The strong adhesion of sub-micron sized particles to surfaces is a nuisance, both for removing contaminating colloids from surfaces and for conscious manipulation of particles to create and test ...novel micro/nano-scale assemblies. The obvious idea of using detergents to ease these processes suffers from a lack of control: the action of any conventional surface-modifying agent is immediate and global. With photosensitive azobenzene containing surfactants we overcome these limitations. Such photo-soaps contain optical switches (azobenzene molecules), which upon illumination with light of appropriate wavelength undergo reversible trans-cis photo-isomerization resulting in a subsequent change of the physico-chemical molecular properties. In this work we show that when a spatial gradient in the composition of trans- and cis- isomers is created near a solid-liquid interface, a substantial hydrodynamic flow can be initiated, the spatial extent of which can be set, e.g., by the shape of a laser spot. We propose the concept of light induced diffusioosmosis driving the flow, which can remove, gather or pattern a particle assembly at a solid-liquid interface. In other words, in addition to providing a soap we implement selectivity: particles are mobilized and moved at the time of illumination, and only across the illuminated area.
Extreme value analysis (EVA) is well-established to derive hydrometeorological design values for infrastructures that have to withstand extreme events. Since there is concern about increased extremes ...with higher hazard potential under climate change, alterations of EVA are introduced for which statistical properties are no longer assumed to be constant but vary over time. In this study, both stationary and non-stationary EVA models are used to derive design life levels (DLLs) of daily precipitation in the pre-alpine Oberland region of Southern Germany, an orographically complex region characterized by heavy precipitation events and climate change. As EVA is fraught with uncertainties, it is crucial to quantify its methodological impacts: two theoretical distributions (i.e., Generalized Extreme Value (GEV) and Generalized Pareto (GP) distribution), four different parameter estimation techniques (i.e., Maximum Likelihood Estimation (MLE), L-moments, Generalized Maximum Likelihood Estimation (GMLE), and Bayesian estimation method) are evaluated and compared. The study reveals large methodological uncertainties. Discrepancies due to the parameter estimation methods may reach up to 45% of the mean absolute value, while differences between stationary and non-stationary models are of the same magnitude (differences in DLLs up to 40%). For the end of this century in the Oberland region, there is no robust tendency towards increased extremes found.
Vertical interface effect on the physical properties of epitaxial metal‐oxide films is demonstrated. Self‐assembled (BiFeO3)0.5:(Sm2O3)0.5 nanocomposite films are fabricated with three‐dimensional ...heteroepitaxy having an ordered nano‐columnar structure on a large scale. The vertical interface effect on lattice parameters, dielectric properties, and leakage currents is investigated.
We investigate light-induced changes in thickness and roughness of photosensitive polymer brushes containing azobenzene cationic surfactants by atomic force microscopy (AFM) in real time during light ...irradiation. Because the cis-state of azobenzene unit requires more free volume than its trans counterpart, the UV light-induced expansion of polymer thin films associated with the trans-to-cis isomerism of azobenzene groups is expected to occur. This phenomenon is well documented in physisorbed polymer films containing azobenzene groups. In contrast, photosensitive polymer brushes show a decrease in thickness under UV irradiation. We have found that the azobenzene surfactants in their trans-state form aggregates within the brush. Under irradiation, the surfactants undergo photoisomerization to the cis-state, which is more hydrophilic. As a consequence, the aggregates within the brush are disrupted, and the polymer brush contracts. When subsequently irradiated with blue light the polymer brush thickness returns back to its initial value. This behavior is related to isomerization of the surfactant to the more hydrophobic trans-state and subsequent formation of surfactant aggregates within the polymer brush. The photomechanical function of the dry polymer brush, i.e., contraction and expansion, was found to be reversible with repeated irradiation cycles and requires only a few seconds for switching. In addition to the thickness change, the roughness of the brush also changes reversibly between a few Angstroms (blue light) and several nanometers (UV light). Photosensitive polymer brushes represent smart films with light responsive thickness and roughness that could be used for generating dynamic fluctuating surfaces, the function of which can be turned on and off in a controllable manner on a nanometer length scale.
It is indispensable to use thin films for many technological applications. This is the first report of epitaxial growth of ternary nitride AMN2 films. Epitaxial tetragonal SrTiN2 films have been ...successfully prepared by a chemical solution approach, polymer-assisted deposition. The structural, electrical, and optical properties of the films are also investigated.
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Biphilic surfaces, namely surfaces comprising hydrophilic areas with a (super)hydrophobic background, are used in nature and engineering for controlled dropwise condensation and ...liquid transport. These, however, are highly dependent on the surface temperature and subcooling.
Here, biphilic surfaces were cooled inside a rotatable environmental chamber under controlled humidity. The condensation dynamics on the surface was quantified, depending on the subcooling, and compared to uniform superhydrophobic (USH) surfaces. Rates of condensation and transport were analyzed in terms of droplet number and size, covered area and fluid volume over several length scales. Specifically, from microscale condensation to macroscale droplet roll-off.
Four phases of condensation were identified: a) initial nucleation, b) droplets on single patches, c) droplets covering adjacent patches and d) multi-patch droplets. Only the latter become mobile and roll off the surface. Cooling the surface to temperatures between T = 2–16 °C shows that lowering the temperature shortens some of the condensation parameters linearly, while others follow a power law, as expected from the theory of condensation. The temperature dependent condensation dynamics on (super)biphilic surfaces is faster in comparison to uniform superhydrophobic surfaces. Nevertheless, within time intervals of a few hours, droplets are mostly immobile. This sets guiding lines for using biphilic surfaces in applications such as water collection, heat transfer and separation processes. Generally, biphilic surfaces are suitable for applications in which fluids should be collected, concentrated and immobilized in specific areas.
Roughness is the key parameter for surface runoff simulations. This study aims to determine robust Manning resistance coefficients (n) on the basis of consecutive artificial rainfall experiments on ...natural hillslopes available in literature, obtained at 22 different sites with different degrees of vegetation cover and type. The Manning resistance coefficient is particularly important in the context of two-dimensional (2D) hydraulic heavy rainfall simulations. Since there is a wide range of possible resistance values available leading to significantly different results regarding the accumulation of surface runoff, especially for shallow water depths. The planning of flood protection structures is directly affected by these uncertainties. This work also improves the knowledge between roughness and the shape of the hydrograph allowing a better calibration of infiltration models. As flow velocity, water depth, and infiltration rate were not observed during the rainfall experiments, only the outflow of the test field and rain intensity are known. For this purpose, a framework was developed to parameterize shallow water depth (<1 cm) -dependent roughness coefficients. To test the robustness of the framework, three different formulations of depth-dependent roughness and a constant Manning coefficient are used by comparing the measured discharge under different rainfall intensities with simulations in a 2D-hydraulic model. We identified a strong dependency of Manning’s n on the degree of vegetation cover and -type as well as an influence of consecutive rainfall events. This finally leads to a more robust parameterization of near surface roughness for hydrodynamic modelling, which is particularly important for the simulation of heavy rainfall events.
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•Framework to estimate Manning roughness by artificial rainfall experiments.•Robust roughness coefficients for shallow water runoff for multiple vegetation covers.•Improving hydrodynamic flash flood simulations.
The nature of adhesion of droplets to surfaces is a long pending scientific question. With the evolution of complex surfaces, quantification and prediction of these adhesion forces become intricate. ...Nevertheless, understanding these forces is highly relevant for explaining liquid transport in nature and establishing design guidelines for manmade interfaces. Here, it is shown that adhesion of droplets is highly sensitive to the direction of chemical heterogeneities, both in the static and dynamic regimes. This dependency is quantified by bending beam and droplet roll-off experiments. The shape of the fluid contact line on the microscale elucidates the origin of the direction-dependent adhesion. Namely, the droplet receding part pins to a higher number of patches when moving toward to the apex in comparison to the opposite direction. These findings improve the understanding of droplet adhesion to surfaces with chemical heterogeneities and directional transport phenomena.
We report on rendering polyelectrolyte brushes photosensitive by loading them with azobenzene-containing cationic surfactants. Planar poly(methacrylic acid) (PMAA) brushes are synthesized using the ...“grafting from” free-radical polymerization scheme followed by exposure to a solution of photosensitive surfactants consisting of positively-charged head groups and hydrophobic tails into which azobenzene moieties are inserted. In this study the length of the hydrophobic methylene spacer connecting the azobenzene and the charged head group ranges from 4 to 10 CH2 groups. Under irradiation with UV light, the photo-isomerization of azobenzene integrated into a surfactant results in a change in size, geometry, dipole moment and free volume of the whole molecule. When the brush loaded with photosensitive surfactants is exposed to irradiation with UV interference patterns, the topography of the brush deforms following the distribution of the light intensity, exhibiting surface relief gratings (SRG). Since SRG formation is accompanied by a local rupturing of polymer chains in areas from which the polymer material is receding, most of the polymer material is removed from the surface during treatment with good solvent, leaving behind characteristic patterns of lines or dots. The azobenzene molecules still integrated within the polymer film can be removed by washing the brush with water. The remaining nano-structured brush can then be re-used for further functionalization. Although the opto-mechanically induced rupturing occurs for all surfactants, larger species do not penetrate deep enough into the brush such that after rupturing a leftover layer of polymer material remains on the substrate. This indicates that rupturing occurs predominantly in regions of high surfactant density.
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We report on the adsorption kinetics of azobenzene-containing surfactants on solid surfaces of different hydrophobicity. The understanding of this processes is of great importance for many ...interfacial phenomena that can be actuated and triggered by light, since the surfactant molecules contain a photoresponsive azobenzene group in their hydrophobic tail. Three surfactant types are studied, differing in the spacer connecting the headgroup and the azobenzene unit by between 6 and 10 CH2 groups. Under irradiation with light of a suitable wavelength, the azobenzene undergoes reversible photoisomerization between two states, a nonpolar trans-state and a highly polar cis-state. Consequently, the surfactant molecule changes its hydrophobicity and thus affinity to a surface depending on the photoisomerization state of the azobenzene. The adsorption behavior on hydrophilic (glass) and hydrophobic (TeflonAF) surfaces is analyzed using quartz crystal microbalance with dissipation (QCM-D) and ζ-potential measurements. At equilibrium, the adsorbed surfactant amount is almost twice as large on glass compared to TeflonAF for both isomers. The adsorption rate for the trans-isomers on both surfaces is similar, but the desorption rate of the trans-isomers is faster at the glass–water interface than at the Teflon–water interface. This result demonstrates that the trans-isomers have higher affinity for the glass surface, so the trans-to-cis ratios on glass and TeflonAF are 80/1 and 2/1, respectively, with similar trends for all three surfactant types.
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