Longitudinal piezoelectric strain measurements of poly(vinylidene fluoride) films

The longitudinal piezoelectric strain of poly(vinylidene fluoride) (PVF₂) films has been measured at room temperature using a high-sensitivity ac capacitance-type dilatometer. The dc bias field dependence of the piezoelectric strain coefficient d₃₃ has been determined. The polarization-related electrostrictive coefficient Q₃₃ obtained is several hundred times larger than the value in normal piezoelectric oxide crystals and is of opposite sign.     

Effects of doping and free carriers on the refractive index of direct-gap semiconductors

A model for the doping and current dependence of the refractive index of direct-gap semiconductors has been developed and applied to GaAs in order to explain certain properties of single heterostructure injection lasers. The model involves the concept of an effective energy gap which takes account of the effects of doping and free carriers via the Burstein shift, the exchange interaction, and the average screened Coulomb potential of the impurities. This effective gap, together with empirical results for the energy dependence of the refractive index, facilitates the calculation of refractive index changes with doping and current. Numerical results are given for GaAs, and the model is applied particularly to the substrate and active regions of single heterostructure injection lasers. In these devices the refractive index values are particularly important in determining the dielectric waveguide properties. With the aid of our model, this feature can be discussed in detail, with special reference to the breakdown of the waveguide effect which occurs (a) for substrate doping levels below a critical value, and (b) for currents well above threshold ('saturation').     

PISEMA powder patterns and PISA wheels

Resonance patterns observed in 2D PISEMA (polarization inversion spin exchange at magic angle) spectra from a transmembrane alpha-helix have been demonstrated to yield structural details of the protein. This paper presents a mathematical discussion of the PISEMA powder spectrum as the image in the frequency plane of a quadratic function from the sphere of unit vectors. The simplicity of this function allows easy calculation of the powder spectrum. Based on this analysis of powder patterns, four degeneracies are discussed which arise in determining possible orientations associated with PISA spectra. This paper also gives parametric equations for PISA wheels, which are specific patterns observed in PISEMA spectra of oriented peptides. These wheels are useful both in assigning the resonances and in determining the orientation of the helix with respect to the magnetic field. The union of these PISA wheels gives the entire powder spectrum.     

Cover Picture

The cover picture shows the process of hydrogen and helium insertion/expulsion which has been achieved for the first time with an open fullerene derivative (outlined in the background). The experimental activation barrier for helium decomplexation could be obtained and fully agrees with the calculated value (density functional theory). The barrier for H(2) complexation/decomplexation is interestingly almost double that of helium, as illustrated by the energy diagram shown in the foreground. This difference arises from the larger, elongated surface of H(2) undergoing greater van der Waals interaction at the transition state relative to that of helium, even though both atoms have the same radii. More about this process can be found in the article by Rubin, Houk, Saunders, Cross et al. on p. 1543 ff.     

High-precision half-life measurement for the superallowed β+ emitter ²⁶Al(m)

A high-precision half-life measurement for the superallowed β+ emitter 26Al(m) was performed at the TRIUMF-ISAC radioactive ion beam facility yielding T 1/2 6346.54 ± 0.46(stat) ± 0.60 (syst) ms, consistent with, but 2.5 times more precise than, the previous world average. The 26Al(m) half-life and ft value, 3037.53(61) s, are now the most precisely determined for any superallowed β decay. Combined with recent theoretical corrections for isospin-symmetry-breaking and radiative effects, the corrected Ft value for (26)Al(m), 3073.0(12) s, sets a new benchmark for the high-precision superallowed Fermi β-decay studies used to test the conserved vector current hypothesis and determine the V(ud) element of the Cabibbo-Kobayashi-Maskawa quark mixing matrix.     

Analysis of Strain Energy Behavior Throughout a Fatigue Process

The dissipation of strain energy density per cycle was analyzed to understand its trend through a fatigue process. The motivation behind this analysis is to improve a fatigue life prediction method, which is based on a strain energy and failure correlation. The correlation states that the same amount of strain energy is dissipated during both monotonic fracture and cyclic fatigue. This means the summation of strain energy density per cycle is equal to the total strain energy density dissipated monotonically. In order to validate this understanding, the strain energy density per cycle was analyzed at several alternating stress levels for fatigue life of Aluminum 6061-T6 (Al 6061-T6) between 10³ and 10⁵ cycles. The analysis includes the following: Alternating between high and low operating frequencies (50x magnitude difference), interruption of cyclic load during testing, and idle/zero-loading intervals of 20–40 minutes in-between cyclic loading sequences. All experimental results show a consistent trend of cyclic softening as the loading cycles approach failure; however, due to an inefficient curve fit procedure of the stress-dependent strain equation at low alternating stresses onto the experimental stress-strain data, a new approach for calculating the strain energy density per cycle is explored and shows promising results.     

Geometry of kinked protein helices from NMR data

Residual dipolar couplings between spin-1/2 and quadrupolar nuclei are often observed and exploited in the magic-angle spinning (MAS) NMR spectra of spin-1/2 nuclei. These orientation-dependent splittings contain information on the dipolar interaction, which can be translated into structural information. The same type of splittings may also be observed for pairs of quadrupolar nuclei, although information is often difficult to extract from the quadrupolar-broadened lineshapes. Here, the complete theory for describing the dipolar coupling between two quadrupolar nuclei in the frequency domain by Hamiltonian diagonalization is given. The theory is developed under MAS and double-rotation (DOR) conditions, and is valid for any spin quantum numbers, quadrupolar coupling constants, asymmetry parameters, and tensor orientations at both nuclei. All terms in the dipolar Hamiltonian become partially secular and contribute to the NMR spectrum. The theory is validated using experimental 11B and 35/37Cl NMR experiments carried out on powdered B-chlorocatecholborane, where both MAS and DOR are used to help separate effects of the quadrupolar interaction from those of the dipolar interaction. It is shown that the lineshapes are sensitive to the quadrupolar coupling constant of both nuclei and to the J coupling (including its sign). From these experiments, the dipolar coupling constant for a heteronuclear spin pair of quadrupolar nuclei may be obtained as well as the sign of the quadrupolar coupling constant of the perturbing nucleus; these are two parameters that are difficult to obtain experimentally otherwise.     

Rate mechanisms of a novel thiol-ene photopolymerization reaction

A novel thiol-ene photopolymerization reaction involving copolymerization of tetrathiol monomer with vinyl silazane is experimentally characterized and is modeled successfully. The overall polymerization rate is found to be controlled by the ratio of the propagation to chain transfer kinetic parameters. The polymerization rate of this mixture, in the presence of added photoinitiator, is approximately first order in ene functionality and is independent of thiol functional group concentration. Initiation rates in this system, when cured utilizing a light centered around 365 nm light, and in the presence of no added photoinitiator, are shown to be proportional to the ene monomer concentration. When the mixture is polymerized utilizing light centered at 254 nm light, and without photoinitiator, the initiation rates are proportional to the thiol monomer concentrations. This novel reaction scheme is further utilized to form ultra rapidly polymerizable polymer derived ceramic structures with high aspect ratios.