Growth Of Oxide Films Research Articles

Influence of composition and temperature on oxide film formation for Fe-Cr-Ni alloys in simulated PWR primary water

ABSTRACT The growth of oxide films on Fe-Cr-Ni alloys in simulated pressurized water reactor (PWR) primary system environments was investigated, with focus on the influence of alloy composition and temperature. Oxide film thicknesses were measured for 90 specimens prepared from compact tension (CT) test pieces. Cross-sectional observations were also conducted on coupon specimens using scanning transmission electron microscopy (STEM). The behavior of Ni-based alloys, specifically Alloy 600, and Fe-based alloys, specifically Type 316 stainless steel, were compared. Ni-based alloys exhibit superior corrosion resistance due to slower Fe diffusion kinetics compared to Fe-based alloys, leading to the formation of a nickel-enriched protective layer at the metal-oxide interface. The oxidation rates of Ni-based alloys follow an Arrhenius-type temperature dependence. In contrast, Fe-based alloys show a more complex temperature-dependent behavior, with reduced oxidation rates at higher temperatures that are likely due to changes in oxide dissolution. Higher chromium concentrations in both alloy types improve the protectiveness of the oxide film towards corrosion by forming a more compact inner oxide layer. The study identifies three primary factors influencing oxide film growth: reactions at the metal-oxide interface, diffusion within the oxide layer, and processes at the oxide-solution interface. The relative significance of these processes varies depending on the alloy composition and temperature.

Bridging to Commercialization: Record-Breaking of Ultra-Large and Superior Cyclic Stability Tungsten Oxide Electrochromic Smart Window.

Electrochromic smart windows (ESWs) can significantly reduce energy consumption in buildings, but their cost-effective, large-scale production remains a challenge. In this study, the instability of black phosphorus is leveraged to induce the growth of the tungsten oxide film through its decomposition process, inspired by the 2D material-assisted in situ growth (TAIG) method. This approach results in the preparation of large-scale, high-performance WO3-x·nH2O (n<2) films. Characterization techniques and DFT calculations confirm efficient regulation ofstructural water and oxygen vacancies during TAIG preparation. The WO3-x·nH2O films exhibit excellent electrochromic (EC) properties, including high transmittance modulation (74.2%@1100nm), fast switching time (tc=5.5s, tb=3.8s), high coloration efficiency (124.7cm2C-1), and superior cyclic stability (transmittance modulation retained 94.7% after 20000 cycles). Ultra-largeWO3-x·nH2O film are prepared via a simple immersion process, and fabricated into a large-area ESW under facile laboratory conditions, demonstrating the economic and practical feasibility of this approach in industrial-scale production. Operated by the intelligent control circuit, the ESWexhibits remarkable EC properties and cyclic stability This research represents a milestone in improving the performance and industrial-scale production of ESWs, bridging the gap to the commercialization of EC technology.

Effect of Zr addition on the corrosion resistance of Ti-Mo alloy in the H2O2-containing inflammatory environment

Reactive oxygen species (ROS), produced by immune cells during inflammatory reaction, are known to promote corrosion of standard biomedical materials such as CP-Ti and Ti-6Al-4V. Electrochemical corrosion in the ROS environment can be further accelerated in the vicinity of fretting regions, where titanium can be polarized towards negative potentials. This study considers both of these aspects and presents corrosion analysis under complex inflammatory conditions for Ti-Mo and Ti-Mo-Zr alloys, which offer exceptional strain-hardening behavior and ductility. Combining electrochemical impedance spectroscopy (EIS) and atomic emission spectroelectrochemistry (AESEC) allowed us to understand the origin of ROS-induced corrosion. At free corrosion conditions, Zr was found to suppress oxide layer growth without any significant effect on the dissolution process. On the other hand, Zr suppressed dissolution rate under cathodic potentials. Although applying cathodic potential resulted in a rapid increase of dissolution rate, cross-section transmission electron microscopy (TEM) analysis did not reveal significant influence of the short cathodic polarization on the oxide film growth during further prolonged exposure at free corrosion conditions.

On-demand performance optimization of AlGaN/GaN high electron mobility transistors using stoichiometric variation of dielectric alloy AlxTayO

The current research investigates the potential advantages of optimally combining wide bandgap Al2O3 with high dielectric constant (high-κ) Ta2O5 for gate dielectric applications. Various compositions of 10 nm AlxTayO oxide films are grown on the Al0.3Ga0.7N/GaN heterostructure by co-sputtering Al and Ta metals, followed by thermal oxidation at 500 °C. The average root-mean-square roughness of the grown oxide films is ∼1.2–1.4 nm compared to 0.4 nm for as-deposited metal. X-ray photoelectron spectroscopy and transmission electron microscopyconfirm the formation and thickness of the grown oxide films. The bandgap (Eg) of the oxide films calculated from O1s electron energy loss spectra show a linear increase from 4.85 eV for pure Ta2O5 to 6.4 eV for pure Al2O3. The dielectric constant (εox) calculated from capacitance–voltage (CG−VG) measurements decreases linearly from 25.7 for Ta2O5 to 7.9 for Al2O3. The interface trap density (Dit) is estimated from the frequency dispersion of capacitance–voltage (CG−VG) characteristics. The DC and radio frequency (RF) characteristics of AlxTayO/Al0.3Ga0.7N/GaN high electron mobility transistor (HEMT) devices are measured and compared with the Schottky HEMT devices (without any gate oxide). Compared to Schottky HEMT devices, AlxTayO/Al0.3Ga0.7N/GaN HEMT devices show superior DC characteristics, which helps us achieve maximum RF output power. Furthermore, the OFF-state measurements show that the AlxTayO/Al0.3Ga0.7N/GaN HEMT devices can sustain higher source-to-drain voltages, from a minimum of 88 V on pure Ta2O5 metal-oxide-semiconductor (MOS)-HEMTs to a maximum of 138 V on pure Al2O3 MOS-HEMTs before the dielectric breakdown happens, compared to a 57 V breakdown voltage on Schottky HEMT devices. An oxide variation of AlxTayO, with Al composition ratio of 0.34, shows an exceptional ION/IOFF ratio of 4 × 1011, a gate leakage current of 8 × 10−12 A/mm, a near-ideal subthreshold slope of 63.8 mV/dec, and the unity current gain frequency (fT) of 25.6 GHz.

Atomistic insight into structure and properties of oxide films formed upon oxidation of Al–Mg alloys – reactive molecular dynamics study

Oxidation phenomena on metal surfaces can be advanced using atomistic modeling for the study of the structure and properties of the growing oxide films. Molecular dynamics investigations were performed to study thermal oxidation of single-crystal and polycrystalline Al–Mg alloys with low Mg content of up to 2.5 at. %. Structure, topological atom network and surface topography of the oxide films grown on Al–Mg surfaces at 300, 475 and 663 K are determined. Mg-content and temperature dependent oxide films developed on Al-Mg alloy substrates with two-phase oxide film formation as also confirmed experimentally. It is related with a gradual long-range order formation above 475 K for (Al,Mg)-oxide films, for which solid amorphous phase predominates over crystalline phase. The 1.12-nm-thick oxide films grown at 300 K are fully amorphous and build up from (Al, Mg)-oxide which the Al2O3 dominates. Increase of Mg coefficient confirms faster Mg diffusion to oxide/alloy interface at high oxidation temperature and the formation of MgO-like network. The presence of planar crystal defect (grain boundary, GB) into Al-Mg alloy substrate governs the kinetics of oxide film growth and its structure evolution. GB also compensate internal stresses during oxide film growth. Obtained results are in good agreement with experimental observations.

Review of Anodic Tantalum Oxide Nanostructures: From Morphological Design to Emerging Applications.

Anodization of transition metals, particularly the valve metals (V, W, Ti, Ta, Hf, Nb, and Zr) and their alloys, has emerged as a powerful tool for controlling the morphology, purity, and thickness of oxide nanostructures. The present review is focused on the advances in the synthesis of micro/nanostructures of anodic tantalum oxides (ATO) in inorganic, organic, and mixed inorganic-organic type electrolytes with critically highlighting anodization parameters, such as applied voltage, current, time, and electrolyte temperature. Particularly, the growth of ATO nanostructures in fluoride containing electrolytes and their applications are briefly covered. The details of the current- or voltage-time transient and its relation to the growth of the anodic oxide films are presented systematically. The main discussion revolves around the incorporation of various electrolyte species into the surface of ATO structures and its effects on their physicochemical properties. The latest progress in understanding the growth mechanism of nanoporous/nanotubular ATO structures is outlined. Additionally, the impact of annealing temperature (ranging from 400-1000 °C) and atmosphere on the crystalline structure, morphology, impurity content, and physical properties of the ATOs is briefly described. The common modification methods, such as decorating with other transition metal/metal oxide, heteroatom doping, or generating defects in the ATO structures, are discussed. Besides, the review also covers the most promising applications of these materials in the fields of capacitors, supercapacitors, memristive devices, corrosion protection, photocatalysis, photoelectrochemical (PEC) water splitting, and biomaterials. Finally, future research directions for designing ATO-based nanomaterials and their utilities are indicated.

Laser-induced growth of metal oxide films on quartz tubes for photocatalytic water treatments

A solid-state pulsed laser technique was developed to in situ grow arbitrary immobilized catalysts (Fe3O4, CeO2, WO3 etc.) on the inner surface of quartz tube with robust adhering strength. In a case study, anatase/rutile hetero-phase TiO2 film was deposited to serve as immobilized photocatalysts for the effective removal of antibiotics from aqueous environment. The X-ray absorption spectroscopy, low temperature electron paramagnetic resonance and the density functional theory simulation directly confirm a defect-assisted type-II band alignment was established to facilitate the charge transfer at the hereto-interphase. In addition, the oxygen vacancy enriched anatase phase with greater binding energy towards the dissolved oxygen facilitated the O2– generation. Meanwhile, the rutile phase enriched with Ti3+ could effectively activate the antibiotics to promote the direct h+ mediated oxidation. Such integration of unique atomic vacancies prevent defects from becoming electron-hole recombination centers and consequently extend the lifetime of the photoexcited charge carrier. The degradation mechanism of oxytetracycline was thoroughly examined by ultra-high resolution electrospray time-of-flight mass spectrometry and Fukui function, while the ecological structure–activity relationships program assessed the toxicity of contaminant to the environment. Milewhile, a continuous water treatment apparatus employing the catalytic tubes as reactors was established and demonstrated a ∼ 95 % OTC degradation under the natural sunlight adopting river water as the background. The experimental studies also claimed that ∼ 90 % of the initial activity could be retained after 100 cycles reuse, which permits their great potential for the applicational scenarios.

High-temperature oxidation behavior of Mar-M247 and Mar-M247LC for aero-engines at 800–950 °C in air

The isothermal oxidation behavior of Mar-M247 and Mar-M247LC was investigated in air at 800–950 °C for 500 h. The oxidation activation energies of 327.7 kJ/mol and 281.4 kJ/mol were obtained, respectively. The oxidation kinetics and oxide layer evolution indicated that the Cr3+ outward diffusion dominated the oxide film growth. Firstly, NiO replaced Cr2O3 as the outer layer above 900 °C. Next, the formation of the internal Al2O3 was closely related to the γ' phase dissolution. The size of the γ' and the γ/γ' interfacial area may be one of the possible reasons for the minor differences in the Mar-M247 and Mar-M247LC oxidation properties. And finally, it is speculated that the oxide pegs in the oxide layer enhance the adherence of the oxide film to the substrate.

Crystal orientation of epitaxial film deposited on silicon surface

Direct growth of oxide film on silicon is usually prevented by extensive diffusion or chemical reaction between silicon (Si) and oxide materials. Thermodynamic stability of binary oxides is comprehensively investigated on Si substrates and shows possibility of chemical reaction of oxide materials on Si surface. However, the thermodynamic stability does not include any crystallographic factors, which is required for epitaxial growth. Adsorption energy evaluated by total energy estimated with the density functional theory predicted the orientation of epitaxial film growth on Si surface. For lower computing cost, the adsorption energy was estimated without any structural optimization (simple total of energy method). Although the adsorption energies were different on simple ToE method, the crystal orientation of epitaxial growth showed the same direction with/without the structural optimization. The results were agreed with previous simulations including structural optimization. Magnesium oxide (MgO), as example of epitaxial film, was experimentally deposited on Si substrates and compared with the results from the adsorption evaluation. X-ray diffraction showed cubic on cubic growth [MgO(100)//Si(100) and MgO(001)//Si(001)] which agreed with the results of the adsorption energy.

Growth and physical-chemical characterization of manganese oxide and graphene-manganese oxide films for potential applications in energy store devices

The need for progress in the development of energy supply devices such as batteries and large capacitors has led to the improvement and innovation of these devices so that they can store energy efficiently, and additionally, they must be small, light, with low production costs, and friendly to the environment. For these reasons, in this investigation results of the characterization of physical and chemical behaviors of graphene-manganese oxide and copper and manganese oxide-copper systems are studied. The graphene was synthesized through the electrochemical exfoliation technique and deposited as a film on common glass and silicon substrates via the spray technique, and over this film, Mn2O3 films were deposited through spin coating. The Raman results showed the presence of peaks D and G, located at 1534 and 1597 cm−1, respectively. XPS analysis demonstrated that the graphene is made up of three layers. TEM studies determined that the graphene is polycrystalline, and XRD established the manganese oxide coatings’ growth along the (222) and (440) planes of Mn2O3. The optical behavior indicated that the absorbance of the graphene-Mn2O3 system decreases the energy gap in 0.8 eV concerning Mn2O3 films. The voltage-current measurements suggest that the density current in the discharge process of the Mn2O3–Cu electrode system was improved approximately 3-fold with the graphene-Mn2O3–Cu electrode system. The obtained results conclude that the addition of graphene to manganese oxide coatings increases their electrochemical performance, so graphene-manganese oxide could be used in energy storage devices.

Tin oxide thin films on Ag(111): Thickness and temperature dependent study of surface structure and electronic properties

Growth and structure of tin oxide films on Ag(111) from submonolayer to 10 monolayer equivalent thickness have been studied using low energy electron diffraction (LEED), x-ray photoemission spectroscopy (XPS) and angle-resolved photoemission spectroscopy techniques for room temperature (RT) and high temperature (HT) (573 K). For RT growth, most of the tin is oxidised to form tin oxide (SnOx) as confirmed by XPS where no metallic component is noticed. However, the grown films are not epitaxial or ordered which can be confirmed by no spots in LEED for higher coverage. Metallic Sn along with two oxidation states of Sn are noticed for HT growth, with the surface mainly composed of SnO2. LEED pattern shows the presence of c(2 × 2) and (3 × 1) along with two different hexagonal multidomain type patterns. The electronic structure for lower coverage resembled the Sn/Ag(111) alloy structures for lower coverage. For higher coverages appearance of three bands below 2 eV binding energy was noticed.

Hydroxyl transport mechanisms upon passivation of Cr-Fe-Co-Ni-Mo multi-principal element alloy surfaces investigated by isotopic labelling

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) combined with deuterium labelling (D2O), and X-ray photoelectron spectroscopy (XPS) were applied to investigate the interfacial transport mechanisms of hydroxyls between aqueous electrolyte and outer part of the protective oxide film during passivation of Cr15Fe10Co5Ni60Mo10 multi-principal element alloy surfaces. A ToF-SIMS signal treatment methodology was developed to retrieve the in-depth distribution of deuterated hydroxides in the nanometer-thick surface oxide film. After immersion at free potential or anodic passivation in acidified D2O, the initial bilayer structure is retained. The use of heavy water electrolyte has no effect on the composition alterations induced by passivation. Deuterated species were detected mostly in the outer layer of the surface oxide film. Pure inward hydroxyl diffusion from electrolyte/oxide to oxide/metal interface is excluded from being primarily responsible for oxide film growth induced by anodic passivation. The hydroxyls from the dissolving hydroxide species are retained in the oxide film and participate in forming Cr hydroxide, thus reducing the hydroxyl surface uptake from the electrolyte. This work provides deeper insight into the mechanisms of oxide growth and corrosion protection induced by anodic passivation.

Growth of ultrathin cobalt oxide films on Pd(100): Refined structural model

We present an atomistic-level study on the growth of cobalt oxide ultra-thin films prepared on Pd(100) substrate performed by a combination of scanning tunneling microscopy (STM) and Low Energy Electron Diffraction (LEED). In this contribution, we report a new surface structure c(12×2)-CoO(111), which co-exist with the previously reported extended c(4 × 2)-CoO(100) domains at low Co deposition coverages. We demonstrate that the lattice parameters derived for the newly observed hexagonal c(12×2)-CoO(111) phase fit the three- or sixfold lattice parameter of the c(4 × 2)-CoO(100) layer. The c(12×2)-CoO(111) layer was shown to grow directly on top of the c(4 × 2)-CoO(100) structure, offering a transition mechanism from rectangularly to hexagonally terminated CoO surface. At growing Co coverages, HEX-CoO(111) domains exhibiting a Moiré pattern followed by the formation of well-defined Co3O4(111) islands, were prepared and structurally characterized. Both latter phases have been previously reported in the literature. Finally, we provide a refined model for the epitaxial growth of cobalt oxide thin films on Pd(100), including the formation of new c(12×2)-CoO(111) phase.

Effect of Al–Fe–Mn–Si particle characteristics on the growth morphology and corrosion resistance of anodic oxide film on AA 3003 aluminium alloy

This study examines the impact of Al–Fe–Mn–Si particle characteristics in AA3003 alloy on the morphology and resistance of anodic oxide films against corrosion. The results show that low-silicon-content Al–Fe–Mn–Si particles oxidise simultaneously with the matrix to form a discontinuous porous oxide film, and complex small pores are formed in the porous layer; although high-silicon-content Al–Fe–Mn–Si particles have the same oxidation rate as the alloy matrix, the growth of the oxide film is hindered by unoxidised particles in the porous layer due to the influence of particle size and chemical composition, resulting in uneven growth of the oxide film and ultimately causing defects such as enlarged pores and cracks. A mechanism model for Al–Fe–Mn–Si particles affecting the morphology of oxide film growth was established. Electrochemical test results show that compared with the oxide film of the high-silicon-content alloy, the oxide film of the low-silicon-content alloy has better corrosion resistance performance, with a corrosion potential of −0.512V (compared with −0.836V for the high-silicon alloy) and a corrosion current density of 3.34 × 10−8A/cm2 (compared with 9.614 × 10−7 A/cm2 for high-silicon alloy). The barrier layer attained an elevated impedance value and exhibited self-repairing capabilities.

Controlling Nucleation Sites for Metal Oxide Film Growth on Glassy Carbon via Electrochemical Preoxidation.

Coating electrode materials with metal oxide thin films can improve the performance of electrocatalysts and charge storage materials. Atomic layer deposition (ALD) enables the deposition of conformal, uniform films on a wide range of electrodes; however, an even film depends on the availability of nucleation sites directly on the electrode surface. Here, we show that the electrochemical oxidation of glassy carbon electrodes prior to the deposition of alumina thin films by ALD leads to more uniform electrochemically passivating films. Cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) demonstrate that film uniformity increases with the increasing potential of preoxidation until 2.50 V versus Ag/AgCl, at which point the films are fully passivating and appear continuous by SEM. Further increasing the potential of preoxidation leads to uniform but less consistently passivating alumina films. These findings show that electrochemical preoxidation is a rapid and readily tunable strategy for controlling oxygenic nucleation sites and therefore the growth of thin metal oxide films on glassy carbon electrodes.

Isotopic Tracer Study of Initiation of Porosity in Anodic Alumina Formed in Chromic Acid.

In this paper, we focused on the initiation of porosity in the anodic alumina under galvanostatic conditions in chromic acid, using an 18O isotope tracer. The general concept of the initiation and growth of porous anodic oxide films on metals has undergone constant development over many years. A mechanism of viscous flow of the oxide from the barrier layer to the pore walls has recently been proposed. In this work, two types of pre-formed oxide films were analysed: pure Al2O3 formed in chromic acid, and a film containing As ions formed in a sodium arsenate solution. Both were anodized in chromic acid for several different time durations. Both pre-formed films contained the oxygen isotope 18O. The locations and quantities of 18O and As were analysed by means of ion accelerator-based methods supported by transmission electron microscopy. The significant difference observed between the two oxide films is in the 18O distribution following the second step of anodization, when compared with galvanostatic anodization in phosphoric or sulfuric acid reported in previous works. From the current experiment, it is evident that a small amount of As in the pre-formed barrier layer appears to alter the ionic conductivity of the film; thus, somehow, it inhibits the movement of oxygen ions ahead of advancing pores during anodization in chromic acid. However, anodising pure alumina film under these conditions does not enhance oxygen movement within the oxide layer. In addition, the tracer stays in the outer part of the growing porous oxide film. A lower-than-expected value for pure alumina enrichment in 18O in the pre-formed films suggests, indirectly, that the pre-formed film may contain hydrogen species, as well as trapped electrons, since no Cr is detected. This may lead to the presence of space charge distribution, which has a dual effect: it both retards the ejection of Al3+ ions and prevents O2- ions from migrating inward. Thus, the negative- and positive-charge distributions might play a role in the initiation of pores via a flow mechanism.

Understanding the High Scan Rate PDP Curves Obtained By Seccm

Scanning electrochemical cell microscopy (SECCM) is progressively employed for investigating corrosion behaviors at localized sites on metal surfaces. Normally, hundreds of potentiodynamic polarization (PDP) measurements are conducted on the sample using a high potential scan rate to reduce the experimental duration. However, polarization curves obtained under such conditions would yield inaccurate Tafel kinetics. In this research, we performed PDP measurements on Al sample at various scan rates using SECCM and obtained reproducible results. The experimental polarization curves were successfully simulated by a high field model that accounted for the cathodic contribution from oxygen reduction reaction and the anodic contribution from Al oxide film growth. By utilizing this model, we were able to extract the true corrosion kinetic properties from the high scan rate polarization curves, which has not been reported previously. This study represents a significant contribution towards enhancing SECCM-based micro-polarization as a robust quantitative technique for corrosion study.

Elemental partitioning and corrosion resistance of Ni–Cr alloys revealed by accurate ab-initio thermodynamic and electrochemical calculations

Elemental partitioning during thermal processing can significantly affect the corrosion resistance of bulk alloys operating in aggressive electrochemical environments, for which, despite decades of experimental and theoretical studies, the thermodynamic and electrochemical mechanisms still lack accurate quantitative descriptions. Here, we formulate an ab initio thermodynamic model to obtain the composition- and temperature-dependent free energies of formation (ΔfG) for Ni–Cr alloys, a prototypical group of corrosion-resistant metals, and discover two equilibrium states that produce the driving forces for the elemental partitioning in Ni–Cr. The results are in quantitative agreement with the experimental studies on the thermodynamic stability of Ni–Cr. We further construct electrochemical (potential–pH) diagrams by obtaining the required ΔfG values of native oxides and (oxy)hydroxides using high-fidelity ab-initio calculations that include exact electronic exchange and phononic contributions. We then analyze the passivation and electrochemical trends of Ni–Cr alloys, which closely explain various oxide-film growth and corrosion behaviors observed on alloy surfaces. We finally determine the optimal Cr content range of 14–34 at%, which provides the Ni–Cr alloys with both the preferred heat-treatment stability and superior corrosion resistance. We conclude by discussing the consequences of these findings on other Ni–Cr alloys with more complex additives, which can guide the further optimization of industrial Ni–Cr-based alloys.

Corrosion and stress corrosion cracking characteristics of 4043 aluminium alloy fabricated through directed energy deposition process

Additive manufacturing (AM) has emerged as a crucial element of Industry 4.0. In the pursuit of fabricating lightweight components, AM of aluminium alloys has become the centre of focus in recent years. This study investigates aluminium alloy (ER4043) components fabricated by arc-based directed energy deposition (DED-arc) for their corrosion and stress corrosion cracking (SCC) behaviour in 0.6 M NaCl solution at room temperature. Electrochemical characteristics in 0.6 M NaCl solution were investigated using open circuit potential (OCP), potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) tests. Electrochemical results revealed that the DED samples fabricated using a tungsten inert gas (TIG) welder as the energy source demonstrated better resistance against corrosion when compared to those developed through cold metal transfer (CMT) based DED. The prolonged exposure of samples in 0.6 M NaCl facilitated the growth of a stable passive oxide film leading to enhanced corrosion resistance. Slow strain rate tests (SSRT) conducted in air and 0.6 M NaCl solution showed that DED samples are susceptible to SCC. The fractography of the fractured SSRT samples indicated the mode of failure to be intergranular.

Electro-chemo-mechanical properties of anodic oxide (passive) films formed on Cu, Ni and Fe

Abstract Electro-chemo-mechanical properties of anodic oxide (passive) films formed on metals have been reviewed focusing on the results of stress variations caused by anodic oxidation of Cu, Ni, and Fe thin film electrodes in deaerated pH 8.4 borate buffer solution at 25 °C. The surface stress varies toward compressive direction due to adsorption of OH on Cu from aqueous solution as well as adsorption of oxygen on metals from gas phase. The stresses are generated with the growth of three-dimensional anodic oxide films on metals. The magnitude and sign (tensile or compressive) of the intrinsic film stress were determined by taking the residual stress of the substrate and the dielectrostriction into consideration. The tensile or compressive intrinsic film stress depends on p-type or n-type semiconductive properties of the anodic oxide films, which is explained in terms of the void formation or oxide formation in the metal side at the metal/film interface. Furthermore, the stress variation toward compressive direction during cathodic reduction of the anodic oxide films is explained in terms of the volume expansion due to the formation of intermediate species.