Publikationen

How friction affects adhesion is addressed. The problem is considered in the context of a very stiff sphere adhering to a compliant, isotropic, linear elastic substrate and experiencing adhesion and frictional slip relative to each other. The adhesion is considered to be driven by very large attractive tractions between the sphere and the substrate that can act only at very small distances between them. As a consequence, the adhesion behavior can be represented by the Johnson–Kendall–Roberts model, and this is assumed to prevail also when frictional slip is occurring. Frictional slip is considered to be resisted by a uniform, constant shear traction at the slipping interface, a model that is considered to be valid for small asperities and for compliant elastomers in contact with stiff material. A simple model for the interaction of friction and adhesion is utilized, in which some of the work done against frictional resistance is assumed to be stored reversibly. This behavior is considered to arise from surface microstructures associated with frictional slip such as interface dislocations, where these microstructures store some elastic strain energy in a reversible manner. When it is assumed that a fixed fraction of the work done against friction is stored reversibly, we obtain good agreement with data.

A platform material composed of 2D gold (Au) nanodot plasmonic single-lattices (Au-nD-PSLs) featuring tailor-engineered geometric features for visible-NIR light-driven enhanced photocatalysis is presented. Au-nD-PSLs efficiently harness incident visible-NIR electromagnetic waves to accelerate photo-chemical reactions by localized surface plasmon resonance (LSPR) effects. Au-nD-PSLs are fabricated by a straightforward, industrially scalable template-assisted approach, using nanopatterned aluminum substrates as templates. The method overcomes the constraints of direct writing lithography and allows Au-nD-PSLs to be transferred to arbitrary functional flexible substrates. Triangular lattice Au-nD-PSLs feature tunable and controllable characteristic LSPR bands across the visible spectrum. Strongly localized electromagnetic fields around Au-nD-PSLs are responsible for the outstanding photocatalytic performance of these plasmonic nanostructures, as demonstrated by finite-difference time-domain simulations and experimental observations. Our approach of rational engineering of LSPR effects in Au-nD-PSLs provides exciting opportunities to develop high-performing and reusable photocatalysts that harvest the visible-NIR spectrum for a broad range of optoelectronic and plasmonic applications.

Use of lithium metal electrodes in solid state batteries requires well-balanced electrochemical and mechanical properties for high performance yet safe application. We present a new methodology to account for coupling mechanisms between electrochemistry and mechanics, understand morphological stability and deduce stability maps for solid polymer electrolytes adjacent to metal electrodes. We use a rigorous electro-chemo-mechanical description of the polymer electrolyte and its reaction kinetics to predict the interface current density along a deformed electrolyte interface as a function of e.g. mechanical stiffness, transport and interface properties. With these results, we explore the stability of the electrolyte-electrode interface in regard to the tendency for protrusions to grow on the metal electrode. We find that there is a critical Young’s modulus of the electrolyte above which protrusion growth is suppressed. However, the critical Young’s modulus depends on the charging rate, and on the electrochemical transport properties of the electrolyte and the interface. We develop a morphological stability map in which the critical Young’s modulus separating stable and unstable behavior is identified. The results agree well with experimental findings and might help in predicting new classes of polymer electrolytes which are more likely to perform well in the effort to suppress dendrite growth.

The statistical anionic copolymerization of isoprene (I) and styrene (S) is commonly used to synthesize tapered block copolymers, enabling control of the phase behavior by adjusting the order–disorder transition temperature, TODT. Alkyllithium initiation in hydrocarbons is known to afford tapered block copolymers of I and S in one step. The effect of tetrahydrofuran (THF) on the copolymerization kinetics and the resulting copolymers was systematically investigated by increasing the [THF]/[Li] ratio from 0 to 2500 (0 to 29%vol THF). For this purpose, in situ near-infrared (NIR) spectroscopy was employed as a versatile and fast method to track the highly accelerated consumption of the individual monomers. Changes in the I/S comonomer sequence and in the polyisoprene (PI) regioisomers, caused by variation of the THF concentration, were independently determined via NMR and in situ NIR spectroscopy. Reactivity ratios were determined as a function of the [THF]/[Li] ratio. They revealed a gradual reversal from rI ≫ rS over rI ≈ rS to rI ≪ rS. Corresponding changes in the copolymer composition profile up to a complete inversion are evident in thermal properties and morphologies. Although all copolymers possess the same comonomer composition (50%mol = 57%vol polystyrene (PS) units), small-angle X-ray scattering and transmission electron microscopy give evidence of a wide variation in bulk morphologies depending on the gradient profile. Overall, the phase diagram is symmetric, and the succession of phases bears certain similarities to the PI-b-PS case. This is discussed in terms of the increasing incompatibility of PS with 3,4-PI and the more symmetric polymer conformational parameter. The degree of segregation, as well as the nanodomain structure, was found to control the mechanical properties, showing a remarkably different viscoelastic response leading to either hard/brittle or ductile/soft materials. The accessibility of tailored gradient profiles, as well as their in-depth understanding by simply using THF as a microstructural modifier, opens a variety of possible applications. As an example, the synthesis of a PI-selective hydrogenated tapered triblock, possessing a THF-modified, phase-compatibilizing tapered block incorporated in the well-established SIS block architecture, is presented.

Abstract Switchable underwater adhesion can be useful for numerous applications, but is extremely challenging due to the presence of water at the contact interface. Here, deformable cupped microstructures (diameter typically 100 µm, rim thickness 5 µm) are reported that can switch between high (≈1 MPa) and low (<0.2 MPa) adhesion strength by adjusting the retraction velocity from 100 to 0.1 µm s–1. The velocity at which the switch occurs is determined by specific design parameters of the cupped microstructure, such as the cup width and angle. The results are compared with theoretical estimates of water penetration into the contact zone and expansion of the cup during retraction. This work paves the way for controlling wet adhesion on demand and may inspire further applications in smart adhesives.

Thiol-maleimide and thiol-vinylsulfone cross-linked hydrogels are widely used systems in 3D culture models, in spite of presenting uncomfortable reaction kinetics for cell encapsulation: too fast (seconds for thiol-maleimide) or too slow (minutes-hours for thiol-vinylsulfone). Here, we introduce the thiol-methylsulfone reaction as alternative cross-linking chemistry for cell encapsulation, particularized for PEG-hydrogels. The thiol-methylsulfone reaction occurs at high conversion and at intermediate reaction speed (seconds-minutes) under physiological pH range. These properties allow easy mixing of hydrogel precursors and cells to render homogeneous cell-laden gels at comfortable experimental time scales. The resulting hydrogels are cytocompatible and show comparable hydrolytic stability to thiol-vinylsulfone gels. They allow direct bioconjugation of thiol-derivatized ligands and tunable degradation kinetics by cross-linking with degradable peptide sequences. 3D cell culture of two cell types, fibroblasts and human umbilical vein endothelial cells (HUVECs), is demonstrated.

Hydroxyapatite coatings need similarly shaped splats as building blocks and then a homogeneous microstructure to unravel the structural and chemical hierarchy for more refined improvements to implant surfaces. Coatings were thermally sprayed with differently sized powders (20–40, 40–63 and 63–80 µm) to produce flattened homogeneous splats. The surface was characterized for splat shape by profilometry and Atomic force microscopy (AFM), crystal size by AFM, crystal orientation by X-ray diffraction (XRD) and structural variations by XRD. Chemical composition was assessed by phase analysis, but variations in chemistry were detected by XRD and Raman spectroscopy. The resulting surface electrical potential was measured by Kelvin probe AFM. Five levels of structural hierarchy were suggested: the coating, the splat, oriented crystals, alternate layers of oxyapatite and hydroxyapatite (HAp) and the suggested anion orientation. Chemical hierarchy was present over a lower range of order for smaller splats. Coatings made from smaller splats exhibited a greater electrical potential, inferred to arise from oxyapatite, and supplemented by ordered OH− ions in a rehydroxylated surface layer. A model has been proposed to show the influence of structural hierarchy on the electrical surface potential. Structural hierarchy is proposed as a means to further refine the properties of implant surfaces.

Abstract Space cooling and heating currently result in huge amounts of energy consumption and various environmental problems. Herein, a switching strategy is described for efficient energy-saving cooling and heating based on the dynamic cavitation of silicone coatings that can be reversibly and continuously tuned from a highly porous state to a transparent solid. In the porous state, the coatings can achieve efficient solar reflection (93%) and long-wave infrared emission (94%) to induce a subambient temperature drop of about 5 °C in hot weather (≈35 °C). In the transparent solid state, the coatings allow active sunlight permeation (95%) to induce solar heating to raise the ambient temperature from 10 to 28 °C in cold weather. The coatings are made from commercially available, cheap materials via a facile, environmentally friendly method, and are durable, reversible, and patternable. They can be applied immediately to various existed objects including rigid substrates.

Most everyday surfaces are randomly rough and self-similar on sufficiently small scales. We investigated the tactile perception of randomly rough surfaces using 3D-printed samples, where the topographic structure and the statistical properties of scale-dependent roughness were varied independently. We found that the tactile perception of similarity between surfaces was dominated by the statistical micro-scale roughness rather than by their topographic resemblance. Participants were able to notice differences in the Hurst roughness exponent of 0.2, or a difference in surface curvature of 0.8 $$\hbox {mm}^{-1}$$mm-1for surfaces with curvatures between 1 and 3 $$\hbox {mm}^{-1}$$mm-1. In contrast, visual perception of similarity between color-coded images of the surface height was dominated by their topographic resemblance. We conclude that vibration cues from roughness at the length scale of the finger ridge distance distract the participants from including the topography into the judgement of similarity. The interaction between surface asperities and fingertip skin led to higher friction for higher micro-scale roughness. Individual friction data allowed us to construct a psychometric curve which relates similarity decisions to differences in friction. Participants noticed differences in the friction coefficient as small as 0.035 for samples with friction coefficients between 0.34 and 0.45.