Phase Transition Hysteresis Research Articles

Dielectric properties of ferroelectric composites (NaNO2)0.95/(PbTiO3)0.05

ABSTRACTThe temperature and frequency dependences of dielectric properties of the ferroelectric composite (NaNO2)0,95/(PbTiO3)0,05 near the phase transition of sodium nitrite have been studied. A significant increase in the real part of the dielectric constant at low frequencies and its strong decrease with increasing frequency were discovered. The temperature hysteresis of phase transition is about 1.5 K. The dielectric constant upon cooling from the paraelectric phase to 273 K is less than during heating, while a similar dependence is observed for conductivity. The results are analyzed in the Landau – Ginzburg theory framework.

Domain structures and correlated out-of-plane and in-plane polarization reorientations in Pb(Zr0.96Ti0.04)O3 single crystal via piezoresponse force microscopy

Pb(Zr1-xTix)O3 single crystal with a low titanium content (x = 4%) was studied by the piezoresponse force microscopy (PFM) and X-ray diffraction (XRD). The XRD studies showed that the crystal faces are orthogonal to the principal cubic axes and confirmed the existence of an intermediate phase between the high-temperature paraelectric (PE) phase and the low-temperature antiferroelectric (AFE) one. A significant temperature hysteresis of phase transitions was observed by the XRD: On heating, the AFE state transforms into the intermediate one at about 373 K and the PE phase appears at 508 K, whereas on cooling the intermediate phase forms at 503 K and persists down to at least 313 K. The PFM investigation was focused on the intermediate phase and involved measurements of both out-of-plane and in-plane electromechanical responses of the (001)-oriented crystal face. The PFM images revealed the presence of polarization patterns switchable by an applied electric field, which confirms the ferroelectric character of the intermediate phase. Importantly, two types of regular domain structures were found, which differ by the spatial orientation of domain walls. The reconstruction of polarization configurations in the observed domain structures showed that one of them is a purely ferroelectric 180° structure with domain walls orthogonal to the crystal surface and parallel to one of the ⟨111⟩ pseudocubic directions. Another one is a ferroelectric-ferroelastic domain structure with the 71° walls parallel to the {101} or {011} crystallographic planes. Remarkably, this domain structure shows correlated out-of-plane and in-plane polarization reorientations after the poling with the aid of the microscope tip.

Temperature hysteresis of AgI phase transition in AgI–chalcogenide glass nanolayered films

Using a method of laser ablation, a number of AgI–chalcogenide glass nanolayered films has been obtained with different thicknesses of the layers (10, 25, 50, and 100 nm). In order to study α ⇆ β phase transition in AgI, X-ray phase analysis has been carried out in the temperature range from 30 to 200°C. A correlation between the layer thickness and the temperature of the α → β phase transition during the lowering of the temperature is found. An explanation of the correlation is proposed.

Shift of Phase Transitions in a (NaNO2)1–x /(KNO2) x Ferroelectric Composite

Temperature and frequency dependence of the dielectric properties of a (NaNO2)1–x/(KNO2)x composite is investigated. The temperature hysteresis of the upper phase transition and the change of the interval of existence of the disproportionate phase are established. Upon cooling, the real component of the dielectric permittivity at low frequencies f < 105 Hz is less than upon heating, whereas the inverse dependence is observed for tan δ.

High pressure Raman spectroscopy of H2O-CH3OH mixtures.

Complex intra-molecular interactions and the hydrogen-bonding network in H2O-volatile mixtures play critical roles in many dynamics processes in physical chemistry, biology, and Earth and planetary sciences. We used high pressure Raman spectroscopy to study the pressure evolution of vibrational frequencies and bonding behavior in H2O-CH3OH mixtures. We found that the presence of low CH3OH content in H2O increases the transition pressure where water crystallizes to ice VI, but does not significantly change the pressure where ice VI transforms to ice VII. Furthermore, the stiffening rates of C-H stretching frequencies dω/dP in CH3OH significantly decrease upon the crystallization of water, and the softening rates of the O-H stretching frequencies of ice VII are suppressed over a narrow pressure range, after which the frequencies of these modes shift with pressure in ways similar to pure CH3OH and ice VII, respectively. Such complex pressure evolution of Raman frequencies along with pronounced variations in Raman intensities of CH3OH within the sample, and the hysteresis of the water-ice VI phase transition suggest pressure-induced segregation of low content CH3OH from ice VII. These findings indicate the significant influence of volatiles on the crystallization of sub-surface ocean and thermal evolution within large icy planets and satellites.

The effect of heating rate on the phase transition and crystallization kinetics of Ag2Se0.2Te0.8 alloy

The Ag2Se0.2Te0.8 bulk alloy has been prepared by slow cooling method. Differential scanning calorimetric analysis is carried out at different heating and cooling rates on the bulk alloy. It is confirmed that bulk alloy undergoes a structural phase transition with hysteresis influenced by the heating rates. The effect of heating rate on the phase transition temperature and hysteresis is discussed. The activation energy of phase transition (Ec) and latent heat of the phase transition are calculated. The thermo gravimetric analysis has also been made on the sample, and the results are reported.

Pressure-induced elastic and structural changes in hydrous basalt glasses: The effect of H2O on the gravitational stability of basalt melts at the base of the upper mantle

To understand the effect of hydration on the elastic properties of silicate melts, we conducted in situ high-pressure Brillouin scattering measurements on two hydrous basalt glasses with different water contents in diamond anvil cells. Second-order phase transitions were observed in the hydrous basalt glasses and are due to the topological rearrangement of the silicate network to a high [Si, Al]–O coordination. Up to a pressure of 10 GPa at 300 K, the extra 2.23 wt% H2O lowers the elastic moduli of FX-2 basalt glass (2.69 wt% H2O) by 10%–18%, but does not affect the pressure derivatives of the elastic moduli, compared with FX-1 (0.46 wt% H2O) basalt glass. The phase transition takes place at a higher pressure in FX-2 compared with FX-1, possibly because of the depolymerization of water to silicate glass. Water interacts with network-forming cations and creates Si–OH and Al–OH groups, and prohibits nonbridging oxygen ions from being connected to other nearby framework cations (i.e., [5,6](Si, Al)), resulting in the hysteresis of the second-order phase transition. The density contrasts of our hydrous basalt melts with previous mid-ocean ridge basalt and preliminary reference Earth model data indicate that basalt melts may need very low water content (<0.46 wt% H2O) to maintain gravitational stability at the base of the upper mantle. Our results show that the elastic properties of hydrous silicate melts may have important implications for the dynamic evolution and chemical differentiation of the mantle.

Monte Carlo simulation of the magnetic properties of a spin-1 Blume–Capel nanowire

Monte Carlo simulation has been used to study the magnetic properties and hysteresis loops of a Blume–Capel nanowire, consisting of a ferromagnetic core of spin-1 atoms surrounded by a ferromagnetic shell of spin-1 atoms with ferromagnetic or anti-ferromagnetic interfacial coupling. We have examined the influence of the crystal field, the temperature, and the interfacial coupling on the hysteresis behavior, susceptibility, specific heat and internal energy. The remanent magnetization and the coercive field as a function of the temperature have also been investigated. We have found that the system exhibits the first order phase transition, one or double hysteresis loops in the ferromagnetic case, and one or triple hysteresis loops in the ferrimagnetic case.

Programmable Polymer‐Based Supramolecular Temperature Sensor with a Memory Function

A new class of polymeric thermometers with a memory function is reported that is based on the supramolecular host-guest interactions of poly(N-isopropylacrylamide) (PNIPAM) with side-chain naphthalene guest moieties and the tetracationic macrocycle cyclobis(paraquat-p-phenylene) (CBPQT(4+)) as the host. This supramolecular thermometer exhibits a memory function for the thermal history of the solution, which arises from the large hysteresis of the thermoresponsive LCST phase transition (LCST = lower critical solution temperature). This hysteresis is based on the formation of a metastable soluble state that consists of the PNIPAM-CBPQT(4+) host-guest complex. When heated above the transition temperature, the polymer collapses, and the host-guest interactions are disrupted, making the polymer more hydrophobic and less soluble in water. Aside from providing fundamental insights into the kinetic control of supramolecular assemblies, the developed thermometer with a memory function might find use in applications spanning the physical and biological sciences.

Programmable Polymer‐Based Supramolecular Temperature Sensor with a Memory Function

AbstractA new class of polymeric thermometers with a memory function is reported that is based on the supramolecular host–guest interactions of poly(N‐isopropylacrylamide) (PNIPAM) with side‐chain naphthalene guest moieties and the tetracationic macrocycle cyclobis(paraquat‐p‐phenylene) (CBPQT4+) as the host. This supramolecular thermometer exhibits a memory function for the thermal history of the solution, which arises from the large hysteresis of the thermoresponsive LCST phase transition (LCST=lower critical solution temperature). This hysteresis is based on the formation of a metastable soluble state that consists of the PNIPAM–CBPQT4+ host–guest complex. When heated above the transition temperature, the polymer collapses, and the host–guest interactions are disrupted, making the polymer more hydrophobic and less soluble in water. Aside from providing fundamental insights into the kinetic control of supramolecular assemblies, the developed thermometer with a memory function might find use in applications spanning the physical and biological sciences.

Martensitic and austenitic transformations in core-surface cubic nanoparticles

As a continuation of our recently published work, we have used the pair approximation in Kikuchi version to investigate martensitic and austenitic transformations in homogeneous (HM) and composite (CM) cubic nanoparticles (CNPs) based on the Blume–Emery–Griffiths model. A single cubic nanoparticle made of a core surrounded by a surface is considered as shaped in two dimensional (2D) square arrays instead of hexagonal array. From the phase diagrams of HM and CM-CNPs it has been observed that the martensitic–austenitic transformations (MT–AT) occurred. The influence of the exchange coupling and single-ion anisotropy parameters in the model Hamiltonian on the MT–AT is studied and analyzed in comparison with the results for hexagonal nanoparticles. Significant changes of the phase transition points and hysteresis behaviours depending upon the particle structure have been discussed. • This paper realized cubic nanoparticles. • This nanoparticles are investigated with single-ion anisotropy. • The hysteretic splitting are plotted.

Influence of the thickness of [N(CH3)4]2Zn0.75Mn0.25Cl4 crystal on the phase-transition temperature

The change in the phase-transition temperature of [N(CH3)4]2Zn0.75Mn0.25Cl4 crystal as a function of its size (3500 μm-1 μm) has been investigated. It is established that a decrease in crystal sizes along the spontaneous-polarization axis is accompanied by several effects: a shift of the initial phase-incommensurate phase transition point to higher temperatures, an increase in the temperature range of existence of incommensurate phase, an increase in the temperature range of existence of metastable states of incommensurate structure, the occurrence of new long-period commensurate phases, and an increase in phase-transition temperature hysteresis at Tc and T3. The possibility that a size effect exists in the phase diagram of this crystal is discussed.

Phase transitions and interface phenomena in the cryogenic temperature domain of a niobate nanostructured ceramic.

Powder neutron diffraction and dielectric spectroscopy were used to investigate both crystallographic and dielectric permittivity properties of a Sr2KNb5O15 single phase ferroelectric oxide with nanosized grains ranging from 35 nm to 90 nm. Measurements were carried out in the temperature range from 10 K (cryogenic) to 550 K. All neutron diffraction data were indexed on the basis of a tetragonal double unit cell. From 10 K to room temperature the space group of the Sr2KNb5O15 ferroelectric phase was considered to be P4bm. The refinement of the paraelectric phase (at 550 K) was determined in the centrosymmetric space group P4/mbm. Dielectric spectroscopy measurements were performed in a thermal cycle. A set of four phase transitions non-related to symmetry changing was detected from Rietveld analysis of neutron powder diffraction data. During a thermal cycle, in the cryogenic temperature domain, strong thermal hysteresis is developed. Both phase transition and thermal hysteresis were correlated. These phenomena are associated with Nb-cation atomic displacements in the NbO6 octahedra along the c-axis direction and of the domain with different frequencies involving grains as well as an excess of interfaces ascribed to the grain boundary. The bulk/grain boundary interfaces in nanostructured ceramics are correlated with the thermal stability phenomenon.

First-Order Phase Transition and Anomalous Hysteresis of Binary Bose Mixtures in an Optical Lattice

We study a first-order phase transition between superfluid and Mott insulator phases in binary Bose mixtures loaded into a hypercubic optical lattice. The system is described by a two-component Bose-Hubbard model. Considering the difference between the two kinds of bosons in the intra-component interaction strength, we discuss the metastability of the system and the hysteresis associated with the first-order superfluid-Mott insulator transition. It is found that the sweeping of hopping amplitude induces a conventional hysteresis-loop behavior. We also find an anomalous hysteresis behavior when the chemical potential is varied. In the anomalous hysteresis, the phase transition occurs in a unidirectional way and a hysteresis loop does not form.

First-order phase transition and anomalous hysteresis of Bose gases in optical lattices

We study the first-order quantum phase transitions of Bose gases in optical lattices. A special emphasis is placed on an anomalous hysteresis behavior, in which the phase transition occurs in a unidirectional way and a hysteresis loop does not form. We first revisit the hardcore Bose-Hubbard model with dipole-dipole interactions on a triangular lattice to analyze accurately the ground-state phase diagram and the hysteresis using the cluster mean-field theory combined with cluster-size scaling. Details of the anomalous hysteresis are presented. We next consider the two-component and spin-1 Bose-Hubbard models on a hypercubic lattice and show that the anomalous hysteresis can emerge in these systems as well. In particular, for the former model, we discuss the experimental feasibility of the first-order transitions and the associated hysteresis. We also explain an underlying mechanism of the anomalous hysteresis by means of the Ginzburg-Landau theory. From the given cases, we conclude that the anomalous hysteresis is a ubiquitous phenomenon of systems with a phase region of lobe shape that is surrounded by the first-order boundary.

Polyamorphism in cerium based bulk metallic glasses: Electronic and structural properties under pressure and temperature by x-ray absorption techniques

High pressure and high temperature x-ray absorption near edge spectroscopy experiments have been carried out on Ce60Al20Cu20 bulk metallic glass showing an electronic delocalization of the 4f-electron of cerium under pressure. In parallel, high pressure extended x-ray absorption fine structure spectroscopy reveals large structural modifications of the cerium local environment. This study provides experimental evidence that an electronic driven structural transformation occurs in cerium based bulk metallic glasses (Ce-BMGs). The effect of temperature on the hysteresis of this amorphous-amorphous phase transition is also discussed, suggesting the existence of a critical point in the phase diagram of Ce-BMGs. This work will encourage further investigations on Ce-based metallic glasses phase diagrams in order to support, or refute, the actual theoretical understanding of polyamorphism.

Irreversible Thermodynamic Discussions about Ferroelectric Phase Transitions

The irreversibility of ferroelectric phase transitions has been studied by using the irreversible thermodynamics. The thermal hysteresis of first-order ferroelectric phase transitions and the polydomain structure of ferroelectrics can be explained on the basis of the principle of minimum entropy production. A conclusion has been derived that the thermal hysteresis is not an intrinsic property of a system in which a first-order ferroelectric phase transition occurs. The finiteness of the systems surface is connected with the thermal hysteresis.

Reversible aggregation kinetics of poly(N-isopropylacrylamide-co-N-vinylpyrrolidone) in aqueous solutions revealed by elastic light scattering spectroscopy

Poly(N-isopropylacrylamide-co-N-vinylpyrrolidone) [P(NIPAM-co-NVP)] copolymers with different content of N-vinylpyrrolidone (NVP) were synthesized, and reversible aggregation kinetics of the copolymers in aqueous solutions was investigated with elastic light scattering (ELS) spectra. The results indicated that the apparent activation energy of aggregation process during heating and dissociation process during cooling increased with the NVP content increasing. The phase transition temperature also increased as the content of NVP increased, suggesting that the hydrophilic nature of NVP strongly affected the phase behavior of the copolymer solutions. The higher the content of NVP, the higher the temperature required to break the balance between the hydrophilic and hydrophobic interaction. Besides, during heating and cooling process, the phase transition hysteresis of P(NIPAM-co-NVP) chains decreased when the hydrophilic comonomer increased.

Preparation and investigation of sputtered vanadium dioxide films with large phase-transition hysteresis loops

Vanadium dioxide (VO2) films with large phase-transition hysteresis loops were fabricated on glass substrates by reactive direct current (DC) magnetron sputtering in Ar/O2 atmosphere and subsequent in situ annealing process in pure oxygen. The crystal structure, chemical composition, morphology and metal-insulator transition (MIT) properties of the deposited films were investigated. The results reveal that the films show a polycrystalline nature with a (011) preferred orientation and consist of small spheroidal nanoparticles. All the deposited VO2 films show large hysteresis loops due to the small density of nucleating defects and the large interfacial energies, which are determined by the characteristics of the particles in the films, namely the small transversal grain size and the spheroidal shape. The film comprising the smallest spheroidal nanoparticles not only shows a large hysteresis width of 36.3°C but also shows a low transition temperature of 32.2°C upon cooling. This experiment facilitates the civilian applications of the VO2 films on glass substrates in optical storage-type devices.

그래핀/사파이어 기판상에 스퍼터링 후 열처리된 VO2박막의 구조 및 광학적 특성변화 연구

이산화바나듐(<TEX>$VO_2$</TEX>)는 써모크로믹(thermochromic) 물질로서 온도변화에 따른 구조적 상전이에 의해 전기적, 광학적 특성을 스위칭 할 수 있는 매력적인 소재이며, 최근 신소재로써 그 연구가 활발한 그래핀 역시, 전기적으로나 광학적으로 그 특성이 우수하여 투명전극에 관한 연구가 아주 활발하게 진행되고 있다. 이에 우리는 <TEX>$VO_2$</TEX>와 그래핀 두 가지 소재를 접목했을 경우 나타나는 현상을 그래핀의 층 수와 온도를 변수로 하여 형성된 박막의 구조와 광학적 특성을 측정하고 분석하였다. 본 연구 결과에 따르면 그래핀 필름이 전사된 사파이어 기판 위에 형성된 <TEX>$VO_2$</TEX> 박막의 표면구조 및 특성이 bare 사파이어 기판 위의 <TEX>$VO_2$</TEX> 박막보다 그레인이 작고 밀도가 높아 균일하였으며, IR 영역에서의 광투과도 역시 그래핀 필름이 있을 경우 ~10% 정도 개선됨을 확인하였다. 아울러 평균상전이 온도를 낮출 수 있으며, 상전이 히스테리시스 변화폭 또한 좁아지는 것을 확인하였다. <TEX>$VO_2$</TEX> is an attractive thermochromic material, in which its electrical and optical properties can be switched by the structural phase-transition about <TEX>$68^{\circ}C$</TEX>. Recently, graphene is also a rising material which is researched as a transparent electrode because of its superior electrical and optical characteristics. In this respect, we try to fabricate the hybridized films using <TEX>$VO_2$</TEX> and graphene on transparent sapphire substrate and then we investigate a structure and characterize an optical property for the samples as a function of temperature. According to the result of IR-transmittance analysis of <TEX>$VO_2$</TEX> films as a function of temperature, the graphene-supported sapphire substrates are better about 10% than the bare sapphire substrates. The mean phase transition temperatures are also decreased as the number of graphene-layers increased and the hysteresis of phase transitions are narrowed.