Liquid State Properties Research Articles

A paradigm for natural eutectic solvents based on fatty acids: Molecular interactions and toxicological considerations

In this work, we present experimental and molecular modeling results on archetypal hydrophobic natural deep eutectic solvents (NADES) based on fatty acids (octanoic and dodecanoic acid) and menthol, a representative monoterpenoid. Our goal is to provide a multiscale characterization to enhance the understanding of this field by studying these selected archetypical mixtures. We examine their liquid state properties, intermolecular forces, nanoscopic arrangements, toxicity, and environmental impact.The computational study integrates quantum chemistry, molecular dynamics (both all-atom and coarse-grained approaches), and thermodynamic modeling (COSMO-RS approach) to analyze the fluids and their interactions with biological entities, such as proteins and plasma membranes. The experimental characterization focuses on elucidating intermolecular interactions and liquid phase dynamics using NMR spectroscopy, visible and UV Resonance Raman spectroscopy (UVRR). Notably, this is the first report of UVRR data on NADES.Additionally, we simulate the effect of the molecular moieties forming the solvents on biological targets—specifically, protein and cell membrane models –. This in silico analysis aims to rationalize and predict their potential toxicity.Overall, our experimental findings and in silico simulations contribute to a deeper understanding of these novel solvents in terms of their network of interactions. Additionally, they highlight the potential impact on biological targets, providing new data to accurately define the eco-friendliness of type V DES and their suitability as sustainable alternatives to traditional molecular solvents.

Prediction of azeotropic behavior using physicochemical properties for Sn-based binary liquid alloys in vacuum distillation

Crude tin must undergo separation from impurities to enhance its value and expand its applications. The phase diagrams and physical properties in liquid state of Sn-based alloys are the theoretical basis for vacuum impurity removal from crude tin. The formation of azeotrope affects the effect of impurity removal in vacuum distillation. This study focuses on the correlation between the azeotropic region and the parameters of the Wilson equation of 13 Sn-based binary systems under 10 Pa. The results reveal that the Al–Sn, Cu–Sn, and Ti–Sn systems can form azeotropes that are challenging to separate through straightforward vacuum distillation. In contrast, the other Sn-based binary alloys could not form azeotropes at the experimental conditions, thereby facilitating their removal through vacuum distillation. This method provides a reliable support for the separation and purification of crude tin by vacuum distillation.

Time-Resolved X-ray Emission Spectroscopy and Resonant Inelastic X-ray Scattering Spectroscopy of Laser Irradiated Carbon.

The existence of liquid carbon as an intermediate phase preceding the formation of novel carbon materials has been a point of contention for several decades. Experimental observation of such a liquid state requires nonthermal melting of solid carbon materials at various laser fluences and pulse properties. Reflectivity experiments performed in the mid-1980s reached opposing conclusions regarding the metallic or insulating properties of the purported liquid state. Time-resolved X-ray absorption studies showed shortening of C-C bonds and increasing diffraction densities, thought to evidence a liquid or glassy carbon state, respectively. Nevertheless, none of these experiments provided information on the electronic structure of the proposed liquid state. Herein, we report the results of time-resolved resonant inelastic X-ray scattering (RIXS) and time-resolved X-ray emission spectroscopy (XES) studies on amorphous carbon (a-C) and ultrananocrystalline diamond (UNCD) as a function of delay time between the irradiating pulse and X-ray probe. For both a-C and UNCD, we attribute decreases in RIXS or XES signals to transition blocking, relaxation, and finally, ablation. Increased signal at 20 ps following the irradiation of the UNCD is attributed to the probable formation of nanoscale structures in the ablation plume. Differences in the amount of signal observed between a-C and UNCD are explained by the difference in sample thickness and, specifically, incomplete melting of the UNCD film. Comparisons to spectral simulations based on MD trajectories at extreme conditions indicate that the carbon state in our experiments is crystalline. Normal mode analysis confirmed that symmetrical bending or stretching of the C-C bonds in the diamond lattice results in XES spectra with small intensity differences. Overall, we observed no evidence of melting to a liquid state, as determined by the lack of changes in the spectral properties for up to 100 ps delays following the melting pulses.

Structural fluctuations in active glasses.

The glassy dynamics of dense active matter have recently become a topic of interest due to their importance in biological processes such as wound healing and tissue development. However, while the liquid-state properties of dense active matter have been studied in relation to the glass transition of active matter, the solid-state properties of active glasses have yet to be understood. In this work, we study the structural fluctuations in the active glasses composed of self-propelled particles. We develop a formalism to describe the solid-state properties of active glasses in the harmonic approximation limit and use it to analyze the displacement fields in the active glasses. Our findings reveal that the dynamics of high-frequency normal modes become quasi-static with respect to the active forces, and consequently, excitations of these modes are significantly suppressed. This leads to a violation of the equipartition law, suppression of particle displacements, and the apparent collective motion of active glasses. Overall, our results provide a fundamental understanding of the solid-state properties of active glasses.

Tutorial: Deep learning prediction of thermophysical properties for liquid multicomponent alloys

The thermophysical properties of liquid metals and alloys are crucial to explore the intrinsic mechanisms of the solidification process, glass formation, and fluid dynamics. The deep learning approaches have emerged as powerful tools in numerous scientific fields and exhibit extraordinary accuracy in the estimation of physical properties and structural characteristics for various materials. In this Tutorial, focusing on the thermophysical properties of liquid multicomponent alloys, deep learning methods, including both supervised learning and active learning, are introduced. Combined with the verification from electrostatic and electromagnetic levitation experiments, the influences of training parameters and methods on the accuracy to obtain interatomic potential by deep learning are revealed on the basis of deep neural network algorithm. As a result, this prediction method of liquid state properties for multicomponent alloys exhibited the dual advantages of high accuracy derived from density functional theory and low computational cost associated with empirical potential.

Liquid state properties and rapid solidification mechanism of Fe-Nd-B alloy investigated under space simulation conditions

The thermophysical properties of liquid Fe84Nd10B6 alloy from superheated to undercooled state were investigated by space simulation technology combined with ab initio molecular dynamics (AIMD) simulations. The liquid density at liquidus temperature and its temperature coefficient were determined as 7.17 g·cm−3 and 5.51 × 10−4 g·cm−3·K−1, while its liquid thermal expansion coefficient was measured as 7.69 × 10−5 K−1. The ratio of specific heat to emissivity decayed as a quadratic power function. Under electrostatic levitation (ESL) condition, even though the cooling rate of liquid alloy was only 23.6–35.3 K/s, a maximum 131 K undercooling was realized. As alloy undercooling rose, the grain size of primary α(Fe) dendrite was refined, whose volume fraction decreased from 26.2% to 22.0%. Meanwhile, the volume fraction of major peritectic τ1(Nd2Fe14B) phase was increased from 68.6% to 76.8%, which was accompanied by the reduction of peri-eutectoid τ2(Nd1.1Fe4B4) phase down to 1.2%. In the case of microgravity processing by drop tube, liquid undercooling and cooling rate respectively reached up to 260 K (0.16 TL) and 3.9 × 104 K/s for the falling alloy droplets. Instead of τ1 phase, the primary α(Fe) phase occupied the largest volume fraction of 49.7% in large alloy droplets. At enhanced undercooling and cooling rate, the peritectic τ1 phase only increased from 26.2% up to 43.5%, whereas those of α(Fe) and τ2 phases declined to 44.0% and 12.5%, respectively. It was found that the increase of liquid alloy undercooling promoted the peritectic transformation to some extent, but high cooling rate greatly restricted peritectic reaction by reducing reaction time. The coupled effect of liquid undercooling and cooling rate controlled the volume fraction of each phase in rapidly solidified microstructures.

Coassembly of Cellulose Nanocrystals and Neutral Polymers in Iridescent Chiral Nematic Films.

Photonic materials based on composite films of cellulose nanocrystals (CNCs) and polymers are promising as they can be renewable and show tunable optical and mechanical properties. However, the influence of polymers on CNC self-assembly is not always well understood, and conflicting results are present in the literature. In this study, we incorporate three neutral, water-soluble polymers-poly(ethylene glycol) (PEG), poly(vinyl pyrrolidone) (PVP), and poly(acrylic acid) (PAA)-with different molecular weights into CNC suspensions at various concentrations prior to obtaining iridescent composite thin films by solvent evaporation. Through spectroscopic, potentiometric, and rheological analyses, we find that PVP physically adsorbs to the surface of CNCs resulting in a bathochromic shift in film color with both increasing concentration and polymer molecular weight. In contrast, PEG induces depletion interactions that result in a decrease in the size of chiral nematic CNC domains, with a negligible change in film color. Finally, PAA hydrogen bonds to the hydroxyl groups of CNCs, resulting in a bathochromic color shift along with interesting rheological and liquid-state properties. This work demonstrates a deeper understanding of CNC-polymer interactions during coassembly and formation of iridescent chiral nematic films, allowing for greater control over optical properties of future CNC-based materials.

Soluplus® promotes efficient transport of meloxicam to the central nervous system via nasal administration

In our present series of experiments, we investigated the nasal applicability of the previously developed Soluplus® - meloxicam polymeric micelle formulation. Utilizing the nasal drug investigations, moderately high mucoadhesion was experienced in nasal conditions which alongside the appropriate physicochemical properties in liquid state, contributed to rapid drug absorption through human RPMI 2650 cell line. Ex vivo studies also confirmed that higher nasal mucosal permeation could be expected with the polymeric micelle nanoformulation compared to a regular MEL suspension. Also, the nanoformulation met the requirements to provide rapid drug permeation in less 1 h of our measurement. The non-toxic, non-cell barrier damaging formulation also proved to provide a successful passive transport across excides human nasal mucosa. Based on our in vivo investigations, it can be concluded that the polymeric micelle formulation provides higher meloxicam transport to the central nervous system followed by a slow and long-lasting elimination process compared to prior results where physical particle size reduction methods were applied. With these results, a promising solution and nanocarrier is proposed for the successful transport of non-steroidal anti-inflammatory drugs with acidic character to the brain.

Formation of intermediate gas-liquid system in aromatics’ thin layers

The present work discusses IR spectroscopic experiments and quantum- chemical DFT study of structure and intermolecular binding in the intermediate gas?liquid systems of aromatics, namely, benzene, furane, pyridine and thiophene. These systems can be generated in thin layers near a solid surface by two different methods, depending on the physical properties of the sample. The first method includes evaporation with a subsequent compression of a sample in an optical cell of variable thickness, and it is applied to volatile components: benzene, furane, thiophene. For benzene and pyridine the second method is used, which involves a heating-initiated evaporation into a closed inter-window space with an after-cooling of a sample. It was shown that the formed layer is not an adsorbate or a condensate. The IR data obtained by these two methods lead to conclusion that the given systems of the considered aromatics manifest dual gas?liquid spectral properties which can change each into other by varying external conditions. According to the DFT calculation results, the spatial arrangement in the aromatic thin layers can be described as a combination of ?- and ?-bonded clusters, which simulate the gas and the liquid phase state properties.

Density Scaling of Translational and Rotational Molecular Dynamics in a Simple Ellipsoidal Model near the Glass Transition.

In this paper, we show that a simple anisotropic model of supercooled liquid properly reflects some density scaling properties observed for experimental data, contrary to many previous results obtained from isotropic models. We employ a well-known Gay–Berne model earlier parametrized to achieve a supercooling and glass transition at zero pressure to find the point of glass transition and explore volumetric and dynamic properties in the supercooled liquid state at elevated pressure. We focus on dynamic scaling properties of the anisotropic model of supercooled liquid to gain a better insight into the grounds for the density scaling idea that bears hallmarks of universality, as follows from plenty of experimental data collected near the glass transition for different dynamic quantities. As a result, the most appropriate values of the scaling exponent γ are established as invariants for a given anisotropy aspect ratio to successfully scale both the translational and rotational relaxation times considered as single variable functions of densityγ/temperature. These scaling exponent values are determined based on the density scaling criterion and differ from those obtained in other ways, such as the virial–potential energy correlation and the equation of state derived from the effective short-range intermolecular potential, which is qualitatively in accordance with the results yielded from experimental data analyses. Our findings strongly suggest that there is a deep need to employ anisotropic models in the study of glass transition and supercooled liquids instead of the isotropic ones very commonly exploited in molecular dynamics simulations of supercooled liquids over the last decades.

Role of non-d valence electrons for the study of transport properties of some transition metals

In the present communication, the local form of pseudopotential with an effectively single parameter is used to carry out the comparative study of liquid metal resistivity using nearly free electron (NFE) Ziman's approach and transition matrix (T-matrix) Evan's approach. We have proposed a simple method to determine pseudopotential parameters by keeping account of non-d valence electrons. Our results of transport properties particularly T-matrix resistivity are in excellent agreement with experimental results and are better than other theoretical results which proves that the present proposed model is better for the theoretical understanding of transport properties. Moreover, the T-matrix approach for the understanding of liquid metal resistivity of transition metals is more reliable and physically sound. In absence of experimental results and other theoretical results, the study of electron dispersion, Fermi energy and density of states at Fermi energy will be helpful for the understanding of many liquid state properties and provide a base in future for comparison.

Liquid-State Volumetric Properties of a Set of Alcohols with Up to Five Carbon Atoms

This work provides density data (~1300 values) of 14 alcohols with up to five carbon atoms at p ∈ [0.1–40] MPa and T ∈ [278–358] K. The information obtained is modeled with a convenient reformulation of the Tait equation from which the volumetric coefficients, α and β, are derived both analytically and numerically. The general EoS containing α and β is also used for checking the consistency of the hypothesis on the invariability of the cited thermophysic parameters. The results obtained can be considered reliable because of the low estimated errors between the experimental data and those of the literature, which are below 0.4% for volume, while for the volumetric coefficients there is always a reference diverging 10%, or less, from the proposed model estimations. By including the averages of α and β into the general state of equation the errors increase, being <15%, compared to those based on the Tait equation. Hence, the assumption on the stability of the volumetric coefficients in this working interval is sufficient to make rough estimations of the molar volume of the selected alcohols.

Thermal, Viscoelastic and Surface Properties of Oxidized Field's Metal for Additive Microfabrication.

Field’s metal, a low-melting-point eutectic alloy composed of 51% In, 32.5 Bi% and 16.5% Sn by weight and with a melting temperature of 333 K, is widely used as liquid metal coolant in advanced nuclear reactors and in electro–magneto–hydrodynamic two-phase flow loops. However, its rheological and wetting properties in liquid state make this metal suitable for the formation of droplets and other structures for application in microfabrication. As with other low-melting-point metal alloys, in the presence of air, Field’s metal has an oxide film on its surface, which provides a degree of malleability and stability. In this paper, the viscoelastic properties of Field’s metal oxide skin were studied in a parallel-plate rheometer, while surface tension and solidification and contact angles were determined using drop shape analysis techniques.

Liquid state properties of SEI components in dimethoxyethane

The solid-electrolyte interphase (SEI) layer is a critical constituent of battery technology, which incorporates the use of lithium metals. Since the formation of the SEI is difficult to avoid, the engineering and harnessing of the SEI are absolutely critical to advancing energy storage. One problem is that much fundamental information about SEI properties is lacking due to the difficulty in probing a chemically complex interfacial system. One such property that is currently unknown is the dissolution of the SEI. This process can have significant effects on the stability of the SEI, which is critical to battery performance but is difficult to probe experimentally. Here, we report the use of ab initio computational chemistry simulations to probe the solution state properties of SEI components LiF, Li2O, LiOH, and Li2CO3 in order to study their dissolution and other solution-based characteristics. Ab initio molecular dynamics was used to study the solvation structures of the SEI with a combination of radial distribution functions, discrete solvation structure maps, and vibrational density of states, which allows for the determination of free energies. From the change in free energy of dissolution, we determined that LiOH is the most likely component to dissolve in the electrolyte followed by LiF, Li2CO3, and Li2O although none were favored thermodynamically. This indicates that dissolution is not probable, but Li2O would make the most stable SEI with regard to dissolution in the electrolyte.

Liquid state properties and solidification features of the pseudo binary BaS-La2S3

The high temperature thermodynamic properties of chalcogenides materials based on BaS remain elusive. Herein the pseudo binary BaS-La2S3 is investigated above 1573 K. The liquid properties of BaS-La2S3 are measured by means of high resolution in-situ visualization coupled with thermal arrest measurements in a thermal imaging furnace. This enables to report the first observation of such melts in a container-less setting. The melting points of BaS and La2S3 are revisited at 2454 K and 2004 K respectively. La2S3 demonstrates a high stability in its liquid state, in strike difference with the sublimation observed for BaS. BaS is however partially stabilized with the addition of few percents of La2S3. The remarkable chemical and thermal stability of La2S3-rich samples contrasts with the partial decomposition and high vapor pressure observed for BaS-rich samples. Observations and analysis of the solidified samples suggest three different solid solutions. Solid and liquid densities are investigated along the different compositions, supporting a first estimate of the volumetric thermal expansion coefficient for La2S3.

New Force-Field for Organosilicon Molecules in the Liquid Phase.

In this paper, we present a new molecular model that can accurately predict thermodynamic liquid state and phase-change properties for organosilicon molecules including several functional groups (alkylsilane, alkoxysilane, siloxane, and silanol). These molecules are of great importance in geological processes, biological systems, and material science, yet no force field currently exists that is widely applicable to organosilicates. The model is parametrized according to the recent Polarization-Consistent Approach (PolCA), which allows for polarization effects to be incorporated into a nonpolarizable model through post facto correction terms and is therefore consistent with previous parametrizations of the PolCA force field. Alkyl groups are described by the United-Atom approach, bond and angle parameters were taken from previous literature studies, dihedral parameters were fitted to new quantum chemical energy profiles, point charges were calculated from quantum chemical optimizations in a continuum solvent, and Lennard-Jones dispersion/repulsion parameters were fitted to match the density and enthalpy of vaporization of a small number of selected compounds. Extensive validation efforts were carried out, after careful collection and curation of experimental data for organosilicates. Overall, the model performed quite well for the density, enthalpy of vaporization, dielectric constant, and self-diffusion coefficient, but it slightly overestimated the magnitude of self-solvation free energies. The modular and transferable nature of the PolCA force field allows for further extensions to other types of silicon-containing compounds.

Fluorescent Carbon Nitride Macrostructures Derived from Triazine‐Based Cocrystals

AbstractCarbon nitride (CN) based materials have emerged as efficient photo‐ and electrocatalysts for various reactions. However, despite their intriguing optical properties (i.e., fluorescence), their utilization as solid‐state sensing platforms remains in its infancy, owing to the formation of defect states during the materials synthesis, leading to low emission for the CN powder. Here, a bottom‐up synthesis of CN macrostructures with good photoluminescence properties in both liquid and solid state is introduced, from designed triazine‐based cocrystals with ordered morphology and tailored chemical composition. Upon calcination at 500 °C, the starting morphology and chemical composition are retained, resulting in the alteration of the HOMO‐LUMO distribution of the CN materials, as further supported by density functional theory (DFT) calculations. The good photoluminescence properties of the new CN materials enable their exploitation as environmentally friendly, robust, and cheap sensing material for latent fingerprints labeling and metal‐ion detection in water.

The Role of Non-Specific Interactions in Canonical and ALT-Associated PML-Bodies Formation and Dynamics.

In this work, we put forward a hypothesis about the decisive role of multivalent nonspecific interactions in the early stages of PML body formation. Our analysis of the PML isoform sequences showed that some of the PML isoforms, primarily PML-II, are prone to phase separation due to their polyampholytic properties and the disordered structure of their C-terminal domains. The similarity of the charge properties of the C-terminal domains of PML-II and PML-VI isoforms made it possible for the first time to detect migration of PML-VI from PML bodies to the periphery of the cell nucleus, similar to the migration of PML-II isoforms. We found a population of “small” (area less than 1 µm2) spherical PML bodies with high dynamics of PML isoforms exchange with nucleoplasm and a low fraction of immobilized proteins, which indicates their liquid state properties. Such structures can act as “seeds” of functionally active PML bodies, providing the necessary concentration of PML isoforms for the formation of intermolecular disulfide bonds between PML monomers. FRAP analysis of larger bodies of toroidal topology showed the existence of an insoluble scaffold in their structure. The hypothesis about the role of nonspecific multiple weak interactions in the formation of PML bodies is further supported by the change in the composition of the scaffold proteins of PML bodies, but not their solidification, under conditions of induction of dimerization of PML isoforms under oxidative stress. Using the colocalization of ALT-associated PML bodies (APBs) with TRF1, we identified APBs and showed the difference in the dynamic properties of APBs and canonical PML bodies.

Classical magnetic vortex liquid and large thermal Hall conductivity in frustrated magnets with bond-dependent interactions

Recently, the observation of large thermal Hall conductivities in correlated insulators with no apparent broken symmetry has generated immense interest and debates on the underlying ground states. Here, considering frustrated magnets with bond-dependent interactions, which are realized in the so-called Kitaev materials, we theoretically demonstrate that a large thermal Hall conductivity can originate from a classical ground state without any magnetic order. We discover a liquid state of magnetic vortices, which are inhomogeneous spin textures embedded in the background of polarized spins, under out-of-plane magnetic fields. In the classical regime, different configurations of vortices form an effectively degenerate manifold. We study the static and dynamical properties of the magnetic vortex liquid state at zero and finite temperatures. In particular, we show that the spin excitation spectrum resembles a continuum of nearly flat Chern bands, which ultimately leads to a large thermal Hall conductivity. Possible connections to experiments are discussed.

SlagCalculator: A Framework for Slag and Metallurgical Properties

Physical properties of multi-component slag systems are of great importance for metallurgical processes, thereby many studies have shown that properties such as density, surface tension or viscosity can be predicted using previously developed models. However, nowadays there is no such framework integrating published models for calculation of slag properties and allowing for user-friendly post-processing of data. In this study, a web-based application for calculation of slag properties both in solid and liquid state was developed in Python. The web-application predicts density, heat capacity, surface tension and other properties from temperature and slag composition provided by the user and subsequently the user has the possibility to interact with and visualize data, and compare results from various models. The architecture of the web-application was designed to address interoperability and data security concepts. In addition, the modularity of the web-application was based on standardized web architectural styles to facilitate the addition of new models or functions in the future. The current work is aimed at demonstrating the key functionality of the application and initiating discussion and further collaboration for its development.