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.     

Characterization of chemicals mediating ovipositional host-plant finding byAmyelois transitella females

Ovipositional host-finding in the navel orangeworm,Amyelois transitella (Walker), is brought about by an in-flight response to host odors. Wind-tunnel studies of the response of gravid females to almonds showed that this response is mediated primarily by long-chain fatty acids, particularly oleic acid and linoleic acid. Evidence for the behavioral activity of fatty acids is based on the fact that: (1) behavioral activity of almond oil was concentrated in a single liquid chromatographic fraction whose composition was predominantly long-chain fatty acids, (2) behavioral activity was lost when either almond oil or the active fraction of that oil was treated with diazomethane, (3) full activity was elicited by a selective extraction of free fatty acids from crude almond oil, and (4) upwind response by females was elicited by a blend of synthetic oleic and linoleic acids, albeit at a level less than that elicited by almond oil. Five fatty acids identified from the almond oil were: myristic acid (1%), palmitic acid (16%), stearic acid (3%), oleic acid (58%), and linoleic (22%). Attraction to various combinations of synthetic acids was observed only when oleic acid was present, and oleic acid elicited upwind flights to the source when presented alone; however, short-range responses were enhanced by the addition of linoleic acid, which elicited no long-range orientation by itself. Despite significant levels of attraction to synthetic blends, the percentage of females flying to the source was lower than that flying to acidulated almond oil, the best natural attractant tested. Thus, although longrange response may be mediated primarily by a blend of oleic and linoleic acids, additional and as yet unidentified components must also play an important role. Long-range chemically modulated host finding in this and other generalist plant feeders is discussed with respect to current models of the evolution of host finding, and it is argued that suggestions that long-range host finding should be correlated with narrowness of host utilization are logically flawed and are not supported by our current understanding of specific examples of host finding.     

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...     

频率响应法研究噻吩在CeY分子筛上的吸附行为

以NaY、液相Ce离子交换改性的Y型分子筛(L-CeY)为研究对象,运用N2吸附、XRD、NH3-TPD和Py-FTIR等实验方法表征两种Y型分子筛的物化性能。采用频率响应技术(FR)和智能重量分析仪(IGA)研究噻吩在两种分子筛上的吸附行为,并考察噻吩在稀土离子改性Y型分子筛上的不同吸附作用模式。结果表明,频率响应技术能够有效识别分子筛孔道内发生的不同传质过程。噻吩在NaY分子筛上的吸附行为较为简单,存在孔道吸附和π电子相互作用两种吸附过程;而在L-CeY分子筛上吸附行为较为复杂,同时存在孔道吸附和"S-M"吸附等多种吸附过程,另外,在高温条件下,还存在复杂的催化反应过程。     

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.