MC(Mid-Century)催化氧化过程的研究进展

介绍了MC催化氧化过程规律；从催化荆体系的改进、新型溶剂体系的开发、反应器构型和配套设施的改进、富氧氧化技术的开发等方面综述了近年来MC技术的发展；探讨了MC液相催化氧化技术应用范围的拓展以及MC液相催化氧化过程的发展方向。     

Oxidation and Fracture Strength of High-Purity Reaction-Bonded Silicon Nitride

Reaction-bonded Si₃N₄ (RBSN) made from high-purity Si powder is unusually resistant to degradation caused by exposures to air for up to 50 h at temperatures up to 1400°C. The weight gain during oxidation of this SiH₄-originating RBSN is approximately 10 times less than conventional RBSN. Contrary to normally observed strength degradations, room-temperature strengths of this high-purity, oxidized RBSN (avg = 435 MPa, max. = 668 MPa) remained at their unusually high, as-processed levels after 1000° and 1400°C oxidizing exposures. Fracture toughness values were unaffected by oxidation ( K _IC= 2.3 to 2.4 MPa · m^1/2). This superior oxidation resistance results from the high purity and the small diameter pore channels (0.01 to 0.06 μm) achieved in this SiH₄-originating RBSN.     

On the oxidation kinetics and mechanisms of various SiC-coated carbon-carbon composites

SiC coatings on the surface of C-C were produced by either silicone resin impregnation/ pyrolysis or reaction sintering. Cycles of resin impregnation/pyrolysis produced an SiC coating, on the walls of fine open pores, which was effective in reducing the oxidation rate of C-C and in shifting the transition temperature to a higher value. Unless it is pre-coated with a pyrocarbon layer before sintering, plain reaction sintered SiC has oxidation behaviors similar to those of the above-mentioned SiC. The dense pyrocarbon film deposition on the surface of C-C could form a better SiC film than others. The carbon film homogenized the surface of C-C and a dense SiC film was established. The oxidation of the coated C-C can be modelled by a set of “oxidation resistors” in series and/or in parallel, with each resistor corresponding to an oxidation element. The controlling mechanism can be resolved from the activation energy. A combined resistant layer, consisting of resin impregnation, pyrocarbon film and reaction sintering SiC, showed the best oxidation resistance of any single-layer coated C-C composite.     

The mechanism of CO oxidation over Cu(110): Effect of CO gas energy

The effect of the temperature of gas phase CO upon the kinetics of the oxygen titration reaction: CO_g +O_a CO_2,g, has been studied. It is found that the reaction's rate is independant of CO gas temperature between 300 and 623 K. The activation energy (6.5 kcal/mole), dependence upon CO pressure (first-order), and independence upon oxygen coverage for 0.1 _o 0.4 are all independant of the CO gas phase temperature. This result rules out any Eley-Rideal type mechanism whereby CO reacts directly from the gas phase with an oxygen adatom without first being accommodated to the surface temperature in an absorbed state. The result is instead interpretable in terms of a Langmuir-Hinshelwood mechanism.Camille and Henry Dreyfus Foundation Teacher-Scholar Fellowship.     

Intergranular oxidation of silicon in 20Cr-25Ni niobium-stabilized stainless steel at 1140–1230 K

The kinetics of intergranular oxidation of silicon in a 20Cr-25Ni Nb-stabilized stainless steel are reported, at temperatures in the range 1140–1230 K, in CO₂ at 40 bar pressure. The depth of attack increased parabolically with respect to time, with an activation energy of 335±30 kJ/mol. The mechanism of growth is discussed in terms of classical internal-oxidation theories, and an alternative explanation based on an available-space theory is developed. The internal oxidation rates in a number of different alloys are compared with diffusivities of metals in the base alloy. It is proposed that intergranular oxidation in the 20–25 Nb steel is controlled by the rate of outward diffusion of iron or chromium in the alloy.     

Evolution of insoluble eutectic Si particles in anodic oxidation films during adipic-sulfuric acid anodizing processes of ZL114A aluminum alloys

The effects of insoluble eutectic Si particles on the growth of anodic oxide films on ZL114A aluminum alloy substrates were in-vestigated by optical microscopy (OM) and scanning electron microscopy (SE...     

Oxidation behavior and mechanism of aluminum oxynitride (AlON) at elevated temperatures

The oxidation behavior and mechanism of aluminum oxynitride (AlON) powder exposed to air at elevated temperatures between 800°C and 1300°C was investigated by X-ray diffractometry (XRD), scanning electron microscope (SEM), electron spin resonance (ESR), nuclear magnetic resonance (NMR), and simultaneous thermogravimetry, differential thermal analysis, and mass spectrometry techniques (TG-DTA-MS). The weight of AlON gradually increases to a maximum value at 1150°C and then decreases with further heating. Meanwhile, AlON powder undergoes chemical changes, as evidenced by lattice expansion, and turns eventually into alumina. ESR spectra reveal the occurrence of lone pair electrons in the oxidized products and the intensity of corresponding resonance signal increases before disappearing with the increase in temperature. Combined with the results of NMR and TG-DTA-MS, the measured data suggest that Al-N in [AlO₃N] tetrahedron and [AlO₅N] octahedron are gradually oxidized into Al-O-N group with lone pair electrons, which causes continuous weight gain and lattice expansion. Further oxidation at higher temperatures results in alumina and N₂.     

Localized swelling of Fe-Cr-Ni alloy rollers in high-temperature applications

Localized swelling has been observed in 24Cr-24Ni-Nb steel transportation rollers used in the normalizing furnace of a plate mill after prolonged service at high temperature. Due to high localized thermal and mechanical stresses, the chromia layer formed on the roller surface ruptures, exposing the roller substrate to furnace oxygen. Oxidation of second-phase carbides results in the formation of carbon monoxide at very high partial pressure. This leads to formation of voids, leading in turn to localized swelling of the roller material.     

Numerical Simulation of Internal Oxidation of Steels during Annealing Treatments

This paper presents a new model for simultaneous diffusion and precipitation of chemical elements in metallic matrices, a scheme for its numerical solution, and several applications to problems of internal oxidation. The model basically stands as an extension of the classical Wagner model for internal oxidation of steels, but is more much general in that it allows for an arbitrary number of diffusing chemical elements, an arbitrary number of precipitate phases with arbitrary compositions, dependence of diffusion coefficients and solubility products upon (time-dependent) temperature, etc., thus allowing for a much broader range of applications. As a counterpart, it is generally impossible to solve the complex, non-linear equations of the model analytically, but this can be done numerically. The simple but efficient numerical scheme proposed is based on explicit 1D finite differences. Experience has shown that this scheme, in spite of its rusticity and the restrictions it imposes on the time-step, is more efficient than more elaborate strategies based on the finite-element method. The applications presented are concerned with internal oxidation of steels during annealing processes. The model and associated numerical scheme allow for evaluation of the amounts of the various oxide precipitates in the external layer of the sheet. This opens the way, through numerical parametric studies of the influence of the process parameters and the chemical composition, to the improvement of existing treatments and the development of new steel grades.     

Oxidation Performance of Fe-Al/WC Composite Coatings Produced by High Velocity Arc Sprayed at 650 ℃

Fe-Al intermetallics with remarkable high-temperatureintensity and excellent erosion,high-temperatureoxidation and sulfuration resistance are potential lowcost high-temperature structural material.ProducingFe-Al/WC composite coating by high velocity arcspraying(HVAS)on structural materials would notonly obviate the problems faced in fabrication of thesealloys into useful shapes,but also allow the effectiveuse of their outstanding high-temperature performance,which might thus promisingly mak…