Spherulitic growth rates and microstructure of syndiotactic polystyrene (sPS) cold-crystallized isothermally at various temperatures, Tc (115–240 °C), have been investigated by small-angle light scattering (SALS), optical microscopy and transmission electron microscopy. The derived activation energy for sPS chain mobility at the crystal growing front is 5.4 kJ/mol, which is relatively lower than that of isotactic polystyrene, 6.5 kJ/mol. In addition, the Hv scattering invariant (QHv) measured by SALS on the crystallized sPS samples displays a pronounced minimum at 150 °C. Despite a wide range of Tc used, however, the sample crystallinity estimated by Fourier transformation infrared spectroscopy remains unchanged. Prior to crystallization, the correlation length derived from the Vv patterns on the basis of Debye–Bueche model is ca. 1.13 μm regardless of Tc used. Interconnected domains with a width of ca. 1.8±0.5 μm are readily observed in all the crystallized samples under phase contrast microscopy and the phase-separated structure is conserved within sPS spherulites whose diameters are increased with increasing Tc.
Based on the above facts, we conclude that the presence of a QHv minimum is ascribed to the resultant events of the two competitive transitions i.e. liquid–solid crystallization, and liquid–liquid demixing resulting from the spinodal decomposition (SD). At lower Tc, the unstable SD transition overwhelms the crystallization. Despite the low chain mobility, the coarsening process driven by the interfacial energies has reached a certain level before crystalline nucleation takes place. At higher Tc, on the other hand, cold crystallization becomes the dominant process due to the enhanced chain mobility, leading to the suppression of ongoing SD coarsening process. At an intermediate Tc range, comparable competition of the phase separation and crystallization prohibits the development of ordered symmetry within spherulites, giving the presence of QHv minimum. 相似文献
In this paper, ZnCo2O4 was deposited on nickel substrate by electrophoretic deposition (EPD) method as electrocatalyst for the oxygen evolution reaction. The effect of electrophoresis variables including the deposition time, the applied voltages was discussed. XRD, SEM, and electrochemical measurement techniques were used to characterize the deposit and ZnCo2O4/Ni electrode. Compared with the ZnCo2O4 electrode prepared by nitrate decomposition method, the electrophoretic ZnCo2O4 electrodes exhibit better electrocatalytic properties and higher mechanical stability. And the electrode prepared at 10 V for 5 min has the best electrocatalytic properties with the overpotential of only 0.203 V at current density of 100 mA cm−2. 相似文献
Extensive morphological studies on a syndiotactic polystyrene (sPS) sample prepared from compression molding were carried out using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). SAXS was conducted at 25C as well as at 150C to enhance the scattering contrast in order to obtain more reliable morphological parameters. The compression-molded sample was crystallized into a orthorhombic crystal lattice characterized by wide-angle X-ray diffraction (WAXD). A similar weight fraction of crystallinity, ca. 0.37, was obtained from both WAXD and differential scanning calorimetry measurements.In addition to the scattering peak at a scattering vector of ca. 0.36 nm–1 attributable to the presence of lamellar/amorphous layers, anomalous scattering at the zero angle was found from the SAXS intensity profiles. Based on the Debye–Bueche theory, the scattering profile of this peculiar zero-angle scattering was deduced and was subtracted from the raw intensity profile to obtain the intensity profile exclusively associated with the lamellar/amorphous structure. A consistent long period was obtained for SAXS measured either at 25 or 150C, provided that the appropriate subtraction of intensities due to the zero-angle scattering was conducted. Moreover, the lamellar thickness deduced from the one-dimensional correlation function was in good agreement with TEM results. A difference scattering pattern derived from SAXS measured at 150 and 25C was obtained and a comparison of the morphological parameters was provided as well. 相似文献