Michael Rohwerder

The Physical Meaning of Electrode Potentials at Metal Surfaces and Polymer/Metal Interfaces: Consequences for Delamination

A key parameter that controls the formation of a local galvanic element during the deadhesion of paint from base metals is the potential gradient between a defect in the paint and the intact metal oxide/polymer interface. The suitable development of zinc coatings allows for control of the potential at the intact interface and thus improvement of the delamination behavior. However, no systematic in-depth study on the origin and meaning of electrode potentials at polymer/metal interfaces or even bare metal surfaces has been presented yet, although in many recent publications Volta potential differences between inclusions and matrix measured on the surfaces of alloys are often interpreted as providing information on the galvanic activity during corrosion. It is the focus of this paper to present a detailed analysis of the origin of the potentials measured on the different materials and to point out what conclusion can be drawn from their values. Special focus is given to the technologically important system Zn-Mg.

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.

Hydrogen detection in metals: a review and introduction of a Kelvin probe approach

Abstract Hydrogen in materials is an important topic for many research fields in materials science. Hence in the past quite a number of different techniques for determining the amount of hydrogen in materials and for measuring hydrogen permeation through them have been developed. Some of these methods have found widespread application. But for many problems the achievable sensitivity is usually not high enough and ready-to-use techniques providing also good spatial resolution, especially in the submicron range, are very limited, and mostly not suitable for widespread application. In this work this situation will be briefly reviewed and a novel scanning probe technique based method introduced.

Formation of Highly Ordered and Orientated Gold Islands: Effect of Immersion Time on the Molecular Adlayer Structure of Pentafluorobenzenethiols (PFBT) SAMs on Au(111)

Self-assembled monolayers (SAMs) of pentafluorobenzenethiol (PFBT) on Au(111) substrates, prepared with different immersion times (ITs) at room temperature, were studied using scanning tunneling microscopy (STM) and infrared reflection-absorption spectroscopy (IRRAS). In the present study, the focus was on several important points of interest in the field of SAMs. First, the gold islands formed upon adsorption of PFBT molecules on the gold surface were monitored at different ITs in terms of their size, density, and shape. After short ITs (5 to 30 min), small gold islands with rounded shape were formed. These gold islands were arranged in a rather regular fashion and found to be quite mobile under the influence of the STM-tip during the scanning. When the IT was increased to 16 h, the results revealed the formation of highly ordered and orientated gold islands with very unusual shapes with straight edges meeting at 60° or 120° running preferentially along the [11(-)0] substrate directions. The density of the gold islands was found to decrease with increasing IT until they almost disappeared from the SAMs prepared after 190 h of IT. On top of the gold islands, the PFBT molecules were found to adopt the closely packed (10√3 × 2) structure. Second, a number of structural defects such as disordered regions at the domain boundaries and dark row(s) of molecules within the ordered domains of the PFBT SAMs were observed at different ITs. The SAMs prepared after 190 h of IT were found to be free of these defects. Third, at low and moderate ITs, a variation in the PFBT molecular contrast was observed. This contrast variation was found to depend mainly on the tunneling parameters. Finally, our results revealed that the organization process of PFBT SAMs is IT-dependent. Consequently, a series of structural phases, namely, α, β, γ, δ, and ε were found. The α-, β-, γ-, and δ-phases were typically accompanied by the ε-phase that appeared on top of gold islands. With increasing IT, the α→β→ γ→δ→ε phase transitions took place. The resulting ε-phase, which covered the entire gold surface after 190 h of IT, yielded well-ordered self-assembled monolayers with large domains having a (10√3 × 2) superlattice structure.

Polymorphism in self-assembled terphenylthiolate monolayers on Au(111)

Self-assembled monolayers (SAMs) of terphenylthiol (TPT) on gold Au(111) substrates exhibit well-ordered structures over large scales if they are annealed in ethanol at 40 °C after their formation. Using high-resolution STM, two distinct, ordered phases could be observed. The simpler phase, designated as α-phase, consists of closely packed molecules in the well-known (2√3 × √3)R30° structure. It could be demonstrated that under less suitable imaging conditions this phase can be mistaken as the hexagonal (√3 × √3)R30°, which resolves a discrepancy in between previous reports. The second phase is characterized by a stripe pattern with a periodicity of 2.0 nm and can be described by a point-on-line incommensurate (4 × n) ([Formula: see text]) lattice with n close to 8. This β-phase contains four pairs of terphenylthiolate molecules, which might be held together by either disulfide bonds or the recently discussed S-Au-S motif, and is thus 35% ± 15% less densely packed than the α-phase. The coexistence of these phases explains the variability of spectroscopic results obtained in the past for terphenylthiolate layers, since their relative proportion determines the average thicknesses/tilt angles found in these studies.

Modulation of electrochemical hydrogen evolution rate by araliphatic thiol monolayers on gold

Electroreductive desorption of a highly ordered self-assembled monolayer (SAM) formed by the araliphatic thiol (4-(4-(4-pyridyl)phenyl)phenyl)methanethiol leads to a concurrent rapid hydrogen evolution reaction (HER). The desorption process and resulting interfacial structure were investigated by voltammetric techniques, in situ spectroscopic ellipsometry, and in situ vibrational sum-frequency-generation (SFG) spectroscopy. Voltammetric experiments on SAM-modified electrodes exhibit extraordinarily high peak currents, which di er between Au(111) and polycrystalline Au substrates. Association of reductive desorption with HER is shown to be the origin of the observed excess cathodic charges. The studied SAM preserves its two-dimensional order near Au surface throughout a fast voltammetric scan even when the vertex potential is set several hundred millivolt beyond the desorption potential. A model is developed for the explanation of the observed rapid HER involving ordering and pre-orientation of water present in the nanometer-sized reaction volume between desorbed SAM and the Au electrode, by the structurally extremely stable monolayer, leading to the observed catalysis of the HER.

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.

Integrated scanning kelvin probe-scanning electrochemical microscope system: Development and first applications

The integration of a scanning Kelvin probe (SKP) and a scanning electrochemical microscope (SECM) into a single SKP-SECM setup, the concept of the proposed system, its technical realization, and first applications are presented and discussed in detail. A preloaded piezo actuator placed in a grounded stainless steel case was used as the driving mechanism for oscillation of a Pt disk electrode as conventionally used in SECM when the system was operated in the SKP mode. Thus, the same tip is recording the contact potential difference (CPD) during SKP scanning and is used as a working electrode for SECM imaging in the redox-competition mode (RC-SECM). The detection of the local CPD is established by amplification of the displacement current at an ultralow noise operational amplifier and its compensation by application of a variable backing potential (V(b)) in the external circuit. The control of the tip-to-sample distance is performed by applying an additional alternating voltage with a much lower frequency than the oscillation frequency of the Kelvin probe. The main advantage of the SKP-SECM system is that it allows constant distance measurements of the CPD in air under ambient conditions and in the redox-competition mode of the SECM in the electrolyte of choice over the same sample area without replacement of the sample or exchange of the working electrode. The performance of the system was evaluated using a test sample made by sputtering thin Pt and W films on an oxidized silicon wafer. The obtained values of the CPD correlate well with known data, and the electrochemical activity for oxygen reduction is as expected higher over Pt than W.

On the complexation kinetics for metallization of organic layers: palladium onto a pyridine-terminated araliphatic thiol film

Palladium nanoparticles have been deposited electrochemically onto self-assembled monolayers (SAMs) of 4-(4-(4-pyridyl)phenyl)phenylmethanethiol. A pronounced correlation between the kinetics of the complexation between pyridine nitrogens and Pd cations and the sample potential has been observed. The amount of the Pd deposit significantly increases by adjusting the sample potential during the complexation step to values below the point of zero charge. The size of the spherical shaped Pd nanoparticles varies within a certain limit according to the amount of Pd(2+) ions initially coordinated on top of the SAM. The metallic state of these particles was confirmed by X-ray photoelectron spectroscopy and infrared reflection-absorption spectroscopy. Moreover, CO adsorption on the clean Pd deposit revealed further information about the crystallographic orientation of the nanoparticles.

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.