Liquid Phase Transition Research Articles

Enhanced Nitrate Fraction: Enabling Urban Aerosol Particles to Remain in a Liquid State at Reduced Relative Humidity

AbstractNitrate has become the primary inorganic compound in urban aerosol particles, but its effects on particle phase state, which is crucial in multiphase chemistry, remains largely unknown. Herein, particle rebound measurements were conducted to explore the relationship between the liquid–phase–transition threshold relative humidity (RHthreshold) and the inorganic compounds mass fraction in dry particles (Finorg). Results revealed negative correlations between RHthreshold and Finorg, with more nitrate leading to lower RHthreshold. Even with RH < 20%, particles with ∼50% nitrate mass fraction remained in non‐solid state. Taking Beijing as an example, decreases were observed in RHthreshold from 64% in 2015 to below 53% nowadays during the moderate‐pollution periods (PM2.5 = 35–75 μg/m3) due to an enhanced nitrate fraction. This allowed urban aerosol particles to exist in liquid state at lower RH, and consequently, kinetic limitation by bulk diffusion in nitrate‐dominated particles might be negligible, making them key seeds for secondary aerosol formation through multiphase reactions.

Dynamical behaviour of phase transitions in liquid crystals under ultrasound field

The study investigates the influence of an acoustic field on the process of interface formation, phase boundary propagation kinetics, and isotropic phase nucleation in a nematic liquid crystal (NLC) during the NLC → isotropic liquid (IL) phase transition. Experimental studies were conducted using acoustically "rigid" drops and both "rigid" and "soft" cells of sandwich type, with one substrate being a piezo quartz’s X-cut plate. The thickness of the investigated LC layers with planar and homotropic orientations was 20, 50, and 100 μm. The frequency of the ultrasonic field ranged from 3.77 to 4 MHz. Additionally, we computed the values of isotropic germ’s radius in NLC during the NLC → IL phase transition both without and under the ultrasonic field. The obtained data indicate an increased probability of forming a germ of an isotropic phase during the NLC → IL phase transition under the influence of ultrasound. These findings align well with the experimentally observed trends in the changes of phase transition temperature, specifically with the depression of the NLC → IL phase transition temperature in the presence of an ultrasound field.

Influence of acidity on liquid–liquid phase transitions of mixed secondary organic aerosol (SOA) proxy–inorganic aerosol droplets

Abstract. The phase state and morphology of aerosol particles play a critical role in determining their effect on climate. While aerosol acidity has been identified as a key factor affecting multiphase chemistry and phase transitions, the impact of acidity on the phase transition of multicomponent aerosol particles has not been extensively studied in situ. In this work, we employed aerosol optical tweezers (AOT) to probe the impact of acidity on the phase transition behavior of levitated aerosol particles. Our results revealed that higher acidity decreases the separation relative humidity (SRH) of aerosol droplets mixed with ammonium sulfate (AS) and secondary organic aerosol (SOA) proxy, such as 3-methylglutaric acid (3-MGA), 1,2,6-hexanetriol (HEXT) and 2,5-hexanediol (HEXD) across aerosol pH in atmospheric conditions. Phase separation of organic acids was more sensitive to acidity compared to organic alcohols. We found the mixing relative humidity (MRH) was consistently higher than the SRH in several systems. Phase-separating systems, including 3-MGA / AS, HEXT / AS and HEXD / AS, exhibited oxygen-to-carbon ratios (O:C) of 0.67, 0.50 and 0.33, respectively. In contrast, liquid–liquid phase separation (LLPS) did not occur in the high-O:C system of glycerol / AS, which had an O:C ratio of 1.00. Additionally, the morphology of 42 out of the 46 aerosol particles that underwent LLPS was observed to be a core–shell structure. Our findings provide a comprehensive understanding of the pH-dependent LLPS in individual suspended aerosol droplets and pave the way for future research on phase separation of atmospheric aerosol particles.

VLE measurement of binary systems 1-butyl-3-methylimidazolium-based ionic liquids and ethanol or water

Experimental vapor–liquid equilibrium (VLE) data for binary systems of ethanol or water with four ionic liquids (ILs) comprising 1-butyl-3-methylimidazolium cation and different anions were measured at atmospheric pressure within a broad region of IL concentrations, IL mole fraction ranging between 0 and 0.7 or even 0.87. Siwoloboff procedure of vapor–liquid phase transition temperature measurement was applied to estimate VLE of the binary mixtures. Obtained t–x data were fitted assuming ideal vapor and non-ideal liquid phase behavior, using the original NRTL equation to calculate component activity coefficients. VLE description results are presented in form of equilibrium diagrams and as the variation of activity coefficients with mixture composition. Quality of the VLE data fitting was assessed based on root mean square deviations and mean deviations in temperature. Some experimental binary t–x data sets were compared to those available in literature (measured in much narrower concentration range) or predicted from ternary VLE data. The selection of ILs in this study was related to the separation of ethanol−water mixture by extractive distillation. Principal IL selection criterium was its ability to affect the ethanol–water relative volatility. Thermodynamic description of the VLE data of IL-containing systems within a wide concentration range is an essential building block of the mathematical model of separation devices, especially in case of regeneration equipment where concentrated IL is present.

Novel star-shaped liquid crystal macromolecules based on conjugated structures of azo and Schiff bases: synthesis and properties

ABSTRACT In this paper, a series of novel liquid crystal units (ASE-n, n = 4, 6, 8) of azo Schiff bases with sulphonic acid (-SO3H) as terminal substituents and different alkyl chain lengths were designed and synthesised. Nine star-shaped liquid crystal macromolecules with different central groups (ASE-P-n, ASE-T-n, ASE-G-n, n = 4, 6, 8) were synthesised by esterification of three novel azo Schiff base liquid crystal units (ASE-n, n = 4, 6, 8) with phloroglucinol, pentaerythritol and glucose. The structure of the synthesised compounds were analysed by infrared spectroscopy and 1H NMR. The results showed that all the compounds were consistent with the molecular structure design. The properties of liquid crystal such as phase transition temperature and liquid crystal mesophase range were characterised by POM and DSC. The effects of alkyl chain length and branched degree on the properties of liquid crystal were studied. The maximum absorption spectrum of the compound was determined by UV-Vis spectrophotometry. The photoisomerisation reaction of the compound was also studied. Under ultraviolet light (λ = 365 nm) irradiation, the effect of different duration on the cis-absorption percentage of azo (-N=N-) bond in the compound was studied.

Role of site–site interaction on the phase equilibria of multiple-site associating fluids in a functionalized slit pore

Vapor–liquid phase equilibria for multiple sites associating fluids with different associating strengths are investigated in a slit pore using grand-canonical transition matrix Monte Carlo method. The increase of critical temperature from two-site to four-site associating fluids at constant site strength is quite significant as compared to that of the one-site to two-site associating fluids, which is more pronounced at higher associating strength (ϵ* = 6). Monomer fraction and cluster size distribution are used to investigate the association of fluid particles in coexistence phases. The monomer fraction for both phases decreases with increased associating sites on the fluid particles due to more site–site interaction with neighboring fluid particles and forming a larger cluster. Therefore, the number of associating sites and their distribution play a vital role in the association of fluid particles. Moreover, the saturation chemical potential changes with the arrangement of the sites. For two-site associating fluids, we observe early vapor–liquid transition when the sites are oppositely placed, and when the sites are placed at 90°, the vapor–liquid transition is observed at the higher chemical potential. Moreover, four-site associating fluids with a square arrangement show early vapor–liquid phase transition, mainly because these arrangements of sites effectively interact with surface sites and the molecules in the next layer.

Crystal polymorphs and multiple pathways of phase transitions in ionic liquids

Crystal polymorphs and multiple pathways of phase transitions in ionic liquids

Solid–Liquid Phase Transitions of Triglycerides in Griebenschmalz, Smalec, and Fedt Studied Using 13C Solid-State NMR with Dynamics-Based Spectral Filtering

The consumer satisfaction of lard-based bread spreads depends on a delicate balance between a liquid fat phase, allowing the spread to flow, and solid fat crystals, providing the product with substance sometimes further enhanced by crispy pork cracklings. Here we apply 13C solid-state NMR with dynamics-based spectral filtering to characterize and follow the temperature dependence of the co-existing solid and liquid triglyceride phases in commercial German Griebenschmalz and Polish smalec, both containing cracklings, as well as home-made Danish fedt and, as a chemically more pure reference, German Schweineschmalz intended for baking. The NMR method allows detection of carbon atoms representative of saturated, unsaturated, and polyunsaturated acyl chains in both solid and liquid states. The results show that the solid comprises multiple crystal forms with different melting temperatures, while the liquid is at low temperature enriched in triglycerides with shorter acyl chains and higher degree of unsaturation, which become diluted with long-chain saturated triglycerides as the solids are melting. The obtained deeper understanding of the concomitant aspects of the phase transitions may pave the way for future efforts of rational optimization of fat blend composition to extend the temperature range over which the product contains sufficient amounts of both solids and liquids to give texture properties appealing to consumers.

Robust and adhesive double-solvent phase change hydrogel with reversible transparency and shape memory for thermal management and information encryption

The excellent energy storage capacity of solid–liquid phase change materials has attracted considerable attention, but the vulnerability to leakage limits their applications. Therefore, the development of composite phase change materials has become a hot research topic in recent years. Therefore, a double-solvent (DS) phase change hydrogel (PCH) prepared by random copolymerization of acrylic acid (AA) and hydroxyethyl methacrylate (HEMA) with water and polyethylene glycol (PEG) as solvents was proposed. The phase transition enthalpies of melting and crystallization of the gel reached 116.2 J·g−1 and 113.5 J·g−1, respectively. PCH exhibits good morphological stability while storing thermal energy, which can effectively encapsulate phase change materials without leakage at high temperatures and be recyclable. PEG is used as both solvent and phase change part and the prepared gel reveals a high phase change material loading rate (76.2%), high breaking stress (4.7 MPa) and excellent compression resistance (1.2 MPa), superior to existing counterparts. The presence of a small amount of water in the system endows the gel with certain flexibility. Moreover, due to the solid–liquid phase transition behavior of PEG during temperature changes, PCHs possesses reversible adhesion and transparency, as well as shape memory properties. In addition, its low thermal conductivity and high energy storage efficiency make it perform well in the field of infrared stealth.

Coexistence of slow and fast dynamics in interfacial water around a carbon nanotube

We investigated the dynamics of water molecules in the interfacial water around a carbon nanotube (CNT) by analyzing the rotational autocorrelation function (RACF) for water molecules using molecular dynamics simulations. We found that the function undergoes a gradual crossover with temperature for the interfacial water with double-molecular-layer structure around the CNT, in contrast to bulk water, which shows a discontinuous change in the RACF at 0 °C. This is consistent with recent experimental results showing that interfacial water does not exhibit a solid–liquid phase transition. In addition, the RACF results can be fitted by exponential functions with two different time constants, indicating that the proportion of disordered structures relative to ordered structures, in which water molecules have more restricted rotation, increases continuously with temperature. The continuous structural change yields the gradual solid–liquid crossover.

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.

Engineering a triple-functional magnetic gel driving mutually-synergistic mild hyperthermia-starvation therapy for osteosarcoma treatment and augmented bone regeneration

Malignant bone tumors result in high rates of disability and death and are difficult to treat in terms of killing tumors and repairing bone defects. Compared with other hyperthermia strategies, magnetic hyperthermia has become an effective therapy for treating malignant bone tumors due to its lack of depth limitations. However, tumor cells express heat shock protein (HSP) to resist hyperthermia, which reduces its curative effect. Competitive ATP consumption can reduce HSP production; fortunately, the basic principle of starvation therapy by glucose oxidase (GOx) is consuming glucose to control ATP production, thereby restricting HSP generation. We developed a triple-functional magnetic gel (Fe3O4/GOx/MgCO3@PLGA) as a magnetic bone repair hydrogels (MBRs) with liquid‒solid phase transition capability to drive magneto-thermal effects to simultaneously trigger GOx release and inhibit ATP production, reducing HSP expression and thereby achieving synergistic therapy for osteosarcoma treatment. Moreover, magnetic hyperthermia improves the effect of starvation therapy on the hypoxic microenvironment and achieves a reciprocal strengthening therapeutic effect. We further demonstrated that in situ MBRs injection effectively suppressed tumor growth in 143B osteosarcoma tumor-bearing mice and an in-situ bone tumor model in the rabbit tibial plateau. More importantly, our study also showed that liquid MBRs could effectively match bone defects and accelerate their reconstruction via magnesium ion release and enhanced osteogenic differentiation to augment the regeneration of bone defects caused by bone tumors, which generates fresh insight into malignant bone tumor treatment and the acceleration of bone defect repair.

Numerical Investigation of the Cavitation Characteristics in Venturi Tubes: The Role of Converging and Diverging Sections

Cavitation is a typical physical process that has shown to be highly valuable in the wastewater treatment field. This study aims to investigate the effects of the converging and diverging sections of a Venturi tube on the cavitation flow field. Multiphase flows in tubes are presented using the mixture model and the standard k-ε model. And the Schnerr and Sauer cavitation model is employed to simulate the vapor–liquid phase transition process. Both grid independence and the numerical method’s feasibility were validated before the research. The results showed that the influence of the divergence section length on Venturi cavitation characteristics depends on the provided pressure conditions. As the pressure increases, shorter divergence sections result in more significant cavitation effects. The length of the convergence section displays various cavitation behaviors under different pressure situations. A small contraction section length can achieve better cavitation effects in high-pressure applications, whereas the opposite is true in low-pressure cases. Within the scope of this study, it was observed that the Venturi tube with a divergent section of 14 Lt and a convergent one of 2.4 Lt provided enhanced cavitation performance when subjected to inlet pressures ranging from 0.8 to 1.2 MPa. Our findings indicate that the selection of converging and diverging section lengths in Venturi tubes should consider the corresponding operational pressure conditions, which provides valuable guidance and engineering significance in the research and development of Venturi cavitation devices in hydraulic engineering.

Principle and Feasibility Study of Proposed Hydrate-Based Cyclopentane Purification Technology

The separation of azeotropic mixtures has conventionally been one of the most challenging tasks in industrial processes due to the fact that components in the mixture will undergo gas–liquid phase transition at the same time. We proposed a method for separating azeotropes using hydrate formation as a solid–liquid phase transition. The feasibility of hydrate-based separation is determined by analyzing the crystal structure and chemical bonds of hydrate. Taking the azeotrope cyclopentane and neohexane in petroleum as an example, cyclopentane (95%) was purified to 98.56% yield using the proposed hydrate-based cyclopentane purification technology. However, this is difficult to achieve using conventional distillation methods. The proposed method is simple in operation and yields a good separation effect. This study provides a new method for separating cyclopentane and neohexane.

Thermal and Electrical Properties of Liquid Metal Gallium During Phase Transition

Liquid metal gallium has been widely used in numerous fields, from nuclear engineering, catalysts, and energy storage to electronics owing to its remarkable thermal and electrical properties along with low viscosity and nontoxicity. Compared with high-temperature liquid metals, room-temperature liquid metals, such as gallium (Ga), are emerging as promising alternatives for fabricating advanced energy storage devices, such as phase change materials, by harvesting the advantageous properties of their liquid state maintained without external energy input. However, the thermal and electrical properties of liquid metals at the phase transition are rather poorly studied, limiting their practical applications. In this study, we reported on the physical properties of the solid–liquid phase transition of Ga using a custom-designed, solid–liquid electrical and thermal measurement system. We observed that the electrical conductivity of Ga progressively decreases with an increase in temperature. However, the Seebeck coefficient of Ga increases from 0.2 to 2.1 µV/K, and thermal conductivity from 7.6 to 33 W/(K∙m). These electrical and thermal properties of Ga at solid–liquid phase transition would be useful for practical applications.

Study on Liquid Phase Transition of Shaped Charge Jet Penetrating Liquid

Study on Liquid Phase Transition of Shaped Charge Jet Penetrating Liquid

Fast Charging of a Thermal Accumulator Based on Paraffin with the Addition of 0.3 wt. % rGO

The composite of paraffin with reduced graphene oxide (paraffin/rGO) was obtained at 70 °C by the mechanical mixing of the components followed by ultrasonic dispersion. The introduction of only 0.3 wt.% rGO stained the paraffin black. It has been shown that thermal batteries made from 160 grams of pure paraffin and 160 grams of the composite are equally slow at charging when placed in boiling water. However, two minutes of microwave heating increases the temperature of the pure paraffin battery to only 32 °C, while the temperature of the paraffin/rGO composite battery rises to 74 °C, which is above the paraffin solid–liquid phase transition temperature.

Proposal to detect emergent gauge field and its Meissner effect in spin liquids using NV centers

We show that NV centers could provide distinct signatures of emergent gauge fields in certain phase transitions in spin liquids. We consider the relaxation rate $1/T_1$ of a diamond NV center placed a distance $z_0$ above a crystal consisting of two dimensional layers which hosts a $U(1)$ quantum spin liquid with spinon Fermi surface. We show that during a spinon pairing transition from a $U(1)$ to a $\mathbb{Z}_2$ spin liquid, the relaxation rate exhibits a rapid fall just below the pairing transition. The drop is much faster than what can be accounted for by the opening of the energy gap. Instead, the rapid fall with a unique $z_0$ dependence of its height and width, is the signature of the Meissner effect of the gauge field. We identify the organic ET compound which has a phase transition at 6K as a candidate for the experimental observation of this phenomenon.

Shape-stabilized 1-hexadecanol/g-C3N4/Cu composite phase change material with high thermal conductivity for efficient photo-thermal conversion

Phase change materials (PCM) have received much attention for thermal energy storage and release in the form of latent heat. 1-hexadecanol (HD), as a representative of organic phase change materials, has the advantages of high thermal storage density, almost constant operating temperature and stable thermochemical properties, which shows outstanding potential in the field of phase change energy storage. Nevertheless, single HD as thermal storage material inevitably faces challenges in terms of liquid phase leakage, low thermal conductivity, and poor photo-thermal conversion. To further improve the practical application of HD, we demonstrate a convenient encapsulation and modification strategy of composite phase change materials (CPCMs) with low liquid leakage and high thermal conductivity. Hence, a novel shape-stabilized Cu-doped HD/ graphitic carbon nitride (g-C3N4) CPCM was developed for efficient photo-thermal storage. By the melt blending method, HD is infiltrated into tightly stacked and aligned nano-porous g-C3N4, and the carbon-based lattice inlay achieves the encapsulation of HD to solve the leakage problem during the solid–liquid phase transition. Then, metallic Cu powder is introduced to further strengthen the thermal conductivity of the materials. With this encapsulation and modification strategy, the obtained 5 wt% Cu-doped HD/g-C3N4 composites (CPCM3) exhibits superior performance in both thermal and optical energy storage. This composite has appropriate phase change temperature and extremely high heat storage density, with melting temperature and latent heat of 48.88 °C and 249.63 J/g. The corresponding solidification temperature and latent heat is 48.52 °C and 242.22 J/g, respectively. Its thermal conductivity is enhanced to 0.5307 W/m·K, which is 59.8% higher than pure HD. The photo-thermal conversion efficiency is up to 81.6% for rapid solar energy harvesting and delivery. In particular, after 100 times thermal cycling tests and thermogravimetric analysis, this special CPCM can maintain good thermal reliability and thermal stability. In conclusion, the composite phase change materials obtained by the synergistic modification strategy of nano-porous g-C3N4 and metallic Cu significantly improved the thermochemical properties of HD. This work provides a practical and efficient synthetic strategy for the preparation of CPCMs, which is expected to present a promising future in the field of solar conversion and storage.

An anomalous structure disordering in Zr–Cu–Ag supercooled glass-forming liquids

An anomalous ordering-to-disordering transition in a Zr–Cu–Ag supercooled glass-forming liquid has been revealed by in situ high-energy x-ray diffraction. Upon heating, the supercooled liquid exhibits a structural crossover at Tc = 716 K, evident by the change in statistical characteristics of the first sharp diffraction peak. When annealed in the vicinity of Tc, the supercooled liquid first relaxes from its initial state to a denser and more ordered state. Subsequently, it becomes disordered at the medium-range scale with a slowing down of densification, as demonstrated by the broadening of the first sharp diffraction peak and a decrease in the peak intensities of the higher atomic shells in the reduced pair distribution function. A scenario for the evolution of less correlated locally favored clusters in the liquid–liquid phase transition is discussed.