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At least 343 records · Page 19

On Surface Order and Disorder of α-Pinene-Derived Secondary Organic Material

The surfaces of secondary organic aerosol particles are notoriously difficult to access experimentally, even though they are the key location where exchange between the aerosol particle phase and its gas phase occurs. Here, we overcome this difficulty by applying standard and sub 1-cm-1 resolution vibrational sum frequency generation (SFG) spectroscopy to detect C–H oscillators at the surfaces of secondary organic material (SOM) prepared from the ozonolysis of α-pinene at Harvard University and at the University of California, Irvine that were subsequently collected on Teflon filters as well as CaF2 windows using electrostatic deposition. We find both samples yield comparable SFG spectra featuring an intense peak at 2940 cm-1 that are independent of spectral resolution and location or method of preparation. We hypothesize that the SFG spectra are due to surface-active C–H oscillators associated with the four-membered ring motif of α-pinene, which produces an unresolvable spectral continuum of approximately 50 cm-1 width reminiscent of the similar, albeit much broader, O–H stretching continuum observed in the SFG spectra of aqueous surfaces. Upon subjecting the SOM samples to cycles in relative humidity (RH) between <2% RH and 95% RH, we observe reversible changes in the SFG signal intensity across the entire spectral range surveyed for a polarization combination probing components of the vibrational transition dipole moments that are oriented parallel to the plane of incidence, but no signal intensity changes for any other polarization combination investigated. These results support the notion that the C–H oscillators at the surfaces of α-pinene-derived SOM deposited on CaF2 windows shift back and forth between two different molecular orientation distributions as the RH is lowered (more ordered) or raised (less ordered). The findings thus point towards the presence of a reversible surface switch for hindering (more ordered, <2%RH) and promoting (less ordered, 95%RH) exchange between the aerosol particle phase and its gas phase.

Environmental Molecular Sciences Laboratory↗

Humidity effects on tip-induced polarization switching in lithium niobate

In the last several decades, ferroelectrics have attracted much attention as perspective materials for nonlinear optics and data storage devices. Scanning probe microscopy (SPM) has emerged as a powerful tool both for studies of domain structures with nanoscale spatial resolution and for writing the isolated nanodomains by local application of the electric field. Quantitative analysis of the observed behavior requires understanding the role of environmental factors on imaging and switching process. Here, we study the influence of the relative humidity in the SPM chamber on tip-induced polarization switching. The observed effects are attributed to existence of a water meniscus between the tip and the sample surface in humid atmosphere. These results are important for a deeper understanding of complex investigations of ferroelectric materials and their applications and suggest the necessity for fundamental studies of electrocapillary phenomena at the tip-surface junction and their interplay with bias-induced materials responses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Three-dimensional interaction force and tunneling current spectroscopy of point defects on rutile TiO 2 (110)

Here, the extent to which point defects affect the local chemical reactivity and electronic properties of an oxide surface was evaluated with picometer resolution in all three spatial dimensions using simultaneous atomic force/scanning tunneling microscopy measurements performed on the (110) face of rutile TiO 2 . Oxygen atoms were imaged as protrusions in both data channels, corresponding to a rarely observed imaging mode for this prototypical metal oxide surface. Three-dimensional spectroscopy of interaction forces and tunneling currents was performed on individual surface and subsurface defects as a function of tip-sample distance. An interstitial defect assigned to a subsurface hydrogen atom is found to have a distinct effect on the local density of electronic states on the surface, but no detectable influence on the tip-sample interaction force. Meanwhile, spectroscopic data acquired on an oxygen vacancy highlight the role of the probe tip in chemical reactivity measurements.

36 MATERIALS SCIENCE↗

SIMS Analyses of Aerodynamic Fallout from a Uranium-Fueled Test

Five silicate fallout glass spherules produced in a uranium-fueled, near-surface nuclear test were characterized by secondary ion mass spectrometry, electron probe microanalysis, autoradiography, scanning electron microscopy, and energy-dispersive x ray spectroscopy. Several samples display distinctive compositional heterogeneity suggestive of incomplete mixing, and exhibit heterogeneity in U isotopes with 0.02 < 235 U/ 238 U < 11.8 among all five samples and 0.02 < 235 U/ 238 U < 7.81 within a single sample. In two samples, the 235 U/ 238 U ratio is correlated with major element composition, consistent with the agglomeration of chemically and isotopically distinct molten precursors. Two samples are quasi-homogeneous with respect to composition and uranium isotopic composition, suggesting extensive mixing possibly due longer residence time in the fireball. Correlated variations between 234 U, 235 U, 236 U and 238 U abundances point to mixing of end-members corresponding to uranium derived from the device and natural U ( 238 U/ 235 U = 0.00725) found in soil.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermospheric temperature measurement technique.

A method for measurement of temperature in the earth's lower thermosphere from a high-velocity probes is described. An undisturbed atmospheric sample is admitted to the instrument by means of a free molecular flow inlet system of skimmers which avoids surface collisions of the molecules prior to detection. Measurement of the time-of-flight distribution of an initially well-localized group of nitrogen metastable molecular states produced in an open, crossed electron-molecular beam source, yields information on the atmospheric temperature. It is shown that for high vehicle velocities, the time-of-flight distribution of the metastable flux is a sensitive indicator of atmospheric temperature. The temperature measurement precision should be greater than 94% at the 99% confidence level over the range of altitudes from 120-170 km. These precision and altitude range estimates are based on the statistical consideration of the counting rates achieved with a multichannel analyzer using realistic values for system parameters.

Hueser, J. E.↗

Titan Orbiter with Aerorover Mission (TOAM)

We propose to develop a new mission to Titan called Titan Orbiter with Aerorover Mission (TOAM). This mission is motivated by the recent discoveries of Titan, its atmosphere and its surface by the Huygens Probe, and a combination of in situ, remote sensing and radar mapping measurements of Titan by the Cassini orbiter. Titan is a body for which Astrobiology (i.e., prebiotic chemistry) will be the primary science goal of any future missions to it. TOAM is planned to use an orbiter and balloon technology (i.e., aerorover). Aerobraking will be used to put payload into orbit around Titan. The Aerorover will probably use a hot air balloon concept using the waste heat from the MMRTG approx. 500 watts. Orbiter support for the Aerorover is unique to our approach for Titan. Our strategy to use an orbiter is contrary to some studies using just a single probe with balloon. Autonomous operation and navigation of the Aerorover around Titan will be required, which will include descent near to the surface to collect surface samples for analysis (i.e., touch and go technique). The orbiter can provide both relay station and GPS roles for the Aerorover. The Aerorover will have all the instruments needed to sample Titan's atmosphere, surface, possible methane lakes-rivers, use multi-spectral imagers for surface reconnaissance; to take close up surface images; take core samples and deploy seismometers during landing phase. Both active and passive broadband remote sensing techniques will be used for surface topography, winds and composition measurements.

Sittler, Edward C.↗

Titan Orbiter with Aerorover Mission (TOAM)

We propose to develop a new mission to Titan called Titan Orbiter with Aerorover Mission (TOAM). This mission is motivated by the recent discoveries of Titan, its atmosphere and its surface by the Huygens Probe, and a combination of in situ, remote sensing and radar mapping measurements of Titan by the Cassini orbiter. Titan is a body for which Astrobiology (i.e., prebiotic chemistry) will be the primary science goal of any future missions to it. TOAM is planned to use an orbiter and balloon technology (i.e., aerorover). Aerobraking will be used to put payload into orbit around Titan. One could also use aerobraking to put spacecraft into orbit around Saturn first for an Enceladus phase of the mission and then later use aerocapture to put spacecraft into orbit around Titan. The Aerorover will probably use a hot air balloon concept using the waste heat from the MMRTG approx. 1000 watts. Orbiter support for the Aerorover is unique to our approach for Titan. Our strategy to use an orbiter is contrary to some studies using just a single probe with balloon. Autonomous operation and navigation of the Aerorover around Titan will be required, which will include descent near to the surface to collect surface samples for analysis (i.e., touch and go technique). The orbiter can provide both relay station and GPS roles for the Aerorover. The Aerorover will have all the instruments needed to sample Titan's atmosphere, surface, possible methane lakes-rivers, use multi-spectral imagers for surface reconnaissance; to take close up surface images; take core samples and deploy seismometers during landing phase. Both active and passive broadband remote sensing techniques will be used for surface topography, winds and composition measurements.

Sittler, E. C., Jr.↗

Nonlinear Dynamics of Cantilever-Sample Interactions in Atomic Force Microscopy

The interaction of the cantilever tip of an atomic force microscope (AFM) with the sample surface is obtained by treating the cantilever and sample as independent systems coupled by a nonlinear force acting between the cantilever tip and a volume element of the sample surface. The volume element is subjected to a restoring force from the remainder of the sample that provides dynamical equilibrium for the combined systems. The model accounts for the positions on the cantilever of the cantilever tip, laser probe, and excitation force (if any) via a basis set of set of orthogonal functions that may be generalized to account for arbitrary cantilever shapes. The basis set is extended to include nonlinear cantilever modes. The model leads to a pair of coupled nonlinear differential equations that are solved analytically using a matrix iteration procedure. The effects of oscillatory excitation forces applied either to the cantilever or to the sample surface (or to both) are obtained from the solution set and applied to the to the assessment of phase and amplitude signals generated by various acoustic-atomic force microscope (A-AFM) modalities. The influence of bistable cantilever modes of on AFM signal generation is discussed. The effects on the cantilever-sample surface dynamics of subsurface features embedded in the sample that are perturbed by surface-generated oscillatory excitation forces and carried to the cantilever via wave propagation are accounted by the Bolef-Miller propagating wave model. Expressions pertaining to signal generation and image contrast in A-AFM are obtained and applied to amplitude modulation (intermittent contact) atomic force microscopy and resonant difference-frequency atomic force ultrasonic microscopy (RDF-AFUM). The influence of phase accumulation in A-AFM on image contrast is discussed, as is the effect of hard contact and maximum nonlinearity regimes of A-AFM operation.

Cantrell, John H.↗

Feedback on Forty-year Long Clean-up Operations of a Contaminated Soil for Environmental Purpose - 20026

One of the CEA facilities in France is the place of miscellaneous mapping and clean-up operations since the 1980's. The final purpose of the conducted work deals with the environmental remediation of the building. In France, the absence of a regulatory framework for the management of sites polluted by radioactive substances, especially as the lack of release thresholds, has led to develop different approaches of soil radiological characterization. The geostatistical approach is part of them. Preliminary investigations are an unavoidable step prior to clearance and remediation. First, historical analysis enables to define site perimeters to investigate as well as to precisely locate expected contaminated parts. For radioactive pollutants, the media (water, soil, air) and transfer routes participate in the definition of the investigation perimeter and thus also need to be identified through a geological study. At the same time, functional analysis leads to choose the best measurement means which could provide useful information when combined with visual inspection. An equipment well adapted to easy-to-measure radionuclides as gamma emitters, such as gamma probe or on-site gamma spectrometry, is usually selected as a non-destructive assay. Coupled with spatial positions, processed on-site radiological data can be mapped. Data processing consists in mapping and kriging before a geostatistical analysis in order to identify the zones of interest to be targeted. Selected zones are not only linked to high level count rates but also to low level ones so that a pollution-free reference is known in the area. This data processing also enables to categorize waste types according to their origin and contamination levels. An expected volume of different waste then follows as well as the waste characterization equipments. In-depth investigations, e.g. core drillings and samplings, naturally ensue to aim at remediation optimization through the assessment of environmental impact. After clean-up operations, non-destructive assays as well as destructive samplings enable to check the effective clearance. Following this methodology in the present remediation work, results of the first non-destructive assay campaign highlighted a long-lived transuranic radionuclides contamination in the concrete flagstone. Successive non-destructive assays were then performed in the defined zones of interest. Count rates measured with a surface probe were first mapped. The best localization of destructive assays, i.e. core drillings at a 1 meter depth, came from this surface mapping followed by a geostatistical analysis. The concrete flagstone was totally removed. Then, the depth of soil to remove under the flagstone was optimized from the results of radiological activities measured in core drillings samples. A new surface mapping was then drawn after this partial soil excavation. The sand and demolition rubble samples, homogeneously constituted from the flagstone fragments, were analyzed by gamma spectrometry. Meanwhile, waste drums and other containers were also measured by gamma spectrometry and passive neutron measurement devices. All these results have brought miscellaneous pieces of information. In this context, major issues appear in terms of physical constraints such as the premises tininess as well as of soil sampling techniques and in terms of measurement performances assessment and the representativeness of homogeneous samples. The choice of radiological soil and waste characterization devices is described in the light of enhanced performances by keeping in mind radiation protection requirements and a willing to always optimize waste categories (very low level waste) and volume. The improvement of the characterization methods appears through this forty-year long work while sharing the feedback of encountered difficulties. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Time and space resolved interferometry for laser-generated fast electron measurements

A technique developed to measure in time and space the dynamics of the electron populations resulting from the irradiation of thin solids by ultraintense lasers is presented. It is a phase reflectometry technique that uses an optical probe beam reflecting off the target rear surface. The phase of the probe beam is sensitive to both laser-produced fast electrons of low-density streaming into vacuum and warm solid density electrons that are heated by the fast electrons. A time and space resolved interferometer allows to recover the phase of the probe beam sampling the target. The entire diagnostic is computationally modeled by calculating the probe beam phase when propagating through plasma density profiles originating from numerical calculations of plasma expansion. Matching the modeling to the experimental measurements allows retrieving the initial electron density and temperature of both populations locally at the target surface with very high temporal and spatial resolution ({approx}4 ps,6 {mu}m). Limitations and approximations of the diagnostic are discussed and analyzed.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

A comparison of ship and Coastal Zone Color Scanner mapped distribution of phytoplankton in the southeastern Bering Sea

Twenty-one Coastal Zone Color Scanner (CZCS) images of the southeastern Bering Sea are examined in order to map the near-surface distribution of phytoplankton during 1979 and 1980. The information is compared with the mesoscale (100-1000 km) distribution of phytoplankton inferred from pooled ship sampling obtained during the Processes and Resources of the Bering Shelf (PROBES) intensive field study during the late 1970s and early 1980s. The imagery indicates that open-water phytoplankton blooms occur first in late April in coastal waters, peak in early May over the middle shelf, and decay rapidly afterwards, reaching concentration minima in June in both regions. These patterns show that the earlier ship observations are valid for most of the eastern Bering shelf. A very tight correlation is found between the PROBES surface chlorophyll a concentrations and mean mixed-layer chlorophyll concentrations. The significant discrepancies between CZCS and ship-based chlorophyll estimates may be due to aliasing in time by the CZCS. It is concluded that neither satellite nor ship alone can do an adequate job of characterizing the physics or biological dynamics of the ocean.

Mcclain, C. R.↗

Spatially resolved chemical imaging of individual atmospheric particles using nanoscale imaging mass spectrometry: Insighs into particle origin and chemistry

Knowledge of the spatially-resolved composition of atmospheric particles is essential for differentiating between their surface versus bulk chemistry, understanding particle reactivity and the potential environmental impact. We demonstrate the application of nanometer-scale secondary ion mass spectrometry (Cameca NanoSIMS 50 ion probe) for 3D chemical imaging of individual atmospheric particles without any sample pre-treatment, such as the sectioning of particles. Use of NanoSIMS depth profile analysis enables elemental mapping of particles with nanometer spatial resolution over a broad of range of particle sizes. We have used this technique to probe spatially resolved composition of ambient particles collected during a field campaign in Mexico City. Particles collected during this campaign have been extensively characterized in the past using other particle analysis techniques and hence offer a unique opportunity for exploring the utility of depth resolved chemical imaging in ambient particle research. 1 Particles examined in this study include those collected during a pollution episode related to urban waste incineration as well as background particles from the same location prior to the episode. Particles from the pollution episode show substantial intra-particle compositional variability typical of particles resulting from multiple emission sources. In contrast, the background particles have relatively homogeneous compositions with enhanced presence of nitrogen, oxygen and chlorine at the particle surface. The observed surface enhancement of nitrogen and oxygen species is consistent with the presence of surface nitrates resulting from gas-particle heterogeneous interactions and is indicative of atmospheric ageing of the particles. The results presented here illustrate 3D characterization of ambient particles for insights into their chemical history.

Environmental Molecular Sciences Laboratory↗

Spatially-Resolved Analyses of Aerodynamic Fallout from a Uranium-Fueled Nuclear Test

The fiive silicate fallout glass spherules produced in a uranium-fueled, near-surface nuclear test were characterized by secondary ion mass spectrometry, electron probe microanalysis, autoradiography, scanning electron microscopy, and energy-dispersive x-ray spectroscopy. Several samples display compositional heterogeneity suggestive of incomplete mixing between major elements and natural U ( 238 U/ 235 U = 0.00725) and enriched U. Samples exhibit extreme spatial heterogeneity in U isotopic composition with 0.02 < 235 U/ 238 U < 11.84 among all five spherules and 0.02 < 235 U/ 238 U < 7.41 within a single spherule. Moreover, in two spherules, the 235 U/ 238 U ratio is correlated with changes in major element composition, suggesting the agglomeration of chemically and isotopically distinct molten precursors. Two samples are nearly homogenous with respect to major element and uranium isotopic composition, suggesting extensive mixing possibly due to experiencing higher temperatures or residing longer in the fireball. Linear correlations between 234 U/ 238 U, 235 U/ 238 U, and 236 U/ 238 U ratios are consistent with a two-component mixing model, which is used to illustrate the extent of mixing between natural and enriched U end members.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Scalable synthesis of supported catalysts using fluidized bed atomic layer deposition

Overcoating layers deposited on the surface of heterogeneous catalysts using atomic layer deposition (ALD) have been shown to increase catalyst activity, lifetime, and selectivity. In this study, we performed Al 2 O 3 ALD and Pd ALD in a commercial fluidized bed reactor on high surface area mesoporous powder supports to create overcoated catalysts with high precursor utilization. We investigated the reaction mechanism for both Al 2 O 3 ALD and Pd ALD using in situ mass spectrometry and developed a mathematical model to understand the precursor saturation behaviors. We characterized the catalyst samples using a variety of techniques to measure the surface area, porosity, composition, and surface chemistry of the overcoated catalysts. Finally, we used propane dehydrogenation as a probe reaction to evaluate the performance of the catalysts prepared by fluidized bed ALD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Picosecond ultrasonic study of surface acoustic waves on titanium nitride nanostructures

We have measured surface acoustic waves on nanostructured TiN wires overlaid on multiple thin films on a silicon substrate using the ultrafast pump-probe technique known as picosecond ultrasonics. We find a prominent oscillation in the range of 11–54 GHz for samples with varying pitch ranging from 420 nm down to 168 nm. We find that the observed oscillation increases monotonically in frequency with decrease in pitch, but that the increase is not linear. By comparing our data to two-dimensional mechanical simulations of the nanostructures, we find that the type of surface oscillation to which we are sensitive changes depending on the pitch of the sample. Surface waves on substrates that are loaded by thin films can take multiple forms, including Rayleigh-like waves, Sezawa waves, and radiative (leaky) surface waves. We describe evidence for detection of modes that display characteristics of these three surface wave types.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Fermi surface, possible unconventional fermions, and unusually robust resistive critical fields in the chiral-structured superconductor AuBe

The noncentrosymmetric superconductor (NCS) AuBe is investigated using a variety of thermodynamic and resistive probes in magnetic fields of up to 65 T and temperatures down to 0.3 K. Despite the polycrystalline nature of the samples, the observation of a complex series of de Haas–van Alphen (dHvA) oscillations has allowed the calculated band structure for AuBe to be validated. This permits a variety of BCS parameters describing the superconductivity to be estimated, despite the complexity of the measured Fermi surface. In addition, AuBe displays a nonstandard field dependence of the phase of dHvA oscillations associated with a band thought to host unconventional fermions in this chiral lattice. Overall, this result demonstrates the power of the dHvA effect to establish the properties of a single band despite the presence of other electronic bands with a larger density of states, even in polycrystalline samples. In common with several other NCSs, we find that the resistive upper critical field exceeds that measured by heat capacity and magnetization by a considerable factor. We suggest that our data exclude mechanisms for such an effect associated with disorder, implying that topologically protected superconducting surface states may be involved.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Thermoreflectance Detection of Point Defects Resulting from Focused Ion Beam Milling

Focused ion beam (FIB) milling is a commonly used tool for nanoscale material processing, such as for transmission electron microscopy (TEM) sample preparation, or the creation of fiducial markers prior to other processes and measurements. During milling, a high energy ion beam is used to remove material via sputtering. The expelled target material may return to the sample surface however, affecting subsequent measurements. Beam spreading or irradiation due to neutral gallium may also irradiate a larger area than intended. Extensive research has explored the effects of FIB milling on the prepared TEM sample, but few have looked at the effects of milling on the properties of the sample surrounding the milled region. We use multiple pump-probe laser-based techniques (time domain thermoreflectance and steady-state thermoreflectance) to measure the spatial extent of FIB-induced surface/subsurface changes on a series of silicon wafers milled at multiple currents and doses. We supplement these measurements with high-resolution scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, stylus profilometry, and time-of-flight secondary ion mass spectroscopy. We find a sample surface affected by the FIB up to 1 mm from where milling occurred, with a notable dependence on the ion beam current. We also note remarkably high sensitivity to surface defects using the thermoreflectance metrologies, including detection where other measurements failed.

defects↗