Stresses in thermally grown SiO2 films on silicon have traditionally been determined by substrate curvature measurements. This technique is useful for studying stresses in thin films, but it cannot be used to investigate stresses generated in the substrate during film growth. In the present work, we used microelectromechanical systems-based microstrain gauge devices fabricated from single-crystal and polycrystalline silicon (henceforth silicon and polysilicon, respectively) to measure oxidation-induced stresses in both dry and wet oxidizing ambients. Our microstrain gauges had thicknesses on the micrometer scale, and were themselves used as the substrates to be oxidized. Stresses could be detected in both the SiO2 scales and the silicon and polysilicon substrates. In the SiO2 scales, the stresses were compressive and exhibited viscoelastic relaxation. The as-grown compressive stresses were greater for wet oxidation than they were for dry oxidation, and greater in scales grown on polysilicon than they were in scales grown on silicon. The viscosity of thermally grown SiO2 was the same whether scales formed by wet or dry oxidation, and the same for oxide scales on silicon and polysilicon. Significant compressive stresses were also generated in polysilicon during oxidation, but not in silicon.

In this research, the influences of the oxygen impurity contained in the commercially available nitrogen gas on the reactions of chromium pellets with nitrogen were investigated in the temperature range 600–1350 °C. A small amount of oxygen competed with the majority N2 to react with chromium in the annealing process. Analyzing the in situ oxygen partial pressure changes during annealing proved that the dissolution of oxygen in Cr and/or resultant CrxN (CrN or Cr2N) was exothermic and the solubility decreased with increasing temperature. It was found that the oxygen partial pressure decreased drastically to about 10−22 atm when specimens were annealed at 600 °C compared to a mere 10−5 atm for a blank test, while its value increased with temperature. The oxidation involved simultaneous dissolution of oxygen in specimens and formation of oxide scale. Moreover, comparing the aforementioned results with those obtained from additional annealing experiments preformed in argon gas showed that the formation of Cr2O3 might stem mainly from oxidation of the resultant nitrides instead of the metallic chromium.

The oxidation kinetics and the effects of alloying on the oxidation behaviors of copper-based bulk metallic glasses were studied. The oxidation kinetics, oxide compositions, and structures were investigated by thermogravimetric analysis (TGA), x-ray diffraction, x-ray photoelectron spectroscopy (XPS), and scanning electron microscopy. Both the TGA results and the XPS depth profile measurements showed that the oxidation resistance of Cu60Zr30Ti10 bulk metallic glass was improved by adding Hf, but it deteriorated when it was alloyed with Y. The oxide phases were found to be ZrO2, Cu2O, and CuO in samples heated at 573 K while an additional metallic Cu phase was detected in the ones heated at 773 K. A porous oxide structure was observed in the (Cu0.6Zr0.3Ti0.1)98Y2 metallic glass oxidized at 673 K, and the poor oxidation resistance of the alloy is attributed to the porous structure.

The initial oxidation behaviors of Cu–50 at.% Au (001) single-crystal thin film were studied by in situ ultra-high-vacuum transmission electron microscopy to model nano-oxidation of alloys with one oxidizing component and one inert component. The oxidation behaviors such as incubation time, oxide nucleation rate, oxide growth kinetics as well as nucleation activation energy were greatly changed by the addition of nonoxidizing Au. The reasons for these changes, such as Au segregation to the top surface, a decrease in Cu activity, and reduced lattice mismatch due to the addition of Au, were discussed, and a qualitative analysis of nucleation energetics was given.

The initial oxidation stages of Cu(100), (110), and (111) surfaces have been investigated by using in situ ultra-high-vacuum transmission electron microscopy (TEM) techniques to visualize the nucleation and growth of oxide islands. The kinetic data on the nucleation and growth of oxide islands shows a highly enhanced initial oxidation rate on the Cu(110) surface as compared with Cu(100), and it is found that the dominant mechanism for the nucleation and growth is oxygen surface diffusion in the oxidation of Cu(100) and (110). The oxidation of Cu(111) shows a dramatically different behavior from that of the other two orientations, and the in situ TEM observation reveals that the initial stages of Cu(111) oxidation are dominated by the nucleation of oxide islands at temperatures lower than 550 °C, and are dominated by two-dimensional oxide growth at temperatures higher than 550 °C. This dependence of the oxidation behavior on the crystal orientation and temperature is attributed to the structures of the oxygen-chemisorbed layer, oxygen surface diffusion, surface energy, and the interfacial strain energy.

The world of nanomaterials has become the real world for most applications in the area of nanotechnology. As postsynthesis handling of materials at the nanoscale level is impractical, nanomaterials must be synthesized directly as part of a device or circuit. The demands of nanotechnology have led to modifications in the design of transmission electron microscopes (TEMs) that enable in situ synthesis and characterization simultaneously. The environmental TEM (ETEM) is one such modified instrument that has often been used to follow gas–solid and/or liquid–solid interactions at elevated temperatures. Although the history and development of the ETEM, also called the controlled atmosphere or environmental cell TEM, is as old as transmission electron microscopy itself, developments in the design of medium-voltage TEMs have succeeded in bringing resolutions down to the subnanometer level. A modern ETEM equipped with a field-emission gun, energy filter or electron energy-loss spectrometer, scanning transmission electron microscopy coils, and bright-field and dark-field detectors can be a versatile tool for understanding chemical processes at the nanometer level. This article reviews the design and operations of a dedicated ETEM. Its applications range from the in situ characterization of reaction steps, such as oxidation-reduction and hydroxylation, to the in situ synthesis of nanomaterials, such as quantum dots and carbon nanotubes. Some examples of the current and the future applications for the synthesis and characterization of nanomaterials are also discussed.

The oxidation kinetics of Cu60Zr30Ti10 bulk metallic glass and its crystalline counterpart were studied in oxygen environment over the temperature range of 573–773 K. The oxidation kinetics, measured with thermogravimetric analysis, of the metallic glass follows a linear rate law between 573 and 653 K and a parabolic rate law between 673 and 733 K. It was also found that the oxidation activation energy of metallic glass is lower than that of its crystalline counterpart. The x-ray diffraction pattern showed that the oxide layer is composed of Cu2O, CuO, ZrO2, and metallic Cu. Cu enrichment on the topmost oxide layer of the metallic glass oxidized at 573 K was revealed by x-ray photoelectron spectroscopy while there was a decrease in Cu content in the innermost oxide layer. The oxide surface morphologies observed from scanning electron microscopy showed that ZrO2 granules formed at low temperatures while whiskerlike copper oxides formed at higher temperatures.

Ultra-refractory ceramic composites of composition ZrB2 + (5 to 20) vol% MoSi2were produced by pressureless sintering at 1830 °C under argon atmosphere.Sintering cycles and microstructural analysis point out that at least 20 vol% molybdenum disilicide is necessary for obtaining a dense material. Thereafter, the composite 80 vol% ZrB2 + 20 vol% MoSi2 was used to test the thermal stabilityunder oxidizing environment. Oxidation tests were carried out in flowing syntheticair in a thermogravimetric analyzer from 700 to 1400 °C with exposure time of30 h. In the low-temperature range (700–1000 °C), the oxidation of the composite resembles that of monolithic ZrB2 ceramics, for temperatures >1200 °C the silica resulting from oxidation of molybdenum disilicide seals the sample surface, preventing zirconium diboride from fast degradation.

Adhesion of thin films of epitaxial oxides to nickel-based metallic substrates is important for the successful development of high-temperature superconductor coated conductors. Detachment of epitaxial oxide buffer layers at the oxide/metal interface during either oxide growth or subsequent processing renders the conductor useless. In this study, thermal desorption spectroscopy (TDS) has been used to identify and understand one of the causes of buffer layer detachment, oxidation of carbon at the oxide–metal interface to form carbon monoxide. Results of TDS indicate that on the surface of a bare nickel-based alloy substrate, the rate of carbon oxidation depends on both the supply of carbon from the substrate and the supply of oxygen from the vapor. Sulfur at the surface of the alloy substrate reduces the rate of carbon oxidation. The effectiveness of various treatments of the bare substrate to eliminate CO formation and epitaxial oxide detachment has been demonstrated. TDS provides both a means to evaluate the kinetics of the oxidation reaction and a tool to assess the need and effectiveness of a substrate oxidation treatment.

In this work, the microstructure and oxidation resistance of pure Cu, Cu(0.2 at.% Zr) and Cu(2.5 at.% Zr) alloy films deposited on SiO2/Si by sputtering were explored. Upon annealing, the Zr additives diffused to the free surface and reacted with the residual oxygen in the vacuum system. An additional ZrO2 layer formed and covered the Cu(2.5 at.% Zr) film surface after annealing at 700 °C for 30 min. Simultaneously, of the three films, the Cu(2.5 at.% Zr) film exhibited the highest degree of Cu(111) preferred orientation and the lowest degree of void growth upon annealing. Additionally, the Cu(2.5 at.% Zr) film pre-annealed at 700 °C showed a superior oxidation resistance when annealed at 200 °C in air for 15 min. Microstructure and oxidation resistance of Cu(Zr) alloy films were clearly affected by the ZrO2 layer formed via the segregation of Zr additives, and the connection is discussed.

The effects of heat treatments on strength and electrical conductivity after 100 h in air up to 1500 °C were evaluated on hot-pressed Si3N4–35 vol% MoSi2 composite. The long-term oxidation involves microstructural changes at the material surface and subsurface, such as the formation of oxide scales and of a multilayered microstructure. At T ⩾ 1200 °C, a glassy silicate phase is formed, which embeds cristobalite grains and highly textured Y2Si2O7 crystals. At the same time, MoSi2, assisted by oxygen, reacts with Si3N4 forming Mo5Si3, Si2N2O, and SiO2. The decrease of the room temperature flexural strength reached about 25% in the samples exposed at 1000 °C for 100 h, compared to the as-produced materials. On the contrary, after treatments at higher temperatures, the strength decrease is lower at 1500 °C, the residual strength is 836 ± 62 MPa with a strength decrease of about 8%. The surface oxide scale is an insulator and, consequently, the electrical resistivity of the composite rises from 10-3 to 107–109 Ωcm.