Development of plasma nitrocarburizing and post-oxidation technology for the replacement of Cr<Superscript>6+</Superscript> plating for application to vehicle engine shafts

Plasma nitrocarburizing and post-oxidation treatments were performed to improve the wear and corrosion resistance of S45C steel. Plasma nitrocarburizing was conducted for 3 h at 570°C in a nitrogen, hydrogen and methane atmosphere to produce the ε-Fe₂₋₃(N,C) phase. It was found that the compound layer produced by plasma nitrocarburising was predominantly composed of the ∈-phase with traces of the γ′-Fe₄(N,C) phase. The thickness of the compound layer was approximately 12 μm and the diffusion layer was approximately 300 μm in thickness. Plasma post oxidation was performed on nitrocarburized samples with various oxygen/hydrogen ratios at a constant temperature of 500°C for 1 h. The very thin magnetite (Fe₃O₄) layer 1 μm to 2 μm in thickness on top of the compound layer was obtained by plasma post oxidation. It was also confirmed that further improvement of the corrosion characteristics of the nitrocarburized compound layer was possible with an application of the superficial magnetite layer. Finally, throttle valve shafts of S45C steel were treated under optimum plasma processing conditions. Accelerated life time test results using a throttle body assembled with a shaft treated by plasma nitrocarburising and post oxidation showed that plasma nitrocarburizing and plasma post-oxidation processes could be a viable technology in the very near future in place of Cr⁶ plating.     

Gamma-radiation-induced corrosion of carbon steel in neutral and mildly basic water at 150 °C

The effect of γ-radiation on the kinetics of carbon steel corrosion has been investigated by characterizing the oxide films formed on steel coupons at 150 °C and at two pH values. Results show that continuous irradiation enhances surface oxide formation with the type of oxide formed dependant on the solution pH. For experiments at 150 °C and a [OH⁻] equivalent to that for pH_{25 °C} = 10.6, the surface oxide on carbon steel after γ-irradiation was non-porous and uniform, and no localized corrosion was observed. This oxide, however, appears to be susceptible to brittle fracture during cooling. Raman spectroscopy of the surface film indicates that it is a mixture of the phases of Fe₃O₄ and γ-Fe₂O₃. In contrast, at 150 °C with [OH⁻] equivalent to neutral pH_{25 °C}, metal dissolution is significant and the surface oxide film is very porous. Raman spectra show that this oxide film is also composed of a mixture of Fe₃O₄ and γ-Fe₂O_3. The results from this work combined with previously reported electrochemical studies of the same system as a function of pH and temperature can be used to deconvolute the effects of radiation, pH and temperature on the nature of the corrosion process.     

Tunneling magnetoresistance in sintered Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> samples diluted with Fe and α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

Electric transport and magnetoresistance characteristics were investigated for Fe₃O₄-x Fe(x=0, 10, 20 wt.%) samples and Fe₃O₄-α-Fe₂O₃ samples sintered at 500°C. For composition dependence of Fe₃O₄-x Fe samples, the largest room temperature MR, 3.3% at 10 kOe, was obtained from a Fe₃O₄-10 Fe sample. For the surface heat treatment dependence of Fe₃O₄ powders, the largest room temperature MR, 4% at 10 kOe, was obtained from a Fe₃O₄-α-Fe₂O₃ sample sintered with Fe₃O₄ powders heated at 200°C in air. It was found that these enhanced MR ratios always appear together with the appropriate excess resistance which is regarded as the tunneling barrier. These enhanced MR ratios of Fe₃O₄-10 Fe and Fe₃O₄-α-Fe₂O₃ samples can be explained by the increased interparticle contact sites and the appropriate thickness of α-Fe₂O₃, respectively.     

Modification of Low-Alloy Steel Surface by Plasma Electrolytic Nitriding

The structure of the low-alloy steel after plasma electrolytic nitriding (PEN) in electrolyte containing ammonium nitrate was investigated. The cross-sectional microstructure, composition, and phase constituents of modified layer under different processing conditions were characterized. It is shown that anode PEN provides the saturation of steel with nitrogen and formation of α-Fe₂O₃, FeO, and Fe₃O₄ oxides, Fe_2-3N nitride, and martensite. The aqueous solution that contained 15 wt.% NH₄Cl and 5 wt.% NH₄NO₃ allows one to obtain the hardened layer with a thickness of 80 μm and a microhardness up to 740 HV during 5 min at 850 °C. Surface roughness decreases from 1.5 to 0.8 μm after 5-min PEN at 650 °C. The proposed electrolyte and processing mode (750 °C, 10 min) enable to obtain the decrease in the weight loss after lubricate wear testing by a factor of 2.7. The base-nitrate electrolyte conditioned a decrease in the corrosion current density by a factor of 9 due to passivating effect of the oxide and nitride of iron.     

Hot corrosion of a novel (Ni,Co)O/(Ni,Co)Fe2O4 composite coating thermally converted from an electrodeposited Ni–Co–Fe2O3 composite coating

Ni–Co–Fe₂O₃ composite coatings were successfully developed by sediment co-deposition. In order to improve their hot corrosion resistance, a pre-oxidation treatment was conducted at 1000 °C for 6 h. The corrosion behaviour of the oxidised composite coating was investigated at 960 °C in an atmosphere consisting of a mixture of Na₃AlF₆–AlF₃–CaF molten salts and air. They exhibited good hot corrosion resistance due to not only the pre-formed oxide scale with (Ni,Co)O and (Ni,Co)Fe₂O₄ phases after pre-oxidation, but also the formation of (Ni,Co,Fe)Al₂O₄ phases in the outer layer and a well-distributed NiFe₂O₄-enriched phase along the grain boundaries in the subscale area during the corrosion process.     

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.     

Field sludge characterization obtained from inner of pipelines

Physicochemical characterization of sludge obtained from refined hydrocarbons transmission pipeline was carried out through Mössbauer spectroscopy and X-ray diffraction. The Mössbauer and X-ray patterns indicate the presence of corrosion products composed of different iron oxide and sulfide phases. Hematite (α-Fe₂O₃), magnetite (Fe₃O₄), maghemite (γ-Fe₂O₃), magnetic and superparamagnetic goethite (α-FeOOH), pyrrhotite (Fe_1−xS), akaganeite (β-FeOOH), and lepidocrocite (γ-FeOOH) were identified as corrosion products in samples obtained from pipeline transporting Magna and Premium gasoline. For diesel transmission pipeline, hematite, magnetite, and magnetic goethite were identified. Corrosion products follow a simple reaction mechanism of steel dissolution in aerated aqueous media at a near-neutral pH. Chemical composition of the corrosion products depends on H₂O and sulfur inherent in fluids (traces). These results can be useful for decision-making with regard to pipeline corrosion control.     

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)     

Metal-oxide heterophase structures formed at low temperature activation of iron. 2. IR spectroscopy

Low-temperature activation of iron is observed during its isothermal oxidation at a temperature of 300°C and an oxygen pressure of 10⁻² Torr. A 1-h treatment provides the maximum gain in the oxide layer thickness for this oxygen pressure. According to IR spectroscopic data, the amount of Fe₃O₄ in the oxide reaches the maximum in the oxygen pressure interval from 10⁻³ to 10⁻² Torr and decreases with a further increase in the oxygen pressure. In contrast, the haematite content increases with an increase in the oxygen pressure. In the latter case, first, the content of the α-Fe₂O₃ phase increases to reach its maximum at pressures from 5×10⁻³ to 10⁻² Torr, while the phase of haematite γ-Fe₂O₃ appears at 0.1 Torr. This confirms the earlier assumption that the haematite islets layer plays the decisive roles in the low-temperature activation and the active-passive transition of iron. Original Russian Text ? V.A. Kotenev, N.P. Sokolova, A.M. Gorbunov, A.Yu. Tsivadze, 2007, published in Zashchita Metallov, 2007, Vol. 43, No. 6, pp. 630–634.     

Corrosion of a stainless steel and nickel-based alloys in high temperature supercritical carbon dioxide environment

Corrosion of four alloys has been studied in supercritical carbon dioxide at 650 °C and 20 MPa, specifically AL-6XN stainless steel and three nickel-based alloys, PE-16, Haynes 230, and Alloy 625. The tests were performed for exposure durations of up to 3000 h with samples being removed for analyses at 500 h intervals. The corrosion performance of the alloys was evaluated by weight change measurements, and the surface oxide layers were characterized by scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Weight gain measurements showed that the Al-6XN stainless steel exhibited the least corrosion resistance while the weight gains were nearly similar for the other alloys. The oxide layer in AL-6XN stainless steel was composed of large equiaxed grained outer layer of Fe₃O₄ (magnetite) and an inner layer of FeCr₂O₄. Oxide spallation was observed in this stainless steel even after 500 h exposure. In all alloys, Cr-rich oxides phases of Cr₂O₃ and Cr_1.4Fe_0.7O₃ were identified as the protective layers. In alloy PE-16 a thin layer of aluminum oxide formed that promoted the corrosion resistance of the alloy. Cr₂O₃ was identified as the main protective oxide layer in nickel base alloys Haynes 230 and 625.     

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.     

Plasma post-oxidation mechanisms of nitrided ferrous alloys

The mechanisms of plasma post-oxidation of plasma nitrided AISI 1045 plain steel were investigated. The influence of plasma post-oxidation temperature and time on the oxide layer thickness, morphology, and composition were addressed. The oxide thickness grows exponentially with temperature, with activation energy of 68 ± 5 kJ mol ^− 1. The time dependence of the oxide layer thickness, on the other hand, is governed by a diffusion-reaction process. It was verified that temperature plays an important role on the morphology of the oxide. Indeed, at the highest temperature, 550 °C, the oxide layer is not homogeneous and has a lower hardness than oxide layers obtained at 480 to 500 °C. The latter seem to be more favorable temperatures to grow compact, homogeneous, and harder oxide layers. The oxide-nitride bi-layer produced here contains a mixture of γ′-Fe₄N and ε-Fe_2-3N and only one iron oxide, Fe₃O₄ (magnetite). The proportions between these phases vary with the plasma processing temperature and time.     

XPS study of oxides on carbon steel in LiOH at 250°C

Using X-ray photo-electron spectroscopy (XPS), the compositions of the oxides formed at 250°C on carbon steel in 10.5 pH LiOH solution containing 0.05 ppm and 3.5 ppm dissolved oxygen were studied. Magnetite (Fe₃O₄) was found to be bulk oxide in both cases. A layer of γ-Fe₂O₃ was found on the outer surface of the sample exposed to the low oxygen environment, while α-Fe₂O₃ in small amounts, together with bulk Fe₃O₄, was found for the case of the high oxygen environment. Chemisorption of water molecules on the outer surface was observed in both the environments with the additional possibility of formation of FeOOH. Weak signals of Li 1s peak indicated the formation of small amounts of LiFeO₂ in both cases.     

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.     

An electrochemical study of phase-transitions in rust layers

Isolated rust layers have been investigated by electrochemical methods to find out whether their reduction and re-oxidation can affect the atmospheric corrosion of iron. At potentials below 0 mV, first a thin Fe²⁺-containing surface layer is formed on top of the γ-FeOOH. This reduced surface layer can dissolve into the cell electrolyte at acid pH, or at lower potentials the Fe²⁺-ions can react with γ-FeOOH to Fe₃O₄. The formation of magnetite could be followed by in-situ magnetic measurements. The reduced surface layer can easily be oxidized back to γ-FeOOH, magnetite can partly be oxidized to γ-Fe₂O₃.     

Fe-30Ni-5NiO alloy as inert anode for low-temperature aluminum electrolysis

Fe-30Ni-5NiO alloy anodes were prepared by a spark plasma sintering process for aluminum electrolysis. NiO nano-particles with the size of ∼20 nm were dispersed in the anodes. The oxidation behaviors of the anodes were investigated at 800°C and 850°C, respectively. The electrolysis corrosion behaviors were tested in a cryolite-alumina electrolyte at a low temperature of 800°C with anodic current densities of ∼0.5 A/cm². The results indicated that the oxidation kinetic of the anodes followed a parabolic law. A continuous Fe₂O₃ film selectively formed on the surface of the anode during the electrolysis process. A semi-continuous Al₂O₃ layer was observed at oxide film/alloy interface, probably caused by an in-situ chemical dissolution process.     

Identification of corrosion products resulting from accelerated oxidation process

Abstract

Scanning electron microscopy analysis, X-ray powder diffraction and room temperature ⁵⁷Fe Mössbauer spectroscopy were used to identify the corrosion products of uncoated and coated low alloy steels (LAS) and low carbon steels (LCS) resulting from an accelerated steam oxidation test for 180 h at 660°C. From the Mössbauer spectral analysis, it was shown that in all cases, a series of iron compounds such as α-Fe₂O₃, Fe₃O₄, γ-Fe₂O₃, δ-FeOOH, α-FeOOH, Fe(OH)₂ and Fe(OH)₃ were formed, while XRD measurements revealed only the α-Fe₂O₃ and/or Fe₃O₄/γ-Fe₂O₃ phases. In the LAS uncoated sample, an amorphous phase with magnetic features is found. In the spectra of the borided samples and of the uncoated LCS, an additional doublet was observed, which reveals the presence of a superparamagnetic phase. From the relative areas of the subspectra, it is concluded that the boron aluminised sample underwent the lowest degradation. The mechanism proposed for corrosion products formation is based on the dissociation process.     

The growth and structure of oxide films formed on Fe in O2 and CO2 at 550°C

A study has been made of the structure of oxide layers formed at different times on abraded Fe oxidized in 1 atm O₂ and CO₂ at 550°C. A duplex Fe₃O₄ layer was formed and the inner layer was considered to grow by an oxide dissociation mechanism. The growth of both layers has been explained by a model, which correlates the overall kinetics with oxide grain growth. Derived values of the parabolic rate constant for lattice diffusion have been used to calculate self-diffusion coefficients, which were in good agreement with literature values for Fe diffusion in Fe₃O₄, but were very much larger than the values for either Fe or O in -Fe₂O₃.     

Influence of heat treatment on phase transformation of clay-iron oxide composite

Magnetic clay composite prepared by the method of precipitation of iron oxide onto the clay surface was subjected to a heat treatment. The presence of iron oxide phase in composite before the heating was determined by the Mössbauer spectroscopy method as γ-Fe₂O₃. Structural changes of maghemite in clay composite after heating at selected temperatures in N₂ and Ar/H₂ atmosphere were studied using Mössbauer spectroscopy, X-ray diffraction, TG/DSC and SEM methods. It was shown the full transformation of γ-Fe₂O₃ to α-Fe₂O₃ in the inert atmosphere at temperature 650 °C and only a partial transformation to Fe₃O₄ in the reductive atmosphere at 300 °C.     

Some aspects of the Aluminide coating on Fe-18Cr alloy

Diffusion aluminide coating was formed on Fe-18Cr alloy by the pack cementation method. Electron and X-ray diffraction techniques were used to identify the phases formed on the aluminide coating layer. This coating layer was found to consist of the FeAl and Fe₃Al phases. Furthermore, coated specimens were exposed to air at 1200°C for 60 hours, and the oxide scales formed on the coating layer consist of randomly oriented spinel Fe(AlCr)₂O₄ and α-Al₂O₃.