Polymer‐TiO2 Nanocomposites: A Route Towards Visually Transparent Broadband UV Filters and High Refractive Index Materials

Colloids of TiO₂, where rutile was the only crystal modification which could be detected, with ca. 2.5 nm average particle diameter were synthesized by hydrolysis of TiCl₄ in acidic solutions. The as‐prepared particles were incorporated in polymers such as poly(vinyl alcohol) (PVAL), partially hydrolyzed poly(vinyl acetate) (PVAC88), polyvinylpyrrolidone, and poly(4‐vinylpyridine). Nanocomposites transparent in the visible range were obtained. The highest TiO₂ contents in such materials were achieved with PVAL and PVAC88, with TiO₂ contents of ca. 35 wt.‐% (i.e. 10.5 vol.‐%). In particular, the nanocomposites with TiO₂ contents above 24 wt.‐% acted as efficient UV filters for radiation up to ca. 360 nm. At very low TiO₂ contents, an absorption maximum of the embedded TiO₂ particles was observed at 225 nm with an extinction coefficient of 140 000 cm^?1 and a full width at half maximum of 45 nm, i.e. not only the absorption at the maximum at 225 nm but also at the flank of this band contributed significantly to the broadband UV absorption in the nanocomposites at higher TiO₂ fractions. The incorporation of TiO₂ enhanced the refractive index of the nanocomposites: for instance a refractive index of 1.609 was measured for a nanocomposite comprising 10.5 vol.‐% TiO₂ in PVAL, compared with 1.521 for the pristine polymer.

TEM image of a section of a nanocomposite of poly(vinyl alcohol) and 11 wt.‐% TiO₂ (appearing dark).     

Effects of aerobic and anaerobic conditions on P, N, Fe, Mn, and Hg accumulation in waters overlaying profundal sediments of an oligo-mesotrophic lake

Concentrations of key nutrients and metals in water overlaying profundal sediments were evaluated in replicate experimental chambers containing undisturbed sediment-water interface samples from Deer Lake, an oligo-mesotrophic lake in eastern Washington. Chambers were incubated under three sequential phases: aerobic (21d), anaerobic (27d), and second aerobic (14d). In general, nutrients and metals in chamber water were lower under aerobic versus anaerobic conditions. However, in some cases compounds anticipated to appear only under anaerobic conditions, including ammonia, phosphate, and manganese, were observed during aerobic conditions. Correlation analysis elucidated a number of interactions between compounds. Phosphate correlated significantly (p<0.05) with iron during all incubation phases, suggesting that phosphorus cycling was controlled by iron. Cycling of nitrate and ammonia was tightly and significantly coupled under aerobic conditions. During both aerobic phases, nitrate increased while ammonia decreased, likely as a result of biological nitrification. Finally, mercury appeared during mildly reducing conditions and showed a significant correlation with manganese during the anaerobic phase, suggesting that Mn oxide reduction was the source of Hg in chamber water.     

Determination of Bridging Stresses in Reinforced Al2O3

The determination of bridging stresses by evaluation of crack opening profiles is outlined for a whisker-reinforced alumina. The application of the fracture mechanics weight function procedure results in an integral equation between bridging stresses and crack opening displacements. Its solution provides the bridging stress relation.     

A model of multi-purpose shopping trip behavior

Existing utility-based models of complex choice behavior do not adequately deal with the interdependencies of chained choices. In this paper, we introduce a model of multi-purpose shopping which is aimed at overcoming this shortcoming. In the proposed model, dependencies between choices within as well as between trips are covered by a recursive definition of trip utility. The standard log-likelihood estimation procedure is used to calibrate the model. Simulation experiments show that estimation results are satisfactorily accurate and robust. Comparison of the model to a conventional choice model using simulated data indicates that even low tendencies to make multi-purpose trips have a significant influence on predicted destination choice. Furthermore, it is shown that conventional models do not satisfactorily predict simulated multi-purpose behavior.     

Influence of Short-Chain Carboxylic Acids on the Mechanical Properties and Structure of Coagulated Alumina Suspensions

Three different short-chained carboxylic acids, formic, acetic, and propionic acid, were compared as additives to increase the green strength of wet particle networks produced with the direct coagulation casting process, which allows the internal coagulation of a suspension. Small acid additions do not alter the favorable low viscosity of the stabilized slurry, and yet increase the compressive strength of wet coagulated bodies. The strengthening effect increases with increasing chain length of the carboxylic acid. The maximum effect was observed upon addition of propionic acid (0.3 wt% to alumina), which resulted in a sixfold increase in compressive strength of wet coagulated bodies compared with that without propionic acid.     

Crack-Tip Structure in Soda–Lime–Silicate Glass

The topology of crack tips in soda–lime–silicate glass was investigated using atomic force microscopy (AFM). Studies were conducted on cracks that were first propagated in water and then subjected to stress intensity factors either at or below the crack growth threshold. Exposure to loads at the crack growth threshold resulted in long delays to restart crack growth after increasing the stress intensity factor to higher values. After breaking the fracture specimen in two, the "upper" and "lower" fracture surfaces were mapped and compared using AFM. Fracture surfaces matched to an accuracy of better than 0.5 nm normal to the fracture plane and 5 nm within the fracture plane. Displacements between the upper and lower fracture surfaces that developed after a critical holding time were independent of distance from the crack tip, and increased with holding time. Despite the surface displacement, crack tips appeared to be sharp. Results are discussed in terms of a hydronium ion–alkali ion exchange along the crack surfaces and corrosion of the glass surface near the crack tip by hydroxyl ions.     

Image formation and tomogram reconstruction in optical coherence microscopy

In this work we present a model for image formation in optical coherence microscopy. In the spectral domain detection, each wavenumber has a specific coherent transfer function that samples a different part of the object's spatial frequency spectrum. The reconstruction of the tomogram is usually accurate only in a short depth of field. Using numerical simulations based on the developed model, we identified two distinct mechanisms that influence the signal of out-of-focus sample information. Besides the lateral blurring induced through defocusing, an additional axial envelope contributing equally to the signal degradation was found.     

Linear patterning of mesenchymal condensations is modulated by geometric constraints

The development of the vertebral column starts with the formation of a linear array of mesenchymal condensations, forming the blueprint for the eventual alternating pattern of bone and cartilage. Despite growing insight into the molecular mechanisms of morphogenesis, the impact of the physical aspects of the environment is not well understood. We hypothesized that geometric boundary conditions may play a pivotal role in the linear patterning of condensations, as neighbouring tissues provide physical constraints to the cell population. To study the process of condensation and the patterning thereof under tightly controlled geometric constraints, we developed a novel in vitro model that combines micropatterning with the established micromass assay. The spacing and alignment of condensations changed with the width of the cell adhesive patterns, a phenomenon that could not be explained by cell availability alone. Moreover, the extent of chondrogenic commitment was increased on substrates with tighter geometric constraints. When the in vivo pattern of condensations was investigated in the developing vertebral column of chicken embryos, the measurements closely fit into the quantitative relation between geometric constraints and inter-condensation distance found in vitro. Together, these findings suggest a potential role of geometric constraints in skeletal patterning in a cellular process of self-organization.     

Mixed‐Mode Stress Intensity Factors for Partially Opened Cracks

Failure considerations under mixed-mode loading require knowledge about the influence of friction between partially closed crack faces in the case of a negative mode-I stress intensity factor. A simple relation is derived, which allowes to compute friction contributions to the mode-II stress intensity factor K_II for the case of negative mode-I stress intensity factors K_I. The relation is exact for the limit case of an edge crack in a half-space. It can be shown that small cracks in finite bodies can also be described with sufficient accuracy.