Stability control of the electrooptic effect with new maleimide copolymers containing photoreactive tricyanopyrrolidene‐based chromophores

New photocrosslinkable maleimide copolymers have been synthesized by the attachment of a tricyanopyrrolidene‐based chromophore. The 2‐(3‐cyano‐4‐(2‐{4‐[hexyl‐(6‐hydroxy‐hexyl)‐amino]‐phenyl}‐vinyl)‐5‐oxo‐1‐{4‐[4‐(3‐oxo‐3‐phenyl‐propenyl)‐ phenoxy]‐butyl}‐1,5‐dihydro‐pyrrol‐2‐ylidene)‐malononitrile chromophore exhibits nonlinear optical activity and contains a chalcone moiety that is sensitive to UV light (λ = 330–360 nm) for crosslink formation. The maleimide monomers have also been functionalized with chalcone moieties. The resultant copolymers exhibit great processability, and one of them shows a maximum electrooptic coefficient of 90 pm/V at 1300 nm. We could control the thermal stability of the electrooptic coefficient with the newly synthesized photoreactive copolymers successfully. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 531–542, 2007     

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Glass transitions and mixed phases in block SBS

Differential scanning calorimetry (DSC) does not allow for easy determination of the glass‐transition temperature (T_g) of the polystyrene (PS) block in styrene–butadiene–styrene (SBS) block copolymers. Modulated DSC (MDSC), which deconvolutes the standard DSC signal into reversing and nonreversing signals, was used to determine the (T_g) of both the polybutadiene (PB) and PS blocks in SBS. The T_g of the PB block was sharp, at ?92 °C, but that for the PS blocks was extremely broad, from ?60 to 125 °C with a maximum at 68 °C because of blending with PB. PS blocks were found only to exist in a mixed PS–PB phase. This concurred with the results from dynamic mechanical analysis. Annealing did not allow for a segregation of the PS blocks into a pure phase, but allowed for the segregation of the mixed phase into two mixed phases, one that was PB‐rich and the other that was PS‐rich. It is concluded that three phases coexist in SBS: PB, PB‐rich, and PS‐rich phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 276–279, 2005     

Structure of norbornene-fused 3,1-oxazine double cycloadducts

Pentacyclic isoxazolines were obtained by the cycloaddition of benzonitrile oxide to norbornene-azetidinone-fused 3,1-oxazines. The constitutions of two of the isomers obtained, and the configurations and conformations of all products, were determined by means of ¹H and ¹³C NMR spectroscopy and DNOE experiments.     

Galactic model of element formation

A cosmological model is presented that produces He, C, O, D, Li, Be, and B in their observed abundances without a Big Bang. The elements are produced during the 1.5-Gy formation period of a galaxy, with C, O, and other heavy elements produced by stars of M>12 M₃ , He by stars of 6 M_s<M<12 M_s, and D, Li, Be, and B by cosmic-ray reactions in a nearly pure H plasma halo. Thus, the model shows that the major elements used in astrophysical studies can be produced during galactic formation by exactly the same processes known to function today at much lower rates     

The effect of geoacoustic characteristics of the bottom on the long-range sound propagation in an inhomogeneous ocean

The long-range sound propagation from a deep ocean to a receiving system located on the shelf is modeled. The waveguide model is constructed on the basis of the data of an acoustic-oceanographic experiment carried out in the northwestern Pacific. The sensitivity and the frequency dependence of the difference in the sound field levels at the crossing of the frontal zone on the geoacoustic characteristics of the bottom of the shelf and the continental slope are investigated. It is shown that the level difference decreases by 8.2 dB as the velocity of longitudinal waves increases by 100 m/s in the range within 1490–1820 m/s.     

Isothermal crystallization kinetics of poly(3‐hydroxybutyrate)/layered double hydroxide nanocomposites

Poly(3‐hydroxybutyrate) (PHB)/layered double hydroxides (LDHs) nanocomposites were prepared by mixing PHB and poly(ethylene glycol) phosphonates (PEOPAs)‐modified LDH (PMLDH) in chloroform solution. Both X‐ray diffraction data and TEM micrographs of PHB/PMLDH nanocomposites indicate that the PMLDHs are randomly dispersed and exfoliated into the PHB matrix. In this study, the effect of PMLDH on the isothermal crystallization behavior of PHB was investigated using a differential scanning calorimeter (DSC) and polarized optical microscopy. Isothermal crystallization results of PHB/PMLDH nanocomposites show that the addition of 2 wt % PMLDH into PHB induced more heterogeneous nucleation in the crystallization significantly increasing the crystallization rate and reducing their activation energy. By adding more PMLDH into the PHB probably causes more steric hindrance of the diffusion of PHB, reducing the transportation ability of polymer chains during crystallization, thus increasing the activation energy. The correlation among crystallization kinetics, melting behavior and crystalline structure of PHB/PMLDH nanocomposites can also be discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3337–3347, 2006     

A Symmetric-Impulse Approximation Applied to the Faddeev Theory on the Charge Transfer Amplitude

Off-the-shell anomalous factors of the two-body Coulomb transition matrices appear in the integral form of the Faddeev second-order nuclear-electronic amplitude, for proton-hydrogen charge transfer scattering in a typical nlm → n′l′m′ transition. A symmetric-impulse approximation (SIA) is applied to eliminate these factors and an induction method is proposed to analytically calculate the remaining integrals. The nuclear-electronic amplitude is derived for the general case, and for totally symmetric collisions, in terms of generalized hypergeometric functions of two variables, F ₄, and of one variable, ₃ F ₂, respectively. The angular distribution of the second-order nuclear-electronic charge transfer amplitude shows the Thomas mechanism as a peak or a hump for symmetric and asymmetric collisions. There also exists a peak in the forward angular distribution of the second-order nuclear-electronic amplitude, which partly cancels the kinematic peak in the angular distribution of the charge transfer differential cross sections.     

Phasing of three vircators simulated in terms of coupled van der Pol oscillators

Phase synchronization in a system of three virtual-cathode microwave oscillators (vircators) simulated by coupled van der Pol oscillators is studied. The phasing dynamics of the vircators is visualized with the phase portraits of the system in the triangular coordinates. Different phasing conditions are found.