Zinc treatment effects on corrosion behavior of 304 stainless steel in high temperature, hydrogenated water

Trace levels of soluble zinc(II) ions (30 ppb) maintained in mildly alkaline, hydrogenated water at 260 °C were found to lower the corrosion rate of austenitic stainless steel (UNS S30400) by about a factor of five, relative to a non-zinc baseline test [S.E. Ziemniak, M. Hanson, Corros. Sci. 44 (2002) 2209] after 10,000 h. Characterizations of the corrosion oxide layer via grazing incidence X-ray diffraction and X-ray photoelectron spectroscopy in combination with argon ion milling and target factor analysis, revealed that miscibility gaps in two spinel binaries—Fe(Fe_1−mCr_m)₂O₄ and (Fe_1−nZn_n)Fe₂O₄—play a significant role in determining the composition and structure of the corrosion layer(s). Although compositions of the inner and outer corrosion oxide layers represent solvus phases in the Fe₃O₄-FeCr₂O₄ binary, zinc(II) ion incorporation into both phases leads to further phase separation in the outer (ferrite) layer. Recrystallization of the low zinc content ferrite solvus phase is seen to produce an extremely fine grain size (∼20 nm), which is comparable in size to grains in the inner layer and which is known to impart resistance to corrosion. Zinc(II) ion incorporation into the inner layer creates additional corrosion oxide film stabilization by further reducing the unit cell dimension via the substitution reaction

0.2Zn²⁺(aq)+Fe(Fe_0.35Cr_0.65)₂O₄(s)?0.2Fe²⁺(aq)+(Zn_0.2Fe_0.8)(Fe_0.35Cr_0.65)₂O₄(s)     

Anodic oxides on InAlP formed in sodium tungstate electrolyte

Amorphous anodic oxide films on InAlP have been grown at high efficiency in sodium tungstate electrolyte. The films are shown to comprise an outer layer containing indium species, an intermediate layer containing indium and aluminium species and an inner layer containing indium, aluminium and phosphorus species_. The layering correlates with the influence on cation migration rates of the energies of In³⁺-O, Al³⁺-O and P⁵⁺-O bonds, which increase in this order. The film surface becomes increasingly rough with increase of the anodizing voltage as pores develop in the film, which appear to be associated with generation of oxygen gas.     

Orientation dependence of the electrochemical corrosion properties of electrodeposited Cu foils

In this study, the electrochemical corrosion properties of electrodeposited Cu foils in a CuCl₂-containing acidic etching solution were investigated. The main passive product was CuCl and a trace amount of Cu₂O can also be detected. The (2 2 0)-oriented Cu foils exhibited higher corrosion potential and lower corrosion current density than those with (1 1 1) or (2 0 0) texture, suggesting a superior corrosion resistance against the etching solution. It is proposed that the preferred orientation and thus the differences in atomic stacking density on specific planes dominated the corrosion properties of the electrodeposited Cu foils instead of grain size or surface roughness.     

Oxidation behavior of molten magnesium in atmospheres containing SO2

The microchemistry and morphology of the oxide layer formed on molten magnesium in atmospheres containing SO₂ were examined. Based on the results and the thermodynamic and kinetic calculations of oxide-growth process, a schematic oxidation mechanism is presented. The results showed that the oxide scales with network structure were generally composed of MgO, MgS, and MgSO₄ with different layers, depending on the SO₂ content, the time and the temperature. The formation of MgSO₄ was important for the formation of the protective oxide scales. The growth of the oxide scales followed the parabolic law at 973 K and was controlled by diffusion.     

Effect of Dy on oxide scale adhesion of NiAl coatings at 1200 °C

The cyclic oxidation behaviour of β-NiAlDy coatings produced by electron beam physical vapour deposition (EB-PVD) was investigated. For the Dy-free NiAl coating, numerous voids developed at the Al₂O₃ scale/NiAl interface and sulfur was found to segregate at the void surfaces, leading to early spallation of the scale. The addition of Dy prevented sulfur segregation and void formation at the scale/NiAl interface. As a result, the scale grown on the NiAlDy coating remained adherent and no spallation occurred even after 400 h cyclic oxidation. The 0.05 at.% Dy doped coating revealed lower oxidation rate than the more Dy doped coatings.     

Oxidation behaviour of molten magnesium and AZ91D magnesium alloy in 1,1,1,2-tetrafluoroethane/air atmospheres

The oxidation rates, the morphologies and compositions of the surface films on molten magnesium and AZ91D alloy in covering gas of 1,1,1,2-tetrafluoroethane/air at 760 °C were investigated using thermogravimetric techniques, SEM, XRD and XPS. The oxidation rates of the two melts followed parabolic law in the atmosphere of high concentrate 1,1,1,2-tetrafluoroethane, and obeyed linear law in the atmosphere of low concentrate 1,1,1,2-tetrafluoroethane. But the oxidation rates of molten magnesium and AZ91D alloy presented a certain difference. The oxidation products on its surface films were composed of MgF₂ which played an import role to prevent the molten oxidation and other compounds.     

Zinc treatment effects on corrosion behavior of Alloy 600 in high temperature, hydrogenated water

Trace levels of soluble zinc(II) ions (30 ppb) maintained in mildly alkaline, hydrogenated water at 260 °C were found to reduce the corrosion rate of Alloy 600 (UNS N06600) by about 40% relative to a non-zinc baseline test [S.E. Ziemniak, M. Hanson, Corros. Sci., in press, doi:10.1016/j.corsci.2005.01.006]. Characterizations of the corrosion oxide layer via SEM/TEM and grazing incidence X-ray diffraction confirmed the presence of a chromite-rich oxide phase and recrystallized nickel. The oxide crystals had an approximate surface density of 3500 μm⁻² and an average size of 11 ± 5 nm. Application of X-ray photoelectron spectroscopy with argon ion milling, followed by target factor analyses, permitted speciated composition versus depth profiles to be obtained. Numerical integration of the profiles revealed that: (1) alloy oxidation occurred non-selectively and (2) zinc(II) ions were incorporated into the chromite-rich spinel: (Zn_0.55Ni_0.3Fe_0.15)(Fe_0.25Cr_0.75)₂O₄. Spinel stoichiometry places the trivalent ion composition in the single phase oxide region, consistent with the absence of the usual outer, ferrite-rich solvus layer. By comparison with compositions of the chromite-rich spinel obtained in the non-zinc baseline test, it is hypothesized that zinc(II) ion incorporation was controlled by the equilibrium for

0.55Zn²⁺(aq)+(Ni_0.7Fe_0.3)(Fe_0.3Cr_0.7)₂O₄(s)?0.40Ni²⁺(aq)+0.15Fe²⁺(aq)+(Zn_0.55Ni_0.3Fe_0.15)(Fe_0.3Cr_0.7)₂O₄(s)     

Electropolishing effects on corrosion behavior of 304 stainless steel in high temperature, hydrogenated water

The corrosion rate of electropolished 304 stainless steel surfaces (UNS S30400) is found to be lower by more than a factor of three relative to that determined previously for machined surfaces in mildly alkaline, hydrogenated water at 260 °C. This favorable result is attributed to significant changes in nanocrystallinity of the corrosion oxide layer caused by the removal of surface microstrain, which had been imparted during the machining process. In the absence of microstrain, a low-porosity, protective, corrosion layer forms that is composed of extremely small and uniformly-sized spinel oxide crystals. Application of scanning electron microscopy (FEG-SEM), X-ray diffraction and X-ray photoelectron spectroscopy (XPS) in conjunction with ion milling and target factor analyses, found the corrosion layer to consist of micrometer-size crystals of a ferrite-based spinel oxide (non-protective) over-laying nanometer-size crystals of a chromite-based spinel oxide (protective). Composition of both phases is unchanged from that previously observed on corroded, machined surfaces and is representative of solvus phases in the immiscible Fe(Fe_1−nCr_n)₂O₄ spinel binary. The smaller size (10 vs. 26 nm) and greater surface density (∼10,000 vs. 835 μm⁻²) of the chromite-based crystals relative to those formed on machined (i.e., cold-worked) surfaces, however, is consistent with the absence of preferred high energy nucleation sites on strain-free surfaces. Therefore, electropolishing, which removes surface microstrain induced by cold-working, represents a preferred reference surface condition.     

High temperature oxidation of Fe-Al and Fe-Cr-Al alloys: The role of Cr as a chemically active element

Good high-temperature corrosion resistance of Fe-Al alloys in oxidizing environments is due to the α-Al₂O₃ film which is formed on the surface provided temperature is above 900 °C and the Al-content of the alloy exceeds the critical value. Ab initio calculations combined with experiments on Fe-13Al, Fe-18Al, Fe-23Al and Fe-10Cr-10Al alloys show that the beneficial effect of Cr on the oxidation resistance is significantly related to bulk effects. The comparison of experimental and calculated results indicates a clear correlation between the Fe-Cr chemical potential difference and the formation of the protective oxide scales.     

Oxidation behavior of silicon carbide at 1200 °C in both air and water–vapor-rich environments

Oxidation of SiC in both air and water–vapor–rich environments was carried out at 1200 °C to examine the effects of different oxidation conditions on the early-stage oxidation behavior of SiC. Two different types of SiC oxidation behavior were found, passive or active, depending on the oxidation environment. All the samples possessed amorphous oxide layers, regardless of the oxidation environment. Three Si oxidation states (SiO, Si₂O₃, and SiO₂) were observed in this layer. The amorphous Si₂O₃ state was dominant, and the ratio of the three different states changed with the test conditions.     

Microstructure and corrosion resistance of Cr/Cr2N multilayer film deposited on the surface of depleted uranium

Depleted uranium is widely used in national defence and nuclear energy fields. However, the inferior corrosion resistance limits its application. A Cr/Cr₂N film was prepared by magnetron sputtering on the uranium to improve its corrosion resistance. The Cr/Cr₂N film exhibits modulation structure. The introduction of the Cr/Cr₂N increases the corrosion potential; the corresponding current density decreases about three orders of magnitude. After polarization corrosion, the surface morphology of the Cr/Cr₂N-coated on uranium keeps integrated. Only a thin layer of film (∼40 nm) is oxidized. The Cr/Cr₂N film shows great potential in improving oxidation and corrosion resistance of depleted uranium.     

Oxidation behaviour of Ti–Al–C films composed mainly of a Ti2AlC phase

This paper addresses the oxidation behaviour of Ti–Al–C films composed mainly of a Ti₂AlC phase. The films exhibited rather low oxidation rates at 600 and 700 °C, with an oxygen-rich zone or a thin oxide layer appearing on the film surfaces. Much faster oxidation rates were observed at 800 and 900 °C. The Ti₂AlC phase was quickly consumed by oxidation. From the film surface to the inner zone, TiO₂-rich layer, Al₂O₃-rich layer, and TiO₂ + Al₂O₃ mixed layer was observed, respectively. The oxidation mechanism of the Ti–Al–C film is discussed based on the experimental results.     

Oxidation behavior and phase transition of ZrB2–SiCw–ZrO2f ceramic

The oxidation behavior and phase transition of ZrB₂–SiC_w–ZrO_2f ceramic had been investigated by in situ high-temperature XRD, XPS, SEM, EDS and TEM measurements. The initial oxidation temperature of most ZrB₂ was 1000 °C and no significant oxidation of SiC was found up to 1200 °C. The oxidation products formed at lower temperatures would penetrate into the pores and flaws on the surface, which was beneficial to crack healing. In order to improve the oxidation resistance of this system, it should be focused on decreasing the oxygen diffusivity and the volume expansion caused by phase transition.     

Barrier and porous anodic oxides on InSb

Anodizing of InSb at 5 mA cm⁻² in sodium tungstate electrolyte is shown to produce barrier-type amorphous oxide at relatively low voltages, to about 40 V, and porous-type amorphous oxide at increased voltages. The barrier-type amorphous oxide, consisting of units of In₂O₃ and Sb₂O₃, distributed relatively uniformly throughout the film, develops at a formation ratio of 2.2 ± 0.2 nm V⁻¹. The outer 15–20% of the film also contains tungsten species. The relatively high efficiency of barrier film growth reduces significantly with transition to porous oxide, which is associated additionally with generation of oxygen at the film surface. The final oxide, at 65 V, comprises pores, of typical diameter 80 nm, orientated approximately normal to the substrate and extending from a barrier region to the film surface.     

Oxidation kinetics and mechanisms of Ni-base alloys in pressurised water reactor primary conditions: Influence of subsurface defects

Oxidation of Alloy 690 in PWR primary water conditions has been investigated, considering particularly the role played by subsurface structural defects. To simulate a defective surface state, Xe implantation has been set up on samples. Corrosion experiments were thereafter performed in a corrosion loop simulating the PWR medium with durations between 24 h and 1000 h. Microstructural observations and NRA measurements underlined the role played by defects on the crystallinity of the continuous oxide spinel layer, on the nucleation of Cr₂O₃ nodules and on the oxidation rate. The higher defects concentration seemed to modify the oxygen diffusion in the oxide scale.     

Electrochemical corrosion behaviour of Bi-11Ag alloy for electronic packaging applications

This study investigated the electrochemical corrosion properties of the solders for die-attach applications in 3.5% NaCl solution. Compared with Pb-5Sn and Zn-40Sn, Bi-11Ag exhibited higher corrosion potential and relatively low corrosion current density. The ductile Ag-rich phase which dispersed in the Bi matrix was able to accommodate the stress arising from the formation of a passive layer and contributed to the two-stage passivation. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) results confirm that the corrosion products comprised BiOCl, Bi₂O₃ and AgCl.     

Electrochemical properties and growth mechanism of passive films on Alloy 690 in high-temperature alkaline environments

Passive films formed on Alloy 690 in high-temperature alkaline environments were investigated by potentiodynamic polarization, X-ray photoelectron spectroscopy, transmission electron microscopy and Mott-Schottky approach. Passive current density and donor density of the passive films increase with increasing temperature, due to increased diffusion rates of metallic ions and dehydration of hydroxide phases. The passive films show a duplex structure including an inner layer of fine-grained Cr oxide or spinel oxide and an outer layer of Ni-Fe spinel oxide and Ni hydroxide. A growth model of the passive films on Alloy 690 in high-temperature alkaline environments is proposed and discussed.     

The mechanism of oxide film formation on Alloy 690 in oxygenated high temperature water

Oxide films formed on Alloy 690 exposed to 290 °C water containing 3 ppm O₂ were investigated. It was found that Cr rich oxides form initially through solid-state reactions. Ni–Fe spinels gradually develop on surface layer by precipitation with increasing immersion time. Initially formed Cr rich oxides react with outwards diffusing Ni and Fe to form small spinel particles which then vanish gradually. An inner layer develops from oxide/matrix interface through inward diffusion of oxidant. Cr is preferentially oxidized and tends to dissolve into solution. The resultant inner layer consists of predominant NiO which cannot serve as a protective barrier layer.     

Spectroscopic investigation of oxidized solder surfaces

For further understanding of the discoloration of solder surfaces due to oxidation during the assembly and operation of electronic devices, UV–vis and X-ray photoelectron spectroscopic analyses were applied to evaluate the degree of discoloring and identify the surface oxides. The decrease in reflectance of the oxidized solder surface is related to SnO whose absorption band is located within the visible region. A trace of P can effectively depress the discoloration of solders under both solid and semi-solid states through the suppression of SnO.     

Comparison of the cyclic oxidation behavior of a low expansion Ni + CrAlYSiN nanocomposite and a NiCrAlYSi coating

Ni + CrAlYSiN nanocomposite coatings and NiCrAlYSi coatings were prepared on a nickel-based superalloy K417 by vacuum arc evaporation. Both coatings exhibited excellent cyclic oxidation resistance at 1000 °C for 200 1-h cycles. Cracking/spallation of thermally grown oxide (TGO) scale occurred only on NiCrAlYSi coatings, due to the lower thermal stresses level in the TGO on Ni + CrAlYSiN coatings. An hcp-AlN interlayer eliminated the interdiffusion between the nanocomposite coating and substrate. The thickness of the TGO scale on NiCrAlYSi coatings was twice that of the scale on the AlN/Ni + CrAlYSiN coatings, probably due to the crack and healing effect.