More Like this

1. Nonequilibrium interfacial properties of chemically driven fluids

   https://doi.org/10.1063/5.0166824  

   Cho, Yongick; Jacobs, William M. (October 2023, The Journal of Chemical Physics)

   Chemically driven fluids can demix to form condensed droplets that exhibit phase behaviors not observed at equilibrium. In particular, nonequilibrium interfacial properties can emerge when the chemical reactions are driven differentially between the interior and exterior of the phase-separated droplets. Here, we use a minimal model to study changes in the interfacial tension between coexisting phases away from equilibrium. Simulations of both droplet nucleation and interface roughness indicate that the nonequilibrium interfacial tension can either be increased or decreased relative to its equilibrium value, depending on whether the driven chemical reactions are accelerated or decelerated within the droplets. Finally, we show that these observations can be understood using a predictive theory based on an effective thermodynamic equilibrium. 

   more » « less
2. Nonequilibrium statistical thermodynamics of multicomponent interfaces

   https://doi.org/10.1073/pnas.2121405119  

   Rauscher, Phillip M.; Öttinger, Hans Christian; de Pablo, Juan J. (June 2022, Proceedings of the National Academy of Sciences)

   Nonequilibrium interfacial thermodynamics has important implications for crucial biological, physical, and industrial-scale transport processes. Here, we discuss a theory of local equilibrium for multiphase multicomponent interfaces that builds upon the “sharp” interface concept first introduced by Gibbs, allowing for a description of nonequilibrium interfacial processes such as those arising in evaporation, condensation, adsorption, etc. By requiring that the thermodynamics be insensitive to the precise location of the dividing surface, one can identify conditions for local equilibrium and develop methods for measuring the values of intensive variables at the interface. We then use extensive, high-precision nonequilibrium molecular dynamics (NEMD) simulations to verify the theory and establish the validity of the local equilibrium hypothesis. In particular, we demonstrate that equilibrium equations of state are also valid out of equilibrium, and can be used to determine interfacial temperature and chemical potential(s) that are consistent with nonequilibrium generalizations of the Clapeyron and Gibbs adsorption equations. We also show, for example, that, far from equilibrium, temperature or chemical potential differences need not be uniform across an interface and may instead exhibit pronounced discontinuities. However, even in these circumstances, we demonstrate that the local equilibrium hypothesis and its implications remain valid. These results provide a thermodynamic foundation and computational tools for studying or revisiting a wide variety of interfacial transport phenomena. 

   more » « less
3. Tuning nonequilibrium phase transitions with inertia

   https://doi.org/10.1063/5.0138256  

   Omar, Ahmad K.; Klymko, Katherine; GrandPre, Trevor; Geissler, Phillip L.; Brady, John F. (February 2023, The Journal of Chemical Physics)

   In striking contrast to equilibrium systems, inertia can profoundly alter the structure of active systems. Here, we demonstrate that driven systems can exhibit effective equilibrium-like states with increasing particle inertia, despite rigorously violating the fluctuation–dissipation theorem. Increasing inertia progressively eliminates motility-induced phase separation and restores equilibrium crystallization for active Brownian spheres. This effect appears to be general for a wide class of active systems, including those driven by deterministic time-dependent external fields, whose nonequilibrium patterns ultimately disappear with increasing inertia. The path to this effective equilibrium limit can be complex, with finite inertia sometimes acting to accentuate nonequilibrium transitions. The restoration of near equilibrium statistics can be understood through the conversion of active momentum sources to passive-like stresses. Unlike truly equilibrium systems, the effective temperature is now density dependent, the only remnant of the nonequilibrium dynamics. This density-dependent temperature can in principle introduce departures from equilibrium expectations, particularly in response to strong gradients. Our results provide additional insight into the effective temperature ansatz while revealing a mechanism to tune nonequilibrium phase transitions. 

   more » « less
4. Formation of microfluidic droplets and jets in a solvent-rich oil phase

   https://doi.org/10.1017/flo.2025.10017  

   Joseph, Victoria; Cubaud, Thomas (January 2025, Flow)

   Abstract We develop original flow-based methods to interrogate and manipulate out-of-equilibrium behaviour of ternary fluids systems at the small scale. In particular, we examine droplet and jet formation of ternary fluid systems in coaxial microchannels when an aqueous phase is injected into a solvent-rich oil phase using common fluids, such as ethanol for the aqueous phase, silicone oil for the oil phase and isopropanol for the solvent. Alcohols are often employed to impart oil and water properties with a myriad of practical uses as extractants, antiseptics, wetting agents, emulsifiers or biofuels. Here, we systematically examine the role of alcohol solvents on the hydrodynamic stability of aqueous–oil multiphase flows in square microchannels. Broad variations of flow rates and solvent concentration reveal a variety of intriguing droplet and jet flow regimes in the presence of spontaneous emulsification phenomena and significant mass transfer across the fluid interface. Typical flow patterns include dripping and jetting droplets, phase inversion and dynamic wetting and conjugate jets. Functional relationships are developed to model the evolution of multiphase flow characteristics with solvent concentration. This work provides insights into complex natural phenomena relevant to the application of microfluidic droplet systems to chemical assays as well as fluid measurement and characterisation technologies. 

   more » « less
5. Electrowetting-assisted droplet coalescence and roll-off for condensation heat trasnfer

   Wikramanayake, Enakshi D.; Bahadur, Vaibhav (December 2019, Proceedings of the International Heat and Mass Transfer Conference)

   Dropwise condensation heat transfer is significantly higher than filmwise condensation heat transfer due to the absence of the thermal resistance associated with the condensed water film. This study uses electrowetting to enhance coalescence and roll-off of condensed droplets, with the objective of enhancing the condensation rate. Coalescence enhancement is achieved by electric field-driven droplet motion such as translation of droplets, and oscillations of the three-phase line. Experiments are conducted to study early-stage droplet growth dynamics, and steady state condensation under electrowetting fields. Results show that droplet growth and roll-off increases with the voltage and frequency of the applied AC field. AC electric fields are seen to be more effective than DC electric fields. The overall condensation rate depends on the roll-off size of droplets, frequency of roll-off events, and on the interactions of the rolled-off droplets with the remainder of the droplets. All these phenomena can be altered by the applied electric field. An analytical heat transfer model is developed which uses the measured droplet size distribution to estimate the surface heat flux. Overall, this study reports that electric fields can enhance the condensation rate by more than 30 %. 

   more » « less