Supercooled State Research Articles

Understanding the relationship between structural and dynamic properties in binary Mg-Al metallic liquids from molecular dynamics simulations

The structure and dynamics of the Mg-Al alloy for the different compositions were investigated using the embedded atom method (EAM) of molecular dynamics modeling. The results found that the icosahedral-like, mixed, and crystal-like increases with the temperature during the cooling process. When the temperature reaches the glass transition temperature (Tg) the last two types of clusters decrease with the temperature. The temperature Tg was determined using the Wendt-Abraham parameter, which found that it increases with increases in the fraction of Al. Investigations also revealed that the activation energy (Ea) decreases at higher temperatures and increases at temperatures below Tg. Additionally, viscosity was computed using the Vogel–Fulcher–Tammann (VFT) equation, showing a decrease in temperature in the supercooled liquid state. Moreover, an increase in the fraction of Al resulted in reduced fragility of the liquids.

Temperature dependence of spatial nanoheterogeneities of shear modulus in supercooled glycerol.

The boson peak in the terahertz vibrational spectrum carries information about nano-heterogeneities in the shear modulus in glass formers. Its evolution upon heating or cooling in a supercooled liquid state may shed light on the temperature dependence of heterogeneities. For this purpose, an analysis of the light scattering spectra of supercooled glycerol in the spectral range of the boson peak and fast relaxation was carried out and the parameters of the boson peak in the temperature range 180-330K were determined. The temperature dependent frequency of the boson peak was then expressed in terms of the mean-square amplitude of the shear modulus fluctuations. This was done using the heterogeneous elasticity theory in combination with the perturbation theory on small fluctuations and Ioffe-Regel criterion for transverse vibrations in glass formers. The contribution of structural relaxation effects to phonon damping becomes significant with increasing temperature. It is shown here that structural relaxation largely determines the temperature dependence of the mean-square fluctuations of the shear modulus at high temperatures. By solving the inverse problem, the temperature dependence of shear modulus fluctuations was obtained. It shows a rapid decrease above ∼250K with a linear extrapolation going to zero at the so-called Arrhenius temperature TA = 350K. Comparison with literature data on the Landau-Placzek ratio shows that they have a similar temperature dependence at T < TA, which is explained by the appearance of nanometer scale spatial heterogeneities below TA. This is confirmed by the temperature dependence of the amplitude of the boson peak.

Formation of Self-Healing Granular Eutectogels through Jammed Carbopol Microgels in Supercooled Deep Eutectic Solvent.

Typically, gel-like materials consist of a polymer network structure in a solvent. In this work, a gel-like material is developed in a deep eutectic solvent (DES) without the presence of a polymer network, achieved simply by adding microgels. The DES is composed of choline chloride and citric acid and remains stably in a supercooled state at room temperature, exhibiting Newtonian fluid behavior with high viscosity. When the microgel (Carbopol) concentration exceeds 2 wt %, the DES undergoes a transition from a liquid to a soft gel state, characterized as a granular eutectogel. The soft gel characteristics of eutectogels exhibit a yield stress, and their storage moduli exceed the loss moduli. The yield stress and storage moduli are observed to increase with increasing microgel concentration. In contrast, the ion conductivity decreases with increasing microgel concentration but eventually levels off. Because the eutectogel can dissolve completely in excess water, it is a physical gel-like material, attributed to the densely packed structure of microgels in the supercooled DES. Due to the absence of networks, the granular eutectogel has the capability to self-heal simply by being pushed together after being cut into two pieces.

Study on effects of anti-freeze protein and polyvinyl alcohol on the production and flow behavior of ice slurry

Ice slurry is a promising functional fluid with high thermal energy density and high heat transfer rate. However, the agglomeration of the ice particles in flowing ice slurry can cause blocking of tubes. In this study, anti-freeze protein (AFP) and polyvinyl alcohol (PVA) were selected as additives to prevent the agglomeration of ice particles in ice slurry. Ice slurry was generated using the release of the supercooled state of 3 mass% NaCl solution containing the additives. The size of the ice particles in the ice slurry was observed, and the average area of the ice particles was evaluated to reveal the effects of the additives on the ice particle size. Furthermore, the flow behavior of the ice slurry in a tube was observed, and the effects of the additives on the flow behavior and prevention of the agglomeration of the ice particles were evaluated experimentally. It was found that the average area decreased with increasing concentration of the additives, and the effect of AFP on the average area was particularly significant. In the case of without the additives, the ice particles flowed in the tube while the ice particles agglomerated. On the other hand, the ice particles in the ice slurry with the additives flowed without agglomeration in the tube, especially in the case of AFP addition. It was found that AFP prevented the agglomeration of the ice particles in the ice slurry flow. Moreover, the ice slurries with AFP show the significant tendency for pseudo-plastic fluid.

Compressibility, diffusivity, and elasticity in relationship with ionic conduction: An atomic scale description of densified Li2S${\rm Li}_2{\rm S}$–SiS2${\rm SiS}_2$ glasses

AbstractWe examine the dynamic and ionic properties of a typical sulfide glass electrolyte 50–50 using molecular dynamics simulations and a previously parameterized force‐field able to describe both the crystalline phase and the corresponding glass. We especially focus on the effect of moderate pressures on the glassy and supercooled state since the design of all‐solid state batteries use molding conditions at moderate pressures in order to achieve contact between the electrolyte and the electrodes. The behavior of the conductivity with pressure permits to define an activation volume and to infer the role of compressibility and diffusivity, the latter contributing dominantly to ionic conduction, whereas temperature does not seem to impact the structural properties. These features are linked with the underlying dynamics of the Li ions as studied here by computing the longitudinal and transversal atomic species current correlations. The resulting elasticity is found to be close to experimental values.

Experimental analysis of freezing desalination using gravity and centrifugal methods with economic evaluation of coupled freezing desalination and ice storage system

This study conducted experiments to compare the desalination efficiency of gravity and centrifugal desalination methods for freezing desalination, showing the superiority of centrifugal desalination. Moreover, through experiments on supercooled water production, it was determined that supercooled water can operate stably at an evaporator temperature of −4.5 °C, and its supercooling state can be released using ultrasound. Based on the experimental results, a novel system that combines freezing desalination with ice storage is proposed. The proposed system utilizes supercooled water for ice production and centrifugal post-treatment, using desalinated ice as a cold storage medium to integrate desalination and ice storage. The proposed system showed a 30 % lower total capital cost compared to conventional systems, with a payback period of 38.18 % lower than conventional system (5.42 years). Additionally, the system demonstrated optimal economic performance when utilizing 80 % of its ice storage capacity, with a payback period of 3.38 years, contrasting with 7.62 years when utilizing 20 % storage capacity. The application of this system in four regions with varying peak and off-peak electricity prices, including Guangdong, Fujian, Hainan, and, France revealed that the system demonstrates greater economic viability in areas with significant disparities in electricity pricing.

Diffusion proxies reveal the dynamic process in supercooled and glassy lithium diborate

Understanding the effective diffusion coefficient (D) is crucial for describing atomic transport during crystal nucleation in supercooled liquids and glasses. However, pinpointing the key structural units driving crystallization in intricate, multicomponent glass-formers remains a challenge. This study presents a novel analysis of lithium diborate (Li₂O·2 B₂O₃ - LB₂) crystallization in supercooled and glassy states by using available viscosity and crystallization data for samples of the same batch. An original key feature is that the nucleation rates were measured using a single-stage rather than the traditional double-stage heat treatment. We compared three proxies for D: Dη obtained from viscosity, DU derived from crystal growth rates, and Dτ estimated from nucleation time-lags. Our analysis revealed that at deep supercoolings, below the glass transition temperature, DU and Dτ yield similar steady-state nucleation rate estimates, which significantly exceed those predicted by using Dη (the most frequently used diffusion proxy). This result suggests that the atomic jumps governing crystal nucleation may be comparable to those in crystal growth, but distinct from those associated with cooperative rearrangements controlling viscous flow. Additionally, the estimated kinetic spinodal temperature (Tks) is above the Kauzmann temperature Tk, implying that crystal nucleation precedes relaxation to the supercooled liquid state, circumventing the entropy paradox and corroborating recent MD simulations for other substances. These findings are valuable for refining theoretical models of crystal nucleation and highlight the complexities of the glassy state.

Supercooled erythritol for high-performance seasonal thermal energy storage

Seasonal storage of solar thermal energy through supercooled phase change materials (PCM) offers a promising solution for decarbonizing space and water heating in winter. Despite the high energy density and adaptability, natural PCMs often lack the necessary supercooling for stable, long-term storage. Leveraging erythritol, a sustainable mid-temperature PCM with high latent heat, we introduce a straightforward method to stabilize its supercooling by incorporating carrageenan (CG), a bio-derived food thickener. By improving the solid-liquid interfacial energy with the addition of CG the latent heat of erythritol can be effectively locked at a very low temperature. We show that the composite PCM can sustain an ultrastable supercooled state below −30 °C, which guarantees no accidental loss of the latent heat in severe cold regions on Earth. We further demonstrate that the common ultrasonication method can be used as the key to unlocking the latent heat stored in the CG-thickened erythritol, showing its great potential to serve as a high-performance, eco-friendly PCM for long-term seasonal solar energy storage.

Frost fighters: unveiling the potential of microbial antifreeze proteins in biotech innovation.

Polar environments pose extreme challenges for life due to low temperatures, limited water, high radiation, and frozen landscapes. Despite these harsh conditions, numerous macro and microorganisms have developed adaptive strategies to reduce the detrimental effects of extreme cold. A primary survival tactic involves avoiding or tolerating intra and extracellular freezing. Many organisms achieve this by maintaining a supercooled state by producing small organic compounds like sugars, glycerol, and amino acids, or through increasing solute concentration. Another approach is the synthesis of ice-binding proteins, specifically antifreeze proteins (AFPs), which hinder ice crystal growth below the melting point. This adaptation is crucial for preventing intracellular ice formation, which could be lethal, and ensuring the presence of liquid water around cells. AFPs have independently evolved in different species, exhibiting distinct thermal hysteresis and ice structuring properties. Beyond their ecological role, AFPs have garnered significant attention in biotechnology for potential applications in the food, agriculture, and pharmaceutical industries. This review aims to offer a thorough insight into the activity and impacts of AFPs on water, examining their significance in cold-adapted organisms, and exploring the diversity of microbial AFPs. Using a meta-analysis from cultivation-based and cultivation-independent data, we evaluate the correlation between AFP-producing microorganisms and cold environments. We also explore small and large-scale biotechnological applications of AFPs, providing a perspective for future research.

Theoretical and experimental analysis of sea ice centrifugal desalination and supercooled water production for slurry ice

This study presents a comprehensive investigation of centrifugal desalination of sea ice and the production of slurry ice from supercooled water. A mathematical model for centrifugal desalination was established and validated through experiments. The results displayed a high level of accuracy in both the theoretical and experimental analyses, with an average goodness of fit of approximately 0.94. An experimental platform is established to produce supercooled water, using different types of water as ice-making solutions. The slurry ice is more suitable for centrifugal desalination than solid ice, and it can be obtained by disrupting the supercooled state of supercooled water, with finer ice crystals produced through ultrasonic supercooling release compared to natural methods. Decreasing the refrigerant temperature benefits enhancing the supercooling degree while compromising the stability of supercooled water generation. The stability is investigated with variations in refrigerant temperature to generate a solution temperature 2.0 °C higher than the refrigerant. When the supercooling degree is 1.0 °C, all of these solutions have a high stability of 80 %, however, it becomes worse as the supercooling degree increases. At the supercooling degree of 2.0 °C, saltwater has the highest stability of only 35 %, and seawater has the lowest stability of 15% due to its complicated composition. This phenomenon also reveals that conducting experiments using saline solution instead of seawater can lead to significant misleading effects. Additionally, the impact of flow rate on the supercooling degree is investigated, showing a minor influence.

Multibubble sonoluminescence in supercooled water.

Cavitation in supercooled water has been induced by the short ultrasound pulses of an ultrasonic horn driven at 20kHz. The cavitation during the ultrasonic pulses and occasionally the crystallization events thereafter have been imaged by a high-speed camera. The probability of ice crystallization in dependence on the pulse duration and temperature showed a high chance for the water to remain liquid if sufficiently short bursts of moderate acoustic power were applied. This regime has been used for the assessment of sonoluminescence (SL) from the generated cavitation bubbles in the supercooled liquid state. To this end, light emitting events were summed up over a number of ultrasonic pulses by an image intensifier. SL appeared mostly directly under the tip of the ultrasonic horn and sometimes also a few millimeters below the tip. The intensity of SL events showed a slight rise for a decrease in temperature, i.e., for an increase in supercooling. This behavior is in accord with the SL dependence on temperature above the freezing point and might be attributed to a further lowering of vapor pressure. An increase in the bubble collapse peak temperature for increased supercooling is calculated on the basis of spherical bubble model calculations, which supports the findings. The simulations predict further that the peak temperature will fall off again beyond a certain supercooling level.

Rheological Behavior of a New Amorphous Alloy (Al74Cu16Mg10)99,7Zr0.3

A new amorphous alloy (Al74Cu16Mg10)99,7Zr0.3 was prepared the applying a melt-spinning technique. Temperature dependence of viscosity of the alloy was determined using data from a PerkinElmer TMS2 thermo-mechanical analyzer processed according to a methodology based on the Free Volume Model (FVM). The strength of the alloy was calculated according to the Yang equation and the glass-forming ability was calculated according to the values of the Angell index mA. The activation energy of crystallization and the activation energy of the glass transition were computed using data from differential scanning calorimetry and thermomechanical experiments respectively. The activation energy of crystallization Еx = 168 ± 3.7 kJ/mol, was found to be higher than the activation energy of the glass transition Еg = 156 ± 1.4 kJ/mol, which means a dominant contribution of the atomic transport barrier, compared to the nucleation barrier. The relatively high temperature interval of the supercooled melt state Tx-Tg = 32 K and the low viscosity values in the same range ƞ(Тg) = 3.40E + 11 Pa.s and ƞ(Тx) = 1.87E + 10 Pa.s would allow thermomechanical treatment of the alloy in the temperature range of supercooled melt.

Normal-to-Supercooled Liquid Transition in Molecular Glass-Formers: A Hidden Structural Transformation Fuelled by Conformational Interconversion.

Molecular dynamics and transport coefficients change significantly around the so-called Arrhenius crossover in glass-forming systems. In this article, we revisit the dynamic processes occurring in a glass-forming macrocyclic crown thiaether MeBzS2O above its glass transition, revealing two crossover temperatures: TB at 309 and TA at 333 K. We identify the second one as the Arrhenius crossover that is closely related to the normal-to-supercooled liquid transition in this compound. We show that the transformation occurring at this point goes far beyond molecular dynamics (where the temperature dependence of structural relaxation times changes its character from activation-like to super-Arrhenius), being reflected also in the internal structure and diffraction pattern. In this respect, we found a twofold local organization of the nearest-neighbor molecules via weak van der Waals forces, without the formation of any medium-range order or mesophases. The nearest surrounding of each molecule evolves structurally in time due to the ongoing fast conformational changes. We identify several conformers of MeBzS2O, demonstrating that its lowest-energy conformation is preferred mainly at lower temperatures, i.e., in the supercooled liquid state. Its increased prevalence modifies locally the short-range intermolecular order and promotes vitrification. Consequently, we indicate that the Arrhenius transition is fuelled rather by conformational changes in this glass-forming macrocyclic crown thiaether, which is a different scenario from the so-far existing concepts. Our studies combine broadband dielectric spectroscopy (BDS), X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, molecular dynamics (MD) simulations, and density functional theory (DFT) calculations.

Effect of long-term supercooling preservation using a stepwise algorithm on the freshness of kimchi cabbage

Kimchi cabbage is a Korean traditional fermented vegetable that is rich in nutrients and probiotics. Temperature changes caused microbial growth adversely affect the quality of kimchi. Therefore, controlling the preservation temperature is important to prevent over-fermentation of kimchi. Supercooling has emerged as an alternative storage method; however, maintaining the supercooled state of food is challenging. In this study, a stepwise cooling algorithm for supercooling preservation was developed and applied. All samples were maintained in a supercooled state, and no ice nucleation was detected. Assessments of CO2 content, pH, and titratable acidity revealed that supercooled samples exhibited more delayed fermentation than refrigerated samples. However, moisture content and hardness of the unfrozen (refrigerated and supercooled) samples were not significantly different. Microbial analysis and community composition indicated that the supercooling treatment delayed kimchi fermentation by approximately three months. Conclusively, supercooling is effective for maintaining the freshness of kimchi cabbage during long-term storage. This study contributes to the optimization of kimchi preservation strategies, offering potential benefits for both consumers and producers in terms of product quality, shelf life, and food safety.

Phase Transition Thermodynamics of 1,3,5-Tris-(α-naphthyl)benzene: Theory and Experiment.

1,3,5-Tris-(α-naphthyl)benzene is an organic non-electrolyte with notable stability of an amorphous phase. Its glassy and supercooled liquid states were previously studied by spectroscopic and calorimetric methods. Despite the continuing interest in its amorphous state and, particularly, vapor-deposited glasses, the thermodynamic parameters of the vaporization of 1,3,5-tris-(α-naphthyl)benzene have not been obtained yet. Likewise, the reliable evaluation of the thermodynamic parameters of fusion below the melting point, required to establish the thermodynamic state of its glass, is still an unsolved problem. In this work, the heat capacities of crystalline and liquid phases, the temperature dependence of the saturated vapor pressures, fusion and vaporization enthalpies were determined using differential and fast scanning calorimetry and were verified using the estimates based on solution calorimetry. The structural features of 1,3,5-tris-(α-naphthyl)benzene are discussed based on the computations performed and the data on the molecular refractivity. The consistency between the values obtained by independent techniques was demonstrated.

Structure and Properties of Na2S-SiS2-P2S5-NaPO3 Glassy Solid Electrolytes.

In the development of sodium all-solid-state batteries (ASSBs), research efforts have focused on synthesizing highly conducting and electrochemically stable solid-state electrolytes. Glassy solid electrolytes (GSEs) have been considered very promising due to their tunable chemistry and resistance to dendrite growth. For these reasons, we focus here on the atomic-level structures and properties of GSEs in the compositional series (0.6-0.08y)Na2S + (0.4 + 0.08y)[(1 - y)[(1 - x)SiS2 + xPS5/2] + yNaPO3] (NaPSiSO). The mechanical moduli, glass transition temperatures, and temperature-dependent conductivity were determined and related to their short-range order structures that were determined using Raman, Fourier transform infrared, and 31P and 29Si magic angle spinning nuclear magnetic resonance spectroscopies. In addition, the conductivity activation energies were modeled using the Christensen-Martin-Anderson-Stuart model. These GSEs appear to be highly crystallization-resistant in the supercooled liquid region where no measurable crystallization below 450 °C could be observed in differential scanning calorimetry studies. Additionally, these GSEs were found to be highly conducting, with conductivities on the order of 10-5 (Ω cm)-1 at room temperature, and processable in the supercooled state without crystallization. For all these reasons, these NaPSiSO GSEs are considered to be highly competitive and easily processable candidate GSEs for enabling sodium ASSBs.

Tuning the Physical State of Aripiprazole by Mesoporous Silica.

The main purpose of our studies is to demonstrate that commercially available mesoporous silica (MS) can be used to control the physical state of aripiprazole (ARP). The investigations performed utilizing differential scanning calorimetry and broadband dielectric spectroscopy reveal that silica can play different roles depending on its concentration in the system with amorphous ARP. At low MS content, it activates recrystallization of the active pharmaceutical ingredient and supports forming the III polymorphic form of ARP. At intermediate MS content (between ca. 27 and 65 wt %), MS works as a recrystallization inhibitor of ARP. At these concentrations, the formation of III polymorphic form is no longer favorable; therefore, it is possible to use this additive to obtain ARP in either IV or X polymorphic form. At the same time, employing MS in concentrations >65 wt % amorphous form of ARP with high physical stability can be obtained. Finally, regardless of the polymorphic form it crystallizes into, each composite is characterized by the same temperature dependence of relaxation times in the supercooled and glassy states.

Ionic Conductivity of a Lithium-Doped Deep Eutectic Solvent: Glass Formation and Rotation-Translation Coupling.

Deep eutectic solvents with admixed lithium salts are considered as electrolytes in electrochemical devices, such as batteries or supercapacitors. Compared to eutectic mixtures of hydrogen-bond donors and lithium salts, their raw-material costs are significantly lower. Not much is known about glassy freezing and rotational-translation coupling of such systems. Here, we investigate these phenomena by applying dielectric spectroscopy to the widely studied deep eutectic solvent glyceline, to which 1 and 5 mol % LiCl were added. Our study covers a wide temperature range, including a deeply supercooled state. The temperature dependences of the detected dipolar reorientation dynamics and ionic direct current (dc) conductivity reveal the signatures of glassy freezing. In comparison to pure glyceline, the lithium admixture leads to a reduction of ionic conductivity, which is accompanied by a reduction of the rotational dipolar mobility. However, this reduction is much smaller than that for deep eutectic solvents (DESs), where one main component is lithium salt, which we trace back to the lower glass-transition temperatures of lithium-doped DESs. In contrast to pure glyceline, the ionic and dipolar dynamics become increasingly decoupled at low temperatures and obey a fractional Debye-Stokes-Einstein relation, as previously found in other glass-forming liquids. The obtained results demonstrate the relevance of decoupling effects and glass transition to the enhancement of the technically relevant ionic conductivity in such lithium-doped DESs.

Quantitative Investigation of Intestinal Drug Absorption Enhancement by Drug-Rich Nanodroplets Generated via Liquid-Liquid Phase Separation.

Drug-rich droplets formed through liquid-liquid phase separation (LLPS) have the potential to enhance the oral absorption of drugs. This can be attributed to the diffusion of these droplets into the unstirred water layer (UWL) of the gastrointestinal tract and their reservoir effects on maintaining drug supersaturation. However, a quantitative understanding of the effect of drug-rich droplets on intestinal drug absorption is still lacking. In this study, the enhancement of intestinal drug absorption through the formation of drug-rich droplets was quantitatively evaluated on a mechanistic basis. To obtain fenofibrate (FFB)-rich droplets, an amorphous solid dispersion (ASD) of FFB/hypromellose (HPMC) was dispersed in an aqueous medium. Physicochemical characterization confirmed the presence of nanosized FFB-rich droplets in the supercooled liquid state within the FFB/HPMC ASD dispersion. An in situ single-pass intestinal perfusion (SPIP) assay in rats demonstrated that increased quantities of FFB-rich nanodroplets enhanced the intestinal absorption of FFB. The effective diffusion of FFB-rich nanodroplets through UWL would partially contribute to the improved FFB absorption. Additionally, confocal laser scanning microscopy (CLSM) of cross sections of the rat intestine after the administration of fluorescently labeled FFB-rich nanodroplets showed that these nanodroplets were directly taken up by small intestinal epithelial cells. Therefore, the direct uptake of drug-rich nanodroplets by the small intestine is a potential mechanism for improving FFB absorption in the intestine. To quantitatively evaluate the impact of FFB-rich droplets on the FFB absorption enhancement, we determined the apparent permeabilities of the FFB-rich nanodroplets and dissolved FFB based on the SPIP results. The apparent permeability of the FFB-rich nanodroplets was 110-130 times lower than that of dissolved FFB. However, when the FFB-rich nanodroplet concentration was several hundred times higher than that of dissolved FFB, the FFB-rich nanodroplets contributed significantly to FFB absorption improvement. The present study highlights that drug-rich nanodroplets play a direct role in enhancing drug absorption in the gastrointestinal tract, indicating their potential for further improvement of oral absorption from ASD formulations.

Fragility and Tendency to Crystallization for Structurally Related Compounds.

The present study was designed to investigate the physical stability of three organic materials with similar chemical structures. The examined compounds revealed completely different crystallization tendencies in their supercooled liquid states and were classified into three distinct classes based on their tendency to crystallize. (S)-4-Benzyl-2-oxazolidinone easily crystallizes during cooling from the melt; (S)-4-Benzylthiazolidine-2-thione does not crystallize during cooling from the melt, but crystallizes easily during subsequent reheating above Tg; and (S)-4-Benzyloxazolidine-2-thione does not crystallize either during cooling from the melt or during reheating. Such different tendencies to crystallize are observed despite the very similar chemical structures of the compounds, which only differ in oxide or sulfur atoms in one of their rings. We also studied the isothermal crystallization kinetics of the materials that were shown to transform into a crystalline state. Molecular dynamics and thermal properties were thoroughly investigated using broadband dielectric spectroscopy, as well as conventional and temperature-modulated differential scanning calorimetry in the wide temperature range. It was found that all three glass formers have the same dynamic fragility (m = 93), calculated directly from dielectric structural relaxation times. This result verifies that dynamic fragility is not related to the tendency to crystallize. In addition, thermodynamic fragility predictions were also made using calorimetric data. It was found that the thermodynamic fragility evaluated based on the width of the glass transition, observed in the temperature dependence of heat capacity, correlates best with the tendency to crystallize.