Enhancement of the Rate of Surface Reactions by the Elastocapillary Effect.

We examined the effect of deformability of a solid substrate on the kinetics of a surface reaction that occurs between chemical species present in it and a liquid dispensed on it. In particular, we have dispensed aqueous solutions of gold and silver salt as sessile drops or as a liquid pool on a cross-linked film of poly(dimethylsiloxane) (PDMS). The PDMS surface contains organosilane (SiH), which reduces the salt, producing metallic nanoparticles at the solid-liquid interface. These experiments reveal that, for a sufficiently soft solid, the reaction proceeds about three times faster in the drop mode than in the pool mode. The reaction conditions in both cases remain exactly identical except that, for the drop, the vertical component of the liquid surface tension deforms the solid substrate at the three-phase contact line. We have estimated the solid-liquid and solid-air interfacial energy, which along with the surface energy of the liquid gives an estimate of excess free energy. This energy is found to be different for the drop and pool modes. By considering that this excess free energy decreases the activation energy barrier for the reaction, we have shown that the reaction rate constant in the drop mode should indeed exceed that in the pool mode by about three times.

Studying kinetics of a surface reaction using elastocapillary effect.

HYPOTHESIS: When a liquid is inserted inside a microfluidic channel, embedded within a soft elastomeric layer, e.g. poly(dimethylsiloxane) (PDMS), the thin wall of the channel deforms, due to change in solid-liquid interfacial energy. This phenomenon is known as Elastocapillary effect. The evolution of a new species at this interface too alters the interfacial energy and consequently the extent of deformation. Hence, it should be possible to monitor dynamics of physical and chemical events occurring near to the solid-liquid interface by measuring this deformation by a suitable method, e.g., optical profilometer. EXPERIMENTS: Aqueous solution of a metal salt inserted into these channels reacts with Silicon-hydride present in PDMS, yielding metallic nanoparticles at the channel surface. The kinetics of this reaction was captured in real time, by measuring the wall deformation. Similarly, physical adsorption of a protein: Bovine Serum Albumin, on PDMS surface too was monitored. FINDING: The rate of change in deformation can be related to rate of these processes to extract the respective reaction rate constant. These results show that Elastocapillary effect can be a viable analytical tool for in-situ monitoring of many physical and chemical processes for which, the reaction site is inaccessible to conventional analytical methods.

How does a lizard shed its tail?

Hierarchical microstructures help a lizard self-amputate its tail when needed.

Liquid Spreading Induced by In Situ Generation of Metallic Nanoparticles.

Spreading or pinning of a liquid drop on a solid substrate is determined by the surface energy of solid and liquid, topography of substrate surface, and different external forces like electric field, magnetic field, and vibration. Here we present a novel mechanism of depinning, driven by in situ generation of a species following reaction between a constituent of the droplet and one in the substrate. In particular, fluoro-carbon (FC) functionalized agarose and pHEMA gels are used as the substrates; the substrate is soaked with chloroauric acid. A drop of poly(dimethylsiloxane) (PDMS) mixed with the cross-linking agent is dispensed on it. The drop does not spread in absence of the salt, but as the salt concentration increases, the spreading diameter increases with decrease in the contact angle. The Si-H group, present as a constituent in the cross-linking agent, reduces the salt, leading to in situ generation of gold nanoparticles, that mitigates the pinning effect of the drop and the drop spreads.

Fingering instability during fracture of a gel block subjected to shear loading.

We report here an alternative kind of fingering instability observed during fracture of an unconfined gel consisting of two cuboids joined by a thin gel disk, and all prepared monolithically. When the blocks are sheared across the joint, fracture ensues with the appearance of fingers at the fracture front. The spacing between the fingers remains independent of the shearing speed, planar shape of the joint, and the shear modulus of gel. Importantly this instability appears without any effect of confinement of the gel block, and its wavelength remains dependent on the lateral size of the disk, in contrast to all known instances of fingering phenomena in confined viscous, elastic, and viscoelastic systems.

Confinement-Induced Alteration of Morphologies of Oil-Water Emulsions.

Reversible alteration between different emulsion morphologies like core-shell and Janus is conventionally triggered by altering the interfacial energy between different phases. In contrast, here, we show that the morphology of dispersed droplets can be changed also when the emulsion is sufficiently confined between two parallel plates. In particular, we use three immiscible phases: silicone oil, paraffin oil, and aqueous solution of surface-active agents like agarose, sodium dodecylsulfate, dioctyl sodium sulfosuccinate, and cetyl trimethylammonium bromide to generate oil-in-water emulsions consisting of complex morphologies of the dispersed droplets. In the unconfined state, the core-shell drops appear with paraffin oil at the core and silicone oil at the shell. However, the morphology of oil droplets changes to Janus when the emulsion is confined between two parallel plates. We have shown that the meniscus of the continuous phase that forms between the parallel plates alters the pressure field in the emulsion and the total energy of the system, which trigger such morphological transition.

The effect of shape on the fracture of a soft elastic gel subjected to shear load.

For brittle solids, the fracture energy is the energy required to create a unit area of new surface through the process of division. For crosslinked materials, it is a function of the intrinsic properties like crosslinking density and bond strength of the crosslinks. Here we show that the energy released due to fracture can depend also on the shape of a joint made of this material. Our experiment involves two gel blocks connected via a thin gel disk. The disk is formed into different regular and exotic shapes, but with identical areas of cross-section. When one of the blocks is sheared with respect to the other, the shear load increases with vertical displacement, eventually causing a fracture at a threshold load. The maximum fracture load is different for different disks and among different regularly shaped disks, it is at a maximum for pentagon and hexagon shapes. The fracture energy release rate of the joint depends also on the aspect ratio (height/width) of the shapes. Our experiments also throw light on possible reasons for such a dependence on the shape of the joints.

Generation of Aspherical Optical Lenses via Arrested Spreading and Pinching of a Cross-Linkable Liquid.

Aspherical optical lenses with spatially varying curvature are desired for capturing high quality, aberration free images in numerous optical applications. Conventionally such lenses are prepared by multistep top-down processes which are expensive, time-consuming, and prone to high failure rate. In this context, an alternate method is presented here based on arrested spreading of a sessile drop of a transparent, cross-linkable polymeric liquid on a solid substrate heated to an elevated temperature. Whereas surface tension driven flow tends to render it spherical, rapid cross-linking arrests such flow so that nonequilibrium aspherical shapes are attained. It is possible to tune also the initial state of the drop via delayed pinching of a liquid cylinder which precedes its release on the substrate. This method has led to the generation of a wide variety of optical lenses, ranging from spherical plano convex to superspherical solid immersion to exotic lenses not achieved via conventional methods.

Estimation of solid-liquid interfacial tension using curved surface of a soft solid.

Unlike liquids, for crystalline solids the surface tension is known to be different from the surface energy. However, the same cannot be said conclusively for amorphous materials like soft cross-linked elastomers. To resolve this issue we have introduced here a direct method for measuring solid-liquid interfacial tension by using the curved surface of a solid. In essence, we have used the inner surface of tiny cylindrical channels embedded inside a soft elastomeric film for sensing the effect of the interfacial tension. When a liquid is inserted into the channel, because of wetting-induced alteration in interfacial tension, its thin wall deflects considerably; the deflection is measured with an optical profilometer and analyzed using the Föppl-von Kármán equation. We have used several liquids and cross-linked poly(dimethylsiloxane) as the solid to show that the estimated values of the solid-liquid interfacial tension matches with the corresponding solid-liquid interfacial energy reasonably well.

Adhesion-induced instabilities and pattern formation in thin films of elastomers and gels.

A hydrostatically stressed soft elastic film circumvents the imposed constraint by undergoing a morphological instability, the wavelength of which is dictated by the minimization of the surface and the elastic strain energies of the film. While for a single film, the wavelength is entirely dependent on its thickness, a co-operative energy minimization dictates that the wavelength depends on both the elastic moduli and thicknesses of two contacting films. The wavelength can also depend on the material properties of a film if its surface tension has a pronounced effect in comparison to its elasticity. When such a confined film is subjected to a continually increasing normal displacement, the morphological patterns evolve into cracks, which, in turn, govern the adhesive fracture behavior of the interface. While, in general, the thickness provides the relevant length scale underlying the well-known Griffith-Kendall criterion of debonding of a rigid disc from a confined film, it is modified non-trivially by the elasto-capillary number for an ultra-soft film. Depending upon the degree of confinement and the spatial distribution of external stress, various analogs of the canonical instability patterns in liquid systems can also be reproduced with thin confined elastic films.

A co-operative effect of closely spaced intruding objects puncturing into a soft solid.

When two or more closely spaced indenters puncture a soft solid, the puncturing load diminishes from that required when they are far apart. We have developed a method to examine this effect by embedding a planar tracer grid within a block of an elastic gel and by driving closely spaced syringe needles of different inter-tip spacing through this plane. These experiments show that in addition to a primary crack ahead of the needle-tip, there occurs also a periodically appearing secondary radial crack from its side. The strain field around the side crack remains non-monotonic with a characteristic length scale which varies with both solid modulus and needle diameter. For closely spaced multiple indenters the overlapping strain profiles cause compressive stress at the vicinity of the needles, which arrest the side cracks, the diminishing effect of which leads to stress concentration for the primary crack and the resultant decrease in required load for driving the indenters through the solid. We have shown that such a co-operative effect remains valid for materials of different types, e.g. brittle and ductile and for multiple-tip needles consisting of constituent tips of equal and unequal diameters.

Peeling off an adhesive layer with spatially varying topography and shear modulus.

Inspired by recent experiments on hierarchically structured adhesives, we analyze here the effect of spatial variation in surface topography and shear modulus of an elastomeric adhesive on its ability to adhere strongly to a flexible contactor. The undulation of surface and modulus both were assumed to be periodic with periodicity, which is either identical or different for the two parameters; for identical periodicity, the phase lag between the respective undulations is also systematically varied. Calculations show that during continuous lifting of the flexible contactor from complete initial contact, the interfacial crack between the two adherents does not propagate continuously but intermittently, with crack arrest and initiation at the vicinity of minimum thickness and modulus of the layer; the torque required to initiate an arrested crack increases significantly over that required to propagate it on a smooth adhesive surface. The adhesion strength estimated from the corresponding force vs displacement plot is calculated to be higher than that achieved on a smooth and featureless adhesive surface. For in-phase variation in topography and shear modulus of the layer, the adhesive strength is found to be higher than for nonzero phase lag between the two parameters. The adhesion strength is found to diminish also for nonidentical periodicity between modulus and surface undulation. We have derived a scaling law for relating adhesion strength to several of these parameters.

Harvesting energy of interaction between bacteria and bacteriophage in a membrane-less fuel cell.

When a fuel and oxidant flow in laminar contact through a micro-fluidic channel, a sharp interface appears between the two liquids, which eliminate the need of a proton exchange membrane. This principle has been used to generate potential in a membrane-less fuel cell. This study use such a cell to harvest energy of interaction between a bacteria having negative charge on its surface and a bacteriophage with positive and negative charges on its tail and head, respectively. When Klebsiella pneumoniae (Kp6) and phage (P-Kp6) are pumped through a fuel cell fitted with two copper electrodes placed at its two sides, interaction between these two charged species at the interface results in a constant open circuit potential which varies with concentration of charged species but gets generated for both specific and non-specific bacteria and phage system. Oxygenation of bacteria or phage however diminishes the potential unlike in conventional microbial fuel cells.

Disordered nanowrinkle substrates for inducing crystallization over a wide range of concentration of protein and precipitant.

There are large number of proteins, the existence of which are known but not their crystal structure, because of difficulty in finding the exact condition for their crystallization. Heterogeneous nucleation on disordered porous substrates with small yet large distribution of pores is considered a panacea for this problem, but a universal nucleant suitable for crystallizing large variety of proteins does not really exist. To this end, we report here a nanowrinkled substrate which displays remarkable ability and control over protein crystallization. Experiments with different proteins show that on these substrates crystals nucleate even at very low protein concentration in buffer. A small number of very large crystals appear for precipitant concentrations varied over orders of magnitude, ~0.003-0.3 M; for some proteins, crystals appear even without addition of any precipitant, not seen with any other heterogeneous substrates. In essence, these substrates significantly diminish the influence of the above two parameters, thought to be key factors for crystallization, signifying that this advantage can be exploited for finding out crystallization condition for other yet-to-be-crystallized proteins.

Surface-tension-induced flattening of a nearly plane elastic solid.

We report direct measurement of surface deformation in soft solids due to their surface tension. Gel replicas of poly(dimethysiloxane) masters with rippled surfaces are found to have amplitudes that decrease with decreasing gel modulus. Surface undulations of a thin elastomeric film are attenuated when it is oxidized by brief exposure to oxygen plasma. Surface deformation in both cases is modeled successfully as driven by surface tension and resisted by elasticity. Our results show that surface tension of soft solids drives significant deformation, and that the latter can be used to determine the former.

Control of adhesion via internally pressurized subsurface microchannels.

While pressure sensitive adhesives in general consist of a layer of viscoelastic glue sandwiched between two adherents, we explore here the design of an adhesive embedded with microchannels which remain either open to atmosphere or pressurized to different positive and negative pressures. We subject these layers to indentation by a rigid cylinder such that in addition to adhesion between the indenter and the adhesive surface, the inner walls of the channels too self-adhere; during retraction of the indenter, these surfaces debond, but at a different load, thus resulting in hysteresis. When these channels are pressurized to different extents, the contact areas of various interfaces vary, so also the resultant hysteresis. For experiments with constant depth of indentation, the hysteresis increases and attains maxima at an intermediate value of the internal pressure inside the channels. The hysteresis increases also with the skin thickness of the adhesive over the channels. These results show that subsurface channels in an adhesive allow active manipulation of adhesion over a large range via coupled effect of geometry of channels, their surface characteristics, and the pressure inside.

Reusable antifouling viscoelastic adhesive with an elastic skin.

Although the viscoelasticity or tackiness of a pressure-sensitive adhesive gives it strength owing to energy dissipation during peeling, it also renders it nonreusable because of structural changes such as the formation of fibrils, cohesive failure, and fouling. However, an elastic layer has good structural integrity and cohesive strength but low adhesive energy. We demonstrate an effective composite adhesive in which a soft viscoelastic bulk layer is imbedded in a largely elastic thin skin layer. The composite layer is able to meet the conflicting demands of the high peel strength comparable to the viscoelastic core and the structural integrity, reusability, and antifouling properties of the elastic skin. Our model adhesive is made of poly(dimethylsiloxane), where its core and skin are created by varying the cross-linking percentage from 2 to 10%.

Peeling off an adhesive layer with spatially varying modulus.

We analyze here displacement controlled peeling of a flexible adherent off a thin layer of elastic adhesive, the elastic modulus of which does not remain uniform but varies periodically along the direction of peeling. Calculation shows that with progressive peeling, the crack front does not propagate continuously at the interface but intermittently with crack arrests and subsequent initiations. The crack gets arrested close to the location of the minimum shear modulus of the layer and initiates again only at a sufficiently large peel off load. This effect is very similar to the peeling experiment off surface patterned and microchannel embedded adhesives which results in significant enhancement of fracture toughness of the interface over smooth adhesive layers. The fracture toughness of the interface increases with the increase in thickness of the layer and the amplitude of variation in modulus. Fracture toughness is calculated to be high also for the larger value of critical stress at the opening of the crack. With the wavelength of modulus variation, it varies nonmonotonically, maximizing at an intermediate value. These results define the criterion for designing adhesive layers with spatially modulated physical properties useful for variety of applications.

A bioinspired wet/dry microfluidic adhesive for aqueous environments.

A pressure-sensitive, nonreacting and nonfouling adhesive which can perform well both in air and underwater is very desirable because of its potential applications in various settings such as biomedical, marine, and automobile. Taking a clue from nature that many natural adhesive pads have complex structures underneath the outer adhesive layer, we have prepared thin elastic adhesive films with subsurface microstructures using PDMS (poly(dimethylsiloxane)) and investigated their performance underwater. The presence of embedded structure enhances the energy of adhesion considerably both in air and underwater. Furthermore, filling the channels with liquid of suitable surface tension modifies the internal stress profile, resulting into significant enhancement in adhesive performance. As this increase in adhesion is mediated by mechanics and not by surface chemistry, the presence of water does not alter its performance much. For the same reason, this adhesion mechanism works with both hydrophobic and hydrophilic surfaces. The adhesive can be reused because of its elastic surface. Moreover, unlike many other present-day adhesives, its performance does not decrease with time.

Hysteresis of soft joints embedded with fluid-filled microchannels.

Many arthropods are known to achieve dynamic stability during rapid locomotion on rough terrains despite the absence of an elaborate nervous system. While muscle viscoelasticity and its inherent friction have been thought to cause this passive absorption of energy, the role of embedded microstructures in muscles and muscle joints has not yet been investigated. Inspired by the soft and flexible hinge joints present in many of these animals, we have carried out displacement-controlled bending of thin elastic slabs embedded with fluid-filled microchannels. During loading, the slab bends uniformly to a critical curvature, beyond which the skin covering the channel buckles with a catastrophic decrease in load. In the reverse cycle, the buckled skin straightens out but at a significantly lower load. In such a loading-unloading cycle, this localized buckling phenomenon results in a dynamic change in the geometry of the joint, which leads to a significant hysteresis in elastic energy. The hysteresis varies nonlinearly with channel diameters and thicknesses of the slab, which is captured by a simple scaling analysis of the phenomenon.