On the structural phase transitions in the incommensurate Cs2CdBr4

Abstract

In the series of incommensurate A₂BX₄ halides with the β-K₂SO₄ type structure, Cs₂CdBr₄ exhibits an unusual behaviour since the “lock-in” phase transition occurs at the centre of the Brillouin zone. The observed phase sequence is the following: Pnma (Z = 4)?INC(k₀ ≈ 1/6a*)?P2_1/n(Z = 4)?P1 (Z = 4). These phase transitions have been studied by means of Raman scattering and ultrasonic measurements. It is shown that the Pnma?INC?P2_1/n sequence is governed by order-disorder processes due to CdB2-₄ tetrahedra reorientations coupled with translations of the Cs⁺ cations, and that the low-temperature P2_1/n?P1 transition is of a displacive nature, governed by a soft optical mode. The “pseudo-proper” ferroelastic character of these transformations is clearly established. A model potential developed in the framework of Landau theory is proposed; this model is able to reproduce the general trends observed in the temperature dependence of the soft-modes and of the elastic constants in the different phases.     

NQR Study of Phase Transition and Cationic Motion in 4-NH2C5H4NHBiBr4·H2O

Four ⁸¹Br NQR lines in 4-NH₂C₅H₄NHBiBr₄·H₂O were observed in the temperature range between 77 and ca. 380 K; with increasing temperatures the respective sets of higher and lower two resonance lines coalesced into single lines discontinuously at 274 K, showing the occurrence of a first-order type phase transition of this crystal. The transition was confirmed with heat anomaly on a DTA curve. Each higher and lower line of high-temperature phase is assignable to the terminal Br atoms and the bridging ones of one-dimensional poly anions (BiBr₄ ⁻) _n in the crystal structure (C2/c), which was investigated by a X-ray structure analysis at room temperature. The 1/T ₁ temperature dependence of ⁸¹Br NQR follows the usual T ² law in the temperature range between 77 and ca. 140 K, being explained by fluctuation of the EFG at Br nucleus due to lattice vibrations. The T ₁ vs. 1/T curve in the temperature range between about 160 and 190 K was describable by the exponential curves, allowing us the estimation of activation energies. These exponential behaviors of T ₁ of ⁸¹Br NQR are attributable to the fluctuations caused by the thermal motion of 4-NH₂C₅H₄H⁺ ions. Echo signals of the ⁸¹Br NQR could not be detected above 190 K owing to poor S/N with very short T ₂.     

X-ray study of the anomalous thermal hystereses of the modulation wavevectors in Cs2HgCl4

A rich sequence of structural modulations in Cs₂HgCl₄ as a function of temperature was studied by means of X-ray diffraction. Accurate satellite-position measurements on the cooling and heating paths of the crystal revealed abnormal thermal hystereses for incommensurate phases and coexistences of neighboring commensurate phases. A well-defined X-ray picture of the a-axis modulated phases in the range of 221–184 K were observed on the heating path, while the c-axis modulated phases existing below 184 K were definitely detected on the cooling path. The proper conditions for a precise phase diagram of Cs₂HgCl₄ can be correlated with relatively defect-free transformations of a-axis modulations at heating and of c-axis modulations at cooling. The peculiarity of Cs₂HgCl₄ to switch modulation direction among the a- and c-axes at 184 K allows us deliberately accumulate and thus control a majority of mobile defects on the mutually perpendicular (100) or (001) planes by possessing crystal within temperature domain of a- or c-axes modulations, respectively.     

Pressure-induced change of the interlayer exchange interaction from ferromagnetic to antiferromagnetic in CS2CuF4 observed by neutron scattering experiments up to 2 GPa

Abstract

Neutron scattering experiments on the two-dimensional Heisenberg ferromagnets Cs₂ CuF₄ and K₂CuF₄ have been performed around 2 ～ 3 GPa over 1·4–15 K. At ambient pressure both the intralayer and the interlayer exchange interactions in these two compounds are ferromagnetic. At about 2 GPa, the interlayer exchange coupling in Cs₂ CuF₄ is found to change from ferromagnetic to antiferromagnetic, while the ferromagnetic intralayer exchange interaction is maintained. Contrary to Cs₂CuF₄, the ferromagnetism in K₂Cuf₄ is not destroyed by pressure up to 9 GPa, that was confirmed in the early study of the magnetic susceptibility measurements.     

Linear birefringence studies of incommensurate systems: II. KFeF4

Abstract

The temperature dependence of the linear birefringence (LB), Δn _c , is measured in the range 5 K ? T ? 500 K on samples of KFeF₄, which originate from hydrothermal, flux and Bridgman growth techniques. Pronounced anomalies are found at the orthorhombic-orthorhomic phase transition at T _c ∽ 400 K. It is weakly discontinuous with a near-tricritical exponent β ∽ 0.2. Weak anomalies near T _i ∽ T _c + (25 … 40 K) seem to indicate a transition into an intermediate incommensurate phase. Its XY-model character is reflected by the critical LB exponent β = 0.8 ± 0.1. A smooth LB anomaly below 200 K is due to 2-dimensional ferromagnetic spin-order.     

Electronic absorption spectrum of Cs<Subscript>2</Subscript>ZnI<Subscript>4</Subscript> thin films

The absorption spectrum of Cs₂ZnI₄ thin films in the energy range 3–6 eV at temperatures from 90 to 340 K has been investigated. It is established that this compound belongs to direct-gap insulators. Low-frequency exciton excitations are localized in ZnI₄ structural elements of the lattice. Phase transitions at 280 K (paraelectric phase ? incommensurate phase), 135 K (incommensurate phase ? monoclinic ferroelastic phase), and 96 K (monoclinic phase ? triclinic ferroelastic phase) have been found from the temperature dependences of the spectral position and halfwidth of the low-frequency exciton band. Additional broadening of the exciton band is observed for ferroelastic phases; it is likely to be due to exciton scattering from strain fluctuations near domain walls.     

Structure determination of Cs0.864Rb1.136SeO4

The present structure determination of Cs _x Rb_2-x SeO₄ shows that the crystal belongs to the β - K₂SO₄ family, like the related compounds Cs₂SeO₄ and Rb₂SeO₄. In β - K₂SO₄ compounds the cations occupy two different sites; one of these sites, which is surrounded by 11 anionic atoms, is occupied preferentially by Cs, while the other one with 9 neighbours by Rb. A slight excess of Rb has been determined by X-ray structure analysis in a single crystal prepared at 292 K; its formula is Cs_0.864(9)Rb_1.136(9)SeO₄.

Crystals were grown by evaporation from equimolar water solutions of Cs₂SeO₄ and Rb₂SeO₄ at 292 and 301 K. No phase transition was detected by DSC in the range 103-323 K for either of the samples. Lattice parameters of different crystals isolated at various stages of crystallization indicate formation of crystals with a different proportion of Cs/Rb cations. The lattice parameters as well as their ratios differed significantly from those given by Endo et al., (1983).     

The invar effect and phase transitions in Cs2ZnI4 crystals

An in situ x-ray diffraction study of Cs₂ZnI₄ crystals performed in the 4.2–300 K temperature range is reported. The lattice parameter measurements have revealed three anomalies corresponding to phase transitions. The thermal expansion coefficient along the c axis was found to vanish in the region of incommensurate and commensurate modulated phases, 120–96 K (the invar effect). A possible crystallographic model relating modulated atomic displacements to the invar effect is discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 137–142 (January 1999)     

Ferroic phase transitions in β-LiNH4SO4

Abstract

The paper reviews the results of experimental and theoretical studies of ferroic phase transitions in β-LiNH₄SO₄ and its deuterated analogue. β-LiNH₄SO₄ undergoes succesive phase transitions: a paraelectric - ferroelectric phase transition at T₁ ? 462 K, a ferroelectric - ferroelastic phase transition at T₂ ? 283 K and a transition from one ferroelastic phase to the other at T₃ ? 28 K. Attention is focused on the influence of the order of phase transitions on the pattern of ferroelectric and ferroelastic domain structure, and also on the role played by the dynamics of molecular groups in the mechanism of transitions. The pre-transition effect connected with the ferroelectric-paraelectric transition: heterophase, capable of accounting for anomalies in different physical properties present 1-3 K below T₁ is shown. The anomalous temperature variation of spontaneous polarisation of the crystal is discussed within the framework of the phenomenological model of weak ferroelectrics.     

Phase diagram and domain structure of the Rb2 x Tl2(1− x )Cd2(SO4)3 solid solutions

From measurements of temperature dependences of the birefringence and from observations of the domain structure the x, T–phase diagram for the Rb_{2 x} Tl_{2(1? x )}Cd₂(SO₄)₃ solid solutions have been obtained. Ferroelastic domain structure and movement of phase boundaries have been studied in the course of phase transitions in Rb_{2 x} Tl_{2(1? x )}Cd₂(SO₄)₃ crystals. Possible reasons for the appearance of mechanically non-compatible (‘forbidden’) ferroelastic domain walls are given.     

A nuclear magnetic resonance study of the structural properties and molecular motions of Li2KH(SO4)2 and LiKSO4 single crystals

The structural properties and relaxation mechanisms of Li₂KH(SO₄)₂ crystals were determined using the temperature dependences of NMR spectra and the spin-lattice relaxation times (T₁) of their ¹H, ⁷Li, and ³⁹K nuclei. The results obtained were compared with the previously reported physical properties of LiKSO₄ crystals. The substitution of the potassium ions with protons in the LiKSO₄ crystals were variations in the phase transition temperatures, and the non-appearance of ferroelastic properties. The ⁷Li T₁ for the Li₂KH(SO₄)₂ crystals was much shorter than the ⁷Li T₁ for the LiKSO₄ crystals, and these findings indicate that the presence of the protons in Li₂KH(SO₄)₂ causes the Li ions to move with greater freedom.     

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.     

Dielectric behavior and low temperature phase transition in NH4IO3

The electrical properties namely ac conductivity σ(ω,?T) and the complex dielectric permittivity (ε*) are measured at selected frequencies (5–100?kHz) as function of temperature (95?K?T?4IO₃. The ferroelectric hysteresis loops and the X-ray diffraction pattern are also measured. The analysis of the data indicates that the compound undergoes a structural phase transition at ～103?K and the behavior of σ(ω,?T) obeys the power law. The trend of the temperature dependence of the angular frequency exponent s (0?s?4IO₃; (2) the data indicate that the compound undergoes a structural phase transition at 103?K; (3) the originality of this transition has been confirmed by X-ray diffraction; (4) no evidence for the existence of a ferroelectric transition at 103?K as mentioned earlier; and (5) the quantum mechanical tunneling is proposed as the main mechanism of the electric conduction.     

Renormalization phenomena in Ba-diluted ferroelastic lead phosphate, (Pb1-x Ba x )3(PO4)2

Abstract

In the improper ferroelastic palmierite-type lead phosphate order parameter coupling with a defect induced conjugate field leads to the renormalization of the two different critical temperatures of three order parameter components {Q ₃} and {Q ₁ Q ₂}. The influence of the lead dilution by barium on the ferroelastic domain pattern, the critical temperature of the ferroelastic transformation R m–C2/c and the development of the intermediate regime in (Pb_1–x Ba _x )₃(PO₄)₂ is studied using optical birefringence measurements, Raman and infrared spectroscopy. At the ferroelastic transition temperature T _c the orientational contribution of the three-states Potts model becomes critical. T _c is reduced from 453 K (x = 0) to zero K at x? 0.12. Modifications of the shape of zigzag needle domains as well as the angle between the monoclinic binary axis and the W walls along [031] with temperature and increasing Ba-content are reported. Above the ferroelastic transition point the component Q ₃, which corresponds to the displacive part in the Gibbs free energy, leads to dynamic short-range monoclinic deformation in the trigonal matrix. The temperature where Q ₃ shows critical behaviour is renormalized to 720 K (x = 0.12) as compared with 563 K in pure lead phosphate. For x>0.13 no monoclinic precursor clusters were found.     

Ferroelectric phase transition in Cs3Bi2I9

Single crystals of Cs₃Bi₂I₉ have been grown. Polarized-optical, dielectric, and calorimetric studies have been performed, along with measurements of birefringence, and the coefficients of elasticity c ₄₄, and linear expansion a over a wide temperature range. It is found that an intrinsic (pseudo-intrinsic) second-order phase transition to the ferroelastic phase takes place at T ₀=220.0±0.6 K accompanied by a change of the crystal symmetry from 6/mmc to 2/m. The transition parameter depends linearly on the shear strain x ₅ and varies with temperature according to a power law with exponent β=0.5. Zh. éksp. Teor. Fiz. 39, 1850–1852 (October 1997)     

X-ray study of the low-temperature phase transition in K2CoCl4

Precise lattice parameter measurements and intensity measurements of selected main and satellite reflections of K₂CoCl₄ have been performed in the temperature range 100 to 300 K in the vicinity of the low-temperature phase transition (commensurate-commensurate phase transition, T _c = 142 K). A broadening of the FWHM for the h01 reflections was observed below 142 K which suggests a transition from an orthorhombic phase to a monoclinic phase.     

Optical studies of the ferroelastic phase transitions in KFe(MoO4)2

ABSTRACT

The ferroelastic phase transitions in KFe(MoO₄)₂ have been studied by means of polarized light microscopy. The crystal undergoes a sequence of ferroelastic phase transitions. It has been found that the second transition consists of two transitions separated by the temperature interval of about 0.4 K. Both these transitions are of the first order and are evidenced through a phase front passing, without the domain structure rebuilding. The disposition of optical indicatrix axes n_g, n_m has been established, and the birefringence has been measured in the plane (0001) in the temperature range covering all ferroelastic phases. From temperature studies of the morphic birefringence, a critical exponent of the order parameter has been estimated.     

Proton conductivity and ferroelectric phase transition in hydrogen-bonded ferroelectric NH4IO3

We report on the ac dielectric permittivity (ε) and the electric conductivity (σ_ω), as function of the temperature 300?K?T4IO₃. The main feature of our measured parameters is that, the compound undergoes a ferroelectric phase transition of an improper character, at (368?±?1)K from a high temperature paraelectric phase I (Pm2₁ b) to a low temperature ferroelectric phase II (Pc21n). The electric conduction seems to be protonic. The frequency dependent conductivity has a linear response following the universal power law (σ_{( ω )}?=?A(T)ω ^{s (T)}). The temperature dependence of the frequency exponent s suggests the existence of two types of conduction mechanisms.