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Sample records for additional carbon atom

  1. Heat conduction in double-walled carbon nanotubes with intertube additional carbon atoms.

    PubMed

    Cui, Liu; Feng, Yanhui; Tan, Peng; Zhang, Xinxin

    2015-07-07

    Heat conduction of double-walled carbon nanotubes (DWCNTs) with intertube additional carbon atoms was investigated for the first time using a molecular dynamics method. By analyzing the phonon vibrational density of states (VDOS), we revealed that the intertube additional atoms weak the heat conduction along the tube axis. Moreover, the phonon participation ratio (PR) demonstrates that the heat transfer in DWCNTs is dominated by low frequency modes. The added atoms cause the mode weight factor (MWF) of the outer tube to decrease and that of the inner tube to increase, which implies a lower thermal conductivity. The effects of temperature, tube length, and the number and distribution of added atoms were studied. Furthermore, an orthogonal array testing strategy was designed to identify the most important structural factor. It is indicated that the tendencies of thermal conductivity of DWCNTs with added atoms change with temperature and length are similar to bare ones. In addition, thermal conductivity decreases with the increasing number of added atoms, more evidently for atom addition concentrated at some cross-sections rather than uniform addition along the tube length. Simultaneously, the number of added atoms at each cross-section has a considerably more remarkable impact, compared to the tube length and the density of chosen cross-sections to add atoms.

  2. A New Nitrogenase Mechanism Using a CFe8S9 Model: Does H2 Elimination Activate the Complex to N2 Addition to the Central Carbon Atom?

    PubMed

    McKee, Michael L

    2016-02-11

    A truncated model of the FeMo cofactor is used to explore a new mechanism for the conversion of N2 to NH3 by the nitrogenase enzyme. After four initial protonation/reduction steps, the H4CFe8S9 cluster has two hydrogen atoms attached to sulfur, one hydrogen bridging two iron centers and one hydrogen bonded to carbon. The loss of the CH and FeHFe hydrogens as molecular hydrogen activates the cluster to addition of N2 to the carbon center. This unique step takes place at a nearly planar four-coordinate carbon center and leads to an intermediate with a significantly weakened N-N bond. A hydrogen attached to a sulfur atom is then transferred to the distal nitrogen atom. Additional prontonation/reduction steps are modeled by adding a hydrogen atom to sulfur and locating the transition states for transfer to nitrogen. The first NH3 is lost in a thermal neutral step, while the second step is endothermic. The loss of H2 activates the complex by reducing the barrier for N2 addition by 3.5 kcal/mol. Since this is the most difficult step in the mechanism, reducing the barrier for this step justifies the "extra expense" of H2 production.

  3. Reversible Oxidative Addition at Carbon.

    PubMed

    Eichhorn, Antonius F; Fuchs, Sonja; Flock, Marco; Marder, Todd B; Radius, Udo

    2017-04-07

    The reactivity of N-heterocyclic carbenes (NHCs) and cyclic alkyl amino carbenes (cAACs) with arylboronate esters is reported. The reaction with NHCs leads to the reversible formation of thermally stable Lewis acid/base adducts Ar-B(OR)2 ⋅NHC (Add1-Add6). Addition of cAAC(Me) to the catecholboronate esters 4-R-C6 H4 -Bcat (R=Me, OMe) also afforded the adducts 4-R-C6 H4 Bcat⋅cAAC(Me) (Add7, R=Me and Add8, R=OMe), which react further at room temperature to give the cAAC(Me) ring-expanded products RER1 and RER2. The boronate esters Ar-B(OR)2 of pinacol, neopentylglycol, and ethyleneglycol react with cAAC at RT via reversible B-C oxidative addition to the carbene carbon atom to afford cAAC(Me) (B{OR}2 )(Ar) (BCA1-BCA6). NMR studies of cAAC(Me) (Bneop)(4-Me-C6 H4 ) (BCA4) demonstrate the reversible nature of this oxidative addition process.

  4. Atomic transportation via carbon nanotubes.

    PubMed

    Wang, Quan

    2009-01-01

    The transportation of helium atoms in a single-walled carbon nanotube is reported via molecular dynamics simulations. The efficiency of the atomic transportation is found to be dependent on the type of the applied loading and the loading rate as well as the temperature in the process. Simulations show the transportation is a result of the van der Waals force between the nanotube and the helium atoms through a kink propagation initiated in the nanotube.

  5. Carbon Slurry Secondary Atomization.

    DTIC Science & Technology

    1986-09-01

    from work with coal -water mixtures, that agglomeration of carbon particles in the former instance and coal particles in the latter occurs. To improve...volatiles and a higher concentration of coal . This leads to agglomeration . As Law points out, a 100-pm droplet containing 1 percent coal will yield a 20-im...to get to the surface and evaporate, so that batch distillation occurs and the non-volatile coal particles agglomerate . Agglomeration can be

  6. Collective electronic excitations in the ultra violet regime in 2-D and 1-D carbon nanostructures achieved by the addition of foreign atoms

    NASA Astrophysics Data System (ADS)

    Bangert, U.; Pierce, W.; Boothroyd, C.; Pan, C.-T.; Gwilliam, R.

    2016-06-01

    Plasmons in the visible/UV energy regime have attracted great attention, especially in nano-materials, with regards to applications in opto-electronics and light harvesting; tailored enhancement of such plasmons is of particular interest for prospects in nano-plasmonics. This work demonstrates that it is possible, by adequate doping, to create excitations in the visible/UV regime in nano-carbon materials, i.e., carbon nanotubes and graphene, with choice of suitable ad-atoms and dopants, which are introduced directly into the lattice by low energy ion implantation or added via deposition by evaporation. Investigations as to whether these excitations are of collective nature, i.e., have plasmonic character, are carried out via DFT calculations and experiment-based extraction of the dielectric function. They give evidence of collective excitation behaviour for a number of the introduced impurity species, including K, Ag, B, N, and Pd. It is furthermore demonstrated that such excitations can be concentrated at nano-features, e.g., along nano-holes in graphene through metal atoms adhering to the edges of these holes.

  7. Collective electronic excitations in the ultra violet regime in 2-D and 1-D carbon nanostructures achieved by the addition of foreign atoms

    PubMed Central

    Bangert, U.; Pierce, W.; Boothroyd, C.; Pan, C.-T.; Gwilliam, R.

    2016-01-01

    Plasmons in the visible/UV energy regime have attracted great attention, especially in nano-materials, with regards to applications in opto-electronics and light harvesting; tailored enhancement of such plasmons is of particular interest for prospects in nano-plasmonics. This work demonstrates that it is possible, by adequate doping, to create excitations in the visible/UV regime in nano-carbon materials, i.e., carbon nanotubes and graphene, with choice of suitable ad-atoms and dopants, which are introduced directly into the lattice by low energy ion implantation or added via deposition by evaporation. Investigations as to whether these excitations are of collective nature, i.e., have plasmonic character, are carried out via DFT calculations and experiment-based extraction of the dielectric function. They give evidence of collective excitation behaviour for a number of the introduced impurity species, including K, Ag, B, N, and Pd. It is furthermore demonstrated that such excitations can be concentrated at nano-features, e.g., along nano-holes in graphene through metal atoms adhering to the edges of these holes. PMID:27271352

  8. Collective electronic excitations in the ultra violet regime in 2-D and 1-D carbon nanostructures achieved by the addition of foreign atoms.

    PubMed

    Bangert, U; Pierce, W; Boothroyd, C; Pan, C-T; Gwilliam, R

    2016-06-07

    Plasmons in the visible/UV energy regime have attracted great attention, especially in nano-materials, with regards to applications in opto-electronics and light harvesting; tailored enhancement of such plasmons is of particular interest for prospects in nano-plasmonics. This work demonstrates that it is possible, by adequate doping, to create excitations in the visible/UV regime in nano-carbon materials, i.e., carbon nanotubes and graphene, with choice of suitable ad-atoms and dopants, which are introduced directly into the lattice by low energy ion implantation or added via deposition by evaporation. Investigations as to whether these excitations are of collective nature, i.e., have plasmonic character, are carried out via DFT calculations and experiment-based extraction of the dielectric function. They give evidence of collective excitation behaviour for a number of the introduced impurity species, including K, Ag, B, N, and Pd. It is furthermore demonstrated that such excitations can be concentrated at nano-features, e.g., along nano-holes in graphene through metal atoms adhering to the edges of these holes.

  9. Theory of atomic additivity in molecular hyperpolizabilities

    NASA Technical Reports Server (NTRS)

    Baird, James K.

    1987-01-01

    Hyperpolarizability is a function of frequency. This is called dispersion. Because of the Kramers-Kronig relations, researchers expect that a material that is dispersing light is also absorbing it. Where there is both dispersion and absorption, the molecular polarizabilities are complex functions of the frequency. This led researchers to consider atomic additivity in both the real and imaginary parts of the ordinary and hyperpolarizabilities. This effort is desirable not only from a theoretical point of view, but also because of the existence of a large body of complex refractive index data, which may be used to test the additivity principle with the complex valued ordinary dipole polarizability.

  10. Strong gold atom strands formed by incorporation of carbon atoms

    NASA Astrophysics Data System (ADS)

    Oshima, Yoshifumi; Kurui, Yoshihiko; Nguyen, Huy Duy; Ono, Tomoya; Takayanagi, Kunio

    2011-07-01

    Single metal atom strands have attracted significant interest because of their unique properties, such as quantization effects and a high degree of strength. Recently it was suggested that the strength of a gold atom strand can be enhanced by the insertion of an impurity atom, but it has not been experimentally investigated. Using a transmission electron microscope under ultrahigh vacuum conditions, we observed that gold atoms were pulled out one by one from a carbon-contaminated gold (111) surface to form a long atom strand. The strand was so strong that it did not break even upon bending. Supported by first-principles calculations, the strand was found to have two carbon atoms at each gold atom interval. Our observations suggest that the carbon atoms act as a glue to form a long gold atom strand.

  11. Functionalization of Carbon Nanotubes using Atomic Hydrogen

    NASA Technical Reports Server (NTRS)

    Khare, Bishun N.; Cassell, Alan M.; Nguyen, Cattien V.; Meyyappan, M.; Han, Jie; Arnold, Jim (Technical Monitor)

    2001-01-01

    We have investigated the irradiation of multi walled and single walled carbon nanotubes (SWNTs) with atomic hydrogen. After irradiating the SWNT sample, a band at 2940/cm (3.4 microns) that is characteristic of the C-H stretching mode is observed using Fourier transform infrared (FTIR) spectroscopy. Additional confirmation of SWNT functionalization is tested by irradiating with atomic deuterium. A weak band in the region 1940/cm (5.2 micron) to 2450/cm (4.1 micron) corresponding to C-D stretching mode is also observed in the FTIR spectrum. This technique provides a clean gas phase process for the functionalization of SWNTs, which could lead to further chemical manipulation and/or the tuning of the electronic properties of SWNTs for nanodevice applications.

  12. Local Atomic Density of Microporous Carbons

    SciTech Connect

    Dmowski, Wojtek; Contescu, Cristian I.; Llobet, Anna; Gallego, Nidia C.; Egami, Takeskhi

    2012-07-12

    We investigated the structure of two disordered carbons: activated carbon fibers (ACF) and ultramicroporous carbon (UMC). These carbons have highly porous structure with large surface areas and consequently low macroscopic density that should enhance adsorption of hydrogen. We used the atomic pair distribution function to probe the local atomic arrangements. The results show that the carbons maintain an in-plane local atomic structure similar to regular graphite, but the stacking of graphitic layers is strongly disordered. Although the local atomic density of these carbons is lower than graphite, it is only {approx}20% lower and is much higher than the macroscopic density due to the porosity of the structure. For this reason, the density of graphene sheets that have optimum separation for hydrogen adsorption is lower than anticipated.

  13. Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds

    DOEpatents

    Hartwig, John F.; Kawatsura, Motoi; Loeber, Oliver

    2002-01-01

    The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.

  14. Reactions of carbon atoms in pulsed molecular beams

    SciTech Connect

    Reisler, H.

    1993-12-01

    This research program consists of a broad scope of experiments designed to unravel the chemistry of atomic carbon in its two spin states, P and D, by using well-controlled initial conditions and state-resolved detection of products. Prerequisite to the proposed studies (and the reason why so little is known about carbon atom reactions), is the development of clean sources of carbon atoms. Therefore, in parallel with the studies of its chemistry and reaction dynamics, the authors continuously explore new, state-specific and efficient ways of producing atomic carbon. In the current program, C({sup 3}P) is produced via laser ablation of graphite, and three areas of study are being pursued: (i) exothermic reactions with small inorganic molecules (e.g., O{sub 2}, N{sub 2}O, NO{sub 2}) that can proceed via multiple pathways; (ii) the influence of vibrational and translational energy on endothermic reactions involving H-containing reactants that yield CH products (e.g., H{sub 2}O H{sub 2}CO); (iii) reactions of C({sup 3}P) with free radicals (e.g., HCO, CH{sub 3}O). In addition, the authors plan to develop a source of C({sup 1}D) atoms by exploiting the pyrolysis of diazotetrazole and its salts in the ablation source. Another important goal involves collaboration with theoreticians in order to obtain relevant potential energy surfaces, rationalize the experimental results and predict the roles of translational and vibrational energies.

  15. Atomic Carbon in the Southern Milky Way

    NASA Astrophysics Data System (ADS)

    Oka, Tomoharu; Kamegai, Kazuhisa; Hayashida, Masaaki; Nagai, Makoto; Ikeda, Masafumi; Kuboi, Nobuyuki; Tanaka, Kunihiko; Bronfman, Leonardo; Yamamoto, Satoshi

    2005-04-01

    We present a coarsely sampled longitude-velocity (l-V) map of the region l=300deg-354°, b=0deg in the 492 GHz fine-structure transition of neutral atomic carbon (C0 3P1-3P0 [C I]), observed with the Portable 18 cm Submillimeter-wave Telescope (POST18). The l-V distribution of the [C I] emission resembles closely that of the CO J=1-0 emission, showing a widespread distribution of atomic carbon on the Galactic scale. The ratio of the antenna temperatures, RCI/CO, concentrates on the narrow range from 0.05 to 0.3. A large velocity gradient (LVG) analysis shows that the [C I] emission from the Galactic disk is dominated by a population of neutral gas with high C0/CO abundance ratios and moderate column densities, which can be categorized as diffuse translucent clouds. The ratio of bulk emissivity, JCI/JCO, shows a systematic trend, suggesting the bulk C0/CO abundance ratio increasing with the Galactic radius. A mechanism related to kiloparsec-scale structure of the Galaxy may control the bulk C0/CO abundance ratio in the Galactic disk. Two groups of high-ratio (RCI/CO>0.3) areas reside in the l-V loci several degrees inside of tangential points of the Galactic spiral arms. These could be gas condensations just accumulated in the potential well of spiral arms and be in the early stages of molecular cloud formation.

  16. Carbon based thirty six atom spheres

    DOEpatents

    Piskoti, Charles R.; Zettl, Alex K.; Cohen, Marvin L.; Cote, Michel; Grossman, Jeffrey C.; Louie, Steven G.

    2005-09-06

    A solid phase or form of carbon is based on fullerenes with thirty six carbon atoms (C.sub.36). The C.sub.36 structure with D.sub.6h symmetry is one of the two most energetically favorable, and is conducive to forming a periodic system. The lowest energy crystal is a highly bonded network of hexagonal planes of C.sub.36 subunits with AB stacking. The C.sub.36 solid is not a purely van der Waals solid, but has covalent-like bonding, leading to a solid with enhanced structural rigidity. The solid C.sub.36 material is made by synthesizing and selecting out C.sub.36 fullerenes in relatively large quantities. A C.sub.36 rich fullerene soot is produced in a helium environment arc discharge chamber by operating at an optimum helium pressure (400 torr). The C.sub.36 is separated from the soot by a two step process. The soot is first treated with a first solvent, e.g. toluene, to remove the higher order fullerenes but leave the C.sub.36. The soot is then treated with a second solvent, e.g. pyridine, which is more polarizable than the first solvent used for the larger fullerenes. The second solvent extracts the C.sub.36 from the soot. Thin films and powders can then be produced from the extracted C.sub.36. Other materials are based on C.sub.36 fullerenes, providing for different properties.

  17. Carbon nanotube-clamped metal atomic chain

    PubMed Central

    Tang, Dai-Ming; Yin, Li-Chang; Li, Feng; Liu, Chang; Yu, Wan-Jing; Hou, Peng-Xiang; Wu, Bo; Lee, Young-Hee; Ma, Xiu-Liang; Cheng, Hui-Ming

    2010-01-01

    Metal atomic chain (MAC) is an ultimate one-dimensional structure with unique physical properties, such as quantized conductance, colossal magnetic anisotropy, and quantized magnetoresistance. Therefore, MACs show great potential as possible components of nanoscale electronic and spintronic devices. However, MACs are usually suspended between two macroscale metallic electrodes; hence obvious technical barriers exist in the interconnection and integration of MACs. Here we report a carbon nanotube (CNT)-clamped MAC, where CNTs play the roles of both nanoconnector and electrodes. This nanostructure is prepared by in situ machining a metal-filled CNT, including peeling off carbon shells by spatially and elementally selective electron beam irradiation and further elongating the exposed metal nanorod. The microstructure and formation process of this CNT-clamped MAC are explored by both transmission electron microscopy observations and theoretical simulations. First-principles calculations indicate that strong covalent bonds are formed between the CNT and MAC. The electrical transport property of the CNT-clamped MAC was experimentally measured, and quantized conductance was observed. PMID:20427743

  18. Chains of carbon atoms: A vision or a new nanomaterial?

    PubMed Central

    2015-01-01

    Summary Linear strings of sp1-hybridized carbon atoms are considered as a possible phase of carbon since decades. Whereas the debate about the stability of the corresponding bulk phase carbyne continues until today, the existence of isolated chains of carbon atoms has meanwhile been corroborated experimentally. Since graphene, as the two-dimensional sp2-bonded allotrope of carbon, has become a vast field, the question about the importance of one-dimensional carbon became of renewed interest. The present article gives an overview of the work that has been carried out on chains of carbon atoms in the past one or two decades. The review concentrates on isolated chains of carbon atoms and summarizes the experimental observations to date. While the experimental information is still very limited, many calculations of the physical and chemical properties have been published in the past years. Some of the most important theoretical studies and their importance in the present experimental situation are reviewed. PMID:25821697

  19. Chains of carbon atoms: A vision or a new nanomaterial?

    PubMed

    Banhart, Florian

    2015-01-01

    Linear strings of sp(1)-hybridized carbon atoms are considered as a possible phase of carbon since decades. Whereas the debate about the stability of the corresponding bulk phase carbyne continues until today, the existence of isolated chains of carbon atoms has meanwhile been corroborated experimentally. Since graphene, as the two-dimensional sp(2)-bonded allotrope of carbon, has become a vast field, the question about the importance of one-dimensional carbon became of renewed interest. The present article gives an overview of the work that has been carried out on chains of carbon atoms in the past one or two decades. The review concentrates on isolated chains of carbon atoms and summarizes the experimental observations to date. While the experimental information is still very limited, many calculations of the physical and chemical properties have been published in the past years. Some of the most important theoretical studies and their importance in the present experimental situation are reviewed.

  20. Roles of additives and surface control in slurry atomization

    SciTech Connect

    Tsai, S.C.

    1992-01-01

    This project studies the rheology and airblast atomization of micronized coal slurries. Its major objectives are (1) to promote further understanding of the mechanisms and the roles of additives in airblast atomization of coal water slurry (CWS), and (2) to investigate the impacts of coal particle surface properties and interparticle forces on CWS rheology. We have found that the flow behavior index (n) of a suspension (or slurry) is determined by the relative importance of the interparticle van der Waals attraction and the interparticle electrostatic repulsion. The interparticle attraction, measured by the Hamaker constant scaled to the thermal energy at 25[degrees]C (A/kT), causes particle aggregation, which breaks down at high shear rates, and thus leads to slurry pseudoplastic behavior (n< 1). At a constant particle volume fraction and surface charge density (qualitatively measured by the zeta potential in deionized water), n decreases linearly as A/kT increases. The relative viscosity of the pseudoplastic suspension with respect to that of the suspending liquid is found to be independent of particle density and correlate well with the particle Peclet number which equals the particle diffusional relaxation time multiplied by shear rate. Specifically, the relative viscosities of the pseudoplastic glycerol/water coal slurry and the ethylene glycol/glycerol sand slurry, at same volume fractions as well as similar particle size distributions and liquid viscosities, as functions of the particle Peclet number fall along the same line.

  1. ATOMIC CARBON IN THE UPPER ATMOSPHERE OF TITAN

    SciTech Connect

    Zhang, X.; Yung, Y. L.; Ajello, J. M.

    2010-01-01

    The atomic carbon emission C I line feature at 1657 A ({sup 3} P {sup 0} {sub J}-{sup 3} P{sub J} ) in the upper atmosphere of Titan is first identified from the airglow spectra obtained by the Cassini Ultra-violet Imaging Spectrograph. A one-dimensional photochemical model of Titan is used to study the photochemistry of atomic carbon on Titan. Reaction between CH and atomic hydrogen is the major source of atomic carbon, and reactions with hydrocarbons (C{sub 2}H{sub 2} and C{sub 2}H{sub 4}) are the most important loss processes. Resonance scattering of sunlight by atomic carbon is the dominant emission mechanism. The emission intensity calculations based on model results show good agreement with the observations.

  2. Roles of additives and surface control in slurry atomization

    SciTech Connect

    Tsai, S.C.

    1990-01-01

    This report focuses on the effects of interparticle forces on the rheology and airblast atomization of micronized coal water slurry (CWS). We found that the CWS flow behavior index is determined by the relative importance of the interparticle van der Waals attraction and the interparticle electrostatic repulsion. The former intensifies as the Hamaker constant increases and the interparticle distance reduces while the latter increases as the particle surface charge density increases. The interparticle attraction causes particle aggregation, which breaks down at high shear rates, and thus leads to slurry pseudoplastic behavior. In contrast, the interparticle repulsion prevents particle aggregation and thus leads to Newtonian behavior. Both atomized at low atomizing air pressures (less than 270 kPa) using twin-fluid jet atomizers of various distributor designs. We found that the atomized drop sizes of micronized coal water slurries substantially decrease as the atomizing air pressure exceeds a threshold value. The effects of coal volume fraction, coal particle surface charge, liquid composition and liquid viscosity on slurry atomization can be accounted for by their effects on slurry rheology. 26 refs.

  3. Carbon additives for electrical double layer capacitor electrodes

    NASA Astrophysics Data System (ADS)

    Weingarth, D.; Cericola, D.; Mornaghini, F. C. F.; Hucke, T.; Kötz, R.

    2014-11-01

    Electrochemical double layer capacitors (EDLCs) are inherently high power devices when compared to rechargeable batteries. While capacitance and energy storage ability are mainly increased by optimizing the electrode active material or the electrolyte, the power capability could be improved by including conductive additives in the electrode formulations. This publication deals with the use of four different carbon additives - two carbon blacks and two graphites - in standard activated carbon based EDLC electrodes. The investigations include: (i) physical characterization of carbon powder mixtures such as surface area, press density, and electrical resistivity measurements, and (ii), electrochemical characterization via impedance spectroscopy and cyclic voltammetry of full cells made with electrodes containing 5 wt.% of carbon additive and compared to cells made with pure activated carbon electrodes in organic electrolyte. Improved cell performance was observed in both impedance and cyclic voltammetry responses. The results are discussed considering the main characteristics of the different carbon additives, and important considerations about electrode structure and processability are drawn.

  4. Angular distribution of photoelectrons from atomic oxygen, nitrogen, and carbon

    NASA Technical Reports Server (NTRS)

    Manson, S. T.; Kennedy, D. J.; Starace, A. F.; Dill, D.

    1974-01-01

    The angular distribution of photoelectrons from atomic oxygen is investigated using Hartree-Fock (HF) wave functions. The correct formulation is used to compare HS and HF results. Agreement between these results is good and the HS calculations have been extended to atomic nitrogen and carbon as well.

  5. Automated manipulation of carbon nanotubes using atomic force microscopy.

    PubMed

    Zhang, Chao; Wu, Sen; Fu, Xing

    2013-01-01

    The manipulation of carbon nanotubes is an important and essential step for carbon-based nanodevice or nanocircuit assembly. However, the conventional push-and-image approach of manipulating carbon nanotubes using atomic force microscopy has low efficiency on account of the reduplicated scanning process during manipulation. In this article, an automated manipulation system is designed and tested. This automated manipulation system, which includes an atomic force microscope platform and a self-developed computer program for one-dimensional manipulation, is capable of automatically moving any assigned individual carbon nanotube to a defined target location without any intermediate scanning procedure. To demonstrate the high-efficiency of this automated manipulation system and its potential applications in nanoassembly, two experiments were conducted. The first experiment used this system to manipulate a carbon nanotube to a defined target location. In the second experiment, this system was used to automatically manipulate several carbon nanotubes for generating and translating a defined pattern of nanotubes.

  6. Atomic scale simulation of carbon nanotube nucleation from hydrocarbon precursors

    PubMed Central

    Khalilov, Umedjon; Bogaerts, Annemie; Neyts, Erik C.

    2015-01-01

    Atomic scale simulations of the nucleation and growth of carbon nanotubes is essential for understanding their growth mechanism. In spite of over twenty years of simulation efforts in this area, limited progress has so far been made on addressing the role of the hydrocarbon growth precursor. Here we report on atomic scale simulations of cap nucleation of single-walled carbon nanotubes from hydrocarbon precursors. The presented mechanism emphasizes the important role of hydrogen in the nucleation process, and is discussed in relation to previously presented mechanisms. In particular, the role of hydrogen in the appearance of unstable carbon structures during in situ experimental observations as well as the initial stage of multi-walled carbon nanotube growth is discussed. The results are in good agreement with available experimental and quantum-mechanical results, and provide a basic understanding of the incubation and nucleation stages of hydrocarbon-based CNT growth at the atomic level. PMID:26691537

  7. 46 CFR 151.50-40 - Additional requirements for carbon disulfide (carbon bisulfide) and ethyl ether.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Additional requirements for carbon disulfide (carbon... Special Requirements § 151.50-40 Additional requirements for carbon disulfide (carbon bisulfide) and ethyl... waterways at the loading and unloading points. (f) The special requirements of § 151.50-41 for...

  8. 46 CFR 151.50-40 - Additional requirements for carbon disulfide (carbon bisulfide) and ethyl ether.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Additional requirements for carbon disulfide (carbon... Special Requirements § 151.50-40 Additional requirements for carbon disulfide (carbon bisulfide) and ethyl... waterways at the loading and unloading points. (f) The special requirements of § 151.50-41 for...

  9. 46 CFR 151.50-40 - Additional requirements for carbon disulfide (carbon bisulfide) and ethyl ether.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Additional requirements for carbon disulfide (carbon... Special Requirements § 151.50-40 Additional requirements for carbon disulfide (carbon bisulfide) and ethyl... waterways at the loading and unloading points. (f) The special requirements of § 151.50-41 for...

  10. 46 CFR 151.50-40 - Additional requirements for carbon disulfide (carbon bisulfide) and ethyl ether.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Additional requirements for carbon disulfide (carbon... Special Requirements § 151.50-40 Additional requirements for carbon disulfide (carbon bisulfide) and ethyl... waterways at the loading and unloading points. (f) The special requirements of § 151.50-41 for...

  11. 46 CFR 151.50-40 - Additional requirements for carbon disulfide (carbon bisulfide) and ethyl ether.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Additional requirements for carbon disulfide (carbon... Special Requirements § 151.50-40 Additional requirements for carbon disulfide (carbon bisulfide) and ethyl... waterways at the loading and unloading points. (f) The special requirements of § 151.50-41 for...

  12. The Importance of Carbon Fiber to Polymer Additive Manufacturing

    SciTech Connect

    Love, Lonnie J; Kunc, Vlastimil; Rios, Orlando; Duty, Chad E; Post, Brian K; Blue, Craig A

    2014-01-01

    Additive manufacturing holds tremendous promise in terms of revolutionizing manufacturing. However, fundamental hurdles limit mass adoption of the technology. First, production rates are extremely low. Second, the physical size of parts is generally small, less than a cubic foot. Third, while there is much excitement about metal additive manufacturing, the major growth area is in polymer additive manufacturing systems. Unfortunately, the mechanical properties of the polymer parts are poor, limiting the potential for direct part replacement. To address this issue, we describe three benefits of blending carbon fiber with polymer additive manufacturing. First, development of carbon fiber reinforced polymers for additive manufacturing achieves specific strengths approaching aerospace quality aluminum. Second, carbon fiber radically changes the behavior of the material during deposition, enabling large scale, out-of-the-oven, high deposition rate manufacturing. Finally, carbon fiber technology and additive manufacturing complement each other. Merging the two manufacturing processes enables the construction of complex components that would not be possible otherwise.

  13. Photoluminescent carbon dots from 1,4-addition polymers.

    PubMed

    Jiang, Zhiqiang; Nolan, Andrew; Walton, Jeffrey G A; Lilienkampf, Annamaria; Zhang, Rong; Bradley, Mark

    2014-08-25

    Photoluminescent carbon dots were synthesised directly by thermopyrolysis of 1,4-addition polymers, allowing precise control of their properties. The effect of polymer composition on the properties of the carbon dots was investigated by TEM, IR, XPS, elemental analysis and fluorescence analysis, with carbon dots synthesised from nitrogen-containing polymers showing the highest fluorescence. The carbon dots with high nitrogen content were observed to have strong fluorescence in the visible region, and culture with cells showed that the carbon dots were non-cytotoxic and readily taken up by three different cell lines.

  14. Relative stopping powers for atomic and molecular ions in carbon

    NASA Astrophysics Data System (ADS)

    Steuer, Malcolm F.

    1986-03-01

    Electronic stopping powers of carbon for atomic and molecular nitrogen ions have been calculated using semi-classical free electron scattering from Herman-Skillman potentials, parametrized to include an adjustable exponential screening factor F( tv, Z), representing atomic ions. For molecular ions, aligned along the beam direction and having velocity 1.2 a.u., the stopping powers for individual atomic components were calculated as a function of internuclear separation. Screening factors for the two centers of force were assumed to decrease linearly from the value at zero internuclear separation, equivalent to that of a silicon ion, to that for nitrogen ions at large separations. Results are consistent with the diminishment of average stopping power per atomic ion which has been observed for beam-aligned nitrogen molecular ions. Similar calculations for molecular hydrogen in carbon agree with the enhancement of stopping power which has been observed. Evidence of nonlinear effects is indicated.

  15. Atomic migration of carbon in hard turned layers of carburized bearing steel

    DOE PAGES

    Bedekar, Vikram; Poplawsky, Jonathan D.; Guo, Wei; ...

    2016-01-01

    In grain finement and non-equilibrium there is carbon segregation within grain boundaries alters the mechanical performance of hard turning layers in carburized bearing steel. Moreover, an atom probe tomography (APT) study on the nanostructured hard turning layers reveals carbon migration to grain boundaries as a result of carbide decomposition during severe plastic deformation. In addition, samples exposed to different cutting speeds show that the carbon migration rate increases with the cutting speed. For these two effects lead to an ultrafine carbon network structure resulting in increased hardness and thermal stability in the severely deformed surface layer.

  16. Surface modification of carbon post arrays by atomic layer deposition of ZnO film.

    PubMed

    Lee, Hyun Ae; Byun, Young-Chul; Singh, Umesh; Cho, Hyoung J; Kim, Hyoungsub

    2011-08-01

    The applicability of atomic layer deposition (ALD) process to the carbon microelectromechanical system technology was studied for a surface modification method of the carbon post electrodes. A conformal coating of the ALD-ZnO film was successfully demonstrated on the carbon post arrays which were fabricated by the traditional photolithography and subsequent two-step pyrolysis. A significant Zn diffusion into the underlying carbon posts was observed during the ALD process. The addition of a sputter-deposited ZnO interfacial layer efficiently blocked the Zn diffusion without altering the microstructure and surface morphology of the ALD-ZnO film.

  17. ENERGETIC NEUTRAL ATOMS: AN ADDITIONAL SOURCE FOR HELIOSPHERIC PICKUP IONS

    SciTech Connect

    Bochsler, Peter; Moebius, Eberhard

    2010-09-20

    Recently, Schwadron and McComas discussed the possibility of inner source pickup particles originating from the ionization of energetic neutral atoms (ENAs), based on new data from the IBEX mission. This proposition has some interesting features, namely, it might be able to explain why inner source pickup ions (PUIs) have a composition resembling solar abundances and show no indication of overabundance of refractory elements, although this should be expected, if the conventional explanation of solar wind-dust interaction for the origin of this heliospheric component were correct. In this Letter, we explore further consequences for ENA-related PUIs and investigate their velocity distributions. We conclude that this model will not reproduce the observed velocity distributions of inner source PUIs and point out a substantial deviation in their composition. However, it seems likely that the ionization of ENAs as observed with IBEX could contribute a significant amount of heliospheric suprathermal tail ions. Some possible consequences of our investigation for heliospheric particle populations are briefly discussed.

  18. Growth and Destruction of PAH Molecules in Reactions with Carbon Atoms

    NASA Astrophysics Data System (ADS)

    Krasnokutski, Serge A.; Huisken, Friedrich; Jäger, Cornelia; Henning, Thomas

    2017-02-01

    A very high abundance of atomic carbon in the interstellar medium (ISM), and the high reactivity of these species toward different hydrocarbon molecules including benzene, raise questions regarding the stability of polycyclic aromatic hydrocarbon (PAH) molecules in space. To test the efficiency of destruction of PAH molecules via reactions with atomic carbon, we performed a set of laboratory and computational studies of the reactions of naphthalene, anthracene, and coronene molecules with carbon atoms in the ground state. The reactions were investigated in liquid helium droplets at T = 0.37 K and by quantum chemical computations. Our studies suggest that all small and all large catacondensed PAHs react barrierlessly with atomic carbon, and therefore should be efficiently destroyed by such reactions in a broad temperature range. At the same time, large compact pericondensed PAHs should be more inert toward such a reaction. In addition, taking into account their higher photostability, much higher abundances of pericondensed PAHs should be expected in various astrophysical environments. The barrierless reactions between carbon atoms and small PAHs also suggest that, in the ISM, these reactions could lead to the bottom-up formation of PAH molecules.

  19. Neutral atomic carbon in dense molecular clouds

    NASA Technical Reports Server (NTRS)

    Zmuidzinas, J.; Betz, A. L.; Boreiko, R. T.; Goldhaber, D. M.

    1988-01-01

    The 370 micron 3P2-3P1 fine-structure line of neutral carbon was detected in seven sources: OMC 1, NGC 2024, S140, W3, DR 21, M17, and W51. Simultaneous analysis of J = 2-1 data and available observations of the J = 1-0 line make it possible to deduce optical depths and excitation temperatures for these lines. These data indicate that both C I lines are likely to be optically thin, and that the ratio of C I to CO column densities in these clouds is typically about 0.1.

  20. 48 CFR 204.470 - U.S.-International Atomic Energy Agency Additional Protocol.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 48 Federal Acquisition Regulations System 3 2011-10-01 2011-10-01 false U.S.-International Atomic Energy Agency Additional Protocol. 204.470 Section 204.470 Federal Acquisition Regulations System DEFENSE... Information Within Industry 204.470 U.S.-International Atomic Energy Agency Additional Protocol....

  1. 48 CFR 204.470 - U.S.-International Atomic Energy Agency Additional Protocol.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 48 Federal Acquisition Regulations System 3 2010-10-01 2010-10-01 false U.S.-International Atomic Energy Agency Additional Protocol. 204.470 Section 204.470 Federal Acquisition Regulations System DEFENSE... Information Within Industry 204.470 U.S.-International Atomic Energy Agency Additional Protocol....

  2. Carbon concentration measurements by atom probe tomography in the ferritic phase of high-silicon steels

    DOE PAGES

    Rementeria, Rosalia; Poplawsky, Jonathan D.; Aranda, Maria M.; ...

    2016-12-19

    Current studies using atom probe tomography (APT) show that bainitic ferrite formed at low temperature contains more carbon than what is consistent with the paraequilibrium phase diagram. However, nanocrystalline bainitic ferrite exhibits a non-homogeneous distribution of carbon atoms in arrangements with specific compositions, i.e. Cottrell atmospheres, carbon clusters, and carbides, in most cases with a size of a few nanometers. The ferrite volume within a single platelet that is free of these carbon-enriched regions is extremely small. Proximity histograms can be compromised on the ferrite side, and a great deal of care should be taken to estimate the carbon contentmore » in regions of bainitic ferrite free from carbon agglomeration. For this purpose, APT measurements were first validated for the ferritic phase in a pearlitic sample and further performed for the bainitic ferrite matrix in high-silicon steels isothermally transformed between 200 °C and 350 °C. Additionally, results were compared with the carbon concentration values derived from X-ray diffraction (XRD) analyses considering a tetragonal lattice and previous APT studies. In conclusion, the present results reveal a strong disagreement between the carbon content values in the bainitic ferrite matrix as obtained by APT and those derived from XRD measurements. Those differences have been attributed to the development of carbon-clustered regions with an increased tetragonality in a carbon-depleted matrix.« less

  3. Carbon concentration measurements by atom probe tomography in the ferritic phase of high-silicon steels

    SciTech Connect

    Rementeria, Rosalia; Poplawsky, Jonathan D.; Aranda, Maria M.; Guo, Wei; Jimenez, Jose A.; Garcia-Mateo, Carlos; Caballero, Francisca G.

    2016-12-19

    Current studies using atom probe tomography (APT) show that bainitic ferrite formed at low temperature contains more carbon than what is consistent with the paraequilibrium phase diagram. However, nanocrystalline bainitic ferrite exhibits a non-homogeneous distribution of carbon atoms in arrangements with specific compositions, i.e. Cottrell atmospheres, carbon clusters, and carbides, in most cases with a size of a few nanometers. The ferrite volume within a single platelet that is free of these carbon-enriched regions is extremely small. Proximity histograms can be compromised on the ferrite side, and a great deal of care should be taken to estimate the carbon content in regions of bainitic ferrite free from carbon agglomeration. For this purpose, APT measurements were first validated for the ferritic phase in a pearlitic sample and further performed for the bainitic ferrite matrix in high-silicon steels isothermally transformed between 200 °C and 350 °C. Additionally, results were compared with the carbon concentration values derived from X-ray diffraction (XRD) analyses considering a tetragonal lattice and previous APT studies. In conclusion, the present results reveal a strong disagreement between the carbon content values in the bainitic ferrite matrix as obtained by APT and those derived from XRD measurements. Those differences have been attributed to the development of carbon-clustered regions with an increased tetragonality in a carbon-depleted matrix.

  4. Dielectric barrier discharge carbon atomic emission spectrometer: universal GC detector for volatile carbon-containing compounds.

    PubMed

    Han, Bingjun; Jiang, Xiaoming; Hou, Xiandeng; Zheng, Chengbin

    2014-01-07

    It was found that carbon atomic emission can be excited in low temperature dielectric barrier discharge (DBD), and an atmospheric pressure, low power consumption, and compact microplasma carbon atomic emission spectrometer (AES) was constructed and used as a universal and sensitive gas chromatographic (GC) detector for detection of volatile carbon-containing compounds. A concentric DBD device was housed in a heating box to increase the plasma operation temperature to 300 °C to intensify carbon atomic emission at 193.0 nm. Carbon-containing compounds directly injected or eluted from GC can be decomposed, atomized, and excited in this heated DBD for carbon atomic emission. The performance of this new optical detector was first evaluated by determination of a series of volatile carbon-containing compounds including formaldehyde, ethyl acetate, methanol, ethanol, 1-propanol, 1-butanol, and 1-pentanol, and absolute limits of detection (LODs) were found at a range of 0.12-0.28 ng under the optimized conditions. Preliminary experimental results showed that it provided slightly higher LODs than those obtained by GC with a flame ionization detector (FID). Furthermore, it is a new universal GC detector for volatile carbon-containing compounds that even includes those compounds which are difficult to detect by FID, such as HCHO, CO, and CO2. Meanwhile, hydrogen gas used in conventional techniques was eliminated; and molecular optical emission detection can also be performed with this GC detector for multichannel analysis to improve resolution of overlapped chromatographic peaks of complex mixtures.

  5. Bias in bonding behavior among boron, carbon, and nitrogen atoms in ion implanted a-BN, a-BC, and diamond like carbon films

    SciTech Connect

    Genisel, Mustafa Fatih; Uddin, Md. Nizam; Say, Zafer; Bengu, Erman; Kulakci, Mustafa; Turan, Rasit; Gulseren, Oguz

    2011-10-01

    In this study, we implanted N{sup +} and N{sub 2}{sup +} ions into sputter deposited amorphous boron carbide (a-BC) and diamond like carbon (DLC) thin films in an effort to understand the chemical bonding involved and investigate possible phase separation routes in boron carbon nitride (BCN) films. In addition, we investigated the effect of implanted C{sup +} ions in sputter deposited amorphous boron nitride (a-BN) films. Implanted ion energies for all ion species were set at 40 KeV. Implanted films were then analyzed using x-ray photoelectron spectroscopy (XPS). The changes in the chemical composition and bonding chemistry due to ion-implantation were examined at different depths of the films using sequential ion-beam etching and high resolution XPS analysis cycles. A comparative analysis has been made with the results from sputter deposited BCN films suggesting that implanted nitrogen and carbon atoms behaved very similar to nitrogen and carbon atoms in sputter deposited BCN films. We found that implanted nitrogen atoms would prefer bonding to carbon atoms in the films only if there is no boron atom in the vicinity or after all available boron atoms have been saturated with nitrogen. Implanted carbon atoms also preferred to either bond with available boron atoms or, more likely bonded with other implanted carbon atoms. These results were also supported by ab-initio density functional theory calculations which indicated that carbon-carbon bonds were energetically preferable to carbon-boron and carbon-nitrogen bonds.

  6. Abundance of atomic carbon /C I/ in dense interstellar clouds

    NASA Technical Reports Server (NTRS)

    Phillips, T. G.; Huggins, P. J.

    1981-01-01

    The abundance of interstellar neutral atomic carbon is investigated by means of its ground state fine-structure line emission at 492 GHz using the 91.5 cm telescope of NASAs Kuiper Airborne Observatory. Atomic carbon is found to be very abundant in dense interstellar molecular clouds with column densities of about 10 to the 19th per sq cm. Because the observations have considerably greater column densities than current theories of carbon chemistry, it is suggested that the physical conditions of these clouds are not as simple as assumed in the models. Various situations are discussed which would lead to large C I abundances, including the possibility that the chemical lifetimes of the clouds are relatively short.

  7. Integrated atom detector based on field ionization near carbon nanotubes

    SciTech Connect

    Gruener, B.; Jag, M.; Stibor, A.; Visanescu, G.; Haeffner, M.; Kern, D.; Guenther, A.; Fortagh, J.

    2009-12-15

    We demonstrate an atom detector based on field ionization and subsequent ion counting. We make use of field enhancement near tips of carbon nanotubes to reach extreme electrostatic field values of up to 9x10{sup 9} V/m, which ionize ground-state rubidium atoms. The detector is based on a carpet of multiwall carbon nanotubes grown on a substrate and used for field ionization, and a channel electron multiplier used for ion counting. We measure the field enhancement at the tips of carbon nanotubes by field emission of electrons. We demonstrate the operation of the field ionization detector by counting atoms from a thermal beam of a rubidium dispenser source. By measuring the ionization rate of rubidium as a function of the applied detector voltage we identify the field ionization distance, which is below a few tens of nanometers in front of nanotube tips. We deduce from the experimental data that field ionization of rubidium near nanotube tips takes place on a time scale faster than 10{sup -10} s. This property is particularly interesting for the development of fast atom detectors suitable for measuring correlations in ultracold quantum gases. We also describe an application of the detector as partial pressure gauge.

  8. Dynamics of carbon-hydrogen and carbon-methyl exchanges in the collision of 3P atomic carbon with propene

    NASA Astrophysics Data System (ADS)

    Lee, Shih-Huang; Chen, Wei-Kan; Chin, Chih-Hao; Huang, Wen-Jian

    2013-11-01

    We investigated the dynamics of the reaction of 3P atomic carbon with propene (C3H6) at reactant collision energy 3.8 kcal mol-1 in a crossed molecular-beam apparatus using synchrotron vacuum-ultraviolet ionization. Products C4H5, C4H4, C3H3, and CH3 were observed and attributed to exit channels C4H5 + H, C4H4 + 2H, and C3H3 + CH3; their translational-energy distributions and angular distributions were derived from the measurements of product time-of-flight spectra. Following the addition of a 3P carbon atom to the C=C bond of propene, cyclic complex c-H2C(C)CHCH3 undergoes two separate stereoisomerization mechanisms to form intermediates E- and Z-H2CCCHCH3. Both the isomers of H2CCCHCH3 in turns decompose to C4H5 + H and C3H3 + CH3. A portion of C4H5 that has enough internal energy further decomposes to C4H4 + H. The three exit channels C4H5 + H, C4H4 + 2H, and C3H3 + CH3 have average translational energy releases 13.5, 3.2, and 15.2 kcal mol-1, respectively, corresponding to fractions 0.26, 0.41, and 0.26 of available energy deposited to the translational degrees of freedom. The H-loss and 2H-loss channels have nearly isotropic angular distributions with a slight preference at the forward direction particularly for the 2H-loss channel. In contrast, the CH3-loss channel has a forward and backward peaked angular distribution with an enhancement at the forward direction. Comparisons with reactions of 3P carbon atoms with ethene, vinyl fluoride, and vinyl chloride are stated.

  9. Single-shell carbon nanotubes imaged by atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Höper, Ralf; Workman, Richard K.; Chen, Dong; Sarid, Dror; Yadav, Tapesh; Withers, James C.; Loutfy, Raouf O.

    1994-05-01

    Single-shell carbon nanotubes, approximately 1 nm in diameter, have been imaged for the first time by atomic force microscopy operating in both the contact and tapping modes. For the contact mode, the height of the imaged nanotubes has been calibrated using the atomic steps of the silicon substrate on which the nanotubes were deposited. For the tapping mode, the calibration was performed using an industry-standard grating. The paper discusses substrate and sample preparation methods for the characterization by scanning probe microscopy of nanotubes deposited on a substrate.

  10. Ab initio quantum transport in atomic carbon chains

    NASA Astrophysics Data System (ADS)

    Botello-Méndez, Andrés R.; Charlier, Jean-Christophe; Banhart, Florian; NAPS Team; Carbyne Collaboration

    2015-03-01

    Carbyne, the sp-hybridized phase of carbon, is still a missing link in the family of carbon allotropes. Recently, detailed electrical measurements and first-principles electronic transport calculations have been performed on monoatomic carbon chains. When the 1D system is under strain, the current-voltage curves exhibit a semiconducting behavior, which corresponds to the polyyne structure of the atomic chain with alternating single and triple bonds. Conversely, when the chain is unstrained, the ohmic behavior is observed in agreement with the metallic cumulene structure with double bonds, confirming recent theoretical predictions, namely that a metal-insulator transition can be induced by adjusting the strain. The key role of the contacting leads is also scrutinized by ab initio quantum conductance calculations, explaining the rectifying behavior measured in monoatomic carbon chains in a non-symmetric contact configuration.

  11. Energy of the Isolated Metastable Iron-Nickel FCC Nanocluster with a Carbon Atom in the Tetragonal Interstice

    NASA Astrophysics Data System (ADS)

    Bondarenko, Natalya V.; Nedolya, Anatoliy V.

    2017-02-01

    The energy of the isolated iron-nickel nanocluster was calculated by molecular mechanics method using Lennard-Jones potential. The cluster included a carbon atom that drifted from an inside octahedral interstice to a tetrahedral interstice in direction and after that in <222> direction to the surface. In addition, one of 14 iron atoms was replaced by a nickel atom, the position of which was changing during simulation.

  12. Study of the structure of steel 12Kh12M1BFP modified with additions of fullerenes and carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Glebov, V. A.; Bakulina, A. S.; Efremov, I. V.; Shchetinin, I. V.; Yagodkin, Yu. D.; Glezer, A. M.; Rashkovskii, A. Yu.; Vainshtein, D. L.

    2010-12-01

    X-ray structural analysis, scanning electron microscopy, x-ray photoelectron spectroscopy, atomic force microscopy are used to study the structure of compacted specimens of steel 12Kh12M1BFP, modified with additions of fullerenes and carbon nanotubes. The effect of additions on the microhardness of compacted specimens is established.

  13. Carbon nanotube forests growth using catalysts from atomic layer deposition

    SciTech Connect

    Chen, Bingan; Zhang, Can; Esconjauregui, Santiago; Xie, Rongsi; Zhong, Guofang; Robertson, John; Bhardwaj, Sunil; Cepek, Cinzia

    2014-04-14

    We have grown carbon nanotubes using Fe and Ni catalyst films deposited by atomic layer deposition. Both metals lead to catalytically active nanoparticles for growing vertically aligned nanotube forests or carbon fibres, depending on the growth conditions and whether the substrate is alumina or silica. The resulting nanotubes have narrow diameter and wall number distributions that are as narrow as those grown from sputtered catalysts. The state of the catalyst is studied by in-situ and ex-situ X-ray photoemission spectroscopy. We demonstrate multi-directional nanotube growth on a porous alumina foam coated with Fe prepared by atomic layer deposition. This deposition technique can be useful for nanotube applications in microelectronics, filter technology, and energy storage.

  14. Carbon fiber CVD coating by carbon nanostructured for space materials protection against atomic oxygen

    NASA Astrophysics Data System (ADS)

    Pastore, Roberto; Bueno Morles, Ramon; Micheli, Davide

    2016-07-01

    adhesion and durability in the environment. Though these coatings are efficient in protecting polymer composites, their application imposes severe constraints. Their thermal expansion coefficients may differ markedly from those of polymer composite substrates: as a result, cracks develop in the coatings on thermal cycling and AO can penetrate through them to the substrate. In addition to the technicalities of forming an effective barrier, such factors as cost, convenience of application and ease of repair are important considerations in the selection of a coating for a particular application. The latter issues drive the aerospace research toward the development of novel light composite materials, like the so called polymer nanocomposites, which are materials with a polymer matrix and a filler with at least one dimension less than 100 nanometers. Current interest in nanocomposites has been generated and maintained because nanoparticle-filled polymers exhibit unique combinations of properties not achievable with traditional composites. These combinations of properties can be achieved because of the small size of the fillers, the large surface area the fillers provide, and in many cases the unique properties of the fillers themselves. In particular, the carbon fiber-based polymeric composite materials are the basic point of interest: the aim of the present study is to find new solution to produce carbon fiber-based composites with even more upgraded performances. One intriguing strategy to tackle such an issue has been picked out in the coupling between the carbon fibers and the carbon nanostructures. That for two main reasons: first, carbon nanostructures have shown fancy potentialities for any kind of technological applications since their discovery, second, the chemical affinity between fiber and nanostructure (made of the same element) should be a likely route to approach the typical problems due to thermo-mechanical compatibility. This work is joined in such framework

  15. Probing the improbable: imaging carbon atoms in alumina

    SciTech Connect

    Marquis, E A; Yahia, Noor; Larson, David J.; Miller, Michael K; Todd, Richard

    2010-01-01

    Atom-probe tomography has proven very powerful to analyze the detailed structure and chemistry of metallic alloys and semiconductor structures while ceramic materials have remained outside its standard purview. In the current work, we demonstrate that bulk alumina can be quantitatively analyzed and microstructural features observed. The analysis of grain boundary carbon segregation - barely achievable by electron microscopy - opens the possibility of understanding the mechanistic effects of dopants on mechanical properties, fracture and wear properties of bulk oxides.

  16. Stability of conductance oscillations in carbon atomic chains

    NASA Astrophysics Data System (ADS)

    Yu, Jing-Xin; Hou, Zhi-Wei; Liu, Xiu-Ying

    2015-06-01

    The conductance stabilities of carbon atomic chains (CACs) with different lengths are investigated by performing theoretical calculations using the nonequilibrium Green’s function method combined with density functional theory. Regular even-odd conductance oscillation is observed as a function of the wire length. This oscillation is influenced delicately by changes in the end carbon or sulfur atoms as well as variations in coupling strength between the chain and leads. The lowest unoccupied molecular orbital in odd-numbered chains is the main transmission channel, whereas the conductance remains relatively small for even-numbered chains and a significant drift in the highest occupied molecular orbital resonance toward higher energies is observed as the number of carbon atoms increases. The amplitude of the conductance oscillation is predicted to be relatively stable based on a thiol joint between the chain and leads. Results show that the current-voltage evolution of CACs can be affected by the chain length. The differential and second derivatives of the conductance are also provided. Project supported by the National Natural Science Foundation of China (Grant Nos. 11304079, 11404094, and 51201059), the Priority Scientific and Technological Project of Henan Province, China (Grant No. 14A140027), the School Fund (Grant No. 2012BS055), and the Plan of Natural Science Fundamental Research of Henan University of Technology, China (Grant No. 2014JCYJ15).

  17. Carbon Nanotube Atomic Force Microscopy for Proteomics and Biological Forensics

    SciTech Connect

    Noy, A; De Yoreo, J J; Malkin, A J

    2002-01-01

    The Human Genome Project was focused on mapping the complete genome. Yet, understanding the structure and function of the proteins expressed by the genome is the real end game. But there are approximately 100,000 proteins in the human body and the atomic structure has been determined for less than 1% of them. Given the current rate at which structures are being solved, it will take more than one hundred years to complete this task. The rate-limiting step in protein structure determination is the growth of high-quality single crystals for X-ray diffraction. Synthesis of the protein stock solution as well as X-ray diffraction and analysis can now often be done in a matter of weeks, but developing a recipe for crystallization can take years and, especially in the case of membrane proteins, is often completely unsuccessful. Consequently, techniques that can either help to elucidate the factors controlling macromolecular crystallization, increase the amount of structural information obtained from crystallized macromolecules or eliminate the need for crystallization altogether are of enormous importance. In addition, potential applications for those techniques extend well beyond the challenges of proteomics. The global spread of modern technology has brought with it an increasing threat from biological agents such as viruses. As a result, developing techniques for identifying and understanding the operation of such agents is becoming a major area of forensic research for DOE. Previous to this project, we have shown that we can use in situ atomic force microscopy (AFM) to image the surfaces of growing macromolecular crystals with molecular resolution (1-5) In addition to providing unprecedented information about macromolecular nucleation, growth and defect structure, these results allowed us to obtain low-resolution phase information for a number of macromolecules, providing structural information that was not obtainable from X-ray diffraction(3). For some virus systems

  18. Voronoi analysis of the short–range atomic structure in iron and iron–carbon melts

    SciTech Connect

    Sobolev, Andrey; Mirzoev, Alexander

    2015-08-17

    In this work, we simulated the atomic structure of liquid iron and iron–carbon alloys by means of ab initio molecular dynamics. Voronoi analysis was used to highlight changes in the close environments of Fe atoms as carbon concentration in the melt increases. We have found, that even high concentrations of carbon do not affect short–range atomic order of iron atoms — it remains effectively the same as in pure iron melts.

  19. Carbon Nanotube Chopped Fiber for Enhanced Properties in Additive Manufacturing

    SciTech Connect

    Menchhofer, Paul A.; Johnson, Joseph E.; Lindahl, John M.

    2016-06-06

    Nanocomp Technologies, Inc. is working with Oak Ridge National Laboratory to develop carbon nanotube (CNT) composite materials and evaluate their use in additive manufacturing (3D printing). The first phase demonstrated feasibility and improvements for carbon nanotube (CNT)- acrylonitrile butadiene styrene (ABS) composite filaments use in additive manufacturing, with potential future work centering on further improvements. By focusing the initial phase on standard processing methods (developed mainly for the incorporation of carbon fibers in ABS) and characterization techniques, a basis of knowledge for the incorporation of CNTs in ABS was learned. The ability to understand the various processing variables is critical to the successful development of these composites. From the degradation effects on ABS (caused by excessive temperatures), to the length of time the ABS is in the melt state, to the order of addition of constituents, and also to the many possible mixing approaches, a workable flow sequence that addresses each processing step is critical to the final material properties. Although this initial phase could not deal with each of these variables in-depth, a future study is recommended that will build on the lessons learned for this effort.

  20. Tribological Properties of Carbon Nanocapsule Particles as Lubricant Additive.

    PubMed

    Jeng, Yeau-Ren; Huang, Yao-Huei; Tsai, Ping-Chi; Hwang, Gan-Lin

    2014-10-01

    An experimental investigation is performed into the tribological properties of mineral oil lubricants containing carbon nanocapsules (CNCs) additives with various concentrations (wt.%). Friction characteristics and wear behaviors at contact interfaces are examined by the block-on-ring tests, high-resolution transmission electron microscopy (HRTEM), and mapping (MAP) analysis. The results suggest that the addition of CNCs to the mineral oil yields an effective reduction in the friction coefficient at the contact interface. Molecular dynamics (MD) simulations clarify the lubrication mechanism of CNCs at the sliding system, indicating the tribological properties are essentially sensitive to the structural evolutions of CNCs.

  1. Theoretical realization of cluster-assembled hydrogen storage materials based on terminated carbon atomic chains.

    PubMed

    Liu, Chun-Sheng; An, Hui; Guo, Ling-Ju; Zeng, Zhi; Ju, Xin

    2011-01-14

    The capacity of carbon atomic chains with different terminations for hydrogen storage is studied using first-principles density functional theory calculations. Unlike the physisorption of H(2) on the H-terminated chain, we show that two Li (Na) atoms each capping one end of the odd- or even-numbered carbon chain can hold ten H(2) molecules with optimal binding energies for room temperature storage. The hybridization of the Li 2p states with the H(2)σ orbitals contributes to the H(2) adsorption. However, the binding mechanism of the H(2) molecules on Na arises only from the polarization interaction between the charged Na atom and the H(2). Interestingly, additional H(2) molecules can be bound to the carbon atoms at the chain ends due to the charge transfer between Li 2s2p (Na 3s) and C 2p states. More importantly, dimerization of these isolated metal-capped chains does not affect the hydrogen binding energy significantly. In addition, a single chain can be stabilized effectively by the C(60) fullerenes termination. With a hydrogen uptake of ∼10 wt.% on Li-coated C(60)-C(n)-C(60) (n = 5, 8), the Li(12)C(60)-C(n)-Li(12)C(60) complex, keeping the number of adsorbed H(2) molecules per Li and stabilizing the dispersion of individual Li atoms, can serve as better building blocks of polymers than the (Li(12)C(60))(2) dimer. These findings suggest a new route to design cluster-assembled hydrogen storage materials based on terminated sp carbon chains.

  2. Ecotoxicological effects of activated carbon addition to sediments.

    PubMed

    Jonker, Michiel T O; Suijkerbuijk, Martin P W; Schmitt, Heike; Sinnige, Theo L

    2009-08-01

    Activated carbon (AC) addition is a recently developed technique for the remediation of sediments and soils contaminated with hydrophobic organic chemicals. Laboratory and field experiments have demonstrated that the addition of 3-4% of AC can reduce aqueous concentrations and the bioaccumulation potential of contaminants. However, one aspect of the technique that has hardly received any attention is the possible occurrence of secondary, eco(toxico)logical effects, i.e., effects of AC addition on the health, behavior, and habitat quality of local organisms. In the present study, several ecotoxicological effects were investigated in AC-water and AC-enriched (0-25%) sediment systems. It was demonstrated that (i) powdered activated carbons can be toxic to aquatic invertebrates (Lumbriculus variegatus, Daphnia magna, and Corophium volutator) based on different mechanisms and preferably should be washed prior to application; (ii) Asellus aquaticus and Corophium volutator may physically avoid AC-enriched sediments; (iii) exposure of Lumbriculus variegatus to AC-enriched sediments lead to a time and dose-dependent reduction in the worms' lipid content, which was most probably caused by the observation that (iv) worm egestion rates decreased drastically upon AC addition, indicating that the presence of AC disturbed feeding behavior; and (v) there were no obvious effects on the microbiological community structure. All in all, these results suggest potential ecotoxicological effects of powdered AC addition and stress the need for a detailed further investigation of secondary effects of the technique, prior to any large-scale field application.

  3. Diamond like carbon coatings: Categorization by atomic number density

    NASA Technical Reports Server (NTRS)

    Angus, John C.

    1986-01-01

    Dense diamond-like hydrocarbon films grown at the NASA Lewis Research Center by radio frequency self bias discharge and by direct ion beam deposition were studied. A new method for categorizing hydrocarbons based on their atomic number density and elemental composition was developed and applied to the diamond-like hydrocarbon films. It was shown that the diamond-like hydrocarbon films are an entirely new class of hydrocarbons with atomic number densities lying between those of single crystal diamond and adamantanes. In addition, a major review article on these new materials was completed in cooperation with NASA Lewis Research Center personnel.

  4. Atomic-focuser imaging in electron nanodiffraction from carbon nanoshells

    PubMed

    Cowley

    2000-03-01

    When nanodiffraction patterns are obtained by transmission through the top and bottom walls of near-spherical, hollow carbon nano-shells, using the focused probe of a STEM instrument, a graphitic crystal in one wall may act as an atomic focuser to produce high-resolution images of small regions of the other wall within the central beam and the diffraction disks of the nanodiffraction pattern. A theoretical analysis of the imaging process is given. Images showing one- and two-dimensional periodicities, with fringe spacings as small as 0.124 nm, and also images showing non-periodic features have been obtained from carbon nanoshells having diameters of the order of 100 nm.

  5. An important atomic process in the CVD growth of graphene: Sinking and up-floating of carbon atom on copper surface

    NASA Astrophysics Data System (ADS)

    Li, Yingfeng; Li, Meicheng; Gu, TianSheng; Bai, Fan; Yu, Yue; Trevor, Mwenya; Yu, Yangxin

    2013-11-01

    By density functional theory (DFT) calculations, the early stages of the growth of graphene on copper (1 1 1) surface are investigated. At the very first time of graphene growth, the carbon atom sinks into subsurface. As more carbon atoms are adsorbed nearby the site, the sunken carbon atom will spontaneously form a dimer with one of the newly adsorbed carbon atoms, and the formed dimer will up-float on the top of the surface. We emphasize the role of the co-operative relaxation of the co-adsorbed carbon atoms in facilitating the sinking and up-floating of carbon atoms. In detail: when two carbon atoms are co-adsorbed, their co-operative relaxation will result in different carbon-copper interactions for the co-adsorbed carbon atoms. This difference facilitates the sinking of a single carbon atom into the subsurface. As a third carbon atom is co-adsorbed nearby, it draws the sunken carbon atom on top of the surface, forming a dimer. Co-operative relaxations of the surface involving all adsorbed carbon atoms and their copper neighbors facilitate these sinking and up-floating processes. This investigation is helpful for the deeper understanding of graphene synthesis and the choosing of optimal carbon sources or process.

  6. Carbon atom adsorption on and diffusion into Fe(110) and Fe(100) from first principles

    NASA Astrophysics Data System (ADS)

    Jiang, D. E.; Carter, Emily A.

    2005-01-01

    We employ spin-polarized periodic density functional theory (DFT) to examine carbon atom adsorption on, absorption in, and diffusion into Fe(110) and Fe(100). We find that carbon atoms bind strongly with Fe surfaces and prefer high coordination sites. The carbon atom is predicted to adsorb on the long-bridge site on Fe(110) and the fourfold hollow site on Fe(100). Due to the very short distance between the carbon atom and the subsurface Fe atom of Fe(100), the carbon atom binds more strongly with Fe(100) than with Fe(110). In the subsurface region, the carbon atom prefers the octahedral site, as in bulk Fe. We find that the carbon atom is more stable in the subsurface octahedral site of Fe(110) than that of Fe(100), since the strain caused by the interstitial carbon atom is released by pushing one surface Fe atom towards vacuum by 0.5 Å in Fe(110), while the distortion in Fe(100) propagates far into the lattice. Diffusion of carbon atoms into Fe(110) and Fe(100) subsurfaces goes through transition states where the carbon atom is coordinated to four Fe atoms. The barriers to diffusion into Fe(110) and Fe(100) are 1.18 eV and 1.47 eV, respectively. The larger diffusion barrier into Fe(100) is mainly due to the stronger bonding between carbon and the Fe(100) surface. We predict that the rate-limiting step for C incorporation into bulk Fe is the initial diffusion to subsurface sites, while the rate-limiting step for absorbed carbon segregation to the surface is bulk diffusion, with no expected difference between rates to segregate to different surfaces. Lastly, we predict that graphite formation will be more favorable on C -covered Fe(110) than C -covered Fe(100).

  7. Reactions of atomic carbon with oxygenated compounds and the investigation of fullerene chemistry

    SciTech Connect

    Chang, Tsongming.

    1993-01-01

    The reaction of atomic carbon with oxygenated organics produces CO and an energetic fragment. Reactions involving deoxygenation of carbonyl compounds to carbenes, epoxides to alkenes, and ethers to a pair of radicals have been investigated. Carbon atom deoxygenation of cyclopentanone and cylcopentene oxide give the cleavage products, ethylene and allene, along with cyclopentene. The use of 2,2,5,5-d[sub 4]-cyclopentanone as the substrate reveals the direct cleavage of cyclopentanylidene carbene is occurring. A calculation of the energetics of this reaction at the MP4/6-31G[sup *]//6-31G[sup *] level suggests a nonconcerted cleavage via a biradical intermediate. Carbon atoms deoxygenate cyclohexene. Inert gas deactivated energetic cyclohexene. The deoxygenation of other oxygenated compounds by atomic carbon, such as 7-oxabicyclo[2.2.1]heptane to cyclohexane-1,4-diyl biradical, 1,2-epoxy-5-hexane to energetic 1,S-hexadiene, allyl ether to allyl radicals, and [gamma]-butyrolactone to trimethylene-1,3-diyl biradical have also been carried out. Methylketene was deoxygenated to vinylidene carbene which rearranges to propyne via a 1,2-H shift. Dimethylketene was deoxygenated to dimethylethylidene carbene which gives 2-butyne via a 1,2-methyl shift and 1,3-butadiene via a vicinal C-H bond insertion. The addition of hydrogen donors to systems in which C[sub 60] is generated results in the formation of polycyclic aromatic hydrocarbons whose carbon skeleton might represent intermediates in fullerene formation. Based on this result, the author proposed a mechanism of fullerene formation. The use of various amounts of propene as a trap showed that the yield of fullerenes decreases as the amount of the trapped product increases. Attempts to trap intermediates in fullerene formation using halides and metals have been studied. The author has attempted metal encapsulation reactions and investigated some possible chemical reactions of fullerenes.

  8. A first-principle study of one-dimensional carbon atomic chain inserted single-wall carbon nanotubes.

    PubMed

    Mao, Yuliang; Zhong, JianXin; Yuan, JianMei; Zhao, Xinluo; Ando, Yoshinori

    2006-05-01

    Using first principles calculations, we investigate the atomic and electronic structure of carbon nanowires (CNWs) as the carbon chain inserted into single wall carbon nanotubes (SWCNTs). It indicates that the (5,5) CNW system exhibits metallic character, however, the insertion of carbon chain can transit a semi-conducting (9,0) SWCNT into a metallic.

  9. Atomic layer confined vacancies for atomic-level insights into carbon dioxide electroreduction

    PubMed Central

    Gao, Shan; Sun, Zhongti; Liu, Wei; Jiao, Xingchen; Zu, Xiaolong; Hu, Qitao; Sun, Yongfu; Yao, Tao; Zhang, Wenhua; Wei, Shiqiang; Xie, Yi

    2017-01-01

    The role of oxygen vacancies in carbon dioxide electroreduction remains somewhat unclear. Here we construct a model of oxygen vacancies confined in atomic layer, taking the synthetic oxygen-deficient cobalt oxide single-unit-cell layers as an example. Density functional theory calculations demonstrate the main defect is the oxygen(II) vacancy, while X-ray absorption fine structure spectroscopy reveals their distinct oxygen vacancy concentrations. Proton transfer is theoretically/experimentally demonstrated to be a rate-limiting step, while energy calculations unveil that the presence of oxygen(II) vacancies lower the rate-limiting activation barrier from 0.51 to 0.40 eV via stabilizing the formate anion radical intermediate, confirmed by the lowered onset potential from 0.81 to 0.78 V and decreased Tafel slope from 48 to 37 mV dec−1. Hence, vacancy-rich cobalt oxide single-unit-cell layers exhibit current densities of 2.7 mA cm−2 with ca. 85% formate selectivity during 40-h tests. This work establishes a clear atomic-level correlation between oxygen vacancies and carbon dioxide electroreduction. PMID:28220847

  10. Atomic layer confined vacancies for atomic-level insights into carbon dioxide electroreduction

    NASA Astrophysics Data System (ADS)

    Gao, Shan; Sun, Zhongti; Liu, Wei; Jiao, Xingchen; Zu, Xiaolong; Hu, Qitao; Sun, Yongfu; Yao, Tao; Zhang, Wenhua; Wei, Shiqiang; Xie, Yi

    2017-02-01

    The role of oxygen vacancies in carbon dioxide electroreduction remains somewhat unclear. Here we construct a model of oxygen vacancies confined in atomic layer, taking the synthetic oxygen-deficient cobalt oxide single-unit-cell layers as an example. Density functional theory calculations demonstrate the main defect is the oxygen(II) vacancy, while X-ray absorption fine structure spectroscopy reveals their distinct oxygen vacancy concentrations. Proton transfer is theoretically/experimentally demonstrated to be a rate-limiting step, while energy calculations unveil that the presence of oxygen(II) vacancies lower the rate-limiting activation barrier from 0.51 to 0.40 eV via stabilizing the formate anion radical intermediate, confirmed by the lowered onset potential from 0.81 to 0.78 V and decreased Tafel slope from 48 to 37 mV dec-1. Hence, vacancy-rich cobalt oxide single-unit-cell layers exhibit current densities of 2.7 mA cm-2 with ca. 85% formate selectivity during 40-h tests. This work establishes a clear atomic-level correlation between oxygen vacancies and carbon dioxide electroreduction.

  11. First principles study of foreign interstitial atom (carbon, nitrogen) interactions with intrinsic defects in tungsten

    NASA Astrophysics Data System (ADS)

    Kong, Xiang-Shan; You, Yu-Wei; Song, Chi; Fang, Q. F.; Chen, Jun-Ling; Luo, G.-N.; Liu, C. S.

    2012-11-01

    center, as presented in Fig. 2. The differential charge density is defined as the difference between the charge density of the interstitial-containing tungsten system and the superposition densities of tungsten host and the free interstitial. In Fig. 2, there are significant charge accumulations around the FIA and depletions on tungsten. This shows that the FIA not only attracts electrons from metals, but also induces electron redistribution nearby. The charge depletion on tungsten atoms around FIA leads to the weakening of the W-W bond, which in turn results in the decrease of vacancy formation energy. The charge transfer between the FIA and its nearest-neighbors is more significant for nitrogen than for carbon. This explains why nitrogen reduces the vacancy formation energy much more than carbon. To give a further confirmation, we list the charges of neighbor tungsten atoms from bader charge analysis [35,36] in Table 3. The bader charge analysis uses as sole input the charge density and considers the zero-flux surfaces as the borders between different atoms. Using these borders to define the volume related to each atom, the charge of each atom is obtained by integrating the density over this volume. Here, the bader charge is calculated using a grid based on the algorithm developed by Henkelman et al. [35,36] As can be seen, the charges of tungsten atoms nearest-neighbor to nitrogen are more positive than that to carbon. In addition, as shown in Fig. 2, for carbon, the charge transfer is only clearly visible between the FIA and its 1nn, while for nitrogen, both the 1nn and 2nn contribute remarkably. This implies that the influence range is larger for a nitrogen atom than for a carbon atom.Besides the charge differences, the partial density of states for FIA (p-DOS) and its 1nn and 2nn tungsten atoms (d-DOS) are shown in Fig. 3. The depletion in the tungsten 5d states of the density of states is observed compared to that of pure bcc tungsten. There is a hybridization

  12. Atom-probe tomography of tribological boundary films resulting from boron-based oil additives

    SciTech Connect

    Kim, Yoon-Jun; Baik, Sung-Il; Bertolucci-Coelho, Leonardo; Mazzaferro, Lucca; Ramirez, Giovanni; Erdemir, Ali; Seidman, D K

    2016-01-15

    Correlative characterization using atom-probe tomography (APT) and transmission electron microscopy (TEM) was performed on a tribofilm formed during sliding frictional testing with a fully formulated engine oil, which also contains a boron-based additive. The tribofilm formed is ~15 nm thick and consists of oxides of iron and compounds of B, Ca, P, and S, which are present in the additive. This study provides strong evidence for boron being embedded in the tribofilm, which effectively reduces friction and wear losses.

  13. Optimization of antioxidant additives in carbon-containing castables

    NASA Astrophysics Data System (ADS)

    He, Huiqing

    Oxidation of carbon is a major drawback for oxide-carbon composite refractories, especially for a castable which is inherently more porous than a brick. Magnesia-based material system hold a potential to be used in slag line of steelmaking ladles due to their high corrosion resistance to basic slag and are chosen as the material of study in this thesis. Overcoming the difficulties of introducing flake graphite into such castables and of protecting it from oxidation have constituted the principal goals of this work. The results have demonstrated that important factors to minimize oxidation of carbon-containing castables are the nature of carbon source, the antioxidants and the densification of the materials. In this thesis it has been shown that: 1. The mode of incorporating flake graphite into castables plays a decisive role in developing graphite containing castables. Modified flake graphite pellets by extruding (EG) and coating (CG) efficiently reduce water addition and pore size, increasing bulk density, CMOR, thermal shock parameter and oxidation resistance of the castables. 2. Packaging natural flake graphite by incorporating antioxidants and oxide fillers into extruded graphite pellets sufficiently improve densification, pore size distribution, new compound formations and oxidation resistance of the pellets. The best EG pellets for the MgO-MA-C system contains 80% graphite, 15% Al2O3 and 5% B4C or 80% graphite, 15%Al and 5% B4C. The best EG pellets for the MgO-M2S-C system contains 80% graphite and 20% Si or 80% graphite and 20% SIC. 3. Specific antioxidants sufficiently improve oxidation resistance both locally in extruded graphite pellets and overall in the matrix of the castables. Based upon our findings it is more appropriate to use aluminium buried in EG pellets and a minimum amount into the castable matrix part. 4. The antioxidants not only protect graphite from oxidation but also improve the mechanical properties of the EG pellets and the castables

  14. Reduction of nitrate in aquifer microcosms by carbon additions

    USGS Publications Warehouse

    Obenhuber, Donald C.; Lowrance , Richard

    1991-01-01

    Aquifer microcosms were used to examine the effects of NO−3 and C amendments on groundwater from the Claiborne aquifer. Nitrate concentrations of 12.17 mg L−1 in aquifer microcosms were reduced 0.92%/d to 5.84 mg L−1 by the addition of 10 mg C L−1 for 35 d. Nitrate disappearance correlated with increases in number of denitrifiers and dissolved N2O concentration and decreases in dissolved oxygen, suggesting biological denitrification. Nitrate/chloride ratios decreased in microcosms with 10 mg C L−1 added and then increased when the C addition was removed. Carbon additions of 0.4 mg C L−1 had no effect on the microbial or chemical properties of the microcosms. Nitrous oxide levels in wells sampling the Claiborne aquifer showed an increase with depth, indicating N2O production within the aquifer. Microcosms are useful tools to examine biological transformations of chemical contaminants in unconsolidated aquifer material. The remediation of NO−3 contaminated aquifers by organic infusion is possible and appears to be a function of microbial denitrification.

  15. Atomic nanotube welders: boron interstitials triggering connections in double-walled carbon nanotubes.

    PubMed

    Endo, Morinobu; Muramatsu, Hiroyuki; Hayashi, Takuya; Kim, Yoong-Ahm; Van Lier, Gregory; Charlier, Jean-Christophe; Terrones, Humberto; Terrones, Mauricio; Dresselhaus, Mildred S

    2005-06-01

    Here we demonstrate that the incorporation of boron (B) atoms between double-walled carbon nanotubes (DWNTs) during thermal annealing (1400-1600 degrees C) results in covalent nanotube "Y" junctions, DWNT coalescence, and the formation of flattened multiwalled carbon nanotubes (MWNTs). These processes occur via the merging of adjacent tubes, which is triggered by B interstitial atoms. We observe that B atom interstitials between DWNTs are responsible for the rapid establishment of covalent connections between neighboring tubes (polymerization), thereby resulting in the fast annealing of the carbon cylinders with B atoms embedded in the newly created carbon nanotube network. Once B is in the lattice, tube faceting (polygonization) starts to occur, and the electronic properties are expected to change dramatically. Therefore, B atoms indeed act as atomic nanotube fusers (or welders), and this process could now be used in assembling novel electronic nanotube devices, nanotube networks, carbon nanofoams and heterojunctions exhibiting p-type electronic properties.

  16. Atomic-Scale Investigations of Multiwall Carbon Nanotube Growth

    NASA Astrophysics Data System (ADS)

    Behr, Michael John

    The combination of unique mechanical, thermal, optical, and electronic properties of carbon nanotubes (CNTs) make them a desirable material for use in a wide range of applications. Many of these unique properties are highly sensitive to how carbon atoms are arranged within the graphene nanotube wall. Precise structural control of this arrangement remains the key challenge of CNT growth to realizing their technological potential. Plasma-enhanced chemical vapor deposition (PECVD) from methane-hydrogen gas mixtures using catalytic nanoparticles enables large-scale growth of CNT films and controlled spatial placement of CNTs on a substrate, however, much is still unknown about what happens to the catalyst particle during growth, the atomistic mechanisms involved, and how these dictate the final nanotube structure. To investigate the fundamental processes of CNT growth by PECVD, a suite of characterization techniques were implemented, including attenuated total-reflection Fourier transform infrared spectroscopy (ATR-FTIR), optical emission spectroscopy (OES), Raman spectroscopy, convergent-beam electron diffraction (CBED), high-resolution transmission and scanning-transmission electron microscopy (TEM, STEM), energy dispersive x-ray spectroscopy, and electron energy-loss spectroscopy (EELS). It is found that hydrogen plays a critical role in determining the final CNT structure through controlling catalyst crystal phase and morphology. At low hydrogen concentrations in the plasma iron catalysts are converted to Fe3C, from which high-quality CNTs grow; however, catalyst particles remain as pure iron when hydrogen is in abundance, and produce highly defective CNTs with large diameters. The initially faceted and equiaxed catalyst nanocrystals become deformed and are elongated into a teardrop morphology once a tubular CNT structure is formed around the catalyst particles. Although catalyst particles are single crystalline, they exhibit combinations of small-angle (˜1°-3

  17. Improvement of capacitive performances of symmetric carbon/carbon supercapacitors by addition of nanostructured polypyrrole powder

    NASA Astrophysics Data System (ADS)

    Benhaddad, L.; Gamby, J.; Makhloufi, L.; Pailleret, A.; Pillier, F.; Takenouti, H.

    2016-03-01

    A nanostructured polypyrrole powder was synthesized in a previous work from the oxidation of pyrrole by a nanostructured MnO2 powder used simultaneously as an oxidizing agent and a sacrificial template in a redox heterogeneous mechanism. In this study, this original PPy powder was used as an active additive material with different ratio in carbon/carbon symmetrical supercapacitors whose performances were studied by cyclic voltammetry and electrochemical impedance spectroscopy (EIS) using a Swagelok-type cell. From the EIS spectra, the complex capacitance was extracted using a model involving two Cole-Cole type complex capacitances linked in series. The specific capacitance values evaluated by EIS and cyclic voltammetry are in a good agreement between them. The results show that the addition of nanostructured polypyrrole powder improves significantly the specific capacitance of the carbon electrode and consequently the performances of carbon/carbon supercapacitors. The original and versatile synthesis method used to produce this polypyrrole powder appears to be attractive for large scale production of promising additives for electrode materials of supercapacitors.

  18. Insights into the Electronic Structure of Ozone and Sulfur Dioxide from Generalized Valence Bond Theory: Addition of Hydrogen Atoms.

    PubMed

    Lindquist, Beth A; Takeshita, Tyler Y; Dunning, Thom H

    2016-05-05

    Ozone (O3) and sulfur dioxide (SO2) are valence isoelectronic species, yet their properties and reactivities differ dramatically. In particular, O3 is highly reactive, whereas SO2 is chemically relatively stable. In this paper, we investigate serial addition of hydrogen atoms to both the terminal atoms of O3 and SO2 and to the central atom of these species. It is well-known that the terminal atoms of O3 are much more amenable to bond formation than those of SO2. We show that the differences in the electronic structure of the π systems in the parent triatomic species account for the differences in the addition of hydrogen atoms to the terminal atoms of O3 and SO2. Further, we find that the π system in SO2, which is a recoupled pair bond dyad, facilitates the addition of hydrogen atoms to the sulfur atom, resulting in stable HSO2 and H2SO2 species.

  19. The Relativistic Effects on the Carbon-Carbon Coupling Constants Mediated by a Heavy Atom.

    PubMed

    Wodyński, Artur; Malkina, Olga L; Pecul, Magdalena

    2016-07-21

    The (2)JCC, (3)JCC, and (4)JCC spin-spin coupling constants in the systems with a heavy atom (Cd, In, Sn, Sb, Te, Hg, Tl, Pb, Bi, and Po) in the coupling path have been calculated by means of density functional theory. The main goal was to estimate the relativistic effects on spin-spin coupling constants and to explore the factors which may influence them, including the nature of the heavy atom and carbon hybridization. The methods applied range, in order of reduced complexity, from the Dirac-Kohn-Sham (DKS) method (density functional theory with four-component Dirac-Coulomb Hamiltonian), through DFT with two- and one-component zeroth-order regular approximation (ZORA) Hamiltonians, to scalar effective core potentials (ECPs) with the nonrelativistic Hamiltonian. The use of DKS and ZORA methods leads to very similar results, and small-core ECPs of the MDF and MWB variety reproduce correctly the scalar relativistic effects. Scalar relativistic effects usually are larger than the spin-orbit coupling effects. The latter tend to influence the most the coupling constants of the sp(3)-hybridized carbon atoms and in compounds of the p-block heavy atoms. Large spin-orbit coupling contributions for the Po compounds are probably connected with the inverse of the lowest triplet excitation energy.

  20. Rotational Spectrum and Carbon Atom Structure of Dihydroartemisinic Acid

    NASA Astrophysics Data System (ADS)

    Evangelisti, Luca; Seifert, Nathan A.; Spada, Lorenzo; Pate, Brooks

    2016-06-01

    Dihydroartemisinic acid (DHAA, C15H24O2, five chiral centers) is a precursor in proposed low-cost synthetic routes to the antimalarial drug artemisinin. In one reaction process being considered in pharmaceutical production, DHAA is formed from an enantiopure sample of artemisinic acid through hydrogenation of the alkene. This reaction needs to properly set the stereochemistry of the asymmetric carbon for the synthesis to produce artemisinin. A recrystallization process can purify the diastereomer mixture of the hydrogenation reaction if the unwanted epimer is produced in less than 10% abundance. There is a need in the process analytical chemistry to rapidly (less than 1 min) measure the diastereomer excess and current solutions, such a HPLC, lack the needed measurement speed. The rotational spectrum of DHAA has been measured at 300:1 signal-to-noise ratio in a chirped-pulsed Fourier transform microwave spectrometer operating from 2-8 GHz using simple heating of the compound. The 13C isotope analysis provides a carbon atom structure that confirms the diastereomer. This structure is in excellent agreement with quantum chemistry calculations at the B2PLYPD3/ 6-311++G** level of theory. The DHAA spectrum is expected to be fully resolved from the unwanted diastereomer raising the potential for fast diastereomer excess measurement by rotational spectroscopy in the pharmaceutical production process.

  1. Characterization of carbon nanotube yarn after exposure to hyperthermal atomic oxygen and thermal fatigue

    NASA Astrophysics Data System (ADS)

    Misak, H. E.; Mall, S.

    2016-12-01

    Carbon nanotube (CNT)-yarn was evaluated for the survivability under hazardous space environmental conditions which were thermal fatigue, atomic oxygen and additive effect of these two exposures. Its tensile strength, tenacity, stiffness, strain to failure and electrical conductivity were characterized at the two extreme space temperatures of -150 and 120 °C before and after exposure to these environmental conditions. Tensile strength, stiffness and electrical conductivity of unexposed CNT yarn increased at the cryogenic temperature relative to at the elevated temperature. There was no change in the tensile properties after exposure to the space environmental conditions when measured at the elevated and cryogenic temperatures. Electrical conductivity decreased after exposure to three hazardous environments involving thermal fatigue, but it had no or small decrease when exposed to atomic oxygen only. No additive effect of thermal fatigue followed by atomic oxygen or by atomic oxygen followed by thermal fatigue environments on the CNTs' tensile properties and electrical conductivity was observed. Considering the low density 0.59 g/cc and good resistant to the extreme hazardous space environment, CNT-yarns have potential for applications in spacecraft and satellites.

  2. Atomic Layer Deposition on Carbon Nanotubes and their Assemblies

    NASA Astrophysics Data System (ADS)

    Stano, Kelly Lynn

    Global issues related to energy and the environment have motivated development of advanced material solutions outside of traditional metals ceramics, and polymers. Taking inspiration from composites, where the combination of two or more materials often yields superior properties, the field of organic-inorganic hybrids has recently emerged. Carbon nanotube (CNT)-inorganic hybrids have drawn widespread and increasing interest in recent years due to their multifunctionality and potential impact across several technologically important application areas. Before the impacts of CNT-inorganic hybrids can be realized however, processing techniques must be developed for their scalable production. Optimization in chemical vapor deposition (CVD) methods for synthesis of CNTs and vertically aligned CNT arrays has created production routes both high throughput and economically feasible. Additionally, control of CVD parameters has allowed for growth of CNT arrays that are able to be drawn into aligned sheets and further processed to form a variety of aligned 1, 2, and 3-dimensional bulk assemblies including ribbons, yarns, and foams. To date, there have only been a few studies on utilizing these bulk assemblies for the production of CNT-inorganic hybrids. Wet chemical methods traditionally used for fabricating CNT-inorganic hybrids are largely incompatible with CNT assemblies, since wetting and drying the delicate structures with solvents can destroy their structure. It is therefore necessary to investigate alternative processing strategies in order to advance the field of CNT-inorganic hybrids. In this dissertation, atomic layer deposition (ALD) is evaluated as a synthetic route for the production of large-scale CNT-metal oxide hybrids as well as pure metal oxide architectures utilizing CNT arrays, ribbons, and ultralow density foams as deposition templates. Nucleation and growth behavior of alumina was evaluated as a function of CNT surface chemistry. While highly graphitic

  3. In situ nucleation of carbon nanotubes by the injection of carbon atoms into metal particles

    NASA Astrophysics Data System (ADS)

    Rodríguez-Manzo, Julio A.; Terrones, Mauricio; Terrones, Humberto; Kroto, Harold W.; Sun, Litao; Banhart, Florian

    2007-05-01

    The synthesis of carbon nanotubes (CNTs) of desired chiralities and diameters is one of the most important challenges in nanotube science and achieving such selectivity may require a detailed understanding of their growth mechanism. We report the formation of CNTs in an entirely condensed phase process that allows us, for the first time, to monitor the nucleation of a nanotube on the spherical surface of a metal particle. When multiwalled CNTs containing metal particle cores are irradiated with an electron beam, carbon from graphitic shells surrounding the metal particles is ingested into the body of the particle and subsequently emerges as single-walled nanotubes (SWNTs) or multiwalled nanotubes (MWNTs) inside the host nanotubes. These observations, at atomic resolution in an electron microscope, show that there is direct bonding between the tubes and the metal surface from which the tubes sprout and can be readily explained by bulk diffusion of carbon through the body of catalytic particles, with no evidence of surface diffusion.

  4. Hydrogen atom addition to the surface of graphene nanoflakes: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Tachikawa, Hiroto

    2017-02-01

    Polycyclic aromatic hydrocarbons (PAHs) provide a 2-dimensional (2D) reaction surface in 3-dimensional (3D) interstellar space and have been utilized as a model of graphene surfaces. In the present study, the reaction of PAHs with atomic hydrogen was investigated by means of density functional theory (DFT) to systematically elucidate the binding nature of atomic hydrogen to graphene nanoflakes. PAHs with n = 4-37 were chosen, where n indicates the number of benzene rings. Activation energies of hydrogen addition to the graphene surface were calculated to be 5.2-7.0 kcal/mol at the CAM-B3LYP/6-311G(d,p) level, which is almost constant for all PAHs. The binding energies of hydrogen atom were slightly dependent on the size (n): 14.8-28.5 kcal/mol. The absorption spectra showed that a long tail is generated at the low-energy region after hydrogen addition to the graphene surface. The electronic states of hydrogenated graphenes were discussed on the basis of theoretical results.

  5. Additives to reduce susceptibility of thermosets and thermoplastics to erosion from atomic oxygen

    NASA Technical Reports Server (NTRS)

    Orwoll, Robert A.

    1990-01-01

    Polymeric materials have many attractive features such as light weight, high strength, and broad applicability in the form of films, fibers, and molded objects. In low earth orbit (LEO), these materials, when exposed on the exterior of the spacecraft, have the serious disadvantage of being susceptible to erosion by atomic oxygen (AO). AO is the most common chemical species at LEO altitudes. AO can be an extremely efficient oxidizing agent as was apparent from the extensive erosion of organic films exposed in STS missions. The mechanism for erosion involves the reaction of oxygen atoms at the surface of the substrate to form small molecular species. The susceptibility of polymeric materials varies with their chemical composition. Films with silicon atoms incorporated in the molecular structures have large coefficients of thermal expansion. This limits their utility. In an alternative approach additives were sought that mix physically and form a protective oxide layer when the film is exposed to AO. A large number of organic compounds containing silicon, germanium, or tin atoms were screened. Most were found to have very limited solubility in the polyetherimide (Ultem) films that were being protected from AO. However, one, bis(triphenyl tin) oxide, (BTO), is miscible in Ultem up to about 25 percent. Films of Ultem polyimide containing up to 25 wt percent BTO were prepared by evaporation of solvent from a solution of Ultem and BTO. The effects of AO on these films were simulated in the oxygen atmosphere of a radio frequency glow-discharge chamber. In the second part of this study, atoms were incorporated in epoxy resins. Experiments are in progress to measure the resistance of films of the cured epoxy to AO in the discharge chamber.

  6. Energy of the Isolated Metastable Iron-Nickel FCC Nanocluster with a Carbon Atom in the Tetragonal Interstice.

    PubMed

    Bondarenko, Natalya V; Nedolya, Anatoliy V

    2017-12-01

    The energy of the isolated iron-nickel nanocluster was calculated by molecular mechanics method using Lennard-Jones potential. The cluster included a carbon atom that drifted from an inside octahedral interstice to a tetrahedral interstice in [Formula: see text] direction and after that in <222> direction to the surface. In addition, one of 14 iron atoms was replaced by a nickel atom, the position of which was changing during simulation.The energy of the nanocluster was estimated at the different interatomic distances. As a result of simulation, the optimal interatomic distances of Fe-Ni-C nanocluster was chosen for the simulation, in which height of the potential barrier was maximal and face-centered cubic (FCC) nanocluster was the most stable.It is shown that there were three main positions of a nickel atom that significantly affected nanocluster's energy.The calculation results indicated that position of the carbon atom in the octahedral interstice was more energetically favorable than tetrahedral interstice in the case of FCC nanocluster. On the other side, the potential barrier was smaller in the direction [Formula: see text] than in the direction <022>.This indicates that there are two ways for carbon atom to drift to the surface of the nanocluster.

  7. Site specific atomic polarizabilities in endohedral fullerenes and carbon onions

    SciTech Connect

    Zope, Rajendra R. Baruah, Tunna; Bhusal, Shusil; Basurto, Luis; Jackson, Koblar

    2015-08-28

    We investigate the polarizability of trimetallic nitride endohedral fullerenes by partitioning the total polarizability into site specific components. This analysis indicates that the polarizability of the endohedral fullerene is essentially due to the outer fullerene cage and has insignificant contribution from the encapsulated unit. Thus, the outer fullerene cages effectively shield the encapsulated clusters and behave like Faraday cages. The polarizability of endohedral fullerenes is slightly smaller than the polarizability of the corresponding bare carbon fullerenes. The application of the site specific polarizabilities to C{sub 60}@C{sub 240} and C{sub 60}@C{sub 180} onions shows that, compared to the polarizability of isolated C{sub 60} fullerene, the encapsulation of the C{sub 60} in C{sub 240} and C{sub 180} fullerenes reduces its polarizability by 75% and 83%, respectively. The differences in the polarizability of C{sub 60} in the two onions is a result of differences in the bonding (intershell electron transfer), fullerene shell relaxations, and intershell separations. The site specific analysis further shows that the outer atoms in a fullerene shell contribute most to the fullerene polarizability.

  8. Site specific atomic polarizabilities in endohedral fullerenes and carbon onions

    NASA Astrophysics Data System (ADS)

    Zope, Rajendra R.; Bhusal, Shusil; Basurto, Luis; Baruah, Tunna; Jackson, Koblar

    2015-08-01

    We investigate the polarizability of trimetallic nitride endohedral fullerenes by partitioning the total polarizability into site specific components. This analysis indicates that the polarizability of the endohedral fullerene is essentially due to the outer fullerene cage and has insignificant contribution from the encapsulated unit. Thus, the outer fullerene cages effectively shield the encapsulated clusters and behave like Faraday cages. The polarizability of endohedral fullerenes is slightly smaller than the polarizability of the corresponding bare carbon fullerenes. The application of the site specific polarizabilities to C60@C240 and C60@C180 onions shows that, compared to the polarizability of isolated C60 fullerene, the encapsulation of the C60 in C240 and C180 fullerenes reduces its polarizability by 75% and 83%, respectively. The differences in the polarizability of C60 in the two onions is a result of differences in the bonding (intershell electron transfer), fullerene shell relaxations, and intershell separations. The site specific analysis further shows that the outer atoms in a fullerene shell contribute most to the fullerene polarizability.

  9. Site specific atomic polarizabilities in endohedral fullerenes and carbon onions.

    PubMed

    Zope, Rajendra R; Bhusal, Shusil; Basurto, Luis; Baruah, Tunna; Jackson, Koblar

    2015-08-28

    We investigate the polarizability of trimetallic nitride endohedral fullerenes by partitioning the total polarizability into site specific components. This analysis indicates that the polarizability of the endohedral fullerene is essentially due to the outer fullerene cage and has insignificant contribution from the encapsulated unit. Thus, the outer fullerene cages effectively shield the encapsulated clusters and behave like Faraday cages. The polarizability of endohedral fullerenes is slightly smaller than the polarizability of the corresponding bare carbon fullerenes. The application of the site specific polarizabilities to C60@C240 and C60@C180 onions shows that, compared to the polarizability of isolated C60 fullerene, the encapsulation of the C60 in C240 and C180 fullerenes reduces its polarizability by 75% and 83%, respectively. The differences in the polarizability of C60 in the two onions is a result of differences in the bonding (intershell electron transfer), fullerene shell relaxations, and intershell separations. The site specific analysis further shows that the outer atoms in a fullerene shell contribute most to the fullerene polarizability.

  10. Reactions of Atomic Carbon with Butene Isomers: Implications for Molecular Growth in Carbon-Rich Environments

    DOE PAGES

    Bourgalais, J.; Spencer, Michael; Osborn, David L.; ...

    2016-10-31

    We carried out the product detection studies of C(3P) atom reactions with butene (C4H8) isomers (but-1-ene, cis-but-2-ene, trans-but-2-ene) in a flow tube reactor at 353 K and 4 Torr under multiple collision conditions. Ground state carbon atoms are generated by 248 nm laser photolysis of tetrabromomethane, CBr4, in a buffer of helium. Thermalized reaction products are detected using synchrotron tunable VUV photoionization and time-of-flight mass spectrometry. The temporal profiles of the detected ions are used to discriminate products from side or secondary reactions. Furthermore, for the C(3P) + trans-but-2-ene and C(3P) + cis-but-2-ene reactions, various isomers of C4H5 and C5H7more » are identified as reaction products formed via CH3 and H elimination. Assuming equal ionization cross sections for all C4H5 and C5H7 isomers, C4H5:C5H7 branching ratios of 0.63:1 and 0.60:1 are derived for the C(3P) + trans-but-2-ene and the C(3P) + cis-but-2-ene reactions, respectively. For the C(3P) + but-1-ene reaction, two reaction channels are observed: the H-elimination channel, leading to the formation of the ethylpropargyl isomer, and the C3H3 + C2H5 channel. Assuming equal ionization cross sections for ethylpropargyl and C3H3 radicals, a branching ratio of 1:0.95 for the C3H3 + C2H5 and H + ethylpropargyl channels is derived. Finally, the experimental results are compared to previous H atom branching ratios and used to propose the most likely mechanisms for the reaction of ground state carbon atoms with butene isomers.« less

  11. Reactions of Atomic Carbon with Butene Isomers: Implications for Molecular Growth in Carbon-Rich Environments

    NASA Astrophysics Data System (ADS)

    Bourgalais, J.; Spencer, Michael; Osborn, David L.; Goulay, F.; Le Picard, S. D.

    2016-10-01

    Product detection studies of C(3P) atom reactions with butene (C4H8) isomers (but-1-ene, cis-but-2-ene, trans-but-2-ene) are carried out in a flow tube reactor at 353 K and 4 Torr under multiple collision conditions. Ground state carbon atoms are generated by 248 nm laser photolysis of tetrabromomethane, CBr4, in a buffer of helium. Thermalized reaction products are detected using synchrotron tunable VUV photoionization and time-of-flight mass spectrometry. The temporal profiles of the detected ions are used to discriminate products from side or secondary reactions. For the C(3P) + trans-but-2-ene and C(3P) + cis-but-2-ene reactions, various isomers of C4H5 and C5H7 are identified as reaction products formed via CH3 and H elimination. Assuming equal ionization cross sections for all C4H5 and C5H7 isomers, C4H5:C5H7 branching ratios of 0.63:1 and 0.60:1 are derived for the C(3P) + trans-but-2-ene and the C(3P) + cis-but-2-ene reactions, respectively. For the C(3P) + but-1ene reaction, two reaction channels are observed: the H-elimination channel, leading to the formation of the ethylpropargyl isomer, and the C3H3 + C2H5 channel. Assuming equal ionization cross sections for ethylpropargyl and C3H3 radicals, a branching ratio of 1:0.95 for the C3H3 + C2H5 and H + ethylpropargyl channels is derived. The experimental results are compared to previous H atom branching ratios and used to propose the most likely mechanisms for the reaction of ground state carbon atoms with butene isomers.

  12. Determination of mercury in carbon black by cold vapor atomic absorption spectrometry.

    PubMed

    Hepp, Nancy M

    2006-01-01

    Recently, a new color additive, D&C Black No. 2, a high-purity furnace black in the general category of carbon blacks, was listed as a color subject to batch certification by the U.S. Food and Drug Administration. A simple procedure was developed to determine mercury (Hg) in D&C Black No. 2, which is limited by specification to not more than 1 ppm Hg. The method uses partial acid digestion followed by cold vapor atomic absorption and was developed by modifying a method used for other color additives. The carbon black samples are treated with a mixture of nitric and hydrochloric acids and heated by microwave in sealed Teflon vessels. The resulting solutions, which are stable to Hg loss for at least 1 week, are diluted and analyzed for Hg using cold vapor atomic absorption spectrometry. Validation was performed by spiking carbon black samples with inorganic Hg (HgNO3) at levels from 0.1 to 1.5 microg/g, and by analyzing 2 standard reference materials. At the specification level of 1 ppm Hg (1 microg Hg/g), the 95% confidence interval was +/-0.01 ppm Hg (0.01 microg Hg/g). The method developed in this study gave good results for very difficult-to-analyze materials, such as coal standard reference materials and carbon black. By eliminating volatility and adsorption factors through the formation of HgCl4(-2) complexes, one can avoid using extremely hazardous acids such as HF and HClO4.

  13. Carbon–carbon bond activation of cyclobutenones enabled by the addition of chiral organocatalyst to ketone

    PubMed Central

    Li, Bao-Sheng; Wang, Yuhuang; Jin, Zhichao; Zheng, Pengcheng; Ganguly, Rakesh; Chi, Yonggui Robin

    2015-01-01

    The activation of carbon–carbon (C–C) bonds is an effective strategy in building functional molecules. The C–C bond activation is typically accomplished via metal catalysis, with which high levels of enantioselectivity are difficult to achieve due to high reactivity of metal catalysts and the metal-bound intermediates. It remains largely unexplored to use organocatalysis for C–C bond activation. Here we describe an organocatalytic activation of C–C bonds through the addition of an NHC to a ketone moiety that initiates a C–C single bond cleavage as a key step to generate an NHC-bound intermediate for chemo- and stereo-selective reactions. This reaction constitutes an asymmetric functionalization of cyclobutenones using organocatalysts via a C–C bond activation process. Structurally diverse and multicyclic compounds could be obtained with high optical purities via an atom and redox economic process. PMID:25652912

  14. ADME evaluation in drug discovery. 2. Prediction of partition coefficient by atom-additive approach based on atom-weighted solvent accessible surface areas.

    PubMed

    Hou, T J; Xu, X J

    2003-01-01

    A novel method for the calculations of 1-octanol/water partition coefficient (log P) of organic molecules has been presented here. The method, SLOGP v1.0, estimates the log P values by summing the contribution of atom-weighted solvent accessible surface areas (SASA) and correction factors. Altogether 100 atom/group types were used to classify atoms with different chemical environments, and two correlation factors were used to consider the intermolecular hydrophobic interactions and intramolecular hydrogen bonds. Coefficient values for 100 atom/group and two correction factors have been derived from a training set of 1850 compounds. The parametrization procedure for different kinds of atoms was performed as follows: first, the atoms in a molecule were defined to different atom/group types based on SMARTS language, and the correction factors were determined by substructure searching; then, SASA for each atom/group type was calculated and added; finally, multivariate linear regression analysis was applied to optimize the hydrophobic parameters for different atom/group types and correction factors in order to reproduce the experimental log P. The correlation based on the training set gives a model with the correlation coefficient (r) of 0.988, the standard deviation (SD) of 0.368 log units, and the absolute unsigned mean error of 0.261. Comparison of various procedures of log P calculations for the external test set of 138 organic compounds demonstrates that our method bears very good accuracy and is comparable or even better than the fragment-based approaches. Moreover, the atom-additive approach based on SASA was compared with the simple atom-additive approach based on the number of atoms. The calculated results show that the atom-additive approach based on SASA gives better predictions than the simple atom-additive one. Due to the connection between the molecular conformation and the molecular surface areas, the atom-additive model based on SASA may be a more

  15. Exchange of carbon-bound hydrogen atoms ortho to the hydroxyl group in tyrosine.

    PubMed

    Martin, R B; Morlino, V J

    1965-10-22

    The carbon-bound hydrogen atoms of tyrosine that exchange with solvent protons in strongly acid solutions at about 100 degrees C are not the methylene hydrogen atoms but a pair on the aromatic ring. Of the two pairs of protons on the aromatic ring, observed in the proton magnetic resonance spectra, the pair at higher field undergoes exchange in 2.4N DCI at 100 degrees C. Other hydrogen atoms, attached either to aliphatic or aromatic carbon atoms, exhibit no noticeable exchange under the same conditions. From a chemicalshift analysis the exchanging protons are assigned as those ortho to the hydroxyl group on the aromatic ring.

  16. LETTER TO THE EDITOR: Enhancement of neutron radiation dose by the addition of sulphur-33 atoms

    NASA Astrophysics Data System (ADS)

    Porras, I.

    2008-04-01

    The use of neutrons in radiotherapy allows the possibility of producing nuclear reactions in a specific target inserted in the medium. 10B is being used to induce reactions (n, α), a technique called boron neutron capture therapy. I have studied the possibility of inducing a similar reaction using the nucleus of 33S, for which the reaction cross section presents resonances for keV neutrons, the highest peak occurring at 13.5 keV. Here shown, by means of Monte Carlo simulation of point-like sources of neutrons in this energy range, is an enhancement effect on the absorbed dose in water by the addition of 33S atoms. In addition to this, as the range of the alpha particle is of the order of a mammalian cell size, the energy deposition via this reaction results mainly inside the cells adjacent to the interaction site. The main conclusion of the present work is that the insertion of these sulphur atoms in tumoral cells would enhance the effect of neutron irradiation in the keV range.

  17. Effect of carbon and alloying solute atoms on helium behaviors in α-Fe

    NASA Astrophysics Data System (ADS)

    Zhang, Yange; You, Yu-Wei; Xu, Yichun; Liu, C. S.; Chen, J. L.; Luo, G.-N.

    2017-02-01

    Helium bubbles could strongly degrade the mechanical properties of ferritic steels in fission and fusion systems. The formation of helium bubble is directly affected by the interactions between helium and the compositions in steels, such as solute atoms, carbon and irradiation defects. We thereby performed systematical first-principles calculations to investigate the interactions of solute-helium and carbon-solute-helium. It is found that substitutional helium is more attractive than interstitial helium to all the considered 3p, 4p, 5p and 6p solutes. The attraction between carbon and substitutional helium suggests the carbon-solute-helium complex can be formed stably. By examining the charge density difference and thermal stability, it is found that the ternary complex shows stronger attraction with He than that of solute-helium pair for some solutes (S, Se, In, Te, Pb and Bi) and the complex could existed in iron stably at 700 K. The present theoretical results may be helpful for exploring alloy additions to mitigate the formation of large helium bubbles.

  18. Ab initio study of semiconductor atoms impurities in zigzag edge (10,0) carbon nanotubes

    SciTech Connect

    Muttaqien, Fahdzi Suprijadi

    2015-04-16

    The substitutional impurities in zigzag edge (10,0) carbon nanotubes have been studied by using first principles calculations. Silicon (Si), gallium (Ga), and arsenic (As) atom have been chosen as semiconductor based-atom for replacing carbon atoms in CNT’s surface. The silicon atom changes the energy gap of pristine zigzag (10,0) CNT, it is 0.19 eV more narrow than that of pristine CNT. Geometrically, the silicon atom creates sp{sup 3} bond with three adjacent carbon atoms, where the tetrahedral form of its sp{sup 3} bond is consisted of free unoccupied state. The silicon atom does not induce magnetism to zigzag CNT. Due to gallium (Ga) and arsenic (As) atom substitution, the zigzag CNT becomes metallic and has magnetic moment of 1 µ{sub B}. The valance and conduction band are crossed each other, then the energy gap is vanished. The electronic properties of GaAs-doped CNT are dominantly affected by gallium atom and its magnetic properties are dominantly affected by arsenic atom. These results prove that the CNT with desired properties can be obtained with substitutional impurities without any giving structural defect.

  19. Mechanical strength of additive manufactured carbon fiber reinforced polyetheretherketone

    NASA Astrophysics Data System (ADS)

    Chumaevskii, A. V.; Tarasov, S. Yu.; Filippov, A. V.; Kolubaev, E. A.; Rubtsov, V. E.; Eliseev, A. A.

    2016-11-01

    Mechanical properties of both pure and chopped carbon fiber reinforced polyetheretherketone samples have been carried out. It was shown that the reinforcement resulted in increasing the elasticity modulus, compression and tensile ultimate strength by a factor of 3.5, 2.9 and 2.8, respectively. The fracture surfaces have been examined using both optical and scanning electron microscopy.

  20. A simple and clean source of low-energy atomic carbon

    SciTech Connect

    Krasnokutski, S. A.; Huisken, F.

    2014-09-15

    A carbon source emitting low-energy carbon atoms from a thin-walled, sealed tantalum tube via thermal evaporation has been constructed. The tube is made from a 0.05 mm thick tantalum foil and filled with {sup 12}C or {sup 13}C carbon powder. After being sealed, it is heated by direct electric current. The solvated carbon atoms diffuse to the outer surface of the tube and, when the temperature rises over 2200 K, the evaporation of atomic carbon from the surface of the tantalum tube is observed. As the evaporated species have low energy they are well-suited for the incorporation into liquid helium droplets by the pick-up technique. Mass analysis of the incorporated species reveals the dominant presence of atomic carbon and very low abundances of C{sub 2} and C{sub 3} molecules (<1%). This is in striking contrast to the thermal evaporation of pure carbon, where C{sub 3} molecules are found to be the dominant species in the gas phase. Due to the thermal evaporation and the absence of high-energy application required for the dissociation of C{sub 2} and C{sub 3} molecules, the present source provides carbon atoms with rather low energy.

  1. Roles of additives and surface control in slurry atomization. Final project report

    SciTech Connect

    Tsai, S.C.

    1992-12-31

    This project studies the rheology and airblast atomization of micronized coal slurries. Its major objectives are (1) to promote further understanding of the mechanisms and the roles of additives in airblast atomization of coal water slurry (CWS), and (2) to investigate the impacts of coal particle surface properties and interparticle forces on CWS rheology. We have found that the flow behavior index (n) of a suspension (or slurry) is determined by the relative importance of the interparticle van der Waals attraction and the interparticle electrostatic repulsion. The interparticle attraction, measured by the Hamaker constant scaled to the thermal energy at 25{degrees}C (A/kT), causes particle aggregation, which breaks down at high shear rates, and thus leads to slurry pseudoplastic behavior (n< 1). At a constant particle volume fraction and surface charge density (qualitatively measured by the zeta potential in deionized water), n decreases linearly as A/kT increases. The relative viscosity of the pseudoplastic suspension with respect to that of the suspending liquid is found to be independent of particle density and correlate well with the particle Peclet number which equals the particle diffusional relaxation time multiplied by shear rate. Specifically, the relative viscosities of the pseudoplastic glycerol/water coal slurry and the ethylene glycol/glycerol sand slurry, at same volume fractions as well as similar particle size distributions and liquid viscosities, as functions of the particle Peclet number fall along the same line.

  2. Reactions of Atomic Carbon with Butene Isomers: Implications for Molecular Growth in Carbon-Rich Environments

    SciTech Connect

    Bourgalais, J.; Spencer, Michael; Osborn, David L.; Goulay, F.; Le Picard, S. D.

    2016-10-31

    We carried out the product detection studies of C(3P) atom reactions with butene (C4H8) isomers (but-1-ene, cis-but-2-ene, trans-but-2-ene) in a flow tube reactor at 353 K and 4 Torr under multiple collision conditions. Ground state carbon atoms are generated by 248 nm laser photolysis of tetrabromomethane, CBr4, in a buffer of helium. Thermalized reaction products are detected using synchrotron tunable VUV photoionization and time-of-flight mass spectrometry. The temporal profiles of the detected ions are used to discriminate products from side or secondary reactions. Furthermore, for the C(3P) + trans-but-2-ene and C(3P) + cis-but-2-ene reactions, various isomers of C4H5 and C5H7 are identified as reaction products formed via CH3 and H elimination. Assuming equal ionization cross sections for all C4H5 and C5H7 isomers, C4H5:C5H7 branching ratios of 0.63:1 and 0.60:1 are derived for the C(3P) + trans-but-2-ene and the C(3P) + cis-but-2-ene reactions, respectively. For the C(3P) + but-1-ene reaction, two reaction channels are observed: the H-elimination channel, leading to the formation of the ethylpropargyl isomer, and the C3H3 + C2H5 channel. Assuming equal ionization cross sections for ethylpropargyl and C3H3 radicals, a branching ratio of 1:0.95 for the C3H3 + C2H5 and H + ethylpropargyl channels is derived. Finally, the experimental results are compared to previous H atom branching ratios and used to propose the most likely mechanisms for the reaction of ground state carbon atoms with butene isomers.

  3. Tailoring Thermal Conductivity of Single-stranded Carbon-chain Polymers through Atomic Mass Modification

    PubMed Central

    Liao, Quanwen; Zeng, Lingping; Liu, Zhichun; Liu, Wei

    2016-01-01

    Tailoring the thermal conductivity of polymers is central to enlarge their applications in the thermal management of flexible integrated circuits. Progress has been made over the past decade by fabricating materials with various nanostructures, but a clear relationship between various functional groups and thermal properties of polymers remains to be established. Here, we numerically study the thermal conductivity of single-stranded carbon-chain polymers with multiple substituents of hydrogen atoms through atomic mass modification. We find that their thermal conductivity can be tuned by atomic mass modifications as revealed through molecular dynamics simulations. The simulation results suggest that heavy homogeneous substituents do not assist heat transport and trace amounts of heavy substituents can in fact hinder heat transport substantially. Our analysis indicates that carbon chain has the biggest contribution (over 80%) to the thermal conduction in single-stranded carbon-chain polymers. We further demonstrate that atomic mass modifications influence the phonon bands of bonding carbon atoms, and the discrepancies of phonon bands between carbon atoms are responsible for the remarkable drops in thermal conductivity and large thermal resistances in carbon chains. Our study provides fundamental insight into how to tailor the thermal conductivity of polymers through variable substituents. PMID:27713563

  4. Tailoring Thermal Conductivity of Single-stranded Carbon-chain Polymers through Atomic Mass Modification.

    PubMed

    Liao, Quanwen; Zeng, Lingping; Liu, Zhichun; Liu, Wei

    2016-10-07

    Tailoring the thermal conductivity of polymers is central to enlarge their applications in the thermal management of flexible integrated circuits. Progress has been made over the past decade by fabricating materials with various nanostructures, but a clear relationship between various functional groups and thermal properties of polymers remains to be established. Here, we numerically study the thermal conductivity of single-stranded carbon-chain polymers with multiple substituents of hydrogen atoms through atomic mass modification. We find that their thermal conductivity can be tuned by atomic mass modifications as revealed through molecular dynamics simulations. The simulation results suggest that heavy homogeneous substituents do not assist heat transport and trace amounts of heavy substituents can in fact hinder heat transport substantially. Our analysis indicates that carbon chain has the biggest contribution (over 80%) to the thermal conduction in single-stranded carbon-chain polymers. We further demonstrate that atomic mass modifications influence the phonon bands of bonding carbon atoms, and the discrepancies of phonon bands between carbon atoms are responsible for the remarkable drops in thermal conductivity and large thermal resistances in carbon chains. Our study provides fundamental insight into how to tailor the thermal conductivity of polymers through variable substituents.

  5. Structure and stability of a silicon cluster on sequential doping with carbon atoms

    NASA Astrophysics Data System (ADS)

    AzeezullaNazrulla, Mohammed; Joshi, Krati; Israel, S.; Krishnamurty, Sailaja

    2016-02-01

    SiC is a highly stable material in bulk. On the other hand, alloys of silicon and carbon at nanoscale length are interesting from both technological as well fundamental view point and are being currently synthesized by various experimental groups (Truong et. al., 2015 [26]). In the present work, we identify a well-known silicon cluster viz., Si10 and dope it sequentially with carbon atoms. The evolution of electronic structure (spin state and the structural properties) on doping, the charge redistribution and structural properties are analyzed. It is interesting to note that the ground state SiC clusters prefer to be in the lowest spin state. Further, it is seen that carbon atoms are the electron rich centres while silicon atoms are electron deficient in every SiC alloy cluster. The carbon-carbon bond lengths in alloy clusters are equivalent to those seen in fullerene molecules. Interestingly, the carbon atoms tend to aggregate together with silicon atoms surrounding them by donating the charge. As a consequence, very few Si-Si bonds are noted with increasing concentrations of C atoms in a SiC alloy. Physical and chemical stability of doped clusters is studied by carrying out finite temperature behaviour and adsorbing O2 molecule on Si9C and Si8C2 clusters, respectively.

  6. Tailoring Thermal Conductivity of Single-stranded Carbon-chain Polymers through Atomic Mass Modification

    NASA Astrophysics Data System (ADS)

    Liao, Quanwen; Zeng, Lingping; Liu, Zhichun; Liu, Wei

    2016-10-01

    Tailoring the thermal conductivity of polymers is central to enlarge their applications in the thermal management of flexible integrated circuits. Progress has been made over the past decade by fabricating materials with various nanostructures, but a clear relationship between various functional groups and thermal properties of polymers remains to be established. Here, we numerically study the thermal conductivity of single-stranded carbon-chain polymers with multiple substituents of hydrogen atoms through atomic mass modification. We find that their thermal conductivity can be tuned by atomic mass modifications as revealed through molecular dynamics simulations. The simulation results suggest that heavy homogeneous substituents do not assist heat transport and trace amounts of heavy substituents can in fact hinder heat transport substantially. Our analysis indicates that carbon chain has the biggest contribution (over 80%) to the thermal conduction in single-stranded carbon-chain polymers. We further demonstrate that atomic mass modifications influence the phonon bands of bonding carbon atoms, and the discrepancies of phonon bands between carbon atoms are responsible for the remarkable drops in thermal conductivity and large thermal resistances in carbon chains. Our study provides fundamental insight into how to tailor the thermal conductivity of polymers through variable substituents.

  7. Effects of Atomic-Scale Structure on the Fracture Properties of Amorphous Carbon - Carbon Nanotube Composites

    NASA Technical Reports Server (NTRS)

    Jensen, Benjamin D.; Wise, Kristopher E.; Odegard, Gregory M.

    2015-01-01

    The fracture of carbon materials is a complex process, the understanding of which is critical to the development of next generation high performance materials. While quantum mechanical (QM) calculations are the most accurate way to model fracture, the fracture behavior of many carbon-based composite engineering materials, such as carbon nanotube (CNT) composites, is a multi-scale process that occurs on time and length scales beyond the practical limitations of QM methods. The Reax Force Field (ReaxFF) is capable of predicting mechanical properties involving strong deformation, bond breaking and bond formation in the classical molecular dynamics framework. This has been achieved by adding to the potential energy function a bond-order term that varies continuously with distance. The use of an empirical bond order potential, such as ReaxFF, enables the simulation of failure in molecular systems that are several orders of magnitude larger than would be possible in QM techniques. In this work, the fracture behavior of an amorphous carbon (AC) matrix reinforced with CNTs was modeled using molecular dynamics with the ReaxFF reactive forcefield. Care was taken to select the appropriate simulation parameters, which can be different from those required when using traditional fixed-bond force fields. The effect of CNT arrangement was investigated with three systems: a single-wall nanotube (SWNT) array, a multi-wall nanotube (MWNT) array, and a SWNT bundle system. For each arrangement, covalent bonds are added between the CNTs and AC, with crosslink fractions ranging from 0-25% of the interfacial CNT atoms. The SWNT and MWNT array systems represent ideal cases with evenly spaced CNTs; the SWNT bundle system represents a more realistic case because, in practice, van der Waals interactions lead to the agglomeration of CNTs into bundles. The simulation results will serve as guidance in setting experimental processing conditions to optimize the mechanical properties of CNT

  8. Unexpected Huge Dimerization Ratio in One-Dimensional Carbon Atomic Chains.

    PubMed

    Lin, Yung-Chang; Morishita, Shigeyuki; Koshino, Masanori; Yeh, Chao-Hui; Teng, Po-Yuan; Chiu, Po-Wen; Sawada, Hidetaka; Suenaga, Kazutomo

    2017-01-11

    Peierls theory predicted atomic distortion in one-dimensional (1D) crystal due to its intrinsic instability in 1930. Free-standing carbon atomic chains created in situ in transmission electron microscope (TEM)1-3 are an ideal example to experimentally observe the dimerization behavior of carbon atomic chain within a finite length. We report here a surprisingly huge distortion found in the free-standing carbon atomic chains at 773 K, which is 10 times larger than the value expected in the system. Such an abnormally distorted phase only dominates at the elevated temperatures, while two distinct phases, distorted and undistorted, coexist at lower or ambient temperatures. Atom-by-atom spectroscopy indeed shows considerable variations in the carbon 1s spectra at each atomic site but commonly observes a slightly downshifted π* peak, which proves its sp(1) bonding feature. These results suggest that the simple model, relaxed and straight, is not fully adequate to describe the realistic 1D structure, which is extremely sensitive to perturbations such as external force or boundary conditions.

  9. Stable Gold(III) Catalysts by Oxidative Addition of a Carbon-Carbon Bond

    PubMed Central

    Wu, Chung-Yeh; Horibe, Takahiro; Jacobsen, Christian Borch

    2014-01-01

    Whereas low-valent late transition metal catalysis has become indispensible for chemical synthesis, homogeneous high-valent transition metal catalysis is underdeveloped, mainly due to the reactivity of high-valent transition metal complexes and the challenges associated with synthesizing them. In this manuscript, we report a mild carbon-carbon bond cleavage reaction by a Au(I) complex that generates a stable Au(III) cationic complex. Complementary to the well-established soft and carbophilic Au(I) catalyst, this Au(III) complex exhibits hard, oxophilic Lewis acidity. This is exemplified by catalytic activation of α,β-unsaturated aldehydes towards selective conjugate additions as well as activation of an unsaturated aldehyde-allene for a [2 + 2] cycloaddition reaction. The origin of the regioselectivity and catalytic activity was elucidated by X-ray crystallographic analysis of an isolated Au(III)-activated cinnamaldehyde intermediate. The concepts revealed in this study provide a strategy for accessing high-valent transition metal catalysis from readily available precursors. PMID:25612049

  10. Stable gold(III) catalysts by oxidative addition of a carbon-carbon bond

    NASA Astrophysics Data System (ADS)

    Wu, Chung-Yeh; Horibe, Takahiro; Jacobsen, Christian Borch; Toste, F. Dean

    2015-01-01

    Low-valent late transition-metal catalysis has become indispensable to chemical synthesis, but homogeneous high-valent transition-metal catalysis is underdeveloped, mainly owing to the reactivity of high-valent transition-metal complexes and the challenges associated with synthesizing them. Here we report a carbon-carbon bond cleavage at ambient conditions by a Au(I) complex that generates a stable Au(III) cationic complex. In contrast to the well-established soft and carbophilic Au(I) catalyst, this Au(III) complex exhibits hard, oxophilic Lewis acidity. For example, we observed catalytic activation of α,β-unsaturated aldehydes towards selective conjugate additions as well as activation of an unsaturated aldehyde-allene for a [2 + 2] cycloaddition reaction. The origin of the regioselectivity and catalytic activity was elucidated by X-ray crystallographic analysis of an isolated Au(III)-activated cinnamaldehyde intermediate. The concepts revealed suggest a strategy for accessing high-valent transition-metal catalysis from readily available precursors.

  11. Determination of additives in PVC material by UV laser ablation inductively coupled plasma atomic emission spectrometry

    NASA Astrophysics Data System (ADS)

    Hemmerlin, M.; Mermet, J. M.; Bertucci, M.; Zydowicz, P.

    1997-04-01

    UV laser ablation inductively coupled plasma atomic emission spectrometry (LA-ICP-AES) has been applied to the direct determination of additives in solid poly(vinyl chloride) materials. A Nd:YAG laser, operating at its fourth harmonic (266 nm), was used with a beam masking device, in the most reproducible conditions, to introduce solid particles into the plasma torch of a simultaneous ICP-AES system. Emphasis was placed on both precision and accuracy in the analysis of PVC materials by LA-ICP-AES. A series of six in-house PVC reference materials was prepared by incorporating several additives in increasing concentrations. Three alternative methods were evaluated to certify the amount of incorporated elements: ICP-AES with sample dissolution, NAA and XRF. Satisfactory results and good agreement were obtained for seven elements (Al, Ca, Cd, Mg, Sb, Sn and Ti) among the ten incorporated. Sample homogeneity appeared to be satisfactory, and calibration graphs obtained by LA-ICP-AES for several elements are presented. Finally, the performance of the technique in terms of repeatability (1.6-5%), reproducibility (2-5%), and limits of detection was investigated.

  12. Synthetic Strategies toward Natural Products Containing Contiguous Stereogenic Quaternary Carbon Atoms.

    PubMed

    Büschleb, Martin; Dorich, Stéphane; Hanessian, Stephen; Tao, Daniel; Schenthal, Kyle B; Overman, Larry E

    2016-03-18

    Strategies for the total synthesis of complex natural products that contain two or more contiguous stereogenic quaternary carbon atoms in their intricate structures are reviewed with 12 representative examples. Emphasis has been put on methods to create quaternary carbon stereocenters, including syntheses of the same natural product by different groups, thereby showcasing the diversity of thought and individual creativity. A compendium of selected natural products containing two or more contiguous stereogenic quaternary carbon atoms and key reactions in their total or partial syntheses is provided in the Supporting Information.

  13. Production of complex organic molecules:H-atom addition versus UV irradiation

    NASA Astrophysics Data System (ADS)

    Chuang, K.-J.; Fedoseev, G.; Qasim, D.; Ioppolo, S.; van Dishoeck, E. F.; Linnartz, H.

    2017-01-01

    Complex organic molecules (COMs) have been identified in different environments in star-forming regions. Laboratory studies show that COMs form in the solid state, on icy grains, typically following a `non-energetic' (atom-addition) or `energetic' (UV photon absorption) trigger. So far, such studies have been largely performed for single processes. Here we present the first work that quantitatively investigates both the relative importance and the cumulative effect of `(non)energetic' processing. We focus on astronomically relevant CO:CH3OH = 4:1 ice analogues exposed to doses relevant for the collapse stage of dense clouds. Hydrogenation experiments result in the formation of methyl formate (MF; HC(O)OCH3), glycolaldehyde (GA; HC(O)CH2OH) and ethylene glycol (EG; H2C(OH)CH2OH) at 14 K. The absolute abundances and the abundance fractions are found to be dependent on the H-atom/CO:CH3OH-molecule ratios and on the overall deposition rate. In the case that ices are exposed to UV photons only, several different COMs are found. Typically, the abundance fractions are 0.2 for MF, 0.3 for GA, and 0.5 for EG as opposed to the values found in pure hydrogenation experiments without UV in which MF is largely absent: 0.0, 0.2-0.6 and 0.8-0.4, respectively. In experiments where both are applied, overall COM abundances drop to about half of those found in the pure UV irradiation experiments, but the composition fractions are very similar. This implies COM ratios can be used as a diagnostic tool to derive the processing history of an ice. Solid-state branching ratios derived here for GA and EG compare well with observations, while the MF case cannot be explained by solid state conditions investigated here.

  14. Pairwise additivity in the nuclear magnetic resonance interactions of atomic xenon.

    PubMed

    Hanni, Matti; Lantto, Perttu; Vaara, Juha

    2009-04-14

    Nuclear magnetic resonance (NMR) of atomic (129/131)Xe is used as a versatile probe of the structure and dynamics of various host materials, due to the sensitivity of the Xe NMR parameters to intermolecular interactions. The principles governing this sensitivity can be investigated using the prototypic system of interacting Xe atoms. In the pairwise additive approximation (PAA), the binary NMR chemical shift, nuclear quadrupole coupling (NQC), and spin-rotation (SR) curves for the xenon dimer are utilized for fast and efficient evaluation of the corresponding NMR tensors in small xenon clusters Xe(n) (n = 2-12). If accurate, the preparametrized PAA enables the analysis of the NMR properties of xenon clusters, condensed xenon phases, and xenon gas without having to resort to electronic structure calculations of instantaneous configurations for n > 2. The binary parameters for Xe(2) at different internuclear distances were obtained at the nonrelativistic Hartree-Fock level of theory. Quantum-chemical (QC) calculations at the corresponding level were used to obtain the NMR parameters of the Xe(n) (n = 2-12) clusters at the equilibrium geometries. Comparison of PAA and QC data indicates that the direct use of the binary property curves of Xe(2) can be expected to be well-suited for the analysis of Xe NMR in the gaseous phase dominated by binary collisions. For use in condensed phases where many-body effects should be considered, effective binary property functions were fitted using the principal components of QC tensors from Xe(n) clusters. Particularly, the chemical shift in Xe(n) is strikingly well-described by the effective PAA. The coordination number Z of the Xe site is found to be the most important factor determining the chemical shift, with the largest shifts being found for high-symmetry sites with the largest Z. This is rationalized in terms of the density of virtual electronic states available for response to magnetic perturbations.

  15. A nine-atom rhodium–aluminum oxide cluster oxidizes five carbon monoxide molecules

    PubMed Central

    Li, Xiao-Na; Zhang, Hua-Min; Yuan, Zhen; He, Sheng-Gui

    2016-01-01

    Noble metals can promote the direct participation of lattice oxygen of very stable oxide materials such as aluminum oxide, to oxidize reactant molecules, while the fundamental mechanism of noble metal catalysis is elusive. Here we report that a single atom of rhodium, a powerful noble metal catalyst, can promote the transfer of five oxygen atoms to oxidize carbon monoxide from a nine-atom rhodium–aluminum oxide cluster. This is a sharp improvement in the field of cluster science where the transfer of at most two oxygen atoms from a doped cluster is more commonly observed. Rhodium functions not only as the preferred trapping site to anchor and oxidize carbon monoxide by the oxygen atoms in direct connection with rhodium but also the primarily oxidative centre to accumulate the large amounts of electrons and the polarity of rhodium is ultimately transformed from positive to negative. PMID:27094921

  16. Study on nitrogen doped carbon atom chains with negative differential resistance effect

    NASA Astrophysics Data System (ADS)

    Shen, Ji-Mei; Liu, Jing; Min, Yi; Zhou, Li-Ping

    2016-05-01

    Recent calculations (Mahmoud and Lugli, 2013, [21]) of gold leads sandwiching carbon chains which are separated by diphenyl-dimethyl demonstrated that the negative differential resistance (NDR) effect appears only for ;odd; numbers of carbon atoms. In this paper, according to a first-principles study based on non-equilibrium Green's function combining density functional theory, we find that the NDR effect appears both for ;odd; and for ;even; numbers of carbon atoms when the chains are doped by nitrogen atom. Our calculations remove the restriction of ;odd/even; chains for the NDR effect, which may promise the potential applications of carbon chains in the nano-scale or molecular devices in the future.

  17. Response of annual grassland carbon cycling to experimental rainfall additions

    NASA Astrophysics Data System (ADS)

    Chou, W. W.; Silver, W. L.; Allen-Diaz, B.; Thompson, A.; Jackson, R.

    2006-12-01

    Annual grassland ecosystems are likely to be sensitive to changes in the timing and amount of rainfall, with important implications for climate feedback effects. Many climate models have forecasted rainfall increases for northern California over the next century. We hypothesized that increased rainfall in annual grasslands would increase soil respiration and decrease soil carbon (C) storage. Using microsprinklers, we augmented wet- season (typically November to April) rain events by 50 %, and each year, we added an early-season and a late-season rainfall event to extend wet-season length. Control plots received ambient rainfall only. We measured soil respiration and net primary production over three water years (defined as September to August) to estimate the net change in the soil C pool. The added early- and late-season rain events significantly increased soil respiration for three to four weeks after wetting, but did not significantly increase C respired per year. Soil respiration was not significantly increased by 50 % augmentation of wet-season rainfall over the study. An ANOVA of annual respiration from control plots showed significantly more respired carbon (F = 8.157, p = 0.02) in water year 2004 (WY 04; 1452 ± 152 g m-2 y-1), compared to WY 03 or WY 05 (998 ± 40 and 925 ± 71 g m-2 y-1, respectively). Greater soil respiration in WY 04 resulted not from higher annual rainfall totals, but from unusually late natural storms which occurred under warm summer conditions. Relative to controls, grass in treatment plots allocated more C to roots in the first (drier) year, and slightly more C to shoots in the second (wetter) year. Combined above- and below-ground net primary production was greater in WY04 (913 ± 171 g m-2 y-1 and 668 ± 93 g m-2 y-1 for treatment and control plots, respectively) than in WY03 (588 ± 85 g m-2 y-1 and 483 ± 46 g m-2 y-1 for treatment and controls, respectively), partly offsetting increased C losses from respiration. Our results

  18. Stabilizing Nanosized Si Anodes with the Synergetic Usage of Atomic Layer Deposition and Electrolyte Additives for Li-Ion Batteries.

    PubMed

    Hy, Sunny; Chen, Yi-Hsiu; Cheng, Ho-Ming; Pan, Chun-Jern; Cheng, Ju-Hsiang; Rick, John; Hwang, Bing-Joe

    2015-07-01

    A substantial increase in charging capacity over long cycle periods was made possible by the formation of a flexible weblike network via the combination of Al2O3 atomic layer deposition (ALD) and the electrolyte additive vinylene carbonate (VC). Transmission electron microscopy shows that a weblike network forms after cycling when ALD and VC were used in combination that dramatically increases the cycle stability for the Si composite anode. The ALD-VC combination also showed reduced reactions with the lithium salt, forming a more stable solid electrolyte interface (SEI) absent of fluorinated silicon species, as evidenced by X-ray photoelectron spectroscopy. Although the bare Si composite anode showed only an improvement from a 56% to a 45% loss after 50 cycles, when VC was introduced, the ALD-coated Si anode showed an improvement from a 73% to a 11% capacity loss. Furthermore, the anode with the ALD coating and VC had a capacity of 630 mAh g(-1) after 200 cycles running at 200 mA g(-1), and the bare anode without VC showed a capacity of 400 mAh g(-1) after only 50 cycles. This approach can be extended to other Si systems, and the formation of this SEI is dependent on the thickness of the ALD that affects both capacity and stability.

  19. Quantum-chemical model evaluations of thermodynamics and kinetics of oxygen atom additions to narrow nanotubes.

    PubMed

    Slanina, Zdenĕk; Stobinski, Leszek; Tomasik, Piotr; Lin, Hong-Ming; Adamowicz, Ludwik

    2003-01-01

    This paper reports a computational study of oxygen additions to narrow nanotubes, a problem frequently studied with fullerenes. In fact, fullerene oxides were the first observed fullerene derivatives, and they have naturally attracted the attention of both experiment and theory. C60O had represented a long-standing case of experiment-theory disagreement, and there has been a similar problem with C60O2. The disagreement has been explained by kinetic rather than thermodynamic control. In this paper a similar computational approach is applied to narrow nanotubes. Recently, very narrow nanotubes have been observed with a diameter of 5 A and even with a diameter of 4 A. It has been supposed that the narrow nanotubes are closed by fragments of small fullerenes like C36 or C20. In this report we perform calculations for oxygen additions to such model nanotubes capped by fragments of D2d C36, D4d C32, and Ih C20 fullerenic cages (though the computational models have to be rather short). The three models have the following carbon contents: C84, C80, and C80. Both thermodynamic enthalpy changes and kinetic activation barriers for oxygen addition to six selected bonds are computed and analyzed. The lowest isomer (thermodynamically the most stable) is never of the 6/6 type, that is, the enthalpically favored structures are produced by oxygen additions to the nanotube tips. Interestingly enough, the lowest energy isomer has, for the D2d C36 and D4d C32 cases, the lowest kinetic activation barrier as well.

  20. Migration Mechanism for Atomic Hydrogen in Porous Carbon Materials

    SciTech Connect

    Narayanan, B.; Zhao, Y. F.; Ciobanu, C. V.

    2012-05-14

    To explain the fast kinetics of H in porous carbon, we propose that the migration relies on H hopping from a carbon nanotube (CNT) to another. Using density functional theory, we have found that the barrier for H hopping becomes smaller than that for diffusion along a tube for certain CNT separations, decreasting to less than 0.5 eV for separations of -3.1 {angstrom}. Such significant reduction occurs irrespective of radius, chirality, registry, and orientation of the two CNTs: the diffusion is thus facilitated by the porous nature of the material itself. The mechanism proposed is applicable for any porous carbon-based nanomaterials.

  1. Insights into hydrogen atom adsorption on and the electrochemical properties of nitrogen-substituted carbon materials.

    PubMed

    Zhu, Z H; Hatori, H; Wang, S B; Lu, G Q

    2005-09-08

    The nitrogen substitution in carbon materials is investigated theoretically using the density functional theory method. Our calculations show that nitrogen substitution decreases the hydrogen adsorption energy if hydrogen atoms are adsorbed on both nitrogen atoms and the neighboring carbon atoms. On the contrary, the hydrogen adsorption energy can be increased if hydrogen atoms are adsorbed only on the neighboring carbon atoms. The reason can be explained by the electronic structures analysis of N-substituted graphene sheets. Nitrogen substitution reduces the pi electron conjugation and increases the HOMO energy of a graphene sheet, and the nitrogen atom is not stable due to its 3-valent character. This raises an interesting research topic on the optimization of the N-substitution degree, and is important to many applications such as hydrogen storage and the tokamaks device. The electronic structure studies also explain well why nitrogen substitution increases the capacitance but decreases the electron conductivity of carbon electrodes as was experimentally observed in our experiments on the supercapacitor.

  2. Highly oriented carbon fiber–polymer composites via additive manufacturing

    SciTech Connect

    Tekinalp, Halil L.; Kunc, Vlastimil; Velez-Garcia, Gregorio M.; Duty, Chad E.; Love, Lonnie J.; Naskar, Amit K.; Blue, Craig A.; Ozcan, Soydan

    2014-10-16

    Additive manufacturing, diverging from traditional manufacturing techniques, such as casting and machining materials, can handle complex shapes with great design flexibility without the typical waste. Although this technique has been mainly used for rapid prototyping, interest is growing in using this method to directly manufacture actual parts of complex shape. To use 3D-printing additive manufacturing in wide spread applications, the technique and the feedstock materials require improvements to meet the mechanical requirements of load-bearing components. Thus, we investigated the short fiber (0.2 mm to 0.4 mm) reinforced acrylonitrile-butadiene-styrene composites as a feedstock for 3D-printing in terms of their processibility, microstructure and mechanical performance; and also provided comparison with traditional compression molded composites. The tensile strength and modulus of 3D-printed samples increased ~115% and ~700%, respectively. 3D-printer yielded samples with very high fiber orientation in printing direction (up to 91.5 %), whereas, compression molding process yielded samples with significantly less fiber orientation. Microstructure-mechanical property relationships revealed that although the relatively high porosity is observed in the 3D-printed composites as compared to those produced by the conventional compression molding technique, they both exhibited comparable tensile strength and modulus. Furthermore, this phenomena is explained based on the changes in fiber orientation, dispersion and void formation.

  3. Highly oriented carbon fiber–polymer composites via additive manufacturing

    DOE PAGES

    Tekinalp, Halil L.; Kunc, Vlastimil; Velez-Garcia, Gregorio M.; ...

    2014-10-16

    Additive manufacturing, diverging from traditional manufacturing techniques, such as casting and machining materials, can handle complex shapes with great design flexibility without the typical waste. Although this technique has been mainly used for rapid prototyping, interest is growing in using this method to directly manufacture actual parts of complex shape. To use 3D-printing additive manufacturing in wide spread applications, the technique and the feedstock materials require improvements to meet the mechanical requirements of load-bearing components. Thus, we investigated the short fiber (0.2 mm to 0.4 mm) reinforced acrylonitrile-butadiene-styrene composites as a feedstock for 3D-printing in terms of their processibility, microstructuremore » and mechanical performance; and also provided comparison with traditional compression molded composites. The tensile strength and modulus of 3D-printed samples increased ~115% and ~700%, respectively. 3D-printer yielded samples with very high fiber orientation in printing direction (up to 91.5 %), whereas, compression molding process yielded samples with significantly less fiber orientation. Microstructure-mechanical property relationships revealed that although the relatively high porosity is observed in the 3D-printed composites as compared to those produced by the conventional compression molding technique, they both exhibited comparable tensile strength and modulus. Furthermore, this phenomena is explained based on the changes in fiber orientation, dispersion and void formation.« less

  4. Molecular dynamics simulation for arrangement of nickel atoms filled in carbon nanotubes

    SciTech Connect

    Bai, Liu Zhenyu, Zhao; Lirui, Liu

    2014-08-28

    Carbon Nanotubes (CNTs) filled with metals can be used in capacitors, sensors, rechargeable batteries, and so on. Atomic arrangement of the metals has an important role in the function of the composites. The tips of CNTs were opened, and then nickel was filled by means of hydrothermal oxidation/ultrasonic vibration method. The tests of TEM, HREM, and EDX (energy-dispersive X-ray spectroscopy) analysis showed that Ni was filled in CNTs successfully. The atomic arrangement of nickel filled into single wall carbon nanotubes was investigated by molecular dynamics simulation. The radial distribution function and bond orientation order were established to analyze the atomic arrangement of nickel filled in carbon nanotubes during the cooling process. The results show that nickel atoms became in order gradually and preferably crystallized on the inner wall of carbon nanotubes when the temperature decreased from 1600 K. After it cooled to 100 K, the arrangement of nickel atoms in outermost circle was regular and dense, but there were many defects far from the wall of CNTs. According to the calculation of bond orientation order parameters Q{sub 6} and its visualization, the structure of nickel is Face-centered cube (f.c.c). (1,1,1){sub Ni} was close on the inner surface of carbon nanotubes. Radial direction of CNTs was [1,1,1] crystal orientation. Axial direction of CNTs, namely, filling direction, was [1{sup ¯}, 1{sup ¯},2] crystal orientation.

  5. Molecular dynamics simulation for arrangement of nickel atoms filled in carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Bai, Liu; Lirui, Liu; Zhenyu, Zhao

    2014-08-01

    Carbon Nanotubes (CNTs) filled with metals can be used in capacitors, sensors, rechargeable batteries, and so on. Atomic arrangement of the metals has an important role in the function of the composites. The tips of CNTs were opened, and then nickel was filled by means of hydrothermal oxidation/ultrasonic vibration method. The tests of TEM, HREM, and EDX (energy-dispersive X-ray spectroscopy) analysis showed that Ni was filled in CNTs successfully. The atomic arrangement of nickel filled into single wall carbon nanotubes was investigated by molecular dynamics simulation. The radial distribution function and bond orientation order were established to analyze the atomic arrangement of nickel filled in carbon nanotubes during the cooling process. The results show that nickel atoms became in order gradually and preferably crystallized on the inner wall of carbon nanotubes when the temperature decreased from 1600 K. After it cooled to 100 K, the arrangement of nickel atoms in outermost circle was regular and dense, but there were many defects far from the wall of CNTs. According to the calculation of bond orientation order parameters Q6 and its visualization, the structure of nickel is Face-centered cube (f.c.c). (1,1,1)Ni was close on the inner surface of carbon nanotubes. Radial direction of CNTs was [1,1,1] crystal orientation. Axial direction of CNTs, namely, filling direction, was [1¯, 1¯,2] crystal orientation.

  6. Strain-induced metal–semiconductor transition observed in atomic carbon chains

    PubMed Central

    La Torre, A.; Botello-Mendez, A.; Baaziz, W.; Charlier, J. -C.; Banhart, F.

    2015-01-01

    Carbyne, the sp1-hybridized phase of carbon, is still a missing link in the family of carbon allotropes. While the bulk phases of carbyne remain elusive, the elementary constituents, that is, linear chains of carbon atoms, have already been observed using the electron microscope. Isolated atomic chains are highly interesting one-dimensional conductors that have stimulated considerable theoretical work. Experimental information, however, is still very limited. Here we show electrical measurements and first-principles transport calculations on monoatomic carbon chains. When the 1D system is under strain, the chains are semiconducting corresponding to the polyyne structure with alternating bond lengths. Conversely, when the chain is unstrained, the ohmic behaviour of metallic cumulene with uniform bond lengths is observed. This confirms the recent prediction of a metal–insulator transition that is induced by strain. The key role of the contacting leads explains the rectifying behaviour measured in monoatomic carbon chains in a nonsymmetric contact configuration. PMID:25818506

  7. Strain-induced metal-semiconductor transition observed in atomic carbon chains

    NASA Astrophysics Data System (ADS)

    La Torre, A.; Botello-Mendez, A.; Baaziz, W.; Charlier, J.-C.; Banhart, F.

    2015-03-01

    Carbyne, the sp1-hybridized phase of carbon, is still a missing link in the family of carbon allotropes. While the bulk phases of carbyne remain elusive, the elementary constituents, that is, linear chains of carbon atoms, have already been observed using the electron microscope. Isolated atomic chains are highly interesting one-dimensional conductors that have stimulated considerable theoretical work. Experimental information, however, is still very limited. Here we show electrical measurements and first-principles transport calculations on monoatomic carbon chains. When the 1D system is under strain, the chains are semiconducting corresponding to the polyyne structure with alternating bond lengths. Conversely, when the chain is unstrained, the ohmic behaviour of metallic cumulene with uniform bond lengths is observed. This confirms the recent prediction of a metal-insulator transition that is induced by strain. The key role of the contacting leads explains the rectifying behaviour measured in monoatomic carbon chains in a nonsymmetric contact configuration.

  8. Additives

    NASA Technical Reports Server (NTRS)

    Smalheer, C. V.

    1973-01-01

    The chemistry of lubricant additives is discussed to show what the additives are chemically and what functions they perform in the lubrication of various kinds of equipment. Current theories regarding the mode of action of lubricant additives are presented. The additive groups discussed include the following: (1) detergents and dispersants, (2) corrosion inhibitors, (3) antioxidants, (4) viscosity index improvers, (5) pour point depressants, and (6) antifouling agents.

  9. Racing carbon atoms. Atomic motion reaction coordinates and structural effects on Newtonian kinetic isotope effects.

    PubMed

    Andujar-De Sanctis, Ivonne L; Singleton, Daniel A

    2012-10-19

    Intramolecular (13)C kinetic isotope effects were determined for the dimerization of methacrolein. Trajectory studies accurately predict the isotope effects and support an origin in Newton's second law of motion, with no involvement of zero-point energy or transition state recrossing. Atomic motion reaction coordinate diagrams are introduced as a way to qualitatively understand the selectivity.

  10. Integrating Carbon Nanotubes For Atomic Force Microscopy Imaging Applications

    NASA Technical Reports Server (NTRS)

    Ye, Qi; Cassell, Alan M.; Liu, Hongbing; Han, Jie; Meyyappan, Meyya

    2004-01-01

    Carbon nanotube (CNT) related nanostructures possess remarkable electrical, mechanical, and thermal properties. To produce these nanostructures for real world applications, a large-scale controlled growth of carbon nanotubes is crucial for the integration and fabrication of nanodevices and nanosensors. We have taken the approach of integrating nanopatterning and nanomaterials synthesis with traditional silicon micro fabrication techniques. This integration requires a catalyst or nanomaterial protection scheme. In this paper, we report our recent work on fabricating wafer-scale carbon nanotube AFM cantilever probe tips. We will address the design and fabrication considerations in detail, and present the preliminary scanning probe test results. This work may serve as an example of rational design, fabrication, and integration of nanomaterials for advanced nanodevice and nanosensor applications.

  11. Synthesis of novel amorphous calcium carbonate by sono atomization for reactive mixing.

    PubMed

    Kojima, Yoshiyuki; Kanai, Makoto; Nishimiya, Nobuyuki

    2012-03-01

    Droplets of several micrometers in size can be formed in aqueous solution by atomization under ultrasonic irradiation at 2 MHz. This phenomenon, known as atomization, is capable of forming fine droplets for use as a reaction field. This synthetic method is called SARM (sono atomization for reactive mixing). This paper reports on the synthesis of a novel amorphous calcium carbonate formed by SARM. The amorphous calcium carbonate, obtained at a solution concentration of 0.8 mol/dm(3), had a specific surface area of 65 m(2)/g and a composition of CaCO(3)•0.5H(2)O as determined using thermogravimetric/differential thermal analysis (TG-DTA). Because the ACC had a lower hydrate composition than conventional amorphous calcium carbonate (ACC), the ACC synthesized in this paper was very stable at room temperature.

  12. High performance current and spin diode of atomic carbon chain between transversely symmetric ribbon electrodes

    PubMed Central

    Dong, Yao-Jun; Wang, Xue-Feng; Yang, Shuo-Wang; Wu, Xue-Mei

    2014-01-01

    We demonstrate that giant current and high spin rectification ratios can be achieved in atomic carbon chain devices connected between two symmetric ferromagnetic zigzag-graphene-nanoribbon electrodes. The spin dependent transport simulation is carried out by density functional theory combined with the non-equilibrium Green's function method. It is found that the transverse symmetries of the electronic wave functions in the nanoribbons and the carbon chain are critical to the spin transport modes. In the parallel magnetization configuration of two electrodes, pure spin current is observed in both linear and nonlinear regions. However, in the antiparallel configuration, the spin-up (down) current is prohibited under the positive (negative) voltage bias, which results in a spin rectification ratio of order 104. When edge carbon atoms are substituted with boron atoms to suppress the edge magnetization in one of the electrodes, we obtain a diode with current rectification ratio over 106. PMID:25142376

  13. Effects of aluminum additions to gas atomized reaction synthesis produced oxide dispersion strengthened alloys

    NASA Astrophysics Data System (ADS)

    Spicher, Alexander Lee

    The production of an aluminum containing ferritic oxide dispersion strengthened (ODS) alloy was investigated. The production method used in this study was gas atomization reaction synthesis (GARS). GARS was chosen over the previously commercial method of mechanical alloying (MA) process due to complications from this process. The alloy compositions was determined from three main components; corrosion resistance, dispersoid formation, and additional elements. A combination of Cr and Al were necessary in order to create a protective oxide in the steam atmosphere that the boiler tubing in the next generation of coal-fired power plants would be exposed to. Hf and Y were chosen as dispersoid forming elements due to their increased thermal stability and potential to avoid decreased strength caused by additions of Al to traditional ODS materials. W was used as an additive due to benefits as a strengthener as well as its benefits for creep rupture time. The final composition chosen for the alloy was Fe-16Cr-12Al-0.9W-0.25Hf-0.2Y at%. The aforementioned alloy, GA-1-198, was created through gas atomization with atomization gas of Ar-300ppm O2. The actual composition created was found to be Fe-15Cr-12.3Al-0.9W-0.24Hf-0.19Y at%. An additional alloy that was nominally the same without the inclusion of aluminum was created as a comparison for the effects on mechanical and corrosion properties. The actual composition of the comparison alloy, GA-1-204, was Fe-16Cr-0Al-0.9W-0.25Hf-0.24Y at%. An investigation on the processing parameters for these alloys was conducted on the GA-1-198 alloy. In order to predict the necessary amount of time for heat treatment, a diffusion study was used to find the diffusion rate of oxygen in cast alloys with similar composition. The diffusion rate was found to be similar to that of other GARS compositions that have been created without the inclusion of aluminum. The effect of heat treatment time was investigated with temperatures of 950°C, 1000

  14. Single Atom (Pd/Pt) Supported on Graphitic Carbon Nitride as an Efficient Photocatalyst for Visible-Light Reduction of Carbon Dioxide.

    PubMed

    Gao, Guoping; Jiao, Yan; Waclawik, Eric R; Du, Aijun

    2016-05-18

    Reducing carbon dioxide to hydrocarbon fuel with solar energy is significant for high-density solar energy storage and carbon balance. In this work, single atoms of palladium and platinum supported on graphitic carbon nitride (g-C3N4), i.e., Pd/g-C3N4 and Pt/g-C3N4, respectively, acting as photocatalysts for CO2 reduction were investigated by density functional theory calculations for the first time. During CO2 reduction, the individual metal atoms function as the active sites, while g-C3N4 provides the source of hydrogen (H*) from the hydrogen evolution reaction. The complete, as-designed photocatalysts exhibit excellent activity in CO2 reduction. HCOOH is the preferred product of CO2 reduction on the Pd/g-C3N4 catalyst with a rate-determining barrier of 0.66 eV, while the Pt/g-C3N4 catalyst prefers to reduce CO2 to CH4 with a rate-determining barrier of 1.16 eV. In addition, deposition of atom catalysts on g-C3N4 significantly enhances the visible-light absorption, rendering them ideal for visible-light reduction of CO2. Our findings open a new avenue of CO2 reduction for renewable energy supply.

  15. Carbon materials as additives to WO3 for an enhanced conversion of simulated solar light

    NASA Astrophysics Data System (ADS)

    Carmona, Rocío; Velasco, Leticia; Laurenti, Enzo; Maurino, Valter; Ania, Conchi

    2016-02-01

    We have explored the impact of the incorporation of nanoporous carbons as additives to tungsten oxide on the photocatalytic degradation of two recalcitrant pollutants: rhodamine B and phenol, under simulated solar light. For this purpose, WO3/carbon mixtures were prepared using three carbon materials with different properties (in terms of porosity, structural order and surface chemistry). Despite the low carbon content used (2 wt. %), a significant increase in the photocatalytic performance of the semiconductor was observed for all the catalysts. Moreover, the influence of the carbon additive on the performance of the photocatalysts was found to be very different for the two pollutants. Carbon additives of hydrophobic nature increased the photodegradation yield of phenol compared to bare WO3, likely due to the higher affinity and stronger interactions of phenol molecules towards basic nanoporous carbons. Oppositely, the use of acidic carbon additives led to higher rhodamine B conversions due to increased acidity of the WO3/carbon mixtures and the stronger affinity of the pollutant for acidic catalyst’s surfaces. As a result, the photooxidation of rhodamine B is favored by means of a coupled (photosensitized and photocatalytic) degradation mechanism. All these results highlight the importance of favoring the interactions of the pollutant with the catalyst’s surface through a detailed design of the features of the photocatalyst.

  16. Shining Light on Copper: Unique Opportunities for Visible-Light-Catalyzed Atom Transfer Radical Addition Reactions and Related Processes.

    PubMed

    Reiser, Oliver

    2016-09-20

    Visible-light photoredox catalysis offers exciting opportunities to achieve challenging carbon-carbon bond formations under mild and ecologically benign conditions. Desired features of photoredox catalysts are photostability, long excited-state lifetimes, strong absorption in the visible region, and high reduction or oxidation potentials to achieve electron transfer to substrates, thus generating radicals that can undergo synthetic organic transformations. These requirements are met in a convincing way by Ru(II)(phenanthroline)3- and Ir(III)(phenylpyridine)3-type complexes and, as a low-cost alternative, by organic dyes that offer a metal-free catalyst but suffer in general from lower photostability. Cu(I)(phenanthroline)2 complexes have been recognized for more than 30 years as photoresponsive compounds with highly negative Cu(I)* → Cu(II) oxidation potentials, but nevertheless, they have not been widely considered as suitable photoredox catalysts, mainly because their excited lifetimes are shorter by a factor of 5 to 10 compared with Ru(II) and Ir(III) complexes, their absorption in the visible region is weak, and their low Cu(II) → Cu(I) reduction potentials might impede the closure of a catalytic cycle for a given process. Contrasting again with Ru(II)L3 and Ir(III)L3 complexes, Cu(I)L2 assemblies undergo more rapid ligand exchange in solution, thus potentially reducing the concentration of the photoactive species. Focusing on atom transfer radical addition (ATRA) reactions and related processes, we highlight recent developments that show the utility of Cu(I)(phenanthroline)2 complexes as photoredox catalysts, demonstrating that despite their short excited-state lifetimes and weak absorption such complexes are efficient at low catalyst loadings. Moreover, some of the inherent disadvantages stated above can even be turned to advantages: (1) the low Cu(II) → Cu(I) reduction potential might efficiently promote reactions via a radical chain pathway, and (2

  17. Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock

    DOEpatents

    Narula, Chaitanya K.; Davison, Brian H.

    2015-11-13

    A method for producing a hydrocarbon blendstock, the method comprising contacting at least one saturated acyclic alcohol having at least three and up to ten carbon atoms with a metal-loaded zeolite catalyst at a temperature of at least 100°C and up to 550°C, wherein the metal is a positively-charged metal ion, and the metal-loaded zeolite catalyst is catalytically active for converting the alcohol to the hydrocarbon blendstock, wherein the method directly produces a hydrocarbon blendstock having less than 1 vol % ethylene and at least 35 vol % of hydrocarbon compounds containing at least eight carbon atoms.

  18. The influence of the atomic structure of basal planes on interplanar distance in pyrolytic carbon materials

    NASA Astrophysics Data System (ADS)

    Borgardt, N. I.; Prihodko, A. S.; Seibt, M.

    2016-12-01

    The atomic structure of carbon materials is studied using the example of pyrocarbon and boronrich pyrocarbon by means of the method of reconstruction of the wave function in transmission electron microscopy. It is shown that the digital processing of the phase distributions of these functions allows us to find the average distance between the basal planes. Using the method of molecular dynamics for the formation of the test structures and obtaining for them the calculated phase distributions, the effect of depletion of the basal planes of the carbon atoms on the interplanar distance in the pyrocarbon materials is quantified.

  19. Graphene as conductive additives in binderless activated carbon electrodes for power enhancement of supercapacitor

    NASA Astrophysics Data System (ADS)

    Nor, N. S. M.; Deraman, M.; Suleman, M.; Norizam, M. D. M.; Basri, N. H.; Sazali, N. E. S.; Hamdan, E.; Hanappi, M. F. Y. M.; Tajuddin, N. S. M.; Othman, M. A. R.; Shamsudin, S. A.; Omar, R.

    2016-11-01

    Carbon based supercapacitor electrodes from composite of binderless activated carbon and graphene as a conductive additive were fabricated with various amount of graphene (0, 2, 4, 6, 8 and 10 wt%). Graphene was mixed in self-adhesive carbon grains produced from pre-carbonized powder derived from fibers of oil palm empty fruit bunches and converted into green monoliths (GMs). The GMs were carbonized (N2) and activated (CO2) to produce activated carbon monoliths (ACMs) electrodes. Porosity characterizations by nitrogen adsorption-desorption isotherm method shows that the pore characteristics of the ACMs are influenced by the graphene additive. The results of galvanostatic charge-discharge tests carried out on the supercapacitor cells fabricated using these electrodes shows that the addition of graphene additive (even in small amount) decreases the equivalent series resistance and enhances the specific power of the cells but significantly lowers the specific capacitance. The supercapacitor cell constructed with the electrode containing 4 wt % of graphene offers the maximum power (175 W kg-1) which corresponds to an improvement of 55%. These results demonstrate that the addition of graphene as conductive additive in activated carbon electrodes can enhance the specific power of the supercapacitor.

  20. Coke formation and carbon atom economy of methanol-to-olefins reaction.

    PubMed

    Wei, Yingxu; Yuan, Cuiyu; Li, Jinzhe; Xu, Shutao; Zhou, You; Chen, Jingrun; Wang, Quanyi; Xu, Lei; Qi, Yue; Zhang, Qing; Liu, Zhongmin

    2012-05-01

    The methanol-to-olefins (MTO) process is becoming the most important non-petrochemical route for the production of light olefins from coal or natural gas. Maximizing the generation of the target products, ethene and propene, and minimizing the production of byproducts and coke, are major considerations in the efficient utilization of the carbon resource of methanol. In the present work, the heterogeneous catalytic conversion of methanol was evaluated by performing simultaneous measurements of the volatile products generated in the gas phase and the confined coke deposition in the catalyst phase. Real-time and complete reaction profiles were plotted to allow the comparison of carbon atom economy of methanol conversion over the catalyst SAPO-34 at varied reaction temperatures. The difference in carbon atom economy was closely related with the coke formation in the SAPO-34 catalyst. The confined coke compounds were determined. A new type of confined organics was found, and these accounted for the quick deactivation and low carbon atom economy under low-reaction-temperature conditions. Based on the carbon atom economy evaluation and coke species determination, optimized operating conditions for the MTO process are suggested; these conditions guarantee high conversion efficiency of methanol.

  1. Atomically isolated nickel species anchored on graphitized carbon for efficient hydrogen evolution electrocatalysis

    NASA Astrophysics Data System (ADS)

    Fan, Lili; Liu, Peng Fei; Yan, Xuecheng; Gu, Lin; Yang, Zhen Zhong; Yang, Hua Gui; Qiu, Shilun; Yao, Xiangdong

    2016-02-01

    Hydrogen production through electrochemical process is at the heart of key renewable energy technologies including water splitting and hydrogen fuel cells. Despite tremendous efforts, exploring cheap, efficient and durable electrocatalysts for hydrogen evolution still remains as a great challenge. Here we synthesize a nickel-carbon-based catalyst, from carbonization of metal-organic frameworks, to replace currently best-known platinum-based materials for electrocatalytic hydrogen evolution. This nickel-carbon-based catalyst can be activated to obtain isolated nickel atoms on the graphitic carbon support when applying electrochemical potential, exhibiting highly efficient hydrogen evolution performance with high exchange current density of 1.2 mA cm-2 and impressive durability. This work may enable new opportunities for designing and tuning properties of electrocatalysts at atomic scale for large-scale water electrolysis.

  2. Atomically isolated nickel species anchored on graphitized carbon for efficient hydrogen evolution electrocatalysis

    PubMed Central

    Fan, Lili; Liu, Peng Fei; Yan, Xuecheng; Gu, Lin; Yang, Zhen Zhong; Yang, Hua Gui; Qiu, Shilun; Yao, Xiangdong

    2016-01-01

    Hydrogen production through electrochemical process is at the heart of key renewable energy technologies including water splitting and hydrogen fuel cells. Despite tremendous efforts, exploring cheap, efficient and durable electrocatalysts for hydrogen evolution still remains as a great challenge. Here we synthesize a nickel–carbon-based catalyst, from carbonization of metal-organic frameworks, to replace currently best-known platinum-based materials for electrocatalytic hydrogen evolution. This nickel-carbon-based catalyst can be activated to obtain isolated nickel atoms on the graphitic carbon support when applying electrochemical potential, exhibiting highly efficient hydrogen evolution performance with high exchange current density of 1.2 mA cm−2 and impressive durability. This work may enable new opportunities for designing and tuning properties of electrocatalysts at atomic scale for large-scale water electrolysis. PMID:26861684

  3. Dynamics of carbon-hydrogen and carbon-methyl exchanges in the collision of {sup 3}P atomic carbon with propene

    SciTech Connect

    Lee, Shih-Huang Chen, Wei-Kan; Chin, Chih-Hao; Huang, Wen-Jian

    2013-11-07

    We investigated the dynamics of the reaction of {sup 3}P atomic carbon with propene (C{sub 3}H{sub 6}) at reactant collision energy 3.8 kcal mol{sup −1} in a crossed molecular-beam apparatus using synchrotron vacuum-ultraviolet ionization. Products C{sub 4}H{sub 5}, C{sub 4}H{sub 4}, C{sub 3}H{sub 3}, and CH{sub 3} were observed and attributed to exit channels C{sub 4}H{sub 5} + H, C{sub 4}H{sub 4} + 2H, and C{sub 3}H{sub 3} + CH{sub 3}; their translational-energy distributions and angular distributions were derived from the measurements of product time-of-flight spectra. Following the addition of a {sup 3}P carbon atom to the C=C bond of propene, cyclic complex c-H{sub 2}C(C)CHCH{sub 3} undergoes two separate stereoisomerization mechanisms to form intermediates E- and Z-H{sub 2}CCCHCH{sub 3}. Both the isomers of H{sub 2}CCCHCH{sub 3} in turns decompose to C{sub 4}H{sub 5} + H and C{sub 3}H{sub 3} + CH{sub 3}. A portion of C{sub 4}H{sub 5} that has enough internal energy further decomposes to C{sub 4}H{sub 4} + H. The three exit channels C{sub 4}H{sub 5} + H, C{sub 4}H{sub 4} + 2H, and C{sub 3}H{sub 3} + CH{sub 3} have average translational energy releases 13.5, 3.2, and 15.2 kcal mol{sup −1}, respectively, corresponding to fractions 0.26, 0.41, and 0.26 of available energy deposited to the translational degrees of freedom. The H-loss and 2H-loss channels have nearly isotropic angular distributions with a slight preference at the forward direction particularly for the 2H-loss channel. In contrast, the CH{sub 3}-loss channel has a forward and backward peaked angular distribution with an enhancement at the forward direction. Comparisons with reactions of {sup 3}P carbon atoms with ethene, vinyl fluoride, and vinyl chloride are stated.

  4. Single Pd atoms in activated carbon fibers and their contribution to hydrogen storage

    SciTech Connect

    Contescu, Cristian I; van Benthem, Klaus; Li, Sa; Bonifacio, Cecile S; Pennycook, Stephen J; Jena, Puru; Gallego, Nidia C

    2011-01-01

    Palladium-modified activated carbon fibers (Pd-ACF) were synthesized by meltspinning, carbonization and activation of an isotropic pitch carbon precursor premixed with an organometallic Pd compound. The hydrogen uptake at 25 oC and 20 bar on Pd- ACF exceeded the expected capacity based solely on Pd hydride formation and hydrogen physisorption on the microporous carbon support. Aberration-corrected scanning transmission electron microscopy (STEM) with sub- ngstrom spatial resolution provided unambiguous identification of isolated Pd atoms occurring in the carbon matrix that coexist with larger Pd particles. First principles calculations revealed that each single Pd atom can form Kubas-type complexes by binding up to three H2 molecules in the pressure range of adsorption measurements. Based on Pd atom concentration determined from STEM images, the contribution of various mechanisms to the excess hydrogen uptake measured experimentally was evaluated. With consideration of Kubas binding as a viable mechanism (along with hydride formation and physisorption to carbon support) the role of hydrogen spillover in this system may be smaller than previously thought.

  5. Evaluation of a carbon-rod atomizer for routine determination of trace metals by atomic-absorption spectroscopy applications to analysis of lubricating oil and crude oil.

    PubMed

    Hall, G; Bratzel, M P; Chakrabarti, C L

    1973-08-01

    A carbon-rod atomizer (CRA) fitted with a 'mini-Massmann' carbon rod was evaluated for routine analysis of petroleum and petroleum products for trace metal content by atomic-absorption spectroscopy. Aspects investigated included sensitivity, detection limit, effect of solvent type, and interferences. The results of analysis of oil samples with this technique were compared with those obtained by other techniques. Metals studied were silver, copper, iron, nickel, and lead. Sensitivity and detection limit values obtained with the CRA were similar to those obtained with the carbon-filament atomizer. Strong 'solvent effects' were observed as well as interference by cations. On the basis of this study, design changes for the CRA are suggested, with the object of minimizing 'solvent effects' and interferences, increasing the atomization efficiency, and increasing the residence time of the atomic vapour in the optical path of the instrumental system.

  6. Ultrasmooth submicrometer carbon spheres as lubricant additives for friction and wear reduction.

    PubMed

    Alazemi, Abdullah A; Etacheri, Vinodkumar; Dysart, Arthur D; Stacke, Lars-Erik; Pol, Vilas G; Sadeghi, Farshid

    2015-03-11

    Ultrasmooth submicrometer carbon spheres are demonstrated as an efficient additive for improving the tribological performance of lubricating oils. Carbon spheres with ultrasmooth surfaces are fabricated by ultrasound assisted polymerization of resorcinol and formaldehyde followed by controlled heat treatment. The tribological behavior of the new lubricant mixture is investigated in the boundary and mixed lubrication regimes using a pin-on-disk apparatus and cylinder-on-disk tribometer, respectively. The new lubricant composition containing 3 wt % carbon spheres suspended in a reference SAE 5W30 engine oil exhibited a substantial reduction in friction and wear (10-25%) compared to the neat oil, without change in the viscosity. Microscopic and spectroscopic investigation of the carbon spheres after the tribological experiments illustrated their excellent mechanical and chemical stability. The significantly better tribological performance of the hybrid lubricant is attributed to the perfectly spherical shape and ultrasmooth surface of carbon sphere additive filling the gap between surfaces and acting as a nanoscale ball bearing.

  7. Chemical and biological consequences of using carbon dioxide versus acid additions in ocean acidification experiments

    USGS Publications Warehouse

    Yates, Kimberly K.; DuFore, Christopher M.; Robbins, Lisa L.

    2013-01-01

    Use of different approaches for manipulating seawater chemistry during ocean acidification experiments has confounded comparison of results from various experimental studies. Some of these discrepancies have been attributed to whether addition of acid (such as hydrochloric acid, HCl) or carbon dioxide (CO2) gas has been used to adjust carbonate system parameters. Experimental simulations of carbonate system parameter scenarios for the years 1766, 2007, and 2100 were performed using the carbonate speciation program CO2SYS to demonstrate the variation in seawater chemistry that can result from use of these approaches. Results showed that carbonate system parameters were 3 percent and 8 percent lower than target values in closed-system acid additions, and 1 percent and 5 percent higher in closed-system CO2 additions for the 2007 and 2100 simulations, respectively. Open-system simulations showed that carbonate system parameters can deviate by up to 52 percent to 70 percent from target values in both acid addition and CO2 addition experiments. Results from simulations for the year 2100 were applied to empirically derived equations that relate biogenic calcification to carbonate system parameters for calcifying marine organisms including coccolithophores, corals, and foraminifera. Calculated calcification rates for coccolithophores, corals, and foraminifera differed from rates at target conditions by 0.5 percent to 2.5 percent in closed-system CO2 gas additions, from 0.8 percent to 15 percent in the closed-system acid additions, from 4.8 percent to 94 percent in open-system acid additions, and from 7 percent to 142 percent in open-system CO2 additions.

  8. Atomic scale observation of oxygen delivery during silver-oxygen nanoparticle catalysed oxidation of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Yue, Yonghai; Yuchi, Datong; Guan, Pengfei; Xu, Jia; Guo, Lin; Liu, Jingyue

    2016-07-01

    To probe the nature of metal-catalysed processes and to design better metal-based catalysts, atomic scale understanding of catalytic processes is highly desirable. Here we use aberration-corrected environmental transmission electron microscopy to investigate the atomic scale processes of silver-based nanoparticles, which catalyse the oxidation of multi-wall carbon nanotubes. A direct semi-quantitative estimate of the oxidized carbon atoms by silver-based nanoparticles is achieved. A mechanism similar to the Mars-van Krevelen process is invoked to explain the catalytic oxidation process. Theoretical calculations, together with the experimental data, suggest that the oxygen molecules dissociate on the surface of silver nanoparticles and diffuse through the silver nanoparticles to reach the silver/carbon interfaces and subsequently oxidize the carbon. The lattice distortion caused by oxygen concentration gradient within the silver nanoparticles provides the direct evidence for oxygen diffusion. Such direct observation of atomic scale dynamics provides an important general methodology for investigations of catalytic processes.

  9. The Reception of J. H. van't Hoff's Theory of the Asymmetric Carbon Atom

    ERIC Educational Resources Information Center

    Snelders, H. A. M.

    1974-01-01

    Discusses Jacobus Henricus van't Hoff's revolutionary theory of the asymmetric carbon atom and its early reception among his contemporaries in the Netherlands. Indicates that the extension of the new idea to practical problems gives the impetus to the development of stereochemistry. (CC)

  10. Atomic scale observation of oxygen delivery during silver–oxygen nanoparticle catalysed oxidation of carbon nanotubes

    PubMed Central

    Yue, Yonghai; Yuchi, Datong; Guan, Pengfei; Xu, Jia; Guo, Lin; Liu, Jingyue

    2016-01-01

    To probe the nature of metal-catalysed processes and to design better metal-based catalysts, atomic scale understanding of catalytic processes is highly desirable. Here we use aberration-corrected environmental transmission electron microscopy to investigate the atomic scale processes of silver-based nanoparticles, which catalyse the oxidation of multi-wall carbon nanotubes. A direct semi-quantitative estimate of the oxidized carbon atoms by silver-based nanoparticles is achieved. A mechanism similar to the Mars–van Krevelen process is invoked to explain the catalytic oxidation process. Theoretical calculations, together with the experimental data, suggest that the oxygen molecules dissociate on the surface of silver nanoparticles and diffuse through the silver nanoparticles to reach the silver/carbon interfaces and subsequently oxidize the carbon. The lattice distortion caused by oxygen concentration gradient within the silver nanoparticles provides the direct evidence for oxygen diffusion. Such direct observation of atomic scale dynamics provides an important general methodology for investigations of catalytic processes. PMID:27406595

  11. Atom Vacancies on a Carbon Nanotube: To What Extent Can We Simulate their Effects?

    PubMed

    Kroes, Jaap M H; Pietrucci, Fabio; van Duin, Adri C T; Andreoni, Wanda

    2015-07-14

    Atom vacancies are intrinsic defects of carbon nanotubes. Using a zigzag nanotube as reference, this paper focuses on the comparison of calculations performed within density functional theory and a number of classical force fields widely used for carbon systems. The results refer to single and double vacancies and, in particular, to the induced structural changes, the formation energies, and the energy barriers relative to elementary processes such as reconstruction, migration, and coalescence. Characterization of these processes is remarkably different in the different approaches. These findings are meant to contribute to the construction of DFT-based classical schemes for carbon nanostructures.

  12. Spatial Distributions of Metal Atoms During Carbon SWNTs Formation: Measurements and Modelling

    NASA Technical Reports Server (NTRS)

    Cau, M.; Dorval, N.; Attal-Tretout, B.; Cochon, J. L.; Loiseau, A.; Farhat, S.; Hinkov, I.; Scott, C. D.

    2004-01-01

    Experiments and modelling have been undertaken to clarify the role of metal catalysts during single-wall carbon nanotube formation. For instance, we wonder whether the metal catalyst is active as an atom, a cluster, a liquid or solid nanoparticle [1]. A reactor has been developed for synthesis by continuous CO2-laser vaporisation of a carbon-nickel-cobalt target in laminar helium flow. The laser induced fluorescence technique [2] is applied for local probing of gaseous Ni, Co and CZ species throughout the hot carbon flow of the target heated up to 3500 K. A rapid depletion of C2 in contrast to the spatial extent of metal atoms is observed in the plume (Fig. 1). This asserts that C2 condenses earlier than Ni and Co atoms.[3, 4]. The depletion is even faster when catalysts are present. It may indicate that an interaction between metal atoms and carbon dimers takes place in the gas as soon as they are expelled from the target surface. Two methods of modelling are used: a spatially I-D calculation developed originally for the arc process [5], and a zero-D time dependent calculation, solving the chemical kinetics along the streamlines [6]. The latter includes Ni cluster formation. The peak of C2 density is calculated close to the target surface where the temperature is the highest. In the hot region, C; is dominant. As the carbon products move away from the target and mix with the ambient helium, they recombine into larger clusters, as demonstrated by the peak of C5 density around 1 mm. The profile of Ni-atom density compares fairly well with the measured one (Fig. 2). The early increase is due to the drop of temperature, and the final decrease beyond 6 mm results from Ni cluster formation at the eutectic temperature (approx.1600 K).

  13. Multiphoton inner-shell ionization of the carbon atom

    NASA Astrophysics Data System (ADS)

    Rey, H. F.; van der Hart, H. W.

    2015-07-01

    We apply time-dependent R -matrix theory to study inner-shell ionization of C atoms in ultrashort high-frequency light fields with a photon energy between 170 and 245 eV. At an intensity of 1017 W /cm2, ionization is dominated by single-photon emission of a 2 ℓ electron, with two-photon emission of a 1 s electron accounting for about 2-3% of all emission processes, and two-photon emission of 2 ℓ contributing about 0.5-1%. Three-photon emission of a 1 s electron is estimated to contribute about 0.01-0.03%. Around a photon energy of 225 eV, two-photon emission of a 1 s electron, leaving C+ in either 1 s 2 s 2 p3 or 1 s 2 p4 , is resonantly enhanced by intermediate 1 s 2 s22 p3 states. The results demonstrate the capability of time-dependent R -matrix theory to describe inner-shell ionization processes including rearrangement of the outer electrons.

  14. A new material with atomized cobalt-multiwalled carbon nanotubes: a possible substitute for human implants.

    PubMed

    Joshi, Bharat; Gupta, Sachin; Kalra, Nitin; Gudyka, Russell; Santhanam, K S V

    2010-06-01

    A new material composed of atomized cobalt-multiwalled carbon nanotube has been produced and characterized by thermogravimetric analysis and polarization studies to estimate its lifetime. This does not show cobalt thermal oxidation suggesting that it is confined inside the carbon nanotube matrix. The density functional calculations in the literature predict a strong interaction leading to higher hybridization of cobalt atom and carbon nanotubes. A detailed investigation of the corrosion measurements shows that the new material of thickness 0.8 mm, 1 mm, 1.5 mm and 2 mm would last for 31, 39, 60 and 79 years and it would substitute with cobalt-chromium alloy that is used as a load bearing implant for patients with knee pain or partial denture implant.

  15. Carbonate fuel cell and components thereof for in-situ delayed addition of carbonate electrolyte

    DOEpatents

    Johnsen, Richard; Yuh, Chao-Yi; Farooque, Mohammad

    2011-05-10

    An apparatus and method in which a delayed carbonate electrolyte is stored in the storage areas of a non-electrolyte matrix fuel cell component and is of a preselected content so as to obtain a delayed time release of the electrolyte in the storage areas in the operating temperature range of the fuel cell.

  16. Atomic-layer-deposition-assisted formation of carbon nanoflakes on metal oxides and energy storage application.

    PubMed

    Guan, Cao; Zeng, Zhiyuan; Li, Xianglin; Cao, Xiehong; Fan, Yu; Xia, Xinhui; Pan, Guoxiang; Zhang, Hua; Fan, Hong Jin

    2014-01-29

    Nanostructured carbon is widely used in energy storage devices (e.g., Li-ion and Li-air batteries and supercapacitors). A new method is developed for the generation of carbon nanoflakes on various metal oxide nanostructures by combining atomic layer deposition (ALD) and glucose carbonization. Various metal oxide@nanoflake carbon (MO@f-C) core-branch nanostructures are obtained. For the mechanism, it is proposed that the ALD Al2 O3 and glucose form a composite layer. Upon thermal annealing, the composite layer becomes fragmented and moves outward, accompanied by carbon deposition on the alumina skeleton. When tested as electrochemical supercapacitor electrode, the hierarchical MO@f-C nanostructures exhibit better properties compared with the pristine metal oxides or the carbon coating without ALD. The enhancement can be ascribed to increased specific surface areas and electric conductivity due to the carbon flake coating. This peculiar carbon coating method with the unique hierarchical nanostructure may provide a new insight into the preparation of 'oxides + carbon' hybrid electrode materials for energy storage applications.

  17. Metal-Assisted Oxo Atom Addition to an Fe(III) Thiolate.

    PubMed

    Villar-Acevedo, Gloria; Lugo-Mas, Priscilla; Blakely, Maike N; Rees, Julian A; Ganas, Abbie S; Hanada, Erin M; Kaminsky, Werner; Kovacs, Julie A

    2017-01-11

    Cysteinate oxygenation is intimately tied to the function of both cysteine dioxygenases (CDOs) and nitrile hydratases (NHases), and yet the mechanisms by which sulfurs are oxidized by these enzymes are unknown, in part because intermediates have yet to be observed. Herein, we report a five-coordinate bis-thiolate ligated Fe(III) complex, [Fe(III)(S2(Me2)N3(Pr,Pr))](+) (2), that reacts with oxo atom donors (PhIO, IBX-ester, and H2O2) to afford a rare example of a singly oxygenated sulfenate, [Fe(III)(η(2)-S(Me2)O)(S(Me2))N3(Pr,Pr)](+) (5), resembling both a proposed intermediate in the CDO catalytic cycle and the essential NHase Fe-S(O)(Cys114) proposed to be intimately involved in nitrile hydrolysis. Comparison of the reactivity of 2 with that of a more electron-rich, crystallographically characterized derivative, [Fe(III)S2(Me2)N(Me)N2(amide)(Pr,Pr)](-) (8), shows that oxo atom donor reactivity correlates with the metal ion's ability to bind exogenous ligands. Density functional theory calculations suggest that the mechanism of S-oxygenation does not proceed via direct attack at the thiolate sulfurs; the average spin-density on the thiolate sulfurs is approximately the same for 2 and 8, and Mulliken charges on the sulfurs of 8 are roughly twice those of 2, implying that 8 should be more susceptible to sulfur oxidation. Carboxamide-ligated 8 is shown to be unreactive towards oxo atom donors, in contrast to imine-ligated 2. Azide (N3(-)) is shown to inhibit sulfur oxidation with 2, and a green intermediate is observed, which then slowly converts to sulfenate-ligated 5. This suggests that the mechanism of sulfur oxidation involves initial coordination of the oxo atom donor to the metal ion. Whether the green intermediate is an oxo atom donor adduct, Fe-O═I-Ph, or an Fe(V)═O remains to be determined.

  18. ALMA observations of atomic carbon in z ∼ 4 dusty star-forming galaxies

    NASA Astrophysics Data System (ADS)

    Bothwell, M. S.; Aguirre, J. E.; Aravena, M.; Bethermin, M.; Bisbas, T. G.; Chapman, S. C.; De Breuck, C.; Gonzalez, A. H.; Greve, T. R.; Hezaveh, Y.; Ma, J.; Malkan, M.; Marrone, D. P.; Murphy, E. J.; Spilker, J. S.; Strandet, M.; Vieira, J. D.; Weiß, A.

    2017-04-01

    We present Atacama Large Millimeter Array [C I](1 - 0) (rest frequency 492 GHz) observations for a sample of 13 strongly lensed dusty star-forming galaxies (DSFGs) originally discovered at 1.4 mm in a blank-field survey by the South Pole Telescope (SPT). We compare these new data with available [C I] observations from the literature, allowing a study of the interstellar medium (ISM) properties of ∼30 extreme DSFGs spanning a redshift range 2 < z < 5. Using the [C I] line as a tracer of the molecular ISM, we find a mean molecular gas mass for SPT-DSFGs of 6.6 × 1010 M⊙. This is in tension with gas masses derived via low-J 12CO and dust masses; bringing the estimates into accordance requires either (a) an elevated CO-to-H2 conversion factor for our sample of αCO ∼ 2.5 and a gas-to-dust ratio ∼200, or (b) an high carbon abundance X_{C I} ˜ 7× 10^{-5}. Using observations of a range of additional atomic and molecular lines (including [C I], [C II]and multiple transitions of CO), we use a modern photodissociation region code (3D-PDR) to assess the physical conditions (including the density, UV radiation field strength and gas temperature) within the ISM of the DSFGs in our sample. We find that the ISM within our DSFGs is characterized by dense gas permeated by strong UV fields. We note that previous efforts to characterize photodissociation region regions in DSFGs may have significantly under-estimated the density of the ISM. Combined, our analysis suggests that the ISM of extreme dusty starbursts at high redshift consists of dense, carbon-rich gas not directly comparable to the ISM of starbursts in the local Universe.

  19. The CH + CO reaction: Rate coefficient for carbon atom exchange at 294 K

    SciTech Connect

    Anderson, S.M.; McCurdy, K.E.; Kolb, C.E. )

    1989-02-09

    A fast-flow reactor equipped with isotope-specific laser-excited fluorescence detection of CH radicals has been used to study carbon atom exchange in the reaction between CH and CO at 294 K and 2 Torr of total pressure. The rate coefficient for exchange, k{sub 3} = (2.1 {times} 0.3) {times} 10{sup {minus}12} cm{sup 3} s{sup {minus}1}, is about an order of magnitude larger than the bimolecular rate for the addition reaction, k{sub 2} = (2.7 {plus minus} 0.4) {times} 10{sup {minus}13}. High-pressure limiting bimolecular and low-pressure termolecular recombination rate coefficients of 1.1 {times} 10{sup {minus}10} cm{sup 3} s{sup {minus}1} and 4.9 {times} 10{sup {minus}30} cm{sup 6} s{sup {minus}1} are derived. The results are discussed in the context of previous work on the title reaction and on the chemistry of singlet CH{sub 2}.

  20. Atomic Force Microscopy of DNA-wrapped Single-walled Carbon Nanotubes in Aqueous Solution.

    PubMed

    Hayashida, Takuya; Umemura, Kazuo

    2016-07-01

    We evaluated hybrids of DNA and single-walled carbon nanotubes (SWNTs) in aqueous solution and in air using atomic force microscopy (AFM). Although intensive AFM observations of these hybrids were previously carried out for samples in air, this is the first report on AFM observations of these hybrids in solution. As expected, diameters of DNA-SWNT hybrids dramatically increased in tris(hydroxymethyl)aminomethane-ethylenediaminetetraacetic acid (TE) buffer solution. The data suggest that DNA molecules maintain their structures even on the SWNT surfaces. Furthermore, we simultaneously observed single DNA-SWNT hybrids using three different AFM modes in air and in the TE buffer solution. Height value of the hybrids was largest in the solution, and lowest for the mode that repulsive force is expected in air. For the bare SWNT molecules, height differences among the three AFM modes were much lower than those of the DNA-SWNT hybrids. DNA molecules adsorbed on SWNT surfaces flexibly changed their morphology as well as DNA molecules on flat surfaces such as mica. This is hopeful results for biological applications of DNA-SWNT hybrids. In addition, our results revealed the importance of the single-molecule approach to evaluate DNA structures on SWNT surfaces.

  1. Recent Advances in Atomic Metal Doping of Carbon-based Nanomaterials for Energy Conversion.

    PubMed

    Bayatsarmadi, Bita; Zheng, Yao; Vasileff, Anthony; Qiao, Shi-Zhang

    2017-04-12

    Nanostructured metal-contained catalysts are one of the most widely used types of catalysts applied to facilitate some of sluggish electrochemical reactions. However, the high activity of these catalysts cannot be sustained over a variety of pH ranges. In an effort to develop highly active and stable metal-contained catalysts, various approaches have been pursued with an emphasis on metal particle size reduction and doping on carbon-based supports. These techniques enhances the metal-support interactions, originating from the chemical bonding effect between the metal dopants and carbon support and the associated interface, as well as the charge transfer between the atomic metal species and carbon framework. This provides an opportunity to tune the well-defined metal active centers and optimize their activity, selectivity and stability of this type of (electro)catalyst. Herein, recent advances in synthesis strategies, characterization and catalytic performance of single atom metal dopants on carbon-based nanomaterials are highlighted with attempts to understand the electronic structure and spatial arrangement of individual atoms as well as their interaction with the supports. Applications of these new materials in a wide range of potential electrocatalytic processes in renewable energy conversion systems are also discussed with emphasis on future directions in this active field of research.

  2. Atomic Environment Changes Induced by Iron Addition to Gallium Bismuthate Glasses

    NASA Astrophysics Data System (ADS)

    Simon, V.; BarzǍ, L.; Simon, S.; ChiuzbǍIAN, S. G.; Neumann, M.

    Atomic environment of xFe2O3·(80-x)Bi2O3·20Ga2O3 heavy glasses (0≤x≤20 mol%) was investigated with respect to electronic structure of the samples. Data obtained from Bi 4f, Ga 2p, Fe 2p, and O 1s core-level photoelectron spectra indicate changes in the local order on the account of partial substitution of bismuth by iron. The bismuth cations behave essentially as network formers while the iron and gallium ones acts as network modifiers. The number of nonbridging oxygens depends on Fe2O3 content.

  3. Treatment of Scumming Effects of Pottery Clay by Sodium Carbonate Addition

    NASA Astrophysics Data System (ADS)

    Wasanapiarnpong, T.; Thueploy, A.; Nilpairach, S.; Arayaphong, D.

    2011-10-01

    Earthenware pottery products made by using red plastic clay in Ratchaburi province of Thailand and fired at 850-1000 °C, always shows some blemishes, caused by scumming on the surface. This scumming contains calcium sulfate, contaminated in the raw clay as gypsum form. The addition of barium carbonate is a suggested solution to prevent this white stain. However, it is difficult for barium carbonate to spread throughout the clay so that it takes a long time to complete the reaction. This research aims to find the solution by using sodium carbonate as an alternative chemical. Sodium carbonate was mixed in the clay at 1wt% dissolved in distilled water controlled the moisture at 22 % by wet weight. The mixture was kneaded and aged for 24 h, then formed, dried and fired at 850-950 °C. The types and quantities of ion in mixed clay and deposited on the surface product were determined after drying. It was found that the white stain areas were diminished, as same as the result from the addition of barium carbonate. Moreover, the sample after firing at 950 °C had lower water absorption as 12.22 %, higher three point bending strength as 32.53 MPa when compared to the addition of barium carbonate, which had higher water absorption as 15.58 % and lower three point bending strength as 25.25 MPa.

  4. Addition of Carbon to the Culture Medium Improves the Detection Efficiency of Aflatoxin Synthetic Fungi

    PubMed Central

    Suzuki, Tadahiro; Iwahashi, Yumiko

    2016-01-01

    Aflatoxin (AF) is a harmful secondary metabolite that is synthesized by the Aspergillus species. Although AF detection techniques have been developed, techniques for detection of AF synthetic fungi are still required. Techniques such as plate culture methods are continually being modified for this purpose. However, plate culture methods require refinement because they suffer from several issues. In this study, activated charcoal powder (carbon) was added to a culture medium containing cyclodextrin (CD) to enhance the contrast of fluorescence and improve the detection efficiency for AF synthetic fungi. Two culture media, potato dextrose agar and yeast extract sucrose agar, were investigated using both plate and liquid cultures. The final concentrations of CD and carbon in the media were 3 mg/mL and 0.3 mg/mL, respectively. Addition of carbon improved the visibility of fluorescence by attenuating approximately 30% of light scattering. Several fungi that could not be detected with only CD in the medium were detected with carbon addition. The carbon also facilitated fungal growth in the potato dextrose liquid medium. The results suggest that addition of carbon to media can enhance the observation of AF-derived fluorescence. PMID:27854283

  5. Confinement induced binding in noble gas atoms within a BN-doped carbon nanotube

    NASA Astrophysics Data System (ADS)

    Chakraborty, Debdutta; Chattaraj, Pratim Kumar

    2015-02-01

    Confinement induced binding interaction patterns for noble gas atoms (Hen/m, Arn, Krn; n = 2, m = 3) atoms inside pristine and -BN doped (3, 3) single walled carbon nanotube (SWCNT) have been studied through density functional theory calculations. The kinetic stability for He dimer and trimer has been investigated at 100 K and 300 K through an ab initio molecular dynamics simulation. The positive role of doping in SWCNT in enhancing the nature of interaction as well as the kinetic stability of the said systems has been found.

  6. Effect of inorganic additives on the growth of silica-carbonate biomorphs

    NASA Astrophysics Data System (ADS)

    Nakouzi, Elias; Rendina, Ryan; Palui, Goutam; Steinbock, Oliver

    2016-10-01

    Silica-barium carbonate biomorphs are complex precipitate microstructures that form by purely inorganic processes. They display life-like morphologies with smoothly curved surfaces that are not restricted to crystallographic symmetries. We investigate the morphogenetic influence of inorganic dopants that compete with the barium carbonate precipitation. Trace deposition of alkaline earth or transition metal additives causes significant changes to the crystal morphologies. In the case of Pb2+ and Ag+ ions, biomorph growth is disrupted by the formation of competing precipitates. Similarly, the addition of Ca2+, Mg2+, and Zn2+ induces the rapid crystallization of witherite or amorphous silica-carbonate aggregates at enhanced growth rates. By comparison, the addition of strontium ions results in the assembly of classic biomorphs such as cardioid sheets and helices. The procedures reported here exemplify the use of co-depositing agents to influence the compositional and crystallographic properties in a manner similar to magnesium-doped biogenic calcites.

  7. Octagraphene as a versatile carbon atomic sheet for novel nanotubes, unconventional fullerenes, and hydrogen storage

    NASA Astrophysics Data System (ADS)

    Sheng, Xian-Lei; Cui, Hui-Juan; Ye, Fei; Yan, Qing-Bo; Zheng, Qing-Rong; Su, Gang

    2012-10-01

    We study a versatile structurally favorable periodic sp2-bonded carbon atomic planar sheet with C4v symmetry by means of the first-principles calculations. This carbon allotrope is composed of carbon octagons and squares with two bond lengths and is thus dubbed as octagraphene. It is a semimetal with the Fermi surface consisting of one hole and one electron pocket, whose low-energy physics can be well described by a tight-binding model of π-electrons. Its Young's modulus, breaking strength, and Poisson's ratio are obtained to be 306 N/m, 34.4 N/m, and 0.13, respectively, which are close to those of graphene. The novel sawtooth and armchair carbon nanotubes as well as unconventional fullerenes can also be constructed from octagraphene. It is found that the Ti-absorbed octagraphene can be allowed for hydrogen storage with capacity around 7.76 wt. %.

  8. Angular distribution of photoelectrons from atomic oxygen, nitrogen and carbon. [in upper atmosphere

    NASA Technical Reports Server (NTRS)

    Manson, S. J.; Kennedy, D. J.; Starace, A. F.; Dill, D.

    1974-01-01

    The angular distributions of photoelectrons from atomic oxygen, nitrogen, and carbon are calculated. Both Hartree-Fock and Hartree-Slater (Herman-Skillman) wave functions are used for oxygen, and the agreement is excellent; thus only Hartree-Slater functions are used for carbon and nitrogen. The pitch-angle distribution of photoelectrons is discussed, and it is shown that previous approximations of energy-independent isotropic or sin squared theta distributions are at odds with the authors' results, which vary with energy. This variation with energy is discussed, as is the reliability of these calculations.

  9. Fabrication and Characterization of Oriented Carbon Atom Wires Assembled on Gold

    SciTech Connect

    Xue,K.H.; Wu,L.; Chen, S.-P.; Wanga, L.X.; Wei, R.-B.; Xu, S.-M.; Cui, L.; Mao, B.-W.; Tian, Z.-Q.; Zen, C.-H.; Sun, S.-G.; Zhu, Y.-M.

    2009-02-17

    Carbon atom wires (CAWs) are of the sp-hybridized allotrope of carbon. To augment the extraordinary features based on sp-hybridization, we developed an approach to make CAWs be self-assembled and orderly organized on Au substrate. The self-assembling process was investigated in situ by using scanning tunneling microscopy (STM) and electrochemical quartz crystal microbalance (EQCM). The properties of the assembled film were characterized by voltammetry, Raman spectroscopy, electron energy loss spectroscopy (EELS), and the contact angle measurements. Experimental results indicated that the assembled CAW film was of the good structural integrity and well organized, with the sp-hybridized features enhanced.

  10. A Molecular Dynamics of Cold Neutral Atoms Captured by Carbon Nanotube Under Electric Field and Thermal Effect as a Selective Atoms Sensor.

    PubMed

    Santos, Elson C; Neto, Abel F G; Maneschy, Carlos E; Chen, James; Ramalho, Teodorico C; Neto, A M J C

    2015-05-01

    Here we analyzed several physical behaviors through computational simulation of systems consisting of a zig-zag type carbon nanotube and relaxed cold atoms (Rb, Au, Si and Ar). These atoms were chosen due to their different chemical properties. The atoms individually were relaxed on the outside of the nanotube during the simulations. Each system was found under the influence of a uniform electric field parallel to the carbon nanotube and under the thermal effect of the initial temperature at the simulations. Because of the electric field, the cold atoms orbited the carbon nanotube while increasing the initial temperature allowed the variation of the radius of the orbiting atoms. We calculated the following quantities: kinetic energy, potential energy and total energy and in situ temperature, molar entropy variation and average radius of the orbit of the atoms. Our data suggest that only the action of electric field is enough to generate the attractive potential and this system could be used as a selected atoms sensor.

  11. The abundance of atomic carbon near the ionization fronts in M17 and S140

    NASA Technical Reports Server (NTRS)

    Keene, J.; Blake, G. A.; Phillips, T. G.; Huggins, P. J.; Beichman, C. A.

    1985-01-01

    The 492 GHz ground-state line of atomic carbon in the edge-on ionization fronts in M17 and S140 were observed. It was found that, contrary to expectation, the C I emission peaks farther into the molecular cloud from the ionization front than does the CO. In fact the peak C I abundance in M17 occurs more than 60 mag of visual extinction into the cloud from the ionization front. Calculations of the ratio of C I to CO column densities yield values of 0.1-0.2. These observations do not support chemical models which predict that neutral atomic carbon should be found only near the edges of molelcular clouds. Other models are discussed which may explain the observations.

  12. An upper limit to the atomic carbon abundance in the Orion plateau

    NASA Technical Reports Server (NTRS)

    Beichman, C. A.; Phillips, T. G.; Wootten, H. A.; Frerking, M.

    1982-01-01

    Observations made of the atomic carbon line at 492 GHz toward OMC-1 show no evidence for the high velocity dispersion wings observed for many molecular rotational lines. The 3sigma upper limit to the CI column density, NCI, is 6.9 x 10 to the 17th per sq cm for velocities greater than or equal to 4 km per sec from the line center. This upper limit corresponds to a ratio of CI to CO abundances as low as less than 0.13, depending on the assumed CO column density. Atomic carbon is apparently depleted by a factor as large as five in the hot plateau gas, relative to its abundance in other molecular clouds. The lack of CI in the plateau source may mean that the shocks thought to be present in the region are not dissociative in nature and thus do not produce the UV radiation required to convert CO into CI.

  13. Doping of carbon nanotubes with aluminum atom to improve Pt adsorption

    NASA Astrophysics Data System (ADS)

    Ganji, M. D.; Ahangari, M. Ghorbanzadeh; Khosravi, A.

    2014-01-01

    We implement the ab initio van der Waals (vdW) calculations at the density functional level of theory (vdW-DF) for the investigation of Pt adsorption ability of Al-doped carbon nanotubes (Al-CNTs). We present and discuss the energetically favorable sites for a single Pt atom adsorbed on the surface of Al-CNTs. Our results show significantly increment in the binding energy of Pt on the Al-CNT compared with pristine CNTs. We also find that Pt adsorption ability of Al-CNTs is more stronger than that of B- and N-doped CNTs. This is explained by the negative charges introduced in the neighboring C atoms by dopant atom. Our results verify that Al-doped CNTs seems to be more suitable materials for Pt adsorption than pure and also B- and N-doped CNTs.

  14. Detection of the 610 micron /492 GHz/ line of interstellar atomic carbon

    NASA Technical Reports Server (NTRS)

    Phillips, T. G.; Huggins, P. J.; Kuiper, T. B. H.; Miller, R. E.

    1980-01-01

    The ground-state transition of neutral atomic carbon, 3P1-3P0, has been detected in the interstellar medium at the frequency of 492.162 GHz determined in the laboratory by Saykally and Evenson (1980). The observations were made from the NASA Kuiper Airborne Observatory using an InSb heterodyne bolometer receiver. The line was detected as strong emission from eight molecular clouds and apparently provides a widely useful probe of the interstellar medium.

  15. An atomic view of additive mutational effects in a protein structure

    SciTech Connect

    Skinner, M.M.; Terwilliger, T.C.

    1996-04-01

    Substitution of a single amino acid in a protein will often lead to substantial changes in properties. If these properties could be altered in a rational way then proteins could be readily generated with functions tailored to specific uses. When amino acid substitutions are made at well-separated locations in a single protein, their effects are generally additive. Additivity of effects of amino acid substitutions is very useful because the properties of proteins with any combination of substitutions can be inferred directly from those of the proteins with single changes. It would therefore be of considerable interest to have a means of knowing whether substitutions at a particular pair of sites in a protein are likely to lead to additive effects. The structural basis for additivity of effects of mutations on protein function was examined by determining crystal structures of single and double mutants in the hydrophobic core of gene V protein. Structural effects of mutations were found to be cumulative when two mutations were made in a single protein. Additivity occurs in this case because the regions structurally affected by mutations at the two sites do not overlap even though the sites are separated by only 9 {angstrom}. Structural distortions induced by mutations in gene V protein decrease rapidly, but not isotropically, with distance from the site of mutation. It is anticipated that cases where structural and functional effects of mutations will be additive could be identified simply by examining whether the regions structurally affected by each component mutation overlap.

  16. Suppression of hydrogenated carbon film deposition and hydrogen isotope retention by nitrogen addition into cold remote H/D and CH4 mixture plasmas

    NASA Astrophysics Data System (ADS)

    Iida, K.; Notani, M.; Uesugi, Y.; Tanaka, Y.; Ishijima, T.

    2015-08-01

    Control of tritium retention and its removal from the first wall of future fusion devices are one of the most crucial issues for safety and effective use for fuel. Nitrogen addition into remote edge plasmas has been considered and tested as an effective method for suppression of carbon film deposition and reduction of hydrogen isotope absorption in the deposited films. In this paper we have investigated the scavenger effects of nitrogen injected into low temperature D2/CH4 plasmas on hydrogenated carbon film growth using a small helical device. The result of the deposition shows that the key reactive particles with CN and ND(H) bonds to suppression of hydrogenated carbon film growth and hydrogen isotope absorption are much slowly generated compared with hydrocarbon particles such as CD(H)x and C2D(H)x. This may be due to the slow atomic nitrogen diffusion into hydrogenated carbon layer and the chemical equilibrium between nitrogen absorption.

  17. ATOMIC-LEVEL IMAGING OF CO2 DISPOSAL AS A CARBONATE MINERAL: OPTIMIZING REACTION PROCESS DESIGN

    SciTech Connect

    M.J. McKelvy; R. Sharma; A.V.G. Chizmeshya; H. Bearat; R.W. Carpenter

    2002-11-01

    Fossil fuels, especially coal, can support the energy demands of the world for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Permanent and safe methods for CO{sub 2} capture and disposal/storage need to be developed. Mineralization of stationary-source CO{sub 2} emissions as carbonates can provide such safe capture and long-term sequestration. Mg-rich lamellar-hydroxide based minerals (e.g., brucite and serpentine) offer a class of widely available, low-cost materials, with intriguing mineral carbonation potential. Carbonation of such materials inherently involves dehydroxylation, which can disrupt the material down to the atomic level. As such, controlled dehydroxylation, before and/or during carbonation, may provide an important parameter for enhancing carbonation reaction processes. Mg(OH){sub 2} was chosen as the model material for investigating lamellar hydroxide mineral dehydroxylation/carbonation mechanisms due to (1) its structural and chemical simplicity, (2) interest in Mg(OH){sub 2} gas-solid carbonation as a potentially cost-effective CO{sub 2} mineral sequestration process component, and (3) its structural and chemical similarity to other lamellar-hydroxide-based minerals (e.g., serpentine-based minerals) whose carbonation reaction processes are being explored due to their low-cost CO{sub 2} sequestration potential. Fundamental understanding of the mechanisms that govern dehydroxylation/carbonation processes is essential for minimizing the cost of any lamellar-hydroxide-based mineral carbonation sequestration process. This final report covers the overall progress of this grant.

  18. Development of carbon electrodes for electrochemistry, solid-state electronics and multimodal atomic force microscopy imaging

    NASA Astrophysics Data System (ADS)

    Morton, Kirstin Claire

    Carbon is one of the most remarkable elements due to its wide abundance on Earth and its many allotropes, which include diamond and graphite. Many carbon allotropes are conductive and in recent decades scientists have discovered and synthesized many new forms of carbon, including graphene and carbon nanotubes. The work in this thesis specifically focuses on the fabrication and characterization of pyrolyzed parylene C (PPC), a conductive pyrocarbon, as an electrode material for diodes, as a conductive coating for atomic force microscopy (AFM) probes and as an ultramicroelectrode (UME) for the electrochemical interrogation of cellular systems in vitro. Herein, planar and three-dimensional (3D) PPC electrodes were microscopically, spectroscopically and electrochemically characterized. First, planar PPC films and PPC-coated nanopipettes were utilized to detect a model redox species, Ru(NH3) 6Cl3. Then, free-standing PPC thin films were chemically doped, with hydrazine and concentrated nitric acid, to yield p- and n-type carbon films. Doped PPC thin films were positioned in conjunction with doped silicon to create Schottky and p-n junction diodes for use in an alternating current half-wave rectifier circuit. Pyrolyzed parylene C has found particular merit as a 3D electrode coating of AFM probes. Current sensing-atomic force microscopy imaging in air of nanoscale metallic features was undertaken to demonstrate the electronic imaging applicability of PPC AFM probes. Upon further insulation with parylene C and modification with a focused ion beam, a PPC UME was microfabricated near the AFM probe apex and utilized for electrochemical imaging. Subsequently, scanning electrochemical microscopy-atomic force microscopy imaging was undertaken to electrochemically quantify and image the spatial location of dopamine exocytotic release, elicited mechanically via the AFM probe itself, from differentiated pheochromocytoma 12 cells in vitro.

  19. Rare Potassium-Bearing Mica in Allan Hills 84001: Additional Constraints on Carbonate Formation

    NASA Technical Reports Server (NTRS)

    Brearley, A. J.

    1998-01-01

    There have been presented several intriguing observations suggesting evidence of fossil life in martian orthopyroxenite ALH 84001. These exciting and controversial observations have stimulated extensive debate over the origin and history of ALH 84001, but many issues still remain unresolved. Among the most important is the question of the temperature at which the carbonates, which host the putative microfossils, formed. Oxygen- isotopic data, while showing that the carbonates are generally out of isotopic equilibria with the host rock, cannot constrain their temperature of formation. Both low- and high-temperature scenarios are plausible depending on whether carbonate growth occurred in an open or closed system. Petrographic arguments have generally been used to support a high-temperature origin but these appear to be suspect because they assume equilibrium between carbonate compositions that are not in contact. Some observations appear to be consistent with shock mobilization and growth from immiscible silicate-carbonate melts at high temperatures. Proponents of a low-temperature origin for the carbonates are hampered by the fact that there is currently no evidence of hydrous phases that would indicate low temperatures and the presence of a hydrous fluid during the formation of the carbonates. However, the absence of hydrous phases does not rule out carbonate formation at low temperatures, because the carbonate forming fluids may have been extremely CO2 rich, such that hydrous phases would not have been stabilized. In this study, I have carried out additional Transmission electron microscopy (TEM) studies of ALH-84001 and have found evidence of very rare phyllosilicates, which appear to be convincingly of pre-terrestrial origin. At present these observations are limited to one occurrence: further studies are in progress to determine if the phyllosilicates are more widespread.

  20. Kinetic effect of Pd additions on the hydrogen uptake of chemically activated, ultramicroporous carbon

    SciTech Connect

    Bhat, Vinay V; Contescu, Cristian I; Gallego, Nidia C

    2010-01-01

    The effect of mixing chemically-activated ultramicroporous carbon (UMC) with Pd nanopowder is investigated. Results show that Pd addition doubles the rate of hydrogen uptake, but does not enhance the hydrogen capacity or improve desorption kinetics. The effect of Pd on the rate of hydrogen adsorption supports the occurrence of the hydrogen spillover mechanism in the Pd - UMC system.

  1. The Effect of Boron Addition on the Atomic Structure and Microwave Magnetic Properties of FeGaB Thin Films

    SciTech Connect

    Gao, J.; Yang, A; Chen, Y; Kirkland, J; Lou, J; Sun, N; Vittoria, C; Harris, V

    2009-01-01

    Varying amounts of boron were added to the host FeGa alloy to investigate its impact upon local atomic structure and magnetic and microwave properties. The impact of B upon the local atomic structure in FeGaB films was investigated by extended x-ray absorption fine structure (EXAFS) analysis. The EXAFS fitting results revealed a contraction of lattice parameters with the introduction of B. The Debye-Waller factor determined from EXAFS fitting increases as a function of boron addition and abruptly changes during the structural evolution from crystalline to amorphous that occurs near 9% B. Upon the onset of this transition the static and microwave magnetic properties became exceptionally soft, with values of coercivity and ferromagnetic linewidth reducing to less than 1 Oe and 25 Oe, respectively.

  2. The effect of boron addition on the atomic structure and microwave magnetic properties of FeGaB thin films

    NASA Astrophysics Data System (ADS)

    Gao, Jinsheng; Yang, Aria; Chen, Yajie; Kirkland, J. P.; Lou, Jing; Sun, Nian X.; Vittoria, Carmine; Harris, Vincent G.

    2009-04-01

    Varying amounts of boron were added to the host FeGa alloy to investigate its impact upon local atomic structure and magnetic and microwave properties. The impact of B upon the local atomic structure in FeGaB films was investigated by extended x-ray absorption fine structure (EXAFS) analysis. The EXAFS fitting results revealed a contraction of lattice parameters with the introduction of B. The Debye-Waller factor determined from EXAFS fitting increases as a function of boron addition and abruptly changes during the structural evolution from crystalline to amorphous that occurs near 9% B. Upon the onset of this transition the static and microwave magnetic properties became exceptionally soft, with values of coercivity and ferromagnetic linewidth reducing to less than 1 Oe and 25 Oe, respectively.

  3. Investigation of the Interactions and Bonding between Carbon and Group VIII Metals at the Atomic Scale.

    PubMed

    Zoberbier, Thilo; Chamberlain, Thomas W; Biskupek, Johannes; Suyetin, Mikhail; Majouga, Alexander G; Besley, Elena; Kaiser, Ute; Khlobystov, Andrei N

    2016-03-23

    The nature and dynamics of bonding between Fe, Ru, Os, and single-walled carbon nanotubes (SWNTs) is studied by aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM). The metals catalyze a wide variety of different transformations ranging from ejection of carbon atoms from the nanotube sidewall to the formation of hollow carbon shells or metal carbide within the SWNT, depending on the nature of the metal. The electron beam of AC-HRTEM serves the dual purpose of providing energy to the specimen and simultaneously enabling imaging of chemical transformations. Careful control of the electron beam parameters, energy, flux, and dose allowed direct comparison between the metals, demonstrating that their chemical reactions with SWNTs are determined by a balance between the cohesive energy of the metal particles and the strength of the metal-carbon σ- or π-bonds. The pathways of transformations of a given metal can be drastically changed by applying different electron energies (80, 40, or 20 keV), thus demonstrating AC-HRTEM as a new tool to direct and study chemical reactions. The understanding of interactions and bonding between SWNT and metals revealed by AC-HRTEM at the atomic level has important implications for nanotube-based electronic devices and catalysis.

  4. Practical use of a carbon nanotube attached to a blunt apex in an atomic force microscope

    SciTech Connect

    Kuwahara, Masashi; Abe, Hidekazu; Tokumoto, Hiroshi; Shima, Takayuki; Tominaga, Junji; Fukuda, Hajime

    2004-03-15

    A carbon nanotube (CNT) was successfully attached to a base probe with a blunt apex and subsequently used as a probe for an atomic force microscope (AFM). This setup demonstrates high spatial resolution properties, plus an advantage: we were able to readily identify the loss of the CNT from the end of the probe by the resultant sudden drop in resolution. This design of probe is expected to feature yet another advantage: that of relative immunity to accidental collision compared to a CNT attached to a commercially available sharp tip. We also discuss the problems specific to CNT-attached probes, which are carbon contamination of the sample surface and artifact images formed at the edge of pit structures. We demonstrate that carbon contamination can be suppressed by a rubbing procedure before the scanning use, and that pit artifacts can be eliminated by optimizing the CNT length.

  5. Cross section database for carbon atoms and ions: Electron-impact ionization, excitation, and charge exchange in collisions with hydrogen atoms

    SciTech Connect

    Suno, Hiroya . E-mail: suno@jamstec.go.jp; Kato, Takako

    2006-07-15

    A database has been constructed consisting of the recommended cross sections for electron-impact excitation and ionization of carbon atoms and ions C, C{sup +}-C{sup 5+}, asl as for charge exchange processes between carbon ions C{sup +}-C{sup 6+} and hydrogen atoms. We have collected a large amount of theoretical and experimental cross section data from the literature, and have critically assessed their accuracy. The recommended cross sections, the best values for use, are expressed in the form of simple analytical functions. These are also presented in graphical form.

  6. Atom Probe Tomography Examination of Carbon Redistribution in Quenched and Tempered 4340 Steel

    SciTech Connect

    Clarke, Amy J.; Miller, Michael K.; Alexander, David J.; Field, Robert D.; Clarke, Kester D.

    2012-08-07

    Quenching and tempering produces a wide range of mechanical properties in medium carbon, low alloyed steels - Study fragmentation behavior as a function of heat-treatment. Subtle microstructural changes accompany the mechanical property changes that result from quenching and tempering - Characterize the location and distribution of carbon and alloying elements in the microstructure using atom probe tomography (APT). Perform complementary transmission electron microscopy (TEM). Tempering influences the mechanical properties and fragmentation of quenched 4340 (hemi-shaped samples). APT revealed carbon-enriched features that contain a maximum of {approx}12-14 at.% carbon after quenching to RT (the level of carbon is perhaps associated with the extent of autotempering). TEM confirmed the presence of twinned martensite and indicates {var_epsilon} ({eta}) transition carbides after oil quenching to RT. Tempering at 325 C resulted in carbon-enriched plates (> 25 at.% C) with no significant element partitioning (transition carbides?). Tempering at 450 C and 575 C resulted in cementite ({approx} 25 at.% C) during late stage tempering; Cr, Mn, Mo partitioned to cementite and Si partitioned to ferrite. Tempering at 575 C resulted in P segregation at cementite interfaces and the formation of Cottrell atmospheres.

  7. Study of double bond equivalents and the numbers of carbon and oxygen atom distribution of dissolved organic matter with negative-mode FT-ICR MS.

    PubMed

    Bae, EunJung; Yeo, In Joon; Jeong, Byungkwan; Shin, Yongsik; Shin, Kyung-Hoon; Kim, Sunghwan

    2011-06-01

    A strong linear relationship was observed between the average double bond equivalence (DBE) and the ratio of carbon to oxygen atoms in oxygenated compounds of dissolved organic matter (DOM). Data were acquired by a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS), equipped with a negative-mode electrospray ionization source. The slope and y-intercepts extracted from the linear relationship can be used to compare DOM samples originating from different locations. Significant differences in these parameters were observed between inland riverine and offshore coastal DOM samples. Offshore coastal DOM molecules underwent a change of one DBE for each removal or addition of two oxygen atoms. This suggested the existence of multiple carboxyl groups, each of which contains a double bond and two oxygen atoms. Inland riverine samples exhibited a change of ~1.5 DBE following the addition or removal of two oxygen atoms. This extra change in DBE was attributed to cyclic structures or unsaturated chemical bonds. The DBE value with maximum relative abundance and the minimum DBE value for each class of oxygenated compounds showed that approximately two oxygen atoms contributed to a unity change in DBE. The qualitative analyses given here are in a good agreement with results obtained from analyses using orthogonal analytical techniques. This study demonstrates that DBE and the carbon number distribution, observed by high resolution mass spectrometry, can be valuable in elucidating and comparing structural features of oxygenated molecules of DOM.

  8. Spin-probe ESR and molecular modeling studies on calcium carbonate dispersions in overbased detergent additives.

    PubMed

    Montanari, Luciano; Frigerio, Francesco

    2010-08-15

    Oil-soluble calcium carbonate colloids are used as detergent additives in lubricating oils. They are colloidal dispersions of calcium carbonate particles stabilized by different surfactants; in this study alkyl-aryl-sulfonates and sulfurized alkyl-phenates, widely used in the synthesis of these additives, are considered. The physical properties of surfactant layers surrounding the surfaces of calcium carbonate particles were analyzed by using some nitroxide spin-probes (stable free radicals) and observing the corresponding ESR spectra. The spin-probe molecules contain polar groups which tend to tether them to the carbonate particle polar surface. They can reach these surfaces only if the surfactant layers are not very compact, hence the relative amounts of spin-probe molecules accessing carbonate surfaces are an index of the compactness of surfactant core. ESR signals of spin-probe molecules dissolved in oil or "locked" near the carbonate surfaces are different because of the different molecular mobility. Through deconvolution of the ESR spectra, the fraction of spin-probes penetrating surfactant shells have been calculated, and differences were observed according to the surfactant molecular structures. Moreover, by using specially labeled spin-probes based on stearic acids, functionalized at different separations from the carboxylic acid group, it was possible to interrogate the molecular physical behavior of surfactant shells at different distances from carbonate surfaces. Molecular modeling was applied to generate some three-dimensional micellar models of the colloidal stabilizations of the stabilized carbonate particles with different molecular structures of the surfactant. The diffusion of spin-probe molecules into the surfactant shells were studied by applying a starting force to push the molecules towards the carbonate surfaces and then observing the ensuing behavior. The simulations are in accordance with the ESR data and show that the geometrical

  9. Effect of additives on size and shape of lithium carbonate crystals

    NASA Astrophysics Data System (ADS)

    Taborga, P.; Brito, I.; Graber, T. A.

    2017-02-01

    Generally, properties such internal structure, shape, and size distribution influence the reactivity, fluidity and wettability of the crystals, and may be modified by the use of additives such as polyelectrolytes or surfactants. The aim of this study was to investigate the effect of different additives on the size and morphology of lithium carbonate crystals obtained by reactive crystallization from solutions of LiCl and Na2CO3. The additives used were: polyethylenimine (PEI), polyethylene glycol (PEG), poly (4-styrenesulfonic acid), (P4SA), polyacrylic acid (PAA), sodium dodecyl sulfate (SDS), and sodium dodecyl benzenesulfonate (SDBS). Obtained crystals were observed using scanning electron microscopy, the crystal size distribution was determined by a size image analyzer, and the crystal structure were analyzed by X-ray diffraction. The results showed that the presence of PEI, PEG and P4SA, increased the length of the lithium carbonate particles. The presence of SDS decreases the crystals size. Using SDBS as additive, the crystals had a needle-like shape, Finally PAA allowed the production of Li2CO3 spherulites. Crystal structure of lithium carbonate did not change in the presence of the tested additives.

  10. Growth, characterization, and properties of carbon nitride with and without silicon addition

    SciTech Connect

    Chen, L.C.; Wu, C.T.; Wu, J.J.; Chen, K.H.

    2000-01-30

    Carbon nitride and silicon carbon nitride have been grown by microwave plasma chemical vapor deposition, electron-cyclotron-resonance plasma chemical vapor deposition, magnetron sputtering and ion beam sputtering. Depending on the specific process details, a wide range of microstructure and morphologies has been demonstrated. Effects of Si addition to CN network on the structure of the deposited materials were studied. While Si involvement in CVD process was crucial for crystal growth, excessive Si incorporation led to formation of amorphous phase in PVD process. Various optical constants including the band gap and refractive index of the SiCN phases are also reported.

  11. Catalytic polymerization of carbon monoxide and olefin, with organo nitro or organo nitrite compound additive

    SciTech Connect

    Drent, E.; Wife, R.L.

    1989-02-21

    In the process of producing linear alternating polymers or carbon monoxide and at least one ethylenically unsaturated hydrocarbon by contacting the carbon monoxide and unsaturated hydrocarbon under polymerization conditions in the presence of a catalyst composition formed from a mixture of a palladium compound, the anion of a non-hydrohalogenic acid having a pKa below about 6 and a bidentate phosphorus ligand, the improvement wherein the mixture from which the catalyst composition is formed additionally contains an organic nitro compound or an organic nitride compound.

  12. Diagnostics of Carbon Nanotube Formation in a Laser Produced Plume: An Investigation of the Metal Catalyst by Laser Ablation Atomic Fluorescence Spectroscopy

    NASA Technical Reports Server (NTRS)

    deBoer, Gary; Scott, Carl

    2003-01-01

    atoms survive for several milliseconds while the gaseous carbon atoms and small molecules nucleate more rapidly. Additional experiments and the development of in situ methods for carbon nanotube detection would allow these results to be interpreted from the perspective of carbon nanotube formation.

  13. Soot platelets and PAHs with an odd number of unsaturated carbon atoms and pi electrons: theoretical study of their spin properties and interaction with ozone.

    PubMed

    Giordana, Anna; Maranzana, Andrea; Ghigo, Giovanni; Causà, Mauro; Tonachini, Glauco

    2008-02-07

    PAHs made from an odd number of unsaturated carbon atoms and pi electrons (odd PAHs) have been detected in flames and flank the more familiar even PAHs, having approximately the same quantitative importance, particularly for PAHs containing more than 25 carbon atoms. Similarly, soot platelets containing an odd number of carbon atoms can be reasonably assumed to form during combustion. PAHs are intended here as small models for the investigation of some of their local features. To this end, quantum mechanical calculations were also carried out on periodic models. The spin density patterns were found to be highly dependent on the PAH size and shape. PAHs and soot, once released in the environment, can undergo several oxidation processes. Ozone is then taken as a probe of the reactivity properties of some internal exposed portions of a platelet. A primary ozonide (PO) corresponds to an energy minimum, but the relevant concerted addition pathway does not exist, because a PO-like saddle point is second-order. The reaction begins with a nonconcerted attack that produces a trioxyl radical (TR). Subsequent O2 loss from the TR leaves either an epoxide with a pi-delocalized electron or a pi-delocalized oxepine, by cleavage of the ring carbon-carbon bond. The initial doublet spin multiplicity thus provides a description of the reaction surface unlike that for the internal reactivity of the closed-shell even systems investigated in a previous work, even though the final functionalization is the same.

  14. Influence of additive effective atomic number on alpha-oxide radiolysis

    SciTech Connect

    Doroshenko, V.N.; Entinzon, I.R.; Meleshevich, A.P.

    1988-07-01

    If a monomer or polymer is irradiated in the presence of a filler or on an inorganic substrate, one has to determine how the phase boundaries affect the reaction rates in the organic components. We have restricted consideration to the approximate relation between the additional absorbed energy taken up by the monomer or oligomer f/sub ECH/(P) and P for a composite based on epichlorohydrin (ECH) on /sup 60/Co /gamma/ irradiation. We determined the polymer yield (conversion /chi/ in %) in the ECH-SiO/sub 2/ and ECH-Al/sub 2/O/sub 3/ systems containing 1-50% oxide.

  15. Bridged single-walled carbon nanotube-based atomic-scale mass sensors

    NASA Astrophysics Data System (ADS)

    Ali-Akbari, H. R.; Shaat, M.; Abdelkefi, A.

    2016-08-01

    The potentials of carbon nanotubes (CNTs) as mechanical resonators for atomic-scale mass sensing are presented. To this aim, a nonlocal continuum-based model is proposed to study the dynamic behavior of bridged single-walled carbon nanotube-based mass nanosensors. The carbon nanotube (CNT) is considered as an elastic Euler-Bernoulli beam with von Kármán type geometric nonlinearity. Eringen's nonlocal elastic field theory is utilized to model the interatomic long-range interactions within the structure of the CNT. This developed model accounts for the arbitrary position of the deposited atomic-mass. The natural frequencies and associated mode shapes are determined based on an eigenvalue problem analysis. An atom of xenon (Xe) is first considered as a specific case where the results show that the natural frequencies and mode shapes of the CNT are strongly dependent on the location of the deposited Xe and the nonlocal parameter of the CNT. It is also indicated that the first vibrational mode is the most sensitive when the mass is deposited at the middle of a single-walled carbon nanotube. However, when deposited in other locations, it is demonstrated that the second or third vibrational modes may be more sensitive. To investigate the sensitivity of bridged single-walled CNTs as mass sensors, different noble gases are considered, namely Xe, argon (Ar), and helium (He). It is shown that the sensitivity of the single-walled CNT to the Ar and He gases is much lower than the Xe gas due to the significant decrease in their masses. The derived model and performed analysis are so needed for mass sensing applications and particularly when the detected mass is randomly deposited.

  16. Influence of atomic vacancies on the dynamic characteristics of nanoresonators based on double walled carbon nanotube

    NASA Astrophysics Data System (ADS)

    Patel, Ajay M.; Joshi, Anand Y.

    2015-06-01

    The dynamic analysis of double walled carbon nanotubes (DWCNTs) with different boundary conditions has been performed using atomistic finite element method. The double walled carbon nanotube is modeled considering it as a space frame structure similar to a three dimensional beam. The elastic properties of beam element are calculated by considering mechanical characteristics of covalent bonds between the carbon atoms in the hexagonal lattice. Spring elements are used to describe the interlayer interactions between the inner and outer tubes caused due to the van der Waals forces. The mass of each beam element is assumed as point mass at nodes coinciding with carbon atoms at inner and outer wall of DWCNT. It has been reported that atomic vacancies are formed during the manufacturing process in DWCNT which tend to migrate leading to a change in the mechanical characteristics of the same. Simulations have been carried out to visualize the behavior of such defective DWCNTs subjected to different boundary conditions and when used as mass sensing devices. The variation of such atomic vacancies in outer wall of Zigzag and Armchair DWCNT is performed along the length and the change in response is noted. Moreover, as CNTs have been used as mass sensors extensively, the present approach is focused to explore the use of zigzag and armchair DWCNT as sensing device with a mono-atomic vacancy in it. The results clearly state that the dynamic characteristics are greatly influenced by defects like vacancies in it. A higher frequency shift is observed when the vacancy is located away from the fixed end for both Armchair as well as zigzag type of CNTs. A higher frequency shift is reported for armchair CNT for a mass of 10-22 g which remains constant for 10-21 g and then decreases gradually. Comparison with the other experimental and theoretical studies exhibits good association which suggests that defective DWCNTs can further be explored for mass sensing. This investigation is helpful

  17. Improving the analytical performance of hydride generation non-dispersive atomic fluorescence spectrometry. Combined effect of additives and optical filters

    NASA Astrophysics Data System (ADS)

    D'Ulivo, Alessandro; Bramanti, Emilia; Lampugnani, Leonardo; Zamboni, Roberto

    2001-10-01

    The effects of tetrahydroborate and acid concentration and the presence of L-cysteine and thiourea were investigated in the determination of As, Bi and Sn using continuous flow hydride generation atomic fluorescence spectrometry (HG AFS). The aim was to find conditions allowing the control of those effects exerting negative influence on the analytical performance of the HG AFS apparatus. The effects taken into account were: (i) the radiation scattering generated by carryover of solution from the gas-liquid separator to the atomizer; (ii) the introduction of molecular species generated by tetrahydroborate decomposition into the atomizer; and (iii) interference effects arising from other elements in the sample matrix and from different acids. The effects (i) and (ii) could be controlled using mild reaction conditions in the HG stage. The effect of HG conditions on carryover was studied by radiation scattering experiments without hydride atomization. Compromised HG conditions were found by studying the effects of tetrahydroborate (0.1-20 g l -1) and acid (0.01-7 mol l -1) concentration, and the addition of L-cysteine (10 g l -1) and thiourea (0.1 mol l -1) on the HG AFS signals. The effect of optical filters was investigated with the aim of improving the signal-to-noise ratio. Optical filters with peak wavelengths of 190 and 220 nm provided an improvement of detection limits by factors of approximately 4 and 2 for As and Te, respectively. Under optimized conditions the detection limits were 6, 5, 3, 2, 2 and 9 ng l -1 for As, Sb, Bi, Sn, Se and Te, respectively. Good tolerance to various acid compositions and sample matrices was obtained by using L-cysteine or thiourea as masking agents. Determination of arsenic in sediment and copper certified reference materials, and of bismuth in steel, sediment, soil and ore certified reference material is reported.

  18. Optimization of membrane bioreactors by the addition of powdered activated carbon.

    PubMed

    Ng, Choon Aun; Sun, Darren; Bashir, Mohammed J K; Wai, Soon Han; Wong, Ling Yong; Nisar, Humaira; Wu, Bing; Fane, Anthony G

    2013-06-01

    It was found that with replenishment, powdered activated carbon (PAC) in the membrane bioreactor (MBR) would develop biologically activated carbon (BAC) which could enhance filtration performance of a conventional MBR. This paper addresses two issues (i) effect of PAC size on MBR (BAC) performance; and (ii) effect of sludge retention time (SRT) on the MBR performance with and without PAC. To interpret the trends, particle/floc size, concentration of mixed liquor suspended solid (MLSS), total organic carbon (TOC), short-term filtration properties and transmembrane pressure (TMP) versus time are measured. The results showed improved fouling control with fine, rather than coarse, PAC provided the flux did not exceed the deposition flux for the fine PAC. Without PAC, the longer SRT operation gave lower fouling at modest fluxes. With PAC addition, the shorter SRT gave better fouling control, possibly due to greater replenishment of the fresh PAC.

  19. CASCADES AFTER K-VACANCY PRODUCTION AND ADDITIONAL IONIZATION OR EXCITATION IN ATOMS OF LIGHT ELEMENTS

    SciTech Connect

    Kucas, S.; Momkauskaitė, A.; Karazija, R.

    2015-09-01

    The results of Auger and radiative cascades after the production of a vacancy in the K-shell and the additional ionization or excitation of the other shell are presented for the various ions of astrophysically important elements, namely, Ne, Mg, Si, S, and Ar. The detailed level-by-level calculations are performed using a single-configuration quasi-relativistic approximation. The populations of the levels of the excited configurations produced during a cascade as well as for the final ions are presented. These data enable us to take into account two-electron processes at the K-shell ionization, and thus to supplement the results of our earlier investigation of K-vacancy cascades.

  20. An atomistic study of growth mode and microstructure evolution of amorphous carbon films by different incident carbon atoms

    NASA Astrophysics Data System (ADS)

    Xue, Chen; Zhou, Jianqiu

    2014-09-01

    In this paper, molecular dynamics (MD) simulation has been performed to describe the growth and interfacial microstructure of amorphous carbon films. We focus on the film growth mode and surface morphology for diverse deposition process parameters mainly including incident energy and incident angle. To explore the relationship between the motion of deposition atoms and amorphous films growth, a series of snapshots for each deposition process has been taken for comparison. The snapshots show that the films growth modes are diverse at different incident parameters. In the next step, surface morphology, atom distribution along film growth direction and internal structure including vacancy defects evolution during deposition process are analyzed. The results reveal that incident energy on the horizontal plane dominates the surface roughness, and incident energy on the vertical plane dominates the compactness of the film. We conclude that a suitable incident parameter is not only beneficial to prepare amorphous films with compact and smooth or bump-like surface which will meet different needs, but also can avoid formation of defects during deposition. The simulation results are expected to provide useful guidance for improving amorphous carbon films quality.

  1. Impact of titanium addition on film characteristics of HfO2 gate dielectrics deposited by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Triyoso, D. H.; Hegde, R. I.; Zollner, S.; Ramon, M. E.; Kalpat, S.; Gregory, R.; Wang, X.-D.; Jiang, J.; Raymond, M.; Rai, R.; Werho, D.; Roan, D.; White, B. E.; Tobin, P. J.

    2005-09-01

    The impact of 8-to 45-at. % Ti on physical and electrical characteristics of atomic-layer-deposited and annealed hafnium dioxide was studied using vacuum-ultraviolet spectroscopic ellipsometry, secondary ion mass spectroscopy, transmission electron microscopy, atomic force microscopy, x-ray diffraction, Rutherford backscattering spectroscopy, x-ray photoelectron spectroscopy, and x-ray reflectometry. The role of Ti addition on the electrical performance is investigated using molybdenum (Mo)-gated capacitors. The film density decreases with increasing Ti addition. Ti addition stabilizes the amorphous phase of HfO2, resulting in amorphous films as deposited. After a high-temperature annealing, the films transition from an amorphous to a polycrystalline phase. Orthorhombic Hf-Ti-O peaks are detected in polycrystalline films containing 33-at. % or higher Ti content. As Ti content is decreased, monoclinic HfO2 becomes the predominant microstructure. No TiSi is formed at the dielectric/Si interface, indicating films with good thermal stability. The band gap of Hf-Ti-O was found to be lower than that of HfO2. Well-behaved capacitance-voltage and leakage current density-voltage characteristics were obtained for Hf-Ti-O. However, an increased leakage current density was observed with Ti addition. The data from capacitance-voltage stressing indicate a smaller flatband voltage (Vfb) shift in the HfO2 films with low Ti content when compared with the HfO2 films. This indicates less charge trapping with a small amount of Ti addition.

  2. A first principle study for the adsorption and absorption of carbon atom and the CO dissociation on Ir(100) surface

    SciTech Connect

    Erikat, I. A.; Hamad, B. A.

    2013-11-07

    We employ density functional theory to examine the adsorption and absorption of carbon atom as well as the dissociation of carbon monoxide on Ir(100) surface. We find that carbon atoms bind strongly with Ir(100) surface and prefer the high coordination hollow site for all coverages. In the case of 0.75 ML coverage of carbon, we obtain a bridging metal structure due to the balance between Ir–C and Ir–Ir interactions. In the subsurface region, the carbon atom prefers the octahedral site of Ir(100) surface. We find large diffusion barrier for carbon atom into Ir(100) surface (2.70 eV) due to the strong bonding between carbon atom and Ir(100) surface, whereas we find a very small segregation barrier (0.22 eV) from subsurface to the surface. The minimum energy path and energy barrier for the dissociation of CO on Ir(100) surface are obtained by using climbing image nudge elastic band. The energy barrier of CO dissociation on Ir(100) surface is found to be 3.01 eV, which is appreciably larger than the association energy (1.61 eV) of this molecule.

  3. Formation of the geometrically controlled carbon coils by manipulating the additive gas (SF6) flow rate.

    PubMed

    Jeon, Young-Chul; Kim, Sung-Hoon

    2012-07-01

    Carbon coils could be synthesized using C2H2/H2 as source gases and SF6 as an incorporated additive gas under the thermal chemical vapor deposition system. The nickel catalyst layer deposition and then hydrogen plasma pretreatment were performed prior to the carbon coils deposition reaction. The flow rate and the injection time of SF6 varied according to the different reaction processes. Geometries of carbon coils developed from embryos to nanosized coils with increasing SF, flow rate from 5 to 35 sccm under the short SF6 flow injection time (5 minutes) condition. The gradual development of carbon coils geometries from nanosized to microsized types could be observed with increasing SF6 flow rate under the full time (90 minutes) SF6 flow injection condition. The flow rate of SF6 for the coil-type geometry formation should be more than or at least equal to the flow rate of carbon source gas (C2H2). A longer injection time of SF6 flow would increase the size of coils diameters from nanometer to micrometer.

  4. Synthesis of barium and strontium carbonate crystals with unusual morphologies using an organic additive

    NASA Astrophysics Data System (ADS)

    Chen, Long; Jiang, Jizhong; Bao, Zuben; Pan, Jian; Xu, Weibing; Zhou, Lili; Wu, Zhigang; Chen, Xu

    2013-12-01

    In this paper, strontium carbonate (SrCO3) and barium carbonate (BaCO3) crystals were synthesized in the presence of an organic additive-hexamethylenetetramine (HMT) using two CO2 sources. Scanning electron microscopy and X-ray powder diffractometry were used to characterize the products. The results showed that the morphologies of orthorhombic strontianite SrCO3 transformed from branch-like to flower-like, and to capsicum-like at last, while the morphologies of BaCO3 change from fiber-like to branchlike, and to rod-like finally with an increase of the molar ratio HMT/Sr2+ and HMT/Ba2+ from 0.2 to 10 using ammonium carbonate as CO2 source. When using diethyl carbonate instead of ammonium carbonate as CO2 source, SrCO3 flowers aggregated by rods and BaCO3 shuttles were formed. The possible formation mechanisms of SrCO3 and BaCO3 crystals obtained in different conditions were also discussed.

  5. Tetragonality and the distribution of carbon atoms in the Fe-C martensite: Molecular-dynamics simulation

    NASA Astrophysics Data System (ADS)

    Chirkov, P. V.; Mirzoev, A. A.; Mirzaev, D. A.

    2016-01-01

    In the statistical theory of the ordering of carbon atoms in the z sublattice of martensite, the most important role is played by the parameter of the strain interaction of carbon atoms λ0, which determines the critical temperature of the bcc-bct transition. The values of this parameter (6-11 eV/atom) obtained in recent years by the methods of computer simulation differ significantly from the value λ0 = 2.73 eV/atom obtained by A. G. Khachaturyan. In this article, we calculated the value of λ0 by two methods based on the molecular-dynamics simulation of the ordering of carbon atoms in the lattice of martensite at temperatures of 500, 750, 900, and 1000 K in a wide range of carbon concentrations, which includes c crit. No tails of ordering below c crit have been revealed. It has been shown analytically that there is an inaccuracy in the Khachaturyan theory of ordering for the crystal in an elastic environment. After eliminating this inaccuracy, no tails of the order parameter appear; the tetragonality changes jumpwise from η = 0 to ηcrit = 0.75 at c crit = 2.9 kT/λ0 instead of ηcrit = 0.5 and c crit= 2.77 kT/λ0 for an isolated crystal. Upon the simulation, clustering of carbon atoms was revealed in the form of platelike pileups along {102} planes separated by flat regions where no carbon atoms were present. The influence of short-range order in the arrangement of neighboring carbon atoms on the thermodynamics of ordering is discussed.

  6. High temperature hydrogen sulfide adsorption on activated carbon - I. Effects of gas composition and metal addition

    USGS Publications Warehouse

    Cal, M.P.; Strickler, B.W.; Lizzio, A.A.

    2000-01-01

    Various types of activated carbon sorbents were evaluated for their ability to remove H2S from a simulated coal gas stream at a temperature of 550 ??C. The ability of activated carbon to remove H2S at elevated temperature was examined as a function of carbon surface chemistry (oxidation, thermal desorption, and metal addition), and gas composition. A sorbent prepared by steam activation, HNO3 oxidation and impregnated with Zn, and tested in a gas stream containing 0.5% H2S, 50% CO2 and 49.5% N2, had the greatest H2S adsorption capacity. Addition of H2, CO, and H2O to the inlet gas stream reduced H2S breakthrough time and H2S adsorption capacity. A Zn impregnated activated carbon, when tested using a simulated coal gas containing 0.5% H2S, 49.5% N2, 13% H2, 8.5% H2O, 21% CO, and 7.5% CO2, had a breakthrough time of 75 min, which was less than 25 percent of the length of breakthrough for screening experiments performed with a simplified gas mixture of 0.5% H2S, 50% CO2, and 49.5% N2.

  7. Atomic scale enhancement of the adhesion of beryllium films to carbon substrates

    SciTech Connect

    Musket, R.G.; Wirtenson, G.R.

    1995-12-01

    We have used 200 keV carbon ions to enhance the adhesion of 240-nm thick Be films to polished, vitreous carbon substrates. Adhesion of the as-deposited films was below that necessary to pass the scotch-tape test. Carbon ion fluences less than 1.6x10{sup 14} C/cm{sup 2} were sufficient to ensure the passage of the tape test without affecting the optical properties of the films. Adhesion failure of the as-deposited film was attributed to an inner oxide layer between the Be and the carbon. Because this oxide ({approximately}5 nm of BeO) was not measurably changed by the irradiation process, these results are consistent with adhesion enhancement occurring on the atomic scale at the interface between the inner oxide and the carbon substrate. This conclusion was supported by Rutherford backscattering (RBS) data, and potential adhesion mechanisms are discussed with consideration of relative contributions from electronic and nuclear stopping.

  8. Inelastic and reactive scattering of hyperthermal atomic oxygen from amorphous carbon

    NASA Technical Reports Server (NTRS)

    Minton, Timothy K.; Nelson, Christine M.; Brinza, David E.; Liang, Ranty H.

    1991-01-01

    The reaction of hyperthermal oxygen atoms with an amorphous carbon-13 surface was studied using a modified universal crossed molecular beams apparatus. Time-of-flight distributions of inelastically scattered O-atoms and reactively scattered CO-13 and CO2-13 were measured with a rotatable mass spectrometer detector. Two inelastic scattering channels were observed, corresponding to a direct inelastic process in which the scattered O-atoms retain 20 to 30 percent of their initial kinetic energy and to a trapping desorption process whereby O-atoms emerge from the surface at thermal velocities. Reactive scattering data imply the formation of two kinds of CO products, slow products whose translational energies are determined by the surface temperature and hyperthermal (Approx. 3 eV) products with translational energies comprising roughly 30 percent of the total available energy (E sub avl), where E sub avl is the sum of the collision energy and the reaction exothermicity. Angular data show that the hyperthermal CO is scattered preferentially in the specular direction. CO2 product was also observed, but at much lower intensities than CO and with only thermal velocities.

  9. Interaction between a single Pt atom and a carbon nanotube studied by density functional theory

    NASA Astrophysics Data System (ADS)

    Chen, G.; Kawazoe, Y.

    2006-03-01

    Using density functional theory with the generalized gradient approximation, we have studied the interaction between a single Pt atom and a carbon nanotube. The bridge adsorption site on the outer wall of nanotube is favorable. The curvature affects the binding strength. Compared to the larger nanotube, Pt could bind stronger to the outer wall of a small radius nanotube. For zigzag nanotube, the most stable site on the outer wall is the bridge site with the underlying C-C bond being parallel to the axis of the nanotube, while for the armchair nanotube it is the bridge site with the underlying C-C bond being tilted to the axis of the nanotube. The energy in average differs by ˜1.5eV for adsorbing on both sidewalls of small radius nanotube, while it decreases much for the larger nanotube. Either by penetrating the wall or by substituting one C atom on the wall, the Pt atom is found to be hard to diffuse from the outside to the inside. The studied charge density suggests the weak covalentlike bonding between Pt and C atoms.

  10. Probing spin-orbit-interaction-induced electron dynamics in the carbon atom by multiphoton ionization

    NASA Astrophysics Data System (ADS)

    Rey, H. F.; van der Hart, H. W.

    2014-09-01

    We use R-matrix theory with time dependence (RMT) to investigate multiphoton ionization of ground-state atomic carbon with initial orbital magnetic quantum number ML=0 and ML=1 at a laser wavelength of 390 nm and peak intensity of 1014W/cm2. Significant differences in ionization yield and ejected-electron momentum distribution are observed between the two values for ML. We use our theoretical results to model how the spin-orbit interaction affects electron emission along the laser polarization axis. Under the assumption that an initial C atom is prepared at zero time delay with ML=0, the dynamics with respect to time delay of an ionizing probe pulse modeled by using RMT theory is found to be in good agreement with available experimental data.

  11. Asymmetric catalysis for the construction of quaternary carbon centres: nucleophilic addition on ketones and ketimines.

    PubMed

    Riant, Olivier; Hannedouche, Jérôme

    2007-03-21

    There is a growing need in organic synthesis for efficient methodologies for the asymmetric synthesis of quaternary carbon centres. One of the most attractive and straightforward methods focuses on the use of asymmetric catalysis for the addition of various types of nucleophiles on prochiral ketones and ketimines. A view of the literature from this growing area of research will be presented in this review, with an emphasis on the pioneer works and milestones brought by the main players in this field.

  12. Controlling the Electrostatic Discharge Ignition Sensitivity of Composite Energetic Materials Using Carbon Nanotube Additives

    DTIC Science & Technology

    2014-08-10

    Michelle L. Pantoya, Michael A. Daniels Se. TASK NUMBER Sf. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAMES AND ADDRESSES 8. PERFORMING ORGANIZATION...of composite energetic materials using carbon nanotube additives Kade H. Poper a, Eric S. Collins a, Michelle L. Pantoya a, *, Michael A. Daniels b a...Thermochim. Acta 451 (1 2) (2006). [2] Chelsea Weir, Michelle L. Pantoya, Michael Daniels , Electrostatic discharge sensitivity and electrical conductivity

  13. PCB bioavailability control in Lumbriculus variegatus through different modes of activated carbon addition to sediments

    SciTech Connect

    Xueli Sun; Upal Ghosh

    2007-07-01

    PCB bioavailability to a freshwater oligochaete (Lumbriculus variegatus) was studied using sediments from a PCB-impacted river that was treated with different modes of granular activated carbon (GAC) addition. The GAC used was bituminous coal-based type TOP. For sediment treated with 2.6% GAC and mixed for 2 min prior to L. variegatus addition, the reduction in total PCB biouptake was 70% for 75-300 {mu}m size carbon, and 92% for the 45-180 {mu}m size carbon. For the case where the GAC was placed as a thin layer on top of the sediments without mixing, the reduction in total PCB uptake was 70%. PCB biouptake kinetics study using treated and untreated sediment showed that the maximum PCB uptake in tissue was achieved at 28 days and decreased after that time. Although the absolute uptake of PCB changed over time, the percent reduction in total PCB uptake upon GAC amendment remained constant after the first few days. Our results indicated that PCB bioavailability was reduced upon the addition and little or no mixing of GAC into sediments. PCB aqueous equilibrium concentration and desorption rates were greatly reduced after GAC amendment, indicating reductions in the two primary mechanisms of PCB bioavailability in sediments: chemical activity and chemical accessibility. 29 refs., 5 figs., 1 tab.

  14. PCB bioavailability control in Lumbriculus variegatus through different modes of activated carbon addition to sediments.

    PubMed

    Sun, Xueli; Ghosh, Upal

    2007-07-01

    PCB bioavailability to a freshwater oligochaete (Lumbriculus variegatus) was studied using sediments from a PCB-impacted river that was treated with different modes of granular activated carbon (GAC) addition. For sedimenttreated with 2.6% GAC and mixed for 2 min prior to L. variegatus addition, the reduction in total PCB biouptake was 70% for 75-300 microm size carbon, and 92% for the 45-180 microm size carbon. For the case where the GAC was placed as a thin layer on top of the sediments without mixing, the reduction in total PCB uptake was 70%. PCB biouptake kinetics study using treated and untreated sediment showed that the maximum PCB uptake in tissue was achieved at 28 days and decreased after that time. Although the absolute uptake of PCB changed over time, the percent reduction in total PCB uptake upon GAC amendment remained constant after the first few days. Our results indicated that PCB bioavailability was reduced upon the addition and little or no mixing of GAC into sediments. PCB aqueous equilibrium concentration and desorption rates were greatly reduced after GAC amendment, indicating reductions in the two primary mechanisms of PCB bioavailability in sediments: chemical activity and chemical accessibility.

  15. Reconstruction of carbon atoms around a point defect of a graphene: a hybrid quantum/classical molecular-dynamics simulation.

    PubMed

    Kowaki, Y; Harada, A; Shimojo, F; Hoshino, K

    2009-02-11

    We have investigated the rearrangement of carbon atoms around a point defect of a graphene using a hybrid ab initio/classical molecular-dynamics (MD) simulation method, in which 36 carbon atoms surrounding a point defect are treated by the ab initio MD method and the other 475 carbon atoms relatively far from the point defect are treated by the classical MD method. We have confirmed a formation of a 5-1DB defect (a pentagon and a dangling bond) from the time dependence of atomic configurations and electron density distributions obtained by our simulation. We have found that the pentagon is formed in two different positions around the point defect, and that the two positions appear alternately during the simulation, the frequency of which increases with increasing temperature.

  16. Carbon nanotubes as solid-phase extraction sorbents prior to atomic spectrometric determination of metal species: a review.

    PubMed

    Herrero Latorre, C; Álvarez Méndez, J; Barciela García, J; García Martín, S; Peña Crecente, R M

    2012-10-24

    New materials have significant impact on the development of new methods and instrumentation for chemical analysis. From the discovery of carbon nanotubes in 1991, single and multi-walled carbon nanotubes--due to their high adsorption and desorption capacities--have been employed as sorption substrates in solid-phase extraction for the preconcentration of metal species from diverse matrices. Looking for successive improvements in sensitivity and selectivity, in the past few years, carbon nanotubes have been utilized as sorbents for solid phase extraction in three different ways: like as-grown, oxidized and functionalized nanotubes. In the present paper, an overview of the recent trends in the use of carbon nanotubes for solid phase extraction of metal species in environmental, biological and food samples is presented. The determination procedures involved the adsorption of metals on the nanotube surface, their quantitative desorption and subsequent measurement by means of atomic spectrometric techniques such as flame atomic absorption spectrometry, electrothermal atomic absorption spectrometry or inductively coupled plasma atomic emission spectrometry/mass spectrometry, among others. Synthesis, purification and types of carbon nanotubes, as well as the diverse chemical and physical strategies for their functionalization are described. Based on 140 references, the performance and general properties of the applications of solid phase extraction based on carbon nanotubes for metal species atomic spectrometric determination are discussed.

  17. Boosting Bifunctional Oxygen Electrolysis for N-Doped Carbon via Bimetal Addition.

    PubMed

    Wang, Jian; Ciucci, Francesco

    2017-02-15

    The addition of transition metals, even in a trace amount, into heteroatom-doped carbon (M-N/C) is intensively investigated to further enhance oxygen reduction reaction (ORR) activity. However, the influence of metal decoration on the electrolysis of the reverse reaction of ORR, that is, oxygen evolution reaction (OER), is seldom reported. Moreover, further improving the bifunctional activity and corrosion tolerance for carbon-based materials remains a big challenge, especially in OER potential regions. Here, bimetal-decorated, pyridinic N-dominated large-size carbon tubes (MM'-N/C) are proposed for the first time as highly efficient and durable ORR and OER catalysts. FeFe-N/C, CoCo-N/C, NiNi-N/C, MnMn-N/C, FeCo-N/C, NiFe-N/C, FeMn-N/C, CoNi-N/C, MnCo-N/C, and NiMn-N/C are systematically investigated in terms of their structure, composition, morphology, surface area, and active site densities. In contrast to conventional monometal and N-decorated carbon, small amounts of bimetal (≈2 at%) added during the one-step template-free synthesis contribute to increased pyridinic N content, much longer and more robust carbon tubes, reduced metal particle size, and stronger coupling between the encapsulated metals and carbon support. The synergy of those factors accounts for the dramatically improved ORR and OER activity and stability. By comparison, NiFe-N/C and MnCo-N/C stand out and achieve superior bifunctional oxygen catalytic performance, exceeding most of state-of-the-art catalysts.

  18. Addition of carbon sorbents to reduce PCB and PAH bioavailability in marine sediments: physicochemical tests.

    PubMed

    Zimmerman, John R; Ghosh, Upal; Millward, Rod N; Bridges, Todd S; Luthy, Richard G

    2004-10-15

    The addition of activated carbon as particulate sorbent to the biologically active layer of contaminated sediment is proposed as an in-situ treatment method to reduce the chemical and biological availability of hydrophobic organic contaminants (HOCs) such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). We report results from physicochemical experiments that assess this concept. PCB- and PAH-contaminated sediment from Hunters Point Naval Shipyard, San Francisco Bay, CA, was contacted with coke and activated carbon for periods of 1 and 6 months. Sediment treated with 3.4 wt % activated carbon showed 92% and 84% reductions in aqueous equilibrium PCB and PAH concentrations, 77% and 83% reductions in PCB and PAH uptake by semipermeable membrane devices (SPMD), respectively, and reductions in PCB flux to overlying water in quiescent systems up to 89%. Adding coke to contaminated sediment did not significantly decrease aqueous equilibrium PCB concentrations nor PCB or PAH availability in SPMD measurements. Coke decreased PAH aqueous equilibrium concentrations by 38-64% depending on coke dose and particle size. The greater effectiveness of activated carbon as compared to coke is attributed to its much greater specific surface area and a pore structure favorable for binding contaminants. The results from the physicochemical tests suggest that adding activated carbon to contaminated field sediment reduces HOC availability to the aqueous phase. The benefit is manifested relatively quickly under optimum contact conditions and improves in effectiveness with contact time from 1 to 6 months. Activated carbon application is a potentially attractive method for in-situ, nonremoval treatment of marine sediment contaminated with HOCs.

  19. Does the Use of Diamond-Like Carbon Coating and Organophosphate Lubricant Additive Together Cause Excessive Tribochemical Material Removal?

    SciTech Connect

    Zhou, Yan; Leonard, Donovan N.; Meyer, Harry M.; Luo, Huimin; Qu, Jun

    2015-08-22

    We observe unexpected wear increase on a steel surface that rubbed against diamond-like carbon (DLC) coatings only when lubricated by phosphate-based antiwear additives. Contrary to the literature hypothesis of a competition between zinc dialkyldithiophosphate produced tribofilms and DLC-induced carbon transfer, here a new wear mechanism based on carbon-catalyzed tribochemical interactions supported by surface characterization is proposed

  20. Branched aliphatic alkanes with quaternary substituted carbon atoms in modern and ancient geologic samples.

    SciTech Connect

    Kenig, F.; Simons, D.-J. H.; Crich, D.; Cowen, J. P.; Ventura, G. T.; Rehbein-Khalily, T.; Brown, T. C.; Anderson, K. B.; Chemistry; Univ. of Illinois at Chicago; Univ. of Hawaii

    2003-01-01

    A pseudohomologous series of branched aliphatic alkanes with a quaternary substituted carbon atom (BAQCs, specifically 2,2-di-methylalkanes and 3,3- and 5,5-diethylalkanes) were identified in warm (65{sup o}C) deep-sea hydrothermal waters and Late Cretaceous black shales. 5,5-Diethylalkanes were also observed in modern and Holocene marine shelf sediments and in shales spanning the last 800 million years of the geological record. The carbon number distribution of BAQCs indicates a biological origin. These compounds were observed but not identified in previous studies of 2.0 billion- to 2.2 billion-year-old metasediments and were commonly misidentified in other sediment samples, indicating that BAQCs are widespread in the geological record. The source organisms of BAQCs are unknown, but their paleobiogeographic distribution suggests that they have an affinity for sulfides and might be nonphotosynthetic sulfide oxidizers.

  1. Effect of atomic interconnects on percolation in single-walled carbon nanotube thin film networks.

    PubMed

    Tian, Xiaojuan; Moser, Matthew L; Pekker, Aron; Sarkar, Santanu; Ramirez, Jason; Bekyarova, Elena; Itkis, Mikhail E; Haddon, Robert C

    2014-07-09

    The formation of covalent bonds to single-walled carbon nanotube (SWNT) or graphene surfaces usually leads to a decrease in the electrical conductivity and mobility as a result of the structural rehybridization of the functionalized carbon atoms from sp(2) to sp(3). In the present study, we explore the effect of metal deposition on semiconducting (SC-) and metallic (MT-) SWNT thin films in the vicinity of the percolation threshold and we are able to clearly delineate the effects of weak physisorption, ionic chemisorption with charge transfer, and covalent hexahapto (η(6)) chemisorption on these percolating networks. The results support the idea that for those metals capable of forming bis-hexahapto-bonds, the generation of covalent (η(6)-SWNT)M(η(6)-SWNT) interconnects provides a conducting pathway in the SWNT films and establishes the transition metal bis-hexahapto organometallic bond as an electronically conjugating linkage between graphene surfaces.

  2. Removal of carbon and nanoparticles from lithographic materials by plasma assisted cleaning by metastable atom neutralization (PACMAN)

    NASA Astrophysics Data System (ADS)

    Lytle, W. M.; Lofgren, R. E.; Surla, V.; Neumann, M. J.; Ruzic, D. N.

    2010-04-01

    System cleanliness is a major issue facing the lithographic community as the prospects of integrating EUV lithography into integrated circuit manufacturing progress. Mask cleanliness, especially of particles in the sub-micron range, remains an issue for the implementation of EUV lithography since traditional mask cleaning processes are limited in their ability to remove nanometer scale contaminants. The result is lower wafer throughput due to errors in pattern transfer to the wafer from the particulate defects on the mask. Additionally, carbon contamination and growth on the collector optics due to energetic photon interactions degrade the mirror and shortens its functional life. Plasma cleaning of surfaces has been used for a variety of applications in the past, and now is being extended to cleaning surfaces for EUV, specifically the mask and collector optics, through a process developed in the Center for Plasma-Material Interactions (CPMI) called Plasma Assisted Cleaning by Metastable Atom Neutralization (PACMAN). This process uses energetic neutral atoms (metastables) in addition to a high-density plasma (Te ~ 3 eV and ne ~ 1017 m-3) to remove particles. The PACMAN process is a completely dry process and is carried out in a vacuum which makes it compatible with other EUV related processing steps. Experiments carried out on cleaning polystyrene latex (PSL) nanoparticles (30 nm to 500 nm) on silicon wafers, chrome coated mask blanks, and EUV mask blanks result in 100 % particle removal with a helium plasma and helium metastables. Removal rates greater than 20 nm/min have been achieved for PSL material. Similar removal rates have been achieved for the PACMAN cleaning of carbon from silicon wafers (simulating collector optic material) with 100% removal with helium plasma and helium metastables. The PACMAN cleaning technique has not caused any damage to the substrate type being cleaned either through roughening or surface sputtering. Current results of cleaning

  3. Raman spectroscopy as a tool to investigate the structure and electronic properties of carbon-atom wires

    PubMed Central

    Milani, Alberto; Tommasini, Matteo; Russo, Valeria; Li Bassi, Andrea; Lucotti, Andrea; Cataldo, Franco

    2015-01-01

    Summary Graphene, nanotubes and other carbon nanostructures have shown potential as candidates for advanced technological applications due to the different coordination of carbon atoms and to the possibility of π-conjugation. In this context, atomic-scale wires comprised of sp-hybridized carbon atoms represent ideal 1D systems to potentially downscale devices to the atomic level. Carbon-atom wires (CAWs) can be arranged in two possible structures: a sequence of double bonds (cumulenes), resulting in a 1D metal, or an alternating sequence of single–triple bonds (polyynes), expected to show semiconducting properties. The electronic and optical properties of CAWs can be finely tuned by controlling the wire length (i.e., the number of carbon atoms) and the type of termination (e.g., atom, molecular group or nanostructure). Although linear, sp-hybridized carbon systems are still considered elusive and unstable materials, a number of nanostructures consisting of sp-carbon wires have been produced and characterized to date. In this short review, we present the main CAW synthesis techniques and stabilization strategies and we discuss the current status of the understanding of their structural, electronic and vibrational properties with particular attention to how these properties are related to one another. We focus on the use of vibrational spectroscopy to provide information on the structural and electronic properties of the system (e.g., determination of wire length). Moreover, by employing Raman spectroscopy and surface enhanced Raman scattering in combination with the support of first principles calculations, we show that a detailed understanding of the charge transfer between CAWs and metal nanoparticles may open the possibility to tune the electronic structure from alternating to equalized bonds. PMID:25821689

  4. Acidification of East Siberian Arctic Shelf waters through addition of freshwater and terrestrial carbon

    NASA Astrophysics Data System (ADS)

    Semiletov, Igor; Pipko, Irina; Gustafsson, Örjan; Anderson, Leif G.; Sergienko, Valentin; Pugach, Svetlana; Dudarev, Oleg; Charkin, Alexander; Gukov, Alexander; Bröder, Lisa; Andersson, August; Spivak, Eduard; Shakhova, Natalia

    2016-05-01

    Ocean acidification affects marine ecosystems and carbon cycling, and is considered a direct effect of anthropogenic carbon dioxide uptake from the atmosphere. Accumulation of atmospheric CO2 in ocean surface waters is predicted to make the ocean twice as acidic by the end of this century. The Arctic Ocean is particularly sensitive to ocean acidification because more CO2 can dissolve in cold water. Here we present observations of the chemical and physical characteristics of East Siberian Arctic Shelf waters from 1999, 2000-2005, 2008 and 2011, and find extreme aragonite undersaturation that reflects acidity levels in excess of those projected in this region for 2100. Dissolved inorganic carbon isotopic data and Markov chain Monte Carlo simulations of water sources using salinity and δ18O data suggest that the persistent acidification is driven by the degradation of terrestrial organic matter and discharge of Arctic river water with elevated CO2 concentrations, rather than by uptake of atmospheric CO2. We suggest that East Siberian Arctic Shelf waters may become more acidic if thawing permafrost leads to enhanced terrestrial organic carbon inputs and if freshwater additions continue to increase, which may affect their efficiency as a source of CO2.

  5. The Effect of Carbon Additions on the Creep Resistance of Fe-25Al-5Zr Alloy

    NASA Astrophysics Data System (ADS)

    Dobeš, Ferdinand; Vodičková, Věra; Veselý, Jozef; Kratochvíl, Petr

    2016-12-01

    Creep experiments were conducted on Fe-25 at. pct Al-5 at. pct Zr alloy with carbon additions at the temperatures of 973 K and 1173 K (700 °C and 900 °C). The alloys were tested in two different states: (i) cast and (ii) annealed at 1273 K (1000 °C) for 50 hours. Stress exponents and activation energies were estimated. The values of the stress exponent n could be explained by the dislocation motion controlled by climb. The increased values of n in the high-carbon alloy at the temperature of 1173 K (900 °C) can be described by means of the threshold stress concept. The creep resistance at 973 K (700 °C) decreased with the increasing content of carbon. This result is discussed in terms of the ratio of zirconium to carbon in the alloy. An increase of the creep resistance with increasing ratio Zr:C is in agreement with the behavior observed previously in alloys with substantially lower concentrations of zirconium.

  6. Soluble organic additive effects on stress development during drying of calcium carbonate suspensions.

    PubMed

    Wedin, Pär; Lewis, Jennifer A; Bergström, Lennart

    2005-10-01

    The effect of polymer, plasticizer, and surfactant additives on stress development during drying of calcium carbonate particulate coatings was studied using a controlled-environment apparatus that simultaneously monitors drying stress, weight loss, and relative humidity. We found that the calcium carbonate coatings display a drying stress evolution typical of granular films, which is characterized by a sharp capillary-induced stress rise followed by a rapid stress relaxation. The addition of a soluble polymer to the CaCO3 suspension resulted in a two-stage stress evolution process. The initial stress rise stems from capillary-pressure-induced stresses within the film, while the second, larger stress rise occurs due to solidification and shrinkage of the polymeric species. Measurements on the corresponding pure polymer solutions established a clear correlation between the magnitude of residual stress in both the polymer and CaCO3-polymer films to the physical properties of the polymer phase, i.e. its glass transition temperature, T(g), and Young's modulus. The addition of small organic molecules can reduce the residual stress observed in the CaCO3-polymer films; e.g., glycerol, which acts as a plasticizer, reduces the drying stress by lowering T(g), while surfactant additions reduce the surface tension of the liquid phase, and, hence, the magnitude of the capillary pressure within the film.

  7. Enhancement of nitrate removal at the sediment-water interface by carbon addition plus vertical mixing.

    PubMed

    Chen, Xuechu; He, Shengbing; Zhang, Yueping; Huang, Xiaobo; Huang, Yingying; Chen, Danyue; Huang, Xiaochen; Tang, Jianwu

    2015-10-01

    Wetlands and ponds are frequently used to remove nitrate from effluents or runoffs. However, the efficiency of this approach is limited. Based on the assumption that introducing vertical mixing to water column plus carbon addition would benefit the diffusion across the sediment-water interface, we conducted simulation experiments to identify a method for enhancing nitrate removal. The results suggested that the sediment-water interface has a great potential for nitrate removal, and the potential can be activated after several days of acclimation. Adding additional carbon plus mixing significantly increases the nitrate removal capacity, and the removal of total nitrogen (TN) and nitrate-nitrogen (NO3(-)-N) is well fitted to a first-order reaction model. Adding Hydrilla verticillata debris as a carbon source increased nitrate removal, whereas adding Eichhornia crassipe decreased it. Adding ethanol plus mixing greatly improved the removal performance, with the removal rate of NO3(-)-N and TN reaching 15.0-16.5 g m(-2) d(-1). The feasibility of this enhancement method was further confirmed with a wetland microcosm, and the NO3(-)-N removal rate maintained at 10.0-12.0 g m(-2) d(-1) at a hydraulic loading rate of 0.5 m d(-1).

  8. Carbon doped PDMS: conductance stability over time and implications for additive manufacturing of stretchable electronics

    NASA Astrophysics Data System (ADS)

    Tavakoli, Mahmoud; Rocha, Rui; Osorio, Luis; Almeida, Miguel; de Almeida, Anibal; Ramachandran, Vivek; Tabatabai, Arya; Lu, Tong; Majidi, Carmel

    2017-03-01

    Carbon doped PDMS (cPDMS), has been used as a conductive polymer for stretchable electronics. Compared to liquid metals, cPDMS is low cost and is easier to process or to print with an additive manufacturing process. However, changes on the conductance of the carbon based conductive PDMS (cPDMS) were observed over time, in particular after integration of cPDMS and the insulating polymer. In this article we investigate the process parameters that lead to improved stability over conductance of the cPDMS over time. Slight modifications to the fabrication process parameters were conducted and changes on the conductance of the samples for each method were monitored. Results suggested that change of the conductance happens mostly after integration of a pre-polymer over a cured cPDMS, and not after integration of the cPDMS over a cured insulating polymer. We show that such changes can be eliminated by adjusting the integration priority between the conductive and insulating polymers, by selecting the right curing temperature, changing the concentration of the carbon particles and the thickness of the conductive traces, and when possible by changing the insulating polymer material. In this way, we obtained important conclusions regarding the effect of these parameters on the change of the conductance over time, that should be considered for additive manufacturing of soft electronics. Also, we show that these changes can be possibly due to the diffusion from PDMS into cPDMS.

  9. Tuning the oscillation of nested carbon nanotubes by insertion of an additional inner tube

    NASA Astrophysics Data System (ADS)

    Motevalli, B.; Liu, Jefferson Z.

    2013-12-01

    Different mechanisms of nano-oscillators with telescopic oscillations have attracted lots of attention due to the possible generation of GHz frequencies. In particular, nested carbon nanotubes are of special interest for which different mechanisms have been examined. In this paper, we will show that insertion of an additional inner tube into a conventional double walled carbon nanotube (DWCNT) oscillator not only can increase the oscillatory frequency considerably but also provides a wide range of system parameters for tuning the oscillatory behavior as well as its frequency. The insertion of an additional tube results in a number of different vdW force profiles (which only depend on the length ratios of the three tubes). Being subject to these different vdW force profiles and trigged with different initial velocity, an oscillating tube can exhibit various types of motions. We use a phase division diagram to discriminate the system parameters according to the different types of motions. Accordingly, a comprehensive study of the oscillatory frequency is also carried out. To perceive an insight into the effectiveness of insertion, a comparison is also made with the counterpart DWCNT oscillator. It is observed that this new mechanism offers a number of new possibilities in designing and characterizing a carbon nanotube based oscillator.

  10. 12 Years of NPK Addition Diminishes Carbon Sink Potential of a Nutrient Limited Peatland

    NASA Astrophysics Data System (ADS)

    Larmola, T.; Bubier, J. L.; Juutinen, S.; Moore, T. R.

    2011-12-01

    Peatlands store about a third of global soil carbon. Our aim was to study whether the vegetation feedbacks of nitrogen (N) deposition lead to stronger carbon sink or source in a nutrient limited peatland ecosystem. We investigated vegetation structure and ecosystem CO2 exchange at Mer Bleue Bog, Canada, that has been fertilized for 7-12 years. We have applied 5 and 20 times ambient annual wet N deposition (0.8 g N m-2) with or without phosphorus (P) and potassium (K). Gross photosynthesis, ecosystem respiration and net CO2 exchange (NEE) were measured weekly during the growing season using chamber technique. Under the highest N(PK) treatments, the light saturated photosynthesis (PSmax) was reduced by 20-30% compared to the control treatment, whereas under moderate N and PK additions PSmax slightly increased or was similar to the control. The ecosystem respiration showed similar trends among the treatments, but changes in the rates were less pronounced. High nutrient additions led to up to 65% lower net CO2 uptake than that in the control: In the NPK plots with cumulative N additions of 70, 19, and 0 g N m-2, the daytime NEE in May-July 2011 averaged 0.8 (se. 0.3), 2.0 (se. 0.4), and 2.4 (se. 0.3) μmol m-2 s-1, respectively. In the N only plots with cumulative N additions of 45, 19, and 0 g N m-2, the daytime NEE in May-July 2011 averaged 0.8 (se. 0.2), 2.6 (se. 0.4), and 1.8 (se. 0.3) μmol m-2 s-1, respectively. The reduced plant photosynthetic capacity and diminished carbon sink potential in the highest nutrient treatments correlated with the loss of peat mosses and were not compensated for by the increased vascular plant biomass that has mainly been allocated to woody shrub stems.

  11. Dynamic compaction of yttria-stabilized zirconia with the addition of carbon-nanotubes

    NASA Astrophysics Data System (ADS)

    Sable, P. A.; LaJeunesse, J.; Sullivan, C.; Kamavaram, V.; Borg, J. P.

    2017-01-01

    Yttria-stabilized zirconia (YSZ) is a versatile ceramic utilized for its hardness as well as thermal stability. In these experiments, carbon nanotubes (3% and 5% by weight) were added to powdered YSZ before it was statically compacted. These compacted samples were then dynamically compressed and monitored using a Photon Doppler Velocimetry (PDV) system. The objective was to better develop an understanding of how carbon nano-tubes (CNT) affects the initial shock response of the powder system. Experiments indicate the CNT both steepen the rise and increase the Hugoniot state of the YSZ-CNT system as compared to YSZ alone. Additionally, the PDV data is in good agreement with simple hydrocode simulations. The results of experiments and simulations are discussed.

  12. Effect of conductive additives to gel electrolytes on activated carbon-based supercapacitors

    NASA Astrophysics Data System (ADS)

    Barzegar, Farshad; Dangbegnon, Julien K.; Bello, Abdulhakeem; Momodu, Damilola Y.; Johnson, A. T. Charlie; Manyala, Ncholu

    2015-09-01

    This article is focused on polymer based gel electrolyte due to the fact that polymers are cheap and can be used to achieve extended potential window for improved energy density of the supercapacitor devices when compared to aqueous electrolytes. Electrochemical characterization of a symmetric supercapacitor devices based on activated carbon in different polyvinyl alcohol (PVA) based gel electrolytes was carried out. The device exhibited a maximum energy density of 24 Wh kg-1 when carbon black was added to the gel electrolyte as conductive additive. The good energy density was correlated with the improved conductivity of the electrolyte medium which is favorable for fast ion transport in this relatively viscous environment. Most importantly, the device remained stable with no capacitance lost after 10,000 cycles.

  13. Nonlinear resistance of polymer composites with carbon nanotube additives in the percolation state

    NASA Astrophysics Data System (ADS)

    Bocharov, G. S.; Eletskii, A. V.; Knizhnik, A. A.

    2016-10-01

    The electrical properties of a polymer composite with carbon nanotube additives have been analyzed. The state of the system near the percolation threshold, when charge is transferred along a single percolation path, has been considered. For this state, the current-voltage characteristics of a percolation chain made up of carbon nanotubes have been calculated under the assumption that the contact resistance between neighboring nanotubes is much higher than the intrinsic resistance of the nanotubes. According to recent data, the distance between neighboring (contacting) nanotubes has been assumed to be randomly distributed. It has been shown that, under the given conditions, the current-voltage characteristic is essentially nonlinear. This indicates the nonohmic conductivity of the composites. The dependence of the current-voltage characteristic on the spread of the contact distribution over distances has been discussed.

  14. Cluster protein structures using recurrence quantification analysis on coordinates of alpha-carbon atoms of proteins

    NASA Astrophysics Data System (ADS)

    Zhou, Yu; Yu, Zu-Guo; Anh, Vo

    2007-08-01

    The 3-dimensional coordinates of alpha-carbon atoms of proteins are used to distinguish the protein structural classes based on recurrence quantification analysis (RQA). We consider two independent variables from RQA of coordinates of alpha-carbon atoms, %determ1 and %determ2, which were defined by Webber et al. [C.L. Webber Jr., A. Giuliani, J.P. Zbilut, A. Colosimo, Proteins Struct. Funct. Genet. 44 (2001) 292]. The variable %determ2 is used to define two new variables, %determ21 and %determ22. Then three variables %determ1, %determ21 and %determ22 are used to construct a 3-dimensional variable space. Each protein is represented by a point in this variable space. The points corresponding to proteins from the α, β, α+β and α/β structural classes position into different areas in this variable space. In order to give a quantitative assessment of our clustering on the selected proteins, Fisher's discriminant algorithm is used. Numerical results indicate that the discriminant accuracies are very high and satisfactory.

  15. Effects of magnesium chloride and organic additives on the synthesis of aragonite precipitated calcium carbonate

    NASA Astrophysics Data System (ADS)

    Park, Woon Kyoung; Ko, Sang-Jin; Lee, Seung Woo; Cho, Kye-Hong; Ahn, Ji-Whan; Han, Choon

    2008-05-01

    The synthesis of aragonite precipitated calcium carbonate by treating a suspension of Ca(OH) 2 with CO 2 gas was investigated with regard to the effects of Mg 2+ ions and organic additives on polymorphism and alternative orientations. In the presence of a small amount of Mg 2+, Mg-calcite formed, but as the Mg 2+ ion concentration increased, the amount of Mg-calcite decreased and the amount of aragonite increased. Thus, the formation of Mg-calcite is suppressed and only aragonite is formed in the presence of 60 mol% MgCl 2. As the Mg 2+ ion concentration increased, the aragonite that formed was found to have decreased in terms of its longitude and aspect ratio. Furthermore, the effect of Mg 2+ ions in conjunction with organic additives was also investigated with regard to polymorphs and morphology and the structure-forming properties of the organic additives.

  16. Charcoal addition to soils in NE England: a carbon sink with environmental co-benefits?

    PubMed

    Bell, M J; Worrall, F

    2011-04-01

    Interest in the application of biochar (charcoal produced during the pyrolysis of biomass) to agricultural land is increasing across the world, recognised as a potential way to capture and store atmospheric carbon. Its interest is heightened by its potential co-benefits for soil quality and fertility. The majority of research has however been undertaken in tropical rather than temperate regions. This study assessed the potential for lump-wood charcoal addition (as a substitute for biochar) to soil types which are typically under arable and forest land-use in North East England. The study was undertaken over a 28 week period and found: i) No significant difference in net ecosystem respiration (NER) between soils containing charcoal and those without, other than in week 1 of the trial. ii) A significantly higher dissolved organic carbon (DOC) flux from soils containing large amounts of charcoal than from those untreated, when planted with ryegrass. iii) That when increased respiration or DOC loss did occur, neither was sufficiently large to alter the carbon sink benefits of charcoal application. iv) That charcoal incorporation resulted in a significantly lower nitrate flux in soil leachate from mineral soils. v) That charcoal incorporation caused significant increases in soil pH, from 6.98 to 7.22 on bare arable soils when 87,500 kg charcoal/ha was applied. Consideration of both the carbon sink and environmental benefits observed here suggests that charcoal application to temperate soils typical of North East England should be considered as a method of carbon sequestration. Before large scale land application is encouraged, further large scale trials should be undertaken to confirm the positive results of this research.

  17. Soil microbial community structure and nitrogen cycling responses to agroecosystem management and carbon substrate addition

    NASA Astrophysics Data System (ADS)

    Berthrong, S. T.; Buckley, D. H.; Drinkwater, L. E.

    2011-12-01

    Fertilizer application in conventional agriculture leads to N saturation and decoupled soil C and N cycling, whereas organic practices, e.g. complex rotations and legume incorporation, often results in increased SOM and tightly coupled cycles of C and N. These legacy effects of management on soils likely affect microbial community composition and microbial process rates. This project tested if agricultural management practices led to distinct microbial communities and if those communities differed in ability to utilize labile plant carbon substrates and to produce more plant available N. We addressed several specific questions in this project. 1) Do organic and conventional management legacies on similar soils produce distinct soil bacterial and fungal community structures and abundances? 2) How do these microbial community structures change in response to carbon substrate addition? 3) How do the responses of the microbial communities influence N cycling? To address these questions we conducted a laboratory incubation of organically and conventionally managed soils. We added C-13 labelled glucose either in one large dose or several smaller pulses. We extracted genomic DNA from soils before and after incubation for TRFLP community fingerprinting. We measured C in soil pools and respiration and N in soil extracts and leachates. Management led to different compositions of bacteria and fungi driven by distinct components in organic soils. Biomass did not differ across treatments indicating that differences in cycling were due to composition rather than abundance. C substrate addition led to convergence in bacterial communities; however management still strongly influenced the difference in communities. Fungal communities were very distinct between managements and plots with substrate addition not altering this pattern. Organic soils respired 3 times more of the glucose in the first week than conventional soils (1.1% vs 0.4%). Organic soils produced twice as much

  18. Effects of Nitrogen and Phosphorus Additions on Carbon Cycling of Tropical Mountain Rainforests in Hainan, China

    NASA Astrophysics Data System (ADS)

    Lai, J.

    2015-12-01

    Nitrogen (N) and Phosphorus (P) deposition is projected to increase significantly in tropical regions in the coming decades, which has changed and will change the structure and function of ecosystems, and affects on ecosystem Carbon (C) cycle. As an important part in global C cycle, how the C cycle of tropical rainforests will be influenced by the N and P deposition should be focused on. This study simulated N and P deposition in a primary and secondary forest of tropical mountain rainforest in Jianfengling, Hainan, China, during five-year field experiment to evaluate the effects of N and P deposition on C cycling processes and relate characteristics. Six levels of N and P treatments were treated: Control, Low-N, Medium-N, High-N, P and N+P. The relative growth rates (RGR) of tree layer in treatment plots were different from that in control plots after years of N and P addition. Simulated N and P deposition also increased ANPP in primary forest. N and P addition changed the growth of trees by altering soil nutrient and microbial activities. N and P addition increased soil organic carbon (SOC) and total N (TN) content, and significantly increased soil total P (TP) content, not changing soil pH. During the whole process of N and P addition, as net nitrification rate and net N mineralization rate were promoted by N and P addition, and effective N content (nitrate) of soil increased in the plot treated with N treatments compared to the control treatment. The microbial P content was increased by N and P addition, and microbial N was not changed. The increasing N deposition may enhance soil nutrient and stimulate growth of trees, which will lead to an increase of the C sequestration.

  19. Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina

    SciTech Connect

    Peterson, Eric J.; DelaRiva, Andrew T.; Lin, Sen; Johnson, Ryan S.; Guo, Hua; Miller, Jeffrey T.; Kwak, Ja Hun; Peden, Charles H.F.; Kiefer, Boris; Allard, Lawrence F.; Ribeiro, Fabio H.; Datye, Abhaya K.

    2014-09-15

    Catalysis by single isolated atoms of precious metals has attracted much recent interest since it promises the ultimate economy in atom efficiency. Previous reports have been confined to reducible oxide supports such as FeOx, TiO₂ or CeO₂. Here we show that isolated Pd atoms can be stabilized on industrially relevant gamma-alumina supports. At low Pd loadings (≤0.5 wt%) these catalysts contain exclusively atomically dispersed Pd species. The addition of lanthanum-oxide to the alumina, long known for its ability to improve alumina stability, is found to also help in the stabilization of isolated Pd atoms. Aberration-corrected scanning transmission electron microscopy (AC-STEM) confirms the presence of intermingled Pd and La on the gamma-alumina surface. Operando X-ray absorption spectroscopy, performed on Pd/La-alumina and Pd/gamma-alumina (0.5 wt% Pd) demonstrates the presence of catalytically active atomically dispersed ionic Pd in the Pd/La-doped gamma-alumina system. CO oxidation reactivity measurements show onset of catalytic activity at 40 °C, indicating that the ionic Pd species are not poisoned by CO. The reaction order in CO and O₂ is positive, suggesting a reaction mechanism that is different from that on metallic Pd. The catalyst activity is lost if the Pd species are reduced to their metallic form, but the activity can be regenerated by oxidation at 700 °C in air. The high-temperature stability of these ionic Pd species on commercial alumina supports makes this catalyst system of potential interest for low-temperature exhaust treatment catalysts.

  20. Carbon-, sulfur-, and phosphorus-based charge transfer reactions in inductively coupled plasma-atomic emission spectrometry

    NASA Astrophysics Data System (ADS)

    Grindlay, Guillermo; Gras, Luis; Mora, Juan; de Loos-Vollebregt, Margaretha T. C.

    2016-01-01

    In this work, the influence of carbon-, sulfur-, and phosphorus-based charge transfer reactions on the emission signal of 34 elements (Ag, Al, As, Au, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, I, In, Ir, K, Li, Mg, Mn, Na, Ni, P, Pb, Pd, Pt, S, Sb, Se, Sr, Te, and Zn) in axially viewed inductively coupled plasma-atomic emission spectrometry has been investigated. To this end, atomic and ionic emission signals for diluted glycerol, sulfuric acid, and phosphoric acid solutions were registered and results were compared to those obtained for a 1% w w- 1 nitric acid solution. Experimental results show that the emission intensities of As, Se, and Te atomic lines are enhanced by charge transfer from carbon, sulfur, and phosphorus ions. Iodine and P atomic emission is enhanced by carbon- and sulfur-based charge transfer whereas the Hg atomic emission signal is enhanced only by carbon. Though signal enhancement due to charge transfer reactions is also expected for ionic emission lines of the above-mentioned elements, no experimental evidence has been found with the exception of Hg ionic lines operating carbon solutions. The effect of carbon, sulfur, and phosphorus charge transfer reactions on atomic emission depends on (i) wavelength characteristics. In general, signal enhancement is more pronounced for electronic transitions involving the highest upper energy levels; (ii) plasma experimental conditions. The use of robust conditions (i.e. high r.f. power and lower nebulizer gas flow rates) improves carbon, sulfur, and phosphorus ionization in the plasma and, hence, signal enhancement; and (iii) the presence of other concomitants (e.g. K or Ca). Easily ionizable elements reduce ionization in the plasma and consequently reduce signal enhancement due to charge transfer reactions.

  1. Tribological properties of graphene oxide and carbon spheres as lubricating additives

    NASA Astrophysics Data System (ADS)

    Song, Haojie; Wang, Zhiqiang; Yang, Jin

    2016-10-01

    The purpose of this paper was to investigate the tribological properties of carbon materials with various morphologies [i.e., graphene oxide (GO) and carbon spheres (CSs)] utilized as lubricating additives on a ball-plate tribotester. The morphology and spectroscopy characterization of GO and CSs were investigated by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectrometry, and thermogravimetric analysis. Friction and wear properties of the sunflower seed oil filled with GO and CSs were investigated by using a MS-T3000 ball-on-disk apparatus. Results show that the sunflower seed oil containing 0.3 wt% GO nanosheets exhibited a substantial diminution in friction and wear compared with the 3.0 wt% CSs as sunflower seed oil additives. Formation of low-shear strength tribofilms containing GO and its self-lubricating behavior was the key factor in reduction of the friction and prevention from wear and deformation. In addition, friction mechanism of CSs was also discussed.

  2. Plant interspecific differences in arbuscular mycorrhizal colonization as a result of soil carbon addition.

    PubMed

    Eschen, René; Müller-Schärer, Heinz; Schaffner, Urs

    2013-01-01

    Soil nutrient availability and colonization by arbuscular mycorrhizal fungi are important and potentially interacting factors shaping vegetation composition and succession. We investigated the effect of carbon (C) addition, aimed at reducing soil nutrient availability, on arbuscular mycorrhizal colonization. Seedlings of 27 plant species with different sets of life-history traits (functional group affiliation, life history strategy and nitrophilic status) were grown in pots filled with soil from a nutrient-rich set-aside field and amended with different amounts of C. Mycorrhizal colonization was progressively reduced along the gradient of increasing C addition in 17 out of 27 species, but not in the remaining species. Grasses had lower colonization levels than forbs and legumes and the decline in AM fungal colonization was more pronounced in legumes than in other forbs and grasses. Mycorrhizal colonization did not differ between annual and perennial species, but decreased more rapidly along the gradient of increasing C addition in plants with high Ellenberg N values than in plants with low Ellenberg N values. Soil C addition not only limits plant growth through a reduction in available nutrients, but also reduces mycorrhizal colonization of plant roots. The effect of C addition on mycorrhizal colonization varies among plant functional groups, with legumes experiencing an overproportional reduction in AM fungal colonization along the gradient of increasing C addition. We therefore propose that for a better understanding of vegetation succession on set-aside fields one may consider the interrelationship between plant growth, soil nutrient availability and mycorrhizal colonization of plant roots.

  3. Stimulation of terrestrial ecosystem carbon storage by nitrogen addition: a meta-analysis

    PubMed Central

    Yue, Kai; Peng, Yan; Peng, Changhui; Yang, Wanqin; Peng, Xin; Wu, Fuzhong

    2016-01-01

    Elevated nitrogen (N) deposition alters the terrestrial carbon (C) cycle, which is likely to feed back to further climate change. However, how the overall terrestrial ecosystem C pools and fluxes respond to N addition remains unclear. By synthesizing data from multiple terrestrial ecosystems, we quantified the response of C pools and fluxes to experimental N addition using a comprehensive meta-analysis method. Our results showed that N addition significantly stimulated soil total C storage by 5.82% ([2.47%, 9.27%], 95% CI, the same below) and increased the C contents of the above- and below-ground parts of plants by 25.65% [11.07%, 42.12%] and 15.93% [6.80%, 25.85%], respectively. Furthermore, N addition significantly increased aboveground net primary production by 52.38% [40.58%, 65.19%] and litterfall by 14.67% [9.24%, 20.38%] at a global scale. However, the C influx from the plant litter to the soil through litter decomposition and the efflux from the soil due to microbial respiration and soil respiration showed insignificant responses to N addition. Overall, our meta-analysis suggested that N addition will increase soil C storage and plant C in both above- and below-ground parts, indicating that terrestrial ecosystems might act to strengthen as a C sink under increasing N deposition. PMID:26813078

  4. Stimulation of terrestrial ecosystem carbon storage by nitrogen addition: a meta-analysis

    NASA Astrophysics Data System (ADS)

    Yue, Kai; Peng, Yan; Peng, Changhui; Yang, Wanqin; Peng, Xin; Wu, Fuzhong

    2016-01-01

    Elevated nitrogen (N) deposition alters the terrestrial carbon (C) cycle, which is likely to feed back to further climate change. However, how the overall terrestrial ecosystem C pools and fluxes respond to N addition remains unclear. By synthesizing data from multiple terrestrial ecosystems, we quantified the response of C pools and fluxes to experimental N addition using a comprehensive meta-analysis method. Our results showed that N addition significantly stimulated soil total C storage by 5.82% ([2.47%, 9.27%], 95% CI, the same below) and increased the C contents of the above- and below-ground parts of plants by 25.65% [11.07%, 42.12%] and 15.93% [6.80%, 25.85%], respectively. Furthermore, N addition significantly increased aboveground net primary production by 52.38% [40.58%, 65.19%] and litterfall by 14.67% [9.24%, 20.38%] at a global scale. However, the C influx from the plant litter to the soil through litter decomposition and the efflux from the soil due to microbial respiration and soil respiration showed insignificant responses to N addition. Overall, our meta-analysis suggested that N addition will increase soil C storage and plant C in both above- and below-ground parts, indicating that terrestrial ecosystems might act to strengthen as a C sink under increasing N deposition.

  5. New bonding modes of carbon and heavier group 14 atoms Si-Pb.

    PubMed

    Frenking, Gernot; Tonner, Ralf; Klein, Susanne; Takagi, Nozomi; Shimizu, Takayazu; Krapp, Andreas; Pandey, Krishna K; Parameswaran, Pattiyil

    2014-07-21

    Recent theoretical studies are reviewed which show that the naked group 14 atoms E = C-Pb in the singlet (1)D state behave as bidentate Lewis acids that strongly bind two σ donor ligands L in the donor-acceptor complexes L→E←L. Tetrylones EL2 are divalent E(0) compounds which possess two lone pairs at E. The unique electronic structure of tetrylones (carbones, silylones, germylones, stannylones, plumbylones) clearly distinguishes them from tetrylenes ER2 (carbenes, silylenes, germylenes, stannylenes, plumbylenes) which have electron-sharing bonds R-E-R and only one lone pair at atom E. The different electronic structures of tetrylones and tetrylenes are revealed by charge- and energy decomposition analyses and they become obvious experimentally by a distinctively different chemical reactivity. The unusual structures and chemical behaviour of tetrylones EL2 can be understood in terms of the donor-acceptor interactions L→E←L. Tetrylones are potential donor ligands in main group compounds and transition metal complexes which are experimentally not yet known. The review also introduces theoretical studies of transition metal complexes [TM]-E which carry naked tetrele atoms E = C-Sn as ligands. The bonding analyses suggest that the group-14 atoms bind in the (3)P reference state to the transition metal in a combination of σ and π∥ electron-sharing bonds TM-E and π⊥ backdonation TM→E. The unique bonding situation of the tetrele complexes [TM]-E makes them suitable ligands in adducts with Lewis acids. Theoretical studies of [TM]-E→W(CO)5 predict that such species may becomes synthesized.

  6. Perfluoroalkyl carboxylic acids with up to 22 carbon atoms in snow and soil samples from a ski area.

    PubMed

    Plassmann, Merle M; Berger, Urs

    2013-05-01

    The use of fluorinated ski waxes as a direct input route of perfluoroalkyl carboxylic acids (PFCAs) to the environment was investigated. PFCA homologues with 6-22 carbon atoms (C6-22 PFCAs) were detected in fluorinated ski waxes and their raw materials by liquid chromatography coupled to tandem mass spectrometry. Snow and soil samples from a ski area in Sweden were taken after a skiing competition and after snowmelt, respectively. In both snow and soil samples C6-22 PFCAs were detected, representing the first report of PFCAs with up to 22 carbon atoms in environmental samples. Single analyte concentrations in snow (analyzed as melt water) and soil ranged up to 0.8μgL(-1) and 5ngg(-1) dry weight, respectively. ∑PFCA concentrations in snow and soil decreased from the start to the finish of the ski trail. Distinct differences in PFCA patterns between snow (prevalence of C14-20 PFCAs) and soil samples (C6-14 PFCAs dominating) were observed. Additionally, a PFCA pattern change from the start to about two third of the distance of the ski trail was found both for snow and soil, with a larger fraction of longer chain homologues present in samples from the start. These observations are probably a result of differences in PFCA homologue patterns present in different types of waxes. The calculated PFCA input from snow affected by the skiing competition was smaller than the PFCA inventory in soil for all chain lengths and markedly smaller for C6-15 PFCAs, presenting evidence for long-term accumulation in soil.

  7. A carbonate controlled-addition method for amorphous calcium carbonate spheres stabilized by poly(acrylic acid)s.

    PubMed

    Huang, Shu-Chen; Naka, Kensuke; Chujo, Yoshiki

    2007-11-20

    Stable amorphous calcium carbonate (ACC) composite particle with a size-controlled monodispersed sphere was obtained by a new simple carbonate controlled-addition method by using poly(acrylic acid) (PAA) (Mw = 5000), in which an aqueous ammonium carbonate solution was added into an aqueous solution of PAA and CaCl2 with a different time period. The obtained ACC composite products consist of about 50 wt % of ACC, 30 wt % of PAA, and H2O. Average particle sizes of the ACC spheres increased from (1.8 +/- 0.4) x 102 to (5.5 +/- 1.2) x 102 nm with an increase of the complexation time of the PAA-CaCl2 solution from 3 min to 24 h, respectively. The ACC formed from the complexation time for 3 min was stable for 10 days with gentle stirring as well as 3 months under a quiescent condition in the aqueous solution. Moreover, the ACC was also stable at 400 degrees C. Stability of the amorphous phase decreased with an increase of the complexation time of the PAA-CaCl2 solution. No ACC was obtained when the lower molar mass PAAs (Mw = 1200 and 2100) were used. In the higher molar mass case (Mw = 25 000), a mixture of the amorphous phase and vaterite and calcite crystalline product was produced. The present results demonstrate that the interaction and the reaction kinetics of the PAA-Ca2+-H2O complex play an important role in the mineralization of CaCO3.

  8. Atomic-Layer-Deposition Functionalized Carbonized Mesoporous Wood Fiber for High Sulfur Loading Lithium Sulfur Batteries.

    PubMed

    Luo, Chao; Zhu, Hongli; Luo, Wei; Shen, Fei; Fan, Xiulin; Dai, Jiaqi; Liang, Yujia; Wang, Chunsheng; Hu, Liangbing

    2017-04-14

    Lithium-sulfur battery (LSB) as one of the most promising energy storage devices suffers from poor conductivity of sulfur and fast capacity decay triggered by the dissolution of polysulfides. In this work, functionalized carbonized mesoporous wood fiber (f-CMWF) is employed as a host to accommodate sulfur for the first time. Natural wood microfiber has unique hierarchical and mesoporous structure, which is well maintained after carbonization. With such a hierarchical mesoporous structure, a high sulfur loading of 76 wt% is achieved in CMWF electrodes. The pore size of CMWF is tunable by atomic layer deposition (ALD) of 5 nm Al2O3 coating to form the f-CMWF. Such a thin layer coating slightly decreases the sulfur loading to 70%, but remarkably promotes the cyclic stability of sulfur cathode, which delivers an initial capacity of 1115 mAh g-1, and maintains a reversible capacity of 859 mAh g-1 for 450 cycles, corresponding to a slow capacity decay rate of 0.046% per cycle. More importantly, natural wood microfiber is firstly used as a raw material for sulfur encapsulating. This work is also critical for using low cost and mesoporous biomass carbon as bi-functional scaffold for LSB.

  9. Conformal atomic layer deposition of alumina on millimeter tall, vertically-aligned carbon nanotube arrays.

    PubMed

    Stano, Kelly L; Carroll, Murphy; Padbury, Richard; McCord, Marian; Jur, Jesse S; Bradford, Philip D

    2014-11-12

    Atomic layer deposition (ALD) can be used to coat high aspect ratio and high surface area substrates with conformal and precisely controlled thin films. Vertically aligned arrays of multiwalled carbon nanotubes (MWCNTs) with lengths up to 1.5 mm were conformally coated with alumina from base to tip. The nucleation and growth behaviors of Al2O3 ALD precursors on the MWCNTs were studied as a function of CNT surface chemistry. CNT surfaces were modified through a series of post-treatments including pyrolytic carbon deposition, high temperature thermal annealing, and oxygen plasma functionalization. Conformal coatings were achieved where post-treatments resulted in increased defect density as well as the extent of functionalization, as characterized by X-ray photoelectron spectroscopy and Raman spectroscopy. Using thermogravimetric analysis, it was determined that MWCNTs treated with pyrolytic carbon and plasma functionalization prior to ALD coating were more stable to thermal oxidation than pristine ALD coated samples. Functionalized and ALD coated arrays had a compressive modulus more than two times higher than a pristine array coated for the same number of cycles. Cross-sectional energy dispersive X-ray spectroscopy confirmed that Al2O3 could be uniformly deposited through the entire thickness of the vertically aligned MWCNT array by manipulating sample orientation and mounting techniques. Following the ALD coating, the MWCNT arrays demonstrated hydrophilic wetting behavior and also exhibited foam-like recovery following compressive strain.

  10. Simple-Cubic Carbon Frameworks with Atomically Dispersed Iron Dopants toward High-Efficiency Oxygen Reduction.

    PubMed

    Wang, Biwei; Wang, Xinxia; Zou, Jinxiang; Yan, Yancui; Xie, Songhai; Hu, Guangzhi; Li, Yanguang; Dong, Angang

    2017-03-08

    Iron and nitrogen codoped carbons (Fe-N-C) have attracted increasingly greater attention as electrocatalysts for oxygen reduction reaction (ORR). Although challenging, the synthesis of Fe-N-C catalysts with highly dispersed and fully exposed active sites is of critical importance for improving the ORR activity. Here, we report a new type of graphitic Fe-N-C catalysts featuring numerous Fe single atoms anchored on a three-dimensional simple-cubic carbon framework. The Fe-N-C catalyst, derived from self-assembled Fe3O4 nanocube superlattices, was prepared by in situ ligand carbonization followed by acid etching and ammonia activation. Benefiting from its homogeneously dispersed and fully accessible active sites, highly graphitic nature, and enhanced mass transport, our Fe-N-C catalyst outperformed Pt/C and many previously reported Fe-N-C catalysts for ORR. Furthermore, when used for constructing the cathode for zinc-air batteries, our Fe-N-C catalyst exhibited current and power densities comparable to those of the state-of-the-art Pt/C catalyst.

  11. Decomposition of the fluoroethylene carbonate additive and the glue effect of lithium fluoride products for the solid electrolyte interphase: an ab initio study.

    PubMed

    Okuno, Yukihiro; Ushirogata, Keisuke; Sodeyama, Keitaro; Tateyama, Yoshitaka

    2016-03-28

    Additives in the electrolyte solution of lithium-ion batteries (LIBs) have a large impact on the performance of the solid electrolyte interphase (SEI) that forms on the anode and is a key to the stability and durability of LIBs. We theoretically investigated effects of fluoroethylene carbonate (FEC), a representative additive, that has recently attracted considerable attention for the enhancement of cycling stability of silicon electrodes and the improvement of reversibility of sodium-ion batteries. First, we intensively examined the reductive decompositions by ring-opening, hydrogen fluoride (HF) elimination to form a vinylene carbonate (VC) additive and intermolecular chemical reactions of FEC in the ethylene carbonate (EC) electrolyte, by using density functional theory (DFT) based molecular dynamics and the blue-moon ensemble technique for the free energy profile. The results show that the most plausible product of the FEC reductive decomposition is lithium fluoride (LiF), and that the reactivity of FEC to anion radicals is found to be inert compared to the VC additive. We also investigated the effects of the generated LiF on the SEI by using two model systems; (1) LiF molecules distributed in a model aggregate of organic SEI film components (SFCs) and (2) a LiF aggregate interfaced with the SFC aggregate. DFT calculations of the former system show that F atoms form strong bindings with the Li atoms of multiple organic SFC molecules and play as a joint connecting them. In the latter interface system, the LiF aggregate adsorbs the organic SFCs through the F-Li bindings. These results suggest that LiF moieties play the role of glue in the organic SFC within the SEI film. We also examined the interface structure between a LiF aggregate and a lithiated silicon anode, and found that they are strongly bound. This strong binding is likely to be related to the effectiveness of the FEC additive in the electrolyte for the silicon anode.

  12. Change in surface properties of Microthrix parvicella upon addition of polyaluminium chloride as characterized by atomic force microscopy.

    PubMed

    Hamit-Eminovski, Jildiz; Eskilsson, Krister; Arnebrant, Thomas

    2010-01-01

    The filamentous bacterium Microthrix parvicella causes severe separation and foaming problems at wastewater treatment plants (WWTPs). An effective control of the bacterium in activated sludge WWTPs can be accomplished by dosage with polyaluminium chloride (PAX-14). The purpose of this study was to investigate whether addition of PAX-14 affects surface properties such as the hydrophobicity of the bacterium and to study the exopolymers of M. parvicella that host surface-associated enzymes. To this end, force measurements by atomic force microscopy were carried out to measure the interactions between hydrophilic and hydrophobized tips and the bacterium surface. Addition of PAX-14 caused no changes in the hydrophobicity of the bacterium surface but the data indicate that it collapsed the polymeric layer likely due to electrostatic screening. It is concluded that the collapse of the polymeric layer may affect the transport of substrates (eg free fatty acids) to the bacterium and hence the competitiveness of M. parvicella compared to the other bacteria present in activated sludge.

  13. Study of polymeric additive effect on calcium oxalate dihydrate crystal growth using real-time atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Jung, Taesung; Kim, Jong-Nam; Kim, Woo-Sik; Kyun Choi, Chang

    2011-07-01

    Microscopic events associated with crystal growth and characterization of the growth hillocks on the (1 0 0) and (1 0 1) faces of COD were examined by atomic force microscopy. The (1 0 0) and (1 0 1) faces of COD developed elliptical and triangular hillocks and pits, respectively. Each face exhibited hillocks with step sites that can be assigned to specific crystal planes, enabling direct determination of the growth rates along specific crystallographic directions. The addition of macromolecules with anionic side chains, poly- L-aspartate, poly- L-glutamate, and polyacrylate resulted in inhibition of growth on the hillock step planes. The magnitude of their effect depended on the macromolecule structures and identity of the step site. The isotropic shape of the COD hillocks mimicked the shape of the resulting macroscopic COD crystals based on step-specific binding of the macromolecules to the COD crystal, with stronger step pinning along the [0 1 0] direction than in the [0 0 1] direction. Electrostatic matching between the crystal faces and additives according to the ionic array of calcium oxalate in the COD structure was found to be responsible for the preferential binding of the macromolecules to terraces.

  14. DFT study of Fe-Ni core-shell nanoparticles: Stability, catalytic activity, and interaction with carbon atom for single-walled carbon nanotube growth

    NASA Astrophysics Data System (ADS)

    Yang, Zhimin; Wang, Qiang; Shan, Xiaoye; Li, Wei-qi; Chen, Guang-hui; Zhu, Hongjun

    2015-02-01

    Metal catalysts play an important role in the nucleation and growth of single-walled carbon nanotubes (SWCNTs). It is essential for probing the nucleation and growth mechanism of SWCNTs to fundamentally understand the properties of the metal catalysts and their interaction with carbon species. In this study, we systematically studied the stability of 13- and 55-atom Fe and Fe-Ni core-shell particles as well as these particles interaction with the carbon atoms using the density functional theory calculations. Icosahedral 13- and 55-atom Fe-Ni core-shell bimetallic particles have higher stability than the corresponding monometallic Fe and Ni particles. Opposite charge transfer (or distribution) in these particles leads to the Fe surface-shell displays a positive charge, while the Ni surface-shell exhibits a negative charge. The opposite charge transfer would induce different chemical activities. Compared with the monometallic Fe and Ni particles, the core-shell bimetallic particles have weaker interaction with C atoms. More importantly, C atoms only prefer staying on the surface of the bimetallic particles. In contrast, C atoms prefer locating into the subsurface of the monometallic particles, which is more likely to form stable metal carbides. The difference of the mono- and bimetallic particles on this issue may result in different nucleation and growth mechanism of SWCNTs. Our findings provide useful insights for the design of bimetallic catalysts and a better understanding nucleation and growth mechanism of SWCNTs.

  15. On the effect of carbon monoxide addition on soot formation in a laminar ethylene/air coflow diffusion flame

    SciTech Connect

    Guo, Hongsheng; Thomson, Kevin A.; Smallwood, Gregory J.

    2009-06-15

    The effect of carbon monoxide addition on soot formation in an ethylene/air diffusion flame is investigated by experiment and detailed numerical simulation. The paper focuses on the chemical effect of carbon monoxide addition by comparing the results of carbon monoxide and nitrogen diluted flames. Both experiment and simulation show that although overall the addition of carbon monoxide monotonically reduces the formation of soot, the chemical effect promotes the formation of soot in an ethylene/air diffusion flame. The further analysis of the details of the numerical result suggests that the chemical effect of carbon monoxide addition may be caused by the modifications to the flame temperature, soot surface growth and oxidation reactions. Flame temperature increases relative to a nitrogen diluted flame, which results in a higher surface growth rate, when carbon monoxide is added. Furthermore, the addition of carbon monoxide increases the concentration of H radical owing to the intensified forward rate of the reaction CO + OH = CO{sub 2} + H and therefore increases the surface growth reaction rates. The addition of carbon monoxide also slows the oxidation rate of soot because the same reaction CO + OH = CO{sub 2} + H results in a lower concentration of OH. (author)

  16. Salt additions alter short-term nitrogen and carbon mobilization in a coastal Oregon Andisol.

    PubMed

    Compton, Jana E; Church, M Robbins

    2011-01-01

    Deposition of sea salts is commonly elevated along the coast relative to inland areas, yet little is known about the effects on terrestrial ecosystem biogeochemistry. We examined the influence of NaCl concentrations on N, C, and P leaching from a coastal Oregon forest Andisol in two laboratory studies: a rapid batch extraction (approximately 1 d) and a month-long incubation using microlysimeters. In the rapid extractions, salt additions immediately mobilized significant amounts of ammonium and phosphate but not nitrate. In the month-long incubations, salt additions at concentrations in the range of coastal precipitation increased nitrate leaching from the microcosms by nearly 50% and reduced the mobility of dissolved organic carbon. Our findings suggest that coupled abiotic-biotic effects increase nitrate mobility in these soils: exchange of sodium for ammonium, then net nitrification. Changes in sea salt deposition to land and the interactions with coastal soils could alter the delivery of N and C to sensitive coastal waters.

  17. Role of Carbon-Addition and Hydrogen-Migration Reactions in Soot Surface Growth.

    PubMed

    Zhang, Hong-Bo; Hou, Dingyu; Law, Chung K; You, Xiaoqing

    2016-02-11

    Using density functional theory and master equation modeling, we have studied the kinetics of small unsaturated aliphatic molecules reacting with polycyclic aromatic hydrocarbon (PAH) molecules having a diradical character. We have found that these reactions follow the mechanism of carbon addition and hydrogen migration (CAHM) on both spin-triplet and open-shell singlet potential energy surfaces at a rate that is about ten times those of the hydrogen-abstraction-carbon-addition (HACA) reactions at 1500 K in the fuel-rich postflame region. The results also show that the most active reaction sites are in the center of the zigzag edges of the PAHs. Furthermore, the reaction products are more likely to form straight rather than branched aliphatic side chains in the case of reacting with diacetylene. The computed rate constants are also found to be independent of pressure at conditions of interest in soot formation, and the activation barriers of the CAHM reactions are linearly correlated with the diradical characters.

  18. Polarizabilities and van der Waals C6 coefficients of fullerenes from an atomistic electrodynamics model: Anomalous scaling with number of carbon atoms.

    PubMed

    Saidi, Wissam A; Norman, Patrick

    2016-07-14

    The van der Waals C6 coefficients of fullerenes are shown to exhibit an anomalous dependence on the number of carbon atoms N such that C6 ∝ N(2.2) as predicted using state-of-the-art quantum mechanical calculations based on fullerenes with small sizes, and N(2.75) as predicted using a classical-metallic spherical-shell approximation of the fullerenes. We use an atomistic electrodynamics model where each carbon atom is described by a polarizable object to extend the quantum mechanical calculations to larger fullerenes. The parameters of this model are optimized to describe accurately the static and complex polarizabilities of the fullerenes by fitting against accurate ab initio calculations. This model shows that C6 ∝ N(2.8), which is supportive of the classical-metallic spherical-shell approximation. Additionally, we show that the anomalous dependence of the polarizability on N is attributed to the electric charge term, while the dipole-dipole term scales almost linearly with the number of carbon atoms.

  19. Divalent Fe Atom Coordination in Two-Dimensional Microporous Graphitic Carbon Nitride.

    PubMed

    Oh, Youngtak; Hwang, Jin Ok; Lee, Eui-Sup; Yoon, Minji; Le, Viet-Duc; Kim, Yong-Hyun; Kim, Dong Ha; Kim, Sang Ouk

    2016-09-28

    Graphitic carbon nitride (g-C3N4) is a rising two-dimensional material possessing intrinsic semiconducting property with unique geometric configuration featuring superimposed heterocyclic sp(2) carbon and nitrogen network, nonplanar layer chain structure, and alternating buckling. The inherent porous structure of heptazine-based g-C3N4 features electron-rich sp(2) nitrogen, which can be exploited as a stable transition metal coordination site. Multiple metal-functionalized g-C3N4 systems have been reported for versatile applications, but local coordination as well as its electronic structure variation upon incoming metal species is not well understood. Here we present detailed bond coordination of divalent iron (Fe(2+)) through micropore sites of graphitic carbon nitride and provide both experimental and computational evidence supporting the aforementioned proposition. In addition, the utilization of electronic structure variation is demonstrated through comparative photocatalytic activities of pristine and Fe-g-C3N4.

  20. FORMATION OF FORMALDEHYDE AND CARBON DIOXIDE ON AN ICY GRAIN ANALOG USING FAST HYDROGEN ATOMS

    SciTech Connect

    Madzunkov, S. M.; MacAskill, J. A.; Chutjian, A.; Darrach, M. R.; Vidali, G.; Shortt, B. J.

    2009-05-20

    Formaldehyde (H{sub 2}CO) and carbon dioxide (CO{sub 2}) were produced in collisions of a superthermal, 3 eV beam of H({sup 2}S) atoms with CO molecules adsorbed on a gold surface at 4.8 K. The reaction-generated products were detected and analyzed using the techniques of temperature programmed desorption (TPD), quadrupole mass spectrometry, and a novel application of the Metropolis algorithm, random-walk procedure to identify the unique fractionation patterns of H{sub 2}CO and CO{sub 2} from the patterns of other species such as N{sub 2}, CO, and H{sub 2}O embedded in the CO blanket and devolved in the TPD/mass spectrometry process. Reaction sequences are given to account for the formation of H{sub 2}CO and CO{sub 2}.

  1. Electrochemical behavior of adrenaline at the carbon atom wire modified electrode

    NASA Astrophysics Data System (ADS)

    Xue, Kuan-Hong; Liu, Jia-Mei; Wei, Ri-Bing; Chen, Shao-Peng

    2006-09-01

    Electrochemical behavior of adrenaline at an electrode modified by carbon atom wires (CAWs), a new material, was investigated by cyclic voltammetry combined with UV-vis spectrometry, and forced convection method. As to the electrochemical response of redox of adrenaline/adrenalinequinone couple in 0.50 M H 2SO 4, at a nitric acid treated CAW modified electrode, the anodic and cathodic peak potentials Epa and Epc shifted by 87 mV negatively and 139 mV in the positive direction, respectively, and standard heterogeneous rate constant k0 increased by 16 times compared to the corresponding bare electrode, indicating the extraordinary activity of CAWs in electrocatalysis for the process.

  2. Ultra-low loading Pt nanocatalysts prepared by atomic layer deposition on carbon aerogels

    SciTech Connect

    King, J S; Wittstock, A; Biener, J; Kucheyev, S O; Wang, Y M; Baumann, T F; Giri, S; Hamza, A V; Baeumer, M; Bent, S F

    2008-04-21

    Using atomic layer deposition (ALD), we show that Pt nanoparticles can be deposited on the inner surfaces of carbon aerogels (CA). The resultant Pt-loaded materials exhibit high catalytic activity for the oxidation of CO even at loading levels as low as {approx}0.05 mg Pt/cm{sup 2}. We observe a conversion efficiency of nearly 100% in the temperatures range 150-250 C, and the total conversion rate seems to be only limited by the thermal stability of our CA support in ambient oxygen. Our ALD approach described here is universal in nature, and can be applied to the design of new catalytic materials for a variety of applications, including fuel cells, hydrogen storage, pollution control, green chemistry, and liquid fuel production.

  3. Modeling and optimization of atomic layer deposition processes on vertically aligned carbon nanotubes

    PubMed Central

    Yazdani, Nuri; Chawla, Vipin; Edwards, Eve; Wood, Vanessa

    2014-01-01

    Summary Many energy conversion and storage devices exploit structured ceramics with large interfacial surface areas. Vertically aligned carbon nanotube (VACNT) arrays have emerged as possible scaffolds to support large surface area ceramic layers. However, obtaining conformal and uniform coatings of ceramics on structures with high aspect ratio morphologies is non-trivial, even with atomic layer deposition (ALD). Here we implement a diffusion model to investigate the effect of the ALD parameters on coating kinetics and use it to develop a guideline for achieving conformal and uniform thickness coatings throughout the depth of ultra-high aspect ratio structures. We validate the model predictions with experimental data from ALD coatings of VACNT arrays. However, the approach can be applied to predict film conformality as a function of depth for any porous topology, including nanopores and nanowire arrays. PMID:24778944

  4. Modeling and optimization of atomic layer deposition processes on vertically aligned carbon nanotubes.

    PubMed

    Yazdani, Nuri; Chawla, Vipin; Edwards, Eve; Wood, Vanessa; Park, Hyung Gyu; Utke, Ivo

    2014-01-01

    Many energy conversion and storage devices exploit structured ceramics with large interfacial surface areas. Vertically aligned carbon nanotube (VACNT) arrays have emerged as possible scaffolds to support large surface area ceramic layers. However, obtaining conformal and uniform coatings of ceramics on structures with high aspect ratio morphologies is non-trivial, even with atomic layer deposition (ALD). Here we implement a diffusion model to investigate the effect of the ALD parameters on coating kinetics and use it to develop a guideline for achieving conformal and uniform thickness coatings throughout the depth of ultra-high aspect ratio structures. We validate the model predictions with experimental data from ALD coatings of VACNT arrays. However, the approach can be applied to predict film conformality as a function of depth for any porous topology, including nanopores and nanowire arrays.

  5. Carbon nanotube modified probes for stable and high sensitivity conductive atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Slattery, Ashley D.; Shearer, Cameron J.; Gibson, Christopher T.; Shapter, Joseph G.; Lewis, David A.; Stapleton, Andrew J.

    2016-11-01

    Conductive atomic force microscopy (C-AFM) is used to characterise the nanoscale electrical properties of many conducting and semiconducting materials. We investigate the effect of single walled carbon nanotube (SWCNT) modification of commercial Pt/Ir cantilevers on the sensitivity and image stability during C-AFM imaging. Pt/Ir cantilevers were modified with small bundles of SWCNTs via a manual attachment procedure and secured with a conductive platinum pad. AFM images of topography and current were collected from heterogeneous polymer and nanomaterial samples using both standard and SWCNT modified cantilevers. Typically, achieving a good current image comes at the cost of reduced feedback stability. In part, this is due to electrostatic interaction and increased tip wear upon applying a bias between the tip and the sample. The SWCNT modified tips displayed superior current sensitivity and feedback stability which, combined with superior wear resistance of SWCNTs, is a significant advancement for C-AFM.

  6. Single-walled carbon nanotubes coated with ZnO by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Pal, Partha P.; Gilshteyn, Evgenia; Jiang, Hua; Timmermans, Marina; Kaskela, Antti; Tolochko, Oleg V.; Kurochkin, Alexey V.; Karppinen, Maarit; Nisula, Mikko; Kauppinen, Esko I.; Nasibulin, Albert G.

    2016-12-01

    The possibility of ZnO deposition on the surface of single-walled carbon nanotubes (SWCNTs) with the help of an atomic layer deposition (ALD) technique was successfully demonstrated. The utilization of pristine SWCNTs as a support resulted in a non-uniform deposition of ZnO in the form of nanoparticles. To achieve uniform ZnO coating, the SWCNTs first needed to be functionalized by treating the samples in a controlled ozone atmosphere. The uniformly ZnO coated SWCNTs were used to fabricate UV sensing devices. An UV irradiation of the ZnO coated samples turned them from hydrophobic to hydrophilic behaviour. Furthermore, thin films of the ZnO coated SWCNTs allowed us switch p-type field effect transistors made of pristine SWCNTs to have ambipolar characteristics.

  7. Interactions of Carbon Gain and Nitrogen Addition in a Temperate Forest

    NASA Astrophysics Data System (ADS)

    Bazzaz, F. A.

    2001-12-01

    In plants, carbon and nitrogen are intimately related. The plant gains carbon using nitrogen because it is a major constituent of both the light reaction (chlorophyll) and dark reaction (Rubisco and PEP carboxylase). The plant also gains more nitrogen by using carbon to grow roots that can forage for nitrogen, especially the less mobile (NH4+). Rising CO2 and increased nitrogen deposition are important elements of global change, both of which may affect ecosystem structure and function. They may cause a particularly large shift in species composition in systems where contrasting groups of species co-occur, e.g. evergreen coniferous and deciduous broad-leaved tree species. We studied the impact of nitrogen deposition in a mixed forest in central Massachusetts (Harvard Forest). We found that the early-successional broad-leaved species, yellow birch (Betula alleghaniensis) and red maple (Acer rubrum), both showed large increases in biomass, while the late successional species sugar maple (Acer saccharum) and all the coniferous species, hemlock (Tsuga canadensis), red spruce (Picea rubens) and white pine (Pinus strobus), only showed slight increases. As a result, when these species wre grown together, there was a decrease in species diversity. There was a significant correlation between species growth rate and the growth enhancement following nitrogen addition. We used SORTIE, a spatially explicit forest model to speculate about the future of this community. In both hemlock and red oak stands, nitrogen deposition led to shift in forest composition towards further dominance of young forests by yellow birch. We conclude that seedling physiological and demographic responses to increased nitrogen availability will scale up to exaggerate successional dynamics in mixed temperate forests in the future

  8. The long-range non-additive three-body dispersion interactions for the rare gases, alkali, and alkaline-earth atoms.

    PubMed

    Tang, Li-Yan; Yan, Zong-Chao; Shi, Ting-Yun; Babb, James F; Mitroy, J

    2012-03-14

    The long-range non-additive three-body dispersion interaction coefficients Z(111), Z(112), Z(113), and Z(122) are computed for many atomic combinations using standard expressions. The atoms considered include hydrogen, the rare gases, the alkali atoms (up to Rb), and the alkaline-earth atoms (up to Sr). The term Z(111) arising from three mutual dipole interactions is known as the Axilrod-Teller-Muto coefficient or the DDD (dipole-dipole-dipole) coefficient. Similarly, the terms Z(112), Z(113), and Z(122) arise from the mutual combinations of dipole (1), quadrupole (2), and octupole (3) interactions between atoms and they are sometimes known, respectively, as dipole-dipole-quadrupole, dipole-dipole-octupole, and dipole-quadrupole-quadrupole coefficients. Results for the four Z coefficients are given for the homonuclear trimers, for the trimers involving two like-rare-gas atoms, and for the trimers with all combinations of the H, He, and Li atoms. An exhaustive compilation of all coefficients between all possible atomic combinations is presented as supplementary data.

  9. Enhancing the adsorption of ionic liquids onto activated carbon by the addition of inorganic salts

    PubMed Central

    Neves, Catarina M. S. S.; Lemus, Jesús; Freire, Mara G.; Palomar, Jose; Coutinho, João A. P.

    2014-01-01

    Most ionic liquids (ILs) are either water soluble or present a non-negligible miscibility with water that may cause some harmful effects upon their release into the environment. Among other methods, adsorption of ILs onto activated carbon (AC) has shown to be an effective technique to remove these compounds from aqueous solutions. However, this method has proved to be viable only for hydrophobic ILs rather than for the hydrophilic that, being water soluble, have a larger tendency for contamination. In this context, an alternative approach using the salting-out ability of inorganic salts is here proposed to enhance the adsorption of hydrophilic ILs onto activated carbon. The effect of the concentrations of Na2SO4 on the adsorption of five ILs onto AC was investigated. A wide range of ILs that allow the inspection of the IL cation family (imidazolium- and pyridinium-based) and the anion nature (accounting for its hydrophilicity and fluorination) through the adsorption onto AC was studied. In general, it is shown that the use of Na2SO4 enhances the adsorption of ILs onto AC. In particular, this effect is highly relevant when dealing with hydrophilic ILs that are those that are actually poorly removed by AC. In addition, the COnductor like Screening MOdel for Real Solvents (COSMO-RS) was used aiming at complementing the experimental data obtained. This work contributes with the development of novel methods to remove ILs from water streams aiming at creating “greener” processes. PMID:25516713

  10. Nutrient additions to a tropical rain forest drive substantial soil carbon dioxide losses to the atmosphere.

    PubMed

    Cleveland, Cory C; Townsend, Alan R

    2006-07-05

    Terrestrial biosphere-atmosphere carbon dioxide (CO(2)) exchange is dominated by tropical forests, where photosynthetic carbon (C) uptake is thought to be phosphorus (P)-limited. In P-poor tropical forests, P may also limit organic matter decomposition and soil C losses. We conducted a field-fertilization experiment to show that P fertilization stimulates soil respiration in a lowland tropical rain forest in Costa Rica. In the early wet season, when soluble organic matter inputs to soil are high, P fertilization drove large increases in soil respiration. Although the P-stimulated increase in soil respiration was largely confined to the dry-to-wet season transition, the seasonal increase was sufficient to drive an 18% annual increase in CO(2) efflux from the P-fertilized plots. Nitrogen (N) fertilization caused similar responses, and the net increases in soil respiration in response to the additions of N and P approached annual soil C fluxes in mid-latitude forests. Human activities are altering natural patterns of tropical soil N and P availability by land conversion and enhanced atmospheric deposition. Although our data suggest that the mechanisms driving the observed respiratory responses to increased N and P may be different, the large CO(2) losses stimulated by N and P fertilization suggest that knowledge of such patterns and their effects on soil CO(2) efflux is critical for understanding the role of tropical forests in a rapidly changing global C cycle.

  11. Effect of carbon nanotube addition on the wear behavior of basalt/epoxy woven composites.

    PubMed

    Kim, M T; Rhee, K Y; Lee, B H; Kim, C J

    2013-08-01

    The effect of acid-treated carbon nanotube (CNT) addition on the wear and dynamic mechanical thermal properties of basalt/epoxy woven composites was investigated in this study. Basalt/CNT/epoxy composites were fabricated by impregnating woven basalt fibers into epoxy resin mixed with 1 wt% CNTs which were acid-treated. Wear and DMA (dynamic mechanical analyzer) tests were performed on basalt/epoxy composites and basalt/CNT/epoxy composites. The results showed that the addition of the acid-treated CNTs improved the wear properties of basalt/epoxy woven composites. Specifically, the friction coefficient of the basalt/epoxy composite was stabilized in the range of 0.5-0.6 while it fell in the range of 0.3-0.4 for basalt/CNT/epoxy composites. The wear volume loss of the basalt/CNT/epoxy composites was approximately 68% lower than that of the basalt/epoxy composites. The results also showed that the glass transition temperature of basalt/CNT/epoxy composites was higher than that of basalt/epoxy composites. The improvement of wear properties of basalt/epoxy composites by the addition of acid-treated CNTs was caused by the homogeneous load transfer between basalt fibers and epoxy matrix due to the reinforcement of CNTs.

  12. Carbon Nanotube/Conductive Additive/Space Durable Polymer Nanocomposite Films for Electrostatic Charge Dissipation

    NASA Technical Reports Server (NTRS)

    Smith, Joseph G., Jr.; Watson, Kent A.; Delozier, Donavon M.; Connell, John W.

    2003-01-01

    Thin film membranes of space environmentally stable polymeric materials possessing low color/solar absorptivity (alpha) are of interest for potential applications on Gossamer spacecraft. In addition to these properties, sufficient electrical conductivity is required in order to dissipate electrostatic charge (ESC) build-up brought about by the charged orbital environment. One approach to achieve sufficient electrical conductivity for ESC mitigation is the incorporation of single wall carbon nanotubes (SWNTs). However, when the SWNTs are dispersed throughout the polymer matrix, the nanocomposite films tend to be significantly darker than the pristine material resulting in a higher alpha. The incorporation of conductive additives in combination with a decreased loading level of SWNTs is one approach for improving alpha while retaining conductivity. Taken individually, the low loading level of conductive additives and SWNTs is insufficient in achieving the percolation level necessary for electrical conductivity. When added simultaneously to the film, conductivity is achieved through a synergistic effect. The chemistry, physical, and mechanical properties of the nanocomposite films will be presented.

  13. Performance enhancement with powdered activated carbon (PAC) addition in a membrane bioreactor (MBR) treating distillery effluent.

    PubMed

    Satyawali, Yamini; Balakrishnan, Malini

    2009-10-15

    This work investigated the effect of powdered activated carbon (PAC) addition on the operation of a membrane bioreactor (MBR) treating sugarcane molasses based distillery wastewater (spentwash). The 8L reactor was equipped with a submerged 30 microm nylon mesh filter with 0.05 m(2) filtration area. Detailed characterization of the commercial wood charcoal based PAC was performed before using it in the MBR. The MBR was operated over 200 days at organic loading rates (OLRs) varying from 4.2 to 6.9 kg m(-3)d(-1). PAC addition controlled the reactor foaming during start up and enhanced the critical flux by around 23%; it also prolonged the duration between filter cleaning. Operation at higher loading rates was possible and for a given OLR, the chemical oxygen demand (COD) removal was higher with PAC addition. However, biodegradation in the reactor was limited and the high molecular weight compounds were not affected by PAC supplementation. The functional groups on PAC appear to interact with the polysaccharide portion of the sludge, which may reduce its propensity to interact with the nylon mesh.

  14. Influence of Helium Atoms Absorption on the Emission Properties of Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Umaev, S. M.; Levchenko, A. A.; Kolesnikov, N. N.; Filatov, S. V.

    2017-04-01

    We investigated the emission properties of charge sources based on carbon nanotubes prepared by arc discharge deposition of nanotubes onto a flat copper substrate (Borisenko et al. in Instrum Exp Tech 57(6):755, 2014; Low Temp Phys 41(7):567, 2015). The charge sources were submerged into superfluid helium at temperature T=1.3 K. The collector fixed above the charge source at a distance of 0.3 mm was connected to an electrometer. The current of charges was measured by the electrometer when a high voltage was applied to the charge source. In the originally prepared source, the emission of charges (electrons) on the level of 10^{-10}A is observed at a negative voltage above U=80 V and increases with increasing voltage. If the source of charge was kept in liquid helium for 15 h, the current-voltage characteristic changed significantly. The current of charges on the same level of 10^{-10} A was registered at a voltage of U=150 V. Extraction of gases from the source placed in a vacuum chamber at room temperature for 48 h leads to the complete recovery of the emission properties. One can assume that the degradation of the emission properties of the sources is associated with the adsorption of helium atoms by carbon nanotubes at low temperatures. We did not observe any degradation of the emission properties of the charge sources in the case of positive charges injection into superfluid helium.

  15. Boosting the local anodic oxidation of silicon through carbon nanofiber atomic force microscopy probes.

    PubMed

    Rius, Gemma; Lorenzoni, Matteo; Matsui, Soichiro; Tanemura, Masaki; Perez-Murano, Francesc

    2015-01-01

    Many nanofabrication methods based on scanning probe microscopy have been developed during the last decades. Local anodic oxidation (LAO) is one of such methods: Upon application of an electric field between tip and surface under ambient conditions, oxide patterning with nanometer-scale resolution can be performed with good control of dimensions and placement. LAO through the non-contact mode of atomic force microscopy (AFM) has proven to yield a better resolution and tip preservation than the contact mode and it can be effectively performed in the dynamic mode of AFM. The tip plays a crucial role for the LAO-AFM, because it regulates the minimum feature size and the electric field. For instance, the feasibility of carbon nanotube (CNT)-functionalized tips showed great promise for LAO-AFM, yet, the fabrication of CNT tips presents difficulties. Here, we explore the use of a carbon nanofiber (CNF) as the tip apex of AFM probes for the application of LAO on silicon substrates in the AFM amplitude modulation dynamic mode of operation. We show the good performance of CNF-AFM probes in terms of resolution and reproducibility, as well as demonstration that the CNF apex provides enhanced conditions in terms of field-induced, chemical process efficiency.

  16. Boosting the local anodic oxidation of silicon through carbon nanofiber atomic force microscopy probes

    PubMed Central

    Lorenzoni, Matteo; Matsui, Soichiro; Tanemura, Masaki; Perez-Murano, Francesc

    2015-01-01

    Summary Many nanofabrication methods based on scanning probe microscopy have been developed during the last decades. Local anodic oxidation (LAO) is one of such methods: Upon application of an electric field between tip and surface under ambient conditions, oxide patterning with nanometer-scale resolution can be performed with good control of dimensions and placement. LAO through the non-contact mode of atomic force microscopy (AFM) has proven to yield a better resolution and tip preservation than the contact mode and it can be effectively performed in the dynamic mode of AFM. The tip plays a crucial role for the LAO-AFM, because it regulates the minimum feature size and the electric field. For instance, the feasibility of carbon nanotube (CNT)-functionalized tips showed great promise for LAO-AFM, yet, the fabrication of CNT tips presents difficulties. Here, we explore the use of a carbon nanofiber (CNF) as the tip apex of AFM probes for the application of LAO on silicon substrates in the AFM amplitude modulation dynamic mode of operation. We show the good performance of CNF-AFM probes in terms of resolution and reproducibility, as well as demonstration that the CNF apex provides enhanced conditions in terms of field-induced, chemical process efficiency. PMID:25671165

  17. Mechanism of wiggling enhancement due to HBr gas addition during amorphous carbon etching

    NASA Astrophysics Data System (ADS)

    Kofuji, Naoyuki; Ishimura, Hiroaki; Kobayashi, Hitoshi; Une, Satoshi

    2015-06-01

    The effect of gas chemistry during etching of an amorphous carbon layer (ACL) on wiggling has been investigated, focusing especially on the changes in residual stress. Although the HBr gas addition reduces critical dimension loss, it enhances the surface stress and therefore increases wiggling. Attenuated total reflectance Fourier transform infrared spectroscopy revealed that the increase in surface stress was caused by hydrogenation of the ACL surface with hydrogen radicals. Three-dimensional (3D) nonlinear finite element method analysis confirmed that the increase in surface stress is large enough to cause the wiggling. These results also suggest that etching with hydrogen compound gases using an ACL mask has high potential to cause the wiggling.

  18. Acetylation of glycerol to biofuel additives over sulfated activated carbon catalyst.

    PubMed

    Khayoon, M S; Hameed, B H

    2011-10-01

    Oxygenated fuel additives can be produced by acetylation of glycerol. A 91% glycerol conversion with a selectivity of 38%, 28% and 34% for mono-, di- and triacetyl glyceride, respectively, was achieved at 120 °C and 3 h of reaction time in the presence of a catalyst derived from activated carbon (AC) treated with sulfuric acid at 85 °C for 4h to introduce acidic functionalities to its surface. The unique catalytic activity of the catalyst, AC-SA5, was attributed to the presence of sulfur containing functional groups on the AC surface, which enhanced the surface interaction between the glycerol molecule and acyl group of the acetic acid. The catalyst was reused in up to four consecutive batch runs and no significant decline of its initial activity was observed. The conversion and selectivity variation during the acetylation is attributed to the reaction time, reaction temperature, catalyst loading and glycerol to acetic acid molar ratio.

  19. Freshwater ecology. Experimental nutrient additions accelerate terrestrial carbon loss from stream ecosystems.

    PubMed

    Rosemond, Amy D; Benstead, Jonathan P; Bumpers, Phillip M; Gulis, Vladislav; Kominoski, John S; Manning, David W P; Suberkropp, Keller; Wallace, J Bruce

    2015-03-06

    Nutrient pollution of freshwater ecosystems results in predictable increases in carbon (C) sequestration by algae. Tests of nutrient enrichment on the fates of terrestrial organic C, which supports riverine food webs and is a source of CO2, are lacking. Using whole-stream nitrogen (N) and phosphorus (P) additions spanning the equivalent of 27 years, we found that average terrestrial organic C residence time was reduced by ~50% as compared to reference conditions as a result of nutrient pollution. Annual inputs of terrestrial organic C were rapidly depleted via release of detrital food webs from N and P co-limitation. This magnitude of terrestrial C loss can potentially exceed predicted algal C gains with nutrient enrichment across large parts of river networks, diminishing associated ecosystem services.

  20. Intensified nitrogen removal in immobilized nitrifier enhanced constructed wetlands with external carbon addition.

    PubMed

    Wang, Wei; Ding, Yi; Wang, Yuhui; Song, Xinshan; Ambrose, Richard F; Ullman, Jeffrey L

    2016-10-01

    Nitrogen removal performance response of twelve constructed wetlands (CWs) to immobilized nitrifier pellets and different influent COD/N ratios (chemical oxygen demand: total nitrogen in influent) were investigated via 7-month experiments. Nitrifier was immobilized on a carrier pellet containing 10% polyvinyl alcohol (PVA), 2.0% sodium alginate (SA) and 2.0% calcium chloride (CaCl2). A batch experiment demonstrated that 73% COD and 85% ammonia nitrogen (NH4-N) were degraded using the pellets with immobilized nitrifier cells. In addition, different carbon source supplement strategies were applied to remove the nitrate (NO3-N) transformed from NH4-N. An increase in COD/N ratio led to increasing reduction in NO3-N. Efficient nitrification and denitrification promoted total nitrogen (TN) removal in immobilized nitrifier biofortified constructed wetlands (INB-CWs). The results suggested that immobilized nitrifier pellets combined with high influent COD/N ratios could effectively improve the nitrogen removal performance in CWs.

  1. In vitro comparison of the hemocompatibility of diamond-like carbon and carbon nitride coatings with different atomic percentages of N.

    PubMed

    Zhao, Mengli; Li, Dejun; Zhang, Yiteng; Guo, Meixian; Deng, Xiangyun; Gu, Hanqing; Wan, Rongxin

    2012-04-01

    Carbon nitride (CN( x )) and diamond-like carbon (DLC) coatings were prepared by dc magnetron sputtering at room temperature. Different partial pressures of N(2) were used to synthesize CN( x ) to evaluate the relationship between the atomic percentage of nitrogen and hemocompatibility. Auger electron spectroscopy and atomic force microscopy indicated atomic percentages of N of 0.12 and 0.22 and that the CN( x ) coatings were smooth. An in vitro study of the hemocompatibility of the coatings revealed that both CN( x ) coatings had better anticoagulant properties and lower platelet adhesion than DLC. Compared with CN(0.12), the CN(0.22) coating showed longer dynamic clotting time (about 42 min), static clotting time (23.6 min) and recalcification time (45.6 s), as well as lower platelet adhesion (102 cells μm(-2)), aggregation, and activation. The presence of nitrogen in the CN( x ) coatings induced their enhanced hemocompatibility compared with DLC.

  2. Effects of Litter and Nutrient Additions on Soil Carbon Cycling in a Tropical Forest

    NASA Astrophysics Data System (ADS)

    Cusack, D. F.; Halterman, S.; Turner, B. L.; Tanner, E.; Wright, S. J.

    2014-12-01

    Soil carbon (C) dynamics present one of the largest sources of uncertainty in global C cycle models, with tropical forest soils containing some of the largest terrestrial C stocks. Drastic changes in soil C storage and loss are likely to occur if global change alters plant net primary production (NPP) and/or nutrient availability in these ecosystems. We assessed the effects of litter removal and addition, as well as fertilization with nitrogen (N), phosphorus (P), and/or potassium (K), on soil C stocks in a tropical seasonal forest in Panama after ten and sixteen years, respectively. We used a density fractionation scheme to assess manipulation effects on rapidly and slowly cycling pools of C. Soil samples were collected in the wet and dry seasons from 0-5 cm and 5-10 cm depths in 15- 45x45 m plots with litter removal, 2x litter addition, and control (n=5), and from 32- 40x40 m fertilization plots with factorial additions of N, P, and K. We hypothesized that litter addition would increase all soil C fractions, but that the magnitude of the effect on rapidly-cycling C would be dampened by a fertilization effect. Results for the dry season show that the "free light" C fraction, or rapidly cycling soil C pool, was significantly different among the three litter treatments, comprising 5.1 ± 0.9 % of total soil mass in the litter addition plots, 2.7 ± 0.3 % in control plots, and 1.0 ± 0.1 % in litter removal plots at the 0-5cm depth (means ± one standard error, p < 0.05). Bulk soil C results are similar to observed changes in the rapidly cycling C pool for the litter addition and removal. Fertilization treatments on average diminished this C pool size relative to control plots, although there was substantial variability among fertilization treatments. In particular, addition of N and P together did not significantly alter rapidly cycling C pool sizes (4.1 ± 1.2 % of total soil mass) relative to controls (3.5 ± 0.4 %), whereas addition of P alone resulted in

  3. Studies of single walled carbon nanotubes for biomedical, mechanical and electrical applications using atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Lahiji, Roya Roientan

    The promise of carbon nanotubes to provide high-strength composites implies that carbon nanotubes might find widespread use throughout the world, implying that humans everywhere will be exposed to carbon nanotube-containing materials. In order to study what effects if any carbon nanotubes might have on the function of living cells, we have studied the association of single stranded DNA (ssDNA) with single wall carbon nanotubes (SWCNTs) as a first step toward understanding the interaction of SWCNTs with living matter. Studies have been performed on both as-received and chemically oxidized SWCNTs to better understand the preferential association of ssDNA with SWCNTs. Samples of T30 ssDNA:SWCNT were examined under ambient conditions using non-contact Atomic Force Microscopy (AFM)) techniques. AFM images of well-dispersed, as-received SWCNTs revealed isolated features on the SWCNT that are 1.4 to 2.8 nm higher than the bare SWCNT itself. X-ray Photoemission Spectroscopy (XPS) confirmed these features to be T30 ssDNA in nature. Chemically oxidizing SWCNTs before dispersion by sonication is found to be an effective way to increase the number of T30 ssDNA features. A series of experiments showed that free radical scavengers such as ascorbic acid and trolox can effectively prevent the conjugation of ssDNA to SWCNTs, suggesting a significant role of free radicals in this association. Also hybridization of the complimentary ssDNA sequences showed the covalent nature of this association. These results are important to understanding the precise mechanism of ssDNA:SWCNT association and provide valuable information for future use in electronics, biosensors and as a possible drug carrier into individual cells. If SWCNTs are used in biosensor or circuit design applications then it is important to note how much energy can be stored in a SWCNT based on its shape and configuration before a permanent damage is introduced to it. Therefore a study has been done on bending SWCNTs into

  4. Surface modification of nitrogen-doped carbon nanotubes by ozone via atomic layer deposition

    SciTech Connect

    Lushington, Andrew; Liu, Jian; Tang, Yongji; Li, Ruying; Sun, Xueliang

    2014-01-15

    The use of ozone as an oxidizing agent for atomic layer deposition (ALD) processes is rapidly growing due to its strong oxidizing capabilities. However, the effect of ozone on nanostructured substrates such as nitrogen-doped multiwalled carbon nanotubes (NCNTs) and pristine multiwalled carbon nanotubes (PCNTs) are not very well understood and may provide an avenue toward functionalizing the carbon nanotube surface prior to deposition. The effects of ALD ozone treatment on NCNTs and PCNTs using 10 wt. % ozone at temperatures of 150, 250, and 300 °C are studied. The effect of ozone pulse time and ALD cycle number on NCNTs and PCNTs was also investigated. Morphological changes to the substrate were observed by scanning electron microscopy and high resolution transmission electron microscopy. Brunauer-Emmett-Teller measurements were also conducted to determine surface area, pore size, and pore size distribution following ozone treatment. The graphitic nature of both NCNTs and PCNTs was determined using Raman analysis while x-ray photoelectron spectroscopy (XPS) was employed to probe the chemical nature of NCNTs. It was found that O{sub 3} attack occurs preferentially to the outermost geometric surface of NCNTs. Our research also revealed that the deleterious effects of ozone are found only on NCNTs while little or no damage occurs on PCNTs. Furthermore, XPS analysis indicated that ALD ozone treatment on NCNTs, at elevated temperatures, results in loss of nitrogen content. Our studies demonstrate that ALD ozone treatment is an effective avenue toward creating low nitrogen content, defect rich substrates for use in electrochemical applications and ALD of various metal/metal oxides.

  5. In situ observation of atomic hydrogen etching on diamond-like carbon films produced by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Cheng, C.-L.; Chia, C.-T.; Chiu, C.-C.; Wu, C.-C.; Cheng, H.-F.; Lin, I.-N.

    2001-04-01

    Atomic hydrogen etching on the pulsed laser deposited (PLD) diamond-like carbon (DLC) films were examined in situ by using Raman spectroscopy. Thermal annealing of the as-prepared DLC films was found to alter the D-band (˜1355 cm -1) and G-band (˜1582 cm -1) from unresolved features at room temperature to clearly separated bands at above 500°C, indicating graphitization of the films. The presence of atomic hydrogen retards graphitization at temperatures lower than 500°C, presumably because reactive atomic hydrogen formed sp 3-bonding carbons which prevented graphitization at below 500°C, while at above 500°C, the hydrogen etches away disordered structure of the DLC film as the intensity changes of the D-bands demonstrate.

  6. Activation of extended red emission photoluminescence in carbon solids by exposure to atomic hydrogen and UV radiation

    NASA Technical Reports Server (NTRS)

    Furton, Douglas G.; Witt, Adolf N.

    1993-01-01

    We report on new laboratory results which relate directly to the observation of strongly enhanced extended red emission (ERE) by interstellar dust in H2 photodissociation zones. The ERE has been attributed to photoluminescence by hydrogenated amorphous carbon (HAC). We are demonstrating that exposure to thermally dissociated atomic hydrogen will restore the photoluminescence efficiency of previously annealed HAC. Also, pure amorphous carbon (AC), not previously photoluminescent, can be induced to photoluminesce by exposure to atomic hydrogen. This conversion of AC into HAC is greatly enhanced by the presence of UV irradiation. The presence of dense, warm atomic hydrogen and a strong UV radiation field are characteristic environmental properties of H2 dissociation zones. Our results lend strong support to the HAC photoluminescence explanation for ERE.

  7. Vegetation feedbacks of nutrient addition lead to a weaker carbon sink in an ombrotrophic bog.

    PubMed

    Larmola, Tuula; Bubier, Jill L; Kobyljanec, Christine; Basiliko, Nathan; Juutinen, Sari; Humphreys, Elyn; Preston, Michael; Moore, Tim R

    2013-12-01

    To study vegetation feedbacks of nutrient addition on carbon sequestration capacity, we investigated vegetation and ecosystem CO2 exchange at Mer Bleue Bog, Canada in plots that had been fertilized with nitrogen (N) or with N plus phosphorus (P) and potassium (K) for 7-12 years. Gross photosynthesis, ecosystem respiration, and net CO2 exchange were measured weekly during May-September 2011 using climate-controlled chambers. A substrate-induced respiration technique was used to determine the functional ability of the microbial community. The highest N and NPK additions were associated with 40% less net CO2 uptake than the control. In the NPK additions, a diminished C sink potential was due to a 20-30% increase in ecosystem respiration, while gross photosynthesis rates did not change as greater vascular plant biomass compensated for the decrease in Sphagnum mosses. In the highest N-only treatment, small reductions in gross photosynthesis and no change in ecosystem respiration led to the reduced C sink. Substrate-induced microbial respiration was significantly higher in all levels of NPK additions compared with control. The temperature sensitivity of respiration in the plots was lower with increasing cumulative N load, suggesting more labile sources of respired CO2 . The weaker C sink potential could be explained by changes in nutrient availability, higher woody : foliar ratio, moss loss, and enhanced decomposition. Stronger responses to NPK fertilization than to N-only fertilization for both shrub biomass production and decomposition suggest that the bog ecosystem is N-P/K colimited rather than N-limited. Negative effects of further N-only deposition were indicated by delayed spring CO2 uptake. In contrast to forests, increased wood formation and surface litter accumulation in bogs seem to reduce the C sink potential owing to the loss of peat-forming Sphagnum.

  8. Carbon and nitrogen additions induce distinct priming effects along an organic-matter decay continuum

    NASA Astrophysics Data System (ADS)

    Qiao, Na; Xu, Xingliang; Hu, Yuehua; Blagodatskaya, Evgenia; Liu, Yongwen; Schaefer, Douglas; Kuzyakov, Yakov

    2016-01-01

    Decomposition of organic matter (OM) in soil, affecting carbon (C) cycling and climate feedbacks, depends on microbial activities driven by C and nitrogen (N) availability. However, it remains unknown how decomposition of various OMs vary across global supplies and ratios of C and N inputs. We examined OM decomposition by incubating four types of OM (leaf litter, wood, organic matter from organic and mineral horizons) from a decay continuum in a subtropical forest at Ailao Mountain, China with labile C and N additions. Decomposition of wood with high C:N decreased for 3.9 to 29% with these additions, while leaf decomposition was accelerated only within a narrow C:N range of added C and N. Decomposition of OM from organic horizon was accelerated by high C:N and suppressed by low C:N, but mineral soil was almost entirely controlled by high C:N. These divergent responses to C and N inputs show that mechanisms for priming (i.e. acceleration or retardation of OM decomposition by labile inputs) vary along this decay continuum. We conclude that besides C:N ratios of OM, those of labile inputs control the OM decay in the litter horizons, while energy (labile C) regulates decomposition in mineral soil. This suggests that OM decomposition can be predicted from its intrinsic C:N ratios and those of labile inputs.

  9. Additive Manufacturing of Multifunctional Components Using High Density Carbon Nanotube Yarn Filaments

    NASA Technical Reports Server (NTRS)

    Gardner, John M.; Sauti, Godfrey; Kim, Jae-Woo; Cano, Roberto J.; Wincheski, Russell A.; Stelter, Christopher J.; Grimsley, Brian W.; Working, Dennis C.; Siochi, Emilie J.

    2016-01-01

    Additive manufacturing allows for design freedom and part complexity not currently attainable using traditional manufacturing technologies. Fused Filament Fabrication (FFF), for example, can yield novel component geometries and functionalities because the method provides a high level of control over material placement and processing conditions. This is achievable by extrusion of a preprocessed filament feedstock material along a predetermined path. However if fabrication of a multifunctional part relies only on conventional filament materials, it will require a different material for each unique functionality printed into the part. Carbon nanotubes (CNTs) are an attractive material for many applications due to their high specific strength as well as good electrical and thermal conductivity. The presence of this set of properties in a single material presents an opportunity to use one material to achieve multifunctionality in an additively manufactured part. This paper describes a recently developed method for processing continuous CNT yarn filaments into three-dimensional articles, and summarizes the mechanical, electrical, and sensing performance of the components fabricated in this way.

  10. Carbon and nitrogen additions induce distinct priming effects along an organic-matter decay continuum

    PubMed Central

    Qiao, Na; Xu, Xingliang; Hu, Yuehua; Blagodatskaya, Evgenia; Liu, Yongwen; Schaefer, Douglas; Kuzyakov, Yakov

    2016-01-01

    Decomposition of organic matter (OM) in soil, affecting carbon (C) cycling and climate feedbacks, depends on microbial activities driven by C and nitrogen (N) availability. However, it remains unknown how decomposition of various OMs vary across global supplies and ratios of C and N inputs. We examined OM decomposition by incubating four types of OM (leaf litter, wood, organic matter from organic and mineral horizons) from a decay continuum in a subtropical forest at Ailao Mountain, China with labile C and N additions. Decomposition of wood with high C:N decreased for 3.9 to 29% with these additions, while leaf decomposition was accelerated only within a narrow C:N range of added C and N. Decomposition of OM from organic horizon was accelerated by high C:N and suppressed by low C:N, but mineral soil was almost entirely controlled by high C:N. These divergent responses to C and N inputs show that mechanisms for priming (i.e. acceleration or retardation of OM decomposition by labile inputs) vary along this decay continuum. We conclude that besides C:N ratios of OM, those of labile inputs control the OM decay in the litter horizons, while energy (labile C) regulates decomposition in mineral soil. This suggests that OM decomposition can be predicted from its intrinsic C:N ratios and those of labile inputs. PMID:26806914

  11. The atomic scale structure of CXV carbon: wide-angle x-ray scattering and modeling studies

    NASA Astrophysics Data System (ADS)

    Hawelek, L.; Brodka, A.; Dore, J. C.; Honkimaki, V.; Burian, A.

    2013-11-01

    The disordered structure of commercially available CXV activated carbon produced from finely powdered wood-based carbon has been studied using the wide-angle x-ray scattering technique, molecular dynamics and density functional theory simulations. The x-ray scattering data has been converted to the real space representation in the form of the pair correlation function via the Fourier transform. Geometry optimizations using classical molecular dynamics based on the reactive empirical bond order potential and density functional theory at the B3LYP/6-31g* level have been performed to generate nanoscale models of CXV carbon consistent with the experimental data. The final model of the structure comprises four chain-like and buckled graphitic layers containing a small percentage of four-fold coordinated atoms (sp3 defects) in each layer. The presence of non-hexagonal rings in the atomic arrangement has been also considered.

  12. Prismatic modifications of single-walled carbon nanotubes and their electronic properties: Regular adsorption of fluorine atoms on graphene surfaces of nanotubes

    NASA Astrophysics Data System (ADS)

    Tomilin, O. B.; Stankevich, I. V.; Muryumin, E. E.; Lesin, S. A.; Syrkina, N. P.

    2011-01-01

    The regular adsorption of fluorine atoms on surfaces of single-walled carbon nanotubes along their axes can lead to a modification of cylindrical carbon cores of these single-walled carbon nanotubes to carbon cores that have a nearly prismatic shape (prismatic modification). In faces of these modified single-walled carbon nanotubes, there can arise quasi-one-dimensional isolated carbon conjugated subsystems (tracks) with different structures. It has been established that the main characteristics of the single-walled carbon nanotubes thus modified are rather close to the corresponding characteristics of the related isostructural polymer conjugated systems (such as cis-polyenes, polyphenylenes, poly(periacenes), or polyphenantrenes). Fragments of model nanotubes of the ( n, n) and ( n, 0) types that contain up to 360 carbon atoms and their derivatives doped with fluorine atoms have been calculated using the semiempirical parametric method 3.

  13. Atom probe tomography and nano secondary ion mass spectroscopy investigation of the segregation of boron at austenite grain boundaries in 0.5 wt.% carbon steels

    NASA Astrophysics Data System (ADS)

    Seol, J. B.; Lim, N. S.; Lee, B. H.; Renaud, L.; Park, C. G.

    2011-06-01

    The grain boundary segregation of boron atoms in high strength low alloy steels containing 50 ppm boron was accomplished using atom probe tomography (APT) and nano-beam secondary ion mass spectroscopy (SIMS). The formation of boro-carbides under an excessive addition of boron to the steels was identified through the SIMS and TEM. The APT was performed in order to evaluate the composition of the alloying elements, such as, boron and carbon, segregated at prior austenite grain boundaries. The boron contents at the prior austenite grain boundaries were approximately 1.7 ± 0.2 at.%, which was approximately 70 times more than the amount of boron added to the steels.

  14. Perfluoroalkyl-substituted ethylene carbonates: Novel electrolyte additives for high-voltage lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhu, Ye; Casselman, Matthew D.; Li, Yan; Wei, Alexander; Abraham, Daniel P.

    2014-01-01

    A new family of polyfluoroalkyl-substituted ethylene carbonates is synthesized and tested as additives in lithium-ion cells containing EC:EMC + LiPF6-based electrolyte. The influence of these compounds is investigated in Li1.2Ni0.15Mn0.55Co0.1O2//graphite cells via a combination of galvanostatic cycling and electrochemical impedance spectroscopy (EIS) tests. Among the four additives studied in this work (4-(trifluoromethyl)-1,3-dioxolan-2-one (TFM-EC), 4-(perfluorobutyl)-1,3-dioxolan-2-one (PFB-EC), 4-(perfluorohexyl)-1,3-dioxolan-2-one (PFH-EC), and 4-(perfluorooctyl)-1,3-dioxolan-2-one (PFO-EC)), small amounts (0.5 wt%) of PFO-EC is found to be most effective in lessening cell performance degradation during extended cycling. Linear sweep voltammetry (LSV), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy are used to further characterize the effects of PFO-EC on the positive and negative electrodes. LSV data from the electrolyte, and XPS analyses of electrodes harvested after cycling, suggest that PFO-EC is oxidized on the cathode forming surface films that slow electrode/cell impedance rise. Differential capacity (dQ/dV) plots from graphite//Li cells suggest that PFO-EC is involved in solid electrolyte interphase (SEI) formation. Raman data from anodes after cycling suggest that structural disordering of graphite is reduced by the addition of PFO-EC, which may explain the improved cell capacity retention.

  15. Excited-state intramolecular proton transfer to carbon atoms: nonadiabatic surface-hopping dynamics simulations.

    PubMed

    Xia, Shu-Hua; Xie, Bin-Bin; Fang, Qiu; Cui, Ganglong; Thiel, Walter

    2015-04-21

    Excited-state intramolecular proton transfer (ESIPT) between two highly electronegative atoms, for example, oxygen and nitrogen, has been intensely studied experimentally and computationally, whereas there has been much less theoretical work on ESIPT to other atoms such as carbon. We have employed CASSCF, MS-CASPT2, RI-ADC(2), OM2/MRCI, DFT, and TDDFT methods to study the mechanistic photochemistry of 2-phenylphenol, for which such an ESIPT has been observed experimentally. According to static electronic structure calculations, irradiation of 2-phenylphenol populates the bright S1 state, which has a rather flat potential in the Franck-Condon region (with a shallow enol minimum at the CASSCF level) and may undergo an essentially barrierless ESIPT to the more stable S1 keto species. There are two S1/S0 conical intersections that mediate relaxation to the ground state, one in the enol region and one in the keto region, with the latter one substantially lower in energy. After S1 → S0 internal conversion, the transient keto species can return back to the S0 enol structure via reverse ground-state hydrogen transfer in a facile tautomerization. This mechanistic scenario is verified by OM2/MRCI-based fewest-switches surface-hopping simulations that provide detailed dynamic information. In these trajectories, ESIPT is complete within 118 fs; the corresponding S1 excited-state lifetime is computed to be 373 fs in vacuum. Most of the trajectories decay to the ground state via the S1/S0 conical intersection in the keto region (67%), and the remaining ones via the enol region (33%). The combination of static electronic structure computations and nonadiabatic dynamics simulations is expected to be generally useful for understanding the mechanistic photophysics and photochemistry of molecules with intramolecular hydrogen bonds.

  16. Carbon flux from plants to soil microbes is highly sensitive to nitrogen addition and biochar amendment

    NASA Astrophysics Data System (ADS)

    Kaiser, C.; Solaiman, Z. M.; Kilburn, M. R.; Clode, P. L.; Fuchslueger, L.; Koranda, M.; Murphy, D. V.

    2012-04-01

    The release of carbon through plant roots to the soil has been recognized as a governing factor for soil microbial community composition and decomposition processes, constituting an important control for ecosystem biogeochemical cycles. Moreover, there is increasing awareness that the flux of recently assimilated carbon from plants to the soil may regulate ecosystem response to environmental change, as the rate of the plant-soil carbon transfer will likely be affected by increased plant C assimilation caused by increasing atmospheric CO2 levels. What has received less attention so far is how sensitive the plant-soil C transfer would be to possible regulations coming from belowground, such as soil N addition or microbial community changes resulting from anthropogenic inputs such as biochar amendments. In this study we investigated the size, rate and sensitivity of the transfer of recently assimilated plant C through the root-soil-mycorrhiza-microbial continuum. Wheat plants associated with arbuscular mycorrhizal fungi were grown in split-boxes which were filled either with soil or a soil-biochar mixture. Each split-box consisted of two compartments separated by a membrane which was penetrable for mycorrhizal hyphae but not for roots. Wheat plants were only grown in one compartment while the other compartment served as an extended soil volume which was only accessible by mycorrhizal hyphae associated with the plant roots. After plants were grown for four weeks we used a double-labeling approach with 13C and 15N in order to investigate interactions between C and N flows in the plant-soil-microorganism system. Plants were subjected to an enriched 13CO2 atmosphere for 8 hours during which 15NH4 was added to a subset of split-boxes to either the root-containing or the root-free compartment. Both, 13C and 15N fluxes through the plant-soil continuum were monitored over 24 hours by stable isotope methods (13C phospho-lipid fatty acids by GC-IRMS, 15N/13C in bulk plant

  17. Determination of antimony, arsenic, bismuth, selenium, tellurium and tin by low pressure atomic absorption spectrometry with a quartz tube furnace atomizer and hydride generation with air addition.

    PubMed

    Zhang, B; Wang, Y; Wang, X; Chen, X; Feng, J

    1995-08-01

    A new method has been developed for the determination of antimony, arsenic, bismuth, selenium, tellurium and tin by hydride generation-atomic absorption spectrometry in an electrically heated quartz tube furnace under sub-atmospheric pressure. The hydride generator, operating at a pressure lower than atmospheric, is used to generate and collect the hydrides of these elements. A certain volume (at atmospheric pressure) of air is then added to the generator after the formation of the volatile hydride. The gaseous mixture of the hydride and air is drawn into an evacuated, heated quartz tube by a vacuum pump. The proposed method gives improved sensitivities and detection limits.

  18. Direct determination and speciation of mercury compounds in environmental and biological samples by carbon bed atomic absorption spectroscopy

    SciTech Connect

    Skelly, E.M.

    1982-01-01

    A method was developed for the direct determination of mercury in water and biological samples using a unique carbon bed atomizer for atomic absorption spectroscopy. The method avoided sources of error such as loss of volatile mercury during sample digestion and contamination of samples through added reagents by eliminating sample pretreatment steps. The design of the atomizer allowed use of the 184.9 nm mercury resonance line in the vacuum ultraviolet region, which increased sensitivity over the commonly used spin-forbidden 253.7 nm line. The carbon bed atomizer method was applied to a study of mercury concentrations in water, hair, sweat, urine, blood, breath and saliva samples from a non-occupationally exposed population. Data were collected on the average concentration, the range and distribution of mercury in the samples. Data were also collected illustrating individual variations in mercury concentrations with time. Concentrations of mercury found were significantly higher than values reported in the literature for a ''normal'' population. This is attributed to the increased accuracy gained by eliminating pretreatment steps and increasing atomization efficiency. Absorption traces were obtained for various solutions of pure and complexed mercury compounds. Absorption traces of biological fluids were also obtained. Differences were observed in the absorption-temperatures traces of various compounds. The utility of this technique for studying complexation was demonstrated.

  19. The Suess Effect and Additional Impacts on the Carbon Isotope Composition of a Belizean Coral

    NASA Astrophysics Data System (ADS)

    Greer, L.; Bunn, S.; Humston, R.; Swart, P. K.; Curran, H.; Rose, L. E.

    2011-12-01

    Recent work has shown that the geochemistry of coral skeletons can reflect large-scale changes in the ocean carbon isotope budget as influenced by the anthropogenic influx of fossil fuel carbon to the atmosphere (the Suess Effect). Yet not all coral carbon records reflect just atmospheric controls on carbon. This study assesses the relative influence of the Suess Effect on carbon chemistry within a Belizean Montastrea faveolota colony and interprets deviations from the Suess Effect signal. The coral sample used for this study was collected off Wee Wee Caye, in South-Central Belize offshore of the Sittee River, Stann Creek District in 2003. Coral carbonate was sampled at an average resolution of 15 samples per coral year. Carbon isotope data from the Belizean coral were compared with mean annual carbon isotope data from Atlantic corals in a study by Swart et. al (2010) to analyze the relative contribution of the Suess Effect and competing controls on the carbon isotope composition of Belizean waters. The observed pattern in the Belize coral suggested two distinct trends in carbon isotopic composition, and segmented regression analysis indicated a significant breakpoint occurs in this record in approximately 1965. Deforestation rates in Belize after the 1960's have been almost double that for the rest of Central America (2.3% vs. 1.2% annually) corresponding with a general shift from rural farming to large scale agriculture in Belize. Consequently, increased rates of deforestation in Belize may have been an important factor in carbon isotope budgets of the area over the last several decades. Compared with data averaged from Atlantic coral samples, annual carbon isotope values in Belizean coral declined more rapidly since the 1960's. We attribute this sharper decline in the Belizean coral to enhanced influx of terrestrial 'light' organic carbon to the reef over the study period.

  20. X-ray diffraction analysis of LiCu2O2 crystals with additives of silver atoms

    NASA Astrophysics Data System (ADS)

    Sirotinkin, V. P.; Bush, A. A.; Kamentsev, K. E.; Dau, H. S.; Yakovlev, K. A.; Tishchenko, E. A.

    2015-09-01

    Silver-containing LiCu2O2 crystals up to 4 × 8 × 8 mm in size were grown by the crystallization of 80(1- x)CuO · 20 x AgNO3 · 20Li2CO3 (0 ≤ х ≤ 0.5) mixture melt. According to the X-ray spectral and Rietveld X-ray diffraction data, the maximum amount of silver incorporated in the LiCu2O2 structure is about 4 at % relative to the copper content. It was established that silver atoms occupy statistically crystallographic positions of lithium atoms. The incorporation of silver atoms is accompanied by a noticeable increase in parameter с of the LiCu2O2 rhombic unit cell, a slight increase in parameter а, and a slight decrease in parameter b.

  1. Effects of nitrogen additions on above- and belowground carbon dynamics in two tropical forests

    SciTech Connect

    Cusack, D.; Silver, W.L.; Torn, M.S.; McDowell, W.H.

    2011-04-15

    Anthropogenic nitrogen (N) deposition is increasing rapidly in tropical regions, adding N to ecosystems that often have high background N availability. Tropical forests play an important role in the global carbon (C) cycle, yet the effects of N deposition on C cycling in these ecosystems are poorly understood. We used a field N-fertilization experiment in lower and upper elevation tropical rain forests in Puerto Rico to explore the responses of above- and belowground C pools to N addition. As expected, tree stem growth and litterfall productivity did not respond to N fertilization in either of these Nrich forests, indicating a lack of N limitation to net primary productivity (NPP). In contrast, soil C concentrations increased significantly with N fertilization in both forests, leading to larger C stocks in fertilized plots. However, different soil C pools responded to N fertilization differently. Labile (low density) soil C fractions and live fine roots declined with fertilization, while mineral-associated soil C increased in both forests. Decreased soil CO2 fluxes in fertilized plots were correlated with smaller labile soil C pools in the lower elevation forest (R2 = 0.65, p\\0.05), and with lower live fine root biomass in the upper elevation forest (R2 = 0.90, p\\0.05). Our results indicate that soil C storage is sensitive to N deposition in tropical forests, even where plant productivity is not N-limited. The mineral-associated soil C pool has the potential to respond relatively quickly to N additions, and can drive increases in bulk soil C stocks in tropical forests.

  2. Magnetically anisotropic additive for scalable manufacturing of polymer nanocomposite: iron-coated carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Yamamoto, Namiko; Manohara, Harish; Platzman, Ellen

    2016-02-01

    Novel nanoparticles additives for polymer nanocomposites were prepared by coating carbon nanotubes (CNTs) with ferromagnetic iron (Fe) layers, so that their micro-structures can be bulk-controlled by external magnetic field application. Application of magnetic fields is a promising, scalable method to deliver bulk amount of nanocomposites while maintaining organized nanoparticle assembly throughout the uncured polymer matrix. In this work, Fe layers (˜18 nm thick) were deposited on CNTs (˜38 nm diameter and ˜50 μm length) to form thin films with high aspect ratio, resulting in a dominance of shape anisotropy and thus high coercivity of ˜50-100 Oe. The Fe-coated CNTs were suspended in water and applied with a weak magnetic field of ˜75 G, and yet preliminary magnetic assembly was confirmed. Our results demonstrate that the fabricated Fe-coated CNTs are magnetically anisotropic and effectively respond to magnetic fields that are ˜103 times smaller than other existing work (˜105 G). We anticipate this work will pave the way for effective property enhancement and bulk application of CNT-polymer nanocomposites, through controlled micro-structure and scalable manufacturing.

  3. Soil carbon sequestration in prairie grasslands increased by chronic nitrogen addition.

    PubMed

    Fornara, Dario A; Tilman, David

    2012-09-01

    Human-induced increases in nitrogen (N) deposition are common across many terrestrial ecosystems worldwide. Greater N availability not only reduces biological diversity, but also affects the biogeochemical coupling of carbon (C) and N cycles in soil ecosystems. Soils are the largest active terrestrial C pool and N deposition effects on soil C sequestration or release could have global importance. Here, we show that 27 years of chronic N additions to prairie grasslands increased C sequestration in mineral soils and that a potential mechanism responsible for this C accrual was an N-induced increase in root mass. Greater soil C sequestration followed a dramatic shift in plant community composition from native-species-rich C4 grasslands to naturalized-species-rich C3 grasslands, which, despite lower soil C gains per unit of N added, still acted as soil C sinks. Since both high plant diversity and elevated N deposition may increase soil C sequestration, but N deposition also decreases plant diversity, more research is needed to address the long-term implications for soil C storage of these two factors. Finally, because exotic C3 grasses often come to dominate N-enriched grasslands, it is important to determine if such N-dependent soil C sequestration occurs across C3 grasslands in other regions worldwide.

  4. Calcium carbonate crystallization in the presence of modified polysaccharides and linear polymeric additives

    NASA Astrophysics Data System (ADS)

    Matahwa, H.; Ramiah, V.; Sanderson, R. D.

    2008-10-01

    Crystallization of calcium carbonate was performed in the presence of grafted polysaccharides, polyacrylamide (PAM) and polyacrylic acid (PAA). The grafted polysaccharides gave crystal morphologies that were different from the unmodified polysaccharides but similar to the ones given by homopolymers of the grafted chains. PAM-grafted α-cellulose gave rectangular platelets that aggregated to form 'spherical' crystals on the surface of the fiber, whereas PAA grafted α-cellulose gave spherical crystals on the surface of the fiber. X-ray diffraction (XRD) spectroscopy showed that PAM-grafted α-cellulose, PAM as well as the control (no polymeric additive) gave calcite crystals at both 25 and 80 °C. However, the PAA-grafted α-cellulose and PAA homopolymer gave calcite and vaterite crystals at 25 °C with calcite and aragonite crystals along with traces of vaterite being formed at 80 °C. The fiber surface coverage by these crystals was more on the acrylic- and acrylamide-grafted cellulose than on the ungrafted α-cellulose. The evolution of CaCO 3 polymorphs as well as crystal morphology in PAA-grafted starch was similar to that of PAA-grafted α-cellulose at the two temperatures employed.

  5. Sub-5 nm nanostructures fabricated by atomic layer deposition using a carbon nanotube template

    NASA Astrophysics Data System (ADS)

    Woo, Ju Yeon; Han, Hyo; Kim, Ji Weon; Lee, Seung-Mo; Ha, Jeong Sook; Shim, Joon Hyung; Han, Chang-Soo

    2016-07-01

    The fabrication of nanostructures having diameters of sub-5 nm is very a important issue for bottom-up nanofabrication of nanoscale devices. In this work, we report a highly controllable method to create sub-5 nm nano-trenches and nanowires by combining area-selective atomic layer deposition (ALD) with single-walled carbon nanotubes (SWNTs) as templates. Alumina nano-trenches having a depth of 2.6 ∼ 3.0 nm and SiO2 nano-trenches having a depth of 1.9 ∼ 2.2 nm fully guided by the SWNTs have been formed on SiO2/Si substrate. Through infilling ZnO material by ALD in alumina nano-trenches, well-defined ZnO nanowires having a thickness of 3.1 ∼ 3.3 nm have been fabricated. In order to improve the electrical properties of ZnO nanowires, as-fabricated ZnO nanowires by ALD were annealed at 350 °C in air for 60 min. As a result, we successfully demonstrated that as-synthesized ZnO nanowire using a specific template can be made for various high-density resistive components in the nanoelectronics industry.

  6. Atomic-force-microscopy nanowriting on ultrathin tetrahedral amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Pivovarov, Pavel A.; Zavedeev, Evgeny V.; Frolov, Vadim D.; Roch, Teja; Scheibe, Hans-Joachim; Pimenov, Sergei M.

    2016-11-01

    We report the atomic-force-microscopy (AFM)-based nanolithography writing of surface patterns on ultrathin (<100 nm thick) ta-C films in ambient air and following contact-mode AFM reading of nanoscale topography, nanofriction properties, and local electrical conductivity of the produced nanopatterns. AFM writing of various patterns such as single nanospots, linear nanostructures, and raster images (`nanoletters') is demonstrated, depending on the magnitude and duration of the voltage pulses applied between the ta-C film and conductive probe, and the relative humidity of ambient air. It is found that the AFM tip-assisted nanowriting process occurring under (1) the presence of adsorbed water layers on the ta-C surface, (2) the applied voltage of >4 V, and (3) the contact pressures in the GPa range results in the formation of a novel carbon phase in a nm-thick surface layer characterized by the lower density, lower mechanical strength, lower electrical conductivity, and increased nanofriction as compared to the original film. The structure of the tip-modified nm-thick layer on the ta-C film is assumed to be a structure of graphite oxide which can be further modified in the presence of water under high contact pressures.

  7. Study of adhesion of vertically aligned carbon nanotubes to a substrate by atomic-force microscopy

    NASA Astrophysics Data System (ADS)

    Ageev, O. A.; Blinov, Yu. F.; Il'ina, M. V.; Il'in, O. I.; Smirnov, V. A.; Tsukanova, O. G.

    2016-02-01

    The adhesion to a substrate of vertically aligned carbon nanotubes (VA CNT) produced by plasmaenhanced chemical vapor deposition has been experimentally studied by atomic-force microscopy in the current spectroscopy mode. The longitudinal deformation of VA CNT by applying an external electric field has been simulated. Based on the results, a technique of determining VA CNT adhesion to a substrate has been developed that is used to measure the adhesion strength of connecting VA CNT to a substrate. The adhesion to a substrate of VA CNT 70-120 nm in diameter varies from 0.55 to 1.19 mJ/m2, and the adhesion force from 92.5 to 226.1 nN. When applying a mechanical load, the adhesion strength of the connecting VA CNT to a substrate is 714.1 ± 138.4 MPa, and the corresponding detachment force increases from 1.93 to 10.33 μN with an increase in the VA CNT diameter. As an external electric field is applied, the adhesion strength is almost doubled and is 1.43 ± 0.29 GPa, and the corresponding detachment force is changed from 3.83 to 20.02 μN. The results can be used in the design of technological processes of formation of emission structures, VA CNT-based elements for vacuum microelectronics and micro- and nanosystem engineering, and also the methods of probe nanodiagnostics of VA CNT.

  8. Controlled manipulation of flexible carbon nanotubes through shape-dependent pushing by atomic force microscopy.

    PubMed

    Yang, Seung-Cheol; Qian, Xiaoping

    2013-09-17

    A systematic approach to manipulating flexible carbon nanotubes (CNTs) has been developed on the basis of atomic force microscope (AFM) based pushing. Pushing CNTs enables efficient transport and precise location of individual CNTs. A key issue for pushing CNTs is preventing defective distortion in repetitive bending and unbending deformation. The approach presented here controls lateral movement of an AFM tip to bend CNTs without permanent distortion. The approach investigates possible defects caused by tensile strain of the outer tube under uniform bending and radial distortion by kinking. Using the continuum beam model and experimental bending tests, dependency of maximum bending strain on the length of bent CNTs and radial distortion on bending angles at a bent point have been demonstrated. Individual CNTs are manipulated by limiting the length of bent CNTs and the bending angle. In our approach, multiwalled CNTs with 5-15 nm diameter subjected to bending deformation produce no outer tube breakage under uniform bending and reversible radial deformation with bending angles less than 110°. The lateral tip movement is determined by a simple geometric model that relies on the shape of multiwalled CNTs. The model effectively controls deforming CNT length and bending angle for given CNT shape. Experimental results demonstrate successful manipulation of randomly dispersed CNTs without visual defects. This approach to pushing can be extended to develop a wide range of CNT based nanodevice applications.

  9. Atomic layer deposition of aluminum oxide films for carbon nanotube network transistor passivation.

    PubMed

    Grigoras, Kestutis; Zavodchikova, Marina Y; Nasibulin, Albert G; Kauppinen, Esko I; Ermolov, Vladimir; Franssila, Sami

    2011-10-01

    Ultra-thin (2-5 nm thick) aluminum oxide layers were grown on non-functionalized individual single walled carbon nanotubes (SWCNT) and their bundles by atomic layer deposition (ALD) technique in order to investigate the mechanism of the coating process. Transmission electron microscopy (TEM) was used to examine the uniformity and conformality of the coatings grown at different temperatures (80 degrees C or 220 degrees C) and with different precursors for oxidation (water and ozone). We found that bundles of SWCNTs were coated continuously, but at the same time, bare individual nanotubes remained uncoated. The successful coating of bundles was explained by the formation of interstitial pores between the individual SWCNTs constituting the bundle, where the precursor molecules can adhere, initiating the layer growth. Thicker alumina layers (20-35 nm thick) were used for the coating of bottom-gated SWCNT-network based field effect transistors (FETs). ALD layers, grown at different conditions, were found to influence the performance of the SWCNT-network FETs: low temperature ALD layers caused the ambipolarity of the channel and pronounced n-type conduction, whereas high temperature ALD processes resulted in hysteresis suppression in the transfer characteristics of the SWCNT transistors and preserved p-type conduction. Fixed charges in the ALD layer have been considered as the main factor influencing the conduction change of the SWCNT network based transistors.

  10. Quantitative Conductive Atomic Force Microscopy on Single-Walled Carbon Nanotube-Based Polymer Composites.

    PubMed

    Bârsan, Oana A; Hoffmann, Günter G; van der Ven, Leendert G J; de With, Gijsbertus

    2016-08-03

    Conductive atomic force microscopy (C-AFM) is a valuable technique for correlating the electrical properties of a material with its topographic features and for identifying and characterizing conductive pathways in polymer composites. However, aspects such as compatibility between tip material and sample, contact force and area between the tip and the sample, tip degradation and environmental conditions render quantifying the results quite challenging. This study aims at finding the suitable conditions for C-AFM to generate reliable, reproducible, and quantitative current maps that can be used to calculate the resistance in each point of a single-walled carbon nanotube (SWCNT) network, nonimpregnated as well as impregnated with a polymer. The results obtained emphasize the technique's limitation at the macroscale as the resistance of these highly conductive samples cannot be distinguished from the tip-sample contact resistance. Quantitative C-AFM measurements on thin composite sections of 150-350 nm enable the separation of sample and tip-sample contact resistance, but also indicate that these sections are not representative for the overall SWCNT network. Nevertheless, the technique was successfully used to characterize the local electrical properties of the composite material, such as sample homogeneity and resistance range of individual SWCNT clusters, at the nano- and microscale.

  11. Atomically precise understanding of nanofluids: nanodiamonds and carbon nanotubes in ionic liquids.

    PubMed

    Chaban, Vitaly V; Fileti, Eudes Eterno

    2016-09-29

    A nanofluid (NF) is composed of a base liquid and suspended nanoparticles (NPs). High-performance NFs exhibit significantly better heat conductivities, as compared to their base liquids. In the present work, we applied all-atom molecular dynamics (MD) simulations to characterize diffusive and ballistic energy transfer mechanisms within nanodiamonds (NDs), carbon nanotubes (CNTs), and N-butylpyridinium tetrafluoroborate ionic liquid (IL). We showed that heat transfer within both NDs and CNTs is orders of magnitude faster than that in the surrounding IL, whereas diffusion of all particles in the considered NF is similar. Intramolecular heat transfer in NPs is a key factor determining the difference of NFs from base liquids. Solvation free energy of NDs and CNTs in ILs was estimated from MD simulations. The geometric dimensions of NPs were shown to be a major source of entropic penalty. Temperature adjusts the entropic factor substantially by modifying a genuine local structure of the bulk base liquid. Our work contributes to engineering more stable and productive suspensions of NPs in ILs, which are necessary for essential progress in the field of NFs.

  12. Increased loss of soil-derived carbon in response to litter addition and temperature

    NASA Astrophysics Data System (ADS)

    Creamer, C.; Krull, E. S.; Sanderman, J.; Farrell, M.

    2013-12-01

    In order to predict the response of soil organic matter (SOM) to increasing temperatures, a mechanistic understanding of the interactions between OM quality, OM availability, and microbial community structure and function is needed. We used short-term incubations of 13C enriched (20 atom%) fresh and pre-incubated eucalyptus leaf litter in an Australian woodland soil to determine changes in allocation of C to various OM pools, as dictated by microbial activity, in response to temperature and substrate quality. The quantity and isotopic composition of microbial phospholipid fatty acids (PLFA) and dissolved organic C (DOC) were measured along with the quantity of dissolved inorganic and organic nitrogen at four destructive time points. The quantity and isotopic composition of respired CO2 was measured throughout the incubation. Although the temperature sensitivities of the two litters were similar (despite different chemical compositions), soil-C was significantly more temperature sensitive than litter-C. We also observed negative priming of soil-C in the fresh litter treatment and positive priming of soil-C in the pre-incubated litter treatment relative to the control (no litter addition). The extent of positive priming in the pre-incubated litter treatment also increased significantly with temperature. The quantity of soil-derived DOC was consistent between both litter treatments and the control, confirming that differences in soil-C availability were not controlling the observed differences in soil-C mineralization. In contrast, dissolved N was significantly higher in the pre-incubated litter treatment and increased with temperature, suggesting enhanced SOM decomposition in the pre-incubated litter treatment resulted in greater N cycling, production, or destabilization from SOM. The pre-incubated litter treatment also had greater proportions of PLFA that predominately cycled soil-derived OM (gram-positive bacteria), and increased in response to elevated temperature

  13. Effect of Additives and pH on the Formation of Carbonate Mineral by CO2 Sequestration of Cement Paste

    NASA Astrophysics Data System (ADS)

    Lee, J. H.; Hwang, J.; Lee, H.; Son, B. S.; Oh, J.

    2015-12-01

    CO2 in the atmosphere causes a global warming that is a big issue nowadays. Many studies of CO2 capture and storage (CCS) technologies have been studied all over the world. Waste cement is a good source for aqueous carbonation because it is rich in calcium. Therefore, this study was performed to develop the aqueous carbonation method for waste cement powder. Cement paste was made with water/cement ratio of 6:4 and cured for 28 days in water bath. The cement paste was pulverized into a fine powder sizing less than 0.15 mm. To study effect of additives and pH on the formation of carbonate minerals, aqueous carbonation experiments were conducted. The mineral compositions and morphology of carbonate mineral were identified by XRD and SEM/EDS analysis. 1.0 M NaCl and 0.25 M MgCl2 were applied as additives. Aqueous carbonation experiment was conducted with injecting pure CO2 gas (99.9%) to a reactor containing 200 ㎖ of reacting solution. The pH of reacting solution was controled to determine formational condition of carbonate minerals. In 0.25 M MgCl2 solution, calcite was dominant mineral at high pH. More aragonite, however, formed as decreasing pH of solution with injection of CO2. The presence of Mg2+ in solution makes aragonite more dominant than calcite. Aragonite was mainly formed at the high pH of solution with 1.0 M NaCl additive, whereas calcite was more preponderant mineral than aragonite as falling pH. It show that unstable aragonite transformed to calcite as decreasing pH. In no additive solution, vaterite was dominantly formed at the initial stage of experiement, but unstable vaterite transformed to well crystallized calcite with further carbonation.

  14. Topsoil organic carbon content of Europe, a new map based on a generalised additive model

    NASA Astrophysics Data System (ADS)

    de Brogniez, Delphine; Ballabio, Cristiano; Stevens, Antoine; Jones, Robert J. A.; Montanarella, Luca; van Wesemael, Bas

    2014-05-01

    There is an increasing demand for up-to-date spatially continuous organic carbon (OC) data for global environment and climatic modeling. Whilst the current map of topsoil organic carbon content for Europe (Jones et al., 2005) was produced by applying expert-knowledge based pedo-transfer rules on large soil mapping units, the aim of this study was to replace it by applying digital soil mapping techniques on the first European harmonised geo-referenced topsoil (0-20 cm) database, which arises from the LUCAS (land use/cover area frame statistical survey) survey. A generalized additive model (GAM) was calibrated on 85% of the dataset (ca. 17 000 soil samples) and a backward stepwise approach selected slope, land cover, temperature, net primary productivity, latitude and longitude as environmental covariates (500 m resolution). The validation of the model (applied on 15% of the dataset), gave an R2 of 0.27. We observed that most organic soils were under-predicted by the model and that soils of Scandinavia were also poorly predicted. The model showed an RMSE of 42 g kg-1 for mineral soils and of 287 g kg-1 for organic soils. The map of predicted OC content showed the lowest values in Mediterranean countries and in croplands across Europe, whereas highest OC content were predicted in wetlands, woodlands and in mountainous areas. The map of standard error of the OC model predictions showed high values in northern latitudes, wetlands, moors and heathlands, whereas low uncertainty was mostly found in croplands. A comparison of our results with the map of Jones et al. (2005) showed a general agreement on the prediction of mineral soils' OC content, most probably because the models use some common covariates, namely land cover and temperature. Our model however failed to predict values of OC content greater than 200 g kg-1, which we explain by the imposed unimodal distribution of our model, whose mean is tilted towards the majority of soils, which are mineral. Finally, average

  15. A journey from order to disorder - atom by atom transformation from graphene to a 2D carbon glass.

    PubMed

    Eder, Franz R; Kotakoski, Jani; Kaiser, Ute; Meyer, Jannik C

    2014-02-11

    One of the most interesting questions in solid state theory is the structure of glass, which has eluded researchers since the early 1900's. Since then, two competing models, the random network theory and the crystallite theory, have both gathered experimental support. Here, we present a direct, atomic-level structural analysis during a crystal-to-glass transformation, including all intermediate stages. We introduce disorder on a 2D crystal, graphene, gradually, utilizing the electron beam of a transmission electron microscope, which allows us to capture the atomic structure at each step. The change from a crystal to a glass happens suddenly, and at a surprisingly early stage. Right after the transition, the disorder manifests as a vitreous network separating individual crystallites, similar to the modern version of the crystallite theory. However, upon increasing disorder, the vitreous areas grow on the expense of the crystallites and the structure turns into a random network. Thereby, our results show that, at least in the case of a 2D structure, both of the models can be correct, and can even describe the same material at different degrees of disorder.

  16. Validating a nondestructive optical method for apportioning colored particulate matter into black carbon and additional components

    PubMed Central

    Yan, Beizhan; Kennedy, Daniel; Miller, Rachel L.; Cowin, James P.; Jung, Kyung-hwa; Perzanowski, Matt; Balletta, Marco; Perera, Federica P.; Kinney, Patrick L.; Chillrud, Steven N.

    2011-01-01

    Exposure of black carbon (BC) is associated with a variety of adverse health outcomes. A number of optical methods for estimating BC on Teflon filters have been adopted but most assume all light absorption is due to BC while other sources of colored particulate matter exist. Recently, a four-wavelength-optical reflectance measurement for distinguishing second hand cigarette smoke (SHS) from soot-BC was developed (Brook et al., 2010; Lawless et al., 2004). However, the method has not been validated for soot-BC nor SHS and little work has been done to look at the methodological issues of the optical reflectance measurements for samples that could have SHS, BC, and other colored particles. We refined this method using a lab-modified integrating sphere with absorption measured continuously from 350 nm to 1000 nm. Furthermore, we characterized the absorption spectrum of additional components of particulate matter (PM) on PM2.5 filters including ammonium sulfate, hematite, goethite, and magnetite. Finally, we validate this method for BC by comparison to other standard methods. Use of synthesized data indicates that it is important to optimize the choice of wavelengths to minimize computational errors as additional components (more than 2) are added to the apportionment model of colored components. We found that substantial errors are introduced when using 4 wavelengths suggested by Lawless et al. to quantify four substances, while an optimized choice of wavelengths can reduce model-derived error from over 10% to less than 2%. For environmental samples, the method was sensitive for estimating airborne levels of BC and SHS, but not mass loadings of iron oxides and sulfate. Duplicate samples collected in NYC show high reproducibility (points consistent with a 1:1 line, R2 = 0.95). BC data measured by this method were consistent with those measured by other optical methods, including Aethalometer and Smoke-stain Reflectometer (SSR); although the SSR looses sensitivity at

  17. Validating a nondestructive optical method for apportioning colored particulate matter into black carbon and additional components.

    PubMed

    Yan, Beizhan; Kennedy, Daniel; Miller, Rachel L; Cowin, James P; Jung, Kyung-Hwa; Perzanowski, Matt; Balletta, Marco; Perera, Federica P; Kinney, Patrick L; Chillrud, Steven N

    2011-12-01

    Exposure of black carbon (BC) is associated with a variety of adverse health outcomes. A number of optical methods for estimating BC on Teflon filters have been adopted but most assume all light absorption is due to BC while other sources of colored particulate matter exist. Recently, a four-wavelength-optical reflectance measurement for distinguishing second hand cigarette smoke (SHS) from soot-BC was developed (Brook et al., 2010; Lawless et al., 2004). However, the method has not been validated for soot-BC nor SHS and little work has been done to look at the methodological issues of the optical reflectance measurements for samples that could have SHS, BC, and other colored particles. We refined this method using a lab-modified integrating sphere with absorption measured continuously from 350 nm to 1000 nm. Furthermore, we characterized the absorption spectrum of additional components of particulate matter (PM) on PM(2.5) filters including ammonium sulfate, hematite, goethite, and magnetite. Finally, we validate this method for BC by comparison to other standard methods. Use of synthesized data indicates that it is important to optimize the choice of wavelengths to minimize computational errors as additional components (more than 2) are added to the apportionment model of colored components. We found that substantial errors are introduced when using 4 wavelengths suggested by Lawless et al. to quantify four substances, while an optimized choice of wavelengths can reduce model-derived error from over 10% to less than 2%. For environmental samples, the method was sensitive for estimating airborne levels of BC and SHS, but not mass loadings of iron oxides and sulfate. Duplicate samples collected in NYC show high reproducibility (points consistent with a 1:1 line, R(2) = 0.95). BC data measured by this method were consistent with those measured by other optical methods, including Aethalometer and Smoke-stain Reflectometer (SSR); although the SSR looses sensitivity at

  18. Validating a nondestructive optical method for apportioning colored particulate matter into black carbon and additional components

    NASA Astrophysics Data System (ADS)

    Yan, Beizhan; Kennedy, Daniel; Miller, Rachel L.; Cowin, James P.; Jung, Kyung-hwa; Perzanowski, Matt; Balletta, Marco; Perera, Federica P.; Kinney, Patrick L.; Chillrud, Steven N.

    2011-12-01

    Exposure of black carbon (BC) is associated with a variety of adverse health outcomes. A number of optical methods for estimating BC on Teflon filters have been adopted but most assume all light absorption is due to BC while other sources of colored particulate matter exist. Recently, a four-wavelength-optical reflectance measurement for distinguishing second hand cigarette smoke (SHS) from soot-BC was developed (Brook et al., 2010; Lawless et al., 2004). However, the method has not been validated for soot-BC nor SHS and little work has been done to look at the methodological issues of the optical reflectance measurements for samples that could have SHS, BC, and other colored particles. We refined this method using a lab-modified integrating sphere with absorption measured continuously from 350 nm to 1000 nm. Furthermore, we characterized the absorption spectrum of additional components of particulate matter (PM) on PM 2.5 filters including ammonium sulfate, hematite, goethite, and magnetite. Finally, we validate this method for BC by comparison to other standard methods. Use of synthesized data indicates that it is important to optimize the choice of wavelengths to minimize computational errors as additional components (more than 2) are added to the apportionment model of colored components. We found that substantial errors are introduced when using 4 wavelengths suggested by Lawless et al. to quantify four substances, while an optimized choice of wavelengths can reduce model-derived error from over 10% to less than 2%. For environmental samples, the method was sensitive for estimating airborne levels of BC and SHS, but not mass loadings of iron oxides and sulfate. Duplicate samples collected in NYC show high reproducibility (points consistent with a 1:1 line, R2 = 0.95). BC data measured by this method were consistent with those measured by other optical methods, including Aethalometer and Smoke-stain Reflectometer (SSR); although the SSR looses sensitivity at

  19. Effects of mineral additives on biochar formation: carbon retention, stability, and properties.

    PubMed

    Li, Feiyue; Cao, Xinde; Zhao, Ling; Wang, Jianfei; Ding, Zhenliang

    2014-10-07

    Biochar is being recognized as a promising tool for long-term carbon sequestration, and biochar with high carbon retention and strong stability is supposed to be explored for that purpose. In this study, three minerals, including kaolin, calcite (CaCO3), and calcium dihydrogen phosphate [Ca(H2PO4)2], were added to rice straw feedstock at the ratio of 20% (w/w) for biochar formation through pyrolysis treatment, aiming to improve carbon retention and stabilization in biochar. Kaolin and CaCO3 had little effect on the carbon retention, whereas Ca(H2PO4)2 increased the carbon retention by up to 29% compared to untreated biochar. Although the carbon loss from the kaolin-modified biochar with hydrogen peroxide oxidation was enhanced, CaCO3 and Ca(H2PO4)2 modification reduced the carbon loss by 18.6 and 58.5%, respectively. Moreover, all three minerals reduced carbon loss of biochar with potassium dichromate oxidation from 0.3 to 38.8%. The microbial mineralization as CO2 emission in all three modified biochars was reduced by 22.2-88.7% under aerobic incubation and 5-61% under anaerobic incubation. Enhanced carbon retention and stability of biochar with mineral treatment might be caused by the enhanced formation of aromatic C, which was evidenced by cross-polarization magic angle spinning (13)C nuclear magnetic resonance spectra and Fourier transform infrared spectroscopy analysis. Our results indicated that the three minerals, especially Ca(H2PO4)2, were effective in increasing carbon retention and strengthening biochar stabilization, which provided a novel idea that people could explore and produce the designated biochar with high carbon sequestration capacity and stability.

  20. Atomic Scale Interface Manipulation, Structural Engineering, and Their Impact on Ultrathin Carbon Films in Controlling Wear, Friction, and Corrosion.

    PubMed

    Dwivedi, Neeraj; Yeo, Reuben J; Yak, Leonard J K; Satyanarayana, Nalam; Dhand, Chetna; Bhat, Thirumaleshwara N; Zhang, Zheng; Tripathy, Sudhiranjan; Bhatia, Charanjit S

    2016-07-13

    Reducing friction, wear, and corrosion of diverse materials/devices using <2 nm thick protective carbon films remains challenging, which limits the developments of many technologies, such as magnetic data storage systems. Here, we present a novel approach based on atomic scale interface manipulation to engineer and control the friction, wear, corrosion, and structural characteristics of 0.7-1.7 nm carbon-based films on CoCrPt:oxide-based magnetic media. We demonstrate that when an atomically thin (∼0.5 nm) chromium nitride (CrNx) layer is sandwiched between the magnetic media and an ultrathin carbon overlayer (1.2 nm), it modifies the film-substrate interface, creates various types of interfacial bonding, increases the interfacial adhesion, and tunes the structure of carbon in terms of its sp(3) bonding. These contribute to its remarkable functional properties, such as stable and lowest coefficient of friction (∼0.15-0.2), highest wear resistance and better corrosion resistance despite being only ∼1.7 nm thick, surpassing those of ∼2.7 nm thick current commercial carbon overcoat (COC) and other overcoats in this work. While this approach has direct implications for advancing current magnetic storage technology with its ultralow thickness, it can also be applied to advance the protective and barrier capabilities of other ultrathin materials for associated technologies.

  1. Quantum dynamics of hydrogen interacting with single-walled carbon nanotubes: multiple H-atom adsorbates.

    PubMed

    McAfee, Jason L; Poirier, Bill

    2011-02-21

    In a previous paper [J. L. McAfee and B. Poirier, J. Chem. Phys. 130, 064701 (2009)], using spin-polarized density functional theory (DFT), the authors reported a binding energy of 0.755 eV, for a single hydrogen atom adsorbed on a pristine (unrelaxed) (5,5) single-walled carbon nanotube (SWNT) substrate. A full three-dimensional (3D) potential energy surface (PES) for the SWNT-H system was also developed, and used in a quantum dynamics calculation to compute all rovibrational bound states, and associated equatorial and longitudinal adsorbate migration rates. A highly pronounced preference for the latter migration pathway at ambient temperatures was observed. In this work, we extend the aforementioned study to include multiple H-atom adsorbates. Extensive DFT calculations are performed, in order to ascertain the most relevant dynamical pathways. For two adsorbates, the SWNT-H-H system is found to exhibit highly site-specific binding, as well as long-range correlation and pronounced binding energy enhancement. The latter effect is even more pronounced in the full-hydrogenation limit, increasing the per-adsorbate binding energy to 2.6 eV. To study migration dynamics, a single-hole model is developed, for which the binding energy drops to 2.11 eV. A global 3D PES is developed for the hole migration model, using 40 radial × 18 cylindrical ab initio geometries, fit to a Fourier basis with radially dependent expansion coefficients (rms error 4.9 meV). As compared with the single-adsorbate case, the hole migration PES does not exhibit separate chemisorption and physisorption wells. The barrier to longitudinal migration is also found to be much lower. Quantum dynamics calculations for all rovibrational states are then performed (using a mixed spectral basis/phase-space optimized discrete variable representation), and used to compute longitudinal migration rates. Ramifications for the use of SWNTs as potential hydrogen storage materials are discussed.

  2. Permeation of low-Z atoms through carbon sheets: Density functional theory study on energy barriers and deformation effects

    SciTech Connect

    Huber, Stefan E. E-mail: Michael.probst@uibk.ac.at; Mauracher, Andreas; Probst, Michael E-mail: Michael.probst@uibk.ac.at

    2013-12-15

    Energetic and geometric aspects of the permeation of the atoms hydrogen to neon neutral atoms through graphene sheets are investigated by investigating the associated energy barriers and sheet deformations. Density functional theory calculations on cluster models, where graphene is modeled by planar polycyclic aromatic hydrocarbons (PAHs), provide the energies and geometries. Particularities of our systems, such as convergence of both energy barriers and deformation curves with increasing size of the PAHs, are discussed. Three different interaction regimes, adiabatic, planar and vertical, are investigated by enforcing different geometrical constraints. The adiabatic energy barriers range from 5 eV for hydrogen to 20 eV for neon. We find that the permeation of oxygen and carbon into graphene is facilitated by temporary chemical bonding while for other, in principle reactive atoms, it is not. We discuss implications of our results for modeling chemical sputtering of graphite.

  3. Protection of Diamond-like Carbon Films from Energetic Atomic Oxygen Degradation Through Si-doping Technology

    SciTech Connect

    Yokota, Kumiko; Tagawa, Masahito; Kitamura, Akira; Matsumoto, Koji; Yoshigoe, Akitaka; Teraoka, Yuden; Fontaine, Julien; Belin, Michel

    2009-01-05

    The effect of hyperthermal atomic oxygen (AO) exposure on the surface properties of Si-doped diamond-like carbon (DLC) was investigated. Two types of DLC were tested that contain approximately 10 at% and 20 at% of Si atoms. Surface analytical results of high-resolution x-ray photoelectron spectroscopy using synchrotron radiation (synchrotron radiation photoemission spectroscopy; SR-PES) as well as Rutherford backscattering spectroscopy (RBS) have been used for characterization of the AO-exposed Si-doped DLC. It was identified by SR-PES that a SiO{sub 2} layer was formed by the hyperthermal AO exposure at the Si-doped DLC surface. RBS data indicates that AO exposure leads to severe thickness loss on the undopedd DLC. In contrast, a SiO{sub 2} layer formed by the hyperthermal atomic oxygen reaction of Si-doped DLC protects the DLC underneath the SiO{sub 2} layer.

  4. Atom probe tomography investigation of assisted precipitation of secondary hardening carbides in a medium carbon martensitic steels.

    PubMed

    Danoix, F; Danoix, R; Akre, J; Grellier, A; Delagnes, D

    2011-12-01

    A medium carbon martensitic steel containing nanometer scale secondary hardening carbides and intermetallic particles is investigated by field ion microscopy and atom probe tomography. The interaction between the concomitant precipitations of both types of particles is investigated. It is shown that the presence of the intermetallic phase affects the nucleation mechanism and the spatial distribution of the secondary hardening carbides, which shifts from heterogeneous on dislocations to heterogeneous on the intermetallic particles.

  5. Regulation of Soil Microbial Carbon-use Efficiency by Soil Moisture, Substrate Addition, and Incubation Time

    NASA Astrophysics Data System (ADS)

    Stark, J.

    2015-12-01

    Microbial carbon-use efficiency (CUE) is a key variable in biogeochemical cycling that regulates soil C sequestration, greenhouse gas emissions, and retention of inorganic nutrients. Microbial CUE is the fraction of C converted to biomass rather than respired as CO2. Biogeochemical models have been shown to be highly sensitive to variation in CUE; however, we currently have a poor understanding of how CUE responds to environmental variables such as soil moisture and nutrient limitations. We examined the effect of soil moisture and C supply on CUE in soil from a western hemlock / sitka spruce forest in Oregon, USA, using a novel technique which supplies 13C and 15N substrates through the gas phase so that water addition is not necessary. Soil samples (28 g oven-dry equiv. wt) at two water potentials (-0.03 and -3.55 MPa) were exposed to 13C-acetic acid vapor for either 6 or 30 sec to provide two different concentrations of acetate to soil microbial communities. The soils were also injected with small amounts of 15NH3 gas to allow quantification of microbial N assimilation rates and to provide an alternate method of calculating CUE. Rates of 13CO2 respiration were measured continuously during a 48-h incubation using cavity ring-down spectroscopy. Soil samples were extracted at seven time intervals (0, 0.5, 1.5, 4.5, 12, 24, and 48 h) in 0.5 M K2SO4 and analyzed for DO13C, microbial 13C, DO15N, inorganic 15N, and microbial 15N to calculate how gross rates of C and N assimilation and microbial CUE change with incubation time. As expected, microbial C and N assimilation rates and CUE increased with soil moisture and the quantity of acetate added; however, C:N assimilated was higher at lower soil moisture, suggesting that either C-storage compounds were being created, or that fungal communities were responsible for a greater proportion of the assimilation in drier soils. Assimilation rates and CUE also changed with incubation time, demonstrating that estimates of CUE

  6. Atomic-scale wear of amorphous hydrogenated carbon during intermittent contact: a combined study using experiment, simulation, and theory.

    PubMed

    Vahdat, Vahid; Ryan, Kathleen E; Keating, Pamela L; Jiang, Yijie; Adiga, Shashishekar P; Schall, J David; Turner, Kevin T; Harrison, Judith A; Carpick, Robert W

    2014-07-22

    In this study, we explore the wear behavior of amplitude modulation atomic force microscopy (AM-AFM, an intermittent-contact AFM mode) tips coated with a common type of diamond-like carbon, amorphous hydrogenated carbon (a-C:H), when scanned against an ultra-nanocrystalline diamond (UNCD) sample both experimentally and through molecular dynamics (MD) simulations. Finite element analysis is utilized in a unique way to create a representative geometry of the tip to be simulated in MD. To conduct consistent and quantitative experiments, we apply a protocol that involves determining the tip-sample interaction geometry, calculating the tip-sample force and normal contact stress over the course of the wear test, and precisely quantifying the wear volume using high-resolution transmission electron microscopy imaging. The results reveal gradual wear of a-C:H with no sign of fracture or plastic deformation. The wear rate of a-C:H is consistent with a reaction-rate-based wear theory, which predicts an exponential dependence of the rate of atom removal on the average normal contact stress. From this, kinetic parameters governing the wear process are estimated. MD simulations of an a-C:H tip, whose radius is comparable to the tip radii used in experiments, making contact with a UNCD sample multiple times exhibit an atomic-level removal process. The atomistic wear events observed in the simulations are correlated with under-coordinated atomic species at the contacting surfaces.

  7. Structural modifications of graphyne layers consisting of carbon atoms in the sp- and sp{sup 2}-hybridized states

    SciTech Connect

    Belenkov, E. A.; Mavrinskii, V. V.; Belenkova, T. E.; Chernov, V. M.

    2015-05-15

    A model scheme is proposed for obtaining layered compounds consisting of carbon atoms in the sp- and (vnsp){sup 2}-hybridized states. This model is used to find the possibility of existing the following seven basic structural modifications of graphyne: α-, β1-, β2-, β3-, γ1-, γ2-, and γ3-graphyne. Polymorphic modifications β3 graphyne and γ3 graphyne are described. The basic structural modifications of graphyne contain diatomic polyyne chains and consist only of carbon atoms in two different crystallographically equivalent states. Other nonbasic structural modifications of graphyne can be formed via the elongation of the carbyne chains that connect three-coordinated carbon atoms and via the formation of graphyne layers with a mixed structure consisting of basic layer fragments, such as α-β-graphyne, α-γ-graphyne, and β-γ-graphyne. The semiempirical quantum-mechanical MNDO, AM1, and PM3 methods and ab initio STO6-31G basis calculations are used to find geometrically optimized structures of the basic graphyne layers, their structural parameters, and energies of their sublimation. The energy of sublimation is found to be maximal for γ2-graphyne, which should be the most stable structural modification of graphyne.

  8. Torsional behaviors of polymer-infiltrated carbon nanotube yarn muscles studied with atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Kwon, Cheong Hoon; Chun, Kyoung-Yong; Kim, Shi Hyeong; Lee, Jae-Hyeok; Kim, Jae-Ho; Lima, Márcio D.; Baughman, Ray H.; Kim, Seon Jeong

    2015-01-01

    Torsional behaviors of polymer-infiltrated carbon nanotube (CNT) yarn muscles have been investigated in relation to molecular architecture by using atomic force microscopy (AFM). Two polymers with different stiffnesses, polystyrene (PS) and poly(styrene-b-isoprene-b-styrene) (SIS), were uniformly infiltrated into CNT yarns for electrothermal torsional actuation. The torsional behaviors of hybrid yarn muscles are completely explained by the volume change of each polymer, based on the height and full width at half maximum profiles from the AFM morphological images. The volume expansion of the PS yarn muscle (1.7 nm of vertical change and 22 nm of horizontal change) is much larger than that of the SIS yarn muscle (0.3 nm and 11 nm change in vertical and horizontal directions) at 80 °C, normalized by their values at 25 °C. We demonstrate that their maximum rotations are consequently 29.7 deg mm-1 for the PS-infiltrated CNT yarn muscle (relatively larger rotation) and 14.4 deg mm-1 for the SIS-infiltrated CNT yarn muscle (smaller rotation) at 0.75 V m-1. These hybrid yarn muscles could be applied in resonant controllers or damping magnetoelectric sensors.Torsional behaviors of polymer-infiltrated carbon nanotube (CNT) yarn muscles have been investigated in relation to molecular architecture by using atomic force microscopy (AFM). Two polymers with different stiffnesses, polystyrene (PS) and poly(styrene-b-isoprene-b-styrene) (SIS), were uniformly infiltrated into CNT yarns for electrothermal torsional actuation. The torsional behaviors of hybrid yarn muscles are completely explained by the volume change of each polymer, based on the height and full width at half maximum profiles from the AFM morphological images. The volume expansion of the PS yarn muscle (1.7 nm of vertical change and 22 nm of horizontal change) is much larger than that of the SIS yarn muscle (0.3 nm and 11 nm change in vertical and horizontal directions) at 80 °C, normalized by their values at 25

  9. The warm ISM in the Sgr A region: mid-J CO, atomic carbon, ionized atomic carbon, and ionized nitrogen line observations with the Herschel/HIFI and NANTEN2/SMART Telescopes

    NASA Astrophysics Data System (ADS)

    García, Pablo; Simon, Robert; Stutzki, Jürgen; Requena-Torres, Miguel; Güsten, Rolf; Fukui, Yasuo; Yamamoto, Hiroaki; Bertoldi, Frank; Burton, Michael; Bronfman, Leonardo; Ogawa, Hideo

    2014-05-01

    We present Herschel/HIFI sub-mm atomic carbon ([Ci] 3 P 1 - 3 P 0 and [Ci] 3 P 2 - 3 P 1), ionized carbon ([Cii] 2 P 3/2 - 2 P 1/2), and ionized nitrogen ([Nii] 3 P 1 - 3 P 0) line observations obtained in the frame of the Herschel Guaranteed Time HEXGAL (Herschel EXtraGALactic) key program (P. I. Rolf Güsten, MPIfR), and NANTEN2/SMART carbon monoxide (CO(J = 4 - 3)) observations of the warm gas around the Sgr A region. The spectrally resolved emission from all lines, and the corresponding line intensity ratios, show a very complex morphology. The determination of spatial and spectral (anti)correlation with known sources in the Sgr A region such as the Arched Filaments, NTF filaments, the Sickle, Quintuplet cluster, CND clouds, is ongoing work.

  10. Evaluation of carbon nanotube probes in critical dimension atomic force microscopes.

    PubMed

    Choi, Jinho; Park, Byong Chon; Ahn, Sang Jung; Kim, Dal-Hyun; Lyou, Joon; Dixson, Ronald G; Orji, Ndubuisi G; Fu, Joseph; Vorburger, Theodore V

    2016-07-01

    The decreasing size of semiconductor features and the increasing structural complexity of advanced devices have placed continuously greater demands on manufacturing metrology, arising both from the measurement challenges of smaller feature sizes and the growing requirement to characterize structures in more than just a single critical dimension. For scanning electron microscopy, this has resulted in increasing sophistication of imaging models. For critical dimension atomic force microscopes (CD-AFMs), this has resulted in the need for smaller and more complex tips. Carbon nanotube (CNT) tips have thus been the focus of much interest and effort by a number of researchers. However, there have been significant issues surrounding both the manufacture and use of CNT tips. Specifically, the growth or attachment of CNTs to AFM cantilevers has been a challenge to the fabrication of CNT tips, and the flexibility and resultant bending artifacts have presented challenges to using CNT tips. The Korea Research Institute for Standards and Science (KRISS) has invested considerable effort in the controlled fabrication of CNT tips and is collaborating with the National Institute of Standards and Technology on the application of CNT tips for CD-AFM. Progress by KRISS on the precise control of CNT orientation, length, and end modification, using manipulation and focused ion beam processes, has allowed us to implement ball-capped CNT tips and bent CNT tips for CD-AFM. Using two different generations of CD-AFM instruments, we have evaluated these tip types by imaging a line/space grating and a programmed line edge roughness specimen. We concluded that these CNTs are capable of scanning the profiles of these structures, including re-entrant sidewalls, but there remain important challenges to address. These challenges include tighter control of tip geometry and careful optimization of scan parameters and algorithms for using CNT tips.

  11. Evaluation of carbon nanotube probes in critical dimension atomic force microscopes

    NASA Astrophysics Data System (ADS)

    Choi, Jinho; Park, Byong Chon; Ahn, Sang Jung; Kim, Dal-Hyun; Lyou, Joon; Dixson, Ronald G.; Orji, Ndubuisi G.; Fu, Joseph; Vorburger, Theodore V.

    2016-07-01

    The decreasing size of semiconductor features and the increasing structural complexity of advanced devices have placed continuously greater demands on manufacturing metrology, arising both from the measurement challenges of smaller feature sizes and the growing requirement to characterize structures in more than just a single critical dimension. For scanning electron microscopy, this has resulted in increasing sophistication of imaging models. For critical dimension atomic force microscopes (CD-AFMs), this has resulted in the need for smaller and more complex tips. Carbon nanotube (CNT) tips have thus been the focus of much interest and effort by a number of researchers. However, there have been significant issues surrounding both the manufacture and use of CNT tips. Specifically, the growth or attachment of CNTs to AFM cantilevers has been a challenge to the fabrication of CNT tips, and the flexibility and resultant bending artifacts have presented challenges to using CNT tips. The Korea Research Institute for Standards and Science (KRISS) has invested considerable effort in the controlled fabrication of CNT tips and is collaborating with the National Institute of Standards and Technology on the application of CNT tips for CD-AFM. Progress by KRISS on the precise control of CNT orientation, length, and end modification, using manipulation and focused ion beam processes, has allowed us to implement ball-capped CNT tips and bent CNT tips for CD-AFM. Using two different generations of CD-AFM instruments, we have evaluated these tip types by imaging a line/space grating and a programmed line edge roughness specimen. We concluded that these CNTs are capable of scanning the profiles of these structures, including re-entrant sidewalls, but there remain important challenges to address. These challenges include tighter control of tip geometry and careful optimization of scan parameters and algorithms for using CNT tips.

  12. Evaluation of carbon nanotube probes in critical dimension atomic force microscopes

    PubMed Central

    Choi, Jinho; Park, Byong Chon; Ahn, Sang Jung; Kim, Dal-Hyun; Lyou, Joon; Dixson, Ronald G.; Orji, Ndubuisi G.; Fu, Joseph; Vorburger, Theodore V.

    2016-01-01

    The decreasing size of semiconductor features and the increasing structural complexity of advanced devices have placed continuously greater demands on manufacturing metrology, arising both from the measurement challenges of smaller feature sizes and the growing requirement to characterize structures in more than just a single critical dimension. For scanning electron microscopy, this has resulted in increasing sophistication of imaging models. For critical dimension atomic force microscopes (CD-AFMs), this has resulted in the need for smaller and more complex tips. Carbon nanotube (CNT) tips have thus been the focus of much interest and effort by a number of researchers. However, there have been significant issues surrounding both the manufacture and use of CNT tips. Specifically, the growth or attachment of CNTs to AFM cantilevers has been a challenge to the fabrication of CNT tips, and the flexibility and resultant bending artifacts have presented challenges to using CNT tips. The Korea Research Institute for Standards and Science (KRISS) has invested considerable effort in the controlled fabrication of CNT tips and is collaborating with the National Institute of Standards and Technology on the application of CNT tips for CD-AFM. Progress by KRISS on the precise control of CNT orientation, length, and end modification, using manipulation and focused ion beam processes, has allowed us to implement ball-capped CNT tips and bent CNT tips for CD-AFM. Using two different generations of CD-AFM instruments, we have evaluated these tip types by imaging a line/space grating and a programmed line edge roughness specimen. We concluded that these CNTs are capable of scanning the profiles of these structures, including re-entrant sidewalls, but there remain important challenges to address. These challenges include tighter control of tip geometry and careful optimization of scan parameters and algorithms for using CNT tips. PMID:27840664

  13. Carbon addition during the Paleocene-Eocene Thermal Maximum: Model inversion of a new, high-resolution carbon isotope record from Svalbard

    NASA Astrophysics Data System (ADS)

    Cui, Y.; Kump, L.; Ridgwell, A.; Junium, C.; Diefendorf, A. F.; Freeman, K. H.; Urban, N.

    2010-12-01

    Newly analyzed core material from Svalbard presents the most expanded sedimentary section spanning the Paleocene Eocene Thermal Maximum (PETM) studied to date. Carbon isotopic analysis of the bulk organic matter extracted from core BH9-05 details the onset of the negative carbon isotope excursion (CIE) of approximately 4.2‰ over 19,000 years (8 m of section, sampled every 30 cm) and its recovery over 50 m of section, representing 150,000 years. The CIE of terrestrial higher plant n-alkanes (~6‰) is larger than that of the bulk organic carbon (4.2‰), suggesting the CIE of the atmospheric CO2 is in the range of 4.2 to 6‰. We use a novel approach to modeling the excursion, forcing an Earth system model of intermediate complexity to conform to the total organic carbon isotope record, yielding rates of carbon release at the PETM for a specified isotopic composition representing end-member potential sources (methane or fossil organic matter). We find that the peak rate of carbon addition is only a small fraction of the current rate of fossil fuel burning (9 Pg C/yr) whether the source is methane (0.3 Pg C/yr; δ13C = -60‰) or organic matter (1.7 Pg C/yr; δ13C = -22‰). Model/data comparison, especially the observed and modeled seafloor carbonate dissolution record, favors the higher peak rate and larger (~13,000 Pg C) cumulative addition associated with an organic-matter source, such as rapid oxidation of peat/coal/marine organic matter, thermal alteration of marine organic matter during emplacement of the N. Atlantic Volcanic Province, or a mix of relatively 13C enriched (volcanic) and relatively 13C depleted (methane) sources. However, model sensitivity analysis shows that while the rate and amount of carbon added (for a specified source type) is relatively insensitive to key model uncertainties, the predicted seafloor carbonate dissolution response is quite sensitive to the presumed initial ocean alkalinity and seafloor carbonate distribution (i.e., the

  14. Enhanced Production of Green Tide Algal Biomass through Additional Carbon Supply

    PubMed Central

    de Paula Silva, Pedro H.; Paul, Nicholas A.; de Nys, Rocky; Mata, Leonardo

    2013-01-01

    Intensive algal cultivation usually requires a high flux of dissolved inorganic carbon (Ci) to support productivity, particularly for high density algal cultures. Carbon dioxide (CO2) enrichment can be used to overcome Ci limitation and enhance productivity of algae in intensive culture, however, it is unclear whether algal species with the ability to utilise bicarbonate (HCO3−) as a carbon source for photosynthesis will benefit from CO2 enrichment. This study quantified the HCO3− affinity of three green tide algal species, Cladophora coelothrix, Cladophora patentiramea and Chaetomorpha linum, targeted for biomass and bioenergy production. Subsequently, we quantified productivity and carbon, nitrogen and ash content in response to CO2 enrichment. All three species had similar high pH compensation points (9.7–9.9), and grew at similar rates up to pH 9, demonstrating HCO3− utilization. Algal cultures enriched with CO2 as a carbon source had 30% more total Ci available, supplying twenty five times more CO2 than the control. This higher Ci significantly enhanced the productivity of Cladophora coelothrix (26%), Chaetomorpha linum (24%) and to a lesser extent for Cladophora patentiramea (11%), compared to controls. We demonstrated that supplying carbon as CO2 can enhance the productivity of targeted green tide algal species under intensive culture, despite their clear ability to utilise HCO3−. PMID:24324672

  15. Enhanced production of green tide algal biomass through additional carbon supply.

    PubMed

    de Paula Silva, Pedro H; Paul, Nicholas A; de Nys, Rocky; Mata, Leonardo

    2013-01-01

    Intensive algal cultivation usually requires a high flux of dissolved inorganic carbon (Ci) to support productivity, particularly for high density algal cultures. Carbon dioxide (CO2) enrichment can be used to overcome Ci limitation and enhance productivity of algae in intensive culture, however, it is unclear whether algal species with the ability to utilise bicarbonate (HCO3 (-)) as a carbon source for photosynthesis will benefit from CO2 enrichment. This study quantified the HCO3 (-) affinity of three green tide algal species, Cladophora coelothrix, Cladophora patentiramea and Chaetomorpha linum, targeted for biomass and bioenergy production. Subsequently, we quantified productivity and carbon, nitrogen and ash content in response to CO2 enrichment. All three species had similar high pH compensation points (9.7-9.9), and grew at similar rates up to pH 9, demonstrating HCO3 (-) utilization. Algal cultures enriched with CO2 as a carbon source had 30% more total Ci available, supplying twenty five times more CO2 than the control. This higher Ci significantly enhanced the productivity of Cladophora coelothrix (26%), Chaetomorpha linum (24%) and to a lesser extent for Cladophora patentiramea (11%), compared to controls. We demonstrated that supplying carbon as CO2 can enhance the productivity of targeted green tide algal species under intensive culture, despite their clear ability to utilise HCO3 (-).

  16. Soil carbon sequestration in semi-arid soil through the addition of fuel gas desulfurization gypsum (FGDG)

    NASA Astrophysics Data System (ADS)

    Han, Young-Soo; Tokunaga, Tetsu; Oh, Chamteut

    2014-05-01

    This study investigated a new strategy for increasing carbon retention in slightly alkaline soils through addition of fuel gas desulfurization gypsum (FGDG, CaSO4•2H2O). FGDG is moderately soluble and thus the FGDG amendment may be effective to reduce microbial respiration, to accelerate calcite (CaCO3) precipitation, and to promote soil organic carbon (SOC) complexation on mineral surfaces, but rates of these processes need to be understood. The effects of FGDG addition were tested in laboratory soil columns with and without FGDG-amended layers, and in greenhouse soil columns planted with switchgrass, a biofuel crop. The results of laboratory column experiments demonstrated that additions of FGDG promote soil carbon sequestration through suppressing microbial respiration to the extent of ~200 g per m2 soil per m of supplied water, and promoting calcite precipitation at similar rates. The greenhouse experiments showed that the FGDG treatments did not adversely affect biomass yield (~600 g dry biomass/m2/harvest) at the higher irrigation rate (50 cm/year), but substantially reduced recoverable biomass under the more water-limited conditions (irrigation rate = 20 cm/year). The main achievements of this study are (1) the identification of conditions in which inorganic and organic carbon sequestration is practical in semi-arid and arid soils, (2) development of a method for measuring the total carbon balance in unsaturated soil columns, and (3) the quantification of different pathways for soil carbon sequestration in response to FGDG amendments. These findings provide information for evaluating land use practices for increased soil carbon sequestration under semi-arid region biofuel crop production.

  17. Probing the Role of an Atomically Thin SiNx Interlayer on the Structure of Ultrathin Carbon Films

    PubMed Central

    Dwivedi, Neeraj; Rismani-Yazdi, Ehsan; Yeo, Reuben J.; Goohpattader, Partho S.; Satyanarayana, Nalam; Srinivasan, Narasimhan; Druz, Boris; Tripathy, S.; Bhatia, C. S.

    2014-01-01

    Filtered cathodic vacuum arc (FCVA) processed carbon films are being considered as a promising protective media overcoat material for future hard disk drives (HDDs). However, at ultrathin film levels, FCVA-deposited carbon films show a dramatic change in their structure in terms of loss of sp3 bonding, density, wear resistance etc., compared to their bulk counterpart. We report for the first time how an atomically thin (0.4 nm) silicon nitride (SiNx) interlayer helps in maintaining/improving the sp3 carbon bonding, enhancing interfacial strength/bonding, improving oxidation/corrosion resistance, and strengthening the tribological properties of FCVA-deposited carbon films, even at ultrathin levels (1.2 nm). We propose the role of the SiNx interlayer in preventing the catalytic activity of Co and Pt in media, leading to enhanced sp3C bonding (relative enhancement ~40%). These findings are extremely important in view of the atomic level understanding of structural modification and the development of high density HDDs. PMID:24846506

  18. Probing the role of an atomically thin SiNx interlayer on the structure of ultrathin carbon films.

    PubMed

    Dwivedi, Neeraj; Rismani-Yazdi, Ehsan; Yeo, Reuben J; Goohpattader, Partho S; Satyanarayana, Nalam; Srinivasan, Narasimhan; Druz, Boris; Tripathy, S; Bhatia, C S

    2014-05-21

    Filtered cathodic vacuum arc (FCVA) processed carbon films are being considered as a promising protective media overcoat material for future hard disk drives (HDDs). However, at ultrathin film levels, FCVA-deposited carbon films show a dramatic change in their structure in terms of loss of sp3 bonding, density, wear resistance etc., compared to their bulk counterpart. We report for the first time how an atomically thin (0.4 nm) silicon nitride (SiNx) interlayer helps in maintaining/improving the sp3 carbon bonding, enhancing interfacial strength/bonding, improving oxidation/corrosion resistance, and strengthening the tribological properties of FCVA-deposited carbon films, even at ultrathin levels (1.2 nm). We propose the role of the SiNx interlayer in preventing the catalytic activity of Co and Pt in media, leading to enhanced sp3C bonding (relative enhancement~40%). These findings are extremely important in view of the atomic level understanding of structural modification and the development of high density HDDs.

  19. Voltage-pulsed and laser-pulsed atom probe tomography of a multiphase high-strength low-carbon steel.

    PubMed

    Mulholland, Michael D; Seidman, David N

    2011-12-01

    The differences in artifacts associated with voltage-pulsed and laser-pulsed (wavelength = 532 or 355 nm) atom-probe tomographic (APT) analyses of nanoscale precipitation in a high-strength low-carbon steel are assessed using a local-electrode atom-probe tomograph. It is found that the interfacial width of nanoscale Cu precipitates increases with increasing specimen apex temperatures induced by higher laser pulse energies (0.6-2 nJ pulse(-1) at a wavelength of 532 nm). This effect is probably due to surface diffusion of Cu atoms. Increasing the specimen apex temperature by using pulse energies up to 2 nJ pulse(-1) at a wavelength of 532 nm is also found to increase the severity of the local magnification effect for nanoscale M2C metal carbide precipitates, which is indicated by a decrease of the local atomic density inside the carbides from 68 ± 6 nm(-3) (voltage pulsing) to as small as 3.5 ± 0.8 nm(-3). Methods are proposed to solve these problems based on comparisons with the results obtained from voltage-pulsed APT experiments. Essentially, application of the Cu precipitate compositions and local atomic density of M2C metal carbide precipitates measured by voltage-pulsed APT to 532 or 355 nm wavelength laser-pulsed data permits correct quantification of precipitation.

  20. Characterization of carbon contamination under ion and hot atom bombardment in a tin-plasma extreme ultraviolet light source

    NASA Astrophysics Data System (ADS)

    Dolgov, A.; Lopaev, D.; Lee, C. J.; Zoethout, E.; Medvedev, V.; Yakushev, O.; Bijkerk, F.

    2015-10-01

    Molecular contamination of a grazing incidence collector for extreme ultraviolet (EUV) lithography was experimentally studied. A carbon film was found to have grown under irradiation from a pulsed tin plasma discharge. Our studies show that the film is chemically inert and has characteristics that are typical for a hydrogenated amorphous carbon film. It was experimentally observed that the film consists of carbon (∼70 at.%), oxygen (∼20 at.%) and hydrogen (bound to oxygen and carbon), along with a few at.% of tin. Most of the oxygen and hydrogen are most likely present as OH groups, chemically bound to carbon, indicating an important role for adsorbed water during the film formation process. It was observed that the film is predominantly sp3 hybridized carbon, as is typical for diamond-like carbon. The Raman spectra of the film, under 514 and 264 nm excitation, are typical for hydrogenated diamond-like carbon. Additionally, the lower etch rate and higher energy threshold in chemical ion sputtering in H2 plasma, compared to magnetron-sputtered carbon films, suggests that the film exhibits diamond-like carbon properties.

  1. Measurement of the resistance induced by a single atomic impurity on a (7,6) semiconducting carbon nanotube: scattering strength of individual potassium atoms as a function of gate voltage

    NASA Astrophysics Data System (ADS)

    Tsuchikawa, Ryuichi; Ahmadi, Amin; Heligman, Daniel; Zhang, Zhengyi; Mucciolo, Eduardo; Hone, James; Ishigami, Masa

    2015-03-01

    Despite many years of research, no measurements have been performed to determine resistance induced by impurities in carbon nanotubes. Over the last few years, we have developed a capability to measure the resistance induced by a single impurity atom on nanotubes with known chirality. Using this capability, we measured the resistance induced by an individual potassium atom on a (7,6) semiconducting carbon nanotube. The ``atomic'' resistance of potassium is found to be in the kohm range and has a strong dependence on the applied gate voltage. The scattering strength of the p-type (valence band) channel is approximately 20 times greater than that of the n-type (conduction band) channel. We integrate our atomically-controlled experimental result to a numerical recursive Green's function technique, which can precisely model the experiment, to understand the measured ``atomic'' resistance and the asymmetry. This work is based upon research supported by the National Science Foundation under Grant No. 0955625 and 1006230.

  2. A crossed beams study of the reaction of carbon atoms, C(3Pj), with vinyl cyanide, C2H3CN(X 1A')--investigating the formation of cyano propargyl radicals.

    PubMed

    Guo, Y; Gu, X; Zhang, F; Tang, M S; Sun, B J; H Chang, A H; Kaiser, R I

    2006-12-14

    The chemical dynamics of the reaction of ground state carbon atoms, C(3Pj), with vinyl cyanide, C2H3CN(X 1A'), were examined under single collision conditions at collision energies of 29.9 and 43.9 kJ mol(-1) using the crossed molecular beams approach. The experimental studies were combined with electronic structure calculations on the triplet C4H3N potential energy surface (H. F. Su, R. I. Kaiser, A. H. H. Chang, J. Chem. Phys., 2005, 122, 074320). Our investigations suggest that the reaction follows indirect scattering dynamics via addition of the carbon atom to the carbon-carbon double bond of the vinyl cyanide molecule yielding a cyano cyclopropylidene collision complex. The latter undergoes ring opening to form cis/trans triplet cyano allene which fragments predominantly to the 1-cyano propargyl radical via tight exit transition states; the 3-cyano propargyl isomer was inferred to be formed at least a factor of two less; also, no molecular hydrogen elimination channel was observed experimentally. These results are in agreement with the computational studies predicting solely the existence of a carbon versus hydrogen atom exchange pathway and the dominance of the 1-cyano propargyl radical product. The discovery of the cyano propargyl radical in the reaction of atomic carbon with vinyl cyanide under single collision conditions implies that this molecule can be an important reaction intermediate in combustion flames and also in extraterrestrial environments (cold molecular clouds, circumstellar envelopes of carbon stars) which could lead to the formation of cyano benzene (C6H5CN) upon reaction with a propargyl radical.

  3. Adsorption of carbon monoxide on small aluminum oxide clusters: Role of the local atomic environment and charge state on the oxidation of the CO molecule.

    PubMed

    Ornelas-Lizcano, J C; Guirado-López, R A

    2015-03-28

    We present extensive density functional theory (DFT) calculations dedicated to analyze the adsorption behavior of CO molecules on small AlxOy (±) clusters. Following the experimental results of Johnson et al. [J. Phys. Chem. A 112, 4732 (2008)], we consider structures having the bulk composition Al2O3, as well as smaller Al2O2 and Al2O units. Our electron affinity and total energy calculations are consistent with aluminum oxide clusters having two-dimensional rhombus-like structures. In addition, interconversion energy barriers between two- and one-dimensional atomic arrays are of the order of 1 eV, thus clearly defining the preferred isomers. Single CO adsorption on our charged AlxOy (±) clusters exhibits, in general, spontaneous oxygen transfer events leading to the production of CO2 in line with the experimental data. However, CO can also bind to both Al and O atoms of the clusters forming aluminum oxide complexes with a CO2 subunit. The vibrational spectra of AlxOy + CO2 provides well defined finger prints that may allow the identification of specific isomers. The AlxOy (+) clusters are more reactive than the anionic species and the final Al2O(+) + CO reaction can result in the production of atomic Al and carbon dioxide as observed from experiments. We underline the crucial role played by the local atomic environment, charge density distribution, and spin-multiplicity on the oxidation behavior of CO molecules. Finally, we analyze the importance of coadsorption and finite temperature effects by performing DFT Born-Oppenheimer molecular dynamics. Our calculations show that CO oxidation on AlxOy (+) clusters can be also promoted by the binding of additional CO species at 300 K, revealing the existence of fragmentation processes in line with the ones experimentally inferred.

  4. Adsorption of carbon monoxide on small aluminum oxide clusters: Role of the local atomic environment and charge state on the oxidation of the CO molecule

    NASA Astrophysics Data System (ADS)

    Ornelas-Lizcano, J. C.; Guirado-López, R. A.

    2015-03-01

    We present extensive density functional theory (DFT) calculations dedicated to analyze the adsorption behavior of CO molecules on small AlxOy± clusters. Following the experimental results of Johnson et al. [J. Phys. Chem. A 112, 4732 (2008)], we consider structures having the bulk composition Al2O3, as well as smaller Al2O2 and Al2O units. Our electron affinity and total energy calculations are consistent with aluminum oxide clusters having two-dimensional rhombus-like structures. In addition, interconversion energy barriers between two- and one-dimensional atomic arrays are of the order of 1 eV, thus clearly defining the preferred isomers. Single CO adsorption on our charged AlxOy± clusters exhibits, in general, spontaneous oxygen transfer events leading to the production of CO2 in line with the experimental data. However, CO can also bind to both Al and O atoms of the clusters forming aluminum oxide complexes with a CO2 subunit. The vibrational spectra of AlxOy + CO2 provides well defined finger prints that may allow the identification of specific isomers. The AlxOy+ clusters are more reactive than the anionic species and the final Al2O+ + CO reaction can result in the production of atomic Al and carbon dioxide as observed from experiments. We underline the crucial role played by the local atomic environment, charge density distribution, and spin-multiplicity on the oxidation behavior of CO molecules. Finally, we analyze the importance of coadsorption and finite temperature effects by performing DFT Born-Oppenheimer molecular dynamics. Our calculations show that CO oxidation on AlxOy+ clusters can be also promoted by the binding of additional CO species at 300 K, revealing the existence of fragmentation processes in line with the ones experimentally inferred.

  5. The addition of organic carbon and nitrate affects reactive transport of heavy metals in sandy aquifers.

    PubMed

    Satyawali, Yamini; Seuntjens, Piet; Van Roy, Sandra; Joris, Ingeborg; Vangeel, Silvia; Dejonghe, Winnie; Vanbroekhoven, Karolien

    2011-04-25

    Organic carbon introduction in the soil to initiate remedial measures, nitrate infiltration due to agricultural practices or sulphate intrusion owing to industrial usage can influence the redox conditions and pH, thus affecting the mobility of heavy metals in soil and groundwater. This study reports the fate of Zn and Cd in sandy aquifers under a variety of plausible in-situ redox conditions that were induced by introduction of carbon and various electron acceptors in column experiments. Up to 100% Zn and Cd removal (from the liquid phase) was observed in all the four columns, however the mechanisms were different. Metal removal in column K1 (containing sulphate), was attributed to biological sulphate reduction and subsequent metal precipitation (as sulphides). In the presence of both nitrate and sulphate (K2), the former dominated the process, precipitating the heavy metals as hydroxides and/or carbonates. In the presence of sulphate, nitrate and supplemental iron (Fe(OH)(3)) (K3), metal removal was also due to precipitation as hydroxides and/or carbonates. In abiotic column, K4, (with supplemental iron (Fe(OH)(3)), but no nitrate), cation exchange with soil led to metal removal. The results obtained were modeled using the reactive transport model PHREEQC-2 to elucidate governing processes and to evaluate scenarios of organic carbon, sulphate and nitrate inputs.

  6. Re-use of drinking water treatment plant (DWTP) sludge: Characterization and technological behaviour of cement mortars with atomized sludge additions

    SciTech Connect

    Husillos Rodriguez, N.; Martinez Ramirez, S.; Blanco Varela, M.T.; Guillem, M.; Puig, J.; Larrotcha, E.; Flores, J.

    2010-05-15

    This paper aims to characterize spray-dried DWTP sludge and evaluate its possible use as an addition for the cement industry. It describes the physical, chemical and micro-structural characterization of the sludge as well as the effect of its addition to Portland cements on the hydration, water demand, setting and mechanical strength of standardized mortars. Spray drying DWTP sludge generates a readily handled powdery material whose particle size is similar to those of Portland cement. The atomized sludge contains 12-14% organic matter (mainly fatty acids), while its main mineral constituents are muscovite, quartz, calcite, dolomite and seraphinite (or clinoclor). Its amorphous material content is 35%. The mortars were made with type CEM I Portland cement mixed with 10 to 30% atomized sludge exhibited lower mechanical strength than the control cement and a decline in slump. Setting was also altered in the blended cements with respect to the control.

  7. Self-Assembled Fe-N-Doped Carbon Nanotube Aerogels with Single-Atom Catalyst Feature as High-Efficiency Oxygen Reduction Electrocatalysts

    DOE PAGES

    Zhu, Chengzhou; Fu, Shaofang; Song, Junhua; ...

    2017-02-06

    In this study, self-assembled M–N-doped carbon nanotube aerogels with single-atom catalyst feature are for the first time reported through one-step hydrothermal route and subsequent facile annealing treatment. By taking advantage of the porous nanostructures, 1D nanotubes as well as single-atom catalyst feature, the resultant Fe–N-doped carbon nanotube aerogels exhibit excellent oxygen reduction reaction electrocatalytic performance even better than commercial Pt/C in alkaline solution.

  8. Self-Assembled Fe-N-Doped Carbon Nanotube Aerogels with Single-Atom Catalyst Feature as High-Efficiency Oxygen Reduction Electrocatalysts.

    PubMed

    Zhu, Chengzhou; Fu, Shaofang; Song, Junhua; Shi, Qiurong; Su, Dong; Engelhard, Mark H; Li, Xiaolin; Xiao, Dongdong; Li, Dongsheng; Estevez, Luis; Du, Dan; Lin, Yuehe

    2017-04-01

    Self-assembled M-N-doped carbon nanotube aerogels with single-atom catalyst feature are for the first time reported through one-step hydrothermal route and subsequent facile annealing treatment. By taking advantage of the porous nanostructures, 1D nanotubes as well as single-atom catalyst feature, the resultant Fe-N-doped carbon nanotube aerogels exhibit excellent oxygen reduction reaction electrocatalytic performance even better than commercial Pt/C in alkaline solution.

  9. Effects of titanium addition on the microstructure of carbon/copper composite materials

    NASA Astrophysics Data System (ADS)

    Oku, Takeo; Oku, Tatsuo

    2007-01-01

    Carbon(C)/copper(Cu)-based materials with high thermal conductivity and good stability at high temperatures were developed by adding a small amount of titanium, which has a low enthalpy of alloy formation with C and Cu. The isotropic fine-grained nuclear grade graphite and felt type C/C composite, which were impregnated by Cu and titanium, provided 1.3 times higher thermal conductivity at 1200 K than the original carbon materials. Microstructural analysis showed that the increase of thermal conductivity is due to the formation of titanium compounds at the C/Cu interface. These carbon-based materials could be a candidate material for the plasma facing components of fusion devices.

  10. Additional development of large diameter carbon monofilament. [from boron, hydrogen, and methane gas mixture

    NASA Technical Reports Server (NTRS)

    Jacob, B. A.; Veltri, R. D.

    1974-01-01

    The chemical vapor process for preparing a large diameter carbon-base monofilament from a BCl3, Ch4 and H2 gas mixture with a carbon substrate fiber was studied. The effect of reactor geometry, total gas flows and deposition temperature on the tensile strength of the monofilament were investigated. It was noted that consistent results could only be obtained when the carbon substrate fiber was cleaned. The strength of the monofilament was found to depend on the highest temperature and the temperature profile of the monofilament in the reactor. The strength of monofilament produced in the dc and RF reactors were found to be similar and similar alloy compositions in the monofilament were attained when the same gas ratios were used. The tensile strength of the monofilament at 500 C was found to be 60 to 70% of the room temperature tensile strength. No degradation was noted after exposure to molten aluminum.

  11. Vertical Alignment of Single-Walled Carbon Nanotubes on Nanostructure Fabricated by Atomic Force Microscope

    DTIC Science & Technology

    2009-12-16

    Kobayashi Y, Yamashita T, Ueno Y, Niwa O, Homma Y, Ogino T. Extremely intense Raman signals from single-walled carbon nanotubes suspended between Si...carbon nanotube field effect transistors with carbon nanotube electrodes. Appl Phys Lett. 2008;92(4):043110-3. [13] Jung YJ, Homma Y, Ogino T...Homma Y, Yamashita T, Kobayashi Y, Ogino T. Interconnection of nanostructures using carbon nanotubes. Physica B. 2002;323(1-4):122-3. [23] Searson

  12. Effect of organic additives on characteristics of carbon-coated LiCoPO4 synthesized by hydrothermal method

    NASA Astrophysics Data System (ADS)

    Maeyoshi, Yuta; Miyamoto, Shohei; Noda, Yusaku; Munakata, Hirokazu; Kanamura, Kiyoshi

    2017-01-01

    Carbon-coated LiCoPO4 particles are synthesized by one-pot hydrothermal process using three different organic additives (carboxymethylcellulose sodium salt (CMC), glucose, and ascorbic acid). The effect of the organic additives on particle size, morphology, nature of carbon coating, and electrochemical property of the resulting LiCoPO4 is investigated. CMC plays important roles to decrease the particle size and form well-covered carbon coating on the surface. Carbon-coated LiCoPO4 prepared using CMC delivers higher initial discharge capacity of 135 mA h g-1 at 0.1 C, and shows superior rate capability and cyclic performance than the other samples. The improved electrochemical characteristics are attributed to not only the fine particle which allows facile electronic and ionic transport, but also the high coverage of carbon coating which improves the electrical conductivity and prevents the irreversible reactions of the charged LiCoPO4 with electrolyte.

  13. Mechanical and Electrical Properties of a Polyimide Film Significantly Enhanced by the Addition of Single-Wall Carbon Nanotubes

    NASA Technical Reports Server (NTRS)

    Meador, Michael A.

    2005-01-01

    Single-wall carbon nanotubes have been shown to possess a combination of outstanding mechanical, electrical, and thermal properties. The use of carbon nanotubes as an additive to improve the mechanical properties of polymers and/or enhance their thermal and electrical conductivity has been a topic of intense interest. Nanotube-modified polymeric materials could find a variety of applications in NASA missions including large-area antennas, solar arrays, and solar sails; radiation shielding materials for vehicles, habitats, and extravehicular activity suits; and multifunctional materials for vehicle structures and habitats. Use of these revolutionary materials could reduce vehicle weight significantly and improve vehicle performance and capabilities.

  14. Enrichment and Location of Uranium Precipitates from Uranyl Carbonate Addition to Tank 43

    SciTech Connect

    d'Entremont, P.D.

    2001-06-04

    In order to safety restart the 2H evaporator, plans are to add depleted uranium (DU) as uranyl carbonate to Tank 43 to lower the 235U enrichment in the supernate. This memo examines the enrichment and location of uranium precipitates formed in Tank 43. An assessment of the risks associated with precipitating uranium shows that there is no criticality concern during this operation.

  15. Impacts of carbon source addition on denitrification and phosphorus uptake in enhanced biological phosphorus removal systems.

    PubMed

    Begum, Shamim A; Batista, Jacimaria R

    2013-01-01

    In this study, simultaneous denitrification and phosphorus (P) removal were investigated in batch tests using nitrified mixed liquor and secondary wastewater influent from a full-scale treatment plant and different levels of acetate and propionate as supplemental carbon sources. Without supplemental carbon source, denitrification occurred at low rate and P release and P uptake was negatively affected (i.e., P removal of only 59.7%). When acetate and propionate were supplied, denitrification and P release occurred simultaneously under anoxic conditions. For acetate and propionate at a C/N stoichiometric ratio of 7.6, P release was negatively affected by denitrification. For acetate, the percent P removal and denitrification were very similar for C/N ratios of 22 (5X stoichiometric) and 59 (10X stoichiometric). For propionate, both percent P removal and denitrification deteriorated for C/N ratios of 22 (5X stoichiometric) and 45 (10X stoichiometric). It was observed that carbon source added in excess to stoichiometric ratio was consumed in the aerobic zone, but P was not taken up. This implies that PAO bacteria may utilize the excess carbon source in the aerobic zone rather than their polyhydroxyalkanoate (PHA) reserves, thereby promoting deterioration of the system.

  16. Effect of powdered activated carbon (PAC) on MBR performance and effluent trihalomethane formation: At the initial stage of PAC addition.

    PubMed

    Gao, Yue; Ma, Defang; Yue, Qinyan; Gao, Baoyu; Huang, Xia

    2016-09-01

    In this study, the MBR was used to treat municipal wastewater for reuse. Effects of powdered activated carbon (PAC) addition on MBR system in terms of effluent water quality, trihalomethane (THM) formation and membrane organic fouling tendency of MBR sludge supernatant at the initial stage of PAC addition were investigated. Effects of chlorine dose and contact time on THM formation and speciation were also studied. PAC addition enhanced the removal of organic matters, especially aromatic components, which improved the UV254 removal rate from 34% to 83%. PAC addition greatly reduced the membrane organic fouling tendency of MBR sludge supernatant. PAC addition reduced the MBR effluent trihalomethane formation potential (THMFP) from 351.29 to 241.95μg/L, while increased THM formation reactivity by 42%. PAC addition enhanced the formation of higher toxic bromine-containing THMs. High chlorine dose and contact time resulted in higher THM formation but lower proportion of bromine-containing THMs.

  17. Stereochemical Control of Enzymatic Carbon-Carbon Bond-Forming Michael-Type Additions by "Substrate Engineering".

    PubMed

    Miao, Yufeng; Tepper, Pieter G; Geertsema, Edzard M; Poelarends, Gerrit J

    2016-11-01

    The enzyme 4-oxalocrotonate tautomerase (4-OT) promiscuously catalyzes the Michael-type addition of acetaldehyde to β-nitrostyrene derivatives to yield chiral γ-nitroaldehydes, which are important precursors for pharmaceutically active γ-aminobutyric acids. In this study, we investigated the effect of different substituents at the aromatic ring of the Michael acceptor on the catalytic efficiency and stereoselectivity of the 4-OT-catalyzed acetaldehyde addition reactions. Highly enantioenriched (R)- and (S)-γ-nitroaldehydes and 4-substituted chroman-2-ol could be obtained in good to excellent yields by applying different substituents at appropriate positions of the aromatic substrate. Stereochemical control of these enzymatic Michael-type additions by "substrate engineering" allowed the enantioselective synthesis of valuable γ-aminobutyric acid precursors. In addition, the results suggest a novel enzymatic synthesis route towards precursors for chromans and derivatives, which are valuable scaffolds for preparing biologically active natural products.

  18. Comparative investigation of solid electrolyte interphases created by the electrolyte additives vinyl ethylene carbonate and dicyano ketene vinyl ethylene acetal

    NASA Astrophysics Data System (ADS)

    Forestier, Coralie; Jankowski, Piotr; Wizner, Agnieszka; Davoisne, Carine; Gachot, Grégory; Sannier, Lucas; Grugeon, Sylvie; Johansson, Patrik; Armand, Michel; Laruelle, Stephane

    2017-03-01

    The effect of the replacement of the carbonyl oxygen in VEC additive by dbnd C(CN)2 in the analogous dicyano ketene vinyl ethylene acetal (DCKVEA) on the electrochemical reduction profile is significant. Yet, the additives were proven, through IR spectroscopy supported by DFT computations, by applying EELS techniques and performing synthesis of a reduction product, to reduce in a similar way. Interestingly, the reduction-induced capacities were found to be quite different and can be explained either by the different properties of the SEI, from lithium carbonate and its malononitrile homologue, or by the different abilities of the two additives to solvate Li+.

  19. The atomic-scale mechanism for the enhanced glass-forming-ability of a Cu-Zr based bulk metallic glass with minor element additions

    NASA Astrophysics Data System (ADS)

    Wang, Q.; Liu, C. T.; Yang, Y.; Liu, J. B.; Dong, Y. D.; Lu, J.

    2014-04-01

    It is known that the glass forming-ability (GFA) of bulk metallic glasses (BMGs) can be greatly enhanced via minor element additions. However, direct evidence has been lacking to reveal its structural origin despite different theories hitherto proposed. Through the high-resolution transmission-electron-microscopy (HRTEM) analysis, here we show that the content of local crystal-like orders increases significantly in a Cu-Zr-Al BMG after a 2-at% Y addition. Contrasting the previous studies, our current results indicate that the formation of crystal-like order at the atomic scale plays an important role in enhancing the GFA of the Cu-Zr-Al base BMG.

  20. Implications of Export/Import Reporting Requirements in the United States - International Atomic Energy Agency Safeguards Additional Protocol

    SciTech Connect

    Killinger, Mark H.; Benjamin, Eugene L.; McNair, Gary W.

    2001-02-20

    The United States has signed but not ratified the US/IAEA Safeguards Additional Protocol. If ratified, the Additional Protocol will require the US to report to the IAEA certain nuclear-related exports and imports to the IAEA. This document identifies and assesses the issues associated with the US making those reports. For example, some regulatory changes appear to be necessary. The document also attempts to predict the impact on the DOE Complex by assessing the historical flow of exports and imports that would be reportable if the Additional Protocol were in force.

  1. [High Throughput Screening Analysis of Preservatives and Sweeteners in Carbonated Beverages Based on Improved Standard Addition Method].

    PubMed

    Wang, Su-fang; Liu, Yun; Gong, Li-hua; Dong, Chun-hong; Fu, De-xue; Wang, Guo-qing

    2016-02-01

    Simulated water samples of 3 kinds of preservatives and 4 kinds of sweeteners were formulated by using orthogonal design. Kernel independent component analysis (KICA) was used to process the UV spectra of the simulated water samples and the beverages added different amounts of the additive standards, then the independent components (ICs), i. e. the UV spectral profiles of the additives, and the ICs' coefficient matrices were used to establish UV-KICA-SVR prediction model of the simulated preservatives and sweeteners solutions using support vector regression (SVR) analysis. The standards added beverages samples were obtained by adding different amounts level of additives in carbonated beverages, their UV spectra were processed by KICA, then IC information represented to the additives and other sample matrix were obtained, and the sample background can be deducted by removing the corresponding IC, other ICs' coefficient matrices were used to estimate the amounts of the additives in the standard added beverage samples based on the UV-KICA-SVR model, while the intercept of linear regression equation of predicted amounts and the added amounts in the standard added samples is the additive content in the raw beverage sample. By utilization of chemometric "blind source separation" method for extracting IC information of the tested additives in the beverage and other sample matrix, and using SVR regression modeling to improve the traditional standard addition method, a new method was proposed for the screening of the preservatives and sweeteners in carbonated beverages. The proposed UV-KICA-SVR method can be used to determine 3 kinds of preservatives and 4 kinds of sweetener in the carbonate beverages with the limit of detection (LOD) are located with the range 0.2-1.0 mg · L⁻¹, which are comparable to that of the traditional high performance liquid chromatographic (HPLC) method.

  2. Microbial biomass and carbon mineralization in agricultural soils as affected by pesticide addition.

    PubMed

    Kumar, Anjani; Nayak, A K; Shukla, Arvind K; Panda, B B; Raja, R; Shahid, Mohammad; Tripathi, Rahul; Mohanty, Sangita; Rath, P C

    2012-04-01

    A laboratory study was conducted with four pesticides, viz. a fungicide (carbendazim), two insecticides (chlorpyrifos and cartap hydrochloride) and an herbicide (pretilachlor) applied to a sandy clay loam soil at a field rate to determine their effect on microbial biomass carbon (MBC) and carbon mineralization (C(min)). The MBC content of soil increased with time up to 30 days in cartap hydrochloride as well as chlorpyrifos treated soil. Thereafter, it decreased and reached close to the initial level by 90th day. However, in carbendazim treated soil, the MBC showed a decreasing trend up to 45 days and subsequently increased up to 90 days. In pretilachlor treated soil, MBC increased through the first 15 days, and thereafter decreased to the initial level. Application of carbendazim, chlorpyrifos and cartap hydrochloride decreased C(min) for the first 30 days and then increased afterwards, while pretilachlor treated soil showed an increasing trend.

  3. Benchmark calculations of excess electrons in water cluster cavities: balancing the addition of atom-centered diffuse functions versus floating diffuse functions.

    PubMed

    Zhang, Changzhe; Bu, Yuxiang

    2016-09-14

    Diffuse functions have been proved to be especially crucial for the accurate characterization of excess electrons which are usually bound weakly in intermolecular zones far away from the nuclei. To examine the effects of diffuse functions on the nature of the cavity-shaped excess electrons in water cluster surroundings, both the HOMO and LUMO distributions, vertical detachment energies (VDEs) and visible absorption spectra of two selected (H2O)24(-) isomers are investigated in the present work. Two main types of diffuse functions are considered in calculations including the Pople-style atom-centered diffuse functions and the ghost-atom-based floating diffuse functions. It is found that augmentation of atom-centered diffuse functions contributes to a better description of the HOMO (corresponding to the VDE convergence), in agreement with previous studies, but also leads to unreasonable diffuse characters of the LUMO with significant red-shifts in the visible spectra, which is against the conventional point of view that the more the diffuse functions, the better the results. The issue of designing extra floating functions for excess electrons has also been systematically discussed, which indicates that the floating diffuse functions are necessary not only for reducing the computational cost but also for improving both the HOMO and LUMO accuracy. Thus, the basis sets with a combination of partial atom-centered diffuse functions and floating diffuse functions are recommended for a reliable description of the weakly bound electrons. This work presents an efficient way for characterizing the electronic properties of weakly bound electrons accurately by balancing the addition of atom-centered diffuse functions and floating diffuse functions and also by balancing the computational cost and accuracy of the calculated results, and thus is very useful in the relevant calculations of various solvated electron systems and weakly bound anionic systems.

  4. Effects of experimental fuel additions on fire intensity and severity: unexpected carbon resilience of a neotropical forest.

    PubMed

    Brando, Paulo M; Oliveria-Santos, Claudinei; Rocha, Wanderley; Cury, Roberta; Coe, Michael T

    2016-07-01

    Global changes and associated droughts, heat waves, logging activities, and forest fragmentation may intensify fires in Amazonia by altering forest microclimate and fuel dynamics. To isolate the effects of fuel loads on fire behavior and fire-induced changes in forest carbon cycling, we manipulated fine fuel loads in a fire experiment located in southeast Amazonia. We predicted that a 50% increase in fine fuel loads would disproportionally increase fire intensity and severity (i.e., tree mortality and losses in carbon stocks) due to multiplicative effects of fine fuel loads on the rate of fire spread, fuel consumption, and burned area. The experiment followed a fully replicated randomized block design (N = 6) comprised of unburned control plots and burned plots that were treated with and without fine fuel additions. The fuel addition treatment significantly increased burned area (+22%) and consequently canopy openness (+10%), fine fuel combustion (+5%), and mortality of individuals ≥5 cm in diameter at breast height (dbh; +37%). Surprisingly, we observed nonsignificant effects of the fuel addition treatment on fireline intensity, and no significant differences among the three treatments for (i) mortality of large trees (≥30 cm dbh), (ii) aboveground forest carbon stocks, and (iii) soil respiration. It was also surprising that postfire tree growth and wood increment were higher in the burned plots treated with fuels than in the unburned control. These results suggest that (i) fine fuel load accumulation increases the likelihood of larger understory fires and (ii) single, low-intensity fires weakly influence carbon cycling of this primary neotropical forest, although delayed postfire mortality of large trees may lower carbon stocks over the long term. Overall, our findings indicate that increased fine fuel loads alone are unlikely to create threshold conditions for high-intensity, catastrophic fires during nondrought years.

  5. An in situ generated carbon as integrated conductive additive for hierarchical negative plate of lead-acid battery

    NASA Astrophysics Data System (ADS)

    Saravanan, M.; Ganesan, M.; Ambalavanan, S.

    2014-04-01

    In this work, we report an in situ generated carbon from sugar as additive in the Negative Active Mass (NAM) which enhances the charge-discharge characteristics of the lead-acid cells. In situ formed sugar derived carbon (SDC) with leady oxide (LO) provides a conductive network and excellent protection against NAM irreversible lead sulfation. The effect of SDC and carbon black (CB) added negative plates are characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), galvanostatic charge-discharge, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), respectively. The results show that subtle changes in the addition of carbon to NAM led to subsequent changes on the performance during partial-state-of-charge (PSoC) operations in lead-acid cells. Furthermore, SDC added cells exhibit remarkable improvement in the rate capability, active material utilization, cycle performance and charge acceptance compared to that of the conventional CB added cells. The impact of SDC with LO at various synthesis conditions on the electrochemical performance of the negative plate is studied systematically.

  6. Effect of doping by boron, carbon, and nitrogen atoms on the magnetic and photocatalytic properties of anatase

    NASA Astrophysics Data System (ADS)

    Zainullina, V. M.; Zhukov, V. P.; Korotin, M. A.; Polyakov, E. V.

    2011-07-01

    The effect of doping of titanium dioxide with the anatase structure by boron, carbon, and nitrogen atoms on the magnetic and optical properties and the electronic spectrum of this compound has been investigated using the ab initio tight-binding linear muffin-tin orbital (TB-LMTO) band-structure method in the local spin density approximation explicitly including Coulomb correlations (LSDA + U) in combination with the semiempirical extended Hückel theory (EHT) method. The LSDA + U calculations of the electronic structure, the imaginary part of the dielectric function, the total magnetic moments, and the magnetic moments at the impurity atoms have been carried out. The diagrams of the molecular orbitals of the clusters Ti3 X ( X = B, C, N) have been calculated and the pseudo-space images of the molecular orbitals of the clusters have been constructed. The effect of doping on the nature and origin of photocatalytic activity in the visible spectral range and the specific features of the generation of ferromagnetic interactions in doped anatase have been discussed based on the analysis of the obtained data. It has been shown that, in the sequence TiO2 - y N y → TiO2 - y C y → TiO2 - y B y ( y = 1/16), the photocatalytic activity can increase with the generation of electronic excitations with the participation of impurity bands. The calculated magnetic moments for boron and nitrogen atoms are equal to 1 μB, whereas the impurity carbon atoms are nonmagnetic.

  7. Computational design of organometallic oligomers featuring 1,3-metal-carbon bonding and planar tetracoordinate carbon atoms.

    PubMed

    Zhao, Xue-Feng; Yuan, Cai-Xia; Wang, Xiang; Li, Jia-Jia; Wu, Yan-Bo; Wang, Xiaotai

    2016-01-15

    Density functional theory computations (B3LYP) have been used to explore the chemistry of titanium-aromatic carbon "edge complexes" with 1,3-metal-carbon (1,3-MC) bonding between Ti and planar tetracoordinate Cβ . The titanium-coordinated, end-capping chlorides are replaced with OH or SH groups to afford two series of difunctional monomers that can undergo condensation to form oxide- and sulfide-bridged oligomers. The sulfide-linked oligomers have less molecular strain and are more exergonic than the corresponding oxide-linked oligomers. The HOMO-LUMO gap of the oligomers varies with their composition and decreases with growing oligomer chain. This theoretical study is intended to enrich 1,3-MC bonding and planar tetracoordinate carbon chemistry and provide interesting ideas to experimentalists. Organometallic complexes with the TiE2 (E = OH and SH) decoration on the edge of aromatic hydrocarbons have been computationally designed, which feature 1,3-metal-carbon (1,3-MC) bonding between titanium and planar tetracoordinate β-carbon. Condensation of these difunctional monomers by eliminating small molecules (H2O and H2S) produce chain-like oligomers. The HOMO-LUMO gaps of the oligomers decreases with growing oligomer chain, a trend that suggests possible semiconductor properties for oligomers with longer chains.

  8. Unraveling the formation of HCPH(X2A') molecules in extraterrestrial environments: crossed molecular beam study of the reaction of carbon atoms, C(3Pj), with phosphine, PH3(X1A1).

    PubMed

    Guo, Y; Gu, X; Zhang, F; Sun, B J; Tsai, M F; Chang, A H H; Kaiser, R I

    2007-05-03

    The reaction between ground state carbon atoms, C(3P(j)), and phosphine, PH3(X(1)A1), was investigated at two collision energies of 21.1 and 42.5 kJ mol(-1) using the crossed molecular beam technique. The chemical dynamics extracted from the time-of-flight spectra and laboratory angular distributions combined with ab initio calculations propose that the reaction proceeds on the triplet surface via an addition of atomic carbon to the phosphorus atom. This leads to a triplet CPH3 complex. A successive hydrogen shift forms an HCPH2 intermediate. The latter was found to decompose through atomic hydrogen emission leading to the cis/trans-HCPH(X(2)A') reaction products. The identification of cis/trans-HCPH(X(2)A') molecules under single collision conditions presents a potential pathway to form the very first carbon-phosphorus bond in extraterrestrial environments like molecular clouds and circumstellar envelopes, and even in the postplume chemistry of the collision of comet Shoemaker-Levy 9 with Jupiter.

  9. Transition metal-catalyzed/mediated reaction of allenes with a nucleophilic functionality connected to the alpha-carbon atom.

    PubMed

    Ma, Shengming

    2003-09-01

    Allenes with a nucleophilic functionality connected to the alpha-carbon atom have been shown to be versatile building blocks for the syn-thesis of gamma-butenolides, gamma-lactams, gamma-iminolactones, vinylic epoxides, 4-amino-2-alkenols, 2-amino-3-alkenols, 2,5-dihydrofurans, furans, vinylic cyclopropanes, and cyclopentenes, depending on the nature of the nucleophilic centers. The reaction may proceed via the carbometalation-nucleophilic attack mechanism or nucleometallation-reductive elimination. The stereochemical outcomes by these two pathways are different.

  10. Large-Scale Fabrication of Carbon Nanotube Probe Tips For Atomic Force Microscopy Critical Dimension Imaging Applications

    NASA Technical Reports Server (NTRS)

    Ye, Qi Laura; Cassell, Alan M.; Stevens, Ramsey M.; Meyyappan, Meyya; Li, Jun; Han, Jie; Liu, Hongbing; Chao, Gordon

    2004-01-01

    Carbon nanotube (CNT) probe tips for atomic force microscopy (AFM) offer several advantages over Si/Si3N4 probe tips, including improved resolution, shape, and mechanical properties. This viewgraph presentation discusses these advantages, and the drawbacks of existing methods for fabricating CNT probe tips for AFM. The presentation introduces a bottom up wafer scale fabrication method for CNT probe tips which integrates catalyst nanopatterning and nanomaterials synthesis with traditional silicon cantilever microfabrication technology. This method makes mass production of CNT AFM probe tips feasible, and can be applied to the fabrication of other nanodevices with CNT elements.

  11. Synergic effect of atomic oxygen and outgassing phenomena on Carbon/SiC composites for space applications

    NASA Astrophysics Data System (ADS)

    Albano, Marta

    The space environment is one of the most critical for space structures. The low earth orbit (LEO) space environment includes hazards such as atomic oxygen, UV radiation, ionizing radiation (electrons, protons), high vacuum, plasma, micrometeoroids and debris, as well as severe temperature cycles. Exposure of composites to the space environment may result in different detrimental effects via modification of their chemical, electrical, thermal, optical and mechanical properties as well as surface erosion. The high vacuum induces material outgassing (e.g. low-molecular weight residues, plasticizers and additives) and consequent contamination of nearby surfaces. At LEO altitudes the neutral atmosphere consists primarily of ATOX (˜80%) and nitrogen molecules (˜20%). ATOX, which is formed by photo-dissociation of molecular oxygen in the upper atmosphere, is a severe hazard for composites. The number density of ATOX at about 300 km altitude is ˜2 × 109 to 8 × 109 atoms/cm3, for minimum and maximum solar activity, respectively. Front surfaces (ram direction) of space vehicles orbiting at a velocity of about 8 km/s collide with the ATOX species with impingement kinetic energy of approximately 5 eV. The ATOX flux is determined by such parameters as altitude, orbital inclination, solar activity and time of day. A nominal range of values for LEO is 1014-1015 atoms/cm2 s. The Low Earth Orbit is a complex and dynamic environment where constituents vary with position, local time, season and solar activity. Effects of different constituents of the space environment on spacecraft materials play an important role in determining the system function, reliability and lifetime. This is more crucial if the structure has to be used for the re-entry as thermal protection systems for example. In this case the integrity of the surface and its coating is crucial for the success of the entire mission. During the re-entry, resistance of materials is hard tested by fast chemical reactions

  12. The effect of diborane additive on the plasma-chemical properties of deposited carbon films

    NASA Astrophysics Data System (ADS)

    Shubina, E. N.; Karasev, P. A.; Titov, A. I.; Podsvirov, O. A.; Vinogradov, A. Ya.; Karasev, N. N.; Pozdnyakov, A. V.

    2017-01-01

    We present the results of studies of the optical, electrical, and mechanical properties of diamondlike carbon films prepared by plasma-chemical vapor deposition from a mixture of methane and diborane in various proportions. Upon reaching the threshold concentration ( 12%) of diborane in the mixture, inclusions of a new phase start to form in the structure of the films. This leads to nonlinear dependence of the interior stresses and the surface resistance of coatings on the composition of the mixture with minimum values corresponding to a diborane concentration of about 12%.

  13. Controlling the Electrostatic Discharge Ignition Sensitivity of Composite Energetic Materials Using Carbon Nanotube Additives

    SciTech Connect

    Kade H. Poper; Eric S. Collins; Michelle L. Pantoya; Michael Daniels

    2014-10-01

    Powder energetic materials are highly sensitive to electrostatic discharge (ESD) ignition. This study shows that small concentrations of carbon nanotubes (CNT) added to the highly reactive mixture of aluminum and copper oxide (Al + CuO) significantly reduces ESD ignition sensitivity. CNT act as a conduit for electric energy, bypassing energy buildup and desensitizing the mixture to ESD ignition. The lowest CNT concentration needed to desensitize ignition is 3.8 vol.% corresponding to percolation corresponding to an electrical conductivity of 0.04 S/cm. Conversely, added CNT increased Al + CuO thermal ignition sensitivity to a hot wire igniter.

  14. Energy budgeting and carbon footprint of transgenic cotton-wheat production system through peanut intercropping and FYM addition.

    PubMed

    Singh, Raman Jeet; Ahlawat, I P S

    2015-05-01

    Two of the most pressing sustainability issues are the depletion of fossil energy resources and the emission of atmospheric green house gases like carbon dioxide to the atmosphere. The aim of this study was to assess energy budgeting and carbon footprint in transgenic cotton-wheat cropping system through peanut intercropping with using 25-50% substitution of recommended dose of nitrogen (RDN) of cotton through farmyard manure (FYM) along with 100% RDN through urea and control (0 N). To quantify the residual effects of previous crops and their fertility levels, a succeeding crop of wheat was grown with varying rates of nitrogen, viz. 0, 50, 100, and 150 kg ha(-1). Cotton + peanut-wheat cropping system recorded 21% higher system productivity which ultimately helped to maintain higher net energy return (22%), energy use efficiency (12%), human energy profitability (3%), energy productivity (7%), carbon outputs (20%), carbon efficiency (17%), and 11% lower carbon footprint over sole cotton-wheat cropping system. Peanut addition in cotton-wheat system increased the share of renewable energy inputs from 18 to 21%. With substitution of 25% RDN of cotton through FYM, share of renewable energy resources increased in the range of 21% which resulted into higher system productivity (4%), net energy return (5%), energy ratio (6%), human energy profitability (74%), energy productivity (6%), energy profitability (5%), and 5% lower carbon footprint over no substitution. The highest carbon footprint (0.201) was recorded under control followed by 50 % substitution of RDN through FYM (0.189). With each successive increase in N dose up to 150 kg N ha(-1) to wheat, energy productivity significantly reduced and share of renewable energy inputs decreased from 25 to 13%. Application of 100 kg N ha(-1) to wheat maintained the highest grain yield (3.71 t ha(-1)), net energy return (105,516 MJ ha(-1)), and human energy profitability (223.4) over other N doses applied to wheat

  15. Operando atomic structure and active sites of TiO2(110)-supported gold nanoparticles during carbon monoxide oxidation.

    PubMed

    Saint-Lager, Marie-Claire; Laoufi, Issam; Bailly, Aude

    2013-01-01

    It is well known that gold nanoparticles supported on TiO2 act as a catalyst for CO oxidation, even below room temperature. Despite extensive studies, the origin of this catalytic activity remains under debate. Indeed, when the particle size decreases, many changes may occur; thus modifying the nanoparticles' electronic properties and consequently their catalytic performances. Thanks to a state-of-the-art home-developed setup, model catalysts can be prepared in ultra-high vacuum and their morphology then studied in operando conditions by Grazing Incidence Small Angle X-ray Scattering, as well as their atomic structure by Grazing Incidence X-ray Diffraction as a function of their catalytic activity. We previously reported on the existence of a catalytic activity maximum observed for three-dimensional gold nanoparticles with a diameter of 2-3 nm and a height of 6-7 atomic planes. In the present work we correlate this size dependence of the catalytic activity to the nanoparticles' atomic structure. We show that even when their size decreases below the optimum diameter, the gold nanoparticles keep the face-centered cubic structure characteristic of bulk gold. Nevertheless, for these smallest nanoparticles, the lattice parameter presents anisotropic strains with a larger contraction in the direction perpendicular to the surface. Moreover a careful analysis of the atomic-scale morphology around the catalytic activity maximum tends to evidence the role of sites with a specific geometry at the interface between the nanoparticles and the substrate. This argues for models where atoms at the interface periphery act as catalytically active sites for carbon monoxide oxidation.

  16. Biofuels from pyrolysis in perspective: trade-offs between energy yields and soil-carbon additions.

    PubMed

    Woolf, Dominic; Lehmann, Johannes; Fisher, Elizabeth M; Angenent, Largus T

    2014-06-03

    Coproduction of biofuels with biochar (the carbon-rich solid formed during biomass pyrolysis) can provide carbon-negative bioenergy if the biochar is sequestered in soil, where it can improve fertility and thus simultaneously address issues of food security, soil degradation, energy production, and climate change. However, increasing biochar production entails a reduction in bioenergy obtainable per unit biomass feedstock. Quantification of this trade-off for specific biochar-biofuel pathways has been hampered by lack of an accurate-yet-simple model for predicting yields, product compositions, and energy balances from biomass slow pyrolysis. An empirical model of biomass slow pyrolysis was developed and applied to several pathways for biochar coproduction with gaseous and liquid biofuels. Here, we show that biochar production reduces liquid biofuel yield by at least 21 GJ Mg(-1) C (biofuel energy sacrificed per unit mass of biochar C), with methanol synthesis giving this lowest energy penalty. For gaseous-biofuel production, the minimum energy penalty for biochar production is 33 GJ Mg(-1) C. These substitution rates correspond to a wide range of Pareto-optimal system configurations, implying considerable latitude to choose pyrolysis conditions to optimize for desired biochar properties or to modulate energy versus biochar yields in response to fluctuating price differentials for the two commodities.

  17. Adsorption and corrosion inhibition behavior of hydroxyethyl cellulose and synergistic surfactants additives for carbon steel in 1M HCl.

    PubMed

    Mobin, Mohammad; Rizvi, Marziya

    2017-01-20

    The inhibitory effect of hydroxyethylcellulose (HEC) on A1020 carbon steel corrosion in 1M HCl solution was evaluated at different concentrations and temperatures using weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), UV-vis spectrophotometry, scanning electron microscopy (SEM), energy dispersive x-ray analysis (EDX), atomic force microscopy (AFM) and quantum chemical analysis. Inhibition efficiency was found to increase with increase in concentration of HEC but decreased with increasing temperature. Inhibitory effect of HEC mixed with minimal concentration of surfactants, triton X 100 (TX), cetyl pyridinium chloride (CPC) and sodium dodecyl sulfate (SDS) was also evaluated. HEC gets adsorbed onto the mild steel surface via mixed type adsorption. Ea, ΔH, ΔS and ΔG⁰ads, the thermodynamic and activation parameters, were calculated and discussed. Adsorption of inhibitor on the steel/solution interface follows Langmuir adsorption isotherm. EIS suggests formation of protective layer over the carbon steel surface. Results of different experimental techniques pertaining to the inhibitory effect of HEC and HEC mixed with surfactants are in good agreement with theoretical quantum chemical investigation.

  18. Novel carbon-rich additives preparation by degradative solvent extraction of biomass wastes for coke-making.

    PubMed

    Zhu, Xianqing; Li, Xian; Xiao, Li; Zhang, Xiaoyong; Tong, Shan; Wu, Chao; Ashida, Ryuichi; Liu, Wenqiang; Miura, Kouichi; Yao, Hong

    2016-05-01

    In this work, two extracts (Soluble and Deposit) were produced by degradative solvent extraction of biomass wastes from 250 to 350°C. The feasibilities of using Soluble and Deposit as additives for coke-making were investigated for the first time. The Soluble and Deposit, having significantly higher carbon content, lower oxygen content and extremely lower ash content than raw biomasses. All Solubles and most of Deposits can melt completely at the temperature ranged from 80 to 120°C and 140 to 180°C, respectively. The additions of Soluble or Deposit into the coke-making coal significantly improved their thermoplastic properties with as high as 9°C increase of the plastic range. Furthermore, the addition of Deposit or Soluble also markedly enhanced the coke quality through increasing coke strength after reaction (CSR) and reducing coke reactivity index (CRI). Therefore, the Soluble and Deposit were proved to be good additives for coke-making.

  19. Improving the performance of an aerobic membrane bioreactor (MBR) treating pharmaceutical wastewater with powdered activated carbon (PAC) addition.

    PubMed

    Kaya, Yasemin; Bacaksiz, A Murat; Golebatmaz, Ugur; Vergili, Ilda; Gönder, Z Beril; Yilmaz, Gulsum

    2016-04-01

    In this study, the effects of organic loading rate (OLR) and the addition of powdered activated carbon (PAC) on the performance and membrane fouling of MBR were conducted to treat real pharmaceutical process wastewater. Over 145 days of operation, the MBR system was operated at OLRs ranging from 1 to 2 kg COD m(-3) day(-1) without sludge wasting. The addition of PAC provided an improvement in the flux, despite an increase in the OLR:PAC ratio. The results demonstrated that the hybrid PAC-MBR system maintained a reduced amount of membrane fouling and steadily increased the removal performance of etodolac. PAC addition reduced the deposition of extracellular polymeric substance and organic matter on the membrane surface and resulted an increase in COD removal even at higher OLRs with low PAC addition. Membrane fouling mechanisms were investigated using combined adsorption fouling models. Modified fouling index values and normalized mass transfer coefficient values indicated that predominant fouling mechanism was cake adsorption.

  20. Impacts of powdered activated carbon addition on trihalomethane formation reactivity of dissolved organic matter in membrane bioreactor effluent.

    PubMed

    Ma, Defang; Gao, Yue; Gao, Baoyu; Wang, Yan; Yue, Qinyan; Li, Qian

    2014-12-01

    Characteristics and trihalomethane (THM) formation reactivity of dissolved organic matter (DOM) in effluents from two membrane bioreactors (MBRs) with and without powdered activated carbon (PAC) addition (referred to as PAC/MBR and MBR, respectively) were examined to investigate the effects of PAC addition on THM formation of MBR effluent during chlorination. PAC addition increased the specific UV absorbance. Hydrophobic DOM especially hydrophobic acids in PAC/MBR effluent (50%) were more than MBR effluent (42%). DOM with molecular weight <1 kDa constituted 12% of PAC/MBR effluent DOM, which was less than that of MBR effluent (16%). Data obtained from excitation and emission matrix fluorescence spectroscopy revealed that PAC/MBR effluent DOM contained more simple aromatic protein, but had less fulvic acid-like and soluble microbial by-product-like. PAC addition reduced the formation of bromine-containing THMs during chlorination of effluents, but increased THM formation reactivity of effluent DOM.

  1. An atom probe study of carbon distribution in martensite in 2[1/4]Cr1Mo steel

    SciTech Connect

    Thomson, R.C. . Dept. of Materials Science and Metallurgy); Miller, M.K. . Metals and Ceramics Division)

    1995-01-15

    2[1/4]Cr1Mo steel is used widely for superheater tubing in power plants, and as a filler material for joining [1/2]Cr[1/2]Mo[1/4]V steam piping. Components in power plants can be massive and therefore differences in cooling rates can result in a mixed microstructure of allotriomorphic ferrite, bainite and martensite. The creep strength of the steel is critically dependent on the carbide distribution within the microstructure. The position and nature of carbides within the microstructure is itself a critical function of the movement of carbon through the microstructure during the early stages of tempering. In this paper, atom probe field ion microscopy has been used to examine carbon segregation to lath boundaries in martensite in 2[1/4]Cr1Mo steel. Significant carbon enrichment was observed at the lath boundaries. This enrichment is consistent with the observation of retained austenite films at the lath boundaries in the transmission electron microscope, and with carbon levels previously found in retained austenite in low alloy ferrous martensites.

  2. Depolarized light scattering in dilute solutions of alkanes: A comparison of the bond additive and interacting atom approximations to the molecular polarizability

    SciTech Connect

    Keyes, T.; Evans, G.T.; Ladanyi, B.M.

    1981-04-01

    The molecular polarizability of a few small alkane (4--10 bond) chains has been represented by (1) an interacting atom model (IAM), wherein the atoms are treated as isotropic point polarizabilities interacting by the dipole tensor; and (2) the bond additive approximation (BAA) in which each bond is assigned an axially symmetric polarizability tensor, and the total molecular polarizability is the sum of the individual bond values. For selected values of the gauche--trans energy difference (0.3 kcal/mole), the calculated mean anisotropy per backbone atom /N increases linearly with N for the IAM and is essentially independent of N in the BAA. Orientational correlation functions have been determined for several second rank tensors characterizing the flexible chains using a modified version of Fixman's Brownian dynamics programs. The orientational correlation functions displayed an effective nonanalytic decay for short times merging into an exponential for long times. Single particle correlation times for the IAM increased more rapidly with N than did those of the BAA. Relaxation of the end-to-end vector (actually its second rank analog) was found to be the slowest process, followed by the IAM and the BAA polarizabilities, and finally the fastest was a local rotational mode.

  3. Efficient Cu-catalyzed atom transfer radical addition reactions of fluoroalkylsulfonyl chlorides with electron-deficient alkenes induced by visible light.

    PubMed

    Tang, Xiao-Jun; Dolbier, William R

    2015-03-27

    Fluoroalkylsulfonyl chlorides, R(f)SO2Cl, in which R(f)=CF3, C4F9, CF2H, CH2F, and CH2CF3, are used as a source of fluorinated radicals to add fluoroalkyl groups to electron-deficient, unsaturated carbonyl compounds. Photochemical conditions, using Cu mediation, are used to produce the respective α-chloro-β-fluoroalkylcarbonyl products in excellent yields through an atom transfer radical addition (ATRA) process. Facile nucleophilic replacement of the α-chloro substituent is shown to lead to further diverse functionalization of the products.

  4. Agricultural management and labile carbon additions affect soil microbial community structure and interact with carbon and nitrogen cycling.

    PubMed

    Berthrong, Sean T; Buckley, Daniel H; Drinkwater, Laurie E

    2013-07-01

    We investigated how conversion from conventional agriculture to organic management affected the structure and biogeochemical function of soil microbial communities. We hypothesized the following. (1) Changing agricultural management practices will alter soil microbial community structure driven by increasing microbial diversity in organic management. (2) Organically managed soil microbial communities will mineralize more N and will also mineralize more N in response to substrate addition than conventionally managed soil communities. (3) Microbial communities under organic management will be more efficient and respire less added C. Soils from organically and conventionally managed agroecosystems were incubated with and without glucose ((13)C) additions at constant soil moisture. We extracted soil genomic DNA before and after incubation for TRFLP community fingerprinting of soil bacteria and fungi. We measured soil C and N pools before and after incubation, and we tracked total C respired and N mineralized at several points during the incubation. Twenty years of organic management altered soil bacterial and fungal community structure compared to continuous conventional management with the bacterial differences caused primarily by a large increase in diversity. Organically managed soils mineralized twice as much NO3 (-) as conventionally managed ones (44 vs. 23 μg N/g soil, respectively) and increased mineralization when labile C was added. There was no difference in respiration, but organically managed soils had larger pools of C suggesting greater efficiency in terms of respiration per unit soil C. These results indicate that the organic management induced a change in community composition resulting in a more diverse community with enhanced activity towards labile substrates and greater capacity to mineralize N.

  5. Design of a Soil Science practical exercise to understand the soil carbon sequestration after biochar addition

    NASA Astrophysics Data System (ADS)

    Gascó, Gabriel; Cely, Paola; Saa-Requejo, Antonio; Mendez, Ana; Antón, Jose Manuel; Sánchez, Elena; Moratiel, Ruben; Tarquis, Ana M.

    2014-05-01

    The adaptation of the Universities to European Higher Education Area (EHEA) involves changes in the learning system. Students must obtain specific capabilities in the different degrees or masters. For example, in the degree of Agronomy at the Universidad Politécnica de Madrid (UPM, Spain), they must command Soil science, Mathematics or English. Sometimes, There is not a good communication between teachers and it causes that students do not understand the importance of the different subjects of a career. For this reason, teachers of the Soil Science and Mathematics Departments of the UPM designed a common practice to teach to the students the role of soil on the carbon sequestration. The objective of this paper is to explain the followed steps to the design of the practice. Acknowledgement to Universidad Politécnica de Madrid for the Projects in Education Innovation IE12_13-02009 and IE12_13-02012.

  6. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel

    NASA Astrophysics Data System (ADS)

    Gao, Shan; Lin, Yue; Jiao, Xingchen; Sun, Yongfu; Luo, Qiquan; Zhang, Wenhua; Li, Dianqi; Yang, Jinlong; Xie, Yi

    2016-01-01

    Electroreduction of CO2 into useful fuels, especially if driven by renewable energy, represents a potentially ‘clean’ strategy for replacing fossil feedstocks and dealing with increasing CO2 emissions and their adverse effects on climate. The critical bottleneck lies in activating CO2 into the CO2•- radical anion or other intermediates that can be converted further, as the activation usually requires impractically high overpotentials. Recently, electrocatalysts based on oxide-derived metal nanostructures have been shown to enable CO2 reduction at low overpotentials. However, it remains unclear how the electrocatalytic activity of these metals is influenced by their native oxides, mainly because microstructural features such as interfaces and defects influence CO2 reduction activity yet are difficult to control. To evaluate the role of the two different catalytic sites, here we fabricate two kinds of four-atom-thick layers: pure cobalt metal, and co-existing domains of cobalt metal and cobalt oxide. Cobalt mainly produces formate (HCOO-) during CO2 electroreduction; we find that surface cobalt atoms of the atomically thin layers have higher intrinsic activity and selectivity towards formate production, at lower overpotentials, than do surface cobalt atoms on bulk samples. Partial oxidation of the atomic layers further increases their intrinsic activity, allowing us to realize stable current densities of about 10 milliamperes per square centimetre over 40 hours, with approximately 90 per cent formate selectivity at an overpotential of only 0.24 volts, which outperforms previously reported metal or metal oxide electrodes evaluated under comparable conditions. The correct morphology and oxidation state can thus transform a material from one considered nearly non-catalytic for the CO2 electroreduction reaction into an active catalyst. These findings point to new opportunities for manipulating and improving the CO2 electroreduction properties of metal systems

  7. Xylem-Transported Glucose as an Additional Carbon Source for Leaf Isoprene Formation in Quercus Robur L.

    NASA Astrophysics Data System (ADS)

    Graus, M.; Kreuzwieser, J.; Schnitzler, J.; Wisthaler, A.; Hansel, A.; Rennenberg, H.

    2003-04-01

    Isoprene is emitted from mature, photosynthesizing leaves of many plant species, particularly of trees. Current interest in understanding the biochemical and physiological mechanisms controlling isoprene formation is caused by the important role isoprene plays in atmospheric chemistry. Isoprene reacts with hydroxyl radicals (OH) thereby generating oxidizing agents such as ozone and organic peroxides. Ozone causes significant deterioration in air quality and can pose threats to human health therefore its control is a major goal in Europe and the United States. In recent years, much progress has been made in elucidating the pathways of isoprene biosynthesis. Nevertheless the regulatory mechanisms controlling isoprene emission are not completely understood. Light and temperature appear to be the main factors controlling short-term variations in isoprene emission. Exposure of plants to C-13 labeled carbon dioxide showed instantaneous assimilated carbon is the primary carbon source for isoprene formation. However, variations in diurnal and seasonal isoprene fluxes, which cannot be explained by temperature, light, and leaf development led to the suggestion that alternative carbon sources may exist contributing to isoprene emissions. The aim of the present study was to test whether xylem-transported carbohydrates act as additional sources for isoprene biosynthesis. For this purpose, [U-C-13] alpha-D-glucose was fed to photosynthesizing leaves via the xylem of Quercus robur L. seedlings and the incorporation of glucose derived C-13 into emitted isoprene was monitored in real time using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS). A rapid incorporation of C-13 from xylem-fed glucose into single (mass 70) and double (mass 71) C-13 labeled isoprene molecules was observed after a lag phase of approximately 5 to 10 minutes. This incorporation was temperature dependent and was highest (up to 13% C-13 of total carbon emitted as isoprene) at the temperature optimum of

  8. Effects of water and nitrogen addition on ecosystem carbon exchange in a meadow steppe.

    PubMed

    Wang, Yunbo; Jiang, Qi; Yang, Zhiming; Sun, Wei; Wang, Deli

    2015-01-01

    A changing precipitation regime and increasing nitrogen deposition are likely to have profound impacts on arid and semiarid ecosystem C cycling, which is often constrained by the timing and availability of water and nitrogen. However, little is known about the effects of altered precipitation and nitrogen addition on grassland ecosystem C exchange. We conducted a 3-year field experiment to assess the responses of vegetation composition, ecosystem productivity, and ecosystem C exchange to manipulative water and nitrogen addition in a meadow steppe. Nitrogen addition significantly stimulated aboveground biomass and net ecosystem CO2 exchange (NEE), which suggests that nitrogen availability is a primary limiting factor for ecosystem C cycling in the meadow steppe. Water addition had no significant impacts on either ecosystem C exchange or plant biomass, but ecosystem C fluxes showed a strong correlation with early growing season precipitation, rather than whole growing season precipitation, across the 3 experimental years. After we incorporated water addition into the calculation of precipitation regimes, we found that monthly average ecosystem C fluxes correlated more strongly with precipitation frequency than with precipitation amount. These results highlight the importance of precipitation distribution in regulating ecosystem C cycling. Overall, ecosystem C fluxes in the studied ecosystem are highly sensitive to nitrogen deposition, but less sensitive to increased precipitation.

  9. Effects of Water and Nitrogen Addition on Ecosystem Carbon Exchange in a Meadow Steppe

    PubMed Central

    Wang, Yunbo; Jiang, Qi; Yang, Zhiming; Sun, Wei; Wang, Deli

    2015-01-01

    A changing precipitation regime and increasing nitrogen deposition are likely to have profound impacts on arid and semiarid ecosystem C cycling, which is often constrained by the timing and availability of water and nitrogen. However, little is known about the effects of altered precipitation and nitrogen addition on grassland ecosystem C exchange. We conducted a 3-year field experiment to assess the responses of vegetation composition, ecosystem productivity, and ecosystem C exchange to manipulative water and nitrogen addition in a meadow steppe. Nitrogen addition significantly stimulated aboveground biomass and net ecosystem CO2 exchange (NEE), which suggests that nitrogen availability is a primary limiting factor for ecosystem C cycling in the meadow steppe. Water addition had no significant impacts on either ecosystem C exchange or plant biomass, but ecosystem C fluxes showed a strong correlation with early growing season precipitation, rather than whole growing season precipitation, across the 3 experimental years. After we incorporated water addition into the calculation of precipitation regimes, we found that monthly average ecosystem C fluxes correlated more strongly with precipitation frequency than with precipitation amount. These results highlight the importance of precipitation distribution in regulating ecosystem C cycling. Overall, ecosystem C fluxes in the studied ecosystem are highly sensitive to nitrogen deposition, but less sensitive to increased precipitation. PMID:26010888

  10. Modeling the Effect of External Carbon Source Addition under Different Electron Acceptor Conditions in Biological Nutrient Removal Activated Sludge Systems.

    PubMed

    Hu, Xiang; Wisniewski, Kamil; Czerwionka, Krzysztof; Zhou, Qi; Xie, Li; Makinia, Jacek

    2016-02-16

    The aim of this study was to expand the International Water Association Activated Sludge Model No. 2d (ASM2d) to predict the aerobic/anoxic behavior of polyphosphate accumulating organisms (PAOs) and "ordinary" heterotrophs in the presence of different external carbon sources and electron acceptors. The following new aspects were considered: (1) a new type of the readily biodegradable substrate, not available for the anaerobic activity of PAOs, (2) nitrite as an electron acceptor, and (3) acclimation of "ordinary" heterotrophs to the new external substrate via enzyme synthesis. The expanded model incorporated 30 new or modified process rate equations. The model was evaluated against data from several, especially designed laboratory experiments which focused on the combined effects of different types of external carbon sources (acetate, ethanol and fusel oil) and electron acceptors (dissolved oxygen, nitrate and nitrite) on the behavior of PAOs and "ordinary" heterotrophs. With the proposed expansions, it was possible to improve some deficiencies of the ASM2d in predicting the behavior of biological nutrient removal (BNR) systems with the addition of external carbon sources, including the effect of acclimation to the new carbon source.

  11. Lead acid battery performance and cycle life increased through addition of discrete carbon nanotubes to both electrodes

    NASA Astrophysics Data System (ADS)

    Sugumaran, Nanjan; Everill, Paul; Swogger, Steven W.; Dubey, D. P.

    2015-04-01

    Contemporary applications are changing the failure mechanisms of lead acid batteries. Sulfation at the negative electrode, acid stratification, and dendrite formation now precede positive electrode failures such as grid corrosion and active material shedding. To attenuate these failures, carbon has been explored as a negative electrode additive to increase charge acceptance, eliminate sulfation, and extend cycle life. Frequently, however, carbon incorporation decreases paste density and hinders manufacturability. Discrete carbon nanotubes (dCNT), also known as Molecular Rebar®, are lead acid battery additives which can be stably incorporated into either electrode to increase charge acceptance and cycle life with no change to paste density and without impeding the manufacturing process. Here, full-scale automotive batteries containing dCNT in the negative electrode or both negative and positive electrodes are compared to control batteries. dCNT batteries show little change to Reserve Capacity, improved Cold Cranking, increased charge acceptance, and enhanced overall system efficiency. Life cycle tests show >60% increases when dCNT are incorporated into the negative electrode (HRPSoC/SBA) and up to 500% when incorporated into both electrodes (SBA), with water loss per cycle reduced >20%. Failure modes of cycled batteries are discussed and a hypothesis of dCNT action is introduced: the dCNT/Had Overcharge Reaction Mechanism.

  12. Sodium tetramethoxyborate: an efficient catalyst for Michael additions of stabilized carbon nucleophiles.

    PubMed

    Campaña, Araceli G; Fuentes, Noelia; Gómez-Bengoa, Enrique; Mateo, Cristina; Oltra, J Enrique; Echavarren, Antonio M; Cuerva, Juan M

    2007-10-12

    Sodium tetramethoxyborate, easily prepared by reaction of inexpensive sodium borohydride with methanol, possesses a suitable combination of a Lewis base and a Lewis acid to catalyze Michael reactions at room temperature under practically neutral conditions. This reaction provides good to excellent yields of Michael addition products from a broad scope of Michael donor and Michael acceptor reagents.

  13. Nitrogen-addition effects on leaf traits and photosynthetic carbon gain of boreal forest understory shrubs.

    PubMed

    Palmroth, Sari; Bach, Lisbet Holm; Nordin, Annika; Palmqvist, Kristin

    2014-06-01

    Boreal coniferous forests are characterized by fairly open canopies where understory vegetation is an important component of ecosystem C and N cycling. We used an ecophysiological approach to study the effects of N additions on uptake and partitioning of C and N in two dominant understory shrubs: deciduous Vaccinium myrtillus in a Picea abies stand and evergreen Vaccinium vitis-idaea in a Pinus sylvestris stand in northern Sweden. N was added to these stands for 16 and 8 years, respectively, at rates of 0, 12.5, and 50 kg N ha(-1) year(-1). N addition at the highest rate increased foliar N and chlorophyll concentrations in both understory species. Canopy cover of P. abies also increased, decreasing light availability and leaf mass per area of V. myrtillus. Among leaves of either shrub, foliar N content did not explain variation in light-saturated CO2 exchange rates. Instead photosynthetic capacity varied with stomatal conductance possibly reflecting plant hydraulic properties and within-site variation in water availability. Moreover, likely due to increased shading under P. abies and due to water limitations in the sandy soil under P. sylvestris, individuals of the two shrubs did not increase their biomass or shift their allocation between above- and belowground parts in response to N additions. Altogether, our results indicate that the understory shrubs in these systems show little response to N additions in terms of photosynthetic physiology or growth and that changes in their performance are mostly associated with responses of the tree canopy.

  14. Effects of Carbon Addition on Iron and Phosphorus in a Highly Weathered Tropical Soil

    NASA Astrophysics Data System (ADS)

    Liptzin, D.; Silver, W. L.

    2008-12-01

    In the highly weathered iron (Fe)-rich soils of wet tropical forests, Fe may play a key role in controlling ecosystem processes because of its interactions with carbon (C) and phosphorus (P). The high NPP typical of tropical forests contributes significantly to the global C cycle. In Fe-rich tropical soils, NPP is thought to be limited by P. The periodic reducing conditions that occur in upland tropical soils may be associated with pulses of increased P availability because of the release of Fe-bound P during iron reduction. While little is known about the factors controlling Fe reduction in soils, it is likely that C availability plays a role. Typically, only simple C sources like acetate or glucose have been used to examine this limitation. However, the source of much of the C in nature is the complex mixture of organic compounds leached from leaves and litter. To investigate the linkages between Fe, C, and P, we compared the effects adding either acetate (200 mg C/L) or leaf leachate in low (50-100 mg C/L) or high (150-200 mg C/L) concentrations to incubated soils from a tropical rain forest in Puerto Rico under ambient atmospheric conditions. We measured pools of iron and phosphorus as well as pH at four time points over a month. Both Fe(II) and pH exhibited significant treatment effects, but not until the last sampling date. At this time, the Fe(II) concentration could explain 49% of the variability in soil pH. The pH was significantly higher in the acetate treatments than both the leaf leachate treatments. While Fe(II) concentration was significantly higher in the acetate treatment than the control and low leaf leachate treatment, there was no difference compared to the high leaf leachate treatment After one month microbial biomass P had increased significantly while the NaOH extractable organic P had decreased significantly. These changes suggest the rapid microbial uptake of P liberated from Fe. In conclusion, microbes appear to utilize more complex C in

  15. Regio- and stereoselective 1,2-dihydropyridine alkylation/addition sequence for the synthesis of piperidines with quaternary centers.

    PubMed

    Duttwyler, Simon; Chen, Shuming; Lu, Colin; Mercado, Brandon Q; Bergman, Robert G; Ellman, Jonathan A

    2014-04-07

    The first example of C alkylation of 1,2-dihydropyridines with alkyl triflates and Michael acceptors was developed to introduce quaternary carbon centers with high regio- and diastereoselectivity. Hydride or carbon nucleophile addition to the resultant iminium ion also proceeded with high diastereoselectivity. Carbon nucleophile addition results in an unprecedented level of substitution to provide piperidine rings with adjacent tetrasubstituted carbon atoms.

  16. Effects of dimethyl or diethyl carbonate as an additive on volatility and flash point of an aviation fuel.

    PubMed

    Li, Dan; Fang, Wenjun; Xing, Yan; Guo, Yongsheng; Lin, Ruisen

    2009-01-30

    Vapor pressures and flash points for several mixtures of an aviation fuel with dimethyl carbonate (DMC) or diethyl carbonate (DEC) have been measured, respectively, over the entire composition range. Correlation between the experimental vapor pressures and the equilibrium temperatures by the Antoine equation is performed for each mixture. The bubble-point lines of pressure versus composition at different temperatures and those of temperature versus composition at different pressures are then obtained from the Antoine correlations. It is found that DMC and DEC are the oxygenated hydrocarbon additives that can adjust effectively the volatility and flash point of the aviation fuel. The correlation of the flash points with the vapor pressure data for the pseudo-binary mixtures of the fuel and DMC or DEC gives satisfactory results.

  17. Oxidative N-Heterocyclic Carbene-Catalyzed γ-Carbon Addition of Enals to Imines: Mechanistic Studies and Access to Antimicrobial Compounds.

    PubMed

    Zheng, Peng-Cheng; Cheng, Jiajia; Su, Shihu; Jin, Zhichao; Wang, Yu-Huang; Yang, Song; Jin, Lin-Hong; Song, Bao-An; Chi, Yonggui Robin

    2015-07-06

    The reaction mechanism of the γ-carbon addition of enal to imine under oxidative N-heterocyclic carbene catalysis is studied experimentally. The oxidation, γ-carbon deprotonation, and nucleophilic addition of γ-carbon to imine were found to be facile steps. The results of our study also provide highly enantioselective access to tricyclic sulfonyl amides that exhibit interesting antimicrobial activities against X. oryzae, a bacterium that causes bacterial disease in rice growing.

  18. Diamond crystallization in a CO2-rich alkaline carbonate melt with a nitrogen additive

    NASA Astrophysics Data System (ADS)

    Khokhryakov, Alexander F.; Palyanov, Yuri N.; Kupriyanov, Igor N.; Nechaev, Denis V.

    2016-09-01

    Diamond crystallization was experimentally studied in a CO2-bearing alkaline carbonate melt with an increased content of nitrogen at pressure of 6.3 GPa and temperature of 1500 °C. The growth rate, morphology, internal structure of overgrown layers, and defect-impurity composition of newly formed diamond were investigated. The type of growth patterns on faces, internal structure, and nitrogen content were found to be controlled by both the crystallographic orientation of the growth surfaces and the structure of the original faces of diamond seed crystals. An overgrown layer has a uniform structure on the {100} plane faces of synthetic diamond and a fibrillar (fibrous) structure on the faceted surfaces of a natural diamond cube. The {111} faces have a polycentric vicinal relief with numerous twin intergrowths and micro twin lamellae. The stable form of diamond growth under experimental conditions is a curved-face hexoctahedron with small cube faces. The nitrogen impurity concentration in overgrown layers varies depending on the growth direction and surface type, from 100 to 1100 ppm.

  19. Theoretical exploration of the mechanism of riboflavin formation from 6,7-dimethyl-8-ribityllumazine: nucleophilic catalysis, hydride transfer, hydrogen atom transfer, or nucleophilic addition?

    PubMed

    Breugst, Martin; Eschenmoser, Albert; Houk, K N

    2013-05-01

    The cofactor riboflavin is biochemically synthesized by a constitutionally intricate process in which two molecules of 6,7-dimethyl-8-ribityllumazine react with each other to form one molecule of the cofactor and one molecule of 5-amino-6-(ribitylamino)uracil. Remarkably, this complex molecular transformation also proceeds non-enzymatically in boiling aqueous solution at pH 7.3. Four different mechanistic pathways for this transformation (nucleophilic catalysis, hydride transfer, hydrogen atom transfer, and a nucleophilic addition mechanism) have now been analyzed by density functional theory [M06-2X/def2-TZVPP/CPCM//M06-2X/6-31+G(d,p)/IEFPCM]. On the basis of these computational results, a so far unpublished nucleophilic addition mechanism is the lowest energy pathway yielding riboflavin. The previously proposed mechanism involving nucleophilic catalysis is higher in energy but is still a viable alternative for an enzyme-catalyzed process assisted by suitably positioned catalytic groups. Pathways involving the transfer of a hydride ion or of a hydrogen atom are predicted to proceed through higher energy transition states and intermediates.

  20. The efficiency of quartz addition on electric arc furnace (EAF) carbon steel slag stability.

    PubMed

    Mombelli, D; Mapelli, C; Barella, S; Gruttadauria, A; Le Saout, G; Garcia-Diaz, E

    2014-08-30

    Electric arc furnace slag (EAF) has the potential to be re-utilized as an alternative to stone material, however, only if it remains chemically stable on contact with water. The presence of hydraulic phases such as larnite (2CaO SiO2) could cause dangerous elements to be released into the environment, i.e. Ba, V, Cr. Chemical treatment appears to be the only way to guarantee a completely stable structure, especially for long-term applications. This study presents the efficiency of silica addition during the deslagging period. Microstructural characterization of modified slag was performed by SEM and XRD analysis. Elution tests were performed according to the EN 12457-2 standard, with the addition of silica and without, and the obtained results were compared. These results demonstrate the efficiency of the inertization process: the added silica induces the formation of gehlenite, which, even in caustic environments, does not exhibit hydraulic behaviour.

  1. Xylem-transported Glucose as an Additional Carbon Source for Leaf Isoprene Formation in Quercus Robur L.

    NASA Astrophysics Data System (ADS)

    Graus, M.; Wisthaler, A.; Hansel, A.; Kreuzwieser, J.; Rennenberg, H.; Schnitzler, J.

    2002-12-01

    Isoprene is emitted from mature, photosynthesizing leaves of many plant species, particularly of trees. Current interest in understanding the biochemical and physiological mechanisms controlling isoprene formation is caused by the important role isoprene plays in atmospheric chemistry. Isoprene reacts with hydroxyl radicals (OH) thereby generating oxidizing agents such as ozone and organic peroxides. Ozone causes significant deterioration in air quality and can pose threats to human health therefore its control is a major goal in Europe and the United States. In recent years, much progress has been made in elucidating the pathways of isoprene biosynthesis. Nevertheless the regulatory mechanisms controlling isoprene emission are not completely understood. Light and temperature appear to be the main factors controlling short-term variations in isoprene emission. Exposure of plants to 13CO2 showed instantaneous assimilated carbon is the primary carbon source for isoprene formation. However, variations in diurnal and seasonal isoprene fluxes, which cannot be explained by temperature, light, and leaf development led to the suggestion that alternative carbon sources may exist contributing to isoprene emissions. The aim of the present study was to test whether xylem-transported carbohydrates act as additional sources for isoprene biosynthesis. For this purpose, [U-13C]α-D-glucose was fed to photosynthesizing leaves via the xylem of {Quercus} {robur} L. seedlings and the incorporation of glucose derived 13C into emitted isoprene was monitored in real time using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS). A rapid incorporation of 13C from xylem-fed glucose into single (mass 70) and double (mass 71) 13C-labeled isoprene molecules was observed after a lag phase of approximately 5 to 10 minutes. This incorporation was temperature dependent and was highest (up to 13 % 13C of total carbon emitted as isoprene) at the temperature optimum of isoprene emission (40 - 42

  2. Additional reduction in serum phosphorus levels by pulverized lanthanum carbonate chewable in hemodialysis patients.

    PubMed

    Yamashita, Tetsuri; Ogawa, Tetsuya; Takahashi, Masaki; Mitsuhashi, Tetsuya; Shizuku, Junichi; Takahashi, Naoshi; Ohba, Takashi; Miyajima, Sayako; Kabaya, Takashi; Otsuka, Kuniaki; Nitta, Kosaku

    2013-04-01

    Lanthanum carbonate (LC) is one of the relatively new phosphate binders. The general LC dosage form is a chewable pharmaceutical preparation. This investigation was targeted to subjects who do not chew LC chewable preparations adequately, for the purpose of studying the clinical efficacy of changing to pulverized prescriptions, such as changes in serum phosphorus levels (P levels). The study took place at Minamisenju Hospital in October 2011, with 41 subjects on maintenance hemodialysis. We pulverized all of the LC chewable medicines of the LC insufficient mastication group (non-chewing: NC group, n = 18) using a crusher, and changed them to pulverized prescriptions. The testing period was set at 10 weeks. In the NC group, there was a significant lowering of P levels from 5.86 ± 1.31 mg/dL before pulverization of the LC chewable preparation (week 0) to 5.38 ± 1.26 mg/dL after 2 weeks of administration of the pulverized medication (P = 0.0310), 5.20 ± 1.25 mg/dL after 4 weeks (P = 0.0077), and 5.12 ± 1.34 mg/dL after 6 weeks (P = 0.0167). P levels in other patients than NC group showed no significant change. In this study, the P levels in the NC group was lowered significantly by changing the LC chewable to the pulverized prescription, and the residual LC images on the abdominal X-rays disappeared to the point where they could barely be confirmed.

  3. Artificial stimulation of soil amine production by addition of organic carbon and nitrogen transforming enzymes

    NASA Astrophysics Data System (ADS)

    Kieloaho, Antti-Jussi; Parshintsev, Jevgeni; Riekkola, Marja-Liisa; Kulmala, Markku; Pumpanen, Jukka; Heinonsalo, Jussi

    2013-04-01

    The major part of nitrogen (N) in boreal forest soil is in organic form (Soil Organic Nitrogen, SON). One of the main pathways for amine production is the decay of SON in soil. Amino acids react with specific decarboxylase enzymes which transform them to amines. Amino acid turnover time in forest soil is relatively fast (in hours) because amino acids can be used as N and C source by plants and microbes. Therefore, amino acid production by protease enzymes might be the critical step for amine production and release from forest soil. The aim of the study was to artificially introduce enzymes responsible for protein transformation into amino acids (proteases) as well as soil organic matter (SOM) decomposition (laccase and manganese peroxidase) in order to increase SON transformation and amine synthesis. Glucose addition has been shown to induce natural soil protease activity. Bovine serum albumin (BSA) was used as control protein. Treatments were conducted both in Scots pine seedlings containing as well as non-planted microcosms. N transformations were examined, as well as amine concentration in soil. The experiment consisted of eight different treatments; two as controls concerning enzyme addition, four treatments were planted with one year old nursery grown Scots pine (Pinus sylvestris L.) seedlings and four were non-planted. The experiment lasted approximately six months and the treatments with the additions were conducted within one more month. The protease activity was discovered more commonly after the treatment with protease or glucose additions. In planted BSA-control some natural protease activity was found but not in non-planted controls. Different substrate additions did not cause any differences in total N percentage, but the presence of the seedlings diminished soil N% by approximately 20%. In addition, the same effect was clearly seen in dissolved N, NH4+ and NO3-. Plant has exploited the soluble N forms almost entirely from the system, irrespective of

  4. Carbon source utilization profiles suggest additional metabolic interactions in a synergistic linuron-degrading bacterial consortium.

    PubMed

    Horemans, Benjamin; Smolders, Erik; Springael, Dirk

    2013-04-01

    A bacterial triple-species consortium that synergistically metabolizes the phenylurea herbicide linuron was studied to determine whether synergy is extended toward the metabolism of other C-sources. The metabolic performance and range of the individual consortium members were compared with those of paired and three-species combinations in Biolog GN2 MicroPlate assays. The strain combinations showed an increase in the rate and extent of utilization of 80% of the C-sources that were utilized by either one or more of the individual consortium members and the additional utilization of eight C-sources for which oxidation was not observed for the individual strains. When one of the three strains was replaced by bacterial strains 'foreign' to the consortium, either belonging to the same genus or to other genera, mainly antagonistic effects occurred. The data suggest that the consortium members cooperate in the metabolism of C-sources in addition to linuron. This feature can contribute in consolidating consortium composition when linuron is absent or present at low concentrations.

  5. A high-pressure atomic force microscope for imaging in supercritical carbon dioxide

    SciTech Connect

    Lea, A. S.; Higgins, S. R.; Knauss, K. G.; Rosso, K. M.

    2011-01-01

    A high-pressure atomic force microscope(AFM) that enables in situ, atomic scale measurements of topography of solid surfaces in contact with supercritical CO2 (scCO2) fluids has been developed. This apparatus overcomes the pressure limitations of the hydrothermal AFM and is designed to handle pressures up to 100 atm at temperatures up to ~350 K. A standard optically-based cantilever deflection detection system was chosen. When imaging in compressible supercritical fluids such as scCO2, precise control of pressure and temperature in the fluid cell is the primary technical challenge. Noise levels and imaging resolution depend on minimization of fluid density fluctuations that change the fluidrefractive index and hence the laser path. We demonstrate with our apparatus in situ atomic scale imaging of a calcite (CaCO3) mineral surface in scCO2; both single, monatomic steps and dynamic processes occurring on the (101¯4) surface are presented. Finally, this new AFM provides unprecedented in situ access to interfacial phenomena at solid–fluid interfaces under pressure.

  6. Kinetic and Mechanistic Studies of Carbon-to-Metal Hydrogen Atom Transfer Involving Os-Centered Radicals: Evidence for Tunneling

    SciTech Connect

    Lewandowska-Androlojc, Anna; Grills, David C.; Zhang, Jie; Bullock, R. Morris; Miyazawa, Akira; Kawanishi, Yuji; Fujita, Etsuko

    2014-03-05

    We have investigated the kinetics of novel carbon-to-metal hydrogen atom transfer reactions, in which homolytic cleavage of a C-H bond is accomplished by a single metal-centered radical. Studies by means of time-resolved IR spectroscopic measurements revealed efficient hydrogen atom transfer from xanthene, 9,10-dihydroanthracene and 1,4-cyclohexadiene to Cp(CO)2Os• and (n5-iPr4C5H)(CO)2Os• radicals, formed by photoinduced homolysis of the corresponding osmium dimers. The rate constants for hydrogen abstraction from these hydrocarbons were found to be in the range 1.54 × 105 M 1 s 1 -1.73 × 107 M 1 s-1 at 25 °C. For the first time, kinetic isotope effects for carbon-to-metal hydrogen atom transfer were determined. Large primary kinetic isotope effects of 13.4 ± 1.0 and 16.6 ± 1.4 were observed for the hydrogen abstraction from xanthene to form Cp(CO)2OsH and (n5-iPr4C5H)(CO)2OsH, respectively, at 25 °C. Temperature-dependent measurements of the kinetic isotope effects over a 60 -C temperature range were carried out to obtain the difference in activation energies and the pre-exponential factor ratio. For hydrogen atom transfer from xanthene to (n5-iPr4C5H)(CO)2Os•, the (ED - EH) = 3.25 ± 0.20 kcal/mol and AH/AD = 0.056 ± 0.018 values are greater than the semi-classical limits and thus suggest a quantum mechanical tunneling mechanism. The work at BNL was carried out under contract DE-AC02-98CH10886 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Geosciences & Biosciences, Office of Basic Energy Sciences. RMB also thanks the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences for support. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  7. Adsorption of carbon monoxide on small aluminum oxide clusters: Role of the local atomic environment and charge state on the oxidation of the CO molecule

    SciTech Connect

    Ornelas-Lizcano, J. C.; Guirado-López, R. A.

    2015-03-28

    We present extensive density functional theory (DFT) calculations dedicated to analyze the adsorption behavior of CO molecules on small Al{sub x}O{sub y}{sup ±} clusters. Following the experimental results of Johnson et al. [J. Phys. Chem. A 112, 4732 (2008)], we consider structures having the bulk composition Al{sub 2}O{sub 3}, as well as smaller Al{sub 2}O{sub 2} and Al{sub 2}O units. Our electron affinity and total energy calculations are consistent with aluminum oxide clusters having two-dimensional rhombus-like structures. In addition, interconversion energy barriers between two- and one-dimensional atomic arrays are of the order of 1 eV, thus clearly defining the preferred isomers. Single CO adsorption on our charged Al{sub x}O{sub y}{sup ±} clusters exhibits, in general, spontaneous oxygen transfer events leading to the production of CO{sub 2} in line with the experimental data. However, CO can also bind to both Al and O atoms of the clusters forming aluminum oxide complexes with a CO{sub 2} subunit. The vibrational spectra of Al{sub x}O{sub y} + CO{sub 2} provides well defined finger prints that may allow the identification of specific isomers. The Al{sub x}O{sub y}{sup +} clusters are more reactive than the anionic species and the final Al{sub 2}O{sup +} + CO reaction can result in the production of atomic Al and carbon dioxide as observed from experiments. We underline the crucial role played by the local atomic environment, charge density distribution, and spin-multiplicity on the oxidation behavior of CO molecules. Finally, we analyze the importance of coadsorption and finite temperature effects by performing DFT Born-Oppenheimer molecular dynamics. Our calculations show that CO oxidation on Al{sub x}O{sub y}{sup +} clusters can be also promoted by the binding of additional CO species at 300 K, revealing the existence of fragmentation processes in line with the ones experimentally inferred.

  8. Understanding drivers of the export of dissolved organic carbon from a German headwater catchment using Generalised Additive Models

    NASA Astrophysics Data System (ADS)

    Selle, Benny; Musolff, Andreas; Tittel, Jörg

    2016-04-01

    In the literature, several causes of recently increasing concentrations of dissolved organic carbon (DOC) in headwaters across eastern North America and northern and central Europe have been debated. One likely driver of the widespread increase of DOC concentrations since the early 1990s are decreasing depositions of acid rain resulting in an increased solubility of organic carbon compounds including humic acids. Here, we tested the hypothesis if the reduced availability of nitrate stimulated the microbial reduction of ferric iron soil minerals and the mobilisation of DOC. Forested catchments are relatively unaffected by agricultural and urban nitrate inputs. In these catchments, decreasing depositions often resulted in a reduced availability of nitrate, which are preferred electron acceptors in microbial decomposition processes. As ferric iron minerals act as efficient sorbents of organic compounds in soils its reduction may cause a release of humic substances and hence an export of DOC. To test this hypothesis, time series of DOC, dissolved iron and nitrate from a forested headwater catchment in Germany were examined using Generalised Additive Models. We found that rising DOC concentrations most likely resulted from a reductive dissolution of iron(III) minerals in soils and the associated mobilisation of adsorbed organic carbon. Phosphate, which can trigger undesired algal growth and is also known to be adsorbed by particulate iron(III), was released as well.

  9. The abundances of atomic carbon and carbon monoxide compared with visual extinction in the Ophiuchus molecular cloud complex

    NASA Technical Reports Server (NTRS)

    Frerking, Margaret A.; Keene, Jocelyn; Blake, Geoffrey A.; Phillips, T. G.

    1989-01-01

    Emission from the 492 GHz lines of C I have been observed toward six positions in the Ophiuchus molecular cloud complex for which accurate visual extinctions are available. The column density of C I increases with A(V) to greater than 2 x 10 to the 17th/sq cm at 100 mag, the column-averaged fractional abundance reaches a peak of about 2.2 x 10 to the -5th for A(V) in the range 4-11 mag and the column-averaged abundance ratio of C I to CO decreases with A(V) from about 1 at 2 mag to greater that about 0.03 at 100 mag. These results imply that, while C I is not the primary reservoir of gaseous carbon even at cloud edges, its fractional abundance remains high for at least 10 mag into the cloud and may be significant at even greater depths.

  10. Successful implementation of biochar carbon sequestration in European soils requires additional benefits and close collaboration with the bioenergy sector

    NASA Astrophysics Data System (ADS)

    Hauggaard-Nielsen, Henrik; Müller-Stöver, Dorette; Bruun, Esben W.; Petersen, Carsten T.

    2014-05-01

    Biochar soil application has been proposed as a measure to mitigate climate change and on the same time improve soil fertility by increased soil carbon sequestration. However, while on tropical soils the beneficial effects of biochar application on crop growth often become immediately apparent, it has been shown to be more difficult to demonstrate these effects on the more fertile soils in temperate regions. Therefore and because of the lack of carbon credits for farmers, it is necessary to link biochar application to additional benefits, both related to agricultural as well as to bioenergy production. Thermal gasification of biomass is an efficient (95% energy efficiency) and flexible way (able to cope with many different and otherwise difficult-to-handle biomass fuels) to generate bioenergy, while producing a valuable by-product - gasification biochar, containing recalcitrant carbon and essential crop nutrients. The use of the residual char product in agricultural soils will add value to the technology as well as result in additional soil benefits such as providing plant nutrients and improving soil water-holding capacity while reducing leaching risks. From a soil column (30 x 130 cm) experiment with gasification straw biochar amendment to coarse sandy subsoil increased root density of barley at critical depths in the soil profile reducing the mechanical resistance was shown, increasing yields, and the soil's capacity to store plant available water. Incorporation of residuals from a bioenergy technology like gasification show great potentials to reduce subsoil constraints increasing yield potentials on poor soils. Another advantage currently not appropriately utilized is recovery of phosphorus (P). In a recent pot experiments char products originating from low-temperature gasification of various biofuels were evaluated for their suitability as P fertilizers. Wheat straw gasification biochar generally had a low P content but a high P plant availability. To improve

  11. Exploring the Relationship Between Wetland Methane Emissions and Net Ecosystem Productivity Using Experimental Shading and Labile Carbon Additions.

    NASA Astrophysics Data System (ADS)

    Owens, S.; von Fischer, J. C.

    2007-12-01

    Methane (CH4) emissions from wetlands are positively correlated with net ecosystem productivity (NEP); however the relative importance of proposed controlling mechanisms remains poorly understood. The carbon supply hypothesis suggests that recent photosynthesis contributes labile carbon substrate to methanogenic habitats, resulting in higher CH4 emissions with increases in NEP. Plant gas transport is also hypothesized to be important for conducting gases between the soil and the atmosphere. High CH4 production rates often occur in saturated wetland soils where gas diffusion is extremely slow. The aerenchymous tissues of vascular wetland plants can serve as the primary pathway for CH4 emissions from the soil to the atmosphere, while also allowing CH4 to bypass more aerobic soil regions where CH4 oxidation could occur. Using a hypothesis-driven experimental approach, we established shading treatments in a Juncus- dominated wetland in the northern Colorado Front Range, and measured CH4 and CO2 fluxes with a static chamber technique. In the summer of 2007, the shading manipulations (45% and 65% shade) significantly reduced net ecosystem exchange (NEE; an approximation of NEP) and mean CH4 fluxes compared to control plots (p=0.02 and p=0.01, respectively). To test the carbon supply hypothesis, we injected a solution containing acetate (a primary methanogenic carbon source) to a depth of 20cm below the soil surface. Acetate additions stimulated CH4 emission rates across all plots by an average of 29.3% (p=0.01). However the strength of the CH4 emission response was not significantly related to plot treatment or NEE, indicating that reduced carbon supply could not explain the response to shading. We hypothesize that reduced plant gas transport was more important than labile carbon supply for driving the lower CH4 emission rates in shaded plots. The dry weight of above-ground biomass was lower in shaded plots (p=0.04), suggesting a possible link between plant gas transport

  12. The response of soil organic matter decomposition and carbon cycling to temperature increase and nitrogen addition

    NASA Astrophysics Data System (ADS)

    Choi, I.; Kang, M.; Choi, J.

    2012-12-01

    Global warming caused by greenhouse effects has raised the worldwide air temperature by 1.4~5.8°C from the pre-industrial level. It has been known that the enhanced air temperature leads to increase the rate of soil organic matter decomposition. The enhanced soil organic matter decomposition could increase the emission of GHG (Green House Gas-mostly CO2, CH4) from the terrestrial ecosystem. GHG emission from the decomposition of soil organic matter can be affected by N deposition. N deposition of Asia has significantly grown from 1000mg N m2yr-1 to 2000mg N m2yr-1during the period of 1990s. It is expected that large area of South and East Asia will receive as large as 5000mg N m2yr-1of nitrogen in the future. Therefore, it is interesting to investigate the effects of global change factors, such as elevated temperature and N deposition on GHG emission from the terrestrial ecosystem. Growth chamber experiments were conducted under the enhanced air temperature and N addition (controlled at 10°C(30°C), 20°C(40°C) from ambient air temperature 18°C/23°C(day/night)) and GHG(CH4,CO2)was measured using gas chromatograph. Since combined changes in temperature and N deposition are sensitive to litter quantity and quality, especially C:N ratio of organic material, we select three sites with different C:N ratio (rice paddy, forest, wetland) in the southern part of Han river in Korea. Our results show that, for the case of rice paddy and forest, CO2 flux at 30°C was higher than at 40°C. However, wetland soil produces higher CO2 flux at 40°C than at 30°C. While CH4 flux was not detected at 30°C for all of three soils, only wetland soil produced CH4 flux at 40°C. Every flux under the condition of N addition was higher than that of N limitation. The GHG fluxes clearly related to the temperature, N concentration difference and soil types. Long term laboratory experiments are needed in three different soil types to determine how different soil type affects GHG by

  13. The effect of activated carbon addition on membrane bioreactor processes for wastewater treatment and reclamation - A critical review.

    PubMed

    Skouteris, George; Saroj, Devendra; Melidis, Paraschos; Hai, Faisal I; Ouki, Sabèha

    2015-06-01

    This review concentrates on the effect of activated carbon (AC) addition to membrane bioreactors (MBRs) treating wastewaters. Use of AC-assisted MBRs combines adsorption, biodegradation and membrane filtration. This can lead to advanced removal of recalcitrant pollutants and mitigation of membrane fouling. The relative contribution of adsorption and biodegradation to overall removal achieved by an AC-assisted MBR process can vary, and "biological AC" may not fully develop due to competition of target pollutants with bulk organics in wastewater. Thus periodic replenishment of spent AC is necessary. Sludge retention time (SRT) governs the frequency of spent AC withdrawal and addition of fresh AC, and is an important parameter that significantly influences the performance of AC-assisted MBRs. Of utmost importance is AC dosage because AC overdose may aggravate membrane fouling, increase sludge viscosity, impair mass transfer and reduce sludge dewaterability.

  14. Combined nano-SIMS/AFM/EBSD analysis and atom probe tomography, of carbon distribution in austenite/ε-martensite high-Mn steels.

    PubMed

    Seol, Jae-Bok; Lee, B-H; Choi, P; Lee, S-G; Park, C-G

    2013-09-01

    We introduce a new experimental approach for the identification of the atomistic position of interstitial carbon in a high-Mn binary alloy consisting of austenite and ε-martensite. Using combined nano-beam secondary ion mass spectroscopy, atomic force microscopy and electron backscatter diffraction analyses, we clearly observe carbon partitioning to austenite. Nano-beam secondary ion mass spectroscopy and atom probe tomography studies also reveal carbon trapping at crystal imperfections as identified by transmission electron microscopy. Three main trapping sites can be distinguished: phase boundaries between austenite and ε-martensite, stacking faults in austenite, and prior austenite grain boundaries. Our findings suggest that segregation and/or partitioning of carbon can contribute to the austenite-to-martensite transformation of the investigated alloy.

  15. Reduction of Methane Emission during Slurry Storage by the Addition of Effective Microorganisms and Excessive Carbon Source from Brewing Sugar.

    PubMed

    Bastami, Mohd Saufi B; Jones, Davey L; Chadwick, David R

    2016-11-01

    Storing livestock manure is the primary stage of manure management where microbial processes and chemical reactions result in the release of methane (CH), nitrous oxide (NO), ammonia (NH), and carbon dioxide (CO). This study examined the reduction of CH emissions from slurry storage under two temperatures (cool [10°C] and warm [30°C]) when a glucose-rich substrate (brewing sugar) and activated effective microorganisms were applied at 10% (w/w) and 5% (v/w), respectively. Brewing sugar addition influenced microbial anaerobic respiration, resulting in a reduction of slurry pH to <5.0, through "self-acidification" caused by lactic acid production. Subsequently, CH emissions were significantly reduced by 87 and 99% in the cool and warm environments, respectively. The effective microorganism treatment did not change the chemical characteristics of the slurry but reduced CH emissions by 17 and 27% ( < 0.05) in the cool and warm environments, respectively. These results suggest that self-acidification after addition of a carbon source may be a promising alternative to slurry acidification using concentrated acids.

  16. Comparative studies between the influence of single- and multi-walled carbon nanotubes addition on Gd-123 superconducting phase

    NASA Astrophysics Data System (ADS)

    Abou-Aly, A. I.; Anas, M.; Ebrahim, Shaker; Awad, R.; Eldeen, I. G.

    2016-12-01

    The effect of single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) addition on the phase formation and the superconducting properties of GdBa2Cu3O7-δ phase has been studied. Therefore, composite superconductor samples of type (CNTs)x GdBa2Cu3O7-δ, 0.0 ≤ x ≤ 0.1 wt.% have been synthesized by a standard solid-state reaction technique. The samples have been characterized using X-ray powder diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). The results of XRD show an enhancement in the phase formation up to 0.06 wt.% and 0.08 wt.% for SWCNTs and MWCNTs, respectively. SEM and TEM reveal that CNTs form an electrical network resulting in well-connected superconducting grains. The electrical properties of the prepared samples have been examined by electric resistivity and I-V measurements, and their results reinforce the XRD, SEM and TEM. Consequently, both Tc and Jc improve as the addition percentage increases up to 0.06 wt.% and 0.08 wt.% for SWCNTs and MWCNTs, respectively.

  17. Biofunctionalization of carbon nanotubes/chitosan hybrids on Ti implants by atom layer deposited ZnO nanostructures

    NASA Astrophysics Data System (ADS)

    Zhu, Yizhou; Liu, Xiangmei; Yeung, Kelvin W. K.; Chu, Paul K.; Wu, Shuilin

    2017-04-01

    One-dimensional (1D) nanostructures of ZnO using atomic layer deposition (ALD) on chitosan (CS) modified carbon nanotubes (CNTs) were first introduced onto the surfaces of biomedical implants. When the content of ZnO is not sufficient, CNTs can strengthen the antibacterial activity against E. coli and S. aureus by 8% and 39%, respectively. CS can improve the cytocompatibility of CNTs and ZnO. The amount of Zn content can be controlled by changing the cycling numbers of ALD processes. This hybrid coating can not only endow medical implants with high self-antibacterial efficacy against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) of over 73% and 98%, respectively, but also regulate the proliferation and osteogenic differentiation of osteoblasts by controlling the amount of ZnO.

  18. Atomic layer deposition of ruthenium on plasma-treated vertically aligned carbon nanotubes for high-performance ultracapacitors.

    PubMed

    Kim, Jun Woo; Kim, Byungwoo; Park, Suk Won; Kim, Woong; Shim, Joon Hyung

    2014-10-31

    It is challenging to realize a conformal metal coating by atomic layer deposition (ALD) because of the high surface energy of metals. In this study, ALD of ruthenium (Ru) on vertically aligned carbon nanotubes (CNTs) was carried out. To activate the surface of CNTs that lack surface functional groups essential for ALD, oxygen plasma was applied ex situ before ALD. X-ray photoelectron spectroscopy and Raman spectroscopy confirmed surface activation of CNTs by the plasma pretreatment. Transmission electron microscopy analysis with energy-dispersive x-ray spectroscopy composition mapping showed that ALD Ru grew conformally along CNTs walls. ALD Ru/CNTs were electrochemically oxidized to ruthenium oxide (RuOx) that can be a potentially useful candidate for use in the electrodes of ultracapacitors. Electrode performance of RuOx/CNTs was evaluated using cyclic voltammetry and galvanostatic charge-discharge measurements.

  19. Atomic Layer Deposition on Gram Quantities of Multi-Walled Carbon Nanotubes

    DTIC Science & Technology

    2009-06-03

    Technol. 61 1899 [34] Coleman J N, Khan U, Blau W J and Gun’ko Y K 2006 Carbon 44 1624 [ 35 ] Lau K T, Gu C and Hui D 2006 Composites B 37 425 [36] Breuer...B 22 240 [63] Zhang W, Brongersma S H, Richard O, Brijs B, Palmans R, Froyen L and Maex K 2004 Microelectron. Eng. 76 146 10

  20. Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion

    SciTech Connect

    Chaudhari, Mangesh I.; Nair, Jijeesh R.; Pratt, Lawrence R.; Soto, Fernando A.; Balbuena, Perla B.; Rempe, Susan B.

    2016-10-21

    Lithium-ion solvation and diffusion properties in ethylene carbonate (EC) and propylene carbonate (PC) were studied by molecular simulation, experiments, and electronic structure calculations. Studies carried out in water provide a reference for interpretation. Classical molecular dynamics simulation results are compared to ab initio molecular dynamics to assess nonpolarizable force field parameters for solvation structure of the carbonate solvents. Quasi-chemical theory (QCT) was adapted to take advantage of fourfold occupancy of the near-neighbor solvation structure observed in simulations and used to calculate solvation free energies. The computed free energy for transfer of Li+ to PC from water, based on electronic structure calculations with cluster-QCT, agrees with the experimental value. The simulation-based direct-QCT results with scaled partial charges agree with the electronic structure-based QCT values. The computed Li+/PF6- transference numbers of 0.35/0.65 (EC) and 0.31/0.69 (PC) agree well with NMR experimental values of 0.31/0.69 (EC) and 0.34/0.66 (PC) and similar values obtained here with impedance spectroscopy. These combined results demonstrate that solvent partial charges can be scaled in systems dominated by strong electrostatic interactions to achieve trends in ion solvation and transport properties that are comparable to ab initio and experimental results. Thus, the results support the use of scaled partial charges in simple, nonpolarizable force fields in future studies of these electrolyte solutions.

  1. Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion

    DOE PAGES

    Chaudhari, Mangesh I.; Nair, Jijeesh R.; Pratt, Lawrence R.; ...

    2016-10-21

    Lithium-ion solvation and diffusion properties in ethylene carbonate (EC) and propylene carbonate (PC) were studied by molecular simulation, experiments, and electronic structure calculations. Studies carried out in water provide a reference for interpretation. Classical molecular dynamics simulation results are compared to ab initio molecular dynamics to assess nonpolarizable force field parameters for solvation structure of the carbonate solvents. Quasi-chemical theory (QCT) was adapted to take advantage of fourfold occupancy of the near-neighbor solvation structure observed in simulations and used to calculate solvation free energies. The computed free energy for transfer of Li+ to PC from water, based on electronic structuremore » calculations with cluster-QCT, agrees with the experimental value. The simulation-based direct-QCT results with scaled partial charges agree with the electronic structure-based QCT values. The computed Li+/PF6- transference numbers of 0.35/0.65 (EC) and 0.31/0.69 (PC) agree well with NMR experimental values of 0.31/0.69 (EC) and 0.34/0.66 (PC) and similar values obtained here with impedance spectroscopy. These combined results demonstrate that solvent partial charges can be scaled in systems dominated by strong electrostatic interactions to achieve trends in ion solvation and transport properties that are comparable to ab initio and experimental results. Thus, the results support the use of scaled partial charges in simple, nonpolarizable force fields in future studies of these electrolyte solutions.« less

  2. T-shaped ionic liquid crystals based on the imidazolium motif: exploring substitution of the C-2 imidazolium carbon atom.

    PubMed

    Goossens, Karel; Wellens, Sil; Van Hecke, Kristof; Van Meervelt, Luc; Cardinaels, Thomas; Binnemans, Koen

    2011-04-04

    In this contribution the first examples of so-called rigid-core, T-shaped imidazolium ionic liquid crystals, in which the C-2 atom of the imidazolium ring is substituted with an aryl moiety decorated with one or two alkoxy chains, are described. The length of the alkoxy chain(s) was varied from six to eighteen carbon atoms (n=6, 10, 14-18). Whereas the compounds with one long alkoxy chain display only smectic A phases, the salts containing two alkoxy chains exhibit smectic A, multicontinuous cubic, as well as hexagonal columnar phases, as evidenced by polarising optical microscopy, differential scanning calorimetry, and powder X-ray diffraction. Structural models are proposed for the self-assembly of the molecules within the mesophases. The imidazolium head groups and the iodide counterions were found to adopt a peculiar orientation in the central part of the columns of the hexagonal columnar phases. The enantiotropic cubic phase shown by the 1,3-dimethyl-2-[3,4-bis(pentadecyloxy)phenyl]imidazolium iodide salt has a multicontinuous Pm ̄3m structure. To the best of our knowledge, this is the first example of a thermotropic cubic mesophase of this symmetry.

  3. How surface reparation prevents catalytic oxidation of carbon monoxide on atomic gold at defective magnesium oxide surfaces.

    PubMed

    Töpfer, Kai; Tremblay, Jean Christophe

    2016-07-21

    In this contribution, we study using first principles the co-adsorption and catalytic behaviors of CO and O2 on a single gold atom deposited at defective magnesium oxide surfaces. Using cluster models and point charge embedding within a density functional theory framework, we simulate the CO oxidation reaction for Au1 on differently charged oxygen vacancies of MgO(001) to rationalize its experimentally observed lack of catalytic activity. Our results show that: (1) co-adsorption is weakly supported at F(0) and F(2+) defects but not at F(1+) sites, (2) electron redistribution from the F(0) vacancy via the Au1 cluster to the adsorbed molecular oxygen weakens the O2 bond, as required for a sustainable catalytic cycle, (3) a metastable carbonate intermediate can form on defects of the F(0) type, (4) only a small activation barrier exists for the highly favorable dissociation of CO2 from F(0), and (5) the moderate adsorption energy of the gold atom on the F(0) defect cannot prevent insertion of molecular oxygen inside the defect. Due to the lack of protection of the color centers, the surface becomes invariably repaired by the surrounding oxygen and the catalytic cycle is irreversibly broken in the first oxidation step.

  4. Molybdoenzyme That Catalyzes the Anaerobic Hydroxylation of a Tertiary Carbon Atom in the Side Chain of Cholesterol*

    PubMed Central

    Dermer, Juri; Fuchs, Georg

    2012-01-01

    Cholesterol is a ubiquitous hydrocarbon compound that can serve as substrate for microbial growth. This steroid and related cyclic compounds are recalcitrant due to their low solubility in water, complex ring structure, the presence of quaternary carbon atoms, and the low number of functional groups. Aerobic metabolism therefore makes use of reactive molecular oxygen as co-substrate of oxygenases to hydroxylate and cleave the sterane ring system. Consequently, anaerobic metabolism must substitute oxygenase-catalyzed steps by O2-independent hydroxylases. Here we show that one of the initial reactions of anaerobic cholesterol metabolism in the β-proteobacterium Sterolibacterium denitrificans is catalyzed by an unprecedented enzyme that hydroxylates the tertiary C25 atom of the side chain without molecular oxygen forming a tertiary alcohol. This steroid C25 dehydrogenase belongs to the dimethyl sulfoxide dehydrogenase molybdoenzyme family, the closest relative being ethylbenzene dehydrogenase. It is a heterotrimer, which is probably located at the periplasmic side of the membrane and contains one molybdenum cofactor, five [Fe-S] clusters, and one heme b. The draft genome of the organism contains several genes coding for related enzymes that probably replace oxygenases in steroid metabolism. PMID:22942275

  5. Magnetic properties and microstructure of gas atomized MRE2(Fe,Co)14B powder with ZrC addition (MRE=Nd+Y+Dy)

    NASA Astrophysics Data System (ADS)

    Tang, W.; Wu, Y. Q.; Dennis, K. W.; Oster, N. T.; Kramer, M. J.; Anderson, I. E.; McCallum, R. W.

    2009-04-01

    Gas atomization powder with Zr substitutions for the MRE and ZrC additions were systematically studied. The results show that the partial substitutions of Zr and the ZrC additions effectively improved glass formability in the alloys. Scanning electron microscopy (SEM) revealed that the as-atomized powder with a particle size of less than 32 μm is predominately uniform equiaxed grains with an average grain size of 1.5 μm. X-ray diffraction and differential thermal analysis measurements detected very tiny amounts of amorphous phase. After annealing at 700 °C for 15 min, the SEM grain microstructure exhibits a minor change, but magnetic properties are substantially improved. M versus T measurements reveal that the phase composition evolved from 2:14:1 plus a small amount of 2:17 phases to a single 2:14:1 phase during the annealing process. The sieve analysis of the powders showed a particle size distribution with 90 wt % of the powder less than 45 μm. The magnetic properties of the annealed powder varied with particle size. (BH)max first increases with increasing particle size from 5 μm, reaches the peak value in the size range of 20-25 μm, and then decreases with increasing particle size. For the 20-25 μm powder sample annealed at 700 °C for 15 min, the (BH)max of 9.6 MG Oe at room temperature and 5.6 MG Oe at 200 °C were obtained, respectively.

  6. PHASE EQUILIBRIA INVESTIGATIONS OF BINARY, TERNARY, AND HIGHER ORDER SYSTEMS. PART 2. EFFECT OF RHENIUM AND ALUMINUM ADDITIONS ON THE METAL-RICH EQUILIBRIA IN THE TITANIUM-MOLYBDENIUM-CARBON AND TITANIUM-NIOBIUM-CARBON SYSTEMS

    DTIC Science & Technology

    The solid state phase equilibria of the metal-rich regions of the Titanium-Molybdenum-Carbon and Titanium-Niobium-Carbon systems with up to 12 At...Rhenium and 10 At.% Aluminum additions, respectively, have been determined on hot pressed, heat treated, and in part arc melted alloys. The phase ... equilibria in the metal-rich regions, with these additions, is practically unchanged over that of the ternary Titanium-Molybdenum-Carbon and Titanium

  7. Quenching and partitioning response of carbon-manganese-silicon sheet steels containing nickel, molybdenum, aluminum and copper additions

    NASA Astrophysics Data System (ADS)

    Kahkonen, Joonas

    In order to produce passenger vehicles with improved fuel economy and increased passenger safety, car manufacturers are in need of steels with enhanced strength levels and good formability. Recently, promising combinations of strength and ductility have been reported for several, so-called third generation advanced high-strength steels (AHSS) and quenching and partitioning (Q&P) steels are increasingly being recognized as a promising third generation AHSS candidate. Early Q research used conventional TRIP steel chemistries and richer alloying strategies have been explored in more recent studies. However, systematic investigations of the effects of alloying elements on tensile properties and retained austenite fractions of Q&P steels are sparse. The objective of the present research was to investigate the alloying effects of carbon, manganese, molybdenum, aluminum, copper and nickel on tensile properties and microstructural evolution of Q&P heat treated sheet steels. Seven alloys were investigated with 0.3C-1.5Mn-1.5Si (wt pct) and 0.4C-1.5Mn-1.5Si alloys used to study carbon effects, a 0.3C-5Mn-1.6Si alloy to study manganese effects, 0.3C-3Mn-1.5Si-0.25Mo and 0.3C-3Mn-1.5Si-0.25Mo-0.85Al alloys to study molybdenum and aluminum effects and 0.2C-1.5Mn-1.3Si-1.5Cu and 0.2C-1.5Mn-1.3Si-1.5Cu-1.5Ni alloys to study copper and nickel effects. Increasing alloy carbon content was observed to mainly increase the ultimate tensile strength (UTS) up to 1865 MPa without significantly affecting total elongation (TE) levels. Increasing alloy carbon content also increased the resulting retained austenite (RA) fractions up to 22 vol pct. Measured maximum RA fractions were significantly lower than the predicted maximum RA levels in the 0.3C-1.5Mn-1.5Si and 0.4C-1.5Mn-1.5Si alloys, likely resulting from transition carbide formation. Increasing alloy manganese content increased UTS, TE and RA levels, and decreased yield strength (YS) and austenite carbon content (Cgamma) levels

  8. The Effect of Additional Dead Space on Respiratory Exchange Ratio and Carbon Dioxide Production Due to Training

    PubMed Central

    Smolka, Lukasz; Borkowski, Jacek; Zaton, Marek

    2014-01-01

    The purpose of the study was to investigate the effects of implementing additional respiratory dead space during cycloergometry-based aerobic training. The primary outcome measures were respiratory exchange ratio (RER) and carbon dioxide production (VCO2). Two groups of young healthy males: Experimental (Exp, n = 15) and Control (Con, n = 15), participated in this study. The training consisted of 12 sessions, performed twice a week for 6 weeks. A single training session consisted of continuous, constant-rate exercise on a cycle ergometer at 60% of VO2max which was maintained for 30 minutes. Subjects in Exp group were breathing through additional respiratory dead space (1200ml), while subjects in Con group were breathing without additional dead space. Pre-test and two post-training incremental exercise tests were performed for the detection of gas exchange variables. In all training sessions, pCO2 was higher and blood pH was lower in the Exp group (p < 0.001) ensuring respiratory acidosis. A 12-session training program resulted in significant increase in performance time in both groups (from 17”29 ± 1”31 to 18”47 ± 1”37 in Exp; p=0.02 and from 17”20 ± 1”18 to 18”45 ± 1”44 in Con; p = 0.02), but has not revealed a significant difference in RER and VCO2 in both post-training tests, performed at rest and during submaximal workload. We interpret the lack of difference in post-training values of RER and VCO2 between groups as an absence of inhibition in glycolysis and glycogenolysis during exercise with additional dead space. Key Points The purpose of the study was to investigate the effects of implementing additional respiratory dead space during cycloergometry-based aerobic training on respiratory exchange ratio and carbon dioxide production. In all training sessions, respiratory acidosis was gained by experimental group only. No significant difference in RER and VCO2 between experimental and control group due to the trainings. The lack of

  9. The effect of additional dead space on respiratory exchange ratio and carbon dioxide production due to training.

    PubMed

    Smolka, Lukasz; Borkowski, Jacek; Zaton, Marek

    2014-01-01

    The purpose of the study was to investigate the effects of implementing additional respiratory dead space during cycloergometry-based aerobic training. The primary outcome measures were respiratory exchange ratio (RER) and carbon dioxide production (VCO2). Two groups of young healthy males: Experimental (Exp, n = 15) and Control (Con, n = 15), participated in this study. The training consisted of 12 sessions, performed twice a week for 6 weeks. A single training session consisted of continuous, constant-rate exercise on a cycle ergometer at 60% of VO2max which was maintained for 30 minutes. Subjects in Exp group were breathing through additional respiratory dead space (1200ml), while subjects in Con group were breathing without additional dead space. Pre-test and two post-training incremental exercise tests were performed for the detection of gas exchange variables. In all training sessions, pCO2 was higher and blood pH was lower in the Exp group (p < 0.001) ensuring respiratory acidosis. A 12-session training program resulted in significant increase in performance time in both groups (from 17"29 ± 1"31 to 18"47 ± 1"37 in Exp; p=0.02 and from 17"20 ± 1"18 to 18"45 ± 1"44 in Con; p = 0.02), but has not revealed a significant difference in RER and VCO2 in both post-training tests, performed at rest and during submaximal workload. We interpret the lack of difference in post-training values of RER and VCO2 between groups as an absence of inhibition in glycolysis and glycogenolysis during exercise with additional dead space. Key PointsThe purpose of the study was to investigate the effects of implementing additional respiratory dead space during cycloergometry-based aerobic training on respiratory exchange ratio and carbon dioxide production.In all training sessions, respiratory acidosis was gained by experimental group only.No significant difference in RER and VCO2 between experimental and control group due to the trainings.The lack of difference in post

  10. Increasing addition of autochthonous to allochthonous carbon in nutrient-rich aquatic systems stimulates carbon consumption but does not alter bacterial community composition

    NASA Astrophysics Data System (ADS)

    Attermeyer, K.; Hornick, T.; Kayler, Z. E.; Bahr, A.; Zwirnmann, E.; Grossart, H.-P.; Premke, K.

    2013-08-01

    Dissolved organic carbon (DOC) concentrations - mainly of terrestrial origin - are increasing worldwide in inland waters. The biodegradability of the DOC varies depending on quantity and chemical quality. Heterotrophic bacteria are the main consumers of DOC and thus determine DOC temporal dynamics and availability for higher trophic levels. It is therefore crucial to understand the processes controlling the bacterial turnover of additional allochthonous and autochthonous DOC in aquatic systems. Our aim was to study bacterial carbon (C) turnover with respect to DOC quantity and chemical quality using both allochthonous and autochthonous DOC sources. We incubated a natural bacterial community with allochthonous C (13C-labeled beech leachate) and increased concentrations and pulses (intermittent occurrence of organic matter input) of autochthonous C (algae lysate). We then determined bacterial carbon consumption, activities, and community composition together with the carbon flow through bacteria using stable C isotopes. The chemical analysis of single sources revealed differences in aromaticity and fractions of low and high molecular weight substances (LMWS and HMWS, respectively) between allochthonous and autochthonous C sources. In parallel to these differences in chemical composition, we observed a higher availability of allochthonous C as evidenced by increased DOC consumption and bacterial growth efficiencies (BGE) when solely allochthonous C was provided. In treatments with mixed sources, rising concentrations of added autochthonous DOC resulted in a further, significant increase in bacterial DOC consumption from 52 to 68% when nutrients were not limiting. This rise was accompanied by a decrease in the humic substances (HS) fraction and an increase in bacterial biomass. Stable C isotope analyses of phospholipid fatty acids (PLFA) and respired dissolved inorganic carbon (DIC) supported a preferential assimilation of autochthonous C and respiration of the

  11. Evaluation of the nanotube intrinsic resistance across the tip-carbon nanotube-metal substrate junction by Atomic Force Microscopy

    PubMed Central

    2011-01-01

    Using an atomic force microscope (AFM) at a controlled contact force, we report the electrical signal response of multi-walled carbon nanotubes (MWCNTs) disposed on a golden thin film. In this investigation, we highlight first the theoretical calculation of the contact resistance between two types of conductive tips (metal-coated and doped diamond-coated), individual MWCNTs and golden substrate. We also propose a circuit analysis model to schematize the «tip-CNT-substrate» junction by means of a series-parallel resistance network. We estimate the contact resistance R of each contribution of the junction such as Rtip-CNT, RCNT-substrate and Rtip-substrate by using the Sharvin resistance model. Our final objective is thus to deduce the CNT intrinsic radial resistance taking into account the calculated electrical resistance values with the global resistance measured experimentally. An unwished electrochemical phenomenon at the tip apex has also been evidenced by performing measurements at different bias voltages with diamond tips. For negative tip-substrate bias, a systematic degradation in color and contrast of the electrical cartography occurs, consisting of an important and non-reversible increase of the measured resistance. This effect is attributed to the oxidation of some amorphous carbon areas scattered over the diamond layer covering the tip. For a direct polarization, the CNT and substrate surface can in turn be modified by an oxidation mechanism. PMID:21711904

  12. The Fe-V Cofactor of Vanadium Nitrogenase Contains an Interstitial Carbon Atom.

    PubMed

    Rees, Julian A; Bjornsson, Ragnar; Schlesier, Julia; Sippel, Daniel; Einsle, Oliver; DeBeer, Serena

    2015-11-02

    The first direct evidence is provided for the presence of an interstitial carbide in the Fe-V cofactor of Azotobacter vinelandii vanadium nitrogenase. As for our identification of the central carbide in the Fe-Mo cofactor, we employed Fe Kβ valence-to-core X-ray emission spectroscopy and density functional theory calculations, and herein report the highly similar spectra of both variants of the cofactor-containing protein. The identification of an analogous carbide, and thus an atomically homologous active site in vanadium nitrogenase, highlights the importance and influence of both the interstitial carbide and the identity of the heteroatom on the electronic structure and catalytic activity of the enzyme.

  13. The Fe–V Cofactor of Vanadium Nitrogenase Contains an Interstitial Carbon Atom

    PubMed Central

    Rees, Julian A; Bjornsson, Ragnar; Schlesier, Julia; Sippel, Daniel; Einsle, Oliver; DeBeer, Serena

    2015-01-01

    The first direct evidence is provided for the presence of an interstitial carbide in the Fe–V cofactor of Azotobacter vinelandii vanadium nitrogenase. As for our identification of the central carbide in the Fe–Mo cofactor, we employed Fe Kβ valence-to-core X-ray emission spectroscopy and density functional theory calculations, and herein report the highly similar spectra of both variants of the cofactor-containing protein. The identification of an analogous carbide, and thus an atomically homologous active site in vanadium nitrogenase, highlights the importance and influence of both the interstitial carbide and the identity of the heteroatom on the electronic structure and catalytic activity of the enzyme. PMID:26376620

  14. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    SciTech Connect

    Nandan, Ravi Nanda, Karuna Kar

    2015-06-24

    We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min{sup −1}. The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

  15. A novel table-top device for the single-atom detection of Carbon-14

    NASA Astrophysics Data System (ADS)

    Meyer, Fred W.; Galutschek, Ernst

    2006-05-01

    Carbon-14 labeled compounds are widely used in the pharmaceutical industry, e.g., as tracers to determine the fate of these compounds in vivo. The sensitivities of most present methods are inadequate to permit utilization of sufficiently small quantities of ^14C to avoid the issues of radioactive waste and contamination, both of which are unacceptable for environmental, health and safety, and financial reasons. A new compact ^14C detection apparatus has recently been developed that uses low-energy multicharged carbon beams with charge state of +3 or higher to eliminate molecular isobar interference at mass 14. After magnetic selection of the desired charge state, the ion beam, which will still be dominated by ^14N multicharged ions of the same charge state, is directed to an insulator single-crystal surface at grazing incidence, where efficient negative ion formation takes place without appreciable energy loss of the scattered ions. Two stages of electrostatic analysis spatially separate the desired ^14C^- ions from scattered neutrals and other background prior to their detection on a two-dimensional position-sensitive detector (2-D PSD). Unique characteristics of the apparatus are its small size, low cost, high efficiency (i.e., throughput), and ease of sample preparation, in comparison with the conventional AMS approach. Initial test results using large-area LiF and KBr single crystal targets will be presented.

  16. Enzymatic Electrosynthesis of Formic Acid through CO2 Reduction in Bioelectrochemical System (BES): Effect of Immobilization and Carbonic Anhydrase Addition.

    PubMed

    Srikanth, Sandipam; Alvarez Gallego, Yolanda; Vanbroekhoven, Karolien; Pant, Deepak

    2017-03-17

    Enzymatic electrosynthesis of formic acid from carbon dioxide (CO2) reduction using formate dehydrogenase (FDH) as catalyst at cathode both in its free and immobilized forms was studied in detail in bioelectrochemical system (BES). The essential role of solubilizing CO2 for its conversion was also studied by adding carbonic anhydrase (CA) to the FDH enzyme both in free and immobilized forms. FDH alone in the free form showed large variation in reduction current (-6.2±3.9 A/m2), while the immobilized form showed less variation (-3.8±0.5 A/m2) due to increased enzyme stability. Addition of CA with FDH increased the current consumption in both forms due to the fact that it makes the CO2 rapidly dissolve and available for the catalytic reaction of FDH. Remarkably stable current consumption was observed throughout operation when both the CA and FDH were immobilized onto the electrode (-3.9±0.2 A/m2). The product formation by the immobilized enzyme was also continued for 3 repetitive cycles indicating the longevity of the enzyme after immobilization. NADH recyclability was also clearly evidenced on the derivative voltammetric signature. Extension of this study for continuous and long-term operation may reveal more possibilities for the rapid CO2 capture and conversion.

  17. Understanding drivers of the export of dissolved organic carbon from headwater catchments in Germany using Generalised Additive Models

    NASA Astrophysics Data System (ADS)

    Selle, Benny; Tittel, Jörg; Musolff, Andreas

    2015-04-01

    In the literature, several causes of recently increasing concentrations of dissolved organic carbon (DOC) in headwaters across eastern North America and northern and central Europe have been debated. One likely driver of the widespread increase of DOC concentrations since the early to mid 1990s are decreasing depositions of acid rain resulting in an increased solubility of organic carbon compounds including humic acids. Here, we tested the hypothesis if the reduced availability of both nitrate and sulfate stimulated the reduction of ferric iron soil minerals and the mobilisation of DOC. Decreasing depositions often resulted in a reduced availability of both nitrate and sulphate, which are preferred electron acceptors in microbial decomposition processes. As iron minerals act as efficient sorbents of organic compounds in soils its reduction may have caused a release of humic substances and hence an increasing export of DOC from headwater catchments. To test this hypothesis, time series of DOC, dissolved iron, sulfate and nitrate from several German headwater catchments were examined using Generalised Additive Models. Using this modelling technique, discharge corrected time series of concentrations were represented as a sum of a seasonal and a non-linear trend component. Both, the computed trends and seasonalities supported the redox hypothesis.

  18. The Effect of Fluoroethylene Carbonate as an Additive on the Solid Electrolyte Interphase on Silicon Lithium-Ion Electrodes

    DOE PAGES

    Schroder, Kjell; Li, Juchuan; Dudney, Nancy J.; ...

    2015-08-03

    Fluoroethylene carbonate (FEC) has become a standard electrolyte additive for use with silicon negative electrodes, but how FEC affects solid electrolyte interphase (SEI) formation on the silicon anode’s surface is still not well understood. Herein, SEI formed from LiPF6-based carbonate electrolytes, with and without FEC, were investigated on 50 nm thick amorphous silicon thin film electrodes to understand the role of FEC on silicon electrode surface reactions. In contrast to previous work, anhydrous and anoxic techniques were used to prevent air and moisture contamination of prepared SEI films. This allowed for accurate characterization of the SEI structure and composition bymore » X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry depth profiling. These results show that FEC reduction leads to fluoride ion and LiF formation, consistent with previous computational and experimental results. Surprisingly, we also find that these species decrease lithium-ion solubility and increase the reactivity of the silicon surface. We conclude that the effectiveness of FEC at improving the Coulombic efficiency and capacity retention is due to fluoride ion formation from reduction of the electrolyte, which leads to the chemical attack of any silicon-oxide surface passivation layers and the formation of a kinetically stable SEI comprising predominately lithium fluoride and lithium oxide.« less

  19. Effect of Rare Earth Cerium Addition on Microstructures and Mechanical Properties of Low Carbon High Manganese Steels

    NASA Astrophysics Data System (ADS)

    Jiang, M. Z.; Yu, Y. C.; Li, H.; Ren, X.; Wang, S. B.

    2017-02-01

    Low carbon high manganese steels with different Ce contents were melted in medium frequency vacuum induction furnace. The microstructures and mechanical properties of steels were studied by OM, SEM, EDS and mechanical property testing. The results showed that the microstructures of experimental steels were refined remarkably, inclusions distributed more finely and uniformly, the tensile strength and impact toughness of tested steels both improved greatly after the addition of Ce. Thermodynamic calculation results demonstrated that Ce contained inclusions were Ce2O3 and Ce3S4, which agreed well with the results observed by SEM and EDS. By analysis of two-dimensional lattice disregistry, it was shown that the lattice misfit parameter between δ-Fe and Ce2O3, Ce3S4 are less than 6 %, which indicated that Ce2O3 and Ce3S4 could effectively act as the heterogeneous nuclei of initial δ-Fe. Therefore, the microstructures were refined significantly and the mechanical properties were improved correspondingly in Ce-added low carbon high manganese steels.

  20. The Effect of Fluoroethylene Carbonate as an Additive on the Solid Electrolyte Interphase on Silicon Lithium-Ion Electrodes

    SciTech Connect

    Schroder, Kjell; Li, Juchuan; Dudney, Nancy J.; Meng, Ying Shirley; Stevenson, Keith J.; Alvarado, Judith

    2015-08-03

    Fluoroethylene carbonate (FEC) has become a standard electrolyte additive for use with silicon negative electrodes, but how FEC affects solid electrolyte interphase (SEI) formation on the silicon anode’s surface is still not well understood. Herein, SEI formed from LiPF6-based carbonate electrolytes, with and without FEC, were investigated on 50 nm thick amorphous silicon thin film electrodes to understand the role of FEC on silicon electrode surface reactions. In contrast to previous work, anhydrous and anoxic techniques were used to prevent air and moisture contamination of prepared SEI films. This allowed for accurate characterization of the SEI structure and composition by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry depth profiling. These results show that FEC reduction leads to fluoride ion and LiF formation, consistent with previous computational and experimental results. Surprisingly, we also find that these species decrease lithium-ion solubility and increase the reactivity of the silicon surface. We conclude that the effectiveness of FEC at improving the Coulombic efficiency and capacity retention is due to fluoride ion formation from reduction of the electrolyte, which leads to the chemical attack of any silicon-oxide surface passivation layers and the formation of a kinetically stable SEI comprising predominately lithium fluoride and lithium oxide.

  1. In situ electron microscopy studies of calcium carbonate precipitation from aqueous solution with and without organic additives.

    PubMed

    Verch, Andreas; Morrison, Ian E G; Locht, Renee van de; Kröger, Roland

    2013-08-01

    For the understanding of mineral formation processes from solution it is important to obtain a deeper insight into the dynamics of crystal growth. In this study we applied for this purpose a novel atmospheric scanning electron microscope that allows the investigation of CaCO3 particle formation in solution under atmospheric conditions with a resolution of approximately 10nm. Furthermore it permits the in situ observation of the dynamics of crystal evolution. With this tool the precipitation of CaCO3 was studied in the absence and presence of additives, namely poly(acrylic acid) and poly(styrene sulfonate-co-maleic acid) which are known to influence the crystal growth rate and morphology. We determined particle growth rates and investigated the formation and dissolution dynamics of an observed transient phase, believed to be amorphous calcium carbonate. This technique also enabled us to study the depletion zones, areas of lower intensity due to reduced ion concentrations. Ion flux rates were obtained from the depletion zone width, which amounted to several μm assuming the formation and dissolution dynamics of amorphous calcium carbonate being the rate determining process. This assumption was confirmed since the obtained fluxes were found to be in good agreement with fluxes derived from the experimentally observed crystal growth rates.

  2. Effects of substrate addition on soil respiratory carbon release under long-term warming and clipping in a tallgrass prairie.

    PubMed

    Jia, Xiaohong; Zhou, Xuhui; Luo, Yiqi; Xue, Kai; Xue, Xian; Xu, Xia; Yang, Yuanhe; Wu, Liyou; Zhou, Jizhong

    2014-01-01

    Regulatory mechanisms of soil respiratory carbon (C) release induced by substrates (i.e., plant derived substrates) are critical for predicting ecosystem responses to climate change, but the mechanisms are not well understood. In this study, we sampled soils from a long-term field manipulative experiment and conducted a laboratory incubation to explore the role of substrate supply in regulating the differences in soil C release among the experimental treatments, including control, warming, clipping, and warming plus clipping. Three types of substrates (glucose, C3 and C4 plant materials) were added with an amount equal to 1% of soil dry weight under the four treatments. We found that the addition of all three substrates significantly stimulated soil respiratory C release in all four warming and clipping treatments. In soils without substrate addition, warming significantly stimulated soil C release but clipping decreased it. However, additions of glucose and C3 plant materials (C3 addition) offset the warming effects, whereas C4 addition still showed the warming-induced stimulation of soil C release. Our results suggest that long-term warming may inhibit microbial capacity for decomposition of C3 litter but may enhance it for decomposition of C4 litter. Such warming-induced adaptation of microbial communities may weaken the positive C-cycle feedback to warming due to increased proportion of C4 species in plant community and decreased litter quality. In contrast, clipping may weaken microbial capacity for warming-induced decomposition of C4 litter but may enhance it for C3 litter. Warming- and clipping-induced shifts in microbial metabolic capacity may be strongly associated with changes in plant species composition and could substantially influence soil C dynamics in response to global change.

  3. Carbon dioxide insufflation for chronic subdural haematoma: a simple addition to burr-hole irrigation and closed-system drainage.

    PubMed

    Kubo, S; Takimoto, H; Nakata, H; Yoshimine, T

    2003-12-01

    Burr-hole irrigation with closed-system drainage is a common surgical method used for chronic subdural haematoma. However, the subdural space with air that entered during surgery sometimes remains for a prolonged period after surgery and may hamper uncomplicated healing of the subdural space. We combined a simple procedure, insufflation of carbon dioxide (CO2) into the subdural space through a drainage catheter, with conventional burr-hole irrigation and closed-system drainage. By this additional procedure, both the subdural space and the gas within the space decreased rapidly, and the subdural drain could be removed within 24 h. By promoting obliteration of the subdural space, this simple combined technique may contribute to early recovery and discharge of patients, and to a reduction in the recurrence rate of the disease.

  4. Evaluated kinetics of terminal and non-terminal addition of hydrogen atoms to 1-alkenes: a shock tube study of H + 1-butene.

    PubMed

    Manion, Jeffrey A; Awan, Iftikhar A

    2015-01-22

    Single-pulse shock tube methods have been used to thermally generate hydrogen atoms and investigate the kinetics of their addition reactions with 1-butene at temperatures of 880 to 1120 K and pressures of 145 to 245 kPa. Rate parameters for the unimolecular decomposition of 1-butene are also reported. Addition of H atoms to the π bond of 1-butene results in displacement of either methyl or ethyl depending on whether addition occurs at the terminal or nonterminal position. Postshock monitoring of the initial alkene products has been used to determine the relative and absolute reaction rates. Absolute rate constants have been derived relative to the reference reaction of displacement of methyl from 1,3,5-trimethylbenzene (135TMB). With k(H + 135TMB → m-xylene + CH3) = 6.7 × 10(13) exp(-3255/T) cm(3) mol(-1) s(-1), we find the following: k(H + 1-butene → propene + CH3) = k10 = 3.93 × 10(13) exp(-1152 K/T) cm(3) mol(-1) s(-1), [880-1120 K; 145-245 kPa]; k(H + 1-butene → ethene + C2H5) = k11 = 3.44 × 10(13) exp(-1971 K/T) cm(3) mol(-1) s(-1), [971-1120 K; 145-245 kPa]; k10/k11 = 10((0.058±0.059)) exp [(818 ± 141) K/T), 971-1120 K. Uncertainties (2σ) in the absolute rate constants are about a factor of 1.5, while the relative rate constants should be accurate to within ±15%. The displacement rate constants are shown to be very close to the high pressure limiting rate constants for addition of H, and the present measurements are the first direct determination of the branching ratio for 1-olefins at high temperatures. At 1000 K, addition to the terminal site is favored over the nonterminal position by a factor of 2.59 ± 0.39, where the uncertainty is 2σ and includes possible systematic errors. Combining the present results with evaluated data from the literature pertaining to temperatures of <440 K leads us to recommend the following: k∞(H + 1-butene → 2-butyl) = 1.05 × 10(9)T(1.40) exp(-366/T) cm(3) mol(-1) s(-1), [220-2000 K]; k∞(H + 1-butene → 1

  5. Role of defects in the process of graphene growth on hexagonal boron nitride from atomic carbon

    SciTech Connect

    Dabrowski, J. Lippert, G.; Schroeder, T.; Lupina, G.

    2014-11-10

    Hexagonal boron nitride (h-BN) is an attractive substrate for graphene, as the interaction between these materials is weak enough for high carrier mobility to be retained in graphene but strong enough to allow for some epitaxial relationship. We deposited graphene on exfoliated h-BN by molecular beam epitaxy (MBE), we analyzed the atomistic details of the process by ab initio density functional theory (DFT), and we linked the DFT and MBE results by random walk theory. Graphene appears to nucleate around defects in virgin h-BN. The DFT analysis reveals that sticking of carbon to perfect h-BN is strongly reduced by desorption, so that pre-existing seeds are needed for the nucleation. The dominant nucleation seeds are C{sub N}C{sub B} and O{sub N}C{sub N} pairs and B{sub 2}O{sub 3} inclusions in the virgin substrate.

  6. Modeling external carbon addition in biological nutrient removal processes with an extension of the international water association activated sludge model.

    PubMed

    Swinarski, M; Makinia, J; Stensel, H D; Czerwionka, K; Drewnowski, J

    2012-08-01

    The aim of this study was to expand the International Water Association Activated Sludge Model No. 2d (ASM2d) to account for a newly defined readily biodegradable substrate that can be consumed by polyphosphate-accumulating organisms (PAOs) under anoxic and aerobic conditions, but not under anaerobic conditions. The model change was to add a new substrate component and process terms for its use by PAOs and other heterotrophic bacteria under anoxic and aerobic conditions. The Gdansk (Poland) wastewater treatment plant (WWTP), which has a modified University of Cape Town (MUCT) process for nutrient removal, provided field data and mixed liquor for batch tests for model evaluation. The original ASM2d was first calibrated under dynamic conditions with the results of batch tests with settled wastewater and mixed liquor, in which nitrate-uptake rates, phosphorus-release rates, and anoxic phosphorus uptake rates were followed. Model validation was conducted with data from a 96-hour measurement campaign in the full-scale WWTP. The results of similar batch tests with ethanol and fusel oil as the external carbon sources were used to adjust kinetic and stoichiometric coefficients in the expanded ASM2d. Both models were compared based on their predictions of the effect of adding supplemental carbon to the anoxic zone of an MUCT process. In comparison with the ASM2d, the new model better predicted the anoxic behaviors of carbonaceous oxygen demand, nitrate-nitrogen (NO3-N), and phosphorous (PO4-P) in batch experiments with ethanol and fusel oil. However, when simulating ethanol addition to the anoxic zone of a full-scale biological nutrient removal facility, both models predicted similar effluent NO3-N concentrations (6.6 to 6.9 g N/m3). For the particular application, effective enhanced biological phosphorus removal was predicted by both models with external carbon addition but, for the new model, the effluent PO4-P concentration was approximately one-half of that found from

  7. Initial evaluation and comparison of plasma damage to atomic layer carbon materials using conventional and low T{sub e} plasma sources

    SciTech Connect

    Jagtiani, Ashish V.; Miyazoe, Hiroyuki; Chang, Josephine; Farmer, Damon B.; Engel, Michael; Neumayer, Deborah; Han, Shu-Jen; Engelmann, Sebastian U. Joseph, Eric A.; Boris, David R.; Hernández, Sandra C.; Walton, Scott G.; Lock, Evgeniya H.

    2016-01-15

    The ability to achieve atomic layer precision is the utmost goal in the implementation of atomic layer etch technology. Carbon-based materials such as carbon nanotubes (CNTs) and graphene are single atomic layers of carbon with unique properties and, as such, represent the ultimate candidates to study the ability to process with atomic layer precision and assess impact of plasma damage to atomic layer materials. In this work, the authors use these materials to evaluate the atomic layer processing capabilities of electron beam generated plasmas. First, the authors evaluate damage to semiconducting CNTs when exposed to beam-generated plasmas and compare these results against the results using typical plasma used in semiconductor processing. The authors find that the beam generated plasma resulted in significantly lower current degradation in comparison to typical plasmas. Next, the authors evaluated the use of electron beam generated plasmas to process graphene-based devices by functionalizing graphene with fluorine, nitrogen, or oxygen to facilitate atomic layer deposition (ALD). The authors found that all adsorbed species resulted in successful ALD with varying impact on the transconductance of the graphene. Furthermore, the authors compare the ability of both beam generated plasma as well as a conventional low ion energy inductively coupled plasma (ICP) to remove silicon nitride (SiN) deposited on top of the graphene films. Our results indicate that, while both systems can remove SiN, an increase in the D/G ratio from 0.08 for unprocessed graphene to 0.22 to 0.26 for the beam generated plasma, while the ICP yielded values from 0.52 to 1.78. Generally, while some plasma-induced damage was seen for both plasma sources, a much wider process window as well as far less damage to CNTs and graphene was observed when using electron beam generated plasmas.

  8. Determination of cadmium and lead in urine samples after dispersive solid-liquid extraction on multiwalled carbon nanotubes by slurry sampling electrothermal atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Álvarez Méndez, J.; Barciela García, J.; García Martín, S.; Peña Crecente, R. M.; Herrero Latorre, C.

    2015-04-01

    A new method for the determination of Cd and Pb in urine samples has been developed. The method involves dispersive solid-phase extraction (DSPE), slurry sampling (SS), and subsequent electrothermal atomic absorption spectrometry (ETAAS). Oxidized multiwalled carbon nanotubes (MWCNTs) were used as the sorbent material. The isolated MWCNT/analyte aggregates were treated with nitric acid to form a slurry and both metals were determined directly by injecting the slurry into the ETAAS-atomizer. The parameters that influence the adsorption of the metals on MWCNTs in the DSPE process, the formation and extraction of the slurry, and the ETAAS conditions were studied by different factorial design strategies. The detection and quantification limits obtained for Cd under optimized conditions were 9.7 and 32.3 ng L- 1, respectively, and for Pb these limits were 0.13 and 0.43 μg L- 1. The preconcentration factors achieved were 3.9 and 5.4. The RSD values (n = 10) were less than 4.1% and 5.9% for Cd and Pb, respectively. The accuracy of the method was assessed in recovery studies, with values in the range 96-102% obtained for Cd and 97-101% for Pb. In addition, the analysis of certified reference materials gave consistent results. The DSPE-SS-ETAAS method is a novel and useful strategy for the determination of Pb and Cd at low levels in human urine samples. The method is sensitive, fast, and free of matrix interferences, and it avoids the tedious and time-consuming on-column adsorption and elution steps associated with commonly used SPE procedures. The proposed method was used to determine Cd and Pb in urine samples of unexposed healthy people and satisfactory results were obtained.

  9. Atomic and Molecular Layer Deposition for Enhanced Lithium Ion Battery Electrodes and Development of Conductive Metal Oxide/Carbon Composites

    NASA Astrophysics Data System (ADS)

    Travis, Jonathan

    The performance and safety of lithium-ion batteries (LIBs) are dependent on interfacial processes at the positive and negative electrodes. For example, the surface layers that form on cathodes and anodes are known to affect the kinetics and capacity of LIBs. Interfacial reactions between the electrolyte and the electrodes are also known to initiate electrolyte combustion during thermal runaway events that compromise battery safety. Atomic layer deposition (ALD) and molecular layer deposition (MLD) are thin film deposition techniques based on sequential, self-limiting surface reactions. ALD and MLD can deposit ultrathin and conformal films on high aspect ratio and porous substrates such as composite particulate electrodes in lithium-ion batteries. The effects of electrode surface modification via ALD and MLD are studied using a variety of techniques. It was found that sub-nm thick coatings of Al2O 3 deposited via ALD have beneficial effects on the stability of LIB anodes and cathodes. These same Al2O3 ALD films were found to improve the safety of graphite based anodes through prevention of exothermic solid electrolyte interface (SEI) degradation at elevated temperatures. Ultrathin and conformal metal alkoxide polymer films known as "metalcones" were grown utilizing MLD techniques with trimethylaluminum (TMA) or titanium tetrachloride (TiCl4) and organic diols or triols, such as ethylene glycol (EG), glycerol (GL) or hydroquinone (HQ), as the reactants. Pyrolysis of these metalcone films under inert gas conditions led to the development of conductive metal oxide/carbon composites. The composites were found to contain sp2 carbon using micro-Raman spectroscopy in the pyrolyzed films with pyrolysis temperatures ≥ 600°C. Four point probe measurements demonstrated that the graphitic sp2 carbon domains in the metalcone films grown using GL and HQ led to significant conductivity. The pyrolysis of conformal MLD films to obtain conductive metal oxide/carbon composite films

  10. Atoms in Action

    SciTech Connect

    2009-01-01

    This movie produced with Berkeley Lab's TEAM 0.5 microscope shows the growth of a hole and the atomic edge reconstruction in a graphene sheet. An electron beam focused to a spot on the sheet blows out the exposed carbon atoms to make the hole. The carbon atoms then reposition themselves to find a stable configuration. http://newscenter.lbl.gov/press-releases/2009/03/26/atoms-in-action/

  11. Metal atom oxidation laser

    DOEpatents

    Jensen, R.J.; Rice, W.W.; Beattie, W.H.

    1975-10-28

    A chemical laser which operates by formation of metal or carbon atoms and reaction of such atoms with a gaseous oxidizer in an optical resonant cavity is described. The lasing species are diatomic or polyatomic in nature and are readily produced by exchange or other abstraction reactions between the metal or carbon atoms and the oxidizer. The lasing molecules may be metal or carbon monohalides or monoxides. (auth)

  12. Metal atom oxidation laser

    DOEpatents

    Jensen, R.J.; Rice, W.W.; Beattie, W.H.

    1975-10-28

    A chemical laser which operates by formation of metal or carbon atoms and reaction of such atoms with a gaseous oxidizer in an optical resonant cavity is described. The lasing species are diatomic or polyatomic in nature and are readily produced by exchange or other abstraction reactions between the metal or carbon atoms and the oxidizer. The lasing molecules may be metal or carbon monohalides or monoxides.

  13. Reaction of benzene with atomic carbon: pathways to fulvenallene and the fulvenallenyl radical in extraterrestrial atmospheres and the interstellar medium.

    PubMed

    da Silva, Gabriel

    2014-06-05

    The reaction of benzene with ground-state atomic carbon, C((3)P), has been investigated using the G3X-K composite quantum chemical method. A suite of novel energetically favorable pathways that lead to previously unconsidered products are identified. Reaction is initiated by barrierless C atom cycloaddition to benzene on the triplet surface, producing a vibrationally excited [C7H6]* adduct that can dissociate to the cycloheptatrienyl radical (+ H) via a relatively loose transition state 4.4 kcal mol(-1) below the reactant energies. This study also identifies that this reaction adduct can isomerize to generate five-membered ring intermediates that can further dissociate to the global C7H5 minima, the fulvenallenyl radical (+ H), or to c-C5H4 and acetylene, with limiting barriers around 20 and 10 kcal mol(-1) below the reactants, respectively. If intersystem crossing to the singlet surface occurs, isomerization pathways that are lower-yet in energy are available leading to the C7H6 minima fulvenallene, with all barriers over 40 kcal mol(-1) below the reactants. From here further barrierless fragmentation to fulvenallenyl + H can proceed at ca. 25 kcal mol(-1) below the reactants. In the reducing atmospheres of planets like Jupiter and satellites like Titan, where benzene and C((3)P) are both expected, it is proposed that fulvenallene and the fulvenallenyl radical would be the dominant products of the C6H6 + C((3)P) reaction. Fulvenallenyl may also be a significant reaction product under collision-free conditions representative of the interstellar medium, although further work is required here to confirm the identity of the C7H5 radical product.

  14. Effect of supplementary carbon addition in the treatment of low C/N high-technology industrial wastewater by MBR.

    PubMed

    Kumar, Mathava; Lee, Pei-Yun; Fukusihma, Toshikazu; Whang, Liang-Ming; Lin, Jih-Gaw

    2012-06-01

    The effect of supplementary carbon addition for the treatment of high-technology industrial wastewater in a membrane bioreactor (MBR) was investigated. The MBR was operated for 302 days under different C/N (BOD(L)/NH(4)(+)-N) ratios, i.e. 0.9-1 to 20 days, 1.6-21 to 42 days, 2.9-43 to 82 days, 3.6-83 to 141 days, 4.8-165 to 233 days and 9.3-240 to 302 days. Irrespective of the C/N ratios investigated, SS and BOD(5) removal efficiencies were above 95% and above 80% COD removal efficiency was observed. In addition, complete nitrification was observed throughout the investigation. However, denitrification and total nitrogen removal efficiencies reached their maximum values at the highest C/N ratio (9.3) investigated. Real-time PCR analysis revealed 10 times higher ammonia oxidizing bacteria to total bacteria ratio under the highest C/N ratio condition (9.3) compared to the low C/N ratio condition (1.6).

  15. Corrosion and Heat Transfer Characteristics of Water Dispersed with Carboxylate Additives and Multi Walled Carbon Nano Tubes

    NASA Astrophysics Data System (ADS)

    Moorthy, Chellapilla V. K. N. S. N.; Srinivas, Vadapalli

    2016-10-01

    This paper summarizes a recent work on anti-corrosive properties and enhanced heat transfer properties of carboxylated water based nanofluids. Water mixed with sebacic acid as carboxylate additive found to be resistant to corrosion and suitable for automotive environment. The carboxylated water is dispersed with very low mass concentration of carbon nano tubes at 0.025, 0.05 and 0.1 %. The stability of nanofluids in terms of zeta potential is found to be good with carboxylated water compared to normal water. The heat transfer performance of nanofluids is carried out on an air cooled heat exchanger similar to an automotive radiator with incoming air velocities across radiator at 5, 10 and 15 m/s. The flow Reynolds number of water is in the range of 2500-6000 indicating developing flow regime. The corrosion resistance of nanofluids is found to be good indicating its suitability to automotive environment. There is a slight increase in viscosity and marginal decrease in the specific heat of nanofluids with addition of carboxylate as well as CNTs. Significant improvement is observed in the thermal conductivity of nanofluids dispersed with CNTs. During heat transfer experimentation, the inside heat transfer coefficient and overall heat transfer coefficient has also improved markedly. It is also found that the velocity of air and flow rate of coolant plays an important role in enhancement of the heat transfer coefficient and overall heat transfer coefficient.

  16. Influence of Nb Additions on Microstructural Evolution of a V-Microalloyed High-Carbon Wire Steel During Patenting

    NASA Astrophysics Data System (ADS)

    Miller, Stephanie L.; de Moor, Emmanuel

    2014-08-01

    This study investigated the feasibility of microalloying strategies for improving the strength of high-carbon wire products subjected to industrial patenting heat treatments for two eutectoid steels: a 0.8C-0.5Mn-0.2Cr-0.08 V alloy (wt.%) and the same composition with an additional 100 ppm Nb. A Gleeble 3500 thermomechanical simulator (Dynamic Systems Inc., Poestenkill, NY, USA) was used to perform heat treatments consisting of a 30 s austenitization at 1093 °C, 950 °C, or 880 °C followed by a 15 s isothermal transformation step at 650 °C, 625 °C, 600 °C, or 575 °C. Vickers hardness, field-emission scanning electron microscopy, and pearlite interlamellar spacing measurements were conducted to assess the effects of the heat treatments. Niobium microalloying additions were found to provide no hardness increase, but they extended the pearlitic regime to lower isothermal transformation temperatures.

  17. Carbon isotope ratios suggest no additional methane from boreal wetlands during the rapid Greenland Interstadial 21.2

    NASA Astrophysics Data System (ADS)

    Sperlich, Peter; Schaefer, Hinrich; Mikaloff Fletcher, Sara E.; Guillevic, Myriam; Lassey, Keith; Sapart, Célia J.; Röckmann, Thomas; Blunier, Thomas

    2015-11-01

    Samples from two Greenland ice cores (NEEM and NGRIP) have been measured for methane carbon isotope ratios (δ13C-CH4) to investigate the CH4 mixing ratio anomaly during Greenland Interstadial (GI) 21.2 (85,000 years before present). This extraordinarily rapid event occurred within 150 years, comprising a CH4 mixing ratio pulse of 150 ppb (˜25%). Our new measurements disclose a concomitant shift in δ13C-CH4 of 1‰. Keeling plot analyses reveal the δ13C of the additional CH4 source constituting the CH4 anomaly as -56.8 ± 2.8‰, which we confirm by means of a previously published box model. We propose tropical wetlands as the most probable additional CH4 source during GI-21.2 and present independent evidence that suggests that tropical wetlands in South America and Asia have played a key role. We find no evidence that boreal CH4 sources, such as permafrost degradation, contributed significantly to the atmospheric CH4 increase, despite the pronounced warming in the Northern Hemisphere during GI-21.2.

  18. How does the exchange of one oxygen atom with sulfur affect the catalytic cycle of carbonic anhydrase?

    PubMed

    Schenk, Stephan; Kesselmeier, Jürgen; Anders, Ernst

    2004-06-21

    We have extended our investigations of the carbonic anhydrase (CA) cycle with the model system [(H(3)N)(3)ZnOH](+) and CO(2) by studying further heterocumulenes and catalysts. We investigated the hydration of COS, an atmospheric trace gas. This reaction plays an important role in the global COS cycle since biological consumption, that is, uptake by higher plants, algae, lichens, and soil, represents the dominant terrestrial sink for this gas. In this context, CA has been identified by a member of our group as the key enzyme for the consumption of COS by conversion into CO(2) and H(2)S. We investigated the hydration mechanism of COS by using density functional theory to elucidate the details of the catalytic cycle. Calculations were first performed for the uncatalyzed gas phase reaction. The rate-determining step for direct reaction of COS with H(2)O has an energy barrier of deltaG=53.2 kcal mol(-1). We then employed the CA model system [(H(3)N)(3)ZnOH](+) (1) and studied the effect on the catalytic hydration mechanism of replacing an oxygen atom with sulfur. When COS enters the carbonic anhydrase cycle, the sulfur atom is incorporated into the catalyst to yield [(H(3)N)(3)ZnSH](+) (27) and CO(2). The activation energy of the nucleophilic attack on COS, which is the rate-determining step, is somewhat higher (20.1 kcal mol(-1) in the gas phase) than that previously reported for CO(2). The sulfur-containing model 27 is also capable of catalyzing the reaction of CO(2) to produce thiocarbonic acid. A larger barrier has to be overcome for the reaction of 27 with CO(2) compared to that for the reaction of 1 with CO(2). At a well-defined stage of this cycle, a different reaction path can emerge: a water molecule helps to regenerate the original catalyst 1 from 27, a process accompanied by the formation of thiocarbonic acid. We finally demonstrate that nature selected a surprisingly elegant and efficient group of reactants, the [L(3)ZnOH](+)/CO(2)/H(2)O system, that helps

  19. Self-assembly of endohedral metallofullerenes: a decisive role of cooling gas and metal–carbon bonding† †Electronic supplementary information (ESI) available: Additional information on metal–carbon bonding and MD simulations. See DOI: 10.1039/c5nr08645k Click here for additional data file.

    PubMed Central

    Deng, Qingming; Heine, Thomas

    2016-01-01

    The endohedral metallofullerene (EMF) self-assembly process in Sc/carbon vapor in the presence and absence of an inert cooling gas (helium) is systematically investigated using quantum chemical molecular dynamics simulations. It is revealed that the presence of He atoms accelerates the formation of pentagons and hexagons and reduces the size of the self-assembled carbon cages in comparison with analogous He-free simulations. As a result, the Sc/C/He system simulations produce a larger number of successful trajectories (i.e. leading to Sc-EMFs) with more realistic cage-size distribution than simulations of the Sc/C system. The main Sc encapsulation mechanism involves nucleation of several hexagons and pentagons with Sc atoms already at the early stages of carbon vapor condensation. In such proto-cages, both Sc–C σ-bonds and coordination bonds between Sc atoms and the π-system of the carbon network are present. Sc atoms are thus rather labile and can move along the carbon network, but the overall bonding is sufficiently strong to prevent dissociation even at temperatures around 2000 kelvin. Further growth of the fullerene cage results in the encapsulation of one or two Sc atoms within the fullerene. In agreement with experimental studies, an extension of the simulations to Fe and Ti as the metal component showed that Fe-EMFs are not formed at all, whereas Ti is prone to form Ti-EMFs with small cage sizes, including Ti@C28-T d and Ti@C30-C 2v(3). PMID:26815243

  20. Seasonality, Rather than Nutrient Addition or Vegetation Types, Influenced Short-Term Temperature Sensitivity of Soil Organic Carbon Decomposition.

    PubMed

    Qian, Yu-Qi; He, Feng-Peng; Wang, Wei

    2016-01-01

    The response of microbial respiration from soil organic carbon (SOC) decomposition to environmental changes plays a key role in predicting future trends of atmospheric CO2 concentration. However, it remains uncertain whether there is a universal trend in the response of microbial respiration to increased temperature and nutrient addition among different vegetation types. In this study, soils were sampled in spring, summer, autumn and winter from five dominant vegetation types, including pine, larch and birch forest, shrubland, and grassland, in the Saihanba area of northern China. Soil samples from each season were incubated at 1, 10, and 20°C for 5 to 7 days. Nitrogen (N; 0.035 mM as NH4NO3) and phosphorus (P; 0.03 mM as P2O5) were added to soil samples, and the responses of soil microbial respiration to increased temperature and nutrient addition were determined. We found a universal trend that soil microbial respiration increased with increased temperature regardless of sampling season or vegetation type. The temperature sensitivity (indicated by Q10, the increase in respiration rate with a 10°C increase in temperature) of microbial respiration was higher in spring and autumn than in summer and winter, irrespective of vegetation type. The Q10 was significantly positively correlated with microbial biomass and the fungal: bacterial ratio. Microbial respiration (or Q10) did not significantly respond to N or P addition. Our results suggest that short-term nutrient input might not change the SOC decomposition rate or its temperature sensitivity, whereas increased temperature might significantly enhance SOC decomposition in spring and autumn, compared with winter and summer.

  1. Seasonality, Rather than Nutrient Addition or Vegetation Types, Influenced Short-Term Temperature Sensitivity of Soil Organic Carbon Decomposition

    PubMed Central

    He, Feng-Peng; Wang, Wei

    2016-01-01

    The response of microbial respiration from soil organic carbon (SOC) decomposition to environmental changes plays a key role in predicting future trends of atmospheric CO2 concentration. However, it remains uncertain whether there is a universal trend in the response of microbial respiration to increased temperature and nutrient addition among different vegetation types. In this study, soils were sampled in spring, summer, autumn and winter from five dominant vegetation types, including pine, larch and birch forest, shrubland, and grassland, in the Saihanba area of northern China. Soil samples from each season were incubated at 1, 10, and 20°C for 5 to 7 days. Nitrogen (N; 0.035 mM as NH4NO3) and phosphorus (P; 0.03 mM as P2O5) were added to soil samples, and the responses of soil microbial respiration to increased temperature and nutrient addition were determined. We found a universal trend that soil microbial respiration increased with increased temperature regardless of sampling season or vegetation type. The temperature sensitivity (indicated by Q10, the increase in respiration rate with a 10°C increase in temperature) of microbial respiration was higher in spring and autumn than in summer and winter, irrespective of vegetation type. The Q10 was significantly positively correlated with microbial biomass and the fungal: bacterial ratio. Microbial respiration (or Q10) did not significantly respond to N or P addition. Our results suggest that short-term nutrient input might not change the SOC decomposition rate or its temperature sensitivity, whereas increased temperature might significantly enhance SOC decomposition in spring and autumn, compared with winter and summer. PMID:27070782

  2. Restricted access carbon nanotubes for direct extraction of cadmium from human serum samples followed by atomic absorption spectrometry analysis.

    PubMed

    Barbosa, Adriano F; Barbosa, Valéria M P; Bettini, Jefferson; Luccas, Pedro O; Figueiredo, Eduardo C

    2015-01-01

    In this paper, we propose a new sorbent that is able to extract metal ions directly from untreated biological fluids, simultaneously excluding all proteins from these samples. The sorbent was obtained through the modification of carbon nanotubes (CNTs) with an external bovine serum albumin (BSA) layer, resulting in restricted access carbon nanotubes (RACNTs). The BSA layer was fixed through the interconnection between the amine groups of the BSA using glutaraldehyde as cross-linker. When a protein sample is percolated through a cartridge containing RACNTs and the sample pH is higher than the isoelectric point of the proteins, both proteins from the sample and the BSA layer are negatively ionized. Thus, an electrostatic repulsion prevents the interaction between the proteins from the sample on the RACNTs surface. At the same time, metal ions are adsorbed in the CNTs (core) after their passage through the chains of proteins. The Cd(2+) ion was selected for a proof-of-principle case to test the suitability of the RACNTs due to its toxicological relevance. RACNTs were able to extract Cd(2+) and exclude almost 100% of the proteins from the human serum samples in an online solid-phase extraction system coupled with thermospray flame furnace atomic absorption spectrometry. The limits of detection and quantification were 0.24 and 0.80 μg L(-1), respectively. The sampling frequency was 8.6h(-1), and the intra- and inter-day precisions at the 0.80, 15.0, and 30.0 μg L(-1) Cd(2+) levels were all lower than 10.1% (RSD). The recoveries obtained for human blood serum samples fortified with Cd(2+) ranged from 85.0% to 112.0%. The method was successfully applied to analyze Cd(2+) directly from six human blood serum samples without any pretreatment, and the observed concentrations ranged from

  3. Interaction of carbon atoms with Fe n, Fe n-, and Fe n+ clusters ( n=1-6)

    NASA Astrophysics Data System (ADS)

    Gutsev, Gennady L.; Bauschlicher, Charles W.

    2003-06-01

    The electronic and geometrical structures of the ground and exited states of Fe nC, Fe nC -, and Fe nC + ( n=1-6) are computed using density functional theory (DFT). Several exchange-correlation functionals are tested on FeC, for which a number of experimental results are available for comparison. Fe 2C and Fe 2C - have triangular high-spin ground states, while the ground state of Fe 2C + is a linear asymmetric Fe-C-Fe doublet whose spins at the iron sites are antiferromagnetically coupled. The natural bond analysis (NBO) allows us to qualitatively describe the nature of super exchange coupling in Fe 2C +. There is a competition between twofold and threefold sites in the Fe 3C species. Carbon is threefold coordinated in the Fe 4C and Fe 6C species, while it is fourfold coordinated in the Fe 5C clusters. Generally, attachment of a carbon atom reduces the number of unpaired electrons of an iron cluster. The maximum reduction of four is found for the largest cluster, Fe 6C. The C-Fe n bond energies in the neutral clusters are rather high, ranging from 5.5 (Fe 2C) to 6.5 eV (Fe 6C). These energies are not significantly affected by attachment or detachment of an electron to/from a Fe nC cluster. Surprisingly, the Fe-Fe n-1 , Fe-Fe n-1 C, and Fe-Fe nC bond energies are found to be nearly the same for given n. The results of our computations are in reasonable agreement with experimental data.

  4. Atomic layer deposition of high-k dielectrics on single-walled carbon nanotubes: a Raman study.

    PubMed

    Liyanage, Luckshitha Suriyasena; Cott, Daire J; Delabie, Annelies; Van Elshocht, Sven; Bao, Zhenan; Wong, H-S Philip

    2013-06-21

    Single-wall carbon nanotubes (SWCNTs) have great potential to become the channel material for future high-speed transistor technology. However, to realize a carbon nanotube field effect transistor (CNTFET) with excellent gate control, the high-k dielectrics between the CNT and the metal gate must have superb electrical properties and extremely high uniformity. Thus it is essential to understand the interactions between high-k materials and the SWCNTs to effectively control the transistor characteristics. In this study, we investigate the effects of atomic layer deposited (ALD) high-k dielectrics (Al2O3 and HfO2) on SWCNTs using Raman spectroscopy. We subjected the SWCNTs to various ALD cycles and studied the nucleation and growth of ALD dielectrics at defect sites using scanning electron microscopy and transmission electron microscopy images. We analyzed these samples using Raman spectroscopy and x-ray photoelectron spectroscopy. The Raman peak shifts of the G-peak and the 2D (G') peaks suggest doping and stress induced effects on the CNTs by the surrounding high-k oxide environment. Trends in the G-peak FWHM and G/D-peak ratios were identified and compared between Al2O3 and HfO2. We confirmed the ALD-deposited HfO2 is polycrystalline using x-ray diffraction and analyzed dielectric-CNT bonding states using XPS measurements. This study provides insights on the effects of ALD high-k materials on SWCNTs for future high-speed transistor applications.

  5. Atomic layer deposition of high-k dielectrics on single-walled carbon nanotubes: a Raman study

    NASA Astrophysics Data System (ADS)

    Suriyasena Liyanage, Luckshitha; Cott, Daire J.; Delabie, Annelies; Van Elshocht, Sven; Bao, Zhenan; Wong, H.-S. Philip

    2013-06-01

    Single-wall carbon nanotubes (SWCNTs) have great potential to become the channel material for future high-speed transistor technology. However, to realize a carbon nanotube field effect transistor (CNTFET) with excellent gate control, the high-k dielectrics between the CNT and the metal gate must have superb electrical properties and extremely high uniformity. Thus it is essential to understand the interactions between high-k materials and the SWCNTs to effectively control the transistor characteristics. In this study, we investigate the effects of atomic layer deposited (ALD) high-k dielectrics (Al2O3 and HfO2) on SWCNTs using Raman spectroscopy. We subjected the SWCNTs to various ALD cycles and studied the nucleation and growth of ALD dielectrics at defect sites using scanning electron microscopy and transmission electron microscopy images. We analyzed these samples using Raman spectroscopy and x-ray photoelectron spectroscopy. The Raman peak shifts of the G-peak and the 2D (G‧) peaks suggest doping and stress induced effects on the CNTs by the surrounding high-k oxide environment. Trends in the G-peak FWHM and G/D-peak ratios were identified and compared between Al2O3 and HfO2. We confirmed the ALD-deposited HfO2 is polycrystalline using x-ray diffraction and analyzed dielectric-CNT bonding states using XPS measurements. This study provides insights on the effects of ALD high-k materials on SWCNTs for future high-speed transistor applications.

  6. Effect of surfactant addition on ultrasonic leaching of trace elements from plant samples in inductively coupled plasma-atomic emission spectrometry

    NASA Astrophysics Data System (ADS)

    Borkowska-Burnecka, Jolanta; Jankowiak, Urszula; Zyrnicki, Wieslaw; Anna Wilk, Kazimiera

    2004-04-01

    The applicability of surfactants in sample preparation of plant materials followed by analysis by inductively coupled plasma atomic emission spectrometry has been examined. Reference materials (INCT-MPH-2-Mixed Polish Herbs, INCT-TL-1 black tea leaves and CTA-VTL-2 -Virginia tobacco leaves) and commercially available tea leaves were analyzed. Effects of addition surfactants (Triton X-100, didodecyldimethylammonium bromide and cetyltrimethylammonium bromide) on efficiency of ultrasonic leaching of elements from the plant samples and on plasma parameters were investigated. Low concentrations of the surfactants in solutions did not affect, in practice, analytical line intensities and the nebulization process. Quantitative recovery of some elements could be obtained by ultrasonic diluted acid leaching with the aid of surfactants. However, the element recovery depended on type of surfactant, as well as element and sample material. Plasma parameters, i.e. the excitation temperatures of Ar I, Fe II and Ca II as well as the electron number density and the Mg II/Mg I intensity ratio did not vary significantly due to the surfactants in solutions.

  7. Numerical and experimental study of suspensions containing carbon blacks used as conductive additives in composite electrodes for lithium batteries.

    PubMed

    Cerbelaud, Manuella; Lestriez, Bernard; Ferrando, Riccardo; Videcoq, Arnaud; Richard-Plouet, Mireille; Caldes, Maria Teresa; Guyomard, Dominique

    2014-03-18

    Suspensions of carbon blacks and spherical carbon particles are studied experimentally and numerically to understand the role of the particle shape on the tendency to percolation. Two commercial carbon blacks and one lab-synthesized spherical carbon are used. The percolation thresholds in suspensions are experimentally determined by two complementary methods: impedance spectroscopy and rheology. Brownian dynamics simulations are performed to explain the experimental results taking into account the fractal shape of the aggregates in the carbon blacks. The results of Brownian dynamics simulations are in good agreement with the experimental results and allow one to explain the experimental behavior of suspensions.

  8. Pretransition and progressive softening of bovine carbonic anhydrase II as probed by single molecule atomic force microscopy

    PubMed Central

    Afrin, Rehana; Alam, Mohammad T.; Ikai, Atsushi

    2005-01-01

    To develop a simple method for probing the physical state of surface adsorbed proteins, we adopted the force curve mode of an atomic force microscope (AFM) to extract information on the mechanical properties of surface immobilized bovine carbonic anhydrase II under native conditions and in the course of guanidinium chloride–induced denaturation. A progressive increase in the population of individually softened molecules was probed under mildly to fully denaturing conditions. The use of the approach regime of force curves gave information regarding the height and rigidity of the molecule under compressive stress, whereas use of the retracting regime of the curves gave information about the tensile characteristics of the protein. The results showed that protein molecules at the beginning of the transition region possessed slightly more flattened and significantly more softened conformations compared with that of native molecules, but were still not fully denatured, in agreement with results based on solution studies. Thus the force curve mode of an AFM was shown to be sensitive enough to provide information concerning the different physical states of single molecules of globular proteins. PMID:15929995

  9. UHV-STM of single-walled carbon nanotubes in registration with the atomic lattices of silicon surfaces

    NASA Astrophysics Data System (ADS)

    Albrecht, Peter

    2005-03-01

    A room-temperature UHV-STM is used to elucidate the registration dependence of the electronic and mechanical properties of single-walled carbon nanotubes (SWCNTs) adsorbed onto silicon surfaces. The SWCNTs are deposited onto the Si surface in situ using a dry contact transfer (DCT) technique [1], with the resultant pristine SWCNT-Si interface enabling a joint atomic-resolution topographic and spectroscopic study of individual SWCNTs on both clean and H-passivated Si(100)-2x1 surfaces. Pronounced variations in the I-V and dI/dV-V spectra acquired along an isolated SWCNT were found to correlate with a transition from parallel to perpendicular alignment of the tube with respect to the dimer rows of the clean Si surface. Recent theoretical work [2] suggests that SWCNT-Si alignment is indeed energetically favorable and may give rise to novel nanotube-surface interactions unobserved in previous STM studies of SWCNTs in contact with a metallic substrate. [1] P.M. Albrecht and J.W. Lyding, APL 83, 5029 (2003). [2] W. Orellana, R.H. Miwa, and A. Fazzio, PRL 91, 166802 (2003).

  10. Synthesis of carbon nanotube-nickel nanocomposites using atomic layer deposition for high-performance non-enzymatic glucose sensing.

    PubMed

    Choi, Taejin; Kim, Soo Hyeon; Lee, Chang Wan; Kim, Hangil; Choi, Sang-Kyung; Kim, Soo-Hyun; Kim, Eunkyoung; Park, Jusang; Kim, Hyungjun

    2015-01-15

    A useful strategy has been developed to fabricate carbon-nanotube-nickel (CNT-Ni) nanocomposites through atomic layer deposition (ALD) of Ni and chemical vapor deposition (CVD) of functionalized CNTs. Various techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), were used to characterize the morphology and the structure of as-prepared samples. It was confirmed that the products possess uniform Ni nanoparticles that are constructed by finely controlled deposition of Ni onto oxygen or bromine functionalized CNT surface. Electrochemical studies indicate that the CNT-Ni nanocomposites exhibit high electrocatalytic activity for glucose oxidation in alkaline solutions, which enables the products to be used in enzyme-free electrochemical sensors for glucose determination. It was demonstrated that the CNT-Ni nanocomposite-based glucose biosensor offers a variety of merits, such as a wide linear response window for glucose concentrations of 5 μM-2 mM, short response time (3 s), a low detection limit (2 μM), high sensitivity (1384.1 μA mM(-1) cm(-2)), and good selectivity and repeatability.

  11. Fiber containment for improved laboratory handling and uniform nanocoating of milligram quantities of carbon nanotubes by atomic layer deposition.

    PubMed

    Devine, Christina K; Oldham, Christopher J; Jur, Jesse S; Gong, Bo; Parsons, Gregory N

    2011-12-06

    The presence of nanostructured materials in the workplace is bringing attention to the importance of safe practices for nanomaterial handling. We explored novel fiber containment methods to improve the handling of carbon nanotube (CNT) powders in the laboratory while simultaneously allowing highly uniform and controlled atomic layer deposition (ALD) coatings on the nanotubes, down to less than 4 nm on some CNT materials. Moreover, the procedure yields uniform coatings on milligram quantities of nanotubes using a conventional viscous flow reactor system, circumventing the need for specialized fluidized bed or rotary ALD reactors for laboratory-scale studies. We explored both fiber bundles and fiber baskets as possible containment methods and conclude that the baskets are more suitable for coating studies. An extended precursor and reactant dose and soak periods allowed the gases to diffuse through the fiber containment, and the ALD coating thickness scaled linearly with the number of ALD cycles. The extended dose period produced thicker coatings compared to typical doses on CNT controls not encased in the fibers, suggesting some effects due to the extended reactant dose. Film growth was compared on a range of single-walled NTs, double-walled NTs, and acid-functionalized multiwalled NTs, and we found that ultrathin coatings were most readily controlled on the multiwalled NTs.

  12. Impact of the atomic layer deposition precursors diffusion on solid-state carbon nanotube based supercapacitors performances.

    PubMed

    Fiorentino, Giuseppe; Vollebregt, Sten; Tichelaar, F D; Ishihara, Ryoichi; Sarro, Pasqualina M

    2015-02-13

    A study on the impact of atomic layer deposition (ALD) precursors diffusion on the performance of solid-state miniaturized nanostructure capacitor array is presented. Three-dimensional nanostructured capacitor array based on double conformal coating of multiwalled carbon nanotubes (MWCNTs) bundles is realized using ALD to deposit Al2O3 as dielectric layer and TiN as high aspect-ratio conformal counter-electrode on 2 μm long MWCNT bundles. The devices have a small footprint (from 100 μm(2) to 2500 μm(2)) and are realized using an IC wafer-scale manufacturing process with high reproducibility (≤0.3E-12F deviation). To evaluate the enhancement of the electrode surface, the measured capacitance values are compared to a lumped circuital model. The observed discrepancies are explained with a partial coating of the CNT, that determine a limited use of the available electrode surface area. To analyze the CNT coating effectiveness, the ALD precursors diffusions inside the CNT bundle is studied using a Knudsen diffusion mechanism.

  13. Synthesis of carbon nanofibers by CVD as a catalyst support material using atomically ordered Ni3C nanoparticles

    NASA Astrophysics Data System (ADS)

    Li, Meifeng; Li, Na; Shao, Wei; Zhou, Chungen

    2016-12-01

    Atomically ordered nickel carbide (Ni3C) nanoparticles in polygonal shapes were prepared through the reduction of nickelocene. A novel type of carbon nanofiber (CNF) with twisted conformation was synthesized successfully by catalytic chemical vapor deposition (CCVD) using the obtained Ni3C nanoparticles at a relatively low temperature of 350 °C, which is below the lower limit temperature of 400 °C for the growth of CNFs using metal catalysts. The growth mechanism of the twisted CNFs from Ni3C was freshly derived based on the detailed characterizations. Compared with the growth of CNFs from Ni, graphene layers nucleate at monoatomic step edges and grow in a layer-by-layer manner, while the rotation of the polygonal Ni3C nanoparticles fabricates the twisted conformation during the CNF growth. The electrochemical activity and performance of the twisted CNFs loaded with Pt as electrode catalysts for a polymer electrolyte membrane fuel cell (PEMFC) were measured to be better than those of straight CNFs grown from Ni nanoparticles at 500 °C, since the specific surface conformation helps to make the loaded Pt more homogeneous.

  14. Direct formation of anatase TiO2 nanoparticles on carbon nanotubes by atomic layer deposition and their photocatalytic properties

    NASA Astrophysics Data System (ADS)

    Huang, Sheng-Hsin; Liao, Shih-Yun; Wang, Chih-Chieh; Kei, Chi-Chung; Gan, Jon-Yiew; Perng, Tsong-Pyng

    2016-10-01

    TiO2 with different morphology was deposited on acid-treated multi-walled carbon nanotubes (CNTs) by atomic layer deposition at 100 °C-300 °C to form a TiO2@CNT structure. The TiO2 fabricated at 100 °C was an amorphous film, but became crystalline anatase nanoparticles when fabricated at 200 °C and 300 °C. The saturation growth rates of TiO2 nanoparticles at 300 °C were about 1.5 and 0.4 Å/cycle for substrate-enhanced growth and linear growth processes, respectively. It was found that the rate constants for methylene blue degradation by the TiO2@CNT structure formed at 300 °C were more suitable to fit with second-order reaction. The size of 9 nm exhibited the best degradation efficiency, because of the high specific area and appropriate diffusion length for the electrons and holes.

  15. Fabrication and characterization of tunnel barriers in a multi-walled carbon nanotube formed by argon atom beam irradiation

    SciTech Connect

    Tomizawa, H.; Yamaguchi, T.; Akita, S.; Ishibashi, K.

    2015-07-28

    We have evaluated tunnel barriers formed in multi-walled carbon nanotubes (MWNTs) by an Ar atom beam irradiation method and applied the technique to fabricate coupled double quantum dots. The two-terminal resistance of the individual MWNTs was increased owing to local damage caused by the Ar beam irradiation. The temperature dependence of the current through a single barrier suggested two different contributions to its Arrhenius plot, i.e., formed by direct tunneling through the barrier and by thermal activation over the barrier. The height of the formed barriers was estimated. The fabrication technique was used to produce coupled double quantum dots with serially formed triple barriers on a MWNT. The current measured at 1.5 K as a function of two side-gate voltages resulted in a honeycomb-like charge stability diagram, which confirmed the formation of the double dots. The characteristic parameters of the double quantum dots were calculated, and the feasibility of the technique is discussed.

  16. Fibrous Containment for Improved Laboratory Handling and Uniform Nanocoating of Milligram Quantities of Carbon Nanotubes by Atomic Layer Deposition

    PubMed Central

    Devine, Christina K.; Oldham, Christopher J.; Jur, Jesse S.; Gong, Bo; Parsons, Gregory N.

    2011-01-01

    The presence of nanostructured materials in the work place is bringing attention to the importance of safe practices for nanomaterial handling. We explored novel fiber containment methods to improve the handling of carbon nanotube (CNT) powders in the laboratory, while simultaneously allowing highly uniform and controlled atomic layer deposition (ALD) coatings on the nanotubes, down to less than 4 nm on some CNT materials. Moreover, the procedure yields uniform coatings on milligram quantities of nanotubes using a conventional viscous flow reactor system, circumventing the need for specialized fluidized bed or rotary ALD reactors for lab-scale studies. We explored both fiber bundles and fiber baskets as possible containment methods and conclude that the baskets are more suitable for coating studies. An extended precursor and reactant dose and soak periods allowed the gases to diffuse through the fiber containment, and the ALD coating thickness scaled linearly with the number of ALD cycles. The extended dose period produced thicker coatings compared with typical doses onto CNT controls not encased in the fibers, suggesting some effects due to the extended reactant dose. Film growth was compared on a range of single wall NTs, double wall NTs, and acid functionalized multiwall NTs and we found that ultrathin coatings were most readily controlled on the multi-walled NTs. PMID:22070742

  17. Simple additive simulation overestimates real influence: altered nitrogen and rainfall modulate the effect of warming on soil carbon fluxes.

    PubMed

    Ni, Xiangyin; Yang, Wanqin; Qi, Zemin; Liao, Shu; Xu, Zhenfeng; Tan, Bo; Wang, Bin; Wu, Qinggui; Fu, Changkun; You, Chengming; Wu, Fuzhong

    2016-12-09

    Experiments and models have led to a consensus that there is positive feedback between carbon (C) fluxes and climate warming. However, the effect of warming may be altered by regional and global changes in nitrogen (N) and rainfall levels, but the current understanding is limited. Through synthesizing global data on soil C pool, input and loss from experiments simulating N deposition, drought and increased precipitation, we quantified the responses of soil C fluxes and equilibrium to the three single factors and their interactions with warming. We found that warming slightly increased the soil C input and loss by 5% and 9%, respectively, but had no significant effect on the soil C pool. Nitrogen deposition alone increased the soil C input (+20%), but the interaction of warming and N deposition greatly increased the soil C input by 49%. Drought alone decreased the soil C input by 17%, while the interaction of warming and drought decreased the soil C input to a greater extent (-22%). Increased precipitation stimulated the soil C input by 15%, but the interaction of warming and increased precipitation had no significant effect on the soil C input. However, the soil C loss was not significantly affected by any of the interactions, although it was constrained by drought (-18%). These results implied that the positive C fluxes-climate warming feedback was modulated by the changing N and rainfall regimes. Further, we found that the additive effects of [warming × N deposition] and [warming × drought] on the soil C input and of [warming × increased precipitation] on the soil C loss were greater than their interactions, suggesting that simple additive simulation using single-factor manipulations may overestimate the effects on soil C fluxes in the real world. Therefore, we propose that more multifactorial experiments should be considered in studying Earth systems.

  18. A review of exposure and toxicological aspects of carbon nanotubes, and as additives to fire retardants in polymers.

    PubMed

    Christou, Antonis; Stec, Anna A; Ahmed, Waqar; Aschberger, Karin; Amenta, Valeria

    2016-01-01

    Carbon nanotubes (CNTs) have attracted considerable interest due to their unique physical, chemical, optical and electrical properties opening avenues for a large number of industrial applications. They have shown potential as fire retardant additives in polymers, reducing heat release rate and increasing time to ignition in a number of polymers. Relevant work on the types, properties and applications has been reviewed particularly considering their application in fire situations. There are concerns over the health risks associated with CNTs and many papers have likened CNTs to the health problems associated with asbestos. There are contradictions relating to the toxicity of CNTs with some papers reporting that they are toxic while others state the opposite. Directly comparing various studies is difficult because CNTs come in many combinations of size, type, purity levels and source. CNTs can potentially be released from polymers during the combustion process where human exposure may occur. While this review has shed some light regarding issues relating to toxicity under different fire scenarios much more thorough work is needed to investigate toxicity of CNTs and their evolution from CNT-polymer nanocomposites in order to reach firm conclusions.

  19. Mode-locked ytterbium fiber lasers using a large modulation depth carbon nanotube saturable absorber without an additional spectral filter

    NASA Astrophysics Data System (ADS)

    Pan, Y. Z.; Miao, J. G.; Liu, W. J.; Huang, X. J.; Wang, Y. B.

    2014-09-01

    We demonstrate an all-normal-dispersion ytterbium (Yb)-doped fiber laser mode-locked by a higher modulation depth carbon nanotube saturable absorber (CNT-SA) based on an evanescent field interaction scheme. The laser cavity consists of pure normal dispersion fibers without dispersion compensation and an additional spectral filter. It is exhibited that the higher modulation depth CNT-SA could contribute to stabilize the mode-locking operation within a limited range of pump power and generate the highly chirped pulses with a high-energy level in the cavity with large normal dispersion and strong nonlinearity. Stable mode-locked pulses with a maximal energy of 29 nJ with a 5.59 MHz repetition rate at the operating wavelength around 1085 nm have been obtained. The maximal time-bandwidth product is 262.4. The temporal and spectral characteristics of pulses versus pump power are demonstrated. The experimental results suggest that the CNT-SA provides a sufficient nonlinear loss to compensate high nonlinearity and catch up the gain at a different pump power and thus leads to the stable mode locking.

  20. Morphology and crystallinity control of ultrathin TiO2 layers deposited on carbon nanotubes by temperature-step atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Guerra-Nuñez, Carlos; Zhang, Yucheng; Li, Meng; Chawla, Vipin; Erni, Rolf; Michler, Johann; Park, Hyung Gyu; Utke, Ivo

    2015-06-01

    chemically inert CNTs and appropriate control of the morphology of the TiO2 layer have not been achieved so far. Here, we report a new strategy to obtain ultrathin TiO2 coatings deposited by ``Temperature-step'' Atomic Layer Deposition (TS-ALD) with complete surface coverage of non-functionalized multiwall carbon nanotubes (MWCNTs) and controlled morphology and crystallinity of the TiO2 film. This strategy consists of adjusting the temperature during the ALD deposition to obtain the desired morphology. Complete coverage of long non-functionalized MWCNTs with conformal anatase layers was obtained by using a low temperature of 60 °C during the nucleation stage followed by an increase to 220 °C during the growth stage. This resulted in a continuous and amorphous TiO2 layer, covered with a conformal anatase coating. Starting with the deposition at 220 °C and reducing to 60 °C resulted in sporadic crystal grains at the CNT/TiO2 interface covered with an amorphous TiO2 layer. The results were accomplished through an extensive study of nucleation and growth of titanium oxide films on MWCNTs, of which a detailed characterization is presented in this work. Electronic supplementary information (ESI) available: Additional TEM and SEM images, EDX mapping of the TiO2 coverage along the cross-section of the MWCNTs, the XPS spectra of the C 1s and O 1s peaks of the va-MWCNTs after 300 cycles of H2O and a discussion about the expected thickness against the measured thickness of TS-ALD samples are presented. See DOI: 10.1039/c5nr02106e

  1. Sulfate reduction in sulfuric material after re-flooding: Effectiveness of organic carbon addition and pH increase depends on soil properties.

    PubMed

    Yuan, Chaolei; Fitzpatrick, Rob; Mosley, Luke M; Marschner, Petra

    2015-11-15

    Sulfuric material is formed upon oxidation of sulfidic material; it is extremely acidic, and therefore, an environmental hazard. One option for increasing pH of sulfuric material may be stimulation of bacterial sulfate reduction. We investigated the effects of organic carbon addition and pH increase on sulfate reduction after re-flooding in ten sulfuric materials with four treatments: control, pH increase to 5.5 (+pH), organic carbon addition with 2% w/w finely ground wheat straw (+C), and organic carbon addition and pH increase (+C+pH). After 36 weeks, in five of the ten soils, only treatment +C+pH significantly increased the concentration of reduced inorganic sulfur (RIS) compared to the control and increased the soil pore water pH compared to treatment+pH. In four other soils, pH increase or/and organic carbon addition had no significant effect on RIS concentration compared to the control. The RIS concentration in treatment +C+pH as percentage of the control was negatively correlated with soil clay content and initial nitrate concentration. The results suggest that organic carbon addition and pH increase can stimulate sulfate reduction after re-flooding, but the effectiveness of this treatment depends on soil properties.

  2. Soil respiration characteristics in different land uses and response of soil organic carbon to biochar addition in high-latitude agricultural area.

    PubMed

    Ouyang, Wei; Geng, Xiaojun; Huang, Wejia; Hao, Fanghua; Zhao, Jinbo

    2016-02-01

    The farmland tillage practices changed the soil chemical properties, which also impacted the soil respiration (R s ) process and the soil carbon conservation. Originally, the farmland in northeast China had high soil carbon content, which was decreased in the recent decades due to the tillage practices. To better understand the R s dynamics in different land use types and its relationship with soil carbon loss, soil samples at two layers (0-15 and 15-30 cm) were analyzed for organic carbon (OC), total nitrogen (TN), total phosphorus (TP), total carbon (TC), available nitrogen (AN), available phosphorus (AP), soil particle size distribution, as well as the R s rate. The R s rate of the paddy land was 0.22 (at 0-15 cm) and 3.01 (at 15-30 cm) times of the upland. The average concentrations of OC and clay content in cultivated areas were much lower than in non-cultivated areas. The partial least squares analysis suggested that the TC and TN were significantly related to the R s process in cultivated soils. The upland soil was further used to test soil CO2 emission response at different biochar addition levels during 70-days incubation. The measurement in the limited incubation period demonstrated that the addition of biochar improved the soil C content because it had high concentration of pyrogenic C, which was resistant to mineralization. The analysis showed that biochar addition can promote soil OC by mitigating carbon dioxide (CO2) emission. The biochar addition achieved the best performance for the soil carbon conservation in high-latitude agricultural area due to the originally high carbon content.

  3. Direct in situ observations of single Fe atom catalytic processes and anomalous diffusion at graphene edges.

    PubMed

    Zhao, Jiong; Deng, Qingming; Avdoshenko, Stanislav M; Fu, Lei; Eckert, Jürgen; Rümmeli, Mark H

    2014-11-04

    Single-atom catalysts are of great interest because of their high efficiency. In the case of chemically deposited sp(2) carbon, the implementation of a single transition metal atom for growth can provide crucial insight into the formation mechanisms of graphene and carbon nanotubes. This knowledge is particularly important if we are to overcome fabrication difficulties in these materials and fully take advantage of their distinct band structures and physical properties. In this work, we present atomically resolved transmission EM in situ investigations of single Fe atoms at graphene edges. Our in situ observations show individual iron atoms diffusing along an edge either removing or adding carbon atoms (viz., catalytic action). The experimental observations of the catalytic behavior of a single Fe atom are in excellent agreement with supporting theoretical studies. In addition, the kinetics of Fe atoms at graphene edges are shown to exhibit anomalous diffusion, which again, is in agreement with our theoretical investigations.

  4. Beneficial effects of activated carbon additives on the performance of negative lead-acid battery electrode for high-rate partial-state-of-charge operation

    NASA Astrophysics Data System (ADS)

    Xiang, Jiayuan; Ding, Ping; Zhang, Hao; Wu, Xianzhang; Chen, Jian; Yang, Yusheng

    2013-11-01

    Experiments are made with negative electrode of 2 V cell and 12 V lead-acid battery doped with typical activated carbon additives. It turns out that the negative electrode containing tens-of-micron-sized carbon particles in NAM exhibits markedly increased HRPSoC cycle life than the one containing carbon particles with much smaller size of several microns or the one containing no activated carbon. The improved performance is mainly attributed to the optimized NAM microstructure and the enhanced electrode reaction kinetics by introducing appropriate activated carbon. The beneficial effects can be briefly summarized from three aspects. First, activated carbon acts as new porous-skeleton builder to increase the porosity and active surface of NAM, and thus facilitates the electrolyte diffusion from surface to inner and provides more sites for crystallization/dissolution of lead sulfate; second, activated carbon plays the role of electrolyte supplier to provide sufficient H2SO4 in the inner of plate when the diffusion of H2SO4 from plate surface cannot keep pace of the electrode reaction; Third, activated carbon acts as capacitive buffer to absorb excess charge current which would otherwise lead to insufficient NAM conversion and hydrogen evolution.

  5. Atomic structure of PtCu nanoparticles in PtCu/C catalysts prepared by simultaneous and sequential deposition of components on carbon support

    NASA Astrophysics Data System (ADS)

    Bugaev, L. A.; Srabionyan, V. V.; Pryadchenko, V. V.; Bugaev, A. L.; Avakyan, L. A.; Belenov, S. V.; Guterman, V. E.

    2016-05-01

    Nanocatalysts PtCu/C with different distribution of components in bimetallic PtCu nanoparticles (NPs) were synthesized by simultaneous and sequential deposition of Cu and Pt on carbon support. Electrochemical stability of the obtained samples PtCu/C was studied using the cyclic voltammetry. Characterization of atomic structure of as prepared PtCu NPs and obtained after acid treatment was performed by Pt L 3- and Cu K-edge EXAFS using the technique for determining local structure parameters of the absorbing atom under strong correlations among them. EXAFS derived parameters were used for generation of structural models of PtCu NPs by the method of cluster simulations. Within this approach, the models of atomic structure of PtCu NPs obtained by the two methods of synthesis, before and after post treatment and after two months from their preparation were revealed.

  6. Effects of molecular size and structure on self-diffusion coefficient and viscosity for