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Herein, we report the design and synthesis of a layered redox-active, antiferromagnetic metal organic semiconductor crystals with the chemical formula [Cu(H2O)2V(µ-O)(PPA)2] (where PPA is phenylphosphonate). The crystal structure of [Cu(H2O)2V(µ-O)(PPA)2] shows that the metal phosphonate layers are separated by phenyl groups of the phenyl phosphonate linker. Tauc plotting of diffuse reflectance spectra indicates that [Cu(H2O)2V(µ-O)(PPA)2] has an indirect band gap of 2.19 eV. Photoluminescence (PL) spectra indicate a complex landscape of energy states with PL peaks at 1.8 and 2.2 eV. [Cu(H2O)2V(µ-O)(PPA)2] has estimated hybrid ionic and electronic conductivity values between 0.13 and 0.6 S m−1. Temperature-dependent magnetization measurements show that [Cu(H2O)2V(µ-O)(PPA)2] exhibits short range antiferromagnetic order between Cu(II) and V(IV) ions. [Cu(H2O)2V(µ-O)(PPA)2] is also photoluminescent with photoluminescence quantum yield of 0.02%. [Cu(H2O)2V(µ-O)(PPA)2] shows high electrochemical, and thermal stability.
Electrochemical desalination shows promise for ion-selective, energy-efficient water desalination. This work reviews performance metrics commonly used for electrochemical desalination. We provide a step-by-step guide on acquiring, processing, and calculating raw desalination data, emphasizing informative and reliable figures of merit. A typical experiment uses calibrated conductivity probes to relate measured conductivity to concentration. Using a standard electrochemical desalination cell with activated carbon electrodes, we demonstrate the calculation of desalination capacity, charge efficiency, energy consumption, and ion selectivity metrics. We address potential pitfalls in performance metric calculations, including leakage current (charge) considerations and aging of conductivity probes, which can lead to inaccurate results. The relationships between pH, temperature, and conductivity are explored, highlighting their influence on final concentrations. Finally, we provide a checklist for calculating performance metrics and planning electrochemical desalination tests to ensure accuracy and reliability. Additionally, we offer simplified spreadsheet tools to aid data processing, system design, estimations, and upscaling.
In this study, polyetheretherketone composites were compounded using a two-screw extruder followed by injection moulding. The effects of multi-fillers on the mechanical properties and crystallization performances were investigated. Differential scanning calorimetry results indicate that the addition of fillers slightly increases the crystallization temperature and crystallinity. Compared to neat polyetheretherketone, the incorporation of inorganic filler leads to a significant improvement in matrix hardness, matrix stiffness and a slight increase in tensile strength. However, the material ductility, the impact strength and the fracture toughness of polyetheretherketone composites decrease. Fractography analyses show that the addition of fillers restraints the ductile deformation of polymers, which is responsible for the reduction of material ductility, impact strength as well as fracture toughness of polyetheretherketone composites.
Purpose: A powerful principle in nature is the presence of surface patterns to improve specific characteristics or to enable completely new functions. Here, we present two case studies where bioinspired surface patterns based on the adhesive system of geckos may be applied for biomedical applications: residue-free adhesion to skin and gecko-inspired suture threads for knot-free wound closure. Methods: Gecko-inspired skin adhesives were fabricated by soft lithography of polydimethylsiloxane with successive inking and dipping steps. Their adhesion was measured using a home built adhesion tester designed for patterned surfaces. Preliminary lap shear tests on the back of a human hand were also performed. Commercial suture threads from different materials were patterned in the group of A. del Campo at the Max-Planck-Institute for Polymer Research (Mainz, Germany) using oxygen plasma. The treated threads were pulled through artificial skin in both directions measuring the peak force and the pull through force. Results and Conclusions: Unpatterned reference samples of the skin adhesive did not stick to human skin, while the patterned samples all showed notable adhesion up to 1.2 Newton for a sample size of approximately 3 cm². First results with the patterned suture threads indicated that the surface patterning of the thread has only a minor effect on the pull-through forces. To achieve knot-free sewing the surface geometry of the suture threads needs to be optimized and more realistic testing procedures, e.g. testing on human skin, are necessary.
Ionic liquids (ILs) represent an important class of liquids considered for a broad range of applications such as lubrication, catalysis, or as electrolytes in batteries. It is well-known that in the case of charged surfaces, ILs form a pronounced layer structure that can be easily triggered by an externally applied electrode potential. Information about the time required to form a stable interface under varying electrode potentials is of utmost importance in many applications. For the first time, probing of relaxation times of ILs by friction force microscopy is demonstrated. The friction force is extremely sensitive to even subtle changes in the interfacial configuration of ILs. Various relaxation processes with different time scales are observed. A significant difference dependent on the direction of switching the applied potential, i.e., from a more cation-rich to a more anion-rich interface or vice versa, is found. Furthermore, variations in height immediately after the potential step and the presence of trace amounts of water are discussed as well.
Within the present work, a thermo-responsive ultrafiltration membrane is manufactured based on a polystyrene-block-poly(diethyl acrylamide) block copolymer (BCP). The poly(diethyl acrylamide) block segment features a lower critical solution temperature (LCST) in water, similar to the well-known poly(N-isopropylacrylamide), but having increased biocompatibility and without exhibiting a hysteresis of the thermally induced switching behavior. The BCP is synthesized via sequential “living” anionic polymerization protocols and analyzed by 1H-NMR spectroscopy, size exclusion chromatography, and differential scanning calorimetry. The resulting morphology in the bulk state is investigated by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) revealing the intended hexagonal cylindrical morphology. The BCPs form micelles in a binary mixture of tetrahydrofuran and dimethylformamide, where BCP composition and solvent affinities are discussed in light of the expected structure of these micelles and the resulting BCP membrane formation. The membranes are manufactured using the non-solvent induced phase separation (NIPS) process and are characterized via scanning electron microscopy (SEM) and water permeation measurements. The latter are carried out at room temperature and at 50 °C revealing up to a 23-fold increase of the permeance, when crossing the LCST of the poly(diethyl acrylamide) block segment in water.
The development of hierarchically porous block copolymer (BCP) membranes via the application of the self-assembly and non-solvent induced phase separation (SNIPS) process is one important achievement in BCP science in the last decades. In this work, we present the synthesis of polyacrylonitrile-containing amphiphilic BCPs and their unique microphase separation capability, as well as their applicability for the SNIPS process leading to isoporous integral asymmetric membranes. Poly(styrene-co-acrylonitrile)-b-poly(2-hydroxyethyl methacrylate)s (PSAN-b-PHEMA) are synthesized via a two-step atom transfer radical polymerization (ATRP) procedure rendering PSAN copolymers and BCPs with overall molar masses of up to 82 kDa while maintaining low dispersity index values in the range of Đ = 1.13–1.25. The polymers are characterized using size-exclusion chromatography (SEC) and NMR spectroscopy. Self-assembly capabilities in the bulk state are examined using transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) measurements. The fabrication of isoporous integral asymmetric membranes is investigated, and membranes are examined by scanning electron microscopy (SEM). The introduction of acrylonitrile moieties within the membrane matrix could improve the membranes’ mechanical properties, which was confirmed by nanomechanical analysis using atomic force microscopy (AFM).
Bioinspired fibrillar adhesives have been proposed for novel gripping systems with enhanced scalability and resource efficiency. Here, we propose an in-situ optical monitoring system of the contact signatures, coupled with image processing and machine learning. Visual features were extracted from the contact signature images recorded at maximum compressive preload and after lifting a glass object. The algorithm was trained to cope with several degrees of misalignment and with unbalanced weight distributions by off-center gripping. The system allowed an assessment of the picking process for objects of various mass (200, 300, and 400 g). Several classifiers showed a high accuracy of about 90 % for successful prediction of attachment, depending on the mass of the object. The results promise improved reliability of handling objects, even in difficult situations.
Adhesives for interaction with human skin and tissues are needed for multiple applications. Micropatterned dry adhesives are potential candidates, allowing for a conformal contact and glue-free adhesion based on van der Waals interactions. In this study, we investigate the superior adhesion of film-terminated fibrillar microstructures (fibril diameter, 60 μm; aspect ratio, 3) in contact with surfaces of skin-like roughness (Rz 50 μm). Adhesion decays only moderately with increasing roughness, in contrast to unstructured samples. Sinusoidal model surfaces adhere when their wavelengths exceed about four fibril diameters. The film-terminated microstructure exhibits a saturation of the compressive force during application, implying a pressure safety regime protecting delicate counter surfaces. Applications of this novel adhesive concept are foreseen in the fields of wearable electronics and wound dressing.
Due to their high energy density, Li-ion batteries have become indispensable for energy storage in many technical devices. Prussian blue and its analogs are a versatile family of materials. Apart from their direct use as an alkali-ion battery electrode, they are a promising source for templating other compounds due to the presence of carbon, nitrogen, and metallic elements in their structure, ease of synthesis, and high tunability. In this study, homogeneous iron vanadate derivatization from iron vanadium Prussian blue was successfully carried out using an energy efficient infrared furnace utilizing CO2 gas. Iron-vanadate is an inherently unstable electrode material if cycled at low potentials vs. Li/Li+. Several parameters were optimized to achieve a stable electrochemical performance of this derivative, and the effect of surfactants, such as tannic acid, sodium dodecylbenzene sulfonate, and polyvinylpyrrolidone were shown with their role in the morphology and electrochemical performance. While stabilizing the performance, we demonstrate that the type and order of addition of these surfactants are fundamental for a successful coating formation, otherwise they can hinder the formation of PBA, which has not been reported previously. Step-by-step, we illustrate how to prepare self-standing electrodes for Li-ion battery cells without using an organic solvent or a fluorine-containing binder while stabilizing the electrochemical performance. A 400 mA h g−1 capacity at the specific current of 250 mA g−1 was achieved after 150 cycles while maintaining a Coulombic efficiency of 99.2% over an extended potential range of 0.01–3.50 V vs. Li/Li+.