Influence of Humidity on Grip and Release Adhesion Mechanisms for Gecko-Inspired Microfibrillar Surfaces.

Geckos have developed foot pads that allow them to maintain their unique climbing ability despite vast differences of surfaces and environments, from dry desert to humid rainforest. Likewise, successful gecko-inspired mimics should exhibit adhesive and frictional performance across a similarly diverse range of climates. In this work, we focus on the effect of relative humidity (RH) on the "frictional-adhesion" behavior of gecko-inspired adhesive pads. A surface forces apparatus was used to quantitatively measure adhesion and friction forces of a microfibrillar cross-linked polydimethylsiloxane surface against a smooth hemispherical glass disk at varying relative humidity, from 0 to 100% (including fully submerged under water). Geometrically anisotropic tilted half-cylinder microfibers yield a "grip state" (high adhesion and friction forces after shearing along the tilt of the fibers, Fad+ and F∥+) and a "release state" (low adhesion and friction after shearing against the tilt of the fibers, Fad- and F∥-). By appropriate control of the loading path, this allows for transition between strong attachment and easy detachment. Changing the preload and shear direction gives rise to differences in the effective contact area at each fiber and the microscale and nanoscale structure of the contact while changing the relative humidity results in differences in the relative contributions of van der Waals and capillary forces. In combination, both effects lead to interesting trends in the adhesion and friction forces. At up to 75% RH, the grip state adhesion force remains constant and the ratio of grip to release adhesion force does not drop below 4.0. In addition, the friction forces F∥+ and F∥- and the release state adhesion force Fad- exhibit a maximum at intermediate relative humidity between 40% and 75%.

Stick-slip friction of gecko-mimetic flaps on smooth and rough surfaces.

The discovery and understanding of gecko 'frictional-adhesion' adhering and climbing mechanism has allowed researchers to mimic and create gecko-inspired adhesives. A few experimental and theoretical approaches have been taken to understand the effect of surface roughness on synthetic adhesive performance, and the implications of stick-slip friction during shearing. This work extends previous studies by using a modified surface forces apparatus to quantitatively measure and model frictional forces between arrays of polydimethylsiloxane gecko footpad-mimetic tilted microflaps against smooth and rough glass surfaces. Constant attachments and detachments occur between the surfaces during shearing, as described by an avalanche model. These detachments ultimately result in failure of the adhesion interface and have been characterized in this study. Stick-slip friction disappears with increasing velocity when the flaps are sheared against a smooth silica surface; however, stick-slip was always present at all velocities and loads tested when shearing the flaps against rough glass surfaces. These results demonstrate the significance of pre-load, shearing velocity, shearing distances, commensurability and shearing direction of gecko-mimetic adhesives and provide us a simple model for analysing and/or designing such systems.

JKR theory for the stick-slip peeling and adhesion hysteresis of gecko mimetic patterned surfaces with a smooth glass surface.

Geckos are highly efficient climbers and can run over any kind of surface with impeccable dexterity due to the typical design of their hierarchical foot structure. We have fabricated tilted, i.e., asymmetric, poly(dimethylsiloxane) (PDMS) microflaps of two different densities that mimic the function of the micrometer sized setae on the gecko foot pad. The adhesive properties of these microflaps were investigated in a modified surface forces apparatus; both for normal pure loading and unloading (detachment), as well as unloading after the surfaces were sheared, both along and against the tilt direction. The tilted microflaps showed directional, i.e., anisotropic adhesive behavior when sheared against an optically smooth (RMS roughness ≈ 10 ± 8 nm) SiO2 surface. Enhanced adhesion was measured after shearing the flaps along the tilted (gripping) direction and low adhesion when sheared against the tilted (releasing) direction. A Johnson-Kendall-Roberts (JKR) theory using an effective surface energy and modulus of rigidity (stiffness) quantitatively described the contact mechanics of the tilted microflaps against the SiO2 surface. We also find an increasing adhesion and stick-slip of the surfaces during detachment which we explain qualitatively in terms of the density of flaps, considering it to increase from 0% (no flaps, smooth surface) to 100% (close-packed flaps, effectively smooth surface). Large energy dissipation at the PDMS-silica interface caused by the viscoelastic behavior of the polymer results in stick-slip peeling and hence an enhanced adhesion energy is observed during the separation of the microflaps surface from the smooth SiO2 surface after shearing of the surfaces. For structured multiple contact surfaces, hysteresis as manifested by different loading and unloading paths can be due entirely to the elastic JKR micro-contacts. These results have important implications in the design of biomimetic adhesives.

Importance of loading and unloading procedures for gecko-inspired controllable adhesives.

The importance of loading and unloading procedures has been shown in a variety of different methods for biological dry adhesives, such as the fibers on the feet of the Tokay gecko, but biomimetic dry adhesives have yet to be explored in a similar manner. To date, little work has systematically varied multiple parameters to discern the influence of the testing procedure, and the effect of the approach angle remains uncertain. In this study, a synthetic adhesive is moved in 13 individual approach and retraction angles relative to a flat substrate as well as 9 different shear lengths to discern how loading and unloading procedures influence the preload, adhesion, and shear/friction forces supported. The synthetic adhesive, composed of vertical 10 µm diameter semicircular poly(dimethylsiloxane) fibers, is tested against a 4 mm diameter flat glass puck on a home-built microtribometer using both vertical approach and retraction tests and angled approach and retraction tests. The results show that near maximum adhesion and friction can be obtained for most approach and retraction angles, provided that a sufficient shear length is performed. The results also show that the reaction forces during adhesive placement can be significantly reduced by using specific approach angles, resulting for the vertical fibers in a 38-fold increase in the ratio of adhesion force to preload force, µ', when compared to that when using a vertical approach. These results can be of use to those currently researching gecko-inspired adhesives when designing their testing procedures and control algorithms for climbing and perching robots.

Friction and adhesion of gecko-inspired PDMS flaps on rough surfaces.

Geckos have developed a unique hierarchical structure to maintain climbing ability on surfaces with different roughness, one of the extremely important parameters that affect the friction and adhesion forces between two surfaces. Although much attention has been paid on fabricating various structures that mimic the hierarchical structure of a gecko foot, yet no systematic effort, in experiment or theory, has been made to quantify the effect of surface roughness on the performance of the fabricated structures that mimic the hierarchical structure of geckos. Using a modified surface forces apparatus (SFA), we measured the adhesion and friction forces between microfabricated tilted PDMS flaps and optically smooth SiO(2) and rough SiO(2) surfaces created by plasma etching. Anisotropic adhesion and friction forces were measured when sliding the top glass surface along (+y) and against (-y) the tilted direction of the flaps. Increasing the surface roughness first increased the adhesion and friction forces measured between the flaps and the rough surface due to topological matching of the two surfaces but then led to a rapid decrease in both of these forces. Our results demonstrate that the surface roughness significantly affects the performance of gecko mimetic adhesives and that different surface textures can either increase or decrease the adhesion and friction forces of the fabricated adhesives.

Vertical anisotropic microfibers for a gecko-inspired adhesive.

Geckos are able to adhere strongly and release easily from surfaces because the structurally anisotropic fibers on their toes naturally exhibit force anisotropy based on the direction of articulation. Here, semicircular fibers, with varying amounts of contact area on the two faces, are investigated to ascertain whether fiber shape can be used to gain anisotropy in shear and shear adhesion forces. Testing of 10-µm-diameter polydimethylsiloxane (PDMS) fibers against a 4-mm-diameter flat glass puck show that shear and shear adhesion forces were two to five times greater when in-plane movement caused the flat face, rather than the curved face, of the fiber to come in contact with the glass puck. The directional adhesion and shear force anisotropy results are close to theoretical approximations using the Kendall peel model and clearly demonstrate how fiber shape may be used to influence the properties of the adhesive. This result has broad applicability, and by combining the results shown here with other current vertical and angled designs, synthetic adhesives can be further improved to behave more like their natural counterparts.

Tin-oxide-nanowire-based electronic nose using heterogeneous catalysis as a functionalization strategy.

An electronic nose (e-nose) strategy is described based on SnO(2) nanowire arrays whose sensing properties are modified by changing their operating temperatures and by decorating some of the nanowires with metallic nanoparticles. Since the catalytic processes occurring on the metal nanoparticles depend on the identity of the metal, decorating the semiconducting nanowires with various metal nanoparticles is akin to functionalizing them with chemically specific moieties. Other than the synthesis of the nanowires, all other steps in the fabrication of the e-nose sensors were carried out using top-down microfabrication processes, paving the way to a useful strategy for making low cost, nanowire-based e-nose chips. The sensors were tested for their ability to distinguish three reducing gases (H(2), CO, and ethylene), which they were able to do unequivocally when the data was classified using linear discriminant analysis. The discriminating ability of this e-nose design was not impacted by the lengths or diameters of the nanowires used.

Frictional adhesion of patterned surfaces and implications for gecko and biomimetic systems.

Geckos and smaller animals such as flies, beetles, and spiders have extraordinary climbing abilities: They can firmly attach and rapidly detach from almost any kind of surface. In the case of geckos, this ability is attributed to the surface topography of their attachment pads, which are covered with fine columnar structures (setae). Inspired by this biological system, various kinds of regularly structured or "patterned" surfaces are being fabricated for use as responsive adhesives or in robotic systems. In this study, we theoretically analyze the correlated adhesion and friction (frictional adhesion) of patterned surfaces against smooth (unstructured) surfaces by applying well-established theories of van der Waals forces, together with the classic Johnson-Kendall-Roberts (JKR) theory of contact (or adhesion) mechanics, to recent theories of adhesion-controlled friction. Our results, when considered with recent experiments, suggest criteria for simultaneously optimizing the adhesion and friction of patterned surfaces. We show that both the van der Waals adhesion and the friction forces of flexible, tilted, and optimally spaced setal stalks or (synthetic) pillars are high enough to support not only a large gecko on rough surfaces of ceilings (adhesion) and walls (friction) but also a human being if the foot or toe pads-effectively the area of the hands-have a total area estimated at approximately 230 cm2.

High surface area of porous silicon drives desorption of intact molecules.

The surface structure of porous silicon used in desorption/ionization on porous silicon (DIOS) mass analysis is known to play a primary role in the desorption/ionization (D/I) process. In this study, mass spectrometry and scanning electron microscopy (SEM) are used to examine the correlation between intact ion generation with surface ablation and surface morphology. The DIOS process is found to be highly laser energy dependent and correlates directly with the appearance of surface ions (Si(n)(+) and OSiH(+)). A threshold laser energy for DIOS is observed (10 mJ/cm(2)), which supports that DIOS is driven by surface restructuring and is not a strictly thermal process. In addition, three DIOS regimes are observed that correspond to surface restructuring and melting. These results suggest that higher surface area silicon substrates may enhance DIOS performance. A recent example that fits into this mechanism is the surface of silicon nanowires, which has a high surface energy and concomitantly requires lower laser energy for analyte desorption.

Submicron streptavidin patterns for protein assembly.

Micron and submicron-scale features of aldehyde functionality were fabricated in polymer films by photolithography to develop a platform for protein immobilization and assembly at a biologically relevant scale. Films containing the pH-reactive polymer poly(3,3'-diethoxypropyl methacrylate) and a photoacid generator (PAG) were patterned from 500 nm to 40 mum by exposure to 365 nm (i-line) light. Upon PAG activation and hydrolysis of acetals, aldehyde groups formed. After the films were incubated with a biotinylated aldehyde reactive probe, the X-ray photoelectron spectroscopy results were consistent with biotin being attached to the surface. The background was subsequently passivated by flood exposure and incubation with an aminooxy-terminated poly(ethylene glycol), resulting in a 98% reduction in nonspecific protein adsorption. Protein patterning and assembly was demonstrated using streptavidin, biotinylated anthrax toxin receptor-1, and the protective antigen moiety of anthrax toxin and confirmed by fluorescence microscopy and atomic force microscopy (AFM). AFM demonstrated that 500 nm protein features were achieved. Because of the abundance of biotinylated proteins, this methodology provides a platform for protein immobilization and assembly for various applications in biotechnology.