RESUMO
The effect of repeated cycles of water adsorption/desorption on the structural stability of ordered mesoporous silica SBA-15 is studied by small-angle x-ray scattering (SAXS). In situ sorption measurements are conducted using a custom-built sorption apparatus in connection with a laboratory SAXS setup. Two striking irreversible changes are observed in the sorption isotherms as derived from the integrated SAXS intensity. First, the capillary condensation pressure shifts progressively to lower relative pressure values with increasing number of sorption cycles. This effect is attributed to chemisorption of water at the silica walls, resulting in a change of the fluid-wall interaction. Second, the sorption cycles do not close completely at vanishing vapour pressure, suggesting that progressively more water remains trapped within the porous material after each cycle. This effect is interpreted to be the result of an irreversible collapse of parts of mesopores, originating from pore wall deformation due to the large Laplace pressure of water acting on the pore walls at capillary condensation and capillary evaporation.
RESUMO
A simple explanation is given for the low-temperature density minimum of water confined within cylindrical pores of ordered nanoporous materials of different pore size. The experimental evidence is based on combined data from in-situ small-angle scattering of X-rays (SAXS) and neutrons (SANS), corroborated by additional wide-angle X-ray scattering (WAXS). The combined scattering data cannot be described by a homogeneous density distribution of water within the pores, as was originally suggested from SANS data alone. A two-step density model reveals a wall layer covering approximately two layers of water molecules with higher density than the residual core water in the central part of the pores. The temperature-induced changes of the scattering signal from both X-rays and neutrons are consistent with a minimum of the average water density. We show that the temperature at which this minimum occurs depends monotonically on the pore size. Therefore we attribute this minimum to a liquid-solid transition of water influenced by confinement. For water confined in the smallest pores of only 2 nm in diameter, the density minimum is explained in terms of a structural transition of the surface water layer closest to the hydrophilic pore walls.
RESUMO
A two-step focusing set-up combining a Fresnel zone plate with an ellipsoidal capillary is presented. It is shown that, in addition to the anticipated gain in flux, the employment of the prefocusing micro-optic makes optimal use of the elliptical shape of the capillary by almost eliminating aberrations. A small cross section of the prefocused beam allows a tiny fraction of the capillary surface to be selected, thus reducing the influence of slope errors. An X-ray beam with a 15 keV energy was focused down to a spot size as small as 250 nm, demonstrating the best value that has been achieved up to now for single-bounce capillaries. The use of an ellipsoidal capillary as a micromirror under off-axis illumination by microfocusing optics may open up new opportunities in nanofocusing developments.
RESUMO
A single-bounce capillary with an ellipsoidal shape has been used for two-step focusing in combination with a Fresnel zone plate (FZP). The FZP serves as a first microfocusing element and produces a demagnified micrometer image of the source, before the elliptical capillary makes a last final compression of the beam. With 15 keV X-rays from the European Synchrotron Radiation Facility BM5 bending magnet, the two-step demagnification system produced a focus of about 250 nm with a gain of more than 1000. The use of an ellipsoidal capillary as a micro-mirror under off-axis illumination using micro-prefocusing optics might open up new opportunities in nanofocusing developments.