Michael Kappl

Normal capillary forces

A liquid meniscus between two lyophilic solid surfaces causes an attractive force, the capillary force. The meniscus can form by capillary condensation or by accumulation of adsorbed liquid. Under ambient conditions and between hydrophilic surfaces, capillary forces usually dominate over other surface forces. They are relevant in many processes occurring in nature and technical applications, for example the flow of granular materials and friction between surfaces. Here we review normal capillary forces, focusing on a quantitative description with continuum theory. After introducing the capillary force between spherical surfaces, we extend the discussion to other regular and irregular surfaces. The influence of surface roughness is considered. In addition to capillary forces at equilibrium, we also describe the process of meniscus formation. Assumptions, limits, and perspectives for future work are discussed.

Organic Field-Effect Transistors based on Highly Ordered Single Polymer Fibers

Ultrahigh-mobility organic field-effect transistors (OFETs) based on a CDT-BTZ donor-acceptor copolymer are realized by reaching high molecular order and pronounced alignment in single fibers within a short OFET channel via solution processing. The macromolecules directionally self-assemble in a quasi crystal-like order in the fibers providing in this way an unhindered charge carrier pathway with mobilities as high as 5.5 cm(2) V(-1) s(-1).

The Colloidal Probe Technique and its Application to Adhesion Force Measurements

Knowledge of the interaction forces between colloidal particles and surfaces is a precondition for understanding the stability of dispersed systems and adhesion phenomena. One of the methods available for direct measurement of surface forces is the atomic force microscope (AFM). Based on this method the so called “colloidal probe technique” was developed more than 10 years ago. Using a micron-sized particle glued to the end of an AFM cantilever as the force sensor, this technique is predestined for the study of colloidal interactions. In this review we describe the colloidal probe technique and give an overview of its application in the field of adhesion forces.

Hollow Silica Spheres: Synthesis and Mechanical Properties

Core-shell polystyrene-silica spheres with diameters of 800 nm and 1.9 microm were synthesized by soap-free emulsion and dispersion polymerization of the polystyrene core, respectively. The polystyrene spheres were used as templates for the synthesis of silica shells of tunable thickness employing the Stöber method [Graf et al. Langmuir 2003, 19, 6693]. The polystyrene template was removed by thermal decomposition at 500 degrees C, resulting in smooth silica shells of well-defined thickness (15-70 nm). The elastic response of these hollow spheres was probed by atomic force microscopy (AFM). A point load was applied to the particle surface through a sharp AFM tip, and successively increased until the shell broke. In agreement with the predictions of shell theory, for small deformations the deformation increased linearly with applied force. The Youngs modulus (18 +/- 6 GPa) was about 4 times smaller than that of fused silica [Adachi and Sakka J. Mater. Sci. 1990, 25, 4732] but identical to that of bulk silica spheres (800 nm) synthesized by the Stöber method, indicating that it yields silica of lower density. The minimum force needed to irreversibly deform (buckle) the shell increased quadratically with shell thickness.

Early Homogenous Amorphous Precursor Stages of Calcium Carbonate and Subsequent Crystal Growth in Levitated Droplets

An in situ study of the contact-free crystallization of calcium carbonate in acoustic levitated droplets is reported. The levitated droplet technique allows an in situ monitoring of the crystallization while avoiding any foreign phase boundaries that may influence the precipitation process by heterogeneous nucleation. The diffusion-controlled precipitation of CaCO3 at neutral pH starts in the initial step with the homogeneous formation of a stable, nanosized liquid-like amorphous calcium carbonate phase that undergoes in a subsequent step a solution-assisted transformation to calcite. Cryogenic scanning electron microscopy studies indicate that precipitation is not induced at the solution/air interface. Our findings demonstrate that a liquid-liquid phase separation occurs at the outset of the precipitation under diffusion-controlled conditions (typical for biomineral formation) with a slow increase of the supersaturation at neutral pH.

Rapid charge translocation by the cardiac Na(+)-Ca2+ exchanger after a Ca2+ concentration jump

The kinetics of Na(+)-Ca2+ exchange current after a cytoplasmic Ca2+ concentration jump (achieved by photolysis of DM-nitrophen) was measured in excised giant membrane patches from guinea pig or rat heart. Increasing the cytoplasmic Ca2+ concentration from 0.5 microM in the presence of 100 mM extracellular Na+ elicits an inward current that rises with a time constant tau 1 < 50 microseconds and decays to a plateau with a time constant tau 2 = 0.65 +/- 0.18 ms (n = 101) at 21 degrees C. These current signals are suppressed by Ni2+ and dichlorobenzamil. No stationary current, but a transient inward current that rises with tau 1 < 50 microseconds and decays with tau 2 = 0.28 +/- 0.06 ms (n = 53, T = 21 degrees C) is observed if the Ca2+ concentration jump is performed under conditions that promote Ca(2+)-Ca2+ exchange (i.e., no extracellular Na+, 5 mM extracellular Ca2+). The transient and stationary inward current is not observed in the absence of extracellular Ca2+ and Na+. The application of alpha-chymotrypsin reveals the influence of the cytoplasmic regulatory Ca2+ binding site on Ca(2+)-Ca2+ and forward Na(+)-Ca2+ exchange and shows that this site regulates both the transient and stationary current. The temperature dependence of the stationary current exhibits an activation energy of 70 kj/mol for temperatures between 21 degrees C and 38 degrees C, and 138 kj/mol between 10 degrees C and 21 degrees C. For the decay time constant an activation energy of 70 kj/mol is observed in the Na(+)-Ca2+ and the Ca(2+)-Ca2+ exchange mode between 13 degrees C and 35 degrees C. The data indicate that partial reactions of the Na(+)-Ca2+ exchanger associated with Ca2+ binding and translocation are very fast at 35 degrees C, with relaxation time constants of about 6700 s-1 in the forward Na(+)-Ca2+ exchange and about 12,500 s-1 in the Ca(2+)-Ca2+ exchange mode and that net negative charge is moved during Ca2+ translocation. According to model calculations, the turnover number, however, has to be at least 2-4 times smaller than the decay rate of the transient current, and Na+ inward translocation appears to be slower than Ca2+ outward movement.

Using capillary forces to determine the geometry of nanocontacts

The capillary force between two fine particles or between the tip of an atomic force microscope (AFM) and a surface depends on the precise geometry of the contact region. In this paper we demonstrate that vice versa from a measurement of the adhesion force versus humidity one can calculate the shape of the AFM tip (or the geometry of the contact between particles). This is verified by adhesion experiments with an AFM.

Sticking like sticky tape: tree frogs use friction forces to enhance attachment on overhanging surfaces

To live and clamber about in an arboreal habitat, tree frogs have evolved adhesive pads on their toes. In addition, they often have long and slender legs to facilitate not only long jumps, but also to bridge gaps between leaves when climbing. Both adhesive pads and long limbs are used in conjunction, as we will show in this study. Previous research has shown that tree frogs change from a crouched posture (where the limbs are close to the body) to a sprawled posture with extended limbs when clinging on to steeper inclines such as vertical or overhanging slopes. We investigated this change in posture in Whites tree frogs (Litoria caerulea) by challenging the frogs to cling onto a tiltable platform. The platform consisted of an array of 24 three-dimensional force transducers, which allowed us to measure the ground reaction forces of the frogs during a tilt. Starting from a crouched resting position, the normal forces on the forelimbs changed sign and became increasingly negative with increasing slope angle of the platform. At about 106°±12°, tilt of the platform the frogs reacted by extending one or two of their limbs outwards. At a steeper angle (131°±11°), the frogs spread out all their limbs sideways, with the hindlimbs stretched out to their maximum reach. Although the extension was strongest in the lateral direction, limbs were significantly extended in the fore–aft direction as well. With the extension of the limbs, the lateral forces increased relative to the normal forces. The large contribution of the in-plane forces helped to keep the angle between the force vector and the platform small. The Kendall theory for the peeling of adhesive tape predicts that smaller peel angles lead to higher attachment forces. We compare our data with the predictions of the Kendall model and discuss possible implications of the sliding of the pads on the surface. The forces were indeed much larger for smaller angles and thus can be explained by peeling theory.

Facile and Large-Scale Fabrication of Anisometric Particles from Fibers Synthesized by Colloid-Electrospinning

A new top-down approach is proposed to form large amounts of anisometric particles. Multicompartment fibers that present different domains composed of silica nanoparticles and larger polystyrene nanoparticles are fabricated by colloid-electrospinning and are subsequently calcinated and broken. The obtained fibers containing voids are subsequently cut via sonication to yield anisometric particles. It is shown that the majority of the fibers can be broken at the voids.

Mechanical properties of poly(dimethylsiloxane)-block-poly(2-methyloxazoline) polymersomes probed by atomic force microscopy.

Poly(dimethylsiloxane)-block-poly(2-methyloxazoline) (PDMS-b-PMOXA) vesicles were characterized by a combination of dynamic light scattering (DLS), cryogenic transmission electron microscopy (cryo-TEM), and atomic force microscopy imaging and force spectroscopy (AFM). From DLS data, a hydrodynamic radius of ~150 nm was determined, and cryo-TEM micrographs revealed a bilayer thickness of ~16 nm. In AFM experiments on a silicon wafer substrate, adsorption led to a stable spherical caplike conformation of the polymersomes, whereas on mica, adsorption resulted also in vesicle fusion and formation of bilayer patches or multilayer stacks. This indicates a delicate balance between the mechanical stability of PDMS-b-PMOXA polymersomes on one hand and the driving forces for spreading on the other. A Youngs modulus of 17 ± 11 MPa and a bending modulus of 7 ± 5 × 10(-18) J were derived from AFM force spectroscopy measurements. Therefore, the elastic response of the PDMS-b-PMOXA polymersomes to external stimuli is much closer to that of lipid vesicles compared to other types of polymersomes, such as polystyrene-block-poly(acrylic acid) (PS-b-PAA).