Synthesis and characterization of volatile,fluorine-free beta-ketoiminate lanthanide MOCVD precursors and their implementation in low-temperature growth of epitaxial CeO(2) buffer layers for superconducting electronics

A new class of volatile, low-melting, fluorine-free lanthanide metal-organic chemical vapor deposition (MOCVD) precursors has been developed. The neutral, monomeric Ce, Nd, Gd, and Er complexes are coordinatively saturated by a versatile, multidentate ether-functionalized beta-ketoiminato ligand series, the melting point and volatility characteristics of which can be tuned by altering the alkyl substituents on the keto, imino, and ether sites of the ligand. Direct comparison with conventional lanthanide beta-diketonate complexes reveals that the present precursor class is a superior choice for lanthanide oxide MOCVD. Epitaxial CeO(2) buffer layer films can be grown on (001) YSZ substrates by MOCVD at significantly lower temperatures (450-650 degrees C) than previously possible by using one of the newly developed cerium beta-ketoiminate precursors. Films deposited at 540 degrees C have good out-of-plane (Deltaomega = 0.85 degrees ) and in-plane (Deltaphi = 1.65 degrees ) alignment and smooth surfaces (rms roughness approximately 4.3 A). The film growth rate decreases and the films tend to be smoother as the deposition temperature is increased. High-quality yttrium barium copper oxide (YBCO) films grown on these CeO(2) buffer layers by pulsed organometallic molecular beam epitaxy exhibit very good electrical transport properties (T(c) = 86.5 K, J(c) = 1.08 x 10(6) A/cm(2) at 77.4 K).     

Relating the microscopic and macroscopic response of a polymeric fluid in a shearing flow

The microscopic and macroscopic response of a polymer solution in start-up shear flow was investigated using fluorescence microscopy of single molecules, bulk viscosity measurements, and Brownian dynamics simulations. An overshoot in viscosity was observed upon flow inception and understood via the observed molecular extension and by simulation findings. Increasing the polymer concentration up to six times the overlap concentration ( C(*)) has no effect on the character of the dynamics of individual molecules.     

The element effect and nucleophilicity in nucleophilic aromatic photosubstitution (SN2Ar*). Local atom effects as mechanistic probes of very fast reactions

Photoreactions of 4-nitroanisole and the 2-halo-4-nitroanisoles (halogen = F, Cl, Br, and I) with the nucleophiles hydroxide ion and pyridine have been investigated quantitatively to extend the findings recently communicated for cyanide ion. The halonitroanisoles on excitation form triplet pi,pi* states, which undergo substitution of the halogen by nucleophiles. Chemical yields of photoproducts, Stern-Volmer kinetic plots, triplet lifetimes, and triplet yields are reported for the five compounds with the three nucleophiles. Following a standard kinetic treatment, 73 rate constants are determined for elementary reactions of the triplets including quenching and various nucleophilic addition processes. The photoadditions are roughly 14 orders of magnitude faster than thermal counterparts. Rate constants for attack at the fluorine-bearing carbon of triplet 2-fluoro-4-nitroanisole are 2.9 x 10(9), 1.3 x 10(9), and 6.3 x 10(8) M(-1) s(-1) for cyanide ion, hydroxide ion, and pyridine, respectively. The relative rates for attack at the halogen-bearing carbons for F/Cl/Br/I are 27:1.9:1.9:1 (cyanide ion), 29:2.6:2.4:1 (hydroxide ion), and 39:3.9:3.5:1 (pyridine), respectively. The relative nucleophilicities vary somewhat with the attack site; they are about 5:2:1 for cyanide ion, hydroxide ion, and pyridine for attack at the halogen-bearing carbons. The trend of the element effect opposes that of aliphatic substitution and elimination but is similar in size and parallel to that of thermal nucleophilic aromatic substitution. Relative nucleophilicities in the photoreactions are also similar to those of comparable but vastly slower thermal reactions. The findings imply that the efficiency-determining step of the halogen photosubstitution is simple formation of a sigma-complex through electron-paired bonding within the triplet manifold.     

Plastic buckling of cylindrical shells under biaxial loading

The predictions for plastic buckling of shells are significantly affected by the plasticity model employed, in particular in the case of nonproportional loading. A series of experiments on plastic buckling of cylindrical aluminum alloy shells under biaxial loading (external pressure and axial tension), with well-defined loading and boundary conditions, was therefore carried out to provide experimental data for evaluation of the suitability of different, plasticity models. In the experiments, initial imperfections and their growth under load were measured and special attention was paid to buckling detection and load path control. The Southwell plot was applied with success to smooth the results. The results show that axial tension decreases resistance to buckling under external pressure in the plastic region due to softening of the material behavior. Comparison with numerical calculations usingJ ₂ deformation and incremental theories indicate that both theories do not predict correctly plastic buckling under nonproportional loading.Babcock (SEM Member), deceased, was Professor of Aeronautics and Applied Mechanics, California Institute of Technology, Pasadena, CA 91125.     

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Limits to the polarization for spin-exchange optical pumping of 3He

Based on measurements of the temperature dependence of 3He relaxation in a wide range of spin-exchange optical pumping cells, we report evidence for a previously unrecognized surface relaxation process. The relaxation rate was found to be linearly proportional to the alkali-metal density with a slope that exceeds the spin-exchange rate, which limits the polarization for current applications, including neutron spin filters, polarized targets, and polarized gas magnetic resonance imaging. We find that the magnitude of this excess relaxation can vary widely between cells, and that the variation is larger for cells of higher surface to volume ratio. We have observed 3He polarization as high as 81%, but further improvements require understanding the origin of this relaxation.     

Mechanisms of electron-ion recombination of N2H+/N2D+ and HCO+/DCO+ ions: temperature dependence and isotopic effect

The temperature dependencies of the rate coefficients, alpha(e), for electron-ion dissociative recombination (DR) of N2H+/N2D+ and HCO+/DCO+ ions with electrons have been measured over the range 100-500 K. Also, optical emissions have been detected at approximately 100 K from the N2(B3(pi)g) electronically excited products of N2H+/N2D+ recombination. The measurements were carried out using the classic FALP technique combined with an optical monochromator. For N2H+, there was no variation of alpha(e) with temperature above 200 K, with an average value of alpha(e)(N2H+) = 2.8 x 10(-7) cm3 s(-1). The temperature variation for T approximately 100-300 K observed for alpha(e)(HCO+) is similar to that of N2H+ ions for T approximately 300-500 K. The smaller rate coefficient measured for DCO+ and N2D+ ions shows the influence of an isotope effect. The substantial enhancement of the vibrational level, upsilon' = 6, from the N2B state for N2H+ recombination over N2D+ recombination is consistent with previous result at 300 K and implies the influence of a tunneling mechanism of DR.