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.     

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.     

Dielectric properties of ferroelectric diisopropylammonium iodide

Temperature dependences of dielectric constant, amplitude of the third harmonic and heat capacity for the organic ferroelectric of diisopropylammonium iodide (C₆H₁₆NI) have been investigated. The measurements were carried out through heating and cooling cycles in the range of 300–400?K. It was found that upon the first heating, only one phase transition occurred without the presence of the ferroelectric phase. For samples preheated over 420?K, two phase transitions at 363 and 378?K appeared in the heating process, and the ferroelectric state was also observed between them. Upon cooling, the ferroelectric phase was detected in the range of lower 361?K and persisted up to room temperature.     

Thermal effects in the vicinity of phase transition temperatures in matrix-isolated sodium nitrite NaNO<Subscript>2</Subscript>

Thermal effects in some nanoporous silicate matrices (with different pore sizes) loaded with ferroelectric NaNO₂ from both a saturated solution and from a melt have been studied in a wide temperature range including the phase transition temperatures. All the samples reliably demonstrate maxima of the heat capacity, corresponding to first-order ferroelectric phase transitions. The characteristics of the maxima (intensity, half-width, phase transition temperature, etc.) have been determined. A more complex situation is the observation of an incommensurable phase (sinusoidal antiferroelectric), in particular, in the case of pore sizes comparable to the period of an “incommensurable” wave, the manifestation of which can be explained by the appearance of a corresponding orientation of sodium nitrite nanocrystals in pores of these matrices. It is found that the characteristics of above noted effects depend on the prehistory of the samples under study.     

Caloric characteristics of PbTiO3 in the temperature range of the ferroelectric phase transition

The heat capacity and thermal expansion of the PbTiO₃ ceramic sample have been measured in the temperature range 80?C970 K. The electrocaloric and barocaloric efficiencies of lead titanate in the ferroelectric phase transition range have been investigated by analyzing the experimental data in terms of the thermodynamic theory of phase transitions, the electrical equation of state P(T, E), the Pippard equation, and the S(T, p) diagram.     

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.     

Dielectric studies of nanoporous alumina films filled with the Rochelle salt

Dielectric studies of nanoparticles of the Rochelle salt embedded in pores of porous alumina have been performed in the temperature range from 80 K to the decomposition temperature of the bulk Rochelle salt. It has been revealed that the permittivity exhibits an anomaly corresponding to the lower structural transition to the paraelectric phase, whereas the upper ferroelectric transition is shifted above the decomposition temperature in agreement with the recently published data. The temperature of the lower transition for nanoparticles in pores is found to decrease by 10 K. Possible physical factors that can be responsible for the broadening of the region of existence of the ferroelectric phase have been discussed.     

Shifting of transition temperature of ferroelectric liquid crystals due to addition of dye-An optical and dielectric study

In order to study the shifting of phase transition temperature of ferroelectric liquid crystals due to addition of dye molecules, we have investigated two ferroelectric liquid crystal materials (Felix 16/030 and Felix 16/100) and their five mixtures with Anthraquinone dye (1%, 2%, 3%, 4% and 5% wt/wt). The phase transition scheme has been investigated and analyzed by results obtained from the optical transmittance and the dielectric permittivity study with variation of temperature in the range of 30 to 100 °C. Both the samples clearly show the shifting of phase transition temperature with dye concentration, especially the SmC*-SmA phase transition temperature. It is also clear from the study that SmC*-SmA phase transition phenomenon also becomes stronger with the addition of dye molecules. A theoretical explanation has also been given for shifting of phase transition temperature. The amount of shift in transition temperature agrees well as obtained from optical and dielectric studies.     

Pressure-induced phase transition of crystalline and amorphous silicon and germanium at low temperatures

Abstract

X-ray diffraction has been measured for crystalline silicon, crystalline germanium, amorphous silicon and amorphous germanium at temperatures down to 100 K and pressures up to 20 GPa using a diamond anvil cell and synchrotron radiation. The structural phase transitions, including amorphization, take place in the pressure-temperature range. It has been found that the structures after the phase transitions strongly depend on the path in the pressure-temperature diagram through which the system undergoes the phase transitions. For any of the aforementioned four materials, the high-pressure phase with the p-Sn structure is quenched during a release of pressure at 100 K, and transforms into an amorphous state when heated up to around 2 GPa. The path dependence of the states is discussed in relation to the pressure dependence of the heights of the energy barriers which have to be overcome when phase transitions occur. The effect of a structural disorder on the phase transition is also discussed by comparing the experimental results for the crystalline and amorphous materials.     

Phase transitions in KNO3 embedded in MCM-41 films with regular nanopores

This paper reports on a comparative study of phase transitions in nanocomposites made up of KNO₃ embedded in 10-μm-thick MCM-41 films with unidirectional pores 4.0 nm in size on an aluminum substrate and of nanocomposites prepared in the form of potassium-nitrate-filled pressed MCM-41 powders with 3.7-nm pores. The temperature dependences of linear permittivity and the amplitude of third harmonic generation have been measured under heating and cooling. The structural transition from phase II to phase I shifts under heating relative to that occurring in bulk KNO₃ toward lower temperatures for potassium nitrate in the film and toward higher temperatures for the pressed MCM-41-based nanocomposite. A significant difference has been observed also within the region of existence of ferroelectric phase III. The data obtained suggest that the shifts of phase transition temperatures observed in the conditions of nanoconfinement are influenced markedly not only by pore size and geometry but also by other factors.     

Phase transitions in ferroelectric liquid crystals

Molecular chirality plays an important role in the science of liquid crystals, leading to cholesteric liquid crystal, blue phases, ferroelectric and antiferroelectric smectic phases and twist grain boundary phases. In all of these mesogens, chirality is an intrinsic property built into the chemical structure of mesogenic molecules. The study of ferroelectric liquid crystals has seen substantial experimental strides. In theoretical aspects, there has been relatively little basic work on this fascinating class of material. This review will try to present a comprehensive overview of the current status of the phase transitions in ferroelectric smectic liquid crystals. The article begins with a brief introduction about the symmetry and structure of ferroelectric mesophases. An attempt is made to identify a range of problems and related questions associated with the study of phase transitions. In the remaining parts of the article the important experimental and theoretical developments are summarized. Finally, some of the future directions have been identified.     

Symmetry breaking at the phase transitions in ferroelectric pyridinium salts

The phase transitions in ferroelectric pyridinium tetrafluoroborate (PyBF₄) and pyridinium perchlorate (PyClO₄) have been characterized by structural studies. The continuous ferroelectric phase transition at 238.7 K in PyBF₄ appears to be a unique case for multiaxial ferroelectrics, while the first order phase transition in PyClO₄ at 248 K is consistent with the Landau theorem for deducing the character of phase transitions from symmetry considerations. The phase transition in both materials is caused by ordering of the pyridinium cation as well as tetrahedral anions.     

Investigation of the dielectric properties and thermal expansion of the ferroelectric ceramic PKR-1 in the phase-transition region

The permittivity and thermal expansion of polarized and unpolarized samples of the ferroelectric ceramic PKR-1 have been investigated in the temperature range 300–700 K. Anomalous behavior of the thermal expansion coefficient is found in the range of ferroelectric phase transitions. The results obtained are analyzed taking into account the specific features of the structure of polar ceramics.     

Photostimulated luminescence in PbHPO4 near TC

Optical properties (absorption and photoluminescence) of PbHPO₄ single crystals have been performed in the range 100 – 350 K, spanning the transition temperature (T_C=310 K). An intrinsic luminescene band centered at 450 nm has been observed. The excitation spectrum for this emission shifts with temperature in the ferroelectric phase. The temperature dependence for this shift has been determined as E(T) T, for T<T_C. Similar behaviour had been observed in birrefringence measurements (performed by other authors), which yield n T P_S² (spontaneous polarization). The results show that the flourescence is very useful, as an alternative technique, to study the dynamics of the phase transitions.     

Effect of ionizing radiation on the dielectric characteristics of TlInS2 and TlGaS2 single crystals

The dependences of the permittivity and electrical conductivity of TlInS₂ and TlGaS₂ single crystals on the temperature and electron beam irradiation dose have been studied. It has been established that, as the electron irradiation dose increases, the electrical conductivity σ significantly increases, whereas the permittivity ? decreases over the entire temperature range covered (80–320 K). It has been shown that anomalies in the form of maxima in the temperature dependences σ(T) and ?(T) are observed in the regions characteristic of phase transitions in TlInS₂. Irradiation of the TlInS₂ and TlGaS₂ crystals with electrons to doses of 10¹⁵ and 10¹⁶ cm^?2 does not affect their phase transition temperatures. The dispersion curves of the permittivity ? of the TlGaS₂ crystal have been constructed.     

Effect of confined geometry on linear and nonlinear dielectric properties of triglycine sulfate near the phase transition

The temperature dependence of the linear permittivity and the third harmonic generation amplitude of nanocomposites representing nanoporous silica matrices (opal matrix and SBA-15) with triglycine sulfate embedded in pores has been studied in the region of the ferroelectric phase transition. A broadening of the phase transition and an increase its temperature in comparison with bulk triglycine sulfate have been revealed. The latter becomes more significant as the pore size decreases. It has been shown that the nonlinear dielectric properties of nanocomposites near the phase transition differ significantly from the properties of bulk triglycine sulfate.     

硫酸氢铵高压下相变研究

由于铁电材料在科学研究领域的重要应用,功能铁电材料的设计和机理研究一直是国内外的研究热点。材料的性能离不开结构研究,为了更好的认识和理解一种典型铁电材料-硫酸氢铵的结构和相行为,研究了17GPa压强下硫酸氢铵的高压拉曼光谱。在压力作用下,绝大多数的拉曼谱线向高波数方向移动,并且有两个特征拉曼谱带的强度发生很大的变化(1 018和3 183cm~(-1)),表明硫酸盐与铵离子正四面体的电子云密度发生重构。根据频移-压强曲线关系,得出了硫酸氢铵在6和10.5GPa附近分别存在一阶相变。根据高压下S=O伸缩振动谱带的变化规律,发现了不同相区间氢键的相反作用规律。为AHSO_4系列铁电材料压力作用下结构变化规律提供一定的研究基础。     

Phase transitions and critical phenomena in multiferroic films with orthorhombic magnetic structure

Phase transitions and critical phenomena in materials with strongly correlated magnetic, ferroelectric, and elastic subsystems are studied. A theoretical study of the influence external fields (dc and ac) have on the dynamics of phase transitions in perovskite-type crystals is performed.     

Raman scattering spectra of ceramics, films, and superlattices of ferroelectric perovskites: A review

Raman investigations of the crystal lattice dynamics in classical ferroelectric perovskites SrTiO₃, PbTiO₃, and BaTiO₃ have been analyzed. The specific features revealed in the behavior of soft modes during the phase transitions occurring in ceramics and powders of these compounds, as well as in several related solid solutions, have been described. Particular attention has been paid to the investigations of ferroelectric thin films and superlattices in which the sequences of structural distortions can be radically different from those known for the initial bulk materials.     

Reverse dependences of the permittivity of xPZN − (1 − x)PSN ferroelectric ceramics on the bias electric field

The effect of bias electric fields E ₌ on the dielectric response of xPZN ? (1 ? x)PSN ferroelectric solid solutions with PZN contents x = 0, 0.05, 0.20, and 0.50 is investigated in the temperature ranges corresponding to the smeared phase transitions of the studied compounds. It is concluded that an increase in the PZN content in this system leads to a narrowing of the temperature range of existence of the relaxor phase.