Structural evolution of tensile-deformed high-density polyethylene during annealing: Scanning synchrotron small-angle X-ray scattering study

The structural evolution of high-density polyethylene subjected to uniaxial tensile deformation was investigated as a function of strain and after annealing at different temperatures using a scanning synchrotron small-angle X-ray scattering (SAXS) technique. The results confirm that in the course of tensile deformation intralamellar block slips were activated at small deformations followed by a stress-induced fragmentation and recrystallization process yielding thinner lamellae with their normal parallel to the stretching direction. The original sheared lamellae underwent severe internal deformation so that they were even less stable than the newly developed thinner lamellae. Accordingly, annealing results in a melting of the original crystallites even at moderate strains where the stress-induced fragmentation and recrystallization just sets in and generates a distinctly different form of lamellar stacks aligned along the drawing direction. It was found that the lamellae newly formed during stretching at moderate strains remain stable at lower temperature. Only at a very high annealing temperature of 120 degrees C can they be melted, leading to an isotropic distribution of the lamellar structure.

Mass fractal characteristics of wet sonogels as determined by small-angle x-ray scattering and differential scanning calorimetry

Low density silica sonogels were prepared from acid sonohydrolysis of tetraethoxysilane. Wet gels were studied by small-angle x-ray scattering (SAXS) and differential scanning calorimetry (DSC). The DSC tests were carried out under a heating rate of 2 degrees C/min from -120 degrees C up to 30 degrees C. Aerogels were obtained by CO(2) supercritical extraction and characterized by nitrogen adsorption and SAXS. The DSC thermogram displays two distinct endothermic peaks. The first, a broad peak extending from about -80 degrees C up to practically 0 degrees C, was associated to the melting of ice nanocrystals with a crystal size distribution with pore diameter ranging from 1 or 2 nm up to about 60 nm, as estimated from Thomson's equation. The second, a sharp peak with onset temperature close to 0 degrees C, was attributed to the melting of macroscopic crystals. The DSC incremental nanopore volume distribution is in reasonable agreement with the incremental pore volume distribution of the aerogel as determined from nitrogen adsorption. No macroporosity was detected by nitrogen adsorption, probably because the adsorption method applies stress on the sample during measurement, leading to a underestimation of pore volume, or because often positive curvature of the solid surface is in aerogels, making the nitrogen condensation more difficult. According to the SAXS results, the solid network of the wet gels behaves as a mass fractal structure with mass fractal dimension D=2.20 +/- 0.01 in a characteristic length scale below xi=7.9 +/- 0.1 nm. The mass fractal characteristics of the wet gels have also been probed from DSC data by means of an earlier applied modeling for generation of a mass fractal from the incremental pore volume distribution curves. The results are shown to be in interesting agreement with the results from SAXS.

Structural modifications in stretch-induced crystallization in PVDF films as measured by small-angle X-ray scattering

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A thermoporometry and small-angle x-ray scattering study of wet silica sonogels as the pore volume fraction is varied

Silica sonogels with different porosities were prepared by acid sono-hydrolysis of tetraethoxysilane. Wet sonogels were studied using small-angle x-ray scattering (SAXS) and differential scanning calorimetry (DSC). The DSC shows a broad thermal peak below the normal water melting point associated with the melting of confined ice nanocrystals, or nanoporosity. The nanopore size distribution was determined from the Gibbs-Thomson equation. As the porosity is increased, a second sharp DSC thermal peak with onset temperature at the water melting point is apparent, which was associated with the melting of ice macrocrystals, or macroporosity. The DSC result could be causing misinterpretation of the macroporosity because water may not be exactly confined in very feeble silica network regions in sonogels with high porosity. The structure of the wet gels can be described fairly well as mutually self-similar mass fractal structures with characteristic length. increasing from similar to 1.8 to similar to 5.4 nm and mass fractal dimension D diminishing discretely from similar to 2.6 to similar to 2.3 as the porosity increases in the range studied. More specifically, such a structure could be described using a two-parameter correlation function gamma(r) similar to r(D-3) exp(-r/xi), which is limited at larger scale by the cut-off distance xi but without a well-defined small scale cut-off distance, at least up to the maximum angular domain probed using SAXS in the present study.

Small angle X-ray scattering mapping and kinetics study of sub-critical CO2 sorption by two Australian coals

Time- and position-resolved synchrotron small angle X-ray scattering data were acquired from samples of two Australian coal seams: Bulli seam (Bulli 4, Ro=1.42%, Sydney Basin), which naturally contains CO2 and Baralaba seam (Ro=0.67%, Bowen Basin), a potential candidate for sequestering CO2. This experimental approach has provided unique, pore-size-specific insights into the kinetics of CO2 sorption in the micro- and small mesopores (diameter 5 to 175 Å) and the density of the sorbed CO2 at reservoir-like conditions of temperature and hydrostatic pressure. For both samples, at pressures above 5 bar, the density of CO2 confined in pores was found to be uniform, with no densification in near-wall regions. In the Bulli 4 sample, CO2 first flooded the slit pores between polyaromatic sheets. In the pore-size range analysed, the confined CO2 density was close to that of the free CO2. The kinetics data are too noisy for reliable quantitative analysis, but qualitatively indicate faster kinetics in mineral-matter-rich regions. In the Baralaba sample, CO2 preferentially invaded the smallest micropores and the confined CO2 density was up to five times that of the free CO2. Faster CO2 sorption kinetics was found to be correlated with higher mineral matter content but, the mineral-matter-rich regions had lower-density CO2 confined in their pores. Remarkably, the kinetics was pore-size dependent, being faster for smaller pores. These results suggest that injection into the permeable section of an interbedded coal-clastic sequence could provide a viable combination of reasonable injectivity and high sorption capacity.

Evidence of clustering in an aqueous electrolyte solution: a small-angle X-ray scattering study

The work reported hen was motivated by a desire to verify the existence of structure - specifically MP-rich clusters induced by sodium bromide (NaBr) in the ternary liquid mixture 3-methylpyridine (Mf) + water(W) + NaBr. We present small-angle X-ray scattering (SAXS) measurements in this mixture. These measurements were obtained at room temperature (similar to 298 K) in the one-phase region (below the relevant lower consolute points, T(L)s) at different values of X (i.e., X = 0.02 - 0.17), where X is the weight fraction of NaBr in the mixture. Cluster-size distribution, estimated on the assumption that the clusters are spherical, shows systematic behaviour in that the peak of the distribution shifts rewards larger values of cluster radius as X increases. The largest spatial extent of the clusters (similar to 4.5 nm) is seen at X = 0.17. Data analysis assuming arbitrary shapes and sizes of clusters gives a limiting value of cluster size (- 4.5 nm) that is not very sensitive to X. It is suggested that the cluster size determined may not be the same as the usual critical-point fluctuations far removed from the critical point (T-L). The influence of the additional length scale due to clustering is discussed from the standpoint of crossover from Ising to mean-field critical behaviour, when moving away from the T-L.

pi-conjugation and conformation in a semiconducting polymer: small angle x-ray scattering study

Small angle x-ray scattering (SAXS) in a poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) solution has shown the important role of pi-electron conjugation in controlling the chain conformation and assembly. By increasing the extent of conjugation from 30 to 100%, the persistence length (l(p)) increases from 20 to 66 angstrom. Moreover, a pronounced second peak in the pair distribution function has been observed in a fully conjugated chain, at larger length scales. This feature indicates that the chain segments tend to self-assemble as the conjugation along the chain increases. Xylene enhances the rigidity of the PPV backbone to yield extended structures, while tetrahydrofuran solvates the side groups to form compact coils in which the lp is much shorter.

Small-angle x-ray scattering study of the aggregation of gold nanoparticles during formation at the toluene-water interface

We report the results of an in situ small-angle x-ray scattering (SAXS) study of the aggregation of gold nanoparticles formed by an interfacial reaction at the toluene-water interface. The SAXS data provide a direct evidence for aggregate formation of nanoparticles having 1.3 nm gold core and an organic shell that gives a core-core separation of about 2.5 nm. Furthermore, the nanoparticles do not occupy all the cites of 13-member cluster. This occupancy decreases with reaction time and indicate reorganization of the clusters that generates planner disklike structures. A gradual increase in fractal dimension from 1.82 to 2.05 also indicate compactification of cluster aggregation with reaction time, the final exponent being close to 2 expected for disklike aggregates.

Synchrotron Small-Angle X-ray Scattering Studies of Hemoglobin Nonaggregation Confined inside Polymer Capsules

The effect of confinement on the structure of hemoglobin (Hb) within polymer capsules was investigated here. Hemoglobin transformed from an aggregated state in solution to a nonaggregated state when confined inside the polymer capsules. This was directly confirmed using synchrotron small-angle X-ray scattering (SAXS) studies. The radius of gyration (R-g) and polydispersity (p) of the proteins in the confined state were smaller compared to those in solution. In fact, the R-g value is very similar to theoretical values obtained using protein structures generated from the Protein Databank. In the temperature range (25-85 degrees C, Tm 59 degrees C), the R-g values for the confined Hb remained constant. This observation is in contrary to the increasing R-g values obtained for the bare Hb in solution. This suggested higher thermal stability of Hb when confined inside the polymer capsule than when in solution. Changes in protein configuration were also reflected in the protein function. Confinement resulted in a beneficial enhancement of the electroactivity of Hb. While Hb in solution showed dominance of the cathodic process (Fe3+ -> Fe2+), efficient reversible Fe3+/Fe2+ redox response is observed in the case of the confined Hb. This has important protein functional implications. Confinement allows the electroactive heme to take up positions favorable for various biochemical activities such as sensing of analytes of various sizes from small to macromolecules and controlled delivery of drugs.

Small angle X-ray scattering of the colloidal crystal

The monodisperse polystyrene spheres are assembled into the colloidal crystal on the glass substrate by vertical deposition method, which is aimed at the so-called photonic crystal applications. The structural information of the bulk colloidal crystal is crucial for understanding the crystal growth mechanism and developing the various applications of colloidal crystal. Small-angle X-ray scattering (SAXS) technique was used to obtain the bulk structure of the colloidal crystal at Beamline 1W2A of BSRF. It is found that the SAXS pattern is sensitive to the relative orientation between the colloidal sample and the incident X-ray direction. The crystal lattice was well distinguished and determined by the SAXS data.

The microstructure of hydrogenated microcrystalline silicon thin films studied by small-angle x-ray scattering

The microstructures of hydrogenated microcrystalline silicon (tic-Si: H) thin films, prepared by plasma-enhanced chemical vapor deposition (PECVD), hot wire CVD(HWCVD) and plasma assisted HWCVD (PE-HWCVD), have been analyzed by the small angle x-ray scattering(SAXS) measurement. The SAXS data show that the microstructures of the μ c-Si: H films display different characteristics for different deposition techniques. For films deposited by PECVD, the volume fraction of micro-voids and mean size are smaller than those in HWCVD sample. Aided by suitable ion-bombardment, PE-HWCVD samples show a more compact structure than the HWCVD sample. The microstructure parameters of the μ c-Si: H thin films deposited by two-steps HWCVD and PE-HWCVD with Ar ions are evidently improved. The result of 45° tilting SAXS measurement indicates that the distribution of micro-voids in the film is anisotropic. The Fouriertransform infrared spectra confirm the SAXS data.