Ionic Phase Transition Research Articles

Pressure-induced electronic to ionic phase transition and recurrence of ferroelectricity in PbTiO3

A pressure-induced transition from electronic conduction to ionic conduction was observed in polycrystalline PbTiO3, accompanied by the disappearance and reappearance of ferroelectricity.

Pressure-Induced Neutral to Ionic Phase Transition in TTF-Fluoranil, DimethylTTF-Fluoranil and DimethylTTF-Chloranil: A Comparative THz Raman Study

The Neutral to Ionic phase Transition (NIT) that occurs in few mixed stack charge transfer cocrystals at high pressure or low temperature is a charge instability combined with a structural instability. The lattice contraction, which increases the 3D Coulomb interactions, favors a higher degree of charge transfer. Due to Peierls instability, this leads to the dimerization of the stack, breaking its inversion symmetry. The 3D interactions also determine the arrangement of the adjacent dimerized polar stacks, making the ionic phase ferroelectric or antiferroelectric. The role of these parameters that modulate the NIT has been widely studied in Tetrathiafulvalene-haloquinone cocrystals. Here, we compare the high-pressure behavior of three of them: the newly synthesized TTF-FA and DMTTF-FA with the known DMTTF-CA and isostructural DMTTF-FA. We followed the evolution of the lattice phonons via THz Raman spectroscopy, assessing the pressure-dependent structural changes. While the FA-based crystals undergo strong first-order NIT, DMTTF-CA shows a continuous transition. The high-pressure behavior of each crystal is also compared with the low-temperature behavior.

Topological Excitations in Neutral–Ionic Transition Systems

The existence and physical properties of topological excitations in ferroelectrics, especially mobile topological boundaries in one dimension, are of profound interest. Notably, topological excitations emerging in association with the neutral–ionic (NI) phase transition are theoretically suggested to carry fractional charges and cause anomalous charge transport. In recent years, we experimentally demonstrated mobile topological excitations in a quasi-one-dimensional (1D) ferroelectric, tetrathiafulvalene-p-chloranil [TTF-CA; TTF (C6H4S4) and CA (C6Cl4O2)], which shows the NI transition, using NMR, NQR, and electrical resistivity measurements. Thermally activated topological excitations carry charges and spins in the NI crossover region and in the ionic phase with a dimer liquid. Moreover, free solitons show a binding transition upon a space-inversion symmetry-breaking ferroelectric order. In this article, we review the recent progress in the study of mobile topological excitations emerging in TTF-CA, along with earlier reports that intensively studied these phenomena, aiming to provide the foundations of the physics of electrical conductivity and magnetism carried by topological excitations in the 1D ferroelectric.

Temperature-induced neutral-to-ionic phase transition of the charge-transfer crystal tetrathiafulvalene-fluoranil

The Temperature Induced Neutral to Ionic phase Transition (TI-NIT) is a rare phenomenon occurring in mixed stack charge transfer (CT) crystals made up of alternating $\pi$-electron Donor (D) and Acceptor (A) molecules. We were able to grow crystals of Tetrathiafulvalene-Fluoranil (TTF-FA), and to show that it undergoes TI-NIT like the prototype CT crystal TTF-Chloranil. We characterized both room and low T phases through IR and Raman spectroscopy and XRD, demonstrating that while TTF-FA is quasi-neutral at room T, its ionicity jumps from 0.15 to 0.7 at low T, therefore crossing the Neutral-Ionic borderline. The transition, occuring around 150K, is first order, with large thermal hysteresis and accompanied by crystal cracking. In the high T phase D and A molecules lie on inversion center, i.e. the stacks are regular, whereas the low T phase is characterized by the loss of the inversion symmetry along the stack as the stacks are strongly dimerized and by the doubling of the unit cell.

Tunable thermoresponsive UCST-type alkylimidazolium ionic liquids as a draw solution in the forward osmosis process

Recently, forward osmosis (FO) has been attracting attention as a new energy-saving water treatment technology. To put the FO process to practical use, it is indispensable to develop the optimum draw solution (DS) and construct its low energy regeneration process. In this study, various types of alkylimidazolium tetrafuluoroborate salts were synthesized, and their capabilities as novel thermoresponsive DSs for the FO desalination process were assessed using solution parameters such as phase diagram and osmotic pressure. The carbon number of a cation tunables the upper critical solution temperature (UCST)-point of alkylimidazolium-based ionic liquids' phase transition temperature. Considering the effect on the membrane material, the cooling temperature according to the climate, and the temperature range of low-grade waste heat in FO process, the ionic liquids having UCST points in the range of 25 °C to 50 °C, 1-pentyl-3-methylimidazolium tetrafluoroborate ([C5mim][BF4]), 1-pentyl-2,3-dimethylimidazolium tetrafluoroborate ([C5dmim][BF4]), 1-butyl-3-ethylimidazolium tetrafluoroborate ([C4eim][BF4]) and 1,3-dipropylidazolium tetrafluoroborate ([C3pim][BF4]), were judged to be suitable. The osmolalities of its water mixture varied with temperature, with a larger value at 50 °C than at 25 °C, with ILs with a lower UCST point exhibiting higher osmolality. The concentrated phase of [C4eim][BF4], which was phase-separated at 25 °C, had an osmotic pressure at 50 °C that was 1.6 times that of seawater, implying that it might be used as a DS in the FO seawater desalination process. Moreover, the osmolality at 25 °C dilutive phases of the [C5mim][BF4], [C5dmim][BF4], and [C4eim][BF4] aqueous solutions were all extremely low, these indicating that the osmotic resistance in the post-treatment membrane process can be minimized. The tunable thermoresponsive materials enabled a flexible process design, depending on the environmental and waste heat temperatures. Further, they can be used in various reaction solvents, extraction solvents, and other ingredients of the process.

Approximate Corona Phase Hamiltonian for Individual Cylindrical Nanoparticle-Polymer Interactions.

Nanoparticle surfaces, such as cylindrical nanowires and carbon nanotubes, are commonly coated with adsorbed polymer corona phases to impart solution stabilization and to control molecular interactions. These adsorbed polymer molecules (biological or otherwise), also known as the corona phase, are critical to engineering particle and molecular interactions. However, the prediction of its structure and the corresponding properties remains an unresolved problem in polymer physics. In this work, we construct a Hamiltonian describing the adsorption of an otherwise linear polymer to the surface of a cylindrical nanorod in the form of an integral equation summing up the energetic contributions corresponding to polymer bending, confinement, solvation, and electrostatics. We introduce an approximate functional that allows for the solution of the minimum energy configuration in the strongly bound limit. The functional is shown to predict the pitch and surface area of observed helical corona phases in the literature based on the surface binding energy and persistence length alone. This approximate functional also predicts and quantitatively describes the recently observed ionic strength-mediated phase transitions of charged polymer corona at carbon nanotube surfaces. The Hamiltonian and the approximate functional provide the first theoretical link between the polymer's mechanical and chemical properties and the resulting adsorbed phase configuration and therefore should find widespread utility in predicting corona phase structures around anisotropic nanoparticles.

A two-dimensional type I superionic conductor.

Superionic conductors possess liquid-like ionic diffusivity in the solid state, finding wide applicability from electrolytes in energy storage to materials for thermoelectric energy conversion. Type I superionic conductors (for example, AgI, Ag2Se and so on) are defined by a first-order transition to the superionic state and have so far been found exclusively in three-dimensional crystal structures. Here, we reveal a two-dimensional type I superionic conductor, α-KAg3Se2, by scattering techniques and complementary simulations. Quasi-elastic neutron scattering and ab initio molecular dynamics simulations confirm that the superionic Ag+ ions are confined to subnanometre sheets, with the simulated local structure validated by experimental X-ray powder pair-distribution-function analysis. Finally, we demonstrate that the phase transition temperature can be controlled by chemical substitution of the alkali metal ions that compose the immobile charge-balancing layers. Our work thus extends the known classes of superionic conductors and will facilitate the design of new materials with tailored ionic conductivities and phase transitions.

Pressure-Induced Neutral–Ionic Phase Transition in the Mixed-Stack 2:1 Charge-Transfer Complex (EDT-TTF-I2)2TCNQF

We explored the neutral–ionic phase transition in (EDT-TTF-I2)2TCNQF by measuring the electrical conductivity as a function of temperature and hydrostatic pressure (up to 11.8 kbar). At about 4.3 k...

Ionic conductivity and phase transitions in solid solutions Na3Sc2(1-x)Yb2x(PO4)3

Ionic conductivity and phase transitions in solid solutions Na3Sc2(1-x)Yb2x(PO4)3

A green route for the fabrication of thermo-sensitive chitosan nerve conduits and their property evaluation

To explore a green route for the fabrication of thermo-sensitive chitosan nerve conduits, improve the mechanical properties and decrease the degradation rate of the chitosan nerve conduits. Taking advantage of the ionic specific effect of the thermo-sensitive chitosan, the strengthened chitosan nerve conduits were obtained by immersing the gel-casted conduits in salt solution for ion-induced phase transition, and rinsing, lyophilization, and 60Co sterilization afterwards. The nerve conduits after immersing in NaCl solutions for 0, 4, 12, 24, 36, 48, and 72 hours were obtained and characterized the general observation, diameters and mechanical properties. According to the above results, the optimal sample was chosen and characterized the microstructure, degradation properties, and cytocompatibility. The left sciatic nerve defect 15 mm in length was made in 20 male Sprague Dawley rats. The autologous nerves (control group, n=10) and the nerve conduits (experimental group, n=10) were used to repair the defects. At 8 weeks after operation, the compound muscle action potential (CMAP) was measured. The regenerated nerves were investigated by gross observation and toluidine blue staining. The gastrocnemius muscle was observed by HE staining. With the increased ionic phase transition time, the color of the conduit was gradually deepened and the diameter was gradually decreased, which showed no difference during 12 hours. The tensile strength of the nerve conduit was increased gradually. The ultimate tensile strength showed significant difference between the 48 hours and 12, 24, and 36 hours groups ( P<0.05), and no significant difference between the 48 hours and 72 hours groups ( P>0.05). As a result, the nerve conduit after ion-induced phase transition for 48 hours was chosen for further study. The scanning electron microscope (SEM) images showed that the nerve conduit had a uniform porous structure. The degradation rate of the the nerve conduit after ion-induced phase transition for 48 hours was significantly decreased as compared with that of the conduit without ion-induced phase transition. The nerve conduit could support the attachment and proliferation of rat Schwann cells on the inner surface. The animal experiments showed that at 8 weeks after operation, the CMAPs of the experimental and control groups were (3.5±0.9) and (4.3±1.1) m/V, respectively, which showed no significant difference between the two groups ( P<0.05), and were significantly lower than that of the contralateral site ［(45.6±5.6 m/V), P>0.05］. The nerve conduit of the experimental group could repair the nerve defect. There was no significant difference between the experimental and control groups in terms of the histomorphology of the regenerated nerve fibers and the gastrocnemius muscle. The green route for the fabrication of thermo-sensitive chitosan nerve conduits is free of any toxic reagents, and has simple steps, which is beneficial to the industrial transformation of the chitosan nerve conduit products. The prepared chitosan nerve conduit can be applied to rat peripheral nerve defect repair and nerve tissue engineering.

Ionic Strength-Mediated Phase Transitions of Surface-Adsorbed DNA on Single-Walled Carbon Nanotubes

Single-stranded DNA oligonucleotides have unique, and in some cases sequence-specific molecular interactions with the surface of carbon nanotubes that remain the subject of fundamental study. In this work, we observe and analyze a generic, ionic strength-mediated phase transition exhibited by over 25 distinct oligonucleotides adsorbed to single-walled carbon nanotubes (SWCNTs) in colloidal suspension. The phase transition occurs as monovalent salts are used to modify the ionic strength from 500 mM to 1 mM, causing a reversible reduction in the fluorescence quantum yield by as much as 90%. The phase transition is only observable by fluorescence quenching within a window of pH and in the presence of dissolved O2, but occurs independently of this optical quenching. The negatively charged phosphate backbone increases (decreases) the DNA surface coverage on an areal basis at high (low) ionic strength, and is well described by a two-state equilibrium model. The resulting quantitative model is able to describe and link, for the first time, the observed changes in optical properties of DNA-wrapped SWCNTs with ionic strength, pH, adsorbed O2, and ascorbic acid. Cytosine nucleobases are shown to alter the adhesion of the DNA to SWCNTs through direct protonation from solution, decreasing the driving force for this phase transition. We show that the phase transition also changes the observed SWCNT corona phase, modulating the recognition of riboflavin. These results provide insight into the unique molecular interactions between DNA and the SWCNT surface, and have implications for molecular sensing, assembly, and nanoparticle separations.

Magnetic Sponge with Neutral-Ionic Phase Transitions.

Phase transitions caused by the charge instability between the neutral and ionic phases of compounds, i.e., N–I phase transitions, provide avenues for switching the intrinsic properties of compounds related to electron/spin correlation and dipole generation as well as charge distribution. However, it is extremely difficult to control the transition temperature (T c) for the N–I phase transition, and only chemical modification based on the original material have been investigated. Here, a design overview of the tuning of N–I phase transition by interstitial guest molecules is presented. This study reports a new chain coordination‐polymer [Ru2(3,4‐Cl2PhCO2)4TCNQ(EtO)2]∙DCE (1‐DCE; 3,4‐Cl2PhCO2 − = 3,4‐dichlorobenzoate; TCNQ(EtO)2 2,5‐diethoxy‐7,7,8,8‐tetracyanoquinodimethane; and DCE = 1,2‐dichloroethane) that exhibits a one‐step N–I transition at 230 K (= T c) with the N‐ and I‐states possessing a simple paramagnetic state and a ferrimagnetically correlated state for the high‐ and low‐temperature phases, respectively. The T c continuously decreases depending on the content of DCE, which eventually disappears with the complete evacuation of DCE, affording solvent‐free compound 1 with the N‐state in the entire temperature range (this behavior is reversible). This is an example of tuning the in situ T c for the N–I phase transition via the control of the interstitial guest molecules.

Ionic Strength-Mediated Phase Transitions of Surface-Adsorbed DNA on Single-Walled Carbon Nanotubes.

Single-stranded DNA oligonucleotides have unique, and in some cases sequence-specific molecular interactions with the surface of carbon nanotubes that remain the subject of fundamental study. In this work, we observe and analyze a generic, ionic strength-mediated phase transition exhibited by over 25 distinct oligonucleotides adsorbed to single-walled carbon nanotubes (SWCNTs) in colloidal suspension. The phase transition occurs as monovalent salts are used to modify the ionic strength from 500 mM to 1 mM, causing a reversible reduction in the fluorescence quantum yield by as much as 90%. The phase transition is only observable by fluorescence quenching within a window of pH and in the presence of dissolved O2, but occurs independently of this optical quenching. The negatively charged phosphate backbone increases (decreases) the DNA surface coverage on an areal basis at high (low) ionic strength, and is well described by a two-state equilibrium model. The resulting quantitative model is able to describe and link, for the first time, the observed changes in optical properties of DNA-wrapped SWCNTs with ionic strength, pH, adsorbed O2, and ascorbic acid. Cytosine nucleobases are shown to alter the adhesion of the DNA to SWCNTs through direct protonation from solution, decreasing the driving force for this phase transition. We show that the phase transition also changes the observed SWCNT corona phase, modulating the recognition of riboflavin. These results provide insight into the unique molecular interactions between DNA and the SWCNT surface, and have implications for molecular sensing, assembly, and nanoparticle separations.

Ionic and superionic phases in ammonia dihydrate NH3·2H2O under high pressure

Water and ammonia have long been seen as the main species of extraterrestrial space, especially on solar giants, moons, comets, and numerous extrasolar planets. The phases formed by their admixtures under temperature and pressure conditions of the giant planets are important for understanding many observable properties (gravitational moments, atmospheric composition, and magnetic field). Here we employ a Monte Carlo packing algorithm combined with first-principles calculations to search the low-energy crystal structures of ammonia dihydrate (ADH). At high pressure above 11.81 GPa, we predict an unusual ionic phase (tetragonal, $I{4}_{1}cd)$ consisting of three alternating layers of ${\mathrm{H}}_{2}\mathrm{O},{\mathrm{NH}}_{4}{}^{+}$, and $\mathrm{O}{\mathrm{H}}^{\ensuremath{-}}$. The occurrence of ionic phase is attributed to the ${\mathrm{NH}}_{4}{}^{+}$ and $\mathrm{O}{\mathrm{H}}^{\ensuremath{-}}$ electrostatic interaction induced volume reduction, which lowers the energy barrier of molecular to ionic phase transition. Analysis of proton transfer under pressure further supports the transformation mechanism between molecular and ionic phase. According to the mobility of hydrogen atoms from ab initio molecular dynamics, this ionic crystal will transform into a superionic phase under high temperature and high pressure. The existence of ionic or superionic ADH may have important implications for understanding the interiors of Neptune, Uranus, and many extrasolar planets.

Ionic Mobility and Phase Transitions in Perovskite Oxides for Energy Application

Perovskite oxides find applications or are studied in many fields related to energy production, accumulation and saving. The most obvious application is oxygen or proton conductors in fuel cells (SOFCs), but the (anti)ferroelectric compositions may find application in high energy capacitors for energy storage, efficient electrocaloric cooling, and electromechanical energy harvesting. In SOFCs, the diffusion of O vacancies and other mobile ionic species, such as H+, are at the base of the functioning of the device, while in the other cases they constitute unwanted defects that reduce the performance and life-time of the device. Similarly, the (anti)ferroelectric phase transitions are a requisite for the use of some types of devices, but the accompanying domain walls can generate extended defects detrimental to the life of the material, and structural phase transformations should be avoided in SOFCs. All these phenomena can be studied by mechanical spectroscopy, the measurement of the complex elastic compliance as a function of temperature and frequency, which is the mechanical analogue of the dielectric susceptibility, but probes the elastic response and elastic dipoles instead of the dielectric response and electric dipoles. The two techniques can be combined to provide a comprehensive picture of the material properties. Examples are shown of the study of structural transitions and hopping and tunnelling processes of O vacancies and H in the ion conductor BaCe1-xYxO3-x and in SrTiO3-x, and of the aging and fatigue effects found in PZT at compositions where the ferro- and antiferroelectric states coexist.

Thiophosphates Containing Ag+ and Lone-Pair Cations with Interchiral Double Helix Show Both Ionic Conductivity and Phase Transition.

Quaternary metal thiophosphates containing second-order Jahn-Teller distorted d10 Ag+ and lone-pair cations, Ag3Bi(PS4)2 (1), Ag7Sn(PS4)3 (2), and Ag7Pb(PS4)3 (3), were obtained by solid-state synthesis. The structural frameworks of 2 and 3 feature an infinite 1-D interchiral double helix ∞1(Ag3P2S11), which is rare in inorganic compounds. Compound 3 undergoes a significant first-order structural phase transition from monoclinic to hexagonal at ∼204 °C. This can be ascribed to the significant mismatch in the expansion coefficients between Pb-S (Ag-S) and P-S bonds evaluated by bond valence theory. The three compounds are Ag+ ionic conductors, and Ag+ ion migration pathways are proposed by calculating maps of low bond valence mismatch. Moreover, the optical properties of the three compounds were studied, and electronic structure calculations were performed. The combination of second-order Jahn-Teller distorted d10 cation and lone-pair cation provides a new strategy to explore new metal thiophosphates with interesting structures and promising properties.

Study on dechlorination kinetics from zinc oxide dust by clean metallurgy technology

Abstract Cavity perturbation method was used to determine the dielectric properties (ε′, ε″, and tan δ) of zinc oxide dust. The process of dechlorination from zinc oxide dust by microwave roasting was evaluated considering the effect of different roasting temperatures and holding times. The research results showed that the ZnCl2 and PbCl2 with high-loss factor were heated preferentially by microwave, and the dechlorination rate can reach 97.22% after microwave roasting at 650°C for 40 min. The phases of zinc oxide dust before and after microwave roasting were observed and characterized by X-ray diffraction (XRD) analysis. The kinetics of dechlorination from zinc oxide dust was investigated. The three kinetic factors were obtained by the dynamic isothermal method, which provided a theoretical basis for dechlorination from zinc oxide dust. Thermodynamic analysis showed that the volatilization of chlorides was mainly ionic crystal phase transition process. The volatile kinetics of zinc oxide dust were controlled by the solid state diffusion and interface chemical reaction, during the microwave heating, with an activation energy E=46.6 KJ/mol and the reaction order n is level 1.

Novel approach in determination of ionic conductivity and phase transition temperatures in gel electrolytes based on Low Molecular Weight Gelators

The performance of a method for ionic conductivity measurements in physical gels with use of thermal scanning approach is investigated. It has been shown that this new experimental protocol has several advantages over conventional conductometry with temperature stabilization of the sample. Improved sensitivity of “ongoing” changes, in situ observations of the gel phase and measurements during gelation stage showed interesting features in conductivity and temperature dependences undetectable in conventional conductometry. The comparison of the results for both methods showed very good agreement concerning global features and additional important detail accessible only by the new proposed here method. Ultimately, the method can be used for characterization of the conductivity properties of the system in the gel phase as well as during gelation process, together with detection and validation of the gel-to-sol phase transition temperatures.

Quantum ferroelectricity in charge-transfer complex crystals.

Quantum phase transition achieved by fine tuning the continuous phase transition down to zero kelvin is a challenge for solid state science. Critical phenomena distinct from the effects of thermal fluctuations can materialize when the electronic, structural or magnetic long-range order is perturbed by quantum fluctuations between degenerate ground states. Here we have developed chemically pure tetrahalo-p-benzoquinones of n iodine and 4–n bromine substituents (QBr4–nIn, n=0–4) to search for ferroelectric charge-transfer complexes with tetrathiafulvalene (TTF). Among them, TTF–QBr2I2 exhibits a ferroelectric neutral–ionic phase transition, which is continuously controlled over a wide temperature range from near-zero kelvin to room temperature under hydrostatic pressure. Quantum critical behaviour is accompanied by a much larger permittivity than those of other neutral–ionic transition compounds, such as well-known ferroelectric complex of TTF–QCl4 and quantum antiferroelectric of dimethyl–TTF–QBr4. By contrast, TTF–QBr3I complex, another member of this compound family, shows complete suppression of the ferroelectric spin-Peierls-type phase transition.

Structural phase transitions and conducting properties in Bimetallic sulfates

Bimetallic sulfate minerals, hydrated as well as anhydrous are important multifunctional materials which exhibit interesting properties like fast-ion conduction, ferroelectricity and magnetism with variation in temperature [1,2,3]. These properties are generally entwined with structural phase transitions and show structural frameworks made of interconnection of octahedra and tetrahedra [1]. Bimetallic sulfates, indeed are intercalation compounds of alkali ions generated by these frameworks and they possess high ionic conductivity [1]. In the present study, anhydrous and hydrous compounds of Na6M(SO4)4, (M=Mn, Ni, Co) were synthesized to understand the structural phase transitions and its relation to fast-ion conducting properties. Na6Mn(SO4)4, is monoclinic, space group P21/c with Z=2 and is isostructural to its Co and Ni analogues and shows high ionic conductivity and structural phase transition &gt; 4500C. Na6Co(SO4).2H2O, Na6Ni(SO4).2H2O are isostructural with triclinic system having space group P-1 with Z =1. In addition, structural features and correlation with ionic conductivity in Na6Co(SO4).2H2O, Na6Ni(SO4).2H2O and Na6Mn(SO4) will be outlined. These studies open up the utility of hydrated bimetallic sulfates as possible precursor for the design of functional materials.