Technological solution for the automatic replacement of the catalytic filaments in HWCVD

The degradation of the catalytic filaments is the main factor limiting the industrial implementation of the hot wire chemical vapor deposition (HWCVD) technique. Up to now, no solution has been found to protect the catalytic filaments used in HWCVD without compromising their catalytic activity. Probably, the definitive solution relies on the automatic replacement of the catalytic filaments. In this work, the results of the validation tests of a new apparatus for the automatic replacement of the catalytic filaments are reported. The functionalities of the different parts have been validated using a 0.2 mm diameter tungsten filament under uc-Si:H deposition conditions.

Catalytic gasification of glycerol in supercritical water

The conversion of glycerol in supercritical water (SCW) was studied at 510-550 °C and a pressure of 350 bars using both a bed of inert and non-porous ZrO2 particles (hydrothermal experiments), and a bed of a 1% Ru/ZrO2 catalyst. Experiments were conducted with a glycerol concentration of 5 wt% in a continuous isothermal fixed-bed reactor at a residence time between 2 and 10 s. Hydrothermolysis of glycerol formed water-soluble products such as acetaldehyde, acetic acid, hydroxyacetone and acrolein, and gases like H2, CO and CO2. The catalyst enhanced the formation of acetic acid, inhibited the formation of acrolein, and promoted gasification of the glycerol decomposition products. Hydrogen and carbon oxides were the main gases produced in the catalytic experiments, with minor amounts of methane and ethylene. Complete glycerol conversion was achieved at a residence time of 8.5 s at 510 °C, and at around 5 s at 550 °C with the 1 wt% Ru/ZrO2 catalyst. The catalyst was not active enough to achieve complete gasification since high yields of primary products like acetic acid and acetaldehyde were still present. Carbon balances were between 80 and 60% in the catalytic experiments, decreasing continuously as the residence time was increased. This was attributed partially to the formation of methanol and acetaldehyde, which were not recovered and analyzed efficiently in our set-up, but also to the formation of carbon deposits. Carbon deposition was not observed on the catalyst particles but on the surface of the inert zirconia particles, especially at high residence time. This was related to the higher concentration of acetic acid and other acidic species in the catalytic experiments, which may polymerize to form tar-like carbon precursors. Because of carbon deposition, hydrogen yields were significantly lower than expected; for instance at 550 °C the hydrogen yield potential was only 50% of the stoichiometric value.

20 Myr of eccentricity paced lacustrine cycles in the Cenozoic Ebro Basin

Long-period orbital forcing is a crucial component of the major global climate shifts during the Cenozoic as revealed in marine pelagic records. A complementary regional perspective of climate change can be assessed from internally drained lake basins, which are directly affected by insolation and precipitation balance. The Ebro Basin in northeastern Iberia embraces a 20 Myr long continuous sedimentary record where recurrent expansions and retractions of the central lacustrine system suggest periodic shifts of water balance due to orbital oscillations. In order to test climatic (orbital) forcing a key-piece of the basin, the Los Monegros lacustrine system, has been analyzed in detail. The cyclostratigraphic analysis points to orbital eccentricity as pacemaker of short to long-term lacustrine sequences, and reveals a correlation of maxima of the 100-kyr, 400-kyr and 2.4-Myr eccentricity cycles with periods of lake expansion. A magnetostratigraphy-based chronostratigraphy of the complete continental record allows further assessing long-period orbital forcing at basin scale, a view that challenges alternate scenarios where the stratigraphic architecture in foreland systems is preferably associated to tectonic processes. We conclude that while the location of lacustrine depocenters reacted to the long-term tectonic-driven accommodation changes, shorter wavelenght oscillations of lake environments, still million-year scale, claims for a dominance of orbital forcing. We suggest a decoupling between (tectonic) supply-driven clastic sequences fed from basin margins and (climatic) base level-driven lacustrine sequences in active settings with medium to large sediment transfer systems.