Oxidation of iron at 400-600 °C in dry and wet O2

The oxidation of iron in dry and wet O₂ at 400-600 °C has been re-investigated using gravimetry, SEM/EDX, XRD and FIB. In the presence of O₂, water vapour accelerates iron oxidation at 500 and 600 °C. At 400 and 500 °C the magnetite layer is duplex and exposure to water vapour results in the formation of blades on top of a fine-grained hematite layer. At 600 °C it results in a surface without needles and blades. The increased oxidation rate at 500 and 600 °C is attributed to a smaller grain size in the hematite layer resulting in faster ion transport.     

Thermoelectric properties of novel skutterudites with didymium: DDy(Fe1−xCox)4Sb12 and DDy(Fe1−xNix)4Sb12

In order to improve the thermoelectric properties via efficient phonon scattering Didymium (DD), a mixture of Pr and Nd, was used as a new filler in ternary skutterudites (Fe_1−xCo_x)₄Sb₁₂ and (Fe_1−xNi_x)₄Sb₁₂. DD-filling levels have been determined from combined data of X-ray powder diffraction and electron microprobe analyses (EMPA). Thermoelectric properties have been characterized by measurements of electrical resistivity, thermopower and thermal conductivity in the temperature range from 4.3 to 800 K. The effect of nanostructuring in DD_0.4Fe₂Co₂Sb₁₂ was elucidated from a comparison of both micro-powder (ground in a WC-mortar, 10 μm) and nano-powder (ball-milled, 150 nm), both hot pressed under identical conditions. The figure of merit ZT depends on the Fe/Co and Ni/Co-contents, respectively, reaching ZT > 1. At low temperatures the nanostructured material exhibits a higher thermoelectric figure of merit. The Vickers hardness was measured for all samples being higher for the nanostructured material.     

Oxidation, carburisation and metal dusting of 304 stainless steel in CO/CO2 and CO/H2/H2O gas mixtures

The oxidation and carburisation behaviour of 304 stainless steel was studied during thermal cycling in CO/CO₂ at 700 °C, and also in CO/H₂/H₂O at 680 °C. Thermal cycling caused repeated scale separation which accelerated chromium depletion from the alloy subsurface regions. The CO/CO₂ gas, with a_C=7 and , caused internal precipitation of oxides and carbides, some surface damage, but no dusting. In contrast, the CO/H₂/H₂O gas, with a_C = 19 and caused rapid graphite deposition and metal dusting. This was accompanied by internal oxidation and carburisation. The internal oxide was identified as spinel, which forms in the short term, but not at long reaction time. Its formation produced a significant volume expansion, which disrupted the material and resulted in surface damage in both gas atmospheres. In CO/H₂/H₂O, however, direct graphite deposition and metal disintegration into dust was the main reaction. The very different reaction morphologies produced by the two gas mixtures are discussed in terms of competing gas-alloy reaction steps.     

Influence of thickness on the material characteristics of reactively sputtered W2N layer and electrical properties of W/W2N/SiO2/Si capacitors

The material characteristics of W₂N layer and electrical properties of W/W₂N/SiO₂/Si metal–oxide–semiconductor (MOS) capacitors with different W₂N thickness upon annealing in N₂ + H₂ ambient at 500 °C for 20 min are investigated. The nitrogen concentration of W₂N for the W/W₂N stack with thin W₂N layer (≤10 nm) is lower than that for the W/W₂N stack with thick W₂N layer (≥15 nm). In addition, the crystallinity of W₂N in the W/W₂N (15 nm) stack is better than that in the W/W₂N (10 nm) stack. For all capacitors, the oxide charges decrease significantly after annealing and the amount of oxide charges is independent of the W₂N thickness. However, the work function (Φ_m) of the W/W₂N (≤10 nm) stack (4.6 eV) is smaller than that of W/W₂N (15 nm) stack (5.0 eV). The Φ_m of W/W₂N (15 nm) stack is close to that of W₂N single layer. After annealing, the Φ_m of W/W₂N (15 nm) stack and W₂N single layer decrease, especially for the W₂N single layer. But for the W/W₂N (≤10 nm) stack, the Φ_m increases after annealing.     

Kinetics of H2O2 reaction with oxide films on carbon steel

The nature of carbon steel surfaces in 0.01 M borate solutions (pH 10.6) have been characterized using a range of electrochemical techniques and ex situ analyses such as Raman and Auger spectroscopy. Their subsequent behaviour on exposure to 10⁻³ M H₂O₂-containing solutions has also been studied. The anodically oxidized carbon steel surfaces have been characterized according to three regions: (I) the potential range <−0.5 V (vs SCE), when the surface is active and covered by Fe^II/Fe^III oxide/hydroxide; (II) the potential range −0.5 V to 0.0 V when the surface is passivated by an outer layer of Fe^III oxide/hydroxide over the inner layer of Fe^II/Fe^III oxide/hydroxide; and (III) potentials >0 V when further growth of the underlying layer appears to lead to minor film breakdown/restructuring. The addition of H₂O₂ to films grown in the passive region or above (II and III) leads initially to a degradation of the outer layer allowing increased growth of the inner layer. Subsequently, the outer passivating layer is repaired and passivity re-established. These changes appear to be confirmed by Raman spectroscopy.     

Evidence for Chromium Evaporation Influencing the Oxidation of 304L: The Effect of Temperature and Flow Rate

The influence of temperature and flow rate on the oxidation of 304L steel in O₂/H₂O mixtures was investigated. Polished samples were isothermally exposed to dry O₂ and O₂+40% H₂O at 500–800°C at 0.02–13 cm/sec flow velocity, for 168 hr. The samples were analyzed by gravimetry, XRD, ESEM/EDX, and AES depth profiling. The oxidation of 304L in water vapor/oxygen mixtures at 500–800°C is strongly influenced by chromium evaporation. The loss of chromium tends to convert the protective chromia-rich oxide initially formed into a poorly protective, iron-rich oxide. The rate of oxidation depends on flow rate; high flow rates result in an early breakdown of the protective oxide. The most rapid breakdown of the protective oxide occurs at the highest temperature (800°C) and the highest gas flow (4000 ml/min=13 cm/sec). The oxide formed close to grain boundaries in the metal is more protective, while other parts, grain surfaces suffer breakaway corrosion. The protective oxide consists of a Cr-rich 50–200-nm thick M₂O₃ film, while the parts experiencing breakaway corrosion form a 10–30-m thick Fe-rich M₂O₃/M₃O₄ scale. The results show that chromium evaporation is a key process affecting the oxidation resistance of chromia formers and marginal chromia formers in O₂/H₂O mixtures.     

High-temperature oxidation of Fe-2 1 4 Cr-1Mo in oxygen

The oxidation of a 2 ₁ ⁴ Cr-1Mo steel in dry flowing oxygen has been studied in the temperature range 550–700°C for periods of up to 100 hr. A detailed low-resolution microstructural investigation revealed a layered oxide consisting of a very fine-grained and finely pored innermost layer of doped spinel, a central columnar-grained relatively coarsely pored layer of magnetite, and an outer fine-grained hematite layer with fine pores and covered with whiskers of -Fe₂O₃. This structure is compared with previous results on Fe and model Fe-Cr alloys, as are the kinetics of the oxidation reaction.     

dc-Magnetic susceptibility and EPR studies of vapour phase grown Cd1−xCoxTe crystals

Cd_1−xCo_xTe crystals (x = 0.001, 0.003, 0.005, 0.007 and 0.009) were grown by vapour phase technique. The grown diluted magnetic semiconducting (DMS) crystals were subjected to magnetization and dc-magnetic susceptibilities at room temperature. EPR spectra were recorded at 20 K for samples of all compositions. EPR spectra exhibited a broad resonance band around g  5.43. All the studies indicated the paramagnetic nature of the samples.     

Electrochemical behaviour and corrosion performance of Mg–Li–Al–Zn anodes with high Al composition

This study investigated the electrochemical and corrosion performance of Mg–Li–Al–Zn anodes with Al compositions of 3 wt.% and 9 wt.%. Mg–Li–Al–Zn alloy with 9 wt.% Al had a relatively negative open-circuit potential and a high discharge voltage in MgCl₂ electrolyte, owing to the distribution of numerous AlLi particles in the matrix of the alloy. AlLi particles were believed to transform to Al particles during the corrosion of the Mg–Li–Al–Zn anode. The high-Al anode material exhibited good corrosion performance since a dense and continuous Mg(OH)₂/Al composite layer covered the surface of the high-Al anode. Experimentally, increasing the Li⁺ concentration in the electrolyte improved the corrosion performance of the Mg anode.     

An ESEM in situ investigation of initial stages of the KCl induced high temperature corrosion of a Fe–2.25Cr–1Mo steel at 400 °C

The initial oxidation of a low-alloyed steel (Fe–2.25Cr–1Mo) in the presence of small amounts of KCl(s) have been investigated through ESEM in situ exposure and analysis at 400 °C. The samples were also characterized by XRD, SEM/EDX and FIB. The present study shows the corrosive nature of KCl towards the low alloyed steel. It is concluded that the initial KCl distribution is important and that a KCl/FeCl₂ liquid phase film forms on large parts of the oxide surface in the presence of KCl. It is proposed that Cl increases the oxidation rate (by decorating oxide grain boundaries) and decreases the oxide scale adhesion.     

The Effect of Traces of SO2 on Iron Oxidation: A Microstructural Study

Pure iron has been exposed to pure O₂ and O₂ with 100 ppm SO₂ at 525 °C for 1 and 24 h. The samples were investigated by FIB, SEM, TEM, EDX and EBSD. The oxide scales formed on iron at 525 °C in O₂ and in O₂ + 100 ppm SO₂ are dense and adherent and consist of three layers. The outermost layer consists of hematite. Beneath it there is a duplex-magnetite scale. The two magnetite layers are separated by a straight interface. It is concluded that the inner-magnetite layer grows inward while the outer magnetite layer grows outwards. In the presence of SO₂ the inner-magnetite layer is much thinner, iron sulphate forms at the oxide surface and discrete iron sulphide grains nucleate at the metal/oxide interface. The amount of sulphide at the metal/oxide interface increases with exposure time. The oxidation of iron in oxygen at 525 °C is inhibited by 100 ppm SO₂. The inhibitive effect of SO₂ is attributed to iron sulphate that blocks active sites on the hematite surface, slowing down the formation of oxygen ions. This explains the strong inhibition of the inward growth of magnetite by SO₂. There is also a marked effect on the morphology of the outer oxide, producing hematite whisker growth and a less porous surface in the presence of SO₂.     

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.     

The influence of CO2, AlCl3 · 6H2O, MgCl2 · 6H2O, Na2SO4 and NaCl on the atmospheric corrosion of aluminum

The influence of salt deposits on the atmospheric corrosion of high purity Al (99.999%) was studied in the laboratory. Four chloride and sulfate-containing salts, NaCl, Na₂SO₄, AlCl₃ · 6H₂O and MgCl₂ · 6H₂O were investigated. The samples were exposed to purified humid air with careful control of the relative humidity (95%), temperature (22.0 °C), and air flow. The concentration of CO₂ was 350 ppm or <1 ppm and the exposure time was four weeks. Under the experimental conditions all four salts formed aqueous solutions on the metal surface. Mass gain and metal loss results are reported. The corroded surfaces were studied by ESEM, OM, AES and FEG/SEM equipped with EDX. The corrosion products were analyzed by gravimetry, IC and grazing incidence XRD. In the absence of CO₂, the corrosivity of the chloride salts studied increases in the order MgCl₂ · 6H₂O < AlCl₃ · 6H₂O < NaCl. Sodium chloride is very corrosive in this environment because the sodium ion supports the development of high pH in the cathodic areas, resulting in alkaline dissolution of the alumina passive film and rapid general corrosion. The low corrosivity of MgCl₂ · 6H₂O is explained by the inability of Mg²⁺ to support high pH values in the cathodic areas. In the presence of carbon dioxide, the corrosion induced by the salts studied exhibit similar rates. Carbon dioxide strongly inhibits aluminum corrosion in the presence of AlCl₃ · 6H₂O and especially, NaCl, while it is slightly corrosive in the presence of MgCl₂ · 6H₂O. The corrosion effects of CO₂ are explained in terms of its acidic properties and by the precipitation of carbonates. In the absence of CO₂, Na₂SO₄ is less corrosive than NaCl. This is explained by the lower solubility of aluminum hydroxy sulfates in comparison to the chlorides. The average corrosion rate in the presence of CO₂ is the same for both salts. The main difference is that sulfate is less efficient than chloride in causing pitting of aluminum in neutral or acidic media.     

Effects of additives on synthesis of vanadium carbide (V8C7) nanopowders by thermal processing of the precursor

Vanadium carbide (V₈C₇) nanopowders can be synthesized by thermal processing of the precursor of ammonium vanadate (NH₄VO₃) and nanometer carbon black. Effects of additives (CaF₂, CeCl₃·7H₂O and LaCl₃·7H₂O) on the phase composition and microstructure of the synthesized powders were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that additives (CaF₂, CeCl₃·7H₂O and LaCl₃·7H₂O) can accelerate the solid state reaction during synthesis of V₈C₇, and these additives play a vital role in determining the phase composition and microstructure. V₈C₇ powders with basically single phase can be synthesized at 1100 °C for 0.5 h with the addition of additives (CaF₂, CeCl₃·7H₂O and LaCl₃·7H₂O), and the powders show good dispersion and are mainly composed of uniformly-sized spherical particles with a mean diameter of 50 nm. Further experiment shows that V₈C₇ powders can be prepared at 950 °C for 1 h with 1.0 wt% CaF₂ as additive.     

A theoretical interpretation of the pressure–composition isotherms of RNi5 (, Pr, Nd and Sm) systems based on statistical mechanics

A simple model to understand the phase behavior of RNi₅–H (R=La, Pr, Nd and Sm) systems is proposed based on the statistical mechanics. The essential parameters in the present model, hydrogen site energies and lattice relaxation term, were optimized so as to reproduce the experimentally determined pressure–composition isotherms (PCIs) of these four alloys. The qualitative difference in the PCI of LaNi₅ from other alloys – at room temperature the former tends to show a single plateau while the latter have two plateaux – is explicable in terms of hydrogen site energies as follows. In case of LaNi₅, four hydrogen sites, which are considered to belong to 3f, 12n, 6m and 12o sites, are stable in α phase, leading to a wide single plateau upto N6 where N is in RNi₅H_N below room temperature. At higher temperature, small differences in site energies for these sites brings the appearance of the second plateau. In case of other three alloys, on the other hand, the 6m site (or 12o) is less stable than LaNi₅ in the α phase. After obtaining enough lattice relaxation energy by around N=4 through hydrogenation, the 6m site becomes favorable for hydrogen, bringing the sencond plateau spanning from N4 to N6. Predicted T–C phase diagrams are also shown.     

Ru-based bimetallic alloys for hydrogen generation by hydrolysis of sodium tetrahydroborate

The present study contemplates the application of Ru-based bimetallic alloys for hydrogen generation by hydrolysis of sodium tetrahydroborate (NaBH₄). Ru and Pt, RuCu, RuPd, RuAg and RuPt (atomic ratio 1:1), PtAg, and Ru_xPt_y (atomic ratios x:y of 2:1 or 1:2), all supported over titanium oxide, were prepared. Their activity decreased in the order RuRu₂Pt₁ > RuPtRu₁Pt₂ > RuPd > RuAgPt > RuCu > PtAg. Alloying Ru with an inactive metal like Cu, Pd or Ag did not improve the performances of Ru. The catalytic ability of Ru₂Pt₁-TiO₂ is in the range of the highest values reported so far in the literature with a hydrogen generation rate of 15.2 L(H₂) min⁻¹ g⁻¹(RuPt). After separation from the reaction medium and rinsing with deionised water, the used Ru₂Pt₁-TiO₂ catalyst was re-evaluated and almost the same catalytic activities as fresh catalyst were obtained during several cycles.     

The role of valence electron concentration in the cohesive properties of YBxN1−x, YCxN1−x and YNxO1−x compounds

The mechanical properties are not yet understood at basic levels. Previous works shows that the greatest hardness for rock-salt structures (such as TiC_xN_1−x) is attained for a valence electron concentration (VEC) of 4.2 electrons per atom. The present work is aimed to explore this concept for yttrium-based compounds. By means of first principles calculations we did a systematical investigation where nitrogen in YN (VEC = 4) was supplanted by either of B, C or O to reduce or increase its VEC, forming YB_xN_1−x, YC_xN_1−x and YN_1−xO_x ternary compounds. We have calculated the cohesive energy (E_O), cell volume (V_O), bulk modulus (B_O) and density of states (DoS) as a function of VEC. The Fermi level (E_f,) is shifted toward the valence band by substituting B or C in YN, and toward the conduction band by means of O. It is concluded that the optimal position for E_f (maximum B_O) is linked to the saturation of electronic states with e_g-symmetry. At this point the excess of electrons provided by O starts filling antibonding states with t_2g-symmetry. That is, B_O increases monotonically as a function of VEC until VEC  4.1, after that point B_O decrease.     

Oxidation of Fe-3 wt.% Cr alloy

The oxidation behavior and the oxide microstructure on Fe-3 wt. % Cr alloy were investigated at 800°C in dry air at atmospheric pressure. Two distinct oxidation rate laws were observed: initial parabolic oxidation was followed by nonparabolic growth. The change in the oxidation kinetics was caused by microchemical and microstructural developments in the oxide scale. Several layers developed in the oxide scale, consisting of an innermost layer of (Fe,Cr)₃O₄ spinel, an intermediate layer of (Fe,Cr)₂O₃ sesquioxide, and two outer layers of Fe₂O₃ hematite, each with different morphologies. Wustite (Fe_1–xO) and distorted cubic oxide (-(Fe,Cr)₂O₃) were observed during the iniital parabolic oxidation only.     

Analytical Electron Microscopy Study of Interfacial Oxides formed on a Hot-rolled Low-Carbon Steel

The detailed microstructure of oxides at the metal–scale interface of a commercial, hot-rolled steel strip has been examined using analytical electron microscopy. A continuous magnetite layer of about 1–2 m thick was observed at the interface. The magnetite layer often contained cracks propagating in directions parallel to the interface. In the vicinity of the cracks, the magnetite was oxidized to nanosized maghemite (-Fe₂O₃). We also observed evidence indicating the existence of microchannels which were roughly perpendicular to the interface and might allow oxygen to reach the embedded cracks. Oxide above the magnetite layer was a mixture of -iron and magnetite produced by wustite decomposition.     

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.