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The sections in this article are Introduction Individual Steps of the Hydrogen Spillover Process Adsorption and Activation Primary Spillover Diffusion on the Support Secondary Spillover Phenomena of Hydrogen Spillover A Enhanced Adsorption B Interaction with Support C Spillover‐Assisted Catalytic Phenomena D Reverse Spillover The Nature of Spilling Hydrogen Species A Indications for Ion Pairs B Indications for H 3 Species C Indications for H Atoms D Indication for H + Ions E Theoretical Approach Oxygen Spillover Oxidation Reactions The NEMCA Effect Conclusions
The sections in this article are Introduction Individual Steps of the Hydrogen Spillover Process Adsorption and Activation Primary Spillover Diffusion on the Support Secondary Spillover Phenomena of Hydrogen Spillover A Enhanced Adsorption B Interaction with Support C Spillover‐Assisted Catalytic Phenomena D Reverse Spillover The Nature of Spilling Hydrogen Species A Indications for Ion Pairs B Indications for H 3 Species C Indications for H Atoms D Indication for H + Ions E Theoretical Approach Oxygen Spillover Oxidation Reactions The NEMCA Effect Conclusions
In dental applications, the contact between the metal implant and the receiving living tissue is made through the oxide layer on the implant surface, which allows the osseointegration process. In dentistry, the passive film formed on titanium seems to be more stable and protective than that formed on the Ti alloys, customarily used in other medical applications. Corrosion of titanium alloys in the mouth can result from the presence of a number of corrosive species, such as the hydrogen ion (H(+)), sulfide compounds (S(2-)), dissolved oxygen (O(2)) and Cl(-) and can result in the release of Ti(4+) ions that, in turn, brings about the reduction of alkaline phosphatase activity of osteoblastic cells. The present study reports a time-dependent electrochemical corrosion study of titanium in contact with the following biologically relevant solutions: (i) SBF (simulating the inorganic part of human plasma), (ii) SBF with added ovalbumin (a protein simulating the post-implant environment) and (iii) human plasma. To the best of the authors' knowledge, this is the first report on the corrosion of Ti in human plasma. The electrochemical measurements are based on electrochemical impedance spectrometry. Impedance spectra were interpreted on the basis of the equivalent-circuit approach and estimates of the time-variation of oxide film thickness and resistance were computed. Surface Raman spectroscopy was used to characterise the structure of as-anodised and corroded TiO(2) films: the effects of phosphate and organic incorporation were highlighted. EIS and surface Raman measurements have demonstrated that the corrosion resistance of the oxide films formed on Ti is strongly affected by the presence of biomolecules in the chloride- and phosphate-based aqueous solution. In particular, ovalbumin increases corrosion performance and human plasma is found to be remarkably more aggressive in comparison to SBF. These results suggest some caution in extrapolating corrosion results obtained in simulated biological fluids to the actual behaviour in vivo.
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