Microstructural prototyping of ceramics by kinetic engineering: applications of spark plasma sintering

The significance of kinetics on the development of microstructures in connection with sintering of ceramics is well recognized. In practice, however, it still remains a challenge to prepare designed microstructures via engineering the sintering kinetics because of an insufficient understanding of the different operative mechanisms that are in many cases overlapping. In this article the kinetic issues involved in sintering are described and discussed with respect to their potential for prototyping microstructures that yield desired properties. By exploiting and mastering the differences present in the kinetics of grain sliding, densification, chemical reactions, and grain growth, respectively, we have established processing principles for producing bulk ceramics with microstructures consisting of nano-sized grains, aligned grains, and/or non-equilibrium-phase constitutions, and for achieving radically improved superplasticity in brittle ceramics. Although the studies quoted in this article were mainly carried out by spark plasma sintering, more general implications of them are expected, including efficient particle sliding, deformation-induced dynamic ripening, superplastic deformation-induced dynamic ripening, and non-equilibrium integration.     

Generalized anisotropic scaling theory and the transverse meissner transition

We consider a depinning transition in vortex systems with columnar disorder and tilted applied magnetic fields. From scaling arguments and Monte Carlo simulations, we find that this transverse Meissner transition is governed by a fixed point which is anisotropic in all three directions. This generalization of conventional anisotropic scaling means that the correlation length in different directions diverges with different rates, and we derive exact results for the anisotropy exponents. We make predictions which can be tested in experiments on superconductors with columnar disorder.     

Object characterization with refractometric digital Fourier holography

We demonstrate a digital holographic method in which two different substances in a blend are discerned. The method requires only one set of exposures and one reconstruction in the plane of focus. The phase is unwrapped by Flynn's discontinuity algorithm to produce an image of the variation of the optical distance of the illuminating wave. Objects with indices of refraction that are higher and lower than the mounting liquid are detected as regions in which the phase is increased and decreased, respectively. We also present a method for calculating the volume distribution of substrates in a sample. The method is experimentally demonstrated with crystals of NaCl and KCl.     

Scanning tunneling spectroscopy of Cl vacancies in NaCl films: strong electron-phonon coupling in double-barrier tunneling junctions

Broad Gaussian line shapes are observed in scanning tunneling spectroscopy of single, localized electronic states induced by Cl vacancies in ultrathin NaCl films on Cu surfaces. Using a simple inelastic resonance tunneling model, we show that the observed broad line shapes are caused by a strong coupling between the localized state and the optical phonons in the film. The parameters for the model are obtained from density functional calculations, in which the occupation of the vacancy state temporarily taking place in the experiment has also been accounted for.     

Parity-violating electron deuteron scattering and the proton's neutral weak axial vector form factor

We report on a new measurement of the parity-violating asymmetry in quasielastic electron scattering from the deuteron at backward angles at Q2=0.038 (GeV/c)2. This quantity provides a determination of the neutral weak axial vector form factor of the nucleon, which can potentially receive large electroweak corrections. The measured asymmetry A=-3.51+/-0.57 (stat)+/-0.58 (syst) ppm is consistent with theoretical predictions. We also report on updated results of the previous experiment at Q2=0.091 (GeV/c)2, which are also consistent with theoretical predictions.     

Dioxygen-promoted regioselective oxidative heck arylations of electron-rich olefins with arylboronic acids

Arylations of electron-rich heteroatom-substituted olefins were performed with arylboronic acids. This appears to constitute the first example of palladium(II)-catalyzed internal Heck arylations. The novel protocol exploits oxygen gas for environmentally benign reoxidation and a stable 1,10-phenanthroline bidentate ligand to promote the palladium(II) regeneration and to control the regioselectivity. Internal arylation is strongly favored with electron-rich arylboronic acids. DFT calculations support a charge-driven selectivity rationale, where phenyls substituted with electron-donating groups prefer the electron-poor alpha-carbon of the olefin. Experiments, verified by calculations, confirm the cationic nature of the catalytic route. This Heck methodology provides a facile and mild access to functionalized enamides. Controlled microwave heating and increased oxygen pressure were used to further reduce the reaction time to 1 h.     

Microwave-promoted and chelation-controlled double arylations of terminal olefinic carbon of vinyl ethers

Herein we report a rapid, palladium-catalyzed terminal diarylation of the chelating olefin N,N-dimethyl(2-ethenyloxy)ethanamine under noninert conditions utilizing controlled microwave heating as a convenient energy source. Among the aryl bromides examined, both electron-rich and electron-poor substrates were demonstrated to furnish useful yields after only 10-120 min of directed microwave heating at 160-200 degrees C. The good terminal regioselectivity suggests that the precatalyst (Herrmann's palladacycle) serves as a source of weakly coordinated palladium(0) in the investigated high-temperature Heck process.     

An efficient method to perform milliliter-scale PCR utilizing highly controlled microwave thermocycling

This communication describes the development of a controlled microwave methodology for rapid milliliter-scale PCR.     

Far-infrared absorption by collisionally interacting nitrogen and methane molecules

Quantum line shape calculations of the rototranslational enhancement spectra of nitrogen-methane gaseous mixtures are reported. The calculations are based on a recent theoretical dipole function for interacting N(2) and CH(4) molecules, which accounts for the long-range induction mechanisms: multipolar inductions and dispersion force-induced dipoles. Multipolar induction alone was often found to approximate the actual dipole surfaces of pairs of interacting linear molecules reasonably well. However, in the case of the N(2)-CH(4) pair, the absorption spectra calculated with such a dipole function still show a substantial intensity defect at the high frequencies (>250 cm(-1)) when compared to existing measurements at temperatures from 126 to 297 K, much as was previously reported.