In situ SEM study of the high-temperature oxidation of an Fe-Mn-Al-Si alloy

The oxidation behavior of a low-carbon Fe-30Mn-10Al-Si alloy was studied at 1100 and 1150C in a hot-stage environmental scanning electron microscope. The oxidation experiments were performed in pure oxygen at a partial pressure of 10 ^–4 atm. Under these conditions, nodule nuclei of manganese and iron oxide appeared after a few minutes of oxidation, indicating the local destruction of the protective Al₂O₃ scale. The nodules grew and coalesced and finally overgrew the entire specimen surface. The composition of the nodules changed during the growth process; the amount of iron decreased, and the manganese content increased to about 95 wt%. All the nodules were located in symmetrically shaped pits which intrude into the metal.     

Influence of ceria coatings on growth stresses developed in wüstite scales formed on pure iron at 800°C

In situ XRD stress determinations have been performed during oxidation of pure iron (p(O₂=2 × 10^–3 Pa,T=800°C)). The compressive stress, initially present in the substrate due to surface preparation, is completely released at 400°C. Under the test conditions, the in situ compressive-stress level determined in the FeO scale during oxidation is not strongly dependent upon the presence of a ceria coating. On blank and coated specimens, the compressive stress varies from –400 ± 80 MPa to –150 ± 100 MPa during 30 hr oxidation. The decrease is quicker at the beginning of the test performed on blank specimens. Epitaxial relationships between the wüstite scale and iron (under low-pressure starting conditions) caused thein situ compressive stress in the oxide scale to be two times greater compared to the usual test conditions. This indicates that epitaxial relationships can be a source of stress in an oxide scale that ceria coatings may lower compressive stresses.     

In situ oxidation studies on (001) copper-nickel alloy thin films

The (001)-oriented, single crystalline thin films of Cu-3% Ni, Cu-4.6% Ni, and Cu-50% Ni alloy were prepared by vapor deposition onto (001) NaCl substrates. The films were subsequently annealed at around 1100°K and oxidized at 725°K at an oxygen partial pressure of 5×10^–1 N · m^–2 (5× 10^–6 atm). High-resolution transmission electron microscopy was employed to observe the changes in situ. For all the alloy concentrations Cu₂O and NiO were observed to nucleate and grow independently; no mixed oxides were noted. The shape and growth rates of Cu₂O nuclei were similar to those found in previous work on pure copper films. For low-nickel alloy concentrations the NiO nuclei were larger and the number density of NiO was less when compared to the oxidation of pure nickel films. For the Cu-50% Ni films the shape and growth rates of NiO were identical to those for the oxidation of pure nickel films. Low nickel concentrations exhibited a reduced induction period for Cu₂O when compared to pure copper films. Cu-50%Ni films showed surface precipitation and growth of NiO first, followed by Cu₂O in a typical through -thickness growth after a prolonged induction period. The results are consistent with the previously established oxidation mechanisms of pure copper and pure nickel films.This work was performed at the Ames Research Center and funded by NASA Grants NCA2-OP390-403 and NSG-2025.     

Oxide removal and desorption of oxygen from partly oxidized thin films of copper at low pressures

Partly oxidized copper films were annealed in a controlled vacuum of 10^–7 Pa at a temperature of 450° C. The changes discussed below were observed in situ with a specially designed high-resolution transmission electron microscope. The thin, (100)-oriented, single-crystal films of copper had been oxidized immediately prior to the annealing studies at the same temperature and at an oxygen partial pressure of 7×10 ^–1 Pa, until the desired fraction of the copper film was converted to oxide. It was observed that the oxide disappeared during annealing as long as some copper was left unoxidized. The disappearance of the oxide is explained as being due to dissociation of the oxide at the oxide-metal interface followed by diffusion of oxygen into the metal and desorption of oxygen from the surface of the unoxidized copper. The rate of disappearance of the oxide was found to be proportional to the surface area of unoxidized copper, i.e., the desorption was found to be the rate — limiting step. In the case of heavily oxidized films (>50%), holes were observed to develop in the oxide near the oxide-metal interface after an annealing period of 2–3 hr. Upon resumption of the oxidation, these holes first disappeared, and the normal oxidation behavior was then resumed. The formation of holes may be explained by vacancy clustering. When completely oxidized films were annealed, recrystallization of the oxide was observed.This work was performed at the Ames Research Center and funded by NASA Grants Nos. NCA2-OP390-403 and NSG-2025.     

In Situ observation of the effect of temperature on Cu2O scale morphology

The effect of temperature on copper oxide scale morphology was studied during in situ oxidation of OFHC copper in a hot-stage environmental scanning electron microscope (HSESEM). Cuprous oxide scales grown at low temperature [0.2T_m(Cu₂O)] and intermediate temperatures 0.6–0.7T_m(Cu₂O)] were found to be crystallographically oriented. At intermediate temperatures, scales exhibited nonplanar features such as ridges and growth pyramids. At high temperatures [T> 0.8T_m(Cu₂O)], scales had planar morphologies and a few dislocation growth pits. Downquenching and upquenching of the Cu₂O scales from steady-state oxidation temperatures induced morphological changes such as cavity formation and surface reconstruction.     

The influence of reactive-element coatings on the high-temperature oxidation of pure-Cr and high-Cr-content alloys

The influence of various reactive-element (RE) oxide coatings (Y₂O₃, CeO₂, La₂O₃, CaO, HfO₂, and Sc₂O₃) on the oxidation behavior of pure Cr, Fe–26Cr, Fe–16Cr and Ni–25Cr at 900°C in O₂ at 5×10^–3 torr has been investigated using the¹⁸O/SIMS technique. Polished samples were reactively sputtercoated with 4 nm of the RE oxide and oxidized sequentially first in¹⁶O₂ and then in¹⁸O₂. The effectiveness of each RE on the extent of oxidation-rate reduction varied with the element used. Y₂O₃ and CeO₂ coatings were found to be the most beneficial, whereas Sc₂O₃ proved to be ineffective, for example, for the oxidation of Cr. SIMS sputter profiles showed that the maximum in the RE profile moved away from the substrate-oxide interface during the early stages of oxidation. After a certain time the RE maximum remained fixed in position with respect to this interface, its final relative position being dependent on the particular RE. The position of the RE maximum within the oxide layer also varied with the substrate composition. For all coatings¹⁸O was found to have diffused through the oxide to the substrate-oxide interface during oxidation, the amount of oxide at this interface increasing with increasing time. The SIMS data confirm that for coated substrates there has been a change in oxidegrowth mechanism to predominantly anion diffusion. The RE most probably concentrates at the oxide grain boundaries, generally as the binary oxide (RE) CrO₃. Cr³⁺ diffusion is impeded, while oxygen diffusion remains unaffected.     

Kinetics and mechanism of high-temperature oxidation of dilute cobalt-chromium alloys

Kinetics of oxidation of Co-Cr alloys containing 0.4%–15% Cr was studied as a function of temperature (1273–1573 K) and oxygen pressure (4 × 10²–10⁵Pa). The oxidation process was found to be approximately parabolic and faster than that for pure cobalt. The scales are double-layered and consist of a compact outer CoO layer and a porous inner layer containing CoO slightly doped by chromium and spinel CoCr₂O₄. The oxidation mechanism was investigated by means of platinum markers and the¹⁸O isotope. The scale on the alloys containing less than 1% Cr grows exclusively by outward diffusion of cobalt, while that on the alloys containing more chromium—with a significant contribution of inward oxygen transport from atmosphere. This transport is not a lattice diffusion, but proceeds presumably through microfissures resulting from the secondary process of perforating dissociation of the outer scale layer.     

The influence of grain-boundary segregation of Y in Cr2O3 on the oxidation of Cr metal

The oxidation behavior at 900°C of pure Cr and Cr implanted with 2×10¹⁶ Y ions/cm² was studied. The kinetics of oxidation were measured thermogravimetrically and manometrically. The mechanisms of oxide growth were studied using¹⁸O-tracer oxidation experiments, and the composition and microstructure of the oxide scales were characterized by TEM and STEM. Segregation of Y cations at Cr₂O₃ grain boundaries was found to be the critical factor governing changes in the oxidation behavior of Cr upon the addition of Y. In the absence of Y, pure Cr oxidized by the outward diffusion of cations via grain boundaries in the Cr₂O₃ scale. When Y was present at high concentration in the scale, as when Cr implanted with 2×10¹⁰ Y ions/cm² was oxidized, anion diffusion predominated. It is concluded that strain-induced segregation of Y at grain boundaries in the oxide reduced the cation flux along the grain boundaries. The rate of oxidation was reduced because the grain-boundary diffusivity of cations became lower than the grain-boundary diffusivity of the anions, which then controlled the rate of oxidation. Changes in the relative rates of Cr³⁺ and O^2– transport, as well as a solute-drag effect exerted by Y on the oxide grain boundaries, resulted in changes in the microstructure of the oxide.     

The Oxidation of TiB2 Ceramics Containing Cr and Fe

The oxidation behavior of TiB₂, TiB₂–0.5 wt.% Cr–0.5 wt.% Fe and TiB₂–1 wt.% Cr–1 wt.% Fe was studied at 800, 900, and 1000°C in static air. These ceramics oxidized rather rapidly and formed thick oxide scales. The oxidation rates of TiB₂-base ceramics were comparable to TiO₂ formation on pure titanium. The scale formed on TiB₂ consisted of TiO₂ and B₂O₃. For TiB–Cr–Fe ceramics, a small amount of Cr- and Fe-oxides was additionally formed. B₂O₃ formed during oxidation tended to evaporate because of its high vapor pressure, making oxide scales porous and fragile. The oxidation of the TiB₂-base ceramics appeared to be governed by the inward transport of oxygen via the highly porous oxide scale. The oxidation resistance of TiB₂–Cr–Fe ceramics was similar to or better than that of TiB₂.     

TEM Study of the Internal Oxidation of an Fe–Mn–Al–C Alloy After Hot Corrosion

The internal oxides formed in Fe–31.1Mn–9.07Al–0.89C at 750–850°C in air with 2 mg/cm² NaCl deposits initially were investigated by means of transmission electron microscopy (TEM). The results showed that the volatile species generated by hot corrosion accelerated internal oxidation in the internal voids. The alloys suffered severe subscale attack at 750 and 800°C because a protective alumina scale was not formed. The morphology of attacked subscale can be divided into three layers. The interconnecting voids in the outer subscale are finer and denser than those in the inner subscale. The products inside the voids of the outer subscale are metal oxides, while the oxides inside the voids of the inner subscale are filled with fine Fe₃O₄ particles. However, due to the formation of an aluminum-rich oxide scale at 850°C, only a small amount of internal oxidation was generated in the subscale, which provided the best corrosion resistance in this study.     

Oxygen Transport during the High Temperature Oxidation of Pure Nickel

The high temperature oxidation of nickel has been investigated in air under atmospheric pressure in the temperature range 600–900°C. The oxidation kinetic curves deviate from the parabolic law for temperatures over 800°C. The observation of scale morphologies and the use of two stage oxidation experiments under ¹⁶O₂/¹⁸O₂ atmospheres showed that oxygen transport through the NiO scale had to be taken into consideration during the oxidation process. Despite the main outward diffusion of Ni species through the oxide scale, the inward oxygen diffusion at lower temperatures (<800°C) or the oxygen transport, probably as molecular species, via pores or micro-cracks were found to play a major role in the formation of duplex oxide scales, made of small equiaxed oxide grains at the metal/oxide interface overgrown by larger columnar grains at the gas/oxide interface. Oxygen diffusion coefficients into thermally grown NiO scales were determined and compared to the values of Ni diffusion coefficients from the literature.     

An analysis of the internal oxidation of binary M-Nb alloys under low oxygen pressures at 600–800°C

The corrosion of M–Nb alloys based on iron, cobalt, and nickel and containing 15 and 30 wt% Nb has been studied at 600–800°C under low oxygen pressures (10^–24 atm at 600°C and 10^–20 atm at 700–800°C). Except for the Co–Nb and Ni–Nb alloys corroded at 800°C, which formed external scales of niobium oxides, corrosion under low O₂ pressures produced an internal oxidation of niobium. This attack was much faster than expected on the basis of the classical theory. Furthermore, the distribution of the internal oxide in the alloys containing two metal phases was very close to that of the Nb-rich phase in the original alloys. These kinetic, microstructural, and thermodynamic aspects are examined by taking into account the effects of the limited solubility of niobium in the various base metals and of the two-phase nature of the alloys.     

In situ observation of whiskers,pyramids and pits during the high-temperature oxidation of metals

A hot-stage, environmental scanning electron microscope has been used to observe the in situ development of oxide whiskers, pyramids, and pits in the oxidation of copper and nickel at elevated temperatures. The effects of oxidation temperature, metal deformation, and the presence of water vapor on these irregular oxidation features were studied. In each case, the feature results from the presence of a central screw dislocation which provides ledges for the extension of the oxide lattice, but the specific geometries are decided by factors such as surface diffusion along the dislocation core, the rate of the molecular dissociation step, and the balance of surface energy and dislocation line tension forces.     

Hot-stage scanning electron microscope for high-temperaturein-situ oxidation studies

The design of a hot stage for a Cambridge S 4 scanning electron microscope (SEM) is described. Provision is made for the entry of noncondensible reactive gases to the specimen chamber through a leak tube connected to a microvalve. Preliminary oxidation studies on copper at 850°C and = 3 × 10^–4 have shown exceptional promise for the continuous observation of the scalegas interface at magnifications of up to 20,000x. Growth strains resulted in fractures at the grain boundaries of the oxide scale. Growth and random nucleation of oxides are all important features which have been observed here, and clearly show the usefulness of the modified stage of the SEM for future studies of oxidation of metals and alloys.     

The corrosion behavior of Fe-Al alloys in H2/H2S/H2O atmospheres at 700–900°C

The corrosion behavior of five Fe-Al binary alloys containing up to 40 at. % Al was studied over the temperature range of 700–900°C in a H₂/H₂S/H₂O mixture with varying sulfur partial pressures of 10^–7–10^–5 atm. and oxygen partial pressures of 10^–24–10^–2° atm. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants decreased with increasing Al content. The scales formed on Fe-5 and –10 at.% Al were duplex, consisting of an outer layer of iron sulfide (FeS or Fe_1–xS) and an inner complex scale of FeAl₂S₄ and FeS. Alloys having intermediate Al contents (Fe-18 and –28 at.% Al) formed scales that consisted of mostly iron sulfide and Al₂O₃ as well as minor a amount of FeAl₂S₄. The amount of Al₂O₃ increased with increasing Al content. The Fe 40 at.% Al formed only Al₂O₃ at 700°C, while most Al₂O₃ and some FeS were detected at T800°C. The formation of Al₂O₃ was responsible for the reduction of the corrosion rates.     

Roles of humidity and heat treatment temperatures on YBa2Cu3O7-x coated conductors by trifluoroacetic acid-metal organic deposition process

YBa₂Cu₃O_7−x(YBCO) films were fabricated on an LAO substrate using the trifluoroacetic acid-metal organic deposition (TFA-MOD) method and the effects of the humidity and heat treatment temperatures on the microstructure, degree of texture and critical properties of the films were evaluated. In order to understand the combined effects of the humidity and the calcining and firing temperatures on critical properties, heat-treatment was performed at various temperatures with the other processing variables fixed. The films were calcined at 400–430 and fired at 750–800 °C in a 0–12.1% humidified Ar-O₂ atmosphere. The texture was determined by pole-figure analysis. The amount of the BaF₂ phase was effectively reduced and a sharp and strong biaxial texture was formed under a humidified atmosphere, which led to increased critical properties. In addition, the microstructure varied significantly with firing temperature but changed little with calcining temperature. The highest I_C of 40 A/cm-width, which corresponds to J_C value of 1.8 MA/cm², was obtained for the films fired at 775 (in 12.1% humidity) after calcining at 400–430 °C. It is likely that °C the highest I_C value is due to the formation of a more pure YBCO phase, c-axis grains, and a denser microstructure.     

Polymer-induced generation and characterization of electrophoretic properties of hollow TiOX nanospheres for electronic paper

Hollow TiO_X nanospheres have been successfully prepared using hollow core–double shell latex particles (poly(styrene-co-methyl methacrylate-co-butyl acrylate-co-methacrylic acid) (abbreviated in poly(St-co-MMA-co-BA-co-MAA)) as template, which involves the deposition of inorganic coating on the surface of hollow core–shell latex particles and subsequent removal of the latex by calcinations in air or ammonia gas. Ti(OBu)₄ was used as precursor for the preparation of hollow TiO_X nanospheres. TEM of white hollow core–double shell polymers particles with an aperture of approximately 225 nm displays the perfect characteristic hollow nanospheres structure of primary core–double shell particles. The formation of TiO_X was confirmed by XRD analysis and hollow structure of the particles was revealed by transmission electron microscopy (TEM). When the calcined temperature was at 800 °C, hollow TiO₂ nanospheres were arranged regularly with the diameter range of 130–170 nm. The electrophoretic properties were characterized by JS94J micro-electrophoresis apparatus. The electrophoretic mobility of white TiO₂ and black TiO hollow spheres in tetrachloroethylene were 1.09 × 10⁻⁵ and 3.12 × 10⁻⁵ cm²/V s, and the zeta potentials were 7.10 and 20.24 mV, respectively. The results show that white TiO₂ particles and black TiO hollow nanoparticles are suitable as electrophoretic particles and possess the application potential in the future electrophoretic display.     

High-Temperature Oxidation Behavior of Ti2AlC in Air

The isothermal oxidation behavior of bulk Ti₂AlC in air has been investigated in temperature range 1000–1300°C for exposure time up to 20 hr by TGA, XRD, and SEM/EDS. The results demonstrated that Ti₂AlC had excellent oxidation resistance. The oxidation of Ti₂AlC obeyed a cubic law with cubic rate constants, k_c, increasing from 2.38×10^-12 to 2.13×10^-10 kg³/m⁶/sec as the temperature increased from 1000 to 1300°C. As revealed by X-ray diffraction (XRD) and SEM/EDS results, scales consisting of a continuous inner -Al₂O₃ layer and a discontinuous outer TiO₂ (rutile) layer formed on the Ti₂AlC substrate. A possible mechanism for the selective oxidation of Al to form protective alumina is proposed in comparison with the oxidation of Ti–Al alloys. In addition, the scales had good adhesion to the Ti₂AlC substrate during thermal cycling.     

Oxidation Behavior of a Ti3Al–Nb Alloy with Surface Thin Oxide Films

Thin films of aluminum, cerium, and yttrium oxides were applied onto the surfaces of Ti₃Al–11Nb samples using an electrodeposition technique. The oxidation behaviors of the Ti₃Al–Nb alloy, with and without these surface-applied films, were studied in air at 800–1000°C. The results showed that the oxidation rate of the alloy can be reduced by Ce oxide and Y oxide films, and the greatest improvement comes from oxidation of the Y oxide-coated specimens at 800°C. With increasing oxidation temperature, the difference between the Co-oxide and Y-oxide films becomes smaller. The results also indicated that the Ce-oxide and Y-oxide films can significantly improve the oxide scale-spallation resistance. On the other hand, Al-oxide films result in detrimental effects on the oxidation and scale-spallation resistance of the Ti₃Al–Nb alloy. Based on the experimental results, the effects of the different surface films on the oxidation mechanism are discussed.     

The Inhibitive Effect of Traces of SO2 on the Oxidation of Iron

The oxidation of Fe was investigated at 500–700°C in the presence of O₂ with 0–1000 ppm SO₂. The exposures were carried out in a thermobalance and lasted for 24 h. The oxidized samples were investigated by grazing-angle XRD, SEM/EDX, GDOES and XPS. The rate of oxidation of pure iron is slowed down by traces of O₂ in O₂ below 600°C while SO₂ has no effect on oxidation rate at higher temperatures. Exposure to SO₂<600°C resulted in the formation of small amounts of sulfate at the gas/oxide interface. In addition, sulfur, probably sulfide, accumulated at the metal/oxide interface. The influence of SO₂ on oxidation rate is attributed to surface sulfate. The sulfur distribution in the scale is rationalized in terms of the thermodynamic stability of compounds in the Fe–O–S system. Exposure to SO₂ caused the formation of hematite whiskers.