In the present work, the electronic structure of the passive film formed on austenitic stainless steel of the 304 type and its implications on the initiation of localised corrosion are investigated taking into account concepts developed in semiconductor physics and semiconductor electrochemistry. Capacitance measurements (Mott-Schottky approach), show that the susceptibility of AISI 304 stainless steel to stress corrosion cracking (SCC) in boiling chloride containing aqueous solutions is closely linked to the formation of a chromium rich passive oxide film with p-type semiconductivity. A small polarisation is required to drastically change the electric field at the film-electrolyte interface, as a consequence of the high doping level of the passive film. Initiation of the SCC phenomenon is described as the consequence of localised changes in the semiconductive properties of the passive film.

L'étude concerne la structure électronique des films passifs formés dans l'eau de mer artificielle, sur deux nuances d'acier inoxydable. Elle vise plus précisément à établir l'influence des principaux éléments d'alliage (Cr, Ni) sur les situations soit de déplétion soit d'accumulation dans les zones de charge d'espace formées par la polarisation aux interfaces métal/filme et film/électrolyte. Le travail expérimental repose sur les mesures de capacité (méthode de Mott-Schottky) et de photoélectrochimie. La caractérisation analytique des films passifs a été faite par spectroscopie des électrons Auger.

The electronic structure of the passive films formed on stainless steels of different chemical composition in artificial sea water is examined by capacitance measurements (Mott-Schottky approach) and photo-electrochemistry. Analytical characterization is carried out by Auger Electron Spectroscopy. The influence of the main alloying elements (Cr, Ni) on the development of space charge regions, which can be described as a depletion or accumulation layers are discussed.

Recent studies have employed tympanic thermometry to assess lateralization of cognitive and emotional functions in primates. However, no studies using this technique have investigated the possibility of hemispheric specialization in New World monkeys. Therefore, the aim of the present study was to investigate tympanic membrane (TM) temperature asymmetries and their possible correlation with stress responses in marmosets (Callithrix penicillata). Infrared TM thermometry was completed bilaterally in 24 animals (14 males and 10 females) during a stressful situation of capture and restraint. There were no significant differences between gender. A significant negative correlation was observed between TM temperature of the right ear and the number of captures (r = -0.633; P<0.001). Subjects with a more frequent previous history of captures (5 to 9 captures; N = 11) showed lower TM temperature when compared to those with fewer previous captures (1 to 4 captures; N = 13). No differences were observed for the left TM temperature. These results suggest that under intense emotional challenge (capture and restraint) there is a stronger activation of the neural structures situated in the right brain hemisphere. Taken together, the data reveal for the first time evidence of hemispheric specialization in emotional physiological processing in a New World monkey.

Estudaram-se as propriedades semicondutoras de filmes passivos formados em aço inoxidável AISI 304 e em ligas de base Ni (Alloy 600) em soluções tampão de borato. Os filmes foram estudados por medidas de capacidade (Mott-Schottky ) e de fotocorrente. Estudaram-se também filmes formados em aço inoxidável AISI 304 por oxidação ao ar, à temperatura de 350ºC. Os resultados mostram que a estrutura electrónica dos filmes é comparável à de uma heterojunção do tipo p-n, onde as cargas de espaço desenvolvidas nas interfaces filme -- metal e filme -- electrólito devem ser consideradas. O estudo electroquímico está de acordo com os resultados analíticos que demonstram que os filmes de óxido são, em todos os casos, compostos por uma região interna rica em óxido de crómio e por uma região externa rica em óxido de ferro.

The semiconducting properties of passive films formed on AISI 304 stainless steel and Alloy 600 in borate buffer solution were studied by capacitance (Mott-Schottky approach) and photocurrent measurements. Oxide films formed on 304 stainless steel in air at 350 ºC have also been studied. The results obtained show that, in all cases the electronic structure of the films is comparable to that of a p-n heterojunction in which the space charges developed at the metal-film and film-electrolyte interfaces have also to be considered. This is in accordance with analytical results showing that the oxide films are in all cases composed of an inner region rich in chromium oxide and an outer region rich in iron oxide.