Neue Erkenntnisse zum Korrosionsschutz von organischen Beschichtungen auf Eisen

New model of corrosion protection of organic coatings on iron The corrosion kinetics of polymer-coated iron is investigated in 0.1 M NaCl. As special samples are prepared with the reference electrode located at the metal/polymer interface a direct polarization of this interface is possible by AC and DC techniques. A combination of these measurements with results obtained by non-electrochemical techniques like Kelvin-probe, Mößbauerspectroscopy and O₂-consumption allows to derive a new model of the corrosion kinetics below a polymer coating. The metal surface is covered by a swollen polymer layer and during corrosion at first iron cations are dissolved in the organic matrix. This results in a strong inhibition of the anodic partial reaction (Tafel-slope several 100 mV). Also the cathodic partial reaction (O₂-reduction) is not transport-limited but its rate is given by the electron transfer reaction. The diffusion of water and oxygen is investigated on adherent polymer films.     

In situ scanning tunneling microscopy study of selective dissolution of Au3Cu and Cu3Au (0 0 1)

We present an electrochemical study of Au₃Cu (0 0 1) single crystal surfaces in 0.1 mol dm⁻³ H₂SO₄ and 0.1 mol dm⁻³ H₂SO₄ + 0.1 mmol dm⁻³ HCl, and of Cu₃Au (0 0 1) in 0.1 mol dm⁻³ H₂SO₄. The focus is on in situ scanning tunneling microscopy experiments. The changes of the surface morphology, which are time- and potential-dependent, have been observed, clearly resolving single atomic steps and mono-atomic islands and pits. Chloride additives enhance the surface diffusion and respective morphologies are observed earlier. All surfaces have shown considerable roughening already in the passive region far below the critical potential.     

New Adhesion Promoters for Copper Leadframes and Epoxy Resin

New primer molecules have been synthesized to increase the adhesion strength between a copper leadframe and an epoxy molding compound in microelectronical devices. The coupling agents were preliminarily chemisorbed at the surface of copper plates via special binding groups like thiol, disulfide, ethylene diamine and phthalocyanine. Binding to the epoxy resin was performed via an hydroxyl group. Linear hydrocarbon spacers with various chain lengths connected the copper- and epoxy-binding groups. The self-assembled layers of the organic coupling agents at the metal surface were characterized by X-ray photoelectron spectroscopy. Thermogravimetric analysis was used to study the coating with respect to its corrosion oxidation inhibition. Shear tests clearly indicated that the coupling agents increase adhesion strength and are stable even in extreme humidity and thermal conditions in analogy to IPC-Level-1 pretreatment. Thus, delamination of the microelectronical packages was prevented.     

New Adhesion Promoters for Copper Leadframes and Epoxy Resin

New primer molecules have been synthesized to increase the adhesion strength between a copper leadframe and an epoxy molding compound in microelectronical devices. The coupling agents were preliminarily chemisorbed at the surface of copper plates via special binding groups like thiol, disulfide, ethylene diamine and phthalocyanine. Binding to the epoxy resin was performed via an hydroxyl group. Linear hydrocarbon spacers with various chain lengths connected the copper- and epoxy-binding groups. The self-assembled layers of the organic coupling agents at the metal surface were characterized by X-ray photoelectron spectroscopy. Thermogravimetric analysis was used to study the coating with respect to its corrosion oxidation inhibition. Shear tests clearly indicated that the coupling agents increase adhesion strength and are stable even in extreme humidity and thermal conditions in analogy to IPC-Level-1 pretreatment. Thus, delamination of the microelectronical packages was prevented.     

Material‐Auswahlbox zur Herstellung fortgeschrittener Polymermembranen für die Wasseraufbereitung

Within the framework of the MABMEM research project, new high‐performance membranes are being developed for sustainable water management. The performance of the membranes will be evaluated in comparative and standardized fouling tests as well as in terms of the removal of trace impurities on a laboratory scale. Seven candidates are currently being tested in demonstrator trials with real‐water matrix in a waterworks for the direct treatment of dam water without prior coagulation over a period of 6 months. Subsequently, the new membrane materials will be operated with the effluent of a wastewater treatment plant.     

Application of SKP for in situ monitoring of ion mobility along insulator/insulator interfaces

From corrosion to batteries and super-capacitors, mobility of ions at interfaces, a pre-requisite for many electrochemical processes, plays a key role in a great number of applications. In this paper we show for the first time that the Scanning Kelvin Probe (SKP) technique can be applied for studying ion mobility along any kind of insulator/insulator interface. As across these interfaces high biases can be applied, the determination of the mobility constants should be possible. Since for practically all kinds of interfaces model samples based on insulating substrate can be prepared, this is a break-through for studying ion mobility along any kind of interface, as well as mobility of ions adsorbed on a surface. While it has been shown nearly two decades ago that delamination of polymer/metal interfaces and also diffusion or migration of ions along such interfaces can be monitored in situ by SKP, no attempts have been made so far to apply this technique for investigating the mobility of ions also along interfaces between insulating materials. Here we show that this is possible. This opens up the use of SKP for a vast field of research that is of critical importance for many applications.     

Quantitative electron spectroscopic diffraction analyses of the crystal formation in dentine

Newly formed apatitic crystallites of different hard tissues consist, according to our investigations, of chains composed of nanometre-sized particles (islands, dots) arising at nucleating sites of the collagenous and noncollagenous matrix macromolecules. In dentine these islands coalesce rapidly in longitudinal direction to form needle-like crystallites which further coalesce to ribbon-like crystallites. We have concluded that the centre-to-centre distances between these islands represent the distances between the nucleating sites of the matrix macromolecules. We have applied energy-filtering transmission electron microscopy in the selected area electron diffraction mode at different stages of crystal formation in dentine and have obtained quantitative information of the degree of crystal disorder on the basis of the paracrystal theory. The fluctuation of the lattice plane distances in c -axis direction decreases, proceeding from the region near the dentine/predentine border to the dentine/enamel border.     

beta-Amyloid precursor protein isoforms show correlations with neurones but not with glia of demented subjects

Post-mortem cerebral cortex from 15 demented patients was specially collected to minimise autolysis and two membrane fractions and one soluble fraction were quantitatively examined for the major species of beta-amyloid precursor protein (APP) of high apparent molecular mass (> or = 80 kDa) together with the major mRNA species encoding APP isoforms. The number of pyramidal neurones and astrocytes, putative biochemical indices of interneurones and pyramidal neurones, and choline acetyl transferase activity were also determined. Multiple regression analysis has been used to investigate intercorrelations of APP species with biochemical and morphometric measures, free of any effects of confounding demographic variables. Subjects with Alzheimer's disease showed a loss of cholinergic activity and D-aspartate uptake compared with patients with other causes of dementia. The major finding of the study is that measures of neurones rather than astrocytes most closely correlate with the concentration of APP. Pyramidal cell numbers were positively correlated with mRNA for APP695. APP in the soluble fraction showed a negative correlation with pyramidal cell numbers and cholinergic activity. These results indicate that neurones within the cerebral cortex are the major source of APP, and that secretion of APP is dependent upon cortical pyramidal neuronal activity and cholinergic activity.     

Anbindungsverhalten organischer Monomere auf Eisenoberflächen und Korrosion der durch die Anbindung chemisch modifizierten Oberflächen

Binding behaviour of organic monomers on iron surfaces and corrosion of the resultant chemically modified surfaces In this study a new concept is discussed, to anchor polymers onto metal surfaces by primary chemical bonds. Organic molecules with two functional groups are positioned between polymer and substrate, which should be bonded to reactive centers of the metal surface by one functional group and to the polymer by conventional C-C bonds. As a first in this direction, the reaction between simple aliphatic mercaptanes and iron surfaces has been studied in detail. Surface analytical investigations have proven, that mercaptane molecules can be bonded to metallic clean iron surfaces by Fe-S-R bonds. The reaction itself has to be performed under well controlled electro-chemical conditions. The stability of the bonds is quite large as well in air as in many different electrolytes. The stability is limited by a prolonged oxygen reduction at large cathodic overpotentials. Probably, the mercaptane molecules are chemically oxidised by the H₂O₂ formed during the reduction of oxygen and the resulting sulfonic acid desorbs from the electrode surface.