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41 records · Page 3

Low gravity synthesis of polymers with controlled molecular configuration

Heterogeneous chemical systems have been studied for the synthesis of isotactic polypropylene in order to establish baseline parameters for the reaction process and to develop sensitive and accurate methods of analysis. These parameters and analytical methods may be used to make a comparison between the polypropylene obtained at one g with that of zero g (gravity). Baseline reaction parameters have been established for the slurry (liquid monomer in heptane/solid catalyst) polymerization of propylene to yield high purity, 98% isotactic polypropylene. Kinetic data for the slurry reaction showed that a sufficient quantity of polymer for complete characterization can be produced in a reaction time of 5 min; this time is compatible with that available on a sounding rocket for a zero-g simulation experiment. The preformed (activated) catalyst was found to be more reproducible in its activity than the in situ formed catalyst.

Heimbuch, A. H.↗

The study of excited oxygen molecule gas species production and quenching on thermal protection system materials

The detection of excited oxygen and ozone molecules formed by surface catalyzed oxygen atom recombination and reaction was investigated by laser induced fluorescence (LIF), molecular beam mass spectrometric (MBMS), and field ionization (FI) techniques. The experiment used partially dissociated oxygen flows from a microwave discharge at pressures in the range from 60 to 400 Pa or from an inductively coupled RF discharge at atmospheric pressure. The catalyst materials investigated were nickel and the reaction cured glass coating used for Space Shuttle reusable surface insulation tiles. Nonradiative loss processes for the laser excited states makes LIF detection of O2 difficult such that formation of excited oxygen molecules could not be detected in the flow from the microwave discharge or in the gaseous products of atom loss on nickel. MBMS experiments showed that ozone was a product of heterogeneous O atom loss on nickel and tile surfaces at low temperatures and that ozone is lost on these materials at elevated temperatures. FI was separately investigated as a method by which excited oxygen molecules may be conveniently detected. Partial O2 dissociation decreases the current produced by FI of the gas.

Nordine, Paul C.↗

Calorimetry, activity, and micro-FTIR analysis of CO chemisorption, titration, and oxidation on supported Pt

The value of in situ analysis on CO chemisorption, titration and oxidation over supported Pt catalysts using calorimetry, catalytic and micro-FTIR methods is illustrated using silica- and titania-supported samples. Isothermal CO-O and O2-CO titrations have not been widely used on metal surfaces and may be complicated if some oxide supports are reduced by CO titrant. However, they can illuminate the kinetics of CO oxidation on metal/oxide catalysts since during such titrations all O and CO coverages are scanned as a function of time. There are clear advantages in following the rates of the catalyzed CO oxidation via calorimetry and gc-ms simultaneously. At lower temperatures the evidence they provide is complementary. CO oxidation and its catalysis of CO oxidation have been extensively studied with hysteresis and oscillations apparent, and the present results suggest the benefits of a combined approach. Silica support porosity may be important in defining activity-temperature hysteresis. FTIR microspectroscopy reveals the chemical heterogeneity of the catalytic surfaces used; it is interesting that the evidence with regard to the dominant CO surface species and their reactivities with regard to surface oxygen for present oxide-supported Pt are different from those seen on graphite-supported Pt.

Sermon, Paul A.↗

Catalytic Combustion of Propane/Air Mixtures on Platinum

A honeycomb catalyst of platinum (4.2 kg/cu m loading) over cordierite, with gamma-alumina washcoat, a cross section of 2.4 x 2.4 sq cm, a length of 7.6 cm, and a characteristic channel diameter of 1.4 mm is used as a steady flow reactor. Measurements are made with C3H8/air mixtures at 650 to 800 K inlet temperatures, 110 KPa pressure, 10 to 40 m/s inlet velocity, 0.19 to 0.32 equivalence ratios, and approximately 1.5 mole percent water content. The measured quantities are the substrate tempeature at ten axial locations, the exhaust gas temperature, the exhaust concentrations of CO, CO2, O2, and total hydrocarbons, and the pressure drop across the monolith. The measured quantities are compared with those computed with a two-dimensional steady-state model for axial and radial convection and diffusion of mass, momentum, energy and homogeneous (three overall reactions) and heterogeneous (infinitely fast) reactions. It is found that, under the tested conditions, most of the fuel is converted to CO2 and H2O at the surface. Gas-phase reactions tend rapidly to become more important as the temperature and equivalence ratio are increased and the flow velocity is decreased. Surface fuel conversion is much more rapid than fuel diffusion, resulting in diffusion-controlled oxidation.

Bruno, C.↗

Feasibility of Ultraviolet Light Emitting Diodes as an Alternative Light Source for Photocatalysis

The objective of this study was to determine whether ultraviolet light emitting diodes (UV-LEDs) could serve as an alternative photon source efficiently for heterogeneous photocatalytic oxidation (PCO). An LED module consisting of 12 high-power UV-A LEDs was designed to be interchangeable with a UV-A fluorescent black light blue (BLB) lamp in a Silica-Titania Composite (STC) packed bed annular reactor. Lighting and thermal properties were characterized to assess the uniformity and total irradiant output. A forward current of (I(sub F)) 100 mA delivered an average irradiance of 4.0 m W cm(exp -2), which is equivalent to the maximum output of the BLB, but the irradiance of the LED module was less uniform than that of the BLB. The LED- and BLB-reactors were tested for the oxidization of 50 ppmv ethanol in a continuous flow-through mode with 0.94 sec space time. At the same irradiance, the UV-A LED reactor resulted in a lower PCO rate constant than the UV-A BLB reactor (19.8 vs. 28.6 nM CO2 sec-I), and consequently lower ethanol removal (80% vs. 91%) and mineralization efficiency (28% vs. 44%). Ethanol mineralization increased in direct proportion to the irradiance at the catalyst surface. This result suggests that reduced ethanol mineralization in the LED- reactor could be traced to uneven irradiance over the photocatalyst, leaving a portion of the catalyst was under-irradiated. The potential of UV-A LEDs may be fully realized by optimizing the light distribution over the catalyst and utilizing their instantaneous "on" and "off' feature for periodic irradiation. Nevertheless, the current UV-A LED module had the same wall plug efficiency (WPE) of 13% as that of the UV-A BLB. These results demonstrated that UV-A LEDs are a viable photon source both in terms of WPE and PCO efficiency.

Levine, Langanf H.↗