Nanoporous-carbon adsorbers for chemical microsensors.

Chemical microsensors rely on partitioning of airborne chemicals into films to collect and measure trace quantities of hazardous vapors. Polymer sensor coatings used today are typically slow to respond and difficult to apply reproducibly. The objective of this project was to produce a durable sensor coating material based on graphitic nanoporous-carbon (NPC), a new material first studied at Sandia, for collection and detection of volatile organic compounds (VOC), toxic industrial chemicals (TIC), chemical warfare agents (CWA) and nuclear processing precursors (NPP). Preliminary studies using NPC films on exploratory surface-acoustic-wave (SAW) devices and as a {micro}ChemLab membrane preconcentrator suggested that NPC may outperform existing, irreproducible coatings for SAW sensor and {micro}ChemLab preconcentrator applications. Success of this project will provide a strategic advantage to the development of a robust, manufacturable, highly-sensitive chemical microsensor for public health, industrial, and national security needs. We use pulsed-laser deposition to grow NPC films at room-temperature with negligible residual stress, and hence, can be deposited onto nearly any substrate material to any thickness. Controlled deposition yields reproducible NPC density, morphology, and porosity, without any discernable variation in surface chemistry. NPC coatings > 20 {micro}m thick with density < 5% that of graphite have been demonstrated. NPC can be 'doped' with nearly any metal during growth to provide further enhancements in analyte detection and selectivity. Optimized NPC-coated SAW devices were compared directly to commonly-used polymer coated SAWs for sensitivity to a variety of VOC, TIC, CWA and NPP. In every analyte, NPC outperforms each polymer coating by multiple orders-of-magnitude in detection sensitivity, with improvements ranging from 103 to 108 times greater detection sensitivity! NPC-coated SAW sensors appear capable of detecting most analytes tested to concentrations below parts-per-billion. In addition, the graphitic nature of NPC enables thermal stability > 600 C, several hundred degrees higher than the polymers. This superior thermal stability will enable higher-Temperature preconcentrator operation, as well as greatly prolonged device reliability, since polymers tend to degrade with time and repeated thermal cycling

A dual neutron/gamma source for the Fissmat Inspection for Nuclear Detection (FIND) system.

Shielded special nuclear material (SNM) is very difficult to detect and new technologies are needed to clear alarms and verify the presence of SNM. High-energy photons and neutrons can be used to actively interrogate for heavily shielded SNM, such as highly enriched uranium (HEU), since neutrons can penetrate gamma-ray shielding and gamma-rays can penetrate neutron shielding. Both source particles then induce unique detectable signals from fission. In this LDRD, we explored a new type of interrogation source that uses low-energy proton- or deuteron-induced nuclear reactions to generate high fluxes of mono-energetic gammas or neutrons. Accelerator-based experiments, computational studies, and prototype source tests were performed to obtain a better understanding of (1) the flux requirements, (2) fission-induced signals, background, and interferences, and (3) operational performance of the source. The results of this research led to the development and testing of an axial-type gamma tube source and the design/construction of a high power coaxial-type gamma generator based on the {sup 11}B(p,{gamma}){sup 12}C nuclear reaction

Investigation of the effects of intense pulsed particle beams on the durability of metal-to-plastic interfaces.

We have investigated the potential for intense particle beam surface modification to improve the mechanical properties of materials commonly used in the human body for contact surfaces in, for example, hip and knee implants. The materials studied include Ultra-High Molecular Weight Polyethylene (UHMWPE), Ti-6Al-4Al (titanium alloy), and Co-Cr-Mo alloy. Samples in flat form were exposed to both ion and electron beams (UHMWPE), and to ion beam treatment (metals). Post-analysis indicated a degradation in bulk properties of the UHMWPE, except in the case of the lightest ion fluence tested. A surface-alloyed Hf/Ti layer on the Ti-6Al-4V is found to improve surface wear durability, and have favorable biocompatibility. A promising nanolaminate ceramic coating is applied to the Co-Cr-Mo to improve surface hardness

Iron Oxide-Rich Filaments: Possible Fossil Bacteria in Lechuguilla Cave, New Mexico

Reddish filaments in two fragments of unusual iron oxide bearing stalactites, the Rusticles from Lechuguilla Cave, New Mexico, are found only within the central canals of the Rusticles. The curved, helical, and/or vibrioidal filaments vary from 1 to 6 w m in outer diameter and 10 to \u3e 50 w m in length. SEM and TEM show the filaments have 0.5- w m diameter central tubes, with goethite crystals radiating outwardly along their lengths. The diameter of the central tubes is consistent with the diameter of many ironoxidizing filamentous bacteria. Although most iron oxide depositing bacteria do not deposit well-crystallized radiating goethite, we propose thick hydrous iron oxide was slowly crystallized from amorphous material to goethite, in place, over a relatively long period of time. From the gross morphology and the particular setting, we suggest this represents an occurrence of fossilized, acidophilic iron-oxidizing bacteria

U-Pb dating of speleogenetic dolomite: A new sulfuric acid speleogenesis chronometer

The 1100-meter Big Room elevation level of Carlsbad Cavern, New Mexico USA, formed 4 Ma by hypogenic sulfuric acid speleogenesis (SAS). The age of the Big Room level of 4.0 ± 0.2 Ma was previously determined by dating alunite, a byproduct of speleogenesis, using the 40Ar/39Ar method. Duplication of these results is possible by radiometric dating of other byproducts interpreted to be speleogenetic (a byproduct of speleogenesis) such as calcite and dolomite in certain settings. XRD and TEM analyses of sample 94044, a piece of crust collected within the Big Room level of SAS just below Left Hand Tunnel indicate that this dolomite sample we interpret to be speleogenetic is as well-ordered crystallographically as the Permian bedrock dolomite, possibly reflecting its SAS origin. Three U-Pb analyses were performed on subsamples A1, A2, and A3 of sample 94044, and two, A1 & A2, produced out-of-secular equilibrium results due to the presence of authigenic quartz and/or later re-distribution of uranium in the dolomite crust, which prevented the calculation of an isochron age. Because subsample 94044-A3 exhibited δ234U and 230Th/238U values consistent with secular equilibrium, we were able to generate a 238U/204Pb-206Pb/204Pb model age of 4.1 ± 1.3 Ma on the dolomite crust (94044) that we interpret to be reliable. The 4.1 Ma age of the speleogenetic dolomite crust agrees with the 4 Ma 40Ar/39Ar age for the timing of speleogenesis of the Big Room level. While 40Ar/39Ar-dating of speleogenetic alunite- and jarosite-group minerals remains the primary way to determine absolute timing of hypogenic SAS, here we demonstrate that U-Pb dating of speleogenetic dolomite can be used to compliment or independently measure the timing of SAS. This method of dating SAS could be applicable in caves where the more soluble SAS-indicator minerals such as gypsum, alunite, and jarosite have been removed

Age and Origin of Carlsbad Cavern and Related Caves from 40Ar/39Ar of Alunite

40Ar/39Ar dating of fine-grained alunite that formed during cave genesis provides ages of formation for the Big Room level of Carlsbad Cavern [4.0 to 3.9 million years ago (Ma)], the upper level of Lechuguilla Cave (6.0 to 5.7 Ma), and three other hypogene caves (11.3 to 6.0 Ma) in the Guadalupe Mountains of New Mexico. Alunite ages increase and are strongly correlative with cave elevations, which indicates an 1100-meter decline in the water table, apparently related to tectonic uplift and tilting, from 11.3 Ma to the present. 40Ar/39Ar dating studies of the hypogene caves have the potential to help resolve late Cenozoic climatic, speleologic, and tectonic questions

Ion-induced gammas for photofission interrogation of HEU.

High-energy photons and neutrons can be used to actively interrogate for heavily shielded special nuclear material (SNM), such as HEU (highly enriched uranium), by detecting prompt and/or delayed induced fission signatures. In this work, we explore the underlying physics for a new type of photon source that generates high fluxes of mono-energetic gamma-rays from low-energy (<500 keV) proton-induced nuclear reactions. The characteristic energies (4- to 18-MeV) of the gamma-rays coincide with the peak of the photonuclear cross section. The source could be designed to produce gamma-rays of certain selected energies, thereby improving the probability of detecting shielded HEU or providing a capability to determine enrichment inside sealed containers. The fundamental physics of such an interrogation source were studied in this LDRD through scaled ion accelerator experiments and radiation transport modeling. The data were used to assess gamma and neutron yields, background, and photofission-induced signal levels from several (p,{gamma}) target materials under consideration

The West Water Formation (Hualapai Plateau, Arizona, USA) as a calcrete-paleosol sequence, and its implications for the Paleogene-Neogene evolution of the southwestern Colorado Plateau

Analyses of stratigraphic sequences within the paleocanyons of the Hualapai Plateau, Arizona, are important because these deposits offer the only evidence for the Paleogene-Neogene geological history of the Grand Canyon area. In this paper, we focus on the origins and paleoenvironmental significance of the West Water Formation, located within the Milkweed and West Water paleocanyons on the Hualapai Plateau. We propose that the supposed “limestone unit” of the West Water Formation at and near its type section is not a limestone; rather, it is a 21 m-thick valley calcrete, overprinted by a ~ 1–2 m-thick pedogenic calcrete, and subsequently dolomitized in its upper-to-middle sections, with a superimposed 4 m-thick red paleosol. We also propose that this unit is not coeval in age or origin with the Long Point limestone on the Coconino Plateau, and that the presence of a complex calcrete-dolocrete-paleosol alters previous interpretations associated with this unit. Evidence for a calcrete-paleosol origin, beyond the West Water Formation\u27s lack of fossils, includes: its predominantly micritic calcite-palygorskite composition; its textures characteristic of valley and pedogenic calcrete deposits (as exhibited by thin section, SEM, and TEM analyses); and its association with a relatively thick overlying red paleosol that also contains abundant palygorskite. Stable carbon and oxygen isotope values from carbonate cements are also within the range expected of a near-surface calcrete. Carbonate minerals within the calcrete-dolocrete were precipitated at or near the water table in a valley setting due to evaporation and/or CO2 degassing in a semi-arid to arid environment of deposition. High 87Sr/86Sr values within the calcrete were inherited from groundwater infiltrating through Music Mountain Formation arkosic sediments, which were derived from a Precambrian source terrane to the south and southwest. No absolute ages exist for the Music Mountain Formation and West Water Formation in the Milkweed and West Water paleocanyons;

Synthesis and structure of undoped and indium-doped thermoelectric lead telluride nanoparticles

Undoped and indium (In)-doped lead telluride (PbTe) nanostructures were synthesized via solvothermal/hydrothermal route. The crystalline structure of the as-prepared undoped and In-doped PbTe samples was examined by X-ray diffraction (XRD) which indicated the formation of face-centered single-phase cubic crystal. A first principle calculation on indium doping shows that the indium atoms are more likely to replace lead (Pb) rather than to take the interstitial sites. Laser-induced breakdown spectroscopy (LIBS) analysis confirms that indium is incorporated into the PbTe matrix of the indium-doped PbTe samples. The effects of surfactant and synthesis temperature on the structure and morphology of the undoped PbTe were also investigated; it was found that PbTe nanostructures synthesized with the addition of surfactants exhibited uniform shapes and their size increased with the synthesis temperature

Room temperature synthesis of Ni-based alloy nanoparticles by radiolysis.

Room temperature radiolysis, density functional theory, and various nanoscale characterization methods were used to synthesize and fully describe Ni-based alloy nanoparticles (NPs) that were synthesized at room temperature. These complementary methods provide a strong basis in understanding and describing metastable phase regimes of alloy NPs whose reaction formation is determined by kinetic rather than thermodynamic reaction processes. Four series of NPs, (Ag-Ni, Pd-Ni, Co-Ni, and W-Ni) were analyzed and characterized by a variety of methods, including UV-vis, TEM/HRTEM, HAADF-STEM and EFTEM mapping. In the first focus of research, AgNi and PdNi were studied. Different ratios of Ag{sub x}- Ni{sub 1-x} alloy NPs and Pd{sub 0.5}- Ni{sub 0.5} alloy NP were prepared using a high dose rate from gamma irradiation. Images from high-angle annular dark-field (HAADF) show that the Ag-Ni NPs are not core-shell structure but are homogeneous alloys in composition. Energy filtered transmission electron microscopy (EFTEM) maps show the homogeneity of the metals in each alloy NP. Of particular interest are the normally immiscible Ag-Ni NPs. All evidence confirmed that homogeneous Ag-Ni and Pd-Ni alloy NPs presented here were successfully synthesized by high dose rate radiolytic methodology. A mechanism is provided to explain the homogeneous formation of the alloy NPs. Furthermore, studies of Pd-Ni NPs by in situ TEM (with heated stage) shows the ability to sinter these NPs at temperatures below 800 C. In the second set of work, CoNi and WNi superalloy NPs were attempted at 50/50 concentration ratios using high dose rates from gamma irradiation. Preliminary results on synthesis and characterization have been completed and are presented. As with the earlier alloy NPs, no evidence of core-shell NP formation occurs. Microscopy results seem to indicate alloying occurred with the CoNi alloys. However, there appears to be incomplete reduction of the Na{sub 2}WO{sub 4} to form the W{sup 2+} ion in solution; the predominance of WO{sup +} appears to have resulted in a W-O-Ni complex that has not yet been fully characterized