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N- heterocyclic carbene (NHC) self-assembled monolayers (SAMs) on gold have received considerable attention, but little is known about the lateral interactions between neighboring NHC molecules, their stability when subjected to aggressive oxidizing/reducing conditions, and their interactions with solution ions, all of which are essential for their use in a wide range of applications. To address these deficiencies, we present a comprehensive investigation of two different ferrocene (Fc)-terminated NHC SAMs with different chain lengths and linking groups. Pure monolayers of Fc-terminated NHCs display only a single, symmetrical pair of redox peaks, implying the formation of a homogeneous SAM structure with uniformly distributed Fc/Fc + redox centers. By comparison, pure Fc-alkylthiol SAMs exhibit complex and impractical redox chemistry and require surface dilution in order to achieve reproducible properties. The NHC SAMs examined in this study exhibit very fast Fc redox kinetics and comparable or even superior stability against the application of multiple potential cycles or long-time holding at constant potential compared to alkylthiol SAMs. Furthermore, ion pairing of Fc + and hydrophobic perchlorate and other hydrophilic anions is observed with Fc-NHC SAMs, highlighting conditions favorable for future applications of these monolayers. This study should therefore shed light on the very promising characteristics of redox-active NHC SAMs as an alternative to traditional Fc-alkylthiol SAMs for multiple practical applications, including in sensors and electrocatalysis.

An engineered nanoporous carbon scaffold (NCS) consisting of a 3-D interconnected 85 nm nanopore network was used here as a model material to investigate the nanoscale transport of liquids as a function of the polarity and magnitude of an applied potential ('electro-imbibition'), all in 1 M KCl solution. A camera was used to track both meniscus formation and meniscus jump, front motion dynamics, and droplet expulsion, while also quantifying the electrocapillary imbibition height ( H ) as a function of the applied potential of the NCS material. Although no imbibition was seen over a wide range of potentials, at positive potentials (+1.2 V vs. the potential of zero charge (pzc)), imbibition was correlated with carbon surface electro-oxidation, as confirmed by both electrochemistry and post-imbibition surface analysis, with gas evolution (O 2 , CO 2 ) seen visually only after imbibition was well underway. At negative potentials, vigorous hydrogen evolution reaction was observed at the NCS/KCl solution interface, well before imbibition began at -0.5 V pzc , proposed to be nucleated by an electrical double layer charging-driven meniscus jump, followed by processes such as Marangoni flow, adsorption induced deformation, and hydrogen pressure driven flow. This study improves the understanding of electrocapillary imbibition at the nanoscale, being highly relevant in a wide range of multidisciplinary practical applications, including in energy storage and conversion devices, energy-efficient desalination, and electrical-integrated nanofluidics design., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A detailed study aimed at understanding and confirming the reported highly promising performance of a La 0.3 Sr 0.7 Fe 0.7 Cr 0.3 O 3-δ (LSFCr) perovskite catalyst in CO 2 /CO mixtures, for use in reversible solid oxide fuel cells (RSOFCs), is reported in this work, with an emphasis on chemical and performance stability. This work includes an X-ray diffraction (XRD), thermogravimetric analysis (TGA), and electrochemical study in a range of pO 2 atmospheres (pure CO 2 , CO alone (balance N 2 ), and a 90-70% CO 2 /10-30% CO containing mixture), related to the different conditions that could be encountered during CO 2 reduction at the cathode. Powdered LSFCr remains structurally stable in 20-100% CO 2 (balance N 2 , pO 2 = 10 -11 -10 -12 atm) without any decomposition. However, in 30% CO (balance N 2 , pO 2 ∼ 10 -26 atm), a Ruddlesden-Popper phase, Fe nanoparticles, and potentially some coke are observed to form at 800 °C. However, this can be reversed and the original perovskite can be recovered by heat treatment in air at 800 °C. While no evidence for coke formation is obtained in 90-70% CO 2 /10-30% CO (pO 2 = 10 -17 -10 -18 atm) mixtures at 800 °C, in 70 CO 2 /30 CO, minor impurities of SrCO 3 and Fe nanoparticles were observed, with the latter potentially beneficial to the electrochemical activity of the perovskite. Consistent with prior work, symmetrical two-electrode full cells (LSFCr used at both electrodes), fed with the various CO 2 /CO gas mixtures at one electrode and air at the other, showed excellent electrochemical performance at 800 °C, both in the SOFC and in SOEC modes. Also, LSFCr exhibits excellent stability during CO 2 electrolysis in medium-term potentiostatic tests in all gas mixtures, indicative of its excellent promise as an electrode material for use in symmetrical solid oxide cells.

Hypothesis: The Lucas-Washburn (L-W) equation is the classical theory to describe the dynamics of spontaneous imbibition in single micro-channels and micro-scale porous media. However, for nanoliter droplets imbibition in nanoporous media, the L-W equation may not be suitable, due to the nanoscale liquid-solid interactions, e.g., contact line pinning and capillary condensation. In addition, for an intrinsically hydrophobic nanoporous substrate, spontaneous imbibition of a nanoliter droplet is hypothesized to occur if capillary condensation had occurred internally already., Experiments: A nanoporous carbon scaffold was synthesized and used as a model nanoporous medium. A recently-developed micro-injection technique was used to generate a series of nanoliter water droplets (2.8-34 nL); the entire wetting dynamics (i.e., apparent contact angle and droplet volume as a function of time) were observed inside an environmental scanning electron microscope., Findings: The L-W equation does not describe the wetting dynamics of nanoliter water droplets in nanoporous media. A new theoretical model is developed to characterize the corresponding dynamics. It is demonstrated that, even for an intrinsically hydrophobic nanoporous substrate, spontaneous imbibition of a nanoliter droplet can occur if capillary condensation had occurred internally already., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

With the current intense need for rapid and accurate detection of viruses due to COVID-19, we report on a platform technology that is well suited for this purpose, using intact measles virus for a demonstration. Cases of infection due to the measles virus are rapidly increasing, yet current diagnostic tools used to monitor for the virus rely on slow (>1 h) technologies. Here, we demonstrate the first biosensor capable of detecting the measles virus in minutes with no preprocessing steps. The key sensing element is an electrode coated with a self-assembled monolayer containing the measles antibody, immobilized through an N-heterocyclic carbene (NHC). The intact virus is detected by changes in resistance, giving a linear response to 10-100 μg/mL of the intact measles virus without the need to label or process the sample. The limit of detection is 6 μg/mL, which is at the lower limit of concentrations that can cause infections in primates. The NHC-based biosensors are shown to be superior to thiol-based systems, producing an approximately 10× larger response and significantly greater stability toward repeated measurements and long-term storage. This NHC-based biosensor thus represents an important development for both the rapid detection of the measles virus and as a platform technology for the detection of other biological targets of interest.

A major challenge in effectively treating infections is to provide timely diagnosis of a bacterial or viral agent. Current cell culture methods require >24 h to identify the cause of infection. The Toll-like Receptor (TLR) family of proteins can identify classes of pathogens and has been shown to work well in an impedance-based biosensor, where the protein is attached to an electrode via a self-assembled monolayer (SAM). While the sensitivity of these sensors has been good, they contain a high resistance (>1 kΩ) SAM, generating relatively small signals and requiring longer data collection, which is ill-suited to implementation outside of a laboratory. Here, we describe a novel approach to increase the signal magnitude and decrease the measurement time of a TLR-4 biosensor by inserting a redox-active ferrocenyl-terminated alkanethiol into a mixed SAM containing hydroxyl- and carboxyl-terminated alkanethiols. The SAM formation and modification was confirmed via contact angle and X-ray photoelectron spectroscopy measurements, with TLR-4 immobilization demonstrated through a modified immunosorbent assay. It is shown that these TLR-4 biosensors respond selectively to their intended target, Gram-negative bacteria at levels between 1 and 10 5 lysed cells/mL, while remaining insensitive to Gram-positive bacteria or viral particles at up to 10 5 particles/mL. Furthermore, the signal enhancement due to the addition of ferrocene decreased the measurement time to less than 1 min and has enabled this sensor to be used with an inexpensive, portable, hand-held potentiostat that could be easily implemented in field settings.

The design and application of bimetallic alloy nanoparticles (NPs) for electrocatalytic applications are challenged by the need to clearly identify and understand the individual effect of each component. In the present work, the focus has been on PtIr NPs, with alloyed NPs being previously shown to be active toward the methanol oxidation reaction (MOR), but for which the mode of action of the Ir component remains uncertain. We have therefore nanoengineered a family of Ir core @Pt shell NPs, using a modified polyol method, to control the Pt shell coverage (up to 2 monolayers) and thus to allow the separation of the bifunctional and electronic effects of Ir on the Pt activity. It is shown that the Ir core size and crystallinity do not change with the deposition of the Pt shell, as confirmed by transmission electron microscopy and X-ray diffraction. CO stripping and hydrogen underpotential deposition/removal were used for the first time to determine the surface composition of the Ir core @Pt shell NPs. It is shown that the Ir core enhances the MOR activity of the Pt shell primarily through the bifunctional effect, with an optimum Pt coverage of 0.4 of a monolayer. At 60 °C, an additional electronic effect of Ir on Pt can be discerned, causing an inhibition in the MOR rate by weakening the adsorption of methanol on the Pt shell , thus helping to remove the adsorbed CO intermediate from the shell surface.

The design and facile fabrication of an amphipathic, mechanically durable, nanoparticle (NP)-decorated film has been realized at a liquid/liquid interphase. The innovative film is prepared by applying a changing electric field across an organic-aqueous interphase in the presence of 1-2 nm metal NPs, with a specific focus on Ir NPs in this work, self-assembled at the interphase, where the organic phase consists of a dissolved hydrophobic polymer in a volatile solvent. The electrochemical process leads to the oxidation of the Ir to IrOx, forming a hydrous oxide matrix at the interphase. With evaporation of the residual volatile solvent and precipitation of the polymer backbone, an isolable Ir/IrOx-decorated film is realized. The novelty of this technique stems from the ability to fabricate a substrate material in situ around a nanoparticle matrix, as opposed to transferring the matrix onto a substrate. The subsequent film exhibits a hydrophobic and a hydrophilic surface, permitting the film to reside at a water/oil, water/air, or oil/air interphase. The differences in wettability are attributed to the differences in the chemical and physical properties of the two sides of the film. Interestingly, despite both sides of the film exhibiting different wettabilities, both sides are electrochemically accessible. Several potential applications exist for this film, including the separation and collection of oil from water, in biosensors, and as catalyst layers.

Infections affect millions of people each year and yet methods to ascertain their cause can take more than 24h to be effective. This delay between the presentation with symptoms and the ability to make an informed decision about treatment can have adverse consequences, including death in severe cases. Additionally, pathogen identification is a concern for public safety amid the growing threat of bioterrorism. Developing a detection system based on the immune system offers the advantage of broad specificity, while still remaining pertinent to human health. In this work, human Toll-Like Receptor-4 (TLR-4), a protein responsible for detecting lipopolysaccharide (LPS) of Gram-negative bacteria, was immobilized on both a large area and micro gold electrode via the tethering interaction of a modified Self-Assembled Monolayer (mSAM). In response to varying concentrations of its target, the protein-electrode combination showed a logarithmically proportional increased resistance to charge transfer from a solution-based redox probe, due to the formation of TLR-4 protein dimers. It also demonstrated excellent sensitivity to trace levels of Gram-negative bacteria, while remaining insensitive to both Gram-positive and viral challenges. Further characterization of our mSAM revealed that maintaining the appropriate receptor orientation on the electrode surface, mimicking TLR-4's role in a cellular context, was essential in producing a responsive sensor., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The catalytic activity of Rucore@Ptshell nanoparticles (NPs) towards CO oxidation, a strongly adsorbed intermediate that compromises the performance of direct methanol fuel cells, is known to be significantly better than at Pt alone. However, a systematic study aimed at understanding the beneficial effect of Ru on Pt during the methanol oxidation reaction (MOR) has not been carried out as yet. Here, Rucore@Ptshell NPs, having a controlled Ptshell coverage of zero to two monolayers and two different Rucore sizes (2 and 3 nm), were synthesized using the simple polyol method to determine the precise role and impact of Ru on the MOR in 0.5 M H2SO4 + 1 M methanol at RT and 60 °C. Because the structure of our Rucore@Ptshell NPs is known with such certainty, we were able to show here that the rate of methanol adsorption/dehydrogenation can be accelerated either by compression of the Ptshell (by making the Rucore larger) when it is less than one monolayer in thickness, or by decreasing the electronic effect of the Rucore on the Ptshell (achieved by adding a second Pt layer to the Ptshell). At low overpotentials, decreasing the Ptshell thickness also helps in increasing the rate of the MOR by enhancing the rate of oxidation of adsorbed CO. Finally, it is shown that the bi-functional effect of Ru on the Ptshell plays only a minor role in the catalysis of the MOR, especially at large particles where CO surface diffusion is facilitated.

In this work, anodically grown ZrO2 nanotubes (NTs) are examined for the first time for use in micro solid oxide fuel cell (μ-SOFC) applications. This is due to their high surface area to volume ratio and useful nanoscale morphological features (e.g., 5-100 nm thick NT bases that could serve as the electrolyte layer). To understand their full potential for these applications, the determination of their electrical properties is necessary. Therefore, ZrO2 NTs, in the form of a uniform and crack-free film, were obtained by the two-step anodization of Zr foil in aqueous solutions. The films exhibited excellent adhesion to the Zr substrate, which facilitated impedance spectroscopy analyses, used for the first time to obtain the resistivity of the nanotubular array separately from the contact resistances. This gave a conductivity of the ZrO2 NTs of 1.6 × 10(-6) S cm(-1) at 600 °C in N2, approximately twice that reported for dense ZrO2 films measured at the same temperature in air, and also a very reasonable activation energy of 0.90 eV in the 400-600 °C temperature range.

Here we show that pulsed laser-induced dewetting (PLiD) of a thin Au metallic film on a nano-scale ordered dimpled tantalum (DT) surface results in the formation of a high quality Au nanoparticle (NP) array. In contrast to thermal dewetting, PLiD does not result in deformation of the substrate, even when the Au film is heated to above its melting point. PLiD causes local heating of only the metal film and thus thermal oxidation of the Ta substrate can be avoided, also because of the high vacuum (low pO2) environment employed. Therefore, this technique can potentially be used to fabricate NP arrays composed of high melting point metals, such as Pt, not previously possible using conventional thermal annealing methods. We also show that the Au NPs formed by PLiD are more spherical in shape than those formed by thermal dewetting, likely demonstrating a different dewetting mechanism in the two cases. As the metallic NPs formed on DT templates are electrochemically addressable, a longer-term objective of this work is to determine the effect of NP size and shape (formed by laser vs. thermal dewetting) on their electrocatalytic properties.

The surface composition of nanoparticles is critical in defining their chemical and electrochemical properties. However, there are a limited number of tools that can rapidly and reliably establish these important characteristics at this small scale. In the present work, a series of Rucore@Ptshell nanoparticles (2 or 3 nm diameter Ru core, 0 to 2 monolayers of Pt in the shell layer) were synthesized and several novel electrochemical fingerprinting methods were developed to determine the Pt shell characteristics. These involved tracking the charge associated with the reduction of the oxide film formed on the exposed Rucore, as well as the potential and charge associated with COads stripping, giving the precise coverage of the first and second Pt monolayer, respectively.

The primary goal of this work is the development of a rapidly responding, sensitive, and biocompatible Ir oxide (IrOx)-based glucose sensor that regenerates solely via IrOx-mediation in both O₂-free and aerobic environments. An important discovery is that, for films composed of IrOx nanoparticles, Nafion® and glucose oxidase (GOx), a Michaelis-Menten constant (K'(m)) of 20-30 mM is obtained in the case of dual-regeneration (O₂ and IrOx), while K'(m) values are much smaller (3-5 mM) when re-oxidation of GOx occurs only through IrOx-mediation. These smaller K'(m) values indicate that the regeneration of GOx via direct electron transfer to the IrOx nanoparticles is more rapid than to O₂. Small K'(m) values, which are obtained more commonly when Nafion® is not present in the films, are also important for the accurate measurement of low glucose concentrations under hypoglycemic conditions. In this work, the sensing film was also optimized for miniaturization. Depending on the IrOx and GOx surface loadings and the use of sonication before film deposition, the i(max) values ranged from 5 to 225 μA cm⁻², showing very good sensitivity down to 0.4 mM glucose., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Ta oxide nanotubes (NTs) were formed by the anodization of Ta at 15 V in a solution of concentrated sulfuric acid containing 0.8-1.0 M hydrofluoric acid. To study the initial stages of NT formation, FESEM images of samples anodized for very short times were obtained. The results contradict the existing explanation of the current-time data collected during anodization, which has persisted in the literature for more than two decades. In addition to providing a first-time morphological study of Ta oxide NT formation at very early stages of anodization, we also propose a new interpretation of the i-t response, showing that pores are already present in the first few milliseconds of anodization and that NTs are formed well before present models predict. This behaviour may also extend to the anodization of other valve metals, such as Al, Ti, Zr, W, and Nb.

Highly ordered dimpled Ta (DT) nanotemplates, prepared by electrochemical anodization of Ta, were recently reported to be ideally suited for the fabrication of a Au nanoparticle (NP) array using a Au thin film dewetting method. Here, we provide guidance and understanding of the effect of the DT fabrication and Au film deposition steps on the characteristics of the resulting NP array. Specifically, the optimum anodization time, voltage and solution composition are established, and the thickness of the sputter-deposited metal film is shown to be a very important parameter in achieving the desired single Au NP per dimple. The resulting high quality Au NP arrays are demonstrated to be electrochemically addressable, with the total Au surface area, measured electrochemically for large-scale samples, agreeing with the calculated area, based on scanning electron microscope determination of average particle shape and distribution. As the NP formation process proceeds via confined thin film dewetting, the protocol developed here should be applicable to the formation of NP arrays of a range of other metals and alloys.

Nanoporous metal oxide structures produced by the electrochemical anodization of valve metals, such as Zr, Ti, W, Nb, Al, and recently Ta, have attracted increasing interest because of their potential use as catalysts, waveguides, and three-dimensionally arranged Bragg-stack reflectors. Here we demonstrate the formation of either supported nanotubular Ta oxide films or free-standing Ta oxide membranes, produced by controlling the conditions of Ta anodization in organic-free aqueous HF/H(2)SO(4) solutions. The supported oxide nanotubes, which are at least 15 mum in length, are characterized by very good adhesion to the Ta substrate, and extremely smooth and homogeneous walls. It is also reported here, for the first time, that these nanotubular films can be removed as free-standing Ta oxide membranes that are easily transferable to other substrates, making them potentially useful in sensors, optics, and catalysis. We also show that, when the Ta oxide nanotubes detach to form the membranes, they leave behind an ordered array of dimples in the Ta surface, with the dimples having the identical distribution and size as the pores in the previously attached nanotubes. Finally, we demonstrate how the in situ electrochemical response during anodization can be used to determine which of these highly useful Ta surface morphologies (nanotubes vs. dimples) are formed, without the need for post factum microscopic analysis. Knowledge of the meaning of these in situ signals can now serve to accelerate the controlled formation of oxide nanotubes or dimpled surfaces using other combinations of metals and anodization conditions.

We report the controlled formation of either high-aspect-ratio Ta(2)O(5) nanotubes or an organized nanoarray of Ta dimples by Ta anodization in a single H(2)SO(4) + HF solution. Dimpled Ta is the stable surface morphology in the first few seconds, followed by the growth of dense and fully vertically aligned Ta(2)O(5) nanotubes (up to 2.5 microm long). After 2 min, the dimpled surface morphology reappears, related to the build-up of a resistive Ta fluoride surface layer.

The primary aim of this work was to establish the mechanism of the oxygen reduction reaction (ORR) at (La(0.8)Sr(0.2))0.98MnO3 (LSM)-based cathodes in solid oxide fuel cells. Rate equations, based on the Butler-Volmer equation and employing either Langmuir or Temkin adsorption conditions for reactant and intermediate species, were derived, yielding predicted reaction orders and transfer coefficients. Experimental data were collected using half-cell cyclic voltammetry in a variable pO2 atmosphere (0.03 to 1 atm) at 600 to 900 degrees C, using both dense and porous LSM-based cathodes, employed to establish the impact of the accessibility of the active site on cathode activity. The rate of the ORR at dense LSM has been found to be limited by the dissociation of O(2ads)- at low currents and by the first electron-transfer step, reducing O(2ads) to O(2ads)-, at high currents. However, at porous LSM cathodes, the reaction mechanism is more difficult to deduce because the electrode morphology impacts significantly on the measured kinetic and mechanistic parameters, giving anomalous transfer coefficients of <0.5.

The rate of an activation-controlled electrochemical reaction is determined by two key parameters, the exchange current density, io, and the transfer coefficient, alpha, which is inversely related to the Tafel slope. Assuming that the symmetry factor, beta, is 0.5, the minimum alpha value should be 0.5 for all standard reaction mechanisms, with alpha values larger than this indicating a better electrocatalytic mechanism. The primary goal of this paper is to better understand why alpha values of < 0.5 are often observed experimentally, with specific examples given for the oxygen reduction reaction. These low alpha values cannot be explained by adsorption behavior, but they can result when reactions occur within a porous electrode structure. Consistent with past literature related to Tafel slope predictions, we show that long and narrow pores, a low ionic or electronic conductivity of the electrode layer, and a high io value can cause alpha to be < 0.5, most typically 0.25. However, alpha values between 0.25 and 0.5 are also encountered in practice. We show here that such alpha values can be obtained for reactions occurring at porous films that have nonuniform properties. We also show that the overpotential range over which alpha changes from 0.5 to 0.25 can be quite broad, especially at high temperatures, and thus can be misinterpreted as a true Tafel region with a transfer coefficient between 0.25 and 0.5.

We report the formation of a new PtRuIr catalyst using an organic colloid synthesis method, involving acetone as the solvent, ethylene glycol as the reducing agent, citrate as a complexing agent and stabilizer, and multiwall carbon nanotubes (CNT, diameter 8-10 nm) as the support. This catalyst has a very high real surface area and is highly active toward the oxidation of methanol, relevant to fuel cell applications. The Ir component appears to act as a promoter, and the splitting of the Pt(111) XRD feature into four peaks and the shift to larger d spacing reflect the high dispersion of the metallic components.

Identification of the species formed during the in situ reduction of hexachloroplatinic acid by sodium ethoxide, forming a Pt sol, is made. The solution phase is shown to consist of suspended metallic Pt nanoparticles (1-3 nm in diameter), acetaldehyde, and a Pt(II) species, identified by NMR and X-ray adsorption near-edge spectroscopy (XANES) to be NaPtCl3(C2H4), a sodium analogue of Zeise's salt [KPtCl3(C2H4)]. The NaPtCl3(C2H4) product exhibits greater stability in both ethanol and air than the conventional Zeise's salt, providing a means of storing the useful Zeise's anion [PtCl3(C2H4)-]. Electrochemistry, X-ray diffraction (XRD), and transmission electron microscopy (TEM) analyses have shown that the precipitate phase formed during the synthesis is composed solely of Pt particles approximately 6 nm in diameter and NaCl. Thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC) showed that the color of the precipitate is an accurate gauge of the ratio of Pt to NaCl, with the lightest to darkest precipitates containing from 1% to 40% nanoparticulate Pt by mass, respectively. A comprehensive characterization of both phases formed has allowed us to propose a mechanism for the conversion of hexachloroplatinic acid to Pt nanoparticles.

A recent advance in metallurgical technology has been the application of rapid solidification techniques to Al alloy production. FVS0812 is the designation given to a microcrystalline Al-based alloy consisting of 8 wt% Fe, 1 wt% V and 2 wt% Si. It is a two-phase alloy, consisting of ca. 27 vol percent of approximately spherical Fe-V-Si-rich dispersoids in an essentially pure Al matrix. The high strength, low density properties of this advanced material, and other related alloys, have not yet been realized, however, due, in part, to the inability of the alloy to form a thick, adherent, abrasion-resistant outer surface oxide film, a feature readily achieved at conventional Al alloys by normal anodizing methods. The present research has involved an electro-chemical study of oxide film growth at the 812 alloy, with the specific goals being to seek an understanding of the origin of the oxide film growth problem and ultimately to propose alternative approaches to the formation of a thick, stable oxide film at this material. The techniques used in this research have included electrochemical methodologies such as cyclic voltammetry and electrochemical impedance spectroscopy. Crucial information has been obtained through transmission electron microscopy (TEM) of ultramicrotomed specimens. Experiments were carried out initially in neutral borate solutions to characterize the compact barrier oxide film formed in this environment and expected to be present beneath the porous oxide film formed in the normal sulfuric acid anodizing medium.(ABSTRACT TRUNCATED AT 250 WORDS)