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.
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 to confirm changes occurring in the soil as a result of incubation. Extended x-ray absorption fine structure (EXAFS) spectroscopy indicated that the 240 d incubated hydroxyapatite treatment caused a change in the average, local molecular bonding environment of soil Pb. Low-temperature EXAFS spectra (chi data and radial structure functions - RSFs) showed a high degree of similarity between the chemical extraction residue and synthetic pyromorphite. Thus, confirming that the change of soil Pb to pyromorphite is possible by simple amendments of hydroxyapatite to soil.
The authors describe the microfabrication of a multi-level diffractive optical element (DOE) onto a micro-electromechanical system (MEMS) as a key element in an integrated compact optical-MEMS laser scanner. The DOE is a four-level off-axis microlens fabricated onto a movable polysilicon shuttle. The microlens is patterned by electron beam lithography and etched by reactive ion beam etching. The DOE was fabricated on two generations of MEMS components. The first generation design uses a shuttle suspended on springs and displaced by a linear rack. The second generation design uses a shuttle guided by roller bearings and driven by a single reciprocating gear. Both the linear rack and the reciprocating gear are driven by a microengine assembly. The compact design is based on mounting the MEMS module and a vertical cavity surface emitting laser (VCSEL) onto a fused silica substrate that contains the rest of the optical system. The estimated scan range of the system is {+-}4{degree} with a spot size of 0.5 mm.
A novel planar resonant tunneling transistor is demonstrated. The growth structure is similar to that of a double-barrier resonant tunneling diode (RTD), except for a fully two-dimensional (2D) emitter formed by a quantum well. Current is fed laterally into the emitter, and the 2D--2D resonant tunneling current is controlled by a surface gate. This unique device structure achieves figures-of-merit, i.e. peak current densities and peak voltages, approaching that of state-of-the-art RTDs. Most importantly, sensitive control of the peak current and voltage is achieved by gating of the emitter quantum well subband energy. This quantum tunneling transistor shows exceptional promise for ultra-high speed and multifunctional operation at room temperature.
Using Low Energy Electron Microscopy (LEEM), the authors have followed Cu(100) surface morphology changes during Pb deposition at different temperatures. Surface steps advance and 2-D islands nucleate and grow as deposited Pb first alloys, and then dealloys, on a 125 C Cu(100)surface. From LEEM images, they determine how much Cu is being displaced at each stage and find that the amount of material added to the top layer for a complete Pb/Cu(100) c(4x4) reconstruction (a surface alloy) is consistent with the expected c(4x4) Cu content of 0.5 monolayer. However, as the surface changes to the Pb/Cu(100) c(2x2) overlayer, they find that the displaced material from surface dealloying, 0.22ML, is more than a factor of two lower than expected based on a pure Pb c(2x2) overlayer. Further, they find that in the 70 to 130 C range the amount of Cu remaining in c(2x2) increases with increasing substrate temperature during the deposition, showing that surface Cu is alloyed with Pb in the c(2x2) structure at these temperatures. When holding the sample at 125 C, the transformation from the c(2x2) structure to the higher coverage c(5{radical}2 x{radical}2)R45{degree} overlayer structure displaces more Cu, confirming the c(2x2) surface alloy model. They also find the c(2x2) surface has characteristically square 2-D islands with step edges parallel to the (100) type crystallographic directions, whereas the c(5{radical}2 x{radical}2)R45{degree} structure has line-like features which run parallel to the dislocation double rows of this surface's atomic structure and which expand into 2-D islands upon coarsening.
The authors have investigated the effects of heme rotational isomerism in sperm-whale carbonmonoxy myoglobin using computational techniques. Several molecular dynamics simulations have been performed for the two rotational isomers A and B, which are related by a 180{degree} rotation around the {alpha}-{gamma} axis of the heme, of sperm-whale carbonmonoxy myoglobin in water. Both neutron diffraction and NMR structures were used as starting structures. In the absence of an experimental structure, the structure of isomer B was generated by rotating the heme in the structure of isomer A. Distortions of the heme from planarity were characterized by normal coordinate structural decomposition and by the angle of twist of the pyrrole rings from the heme plane. The heme distortions of the neutron diffraction structure were conserved in the MD trajectories, but in the NMR-based trajectories, where the heme distortions are less well defined, they differ from the original heme deformations. The protein matrix induced similar distortions on the heroes in orientations A and B. The results suggest that the binding site prefers a particular macrocycle conformation, and a 180{degree} rotation of the heme does not significantly alter the protein's preference for this conformation. The intrinsic rotational strengths of the two Soret transitions, separated according to their polarization in the heme plane, show strong correlations with the ruf-deformation and the average twist angle of the pyrrole rings. The total rotational strength, which includes contributions from the chromophores in the protein, shows a weaker correlation with heme distortions.
The authors report on their recent experimental studies of vertically-coupled quantum point contacts subject to in-plane magnetic fields. Using a novel flip-chip technique, mutually aligned split gates on both sides of a sub micron thick double quantum well heterostructure define a closely-coupled pair of ballistic one-dimensional (1D) constrictions. They observe quantized conductance steps due to each quantum well and demonstrate independent control of each ID constriction width. In addition, a novel magnetoconductance feature at {approximately}6 T is observed when a magnetic field is applied perpendicular to both the current and growth directions. This conductance dip is observed only when 1D subbands are populated in both the top and bottom constrictions. This data is consistent with a counting model whereby the number of subbands crossing the Fermi level changes with field due to the formation of an anticrossing in each pair of 1D subbands.
The design and performance of Love-wave sensors using cross-linked poly-(methyl methacrylate) waveguides of thickness of 0.3--3.2 {micro}m on LiTaO{sub 3} substrates are described. It is found that this layer-substrate combination provides sufficient waveguidance, and electrical isolation of the IDTs from the liquid environment to achieve low acoustic loss and distortion. In bio-sensing experiments, mass sensitivity up to 1,420 Hz/(ng/mm{sup 2}) is demonstrated.
The effect of the nuclear hyperfine interaction on the dc conductivity of 2D electrons under quantum Hall effect conditions at filling factor v= 1 is observed for the first time. The local hyperfine field enhanced by dynamic nuclear polarization is monitored via the Overhauser shift of the 2D conduction electron spin resonance in AlGaAs/GaAs multiquantum-well samples. The experimentally observed change in the dc conductivity resulting from dynamic nuclear polarization is in agreement with a thermal activation model incorporating the Zeeman energy change due to the hyperfine interaction. The relaxation decay time of the dc conductivity is, within experimental error, the same as the relaxation time of the nuclear spin polarization determined from the Overhauser shift. These findings unequivocally establish the nuclear spin origins of the observed conductivity change.
The authors present the results of molecular dynamics simulations of n-butane and isobutane in silicalite. They begin with a comparison of the bulk adsorption and diffusion properties for two different parameterizations of the interaction potential between the hydrocarbon species, both of which have been shown to reproduce experimental gas-liquid coexistence curves. They examine diffusion as a function of the loading of the zeolite, as well as the temperature dependence of the diffusion constant at loading and for infinite dilution. They continue with simulations in which interfaces are formed between single component gases and the zeolite. After reaching equilibrium, they examine the dynamics of exchange between the bulk gas and the zeolite. Finally, they calculate the permeability of the zeolite for n-butane and isobutane as a function of pressure. Their simulations are performed for a number of different gas temperatures and pressures, covering a wide range of state points.
Notwithstanding half a dozen theoretical publications, well-converged density-functional calculations, whether based on a local or generalized-gradient exchange-correlation potential, whether all-electron or employing pseudopotentials underestimate CO's preference for low-coordination binding sites on Pt(111) and vicinals to it. For example, they imply that CO should prefer hollow- to atop-site adsorption on Pt(111), in apparent contradiction to a host of low temperature experimental studies.
Solid Polymer Electrolytes (SPE) are widely used in batteries and fuel cells because of the high ionic conductivity that can be achieved at room temperature. The ions are usually Li or protons, although other ions can be shown to conduct in these polymer films. There has been very little published work on SPE films used as chemical sensors. The authors have found that thin films of polymers like polyethylene oxide (PEO) are very sensitive to low concentrations of volatile organic compounds (VOCs) such as common solvents. Evidence of a new sensing mechanism involving the percolation of ions through narrow channels of amorphous polymer is presented. They present impedance spectroscopy of PEO films in the frequency range 0.0001 Hz to 1 MHz for different concentrations of VOCs and relative humidity. They find that the measurement frequency is important for distinguishing ionic conductivity from the double layer capacitance and the parasitic capacitance.
Accurate predictions of retention times, retention indices, and partition constants are a long sought-after goal for theoretical studies in chromatography. Although advances in computational chemistry have improved the understanding of molecular interactions, little attention has been focused on chromatography, let alone calculations of retention properties. Configurational-bias Monte Carlo simulations in the isobaric-isothermal Gibbs ensemble were used to investigate the partitioning of benzene, toluene, and the three xylene isomers between a squalane liquid phase and a helium vapor phase. The united-atom representation of the TraPPE (Transferable Potentials for Phase Equilibria) force field was used for all solutes and squalane. The Gibbs free energies of transfer and Kovats retention indices of the solutes were calculated directly from the partition constants (which were averaged over several independent simulations). While the calculated Kovats indices of benzene and toluene at T = 403 K are significantly higher than their experimental counterparts, much better agreement is found for the xylene isomers at T = 365 K.
Molecular dynamics simulations of a simple, bead-spring model of semiflexible polyelectrolytes such as DNA are performed. All charges are explicitly treated. Starting from extended, noncondensed conformations, condensed structures form in the simulations with tetravalent or trivalent counterions. No condensates form or are stable for divalent counterions. The mechanism by which condensates form is described. Briefly, condensation occurs because electrostatic interactions dominate entropy, and the favored Coulombic structure is a charge ordered state. Condensation is a generic phenomena and occurs for a variety of polyelectrolyte parameters. Toroids and rods are the condensate structures. Toroids form preferentially when the molecular stiffness is sufficiently strong.
A z-pinch radiation source has been developed that generates 60 {+-} 20 KJ of x-rays with a peak power of 13 {+-} 4 TW through a 4-mm diameter axial aperture on the Z facility. The source has heated NIF (National Ignition Facility)-scale (6-mm diameter by 7-mm high) hohlraums to 122 {+-} 6 eV and reduced-scale (4-mm diameter by 4-mm high) hohlraums to 155 {+-} 8 eV -- providing environments suitable for indirect-drive ICF (Inertial Confinement Fusion) studies. Eulerian-RMHC (radiation-hydrodynamics code) simulations that take into account the development of the Rayleigh-Taylor instability in the r-z plane provide integrated calculations of the implosion, x-ray generation, and hohlraum heating, as well as estimates of wall motion and plasma fill within the hohlraums. Lagrangian-RMHC simulations suggest that the addition of a 6 mg/cm{sup 3} CH{sub 2} fill in the reduced-scale hohlraum decreases hohlraum inner-wall velocity by {approximately}40% with only a 3--5% decrease in peak temperature, in agreement with measurements.
The FETI algorithms are numerically scalable iterative domain decomposition methods. These methods are well documented for solving equations arising from the Finite Element discretization of second or fourth order elasticity problems. The one level FETI method equipped with the Dirichlet preconditioned was shown to be numerically scalable for second order elasticity problems while the two level FETI method was designed to be numerically scalable for fourth order elasticity problems. The second level coarse grid is an enriched version of the original one level FETI method with coarse grid. The coarse problem is enriched by enforcing transverse displacements to be continuous at the corner points. This coarse problem grows linearly with the number of subdomains. Current implementations use a direct solution method to solve this coarse problem. However, the current implementation gives rise to a full matrix system. This full matrix can lead to increased storage requirements especially if working within a distributed memory environment. Also, the factorization and subsequent forward/backward substitutions of the second level coarse problem becomes the dominant factor in solving the global problem as the number of subdomains becomes large (N{sub s} > 1,000). The authors introduce an alternative formulation of the two level coarse problem that leads to a sparse system better suited for a direct method. Then they show extensions to the alternate formulation that allow optional admissible constraints to be added to improve convergence. Lastly, they report on the numerical performance, parallel efficiency, memory requirements, and overall CPU time as compared to the classical two level FETI on some large scale fourth order elasticity problems.
A mechanical isolator has been developed for a piezoresistive accelerometer. The purpose of the isolator is to mitigate high frequency shocks before they reach the accelerometer because the high frequency shocks may cause the accelerometer to resonate. Since the accelerometer is undamped, it often breaks when it resonates. The mechanical isolator was developed in response to impact test requirements for a variety of structures at Sandia National Laboratories (SNL). An Extended Technical Assistance Program (ETAP) with the accelerometer manufacturer has resulted in a commercial mechanically isolated accelerometer that is available to the general public, the ENDEVCO 7270AM6*, for three shock acceleration ranges of 6,000 g, 20,000 g, and 60,000 g. The in-axis response shown in this report has acceptable frequency domain performance from DC to 10 kHz and 10(XO)over a temperature range of {minus}65 F to +185 F. Comparisons with other isolated accelerometers show that the ENDEVCO 7270AM6 has ten times the bandwidth of any other commercial isolator. ENDEVCO 7270AM6 cross-axis response is shown in this report.
The main objective of this project was to develop reliable, low-cost techniques for joining silicon nitride (Si{sub 3}N{sub 4}) to itself and to metals. For Si{sub 3}N{sub 4} to be widely used in advanced turbomachinery applications, joining techniques must be developed that are reliable, cost-effective, and manufacturable. This project addressed those needs by developing and testing two Si{sub 3}N{sub 4} joining systems; oxynitride glass joining materials and high temperature braze alloys. Extensive measurements were also made of the mechanical properties and oxidation resistance of the braze materials. Finite element models were used to predict the magnitudes and positions of the stresses in the ceramic regions of ceramic-to-metal joints sleeve and butt joints, similar to the geometries used for stator assemblies.
Preliminary shielding calculations were performed for a prototype National Spent Nuclear Fuel Program (NSNFP) transport cask. This analysis is intended for use in the selection of cask shield material type and preliminary estimate of shielding thickness. The radiation source term was modeled as cobalt-60 with radiation exposure strength of 100,000 R/hr. Cobalt-60 was chosen as a surrogate source because it simultaneous emits two high-energy gammas, 1.17 MeV and 1.33 MeV. This gamma spectrum is considered to be large enough that it will upper bound the spectra of all the various spent nuclear fuels types currently expected to be shipped within the prototype cask. Point-kernel shielding calculations were performed for a wide range of shielding thickness of lead and depleted uranium material. The computational results were compared to three shielding limits: 200 mrem/hr dose rate limit at the cask surface, 50 mR/hr exposure rate limit at one meter from the cask surface, and 10 mrem/hr limit dose rate at two meters from the cask surface. The results obtained in this study indicated that a shielding thickness of 13 cm is required for depleted uranium and 21 cm for lead in order to satisfy all three shielding requirements without taking credit for stainless steel liners. The system analysis also indicated that required shielding thicknesses are strongly dependent upon the gamma energy spectrum from the radiation source term. This later finding means that shielding material thickness, and hence cask weight, can be significantly reduced if the radiation source term can be shown to have a softer, lower energy, gamma energy spectrum than that due to cobalt-60.
The effects of chemical aging on the behavior of carbon black filled rubber were investigated by two types of tests, aging under no strain and aging under a constant strain. A slight modification of the damage-based theory of Segalman, used previously on unaged samples, was found to be consistent with the experimental data.
The U. S. Department of Energy Strategic Petroleum Reserve currently has approximately 500 million barrels of crude oil stored in 62 caverns solution-mined in salt domes along the Gulf Coast of Louisiana and Texas. One of the challenges of operating these caverns is ensuring that none of the fluids in the caverns are leaking into the environment. The current approach is to test the mechanical integrity of all the wells entering each cavern approximately once every five years. An alternative approach to detecting cavern leaks is to monitor the cavern pressure, since leaking fluid would act to reduce cavern pressure. Leak detection by pressure monitoring is complicated by other factors that influence cavern pressure, the most important of which are thermal expansion and contraction of the fluids in the cavern as they come into thermal equilibrium with the host salt, and cavern volume reduction due to salt creep. Cavern pressure is also influenced by cavern enlargement resulting from salt dissolution following introduction of raw water or unsaturated brine into the cavern. However, this effect only lasts for a month or two following a fluid injection. In order to implement a cavern pressure monitoring program, a software program called CaveMan has been developed. It includes thermal, creep and salt dissolution models and is able to predict the cavern pressurization rate based on the operational history of the cavern. Many of the numerous thermal and mechanical parameters in the model have been optimized to produce the best match between the historical data and the model predictions. Future measurements of cavern pressure are compared to the model predictions, and significant differences in cavern pressure set program flags that notify cavern operators of a potential problem. Measured cavern pressures that are significantly less than those predicted by the model may indicate the existence of a leak.
The spatial and temporal origin of a seismic energy source are estimated with a first grid search technique. This approach has greater likelihood of finding the global rninirnum of the arrival time misiit function compared with conventional linearized iterative methods. Assumption of a homogeneous and isotropic seismic velocity model allows for extremely rapid computation of predicted arrival times, but probably limits application of the method to certain geologic environments and/or recording geometries. Contour plots of the arrival time misfit function in the vicinity of the global minimum are extremely useful for (i) quantizing the uncertainty of an estimated hypocenter solution and (ii) analyzing the resolving power of a given recording configuration. In particular, simultaneous inversion of both P-wave and S-wave arrival times appears to yield a superior solution in the sense of being more precisely localized in space and time. Future research with this algorithm may involve (i) investigating the utility of nonuniform residual weighting schemes, (ii) incorporating linear and/or layered velocity models into the calculation of predicted arrival times, and (iii) applying it toward rational design of microseismic monitoring networks.
We present mathematical proofs for two useful properties of the clusters generated by the visual empirical region of influence (VERI) shape. The first proof shows that, for any d-dimensional vector set with more than one distinct vector, that there exists a bounded spherical volume about each vector v which contains all of the vectors that can VERI cluster with v, and that the radius of this d-dimensional volume scales linearly with the nearest neighbor distance to v. We then prove, using only each vector's nearest neighbor as an inhibitor, that there is a single upper bound on the number of VERI clusterings for each vector in any d-dimensional vector set, provided that there are no duplicate vectors. These proofs guarantee significant improvement in VERI algorithm runtimes over the brute force O(N{sup 3}) implementation required for general d-dimensional region of influence implementations and indicate a method for improving approximate O(NlogN) VERI implementations. We also present a related region of influence shape called the VERI bow tie that has been recently used in certain swam intelligence algorithms. We prove that the VERI bow tie produces connected graphs for arbitrary d-dimensional data sets (if the bow tie boundary line is not included in the region of influence). We then prove that the VERI bow tie also produces a bounded number of clusterings for each vector in any d-dimensional vector set, provided that there are no duplicate vectors (and the bow tie boundary line is included in the region of influence).
Multivariate calibration techniques have been used in a wide variety of spectroscopic situations. In many of these situations, spectral variation can be partitioned into separate classes. For example, suppose that multiple spectra are obtained from each of a number of different objects wherein the level of the analyze of interest varies within each object over time. In such situations, the total spectral variation observed across all measurements has two distinct general sources of variation: intraobject and interobject. One might want to develop a global multivariate calibration model that predicts the analyze of interest accurately both within and across objects, including new objects not involved in developing the calibration model. However, this goal might be hard to realize if the interobject spectral variation is complex and difficult to model. If the intraobject spectral variation is consistent across objects, an effective alternative approach might be to develop a generic intraobject model that can be adapted to each object separately. This paper contains recommendations for experimental protocols and data analysis in such situations. The approach is illustrated with an example involving the noninvasive measurement of glucose using near-infrared reflectance spectroscopy. Extensions to calibration maintenance and calibration transfer are discussed.
Careful characterization of laser beams used in materials processing such as welding and drilling is necessary to obtain robust, reproducible processes and products. Recently, equipment and techniques have become available which make it possible to rapidly and conveniently characterize the size, shape, mode structure, beam quality (Mz), and intensity of a laser beam (incident power/unit area) as a function of distance along the beam path. This facilitates obtaining a desired focused spot size and also locating its position. However, for a given position along the beam axis, these devices typically measure where the beam intensity level has been reduced to I/ez of maximum intensity at that position to determine the beam size. While giving an intuitive indication of the beam shape since the maximum intensity of the beam varies greatly, the contour so determined is not an iso-contour of any parameter related to the beam intensity or power. In this work we shall discuss an alternative beam shape formulation where the same measured information is plotted as contour intervals of intensity.
The authors study multi-photon-assisted transmission of electrons through single-step, single-barrier and double-barrier potential-energy structures as a function of the photon energy and the temperature. Sharp resonances in the spectra of the tunneling current through double-barrier structures are relevant to infra-red detectors.
The diffusion, uptake, and release of H in p-type GaN are modeled employing state energies from density-function theory and compared with measurements of deuterium uptake and release using nuclear-reaction analysis. Good semiquantitative agreement is found when account is taken of a surface permeation barrier.
The switching and memory retention time has been measured in 50 {micro}m gatelength pseudo-non-volatile memory MOSFETs containing, protonated 40 nm gate oxides. Times of the order of 3.3 seconds are observed for fields of 3 MV cm{sup {minus}1}. The retention time with protons placed either at the gate oxide/substrate or gate oxide/gate electrode interfaces is found to better than 96% after 5,000 seconds. Measurement of the time dependence of the source-drain current during switching provides clear evidence for the presence of dispersive proton transport through the gate oxide.
Ethane oxidation reactions were studied over pure and Ca-, Mg-, Sr-, La-, Nd-, and Y-substituted BaCeO3 perovskites under oxygen limited conditions. Several of the materials, notably the Ca- and Y-substituted materials, show activity for complete oxidation of the hydrocarbon to CO2 at temperatures below 650 °C. At higher temperatures, the oxidative dehydrogenation (ODH) to ethylene becomes significant. Conversions and ethylene yields are enhanced by the perovskites above the thermal reaction in our system in some cases. The perovskite structure is not retained in the high temperature reaction environment. Rather, a mixture of carbonates and oxides is formed. Loss of the perovskite structure correlates with a loss of activity and selectivity to ethylene.
The authors are developing a laser radar to meet the needs of NASA for a 5-lb, 150 in{sup 3} image sensor with a pixel range accuracy of 0.1-inch. NASA applications include structural dynamics measurements, navigation guidance in rendezvous and proximity operations, and space vehicle inspection. The sensor is based on the scannerless range imager architecture developed at Sandia. This architecture modulates laser floodlight illumination and a focal plane receiver to phase encode the laser time of flight (TOF) for each pixel. They believe this approach has significant advantages over architectures directly measuring TOF including high data rate, reduced detector bandwidth, and conventional FPA detection. A limitation of the phase detection technique is its periodic nature, which provides relative range information over a finite ambiguity interval. To extend the operating interval while maintaining a given range resolution, a LADAR sensor using dual modulation frequencies has been developed. This sensor also extends the relative range information to absolute range by calibrating a gating function on the receiver to the TOF. The modulation frequency values can be scaled to meet the resolution and range interval requirements of different applications. Results from the miniature NASA sensor illustrate the advantages of the dual-frequency operation and the ability to provide the range images of 640 by 480 pixels at 30 frames per second.
A mobile 480-V, 2-MVA UPS System utilizing battery energy storage was installed at S and C Electric Company's Polymer Products Fabrication Building in Chicago, Illinois in May 1999 to provide uninterrupted power to the building for up to 15 seconds in the event of a voltage sag or momentary interruption in the local utility supply. Similar units can be applied at medium voltage through the application of a step-up transformer to provide momentary power disturbance ride through of up to 30 seconds for loads up to 15 MVA at system voltages ranging from 4.16 kV to 34.5 kV. A power quality evaluation of the installation was performed over a six-month period from July 1999 to early January 2000. This paper describes the details and results of this power quality evaluation, which involved two phases. Phase I involved the collection and review of power disturbance data and the effects on process equipment, while Phase II involved power quality monitoring of utility source and building load voltages and currents over a period of six months. Review of power disturbance data and equipment power-disturbance ride-through characteristics during Phase I of the project indicated that the polymer fabrication process in the building is affected by the tripping of motors driving hydraulic pumps for the thermal set molding machines. The tripping of these motors may have resulted in direct production losses in 1998 of approximately $468,000. The monitoring conducted during Phase II of the project showed that the PureWave UPS operated as intended during 12 utility voltage sag events to protect the building's load against momentary power disturbances. In addition, the unit operated successfully during many staged interruptions involving opening of a source-side circuit breaker.
We have used gas chromatography-mass spectroscopy (GCMS) to study the decomposition of TBA (tert-butylarsine, H2AsC(CH3)3) in storage containers at room temperature. Over a four-week period, as much as 1% of the TBA decomposed to arsine and isobutane in a stainless-steel bottle. Several freeze-thaw purification schemes were tested. Use of a liquid-nitrogen bath left a substantial amount of arsine and isobutane in the bottle, while an ice water bath removed all of the arsine but left residual isobutane. Evacuation of the storage container at room temperature removed both arsine and isobutane to below the GCMS detection limits. However, this approach did lead to significant TBA loss. Storing TBA in a Teflon-lined bottle and in a high-surface-to-volume stainless-steel container did not change the decomposition rate measurably, suggesting that stainless-steel surfaces do not promote TBA decomposition.
Quantitative measurements of the diffusion of adsorbed mixed Ge-Si dimers on the Si(100) surface have been made as a function of temperature using atom-tracking scanning tunneling microscopy. These mixed dimers are distinguishable from pure Si-Si dimers by their characteristic kinetics--a 180-degree rotation between two highly buckled configurations. At temperatures at which the mixed dimers diffuse, atomic-exchange events occur, in which the Ge atom in the adsorbed dimer exchanges with a substrate Si atom. Re-exchange can also occur when the diffusing Si-Si dimer revisits the original site of exchange.
To design more radiation tolerant Integrated Circuits (ICs), it is essential to create and test accurate models of ionizing radiation induced charge collection dynamics within microcircuits. A new technique, Diffusion Time Resolved Ion Beam Induced Charge Collection (DTRIBICC), is proposed to measure the average arrival time of the diffused charge at the junction. Specially designed stripe-like junctions were experimentally studied using a 12 MeV carbon microbeam with a spot size of 1 {micro}m. The relative arrival time of ion-generated charge is measured along with the charge collection using a multiple parameter data acquisition system. The results show the importance of the diffused charge collection by junctions, which is especially significant in accounting for Multiple Bit Upset (MBUs) in digital devices.
Electrode gap is a very important parameter for the safe and successful control of vacuum arc remelting (VAR), a process used extensively throughout the specialty metals industry for the production of nickel base alloys and aerospace titanium alloys. Optimal estimation theory has been applied to the problem of estimating electrode gap and a filter has been developed based on a model of the gap dynamics. Taking into account the uncertainty in the process inputs and noise in the measured process variables, the filter provides corrected estimates of electrode gap that have error variances two-to-three orders of magnitude less than estimates based solely on measurements for the sample times of interest. This is demonstrated through simulations and confined by tests on the VAR furnace at Sandia National Laboratories. Furthermore, the estimates are inherently stable against common process disturbances that affect electrode gap measurement and melting rate. This is not only important for preventing (or minimizing) the formation of solidification defects during VAR of nickel base alloys, but of importance for high current processing of titanium alloys where loss of gap control can lead to a catastrophic, explosive failure of the process.
The authors have shown that the hydroperoxide species in {gamma}-irradiated {sup 13}C-polyethylene can be directly observed by {sup 13}C MAS NMR spectroscopy. The experiment was performed without the need for special sample preparation such as chemical derivatization or dissolution. Annealing experiments were employed to study the thermal decomposition of the hydroperoxide species and to measure an activation energy of 98 kJ/mol. EPR spectroscopy suggests that residual polyenyl and alkylperoxy radicals are predominantly trapped in interracial or crystalline regions, while the peroxy radicals observed after UV-photolysis of hydroperoxides are in amorphous regions.
A solution mining facility at the Eddy Potash Mine, Eddy County, New Mexico has been proposed that will utilize salinity gradient solar pond (SGSP) technology to supply industrial process thermal energy. The process will include underground dissolution of potassium chloride (KCl) from pillars and other reserves remaining after completion of primary room and pillar mining using recirculating solutions heated in the SGSP. Production of KCl will involve cold crystallization followed by a cooling pond stage, with the spent brine being recirculated in a closed loop back to the SGSP for reheating. This research uses SGSP as a renewable, clean energy source to optimize the entire mining process, minimize environmental wastes, provide a safe, more economical extraction process and reduce the need for conventional processing by crushing, grinding and flotation. The applications of SGSP technology will not only save energy in the extraction and beneficiation processes, but also will produce excess energy available for power generation, desalination, and auxiliary structure heating.
A major cause of failures in heat exchangers and steam generators in nuclear power plants is degradation of the tubes within them. The tube failure is often caused by the development of cracks that begin on the outer surface of the tube and propagate both inwards and laterally. A new technique will be described for detection of defects using a continuous-wave radar device within metal tubing. The technique is 100% volumetric, and may find smaller defects, find them more rapidly, and find them less expensively than present methods. Because this project was started only recently, there is no demonstrated performance to report so far. However, the basic engineering concepts will be presented together with a description of the milestone tasks and dates.
A hybrid of a microfabricated planar preconcentrator and a four element chemiresistor array chip has been fabricated and the performance as a chemical sensor system has been demonstrated. The close proximity of the chemiresistor sensor to the preconcentrator absorbent layer allows for fast transfer of the preconcentrated molecules during the heating and resorption step. The hybrid can be used in a conventional flow sampling system for detection of low concentrations of analyte molecules or in a pumpless/valveless mode with a grooved lid to confine the desorption plume from the preconcentrator during heating.
Highly concentrated, aqueous mullite slurries were characterized and stabilized at solids concentrations as high as 60 vol% using less than 2 vol% of an organic polyelectrolyte dispersant. The maximum slurry concentration (60 vol%) is within 3 vol% of the maximum consolidated density of the slurry. The slurries were subsequently cast into parts by a solid freeform fabrication technique termed robocasting and characterized. Sedimentation analysis and viscometry provided the means of slurry characterization, while knowledge of polyelectrolyte and interparticle forces was used to interpret the sedimentation and viscometry data. Through proper control of slurry conditions, pseudoplastic mullite slurries were fabricated for use in the robocasting process. The slurries were robocast at 52 vol% solids and subsequently yielded a green density of 55 vol%. Fired densities of the robocasted slurries were high, with mullite >96% dense at 1,650 C.
The authors use low energy electron microscopy to identify a correlation between the growth shape of three-dimensional Pb islands on Cu(100)and the domain structure of the underlying Pb overlayer. Deposition of 0.6 monolayer Pb on Cu(100) produces a compressed c(2x2) overlayer, designated c(5{radical}2x{radical}2)R45{degree}, with periodic rows of anti-phase boundaries. They found that heating the surface to temperatures above 100 C coarsens the orientational domains of this structure to sizes that are easily resolved in the low energy electron microscope. Three-dimensional Pb islands, grown on the coarsened domains, are found to be asymmetric with orientations that correlate with the domain structure. Once nucleated with a preferred growth orientation, islands continue to grow with the same preferred orientation, even across domain boundaries.
Atomistic computer simulation methods have been employed to model the structure of the (10{bar 1}4) surfaces of calcite, dolomite and magnesite. The authors calculations show that under vacuum conditions, calcite undergoes the greatest degree of surface relaxation with rotation and distortion of the carbonate group accompanied by movement of the calcium ion. The magnesite surface is the least distorted of the three carbonates, with dolomite being intermediate to the two end members. When water molecules are placed on the surface to produce complete monolayer coverage, the calcite surface is stabilized and the amount of relaxation is substantially reduced. In contrast, the dolomite and magnesite surfaces are destabilized by hydration as indicated by a significant increase in the surface energies relative to the dry surface.
The goal of this work is to develop techniques for measuring gradients in particle concentration within filled polymers, such as encapsulant. A high concentration of filler particles is added to such materials to tailor physical properties such as thermal expansion coefficient. Sedimentation and flow-induced migration of particles can produce concentration gradients that are most severe near material boundaries. Therefore, techniques for measuring local particle concentration should be accurate near boundaries. Particle gradients in an alumina-filled epoxy resin are measured with a spatial resolution of 0.2 mm using an x-ray beam attenuation technique, but an artifact related to the finite diameter of the beam reduces accuracy near the specimen's edge. Local particle concentration near an edge can be measured more reliably using microscopy coupled with image analysis. This is illustrated by measuring concentration profiles of glass particles having 40 {micro}m median diameter using images acquired by a confocal laser fluorescence microscope. The mean of the measured profiles of volume fraction agrees to better than 3% with the expected value, and the shape of the profiles agrees qualitatively with simple theory for sedimentation of monodisperse particles. Extending this microscopy technique to smaller, micron-scale filler particles used in encapsulant for microelectronic devices is illustrated by measuring the local concentration of an epoxy resin containing 0.41 volume fraction of silica.
Laser induced fluorescence was used to measure the spatially resolved CF, CF{sub 2} and SiF radical density in inductively driven discharges containing fluorocarbon gases. Measurements of the spatially resolved CF density were performed in C{sub 2}F{sub 6} and CHF{sub 3} containing discharges as functions of inductive power, pressure and bias condition on a silicon substrate. In addition, CF rotational temperatures were calculated, assuming saturated spectra. Measurements of the spatially resolved CF{sub 2} and SiF density were performed in C{sub 4}F{sub 8}, C{sub 2}F{sub 6} and CHF{sub 3} containing discharges as functions of inductive power, pressure and bias condition. SiF rotational temperatures were also estimated. As the induction coil power was increased, the SiF density in the center (r = 0 cm) increased while the CF{sub 2} density decreased and the CF density slightly decreased. In all cases, the radical density in the center of the glow increased with pressure changes from 5 to 30 mTorr while changes in the bias power had little influence on any of the measured radical densities. The spatial distribution of the CF and SiF density peaked in the center of the discharge. The CF{sub 2} density had a local maximum in the center of the plasma with a decreasing density at the edge of the glow. However, the CF{sub 2} density outside the glow region was a factor of 2--6 higher than the density inside the glow region, depending on the gas. CF and SiF rotational temperatures were between 450 and 750 K.
Algorithms developed to enable the use of atomistic molecular simulation methods with parallel computers are reviewed. Methods appropriate for bonded as well as non-bonded (and charged) interactions are included. While strategies for obtaining parallel molecular simulations have been developed for the full variety of atomistic simulation methods, molecular dynamics and Monte Carlo have received the most attention. Three main types of parallel molecular dynamics simulations have been developed, the replicated data decomposition, the spatial decomposition, and the force decomposition. For Monte Carlo simulations, parallel algorithms have been developed which can be divided into two categories, those which require a modified Markov chain and those which do not. Parallel algorithms developed for other simulation methods such as Gibbs ensemble Monte Carlo, grand canonical molecular dynamics, and Monte Carlo methods for protein structure determination are also reviewed and issues such as how to measure parallel efficiency, especially in the case of parallel Monte Carlo algorithms with modified Markov chains are discussed.
Development of a novel metal matrix composite based on the Al-B alloy system has been undertaken. Preparation of this discontinuously reinforced material is based on the precipitation of high aspect ratio AlB{sub 2} from an Al-B alloy. This paper describes a number of efforts forced on preparing high volume fractions (> 30 v%) of AlB{sub 2} in aluminum. New insights into the behavior of the Al-B alloys system allowed this effort to be successful.
Wire array Z-pinches on the Z accelerator provide the most intense laboratory source of soft x-rays in the world. The unique combination of a highly-Planckian radiation source with high x-ray production efficiency (15% wall plug), large x-ray powers and energies ( >150 TW, {ge}1 MJ in 7 ns), large characteristic hohlraum volumes (0.5 to >10 cm{sup 3}), and long pulse-lengths (5 to 20 ns) may make Z-pinches a good match to the requirements for driving high-yield scale ICF capsules with adequate radiation symmetry and margin. The Z-pinch driven hohlraum approach of Hammer and Porter [Phys.Plasmas, 6, 2129(1999)] may provide a conservative and robust solution to the requirements for high yield, and is currently being studied on the Z accelerator. This paper describes a multiple region, 0-d hohlraum energetic model for Z-pinch driven hohlraums in four configurations. The authors observe consistency between the models and the measured x-ray powers and hohlraum wall temperatures to within {+-}20% in flux, for the four configurations.
To address lithium-ion cell safety issues in demanding power applications, electrical and thermal abuse tests were performed on 18650 sized cells. Video and electrically monitored abuse tests in air included short circuit, forced overcharge, forced reversal, and controlled overheating (thermal) modes. Controlled overheating tests to 200 C were performed in a sealed chamber under a helium atmosphere and the gases released from the cell during thermal runaway were analyzed at regular intervals using gas chromatography and mass spectrometry. In addition to alkane and alkene solvent breakdown fragments, significant H{sub 2} was detected and evidence that HF was evolved was also found.
As part of a project for the Defense Advanced Research Projects Agency, Sandia National Laboratories Intelligent Systems and Robotics Center is developing and testing the feasibility of using a cooperative team of robotic sentry vehicles to guard a perimeter, perform a surround task, and travel extended distances. This paper describes the authors most recent activities. In particular, this paper highlights the development of a Differential Global Positioning System (DGPS) leapfrog capability that allows two or more vehicles to alternate sending DGPS corrections. Using this leapfrog technique, this paper shows that a group of autonomous vehicles can travel 22.68 kilometers with a root mean square positioning error of only 5 meters.
A molecular dynamics (MD) study of the lithium ultraphosphate glass series, xLi{sub 2}O{center_dot}(1{minus}x)P{sub 2}O{sub 5} (0 {le} x < 0.5) was used to investigate the changes in the Li environment with increasing modifier concentration. The results from the MD simulations indicate that no major structural variations in the Li coordination environment are observed. Changes in the type of oxygen coordinated to the modifier are observed and correlate with the T{sub g} minimum. Additionally, changes in the number of shared phosphorus vertices are observed with increasing modifier concentration, in support of recent models involving the role of the modifier in the extended range structure of phosphate glasses. Empirical calculations of the {sup 6}Li NMR chemical shifts directly from the MD simulation structures is also reported and compared to recent experimental solid-state NMR results.
A theoretical analysis of laser-driven collisional ejection of inner-shell electrons is presented to explain the previously observed anomalous kilovolt L-shell x-ray emission spectra from atomic Xe cluster targets excited by intense sub-picosecond 248nrn ultraviolet radiation. For incident ponderomotively-driven electrons photoionized by strong above threshold ionization, the collisional ejection mechanism is shown to be highly l-state and significantly n-state (i.e. radially) selective for time periods shorter than the collisional dephasing time of the photoionized electronic wavefunction. The resulting preference for the collisional ejection of 2p electrons by an ionized 4p state produces the measured anomalous Xe(L) emission which contains direct evidence for (i) the generation of Xe{sup 27+}(2p{sup 5}3d{sup 10}) and Xe{sup 28+}(2p{sup 5}3d{sup 9}) ions exhibiting inner-shell population inversion and (ii) a coherent correlated electron state collision responsible for the production of double 2p vacancies. For longer time periods, the selectivity of this coherent impact ionization mechanism is rapidly reduced by the combined effects of intrinsic quantum mechanical spreading and dephasing--in agreement with the experimentally observed and extremely strong {minus}{lambda}{sup {minus}6} pump-laser wavelength dependence of the efficiency of inner-shell (2p) vacancy production in Xe clusters excited in underdense plasmas.
A highly selective, coherent impact ionization mechanism is proposed for the efficient generation of inner-shell population inversion in laser-driven plasmas. The theoretical analysis is consistent with observed L-shell (2p{l_arrow}3d) emission spectra from laser-excited Xe clusters.
We report an evaporation-induced self-assembly procedure to prepare poly(bridged silsesquioxane) thin-film and particulate mesophases that incorporate organic moieties (1-3) into periodic, mesostructured frameworks as molecularly dispersed bridging ligands. Capacitance-voltage measurements along with a variety of structural characterization procedures were performed to begin to elucidate structure-property relationships of this new class of surfactant-templated mesophases. We observed a consistent trend of increasing modulus and hardness and decreasing dielectric constant with substitution of the bridged silsesquioxane (≡Si-(CH2)2-Si≡) for siloxane (≡Si-O-Si≡) in the framework. This preliminary evidence suggests that the introduction of integral organic groups into the frameworks of mesoporous materials can result in synergistic properties, promising an unprecedented ability to tune properties and function.
The need for a telerobotic vehicle with hazard sensing and integral manipulation capabilities has been identified for use in transportation accidents where nuclear weapons are involved. The Accident Response Mobile Manipulation System (ARMMS) platform has been developed to provide remote dexterous manipulation and hazard sensing for the Accident Response Group (ARG) at Sandia National Laboratories. The ARMMS' mobility platform is a military HMMWV [High Mobility Multipurpose Wheeled Vehicle] that is teleoperated over RF or Fiber Optic communication channels. ARMMS is equipped with two high strength Schilling Titan II manipulators and a suite of hazardous gas and radiation sensors. Recently, a modular telerobotic control architecture call SMART (Sandia Modular Architecture for Robotic and Teleoperation) has been applied to ARMMS. SMART enables input devices and many system behaviors to be rapidly configured in the field for specific mission needs. This paper summarizes current SMART developments applied to ARMMS.
A series of arylalcohols [H-OAr where OAr = OC{sub 6}H{sub 5} (OPh), OC{sub 6}H{sub 4}(2-Me) (oMP), OC{sub 6}H{sub 3}(2,6-Me){sub 2} (DMP), OC{sub 6}H{sub 4}(2-Pr{prime}) (oPP), OC{sub 6}H{sub 3}(2,6-Pr{prime}){sub 2} (DIP), OC{sub 6}H{sub 4}(2-Bu{prime}) (oBP), OC{sub 6}H{sub 3}(2,6-Bu{prime}){sub 2} (DBP) where Me = CH{sub 3}, Pr{prime} = CHMe{sub 2}, and Bu{prime} = CMe{sub 3}] were reacted with LiN(SiMe{sub 3}){sub 2} in pyridine (py) to generate the appropriate ``Li(OAr)(py){sub x}'' complex. The resultant products were characterized by single crystal X-ray diffraction as: [Li(OPh)(py){sub 2}]{sub 2} (1), [Li(oMP)(py){sub 2}]{sub 2} (2), [Li(DMP)(py){sub 2}]{sub 2} (3), [Li(oPP)(py){sub 2}]{sub 2} (4), [Li(DIP)(py){sub 2}]{sub 2} (5), [Li(oBP)(py){sub 2}]{sub 2} (6), and [Li(DBP)(py)]{sub 2} (7). Compounds 1--6 adopt a dinuclear, edge-shared tetrahedral complex. For 7, due to the steric crowding of the DBP ligand, only one py is coordinated yielding a dinuclear fused trigonal planar arrangement. Two additional structure types were also characterized for the DIP ligand as [Li(DIP)(H-DIP)(py)]{sub 2} (5b) and [Li{sub 2}(DIP){sub 2}(py){sub 3}] (5c). {sup 6,7}Li and {sup 13}C NMR solid state MAS spectroscopy indicated that the bulk powder was consistent with the crystalline material. Solution state NMR spectroscopy revealed a symmetric molecule existed in solution for 1--7.
Mechanical and hydrological properties of salt provide excellent bases for geological isolation of hazardous materials. Regulatory certification of the Waste Isolation Pilot Plant (WIPP) testifies to the nearly ideal characteristics of bedded salt deposits in southeast New Mexico. The WIPP history includes decades of testing and scientific investigations, which have resulted in a comprehensive understanding of salt's mechanical deformational and hydrological properties over an applicable range of stresses and temperatures. Comprehensive evaluation of salt's favorable characteristics helped demonstrate regulatory compliance and ensure isolation of radioactive waste placed in a salt geological setting.
Selectively oxidized vertical cavity lasers emitting at 1294 nm using InGaAsN quantum wells are reported for the first time which operate continuous wave at and above room temperature. The lasers employ two n-type Al{sub 0.94}Ga{sub 0.06}As/GaAs distributed Bragg reflectors each with a selectively oxidized current aperture adjacent to the optical cavity, and the top output mirror contains a tunnel junction to inject holes into the active region. Continuous wave single mode lasing is observed up to 55 C. These lasers exhibit the longest wavelength reported to date for vertical cavity surface emitting lasers grown on GaAs substrates.
The United States Department of Energy initiated the Nuclear Energy Research Initiative (NERI) to conduct research and development with the objectives of: (1) overcoming the principal technical obstacles to expanded nuclear energy use, (2) advancing the state of nuclear technology to maintain its competitive position in domestic and world markets, and (3) improving the performance, efficiency, reliability, and economics of nuclear energy. Fiscal Year 1999 program funding is $19 Million, with increased finding expected for subsequent years, emphasizing international cooperation. Among the programs selected for funding is the ``Smart Equipment and Systems to Improve Reliability and Safety in Future Nuclear Power Plant Operations''. This program is a 30 month collaborative effort bringing together the technical capabilities of ABB C-E Nuclear Power, Inc. (ABB CENP), Sandia National Laboratories, Duke Engineering and Services (DE and S), Massachusetts Institute of Technology (MIT) and Pennsylvania State University (PSU). The program's goal is to design, develop and evaluate an integrated set of smart equipment and predictive maintenance tools and methodologies that will significantly reduce nuclear plant construction, operation and maintenance costs. To accomplish this goal the Smart Equipment program will: (1) Identify and prioritize nuclear plant equipment that would most likely benefit from adding smart features; (2) Develop a methodology for systematically monitoring the health of individual pieces of equipment implemented with smart features (i.e. smart equipment); (3) Develop a methodology to provide plant operators with real-time information through smart equipment Man-Machine Interfaces (MMI) to support their decision making; (4) Demonstrate the methodology on a targeted component and/or system; (5) Expand the concept to system and plant levels that allow communication and integration of data among smart equipment. This paper will discuss (1) detailed subtask plans for the entire program, including expected achievements, (2) preliminary results from the early program phases and (3) the program's relationship to other NERI programs being conducted by the same team.
Backfills have been part of Sandia National Laboratories' [Sandia's] Waste Isolation Pilot Plant [WIPP] designs for over twenty years. Historically, backfill research at Sandia has depended heavily on the changing mission of the WIPP facility. Early testing considered heat producing, high level, wastes. Bentonite/sand/salt mixtures were evaluated and studies focused on developing materials that would retard brine ingress, sorb radionuclides, and withstand elevated temperatures. The present-day backfill consists of pure MgO [magnesium oxide] in a pelletized form and is directed at treating the relatively low contamination level, non-heat producing, wastes actually being disposed of in the WIPP. Its introduction was motivated by the need to scavenging CO{sub 2} [carbon dioxide] from decaying organic components in the waste. However, other benefits, such as a substantial desiccating capacity, are also being evaluated. The MgO backfill also fulfills a statutory requirement for assurance measures beyond those needed to demonstrate compliance with the US Environmental Protection Agency [EPA] regulatory release limits. However, even without a backfill, the WIPP repository design still operates within EPA regulatory release limits.
This paper has shown that it is possible to get significant air intrusion into a ruptured reactor vessel even from a reactor cavity with restricted access. This suggests that there is some importance to considering the consequences of air intrusion following vessel penetration by core debris. The consequences will depend on the nature of core degradation in air and other oxidizing gases. If, indeed, fuel becomes exposed to strongly oxidizing gases, significant releases of ruthenium and hexavalent urania can be expected. Hexavalent urania could alter the nature of cesium release and cesium revaporization from the reactor coolant system. Hexavalent urania could destabilize CSI and enhance the formation of gaseous iodine unless there are other materials that will react readily with atomic iodine along the flow path to the reactor containment.