Adsorption in periodically ordered mesoporous organosilica materials studied by in situ small-angle X-ray scattering and small-angle neutron scattering.

Modified periodically ordered mesoporous organosilica materials were prepared starting from a recently introduced type of sol-gel precursor, containing both organic moieties and hydrolyzable Si-OR groups. In order to thoroughly characterize the mesoporosity and its accessibility, different probe gases were used in conventional gas adsorption experiments. Furthermore, in situ small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS) were applied to study the mesoporosity and the sorption processes, taking advantage of scattering contrast matching conditions. Thereby, the materials were characterized not only by different probe molecules but also at different temperatures (nitrogen at 77 K, dibromomethane at 290 K and perfluoropentane at 276 K). The comparison between the standard and in situ SAXS/SANS adsorption experiments revealed valuable information about the porosity and microstructure of the materials. It is demonstrated that the organic moieties are homogeneously distributed; that is, they do not phase-separate from silica on the nanometer scale.

Kinetics of nanoparticle reassembly mediated by UV-photolysis of surfactant.

Real-time reassembly of an ordered nanoparticle monolayer due to UV-photolysis of the surfactant shell of nanoparticles was observed. The technique of grazing-incidence small-angle X-ray scattering provided the possibility to track in situ the nanoparticle pair correlation function of the sample processed in a UV-ozone reactor. The analysis revealed a total shift of approximately 1 nm of the nanoparticle nearest-neighbor distance. The temporal evolution of the interparticle distance proved to be the first-order process governed by the UV-photolysis and described by a single-exponential decay function. The nanoparticles tend to agglomerate into a labyrinth-like structure with a typical length scale of some 30 nm.

Preservation of the morphology of a self-encapsulated thin titania film in a functional multilayer stack: an X-ray scattering study.

Tailoring of the titania morphology is achieved by the combination of a triblock copolymer, acting as structure-directing agent, and a sol-gel chemistry enabling the incorporation of the provided inorganic material (titania) into the selected phase of the triblock copolymer. Spin-coating of the solution on FTO-coated glass, followed by plasma etching and calcination of the thin film results in the formation of self-encapsulated crystalline titania nanostructures. The fabricated nanostructures are coated stepwise with dye, conductive polymers and gold forming a functional multilayer stack. An advanced small-angle scattering technique probing the sample with X-ray synchrotron radiation under grazing incidence (GISAXS) is employed for the characterization of the preparation route, as scattering allows accessing the structure inside the multilayers. The tailored titania morphology is preserved during the preparation route towards the functional multilayer stack of a photovoltaic demonstration cell. Two clearly distinguishable structures originate from the substrate and the titania templated by the triblock copolymer; hence the other layers induce no additional structures. Therefore, this investigation provides the evidence that the effort spent to tailor the morphology is justified by the preservation of the self-encapsulated titania morphology that is created by the structure-directing agent throughout the functional multilayer stack build-up.

Analysis of microporosity in ordered mesoporous hierarchically structured silica by combining physisorption with in situ small-angle scattering (SAXS and SANS).

The combination of physisorption experiments with simultaneous in situ small-angle X-ray and neutron scattering (SAXS/SANS) was used to elucidate the porosity in mesoporous silica with a trimodal pore structure. The material ("KLE-IL") contains spherical mesopores of 14 nm in diameter, worm-like mesopores (2-3 nm), and micropores, templated by a block copolymer and an ionic liquid surfactant, while the micropores originate from the hydrophilic block of the block copolymer. The main objective of the study was the quantification of the microporosity and the small mesopores and to find out if they are indeed located between the larger, spherical mesopores. Our in situ SAXS/SANS experiments took advantage of contrast matching of nitrogen (SANS, T = 77 K) and dibromomethane (SAXS, T = 290 K). By using the latter gas with a slightly larger kinetic diameter, it was possible to judge the accessibility of the pores under ambient conditions. The in situ experiments were supported by high-precision ex situ physisorption. Using suitable approaches for the SAXS/SANS analysis, it was possible to separate the content of the micropores and small mesopores.

Small angle x-ray scattering with a beryllium compound refractive lens as focusing optic.

At BW4 at HASYLAB a beryllium compound refractive lens (Be-CRL) is used for the focusing in small-angle x-ray scattering experiments. Using it provides the advantages of higher long-term stability and a much easier alignment compared to a setup with focusing mirrors. In our investigations presented here, we show the advantages of using a Be-CRL in small-angle and also ultra small-angle x-ray scattering. We investigated the beam characteristics at the sample position with respect to spot size and photon flux. The spot size is comparable to that of a setup with focusing mirrors but with a gain in flux and better long-term stability. It is also shown that plane mirrors are still necessary to suppress higher order energies passing the monochromator.

Grazing incidence small-angle X-ray scattering microtomography demonstrated on a self-ordered dried drop of nanoparticles.

We combine grazing-incidence small-angle X-ray scattering (GISAXS) with scanning X-ray microtomography to investigate the nanostructure in a dried gold/polystyrene nanocomposite drop. Local GISAXS structure factors are reconstructed at each position on the surface of this two-dimensionally heterogeneous sample with 30 microm pixel size. Evidence for four types of self-assembled colloidal crystalline structures is provided by the reconstructed data of the drop demonstrating the feasibility of the method.

Structures of regenerated cellulose films revealed by grazing incidence small-angle x-ray scattering.

The characteristic in-plane length scales of ultrathin films of regenerated cellulose are measured using noncontact atomic force microscopy (NC-AFM) and grazing incidence small-angle x-ray scattering (GISAXS) in ambient atmosphere and under various humidity conditions. The aim is to elucidate the structural basis for the excellent compatibility of cellulose supports to planar lipid membranes. Films are deposited on silicon wafers by Langmuir-Blodgett (LB) transfer and spin coating. NC-AFM height profiles and the resulting calculated power spectral density functions indicate that both kinds of cellulose films have almost identical root-mean-square roughness values (0.7-0.8 nm) and very similar characteristic length scales (32 nm), respectively. GISAXS measurements, both above and below the critical angle of total external reflection, show that the dominant length scales in the bulk and near the surface of the films are comparable ( approximately 50 nm). The origin of these length scales can be attributed to the bundle of rodlike molecules of cellulose that result during the regeneration process (i.e., as a consequence of the cleavage of the silyl side chains of trimethylsilylcellulose). Exposure of the cellulose samples to various humidities shows that above a relative humidity of 97% a significant swelling of the films occurs, which is consistent with our previous findings. The swelling of films with more than 30 LB monolayers of cellulose induces a remarkable out-of-plane rearrangement of the cellulose bundles, due to a reduced influence of the solid substrate compared to thinner films with only eight to ten LB monolayers.

Order causes secondary Bragg peaks in soft materials.

Highly ordered soft materials exhibit Bragg peaks that cannot be indexed assuming homogeneous crystal structures. Their origin has been attributed to changes in the crystal structure that are induced by the ordering process such as by application of external fields. This would restrict the use for the generation of highly ordered nano- and microstructured materials where a homogeneous crystal structure is a key requirement. Here, we demonstrate that these Bragg peaks are an inherent property of homogeneous ordered soft materials related to the finite coherence of their crystalline lattice. Their consideration allows a detailed and quantitative analysis of the diffraction patterns of seemingly unrelated materials such as lyotropic liquid-crystalline phases, mesoporous materials, colloidal dispersions, block copolymers, electrorheological fluids and photonic crystals. It further enables us to develop a concise picture of order, line density, field-induced orientation and epitaxial relations for soft-material lattices.