A combined study of the oxidation mechanism and resistance of AISI D6 steel exposed at high temperature environments

In this work it is thoroughly examined the oxidation performance of D6 tool steel under isochronal and isothermal oxidations. Isochronal oxidation tests, from ambient temperature to 1000 °C, revealed the oxidation rate of the coupons at different temperatures. Four different temperatures were selected for the isothermal oxidation test, which correspond to different oxidation rates. The oxidation and the examination of the samples were accomplished by thermogravimetric analysis (TG) in air with which the mass gain of the samples due to oxidation was simultaneously acquired. The samples were, also, examined by scanning electron microscopy (SEM), in order to observe their surface before and after the oxidation tests. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) were used for the accurate identification of the as formed oxides. The results revealed that in every case two distinct layers of oxides were formed while their composition was different, depending on the temperature of oxidation. Furthermore, the thickness of the as formed oxides is increased when the oxidation is performed at higher temperatures.     

Corrosion of aluminium components studied with MIES, UPS and XPS

We use X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and metastable impact electron spectroscopy (MIES) to investigate the corrosion of aluminium components. Clean aluminium films were prepared under ultrahigh vacuum (UHV) conditions and exposed to water and NaCl. We attempt to provide a model for the mechanism of this interaction and its effects on the durability of the components.     

The influence of oxidation with nitric acid on the preparation and properties of active carbon enriched in nitrogen

The effect of oxidation by 20% nitric acid on the properties and performance of active carbons enriched with nitrogen by means of the reaction with urea in the presence of air has been studied. The study has been made on demineralised orthocoking coal and the carbonisates obtained from it at 600 or 700 °C, subjected to the processes of nitrogenation, oxidation and activation with KOH in different sequences. The amount of nitrogen introduced into the carbon with the aid of urea has been found to depend on the stage at which the process of nitrogenation was performed. The process of oxidation of the demineralised coal and the active carbon obtained from the former has been found to favour nitrogen introduction into the carbon structure. In the process of nitrogenation of the carbonisates the amount of nitrogen introduced has inversely depended on the temperature of carbonisation. The modifications of the processes permitted obtaining materials of different textural parameters, different acid-base character of the surface and different iodine sorption capacity.     

Thermal oxidation temperature dependence of 4H-SiC MOS interface

The thermal oxidation temperature dependence of 4H-silicon carbide (SiC) is systematically investigated using X-ray photoelectron spectroscopy (XPS) and capacitance-voltage (C-V) measurements. When SiC is thermally oxidized, silicon oxycarbides (SiC_xO_y) are first grown and then silicon dioxide (SiO₂) is grown. It is identified by XPS that the SiO₂ films fall into two categories, called SiC-oxidized SiO₂ and Si-oxidized SiO₂ in this paper. The products depend on thermal oxidation temperature. The critical temperature is between 1200 and 1300 °C. The interface trap density (D_it) of the sample possessing Si-oxidized SiO₂, at thermal oxidation temperature of 1300 °C, is lower than SiC-oxidized SiO₂ at and below 1200 °C, suggesting that a decrease of the C component in SiO₂ film and SiO₂/SiC interface by higher oxidation temperature improves the metal-oxide-semiconductor (MOS) characteristics.     

Examination of the oxidation resistance of high-alloyed tool steels at elevated temperatures

In the present work the structure of two different tool steels is examined before and after oxidation up to 1000 °C in air. The materials under examination have different chromium contents. Also, the first contains vanadium (S1 tool steel) and the second tungsten (S2 tool steel) as alloying element, while the rest are common. The examination took place by thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy and X-ray diffraction. From this study it is deduced that the structure of the two steels, before oxidation, has several distinguishing differences mostly in the chromium distribution in the iron matrix. The oxidation tests revealed that S2 oxidizes at higher temperatures than S1, but finally, at 1000 °C, S2 tool steel has greater mass gain, because it oxidizes at a higher rate.     

O2 plasma oxidation effect on magnetic properties of spin valves

The use of nano-oxide to improve the performance of spin valves has been extensively studied. But most of the investigations so far have been carried out on different samples. This may make some of the conclusions drawn from the experiments inconsistent because of the fluctuation in deposition conditions and device structures. In this work, the effect of nano-oxide on the properties of spin valves has been investigated through post-growth oxidation of the same sample in oxygen plasma for different rf powers and durations. The sample investigated was a bottom spin valve with the structure Si/SiO₂/Ta/NiFe/IrMn/CoFe/Cu/CoFe/Ta. A relative increase of 20% and 12% was obtained in the giant magnetoresistance (GMR) ratio of as-deposited and annealed samples, respectively. It was found that, at a fixed rf power, there is a peak of the GMR ratio as the oxidation time increases. A higher peak value of the GMR ratio was obtained for lower rf power, although the required oxidation time is longer. This result can be well understood by considering both the enhanced specularity at the insulator/metal interface and the loss of magnetic effective thickness of the free layer by the oxidation. Magnetic parameters such as the interlayer coupling field (H₀) and the coercivity of the free layer (H_cf) were also greatly influenced by the oxidation process. When only the Ta layer was oxidized, H₀ increases very slightly, and H_cf increases with the oxidation time. However, when the CoFe free layer was oxidized, a significant increase was found for H₀, and H_cf changes to decreasing. These results can be explained based on the Néel and RKKY coupling models. Received: 25 October 2001 / Accepted: 21 December 2001 / Published online: 3 June 2002     

Comparative examination of the microstructure and high temperature oxidation performance of NiCrBSi flame sprayed and pack cementation coatings

Coatings formed from NiCrBSi powder were deposited by thermal spray and pack cementation processes on low carbon steel. The microstructure and morphology of the coatings were studied by scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). Flame sprayed coatings exhibited high porosity and were mechanically bonded to the substrate while pack cementation coatings were more compact and chemically bonded to the substrate. The microhardness and the high temperature oxidation resistance of the coated samples were evaluated by a Vickers microhardness tester and by thermogravimetric measurements (TG), respectively. Pack cementation coatings showed higher hardness and were more protective to high temperature environments than the flame sprayed coatings.     

Characterization and structure study of the anodic oxide film on Zircaloy-4 synthesized using NaOH electrolytes at room temperature

Thick crystalline zirconium oxide films were synthesized on Zircaloy-4 substrates by anodic oxidation at room temperature in NaOH solution with a stable applied voltage (300 V). The film is approximately 4.7 μm in thickness. The XPS and SEM analysis shows that the film is a three-layer structure in water, hydroxide and oxide parts. The thickness of that order is ∼0.01 μm, ∼1 μm, ∼3.7 μm, respectively. The oxide layer is composed of tetragonal and monoclinic phases with the volume ratio about 0.2. Furthermore, the thick anodic film acts as a barrier to oxygen and zirconium migrations. It effectively protects zirconium alloys against the worse corrosion. An extremely low passive current density of ∼0.018 μA/cm² and a low oxidation weight gain of ∼0.411 mg/cm² were also observed in the films.     

Effect of surface roughness on the development of protective Al2O3 on Fe-10Al (at.%) alloys containing 0-10 at.% Cr

The effect of alloy surface roughness, achieved by different degrees of surface polishing, on the development of protective alumina layer on Fe-10 at.% Al alloys containing 0, 5, and 10 at.% Cr was investigated during oxidation at 1000 °C in 0.1 MPa oxygen. For alloys that are not strong Al₂O₃ formers (Fe-10Al and Fe-5Cr-10Al), the rougher surfaces increased Fe incorporation into the overall surface layer. On the Fe-10Al, more iron oxides were formed in a uniform layer of mixed aluminum- and iron-oxides since the layer was thicker. On the Fe-5Cr-10Al, more iron-rich nodules developed on an otherwise thin Al₂O₃ surface layer. These nodules nucleated preferentially along surface scratch marks but not on alloy grain boundaries. For the strong Al₂O₃-forming Fe-10Cr-10Al alloy, protective alumina surface layers were observed regardless of the surface roughness. These results indicate that the formation of a protective Al₂O₃ layer on Fe-Cr-Al surfaces is not dictated by Al diffusion to the surface. More cold-worked surfaces caused an enhanced Fe diffusion, hence produced more Fe-rich oxides during the early stage of oxidation.     

Influence of activated carbon surface acidity on adsorption of heavy metal ions and aromatics from aqueous solution

Adsorption of toxic heavy metal ions and aromatic compounds onto activated carbons of various amount of surface C-O complexes were examined to study the optimum surface conditions for adsorption in aqueous phase. Cadmium(II) and zinc(II) were used as heavy metal ions, and phenol and nitrobenzene as aromatic compounds, respectively. Activated carbon was de-ashed followed by oxidation with nitric acid, and then it was stepwise out-gassed in helium flow up to 1273 K to gradually remove C-O complexes introduced by the oxidation. The oxidized activated carbon exhibited superior adsorption for heavy metal ions but poor performance for aromatic compounds. Both heavy metal ions and aromatics can be removed to much extent by the out-gassed activated carbon at 1273 K. Removing C-O complexes, the adsorption mechanisms would be switched from ion exchange to Cπ-cation interaction for the heavy metals adsorption, and from some kind of oxygen-aromatics interaction to π-π dispersion for the aromatics.     

Relaxed SiGe-on-insulator with high Ge fraction obtained by oxidation of SiGe/Si-on-insulator with hydrogen ions implantation

The SiGe-on-insulator (SGOI) materials were obtained by thermal oxidation of SiGe layers on SOI wafers. As a comparison, H ions were implanted into SiGe layer of some samples before oxidation. The high degree relaxed SGOI materials with high Ge fraction were fabricated by two kinds of samples, including the samples without and with H ions implantation, and relaxation degree of SiGe layers is above 93%. The different result is that implantation of H ions decreased the oxidation rate of SiGe layer and decreased the loss of Ge in SiGe layer during oxidation. The effect of implantation of H ions is discussed in the paper.     

Initial oxidation of Mn surface studied by ultraviolet photoelectron spectroscopy and metastable induced electron spectroscopy

Metastable induced electron spectroscopy (MIES) was combined to ultraviolet photoelectron spectroscopy (UPS) to study the initial steps of manganese oxidation. Oxygen exposure directly led to the formation of MnO with no intermediate states. The MnO feature saturation observed by MIES and UPS techniques showed noticeable differences and proved the formation of several oxide layers. The oxidation kinetics was studied by measuring MnO features by UPS, which depend on the surface coverage by oxygen. We observe a decrease of oxygen adsorption probability with oxygen exposure. Oxidation proceeds by oxygen dissolution into the first layers to form a three-dimension MnO. This hypothesis was confirmed by our work function measurements.     

The effect of cerium oxide argon-annealed coatings on the high temperature oxidation of a FeCrAl alloy

Ceria coatings were applied in order to improve the adherence of alumina scales developed on a model Fe–20Cr–5Al alloy during oxidation at high temperature. These coatings were performed by argon annealing of a ceria sol–gel coating at temperatures ranging between 600 and 1000 °C. The influence of these coatings on the alloy oxidation behaviour was studied at 1100 °C. In situ X-ray diffraction (XRD) was performed to characterize the coating crystallographic nature after annealing and during the oxidation process. The alumina scale morphologies were studied by means of scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS). The present work shows that the alumina scale morphology observed on cerium sol–gel coated alloy was very convoluted. On the cerium sol–gel coated alloy, argon annealing results in an increase of the oxidation rate in air, at 1100 °C. The 600 °C argon annealing temperature results in a good alumina scale adherence under thermal cycling conditions at 1100 °C.     

The influence of dew point during annealing on the power loss of electrical steel sheets

Decarburization is a necessary part of the processing of electrical steels if their carbon content is above a certain level. The process is usually carried out in a wet hydrogen–nitrogen atmosphere. Having a high dew point has a negative influence on the power loss, though. This is due to oxidation of the steel, which hinders domain wall motion near the surface. In this study, an increase of the power loss was only observed at a fairly high dew point (>20 °C). It was also only at these high dew points where a subsurface oxide layer was observed. The surfaces of samples with and without this layer were etched in steps. The magnetic properties of the etched samples corresponded well with the expected behavior based on GDOES profiles of the samples.     

Fundamental processes of aluminium corrosion studied under ultra high vacuum conditions

Surface sensitive electron spectroscopy was applied to study the fundamental processes of aluminium corrosion. We used metastable induced electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy (UPS) for the investigation of the densities of states of surface and bulk, respectively. Furthermore we applied X-ray photoelectron spectroscopy (XPS) to investigate the chemical composition of the top surface layers. All measurements were performed under ultra high vacuum conditions.Al films with thicknesses of 7 nm were investigated. Both the interaction of oxygen and water with these films leads to the formation of an aluminium-oxygen layer, which is partly composed of stoichiometric Al₂O₃. Weak heat treatment at 770 K transforms the surface layer into Al₂O₃ with a thickness of about 2 nm. Further gas offer does not lead to an increase of this thickness, neither for oxygen nor for water. Additional to the oxygen offer, water exposure leads to the formation of OH species in the top aluminium-oxygen layer to a small amount. Weak heat treatment to 770 K removes this species completely. Water exposure leads to a much faster oxide formation than oxygen exposure. We try to give a model for the fundamental corrosion processes on a molecular scale.     

MicroRaman study of the effect of oxide layer on nitriding of Ti-6Al-4V

Ti-6Al-4V samples were subjected to nitrogen ion implantation and low pressure RF plasma nitriding in a PIII equipment after chemical etching in Kroll's reagent. The samples were characterized by optical microscopy, AFM, microRaman, XRD and micro hardness measurements. From microRaman, oxides of titanium were found in the inter-granular β region whereas the oxide on the α region was extremely thin. The oxide on the β region was found to be amorphous and from intensity dependent Raman spectra, it was found to have a layered structure. The top layer was rutile and the inner layer anastase. Presence of Ti₂O₃ was also found. After PIII treatment at 600 °C, microRaman showed the presence of nitride in both the regions and the oxide was absent in the β regions. Also, from intensity dependent Raman spectra, it was found that in-take of nitrogen by β regions was higher. The oxide layer remained unaffected after plasma nitriding. Nitride presence in the α was established by microRaman. Even though Raman spectra from β regions were nearly the same as that of oxide, presence of nitrogen was indicated by the spectra. XRD studies of implanted and nitrided samples showed the prsence of TiN and Ti₂N in implanted sample and presence of Ti₂N in the nitrided sample. The β regions were found to have higher microhardness values after PIII and nitriding treatments. This is attributed to the deeper diffusion of nitrogen in these regions.     

Difference in high-temperature oxidation resistance of amorphous Zr-Si-N and W-Si-N films with a high Si content

The high-temperature oxidation resistance of amorphous Zr-Si-N and W-Si-N films with a high Si content (≥20 at.%) deposited by reactive dc magnetron sputtering at different partial pressures of nitrogen was systematically investigated by means of a symmetrical high-resolution thermogravimetry in a flowing air up to an annealing temperature of 1300 °C (a temperature limit for Si(1 0 0) substrate). Additional analyses including X-ray diffraction (XRD), light optical microscopy (LOM), scanning electron microscopy (SEM), atomic force microscopy (AFM), and microhardness measurement were carried out as well. The obtained results showed (i) an excellent high-temperature oxidation resistance of the Zr-Si-N films up to 1300 °C, (ii) a considerably lower oxidation resistance of the W-Si-N films. The W-Si-N films are completely oxidized at 800 °C with a subsequent volatilization of unstable WO_x oxides. On the other hand, the Zr-Si-N films are oxidized only very slightly on the surface, where a stable oxide barrier layer preventing further inward oxygen diffusion is formed. The thickness of the oxide layer is only about of 3% of the total film thickness. The phase composition, thermal stability of individual phases and amorphous structure were found to be key factors to achieve a high oxidation resistance.     

Oxidation of GaN{0001}-11 surfaces at room temperature

The interaction of unexcited oxygen molecules with clean GaN{0001}-11 surfaces was investigated using X-ray photoemission spectroscopy (XPS), Auger electron spectroscopy (AES), and low-energy electron diffraction (LEED). Clean surfaces were prepared by a HF dip followed either by desorption of Ga films deposited at room temperature or by nitrogen-ion bombardment and annealing. During exposures in the range from 0.3 up to 10¹⁵ L-O₂ any excitations of the oxygen were avoided. Oxygen coverages determined from the XPS and the AES data differ by a factor of two. The larger XPS-derived coverages are considered to be more reliable since the AES signals decayed during data recording. The oxygen uptake takes place in two consecutive stages. The first one is identified as dissociative chemisorption and the second one is tentatively attributed to field-assisted diffusion by the Mott-Cabrera mechanism. The dissociative chemisorption is characterized by an initial sticking coefficient of and a saturation coverage of monolayers that is reached after exposures of 10³ L-O₂. The second mechanism sets in at exposures to 10⁸ L-O₂ but reaches no saturation even with the largest doses applied. Received 4 September 1998 and Received in final form 6 November 1998     

Morphology and composition on Al surface irradiated by femtosecond laser pulses

We study the surface chemicals and structures of aluminum plates irradiated by scanning femtosecond laser pulses in air for a wide range of laser fluence from 0.38 to 33.6 J/cm². X-ray photoelectron spectroscopy and X-ray diffraction analyses indicate clearly that crystalline anorthic Al(OH)₃ is formed under femtosecond laser pulse irradiation. Besides aluminum hydroxide, crystalline Al₂O₃ is also found in the samples irradiated at high laser fluence. Field emission scanning electron microscopy demonstrates that the surfaces of the samples irradiated with low laser fluence are colloidal-like and that nanoparticles with a few nanometers in size are embedded in glue-like substances. For high laser fluence irradiated samples, the surfaces are highly porous and covered by nanoparticles with uniform size of less than 20 nm.     

The high quality ZnO growth on c-Al2O3 substrate with Cr2O3 buffer layer using plasma-assisted molecular beam epitaxy

High quality epitaxial ZnO films were grown on c-Al₂O₃ substrates with Cr₂O₃ buffer layer by plasma-assisted molecular beam epitaxy (P-MBE). The hexagonal crystalline Cr₂O₃ layer was formed by oxidation of the Cr-metal layer deposited on the c-Al₂O₃ substrate using oxygen plasma. The epitaxial relationship was determined to be ZnO//Cr₂O₃//Cr//Al₂O₃ and ZnO//Cr₂O₃//[0 0 1]Cr//Al₂O_3. The Cr₂O₃ buffer layer was very effective in improving the surface morphology and crystal quality of the ZnO films. The photoluminescence spectrum showed the strong near band-edge emissions with the weak deep-level emission, which implies high optical quality of the ZnO films grown on the Cr₂O₃ buffer.