Phase transformation and segregation to lattice defects in Ni-base superalloys.

Nanostructural features of nickel-base superalloys as revealed by atom probe field ion microscopy (APFIM) and atom probe tomography (APT) are reviewed. The more salient information provided by these techniques is discussed through an almost exhaustive analysis of literature over the last 30 years. Atom probe techniques are shown to be able to measure the composition of tiny gamma' precipitates, a few nanometers in size, and to reveal chemical order within these precipitates. Phase separation kinetics in model NiCrAl alloys was investigated with both 3DAP and Monte-Carlo simulation. Results are shown to be in good agreement. Plane by plane analysis of {001} planes of Ni(3)Al-type gamma' phase makes it possible to estimate the degree of order as well as the preferential sites of various addition elements (Ti, Cr, Co, W, Ta, Re, Ru, etc.) included in superalloys. Clustering effects of Re in the gamma solid solution were also exhibited. Due to its ultrahigh depth resolution, the microchemistry of interfaces and grain boundaries can be characterized on an atomic scale. Grain boundaries in Astroloy or N18 superalloys were found to be enriched in B, Mo, and Cr and Al depleted.     

Chemie der schweren carben-analogen R2M, M = Si, Ge, Sn : XVIII. Eine unerwartete Ge---C-Spaltung des als Dimethylgermylen-Speicher dienenden 7,7-Dimethyl-7-germanorbornadiens

During thermolysis of the 7-germanorbornadiene 1 in chlorobenzene at 70°C in the presence of concentrated hydrochloric acid, besides the well-known formation of free germylene Me₂Ge and its consecutive product dimethylchlorogermane 2, the polar splitting of only one Ge---C bond in 1 has been observed for the first time. It does not yield Me₂Ge, but instead it rapidly forms the 1-germyl-1,4-dihydronaphthalene 3. The kinetics of this reaction at 53°C are of 2nd order, t_1/2 = 20 min, k = 0.22 l mol⁻¹ min⁻¹. At room temperature 3 is formed quantitatively. Also, at 70°C the slower formation of the germylene Me₂Ge from 1 can be suppressed completely if HCl gas is bubbled through the reaction mixture, thus favouring the rapid formation of 3. As a by-product the 1,2-dihydronaphthalene 5 is generated.     

Synthetic studies on palytoxin. Stereocontrolled,practical synthesis of the C.101–C.115 segment

A stereocontrolled and practical synthetic route to the acetal $\text{2a}$, a degradation product of palytoxin, in optically active form is described.     

Mean Wiener numbers and other mean extensions for alkane trees

The "Wiener number" (the sum over intersite graph distances of a structure) as averaged over all alkane structural isomers of a fixed number N of carbon atoms is considered. This and several other measures of average graphical "extension" of N-site alkanes are computed for N up to 90 (where there are over 10(35) such isomers). Fits are then made for several surmised or derived asymptotic forms, and a heuristic argument is made relating these results to geometric extensions of a random mix of (N-site) alkanes.     

The shape resonance

For a class of Schrödinger operatorsH:=–(²/2m)+V onL ²( ⁿ ), with potentials having minima embedded in the continuum of the spectrum and non-trapping tails, we show the existence of shape resonances exponentially close to the real axis as 0. The resonant energies are given by a convergent perturbation expansion in powers of a parameter exhibiting the expected exponentially small behaviour for tunneling.