Mechanism of phase transitions in the (NH4)2WO2F4 ferroelastic

Precision studies of the thermophysical properties and structure of an (NH₄)₂WO₂F₄ crystal have been performed. It was established reliably that there is a sequence of two phase transitions at T ₁ = 201 K and T ₂ = 160 K characterized by wedging out of an intermediate phase with an increase in pressure. The role of tetrahedral and octahedral ionic groups in the mechanism of the structural transitions was determined.     

Thermal decomposition of ammonium fluoroferrates (NH4)xFeF2x (2≤x≤3)

Different ammonium fluoroferrates (NH₄)_xFeF_2x (2≤x≤3) have been investigated. The thermal decomposition of the compounds obtained can be interpreted by their identical crystal structures (cryolite type). The decomposition products of all ammonium fluoroferrates formed in initial stage are isostructural of NH₄FeF₄. The decomposition is accompanied by the partial reduction of Fe(III) to Fe(II) by ammonium isolated. The end product of the thermal decomposition is FeF₂ and FeF₃ mixture.     

A raman scattering study of the phase transition in the ammonium oxyfluoride (NH4)3TiOF5

Raman spectra of a polycrystalline sample of the perovskite-like oxyfluoride (NH₄)₃TiOF₅ are measured in the frequency region 100–3600 cm^?1 at temperatures ranging from 91 to 370 K under hydrostatic pressures of up to 9 GPa, which include the range of the phase transition from the orientationally disordered cubic phase to the low-symmetry phase. Anomalies in the spectral parameters due to the phase transition are revealed in the range of vibrations of TiOF₅ octahedral groups.     

Investigation of thermal expansion,phase diagrams,and barocaloric effect in the (NH4)2WO2F4 and (NH4)2MoO2F4 oxyfluorides

The thermal expansion along the principal crystallographic axes of the (NH₄)₂WO₂F₄ and (NH₄)₂MoO₂F₄ oxyfluorides has been studied. The anomalous behavior of α _i (T) due to the phase transitions has been revealed at T ₁ = 271.4 K and T ₂ ≈ 180 K for the molybdate and at T ₁ = 201.5 K and T ₂ ≈ 161 K for the tungstate. The quantities dT/dp and dT/dσ _i , which characterize the dependence of the phase transition temperatures on the hydrostatic and uniaxial pressures, have been determined from analyzing the results of studies of the thermal expansion and heat capacity with the use of the Pippard relations. The p-T and α _i -T phase diagrams reflect different characters of the influence of the pressure on the stability of the initial and distorted phases of the oxyfluorides. The magnitudes of the extensive and intensive barocaloric effects determined in the vicinity of the structural phase transitions are as follows: ΔS _BCE varies from approximately −10 to −17 J/mol K and ΔT _AD ≈ 8−17 K for the molybdate and ΔS _BCE varies from approximately −10 to −17 J/mol K and ΔT _AD ≈ 8−13 K for the tungstate.     

A Raman scattering study of the phase transition in the (NH4)3WO3F3 oxyfluoride

The Raman scattering spectra of polycrystalline samples of the (NH₄)₃WO₃F₃ perovskite-like oxyfluoride were measured at frequencies of 70–3600 cm^?1 in the temperature range 93–323 K, including the transition from the orientationally disordered cubic phase to the low-symmetry phase. Transitional anomalies in the spectral parameters were revealed in the frequency ranges of internal vibrations of the ammonium ions and WO₃F₃ octahedral groups. An analysis of the experimental results allowed the conclusion that the phase transition under study is associated primarily with the ordering of the octahedral groups.     

Hydrolysis of Volatile Ammonium Oxofluorotitanate According to 19F, 17O, and 49Ti NMR Data

Hydrolysis of NH₄TiO_xF_5-2x (x0.4) (I) was investigated by ¹⁹F, ¹⁷O, and ⁴⁹Ti NMR. The interaction of complex I with water is accompanied by the formation of [TiF₆]^2- and multinuclear titanium forms. The composition of the main forms resulting from hydrolysis of I has been established. The bonding of titanium octahedra into dimers and other oligomers occurs by formation of hydroxyl bridges, considerably lowering the pH of the solution. Close analogy has been found between hydrolysis of the title complex and that of titanium tetrafluoride.     

Hydrolysis of ammonium oxofluorotungstates: A F, O and W NMR study

Fluorine-19 and natural abundance ¹⁷O and ¹⁸³W NMR spectroscopy were employed for the characterization of aqueous solutions of (NH₄)₂WO₂F₄ and (NH₄)₃WO₃F₃. Dissolution of the (NH₄)₂WO₂F₄ complex is accompanied by its partial acid hydrolysis to give the trans(mer)-dimer, [W₂O₅F₆]⁴⁻, and unreacted cis-[WO₂F₄]²⁻. The cis(fac)-[W₂O₅F₆]⁴⁻ anion is the major soluble product resulting from the alkaline hydrolysis of (NH₄)₂WO₂F₄ along with the isolation of the solid (NH₄)₂WO₃F₂. In addition, the edge-bridging dimer, [W₂O₆F₄]⁴⁻, and the cyclic trimer, [W₃O₉F₆]⁶⁻, are also suggested as hydrolysis products. Decomposition of (NH₄)₃WO₃F₃ occurs in aqueous solution to give NH₄WO₃F.     

Phase transitions in orthorhombic oxyfluoride (NH4)2MoO2F4

(NH₄)₂MoO₂F₄ single crystals were grown and studied using polarization-optical methods, and the birefringence was measured in the temperature range 90–350 K. The following sequence of phase transitions is revealed: G ₀ ? G ₁ ? G ₂. It is established that the phase transition at T ₀₁ ≈ 267 K is of the first order and exhibits thermal hysteresis δT ₀₁ ≈ 0.6 K. A weak anomaly is found in Δn(T) at T ₀₂ ≈ 180 K. The crystals are shown to retain the orthorhombic symmetry during the phase transitions.     

Thermal Behaviour of Ammonium Oxofluorotitanates(IV)

The thermal behaviour of ammonium oxofluorotitanates (NH₄)₃TiOF₅, (NH₄)₂TiOF₄ and NH₄TiOF₃ was investigated by thermoanalytical, X-ray and IR spectroscopic methods. The first decomposition stages under quasi-isobaric conditions are characterized by the formation of (NH₄)₂TiF₆ and ammonium oxofluorotitanate with the less content of ammonium and fluorine than in the initial compound. The decomposition process is accompanied by the Ti(IV) reducing due to ammonia evolved. The new ammonium oxofluorotitanate of high volatility was isolated and characterized. Ammonium-containing non-stoichiometric titanium oxyfluorides are the final products of thermal decomposition of ammonium oxofluorotitanates.This revised version was published online in November 2005 with corrections to the Cover Date.     

Structure and Internal Mobility of Complex Ions in Ammonium Pentafluorotitanate According to XRD and NMR Data

The crystal structure of NH₄TiF₅ (I) was determined (monoclinic crystals, a = 14.683(1), b = 6.392(1), c = 20.821(2) , = 110.538(2); space group P2₁/n, Z = 4). Structure I is built from infinite zigzag chains of TiF₆ octahedra linked by their cis-vertices in the [101] direction; the chains are connected by the ammonium ions forming hydrogen bonds. The chains of octahedra with the surrounding ammonium ions are staggered in the crystal lattice of I. ¹⁹F and ¹H NMR spectroscopy was used to study the dynamics of the complex ions in NH₄TiF₅ in the temperature range 270-530 K. Types of ionic motion in the fluoride and proton subsystems were determined, and activation energies evaluated.