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.     

Effect of electric field on the dielectric permittivity of betaine phosphite crystals in the paraelectric phase

Temperature dependences of the dielectric permittivity of betaine phosphite crystals are studied both without and under application of an electric bias. It is shown that, in view of the fact that the high-temperature improper ferroelastic (antiferrodistorsive) phase transition at T _c1=355 K is nearly tricritical, the nonlinear temperature dependence of inverse dielectric permittivity in the paraelectric phase and the effect of the field on the dielectric permittivity can be described within a phenomenological model containing two coupled (polar and nonpolar) order parameters with a negative coupling coefficient. An analysis of the model revealed that, in the case where two phase transitions, a nonpolar and a ferroelectric one, can occur in the crystal, all of its dielectric properties, including the polarization response in a field, can be described by one dimensionless parameter a. For the crystal under study, we have a=?2.5. This value of the parameter corresponds to a second-order ferroelectric transition far from the tricritical point, at which a=?1. It is shown that the polarization response in the paraelectric phase in an electric field calculated within this model differs radically from that in the ferroelectric phase-transition model for which the Curie-Weiss law holds in the paraelectric phase.     

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.     

Phase mixing in the critical region of the ferroelectric phase transition in KD2PO4

A novel neutron high resolution double crystal arrangement has been used to measure changes in d-spacing, d-spread and mosaicity through the first order ferroelectric phase transition of DKDP. Coexistence of both para and ferroelectric phases was directly observed in the range T_c to T_c — 3 K. No hysteresis could be detected within the precision of the temperature measurement (10^-3K). The origin of the overshoot effect has been elucidated.     

Dielectric properties of betaine phosphite-betaine phosphate solid-solution crystals in the improper ferroelastic phase

Temperature dependences of dielectric permittivity in the improper ferroelastic phase, including the region of the improper ferroelastic phase transition occurring at T=T_c1, were studied in the betaine phosphite-betaine phosphate solid-solution crystals. At a betaine phosphate (BP) concentration of 10%, the phase transition temperature T_c1 was found to shift toward higher temperatures by about 5 K compared to betaine phosphite (BPI) crystals, where T_c1=355 K. The phase transition remains in the vicinity of the tricritical point. As the BP concentration in BPI is increased, the dielectric anomaly at T=T_c1 weakens substantially compared to pure BPI. The nonlinear temperature dependence of reciprocal dielectric permittivity in the improper ferroelastic phase of BPI_xBP_1?x crystals is described in the concentration region 0.9≤x≤1 in terms of a thermodynamic model taking into account the biquadratic relation of the nonpolar order parameter of the improper ferroelastic phase transition to polarization. The decrease in the ferroelectric phase transition temperature T_c1 (or in the temperature of loss of improper ferroelastic phase stability) with increasing BP concentration in the above limits is due to the decreasing effect of the nonpolar mode on the polar instability, which is accompanied by a weakening of the dielectric anomaly at T=T_c1     

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.     

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.     

Effect of γ irradiation on the heat capacity of (CH3)2NH2Al(SO4)2 · 6H2O crystals near the ferroelectric phase transition

The heat capacity of dimethyl ammonium-aluminum sulfate crystals (DMAAS), both nonirradiated and γ-irradiated to fluences of 10⁷, 5×10⁷, and 10⁸ R, has been measured by the adiabatic method near the ferroelectric phase transition (PT) within the 80–300 K temperature range. The C _p =f(T) curve exhibits a λ-shaped anomaly near the phase-transition point T _C =152 K. The PT temperature and the magnitude of the anomaly are shown to decrease with increasing γ-irradiation fluence. It has been established that the ferroelectric PT at T _C =152 K, which lies close to the tricritical point, shifts progressively more under γ irradiation toward the second-order PT, and that the behavior of the anomalous part of the heat capacity in the ferroelectric phase is described by the thermodynamic theory of Landau. The experimental heat-capacity data have been used to calculate the variation of the thermodynamic functions of the DMAAS crystal.     

Features of the low-frequency polarization response in the region of the ferroelectric phase transition in multiferroic TbMnO<Subscript>3</Subscript>

The unusual behavior of the low-frequency (10 Hz–1 MHz) permittivity in single crystals of ferroelectric multiferroic TbMnO₃ has been experimentally and theoretically studied in detail in the region of the narrow temperature peak of the permittivity, associated with the ferroelectric phase transition (T_C ~ 27.4 K). It has been found that the ε_c^′(ω, T) maximum sharply decreases with increasing measured field frequency, while the temperature position of the maximum is independent of frequency. It has been shown that the observed features of the polarization response can be satisfactorily described within the Landau–Khalatnikov polarization relaxation theory.     

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     

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.     

Landau behaviour of the heat capacity of AgNa(NO2)2 close to the nearly tricritical ferroelectric phase transition

The heat capacity of a single crystal of the uniaxial ferroelectric AgNa(NO₂)₂ was measured close to the nearly tricritical phase transition. In the ferroelectric phase a strong temperature dependence of the anomaleous specific heat is found which obeys a temperature law (θ _f —T)^?0.494. A small latent heat was detected nearT _c. The thermal behaviour of AgNa(NO₂)₂ is described by a Landau type theory, from which the non linear coefficientsζ andζ of the free energy expansion are derived. The thermal data fit well to the known dielectric behaviour.     

Critical behavior of heat capacity in the vicinity of phase transitions in [NH2(CH3)2]5Cd3Cl11

The heat capacity of a [NH₂(CH₃)₂]₅Cd₃Cl₁₁ crystal was studied calorimetrically in the temperature interval 100–300 K. The C _p (T) dependence indicates that, as the temperature is lowered, phase transitions occur at temperatures T ₁ = 176.5 K and T ₂ = 123.5 K. The thermodynamic characteristics of this crystal were determined. It is shown that the transition at T ₂ = 123.5 K is an incommensurate-commensurate phase transformation and that the transition at T ₁ = 176.5 K is a normal-incommensurate phase transition.     

Iminodiacetic acid doped ferroelectric triglycine sulphate crystal: Crystal growth and characterization

Single crystals of iminodiacetic acid (HN(CH₂COOH)₂) doped triglycine sulphate (IDATGS) crystals have been grown from aqueous solution containing 1-10 mol% of iminodiacetic acid at constant temperature by slow evaporation technique. The effects of different amounts of doping entities on the growth habit have been investigated. X-ray powder diffraction pattern for pure and doped TGS was collected to determine the lattice parameters. The grown crystals were subjected to Fourier transform infrared (FTIR) spectroscopy studies to find the presence of various functional groups qualitatively. The dielectric permittivity has been studied as a function of temperature. An increase in the transition temperature (49.2-49.7 °C) of IDATGS crystals is observed. The dielectric constant (ε′_max) of IDATGS crystals vary in the range 922-2410 compared to pure TGS (T_c=49.12 °C and ε′_max=3050). Curie Weiss constants C_p and C_f in the paraelectric and ferroelectric phases were determined. The transition temperature (T_c) is found to decrease with increase in dopant concentration. P-E hysteresis studies show the presence of internal bias field in the crystal. Piezoelectric measurements were also carried out at room temperature. Domain patterns on b-cut plates were observed using scanning electron microscope. The micro hardness studies reveal that the doped crystals are harder than the pure TGS crystals. The low dielectric constant, higher transition temperature, internal bias field and hardness suggest that IDATGS crystals could be a potential material for IR detectors.     

The nature of anharmonicity and anomalous piezoelectric properties of ferroelectric SbSBr crystal

The contribution of soft mode at Sb atom's sites, to the temperature dependences of Sb atom's equilibrium position's difference Δz(T) has been studied theoretically, when SbSBr crystal is deformed along a(x), b(y) and c(z)-axis in paraelectric phase and is deformed along c(z)-axis in ferroelectric phase. The largest change of Δz₃₃(T) occurs in the ferroelectric phase near the phase transition temperature in the range from 16 K to 21 K. The temperature dependence of Sb atom's equilibrium position's displacements Δz₃₃ is very similar to the temperature dependence of experimental piezoelectric modulus, when SbSBr crystal is deformed in the direction of c(z)-axis in ferroelectric phase.     

Specific heat of SbSI

The temperature dependence of the specific heat of vapor and flux grown single crystal samples of ferroelectric antimony sulfur iodide (SbSI) was measured over a temperature range from 230K to 400K. C_p^E at T_c of the electrical flux and vapor grown samples are 0.078 cal/gmK and 0.076 cal/gmK respectively. ΔS and ΔQ at T_c are evaluated. The samples measured were grown by two different methods[1,2]. Differences are observed between the measurements made on the samples, both in the magnitude of the specific heat and the temperature at which the ferroelectric transition takes place. These differences are caused by the different levels of oxygen impurities in the samples.     

Anomalous states of the crystal structure of (Rb0.1(NH4)0.9)2SO4 solid solutions in the temperature range 4.2–300 K

Crystals of (Rb_0.1(NH₄)_0.9)₂SO₄ solid solutions are studied using x-ray diffractometry. It is revealed that the temperature dependence of the lattice parameter a exhibits an anomalous behavior, namely, the “invar effect” at temperatures above the ferroelectric phase transition point T _c and an anomalous increase in the temperature range from T _c to the liquid-helium temperature. An anomalous increase in the lattice parameter a and an increase in the intensity of Bragg reflections with a decrease in the temperature are interpreted within the model of the coexistence of two sublattices hypothetically responsible for the ferroelectric phase transition. A series of superstructure reflections observed along the basis axes corresponds to a sublattice formed in the matrix of the host structure. Analysis of the ratio between the lattice parameters of these structures allows the inference that, in the temperature range 4.2–300 K, the structure of the crystal under investigation can be considered an incommensurate single-crystal composite.     

Dielectric studies of phase transitions in the ferroelectric CdTiO3 and the Sr1−x CdxTiO3 solid solution

Temperature dependences of the permittivity and of the dielectric hysteresis loops in ceramic samples of nominally pure CdTiO₃ and a Sr_1?x Cd_xTiO₃ solid solution were studied. At 76.5±0.5 K, CdTiO₃ was established to undergo a ferroelectric phase transition close to the tricritical point. The temperature dependence of spontaneous polarization of CdTiO₃ is described within the Landau theory of phase transitions with the critical order parameter exponent ≈0.25. The phase diagram of the Sr_1?x Cd_xTiO₃ solid solution was drawn in (T, x) coordinates, and the critical concentration x _c =0.002, above which an induced polar state sets in the solid solution, was determined.     

Specific features of dielectric anomalies in Pb<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te(Ga) near a ferroelectric phase transition

The dielectric properties of Pb_{1 ? x} Ge _x Te(Ga) (x = 0.02, 0.03, 0.05) were studied in the temperature range 77–150 K at frequencies of 10⁴–10⁶ Hz. It is revealed that the ferroelectric phase transition temperature T _c and the permittivity ? of Pb_{1 ? x} Ge _x Te(Ga) increase substantially with the Ge content. The temperature dependence of the permittivity of Pb_{1 ? x} Ge _x Te shows two peaks; the main peak is at the ferroelectric phase transition temperature T _c , and an additional peak is at T ₁ > T _c .