Dielectric and calorimetric investigations of KNO3 in pores of nanoporous silica matrices MCM-41

The temperature dependences of the linear dielectric permittivity, the third harmonic amplitude, and the heat capacity of nanoporous silica matrices MCM-41 with cellular channels (3.7 and 2.6 nm in diameter) filled with KNO₃ have been investigated in comparison with those obtained for bulk potassium nitrate. Measurements have been performed during heating and cooling in the range from room temperature to 463 K. Anomalies corresponding to structural phase transitions have been observed. A significant broadening of the temperature region of the existence of the ferroelectric phase III of potassium nitrate upon cooling has been revealed. This broadening increases with a decrease in the size of pores. It has been shown that, in the nanocomposites with potassium nitrate, the ferroelectric phase can also be formed during heating. The efficiency of observation of the third harmonic generation for studying nanocomposites with the ferroelectric phase has been demonstrated.     

Dynamic shift of the phase-transition temperature in (Sn1−x In(2/3)x)2P2S6 crystals with incommensurate phase

The dielectric properties of ferroelectric (Sn_1?x In_(2/3)x )₂P₂S₆ crystals were studied in the region of incommensurate phase transitions occurring upon fast cooling and heating (0.2–11 K/min). The dynamic phase-transition shift observed in these materials was examined.     

Heat capacity of PMN near an electric-field-induced phase transition

The heat capacity of a single crystal of Pb(Mg_1/3Nb_2/3)O₃ (PMN) in an electric filed with E = 3 kV/cm applied along the [111] direction has been measured using adiabatic calorimetry over the temperature range 170–250 K. Anomalies in C _p have been found, which correspond to a field-induced phase transition from a relaxor to a ferroelectric state at 225 K under field cooling conditions or at 235–240 K on the subsequent field heating. The field-induced ferroelectric phase persists in a metastable state at low temperatures and is destroyed on zero-field heating at 210 K. The small entropy change ΔS = 0.028R in the field-induced phase transition suggests an insignificant change in the volume fraction of existing polar nanoregions.     

Low‐temperature Raman spectroscopic studies in NaNbO3

Raman spectroscopic measurements were carried out in the temperature range 10–300 K to understand the low‐temperature antiferroelectric (AFE)–ferroelectric (FE) phase transition in NaNbO₃. Several modes in the low wavenumber range were found to disappear, while some new modes appeared across the transition. The temperature dependence of mode wavenumbers suggests that, during cooling, the AFE–FE phase transition begins to occur at 180 K, while the reverse transition starts at 260 K during heating. During cooling, the two phases were found to coexist in the temperature range of 220–160 K. Upon heating, the FE phase is retained up to 240 K and both FE and AFE phases coexist in the temperature range 240–300 K. In contrast to the earlier reports, the present results suggest a different coexistence region and the reverse transition temperature. The reported relaxor‐type FE behaviour over a broad temperature is consistent with the observed coexistence of phases during cooling and heating cycles. Copyright © 2010 John Wiley & Sons, Ltd.     

Dielectric properties of the nanoporous MCM-41 matrix filled with the (NH4)2SO4 ferroelectric

Variations with temperature of the linear dielectric permittivity and amplitude of the third harmonic were studied for nanoporous MCM-41 matrices with 4.0-nm channel pores filled with the (NH₄)₂SO₄ ferroelectric, in comparison with bulk ammonium sulfate. The measurements were performed upon heating and cooling in the temperature range from 100 K to room temperature. A noticeable shift to low temperatures (by approximately 25 K) for the ferroelectric phase transition in the MCM-41/(NH₄)₂SO₄ nanocomposite as compared to bulk (NH₄)₂SO₄ was revealed. The temperature hysteresis observed at the phase transition in the nanocomposite was approximately 2 K which is close to that in bulk ammonium sulfate. The significant decrease of the transition temperature in nanostructured ammonium sulfate agrees with the theoretical predictions based on the Landau and Ising models of the size effect on the ferroelectric phase transition in isolated small particles.     

铌酸锂钠在低温时的介电铁电和热电性

在300—20K的温度范围内观测了用丘克拉斯基法生长的Li_0.025Na_0.975NbO₃晶体的介电、铁电和热电特性。介电常数,极化强度和热电性的反常表示该晶体在低温时发生相变。此相变有特别大的热滞(约80K),降温时发生于180K附近,升温时发生于260K附近。测量了晶体的室温结构,指出了可能的低温相点群。观测了热电电荷的时间响应,报道了热电电荷随时间改变符号的特异现象,认为其起因是相变过程中两相共存。 关键词：     

Bias field effects on the dielectric properties of 0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3 single crystals with different orientations

The domain states and phase transitions in 0.67Pb(Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ single crystals were investigated by studying their relative permittivity under various dc bias at constant heating and cooling rates. The orientation dependence of the bias field effect was revealed by examining the temperature dependence of relative permittivity as a function of crystal orientation (the 〈111〉, 〈011〉 and 〈001〉 directions) and dc bias field. The crystals basically have a macrodomain rhombohedral ferroelectric state in the ferroelectric phase under zero dc bias. External bias field could modulate the domain state and induce a stable macrodomain state in the crystals. Also, it is proposed that the dc bias applied along the 〈001〉 or 〈011〉 direction could induce a tetragonal ferroelectric phase or an orthorhombic ferroelectric phase, respectively, in an intermediate temperature range.     

Linear and nonlinear dielectric properties of nanocomposites based on the organic ferroelectric of diisopropylammonium bromide

ABSTRACT

The present work aims at investigating linear and nonlinear dielectric properties of nanocomposites based on diisopropylammonium bromide (C₆H₁₆NBr, DIPAB) embedded into Al₂O₃ films having honeycomb structure with pores of 100?nm in diameter, and into opal matrices with three-dimensional structure containing pores of 100 and 60?nm. The obtained results indicated the shift of Curie point toward lower temperatures for DIPAB in porous aluminum oxide and the appearance of two phase transitions, detected upon heating and cooling for DIPAB in opal matrices. In addition, a ferroelectric phase was found to form between these two phase transitions without significant change of Curie temperature.     

High-temperature phase transitions in the improper ferroelectric KIO3

The ac conductivity (σ_ac) and dielectric permittivity (?) are determined in the temperature range 300?K?T3 compound. The results indicated that the compound behaves as an improper ferroelectric and undergoes a ferroelectric phase transition from a high temperature rhombohedral phase I to a low temperature monoclinic phase II at T _c?=?(486?±?1)?K. A second structural phase transition was observed around 345?K. The conductivity varies with temperature range and for T?>?428?K intrinsic conduction prevails. Different activation energies in the different temperature regions were calculated. The frequency dependence of σ(ω) was found to follow the universal dynamic response [σ(ω)∝(ω) ^s(T)]. The thermal behaviour of the frequency exponent s(T) suggests the hopping over the barrier model rather than the quantum mechanical tunneling model for the conduction mechanism.     

Control of the temperature hysteresis and diffuse dielectric anomaly in the temperature range of the ferroelectric-antiferroelectric phase transition in PbZr1 − x TixO3 (0.03 ≤ x ≤ 0.05) ceramics

The magnitudes of the temperature hysteresis and diffuse dielectric anomaly corresponding to the transition from the antiferroelectric phase to the ferroelectric phase in PbZr_{1 ? x} Ti_xO₃ (0.03 ≤ x ≤ 0.05) ceramics can be reversibly changed by varying the temperatures of heating and cooling in the course of thermocycling. The results obtained indicate that the antiferroelectric-ferroelectric transition in the PbZr_{1 ? x} Ti_xO₃ ceramics materials is a smeared first-order phase transition.     

Broad-band dielectric response of 0.5Ba(Ti0.8Zr0.2)O3–0.5(Ba0.7Ca0.3)TiO3 piezoceramics: soft and central mode behaviour

ABSTRACT

Dielectric properties of 0.5Ba(Ti_0.8Zr_0.2)O₃–0.5(Ba_0.7Ca_0.3)TiO₃ ceramics were probed in the frequency range from 10 Hz to 100 THz in a broad temperature range (10–900 K). Polar soft phonon observed in infrared spectra softens with cooling; however, below 500 K, its frequency becomes temperature independent. Simultaneously, a central mode activates in terahertz and microwave spectra; and it actually drives the ferroelectric phase transitions. Consequently, the phase transitions strongly resemble a crossover between the displacive and order–disorder type. The central mode vanishes below 200 K. The dielectric relaxation in the radiofrequency and microwave range anomalously broadens on cooling below T_C1, resulting in the nearly frequency independent dielectric loss below 200 K. This broadening comes from a broad frequency distribution of ferroelectric domain wall vibrations. Raman spectra reveal new phonons below 400 K, i.e. already 15 K above T_C1. Several weak modes are detected in the paraelectric phase up to 500 K in Raman spectra. Activation of these modes is ascribed to the presence of polar nanoclusters in the material.     

Low-temperature phase transitions in LiKSO4: A neutron study

A single crystal neutron diffraction study of the low temperature structural phase transitions in LiKSO₄ has been carried out. Detailed temperature dependence of the Bragg peak profiles and integrated intensities for a group of about 20 reflections has been investigated upon cooling and heating in the temperature range 300 K to 96 K. The crystal undergoes three clear phase transitions at 205 K (from sp. gr. P6₃ to sp. gr. P31c), at 189 K and at about 135 K on cooling. The corresponding temperatures are 250 K, 190 K and 138 K on the heating cycle. These transitions are extremely sluggish, the kinetics depending on the thermal treatment of the crystal.     

Specific Features of the Domain Structure of BaTiO<Subscript>3</Subscript> Crystals during Thermal Heating and Cooling

This paper presents the results of the study of the domain structure of barium titanate crystals in a wide temperature range including the Curie point (T_C) using the polarization-optical method in the reflected light and the force microscopy of the piezoelectric response. It is shown that a new a–c domain structure forms during cyclic heating of the crystal above T_C and subsequent cooling to the ferroelectric phase. The role of uncompensated charges appeared on the crystal surface during the phase transition and their influence on the formation of the domain structure during cooling are discussed.     

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.     

Microstructural evolution in Al–Mn–Cu–(Be) alloys

This study investigates the effects of alloying elements on the microstructural evolution of Al-rich Al–Mn–Cu–(Be) alloys during solidification, and subsequent heating and annealing. The samples were characterised using scanning electron microscopy, energy dispersive X-ray spectroscopy, synchrotron X-ray diffraction, time-of-flight secondary-ion mass spectroscopy, and differential scanning calorimetry. In the ternary Al₉₄Mn₃Cu₃ (at%) alloy, the phases formed during slower cooling (≈1?K?s^?1) can be predicted by the known Al–Mn–Cu phase diagram. The addition of Be prevented the formation of Al₆Mn, decreased the fraction of τ₁-Al₂₉Mn₆Cu₄, and increased the fraction of Al₄Mn. During faster cooling (≈1000?K?s^?1), Al₄Mn predominantly formed in the ternary alloy, whereas, in the quaternary alloys, the icosahedral quasicrystalline phase dominated. Further heating and annealing of the alloys caused an increase in the volume fractions of τ₁ in all alloys and Be₄Al (Mn,Cu) in quaternary alloys, while fractions of all other intermetallic phases decreased. Solidification with a moderate cooling rate (≈1000?K?s^?1) caused considerable strengthening, which was reduced by annealing for up to 25% in the quaternary alloys, while hardness remained almost the same in the ternary alloy.     

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.     

Dielectric properties of crystalline binary KNO3—AgNO3 mixtures embedded in nanoporous silicate matrices

The results of dielectric studies of MCM-41 sili cate matrices with cellular pores (37.0 and 26.1 ? in diameter) filled by binary mixtures of K_1−x Ag _x NO₃ (x=0, 0.05, 0.10) are reported in comparison with those obtained for bulk salts of the same composition in the temperature range of structural phase transitions. It has been revealed that, upon heating, the nanocomposites undergo transitions from crystal modification II to phase I, as in bulk KNO₃, whereas the bulk mixtures with x=0.05 and 0.10 have a complex structure in accordance with the phase diagram. It has been shown that embedding binary salts and pure potassium nitrate in pores with a diameter of 26.1? results in the formation of an intermediate ferroelectric phase upon cooling. The permittivity and electrical conductivity are found to increase with increasing AgNO₃ concentration in bulk samples, as well as with decreasing pore size in the nanocomposites for all values of x.     

Phase transitions in the oxyfluoride (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>NbOF<Subscript>6</Subscript>

(NH₄)₃NbOF₆ single crystals were grown, polarization-optical studies were performed, and birefringence was measured over the temperature range 90–500 K. A sequence of first-order structural phase transitions was found at temperatures T _1↓ = 259.7 K and T _2↓ = 257.7 K with temperature hysteresis δT ₁ = 0.9 K and δT ₂ = 1.9 K. The transitions are accompanied by twinning and the following change in the crystal symmetry: cubic ? tetragonal ? monoclinic. Optical second harmonic generation is found to occur at room temperature, which indicates that the cubic phase is not centrosymmetric. It is assumed that the phase transitions are ferroelastic and ferroelectric in nature.     

The influence of defects in the pb and o sub-lattices on dielectric properties and phase transitions in PbZrO3

From studies of the influence of controlled introduction of defects into the Pb and O sub-lattices of PbZrO₃ it was ascertained that marked changes are caused in the dielectric parameters and the transitions between the antiferroelectric and ferroelectric states and the ferroelectric and paraeiectric states. With increasing amount of defects the temperature range in which the ferroelectric state occurs is narrowed during the heating process and widened during the cooling process. An attempt has been made to explain the observed effects within the context of existing theoretical models.     

The structure of ‘nearly’ ferroelectric RADP

X-ray scattering techniques have been used to study the structures of two crystals of Rb_1–x (NH₄) _x H₂PO₄ withx0.2, near to the boundary between ferroelectric and structural-glass behavior at low temperature. Below about 83K, both crystals develop shortrange incommensurate correlations with a wavevectorq0.13 a ^* which are presumably related to the glass properties. On cooling below 70 K, the crystal with the slightly larger NH ₄ ⁺ concentrationx, develops the ferroelectric structure in a small fraction of the crystal, while the bulk of the crystal retains the tetragonal structure. The other crystal transforms almost wholly to the ferroelectric phase. The transition to the ferroelectric structure shows considerable hysteresis on heating and cooling, and is spread over about 20 K. The transition is certainly of first order, and the spread in temperature may arise from concentration fluctuations. These results and the structure of the incommensurate modulations are compared with the predictions of a theoretical model for this system.