A SAXS method for the quantitative assessment of the morphology of polymer layered silicate nanocomposites is proposed. Fitting the SAXS patterns, the number of clay layers, the periodicity of the layers in the tactoids, the thickness of the regions interposed between the clay platelets and their distributions can be measured. A good agreement with TEM data was obtained, avoiding the inconsistencies with microscopical observations often reported in the literature. 相似文献
This work demonstrated a novel and potentially important application of two-dimensional small-angle X-ray scattering (2D-SAXS) to investigate powder compaction. SAXS from powder compacts of three materials commonly used for pharmaceutical tabletting exhibited azimuthal variations, with stronger intensity in the direction of the applied compaction force, relative to the transverse direction. This implied that compaction of a (macroscopic) powder could also produce changes on the molecular (nanometre) scale, which can be probed by 2D-SAXS. Two possible explanations for this effect were suggested. A combination of anisometric (i.e. elongated or flattened) granules with anisotropic morphologies could result in azimuthal variation in X-ray scattering due to granule orientation. It is expected that this mechanism would require relatively low packing density, so may operate during die filling. Granule re-orientation appeared less likely at higher packing densities and compaction pressures, however. Under these conditions, the changes in the 2D-SAXS patterns would be consistent with the powder granules becoming relatively flattened in the compression direction, with corresponding changes in their nano-scale morphology. The magnitude of this effect was found to vary between the materials used and increased with compaction pressure. This suggested that 2D-SAXS studies could provide useful information on force-transmission within a compressed powder. Further analysis of the data also suggested differences in the compaction mechanisms (i.e. granule re-orientation, deformation or fragmentation) between the materials studied. 相似文献
Summary: The cold crystallization process of initially amorphous poly(L ‐lactic acid), PLLA, with two different molecular weights, during a heating at 2 °C/min, was investigated by DSC and time‐resolved simultaneous SAXS and WAXS, using synchrotron radiation. Equatorial scans of the isotropic 2D‐SAXS patterns showed that the average Bragg long period (LB) of PLLA samples was approximately constant with the development of cold crystallization up to a temperature that corresponded to a melt/re‐crystallization process that took place before the nominal melting peak seen by DSC. LB values were found to be higher for the high molecular weight material. This was in accordance with the higher melting temperature observed in the high molecular weight PLLA that implied the existence of thicker lamellae. WAXS results showed that the molecular weight did not apparently affect the crystal form and the final degree of crystallinity of PLLA. The Avrami parameters from WAXS and DSC were consistent, showing that the non‐isothermal cold crystallization of the two PLLA samples corresponded mainly to a three‐dimensional growth, although an imperfect crystallization process was involved at early times. The crystallization rate of PLLA, observed both by WAXS and DSC, decreased with increasing molecular weight.
SAXS profiles of PLLA2 as a function of temperature. The inset shows the 2D‐SAXS pattern obtained at 180 °C. 相似文献
The lamellar morphology of a melt-miscible blend consisting of two crystalline constituents, poly(3-hydroxybutyrate) (PHB) and poly(ethylene oxide) (PEO) have been investigated by means of small angle X-ray scattering (SAXS). The blend was a crystalline/amorphous system when temperatures lay between the melting point of PEO (ca. TmPEO=60C) and that of PHB (ca. TmPHB=170C), while it became a crystalline/crystalline system below TmPEO. The crystalline microstructures of the blends were induced by two types of crystallization history, i.e. one-step and two-step crystallizations. In the one-step crystallization, the blends were directly quenched from the melt to room temperature to allow simultaneous PHB and PEO crystallization. The two-step crystallization involved first cooling to 70C to allow PHB crystallization for 72 h followed by cooling to room temperature (ca. 19C) to allow PEO crystallization. In the crystalline/crystalline state, two scattering peaks have been observed in the Lorentz-corrected SAXS profiles, irrespective of the crystallization histories, meaning that crystallization created separate PHB and PEO lamellar stack domains. One-step crystallization yielded lamellar stack domains containing almost pure PHB and PEO lamellae. Two-step crystallization generated almost pure PHB lamellar domains and the PEO lamellar domains with inserted PHB lamellae. In the crystalline/amorphous state, the composition dependence of the amorphous layer thickness (la), the presence of zero-angle scattering, and the volume fraction of the PHB lamellar stack (s) revealed that both one-step and two-step crystallizations, generated the interfibrillar segregation morphology, where the extent of interfibrillar segregation of amorphous PEO increased with increasing PEO content. 相似文献
Relationships between the macroscopic deformation behaviour and microstructure of a pure (PBT-b-PTMO) block copolymer and a polymer nanocomposite (PBT-b-PTMO + 0.2 wt% SWCNT) were investigated by simultaneous small- and wide-angle X-ray scattering (SAXS and WAXS) during tensile deformation using synchrotron radiation. The Young's modulus was found to be 15% higher for the nanocomposite than for the pure block copolymer as well as the yield strength, while the elongation-to-break was less than a half. This different behaviour can be explained by taking into account the different structural features revealed by SAXS and WAXS and thus considering that SWCNT act as anchors in the nanocomposite, sharing the applied stress with the PBT crystals and partially preventing the flexible, non-crystallisable PTMO chains to elongate. 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