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At least 343 records · Page 19

Chemical reaction of atomic oxygen with evaporated films of copper, part 4

Evaporated copper films were exposed to an atomic oxygen flux of 1.4 x 10(exp 17) atoms/sq cm per sec at temperatures in the range 285 to 375 F (140 to 191 C) for time intervals between 2 and 50 minutes. Rutherford backscattering spectroscopy (RBS) was used to determine the thickness of the oxide layers formed and the ratio of the number of copper to oxygen atoms in the layers. Oxide film thicknesses ranged from 50 to 3000 A (0.005 to 0.3 microns, or equivalently, 5 x 10(exp -9) to 3 x 10(exp -7); it was determined that the primary oxide phase was Cu2O. The growth law was found to be parabolic (L(t) varies as t(exp 1/2)), in which the oxide thickness L(t) increases as the square root of the exposure time t. The analysis of the data is consistent with either of the two parabolic growth laws. (The thin-film parabolic growth law is based on the assumption that the process is diffusion controlled, with the space charge within the growing oxide layer being negligible. The thick-film parabolic growth law is also based on a diffusion controlled process, but space-charge neutrality prevails locally within very thick oxides.) In the absence of a voltage measurement across the growing oxide, a distinction between the two mechanisms cannot be made, nor can growth by the diffusion of neutral atomic oxygen be entirely ruled out. The activation energy for the reaction is on the order of 1.1 eV (1.76 x 10(exp -19) joule, or equivalently, 25.3 kcal/mole).

Fromhold, A. T.↗

A new approach for simulating inhomogeneous chemical kinetics

Abstract In this paper, inhomogeneous chemical kinetics are simulated by describing the concentrations of interacting chemical species by a linear expansion of basis functions in such a manner that the coupled reaction and diffusion processes are propagated through time efficiently by tailor-made numerical methods. The approach is illustrated through modelling $$\alpha$$ α - and $$\gamma$$ γ -radiolysis in thin layers of water and at their solid interfaces from the start of the chemical phase until equilibrium was established. The method’s efficiency is such that hundreds of such systems can be modelled in a few hours using a single core of a typical laptop, allowing the investigation of the effects of the underlying parameter space. Illustrative calculations showing the effects of changing dose-rate and water-layer thickness are presented. Other simulations are presented which show the approach’s capability to solve problems with spherical symmetry (an approximation to an isolated radiolytic spur), where the hollowing out of an initial Gaussian distribution is observed, in line with previous calculations. These illustrative simulations show the generality and the computational efficiency of this approach to solving reaction-diffusion problems. Furthermore, these example simulations illustrate the method’s suitability for simulating solid-fluid interfaces, which have received a lot of experimental attention in contrast to the lack of computational studies.

97 MATHEMATICS AND COMPUTING↗

Mathematical Model of Transfer and Deposition of Finely Dispersed Particles in a Turbulent Flow of Emulsions and Suspensions

The problem of modeling turbulent transfer of finely dispersed particles in liquids has been considered. An approach is used where the transport of particles is represented in the form of a variety of the diffusion process with the coefficient of turbulent transfer to the wall. Differential equations of transfer are written for different cases, and a solution of the cell model is obtained for calculating the efficiency of separation in a channel. Based on the theory of turbulent transfer of particles and of the boundary layer model, an expression has been obtained for calculating the rate of turbulent deposition of finely dispersed particles. The application of this expression in determining the efficiency of physical coagulation of emulsions in different channels and on the surface of chaotic packings is shown.

42 ENGINEERING↗

Thermodynamic, structural and magnetic studies of phase transformations in MnAl nanocomposite alloys

Highlights: • Small changes in MnAl stoichiometry (5 at.%) produce different phase structure. • In Mn{sub 60}Al{sub 40} as-cast alloy only hcp ε phase can be found • In Mn{sub 55}Al{sub 45} as-cast alloy, there is a mixture of γ{sub 2} (Al{sub 8}Mn{sub 5}) and ε as well as ferromagnetic MnAl τ-phase. • Energies of phase transformation of about 165 kJ/mol for Mn{sub 60}Al{sub 40} and 290 kJ/mol for Mn{sub 55}Al{sub 45} alloys are found. • hcp ε phase decomposes through the migration of interphase interfaces. - Abstract: We have undertaken a temperature-dependent, investigation of the thermodynamics, structure, morphology and magnetism of two MnAl nanocomposite alloys (Mn{sub 60}Al{sub 40} and Mn{sub 55}Al{sub 45}). Differential scanning calorimetry (DSC) studies allowed the determination of the exo-effects occurring in the structural phase transformation of MnAl, while by using temperature-dependent X-ray diffraction of synchrotron radiation we were able to monitor the phase transformation effects and the evolution with temperature of various structural phases occurring in the samples. We have shown that slight changes in stoichiometry (5 at.%) give rise to different phase structure in the as-cast state. While in Mn{sub 60}Al{sub 40} only hcp ε phase can be found, in Mn{sub 55}Al{sub 45} as-cast alloy, there is a quite complex phase structure with a mixture of γ{sub 2} (Al{sub 8}Mn{sub 5}) and ε as well as ferromagnetic MnAl τ-phase. Activation energies of about 165 kJ/mol and 290 kJ/mol have been calculated from the Ozawa-Flynn-Wall analysis of DSC experimental data. These findings are in good agreement with the results obtained from XRD. For the Mn{sub 55}Al{sub 45} as-cast alloy, we have confirmed by temperature-dependent synchrotron XRD that the hcp ε phase decomposes through the migration of interphase interfaces with the transformation rate controlled by boundary diffusion processes. High-resolution transmission electron microscopy have confirmed the phase structure obtained by XRD, while magnetic properties, obtained for the as-cast alloys are consistent with the multiphase character of the samples and in good agreement with previously reported results. The magnetization does not saturate for the maximum applied field of about 4 × 10{sup 6} A/m and a marked coercivity of about 160 kA/m is obtained for the Mn{sub 55}Al{sub 45} as-cast alloy.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Vertical Advection Effects on Hyper-accretion Disks and Potential Link between Gamma-Ray Bursts and Kilonovae

Recent simulations on super-Eddington accretion flows have shown that, apart from the diffusion process, the vertical advection based on magnetic buoyancy can be a more efficient process to release the trapped photons in the optically thick disk. As a consequence, the radiative luminosity from the accretion disk can be far beyond the Eddington value. Following this spirit, we revisit the structure and radiation of hyper-accretion disks with mass accretion rates in the range of 10{sup −3}∼10 M{sub ⊙} s{sup −1}. Our results show that, due to the strong cooling through the vertical advection, the disk temperature becomes lower than that in the classic model without the vertical advection process, and therefore the neutrino luminosity from the disk is lower. On the other hand, the gamma-ray photons released through the vertical advection can be extremely super-Eddington. We argue that the large amount of escaped gamma-ray photons may have more significant contribution to the primordial fireball than the neutrino annihilation, and may hint at a link between gamma-ray bursts and kilonovae in the black hole hyper-accretion scenario.

79 ASTRONOMY AND ASTROPHYSICS↗

Kinetic pathways of fast lithium transport in solid electrolyte interphases with discrete inorganic components

The transport of lithium ions in the solid electrolyte interphase (SEI) has been previously accepted to proceed in two steps: a fast pore diffusion through the outer, porous organic layer followed by a slow knock-off or vacancy diffusion in the inner, dense inorganic layer. The second step is believed to be the rate-limiting step during fast-charging. In this study, we have intentionally constructed a thicker SEI (SEI-rich) structure on the surface of monoclinic Nb 2 O 5 (H-Nb 2 O 5 ) by adding LiNO 3 into a conventional ethylene carbonate based electrolyte. The electrochemical performance of two electrodes, one SEI-rich and one with few SEI (SEI-lean), was found to be almost the same, including their fast-charging capability and cycling stability, despite the significant difference in their SEI structure. Importantly, analysis using cryogenic scanning/transmission electron microscopy showed the discrete decoration of individual inorganic particles (e.g., Li 2 O) and amorphous species (LiN x O y /organic components) over the surface of H-Nb 2 O 5 . These discrete inorganic particles are in contradiction to the formation of dense inner inorganic layer, which has been commonly postulated. Based on these findings, we propose a new mechanism for Li ion transport through the SEI: one-step pore diffusion, without the second step slow diffusion. This one-step pore diffusion process provides an extremely fast Li ion transport, and effectively removes the kinetic limitation of Li ion transport in the SEI for fast charging. Finally, these results strongly suggest that the influence of SEI structure on the transport kinetics of lithium ions is much less significant than previously accepted. These results offer a new understanding of possible lithium ion transport pathway within SEI and may have implications for the future designs of fast-charging battery materials.

25 ENERGY STORAGE↗

Research on solar-wind and magnetospheric electric fields and plasmas

Attempts were made to determine the role of the interplanetary magnetic field in controlling: (1) particle acceleration processes in the earth's polar cap; (2) plasma convection patterns at high latitudes; and, (3) the topology of magnetic field lines in the earth's polar cusps. The primary result of the study on polar-cap particle acceleration regions was that they tend to occur in only one polar cap at a time, and that they occur in the hemisphere for which the magnetospheric tail-lobe field lines have solar-magnetospheric x components that are antiparallel to those of the interplanetary and tail-lobe magnetic field. Southward-directed interplanetary magnetic fields give rise to broad convection throats which cover several hours of local time across the dayside cleft. Under such conditions, solar-wind plasma is channeled efficiently through the polar cusps to populate the plasma mantle and dayside boundary layer. On the other hand, the appearance of strong northward components in the interplanetary magnetic field result in a very constricted throat, resulting in inefficient plasma entry at the cusps by diffusion processes.

Burch, J. L.↗

Experimental and computational investigation into the hydrodynamics and chemical dynamics of laser ablation aluminum plasmas

Laser ablation plasma chemistry is governed by a complex interplay between hydrodynamic plasma-gas mixing processes, thermodynamics, and rapid high-temperature chemical reactions. Here, in this work, we investigate the gas-phase oxidation chemistry of ns-laser ablation aluminum plasmas in air using optical spectroscopy combined with advanced multi-physics modeling. Experimental measurements demonstrate the formation of AlO in the plasma plume as early as 1 μs while computational results reveal that several Al x O y species are distributed in the periphery of the plume at even earlier times (<20 ns) in the presence of large temperature gradients and strong shockwaves. Interactions with the ablation crater during rapid plume expansion are shown to initiate vortex formation, followed by mixing dynamics that work to pull AlO into the vortices to react with gas-phase Al to form Al 2 O. Oxygen and several aluminum oxides are simultaneously pulled up through the stem of the fireball, encouraging further intermixing between reacting species and enhanced molecular formation. This work concludes that chemical dynamics in laser ablation plasmas is driven by diffusion processes, concentration gradients, and plume hydrodynamics while strong shockwaves generated during laser ablation do not impede chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Effect of Boron on the Structure and Conductivity of Thin Films Obtained by Laser Ablation of Diamond with Deposition at 700°C

Structural features of CB{sub x} films obtained by pulsed laser ablation of targets made of pressed diamond powder with boron-powder additions at B/C atomic ratio of x = 0.33 have been studied. The films were deposited on heated substrates, so that diffusion processes involving C and B atoms on the surface and in the volume of films were possible. Selected conditions of film deposition ensured their effective doping with boron (0.4 ≤ x ≤ 0.6). The incorporation of B atoms was accompanied by the formation of B–C chemical bonds, whereas the formation of sp{sup 2} graphite bonds and their ordering in clusters with laminar packing was suppressed. The films possessed very low resistivity (~1.4 mΩ cm) at room temperature and exhibited metallic type of conductance on decreasing the temperature to 77 K.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Atomic-scale analyses of Nb 3 Sn on Nb prepared by vapor diffusion for superconducting radiofrequency cavity applications: a correlative study

We report on atomic-scale analyses of the microstructure of an Nb 3 Sn coating on Nb, prepared by a vapor diffusion process for superconducting radiofrequency (SRF) cavity applications using transmission electron microscopy, electron backscatter diffraction and first-principles calculations. Epitaxial growth of Nb 3 Sn on a Nb substrate is found and four types of orientation relationships (ORs) at the Nb 3 Sn/Nb interface are identified by electron diffraction or high-resolution scanning transmission electron microscopy (HR-STEM) analyses. Thin Nb 3 Sn grains are observed in regions with a low Sn flux and they have a specific OR: Nb 3 Sn (1$\bar{2}$0) //Nb ($\bar{1}$11) and Nb 3 Sn (002) //Nb (0$\bar{1}$1) The Nb 3 Sn/Nb interface of thin grains has a large lattice mismatch, 12.3%, between Nb(0$\bar{1}$1) and Nb 3 Sn (002) and a high density of misfit dislocations as observed by HR-STEM. Based on our microstructural analyses of the thin grains, we conclude that the thin regions are probably a result of a slow interfacial migration with this particular OR. The Sn-deficient regions are seen to form initially at the Nb 3 Sn/Nb interface and remain in the grains due to the slow diffusion of Sn in bulk Nb 3 Sn. The formation of Sn-deficient regions and the effects of interfacial energies on the formation of Sn-deficient regions at different interfaces are estimated by first-principles calculations. The finding of ORs at the Nb 3 Sn/Nb interface provides important information about the formation of imperfections in Nb 3 Sn coatings, such as large thin-regions and Sn-deficient regions, which are critical to the performance of Nb 3 Sn SRF cavities for accelerators.

43 PARTICLE ACCELERATORS↗

Simultaneous enhancement of the coercivity and remanence at high temperatures in a sintered Nd-Fe-B magnet after grain boundary diffusion with Dy60Co40 alloy

Highlights: • Dy and Co enriched shells were formed on the Nd{sub 2}Fe{sub 14}B grain boundaries. • Coercivity and remanence were increased simultaneously at high temperatures. • Remanence stability was improved with little change of the Curie temperature. - Abstract: The grain boundary diffusion process (GBDP) using Dy{sub 60}Co{sub 40} alloy was applied to a sintered Nd-Fe-B magnet. After GBDP the temperature stability of remanence was improved greatly with the remanence temperature coefficient improving from −0.140%/°C to −0.095%/°C while the Curie temperature increased marginally. Both the coercivity and remanence were increased simultaneously at high temperatures. Microstructure and composition analysis revealed that Dy and Co enriched shells were formed on Nd{sub 2}Fe{sub 14}B grain boundaries after GBDP. The Dy enriched shell increased the coercivity while the Co enriched shell decreased the temperature sensitivity of remanence and then increased the remanence at high temperatures.

36 MATERIALS SCIENCE↗

The Role of Diffusion in the Transport of Energetic Electrons during Solar Flares

The transport of the energy contained in suprathermal electrons in solar flares plays a key role in our understanding of many aspects of flare physics, from the spatial distributions of hard X-ray emission and energy deposition in the ambient atmosphere to global energetics. Historically the transport of these particles has been largely treated through a deterministic approach, in which first-order secular energy loss to electrons in the ambient target is treated as the dominant effect, with second-order diffusive terms (in both energy and angle) generally being either treated as a small correction or even neglected. Here, we critically analyze this approach, and we show that spatial diffusion through pitch-angle scattering necessarily plays a very significant role in the transport of electrons. We further show that a satisfactory treatment of the diffusion process requires consideration of non-local effects, so that the electron flux depends not just on the local gradient of the electron distribution function but on the value of this gradient within an extended region encompassing a significant fraction of a mean free path. Our analysis applies generally to pitch-angle scattering by a variety of mechanisms, from Coulomb collisions to turbulent scattering. We further show that the spatial transport of electrons along the magnetic field of a flaring loop can be modeled rather effectively as a Continuous Time Random Walk with velocity-dependent probability distribution functions of jump sizes and occurrences, both of which can be expressed in terms of the scattering mean free path.

79 ASTRONOMY AND ASTROPHYSICS↗

Spiking Neurons for Analysis of Patterns

Artificial neural networks comprising spiking neurons of a novel type have been conceived as improved pattern-analysis and pattern-recognition computational systems. These neurons are represented by a mathematical model denoted the state-variable model (SVM), which among other things, exploits a computational parallelism inherent in spiking-neuron geometry. Networks of SVM neurons offer advantages of speed and computational efficiency, relative to traditional artificial neural networks. The SVM also overcomes some of the limitations of prior spiking-neuron models. There are numerous potential pattern-recognition, tracking, and data-reduction (data preprocessing) applications for these SVM neural networks on Earth and in exploration of remote planets. Spiking neurons imitate biological neurons more closely than do the neurons of traditional artificial neural networks. A spiking neuron includes a central cell body (soma) surrounded by a tree-like interconnection network (dendrites). Spiking neurons are so named because they generate trains of output pulses (spikes) in response to inputs received from sensors or from other neurons. They gain their speed advantage over traditional neural networks by using the timing of individual spikes for computation, whereas traditional artificial neurons use averages of activity levels over time. Moreover, spiking neurons use the delays inherent in dendritic processing in order to efficiently encode the information content of incoming signals. Because traditional artificial neurons fail to capture this encoding, they have less processing capability, and so it is necessary to use more gates when implementing traditional artificial neurons in electronic circuitry. Such higher-order functions as dynamic tasking are effected by use of pools (collections) of spiking neurons interconnected by spike-transmitting fibers. The SVM includes adaptive thresholds and submodels of transport of ions (in imitation of such transport in biological neurons). These features enable the neurons to adapt their responses to high-rate inputs from sensors, and to adapt their firing thresholds to mitigate noise or effects of potential sensor failure. The mathematical derivation of the SVM starts from a prior model, known in the art as the point soma model, which captures all of the salient properties of neuronal response while keeping the computational cost low. The point-soma latency time is modified to be an exponentially decaying function of the strength of the applied potential. Choosing computational efficiency over biological fidelity, the dendrites surrounding a neuron are represented by simplified compartmental submodels and there are no dendritic spines. Updates to the dendritic potential, calcium-ion concentrations and conductances, and potassium-ion conductances are done by use of equations similar to those of the point soma. Diffusion processes in dendrites are modeled by averaging among nearest-neighbor compartments. Inputs to each of the dendritic compartments come from sensors. Alternatively or in addition, when an affected neuron is part of a pool, inputs can come from other spiking neurons. At present, SVM neural networks are implemented by computational simulation, using algorithms that encode the SVM and its submodels. However, it should be possible to implement these neural networks in hardware: The differential equations for the dendritic and cellular processes in the SVM model of spiking neurons map to equivalent circuits that can be implemented directly in analog very-large-scale integrated (VLSI) circuits.

Huntsberger, Terrance↗

Probing the Release and Uptake of Water in α-MnO 2 · x H 2 O

Alpha-MnO 2 is of interest as a cathode material for 3 V lithium batteries and as an electrode/electrocatalyst for higher energy, hybrid Li-ion/Li–O 2 systems. It has a structure with large tunnels that contain stabilizing cations such as Ba 2+ , K + , NH 4 + , and H3O + (or water, H 2 O). When stabilized by H 3 O + /H 2 O, the protons can be ion-exchanged with lithium to produce a Li 2 O-stabilized α-MnO 2 structure. It has been speculated that the electrocatalytic process in Li–O 2 cells may be linked to the removal of lithium and oxygen from the host α-MnO 2 structure during charge, and their reintroduction during discharge. In this investigation, hydrated α-MnO 2 was used, as a first step, to study the release and uptake of oxygen in α-MnO 2 . Temperature-resolved in situ synchrotron X-ray diffraction (XRD) revealed a nonlinear, two-stage, volume change profile, which with the aide of X-ray absorption near-edge spectroscopy (XANES), redox titration, and density functional theory (DFT) calculations, is interpreted as the release of water from the α-MnO 2 tunnels. The two stages correspond to H 2 O release from intercalated H 2 O species at lower temperatures and H 3 O + species at higher temperature. Thermogravimetric analysis confirmed the release of oxygen from α-MnO 2 in several stages during heating–including surface water, occluded water, and structural oxygen–and in situ UV resonance Raman spectroscopy corroborated the uptake and release of tunnel water by revealing small shifts in frequencies during the heating and cooling of α-MnO 2 . Lastly, DFT calculations revealed the likelihood of disordered water species in binding sites in α-MnO 2 tunnels and a facile diffusion process.

36 MATERIALS SCIENCE↗

Fermi Large Area Telescope Observations of the Supernova Remnant GS.7-0.1

We present a detailed analysis of the GeV gamma-ray emission toward the supernova remnant (SNR) G8.7-0.1 with the Large Area Telescope (LAT) onboard the Fermi Gamma-ray Space Telescope. An investigation of the relationship among G8.7-0.1 and the TeV unidentified source HESS J1804-216 provides us with an important clue on diffusion process of cosmic rays if particle acceleration operates in the SNR. The GeV gamma-ray emission is extended with most of the emission in positional coincidence with the SNR G8.7-0.1 and a lesser part located outside the western boundary of G8.7-0.1. The region of the gamma-ray emission overlaps spatially-connected molecular clouds, implying a physical connection for the gamma-ray structure. The total gamma-ray spectrum measured with LAT from 200 MeV-100 GeV can be described by a broken power-law function with a break of 2.4 +/- 0.6 (stat) +/- 1.2 (sys) GeV, and photon indices of2.10 +/- 0.06 (stat) +/- 0.10 (sys) below the break and 2.70 +/- 0.12 (stat) +/- 0.14 (sys) above the break. Given the spatial association among the gamma rays, the radio emission ofG8.7-0.1, and the molecular clouds, the decay of pions produced by particles accelerated in the SNR and hitting the molecular clouds naturally explains the GeV gamma-ray spectrum. We also find that the GeV morphology is not well represented by the TeV emission from HESS Jl804-2l6 and that the spectrum in the Ge V band is not consistent with the extrapolation of the TeV gamma-ray spectrum. The spectral index of the TeV emission is consistent with the particle spectral index predicted by a theory that assumes energy-dependent diffusion of particles accelerated in an SNR. We discuss the possibility that the TeV-spectrum originates from the interaction of particles accelerated in G8.7-0.l with molecular clouds, and we constrain the diffusion coefficient of the particles.

Ferrara, E. C.↗

Fermi Large Area Telescope Observations of the Supernova Remnant GS.7-0.1

We present a detailed analysis of the GeV gamma-ray emission toward the supernova remnant (SNR) G8.7-0.1 with the Large Area Telescope (LAT) on board the Fermi Gamma-ray Space Telescope. An investigation of the relationship among G8.7-0.l and the TeV unidentified source HESS J1804-216 provides us with an important clue on diffusion process of cosmic rays if particle acceleration operates in the SNR. The GeV gamma-ray emission is extended with most of the emission in positional coincidence with the SNR G8.7-0.l and a lesser part located outside the western boundary of G8.7-0.l. The region of the gamma-ray emission overlaps spatially-connected molecular clouds, implying a physical connection for the gamma-ray structure. The total gamma-ray spectrum measured with LAT from 200 MeV-100 GeV can be described by a broken power-law function with a break of 2.4 +/- 0.6 (stat) +/- 1.2 (sys) GeV, and photon indices of 2.10 +/- 0.06 (stat) +/- 0.10 (sys) below the break and 2.70 +/- 0.12 (stat) +/- 0.l4 (sys) above the break. Given the spatial association among the gamma rays, the radio emission of G8.7-0.1, and the molecular clouds, the decay of 1IoS produced by particles accelerated in the SNR and hitting the molecular clouds naturally explains the GeV gamma-ray spectrum. We also find that the GeV morphology is not well represented by the TeV emission from HESS J1804-216 and that the spectrum in the GeV band is not consistent with the extrapolation of the TeV gamma-ray spectrum. The spectral index of the TeV emission is consistent with the particle spectral index predicted by a theory that assumes energy-dependent diffusion of particles accelerated in an SNR. We discuss the possibility that the TeV spectrum originates from the interaction of particles accelerated in G8.7-0.1 with molecular clouds, and we constrain the diffusion coefficient of the particles.

Ajello, M.↗

Effects of Calcite Impurities in Bentonite Buffer Systems on Uranium(VI) Solution Speciation and Sorption Behavior

In many nuclear waste disposal scenarios, bentonite is the proposed buffer material surrounding nuclear waste containers. Its main mineralogical component, Na-montmorillonite clay, is expected to limit radionuclide mobility to slow diffusion processes due to the clay’s low porosity and permeability, and the high sorption affinity of clay surface complexation and cation exchange sites for many radionuclides. Given its mineral structure, montmorillonite provides two types of porosities that can be accessible to radioactive contaminants: macropores between clay particles and interlayer spaces within clay particles, which become dominant at increasing degrees of bentonite compaction. Despite the fact that bentonite naturally contains a variety of mineral impurities (e.g., quartz, feldspars and calcite), most previous studies have only focused on radionuclide interactions with pure Na-montmorillonite phases. Hence, in this study, we will investigate the influence of calcite impurities on uranium(VI) (U(VI)) solution speciation and sorption behavior in bentonite systems. In the presence of water, calcite impurities are expected to lead to milli-molar concentrations of dissolved calcium over a wide range of pH conditions. Consequently, Ca 2+ could – at least partially – replace Na + on clay cation exchange sites, with further implications for exchange reactions of cationic U(VI) species. In addition, ternary U(VI)-Ca-carbonate solution species (CaUO 2 (CO 3 ) 3 2- and Ca 2 UO 2 (CO 3 ) 3 ) will largely replace U(VI)-carbonate species (UO 2 (CO 3 ) 3 4- and UO 2 (CO 3 ) 2 2- ) at alkaline pH. These larger, but lower-charged U(VI) species, may show different sorption and diffusion characteristics, e.g. if their access to negatively-charged clay interlayer spaces is different from binary U(VI)-carbonate complexes. In this presentation, we will first demonstrate the impacts of calcite impurities on U(VI) solution speciation based on PHREEQC simulations. We will then discuss first results from U(VI) sorption studies in these systems. This research is being performed using funding received from the DOE Office of Nuclear Energy's Nuclear Energy University Program.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Elevated Temperature Alpha Spectroscopy with Nickel-Platinum {sup 4}H-SiC Schottky Diodes

In order to protect against the diversion of special nuclear material during pyro-processing of spent nuclear fuel, an online monitoring of the actinide concentrations must be developed. In order to do so, alpha spectroscopy can be employed in order to determine the relative concentrations of various isotopes based on the characteristic alpha spectrum of each isotope of interest. The operating temperatures in the pyro-processing environment are such that high temperature operability of alpha detectors is required. The Idaho National Laboratory (INL) electro-refiner operates at a molten salt temperature of approximately 500 deg. C. The vapor temperature above the molten salt is approximately 100 deg. C. In order to provide reasonably compact online monitoring of the actinide concentrations within the molten salt the detector would be located in this vapor region. The temperature in this location is too high for a commercial silicon detector to operate without serious signal degradation due to thermal noise. As the operating temperature increases, the thermal energy available to the charge carriers within the semiconductor increases. For narrow band-gap semiconductors like silicon, this increase in free charge carriers with increasing temperature leads to unacceptable leakage current at relatively low temperatures when compared with wide band-gap materials. In order to overcome this, a wide band-gap material is employed. An alpha particle sensor utilizing a nickel Schottky barrier {sup 4}HSiC wafer was heated to a temperature of 100 deg. C and an alpha spectrum collected. The performance of the sensor at 100 deg. C was compared to the room temperature performance. Molten salts such as those used in the INL electro-refiner exhibit strong corrosive properties. Any sensor which will be exposed to or submerged in the molten salt must have a ruggedized sensor face capable to withstand the corrosive environment. In the contact design utilized in this paper the Schottky barrier forming metal, nickel, is coated with a thin layer of platinum to serve as a corrosion resistant layer. An additional modification to previous designs was the simplification of the Schottky barrier composition. A Schottky barrier is created when a metal is brought into close physical contact with a semiconductor. To first order, the barrier height of the Schottky barrier is a result of the mismatch between the electron affinity of the semiconductor and the metal work function of the metal. In previous iterations, the high temperature performance of the detectors had been limited by diffusion processes between the various metal layers. In order to reduce the likelihood of such a degradation, the Schottky contact structure was simplified without loss of functionality. By replacing the multiple metal layers with a nickel Schottky forming layer capped with a thin platinum layer, the potential degradation of the Schottky barrier height could be reduced, primarily through the similar Schottky barrier height to nickel formed by platinum with SiC.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗