The “corset effect” of spin-lattice relaxation in polymer melts confined in nanoporous media

Linear polyethylene oxides with molecular weightsM _w of 1665 and 10170 confined in pores with variable diameters in a solid methacrylate matrix were studied by proton field-cycling nuclear magnetic resonance relaxometry. The pore diameter was varied in the range of 9–57 nm. In all cases, the spin-lattice relaxation time shows a frequency dependence close toT ₁∞ v^3/4 in the range ofv=3·10^?1-2·10¹ MHz as predicted by the tube-reptation model. This protonT ₁ dispersion essentially reproduces that found in a previous deuteron study (R. Kimmich, R.-O. Seitter, U. Beginn, M. Möller, N. Fatkullin: Chem. Phys. Lett. 307, 147, 1999). As a feature particularly characteristic for reptation, this finding suggests that reptation is the dominating chain dynamics mechanism under pore confinement in the corresponding time range. The absolute values of the spin-lattice relaxation times indicate that the diameter of the effective tubes in which reptation occurs is much smaller than the pore diameters on the time scale of spin-lattice relaxation experimens. An estimation leads to a valued ^*～0.5 nm. The impenetrability of the solid pore walls, the uncrossability of polymer chains (“excluded volume”) and the low value of the compressibility in polymer melts create the “corset effect” which reduces the lateral motions of polymer chains to a microscopic scale of only a few tenths of a nanometer.     

effect of surface modification on the properties of hydrogen-sensitive GaAs-based Schottky diodes

The surface of hydrogen-sensitive GaAs Schottky diodes is modified by nonpolishing etching and by producing quantum wells and quantum dots in the space-charge region of the semiconductor. The sensitivity to hydrogen is found to increase by a factor of 8–37 after the etching and by two or three orders of magnitude after the introduction of quantum wells and dots. It is shown that the increased sensitivity is associated with the lowering of the barrier at the Pd/GaAs interface, the retardation of hydrogen diffusion into GaAs due to the presence of strained quantum-size layers, and an increase in the recombination current. The presence of the recombination component is supported by luminescence from the quantum wells and quantum dots, as well as from the GaAs substrate. The etch composition is shown to be a decisive factor in raising the sensitivity.     

cos πρ theorems for δ-subharmonic functions

For ϕ a δ-subharmonic function, sharp results are obtained that connectA(r, ϕ), B(r, ϕ) andT(r, ϕ), whereA(r, ϕ)=inf_|z|=r ϕ(z),B(r, ϕ)=sup_|z|=r ϕ(z), andT(r, ϕ) is the Nevanlinna characteristics.     

Polarization dynamics of intracavity frequency-doubled Nd:YAG laser

Experimental study of low-frequency dynamics of an intracavity frequency-doubled Nd:YAG laser demonstrates the influence of the interaction of orthogonally polarized modes, participating in frequency doubling (type II phase matching), on the stability of the laser output. At a sufficiently low pump rate and low conversion efficiency, the laser shows stable operation with a low noise level at the frequencies of relaxation oscillations. At a high pump power and/or a high conversion efficiency, the laser emission becomes unstable as a result of Hopf bifurcation at the frequencies of relaxation oscillations that are responsible for the anti-phase polarization dynamics of the laser.     

Investigations of low- and high-spin states of <Superscript>132</Superscript>La

The fusion evaporation reaction ¹²²Sn(¹⁴N, 4n)¹³²La was used to populate the high-spin states of ¹³²La at the beam energy of 60 MeV. A new band consisting of mostly E2 transitions has been discovered. This band has the interesting links to the ground state 2^- and the isomeric state 6^-. A new transition of energy 351 keV connecting the low-spin states of the positive-parity band based on the πh _11/2 ⊗ νh _11/2 particle configuration, has been found. This has played a very important role in resolving the existing ambiguities and inconsistencies in the spin assignment of the band head. Received: 12 August 2002 / Accepted: 18 March 2003 / Published online: 7 May 2003     

Numerical study of the effects of the rupture process of a secondary diaphragm in expansion tubes

The results of a numerical study are described in which the interactions of a primary shock wave with a secondary diaphragm in expansion tubes are taken into account. The developing wave pattern in the interacting process of the shock with a secondary diaphragm are visualized by many kinds of figures (e.g., the time-distance diagrams of the wave phenomena on the axis, the acoustic impedance contours, and the time histories of the pitot pressure on the axis), and the influences of the shape and rupture process of the diaphragm on the quality of the test gas are explored.     

Effect of short glass fiber on structure and viscoelastic behavior of olefinic polymers synthesized with metallocene catalyst

Several composites were prepared on the basis of an ethylene homopolymer and different copolymers of ethylene and 1‐hexene, synthesized with a metallocene catalyst, as matrices and a content of a 5 wt % of short glass fiber. The effect of the fiber incorporation on the structure and mechanical and viscoelastic behaviors was analyzed for the different samples. The glass fibers induced a slightly higher crystallinity, and the crystallite morphology significantly changed (long spacings and crystal orientation). The incorporation of fibers did not reinforce the different matrices under study at this low content; consequently, the mechanical parameters, such as Young's modulus, yielding stress, and microhardness, were lower in the composites as compared with those values found in the neat polyolefins. The location and apparent activation energies of distinct relaxation processes are also discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1244–1255, 2003     

Ultrasonic spectroscopic evaluation of the ring‐opening metathesis polymerization of dicyclopentadiene

An in situ ultrasonic spectroscopy technique was used to study the ring‐opening metathesis polymerization of dicyclopentadiene catalyzed by bis(tricyclohexylphosphine)benzylidene ruthenium dichloride. A reaction cell employing a flexible poly(ethylene terephthalate) window for pulse echo ultrasonic spectroscopy was used to monitor the polymerization. The changes in the density, wave speed, acoustic modulus, and attenuation were all simultaneously monitored. In comparison with Fourier transform infrared (FTIR) spectroscopy data, the changes in the density, velocity, and modulus only accurately measured the rate constant for the metathesis of the cyclopentyl unsaturation. The ultrasonic values were within 6% of the values determined by FTIR. The activation energy for metathesis of the cyclopentyl unsaturation was 84 kJ mol^?1, following first‐order kinetics. Rate constants for the polymerization of the norbornyl unsaturation could not be determined by ultrasound. The gel point, vitrification, and qualitative information about the reaction rate could be determined from the change in the attenuation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1323–1333, 2003     

An algorithm to locate perinatal facilities in the municipality of Rio de Janeiro

In order to reduce infant mortality in the municipality of Rio de Janeiro it is desired to encourage all mothers-to-be to attend the appropriate health care facilities. A 3-level hierarchical prenatal–neonatal health care system is described together with a basic model for optimising accessibility to facilities. A genetic algorithm to solve the basic model is developed and some numerical experience reported. Extensions to the basic model and planned future research are briefly indicated.