Optimal control design of constant amplitude phase-modulated pulses: application to calibration-free broadband excitation

An optimal control algorithm for generating purely phase-modulated pulses is derived. The methodology is applied to obtain broadband excitation with unprecedented tolerance to RF inhomogeneity. Design criteria were transformation of Iz-->Ix over resonance offsets of +/-25 kHz for constant RF amplitude anywhere in the range 10-20 kHz, with a pulse length of 1 ms. Simulations transform Iz to greater than 0.99 Ix over the targetted ranges of resonance offset and RF variability. Phase deviations in the final magnetization are less than 2-3 degrees over almost the entire range, with sporadic deviations of 6-9 degrees at a few offsets for the lowest RF (10 kHz) in the optimized range. Experimental performance of the new pulse is in excellent agreement with the simulations, and the robustness of the excitation pulse and a derived refocusing pulse are demonstrated by insertion into conventional HSQC and HMBC-type experiments.     

Correction of wandering smoothing effects on static measurements of a wing-tip vortex

Wandering is a typical feature of wing-tip vortices and it consists in random fluctuations of the vortex core. Consequently, vortices measured by static measuring techniques appear to be more diffuse than in reality, so that a correction method is needed. In the present paper statistical simulations of the wandering of a Lamb-Oseen vortex are first performed by representing the vortex core locations through bi-variate normal probability density functions. It is found that wandering amplitudes smaller than 60% of the core radius are well predicted by using the ratio between the RMS value of the mean cross-velocity and its slope measured at the mean vortex center. Furthermore, the principal axes of wandering can be accurately evaluated from the opposite of the cross-correlation coefficient between the spanwise and the normal velocities measured at the mean vortex center. The correction of the wandering smoothing effects is then carried out through four different algorithms that perform the deconvolution of the mean velocity field with the probability density function that represents the wandering. The corrections performed are very accurate for the simulations with wandering amplitudes smaller than 60% of the core radius, whereas errors become larger with increasing wandering amplitudes. Subsequently, the whole procedure to evaluate wandering and to correct the mean velocity field is applied to static measurements, carried out with a fast-response five-hole pressure probe, of a tip vortex generated from a NACA 0012 half-wing model. It is found that the wandering is predominantly in the upward-outboard to downward-inboard direction. Furthermore, the wandering amplitude grows with increasing streamwise distance from the wing, whereas it decreases with increasing angle of attack and free-stream velocity.     

Internal energy content of n-butylbenzene, bromobenzene, iodobenzene and aniline molecular ions generated by two-photon ionization at 266 nm. A photodissociation study

A technique to investigate photodissociation kinetics on a nanosecond time scale has been devised for molecular ions generated by multiphoton ionization (MPI) using mass-analyzed ion kinetic energy spectrometry. The branching ratio or rate constant has been determined for the photodissociation of the n-butylbenzene, bromobenzene, iodobenzene, and aniline molecular ions generated by MPI at 266 nm. The ion internal energies have been estimated by comparing the measured kinetic data with the previous energy dependence data. The analysis has shown that only those molecular ions generated by two-photon ionization contribute to the photodissociation signals. Around half of the available energy has been found to remain as molecular ion internal energy in the two-photon ionization process. Copyright 1999 John Wiley & Sons, Ltd.     

Physical & thermal properties of model polysiloxane rubbers: impact of crosslink density and tin concentration

The influence of the tin octanoate catalyst on the physical and thermal properties of RTV 5370 polysiloxane rubbers has been studied. To assess the likely influence of crosslinking on a number of physical and thermal properties in polysiloxanes, “model siloxane networks” (representing networks of well defined composition/structure) have been formulated by the hydrosilylation of polysiloxane diols of known average molecular weight with tetraethoxysilane curing agent. It was found that linear swell and the crystallisation melting transitions of these systems were both significantly affected by changes in crosslink density. A selection of RTV5370 foamed rubbers with different tin concentrations were prepared in a similar manner to assess the influence of the tin catalyst. For these materials it was found that the area of the crystalline melting transition decreased with increasing tin concentration, an effect indicative of increased crosslinking. Samples with double the standard amount of tin (10% wt catalyst) show a shift in the crystallisation transition to higher temperature with no further effect beyond this concentration. Furthermore, the storage modulus (E') of the rubbers at room temperature appears to be independent of the tin catalyst concentration. Through correlation with the data from the model siloxanes, these results suggests that increasing the catalyst concentration appears to induce additional crosslinking interactions that are stable at low temperatures but not stable at room temperature.