Liquid-like State Research Articles

Experimental observations of marginal criticality in granular materials

SignificanceAmorphous materials, such as grains, foams, colloids, and glasses, are ubiquitous in nature and our daily life. They can undergo glass transitions or jamming transitions to obtain rigidity either by fast quench or compression, but show subtle changes in the structures compared to the liquid states or liquid-like states. Recent progress on the first-principle replica theory unifies the glass transition and the jamming transition and points out the marginal phase with fractal free-energy landscape within the stable glass phase. Independently, marginal stability analysis predicts the relations between the exponents of the marginal phase. Here, we perform experiments with photoelastic disks and provide direct evidence of these theories in real-world amorphous materials.

FuzDrop on AlphaFold: visualizing the sequence-dependent propensity of liquid-liquid phase separation and aggregation of proteins.

Many proteins perform their functions within membraneless organelles, where they form a liquid-like condensed state, also known as droplet state. The FuzDrop method predicts the probability of spontaneous liquid–liquid phase separation of proteins and provides a sequence-based score to identify the regions that promote this process. Furthermore, the FuzDrop method estimates the propensity of conversion of proteins to the amyloid state, and identifies aggregation hot-spots, which can drive the irreversible maturation of the liquid-like droplet state. These predictions can also identify mutations that can induce formation of amyloid aggregates, including those implicated in human diseases. To facilitate the interpretation of the predictions, the droplet-promoting and aggregation-promoting regions can be visualized on protein structures generated by AlphaFold. The FuzDrop server (https://fuzdrop.bio.unipd.it) thus offers insights into the complex behavior of proteins in their condensed states and facilitates the understanding of the functional relationships of proteins.

Flexural Models for Vacuum-Packed Particles as a Variable-Stiffness Mechanism in Smart Structures

Vacuum-packed particle (VPP) systems have been recently used in the development of smart structures due to their ability to actively change material stiffness through the mechanism of granular jamming. By altering the strength of the vacuum pressure applied to the particles, the material can be proportionally and reversibly transitioned from a liquidlike low-stiffness state to a stiff state. The ability to control material stiffness in this way opens up different possibilities for the design of morphing and smart structures by allowing them to soften during deformation to reduce actuation energy requirements and to then stiffen once the desired shape has been achieved to provide a zero-energy holding mechanism. The following research describes two useful models that predict the mechanical response of VPP beams under flexural loading. Firstly, four-point bending tests with digital image correlation strain mapping are performed in order to measure the axial and transverse strains in a bending beam made from vacuum-packed particles. The test results show a nonlinear mechanical response, including a change in beam thickness with deformation, that motivated an analytical model of the structure incorporating a nonlinear material stress model based on the Mohr-Coulomb failure envelope. In addition, finite-element simulations are implemented using a Johnson-Cook model extension to predict the response under loading of three-dimensional beam elements at different vacuum pressure levels. Lastly, the models are compared to the experimental results, indicating good agreement. Both methods are shown to be useful for predicting the variation of stiffness of vacuum-packed particle beams.

Purine biosynthetic enzymes assemble into liquid-like condensates dependent on the activity of chaperone protein HSP90

Enzymes within the de novo purine biosynthetic pathway spatially organize into dynamic intracellular assemblies called purinosomes. The formation of purinosomes has been correlated with growth conditions resulting in high purine demand, and therefore, the cellular advantage of complexation has been hypothesized to enhance metabolite flux through the pathway. However, the properties of this cellular structure are unclear. Here, we define the purinosome in a transient expression system as a biomolecular condensate using fluorescence microscopy. We show that purinosomes, as denoted by formylglycinamidine ribonucleotide synthase granules in purine-depleted HeLa cells, are spherical and appear to coalesce when two come into contact, all liquid-like characteristics that are consistent with previously reported condensates. We further explored the biophysical and biochemical means that drive the liquid–liquid phase separation of these structures. We found that the process of enzyme condensation into purinosomes is likely driven by the oligomeric state of the pathway enzymes and not a result of intrinsic disorder, the presence of low-complexity domains, the assistance of RNA scaffolds, or changes in intracellular pH. Finally, we demonstrate that the heat shock protein 90 KDa helps to regulate the physical properties of the condensate and maintain their liquid-like state inside HeLa cells. We show that disruption of heat shock protein 90 KDa activity induced the transformation of formylglycinamidine ribonucleotide synthase clusters into more irregularly shaped condensates, suggesting that its chaperone activity is essential for purinosomes to retain their liquid-like properties. This refined view of the purinosome offers new insight into how metabolic enzymes spatially organize into dynamic condensates within human cells.

Molecular Aggregation Dynamics via a Liquid-like Cluster Intermediate during Heterogeneous Evaporation as Revealed by Hyperspectral Camera Fluorescence Imaging.

A hyperspectral camera (HSC) is a camera with great potential to obtain spectral information at each pixel, together with spatial imaging. HSC fluorescence imaging enables the molecular aggregation dynamics of the evaporative crystallization process to be followed in real-time. The key intermediate liquid-like cluster state for the two-step nucleation mechanism is visualized by the fluorescence color changes of mechanochromic luminescent dibenzoylmethanatoboron difluoride derivatives. Three types of emissive species (Crystal, BG-aggregates, and Amorphous) are generated from monomers in solution (low order and density) via liquid-like cluster (high density and low order) during solvent evaporation. These emissive species have partially different aggregated states based on fluorescence decay and fluorescence excitation spectral measurements. In terms of crystallization dynamics, our results indicate that it is important not only to generate supersaturated states but also to maintain the survival time of the liquid-like cluster. Moreover, we demonstrate that HSC fluorescence imaging can be a powerful tool for visualizing heterogeneous molecular aggregation processes.

Entropy change at viscous flow of dispersive systems with a phase transition in their particles

Based on the compensation effect, a method has been developed for the correct calculation of entropy changes at viscous flow of liquid dispersed systems using the Eyring equation. At temperature range of 313± 10 K in dispersed systems with a liquid-like state of dispersed phase particles the presence of a specific phase transition is substantiated, at which changes in enthalpy and entropy undergo a jump in these systems. Keywords: Eyring's equation, dispersed systems, phase transition.

Изменения энтропии при вязком течении дисперсных систем с фазовым переходом в их частицах

Based on the compensation effect, a method has been developed for the correct calculation of entropy changes at viscous flow of liquid dispersed systems using the Eyring equation. At temperature range of 313 ± 10 K in dispersed systems with a liquid-like state of dispersed phase particles the presence of a specific phase transition is substantiated, at which changes in enthalpy and entropy undergo a jump in these systems.

On the effect of pseudo-condensation on the design and performance of supercritical CO[formula omitted] gas chillers

Supercritical CO2 is used as a work fluid in both heat pump and power cycles. As a fluid at supercritical pressure is heated or cooled, it may undergo a smooth transition from a liquid-like state to a gas-like state or vice versa. This transition, during which the thermophysical properties vary sharply with temperature, can be referred to as pseudo- boiling or condensation. Using both analytical and numerical methods, it is shown that pseudoboiling theory helps to understand how the unique heat transfer characteristics of a supercritical fluid affect heat exchanger performance and design, in particular a gas chiller. Due to pseudo-condensation, classical approaches such as the ε−NTU and LMTD methods fail when rating or designing a sCO2 gas chiller. Using the heat of pseudo-condensation, the heat exchanger can be regarded to consist of a pre-cooler, condenser and a super-cooler. By further dividing the pre-cooler and super-cooler into two parts and subsequently applying the ε−NTU method per part yields very good results with respect to both the prediction of required size and entropy generation for various operating parameters. The influence of pseudo-condensation is reduced at higher pressures and is negligible when the structural energy required for the transition from liquid-like to a gas-like state is smaller than the required thermal energy required. It is shown that the local effectiveness of the condenser part is reduced (more so than the other parts) when the heat capacity ratio RC is varied from unity to less than unity, leading to enhanced irreversibility due to pseudo-condensation. Furthermore, the enhanced and deteriorated heat transfer regime (such as when a sCO2 downward flow is cooled) lead to significantly different required heat exchanger sizes. Finally, through the use of Monte Carlo simulations, it shown that the uncertainty of a Nusselt correlation complicates designing heat exchangers in which pseudo-condensation occurs. The simulations show that heat exchangers should be 50% larger than the size that is predicted using a Nusselt correlation if the design performance is to be ensured.

Structural and dynamical properties of 13-atom Cu–Co mixed clusters

In this paper, the geometric structures and the melting-like processes of the 13-atom pure copper, pure cobalt cluster and their 13-atom mixed clusters are investigated and compared by the molecular dynamics method. The calculation shows that the pure copper and cobalt clusters have the standard icosahedral structures and the mixed clusters take on the deformed icosahedral structures. The quantitative analysis shows that the deformations are slight. Moreover, an element similarity function is introduced by which the contribution of the compositions of the clusters to the deformation of the mixed clusters is analyzed and discussed. With the increase of the temperature, the migrating and recombination of the atoms on the surface of the clusters are observed, indicating the starting of the transition from solid-like to liquid-like state for the clusters. Through the calculating of the relative root-mean-squared pair separation fluctuation and monitoring the dynamical structures of the clusters, it is found that the mixed clusters experience a multi-step process in the transition.

Polymer Architecture Effects on Poly(N,N-Diethyl Acrylamide)-b-Poly(Ethylene Glycol)-b-Poly(N,N-Diethyl Acrylamide) Thermoreversible Gels and Their Evaluation as a Healthcare Material.

Thermoreversible gels which transition between liquid-like and solid-like states when warmed have enabled significant novel healthcare technologies. Poly(N,N-diethyl acrylamide) (PDEA) is a thermoresponsive polymer which can be used as a trigger to form thermoreversible gels, however its use in these materials is limited and crucial design principles are unknown. Herein ABA copolymers with the structure PDEA-b-poly(ethylene glycol) (PEG)-b-PDEA are synthesized to give four block copolymers with varied molecular weight of PDEA and PEG blocks. Rheometry on solutions of the block copolymers reveals that high molecular weight PEG blocks are required to form thermoreversible gels with predominantly solid-like behavior. Furthermore, small-angle X-ray scattering elucidates clear differences in the nanostructure of the copolymer library which can be linked to distinct rheological behaviors. A thermoreversible gel formulation based on PDEA (20kDa)-b-PEG (10kDa)-b-PDEA (20kDa) is designed by optimizing the polymer concentration and ionic strength. It is found that the gel is mucoadhesive, stable, and non-toxic, as well as giving controlled release of a hydrophobic drug. Overall, this study provides insight into the effect of polymer architecture on the nanostructure and rheology of PDEA-b-PEG-b-PDEA and presents the development of a highly functional thermoreversible gel with high promise for healthcare applications.

Thermo-Responsive Jamming of Nanoparticle Dense Suspensions towards Macroscopic Liquid-Solid Switchable Materials.

Nanoparticle aggregation for constructing functional materials has shown enormous advantages in various applications. Most efforts focused on ordered nanoparticle aggregation for specific functions but were often limited to irreversible aggregation processes due to the thermodynamic equilibrium. Herein, we report a reversible disordered aggregation of SiO2 -PNIPAAm nanoparticles (SPNPs) through thermo-responsive jamming, obtaining smart liquid-solid switchable materials. The smart materials can display a switch between liquid-like state and solid-like state responding to a temperature change. This unique macroscopic behavior originates from the reversible disordered aggregation modulated by temperature-dependent hydrophobic interactions among the SPNPs. Notably, the materials at the solid-like state show anti-impact properties and can withstand the impact of a steel sphere with a speed of 328 cm s-1 . We envision that this finding offers inspiration to design smart liquid-solid switchable materials for impact protection.

Dual Properties of Polyvinyl Alcohol-Based Magnetorheological Plastomer with Different Ratio of DMSO/Water

Polyvinyl alcohol (PVA)-based magnetorheological plastomer (MRP) possesses excellent magnetically dependent mechanical properties such as the magnetorheological effect (MR effect) when exposed to an external magnetic field. PVA-based MRP also shows a shear stiffening (ST) effect, which is very beneficial in fabricating pressure sensor. Thus, it can automatically respond to external stimuli such as shear force without the magnetic field. The dual properties of PVA-based MRP mainly on the ST and MR effect are rarely reported. Therefore, this work empirically investigates the dual properties of this smart material under the influence of different solvent compositions (20:80, 40:60, 60:40, and 80:20) by varying the ratios of binary solvent mixture (dimethyl sulfoxide (DMSO) to water). Upon applying a shear stress with excitation frequencies from 0.01 to 10 Hz, the storage modulus (G′) for PVA-based MRP with DMSO to water ratio of 20:40 increases from 6.62 × 10−5 to 0.035 MPa. This result demonstrates an excellent ST effect with the relative shear stiffening effect (RSTE) up to 52,827%. In addition, both the ST and MR effect show a downward trend with increasing DMSO content to water. Notably, the physical state of hydrogel MRP could be changed with different solvent ratios either in the liquid-like or solid-like state. On the other hand, a transient stepwise experiment showed that the solvent’s composition had a positive effect on the arrangement of CIPs within the matrix as a function of the external magnetic field. Therefore, the solvent ratio (DMSO/water) can influence both ST and MR effects of hydrogel MRP, which need to be emphasized in the fabrication of hydrogel MRP for appropriate applications primarily with soft sensors and actuators for dynamic motion control.

Modeling of chemically active particles at an air-liquid interface.

The collective motion of chemically active particles at an air-liquid interface is studied theoretically as a dynamic self-organization problem. Based on a physical consideration, we propose a minimal model for self-propelled particles by combining hydrodynamic interaction, capillary interaction, driving force by Marangoni effect, and Marangoni flow. Our model has successfully captured the features of chemically active particles, that represent dynamic self-organized states such as crystalline, chain, liquid-like and spreading states.

Universal interrelation between dynamics and thermodynamics and a dynamically driven "c" transition in fluids.

Our very wide survey of the supercritical phase diagram and its key properties reveals a universal interrelation between dynamics and thermodynamics and an unambiguous transition between liquidlike and gaslike states. This is seen in the master plot showing a collapse of the data representing the dependence of specific heat on key dynamical parameters in the system for many different paths on the phase diagram. As a result, the observed transition is path independent. We call it a "c" transition due to the c-shaped curve parametrizing the dependence of the specific heat on key dynamical parameters. The c transition has a fixed inversion point and provides a new structure to the phase diagram, operating deep in the supercritical state (up to, at least, 2000 times the critical pressure and 50 times the critical temperature). The data collapse and path independence as well as the existence of a special inversion point on the phase diagram are indicative of either of a sharp crossover or a new phase transition in the deeply supercritical state.

The influence of CNT-doped carbon aerogels on microstructural, rheological and mechanical properties of epoxy nanocomposites

In this study, CNT-doped carbon aerogel (CNT-CA) and carbon aerogel (CA) were used in different weight ratios (0.1, 0.3, and 0.5 wt%) to reinforce epoxy (Ep) nanocomposites. The relationship between the aerogels’ structure deformation such as the average diameter, the total volume of pores, specific surface area, and interfacial (particle/matrix) interaction, distribution, rheological, mechanical, and thermal properties were investigated systematically. Also, the nanocomposites were investigated by ATR-FTIR, XRD, and Raman spectroscopy. In general, the fabricated nanocomposites showed enhanced properties compared to the neat epoxy which is attributed to the penetration of polymer chains into the porous three-dimensional structure of the distributed aerogels. This phenomenon resulted in a high filler/matrix interaction, resulted in a better load transfer. Ep/CNT-CA showed better properties than Ep/CA which is due to ultrahigh specific surface area in CNT-CA. The rheological analysis showed a significant change in behavior from a liquid-like state to a pseudo-solid state in Ep/CA0.3 and Ep/CNT-CA0.1. Mechanical and thermal investigations of nanocomposites showed 8–17% increment in young modulus, 39–52% in tensile strength, 47–69% in elongation at break, 28–53% in E′ at 40 °C, 2–6% in Tanδ, and 7–11 °C in Tmax (compared to the neat epoxy matrix).

The role of thermal diffusion, particle clusters, hydrodynamic and magnetic forces on the flow behaviour of magneto-polymer composites.

In this paper, we study the shear-induced flow of magneto-polymer composites, consisting of dispersions of magnetic particles in solutions of polymers, as a competition between the colloidal forces amid particles and their bulk transport induced by the hydrodynamic forces. For this aim, we analyse the role of different experimental parameters. Firstly, by using only solutions of a well-known anionic polymer (sodium alginate), we provoke a moderate hindering of particle movement, but keeping the liquid-like state of the samples. On the contrary, a gel-like behaviour is conferred to the samples when a cationic polymer (chitosan) is additionally added, which further reduces the particle movement. We analyse the effect of an applied magnetic field, which is opposed to particle transport by hydrodynamic forces, by inducing magnetic attraction between the particles. We perform the analysis under both stationary and oscillatory shear. We show that by using dimensionless numbers the differences between samples and experimental conditions are emphasized. In all cases, as expected, the transport of particles driven by bulk hydrodynamic forces dominates at high values of the shear rate. This article is part of the theme issue 'Transport phenomena in complex systems (part 1)'.

Self-assembly of binary solutions to complex structures.

Self-assembly in natural and synthetic molecular systems can create complex aggregates or materials whose properties and functionalities rise from their internal structure and molecular arrangement. The key microscopic features that control such assemblies remain poorly understood, nevertheless. Using classical density functional theory, we demonstrate how the intrinsic length scales and their interplay in terms of interspecies molecular interactions can be used to tune soft matter self-assembly. We apply our strategy to two different soft binary mixtures to create guidelines for tuning intermolecular interactions that lead to transitions from a fully miscible, liquid-like uniform state to formation of simple and core-shell aggregates and mixed aggregate structures. Furthermore, we demonstrate how the interspecies interactions and system composition can be used to control concentration gradients of component species within these assemblies. The insight generated by this work contributes toward understanding and controlling soft multi-component self-assembly systems. Additionally, our results aid in understanding complex biological assemblies and their function and provide tools to engineer molecular interactions in order to control polymeric and protein-based materials, pharmaceutical formulations, and nanoparticle assemblies.

Plastic strain rate quantified from dislocation dynamics in dusty plasma shear flows.

Dynamics of dislocations and defects are investigated in 2D dusty plasma experiments with two counterpropagating flows. It is experimentally demonstrated that the Orowan equation is able to accurately determine the plastic strain rate from the motion of dislocations, well agreeing with the shear rate defined from the drift velocity gradient. For a higher shear rate, the studied system is in the liquidlike flow state, as a result, the determined shear rate from the Orowan equation deviates from its definition. The obtained probability distribution function of dislocations from the experiments clearly shows that the dislocation motion can be divided into the local and gliding ones. All findings above are further verified by the corresponding Langevin dynamical simulations with various levels of shear rates. The dislocation and defect analysis results from these simulations clearly indicate that the defect and dislocation dynamics in the sheared dusty plasmas clearly exhibit two stages as the shear rate increases.

Pseudo-boiling and concentration gradient in an enclosed supercritical binary mixture

Recent publications have shown the effectiveness of the analogy between fluids at sub- and supercritical pressures and confirmed there is a distinguishable crossover between liquid-like and gas-like behavior in supercritical fluids. This work is devoted to extending such an analogy to miscible zeotropic binary mixtures, whose well-known feature in liquid-gas coexistence under a subcritical pressure is the concentration difference between liquid and gas. Due to the availability of thermophysical properties, C2H6−CO2 binary mixture is taken as a reference fluid. Through numerical simulations for the steady states of an enclosed binary mixture at supercritical pressures subjected to temperature differences, this paper reveals the coexistence of liquid-like and gas-like states is featured by a concentration gradient naturally established by the critically enhanced Soret effect. It suggests that the concentration gradient is enhanced as the critical pressure is approached or as the temperature difference is enlarged. Besides, the low heat-conducting nature of the gas-like state compared to the liquid-like one gives rise to a pressure drop. This work gives new insights into the similarities of binary mixtures under sub- and supercritical pressures. For the convenience of latter studies, an open-source code is provided to calculate the physical properties of C2H6−CO2 binary mixture.

Hygroscopicity of secondary marine organic aerosols: Mixtures of alkylammonium salts and inorganic components

Field studies have identified alkylammonium salts as important components of secondary marine organic aerosols. In this work, we study the hygroscopic behavior of laboratory-generated alkylammonium aerosol particles, including monomethylammonium chloride (MMACl), dimethylammonium chloride (DMACl), trimethylammonium chloride (TMACl), diethylammonium chloride (DEACl), and their mixtures with inorganic salts containing ammonium sulfate (NH4)2SO4, sodium chloride NaCl, calcium nitrate Ca(NO3)2 and sodium sulfate Na2SO4 at different dry mass ratios with a hygroscopicity tandem differential mobility analyzer (HTDMA). The hygroscopic growth of pure alkylammonium salt particles (except for DEACl) reveals gradual water uptake over the whole studied range of relative humidities (RHs). In general, the impact of the presence of alkylammonium chloride on the phase behavior and hygroscopic growth of mixtures depends on the chemical composition of particles and volume fraction of the alkylammonium chloride in the mixtures. For alkylammonium/(NH4)2SO4 mixed particles (except for TMACl/(NH4)2SO4), the hygroscopic growth shows a smooth growth tendency when the organic content is high, while the deliquescence transition is observed for alkylammonium salt/NaCl mixtures at all mass ratios. Regarding the different mixtures of alkylammonium/Ca(NO3)2 particles, continuous water uptake without phase transition is observed over the studied RH range, indicating that alkylammonium salts impose no effect on the liquid-like state of calcium nitrate. The alkylammonium/Na2SO4 mixtures show obvious particle shrinkage prior to the deliquescence point. A similar behavior is also observed for alkylammonium salt/NaCl mixtures. The observed diameter reduction can be attributed to the transformation of porous or irregularly shaped solid particles into more compact near-spherical particles. In the following, measured growth factors (GFs) are compared with values predicted with the Zdanovskii–Stokes–Robinson (ZSR) mixing rule and ideal solution model. The ZSR predictions for different alkylammonium/inorganic mixtures are similar to the measured GFs as long as the mixed particles are in a liquid-like state.