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Strong Wet and Dry Adhesion by Cupped Microstructures

2019, Wang, Y., Kang, V., Arzt, E., Federle, W., Hensel, R.

Recent advances in bio-inspired microfibrillar adhesives have resulted in technologies that allow reliable attachment to a variety of surfaces. Because capillary and van der Waals forces are considerably weakened underwater, fibrillar adhesives are however far less effective in wet environments. Although various strategies have been proposed to achieve strong reversible underwater adhesion, strong adhesives that work both in air and underwater without additional surface treatments have yet to be developed. In this study, we report a novel design - cupped microstructures (CM) - that generates strong controllable adhesion in air and underwater. We measured the adhesive performance of cupped polyurethane microstructures with three different cup angles (15, 30, and 45°) and the same cup diameter of 100 μm in dry and wet conditions in comparison to standard mushroom-shaped microstructures (MSMs) of the same dimensions. In air, 15°CM performed comparably to the flat MSM of the same size with an adhesion strength (force per real contact area) of up to 1.3 MPa, but underwater, 15°CM achieved 20 times stronger adhesion than MSM (∼1 MPa versus ∼0.05 MPa). Furthermore, the cupped microstructures exhibit self-sealing properties, whereby stronger pulls lead to longer stable attachment and much higher adhesion through the formation of a better seal. © 2019 American Chemical Society.

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Mechanically reinforced catechol-containing hydrogels with improved tissue gluing performance

2017, Feng, Jun, Ton, Xuan-Anh, Zhao, Shifang, Paez, Julieta I., del Campo, Aránzazu

In situ forming hydrogels with catechol groups as tissue reactive functionalities are interesting bioinspired materials for tissue adhesion. Poly(ethylene glycol) (PEG)–catechol tissue glues have been intensively investigated for this purpose. Different cross-linking mechanisms (oxidative or metal complexation) and cross-linking conditions (pH, oxidant concentration, etc.) have been studied in order to optimize the curing kinetics and final cross-linking degree of the system. However, reported systems still show limited mechanical stability, as expected from a PEG network, and this fact limits their potential application to load bearing tissues. Here, we describe mechanically reinforced PEG–catechol adhesives showing excellent and tunable cohesive properties and adhesive performance to tissue in the presence of blood. We used collagen/PEG mixtures, eventually filled with hydroxyapatite nanoparticles. The composite hydrogels show far better mechanical performance than the individual components. It is noteworthy that the adhesion strength measured on skin covered with blood was >40 kPa, largely surpassing (>6 fold) the performance of cyanoacrylate, fibrin, and PEG–catechol systems. Moreover, the mechanical and interfacial properties could be easily tuned by slight changes in the composition of the glue to adapt them to the particular properties of the tissue. The reported adhesive compositions can tune and improve cohesive and adhesive properties of PEG–catechol-based tissue glues for load-bearing surgery applications.

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On the process of co-deformation and phase dissolution in a hard-soft immiscible CuCo alloy system during high-pressure torsion deformation

2016, Bachmaier, Andrea, Schmauch, Jörg, Aboulfadl, Hisham, Verch, Andreas, Motz, Christian

In this study, dual phase Cusingle bondCo composites with a total immiscibility in the solid state and a very different initial phase strength are deformed by severe plastic deformation. Nanocrystalline supersaturated solid solutions are reached in all Cusingle bondCo composites independent of the initial composition. The deformation and mechanical mixing process is studied thoroughly by combining scanning electron microscopy, transmission electron microscopy, three-dimensional atom probe tomography and nanoindentation. The indentation hardness of the Cu and Co phase and its evolution as a function of the applied strain is linked to deformation and mechanical mixing process to gain a better understanding how the phase strength mismatch of the Cu and Co phase effects the amount of co-deformation and deformation-induced mixing. Our results show that co-deformation is not a necessary requirement to achieve mechanical mixing.

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Reversibly compressible and freestanding monolithic carbon spherogels

2019, Salihovic, M., Zickler, G.A., Fritz-Popovski, G., Ulbricht, M., Paris, O., Hüsing, N., Presser, V., Elsaesser, M.S.

We present a versatile strategy to tailor the nanostructure of monolithic carbon aerogels. By use of an aqueous colloidal solution of polystyrene in the sol-gel processing of resorcinol-formaldehyde gels, we can prepare, after supercritical drying and successive carbonization, freestanding monolithic carbon aerogels, solely composed of interconnected and uniformly sized hollow spheres, which we name carbon spherogels. Each sphere is enclosed by a microporous carbon wall whose thickness can be adjusted by the polystyrene concentration, which affects the pore texture as well as the mechanical properties of the aerogel monolith. In this study, we used monodisperse polystyrene spheres of approximately 250 nm diameter, which result in an inner diameter of the final hollow carbon spheres of approximately 200 ± 5 nm due to shrinkage during the carbonization process. The excellent homogeneity of the samples, as well as uniform sphere geometries, are confirmed by small- and angle X-ray scattering. The presence of macropores between the hollow spheres creates a monolithic network with the benefit of being reversibly compressible up to 10% linear strain without destruction. Electrochemical tests demonstrate the applicability of ground and CO2 activated carbon spherogels as electrode materials. © 2019 The Authors

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Toward light‐regulated living biomaterials

2018, Sankaran, Shrikrishnan, Zhao, Shifang, Muth, Christina, Paez, Julieta, Del Campo, Aránzazu

Living materials are an emergent material class, infused with the productive,adaptive, and regenerative properties of living organisms. Property regulation in living materials requires encoding responsive units in the living components to allow external manipulation of their function. Here, an optoregulated Escherichia coli (E. coli)-based living biomaterial that can be externally addressed using light to interact with mammalian cells is demonstrated. This is achieved by using a photoactivatable inducer of gene expression and bacterial surface display technology to present an integrin-specific miniprotein on the outer membrane of an endotoxin-free E. coli strain. Hydrogel surfaces functionalized with the bacteria can expose cell adhesive molecules upon in situ light-activation, and trigger cell adhesion. Surface immobilized bacteria are able to deliver a fluorescent protein to the mammalian cells with which they are interacting, indicating the potential of such a bacterial material to deliver molecules to cells in a targeted manner.

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Funnel-shaped microstructures for strong reversible adhesion

2017, Fischer, Sarah C.L., Groß, Katja, Abad, Oscar Torrents, Becker, MIchael M., Park, Euiyoung, Hensel, René, Arzt, Eduard

The potential of a new design of adhesive microstructures in the micrometer range for enhanced dry adhesion is investigated. Using a two-photon lithography system, complex 3D master structures of funnel-shaped microstructures are fabricated for replication into poly(ethylene glycol) dimethacrylate polymer. The diameter, the flap thickness, and the opening angle of the structures are varied systematically. The adhesion of single structures is characterized using a triboindenter system equipped with a flat diamond punch. The pull-off stresses obtained reaches values up to 5.6 MPa, which is higher than any values reported in literature for artificial dry adhesives. Experimental and numerical results suggest a characteristic attachment mechanism that leads to intimate contact formation from the edges toward the center of the structures. van der Waals interactions most likely dominate the adhesion, while contributions by suction or capillarity play only a minor role. Funnel-shaped microstructures are a promising concept for strong and reversible adhesives, applicable in novel pick and place handling systems or wall-walking robots.

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Composite pillars with a tunable interface for adhesion to rough substrates

2017, Fischer, Sarah C.L., Arzt, Eduard, Hensel, René

The benefits of synthetic fibrillar dry adhesives for temporary and reversible attachment to hard objects with smooth surfaces have been successfully demonstrated in previous studies. However, surface roughness induces a dramatic reduction in pull-off stresses and necessarily requires revised design concepts. Toward this aim, we introduce cylindrical two-phase single pillars, which are composed of a mechanically stiff stalk and a soft tip layer. Adhesion to smooth and rough substrates is shown to exceed that of conventional pillar structures. The adhesion characteristics can be tuned by varying the thickness of the soft tip layer, the ratio of the Young’s moduli and the curvature of the interface between the two phases. For rough substrates, adhesion values similar to those obtained on smooth substrates were achieved. Our concept of composite pillars overcomes current practical limitations caused by surface roughness and opens up fields of application where roughness is omnipresent.

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Mechanochemistry-assisted synthesis of hierarchical porous carbons applied as supercapacitors

2017, Leistenschneider, Desirée, Jäckel, Nicolas, Hippauf, Felix, Presser, Volker, Borchardt, Lars

A solvent-free synthesis of hierarchical porous carbons is conducted by a facile and fast mechanochemical reaction in a ball mill. By means of a mechanochemical ball-milling approach, we obtained titanium(IV) citrate-based polymers, which have been processed via high temperature chlorine treatment to hierarchical porous carbons with a high specific surface area of up to 1814 m2 g−1 and well-defined pore structures. The carbons are applied as electrode materials in electric double-layer capacitors showing high specific capacitances with 98 F g−1 in organic and 138 F g−1 in an ionic liquid electrolyte as well as good rate capabilities, maintaining 87% of the initial capacitance with 1 M TEA-BF4 in acetonitrile (ACN) and 81% at 10 A g−1 in EMIM-BF4.

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Engineering Micropatterned Dry Adhesives: From Contact Theory to Handling Applications

2018, Hensel, René, Moh, Karsten, Arzt, Eduard

Reversible adhesion is the key functionality to grip, place, and release objects nondestructively. Inspired by nature, micropatterned dry adhesives are promising candidates for this purpose and have attracted the attention of research groups worldwide. Their enhanced adhesion compared to nonpatterned surfaces is frequently demonstrated. An important conclusion is that the contact mechanics involved is at least as important as the surface energy and chemistry. In this paper, the roles of the contact geometry and mechanical properties are reviewed. With a focus on applications, the effects of substrate roughness and of temperature variations, and the long-term performance of micropatterned adhesives are discussed. The paper provides a link between the current, detailed understanding of micropatterned adhesives and emerging applications.

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Monitoring the contact stress distribution of gecko-inspired adhesives using mechano-sensitive surface coatings

2018, Neubauer, Jens W., Xue, Longjian, Erath, Johann, Drotlef, Dirk-Michael, del Campo, Aránzazu, Fery, Andreas

The contact geometry of microstructured adhesive surfaces is of high relevance for adhesion enhancement. Theoretical considerations indicate that the stress distribution in the contact zone is crucial for the detachment mechanism, but direct experimental evidence is missing so far. In this work, we propose a method that allows, for the first time, the detection of local stresses at the contact area of biomimetic adhesive microstructures during contact formation, compression and detachment. We use a mechano-sensitive polymeric layer, which turns mechanical stresses into changes of fluorescence intensity. The biomimetic surface is brought into contact with this layer in a well-defined fashion using a microcontact printer, while the contact area is monitored with fluorescence microscopy in situ. Thus, changes in stress distribution across the contact area during compression and pull-off can be visualized with a lateral resolution of 1 μm. We apply this method to study the enhanced adhesive performance of T-shaped micropillars, compared to flat punch microstructures. We find significant differences in the stress distribution of the both differing contact geometries during pull-off. In particular, we find direct evidence for the suppression of crack nucleation at the edge of T-shaped pillars, which confirms theoretical models for the superior adhesive properties of these structures.