Features of medical implant passivation using anodic oxide films

The passivation ability of metals from groups IV and V of the Periodic Table is considered. Anodic treatment is able to neutralize the increase of metal hardening when comminuting grains to nanometre sizes. The deposition of metal oxide film coatings on a cobalt–chromium alloy surface results in substantial passivation of its surface and prevents cobalt and chromium accumulation in bone tissues. The decrease of surface activity of titanium implants can be achieved both by cleaning the surface during vacuum annealing before oxidation and by the increase of the anodic oxide film thickness, which limits mass and charge transfer through the implant surface. Recommended titanium implant treatment regimens are vacuum annealing at 650 °C and anodic oxidation to attain an oxide thickness less or equal to 300 nm

Impact of the type of anodic film formed and deposition time on the characteristics of porous anodic aluminium oxide films containing Ni metal

Porous anodic films containing nickel were prepared by AC electro-deposition. The porosity of the films was controlled by using different working conditions (anodisation electrolyte, voltage, and time). Then nickel was electro-deposited using an alternating voltage. The impact of the anodic film on the current density waveforms and the metal content can largely be explained by the porosity differences, while changing the deposition time caused changes due to over-oxidation of the aluminium substrate, experimentally proved by TEM. Finally, the impact of deposition time on the deposited metal was successfully fitted using an Elovich type law over a large time-span (up to 1800 s), showing the ability to achieve precise control of the metal content

Anodic dissolution of metals in oxide-free cryolite melts

The anodic behavior of metals in molten cryolite-alumina melts has been investigated mostly for use as inert anodes for the Hall-Héroult process. In the present work, gold, platinum, palladium, copper, tungsten, nickel, cobalt and iron metal electrodes were anodically polarized in an oxide-free cryolite melt (11%wt. excess AlF3 ; 5%wt. CaF2) at 1273 K. The aim of the experiments was to characterize the oxidation reactions of the metals occurring without the effect of oxygen-containing dissolved species. The anodic dissolution of each metal was demonstrated, and electrochemical reactions were assigned using reversible potential calculation. The relative stability of metals as well as the possibility of generating pure fluorine is discussed

Contribution of cellular automata to the understanding of corrosion phenomena

We present a stochastic CA modelling approach of corrosion based on spatially separated electrochemical half-reactions, diffusion, acido-basic neutralization in solution and passive properties of the oxide layers. Starting from different initial conditions, a single framework allows one to describe generalised corrosion, localised corrosion, reactive and passive surfaces, including occluded corrosion phenomena as well. Spontaneous spatial separation of anodic and cathodic zones is associated with bare metal and passivated metal on the surface. This separation is also related to local acidification of the solution. This spontaneous change is associated with a much faster corrosion rate. Material morphology is closely related to corrosion kinetics, which can be used for technological applications.Comment: 13 pages, 9 figure

Chemical analysis of a single basic cell of porous anodic aluminium oxide templates

We prepared anodic aluminium oxide (AAO) templates with “honeycomb” geometry, i.e. hexagonally ordered circular pores. The structures were extensively studied and characterized by EPMA coupled with FEG-SEM and FEG-TEM coupled with EDX at meso and nanoscopic scales, in other words, at the scale of a single basic cell making up the highly ordered porous anodic film. The analyses allowed the identification of the chemical compounds present and the evaluation of their levels in the different parts of each cell. Of note was the absence of phosphates inside the “skeleton” and their high content in the “internal part”. Various models of porous anodic film growth are discussed on the basis of the results, contributing to a better understanding of AAO template preparation and selfnanostructuring phenomena

Aligned metal oxide nanotube arrays: key-aspects of anodic TiO2 nanotube formation and properties

Over the past ten years, self-aligned TiO2 nanotubes have attracted tremendous scientific and technological interest due to their anticipated impact on energy conversion, environment remediation and biocompatibility. In the present manuscript, we review fundamental principles that govern the self-organized initiation of anodic TiO2 nanotubes. We start with the fundamental question: Why is self-organization taking place? We illustrate the inherent key mechanistic aspects that lead to tube growth in various different morphologies, such as rippled-walled tubes, smooth tubes, stacks and bamboo-type tubes, and importantly the formation of double-walled TiO2 nanotubes versus single-walled tubes, and the drastic difference in their physical and chemical properties. We show how both double- and single-walled tube layers can be detached from the metallic substrate and exploited for the preparation of robust self-standing membranes. Finally, we show how by selecting the right growth approach to TiO2 nanotubes specific functional features can be significantly improved, e.g., an enhanced electron mobility, intrinsic doping, or crystallization into pure anatase at extremely high temperatures can be achieved. This in turn can be exploited in constructing high performance devices based on anodic TiO2 in a wide range of applications.Comment: from Nanoscale Horiz., 2016, Advance Articl

Unusual synchronization phenomena during electrodissolution of silicon: the role of nonlinear global coupling

The photoelectrodissolution of n-type silicon constitutes a convenient model system to study the nonlinear dynamics of oscillatory media. On the silicon surface, a silicon oxide layer forms. In the lateral direction, the thickness of this layer is not uniform. Rather, several spatio-temporal patterns in the oxide layer emerge spontaneously, ranging from cluster patterns and turbulence to quite peculiar dynamics like chimera states. Introducing a nonlinear global coupling in the complex Ginzburg-Landau equation allows us to identify this nonlinear coupling as the essential ingredient to describe the patterns found in the experiments. The nonlinear global coupling is designed in such a way, as to capture an important, experimentally observed feature: the spatially averaged oxide-layer thickness shows nearly harmonic oscillations. Simulations of the modified complex Ginzburg-Landau equation capture the experimental dynamics very well.Comment: To appear as a chapter in "Engineering of Chemical Complexity II" (eds. A.S. Mikhailov and G.Ertl) at World Scientific in Singapor

Studies on Pitting Corrosion of Al-Cu-Li Alloys Part III: Passivation Kinetics of AA2098-T851 Based on the Point Defect Model.

In this paper, the passivation kinetics of AA2098-T851 was investigated by a fundamental theoretical interpretation of experimental results based on the mixed potential model (MPM). The steady state passive layer formed on the AA2098-T851 in NaHCO3 solution in a CO2 atmosphere upon potentiostatic stepping in the anodic direction followed by stepping in the opposite direction was explored. Potentials were selected in a way that both anodic passive dissolution of the metal and hydrogen evolution reaction (HER) occur, thereby requiring the MPM for interpretation. Optimization of the MPM on the experimental electrochemical impedance spectroscopy (EIS) data measured after each potentiostatic step revealed the important role of the migration of Al interstitials in determining the kinetics of passive layer formation and dissolution. More importantly, it is shown that the inequalities of the kinetics of formation and dissolution of the passive layer as observed in opposite potential stepping directions lead to the irreversibility of the passivation process. Finally, by considering the Butler-Volmer (B-V) equation for the cathodic reaction (HER) in the MPM, and assuming the quantum mechanical tunneling of the charge carriers across the barrier layer of the passive film, it was shown that the HER was primarily controlled by the slow electrochemical discharge of protons at the barrier layer/solution (outer layer) interface

Charge transfer tuning in TiO2 hybrid nanostructures with acceptor-acceptor systems

An interesting interplay between two different modifiers and the surface of titanium dioxide leads to a significant change in photoelectrochemical properties of the designed hybrid materials. The semiconductor is photosensitized by one of the counterparts and exhibits the photoelectrochemical photocurrent switching effect thanks to interactions with graphene oxide - the second modifier mediates charge transfer processes in the system, allowing us to design the materials response at the molecular level. Based on the selection of molecular counterpart we may affect the behaviour of hybrids upon light irradiation in a different manner, which may be useful for the applications in photovoltaics, optoelectronics and photocatalysis. Here we focus particularly on the nanocomposites made of titanium dioxide with graphene oxide combined with either 2,3,5,6-tetrachlorobenzoquinone or 2,3-dichloro-5,6-dihydroxybenzoquinone - for these two materials we observed a major change in the charge transfer processes occurring in the system