The Dominance of Pretransitional Effects in Liquid Crystal-Based Nanocolloids: Nematogenic 4-methoxybenzylidene-4'-butylaniline with Transverse Permanent Dipole Moment and BaTiO3 Nanoparticles.

The report presents static, low-frequency, and dynamic dielectric properties in the isotropic liquid, nematic, and solid phases of MBBA and related nanocolloids with paraelectric BaTiO3 nanoparticles (spherical, d = 50 nm). MBBA (4-methoxybenzylidene-4'-butylaniline) is a liquid crystalline compound with a permanent dipole moment transverse to the long molecular axis. The distortions-sensitive analysis of the dielectric constant revealed its hidden pretransitional anomaly, strongly influenced by the addition of nanoparticles. The evolution of the dielectric constant in the nematic phase shows the split into two regions, with the crossover coinciding with the standard melting temperature. The 'universal' exponential-type behavior of the low-frequency contribution to the real part of the dielectric permittivity is found. The critical-like pretransitional behavior in the solid phase is also evidenced. This is explained by linking the Lipovsky model to the Mossotti catastrophe concept under quasi-negative pressure conditions. The explicit preference for the 'critical-like' evolution of the apparent activation enthalpy is worth stressing for dynamics. Finally, the long-range, 'critical-like' behavior of the dissipation factor (D = tgδ), covering the isotropic liquid and nematic phases, is shown.

Critical Insight into Pretransitional Behavior and Dielectric Tunability of Relaxor Ceramics.

This model discussion focuses on links between the unique properties of relaxor ceramics and the basics of Critical Phenomena Physics and Glass Transition Physics. It indicates the significance of uniaxiality for the appearance of mean-field type features near the paraelectric-to-ferroelectric phase transition. Pretransitional fluctuations, that are increasing up to the size of a grain and leading to inter-grain, random, local electric fields are responsible for relaxor ceramics characteristics. Their impact yields the pseudospinodal behavior associated with "weakly discontinuous" local phase transitions. The emerging model redefines the meaning of the Burns temperature and polar nanoregions (PNRs). It offers a coherent explanation of "dielectric constant" changes with the "diffused maximum" near the paraelectric-to-ferroelectric transition, the sensitivity to moderate electric fields (tunability), and the "glassy" dynamics. These considerations are challenged by the experimental results of complex dielectric permittivity studies in a Ba0.65Sr0.35TiO3 relaxor ceramic, covering ca. 250 K, from the paraelectric to the "deep" ferroelectric phase. The distortion-sensitive and derivative-based analysis in the paraelectric phase and the surrounding paraelectric-to-ferroelectric transition reveal a preference for the exponential scaling pattern for ε(T) changes. This may suggest that Griffith-phase behavior is associated with mean-field criticality disturbed by random local impacts. The preference for the universalistic "critical & activated" evolution of the primary relaxation time is shown for dynamics. The discussion is supplemented by a coupled energy loss analysis. The electric field-related tunability studies lead to scaling relationships describing their temperature changes.

Phase Equilibria and Critical Behavior in Nematogenic MBBA-Isooctane Monotectic-Type Mixtures.

The transition from the isotropic (I) liquid to the nematic-type (N) uniaxial phase appearing as the consequence of the elongated geometry of elements seems to be a universal phenomenon for many types of suspensions, from solid nano-rods to biological particles based colloids. Rod-like thermotropic nematogenic liquid crystalline (LC) compounds and their mixtures with a molecular solvent (Sol) can be a significant reference for this category, enabling insights into universal features. The report presents studies in 4'-methoxybenzylidene-4-n-butylaniline (MBBA) and isooctane (Sol) mixtures, for which the monotectic-type phase diagram was found. There are two biphasic regions (i) for the low (TP1, isotropic liquid-nematic coexistence), and (ii) high (TP2, liquid-liquid coexistence) concentrations of isooctane. For both domains, biphasic coexistence curves' have been discussed and parameterized. For TP2 it is related to the order parameter and diameter tests. Notable is the anomalous mean-field type behavior near the critical consolute temperature. Regarding the isotropic liquid phase, critical opalescence has been detected above both biphasic regions. For TP2 it starts ca. 20 K above the critical consolute temperature. The nature of pretransitional fluctuations in the isotropic liquid phase was tested via nonlinear dielectric effect (NDE) measurements. It is classic (mean-field) above TP1 and non-classic above the TP2 domain. The long-standing problem regarding the non-critical background effect was solved to reach this result.

New insight into 3-picoline-deuterium oxide (D2O) mixtures of limited miscibility with the lower critical consolute temperature.

Coexistence curves in mixtures of limited miscibility with the lower critical consolute temperature (LCT), of 3-picoline with deuterium oxide (D2O), and D2O/H2O have been determined. They were tested with respect to the order parameter, the diameter of the binodal, and coordinates of the critical consolute point (critical temperature [Formula: see text] and critical concentration [Formula: see text]). Studies were carried out using the innovative method based on the analysis of relative volumes occupied by coexisting phases, yielding high-resolution data. The clear violation of the Cailletet-Mathew law of rectilinear diameter for the LCT mixtures of limited miscibility is evidenced. For the order parameter, the new distortion-sensitive analysis method yielded the evidence for the model-value of the order parameter critical exponent [Formula: see text], up to ca. 1 K from [Formula: see text]. Finally, the simple & easy method for determining the critical concentration by testing relative volumes of coexisting phases (or alternatively fractional meniscus heights, h) is presented. The significance of the invariant value [Formula: see text] is highlighted. The appearance of the milky & bluish critical opalescence is also shown.

The impact of ionic contribution to dielectric permittivity in 11CB liquid crystal and its colloids with BaTiO3 nanoparticles.

The report shows the temperature behavior of the real part of dielectric permittivity in the static (dielectric constant) and low-frequency (LF) domains in bulk samples of 11CB and its BaTiO3-based nanocolloids. The study covers the isotropic liquid (I), nematic (N), smectic A (SmA), and solid crystal (Cr) phases. For each phase, the dominance of pretransitional fluctuations, significantly moderated by nanoparticles, is shown. The authors consider separate focuses on the dielectric constant [Formula: see text] evolution in the static domain, yielding mainly response from permanent dipole moment and its arrangement, and in the low-frequency (LF) domain [Formula: see text] (where [Formula: see text] is for the real part of dielectric permittivity in the LF domain), which is associated solely with ionic-related polarization mechanisms. All of these led to new experimental evidence concerning I-N, N-SmA, and SmA-solid transitions, focusing on the strength and extent of pretransitional effects, critical exponents, and phase transitions discontinuities. The strong evidence for pretransitional effects near the SmA-Cr transition is notable, particularly regarding [Formula: see text]. Studies are supplemented by the discussion of DC electric conductivity-a parameter also related to the LF domain. Finally, the validity of the relation [Formula: see text] (where f stands for frequency, and A is a constant parameter), often used for discussing dielectric spectra in LC compound and its nanocolloids in the LF domain, is examined.

Pretransitional of behavior of electrooptic Kerr effect in liquid thymol.

Melting/freezing are canonical examples of discontinuous phase transitions, for which no pretransitional effects in the liquid phase are expected. For the solid phase, weak premelting effects are evidenced. This report shows long-range, critical-like, pretransitional effects in liquid thymol detected in electrooptic Kerr effect (EKE) studies. Notably is the negative sign of EKE pretransitional anomaly. Studies are supplemented by the high-resolution dielectric constant temperature-related scan, which revealed a weak premelting effect in the solid phase. Both EKE and dielectric constant show a 'crossover' change in the liquid phase, ca, 10 K above the freezing temperature. It can be recognized as the hallmark of the challenging liquid-liquid transition phenomenon.

Pressure Evolution of Glass Transition Temperature in LiFePO4.

LiFePO4 is an important base material for generation of new batteries. One of the important developments is its use in the form of a solid glass, which allows an increase in the electrical conductivity after the high-pressure process. Such a treatment allows full control of the vitrification and nanocrystallization processes as well. This report shows the basic reference for the pressure dependence of the glass transition temperature. The unique behavior has been proven with a maximum of Tg (P) already at moderate pressures. The protocol for depicting the resulting evolution is as follows: it enables a reliable extrapolation beyond the experimental domain. The importance of the presented results for the general topic of glass transition physics is also remarkable due to the scant evidence of the existence of systems with clearly inverted vitrification under compression.

History-dependent phase transition character.

We consider history-dependent behavior in domain-type configurations in orientational order that are formed in configurations reached via continuous symmetry-breaking phase transitions. In equilibrium, these systems exhibit in absence of impurities a spatially homogeneous order. We focus on cases where domains are formed via (i) Kibble-Zurek mechanism in fast enough quenches or by (ii) Kibble mechanism in strongly supercooled phases. In both cases, domains could be arrested due to pinned topological defects that are formed at domain walls. In systems exhibiting polar or quadrupolar order, point and line defects (disclinations) dominate, respectively. In particular, the disclinations could form complex entangled structures and are more efficient in stabilizing domains. Domain patterns formed by fast quenches could be arrested by impurities imposing a strong enough random-field type disorder, as suggested by the Imry-Ma theorem. On the other hand, domains formed in supercooled systems could be also formed if large enough energy barriers arresting domains are established due to large enough systems' stiffness. The resulting effective interactions in established domain-type patterns could be described by random matrices. The resulting eigenvectors reveal expected structural excitations formed in such structures. The most important role is commonly played by the random matrix largest eigenvector. Qualitatively different behavior is expected if this eigenvector exhibits a localized or extended character. In the former case, one expects a gradual, non-critical-type transition into a glass-type structure. However, in the latter case, a critical-like phase behavior could be observed.

Criticality-related fundamental bases for new generations of gas-liquid, liquid-liquid, and liquid (LE) extraction technologies.

The report presents experimental results, which can be considered as the reference for innovative generations of supercritical fluids (SCF), liquid-liquid (LL), and liquid (L) extraction technologies. They are related to implementations of Critical Phenomena Physics, for such applications not considered so far. For the gas-liquid critical point, the shift SuperCritical Fluids (SCF) ⇒ SubCritical Fluids, due to the additional exogenic impact of ultrasounds, is indicated. For LL technology, the possibility of increasing process effectiveness when operating near the critical consolute under pressure is indicated. Finally, the discovery of long-range precritical-type changes of dielectric constant in linseed oil, standing even 50 K above the melting temperature, is presented. It suggests that extraction processes linking 'SCF' and 'L' technologies features and exploring the natural carrier, such as linseed oil, are possible. The report recalls the fundamental base for extraction processes via Kirkwood and Noyes-Whitney relations and presents their implementations to 'critical conditions,' including pressure.

The fluctuation-driven dielectric properties of liquid crystalline 8OCB and its nanocolloids.

Results of broadband dielectric spectroscopy studies in liquid crystalline octyloxycyanobiphenyl (8OCB) and its colloids with BaTiO3 nanoparticles (paraelectric, diameter d = 50 nm) are presented. Studies were carried out in isotropic liquid, nematic, smectic A and solid crystalline phases. They are supported by derivative-based and distortion-sensitive analyses, revealing a set of universal scaling patterns for temperature evolution of static and dynamic dielectric properties. All these yielded evidence for a pretransitional fluctuation impact on the dielectric constant, primary relaxation time, loss curve maximum and translational-orientational decoupling associated with anomalous values of the fractional Debye-Stokes-Einstein (DSE) exponent 0.2 < S < 2.2. The evidence for critical like changes in a distribution of relaxation times is shown. For mesophases, a tiny addition of nanoparticles causes permanent orientation of LC molecules, leading even to a 16% increase of the dielectric constant above a maximal value in pure 8OCB. A split of two regions, dominated by pre-isotropic and pre-smectic fluctuations, is evidenced. Model explanations for detected phenomena, particularly in the isotropic liquid phase, are presented. New evidence for a premelting effect in the solid phase is also shown.

New paradigm for configurational entropy in glass-forming systems.

We show that on cooling towards glass transition configurational entropy exhibits more significant changes than predicted by classic relation. A universal formula according to Kauzmann temperature [Formula: see text] is given: [Formula: see text], where [Formula: see text]. The exponent [Formula: see text] is hypothetically linked to dominated local symmetry. Such a behaviour is coupled to previtreous evolution of heat capacity [Formula: see text] associated with finite temperature singularity. These lead to generalised VFT relation, for which the basic equation is retrieved. For many glass-formers, basic VFT equation may have only an effective meaning. A universal-like reliability of the Stickel operator analysis for detecting dynamic crossover phenomenon is also questioned. Notably, distortions-sensitive and derivative-based analysis focused on previtreous changes of configurational entropy and heat capacity for glycerol, ethanol and liquid crystal is applied.

Novel High-Pressure Nanocomposites for Cathode Materials in Sodium Batteries.

A new nanocomposite material was prepared by high pressure processing of starting glass of nominal composition NaFePO4. Thermal, structural, electrical and dielectric properties of the prepared samples were studied by differential thermal analysis (DTA), X-ray diffraction (XRD) and broadband dielectric spectroscopy (BDS). It was demonstrated that high-pressure-high-temperature treatment (HPHT) led to an increase in the electrical conductivity of the initial glasses by two orders of magnitude. It was also shown that the observed effect was stronger than for the lithium analogue of this material studied by us earlier. The observed enhancement of conductivity was explained by Mott's theory of electron hopping, which is more frequent in samples after pressure treatment. The final composite consisted of nanocrystalline NASICON (sodium (Na) Super Ionic CONductor) and alluaudite phases, which are electrochemically active in potential cathode materials for Na batteries. Average dimensions of crystallites estimated from XRD studies were between 40 and 90 nm, depending on the phase. Some new aspects of local dielectric relaxations in studied materials were also discussed. It was shown that a combination of high pressures and BDS method is a powerful method to study relaxation processes and molecular movements in solids. It was also pointed out that high-pressure cathode materials may exhibit higher volumetric capacities compared with commercially used cathodes with carbon additions.

Long-Range Static and Dynamic Previtreous Effects in Supercooled Squalene-Impact of Strong Electric Field.

This article presents evidence for the long-range previtreous changes of two static properties: the dielectric constant (ε) and its strong electric field related counterpart, the nonlinear dielectric effect (NDE). Important evidence is provided for the functional characterizations of ε(T) temperature changes by the 'Mossotti Catastrophe' formula, as well as for the NDE vs. T evolution by the relations resembling those developed for critical liquids. The analysis of the dynamic properties, based on the activation energy index, excluded the Vogel-Fulcher-Tammann (VFT) relation as a validated tool for portraying the evolution of the primary relaxation time. This result questions the commonly applied 'Stickel operator' routine as the most reliable tool for determining the dynamic crossover temperature. In particular, the strong electric field radically affects the distribution of the relaxation times, the form of the evolution of the primary relaxation time, and the fragility. The results obtained in this paper support the concept of a possible semi-continuous phase transition hidden below Tg. The studies were carried out in supercooled squalene, a material with an extremely low electric conductivity, a strongly elongated molecule, and which is vitally important for biology and medicine related issues.

Indentation Response of Calcium Aluminoborosilicate Glasses Subjected to Humid Aging and Hot Compression.

Aluminoborosilicate glasses find a wide range of applications, which require good mechanical reliability such as surface damage resistance. Calcium aluminoborosilicate (CABS) glasses have recently been found to exhibit so-called intermediate behavior in terms of their response to sharp contact loading. That is, these glasses deform with less shear than normal glass and less densification than anomalous glasses. This deformation mechanism is believed to give rise to high crack initiation resistance of certain CABS glasses. In order to further improve and understand the micromechanical properties of this glass family, we studied the indentation response of different CABS glasses subjected to two types of post-treatment, namely hot compression and humid aging. Upon hot compression, density, elastic moduli, and hardness increased. Specifically, elastic modulus increased by as much as 20% relative to the as-made sample, while the largest change in hardness was 1.8 GPa compared to the as-made sample after hot compression. The pressure-induced increase in these properties can be ascribed to the increase in network connectivity and bond density. On the other hand, the crack initiation resistance decreased, as the hot compression increased the residual stress driving the indentation cracking. Humid aging had only a minor impact on density, modulus, and hardness, but an observed decrease in crack initiation resistance. We discuss the correlations between hardness, density, crack resistance, and deformation mechanism and our study thus provides guidelines for tailoring the mechanical properties of oxide glasses.

Pretransitional Effects of the Isotropic Liquid-Plastic Crystal Transition.

We report on strong pretransitional effects across the isotropic liquid-plastic crystal melting temperature in linear and nonlinear dielectric response. Studies were carried out for cyclooctanol (C8H16O) in the unprecedented range of temperatures 120 K < T < 345 K. Such pretransitional effects have not yet been reported in any plastic crystals. Results include the discovery of the experimental manifestation of the Mossotti Catastrophe behavior, so far considered only as a hypothetical paradox. The model interpretations of experimental findings are proposed. We compare the observed pretransitional behavior with the one observed in octyloxycyanobiphenyl (8OCB), typical liquid crystal (LC), displaying a reversed sequence of phase transitions in orientational and translational degrees of order on varying temperature. Furthermore, in its nematic phase, we demonstrate first-ever observed temperature-driven crossover between regions dominated by isotropic liquid and smectic A pretransitional fluctuations. We propose a pioneering minimal model describing plastic crystal phase behavior where we mimic derivation of classical Landau-de Gennes-Ginzburg modeling of Isotropic-Nematic-Smectic A LC phase behavior.

Dynamics and Pretransitional Effects in C60 Fullerene Nanoparticles and Liquid Crystalline Dodecylcyanobiphenyl (12CB) Hybrid System.

The report shows the strong impact of fullerene C60 nanoparticles on phase transitions and complex dynamics of rod-like liquid crystal dodecylcyanobiphenyl (12CB), within the limit of small concentrations. Studies were carried out using broadband dielectric spectroscopy (BDS) via the analysis of temperature dependences of the dielectric constant, the maximum of the primary loss curve, and relaxation times. They revealed a strong impact of nanoparticles, leading to a ~20% change of dielectric constant even at x = 0.05% of C60 fullerene. The application of the derivative-based and distortion-sensitive analysis showed that pretransitional effects dominate in the isotropic liquid phase up to 65 K above the clearing temperature and in the whole Smectic A mesophase. The impact of nanoparticles on the pretransitional anomaly appearance is notable for the smectic-solid phase transition. The fragility-based analysis of relaxation times revealed the universal pattern of its temperature changes, associated with scaling via the "mixed" ("activated" and "critical") relation. Phase behavior and dynamics of tested systems are discussed within the extended Landau-de Gennes-Ginzburg mesoscopic approach.

High-pressure behavior of dielectric constant in a binary critical mixture.

An alternative design of the measurement capacitor for high-pressure studies of complex liquids or soft matter systems is presented. Subsequently, results for the precritical anomaly of dielectric constant in 1-nitropropane-octane critical mixture are reported. First, the pressure dependence of the critical consolute temperature T_{C} up to P=0.55GPa was determined and portrayed using the derivative-based analysis. Second, temperature and pressure evolutions of dielectric constant on approaching the critical consolute point at (T_{C}=304.1K and P_{C}=403MPa) were studied. They revealed that the pretransitional anomaly ɛ(P→P_{C}) is notably more pronounced than for ɛ(T→T_{C}). For both paths, the static domain extends even to as low frequency as f=100Hz, whereas for tests under atmospheric pressure, they require at least f=100kHz. The discussion of the impact of correction-to-scaling terms, including the unique case of the pressure paths, is also presented.

Impact of Pressure on Low-Molecular Weight Near-Critical Mixtures of Limited Miscibility.

Near-critical mixtures of limited miscibility are significant for chemical physics, soft matter physics, and a variety of challenging applications. Their basic properties can be tuned by compressing or a systematic change of one of the components. This report addresses these issues, based on experimental studies in nitro-compound (nitrobenzene, o-nitrotoluene, and 1-nitropropane) and n-alkane (from pentane to eicosane) critical mixtures. Studies reveal new patterns for the evolution of the critical consolute temperature (T C) and concentration (x C, mole fraction) within the tested homologous series: T C(n) ∼ n 2 and x C(n) ∼ n 1/2. They also show two paths of the high-pressure impact: (i) dT C(P)/dP > 0 and overlapping of normalized T C(P) dependences and (ii) the crossover dT C(P)/dP < 0 → dT C(P)/dP > 0 with increasing n-alkane length. The consistent parameterization of all T C(P) dependencies is introduced. Supplementary nonlinear dielectric effect studies indicate a possible molecular origin of the phenomenon. The coexistence curve under high pressure is in the agreement with the isomorphism postulate for critical phenomena but with a surprisingly strong distortion from the Cailletet-Mathias law of the rectilinear diameter. The new and reliable method for estimating the critical concentration and temperature is proposed. It explores the analysis of relative volumes occupied by coexisting phases.

Multifold pressure-induced increase of electric conductivity in LiFe0.75V0.10PO4 glass.

We investigated the impact of high pressure and high-temperature annealing on lithium-vanadium-iron-phosphate (LiFe0.75V0.10PO4) glass materials, proposed for the use in cathodes for high-performance batteries. The treatment was carried out below the glass transition temperature (Tg ≈ 483 °C) at P = 1 GPa pressure, in an argon atmosphere. It led to the multifold electrical conductivity increase. Broadband dielectric spectroscopy (BDS) measurements before and after the process revealed the strong DC-conductivity increase across the whole studied frequency range by two orders of magnitude. The phenomenon is explained using Mott's theory of polaron hopping in disordered solids containing transition metal oxides. The pressure evolution of the glass transition temperature and the crystallisation temperature above Tg is shown.

Polymer matrix ferroelectric composites under pressure: Negative electric capacitance and glassy dynamics.

This report presents the results of high-pressure and broadband dielectric spectroscopy studies in polyvinylidene difluoride (PVDF) and barium strontium titanate (BST) microparticles composites (BST/PVDF). It shows that the Arrhenius behaviour for the temperature-related dynamics under atmospheric pressure is coupled to Super-Arrhenius/Super-Barus isothermal pressure changes of the primary relaxation time. Following these results, an explanation of the unique behaviour of the BST/PVDF composite is proposed. Subsequently, it is shown that when approaching the GPa domain the negative electric capacitance phenomenon occurs.