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Highly mismatched crystalline and amorphous GaN(1-x)As(x) alloys in the whole composition range

Description: Alloying is a commonly accepted method to tailor properties of semiconductor materials for specific applications. Only a limited number of semiconductor alloys can be easily synthesized in the full composition range. Such alloys are, in general, formed of component elements that are well matched in terms of ionicity, atom size, and electronegativity. In contrast there is a broad class of potential semiconductor alloys formed of component materials with distinctly different properties. In most instances these mismatched alloys are immiscible under standard growth conditions. Here we report on the properties of GaN1-xAsx, a highly mismatched, immiscible alloy system that was successfully synthesized in the whole composition range using a nonequilibrium low temperature molecular beam epitaxy technique. The alloys are amorphous in the composition range of 0.17<x<0.75 and crystalline outside this region. The amorphous films have smooth morphology, homogeneous composition, and sharp, well defined optical absorption edges. The band gap energy varies in a broad energy range from ~;;3.4 eV in GaN to ~;;0.8 eV at x~;;0.85. The reduction in the band gap can be attributed primarily to the downward movement of the conduction band for alloys with x>0.2, and to the upward movement of the valence band for alloys with x<0.2. The unique features of the band structure offer an opportunity of using GaN1-xAsx alloys for various types of solar power conversion devices.
Date: August 29, 2009
Creator: Yu, K. M.; Novikov, S. V.; Broesler, R.; Demchenko, I. N.; Denlinger, J. D.; Liliental-Weber, Z. et al.
Partner: UNT Libraries Government Documents Department

EFRT M-12 Issue Resolution: Solids Washing

Description: Pacific Northwest National Laboratory (PNNL) has been tasked by Bechtel National Inc. (BNI) on the River Protection Project-Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed, constructed, and operated as part of a plan to respond to issue M12, “Undemonstrated Leaching Processes.” The PEP is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes. The PEP replicates the WTP leaching processes using prototypic equipment and control strategies. Two operating scenarios were evaluated for the ultrafiltration process (UFP) and leaching operations. The first scenario has caustic leaching performed in the UFP-VSL-T01A/B ultrafiltration feed vessels, identified as Integrated Test A. The second scenario has caustic leaching conducted in the UFP-VSL-T02A ultrafiltration feed preparation vessel, identified as Integrated Test B. Washing operations in PEP Integrated Tests A and B were conducted successfully as per the approved run sheets. However, various minor instrumental problems occurred, and some of the process conditions specified in the run sheet were not met during the wash operations, such as filter-loop flow-rate targets not being met. Five analytes were selected based on full solubility and monitored in the post-caustic-leach wash as successful indicators of washing efficiency. These were aluminum, sulfate, nitrate, nitrite, and free hydroxide. Other analytes, including sodium, oxalate, phosphate, and total dissolved solids, showed indications of changing solubility; therefore, they were unsuitable for monitoring washing efficiency. In the post-oxidative-leach wash, two analytes with full solubility were selected as suitable indicators of washing efficiency. These were chromium and oxalate. Other analytes, including sodium, manganese, nitrate, and total dissolved solids, showed indications of changing solubility; therefore, they were unsuitable for monitoring washing efficiency. An ...
Date: August 14, 2009
Creator: Baldwin, David L.; Schonewill, Philip P.; Toth, James J.; Huckaby, James L.; Eslinger, Paul W.; Hanson, Brady D. et al.
Partner: UNT Libraries Government Documents Department

Transuranic Contamination in Sediment and Groundwater at the U.S. DOE Hanford Site

Description: A review of transuranic radionuclide contamination in sediments and groundwater at the DOE’s Hanford Site was conducted. The review focused primarily on plutonium-239/240 and americium-241; however, other transuranic nuclides were discussed as well, including neptunium-237, plutonium-238, and plutonium-241. The scope of the review included liquid process wastes intentionally disposed to constructed waste disposal facilities such as trenches and cribs, burial grounds, and unplanned releases to the ground surface. The review did not include liquid wastes disposed to tanks or solid wastes disposed to burial grounds. It is estimated that over 11,800 Ci of plutonium-239, 28,700 Ci of americium-241, and 55 Ci of neptunium-237 have been disposed as liquid waste to the near surface environment at the Hanford Site. Despite the very large quantities of transuranic contaminants disposed to the vadose zone at Hanford, only minuscule amounts have entered the groundwater. Currently, no wells onsite exceed the DOE derived concentration guide for plutonium-239/240 (30 pCi/L) or any other transuranic contaminant in filtered samples. The DOE derived concentration guide was exceeded by a small fraction in unfiltered samples from one well (299-E28-23) in recent years (35.4 and 40.4 pCi/L in FY 2006). The primary reason that disposal of these large quantities of transuranic radionuclides directly to the vadose zone at the Hanford Site has not resulted in widespread groundwater contamination is that under the typical oxidizing and neutral to slightly alkaline pH conditions of the Hanford vadose zone, transuranic radionuclides (plutonium and americium in particular) have a very low solubility and high affinity for surface adsorption to mineral surfaces common within the Hanford vadose zone. Other important factors are the fact that the vadose zone is typically very thick (hundreds of feet) and the net infiltration rate is very low due to the desert climate. In some cases where transuranic radionuclides have ...
Date: August 20, 2009
Creator: Cantrell, Kirk J.
Partner: UNT Libraries Government Documents Department

Mild Catalytic methods for Alkyl-Alkyl Bond Formation

Description: Overview of Research Goals and Accomplishments for the Period 07/01/06 – 06/30/07: Our overall research goal is to transform the rapidly emerging synthetic chemistry involving alkyl-alkyl cross-couplings into more of a mechanism-based field so that that new, rationally-designed catalysts can be performed under energy efficient conditions. Our specific objectives for the previous year were 1) to obtain a proper electronic description of an active catalyst for alkyl-alkyl cross-coupling reactions and 2) to determine the effect of ligand structure on the rate, scope, selectivity, and functional group compatibility of C(sp3)-C(sp3) cross-coupling catalysis. We have completed both of these initial objectives and established a firm base for further studies. The specific significant achievements of the current grant period include: 1) we have performed magnetic and computational studies on (terpyridine)NiMe, an active catalyst for alkyl-alkyl cross couplings, and have discovered that the unpaired electron resides heavily on the terpyridine ligand and that the proper electronic description of this nickel complex is a Ni(II)-methyl cation bound to a reduced terpyridine ligand; 2) we have for the first time shown that alkyl halide reduction by terpyridyl nickel catalysts is substantially ligand based; 3) we have shown by isotopic labeling studies that the active catalyst (terpyridine)NiMe is not produced via a mechanism that involves the formation of methyl radicals when (TMEDA)NiMe2 is used as the catalyst precursor; 4) we have performed an extensive ligand survey for the alkyl-alkyl cross-coupling reactions and have found that electronic factors only moderately influence reactivity in the terpyridine-based catalysis and that the most dramatic effects arise from steric and solubility factors; 5) we have found that the use of bis(dialkylphosphino)methanes as ligands for nickel does not produce active catalysts for cross-coupling but rather leads to bridging hydride complexes of varying geometries; 6) we have determined that the geometry of aforementioned bridging ...
Date: August 10, 2009
Creator: Vicic, David A
Partner: UNT Libraries Government Documents Department