Liquid-liquid Transition Research Articles

Liquid-liquid phase transition as a basis for novel materials for skin repair and regeneration.

Inorganic materials are of increasing interest not only for bone repair but also for other applications in regenerative medicine. In this study, the combined effects of energy-providing, regeneratively active inorganic polyphosphate (polyP) and also morphogenetically active pearl powder on wound healing were investigated. Aragonite, the mineralic constituent of pearl nacre and thermodynamically unstable form of crystalline calcium carbonate, was found to be converted into a soluble state in the presence of a Ca2+-containing wound exudate, particularly upon addition of sodium polyP (Na-polyP), driven by the transfer of Ca2+ ions from aragonite to polyP, leading to liquid-liquid phase separation to form an aqueous Ca-polyP coacervate. This process is further enhanced in the presence of Ca-polyP nanoparticles (Ca-polyP-NP). Kinetic studies revealed that the coacervation of polyP and nacre aragonite in wound exudate is a very rapid process that results in the formation of a stronger gel with a porous structure compared to polyP alone. Coacervate formation, enabled by phase transition of crystalline aragonite in the presence of Na-polyP/Ca-polyP-NP and wound exudate, could also be demonstrated in a hydroxyethyl cellulose-based hydrogel used for wound treatment. Furthermore, it is shown that Na-polyP/Ca-polyP-NP together with nacre aragonite strongly enhances the proliferation of mesenchymal stem cells and promotes microtube formation in the in vitro angiogenesis assay with HUVEC endothelial cells. The latter effect was confirmed by gene expression studies, applying real-time polymerase chain reaction, using the biomarker genes VEGF (vascular endothelial growth factor) and hypoxia-inducible factor-1 α (HIF-1α). Division of Escherichia coli is suppressed when suspended in a matrix containing Na-polyP/Ca-polyP-NP and aragonite. The potential medical relevance of these findings is supported by an animal study on genetically engineered diabetic mice (db/db), which demonstrated a marked increase in granulation tissue and microvessel formation in regenerating experimental wounds treated with Ca-polyP-NP compared to controls. Co-administration of aragonite significantly accelerated the wound healing-promoting effect of polyP in db/db mice. Based on these results, we propose that the ability of polyP to form a mixed coacervate with aragonite, in addition to its energy (ATP)-generating function, can decisively contribute to the regenerative activity of this polymer in wound repair.

Spiers Memorial Lecture: From cold to hot, the structure and structural dynamics of dense ionic fluids.

The structure of ionic liquids (ILs), which a decade or two ago was the subject of polite but heated debate, is now much better understood. This has opened opportunities to ask more sophisticated questions about the role of structure in transport, the structure of systems with ions that are not prototypical, and the similarity between ILs and other dense ionic fluids such as the high-temperature inorganic molten salts; let alone the fact that new areas of research have emerged that sprung from our collective understanding of the structure of ILs such as the deep eutectic solvents, the polymerized ionic liquids, and the zwitterionic liquids. Yet, our understanding of the structure of prototypical ILs may not be as complete as we think it to be, given that recent experiments appear to show that in some cases there may be more than one liquid phase resulting in liquid-liquid (L-L) phase transitions. This article presents a perspective on what we think are key topics related to the structure and structural dynamics of ILs and to some extent high-temperature molten salts.

Pressure-induced reversal of Peierls-like distortions elicits the polyamorphic transition in GeTe and GeSe

While polymorphism is prevalent in crystalline solids, polyamorphism draws increasing interest in various types of amorphous solids. Recent studies suggested that supercooling of liquid phase-change materials (PCMs) induces Peierls-like distortions in their local structures, underlying their liquid-liquid transitions before vitrification. However, the mechanism of how the vitrified phases undergo a possible polyamorphic transition remains elusive. Here, using high-energy synchrotron X-rays, we can access the precise pair distribution functions under high pressure and provide clear evidence that pressure can reverse the Peierls-like distortions, eliciting a polyamorphic transition in GeTe and GeSe. Combined with simulations based on machine-learned-neural-network potential, our structural analysis reveals a high-pressure state characterized by diminished Peierls-like distortion, greater coherence length, reduced compressibility, and a narrowing bandgap. Our finding underscores the crucial role of Peierls-like distortions in amorphous octahedral systems including PCMs. These distortions can be controlled through pressure and composition, offering potentials for designing properties in PCM-based devices.

Do Ionic Liquids Slow Down in Stages?

High impact recent articles have reported on the existence of a liquid-liquid (L-L) phase transition as a function of both pressure and temperature in ionic liquids (ILs) containing the popular trihexyltetradecylphosphonium cation (P666,14+), sometimes referred to as the "universal liquifier". The work presented here reports on the structural-dynamic pathway from liquid to glass of the most well-studied IL comprising the P666,14+ cation. We present experimental and computational evidence that, on cooling, the path from the room-temperature liquid to the glass state is one of separate structural-dynamic changes. The first stage involves the slowdown of the charge network, while the apolar subcomponent is fully mobile. A second, separate stage entails the slowdown of the apolar domain. Whereas it is possible that these processes may be related to the liquid-liquid and glass transitions, more research is needed to establish this conclusively.

Control of thermodynamic liquid-liquid phase transition in a fragility-tunable glassy model.

We propose a distinguishable-particle glassy model suitable for the molecular dynamics simulation of structural glasses. This model can sensitively tune the kinetic fragility of supercooled liquids in a wide range by simply changing the distribution of particle interactions. In the model liquid, we observe the occurrence of thermodynamic liquid-liquid phase transitions above glass transition. The phase transition is facilitated by lowering fragility. Prior to the liquid-liquid phase transition, our simulations verify the existence of a constant-volume heat capacity maximum varying with fragility. We reveal the characteristics of the equilibrium potential energy landscape in liquids with different fragility. Within the Gaussian excitation model, the liquid-liquid transition as well as the response to fragility is reasonably interpreted in configuration space.

NiTi2, a New Liquid Glass.

Many endothermic liquid-liquid transitions, occurring at a temperature Tn+ above the melting temperature Tm, are related to previous exothermic transitions, occurring at a temperature Tx after glass formation below Tg, with or without attached crystallization and predicted by the nonclassical homogenous nucleation equation. A new thermodynamic phase composed of broken bonds (configurons), driven by percolation thresholds, varying from ~0.145 to Δε, is formed at Tx, with a constant enthalpy up to Tn+. The liquid fraction Δε is a liquid glass up to Tn+. The solid phase contains glass and crystals. Molecular dynamics simulations are used to induce, in NiTi2, a reversible first-order transition by varying the temperature between 300 and 1000 K under a pressure of 1000 GPa. Cooling to 300 K, without applied pressure, shows the liquid glass presence with Δε = 0.22335 as memory effect and Tn+ = 2120 K for Tm = 1257 K.

Supercooled solutions of sodium perchlorate in TIP4P/2005 water: The effect of martian solutes on thermodynamics and structure.

We study the thermodynamic behavior of sodium perchlorate solutions in supercooled water through molecular dynamics numerical simulations. These solutions are of special interest because of the recent experimental results that led to hypothesize the presence of liquid water in perchlorate solutions beneath the Martian soil. We model water using the TIP4P/2005 potential. The results we obtain for solutions with concentrations 1.63 and 15.4 wt% are in agreement with those of a system undergoing a liquid-liquid phase transition where the liquid-liquid critical point shifts to slightly higher temperatures and lower pressures. The structure of the system is also analyzed, and we come to the conclusion that, even at the highest concentration considered, water retains its anomalous behavior.

Evolution of medium-range order and its correlation with magnetic nanodomains in Fe-Dy-B-Nb bulk metallic glasses

Fe-based metallic glasses are promising functional materials for advanced magnetism and sensor fields. Tailoring magnetic performance in amorphous materials requires a thorough knowledge of the correlation between structural disorder and magnetic order, which remains ambiguous. Two practical difficulties remain: the first is directly observing subtle magnetic structural changes on multiple scales, and the second is precisely regulating the various amorphous states. Here we propose a novel approach to tailor the amorphous structure through the liquid-liquid phase transition. In-situ synchrotron diffraction has unraveled a medium-range ordering process dominated by edge-sharing cluster connectivity during the liquid-liquid phase transition. Moreover, nanodomains with topological order have been found to exist in composition with liquid-liquid phase transition, manifesting as hexagonal patterns in small-angle neutron scattering profiles. The liquid-liquid phase transition can induce the nanodomains to be more locally ordered, generating stronger exchange interactions due to the reduced Fe–Fe bond length and the enhanced structural order, leading to the increment of saturation magnetization. Furthermore, the increased local heterogeneity at the medium-range scale enhances the magnetic anisotropy, promoting the permeability response under applied stress and leading to a better stress-impedance effect. These experimental results pave the way to tailor the magnetic structure and performance through the liquid-liquid phase transition.

A topological entanglement model for metastable water undergoing liquid-liquid phase transition

Due to the coexistence of two distinct states, namely low-density liquid (LDL) and high-density liquid (HDL), water exhibits many anomalous properties and has a unique liquid-liquid phase transition (LLPT) behavior. However, the underlying mechanism is not well understood owing to the complex evolution and entanglements of the condensed structures during this LLPT. This study proposes a new topological model to study the LLPTs of LDL and HDL in the metastable water and describe its condensed structures utilizing theoretical models of topological unlink, entanglement and sub-entanglement of the condensed structures. Topological unlinks and topological entangled Hopf links are firstly used to describe the topological characteristics of the LDL and HDL, respectively, where there is no configurational entropy for the LDL owing to its intra-entanglement in a single molecule chain. Moreover, the sub-entanglement model is developed to formulate the inter-entanglement dynamics and describe the inter-molecular interactions between LDL and HDL during the LLPT. This model is then extended using the free-volume theory and Adam-Gibbs model to establish constitutive relationships among volume, density, viscosity, diffusion coefficient, glass transition temperature and hydrodynamic radius for the metastable water. Finally, effectiveness of the proposed model is verified by molecular dynamics (MD) simulations and experimental data of the metastable water reported in literature. The proposed topological entanglement model is expected to provide a topological entanglement model to understand the liquid-liquid phase transitions of the metastable water.

Structure and Dynamics of Hybrid Colloid-Polyelectrolyte Coacervates: Insights from Molecular Simulations.

Electrostatic interactions in polymeric systems are responsible for a wide range of liquid-liquid phase transitions that are of importance for biology and materials science. Such transitions are referred to as complex coacervation, and recent studies have sought to understand the underlying physics and chemistry. Most theoretical and simulation efforts to date have focused on oppositely charged linear polyelectrolytes, which adopt nearly ideal-coil conformations in the condensed phase. However, when one of the coacervate components is a globular protein, a better model of complexation should replace one of the species with a spherical charged particle or colloid. In this work, we perform coarse-grained simulations of colloid-polyelectrolyte coacervation using a spherical model for the colloid. Simulation results indicate that the electroneutral cell of the resulting (hybrid) coacervates consists of a polyelectrolyte layer adsorbed on the colloid. Power laws for the structure and the density of the condensed phase, which are extracted from simulations, are found to be consistent with the adsorption-based scaling theory of hybrid coacervation. The coacervates remain amorphous (disordered) at a moderate colloid charge, Q, while an intra-coacervate colloidal crystal is formed above a certain threshold, at Q > Q*. In the disordered coacervate, if Q is sufficiently low, colloids diffuse as neutral nonsticky nanoparticles in the semidilute polymer solution. For higher Q, adsorption is strong and colloids become effectively sticky. Our findings are relevant for the coacervation of polyelectrolytes with proteins, spherical micelles of ionic surfactants, and solid organic or inorganic nanoparticles.

Improved wear resistance of metallic glacier glass

Metallic glasses (MGs) have garnered significant attention due to their excellent properties, like high wear resistance, making them highly promising for a wide range of engineering applications. However, it is of significance to further increase the wear resistance of MGs, which has rarely been studied. Here we present a remarkable enhancement of wear resistance when some MGs undergo a liquid-liquid transition to form a new metallic glacial glass (MGG) state. Within an identical composition of La65Ni20Al15, the wear resistance of the MGG exhibits a notable superiority of 104% compared to the as-cast MG, and an even more remarkable advantage of 349% compared to its crystalline counterpart. The excellent wear resistance of the MGG is attributed to its ultrastable nature in energy confirmed by dynamic relaxation changes. This work not only offers a unique perspective on MGGs, but also provides an effective technique for developing wear-resistant materials.

Slow solvation dynamics beyond dielectric relaxation by three-pulse photon echo peak shift.

The dynamics of a liquid and its coupling to a solute are crucial for a better understanding of chemical processes in the liquid phase. In isotropic and homogeneous solutions, the time-correlation function of a solute is expected to vanish over time due to the translational and diffusive motions of the solvent. The three-pulse photon echo peak shift (3PEPS) is a third-order nonlinear spectroscopy technique that records the time-correlation function of a solute molecule in a solution, including an offset (inhomogeneity). In this work, we utilized a diffractive optics-based 3PEPS apparatus to fully resolve the dynamics in liquids from femtoseconds to nanoseconds while varying the temperature in the range of 80-298K and the probe solute molecules. Our observations reveal dynamics slower than the dielectric relaxation of n-alcohols, even at room temperature, consisting of a ∼0.5ns time constant that persists below the melting points and a static component (offset) on a nanosecond timescale. Based on the experiments, we suggest that locally formed glass-like clusters in liquids can be responsible for the slow dynamics. Our results may provide new insights into the dynamics of liquids and related phenomena such as liquid-glass and liquid-liquid phase transitions.

Melting curves of ice polymorphs in the vicinity of the liquid-liquid critical point.

The possible existence of a liquid-liquid critical point in deeply supercooled water has been a subject of debate due to the challenges associated with providing definitive experimental evidence. The pioneering work by Mishima and Stanley [Nature 392, 164-168 (1998)] sought to shed light on this problem by studying the melting curves of different ice polymorphs and their metastable continuation in the vicinity of the expected liquid-liquid transition and its associated critical point. Based on the continuous or discontinuous changes in the slope of the melting curves, Mishima [Phys. Rev. Lett. 85, 334 (2000)] suggested that the liquid-liquid critical point lies between the melting curves of ice III and ice V. We explore this conjecture using molecular dynamics simulations with a machine learning model based on abinitio quantum-mechanical calculations. We study the melting curves of ices III, IV, V, VI, and XIII and find that all of them are supercritical and do not intersect the liquid-liquid transition locus. We also find a pronounced, yet continuous, change in the slope of the melting lines upon crossing of the liquid locus of maximum compressibility. Finally, we analyze the literature in light of our findings and conclude that the scenario in which the melting curves are supercritical is favored by the most recent computational and experimental evidence. Although the preponderance of evidence is consistent with the existence of a second critical point in water, the behavior of ice polymorph melting lines does not provide strong evidence in support of this viewpoint, according to our calculations.

The fragile-to-strong kinetics features of two-dimensional confined ultrathin Ag-In-Sb-Te film

The crystallization kinetics of supercooled Ag-In-Sb-Te liquids (in thick single film) has recently been shown to exhibit a fragile-to-strong crossover (FSC) behavior, which is beneficial to balance the contradiction between fast crystallization rate around the melting temperature (Tm) and good thermal stability (low crystallization rate) nearby the glass transition temperature (Tg). In this work, we fabricated an ultrathin Ag-In-Sb-Te film (∼7 nm) that is confined in a 2D structure. Does this confined ultrathin film exhibit FSC behavior? Focusing on this issue, we studied the crystallization features of 2D confined Ag-In-Sb-Te ultrathin film by using the method of ultrafast differential scanning calorimetry and the viscosity model of generalized Mauro-Yue-Ellison-Gupta-Allan. It was found that, the FSC behavior is presented and enhanced in this confined Ag-In-Sb-Te film. Interestingly, the FSC temperature of this confined Ag-In-Sb-Te is 473 K (∼1.25 Tg), which is equal to that of thick single Ag-In-Sb-Te film, indicating the structural origins of FSC behavior are same in these Ag-In-Sb-Te supercooled liquids, i.e., the FSC behavior stems from liquid-liquid phase transition that is predominantly caused by the increase of Peierls distortions with the competition between short range and medium range cluster. This reveals the crystallization features of ultrathin Ag-In-Sb-Te film, enabling a systematic optimization of the memory-switching kinetics in low-dimensional phase-change device.

Fluid phase equilibria of Brazilian presalt crude oil – CO2 systems at high pressure and high temperature

This paper aims to conduct an experimental investigation of the fluid phase behavior of a highly opaque Brazilian pre-salt crude oil-CO2 system, specifically focusing on the occurrence of highly dispersed liquid-liquid transitions. The study involves examining the phase behavior of five global mole compositions [zCO2= (37.9, 50.0, 76.6, 80.6, and 84.2) mol%] by using conventional PVT techniques as light scattering, pressure-volume curve, and direct fluid observation through sapphire windows. When other techniques were ineffective, a high-pressure microscope coupled with a short-wave infrared apparatus (SWIR camera and light source) was used for complex fluid inspection.

A phase transition model in dual-amorphous water undergoing liquid–liquid transition

An in-depth understanding of liquid–liquid phase transition (LLPT) in condensed water will gain insight into anomalous behaviors of dual-amorphous condensed water. Despite numerous experimental, molecular simulation, and theoretical studies, it is yet to achieve a widely accepted consensus with convinced evidence in the condensed matter physics for two-state liquid–liquid transition of water. In this work, a theoretical model is proposed based on the Avrami equation, commonly used to describe first-order phase transitions, to elucidate complex homogeneous and inhomogeneous condensation from high-density liquid (HDL) water to low-density liquid (LDL) water for both pure and ionic dual-amorphous condensed water. This model unifies the coupling effects of temperature and electrolyte concentration based on the new theoretical framework. The Adam–Gibbs theory is then introduced to characterize the synergistic motion and relaxation behavior of condensed water. Variations in the configurational entropy under electrostatic forces are further explored, and an analytical 2D cloud chart is developed to visualize the synergistic effect of temperature and electrolyte concentration on the configurational entropy of ionic water. The constitutive relationships among viscosity, temperature, and electrolyte concentration are derived to analyze their synergistic effects under different condensation fractions of LDL and HDL. The Stokes–Einstein relation and free volume theory are further used to analyze diffusion coefficients and densities (or apparent density) during both pure and ionic LLPT. Finally, theoretical results obtained from these models are compared with experimental results reported in literature to validate the accuracy and applicability of the proposed models, which offer significant benefits and advancements in effectively predicting physical property changes of dual-amorphous condensed water.

Analysis of Structural Change across the Liquid-Liquid Transition and the Widom Line in Supercooled Stillinger-Weber Silicon.

We consider the changes in the structure of supercooled Stillinger-Weber silicon at pressures at which the studied range of temperatures traverses the liquid-liquid transition or the "Widom line" (at which the isothermal compressibility or the specific heat exhibits a maximum). In addition to the conventional characterizations in terms of the pair-correlation function and bond orientational order, we analyze the statistics of rings in the bond network as well as the statistics of clusters of low density liquid (LDL)- and high density liquid (HDL)-like atoms. We investigate the nature of the change in these structural characterizations when the liquid-liquid transition line or the Widom line is crossed. We find that the isobaric temperature variation of these structural features reveals clear indications of maximal structural heterogeneity or frustration upon crossing the liquid-liquid transition or the Widom line, as in the case of water, but with some differences in detail, which we discuss.

Solid Phase Transitions in the Liquid Limit

We address the fundamental difference between solid-solid and liquid-liquid phase transitions within the Ericksen's nonlinear elasticity paradigm. To highlight ideas, we consider the simplest nontrivial 2D problem and work with a prototypical two-phase Hadamard material which allows one to weaken the rigidity and explore the nature of solid-solid phase transitions in a ``near-liquid'' limit. In the language of calculus of variations we probe limits of quasiconvexity in an ``almost liquid'' solid by comparing the thresholds for cooperative (laminate based) and non-cooperative (inclusion based) nucleation. Using these two types of nucleation tests we obtain for our model material surprisingly tight two-sided bounds on the elastic binodal without directly computing the quasiconvex envelope.

High-Temperature Liquid-Liquid Phase Transition in Glass-Forming Liquid Pd43Ni20Cu27P10.

Liquid-liquid phase transition (LLPT) is a transition from one liquid state to another with the same composition but distinct structural change, which provides an opportunity to explore the relationships between structural transformation and thermodynamic/kinetic anomalies. Herein the abnormal endothermic LLPT in Pd43Ni20Cu27P10 glass-forming liquid was verified and studied by flash differential scanning calorimetry (FDSC) and ab initio molecular dynamics (AIMD) simulations. The results show that the change of the atomic local structure of the atoms around the Cu-P bond leads to the change in the number of specific clusters <0 2 8 0> and <1 2 5 3>, which leads to the change in the liquid structure. Our findings reveal the structural mechanisms that induce unusual heat-trapping phenomena in liquids and advance the understanding of LLPT.

The liquid-liquid structure change in eutectic Ga-Sn alloy

• The liquid-liquid structure transition did occur around the liquidus temperature. • Another liquid-liquid structure transition did occur in the range from 1073-1273 K. • Below and above the liquidus temperature, the liquid exhibits differences in viscosity, coordination numbers, correlation radius of cluster. The effect of temperature on dynamic viscosity and atomistic structure in liquid eutectic Ga-Sn alloy have been investigated by using a torsional oscillating viscometer, an X-ray diffractometer and the ab initio molecular dynamics simulation. The results indicated that the liquid-liquid structure transitions did occur around the liquidus temperature and in the range from 1073-1273 K. Below and above these temperatures the liquid exhibits differences in viscosity, coordination numbers, correlation radius of cluster, which are reflected from structural changes of structural disorder and local atomic packing. This work will trigger a further study on the liquid-to-liquid crossover in the liquid-solid transition.