Effect of an organic dye on the ferroelectric phase transition in KH2PO4 (KDP)

This paper reports on the first measurement of the dielectric permittivity and heat capacity of a KDP crystal doped by Chicago Sky Blue organic dye within a temperature interval including the ferroelectric phase transition at T _c =122 K. Similar measurements were made on a pure KDP crystal under the same conditions for the sake of comparison. The heat capacities of the pure and doped crystals were shown to differ substantially within an interval 1 K wide in the vicinity of T _c , where an anomaly in the heat capacity of the doped crystal was observed to wash out without producing any change in the temperature position of its maximum. The doping reduces the permittivity in the polar phase markedly. The observed effects are associated with the influence of nonisomorphic defects on the ferroelectric phase transition in a piezoelectric crystal.     

Critical anomaly in the electron spin-lattice relaxation at the ferroelectric phase transition of X-irradiated KDA

The spin-lattice relaxation of X-irradiated ferroelectric KDA has been investigated by means of the electron spin-echo method in the range between 2 and 200 K. In the vicinity of the phase transition point an anomalous increase of T₁ has been observed. This effect could not be detected for KDA-KDP mixed crystals with a high concentration of KDP. The anomaly of the spin-lattice relaxation at the phase transition is explained by the increased damping of the “hard” optical mode which governs the relaxation behaviour at this temperature region.     

A shell model for the H-bonded ferroelectric KH2PO4

A shell model for KH₂PO₄ (KDP), the prototype compound of the family of H-bonded ferroelectric materials, has been constructed by adjusting the interaction parameters to first-principles calculations. Structural properties, energy barriers, phonons, and the relative stability between the ferroelectric (FE) phase and a relevant antiferroelectric metastable structure associated to domain walls, compare very favorably to available first-principles and experimental data. Molecular dynamics simulations show that the model behaves satisfactorily within the FE phase. This model will be used to study the elusive structure of the paraelectric (PE) phase and the nature of the FE–PE phase transition.     

Capacity and thermal conductivity of a nanocomposite chrysolite asbestos-KDP (KH2PO4)

A nanocomposite chrysotile-KDP (KH₂PO₄) was prepared. KDP was introduced into empty nanochannels of chrysotile asbestos with diameters of ～5 nm. Thermal conductivity κ and heat capacity at a constant pressure C _p of the samples of chrysotile asbestos and nanocomposite chrysotile asbestos-KDP were measured in a temperature range of 80–300 K. Based on the analysis of the behavior of temperature dependences κ(T) and C _p (T) of the composite, temperatures of the ferroelectric transition T _F for KDP in nanochannels of chrysotile asbestos were determined. It turned out to be equal to ～250 K at T _F ～ 122 K for massive KDP samples.     

On the universal regularities of the lattice dynamics in ferroelectrics

The main regularities revealed for the dynamic response in recent Raman spectroscopic investigations of ferroelectric crystals of the displacive type (LiNbO₃, LiTaO₃) and the order-disorder type (KDP, DKDP) are discussed. The characteristic feature of the dynamic response for all the crystals (KDP, DKDP, LiNbO₃, LiTaO₃) under investigation in the vicinity of the phase transition temperature is an intense central peak that follows from the theoretical predictions for the order-disorder phase transition. The possible factors responsible for the central peak, the character of the behavior of this peak outside the aforementioned temperature range, and the specific features of the behavior of the width and intensity of the central peak over a wide range of temperatures for order-disorder crystals are analyzed.     

Phase transitions in xPbZr0.53Ti0.47O3-(1 − x)Mn0.4Zn0.6Fe2O4 magnetoelectric composites

The elastic, inelastic, and dielectric properties of the magnetoelectric composite xPbZr_0.53Ti_0.47O₃-(1 ? x)Mn_0.4Zn_0.6Fe₂O₄ (PZT-MZF) are studied in the temperature range from room temperature to 673 K. The influence of the ferroelectric PZT phase on the magnetic phase transition and the magnetic MZF phase on the ferroelectric phase transition is revealed. It is established that, as the PZT content increases, the degree of diffuseness of the phase transition decreases and a gradual crossover from a pronounced relaxor behavior to a more ordered ferroelectric behavior occurs.     

On the drastic temperature broadening of hard mode Raman lines of ferroelectric KDP type crystals near Tc

The drastic broadening of a few A₁ Raman lines of ferroelectric KH₂PO₄(KDP) and KH₂AsO₄(KDA) crystals have been measured at various temperatures near T_c. The results in KDP are in fair agreement with two different simplified expressions of linewidths, which are based on pseudospin-phonon interaction arguments. No such agreement is found between the results and a simplified linewidth expression derived from a theory based on soft mode-hard mode interaction arguments. The linewidths and the reciprocal of the proton spin-lattice relaxation time in KDP exhibit a very similar temperature dependence below T_c but behave differently above T_c. This phenomena is presented in detail, and discussed.     

Temperature‐dependent Raman scattering of KDP:Mn (0.9% weight of Mn) crystal

Low temperature polarized Raman scattering measurements of KDP:Mn (0.9% weight of Mn) were performed at temperatures ranging from 14 to 300 K, over the spectral range 50–1250 cm⁻¹. In the present results we can see that the spectra of undoped and doped samples at room temperature are very different. Doped samples maintain the KDP structure as tetragonal, with the same factor group D_2d but with a different class of the space group, different from the original 12. The results show that the crystal undergoes a phase transition at temperature between 115 and 97 K, which is much lower than the phase transition temperature of undoped KDP that occurs at 122 K, where the crystal changes from the para‐electric to the ferroelectric phase. Further, at very low temperature (14 K) we can see that the spectra of KDP:Mn (0.9% weight of Mn) present a behavior very different from the behavior presented by the spectra of KDP doped with low Mn concentration. Copyright © 2010 John Wiley & Sons, Ltd.     

Propagation of longitudinal ultrasonic waves in RbH2PO4 near its ferroelectric phase transition temperature

Ferroelectric phase transition in RbH₂PO₄ has been investigated using propagation of longitudinal acoustic waves along the polar axis near the transition temperature. The velocity of this mode is continuous across the transition temperature. Velocity data in the ferroelectric phase are analyzed in terms of coupled soft modeacoustic mode model of Pytte to obtain the temperature dependence of the soft mode frequency. The attenuation data in the ferroelectric phase show power law dependence. It follows scaling behaviour of the type predicted by Kawasaki from the mode-mode coupling theory and the dynamical scaling.     

Structural studies of the monoclinic dihydrogen phosphates: A neutron-diffraction study of paraelectric CsH2PO4

The crystal structure of paraelectric CsH₂PO₄ at room temperature is presented. As suggested by the strong deuteration-dependence of the transition temperature and the distribution of quasielastic scattering, one of the hydrogen bonds is found to be very probably (97.5%) disordered, with H-H=0.48(4)Å. This work is set in the context of the interest now being shown in the group of monoclinic dihydrogen phosphates-deuterated KDP, NaDP, the ferroelectric CsDP and the presumed ferroelectric T1DP (DP denotes H₂PO₄). Recent work on these other compounds is surveyed briefly.     

High-pressure dielectric studies of a novel hydrogen-bonded ferroelectric (NH4)2H2P2O6

The hydrostatic pressure effect on the dielectric properties of (NH₄)₂H₂P₂O₆ ferroelectric crystal was studied for pressures from 0.1 MPa to 360 MPa and for temperatures from 100 to 190 K. The pressure–temperature phase diagram obtained is linear with increasing pressure. The paraelectric–ferroelectric phase transition temperature decreases with increasing pressure with the pressure coefficient dT_c/dp=?5.16×10^?2 K MPa^?1. Additionally, the pressure dependences of Curie–Weiss constants for the crystal in paraelectric (C₊) and ferroelectric (C_?) phases are evaluated and discussed. The possible mechanism of paraelectric–ferroelectric phase transition is also discussed.     

EPR study of the ferroelectric phase transition in chromium-doped DMAAS

X-band electron paramagnetic resonance (EPR) investigations of single crystals of Cr³⁺-doped dimethylammonium aluminium sulphate hexahydrate are presented from 100 K to room temperature. The crystal undergoes a phase transition at 152 K from the ferroelastic to the ferroelectric phase. The spin-Hamiltonian parameters have been determined for both phases. The spin-Hamiltonian parameters in the ferroelectric phase are:g=1.980±0.003,b ₂ ⁰ =(1140±15)·10^?4 cm^?1,b ₂ ² =(214±10)·10^?4 cm^?1. Remarkable EPR line width changes confirm the order-disorder character of the ferroelectric phase transition on a microscopic level and demonstrate that the dimethylammonium reorientation freezing-out is the prime reason for this transition.     

Modified strong dipole-proton coupling model and local properties of EPR probe in KDP-type ferroelectrics

The modified strong dipole-proton coupling (MSDPC) model, which predicts several static and dynamic dielectric properties of KDP-type ferroelectrics, is used to investigate the properties of the paramagnetic center SeO ₄ ^3? introduced in the KH₂PO₄ (KDP) and KD₂PO₄ (DKDP) lattice as a local probe in an electron paramagnetic resonance experiment. Paramagnetic center is treated within the MSDPC model as a soft impurity, with anA _probe value of the elastic constant for the dipolec-component induction lower than theA value for the original PO ₄ ^3? group. ForA _probe=0.45A, the molecular dynamics simulations in the paraelectric phase of KDP and DKDP show the effective local double-well potential of the probe, and the temperature dependence of the calculated correlation time τ for the dipole reorientational jumps over the barrier can be fitted by the Arrhenius law. The obtained Arrhenius parameters for KDP are close to the experimental ones, and the experimentally detected higher activation energy in DKDP is reproduced. Also, the high-temperature line broadening and the temperature dependence of the⁷⁷Se hyperfine coupling observed in experiment are discussed within the MSDPC model.     

Intermediate-temperature polymorphic phase transition in KH2PO4: A synchrotron X-ray diffraction study

We have used synchrotron X-ray diffraction to investigate the structural and chemical changes undergone by polycrystalline KH₂PO₄ (KDP) upon heating within the 30-250 °C temperature interval. Our data show evidence of a polymorphic transition at T∼190 °C from the room-temperature tetragonal KDP phase to a new intermediate-temperature monoclinic KDP modification (spacegroup P2₁/m and lattice parameters a=7.590, b=6.209, c=4.530 Å, and β=107.36°). The monoclinic RDP polymorph remains stable upon further heating to 235 °C, and is isomorphic to its RbH₂PO₄ and CsH₂PO₄ counterparts.     

Unusual spontaneous twisting of an (NH4)2SO4 crystal in a torsion pendulum below the curie point

It is found that the ferroelectric phase transition in the ammonium sulphate crystal (NH₄)₂SO₄ at T _C=223 K is accompanied by spontaneous twisting of samples around the a, b, and c crystallographic axes in the ferroelectric phase. This twisting, observed with a torsion pendulum, cannot be explained solely by the change in symmetry mmm → mm2 at the Curie point. It is supposed that the twisting is connected with a complex rearrangement of the structural elements of the crystalline lattice below the Curie temperature.     

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.     

Effect of γ-irradiation on the heat capacity of an [NH2(CH3)2]2 · CuCl4 crystal in the temperature range 80–300 K

The heat capacity of [NH₂(CH₃)₂]₂ · CuCl₄ crystals prior to and after γ-irradiation with doses of 1, 5, 10, and 50 MR is measured by the calorimetric method in the temperature range 80–300 K. It is found that, as the temperature decreases, the temperature dependence C _p (T) exhibits two anomalies which correspond to phase transitions from the incommensurate to the ferroelectric phase at T _c =281 K and from the ferroelectric to the ferroelastic phase at T ₁=255 K. The nature of the anomalies is typical of a first-order phase transition. In addition, a smeared anomaly in the form of a small increase in the heat capacity of the ferroelectric phase is observed at T≈275 K. It is demonstrated that when the dose of γ-irradiation increases, the anomalies decrease in magnitude and the phase transition temperatures are displaced: T _c increases and T ₁ decreases.     

Phase transitions sequence in pyrochlore Cd2Nb2O7 studied by IR reflectivity

The infrared reflectivity of Cd₂Nb₂O₇ single crystal was studied in the temperature interval of 10-540 K, together with complementary dielectric measurements. A ferroelectric soft mode was revealed above the ferroelectric phase transition at T _c = 196 K coupled with a central-mode type dispersion in the near-millimetre range. This proves the mixed displacive and order-disorder nature of the transition. Below T _c many new modes were detected due to lowering of the symmetry, especially below the previously suggested incommensurate transition at 85 K. Discussion of the possible phase transitions based on symmetry considerations is presented with the conclusion that the ferroelectric transition is proper with the F_1u symmetry of the order parameter, whereas the intermediate ferroelastic transition is improper and triggered by the coupling with the ferroelectric order parameter. Received 17 July 2000     

Ferroelectricity and phase transition from incommensurate phase into commensurate one in (NH4)2ZnCl4

Phase transition has been found in (NH₄)₂ZnCl₄ at T = 266 ± 0.5 K by NQR method. There is a ferroelectric phase below T_c with a space group P2₁cn and with the trebling of the elementary lattice parameter along the axis c. Above the phase transition temperature in the crystal (NH₄)₂ZnCl₄ an incommensurate phase is realized.     

Origin of the structural local transition in the molecular impurity ion MnO<Stack><Subscript>4</Subscript><Superscript>2−</Superscript></Stack> in the K<Subscript>3</Subscript>Na(CrO<Subscript>4</Subscript>)<Subscript>2</Subscript> ferroelastic

A new model is proposed for a local transition in a Jahn-Teller impurity center in a crystal with a ferroelastic (ferroelectric) phase transition. This model is based on direct interaction of the order parameter of the phase transition in the matrix with the Jahn-Teller impurity degrees of freedom. It is shown that, under these conditions, the order parameter field can induce lifting of degeneracy of the electronic states active in the Jahn-Teller effect, which is accompanied by a transition from the Jahn-Teller effect to the pseudo-Jahn-Teller effect with its subsequent suppression. As a result, a decrease in temperature gives rise to a structural local transition in the region of the low-symmetry ferroelastic (ferroelectric) matrix phase from the many-well local adiabatic to a single-well potential. The model proposed allows interpretation of experimental data obtained in an EPR study of the molecular impurity ion MnO ₄ ^2? in the K₃Na(CrO₄)₂ ferroelastic.