Syntheses and structures of Ta2(WO2)0.87H0.26(PO4)4 and Ta2(MoO2)(PO4)4

Tantalum hydrogen phosphate, β-TaH(PO₄)₂, has a three-dimensional structure that is stable to remarkably high temperature (∼600 °C) presumably due to the presence of strong hydrogen bonds. Impedance measurements indicate a low conductivity, 2.0 × 10⁻⁶ S/cm at 200 °C in 5% H₂. In further studies aimed at enhancing the conductivity by aliovalent doping, we have investigated systematically the synthesis of compounds in the TaH(PO₄)₂-W₂P₂O₁₁ system at 380 °C. As a result, a new phase, Ta₂(WO₂)_0.87H_0.26(PO₄)₄, was identified and subsequently the molybdenum analog Ta₂(MoO₂)(PO₄)₄ was also prepared. The structures were determined by single crystal X-ray diffraction techniques. The structures of Ta₂(WO₂)_0.87H_0.26(PO₄)₄ and Ta₂(MoO₂)(PO₄)₄ can be formally derived from the structure of β-TaH(PO₄)₂ by the replacement of two P-OH protons with an MO₂²⁺ (M = Mo and W) group together with a change in the orientation of some phosphate tetrahedra.     

Preparation of (NH4)Zr2(PO4)3 and HZr2(PO4)3

(NH₄)Zr₂(PO₄)₃ has been prepared, hydrothermally, from α-zirconium phosphate in three different ways; (1) from amine intercalates at 300°C, (2) from mixtures of ZrOCl₂·8H₂O in excess (NH₄)H₂PO₄ and (3) reaction of NH₄Cl with Zr(NaPO₄)₂. Ammonium dizirconium triphosphate is rhombohedral with a = 8.676(1) and $\text{c}\text{= 24.288(5)}\text{A}\text{?}$. It decomposed on heating to HZr₂(PO₄)₃. Below 600°C a complex, as yet unindexed, X-ray pattern was obtained. A very similar X-ray pattern was obtained by washing LiTi_0.1Zr_1.9(PO₄)₃ with 0.3N HCl. Heating this phase or NH₄Zr₂(PO₄)₃, above 600°C resulted in the appearance of a rhombohedral phase of HZr₂(PO₄)₃ with cell dimensions a = 8.803(5) and $\text{c}\text{= 23.23(1)}\text{A}\text{?}$. The protons were not completely removed until about 1150°C. Decomposition of (NH₄)Zr₂(PO₄)₃ at 450°C yielded an acidic gas whereas at 700°C NH₃ was evolved. A possible explanation for this behavior is presented.     

Ferroelastic effect in RbFeF4 and CsFeF4

Orthorhombic CsFeF₄, with spontaneous lattice strain at room temperature of 3.21×10⁻⁴, is ferroelastic. A uniaxial compressive stress of 22 MNm⁻² applied along [001] interchanges the a- and c-axes. The ferroelastic atomic displacements in isostructural RbFeF₄ at room temperature are 0.37 Å for Rb, 0.07 Å for F(1) interchanging with F(2), and 0.10 Å for F(3). At 4.5°K, these displacements are estimated as 0.45, 0.30 and 0.11 A. The Fe atom remains invariant under ferroelastic reversal.     

Bi3(FeO4)(MoO4)2 and Bi3(GaO4)(MoO4)2 - new compounds with scheelite related structures

The title compounds have been prepared for the first time. They have monoclinic structures related to the scheelite (CaWO₄) structure, and they represent the first example of trivalent cations on tetrahedral sites of the scheelite structure. A superstructure is observed due to an ordering of the cations on the tetrahedral sites.     

The synthesis and selected properties of new compounds: Mg3Fe4(VO4)6 and Zn3Fe4(VO4)6

New compounds: Mg₃Fe₄(VO₄)₆ and Zn₃Fe₄(VO₄)₆ were obtained from a solid state reaction. The temperatures of melting of Mg₃Fe₄(VO₄)₆ and Zn₃Fe₄(VO₄)₆ amount to 950±5 and 850±5°C, respectively. The indexing results and the calculated unit cell parameters for both compounds are given and suggest that both phases are isotypic with Mn₃Fe₄(VO₄)₆. The IR spectra of the above-mentioned compounds are presented.     

Hydrogen bonding in NH4HSO4. NH4H2PO4

NH₄HSO₄·NH₄H₂PO₄ is monoclinic $\text{P}\text{2}{}_1\text{n}$ with Z = 2 and the following unit cell dimensions : a = 7.723(5), b = 7.540(5), $\text{c}\text{= 7.482(5)}\text{A}\text{?}$, β = 101.32(5)°. Crystal structure of this salt has been solved with a final R value 0.028. As in the corresponding potassium salt PO₄ and SO₄ tetrahedra are randomly distributed.A complete hydrogen bonding pattern is given.     

AlPO4 tridymite stabilized with KMgPO4

AlPO₄ has been found to dissolve KMgPO₄ up to 7 mol% at 1145°C. The solid solution is of tridymite form and the high-tridymite form is stabilized to room temperature when the content of KMgPO₄ is more than 4.5 mol%.     

High-pressure modifications of CaAl2O4 and CaGa2O4

The modifications of CaAl₂O₄ and CaGa₂O₄ with the stuffed tridymite structure were examined under high temperatures (600 ～ 1500 °C) and high pressures (10 ～ 40 kb). Calcium monoaluminate CaAl₂O₄ was found to transform to three kinds of high-pressure modifications. The original CaAl₂O₄ (CA-I) changed to the phase CA-II which had m-CaGa₂O₄ type structure with a different array of tetrahedra in the six-membered rings of tetrahedron. The phase CA-II transformed either to the phase CA-IV with CaFe₂O₄ type structure or to an unknown phase (CA-III) under high pressures. The phase CA-IV was obtained under the pressures above 30 kb and at the temperatures above 1000 °C. Calcium monogallate CaGa₂O₄ transformed to the CaFe₂O₄ type structure above 30kb and 700 °C. No phases such as CA-II and CA-III were found. The structural relations among these modifications were discussed.     

New arsenates (V) NaKAl2O[AsO4]2 and Na2KAl3[AsO4]4

The title compounds have been synthesized by a solid state reaction route using a salt flux. Their crystal structures were determined from single crystal X-ray data. NaKAl₂O[AsO₄]₂ crystallizes with the orthorhombic K₂Fe₂O[AsO₄]₂-type, Pnma, a = 8.2368(6) Å, b = 5.5228(3) Å, c = 17.0160(13) Å and Z = 4, whereas Na₂KAl₃[AsO₄]₄ crystallizes with the orthorhombic K₃Fe₃[AsO₄]₄-type, Cmce, a = 10.5049(9), b = 20.482(2), c = 6.3574(6) Å and Z = 4. The NaKAl₂O[AsO₄]₂ structure is built up of [Al₂As₂O₉]²⁻ layers perpendicular to the c-axis which are separated by A⁺ alkali layers. The [Al₂As₂O₉]²⁻ layers consist of ribbons of edge-sharing AlO₆ octahedra, running along the a direction and which are connected through AsO₄ tetrahedra by sharing corners. The Na₂KAl₃[AsO₄]₄ structure contains [Al₃As₄O₁₆]³⁻ layers perpendicular to the b-axis separated by A⁺ alkali layers. The [Al₃As₄O₁₆]³⁻ layer consists of a layer of corner-sharing AlO₆ octahedra which are also connected to the AsO₄ tetrahedra by sharing corners.     

Lithium ion conduction in Li5A104, Li5GaO4 and Li6ZnO4

Polycrystalline samples of Li₅Al0₄, Li₅Ga0₄, and Li₆Zn0₄ have been synthesized, and their ionic conductivity measured over a range of temperature. These materials, which have the antifluorite structure with large concentrations of intrinsic cation vacancies, have Arrhenius-like conductivities at low temperatures, with a steep rise in the range 385–450°C, reaching very high values, with a very small temperature dependence, thereafter. Materials of this type, which exhibit the highest values of lithium ion conductivity yet found, may have important practical applications in devices such as elevated temperature batteries.     

New high-pressure phase of HfTiO4 and ZrTiO4 ceramics

We studied the high-pressure effects on the crystalline structure of monoclinic HfTiO₄ and ZrTiO₄. We found that the compressibility of these ceramics is highly non-isotropic, being the b-axis the most compressible one. In addition, the a-axis is found to have a small and negative compressibility. At 2.7 GPa (10.7 GPa) we discovered the onset of a structural phase transition in HfTiO₄ (ZrTiO₄), coexisting the low- and high-pressure phases in a broad pressure range. The new high-pressure phase has a monoclinic structure which involves an increase in the Ti-O coordination and a collapse of the cell volume. The equation of state for the low-pressure phase is also determined.     

Crystal structure of KHSO4 · KH2PO4

KHSO₄ · KH₂PO₄ is monoclinic $\text{P}\text{2}{}_1\text{n}$ with Z = 2 and the following unit cell dimensions: a = 7.434(3); b = 7.341(3); $\text{c}\text{= 7.148(3)}\text{A}\text{?}$; β = 99.56(5)°.Crystal structure of this salt has been solved, using 1699 independent reflexions with a final R value: 0.034. PO₄ and SO₄ tetrahedra are randomly distributed in the arrangement with a resulting (P.S)-O mean distance of 1.508(3) Å.     

Donnees cristallographiques sur ZnKPO4 et ZnKAsO4

Crystal data for ZnKPO₄ and ZnKAsO₄ are given. The two compounds are isotypic and crystallize in the hexagonal system.     

Dielectric properties of Pb3 (PO4)2 | Pb3 (AsO4)2

The dielectric constants of Pb₃ (PO₄)₂ | Pb₃ (AsO₄)₂ at room temperature are intrinsic and fulfill the Lyddane - Teller - Sachs relation. At higher temperatures the specific conductivity increases with an activation energy of 0.56 eV leading to Maxwell - Wagner polarization effects thereby increasing the effective dielectric constant. Corresponding peaks in ∈' (T) are extrinsic and not attributed to structural phase transformations.     

Reinvestigation of the binary diagram Na3PO4-FePO4 and crystal structure of a new iron phosphate Na3Fe3(PO4)4

A new iron(III) phosphate Na₃Fe₃(PO₄)₄ has been synthesized and characterized. It decomposes before melting at 860°C into FePO₄ and Na₃Fe₂(PO₄)₃. The structure of the compound was determined by single-crystal X-ray diffraction. The unit cell is monoclinic with the following parameters: a=19.601(8) Å, b=6.387(1) Å, c=10.575(6) Å and β=91.81(4)°; Z=4; space group: C2/c. Na₃Fe₃(PO₄)₄ exhibits a layered structure involving corner-linkage between FeO₆ octahedra, and corner- and edge-sharing between FeO₆ octahedra and PO₄ tetrahedra. The Na⁺ cations occupying the interlayer space are six- and seven-fold coordinated by oxygen atoms. The relationship between the structure of Na₃Fe₃(PO₄)₄ and the previous reported hydrate K₃Fe₃(PO₄)₄·H₂O will be discussed.     

Neutron diffraction studies of NiCoP4O12 and NiZnP4O12

The title compounds belong to a group of isostructural $\text{M}$₂P₄O₁₂ tetrametaphosphates with monoclinic ($\text{C}$2/$\text{c}$) symmetry. The two structures have been profile-refined by means of the Rietveld technique on the basis of neutron powder diffraction data. The three-dimensional framework is built up of tetrametaphosphate anions and two distinct metal-oxygen octahedra, (M1)O₆ and (M2)O₆. The latter octahedron is somewhat larger and more distorted than (M1)O₆. The results show that in both solid solutions nickel preferentially enters the M1 sites, a tendency also observed in olivine and sarcopside, which contain $\text{M}$O₆ octahedra similar in shape and symmetry to those in $\text{M}$₂P₄O₁₂.     

Spectroscopic evidence of inhomogeneous distribution of Nd in YVO4, YPO4 and YAsO4 crystals

Nd³⁺ : YVO₄ is one of the most interesting laser hosts for micro and diode-pumped solid state lasers. We have studied magnetic and optical properties of Nd³⁺ in three zircon type crystals YMO₄ (M=V, As, P). In particular, Nd³⁺ ions exhibit in the three hosts a multisite character observed in the absorption and emission spectra. However, the emission and its dynamics are strongly dependant on the reabsorption mechanisms. In Nd : YVO₄, single crystals containing 7 ± 1 × 10¹⁸ Nd³⁺ ions/cm³, the lifetime is 95 ± 2 μs in good agreement with the calculated radiative lifetime. Electron Paramagnetic Resonance (EPR) measurements are performed to identify the nature of the different substitution sites for Nd³⁺ ions. Nd³⁺ ions are found to be inhomogeneously distributed in tetragonal D_2d symmetry sites, in isolated ions, “shallow clusters” and pairs. Proportions of the different local environments depend on the total neodymium concentration. For instance, 15% of the Nd³⁺ ions are gathered in Nd³⁺–Nd³⁺ pairs for 7.2 ± 0.2 × 10¹⁹ Nd³⁺ ions/cm³.     

Luminescence properties of monoclinic Cu4I4(Piperidine)4

A new modification of Cu₄I₄Pip₄ has been synthesized under hydrothermal conditions. X-ray crystallography revealed that this compound crystallized in the monoclinic system and consists of a tetrahedral core with composition Cu₄I₄, in which each Cu atom is coordinated by a piperidine molecule via the N atom. In contrast to a previously reported modification of Cu₄I₄Pip₄, the present modification shows luminescent properties when exposed to UV-light. In addition, we have used time-dependent density functional theory calculations to characterize both compounds in term of both absorption and emission.     

The solid electrolyte system,Li3PO4Li4SiO4

The phase diagram of the system Li₄SiO₄Li₃PO₄ has been studied. At subsolidus temperatures, ? 1000°C, Li₄SiO₄ forms a short range of equilibrium solid solutions between 0 and ～ 12 mole % Li₃PO₄; γ-Li₃PO₄ forms a range of equilibrium solid solutions between ～ 58 and 100% Li₃PO₄. In addition to these equilibrium solid solutions, Li₄SiO₄ forms an extensive range of metastable solid solutions containing up to ～ 60% Li₃PO₄, on quenching melts from ? 1050°C. Hence compositions around 60% Li₃PO₄, 40% Li₄SiO₄ may be prepared in two structural forms, i.e. as solid solutions of either Li₄SiO₄ or γ Li₃PO₄. Conductivity measurements show that, at these compositions, the two solid solution structures have similar, high conductivity of Li⁺ ions.     

Preparation and properties of the Pb3(VO4)2Pb3(PO4)2 system

Single crystals of the pseudobinary system Pb₃(V_1?xP_xO₄)₂ were grown via the Czochralski technique and were studied over wide ranges of x, particularly with regard to the influence of substitution on the $\text{3}\text{?}\text{mF}\text{2}\text{m}$ transition as a function of temperature.