The effect of hydrostatic pressure on the ferroelectric phase transition in [NH2(CH3)2]3[Sb2Cl9]

The effect of hydrostatic pressure on the ferroelectric phase transition temperature in [NH₂(CH₃)₂]₃[Sb₂Cl₉] (DMACA) has been studied by electric permittivity measurements at pressures up to 400 MPa. The pressure-temperature phase diagram is given. The phase transition temperature (T_c) increases with increasing pressure up to 150 MPa, passes through a maximum and then decreases with a further increase of pressure. The unexpected nonlinear decrease in T_c with pressure increasing above 150 MPa suggests that the mechanism of ferroelectric phase transition in DMACA is different from hitherto assumed.     

Esr study of (SO4)2− dynamics in relation to the ferroelectric phase transition in ammonium sulfate

Ferroelectric phase transition in ammonium sulfate has been studied by ESR of CrO₄^3? radical substituting for SO₄^2? ion in (NH₄)₂SO₄. In addition to discontinuous changes at T_c, certain continuous changes are observed in ESR parameters of this probe below T_c, which reflect the role of the sulfate ion in the phase transition. A microscopic mechanism of the phase transition is proposed and discussed in terms of the change of orientation of the sulfate tetrahedron through a finite angle. The degree of the change of orientation below T_c is thought to be the possible order parameter of the phase transition.     

Dielectric dispersion in the microwave range of the incommensurate phase (NH4)2BeF4

The complex dielectric constant of (NH₄)₂BeF₄ single crystals was measured in the frequency range from 0.6 to 300 MHz in the vicinity of the transition temperature T_c. It was found that, the relaxation frequency is about 1 × 10⁸Hz atT_c. Dielectric relaxation can be described by a polydispersive process.     

Decoupling of the order-disorder and displacive contributions to the phase transition in NH4H(ClH2CCOO)2

The effects of hydrostatic pressure and substitution of Rb⁺for the ammonium cations on the ferroelectric phase transition temperature in NH₄H(ClH₂CCOO)₂ have been studied by electric permittivity measurements. The transition temperature (T_c) decreases with increasing pressure up to 800 MPa and the pressure coefficient dT_c/dp=−1.4×10⁻² [K/MPa] has been experimentally determined. The substitution of Rb⁺ for the ammonium cations has been shown to considerably lower the ferroelectric phase transition temperature T_c. In mixed crystals, additional electric permittivity anomaly has been clearly evidenced. The results are discussed assuming a model, which combines polarizability effects, related to the heavy ion units, with the pseudo-spin tunnelling.     

Dielectric dispersion in the incommensurate phases of [N(CH3)4]2CoCl4 and [N(CH3)4]2ZnCl4

The complex dielectric permittivity ?(ω) of [N(CH₃)₄]₂CoCl₄ and [N(CH₃)₄]₂ZnCl₄ along the a-axis was measured between 0.35 MHz and 100 MHz. It has been found that for both substances the relaxation frequencies are about 5 MHz at T_c. The dielectric relaxation of both substances could be described by a polydispersive process β = 0.74 in the vicinity of T_c. However, for the temperature region of (T?T_c) > 0.6 for [N(CH₃)₄]₂CoCl₄ the dielectric absorption seems to be rather monodispersive.     

H nuclear magnetic resonance study of the ferroelastic and superionic phase transitions of (NH4)4LiH3(SO4)4 single crystals

We investigated the temperature dependences of the line shape, spin-lattice relaxation time, T₁, and spin-spin relaxation time, T₂, of the ¹H nuclei in (NH₄)₄LiH₃(SO₄)₄ single crystals. On the basis of the data obtained, we were able to distinguish the “ammonium” and “hydrogen-bond” protons in the crystals. For both the ammonium and hydrogen-bond protons in (NH₄)₄LiH₃(SO₄)₄, the curves of T₁ and T₂ versus temperature changed significantly near the ferroelastic and superionic phase transitions at T_C (=232 K) and T_S (=405 K), respectively. In particular, near T_S, the ¹H signal due to the hydrogen-bond protons abruptly narrowed and the T₂ value for these protons abruptly increased, indicating that these protons play an important role in this superionic phase transition. The marked increase in the T₂ of the hydrogen-bond protons above T_S indicates that the breaking of O-H?O bonds and the formation of new H-bonds with HSO₄^- contribute significantly to the high-temperature conductivity of (NH₄)₄LiH₃(SO₄)₄ crystals.     

杂质对K2ZnCl4晶体无公度结构相变的影响

对K₂ZnCl₄铁电晶体在无公度-公度转变的相变点附近的孤子行为进行了研究。发现在相变点附近杂质使介电函数明显偏离居里-外斯定律,并导致介电峰值的明显下降;同时还发现杂质对升温相变点T_c^h较之对降温相变点T_c^c有更大的影响,这与Rb₂ZnCl₄等晶体中的情况恰好相反。采用朗道自由能理论可较好地描述杂质在相变点附近对介电函数的影响。分 关键词：     

The pressure influence on the incommensurate-commensurate ferroelectric phase transition in [4-NH2C5H4NH][SbCl4]

The dielectric properties of the [4-NH₂C₅H₄NH] SbCl₄ (abbreviated as 4-APCA) crystal were investigated under hydrostatic pressure up to 300 Mpa. The pressure-temperature phase diagram was given. The paraelectric-ferroelectric phase transition (II→III) temperature (T_c) increases linearly with increasing pressure with a slope dT_c/dp=21×10⁻² K/MPa. The pressure dependence of Curie-Weiss constants has been evaluated also. In the paraelectric phase (II) the Curie constant (C₊) was pressure dependent whereas the C₋ constant over the ferroelectric phase (III) was almost constant. The results are interpreted in terms of improper and displacive type phase transition model with a soft phonon at a zone boundary.     

Metastable chaotic state in K2ZnCl4

The ³⁵Cl NQR frequencies of K₂ZnCl₄ have been measured close to the incommensurate-commensurate transition. A calculation of the temperature dependence of the soliton density n_s from the NQR data showed that in K₂ZnCl₄ close to T_c exists a metastable chaotic state.     

Cl35 NQR study of the structural phase transition in (CH3NH3)HgCl3

The Cl³⁵ nuclear quadrupole resonance spectra of (CH₃NH₃)HgCl₃ have been measured between -150°C and + 100°C. The spectra clearly show that a structural phase transition of first order takes place around T_c? 60°C. The transition may be related to a disordering of the CH₃NH₃ groups which are reorienting both above and below T_c. The positive temperature coefficient of the Cl NQR frequency, dv/dT may be also explained by the CH₃NH₃ motion.     

Two-dimensional critical behaviour in antiferrodistortive Al ur6(CIO4)3 and Ga ur6(ClO4)3

Critical behaviour with dimensionality d = 2 has been observed for the 300 K antiferrodistortive phase transition in Al ur₆(ClO₄)₃ and Ga ur₆(ClO₄)₃ by means of the temperature dependence of the ESR parameter D. The systems exhibited d = 2 behaviour in the static critical behaviour for T<T_c?40 K for T>T_c + 40 K. From the ESR data including line width measurements the local order parameter relaxation rate ω₁ has been obtained for various temperatures above T_c, with a lowest value of ω₁ = 150 MHz at T_c + 15 K     

Polarisation remanente dans les varietes de basse temperature de (NH4) 3AlF6 ET (NH4) 3FeF6

Dielectric and thermocurrent measurements have been carried out on (NH₄) ₃AlF₆ and (NH₄) ₃FeF₆ ceramic samples. A maximum of permittivity is observed close to the transition temperature (T_{T(NH4) 3AlF6} = 217K; T_T(NH43FeF6 = 264K. In the low-temperature phase a polarization current of about 10^-9A is obtained and can be reversed when the sign of the polarization field is changed, a property which could correspond to a ferroelectric behavior. However, no pyroelectric current is detected when the temperature decreases from T_T. Another hypothesis, based on a field-induced polarization, has been considered : the depolarization current could be due to charge displacements from potential minima favored by rising temperature. In any way, the low-temperature phase is characterized by a remanent polarization.     

Evidence for a new phase transition in Rb2ZnCl4 by Raman scattering

The Raman spectra of an oriented single crystal of Rb₂ZnCl₄ give evidence for the existence of a phse mode at low temperature, as predicted by Wada et al. A new soft mode whose frequency decreases as the temperature T₃?72 K is approached from below, was observed in the a(cc)b scattering orientation, strongly supporting the onset of a new phase transition.     

Electrical and thermal studies in the commensurate incommensurate phase region of (NH4)2ZnCl4 single crystal

DC electrical conductivity for a virgin and poled annealed (NH₄)₂ZnCl₄b-axis single crystal shows a defect controlled property. A Schottky mechanism is a probable mechanism of conduction in regions of strong structural transitions. The rise of conductivity in the incommensurate and paraelectric phases is linked to an increase in discommensurations density. The activation energies (ΔE) in the three phases region were calculated. DTA measurements shows that the crystal is stable up to 200 °C and the phase transition temperatures were observed at 42, 94.8 and 137 °C. The effective activation energy (E_e) was obtained using Kissinger and Mahadevan equations. It was found to be equal to 0.49 eV. This correlates with the value obtained through DC conductivity.     

Influence of defects on the phase transition in squaric acid (H2C4O4)

We have investigated the influence of defects induced by chromium and deuterium doping on the phase transition in solid squaric acid (H₂C₄O₄) by high resolution ¹³C NMR. Deuterium doping alone is observed to increase the phase transition temperature T_c linearly with the ²H concentration, whereas chromium defects, destroy the local order and lead to clusters of the high temperature phase. Correspondingly the critical temperature decreases with increasing chromium doping and the critical temperature region is smeared out.     

Elastic anomaly in K2ZnCl4 around the normal-incommensurate-commensurate phase transition points

The ultrasonic velocities in K₂ZnCl₄ were measured as functions of temperature. At the incommensurate-commensurate phase transition point the velocity of the c₅₅ mode showed a clear anomaly, whereas anomalies were hardly observable in all other modes. The results are analyzed in terms of a phenomenological theory.     

X-ray diffraction study of a structural phase transition in (NbSe4)3I

The second-order structural phase transition was observed by X-ray diffraction technique in (NbSe₄)₃I. The transition temperature (T_c) was 274.2 K. No evidence of the formation of the charge-density wave was found out. Temperature dependence of the intensity of (0,5,12) reflection obeys the Landau theory of the second kind of phase transition near T_c. Temperature dependence of the integral breadth of (0,0,12) reflection indicates the effect of the soft-phonon mode below T_c. The existence of the structural phase transition, probably not associated with charge-density-wave formation, suggests the unique nature of (NbSe₄)Z₃I in the new series of compounds (MSe₄)_xI (M=Nb, Ta).     

Ferroelectric properties of partly deuterated NH4HSeO4 crystals

Partly deuterated NH₄HSeO₄ crystals were grown from solutions containing 10, 20, 30, 40, 50 and 60% molar deuterium. The deuteration process leads to an increase in the phase transition temperatures. The extrapolated value of ΔT_c(∞) for completely deuterated crystals is 25 K. The I2 ? B2(C³₂) (if a axis is parallel to [110]) symmetry and the ferroelectric transition related to it is observed only in crystals growing from solution containing less than 50% deuterium. The crystals growing from solution containing more than 50% deuterium have a P2₁2₁2₁(D⁴₂) symmetry.     

On the phase diagram of the [(CH3)4N]2ZnCl4−xBrx system

The [(CH₃)₄N]₂ZnCl_4?xBr_x system shows a complete miscibility with a common Pnma high temperature phase. The (x,T)-phase diagram (x given by [(CH₃)₄N]₂ZnCl_4?xBr_x) was determined by means of DSC- and X-ray measurements. In the vicinity of both end members an analogy to the (P,T)-phase diagrams of pure compounds is observed with an increasing x corresponding to an increase of pressure. In the intermediate part of the system other effects become important leading to large coexistence regions of different phases. This is evidently due to the simultaneous occupancy of anion tetrahedra by different numbers of Cl and Br atoms. The non-equivalent ZnX₄-tetrahedra of solid solutions do not suppress the occurence of the incommensurate phases. They exist between x = 0 to ?3 and are interrupted by a supposedly ferroelectric phase occuring up to x ?0.4. Around x ? 3 a triple point occurs the nature of which needs a closer elucidation.     

Studies of the electrical properties of nearly perfect K2ZnCl4 single crystals as measured during commensurate incommensurate-paraelectric phase transitions

Electrical conductivity and dielectric measurements were carried in the temperature range covering the commensurate ferroelectric-incommensurate-paraelectric normal phases (300-600 K) for the three main crystallographic axes of K₂ZnCl₄ single crystals. The values of activation energies in the three phases were calculated and discussed. A thermal hysteresis of about 12 K is observed which deduce the presence of first order transition for the lock-in ferroelectric transition at T_c=404 K. Conductivity anomalies were observed in both ferroelectric and paraelectric phases. The conduction mechanism was discussed. The suggested occurrence of discommensuration in K₂ZnCl₄ crystals upon the lock-in transition in contrast with conductivity and dielectric results explains the anomalous behavior for the b-axis measurements. The orientation of these discommensuration was discussed on a view of projection in the three standard crystallographic directions.