Chemistry-dependent X-ray-induced surface charging.

Materials science in general, and surface/interface science in particular, have greatly benefited from the development of high energy synchrotron radiation facilities. Irradiation with intense ionizing beams can however influence relevant sample properties. Permanent radiation damage and irradiation-induced sample modifications have been investigated in detail during the last decades. Conversely, reversible sample alterations taking place only during irradiation are still lacking comprehensive in situ characterization. Irradiation-induced surface charging phenomena are particularly relevant for a wide range of interface science investigations, in particular those involving surfaces of solid substrates in contact with gaseous or liquid phases. Here, we demonstrate partially reversible radiation-induced surface charging phenomena, which extend far beyond the spatial dimensions of the X-ray beam mainly as a consequence of the interaction between the surface and ionized ambient molecules. The charging magnitude and sign are found to be surface chemistry specific and dependent on the substrates' bulk conductivity and grounding conditions. These results are obtained by combining a scanning Kelvin probe with a synchrotron surface diffractometer to allow simultaneous in situ work function measurements during precisely controlled hard X-ray micro-beam irradiation.

Structure and Dynamics of Aqueous 2-Aminothiazole/NaCl Electrolytes at Electrified Interfaces.

A computational study was performed to investigate the dynamics of aqueous electrolytes containing organic corrosion inhibitors near electrified interfaces by using the constant-charge model in classical molecular dynamics simulations. The results showed that when inhibitors form films at the interface, the surface charge of the electrode causes displacement of the molecules, referred to as electroporation. The hydrophobicity of the inhibitor molecules affects both the stability of the films and their recovery time. This study highlights the value of computational investigations of the dynamics within inhibitor films as a complementary approach to the traditional focus on inhibitor-substrate interactions, leading to deeper insights into the mechanisms of corrosion inhibition mechanisms.

Molybdate and Phosphate Cross-Linked Chitosan Films for Corrosion Protection of Hot-Dip Galvanized Steel.

Environmentally friendly and sustainable methods to protect hot-dip galvanized (HDG) steel from corrosion are extensively studied. Films of the biopolymer polyelectrolyte chitosan were ionically cross-linked in this work with the well-known corrosion inhibitors phosphate and molybdate. Layers on this basis are presented as components in a protective system and could, e.g., be applied in pretreatments similar to a conversion coating. For the preparation of the chitosan-based films, a procedure involving sol-gel chemistry and wet-wet application was utilized. Homogeneous films of few micrometers thickness were obtained on HDG steel substrates after thermal curing. Properties of chitosan-molybdate and chitosan-phosphate films were compared with purely passive epoxysilane-cross-linked chitosan, and pure chitosan. Delamination behavior of a poly(vinyl butyral) (PVB) weak model top coating studied by scanning Kelvin probe (SKP) showed an almost linear time dependence over >10 h on all systems. Delamination rates were 0.28 mm h-1 (chitosan-molybdate) and 0.19 mm h-1 (chitosan-phosphate), ca. 5% of a non-cross-linked chitosan reference and slightly higher than of the epoxsyilane cross-linked chitosan. Immersion of the treated zinc samples over 40 h in 5% NaCl solution yielded a 5-fold increase of the resistance in the chitosan-molybdate system, as evidenced by electrochemical impedance spectroscopy (EIS). Ion exchange of electrolyte anions with molybdate and phosphate triggers corrosion inhibition, presumably by reaction with the HDG surface as well described in the literature for these inhibitors. Thus, such surface treatments have potential for application, e.g., in temporary corrosion protection.

Initiation and inhibition of dealloying of single crystalline Cu3Au (111) surfaces.

Dealloying is widely utilized but is a dangerous corrosion process as well. Here we report an atomistic picture of the initial stages of electrochemical dealloying of the model system Cu(3)Au (111). We illuminate the structural and chemical changes during the early stages of dissolution up to the critical potential, using a unique combination of advanced surface-analytical tools. Scanning tunneling microscopy images indicate an interlayer exchange of topmost surface atoms during initial dealloying, while scanning Auger-electron microscopy data clearly reveal that the surface is fully covered by a continuous Au-rich layer at an early stage. Initiating below this first layer a transformation from stacking-reversed toward substrate-oriented Au surface structures is observed close to the critical potential. We further use the observed structural transitions as a reference process to evaluate the mechanistic changes induced by a thiol-based model-inhibition layer applied to suppress surface diffusion. The initial ultrathin Au layer is stabilized with the intermediate island morphology completely suppressed, along an anodic shift of the breakdown potential. Thiol-modification induces a peculiar surface microstructure in the form of microcracks exhibiting a nanoporous core. On the basis of the presented atomic-scale observations, an interlayer exchange mechanism next to pure surface diffusion becomes obvious which may be controlling the layer thickness and its later change in orientation.

Inhibition of Steel Corrosion and Alkaline Zinc Oxide Dissolution by Dicarboxylate Bola-Amphiphiles: Self-Assembly Supersedes Host-Guest Conception.

For many decorative applications like industrial and architectural paints, prevention of metal substrates from corrosion is a primary function of organic coatings. Triggered release of inhibitor species is generally accepted as a remedy for starting corrosion in case of coatings damage. A polyurethane based coating, doped with bola-amphiphiles of varying molecular weight but with a common head group motif that stems from ring-opened alkenyl succinic anhydride, enables passivation of the defect and mitigates cathodic delamination, if applied on cold rolled steel. An antagonistic effect results from the intercalation of the bola-amphiphiles into layered double hydroxide Zn2Al(OH)6 and subsequent incorporation of the hybrid phase into the organic matrix. In particular higher molecular weight bola-amphiphiles get immobilized through alkaline degradation of the layered framework in the basic milieu at the cathode. By means of sediments from colloidal states it is demonstrated that in-situ formed zinc oxide encapsulates the hybrid phase, evidenced by impeded dissolution of the ZnO based shell into caustic soda. While inhibition of steel corrosion results from a Donnan barrier layer, impeded zinc oxide dissolution is rooted in zinc catalyzed bola-amphiphile hydrolysis and layered deposition of the crystalline spacer diol hydrogenated bisphenol-A.

Backside SERS studies of inhibitor transport through polyelectrolyte films on Ag-substrates.

In situ backside surface enhanced Raman spectroscopy (in situ-SERS) was newly employed for the study of the transport of inhibiting molecules through a polymer film. The barrier properties of layer-by-layer polyelectrolyte films (PE) composed of polyacrylic acid and polyallylamine hydro-chloride layers on Ag-surfaces were compared between untreated, thermally crosslinked, and Ag-nanoparticles containing samples. IB-SERS enabled the study of the transport of 2-mercaptobenzimidazole (MBI) as an inhibitor through the film. Water barrier properties of the treated PE films determined by Electrochemical Impedance Spectroscopy were correlated to the MBI diffusion kinetics. The PE stability against MBI diffusion and thermal treatment was analyzed by Infra-Red Reflection Absorption Spectroscopy (IRRAS). IRRAS showed that the thermally treated PE films formed chemical crosslinking via amide bonds and lowered the diffusion of water and the water uptake in the films. Moreover, the MBI diffusion kinetics can be followed by means of SERS. However, MBI adsorption at the PE film/metal interface was not detected after the heat treatment. In this case the adsorbed PE on the Ag surface was not substituted by the competing adsorption of MBI. Moreover, the presence of Ag-nanoparticles in the film decelerated MBI diffusion to the SERS substrate due to the trapping effect of MBI molecules.

XANES studies on Eu-doped fluorozirconate based glass ceramics.

The influence of adding InF3 as a reducing agent on the oxidation state of Eu in fluorochloro- (FCZ) and fluorobromozirconate (FBZ) glass ceramics was investigated using x-ray absorption near edge (XANES) and photoluminescence (PL) spectroscopy. For both materials, it was found that InF3 decreases the Eu2+-to-Eu3+ ratio significantly. PL spectroscopy proved that an annealing step leads to the formation of Eu-doped BaCl2 and BaBr2 nanocrystals in the FCZ and FBZ glasses, respectively. In the case of FCZ glass ceramics the hexagonal phase of BaCl2 could be detected in indium-free and InF3-doped ceramics, but only for InF3 containing FCZ glass ceramics a phase transition of the nanoparticles from hexagonal to orthorhombic structure is observed. For the FBZ glass ceramics, the hexagonal phase of BaBr2 can be formed with and without indium doping, but only in the indium-free case a phase transition to orthorhombic BaBr2 could be found.

Comparing the growth of PVD silver nanoparticles on ultra thin fluorocarbon plasma polymer films and self-assembled fluoroalkyl silane monolayers.

Adsorbed silver nanoparticles were prepared by means of electron beam evaporation of silver on ultra thin Si-supported heptadecafluoro-1-decene plasma polymer films and self-assembled heptadecafluorodecyl-trimethoxysilane monolayers. The morphology of the silver nanoparticles, characterized by their size, size distribution, shape and interparticle separation, was observed to depend on the type, chemical composition and surface energy of the sub-layer as well as the amount of silver deposited. Field emission-scanning electron microscopy was used to study the change in the morphology of the silver nanoparticles as a function of the preparation parameters. The silver nanoparticles on the ultra thin plasma polymer films demonstrated a much smaller and narrower size distribution due to the cross-linking within the film, which more effectively hinders the penetration of silver through the film in comparison to the self-assembled monolayers. Moreover, the optical properties of the resulting silver nanoparticles on the ultra thin fluorocarbon plasma polymers and their correlation to size and size distribution were investigated by spectroscopic ellipsometry in the wavelength range between 300 and 800 nm.