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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Unique dynamic crossover in supercooled x,3-dihydroxypropyl acrylate (x = 1, 2) isomers mixture.

The previtreous dynamics in the glass-forming monomer, glycerol monoacrylate (GMA), was tested using the broadband dielectric spectroscopy (BDS). The measurements revealed a clear dynamic crossover at the temperature [Formula: see text] K and the time scale [Formula: see text] ns for the primary (structural) relaxation time and no hallmarks for the crossover for the DC electric conductivity [Formula: see text]. This result was revealed via the derivative-based and distortions-sensitive analysis [Formula: see text] vs. [Formula: see text] , where [Formula: see text] stands for the apparent activation energy. Subsequent tests of the fractional Debye-Stokes-Einsten relation [Formula: see text] showed that the crossover is associated with [Formula: see text] [Formula: see text] (for [Formula: see text]. The crossover coexists with the emergence of the secondary beta relaxation, which smoothly develops deeply into the solid amorphous phase below the glass temperature [Formula: see text].

The super- and sub-critical effects for dielectric constant in diethyl ether.

Results of dielectric constant (ε) studies in diethyl ether for the surrounding of the gas - liquid critical point, TC - 130 K < T < TC + 50 K, are presented. The analysis recalls the physics of critical phenomena for portraying ε (T) evolution along branches of the coexistence curve, along its diameter (d(T)) and in the supercritical domain for T > TC. For the ultrasound sonicated system, the split into coexisting phases disappeared and dielectric constant approximately followed the pattern of the diameter. This may indicate the possibility of the extension of the "supercritical technology" into the ultrasound "homogenized" subcritical domain: the "strength" and the range of the precritical effect of d(T) are ca. 10× larger than for ε (T > TC).

Nonlinear dielectric effect in supercritical diethyl ether.

Nonlinear dielectric effect (NDE) describes changes of dielectric permittivity induced by a strong electric field in a liquid dielectric. The most classical finding related to this magnitude is the negative sign of NDE in liquid diethyl ether (DEE), recalled by Peter Debye in his Nobel Prize lecture. This article shows that the positive sign of NDE in DEE is also possible, in the supercritical domain. Moreover, NDE on approaching the gas-liquid critical point exhibits a unique critical effect described by the critical exponent ψ ≈ 0.4 close to critical temperature (T(C)) and ψ ≈ 0.6 remote from T(C). This can be linked to the emergence of the mean-field behavior in the immediate vicinity of T(C), contrary to the typical pattern observed for critical phenomena. The multi-frequency mode of NDE measurements made it possible to estimate the evolution of lifetime of critical fluctuations. The new way of data analysis made it possible to describe the critical effect without a knowledge of the non-critical background contribution in prior.

Global population: from Super-Malthus behavior to Doomsday criticality.

The report discusses global population changes from the Holocene beginning to 2023, via two Super Malthus (SM) scaling equations. SM-1 is the empowered exponential dependence: P t = P 0 e x p ± t / τ ß , and SM-2 is the Malthus-type relation with the time-dependent growth rate r ( t ) or relaxation time τ ( t ) = 1 / r ( t ) : P t = P 0 e x p r t × t = P 0 e x p τ t / t . Population data from a few sources were numerically filtered to obtain a 'smooth' dataset, allowing the distortions-sensitive and derivative-based analysis. The test recalling SM-1 equation revealed the essential transition near the year 1970 (population: ~ 3 billion): from the compressed exponential behavior ( ß > 1 ) to the stretched exponential one ( ß < 1 ). For SM-2 dependence, linear changes of τ T during the Industrial Revolutions period, since ~ 1700, led to the constrained critical behavior P t = P 0 e x p b ' t / T C - t , where T C ≈ 2216 is the extrapolated year of the infinite population. The link to the 'hyperbolic' von Foerster Doomsday equation is shown. Results are discussed in the context of complex systems physics, the Weibull distribution in extreme value theory, and significant historic and prehistoric issues revealed by the distortions-sensitive analysis.

Food Preservation in the Industrial Revolution Epoch: Innovative High Pressure Processing (HPP, HPT) for the 21st-Century Sustainable Society.

The paper presents the 'progressive review' for high pressure preservation/processing (HPP) (cold pasteurization) of foods and the next-generation high-pressure and high temperature (HPHT, HPT) food sterilization technologies. It recalls the basics of HPP and HPT, showing their key features and advantages. It does not repeat detailed results regarding HPP and HPT implementations for specific foods, available in numerous excellent review papers. This report focuses on HPP and HPT-related issues that remain challenging and can hinder further progress. For HPP implementations, the reliable modeling of microorganisms' number decay after different times of high pressure treatment or product storage is essential. This report indicates significant problems with model equations standard nonlinear fitting paradigm and introduces the distortion-sensitive routine enabling the ultimate validation. An innovative concept based on the barocaloric effect is proposed for the new generation of HPT technology. The required high temperature appears only for a strictly defined short time period controlled by the maximal pressure value. Results of the feasibility test using neopentyl glycol as the barocaloric medium are presented. Attention is also paid to feedback interactions between socioeconomic and technological issues in the ongoing Industrial Revolution epoch. It indicates economic constraints for HPP and HPT developments and emerging business possibilities. The discussion recalls the inherent feedback interactions between technological and socioeconomic innovations as the driving force for the Industrial Revolution epoch.

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 Model Insight into Broadband Dielectric Properties of Neopentyl Glycol (NPG).

This report presents the low-frequency (LF), static, and dynamic dielectric properties of neopentyl glycol (NPG), an orientationally disordered crystal (ODIC)-forming material important for the barocaloric effect applications. High-resolution tests were carried out for 173K

Are Critical Fluctuations Responsible for Glass Formation?

The dynamic heterogeneities occurring just before the transition to the glassy phase have been named as the cause of amorphization in supercooled systems. Numerous studies conducted so far have confirmed this hypothesis, and based on it, a widely accepted solution to the puzzle of glass transition has been developed. This report focuses on verifying the existence of a strong pretransitional anomaly near the glass transition Tg. For this purpose, supercooled liquid-crystalline systems with a strong rod-like structure were selected. Based on the obtained experimental data, we demonstrate in this article that the previously postulated dynamic heterogeneities exhibit a critical characteristic, meaning a strong pretransitional anomaly can be observed with the described critical exponent α=0.5. Due to this property, it can be concluded that these heterogeneities are critical fluctuations, and consequently, the transition to the glassy state can be described based on the theory of critical phenomena. To measure the pretransitional anomaly near Tg in supercooled liquid-crystalline systems, broadband dielectric spectroscopy (BDS) and nonlinear dielectric effect (NDE) methods were applied. The exponent α provides insight into the nature and intensity of critical fluctuations in the system. A value of α=0.5 suggests that the fluctuations become increasingly intense as the system approaches the critical point, contributing to the divergence in specific heat. Understanding the role of critical fluctuations in the glass transition is crucial for innovating and improving a wide range of materials for energy storage, materials design, biomedical applications, food preservation, and environmental sustainability. These advancements can lead to materials with superior properties, optimized manufacturing processes, and applications that meet the demands of modern technology and sustainability challenges.

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.

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.