Self-assembled ordered carbon-nanotube arrays and membranes.

Imagine free-standing flexible membranes with highly-aligned arrays of carbon nanotubes (CNTs) running through their thickness. Perhaps with both ends of the CNTs open for highly controlled nanofiltration? Or CNTs at heights uniformly above a polymer membrane for a flexible array of nanoelectrodes or field-emitters? How about CNT films with incredible amounts of accessible surface area for analyte adsorption? These self-assembled crystalline nanotubes consist of multiple layers of graphene sheets rolled into concentric cylinders. Tube diameters (3-300 nm), inner-bore diameters (2-15 nm), and lengths (nanometers - microns) are controlled to tailor physical, mechanical, and chemical properties. We proposed to explore growth and characterize nanotube arrays to help determine their exciting functionality for Sandia applications. Thermal chemical vapor deposition growth in a furnace nucleates from a metal catalyst. Ordered arrays grow using templates from self-assembled hexagonal arrays of nanopores in anodized-aluminum oxide. Polymeric-binders can mechanically hold the CNTs in place for polishing, lift-off, and membrane formation. The stiffness, electrical and thermal conductivities of CNTs make them ideally suited for a wide-variety of possible applications. Large-area, highly-accessible gas-adsorbing carbon surfaces, superb cold-cathode field-emission, and unique nanoscale geometries can lead to advanced microsensors using analyte adsorption, arrays of functionalized nanoelectrodes for enhanced electrochemical detection of biological/explosive compounds, or mass-ionizers for gas-phase detection. Materials studies involving membrane formation may lead to exciting breakthroughs in nanofiltration/nanochromatography for the separation of chemical and biological agents. With controlled nanofilter sizes, ultrafiltration will be viable to separate and preconcentrate viruses and many strains of bacteria for 'down-stream' analysis

Nanotube cathodes.

Carbon nanotubes have shown promise for applications in many diverse areas of technology. In this report we describe our efforts to develop high-current cathodes from a variety of nanotubes deposited under a variety of conditions. Our goal was to develop a one-inch-diameter cathode capable of emitting 10 amperes of electron current for one second with an applied potential of 50 kV. This combination of current and pulse duration significantly exceeds previously reported nanotube-cathode performance. This project was planned for two years duration. In the first year, we tested the electron-emission characteristics of nanotube arrays fabricated under a variety of conditions. In the second year, we planned to select the best processing conditions, to fabricate larger cathode samples, and to test them on a high-power relativistic electron beam generator. In the first year, much effort was made to control nanotube arrays in terms of nanotube diameter and average spacing apart. When the project began, we believed that nanotubes approximately 10 nm in diameter would yield sufficient electron emission properties, based on the work of others in the field. Therefore, much of our focus was placed on measured field emission from such nanotubes grown on a variety of metallized surfaces and with varying average spacing between individual nanotubes. We easily reproduced the field emission properties typically measured by others from multi-wall carbon nanotube arrays. Interestingly, we did this without having the helpful vertical alignment to enhance emission; our nanotubes were randomly oriented. The good emission was most likely possible due to the improved crystallinity, and therefore, electrical conductivity, of our nanotubes compared to those in the literature. However, toward the end of the project, we learned that while these 10-nm-diameter CNTs had superior crystalline structure to the work of others studying field emission from multi-wall CNT arrays, these nanotubes still had a thin coating of glassy carbon surrounding them in a sheath-like manner. This glassy carbon, or nano-crystalline graphite, is likely to be a poor conductor due to phonon scattering, and should actually be deleterious for extracting electrons with electric fields. While we did not achieve the field emission reported for single-wall carbon nanotubes that spurred the idea for this project, at the year's very end, we had a breakthrough in materials growth and learned to control the growth of very-small diameter nanotubes ranging from 1.4 to 7 nm. The 1.4-nm nanotubes are single-walled and grow at only 530 C. This is the lowest temperature known to result in single-wall carbon nanotubes, and may be very important for many applications that where certain substrates could not be used due to the high temperatures commonly used for CNT growth. Critically important for field emission, these small diameter nanotubes, consisting of only a few concentric graphene cylindrical walls, do not show the presence of a poorly-conductive sheath material. Therefore, these nanotubes will almost definitely have superior field emission properties to those we already measured, and it is possible that they could provide the necessary field emission to make this project successful. Controlled spacing and lengths of these single-wall nanotubes have yet to be explored, along with correlating their structures to their improved field emission. Unfortunately, we did not discover the methods to grow these highly-crystalline and small diameter CNTs until late in the year. Since we did not achieve the necessary emission properties by mid-year, the project was ''prematurely'' terminated prior to the start of the second year. However, it should be noted that with the late developments, this work has not hit the proverbial ''brick wall''. Clearly the potential still exists to reproduce and even exceed the high emission results reported for randomly-oriented and curly single-wall carbon nanotubes, both in terms of total field emitting currents and perhaps more importantly, in reproducibility

Electroforming of Bi(1-x)Sb(x) nanowires for high-efficiency micro-thermoelectric cooling devices on a chip.

Active cooling of electronic systems for space-based and terrestrial National Security missions has demanded use of Stirling, reverse-Brayton, closed Joule-Thompson, pulse tube and more elaborate refrigeration cycles. Such cryocoolers are large systems that are expensive, demand large powers, often contain moving parts and are difficult to integrate with electronic systems. On-chip, solid-state, active cooling would greatly enhance the capabilities of future systems by reducing the size, cost and inefficiencies compared to existing solutions. We proposed to develop the technology for a thermoelectric cooler capable of reaching 77K by replacing bulk thermoelectric materials with arrays of Bi{sub 1-x}Sb{sub x} nanowires. Furthermore, the Sandia-developed technique we will use to produce the oriented nanowires occurs at room temperature and can be applied directly to a silicon substrate. Key obstacles include (1) optimizing the Bi{sub 1-x}Sb{sub x} alloy composition for thermoelectric properties; (2) increasing wire aspect ratios to 3000:1; and (3) increasing the array density to {ge} 10{sup 9} wires/cm{sup 2}. The primary objective of this LDRD was to fabricate and test the thermoelectric properties of arrays of Bi{sub 1-x}Sb{sub x} nanowires. With this proof-of-concept data under our belts we are positioned to engage National Security systems customers to invest in the integration of on-chip thermoelectric coolers for future missions

Short pulse laser-induced optical damage and fracto-emission of amorphous, diamond-like carbon

Short pulse laser damage and ablation of amorphous, diamond-like carbon films is investigated. Material removal is due to fracture of the film and ejection of large fragments, which exhibit a broadband emission of microsecond duration

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

Genetic mapping of microbial and host traits reveals production of immunomodulatory lipids by Akkermansia muciniphila in the murine gut.

The molecular bases of how host genetic variation impacts the gut microbiome remain largely unknown. Here we used a genetically diverse mouse population and applied systems genetics strategies to identify interactions between host and microbe phenotypes including microbial functions, using faecal metagenomics, small intestinal transcripts and caecal lipids that influence microbe-host dynamics. Quantitative trait locus (QTL) mapping identified murine genomic regions associated with variations in bacterial taxa; bacterial functions including motility, sporulation and lipopolysaccharide production and levels of bacterial- and host-derived lipids. We found overlapping QTL for the abundance of Akkermansia muciniphila and caecal levels of ornithine lipids. Follow-up in vitro and in vivo studies revealed that A. muciniphila is a major source of these lipids in the gut, provided evidence that ornithine lipids have immunomodulatory effects and identified intestinal transcripts co-regulated with these traits including Atf3, which encodes for a transcription factor that plays vital roles in modulating metabolism and immunity. Collectively, these results suggest that ornithine lipids are potentially important for A. muciniphila-host interactions and support the role of host genetics as a determinant of responses to gut microbes

The dopamine β-hydroxylase -1021C/T polymorphism is associated with the risk of Alzheimer's disease in the Epistasis Project

Contains fulltext : 88930.pdf (publisher's version ) (Open Access)BACKGROUND: The loss of noradrenergic neurones of the locus coeruleus is a major feature of Alzheimer's disease (AD). Dopamine beta-hydroxylase (DBH) catalyses the conversion of dopamine to noradrenaline. Interactions have been reported between the low-activity -1021T allele (rs1611115) of DBH and polymorphisms of the pro-inflammatory cytokine genes, IL1A and IL6, contributing to the risk of AD. We therefore examined the associations with AD of the DBH -1021T allele and of the above interactions in the Epistasis Project, with 1757 cases of AD and 6294 elderly controls. METHODS: We genotyped eight single nucleotide polymorphisms (SNPs) in the three genes, DBH, IL1A and IL6. We used logistic regression models and synergy factor analysis to examine potential interactions and associations with AD. RESULTS: We found that the presence of the -1021T allele was associated with AD: odds ratio = 1.2 (95% confidence interval: 1.06-1.4, p = 0.005). This association was nearly restricted to men < 75 years old: odds ratio = 2.2 (1.4-3.3, 0.0004). We also found an interaction between the presence of DBH -1021T and the -889TT genotype (rs1800587) of IL1A: synergy factor = 1.9 (1.2-3.1, 0.005). All these results were consistent between North Europe and North Spain. CONCLUSIONS: Extensive, previous evidence (reviewed here) indicates an important role for noradrenaline in the control of inflammation in the brain. Thus, the -1021T allele with presumed low activity may be associated with misregulation of inflammation, which could contribute to the onset of AD. We suggest that such misregulation is the predominant mechanism of the association we report here

High J{sub c} YBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} Films via Rapid, Low pO{sub 2} Pyrolysis

In this investigation, YBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} (YBCO) films were fabricated via a metal acetate, trifluoroacetic acid based sol-gel route, and spin-coat deposited on (100) LaAlO{sub 3} with a focus on maximizing J{sub c}, while minimizing processing time. We demonstrate that the use of a low pO{sub 2} atmosphere during the pyrolysis stage can lead to at least a tetiold reduction in pyrolysis time, compared to a 1 atm. O{sub 2} ambient. High-quality YBCO films on LaAlO{sub 3}, with J{sub c} values up to 3 MA/cm{sup 2} at 77 K, can be routinely crystallized from these rapidly pyrolyzed films

Ultrahard carbon nanocomposite films

Modest thermal annealing to 600 C of diamondlike amorphous-carbon (a-C) films grown at room temperature results in the formation of carbon nanocomposites with hardness similar to diamond. These nanocomposite films consist of nanometer-sized regions of high density a-C embedded in an a-C matrix with a reduced density of 5--10%. The authors report on the evolution of density and bonding topologies as a function of annealing temperature. Despite a decrease in density, film hardness actually increases {approximately} 15% due to the development of the nanocomposite structure