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.

Imbibition Dynamics in a U-Groove Microchannel with Sudden Enlargement.

Imbibition dynamics in a rectangular U-groove that is connected to a sudden enlargement and complicated by the presence of Concus-Finn (CF) filaments is investigated using many-body dissipative particle dynamics. For open-ended sudden enlargement, four flow types are identified and depend on the contact angle θy, the critical angle θf associated with the occurrence of CF filaments, and the critical angle θc associated with the occurrence of main flow. First, for θy > θf and θy > θc, the corner flow is absent, and the main flow stops at the end of the small U-groove. Second, for θc > θy > θf, the corner flow vanishes, but the main flow occurs. Third, for θf > θy > θc, the corner flow takes place in the large U-groove, but the main flow is still absent. Fourth, for θy < θf and θy < θc, both the corner and main flows appear in the large U-groove. Additionally, the flow dynamics is greatly influenced by the length of the large U-groove (le). For closed-ended sudden enlargement, similar findings can be obtained. However, the outcome of the third case is altered for sufficiently small le, and the sudden enlargement can eventually be filled.

Atypical vesicles and membranes with monolayer and multilayer structures formed by graft copolymers with diblock side-chains: nonlamellar structures and curvature-enhanced permeability.

Graft copolymers with diblock side-chains Am(-graft-B3Ay)n in a selective solvent have been reported to self-assemble into vesicles, but the structure is expected to differ distinctly from those of lipid bilayers. Surprisingly, the number of alternating hydrophobic A-block and hydrophilic B-block layers in the vesicle can vary from a monolayer to multilayers such as the hepta-layer, subject to the same copolymer concentration. The area density of the copolymer layer is not uniform across the membrane. This structural difference among different layers is attributed to the neighboring environment and the curvature of the layer. Because of the unusual polymer conformations, nonlamellar structures of polymersomes are formed, and they are much more intricate than those of liposomes. In fact, a copolymer can contribute to a single or two hydrophilic layers, and it can provide up to three hydrophobic layers. The influence of the backbone length (m) and side-chain length (y) and the permeation dynamics are also studied. The thickness of hydrophobic layers is found to increase with increasing side-chain length but is not sensitive to the backbone length. Although the permeation time increases with the layer number for planar membranes, the opposite behavior is observed for spherical vesicles owing to the curvature-enhanced permeability associated with Laplace pressure.

Floating and Diving Loops of ABA Triblock Copolymers in Lipid Bilayers and Stability Enhancement for Asymmetric Membranes.

Hybrid membranes of lipids and AxByAz triblock copolymers can possess better biocompatibility and mechanical stability. In this work, triblock copolymer conformations and stability of asymmetric membranes are explored by dissipative particle dynamics. The triblock copolymers in the membranes exhibit either the bridge or loop conformation. As hydrophobic B-blocks interact attractively with lipid heads, bridge-shaped copolymers are significantly inhibited and loop-shaped copolymers prefer to stay at the interface between hydrophilic and hydrophobic layers. This floating loop has a flattened conformation, consistent with the experimental findings. In contrast, for repulsive interactions between B-blocks and lipid heads, bridge-shaped copolymers are abundant and loop-shaped copolymers tend to plunge into the hydrophobic layer. This diving loop displays a random coil conformation. The asymmetric membrane in which the fractions of loop-shaped copolymers in the upper and lower leaflets are different is thermodynamically unstable. Two approaches are proposed to acquire kinetically stable asymmetric membranes. First, membrane symmetrization is arrested by eliminating bridge-shaped copolymers, which is achieved by B-block/lipid head attraction and B-block/lipid tail repulsion. Second, asymmetric triblock copolymers (x ≠ z) are used to prevent the passage of the long A-block through the hydrophobic layer.

Strengthening mechanism of the mechanical properties of graft copolymers with incompatible pendant groups: nano-clusters and weak cross-linking.

It is known that the adhesive property and mechanical strength of an apolar polymer can be improved by grafting with polar side chains, whereas the underlying mechanism is still elusive. In this work, the equilibrium structure and mechanical moduli of the melt of graft copolymers have been explored by dissipative particle dynamics. Due to the strong immiscibility of the non-polar backbone and polar side chains, nano-clusters of side chains formed and acted as physical crosslinkers. Moreover, non-affinity adsorption of polar side chains in the melt to the wall was observed, revealing an improvement in the adhesion property. Subjecting graft copolymers to cyclic deformation, the storage and loss moduli were acquired, and they grew with increasing grafting density. The melt strength in terms of the crossover frequency ascended with more side chains on the backbone. Our findings reveal that the strengthening of the mechanical properties of graft copolymers can be attributed to the formation of weakly cross-linked structures, thus offering an insight into the molecular design to aid the development of stronger graft copolymers.

Non-affinity adsorption of nanorods onto smooth walls via an entropy driven mechanism.

Preferential adsorption of nanorods onto smooth walls is investigated using dissipative particle dynamics in the absence of specific attraction and a depletant. Although the translational and rotational entropy of nanorods is significantly reduced after adsorption, the effective attraction between the nanorod and wall is clearly identified based on the distribution profile of rods. As the rod length increases, the attractive interaction grows stronger and clusters of aligned nanorods can emerge on the smooth wall. However, the presence of a depletion zone of nanorods adjacent to the adsorbed layer gives zero surface excess. These two regions correspond to the primary minimum and maximum mean force potentials observed. Since adsorbed nanorods lose their rotational and translational entropy, the strong adsorption of long nanorods has to be attributed to the entropy gain associated with the increase in free volume for the solvent in this athermal system. Nonetheless, as the surface roughness is present, entropy-driven attraction is lessened, similar to the depletion force between colloids.

Preferred penetration of active nano-rods into narrow channels and their clustering.

In a channel connected to a reservoir, passive particles prefer staying in the reservoir than the channel due to the entropic effect, as the size of the particles is comparable to that of the channel. Self-propelled rods can exhibit out-of-equilibrium phenomena, and their partition behavior may differ from that of passive rods due to their persistent swimming ability. In this work, the distribution of active nano-rods between the nanoscale channel and reservoir is explored using dissipative particle dynamics. The ratio of the nano-rod concentration in the slit to that in the reservoir, defined as the partition ratio Ψ, is a function of active force, channel width, and rod length. Although passive nano-rods prefer staying in bulk (Ψ < 1), active rods can overcome the entropic barrier and show favorable partition toward narrow channels (Ψ > 1). As the slit width decreases to about the rod's width, active rods entering the slit behave like a quasi-two-dimensional system dynamically. At sufficiently high concentrations and Peclet numbers, nano-rods tend to align and move together in the same direction for a certain time. The distribution (PM) of the cluster size (M) follows a power law, PM ∝ M-2, for small clusters.

Partition of nanoswimmers between two immiscible phases: a soft and penetrable boundary.

The behavior of run-and-tumble nanoswimmers which can self-propel in two immiscible liquids such as water-oil systems and are able to cross the interface is investigated by dissipative particle dynamics. At the steady-state, the partition ratio (φ) of nanoswimmers between the two immiscible liquids is obtained, and it depends on the active force (Fa), run time (τ), and swimmer-solvent interactions. The partition ratio φ is found to grow generally with increasing Fa2τ. At sufficiently large Fa, it is surprising to find that hydrophilic nanoswimmers prefer to stay in the oil phase rather than in the water phase. The partition ratio is also influenced by the hydrophobicity of swimmers in the oil phase. Two simple models are proposed to describe the partition ratio, including a near-equilibrium model and a kinetic model. Surface accumulation appearing at an impenetrable interface is also observed at the fluid-fluid interface for small Fa but it vanishes for sufficiently large Fa.

Size-dependence and interfacial segregation in nanofilms and nanodroplets of homologous polymer blends.

The size-dependent behavior of nanofilms and nanodroplets of homologous polymer blends was explored by many-body dissipative particle dynamics. Although a homologous blend can be regarded as a completely miscible and athermal system, enrichment of the surface in short polymers always takes place. First, liquid-gas and solid-liquid interfacial tensions of polymer melts were acquired. It is found that they increase and approach asymptotes with increasing chain lengths. The molecular weight dependence can be depicted using two semi-empirical expressions. Second, the variation of surface tension and surface excess of polymer blend nanofilms with the thickness was observed. Surface tension of the blend is observed to increase but the extent of surface segregation decreases upon increasing the film thickness. Finally, the wetting phenomenon of nanodroplets of homologous blends was examined. The contact angle is found to increase as the droplet size is reduced. Our simulation results indicate that the size-dependence of nanofilms and nanodroplets is closely related to surface segregation in homologous blends.

Zeolite-Based Antifogging Coating via Direct Wet Deposition.

Zeolites are strongly hydrophilic materials that are widely used as water adsorbents. They are also promising candidates for antifogging coatings; however, researchers have yet to devise a suitable method for coating glass substrates with zeolite-based films. Here, we report on a direct wet deposition technique that is capable of casting zeolite films on glass substrates without exposing the glass to highly basic solutions or the vapors used in zeolite synthesis. We began by preparing cast solutions of pure silica zeolite MFI synthesized in hydrothermal reactions of various durations. The solutions were then applied to glass substrates via spin-on deposition to form zeolite films. The resulting zeolite MFI thin films were characterized in terms of transmittance to visible light, surface topography, thin film morphology, and crystallinity. Wetting and antifogging properties were also probed. We found that hydrophilicity and antifogging capability increased with the degree of thin film crystallinity. We also determined that the presence of the amorphous silica in the thin films is critical to transparency. Fabricating high-performance zeolite-based antifogging coatings requires an appropriate composition of zeolite crystals and amorphous silica.

Bilayered membranes of Janus dendrimers with hybrid hydrogenated and fluorinated dendrons: microstructures and coassembly with lipids.

A biomimetic membrane formed by hybrid Janus dendrimers (JDs) which contain hydrogenated and fluorinated dendrons was explored by dissipative particle dynamics simulations. The JD membrane is bilayered and shows a bicontinuous morphology which is also observed in nano-sized dendrimersomes. The thickness of the dendrimersome is significantly less than that of the planar membrane. The co-assembly of lipids with JDs to develop a hybrid membrane was studied as well. Lipids tend to locate in the hydrocarbon domain of the bicontinuous structure of the JD-rich membrane, while 2-dimensional micelles of JDs float in the leaflet of the lipid-rich membrane. The microstructure of the hybrid membrane was quantified by interdigitation lengths in the hydrocarbon, fluorocarbon, and lipid domains. Finally, the influence of lipid concentration on lipid fluidity was examined in terms of lipid diffusivity, which is found to be closely associated with the membrane microstructure.

Mechanical pressure, surface excess, and polar order of a dilute rod-like nanoswimmer suspension: role of swimmer-wall interactions.

The mechanical pressure, surface excess, and polar order of a dilute rod-like nanoswimmer suspension confined by two parallel plates are explored by dissipative particle dynamics. The accumulation and preferred orientation of swimmers near the walls are distinctly shown through the density and polar order distributions for various active force, Fa, values and rod lengths. As Fa is increased, it is interesting to observe that there exists a maximum of the polar order, revealing that the dominant mechanism of the swimmer behavior can be altered by the coupling between the active force and the rod-wall interaction. As a result, the influences of the active force on the swim pressure Π(w)a contributed by the swimmers directly and the surface excess Γ* can be classified into two scaling regimes, natural rotation (weak propulsion) and forced rotation (strong propulsion). Π(w)a and Γ* are proportional to Fa2 in the former regime but become proportional to Fa in the latter regime. For all rod-wall repulsions, the swim pressure of active rods in confined systems Π(w)a always differs from that in unbounded systems Π(b)a which is simply proportional to Fa2 associated with the active diffusivity. That is, unlike thermal equilibrium systems, Π(w)a is not a state function because of the presence of the wall-torque.

Hydrodynamic interaction induced breakdown of the state properties of active fluids.

The mechanical pressure of active fluids in which swimmers are modeled by soft run-and-tumble spheres is investigated by dissipative particle dynamics simulations. The incremental pressure (Π) with respect to the system pressure with inactive swimmers comprises the direct contribution of the swimmers (π) and the indirect contribution of fluids associated with hydrodynamic interactions (HIs). The pressure can be determined from the bulk and confining wall and the former is always less than the latter. The π of dilute active dispersions is proportional to their active diffusivity while Π grows generally with propulsive force and run time. However, Π is always substantially less than π because of negative contributions to pressure by HIs. The wall pressure depends on the swimmer-wall interactions, verifying that pressure is not a state function for active spheres due to the HIs. Owing to the distinct flow patterns, Π varies with the swim-type (pusher and puller) subject to the same run-and-tumble parameters at high concentrations.

Self-healing and dewetting dynamics of a polymer nanofilm on a smooth substrate: strategies for dewetting suppression.

The self-healing and dewetting dynamics of a polymer nanofilm on a smooth, partial wetting surface are explored by many-body dissipative particle dynamics. Three types of dewetting phenomena are identified, (i) spinodal decomposition, (ii) nucleation and growth, and (iii) metastable self-healing. The outcome depends on the surface wettability (θY), the polymer film thickness (h0), and the radius of the dry hole (R0). The phase diagram of the dewetting mechanism as a function of θY and h0 is obtained for a specified R0. As the surface wettability decreases (increasing θY), the critical film thickness associated with the nucleation/self-healing crossover (hc) grows so that the metastability of the film can be retained by the self-healing process. In addition to θY and R0, hc depends on the polymer length (N) as well. It is found that a longer polymer requires a thicker nanofilm to avoid dewetting by nucleation. Two strategies for dewetting suppression are proposed. The metastability of a film of polymers with a large molecular weight can be promoted either by the addition of short polymers or by employing compact polymers such as star polymers. In the latter approach, the increment of the arm number enhances the nanofilm stability.

Branching pattern effect and co-assembly with lipids of amphiphilic Janus dendrimersomes.

The influence of the branching patterns on the membrane properties of Janus dendrimers in water has been investigated by dissipative particle dynamics simulations. The hydrophobic fluorinated dendron (RF) contains three types of branching patterns, including 3,4-, 3,5-, and 3,4,5-RF. Consistent with experimental results, the hydrophobic layer thickness (HB) follows the order: 3,5-RF < 3,4-RF < 3,4,5-RF, which can be explained by the extent of interdigitation (Δh): 3,5-RF > 3,4-RF > 3,4,5-RF. Moreover, the 3,4,5-RF membrane shows the highest stretching modulus (KA) and the lowest lateral diffusivity (D). The 3,5-RF membrane is similar to the 3,4-RF membrane but exhibits a higher KA and smaller D. For the nano-sized dendrimersome, its bilayer thickness is less than that of the planar membrane due to its larger extent of interdigitation. The co-assembly of dendrimersomes with lipids has been studied as well. The thickness and the extent of interdigitation of the lipid-rich domain for the hybrid membrane are significantly affected by the lipid concentration (φl) and the branching patterns. As φl increases, the thickness of the lipid-rich domain grows corresponding to the decrease of interdigitation of the lipid-rich domain.

Dynamics of bridge-loop transformation in a membrane with mixed monolayer/bilayer structures.

Instead of forming a typical bilayer or monolayer membrane, both the bridge (I-shape) and loop (U-shape) conformations coexist in the planar membranes formed by ABA triblock copolymers in a selective solvent. The non-equilibrium and equilibrium relaxation dynamics of polymer conformations are monitored. The non-equilibrium relaxation time depends on the initial composition and increases with an increase in the immiscibility between A and B blocks. The equilibrium composition of the loop-shape polymer is independent of the initial composition and A-B immiscibility. However, the extent of equilibrium composition fluctuations subsides as the A and B blocks become highly incompatible. The influences of the A-B immiscibility on the geometrical, mechanical, and transport properties of the membrane have also been investigated. As the immiscibility increases, the overall membrane thickness and the B block layer thickness (h) increase because of the increment in the molecular packing density. As a result, both the stretching (KA) and bending (KB) moduli grow significantly with the increasing A-B immiscibility. Consistent with the case of typical membranes, the ratio KB/KAh2 = 2 × 10-3 is a constant. Although the lateral diffusivity of polymers is insensitive to immiscibility, the membrane permeability decreases substantially as the A-B immiscibility is increased.

Forced Spreading of Aqueous Solutions on Zwitterionic Sulfobetaine Surfaces for Rapid Evaporation and Solute Separation.

Solute separation of aqueous mixtures is mainly dominated by water vaporization. The evaporation rate of an aqueous drop grows with increasing the liquid-gas interfacial area. The spontaneous spreading behavior of a water droplet on a total wetting surface provides huge liquid-gas interfacial area per unit volume; however, it is halted by the self-pinning phenomenon upon addition of nonvolatile solutes. In this work, it is shown that the solute-induced self-pinning can be overcome by gravity, leading to anisotropic spreading much faster than isotropic spreading. The evaporation rate of anisotropic spreading on a zwitterionic sulfobetaine surface is 25 times larger as that on a poly(methyl methacrylate) surface. Dramatic enhancement of evaporation is demonstrated by simultaneous formation of fog atop liquid film. During anisotropic spreading, the solutes are quickly precipitated out within 30 s, showing the rapid solute-water separation. After repeated spreading process for the dye-containing solution, the mean concentration of the collection is doubled, revealing the concentration efficiency as high as 100%. Gravity-enhanced spreading on total wetting surfaces at room temperature is easy to scale-up with less energy consumption, and thus it has great potentials for the applications of solute separation and concentration.

Self-Propulsion and Shape Restoration of Aqueous Drops on Sulfobetaine Silane Surfaces.

The motion of droplets on typical surfaces is generally halted by contact line pinning associated with contact angle hysteresis. In this study, it was shown that, on a zwitterionic sulfobetaine silane (SBSi)-coated surface, aqueous drops with appropriate solutes can demonstrate hysteresis-free behavior, whereas a pure water drop shows spontaneous spreading. By adding solutes such as polyethylene glycol, 2(2-butoxy ethoxy) ethanol, or sodium n-dodecyl sulfate, an aqueous drop with a small contact angle (disappearance of spontaneous spreading) was formed on SBSi surfaces. The initial drop shape was readily relaxed back to a circular shape (hysteresis-free behavior), even upon severe disturbances. Moreover, it was interesting to observe the self-propulsion of such a drop on horizontal SBSi surfaces in the absence of externally provided stimuli. The self-propelled drop tends to follow a random trajectory, and the continuous movement can last for at least 10 min. This self-propelled random motion can be attributed to the combined effects of the hysteresis-free surface and the Marangoni stress. The former comes from the total wetting property of the surface, while the latter originates from surface tension gradient due to fluctuating evaporation rates along the drop border.