Magnesium aryloxides were prepared in a variety of solvents through the reaction of dibutyl magnesium with sterically varied aryl alcohols: 2,6-dimethylphenol (H-DMP), 2,6-diisopropylphenol (H-DIP), and 2,4,6-trichlorophenol (H-TCP). Upon using a sufficiently strong Lewis-basic solvent, the monomeric species Mg(DMP){sub 2}(py){sub 3} (1, py = pyridine), Mg(DIP){sub 2}(THF){sub 3}, (2a, THF = tetrahydrofuran) Mg(TCP){sub 2}(THF){sub 3} (3) were isolated. Each of these complexes possesses a five-coordinate magnesium that adopts a trigonal bipyramidal geometry. In the absence of a Lewis base, the reaction with H-DIP yields a soluble trinuclear complex, [Mg(DIP){sub 2}]{sub 3} (2b). The Mg metal centers in 2b adopt a linear arrangement with a four-coordinate central metal while the outer metal centers are reduced to just three-coordinate. Solution spectroscopic methods suggest that while 2b remains intact, the monomeric species (1, 2a, and 3) are involved in equilibria, which facilitate intermolecular ligand transfer.

The syntheses, crystal structures and some properties of {alpha}- and {beta}-ZnHPO{sub 3}{center_dot}N{sub 4}C{sub 2}H{sub 4} are reported. These two polymorphs are the first organically-templated hydrogen phosphites. They are built up from vertex-sharing HPO{sub 3} pseudo pyramids and ZnO{sub 3}N tetrahedra, where the Zn-N bond represents a direct link between zinc and the neutral 2-cyanoguanidine template. {alpha}-ZnHPO{sub 3}{center_dot}N{sub 4}C{sub 2}H{sub 4} is built up from infinite layers of vertex-sharing ZnO{sub 3}N and HPO{sub 3} groups forming 4-rings and 8-rings. {beta}-ZnHPO{sub 3}{center_dot}N{sub 4}C{sub 2}H{sub 4} has strong one-dimensional character, with the polyhedral building units forming 4-ring ladders. Similarities and differences to related zinc phosphates are discussed. Crystal data: {alpha}-ZnHPO{sub 3}{center_dot}N{sub 4}C{sub 2}H{sub 4}, M{sub r} = 229.44, monoclinic, P2{sub 1}/c, a = 9.7718 (5) {angstrom}, b = 8.2503 (4) {angstrom}, c = 9.2491 (5) {angstrom}, {beta} = 104.146 (1){sup 0}, V = 723.1 (1) {angstrom}{sup 3}, R(F) = 2.33%, wR(F) = 2.52%. {beta}-ZnHPO{sub 3}{center_dot}N{sub 4}C{sub 2}H{sub 4}, M{sub r} = 229.44, monoclinic, C2/c, a = 14.5092 (9) {angstrom}, b = 10.5464 (6) {angstrom}, c = 10.3342 (6) {angstrom}, {beta} = 114.290 (1){sup 0}, V = 1441.4 (3) {angstrom}{sup 3}, R(F) = 3.01%, wR(F) = 3.40%.

This paper describes the evolution of the process for assessing the hazards of a geologic disposal system for radioactive waste and, similarly, nuclear power reactors, and the relationship of this process with other assessments of risk, particularly assessments of hazards from manufactured carcinogenic chemicals during use and disposal. This perspective reviews the common history of scientific concepts for risk assessment developed to the 1950s. Computational tools and techniques developed in the late 1950s and early 1960s to analyze the reliability of nuclear weapon delivery systems were adopted in the early 1970s for probabilistic risk assessment of nuclear power reactors, a technology for which behavior was unknown. In turn, these analyses became an important foundation for performance assessment of nuclear waste disposal in the late 1970s. The evaluation of risk to human health and the environment from chemical hazards is built upon methods for assessing the dose response of radionuclides in the 1950s. Despite a shared background, however, societal events, often in the form of legislation, have affected the development path for risk assessment for human health, producing dissimilarities between these risk assessments and those for nuclear facilities. An important difference is the regulator's interest in accounting for uncertainty and the …

A key uncertainty in models of the global carbonate-silicate cycle and long-term climate is the way that silicates weather under different climatologic conditions, and in the presence or absence of organic activity. Digital imaging of basalts in Hawaii resolves the coupling between temperature, rainfall, and weathering in the presence and absence of lichens. Activation energies for abiotic dissolution of plagioclase (23.1{+-} 2.5 kcal/mol) and olivine (21.3 {+-} 2.7 kcal/mol) are similar to those measured in the laboratory, and are roughly double those measured from samples taken underneath lichen. Abiotic weathering rates appear to be proportional to rainfall. Dissolution of plagioclase and olivine underneath lichen is far more sensitive to rainfall.

The structures of the high and low-density amorphous phases of ice are studied using several techniques. The diffraction patterns of high and low density amorphous ice are analyzed using reverse Monte Carlo methods and compared with molecular dynamics simulations of these phases. The spectra of crystalline and amorphous phases of ice obtained by Raman and incoherent inelastic neutron scattering are analyzed to yield structural features for comparison with the results of molecular dynamics and Reverse Monte Carlo analysis. The structural details obtained indicate that there are significant differences between the structure of liquid water and the amorphous phases of ice.

The study of a homologous series of silsesquioxane monomers has uncovered striking discontinuities in gelation behavior. An investigation of the chemistry during the early stages of the polymerization has provided a molecular basis for these observations. Monomers containing from one to four carbon atoms exhibit a pronounced tendency to undergo inter or intramolecular cyclization. The cyclic intermediates have been characterized by {sup 29}Si NMR, chemical ionization mass spectrometry and isolation from the reaction solution. These carbosiloxanes are local thermodynamic sinks that produce kinetic bottlenecks in the production of high molecular weight silsesquioxanes. The formation of cyclics results in slowing down or in some cases completely shutting down gelation. An additional finding is that the cyclic structures are incorporated intact into the final xerogel. Since cyclization alters the structure of the building block that eventually makes up the xerogel network, it is expected that this will contribute importantly to the bulk properties of the xerogel as well.

To confirm conversion of soil Pb to pyromorphite [Pb{sub 5}(PO{sub 4}){sub 3}Cl], a Pb contaminated soil collected adjacent to a historical smelter was reacted with hydroxyapatite in slurries of soil and hydroxyapatite separated by a dialysis membrane and incubated. A crystalline precipitate formed on the dialysis membrane in the slurry systems was identified as chloropyromorphite. Soluble species measured in the soil slurry indicated that dissolution of solid-phase soil Pb was the rate-limiting step for pyromorphite formation. Additionally samples reacted with hydroxyapatite were incubated at field-capacity moisture content. The sequential chemical extraction used to identify species in the field-moist soil incubation experiment showed that hydroxyapatite treatment reduced the first four fractions of extractable Pb and correspondingly increased the recalcitrant extraction residue fraction by 35% of total Pb at 0 d incubation and by 45% after 240 d incubation. the increase in the extraction residue fraction in the 240 d incubation as compared to the 0 d incubation implies that the reaction occurs in the soil but the increase in the hydroxyapatite amended 0 d incubated soil as compared to the control soil illustrates the chemical extraction procedure caused changes in the extractability. Thus, the chemical extraction procedure cannot easily be utilized …

A study of zeolite crystallization from sol-gel precursors using the vapor phase transport synthesis method has been performed. Zeolites (ZSM-5, ZSM-48, Zeolite P, and Sodalite) were crystallized by contacting vapor phase organic or organic-water mixtures with dried sodium silicate and dried sodium alumino-silicate gels. For each precursor gel, a ternary phase system of vapor phase organic reactant molecules was explored. The vapor phase reactant mixtures ranged from pure ethylene diamene, triethylamine, or water, to an equimolar mixture of each. In addition, a series of gels with varied physical and chemical properties were crystallized using the same vapor phase solvent mixture for each gel. The precursor gels and the crystalline products were analyzed via Scanning Electron Microscopy, Electron Dispersive Spectroscopy, X-ray mapping, X-ray powder diffraction, nitrogen surface area, Fourier Transform Infrared Spectroscopy, and thermal analyses. The product phase and purity as a function of the solvent mixture, precursor gel structure, and precursor gel chemistry is discussed.

The National Spherical Torus Experiment (NSTX) started plasma operations i n February 1999. In the first extended period of experiments, NSTX achieved high current, inner wall limited, double null, and single null plasma discharges, initial Coaxial Helicity Injection, and High Harmonic Fast Wave results. As expected, discharge reproducibility and performance were strongly affected by wall conditions. In this paper, the authors describe the internal geometry, and initial plasma discharge, impurity control, wall conditioning, erosion, and deposition results.

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Trialkoxysilyl-containing monomers of the type (RO){sub 3}Si(CH{sub 2}){sub 3}C(O)OtBu (R = Me, Et) were prepared by hydrosilation of the corresponding vinylic tert-butyl esters CH{sub 3}CHCH{sub 2}C(O)OtBu. Acid- or base-catalyzed polymerization of the monomers leads to very high molecular weight polymers with relatively narrow polydispersities. The polymerization results in complete condensation of the alkoxy groups while the tert-butyl ester functionality remains fully intact. Partial or full deprotection of the tert-butyl group can easily be achieved to yield the corresponding carboxylic acid polymers. The ester and carboxylic acid functionalities of these new materials allow for their potential use in a variety of applications such as scavenging of heavy metals.

The structure of Na{sub 16}Nb{sub 12.8}Ti{sub 3.2}O{sub 44.8}(OH){sub 3.2} {center_dot} 8H{sub 2}O, a member of a new family of Sandia Octahedral Molecular Sieves (SOMS) having a Nb/Na/M{sup IV} (M= Ti, Zr) oxide framework and exchangeable Na and water in open channels, was determined from Synchrotron X-ray data. The SOMS phases are isostructural with variable M{sup IV}:Nb(1:50--1:4) ratios. The SOMS are extremely selective for sorption of divalent cations, particularly Sr{sup 2+}. The ion-exchanged SOMS undergo direct thermal conversion to a perovskite-type phase, indicating this is a promising new method for removal and sequestration of radioactive Sr-90 from mixed nuclear wastes.

The miscibility of polypropylene (PP) melts in which the chains differ only in stereochemical composition has been investigated by two different procedures. One approach used detailed local information from a Monte Carlo simulation of a single chain, and the other approach takes this information from a rotational isomeric state model devised decades ago, for another purpose. The first approach uses PRISM theory to deduce the intermolecular packing in the polymer blend, while the second approach uses a Monte Carlo simulation of a coarse-grained representation of independent chains, expressed on a high-coordination lattice. Both approaches find a positive energy change upon mixing isotactic PP (iPP) and syndiotactic polypropylene (sPP) chains in the melt. This conclusion is qualitatively consistent with observations published recently by Muelhaupt and coworkers. The size of the energy chain on mixing is smaller in the MC/PRISM approach than in the RIS/MC simulation, with the smaller energy change being in better agreement with the experiment. The RIS/MC simulation finds no demixing for iPP and atactic polypropylene (aPP) in the melt, consistent with several experimental observations in the literature. The demixing of the iPP/sPP blend may arise from attractive interactions in the sPP melt that are disrupted when the sPP …

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Analysis of the volatile and semivolatile fractions collected after use of the TOR lubricant indicated that other than contaminants in the collection laboratory, no compounds on the EPA's Target Compound Lists (Tables 2 and 5) were detected in these fractions. The data of these qualitative analyses, given in the various tables in the text, indicate only the relative amounts of the tentatively identified compounds. The authors recommend that quantitative analysis be performed on the volatile and semivolatile fractions to allow confirmation of the tentatively identified compounds and to obtain absolute amounts of the detected compounds. Additionally, the semivolatile fraction should be analyzed by liquid chromatography/mass spectrometry to identify compounds that are not chromatographable under the temperature program used for determination of semivolatile compounds. Introducing the top-of-rail (TOR) lubricant into the wheel/rail interface results in a reduction of almost 60% of lateral friction force over the forces encountered under dry conditions. This reveals good potential for energy savings, as well as wear reduction, for railroad companies. In TOR lubrication, an increase in the angle of attack and axle load results in increased lateral friction and rate of lubricant consumption. The most efficient TOR lubricant quantity to be used in the wheel/rail …

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There is a clear gulf between the capabilities of modern synchrotrons to deliver high photon fluxes, and the capabilities of detectors to measure the resulting photon, electron or ion signals. While a huge investment has been made in storage ring technology, there has not to date been a commensurate investment in detector systems. With appropriate detector technology, gains in data rates could be 3 to 4 orders of magnitude in some cases. The US community working in detector technology is under-funded and fragmented and works without the long term funding commitment required for development of the most advanced detector systems. It is becoming apparent that the US is falling behind its international competitors in provision of state-of-the-art detector technology for cutting edge synchrotron radiation based experiments.

The objectives of the program are to provide an improved TBC system with increased temperature capability and improved reliability relative to current state of the art TBC systems. The development of such a coating system is essential to the ATS engine meeting its objectives. The base program consists of three phases: Phase I: Program Planning - Complete; Phase II: Development - Complete; and Phase III: Selected Specimen - Bench Test. Work was performed on the Phase II final report and on III of the program during the reporting period.

The last major development effort for nuclear power and propulsion systems ended in 1993. Currently, there is not an initiative at either the National Aeronautical and Space Administration (NASA) or the U.S. Department of Energy (DOE) that requires the development of new nuclear power and propulsion systems. Studies continue to show nuclear technology as a strong technical candidate to lead the way toward human exploration of adjacent planets or provide power for deep space missions, particularly a 15,000 lbf bimodal nuclear system with 115 kW power capability. The development of nuclear technology for space applications would require technology development in some areas and a major flight qualification program. The last major ground test facility considered for nuclear propulsion qualification was the U.S. Air Force/DOE Space Nuclear Thermal Propulsion Project. Seven years have passed since that effort, and the questions remain the same, how to qualify nuclear power and propulsion systems for future space flight. It can be reasonably assumed that much of the nuclear testing required to qualify a nuclear system for space application will be performed at DOE facilities as demonstrated by the Nuclear Rocket Engine Reactor Experiment (NERVA) and Space Nuclear Thermal Propulsion (SNTP) programs. The nuclear infrastructure …

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This report discusses the accomplishments of the environmental protection program at Argonne National Laboratory-East (ANL-E) for calendar year 2002. The status of ANL-E environmental protection activities with respect to the various laws and regulations that govern waste handling and disposal is discussed, along with the progress of environmental corrective actions and restoration projects. To evaluate the effects of ANL-E operations on the environment, samples of environmental media collected on the site, at the site boundary, and off the ANL-E site were analyzed and compared with applicable guidelines and standards. A variety of radionuclides were measured in air, surface water, on-site groundwater, and bottom sediment samples. In addition, chemical constituents in surface water, groundwater, and ANL-E effluent water were analyzed. External penetrating radiation doses were measured, and the potential for radiation exposure to off-site population groups was estimated. Results are interpreted in terms of the origin of the radioactive and chemical substances (i.e., natural, fallout, ANL-E, and other) and are compared with applicable environmental quality standards. A U.S. Department of Energy dose calculation methodology, based on International Commission on Radiological Protection recommendations and the U.S. Environmental Protection Agency's CAP-88 (Clean Air Act Assessment Package-1988) computer code, was used in preparing this …

OAK A271 Hydroacoustic Studies Using HydroCAM - Station-centric Integration of Models and Observations Quarterly Report No. 3 April 2003 - June 2003. BBN's work from April through June of 2003 was focused on the testing and release of HydroCAM 4.0, development of HydroCAM 4.1 software, continued data collection and analysis, and initial preparations for the 2003 Seismic Research Review. HydroCAM 4.0 was released and sent to DOE and AFTAC on June 9. This is the first release of new software on this contract. The code addresses the problems and issues that BBN and AFTAC had identified in the Fall of 2003. HydroCAM 4.1 is under development. A description of that development is shown in section 3.2. We continued our efforts to collect ground truth hydroacoustic data from sub-sea earthquakes in the Indian Ocean. To date, we have collected over 130 events. These data are recorded on the International Monitoring System stations at Diego Garcia and Cape Leeuwin. Finally, BBN submitted an abstract for the 2003 Seismic Research Review meeting. However, after discussions with Phil Harben at Lawrence Livermore Labs, we have decided to collaborate on one program-wide paper for the meeting.