Hysteresis in the Active Oxidation of SiC

Si and SiC show both passive oxidation behavior where a protective film of SiO2 forms and active oxidation behavior where a volatile suboxide SiO(g) forms. The active-to-passive and passive-to-active oxidation transitions are explored for both Si and SiC. Si shows a dramatic difference between the P(O2) for the two transitions of ~10-4 bar. The active-to-passive transition is controlled by the condition for SiO2/Si equilibrium and the passive-to-active transition is controlled by the decomposition of SiO2. In the case of SiC, the P(O2) for these transitions are much closer. The active-to-passive transition appears to be controlled by the condition for SiO2/SiC equilibrium. The passive-to-active transition appears to be controlled by the interfacial reaction of SiC and SiO2 and subsequent generation of gases at the interface which leads to scale breakdown

Active Oxidation of SiC

The high temperature oxidation of silicon carbide occurs in either a passive or active mode, depending on temperature and oxygen potential. Passive oxidation forms a protective oxide film which limits attack of the SiC:SiC(s) + 3/2 O2(g) = SiO2(s) + CO(g.) Active oxidation forms a volatile oxide and leads to extensive attack of the SiC: SiC(s) + O2(g) = SiO(g) + CO(g). The transition points and rates of active oxidation are a major issue. Previous studies are reviewed and the leading theories of passive/active transitions summarized. Comparisons are made to the active/passive transitions in pure Si, which are relatively well-understood. Critical questions remain about the difference between the active-to-passive transition and passive-to-active transition. For Si, Wagner [2] points out that the active-to-passive transition is governed by the criterion for a stable Si/SiO2 equilibria and the passive-to-active transition is governed by the decomposition of the SiO2 film. This suggests a significant oxygen potential difference between these two transitions and our experiments confirm this. For Si, the initial stages of active oxidation are characterized by the formation of SiO(g) and further oxidation to SiO2(s) as micron-sized rods, with a distinctive morphology. SiC shows significant differences. The active-to-passive and the passive-to-active transitions are close. The SiO2 rods only appear as the passive film breaks down. These differences are explained in terms of the reactions at the SiC/SiO2 interface. In order to understand the breakdown of the passive film, pre-oxidation experiments are conducted. These involve forming dense protective scales of 0.5, 1, and 2 microns and then subjecting the samples with these scales to a known active oxidation environment. Microstructural studies show that SiC/SiO2 interfacial reactions lead to a breakdown of the scale with a distinct morphology

Further Observations on the Behavior of Vanillin Substitution Products: (a) The Perkin Reaction; (b) The Preparation of Substituted Vanillic Acids

When the carbonyl group is joined directly to carbon and hydrogen (aldehydic) or to carbon and carbon (ketonic) it reacts with phenylhydrazine to give the corresponding phenylhydrazone. When the radical is joined directly to nitrogen and hydrogen, as in formanilide, the products are aniline and formylphenylhydrazine. Substitution productions of formanilide behave similarly. If the radical is joined directly to nitrogen and nitrogen, as in diphenylurea, the products are aniline and a semicarbazide. The corresponding thiourea behaves similarly, and gives a thiosemicarbazide. If the reaction with the thioureas is carried out in the presence of a desulphurizing agent, guanidine derivatives are obtained

Magnetic order in GdBiPt studied by x-ray resonant magnetic scattering

Rare earth (R) half-Heusler compounds, RBiPt, exhibit a wide spectrum of novel ground states. Recently, GdBiPt has been proposed as a potential antiferromagnetic topological insulator (AFTI). We have employed x-ray resonant magnetic scattering to elucidate the microscopic details of the magnetic structure in GdBiPt below T_N = 8.5 K. Experiments at the Gd L_2 absorption edge show that the Gd moments order in an antiferromagnetic stacking along the cubic diagonal [1 1 1] direction satisfying the requirement for an AFTI, where both time-reversal symmetry and lattice translational symmetry are broken, but their product is conserved.Comment: 4 pages, 4 figure

Computational Study of Turbulent-Laminar Patterns in Couette Flow

Turbulent-laminar patterns near transition are simulated in plane Couette flow using an extension of the minimal flow unit methodology. Computational domains are of minimal size in two directions but large in the third. The long direction can be tilted at any prescribed angle to the streamwise direction. Three types of patterned states are found and studied: periodic, localized, and intermittent. These correspond closely to observations in large aspect ratio experiments.Comment: 4 pages, 5 figure

Experimental and Theoretical Study of Thermodynamics of the Reaction of Titania and Water at High Temperatures

The transpiration method was used to determine the volatility of titanium dioxide (TiO2) in water vapor-containing environments at temperatures between 1473 and 1673 K. Water contents ranged from 0 to 76 mole % in oxygen or argon carrier gases for 20 to 250 hr exposure times. Results indicate that oxygen is not a key contributor to volatilization and the primary reaction for volatilization in this temperature range is: TiO2(s) + H2O(g) = TiO(OH)2(g). Data were analyzed with both the second and third law methods to extract an enthalpy and entropy of formation. The geometry and vibrational frequencies of TiO(OH)2(g) were computed using B3LYP density functional theory, and the enthalpy of formation was computed using the coupled-cluster singles and doubles method with a perturbative correction for connected triple substitutions [CCSD(T)]. Thermal functions are calculated using both a structure with bent and linear hydroxyl groups. Calculated second and third heats show closer agreement with the linear hydroxyl group, suggesting more experimental and computational spectroscopic and structural work is needed on this system

A Mechanistic Study of Halogen Addition and Photoelimination from ?-Conjugated Tellurophenes

The ability to drive reactivity using visible light is of importance for many disciplines of chemistry and has significant implications for sustainable chemistry. Identifying photochemically active compounds and understanding photochemical mechanisms is important for the development of useful materials for synthesis and catalysis. Here we report a series of photoactive diphenyltellurophene compounds bearing electron-withdrawing and electron-donating substituents synthesized by alkyne coupling/ring closing or palladium-catalyzed ipso-arylation chemistry. The redox chemistry of these compounds was studied with respect to oxidative addition and photoelimination of bromine, which is of importance for energy storage reactions involving X₂. The oxidative addition reaction mechanism was studied using density functional theory, the results of which support a three-step mechanism involving the formation of an initial η¹ association complex, a monobrominated intermediate, and finally the dibrominated product. All of the tellurophene derivatives undergo photoreduction using 430, 447, or 617 nm light depending on the absorption properties of the compound. Compounds bearing electron-withdrawing substituents have the highest photochemical quantum efficiencies in the presence of an alkene trap, with efficiencies of up to 42.4% for a pentafluorophenyl-functionalized tellurophene. The photoelimination reaction was studied in detail through bromine trapping experiments and laser flash photolysis, and a mechanism is proposed. The photoreaction, which occurs by release of bromine radicals, is competitive with intersystem crossing to the triplet state of the brominated species, as evidenced by the formation of singlet oxygen. These findings should be useful for the design of new photochemically active compounds supported by main-group elements

Magnetoresistance, specific heat and magnetocaloric effect of equiatomic rare-earth transition-metal magnesium compounds

We present a study of the magnetoresistance, the specific heat and the magnetocaloric effect of equiatomic $RET$Mg intermetallics with $RE = {\rm La}$, Eu, Gd, Yb and $T = {\rm Ag}$, Au and of GdAuIn. Depending on the composition these compounds are paramagnetic ($RE = {\rm La}$, Yb) or they order either ferro- or antiferromagnetically with transition temperatures ranging from about 13 to 81 K. All of them are metallic, but the resistivity varies over 3 orders of magnitude. The magnetic order causes a strong decrease of the resistivity and around the ordering temperature we find pronounced magnetoresistance effects. The magnetic ordering also leads to well-defined anomalies in the specific heat. An analysis of the entropy change leads to the conclusions that generally the magnetic transition can be described by an ordering of localized $S=7/2$ moments arising from the half-filled $4f^7$ shells of Eu$^{2+}$ or Gd$^{3+}$. However, for GdAgMg we find clear evidence for two phase transitions indicating that the magnetic ordering sets in partially below about 125 K and is completed via an almost first-order transition at 39 K. The magnetocaloric effect is weak for the antiferromagnets and rather pronounced for the ferromagnets for low magnetic fields around the zero-field Curie temperature.Comment: 12 pages, 7 figures include

Managing Risk and Growth of Nonprofit Revenue

Managers of nonprofit organizations are challenged to manage revenue growth and risk (i.e., volatility) in order to sustain current and future financial operations. Although the negative repercussions of revenue risk are generally perceived as undesirable, not all risk is bad. If higher levels of revenue risk are compensated with a greater amount of revenue growth, then organizations may rationally pursue volatile revenues that produce growth. This article examines the extent to which a reliance on major revenue sources by nonprofit organizations affects the magnitude of total revenue volatility as well as the pace of total revenue growth. A monitoring application is introduced that can be used to compare the effectiveness of revenue management among similar nonprofit organizations. It can also be used to guide nonprofit managers striving to achieve sustainable financial growth for their organizations