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At least 1,333 records · Page 74

Secondary channels in the thermal decomposition of monomethylhydrazine (CH 3 NHNH 2 )

Mass spectrometric observations in a very low pressure pyrolysis study of the decomposition of the prototypical rocket fuel monomethylhydrazine (MMH) indicated a dominant role for the molecular channels producing NH 3 and H 2 and their coproducts. In contrast, a recent ab initio transition state theory based master equation theoretical study indicated that simple N–N and C–N bond fissions dominate the kinetics. In this work, the possible role of molecular decomposition channels in MMH is explored further through additional investigations of the potential energy surface. These investigations consider the role of triplet channels, of roaming radical channels, and of some previously unexplored pathways for molecular decomposition. New ab initio transition state theory based master equation calculations provide revised predictions for the temperature and pressure dependence of the MMH decomposition kinetics that are in excellent agreement with recent shock tube measurements. These calculations continue to suggest only a very limited contribution from the molecular elimination channels. A roaming pathway is suggested to provide the dominant route for direct formation of ammonia. The possible role of secondary abstraction reactions in the very-low-pressure pyrolysis experiments is briefly discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electron-beam activated thermal sputtering of thermoelectric materials

Thermoelectricity and Seebeck effect have long been observed and validated in bulk materials. With the development of advanced tools of materials characterization, here we report the first observation of such an effect in the nanometer scale: in situ directional sputtering of several thermoelectric materials inside electron microscopes. The temperature gradient introduced by the electron beam creates a voltage-drop across the samples, which enhances spontaneous sputtering of specimen ions. The sputtering occurs along a preferential direction determined by the direction of the temperature gradient. A large number of nanoparticles form and accumulate away from the beam location as a result. The sputtering and re-crystallization are found to occur at temperatures far below the melting points of bulk materials. The sputtering occurs even when a liquid nitrogen cooling holder is used to keep the overall temperature at -170 deg. C. This unique phenomenon that occurred in the nanometer scale may provide useful clues to understanding the mechanism of thermoelectric effect.

36 MATERIALS SCIENCE↗

Thermal decomposition of CH{sub 3}CHO studied by matrix infrared spectroscopy and photoionization mass spectroscopy

A heated SiC microtubular reactor has been used to decompose acetaldehyde and its isotopomers (CH{sub 3}CDO, CD{sub 3}CHO, and CD{sub 3}CDO). The pyrolysis experiments are carried out by passing a dilute mixture of acetaldehyde (roughly 0.1%-1%) entrained in a stream of a buffer gas (either He or Ar) through a heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 50-200 Torr with the SiC tube wall temperature in the range 1200-1900 K. Characteristic residence times in the reactor are 50-200 {mu}s after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 {mu}Torr. The reactor has been modified so that both pulsed and continuous modes can be studied, and results from both flow regimes are presented. Using various detection methods (Fourier transform infrared spectroscopy and both fixed wavelength and tunable synchrotron radiation photoionization mass spectrometry), a number of products formed at early pyrolysis times (roughly 100-200 {mu}s) are identified: H, H{sub 2}, CH{sub 3}, CO, CH{sub 2}=CHOH, HC{identical_to}CH, H{sub 2}O, and CH{sub 2}=C=O; trace quantities of other species are also observed in some of the experiments. Pyrolysis of rare isotopomers of acetaldehyde produces characteristic isotopic signatures in the reaction products, which offers insight into reaction mechanisms that occur in the reactor. In particular, while the principal unimolecular processes appear to be radical decomposition CH{sub 3}CHO (+M) {yields} CH{sub 3}+ H + CO and isomerization of acetaldehyde to vinyl alcohol, it appears that the CH{sub 2}CO and HCCH are formed (perhaps exclusively) by bimolecular reactions, especially those involving hydrogen atom attacks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermal island destabilization and the Greenwald limit

Magnetic reconnection is ubiquitous in the magnetosphere, the solar corona, and in toroidal fusion research discharges. A magnetic island saturates at a width which produces a minimum in the magnetic energy of the configuration is evident in a fusion device. At saturation, the modified current density profile, a function of the flux in the island, is essentially flat, the growth rate proportional to the difference in the current at the O-point and the X-point. Furthermore, modification of the current density profile in the island interior causes a change in the island stability and additional growth or contraction of the saturated island. Because field lines in an island are isolated from the outside plasma, an island can heat or cool preferentially depending on the balance of Ohmic heating and radiation loss in the interior, changing the resistivity and hence the current in the island. A simple model of island destabilization due to radiation cooling of the island is constructed, and the effect of modification of the current within an island is calculated. In addition destabilization effect is described, and it is shown that a small imbalance of heating can lead to exponential growth of the island. A destabilized magnetic island near the plasma edge can lead to plasma loss, and because the radiation is proportional to plasma density and charge, this effect can cause an impurity dependent density limit.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗