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At least 541 records · Page 30

The effects of acid deposition on sulfate reduction and methane production in peatlands

Peatlands, as fens and bods, make up a large percentage of northern latitude terrestrial environments. They are organic rich and support an active community of anaerobic bacteria, such as methanogenic and sulfate-reducing bacteria. The end products of these microbial activities, methane and hydrogen sulfide, are important components in the global biogeochemical cycles of carbon and sulfur. Since these two bacterial groups compete for nutritional substrates, increases in sulfate deposition due to acid rain potentially can disrupt the balance between these processes leading to a decrease in methane production and emission. This is significant because methane is a potent greenhouse gas that effects the global heat balance. A section of Mire 239 in the Experimental Lakes Area, in Northwestern Ontario, was artificially acidified and rates of sulfate reduction and methane production were measured with depth. Preliminary results suggested that methane production was not affected immediately after acidification. However, concentrations of dissolved methane decreased and dissolved sulfide increased greatly after acidification and both took several days to recover. The exact mechanism for the decrease in methane was not determined. Analyses are under way which will be used to determine rates of sulfate reduction. These results will be available by Spring and will be discussed.

Murray, Georgia L.↗

Application of Chlorine-Assisted Chemical Vapor Deposition of Diamond at Low Temperatures

Low temperature deposition of diamond has been achieved by a chlorine-assisted diamond chemical vapor deposition (CA-CVD) process. This method begins with the thermal dissociation of molecular chlorine into atomic chlorine in a resistively heated graphite furnace at temperatures between 1300 and 1500 deg. C. The atomic chlorine, upon mixing, subsequently reacts with molecular hydrogen and hydrocarbons. The rapid exchange reactions between the atomic chlorine, molecular hydrogen, and hydrocarbons give rise to the atomic hydrogen and carbon precursors required for diamond deposition. Homoepitaxial diamond growth on diamond substrates has been studied over the substrate temperature range of 100-950 C. It was found that the diamond growth rates are approximately 0.2 microns/hr in the temperature range between 102 and 300 C and that the growth rates do not decrease significantly with a decrease in substrate temperature. This is unique because the traditional diamond deposition using H2/CH4 systems usually disappears at substrate temperatures below approx. 500 deg. C. This opens up a possible route to the deposition of diamond on low-melting point materials such as aluminum and its alloys.

Pan, Chenyu↗

Cryo-Etched Black Silicon for Use as Optical Black

Stray light reflected from the surface of imaging spectrometer components in particular, the spectrometer slit degrade the image quality. A technique has been developed for rapid, uniform, and cost-effective black silicon formation based on inductively coupled plasma (ICP) etching at cryogenic temperatures. Recent measurements show less than 1-percent total reflectance from 350 2,500 nm of doped black silicon formed in this way, making it an excellent option for texturing of component surfaces for reduction of stray light. Oxygen combines with SF6 + Si etch byproducts to form a passivation layer atop the Si when the etch is performed at cryogenic temperatures. Excess flow of oxygen results in micromasking and the formation of black silicon. The process is repeatable and reliable, and provides control over etch depth and sidewall profile. Density of the needles can be controlled to some extent. Regions to be textured can be patterned lithographically. Adhesion is not an issue as the nanotips are part of the underlying substrate. This is in contrast to surface growth/deposition techniques such as carbon nanotubes (CNTs). The black Si surface is compatible with wet processing, including processing with solvents, the textured surface is completely inorganic, and it does not outgas. In radiometry applications, optical absorbers are often constructed using gold black or CNTs. This black silicon technology is an improvement for these types of applications.

Yee, Karl Y.↗

Silicon/Carbon Nanotube Photocathode for Splitting Water

A proof-of-concept device is being developed for hydrogen gas production based on water-splitting redox reactions facilitated by cobalt tetra-aryl porphyrins (Co[TArP]) catalysts stacked on carbon nanotubes (CNTs) that are grown on n-doped silicon substrates. The operational principle of the proposed device is based on conversion of photoelectron energy from sunlight into chemical energy, which at a later point, can be turned into electrical and mechanical power. The proposed device will consist of a degenerately n-doped silicon substrate with Si posts covering the surface of a 4-in. (approximately equal to 10cm) wafer. The substrate will absorb radiation, and electrons will move radially out of Si to CNT. Si posts are designed such that the diameters are small enough to allow considerable numbers of electrons to transport across to the CNT layer. CNTs will be grown on top of Si using conformal catalyst (Fe/Ni) deposition over a thin alumina barrier layer. Both metallic and semiconducting CNT will be used in this investigation, thus allowing for additional charge generation from CNT in the IR region. Si post top surfaces will be masked from catalyst deposition so as to prevent CNT growth on the top surface. A typical unit cell will then consist of a Si post covered with CNT, providing enhanced surface area for the catalyst. The device will then be dipped into a solution of Co[TArP] to enable coating of CNT with Co(P). The Si/CNT/Co [TArP] assembly then will provide electrons for water splitting and hydrogen gas production. A potential of 1.23 V is needed to split water, and near ideal band gap is approximately 1.4 eV. The combination of doped Si/CNT/Co [TArP] will enable this redox reaction to be more efficient.

Amashukeli, Xenia↗

Atmospheric Pressure Plasma Jet as a Dry Alternative to Inkjet Printing in Flexible Electronics

We have developed an atmospheric pressure plasma jet printing system that works at room temperature to 50 deg C unlike conventional aerosol assisted techniques which require a high temperature sintering step to obtain desired thin films. Multiple jets can be configured to increase throughput or to deposit multiple materials, and the jet(s) can be moved across large areas using a x-y stage. The plasma jet has been used to deposit carbon nanotubes, graphene, silver nanowires, copper nanoparticles and other materials on substrates such as paper, cotton, plastic and thin metal foils.

Printable electronics↗

Method and system for membrane carbonation

Disclosed herein are methods and systems for membrane carbonation for cultivating microalgae and other microorganisms that utilize a gaseous substrate, as well as to upgrade the quality of mixed-gas streams.

Rittmann, Bruce↗

Determination of the Wetting Angle of Germanium and Germanium-Silicon Melts on Different Substrate Materials

During Bridgman growth of semiconductors detachment of the crystal and the melt meniscus has occasionally been observed, mainly under microgravity (microg) conditions. An important factor for detached growth is the wetting angle of the melt with the crucible material. High contact angles are more likely to result in detachment of the growing crystal from the ampoule wall. In order to achieve detached growth of germanium (Ge) and germanium-silicon (GeSi) crystals under 1g and microg conditions, sessile drop measurements were performed to determine the most suitable ampoule material as well as temperature dependence of the surface tension for GeSi. Sapphire, fused quartz, glassy carbon, graphite, SiC, pyrolytic Boron Nitride (pBN), AIN, and diamond were used as substrates. Furthermore, different cleaning procedures and surface treatments (etching, sandblasting, etc.) of the same substrate material and their effect on the wetting behavior were studied during these experiments. pBN and AIN substrates exhibited the highest contact angles with values around 170 deg.

Kaiser, Natalie↗

Fe-N 4 O-C Nanoplates Covalently Bonding on Graphene for Efficient CO 2 Electroreduction and Zn-CO 2 Batteries

Electrochemical carbon dioxide (CO 2 ) reduction into value-added products holds great promise in moving toward carbon neutrality but remains a grand challenge due to lack of efficient electrocatalysts. Herein, the nucleophilic substitution reaction is elaborately harnessed to synthesize carbon nanoplates with a Fe-N 4 O configuration anchored onto graphene substrate (Fe-N 4 O-C/Gr) through covalent linkages. Density functional theory calculations demonstrate the unique configuration of Fe-N 4 O with one oxygen (O) atom in the axial direction not only suppresses the competing hydrogen evolution reaction, but also facilitates the desorption of *CO intermediate compared with the commonly planar single-atomic Fe sites. The Fe-N 4 O-C/Gr shows excellent performance in the electroreduction of CO 2 into carbon monoxide (CO) with an impressive Faradaic efficiency of 98.3% at -0.7 V versus reversible hydrogen electrode (RHE) and a high turnover frequency of 3511 h -1 . Furthermore, as a cathode catalyst in an aqueous zinc (Zn)-CO 2 battery, the Fe-N 4 O-C/Gr achieves a high CO Faradaic efficiency (≈91%) at a discharge current density of 3 mA cm -2 and long-term stability over 74 h. Here this work opens up a new route to simultaneously modulate the geometric and electronic structure of single-atomic catalysts toward efficient CO 2 conversion.

25 ENERGY STORAGE↗

Superlubricity coating containing carbon nanotubes

A method for producing a structure containing an array of MWCNTs on a metal substrate, comprising: (i) subjecting a metal substrate to a surface oxidation process at a first elevated temperature in an oxygen-containing atmosphere and under a first reduced pressure; (ii) subjecting the metal substrate to a surface reduction process at a second elevated temperature in a reducing atmosphere and under a second reduced pressure of at least 0.01 atm and less than 1 atm to result in reduction of the surface of said metal substrate, wherein the reducing atmosphere contains hydrogen gas; (iii) subjecting the metal substrate to a third reduced pressure of no more than 0.1 atm; and (iv) contacting the metal substrate, while at the third reduced pressure and under an inert or reducing atmosphere, with an organic substance at a third elevated temperature for suitable time to produce the MWCNTs on the metal substrate.

Ihala Gamaralalage, Chanaka Kapila↗

Substrate availability and not thermal acclimation controls microbial temperature sensitivity response to long-term warming

Microbes are responsible for cycling carbon (C) through soils, and predicted changes in soil C stocks under climate change are highly sensitive to shifts in the mechanisms assumed to control the microbial physiological response to warming. Two mechanisms have been suggested to explain the long-term warming impact on microbial physiology: microbial thermal acclimation and changes in the quantity and quality of substrates available for microbial metabolism. Yet studies disentangling these two mechanisms are lacking. To resolve the drivers of changes in microbial physiology in response to long-term warming, we sampled soils from 13- and 28-year-old soil warming experiments in different seasons. We performed short-term laboratory incubations across a range of temperatures to measure the relationships between temperature sensitivity of physiology (growth, respiration, carbon use efficiency, and extracellular enzyme activity) and the chemical composition of soil organic matter. We observed apparent thermal acclimation of microbial respiration, but only in summer, when warming had exacerbated the seasonally-induced, already small dissolved organic matter pools. Irrespective of warming, greater quantity and quality of soil carbon increased the extracellular enzymatic pool and its temperature sensitivity. We propose that fresh litter input into the system seasonally cancels apparent thermal acclimation of C-cycling processes to decadal warming. Our findings reveal that long-term warming has indirectly affected microbial physiology via reduced C availability in this system, implying that earth system models including these negative feedbacks may be best suited to describe long-term warming effects on these soils.

59 BASIC BIOLOGICAL SCIENCES↗

Effects of varying oxygen partial pressure on molten silicon-ceramic substrate interactions

The silicon sessile drop contact angle was measured on hot pressed silicon nitride, silicon nitride coated on hot pressed silicon nitride, silicon carbon coated on graphite, and on Sialon to determine the degree to which silicon wets these substances. The post-sessile drop experiment samples were sectioned and photomicrographs were taken of the silicon-substrate interface to observe the degree of surface dissolution and degradation. Of these materials, silicon did not form a true sessile drop on the SiC on graphite due to infiltration of the silicon through the SiC coating, nor on the Sialon due to the formation of a more-or-less rigid coating on the liquid silicon. The most wetting was obtained on the coated Si3N4 with a value of 42 deg. The oxygen concentrations in a silicon ribbon furnace and in a sessile drop furnace were measured using the protable thoria-yttria solid solution electrolyte oxygen sensor. Oxygen partial pressures of 10 to the minus 7 power atm and 10 to the minus 8 power atm were obtained at the two facilities. These measurements are believed to represent nonequilibrium conditions.

Ownby, D. P.↗

Radiocarbon Analyses Quantify Peat Carbon Losses With Increasing Temperature in a Whole Ecosystem Warming Experiment

Abstract Climate warming is expected to accelerate peatland degradation and release rates of carbon dioxide (CO 2 ) and methane (CH 4 ). Spruce and Peatlands Responses Under Changing Environments is an ecosystem‐scale climate manipulation experiment, designed to examine peatland ecosystem response to climate forcings. We examined whether heating up to +9 °C to 3 m‐deep in a peat bog over a 7‐year period led to higher C turnover and CO 2 and CH 4 emissions, by measuring 14 C of solid peat, dissolved organic carbon (DOC), CH 4 , and dissolved CO 2 (DIC). DOC, a major substrate for heterotrophic respiration, increased significantly with warming. There was no 7‐year trend in the DI 14 C of the ambient plots which remained similar to their DO 14 C. At +6.75 °C and +9 °C, the 14 C of DIC, a product of microbial respiration, initially resembled ambient plots but became more depleted over 7 years of warming. We attributed the shifts in DI 14 C to the increasing importance of solid phase peat as a substrate for microbial respiration and quantified this shift via the radiocarbon mass balance. The mass‐balance model revealed increases in peat‐supported respiration of the catotelm depths in heated plots over time and relative to ambient enclosures, from a baseline of 20%–25% in ambient enclosures, to 35%–40% in the heated plots. We find that warming stimulates microorganisms to respire ancient peat C, deposited under prior climate (cooler) conditions. This apparent destabilization of the large peat C reservoir has implications for peatland‐climate feedbacks especially if the balance of the peatland is tipped from net C sink to C source.

54 ENVIRONMENTAL SCIENCES↗

Cyanate Ester and Phthalonitrile Impregnated Carbon Ablative TPS

Phenolic resin has extensive heritage as a TPS (Thermal Protection Systems) material, however, alternative resin systems such as Cyanate Ester and Phthalonitrile may offer improved performance compared to state-of-the-art phenolic resin. These alternative resin systems may have higher char yield, higher char strength, lower thermal conductivity and improved mechanical properties. In current work at NASA Ames alternative resin systems were uniformly infused into fibrous substrates and preliminary properties characterized. The density of the cyanate ester infused in fibrous substrate ranged from 0.25-0.3 grams per cubic centimeter compared to PICA (Phenolic resin impregnated carbon ablative) having a density of approximately 0.25 grams per cubic centimeter. The density of Phthalonitrile varies from 0.22-0.25 grams per cubic centimeter. Initial formulations of these new resin systems were recently tested at the LARC HyMETs (Hypersonic Materials Environmental Test System) facility to evaluate their performance and data such as back face temperature, char yield, and recession are compared to PICA. Cyanate Ester and Phthalonitrile impregnated carbon ablative samples showed comparable performance to phenolic resin impregnated carbon ablative samples.

Polymer↗

Effect of Alignment on Transport Properties of Carbon Nanotube/Metallic Junctions

Ballistic and spin coherent transport in single walled carbon nanotubes (SWCNT) are predicted to enable high sensitivity single-nanotube devices for strain and magnetic field sensing. Based upon these phenomena, electron beam lithography procedures have been developed to study the transport properties of purified HiPCO single walled carbon nanotubes for development into sensory materials for nondestructive evaluation. Purified nanotubes are dispersed in solvent suspension and then deposited on the device substrate before metallic contacts are defined and deposited through electron beam lithography. This procedure produces randomly dispersed ropes, typically 2 - 20 nm in diameter, of single walled carbon nanotubes. Transport and scanning probe microscopy studies have shown a good correlation between the junction resistance and tube density, alignment, and contact quality. In order to improve transport properties of the junctions a technique has been developed to align and concentrate nanotubes at specific locations on the substrate surface. Lithographic techniques are used to define local areas where high frequency electric fields are to be concentrated. Application of the fields while the substrate is exposed to nanotube-containing solution results in nanotube arrays aligned with the electric field lines. A second electron beam lithography layer is then used to deposit metallic contacts across the aligned tubes. Experimental measurements are presented showing the increased tube alignment and improvement in the transport properties of the junctions.

Wincheski, Buzz↗

Passivation of Flexible YBCO Superconducting Current Lead With Amorphous SiO2 Layer

Adiabatic demagnetization refrigerators (ADR) are operated in space to cool detectors of cosmic radiation to a few 10s of mK. A key element of the ADR is a superconducting magnet operating at about 0.3 K that is continually energized and de-energized in synchronism with a thermal switch, such that a piece of paramagnetic salt is alternately warm in a high magnetic field and cold in zero magnetic field. This causes the salt pill or refrigerant to cool, and it is able to suck heat from an object, e.g., the sensor, to be cooled. Current has to be fed into and out of the magnets from a dissipative power supply at the ambient temperature of the spacecraft. The current leads that link the magnets to the power supply inevitably conduct a significant amount of heat into the colder regions of the supporting cryostat, resulting in the need for larger, heavier, and more powerful supporting refrigerators. The aim of this project was to design and construct high-temperature superconductor (HTS) leads from YBCO (yttrium barium copper oxide) composite conductors to reduce the heat load significantly in the temperature regime below the critical temperature of YBCO. The magnet lead does not have to support current in the event that the YBCO ceases to be superconducting. Cus - tomarily, a normal metal conductor in parallel with the YBCO is a necessary part of the lead structure to allow for this upset condition; however, for this application, the normal metal can be dispensed with. Amorphous silicon dioxide is deposited directly onto the surface of YBCO, which resides on a flexible substrate. The silicon dioxide protects the YBCO from chemically reacting with atmospheric water and carbon dioxide, thus preserving the superconducting properties of the YBCO. The customary protective coating for flexible YBCO conductors is silver or a silver/gold alloy, which conducts heat many orders of magnitude better than SiO2 and so limits the use of such a composite conductor for passing current across a thermal gradient with as little flow of heat as possible to make an efficient current lead. By protecting YBCO on a flexible substrate of low thermal conductivity with SiO2, a thermally efficient and flexible current lead can be fabricated. The technology is also applicable to current leads for 4 K superconducting electronics current biasing. A commercially available thin-film YBCO composite tape conductor is first stripped of its protective silver coating. It is then mounted on a jig that holds the sample flat and acts as a heat sink. Silicon dioxide is then deposited onto the YBCO to a thickness of about 1 micron using PECVD (plasma-enhanced chemical vapor deposition), without heating the YBCO to the point where degradation occurs. Since SiO2 can have good high-frequency electrical properties, it can be used to coat YBCO cable structures used to feed RF signals across temperature gradients. The prime embodiment concerns the conduction of DC current across the cryogenic temperature gradient. The coating is hard and electrically insulating, but flexible.

Johannes, Daniel↗

The Role of Plasma in Plasma Enhanced Chemical Vapour Deposition of Nanostructure Growth

Chemical vapour deposition (CVD) has become the preferred process for high yield growth of carbon nanotubes and nanofibres because of its ability to pattern growth through lithographic positioning of transition metal catalysts on substrates. Many potential applications of nanotubes such as field emitters [1] require not only patterned growth but also vertical alignment. Some degree of ali,ment in thermal CVD processes can be obtained when carbon nanotubes are grown closely together as a result of van der Waals interactions. The ali,onment however is marginal, and the van der Waals prerequisite makes growth of freestanding nanofibres with thermal CVD unrealizable. The application of electric fields as a means of ali,onment has been shown to overcome this limitation [2-5], and highly aligned nanostructures can be grown if electric fields on the order of 0.5 V/microns are employed. Plasma enhanced CVD in various configurations including dc, rf, microwave, inductive and electron cyclotron resonance has been pursued as a means of enabling alignment in the CVD process. However, the sheath fields for the non-dc sources are in general not sufficient for a high degree of ali,pment and an additional dc bias is usually applied to the growth substrate. This begs the question as to the actual role of the plasma. It is clear that the plasma itself is not required for aligned growth as references [3] and [4] employed fields through small applied voltages (3-20 V) across very small electrode spacings (10-100 microns) and thus avoided striking a discharge.

Hash, David B.↗

Addressing genome scale design tradeoffs in Pseudomonas putida for bioconversion of an aromatic carbon source

Genome-scale metabolic models (GSMM) are commonly used to identify gene deletion sets that result in growth coupling and pairing product formation with substrate utilization and can improve strain performance beyond levels typically accessible using traditional strain engineering approaches. However, sustainable feedstocks pose a challenge due to incomplete high-resolution metabolic data for non-canonical carbon sources required to curate GSMM and identify implementable designs. Here we address a four-gene deletion design in the Pseudomonas putida KT2440 strain for the lignin-derived non-sugar carbon source, p-coumarate (p-CA), that proved challenging to implement. We examine the performance of the fully implemented design for p-coumarate to glutamine, a useful biomanufacturing intermediate. In this study glutamine is then converted to indigoidine, an alternative sustainable pigment and a model heterologous product that is commonly used to colorimetrically quantify glutamine concentration. Through proteomics, promoter-variation, and growth characterization of a fully implemented gene deletion design, we provide evidence that aromatic catabolism in the completed design is rate-limited by fumarase hydratase (FUM) enzyme activity in the citrate cycle and requires careful optimization of another fumarate hydratase protein (PP_0897) expression to achieve growth and production. A double sensitivity analysis also confirmed a strict requirement for fumarate hydratase activity in the strain where all genes in the growth coupling design have been implemented. Metabolic cross-feeding experiments were used to examine the impact of complete removal of the fumarase hydratase reaction and revealed an unanticipated nutrient requirement, suggesting additional functions for this enzyme. While a complete implementation of the design was achieved, this study highlights the challenge of completely inactivating metabolic reactions encoded by under-characterized proteins, especially in the context of multi-gene edits.

59 BASIC BIOLOGICAL SCIENCES↗

Planarizing Spalled GaAs(100) Surfaces by MOVPE Growth

III-V photovoltaic devices have demonstrated remarkable performance in many applications, and spalling is a promising technique for reducing device costs by recovering the substrate for reuse. In this study, we investigate the in situ planarization of A-directionally spalled GaAs(100) substrates using metal-organic vapor phase epitaxy (MOVPE) grown C:GaAs with CCl4 as the carbon source. We have characterized the (100)-oriented growth for various CCl4 flow rates and observed that the CCl4 or its by-products promote material diffusion from the facet tops to the underlying valleys. For facets with a height of 5 ..mu..m on a substrate with an A-spall and 6 degreesB -offcut, it took 7 ..mu..m of C:GaAs to planarize the substrate. For a similar sample, with a 6 degreesA -offcut, it required 2 ..mu..m of growth to fill the valleys but there were remnant facets.

III-V↗