Corrosion behavior of NiCrFe Alloy 600 in high temperature, hydrogenated water

The corrosion behavior of Alloy 600 (UNS N06600) is investigated in hydrogenated water at 260 °C. The corrosion kinetics are observed to be parabolic, the parabolic rate constant being determined by chemical descaling to be 0.055 mg dm⁻² h^−1/2. A combination of scanning and transmission electron microscopy, supplemented by energy dispersive X-ray spectroscopy and grazing incidence X-ray diffraction, are used to identify the oxide phases present (i.e., spinel) and to characterize their morphology and thickness. Two oxide layers are identified: an outer, ferrite-rich layer and an inner, chromite-rich layer. X-ray photoelectron spectroscopy with argon ion milling and target factor analysis is applied to determine spinel stoichiometry; the inner layer is (Ni_0.7Fe_0.3)(Fe_0.3Cr_0.7)₂O₄, while the outer layer is (Ni_0.9Fe_0.1)(Fe_0.85Cr_0.15)₂O₄. The distribution of trivalent iron and chromium cations in the inner and outer oxide layers is essentially the same as that found previously in stainless steel corrosion oxides, thus confirming their invariant nature as solvi in the immiscible spinel binary Fe₃O₄-FeCr₂O₄ (or NiFe₂O₄-NiCr₂O₄). Although oxidation occurred non-selectively, excess quantities of nickel(II) oxide were not found. Instead, the excess nickel was accounted for as recrystallized nickel metal in the inner layer, as additional nickel ferrite in the outer layer, formed by pickup of iron ions from the aqueous phase, and by selective release to the aqueous phase.     

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.     

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)     

Effect of hydrogen in Inconel Alloy 600 on corrosion in high temperature oxygenated water

Corrosion test on hydrogen charged and uncharged coupons of Inconel Alloy 600 in high temperature oxygenated water showed more weight loss of charged coupon. Observation of the oxide film by transmission electron microscopy (TEM) showed a defective, thicker oxide layer on charged coupon. Analyses of the oxide film by TEM-energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy indicated enrichment of Ni but depletion of Cr in the oxide film on charged coupon. The changes in corrosion behavior and microstructure of the oxide film were most likely due to the hydrogen enhanced preferential dissolution of Cr cations in the water.     

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.     

The structure and high temperature corrosion performance of medium-thickness aluminide coatings on nickel-based superalloy GTD-111

Simple and Si-modified aluminide coatings having medium-thickness (40-60 μm) have been applied on the superalloy GTD-111 by a slurry technique. Hot corrosion and cyclic oxidation performance of the uncoated and the coated superalloy were investigated by exposing samples to a molten film of Na₂SO₄-40 %wt NaVO₃-10%wt NaCl at 780 °C and 1 h cyclic oxidation at 1100 °C in air, respectively. The presence of silicon in the aluminide structure increased the oxidation resistance by a factor of 1.7 times. In addition, a SiO₂-containing scale, which formed on the Si-containing coating surface, was stable during of the hot corrosion testing.     

Investigation on carbon dioxide corrosion behaviour of HP13Cr110 stainless steel in simulated stratum water

The carbon dioxide corrosion behaviour of HP13Cr110 stainless steel in simulated stratum water is studied by potentiodynamic curve and electrochemical impedance spectroscopy (EIS); the micro-structure and composition of the corrosion scale formed at high-temperature and high-pressure are analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results show that 13Cr stainless steel is in passive state in the stratum water, the passive current density increases and the passive potential region decreases with increasing temperature. The corrosion scale formed at high-temperature and high-pressure is mainly composed of iron/chromium oxides and a little amount of FeCO₃.     

Oxidation of III-V semiconductors

This paper focuses on the characterization of anodic films (formed in aqueous electrolytes) and thermal oxides (formed at ∼500 °C) on GaAs, InP, AlGaAs, InAlAs, InAlP and heterostructures for GaAs- and InP-based devices. Emphasis is placed on Al-containing oxides, particularly on InAlP which possess good insulating properties. The composition and nature of the oxides have been determined by Auger electron spectroscopy, X-ray photoelectron spectroscopy, ¹⁶O/¹⁸O secondary ion mass spectrometry, Rutherford backscattering spectroscopy, scanning and transmission electron microscopy. Electrical measurements performed on metal-insulator-semiconductor (MIS) structures indicate that the Al-containing oxides have good electrical properties making the films potentially useful for some device applications.     

Corrosion behavior of NiCrMo Alloy 625 in high temperature, hydrogenated water

The corrosion behavior of NiCrMo Alloy 625 (UNS N06625) has been characterized in a 10,000 h test conducted in hydrogenated water at 260 °C. The corrosion kinetics were observed to be parabolic, the parabolic rate constant being determined by chemical descaling to be 0.074 mg dm⁻² h^−1/2. 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 the presence of two spinel oxide phases and significant amounts of recrystallized nickel. Based on the distribution of three oxidized alloying constituents (Ni, Cr, Fe) with respect to depth and oxidation state, it was concluded that: (a) corrosion occurs in a non-selective manner, but significant amounts of nickel(II) ions are released to the water, and (b) the spinel oxides exist as a chromite-rich inner layer (Ni_0.7Fe_0.3)(Cr_0.8Fe_0.2)₂O₄ underneath a coarser, ferrite-rich outer layer (Ni_0.9Fe_0.1)(Cr_0.1Fe_0.9)₂O₄. The trivalent cation distribution in each of these phases appears to represent a solvus in the immiscible NiCr₂O₄-NiFe₂O₄ binary.     

Electrochemical behaviour of Alloy 600 tubing in thiosulphate solution

Electrochemical and surface properties of passive films formed on Alloy 600 in a thiosulphate solution were studied. Oxide films formed at various passive potentials contained a bilayer oxide, whose composition changed as a function of the applied potential resulting in a change in the impedance behaviour. Destabilisation of the oxide film at potentials within the passive region was observed, which was due to the breakdown of the oxide film and coincided with the loss of Cr within the passive film. In contrast, a higher degree of corrosion protection was obtained when the Cr content within the oxide film was elevated.     

KCl-induced high temperature corrosion of the austenitic Fe-Cr-Ni alloys 304L and Sanicro 28 at 600 °C

The influence of KCl(s) on the high temperature oxidation of the austenitic alloys 304L and Sanicro 28 at 600 °C in O₂ + H₂O environment is reported. 0.10 mg/cm² KCl(s) was added before exposure. The samples are investigated by grazing angle XRD, SEM/EDX, and AES. In the absence of KCl, both alloys show protective behaviour in dry O₂. In O₂ + H₂O environment, alloy 304L suffers local breakaway corrosion while Sanicro 28 still shows protective behaviour. The oxidation of both alloys is strongly accelerated by KCl. KCl reacts with chromium in the normally protective corundum-type oxide, forming K₂CrO₄. This depletes the scale in chromia and leads to the formation of a non-protective, iron-rich scale. The significance of KCl-induced corrosion in real applications is discussed and the oxidation behaviour of the two steels is compared.     

Influence of Zn on oxide films on Alloy 690 in borated and lithiated high temperature water

To clarify the corrosion control effect of Zn injection into hydrothermal environments, the oxide films on Alloy 690 in the deaerated borated and lithiated water have been investigated using potentiodynamic polarization curves, electrochemical impedance spectra at 300 °C and ex-situ X-ray photoelectron spectroscopy. With Zn injection in the solution, ZnCr₂O₄ and ZnFe₂O₄ were formed in the inner and outer layers of the oxide films on Alloy 690, respectively, through exchange reactions between Zn²⁺ and Fe²⁺/Ni²⁺. A simple model for oxide film structure change and the mechanism of corrosion inhibition by Zn injection is proposed and discussed.     

Zinc carboxylating: a new conversion treatment of zinc

This study is devoted to a new surface treatment of zinc, called “carboxylating”, which could be an environmentally friendly alternative to the usual conversion treatments. Carboxylating requires use of both n-alkyl carboxylic acid and peroxoborate as oxidizing agent, in a water-ethanol mixture. As in the phosphating process, the carboxylating one is carried out in four steps: the activation step, oxidation of the zinc substrate at an acidic pH, germination and growth of zinc carboxylate crystals. Influence of the activator content, treatment time, oxidizing agent concentration, and chain length of the carboxylic acid was successively examined. Carboxylates covered zinc samples were tested in corrosion conditions. The longer the carbon chain length, the more corrosion resistant the coating; its layered structure easily allows exchanging anions and a hydroxocarboxylate of zinc is stabilized during the corrosion test then delays the white rust formation.     

Oxide properties and stress corrosion cracking behaviour for Alloy 600 in leaded caustic solutions at high temperature

The stress corrosion cracking behaviour of Alloy 600 in caustic solutions with and without PbO at 315 °C was investigated by means of slow strain rate tension tests. The characterisation of the oxide that formed on Alloy 600 was derived from transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy. Lead was incorporated into the oxide in a metallic lead state and a lead oxide state, which degraded the passivity and induced PbSCC susceptibility. NiB was used as an inhibitor. It reduced the lead incorporation level in the oxide layer and decreased PbSCC susceptibility.     

The effects of Cr and Al concentrations on the oxidation behavior of oxide dispersion strengthened ferritic alloys

The oxidation of six oxide dispersion strengthened (ODS) ferritic alloys was investigated at 1050 °C in air up to 200 h. Al plays the dominant role in improving the oxidation resistance of the ODS alloys. Cr and Y are of importance in forming the stable Al₂O₃ scale. To produce the dense alumina layer with enhanced adherence to the metal substrate, the concentrations of Al and Cr should be larger than 2 and 14 wt.%, respectively.     

Role of TiN inclusion on corrosion fatigue behavior of Alloy 690 steam generator tubes in borated and lithiated high temperature water

Influence of TiN inclusion on corrosion fatigue behavior of three types of as-received Alloy 690 steam generator tubes (J, C1 and C2) in borated and lithiated high temperature water was investigated. The volume fraction of inclusions in tube J, C1 and C2 were about 0.0894%, 0.0384% and 0.1843%. The fatigue life of tube C2 was slightly shorter than that of tube J and C1. Large broken TiN inclusions and TiN-inclusion clusters played a significant role on fatigue crack initiation and propagation for tube C2 in high temperature water. The inclusion-involved fatigue cracking mechanisms are discussed.     

Internal oxidation of Alloy 600 exposed to hydrogenated steam and the beneficial effects of thermal treatment

Alloy 600 in the solution annealed (SA) and thermally treated (TT) conditions was exposed to a hydrogenated steam environment considered to simulate primary water in pressurized water reactors. The likely susceptibility to primary water stress corrosion cracking (PWSCC) was evaluated using the internal oxidation model. A FIB was used to extract cross-sections from Alloy 600 samples and elemental maps were generated; internal oxidation was observed intragranularly in all cases, resulting in expulsion of metallic nickel to the surface. Intergranular oxidation and embrittlement was observed in SA samples, while a thick and dense Cr-rich oxide was formed intergranularly on TT samples.     

Quantification of growth kinetics and adherence of oxide scales formed on Ni-based superalloys at high temperature

Cyclic and isothermal oxidation behaviors of first and fourth-generation superalloys AM1 and MCNG were investigated to evaluate the ability of the scratch test to quantify the adhesion of multi-layered oxide scales. Effects of sulfur content and of scale thickness were studied independently. Available models lead to large discrepancies in the calculated work of adhesion values with the evaluation of the residual stress being the largest source of error. Nevertheless, models can assess the effect of sulfur content and the scratch test can be used to correlate the long-term cyclic oxidation behavior and the adhesion of oxide scales.     

Influence of Zn injection on characteristics of oxide film on 304 stainless steel in borated and lithiated high temperature water

The oxide film on 304 stainless steel exposed to the hydrothermal environments at 573.15 K up to 20 days without/with 10 ppb Zn injection has been investigated ex situ by X-ray photoelectron spectroscopy (XPS). ZnFe₂O₄ and ZnCr₂O₄ were found to be formed in the oxide film at the initial stage of immersion by substitution reaction between Zn²⁺ and Fe²⁺, and ZnCr₂O₄ became dominant after long-term immersion. The calculations of potential-pH diagrams, solubilities and crystallographic features of spinels have been done to evaluate the oxide film structure and the inhibition mechanism caused by Zn injection.