The relationship between nanosilica dispersion degree and the tensile properties of polyurethane nanocomposites

The tensile properties and structure of silica-based polyurethane (PU) nanocomposites were parametrically studied as a function of silica type and weight concentration, polyol OH number, and mixing methods. The variation of the silica functionalization groups (from silanols to silazanes) had a relevant effect on dispersion. An elevated interparticle distance of the silica agglomerates improved substantially the tensile strength (from 44.3 to 82.8 MPa) and strain to failure (from 3.0 to 7.95) while maintaining elastic modulus (from 2.08 to 2.31 GPa) with respect to the neat PU matrix. Polyol’s with different OH numbers have shown to dramatically modify the silica dispersion degree by the modification of the stability of the colloidal dispersion. An increase of its value deteriorated dispersion and the tensile properties of the nanocomposites. The effect of three dispersion methods (ultrasonic dispersion, high shear mixing, and tip sonication) has shown to have a relative effect on the reduction of agglomerate size and the interparticle distance. High power sonication methods were more effective in reducing agglomerate size in contrast to shear methods. Classical theories of colloidal dispersion (Derjaguin, Landau, Verwey, and Overbeek) have been able to explain the correlation between the silica aggregation state and the final tensile properties of the nanocomposite.     

Potassium-intercalated H(2)Pc films: Alkali-induced electronic and geometrical modifications

X-ray spectroscopy studies of potassium intercalated metal-free phthalocyanine multilayers adsorbed on Al(110) have been undertaken. Photoelectron spectroscopy measurements show the presence of several charge states of the molecules upon K intercalation, due to a charge transfer from the alkali. In addition, the comparison of valence band photoemission spectra with the density functional theory calculations of the density of states of the H(2)Pc(-) anion indicates a filling of the formerly lowest unoccupied molecular orbital by charge transfer from the alkali. This is further confirmed by x-ray absorption spectroscopy (XAS) studies, which show a decreased density of unoccupied states. XAS measurements in different experimental geometries reveal that the molecules in the pristine film are standing upright on the surface or are only slightly tilted away from the surface normal but upon K intercalation, the molecular orientation is changed in that the tilt angle of the molecules increases.     

Molecular orientation of thiol-derivatized tetraphenylporphyrin on gold studied by XPS and NEXAFS

Tetraphenylporphyrins bearing four linkers consisting of thioacetyl-functionalized carbon chains were immobilized on a gold surface via thiolate-gold bonds using two different preparation routes. The structure of these molecular layers was characterized in detail with synchrotron radiation based core-level spectroscopy, X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The results show that the geometry of the molecular layers and the number of linkers that bind to the gold surface depends on the preparation schemes. The deprotection of the linkers through removal of the terminal acetyl group before the molecular adsorption (deprotected systems) resulted in porphyrins bound to the gold surface with on the average three linkers, their normal axis being tilted ∼38° with respect to the surface normal. On the other hand, porphyrin layers prepared directly with the acetyl group still in place on the linkers (protected systems) are made of molecules bound to the gold surface via two linkers on the average. The resulting orientation is more upright, with the normal axis of the porphyrin plane tilted ∼50° with respect to the surface normal. Moreover, NEXAFS measurements revealed that the acetyl deprotected porphyrin layers have a higher degree of ordering than the protected systems.     

Measurement of the 20 and 90 keV resonances in the 18O(p,alpha)15N reaction via the Trojan horse method

The 18O(p,alpha)15N reaction is of primary importance in several astrophysical scenarios, including fluorine nucleosynthesis inside asymptotic giant branch stars as well as oxygen and nitrogen isotopic ratios in meteorite grains. Thus the indirect measurement of the low energy region of the 18O(p,alpha)15N reaction has been performed to reduce the nuclear uncertainty on theoretical predictions. In particular the strength of the 20 and 90 keV resonances has been deduced and the change in the reaction rate evaluated.     

Effect of ethylene-co-vinyl acetate-glycidylmethacrylate and cellulose microfibers on the thermal,rheological and biodegradation properties of poly(lactic acid) based systems

The properties and biodegradation behavior of blends of poly(lactic acid) (PLA) and ethylene-vinyl acetate-glycidylmethacrylate copolymer (EVA-GMA), and their composites with cellulose microfibers (CF) were investigated. The blends and composites were obtained by melt mixing and the morphology, phase behavior, thermal and rheological properties of PLA/EVA-GMA blends and PLA/EVA-GMA/CF composite films were investigated as a function of the composition. The disintegrability in composting conditions was examined by means of morphological, thermal and chemical analyses to gain insights into the post-use degradation processes. The results indicated a good compatibility of the two polymers in the blends with copolymer content up to 30 wt.%, while at higher EVA-GMA content a phase separation was observed. In the composites, the presence of EVA-GMA contributes to improve the interfacial adhesion between cellulose fibers and PLA, due to interactions of the epoxy groups of GMA with hydroxyls of CF. The addition of cellulose microfibers in PLA/EVA-GMA system modifies the rheological behavior, since complex viscosity increased in presence of fibers and decreased with an increase in frequency. Disintegration tests showed that the addition of EVA-GMA influence the PLA disintegration process, and after 21 days in composting conditions, blends and composites showed faster degradation rate in comparison with neat PLA due to the different morphologies induced by the presence of EVA-GMA and CF phases able to allow a faster water diffusion and an efficient PLA degradation process.     

Molecular ordering in isonicotinic acid on rutile TiO2(110) investigated with valence band photoemission

The adsorption of isonicotinic acid on rutile TiO(2)(110) has been investigated using synchrotron-based valence band photoemission. Structural ordering in multilayer films of the molecules is found to give rise to a strong angular dependence in the valence band intensities when measured using linearly polarized radiation. Molecular ordering in this case is proposed to be induced by intermolecular hydrogen bonding which is found to be highly dependent upon the deposition rate of the isonicotinic acid. Through comparison of the experimental data with density functional calculated valence band spectra of hydrogen-bonded isonicotinic acid molecules, we can account for the angular dependence in terms of the spatial distribution of the molecular orbitals.