Michael Auinger

Dissolution of Platinum: Limits for the Deployment of Electrochemical Energy Conversion?

Platinum stability: Dissolution of Pt, which is one major degradation mechanism in, for example, hydrogen/air fuel cells, was monitored under potentiodynamic and potentiostatic conditions. The highly sensitive and time-resolving dissolution monitoring enables the distinction between anodic and cathodic dissolution processes during potential transient and chronoamperometric experiments, and the precise quantification of the amount of dissolved Pt.

Fabrication and characterization of solution-processed methanofullerene-based organic field-effect transistors

The fabrication and characterization of high-mobility, n-channel organic field-effect transistors (OFET) based on methanofullerene [6,6]-phenyl C61-butyric acid methyl ester using various organic insulators as gate dielectrics is presented. Gate dielectrics not only influence the morphology of the active semiconductor, but also the distribution of the localized states at the semiconductor-dielectric interface. Spin-coated organic dielectrics with very smooth surfaces provide a well-defined interface for the formation of high quality organic semiconductor films. The charge transport and mobility in these OFET devices strongly depend on the choice of the gate dielectric. The electron mobilities obtained are in the range of 0.05-0.2 cm2 V-1 s-1. Most of the OFETs fabricated using organic dielectrics exhibit an inherent hysteresis due to charge trapping at the semiconductor-dielectric interface. Devices with a polymeric electret as gate dielectric show a very large and metastable hysteresis in its transfer characteristics. The observed hysteresis is found to be temperature dependent and has been used to develop a bistable memory element.

Near-surface ion distribution and buffer effects during electrochemical reactions

The near-surface ion distribution at the solid-liquid interface during the Hydrogen Oxidation Reaction (HOR)/Hydrogen Evolution Reaction (HER) on a rotating platinum disc electrode is demonstrated in this work. The relation between reaction rate, mass transport and the resulting surface pH-value is used to theoretically predict cyclic voltammetry behaviour using only thermodynamic and diffusion data obtained from the literature, which were confirmed by experimental measurements. The effect of buffer addition on the current signal, the surface pH and the ion distribution is quantitatively described by analytical solutions and the fragility of the surface pH during reactions that form or consume H(+) in near-neutral unbuffered solutions or poorly buffered media is highlighted. While the ideal conditions utilized in this fundamental study cannot be directly applied to real scenarios, they do provide a basic understanding of the surface pH concept for more complex heterogeneous reactions.

Electrodeposition of zinc?silica composite coatings: challenges in incorporating functionalized silica particles into a zinc matrix

Abstract Zinc is a well-known sacrificial coating material for iron and co-deposition of suitable particles is of interest for further improving its corrosion protection performance. However, incorporation of particles that are well dispersible in aqueous electrolytes, such as silica particles, is extremely difficult. Here, we report a detailed study of Zn–SiO2 nanocomposite coatings deposited from a zinc sulfate solution at pH 3. The effect of functionalization of the silica particles on the electro-codeposition was investigated. The best incorporation was achieved for particles modified with SiO2–SH, dithiooxamide or cysteamine; these particles have functional groups that can strongly interact with zinc and therefore incorporate well into the metal matrix. Other modifications (SiO2–NH3+, SiO2–Cl and N,N-dimethyldodecylamine) of the silica particles lead to adsorption and entrapment only.

Controlling the conformational changes in donor-acceptor [4]-dendralenes through intramolecular charge-transfer processes

The synthesis of two [4]-dendralene compounds incorporating thiophene-(p-nitrophenyl) donor–acceptor units is presented. The dendralenes adopt two different conformers in solution and solid state and the transformation between the structures can be controlled by light and heat. The electron-donating components of the dendralenes are represented by bromothienyl (in 13) and ethylenedioxythiophene(EDOT)-thienyl (in 15) end-groups. The most facile transformation involves the isomerisation of donor–acceptor conjugated systems (a conformers) into structures in which only the thiophenes are conjugated (b conformers), and this process is driven by ambient light. The structures of the two conformers of compound 13 are confirmed by single-crystal X-ray diffraction studies and the structural changes in both compounds have been monitored by 1H NMR spectroscopy and absorption studies. The transformations were found to be first-order processes with rate constants of k = 0.0027 s−1 and k = 0.00022 s−1 for 13 and 15, respectively. Density functional theory calculations at the B3LYP/6-31G∗ level give credence to the proposed mechanism for the a→b conversion, which involves photoinduced intramolecular charge transfer (ICT) as the key step. The EDOT derivative (15) can be polymerised by electrochemical oxidation and a combination of cyclic voltammetry and UV/Vis spectroelectrochemical experiments indicate that the a conformer can be trapped and stabilised in the solid state.

A novel laboratory set-up for investigating surface and interface reactions during short term annealing cycles at high temperatures.

High temperature oxidation is an important research discipline that covers many topics in steel manufacture and modern energy research. To account for the need of adjusting accurate processing conditions, recent developments of the high temperature laboratory setup at the Max-Planck-Institut für Eisenforschung GmbH will be presented. The experimental assembly has been optimized to investigate surface and interface reactions at elevated temperatures in low oxygen activity gases, covering a large field of experimental possibilities. Many efforts have been taken to enable an accurate control and in situ monitoring of process conditions such as gas flow, gas composition, impurity content, and mass change of the sample.

Hydrogen Transport in Non‐Ideal Crystalline Materials

Hydrogen-transport behaviour under (non-)isothermal conditions is discussed. An extended modelling approach based on the effective diffusion coefficient is outlined for arbitrary temperature programmes, defect properties and hydrogen-loading pressures. The influence of mathematical terms, such as the trap equilibrium reaction or microstructural changes, is critically discussed and examples of thermal desorption spectra and isothermal diffusion behaviour are given.

Coupling Diffusion and Thermodynamics - Exemplified for the gas nitriding of ironchromium alloys

Kurzfassung Aufgrund der hervorragenden Eigenschaften nitrierter Stähle ist der Einsatz dieser Technik von großem Interesse für verschiedenste industrielle Anwendungen. Große Erfolge konnten während der letzten Jahrzehnte auf dem Gebiet der Nitrierhärtung erzielt werden und neben mannigfaltigen Prozessausführungen zählt das Gasnitrieren heute zu den am häufigsten eingesetzten Verfahren für eine breite Palette an Stahlsorten.Kurzfassung Aufgrund der hervorragenden Eigenschaften nitrierter Stahle ist der Einsatz dieser Technik von grosem Interesse fur verschiedenste industrielle Anwendungen. Grose Erfolge konnten wahrend der letzten Jahrzehnte auf dem Gebiet der Nitrierhartung erzielt werden und neben mannigfaltigen Prozessausfuhrungen zahlt das Gasnitrieren heute zu den am haufigsten eingesetzten Verfahren fur eine breite Palette an Stahlsorten.

Statistical evaluations of single-ion Gibbs energies of transfer

A statistical approach for the evaluation of single-ion Gibbs energies of transfer of the cations Li+, Na+, K+, Rb+, Cs+, Ba2+, Ag+, Tl+, Cu+, Zn2+, Cu2+, Cd2+, Hg2+ and Pb2+ into 40 solvents based on the principal component analysis is presented. It is shown that the Gibbs energies of transfer depend both on the nature of the cation and on the donor site of the respective solvent molecule. Correlation of the data for the investigated cations required separating the solvents into subgroups according to their donor atoms in the solvent molecule. Gibbs energies of transfer into oxygen donor solvents could be correlated with the Born term [NL(zie0)2/(8πε0ri)]. Several cation parameters were investigated with respect to the transfer data into nitrogen and sulfur donor solvents. No correlations were found. Thus the use of cation parameters derived from the statistical analysis are proposed to account for the Gibbs energies of transfer into nitrogen and sulfur donor solvents.

Formation pathways in the synthesis and properties of (Tl0.5Pb0.5)(Sr0.9Ba0.1)2Ca2Cu3Oz and (Tl0.5Pb0.5)(Sr0.8Ba0.2)2Ca2Cu3Oz-1223 superconductors

The formation pathway of (Tl0.5Pb0.5)(Sr0.9Ba0.1)2Ca2Cu3Oz and (Tl0.5Pb0.5)(Sr0.8Ba0.2)2Ca2Cu3Oz was studied by neutron and x-ray diffraction. The following reaction pathway was proposed: thallium oxide and lead oxide react with Sr-rich (Sr1-xCax )CuO2 and Ca-rich (CaxSr1-x)O to form Sr4Tl2O7 and (CaxSr1-x)PbO3, respectively. The thallate and the plumbate compounds then form the (Tl0.5Pb0.5)-1212 phase starting at a temperature of 600 ◦C. Finally, between 850 and 900 ◦C, the 1223 phase is formed from (Tl0.5Pb0.5)-1212, (CaxSr1-x)2CuO3 and CuO. Parallel experiments to fabricate the (Tl, Pb)-1223 superconductor resulted in specimens with critical temperatures of 117.5 K and 116 K, respectively, and transition widths of 2 K. Differences between the pathways for the formation of Pb-doped, Sr-rich and Pb-free, Ba-rich Tl-1223 superconductors are discussed.