)-OW; Ti(2)-OW, 2.25-2.23 Å] along c-axis and connected via [PO4] tetrahedra. Oxygen atom denoted O(12) is only linked to two titanium atoms and Oxygen atom denoted OW is linked to two titanium atoms and two hydrogen atoms. O(12) and OW are not linked to P atoms and justify the titanyl phosphate formulation Ti2O(H2O)(PO4)2. The infrared and Raman spectra presents peaks due to vibrations of Ti-O, P-O and O-H bonds. The 31P MAS NMR spectrum reveals two 31P resonance lines, in agreement with the structure which showed two crystallographic sites for phosphorus. The thermogravimetric analysis show that Ti2O(H2O)(PO4)2 is thermally stable until 400 °C. Above this temperature, it losses water and decomposes to Ti5O4(PO4)4 and TiP2O7.  相似文献   

13.
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   

14.
The perovskite-related phase Ca3Nb2O8, when grown as single crystals from a calcium vanadate flux, incorporates a small amount of vanadium from the flux to form the composition Ca3Nb2−xVxO8 with x=0.025. The crystals have pseudo-cubic symmetry with a=6×ac(perovskite). The actual symmetry is rhombohedral, space group R3, with ah=16.910(1) Å, ch=41.500(2) Å. The structure was solved using a combination of single-crystal methods together with constrained refinements of powder X-ray and neutron powder data. The unit-cell composition is [Ca13824]A [Ca42Nb117V3]B[O4806], with vacancies in both the anion sites and A-cation sites. The Ca and Nb atoms are fully ordered in the B-sites such that (001) layers containing only Nb-centered octahedra alternate with layers containing both Nb-centered and Ca-centered octahedra. At the origin B-site, ordered oxygen vacancies result in the octahedron being transformed to a tetrahedron, which, in the single crystals, is occupied by vanadium. The structure displays a new type of octahedral tilt system in which 3×3×3 blocks of (a+a+a+) tilts are periodically twinned on the pseudo-cubic {1 0 0}c planes.  相似文献   

15.
Investigations on phase relationships and crystal structures have been conducted on several ternary rare-earth titanium antimonide systems. The isothermal cross-sections of the ternary RE-Ti-Sb systems containing a representative early (RE=La) and late rare-earth element (RE=Er) have been constructed at 800 °C. In the La-Ti-Sb system, the previously known compound La3TiSb5 was confirmed and the new compound La2Ti7Sb12 (own type, Cmmm, Z=2, a=10.5446(10) Å, b=20.768(2) Å, and c=4.4344(4) Å) was discovered. In the Er-Ti-Sb system, no ternary compounds were found. The structure of La2Ti7Sb12 consists of a complex arrangement of TiSb6 octahedra and disordered fragments of homoatomic Sb assemblies, generating a three-dimensional framework in which La atoms reside. Other early rare-earth elements (RE=Ce, Pr, Nd) can be substituted in this structure type. Attempts to prepare crystals in these systems through use of a tin flux resulted in the discovery of a new Sn-containing pseudoternary phase RETi3(SnxSb1−x)4 for RE=Nd, Sm (own type, Fmmm, Z=8; a=5.7806(4) Å, b=10.0846(7) Å, and c=24.2260(16) Å for NdTi3(Sn0.1Sb0.9)4; a=5.7590(4) Å, b=10.0686(6) Å, and c=24.1167(14) Å for SmTi3(Sn0.1Sb0.9)4). Its structure consists of double-layer slabs of Ti-centred octahedra stacked alternately with nets of the RE atoms; the Ti atoms are arranged in kagome nets.  相似文献   

16.
A comparative study of two Sn-based composite materials as negative electrode for Li-ion accumulators is presented. The former SnB0.6P0.4O2.9 obtained by in-situ dispersion of SnO in an oxide matrix is shown to be an amorphous tin composite oxide (ATCO). The latter Sn0.72[BPO4]0.28 obtained by ex-situ dispersion of Sn in a borophosphate matrix consists of Sn particles embedded in a crystalline BPO4 matrix. The electrochemical responses of ATCO and Sn0.72[BPO4]0.28 composite in galvanostatic mode show reversible capacities of about 450 and 530 mAh g−1, respectively, with different irreversible capacities (60% and 29%). Analysis of these composite materials by 119Sn Mössbauer spectroscopy in transmission (TMS) and emission (CEMS) modes confirms that ATCO is an amorphous SnII composite oxide and shows that in the case of Sn0.72[BPO4]0.28, the surface of the tin clusters is mainly formed by SnII in an amorphous interface whereas the bulk of the clusters is mainly formed by Sn0. The determination of the recoilless free fractions f (Lamb-Mössbauer factors) leads to the effective fraction of both Sn0 and SnII species in such composites. The influence of chemical composition and especially of the surface-to-bulk tin species ratio on the electrochemical behaviour has been analysed for several Snx[BPO4]1−x composite materials (0.17<x<0.91). The cell using the compound Sn0.72[BPO4]0.28 as active material exhibits interesting electrochemical performances (reversible capacity of 500 mAh g−1 at C/5 rate).  相似文献   

17.
In the course of an excursion into the system K2O-CaO-SiO2, single crystalline material of the previously unknown compound K2Ca6Si4O15 has been obtained. Single crystal X-ray diffraction experiments revealed that the new phase is monoclinic (space group P12/c1) with the following basic crystallographic data: a=7.3782(8) Å, b=5.5677(5) Å, c=17.2466(17) Å, β=90.005(8)°, Z=2. According to Liebau's nomenclature, the compound can be classified as a mixed anion silicate containing insular [SiO4]-groups as well as [Si2O7]-dimers in the ratio 2:1, i.e. the crystallochemical formula can be written as K2Ca6[SiO4]2[Si2O7]. The silicate anions are linked by K- and Ca-ions distributed among five different non-tetrahedral M-positions and coordinated by six to eight nearest oxygen neighbors. Alternatively, the structure can be described as a heteropolyhedral framework built up by kröhnkite-type [M(SiO4)2O2]-chains in which the MO6 octahedra are corner-linked to bridging SiO4 tetrahedra. The chains (running parallel to [0 1 0]) are located in 4.6 Å wide layers parallel to (1 0 0). Neighboring sheets are shifted relative to each other by an amount of +δ or −δ along [0 0 1]. In the derived two layer …ABABAB… stacking sequence, chains belonging to adjacent sheets are linked by corner sharing of common oxygen atoms. The resulting network contains tunnels in which the more irregularly coordinated K- and Ca-ions are incorporated for charge compensation. A comparison between the present compound and structurally related mixed tetrahedral-octahedral frameworks is given. The characterization has been completed by Raman and FTIR-spectroscopy. An allocation of the bands to certain vibrational species has been aided by density functional theory (DFT) calculations.  相似文献   

18.
Na11[CuO4][SO4]3 was obtained from a redox reaction of CuO with Na2O2 in the presence of Na2O and Na2SO4 in sealed Ag containers under Ar atmosphere at 600°C. The crystal structure has been determined from X-ray single crystal data at 293 and 170 K (Pnma, Z=4). The lattice parameters have been refined from X-ray powder data at 293 K as well: a=1597.06(6) pm, b=703.26(3) pm, c=1481.95(6) pm. The structure contains isolated distorted square-planar [CuO4]5− anions and non-coordinating sulfate groups. Furthermore, we report calculations of the Madelung Part of the Lattice Energy (MAPLE) and some of the physical properties of Na11[CuO4][SO4]3.  相似文献   

19.
Zn7Sb2O12 forms a full range of Co-containing α solid solutions, Zn7−xCoxSb2O12, with an inverse-spinel structure at high temperature. At low temperatures for x<2, the solid solutions transform into the low temperature β-polymorph. For x=0, the βα transition occurs at 1225±25 °C; the transition temperature decreases with increasing x. At high x and low temperatures, α solid solutions are formed but are non-stoichiometric; the (Zn+Co):Sb ratio is >7:2 and the compensation for the deficiency in Sb is attributed to the partial oxidation of Co2+ to Co3+. From Rietveld refinements using ND data, Co occupies both octahedral and tetrahedral sites at intermediate values of x, but an octahedral preference attributed to crystal field stabilisation, causes the lattice parameter plot to deviate negatively from the Vegard's law. Sub-solidus compatibility relations in the ternary system ZnO-Sb2O5-CoO have been determined at 1100 °C for the compositions containing ?50% Sb2O5.  相似文献   

20.
The rare-earth dicarboxylate hybrid materials [Ce(H2O)]2[O2C(CH2)2CO2]3 ([Ce(Suc)]) and [Sm(H2O)]2[O2C(CH2)2CO2]3·H2O ([Sm(Suc)]) have been hydrothermally synthesized (200°C, 3 days) under autogenus pressure. [Ce(Suc)] is triclinic, a=7.961 (3) Å, b=8.176 (5) Å, c=14.32 (2) Å, α=97.07° (7), β=96.75° (8), γ=103.73° (6), and z=2. The crystal structure of this compound has been determined using 3120 unique single crystal data. The final refinements let the agreement factors R1 and wR2(F2) converge to 0.0138 and 0.0363, respectively. [Ce(Suc)] is built up from infinite chains of edge-sharing nine-fold coordinated cerium atoms running along [100]. These chains are interconnected by the carbon atoms of the succinate anions, leading to a three-dimensional hybrid framework. The cell constants of [Sm(Suc)], isotypic with monoclinic C2/c [Pr(H2O)]2[O2C(CH2)2CO2]3·H2O ([Pr(Suc)]), were refined starting from X-ray powder data: a=20.275 (3) Å, b=7.919 (6) Å, c=14.130 (3) Å, and β=121.45° (1). Despite its lower symmetry, [Ce(Suc)] presents an important structural filiation with [Sm(Suc)]  相似文献   

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