Solid-liquid Phase Transition Research Articles

Temperature-Dependent Modulation of Short-Wave-Infrared Light Transparency Based on Associated Structures of a Liquescent Nickel(III) Complex.

A liquescent bis(malononitriledithiolato)nickel(III) complex with a bis(methoxyethyl)imidazolium cation, 1[Ni(mnt)2 ], exhibits three-stage thermochromic modulation of transparency/absorption in the short-wave-infrared (SWIR) region (1000-2500nm), driven by associated structural changes. Upon heating, the electronic spectra of 1[Ni(mnt)2 ] in the SWIR region shift to shorter wavelengths accompanying with the solid-liquid phase transition at 76°C. Further heating to over 109°C induces a second transition of the electronic spectra, characterized by a blue-shift of the SWIR absorption in the liquid phase. The results of temperature-dependent electronic spectra and magnetic susceptibility indicated that the thermochromic changes can be attributed to the two-step dissociation of the associated structures of [Ni(mnt)2 ]- , occurring during the solid-liquid phase transition and the shift of dimer-monomer equilibrium in the liquid state. These changes can be visualized using an SWIR imaging camera under appropriate SWIR lights.

Complex Ga2O3 polymorphs explored by accurate and general-purpose machine-learning interatomic potentials

Ga2O3 is a wide-band gap semiconductor of emergent importance for applications in electronics and optoelectronics. However, vital information of the properties of complex coexisting Ga2O3 polymorphs and low-symmetry disordered structures is missing. We develop two types of machine-learning Gaussian approximation potentials (ML-GAPs) for Ga2O3 with high accuracy for β/κ/α/δ/γ polymorphs and generality for disordered stoichiometric structures. We release two versions of interatomic potentials in parallel, namely soapGAP and tabGAP, for high accuracy and exceeding speedup, respectively. Both potentials can reproduce the structural properties of all the five polymorphs in an exceptional agreement with ab initio results, meanwhile boost the computational efficiency with 5 × 102 and 2 × 105 computing speed increases compared to density functional theory, respectively. Moreover, the Ga2O3 liquid-solid phase transition proceeds in three different stages. This experimentally unrevealed complex dynamics can be understood in terms of distinctly different mobilities of O and Ga sublattices in the interfacial layer.

New liquid fraction measurement methodology for phase change material analysis based on X-ray computed tomography

To tackle climate change, it is of fundamental importance to develop more efficient systems to convert and manage energy. Latent Thermal Energy Storage (LTES) systems, which are based on Phase Change Materials (PCMs), present many interesting features that can lead us to achieve energy sustainability. In fact, these systems can be employed in many applications (e.g., HVAC, buildings thermal management, thermal energy recovery). To use PCMs, it is crucial to understand and monitor their phase-change behaviour. However, the evaluation of two-phase systems is still difficult because of the intrinsic complexity and transient behaviour.In the present study, a new methodology to measure liquid fraction is proposed. X-ray Computed Tomography (XCT) is used to follow the solidification process of eicosane. XCT and the acquisition settings were optimised to ensure maximum contrast between the phases. Then, the solidification process of eicosane was dynamically studied and the volumetric liquid fraction was extracted. Finally, via the Ansys Fluent software, a CFD model, based on the enthalpy-porosity method, was implemented to simulate the solidification of eicosane. The numerical results were compared against the experimental data, showing excellent agreement. This novel experimental methodology opens new possibilities to characterise and understand the solid-liquid phase transition process of PCMs, by directly observing and quantifying the solid/liquid phase evolution in time, the volumetric shrinkage, the presence of voids and the different phases that might occur during the phase-change process.

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.

Microextraction based on liquid-solid phase transition of benzoic acid: Extraction of statins from human urine followed by chromatographic analysis

Herein, a microextraction method was reported based on the liquid-solid phase transition of benzoic acid to quantify two statins, namely lovastatin and simvastatin in authentic human urine. The principle of the method is based on the phase transition of benzoic acid by altering the pH of the sample solution enabling efficient dispersion and phase separation in one step. Due to the moderate melting point of benzoic acid, its solidification is performed at ambient temperature without the need for sample cooling. Various experimental parameters that affect the performance of the analytes (i.e. extractant type and its concentration, acid type and concentration, and sample volume) have been examined and optimized. The method was validated based on the total error concept. For this purpose, accuracy profiles were constructed in the concentration range of 100–5000 ng mL−1 while β-expectation tolerance intervals fell within ±15% demonstrating that 95% of future results will not exceed the defined bias limits. The intra-day and inter-day method precision was less than 4.7% and 4.3% for both analytes, while the limit of detection was 15 ng mL−1 for both analytes. It was also proved that the usage of benzoic acid is advantageous in minimizing the potential inter-conversion of the analytes during the acidification step of the extraction procedure. The green potential of the proposed analytical scheme was examined based on Green Analytical Procedure index. The proposed sample pretreatment technique proved to be a valuable tool offering selectivity and rapidness. The developed method was used for the analysis of real human urine obtained after the administration of statin-based pharmaceutical formulations.

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.

Research on forming method of additive manufacturing of frozen sand mold

In order to promote the green and sustainable development of the foundry industry, it is necessary to further explore new methods and technologies for green foundry. This paper innovatively proposes a method of additive manufacturing of frozen sand mold, using water as the binder instead of resin binders for additive manufacturing in low-temperature environments, which effectively solves the problems of harmful gas emissions during the pouring process and the difficulty of direct recycling of molding sand, and realizes high-performance green casting of complex castings. In this paper, the liquid-solid phase transition mechanism of the binder for additive manufacturing of frozen sand mold and the change law of the normal temperature field and phase transition field of the pre-cooled powder bed porous medium at different temperatures are studied, and the process window of additive manufacturing of frozen sand mold is obtained, which provides a new green casting method for the foundry field.

Novel Latent Heat Storage Systems Based on Liquid Metal Matrices with Suspended Phase Change Material Microparticles.

Phase change materials (PCMs) are considered useful tools for efficient thermal management and thermal energy utilization in various application fields. In this study, a colloidal PCM-in-liquid metal (LM) system is demonstrated as a novel platform composite with excellent latent heat storage capability, high thermal and electrical conductivities, and unique viscoelastic properties. In the proposed formulation, eutectic Ga-In is utilized as a high-thermal-conductivity and high-fluidity liquid matrix in which paraffinic PCM microparticles with various solid-liquid phase transition temperatures are suspended as fillers. Good compatibility between the fillers and matrix is achieved by the nanosized inorganic oxides (titania) adsorbed at the filler-matrix interface; thus, the composite is produced via simple vortex mixing without tedious pre- or post-processing. The composite shows unique trade-off effects among various properties, i.e., elastic modulus, yield stress, density, thermal conductivity, and melting or crystallization enthalpy, which can be easily controlled by varying the contents of the suspended fillers. A Joule heating device incorporating the composite exhibits improved electrothermal performance owing to the synergy between the high electrical conductivity and latent heat storage capability of the composite. The proposed platform may be exploited for the rational design and facile manufacture of high-performance form-factor-free latent heat storage systems for various potential applications such as battery thermal management and flexible heaters.

Imaging Field-Driven Melting of a Molecular Solid at the Atomic Scale.

Solid-liquid phase transitions are basic physical processes, but atomically-resolved microscopy has yet to capture their full dynamics. We have developed a new technique for controlling the melting and freezing of self-assembled molecular structures on a graphene field-effect transistor (FET) that allows phase transition behavior to be imaged using atomically-resolved scanning tunneling microscopy. This is achieved by applying electric fields to F4 TCNQ-decorated FETs to induce reversible transitions between molecular solid and liquid phases at the FET surface. Nonequilibrium melting dynamics are visualized by rapidly heating the graphene substrate with electrical current and imaging the resulting evolution toward new 2D equilibrium states. An analytical model has been developed that explains observed mixed-state phases based on spectroscopic measurement of solid and liquid molecular energy levels. The observed non-equilibrium melting dynamics are consistent with Monte Carlo simulations. This article is protected by copyright. All rights reserved.

Observation of Solid-Liquid Phase Transitions of Brine Using the Far-Ultraviolet Charge-Transfer-to-Solvent Band.

Although determining the chemical states of salts and ions is critical in numerous fields, such as elucidating biological functions and maintaining food quality, the current direct observation methods are insufficient. We propose a spectral analysis method of directly observing the phase transitions of NaCl solutions using the changes in the charge-transfer-to-solvent band and the absorption band representing the first electron transition (Ã ← X̃) of H2O. The intensities of these bands may be observed using attenuated total reflection far-ultraviolet spectroscopy. According to the well-known phase diagram of aqueous NaCl, we observe spectral changes during freezing-thawing and may spectroscopically detect the phase transitions from liquid to mixed liquid-solid and solid phases, including eutectic crystals, in addition to their coexistence curves.

Solid-Liquid Crystal Biphasic Ferroelectrics with Tunable Biferroelectricity.

Ferroelectricity has been separately found in numerous solid and liquid crystal materials since its first discovery in 1920. However, a single material with biferroelectricity existing in both solid and liquid crystal phases is very rare, and the regulation of biferroelectricity has never been studied. Here, solid-liquid crystal biphasic ferroelectrics, cholestanyl 4-X-benzoate (4X-CB, X = Cl, Br, and I), which exhibits biferroelectricity in both the solid and liquid crystal phases, is presented. It is noted that the ferroelectric liquid crystal phase of 4X-CB is a cholesteric one, distinct from the ordinary chiral smectic ferroelectric liquid crystal phase. Moreover, 4X-CB shows solid-solid and solid-liquid crystal phase transitions, of which the transition temperatures gradually increase from Cl to Br to I substitution. The spontaneous polarization (Ps ) of 4X-CB in both solid and liquid crystal phases can also be regulated by different halogen substitutions, where the 4Br-CB has the optimal Ps because of the larger molecular dipole moment. To the authors' knowledge, 4X-CB is the first ferroelectric with tunable biferroelectricity, which offers a feasible case for the performance optimization of solid-liquid crystal biphasic ferroelectrics.

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.

Comprehensive Characterization of Kukui Nuts as Feedstock for Energy Production in Hawaii.

Fuel properties of oil-bearing kukui (Aleurites moluccana) nuts, a commonly found crop in Hawaii and tropical Pacific regions, were comprehensively studied to evaluate their potential for bioenergy production. Proximate and ultimate analyses, heating value, and elemental composition of the seed, shell, and de-oiled seed cake were determined across five sampling locations in Hawaii. The aged and freshly harvested kukui seeds were found to have similar oil contents, ranging from 61 to 64%wt. Aged seeds, however, have 2 orders of magnitude greater free fatty acids than those freshly harvested (50% vs 0.4%). The nitrogen content of the de-oiled kukui seed cake was found to be comparable to that of the soybean cake. Aging of kukui seeds can decrease the flashpoint temperature and increase the liquid-solid phase transition temperatures of kukui oil obtained. Mg and Ca are the major ash-forming elements present in the kukui shells, >80%wt of all metal elements detected, which may reduce deposition problems for thermochemical conversion in comparison with hazelnut, walnut, and almond shells. The study also revealed that kukui oil has similar characteristics to canola, indicating that it is well-suited for biofuel production.

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.

Free electron laser stochastic spectroscopy revealing silicon bond softening dynamics

Time-resolved x-ray emission/absorption spectroscopy (Tr-XES/XAS) is an informative experimental tool sensitive to electronic dynamics in materials, widely exploited in diverse research fields. Typically, Tr-XES/XAS requires x-ray pulses with both a narrow bandwidth and subpicosecond pulse duration, a combination that in principle finds its optimum with Fourier transform-limited pulses. In this work, we explore an alternative experimental approach, capable of simultaneously retrieving information about unoccupied (XAS) and occupied (XES) states from the stochastic fluctuations of broadband extreme ultraviolet pulses of a free electron laser. We used this method, in combination with singular-value decomposition and Tikhonov regularization procedures, to determine the XAS/XES response from a crystalline silicon sample at the ${L}_{2,3}$ edge, with an energy resolution of a few tens of meV. Finally, we combined this spectroscopic method with a pump-probe approach to measure structural and electronic dynamics of a silicon membrane. Tr-XAS/XES data obtained after photoexcitation with an optical laser pulse at 390 nm allowed us to observe perturbations of the band structure, which are compatible with the formation of the predicted precursor state of a nonthermal solid-liquid phase transition associated with a bond softening phenomenon.

Effect of filling configurations on melting heat transfer characteristic of phase change materials partially filled with metal foam

Metal foam embedded in phase change materials (PCM) has been shown to significantly improve the storage of latent heat thermal energy. Nonetheless the presence of metal foam also reduces natural convection, energy storage and increases cost. To address this issue, we modelled the internal flow of heat transfer in a PCM, paraffin wax, filled with metal foam at the top or the bottom, with filling height ratio ξ of 0.25, 0.5 and 0.75. The liquid-solid phase transition was studied by numerical simulations. Results show that natural convection in the pure paraffin wax area is higher, and melting time is shorter, in the bottom-filled than in the top-filled configuration. These differences increase with filling height ratio. By contrast, in metal foam-paraffin composite region, melting time is longer in the bottom-filled configuration due to heat loss. Interestingly, we observed significant changes in the interface shape of liquid-solid PCM at the junction of the pure paraffin and the metal foam-paraffin composite region. The liquid fraction formulas for different metal foam filled configurations are established as the function of Fourier number, Rayleigh number and filling height ratio.

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.

A phase transition approach to elucidate the propagation of shear waves in viscoelastic materials

In the field of acoustics, a medium has traditionally been considered a liquid if shear waves cannot propagate. For more complex liquids, such as those containing polymer chains or surfactant aggregates, this definition begins to be unclear. By adopting a rheological model-independent approach, this work investigated by means of dynamic elastography, the liquid–solid phase transitions in viscoelastic liquid media. When the storage shear modulus G′ dominated the loss shear modulus G″, a minimal shear wave attenuation frequency region was defined and the medium was considered solid. When G″ dominated G′, the shear waves were strongly attenuated and the medium was considered liquid. The investigated medium, an aqueous solution of xanthan gum, behaved as a bandpass filter with transition bands, showing liquid–solid–liquid behavior from low to high frequency. During these transitions bands, shear waves still propagated but highly attenuated. The limiting values where shear waves were no longer observed were identified as the low and high cutoff frequencies. Finally, the ability of various rheological models to predict the phase transition frequencies and describe the dispersion curves was tested. A three-element rheological model, the Jeffreys model, was required to accurately fit the experimental response of the medium at different concentrations over the entire frequency range. Shear wave propagation methods can overcome the technical limitations of traditional rheometry and explore higher frequencies, rarely investigated in viscoelastic liquids.

Oriented High Thermal Conductivity Solid-Solid Phase Change Materials for Mid-Temperature Solar-Thermal Energy Storage.

As the global energy crisis intensifies, the development of solar energy has become a vital area of focus for many nations. The utilization of phase change materials (PCMs) for photothermal energy storage in the medium temperature range holds great potential for various applications, but their conventional forms face several challenges. For instance, the longitudinal thermal conductivity of photothermal PCMs is inadequate for effective heat storage on the photothermal conversion surface, and there is a risk of leakage due to repeated solid-liquid phase transitions. Here, we report a solid-solid phase change material, tris(hydroxymethyl)aminomethane (TRIS), which has a phase change temperature of 132 °C in the medium temperature range, enabling high-grade and stable solar energy storage. To overcome the low thermal conductivity problem, we propose a large-scale production of oriented high thermal conductivity composites by compressing a mixture of TRIS and expanded graphite (EG) using the pressure induction method to create in-plane highly thermally conductive channels. Remarkably, the resulting phase change composites (PCCs) exhibit a directional thermal conductivity of 21.3 W/(m·K). Furthermore, the high phase change temperature (132 °C) and large phase change entropy (213.47 J/g) enable a large-capacity high-grade thermal energy to be used. The developed PCCs, when combined with selected photo-absorbers, exhibit efficient integration of solar-thermal conversion and storage. Additionally, we also demonstrated a solar-thermoelectric generator device with an energy output of 93.1 W/m2, which is close to the power of photovoltaic systems. Overall, this work provides a technological route to the large-scale fabrication of mid-temperature solar energy storage materials with high thermal conductivity, high phase change enthalpy, and no risk of leakage, and also offers a potential alternative to photovoltaic technology.