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)     

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.     

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.     

Corrosion behavior of 304 stainless steel in high temperature, hydrogenated water

The corrosion behavior of an austenitic stainless steel (UNS S30400) has been characterized in a 10,000 h test conducted in hydrogenated, ammoniated water at 260 °C. The corrosion kinetics were observed to be parabolic, the parabolic rate constant being determined by chemical descaling to be 1.16 mg dm⁻² h^−1/2. X-ray photoelectron spectroscopy, in combination with argon ion milling and target factor analysis, was applied to provide an independent estimate of the rate constant that agreed with the gravimetric result. Based on the distribution of the three oxidized alloying constituents (Fe, Cr, Ni) with respect to depth and elemental state, it was found that: (a) corrosion occurs in a non-selective manner, and (b) the corrosion film consists of two spinel oxide layers--a ferrite-based outer layer (Ni_0.2Fe_0.8)(Fe_0.95Cr_0.05)₂O₄ on top of a chromite-based inner layer (Ni_0.2Fe_0.8)(Cr_0.7Fe_0.3)₂O₄. These compositions agree closely with the solvi phases created by immiscibility in the Fe₃O₄-FeCr₂O₄ binary, implying that immiscibility plays an important role in the phase separation process.     

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.     

Preparation of Ni0.5Zn0.5Fe2O4/SiO2 nanocomposites and their adsorption of bovine serum albumin

The magnetic nanocomposites of (1 − x)Ni_0.5Zn_0.5Fe₂O₄/xSiO₂ (x = 0-0.2) were synthesized by the citrate-gel process and their absorption behavior of bovine serum albumin (BSA) was investigated by UV spectroscopy at room temperature. The gel precursor and resultant nanocomposites were characterized by FTIR, XRD, TEM and BET techniques. The results show that the single ferrite phase of Ni_0.5Zn_0.5Fe₂O₄ is formed at 400 °C, with high saturation magnetization and small coercivity. A porous, amorphous silica layer is located at the ferrite nanograin boundaries, with the silica content increasing from 0 to 0.20, the average grain size of Ni_0.5Zn_0.5Fe₂O₄ calcined at 400 °C reduced from about 18-8 nm. Consequently, the specific surface area of the nanocomposites ascends clearly with the increase of silica content, which is largely contributed by the increase in the thickness of the porous silica layer. The Ni_0.5Zn_0.5Fe₂O₄/SiO₂ nanocomposites demonstrate a better adsorption capability than the bare Ni_0.5Zn_0.5Fe₂O₄ nanoparticles for BSA. With the increase of the silica content from 0 to 0.05 and the specific surface area from about 49-57 m²/g, the BSA adsorption capability of the Ni_0.5Zn_0.5Fe₂O₄/SiO₂ nanocomposites calcined at 400 °C improve dramatically from 22 to 49 mg/g. However, with a further increase of the silica content from 0.05 to 0.2, the specific surface area increase from about 57-120 m²/g, the BSA adsorption for the nanocomposites remains around 49 mg/g, owing to the pores in the porous silica layer which are too small to let the BSA protein molecules in.     

The corrosion of Fe3Al alloy in liquid zinc

A systematic study of the isothermal corrosion testing and microscopic examination of Fe₃Al alloy in liquid zinc containing small amounts of aluminum (less than 0.2 wt.%) at 450 °C was carried out in this work. The results showed the corrosion of Fe₃Al alloy in molten zinc was controlled by the dissolution mechanism. The alloy exhibited a regular corrosion layer, constituted of small metallic particles (diameter: 2-5 μm) separated by channels filled with liquid zinc, which represented a porosity of about 29%. The XRD result of the corrosion layer formed at the interface confirmed the presence of Zn and FeZn_6.67. The corrosion rate of Fe₃Al alloy in molten zinc was calculated to be approximately 1.5 × 10⁻⁷ g cm⁻² s⁻¹. Three steps could occur in the whole process: the superficial dissolution of metallic Cr in the corrosion layer, the new phase formation of FeZn_6.67 and the diffusion of the dissolved species in the channels of the corrosion layer.     

Early stages of the oxidation of a FeCrAlRE alloy (Kanthal AF) at 900 °C: A detailed microstructural investigation

Early stages of the evolution of Al₂O₃ scales formed on a FeCrAlRE alloy (Kanthal AF) have been investigated by analytical TEM. The samples were oxidized isothermally at 900 °C in dry O₂ or O₂ + 40% H₂O for 1 h or 24 h. All oxide scales exhibited a two-layered structure, with a continuous inward growing α-Al₂O₃ inner layer and an outward growing outer layer. After 1 h, the outer oxide layer consisted of γ-Al₂O₃ in both environments. After 24 h exposure in dry O₂, the γ-Al₂O₃ in the outer oxide layer was partly transformed to α-Al₂O₃ and spinel oxide (Mg_1−xFe_xAl₂O₄). In contrast, the γ-Al₂O₃ in the outer layer was not transformed after 24 h in O₂ + 40% H₂O, showing that water vapour stabilizes γ-Al₂O₃. All oxide scales contained a Cr-rich band, a product of the initial oxidation. The inner α-Al₂O₃ layer is suggested to nucleate on Cr₂O₃ or Cr_2−xFe_xO₃ in the initial oxide.     

Self-healing mechanism of a protective film prepared on a Ce(NO3)3-pretreated zinc electrode by modification with Zn(NO3)2 and Na3PO4

Self-healing mechanism of a protective film against corrosion of zinc at scratches in an aerated 0.5 M NaCl solution was investigated by polarization measurements, X-ray photoelectron spectroscopy (XPS) and electron-probe microanalysis (EPMA). The film was prepared on a zinc electrode by treatment in a Ce(NO₃)₃ solution and addition of aqueous solutions containing 9.98 or 19.9 μg/cm² of Zn(NO₃)₂ · 6H₂O and 55.2 μg/cm² of Na₃PO₄ · 12H₂O. After the coated electrode was scratched with a knife-edge crosswise and immersed in the NaCl solution for many hours, polarization measurements, observation of pit formation at the scratches, XPS and EPMA were carried out. This film was remarkably protective and self-healing against zinc corrosion on the scratched electrode. The cathodic and anodic processes of zinc corrosion were markedly suppressed by coverage of the surface except for scratches with a thin Ce₂O₃ layer containing a small amount of Ce⁴⁺ and the surface of scratches with a layer composed of Zn₃(PO₄)₂ · 4H₂O, Zn(OH)₂ and ZnO mostly.     

Synthesis of nanocrystalline nickel-zinc ferrite (Ni0.8Zn0.2Fe2O4) thin films by chemical bath deposition method

The nickel-zinc ferrite (Ni_0.8Zn_0.2Fe₂O₄) thin films have been successfully deposited on stainless steel substrates using a chemical bath deposition method from alkaline bath. The films were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), static water contact angle and cyclic voltammetry measurements. The X-ray diffraction pattern shows that deposited Ni_0.8Zn_0.2Fe₂O₄ thin films were oriented along (3 1 1) plane. The FTIR spectra showed strong absorption peaks around 600 cm⁻¹ which are typical for cubic spinel crystal structure. SEM study revealed compact flakes like morphology having thickness ∼1.8 μm after air annealing. The annealed films were super hydrophilic in nature having a static water contact angle (θ) of 5°.The electrochemical supercapacitor study of Ni_0.8Zn_0.2Fe₂O₄ thin films has been carried out in 6 M KOH electrolyte.The values of interfacial and specific capacitances obtained were 0.0285 F cm⁻² and 19 F g⁻¹, respectively.     

High temperature corrosion of pure Fe, Cr and Fe-Cr binary alloys in O2 containing trace KCl vapour at 750 °C

Pure Fe, Cr and Fe-Cr binary alloys were corroded in O₂ containing 298 ppm KCl vapour at 750 °C. The corrosion kinetics were determined, and the microstructure and the composition of oxide scales were examined. During corrosion process, KCl vapour reacted with the formed oxide scales and generated Cl₂ gas. As Cl₂ gas introduced the active oxidation, a multilayer oxide scales consisted of an outmost Fe₂O₃ layer and an inner Cr₂O₃ layer formed on the Fe-Cr alloys with lower Cr concentration. In the case of Fe-60Cr or Fe-80Cr alloys, monolayer Cr₂O₃ formed as the healing oxidation process. However, multilayer Cr₂O₃ formed on pure Cr.     

Role of Cr ions on the microstructure development, and magnetic phase evolution of Ni0.7Zn0.3Fe2O4 ferrite nanoparticles

A series of ferrite samples with the chemical formula Ni_0.7Zn_0.3Cr_xFe_2−xO₄ (x = 0.0-0.5) were prepared by a sol-gel auto-combustion method and annealed at 600 °C for 4 h. The resultant powders were investigated by various techniques, including X-ray diffractometry (XRD), vibrating sample magnetometry (VSM), and permeability studies. The prepared samples have a cubic spinel structure with no impurity phase. As the Cr³⁺ content x increases, bulk density and crystallite size decrease, whereas porosity increases. The saturation magnetization decreases linearly from 58.31 to 42.90 emu/g with increasing Cr³⁺ content. However, coercivity increases with increasing Cr³⁺ substitution. The magnetic moments calculated from Neel's molecular-field model are in agreement in the experiment results. The initial permeability (μ_i) decreases with increasing Cr³⁺ substitution. The decrease in initial permeability (μ_i) is attributed to decrease in magnetization on addition of Cr³⁺. The real part of the permeability decreases gradually with increasing frequency in accordance with Snoek's law. The Curie temperature decreases linearly with increasing Cr³⁺ content.     

The corrosion behavior of plasma sprayed Fe2Al5 coating in molten Zn

Aluminum coating was plasma sprayed on Fe-0.14-0.22 wt.% C steel substrate, and heat diffusion treatment at 923 °C for 4 h was preformed to the aluminum coating to form Fe₂Al₅ inter-metallic compound coating. The corrosion mechanism of the Fe₂Al₅ coating in molten zinc was investigated. SEM and EDS analysis results show that the corrosion process of the Fe₂Al₅ layer in molten zinc is as follows: Fe₂Al₅ → Fe₂Al₅Zn_x (η) → η + L(liquid phase) → L + η + δ(FeZn₇) → L + δ → L. The η phase and the eutectic structure (η + δ) prevent the diffusion of zinc atoms efficiently. Therefore the Fe₂Al₅ coating delays the reaction between the substrate and molten zinc, promoting the corrosion resistance of the substrate.     

Studies on the magnetic, magnetostrictive and electrical properties of sol-gel synthesized Zn doped nickel ferrite

Zinc doped nickel ferrite i.e., Ni_1−xZn_xFe₂O₄ (0 ≤ x ≤ 0.6) have been prepared by using sol-gel method. X-ray diffraction of these samples shows the presence of single-phase cubic spinel structure. The room temperature magnetic measurements showed that saturation magnetization (M_s) increases with the substitution of Zn²⁺ ions up to x = 0.4 and thereafter it begins to decrease, whereas magnetostriction (λ) value decreases with the addition of Zn²⁺ in the Ni-Zn ferrite. Dielectric permittivity (?′), dielectric loss tangent (tan δ) and AC conductivity (σ_AC) for all the prepared samples have been studied as a function of frequency and composition in the range from 0.05 Hz to 10 MHz at room temperature. It has been observed that initially ?′, tan δ and σ_AC decreases with the substitution of Zn²⁺ up to x = 0.4 and then increases with the further addition of Zn²⁺ ions. Variation in the slope parameter s with zinc contents indicates the presence of different type of conduction mechanism in different compositions. The dielectric loss curves exhibit relaxation peaks which shift with the addition of Zn contents. The results have been explained on the basis of space charge polarization according to Maxwell-Wagner's two-layer model and the hopping of charges between Fe²⁺ and Fe³⁺ as well as between Ni³⁺ and Ni²⁺ ions at the octahedral sites.     

The effects of niobium and nickel on the corrosion resistance of the zinc phosphate layers

In this investigation the viability of nickel substitution by niobium in zinc phosphate (PZn) baths has been studied. Samples of carbon steel (SAE 1010) were phosphated in two baths, one containing nickel (PZn + Ni) and the other with niobium substituting nickel (PZn + Nb). Potentiodynamic polarization curves (anodic and cathodic, separately) and electrochemical impedance spectroscopy (EIS) were used to evaluate the corrosion resistance of the phosphated carbon steels in a 0.5 mol L^− 1 NaCl electrolyte. The phosphate layers obtained were analysed by X-ray diffraction and it was found that they are composed of Zn₃(PO₄)₂.4H₂O (hopeite) and Zn₂Fe(PO₄)₂.4H₂O (phosphophylite). Surface observation by scanning electron microscopy (SEM) showed that the PZn + Ni layer is deposited as needle-like crystals, whereas the PZn + Nb layer shows a granular morphology. The electrochemical results showed that the PZn + Nb coating was more effective in the corrosion protection of the carbon steel substrate than the PZn + Ni layer. The results also suggested that nickel can be replaced by niobium in zinc phosphate baths with advantageous corrosion properties of the layer formed.     

Chemistry of corrosion products on Zn-Al-Mg alloy coated steel

Zn-Al-Mg alloy (ZM) coating provides a decisively enhanced corrosion resistance in a salt spray test according to DIN EN ISO 9227 (NSS) compared to conventional hot-dip galvanised zinc (Z) coating because of its ability to form a very stable, well adherent protecting layer of zinc aluminium carbonate hydroxide, Zn₆Al₂(CO₃)(OH)₁₆·4H₂O on the steel substrate. This protecting layer is the main reason for the enhanced corrosion resistance of the ZM coating. Surface corrosion products on ZM coated steel consist mainly of Zn₅(OH)₆(CO₃)₂, ZnCO₃ and Zn(OH)₂ with additions of Zn₅(OH)₈Cl₂ · H₂O and a carbonate-containing magnesium species.     

Oxidation of 316 stainless steel in supercritical water

The oxide scales of 316 stainless steel (316 SS) have been examined after exposure to supercritical water (SCW) with 2.0% H₂O₂ for up to 250 h. The exposed samples were analyzed using weight measurement, scanning electron microscopy (SEM), and X-ray diffraction analysis (XRD). It was found that mass gain of all samples increased with increasing temperature and exposure time. Higher temperature SCW resulted in rougher surfaces and thicker oxide scales. Duplex layer oxide structures with Ni-enrichment at the oxide/metal interface developed on all samples exposed to SCW, which were identified as Fe₂O₃/Fe₃O₄ + spinel/Cr₂O₃/Ni-enrichment/316 SS from the outer to inner layer. The possible oxidation mechanisms are also discussed.     

Synergistic corrosion inhibition study of Armco iron in sodium chloride by piperidin-1-yl-phosphonic acid-Zn system

Electrochemical techniques, weight loss method and surface analysis were used to study the synergistic inhibition offered by Zn²⁺ and piperidin-1-yl-phosphonic acid (PPA) to the corrosion of Armco iron in 3% chloride solution. It is observed that the combination between PPA and Zn²⁺ shows excellent inhibition efficiency. The potentiodynamic polarization curves reveal that 5 × 10⁻³ mol l⁻¹ of PPA has only 76.7% inhibition efficiency whereas the mixture containing 5 × 10⁻³ mol l⁻¹ PPA -20%Zn²⁺ has 90.2% inhibition efficiency. This suggests that a synergistic effect exists between Zn²⁺ and PPA. The Fourier transform infrared (FTIR) spectrum of the film formed on iron indicates phosphonates zinc salt formation. A suitable mechanism of corrosion inhibition is proposed based on the results obtained. The surface film analysis showed that in the absence of Zn²⁺, the protective film consists of Fe²⁺-PPA complex formed on the anodic sites of the metal surface, whereas in the presence of Zn²⁺, the protective film consists of Fe²⁺-PPA complex and Zn(OH)₂.     

Influence of chromium substitution on structural and magnetic properties of BaFe12O19 powder prepared by sol-gel auto combustion method

The nanocrystalline Cr³⁺ substituted barium hexaferrite having generic formula BaFe_12−xCr_xO₁₉ (where x = 0.00, 0.25, 0.50, 0.75, and 1.00) samples were synthesized by sol-gel auto-combustion technique. The precursors were prepared by using stoichiometric amounts of Ba²⁺, Fe³⁺ and Cr³⁺ nitrate solutions with citric acid as a chelating agent. The metal nitrate to citric acid ratio was taken as 1:2 while pH of the solution was kept at 8. The thermal decomposition of nitrate-citrate gels of as-prepared powder was investigated by TG/DTA. The as-prepared powder of BaFe_12−xCr_xO₁₉ was sintered at 900 °C for 8 h. The sintered powder was characterized by XRD, EDAX, SEM and VSM technique. The pure barium hexaferrite shows only single phase hexagonal structure, while for the samples at x = 0.25, 0.50, 0.75 and 1.00 shows α-Fe₂O₃ peaks with M-phase of barium hexaferrite. The lattice parameters (a and c) decreases with increase in chromium content x. The particle size obtained from XRD data is in the range of 30-40 nm which confirms the nanocrystalline nature of the samples. The magnetic properties were investigated by means of vibrating sample magnetometer (VSM) technique. The saturation magnetization (M_s), remanence magnetization (M_r), coercivity (H_c) and magneton number (n_B) decreases with increase in chromium content x.     

Corrosion behavior of steel under wet and dry cycles containing Cr ion

The corrosion behavior of mild steel has been investigated during the wet and dry cyclic transitions containing Cr³⁺ ion added as sulfate in order to gain a better understanding of the influence of Cr on the atmospheric corrosion of steels. The corrosion rate during drying is greatly suppressed by the existence of Cr³⁺ ion in the electrolyte covered with the surface. Lower corrosion rates are observed during drying even if the surface have been polarized to negative potentials below −200 mV_SHE during the wet corrosion conditions in which the surface-covered electrolyte contains Cr³⁺ ion. This corrosion behavior is identical to the case of Cr-containing steel for the wet and dry cyclic transitions without the addition of Cr³⁺ ion. The composition of rust layer after the wet and dry cyclic transitions is composed of α-FeOOH, γ-FeOOH and Fe_3−δO₄ for both cases of non-Cr³⁺ and Cr³⁺-containing condition, and no significant difference in the mass fraction of the above rust substances between two conditions is observed by means of Mössbauer spectroscopy. The only difference in the rust layer is that the rust formed under the wet and dry cyclic transitions containing Cr³⁺ ion contains a certain amount of Cr near the steel/rust interface. Those results suggest that the role of Cr during the wet and dry cyclic transitions is the inhibition of the rust reduction and the formation of Fe²⁺-state intermediate by the existence of Cr in the rust layer. This can lead to the inhibition of the oxygen reduction during drying.