Real Time Development of Structure in Partially Molten State Stretching of Polypropylene as Detected by Spectral Birefringence Technique: Effect of Isotacticity

The uniaxial deformation behavior of three polypropylene films with isotacticity indices varying from 43 to 95 was investigated in the partially molten state using real time, true stress, true strain, and birefringence measurement system. These polymers generally exhibit three regime stress‐birefringence behaviors during stretching. The unmelted crystalline regions act as physical junctions. If the films contain crystallinity that is too low (less than ca. 10%) the Regime I disappears. Under these conditions, the films were found to exhibit large linearity in strain and stress optical behavior. If, however, too low a deformation rate is employed, these relationships become non‐linear.

The increase of isotacticity increases the magnitude of the birefringence at all deformation levels primarily as a result of the increase in crystallinity that helps in establishing a long‐range physical network. This increase in the long‐range connectivity was found to promote not only the orientation in crystalline domains but also in the amorphous domains. The increased long‐range connectivity in high isotacticity films was also found to result in destruction of local initial structures that generate a large fraction of the oriented amorphous chain regions. This translates into larger stress decrease and birefringence increase changes during the holding stage where the oriented amorphous chains undergo complex relaxation/oriented crystallization processes.     

Inhomogeneous superconducting state in the overdoped regime of La2−xSrxCuO4: Comparison with the superconducting state of NbSe2

We have measured the temperature dependence of the magnetic susceptibility, χ vs. T, and the magnetization curve, M vs. H, for NbSe₂ single crystals, in order to compare the superconducting (SC) state in the overdoped regime of La_2−xSr_xCuO₄ (LSCO) with the SC state of the layered conventional superconductor NbSe₂. While a plateau in χ vs. T in a moderate magnetic field and a so-called second peak in M vs. H, which is due to the marked enhancement of vortex pinning, have been observed in the overdoped regime of LSCO, these behaviors have not been observed in NbSe₂. The present results indicate that the anomalously marked enhancement of vortex pinning is a characteristic feature in the overdoped LSCO where a microscopic phase separation into SC and normal-state regions takes place.     

Damping constant of Co/Pt multilayer thin-film media

Gilbert's damping constants, α, of Co(t_Co)/Pt (1.4 nm) multilayer thin films are investigated by Q-band FMR analysis. α is calculated from the resonance width of the FMR spectrum. With decreasing t_Co, the α value decreases from 0.034 (t_Co=8.7 nm) to 0.023 (t_Co=1.8 nm), and then increases to 0.037 (t_Co=1.0 nm). The decrease of α with t_Co>1.8 nm is probably due to the eddy current loss effects. The increase of α with t_Co<1.8 nm would be caused by the increase of the distortion between the Co and the Pt layers at the interface. When the magnetic field direction was changed from θ=90° (parallel to the specimen) to θ=0° (perpendicular to the specimen), the α of all the specimens increased, and a sharp step in α was observed around θ=40°, where the α has the maximum value.     

Exponential structural relaxation of a high purity silica glass

While most other glasses exhibit non-exponential structural relaxation characteristics even when the change of fictive temperature is small, a high purity silica glass exhibited exponential structural relaxation. This was demonstrated by showing that the non-exponential exponent or β value of the KWW function of the high purity silica glass approaches unity when the change of the fictive temperature approaches zero both from higher and lower temperature sides of the heat-treatment temperature. The non-exponentiality of the structural relaxation of this glass when fictive temperature change is finite is due to the change of relaxation time during the structural relaxation.     

Direct through anionic,cationic, and radical active species: Terminal carbon–halogen bond for “controlled”/living polymerizations of styrene

In this work, we examined the synthesis of novel block (co)polymers by mechanistic transformation through anionic, cationic, and radical living polymerizations using terminal carbon–halogen bond as the dormant species. First, the direct halogenation of growing species in the living anionic polymerization of styrene was examined with CCl₄ to form a carbon–halogen terminal, which can be employed as the dormant species for either living cationic or radical polymerization. The mechanistic transformation was then performed from living anionic polymerization into living cationic or radical polymerization using the obtained polymers as the macroinitiator with the SnCl₄/n‐Bu₄NCl or RuCp^*Cl(PPh₃)/Et₃N initiating system, respectively. Finally, the combination of all the polymerizations allowed the synthesis block copolymers including unprecedented gradient block copolymers composed of styrene and p‐methylstyrene. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 465–473     

On the rate of convergence of solutions in free boundary problems via penalization

The rate of convergence of approximate solutions via penalization for free boundary problems are concerned. A key observation is to obtain global bounds of penalized terms which give necessary estimates on integrations by the nonlinear adjoint method by L.C. Evans.     

Formal total synthesis of fostriecin via 1,4-asymmetric induction using cobalt-alkyne complex

The synthesis of a protected dephosphofostriecin, and thereby a formal synthesis of fostriecin, has been accomplished. Two of the four chiral centers are controlled by an external chiral auxiliary and the other two are synthesized stereoselectively, one by a novel 1,4-asymmetric induction using cobalt-alkyne complex, and the other by 1,3-asymmetric induction.     

Direct construction of bicyclic heterocycles by palladium-catalyzed domino cyclization of propargyl bromides

The palladium-catalyzed domino cyclization of propargyl bromides having two nucleophilic functional groups is described. Treatment of 1,7-diamino-5-bromohept-3-yne derivatives with catalytic Pd(PPh3)4 in the presence of NaH in MeOH gives the 2,7-diazabicyclo[4.3.0]non-5-enes in good yields. Interestingly, the regioselectivity of the reaction is completely controlled by the relative reactivity of the amine functional groups, irrespective of the position of the nucleophiles. The malonate derivative also undergoes domino cyclization to produce a hexahydroindole derivative.