Analysis of Cellulose Nanocrystal Aerogels

Aerogels are interesting material systems with outstanding properties such as low density, high surface area, and low thermal conductivity. They can be used for a variety of applications, such as solar cells, sensors, or catalysts. Additionally they provide a unique model system to study the properties of small particles. Cellulose Nanocrystals (CNCs) are the nanoscale extractions of large cellulose fibers in a variety of plants and animals such as wood, paper, cotton, or tunicates. Their nanoscale size coupled with high mechanical strength, biodegradability, and renewability make them an interesting alternative to oil based materials for composites with applications in various areas such as electronics, packaging, or tissue engineering. In this work aerogels are used to study CNCs by first creating CNC aerogels followed by structure investigations of aerogels, and finally the study of their mechanical properties to find the strength of CNC bonds. With the understanding of the bond strength, CNC nanocomposite material system development can advance to the next level. CNC aerogels are produced from carboxylated nanocrystalline cellulose organogels by acetone exchange followed by supercritical CO₂ drying. Atomic layer deposition is used to coat CNC aerogels with a thin conformal layer of Al₂O₃. The resulting three dimensional nanoporous structure is analyzed via transmission electron microscope tomography to find the number of CNC bonds within the aerogel. Uniaxial compression tests are performed to determine the mechanical properties of the aerogels. The resulting aerogels are highly transparent, extremely light weight and have a large surface area. The deposited layer of alumina increases the resistance of the aerogels to moisture and elevated temperatures, and provides protection for CNCs against the electron beam for imaging. Tomographic data shows the nanoscale structure of the CNCs in the aerogel and enables the qualitative and quantitative characterization of the bonds. The mechanical properties are found to depend mostly on the density of the aerogel including the number of CNCs and the number of bonds. The required work to mechanically break CNC bonds is measured and the resulting CNC bond strength suggests that the CNCs are bonded together by hydrogen bonds located at the surface of the CNCs

Decreasing Slip Rates From12.8 Ma to Present on the Solitario Canyon Fault at Yucca Mountain, Nevada

The Solitario Canyon fault, which bounds the west side of Yucca Mountain, Nevada, is the closest fault with Quaternary offset adjacent to the proposed spent nuclear fuel and high-level radioactive waste repository. Dip-slip offset between 12.8 and 10.7 Ma is determined from lithostratigraphic displacement in boreholes USW H-3 and USW WT-7, drilled in the footwall and hanging wall, respectively. The base of the 12.8-Ma Topopah Spring Tuff is interpreted to have 463.3 m of separation across the fault, an average dip slip rate of 0.036 mm/yr. Previous researchers identified a geothermal system active from 11.5 to 10.0 Ma with peak activity at 10.7 Ma that resulted in pervasive alteration of vitric rock to zeolitic minerals where the rocks were in the ground-water saturated zone. The contact between vitric (V) and pervasively zeolitic (Z) rocks cuts across the lithostratigraphic section and offset of this V-Z boundary can be used to measure slip rates between 12.8 and 10.7 Ma. In H-3, the V-Z boundary is 138.4 m below the base of the vitric, densely welded subzone of the Topopah Spring Tuff (Tptpv3). In WT-7, although the V-Z boundary is identified at the base of the Tptpv3, borehole video, cuttings, and geophysical log data indicate the Tptpv3 has well-developed zeolitic alteration along fractures, and this implies 19.5 m of the total thickness of Tptpv3 (and probably additional overlying crystallized rocks) also were in the saturated zone by 10.7 Ma. The V-Z relations across the Solitario Canyon fault in H-3 and WT-7 indicate a minimum of 157.9 m of separation before 10.7 Ma, which is 34.1 percent of the total slip of the Topopah Spring Tuff, and a minimum dip slip rate of 0.075 mm/yr from 12.8 to 10.7 Ma. These data are consistent with the broader structural history of the area near Yucca Mountain. Previous workers used angular unconformities, tilting of structural blocks, and paleomagnetic data to constrain the main period of extensional faulting between 12.7 and 8.5 Ma. Paleoseismic studies in Quaternary deposits documented slip rates on the Solitario Canyon fault from 0.01 to 0.02 mm/yr since 0.077 and 0.20 Ma. The decrease of extensional activity slip rates data on the Solitario Canyon fault provide evidence of decreasing tectonic activity from the middle Miocene to present

LITHOSTRATIGRAPHY AND SHEAR-WAVE VELOCITY IN THE CRYSTALLIZED TOPOPAH SPRING TUFF, YUCCA MOUNTAIN, NEVADA

Evaluation of the seismic response of the proposed spent nuclear fuel and high-level radioactive waste repository at Yucca Mountain, Nevada, is in part based on the seismic properties of the host rock, the 12.8-million-year-old Topopah Spring Tuff. Because of the processes that formed the tuff, the densely welded and crystallized part has three lithophysal and three nonlithophysal zones, and each zone has characteristic variations in lithostratigraphic features and structures of the rocks. Lithostratigraphic features include lithophysal cavities, rims on lithophysae and some fractures, spots (which are similar to rims but without an associated cavity or aperture), amounts of porosity resulting from welding, crystallization, and vapor-phase corrosion and mineralization, and fractures. Seismic properties, including shear-wave velocity (V{sub s}), have been measured on 38 pieces of core, and there is a good ''first order'' correlation with the lithostratigraphic zones; for example, samples from nonlithophysal zones have larger V{sub s} values compared to samples from lithophysal zones. Some samples have V{sub s} values that are beyond the typical range for the lithostratigraphic zone; however, these samples typically have one or more fractures, ''large'' lithophysal cavities, or ''missing pieces'' relative to the sample size. Shear-wave velocity data measured in the tunnels have similar relations to lithophysal and nonlithophysal rocks; however, tunnel-based values are typically smaller than those measured in core resulting from increased lithophysae and fracturing effects. Variations in seismic properties such as V{sub s} data from small-scale samples (typical and ''flawed'' core) to larger scale traverses in the tunnels provide a basis for merging our understanding of the distributions of lithostratigraphic features (and zones) with a method to scale seismic properties

Proposed stratigraphic nomenclature and macroscopic identification of lithostratigraphic units of the Paintbrush Group exposed at Yucca Mountain, Nevada

This paper describes the formations of the Paintbrush Group exposed at Yucca Mountain, Nevada, presents a detailed stratigraphic nomenclature for the Tiva Canyon and Topopah spring Tuffs, and discusses the criteria that define lithostratigraphic units. The Tiva Canyon and Topopah Spring Tuffs are divided into zones, subzones, and intervals on the basis of macroscopic features observed in surface exposures and borehole samples. Primary divisions reflect depositional and compositional zoning that is expressed by variations in crystal content, phenocryst assemblage, pumice content and composition, and lithic content. Secondary divisions define welding and crystlalization zones, depositional features, or fracture characteristics. Both formations are divided into crystal-rich and crystal-poor members that have an identical sequency of zones, although subzone designations vary slightly between the two units. The identified lithostratigraphic divisions can be used to approximate thermal-mechanical and hydrogeologic boundaries in the field. Linking these three systems of nomenclature provides a framework within which to correlate these properties through regions of sparse data

Improved oxidation resistance of organic/inorganic composite atomic layer deposition coated cellulose nanocrystal aerogels

Cellulose nanocrystal (CNC) aerogels are coated with thin conformal layers of Al₂O₃ using atomic layer deposition to form hybrid organic/inorganic nanocomposites. Electron probe microanalysis and scanning electron microscopy analysis indicated the Al₂O₃ penetrated more than 1500 μm into the aerogel for extended precursor pulse and exposure/purge times. The measured profile of coated fiber radius versus depth from the aerogel surface agrees well with simulations of precursor penetration depth in modeled aerogel structures. Thermogravimetric analysis shows that Al₂O₃ coated CNC aerogel nanocomposites do not show significant thermal degradation below 295°C as compared with 175°C for uncoated CNC aerogels, an improvement of over 100°C.This is the publisher’s final pdf. The published article is copyrighted by the American Vacuum Society and can be found at: http://scitation.aip.org/content/avs/journal/jvsta

Distribution of lithostratigraphic units within the central block of Yucca Mountain, Nevada: A three-dimensional computer-based model, Version YMP.R2.0

Yucca Mountain, Nevada is underlain by 14.0 to 11.6 Ma volcanic rocks tilted eastward 3{degree} to 20{degree} and cut by faults that were primarily active between 12.7 and 11.6 Ma. A three-dimensional computer-based model of the central block of the mountain consists of seven structural subblocks composed of six formations and the interstratified-bedded tuffaceous deposits. Rocks from the 12.7 Ma Tiva Canyon Tuff, which forms most of the exposed rocks on the mountain, to the 13.1 Ma Prow Pass Tuff are modeled with 13 surfaces. Modeled units represent single formations such as the Pah Canyon Tuff, grouped units such as the combination of the Yucca Mountain Tuff with the superjacent bedded tuff, and divisions of the Topopah Spring Tuff such as the crystal-poor vitrophyre interval. The model is based on data from 75 boreholes from which a structure contour map at the base of the Tiva Canyon Tuff and isochore maps for each unit are constructed to serve as primary input. Modeling consists of an iterative cycle that begins with the primary structure-contour map from which isochore values of the subjacent model unit are subtracted to produce the structure contour map on the base of the unit. This new structure contour map forms the input for another cycle of isochore subtraction to produce the next structure contour map. In this method of solids modeling, the model units are presented by surfaces (structure contour maps), and all surfaces are stored in the model. Surfaces can be converted to form volumes of model units with additional effort. This lithostratigraphic and structural model can be used for (1) storing data from, and planning future, site characterization activities, (2) preliminary geometry of units for design of Exploratory Studies Facility and potential repository, and (3) performance assessment evaluations

Commissioning of the vacuum system of the KATRIN Main Spectrometer

The KATRIN experiment will probe the neutrino mass by measuring the beta-electron energy spectrum near the endpoint of tritium beta-decay. An integral energy analysis will be performed by an electro-static spectrometer (Main Spectrometer), an ultra-high vacuum vessel with a length of 23.2 m, a volume of 1240 m^3, and a complex inner electrode system with about 120000 individual parts. The strong magnetic field that guides the beta-electrons is provided by super-conducting solenoids at both ends of the spectrometer. Its influence on turbo-molecular pumps and vacuum gauges had to be considered. A system consisting of 6 turbo-molecular pumps and 3 km of non-evaporable getter strips has been deployed and was tested during the commissioning of the spectrometer. In this paper the configuration, the commissioning with bake-out at 300{\deg}C, and the performance of this system are presented in detail. The vacuum system has to maintain a pressure in the 10^{-11} mbar range. It is demonstrated that the performance of the system is already close to these stringent functional requirements for the KATRIN experiment, which will start at the end of 2016.Comment: submitted for publication in JINST, 39 pages, 15 figure

Burden of paediatric Rotavirus Gastroenteritis (RVGE) and potential benefits of a universal Rotavirus vaccination programme with a pentavalent vaccine in Spain

<p>Abstract</p> <p>Background</p> <p>Rotavirus is the most common cause of gastroenteritis in young children worldwide. The aim of the study was to assess the health outcomes and the economic impact of a universal rotavirus vaccination programme with RotaTeq, the pentavalent rotavirus vaccine, versus no vaccination programme in Spain.</p> <p>Methods</p> <p>A birth cohort was followed up to the age of 5 using a cohort model. Epidemiological parameters were taken from the REVEAL study (a prospective epidemiological study conducted in Spain, 2004-2005) and from the literature. Direct and indirect costs were assessed from the national healthcare payer and societal perspectives by combining health care resource utilisation collected in REVEAL study and unit costs from official sources. RotaTeq per protocol efficacy data was taken from a large worldwide rotavirus clinical trial (70,000 children). Health outcomes included home care cases, General Practioner (GP)/Paediatrician, emergency department visits, hospitalisations and nosocomial infections.</p> <p>Results</p> <p>The model estimates that the introduction of a universal rotavirus vaccination programme with RotaTeq (90% coverage rate) would reduce the rotavirus gastroenteritis (RVGE) burden by 75% in Spain; 53,692 home care cases, 35,187 GP/Paediatrician visits, 34,287 emergency department visits, 10,987 hospitalisations and 2,053 nosocomial infections would be avoided. The introduction of RotaTeq would avoid about 76% of RVGE-related costs from both perspectives: €22 million from the national health system perspective and €38 million from the societal perspective.</p> <p>Conclusions</p> <p>A rotavirus vaccination programme with RotaTeq would reduce significantly the important medical and economic burden of RVGE in Spain.</p

Novel post-synthetic generation, isomeric resolution, and characterization of Fapy-dG within oligodeoxynucleotides: differential anomeric impacts on DNA duplex properties

Accumulation of damaged guanine nucleobases within genomic DNA, including the imidazole ring opened N6-(2-Deoxy-α,β-D-erythro-pentafuranosyl)-2,6-diamino-4-hydroxy-5-formylamidopyrimidine (Fapy-dG), is associated with progression of age-related diseases and cancer. To evaluate the impact of this mutagenic lesion on DNA structure and energetics, we have developed a novel synthetic strategy to incorporate cognate Fapy-dG site-specifically within any oligodeoxynucleotide sequence. The scheme involves the synthesis of an oligonucleotide precursor containing a 5-nitropyrimidine moiety at the desired lesion site via standard solid-phase procedures. Following deprotection and isolation, the Fapy-dG lesion is generated by catalytic hydrogenation and subsequent formylation. NMR assignment of the Fapy-dG lesion (X) embedded within a TXT trimer reveals the presence of rotameric and anomeric species. The latter have been characterized by synthesizing the tridecamer oligodeoxynucleotide d(GCGTACXCATGCG) harboring Fapy-dG as the central residue and developing a protocol to resolve the isomeric components. Hybridization of the chromatographically isolated fractions with their complementary d(CGCATGCGTACGC) counterpart yields two Fapy-dG·C duplexes that are differentially destabilized relative to the canonical G·C parent. The resultant duplexes exhibit distinct thermal and thermodynamic profiles that are characteristic of α- and β-anomers, the former more destabilizing than the latter. These anomer-specific impacts are discussed in terms of differential repair enzyme recognition, processing and translesion synthesis