Jiajia Zhou

Adaptive and freeze-tolerant heteronetwork organohydrogels with enhanced mechanical stability over a wide temperature range

Many biological organisms with exceptional freezing tolerance can resist the damages to cells from extra-/intracellular ice crystals and thus maintain their mechanical stability at subzero temperatures. Inspired by the freezing tolerance mechanisms found in nature, here we report a strategy of combining hydrophilic/oleophilic heteronetworks to produce self-adaptive, freeze-tolerant and mechanically stable organohydrogels. The organohydrogels can simultaneously use water and oil as a dispersion medium, and quickly switch between hydrogel- and organogel-like behaviours in response to the nature of the surrounding phase. Accordingly, their surfaces display unusual adaptive dual superlyophobic in oil/water system (that is, they are superhydrophobic under oil and superoleophobic under water). Moreover, the organogel component can inhibit the ice crystallization of the hydrogel component, thus enhancing the mechanical stability of organohydrogel over a wide temperature range (−78 to 80 °C). The organohydrogels may have promising applications in complex and harsh environments.

Highly Stretchable, Shape Memory Organohydrogels Using Phase‐Transition Microinclusions

Shape memory effect in polymer materials has attracted considerable attention due to its promising applications in a variety of fields. However, shape memory polymers prepared by conventional strategy suffer from a common problem, in which high strain capacity and excellent shape memory behavior cannot be simultaneously achieved. This study reports a general and synergistic strategy to fabricate high-strain and tough shape memory organohydrogels that feature binary cooperative phase. The phase- transition micro-organogels and elastic hydrogel framework act synergistically to provide excellent thermomechanical performance and shape memory effect. During shape memory process, the organohydrogels exhibit high strain capacity, featuring fully recoverable stretching deformation by up to 2600% and compression by up to 85% beneath a load ≈20 times the organohydrogels weight. Furthermore, owing to the micro-organogel and hydrogel heterostructures, the interfacial tension derived from heterophases dominates the shape recovery of the organohydrogel material. Simple processing and smart surface patterning of the shape memory behavior and multiple shape memory effects can also be realized. Meanwhile, these organohydrogels are also nonswellable in water and oil, which is important for multimedia applications.

Size Fractionation of Graphene Oxide Nanosheets via Controlled Directional Freezing

The properties and functions of graphene oxide (GO)-based materials strongly depend on the lateral size and size distribution of GO nanosheets; therefore, GO and its derivatives with narrow size distributions are highly desired. Here we report the size fractionation of GO nanosheets by controlled directional freezing of GO aqueous dispersions. GO nanosheets with a narrow size distribution can be obtained by controlling the growth rate of the freezing front. This interesting phenomenon can be explained by the adsorption of GO nanosheets on the ice crystal surface in combination with the stratification of GO nanosheets at the ice growth front. Such a convenient size fractionation approach will be essential for practical applications of chemically modified graphene, including GO, reduced GO, and their assemblies or composites.

3D Porous Hydrogel/Conducting Polymer Heterogeneous Membranes with Electro-/pH-Modulated Ionic Rectification

Heterogeneous membranes composed of asymmetric structures or compositions have enormous potential in sensors, molecular sieves, and energy devices due to their unique ion transport properties such as ionic current rectification and ion selectivity. So far, heterogeneous membranes with 1D nanopores have been extensively studied. However, asymmetric structures with 3D micro-/nanoscale pore networks have never been investigated. Here, a simple and versatile approach to low-costly fabricate hydrogel/conducting polymer asymmetric heterogeneous membranes with electro-/pH-responsive 3D micro-/nanoscale ion channels is introduced. Due to the asymmetric heterojunctions between positively charged nanoporous polypyrrole (PPy) and negatively charged microscale porous hydrogel poly (acrylamide-co-acrylic acid) (P(AAm-co-AA)), the membrane can rectify ion transmembrane transport in response to both electro- and pH-stimuli. Numerical simulations based on coupled Poisson and Nernst-Plank equations are carried out to explain the ionic rectification mechanisms for the membranes. The membranes are not dependent on elaborately fabricated 1D ion channel substrates and hence can be facilely prepared in a low-cost and large-area way. The hybridization of hydrogel and conducting polymer offers a novel strategy for constructing low-cost, large-area and multifunctional membranes, expanding the tunable ionic rectification properties into macroscopic membranes with micro-/nanoscale pores, which would stimulate practical applications of the membranes.

Structure Formation in Soft-Matter Solutions Induced by Solvent Evaporation

Solvent evaporation in soft-matter solutions (solutions of colloidal particles, polymers, and their mixtures) is an important process in material making and in the printing and coating industries. The solvent-evaporation process determines the structure of materials and strongly affects their performance. Solvent evaporation involves many physicochemical processes: flow, diffusion, crystallization, gelation, glass transition, etc. and is quite complex. Here, recent progress in this important process is reported, with a special focus on theoretical and simulation studies.

Thin film dynamics in coating problems using Onsager principle

A new variational method is proposed to investigate the dynamics of the thin film in a coating flow where a liquid is delivered through a fixed slot gap onto a moving substrate. A simplified ODE system has also been derived for the evolution of the thin film whose thickness is asymptotically constant behind the coating front. We calculate the phase diagram as well as the film profiles and approximate the film thickness theoretically, and agreement with the well-known scaling law as is found.

Theory on Capillary Filling of Polymer Melts in Nanopores

A unified theory for the imbibition dynamics of entangled polymer melting into nanopores is presented. Experiments demonstrate the validity of t1/2 dependence but contradict the predictions of the classical Lucas-Washburn equation because of the prefactor. A reversal in dynamics of capillary filling is reported with increasing polymer molecular weight. Polymer imbibition under nanometer confinement can be discussed by two mechanisms: one is the standard hydrodynamic flow, resulting in a parabolic flow profile. When the inner wall has a strong attraction to the polymer, a layer of immobile chains is created, resulting in an increase of the effective viscosity and to slower imbibition. The other is the reptation model proposed by Johner et al., leading to a plug flow profile and to the reduction in the effective viscosity (faster imbibition). The reversal in dynamics of polymer imbibition can be explained by the competition between these two mechanisms.

Capillary filling in closed-end nanotubes

Capillary filling in small length scale is an important process in nanotechnology and microfabrication. When one end of the tube or channel is sealed, it is important to consider the escape of the trapped gas. We develop a dynamic model on capillary filling in closed-end tubes, based on the diffusion-convection equation and Henrys law of gas dissolution. We systematically investigate the filling dynamics for various sets of parameters, and compare the results with a previous model which assumes a linear density profile of dissolved gas and neglect the convective term.