Magnetic-field-assisted electrodeposition at conically structured metal layers

Konische Mikro- und Nanostrukturen besitzen spezifische magnetische, superhydrophobe und elektrokatalytische Eigenschaften und sind deshalb von hohem Interesse für eine Vielzahl von Anwendungen. Eine einfache und kostengünstige Methode zur Synthese dieser strukturierten Schichten ist die elektrochemische Abscheidung. Neben dem Einsatz von Capping-Reagenzien (engl. Capping agents) könnten Magnetfelder das lokale Konuswachstum auf einer planaren Elektrode unterstützen. In der vorliegenden Dissertation wird die Elektroabscheidung an konisch strukturierten Metallschichten in Magnetfeldern untersucht. Je nach Ausrichtung und Stärke des Magnetfeldes können die Lorentzkraft und die magnetische Gradientenkraft die Strömung des mit Metallionen angereicherten Elektrolyts in Richtung der Konusspitze gezielt antreiben. Folglich erhöht das Magnetfeld die lokale Abscheidungsrate und fördert das Konuswachstum. Für ein grundlegendes Verständnis des Effektes werden systematische numerische und theoretische Untersuchungen für die Elektroabscheidung an mm-großen Konen unterschiedlicher Materialien, Formen und Anordnungen unter verschiedenen elektrochemischen und magnetischen Bedingungen durchgeführt. Ein parallel zur Konusachse ausgerichtetes homogenes externes Magnetfeld erzeugt durch die Magnetisierung der ferromagnetischen Konen eine magnetische Gradientenkraft, die zu einer starken Unterstützung für das Konuswachstum führt. Dabei überwiegt sie oft gegenüber der Lorentzkraft und der Auftriebskraft, die durch Elektrodenreaktionen entsteht. Diese unterstützende Wirkung wird nur geringfügig abgeschwächt, wenn sich benachbarte Konusse einander annähern. Die numerischen Ergebnisse werden durch experimentelle Daten für verschiedene Konfigurationen und Abscheidungsparameter validiert. Um den Effekt der Magnetfelder zur Unterstützung des Wachstums kleinerer konischer Strukturen im Mikro- und Nanometerbereich zu ermitteln, werden die Skalengesetze für die Geschwindigkeiten der magnetisch angetriebenen lokalen Strömungen beim Verkleinern der Konusgröße aus numerischen Simulationen abgeleitet und durch eine analytische Lösung bestätigt. Obwohl die magnetische Gradientenkraft eine günstige Strömung bei ferromagnetischen Konussen erzeugt, limitieren die kleine Größe der Strömungsregion und die nahezu konstant verbleibende Dicke der Konzentrationsgrenzschicht die Unterstützung der Magnetfelder. Diese kann jedoch durch die Anwendung gepulster Ströme sowie moderat auch durch den Einsatz stärkerer Magnetfelder weiter erhöht werden. Weiterhin wird eine einfache Modellierung entwickelt, um den Einfluss von Capping-Reagenzien bei der Abscheidung von Nano-Strukturen numerisch zu simulieren. Experimentelle Resultate der von Partnern in Krakau durchgeführten Elektroabscheidung von nanostrukturierten Ni-Schichten in magnetischen Feldern werden mittels Simulationen sowohl globalen Zellströmung als auch der lokalen Strömung analysiert. Die Betrachtung beider Aspekte liefert eine Interpretation der experimentellen Ergebnisse und ermöglicht ein besseres Verständnis der Wirkung des capping agents. Zum Schluss wird der Einfluss der Wasserstoff-Nebenreaktion einbezogen. Die numerischen Ergebnisse zeigen, dass an der Konusspitze sitzende Wasserstoffblasen das Konuswachstum verringern können. Gleichzeig wird die durch die magnetischen Kräfte getriebene Strömung die Ablösung der Wasserstoffblase geringfügig verzögern.Micro- and nano-sized conical structures possess specific magnetic, superhydrophobic and electrocatalytic properties and are therefore attractive for numerous applications. Among the various methods of manufacturing such structured layers, electrodeposition appears a simple and inexpensive method. Beside the use of capping agents, the application of magnetic fields could support the local growth of cones on a non-templated planar electrode. This dissertation investigates electrodeposition at conically structured metal layers in external magnetic fields. Depending on the direction and the intensity of the magnetic field, the Lorentz force and the magnetic gradient force can generate electrolyte flow and bring electrolyte enriched with metal ions towards the cone tips. As a result, the local deposition rate is increased and conical growth is promoted. In order to obtain a basic understanding of the magnetic field effects, systematic numerical and theoretical investigations are performed for electrodeposition at mm-sized cones of different materials, shapes and arrangements under different electrochemical and magnetic conditions. If a uniform external magnetic field is oriented parallel to the cone axis, the magnetic gradient force enabled by the magnetization of ferromagnetic cones provides a strong support for conical growth, thereby often dominating over the Lorentz force and the buoyancy force arising from electrode reactions. This supporting effect is only slightly mitigated when neighboring cones are getting closer. The numerical results shown are validated by experimental data for different configurations and deposition parameters. In order to explore the prospects of magnetic fields to enhance the growth of smaller, micro- and nanometer sized conical structures, scaling laws of the local flows driven by the magnetic forces are derived numerically and confirmed analytically for shrinking cone sizes. Although the magnetic gradient force can generate a beneficial flow at ferromagnetic cones, the small flow region and the nearly constant thickness of the concentration boundary layer limit the support of the magnetic field. Enhancements of the structuring effect are observed for pulsed deposition and, despite only moderately, at higher magnetic field intensities. Furthermore, a simplified modeling approach is developed to simulate the growth mechanism of nano-cones with respect to the influence of capping agents. Experimental results of the electrodeposition of Ni cones in magnetic fields obtained by partners in Krakow are analyzed by performing simulations of both the global cell flow and the local flows generated by magnetic fields of different orientations. This two-step approach provides an interpretation of the experimental results, and gives a deeper insight on how the capping agent influences the local growth. Finally, the impact of the hydrogen side reaction on the electrodeposition in magnetic fields is considered. The numerical results indicate that hydrogen bubbles sitting at the cone tips may damp conical growth, while the magnetic-field-driven flow imposes a weak stabilizing force on the bubble

Managerial ability, financial performance and goodwill impairment: A moderated mediation analysis

This paper examines whether and how managerial ability affects the likelihood of goodwill impairment of Chinese publicly listed companies over the period 2007-2017. We document a negative relationship between goodwill impairment and managerial ability, and uncover the mediation effect of corporate financial performance. Moreover, we find that the mediation effect is moderated by firms’ earnings smoothing motivation and state ownership. The results suggest that when a company has the motivation to smooth earnings or is owned by the government, higher managerial ability of the company does not necessarily reduce the likelihood of goodwill impairment. The findings have important implications for investors and regulators

Does managerial ability affect corporate financial constraints? Evidence from China

We study the effect of managerial ability on financial constraints of Chinese listed companies. Our results indicate a negative relationship between managerial ability and corporate financial constraints. Further analyses show that managerial ability helps alleviate financial constraints probably through lowering information asymmetry, reducing agency conflicts and enhancing corporate profitability. In addition, we find evidence that private firms suffer from more severe financial constraints than state- and foreign-owned firms, and the effect of managerial ability in alleviating financial constraints is more pronounced for private firms. Overall, our findings help understand the role and highlight the importance of managerial ability in alleviating financial constraints

Pulse Reverse Plating of Copper Micro-Structures in Magnetic Gradient Fields

Micro-structured copper layers are obtained from pulse-reverse electrodeposition on a planar gold electrode that is magnetically patterned by magnetized iron wires underneath. 3D numerical simulations of the electrodeposition based on an adapted reaction kinetics are able to nicely reproduce the micro-structure of the deposit layer, despite the height values still remain underestimated. It is shown that the structuring is enabled by the magnetic gradient force, which generates a local flow that supports deposition and hinders dissolution in the regions of high magnetic gradients. The Lorentz force originating from radial magnetic field components near the rim of the electrode causes a circumferential cell flow. The resulting secondary flow, however, is superseded by the local flow driven by the magnetic gradient force in the vicinity of the wires. Finally, the role of solutal buoyancy effects is discussed to better understand the limitations of structured growth in different modes of deposition and cell geometries

Impact of tracer particles on the electrolytic growth of hydrogen bubbles

The thermocapillary effect at gas bubbles growing at micro-electrodes seems well understood. However, the interfacial flow measured in the upper bubble part decays faster than found in first simulations by Massing et al. ["Thermocapillary convection during hydrogen evolution at microelectrodes,"Electrochim. Acta 297, 929 (2019)]. Recently, Meulenbroek et al. attributed the origin of the difference to the influence of surfactants being present in the electrolyte ["Competing Marangoni effects from a stagnant cap on the interface of a hydrogen bubble attached to a microelectrode,"Electrochim. Acta 385, 138298 (2021)]. Surprisingly, the presence of tracer particles added to the electrolyte for measuring its flow was not yet considered. Our recent experiments reveal that varying the small amount of tracer particles added influences the bubble shape, its dynamics, and also the electrolyte flow nearby. We therefore present a model to describe the particle attraction to and the particle dynamics at the bubble interface, which allows us to quantify the impact. Corresponding simulations are validated against measurements for different bulk particle concentrations and show a good agreement of the tangential velocity profile at the bubble interface caused by thermo- and solutocapillary effects. Depending on the particle concentration, parts of the upper bubble interface are found to become stagnant. The results allow a deeper insight into the complex phenomena of electrolytic gas evolution and further put attention to a careful application of particle-based measurement techniques in gas-liquid systems.</p

PRNet:Pyramid Restoration Network for RAW Image Super-Resolution

Typically, image super-resolution (SR) methods are applied to the standard RGB (sRGB) images produced by the image signal processing (ISP) pipeline of digital cameras. However, due to error accumulation, low bit depth and the nonlinearity with scene radiance in sRGB images, performing SR on them is sub-optimal. To address this issue, a RAW image SR method called pyramid restoration network (PRNet) is proposed in this paper. Firstly, PRNet takes the low-resolution (LR) RAW image as input, and generates a rough estimation of the SR result in the linear color space. Afterwards, a pyramid refinement (PR) sub-network refines image details in the intermediate SR result and corrects its colors in a divide-and-conquer manner. To learn the appropriate colors for displaying, external guidance is extracted from the LR reference image in the sRGB color space, and then fed to the PR sub-network. To effectively incorporate the external guidance, the cross-layer correction module (CLCM), which fully investigates the long-range interactions between two input features, is introduced in the PR sub-network. Moreover, as different frequency components decomposed from the same image are highly correlated, in the PR sub-network, the refined features from a lower layer are utilized to support the feature refinement in an upper layer. Extensive experiments presented in this paper demonstrate that the proposed method is capable of recovering fine details and small structures in images while producing vivid colors that align with the output of a specific camera ISP pipeline

Selective delivery of interleukine-1 receptor antagonist to inflamed joint by albumin fusion

BACKGROUND: Interleukin-1 receptor antagonist, a cytokine that is highly therapeutic to rheumatoid arthritis and several other inflammatory diseases, exhibits rapid blood clearance and poor retention time on the target in clinical application due to its small size and lack of specificity to target tissue. Albumin has been widely employed as macromolecular carrier for drug delivery purpose to extend the plasma half-life of therapeutic molecules and has been shown to selectively accumulate and to be metabolized in the inflamed joints of patients with rheumatoid arthritis. This suggests that genetic fusion of IL-1ra to albumin can probably overcome the drawbacks of in vivo application of IL-1ra. RESULT: A recombinant protein, engineered by fusing human serum albumin (HSA) to the carboxyl terminal of IL-1ra, was produced in Pichia pastoris and purified to homogeneity. The fusion protein retained the antagonist activity of IL-1ra and had a plasma half-life of approximately 30-fold more than that of IL-1ra in healthy mice. In vivo bio-distribution studies demonstrated that the fusion protein selectively accumulated in arthritic paws for a long period of time in mice with collagen-induced arthritis, showing low uptake rates in normal organs such as liver, kidney, spleen and lung in contrast to IL-1ra alone. Moreover, this fusion protein was able to significantly improve the therapeutic efficacy of IL-1ra in collagen-induced arthritis mouse model. CONCLUSIONS: The fusion protein described here, able to selectively deliver IL-1ra to inflamed tissue, could yield important contributions for the therapy of rheumatoid arthritis and other inflammatory diseases