Janus Droplet Formation via Thermally Induced Phase Separation: A Numerical Model with Diffusion and Convection

[Image: see text] Microscale Janus particles have versatile potential applications in many physical and biomedical fields, such as microsensor, micromotor, and drug delivery. Here, we present a phase-field approach of multicomponent and multiphase to investigate the Janus droplet formation via thermally induced phase separation. The crucial kinetics for the formation of Janus droplets consisting of two polymer species and a solvent component via an interplay of both diffusion and convection is considered in the Cahn–Hilliard–Navier–Stokes equation. The simulation results of the phase-field model show that unequal interfacial tensions between the two polymer species and the solvent result in asymmetric phase separation in the formation process of Janus droplets. This asymmetric phase separation plays a vital role in the establishment of the so-called core–shell structure that has been observed in previous experiments. By varying the droplet size, the surface tension, and the molecular interaction between the polymer species, several novel droplet morphologies are predicted in the development process of Janus droplets. Moreover, we stress that the hydrodynamics should be reckoned as a non-negligible mechanism that not only accelerates the Janus droplet evolution but also has great impacts on the coarsening and coalescence of the Janus droplets

Brownian motion of droplets induced by thermal noise

Brownian motion (BM) is pivotal in natural science for the stochastic motion of microscopic droplets. In this study, we investigate BM driven by thermal composition noise at sub-micro scales, where inter-molecular diffusion and surface tension both are significant. To address BM of microscopic droplets, we develop two stochastic multi-phase-field models coupled with the full Navier-Stokes equation, namely Allen-Cahn-Navier-Stokes (ACNS) and Cahn-Hilliard-Navier-Stokes (CHNS). Both models are validated against capillary wave theory; the Einstein's relation for the Brownian coefficient at thermodynamic equilibrium is recovered. Moreover, by adjusting the co-action of the diffusion, Marangoni effect, and viscous friction, two non-equilibrium phenomena are observed. (I) The droplet motion transits from the Brownian to Ballistic with increasing Marangoni effect which is emanated from the energy dissipation mechanism distinct from the conventional fluctuation-dissipation theorem. (II) The deterministic droplet motion is triggered by the noise induced non-uniform velocity field which leads to a novel droplet coalescence mechanism associated with the thermal noise

A thermodynamically consistent diffuse interface model for the wetting phenomenon of miscible and immiscible ternary fluids

The wetting effect has attracted great scientific interest because of its natural significance as well as technical applications. Previous models mostly focus on one-component fluids or binary immiscible liquid mixtures. Modelling of the wetting phenomenon for multicomponent and multiphase fluids is a knotty issue. In this work, we present a thermodynamically consistent diffuse interface model to describe the wetting effect for ternary fluids, as an extension of Cahn\u27s theory for binary fluids. In particular, we consider both immiscible and miscible ternary fluids. For miscible fluids, we validate the equilibrium contact angle and the thermodynamic pressure with Young\u27s law and the Young–Laplace equation, respectively. Distinct flow patterns for dynamic wetting are presented when the surface tension and the viscous force dominate the wetting effect. For immiscible ternary fluids, we manipulate the wettability of two contact droplets deposited on a solid substrate according to three scenarios: (I) both droplets are hydrophilic; (II) a hydrophilic droplet in contact with a hydrophobic one; (III) both droplets are hydrophobic. The contact angles at each triple junction from the simulations are compared with Young\u27s contact angle and Neumann\u27s triangle rule. Simulations for the validation of our work are performed in two and three dimensions. In addition, we model the evaporation process of a ternary droplet and obtain the same power law as that of previous experiments. Our model allows one to relate the interfacial energies with surface composition, enabling the modelling of the coffee-ring phenomenon in further perspective

Phase-field simulation for the formation of porous microstructures due to phase separation in polymer solutions on substrates with different wettabilities

The porous microstructure has been widely observed in a variety of polymer solutions that have been broadly applied in many industry fields. Phase separation is one of the common mechanisms for the formation of the porous microstructure in binary polymeric mixtures. Previous studies for the formation of porous microstructures mostly focus on the separation of the bulk phase. However, there is a paucity of investigation for the phase separation of polymer mixtures contacting the solid substrate. When the polymeric liquid mixtures interact with the solid substrate, the wetting boundary condition has to be taken into account. In this work, we present a phase-field model which is coupled with the wetting boundary condition to study the phase separation in binary polymer solutions. Our consideration is based on the polymerization-induced phase separation, and thermally induced phase separation by using the Flory-Huggins model. By taking the wetting effect into account, we find that polymer droplets spontaneously occur in the microstructure, even though the bulk composition is outside the spinodal region. This phenomenon is caused by the surface composition resulting from the wetting effect that was often overlooked in literature. For the phase separation in the binary polymer mixture, we also study the impact of the temperature gradient on the microstructural evolution. The porosity, the number of droplets, and the mean radius of the droplets are rationalized with the temperature gradient

3D printing of inherently nanoporous polymers via polymerization-induced phase separation

3D printing offers enormous flexibility in fabrication of polymer objects with complex geometries. However, it is not suitable for fabricating large polymer structures with geometrical features at the sub-micrometer scale. Porous structure at the sub-micrometer scale can render macroscopic objects with unique properties, including similarities with biological interfaces, permeability and extremely large surface area, imperative inter alia for adsorption, separation, sensing or biomedical applications. Here, we introduce a method combining advantages of 3D printing via digital light processing and polymerization-induced phase separation, which enables formation of 3D polymer structures of digitally defined macroscopic geometry with controllable inherent porosity at the sub-micrometer scale. We demonstrate the possibility to create 3D polymer structures of highly complex geometries and spatially controlled pore sizes from 10 nm to 1000 µm. Produced hierarchical polymers combining nanoporosity with micrometer-sized pores demonstrate improved adsorption performance due to better pore accessibility and favored cell adhesion and growth for 3D cell culture due to surface porosity. This method extends the scope of applications of 3D printing to hierarchical inherently porous 3D objects combining structural features ranging from 10 nm up to cm, making them available for a wide variety of applications

Effect of Grain Coalescence on Dislocation and Stress Evolution of GaN Films Grown on Nanoscale Patterned Sapphire Substrates

Two types of nucleation layers (NLs), including in-situ low-temperature grown GaN (LT-GaN) and ex-situ sputtered physical vapor deposition AlN (PVD-AlN), are applied on cone-shaped nanoscale patterned sapphire substrate (NPSS). The initial growth process of GaN on these two NLs is comparably investigated by a series of growth interruptions. The coalescence process of GaN grains is modulated by adjusting the three-dimensional (3D) temperatures. The results indicate that higher 3D temperatures reduce the edge dislocation density while increasing the residual compressive stress in GaN films. Compared to the LT-GaN NLs, the PVD-AlN NLs effectively resist Ostwald ripening and facilitate the uniform growth of GaN grains on NPSS. Furthermore, GaN films grown on NPSS with PVD-AlN NLs exhibit a reduction of over 50% in both screw and edge dislocation densities compared to those grown on LT-GaN NLs. Additionally, PVD-AlN NLs result in an increase of about 0.5 GPa in the residual compressive stress observed in GaN films