Uniaxial deformation of overstretched polyethylene: In-situ synchrotron small angle X-ray scattering study

Synchrotron small angle X-ray scattering was used to study the deformation mechanism of high-density polyethylene that was stretched beyond the natural draw ratio. New insight into the cooperative deformational behavior being mediated via slippage of micro-fibrils was gained. The scattering data confirm on the one hand the model proposed by Peterlin on the static structure of oriented polyethylene being composed of oriented fibrils, which are built by bundles of micro-fibrils. On the other hand it was found that deformation is mediated by the slippage of the micro-fibrils and not the slippage of the fibrils. In the micro-fibrils, the polymer chains are highly oriented both in the crystalline and in the amorphous regions. When stretching beyond the natural draw ratio mainly slippage of micro-fibrils past each other takes place. The thickness of the interlamellar amorphous layers increases only slightly. The coupling force between micro-fibrils increases during stretching due to inter-microfibrillar polymer segments being stretched taut thus increasingly impeding further sliding of the micro-fibrils leading finally to slippage of the fibrils.

SMALL-ANGLE X-RAY-SCATTERING STUDY ON THE INTERFACE IN BLOCK-COPOLYMERS WITH FRACTAL PROPERTIES

The interface thickness in two triblock copolymers were determined using small-angle x-ray scattering in the context of the theory proposed by Ruland. The thickness was found to be nonexistent for the samples at three different temperatures. By viewing th

Small-angle x-ray scattering study of flow alignment of a thermotropic liquid crystal in the nematic and smectic phases

WThe capillary flow alignment of the thermotropic liquid crystal 4-n-octyl-4′-cyanobiphenyl in the nematic and smectic phases is investigated using time-resolved synchrotron small-angle x-ray scattering. Samples were cooled from the isotropic phase to erase prior orientation. Upon cooling through the nematic phase under Poiseuille flow in a circular capillary, a transition from the alignment of mesogens along the flow direction to the alignment of layers along the flow direction (mesogens perpendicular to flow) appears to occur continuously at the cooling rate applied. The transition is centered on a temperature at which the Leslie viscosity coefficient α3 changes sign. The configuration with layers aligned along the flow direction is also observed in the smectic phase. The transition in the nematic phase on cooling has previously been ascribed to an aligning-nonaligning or tumbling transition. At high flow rates there is evidence for tumbling around an average alignment of layers along the flow direction. At lower flow rates this orientation is more clearly defined. The layer alignment is ascribed to surface-induced ordering propagating into the bulk of the capillary, an observation supported by the parallel alignment of layers observed for a static sample at low temperatures in the nematic phase.

Control and analysis of oriented thin films of lipid inverse bicontinuous cubic phases using grazing incidence small-angle X‑ray scattering

Lipid cubic phases are complex nanostructures that form naturally in a variety of biological systems, with applications including drug delivery and nanotemplating. Most X-ray scattering studies on lipid cubic phases have used unoriented polydomain samples as either bulk gels or suspensions of micrometer-sized cubosomes. We present a method of investigating cubic phases in a new form, as supported thin films that can be analyzed using grazing incidence small-angle X-ray scattering (GISAXS). We present GISAXS data on three lipid systems: phytantriol and two grades of monoolein (research and industrial). The use of thin films brings a number of advantages. First, the samples exhibit a high degree of uniaxial orientation about the substrate normal. Second, the new morphology allows precise control of the substrate mesophase geometry and lattice parameter using a controlled temperature and humidity environment, and we demonstrate the controllable formation of oriented diamond and gyroid inverse bicontinuous cubic along with lamellar phases. Finally, the thin film morphology allows the induction of reversible phase transitions between these mesophase structures by changes in humidity on subminute time scales, and we present timeresolved GISAXS data monitoring these transformations.

Small-angle X-ray and nuclear-magnetic resonance study of siloxane-PMMA hybrids prepared by the sol-gel process

Transparent siloxane-polymethylmethacrylate (PMMA) hybrids were synthesized by the sol-gel process through hydrolysis of methacryloxyproyltrimethoxysilane (TMSM), tetramethoxysilane (TMOS) and polymerization of methylmethacrylate (MMA) using benzol peroxide (BPO) as catalyst. These composites have a good chemical stability due to the presence of covalent bonds between the inorganic (siloxane) and organic (PMMA) phases. The effects of siloxane content, pH of the initial sol and BPO content on the structure of the dried gels were analyzed by small-angle X-ray scattering (SAXS). SAXS results revealed the presence of an interference (or correlation) peak at medium q-range for all compositions, suggesting that siloxane groups located at the ends of PMMA chains form isolated clusters that are spatially correlated. The average intercluster distance - estimated from the q-value corresponding to the maximum in SAXS spectra - decreases for samples prepared with increasing amount of TMSM-TMOS. This effect was assigned to the expected increase in the number density of siloxane groups for progressively higher siloxane content. The increase of BPO content promotes a more efficient polymerization of MMA monomers but has no noticeable effect on the average intercluster distance. High pH favors polycondensation reactions between silicon species of both TMOS and TMSM silicon alcoxides, leading to a structure in which all siloxane clusters are bonded to PMMA chains. This effect was confirmed by Si-29 nuclear-magnetic resonance (NMR) measurements.

Annealing effects on nanostructured gold-polymethylmethacrylate composites: Small-angle x-ray scattering analysis

Composites formed of a polymer-embedded layer of sub-10 nm gold nanoclusters were fabricated by very low energy (49 eV) gold ion implantation into polymethylmethacrylate. We used small angle x-ray scattering to investigate the structural properties of these metal-polymer composite layers that were fabricated at three different ion doses, both in their original form (as-implanted) and after annealing for 6 h well above the polymer glass transition temperature (150 degrees C). We show that annealing provides a simple means for modification of the structure of the composite by coarsening mechanisms, and thereby changes its properties. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4720464]

On the absolute calibration of bench-top small-angle X-ray scattering instruments: a comparison of different standard methods

Absolute calibration relates the measured (arbitrary) intensity to the differential scattering cross section of the sample, which contains all of the quantitative information specific to the material. The importance of absolute calibration in small-angle scattering experiments has long been recognized. This work details the absolute calibration procedure of a small-angle X-ray scattering instrument from Bruker AXS. The absolute calibration presented here was achieved by using a number of different types of primary and secondary standards. The samples were: a glassy carbon specimen, which had been independently calibrated from neutron radiation; a range of pure liquids, which can be used as primary standards as their differential scattering cross section is directly related to their isothermal compressibility; and a suspension of monodisperse silica particles for which the differential scattering cross section is obtained from Porod's law. Good agreement was obtained between the different standard samples, provided that care was taken to obtain significant signal averaging and all sources of background scattering were accounted for. The specimen best suited for routine calibration was the glassy carbon sample, due to its relatively intense scattering and stability over time; however, initial calibration from a primary source is necessary. Pure liquids can be used as primary calibration standards, but the measurements take significantly longer and are, therefore, less suited for frequent use.

Bioactive glass sol-gel foam scaffolds:evolution of nanoporosity during processing and in situ monitoring of apatite layer formation using small- and wide-angle X-ray scattering

Recent work has highlighted the potential of sol-gel-derived calcium silicate glasses for the regeneration or replacement of damaged bone tissue. The work presented herein provides new insight into the processing of bioactive calcia-silica sol-gel foams, and the reaction mechanisms associated with them when immersed in vitro in a simulated body fluid (SBF). Small-angle X-ray scattering and wide-angle X-ray scattering (diffraction) have been used to study the stabilization of these foams via heat treatment, with analogous in situ time-resolved data being gathered for a foam immersed in SBF. During thermal processing, pore sizes have been identified in the range of 16.5-62.0 nm and are only present once foams have been heated to 400 degrees C and above. Calcium nitrate crystallites were present until foams were heated to 600 degrees C; the crystallite size varied from 75 to 145 nm and increased in size with heat treatment up to 300 degrees C, then decreased in size down to 95 rim at 400 degrees C. The in situ time-resolved data show that the average pore diameter decreases as a function of immersion time in SBF, as calcium phosphates grow on the glass surfaces. Over the same time, Bragg peaks indicative of tricalcium phosphate were evident after only 1-h immersion time, and later, hydroxycarbonate apatite was also seen. The hydroxycarbonate apatite appears to have preferred orientation in the (h,k,0) direction.

X-ray scattering and diffraction enhanced imaging studies of in vitro breast tissues

This thesis is a study of the x-ray scattering properties of tissues and tumours of the breast. Clinical radiography is based on the absorption of the x-rays when passing right through the human body and gives information about the densities of the tissues. Besides being absorbed, x-rays may change their direction within the tissues due to elastic scattering or even to refraction. The phenomenon of scattering is a nuisance to radiography in general, and to mammography in particular, because it reduces the quality of the images. However, scattered x-rays bear very useful information about the structure of the tissues at the supra-molecular level. Some pathologies, like breast cancer, produce alterations to the structures of the tissues, being especially evident in collagen-rich tissues. On the other hand, the change of direction due to refraction of the x-rays on the tissue boundaries can be mapped. The diffraction enhanced imaging (DEI) technique uses a perfect crystal to convert the angular deviations of the x-rays into intensity variations, which can be recorded as images. This technique is of especial interest in the cases were the densities of the tissues are very similar (like in mammography) and the absorption images do not offer enough contrast. This thesis explores the structural differences existing in healthy and pathological collagen in breast tissue samples by the small-angle x-ray scattering (SAXS) technique and compares these differences with the morphological information found in the DEI images and the histo-pathology of the same samples. Several breast tissue samples were studied by SAXS technique in the European Synchrotron Radiation Facility (ESRF) in Grenoble, France. Scattering patterns of the different tissues of the breast were acquired and compared with the histology of the samples. The scattering signals from adipose tissue (fat), connective tissue (collagen) and necrotic tissue were identified. Moreover, a clear distinction could be done between the scattering signals from healthy collagen and from collagen from an invasive tumour. Scattering from collagen is very characteristic. It includes several scattering peaks and scattering features that carry information about the size and the spacing of the collagen fibrils in the tissues. It was found that the collagen fibrils in invaded tumours were thinner and had a d-spacing length 0,7% longer that fibrils from healthy tumours. The scattering signals from the breast tissues were compared with the histology by building colour-coded maps across the samples. They were also imaged with the DEI technique. There was a total agreement between the scattering maps, the morphological features seen in the images and the information of the histo- pathological examination. The thesis demonstrates that the x-ray scattering signal can be used to characterize tissues and that it carries important information about the pathological state of the breast tissues, thus showing the potential of the SAXS technique as a possible diagnostic tool for breast cancer.

Small angle scattering characterisation of micellar systems and templated architectures

The work described in this thesis reports the structural changes induced on micelles under a variety of conditions. The micelles of a liquid crystal film and dilute solutions of micelles were subjected to high pressure CO2 and selected hydrocarbon environments. Using small angle neutron scattering (SANS) techniques the spacing between liquid crystal micelles was measured in-situ. The liquid crystals studied were templated from different surfactants with varying structural characteristics. Micelles of a dilute surfactant solution were also subjected to elevated pressures of varying gas atmospheres. Detailed modelling of the in-situ SANS experiments revealed information of the size and shape of the micelles at a number of different pressures. Also reported in this thesis is the characterisation of mesoporous materials in the confined channels of larger porous materials. Periodic mesoporous organosilicas (PMOs) were synthesised within the channels of anodic alumina membranes (AAM) under different conditions, including drying rates and precursor concentrations. In-situ small angle x-ray scattering (SAXS) and transmission electron microscopy (TEM) was used to determine the pore morphology of the PMO within the AAM channels. PMO materials were also used as templates in the deposition of gold nanoparticles and subsequently used in the synthesis of germanium nanostructures. Polymer thin films were also employed as templates for the directed deposition of gold nanoparticles which were again used as seeds for the production of germanium nanostructures. A supercritical CO2 (sc-CO2) technique was successfully used during the production of the germanium nanostructures.