Proton magnetic resonance study of the low-temperature phase transition in a LiNH4SO4 single crystal

The proton NMR line width and spin-lattice relaxation times for LiNH₄SO₄ single crystal were studied at low temperature range of 6 and 280 K. The changes in the proton relaxation behavior near the phase transition temperature indicates a change in the state of internal motion at the transition. The molecular motions obtained by the spin-lattice relaxation processes were found to be determined by molecular reorientation of the NH₄ ions in phases III, IV, and V. We also confirmed that the phase transitions occur at 26 and 133 K.     

Ionic conductivity of Li2NaK(SO4)2

A DSC study of Li₂NaK(SO₄)₂ in the range 300∽925 K has revealed that the compound undergoes phase transitions at 654, 682, 778 and 866 K, before melting congruently at 900 K. The five phase which are observed are designated I, II, III, IV and V with increasing order of temperature. A comparison of the enthalpy of melting with the transition enthalpies suggests that the phases IV and V are plastic phases. The ionic conductivity was measured in the range 584∽895 K by an ac impedance technique. The phase IV showed the smallest activation energy as determined from the temperature dependence of the conductivity (E_a=0.82 eV). The highest conductivity (1.0 Ω⁻¹ cm⁻¹) was observed in phase V at 895 K.     

Thermal resistivity,heat capacity and phase diagram of CBr4 under pressure

We have measured simultaneously the thermal resistivity and the heat capacity per unit volume for phases I, II, III and IV of CBr₄. We have used the transient hot-wire method, and have made measurements over the ranges 170 K to 425 K, and up to 2 GPa. Our results, and other evidence, indicate that I and III are plastic crystal phases, and that there is a significant degree of structural disorder in phase II. Three-phonon interactions probably provide the dominant contribution to the thermal resistivity of phase IV. Using structural analogies with the phases of CCl₄, we find that the relative values of the thermal resistivities are roughly as predicted by simple theory.     

Mixed alkali metal selenate proton conductors: Phase transitions and crystal structure of [Rb0.54(Nh4)0.46]3H(SeO4)2

Optical birefringence, calorimetric, thermal expansion, powder and single crystal X-ray diffraction investigations of mixed proton conductors [Rb_1-x(NH₄)_x]₃H(SeO₄)₂ were performed with the aim of studying the influence of partial substitution of cations on the superprotonic phase transition, on the atomic structure and on other characteristic features of this type of crystals.     

On the magnetic phase diagram of (Mn,Fe)WO4 wolframite

The magnetic phase diagram of mixed crystals of type (Mn, Fe)WO₄ is discusses within molecular field approximation. The two species of magnetic ions tend to align in different orderings. Depending on the interaction strengths the two ordered phases are separated either by a phase in which both orderings are superimposed or by a first order transition.     

Studies of structure, thermal, and electrical properties for Cs 5 H 3 (SO 4 ) 4 crystal

Electrical conductivity, differential scanning calorimetry, and X-ray diffraction measurements were performed on a pentacesium trihydrogen tetrasulfate, Cs₅H₃(SO₄)₄, crystal. The transition entropy at a superionic phase transition and the activation energy of proton migrations in the superionic phase were determined to be 58.2 J K⁻¹ mol⁻¹ and 0.48 eV, respectively. The crystal structure of Cs₅H₃(SO₄)₄ at room temperature was refined. The electrical conduction in Cs₅H₃(SO₄)₄ was discussed with the refined structure.     

Theoretical pressure-temperature phase diagram for [N(CH3)4]2CuCl4

The pressure-temperature phase diagram for a [N(CH₃)₄]₂CuCl₄ crystal has been theoretically constructed using the phenomenological approach developed earlier. The relationships for the thermodynamic potentials of different phases and the boundaries between these phases are derived. The theoretical and experimental diagrams are in reasonable agreement. The approximations and assumptions made in the construction of the diagrams are discussed.     

Plastic domain and ionic conductivity of (C4H9)4NI

Unusual ionic transport in tetrabutylammonium iodide (C₄H₉)₄NI (TBAI) was observed by high resolution proton NMR spectroscopy accompanied by diffusion experiments. Some parts of the TBA cations are diffusing not only in the plastic phase II, but in the low temperature ordered phase I as well. The diffusing TBA ions are considered to be inside the remaining plastic domains dispersed in the ordered crystal matrix. The volume fraction of the plastic domain is evaluated from the observed narrow component of the proton NMR spectra. The observed unusual temperature dependence of the diffusion coefficient can be explained by assuming a manifold decrease of the dimension of the plastic domain in phase I. The differences in degree of crystallinity at the interface of plastic domains with respect to its surroundings led to the surface enhancement of diffusivity in phase I. Finally, the observed ionic conductivity is compared with the estimation from the diffusion coefficient and mobile cation densities. The results suggest that only a fraction of the cations take part in the observed ionic conductivity.     

Phase transitions and molecular motions in [Zn(NH3)4](BF4)2 studied by nuclear magnetic resonance, infrared and Raman spectroscopy

Middle infrared absorption, Raman scattering and proton magnetic resonance relaxation measurements were performed for [Zn(NH₃)₄](BF₄) in order to establish relationship between the observed phase transitions and reorientational motions of the NH₃ ligands and BF₄⁻ anions. The temperature dependence of spin-lattice relaxation time (T₁(¹H)) and of the full width at half maximum (FWHM) of the bands connected with ρ_r(NH₃), ν₂(BF₄) and ν₄(BF₄) modes in the infrared and in the Raman spectra have shown that in the high temperature phase of [Zn(NH₃)₄](BF₄)₂ all molecular groups perform the following stochastic reorientational motions: fast (τ_R≈10⁻¹² s) 120° flips of NH₃ ligands about three-fold axis, fast isotropic reorientation of BF₄⁻ anions and slow (τ_R≈10⁻⁴ s) isotropic reorientation (“tumbling”) of the whole [Zn(NH₃)₄]²⁺ cation. Mean values of the activation energies for uniaxial reorientation of NH₃ and isotropic reorientation of BF₄⁻ at phases I and II are ca. 3 kJ mol⁻¹ and ca. 5 kJ mol⁻¹, respectively. At phases III and IV the activation energies values for uniaxial reorientation of both NH₃ and of BF₄⁻ equal to ca. 7 kJ mol⁻¹. Nearly the same values of the activation energies, as well as of the reorientational correlation times, at phases III and IV well explain existence of the coupling between reorientational motions of NH₃ and BF₄⁻. Splitting some of the infrared bands at T_C2=117 K suggests reducing of crystal symmetry at this phase transition. Sudden narrowing of the bands connected with ν₂(BF₄), ν₄(BF₄) and ρ_r(NH₃) modes at T_C3=101 K implies slowing down (τ_R?10⁻¹⁰ s) of the fast uniaxial reorientational motions of the BF₄⁻ anions and NH₃ ligands at this phase transition.     

Pressure-induced ferroelectricity in {N(CH3)4}2FeCl4

The hydrostatic pressure effect on the stability of phases I, II, III and IV in {N(CH₃)₄}₂FeCl₄ was studied by dielectric and DTA measurements in the temperature and pressure region of -40-30°C and 0–2 kbar. The pressure-induced new phase V found at applied pressures between 0.3 and 1.0 kbar was confirmed to be ferroelectric by the observation of D-E hysteresis loop. These results are compared with those of {N(CH₃)₄}₂XCl₄ (X: Co, Zn and Mn) in this paper.     

The thermoelastic properties of [N(CH3)4]2ZnBr4 and [N(CH3)4]2MnBr4

The ferrodistortive phase transition in the bis-tetramethylammonium tetrabromide crystals below room temperature is studied within the framework of the Landau theory. The specific heats of [N(CH₃)₄]₂MnBr₄ and [N(CH₃)₄]₂ZnBr₄ are correctly described down to 40°C below the transition temperature. The phenomenological parameters are determined from calorimetric results, elastic constants and thermal expansion data. Using these coefficients, the monoclinic angle in the ferrodistortive phases is obtained. The anharmonic quantities, such as the isothermal compressibility, calculated from the specific heat data, are in good agreement with the values derived from the elastic measurements.     

Vibrational spectroscopy study of hydrothermally produced scorodite (FeAsO4·2H2O), ferric arsenate sub‐hydrate (FAsH; FeAsO4·0.75H2O) and basic ferric arsenate sulfate (BFAS; Fe[(AsO4)1−x(SO4)x(OH)x]·wH2O)

Three crystalline ferric arsenate phases: (1) scorodite; FeAsO₄·2H₂O, (2) ferric arsenate sub‐hydrate (FAsH; FeAsO₄·0.75H₂O) and (3) basic ferric arsenate sulfate (BFAS; Fe[(AsO₄)_1−x(SO₄)_x(OH)_x]·wH₂O) synthesized by hydrothermal precipitation (175–225 °C) from Fe(III)‐AsO₄³⁻–SO₄²⁻ solutions have been investigated via Raman and infrared spectroscopies. The spectroscopic nature of these high‐temperature Fe(III)‐ AsO₄³⁻–SO₄²⁻ phases has not been extensively studied despite their importance to the hydrometallurgical industrial processing of precious metal (Au and Cu) arsenic sulfidic ores. It was found that scorodite, FAsH and BFAS all gave rise to very distinct arsenate, sulfate and hydroxyl vibrations. In scorodite and FAsH, the distribution of the internal arsenate modes was found to be distinct, with the factor effect being more predominant in the crystal system. For the crystallographically unknown BFAS phase, vibrational spectroscopy was used to monitor the arsenate ↔ sulfate solid solution behavior that occurs in this phase where the molecular symmetry of arsenate and sulfate in the crystal structure is reduced from an ideal T_d to a distorted T_d or C₂/C_2v symmetry. With the new collected vibrational data of the pure phases, the use of attenuated total reflectance infrared (ATR‐IR) spectroscopy was finally extended to investigate the nature of the arsenate in an industrial residue generated by pressure oxidation of a gold ore, where it was found that the arsenate was present in the form of BFAS. Copyright © 2009 John Wiley & Sons, Ltd.     

Ultraviolet reflectivity of NH4Cl and NH4I in ordered and disordered phases

Near-normal incidence reflectivity spectra below 10 eV of NH₄Cl in phases II and IV and of NH₄I in phases II and III are reported. An interpretation is given by comparing these spectra with those of alkali halides. A temperature shift of the first exciton peak of NH₄I due to ordering of the crystal was found as was the case with NH₄Br. The absence of this effect in NH₄Cl strongly implies the relation to the transition II–III and the tetragonal distortion of the lattice.     

Structural transformations and the critical and noncritical parameters during the phase transition in the (NH4)2KWO3F3 oxyfluoride

The structures of two phases of the (NH₄)₂KWO₃F₃ crystal have been determined from X-ray diffraction data obtained for a powder sample. The profile and structural parameters have been refined according to the procedure implemented in the DDM program. The results obtained have been discussed with invoking the group-theoretical analysis of the complete order parameter condensate, which takes into account the critical and noncritical atomic orderings and allows one to interpret the experimental data. It has been found that the symmetry transformation in the crystal can be schematically represented in the form Fm[`3]m\xrightarrow[(h,0,0,0,0,0)]10 - 10(X₅^- )PmmnFm\bar 3m\xrightarrow[{(\eta ,0,0,0,0,0)}]{{10 - 10(X_5^ - )}}Pmmn. This transformation is accompanied by the ordering of WO₃F₃ polyhedra and the displacement of NH₄ and K ions.     

Processes of ordering of structural elements, critical and noncritical parameters of phase transitions in the (NH4)3WO3F3 crystal

The structure of the low-temperature triclinic phase of the (NH₄)₃WO₃F₃ crystal has been determined and the structure of the cubic phase of this crystal has been refined from data of an X-ray diffraction experiment performed for a powder sample. The profile and structural parameters have been refined according to the procedure implemented in the DDM program. The results obtained have been discussed with invoking the group-theoretical analysis of the complete order parameter condensate, which takes into account the critical and noncritical atomic orderings and allows one to interpret the obtained experimental data. It has been found that the symmetry transformation in the crystal can be schematically represented in the following form: Fm[`3]m(Z = 4) ? P[`1](Z = 1) ? P[`1](Z = 6)Fm\bar 3m(Z = 4) \to P\bar 1(Z = 1) \to P\bar 1(Z = 6). This transformation is accompanied by the complete ordering of WO₃F₃ polyhedra and the displacement of NH₄ ions.     

Symmetry analysis of the possible low-temperature phases in KDy(MoO4)2

The possible asymmetric phases in the Jahn-Teller crystal of KDy(MoO₄)₂ are analyzed. Phases appearing upon a second-order phase transition from an orthorhombic D _2h ¹⁴ group with the unit cell volume doubling are described. It is shown that KDy(MoO₄)₂ crystals are capable of featuring the Jahn-Teller pseudoeffect caused by the interaction between the electron states of dysprosium ions and the compressive (tensile) or shear deformations.     

Features of elastic phase interaction in the crystal Gd2(MoO4)3

The elastic interaction of paraelastic-paraelectric (¯42m) and ferroelastic-improper ferroelectric (mm2) phases coexisting in a Gd₂ (MoO₄)₃ crystal is investigated for a phase transition in the neighborhood of T_c=433 K. The energetic favorability of the monodomain state of the ferroelastic phase being formed is shown and the reasons for the impossibility of reaching the plane of zero mean strains on the phase interface boundary are analyzed.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 68–72, March, 1990.The authors are grateful to I. M. Vitebskii for useful discussion and valuable remarks.     

DSC study of superionic phase transition in (NH4)4H2(SeO4)3 single crystals

DSC and complex impedance studies of the protonic conductor (NH₄)₄H₂(SeO₄)₃, which undergoes a superionic phase transition of first order at T_s = 378 K show that the activation energy of ionic conductivity d(lg σ)/dt and the ordering enthalpy ΔC_p of the crystal are proportional: d(lg σ)/dT = XΔC_p/RT_s + const, as found for MAg₄I₅ crystals undergoing a second-order superionic phase transition. Thus the short-range order environment of the species involved in fast-ion transport plays the main role in the superionic phase transition. This is also supported by the value of the entropy change at T_s, ΔS = 43 J/mole·K. A new metastable phase was found to be induced on heating the (NH₄)₄H₂(SeO₄)₃ crystal above T_s.     

Phase transitions and lattice dynamics in Ag2H3IO6 and (NH4)2H3IO6

The investigation of thermal, optical and dielectric properties of Ag₂H₃IO₆ and (NH₄)₂H₃IO₆ revealed phase transitions in two steps with unknown intermediate phases. Reflectivity measurements in the far infrared region confirm that the main step is caused by a freezing in of the proton tunnelling modes. From the results of NMR-NQR-spectroscopy the low temperature structures for both compounds are deduced. The complete group analysis of lattice vibrations and proton ordering modes of the room temperature phases is performed. In the case of Ag₂H₃IO₆ the transitions can be discussed in the frame-work of the Landau theory, starting with a condensation of an antiphase vibration of the silver atoms in theF point of the trigonal Brillouin zone, whereas in the case of (NH₄)₂H₃IO₆ a simultaneous ordering of protons inZ, F, andL-points of the Brillouin zone is proposed for the first step. A new definition of antiferroelectric transitions is suggested which is based on symmetry arguments only. The proton-ordering transitions in both compounds can then be classified as antiferroelectric.     

Phase transitions in triammonium hydrogen diselenate, (NH4)3 H(SeO4)2

The Raman and infrared spectra of triammonium hydrogen diselenate (NH₄)₃H(SeO₄)₂ (NHSe) have been recorded between 100 and 400 K. The present spectroscopic investigation cofirms the existence of five phases previously observed by other techniques. The analysis shows a progressive ordering with decreasing temperature. The ferroelectric IV → V tansition in this compound is also believed to be of the order-disorder type. The vibrational modes have been assigned by comparison with the sulphate compound (NH₄)₃H(SO₄)₂ (NHS).