Science.gov

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

    2015-07-01

    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. From carbon nanotubes to carbon atomic chains

    NASA Astrophysics Data System (ADS)

    Casillas García, Gilberto; Zhang, Weijia; José-Yacamán, Miguel

    2010-10-01

    Carbyne is a linear allotrope of carbon. It is formed by a linear arrangement of carbon atoms with sp-hybridization. We present a reliable and reproducible experiment to obtain these carbon atomic chains using few-layer-graphene (FLG) sheets and a HRTEM. First the FLG sheets were synthesized from worm-like exfoliated graphite and then drop-casted on a lacey-carbon copper grid. Once in the TEM, two holes are opened near each other in a FLG sheet by focusing the electron beam into a small spot. Due to the radiation, the carbon atoms rearrange themselves between the two holes and form carbon fibers. The beam is concentrated on the carbon fibers in order excite the atoms and induce a tension until multi wall carbon nanotube (MWCNT) is formed. As the radiation continues the MWCNT breaks down until there is only a single wall carbon nanotube (SWCNT). Then, when the SWCNT breaks, an atomic carbon chain is formed, lasts for several seconds under the radiation and finally breaks. This demonstrates the stability of this carbon structure.

  3. 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

  4. 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.

  5. 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.

  6. Atomic Entanglement in Carbon Nanotubes.

    NASA Astrophysics Data System (ADS)

    Bondarev, Igor; Vlahovic, Branislav

    2006-03-01

    The development of materials that may host quantum coherent states is a critical research problem for the nearest future. Recent progress in the growth of centimeter-long small-diameter single-walled carbon nanotubes (CNs)[1] and successful experiments on the encapsulation of single atoms into CNs[2], stimulate the study of dynamical quantum processes in atomically doped CN systems. We have recently shown[3] that atomic states may be strongly coupled to vacuum surface photonic modes in the CN, thus forming quasi-1D cavity polaritons similar to those observed for quantum dots in semiconductor nanocavities[4], which were recently suggested to be a possible way to produce the excitonic qubit entanglement[5]. Here, we show that, being strongly coupled to the (resonator-like) cylindrical nanotube environment, the two atomic quasi-1D polaritons can be easily entangled as well, thus challenging a novel alternative approach towards quantum information transfer over centimeter-long distances. [1]L.X.Zheng et al, Proc. Nanotech 2005 (May 8-12, 2005, Anaheim, CA, USA), vol.3, p.126. [2]G.-H.Jeong et al, Phys. Rev. B68,075410(2003). [3]I.V.Bondarev and Ph.Lambin, in: Trends in Nanotubes Reasearch (NovaScience, NY, 2005); Phys. Rev. B70,035407(2004); Phys. Rev. B72,035451(2005). [4]T.Yoshie et al, Nature 432,200(2004). [5]S.Hughes, Phys. Rev. Lett.94,227402(2005).

  7. Atom probe tomography (APT) of carbonate minerals.

    PubMed

    Pérez-Huerta, Alberto; Laiginhas, Fernando; Reinhard, David A; Prosa, Ty J; Martens, Rich L

    2016-01-01

    Atom probe tomography (APT) combines the highest spatial resolution with chemical data at atomic scale for the analysis of materials. For geological specimens, the process of field evaporation and molecular ion formation and interpretation is not yet entirely understood. The objective of this study is to determine the best conditions for the preparation and analysis by APT of carbonate minerals, of great importance in the interpretation of geological processes, focusing on the bulk chemical composition. Results show that the complexity of the mass spectrum is different for calcite and dolomite and relates to dissimilarities in crystalochemical parameters. In addition, APT bulk chemistry of calcite closely matches the expected stoichiometry but fails to provide accurate atomic percentages for elements in dolomite under the experimental conditions evaluated in this work. For both calcite and dolomite, APT underestimates the amount of oxygen based on their chemical formula, whereas it is able to detect small percentages of elemental substitutions in crystal lattices. Overall, our results demonstrate that APT of carbonate minerals is possible, but further optimization of the experimental parameters are required to improve the use of atom probe tomography for the correct interpretation of mineral geochemistry. PMID:26519815

  8. Atom probe tomography (APT) of carbonate minerals.

    PubMed

    Pérez-Huerta, Alberto; Laiginhas, Fernando; Reinhard, David A; Prosa, Ty J; Martens, Rich L

    2016-01-01

    Atom probe tomography (APT) combines the highest spatial resolution with chemical data at atomic scale for the analysis of materials. For geological specimens, the process of field evaporation and molecular ion formation and interpretation is not yet entirely understood. The objective of this study is to determine the best conditions for the preparation and analysis by APT of carbonate minerals, of great importance in the interpretation of geological processes, focusing on the bulk chemical composition. Results show that the complexity of the mass spectrum is different for calcite and dolomite and relates to dissimilarities in crystalochemical parameters. In addition, APT bulk chemistry of calcite closely matches the expected stoichiometry but fails to provide accurate atomic percentages for elements in dolomite under the experimental conditions evaluated in this work. For both calcite and dolomite, APT underestimates the amount of oxygen based on their chemical formula, whereas it is able to detect small percentages of elemental substitutions in crystal lattices. Overall, our results demonstrate that APT of carbonate minerals is possible, but further optimization of the experimental parameters are required to improve the use of atom probe tomography for the correct interpretation of mineral geochemistry.

  9. 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.

  10. 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.

  11. Detection of gas atoms with carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Arash, B.; Wang, Q.

    2013-05-01

    Owning to their unparalleled sensitivity resolution, nanomechanical resonators have excellent capabilities in design of nano-sensors for gas detection. The current challenge is to develop new designs of the resonators for differentiating distinct gas atoms with a recognizably high sensitivity. In this work, the characteristics of impulse wave propagation in carbon nanotube-based sensors are investigated using molecular dynamics simulations to provide a new method for detection of noble gases. A sensitivity index based on wave velocity shifts in a single-walled carbon nanotube, induced by surrounding gas atoms, is defined to explore the efficiency of the nano-sensor. The simulation results indicate that the nano-sensor is able to differentiate distinct noble gases at the same environmental temperature and pressure. The inertia and the strengthening effects by the gases on wave characteristics of carbon nanotubes are particularly discussed, and a continuum mechanics shell model is developed to interpret the effects.

  12. 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.

  13. Dimethyl carbonate production for fuel additives

    SciTech Connect

    Okada, Y.; Kondo, T.; Asaoka, S.

    1996-12-31

    We have taken note of the transesterification reaction as a highly safe process of dimethyl carbonate (DMC) production for fuel additives. The reaction proceeds under the low corrosiveness and in the relatively mild condition. We have aimed to use an inorganic solid catalyst for this process. The inorganic solid catalyst is thermally stable and can be used in the large-scale fixed bed reactors without a catalyst separation unit. Through the transesterification of ethylene carbonate (EG) with methanol, DMC and ethylene glycol (EG) are co-generated as the products. EG is one of the bulk chemicals produced in the large scale plant comparable to one for the fuel additives. The market balance is important in the coproduction process. On the assumption that the amount of the co-production meets the market balance, the coproduction of DMC and EG is commercially viable. If we can control the amount of the EG coproduction in this process, it makes the process more flexible in the commercial production. Accordingly we have proposed a conceptual process scheme to control the amount of the EG coproduction. In this symposium, the inorganic solid catalyst system applying to the transesterification process and the conceptual process scheme how to control the amount of co-product will be discussed.

  14. Denitrification with carbon addition--kinetic considerations.

    PubMed

    Dold, P; Takács, I; Mokhayeri, Y; Nichols, A; Hinojosa, J; Riffat, R; Bott, C; Bailey, W; Murthy, S

    2008-05-01

    The Blue Plains Advanced Wastewater Treatment Plant (Washington, D.C.) uses methanol as an external carbon source in a postdenitrification process, to achieve low effluent total nitrogen concentrations. This becomes more difficult in winter, at lower mixed liquor temperatures and higher flows, as a consequence of the kinetic behavior of the methanol-utilizing heterotrophs. The paper reports on an experimental batch test study conducted on Blue Plains postdenitrification sludge to investigate (1) the maximum specific growth rate of methanol-utilizing heterotrophs (Mu(METH)); (2) the temperature dependency of the growth rate; and (3) the efficacy of alternate substrates (ethanol, acetate, and sugar). A limited number of tests were conducted on sludge from two other treatment plants with methanol addition. PMID:18605381

  15. Structurally uniform and atomically precise carbon nanostructures

    NASA Astrophysics Data System (ADS)

    Segawa, Yasutomo; Ito, Hideto; Itami, Kenichiro

    2016-01-01

    Nanometre-sized carbon materials consisting of benzene units oriented in unique geometric patterns, hereafter named nanocarbons, conduct electricity, absorb and emit light, and exhibit interesting magnetic properties. Spherical fullerene C60, cylindrical carbon nanotubes and sheet-like graphene are representative forms of nanocarbons, and theoretical simulations have predicted several exotic 3D nanocarbon structures. At present, synthetic routes to nanocarbons mainly lead to mixtures of molecules with a range of different structures and properties, which cannot be easily separated or refined into pure forms. Some researchers believe that it is impossible to synthesize these materials in a precise manner. Obtaining ‘pure’ nanocarbons is a great challenge in the field of nanocarbon science, and the construction of structurally uniform nanocarbons, ideally as single molecules, is crucial for the development of functional materials in nanotechnology, electronics, optics and biomedical applications. This Review highlights the organic chemistry approach — more specifically, bottom-up construction with atomic precision — that is currently the most promising strategy towards this end.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Carbon-atom wires: 1-D systems with tunable properties

    NASA Astrophysics Data System (ADS)

    Casari, C. S.; Tommasini, M.; Tykwinski, R. R.; Milani, A.

    2016-02-01

    This review provides a discussion of the current state of research on linear carbon structures and related materials based on sp-hybridization of carbon atoms (polyynes and cumulenes). We show that such systems have widely tunable properties and thus represent an intriguing and mostly unexplored field for both fundamental and applied sciences. We discuss the rich interplay between the structural, vibrational, and electronic properties focusing on recent advances and the future perspectives of carbon-atom wires and novel hybrid sp-sp2-carbon architectures.

  2. 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.

  3. 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.

  4. 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...

  5. 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...

  6. 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...

  7. 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...

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

    PubMed

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

    2015-12-22

    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.

  10. 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

  11. Dispersion forces between ultracold atoms and a carbon nanotube.

    PubMed

    Schneeweiss, P; Gierling, M; Visanescu, G; Kern, D P; Judd, T E; Günther, A; Fortágh, J

    2012-08-01

    Dispersion forces are long-range interactions between polarizable objects that arise from fluctuations in the electromagnetic field between them. Dispersion forces have been observed between microscopic objects such as atoms and molecules (the van der Waals interaction), between macroscopic objects (the Casimir interaction) and between an atom and a macroscopic object (the Casimir-Polder interaction). Dispersion forces are known to increase the attractive forces between the components in nanomechanical devices, to influence adsorption rates onto nanostructures, and to influence the interactions between biomolecules in biological systems. In recent years, there has been growing interest in studying dispersion forces in nanoscale systems and in exploring the interactions between carbon nanotubes and cold atoms. However, there are considerable difficulties in developing dispersion force theories for general, finite geometries such as nanostructures. Thus, there is a need for new experimental methods that are able to go beyond measurements of planar surfaces and nanoscale gratings and make measurements on isolated nanostructures. Here, we measure the dispersion force between a rubidium atom and a multiwalled carbon nanotube by inserting the nanotube into a cloud of ultracold rubidium atoms and monitoring the loss of atoms from the cloud as a function of time. We perform these experiments with both thermal clouds of ultracold atoms and with Bose-Einstein condensates. The results obtained with this approach will aid the development of theories describing quantum fields near nanostructures, and hybrid cold-atom/solid-state devices may also prove useful for applications in quantum sensing and quantum information.

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

    DOE PAGES

    Bedekar, Vikram; Poplawsky, Jonathan D.; Guo, Wei; Shivpuri, Rajiv; Scott Hyde, R.

    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.

  13. Interpretation of Hund's multiplicity rule for the carbon atom.

    PubMed

    Hongo, Kenta; Maezono, Ryo; Kawazoe, Yoshiyuki; Yasuhara, Hiroshi; Towler, M D; Needs, R J

    2004-10-15

    Hund's multiplicity rule is investigated for the carbon atom using quantum Monte Carlo methods. Our calculations give an accurate account of electronic correlation and obey the virial theorem to high accuracy. This allows us to obtain accurate values for each of the energy terms and therefore to give a convincing explanation of the mechanism by which Hund's rule operates in carbon. We find that the energy gain in the triplet with respect to the singlet state is due to the greater electron-nucleus attraction in the higher spin state, in accordance with Hartree-Fock calculations and studies including correlation. The method used here can easily be extended to heavier atoms.

  14. 48 CFR 204.470 - U.S.-International Atomic Energy Agency Additional Protocol.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 48 Federal Acquisition Regulations System 3 2013-10-01 2013-10-01 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....

  15. 48 CFR 204.470 - U.S.-International Atomic Energy Agency Additional Protocol.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 48 Federal Acquisition Regulations System 3 2012-10-01 2012-10-01 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....

  16. 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....

  17. 48 CFR 204.470 - U.S.-International Atomic Energy Agency Additional Protocol.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 48 Federal Acquisition Regulations System 3 2014-10-01 2014-10-01 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....

  18. 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....

  19. Trapping cold atoms using surface-grown carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Petrov, P. G.; Machluf, S.; Younis, S.; Macaluso, R.; David, T.; Hadad, B.; Japha, Y.; Keil, M.; Joselevich, E.; Folman, R.

    2009-04-01

    We present a feasibility study for loading cold atomic clouds into magnetic traps created by single-wall carbon nanotubes grown directly onto dielectric surfaces. We show that atoms may be captured for experimentally sustainable nanotube currents, generating trapped clouds whose densities and lifetimes are sufficient to enable detection by simple imaging methods. This opens the way for a different type of conductor to be used in atomchips, enabling atom trapping at submicron distances, with implications for both fundamental studies and for technological applications.

  20. Mechanistic and computational studies of the atom transfer radical addition of CCl4 to styrene catalyzed by copper homoscorpionate complexes.

    PubMed

    Muñoz-Molina, José María; Sameera, W M C; Álvarez, Eleuterio; Maseras, Feliu; Belderrain, Tomás R; Pérez, Pedro J

    2011-03-21

    Experimental as well as theoretical studies have been carried out with the aim of elucidating the mechanism of the atom transfer radical addition (ATRA) of styrene and carbon tetrachloride with a Tp(x)Cu(NCMe) complex as the catalyst precursor (Tp(x) = hydrotrispyrazolyl-borate ligand). The studies shown herein demonstrate the effect of different variables in the kinetic behavior. A mechanistic proposal consistent with theoretical and experimental data is presented.

  1. Crossed beam study of the atom-radical reaction of ground state carbon atoms (C(3P)) with the vinyl radical (C2H3(X2A')).

    PubMed

    Wilson, Antony V; Parker, Dorian S N; Zhang, Fangtong; Kaiser, Ralf I

    2012-01-14

    The atom-radical reaction of ground state carbon atoms (C((3)P)) with the vinyl radical (C(2)H(3)(X(2)A')) was conducted under single collision conditions at a collision energy of 32.3 ± 2.9 kJ mol(-1). The reaction dynamics were found to involve a complex forming reaction mechanism, which is initiated by the barrier-less addition of atomic carbon to the carbon-carbon-double bond of the vinyl radical forming a cyclic C(3)H(3) radical intermediate. The latter has a lifetime of at least 1.5 times its rotational period and decomposes via a tight exit transition state located about 45 kJ mol(-1) above the separated products through atomic hydrogen loss to the cyclopropenylidene isomer (c-C(3)H(2)) as detected toward cold molecular clouds and in star forming regions.

  2. The influence hydrogen atom addition has on charge switching during motion of the metal atom in endohedral Ca@C60H4 isomers.

    PubMed

    Raggi, G; Besley, E; Stace, A J

    2016-09-13

    Density functional theory has been applied in a study of charge transfer between an endohedral calcium atom and the fullerene cage in Ca@C60H4 and [Ca@C60H4](+) isomers. Previous calculations on Ca@C60 have shown that the motion of calcium within a fullerene is accompanied by large changes in electron density on the carbon cage. Based on this observation, it has been proposed that a tethered endohedral fullerene might form the bases of a nanoswitch. Through the addition of hydrogen atoms to one hemisphere of the cage it is shown that, when compared with Ca@C60, asymmetric and significantly reduced energy barriers can be generated with respect to motion of the calcium atom. It is proposed that hydrogen atom addition to a fullerene might offer a route for creating a bi-stable nanoswitch that can be fine-tuned through the selection of an appropriate isomer and number of atoms attached to the cage of an endohedral fullerene.This article is part of the themed issue 'Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene'.

  3. The influence hydrogen atom addition has on charge switching during motion of the metal atom in endohedral Ca@C60H4 isomers.

    PubMed

    Raggi, G; Besley, E; Stace, A J

    2016-09-13

    Density functional theory has been applied in a study of charge transfer between an endohedral calcium atom and the fullerene cage in Ca@C60H4 and [Ca@C60H4](+) isomers. Previous calculations on Ca@C60 have shown that the motion of calcium within a fullerene is accompanied by large changes in electron density on the carbon cage. Based on this observation, it has been proposed that a tethered endohedral fullerene might form the bases of a nanoswitch. Through the addition of hydrogen atoms to one hemisphere of the cage it is shown that, when compared with Ca@C60, asymmetric and significantly reduced energy barriers can be generated with respect to motion of the calcium atom. It is proposed that hydrogen atom addition to a fullerene might offer a route for creating a bi-stable nanoswitch that can be fine-tuned through the selection of an appropriate isomer and number of atoms attached to the cage of an endohedral fullerene.This article is part of the themed issue 'Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene'. PMID:27501967

  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

    2014-01-01

    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. PMID:24328147

  5. Computational studies of gas phase reactions of carbon chain anions with N and O atoms.

    PubMed

    Yang, Zhibo; Snow, Theodore P; Bierbaum, Veronica M

    2010-10-28

    Experimental studies of gas phase reactions of carbanions with N and O atoms have been reported previously to understand ion chemistry relevant to the interstellar medium. In all cases reactions of anions with O atoms exhibit larger reaction rate constants compared to the corresponding N atom reactions. In addition, the open-shell carbon chain anions exhibit higher reactivities than the corresponding closed-shell species in N atom reactions, whereas similar reactivities were observed for both open and closed-shell anions in O atom reactions. These trends are investigated by the current theoretical study of the reactions of HC(n)(-)(n = 2, 4, and 6) and C(n)(-) (n = 2, 4-7) with N and O atoms. Our results indicate that spin-forbidden processes are the probable pathways in reactions of closed-shell anions HC(n)(-) with N atoms, and spin conversion limits the reaction efficiency. In reactions of open-shell anions C(n)(-) with N atoms, about 50% of the collisions may proceed through spin-allowed barrierless pathways, which results in relatively higher reaction efficiencies than for the closed-shell reactions. For reactions of all anions with O atoms, the spin-allowed barrierless pathways are the only channels, such that all reactions occur with very high efficiencies. This work provides a greater understanding of the influence of spin effects on the reactivities of anion reactions involving N and O atoms that may be important in the interstellar medium.

  6. Chemical control of electrical contact to sp2 carbon atoms

    PubMed Central

    Frederiksen, Thomas; Foti, Giuseppe; Scheurer, Fabrice; Speisser, Virginie; Schull, Guillaume

    2014-01-01

    Carbon-based nanostructures are attracting tremendous interest as components in ultrafast electronics and optoelectronics. The electrical interfaces to these structures play a crucial role for the electron transport, but the lack of control at the atomic scale can hamper device functionality and integration into operating circuitry. Here we study a prototype carbon-based molecular junction consisting of a single C60 molecule and probe how the electric current through the junction depends on the chemical nature of the foremost electrode atom in contact with the molecule. We find that the efficiency of charge injection to a C60 molecule varies substantially for the considered metallic species, and demonstrate that the relative strength of the metal-C bond can be extracted from our transport measurements. Our study further suggests that a single-C60 junction is a basic model to explore the properties of electrical contacts to meso- and macroscopic sp2 carbon structures. PMID:24736561

  7. Interaction of scandium and titanium atoms with a carbon surface containing five- and seven-membered rings

    SciTech Connect

    Krasnov, P. O.; Eliseeva, N. S.; Kuzubov, A. A.

    2012-01-15

    The use of carbon nanotubes coated by atoms of transition metals to store molecular hydrogen is associated with the problem of the aggregation of these atoms, which leads to the formation of metal clusters. The quantum-chemical simulation of cluster models of the carbon surface of a graphene type with scandium and titanium atoms has been performed. It has been shown that the presence of five- and seven-membered rings, in addition to six-membered rings, in these structures makes it possible to strongly suppress the processes of the migration of metal atoms over the surface, preventing their clustering.

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

    PubMed

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

    2013-11-01

    We investigated the dynamics of the reaction of (3)P 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 (3)P 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 (3)P carbon atoms with ethene, vinyl fluoride, and vinyl chloride are stated.

  10. 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.

  11. Intermolecular Atom Transfer Radical Addition to Olefins Mediated by Oxidative Quenching of Photoredox Catalysts

    PubMed Central

    Nguyen, John D.; Tucker, Joseph W.; Konieczynska, Marlena D.; Stephenson, Corey R. J.

    2011-01-01

    Atom transfer radical addition of haloalkanes and α-halocarbonyls to olefins is efficiently performed with the photocatalyst Ir[(dF(CF3)ppy)2(dtbbpy)]PF6. This protocol is characterized by excellent yields, mild conditions, low catalyst loading, and broad scope. In addition, the atom transfer protocol can be used to quickly and efficiently introduce vinyl trifluoromethyl groups to olefins and access 1,1-cyclopropane diesters. PMID:21381734

  12. Encapsulating "armchair" carbon nanotubes with "zigzag" chains of Fe atoms

    NASA Astrophysics Data System (ADS)

    Boutko, V. G.; Gusev, A. A.; Shevtsova, T. N.; Pashkevich, Yu. G.

    2016-05-01

    Ab initio calculations of structural, electron, and magnetic properties of "armchair" carbon nanotubes (NT) encapsulated by a "zigzag" chain of Fe atoms Fe2@(n,n)m (m = 1, 2; n = 4, 5, 6, 7, 8, 9), are performed within the framework of the density functional theory. It is shown that optimizing the structure along the NT axis can significantly impact the binding energy of the NT and the Fe atom chain. It follows from the calculations that Fe2@(5,5) is the most stable of all the investigated encapsulated nanotubes. A two-fold decrease in the concentration of Fe in an encapsulated NT converts the system from exothermic to endothermic (Fe2@(5,5)m) and vice versa (Fe2@(6,6)m)). For large radii of an encapsulated NT (>4.13 Å) the binding energy of the NT and the Fe atom chain goes to zero, and the magnetic moments of the Fe atoms and the deviation of the Fe atoms from the NT axis go toward analogous values of the free "zigzag" Fe atom chain.

  13. Atomic force microscopy investigation of electrochemically produced carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Miklósi, J.; Póczik, P.; Sytchev, I.; Papp, K.; Kaptay, G.; Nagy, P.; Kálmán, E.

    Carbon nanostructures have been synthesized in NaCl-MgCl2 and in NaCl-CaCl2 salt melts and the extracted material was investigated by tapping-mode atomic force microscopy (TM-AFM) and scanning electron microscopy. Some interesting new nanostructures were found and investigated as torus-shaped carbon structures with a ring diameter of 300-400 nm and 10-15 nm height. These tori are closely related to the wrapped SWNT rings described recently. They are probably formed during the electrolysis. A chain-like structure was also revealed.

  14. Interpretation of Hund's multiplicity rule for the carbon atom.

    PubMed

    Hongo, Kenta; Maezono, Ryo; Kawazoe, Yoshiyuki; Yasuhara, Hiroshi; Towler, M D; Needs, R J

    2004-10-15

    Hund's multiplicity rule is investigated for the carbon atom using quantum Monte Carlo methods. Our calculations give an accurate account of electronic correlation and obey the virial theorem to high accuracy. This allows us to obtain accurate values for each of the energy terms and therefore to give a convincing explanation of the mechanism by which Hund's rule operates in carbon. We find that the energy gain in the triplet with respect to the singlet state is due to the greater electron-nucleus attraction in the higher spin state, in accordance with Hartree-Fock calculations and studies including correlation. The method used here can easily be extended to heavier atoms. PMID:15473780

  15. 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.

  16. 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

  17. Single and double addition of oxygen atoms to propyne on surfaces at low temperatures.

    PubMed

    Kimber, Helen J; Ennis, Courtney P; Price, Stephen D

    2014-01-01

    Experiments designed to simulate the low temperature surface chemistry occurring in interstellar clouds provide clear evidence of a reaction between oxygen atoms and propyne ice. The reactants are dosed onto a surface held at a fixed temperature between 14 and 100 K. After the dosing period, temperature programmed desorption (TPD), coupled with time-of-flight mass spectrometry, are used to identify two reaction products with molecular formulae C3H4O and C3H4O2. These products result from the addition of a single oxygen atom, or two oxygen atoms, to a propyne reactant. A simple model has been used to extract kinetic data from the measured yield of the single-addition (C3H4O) product at surface temperatures from 30-100 K. This modelling reveals that the barrier of the solid-state reaction between propyne and a single oxygen atom (160 +/- 10 K) is an order of magnitude less than that reported for the gas-phase reaction. In addition, estimates for the desorption energy of propyne and reaction rate coefficient, as a function of temperature, are determined for the single addition process from the modelling. The yield of the single addition product falls as the surface temperature decreases from 50 K to 30K, but rises again as the surface temperature falls below 30 K. This increase in the rate of reaction at low surface temperatures is indicative of an alternative, perhaps barrierless, pathway to the single addition product which is only important at low surface temperatures. The kinetic model has been further developed to characterize the double addition reaction, which appears to involve the addition of a second oxygen atom to C3H4O. This modelling indicates that this second addition is a barrierless process. The kinetic parameters we extract from our experiments indicate that the reaction between atomic oxygen and propyne could occur under on interstellar dust grains on an astrophysical time scale.

  18. 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

  19. 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.

  20. Voronoi analysis of the short-range atomic structure in iron and iron-carbon melts

    NASA Astrophysics Data System (ADS)

    Sobolev, Andrey; Mirzoev, Alexander

    2015-08-01

    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.

  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. 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

  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. Extremely sharp carbon nanocone probes for atomic force microscopy imaging

    NASA Astrophysics Data System (ADS)

    Chen, I.-Chen; Chen, Li-Han; Ye, Xiang-Rong; Daraio, Chiara; Jin, Sungho; Orme, Christine A.; Quist, Arjan; Lal, Ratnesh

    2006-04-01

    A simple and reliable catalyst patterning technique combined with electric-field-guided growth is utilized to synthesize a sharp and high-aspect-ratio carbon nanocone probe on a tipless cantilever for atomic force microscopy. A single carbon nanodot produced by an electron-beam-induced deposition serves as a convenient chemical etch mask for catalyst patterning, thus eliminating the need for complicated, resist-based, electron-beam lithography for a nanoprobe fabrication. A gradual, sputtering-induced size reduction and eventual removal of the catalyst particle at the probe tip during electric-field-guided growth creates a sharp probe with a tip radius of only a few nanometers. These fabrication processes are amenable for the wafer-scale synthesis of multiple probes. High resolution imaging of three-dimensional features and deep trenches, and mechanical durability enabling continuous operation for many hours without noticeable image deterioration have been demonstrated.

  5. Copper-homoscorpionate complexes as active catalysts for atom transfer radical addition to olefins.

    PubMed

    Muñoz-Molina, José María; Caballero, Ana; Díaz-Requejo, M Mar; Trofimenko, Swiatoslaw; Belderraín, Tomas R; Pérez, Pedro J

    2007-09-17

    Cu(I) complexes containing trispyrazolylborate ligands efficiently catalyze the atom transfer radical addition (ATRA) of polyhalogenated alkanes to various olefins under mild conditions. The catalytic activity is enhanced when bulky and electron donating Tpx ligands are employed. Kinetic data have allowed the proposal of a mechanistic interpretation that includes a Cu(II) pentacoordinated species that regulates the catalytic cycle.

  6. 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.

  7. 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

    2016-05-01

    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.

  8. Linear carbon allotrope carbon atom wires prepared by pyrolysis of starch

    NASA Astrophysics Data System (ADS)

    Xue, Kuan-Hong; Tao, Fei-Fei; Shen, Wei; He, Chun-Jian; Chen, Qiao-Ling; Wu, Li-Jun; Zhu, Yi-Mei

    2004-02-01

    A new method is reported to produce linear carbon allotrope from the pyrolysis of starch catalyzed by Fe. The pyrolytic product termed as carbon atom wires (CAW) is composed of winding lines with the diameter around 2.0 Å, indicated by magnified HRTEM images. The experimental results of UV and Raman spectra revealed a conjugated sequence of cumulated double bonds (CC) n presented in the hexane extract of CAW. Arguments about the sp hybridization bonding structure of CAW can also be supported by EELS and FT-IR measurements.

  9. Observations of neutral atomic carbon at 809 GHz.

    PubMed

    Zmuidzinas, J; Betz, A L; Goldhaber, D M

    1986-08-15

    We have detected the 809 GHz 3P2-3P1 fine-structure line of neutral atomic carbon in four dense molecular clouds: M17, W51, W3, and DR 21(OH). These observations complement the published observations of the 492 GHz 3P1-3P0 line and allow the excitation temperature of the 3P levels along with the line optical depths to be determined. The results indicate excitation temperatures Tx approximately 30-60 K and optical depths of tau 10 < or approximately 1. This implies that the approximately 10(18) cm-2 lower limit to the C I abundance derived from 492 GHz observations is probably the actual abundance, which gives C I/CO approximately 0.1 in dense molecular clouds.

  10. 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.

  11. 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

  12. Improvement in topology measurement accuracy of atomic force microscope using additional sensor

    NASA Astrophysics Data System (ADS)

    Yoon, Yeomin; Jeong, Jiseong; Kim, Junsup; Park, Kyihwan

    2015-07-01

    The topology image of an atomic force microscope is obtained by picking up a controlled output of a force-feedback loop that is proportional to the height of a sample under the assumption that no dynamics in a z-axis actuator exist. However, the dynamic effects such as hysteresis and creep in a PZT driving z-axis actuator cannot be ignored. To solve this problem, a strain-gage sensor is used as an additional sensor, which enables measurement of the absolute displacement of a z-axis PZT nano scanner. The advantage of using an additional sensor is experimentally provided and validated in topology images.

  13. 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.

  14. The initial flow dynamics of light atoms through carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Cannon, James; Kim, Daejoong; Hess, Ortwin

    2011-04-01

    Carbon nanotubes are becoming increasingly viable as membranes for application in a wide variety of nano-fluidic applications, such as nano-scale nozzles. For potential applications that utilize switching on and off of flow through nanotube nozzles, it is important to understand the initial flow dynamics. Furthermore, when the nanotube interacts strongly with the fluid, the flow may be very different from conventional simulations, which consider atoms (such as argon, for example) that interact only weakly with the nanotube. Therefore, to better understand such flows and explore the potential manipulation of flow that can be achieved, we consider the initial flow dynamics of a light fluid through carbon nanotube nozzles, using non-equilibrium molecular dynamics simulations. Our studies show that if the conditions are controlled carefully, unusual phenomena can be generated, such as pulsed flow and very nonlinear increases in flow rate with nanotube diameter. We detail the physical reasons for such phenomena and describe how the pulsation can be controlled using temperature.

  15. 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

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. Note: vibration reduction control of an atomic force microscope using an additional cantilever.

    PubMed

    Kim, Chulsoo; Jung, Jongkyu; Park, Kyihwan

    2011-11-01

    Since an atomic force microscope is used to measure sub-nanometer level precision, it is sensitive to external vibration. If the vibration can be measured by using an additional sensor, we can obtain the vibration-free signal by subtracting the vibration signal from the signal containing the vibration. To achieve a highly effective vibration rejection ratio, it is important to decide where to locate the additional sensor. This is because the vibration measured at the sensing position should have the same phase as that of the vibration in the signal. Vibration reduction control using this electrical sensing method is verified through time domain analysis and topology images of a standard grid sample.

  1. 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.

  2. Enhancement of electrical conductivity and electrochemical activity of hydrogenated amorphous carbon by incorporating boron atoms

    NASA Astrophysics Data System (ADS)

    Naragino, Hiroshi; Yoshinaga, Kohsuke; Nakahara, Akira; Tanaka, Sakuya; Honda, Kensuke

    2013-06-01

    Conductive boron-doped hydrogenated amorphous carbon (B-DLC) thin films were successfully synthesized with RF plasma-enhanced CVD method. By incorporating boron atoms in amorphous carbon, conduction types were changed from n- to p-type, and volume resistivity was decreased from 30.4 (non-doped) to 6.36 × 10-2 Ω cm (B/C = 2.500 atom%). B-DLC film with sp2/(sp2 + sp3) carbons of 75 atom% exhibited high resistance to electrochemically-induced corrosion in strong acid solution. Furthermore, it was clarified that boron atoms in DLC could enhance kinetics of hydrogen evolution during water electrolysis at B-DLC surface. B-DLC is, therefore, a promising electrode material for hydrogen production by increasing the concentration of boron atoms in B-DLC and enhancing the reactivity of H2 evolution.

  3. A first principles study on the CVD graphene growth on copper surfaces: A carbon atom incorporation to graphene edges

    NASA Astrophysics Data System (ADS)

    Tajima, Nobuo; Kaneko, Tomoaki; Nara, Jun; Ohno, Takahisa

    2016-11-01

    Carbon atom reactions in the chemical vapor deposition (CVD) processes for graphene production on copper surfaces have been studied by first principles molecular dynamics (MD) simulations at a typical CVD growth temperature. This study focuses on the processes of a carbon atom incorporation to graphene edges. The energy barriers of these carbon atom incorporation reactions have been calculated as ~ 1 eV, which are comparable or slightly larger than the barriers of carbon atom dimerization. We have also found that the surface copper atoms form step like structures to terminate the carbon dangling bonds at graphene edges, which are markedly different from the graphene-copper interactions observed in static calculations.

  4. Surface reactions of molecular and atomic oxygen with carbon phosphide films.

    PubMed

    Gorham, Justin; Torres, Jessica; Wolfe, Glenn; d'Agostino, Alfred; Fairbrother, D Howard

    2005-11-01

    The surface reactions of atomic and molecular oxygen with carbon phosphide films have been studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Carbon phosphide films were produced by ion implantation of trimethylphosphine into polyethylene. Atmospheric oxidation of carbon phosphide films was dominated by phosphorus oxidation and generated a carbon-containing phosphate surface film. This oxidized surface layer acted as an effective diffusion barrier, limiting the depth of phosphorus oxidation within the carbon phosphide film to < 3 nm. The effect of atomic oxygen (AO) exposure on this oxidized carbon phosphide layer was subsequently probed in situ using XPS. Initially AO exposure resulted in a loss of carbon atoms from the surface, but increased the surface concentration of phosphorus atoms as well as the degree of phosphorus oxidation. For more prolonged AO exposures, a highly oxidized phosphate surface layer formed that appeared to be inert toward further AO-mediated erosion. By utilizing phosphorus-containing hydrocarbon thin films, the phosphorus oxides produced during exposure to AO were found to desorb at temperatures >500 K under vacuum conditions. Results from this study suggest that carbon phosphide films can be used as AO-resistant surface coatings on polymers.

  5. 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.

  6. 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

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

    PubMed

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

    2015-01-22

    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.

  8. 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.

  9. Evaluation of phenyl carbonates as electrolyte additives in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Petibon, R.; Rotermund, L. M.; Dahn, J. R.

    2015-08-01

    The impact of the electrolyte additives methyl phenyl carbonate, ethyl phenyl carbonate, and diphenyl carbonate was evaluated in Li[Ni0.33Mn0.33Co0.33]O2/graphite pouch cells with or without 2% vinylene carbonate. Experiments included high precision coulometry, automated storage, electrochemical impedance spectroscopy on symmetric cells and gas chromatography coupled with mass spectrometry. Gas chromatography/mass spectrometry analysis, electrochemical studies during the first charge and impedance spectroscopy on symmetric cells indicated that phenyl carbonates act as solid electrolyte interphase modifiers rather than formers. High precision coulometry showed that cells containing 1-4 wt% methyl phenyl carbonate, ethyl phenyl carbonate or diphenyl carbonate had similar coulombic efficiencies and charge-endpoint capacity slippage as cells filled with 2 wt% vinylene carbonate. Impedance spectroscopy showed that cells containing phenyl carbonates have substantially lower impedance than cells filled with 2 wt% vinylene carbonate and produced minimal volumes of gas during cell use. Results presented in the report show that phenyl carbonates are competitive additives for 4.2 V class cells and should lead to good cycle life, low polarization and low gas evolution during normal use. Phenyl carbonates can also be used as gas-producing safety agents (to trip pressure activated disconnects) in combination with vinylene carbonate in cylindrical or prismatic cells without adverse effects.

  10. Plasmon enhanced Raman scattering effect for an atom near a carbon nanotube.

    PubMed

    Bondarev, I V

    2015-02-23

    Quantum electrodynamics theory of the resonance Raman scattering is developed for an atom in a close proximity to a carbon nanotube. The theory predicts a dramatic enhancement of the Raman intensity in the strong atomic coupling regime to nanotube plasmon near-fields. This resonance scattering is a manifestation of the general electromagnetic surface enhanced Raman scattering effect, and can be used in designing efficient nanotube based optical sensing substrates for single atom detection, precision spontaneous emission control, and manipulation. PMID:25836436

  11. 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.

  12. 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

  13. 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

  14. Enantioselective Nucleophilic β-Carbon-Atom Amination of Enals: Carbene-Catalyzed Formal [3+2] Reactions.

    PubMed

    Wu, Xingxing; Liu, Bin; Zhang, Yuexia; Jeret, Martin; Wang, Honglin; Zheng, Pengcheng; Yang, Song; Song, Bao-An; Chi, Yonggui Robin

    2016-09-26

    An enantioselective β-carbon amination for enals is disclosed. The nitrogen atom from a protected hydrazine with suitable electronic properties readily behaves as a nucleophile. Addition of the nitrogen nucleophile to a catalytically generated N-heterocyclic-carbene-bound α,β-unsaturated acyl azolium intermediate constructs a new carbon-nitrogen bond asymmetrically. The pyrazolidinone products from our catalytic reactions are common scaffolds in bioactive molecules, and can be easily transformed into useful compounds such as β(3) -amino-acid derivatives. PMID:27596365

  15. 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.

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

    DOE PAGES

    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, 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

  17. Atomic carbon emission from photodissociation of CO2. [planetary atmospheric chemistry

    NASA Technical Reports Server (NTRS)

    Wu, C. Y. R.; Phillips, E.; Lee, L. C.; Judge, D. L.

    1978-01-01

    Atomic carbon fluorescence, C I 1561, 1657, and 1931 A, has been observed from photodissociation of CO2, and the production cross sections have been measured. A line emission source provided the primary photons at wavelengths from threshold to 420 A. The present results suggest that the excited carbon atoms are produced by total dissociation of CO2 into three atoms. The cross sections for producing the O I 1304-A fluorescence through photodissociation of CO2 are found to be less than 0.01 Mb in the wavelength region from 420 to 835 A. The present data have implications with respect to photochemical processes in the atmospheres of Mars and Venus.

  18. STEM Imaging of Single Pd Atoms in Activated Carbon Fibers Considered for Hydrogen Storage

    SciTech Connect

    Van Benthem, Klaus; Bonifacio, Cecile S; Contescu, Cristian I; Pennycook, Stephen J; Gallego, Nidia C

    2011-01-01

    Aberration corrected scanning transmission electron microscopy was used to demonstrate the feasibility of imaging individual Pd atoms that are highly dispersed throughout the volume of activated carbon fibers. Simultaneous acquisition of high-angle annular dark-field and bright-field images allows correlation of the location of single Pd atoms with microstructural features of the carbon host material. Sub-Angstrom imaging conditions revealed that 18 wt% of the total Pd content is dispersed as single Pd atoms in three re-occurring local structural arrangements. The identified structural configurations may represent effective storage sites for molecular hydrogen through Kubas complex formation as discussed in detail in the preceding article.

  19. 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.

  20. Understanding the detection of carbon in austenitic high-Mn steel using atom probe tomography.

    PubMed

    Marceau, R K W; Choi, P; Raabe, D

    2013-09-01

    A high-Mn TWIP steel having composition Fe-22Mn-0.6C (wt%) is considered in this study, where the need for accurate and quantitative analysis of clustering and short-range ordering by atom probe analysis requires a better understanding of the detection of carbon in this system. Experimental measurements reveal that a high percentage of carbon atoms are detected as molecular ion species and on multiple hit events, which is discussed with respect to issues such as optimal experimental parameters, correlated field evaporation and directional walk/migration of carbon atoms at the surface of the specimen tip during analysis. These phenomena impact the compositional and spatial accuracy of the atom probe measurement and thus require careful consideration for further cluster-finding analysis.

  1. 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.

  2. Optically promoted bipartite atomic entanglement in hybrid metallic carbon nanotube systems

    SciTech Connect

    Gelin, M. F.; Bondarev, I. V.; Meliksetyan, A. V.

    2014-02-14

    We study theoretically a pair of spatially separated extrinsic atomic type species (extrinsic atoms, ions, molecules, or semiconductor quantum dots) near a metallic carbon nanotube, that are coupled both directly via the inter-atomic dipole-dipole interactions and indirectly by means of the virtual exchange by resonance plasmon excitations on the nanotube surface. We analyze how the optical preparation of the system by using strong laser pulses affects the formation and evolution of the bipartite atomic entanglement. Despite a large number of possible excitation regimes and evolution pathways, we find a few generic scenarios for the bipartite entanglement evolution and formulate practical recommendations on how to optimize and control the robust bipartite atomic entanglement in hybrid carbon nanotube systems.

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. Effect of Axial Torsion on sp Carbon Atomic Wires

    NASA Astrophysics Data System (ADS)

    Ravagnan, Luca; Manini, Nicola; Cinquanta, Eugenio; Onida, Giovanni; Sangalli, Davide; Motta, Carlo; Devetta, Michele; Bordoni, Andrea; Piseri, Paolo; Milani, Paolo

    2009-06-01

    Ab initio calculations within density-functional theory combined with experimental Raman spectra on cluster-beam deposited pure-carbon films provide a consistent picture of sp-carbon chains stabilized by sp3 or sp2 terminations, the latter being sensitive to torsional strain. This unexplored effect promises many exciting applications since it allows one to modify the conductive states near the Fermi level and to switch on and off the on-chain π-electron magnetism.

  8. 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

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. Atomic scale simulations of vapor cooled carbon clusters

    NASA Astrophysics Data System (ADS)

    Bogana, M. P.; Colombo, L.

    2007-03-01

    By means of atomistic simulations we observed the formation of many topologically non-equivalent carbon clusters formed by the condensation of liquid droplets, including: (i) standard fullerenes and onion-like structures, (ii) clusters showing extremely complex surfaces with both positive and negative curvatures and (iii) complex endohedral structures. In this work we offer a thorough structural characterization of the above systems, as well as an attempt to correlate the resulting structure to the actual protocol of growth. The IR and Raman responses of some exotic linear carbon structures have been further investigated, finding good agreement with experimental evidence of carbinoid structures in cluster-assembled films. Towards the aim of fully understanding the process of cluster-to-cluster coalescence dynamics, we further simulated an aerosol of amorphous carbon clusters at controlled temperatures. Various annealing temperatures and times have been observed, identifying different pathways for cluster ripening, ranging from simple coalescence to extensive reconstruction.

  14. 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.

  15. Atomic structure and dynamic behaviour of truly one-dimensional ionic chains inside carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Senga, Ryosuke; Komsa, Hannu-Pekka; Liu, Zheng; Hirose-Takai, Kaori; Krasheninnikov, Arkady V.; Suenaga, Kazu

    2014-11-01

    Materials with reduced dimensionality have attracted much interest in various fields of fundamental and applied science. True one-dimensional (1D) crystals with single-atom thickness have been realized only for few elemental metals (Au, Ag) or carbon, all of which showed very short lifetimes under ambient conditions. We demonstrate here a successful synthesis of stable 1D ionic crystals in which two chemical elements, one being a cation and the other an anion, align alternately inside carbon nanotubes. Unusual dynamical behaviours for different atoms in the 1D lattice are experimentally corroborated and suggest substantial interactions of the atoms with the nanotube sheath. Our theoretical studies indicate that the 1D ionic crystals have optical properties distinct from those of their bulk counterparts and that the properties can be engineered by introducing atomic defects into the chains.

  16. Atomic Step-Templated Formation of Single-Wall Carbon Nanotube Patterns

    NASA Astrophysics Data System (ADS)

    Joselevich, Ernesto; Jorio, Ado; Son, Hyungbin

    2005-03-01

    Single-wall carbon nanotubes catalytically produced on miscut C-plane sapphire wafers grow along the 0.2nm-high atomic steps of the vicinal α-Al2O3 (0001) surfaces, yielding highly aligned, dense arrays of discrete nanotubes on a dielectric material [1]. The nanotubes reproduce the atomic features of the surface, including steps, facets and kinks. Microscopy, X-ray diffraction and single-nanotube Raman spectroscopy [2] shed light into the possible structure and mechanism of the step-templated carbon nanotube growth. The orientation, density and morphology of the atomic steps can be macroscopically controlled by the crystal cutting process. Hence, these findings open up the possibility of assembling nanotube architectures by atomic-scale surface engineering. [1] A. Ismach, et al., Angew. Chem. Int. Ed. 2004, 43, 6140. [2] M. Souza, et al., Phys. Rev. B 2004, 241403R.

  17. 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. PMID:27116595

  18. 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.

  19. 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.

  20. Carbon nanotube synthesis: from large-scale production to atom-by-atom growth.

    PubMed

    Journet, Catherine; Picher, Matthieu; Jourdain, Vincent

    2012-04-13

    The extraordinary electronic, thermal and mechanical properties of carbon nanotubes (CNTs) closely relate to their structure. They can be seen as rolled-up graphene sheets with their electronic properties depending on how this rolling up is achieved. However, this is not the way they actually grow. Various methods are used to produce carbon nanotubes. They all have in common three ingredients: (i) a carbon source, (ii) catalyst nanoparticles and (iii) an energy input. In the case where the carbon source is provided in solid form, one speaks about 'high temperature methods' because they involve the sublimation of graphite which does not occur below 3200 °C. The first CNTs were synthesized by these techniques. For liquid or gaseous phases, the generic term of 'medium or low temperature methods' is used. CNTs are now commonly produced by these latter techniques at temperatures ranging between 350 and 1000 °C, using metal nanoparticles that catalyze the decomposition of the gaseous carbon precursor and make the growth of nanotubes possible. The aim of this review article is to give a general overview of all these methods and an understanding of the CNT growth process. PMID:22433510

  1. Carbon nanotube synthesis: from large-scale production to atom-by-atom growth

    NASA Astrophysics Data System (ADS)

    Journet, Catherine; Picher, Matthieu; Jourdain, Vincent

    2012-04-01

    The extraordinary electronic, thermal and mechanical properties of carbon nanotubes (CNTs) closely relate to their structure. They can be seen as rolled-up graphene sheets with their electronic properties depending on how this rolling up is achieved. However, this is not the way they actually grow. Various methods are used to produce carbon nanotubes. They all have in common three ingredients: (i) a carbon source, (ii) catalyst nanoparticles and (iii) an energy input. In the case where the carbon source is provided in solid form, one speaks about ‘high temperature methods’ because they involve the sublimation of graphite which does not occur below 3200 °C. The first CNTs were synthesized by these techniques. For liquid or gaseous phases, the generic term of ‘medium or low temperature methods’ is used. CNTs are now commonly produced by these latter techniques at temperatures ranging between 350 and 1000 °C, using metal nanoparticles that catalyze the decomposition of the gaseous carbon precursor and make the growth of nanotubes possible. The aim of this review article is to give a general overview of all these methods and an understanding of the CNT growth process.

  2. 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.

  3. 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.

  4. Determination of cadmium in the livers and kidneys of puffins by carbon furnace atomic absorption spectrometry.

    PubMed

    Ottaway, J M; Campbell, W C

    1976-01-01

    A carbon furnace atomic absorption procedure is described for the determination of cadmium in the livers and kidneys of puffins, fratercula arctica. Samples are dried and weighed and 2 to 100 mg are dissolved in sulphuric and nitric acids. These solutions are analysed directly in the carbon furnace against aqueous standards and provide accurate results in the range 0-1 to 100 micrograms/g dry weight. The method is simple and rapid and requires much less of the small total sample than would be required for flame atomic absorption. PMID:1030692

  5. 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.

  6. 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.

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

    PubMed

    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

  8. 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

  9. 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.

  10. Atom-scale insights into carbonate organic-mineral interfaces

    NASA Astrophysics Data System (ADS)

    Branson, O.; Perea, D. E.; Spero, H. J.; Winters, M. A.; Gagnon, A.

    2015-12-01

    Biominerals are formed by the complex interaction between guiding biological structures and the kinetics of inorganic mineral growth. Inorganic crystal growth experiments have advanced our understanding of mineral precipitation in the context of biological systems, but the structure and chemistry of the mineralizing interface between these two systems has remained elusive. We have used laser-pulsed Atom Probe Tomography to reveal the first atom-scale 3D view of an organic-mineral interface in calcite produced by the planktic foraminifera Orbulina universa. We observe elevated Na and Mg throughout the organic, and a 9-fold increase in Na in the surface 2 nm of the organic layer, relative to the adjacent calcite. The surface-specificity of this Na maximum suggests that Na may play an integral role in conditioning the organic layer for calcite nucleation. Na could accomplish this by modifying surface hydration or structure, to modify organic-fluid and/or organic-calcite interfacial energies. Our data constitute the first evidence of the role of 'spectator' ions in facilitating biomineralisation, which could be an overlooked but crucial aspect of the initial steps of skeleton formation in calcifying organisms.

  11. Reaction of matrix-isolated iron atoms with carbon disulfide

    SciTech Connect

    Doeff, M.M.

    1986-07-02

    This study was undertaken to determine the type of bonding, as well as the extent of reactivity between CS/sub 2/ and iron atoms. The results of several matrix isolation experiments in which either pure CS/sub 2/ or SC/sub 2//Ar and CS/sub 2//Kr mixtures were condensed with iron atoms and studied by infrared and Moessbauer spectroscopy are presented. All the spectra indicate the presence of only one product of the reaction between Fe and CS/sub 2/ no matter what the composition of the matrix. Conditions were also such that only monomeric Fe complexes were expected; therefore, it is concluded that the complex formed in these matrices has a composition of Fe(CS/sub 2/). Results of annealing experiments carried out to determine the stability of the complex were interpreted to mean that the Fe(CS/sub 2/) formed in a 100% CS/sub 2/ matrix is stable to at least 60 K, begins to decompose between 60 and 80 K to form a new iron-containing species, and forms a very stable, nonvolatile residue at room temperature. 22 references, 1 figure.

  12. Accurate determination of atomic structure of multiwalled carbon nanotubes by nondestructive nanobeam electron diffraction

    SciTech Connect

    Liu Zejian; Zhang Qi; Qin Luchang

    2005-05-09

    We report a method that allows direct, systematic, and accurate determination of the atomic structure of multiwalled carbon nanotubes by analyzing the scattering intensities on the nonequatorial layer lines in the electron diffraction pattern. Complete structure determination of a quadruple-walled carbon nanotube is described as an example, and it was found that the intertubular distance varied from 0.36 nm to 0.5 nm with a mean value of 0.42 nm.

  13. Visible Light-Driven Atom Transfer Radical Addition to Olefins using Bi2 O3 as Photocatalyst.

    PubMed

    Riente, Paola; Pericàs, Miquel A

    2015-06-01

    Bismuth oxide, an inexpensive and non-toxic semiconductor, has been successfully used as a visible light photocatalyst for the atom transfer radical addition (ATRA) reaction of organobromides to diversely functionalized terminal olefins. The reaction takes place under very mild conditions, in the absence of any additive, and with low catalyst loading (1 mol %). The corresponding ATRA products are obtained with moderate to excellent yields (up to 95 %). PMID:25925199

  14. 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.

  15. Possibilities of Application of Carbon-Fluorine Containing Additions in Submerged-Arc Welding

    NASA Astrophysics Data System (ADS)

    Kozyrev, N. A.; Kryukov, N. E.; Kryukov, R. E.; Igushev, V. F.; Kovalskii, I. I.

    2015-09-01

    The paper provides results of comparative analysis of the effect of carbonaceous components introduced into welding fluxes on molten metal - slag interaction. A positive influence of carbonaceous additives on gas content and mechanical properties of welds is demonstrated. Carbon and fluorine containing additives are emphasized to be promising for automatic submerged arc welding.

  16. 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

  17. 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)

  18. 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.

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

    PubMed

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

    2016-07-13

    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.

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

    PubMed

    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

  1. One-Dimensional Confined Motion of Single Metal Atoms inside Double-Walled Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Warner, Jamie H.; Ito, Yasuhiro; Rümmeli, Mark H.; Gemming, Thomas; Büchner, Bernd; Shinohara, Hisanori; Briggs, G. Andrew D.

    2009-05-01

    Peapods containing La@C82 metallofullerenes are transformed into double-walled carbon nanotubes (DWNTs) using in situ electron beam irradiation at 80 kV. Using this low accelerating voltage we find no damage to the outer single-walled carbon nanotube (SWNT) within this time period and the complete formation of an inner nanotube within 5-7 min of irradiation. The La metal atoms are restricted to the interior of the inner SWNT and remain trapped. We demonstrate that energy from electron beam irradiation can drive the lateral confined motion of single La atoms. The interplay between two La atoms confined within the interior of a DWNT is examined and we find large La-La separation unique to this 1D environment. We also demonstrate the formation of TWNTs from DWNT peapods.

  2. 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

    2000-08-01

    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 (i) its structural and chemical simplicity, (ii) interest in Mg(OH){sub 2} gas-solid carbonation as a potentially cost-effective CO{sub 2} mineral sequestration process component, and (iii) 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 cost optimization of any lamellar-hydroxide-based mineral carbonation sequestration process.

  3. The atom-surface interaction potential for He-NaCl: A model based on pairwise additivity

    NASA Astrophysics Data System (ADS)

    Hutson, Jeremy M.; Fowler, P. W.

    1986-08-01

    The recently developed semi-empirical model of Fowler and Hutson is applied to the He-NaCl atom-surface interaction potential. Ab initio self-consistent field calculations of the repulsive interactions between He atoms and in-crystal Cl - and Na + ions are performed. Dispersion coefficients involving in-crystal ions are also calculated. The atom-surface potential is constructed using a model based on pairwise additivity of atom-ion forces. With a small adjustment of the repulsive part, this potential gives good agreement with the experimental bound state energies obtained from selective adsorption resonances in low-energy atom scattering experiments. Close-coupling calculations of the resonant scattering are performed, and good agreement with the experimental peak positions and intensity patterns is obtained. It is concluded that there are no bound states deeper than those observed in the selective adsorption experiments, and that the well depth of the He-NaCl potential is 6.0 ± 0.2 meV.

  4. 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.

  5. 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).

  6. Chemical control of electrical contact to sp² carbon atoms.

    PubMed

    Frederiksen, Thomas; Foti, Giuseppe; Scheurer, Fabrice; Speisser, Virginie; Schull, Guillaume

    2014-01-01

    Carbon-based nanostructures are attracting tremendous interest as components in ultrafast electronics and optoelectronics. The electrical interfaces to these structures play a crucial role for the electron transport, but the lack of control at the atomic scale can hamper device functionality and integration into operating circuitry. Here we study a prototype carbon-based molecular junction consisting of a single C60 molecule and probe how the electric current through the junction depends on the chemical nature of the foremost electrode atom in contact with the molecule. We find that the efficiency of charge injection to a C60 molecule varies substantially for the considered metallic species, and demonstrate that the relative strength of the metal-C bond can be extracted from our transport measurements. Our study further suggests that a single-C60 junction is a basic model to explore the properties of electrical contacts to meso- and macroscopic sp(2) carbon structures.

  7. 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

  8. Atoms in carbon cages as a source of interstellar diffuse lines

    NASA Technical Reports Server (NTRS)

    Ballester, J. L.; Antoniewicz, P. R.; Smoluchowski, R.

    1990-01-01

    A model to describe the resonance absorption lines of various atoms trapped in closed carbon cages is presented. These systems may be responsible for some of the as yet unexplained diffuse interstellar bands. Model potentials for possible atom-C60 systems are obtained and used to calculate the resonance lines. The trapped atoms considered are O, N, Si, Mg, Al, Na, and S, and in all cases the resonance lines are shifted toward the red as compared to the isolated atoms. The calculated wavelengths are compared to the range of wavelengths observed for the diffuse interstellar bands, and good agreement is found for Mg and Si resonance lines. Other lines may be caused by other than resonance transitions or by trapped molecules. The oscillator strengths and the abundances are evaluated and compared with observation. Mechanisms to explain the observed band width of the lines and the existence of certain correlated pairs of lines are discussed.

  9. Impact ignition of aluminum-teflon based energetic materials impregnated with nano-structured carbon additives

    NASA Astrophysics Data System (ADS)

    Kappagantula, Keerti; Pantoya, Michelle L.; Hunt, Emily M.

    2012-07-01

    The inclusion of graphene into composite energetic materials to enhance their performance is a new area of interest. Studies have shown that the addition of graphene significantly enhances the thermal transport properties of an energetic composite, but how graphene influences the composite's ignition sensitivity has not been studied. The objective of this study is to examine the influence of carbon additives in composite energetic material composed of aluminum and polytetrafluoroethylene (Teflon™) on ignition sensitivity due to low velocity, drop weight impact. Specifically, three forms of carbon additives were investigated and selected based on different physical and structural properties: spherically shaped amorphous nano particles of carbon, cylindrically shaped multi walled carbon nanotubes, and sheet like graphene flakes. Results show an interesting trend: composites consisting of carbon nanotubes are significantly more sensitive to impact ignition and require the lowest ignition energy. In contrast, graphene is least sensitive to ignition exhibiting negligible reduction in ignition energy with low concentrations of graphene additive. While graphene does not significantly sensitize the energetic composite to ignition, graphene does, however, result in greater overall reactivity as observed through images of the reaction. The enhanced thermal transport properties of graphene containing composites may promote greater energy transport once ignited, but those properties do not also increase ignition sensitivity. These results and the understanding of the structural arrangement of particles within a composite as a key parameter affecting impact ignition sensitivity will have an impact on the safe handling and use of composite energetic materials.

  10. 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; K. Streib

    1999-09-01

    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(OH){sub 2} carbonation is a leading process candidate, which generates the stable naturally occurring mineral magnesite (MgCO{sub 3}) and water. Key to process cost and viability are the carbonation reaction rate and its degree of completion. This process, which involves simultaneous dehydroxylation and carbonation is very promising, but far from optimized. In order to optimize the dehydroxylation/carbonation process, an atomic-level understanding of the mechanisms involved is needed. Since Mg(OH){sub 2} dehydroxylation is intimately associated with the carbonation process, its mechanisms are also of direct interest in understanding and optimizing the process. In the first project year, our investigations have focused on developing an atomic-level understanding of the dehydroxylation/carbonation reaction mechanisms that govern the overall carbonation reaction process in well crystallized material. In years two and three, we will also explore the roles of crystalline defects and impurities. Environmental-cell, dynamic high-resolution transmission electron microscopy has been used to directly observe the dehydroxylation process at the atomic-level for the first time. These observations were combined with advanced computational modeling studies to better elucidate the atomic-level process. These studies were combined with direct carbonation studies to better elucidate dehydroxylation/carbonation reaction mechanisms. Dehydroxylation follows a lamellar nucleation and growth process involving oxide layer formation. These layers form lamellar oxyhydroxide regions, which can

  11. 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.

  12. The effect of additional high dose carbon implantation on the tribological properties of titanium implanted steel

    NASA Astrophysics Data System (ADS)

    Hayashi, Kazunori; Sasaki, Jun; Ichiko, Osami; Hashiguchi, Yoshihiro

    1996-08-01

    The tribological properties and the structural changes of hardened steel implanted with titanium followed by carbon were investigated as a function of additional carbon dose. The dose of Ti was 5×10 17 Ti cm -2 and the additional C doses were 0, 4×10 17, 8×10 17 and 1.2×10 18 C cm -2. After Ti implantation, the steel surface transformed to a FeTiC ternary amorphous phase. Additional implantation of carbon to a dose of 4×10 17 C cm -2 produced fine TiC precipitates dispersed in the ternary amorphous matrix. When the additional C dose exceeded 8×10 17 C cm -2, very fine graphite precipitates appeared in the ternary amorphous phase. The steel surface with very fine graphite precipitates exhibited superior tribological properties. The benefits provided by additional high dose carbon implantation are considered as follows: strengthening of the amorphous phase, thickening of the modified layer, dispersion strengthening of the implanted layer by very fine graphite precipitates and lubrication effect by graphite particles. Comparing the friction properties of Ti+C implanted steel with that of C implanted steel, the role of Ti implantation is to reduce the friction of the surface during sliding and the role of C implantation is to increase the lifetime of the surface against wear.

  13. Copper(I)-catalyzed regioselective addition of nucleophilic silicon across terminal and internal carbon-carbon triple bonds.

    PubMed

    Hazra, Chinmoy K; Fopp, Carolin; Oestreich, Martin

    2014-10-01

    The copper(I) alkoxide-catalyzed release of a silicon-based cuprate reagent from a silicon-boron pronucleophile is applied to the addition across carbon-carbon triple bonds. Commercially available CuBr⋅Me2S was found to be a general precatalyst that secures high regiocontrol for both aryl- and alkyl-substituted terminal as well as internal alkynes. The solvent greatly influences the regioisomeric ratio, favoring the linear regioisomer with terminal acceptors. This facile protocol even allows for the transformation of internal acceptors with remarkable levels of regio- and diastereocontrol.

  14. 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.

  15. Analysis of zinc in biological samples by flame atomic absorption spectrometry: use of addition calibration technique.

    PubMed

    Dutra, Rosilene L; Cantos, Geny A; Carasek, Eduardo

    2006-01-01

    The quantification of target analytes in complex matrices requires special calibration approaches to compensate for additional capacity or activity in the matrix samples. The standard addition is one of the most important calibration procedures for quantification of analytes in such matrices. However, this technique requires a great number of reagents and material, and it consumes a considerable amount of time throughout the analysis. In this work, a new calibration procedure to analyze biological samples is proposed. The proposed calibration, called the addition calibration technique, was used for the determination of zinc (Zn) in blood serum and erythrocyte samples. The results obtained were compared with those obtained using conventional calibration techniques (standard addition and standard calibration). The proposed addition calibration was validated by recovery tests using blood samples spiked with Zn. The range of recovery for blood serum and erythrocyte samples were 90-132% and 76-112%, respectively. Statistical studies among results obtained by the addition technique and conventional techniques, using a paired two-tailed Student's t-test and linear regression, demonstrated good agreement among them. PMID:16943611

  16. 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.

  17. Impacts of biochar (black carbon) additions on the sorption and efficacy of herbicides

    Technology Transfer Automated Retrieval System (TEKTRAN)

    There is renewed interest in the soil application of charcoal (biochar) as a means of increasing carbon sequestration and combating climate change. The land areas that are targeted for biochar applications are agricultural land, due to the potential positive impacts that charcoal additions have on o...

  18. Comparisons of short carbon nanotubes containing conductive additives of cathode for lithium ion batteries

    SciTech Connect

    Zhang, Qingtang; Wang, Xiaomei; Lu, Wenjiang; Tang, Fuling; Guo, Junhong; Yu, Weiyuan; Qu, Meizhen; Yu, Zuolong

    2013-08-01

    Graphical abstract: - Highlights: • Short carbon nanotubes (SCNT) containing conductive additives were used. • SCNT/graphite powder (GP) mixture is better than SCNT/mesoporous carbon mixture. • SCNT connect many isolated GP particles to form a more valid conductive network. • SCNT absorb some electrolyte solution allowing quick electrochemical reactions. - Abstract: Short carbon nanotubes (SCNT) containing conductive additives, i.e. SCNT/graphite powder (GP) mixture (SCNTGP) and SCNT/mesoporous carbon (MC) mixture (SCNTMC) were employed as conductive additives for LiCoO{sub 2} cathode. GP and MC have similar particle size, but GP has lower specific surface area and higher electronic conductivity. Electrochemical measurements indicate that SCNTGP is more effective in improving the electrochemical performance of LiCoO{sub 2} composite cathode under the same conditions. The reason is described as follows. SCNT connect the isolated GP particles to form a more valid conductive network. In addition, SCNT has a certain specific mesoporous surface area, which can absorb some electrolyte solution and then provide buffer lithium ions for quick electrochemical reactions. Consequently, the combination of these two factors would be responsible to the improvement in the electrochemical performance of the SCNTGP loaded cathode.

  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. Boron carbide as atomic oxygen protection for the Lexan-carbon filter on the ROSAT wide-field camera

    NASA Astrophysics Data System (ADS)

    Kent, Barry J.; Swinyard, Bruce M.; Maier, Hans-Joerg; Frischke, Dagmar

    1992-01-01

    The ROSAT Wide Field Camera, launched in June 1990, uses large area (50 cm2) thin film (typically 0.5 micrometers thick), band pass filters to select different extreme ultra violet wavelength bands. One of the filters consists of a substrate of the plastic polycarbonate, Lexan$DAG, interleaved with carbon and is thus susceptible to erosion by atomic oxygen in the ROSAT low earth orbit at 580 km altitude. The filter was protected against this erosion mechanism by using a thin overcoating of boron carbide. We describe the boron carbide coating process, the technique used to minimize the heat load on the fragile plastic foil, and the need for an additional adhesion layer of carbon. The chemical composition of the boron carbide as evaporated material on glass slides has been measured using several surface science techniques as well as by analysis of the soft x-ray and EUV transmission of sample foils and completed flight filters. Additionally, using ion and atomic oxygen sources, the effectiveness of the coating has been evaluated by laboratory measurements on sample foils.

  1. 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.

  2. 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.

  3. Microwave absorption properties of carbon nanocoils coated with highly controlled magnetic materials by atomic layer deposition.

    PubMed

    Wang, Guizhen; Gao, Zhe; Tang, Shiwei; Chen, Chaoqiu; Duan, Feifei; Zhao, Shichao; Lin, Shiwei; Feng, Yuhong; Zhou, Lei; Qin, Yong

    2012-12-21

    In this work, atomic layer deposition is applied to coat carbon nanocoils with magnetic Fe(3)O(4) or Ni. The coatings have a uniform and highly controlled thickness. The coated nanocoils with coaxial multilayer nanostructures exhibit remarkably improved microwave absorption properties compared to the pristine carbon nanocoils. The enhanced absorption ability arises from the efficient complementarity between complex permittivity and permeability, chiral morphology, and multilayer structure of the products. This method can be extended to exploit other composite materials benefiting from its convenient control of the impedance matching and combination of dielectric-magnetic multiple loss mechanisms for microwave absorption applications.

  4. The interaction between Boron-carbon-nitride heteronanotubes and lithium atoms: Role of composition proportion

    NASA Astrophysics Data System (ADS)

    Zhong, Rong-Lin; Xu, Hong-Liang; Su, Zhong-Min

    2016-08-01

    A series of Li@BCN models were systematically investigated to explore the physical origin of the interaction between lithium atoms and BCNs. Theoretical results show that the crucial electron population in the BCNs of Li@B-BCN and Li@N-BCN series is dramatically different. As results, the first hyperpolarizability of Li@B-BCN series increases with the increase of carbon proportion whereas that of Li@N-BCN series significantly decreases with the increase of carbon proportion. The results indicate that the physical properties of Li@BCN models are significantly dependent on the different chemical environment of the tube termination.

  5. Biological nitrogen removal from coke plant wastewater with external carbon addition

    SciTech Connect

    Lee, M.W.; Park, J.M.

    1998-07-01

    Coke plant wastewater containing high concentrations of ammonia and toxic compounds such as phenol and cyanide was treated using a biological nitrogen removal (BNR) system comprising carbon removal, nitrification, and denitrification stages. The objective of this study was to investigate the feasibility of complete ammonia removal from the coke plant wastewater using a sequential BNR process with external carbon addition. Sodium acetate was introduced as an external carbon source to the denitrification stage after oxidation of phenol and other carbonaceous compounds in the carbon-removal stage. The efficiency of denitrification was strongly affected by the loading rate of the external carbon source, and its optimal rate was determined based on the ratio of chemical oxygen demand to nitrate- and nitrite-nitrogen (COD:NO{sub x}-N) of the denitrification stage. The overall removal efficiency of major soluble pollutants in the wastewater was greater than 95% in the BNR system. When a step input of phenol was introduced to check the stability of the overall system, the nitrification was markedly inhibited because of the incomplete degradation of phenol in the carbon-removal stage. However, after this brief inhibition, the nitrification stage recovered to its normal efficiency within 18 days.

  6. 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.

  7. Reassessing carbon sequestration in the North China Plain via addition of nitrogen.

    PubMed

    Dong, Wenxu; Duan, Yongmei; Wang, Yuying; Hu, Chunsheng

    2016-09-01

    Soil inorganic carbon (SIC) exerts a strong influence on the carbon (C) sequestered in response to nitrogen (N) additions in arid and semi-arid ecosystems, but limited information is available on in situ SIC storage and dissolution at the field level. This study determined the soil organic/inorganic carbon storage in the soil profile at 0-100cm depths and the concentration of dissolved inorganic carbon (DIC) in soil leachate in 4N application treatments (0, 200, 400, and 600kgNha(-1)yr(-)(1)) for 15years in the North China Plain. The objectives were to evaluate the effect of nitrogen fertilizer on total amount of carbon sequestration and the uptake of atmospheric CO2 in an agricultural system. Results showed that after 15years of N fertilizer application the SOC contents at depths of 0-100cm significantly increased, whereas the SIC contents significantly decreased at depths of 0-60cm. However, the actual measured loss of carbonate was far higher than the theoretical maximum values of dissolution via protons from nitrification. Furthermore, the amount of HCO3(-) and the HCO3(-)/(Ca(2+)+Mg(2+)) ratio in soil leachate were higher in the N application treatments than no fertilizer input (CK) for the 0-80cm depth. The result suggested that the dissolution of carbonate was mainly enhanced by soil carbonic acid, a process which can absorb soil or atmosphere CO2 and less influenced by protons through the nitrification which would release CO2. To accurately evaluate soil C sequestration under N input scenarios in semi-arid regions, future studies should include both changes in SIC storage as well as the fractions of dissolution with different sources of acids in soil profiles. PMID:27135576

  8. Atomic configuration of nitrogen-doped single-walled carbon nanotubes.

    PubMed

    Arenal, Raul; March, Katia; Ewels, Chris P; Rocquefelte, Xavier; Kociak, Mathieu; Loiseau, Annick; Stéphan, Odile

    2014-10-01

    Having access to the chemical environment at the atomic level of a dopant in a nanostructure is crucial for the understanding of its properties. We have performed atomically resolved electron energy-loss spectroscopy to detect individual nitrogen dopants in single-walled carbon nanotubes and compared with first-principles calculations. We demonstrate that nitrogen doping occurs as single atoms in different bonding configurations: graphitic-like and pyrrolic-like substitutional nitrogen neighboring local lattice distortion such as Stone-Thrower-Wales defects. We also show that the largest fraction of nitrogen amount is found in poly aromatic species that are adsorbed on the surface of the nanotube walls. The stability under the electron beam of these nanotubes has been studied in two different cases of nitrogen incorporation content and configuration. These findings provide key information for the applications of these nanostructures.

  9. Atomic layer deposition on suspended single-walled carbon nanotubes via gas-phase noncovalent functionalization.

    PubMed

    Farmer, Damon B; Gordon, Roy G

    2006-04-01

    Alternating exposures of nitrogen dioxide gas and trimethylaluminum vapor are shown to functionalize the surfaces of single-walled carbon nanotubes with a self-limited monolayer. Functionalized nanotube surfaces are susceptible to atomic layer deposition of continuous, radially isotropic material. This allows for the creation of coaxial nanotube structures of multiple materials with precisely controlled diameters. Functionalization involves only weak physical bonding, avoiding covalent modification, which should preserve the unique optical, electrical, and mechanical properties of the nanotubes. PMID:16608267

  10. Controlled fabrication of theophylline imprinted polymers on multiwalled carbon nanotubes via atom transfer radical polymerization.

    PubMed

    Xu, Jianxiong; Gao, Yong; Li, Huaming

    2011-02-01

    Theophylline imprinted polymers were synthesized on the surface of multiwalled carbon nanotubes via atom transfer radical polymerization using brominated multiwalled carbon nanotubes as an initiator. The nanotube-based initiator was prepared by directly reacting acyl chloride-modified multiwalled carbon nanotubes with 2-hydroxylethyl-2'-bromoisobutyrate. The grafting copolymerization of 2-hydroxyethyl-2-methyl-2-propenoate and ethylene glycol dimethacrylate in the presence of template theophylline led to thin molecularly imprinted polymer films coating multiwalled carbon nanotubes. The thickness of molecularly imprinted polymer films prepared in this study was about 5 nm as determined by transmission electron microscopy. Fourier-transform infrared spectroscopy was utilized to follow the introduction of initiator groups as well as polymers on the carbon nanotube surfaces. Thermogravimetric analysis indicated that the molecularly imprinted polymers were successfully grown from the carbon nanotube surfaces, with the final products having a polymer weight percentage of ca. 50 wt%. The adsorption properties, such as adsorption dynamics, special binding and selective recognition capacity, of the as-prepared molecularly imprinted polymer films were evaluated. The results demonstrated that the composite of molecularly imprinted polymers and multiwalled carbon nanotubes not only possessed a rapid dynamics but also exhibited a good selectivity toward theophylline, compared to caffeine.

  11. Miniaturized dielectric barrier discharge carbon atomic emission spectrometry with online microwave-assisted oxidation for determination of total organic carbon.

    PubMed

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

    2014-07-01

    A simple, rapid, and portable system consisted of a laboratory-built miniaturized dielectric barrier discharge atomic emission spectrometer and a microwave-assisted persulfate oxidation reactor was developed for sensitive flow injection analysis or continuous monitoring of total organic carbon (TOC) in environmental water samples. The standard/sample solution together with persulfate was pumped to the reactor to convert organic compounds to CO2, which was separated from liquid phase and transported to the spectrometer for detection of the elemental specific carbon atomic emission at 193.0 nm. The experimental parameters were systematically investigated. A limit of detection of 0.01 mg L(-1) (as C) was obtained based on a 10 mL sample injection volume, and the precision was better than 6.5% (relative standard deviation, RSD) at 0.1 mg L(-1). The system was successfully applied for TOC analysis of real environmental water samples. The obtained TOC value of 30 test samples agreed well with those by the standard high-temperature combustion coupled nondispersive infrared absorption method. Most importantly, the system showed good capability of in situ continuous monitoring of total organic carbon in environmental water.

  12. 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.

  13. 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

    2001-10-01

    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 (i) its structural and chemical simplicity, (ii) interest in Mg(OH){sub 2} gas-solid carbonation as a potentially cost-effective CO{sub 2} mineral sequestration process component, and (iii) 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 report covers the third year progress of this grant, as well as providing an integrated overview of the progress in years 1-3, as we have been granted a one-year no-cost extension to wrap up a few studies and publications to optimize project impact.

  14. 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.

  15. 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. PMID:23612160

  16. Analysis of the benefits of carbon credits to hydrogen addition to midsize gas turbine feedstocks.

    SciTech Connect

    Miller, J.; Towns, B.; Keller, Jay O.; Schefer, Robert W.; Skolnik, Edward G.

    2006-02-01

    The addition of hydrogen to the natural gas feedstocks of midsize (30-150 MW) gas turbines was analyzed as a method of reducing nitrogen oxides (NO{sub x}) and CO{sub 2} emissions. In particular, the costs of hydrogen addition were evaluated against the combined costs for other current NO{sub x} and CO{sub 2} emissions control technologies for both existing and new systems to determine its benefits and market feasibility. Markets for NO{sub x} emissions credits currently exist in California and the Northeast States and are expected to grow. Although regulations are not currently in place in the United States, several other countries have implemented carbon tax and carbon credit programs. The analysis thus assumes that the United States adopts future legislation similar to these programs. Therefore, potential sale of emissions credits for volunteer retrofits was also included in the study. It was found that hydrogen addition is a competitive alternative to traditional emissions abatement techniques under certain conditions. The existence of carbon credits shifts the system economics in favor of hydrogen addition.

  17. Iodinated (Perfluoro)alkyl Quinoxalines by Atom Transfer Radical Addition Using ortho-Diisocyanoarenes as Radical Acceptors.

    PubMed

    Leifert, Dirk; Studer, Armido

    2016-09-12

    A simple method for the preparation of functionalized quinoxalines is reported. Starting from readily accessible ortho-diisocyanoarenes and (perfluoro)alkyl iodides, the quinoxaline core is constructed during (perfluoro)alkylation by atom transfer radical addition (ATRA), resulting in 2-iodo-3-(perfluoro)alkylquinoxalines. The radical cascades are readily initiated either with visible light or by using α,α'-azobisisobutyronitrile (AIBN). The heteroarene products are obtained in high yields (up to 94 %), and the method can be readily scaled up. Useful follow-up chemistry documents the value of the novel radical quinoxaline synthesis.

  18. Iodinated (Perfluoro)alkyl Quinoxalines by Atom Transfer Radical Addition Using ortho-Diisocyanoarenes as Radical Acceptors.

    PubMed

    Leifert, Dirk; Studer, Armido

    2016-09-12

    A simple method for the preparation of functionalized quinoxalines is reported. Starting from readily accessible ortho-diisocyanoarenes and (perfluoro)alkyl iodides, the quinoxaline core is constructed during (perfluoro)alkylation by atom transfer radical addition (ATRA), resulting in 2-iodo-3-(perfluoro)alkylquinoxalines. The radical cascades are readily initiated either with visible light or by using α,α'-azobisisobutyronitrile (AIBN). The heteroarene products are obtained in high yields (up to 94 %), and the method can be readily scaled up. Useful follow-up chemistry documents the value of the novel radical quinoxaline synthesis. PMID:27510610

  19. 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.

  20. Artificial neural network approach for atomic coordinate prediction of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Acı, Mehmet; Avcı, Mutlu

    2016-07-01

    In this paper, four artificial neural network (ANN) models [i.e., feed-forward neural network (FFNN), function fitting neural network (FITNET), cascade-forward neural network (CFNN) and generalized regression neural network] have been developed for atomic coordinate prediction of carbon nanotubes (CNTs). The research reported in this study has two primary objectives: (1) to develop ANN prediction models that calculate atomic coordinates of CNTs instead of using any simulation software and (2) to use results of the ANN models as an initial value of atomic coordinates for reducing number of iterations in calculation process. The dataset consisting of 10,721 data samples was created by combining the atomic coordinates of elements and chiral vectors using BIOVIA Materials Studio CASTEP (CASTEP) software. All prediction models yield very low mean squared normalized error and mean absolute error rates. Multiple correlation coefficient (R) results of FITNET, FFNN and CFNN models are close to 1. Compared with CASTEP, calculation times decrease from days to minutes. It would seem possible to predict CNTs' atomic coordinates using ANN models can be successfully used instead of mathematical calculations.

  1. 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.

  2. Analysis of Tank 43H Samples at the Conclusion of Uranyl Carbonate Addition

    SciTech Connect

    Oji, L.N.

    2002-10-15

    Tank 43H serves as the feed Tank to the 2H evaporator. In the months of July and August 2001, about 21,000 gallons of a depleted uranyl carbonate solution were added to Tank 43H and agitated with two Flygt mixers. The depleted uranium addition served to decrease the U-235 enrichment in the Tank 43H supernate so that the supernate could be evaporated with no risk of accumulating enriched uranium.

  3. 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.

  4. 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.

  5. 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

    We performed a series of first-principles calculations to investigate the foreign interstitial atom (FIA) interactions with intrinsic defects in tungsten. We found the following: (i) The introduction of the FIA reduces the vacancy formation energy, resulting in the increase of the equilibrium concentration of vacancies. (ii) The positive binding energy between two FIAs suggests that the FIA can attract other FIAs. (iii) The FIA is easily trapped by the vacancy, and a single vacancy can accommodate up to 4 and 6 atoms in a stable manner for carbon and nitrogen, respectively. (iv) There is an attraction interaction between the FIA and the self-interstitial atom (SIA), and the FIA can reduce the SIA jump frequency and enhance the formation of SIA clusters in tungsten. Moreover, the difference between carbon and nitrogen are also discussed with respect to the formation of FIA-FIA covalent bond and the accumulation around the saturated -, where d is the ith nearest-neighbor (inn) solute-tungsten distance before relaxation and ▵di=(di-d) is the change in distance due to relaxation. The calculated relaxations are presented in Table 3. The relaxations of 1nn of octahedral interstitial carbon and nitrogen atoms are 23.30% and 22.42%, respectively, which are greatly larger than the relaxations of other nearest-neighbor atoms (0.1-2%). These results indicate that the influence range of FIA is very local. The lattice distortions introduced by the octahedral interstitial carbon or nitrogen atom can be characterized by determining the dipolar tensor from Kanzaki forces. Here, to obtain the dipolar tensor, we adopt a similar calculation procedure as used in Ref. [14], where the dipolar tensor P is calculated from the Kanzaki forces on all the tungsten atoms. The detailed procedure could be found in Ref. [14]. Due to the symmetry of the configuration, the dipolar tensor has two independent values: P11 and P33, which are listed in Table 3. Similarly with Ref. [14], approximate

  6. Design-atom approach for the quantum mechanical/molecular mechanical covalent boundary: a design-carbon atom with five valence electrons.

    PubMed

    Xiao, Chuanyun; Zhang, Yingkai

    2007-09-28

    A critical issue underlying the accuracy and applicability of the combined quantum mechanical/molecular mechanical (QM/MM) methods is how to describe the QM/MM boundary across covalent bonds. Inspired by the ab initio pseudopotential theory, here we introduce a novel design atom approach for a more fundamental and transparent treatment of this QM/MM covalent boundary problem. The main idea is to replace the boundary atom of the active part with a design atom, which has a different number of valence electrons but very similar atomic properties. By modifying the Troullier-Martins scheme, which has been widely employed to construct norm-conserving pseudopotentials for density functional calculations, we have successfully developed a design-carbon atom with five valence electrons. Tests on a series of molecules yield very good structural and energetic results and indicate its transferability in describing a variety of chemical bonds, including double and triple bonds.

  7. 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.

  8. 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

  9. Oxidized carbon nitrides: water-dispersible, atomically thin carbon nitride-based nanodots and their performances as bioimaging probes.

    PubMed

    Oh, Junghoon; Yoo, Ran Ji; Kim, Seung Yeon; Lee, Yong Jin; Kim, Dong Wook; Park, Sungjin

    2015-04-13

    Three-dimensional (3D) carbon nitride (C3 N4 )-based materials show excellent performance in a wide range of applications because of their suitable band structures. To realize the great promise of two-dimensional (2D) allotropes of various 3D materials, it is highly important to develop routes for the production of 2D C3 N4 materials, which are one-atom thick, in order to understand their intrinsic properties and identify their possible applications. In this work, water-dispersible, atomically thin, and small carbon nitride nanodots were produced using the chemical oxidation of graphitic C3 N4 . Various analyses, including X-ray diffraction, X-ray photoelectron, Fourier-transform infrared spectroscopy, and combustion-based elemental analysis, and thermogravimetric analysis, confirmed the production of 3D oxidized C3 N4 materials. The 2D C3 N4 nanodots were successfully exfoliated as individual single layers; their lateral dimension was several tens of nanometers. They showed strong photoluminescence in the visible region as well as excellent performances as cell-imaging probes in an in vitro study using confocal fluorescence microscopy.

  10. 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

  11. 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.

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

    PubMed

    Erikat, I A; Hamad, B A

    2013-11-01

    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.

  13. 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.

  14. 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

    2016-09-01

    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.

  15. Aptamer sandwich-based carbon nanotube sensors for single-carbon-atomic-resolution detection of non-polar small molecular species.

    PubMed

    Lee, Joohyung; Jo, Minjoung; Kim, Tae Hyun; Ahn, Ji-Young; Lee, Dong-ki; Kim, Soyoun; Hong, Seunghun

    2011-01-01

    A portable sensor platform for the detection of small molecular species is crucial for the on-site monitoring of environmental pollutants, food toxicants, and disease-related metabolites. However, it is still extremely difficult to find highly selective and sensitive sensor platforms for general small molecular detection. Herein, we report aptamer sandwich-based carbon nanotube sensor strategy for small molecular detection, where aptamers were utilized to capture target molecules as well as to enhance the sensor signals. We successfully demonstrated the detection of non-polar bisphenol A molecules with a 1 pM sensitivity. Significantly, our sensors were able to distinguish between similar small molecular species with single-carbon-atomic resolution. Furthermore, using the additional biotin modification on labeling aptamer, we enhanced the detection limit of our sensors down to 10 fM. This strategy allowed us to detect non-polar small molecular species using carbon nanotube transistors, thus overcoming the fundamental limitation of field effect transistor-based sensors. Considering the extensive applications of sandwich assay for the detection of rather large biomolecules, our results should open up completely new dimension in small molecular detection technology and should enable a broad range of applications such as environmental protection and food safety.

  16. Atomic layer deposition encapsulated activated carbon electrodes for high voltage stable supercapacitors.

    PubMed

    Hong, Kijoo; Cho, Moonkyu; Kim, Sang Ouk

    2015-01-28

    Operating voltage enhancement is an effective route for high energy density supercapacitors. Unfortunately, widely used activated carbon electrode generally suffers from poor electrochemical stability over 2.5 V. Here we present atomic layer deposition (ALD) encapsulation of activated carbons for high voltage stable supercapacitors. Two-nanometer-thick Al2O3 dielectric layers are conformally coated at activated carbon surface by ALD, well-maintaining microporous morphology. Resultant electrodes exhibit excellent stability at 3 V operation with 39% energy density enhancement from 2.5 V operation. Because of the protection of surface functional groups and reduction of electrolyte degradation, 74% of initial voltage was maintained 50 h after full charge, and 88% of capacitance was retained after 5000 cycles at 70 °C accelerated test, which correspond to 31 and 17% improvements from bare activated carbon, respectively. This ALD-based surface modification offers a general method to enhance electrochemical stability of carbon materials for diverse energy and environmental applications.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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). PMID:25556005

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. Imaging the elastic properties of coiled carbon nanotubes with atomic force microscopy

    PubMed

    Volodin; Ahlskog; Seynaeve; Van Haesendonck C; Fonseca; Nagy

    2000-04-10

    Coiled carbon nanotubes were produced catalytically by thermal decomposition of hydrocarbon gas. After deposition on a silicon substrate, the three-dimensional structure of the helix-shaped multiwalled nanotubes can be visualized with atomic force microscopy. Helical structures of both chiralities are present in the nanotube deposits. For larger coil diameters ( >170 nm), force modulation microscopy allows one to probe the local elasticity along the length of the coil. Our results agree with the classical theory of elasticity. Similar to the case of straight nanotubes, the Young modulus of coiled multiwalled nanotubes remains comparable to the very high Young modulus of hexagonal graphene sheets.

  9. STM Images of Atomic-Scale Carbon Nanotube Defects Produced by Ar+ Irradiation

    SciTech Connect

    Osvath, Z.; Vertesy, G.; Tapaszto, L.; Weber, F.; Horvath, Z.E.; Gyulai, J.; Biro, L.P.

    2005-09-27

    Multi-wall carbon nanotubes (MWCNTs) dispersed on graphite (HOPG) substrate were irradiated with Ar+ ions of 30 keV, using a low-dose of D 5x1011 ions/cm2. The irradiated samples were investigated by scanning tunneling microscopy (STM) under ambient conditions. Atomic resolution STM images reveal individual nanotube defects, which appear as hillocks of 1-2 angstroms in height, due to the locally changed electronic structure. After annealing at 450 deg. C in nitrogen atmosphere, the irradiated MWCNTs were investigated again by STM. The effect of the heat treatment on the irradiation-induced nanotube defects is also discussed.

  10. Fabrication process of carbon nanotube field effect transistors using atomic layer deposition passivation for biosensors.

    PubMed

    Nakashima, Yasuhiro; Ohno, Yutaka; Kishimoto, Shigeru; Okochi, Mina; Honda, Hiroyuki; Mizutani, Takashi

    2010-06-01

    Fabrication process of the carbon nanotube (CNT) field effect transistors (FETs) for biosensors was studied. Atomic layer deposition (ALD) of HfO2 was applied to the deposition of the passivation/gate insulator film. The CNT-FETs did not show the drain current degradation after ALD passivation even though the passivation by Si3N4 deposited by plasma-enhanced chemical vapor deposition (PECVD) resulted in a significant drain current decrease. This indicates the advantage of the present ALD technique in terms of the damage suppression. The biosensing operation was confirmed using thus fabricated CNT-FETs. PMID:20355371

  11. Synthesis and characterization of carbon fibers functionalized with poly (glycidyl methacrylate) via atom transfer radical polymerization

    NASA Astrophysics Data System (ADS)

    Wu, Yongwei; Xiong, Lei; Qin, Xiaokang; Wang, Zhengyue; Ding, Bei; Ren, Huan; Pi, Xiaolong

    2015-07-01

    In this work, polyacrylonitrile (PAN)-based carbon fibers (CF) were chemically modified with poly (glycidyl methacrylate) (PGMA) via atom transfer radical polymerization (ATRP) to improve the interaction between the CF and polymer matrix. The FT-IR, TGA, and XPS were used to determine the chemical structure of the resulting products and the quantities of PGMA chains grafted from the CF surface. The experimental results confirm that the CF surface was functionalized and glycidyl methacrylate was graft-polymerized onto the CF, and the grafting content of polymer could reach 10.2%.

  12. [Effects of nitrogen and carbon addition and arbuscular mycorrhiza on alien invasive plant Ambrosia artemisiifolia].

    PubMed

    Huang, Dong; Sang, Wei-guo; Zhu, Li; Song, Ying-ying; Wang, Jin-ping

    2010-12-01

    A greenhouse control experiment was conducted to explore the effects of nitrogen and carbon addition and arbuscular mycorrhiza (AM) on the growth of alien invasive plant Ambrosia artemisiifolia (common ragweed). Nitrogen addition had no significant effects on the morphological indices, biomass and its allocation, and absolute growth rate of A. artemisiifolia, but increased the nitrogen content in the aboveground and underground parts of the plant significantly. Carbon addition increased the content of soil available nitrogen. In this case, the biomass allocation in root system for nutrient (nitrogen) absorption promoted, resulting in a remarkable decrease of branch number, total leaf area, specific leaf area (SLA), and leaf mass ratio. As a result, the total biomass decreased significantly. The symbiosis of A. artemisiifolia and AM fungi had great influence on the common ragweed's soil nitrogen acclimation, which enhanced its resource-capture by the increase of SLA, and this effect was more significant when the soil nitrogen content was low. AM fungi played an important role in the growth of A. artemisiifolia in low-nitrogen environment.

  13. 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.

  14. 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.

  15. 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.

  16. 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

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

    PubMed Central

    Kenig, Fabien; Simons, Dirk-Jan H.; Crich, David; Cowen, James P.; Ventura, Gregory T.; Rehbein-Khalily, Tatiana; Brown, Todd C.; Anderson, Ken B.

    2003-01-01

    A pseudohomologous series of branched aliphatic alkanes with a quaternary substituted carbon atom (BAQCs, specifically 2,2-dimethylalkanes and 3,3- and 5,5-diethylalkanes) were identified in warm (65°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. PMID:14551322

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

    PubMed

    Kenig, Fabien; Simons, Dirk-Jan H; Crich, David; Cowen, James P; Ventura, Gregory T; Rehbein-Khalily, Tatiana; Brown, Todd C; Anderson, Ken B

    2003-10-28

    A pseudohomologous series of branched aliphatic alkanes with a quaternary substituted carbon atom (BAQCs, specifically 2,2-dimethylalkanes and 3,3- and 5,5-diethylalkanes) were identified in warm (65 degrees 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. PMID:14551322

  19. 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.

  20. Sc3CH@C80: selective (13)C enrichment of the central carbon atom.

    PubMed

    Junghans, Katrin; Rosenkranz, Marco; Popov, Alexey A

    2016-05-01

    Sc3CH@C80 is synthesized and characterized by (1)H, (13)C, and (45)Sc NMR. A large negative chemical shift of the proton, -11.73 ppm in the Ih and -8.79 ppm in the D5h C80 cage isomers, is found. (13)C satellites in the (1)H NMR spectrum enabled indirect determination of the (13)C chemical shift for the central carbon at 173 ± 1 ppm. Intensity of the satellites allowed determination of the (13)C content for the central carbon atom. This unique possibility is applied to analyze the cluster/cage (13)C distribution in mechanistic studies employing either (13)CH4 or (13)C powder to enrich Sc3CH@C80 with (13)C. PMID:27109443

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

    PubMed

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

    2015-01-01

    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

  2. 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

  3. Controlling a toxic shock of pentachlorophenol (PCP) to anaerobic digestion using activated carbon addition.

    PubMed

    Xiao, Yeyuan; De Araujo, Cecilia; Sze, Chun Chau; Stuckey, David C

    2015-04-01

    Several powdered and granular activated carbons (PACs and GACs) were tested for adsorption of pentachlorophenol (PCP) in bench-scale anaerobic digestion reactors to control the toxicity of PCP to acetoclastic methanogenesis. Results showed that the adsorption capacities of PAC were reduced by 21-54%, depending on the PAC addition time, in the presence of the methanogenic sludge compared to the controls without sludge. As a preventive measure, PAC at a low dose of 20% (mass ratio to the VSS) added 24 h prior to, or simultaneously with, the addition of PCP could completely eliminate the toxic effects of PCP. At the same dose, PAC also enabled methanogenesis to recover immediately after the sludge had been exposed to PCP for 24h. GAC was not effective in enabling the recovery of methanogenesis due to its slow adsorption kinetics; however, at a dose of 80% it could partially ameliorate the toxic shock of PCP. PMID:25665874

  4. 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)

  5. 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.

  6. 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. PMID:26799641

  7. 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.

  8. 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. PMID:26948716

  9. 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.

  10. CHARMM additive all-atom force field for carbohydrate derivatives and its utility in polysaccharide and carbohydrate-protein modeling

    PubMed Central

    Guvench, Olgun; Mallajosyula, Sairam S.; Raman, E. Prabhu; Hatcher, Elizabeth; Vanommeslaeghe, Kenno; Foster, Theresa J.; Jamison, Francis W.; MacKerell, Alexander D.

    2011-01-01

    Monosaccharide derivatives such as xylose, fucose, N-acetylglucosamine (GlcNAc), N-acetylgalactosamine (GlaNAc), glucuronic acid, iduronic acid, and N-acetylneuraminic acid (Neu5Ac) are important components of eukaryotic glycans. The present work details development of force-field parameters for these monosaccharides and their covalent connections to proteins via O-linkages to serine or threonine sidechains and via N-linkages to asparagine sidechains. The force field development protocol was designed to explicitly yield parameters that are compatible with the existing CHARMM additive force field for proteins, nucleic acids, lipids, carbohydrates, and small molecules. Therefore, when combined with previously developed parameters for pyranose and furanose monosaccharides, for glycosidic linkages between monosaccharides, and for proteins, the present set of parameters enables the molecular simulation of a wide variety of biologically-important molecules such as complex carbohydrates and glycoproteins. Parametrization included fitting to quantum mechanical (QM) geometries and conformational energies of model compounds, as well as to QM pair interaction energies and distances of model compounds with water. Parameters were validated in the context of crystals of relevant monosaccharides, as well NMR and/or x-ray crystallographic data on larger systems including oligomeric hyaluronan, sialyl Lewis X, O- and N-linked glycopeptides, and a lectin:sucrose complex. As the validated parameters are an extension of the CHARMM all-atom additive biomolecular force field, they further broaden the types of heterogeneous systems accessible with a consistently-developed force-field model. PMID:22125473

  11. Computations on the primary photoreaction of Br2 with CO2: stepwise vs concerted addition of Br atoms.

    PubMed

    Xu, Kewei; Korter, Timothy M; Braiman, Mark S

    2015-04-01

    It was proposed previously that Br2-sensitized photolysis of liquid CO2 proceeds through a metastable primary photoproduct, CO2Br2. Possible mechanisms for such a photoreaction are explored here computationally. First, it is shown that the CO2Br radical is not stable in any geometry. This rules out a free-radical mechanism, for example, photochemical splitting of Br2 followed by stepwise addition of Br atoms to CO2-which in turn accounts for the lack of previously observed Br2+CO2 photochemistry in gas phases. A possible alternative mechanism in liquid phase is formation of a weakly bound CO2:Br2 complex, followed by concerted photoaddition of Br2. This hypothesis is suggested by the previously published spectroscopic detection of a binary CO2:Br2 complex in the supersonically cooled gas phase. We compute a global binding-energy minimum of -6.2 kJ mol(-1) for such complexes, in a linear geometry. Two additional local minima were computed for perpendicular (C2v) and nearly parallel asymmetric planar geometries, both with binding energies near -5.4 kJ mol(-1). In these two latter geometries, C-Br and O-Br bond distances are simultaneously in the range of 3.5-3.8 Å, that is, perhaps suitable for a concerted photoaddition under the temperature and pressure conditions where Br2 + CO2 photochemistry has been observed.

  12. Reaction of homopiperazine with endogenous formaldehyde: a carbon hydrogen addition metabolite/product identified in rat urine and blood.

    PubMed

    Martin, Scott; Lenz, Eva M; Temesi, Dave; Wild, Martin; Clench, Malcolm R

    2012-08-01

    Drug reactivity and bioactivation are of major concern to the development of potential drug candidates in the pharmaceutical industry (Chem Res Toxicol 17:3-16, 2004; Chem Res Toxicol 19:889-893, 2006). Identifying potentially problematic compounds as soon as possible in the discovery process is of great importance, so often early in vitro screening is used to speed up attrition. Identification of reactive moieties is relatively straightforward with appropriate in vitro trapping experiments; however, on occasion unexpected reactive intermediates can be found later during more detailed in vivo studies. Here, we present one such example involving a series of compounds from an early drug discovery campaign. These compounds were found to react with endogenous formaldehyde from a rat in vivo study, resulting in the formation of novel +13-Da bridged homopiperazine products (equivalent to the addition of one carbon and one hydrogen atom), which were detected in urine and blood. The identification of these +13-Da products and their origin and mechanism of formation are described in detail through analyses of a representative homopiperazine compound [N-(3-(3-fluorophenyl)-1,2,4-thiadiazol-5-yl)-4-(4-isopropyl-1,4-diaze-pane-2-carbonyl)piperazine-1-carboxamide (AZX)] by liquid chromatography-UV-mass spectrometry, (1)H NMR, and chemical tests. PMID:22550270

  13. 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.

  14. Mineral elements of subtropical tree seedlings in response to elevated carbon dioxide and nitrogen addition.

    PubMed

    Huang, Wenjuan; Zhou, Guoyi; Liu, Juxiu; Zhang, Deqiang; Liu, Shizhong; Chu, Guowei; Fang, Xiong

    2015-01-01

    Mineral elements in plants have been strongly affected by increased atmospheric carbon dioxide (CO2) concentrations and nitrogen (N) deposition due to human activities. However, such understanding is largely limited to N and phosphorus in grassland. Using open-top chambers, we examined the concentrations of potassium (K), calcium (Ca), magnesium (Mg), aluminum (Al), copper (Cu) and manganese (Mn) in the leaves and roots of the seedlings of five subtropical tree species in response to elevated CO2 (ca. 700 μmol CO2 mol(-1)) and N addition (100 kg N ha(-1) yr(-1)) from 2005 to 2009. These mineral elements in the roots responded more strongly to elevated CO2 and N addition than those in the leaves. Elevated CO2 did not consistently decrease the concentrations of plant mineral elements, with increases in K, Al, Cu and Mn in some tree species. N addition decreased K and had no influence on Cu in the five tree species. Given the shifts in plant mineral elements, Schima superba and Castanopsis hystrix were less responsive to elevated CO2 and N addition alone, respectively. Our results indicate that plant stoichiometry would be altered by increasing CO2 and N deposition, and K would likely become a limiting nutrient under increasing N deposition in subtropics. PMID:25794046

  15. 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.

  16. 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.

  17. Effects of ions and atomic hydrogen in plasma-assisted growth of single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Denysenko, I.; Ostrikov, K.; Yu, M. Y.; Azarenkov, N. A.

    2007-10-01

    The growth of single-walled carbon nanotubes (SWCNTs) in plasma-enhanced chemical vapor deposition (PECVD) is studied using a surface diffusion model. It is shown that at low substrate temperatures (⩽1000K), the atomic hydrogen and ion fluxes from the plasma can strongly affect nanotube growth. The ion-induced hydrocarbon dissociation can be the main process that supplies carbon atoms for SWCNT growth and is responsible for the frequently reported higher (compared to thermal chemical vapor deposition) nanotube growth rates in plasma-based processes. On the other hand, excessive deposition of plasma ions and atomic hydrogen can reduce the diffusion length of the carbon-bearing species and their residence time on the nanotube lateral surfaces. This reduction can adversely affect the nanotube growth rates. The results here are in good agreement with the available experimental data and can be used for optimizing SWCNT growth in PECVD.

  18. 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

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

    SciTech Connect

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

    2015-02-21

    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.

  20. 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.

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

    PubMed Central

    Cleveland, Cory C.; Townsend, Alan R.

    2006-01-01

    Terrestrial biosphere–atmosphere carbon dioxide (CO2) 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 CO2 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 CO2 losses stimulated by N and P fertilization suggest that knowledge of such patterns and their effects on soil CO2 efflux is critical for understanding the role of tropical forests in a rapidly changing global C cycle. PMID:16793925

  2. 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

  3. Mechanical properties of SiB6 addition of carbon sintered body

    NASA Astrophysics Data System (ADS)

    Tanaka, Samon; Fukushima, Noriyuki; Matsushita, Jun-ichi; Akatsu, T.; Niihara, K.; Yasuda, E.

    2001-04-01

    Boride material is said as the useful material, which has high melting point and high strength. B4C in carbide is very hard at the next of the diamond and cubic-BN in the Mohs hardness and B4C has excellent chemical stability and high strength. B4C is being used as the polishing material from the hardness. However, it is difficult to make sintered body from high melting point (2623 K). Several silicon boride phases such as SiB4, SiB6, SiB6-x, SiB6+x, and Si11B31, were previously reported. Silicon hexaboride (SiB6) has proved to be a potentially useful material because of its high degree of hardness, moderate melting point (2123 K), and low specific gravity. We studied the preparation of SiB6-B4C-SiC sintered body in this report. We knew experientially that SiB6 reacts with carbon at the high temperature, and forms B4C or SiC. Carbon addition SiB6 sintered body produced by hot pressing and reaction sintering that sintering condition was 1973 K for 3.6 ks in vacuum under a pressure of 25 MPa. The relative density of sintered bodies (SiB6-0,5,10,15 wt%C) was approximately 100%. Characterization of mechanical properties was used indentation, Vickers hardness and thermal

  4. Effect of Addition of Multiwalled Carbon Nanotubes on the Piezoelectric Properties of Polypropylene Filaments.

    PubMed

    Bayramol, D Vatansever; Soin, N; Hadimani, R L; Shah, T H; Siores, E

    2015-09-01

    The effect of addition of multiwalled carbon nanotubes (CNTs) on the piezoelectric properties of polypropylene (PP) monofilaments has been investigated. Various amounts of CNTs (0%, 0.01%, 0.1% and 1% weight ratios) were melt-blended with PP and the resulting nanocomposites were extruded in a continuous process with simultaneous on-line poling to produce monofilaments. Concurrent stretching at a draw ratio of 5:1 and polarisation at applied electric fields of 15 kV of PP/CNT filaments was observed to enhance the piezoelectric properties. The microstructure and crystallinity of the filaments was analysed using scanning electron microscopy (SEM), differential scanning calorimetric (DSC) and Fourier transform infrared spectroscopy (FTIR) techniques. Voltage generation by the CNT-modified PP filaments was determined by the application of predetermined load impact. The results show that the incorporation of CNTs in the PP fibre structure has a considerable impact on the enhancement of piezoelectric properties of the PP filament obtained that the peak voltage generation was almost four fold (from 0.76 V to 2.92 V) when 0.1 wt% of CNTs added into the polymer. This is owing to the fact that carbon nanotubes act as nucleating agent for enhancing the crystallisation during the melt extrusion process.

  5. Effect of Addition of Multiwalled Carbon Nanotubes on the Piezoelectric Properties of Polypropylene Filaments.

    PubMed

    Bayramol, D Vatansever; Soin, N; Hadimani, R L; Shah, T H; Siores, E

    2015-09-01

    The effect of addition of multiwalled carbon nanotubes (CNTs) on the piezoelectric properties of polypropylene (PP) monofilaments has been investigated. Various amounts of CNTs (0%, 0.01%, 0.1% and 1% weight ratios) were melt-blended with PP and the resulting nanocomposites were extruded in a continuous process with simultaneous on-line poling to produce monofilaments. Concurrent stretching at a draw ratio of 5:1 and polarisation at applied electric fields of 15 kV of PP/CNT filaments was observed to enhance the piezoelectric properties. The microstructure and crystallinity of the filaments was analysed using scanning electron microscopy (SEM), differential scanning calorimetric (DSC) and Fourier transform infrared spectroscopy (FTIR) techniques. Voltage generation by the CNT-modified PP filaments was determined by the application of predetermined load impact. The results show that the incorporation of CNTs in the PP fibre structure has a considerable impact on the enhancement of piezoelectric properties of the PP filament obtained that the peak voltage generation was almost four fold (from 0.76 V to 2.92 V) when 0.1 wt% of CNTs added into the polymer. This is owing to the fact that carbon nanotubes act as nucleating agent for enhancing the crystallisation during the melt extrusion process. PMID:26716297

  6. 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.

  7. Additive-induced morphological tuning of self-assembled silica-barium carbonate crystal aggregates

    NASA Astrophysics Data System (ADS)

    Kellermeier, Matthias; Glaab, Fabian; Carnerup, Anna M.; Drechsler, Markus; Gossler, Benjamin; Hyde, Stephen T.; Kunz, Werner

    2009-04-01

    Crystallisation of barium carbonate from alkaline silica solutions results in the formation of extraordinary micron-scale architectures exhibiting non-crystallographic curved shapes, such as helical filaments and worm-like braids. These so-called "silica biomorphs" consist of a textured assembly of uniform elongated witherite nanocrystallites, which is occasionally sheathed by a skin of amorphous silica. Although great efforts have been devoted to clarifying the physical origin of these fascinating materials, to date little is known about the processes underlying the observed self-organisation. Herein, we describe the effect of two selected additives, a cationic surfactant and a cationic polymer, on the morphology of the forming crystal aggregates, and relate changes to experiments conducted in the absence of additives. Minor amounts of both substances are shown to exert a significant influence on the growth process, leading to the formation of predominantly flower-like spherulitic aggregates. The observed effects are discussed in terms of feasible morphogenesis pathways. Based on the assumption of a template membrane steering biomorph formation, it is proposed that the two additives are capable of performing specific bridging functions promoting the aggregation of colloidal silica which constitutes the membrane. Morphological changes are tentatively ascribed to varying colloid coordination effecting distinct membrane curvatures.

  8. Flux enhancement with powdered activated carbon addition in the membrane anaerobic bioreactor

    SciTech Connect

    Park, H.; Choo, K.H.; Lee, C.H.

    1999-10-01

    The effect of powdered activated carbon (PAC) addition on the performance of a membrane-coupled anaerobic bioreactor (MCAB) was investigated in terms of membrane filterability and treatability through a series of batch and continuous microfiltration (MF) experiments. In both batch and continuous MF of the digestion broth, a flux improvement with PAC addition was achieved, especially when a higher shear rate and/or a higher PAC dose were applied. Both the fouling and cake layer resistances decreased continuously with increasing the PAC dose up to 5 g/L. PAC played an important role in substantially reducing the biomass cake resistance due to its incompressible nature and higher backtransport velocities. PAC might have a scouring effect for removing the deposited biomass cake from the membrane surface while sorbing and/or coagulating dissolved organics and colloidal particles in the broth. The chemical oxygen demand and color in the effluent were much removed with PAC addition, and the system was also more stable against shock loading.

  9. 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.

  10. 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.

  11. Selective determination of antimony(III) and antimony(V) with ammonium pyrrolidinedithiocarbamate, sodium diethyldithiocarbamate and dithizone by atomic-absorption spectrometry with a carbon-tube atomizer.

    PubMed

    Kamada, T; Yamamoto, Y

    1977-05-01

    The extraction behaviour of antimony(III) and antimony(V) with ammonium pyrrolidinedithiocarbamate, sodium diethyldithiocarbamate and dithizone in organic solvents has been investigated by means of frameless atomic-absorption spectrophotometry with a carbon-tube atomizer. The selective extraction of antimony(III) and differential determination of antimony(III) and antimony(V) have been developed. With ammonium pyrrolidinedithiocarbamate and methyl isobutyl ketone, when the aqueous phase/solvent volume ratio is 50 ml/10 ml and the injection volume in the carbon tube is 20 mul, the sensitivity for antimony is 0.2 ng/ml for 1% absorption. The relative standard deviations are ca. 2%. Interferences by many metal ions can be prevented by masking with EDTA. The proposed methods have been applied satisfactorily to determination of antimony(III) and antimony(V) in various types of water. PMID:18962096

  12. Layered growth of crayfish gastrolith: about the stability of amorphous calcium carbonate and role of additives.

    PubMed

    Habraken, Wouter J E M; Masic, Admir; Bertinetti, Luca; Al-Sawalmih, Ali; Glazer, Lilah; Bentov, Shmuel; Fratzl, Peter; Sagi, Amir; Aichmayer, Barbara; Berman, Amir

    2015-01-01

    Previous studies on pre-molt gastroliths have shown a typical onion-like morphology of layers of amorphous mineral (mostly calcium carbonate) and chitin, resulting from the continuous deposition and densification of amorphous mineral spheres on a chitin-matrix during time. To investigate the consequences of this layered growth on the local structure and composition of the gastrolith, we performed spatially-resolved Raman, X-ray and SEM-EDS analysis on complete pre-molt gastrolith cross-sections. Results show that especially the abundance of inorganic phosphate, phosphoenolpyruvate (PEP)/citrate and proteins is not uniform throughout the organ but changes from layer to layer. Based on these results we can conclude that ACC stabilization in the gastrolith takes place by more than one compound and not by only one of these additives.

  13. 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.

  14. 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.

  15. The effects of carbon nanotube addition and oxyfluorination on the glucose-sensing capabilities of glucose oxidase-coated carbon fiber electrodes

    NASA Astrophysics Data System (ADS)

    Im, Ji Sun; Yun, Jumi; Kim, Jong Gu; Bae, Tae-Sung; Lee, Young-Seak

    2012-01-01

    Glucose-sensing electrodes were constructed from carbon fibers by electrospinning and heat treatment. By controlling the pore size, the specific surface area and pore volume of the electrospun carbon fibers were increased for efficient immobilization of the glucose oxidase. Carbon nanotubes were embedded as an electrically conductive additive to improve the electrical property of the porous carbon fibers. In addition, the surface of the porous carbon fibers was modified with hydrophilic functional groups by direct oxyfluorination to increase the affinity between the hydrophobic carbon surface and the hydrophilic glucose oxidase molecules. The porosity of the carbon fibers was improved significantly with approximately 28- and 35-fold increases in the specific surface area and pore volume, respectively. The number of chemical bonds between carbon and oxygen were increased with higher oxygen content during oxyfluorination based on the X-ray photoelectron spectroscopy results. Glucose sensing was carried out by current voltagram and amperometric methods. A high-performance glucose sensor was obtained with high sensitivity and rapid response time as a result of carbon nanotube addition, physical activation and surface modification. The mechanism of the highly sensitive prepared glucose sensor was modeled by an enzyme kinetics study using the Michaelis-Menten equation.

  16. 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. PMID:27421409

  17. 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.

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

    NASA Astrophysics Data System (ADS)

    Saidi, Wissam A.; Norman, Patrick

    2016-07-01

    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 ∝ N2.2 as predicted using state-of-the-art quantum mechanical calculations based on fullerenes with small sizes, and N2.75 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 ∝ N2.8, 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. Enhanced biotransformation of carbon tetrachloride by Acetobacterium woodii upon addition of hydroxocobalamin and fructose

    SciTech Connect

    Hashsham, S.A.; Freedman, D.L.

    1999-10-01

    The objective of this study was to evaluate the effect of hydroxocobalamin (OH-Cbl) on transformation of high concentrations of carbon tetrachloride (CT) by Acetobacterium woodii. Complete transformation of 470 {micro}M CT was achieved by A. woodii within 2.5 days, when 10 {micro}M OH-Cbl was added along with 25.2 mM fructose. This was approximately 30 times faster than A. woodii cultures and medium that did not receive OH-Cbl and 5 times faster than those controls that did receive OH-Cbl, but either live A. woodii or fructose was missing. CT transformation in treatments with only OH-Cbl was indicative of the important contribution of nonenzymatic reactions. Besides increasing the rate of CT transformation, addition of fructose and OH-Cbl to live cultures increased the percentage of [{sup 14}C]CT transformed to {sup 14}CO{sub 2} and {sup 14}C-labeled soluble materials, while decreasing the percentage of CT reduced to chloroform and abiotically transformed to carbon disulfide. {sup 14}CS{sub 2} represented more than 35% of the [{sup 14}C]CT in the presence of reduced medium and OH-Cbl. Conversion of CT to CO was a predominant pathway in formation of CO{sub 2} in the presence of live cells and added fructose and OH-Cbl. These results indicate that the rate and distribution of products during cometabolic transformation of CT by A. woodii can be improved by the addition of fructose and OH-Cbl.

  20. The Absolute Rates of the Solution Phase Addition of Atomic Hydrogen to a Vinyl Ether and a Vinyl Ester. The Effect of Oxygen Substitution on Hydrogen Atom Reactivity with Olefins

    SciTech Connect

    Tanner, D. D.; Kandanarachchi, P.; Das, N. C.; Franz, James A.

    2003-04-08

    The reactions of vinyl butyl ether and vinyl butyrate with atomic hydrogen and deuterium lead to addition of atomic hydrogen to the terminal position of the olefins. This observation is consistent with the reactions carried out earlier with other olefins. Both the absolute rates of addition to vinylbutyl ether and vinyl butyrate in acetone and hexane were carried out at several temperatures. The relative rates are consistent with only modest stabilization of the transition state of the radical adduct by the ??-o substituent compared with hydrogen atom addition to 1-octene. The relative rates measured in acetone and hexane indicate no significant differential solvation of ground state relative to the transition structures of the hydrogen atom addition. The kinetics reveal that the early transition states of hydrogen atom addition exhibit little selectivity (vinyl ether versus simple olefin) in either abstraction of hydrogen ??- to the oxygen or by terminal addition to the olefinic ether, reflecting the modest influence of the increased enthalpy of reaction associated with resonance stabilization by the oxygen substituent at the developing radical site.

  1. Nitrogen Additions Increase the Diversity of Carbon Compounds Degraded by Fungi in Boreal Forests

    NASA Astrophysics Data System (ADS)

    Gartner, T. B.; Turner, K. M.; Treseder, K. K.

    2004-12-01

    Boreal forest soils in North America harbor a large reservoir of organic C, and this region is increasingly exposed to long-range atmospheric N transport from Eurasia. By examining the responses of decomposers to N deposition in these forests, we hope to improve predictions of the fate of boreal carbon pools under global change. We tested the hypothesis that the functional diversity of decomposer fungi would increase under N fertilization in boreal forests where fungal growth was otherwise N-limited, owing to a reduction in competitive exclusion of fungal groups. We collected soil and leaf litter from three Alaskan sites that represent different successional stages at 5, 17, or 80 years following severe forest fire. Each site had been exposed for two years to nitrogen and phosphorus fertilization in a factorial design, with four plots per treatment. Nutrient limitation of fungal growth varied depending on successional stage. The standing hyphal length of decomposer fungi in soil (i.e. Ascomycota and Basidiomycota) responded to neither N nor P in the 5-year old site, increased under N fertilization in the 17-year old site, and increased where N and P was added simultaneously in the 80-year old site (site x N x P interaction: P = 0.001). We used BIOLOG microplates for filamentous fungi to obtain an index of the diversity of carbon use by decomposer fungi; each of 95 wells of these plates contains a different carbon-based compound, as well as a dye that changes color upon metabolism of the compound. Saline leaf litter extracts were mixed with fungal growth medium and then added to the microplates. The number of wells displaying metabolic activity was counted following incubation for five days. We found that N fertilization raised the average number of positive wells per plate from 14 to 27 (P = 0.012), with no significant differences in responses among sites. Phosphorus additions did not alter functional diversity of fungi in any site. Since increases in functional

  2. 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.

  3. 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.

  4. Atomic force microscopy of silica nanoparticles and carbon nanohorns in macrophages and red blood cells

    SciTech Connect

    Tetard, Laurene; Passian, Ali; Farahi, R H; Thundat, Thomas George

    2010-01-01

    The emerging interest in understanding the interactions of nanomaterial with biological systems necessitates imaging tools that capture the spatial and temporal distributions and attributes of the resulting nano-bil amalgam. Studies targeting organ specific response and/ot nanoparticle-specific system toxicity would be profoundly benefited from tools that would allow imaging and tracking of in-vivo or in-vitro processes and particle-fate studies. Recently we demonstrated that mode systhesizing atomic force microscopy (MSAFM) can provide subsurface nanoscale informations on the mechanical properties of materials at the nanoscale. However, the underlying mechanism of this imaging methodology is currently subject to theoretical and experimental investigation. In this paper we present further analysis by investigating tip-sample excitation forces associated with nanomechanical image formation. Images and force curves acquired under various operational frequencies and amplitudes are presented. We examine samples of mouse cells, where buried distributions of single-walled carbon nanohorns and silica nanoparticles are visualized.

  5. 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.

  6. Influence of Force Acting on Side Face of Carbon Nanotube in Atomic Force Microscopy

    NASA Astrophysics Data System (ADS)

    Akita, Seiji; Nishijima, Hidehiro; Kishida, Takayoshi; Nakayama, Yoshikazu

    2000-06-01

    We have examined the nanomechanics of a carbon nanotube by a manipulation technique using a scanning electron microscope. Young’s modulus of the nanotube, estimated from the buckling under force acting on the axial direction of the nanotube, agrees well with the value estimated from the bending under force acting on the side face. This indicates that the nanotube can be treated as an isotropic material in conventional mechanics. The adhesion force between the side face of the nanotube and a pit wall in a 4.7 GB digital versatile disk is estimated to be ˜10 nN using atomic force microscopy. This value is 160 times less than the value estimated using force curve measurement. This discrepancy is due to the finding that the value estimated from the force curve includes not only the adhesion but also the friction force.

  7. 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

  8. 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. PMID:24778944

  9. 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}.

  10. Ultralow loading Pt nanocatalysts prepared by atomic layer deposition on carbon aerogels.

    PubMed

    King, Jeffrey S; Wittstock, Arne; Biener, Juergen; Kucheyev, Sergei O; Wang, Yinmin M; Baumann, Theodore F; Giri, Sandeep K; Hamza, Alex V; Baeumer, Marcus; Bent, Stacey F

    2008-08-01

    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 approximately 0.05 mg Pt/cm2. We observe a conversion efficiency of nearly 100% in the 150-250 degrees C temperatures range, and the total conversion rate seems to be limited only by the thermal stability of the CA support in ambient oxygen. The 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.

  11. H-atom addition and abstraction reactions in mixed CO, H2CO and CH3OH ices - an extended view on complex organic molecule formation

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

    Complex organic molecules (COMs) have been observed not only in the hot cores surrounding low- and high-mass protostars, but also in cold dark clouds. Therefore, it is interesting to understand how such species can be formed without the presence of embedded energy sources. We present new laboratory experiments on the low-temperature solid state formation of three complex molecules - methyl formate (HC(O)OCH3), glycolaldehyde (HC(O)CH2OH) and ethylene glycol (H2C(OH)CH2OH) - through recombination of free radicals formed via H-atom addition and abstraction reactions at different stages in the CO→H2CO→CH3OH hydrogenation network at 15 K. The experiments extend previous CO hydrogenation studies and aim at resembling the physical-chemical conditions typical of the CO freeze-out stage in dark molecular clouds, when H2CO and CH3OH form by recombination of accreting CO molecules and H-atoms on ice grains. We confirm that H2CO, once formed through CO hydrogenation, not only yields CH3OH through ongoing H-atom addition reactions, but is also subject to H-atom-induced abstraction reactions, yielding CO again. In a similar way, H2CO is also formed in abstraction reactions involving CH3OH. The dominant methanol H-atom abstraction product is expected to be CH2OH, while H-atom additions to H2CO should at least partially proceed through CH3O intermediate radicals. The occurrence of H-atom abstraction reactions in ice mantles leads to more reactive intermediates (HCO, CH3O and CH2OH) than previously thought, when assuming sequential H-atom addition reactions only. This enhances the probability to form COMs through radical-radical recombination without the need of UV photolysis or cosmic rays as external triggers.

  12. Modulation of the Reactivity of a WO3/Al Energetic Material with Graphitized Carbon Black as Additive

    NASA Astrophysics Data System (ADS)

    Bach, Arnaud; Gibot, Pierre; Vidal, Loïc; Gadiou, Roger; Spitzer, Denis

    2015-10-01

    Although pyrotechnic performance is fundamental, the strong mechanical and electrostatic intrinsic sensitivities of nanothermite energetic composites represent an obstacle to their development. The addition of a ternary component to the classical binary energetic composite appears to be a promising idea to overcome the problem. A carbon black additive (V3G) was used on a WO3/Al nanothermite. The effect of the pristine and modified carbon particles on the mechanical and electrical sensitivities of the composites was measured together with the pyrotechnic properties. The results show a complete desensitization to friction with a ball-milled carbon when the combustion velocity is slightly reduced.

  13. 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.

  14. 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

  15. 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.

  16. Sensitivity of Arctic Permafrost Carbon in the Mackenzie River Basin: A substrate addition and incubation experiment

    NASA Astrophysics Data System (ADS)

    Hedgpeth, A.; Beilman, D.; Crow, S. E.

    2014-12-01

    Arctic soil organic matter (SOM) mineralization processes are fundamental to the functioning of high latitude soils in relation to nutrients, stability, and feedbacks to atmospheric CO2 and climate. The arctic permafrost zone covers 25% of the northern hemisphere and contains 1672Pg of soil carbon (C). 88% of this C currently resides in frozen soils that are vulnerable to environmental change. For instance, arctic growing seasons may be lengthened, resulting in an increase in plant productivity and rate of below ground labile C inputs as root exudates. Understanding controls on Arctic SOM dynamics requires recognition that labile C inputs have the potential to significantly affect mineralization of previously stable SOM, also known as 'priming effects'. We conducted a substrate addition incubation experiment to quantify and compare respiration in highly organic (42-48 %C) permafrost soils along a north-south transect in western Canada. Near surface soils (10-20 cm) were collected from permafrost peatland sites in the Mackenzie River Basin from 69.2-62.6°N. The surface soils are fairly young (Δ14C values > -140.0) and can be assumed to contain relatively reactive soil carbon. To assess whether addition of labile substrate alters SOM decomposition dynamics, 4.77-11.75 g of permafrost soil were spiked with 0.5 mg D-glucose g-1 soil and incubated at 5°C. A mass balance approach was used to determin substrate-induced respiration and preliminary results suggest a potential for positive priming in these C-rich soils. Baseline respiration rates from the three sites were similar (0.067-0.263 mg CO2 g-1 soil C) yet show some site-specific trends. The rate at which added substrate was utilized within these soils suggests that other factors besides temperature and soil C content are controlling substrate consumption and its effect on SOM decomposition. Microbial activity can be stimulated by substrate addition to such an extent that SOM turnover is enhanced, suggesting that

  17. In situ study of erosion and deposition of amorphous hydrogenated carbon films by exposure to a hydrogen atom beam

    SciTech Connect

    Markelj, Sabina; Pelicon, Primoz; Cadez, Iztok; Schwarz-Selinger, Thomas; Jacob, Wolfgang

    2012-07-15

    This paper reports on the first dual-beam experiment employing a hydrogen atom beam for sample exposure and an ion beam for analysis, enabling in situ and real-time studies of hydrogen atom interaction with materials. The erosion of an amorphous hydrogenated carbon (a-C:H) layer by deuterium atoms at 580 K sample temperature was studied and the uptake of deuterium during the erosion process was measured in real time. The deuterium areal density increased at the beginning to 7.3 Multiplication-Sign 10{sup 15} D cm{sup -2}, but then stabilized at a constant value of 5.5 Multiplication-Sign 10{sup 15} D cm{sup -2}. Formation of a polymer-like deposit on an a-C:H layer held at room temperature and subjected to the deuterium atom beam was observed and also studied in situ. For both erosion and deposition studies an a-{sup 13}C:H layer on top of an Si substrate was used as a sample, making the experiments isotopically fully specified and thereby differentiating the deposited from the original layer and the interacting D atoms from H atoms present in the layer and in the residual vacuum. From the deposition study it was shown that carbon in the deposited layer originates from carbon-carrying species in the background vacuum that interact with hydrogen atoms. The areal density of the carbon at the surface was determined from the energy shift of the Si edge in the Rutherford backscattering spectrum. The cross section for {sup 7}Li on D at 4.3 MeV Li ion energy and at a recoil angle of 30 Degree-Sign was also determined to be (236 {+-} 16) Multiplication-Sign 10{sup -27} cm{sup 2}/sr. This is a factor of 3 {+-} 0.2 times higher than the Rutherford elastic cross section.

  18. Self-trapping of carbon atoms in α'-Fe during the martensitic transformation: A qualitative picture from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Ruban, A. V.

    2014-10-01

    Strain-induced and chemical interactions of interstitial carbon atoms in bcc or α-Fe are obtained in first-principles calculations. Subsequent Monte Carlo simulations show that at low temperatures, carbon atoms prefer to occupy at least two different octahedral sublattices, which is due to quite strong attractive interactions of carbon atoms at the corresponding coordination shells. The direct total-energy calculations of one of the obtained ordered structures with composition Fe16C2, show that it is more stable than the predicted earlier structure with the same composition but carbon atoms occupying only one octahedral sublattice. This indicates that the long-existing thermodynamic mean-field theory of ordering of carbon in α-Fe assuming strong preference of carbon atoms to occupy only one octahedral sublattice is deficient. It is shown that the presence of carbon atoms only at one octahedral sublattice in the experimentally observed martensitic phase, α'-Fe, is a self-trapping effect. It occurs during a displacive martensitic transformation from γ- to α-Fe, which kinematically transfers the carbon atoms from a single fcc octahedral sublattice to one of three octahedral sublattices, where they appear to be locked by a consequent tetragonal distortion minimizing elastic energy of the phase. The latter creates a strong preference for carbon atoms to be only at one already occupied octahedral sublattice preventing them from further distribution over the other sublattices.

  19. Control of hydrogen and carbon impurity inclusion during the growth of GaAsN thin film by atomic layer epitaxy

    NASA Astrophysics Data System (ADS)

    Yokoyama, Yuki; Fukuyama, Atsuhiko; Haraguchi, Tomohiro; Yamauchi, Toshihiro; Ikari, Tetsuo; Suzuki, Hidetoshi

    2016-01-01

    The effects of growth temperature and nitrogen (N) source duration on N, carbon (C), and hydrogen (H) concentrations in GaAsN layers grown by atomic layer epitaxy (ALE) were investigated to understand the incorporation mechanisms of these atoms. In addition, the effects of the above growth conditions on the self-limiting mechanism (SLM) were investigated. The SLM was in effect at growth temperatures of 500 and 520 °C. The origin of the residual C was not N but other sources. With increasing N source duration, the N and H concentrations increased and saturated. The N incorporation mechanisms were discussed by a simple model considering the absorption and desorption of N atoms on the gallium (Ga)-covered surface. H atoms originating from the N source were incorporated in to the GaAsN layer. According to the ratio of the H concentration to the N concentration, the difference in the incorporation processes of N and H atoms in ALE-grown GaAsN layers was discussed.

  20. Mechanism of hydrofluoric acid formation in ethylene carbonate electrolytes with fluorine salt additives

    NASA Astrophysics Data System (ADS)

    Tebbe, Jonathon L.; Fuerst, Thomas F.; Musgrave, Charles B.

    2015-11-01

    We utilized density functional theory to examine HF generation in lithium-ion battery electrolytes from reactions between H2O and the decomposition products of three electrolyte additives: LiPF6, LiPOF4, and LiAsF6. Decomposition of these additives produces PF5, AsF5, and POF3 along with LiF precipitates. We found PF5 and AsF5 react with H2O in two sequential steps to form two HF molecules and POF3 and AsOF3, respectively. PF5 (or AsF5) complexes with H2O and undergoes ligand exchange to form HF and PF4OH (AsF4OH) with an activation barrier of 114.2 (30.5) kJ mol-1 and reaction enthalpy of 14.6 (-11.3) kJ mol-1. The ethylene carbonate (EC) electrolyte forms a Lewis acid-base complex with the PF4OH (AsF4OH) product, reducing the barrier to HF formation. Reactions of POF3 were examined and are not characterized by complexation of POF3 with H2O or EC, while PF5 and AsF5 complex favorably with H2O and EC. HF formation from POF3 occurs with a reaction enthalpy of -3.8 kJ mol-1 and a 157.7 kJ mol-1 barrier, 43.5 kJ mol-1 higher than forming HF from PF5. HF generation in electrolytes employing LiPOF4 should be significantly lower than those using LiPF6 or LiAsF6 and LiPOF4 should be further investigated as an alternative electrolyte additive.

  1. Aligned Carbon Nanotube Array Functionalization for Enhanced Atomic Layer Deposition of Platinum Electrocatalysts

    SciTech Connect

    Dameron, A. A.; Pylypenko, S.; Bult, J. B.; Neyerlin, K. C.; Engtrakul, C.; Bochert, C.; Leong, G. J.; Frisco, S. L.; Simpson, L.; Dinh, H. N.; Pivovar, B.

    2012-04-15

    Uniform metal deposition onto high surface area supports is a key challenge of developing successful efficient catalyst materials. Atomic layer deposition (ALD) circumvents permeation difficulties, but relies on gas-surface reactions to initiate growth. Our work demonstrates that modified surfaces within vertically aligned carbon nanotube (CNT) arrays, from plasma and molecular precursor treatments, can lead to improved catalyst deposition. Gas phase functionalization influences the number of ALD nucleation sites and the onset of ALD growth and, in turn, affects the uniformity of the coating along the length of the CNTs within the aligned arrays. The induced chemical changes for each functionalization route are identified by X-ray photoelectron and Raman spectroscopies. The most effective functionalization routes increase the prevalence of oxygen moieties at defect sites on the carbon surfaces. The striking effects of the functionalization are demonstrated with ALD Pt growth as a function of surface treatment and ALD cycles examined by electron microscopy of the arrays and the individual CNTs. Finally, we demonstrate applicability of these materials as fuel cell electrocatalysts and show that surface functionalization affects their performance towards oxygen reduction reaction.

  2. 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

  3. 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.

  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. Addition of Hetero-Atoms to the Polymer Film by Plasma Enhanced Polymerization and its Optical Properties

    NASA Astrophysics Data System (ADS)

    Moriki, Kazunori; Yumoto, Motoshige

    Plasma enhanced polymerization is an attractive technology to fabricate an optical polymer waveguide, because it has capability to provide an uniform thickness film on a substrate with various surface geometry, and to provide change of refractive index by controlling a proportion of source monomer mixing. In the present paper we discuss optical constants and molecule structures of the films added hetero-atoms, O, N and F in the CHx network of polymer. Refractive index of those films changes from 1.52 to 1.63 at 1.0 μm wavelength, depending on the variety of hetero-atoms. Fluorine atoms added into a film decreases refractive index of the film. Oxygen atoms added into a film, which form ester structure (- COO-), decrease refractive index of the film, and some O atoms token into a film as OH base will increase optical absorption in inferred region for optical communication. Nitrogen atoms added increase optical absorption due to forming NH2 base. Finally, sp3/sp2 fraction controlling in the film will be a suitable to control refractive index of the film for an optical waveguide, for example by using mixed monomer of C6H6 and C6H10.

  6. Absolute Rates of the Solution-Phase Addition of Atomic Hydrogen to a Vinyl Ether and a Vinyl Ester: Effect of Oxygen Substitution on Hydrogen Atom Reactivity with Olefins

    SciTech Connect

    Tanner, D D.; Kandanarachchi, P; Das, N. C.; Franz, James A.

    2003-04-08

    The reactions of vinyl butyl ether and vinyl butyrate with atomic hydrogen and deuterium lead to addition at the terminal position of the olefins. This observation is consistent with the reactions carried out earlier with other olefins. Both of the absolute rates of addition to vinylbutyl ether and vinyl butyrate, in acetone and hexane, were measured at several temperatures. The relative rates are consistent with only modest stabilization of the transition state of the radical adduct by the R-O substituent compared with that of hydrogen atom addition to 1-octene. The relative rates measured in acetone and hexane indicate no significant differential solvation of the ground state relative to the transition structures of the hydrogen atom addition. The kinetics reveal that the early transition states for hydrogen atom addition exhibit little selectivity (vinyl ether versus simple olefin) in either the abstraction of hydrogen R to the oxygen or by terminal addition to the olefinic ether and reflects the modest influence of the increased enthalpy of reaction associated with resonance stabilization by the oxygen substituent at the developing radical site.

  7. 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.

  8. Meta-code for systematic analysis of chemical addition (SACHA): application to fluorination of C70 and carbon nanostructure growth.

    PubMed

    Ewels, Christopher P; Lier, Gregory Van; Geerlings, Paul; Charlier, Jean-Christophe

    2007-01-01

    We present a new computer program able to systematically study chemical addition to and growth or evolution of carbon nanostructures. SACHA is a meta-code able to exploit a wide variety of pre-existing molecular structure codes, automating the otherwise onerous task of constructing, running, and analyzing the large number of input files that are required when exploring structural isomers and addition paths. By way of examples we consider fluorination of the fullerene cage C70 and carbon nanostructure growth through C2 addition. We discuss the possibilities for extension of this technique to rapidly and efficiently explore structural energy landscapes and application to other areas of chemical and materials research.

  9. 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.

  10. 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.

  11. 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. PMID:27396293

  12. 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.

  13. Engineering the atomic structure of carbon nanotubes by a focused electron beam: new morphologies at the sub-nanometer scale.

    PubMed

    Rodríguez-Manzo, Julio A; Krasheninnikov, Arkady V; Banhart, Florian

    2012-07-16

    Carbon atoms are displaced in pre-selected locations of carbon nanotubes by using a focused electron beam in a scanning transmission electron microscope. Sub-nanometer-sized holes are created that change the morphology of double and triple-walled carbon nanotubes and connect the shells in a unique way. By combining in situ transmission electron microscopy experiments with atomistic simulations, we study the bonding between defective shells in the new structures which are reminiscent of the shape of a flute. We demonstrate that in double-walled nanotubes the shells locally merge by forming nanoarches while atoms with dangling bonds can be preserved in triple-walled carbon nanotubes. In the latter system, nanoarches are formed between the inner- and outermost shells, shielding small graphenic islands with open edges between the neighboring shells. Our results indicate that arrays of quantum dots may be produced in carbon nanotubes by spatially localized electron irradiation, generating atoms with dangling bonds that may give rise to localized magnetic moments. PMID:22407751

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

    PubMed

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

    2013-11-13

    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 (sp(3) defects) in each layer. The presence of non-hexagonal rings in the atomic arrangement has been also considered. PMID:24140935

  15. 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.

  16. 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

  17. The influence of polyaspartate additive on the growth and morphology of calcium carbonate crystals

    NASA Astrophysics Data System (ADS)

    Gower, Laurie Anne

    The addition of low levels of polyaspartate to a supersaturated calcium carbonate (CaCOsb3) solution leads to unusual morphologies in the inorganic phase. Spherulitic vaterite aggregates with helical protrusions, and distorted calcite crystals that contain spiral pits, have been produced. The helical particles are coated with an inorganic membrane that appears to be responsible for the helical twist. The polymer also causes deposition of thin CaCOsb3 tablets and films on the glass substrate. Two distinct types of films are deposited; the first is a mosaic of calcite crystals, and the second is spherulitic vaterite. In situ observations of the crystallization reaction have determined that the thin-film morphology is a result of the phase separation of a hydrated CaCOsb3/polymer liquid-precursor, whereby accumulation of isotropic droplets creates a coating on the substrate, and subsequent dehydration and crystallization yields birefringent CaCOsb3 films. During the amorphous to crystalline transition, incremental growth steps lead to "transition bars" and sectored calcite tablets. This in vitro system was originally modeled after certain aspects of CaCOsb3 biomineralization, in which the soluble proteins extracted from biominerals tend to have high levels of aspartic acid residues. Based on the similarities between features exhibited by the products of this system and those in biominerals, an argument has been presented to suggest that this polymer-induced liquid-precursor (PILP) process is involved in the morphogenesis of CaCOsb3 biominerals. These features include the following: thin CaCOsb3 tablets that grow laterally; tablets that express unstable crystallographic faces; non-faceted single crystals with curved surfaces; spatially-delineated single crystals; sectored calcite tablets; hollow-shell spheres; calcium carbonate cements; and magnesium-bearing calcites. This work has demonstrated that a means of morphological control can be accomplished through non

  18. 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

  19. 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

  20. 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

  1. 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.

  2. Forced and natural carbonation of lime-based mortars with and without additives: Mineralogical and textural changes

    SciTech Connect

    Cultrone, G.

    2005-12-15

    We have studied the carbonation process in different types of mortars, with and without pozzolana or air-entraining additives, subject to a CO{sub 2}-rich atmosphere and compared the results with those of similar naturally carbonated mortars. We used X-ray diffraction technique to demonstrate that high CO{sub 2} concentrations favour a faster, more complete carbonation process with 8 days being sufficient to convert portlandite into 90 wt.% calcite. Full carbonation, however, is not reached during the life-span of the tests, not even in forced carbonation experiments. This could be due to at least one of the following phenomena: a premature drying of samples during carbonation reaction, the temperature at which the carbonation process was carried out or the reduction of pore volume occupied by newly formed calcite crystals. This last option seems to be the least probable. We observed a more prolific development of calcite crystals in the pores and fissures through which the carbonic anhydride flows. Under natural conditions, carbonation is much slower and similar levels are not reached for 6 months. These differences suggest that the carbonation process is influenced by the amount of CO{sub 2} used. Both the mineralogy and texture of mortars vary depending on the type of additive used but the speed of the portlandite-calcite transformation does not change significantly. Pozzolana produces hydraulic mortars although the quantity of calcium aluminosilicate crystals is low. The air-entraining agent significantly alters the texture of the mortars creating rounded pores and eliminating or reducing the drying cracks.

  3. 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.

  4. The effect of oligo(trimethylene carbonate) addition on the stiffness of acrylic bone cement

    PubMed Central

    Persson, Cecilia; López, Alejandro; Fathali, Hoda; Hoess, Andreas; Rojas, Ramiro; Ott, Marjam Karlsson; Hilborn, Jöns; Engqvist, Håkan

    2016-01-01

    Abstract With the increasing elderly population an increase in the number of bony fractures associated to age-related diseases such as osteoporosis also follows. The relatively high stiffness of the acrylic bone cements used in these patients has been suggested to give raise to a suboptimal load distribution surrounding the cement in vivo, and hence contribute to clinical complications, such as additional fractures. The aim of this study was to develop a low-modulus bone cement, based on currently used, commercially available poly(methyl methacrylate) (PMMA) cements for vertebroplasty. To this end, acrylate end-functionalized oligo(trimethylene carbonate) (oTMC) was incorporated into the cements, and the resulting compressive mechanical properties were evaluated, as well as the cytotoxic and handling properties of selected formulations. Sixteen wt%oTMC was needed in the vertebroplastic cement Osteopal V to achieve an elastic modulus of 1063 MPa (SD 74), which gave a corresponding compressive strength of 46.1 MPa (SD 1.9). Cement extracts taken at 1 and 12 hours gave a reduced MG-63 cell viability in most cases, while extracts taken at 24 hours had no significant effect on cell behavior. The modification also gave an increase in setting time, from 14.7 min (SD 1.7) to 18.0 min (SD 0.9), and a decrease in maximum polymerization temperature, from 41.5°C (SD 3.4) to 30.7°C (SD 1.4). While further evaluation of other relevant properties, such as injectability and in vivo biocompatibility, remains to be done, the results presented herein are promising in terms of approaching clinically applicable bone cements with a lower stiffness. PMID:26727581

  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. 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.

  7. Merging Single-Atom-Dispersed Silver and Carbon Nitride to a Joint Electronic System via Copolymerization with Silver Tricyanomethanide.

    PubMed

    Chen, Zupeng; Pronkin, Sergey; Fellinger, Tim-Patrick; Kailasam, Kamalakannan; Vilé, Gianvito; Albani, Davide; Krumeich, Frank; Leary, Rowan; Barnard, Jon; Thomas, John Meurig; Pérez-Ramírez, Javier; Antonietti, Markus; Dontsova, Dariya

    2016-03-22

    Herein, we present an approach to create a hybrid between single-atom-dispersed silver and a carbon nitride polymer. Silver tricyanomethanide (AgTCM) is used as a reactive comonomer during templated carbon nitride synthesis to introduce both negative charges and silver atoms/ions to the system. The successful introduction of the extra electron density under the formation of a delocalized joint electronic system is proven by photoluminescence measurements, X-ray photoelectron spectroscopy investigations, and measurements of surface ζ-potential. At the same time, the principal structure of the carbon nitride network is not disturbed, as shown by solid-state nuclear magnetic resonance spectroscopy and electrochemical impedance spectroscopy analysis. The synthesis also results in an improvement of the visible light absorption and the development of higher surface area in the final products. The atom-dispersed AgTCM-doped carbon nitride shows an enhanced performance in the selective hydrogenation of alkynes in comparison with the performance of other conventional Ag-based materials prepared by spray deposition and impregnation-reduction methods, here exemplified with 1-hexyne. PMID:26863408

  8. Merging Single-Atom-Dispersed Silver and Carbon Nitride to a Joint Electronic System via Copolymerization with Silver Tricyanomethanide.

    PubMed

    Chen, Zupeng; Pronkin, Sergey; Fellinger, Tim-Patrick; Kailasam, Kamalakannan; Vilé, Gianvito; Albani, Davide; Krumeich, Frank; Leary, Rowan; Barnard, Jon; Thomas, John Meurig; Pérez-Ramírez, Javier; Antonietti, Markus; Dontsova, Dariya

    2016-03-22

    Herein, we present an approach to create a hybrid between single-atom-dispersed silver and a carbon nitride polymer. Silver tricyanomethanide (AgTCM) is used as a reactive comonomer during templated carbon nitride synthesis to introduce both negative charges and silver atoms/ions to the system. The successful introduction of the extra electron density under the formation of a delocalized joint electronic system is proven by photoluminescence measurements, X-ray photoelectron spectroscopy investigations, and measurements of surface ζ-potential. At the same time, the principal structure of the carbon nitride network is not disturbed, as shown by solid-state nuclear magnetic resonance spectroscopy and electrochemical impedance spectroscopy analysis. The synthesis also results in an improvement of the visible light absorption and the development of higher surface area in the final products. The atom-dispersed AgTCM-doped carbon nitride shows an enhanced performance in the selective hydrogenation of alkynes in comparison with the performance of other conventional Ag-based materials prepared by spray deposition and impregnation-reduction methods, here exemplified with 1-hexyne.

  9. Localised quantum states of atomic and molecular particles physisorbed on carbon-based nanoparticles

    SciTech Connect

    Kaprálová-Žďánská, Petra Ruth; Trachta, Michal; Bludský, Ota; Špirko, Vladimír

    2014-09-21

    The vibrational states of atomic and molecular particles adsorbed on long linear nanographenes are described using reliable theoretical potentials and appropriate vibrational (lateral) Hamiltonians. Although they rigorously obey the Bloch theorem only for infinite nanographenes, the energy patterns of the probed states closely resemble the usual Bloch bands and gaps. In addition, for any finite nanographene, these patterns are enriched by the presence of “solitary” energy levels and the “resonance” structure of the bands. While typical band states are profoundly delocalised due to a fast tunneling of the adsorbed particle, the “solitary” and “resonance” states exhibit strong localisation, similar to the behaviour of the states of the Wannier-Stark ladders in optical and semiconductor superlattices.

  10. Localised quantum states of atomic and molecular particles physisorbed on carbon-based nanoparticles

    NASA Astrophysics Data System (ADS)

    Kaprálová-Žánská, Petra Ruth; Trachta, Michal; Bludský, Ota; Špirko, Vladimír

    2014-09-01

    The vibrational states of atomic and molecular particles adsorbed on long linear nanographenes are described using reliable theoretical potentials and appropriate vibrational (lateral) Hamiltonians. Although they rigorously obey the Bloch theorem only for infinite nanographenes, the energy patterns of the probed states closely resemble the usual Bloch bands and gaps. In addition, for any finite nanographene, these patterns are enriched by the presence of "solitary" energy levels and the "resonance" structure of the bands. While typical band states are profoundly delocalised due to a fast tunneling of the adsorbed particle, the "solitary" and "resonance" states exhibit strong localisation, similar to the behaviour of the states of the Wannier-Stark ladders in optical and semiconductor superlattices.

  11. A vortex line for K-shell ionization of a carbon atom by electron impact

    NASA Astrophysics Data System (ADS)

    Ward, S. J.; Macek, J. H.

    2014-10-01

    We obtained using the Coulomb-Born approximation a deep minimum in the TDCS for K-shell ionization of a carbon atom by electron impact for the electron ejected in the scattering plane. The minimum is obtained for the kinematics of the energy of incident electron Ei = 1801.2 eV, the scattering angle θf = 4°, the energy of the ejected electron Ek = 5 . 5 eV, and the angle for the ejected electron θk = 239°. This minimum is due to a vortex in the velocity field. At the position of the vortex, the nodal lines of Re [ T ] and Im [ T ] intersect. We decomposed the CB1 T-matrix into its multipole components for the kinematics of a vortex, taking the z'-axis parallel to the direction of the momentum transfer vector. The m = +/- 1 dipole components are necessary to obtain a vortex. We also considered the electron to be ejected out of the scattering plane and obtained the positions of the vortex for different values of the y-component of momentum of the ejected electron, ky. We constructed the vortex line for the kinematics of Ei = 1801.2 eV and θf = 4°. S.J.W. and J.H.M. acknowledge support from NSF under Grant No. PHYS- 0968638 and from D.O.E. under Grant Number DE-FG02-02ER15283, respectively.

  12. 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.

  13. 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

    2016-08-01

    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. PMID:27404764

  14. Atomic carbon near the molecular cloud/H II region interface in S 140

    NASA Astrophysics Data System (ADS)

    Hernichel, J.; Krause, D.; Roehrig, R.; Stutzki, J.; Winnewisser, G.

    1992-06-01

    We have observed the (CI) 3P1 - 3P0 fine structure line of atomic carbon at 492 GHz in the edge-on interface between the molecular cloud L 1204 and the S 140 H II region with the KOSMA telescope on Gornergrat, Switzerland. We find that the (CI)-emission near the interface consists of a narrow velocity component with position and line width similar to that of the ambient molecular cloud material, superimposed on a wider component (FWHM is approximately equal to 15 km/s) exhibiting a line profile similar to that of the higher velocity material visible in CO and carrying most of the CI column density. The velocity integrated (CI) emission peaks near the edge of the cloud facing the exciting star. This finding is in contrast to earlier results by Keene et al. (1985) who missed the wide velocity component in their observations. The relative CI/CO abundance is strongly enhanced in the high velocity material (100 percent) relative to the ambient cloud material (11 percent).

  15. 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.

  16. 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.

  17. 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 (-).

  18. 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

  19. 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.

  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. Stabilization and Destabilization of Soil Carbon with Nitrogen Additions in Two Tropical Forests

    NASA Astrophysics Data System (ADS)

    Cusack, D. F.; Silver, W.; Torn, M.; McDowell, W. H.

    2008-12-01

    Nitrogen (N) deposition is known to effect carbon (C) cycling in temperate ecosystems, but less is known about the effects of added N in tropical forests, where N is not generally limiting to plant growth. We examined changes in soil C dynamics with N fertilization in two tropical forest types (lower elevation and montane) in the Luquillo Mountains, Puerto Rico. We hypothesized that increased N would accelerate the decomposition of labile C pools, while decreasing losses of more recalcitrant C compounds. We measured C and C:N in bulk soil C and C fractions (free light, occluded light, and heavy fractions) as measures of C content and chemical properties in fertilized and control plots. To address our hypotheses, we conducted several measures of microbial activity, including extracellular enzyme activities and respiration during a long-term soil incubation. We included measurements of 14C of CO2 respired during the soil incubation to determine whether added N changed the age of respired C. After 3.5 years of N fertilization, plots with added N had higher C content (42.3 ± 6.8 and 40.7 ± 4.7 g/cm2, lower elevation and montane respectively) than control plots (34.2 ± 5.9 and 34.3 ± 1.3 g/cm2) at 0 - 10 cm depth. While the labile fraction of C declined with added N as a proportion of total soil weight, the C concentration of the heavy fraction increased in fertilized plots (2.9 ± 0.3 and 4.0 ± 0.7%) relative to control plots (2.6 ± 0.4 and 2.8 ± 0.5 %), helping explain the increase in bulk soil C content. The soil incubation revealed changes in microbial respiration with added N, and a trend toward higher 14C of CO2 in fertilized plots for the lower elevation forest. Together, these results indicate that rates of C stabilization in the heavy fraction exceeded the increase in respiration of older C with N additions.

  2. Enhancement of carbon sequestration in soil in the temperature grasslands of northern China by addition of nitrogen and phosphorus.

    PubMed

    He, Nianpeng; Yu, Qiang; Wang, Ruomeng; Zhang, Yunhai; Gao, Yang; Yu, Guirui

    2013-01-01

    Increased nitrogen (N) deposition is common worldwide. Questions of where, how, and if reactive N-input influences soil carbon (C) sequestration in terrestrial ecosystems are of great concern. To explore the potential for soil C sequestration in steppe region under N and phosphorus (P) addition, we conducted a field experiment between 2006 and 2012 in the temperate grasslands of northern China. The experiment examined 6 levels of N (0-56 g N m(-2) yr(-1)), 6 levels of P (0-12.4 g P m(-2) yr(-1)), and a control scenario. Our results showed that addition of both N and P enhanced soil total C storage in grasslands due to significant increases of C input from litter and roots. Compared with control plots, soil organic carbon (SOC) in the 0-100 cm soil layer varied quadratically, from 156.8 to 1352.9 g C m(-2) with N addition gradient (R(2) = 0.99, P < 0.001); and logarithmically, from 293.6 to 788.6 g C m(-2) with P addition gradient (R(2) = 0.56, P = 0.087). Soil inorganic carbon (SIC) decreased quadratically with N addition. The net C sequestration on grassland (including plant, roots, SIC, and SOC) increased linearly from -128.6 to 729.0 g C m(-2) under N addition (R(2) = 0.72, P = 0.023); and increased logarithmically, from 248.5 to 698 g C m(-2)under P addition (R(2) = 0.82, P = 0.014). Our study implies that N addition has complex effects on soil carbon dynamics, and future studies of soil C sequestration on grasslands should include evaluations of both SOC and SIC under various scenarios.

  3. Patterned forest-assembly of single-wall carbon nanotubes and carbon nanotube atomic force microscopy nanoprobes

    NASA Astrophysics Data System (ADS)

    Wei, Haoyan

    Single-wall carbon nanotubes (SWNTs) are envisioned to greatly impact future science and technology particularly in the nanoscale range due to their unique one dimensional structure with tunable electrical conductivity. Thus they have received considerable attention in the development of nanodevices, field emitters and biosensors. The ability to place carbon nanotubes (CNTs) with controlled orientation at desired sites presents one major challenge in assembling these remarkable nanostructures into useful functional devices. In this dissertation a metal-assisted self-assembly technique was utilized in which dense rope-lattice-like SWNT forests with upright direction were obtained by immobilizing carboxylated nanotubes from dimethylformamide (DMF) nonaqueous media onto the underlying substrates with the linkage of FeO(OH)/FeOCl crystallites. In comparison with growing CNTs by chemical vapor deposition (CVD) on patterned catalyst pads, this self-assembly approach can take advantage of post-synthesis SWNT separation according to length and type (met allic versus semiconducting). Since FeO(OH)/FeOCl crystallites acted as linkers to bridge CNTs onto the substrates, the appropriate placement of these iron deposits was pivotal to realize the desired SWNT patterns. To assist in localizing these FeO(OH)/FeOCl crystallites, three approaches on diverse substrates including Nafion, Si/SiO x and Au were investigated with the aid of low-energy electron-beam direct writing (on Nafion and Si/SiOx) and photolithography (on Au) by creating preferential precipitation sites for FeO(OH)/FeOCl crystallites. Such differential deposition of FeO(OH)/FeOCl crystallites provided the basis for the patterned site-specific self-assembly of SWNT forests as demonstrated by atomic force microscopy (AFM) and resonance Raman spectroscopy. A second part of this dissertation resulted in CNT nanoprobes on conductive AFM probes fabricated with the help of a positive dielectrophoretic (DEP) process. Under

  4. Regioselective Dichlorination of a Non-Activated Aliphatic Carbon Atom and Phenolic Bismethylation by a Multifunctional Fungal Flavoenzyme.

    PubMed

    Chankhamjon, Pranatchareeya; Tsunematsu, Yuta; Ishida-Ito, Mie; Sasa, Yuzuka; Meyer, Florian; Boettger-Schmidt, Daniela; Urbansky, Barbara; Menzel, Klaus-Dieter; Scherlach, Kirstin; Watanabe, Kenji; Hertweck, Christian

    2016-09-19

    The regioselective functionalization of non-activated carbon atoms such as aliphatic halogenation is a major synthetic challenge. A novel multifunctional enzyme catalyzing the geminal dichlorination of a methyl group was discovered in Aspergillus oryzae (Koji mold), an important fungus that is widely used for Asian food fermentation. A biosynthetic pathway encoded on two different chromosomes yields mono- and dichlorinated polyketides (diaporthin derivatives), including the cytotoxic dichlorodiaporthin as the main product. Bioinformatic analyses and functional genetics revealed an unprecedented hybrid enzyme (AoiQ) with two functional domains, one for halogenation and one for O-methylation. AoiQ was successfully reconstituted in vivo and in vitro, unequivocally showing that this FADH2 -dependent enzyme is uniquely capable of the stepwise gem-dichlorination of a non-activated carbon atom on a freestanding substrate. Genome mining indicated that related hybrid enzymes are encoded in cryptic gene clusters in numerous ecologically relevant fungi. PMID:27559694

  5. Insights in the plasma-assisted growth of carbon nanotubes through atomic scale simulations: effect of electric field.

    PubMed

    Neyts, Erik C; van Duin, Adri C T; Bogaerts, Annemie

    2012-01-18

    Carbon nanotubes (CNTs) are nowadays routinely grown in a thermal CVD setup. State-of-the-art plasma-enhanced CVD (PECVD) growth, however, offers advantages over thermal CVD. A lower growth temperature and the growth of aligned freestanding single-walled CNTs (SWNTs) makes the technique very attractive. The atomic scale growth mechanisms of PECVD CNT growth, however, remain currently entirely unexplored. In this contribution, we employed molecular dynamics simulations to focus on the effect of applying an electric field on the SWNT growth process, as one of the effects coming into play in PECVD. Using sufficiently strong fields results in (a) alignment of the growing SWNTs, (b) a better ordering of the carbon network, and (c) a higher growth rate relative to thermal growth rate. We suggest that these effects are due to the small charge transfer occurring in the Ni/C system. These simulations constitute the first study of PECVD growth of SWNTs on the atomic level. PMID:22126536

  6. Microbiological and Mineralogical Characterization of Columbia River Basalts Prior to Supercritical Carbon Dioxide Addition

    NASA Astrophysics Data System (ADS)

    Colwell, F. S.; Fisk, M. R.; Yip, H.; Schwartz, A.; Briggs, B. R.; Spane, F.

    2009-12-01

    Deep geologic sequestration of supercritical carbon dioxide can remove excess carbon dioxide from the atmosphere but will cause profound changes to the geochemistry and microorganisms in the deep strata where it is injected. Here we report the original subsurface microbial constituents in basalt aquifers where supercritical carbon dioxide will be injected as part of the DOE Big Sky Regional Partnership field pilot investigation. Microbial cells were acquired by filtration of water from five discrete depth intervals in the Columbia River basalts during drilling of the borehole in eastern Washington state. Microbes were present in all five of the groundwater samples collected. DNA extracted from the cells was successfully amplified using 16S rRNA gene primers for bacteria, but not archaea. Terminal restriction fragment length polymorphism suggested that microbial communities in aquifers from the upper Grand Ronde basalt flows (518 to 553 m) were similar to each other, but distinct from those present in groundwater from the shallower, overlying Wanapum and deeper Grand Ronde basalt flows. Quantitative polymerase chain reaction directed at the 16S rRNA gene indicated that the aquifers had approximately 10,000 cells per ml. To date, our analysis demonstrates the presence of diverse microbial communities at and above the depths where a limited field test carbon dioxide injection (ca. 1,000 metric tons) is planned for early in 2010. A variety of secondary mineral assemblages (mainly clay minerals, silicates and carbonates) have been observed in thin section, and X-ray diffraction examination of the basalt cuttings from the pilot characterization borehole. This pre-injection study supports our inquiry of how indigenous microbial communities may be altered by supercritical carbon dioxide injection, and possible processes that may increase basalt reaction/weathering and re-precipitation of carbonate minerals. Microbial communities that become established after the carbon

  7. 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.

  8. 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.

  9. Permeation of low-Z atoms through carbon sheets: Density functional theory study on energy barriers and deformation effects

    NASA Astrophysics Data System (ADS)

    Huber, Stefan E.; Mauracher, Andreas; Probst, Michael

    2013-12-01

    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.

  10. 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.

  11. 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.

  12. 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.

  13. Computational insights into the effect of carbon structures at the atomic level for non-aqueous sodium-oxygen batteries

    NASA Astrophysics Data System (ADS)

    Jiang, H. R.; Wu, M. C.; Zhou, X. L.; Yan, X. H.; Zhao, T. S.

    2016-09-01

    Carbon materials have been widely used to form air cathodes for non-aqueous sodium-oxygen (Nasbnd O2) batteries due to their large specific surface area, high conductivity and low cost. However, the effect of carbon structures at the atomic level remains poorly understood. In this work, a first-principles study is conducted to investigate how representative carbon structures, including graphite (0001) surface, point defects and fractured edge, influence the discharge and charge processes of non-aqueous Nasbnd O2 batteries. It is found that the single vacancy (SV) defect has the largest adsorption energy (5.81 eV) to NaO2 molecule among the structures studied, even larger than that of the NaO2 molecule on NaO2 crystal (2.81 eV). Such high adsorption energy is attributed to two factors: the dangling atoms in SV defects decrease the distance from NaO2 molecules, and the attachment through oxygen atoms increases the electrons transfer. The findings suggest that SV defects can act as the nucleation sites for NaO2 in the discharge process, and increasing the number of SV defects can facilitate the uniform formation of small-sized particles. The uniformly distributed discharge products lower the possibility for pore clogging, leading to an increased discharge capacity and improved cyclability for non-aqueous Nasbnd O2 batteries.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. Turnover of soil carbon pools following addition of switchgrass-derived biochar to four soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The amendment of soils with biochar may improve plant growth and sequester carbon, especially in marginal soils not suitable for the majority of commodity production. While biochar can persist in soils, it is not clear whether its persistence is affected by soil type. Moreover, we know little of how...

  19. 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.

  20. 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. PMID:27318162

  1. 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.

  2. Reaction of cyanoacetylene HCCCN(X 1Sigma+) with ground-state carbon atoms C(3P) in cold molecular clouds.

    PubMed

    Li, H Y; Cheng, W C; Liu, Y L; Sun, B J; Huang, C Y; Chen, K T; Tang, M S; Kaiser, R I; Chang, A H H

    2006-01-28

    The reaction of the simplest cyanopolyyne, cyanoacetylene [HCCCN(X (1)Sigma(+))], with ground-state atomic carbon C((3)P) is investigated theoretically to explore the probable routes for the depletion of the famed interstellar molecule HCCCN, and the formation of carbon-nitrogen-bearing species in extraterrestrial environments particularly of ultralow temperature. Six collision complexes (c1-c6) without entrance barrier as a result of the carbon atom addition to the pi systems of HCCCN are located. The optimized geometries and harmonic frequencies of the intermediates, transition states, and products along the isomerization and dissociation pathways of each collision complex are obtained by utilizing the unrestricted B3YLP6-311G(d,p) level of theory, and the corresponding CCSD(T)/cc-pVTZ energies are calculated. Subsequently, with the facilitation of Rice-Ramsperger-Kassel-Marcus (RRKM) and variational RRKM rate constants at collision energy of 0-10 kcal/mol, the most probable paths for the titled reaction are determined, and the product yields are estimated. Five collision complexes (c1-c3, c5, and c6) are predicted to give the same products, a chained CCCCN (p2)+H, via the linear and most stable intermediate, HCCCCN (i2), while collision complex c4 is likely to dissociate back to C+HCCCN. The study suggests that this class of reaction is an important route to the destruction of cyanoacetylene and cyanopolyynes in general, and to the synthesis of linear carbon-chained nitriles at the temperature as low as 10 K to be incorporated in future chemical models of interstellar clouds.

  3. 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

  4. 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

    2014-01-01

    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

  5. The effects of fire severity on black carbon additions to forest soils - 10 years post fire

    NASA Astrophysics Data System (ADS)

    Poore, R.; Wessman, C. A.; Buma, B.

    2013-12-01

    Wildfires play an active role in the global carbon cycle. While large amounts of carbon dioxide are released, a small fraction of the biomass consumed by the fire is only partially combusted, yielding soot and charcoal. These products, also called black carbon (BC) make up only 1-5% of the biomass burnt, yet they can have a disproportionate effect on both the atmosphere and fluxes in long-term carbon pools. This project specifically considers the fraction that is sequestered in forest soils. Black carbon is not a specific compound, and exists along a continuum ranging from partially burned biomass to pure carbon or graphite. Increasing aromaticity as the result of partial combustion means charcoal is highly resistant to oxidation. Although debated, most studies indicate a turnover time on the order of 500-1,000 years in warm, wet, aerobic soils. Charcoal may function as a long-term carbon sink, however its overall significance depends on its rate of formation and loss. At the landscape level, fire characteristics are one of the major factors controlling charcoal production. A few studies suggest that charcoal production increases with cooler, less-severe fires. However, there are many factors to tease apart, partly because of a lack of specificity in how fire severity is defined. Within this greater context, our lab has been working on a landscape-level study within Routt National Forest, north of Steamboat Springs, Colorado. In 2002, a large fire swept through a subalpine spruce, fir and lodgepole pine forest. In 2011-2013 we sampled BC pools in 44 plots across a range of fire severities from unburned to severe crown We hypothesized that charcoal stocks will be higher in areas of low severity fire as compared to high severity because of decreased re-combustion of charcoal in the organic soil and increased overall charcoal production due to lower temperatures. In each of our plots we measured charcoal on snags and coarse woody debris, sampled the entire organic

  6. [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. PMID:27209754

  7. [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.

  8. 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.

  9. ATOMIC-LEVEL MODELING OF CO2 DISPOSAL AS A CARBONATE MINERAL: A SYNERGETIC APPROACH TO OPTIMIZING REACTION PROCESS DESIGN

    SciTech Connect

    A.V.G. Chizmeshya; M.J. McKelvy; J.B. Adams

    2001-11-01

    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 mineral carbonation is a leading process candidate, which generates the stable naturally occurring mineral magnesite (MgCO{sub 3}) and water. Key to process cost and viability are the carbonation reaction rate and its degree of completion. This process, which involves simultaneous dehydroxylation and carbonation is very promising, but far from optimized. In order to optimize the dehydroxylation/carbonation process, an atomic-level understanding of the mechanisms involved is needed. In this investigation Mg(OH){sub 2} was selected as a model Mg-rich lamellar hydrocide carbonation feedstock material due to its chemical and structural simplicity. Since Mg(OH){sub 2} dehydroxylation is intimately associated with the carbonation process, its mechanisms are also of direct interest in understanding and optimizing the process. The aim of the current innovative concepts project is to develop a specialized advanced computational methodology to complement the ongoing experimental inquiry of the atomic level processes involved in CO{sub 2} mineral sequestration. The ultimate goal is to integrate the insights provided by detailed predictive simulations with the data obtained from optical microscopy, FESEM, ion beam analysis, SIMS, TGA, Raman, XRD, and C and H elemental analysis. The modeling studies are specifically designed to enhance the synergism with, and complement the analysis of, existing mineral-CO{sub 2} reaction process studies being carried out under DOE UCR Grant DE-FG2698-FT40112. Direct contact between the simulations and the experimental

  10. Field Ionization of Cold Atoms near the Wall of a Single Carbon Nanotube

    SciTech Connect

    Goodsell, Anne; Ristroph, Trygve; Golovchenko, J. A.; Hau, Lene Vestergaard

    2010-04-02

    We observe the capture and field ionization of individual atoms near the side wall of a single suspended nanotube. Extremely large cross sections for ionization from an atomic beam are observed at modest voltages due to the nanotube's small radius and extended length. The effects of the field strength on both the atomic capture and the ionization process are clearly distinguished in the data, as are prompt and delayed ionizations related to the locations at which they occur. Efficient and sensitive neutral atom detectors can be based on the nanotube capture and wall ionization processes.

  11. 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.

  12. 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.

  13. Effects of porous carbon additives and induced fluorine on low dielectric constant polyimide synthesized with an e-beam

    SciTech Connect

    Im, Ji Sun; Bae, Tae-Sung; Lee, Sung Kyu; Lee, Sei-Hyun; Jeong, Euigyung; Kang, Phil Hyun; Lee, Young-Seak

    2010-11-15

    We report the synthesis of a polyimide matrix with a low dielectric constant for application as an intercalation material between metal interconnections in electronic devices. Porous activated carbon was embedded in the polyimide to reduce the dielectric constant, and a thin film of the complex was obtained using the spin-coating and e-beam irradiation methods. The surface of the thin film was modified with fluorine functional groups to impart water resistance and reduce the dielectric constant further. The water resistance was significantly improved by the modification with hydrophobic fluorine groups. The dielectric constant was effectively decreased by porous activated carbon. The fluorine modification also resulted in a low dielectric constant on the polyimide surface by reducing the polar surface free energy. The dielectric constant of polyimide film decreased from 2.98 to 1.9 by effects of porous activated carbon additive and fluorine surface modification.

  14. 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.

  15. Multi-Walled Carbon Nanotube Functionalization by Radical Addition Using Hydroxymethylene Groups.

    PubMed

    Rodríguez-Jiménez, Rubén; Alonso-Núñez, Gabriel; Paraguay-Delgado, Francisco; Espinoza-Gómez, Heriberto; Vélez-López, Ernesto; Rogel-Hernández, Eduardo

    2016-01-01

    Synthetic methodology and characterization of multi-walled carbon nanotubes (MWCNTs) function- alized with hydroxymethylene groups are reported. The MWCNTs were synthesized by the spray pyrolysis technique using toluene as carbon source and ferrocene as catalyst. Hydroxymethylation of MWCNTs was carried out by methanol using benzoyl peroxide (BPO) at different quantities (300 to 900 mg); the optimum BPO quantity was 300 mg. The resulting materials were characterized by FT-IR, Raman Spectroscopy, Thermal Gravimetric Analysis (TGA) and Transmission Electron Microscopy (TEM). The presence of the hydroxymethylene group on the MWCNTs surface was demonstrated by FT-IR, Raman Spectroscopy, TGA, EDS, TEM and Mass Spectrometry. The func- tionalized MWCNTs were not damaged by this methodology. PMID:27398563

  16. Synergistic catalysis: highly diastereoselective benzoxazole addition to Morita-Baylis-Hillman carbonates.

    PubMed

    Ceban, Victor; Putaj, Piotr; Meazza, Marta; Pitak, Mateusz B; Coles, Simon J; Vesely, Jan; Rios, Ramon

    2014-07-18

    An expedited method has been developed for the diastereoselective synthesis of highly functionalized alkyl-azaarene systems with good yields and high diastereoselectivities (>15 : 1 dr). The methodology includes a synergistic catalysis event involving organometallic (10 mol% AgOAc) activation of an alkyl azaarene and Lewis base (10 mol% DABCO) activation of a Morita-Baylis-Hillman carbonate. The structure and relative configuration of a representative product were confirmed by X-ray analysis.

  17. 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.

  18. 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. PMID:17119654

  19. 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. PMID:26750627

  20. 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.

  1. Control of ordering and structure in soft templated mesoporous carbon films by use of selective solvent additives.

    PubMed

    Qiang, Zhe; Xue, Jiachen; Stein, Gila E; Cavicchi, Kevin A; Vogt, Bryan D

    2013-07-01

    The structure of ordered mesoporous carbons fabricated using poly(styrene-block-N,N,-dimethyl-n-octadecylamine p-styrenesulfonate) (PS-b-PSS-DMODA) as the template and phenolic resin (resol) as the carbon source can be easily manipulated by inclusion of low concentrations of low volatility selective solvents in the casting solution. Casting from neat methyl ethyl ketone yields a disordered structure even upon thermal annealing. However, addition of both dioctyl phthalate (DOP, PS selective) and dimethyl sulfoxide (DMSO, resol and PSS-DMODA selective) at modest concentrations to this casting solution provides sufficient mobility to produce highly ordered films with cylindrical mesopores. The DOP acts to swell the hydrophobic domain and can more than double the mesopore size, while the DMSO acts to swell the resol phase. Moreover, the surface area of the mesoporous carbons increases significantly as the meosopore size increases. This is a result of the decrease in wall thickness, which can be ascertained by the constant d-spacing of the mesostructure as the pore size increases. This behavior is counter to the typical effect of pore swelling agents that increase the pore size and decrease the surface area. Moreover, with only 4 wt % DOP/DMSO in the solution (20 wt % relative to solids), the scattering profiles exhibit many orders of diffraction, even upon carbonization, which is not typically observed for soft templated films. Variation in the concentration of DOP and DMSO during casting enables facile tuning of the structure of mesoporous carbon films. PMID:23738851

  2. 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.

  3. [Study on degradation of polycyclic aromatic hydrocarbons (PAHs) with different additional carbon sources in aged contaminated soil].

    PubMed

    Yin, Chun-Qin; Jiang, Xin; Wang, Fang; Wang, Cong-Ying

    2012-02-01

    This study was conducted with different additional carbon sources (such as: glucose, DL-malic acid, citrate, urea and ammonium acetate) to elucidate the degradation of polycyclic aromatic hydrocarbons (PAHs) in aged contaminated soil under an indoor simulation experiment. The results showed that the quantity of CO2 emission in different additional carbon sources treatments was obviously much more than that of check treatment in the first week, and the quantity of CO2 emission in DL-malic acid treatment was the largest. The average CO2 production decreased in an order urea > glucose approximately citrate approximately DL-malic acid approximately ammonium acetate > check. Meanwhile, the amount of volatized PAHs in applied carbon sources treatments was significantly less than that in check treatment. The amount of three volatized PAHs decreased in an order phenanthrene > fluoranthene > benzo(b)fluoranthene. Compared with the check treatment, the average degradation rates of the three PAHs were significantly augmented in the supplied carbon sources treatments, in which rates of the three PAHs were much higher in DL-malic acid and urea treatments than those in other treatments. The largest proportion of residual was benzo(b)fluoranthene (from 72% to 81%) among three PAHs compounds, followed by fluoranthene (from 53% to 70% ) and phenanthrene (from 27% to 44%).

  4. Vibrational Relaxation of Ground-State Oxygen Molecules With Atomic Oxygen and Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Saran, D. V.; Pejakovic, D. A.; Copeland, R. A.

    2008-12-01

    Vertical water vapor profiles are key to understanding the composition and energy budget in the mesosphere and lower thermosphere (MLT). The SABER instrument onboard NASA's TIMED satellite measures such profiles by detecting H2O(ν2) emission in the 6.8 μm region. Collisional deactivation of vibrationally excited O2, O2(X3Σ-g, υ = 1) + H2O ↔ O2(X3Σ-g, υ = 0) + H2O(ν2), is an important source of H2O(ν2). A recent study has identified two other processes involving excited O2 that control H2O(ν2) population in the MLT: (1) the vibrational-translational (V-T) relaxation of O2(X3Σ-g, υ = 1) level by atomic oxygen and (2) the V-V exchange between CO2 and excited O2 molecules [1]. Over the past few years SRI researchers have measured the atomic oxygen removal process mentioned above at room temperature [2] and 240 K [3]. These measurements have been incorporated into the models for H2O(ν2) emission [1]. Here we report laboratory studies of the collisional removal of O2(X3Σ-g, υ = 1) by O(3P) at room temperature and below, reaching temperatures relevant to mesopause and polar summer MLT (~150 K). Instead of directly detecting the O2(X3Σ-g, υ = 1) population, a technically simpler approach is used in which the υ = 1 level of the O2(a1Δg) state is monitored. A two-laser method is employed, in which the pulsed output of the first laser near 285 nm photodissociates ozone to produce atomic oxygen and O2(a1Δg, υ = 1), and the pulsed output of the second laser detects O2(a1Δg, υ = 1) via resonance-enhanced multiphoton ionization. With ground-state O2 present, owing to the rapid equilibration of the O2(X3Σ-g, υ = 1) and O2(a1Δg, υ = 1) populations via the processes O2(a1Δg, υ = 1) + O2(X3Σ-g, υ = 0) ↔ O2(a1Δg, υ = 0) + O2(X3Σ-g, υ = 1), the information on the O2(X3Σ-g, υ = 1) kinetics is extracted from the O2(a1Δg, υ = 1) temporal evolution. In addition, measurements of the removal of O2(X3Σ-g, υ = 1) by CO2 at room temperature will also

  5. 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.

  6. 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.

  7. 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. PMID:27522987

  8. Carbon nanotubes randomly decorated with gold clusters: from nano2hybrid atomic structures to gas sensing prototypes.

    PubMed

    Charlier, J-C; Arnaud, L; Avilov, I V; Delgado, M; Demoisson, F; Espinosa, E H; Ewels, C P; Felten, A; Guillot, J; Ionescu, R; Leghrib, R; Llobet, E; Mansour, A; Migeon, H-N; Pireaux, J-J; Reniers, F; Suarez-Martinez, I; Watson, G E; Zanolli, Z

    2009-09-16

    Carbon nanotube surfaces, activated and randomly decorated with metal nanoclusters, have been studied in uniquely combined theoretical and experimental approaches as prototypes for molecular recognition. The key concept is to shape metallic clusters that donate or accept a fractional charge upon adsorption of a target molecule, and modify the electron transport in the nanotube. The present work focuses on a simple system, carbon nanotubes with gold clusters. The nature of the gold-nanotube interaction is studied using first-principles techniques. The numerical simulations predict the binding and diffusion energies of gold atoms at the tube surface, including realistic atomic models for defects potentially present at the nanotube surface. The atomic structure of the gold nanoclusters and their effect on the intrinsic electronic quantum transport properties of the nanotube are also predicted. Experimentally, multi-wall CNTs are decorated with gold clusters using (1) vacuum evaporation, after activation with an RF oxygen plasma and (2) colloid solution injected into an RF atmospheric plasma; the hybrid systems are accurately characterized using XPS and TEM techniques. The response of gas sensors based on these nano(2)hybrids is quantified for the detection of toxic species like NO(2), CO, C(2)H(5)OH and C(2)H(4). PMID:19706940

  9. 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

    2014-06-01

    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.

  10. 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

  11. 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

  12. 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.

  13. 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. PMID:25150685

  14. a Proposal for a General Method for Determining Semi-Experimental Equilibrium Structures of Carbon Atom Backbones

    NASA Astrophysics Data System (ADS)

    Craig, Norman C.

    2010-06-01

    Semi-experimental equilibrium structures are determined from ground state rotational constants derived from the analysis of rotational transitions in high-resolution spectra and from the quantum chemical calculation of spectroscopic alphas. In the full application of this method, spectra of numerous isotopic species must be investigated. Most of these isotopic species require specialized synthesis. We now propose focusing on the carbon atoms, for which microwave spectroscopy routinely yields spectra for polar molecules with 13C substitution in natural abundance. Needed spectroscopic alphas can be computed with Gaussian software. Application of the Kraitchman substitution relationships gives Cartesian coordinates for the carbon atoms and thence bond parameters for the carbon backbone. This method will be evaluated with ethylene, 1,1-difluoroethylene, 1,1-difluorocyclopropane, propene, and butadiene. The method will then be applied to cis-hexatriene and the two conformers of glycidol. R. D. Suenram, B. H. Pate, A. Lessari, J. L. Neill, S. Shipman, R. A. Holmes, M. C. Leyden, and N. C. Craig, J. Phys. Chem. A 113, 1864-1868 (2009). A. R. Conrad, N. H. Teumelsan, P. E. Wang, and M. J. Tubergen, J. Phys. Chem. A 114, 336-342 (2010).

  15. Alteration of belowground carbon dynamics by nitrogen addition in southern California mixed conifer forests

    SciTech Connect

    Nowinski, Nicole S.; Trumbore, Susan E.; Jimenez, Gloria; Fenn, Mark E.

    2009-04-01

    Nitrogen deposition rates in southern California are the highest in North America and have had substantial effects on ecosystem functioning. We document changes in the belowground C cycle near ponderosa pine trees experiencing experimental nitrogen (N) addition (50 and 150 kg N ha 1 a 1 as slow release urea since 1997) at two end member sites along a pollution gradient in the San Bernardino Mountains, California. Despite considerable differences in N deposition between the two sites, we observed parallel changes in microbial substrate use and soil enzyme activity with N addition. 14C measurements indicate that the mean age of C respired by the Oa horizon declined 10 15 years with N addition at both sites. N addition caused an increase in cellulolytic enzyme activity at the polluted site and a decrease in ligninolytic enzyme activity at the unpolluted site. Given the likely differences in lignin and cellulose ages, this could explain the difference in the age of microbial respiration with N addition. Measurements of fractionated soil organic matter did not show the same magnitude of changes in response to N addition as were observed for respired C. This lesser response was likely because the soils are mostly composed of C having turnover times of decades to centuries, and 9 years of N amendment were not enough to affect this material. Consequently, 14C of respired CO2 provided a more sensitive indicator of the effects of N addition than other methods. Results suggest that enhanced N deposition alone may not result in increased soil C storage in xeric ecosystems.

  16. 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

  17. Use of pyrolyzed carbon black as additive in hot mix asphalt

    SciTech Connect

    Park, T.; Lee, K.; Salgado, R.; Lovell, C.W.; Coree, B.J.

    1997-11-01

    This paper deals with the performance of mixtures of asphalt, pyrolyzed carbon black (CB{sub p}), and two aggregates (limestone and slag). Marshall mix design was performed to determine the optimum binder content at 5% of air voids. The range of the optimum binder content was 4.2%--5.5% for limestone mixtures and 6.3%--7.8% for slag mixtures, respectively. Dynamic confined creep tests, gyratory tests, resilient modulus tests, indirect tensile tests, and Hamburg wheel tracking tests were carried out using mixtures at the optimum binder content. The test results indicate that the use of CB{sub p} in asphalt pavements increases Marshall stability, decreases permanent strain, decreases the mix strain rate at 50 C and 138 kPa confinement, increases resilient modulus and tensile strength, and increases the stripping inflection point. These results suggest that CB{sub p} improves asphalt pavement performance.

  18. 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.

  19. Multielement determination of heavy metals in water samples by continuous powder introduction microwave-induced plasma atomic emission spectrometry after preconcentration on activated carbon

    NASA Astrophysics Data System (ADS)

    Jankowski, Krzysztof; Yao, Jun; Kasiura, Krzysztof; Jackowska, Adrianna; Sieradzka, Anna

    2005-03-01

    A novel continuous powder introduction microwave-induced plasma atomic emission spectrometry method (CPI-MIP-AES) has been developed for trace determination of metals in ground and tap water samples after preconcentration on activated carbon. The experimental setup consisted of integrated rectangular cavity TE 101 and vertically positioned plasma torch. The technical arrangement of the sample introduction system has been designed based on the fluidized bed concept. The satisfactory signal stability required for sequential analysis was attained owing to the vertical plasma configuration, as well as the plasma gas flow rate compatibility with sample introduction flow rate. The elements of interest (Cd, Cu, Cr, Fe, Mn, Pb, Zn) were preconcentrated in a batch procedure at pH 8-8.5 after addition of activated carbon and then, after filtering and drying of the activated carbon suspension, introduced to the MIP by the CPI system. An enrichment factor of about 1000-fold for a sample volume of 1 l was obtained. The detection limit values for the proposed method were 17-250 ng l -1. The proposed method was validated by analyzing the certified reference materials: SRW "Warta" Synthetic River Water and BCR CRM 399 major elements in freshwater. The method was successfully applied to the determination of the heavy metals in tap water samples.

  20. Three-dimensional bicomponent supramolecular nanoporous self-assembly on a hybrid all-carbon atomically flat and transparent platform.

    PubMed

    Li, Juan; Wieghold, Sarah; Öner, Murat Anil; Simon, Patrick; Hauf, Moritz V; Margapoti, Emanuela; Garrido, Jose A; Esch, Friedrich; Palma, Carlos-Andres; Barth, Johannes V

    2014-08-13

    Molecular self-assembly is a versatile nanofabrication technique with atomic precision en route to molecule-based electronic components and devices. Here, we demonstrate a three-dimensional, bicomponent supramolecular network architecture on an all-carbon sp(2)-sp(3) transparent platform. The substrate consists of hydrogenated diamond decorated with a monolayer graphene sheet. The pertaining bilayer assembly of a melamine-naphthalenetetracarboxylic diimide supramolecular network exhibiting a nanoporous honeycomb structure is explored via scanning tunneling microscopy initially at the solution-highly oriented pyrolytic graphite interface. On both graphene-terminated copper and an atomically flat graphene/diamond hybrid substrate, an assembly protocol is demonstrated yielding similar supramolecular networks with long-range order. Our results suggest that hybrid platforms, (supramolecular) chemistry and thermodynamic growth protocols can be merged for in situ molecular device fabrication. PMID:25115337

  1. 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

  2. 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. PMID:26783836

  3. 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.

  4. 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.

  5. Kinetic and mechanistic studies of carbon-to-metal hydrogen atom transfer involving Os-centered radicals: evidence for tunneling.

    PubMed

    Lewandowska-Andralojc, Anna; Grills, David C; Zhang, Jie; Bullock, R Morris; Miyazawa, Akira; Kawanishi, Yuji; Fujita, Etsuko

    2014-03-01

    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. Time-resolved IR spectroscopic measurements revealed efficient hydrogen atom transfer from xanthene, 9,10-dihydroanthracene, and 1,4-cyclohexadiene to Cp(CO)2Os(•) and (η(5)-(i)Pr4C5H)(CO)2Os(•) radicals, formed by photoinduced homolysis of the corresponding osmium dimers. The rate constants for hydrogen abstraction from these hydrocarbons are in the range 1.5 × 10(5) M(-1) s(-1) to 1.7 × 10(7) 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 deuterium kinetic isotope effects of 13.4 ± 1.0 and 16.8 ± 1.4 were observed for the hydrogen abstraction from xanthene to form Cp(CO)2OsH and (η(5)-(i)Pr4C5H)(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 (E(D) - E(H)) and the pre-exponential factor ratio (A(H)/A(D)). For hydrogen atom transfer from xanthene to (η(5)-(i)Pr4C5H)(CO)2Os(•), the (E(D) - E(H)) = 3.3 ± 0.2 kcal mol(-1) and A(H)/A(D) = 0.06 ± 0.02 values suggest a quantum mechanical tunneling mechanism.

  6. Solid sampling determination of lithium and sodium additives in microsamples of yttrium oxyorthosilicate by high-resolution continuum source graphite furnace atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Laczai, Nikoletta; Kovács, László; Péter, Ágnes; Bencs, László

    2016-03-01

    Solid sampling high resolution continuum source graphite furnace atomic absorption spectrometry (SS-HR-CS-GFAAS) methods were developed and studied for the fast and sensitive quantitation of Li and Na additives in microsamples of cerium-doped yttrium oxyorthosilicate (Y2SiO5:Ce) scintillator materials. The methods were optimized for solid samples by studying a set of GFAAS conditions (i.e., the sample mass, sensitivity of the analytical lines, and graphite furnace heating programs). Powdered samples in the mass range of 0.099-0.422 mg were dispensed onto graphite sample insertion boats, weighed and analyzed. Pyrolysis and atomization temperatures were optimized by the use of single-element standard solutions of Li and Na (acidified with 0.144 mol/L HNO3) at the Li I 610.353 nm and Na I 285.3013 nm analytical lines. For calibration purposes, the method of standard addition with Li and Na solutions was applied. The correlation coefficients (R values) of the calibration graphs were not worse than 0.9678. The limit of detection for oxyorthosilicate samples was 20 μg/g and 80 μg/g for Li and Na, respectively. The alkaline content of the solid samples were found to be in the range of 0.89 and 8.4 mg/g, respectively. The accuracy of the results was verified by means of analyzing certified reference samples, using methods of standard (solution) addition calibration.

  7. 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.

  8. First principle study of magnetic and electronic properties of single X (X = Al, Si) atom added to small carbon clusters (C n X, n = 2-10)

    NASA Astrophysics Data System (ADS)

    Afshar, M.; Hoseini, S. S.; Sargolzaei, M.

    2016-07-01

    In this paper, the magnetic and electronic properties of single aluminum and silicon atom added to small carbon clusters (C n X; X = Al, Si; n = 2-10) are studied in the framework of generalized-gradient approximation using density functional theory. The calculations were performed for linear, two dimensional and three dimensional clusters based on full-potential local-orbital (FPLO) method. The total energies, HOMO-LUMO energy gap and total magnetic moments of the most stable structures are presented in this work. The calculations show that C n Si clusters have more stability compared to C n Al clusters. In addition, our magnetic calculations were shown that the C n Al isomers are magnetic objects whereas C n Si clusters are nonmagnetic objects.

  9. 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

    2007-05-01

    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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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. PMID:25113518

  15. 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.

  16. 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.

  17. Influence of carbon nanotube addition on sliding wear behaviour of pulse electrodeposited cobalt (Co)-phosphorus (P) coatings

    NASA Astrophysics Data System (ADS)

    Edward Anand, E.; Natarajan, S.

    2015-09-01

    This work examines the sliding wear behaviour of nanostructured cobalt-phosphorus (Co-P) alloy electrodeposits reinforced with multiwalled carbon nanotubes (MWCNTs). Nanocrystalline cobalt-phosphorus alloy coatings reinforced with carbon nanotubes were produced by pulse electrodeposition from an aqueous bath. Tribological properties of the coatings with and without MWCNT addition were characterized. Anisotropic tribological behaviour was observed for the coatings reinforced with MWCNTs when slided against hard steel counterparts. The nanocrystalline Co-P-CNT coatings display better wear resistance and friction reduction compared with the nanocrystalline Co-P coating. The friction coefficients and wear rates of the nanocrystalline Co-P-CNT coating are influenced by the test conditions including the applied load, sliding speed and more importantly the alignment of MWCNTs in the deposits. The wear mechanisms of the nanocrystalline Co-P and Co-P-CNT alloy coatings involved in different sliding conditions are explained related to their friction and wear properties.

  18. Hot isostatic pressing of silicon nitride with boron nitride, boron carbide, and carbon additions

    NASA Technical Reports Server (NTRS)

    Mieskowski, Diane M.; Sanders, William A.

    1989-01-01

    Si3N4 test bars containing additions of BN, B4C, and C, were hot isostatically pressed in Ta cladding at 1900 and 2050 C to 98.9 percent to 99.5 percent theoretical density. Room-temperature strength data on specimens containing 2 wt pct BN and 0.5 wt pct C were comparable to data obtained for Si3N4 sintered with Y2O3, Y2O3 and Al2O3, or ZrO2. The 1370 C strengths were less than those obtained for additions of Y2O3 or ZrO2 but greater than those obtained from a combination of Y2O3 and Al2O3. SEM fractography indicated that, as with other types of Si3N4, room-temperature strength was controlled by processing flaws. The decrease in strength at 1370 C was typical of Si3N4 having an amorphous grain-boundary phase. The primary advantage of nonoxide additions appears to be in facilitating specimen removal from the Ta cladding.

  19. Nutrient removal in wastewater treatment high rate algal ponds with carbon dioxide addition.

    PubMed

    Park, J B K; Craggs, R J

    2011-01-01

    The influence of CO2 addition to high rate algal ponds (HRAPS) on nitrogen removal was investigated using two pilot-scale HRAPs operated with different hydraulic retention times (HRT: 4 and 8 days), and was compared to the nitrogen removal by the 8-day HRT pond before CO2 addition was installed. Nitrogen balances were calculated by partitioning total nitrogen into organic and inorganic nitrogen (NH4+-N and NO3--N), and by separation of the organic nitrogen into particulate (PON) and dissolved organic nitrogen (DON). PON was further divided into algal organic nitrogen (AON) and bacteria organic nitrogen (BON) to investigate nitrogen mass flow in the HRAPS. This research shows that the proportion of algae in the algal/bacterial biomass in the longer 8-day HRT HRAP8d (55.6%) was appreciably lower than that in the shorter 4-day HRT HRAP4d (80.5%) when CO2 was added to control the maximum pH to <8.0 during the summer. Higher bacterial biomass in the longer 8-day HRT HRAP corresponded with higher nitrification rates, indicating that the longer 8-day HRT in the summer was detrimental for two reasons: lower algal productivity and increased nitrogen loss through nitrification/denitrification. Overall nitrogen removal of approximately 60% in the HRAPS with CO2 addition was mainly achieved by algal assimilation followed by sedimentation in the settling unit.

  20. 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.

  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. Stable carbon isotopic composition of the wine and CO2 bubbles of sparkling wines: detecting C4 sugar additions.

    PubMed

    Martinelli, Luiz A; Moreira, Marcelo Z; Ometto, Jean P H B; Alcarde, André R; Rizzon, Luiz A; Stange, Erik; Ehleringer, James R

    2003-04-23

    Sparkling wines have become a popular beverage in recent years, and the production of these wines is subject to adulteration during fermentation. This study investigated the stable carbon isotopic composition (expressed as delta(13)C) of the wine and of the CO(2) bubbles produced during the second fermentation for a number of sparkling wines produced in different countries around the world. Carbon isotope ratio analyses were used to estimate the addition of sugar obtained from C(4) plants (sugar cane or corn). The average delta(13)C values of the Brazilian brut, demi-sec, and doux sparkling wines were -20.5 +/- 1.2 per thousand (n = 18), -18.1 +/- 1.3 per thousand (n = 9), and -15.8 per thousand (n = 1), respectively. These values were statistically heavier (more positive carbon isotope ratio values) than the average delta(13)C of sparkling wines produced in other parts of South America (Argentina and Chile, -26.1 +/- 1.6 per thousand, n = 5) and Europe (France, Germany, Italy, Portugal, and Spain, -25.5 +/- 1.2 per thousand, n = 12), but not statistically different from sparkling wines produced in the United States or Australia. The most likely explanation for differences in the carbon isotope ratios of wines from these different regions is the addition of C(4) sugar during the production of some sparkling wines from Australia, Brazil, and the United States. The isotopic composition of the CO(2) bubbles (delta(13)C-CO(2)) followed similar trends. The average delta(13)C-CO(2) of most of the Brazilian and Argentine sparkling wines was -10.8 +/- 1.2 per thousand (n = 23), indicating that the likely source of carbon for the second fermentation was sugar cane. Conversely, the average delta(13)C-CO(2) of most of the sparkling wines produced in Chile and Europe was -22.0 +/- 1.2 per thousand (n = 13), suggesting that a different sugar (most likely sugar beet) was most used in the second fermentation. It was concluded that in many cases, the carbon isotope ratios of

  3. Size-selective catalytic growth of nearly 100% pure carbon nanocoils with copper nanoparticles produced by atomic layer deposition.

    PubMed

    Wang, Guizhen; Ran, Gu; Wan, Gengping; Yang, Peng; Gao, Zhe; Lin, Shiwei; Fu, Chuan; Qin, Yong

    2014-05-27

    In this paper, Cu nanoparticles with narrow size distribution are synthesized by reduction of CuO films produced by atomic layer deposition (ALD), which are used as catalysts for the catalytic growth of carbon nanostructures. By properly adjusting the ALD cycle numbers, the size of produced Cu nanoparticles can be well controlled. Uniform carbon nanocoils with near 100% purity can be obtained by using 50-80 nm Cu nanoparticles, while thin straight fibers and thick straight fibers are produced by applying 5-35 and 100-200 nm Cu nanoparticles, respectively. The mechanism of the particle size-dependent growth of the carbon nanostructure was analyzed based on the experimental results and theoretical simulation. Our results can provide important information for the preparation of helical carbon nanostructures with high purity. Moreover, this work also demonstrates that ALD is a viable technique for synthesizing nanoparticles with highly controllable size and narrow size distribution suitable for studying particle size-dependent catalytic behavior and other applications.

  4. 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

  5. Effect of biomass addition on the surface and adsorption characterization of carbon-based adsorbents from sewage sludge.

    PubMed

    Wu, Changzi; Song, Min; Jin, Baosheng; Wu, Yimin; Huang, Yaji

    2013-02-01

    Sewage sludge with the additive corn cob was used as prescusor to prepare sludge-based carbon adsorbents by pyrolysis method. And then, the carbonizated products were activated with potassium hydroxide. The mixing ratio of the corn cob to sewage sludge was investigated. The surface area and pore size distribution, elemental composition, surface chemistry structure and the surface physical morphology were determined and compared. The results demonstrated that the addition of corn cob into the sewage sludge sample could effectively improve the surface area (from 287 to 591 m2/g) and the microporosity (from 5% to 48%) of the carbon based adsorbent, thus enhancing the adsorption behavior. The sulfur dioxide adsorption capacity was measured according to breakthrough test. It was found that the sulfur dioxide adsorption capacity of the adsorbents was obviously enhanced after the addition of the corn cob. It is presumed that not only highly porous adsorbents, but also a high metallic content of these materials are required to achieve good performances. PMID:23596963

  6. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel.

    PubMed

    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. 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

  8. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel.

    PubMed

    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

  9. Effect of carbon source addition on toluene biodegradation by an Escherichia coli DH5alpha transconjugant harboring the TOL plasmid.

    PubMed

    Ikuma, Kaoru; Gunsch, Claudia

    2010-10-01

    Horizontal gene transfer (HGT) of plasmids is a naturally occurring phenomenon which could be manipulated for bioremediation applications. Specifically, HGT may prove useful to enhance bioremediation through genetic bioaugmentation. However, because the transfer of a plasmid between donor and recipient cells does not always result in useful functional phenotypes, the conditions under which HGT events result in enhanced degradative capabilities must first be elucidated. The objective of this study was to determine if the addition of alternate carbon substrates could improve toluene degradation in Escherichia coli DH5alpha transconjugants. The addition of glucose (0.5-5 g/L) and Luria-Bertani (LB) broth (10-100%) resulted in enhanced toluene degradation. On average, the toluene degradation rate increased 14.1 (+/-2.1)-fold in the presence of glucose while the maximum increase was 18.4 (+/-1.7)-fold in the presence of 25% LB broth. Gene expression of xyl genes was upregulated in the presence of glucose but not LB broth, which implies different inducing mechanisms by the two types of alternate carbon source. The increased toluene degradation by the addition of glucose or LB broth was persistent over the short-term, suggesting the pulse amendment of an alternative carbon source may be helpful in bioremediation. While the effects of recipient genome GC content and other conditions must still be examined, our results suggest that changes in environmental conditions such as alternate substrate availability may significantly improve the functionality of the transferred phenotypes in HGT and therefore may be an important parameter for genetic bioaugmentation optimization.

  10. Negative ion productions in high velocity collision between small carbon clusters and Helium atom target

    NASA Astrophysics Data System (ADS)

    M, Chabot; K, Béroff; T, Pino; G, Féraud; N, Dothi; Padellec A, Le; G, Martinet; S, Bouneau; Y, Carpentier

    2012-11-01

    We measured absolute double capture cross section of Cn+ ions (n=1,5) colliding, at 2.3 and 2.6 a.u velocities, with an Helium target atom and the branching ratios of fragmentation of the so formed electronically excited anions Cn-*. We also measured absolute cross section for the electronic attachment on neutral Cn clusters colliding at same velocities with He atom. This is to our knowledge the first measurement of neutral-neutral charge exchange in high velocity collision.

  11. A high precision study of the electrolyte additives vinylene carbonate, vinyl ethylene carbonate and lithium bis(oxalate)borate in LiCoO2/graphite pouch cells

    NASA Astrophysics Data System (ADS)

    Wang, David Yaohui; Sinha, N. N.; Burns, J. C.; Petibon, R.; Dahn, J. R.

    2014-12-01

    The effects of three well-known electrolyte additives, used singly or in combination, on LiCoO2/graphite pouch cells has been investigated using the ultra high precision charger (UHPC) at Dalhousie University, electrochemical impedance spectroscopy (EIS) and long term cycling Vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and lithium bis(oxalato) borate (LiBOB) were chosen for study. The results show that combinations of electrolyte additives that act synergistically can be more effective than a single electrolyte additive. However, simply using 2% VC yielded cells very competitive in coulombic efficiency (CE), charge endpoint capacity slippage and charge transfer resistance (Rct). For cells with 1% LiBOB and VC (1, 2, 4 or 6%), adding VC above 2% does not increase the CE, but increases the electrode charge transfer impedances. Rct for cells containing 1% LiBOB and VEC (0.5, 1 or 4%) decreased after long term cycling (1800 h), compared to that tested after the UHPC cycling (500 h) indicating that VEC might be useful for the design of power cells. However, the opposite behaviour (increasing Rct with cycle number) was observed for the control cells or cells containing LiBOB and/or VC.

  12. Use of pyrolyzed carbon black as an additive (part 3. Air-cooled furnace slag). Final report

    SciTech Connect

    Lee, K.H.; Lovell, C.W.; Salgado, R.

    1996-11-20

    Scrap tires, generated at the rate of over 242 million each year in the United States, are recognized as one of the most significant environmental problems. Most of these scrap tires have been disposed of in landfills, stockpiles, and illegal dumps (EPA 1991). There is a need to find more useful, environmentally friendly applications for these tires. Extensive researches have been conducted in the past years on the utilization of the scrap tires. The use of scrap tires for asphalt pavement, which is complicated by the complex behavior of asphalt, has received major attention. This research aims to describe the performance of mixtures of asphalt using pyrolyzed carbon black as an additive.

  13. Chemisorption of Transition-Metal Atoms on Boron- and Nitrogen-Doped Carbon Nanotubes: Energetics and Geometric and Electronic Structures

    SciTech Connect

    An, Wei; Turner, C. H.

    2009-04-30

    The well-defined binding between transition-metals (TM) and the sidewall of carbon nanotubes (CNTs) plays a key role in the performance of CNT-based anoelectronics, as well as the stability of catalysts used in either heterogeneous catalysis or fuel-cell electrocatalysis. Spin-polarized density functional theory calculations demonstrate that either boron or nitrogen doping can increase the binding strength of TM atoms with singlewall carbon nanotubes (SWCNTs), and comparatively, boron doping is more effective. The binding nature can be identified as chemisorption, based on the magnitude of the binding energy and the formation of multiple bonds. The chemisorbed TM atoms can modify the electronic structure of the doped nanotubes in various ways, depending upon the TM and helicity of the CNT, rendering the TM/doped-SWCNT composite viable for a wide range of applications. A total of 11 technologically relevant TMs adsorbed on two distinct and stable doped-SWCNT models have been investigated in this study. The doping sites are arranged in either a locally concentrated or uniform fashion within semiconducting SWCNT(8,0) and metallic SWCNT(6,6). The results serve as a starting point for studying larger, more complex TM nanostructures anchored on the sidewall of boron- or nitrogen-doped CNTs.

  14. Characterization of atomic structure of oxide films on carbon steel in simulated concrete pore solutions using EELS

    NASA Astrophysics Data System (ADS)

    Gunay, H. Burak; Ghods, Pouria; Isgor, O. Burkan; Carpenter, Graham J. C.; Wu, Xiaohua

    2013-06-01

    The atomic structure of oxide films formed on carbon steel that are exposed to highly alkaline simulated concrete pore solutions was investigated using Electron Energy Loss Spectroscopy (EELS). In particular, the effect of chloride exposure on film structure was studied in two types of simulated pore solutions: saturated calcium hydroxide (CH) and a solution prepared to represent typical concrete pore solutions (CP). It was shown that the films that form on carbon steel in simulated concrete pore solutions contained three indistinct layers. The inner oxide film had a structure similar to that of FeIIO, which is known to be unstable in the presence of chlorides. The outer oxide film mainly resembled Fe3O4 (FeIIO·Fe2IIIO3) in the CH solution and α-Fe2IIIO3/Fe3O4 in the CP solution. The composition of the transition layer between the inner and outer layers of the oxide film was mainly composed of Fe3O4 (FeIIO·Fe2IIIO3). In the presence of chloride, the relative amount of the FeIII/FeII increased, confirming that chlorides induce valence state transformation of oxides from FeII to FeIII, and the difference between the atomic structures of oxide film layers diminished.

  15. Effects of silicon, carbon and molybdenum additions on IASCC of neutron irradiated austenitic stainless steels

    NASA Astrophysics Data System (ADS)

    Nakano, J.; Miwa, Y.; Kohya, T.; Tsukada, T.

    2004-08-01

    To study the effects of minor elements on irradiation assisted stress corrosion cracking (IASCC), high purity type 304 and 316 stainless steels (SSs) were fabricated and minor elements, Si or C were added. After neutron irradiation to 3.5 × 10 25 n/m 2 ( E>1 MeV), slow strain rate tests (SSRTs) of irradiated specimens were conducted in oxygenated high purity water at 561 K. Specimen fractured surfaces were examined using a scanning electron microscope (SEM) after the SSRTs. The fraction of intergranular stress corrosion cracking (IGSCC) on the fractured surface after the SSRTs increased with neutron fluence. In high purity SS with added C, the fraction of IGSCC was the smallest in the all SSs, although irradiation hardening level was the largest of all the SSs. Addition of C suppressed the susceptibility to IGSCC.

  16. 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.

  17. 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

  18. 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

  19. Carbon Dioxide Activation by Scandium Atoms and Scandium Monoxide Molecules: Formation and Spectroscopic Characterization of ScCO3 and OCScCO3 in Solid Neon.

    PubMed

    Zhang, Qingnan; Qu, Hui; Chen, Mohua; Zhou, Mingfei

    2016-01-28

    The reactions of carbon dioxide with scandium monoxide molecules and scandium atoms are investigated using matrix isolation infrared spectroscopy in solid neon. The species formed are identified by the effects of isotopic substitution on their infrared spectra as well as density functional calculations. The results show that the ground state ScO molecule reacts with carbon dioxide to form the carbonate complex ScCO3 spontaneously on annealing. The ground state Sc atom reacts with two carbon dioxide molecules to give the carbonate carbonyl complex OCScCO3 via the previously reported OScCO insertion intermediate on annealing. The observation of these spontaneous reactions is consistent with theoretical predictions that both the Sc + 2CO2 → OCScCO3 and ScO + CO2 → ScCO3 reactions are thermodynamically exothermic and are kinetically facile, requiring little or no activation energy. PMID:26738558

  20. Carbon Dioxide Activation by Scandium Atoms and Scandium Monoxide Molecules: Formation and Spectroscopic Characterization of ScCO3 and OCScCO3 in Solid Neon.

    PubMed

    Zhang, Qingnan; Qu, Hui; Chen, Mohua; Zhou, Mingfei

    2016-01-28

    The reactions of carbon dioxide with scandium monoxide molecules and scandium atoms are investigated using matrix isolation infrared spectroscopy in solid neon. The species formed are identified by the effects of isotopic substitution on their infrared spectra as well as density functional calculations. The results show that the ground state ScO molecule reacts with carbon dioxide to form the carbonate complex ScCO3 spontaneously on annealing. The ground state Sc atom reacts with two carbon dioxide molecules to give the carbonate carbonyl complex OCScCO3 via the previously reported OScCO insertion intermediate on annealing. The observation of these spontaneous reactions is consistent with theoretical predictions that both the Sc + 2CO2 → OCScCO3 and ScO + CO2 → ScCO3 reactions are thermodynamically exothermic and are kinetically facile, requiring little or no activation energy.

  1. Effects of Silica Nanoparticle Supported Ionic Liquid as Additive on Thermal Reversibility of Human Carbonic Anhydrase II

    PubMed Central

    Fallahbagheri, Azadeh; Saboury, Ali Akbar; Ma'mani, Leila; Taghizadeh, Mohammad; Khodarahmi, Reza; Ranjbar, Samira; Bohlooli, Mousa; Shafiee, Abbas; Foroumadi, Alireza; Sheibani, Nader; Moosavi-Movahedi, Ali Akbar

    2013-01-01

    Silica nanoparticle supported imidazolium ionic liquid [SNImIL] was synthesized and utilized as a biocompatible additive for studying the thermal reversibility of human carbonic anhydrase II (HCA II). For this purpose, we prepared additive by modification of nanoparticles through the grafting of ionic liquids on the surface of nanoparticles (SNImIL). The SNImIL were fully characterized by Fourier Transform Infrared spectroscopy, scanning electron microscopy and thermo gravimetric analysis. The characterization of HCA II was investigated by various techniques including UV–Vis and ANS fluorescence spectrophotometry, differential scanning calorimetry, and docking study. SNImIL induced disaggregation, enhanced protein stability and increased thermal reversibility of HCA II by up to 42% at pH 7.75. PMID:22829053

  2. 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. PMID:25801795

  3. 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.

  4. A SnO2-samarium doped ceria additional anode layer in a direct carbon fuel cell

    NASA Astrophysics Data System (ADS)

    Yu, Baolong; Zhao, Yicheng; Li, Yongdan

    2016-02-01

    The role of a SnO2-samarium doped ceria (SDC) additional anode layer in a direct carbon fuel cell (DCFC) with SDC-(Li0.67Na0.33)2CO3 composite electrolyte and lithiated NiO-SDC-(Li0.67Na0.33)2CO3 composite cathode is investigated and compared with a NiO-SDC extra anode layer. Catalytic grown carbon fiber mixed with (Li0.67Na0.33)2CO3 is used as a fuel. At 750 °C, the maximum power outputs of 192 and 143 mW cm-2 are obtained by the cells with SnO2-SDC and NiO-SDC layers, respectively. In the SnO2-SDC layer, the reduction of SnO2 and the oxidation of Sn happen simultaneously during the cell operation, and the Sn/SnO2 redox cycle provides an additional route for fuel conversion. The formation of an insulating dense interlayer between the anode and electrolyte layers, which usually happens in DCFCs with metal anodes, is avoided in the cell with the SnO2-SDC layer, and the stability of the cell is improved consequently.

  5. Interaction between carbon dioxide and coal: atomic-scale characteristics and electronic structures

    NASA Astrophysics Data System (ADS)

    Liu, Yingdi; Wang, Sanwu

    2015-03-01

    Geologic sequestration of CO2 in unmineable coal seams has been suggested to mitigate the effect of the increasing of the atmospheric CO2 concentration on global warming. Extensive experimental studies have been performed for the injection of CO2 into coalbeds. However, the atomic-level mechanism for the interaction between CO2 and coal has not been fully explored. We report first-principles density-functional calculations and ab initio molecular dynamics simulations for the interaction between CO2 and the coal network. In particular, we report results about atomic-scale and electronic properties of the interaction. We also report a comparison with the interaction between CH4 and coal. This research used the supercomputer resources at NERSC, of XSEDE, at TACC, and at the Tandy Supercomputing Center.

  6. Atomic and electronic structures of carbon nanotube covalent connecting with graphene by oxygen molecular

    NASA Astrophysics Data System (ADS)

    Wei, Jianwei; Wei, Qiang; Ma, Zengwei; Zeng, Hui

    2016-02-01

    Based on density functional theories, we have investigated the nanostructure in which boron and nitrogen co-doped carbon nanotube (CNT)/graphene (GR) were connected by an oxygen molecular. The geometry structure and electronic properties of the system were calculated carefully. The band structures indicate that the impurity state of oxygen transfer the semiconducting co-doped carbon nanotube/graphene into a semimetallic composite material. The results show that the connection can be achieved with energy release under a wider range of distance between the nanotube and graphene. It indicates that the connection between the nanotube and the graphene might be a self-assemble process.

  7. A high-pressure atomic force microscope for imaging in supercritical carbon dioxide

    SciTech Connect

    Lea, Alan S.; Higgins, Steven R.; Knauss, Kevin G.; Rosso, Kevin M.

    2011-04-26

    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 fluid refractive 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 (10¯14) surface are presented. This new AFM provides unprecedented in-situ access to interfacial phenomena at solid-fluid interfaces under pressure.

  8. 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.

  9. 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. PMID:26871958

  10. 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. PMID:26846538

  11. A Multi-line Study of Atomic Carbon and Carbon Monoxide in the Galactic Star- forming Region W3

    NASA Astrophysics Data System (ADS)

    Jakob, H.; Kramer, C.; Mookerjea, B.; Jeyakumar, S.; Stutzki, J.

    We present results from simultaneous observations of the fine structure line emissions of neutral carbon (C I) at 492 and 809 GHz from selected Galactic star forming regions. These observations include the first results using the the newly installed SMART (SubmilliMeter Array Receiver at Two wavelengths) on KOSMA. The regions observed were selected in order to cover a range of strengths of the incident UV radiation from the exciting star/stars and also densities of the interstellar medium. Extended maps of C I emission from massive star forming regions including W3, S106 and Orion BN/KL have been observed. Simultaneous observation of the two C I lines ensures better relative calibration. The results from these observations will be combined with observed intensities of low-J and mid-J CO and C+ lines and analyzed using radiation transfer based models for Photon Dominated Regions (PDRs).

  12. 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

  13. 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

  14. Carbon kinetic isotope effect in the reaction of CH{sub 4} with Cl atoms

    SciTech Connect

    Saueressig, G.; Bergamaschi, P.; Crowley, J.N.

    1995-05-15

    The authors report laser absorption spectroscopy measurements of the carbon kinetic isotope effect involving chlorine reacting with methane under stratospheric type conditions. The authors find a slight isotope effect of 1.066 {+-} 0.002 at 297 K for the ratio of {sup 13}CH{sub 4}/{sup 12}CH{sub 4}. There was also a slight temperature dependence observed.

  15. 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.

  16. 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.

  17. Atomic data and spectral analysis of carbon, nitrogen, oxygen and silicon ions observed with the International Ultraviolet Explorer

    NASA Technical Reports Server (NTRS)

    Pradhan, Anil K.

    1992-01-01

    According to the plan presented in the original proposal we have now completed most of the atomic calculations involving collision strengths and rate coefficients for electron impact excitation of C II, N III, and O IV ions. These have been reported in the first two publications appended with this report. We have now moved into the applications phase of the project with the new data being used to analyze the International Ultraviolet Explorer (IUE) observations of a variety of objects, as described in the third publication recently submitted (also appended). The analysis and interpretation of archival data will continue well into the next year with several collaborators that the PI and Co-PI are involved with. In addition, the atomic calculations on Si II have been started.

  18. Atomic structure of Zr-Cu glassy alloys and detection of deviations from ideal solution behavior with Al addition by x-ray diffraction using synchrotron light in transmission

    NASA Astrophysics Data System (ADS)

    Georgarakis, K.; Yavari, A. R.; Louzguine-Luzgin, D. V.; Antonowicz, J.; Stoica, M.; Li, Y.; Satta, M.; LeMoulec, A.; Vaughan, G.; Inoue, A.

    2009-05-01

    The atomic structure of Zr-Cu binary amorphous alloys was studied using real space pair distribution functions derived from x-ray diffraction. The structure can be modeled by an ideal solution approximation because of relatively weak Cu-Zr atomic interactions. Addition of Al to Zr-Cu metallic glasses modifies the atomic structure in the short and medium range order because of the strongly attractive interaction between Al and Zr atoms. These interactions generate strong deviations from the ideal solution behavior.

  19. Carbon clusters containing two metals atoms: Structures, growth mechanism, and fullerene formation

    SciTech Connect

    Shelimov, K.B.; Jarrold, M.F.

    1996-02-07

    Gas phase ion mobility measurments have been used to probe the structures and interconversion of La{sub 2}C{sub n}{sup +} (n = 1-100) isomers. The smallest La{sub 2}C{sub n}{sup +} clusters (n = 10) appear to be planar rings. However, planar mono and bicylic rings (the dominant isomers for C{sub n}{sup +} and LaC{sub n}{sup +}, n = 30, clusters) are not observed for the larger La{sub 2}C{sub n}{sup +} species. Instead, isomers which appear to be three-dimensional ring complexes dominate for unannealed La{sub 2}C{sub n}{sup +} (n + 17) clusters. The formation of these complexes is probably driven by electrostatic forces. For n = 30 the three-dimensional ring complexes isomerize into metallofullerenes (and metal-containing graphite sheets for n = 30-37). The estimated activation energies for these isomerization processes are about 1eV lower than those estimated for similar processes for planar C{sub n}{sup +} and LaC{sub n}{sup +} rings. Metallofullerenes with two non-endohedral metal atoms (for n = 28-29), one endohedral metal atom (for n = 31-100), and two endohedral metal atoms (for n > 64, only even n), are identified. Fullerene derivatives (presumably fullerene + ring complexes) are abundant in the unannealed isomer distributions for La{sub 2}C{sub n}{sup +} (n > 50) clusters, but readily isomerize into regular fullerenes upon collisional heating. 47 refs., 9 figs., 2 tabs.

  20. 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. PMID:25490701

  1. 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.

  2. 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.

  3. 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.

  4. 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.; 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 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

  5. 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.

  6. The effects of mediator and granular activated carbon addition on degradation of trace organic contaminants by an enzymatic membrane reactor.

    PubMed

    Nguyen, Luong N; Hai, Faisal I; Price, William E; Leusch, Frederic D L; Roddick, Felicity; Ngo, Hao H; Guo, Wenshan; Magram, Saleh F; Nghiem, Long D

    2014-09-01

    The removal of four recalcitrant trace organic contaminants (TrOCs), namely carbamazepine, diclofenac, sulfamethoxazole and atrazine by laccase in an enzymatic membrane reactor (EMR) was studied. Laccases are not effective for degrading non-phenolic compounds; nevertheless, 22-55% removal of these four TrOCs was achieved by the laccase EMR. Addition of the redox-mediator syringaldehyde (SA) to the EMR resulted in a notable dose-dependent improvement (15-45%) of TrOC removal affected by inherent TrOC properties and loading rates. However, SA addition resulted in a concomitant increase in the toxicity of the treated effluent. A further 14-25% improvement in aqueous phase removal of the TrOCs was consistently observed following a one-off dosing of 3g/L granular activated carbon (GAC). Mass balance analysis reveals that this improvement was not due solely to adsorption but also enhanced biodegradation. GAC addition also reduced membrane fouling and the SA-induced toxicity of the effluent. PMID:24980029

  7. 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.

  8. Nanopatterning on silicon surface using atomic force microscopy with diamond-like carbon (DLC)-coated Si probe

    PubMed Central

    2011-01-01

    Atomic force microscope (AFM) equipped with diamond-like carbon (DLC)-coated Si probe has been used for scratch nanolithography on Si surfaces. The effect of scratch direction, applied tip force, scratch speed, and number of scratches on the size of the scratched geometry has been investigated. The size of the groove differs with scratch direction, which increases with the applied tip force and number of scratches but decreases slightly with scratch speed. Complex nanostructures of arrays of parallel lines and square arrays are further fabricated uniformly and precisely on Si substrates at relatively high scratch speed. DLC-coated Si probe has the potential to be an alternative in AFM-based scratch nanofabrication on hard surfaces. PMID:21888633

  9. FORMATION OF CARBON DIOXIDE, METHANOL, ETHANOL, AND FORMIC ACID ON AN ICY GRAIN ANALOG USING FAST OXYGEN ATOMS

    SciTech Connect

    Madzunkov, S. M.; MacAskill, J. A.; Chutjian, A.

    2010-03-20

    Carbon dioxide (CO{sub 2}), methanol (CH{sub 3}OH), ethanol (CH{sub 3}CH{sub 2}OH), and formic acid (HCOOH) have been formed in collisions of a superthermal, 9 eV beam of O({sup 3} P) atoms with CH{sub 4} molecules, with an over coat of CO molecules, adsorbed on a gold surface at 4.8 K. The products are detected using temperature programmed-desorption and quadrupole mass spectrometry. Identification of the species is carried out through use of the Metropolis random walk algorithm as constrained by the fractionation patterns of the detected species. Relative formation yields are reported and reaction sequences are given to account for possible formation routes.

  10. Adsorption of glycine on diamond (001): Role of bond angle of carbon atoms

    NASA Astrophysics Data System (ADS)

    Li, Lin; Xu, Jing; Xu, Li-Fang; Lian, Chao-Sheng; Li, Jun-Jie; Wang, Jian-Tao; Gu, Chang-Zhi

    2015-05-01

    The adsorption behaviors of glycine on diamond (001) are systematically investigated by first-principles calculations. We have considered all possible adsorption configurations without a surface dangling bond and give a quantitative analysis for the relationship between the deviation of carbon bond angle and adsorption energy. We found that a smaller distortion of carbon covalent bond angle results in a more stable adsorption structure, and the most stable adsorption has a benzene-ring-like structure with the highest adsorption energy of 5.11 eV per molecule and the minimum distortion of carbon covalent bond angle. Project supported by the National Natural Science Foundation of China (Grant Nos. 51272278, 91323304, 10774177, and 11374341), the National Basic Research Program of China (Grand No. 2009CB930502), the Knowledge Innovation Project of Chinese Academy of Sciences (Grand No. KJCX2-EW-W02), the Fundamental Research Funds for the Central Universities of Ministry of Education of China, and the Research Funds of Renmin University of China.

  11. A highly catalytic and selective conversion of carboxylic acids to 1-alkenes of one less carbon atom

    SciTech Connect

    Miller, J.A.; Nelson, J.A.; Byrne, M.P. )

    1993-01-01

    An equimolar mixture of a carboxylic acid and acetic anhydride produces a reagent combination that undergoes a highly efficient decarbonylation/dehydration at 250[degrees]C using either Pd- or Rh-based catalyst systems, affording excellent yields of the corresponding 1-alkenes and one less carbon atom. The stoichiometric and catalytic decarbonylation of aliphatic aldehydes and acid chlorides to alkanes and alkenes, respectively, by transition-metal complexes are well-known and synthetically useful transformations. Relatively little, however, has been reported concerning the analogous decarbonylation/dehydration of aliphatic carboxylic acids to olefins, with generally poor results achieved in terms of catalyst efficiency and selectivity toward terminal olefin formation in the product. For example, the decarbonylation/dehydration of stearic acid to heptadecane using a Rh-based catalyst was reported to proceed with a maximum catalyst turnover number (TON; moles of olefin product formed per mole of catalyst used) of ca. 250, with selectivities toward 1-heptadecene formation typically below 50%. Interestingly, results were presented in this work which suggested that the decarbonylation of stearic acid proceeded via intermediate formation of stearic anhydride. Use of a preformed, symmetrical anhydride is not desirable from an economic or synthetic viewpoint, particularly since its decarbonylation should result in the formation of equal amounts of olefin and carboxylic acid coproducts. The authors now report here that the use of a carboxylic acid substrate as an equimolar mixture with acetic anhydride (Ac[sub 2]O) produces a mixed anhydride system which undergoes an extremely facile decarbonylation reaction to provide a general and highly selective route to the corresponding 1-alkenes of one less carbon atom. 19 refs., 1 tab.

  12. Smooth scaling of valence electronic properties in fullerenes: From one carbon atom, to C60, to graphene

    NASA Astrophysics Data System (ADS)

    Lewis, Greyson R.; Bunting, William E.; Zope, Rajendra R.; Dunlap, Brett I.; Ellenbogen, James C.

    2013-05-01

    Scaling of quantum capacitances and valence electron detachment energies is studied for icosahedral and nonicosahedral fullerenes. Scaling trends are considered from zero to infinite average radius, where a fullerene's local surface properties are similar to those of graphene. Detailed density-functional-theory calculations are performed to determine the geometries and detachment energies of icosahedral fullerenes, while values of these quantities are obtained for nonicosahedral species from previously published experimental results. Strongly linear, quasiclassical scaling versus average radii r¯n is seen for the quantum capacitances, but on two different scaling lines for icosahedral and nonicosahedral species, respectively. By contrast, nonclassical, nonlinear scaling versus 1/r¯n is seen for the electron detachment energies, i.e., the valence ionization potentials and electron affinities. This nonlinearity is not accounted for by classical theories that are used to explain trends in electronic properties of fullerenes and usually give accurate quantitative estimates. Instead, simple quantum equations are derived to account for nonlinearities in the metal-particle-like electron detachment energy scaling and to show that these are responsible for nonclassical, nonzero intercepts in the capacitance scaling lines of the fullerenes. Last, it is found that points representing the carbon atom and the graphene limit lie on scaling lines for icosahedral fullerenes, so their quantum capacitances and their detachment energies scale smoothly from one C atom, to C60, to graphene.

  13. 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. PMID:27345190

  14. 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

  15. CHARMM General Force Field (CGenFF): A force field for drug-like molecules compatible with the CHARMM all-atom additive biological force fields

    PubMed Central

    Vanommeslaeghe, K.; Hatcher, E.; Acharya, C.; Kundu, S.; Zhong, S.; Shim, J.; Darian, E.; Guvench, O.; Lopes, P.; Vorobyov, I.; MacKerell, A. D.

    2010-01-01

    The widely used CHARMM additive all-atom force field includes parameters for proteins, nucleic acids, lipids and carbohydrates. In the present paper an extension of the CHARMM force field to drug-like molecules is presented. The resulting CHARMM General Force Field (CGenFF) covers a wide range of chemical groups present in biomolecules and drug-like molecules, including a large number of heterocyclic scaffolds. The parametrization philosophy behind the force field focuses on quality at the expense of transferability, with the implementation concentrating on an extensible force field. Statistics related to the quality of the parametrization with a focus on experimental validation are presented. Additionally, the parametrization procedure, described fully in the present paper in the context of the model systems, pyrrolidine, and 3-phenoxymethylpyrrolidine will allow users to readily extend the force field to chemical groups that are not explicitly covered in the force field as well as add functional groups to and link together molecules already available in the force field. CGenFF thus makes it possible to perform “all-CHARMM” simulations on drug-target interactions thereby extending the utility of CHARMM force fields to medicinally relevant systems. PMID:19575467

  16. 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

  17. 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

    2015-11-01

    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.

  18. 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

  19. Enhanced binding strength between metal nanoclusters and carbon nanotubes with an atomic nickel defect.

    PubMed

    Sung, Dongchul; Park, Noejung; Kim, Gunn; Hong, Suklyun

    2012-05-25

    Using spin-polarized density functional theory calculations, we study binding properties of small metal nanoclusters (Cu(13) and Al(13)) onto carbon nanotubes (CNTs). On defect-free CNTs, the binding affinity with the Cu or Al cluster is very weak. When various defects such as vacancies, substitutional nickel defects, and nickel adatoms are introduced in CNTs to increase the binding strength, the binding energies of the metal nanoclusters increase substantially irrespective of types of defects. The effect of the Ni adatom is especially noticeable. Our results propose a method for improving the wettability of metal-CNT complex composites.

  20. 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.

  1. Influence of Different Defects in Vertically Aligned Carbon Nanotubes on TiO2 Nanoparticle Formation through Atomic Layer Deposition.

    PubMed

    Acauan, Luiz; Dias, Anna C; Pereira, Marcelo B; Horowitz, Flavio; Bergmann, Carlos P

    2016-06-29

    The chemical inertness of carbon nanotubes (CNT) requires some degree of "defect engineering" for controlled deposition of metal oxides through atomic layer deposition (ALD). The type, quantity, and distribution of such defects rules the deposition rate and defines the growth behavior. In this work, we employed ALD to grow titanium oxide (TiO2) on vertically aligned carbon nanotubes (VACNT). The effects of nitrogen doping and oxygen plasma pretreatment of the CNT on the morphology and total amount of TiO2 were systematically studied using transmission electron microscopy, Raman spectroscopy, and thermogravimetric analysis. The induced chemical changes for each functionalization route were identified by X-ray photoelectron and Raman spectroscopies. The TiO2 mass fraction deposited with the same number of cycles for the pristine CNT, nitrogen-doped CNT, and plasma-treated CNT were 8, 47, and 80%, respectively. We demonstrate that TiO2 nucleation is dependent mainly on surface incorporation of heteroatoms and their distribution rather than structural defects that govern the growth behavior. Therefore, selecting the best way to functionalize CNT will allow us to tailor TiO2 distribution and hence fabricate complex heterostructures.

  2. Influence of Different Defects in Vertically Aligned Carbon Nanotubes on TiO2 Nanoparticle Formation through Atomic Layer Deposition.

    PubMed

    Acauan, Luiz; Dias, Anna C; Pereira, Marcelo B; Horowitz, Flavio; Bergmann, Carlos P

    2016-06-29

    The chemical inertness of carbon nanotubes (CNT) requires some degree of "defect engineering" for controlled deposition of metal oxides through atomic layer deposition (ALD). The type, quantity, and distribution of such defects rules the deposition rate and defines the growth behavior. In this work, we employed ALD to grow titanium oxide (TiO2) on vertically aligned carbon nanotubes (VACNT). The effects of nitrogen doping and oxygen plasma pretreatment of the CNT on the morphology and total amount of TiO2 were systematically studied using transmission electron microscopy, Raman spectroscopy, and thermogravimetric analysis. The induced chemical changes for each functionalization route were identified by X-ray photoelectron and Raman spectroscopies. The TiO2 mass fraction deposited with the same number of cycles for the pristine CNT, nitrogen-doped CNT, and plasma-treated CNT were 8, 47, and 80%, respectively. We demonstrate that TiO2 nucleation is dependent mainly on surface incorporation of heteroatoms and their distribution rather than structural defects that govern the growth behavior. Therefore, selecting the best way to functionalize CNT will allow us to tailor TiO2 distribution and hence fabricate complex heterostructures. PMID:27269125

  3. 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.

  4. 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

    2016-02-01

    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.

  5. Enhancement of the optical response in a biodegradable polymer/azo-dye film by the addition of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Díaz Costanzo, Guadalupe; Ribba, Laura; Goyanes, Silvia; Ledesma, Silvia

    2014-04-01

    A new biodegradable photoresponsive material was developed using poly(lactic acid) (PLA) as the matrix material and Disperse Orange 3 (DO3) as photoisomerizable azo-dye. It was observed that the addition of multi-walled carbon nanotubes (MWCNTs) leads to a new phenomenon consisting of an enhancement of the optical anisotropy in a wide range of temperatures. In particular, the optical anisotropy increases 100% at room temperature. Moreover, the material containing MWCNTs shows a faster optical response that is evidenced as an increase in the growth rate of optical anisotropy. Spectroscopic data is provided to study the interaction among DO3, MWCNTs and PLA. The enhancement of optical anisotropy obtained with the addition of MWCNTs was related to the glass transition temperature (Tg) of each material. Maximum optical anisotropy was obtained 15 °C below the Tg for both materials. Results are interpreted in terms of the interactions among DO3, MWCNTs and PLA and the packing density of the dye into the polymer chains. In memory of Professor Iñaki Mondragon.

  6. Intercalation of multiple carbon atoms between the carbonyls of alpha-diketones.

    PubMed

    Balskus, E P; Méndez-Andino, J; Arbit, R M; Paquette, L A

    2001-10-01

    The reaction of open-chain or cyclic alpha-diketones with specific omega-alkenyl organometallics leads readily under the proper conditions to 1,2-diols bonded to terminal olefinic chains. With 1-phenyl-1,2-propanedione, biacetyl, and cyclohexane-1,2-dione, allylindation in aqueous THF proceeds readily at both adjacent carbonyls. For cyclododecane-1,2-dione, recourse must be made to allylmagnesium bromide for completing the second-stage condensation. Grignard reagents have also served well as reactants for biacetyl monoadducts. In contrast, monoallylated camphorquinone is reluctant to couple to Grignard reagents and reacts only when Barbier-type alkyllithium reactions are applied. The ring closing metatheses of these products have been examined. Where six-membered ring formation operates, cyclization can be performed directly on diols. When larger rings are involved, the diols will react only if structural preorganization capable of facilitating mutual approach of the two double bonds is at play. For this purpose, the prior conversion to a cyclic carbonate holds considerable utility. In the latter setting, saponification must precede the diol cleavage step which has been performed with lead tetraacetate. The latter reagent also exhibits the very beneficial effect of facilitating removal of ruthenium and phosphorus byproducts generated during the metathesis step. This chemistry conveniently lends itself to the controlled intercalation of multiple methylene groups between the carbonyl carbons of readily available alpha-diketones to deliver linear or cyclic products.

  7. 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.

  8. The relaxation of intrinsic compressive stress in complementary metal-oxide-semiconductor transistors by additional N ion implantation treatment with atomic force microscope-Raman stress extraction

    NASA Astrophysics Data System (ADS)

    Liao, M.-H.; Chen, C.-H.; Chang, L.-C.; Yang, C.; Kao, S.-C.

    2012-05-01

    Based on the stress extraction and measurement by atomic force microscope-Raman technique with the nanometer level space resolution, the high compressive stress about 550 MPa on the Si active region (OD) is observed for the current complementary metal-oxide-semiconductor (CMOS) transistor. During the thermal budget for the standard manufacture process of the current CMOS transistor, the difference of thermal expansion coefficients between Si and Shallow Trench Isolation (STI) oxide results in this high compressive stress in Si OD and further degrades the electron carrier mobility seriously. In order to relax this intrinsic processed compressive stress in Si OD and try to recover this performance loss, the novel process is proposed in this work in addition to the usage of one-side pad SiN layer. With this novel process of additional N-ion implantation (IMP) treatment in STI oxide, it can be found that the less compressive stress about 438 MPa in Si OD can be achieved by the smaller difference of thermal expansion coefficients between Si and N-doped SiO2 STI oxide. The formation of Si-N bonding in N-doped SiO2 STI region can be monitored by Fourier transform infrared spectroscopy spectra and thermal expansion coefficients for Si, SiO2, and SiN are 2.6 ppm/K, 0.4 ppm/K, and 2.87 ppm/K, respectively. The effective relaxation of intrinsic processed compressive stress in Si OD about 112 MPa (from 550 MPa to 438 MPa) by this proposed additional N IMP treatment contributes ˜14% electron carrier mobility enhancement/recovery. The experimental electrical data agree well with the theoretical piezoelectricity calculation for the strained-Si theory.

  9. 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

  10. 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.

  11. 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. PMID:27070782

  12. 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.

  13. Graphene as an atomically thin interface for growth of vertically aligned carbon nanotubes

    PubMed Central

    Rao, Rahul; Chen, Gugang; Arava, Leela Mohana Reddy; Kalaga, Kaushik; Ishigami, Masahiro; Heinz, Tony F.; Ajayan, Pulickel M.; Harutyunyan, Avetik R.

    2013-01-01

    Growth of vertically aligned carbon nanotube (CNT) forests is highly sensitive to the nature of the substrate. This constraint narrows the range of available materials to just a few oxide-based dielectrics and presents a major obstacle for applications. Using a suspended monolayer, we show here that graphene is an excellent conductive substrate for CNT forest growth. Furthermore, graphene is shown to intermediate growth on key substrates, such as Cu, Pt, and diamond, which had not previously been compatible with nanotube forest growth. We find that growth depends on the degree of crystallinity of graphene and is best on mono- or few-layer graphene. The synergistic effects of graphene are revealed by its endurance after CNT growth and low contact resistances between the nanotubes and Cu. Our results establish graphene as a unique interface that extends the class of substrate materials for CNT growth and opens up important new prospects for applications. PMID:23712556

  14. TRACING H{sub 2} COLUMN DENSITY WITH ATOMIC CARBON (C I) AND CO ISOTOPOLOGS

    SciTech Connect

    Lo, N.; Bronfman, L.; Cunningham, M. R.; Jones, P. A.; Lowe, V.; Cortes, P. C.; Simon, R.; Fissel, L.; Novak, G.

    2014-12-20

    We present the first results of neutral carbon ([C I] {sup 3} P {sub 1}-{sup 3} P {sub 0} at 492 GHz) and carbon monoxide ({sup 13}CO, J = 1-0) mapping in the Vela Molecular Ridge cloud C (VMR-C) and the G333 giant molecular cloud complexes with the NANTEN2 and Mopra telescopes. For the four regions mapped in this work, we find that [C I] has very similar spectral emission profiles to {sup 13}CO, with comparable line widths. We find that [C I] has an opacity of 0.1-1.3 across the mapped region while the [C I]/{sup 13}CO peak brightness temperature ratio is between 0.2 and 0.8. The [C I] column density is an order of magnitude lower than that of {sup 13}CO. The H{sub 2} column density derived from [C I] is comparable to values obtained from {sup 12}CO. Our maps show that C I is preferentially detected in gas with low temperatures (below 20 K), which possibly explains the comparable H{sub 2} column density calculated from both tracers (both C I and {sup 12}CO underestimate column density), as a significant amount of the C I in the warmer gas is likely in the higher energy state transition ([C I] {sup 3} P {sub 2}-{sup 3} P {sub 1} at 810 GHz), and thus it is likely that observations of both the above [C I] transitions are needed in order to recover the total H{sub 2} column density.

  15. 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

  16. 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.

  17. Impact of 2'-hydroxyl sampling on the conformational properties of RNA: update of the CHARMM all-atom additive force field for RNA.

    PubMed

    Denning, Elizabeth J; Priyakumar, U Deva; Nilsson, Lennart; Mackerell, Alexander D

    2011-07-15

    Here, we present an update of the CHARMM27 all-atom additive force field for nucleic acids that improves the treatment of RNA molecules. The original CHARMM27 force field parameters exhibit enhanced Watson-Crick base pair opening which is not consistent with experiment, whereas analysis of molecular dynamics (MD) simulations show the 2'-hydroxyl moiety to almost exclusively sample the O3' orientation. Quantum mechanical (QM) studies of RNA related model compounds indicate the energy minimum associated with the O3' orientation to be too favorable, consistent with the MD results. Optimization of the dihedral parameters dictating the energy of the 2'-hydroxyl proton targeting the QM data yielded several parameter sets, which sample both the base and O3' orientations of the 2'-hydroxyl to varying degrees. Selection of the final dihedral parameters was based on reproduction of hydration behavior as related to a survey of crystallographic data and better agreement with experimental NMR J-coupling values. Application of the model, designated CHARMM36, to a collection of canonical and noncanonical RNA molecules reveals overall improved agreement with a range of experimental observables as compared to CHARMM27. The results also indicate the sensitivity of the conformational heterogeneity of RNA to the orientation of the 2'-hydroxyl moiety and support a model whereby the 2'-hydroxyl can enhance the probability of conformational transitions in RNA.

  18. 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.

  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. 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.

  1. On the role of block copolymer additives for calcium carbonate crystallization: small angle neutron scattering investigation by applying contrast variation.

    PubMed

    Endo, Hitoshi; Schwahn, Dietmar; Cölfen, Helmut

    2004-05-15

    The role of the double-hydrophilic block copolymer poly(ethylen glycol)-block-poly(methacrylic acid) (PEG-b-PMAA) on the morphogenesis of calcium carbonate (CaCO3) was studied by applying the contrast variation small angle neutron scattering technique. The morphology and size of CaCO3 crystals is strongly affected by the addition of PEG-b-PMAA. In order to determine the partial scattering functions of the polymer and CaCO3 mineral, we developed both an experimental and theoretical approach with a sophisticated method of their determination from the scattering intensity. Partial scattering functions give detailed information for each component. In particular, the partial scattering function of the polymer, Spp, shows a monotonic slope with Q(-2 to -3) where the scattering vector Q is low (Q < 0.01 Angstrom(-1)), which is a clear evidence that the polymer within the CaCO3 mineral has a mass fractal dimension. The other partial scattering functions reflected the geometry of the CaCO3 particles or the "interaction" of polymer and CaCO3 on a microscopic scale, which leads to a coherent view with Spp.

  2. 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/

  3. 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)

  4. 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.

  5. 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. PMID:26024614

  6. 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.

  7. Effect of solution additives on the performance of PMAN carbon anodes in 1M LiPF{sub 6}/EC-DMC solutions

    SciTech Connect

    Guidotti, R.A.; Johnson, B.J.

    1996-12-31

    A study was undertaken to examine the use of a number of solution additives in 1M LiPF{sub 6}/ethylene carbonate (EC)-dimethyl carbonate (DMC) solutions to improve the performance of carbon anodes derived from polymethylacrylonitrile (PMAN)-divinylbenzene (DVB) copolymers. The study goals were to improve the cycle life and reduce the formation of the passivation layer during the first reduction, thereby minimizing the irreversible-capacity losses. Additives studied were 12-crown-4 (12-Cr-4) ether, decalin, and dilithium phthalocyanine (Li{sub 2}Pc). The carbon performance was characterized by galvanostatic cycling, cyclic voltammetry, and complex-impedance spectroscopy. Limited success was obtained with 12-Cr-4 ether at 0.25 M and decalin at 1 v/o. Poor results were noted with Li{sub 2}Pc at 0.025 M and 0.5 M.

  8. 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

  9. Estimation of perimortal percent carboxy-heme in nonstandard postmortem specimens using analysis of carbon monoxide by GC/MS and iron by flame atomic absorption spectrophotometry.

    PubMed

    Middleberg, R A; Easterling, D E; Zelonis, S F; Rieders, F; Rieders, M F

    1993-01-01

    In decomposed, formalin-fixed, embalmed, exhumed, and some fire-dried cases in which normal blood is unavailable, the usual methods for determination of carboxyhemoglobin saturation frequently fail. To address these specimens, a method utilizing both gas chromatography/mass spectrometric (GC/MS) determination of carbon monoxide (CO) and flame atomic absorption spectrophotometry (FAAS) determination of iron (Fe), in the same specimen, was developed. The method is reported here, along with its application to seven pertinent forsensic death investigations. The CO analytical methodology involves acid liberation of the gas from the specimen aliquot in a headspace vial. After heating and equilibrating, a sample of the headspace vapor is injected into the GC/MS system with a gastight syringe. Quantitation is achieved by standard addition comparison utilizing the ideal gas law equation. Iron is quantified by FAAS analysis of the same aliquot used for the CO determination, following nitric acid digestion. The concentration is determined by comparison to a standard curve. A formula for determining the minimum percent carboxy-heme saturation was derived by using the ratio of the amount of CO to the amount of Fe in the aliquot analyzed. Tissue types analyzed include spleen, liver, muscle, dried blood, and unspecified decomposed tissue.

  10. Functionalization of multiwalled carbon nanotubes for the solid-phase extraction of silver, cadmium, palladium, zinc, manganese and copper by flame atomic absorption spectrometry.

    PubMed

    Ghaedi, Mehrorang; Montazerozohori, M; Nazari, E; Nejabat, R

    2013-07-01

    In the present work, multiwalled carbon nanotube (MWCNT) chemically modified with (3-mercaptopropyl) silanetriolate is efficiently used for the solid-phase extraction of Cu(2+), Ag(+), Cd(2+), Pb(2+), Zn(2+) and Mn(2+) ions prior to their flame atomic absorption spectrometric determination. The influences of the various analytical parameters, including pH, amounts of solid phase, sample volume and eluent conditions and so on, on the recoveries of target analytes were investigated and optimized by one at a time optimization method. The influences of alkaline, alkaline earth and some transition metals on the adsorption and elution of the analytes were also examined. The detection limits for all understudied metal ions were between 1.4 and 2.8 ng mL(-1) (3Sb, n = 10). The evaluation of the thermodynamic parameters such as enthalpy (positive value), Gibbs free energy (negative value) in addition to high value of entropy shows the endothermic and spontaneous nature of sorption process. Following the optimization of variables, the adsorption process follows the intraparticle kinetic model with R (2) of 0.98 and the Langmuir isotherm with high correlation coefficient (R (2) > 0.95). The procedure was applied for the analytes determination in the food samples with satisfactory results (recoveries >95% and relative standard deviation's (RSD) lower than 4%).

  11. Separation and Enrichment of Gold in Water, Geological and Environmental Samples by Solid Phase Extraction on Multiwalled Carbon Nanotubes Prior to its Determination by Flame Atomic Absorption Spectrometry.

    PubMed

    Duran, Ali; Tuzen, Mustafa; Soylak, Mustafa

    2015-01-01

    This study proposes the application of multi-walled carbon nanotubes as a solid sorbent for the preconcentration of gold prior to its flame atomic absorption spectrometry determination. Extraction was achieved by using a glass column (15.0 cm in length and 1.0 cm in diameter). Quantitative recoveries were obtained in the pH range of 2.5-4.0; the elution step was carried out with 5.0 ml of 1.0 mol/L HNO3 in acetone. In the ligand-free study, variables such as pH, eluent type, sample volume, flow rates, and matrix effect were examined for the optimum recovery of gold ions. The gold ions were able to be pre-concentrated by a factor of 150 and their LOD was determined to be 1.71 μg/L. In order to evaluate the accuracy of the developed method, addition-recovery tests were applied for the tap water, mineral water, and sea water samples. Gold recovery studies were implemented using a wet digestion technique for mine and soil samples taken from various media, and this method was also applied for anodic slime samples taken from the factories located in the Kayseri Industrial Zone of Turkey.

  12. Estimation of perimortal percent carboxy-heme in nonstandard postmortem specimens using analysis of carbon monoxide by GC/MS and iron by flame atomic absorption spectrophotometry.

    PubMed

    Middleberg, R A; Easterling, D E; Zelonis, S F; Rieders, F; Rieders, M F

    1993-01-01

    In decomposed, formalin-fixed, embalmed, exhumed, and some fire-dried cases in which normal blood is unavailable, the usual methods for determination of carboxyhemoglobin saturation frequently fail. To address these specimens, a method utilizing both gas chromatography/mass spectrometric (GC/MS) determination of carbon monoxide (CO) and flame atomic absorption spectrophotometry (FAAS) determination of iron (Fe), in the same specimen, was developed. The method is reported here, along with its application to seven pertinent forsensic death investigations. The CO analytical methodology involves acid liberation of the gas from the specimen aliquot in a headspace vial. After heating and equilibrating, a sample of the headspace vapor is injected into the GC/MS system with a gastight syringe. Quantitation is achieved by standard addition comparison utilizing the ideal gas law equation. Iron is quantified by FAAS analysis of the same aliquot used for the CO determination, following nitric acid digestion. The concentration is determined by comparison to a standard curve. A formula for determining the minimum percent carboxy-heme saturation was derived by using the ratio of the amount of CO to the amount of Fe in the aliquot analyzed. Tissue types analyzed include spleen, liver, muscle, dried blood, and unspecified decomposed tissue. PMID:8429619

  13. Separation and Enrichment of Gold in Water, Geological and Environmental Samples by Solid Phase Extraction on Multiwalled Carbon Nanotubes Prior to its Determination by Flame Atomic Absorption Spectrometry.

    PubMed

    Duran, Ali; Tuzen, Mustafa; Soylak, Mustafa

    2015-01-01

    This study proposes the application of multi-walled carbon nanotubes as a solid sorbent for the preconcentration of gold prior to its flame atomic absorption spectrometry determination. Extraction was achieved by using a glass column (15.0 cm in length and 1.0 cm in diameter). Quantitative recoveries were obtained in the pH range of 2.5-4.0; the elution step was carried out with 5.0 ml of 1.0 mol/L HNO3 in acetone. In the ligand-free study, variables such as pH, eluent type, sample volume, flow rates, and matrix effect were examined for the optimum recovery of gold ions. The gold ions were able to be pre-concentrated by a factor of 150 and their LOD was determined to be 1.71 μg/L. In order to evaluate the accuracy of the developed method, addition-recovery tests were applied for the tap water, mineral water, and sea water samples. Gold recovery studies were implemented using a wet digestion technique for mine and soil samples taken from various media, and this method was also applied for anodic slime samples taken from the factories located in the Kayseri Industrial Zone of Turkey. PMID:26651587

  14. 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.

  15. 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. PMID:26408119

  16. A transfer of carbon atoms from fatty acids to sugars and amino acids in yellow lupine (Lupinus luteus L.) seedlings.

    PubMed

    Borek, Sławomir; Ratajczak, Wiktoria; Ratajczak, Lech

    2003-05-01

    The metabolism of 14C-acetate was investigated during the in vitro germination of yellow lupine seeds. Carbon atoms (14C) from the C-2 position of acetate were incorporated mainly into amino acids: aspartate, glutamate, and glutamine and into sugars: glucose, sucrose, and fructose. In contrast to this, 14C from the C-1 position of acetate was released mainly as 14CO2. Incorporation of 1-14C and 2-14C from acetate into amino acids and sugars in seedling axes was more intense when sucrose was added to the medium. However, in cotyledons where lipids are converted to carbohydrates, this process was inhibited by exogenous sucrose. Since acetate is the product of fatty acid beta-oxidation, our results indicate that, at least in lupine, seed storage lipids can be converted not only to sucrose, but mainly to amino acids. Inhibitory effects of sucrose on the incorporation of 14C from acetate into amino acids and sugars in cotyledons of lupine seedlings may be explained as the effect of regulation of the glyoxylate cycle by sugars. PMID:12806783

  17. 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.

  18. Direct formation of anatase TiO2 nanoparticles on carbon nanotubes by atomic layer deposition and their photocatalytic properties.

    PubMed

    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.

  19. Facile synthesis of analogous graphene quantum dots with sp(2) hybridized carbon atom dominant structures and their photovoltaic application.

    PubMed

    Huang, Zhengcheng; Shen, Yongtao; Li, Yu; Zheng, Wenjun; Xue, Yunjia; Qin, Chengqun; Zhang, Bo; Hao, Jingxiang; Feng, Wei

    2014-11-01

    Graphene quantum dot (GQD) is an emerging class of zero-dimensional nanocarbon material with many novel applications. It is of scientific importance to prepare GQDs with more perfect structures, that is, GQDs containing negligible oxygenous defects, for both optimizing their optical properties and helping in their photovoltaic applications. Herein, a new strategy for the facile preparation of "pristine" GQDs is reported. The method we presented is a combination of a bottom-up synthetic and a solvent-induced interface separation process, during which the target products with highly crystalline structure were selected by the organic solvent. The obtained organic soluble GQDs (O-GQDs) showed a significant difference in structure and composition compared with ordinary aqueous soluble GQDs, thus leading to a series of novel properties. Furthermore, O-GQDs were applied as electron-acceptors in a poly(3-hexylthiophene) (P3HT)-based organic photovoltaic device. The performance highlights that O-GQD has potential to be a novel electron-acceptor material due to the sp(2) hybridized carbon atom dominant structure and good solubility in organic solvents.

  20. Variation of mechanical property of single-walled carbon nanotubes-treated cells explored by atomic force microscopy.

    PubMed

    Dulińska-Molak, Ida; Mao, Hongli; Kawazoe, Naoki; Chen, Guoping

    2014-04-01

    With a range of biological properties, single-walled carbon nanotubes (SWCNTs) are a promising material for nanobiotechnology. Concerns about their potential effect on human health have led to the interest in understanding the interaction between SWCNTs and cells. There are many reports showing the potential cellular effects of SWCNTs but this issue is quite controversially discussed in the literature. In this study, we used conventional biological evaluation methods and atomic force microscopy (AFM) to compare the effects of SWCNTs on three different cell types: bovine articular chondrocytes, human bone marrow-derived mesenchymal stem cells and HeLa cells. No obvious effects of SWCNTs on cell morphology and viability were observed during 3 days in vitro culture. However, SWCNTs significantly increased the Young's modulus of all the three types of cells. The effect of SWCNTs on Young's modulus was in an increasing order of Hela cells < chondrocytes < mesenchymal stem cells. AFM was shown to be a useful tool for investigation of the effect of nanomaterials on mechanical property of cells.