Low-energy electron diffraction study of potassium adsorbed on single-crystal graphite and highly oriented pyrolytic graphite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferralis, N.; Diehl, R.D.; Pussi, K.

2004-12-15

Potassium adsorption on graphite has been a model system for the understanding of the interaction of alkali metals with surfaces. The geometries of the (2x2) structure of potassium on both single-crystal graphite (SCG) and highly oriented pyrolytic graphite (HOPG) were investigated for various preparation conditions for graphite temperatures between 55 and 140 K. In all cases, the geometry was found to consist of K atoms in the hollow sites on top of the surface. The K-graphite average perpendicular spacing is 2.79{+-}0.03 A , corresponding to an average C-K distance of 3.13{+-}0.03 A , and the spacing between graphite planes ismore » consistent with the bulk spacing of 3.35 A. No evidence was observed for a sublayer of potassium. The results of dynamical LEED studies for the clean SCG and HOPG surfaces indicate that the surface structures of both are consistent with the truncated bulk structure of graphite.« less

Transformation of shock-compressed graphite to hexagonal diamond in nanoseconds

DOE PAGES

Turneaure, Stefan J.; Sharma, Surinder M.; Volz, Travis J.; ...

2017-10-27

The graphite-to-diamond transformation under shock compression has been of broad scientific interest since 1961. The formation of hexagonal diamond (HD) is of particular interest because it is expected to be harder than cubic diamond and due to its use in terrestrial sciences as a marker at meteorite impact sites. However, the formation of diamond having a fully hexagonal structure continues to be questioned and remains unresolved. Using real-time (nanosecond), in situ x-ray diffraction measurements, we show unequivocally that highly oriented pyrolytic graphite, shock-compressed along the c axis to 50 GPa, transforms to highly oriented elastically strained HD with the (100)HDmore » plane parallel to the graphite basal plane. These findings contradict recent molecular dynamics simulation results for the shock-induced graphite-to-diamond transformation and provide a benchmark for future theoretical simulations. Additionally, our results show that an earlier report of HD forming only above 170 GPa for shocked pyrolytic graphite may lead to incorrect interpretations of meteorite impact events.« less

One-step formation of straight nanostripes from a mammal lipid-oleamide directly on highly oriented pyrolytic graphite.

PubMed

Zhang, Renjie; Möhwald, Helmuth; Kurth, Dirk G

2009-02-17

Hierarchical nanostructures are obtained directly on highly oriented pyrolytic graphite (HOPG) by spin coating of dilute chloroform solution of 9-Z-octadecenamide (oleamide), a natural lipid with cis-CdC- conformation, existing in the cerebrospinal fluid of mammal animals and being an additive for medical use and food packaging. Straight separated nanostripes with a length of 70-300 nm exist in the topmost layer and compact nanostripes in the bottom layer contacting HOPG. Compact nanostripes have a periodicity spacing of 3.8 nm, indicating H-bonding between two rows of oleamide molecules. The orientation of the hierarchical nanostructures differs by n60 degrees+/-8 degrees (n=1 or 2), reflecting the epitaxial ordering along theHOPGsubstrate. The nanostripes are stable against annealing.Amolecular packing scheme for the nanostructures is proposed, where the -C=C bond angle in oleamide is 120 degrees and the plane of the carbon skeleton lies parallel to the HOPG substrate. Nanostripes in the topmost layer are formed from separated rows of oleamide molecules, due to the short-range surface potential of the substrate. The scheme involves direct influence ofHOPGon the orientation of oleamide molecules to form nanostripes without any purposely added saturated alkanes and H-bonds between amide groups in adjacent two rows of oleamide molecules.

Electrodeposition of platinum on highly oriented pyrolytic graphite. Part I: electrochemical characterization.

PubMed

Lu, Guojin; Zangari, Giovanni

2005-04-28

The electrochemical deposition of Pt on highly oriented pyrolytic graphite (HOPG) from H2PtCl6 solutions was investigated by cyclic voltammetry and chronoamperometry. The effects of deposition overpotential, H2PtCl6 concentration, supporting electrolyte, and anion additions on the deposition process were evaluated. Addition of chloride inhibits Pt deposition due to adsorption on the substrate and blocking of reduction sites, while SO4(2-) and ClO4- slightly promote Pt reduction. By comparing potentiostatic current-time transients with the Scharifker-Hills model, a transition from progressive to instantaneous nucleation was observed when increasing the deposition overpotential. Following addition of chloride anions the fit of experimental transients with the instantaneous nucleation mode improves, while the addition of SO4(2-) induces only small changes. Chloride anions strongly inhibit the reduction process, which is shifted in the cathodic direction. The above results indicate that the most appropriate conditions for growing Pt nanoparticles on HOPG with narrow size distribution are to use an H2PtCl6 solution with HCl as supporting electrolyte and to apply a high cathodic overpotential.

Extreme-UV electrical discharge source

DOEpatents

Fornaciari, Neal R.; Nygren, Richard E.; Ulrickson, Michael A.

2002-01-01

An extreme ultraviolet and soft x-ray radiation electric capillary discharge source that includes a boron nitride housing defining a capillary bore that is positioned between two electrodes one of which is connected to a source of electric potential can generate a high EUV and soft x-ray radiation flux from the capillary bore outlet with minimal debris. The electrode that is positioned adjacent the capillary bore outlet is typically grounded. Pyrolytic boron nitride, highly oriented pyrolytic boron nitride, and cubic boron nitride are particularly suited. The boron nitride capillary bore can be configured as an insert that is encased in an exterior housing that is constructed of a thermally conductive material. Positioning the ground electrode sufficiently close to the capillary bore outlet also reduces bore erosion.

Nitrogen: Unraveling the Secret to Stable Carbon-Supported Pt-Alloy Electrocatalysts

DTIC Science & Technology

2013-10-01

materials reveal broad N1s spectra, indicative of formation of multiple functionalities including but not limited to pyridinic, graphitic and pyrrolic ...network along with nitrogen substitutional defects, while high-dosage increases vacancy agglomerations and pyridinic and pyrrolic nitrogen defects...Article Online highly oriented pyrolytic graphite (HOPG) surface. Simulated defects included pyridinic (Npyridinic), pyrrolic (Npyrrolic), graphitic

Carbon Materials Research

DTIC Science & Technology

2006-08-01

carbon would be highly oriented pyrolytic graphite ( HOPG ), which is formed by depositing one atom at a time on a surface utilizing the pyrolysis of a... of the crystallites, and baking to 2800 K produces a polycrystalline graphite part that has high strength and conductivity. To make isotropic...pitch fibers) or flexible (Graphoil®), as well as anisotropic ( HOPG ) or isotropic ( polycrystalline graphite ). In addition, porosity, lubricity

Thermophysical properties of graphite HOPG and HAPG in the solid state and under melting (from 2000 K up to 5000 K)

NASA Astrophysics Data System (ADS)

Savvatimskiy, A. I.; Onufriev, S. V.; Konyukhov, S. A.

2017-11-01

Experiments with HOPG graphite grade showed that the melting temperature of graphite equals 4800-4900 K and that the melting of graphite is possible only at elevated pressures. The data were obtained for resistivity, specific heat and input (Joule) energy up to 5000 K. HAPG (Highly Annealing Pyrolytic Graphite) is a form of highly oriented pyrolytic graphite. HAPG specimens in the form of strips (thickness 30 microns) were placed in a cell (between two plates of glass-sapphire). The specimen temperature was measured by a high speed pyrometer. The heat of fusion for both graphite grades (heated in a confined volume) was less (and specific heat - higher) than for the case with nearly free expansion. A possible reason for the observed effects is discussed in the report.

Formation of Nanocones on Highly Oriented Pyrolytic Graphite by Oxygen Plasma

PubMed Central

Vesel, Alenka; Eleršič, Kristina; Modic, Martina; Junkar, Ita; Mozetič, Miran

2014-01-01

Improvement in hemocompatibility of highly oriented pyrolytic graphite (HOPG) by formation of nanostructured surface by oxygen plasma treatment is reported. We have showed that by appropriate fine tuning of plasma and discharge parameters we are able to create nanostructured surface which is densely covered with nanocones. The size of the nanocones strongly depended on treatment time. The optimal results in terms of material hemocompatibility were obtained after treatment with oxygen plasma for 15 s, when both the nanotopography and wettability were the most favorable, since marked reduction in adhesion and activation of platelets was observed on this surface. At prolonged treatment times, the rich surface topography was lost and thus also its antithrombogenic properties. Chemical composition of the surface was always more or less the same, regardless of its morphology and height of the nanocones. Namely, on all plasma treated samples, only a few atomic percent of oxygen was found, meaning that plasma caused mostly etching, leading to changes in the surface morphology. This indicates that the main preventing mechanism against platelets adhesion was the right surface morphology. PMID:28788553

Scanning tunneling microscopy of the formation, transformation, and property of oligothiophene self-organizations on graphite and gold surfaces.

PubMed

Yang, Zhi-Yong; Zhang, Hui-Min; Yan, Cun-Ji; Li, Shan-Shan; Yan, Hui-Juan; Song, Wei-Guo; Wan, Li-Jun

2007-03-06

Two alkyl-substituted dual oligothiophenes, quarterthiophene (4T)-trimethylene (tm)-octithiophene (8T) and 4T-tm-4T, were used to fabricate molecular structures on highly oriented pyrolytic graphite and Au(111) surfaces. The resulted structures were investigated by scanning tunneling microscopy. The 4T-tm-8T and 4T-tm-4T molecules self-organize into long-range ordered structures with linear and/or quasi-hexagonal patterns on highly oriented pyrolytic graphite at ambient temperature. Thermal annealing induced a phase transformation from quasi-hexagonal to linear in 4T-tm-8T adlayer. The molecules adsorbed on Au(111) surface in randomly folded and linear conformation. Based on scanning tunneling microscopy results, the structural models for different self-organizations were proposed. Scanning tunneling spectroscopy measurement showed the electronic property of individual molecules in the patterns. These results are significant in understanding the chemistry of molecular structure, including its formation, transformation, and electronic properties. They also help to fabricate oligothiophene assemblies with desired structures for future molecular devices.

Ultra-thin passivating film induced by vinylene carbonate on highly oriented pyrolytic graphite negative electrode in lithium-ion cell

NASA Astrophysics Data System (ADS)

Matsuoka, O.; Hiwara, A.; Omi, T.; Toriida, M.; Hayashi, T.; Tanaka, C.; Saito, Y.; Ishida, T.; Tan, H.; Ono, S. S.; Yamamoto, S.

We investigated the influence of vinylene carbonate, as an additive molecule, on the decomposition phenomena of electrolyte solution [ethylene carbonate (EC)—ethyl methyl carbonate (EMC) (1:2 by volume) containing 1 M LiPF 6] on a highly oriented pyrolytic graphite (HOPG) negative electrode by using cyclic voltammetry (CV) and atomic force microscopy (AFM). Vinylene carbonate deactivated reactive sites (e.g. radicals and oxides at the defects and the edge of carbon layer) on the cleaved surface of the HOPG negative electrode, and prevented further decomposition of the other solvents there. Further, vinylene carbonate induced an ultra-thin film (less than 1.0 nm in thickness) on the terrace of the basal plane of the HOPG negative electrode, and this film suppressed the decomposition of electrolyte solution on the terraces of the basal plane. We consider that this ultra-thin passivating film is composed of a reduction product of vinylene carbonate (VC), and might have a polymer structure. These induced effects might explain how VC improves the life performance of lithium-ion cells.

Magnetotransport in two dimensional electron systems under microwave excitation and in highly oriented pyrolytic graphite

NASA Astrophysics Data System (ADS)

Ramanayaka, Aruna N.

This thesis consists of two parts. The first part considers the effect of microwave radiation on magnetotransport in high quality GaAs/AlGaAs heterostructure two dimensional electron systems. The effect of microwave (MW) radiation on electron temperature was studied by investigating the amplitude of the Shubnikov de Haas (SdH) oscillations in a regime where the cyclotron frequency o c and the MW angular frequency o satisfy 2o ≤ o c ≤ 3.5o. The results indicate negligible electron heating under modest MW photoexcitation, in agreement with theoretical predictions. Next, the effect of the polarization direction of the linearly polarized MWs on the MW induced magnetoresistance oscillation amplitude was investigated. The results demonstrate the first indications of polarization dependence of MW induced magnetoresistance oscillations. In the second part, experiments on the magnetotransport of three dimensional highly oriented pyrolytic graphite (HOPG) reveal a non-zero Berry phase for HOPG. Furthermore, a novel phase relation between oscillatory magneto- and Hall- resistances was discovered from the studies of the HOPG specimen. INDEX WORDS: Two dimensional electron systems, Magnetoresistance, Microwave induced magnetoresistance oscillations, Graphite, Quantum Hall effect, Hall effect, Resistivity rule, Shubnikov de Haas effect, Shubnikov de Haas oscillation.

Auger mediated positron sticking on graphene and highly oriented pyrolytic graphite

NASA Astrophysics Data System (ADS)

Chirayath, V. A.; Chrysler, M.; McDonald, A.; Lim, Z.; Shastry, K.; Gladen, R.; Fairchild, A.; Koymen, A.; Weiss, A.

Positron annihilation induced Auger electron spectroscopy (PAES) measurements on 6-8 layers graphene grown on polycrystalline copper and the measurements on a highly oriented pyrolytic graphite (HOPG) sample have indicated the presence of a bound surface state for positrons. Measurements carried out with positrons of kinetic energies lower than the electron work function for graphene or HOPG have shown emission of low energy electrons possible only through the Auger mediated positron sticking (AMPS) process. In this process the positron makes a transition from a positive energy scattering state to a bound surface state. The transition energy is coupled to a valence electron which may then have enough energy to get ejected from the sample surface. The positrons which are bound to surface state are highly localized in a direction perpendicular to surface and delocalized parallel to it which makes this process highly surface sensitive and can thus be used for characterizing graphene or graphite surfaces for open volume defects and surface impurities. The measurements have also shown an extremely large low energy tail for the C KVV Auger transition at 263eV indicative of another physical process for low energy emission. This work was supported by NSF Grant No. DMR 1508719 and DMR 1338130.

A scanning tunneling microscope study on an ordered mixed monolayer of bis(4,5-dihydronaphtho[1,2-d])-tetrathiafulvalene and n-tetradecane on highly oriented pyrolytic graphite.

PubMed

Zhao, Miao; Jiang, Peng; Deng, Ke; Jiang, Chao

2010-11-01

Tetrathiafulvalene (TTF) and its derivatives (TTFs) have been successfully used as building blocks to form charge transfer salts and organic semiconductors because of their special structures and rich electron nature. We report the formation of ordered mixed binary-component monolayer consisting of Bis(4,5-dihydronaphtho[1,2-d])tetrathiafulvalene (DH-TTF) and n-tetradecane (n-C14H30) molecules on highly oriented pyrolytic graphite (HOPG) surface. Scanning tunneling microscope (STM) imaging reveals that the two different kinds of molecules can spontaneously form ordered periodic phase separation structures on the substrate, in which ordered DH-TTF double- (or single-) lamella structures are periodically tuned by ordered n-C14H30 double- (or single-) lamella structures. Furthermore, scanning tunneling spectrum (STS) measurements by addressing the individual DH-TTF and n-C14H30 molecules in the ordered monolayer show that the two different kinds of molecules exhibit completely different I(V) characters on the HOPG substrate. The modulated arrangement of the TTF derivative by insulating molecules opens a possible route to construct organic conducting molecule ribbons for potential application in nanodevices.

Magneto-transport properties of As-implanted highly oriented pyrolytic graphite

NASA Astrophysics Data System (ADS)

de Jesus, R. F.; Camargo, B. C.; da Silva, R. R.; Kopelevich, Y.; Behar, M.; Gusmão, M. A.; Pureur, P.

2016-11-01

We report on magneto-transport experiments in a high-quality sample of highly-oriented pyrolytic graphite (HOPG). Magneto-resistance and Hall resistivity measurements were carried out in magnetic inductions up to B = 9 T applied parallel to the c-axis at fixed temperatures between T=2 K and T=12 K. The sample was submitted to three subsequent irradiations with As ions. The implanted As contents were 2.5, 5 and 10 at% at the maximum of the distribution profile. Experiments were performed after each implantation stage. Shubnikov-de Haas (SdH) oscillations were observed in both the magneto-resistance and Hall-effect measurements. Analyses of these results with fast Fourier transform (FFT) lead to fundamental frequencies and effective masses for electrons and holes that are independent of the implantation fluences. The Hall resistivity at low temperatures shows a sign reversal as a function of the field in all implanted states. We interpret the obtained results with basis on a qualitative model that supposes the existence of an extrinsic hole density associated to the defect structure of our sample. We conclude that the As implantation does not produce a semiconductor-type doping in our HOPG sample. Instead, an increase in the extrinsic hole density is likely to occur as a consequence of disorder induced by implantation.

Atomic resolution images of graphite in air

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grigg, D.A.; Shedd, G.M.; Griffis, D.

One sample used for proof of operation for atomic resolution in STM is highly oriented pyrolytic graphite (HOPG). This sample has been imaged with many different STM`s obtaining similar results. Atomic resolution images of HOPG have now been obtained using an STM designed and built at the Precision Engineering Center. This paper discusses the theoretical predictions and experimental results obtained in imaging of HOPG.

SPM observation of nano-dots induced by slow highly charged ions

NASA Astrophysics Data System (ADS)

Nakamura, Nobuyuki; Terada, Masashi; Nakai, Yoichi; Kanai, Yasuyuki; Ohtani, Shunsuke; Komaki, Ken-ichiro; Yamazaki, Yasunori

2005-05-01

We have observed nano-dots on a highly oriented pyrolytic graphite (HOPG) surface produced by highly charged ion impacts with a scanning probe microscope. In order to clarify the role of potential and kinetic energies in surface modification, we have measured the kinetic energy and incident ion charge dependences of the dot size. The results showed that the potential energy or the incident ion charge has strong influence on the surface modification rather than the kinetic energy.

Electrostatic force microscopy on oriented graphite surfaces: coexistence of insulating and conducting behaviors.

PubMed

Lu, Yonghua; Muñoz, M; Steplecaru, C S; Hao, Cheng; Bai, Ming; Garcia, N; Schindler, K; Esquinazi, P

2006-08-18

We present measurements of the electric potential fluctuations on the surface of highly oriented pyrolytic graphite using electrostatic force and atomic force microscopy. Micrometric domainlike potential distributions are observed even when the sample is grounded. Such potential distributions are unexpected given the good metallic conductivity of graphite because the surface should be an equipotential. Our results indicate the coexistence of regions with "metalliclike" and "insulatinglike" behaviors showing large potential fluctuations of the order of 0.25 V. In lower quality graphite, this effect is not observed. Experiments are performed in Ar and air atmospheres.

Structure-Property Relationships in Surface-Modified Ceramics. NATO advanced Science Institutes, Series E: Applied Sciences, Volume 170

DTIC Science & Technology

1989-01-01

channelling and scanning electron microscopy (SEM) of highly oriented pyrolytic graphite ( HOPG ), comparative scratch testing results and some ideas on...electrode graphite , HOPG and carbon fibers also show enhanced wear resistance followoing irradiation (6), the extent of which depends upon the initial...literature dealing with damage effects and physical property changes following neutron irradiation of graphite (single and polycrystalline ) in nuclear

Reflection of Low Energy Positrons from the Surface of Highly Oriented Pyrolytic Graphite and Single Layer Graphene.

NASA Astrophysics Data System (ADS)

Imam, S. K.; Chirayath, V. A.; Chrysler, M. D.; Fairchild, A. J.; Gladen, R. W.; Koymen, A. R.; Weiss, A. H.; UT Arlington Positron Surface Laboratory Team

A time of flight positron annihilation induced Auger electron spectrometer (TOF-PAES) was utilized to measure the reflection of positrons as a function of incident positron energy (0 to 10 eV) from the surface of highly oriented pyrolytic graphite (HOPG) and from a single layer graphene (SLG) on a Cu foil. A NaI scintillation detector was used to measure the annihilation gamma from the reflected positrons as a function of incident positron kinetic energy. The annihilation of the positrons on HOPG and SLG were simultaneously measured using another NaI detector near the sample. The Auger electrons emitted as a result of the annihilation of positrons from the surface of the sample were also measured concurrently. As the positron kinetic energy was increased, the number of reflected positrons calculated from the intensity under the annihilation gamma peak showed a steady decrease. The positronium formation measured at the sample using the gamma spectrum showed a peak at 6 eV. The intensity of the carbon KVV Auger peak showed a dip at the same energy. The correlation of the three signals, intensity of reflected positrons, positrons annihilating at the sample and the Auger intensity are discussed for both samples. This work was supported by NSF Grant No. DMR 1508719 and DMR 1338130.

The Erosion of Diamond and Highly Oriented Pyrolytic Graphite After 1.5 Years of Space Exposure

NASA Technical Reports Server (NTRS)

De Groh, Kim K.; Banks, Bruce A.

2018-01-01

Polymers and other oxidizable materials on the exterior of spacecraft in the low Earth orbit (LEO) space environment can be eroded due to reaction with atomic oxygen (AO). Therefore, in order to design durable spacecraft, it is important to know the LEO AO erosion yield (Ey, volume loss per incident oxygen atom) of materials susceptible to AO reaction. The Polymers Experiment was developed to determine the AO Ey of various polymers and other materials flown in ram and wake orientations in LEO. The experiment was flown as part of the Materials International Space Station Experiment 7 (MISSE 7) mission for 1.5 years on the exterior of the International Space Station (ISS). As part of the experiment, a sample containing Class 2A diamond (100 plane) and highly oriented pyrolytic graphite (HOPG, basal and edge planes) was exposed to ram AO and characterized for erosion. The materials were salt-sprayed prior to flight to provide isolated sites of AO protection. The Ey of the samples was determined through post-flight electron microscopy recession depth measurements. The experiment also included a Kapton H witness sample for AO fluence determination. This paper provides an overview of the MISSE 7 mission, a description of the flight experiment, the characterization techniques used, the mission AO fluence, and the LEO Ey results for diamond and HOPG (basal and edge planes). The data is compared to the Ey of pyrolytic graphite exposed to four years of space exposure as part of the MISSE 2 mission. The results indicate that diamond erodes, but with a very low Ey of 1.58 +/- 0.04 x 10(exp -26) cm(exp 3)/atom. The different HOPG planes displayed significantly different amounts of erosion from each other. The HOPG basal plane had an Ey of 1.05 +/- 0.08 x 10(exp -24) cm(exp 3)/atom while the edge plane had a lower Ey of only 5.38 +/- 0.90 x 10(exp -25) -cm(exp 3)/atom. The Ey data from this ISS spaceflight experiment provides valuable information for understanding of chemistry and chemical structure dependent modeling of AO erosion.

Magnetic Surfaces, Thin Films, and Multilayers

DTIC Science & Technology

1992-01-01

investigations %as the cleaved ((00)I) face of highly oriented pyrolytic graphite ( HOPG ). This surface is inert in air and is easily imaged with the STM[83-86...Parkin IBM Almaden Research Center, San Jose, California, U.S.A. Herbert Hopster University of California -Irvine, Irvine, California, U.S.A. Jean...magnetic fields (typically 10 to 100 kOe). For polycrystalline samples and at normal temperatures more modest increases, typically of a factor of 2 to 10

Transformation of shock-compressed graphite to hexagonal diamond in nanoseconds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turneaure, Stefan J.; Sharma, Surinder M.; Volz, Travis J.

2017-10-01

The graphite-to-diamond transformation under shock compression has been of broad scientific interest since 1961. The formation of hexagonal diamond (HD) is of particular interest because it is expected to be harder than cubic diamond and due to its use in terrestrial sciences as a marker at meteorite impact sites. However, the formation of diamond having a fully hexagonal structure continues to be questioned and remains unresolved. Using real-time (nanosecond), in situ x-ray diffraction measurements, we show unequivocally that highly oriented pyrolytic graphite, shock-compressed along the c axis to 50 GPa, transforms to highly oriented elastically strained HD with the (100)HDmore » plane parallel to the graphite basal plane.« less

Molecular beam epitaxy growth of SrO buffer layers on graphite and graphene for the integration of complex oxides

DOE PAGES

Ahmed, Adam S.; Wen, Hua; Ohta, Taisuke; ...

2016-04-27

Here, we report the successful growth of high-quality SrO films on highly-ordered pyrolytic graphite (HOPG) and single-layer graphene by molecular beam epitaxy. The SrO layers have (001) orientation as confirmed by X-ray diffraction (XRD) while atomic force microscopy measurements show continuous pinhole-free films having rms surface roughness of <1.5 Å. Moreover, transport measurements of exfoliated graphene, after SrO deposition, show a strong dependence between the Dirac point and Sr oxidation. As a result, the SrO is leveraged as a buffer layer for more complex oxide integration via the demonstration of (001) oriented SrTiO3 grown atop a SrO/HOPG stack.

Molecular beam epitaxy growth of SrO buffer layers on graphite and graphene for the integration of complex oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahmed, Adam S.; Wen, Hua; Ohta, Taisuke

Here, we report the successful growth of high-quality SrO films on highly-ordered pyrolytic graphite (HOPG) and single-layer graphene by molecular beam epitaxy. The SrO layers have (001) orientation as confirmed by X-ray diffraction (XRD) while atomic force microscopy measurements show continuous pinhole-free films having rms surface roughness of <1.5 Å. Moreover, transport measurements of exfoliated graphene, after SrO deposition, show a strong dependence between the Dirac point and Sr oxidation. As a result, the SrO is leveraged as a buffer layer for more complex oxide integration via the demonstration of (001) oriented SrTiO3 grown atop a SrO/HOPG stack.

Sound velocities in highly oriented pyrolytic graphite shocked to 18 GPa: Orientational order dependence and elastic instability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lucas, Marcel; Winey, J. M.; Gupta, Y. M.

Previous reports of rapid phase transformation above 18 GPa [Erskine and Nellis, Nature 349, 317 (1991)] and large elastic waves below 18 GPa [Lucas et al., J. Appl. Phys. 114, 093515 (2013)] for shock-compressed ZYB-grade highly-oriented pyrolytic graphite (HOPG), but not for less oriented ZYH-grade HOPG, indicated a link between the orientational order dependence of the HOPG response above and below the phase transformation stress. To gain insight into this link and into the mechanical response of HOPG shocked to peak stresses approaching the phase transformation onset, the compressibility of ZYB- and ZYH-grade HOPG in the shocked state was examinedmore » using front surface impact experiments. Particle velocity histories and sound velocities were measured for peak stresses reaching 18 GPa. Although the locus of the measured peak stress-particle velocity states is indistinguishable for the two grades of HOPG, the measured sound velocities in the peak state reveal significant differences between the two grades. Specifically, 1) The measured sound velocities are somewhat higher for ZYH-grade HOPG, compared to ZYB-grade HOPG. 2) The measured sound velocities for ZYH-grade HOPG increase smoothly with compression, whereas those for ZYB-2 grade HOPG exhibit a significant reduction in the compression dependence from 12 GPa to 17 GPa and an abrupt increase from 17 GPa to 18 GPa. 3) The longitudinal moduli, determined from the measured sound velocities, are smaller than the calculated bulk moduli for ZYB-grade HOPG shocked to peak stresses above 15 GPa, indicating the onset of an elastic instability. The present findings demonstrate that the softening of the longitudinal modulus (or elastic instability) presented here is linked to the large elastic waves and the rapid phase transformation reported previously – all observed only for shocked ZYB-grade HOPG. The elastic instability in shocked ZYB-grade HOPG is likely a precursor to the rapid phase transformation observed above 18 GPa for this HOPG grade.« less

Sound velocities in highly oriented pyrolytic graphite shocked to 18 GPa: Orientational order dependence and elastic instability

DOE PAGES

Lucas, Marcel; Winey, J. M.; Gupta, Y. M.

2015-12-28

Previous reports of rapid phase transformation above 18 GPa [Erskine and Nellis, Nature 349, 317 (1991)] and large elastic waves below 18 GPa [Lucas et al., J. Appl. Phys. 114, 093515 (2013)] for shock-compressed ZYB-grade highly-oriented pyrolytic graphite (HOPG), but not for less oriented ZYH-grade HOPG, indicated a link between the orientational order dependence of the HOPG response above and below the phase transformation stress. To gain insight into this link and into the mechanical response of HOPG shocked to peak stresses approaching the phase transformation onset, the compressibility of ZYB- and ZYH-grade HOPG in the shocked state was examinedmore » using front surface impact experiments. Particle velocity histories and sound velocities were measured for peak stresses reaching 18 GPa. Although the locus of the measured peak stress-particle velocity states is indistinguishable for the two grades of HOPG, the measured sound velocities in the peak state reveal significant differences between the two grades. Specifically, 1) The measured sound velocities are somewhat higher for ZYH-grade HOPG, compared to ZYB-grade HOPG. 2) The measured sound velocities for ZYH-grade HOPG increase smoothly with compression, whereas those for ZYB-2 grade HOPG exhibit a significant reduction in the compression dependence from 12 GPa to 17 GPa and an abrupt increase from 17 GPa to 18 GPa. 3) The longitudinal moduli, determined from the measured sound velocities, are smaller than the calculated bulk moduli for ZYB-grade HOPG shocked to peak stresses above 15 GPa, indicating the onset of an elastic instability. The present findings demonstrate that the softening of the longitudinal modulus (or elastic instability) presented here is linked to the large elastic waves and the rapid phase transformation reported previously – all observed only for shocked ZYB-grade HOPG. The elastic instability in shocked ZYB-grade HOPG is likely a precursor to the rapid phase transformation observed above 18 GPa for this HOPG grade.« less

Coupling Graphene Sheets with Magnetic Nanoparticles for Energy Storage and Microelectronics

DTIC Science & Technology

2015-08-13

sheets obtained from three different synthetic methods: (i) electrochemical exfoliation of highly oriented pyrolytic graphite ( HOPG ) [8], (ii...Figure 8d, the characteristic lattice fringes of ɤ-Fe2O3 nanoparticles in graphene sheet is shown. Typical X-ray diffraction ( XRD ) patterns of the HOPG ...pattern in honey comb crystal lattice, (c) TEM (d) HRTEM image of graphene- PyDop1-MNP hybrid, (e) XRD pattern of the HOPG , exfoliated graphene, PyDop1

Surface analysis of model systems: From a metal-graphite interface to an intermetallic catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwolek, Emma J.

This thesis summarizes research completed on two different model systems. In the first system, we investigate the deposition of the elemental metal dysprosium on highly-oriented pyrolytic graphite (HOPG) and its resulting nucleation and growth. The goal of this research is to better understand the metal-carbon interactions that occur on HOPG and to apply those to an array of other carbon surfaces. This insight may prove beneficial to developing and using new materials for electronic applications, magnetic applications and catalysis.

Pyrolytic graphite gauge for measuring heat flux

NASA Technical Reports Server (NTRS)

Bunker, Robert C. (Inventor); Ewing, Mark E. (Inventor); Shipley, John L. (Inventor)

2002-01-01

A gauge for measuring heat flux, especially heat flux encountered in a high temperature environment, is provided. The gauge includes at least one thermocouple and an anisotropic pyrolytic graphite body that covers at least part of, and optionally encases the thermocouple. Heat flux is incident on the anisotropic pyrolytic graphite body by arranging the gauge so that the gauge surface on which convective and radiative fluxes are incident is perpendicular to the basal planes of the pyrolytic graphite. The conductivity of the pyrolytic graphite permits energy, transferred into the pyrolytic graphite body in the form of heat flux on the incident (or facing) surface, to be quickly distributed through the entire pyrolytic graphite body, resulting in small substantially instantaneous temperature gradients. Temperature changes to the body can thereby be measured by the thermocouple, and reduced to quantify the heat flux incident to the body.

Orientation-dependent energy level alignment and film growth of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on HOPG

NASA Astrophysics Data System (ADS)

Lyu, Lu; Niu, Dongmei; Xie, Haipeng; Cao, Ningtong; Zhang, Hong; Zhang, Yuhe; Liu, Peng; Gao, Yongli

2016-01-01

Combining ultraviolet photoemission spectroscopy, X-ray photoemission spectroscopy, atomic force microscopy, and X-ray diffraction measurements, we performed a systematic investigation on the correlation of energy level alignment, film growth, and molecular orientation of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on highly oriented pyrolytic graphite. The molecules lie down in the first layer and then stand up from the second layer. The ionization potential shows a sharp decrease from the lying down region to the standing up region. When C8-BTBT molecules start standing up, unconventional energy level band-bending-like shifts are observed as the film thickness increases. These shifts are ascribed to gradual decreasing of the molecular tilt angle about the substrate normal with the increasing film thickness.

Orientation-dependent energy level alignment and film growth of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on HOPG.

PubMed

Lyu, Lu; Niu, Dongmei; Xie, Haipeng; Cao, Ningtong; Zhang, Hong; Zhang, Yuhe; Liu, Peng; Gao, Yongli

2016-01-21

Combining ultraviolet photoemission spectroscopy, X-ray photoemission spectroscopy, atomic force microscopy, and X-ray diffraction measurements, we performed a systematic investigation on the correlation of energy level alignment, film growth, and molecular orientation of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on highly oriented pyrolytic graphite. The molecules lie down in the first layer and then stand up from the second layer. The ionization potential shows a sharp decrease from the lying down region to the standing up region. When C8-BTBT molecules start standing up, unconventional energy level band-bending-like shifts are observed as the film thickness increases. These shifts are ascribed to gradual decreasing of the molecular tilt angle about the substrate normal with the increasing film thickness.

Semiconductor cooling apparatus

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor); Gaier, James R. (Inventor)

1993-01-01

Gas derived graphite fibers generated by the decomposition of an organic gas are joined with a suitable binder. This produces a high thermal conductivity composite material which passively conducts heat from a source, such as a semiconductor, to a heat sink. The fibers may be intercalated. The intercalate can be halogen or halide salt, alkaline metal, or any other species which contributes to the electrical conductivity improvement of the graphite fiber. The fibers are bundled and joined with a suitable binder to form a high thermal conductivity composite material device. The heat transfer device may also be made of intercalated highly oriented pyrolytic graphite and machined, rather than made of fibers.

Magnetotransport in Two Dimensional Electron Systems Under Microwave Excitation and in Highly Oriented Pyrolytic Graphite

DTIC Science & Technology

2012-01-01

Phys. Rev. Lett. 82, 2147 (1999). [89] Y. Zhang, Y. Tan, H. L. Stormer and P. Kim, Nature 438, 10 (2005). [90] J. W. McClure, Phys. Rev. 108, 612 (1957...Phys. 2, 595 (2006). [97] H. L. Stormer , J. P. Eisenstein, A. C. Gossard, W. Wiegmann, and K. Baldwin, Phys. Rev. Lett. 56, 85 (1985). [98] B. A...Sadowski, J. M. Schneider, and M. Potemski, J. Phys.: Cond. Matter 20, 454223 (2008). [108] W. Pan, J. S. Xia, H. L. Stormer , D. C. Tsui, C. L

Coupling Graphene Sheets with Iron Oxide Nanoparticles for Energy Storage and Microelectronics

DTIC Science & Technology

2015-08-13

of highly oriented pyrolytic graphite ( HOPG ) flake. Two electrode system containing platinum as counter electrode and HOPG as working electrode is... XRD ) patterns of the HOPG , exfoliated graphene, PyDop1-ɤ-Fe2O3 and PyDop1-ɤ-Fe2O3-graphene are given in Figure 1e. HOPG show a very sharp diffraction...atoms arranged in hexagonal pattern in honey comb crystal lattice, (c) TEM (d) HRTEM image of graphene- PyDop1-MNP hybrid, (e) XRD pattern of the HOPG

Orientation-dependent energy level alignment and film growth of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on HOPG

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lyu, Lu; Niu, Dongmei, E-mail: mayee@csu.edu.cnmailto; Xie, Haipeng

Combining ultraviolet photoemission spectroscopy, X-ray photoemission spectroscopy, atomic force microscopy, and X-ray diffraction measurements, we performed a systematic investigation on the correlation of energy level alignment, film growth, and molecular orientation of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on highly oriented pyrolytic graphite. The molecules lie down in the first layer and then stand up from the second layer. The ionization potential shows a sharp decrease from the lying down region to the standing up region. When C8-BTBT molecules start standing up, unconventional energy level band-bending-like shifts are observed as the film thickness increases. These shifts are ascribed to gradual decreasing of the molecularmore » tilt angle about the substrate normal with the increasing film thickness.« less

Deducing 2D Crystal Structure at the Solid/Liquid Interface with Atomic Resolution by Combined STM and SFG Study

NASA Astrophysics Data System (ADS)

McClelland, Arthur; Ahn, Seokhoon; Matzger, Adam J.; Chen, Zhan

2009-03-01

Supplemented by computed models, Scanning Tunneling Microscopy (STM) can provide detailed structure of 2D crystals formed at the liquid/solid interface with atomic resolution. However, some structural information such as functional group orientations in such 2D crystals needs to be tested experimentally to ensure the accuracy of the deduced structures. Due to the limited sensitivity, many other experimental techniques such as Raman and infrared spectroscopy have not been allowed to provide such structural information of 2D crystals. Here we showed that Sum Frequency Generation Vibrational Spectroscopy (SFG) can measure average orientation of functional groups in such 2D crystals, or physisorbed monolayers, providing key experimental data to aid in the modeling and interpretation of the STM images. The usefulness of combining these two techniques is demonstrated with a phthalate diesters monolayer formed at the 1-phenyloctane/ highly oriented pyrolytic graphite (HOPG) interface. The spatial orientation of the ester C=O of the monolayer was successfully determined using SFG.

Sulfur redox reactions on nanostructured highly oriented pyrolytic graphite (HOPG) electrodes: Direct evidence for superior electrocatalytic performance on defect sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Gongwei; Zheng, Dong; Liu, Dan

Fundamental research of sulfur redox reactions on well-defined controlled model electrode surfaces can provide new information to design high-performance lithium-sulfur batteries. In this paper, we study the electrochemical reduction and oxidation of sulfur on the nanostructured HOPG electrodes with pure basal planes, step plans, and pure edge planes. Finally, our results directly indicate that electrochemical reduction and oxidation of sulfur is significantly affected by the carbon surface structure, namely, the electrochemical reversibility of sulfur redox reaction is much better on edge plane, compared with basal plane and step plane.

Sulfur redox reactions on nanostructured highly oriented pyrolytic graphite (HOPG) electrodes: Direct evidence for superior electrocatalytic performance on defect sites

DOE PAGES

Wang, Gongwei; Zheng, Dong; Liu, Dan; ...

2017-04-28

Fundamental research of sulfur redox reactions on well-defined controlled model electrode surfaces can provide new information to design high-performance lithium-sulfur batteries. In this paper, we study the electrochemical reduction and oxidation of sulfur on the nanostructured HOPG electrodes with pure basal planes, step plans, and pure edge planes. Finally, our results directly indicate that electrochemical reduction and oxidation of sulfur is significantly affected by the carbon surface structure, namely, the electrochemical reversibility of sulfur redox reaction is much better on edge plane, compared with basal plane and step plane.

Femtosecond laser ablation of highly oriented pyrolytic graphite: a green route for large-scale production of porous graphene and graphene quantum dots.

PubMed

Russo, Paola; Hu, Anming; Compagnini, Giuseppe; Duley, Walter W; Zhou, Norman Y

2014-02-21

Porous graphene (PG) and graphene quantum dots (GQDs) are attracting attention due to their potential applications in photovoltaics, catalysis, and bio-related fields. We present a novel way for mass production of these promising materials. The femtosecond laser ablation of highly oriented pyrolytic graphite (HOPG) is employed for their synthesis. Porous graphene (PG) layers were found to float at the water-air interface, while graphene quantum dots (GQDs) were dispersed in the solution. The sheets consist of one to six stacked layers of spongy graphene, which form an irregular 3D porous structure that displays pores with an average size of 15-20 nm. Several characterization techniques have confirmed the porous nature of the collected layers. The analyses of the aqueous solution confirmed the presence of GQDs with dimensions of about 2-5 nm. It is found that the formation of both PG and GQDs depends on the fs-laser ablation energy. At laser fluences less than 12 J cm(-2), no evidence of either PG or GQDs is detected. However, polyynes with six and eight carbon atoms per chain are found in the solution. For laser energies in the 20-30 J cm(-2) range, these polyynes disappeared, while PG and GQDs were found at the water-air interface and in the solution, respectively. The origin of these materials can be explained based on the mechanisms for water breakdown and coal gasification. The absence of PG and GQDs, after the laser ablation of HOPG in liquid nitrogen, confirms the proposed mechanisms.

Kinetics of solvent supported tubule formation of Lotus (Nelumbo nucifera) wax on highly oriented pyrolytic graphite (HOPG) investigated by atomic force microscopy

PubMed Central

Koch, Kerstin; Barthlott, Wilhelm; Wandelt, Klaus

2018-01-01

The time dependence of the formation of lotus wax tubules after recrystallization from various chloroform-based solutions on an HOPG surface at room temperature was studied by atomic force microscopy (magnetic AC mode) taking series of consecutive images of the formation process. The growth of the tubules oriented in an upright fashion follows a sequential rodlet→ring→tubule behavior. The influence of a number of factors, e.g., different wax concentration in chloroform, the additional presence of water, or salts [(NH4)2SO4, NH4NO3] or a mixture of salt/water in the solution on the growth rate and orientation of the tubules is also investigated. Different wax concentrations were found to have no effect on the growth rate or the orientation of tubules in none of the solutions. The presence of water, however, considerably increased the growth rate of tubule formation, while the presence of salt was again found to have no effect on growth rate or orientation of tubules. PMID:29515959

Program for the development of high temperature electrical materials and components

NASA Technical Reports Server (NTRS)

Neff, W. S.; Lowry, L. R.

1972-01-01

Evaluation of high temperature, space-vacuum performance of selected electrical materials and components, high temperature capacitor development, and evaluation, construction, and endurance testing of compression sealed pyrolytic boron nitride slot insulation are described. The first subject above covered the aging evaluation of electrical devices constructed from selected electrical materials. Individual materials performances were also evaluated and reported. The second subject included study of methods of improving electrical performance of pyrolytic boron nitride capacitors. The third portion was conducted to evaluate the thermal and electrical performance of pyrolytic boron nitride as stator slot liner material under varied temperature and compressive loading. Conclusions and recommendations are presented.

Ultrafast compression of graphite observed with sub-ps time resolution diffraction on LCLS

NASA Astrophysics Data System (ADS)

Armstrong, Michael; Goncharov, A.; Crowhurst, J.; Zaug, J.; Radousky, H.; Grivickas, P.; Bastea, S.; Goldman, N.; Stavrou, E.; Belof, J.; Gleason, A.; Lee, H. J.; Nagler, R.; Holtgrewe, N.; Walter, P.; Pakaprenka, V.; Nam, I.; Granados, E.; Presher, C.; Koroglu, B.

2017-06-01

We will present ps time resolution pulsed x-ray diffraction measurements of rapidly compressed highly oriented pyrolytic graphite along its basal plane at the Materials under Extreme Conditions (MEC) sector of the Linac Coherent Light Source (LCLS). These experiments explore the possibility of rapid (<100 ps time scale) material transformations occurring under very highly anisotropic compression conditions. Under such conditions, non-equilibrium mechanisms may play a role in the transformation process. We will present experimental results and simulations which explore this possibility. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Security, LLC under Contract DE-AC52-07NA27344.

Highly sensitive protein detection by biospecific AFM-based fishing with pulsed electrical stimulation.

PubMed

Pleshakova, Tatyana O; Malsagova, Kristina A; Kaysheva, Anna L; Kopylov, Arthur T; Tatur, Vadim Yu; Ziborov, Vadim S; Kanashenko, Sergey L; Galiullin, Rafael A; Ivanov, Yuri D

2017-08-01

We report here the highly sensitive detection of protein in solution at concentrations from 10 -15 to 10 -18 m using the combination of atomic force microscopy (AFM) and mass spectrometry. Biospecific detection of biotinylated bovine serum albumin was carried out by fishing out the protein onto the surface of AFM chips with immobilized avidin, which determined the specificity of the analysis. Electrical stimulation was applied to enhance the fishing efficiency. A high sensitivity of detection was achieved by application of nanosecond electric pulses to highly oriented pyrolytic graphite placed under the AFM chip. A peristaltic pump-based flow system, which is widely used in routine bioanalytical assays, was employed throughout the analysis. These results hold promise for the development of highly sensitive protein detection methods using nanosensor devices.

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.

Understanding the formation mechanism of graphene frameworks synthesized by solvothermal and rapid pyrolytic processes based on an alcohol-sodium hydroxide system.

PubMed

Cui, Huijuan; Zheng, Jianfeng; Yang, Pengju; Zhu, Yanyan; Wang, Zhijian; Zhu, Zhenping

2015-06-03

The determination of ways to facilitate the 2D-oriented assembly of carbons into graphene instead of other carbon structures while restraining the π-π stacking interaction is a challenge for the controllable bulk synthesis of graphene, which is vital both scientifically and technically. In this study, graphene frameworks (GFs) are synthesized by solvothermal and rapid pyrolytic processes based on an alcohol-sodium hydroxide system. The evolution mechanism of GFs is investigated systematically. Under sodium catalysis, the abundant carbon atoms produced by the fast decomposition of solvothermal intermediate self-assembled to graphene. The existence of abundant ether bonds may be favorable for 3D graphene formation. More importantly, GFs were successfully obtained using acetic acid as the carbon source in the synthetic process, suggesting the reasonability of analyzing the formation mechanism. It is quite possible to determine more favorable routes to synthesize graphene under this cognition. The electrochemical energy storage capacity of GFs was also studied, which revealed a high supercapacitor performance with a specific capacitance of 310.7 F/g at the current density of 0.2 A/g.

Pulsed Laser Ablation Synthesis of Diamond Molecules in Supercritical Fluids

NASA Astrophysics Data System (ADS)

Nakahara, Sho; Stauss, Sven; Miyazoe, Hiroyuki; Shizuno, Tomoki; Suzuki, Minoru; Kataoka, Hiroshi; Sasaki, Takehiko; Terashima, Kazuo

2010-09-01

Nanocarbon materials have been synthesized by pulsed laser ablation (532 nm; 52 J/cm2; 7 ns; 10 Hz) of highly oriented pyrolytic graphite in adamantane-dissolved supercritical xenon at a temperature T = 290.2 K and pressure p = 5.86 MPa. Micro-Raman spectroscopy of the products revealed the presence of hydrocarbons possessing sp3 hybridized bonds also found in diamond structures. The synthesis of diamantane was confirmed by gas chromatography-mass spectrometry. The same measurements also indicate the possible synthesis of other diamondoids up to octamantane. Thus, laser ablation in supercritical fluids is proposed as one practical method of synthesizing diamondoids.

Bias-induced conformational switching of supramolecular networks of trimesic acid at the solid-liquid interface

NASA Astrophysics Data System (ADS)

Ubink, J.; Enache, M.; Stöhr, M.

2018-05-01

Using the tip of a scanning tunneling microscope, an electric field-induced reversible phase transition between two planar porous structures ("chickenwire" and "flower") of trimesic acid was accomplished at the nonanoic acid/highly oriented pyrolytic graphite interface. The chickenwire structure was exclusively observed for negative sample bias, while for positive sample bias only the more densely packed flower structure was found. We suggest that the slightly negatively charged carboxyl groups of the trimesic acid molecule are the determining factor for this observation: their adsorption behavior varies with the sample bias and is thus responsible for the switching behavior.

Imaging graphite in air by scanning tunneling microscopy - Role of the tip

NASA Technical Reports Server (NTRS)

Colton, R. J.; Baker, S. M.; Driscoll, R. J.; Youngquist, M. G.; Baldeschwieler, J. D.; Kaiser, W. J.

1988-01-01

Atomically resolved images of highly oriented pyrolytic graphite (HOPG) in air at point contact have been obtained. Direct contact between tip and sample or contact through a contamination layer provides a conduction mechanism in addition to the exponential tunneling mechanism responsible for scanning tunneling microscopy (STM) imaging. Current-voltage (I-V) spectra were obtained while scanning in the current imaging mode with the feedback circuit interrupted in order to study the graphite imaging mechanism. Multiple tunneling tips are probably responsible for images without the expected hexagonal or trigonal symmetry. The observations indicate that the use of HOPG for testing and calibration of STM instrumentation may be misleading.

Mono- and multilayers of molecular spoked carbazole wheels on graphite

PubMed Central

Aggarwal, A Vikas; Kalle, Daniel; Höger, Sigurd

2014-01-01

Summary Self-assembled monolayers of a molecular spoked wheel (a shape-persistent macrocycle with an intraannular spoke/hub system) and its synthetic precursor are investigated by scanning tunneling microscopy (STM) at the liquid/solid interface of 1-octanoic acid and highly oriented pyrolytic graphite. The submolecularly resolved STM images reveal that the molecules indeed behave as more or less rigid objects of certain sizes and shapes – depending on their chemical structures. In addition, the images provide insight into the multilayer growth of the molecular spoked wheels (MSWs), where the first adlayer acts as a template for the commensurate adsorption of molecules in the second layer. PMID:25550744

Mono- and multilayers of molecular spoked carbazole wheels on graphite.

PubMed

Jester, Stefan-S; Aggarwal, A Vikas; Kalle, Daniel; Höger, Sigurd

2014-01-01

Self-assembled monolayers of a molecular spoked wheel (a shape-persistent macrocycle with an intraannular spoke/hub system) and its synthetic precursor are investigated by scanning tunneling microscopy (STM) at the liquid/solid interface of 1-octanoic acid and highly oriented pyrolytic graphite. The submolecularly resolved STM images reveal that the molecules indeed behave as more or less rigid objects of certain sizes and shapes - depending on their chemical structures. In addition, the images provide insight into the multilayer growth of the molecular spoked wheels (MSWs), where the first adlayer acts as a template for the commensurate adsorption of molecules in the second layer.

Size-dependent electrocatalytic activity of gold nanoparticles on HOPG and highly boron-doped diamond surfaces.

PubMed

Brülle, Tine; Ju, Wenbo; Niedermayr, Philipp; Denisenko, Andrej; Paschos, Odysseas; Schneider, Oliver; Stimming, Ulrich

2011-12-06

Gold nanoparticles were prepared by electrochemical deposition on highly oriented pyrolytic graphite (HOPG) and boron-doped, epitaxial 100-oriented diamond layers. Using a potentiostatic double pulse technique, the average particle size was varied in the range from 5 nm to 30 nm in the case of HOPG as a support and between < 1 nm and 15 nm on diamond surfaces, while keeping the particle density constant. The distribution of particle sizes was very narrow, with standard deviations of around 20% on HOPG and around 30% on diamond. The electrocatalytic activity towards hydrogen evolution and oxygen reduction of these carbon supported gold nanoparticles in dependence of the particle sizes was investigated using cyclic voltammetry. For oxygen reduction the current density normalized to the gold surface (specific current density) increased for decreasing particle size. In contrast, the specific current density of hydrogen evolution showed no dependence on particle size. For both reactions, no effect of the different carbon supports on electrocatalytic activity was observed.

Materials International Space Station Experiment-6 (MISSE-6) Atomic Oxygen Fluence Monitor Experiment

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Miller, Sharon K.; Waters, Deborah L.

2010-01-01

An atomic oxygen fluence monitor was flown as part of the Materials International Space Station Experiment-6 (MISSE-6). The monitor was designed to measure the accumulation of atomic oxygen fluence with time as it impinged upon the ram surface of the MISSE 6B Passive Experiment Container (PEC). This was an active experiment for which data was to be stored on a battery-powered data logger for post-flight retrieval and analysis. The atomic oxygen fluence measurement was accomplished by allowing atomic oxygen to erode two opposing wedges of pyrolytic graphite that partially covered a photodiode. As the wedges of pyrolytic graphite erode, the area of the photodiode that is illuminated by the Sun increases. The short circuit current, which is proportional to the area of illumination, was to be measured and recorded as a function of time. The short circuit current from a different photodiode, which was oriented in the same direction and had an unobstructed view of the Sun, was also to be recorded as a reference current. The ratio of the two separate recorded currents should bear a linear relationship with the accumulated atomic oxygen fluence and be independent of the intensity of solar illumination. Ground hyperthermal atomic oxygen exposure facilities were used to evaluate the linearity of the ratio of short circuit current to the atomic oxygen fluence. In flight, the current measurement circuitry failed to operate properly, thus the overall atomic oxygen mission fluence could only be estimated based on the physical erosion of the pyrolytic graphite wedges. The atomic oxygen fluence was calculated based on the knowledge of the space atomic oxygen erosion yield of pyrolytic graphite measured from samples on the MISSE 2. The atomic oxygen fluence monitor, the expected result and comparison of mission atomic oxygen fluence based on the erosion of the pyrolytic graphite and Kapton H atomic oxygen fluence witness samples are presented in this paper.

Improving a high-efficiency, gated spectrometer for x-ray Thomson scattering experiments at the National Ignition Facility.

PubMed

Döppner, T; Kraus, D; Neumayer, P; Bachmann, B; Emig, J; Falcone, R W; Fletcher, L B; Hardy, M; Kalantar, D H; Kritcher, A L; Landen, O L; Ma, T; Saunders, A M; Wood, R D

2016-11-01

We are developing x-ray Thomson scattering for applications in implosion experiments at the National Ignition Facility. In particular we have designed and fielded MACS, a high-efficiency, gated x-ray spectrometer at 7.5-10 keV [T. Döppner et al., Rev. Sci. Instrum. 85, 11D617 (2014)]. Here we report on two new Bragg crystals based on Highly Oriented Pyrolytic Graphite (HOPG), a flat crystal and a dual-section cylindrically curved crystal. We have performed in situ calibration measurements using a brass foil target, and we used the flat HOPG crystal to measure Mo K-shell emission at 18 keV in 2nd order diffraction. Such high photon energy line emission will be required to penetrate and probe ultra-high-density plasmas or plasmas of mid-Z elements.

Beam impingement angle effects on secondary electron emission characteristics of textured pyrolytic graphite

NASA Technical Reports Server (NTRS)

Curren, A. N.; Jensen, K. A.

1984-01-01

Experimentally determined values of true secondary electron emission and relative values of reflected primary electron yield for untreated and ion-textured pyrolytic graphite over a range of primary electron energy levels and electron beam impingement angles are presented. Information required to develop high efficiency multistage depressed collectors (MDC's) for microwave amplifier traveling-wave tubes for space communication and aircraft applications is provided. To attain the highest possible MDC efficiencies, the electrode surfaces must have low secondary electron emission characteristics. Pyrolytic graphite, a chemically vapor-deposited material, is a particularly promising candidate for this application. The pyrolytic graphite surfaces studied were tested over a range of primary electron beam energies and beam impingement angles from 200 to 2000 eV and direct (0 deg) to near-grazing angles (85 deg), respectively. Surfaces both parallel to and normal to the planes of material deposition were examined. The true secondary electron emission and reflected primary electron yield characteristics of the pyrolytic graphite surfaces are compared to those of sooted control surfaces.

Orientation-free and differentially pumped addition of a low-flux reactive gas beam to a surface analysis system.

PubMed

Harthcock, Colin; Jahanbekam, Abdolreza; Eskelsen, Jeremy R; Lee, David Y

2016-11-01

We describe an example of a piecewise gas chamber that can be customized to incorporate a low flux of gas-phase radicals with an existing surface analysis chamber for in situ and stepwise gas-surface interaction experiments without any constraint in orientation. The piecewise nature of this gas chamber provides complete angular freedom and easy alignment and does not require any modification of the existing surface analysis chamber. In addition, the entire gas-surface system is readily differentially pumped with the surface chamber kept under ultra-high-vacuum during the gas-surface measurements. This new design also allows not only straightforward reconstruction to accommodate the orientation of different surface chambers but also for the addition of other desired features, such as an additional pump to the current configuration. Stepwise interaction between atomic oxygen and a highly ordered pyrolytic graphite surface was chosen to test the effectiveness of this design, and the site-dependent O-atom chemisorption and clustering on the graphite surface were resolved by a scanning tunneling microscope in the nm-scale. X-ray photoelectron spectroscopy was used to further confirm the identity of the chemisorbed species on the graphite surface as oxygen.

Calibration and characterization of a highly efficient spectrometer in von Hamos geometry for 7-10 keV x-rays

DOE PAGES

Jarrott, L. C.; Wei, M. S.; McGuffey, C.; ...

2017-04-27

Here, we have built an absolutely calibrated, highly efficient, Bragg crystal spectrometer in von Hamos geometry. This zinc von Hamos spectrometer uses a crystal made from highly oriented pyrolytic graphite that is cylindrically bent along the non-dispersive axis. It is tuned to measure x-ray spectra in the 7–10 keV range and has been designed to be used on a Ten Inch Manipulator for the Omega and OmegaEP target chambers at the Laboratory for Laser Energetics in Rochester, USA. Significant shielding strategies and fluorescence mitigation have been implemented in addition to an imaging plate detector making it well suited for experimentsmore » in high-intensity environments. Here we present the design and absolute calibration as well as mosaicity and integrated reflectivity measurements.« less

P(VDF/TrFE) morphologies and crystalline lamellae orientations dependence on substrates characterized by scanning probe microscopy

NASA Astrophysics Data System (ADS)

Lakbita, Imane; El-Hami, Khalil

2018-02-01

Ultra-thin films of the polyvinylidene fluoride and trifluoroethylene (P(VDF/TrFE)) copolymer were elaborated on various different substrates by the spin coating method. The purpose of this paper is to study the P(VDF/TrFE) morphologies and crystalline lamellae orientation dependence on substrates. We chose the potassium chloride (KCl), Sodium Chloride (NaCl) and Potassium Bromide (KBr) with the [110] direction and the highly ordered pyrolytic graphite (HOPG) substrates because they present different crystallographic structures. The atomic force microscopy is used for imaging P(VDF/TrFE) morphologies with nanometer resolution and determining the surface roughness. The analysis of the AFM topography images revealed that the P(VDF/TrFE) film has, almost, the same texture on KCl, NaCl or on KBr substrates and their crystalline lamellae had grown in two preferred orientations. Unlike the HOPG substrate, their crystalline lamellae were entangled, randomly oriented and positioned adjacent to each other. The growth texture of the P(VDF/TrFE) copolymer showed experimentally a strong dependence on substrate types. Since the P(VDF/TrFE) is ferroelectric, piezoelectric and pyroelectric, this finding may lead to potential applications.

Surface induced selective deposition of Dysprosium Polyoxometalate on HOPG surface studied by STM and STS

NASA Astrophysics Data System (ADS)

Costa Milan, David; Pinilla Cienfuegos, Elena; Cardona Serra, Salvador; Coronado Miralles, Eugenio; Untiedt Lecuona, Carlos

2013-03-01

Scanning Tunneling Microscope (STM) and scanning Tunnelling spectroscopy (STS) techniques have been used to study the Preyssler type Polyoxometalate K12[DyP5W30O110] molecules deposited on Highly Oriented Pyrolytic Graphite surface (HOPG). Chainlike arrangements of clusters containing two or three molecules, as well as different cluster sizes are observed. As many structural artifacts are present on the graphite surface, like Moiré patterns, that could look like the molecular deposits, we have studied their STS and size to ensure the presence of the POM molecules on the surface. This article shows the possibility of addressing POMs on a flat surface to obtain their electronic properties through STS.

Thermal Performance of an Annealed Pyrolytic Graphite Solar Collector

NASA Technical Reports Server (NTRS)

Jaworske, Donald A.; Hornacek, Jennifer

2002-01-01

A solar collector having the combined properties of high solar absorptance, low infrared emittance, and high thermal conductivity is needed for applications where solar energy is to be absorbed and transported for use in minisatellites. Such a solar collector may be used with a low temperature differential heat engine to provide power or with a thermal bus for thermal switching applications. One concept being considered for the solar collector is an Al2O3 cermet coating applied to a thermal conductivity enhanced polished aluminum substrate. The cermet coating provides high solar absorptance and the polished aluminum provides low infrared emittance. Annealed pyrolytic graphite embedded in the aluminum substrate provides enhanced thermal conductivity. The as-measured thermal performance of an annealed pyrolytic graphite thermal conductivity enhanced polished aluminum solar collector, coated with a cermet coating, will be presented.

Neutron transmission measurements of poly and pyrolytic graphite crystals

NASA Astrophysics Data System (ADS)

Adib, M.; Abbas, Y.; Abdel-Kawy, A.; Ashry, A.; Kilany, M.; Kenawy, M. A.

The total neutron cross-section measurements of polycrystalline graphite have been carried out in a neutron wavelength from 0.04 to 0.78 nm. This work also presents the neutron transmission measurements of pyrolytic graphite (PG) crystal in a neutron wavelength band from 0.03 to 0.50 nm, at different orientations of the PG crystal with regard to the beam direction. The measurements were performed using three time-of-flight (TOF) spectrometers installed in front of three of the ET-RR-1 reactor horizontal channels. The average value of the coherent scattering amplitude for polycrystalline graphite was calculated and found to be bcoh = (6.61 ± 0.07) fm. The behaviour of neutron transmission through the PG crystal, while oriented at different angles with regard to the beam direction, shows dips at neutron wavelengths corresponding to the reflections from (hkl) planes of hexagonal graphite structure. The positions of the observed dips are found to be in good agreement with the calculated ones. It was also found that a 40 mm thick PG crystal is quite enough to reduce the second-order contamination of the neutron beam from 2.81 to 0.04, assuming that the incident neutrons have a Maxwell distribution with neutron gas temperature 330 K.

Improving a high-efficiency, gated spectrometer for x-ray Thomson scattering experiments at the National Ignition Facility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Döppner, T., E-mail: doeppner1@llnl.gov; Bachmann, B.; Emig, J.

We are developing x-ray Thomson scattering for applications in implosion experiments at the National Ignition Facility. In particular we have designed and fielded MACS, a high-efficiency, gated x-ray spectrometer at 7.5–10 keV [T. Döppner et al., Rev. Sci. Instrum. 85, 11D617 (2014)]. Here we report on two new Bragg crystals based on Highly Oriented Pyrolytic Graphite (HOPG), a flat crystal and a dual-section cylindrically curved crystal. We have performed in situ calibration measurements using a brass foil target, and we used the flat HOPG crystal to measure Mo K-shell emission at 18 keV in 2nd order diffraction. Such high photonmore » energy line emission will be required to penetrate and probe ultra-high-density plasmas or plasmas of mid-Z elements.« less

Improving a high-efficiency, gated spectrometer for x-ray Thomson scattering experiments at the National Ignition Facility

DOE PAGES

Döppner, T.; Kraus, D.; Neumayer, P.; ...

2016-08-03

We are developing x-ray Thomson scattering for applications in implosion experiments at the National Ignition Facility. In particular we have designed and fielded MACS, a high-efficiency, gated x-ray spectrometer at 7.5-10 keV [T. Döppner et al., Rev. Sci. Instrum. 85, 11D617 (2014)]. Here in this paper we report on two new Bragg crystals based on Highly Oriented Pyrolytic Graphite (HOPG), a flat crystal and a dual-section cylindrically curved crystal. We have performed in situ calibration measurements using a brass foil target, and we used the flat HOPG crystal to measure Mo K-shell emission at 18 keV in 2nd order diffraction.more » Such high photon energy line emission will be required to penetrate and probe ultra-high-density plasmas or plasmas of mid-Z elements.« less

Feasibility of intercalated graphite railgun armatures

NASA Technical Reports Server (NTRS)

Gaier, James R.; Gooden, Clarence E.; Yashan, Doreen; Naud, Steven

1990-01-01

Graphite intercalation compounds may provide an excellent material for the fabrication of electro-magnetic railgun armatures. As a pulse of power is fed into the armature the intercalate could be excited into the plasma state around the edges of the armature, while the bulk of the current would be carried through the graphite block. Such an armature would have the desirable characteristics of both diffuse plasma armatures and bulk conduction armatures. In addition, the highly anisotropic nature of these materials could enable the electrical and thermal conductivity to be tailored to meet the specific requirements of electromagnetic railgun armatures. Preliminary investigations were performed in an attempt to determine the feasibility of using graphite intercalation compounds as railgun armatures. Issues of fabrication, resistivity, stability, and electrical current spreading are addressed for the case of highly oriented pyrolytic graphite.

Soft X-Ray Absorption Spectroscopy of High-Abrasion-Furnace Carbon Black

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muramatsu, Yasuji; Harada, Ryusuke; Gullikson, Eric M.

2007-02-02

The soft x-ray absorption spectra of high-abrasion-furnace carbon black were measured to obtain local-structure/chemical-states information of the primary particles and/or crystallites. The soft x-ray absorption spectral features of carbon black represent broader {pi}* and {sigma}* peak structures compared to highly oriented pyrolytic graphite (HOPG). The subtracted spectra between the carbon black and HOPG, (carbon black) - (HOPG), show double-peak structures on both sides of the {pi}* peak. The lower-energy peak, denoted as the 'pre-peak', in the subtracted spectra and the {pi}*/{sigma}* peak intensity ratio in the absorption spectra clearly depend on the specific surface area by nitrogen adsorption (NSA). Therefore,more » it is concluded that the pre-peak intensity and the {pi}*/{sigma}* ratio reflect the local graphitic structure of carbon black.« less

Differential Sputtering Behavior of Pyrolytic Graphite and Carbon-Carbon Composite Under Xenon Bombardment

NASA Technical Reports Server (NTRS)

Williams, John D.; Johnson, Mark L.; Williams, Desiree D.

2003-01-01

A differential sputter yield measurement technique is described, which consists of a quartz crystal monitor that is swept at constant radial distance from a small target region where a high current density xenon ion beam is aimed. This apparatus has been used to characterize the sputtering behavior of various forms of carbon including polycrystalline graphite, pyrolytic graphite, and PVD-infiltrated and pyrolized carbon-carbon composites. Sputter yield data are presented for pyrolytic graphite and carbon-carbon composite over a range of xenon ion energies from 200 eV to 1 keV and angles of incidence from 0 deg (normal incidence) to 60 deg .

Electron reflection and secondary emission characteristics of sputter-textured pyrolytic graphite surfaces

NASA Technical Reports Server (NTRS)

Wintucky, E. G.; Curren, A. N.; Sovey, J. S.

1981-01-01

Low secondary and reflected primary electron emission from the collector electrode surfaces is important for optimum collector efficiency and hence for high overall efficiency of microwave amplifier tubes used in communication satellites and in military systems. Ion sputter texturing of the surface effectively suppresses electron emission from pyrolytic graphite, which is a promising collector electrode material. Secondary and reflected primary electron emission characteristics of sputter textured pyrolytic graphite surfaces with microstructures of various sizes and densities are presented. The microstructure with the lowest electron emission levels, less than those of soot, consists of a dense array of tall, thin spires.

Deducing 2D crystal structure at the liquid/solid interface with atomic resolution: a combined STM and SFG study.

PubMed

McClelland, Arthur A; Ahn, Seokhoon; Matzger, Adam J; Chen, Zhan

2009-11-17

Sum frequency generation vibrational spectroscopy (SFG) has been applied to study two-dimensional (2D) crystals formed by an isophthalic acid diester on the surface of highly oriented pyrolytic graphite, providing complementary measurements to scanning tunneling microscopy (STM) and computational modeling. SFG results indicate that both aromatic and C=O groups in the 2D crystal tilt from the surface. This study demonstrates that a combination of SFG and STM techniques can be used to gain a more complete picture of 2D crystal structure, and it is necessary to consider solvent-2D crystal interactions and dynamics in the computer models to achieve an accurate representation of interfacial structure.

Chiral symmetry breaking during the self-assembly of monolayers from achiral purine molecules.

PubMed

Sowerby, S J; Heckl, W M; Petersen, G B

1996-11-01

Scanning tunneling microscopy was used to investigate the structure of the two-dimensional adsorbate formed by molecular self-assembly of the purine base, adenine, on the surfaces of the naturally occurring mineral molybdenite and the synthetic crystal highly oriented pyrolytic graphite. Although formed from adenine, which is achiral, the observed adsorbate surface structures were enantiomorphic on molybdenite. This phenomenon suggests a mechanism for the introduction of a localized chiral symmetry break by the spontaneous crystallization of these prebiotically available molecules on inorganic surfaces and may have some role in the origin of biomolecular optical asymmetry. The possibility that purine-pyrimidine arrays assembled on naturally occurring mineral surfaces might act as possible templates for biomolecular assembly is discussed.

Self-assembled monolayers of shape-persistent macrocycles on graphite: interior design and conformational polymorphism.

PubMed

Vollmeyer, Joscha; Eberhagen, Friederike; Höger, Sigurd; Jester, Stefan-S

2014-01-01

Three shape-persistent naphthylene-phenylene-acetylene macrocycles of identical backbone structures and extraannular substitution patterns but different (empty, apolar, polar) nanopore fillings are self-assembled at the solid/liquid interface of highly oriented pyrolytic graphite and 1,2,4-trichlorobenzene. Submolecularly resolved images of the resulting two-dimensional (2D) crystalline monolayer patterns are obtained by in situ scanning tunneling microscopy. A concentration-dependent conformational polymorphism is found, and open and more dense packing motifs are observed. For all three compounds alike lattice parameters are found, therefore the intermolecular macrocycle distances are mainly determined by their size and symmetry. This is an excellent example that the graphite acts as a template for the macrocycle organization independent from their specific interior.

Structural Transformation of Guanine Coordination Motifs in Water Induced by Metal ions and Temperature.

PubMed

Li, Wei; Jin, Jing; Liu, Xiaoqing; Wang, Li

2018-06-15

The transformation effects of metal ions and temperature on the DNA bases guanine (G) metal-organic coordination motifs in water have been investigated by scanning tunneling microcopy (STM). The G molecules form an ordered hydrogen-bonded structure at the water- highly oriented pyrolytic graphite (HOPG) interface. The STM observations reveal that the canonical G/9H form can be transformed into the G/(3H, 7H) tautomer by increasing the temperature of the G solution to 38.6oC. Moreover, metal ions bind with G molecules to form G4Fe13+, G3Fe32+ and the heterochiral intermixed G4Na1+ metal-organic networks after the introduction of the alkali-metal ions in cellular environment.

Investigating the Co-Adsorption Behavior of Nucleic-Acid Base (Thymine and Cytosine) and Melamine at Liquid/Solid Interface

NASA Astrophysics Data System (ADS)

Zhao, Huiling; Li, Yinli; Chen, Dong; Liu, Bo

2016-12-01

The co-adsorption behavior of nucleic-acid base (thymine; cytosine) and melamine was investigated by scanning tunneling microscopy (STM) technique at liquid/solid (1-octanol/graphite) interface. STM characterization results indicate that phase separation happened after dropping the mixed solution of thymine-melamine onto highly oriented pyrolytic graphite (HOPG) surface, while the hetero-component cluster-like structure was observed when cytosine-melamine binary assembly system is used. From the viewpoints of non-covalent interactions calculated by using density functional theory (DFT) method, the formation mechanisms of these assembled structures were explored in detail. This work will supply a methodology to design the supramolecular assembled structures and the hetero-component materials composed by biological and chemical compound.

Nanoscale multiple gaseous layers on a hydrophobic surface.

PubMed

Zhang, Lijuan; Zhang, Xuehua; Fan, Chunhai; Zhang, Yi; Hu, Jun

2009-08-18

The nanoscale gas state at the interfaces of liquids (water, acid, and salt solutions) and highly oriented pyrolytic graphite (HOPG) was investigated via tapping-mode atomic force microscopy (AFM). For the first time, we report that the interfacial gases could form bilayers and trilayers, i.e., on the top of a flat gas layer, there are one or two more gas layers. The formation of these gas layers could be induced by a local supersaturation of gases, which can be achieved by (1) temperature difference between the liquids and the HOPG substrates or (2) exchange ethanol with water. Furthermore, we found that the gas layers were less stable than spherical bubbles. They could transform to bubbles with time or under the perturbation of the AFM tip.

Pyrolytic product characteristics of biosludge from the wastewater treatment plant of a petrochemical industry.

PubMed

Lin, Kuo-Hsiung; Hsu, Hui-Tsung; Ko, Ya-Wen; Shieh, Zhu-Xin; Chiang, Hung-Lung

2009-11-15

Biosludge was produced from the wastewater treatment plant of a petrochemical industry. The element compositions of pyrolytic residues, CO, CO(2), NOx, SOx, total hydrocarbons and detailed volatile organic compounds of pyrolytic gas, and C, H, N, S content and compositions in biofuel were determined in this study. Generally, 75-80% water content in sludge cakes and about 65-70% weight of water vapor and volatile compounds were volatilized during the drying process. Propene, propane, 1-butene, n-butane, isobutene, toluene and benzene were the major volatile organic compounds (VOCs) of the pyrolytic gas, and the concentrations for most of the top 20 VOC species were greater than 5 ppm. C(5)-C(9) compounds contributed 60% by weight of biofuel; 4-hydroxy-4-methyl-2-pentanone was the highest species, accounting for 28-53% of biofuel at various pyrolytic temperatures. Based on the dried residues, there was 8.5-13% weight in pyrolytic residues, 62-82% weight in liquid products (water and crude oil) and 5.8-30% weight in the gas phase after pyrolytic processing at 500-800 degrees C. Finally, 1.5-2.5 wt% liquid fuel was produced after the distillation process. The pyrolytic residues could be reused, the pyrolytic liquid product could be used as a fuel after distillation, and the pyrolytic gas could be recycled in the pyrolytic process to achieve non-toxic discharge and reduce the cost of sludge disposal.

Deposition of an Ultraflat Graphene Oxide Nanosheet on Atomically Flat Substrates

NASA Astrophysics Data System (ADS)

Khan, M. Z. H.; Shahed, S. M. F.; Yuta, N.; Komeda, T.

2017-07-01

In this study, graphene oxide (GO) sheets produced in the form of stable aqueous dispersions were deposited on Au (111), freshly cleaved mica, and highly oriented pyrolytic graphite (HOPG) substrates. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to study the presence and distinct contact of GO sheets on the substrates. It was revealed from the topography images that high-quality ultraflat GO monolayer sheets formed on the substrates without distinct cracking/wrinkling or folding. GO sheets with apparent height variation observed by microscopy also indicate ultraflat deposition with clear underlying steps. It was observed that ultrasonication and centrifuge steps prior to deposition were very effective for getting oxidation debris (OD)-free ultraflat single monolayer GO nanosheets onto substrates and that the process depends on the concentration of supplied GO solutions.

Characterization of submonolayer film composed of soft-landed copper nanoclusters on HOPG

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mondal, Shyamal, E-mail: shyamal.mondal@saha.ac.in; Das, Pabitra; Chowdhury, Debasree

Preformed Copper nanoclusters are deposited on highly oriented pyrolytic graphite (HOPG) at very low energy. For the study of chemical composition X-ray Photoelectron Spectroscopy (XPS) is performed for a wide range of binding energy without exposing the sample in the ambient. Morphological aspects of the supported clusters are characterized employing high resolution scanning electron microscope (SEM). Different types of morphology are observed depending on the nature of the substrate surface. Big fractal islands are formed on terraces while at the step edges small islands are found to form. Ex-situ cathodoluminescence (CL) measurement shows peak at 558 nm wavelength which corresponds tomore » the band gap of 2.22 eV which is due to Cu{sub 2}O nanocrystals formed due to oxidation of the deposited film in ambient.« less

Molecular and electronic structure of thin films of protoporphyrin(IX)Fe(III)Cl

NASA Astrophysics Data System (ADS)

Snyder, Shelly R.; White, Henry S.

1991-11-01

Electrochemical, scanning tunneling microscopy (STM), and tunneling spectroscopy studies of the molecular and electronic properties of thin films of protoporphyrin(IX)Fe(III)Cl (abbreviated as PP(IX)Fe(III)Cl) on highly oriented pyrolytic graphite (HOPG) electrodes are reported. PP(IX)Fe(III)Cl films are prepared by two different methods: (1) adsorption, yielding an electrochemically-active film, and (2) irreversible electrooxidative polymerization, yielding an electrochemically-inactive film. STM images, in conjunction with electro-chemical results, indicate that adsorption of PP(IX)Fe(III)Cl from aqueous solutions onto freshly cleaved HOPG results in a film comprised of molecular aggregates. In contrast, films prepared by irreversible electrooxidative polymerization of PP(IX)Fe(III)Cl have a denser, highly structured morphology, including what appear to be small pinholes (approx. 50A diameter) in an otherwise continuous film.

X-ray photoelectron spectroscopic and morphologic studies of Ru nanoparticles deposited onto highly oriented pyrolytic graphite

NASA Astrophysics Data System (ADS)

Bavand, R.; Yelon, A.; Sacher, E.

2015-11-01

Ruthenium nanoparticles (Ru NPs) function as effective catalysts in specific reactions, such as methanation and Fischer-Tropsch syntheses. It is our purpose to physicochemically characterize their surfaces, at which catalysis occurs, by surface-sensitive X-ray photoelectron spectroscopy (XPS), using the symmetric peak component anaylsis technique developed in our laboratory to reveal previously hidden components. Ru NPs were deposited by evaporation (0.25-1.5 nm nominal deposition range) onto highly oriented pyrolytic graphite (HOPG). In addition to their surfaces being characterized by XPS, an indication of morphology was obtained from transmission electron microscopy (TEM). Our use of symmetric peak component XPS analysis has revealed detailed information on a previously unidentified surface oxide initially formed, as well as on the valence electronic structure and its variation with NP size, information that is of potential importance in the use of these NPs in catalysis. Each of the several Ru core XPS spectra characterized (3d, 3p and 3s) was found to be composed of three symmetric components. Together with two metal oxide O1s components, these give evidence of a rather complex, previously unidentified oxide that is initially formed. The Ru valence band (4d and 5s) spectra clearly demonstrate a loss of metallicity, a simultaneous increase of the Kubo gap, and an abrupt transfer in valence electron density from the 4d to the 5s orbitals (known as electron spill-over), as the NP size decreases below 0.5 nm. TEM photomicrographs, as a function of deposition rate, show that, at a rate that gives insufficient time for the NP condensation energy to dissipate, the initially well-separated NPs are capable of diffusing laterally and aggregating. This indicates weak NP bonding to the HOPG substrate. Carbide is formed, at both high and low deposition rates, at Ru deposition thicknesses greater than 0.25 nm, its formation explained by Ru NPs reacting with residual hydrocarbon vapor, under the influence of the heat of condensation released on Ru deposition, and not by Ru reacting with the HOPG substrate.

Identification and thermochemical analysis of high-lignin feedstocks for biofuel and biochemical production

PubMed Central

2011-01-01

Background Lignin is a highly abundant biopolymer synthesized by plants as a complex component of plant secondary cell walls. Efforts to utilize lignin-based bioproducts are needed. Results Herein we identify and characterize the composition and pyrolytic deconstruction characteristics of high-lignin feedstocks. Feedstocks displaying the highest levels of lignin were identified as drupe endocarp biomass arising as agricultural waste from horticultural crops. By performing pyrolysis coupled to gas chromatography-mass spectrometry, we characterized lignin-derived deconstruction products from endocarp biomass and compared these with switchgrass. By comparing individual pyrolytic products, we document higher amounts of acetic acid, 1-hydroxy-2-propanone, acetone and furfural in switchgrass compared to endocarp tissue, which is consistent with high holocellulose relative to lignin. By contrast, greater yields of lignin-based pyrolytic products such as phenol, 2-methoxyphenol, 2-methylphenol, 2-methoxy-4-methylphenol and 4-ethyl-2-methoxyphenol arising from drupe endocarp tissue are documented. Conclusions Differences in product yield, thermal decomposition rates and molecular species distribution among the feedstocks illustrate the potential of high-lignin endocarp feedstocks to generate valuable chemicals by thermochemical deconstruction. PMID:22018114

Intrinsic activation: the relationship between biomass inorganic content and porosity formation during pyrolysis.

PubMed

Stratford, James P; Hutchings, Tony R; de Leij, Frans A A M

2014-05-01

The utility of pyrolytic carbons is closely related to their porosity and surface area, there is a clear benefit to the development of biomass pyrolysis processes which produce highly porous carbons. The results presented in this work demonstrate that by using biomass precursors with high inorganic content along with specified process conditions, carbons can be consistently produced with specific surface areas between 900 and 1600 m(2)/g. Results from 12 different source materials show that the formation of increased porosity in pyrolytic carbons is strongly associated with the presence of inorganic elements in the precursors including: magnesium, potassium and sulfur. It was found that pyrolysis of macro-algae can produce especially high specific surface area carbons (mean: 1500 m(2)/g), without externally applied activating agents. Using cheap readily available agricultural residues such as oilseed rape straw, pyrolytic carbons can be produced with specific surface areas of around 950 m(2)/g. Copyright © 2014 Elsevier Ltd. All rights reserved.

High repetition pump-and-probe photoemission spectroscopy based on a compact fiber laser system.

PubMed

Ishida, Y; Otsu, T; Ozawa, A; Yaji, K; Tani, S; Shin, S; Kobayashi, Y

2016-12-01

The paper describes a time-resolved photoemission (TRPES) apparatus equipped with a Yb-doped fiber laser system delivering 1.2-eV pump and 5.9-eV probe pulses at the repetition rate of 95 MHz. Time and energy resolutions are 11.3 meV and ∼310 fs, respectively, the latter is estimated by performing TRPES on a highly oriented pyrolytic graphite (HOPG). The high repetition rate is suited for achieving high signal-to-noise ratio in TRPES spectra, thereby facilitating investigations of ultrafast electronic dynamics in the low pump fluence (p) region. TRPES of polycrystalline bismuth (Bi) at p as low as 30 nJ/mm 2 is demonstrated. The laser source is compact and is docked to an existing TRPES apparatus based on a 250-kHz Ti:sapphire laser system. The 95-MHz system is less prone to space-charge broadening effects compared to the 250-kHz system, which we explicitly show in a systematic probe-power dependency of the Fermi cutoff of polycrystalline gold. We also describe that the TRPES response of an oriented Bi(111)/HOPG sample is useful for fine-tuning the spatial overlap of the pump and probe beams even when p is as low as 30 nJ/mm 2 .

Friction and transfer behavior of pyrolytic boron nitride in contact with various metals

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1976-01-01

Sliding friction experiments were conducted with pyrolytic boron nitride in sliding contact with itself and various metals. Auger emission spectroscopy was used to monitor transfer of pyrolytic boron nitride to metals and metals to pyrolytic boron nitride. Results indicate that the friction coefficient for pyrolytic boron nitride in contact with metals can be related to the chemical activity of the metals and more particularly to the d valence bond character of the metal. Transfer was found to occur to all metals except silver and gold and the amount of transfer was less in the presence than in the absence of metal oxide. Friction was less for pyrolytic boron nitride in contact with a metal in air than in vacuum.

Atomic force microscope characterization of self-assembly behaviors of cyclo[8] pyrrole on solid substrates

NASA Astrophysics Data System (ADS)

Xu, Hai; Zhao, Siqi; Xiong, Xiang; Jiang, Jinzhi; Xu, Wei; Zhu, Daoben; Zhang, Yi; Liang, Wenjie; Cai, Jianfeng

2017-04-01

Cyclo [8] pyrrole (CP) is a porphyrin analogue containing eight α-conjugated pyrrole units which are arranged in a nearly coplanar conformation. The π-π interactions between CP molecules lead to regular aggregations through a solution casting process. Using tapping mode atomic force microscope (AFM), we investigated the morphology of self-assembled aggregates formed by deposition of different CP solutions on different substrates. We found that in the n-butanol solution, nanofibrous structures could be formed on the silicon or mica surface. Interestingly, on the highly oriented pyrolytic graphite (HOPG) surface, or silicon and mica surface with a toluene solution, only irregular spherical structures were identified. The difference in the nanomorphology may be attributed to distinct interactions between molecule-molecule, molecule-solvent and molecule-substrate.

[AFM fishing of proteins under impulse electric field].

PubMed

Ivanov, Yu D; Pleshakova, T O; Malsagova, K A; Kaysheva, A L; Kopylov, A T; Izotov, A A; Tatur, V Yu; Vesnin, S G; Ivanova, N D; Ziborov, V S; Archakov, A I

2016-05-01

A combination of (atomic force microscopy)-based fishing (AFM-fishing) and mass spectrometry allows to capture protein molecules from solutions, concentrate and visualize them on an atomically flat surface of the AFM chip and identify by subsequent mass spectrometric analysis. In order to increase the AFM-fishing efficiency we have applied pulsed voltage with the rise time of the front of about 1 ns to the AFM chip. The AFM-chip was made using a conductive material, highly oriented pyrolytic graphite (HOPG). The increased efficiency of AFM-fishing has been demonstrated using detection of cytochrome b5 protein. Selection of the stimulating pulse with a rise time of 1 ns, corresponding to the GHz frequency range, by the effect of intrinsic emission from water observed in this frequency range during water injection into the cell.

Femtosecond laser ablation of highly oriented pyrolytic graphite: a green route for large-scale production of porous graphene and graphene quantum dots

NASA Astrophysics Data System (ADS)

Russo, Paola; Hu, Anming; Compagnini, Giuseppe; Duley, Walter W.; Zhou, Norman Y.

2014-01-01

Porous graphene (PG) and graphene quantum dots (GQDs) are attracting attention due to their potential applications in photovoltaics, catalysis, and bio-related fields. We present a novel way for mass production of these promising materials. The femtosecond laser ablation of highly oriented pyrolytic graphite (HOPG) is employed for their synthesis. Porous graphene (PG) layers were found to float at the water-air interface, while graphene quantum dots (GQDs) were dispersed in the solution. The sheets consist of one to six stacked layers of spongy graphene, which form an irregular 3D porous structure that displays pores with an average size of 15-20 nm. Several characterization techniques have confirmed the porous nature of the collected layers. The analyses of the aqueous solution confirmed the presence of GQDs with dimensions of about 2-5 nm. It is found that the formation of both PG and GQDs depends on the fs-laser ablation energy. At laser fluences less than 12 J cm-2, no evidence of either PG or GQDs is detected. However, polyynes with six and eight carbon atoms per chain are found in the solution. For laser energies in the 20-30 J cm-2 range, these polyynes disappeared, while PG and GQDs were found at the water-air interface and in the solution, respectively. The origin of these materials can be explained based on the mechanisms for water breakdown and coal gasification. The absence of PG and GQDs, after the laser ablation of HOPG in liquid nitrogen, confirms the proposed mechanisms.Porous graphene (PG) and graphene quantum dots (GQDs) are attracting attention due to their potential applications in photovoltaics, catalysis, and bio-related fields. We present a novel way for mass production of these promising materials. The femtosecond laser ablation of highly oriented pyrolytic graphite (HOPG) is employed for their synthesis. Porous graphene (PG) layers were found to float at the water-air interface, while graphene quantum dots (GQDs) were dispersed in the solution. The sheets consist of one to six stacked layers of spongy graphene, which form an irregular 3D porous structure that displays pores with an average size of 15-20 nm. Several characterization techniques have confirmed the porous nature of the collected layers. The analyses of the aqueous solution confirmed the presence of GQDs with dimensions of about 2-5 nm. It is found that the formation of both PG and GQDs depends on the fs-laser ablation energy. At laser fluences less than 12 J cm-2, no evidence of either PG or GQDs is detected. However, polyynes with six and eight carbon atoms per chain are found in the solution. For laser energies in the 20-30 J cm-2 range, these polyynes disappeared, while PG and GQDs were found at the water-air interface and in the solution, respectively. The origin of these materials can be explained based on the mechanisms for water breakdown and coal gasification. The absence of PG and GQDs, after the laser ablation of HOPG in liquid nitrogen, confirms the proposed mechanisms. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr05572h

Low-noise humidity controller for imaging water mediated processes in atomic force microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaponenko, I., E-mail: iaroslav.gaponenko@unige.ch; Gamperle, L.; Herberg, K.

2016-06-15

We demonstrate the construction of a novel low-noise continuous flow humidity controller and its integration with a commercial variable-temperature atomic force microscope fluid cell, allowing precise control of humidity and temperature at the sample during nanoscale measurements. Based on wet and dry gas mixing, the design allows a high mechanical stability to be achieved by means of an ultrasonic atomiser for the generation of water-saturated gas, improving upon previous bubbler-based architectures. Water content in the flow is measured both at the inflow and outflow of the fluid cell, enabling the monitoring of water condensation and icing, and allowing controlled variationmore » of the sample temperature independently of the humidity. To benchmark the performance of the controller, the results of detailed noise studies and time-based imaging of the formation of ice layers on highly oriented pyrolytic graphite are shown.« less

Graphene Nanobubbles Produced by Water Splitting.

PubMed

An, Hongjie; Tan, Beng Hau; Moo, James Guo Sheng; Liu, Sheng; Pumera, Martin; Ohl, Claus-Dieter

2017-05-10

Graphene nanobubbles are of significant interest due to their ability to trap mesoscopic volumes of gas for various applications in nanoscale engineering. However, conventional protocols to produce such bubbles are relatively elaborate and require specialized equipment to subject graphite samples to high temperatures or pressures. Here, we demonstrate the formation of graphene nanobubbles between layers of highly oriented pyrolytic graphite (HOPG) with electrolysis. Although this process can also lead to the formation of gaseous surface nanobubbles on top of the substrate, the two types of bubbles can easily be distinguished using atomic force microscopy. We estimated the Young's modulus, internal pressure, and the thickness of the top membrane of the graphene nanobubbles. The hydrogen storage capacity can reach ∼5 wt % for a graphene nanobubble with a membrane that is four layers thick. The simplicity of our protocol paves the way for such graphitic nanobubbles to be utilized for energy storage and industrial applications on a wide scale.

Graphite, graphene and the flat band superconductivity

NASA Astrophysics Data System (ADS)

Volovik, G. E.

2018-04-01

Superconductivity has been observed in bilayer graphene [1,2]. The main factor, which determines the mechanism of the formation of this superconductivity is the "magic angle" of twist of two graphene layers, at which the electronic band structure becomes nearly flat. The specific role played by twist and by the band flattening, has been earlier suggested for explanations of the signatures of room-temperature superconductivity observed in the highly oriented pyrolytic graphite (HOPG), when the quasi two-dimensional interfaces between the twisted domains are present. The interface contains the periodic array of misfit dislocations (analogs of the boundaries of the unit cell of the Moire superlattice in bilayer graphene), which provide the possible source of the flat band. This demonstrates that it is high time for combination of the theoretical and experimental efforts in order to reach the reproducible room-temperature superconductivity in graphite or in similar real or artificial materials.

A low-temperature scanning tunneling microscope capable of microscopy and spectroscopy in a Bitter magnet at up to 34 T.

PubMed

Tao, W; Singh, S; Rossi, L; Gerritsen, J W; Hendriksen, B L M; Khajetoorians, A A; Christianen, P C M; Maan, J C; Zeitler, U; Bryant, B

2017-09-01

We present the design and performance of a cryogenic scanning tunneling microscope (STM) which operates inside a water-cooled Bitter magnet, which can attain a magnetic field of up to 38 T. Due to the high vibration environment generated by the magnet cooling water, a uniquely designed STM and a vibration damping system are required. The STM scan head is designed to be as compact and rigid as possible, to minimize the effect of vibrational noise as well as fit the size constraints of the Bitter magnet. The STM uses a differential screw mechanism for coarse tip-sample approach, and operates in helium exchange gas at cryogenic temperatures. The reliability and performance of the STM are demonstrated through topographic imaging and scanning tunneling spectroscopy on highly oriented pyrolytic graphite at T = 4.2 K and in magnetic fields up to 34 T.

Influence of carbonization conditions on the pyrolytic carbon deposition in acacia and eucalyptus wood chars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, M.; Gupta, R.C.

1997-04-01

The amount of deposited pyrolytic carbon (resulting from the cracking of volatile matter) was found to depend on wood species and carbonization conditions, such as temperature and heating rate. Maximum pyrolytic carbon deposition in both the acacia and eucalyptus wood chars has been observed at a carbonization temperature of 800 C. Rapid carbonization (higher heating rate) of wood significantly reduces the amount of deposited pyrolytic carbon in resulting chars. Results also indicate that the amount of deposited pyrolytic carbon in acacia wood char is less than that in eucalyptus wood char.

Production and characterization of pyrolytic oils by pyrolysis of waste machinery oil.

PubMed

Sinağ, Ali; Gülbay, Selen; Uskan, Burçin; Uçar, Suat; Ozgürler, Sara Bilge

2010-01-15

The main objective of this work is to propose an alternative method for evaluation of the waste machinery oil which is an environmental problem in Turkey. For this purpose, pyrolysis of waste machinery oil was conducted in a tubular reactor. Effect of the experimental conditions (various temperatures, catalyst type) on the formation of pyrolytic oil, gas, and char was investigated. Nickel supported on silica and zeolite (HZSM-5) were used as catalysts. Properties of the pyrolytic oils were characterized by gas chromatograph equipped with a mass selective detector (GC-MS), gas chromatography with flame ionization detector (GC-FID for boiling point range distribution), nuclear magnetic resonance ((1)H NMR) spectroscopy, higher heating value measurement, and elemental analysis. The behavior of the metals in the waste machinery oil and the pyrolytic oil samples was also quantitatively detected by inductively coupled plasma (ICP) analysis. As, Cd and Cr contents of the all pyrolytic oils were found as <0.05 ppm, while Cu content of the pyrolytic oils varied between 0.3 ppm and 0.61 ppm. Only Vanadium contents of the pyrolytic oils obtained at 800 degrees C (0.342 ppm) and in the presence of HZSM5 (0.57 ppm) increased compared to that obtained by waste machinery oil (0.1 ppm). Lower metal contents of the pyrolytic oils reveal that pyrolysis of the waste machinery oils leads to the formation of environmental friendly pyrolytic oils with higher heating values.

Metal dependent motif transition in a self-assembled monolayer of bipyridine derivatives via coordination: An STM study.

PubMed

Wang, Yi; Yuan, Qunhui; Xu, Hongbo; Zhu, Xuefeng; Gan, Wei

2016-07-21

Low-dimensional molecular motifs with diversity developed via the on-surface chemistry are attracting growing interest for their potential in advanced nanofabrication. In this work, scanning tunneling microscopy was employed to investigate the in situ and ex situ metal coordinations between 4,4'-ditetradecyl-2,2'-bipyridine (bpy) and Zn(ii) or Cu(ii) ions at a highly oriented pyrolytic graphite (HOPG)/1-phenyloctane interface under ambient conditions. The results demonstrate that the bpy adopts a flat-lying orientation with its substituted alkyl chains in a tail-to-tail arrangement in a bpy monolayer. For the in situ coordination, the bpy/Zn(ii) and bpy/Cu(ii) complexes are aligned in edge-on fashions, wherein the bpy stands vertically on the HOPG surface and interdigitates at the alkyl chains. In the two-dimensional arrays of ex situ coordinated complexes, metal dependent motifs have been observed with Zn(ii) and Cu(ii), wherein the bipyridine moieties are parallel to the graphite surface. These results suggest that the desired on-surface coordination architectures may be achieved by the intentional selection of the metal centers.

Toward tunable doping in graphene FETs by molecular self-assembled monolayers

NASA Astrophysics Data System (ADS)

Li, Bing; Klekachev, Alexander V.; Cantoro, Mirco; Huyghebaert, Cedric; Stesmans, André; Asselberghs, Inge; de Gendt, Stefan; de Feyter, Steven

2013-09-01

In this paper, we report the formation of self-assembled monolayers (SAMs) of oleylamine (OA) on highly oriented pyrolytic graphite (HOPG) and graphene surfaces and demonstrate the potential of using such organic SAMs to tailor the electronic properties of graphene. Molecular resolution Atomic Force Microscopy (AFM) and Scanning Tunneling Microscopy (STM) images reveal the detailed molecular ordering. The electrical measurements show that OA strongly interacts with graphene leading to n-doping effects in graphene devices. The doping levels are tunable by varying the OA deposition conditions. Importantly, neither hole nor electron mobilities are decreased by the OA modification. As a benefit from this noncovalent modification strategy, the pristine characteristics of the device are recoverable upon OA removal. From this study, one can envision the possibility to correlate the graphene-based device performance with the molecular structure and supramolecular ordering of the organic dopant.In this paper, we report the formation of self-assembled monolayers (SAMs) of oleylamine (OA) on highly oriented pyrolytic graphite (HOPG) and graphene surfaces and demonstrate the potential of using such organic SAMs to tailor the electronic properties of graphene. Molecular resolution Atomic Force Microscopy (AFM) and Scanning Tunneling Microscopy (STM) images reveal the detailed molecular ordering. The electrical measurements show that OA strongly interacts with graphene leading to n-doping effects in graphene devices. The doping levels are tunable by varying the OA deposition conditions. Importantly, neither hole nor electron mobilities are decreased by the OA modification. As a benefit from this noncovalent modification strategy, the pristine characteristics of the device are recoverable upon OA removal. From this study, one can envision the possibility to correlate the graphene-based device performance with the molecular structure and supramolecular ordering of the organic dopant. Electronic supplementary information (ESI) available: AFM images of self-assembled monolayers of OA on HOPG; AFM height image of the graphene surface on a SiC substrate; high resolution STM image of a self-assembled monolayer of OA on HOPG; transfer curves of a graphene FET with and without baking steps; transfer curves of a graphene FET under high vacuum conditions; transfer curves of a graphene FET and its Raman response before and after OA treatment; transfer curves of a graphene FET before and after rinsing with n-hexane. See DOI: 10.1039/c3nr01255g

Photodeposition of Gold, Platinum, or Silver onto Titanium Dioxide Nanoparticles at Steps of Highly Oriented Pyrolytic Graphite

NASA Astrophysics Data System (ADS)

Taing, James

The photodeposition of gold, platinum, or silver nanoparticles selectively onto isolated titanium dioxide (TiO2) nanoparticles created metal/TiO2 photocatalysts and heterogeneous catalysts, and validated the photocatalytic property of the semiconductor. The isolated and ordered TiO2 nanoparticles permitted clear observations of the stability, and changes in morphology, of the particles in various experimental conditions. The fabrication of TiO2 nanoparticles at the steps of highly oriented pyrolytic graphite (HOPG), utilizing physical vapor deposition, required heating the graphite substrate to a minimum of 800 °C. The production of a photocurrent, and plating of gold nanoparticles, confirmed the photocatalytic property of the TiO2 nanoparticles on HOPG when utilized as a photoelectrode in a two half-cell setup. Employing sodium chloride (1.0 M) as an electrolyte resulted in an increase/decrease of the photocurrent with the addition of gold cations to the half-cell without/with the TiO2 nanoparticles. A poor distribution of gold nanoparticles, roughly 40-45 nm wide, deposited around few of the TiO2 nanoparticles. A lower concentration of sodium chloride (0.1 M) resulted in a coalescence of Au nanoparticles, roughly 10 nm, around many TiO2 nanoparticles. Using sodium nitrate as an electrolyte resulted in a rapid decay in the photocurrent and a growth of an unidentified material on the TiO2 nanoparticles. The unidentified material hindered the reduction of gold cations introduced midway through the experiment. With gold cations present at the onset of the experiment, disperse gold nanoparticles (˜5-10 nm) deposited around the TiO2 nanoparticles. In the absence of additional electrolyte, many disperse gold nanoparticles less than 5 nm deposited onto the TiO2 nanoparticles. More platinum than gold selectively deposited onto the TiO2 nanoparticles. On the contrary, less silver selectively deposited onto the TiO2 nanoparticles. Scanning electron microscopy and atomic force microscopy determined the morphology and distribution of the TiO2 nanoparticles and metal/TiO 2 nanocomposites. Energy dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy identified the composition of the materials.

A comparative study of bio-oils from pyrolysis of microalgae and oil seed waste in a fluidized bed.

PubMed

Kim, Sung Won; Koo, Bon Seok; Lee, Dong Hyun

2014-06-01

The pyrolysis of Scenedesmus sp. and Jatropha seedshell cake (JSC) was investigated under similar operating condition in a fluidized bed reactor for comparison of pyrolytic behaviors from different species of lipids-containing biomass. Microalgae showed a narrower main peak in differential thermogravimetric curve compared to JSC due to different constituents. Pyrolysis liquid yields were similar; liquid's oil proportion of microalgae is higher than JSC. Microalgae bio-oil was characterized by similar carbon and hydrogen contents and higher H/C and O/C molar ratios compared to JSC due to compositional difference. The pyrolytic oils from microalgae and JSC contained more oxygen and nitrogen and less sulfur than petroleum and palm oils. The pyrolytic oils showed high yields of fatty oxygenates and nitrogenous compounds. The microalgae bio-oil features in high concentrations of aliphatic compounds, fatty acid alkyl ester, alcohols and nitriles. Microalgae showed potentials for alternative feedstock for green diesel, and commodity and valuable chemicals. Copyright © 2014 Elsevier Ltd. All rights reserved.

Pyrolytic Synthesis of Carbon Nanotubes from Sucrose on a Mesoporous Silicate

NASA Technical Reports Server (NTRS)

Abdel-Fattah, Tarek; Siochi, Mia; Crooks, Roy

2005-01-01

Multiwall carbon nanotubes were synthesized from sucrose by a pyrolytic technique using mesoporous MCM-41 silicate templates without transition metal catalysts. The Nanotubes were examined in the carbon/silicate composite and after dissolution of the silicate. High resolution transmission electron microscopy study of the multiwall nanotubes showed them to be 15 nm in diameter, 200 nm in length and close-ended. There was variation in crystallinity with some nanotubes showing disordered wall structures.

Analysis of the substrate influence on the ordering of epitaxial molecular layers: The special case of point-on-line coincidence

NASA Astrophysics Data System (ADS)

Mannsfeld, S. C.; Fritz, T.

2004-02-01

The physical structure of organic-inorganic heteroepitaxial thin films is usually governed by a fine balance between weak molecule-molecule interactions and a weakly laterally varying molecule-substrate interaction potential. Therefore, in order to investigate the energetics of such a layer system one has to consider large molecular domains. So far, layer potential calculations for large domains of organic thin films on crystalline substrates were difficult to perform concerning the computational effort which stems from the vast number of atoms which have to be included. Here, we present a technique which enables the calculation of the molecule-substrate interaction potential for large molecular domains by utilizing potential energy grid files. This technique allows the investigation of the substrate influence in systems prepared by organic molecular beam epitaxy (OMBE), like 3,4,9,10-perylenetetracarboxylicdianhydride on highly oriented pyrolytic graphite. For this system the so-called point-on-line coincidence was proposed, a growth mode which has been controversially discussed in literature. Furthermore, we are able to provide evidence for a general energetic advantage of such point-on-line coincident domain orientations over arbitrarily oriented domains which substantiates that energetically favorable lattice structures in OMBE systems are not restricted to commensurate unit cells or coincident super cells.

Catalytic fast pyrolysis of biomass impregnated with potassium phosphate in a hydrogen atmosphere for the production of phenol and activated carbon

NASA Astrophysics Data System (ADS)

Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

2018-02-01

A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550 oC in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1605 m2/g.

Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon

PubMed Central

Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

2018-01-01

A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1,605 m2/g. PMID:29515994

Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon.

PubMed

Lu, Qiang; Zhang, Zhen-Xi; Wang, Xin; Guo, Hao-Qiang; Cui, Min-Shu; Yang, Yong-Ping

2018-01-01

A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K 3 PO 4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K 3 PO 4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K 3 PO 4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO 2 activation method, the specific surface area was as high as 1,605 m 2 /g.

Fabrication of bi-layer graphene and theoretical simulation for its possible application in thin film solar cell.

PubMed

Behura, Sanjay K; Mahala, Pramila; Nayak, Sasmita; Yang, Qiaoqin; Mukhopadhyay, Indrajit; Janil, Omkar

2014-04-01

High quality graphene film is fabricated using mechanical exfoliation of highly-oriented pyrolytic graphite. The graphene films on glass substrates are characterized using field-emission scanning electron microscopy, atomic force microscopy, Raman spectroscopy, UV-vis spectroscopy and Fourier transform infrared spectroscopy. A very high intensity ratio of 2D to G-band (to approximately 1.67) and narrow 2D-band full-width at half maximum (to approximately 40 cm(-1)) correspond to the bi-layer graphene formation. The bi-layer graphene/p-GaN/n-InGaN/n-GaN/GaN/sAl2O3 system is studied theoretically using TCAD Silvaco software, in which the properties of exfoliated bi-layer graphene are used as transparent and conductive film, and the device exhibits an efficiency of 15.24% compared to 13.63% for ITO/p-GaN/n-InGaN/n-GaN/GaN/Al2O3 system.

High translational energy release in H2 (D2) associative desorption from H (D) chemisorbed on C(0001).

PubMed

Baouche, S; Gamborg, G; Petrunin, V V; Luntz, A C; Baurichter, A; Hornekaer, L

2006-08-28

Highly energetic translational energy distributions are reported for hydrogen and deuterium molecules desorbing associatively from the atomic chemisorption states on highly oriented pyrolytic graphite (HOPG). Laser assisted associative desorption is used to measure the time of flight of molecules desorbing from a hydrogen (deuterium) saturated HOPG surface produced by atomic exposure from a thermal atom source at around 2100 K. The translational energy distributions normal to the surface are very broad, from approximately 0.5 to approximately 3 eV, with a peak at approximately 1.3 eV. The highest translational energy measured is close to the theoretically predicted barrier height. The angular distribution of the desorbing molecules is sharply peaked along the surface normal and is consistent with thermal broadening contributing to energy release parallel to the surface. All results are in qualitative agreement with recent density functional theory calculations suggesting a lowest energy para-type dimer recombination path.

Internal and external atomic steps in graphite exhibit dramatically different physical and chemical properties.

PubMed

Lee, Hyunsoo; Lee, Han-Bo-Ram; Kwon, Sangku; Salmeron, Miquel; Park, Jeong Young

2015-04-28

We report on the physical and chemical properties of atomic steps on the surface of highly oriented pyrolytic graphite (HOPG) investigated using atomic force microscopy. Two types of step edges are identified: internal (formed during crystal growth) and external (formed by mechanical cleavage of bulk HOPG). The external steps exhibit higher friction than the internal steps due to the broken bonds of the exposed edge C atoms, while carbon atoms in the internal steps are not exposed. The reactivity of the atomic steps is manifested in a variety of ways, including the preferential attachment of Pt nanoparticles deposited on HOPG when using atomic layer deposition and KOH clusters formed during drop casting from aqueous solutions. These phenomena imply that only external atomic steps can be used for selective electrodeposition for nanoscale electronic devices.

Imaging of subunit complexes of thermophilic bacterium H(+)-ATPase with scanning tunneling microscopy.

PubMed

Masai, J; Shibata, T; Kagawa, Y; Kondo, S

1992-07-01

Using a scanning tunneling microscope (STM), we observed reconstructed subunit complexes of H(+)-ATPase of a thermophilic bacterium. The measurement was carried out in air without conductive coating on the samples deposited on a highly oriented pyrolytic graphite (HOPG). The F1 subunit complex of the H(+)-ATPase, and an H(+)-ATPase whose F0 portion was embedded into liposomes prepared from soybean lecithin were imaged. Overall structural images of the subunit complex F1 were obtained: the structural dimensions of the STM images are in agreement with those deduced from conventional methods such as an transmission electron microscopy (TEM) and small-angle X-ray scattering (SAX) experimentation. Regarding the STM imaging of these samples, we discuss the advantages and disadvantages of the STM over those of conventional methods such as a TEM and SAX.

Self-assembled PCBM bilayers on graphene and HOPG examined by AFM and STM

NASA Astrophysics Data System (ADS)

Li, Yanlong; Chen, Chuanhui; Burton, John; Park, Kyungwha; Heflin, James R.; Tao, Chenggang

2018-05-01

In this work we report fabrication and characterization of phenyl-C61-butyric acid methyl ester (PCBM) bilayer structures on graphene and highly oriented pyrolytic graphite (HOPG). Through careful control of the PCBM solution concentration (from 0.1 to 2 mg ml-1) and the deposition conditions, we demonstrate that PCBM molecules self-assemble into bilayer structures on graphene and HOPG substrates. Interestingly, the PCBM bilayers are formed with two distinct heights on HOPG, but only one unique representative height on graphene. At elevated annealing temperatures, edge diffusion allows neighboring vacancies to merge into a more ordered structure. This is, to the best of our knowledge, the first experimental realization of PCBM bilayer structures on graphene. This work could provide valuable insight into fabrication of new hybrid, ordered structures for applications to organic solar cells.

Formation of Amorphous Carbon Nanoparticles by the Laser Electrodispersion Method

NASA Astrophysics Data System (ADS)

Gurevich, S. A.; Gorokhov, M. V.; Kozhevin, V. M.; Kukushkin, M. V.; Levitskii, V. S.; Markov, L. K.; Yavsin, D. A.

2018-03-01

Experimental results on the laser ablation of the highly oriented pyrolytic graphite by using light pulses of an Nd:YAG laser (pulse width 25 ns, pulse energy 220 mJ) are presented. Analysis of the surface profile of the carbon target shows that the target material melts in the course of the laser ablation. As a result of ablation, a coating consisting of carbon nanoparticles about 10 nm in size is formed on the substrate placed at a distance of 4 cm from the target. It is assumed that such particles are formed as a result of the electrodispersion of carbon droplets detached from the target surface and charged to an unstable state in the laser plasma plume. Raman spectra of the coatings indicate that the carbon nanoparticles being formed have an amorphous structure.

Self-assembled PCBM bilayers on graphene and HOPG examined by AFM and STM.

PubMed

Li, Yanlong; Chen, Chuanhui; Burton, John; Park, Kyungwha; Heflin, James R; Tao, Chenggang

2018-05-04

In this work we report fabrication and characterization of phenyl-C61-butyric acid methyl ester (PCBM) bilayer structures on graphene and highly oriented pyrolytic graphite (HOPG). Through careful control of the PCBM solution concentration (from 0.1 to 2 mg ml -1 ) and the deposition conditions, we demonstrate that PCBM molecules self-assemble into bilayer structures on graphene and HOPG substrates. Interestingly, the PCBM bilayers are formed with two distinct heights on HOPG, but only one unique representative height on graphene. At elevated annealing temperatures, edge diffusion allows neighboring vacancies to merge into a more ordered structure. This is, to the best of our knowledge, the first experimental realization of PCBM bilayer structures on graphene. This work could provide valuable insight into fabrication of new hybrid, ordered structures for applications to organic solar cells.

Nanospectroscopy of thiacyanine dye molecules adsorbed on silver nanoparticle clusters

NASA Astrophysics Data System (ADS)

Ralević, Uroš; Isić, Goran; Anicijević, Dragana Vasić; Laban, Bojana; Bogdanović, Una; Lazović, Vladimir M.; Vodnik, Vesna; Gajić, Radoš

2018-03-01

The adsorption of thiacyanine dye molecules on citrate-stabilized silver nanoparticle clusters drop-cast onto freshly cleaved mica or highly oriented pyrolytic graphite surfaces is examined using colocalized surface-enhanced Raman spectroscopy and atomic force microscopy. The incidence of dye Raman signatures in photoluminescence hotspots identified around nanoparticle clusters is considered for both citrate- and borate-capped silver nanoparticles and found to be substantially lower in the former case, suggesting that the citrate anions impede the efficient dye adsorption. Rigorous numerical simulations of light scattering on random nanoparticle clusters are used for estimating the electromagnetic enhancement and elucidating the hotspot formation mechanism. The majority of the enhanced Raman signal, estimated to be more than 90%, is found to originate from the nanogaps between adjacent nanoparticles in the cluster, regardless of the cluster size and geometry.

Pyrolytic-carbon coating in carbon nanotube foams for better performance in supercapacitors

NASA Astrophysics Data System (ADS)

He, Nanfei; Yildiz, Ozkan; Pan, Qin; Zhu, Jiadeng; Zhang, Xiangwu; Bradford, Philip D.; Gao, Wei

2017-03-01

Nowadays, the wide-spread adoption of supercapacitors has been hindered by their inferior energy density to that of batteries. Here we report the use of our pyrolytic-carbon-coated carbon nanotube foams as lightweight, compressible, porous, and highly conductive current collectors in supercapacitors, which are infiltrated with chemically-reduced graphene oxide and later compressed via mechanical and capillary forces to generate the active electrodes. The pyrolytic carbon coatings, introduced by chemical vapor infiltration, wrap around the CNT junctions and increase the surface roughness. When active materials are infiltrated, the pyrolytic-carbon coatings help prevent the π-stacking, enlarge the accessible surface area, and increase the electrical conductivity of the scaffold. Our best-performing device offers 48% and 57% higher gravimetric energy and power density, 14% and 23% higher volumetric energy and power density, respectively, and two times higher knee frequency, than the device with commercial current collectors, while the "true-performance metrics" are strictly followed in our measurements. We have further clarified the solution resistance, charge transfer resistance/capacitance, double-layer capacitance, and Warburg resistance in our system via comprehensive impedance analysis, which will shed light on the design and optimization of similar systems.

Method for fabricating thin films of pyrolytic carbon

DOEpatents

Brassell, G.W.; Lewis, J. Jr.; Weber, G.W.

1980-03-13

The present invention relates to a method for fabricating ultrathin films of pyrolytic carbon. Pyrolytic carbon is vapor deposited onto a concave surface of a heated substrate to a total uniform thickness in the range of about 0.1 to 1.0 micrometer. The carbon film on the substrate is provided with a layer of adherent polymeric resin. The resulting composite film of pyrolytic carbon and polymeric resin is then easily separated from the substrate by shrinking the 10 polymeric resin coating with thermally induced forces.

Method for fabricating thin films of pyrolytic carbon

DOEpatents

Brassell, Gilbert W.; Lewis, Jr., John; Weber, Gary W.

1982-01-01

The present invention relates to a method for fabricating ultra-thin films of pyrolytic carbon. Pyrolytic carbon is vapor deposited onto a concave surface of a heated substrate to a total uniform thickness in the range of about 0.1 to 1.0 micrometer. The carbon film on the substrate is provided with a layer of adherent polymeric resin. The resulting composite film of pyrolytic carbon and polymeric resin is then easily separated from the substrate by shrinking the polymeric resin coating with thermally induced forces.

Using sewage sludge pyrolytic gas to modify titanium alloy to obtain high-performance anodes in bio-electrochemical systems

NASA Astrophysics Data System (ADS)

Gu, Yuan; Ying, Kang; Shen, Dongsheng; Huang, Lijie; Ying, Xianbin; Huang, Haoqian; Cheng, Kun; Chen, Jiazheng; Zhou, Yuyang; Chen, Ting; Feng, Huajun

2017-12-01

Titanium is under consideration as a potential stable bio-anode because of its high conductivity, suitable mechanical properties, and electrochemical inertness in the operating potential window of bio-electrochemical systems; however, its application is limited by its poor electron-transfer capacity with electroactive bacteria and weak ability to form biofilms on its hydrophobic surface. This study reports an effective and low-cost way to convert a hydrophobic titanium alloy surface into a hydrophilic surface that can be used as a bio-electrode with higher electron-transfer rates. Pyrolytic gas of sewage sludge is used to modify the titanium alloy. The current generation, anodic biofilm formation surface, and hydrophobicity are systematically investigated by comparing bare electrodes with three modified electrodes. Maximum current density (15.80 A/m2), achieved using a modified electrode, is 316-fold higher than that of the bare titanium alloy electrode (0.05 A/m2) and that achieved by titanium alloy electrodes modified by other methods (12.70 A/m2). The pyrolytic gas-modified titanium alloy electrode can be used as a high-performance and scalable bio-anode for bio-electrochemical systems because of its high electron-transfer rates, hydrophilic nature, and ability to achieve high current density.

Aqueous alteration of VHTR fuels particles under simulated geological conditions

NASA Astrophysics Data System (ADS)

Ait Chaou, Abdelouahed; Abdelouas, Abdesselam; Karakurt, Gökhan; Grambow, Bernd

2014-05-01

Very High Temperature Reactor (VHTR) fuels consist of the bistructural-isotropic (BISO) or tristructural-isotropic (TRISO)-coated particles embedded in a graphite matrix. Management of the spent fuel generated during VHTR operation would most likely be through deep geological disposal. In this framework we investigated the alteration of BISO (with pyrolytic carbon) and TRISO (with SiC) particles under geological conditions simulated by temperatures of 50 and 90 °C and in the presence of synthetic groundwater. Solid state (scanning electron microscopy (SEM), micro-Raman spectroscopy, electron probe microanalyses (EPMA) and X-ray photoelectron spectroscopy (XPS)) and solution analyses (ICP-MS, ionique chromatography (IC)) showed oxidation of both pyrolytic carbon and SiC at 90 °C. Under air this led to the formation of SiO2 and a clay-like Mg-silicate, while under reducing conditions (H2/N2 atmosphere) SiC and pyrolytic carbon were highly stable after a few months of alteration. At 50 °C, in the presence and absence of air, the alteration of the coatings was minor. In conclusion, due to their high stability in reducing conditions, HTR fuel disposal in reducing deep geological environments may constitute a viable solution for their long-term management.

Integration of the ferromagnetic insulator EuO onto graphene.

PubMed

Swartz, Adrian G; Odenthal, Patrick M; Hao, Yufeng; Ruoff, Rodney S; Kawakami, Roland K

2012-11-27

We have demonstrated the deposition of EuO films on graphene by reactive molecular beam epitaxy in a special adsorption-controlled and oxygen-limited regime, which is a critical advance toward the realization of the exchange proximity interaction (EPI). It has been predicted that when the ferromagnetic insulator (FMI) EuO is brought into contact with graphene, an overlap of electronic wave functions at the FMI/graphene interface can induce a large spin splitting inside the graphene. Experimental realization of this effect could lead to new routes for spin manipulation, which is a necessary requirement for a functional spin transistor. Furthermore, EPI could lead to novel spintronic behavior such as controllable magnetoresistance, gate tunable exchange bias, and quantized anomalous Hall effect. However, experimentally, EuO has not yet been integrated onto graphene. Here we report the successful growth of high-quality crystalline EuO on highly oriented pyrolytic graphite and single-layer graphene. The epitaxial EuO layers have (001) orientation and do not induce an observable D peak (defect) in the Raman spectra. Magneto-optic measurements indicate ferromagnetism with a Curie temperature of 69 K, which is the value for bulk EuO. Transport measurements on exfoliated graphene before and after EuO deposition indicate only a slight decrease in mobility.

Structure and radical scavenging activity relationships of pyrolytic lignins

USDA-ARS?s Scientific Manuscript database

This work deals with antioxidant properties of pyrolytic lignins against two free radicals, the 1,1-diphenyl-2-picrylhydrazyl and the 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid). Pyrolytic lignins produced by the thermal pyrolysis of the Etek lignin were extracted from the liquid pyrolysi...

Structural Analysis of Pyrolytic Graphite Optics for the HiPEP Ion Thruster

NASA Technical Reports Server (NTRS)

Meckel, Nicole; Polaha, Jonathan; Juhlin, Nils

2006-01-01

The long lifetime requirements of interplanetary exploration missions is driving the need to develop long-life components for the electric propulsion thrusters that are being targeted for these missions. One of the primary life-limiting components of ion thrusters are the optics, which are continuously eroded during the operation of the thruster. Pyrolytic graphite optics are being considered for the High Power Electric Propulsion (HiPEP) ion thruster because of their very high resistance to erosion. This paper describes the structural analysis of the HiPEP pyrolytic graphite. A description of the development of the grid model, as well as the development of the effective properties and stress concentrations in the apertured area of the grids is included. An evaluation of the use of curved grids shows that the increased stiffness (compared to flat grids) prevents intergrid impact during launch, however, the residual stresses introduced by curving the grids pushes the resulting peak stresses beyond the critical stress. As a result, flat grids are recommended as the design solution. Thermally induced grid displacements during normal thruster operation are also presented.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liscio, A.; CNISM and Dipartimento di Fisica, Universita di Roma Tre, Via Vasca Navale 84, 00146 Roma; Ruocco, A.

This paper deals with the mechanism of grazing incidence (e,2e) events from surfaces. Two different approaches are considered. In both cases, elastic scattering with the crystal lattice assists the inelastic collision; these two steps are coupled either coherently or incoherently. Experimental evidence is given that the 'coherent' approach reproduces better the cross section dependence on momentum transfer in the specific case of asymmetric kinematics at moderate electron energies. This model has allowed us to map out the band dispersion of the outermost valence states of highly oriented pyrolytic graphite and to measure the momentum distribution of {pi}-electron states without invokingmore » the contribution of reciprocal lattice vectors in the momentum conservation. Agreement between theory and experiment is satisfactory, though the presence of events where crystal momentum is reconstructed cannot be ruled out. These results, obtained with a significant reduction of the experiment duration by an implemented apparatus, show that reflection (e,2e) can be used to build up a momentum spectroscopy with high surface sensitivity.« less

Scanning tunneling microscopy investigation of copper phthalocyanine and truxenone derivative binary superstructures on graphite.

PubMed

Liu, Jia; Wang, Dong; Wang, Jie-Yu; Pei, Jian; Wan, Li-Jun

2011-02-01

The binary self-assembly of copper phthalocyanine (CuPc) and 2,3,7,8,12,13-hexahexyloxy-truxenone (TrO23) at the solid/liquid interface of highly oriented pyrolytic graphite (HOPG) was investigated by using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Pseduohexagonal and linear patterned superstructures of CuPc are obtained by co-adsorbing with TrO23. High-resolution STM images reveal the structural details of the arrangement of TrO23 and CuPc in the binary assembly structures. The molecular ratio between CuPc and TrO23 in the adlayer can be modulated by the CuPc concentration in liquid phase. The electronic properties of CuPc and TrO23 in the co-adsorbed self-assembly are investigated by STS. The results presented here are helpful to the design and fabrication of multi-component functional molecular nanostructures. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Addressing individual metal ion centers in supramolecules by STS

NASA Astrophysics Data System (ADS)

Alam, M. S.; Ako, A. M.; Ruben, M.; Thompson, L. K.; Lehn, J.-M.

2005-03-01

As the information of STM measurements arises from electronic structure, separating information on the topography is not straightforward for complex molecules. Scanning tunneling spectroscopy (STS) measurements give information about the molecular energy levels, which are next to the molecules Fermi level. Using a home built STM working under ambient conditions, we succeeded to combine high resolution topography mapping with simultaneous current-voltage characteristics (STS) measurements on single molecules deposited on highly oriented pyrolytic graphite surfaces. We present our recent results on grid-type molecules [Co4L4] (L=4,6-bis(2',2''-bipyridyl-6-yl)pyrimidine) and [Mn9L6] (L=2POAP-2H) as well as on ring-shaped Fe ion chains [Fe6Cl6L6] (L=1-Ecosyliminodiethanol). Small, regular molecule clusters as well as separated single molecules were observed. We found a rather large contrast at the expected location of the metal centers in our molecules, i.e. the location of the individual metal ions in their organic matrix is directly addressable by STS.

Diffraction based method to reconstruct the spectrum of the Thomson scattering x-ray source

NASA Astrophysics Data System (ADS)

Chi, Zhijun; Yan, Lixin; Zhang, Zhen; Zhou, Zheng; Zheng, Lianmin; Wang, Dong; Tian, Qili; Wang, Wei; Nie, Zan; Zhang, Jie; Du, Yingchao; Hua, Jianfei; Shi, Jiaru; Pai, Chihao; Lu, Wei; Huang, Wenhui; Chen, Huaibi; Tang, Chuanxiang

2017-04-01

As Thomson scattering x-ray sources based on the collision of intense laser and relativistic electrons have drawn much attention in various scientific fields, there is an increasing demand for the effective methods to reconstruct the spectrum information of the ultra-short and high-intensity x-ray pulses. In this paper, a precise spectrum measurement method for the Thomson scattering x-ray sources was proposed with the diffraction of a Highly Oriented Pyrolytic Graphite (HOPG) crystal and was demonstrated at the Tsinghua Thomson scattering X-ray source. The x-ray pulse is diffracted by a 15 mm (L) ×15 mm (H)× 1 mm (D) HOPG crystal with 1° mosaic spread. By analyzing the diffraction pattern, both x-ray peak energies and energy spectral bandwidths at different polar angles can be reconstructed, which agree well with the theoretical value and simulation. The higher integral reflectivity of the HOPG crystal makes this method possible for single-shot measurement.

Diffraction based method to reconstruct the spectrum of the Thomson scattering x-ray source.

PubMed

Chi, Zhijun; Yan, Lixin; Zhang, Zhen; Zhou, Zheng; Zheng, Lianmin; Wang, Dong; Tian, Qili; Wang, Wei; Nie, Zan; Zhang, Jie; Du, Yingchao; Hua, Jianfei; Shi, Jiaru; Pai, Chihao; Lu, Wei; Huang, Wenhui; Chen, Huaibi; Tang, Chuanxiang

2017-04-01

As Thomson scattering x-ray sources based on the collision of intense laser and relativistic electrons have drawn much attention in various scientific fields, there is an increasing demand for the effective methods to reconstruct the spectrum information of the ultra-short and high-intensity x-ray pulses. In this paper, a precise spectrum measurement method for the Thomson scattering x-ray sources was proposed with the diffraction of a Highly Oriented Pyrolytic Graphite (HOPG) crystal and was demonstrated at the Tsinghua Thomson scattering X-ray source. The x-ray pulse is diffracted by a 15 mm (L) ×15 mm (H)× 1 mm (D) HOPG crystal with 1° mosaic spread. By analyzing the diffraction pattern, both x-ray peak energies and energy spectral bandwidths at different polar angles can be reconstructed, which agree well with the theoretical value and simulation. The higher integral reflectivity of the HOPG crystal makes this method possible for single-shot measurement.

Poly(ethylene oxide) surfactant polymers.

PubMed

Vacheethasanee, Katanchalee; Wang, Shuwu; Qiu, Yongxing; Marchant, Roger E

2004-01-01

We report on a series of structurally well-defined surfactant polymers that undergo surface-induced self-assembly on hydrophobic biomaterial surfaces. The surfactant polymers consist of a poly(vinyl amine) backbone with poly(ethylene oxide) and hexanal pendant groups. The poly(vinyl amine) (PVAm) was synthesized by hydrolysis of poly(N-vinyl formamide) following free radical polymerization of N-vinyl formamide. Hexanal and aldehyde-terminated poly(ethylene oxide) (PEO) were simultaneously attached to PVAm via reductive amination. Surfactant polymers with different PEO:hexanal ratios and hydrophilic/hydrophobic balances were prepared, and characterized by FT-IR, 1H-NMR and XPS spectroscopies. Surface active properties at the air/water interface were determined by surface tension measurements. Surface activity at a solid surface/water interface was demonstrated by atomic force microscopy, showing epitaxially molecular alignment for surfactant polymers adsorbed on highly oriented pyrolytic graphite. The surfactant polymers described in this report can be adapted for simple non-covalent surface modification of biomaterials and hydrophobic surfaces to provide highly hydrated interfaces.

AFM visualization at a single-molecule level of denaturated states of proteins on graphite.

PubMed

Barinov, Nikolay A; Prokhorov, Valery V; Dubrovin, Evgeniy V; Klinov, Dmitry V

2016-10-01

Different graphitic materials are either already used or believed to be advantageous in biomedical and biotechnological applications, e.g., as biomaterials or substrates for sensors. Most of these applications or associated important issues, such as biocompatibility, address the problem of adsorption of protein molecules and, in particular the conformational state of the adsorbed protein molecule on graphite. High-resolution AFM demonstrates highly oriented pyrolytic graphite (HOPG) induced denaturation of four proteins of blood plasma, such as ferritin, fibrinogen, human serum albumin (HSA) and immunoglobulin G (IgG), at a single molecule level. Protein denaturation is accompanied by the decrease of the heights of protein globules and spreading of the denatured protein fraction on the surface. In contrast, the modification of HOPG with the amphiphilic oligoglycine-hydrocarbon derivative monolayer preserves the native-like conformation and provides even more mild conditions for the protein adsorption than typically used mica. Protein unfolding on HOPG may have universal character for "soft" globular proteins. Copyright © 2016 Elsevier B.V. All rights reserved.

Self-assembly of (perfluoroalkyl)alkanes on a substrate surface from solutions in supercritical carbon dioxide.

PubMed

Gallyamov, Marat O; Mourran, Ahmed; Tartsch, Bernd; Vinokur, Rostislav A; Nikitin, Lev N; Khokhlov, Alexei R; Schaumburg, Kjeld; Möller, Martin

2006-06-14

Toroidal self-assembled structures of perfluorododecylnonadecane and perfluorotetradecyloctadecane have been deposited on mica and highly oriented pyrolytic graphite surfaces by exposure of the substrates to solutions of the (pefluoroalkyl)alkanes in supercritical carbon dioxide. Scanning force microscopy (SFM) images have displayed a high degree of regularity of these self-assembled nanoobjects regarding size, shape, and packing in a monolayer. Analysis of SFM images allowed us to estimate that each toroidal domain has an outer diameter of about 50 nm and consists of several thousands of molecules. We propose a simple model explaining the clustering of the molecules to objects with a finite size. The model based on the close-packing principles predicts formation of toroids, whose size is determined by the molecular geometry. Here, we consider the amphiphilic nature of the (perfluoroalkyl)alkane molecules in combination with incommensurable packing parameters of the alkyl- and the perfluoralkyl-segments to be a key factor for such a self-assembly.

Damage to the microbial cell membrane during pyrolytic sugar utilization and strategies for increasing resistance.

PubMed

Jin, Tao; Rover, Marjorie R; Petersen, Elspeth M; Chi, Zhanyou; Smith, Ryan G; Brown, Robert C; Wen, Zhiyou; Jarboe, Laura R

2017-09-01

Lignocellulosic biomass is an appealing feedstock for the production of biorenewable fuels and chemicals, and thermochemical processing is a promising method for depolymerizing it into sugars. However, trace compounds in this pyrolytic sugar syrup are inhibitory to microbial biocatalysts. This study demonstrates that hydrophobic inhibitors damage the cell membrane of ethanologenic Escherichia coli KO11+lgk. Adaptive evolution was employed to identify design strategies for improving pyrolytic sugar tolerance and utilization. Characterization of the resulting evolved strain indicates that increased resistance to the membrane-damaging effects of the pyrolytic sugars can be attributed to a glutamine to leucine mutation at position 29 of carbon storage regulator CsrA. This single amino acid change is sufficient for decreasing EPS protein production and increasing membrane integrity when exposed to pyrolytic sugars.

Design, fabrication and performance of small, graphite electrode, multistage depressed collectors with 200-W, CW, 8- to 18-GHz traveling-wave tubes

NASA Technical Reports Server (NTRS)

Ebihara, Ben T.; Ramins, Peter

1987-01-01

Small multistage depressed collectors (MDC's) which used pyrolytic graphite, ion-beam-textured pyrolytic graphite, and isotropic graphite electrodes were designed, fabricated, and evaluated in conjuntion with 200-W, continuous wave (CW), 8- to 18-GHz traveling-wave tubes (TWT's). The design, construction, and performance of the MDC's are described. The bakeout performance of the collectors, in terms of gas evolution, was indistinguishable from that of typical production tubes with copper collectors. However, preliminary results indicate that some additional radiofrequency (RF) and dc beam processing time (and/or longer or higher temperature bakeouts) may be needed beyond that of typical copper electrode collectors. This is particularly true for pyrolytic graphite electrodes and for TWT's without appendage ion pumps. Extended testing indicated good long-term stability of the textured pyrolytic graphite and isotropic graphite electrode surfaces. The isotropic graphite in particular showed considerable promise as an MDC electrode material because of its high purity, low cost, simple construction, potential for very compact overall size, and relatively low secondary electron emission yield characteristics in the as-machined state. However, considerably more testing experience is required before definitive conclusions on its suitability for electronic countermeasure systems and space TWT's can be made.

Biological conversion of pyrolytic products to ethanol and lipids

NASA Astrophysics Data System (ADS)

Lian, Jieni

Pyrolysis is a promising technology that can convert up to 75 % of lignocellulosic biomass into crude bio-oil. However, due to the complex chemical compositions of bio-oil, its further refining into fuels and high value chemicals faces great challenges. This dissertation research proposed new technologies for biological conversion of pyrolytic products derived from cellulose and hemicellulose, such as anhydrosugars and carbolic acids to fuels and chemicals. First, the pyrolytic anhydrosugars (chiefly levoglucosan (LG)) were hydrolysed into glucose followed by neutralization, detoxification and fermentation to produce ethanol by ethanogenetic yeast and lipids by oleaginous yeasts. Second, a novel process for the conversion of C1-C4 pyrolytic products to lipid with oleaginous yeasts was investigated. Third, oleaginous yeasts that can directly convert LG to lipids were studied and a recombined yeast with LG kinase was constructed for the direct convertion of LG into lipids. This allowed a reduction of existing process for LG fermentation from four steps into two steps and eliminated the need for acids and bases as well as the disposal of chemicals. The development of genetic modified organisms with LG kinase opens a promising avenue for the direct LG fermentation to produce a wide range of fuels and chemicals. The simplification of LG utilization process would enhance the economic viability of this technology.

Ordered water structure at hydrophobic graphite interfaces observed by 4D, ultrafast electron crystallography

PubMed Central

Yang, Ding-Shyue; Zewail, Ahmed H.

2009-01-01

Interfacial water has unique properties in various functions. Here, using 4-dimensional (4D), ultrafast electron crystallography with atomic-scale spatial and temporal resolution, we report study of structure and dynamics of interfacial water assembly on a hydrophobic surface. Structurally, vertically stacked bilayers on highly oriented pyrolytic graphite surface were determined to be ordered, contrary to the expectation that the strong hydrogen bonding of water on hydrophobic surfaces would dominate with suppressed interfacial order. Because of its terrace morphology, graphite plays the role of a template. The dynamics is also surprising. After the excitation of graphite by an ultrafast infrared pulse, the interfacial ice structure undergoes nonequilibrium “phase transformation” identified in the hydrogen-bond network through the observation of structural isosbestic point. We provide the time scales involved, the nature of ice-graphite structural dynamics, and relevance to properties related to confined water. PMID:19246378

Effects of chemical states of carbon on deuterium retention in carbon-containing materials

NASA Astrophysics Data System (ADS)

Oyaidzu, Makoto; Kimura, Hiromi; Nakahata, Toshihiko; Nishikawa, Yusuke; Tokitani, Masayuki; Oya, Yasuhisa; Iwakiri, Hirotomo; Yoshida, Naoaki; Okuno, Kenji

2007-08-01

Deuterium retention behavior in highly oriented pyrolytic graphite (HOPG), poly-crystalline diamond, poly-crystalline SiC, sintered WC, and converted B 4C were investigated to reveal tritium behavior in re-deposition and co-deposition layers. Such layers would contain carbon, when the first wall and/or divertor were made of graphite or carbon-containing materials. Furthermore, the employment of other materials such as tungsten, and first wall conditioning such as boronization would complicate the layers. No different deuterium trapping sites due to carbon from those in HOPG were found in all the samples, where two deuterium trapping processes were observed: hot atom chemical trapping of energetic deuterium by a dangling bond of carbon and thermochemical trapping of thermalized deuterium in a constituent atom vacancy surrounded by carbons. Additionally, the latter reaction could be easily counteracted by or competed with the other deuterium trapping reactions by constituent atoms.

Room temperature stable single molecule rectifiers with graphite electrodes

NASA Astrophysics Data System (ADS)

Rungger, Ivan; Kaliginedi, V.; Droghetti, A.; Ozawa, H.; Kuzume, A.; Haga, M.; Broekmann, P.; Rudnev, A. V.

In this combined theoretical and experimental study we present new molecular electronics device characteristics of unprecedented stability at room temperature by using electrodes based on highly oriented pyrolytic graphite with covalently attached molecules. To this aim, we explore the effect of the anchoring group chemistry on the charge transport properties of graphite/molecule contacts by means of the scanning tunneling microscopy break-junction technique and ab initio simulations. The theoretical approach to evaluate the conductance is based on density functional theory calculations combined with the non-equilibrium Greens function technique, as implemented in the Smeagol electron transport code. We also demonstrate a strong bias dependence and rectification of the single molecule conductance induced by the anchoring chemistry in combination with the very low density of states of graphite around the Fermi energy. We show that the direction of tunneling current rectification can be tuned by anchoring group chemistry.

Crystallographic order and decomposition of [MnIII 6CrIII]3+ single-molecule magnets deposited in submonolayers and monolayers on HOPG studied by means of molecular resolved atomic force microscopy (AFM) and Kelvin probe force microscopy in UHV

NASA Astrophysics Data System (ADS)

Gryzia, Aaron; Volkmann, Timm; Brechling, Armin; Hoeke, Veronika; Schneider, Lilli; Kuepper, Karsten; Glaser, Thorsten; Heinzmann, Ulrich

2014-02-01

Monolayers and submonolayers of [Mn III 6 Cr III ] 3+ single-molecule magnets (SMMs) adsorbed on highly oriented pyrolytic graphite (HOPG) using the droplet technique characterized by non-contact atomic force microscopy (nc-AFM) as well as by Kelvin probe force microscopy (KPFM) show island-like structures with heights resembling the height of the molecule. Furthermore, islands were found which revealed ordered 1D as well as 2D structures with periods close to the width of the SMMs. Along this, islands which show half the heights of intact SMMs were observed which are evidences for a decomposing process of the molecules during the preparation. Finally, models for the structure of the ordered SMM adsorbates are proposed to explain the observations.

Formation mechanism of graphite hexagonal pyramids by argon plasma etching of graphite substrates

NASA Astrophysics Data System (ADS)

Glad, X.; de Poucques, L.; Bougdira, J.

2015-12-01

A new graphite crystal morphology has been recently reported, namely the graphite hexagonal pyramids (GHPs). They are hexagonally-shaped crystals with diameters ranging from 50 to 800 nm and a constant apex angle of 40°. These nanostructures are formed from graphite substrates (flexible graphite and highly ordered pyrolytic graphite) in low pressure helicon coupling radiofrequency argon plasma at 25 eV ion energy and, purportedly, due to a physical etching process. In this paper, the occurrence of peculiar crystals is shown, presenting two hexagonal orientations obtained on both types of samples, which confirms such a formation mechanism. Moreover, by applying a pretreatment step with different time durations of inductive coupling radiofrequency argon plasma, for which the incident ion energy decreases at 12 eV, uniform coverage of the surface can be achieved with an influence on the density and size of the GHPs.

Destruction Chemistry of Mustard Simulants

DTIC Science & Technology

2008-07-04

organosulfur compounds under both pyrolytic and oxidative conditions. We focus on the destruction of alkyl sulfides that are surrogates for chemical...destruction chemistry of organosulfur compounds under both pyrolytic and oxidative conditions. We focus on the destruction of alkyl sulfides that are...ACCOMPLISHMENTS ABSTRACT This study investigates the destruction chemistry of organosulfur compounds under both pyrolytic and oxidative conditions. We

Waste-to-Energy Systems

DTIC Science & Technology

2009-04-01

at hospitals, at schools,” or wherever there are people creating masses of trash.5 Pyrolytic Gasification Pyrolytic gasification is not a new...prevalent with both. Gasification is . . . the chemical reaction and molecular breakdown or degradation of materials. The first pyrolytic gasification...dealing with about 2 tons of mixed solid waste per day, will destroy wood, paper card, food, plastics, and sanitary, clinical, and oil waste and

Electrochemical Functionalization of Graphene at the Nanoscale with Self-Assembling Diazonium Salts.

PubMed

Xia, Zhenyuan; Leonardi, Francesca; Gobbi, Marco; Liu, Yi; Bellani, Vittorio; Liscio, Andrea; Kovtun, Alessandro; Li, Rongjin; Feng, Xinliang; Orgiu, Emanuele; Samorì, Paolo; Treossi, Emanuele; Palermo, Vincenzo

2016-07-26

We describe a fast and versatile method to functionalize high-quality graphene with organic molecules by exploiting the synergistic effect of supramolecular and covalent chemistry. With this goal, we designed and synthesized molecules comprising a long aliphatic chain and an aryl diazonium salt. Thanks to the long chain, these molecules physisorb from solution onto CVD graphene or bulk graphite, self-assembling in an ordered monolayer. The sample is successively transferred into an aqueous electrolyte, to block any reorganization or desorption of the monolayer. An electrochemical impulse is used to transform the diazonium group into a radical capable of grafting covalently to the substrate and transforming the physisorption into a covalent chemisorption. During covalent grafting in water, the molecules retain the ordered packing formed upon self-assembly. Our two-step approach is characterized by the independent control over the processes of immobilization of molecules on the substrate and their covalent tethering, enabling fast (t < 10 s) covalent functionalization of graphene. This strategy is highly versatile and works with many carbon-based materials including graphene deposited on silicon, plastic, and quartz as well as highly oriented pyrolytic graphite.

Production of hydrocarbon fuels from pyrolysis of soybean oils using a basic catalyst.

PubMed

Xu, Junming; Jiang, Jianchun; Sun, Yunjuan; Chen, Jie

2010-12-01

Triglycerides obtained from animals and plants have attracted great attention from researchers for developing an environmental friendly and high-quality fuel, free of nitrogen and sulfur. In the present work, the production of biofuel by catalytic cracking of soybean oil over a basic catalyst in a continuous pyrolysis reactor at atmospheric pressure has been studied. Experiments were designed to study the effect of different types of catalysts on the yield and acid value of the diesel and gasoline fractions from the pyrolytic oil. It was found that basic catalyst gave a product with relatively low acid number. These pyrolytic oils were also further reacted with alcohol in order to decrease their acid value. After esterification, the physico-chemical properties of these biofuels were characterized, and compared with Chinese specifications for conventional diesel fuels. The results showed that esterification of pyrolytic oil from triglycerides represents an alternative technique for producing biofuels from soybean oils with characteristics similar to those of petroleum fuels. Published by Elsevier Ltd.

Biomass-based pyrolytic polygeneration system on cotton stalk pyrolysis: influence of temperature.

PubMed

Chen, Yingquan; Yang, Haiping; Wang, Xianhua; Zhang, Shihong; Chen, Hanping

2012-03-01

To study the process of biomass-based pyrolytic polygeneration and its mechanism in depth, the pyrolysis of cotton stalk was investigated in a packed bed, with focus on the evolution of the chemical and physical structures of the solid, liquid and gaseous products. The evolution of product characteristics could be good explaining the process mechanism of biomass pyrolysis. A relationship between the pore distribution of solid products and the fused aromatic rings system revealed by Raman analysis might be exist and need to quantify in further study. Regarding the optimum conditions for obtaining high-quality pyrolytic products from the polygeneration system, the optimum temperature is 550-750°C, with a higher calorific value of the obtained charcoal (≈ 28 MJ/kg) and a higher surface area (>200 m(2)/g). Meanwhile, the calorific value of the gas reaches 8-9 MJ/m(3) and the liquid oil would be used as a platform product in biorefinery. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

Separation, hydrolysis and fermentation of pyrolytic sugars to produce ethanol and lipids.

PubMed

Lian, Jieni; Chen, Shulin; Zhou, Shuai; Wang, Zhouhong; O'Fallon, James; Li, Chun-Zhu; Garcia-Perez, Manuel

2010-12-01

This paper describes a new scheme to convert anhydrosugars found in pyrolysis oils into ethanol and lipids. Pyrolytic sugars were separated from phenols by solvent extraction and were hydrolyzed into glucose using sulfuric acid as a catalyst. Toxicological studies showed that phenols and acids were the main species inhibiting growth of the yeast Saccharomyces cerevisiae. The sulfuric acids, and carboxylic acids from the bio-oils, were neutralized with Ba(OH)(2). The phase rich in sugar was further detoxified with activated carbon. The resulting aqueous phase rich in glucose was fermented with three different yeasts: S. cerevisiae to produce ethanol, and Cryptococcus curvatus and Rhodotorula glutinis to produce lipids. Yields as high as 0.473 g ethanol/g glucose and 0.167 g lipids/g sugar (0.266 g ethanol equivalent/g sugar), were obtained. These results confirm that pyrolytic sugar fermentation to produce ethanol is more efficient than for lipid production. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Catalytic biorefining of plant biomass to non-pyrolytic lignin bio-oil and carbohydrates through hydrogen transfer reactions.

PubMed

Ferrini, Paola; Rinaldi, Roberto

2014-08-11

Through catalytic hydrogen transfer reactions, a new biorefining method results in the isolation of depolymerized lignin--a non-pyrolytic lignin bio-oil--in addition to pulps that are amenable to enzymatic hydrolysis. Compared with organosolv lignin, the lignin bio-oil is highly susceptible to further hydrodeoxygenation under low-severity conditions and therefore establishes a unique platform for lignin valorization by heterogeneous catalysis. Overall, the potential of a catalytic biorefining method designed from the perspective of lignin utilization is reported. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cascade Production of Lactic Acid from Universal Types of Sugars Catalyzed by Lanthanum Triflate.

PubMed

Liu, Dajiang; Kim, Kwang Ho; Sun, Jian; Simmons, Blake A; Singh, Seema

2018-02-09

Lignocellulosic biomass conversion into value-added platform chemicals in the non-toxic, water-tolerant Lewis acid, and water solutions bears the hallmark of green chemistry. Lactic acid derived from biomass is an important chemical building block for biodegradable polymers such as polylactide. Herein, a universal method of converting lignocellulosic sugars into lactic acid using catalytic amount of water-stable Lewis acid La(OTf) 3 is demonstrated. The lignocellulosic sugars studied in this work include 1) pyrolytic sugars from pyrolysis oil, and 2) sugars derived from ionic liquid (IL)-pretreated biomass. Under moderate conditions (250 °C, 1 h), levoglucosan (major pyrolytic sugar), glucose, and xylose were converted into lactic acid with carbon-based molar yields of 75, 74, and 61 %, respectively. Furthermore, roughly 49 mol % (based on levoglucosan) and 74 wt % (relative to pretreated biomass) of lactic acid were obtained from the conversion of pyrolytic sugars and sugar-rich fraction after lignin removal from switchgrass, respectively. To our knowledge, this is the first reported conversion of pyrolytic sugar into lactic acid by chemocatalysis and also lignocellulosic sugars are converted into lactic acid without hydrolysis. This approach could potentially be extended to other lignocellulosic sugars after simple removal of lignin from biomass pretreatment, rendering moderate to high yields of lactic acid. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal and catalytic slow pyrolysis of Calophyllum inophyllum fruit shell.

PubMed

Alagu, R M; Sundaram, E Ganapathy; Natarajan, E

2015-10-01

Pyrolysis of Calophyllum inophyllum shell was performed in a fixed bed pyrolyser to produce pyrolytic oil. Both thermal (without catalysts) and catalytic pyrolysis process were conducted to investigate the effect of catalysts on pyrolysis yield and pyrolysis oil characteristics. The yield of pyrolytic oil through thermal pyrolysis was maximum (41% wt) at 425 °C for particle size of 1.18 mm and heating rate of 40 °C/min. In catalytic pyrolysis the pyrolytic oil yield was maximum (45% wt) with both zeolite and kaolin catalysts followed by Al2O3 catalyst (44% wt). The functional groups and chemical components present in the pyrolytic oil are identified by Fourier Transform Infrared Spectroscopy (FT-IR) and Gas Chromatography-Mass Spectrometry (GC-MS) techniques. This study found that C. inophyllum shell is a potential new green energy source and that the catalytic pyrolysis process using zeolite catalyst improves the calorific value and acidity of the pyrolytic oil. Copyright © 2015 Elsevier Ltd. All rights reserved.

A comparison of thermal behaviors of raw biomass, pyrolytic biochar and their blends with lignite.

PubMed

Liu, Zhengang; Balasubramanian, Rajasekhar

2013-10-01

In this study, thermal characteristics of raw biomass, corresponding pyrolytic biochars and their blends with lignite were investigated. The results showed that pyrolytic biochars had better fuel qualities than their parent biomass. In comparison to raw biomass, the combustion of the biochars shifted towards higher temperature and occurred at continuous temperature zones. The biochar addition in lignite increased the reactivities of the blends. Obvious interactions were observed between biomass/biochar and lignite and resulted in increased total burnout, shortened combustion time and increased maximum weight loss rate, indicating increased combustion efficiencies than that of lignite combustion alone. Regarding ash-related problems, the tendency to form slagging and fouling increased, when pyrolytic biochars were co-combusted with coal. This present study demonstrated that the pyrolytic biochars were more suitable than raw biomass to be co-combusted with lignite for energy generation in existing coal-fired power plants. Copyright © 2013 Elsevier Ltd. All rights reserved.

Polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs) mitigation in the pyrolysis process of waste tires using CO₂ as a reaction medium.

PubMed

Kwon, Eilhann E; Oh, Jeong-Ik; Kim, Ki-Hyun

2015-09-01

Our work reported the CO2-assisted mitigation of PAHs and VOCs in the thermo-chemical process (i.e., pyrolysis). To investigate the pyrolysis of used tires to recover energy and chemical products, the experiments were conducted using a laboratory-scale batch-type reactor. In particular, to examine the influence of the CO2 in pyrolysis of a tire, the pyrolytic products including C1-5-hydrocarbons (HCs), volatile organic carbons (VOCs), and polycyclic aromatic hydrocarbons (PAHs) were evaluated qualitatively by gas chromatography (GC) with mass spectroscopy (MS) as well as with a thermal conductivity detector (TCD). The mass balance of the pyrolytic products under various pyrolytic conditions was established on the basis of their weight fractions of the pyrolytic products. Our experimental work experimentally validated that the amount of gaseous pyrolytic products increased when using CO2 as a pyrolysis medium, while substantially altering the production of pyrolytic oil in absolute content (7.3-17.2%) and in relative composition (including PAHs and VOCs). Thus, the co-feeding of CO2 in the pyrolysis process can be considered an environmentally benign and energy efficient process. Copyright © 2015 Elsevier Ltd. All rights reserved.

Thermal plasma process for recovering monomers and high value carbons from polymeric materials

DOEpatents

Knight, Richard; Grossmann, Elihu D.; Guddeti, Ravikishan R.

2002-01-01

The present invention relates to a method of recycling polymeric waste products into monomers and high value forms of carbon by pyrolytic conversion using an induction coupled RF plasma heated reactor.

Pyrolysis of de-oiled seed cake of Jatropha Curcas and catalytic steam reforming of pyrolytic bio-oil to hydrogen.

PubMed

Renny, Andrew; Santhosh, Viswanathan; Somkuwar, Nitin; Gokak, D T; Sharma, Pankaj; Bhargava, Sanjay

2016-11-01

The aim of this work was to study the pyrolysis of de-oiled seed cake of Jatropha Curcas and catalytic steam reforming of pyrolytic bio-oil to hydrogen. As per literature, presence of heavy nitrogenous and oxygenated compounds leads to catalyst deactivation. Here, an attempt has been made to tune pyrolytic reactions to optimize the N and O content of the pyrolytic bio-oil. Bio-oil conversion and hydrogen yield decreased as reaction progressed, which attributes to temporary loss of catalytic activity by blockage of catalyst pores by carbon deposition. Further, retention of steam reforming activity after repetitive steam activation suggests long-term catalyst usage. Copyright © 2016 Elsevier Ltd. All rights reserved.

Literature Review: Materials with Negative Poisson’s Ratios and Potential Applications to Aerospace and Defence

DTIC Science & Technology

2006-08-01

and defence industries. In fact, some materials with such anomalous (i.e. NPR) properties have been used in applications such as pyrolytic graphite...real applications such as pyrolytic graphite with NPR of -0.21 for thermal protection in aerospace (Garber, 1963), large single crystals of Ni3Al with...Foundations of Solid Mechanics, Prentice-Hall, p.353, 1968. Garber, A.M., Pyrolytic materials for thermal protection systems, Aerospace Eng., Vol

Direct graphene growth from highly ordered pyrolytic graphite using pulsed Nd: YAG laser on p-Si (100) substrate at 700°c

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Pramod, E-mail: kumarpramod.iitd@gmail.com; Lahiri, Indranil; Mitra, Anirban

Few layer graphene was deposited on p-type Si (100) substrates by pulsed laser deposition of highly ordered pyrolytic graphite (HOPG) target at a relatively low temperature of 700 °C, without any catalytic layer. Effect of laser energy on the ability to produce the crystalline graphene was studied. It was observed that a laser energy of 220 mJ/pulse lead to form few layer graphene while higher laser energy of 440 mJ/pulse was detrimental to precipitation process. The reasons behind this observation are also discussed. Graphene samples were analyzed using Raman spectroscopy and surface morphology of graphene samples was confirmed using fieldmore » emission scanning electron microscope (FE-SEM).« less

Design and fabrication of a fixed-bed batch type pyrolysis reactor for pilot scale pyrolytic oil production in Bangladesh

NASA Astrophysics Data System (ADS)

Aziz, Mohammad Abdul; Al-khulaidi, Rami Ali; Rashid, MM; Islam, M. R.; Rashid, MAN

2017-03-01

In this research, a development and performance test of a fixed-bed batch type pyrolysis reactor for pilot scale pyrolysis oil production was successfully completed. The characteristics of the pyrolysis oil were compared to other experimental results. A solid horizontal condenser, a burner for furnace heating and a reactor shield were designed. Due to the pilot scale pyrolytic oil production encountered numerous problems during the plant’s operation. This fixed-bed batch type pyrolysis reactor method will demonstrate the energy saving concept of solid waste tire by creating energy stability. From this experiment, product yields (wt. %) for liquid or pyrolytic oil were 49%, char 38.3 % and pyrolytic gas 12.7% with an operation running time of 185 minutes.

Two-dimensional network stability of nucleobases and amino acids on graphite under ambient conditions: adenine, L-serine and L-tyrosine.

PubMed

Bald, Ilko; Weigelt, Sigrid; Ma, Xiaojing; Xie, Pengyang; Subramani, Ramesh; Dong, Mingdong; Wang, Chen; Mamdouh, Wael; Wang, Jianguo; Besenbacher, Flemming

2010-04-14

We have investigated the stability of two-dimensional self-assembled molecular networks formed upon co-adsorption of the DNA base, adenine, with each of the amino acids, L-serine and L-tyrosine, on a highly oriented pyrolytic graphite (HOPG) surface by drop-casting from a water solution. L-serine and L-tyrosine were chosen as model systems due to their different interaction with the solvent molecules and the graphite substrate, which is reflected in a high and low solubility in water, respectively, compared with adenine. Combined scanning tunneling microscopy (STM) measurements and density functional theory (DFT) calculations show that the self-assembly process is mainly driven by the formation of strong adenine-adenine hydrogen bonds. We find that pure adenine networks are energetically more stable than networks built up of either pure L-serine, pure L-tyrosine or combinations of adenine with L-serine or L-tyrosine, and that only pure adenine networks are stable enough to be observable by STM under ambient conditions.

Understanding the Growth Mechanism of GaN Epitaxial Layers on Mechanically Exfoliated Graphite

NASA Astrophysics Data System (ADS)

Li, Tianbao; Liu, Chenyang; Zhang, Zhe; Yu, Bin; Dong, Hailiang; Jia, Wei; Jia, Zhigang; Yu, Chunyan; Gan, Lin; Xu, Bingshe; Jiang, Haiwei

2018-04-01

The growth mechanism of GaN epitaxial layers on mechanically exfoliated graphite is explained in detail based on classic nucleation theory. The number of defects on the graphite surface can be increased via O-plasma treatment, leading to increased nucleation density on the graphite surface. The addition of elemental Al can effectively improve the nucleation rate, which can promote the formation of dense nucleation layers and the lateral growth of GaN epitaxial layers. The surface morphologies of the nucleation layers, annealed layers and epitaxial layers were characterized by field-emission scanning electron microscopy, where the evolution of the surface morphology coincided with a 3D-to-2D growth mechanism. High-resolution transmission electron microscopy was used to characterize the microstructure of GaN. Fast Fourier transform diffraction patterns showed that cubic phase (zinc-blend structure) GaN grains were obtained using conventional GaN nucleation layers, while the hexagonal phase (wurtzite structure) GaN films were formed using AlGaN nucleation layers. Our work opens new avenues for using highly oriented pyrolytic graphite as a substrate to fabricate transferable optoelectronic devices.

Evolution of elastic x-ray scattering in laser-shocked warm dense lithium.

PubMed

Kugland, N L; Gregori, G; Bandyopadhyay, S; Brenner, C M; Brown, C R D; Constantin, C; Glenzer, S H; Khattak, F Y; Kritcher, A L; Niemann, C; Otten, A; Pasley, J; Pelka, A; Roth, M; Spindloe, C; Riley, D

2009-12-01

We have studied the dynamics of warm dense Li with near-elastic x-ray scattering. Li foils were heated and compressed using shock waves driven by 4-ns-long laser pulses. Separate 1-ns-long laser pulses were used to generate a bright source of 2.96 keV Cl Ly- alpha photons for x-ray scattering, and the spectrum of scattered photons was recorded at a scattering angle of 120 degrees using a highly oriented pyrolytic graphite crystal operated in the von Hamos geometry. A variable delay between the heater and backlighter laser beams measured the scattering time evolution. Comparison with radiation-hydrodynamics simulations shows that the plasma is highly coupled during the first several nanoseconds, then relaxes to a moderate coupling state at later times. Near-elastic scattering amplitudes have been successfully simulated using the screened one-component plasma model. Our main finding is that the near-elastic scattering amplitudes are quite sensitive to the mean ionization state Z[over ] and by extension to the choice of ionization model in the radiation-hydrodynamics simulations used to predict plasma properties within the shocked Li.

Sb-Te alloy nanostructures produced on a graphite surface by a simple annealing process

NASA Astrophysics Data System (ADS)

Kuwahara, Masashi; Uratsuji, Hideaki; Abe, Maho; Sone, Hayato; Hosaka, Sumio; Sakai, Joe; Uehara, Yoichi; Endo, Rie; Tsuruoka, Tohru

2015-08-01

We have produced Sb-Te alloy nanostructures from a thin Sb2Te3 layer deposited on a highly oriented pyrolytic graphite substrate using a simple rf-magnetron sputtering and annealing technique. The size, shape, and chemical composition of the structures were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), and energy dispersive X-ray spectrometry (EDX), respectively. The shape of the nanostructures was found to depend on the annealing temperature; nanoparticles appear on the substrate by annealing at 200 °C, while nanoneedles are formed at higher temperatures. Chemical composition analysis has revealed that all the structures were in the composition of Sb:Te = 1:3, Te rich compared to the target composition Sb2Te3, probably due to the higher movability of Te atoms on the substrate compared with Sb. We also tried to observe the production process of nanostructures in situ using SEM. Unfortunately, this was not possible because of evaporation in vacuum, suggesting that the formation of nanostructures is highly sensitive to the ambient pressure.

Understanding the Growth Mechanism of GaN Epitaxial Layers on Mechanically Exfoliated Graphite.

PubMed

Li, Tianbao; Liu, Chenyang; Zhang, Zhe; Yu, Bin; Dong, Hailiang; Jia, Wei; Jia, Zhigang; Yu, Chunyan; Gan, Lin; Xu, Bingshe; Jiang, Haiwei

2018-04-27

The growth mechanism of GaN epitaxial layers on mechanically exfoliated graphite is explained in detail based on classic nucleation theory. The number of defects on the graphite surface can be increased via O-plasma treatment, leading to increased nucleation density on the graphite surface. The addition of elemental Al can effectively improve the nucleation rate, which can promote the formation of dense nucleation layers and the lateral growth of GaN epitaxial layers. The surface morphologies of the nucleation layers, annealed layers and epitaxial layers were characterized by field-emission scanning electron microscopy, where the evolution of the surface morphology coincided with a 3D-to-2D growth mechanism. High-resolution transmission electron microscopy was used to characterize the microstructure of GaN. Fast Fourier transform diffraction patterns showed that cubic phase (zinc-blend structure) GaN grains were obtained using conventional GaN nucleation layers, while the hexagonal phase (wurtzite structure) GaN films were formed using AlGaN nucleation layers. Our work opens new avenues for using highly oriented pyrolytic graphite as a substrate to fabricate transferable optoelectronic devices.

Pyrolytic graphite collector development program

NASA Technical Reports Server (NTRS)

Wilkins, W. J.

1982-01-01

Pyrolytic graphite promises to have significant advantages as a material for multistage depressed collector electrodes. Among these advantages are lighter weight, improved mechanical stiffness under shock and vibration, reduced secondary electron back-streaming for higher efficiency, and reduced outgassing at higher operating temperatures. The essential properties of pyrolytic graphite and the necessary design criteria are discussed. This includes the study of suitable electrode geometries and methods of attachment to other metal and ceramic collector components consistent with typical electrical, thermal, and mechanical requirements.

Effects of Prior Aging at Elevated Temperature in Air and in Argon Environments on Creep Response of PMR-15 Neat Resin at 288 deg C

DTIC Science & Technology

2007-03-01

either inert gases or air to distinguish between the pyrolytic and oxidative degradation mechanisms. This exposure is commonly called “aging” of...and performance under use conditions. 4 This thesis explores the effects of both pyrolytic and thermal oxidative degradation on the mechanical...fatigue. A third assumption is that the mechanical properties of the pyrolytically aged samples will approximate the mechanical properties of the inner

Quantized edge modes in atomic-scale point contacts in graphene

NASA Astrophysics Data System (ADS)

Kinikar, Amogh; Phanindra Sai, T.; Bhattacharyya, Semonti; Agarwala, Adhip; Biswas, Tathagata; Sarker, Sanjoy K.; Krishnamurthy, H. R.; Jain, Manish; Shenoy, Vijay B.; Ghosh, Arindam

2017-07-01

The zigzag edges of single- or few-layer graphene are perfect one-dimensional conductors owing to a set of gapless states that are topologically protected against backscattering. Direct experimental evidence of these states has been limited so far to their local thermodynamic and magnetic properties, determined by the competing effects of edge topology and electron-electron interaction. However, experimental signatures of edge-bound electrical conduction have remained elusive, primarily due to the lack of graphitic nanostructures with low structural and/or chemical edge disorder. Here, we report the experimental detection of edge-mode electrical transport in suspended atomic-scale constrictions of single and multilayer graphene created during nanomechanical exfoliation of highly oriented pyrolytic graphite. The edge-mode transport leads to the observed quantization of conductance close to multiples of G0 = 2e2/h. At the same time, conductance plateaux at G0/2 and a split zero-bias anomaly in non-equilibrium transport suggest conduction via spin-polarized states in the presence of an electron-electron interaction.

Time-resolved investigations of the non-thermal ablation process of graphite induced by femtosecond laser pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kalupka, C., E-mail: christian.kalupka@llt.rwth-aachen.de; Finger, J.; Reininghaus, M.

2016-04-21

We report on the in-situ analysis of the ablation dynamics of the, so-called, laser induced non-thermal ablation process of graphite. A highly oriented pyrolytic graphite is excited by femtosecond laser pulses with fluences below the classic thermal ablation threshold. The ablation dynamics are investigated by axial pump-probe reflection measurements, transversal pump-probe shadowgraphy, and time-resolved transversal emission photography. The combination of the applied analysis methods allows for a continuous and detailed time-resolved observation of the non-thermal ablation dynamics from several picoseconds up to 180 ns. Formation of large, μm-sized particles takes place within the first 3.5 ns after irradiation. The following propagation ofmore » ablation products and the shock wave front are tracked by transversal shadowgraphy up to 16 ns. The comparison of ablation dynamics of different fluences by emission photography reveals thermal ablation products even for non-thermal fluences.« less

Direct determination of the local Hamaker constant of inorganic surfaces based on scanning force microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krajina, Brad A.; Kocherlakota, Lakshmi S.; Overney, René M., E-mail: roverney@u.washington.edu

The energetics involved in the bonding fluctuations between nanometer-sized silicon dioxide (SiO{sub 2}) probes and highly oriented pyrolytic graphite (HOPG) and molybdenum disulfide (MoS{sub 2}) could be quantified directly and locally on the submicron scale via a time-temperature superposition analysis of the lateral forces between scanning force microscopy silicon dioxide probes and inorganic sample surfaces. The so-called “intrinsic friction analysis” (IFA) provided direct access to the Hamaker constants for HOPG and MoS{sub 2}, as well as the control sample, calcium fluoride (CaF{sub 2}). The use of scanning probe enables nanoscopic analysis of bonding fluctuations, thereby overcoming challenges associated with largermore » scale inhomogeneity and surface roughness common to conventional techniques used to determine surface free energies and dielectric properties. A complementary numerical analysis based on optical and electron energy loss spectroscopy and the Lifshitz quantum electrodynamic theory of van der Waals interactions is provided and confirms quantitatively the IFA results.« less

Septipyridines as conformationally controlled substitutes for inaccessible bis(terpyridine)-derived oligopyridines in two-dimensional self-assembly

PubMed Central

Caterbow, Daniel; Künzel, Daniela; Mavros, Michael G; Groß, Axel; Landfester, Katharina

2011-01-01

Summary The position of the peripheral nitrogen atoms in bis(terpyridine)-derived oligopyridines (BTPs) has a strong impact on their self-assembly behavior at the liquid/HOPG (highly oriented pyrolytic graphite) interface. The intermolecular hydrogen bonding interactions in these peripheral pyridine units show specific 2D structures for each BTP isomer. From nine possible constitutional isomers only four have been described in the literature. The synthesis and self-assembling behavior of an additional isomer is presented here, but the remaining four members of the series are synthetically inaccessible. The self-assembling properties of three of the missing four BTP isomers can be mimicked by making use of the energetically preferred N–C–C–N transoid conformation between 2,2'-bipyridine subunits in a new class of so-called septipyridines. The structures are investigated by scanning tunneling microscopy (STM) and a combination of force-field and first-principles electronic structure calculations. PMID:22003448

Electrodeposition of Si from an Ionic Liquid Bath at Room Temperature in the Presence of Water.

PubMed

Shah, Nisarg K; Pati, Ranjan Kumar; Ray, Abhijit; Mukhopadhyay, Indrajit

2017-02-21

The electrochemical deposition of Si has been carried out in an ionic liquid medium in the presence of water in a limited dry nitrogen environment on highly oriented pyrolytic graphite (HOPG) at room temperature. It has been found that the presence of water in ionic liquids does not affect the available effective potential window to a large extent. Silicon has been successfully deposited electrochemically in the overpotential regime in two different ionic liquids, namely, BMImTf 2 N and BMImPF 6 , in the presence of water. Although a Si thin film has been obtained from BMImTf 2 N; only distinguished Si crystals protected in ionic liquid droplets have been observed from BMImPF 6 . The most important observation of the present investigation is that the Si precursor, SiCl 4 , instead of undergoing hydrolysis, even in the presence of water, coexisted with ionic liquids, and elemental Si has been successfully electrodeposited.

Substrate Selection for Fundamental Studies of Electrocatalysts and Photoelectrodes: Inert Potential Windows in Acidic, Neutral, and Basic Electrolyte

PubMed Central

Gorlin, Yelena; Jaramillo, Thomas F.

2014-01-01

The selection of an appropriate substrate is an important initial step for many studies of electrochemically active materials. In order to help researchers with the substrate selection process, we employ a consistent experimental methodology to evaluate the electrochemical reactivity and stability of seven potential substrate materials for electrocatalyst and photoelectrode evaluation. Using cyclic voltammetry with a progressively increased scan range, we characterize three transparent conducting oxides (indium tin oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide) and four opaque conductors (gold, stainless steel 304, glassy carbon, and highly oriented pyrolytic graphite) in three different electrolytes (sulfuric acid, sodium acetate, and sodium hydroxide). We determine the inert potential window for each substrate/electrolyte combination and make recommendations about which materials may be most suitable for application under different experimental conditions. Furthermore, the testing methodology provides a framework for other researchers to evaluate and report the baseline activity of other substrates of interest to the broader community. PMID:25357131

Production of sp3 hybridization by swift heavy ion irradiation of HOPG

NASA Astrophysics Data System (ADS)

Zeng, J.; Zhai, P. F.; Liu, J.; Yao, H. J.; Duan, J. L.; Hou, M. D.; Sun, Y. M.; Li, G. P.

2013-07-01

Highly oriented pyrolytic graphite (HOPG) samples were irradiated by swift heavy ions (86Kr, 209Bi and 238U) with the fluence of 1011-1013 ions/cm2 at room temperature. The production of sp3 hybridization by the irradiation process has been confirmed directly by X-ray photoelectron spectroscopy (XPS). In this work, both irradiated and pristine HOPG samples were investigated by XPS and Raman spectroscopy. The existence of sp3 component is confirmed on the surface of the irradiated HOPG samples. XPS result shows that the acreage ratio Isp3/Isp2 increases with the ion fluence and saturates at a higher value of irradiation. It is found that the amount of hybridization (Isp3/Isp2) strongly depends on the electronic energy loss in the sample. Raman spectra of the irradiated samples show the increasing of acreage ratio ID/IG with the ion fluence, which indicates the change of the atomic structure and the phase transition from sp2 to sp3.

Interfacial assembly structures and nanotribological properties of saccharic acids.

PubMed

Shi, Hongyu; Liu, Yuhong; Zeng, Qingdao; Yang, Yanlian; Wang, Chen; Lu, Xinchun

2017-01-04

Saccharides have been recognized as potential bio-lubricants because of their good hydration ability. However, the interfacial structures of saccharides and their derivatives are rarely studied and the molecular details of interaction mechanisms have not been well understood. In this paper, the supramolecular assembly structures of saccharic acids (including galactaric acid and lactobionic acid), mediated by hydrogen bonds O-HN and O-HO, were successfully constructed on a highly oriented pyrolytic graphite (HOPG) surface by introducing pyridine modulators and were explicitly revealed by using scanning tunneling microscopy (STM). Furthermore, friction forces were measured in the saccharic acid/pyridine co-assembled system by atomic force microscopy (AFM), revealing a larger value than a pristine saccharic acid system, which could be attributed to the stronger tip-assembled molecule interactions that lead to the higher potential energy barrier needed to overcome. The effort on saccharide-related supramolecular self-assembly and nanotribological behavior could provide a novel and promising pathway to explore the interaction mechanisms underlying friction and reveal the structure-property relationship at the molecular level.

Cluster formation in laser-induced ablation and evaporation of solids observed by laser ionization time-of-flight mass spectrometry and scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Tench, R. J.; Balooch, M.; Bernardez, L.; Allen, Mike J.; Siekhaus, W. J.; Olander, D. R.; Wang, W.

1990-04-01

Laser ionization time-of-flight mass analysis (LIMA) used pulses (5ns) of a frequency-quadrupled Nd-YAG laser (266 nm) focused onto spots of 4 to 100 microns diameter to ablate material, and a reflectron time of flight tube to mass-analyze the plume. The observed mass spectra for Si, Pt, SiC, and UO 2 varied in the distribution of ablation products among atoms, molecules and clusters, depending on laser power density and target material. Cleaved surfaces of highly oriented pyrolytic graphite (HOPG) positioned at room temperature either 10 cm away from materials ablated at 10(exp -5) Torr by 1 to 3 excimer laser (308 nm) pulses of 20 ns duration or 1 m away from materials vaporized at 10(exp -8) Torr by 10 Nd-Glass laser pulses of 1 ms duration were analyzed by Scanning Tunneling Microscopy (STM) in air with angstrom resolution. Clusters up to 30 A in diameter were observed.

Substrate Selection for Fundamental Studies of Electrocatalysts and Photoelectrodes: Inert Potential Windows in Acidic, Neutral, and Basic Electrolyte

DOE PAGES

Benck, Jesse D.; Pinaud, Blaise A.; Gorlin, Yelena; ...

2014-10-30

The selection of an appropriate substrate is an important initial step for many studies of electrochemically active materials. In order to help researchers with the substrate selection process, we employ a consistent experimental methodology to evaluate the electrochemical reactivity and stability of seven potential substrate materials for electrocatalyst and photoelectrode evaluation. Using cyclic voltammetry with a progressively increased scan range, we characterize three transparent conducting oxides (indium tin oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide) and four opaque conductors (gold, stainless steel 304, glassy carbon, and highly oriented pyrolytic graphite) in three different electrolytes (sulfuric acid, sodium acetate, andmore » sodium hydroxide). Here, we determine the inert potential window for each substrate/electrolyte combination and make recommendations about which materials may be most suitable for application under different experimental conditions. Furthermore, the testing methodology provides a framework for other researchers to evaluate and report the baseline activity of other substrates of interest to the broader community.« less

Direct determination of the local Hamaker constant of inorganic surfaces based on scanning force microscopy

NASA Astrophysics Data System (ADS)

Krajina, Brad A.; Kocherlakota, Lakshmi S.; Overney, René M.

2014-10-01

The energetics involved in the bonding fluctuations between nanometer-sized silicon dioxide (SiO2) probes and highly oriented pyrolytic graphite (HOPG) and molybdenum disulfide (MoS2) could be quantified directly and locally on the submicron scale via a time-temperature superposition analysis of the lateral forces between scanning force microscopy silicon dioxide probes and inorganic sample surfaces. The so-called "intrinsic friction analysis" (IFA) provided direct access to the Hamaker constants for HOPG and MoS2, as well as the control sample, calcium fluoride (CaF2). The use of scanning probe enables nanoscopic analysis of bonding fluctuations, thereby overcoming challenges associated with larger scale inhomogeneity and surface roughness common to conventional techniques used to determine surface free energies and dielectric properties. A complementary numerical analysis based on optical and electron energy loss spectroscopy and the Lifshitz quantum electrodynamic theory of van der Waals interactions is provided and confirms quantitatively the IFA results.

Direct determination of the local Hamaker constant of inorganic surfaces based on scanning force microscopy.

PubMed

Krajina, Brad A; Kocherlakota, Lakshmi S; Overney, René M

2014-10-28

The energetics involved in the bonding fluctuations between nanometer-sized silicon dioxide (SiO2) probes and highly oriented pyrolytic graphite (HOPG) and molybdenum disulfide (MoS2) could be quantified directly and locally on the submicron scale via a time-temperature superposition analysis of the lateral forces between scanning force microscopy silicon dioxide probes and inorganic sample surfaces. The so-called "intrinsic friction analysis" (IFA) provided direct access to the Hamaker constants for HOPG and MoS2, as well as the control sample, calcium fluoride (CaF2). The use of scanning probe enables nanoscopic analysis of bonding fluctuations, thereby overcoming challenges associated with larger scale inhomogeneity and surface roughness common to conventional techniques used to determine surface free energies and dielectric properties. A complementary numerical analysis based on optical and electron energy loss spectroscopy and the Lifshitz quantum electrodynamic theory of van der Waals interactions is provided and confirms quantitatively the IFA results.

Quantized edge modes in atomic-scale point contacts in graphene.

PubMed

Kinikar, Amogh; Phanindra Sai, T; Bhattacharyya, Semonti; Agarwala, Adhip; Biswas, Tathagata; Sarker, Sanjoy K; Krishnamurthy, H R; Jain, Manish; Shenoy, Vijay B; Ghosh, Arindam

2017-07-01

The zigzag edges of single- or few-layer graphene are perfect one-dimensional conductors owing to a set of gapless states that are topologically protected against backscattering. Direct experimental evidence of these states has been limited so far to their local thermodynamic and magnetic properties, determined by the competing effects of edge topology and electron-electron interaction. However, experimental signatures of edge-bound electrical conduction have remained elusive, primarily due to the lack of graphitic nanostructures with low structural and/or chemical edge disorder. Here, we report the experimental detection of edge-mode electrical transport in suspended atomic-scale constrictions of single and multilayer graphene created during nanomechanical exfoliation of highly oriented pyrolytic graphite. The edge-mode transport leads to the observed quantization of conductance close to multiples of G 0  = 2e 2 /h. At the same time, conductance plateaux at G 0 /2 and a split zero-bias anomaly in non-equilibrium transport suggest conduction via spin-polarized states in the presence of an electron-electron interaction.

Role of oxygen-containing functional groups in forest fire-generated and pyrolytic chars for immobilization of copper and nickel.

PubMed

Esfandbod, Maryam; Merritt, Christopher R; Rashti, Mehran Rezaei; Singh, Balwant; Boyd, Sue E; Srivastava, Prashant; Brown, Christopher L; Butler, Orpheus M; Kookana, Rai S; Chen, Chengrong

2017-01-01

Char as a carbon-rich material, can be produced under pyrolytic conditions, wildfires or prescribed burn offs for fire management. The objective of this study was to elucidate mechanistic interactions of copper (Cu 2+ ) and nickel (Ni 2+ ) with different chars produced by pyrolysis (green waste, GW; blue-Mallee, BM) and forest fires (fresh-burnt by prescribed fire, FC; aged char produced by wild fire, AC). The pyrolytic chars were more effective sorbents of Cu 2+ (∼11 times) and Ni 2+ (∼5 times) compared with the forest fire chars. Both cross-polarization (CPMAS-NMR) and Bloch decay (BDMAS-NMR) 13 C NMR spectroscopies showed that forest fire chars have higher woody components (aromatic functional groups) and lower polar groups (e.g. O-alkyl C) compared with the pyrolytic chars. The polarity index was greater in the pyrolytic chars (0.99-1.34) than in the fire-generated chars (0.98-1.15), while aromaticity was lower in the former than in the latter. Fourier transform infrared (FTIR) and Raman spectroscopies indicated the binding of carbonate and phosphate with both Cu 2+ and Ni 2+ in all chars, but with a greater extent in pyrolytic than forest fire-generated chars. These findings have demonstrated the key role of char's oxygen-containing functional groups in determining their sorption capacity for the Cu 2+ and Ni 2+ in contaminated lands. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mechanisms of ultrafast laser-induced deep-subwavelength gratings on graphite and diamond

NASA Astrophysics Data System (ADS)

Huang, Min; Zhao, Fuli; Cheng, Ya; Xu, Ningsheg; Xu, Zhizhan

2009-03-01

Deep-subwavelength gratings with periodicities of 170, 120, and 70 nm can be observed on highly oriented pyrolytic graphite irradiated by a femtosecond (fs) laser at 800 nm. Under picosecond laser irradiation, such gratings likewise can be produced. Interestingly, the 170-nm grating is also observed on single-crystal diamond irradiated by the 800-nm fs laser. In our opinion, the optical properties of the high-excited state of material surface play a key role for the formation of the deep-subwavelength gratings. The numerical simulations of the graphite deep-subwavelength grating at normal and high-excited states confirm that in the groove the light intensity can be extraordinarily enhanced via cavity-mode excitation in the condition of transverse-magnetic wave irradiation with near-ablation-threshold fluences. This field enhancement of polarization sensitiveness in deep-subwavelength apertures acts as an important feedback mechanism for the growth and polarization dependence of the deep-subwavelength gratings. In addition, we suggest that surface plasmons are responsible for the formation of seed deep-subwavelength apertures with a particular periodicity and the initial polarization dependence. Finally, we propose that the nanoscale Coulomb explosion occurring in the groove is responsible for the ultrafast nonthermal ablation mechanism.

Nanoscale electrochemical patterning reveals the active sites for catechol oxidation at graphite surfaces.

PubMed

Patel, Anisha N; McKelvey, Kim; Unwin, Patrick R

2012-12-19

Graphite-based electrodes (graphite, graphene, and nanotubes) are used widely in electrochemistry, and there is a long-standing view that graphite step edges are needed to catalyze many reactions, with the basal surface considered to be inert. In the present work, this model was tested directly for the first time using scanning electrochemical cell microscopy reactive patterning and shown to be incorrect. For the electro-oxidation of dopamine as a model process, the reaction rate was measured at high spatial resolution across a surface of highly oriented pyrolytic graphite. Oxidation products left behind in a pattern defined by the scanned electrochemical cell served as surface-site markers, allowing the electrochemical activity to be correlated directly with the graphite structure on the nanoscale. This process produced tens of thousands of electrochemical measurements at different locations across the basal surface, unambiguously revealing it to be highly electrochemically active, with step edges providing no enhanced activity. This new model of graphite electrodes has significant implications for the design of carbon-based biosensors, and the results are additionally important for understanding electrochemical processes on related sp(2)-hybridized materials such as pristine graphene and nanotubes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oloff, L.-P., E-mail: oloff@physik.uni-kiel.de; Hanff, K.; Stange, A.

With the advent of ultrashort-pulsed extreme ultraviolet sources, such as free-electron lasers or high-harmonic-generation (HHG) sources, a new research field for photoelectron spectroscopy has opened up in terms of femtosecond time-resolved pump-probe experiments. The impact of the high peak brilliance of these novel sources on photoemission spectra, so-called vacuum space-charge effects caused by the Coulomb interaction among the photoemitted probe electrons, has been studied extensively. However, possible distortions of the energy and momentum distributions of the probe photoelectrons caused by the low photon energy pump pulse due to the nonlinear emission of electrons have not been studied in detail yet.more » Here, we systematically investigate these pump laser-induced space-charge effects in a HHG-based experiment for the test case of highly oriented pyrolytic graphite. Specifically, we determine how the key parameters of the pump pulse—the excitation density, wavelength, spot size, and emitted electron energy distribution—affect the measured time-dependent energy and momentum distributions of the probe photoelectrons. The results are well reproduced by a simple mean-field model, which could open a path for the correction of pump laser-induced space-charge effects and thus toward probing ultrafast electron dynamics in strongly excited materials.« less

Nano-structured variable capacitor based on P(VDF-TrFE) copolymer and carbon nanotubes

NASA Astrophysics Data System (ADS)

Lakbita, I.; El-Hami, K.

2018-02-01

A newly organic capacitor was conceived with a variable capacitance using the inverse piezoelectric effect. The device consists of two parallel plates of carbon nanotubes (CNTs), known for their large surface area, high sensitivity and high electric conductivity, separated by a thin film of a dielectric layer of Polyinylidene fluoride and trifluoroehtylene (P(VDF-TrFE)) promising material for piezoelectric and ferroelectric properties. The obtained architecture is the CNT/PVDF-TrFE/CNT capacitor device. In this study, an ultra-thin film of P(VDF-TrFE) (54/46) with thickness of 20 nm was elaborated on highly oriented pyrolytic graphite (HOPG) by spin-coating. The morphology of the ultra-thin film and the mechanical behavior of CNT/P(VDF-TrFE)/CNT system were studied using the atomic force microscopy (AFM) combined with a lock-in amplifier in contact mode. All changes in applied voltage induce a change in thin film thickness according to the inverse piezoelectric effect that affect, consequently the capacitance. The results showed that the ratio of capacitance change ΔC to initial capacitance C0 is ΔC/C0=5%. This value is sufficient to use P(VDF-TrFE) as variable organic capacitor.

Covalent Modification of Highly Ordered Pyrolytic Graphite with a Stable Organic Free Radical by Using Diazonium Chemistry.

PubMed

Seber, Gonca; Rudnev, Alexander V; Droghetti, Andrea; Rungger, Ivan; Veciana, Jaume; Mas-Torrent, Marta; Rovira, Concepció; Crivillers, Núria

2017-01-26

A novel, persistent, electrochemically active perchlorinated triphenylmethyl (PTM) radical with a diazonium functionality has been covalently attached to highly ordered pyrolytic graphite (HOPG) by electrografting in a single-step process. Electrochemical scanning tunneling microscopy (EC-STM) and Raman spectroscopy measurements revealed that PTM molecules had a higher tendency to covalently react at the HOPG step edges. The cross-section profiles from EC-STM images showed that there was current enhancement at the functionalized areas, which could be explained by redox-mediated electron tunneling through surface-confined redox-active molecules. Cyclic voltammetry clearly demonstrated that the intrinsic properties of the organic radical were preserved upon grafting and DFT calculations also revealed that the magnetic character of the PTM radical was preserved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Void forming pyrolytic carbon coating process

DOEpatents

Beatty, Ronald L.; Cook, Jackie L.

2000-01-01

A pyrolytic carbon coated nuclear fuel particle and method of making it. The fuel particle has a core composed of a refractory compound of an actinide metal. The pyrolytic carbon coating surrounds the core so as to provide a void volume therebetween. The coating has an initial density of no greater than 1.45 grams/cm.sup.3 and an anisotropy factor than 3.0 and a final density upon heat treatment above about 2000.degree. C. of greater than 1.7 grams/cm.sup.3 and an anisotropy factor greater than 5.

Pyrolytic Characteristics and Kinetics of Phragmites australis

PubMed Central

Zhao, Hui; Yan, Huaxiao; Zhang, Congwang; Liu, Xiaodong; Xue, Yanhui; Qiao, Yingyun; Tian, Yuanyu; Qin, Song

2011-01-01

The pyrolytic kinetics of Phragmites australis was investigated using thermogravimetric analysis (TGA) method with linear temperature programming process under an inert atmosphere. Kinetic expressions for the degradation rate in devolatilization and combustion steps have been obtained for P. australis with Dollimore method. The values of apparent activation energy, the most probable mechanism functions, and the corresponding preexponential factor were determined. The results show that the model agrees well with the experimental data and provide useful information for the design of pyrolytic processing system using P. australis as feedstock to produce biofuel. PMID:22007256

Pyrolysis characteristics of integrated circuit boards at various particle sizes and temperatures.

PubMed

Chiang, Hung-Lung; Lin, Kuo-Hsiung; Lai, Mei-Hsiu; Chen, Ting-Chien; Ma, Sen-Yi

2007-10-01

A pyrolysis method was employed to recycle the metals and brominated compounds blended into printed circuit boards. This research investigated the effect of particle size and process temperature on the element composition of IC boards and pyrolytic residues, liquid products, and water-soluble ionic species in the exhaust, with the overall goal being to identify the pyrolysis conditions that will have the least impact on the environment. Integrated circuit (IC) boards were crushed into 5-40 mesh (0.71-4.4mm), and the crushed particles were pyrolyzed at temperatures ranging from 200 to 500 degrees C. The thermal decomposition kinetics were measured by a thermogravimetric (TG) analyzer. The composition of pyrolytic residues was analyzed by Energy Dispersive X-ray Spectrometer (EDS), Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). In addition, the element compositions of liquid products were analyzed by ICP-AES and ICP-MS. Pyrolytic exhaust was collected by a water-absorption system in an ice-bath cooler, and IC analysis showed that the absorbed solution comprised 11 ionic species. Based on the pyrolytic kinetic parameters of TG analysis and pyrolytic residues at various temperatures for 30 min, the effect of particle size was insignificant in this study, and temperature was the key factor for the IC board pyrolysis. Two stages of decomposition were found for IC board pyrolysis under nitrogen atmosphere. The activation energy was 38-47 kcal/mol for the first-stage reaction and 5.2-9.4 kcal/mol for the second-stage reaction. Metal content was low in the liquid by-product of the IC board pyrolysis process, which is an advantage in that the liquid product could be used as a fuel. Brominate and ammonium were the main water-soluble ionic species of the pyrolytic exhaust. A plan for their safe and effective disposal must be developed if the pyrolytic recycling process is to be applied to IC boards.

Thermal Pyrolytic Graphite Enhanced Components

NASA Technical Reports Server (NTRS)

Hardesty, Robert E. (Inventor)

2015-01-01

A thermally conductive composite material, a thermal transfer device made of the material, and a method for making the material are disclosed. Apertures or depressions are formed in aluminum or aluminum alloy. Plugs are formed of thermal pyrolytic graphite. An amount of silicon sufficient for liquid interface diffusion bonding is applied, for example by vapor deposition or use of aluminum silicon alloy foil. The plugs are inserted in the apertures or depressions. Bonding energy is applied, for example by applying pressure and heat using a hot isostatic press. The thermal pyrolytic graphite, aluminum or aluminum alloy and silicon form a eutectic alloy. As a result, the plugs are bonded into the apertures or depressions. The composite material can be machined to produce finished devices such as the thermal transfer device. Thermally conductive planes of the thermal pyrolytic graphite plugs may be aligned in parallel to present a thermal conduction path.

Observation of Persistent Currents in Finely Dispersed Pyrolytic Graphite

NASA Astrophysics Data System (ADS)

Saad, M.; Gilmutdinov, I. F.; Kiiamov, A. G.; Tayurskii, D. A.; Nikitin, S. I.; Yusupov, R. V.

2018-01-01

The trapped magnetic flux in the finely ground pyrolytic graphite sample annealed at 670 K in air has been observed. Flux trapping occurs on cooling of the sample from room temperature to 10 K in a magnetic field of 1 T. The magnitude and sign of the induced trapped moment remain unchanged when the applied magnetic field is varied within ±1 T at T K. The trapped magnetic flux is manifested in the displacement of the magnetization curve relative to that of the sample cooled in zero field. Displacement magnitude gradually decreases with the temperature increase up to 350 K, not reaching zero. The set of experimental observations probably reflects the presence in the sample of a granular high-temperature superconducting phase.

Catalytic and thermal depolymerization of low value post-consumer high density polyethylene plastic

USDA-ARS?s Scientific Manuscript database

The feasibility of catalytic and non-catalytic pyrolytic conversion of low value post-consumer high density polyethylene (HDPE) plastic into crude oil and subsequent distillation was explored. Translation of optimized conditions for catalytic and non-catalytic pyrolysis from TGA to a bench-scale sys...

Ellipsometry with polarisation analysis at cryogenic temperatures inside a vacuum chamber

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bauer, S.; Grees, B.; Spitzer, D.

2013-12-15

In this paper we describe a new variant of null ellipsometry to determine thicknesses and optical properties of thin films on a substrate at cryogenic temperatures. In the PCSA arrangement of ellipsometry the polarizer and the compensator are placed before the substrate and the analyzer after it. Usually, in the null ellipsometry the polarizer and the analyzer are rotated to find the searched minimum in intensity. In our variant we rotate the polarizer and the compensator instead, both being placed in the incoming beam before the substrate. Therefore the polarisation analysis of the reflected beam can be realized by anmore » analyzer at fixed orientation. We developed this method for investigations of thin cryogenic films inside a vacuum chamber where the analyzer and detector had to be placed inside the cold shield at a temperature of T≈ 90 K close to the substrate. All other optical components were installed at the incoming beam line outside the vacuum chamber, including all components which need to be rotated during the measurements. Our null ellipsometry variant has been tested with condensed krypton films on a highly oriented pyrolytic graphite substrate (HOPG) at a temperature of T≈ 25 K. We show that it is possible to determine the indices of refraction of condensed krypton and of the HOPG substrate as well as thickness of krypton films with reasonable accuracy.« less

Pyrolytic carbon-coated stainless steel felt as a high-performance anode for bioelectrochemical systems.

PubMed

Guo, Kun; Hidalgo, Diana; Tommasi, Tonia; Rabaey, Korneel

2016-07-01

Scale up of bioelectrochemical systems (BESs) requires highly conductive, biocompatible and stable electrodes. Here we present pyrolytic carbon-coated stainless steel felt (C-SS felt) as a high-performance and scalable anode. The electrode is created by generating a carbon layer on stainless steel felt (SS felt) via a multi-step deposition process involving α-d-glucose impregnation, caramelization, and pyrolysis. Physicochemical characterizations of the surface elucidate that a thin (20±5μm) and homogenous layer of polycrystalline graphitic carbon was obtained on SS felt surface after modification. The carbon coating significantly increases the biocompatibility, enabling robust electroactive biofilm formation. The C-SS felt electrodes reach current densities (jmax) of 3.65±0.14mA/cm(2) within 7days of operation, which is 11 times higher than plain SS felt electrodes (0.30±0.04mA/cm(2)). The excellent biocompatibility, high specific surface area, high conductivity, good mechanical strength, and low cost make C-SS felt a promising electrode for BESs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Aromatics extraction from pyrolytic sugars using ionic liquid to enhance sugar fermentability.

PubMed

Li, Xiaohua; Luque-Moreno, Luis C; Oudenhoven, Stijn R G; Rehmann, Lars; Kersten, Sascha R A; Schuur, Boelo

2016-09-01

Fermentative bioethanol production from pyrolytic sugars was improved via aromatics removal by liquid-liquid extraction. As solvents, the ionic liquid (IL) trihexyltetradecylphosphonium dicyanamide (P666,14[N(CN)2]) and ethyl acetate (EA) were compared. Two pyrolytic sugar solutions were created from acid-leached and untreated pinewood, with levoglucosan contents (most abundant sugar) of 29.0% and 8.3% (w/w), respectively. In a single stage extraction, 70% of the aromatics were effectively removed by P666,14[N(CN)2] and 50% by EA, while no levoglucosan was extracted. The IL was regenerated by vacuum evaporation (100mbar) at 220°C, followed by extraction of aromatics from fresh pyrolytic sugar solutions. Regenerated IL extracted aromatics with similar extraction efficiency as the fresh IL, and the purified sugar fraction from pretreated pinewood was hydrolyzed to glucose and fermented to ethanol, yielding 0.46g ethanol/(g glucose), close to the theoretical maximum yield. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Covalent Attachment of the Water-insoluble Ni(P Cy 2 N Phe 2 ) 2 Electrocatalyst to Electrodes Showing Reversible Catalysis in Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodríguez-Maciá, Patricia; Priyadarshani, Nilusha; Dutta, Arnab

Hydrogenases are a diverse group of metalloenzymes which catalyze the reversible conversion between molecular hydrogen and protons at high rates. The catalytic activity of these enzymes does not require overpotential because their active site has been evolutionarily optimized to operate fast and efficiently. These enzymes have inspired the development of molecular catalysts, which have dramatically improved in efficiency in recent years, to the point that some synthetic catalysts even outperform hydrogenases under certain conditions. In this work, we use a reversible noble-metal-free homogeneous catalyst, the [Ni(PCy2NPhe2)2]2+ complex, and we covalently immobilize it on a functionalized highly oriented pyrolytic graphite “edge”more » (HOPGe) electrode surface. This catalyst is not water soluble, but once it is surface-confined on the electrode, it maintains its catalytic properties in aqueous solutions, showing reversibility for H2 oxidation/reduction. Immobilization of the [Ni(PCy2NPhe2)2]2+ complex onto a multi-walled carbon nanotubes coated electrode leads to even higher catalytic current densities and enhanced stability.« less

Catalytic pyrolysis of car tire waste using expanded perlite.

PubMed

Kar, Y

2011-08-01

In this study, the non-catalytic and catalytic pyrolysis experiments were conducted on the sample of tire waste using expanded perlite as an additive material to determine especially the effect of temperature and catalyst-to-tire ratio on the products yields and the compositions and qualities of pyrolytic oils (NCPO and CPO). Non-catalytic studies, which were carried out under the certain conditions (a nitrogen flow of 100mL/min and a heating rate of 10°C/min), showed that the highest yield of pyrolytic oil (NCPO) was 60.02wt.% at 425°C. Then, the catalytic pyrolysis studies were carried out at catalyst-to-tire ratio range of 0.05-0.25 and the highest catalytic pyrolytic oil (CPO) yield was 65.11wt.% at the ratio of 0.10 with the yield increase of 8.48wt.% compared with the non-catalytic pyrolysis. Lastly, the pyrolytic oils were characterized with applying a various techniques such as elemental analyses and various chromatographic and spectroscopic techniques (GC-MS, (1)H NMR, FT-IR, etc.). The characterization results revealed that the pyrolytic oils which were complex mixtures of C(5)-C(15) organic compounds (predominantly aromatic compounds) and also the CPO compared to the NCPO was more similar to conventional fuels in view of the certain fuel properties. Copyright © 2011 Elsevier Ltd. All rights reserved.

Pyrolytic Carbon Nanosheets for Ultrafast and Ultrastable Sodium-Ion Storage.

PubMed

Cho, Se Youn; Kang, Minjee; Choi, Jaewon; Lee, Min Eui; Yoon, Hyeon Ji; Kim, Hae Jin; Leal, Cecilia; Lee, Sungho; Jin, Hyoung-Joon; Yun, Young Soo

2018-04-01

Na-ion cointercalation in the graphite host structure in a glyme-based electrolyte represents a new possibility for using carbon-based materials (CMs) as anodes for Na-ion storage. However, local microstructures and nanoscale morphological features in CMs affect their electrochemical performances; they require intensive studies to achieve high levels of Na-ion storage performances. Here, pyrolytic carbon nanosheets (PCNs) composed of multitudinous graphitic nanocrystals are prepared from renewable bioresources by heating. In particular, PCN-2800 prepared by heating at 2800 °C has a distinctive sp 2 carbon bonding nature, crystalline domain size of ≈44.2 Å, and high electrical conductivity of ≈320 S cm -1 , presenting significantly high rate capability at 600 C (60 A g -1 ) and stable cycling behaviors over 40 000 cycles as an anode for Na-ion storage. The results of this study show the unusual graphitization behaviors of a char-type carbon precursor and exceptionally high rate and cycling performances of the resulting graphitic material, PCN-2800, even surpassing those of supercapacitors. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pyrolytic carbon-coated nuclear fuel

DOEpatents

Lindemer, Terrence B.; Long, Jr., Ernest L.; Beatty, Ronald L.

1978-01-01

An improved nuclear fuel kernel having at least one pyrolytic carbon coating and a silicon carbon layer is provided in which extensive interaction of fission product lanthanides with the silicon carbon layer is avoided by providing sufficient UO.sub.2 to maintain the lanthanides as oxides during in-reactor use of said fuel.

Covering surface nanobubbles with a NaCl nanoblanket.

PubMed

Berkelaar, Robin P; Zandvliet, Harold J W; Lohse, Detlef

2013-09-10

By letting a NaCl aqueous solution of low (0.01 M) concentration evaporate on a highly oriented pyrolytic graphite (HOPG) surface, it is possible to form a thin film of salt. However, pre-existing surface nanobubbles prevent the homogeneous coverage of the surface with the salt, keeping the footprint areas on the substrate pristine. Comparing the surface nanobubbles in the salt solution with their associated footprint after drying, provides information on the shrinkage of nanobubbles during the hours-long process of drying the liquid film. At a slightly higher NaCl concentration and thus salt layer thickness, the nanobubbles are covered with a thin blanket of salt. Once the liquid film has evaporated until a water film remains that is smaller than the height of the nanobubbles, the blanket of salt cracks and unfolds into a flower-like pattern of salt flakes that is located at the rim of the nanobubble footprint. The formation of a blanket of salt covering the nanobubbles is likely to considerably or even completely block the gas out-flux from the nanobubble, partially stabilizing the nanobubbles against dissolution.

HOPG/ZnO/HOPG pressure sensor

NASA Astrophysics Data System (ADS)

Jahangiri, Mojtaba; Yousefiazari, Ehsan; Ghalamboran, Milad

2017-12-01

Pressure sensor is one of the most commonly used sensors in the research laboratories and industries. These are generally categorized in three different classes of absolute pressure sensors, gauge pressure sensors, and differential pressure sensors. In this paper, we fabricate and assess the pressure sensitivity of the current vs. voltage diagrams in a graphite/ZnO/graphite structure. Zinc oxide layers are deposited on highly oriented pyrolytic graphite (HOPG) substrates by sputtering a zinc target under oxygen plasma. The top electrode is also a slice of HOPG which is placed on the ZnO layer and connected to the outside electronic circuits. By recording the I-V characteristics of the device under different forces applied to the top HOPG electrode, the pressure sensitivity is demonstrated; at the optimum biasing voltage, the device current changes 10 times upon changing the pressure level on the top electrode by 20 times. Repeatability and reproducibility of the observed effect is studied on the same and different samples. All the materials used for the fabrication of this pressure sensor are biocompatible, the fabricated device is anticipated to find potential applications in biomedical engineering.

Thrombin-Binding Aptamer Quadruplex Formation: AFM and Voltammetric Characterization

PubMed Central

Diculescu, Victor Constantin; Chiorcea-Paquim, Ana-Maria; Eritja, Ramon; Oliveira-Brett, Ana Maria

2010-01-01

The adsorption and the redox behaviour of thrombin-binding aptamer (TBA) and extended TBA (eTBA) were studied using atomic force microscopy and voltammetry at highly oriented pyrolytic graphite and glassy carbon. The different adsorption patterns and degree of surface coverage were correlated with the sequence base composition, presence/absence of K+, and voltammetric behaviour of TBA and eTBA. In the presence of K+, only a few single-stranded sequences present adsorption, while the majority of the molecules forms stable and rigid quadruplexes with no adsorption. Both TBA and eTBA are oxidized and the only anodic peak corresponds to guanine oxidation. Upon addition of K+ ions, TBA and eTBA fold into a quadruplex, causing the decrease of guanine oxidation peak and occurrence of a new peak at a higher potential due to the oxidation of G-quartets. The higher oxidation potential of G-quartets is due to the greater difficulty of electron transfer from the inside of the quadruplex to the electrode surface than electron transfer from the more flexible single strands. PMID:20798847

Effect of intermolecular dipole-dipole interactions on interfacial supramolecular structures of C3-symmetric hexa-peri-hexabenzocoronene derivatives.

PubMed

Mu, Zhongcheng; Shao, Qi; Ye, Jun; Zeng, Zebing; Zhao, Yang; Hng, Huey Hoon; Boey, Freddy Yin Chiang; Wu, Jishan; Chen, Xiaodong

2011-02-15

Two-dimensional (2D) supramolecular assemblies of a series of novel C(3)-symmetric hexa-peri-hexabenzocoronene (HBC) derivatives bearing different substituents adsorbed on highly oriented pyrolytic graphite were studied by using scanning tunneling microscopy at a solid-liquid interface. It was found that the intermolecular dipole-dipole interactions play a critical role in controlling the interfacial supramolecular assembly of these C(3)-symmetric HBC derivatives at the solid-liquid interface. The HBC molecule bearing three -CF(3) groups could form 2D honeycomb structures because of antiparallel dipole-dipole interactions, whereas HBC molecules bearing three -CN or -NO(2) groups could form hexagonal superstructures because of a special trimeric arrangement induced by dipole-dipole interactions and weak hydrogen bonding interactions ([C-H···NC-] or [C-H···O(2)N-]). Molecular mechanics and dynamics simulations were performed to reveal the physics behind the 2D structures as well as detailed functional group interactions. This work provides an example of how intermolecular dipole-dipole interactions could enable fine control over the self-assembly of disklike π-conjugated molecules.

Method for applying pyrolytic carbon coatings to small particles

DOEpatents

Beatty, Ronald L.; Kiplinger, Dale V.; Chilcoat, Bill R.

1977-01-01

A method for coating small diameter, low density particles with pyrolytic carbon is provided by fluidizing a bed of particles wherein at least 50 per cent of the particles have a density and diameter of at least two times the remainder of the particles and thereafter recovering the small diameter and coated particles.

Performance and Vibration of 30 cm Pyrolytic Ion Thruster Optics

NASA Technical Reports Server (NTRS)

Haag, Thomas; Soulas, George C.

2004-01-01

Carbon has a sputter erosion rate about an order of magnitude less than that of molybdenum, over the voltages typically used in ion thruster applications. To explore its design potential, 30 cm pyrolytic carbon ion thruster optics have been fabricated geometrically similar to the molybdenum ion optics used on NSTAR. They were then installed on an NSTAR Engineering Model thruster, and experimentally evaluated over much of the original operating envelope. Ion beam currents ranged from 0.51 to 1.76 Angstroms, at total voltages up to 1280 V. The perveance, electron back-streaming limit, and screen-grid transparency were plotted for these operating points, and compared with previous data obtained with molybdenum. While thruster performance with pyrolytic carbon was quite similar to that with molybdenum, behavior variations can reasonably be explained by slight geometric differences. Following all performance measurements, the pyrolytic carbon ion optics assembly was subjected to an abbreviated vibration test. The thruster endured 9.2 g(sub rms) of random vibration along the thrust axis, similar to DS 1 acceptance levels. Despite significant grid clashing, there was no observable damage to the ion optics assembly.

Retrofitting hetrotrophically cultivated algae biomass as pyrolytic feedstock for biogas, bio-char and bio-oil production encompassing biorefinery.

PubMed

Sarkar, Omprakash; Agarwal, Manu; Naresh Kumar, A; Venkata Mohan, S

2015-02-01

Algal biomass grown hetrotrophically in domestic wastewater was evaluated as pyrolytic feedstock for harnessing biogas, bio-oil and bio-char. Freshly harvested microalgae (MA) and lipid extracted microalgae (LEMA) were pyrolysed in packed bed reactor in the presence and absence of sand as additive. MA (without sand additive) depicted higher biogas (420 ml/g; 800 °C; 3 h) and bio-oil (0.70 ml/g; 500 °C; 3 h). Sand addition enhanced biogas production (210 ml/g; 600 °C; 2 h) in LEMA operation. The composition of bio-gas and bio-oil was found to depend on the nature of feedstock as well as the process conditions viz., pyrolytic-temperature, retention time and presence of additive. Sand additive improved the H2 composition while pyrolytic temperature increment caused a decline in CO2 fraction. Bio-char productivity increased with increasing temperature specifically with LEMA. Integration of thermo-chemical process with microalgae cultivation showed to yield multiple resources and accounts for environmental sustainability in the bio-refinery framework. Copyright © 2014 Elsevier Ltd. All rights reserved.

Overliming detoxification of pyrolytic sugar syrup for direct fermentation of levoglucosan to ethanol.

PubMed

Chi, Zhanyou; Rover, Marjorie; Jun, Erin; Deaton, Mark; Johnston, Patrick; Brown, Robert C; Wen, Zhiyou; Jarboe, Laura R

2013-12-01

The application of pyrolytic sugars for biofuel production through fermentation is challenged by inhibitory contaminant compounds. Inhibition is so severe that only 0.25% sugar syrup can be used. In this study, overliming was tested as a simple detoxification method, using the Escherichia coli KO11+ lgk to directly convert levoglucosan into ethanol. After treatment with at least 14.8 g/L of Ca(OH)2, fermentation with 2% (w/v) pyrolytic sugar syrup was observed with no inhibition of ethanol production. Further investigation of treatment time and temperature showed that 8-16 h of treatment at 20°C, and 1-4 h of treatment at 60°C are necessary to obtain consistent ethanol production. The samples treated with 18.5 g/L Ca(OH)2 at 60°C for 4 h showed no inhibition at 2.5%. Multiple contaminants removed by the overliming treatment were identified. This study demonstrates that overliming is a promising method for detoxification of pyrolytic sugars for fermentation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Supercritical Fuel Pyrolysis

DTIC Science & Technology

2007-05-28

be supercritical fluids . These temperatures and pressures will also cause the fuel to undergo pyrolytic reactions, which have the potential of forming...physical properties, supercritical fluids have highly variable densities, no surface tension, and transport properties (i.e., mass, energy, and momentum...are very dependent on pressure, chemical reaction rates in supercritical fluids can be highly pressure-dependent [6-9]. The kinetic reaction rate

A validation of the fibre orientation and fibre length attrition prediction for long fibre-reinforced thermoplastics

NASA Astrophysics Data System (ADS)

Hopmann, Ch.; Weber, M.; van Haag, J.; Schöngart, M.

2015-05-01

To improve the mechanical performance of polymeric parts, fibre reinforcement has established in industrial applications during the last decades. Next to the widely used Short Fibre-reinforced Thermoplastics (SFT) the use of Long Fibre-reinforced Thermoplastics (LFT) is increasingly growing. Especially for non-polar polymeric matrices like polypropylene (PP), longer fibres can significantly improve the mechanical performance. As with every kind of discontinuous fibre reinforcement the fibre orientations (FO) show a high impact on the mechanical properties. On the contrary to SFT where the local fibre length distribution (FLD) can be often neglected, for LFT the FLD show a high impact on the material's properties and has to be taken into account in equal measure to the FOD. Recently numerical models are available in commercial filling simulation software and allow predicting both the local FOD and FLD in LFT parts. The aim of this paper is to compare i.) the FOD results and ii) the FLD results from available orientation- and fibre length attrition-models to those obtained from experimental data. The investigations are conducted by the use of different injection moulded specimens made from long glass fibre reinforced PP. In order to determine the FOD, selected part sections are examined by means of Computed Tomographic (CT) analyses. The fully three dimensional measurement of the FOD is then performed by digital image processing using grey scale correlation. The FLD results are also obtained by using digital image processing after a thermal pyrolytic separation of the polymeric matrix from the fibres. Further the FOD and the FLD are predicted by using a reduced strain closure (RSC) as well as an anisotropic rotary diffusion - reduced strain closure model (ARD-RSC) and Phelps-Tucker fibre length attrition model implemented in the commercial filling software Moldflow, Autodesk Inc., San Rafael, CA, USA.

A validation of the fibre orientation and fibre length attrition prediction for long fibre-reinforced thermoplastics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hopmann, Ch.; Weber, M.; Haag, J. van

2015-05-22

To improve the mechanical performance of polymeric parts, fibre reinforcement has established in industrial applications during the last decades. Next to the widely used Short Fibre-reinforced Thermoplastics (SFT) the use of Long Fibre-reinforced Thermoplastics (LFT) is increasingly growing. Especially for non-polar polymeric matrices like polypropylene (PP), longer fibres can significantly improve the mechanical performance. As with every kind of discontinuous fibre reinforcement the fibre orientations (FO) show a high impact on the mechanical properties. On the contrary to SFT where the local fibre length distribution (FLD) can be often neglected, for LFT the FLD show a high impact on themore » material’s properties and has to be taken into account in equal measure to the FOD. Recently numerical models are available in commercial filling simulation software and allow predicting both the local FOD and FLD in LFT parts. The aim of this paper is to compare i.) the FOD results and ii) the FLD results from available orientation- and fibre length attrition-models to those obtained from experimental data. The investigations are conducted by the use of different injection moulded specimens made from long glass fibre reinforced PP. In order to determine the FOD, selected part sections are examined by means of Computed Tomographic (CT) analyses. The fully three dimensional measurement of the FOD is then performed by digital image processing using grey scale correlation. The FLD results are also obtained by using digital image processing after a thermal pyrolytic separation of the polymeric matrix from the fibres. Further the FOD and the FLD are predicted by using a reduced strain closure (RSC) as well as an anisotropic rotary diffusion - reduced strain closure model (ARD-RSC) and Phelps-Tucker fibre length attrition model implemented in the commercial filling software Moldflow, Autodesk Inc., San Rafael, CA, USA.« less

Laser induced periodic surface structures on pyrolytic carbon prosthetic heart valve

NASA Astrophysics Data System (ADS)

Stepak, Bogusz D.; Łecka, Katarzyna M.; Płonek, Tomasz; Antończak, Arkadiusz J.

2016-12-01

Laser-induced periodic surface structures (LIPSS) can appear in different forms such as ripples, grooves or cones. Those highly periodic wavy surface features which are frequently smaller than incident light wavelength bring possibility of nanostructuring of many different materials. Furthermore, by changing laser parameters one can obtain wide spectrum of periodicities and geometries. The aim of this research was to determine possibility of nanostructuring pyrolytic carbon (PyC) heart valve leaflets using different irradiation conditions. The study was performed using two laser sources with different pulse duration (15 ps, 450 fs) as well as different wavelengths (1064, 532, 355 nm). Both low and high spatial frequency LIPSS were observed for each set of irradiation parameters. In case femtosecond laser pulses we obtained deep subwavelength ripple period which was even ten times smaller than applied wavelength. Obtained ripple period was ranging from 90 up to 860 nm. Raman spectra revealed the increase of disorder after laser irradiation which was comparable for both pico- and femtosecond laser.

Nuclear fuel elements and method of making same

DOEpatents

Schweitzer, Donald G.

1992-01-01

A nuclear fuel element for a high temperature gas nuclear reactor that has an average operating temperature in excess of 2000.degree. C., and a method of making such a fuel element. The fuel element is characterized by having fissionable fuel material localized and stabilized within pores of a carbon or graphite member by melting the fissionable material to cause it to chemically react with the carbon walls of the pores. The fissionable fuel material is further stabilized and localized within the pores of the graphite member by providing one or more coatings of pyrolytic carbon or diamond surrounding the porous graphite member so that each layer defines a successive barrier against migration of the fissionable fuel from the pores, and so that the outermost layer of pyrolytic carbon or diamond forms a barrier between the fissionable material and the moderating gases used in an associated high temperature gas reactor. The method of the invention provides for making such new elements either as generally spherically elements, or as flexible filaments, or as other relatively small-sized fuel elements that are particularly suited for use in high temperature gas reactors.

Comparative study on pyrolysis of lignocellulosic and algal biomass using pyrolysis-gas chromatography/mass spectrometry.

PubMed

Li, Kai; Zhang, Liqiang; Zhu, Liang; Zhu, Xifeng

2017-06-01

The cornstalk and chlorella were selected as the representative of lignocelulosic and algal biomass, and the pyrolysis experiments of them were carried out using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The physicochemical properties of samples and the pyrolytic product distribution were presented. And then the compositional differences between the two kinds of pyrolytic products were studied, the relevant pyrolysis mechanisms were analyzed systematically. Pyrolytic vapor from lignocellulosic biomass contained more phenolic and carbonyl compounds while that from algal biomass contained more long-chain fatty acids, nitrogen-containing compounds and fewer carbonyl compounds. Maillard reaction is conducive to the conversion of carbonyl compounds to nitrogenous heterocyclic compounds with better thermal stability. Copyright © 2017 Elsevier Ltd. All rights reserved.

Recycled-tire pyrolytic carbon made functional: A high-arsenite [As(III)] uptake material PyrC350®.

PubMed

Mouzourakis, E; Georgiou, Y; Louloudi, M; Konstantinou, I; Deligiannakis, Y

2017-03-15

A novel material, PyrC 350 ® , has been developed from pyrolytic-tire char (PyrC), as an efficient low-cost Arsenite [As(III)] adsorbent from water. PyrC 350 ® achieves 31mgg -1 As(III) uptake, that remains unaltered at pH=4-8.5. A theoretical Surface Complexation Model has been developed that explains the adsorption mechanism, showing that in situ formed Fe 3 C, ZnS particles act cooperatively with the carbon matrix for As(III) adsorption. Addressing the key-issue of cost-effectiveness, we provide a comparison of As(III)-uptake effectiveness in conjunction with a cost analysis, showing that PyrC 350 ® stands in the top of [effectiveness/cost] vs. existing carbon-based, low-cost materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Precision blackbody sources for radiometric standards.

PubMed

Sapritsky, V I; Khlevnoy, B B; Khromchenko, V B; Lisiansky, B E; Mekhontsev, S N; Melenevsky, U A; Morozova, S P; Prokhorov, A V; Samoilov, L N; Shapoval, V I; Sudarev, K A; Zelener, M F

1997-08-01

The precision blackbody sources developed at the All-Russian Institute for Optical and Physical Measurements (Moscow, Russia) and their characteristics are analyzed. The precision high-temperature graphite blackbody BB22p, large-area high-temperature pyrolytic graphite blackbody BB3200pg, middle-temperature graphite blackbody BB2000, low-temperature blackbody BB300, and gallium fixed-point blackbody BB29gl and their characteristics are described.

[Study on the determination of trace gallium in molybdenum-coated pyrolytic graphite tube by electrothermal absorption spectrometry].

PubMed

Huang, Yu-an; Zhou, Fang-qin; Long, Si-hua; Yang, Liu

2004-02-01

The effects on gallium atomization in the pyrolytic graphite tube imposed by different matrix modifiers and different coatings were discussed detailedly in this paper. In the presence of matrix modifier of Ni(NO3)2 the matrix interference was eliminated efficiently. The pyrolytic graphite tubes were coated differently with lanthanum, zirconium, and molybdenum to avoid producing gallium carbide. Results showed that the tube with molybdenum coating was the best. On this basis, the mechanism of gallium atomization in the molybdenum-coated pyrolytic graphite tube using Ni(NO3)2 as a matrix modifier was studied furthermore; in addition, the parameters of the operation were optimized. As a result, a new method improved in many aspects was developed to detect trace gallium in complicated sample of gangue. The outcomes of practical applications indicated that the method could satisfy the requests of analysis and that the manipulations were simple to achieve. The characteristic content, the detection limit, and the adding recoveries were 2.12 x 10(-11) g, 1.4 x 10(-10) g and 97.4%-102.7% respectively, and the relative standard deviation was less than or equal to 3.6% (n = 11).

Formation of the reduced form of furaneol® (2,5-dimethyl-4-hydroxy-tetrahydrofuran-3-one) during the Maillard reaction through catalysis of amino acid metal salts.

PubMed

Nashalian, Ossanna; Wang, Xi; Yaylayan, Varoujan A

2016-11-01

Under pyrolytic conditions the acidity/basicity of Maillard reaction mixtures can be controlled through the use of hydrochloride or sodium salts of amino acids to generate a diversity of products. When the degradation of glucose was studied under pyrolytic conditions using excess sodium glycinate the reaction was found to generate a major unknown peak having a molecular ion at m/z 130. Subsequent in-depth isotope labelling studies indicated that acetol was an important precursor of this compound under pyrolytic and aqueous heating conditions. The dimerisation and cyclisation of acetol into 2,5-dimethyl-4-hydroxy-tetrahydrofuran-3-one was found to be catalysed by amino acid metal salts. Also, ESI/qTOF/MS studies indicated that the unknown peak has expected molecular formula of C6H10O3. Finally, a peak having the same retention time and mass spectrum was also generated pyrolytically when furaneol® was reduced with NaBH4 confirming the initial hypothesis regarding the unknown peak to be the reduced form of furaneol®. Copyright © 2016 Elsevier Ltd. All rights reserved.

A collection system for dry solid residues from exhaled breath for analysis via atomic force microscopy.

PubMed

Morozov, Victor N; Mikheev, Andrey Y

2017-01-09

Exhaled air contains sub-micron droplets of lung liquid, which potentially bear biomarkers of lung diseases. After dehydration they form dry residue particles (DRPs). As a first step in developing techniques to characterize individual DRPs, a new electrostatic collector was designed in which DRPs are charged within a unipolar corona charger, concentrated in a cone funnel, and deposited onto a limited area of a highly oriented pyrolytic graphite surface. The collector captures 80%-90% of DRPs at an optimal flow rate of 0.15 l min -1 . Atomic force microscopy (AFM) revealed flattened round particles 20-50 nm high, with notable protrusions at their surface suggestive of an inhomogeneous internal structure. Exposure to humid air resulted in the DRPs spreading over the surface, with a 50%-200% decrease in their heights and an increase in their lateral dimensions so that their volume decreased by only 10% ± 3%. Exposure to saturated chloroform vapor resulted in drainage of 10%-15% of the DRP volume (presumably lipids), forming collar-shaped rings around each particle but leaving the core size and structure unchanged. AFM measurements combined with laser counter measurements of the DRP concentrations were used to estimate that one liter of air exhaled by volunteers contained less than 100 pg of dry residue material.

Reactive Capture of Gold Nanoparticles by Strongly Physisorbed Monolayers on Graphite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Xiaoliang; Tong, Wenjun; Fidler, Vlastimil

2012-12-01

Anthracene Diels Alder adducts (DAa) bearing two long side chains (H-(CH2)22O(CH2)6OCH2-) at the 1- and 5-positions form self-assembled monolayers (SAMs) at the phenyloctane - highly oriented pyrolytic graphite (HOPG) interface. The long DAa side chains promote strong physisorption of the monolayer to HOPG and maintain the monolayer morphology upon rinsing or incubation in ethanol and air-drying of the substrate. Incorporating a carboxylic acid group on the DAa core enables capture of 1 - 4 nm diameter gold nanoparticles (AuNP) provided (i) the monolayer containing DAa-carboxylic acids is treated with Cu2+ ions and (ii) the organic coating on the AuNP containsmore » carboxylic acids (11-mercaptoundecanoic acid, MUA-AuNP). AuNP capture by the monolayer proceeds with formation of Cu2+ - carboxylate coordination complexes. The captured AuNP appear as mono- and multi-layered clusters at high coverage on HOPG. The surface density of the captured AuNPs can be adjusted from AuNP multi-layers to isolated AuNPs by varying incubation times, MUA-AuNP concentration, the number density of carboxylic acids in the monolayer, the number of MUA per AuNP, and the post-incubation treatments.« less

Local atomic order of a metallic glass made visible by scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Luo, Yuansu; Samwer, Konrad

2018-06-01

Exploring the atomic level structure in amorphous materials by STM becomes extremely difficult due to the localized electronic states. Here we carried out STM studies on a quasi-low-dimensional film of metallic glass Zr65Cu27.5Al7.5 which is ‘ultrathin’ compared with the localization length and/or the length scale of short range order. The local electronic structure must appear more inherent, having states at E f available for tip-sample tunneling current. To enhance imaging contrasts between long-range and short-range orders, the highly oriented pyrolytic graphite was chosen as substrate, so that the structural heterogeneity arising from competition between the glass former ability and the epitaxy can be ascertained. A chemical order predicted for this system was observed in atomic ordered regimes (1–2 monolayers), accompanied with a superstructure with the period Zr–Cu(Al)–Zr along three hexagonal axes. The result implies a chemical short range order in disordered regimes, where polyhedral clusters are dominant with the solute atom Cu(Al) in the center. An attempt for the structural modelling was made based on high resolution STM images, giving icosahedral order on the surface and different Voronoi clusters in 3D space.

Application of biomass pyrolytic polygeneration technology using retort reactors.

PubMed

Yang, Haiping; Liu, Biao; Chen, Yingquan; Chen, Wei; Yang, Qing; Chen, Hanping

2016-01-01

To introduce application status and illustrate the good utilisation potential of biomass pyrolytic polygeneration using retort reactors, the properties of major products and the economic viability of commercial factories were investigated. The capacity of one factory was about 3000t of biomass per year, which was converted into 1000t of charcoal, 950,000Nm(3) of biogas, 270t of woody tar, and 950t of woody vinegar. Charcoal and fuel gas had LHV of 31MJ/kg and 12MJ/m(3), respectively, indicating their potential for use as commercial fuels. The woody tar was rich in phenols, while woody vinegar contained large quantities of water and acetic acid. The economic analysis showed that the factory using this technology could be profitable, and the initial investment could be recouped over the factory lifetime. This technology offered a promising means of converting abundant agricultural biomass into high-value products. Copyright © 2015 Elsevier Ltd. All rights reserved.

Evaluation, construction and endurance testing of compression sealed pyrolytic boron nitride slot insulation

NASA Technical Reports Server (NTRS)

Grant, W. L.

1969-01-01

A high-temperature statorette, consisting of an iron-27 percent cobalt magnetic lamination stack and nickel-clad silver conductors, was tested with pyrolytic boron nitride slot insulation. Temperatures were measured in each test to determine characteristics of slot linear heat conductance from statorette conductors. Testing was carried out to temperatures of approximately 1500 F in a vacuum environment of 10-8 torr. Three assemblies were built and tested, each having a different room temperature slot clearance. The final statorette assembly was subjected to a 100-hour vacuum aging test at 1400 F followed by 25 thermal cycles. Temperature data from the three assemblies showed that decreasing slot clearance and increasing compression loading did enhance heat transfer. The temperature difference between slot and lamination at 1400 F increased 4 F during the thermal aging and an additional 10 F during the 25 thermal cycles.

Pyrolytic carbon coated black silicon

NASA Astrophysics Data System (ADS)

Shah, Ali; Stenberg, Petri; Karvonen, Lasse; Ali, Rizwan; Honkanen, Seppo; Lipsanen, Harri; Peyghambarian, N.; Kuittinen, Markku; Svirko, Yuri; Kaplas, Tommi

2016-05-01

Carbon is the most well-known black material in the history of man. Throughout the centuries, carbon has been used as a black material for paintings, camouflage, and optics. Although, the techniques to make other black surfaces have evolved and become more sophisticated with time, carbon still remains one of the best black materials. Another well-known black surface is black silicon, reflecting less than 0.5% of incident light in visible spectral range but becomes a highly reflecting surface in wavelengths above 1000 nm. On the other hand, carbon absorbs at those and longer wavelengths. Thus, it is possible to combine black silicon with carbon to create an artificial material with very low reflectivity over a wide spectral range. Here we report our results on coating conformally black silicon substrate with amorphous pyrolytic carbon. We present a superior black surface with reflectance of light less than 0.5% in the spectral range of 350 nm to 2000 nm.

Synthesis of gold nanoparticles on the surface of pyrolytic graphite using penicillin as a stabilizing reagent and the catalytic oxidation of α-naphthylamine

NASA Astrophysics Data System (ADS)

Song, Y. Z.; Song, Y.; Cheng, Z. P.; Zhou, J. F.; Wei, C.

2013-01-01

Electrochemical synthesis of gold nanoparticles on the surface of pyrolytic graphite using penicillin as a stabilizing reagent was proposed. The gold nanoparticles were characterized by scanning electron microscopy, cyclic voltammetry, IR spectra, UV spectra, and powder X-ray diffraction spectra. The electro-chemical catalysis of penicillin for α-naphthylamine was demonstrated.

Pyrolytic conversion of plastic and rubber waste to hydrocarbons with basic salt catalysts

DOEpatents

Wingfield, Jr., Robert C.; Braslaw, Jacob; Gealer, Roy L.

1985-01-01

The invention relates to a process for improving the pyrolytic conversion of waste selected from rubber and plastic to low molecular weight olefinic materials by employing basis salt catalysts in the waste mixture. The salts comprise alkali or alkaline earth compounds, particularly sodium carbonate, in an amount of greater than about 1 weight percent based on the waste feed.

Engineering Materials for Very High Temperatures: An ONRL Workshop

DTIC Science & Technology

1988-08-29

solving various pro- blems related to high temperature applications in which thermostructural ( turbojet and motor engines) or special (electromagnetic wave...the carbon (glassy carbon, polycrystalline gra- phite, pyrolytic carbon...) and mainly upon the temperature range of use. For the 1000-20000C...Bundesministerium fir Forschung und Technologie, Federal Ministry for Research and Technology), no doubt scared by the oil crisis and encouraged by the activity

Incorporation of low energy activated nitrogen onto HOPG surface: Chemical states and thermal stability studies by in-situ XPS and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Chandran, Maneesh; Shasha, Michal; Michaelson, Shaul; Hoffman, Alon

2016-09-01

In this paper we report the chemical states analysis of activated nitrogen incorporated highly oriented pyrolytic graphite (HOPG) surface under well-controlled conditions. Nitrogen incorporation is carried out by two different processes: an indirect RF nitrogen plasma and low energy (1 keV) N2+ implantation. Bonding configuration, concentration and thermal stability of the incorporated nitrogen species by aforesaid processes are systematically compared by in-situ X-ray photoelectron spectroscopy (XPS). Relatively large concentration of nitrogen is incorporated onto RF nitride HOPG surface (16.2 at.%), compared to N2+ implanted HOPG surface (7.7 at.%). The evolution of N 1s components (N1, N2, N3) with annealing temperature is comprehensively discussed, which indicates that the formation and reorganization of local chemical bonding states are determined by the process of nitridation and not by the prior chemical conditioning (i.e., amorphization or hydrogenation) of the HOPG surface. A combined XPS and Raman spectroscopy studies revealed that N2+ implantation process resulted in a high level of defects to the HOPG surface, which cannot be annealed-out by heat treatment up to 1000 °C. On the other hand, the RF nitrogen plasma process did not produce a high level of surface defects, while incorporating nearly the same amount of stable nitrogen species.

A two-dimensional polymer synthesized at the air/water interface.

PubMed

Schlüter, A Dieter; Müller, Vivian; Hinaut, Antoine; Moradi, Mina; Baljozovic, Milos; Jung, Thomas; Shahgaldian, Patrick; Möhwald, Helmuth; Hofer, Gregor; Kröger, Martin; King, Benjamin; Meyer, Ernst; Glatzel, Thilo

2018-06-11

A trifunctional, partially fluorinated anthracene-substituted triptycene monomer is spread at the air/water interface into a monolayer, which is transformed into a long-range ordered 2D polymer by irradiation with a standard ultraviolet lamp using 365 nm light. The polymer is analyzed by Brewster angle microscopy directly at this interface and by scanning tunneling microscopy measurements and non-contact atomic force microscopy (nc-AFM), both after transfer from below the interface onto highly oriented pyrolytic graphite and then into ultra-high vacuum. Both methods confirm a network structure, the lattice parameters of which are virtually identical to a structural model network based on X-ray diffractometry of a closely related 2D polymer unequivocally established in a single crystal. The nc-AFM images are obtained with unprecedentedly high resolution and prove long-range order over areas of at least 300 × 300 nm2. As required for a 2D polymer, the pore sizes are monodisperse, except for the regions, where the network is somewhat stretched because it spans over protrusions. Together with a previous report on the nature of the cross-links in this network, the structural information provided here leaves no doubt that a 2D polymer has been synthesized under ambient conditions at an air/water interface. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supercritical Fuel Pyrolysis

DTIC Science & Technology

2010-05-30

supercritical fluids . These temperatures and pressures will also cause the fuel to undergo pyrolytic reactions, which have the potential of forming...With regard to physical properties, supercritical fluids have highly variable densities, no surface tension, and transport properties (i.e., mass...effects in supercritical fluids , often affecting chemical reaction pathways by facilitating the formation of certain transition states [6]. Because

Integrated Thermal Modules for Cooling Silicon and Silicon Carbide Power Modules

DTIC Science & Technology

2007-06-11

analyses, bench tests, and motor tests comprise the program. The ITMs, in place of standard heatsinks, use a highly conductive pyrolytic graphite to...passively cool power modules. Initial results show that even simple ITMs can lower chip temperatures by 20 deg. C and 10 deg. C with engine oil and

Pyrolytic Decomposition Studies of AA2, A Double-Base Propellent

DTIC Science & Technology

2001-10-01

broad HMW peaks in each pyrolys - ate, these data were analyzed by manual integration of each major or identified peak. The total percent areas in... pyroly - sis to permit the air peak to elute. NG is highly energetic and it shares a common behavior with NC. The majority of the pyrolysate (96.1

Electrochemical formation and characterization of Au nanostructures on a highly ordered pyrolytic graphite surface

NASA Astrophysics Data System (ADS)

Gómez, José J. Arroyo; Zubieta, Carolina; Ferullo, Ricardo M.; García, Silvana G.

2016-02-01

The electrochemical formation of Au nanoparticles on a highly ordered pyrolytic graphite (HOPG) substrate using conventional electrochemical techniques and ex-situ AFM is reported. From the potentiostatic current transients studies, the Au electrodeposition process on HOPG surfaces was described, within the potential range considered, by a model involving instantaneous nucleation and diffusion controlled 3D growth, which was corroborated by the microscopic analysis. Initially, three-dimensional (3D) hemispherical nanoparticles distributed on surface defects (step edges) of the substrate were observed, with increasing particle size at more negative potentials. The double potential pulse technique allowed the formation of rounded deposits at low deposition potentials, which tend to form lines of nuclei aligned in defined directions leading to 3D ordered structures. By choosing suitable nucleation and growth pulses, one-dimensional (1D) deposits were possible, preferentially located on step edges of the HOPG substrate. Quantum-mechanical calculations confirmed the tendency of Au atoms to join selectively on surface defects, such as the HOPG step edges, at the early stages of Au electrodeposition.

Binary Hierarchical Porous Graphene/Pyrolytic Carbon Nanocomposite Matrix Loaded with Sulfur as a High-Performance Li-S Battery Cathode.

PubMed

Zhang, Hang; Gao, Qiuming; Qian, Weiwei; Xiao, Hong; Li, Zeyu; Ma, Li; Tian, Xuehui

2018-06-06

A N,O-codoped hierarchical porous nanocomposite consisting of binary reduced graphene oxide and pyrolytic carbon (rGO/PC) from chitosan is fabricated. The optimized rGO/PC possesses micropores with size distribution concentrated around 1.1 nm and plenty of meso/macropores. The Brunauer-Emmett-Teller specific surface area is 480.8 m 2 g -1 , and it possesses impressively large pore volume of 2.14 cm 3 g -1 . On the basis of the synergistic effects of the following main factors: (i) the confined space effect in the hierarchical porous binary carbonaceous matrix; (ii) the anchor effects by strong chemical bonds with codoped N and O atoms; and (iii) the good flexibility and conductivity of rGO, the rGO/PC/S holding 75 wt % S exhibits high performance as Li-S battery cathode. Specific capacity of 1625 mA h g -1 can be delivered at 0.1 C (1 C = 1675 mA g -1 ), whereas 848 mA h g -1 can be maintained after 300 cycles at 1 C. Even at high rate of 5 C, 412 mA h g -1 can be restrained after 1000 cycles.

Sealing nuclear graphite with pyrolytic carbon

NASA Astrophysics Data System (ADS)

Feng, Shanglei; Xu, Li; Li, Li; Bai, Shuo; Yang, Xinmei; Zhou, Xingtai

2013-10-01

Pyrolytic carbon (PyC) coatings were deposited on IG-110 nuclear graphite by thermal decomposition of methane at ∼1830 °C. The PyC coatings are anisotropic and airtight enough to protect IG-110 nuclear graphite against the permeation of molten fluoride salts and the diffusion of gases. The investigations indicate that the sealing nuclear graphite with PyC coating is a promising method for its application in Molten Salt Reactor (MSR).

Analysis of HEMCL Railgun Insulator Damage

DTIC Science & Technology

2006-06-01

pyrolytic epoxy degradation and glass fiber softening and liquification in the insulator, it is determined that rail-to-rail plasmas are present behind...produces epoxy decomposition products in the form of gases, oils , waxes and chars solid (heavily cross-linked residues) [4]. The nature of the... pyrolytic decomposition product (wax) of the epoxy as in the fired specimens. Figures 6 and 7 are typical examples of glass fiber softening and

Ultraviolet photoelectron spectroscopy reveals energy-band dispersion for π-stacked 7,8,15,16-tetraazaterrylene thin films in a donor–acceptor bulk heterojunction

NASA Astrophysics Data System (ADS)

Aghdassi, Nabi; Wang, Qi; Ji, Ru-Ru; Wang, Bin; Fan, Jian; Duhm, Steffen

2018-05-01

7,8,15,16-tetraazaterrylene (TAT) thin films grown on highly oriented pyrolytic graphite (HOPG) substrates were studied extensively with regard to their intrinsic and interfacial electronic properties by means of ultraviolet photoelectron spectroscopy (UPS). Merely weak substrate–adsorbate interaction occurs at the TAT/HOPG interface, with interface energetics being only little affected by the nominal film thickness. Photon energy-dependent UPS performed perpendicular to the molecular planes of TAT multilayer films at room temperature clearly reveals band-like intermolecular dispersion of the TAT highest occupied molecular orbital (HOMO) energy. Based on a comparison with a tight-binding model, a relatively narrow bandwidth of 54 meV is derived, which points to the presence of an intermediate regime between hopping and band-like hole transport. Upon additional deposition of 2,2‧:5‧,2″:5″,2″‧-quaterthiophene (4T), a 4T:TAT donor–acceptor bulk heterojunction with a considerable HOMO-level offset at the donor–acceptor interface is formed. The 4T:TAT bulk heterojunction likewise exhibits intermolecular dispersion of the TAT HOMO energy, yet with a significant decreased bandwidth.

Surface science approach to Pt/carbon model catalysts: XPS, STM and microreactor studies

NASA Astrophysics Data System (ADS)

Motin, Abdul Md.; Haunold, Thomas; Bukhtiyarov, Andrey V.; Bera, Abhijit; Rameshan, Christoph; Rupprechter, Günther

2018-05-01

Pt nanoparticles supported on carbon are an important technological catalyst. A corresponding model catalyst was prepared by physical vapor deposition (PVD) of Pt on sputtered HOPG (highly oriented pyrolytic graphite). The carbon substrate before and after sputtering as well as the Pt/HOPG system before and after Pt deposition and annealing were examined by XPS and STM. This yielded information on the surface density of defects, which serve as nucleation centres for Pt, and on the size distribution (mean size/height) of the Pt nanoparticles. Two different model catalysts were prepared with mean sizes of 2.0 and 3.6 nm, both turned out to be stable upon UHV-annealing to 300 °C. After transfer into a UHV-compatible flow microreactor and subsequent cleaning in UHV and under mbar pressure, the catalytic activity of the Pt/HOPG model system for ethylene hydrogenation was examined under atmospheric pressure flow conditions. This enabled to determine temperature-dependent conversion rates, turnover frequencies (TOFs) and activation energies. The catalytic results obtained are in line with the characteristics of technological Pt/C, demonstrating the validity of the current surface science based model catalyst approach.

Comparison of VVV Auger electron spectra from single and multilayer graphene and graphite.

NASA Astrophysics Data System (ADS)

Chirayath, V. A.; Callewaert, V.; Fairchild, A. J.; Chrysler, M. D.; Gladen, R. W.; Imam, S. K.; Koymen, A. R.; Saniz, R.; Barbiellini, B.; Rajeshwar, K.; Partoens, B.; Weiss, A. H.

A direct observation of a low energy electron peak in the positron annihilation induced Auger electron spectra (PAES) from a single layer of graphene was made recently. A low energy positron beam (<1.25 eV) was used to deposit the positron on single layer graphene on a Cu substrate and the low energy peak was designated as VVV following the X-ray notation. The PAES signal is almost entirely from the top graphene layer due to the trapping of positrons in the image potential well on the surface of graphene. We utilize this monolayer sensitivity of PAES to compare the shape of the VVV Auger peak from the single layer graphene to the shapes of the VVV Auger peak obtained from multilayer graphene on Cu and from highly oriented pyrolytic graphite (HOPG). The VVV Auger peak from multilayer graphene on Cu and HOPG shows a systematic shift towards lower energies relative to the VVV Auger peak from the single layer graphene. The influence of the hole-hole interaction in distorting and shifting the VVV Auger spectra are discussed in relation to this observed shift. NSF Grant No. DMR 1508719 and DMR 1338130.

Phonon-assisted indirect transitions in angle-resolved photoemission spectra of graphite and graphene

NASA Astrophysics Data System (ADS)

Ayria, Pourya; Tanaka, Shin-ichiro; Nugraha, Ahmad R. T.; Dresselhaus, Mildred S.; Saito, Riichiro

2016-08-01

Indirect transitions of electrons in graphene and graphite are investigated by means of angle-resolved photoemission spectroscopy (ARPES) with several different incident photon energies and light polarizations. The theoretical calculations of the indirect transition for graphene and for a single crystal of graphite are compared with the experimental measurements for highly-oriented pyrolytic graphite and a single crystal of graphite. The dispersion relations for the transverse optical (TO) and the out-of-plane longitudinal acoustic (ZA) phonon modes of graphite and the TO phonon mode of graphene can be extracted from the inelastic ARPES intensity. We find that the TO phonon mode for k points along the Γ -K and K -M -K' directions in the Brillouin zone can be observed in the ARPES spectra of graphite and graphene by using a photon energy ≈11.1 eV. The relevant mechanism in the ARPES process for this case is the resonant indirect transition. On the other hand, the ZA phonon mode of graphite can be observed by using a photon energy ≈6.3 eV through a nonresonant indirect transition, while the ZA phonon mode of graphene within the same mechanism should not be observed.

Preparation of monolayers of [MnIII 6CrIII]3+ single-molecule magnets on HOPG, mica and silicon surfaces and characterization by means of non-contact AFM

NASA Astrophysics Data System (ADS)

Gryzia, Aaron; Predatsch, Hans; Brechling, Armin; Hoeke, Veronika; Krickemeyer, Erich; Derks, Christine; Neumann, Manfred; Glaser, Thorsten; Heinzmann, Ulrich

2011-08-01

We report on the characterization of various salts of [ Mn III 6 Cr III ] 3+ complexes prepared on substrates such as highly oriented pyrolytic graphite (HOPG), mica, SiO2, and Si3N4. [ Mn III 6 Cr III ] 3+ is a single-molecule magnet, i.e., a superparamagnetic molecule, with a blocking temperature around 2 K. The three positive charges of [ Mn III 6 Cr III ] 3+ were electrically neutralized by use of various anions such as tetraphenylborate (BPh4 -), lactate (C3H5O3 -), or perchlorate (ClO4 -). The molecule was prepared on the substrates out of solution using the droplet technique. The main subject of investigation was how the anions and substrates influence the emerging surface topology during and after the preparation. Regarding HOPG and SiO2, flat island-like and hemispheric-shaped structures were created. We observed a strong correlation between the electronic properties of the substrate and the analyzed structures, especially in the case of mica where we observed a gradient in the analyzed structures across the surface.

Ultraviolet photoelectron spectroscopy reveals energy-band dispersion for π-stacked 7,8,15,16-tetraazaterrylene thin films in a donor-acceptor bulk heterojunction.

PubMed

Aghdassi, Nabi; Wang, Qi; Ji, Ru-Ru; Wang, Bin; Fan, Jian; Duhm, Steffen

2018-05-11

7,8,15,16-tetraazaterrylene (TAT) thin films grown on highly oriented pyrolytic graphite (HOPG) substrates were studied extensively with regard to their intrinsic and interfacial electronic properties by means of ultraviolet photoelectron spectroscopy (UPS). Merely weak substrate-adsorbate interaction occurs at the TAT/HOPG interface, with interface energetics being only little affected by the nominal film thickness. Photon energy-dependent UPS performed perpendicular to the molecular planes of TAT multilayer films at room temperature clearly reveals band-like intermolecular dispersion of the TAT highest occupied molecular orbital (HOMO) energy. Based on a comparison with a tight-binding model, a relatively narrow bandwidth of 54 meV is derived, which points to the presence of an intermediate regime between hopping and band-like hole transport. Upon additional deposition of 2,2':5',2″:5″,2″'-quaterthiophene (4T), a 4T:TAT donor-acceptor bulk heterojunction with a considerable HOMO-level offset at the donor-acceptor interface is formed. The 4T:TAT bulk heterojunction likewise exhibits intermolecular dispersion of the TAT HOMO energy, yet with a significant decreased bandwidth.

Aluminum doped nickel oxide thin film with improved electrochromic performance from layered double hydroxides precursor in situ pyrolytic route

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, Jingjing; Lai, Lincong; Zhang, Ping

Electrochromic materials with unique performance arouse great interest on account of potential application values in smart window, low-power display, automobile anti-glare rearview mirror, and e-papers. In this paper, high-performing Al-doped NiO porous electrochromic film grown on ITO substrate has been prepared via a layered double hydroxides(LDHs) precursor in situ pyrolytic route. The Al{sup 3+} ions distributed homogenously within the NiO matrix can significantly influence the crystallinity of Ni-Al LDH and NiO:Al{sup 3+} films. The electrochromic performance of the films were evaluated by means of UV–vis absorption spectroscopy, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronoamperometry(CA) measurements. In addition, themore » ratio of Ni{sup 3+}/Ni{sup 2+} also varies with Al content which can lead to different electrochemical performances. Among the as-prepared films, NiO film prepared from Ni-Al (19:1) LDH show the best electrochromic performance with a high transparency of 96%, large optical modulation range (58.4%), fast switching speed (bleaching/coloration times are 1.8/4.2 s, respectively) and excellent durability (30% decrease after 2000 cycles). The improved performance was owed to the synergy of large NiO film specific surface area and porous morphology, as well as Al doping stifled the formation of Ni{sup 3+} making bleached state more pure. This LDHs precursor pyrolytic method is simple, low-cost and environmental benign and is feasible for the preparation of NiO:Al and other Al-doped oxide thin film. - Graphical abstract: The ratio of Ni{sup 3+}/Ni{sup 2+} varies with Al content which can lead to different electrochemical performances. Among the as-prepared films, NiO film prepared from Ni-Al (19:1) LDH show the best electrochromic performance with a high transparency of 96%, large optical modulation range, fast switching speed and excellent durability. Display Omitted.« less

Production of clean pyrolytic sugars for fermentation.

PubMed

Rover, Marjorie R; Johnston, Patrick A; Jin, Tao; Smith, Ryan G; Brown, Robert C; Jarboe, Laura

2014-06-01

This study explores the separate recovery of sugars and phenolic oligomers produced during fast pyrolysis with the effective removal of contaminants from the separated pyrolytic sugars to produce a substrate suitable for fermentation without hydrolysis. The first two stages from a unique recovery system capture "heavy ends", mostly water-soluble sugars and water-insoluble phenolic oligomers. The differences in water solubility can be exploited to recover a sugar-rich aqueous phase and a phenolic-rich raffinate. Over 93 wt % of the sugars is removed in two water washes. These sugars contain contaminants such as low-molecular-weight acids, furans, and phenols that could inhibit successful fermentation. Detoxification methods were used to remove these contaminants from pyrolytic sugars. The optimal candidate is NaOH overliming, which results in maximum growth measurements with the use of ethanol-producing Escherichia coli. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Relationship between microstructure and tribological behavior of CFRC composites

NASA Astrophysics Data System (ADS)

de Souza, Maria Aparecida Miranda; Pardini, Luiz Claudio

2017-12-01

Carbon fiber reinforced carbon (CFRC) composites were initially introduced in spacecraft propulsion area and quickly started to be applied in aircraft braking systems, replacing conventional metallic systems, thanks to their excellent tribological properties. Each company develops their own CFRC composite production system, the information is unique to each manufacturer, and little is reported in the literature. In this work, tribological characterizations of three commercial CFRC composites are performed using a pin-on-disc tribometer. The results showed that the pairs assembled with pyrolytic matrix composites of rough or smooth laminar texture with graphitization index between 18 and 40% has an average COF between 0.15 and 0.25, while the pairs assembled with mixed pairs, pyrolytic matrix and glassy matrix, or pair of glassy matrix display average COF between 0.10 and 0.15. Wear which can reach a rate 9 times higher to the tribological pair of glassy composite when compared to a pyrolytic composite.

On the fractography of overload, stress corrosion, and cyclic fatigue failures in pyrolytic-carbon materials used in prosthetic heart-valve devices.

PubMed

Ritchie, R O; Dauskardt, R H; Pennisi, F J

1992-01-01

A scanning electron microscopy study is reported of the nature and morphology of fracture surfaces in pyrocarbons commonly used for the manufacture of mechanical heart-valve prostheses. Specifically, silicon-alloyed low-temperature-isotropic (LTI)-pyrolytic carbon is examined, both as a coating on graphite and as a monolithic material, following overload, stress corrosion (static fatigue), and cyclic fatigue failures in a simulated physiological environment of 37 degrees C Ringer's solution. It is found that, in contrast to most metallic materials yet in keeping with many ceramics, there are no distinct fracture morphologies in pyro-carbons which are characteristic of a specific mode of loading; fracture surfaces appear to be identical for both catastrophic and subcritical crack growth under either sustained or cyclic loading. We conclude that caution should be used in assigning the likely cause of failure of pyrolytic carbon heart-valve components using fractographic examination.

Low temperature conversion of plastic waste into light hydrocarbons.

PubMed

Shah, Sajid Hussain; Khan, Zahid Mahmood; Raja, Iftikhar Ahmad; Mahmood, Qaisar; Bhatti, Zulfiqar Ahmad; Khan, Jamil; Farooq, Ather; Rashid, Naim; Wu, Donglei

2010-07-15

Advance recycling through pyrolytic technology has the potential of being applied to the management of plastic waste (PW). For this purpose 1 l volume, energy efficient batch reactor was manufactured locally and tested for pyrolysis of waste plastic. The feedstock for reactor was 50 g waste polyethylene. The average yield of the pyrolytic oil, wax, pyrogas and char from pyrolysis of PW were 48.6, 40.7, 10.1 and 0.6%, respectively, at 275 degrees C with non-catalytic process. Using catalyst the average yields of pyrolytic oil, pyrogas, wax and residue (char) of 50 g of PW was 47.98, 35.43, 16.09 and 0.50%, respectively, at operating temperature of 250 degrees C. The designed reactor could work at low temperature in the absence of a catalyst to obtain similar products as for a catalytic process. 2010 Elsevier B.V. All rights reserved.

Research into the use of pyrolytic oxides and polymers for the fabrication of thin film high energy capacitors

NASA Technical Reports Server (NTRS)

Nevin, J. H.

1983-01-01

Construction, capacitance and dissipation factor, and electrode materials for single layer capacitors are discussed. Basic construction, phosphosilicate glass, ten layer capacitors, twenty layer capacitors, stress measurements, buffered oxide layers, and 30 layer capacitors are also discussed. Spin-on phosphosilicate glass is addressed. Polymers as dielectric materials are also considered.

The Pyrolytic Profile of Lyophilized and Deep-Frozen Compact Part of the Human Bone

PubMed Central

Lodowska, Jolanta; Wolny, Daniel; Kurkiewicz, Sławomir; Węglarz, Ludmiła

2012-01-01

Background. Bone grafts are used in the treatment of nonunion of fractures, bone tumors and in arthroplasty. Tissues preserved by lyophilization or deep freezing are used as implants nowadays. Lyophilized grafts are utilized in the therapy of birth defects and bone benign tumors, while deep-frozen ones are applied in orthopedics. The aim of the study was to compare the pyrolytic pattern, as an indirect means of the analysis of organic composition of deep-frozen and lyophilized compact part of the human bone. Methods. Samples of preserved bone tissue were subjected to thermolysis and tetrahydroammonium-hydroxide- (TMAH-) associated thermochemolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS). Results. Derivatives of benzene, pyridine, pyrrole, phenol, sulfur compounds, nitriles, saturated and unsaturated aliphatic hydrocarbons, and fatty acids (C12–C20) were identified in the pyrolytic pattern. The pyrolyzates were the most abundant in derivatives of pyrrole and nitriles originated from proteins. The predominant product in pyrolytic pattern of the investigated bone was pyrrolo[1,2-α]piperazine-3,6-dione derived from collagen. The content of this compound significantly differentiated the lyophilized graft from the deep-frozen one. Oleic and palmitic acid were predominant among fatty acids of the investigated samples. The deep-frozen implants were characterized by higher percentage of long-chain fatty acids than lyophilized grafts. PMID:22619606

H/C atomic ratio as a smart linkage between pyrolytic temperatures, aromatic clusters and sorption properties of biochars derived from diverse precursory materials

PubMed Central

Xiao, Xin; Chen, Zaiming; Chen, Baoliang

2016-01-01

Biochar is increasingly gaining attention due to multifunctional roles in soil amelioration, pollution mitigation and carbon sequestration. It is a significant challenge to compare the reported results from world-wide labs regarding the structure and sorption of biochars derived from various precursors under different pyrolytic conditions due to a lack of a simple linkage. By combining the published works on various biochars, we established a quantitative relationship between H/C atomic ratio and pyrolytic temperature (T), aromatic structure, and sorption properties for naphthalene and phenanthrene. A reverse sigmoid shape between T and the H/C ratio was observed, which was independent of the precursors of biochars, including the ash contents. Linear correlations of Freundlich parameters (N, log Kf) and sorption amount (log Qe, log QA) with H/C ratios were found. A rectangle-like model was proposed to predict the aromatic cluster sizes of biochars from their H/C ratios, and then a good structure-sorption relationship was derived. These quantitative relationships indicate that the H/C atomic ratio is a universal linkage to predict pyrolytic temperatures, aromatic cluster sizes, and sorption characteristics. This study would guide the global study of biochars toward being comparable, and then the development of the structure-sorption relationships will benefit the structural design and environmental application of biochars. PMID:26940984

Lateral epitaxial overgowth of GaAs by organometallic chemical vapor deposition

NASA Technical Reports Server (NTRS)

Gale, R. P.; Mcclelland, R. W.; Fan, J. C. C.; Bozler, C. O.

1982-01-01

Lateral epitaxial overgrowth of GaAs by organometallic chemical vapor deposition has been demonstrated. Pyrolytic decomposition of trimethylgallium and arsine, without the use of HCl, was used to deposit GaAs on substrates prepared by coating (110) GaAs wafers with SiO2, then using photolithography to open narrow stripes in the oxide. Lateral overgrowth was seeded by epitaxial deposits formed on the GaAs surfaces exposed by the stripe openings. The extent of lateral overgrowth was investigated as a function of stripe orientation and growth temperature. Ratios of lateral to vertical growth rates greater than five have been obtained. The lateral growth is due to surface-kinetic control for the two-dimensional growth geometry studied. A continuous epitaxial GaAs layer 3 microns thick has been grown over a patterned mask on a GaAs substrate and then cleaved from the substrate.

Kinetic analyses and pyrolytic behavior of Para grass (Urochloa mutica) for its bioenergy potential.

PubMed

Ahmad, Muhammad Sajjad; Mehmood, Muhammad Aamer; Al Ayed, Omar S; Ye, Guangbin; Luo, Huibo; Ibrahim, Muhammad; Rashid, Umer; Arbi Nehdi, Imededdine; Qadir, Ghulam

2017-01-01

The biomass of Urochloa mutica was subjected to thermal degradation analyses to understand its pyrolytic behavior for bioenergy production. Thermal degradation experiments were performed at three different heating rates, 10, 30 and 50°Cmin -1 using simultaneous thermogravimetric-differential scanning calorimetric analyzer, under an inert environment. The kinetic analyses were performed using isoconversional models of Kissenger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO). The high heating value was calculated as 15.04MJmol -1 . The activation energy (E) values were shown to be ranging from 103 through 233 kJmol -1 . Pre-exponential factors (A) indicated the reaction to follow first order kinetics. Gibbs free energy (ΔG) was measured to be ranging from 169 to 173kJmol -1 and 168 to 172kJmol -1 , calculated by KAS and FWO methods, respectively. We have shown that Para grass biomass has considerable bioenergy potential comparable to established bioenergy crops such as switchgrass and miscanthus. Copyright © 2016 Elsevier Ltd. All rights reserved.

Microwave pyrolysis of oily sludge with activated carbon.

PubMed

Chen, Yi-Rong

2016-12-01

The aim of this study is to explore catalytic microwave pyrolysis of crude oil storage tank sludge for fuels using granular activated carbon (GAC) as a catalyst. The effect of GAC loading on the yield of pyrolysis products was also investigated. Heating rate of oily sludge and yield of microwave pyrolysis products such as oil and fuel gas was found to depend on the ratio of GAC to oily sludge. The optimal GAC loading was found to be 10%, while much smaller and larger feed sizes adversely influenced production. During oily sludge pyrolysis, a maximum oil yield of 77.5% was achieved. Pyrolytic oils with high concentrations of diesel oil and gasoline (about 70 wt% in the pyrolytic oil) were obtained. The leaching of heavy metals, such as Cr, As and Pb, was also suppressed in the solid residue after pyrolysis. This technique provides advantages such as harmless treatment of oily sludge and substantial reduction in the consumption of energy, time and cost.

Pyrolytic characteristics of sweet potato vine.

PubMed

Wang, Tipeng; Dong, Xiaochen; Jin, Zaixing; Su, Wenjing; Ye, Xiaoning; Dong, Changqing; Lu, Qiang

2015-09-01

To utilized biomass for optimum application, sweet potato vine (SPV) was studied on its pyrolytic characteristics by TGA and Py-GC/MS analysis as a representative of biomass with low lignin content and high extractives content. Results indicated that lignin, cellulose, hemicellulose and extractives contents were 7.85 wt.%, 33.01 wt.%, 12.25 wt.% and 37.12 wt.%, respectively. In bio-oil, sugars content firstly increased from 8.76 wt.% (350 °C) to 13.97 wt.% (400 °C) and then decreased to 9.19 wt.% (500 °C); linear carbonyls and linear acids contents decreased from 16.58 wt.% and 17.45 wt.% to 5.26 wt.% and 4.03 wt.%, respectively; furans content increased from 7.10 wt.% to 15.47 wt.%. The content 11.86 wt.% of levoglucose at 400 °C, 15.41 wt.% of acetic acid at 350 °C and 6.94 wt.% of furfural at 500 °C suggested good pyrolysis selectivity of SPV. Copyright © 2015 Elsevier Ltd. All rights reserved.

Evaluating the Surface Topography of Pyrolytic Carbon Finger Prostheses through Measurement of Various Roughness Parameters

PubMed Central

Naylor, Andrew; Talwalkar, Sumedh C.; Trail, Ian A.; Joyce, Thomas J.

2016-01-01

The articulating surfaces of four different sizes of unused pyrolytic carbon proximal interphalangeal prostheses (PIP) were evaluated though measuring several topographical parameters using a white light interferometer: average roughness (Sa); root mean-square roughness (Sq); skewness (Ssk); and kurtosis (Sku). The radii of the articulating surfaces were measured using a coordinate measuring machine, and were found to be: 2.5, 3.3, 4.2 and 4.7 mm for proximal, and 4.0, 5.1, 5.6 and 6.3 mm for medial components. ANOVA was used to assess the relationship between the component radii and each roughness parameter. Sa, Sq and Ssk correlated negatively with radius (p = 0.001, 0.001, 0.023), whilst Sku correlated positively with radius (p = 0.03). Ergo, the surfaces with the largest radii possessed the better topographical characteristics: low roughness, negative skewness, high kurtosis. Conversely, the surfaces with the smallest radii had poorer topographical characteristics. PMID:27089375

Pyrolytic carbon coated black silicon

PubMed Central

Shah, Ali; Stenberg, Petri; Karvonen, Lasse; Ali, Rizwan; Honkanen, Seppo; Lipsanen, Harri; Peyghambarian, N.; Kuittinen, Markku; Svirko, Yuri; Kaplas, Tommi

2016-01-01

Carbon is the most well-known black material in the history of man. Throughout the centuries, carbon has been used as a black material for paintings, camouflage, and optics. Although, the techniques to make other black surfaces have evolved and become more sophisticated with time, carbon still remains one of the best black materials. Another well-known black surface is black silicon, reflecting less than 0.5% of incident light in visible spectral range but becomes a highly reflecting surface in wavelengths above 1000 nm. On the other hand, carbon absorbs at those and longer wavelengths. Thus, it is possible to combine black silicon with carbon to create an artificial material with very low reflectivity over a wide spectral range. Here we report our results on coating conformally black silicon substrate with amorphous pyrolytic carbon. We present a superior black surface with reflectance of light less than 0.5% in the spectral range of 350 nm to 2000 nm. PMID:27174890

SIKA—the multiplexing cold-neutron triple-axis spectrometer at ANSTO

NASA Astrophysics Data System (ADS)

Wu, C.-M.; Deng, G.; Gardner, J. S.; Vorderwisch, P.; Li, W.-H.; Yano, S.; Peng, J.-C.; Imamovic, E.

2016-10-01

SIKA is a new cold-neutron triple-axis spectrometer receiving neutrons from the cold source CG4 of the 20MW Open Pool Australian Light-water reactor. As a state-of-the-art triple-axis spectrometer, SIKA is equipped with a large double-focusing pyrolytic graphite monochromator, a multiblade pyrolytic graphite analyser and a multi-detector system. In this paper, we present the design, functions, and capabilities of SIKA, and discuss commissioning experimental results from powder and single-crystal samples to demonstrate its performance.

Wettability of Pyrolytic Boron Nitride by Aluminum

NASA Technical Reports Server (NTRS)

Chiaramonte, Francis P.; Rosenthal, Bruce N.

1991-01-01

The wetting of pyrolytic boron nitride by molten 99.9999 percent pure aluminum was investigated by using the sessile drop method in a vacuum operating at approximately 660 micro-Pa at temperatures ranging from 700 to 1000 C. The equilibrium contact angle decreased with an increase in temperature. For temperatures at 900 C or less, the equilibrium contact angle was greater than 90 deg. At 1000 C a nonwetting-to-wetting transition occurred and the contact angle stabilized at 49 deg.

A high-performance ternary Si composite anode material with crystal graphite core and amorphous carbon shell

NASA Astrophysics Data System (ADS)

Sui, Dong; Xie, Yuqing; Zhao, Weimin; Zhang, Hongtao; Zhou, Ying; Qin, Xiting; Ma, Yanfeng; Yang, Yong; Chen, Yongsheng

2018-04-01

Si is a promising anode material for lithium-ion batteries, but suffers from sophisticated engineering structures and complex fabrication processes that pose challenges for commercial application. Herein, a ternary Si/graphite/pyrolytic carbon (SiGC) anode material with a structure of crystal core and amorphous shell using low-cost raw materials is developed. In this ternary SiGC composite, Si component exists as nanoparticles and is spread on the surface of the core graphite flakes while the sucrose-derived pyrolytic carbon further covers the graphite/Si components as the amorphous shell. With this structure, Si together with the graphite contributes to the high specific capacity of this Si ternary material. Also the graphite serves as the supporting and conducting matrix and the amorphous shell carbon could accommodate the volume change effect of Si, reinforces the integrity of the composite architecture, and prevents the graphite and Si from direct exposing to the electrolyte. The optimized ternary SiGC composite displays high reversible specific capacity of 818 mAh g-1 at 0.1 A g-1, initial Coulombic efficiency (CE) over 80%, and excellent cycling stability at 0.5 A g-1 with 83.6% capacity retention (∼610 mAh g-1) after 300 cycles.

Ultra-facile fabrication of phosphorus doped egg-like hierarchic porous carbon with superior supercapacitance performance by microwave irradiation combining with self-activation strategy

NASA Astrophysics Data System (ADS)

Zhang, Deyi; Han, Mei; Li, Yubing; He, Jingjing; Wang, Bing; Wang, Kunjie; Feng, Huixia

2017-12-01

Herein, we report an ultra-facile fabrication method for a phosphorus doped egg-like hierarchic porous carbon by microwave irradiation combining with self-activation strategy under air atmosphere. Comparing with the traditional pyrolytic carbonization method, the reported method exhibits incomparable merits, such as high energy efficiency, ultra-fast and inert atmosphere protection absent fabrication process. Similar morphology and graphitization degree with the sample fabricated by the traditional pyrolytic carbonization method under inert atmosphere protection for 2 h can be easily achieved by the reported microwave irradiation method just for 3 min under ambient atmosphere. The samples fabricated by the reported method display a unique phosphorus doped egg-like hierarchic porous structure, high specific surface area (1642 m2 g-1) and large pore volume (2.04 cm3 g-1). Specific capacitance of the samples fabricated by the reported method reaches up to 209 F g-1, and over 96.2% of initial capacitance remains as current density increasing from 0.5 to 20 A g-1, indicating the superior capacitance performance of the fabricated samples. The hierarchic porous structure, opened microporosity, additional pseudocapacitance, high electrolyte-accessible surface area and good conductivity make essential contribution to its superior capacitance performance.

Surface science studies of ethene containing model interstellar ices

NASA Astrophysics Data System (ADS)

Puletti, F.; Whelan, M.; Brown, W. A.

2011-05-01

The formation of saturated hydrocarbons in the interstellar medium (ISM) is difficult to explain only by taking into account gas phase reactions. This is mostly due to the fact that carbonium ions only react with H_2 to make unsaturated hydrocarbons, and hence no viable route to saturated hydrocarbons has been postulated to date. It is therefore likely that saturation processes occur via surface reactions that take place on interstellar dust grains. One of the species of interest in this family of reactions is C_2H_4 (ethene) which is an intermediate in several molecular formation routes (e.g. C_2H_2 → C_2H_6). To help to understand some of the surface processes involving ethene, a study of ethene deposited on a dust grain analogue surface (highly oriented pyrolytic graphite) held under ultra-high vacuum at 20 K has been performed. The adsorption and desorption of ethene has been studied both in water-free and water-dominated model interstellar ices. A combination of temperature programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS) have been used to identify the adsorbed and trapped species and to determine the kinetics of the desorption processes. In all cases, ethene is found to physisorb on the carbonaceous surface. As expected water has a very strong influence on the desorption of ethene, as previously observed for other model interstellar ice systems.

Nucleation, aggregative growth and detachment of metal nanoparticles during electrodeposition at electrode surfaces.

PubMed

Lai, Stanley C S; Lazenby, Robert A; Kirkman, Paul M; Unwin, Patrick R

2015-02-01

The nucleation and growth of metal nanoparticles (NPs) on surfaces is of considerable interest with regard to creating functional interfaces with myriad applications. Yet, key features of these processes remain elusive and are undergoing revision. Here, the mechanism of the electrodeposition of silver on basal plane highly oriented pyrolytic graphite (HOPG) is investigated as a model system at a wide range of length scales, spanning electrochemical measurements from the macroscale to the nanoscale using scanning electrochemical cell microscopy (SECCM), a pipette-based approach. The macroscale measurements show that the nucleation process cannot be modelled as either truly instantaneous or progressive, and that step edge sites of HOPG do not play a dominant role in nucleation events compared to the HOPG basal plane, as has been widely proposed. Moreover, nucleation numbers extracted from electrochemical analysis do not match those determined by atomic force microscopy (AFM). The high time and spatial resolution of the nanoscale pipette set-up reveals individual nucleation and growth events at the graphite basal surface that are resolved and analysed in detail. Based on these results, corroborated with complementary microscopy measurements, we propose that a nucleation-aggregative growth-detachment mechanism is an important feature of the electrodeposition of silver NPs on HOPG. These findings have major implications for NP electrodeposition and for understanding electrochemical processes at graphitic materials generally.

Alternative method for steam generation for thermal oxidation of silicon

NASA Astrophysics Data System (ADS)

Spiegelman, Jeffrey J.

2010-02-01

Thermal oxidation of silicon is an important process step in MEMS device fabrication. Thicker oxide layers are often used as structural components and can take days or weeks to grow, causing high gas costs, maintenance issues, and a process bottleneck. Pyrolytic steam, which is generated from hydrogen and oxygen combustion, was the default process, but has serious drawbacks: cost, safety, particles, permitting, reduced growth rate, rapid hydrogen consumption, component breakdown and limited steam flow rates. Results from data collected over a 24 month period by a MEMS manufacturer supports replacement of pyrolytic torches with RASIRC Steamer technology to reduce process cycle time and enable expansion previously limited by local hydrogen permitting. Data was gathered to determine whether Steamers can meet or exceed pyrolytic torch performance. The RASIRC Steamer uses de-ionized water as its steam source, eliminating dependence on hydrogen and oxygen. A non-porous hydrophilic membrane selectively allows water vapor to pass. All other molecules are greatly restricted, so contaminants in water such as dissolved gases, ions, total organic compounds (TOC), particles, and metals can be removed in the steam phase. The MEMS manufacturer improved growth rate by 7% over the growth range from 1μm to 3.5μm. Over a four month period, wafer uniformity, refractive index, wafer stress, and etch rate were tracked with no significant difference found. The elimination of hydrogen generated a four-month return on investment (ROI). Mean time between failure (MTBF) was increased from 3 weeks to 32 weeks based on three Steamers operating over eight months.

Nanosecond formation of diamond and lonsdaleite by shock compression of graphite.

PubMed

Kraus, D; Ravasio, A; Gauthier, M; Gericke, D O; Vorberger, J; Frydrych, S; Helfrich, J; Fletcher, L B; Schaumann, G; Nagler, B; Barbrel, B; Bachmann, B; Gamboa, E J; Göde, S; Granados, E; Gregori, G; Lee, H J; Neumayer, P; Schumaker, W; Döppner, T; Falcone, R W; Glenzer, S H; Roth, M

2016-03-14

The shock-induced transition from graphite to diamond has been of great scientific and technological interest since the discovery of microscopic diamonds in remnants of explosively driven graphite. Furthermore, shock synthesis of diamond and lonsdaleite, a speculative hexagonal carbon polymorph with unique hardness, is expected to happen during violent meteor impacts. Here, we show unprecedented in situ X-ray diffraction measurements of diamond formation on nanosecond timescales by shock compression of pyrolytic as well as polycrystalline graphite to pressures from 19 GPa up to 228 GPa. While we observe the transition to diamond starting at 50 GPa for both pyrolytic and polycrystalline graphite, we also record the direct formation of lonsdaleite above 170 GPa for pyrolytic samples only. Our experiment provides new insights into the processes of the shock-induced transition from graphite to diamond and uniquely resolves the dynamics that explain the main natural occurrence of the lonsdaleite crystal structure being close to meteor impact sites.

Nanosecond formation of diamond and lonsdaleite by shock compression of graphite

DOE PAGES

Kraus, D.; Ravasio, A.; Gauthier, M.; ...

2016-03-14

The shock-induced transition from graphite to diamond has been of great scientific and technological interest since the discovery of microscopic diamonds in remnants of explosively driven graphite. Furthermore, shock synthesis of diamond and lonsdaleite, a speculative hexagonal carbon polymorph with unique hardness, is expected to happen during violent meteor impacts. Here, we show unprecedented in situ X-ray diffraction measurements of diamond formation on nanosecond timescales by shock compression of pyrolytic as well as polycrystalline graphite to pressures from 19 GPa up to 228 GPa. While we observe the transition to diamond starting at 50 GPa for both pyrolytic and polycrystallinemore » graphite, we also record the direct formation of lonsdaleite above 170 GPa for pyrolytic samples only. In conclusion, our experiment provides new insights into the processes of the shock-induced transition from graphite to diamond and uniquely resolves the dynamics that explain the main natural occurrence of the lonsdaleite crystal structure being close to meteor impact sites.« less

Two stages catalytic pyrolysis of refuse derived fuel: production of biofuel via syncrude.

PubMed

Miskolczi, N; Buyong, F; Angyal, A; Williams, P T; Bartha, L

2010-11-01

Thermo-catalytic pyrolysis of refuse derived fuels with different catalysts had been conducted in a two stages process due to its important potential value as fuel. The first stage was a pure thermal pyrolysis in a horizontal tubular reactor with feed rate of 0.5kg hourly. The second stage was a semi-batch process in the presence of catalysts. Results showed that the tested catalysts significantly have affected the quantity of products. E.g. gas yield could be increased with 350% related to the catalyst free case using ZSM-5, while that of pyrolytic oil was 115% over Y-zeolite. Gases consisted of mainly CO and CO(2) obtained from the tubular reactor, while dominantly hydrocarbons from the second stage. Ni-Mo-catalyst and Co-Mo-catalyst had shown activity in pyrolytic oil upgrading via in-situ hydrogenation-dehydrogenation reactions. Sulphur, nitrogen and chlorine level in pyrolytic oils could be significantly declined by using of catalysts.

Lipid accumulation from pinewood pyrolysates by Rhodosporidium diobovatum and Chlorella vulgaris for biodiesel production.

PubMed

Luque, Luis; Orr, Valerie C A; Chen, Sean; Westerhof, Roel; Oudenhoven, Stijn; Rossum, Guus van; Kersten, Sascha; Berruti, Franco; Rehmann, Lars

2016-08-01

This study evaluated the suitability of pinewood pyrolysates as a carbon source for lipid production and cultivation of the oleaginous yeast Rhodosporidium diobovatum and the microalgae Chlorella vulgaris. Thermal decomposition of pinewood and fractional condensation were used to obtain an oil rich in levoglucosan which was upgraded to glucose by acid hydrolysis. Blending of pyrolytic sugars with pure glucose in both nitrogen rich and nitrogen limited conditions was studied for R. diobovatum, and under nitrogen limited conditions for C. vulgaris. Glucose consumption rate decreased with increasing proportions of pyrolytic sugars increasing cultivation time. While R. diobovatum was capable of growth in 100% (v/v) pyrolytic sugars, C. vulgaris growth declined rapidly in blends greater than 20% (v/v) until no growth was detected in blends >40%. Finally, the effects of pyrolysis sugars on lipid composition was evaluated and biodiesel fuel properties were estimated based on the lipid profiles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Copper and boron fixation in wood by pyrolytic resins.

PubMed

Mourant, Daniel; Yang, Dian-Qing; Lu, Xiao; Riedl, Bernard; Roy, Christian

2009-02-01

A phenol-formaldehyde (PF)-resin designed to penetrate wood and immobilize copper and boron in wood cells for protection against decay was investigated. The phenol portion of the PF-resin was partially substituted with pyrolysis oil derived from softwood bark. The objective was to reduce the environmental impact associated with the production of petroleum-borne phenol, as well as to improve the product economics. Leaching tests were conducted with three different formulas of resins containing 50%, 75% or 85% by weight of pyrolytic oil on a total phenol basis. The leachates were analyzed for the presence of copper by atomic absorption spectroscopy while inductively coupled plasma spectroscopy was used for boron detection. Copper leaching was reduced up to 18 times when comparing the treatments with and without the resin. Preservative leaching varied between wood species as well as between the resins containing different concentrations of pyrolytic oil. The organic leachates were measured using gas chromatography and mass spectroscopy. Trace amounts of organics, mostly acetic acid, were found in the leachates.

Nanosecond formation of diamond and lonsdaleite by shock compression of graphite

PubMed Central

Kraus, D.; Ravasio, A.; Gauthier, M.; Gericke, D. O.; Vorberger, J.; Frydrych, S.; Helfrich, J.; Fletcher, L. B.; Schaumann, G.; Nagler, B.; Barbrel, B.; Bachmann, B.; Gamboa, E. J.; Göde, S.; Granados, E.; Gregori, G.; Lee, H. J.; Neumayer, P.; Schumaker, W.; Döppner, T.; Falcone, R. W.; Glenzer, S. H.; Roth, M.

2016-01-01

The shock-induced transition from graphite to diamond has been of great scientific and technological interest since the discovery of microscopic diamonds in remnants of explosively driven graphite. Furthermore, shock synthesis of diamond and lonsdaleite, a speculative hexagonal carbon polymorph with unique hardness, is expected to happen during violent meteor impacts. Here, we show unprecedented in situ X-ray diffraction measurements of diamond formation on nanosecond timescales by shock compression of pyrolytic as well as polycrystalline graphite to pressures from 19 GPa up to 228 GPa. While we observe the transition to diamond starting at 50 GPa for both pyrolytic and polycrystalline graphite, we also record the direct formation of lonsdaleite above 170 GPa for pyrolytic samples only. Our experiment provides new insights into the processes of the shock-induced transition from graphite to diamond and uniquely resolves the dynamics that explain the main natural occurrence of the lonsdaleite crystal structure being close to meteor impact sites. PMID:26972122

Qualitative Analysis and Detection of the Pyrolytic Products of JWH-018 and 11 Additional Synthetic Cannabinoids in the Presence of Common Herbal Smoking Substrates.

PubMed

Raso, Stephen; Bell, Suzanne

2017-07-01

Synthetic cannabinoids have become a ubiquitous challenge in forensic toxicology and seized drug analysis. Thermal degradation products have yet to be identified and evaluated for toxicity in comparison to parent and metabolic compounds. An investigation into these pyrolytic products, as the major route of ingestion is inhalation, may produce additional insight to understand the toxicity of synthetic cannabinoids. The pyrolysis of JWH-018 and 11 additional synthetic cannabinoids and six herbal plant substrates were conducted using an in-house constructed smoking simulator. After pyrolysis of herbal material alone, the plant substrate was spiked with the drug compounds to 2-5% w/w concentrations. Samples were collected, filtered, evaporated under nitrogen gas, reconstituted in methanol, and analyzed via gas chromatograph-mass spectrometer. Pyrolysis of the plant material alone produced 10 consistently observed compounds between the six plant species. The pyrolysis of the synthetic cannabinoids produced a total of 52 pyrolytic compounds, where 32 were unique to a particular parent compound and the remaining 20 were common products between multiple cannabinoids. The thermal degradation followed three major pathways that are outlined to assist in producing a predictive model for new synthetic cannabinoids that may arise in case samples. The observed pyrolytic products are also viable options for analysis in post mortem samples and the evaluation of toxicity. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Fuel Composition and Performance Analysis of Endothermically Heated Fuels for Pulse Detonation Engines

DTIC Science & Technology

2009-03-01

Waste heat from a pulse detonation engine (PDE) was extracted via concentric, counter flow heat exchangers to produce supercritical pyrolytic...mass spectrometry HLPC = High performance liquid chromatography NPT = National pipe thread PAH = Polycyclic aromatic hydrocarbon PDE = Pulse...Precision Liquid Chromatography (HPLC). The resulting “stressed” fuel showed a 29 shift to lower molecular weight compounds, as well as the production

Advanced Survivable Radiator Development Program

DTIC Science & Technology

1993-03-01

pyrolytic process. The ceramic fiber is amorphous with a typical elemental composition of 57% silicon, 28% nitrogen, 10% carbon , and 4% oxygen, and has an...exist: Optimum choice dependent on mission, operational requirements, and threat environment Configurations: Fibers , Rods, Fins Carbon - Carbon e ASpecial... Carbon Fiber Area Density ,,,--Stainless Aluminum Be Diamond BC Bond Copper Weave: Be, Al, SS. Ti, Nitinol Configurations: Low Z or High Z. depending

Characterization of cell cultures in contact with different orthopedic implants biomaterials

NASA Astrophysics Data System (ADS)

Ouenzerfi, G.; Hannoun, A.; Hassler, M.; Brizuela, L.; Youjil, S.; Bougault, C.; Trunfio-Sfarghiu, A.-M.

2016-08-01

The aim of this study is to identify the role of biological and mechanical constraints (at the cellular level) surrounding living tissues (cartilage and bone) in the presence of different joint implant biomaterials. In this fact, cells cultures in the presence of different types of biomaterials (pyrolytic carbon, cobalt-Chromium, titanium) has been performed. These cell cultures were subjected to biological characterization tests and mechanical characterization. The obtained results correlate with the in vivo observations (a promotion of the creation of a neocartilagical tissue in contact with the Pyrolytic Carbon implants).

Oxygen reduction reaction activity and structural stability of Pt-Au nanoparticles prepared by arc-plasma deposition.

PubMed

Takahashi, Shuntaro; Chiba, Hiroshi; Kato, Takashi; Endo, Shota; Hayashi, Takehiro; Todoroki, Naoto; Wadayama, Toshimasa

2015-07-28

The oxygen reduction reaction (ORR) activity and durability of various Au(x)/Pt100 nanoparticles (where x is the atomic ratio of Au against Pt) are evaluated herein. The samples were fabricated on a highly-oriented pyrolytic graphite substrate at 773 K through sequential arc-plasma depositions of Pt and Au. The electrochemical hydrogen adsorption charges (electrochemical surface area), particularly the characteristic currents caused by the corner and edge sites of the Pt nanoparticles, decrease with increasing Au atomic ratio (x). In contrast, the specific ORR activities of the Au(x)/Pt100 samples were dependent on the atomic ratios of Pt and Au: the Au28/Pt100 sample showed the highest specific activity among all the investigated samples (x = 0-42). As for ORR durability evaluated by applying potential cycles between 0.6 and 1.0 V in oxygen-saturated 0.1 M HClO4, Au28/Pt100 was the most durable sample against the electrochemical potential cycles. The results clearly showed that the Au atoms located at coordinatively-unsaturated sites, e.g. at the corners or edges of the Pt nanoparticles, can improve the ORR durability by suppressing unsaturated-site-induced degradation of the Pt nanoparticles.

Broadband optical properties of graphene and HOPG investigated by spectroscopic Mueller matrix ellipsometry

NASA Astrophysics Data System (ADS)

Song, Baokun; Gu, Honggang; Zhu, Simin; Jiang, Hao; Chen, Xiuguo; Zhang, Chuanwei; Liu, Shiyuan

2018-05-01

Optical properties of mono-graphene fabricated by chemical vapor deposition (CVD) and highly oriented pyrolytic graphite (HOPG) are comparatively studied by Mueller matrix ellipsometry (MME) over an ultra-wide energy range of 0.73-6.42 eV. A multilayer stacking model is constructed to describe the CVD mono-graphene, in which the roughness of the glass substrate and the water adsorption on the graphene are considered. We introduce a uniaxial anisotropic dielectric model to parameterize the optical constants of both the graphene and the HOPG. With the established models, broadband optical constants of the graphene and the HOPG are determined from the Mueller matrix spectra based on a point-by-point method and a non-linear regression method, respectively. Two significant absorption peaks at 4.75 eV and 6.31 eV are observed in the extinction coefficient spectra of the mono-graphene, which can be attributed to the von-Hove singularity (i.e., the π-to-π∗ exciton transition) near the M point and the σ-to-σ∗ exciton transition near the Γ point of the Brillouin zone, respectively. Comparatively, only a major absorption peak at 4.96 eV appears in the ordinary extinction coefficient spectra of the HOPG, which is mainly formed by the π-to-π∗ interband transition.

Formation, dissolution and properties of surface nanobubbles

NASA Astrophysics Data System (ADS)

Che, Zhizhao; Theodorakis, Panagiotis E.

2017-02-01

Surface nanobubbles are stable gaseous phases in liquids that form on solid substrates. While their existence has been confirmed, there are many open questions related to their formation and dissolution processes along with their structures and properties, which are difficult to investigate experimentally. To address these issues, we carried out molecular dynamics simulations based on atomistic force fields for systems comprised of water, air (N2 and O2), and a Highly Oriented Pyrolytic Graphite (HOPG) substrate. Our results provide insights into the formation/dissolution mechanisms of nanobubbles and estimates for their density, contact angle, and surface tension. We found that the formation of nanobubbles is driven by an initial nucleation process of air molecules and the subsequent coalescence of the formed air clusters. The clusters form favorably on the substrate, which provides an enhanced stability to the clusters. In contrast, nanobubbles formed in the bulk either move randomly to the substrate and spread or move to the water--air surface and pop immediately. Moreover, nanobubbles consist of a condensed gaseous phase with a surface tension smaller than that of an equivalent system under atmospheric conditions, and contact angles larger than those in the equivalent nanodroplet case. We anticipate that this study will provide useful insights into the physics of nanobubbles and will stimulate further research in the field by using all-atom simulations.

Transmission measurement based on STM observation to detect the penetration depth of low-energy heavy ions in botanic samples.

PubMed

Liu, Feng; Wang, Yugang; Xue, Jianming; Wang, Sixue; Du, Guanhua; Zhao, Weijiang

2003-02-01

The penetration depth of low-energy heavy ions in botanic samples was detected with a new transmission measurement. In the measurement, highly oriented pyrolytic graphite (HOPG) pieces were placed behind the botanic samples with certain thickness. During the irradiation of heavy ions with energy of tens of keV, the energetic particles transmitted from those samples were received by the HOPG pieces. After irradiation, scanning tunneling microscope (STM) was applied to observe protrusion-like damage induced by these transmitted ions on the surface of the HOPG. The statistical average number density of protrusions and the minimum transmission rate of the low-energy heavy ions can be obtained. The detection efficiency of the new method for low-energy heavy ions was about 0.1-1 and the background in the measurement can be reduced to as low as 1.0 x 10(8) protrusions/cm2. With this method, the penetration depth of the energetic particles was detected to be no less than 60 micrometers in kidney bean slices when the slices were irradiated by 100 keVAr+ ion at the fluence of 5 x 10(16) ions/cm2. c2002 Elsevier Science Ltd. All rights reserved.

Peeling the astronomical onion.

PubMed

Rosu-Finsen, Alexander; Marchione, Demian; Salter, Tara L; Stubbing, James W; Brown, Wendy A; McCoustra, Martin R S

2016-11-23

Water ice is the most abundant solid in the Universe. Understanding the formation, structure and multiplicity of physicochemical roles for water ice in the cold, dense interstellar environments in which it is predominantly observed is a crucial quest for astrochemistry as these are regions active in star and planet formation. Intuitively, we would expect the mobility of water molecules deposited or synthesised on dust grain surfaces at temperatures below 50 K to be very limited. This work delves into the thermally-activated mobility of H 2 O molecules on model interstellar grain surfaces. The energy required to initiate this process is studied by reflection-absorption infrared spectroscopy of small quantities of water on amorphous silica and highly oriented pyrolytic graphite surfaces as the surface is annealed. Strongly non-Arrhenius behaviour is observed with an activation energy of 2 kJ mol -1 on the silica surface below 25 K and 0 kJ mol -1 on both surfaces between 25 and 100 K. The astrophysical implication of these results is that on timescales shorter than that estimated for the formation of a complete monolayer of water ice on a grain, aggregation of water ice will result in a non-uniform coating of water, hence leaving bare grain surface exposed. Other molecules can thus be formed or adsorbed on this bare surface.

Transmission measurement based on STM observation to detect the penetration depth of low-energy heavy ions in botanic samples

NASA Technical Reports Server (NTRS)

Liu, Feng; Wang, Yugang; Xue, Jianming; Wang, Sixue; Du, Guanhua; Zhao, Weijiang

2003-01-01

The penetration depth of low-energy heavy ions in botanic samples was detected with a new transmission measurement. In the measurement, highly oriented pyrolytic graphite (HOPG) pieces were placed behind the botanic samples with certain thickness. During the irradiation of heavy ions with energy of tens of keV, the energetic particles transmitted from those samples were received by the HOPG pieces. After irradiation, scanning tunneling microscope (STM) was applied to observe protrusion-like damage induced by these transmitted ions on the surface of the HOPG. The statistical average number density of protrusions and the minimum transmission rate of the low-energy heavy ions can be obtained. The detection efficiency of the new method for low-energy heavy ions was about 0.1-1 and the background in the measurement can be reduced to as low as 1.0 x 10(8) protrusions/cm2. With this method, the penetration depth of the energetic particles was detected to be no less than 60 micrometers in kidney bean slices when the slices were irradiated by 100 keVAr+ ion at the fluence of 5 x 10(16) ions/cm2. c2002 Elsevier Science Ltd. All rights reserved.

Trace element content and magnetic properties of commercial HOPG samples studied by ion beam microscopy and SQUID magnetometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spemann, D., E-mail: spemann@uni-leipzig.de; Esquinazi, P., E-mail: esquin@physik.uni-leipzig.de; Setzer, A.

In this study, the impurity concentration and magnetic response of nine highly oriented pyrolytic graphite (HOPG) samples with different grades and from different providers were determined using ion beam microscopy and SQUID magnetometry. Apart from sideface contaminations in the as-received state, bulk contamination of the samples in most cases consists of disk-shaped micron-sized particles made of Ti and V with an additional Fe contamination around the grain perimeter. The saturation magnetization typically increases with Fe concentration, however, there is no simple correlation between Fe content and magnetic moment. The saturation magnetization of one, respectively six, out of nine samples clearlymore » exceeds the maximum contribution from pure Fe or Fe{sub 3}C. For most samples the temperature dependence of the remanence decreases linearly with T – a dependence found previously for defect-induced magnetism (DIM) in HOPG. We conclude that apart from magnetic impurities, additional contribution to the ferromagnetic magnetization exists in pristine HOPG in agreement with previous studies. A comparative study between the results of ion beam microscopy and the commonly used EDX analysis shows clearly that EDX is not a reliable method for quantitative trace elemental analysis in graphite, clarifying weaknesses and discrepancies in the element concentrations given in the recent literature.« less

Coherent anti-Stokes Raman scattering enhancement of thymine adsorbed on graphene oxide

PubMed Central

2014-01-01

Coherent anti-Stokes Raman scattering (CARS) of carbon nanostructures, namely, highly oriented pyrolytic graphite, graphene nanoplatelets, graphene oxide, and multiwall carbon nanotubes as well CARS spectra of thymine (Thy) molecules adsorbed on graphene oxide were studied. The spectra of the samples were compared with spontaneous Raman scattering (RS) spectra. The CARS spectra of Thy adsorbed on graphene oxide are characterized by shifts of the main bands in comparison with RS. The CARS spectra of the initial nanocarbons are definitely different: for all investigated materials, there is a redistribution of D- and G-mode intensities, significant shift of their frequencies (more than 20 cm-1), and appearance of new modes about 1,400 and 1,500 cm-1. The D band in CARS spectra is less changed than the G band; there is an absence of 2D-mode at 2,600 cm-1 for graphene and appearance of intensive modes of the second order between 2,400 and 3,000 cm-1. Multiphonon processes in graphene under many photon excitations seem to be responsible for the features of the CARS spectra. We found an enhancement of the CARS signal from thymine adsorbed on graphene oxide with maximum enhancement factor about 105. The probable mechanism of CARS enhancement is discussed. PMID:24948887

The Physics and Chemistry of carbides, Nitrides and Borides. Volume 185

DTIC Science & Technology

1990-01-01

and C-B-C chains [15,17]. Clearly, the use of boron-rich solids as electronic materials will place new demands on the quality of materials. In this...first heated in a pyrolytic boron nitride (PBN) crucible ( Union Carbide Corp.) under high vacuum (< 50 mTorr) to 1900°C. This removed surface...contamination of the sample. The powders were loaded into a graphite die with a high-purity BN die liner ( Union Carbide Grade HBC) with inner diameter of 3/8

Upgrading pyrolytic residue from waste tires to commercial carbon black.

PubMed

Zhang, Xue; Li, Hengxiang; Cao, Qing; Jin, Li'e; Wang, Fumeng

2018-05-01

The managing and recycling of waste tires has become a worldwide environmental challenge. Among the different disposal methods for waste tires, pyrolysis is regarded as a promising route. How to effectively enhance the added value of pyrolytic residue (PR) from waste tires is a matter of great concern. In this study, the PRs were treated with hydrochloric and hydrofluoric acids in turn under ultrasonic waves. The removal efficiency for the ash and sulfur was investigated. The pyrolytic carbon black (PCB) obtained after treating PR with acids was analyzed by X-ray fluorescence spectrophotometry, Fourier transform infrared spectrometry, X-ray diffractometry, laser Raman spectrometry, scanning electron microscopy, thermogravimetric (TG) analysis, and physisorption apparatus. The properties of PCB were compared with those of commercial carbon black (CCB) N326 and N339. Results showed PRs from waste tires were mainly composed of carbon, sulfur, and ash. The carbon in PCB was mainly from the CCB added during tire manufacture rather than from the pyrolysis of pure rubbers. The removal percentages for the ash and sulfur of PR are 98.33% (from 13.98 wt % down to 0.24 wt %) and 70.16% (from 1.81 wt % down to 0.54 wt %), respectively, in the entire process. The ash was mainly composed of metal oxides, sulfides, and silica. The surface properties, porosity, and morphology of the PCB were all close to those of N326. Therefore, PCB will be a potential alternative of N326 and reused in tire manufacture. This route successfully upgrades PR from waste tires to the high value-added CCB and greatly increases the overall efficiency of the waste tire pyrolysis industry.

Developmental toxicity of PAH mixtures in fish early life stages. Part I: adverse effects in rainbow trout.

PubMed

Le Bihanic, Florane; Morin, Bénédicte; Cousin, Xavier; Le Menach, Karyn; Budzinski, Hélène; Cachot, Jérôme

2014-12-01

A new gravel-contact assay using rainbow trout, Oncorhynchus mykiss, embryos was developed to assess the toxicity of polycyclic aromatic hydrocarbons (PAHs) and other hydrophobic compounds. Environmentally realistic exposure conditions were mimicked with a direct exposure of eyed rainbow trout embryos incubated onto chemical-spiked gravels until hatching at 10 °C. Several endpoints were recorded including survival, hatching delay, hatching success, biometry, developmental abnormalities, and DNA damage (comet and micronucleus assays). This bioassay was firstly tested with two model PAHs, fluoranthene and benzo[a]pyrene. Then, the method was applied to compare the toxicity of three PAH complex mixtures characterized by different PAH compositions: a pyrolytic extract from a PAH-contaminated sediment (Seine estuary, France) and two petrogenic extracts from Arabian Light and Erika oils, at two environmental concentrations, 3 and 10 μg g(-1) sum of PAHs. The degree and spectrum of toxicity were different according to the extract considered. Acute effects including embryo mortality and decreased hatching success were observed only for Erika oil extract. Arabian Light and pyrolytic extracts induced mainly sublethal effects including reduced larvae size and hemorrhages. Arabian Light and Erika extracts both induced repairable DNA damage as revealed by the comet assay versus the micronucleus assay. The concentration and proportion of methylphenanthrenes and methylanthracenes appeared to drive the toxicity of the three PAH fractions tested, featuring a toxic gradient as follows: pyrolytic < Arabian Light < Erika. The minimal concentration causing developmental defects was as low as 0.7 μg g(-1) sum of PAHs, indicating the high sensitivity of the assay and validating its use for toxicity assessment of particle-bound pollutants.

Enhanced diesel fuel fraction from waste high-density polyethylene and heavy gas oil pyrolysis using factorial design methodology.

PubMed

Joppert, Ney; da Silva, Alexsandro Araujo; da Costa Marques, Mônica Regina

2015-02-01

Factorial Design Methodology (FDM) was developed to enhance diesel fuel fraction (C9-C23) from waste high-density polyethylene (HDPE) and Heavy Gas Oil (HGO) through co-pyrolysis. FDM was used for optimization of the following reaction parameters: temperature, catalyst and HDPE amounts. The HGO amount was constant (2.00 g) in all experiments. The model optimum conditions were determined to be temperature of 550 °C, HDPE = 0.20 g and no FCC catalyst. Under such conditions, 94% of pyrolytic oil was recovered, of which diesel fuel fraction was 93% (87% diesel fuel fraction yield), no residue was produced and 6% of noncondensable gaseous/volatile fraction was obtained. Seeking to reduce the cost due to high process temperatures, the impact of using higher catalyst content (25%) with a lower temperature (500 °C) was investigated. Under these conditions, 88% of pyrolytic oil was recovered (diesel fuel fraction yield was also 87%) as well as 12% of the noncondensable gaseous/volatile fraction. No waste was produced in these conditions, being an environmentally friendly approach for recycling the waste plastic. This paper demonstrated the usefulness of using FDM to predict and to optimize diesel fuel fraction yield with a great reduction in the number of experiments. Copyright © 2014 Elsevier Ltd. All rights reserved.

The theory of cyclic voltammetry of electrochemically heterogeneous surfaces: comparison of different models for surface geometry and applications to highly ordered pyrolytic graphite.

PubMed

Ward, Kristopher R; Lawrence, Nathan S; Hartshorne, R Seth; Compton, Richard G

2012-05-28

The cyclic voltammetry at electrodes composed of multiple electroactive materials, where zones of one highly active material are distributed over a substrate of a second, less active material, is investigated by simulation. The two materials are assumed to differ in terms of their electrochemical rate constants towards any given redox couple. For a one-electron oxidation or reduction, the effect on voltammetry of the size and relative surface coverages of the zones as well as the rate constant of the slower zone are considered for systems where it is much slower than the rate constant of the faster zones. The occurrence of split peak cyclic voltammetry where two peaks are observed in the forward sweep, is studied in terms of the diffusional effects present in the system. A number of surface geometries are compared: specifically the more active zones are modelled as long, thin bands, as steps in the surface, as discs, and as rings (similar to a partially blocked electrode). Similar voltammetry for the band, step and ring models is seen but the disc geometry shows significant differences. Finally, the simulation technique is applied to the modelling of highly-ordered pyrolytic graphite (HOPG) surface and experimental conditions under which it may be possible to observe split peak voltammetry are predicted.

Pollutant formation in the pyrolysis and combustion of materials combining biomass and e-waste.

PubMed

Soler, Aurora; Conesa, Juan A; Iñiguez, María E; Ortuño, Nuria

2018-05-01

Combustion and pyrolysis runs at 850°C were carried out in a laboratory scale horizontal reactor with different materials combining biomass and waste electrical and electronic equipment (WEEE). Analyses are presented of the carbon oxides, light hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), polychlorinated benzenes (ClBzs), polychlorinated phenols (ClPhs), polybrominated phenols (BrPhs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Results showed that gas emissions were mainly composed of CO and CO 2 ; the high level of CO found in the pyrolytic runs was easily transformed into CO 2 by reaction with oxygen. The total amount of light hydrocarbons emitted was higher in the samples containing WEEE, methane being the most abundant light hydrocarbon in all the runs. However, the presence of WEEE reduced the emission of PAHs which decreased with the increase of the oxygen. The total amount of BrPhs increased in the decomposition of the samples containing WEEE, reaching its maximum in pyrolysis runs. Emission of PCDD/Fs was enhanced in pyrolytic conditions and easily decreased in the presence of oxygen. Copyright © 2017 Elsevier B.V. All rights reserved.

Improving hydrocarbon yield from catalytic fast co-pyrolysis of hemicellulose and plastic in the dual-catalyst bed of CaO and HZSM-5.

PubMed

Ding, Kuan; Zhong, Zhaoping; Wang, Jia; Zhang, Bo; Fan, Liangliang; Liu, Shiyu; Wang, Yunpu; Liu, Yuhuan; Zhong, Daoxu; Chen, Paul; Ruan, Roger

2018-08-01

The high concentration of oxygenated compounds in pyrolytic products prohibits the conversion of hemicellulose to important biofuels and chemicals via fast pyrolysis. Herein a dual-catalyst bed of CaO and HZSM-5 was developed to convert acids in the pyrolytic products of xylan to valuable hydrocarbons. Meanwhile, LLDPE was co-pyrolyzed with xylan to supplement hydrogen during the catalysis of HZSM-5. The results showed that CaO could effectively transform acids into ketones. A minimum yield of acids (2.74%) and a maximum yield of ketones (42.93%) were obtained at a catalyst to feedstock ratio of 2:1. The dual-catalyst bed dramatically increased the yield of aromatics. Moreover, hydrogen-rich fragments derived from LLDPE promoted the Diels-Alder reactions of furans and participated in the hydrocarbon pool reactions of non-furanic compounds. As a result, a higher yield of hydrocarbons was achieved. This study provides a fundamental for recovering energy and chemicals from pyrolysis of hemicellulose. Copyright © 2018 Elsevier Ltd. All rights reserved.

Hydrothermal pretreatment of microalgae for production of pyrolytic bio-oil with a low nitrogen content.

PubMed

Du, Zhenyi; Mohr, Michael; Ma, Xiaochen; Cheng, Yanling; Lin, Xiangyang; Liu, Yuhuan; Zhou, Wenguang; Chen, Paul; Ruan, Roger

2012-09-01

Microalgae can be converted to an energy-dense bio-oil via pyrolysis; however, the relatively high nitrogen content of this bio-oil presents a challenge for its direct use as fuels. Therefore, hydrothermal pretreatment was employed to reduce the N content in Nannochloropsis oculata feedstock by removing proteins without requiring significant energy inputs. The effects of reaction conditions on the yield and composition of pretreated algae were investigated by varying the temperature (150-225°C) and reaction time (10-60 min). Compared with untreated algae, pretreated samples had higher carbon contents and enhanced heating values under all reaction conditions and 6-42% lower N contents at 200-225°C for 30-60 min. The pyrolytic bio-oil from pretreated algae contained less N-containing compounds than that from untreated samples and the bio-oil contained mainly (44.9% GC-MS peak area) long-chain fatty acids (C14-C18) which can be more readily converted into hydrocarbon fuels in the presence of simple catalysts. Copyright © 2012 Elsevier Ltd. All rights reserved.

Physical and Chemical Properties of Bio-Oils From Microwave Pyrolysis of Corn Stover

NASA Astrophysics Data System (ADS)

Yu, Fei; Deng, Shaobo; Chen, Paul; Liu, Yuhuan; Wan, Yiqin; Olson, Andrew; Kittelson, David; Ruan, Roger

This study was aimed to understand the physical and chemical properties of pyrolytic bio-oils produced from microwave pyrolysis of corn stover regarding their potential use as gas turbine and home heating fuels. The ash content, solids content, pH, heating value, minerals, elemental ratio, moisture content, and viscosity of the bio-oils were determined. The water content was approx 15.2 wt%, solids content 0.22 wt%, alkali metal content 12 parts per million, dynamic viscosity 185 mPa·s at 40°C, and gross high heating value 17.5 MJ/kg for a typical bio-oil produced. Our aging tests showed that the viscosity and water content increased and phase separation occurred during the storage at different temperatures. Adding methanol and/or ethanol to the bio-oils reduced the viscosity and slowed down the increase in viscosity and water content during the storage. Blending of methanol or ethanol with the bio-oils may be a simple and cost-effective approach to making the pyrolytic bio-oils into a stable gas turbine or home heating fuels.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gerczak, Tyler J.; Smith, Kurt R.; Petrie, Christian M.

Tristructural-isotropic (TRISO)–coated particle fuel is a promising advanced fuel concept consisting of a spherical fuel kernel made of uranium oxide and uranium carbide, surrounded by a porous carbonaceous buffer layer and successive layers of dense inner pyrolytic carbon (IPyC), silicon carbide (SiC) deposited by chemical vapor , and dense outer pyrolytic carbon (OPyC). This fuel concept is being considered for advanced reactor applications such as high temperature gas-cooled reactors (HTGRs) and molten salt reactors (MSRs), as well as for accident-tolerant fuel for light water reactors (LWRs). Development and implementation of TRISO fuel for these reactor concepts support the US Departmentmore » of Energy (DOE) Office of Nuclear Energy mission to promote safe, reliable nuclear energy that is sustainable and environmentally friendly. During operation, the SiC layer serves as the primary barrier to metallic fission products and actinides not retained in the kernel. It has been observed that certain fission products are released from TRISO fuel during operation, notably, Ag, Eu, and Sr [1]. Release of these radioisotopes causes safety and maintenance concerns.« less

Physical and chemical properties of bio-oils from microwave pyrolysis of corn stover.

PubMed

Yu, Fei; Deng, Shaobo; Chen, Paul; Liu, Yuhuan; Wan, Yiqin; Olson, Andrew; Kittelson, David; Ruan, Roger

2007-04-01

This study was aimed to understand the physical and chemical properties of pyrolytic bio-oils produced from microwave pyrolysis of corn stover regarding their potential use as gas turbine and home heating fuels. The ash content, solids content, pH, heating value, minerals, elemental ratio, moisture content, and viscosity of the bio-oils were determined. The water content was approx 15.2 wt%, solids content 0.22 wt%, alkali metal content 12 parts per million, dynamic viscosity 185 mPa.s at 40 degrees C, and gross high heating value 17.5 MJ/kg for a typical bio-oil produced. Our aging tests showed that the viscosity and water content increased and phase separation occurred during the storage at different temperatures. Adding methanol and/or ethanol to the bio-oils reduced the viscosity and slowed down the increase in viscosity and water content during the storage. Blending of methanol or ethanol with the bio-oils may be a simple and cost-effective approach to making the pyrolytic bio-oils into a stable gas turbine or home heating fuels.

Mechanical performance of pyrolytic carbon in prosthetic heart valve applications.

PubMed

Cao, H

1996-06-01

An experimental procedure has been developed for rigorous characterization of the fracture resistance and fatigue crack extension in pyrolytic carbon for prosthetic heart valve application. Experiments were conducted under sustained and cyclic loading in a simulated biological environment using Carbomedics Pyrolite carbon. While the material was shown to have modest fracture toughness, it exhibited excellent resistance to subcritical crack growth. The crack growth kinetics in pyrolytic carbon were formulated using a phenomenological description. A fatigue threshold was observed below which the crack growth rate diminishes. A damage tolerance concept based on fracture mechanics was used to develop an engineering design approach for mechanical heart valve prostheses. In particular, a new quantity, referred to as the safe-life index, was introduced to assess the design adequacy against subcritical crack growth in brittle materials. In addition, a weakest-link statistical description of the fracture strength is provided and used in the design of component proof-tests. It is shown that the structural reliability of mechanical heart valves can be assured by combining effective flaw detection and manufacturing quality control with adequate damage tolerance design.

Anisotropy measurement of pyrolytic carbon layers of coated particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vesyolkin, Ju. A., E-mail: Ju.Ves@yandex.ru; Ivanov, A. S., E-mail: asi.kiae@gmail.com; Trushkina, T. V.

2015-12-15

Equipment at the National Research Center Kurchatov Institute intended for the anisotropy determination of pyrolytic carbon layers in coated particles (CPs) of the GT-MGR reactor is tested and calibrated. The dependence of the anisotropy coefficient on the size of the measurement region is investigated. The results of measuring the optical anisotropy factor (OPTAF) for an aluminum mirror, rutile crystal, and available CP samples with the known characteristics measured previously using ORNL equipment (United States) are presented. In addition, measurements of CP samples prepared at VNIINM are performed. A strong dependence of the data on the preparation quality of metallographic sectionsmore » is found. Our investigations allow us to make the conclusion on the working capacity of the existing equipment for measuring the anisotropy of pyrolytic carbon CP coatings using the equipment at the Kurchatov Institute with the relative error of about 1%. It is shown that the elimination of the errors caused by the stochastic fluctuations in a measuring path by mathematical processing of the signal allows us to decrease the relative error of OPTAF measurements to ∼0.3%.« less

Comparison of pyrolytic products produced from inorganic-rich and demineralized rice straw (Oryza sativa L.) by fluidized bed pyrolyzer for future biorefinery approach.

PubMed

Eom, In-Yong; Kim, Jae-Young; Lee, Soo-Min; Cho, Tae-Su; Yeo, Hwanmyeong; Choi, Joon-Weon

2013-01-01

The objectives of this study were to investigate the effects of inorganic constituents on the fast pyrolysis of the biomass and to determine the yields as well as physicochemical properties of pyrolytic products. The pyrolytic products were obtained from raw and demineralized rice straw using a fluidized bed type pyrolyzer at different temperatures. As pyrolysis temperature increased, total biooil yield gradually decreased from 46.6 to 29.6 wt.% for the raw-straw, and from 55.4 to 35.3 wt.% for the demineralized rice straw. For demineralized rice straw, higher pyrolysis temperatures promoted gasification reactions but reduced char formations. However, char yield for the raw-straw was relatively unaffected by temperature due to an increase in carbonization reactions that were catalyzed by some inorganics. Certain inorganic constituents in the biomass were distinctively distributed in the biooil, and ICP-ES and GC/MS analysis indicated that some inorganics may be chemically bound to cell wall components. Copyright © 2012 Elsevier Ltd. All rights reserved.

Distillation of granulated scrap tires in a pilot plant.

PubMed

López, Félix A; Centeno, Teresa A; Alguacil, Francisco José; Lobato, Belén

2011-06-15

This paper reports the pyrolytic treatment of granulated scrap tires (GST) in a pilot distillation unit at moderate temperature (550°C) and atmospheric pressure, to produce oil, char and gas products. Tire-derived oil is a complex mixture of organic C(5)-C(24) compounds, including a very large proportion of aromatic compounds. This oil has a high gross calorific value (∼ 43 MJ kg(-1)) and N and S contents of 0.4% and 0.6%, respectively, falling within the specifications of certain heating fuels. The distillation gas is composed of hydrocarbons; methane and n-butane are the most abundant, investing the distillation gas with a very high gross calorific value (∼ 68 MJ Nm(-3)). This gas is transformed into electric power by a co-generation turbine. The distillation char is mostly made of carbon but with significant inorganic impurities (∼ 12 wt%). The quality of the solid residue of the process is comparable to that of some commercial chars. The quantity of residual solids, and the qualities of the gas, liquid and solid fractions, are similar to those obtained by conventional pyrolytic treatments of waste tires. However, the simplicity of the proposed technology and its low investment costs make it a very attractive alternative. Copyright © 2011 Elsevier B.V. All rights reserved.

Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

DOEpatents

Sharp, Donald J.; Armstrong, Pamela S.; Panitz, Janda Kirk G.

1998-01-01

A solid electrolytic capacitor having a solid electrolyte comprising manganese dioxide dispersed in an aromatic polyamide capable of further cure to form polyimide linkages, the solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects.

Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

DOEpatents

Sharp, D.J.; Armstrong, P.S.; Panitz, J.K.G.

1998-03-17

A solid electrolytic capacitor is described having a solid electrolyte comprising manganese dioxide dispersed in an aromatic polyamide capable of further cure to form polyimide linkages, the solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects. 2 figs.

Determination of the “NiOOH” charge and discharge mechanisms at ideal activity

DOE PAGES

Merrill, Matthew; Worsley, Marcus; Wittstock, Arne; ...

2014-01-24

Here, optimization of electrodeposition conditions produced Ni(OH) 2 deposits chargeable up to 1.84 ± 0.02 e – per Ni on and the resulting nickel oxide/hydroxide active material could subsequently deliver 1.58 ± 0.02 e – per Ni ion (462 mA h/g) over a potential range <0.2 V. The ability of the “NiOOH” active material to deliver an approximately ideal charge and discharge facilitated a coulometric and thermodynamic analysis through which the charge/discharge mechanisms were determined from known enthalpies of formation. The (dis)charge states were confirmed with in situ Raman spectroscopy. The mechanisms were additionally evaluated with respect to pH andmore » potential dependence, charge quantities, hysteresis, and fluoride ion partial inhibition of the charge mechanism. The results indicate that the “NiOOH” (dis)charges as a solid-state system with mechanisms consistent with known nickel and oxygen redox reactions. A defect chemistry mechanism known for the LiNiO 2 system also occurs for “NiOOH” to cause both high activity and hysteresis. Similar to other cation insertion nickel oxides, the activity of the “NiOOH” mechanism is predominantly due to oxygen redox activity and does not involve the Ni4 + oxidation state. The “NiOOH” was produced from cathodic electrodeposition of Ni(OH) 2 from nickel nitrate solutions onto highly oriented pyrolytic graphite at ideal electrodeposition current efficiencies and the deposition mechanism was also characterized.« less

Tuning role and mechanism of paint sludge for characteristics of sewage sludge carbon: Paint sludge as a new macro-pores forming agent.

PubMed

Li, Siyang; Feng, Jinxi; Tian, Shuanghong; Lan, Shenyu; Fan, Chao; Liu, Xiaosheng; Xiong, Ya

2018-02-15

For the first time, paint sludge waste (PS) was used as a pore forming agent in the preparation of sewage sludge derived carbon (SC). The tuning role and mechanism of PS for characteristics of SC were explored. It was found that a sludge carbon (SC PS-Zn ) with rich macro-, meso- and micro- porous could be produced by one-step pyrolytic process of sludge in the presence of PS and ZnCl 2. Its surface area could reach as high as 680.5m 2 g -1 as 88.4 times and 4.8 times of sludge carbon without addition of PS and ZnCl 2 (SC) and only addition of ZnCl 2 (SC Zn ) , respectively. The macro- pores fabricated by PS provided much inner-space for ZnCl 2 to generate meso- and micro- porous, leading to a hierarchical porous structure. SC PS-Zn showed a high adsorption capacity of 685.4mgg -1 for Chrysophenine, which is 1.3 and 1.7 times that of SC PS and SC Zn respectively. The adsorption difference could be simply attributed to the fact that the great molecules were difficult to enter micro- pores of SC Zn . It was also found that the difference was also dependent on orientation of Chrysophenine, which was related to pH value of solution. Copyright © 2017. Published by Elsevier B.V.

From Graphite to Graphene via Scanning Tunneling Microscopy

NASA Astrophysics Data System (ADS)

Qi, Dejun

The primary objective of this dissertation is to study both graphene on graphite and pristine freestanding grapheme using scanning tunneling microscopy (STM) and density functional theory (DFT) simulation technique. In the experiment part, good quality tungsten metalic tips for experiment were fabricated using our newly developed tip making setup. Then a series of measurements using a technique called electrostatic-manipulation scanning tunneling microscopy (EM-STM) of our own development were performed on a highly oriented pyrolytic graphite (HOPG) surface. The electrostatic interaction between the STM tip and the sample can be tuned to produce both reversible and irreversible large-scale movement of the graphite surface. Under this influence, atomic-resolution STM images reveal that a continuous electronic transition between two distinct patterns can be systematically controlled. DFT calculations reveal that this transition can be related to vertical displacements of the top layer of graphite relative to the bulk. Evidence for horizontal shifts in the top layer of graphite is also presented. Excellent agreement is found between experimental STM images and those simulated using DFT. In addition, the EM-STM technique was also used to controllably and reversibly pull freestanding graphene membranes up to 35 nm from their equilibrium height. Atomic-scale corrugation amplitudes 20 times larger than the STM electronic corrugation for graphene on a substrate were observed. The freestanding graphene membrane responds to a local attractive force created at the STM tip as a highly conductive yet flexible grounding plane with an elastic restoring force.

Atomic Oxygen Fluence Monitor

NASA Technical Reports Server (NTRS)

Banks, Bruce A.

2011-01-01

This innovation enables a means for actively measuring atomic oxygen fluence (accumulated atoms of atomic oxygen per area) that has impinged upon spacecraft surfaces. Telemetered data from the device provides spacecraft designers, researchers, and mission managers with real-time measurement of atomic oxygen fluence, which is useful for prediction of the durability of spacecraft materials and components. The innovation is a compact fluence measuring device that allows in-space measurement and transmittance of measured atomic oxygen fluence as a function of time based on atomic oxygen erosion yields (the erosion yield of a material is the volume of material that is oxidized per incident oxygen atom) of materials that have been measured in low Earth orbit. It has a linear electrical response to atomic oxygen fluence, and is capable of measuring high atomic oxygen fluences (up to >10(exp 22) atoms/sq cm), which are representative of multi-year low-Earth orbital missions (such as the International Space Station). The durability or remaining structural lifetime of solar arrays that consist of polymer blankets on which the solar cells are attached can be predicted if one knows the atomic oxygen fluence that the solar array blanket has been exposed to. In addition, numerous organizations that launch space experiments into low-Earth orbit want to know the accumulated atomic oxygen fluence that their materials or components have been exposed to. The device is based on the erosion yield of pyrolytic graphite. It uses two 12deg inclined wedges of graphite that are over a grit-blasted fused silica window covering a photodiode. As the wedges erode, a greater area of solar illumination reaches the photodiode. A reference photodiode is also used that receives unobstructed solar illumination and is oriented in the same direction as the pyrolytic graphite covered photodiode. The short-circuit current from the photodiodes is measured and either sent to an onboard data logger, or transmitted to a receiving station on Earth. By comparison of the short-circuit currents from the fluence-measuring photodiode and the reference photodiode, one can compute the accumulated atomic oxygen fluence arriving in the direction that the fluence monitor is pointing. The device produces a signal that is linear with atomic oxygen fluence using a material whose atomic oxygen erosion yield has been measured over a period of several years in low-Earth orbit.

Monochromatic X-ray sources based on a mechanism of real and virtual photon diffraction in crystals

NASA Astrophysics Data System (ADS)

Wagner, A. R.; Kuznetsov, S. I.; Potylitsyn, A. P.; Razin, S. V.; Uglov, S. R.; Zabaev, V. N.

2008-09-01

A source of monochromatic X-ray radiation is wanted in industry, science, medicine and so on. Many ways of making such a source are known. The present work describes two mechanisms for the creation of a monochromatic X-ray beam, which are parametric X-ray radiation (PXR) and bremsstrahlung diffraction (DBS). Both the experiments were carried out using an electron beam at a microtron. During the first experiment, the DBS process was investigated as a scattering of the Bremsstrahlung (BS) beam on the crystallographic surfaces of tungsten and pyrolytic graphite crystals. The second experiment consisted in the registration of the PXR and DBS yield during the passage of the electrons through the same crystals as in the first experiment. The spectral and orientation radiation characteristics and simulation results obtained for the DBS and PXR processes are presented. It is shown that the usage of mosaic crystalline targets is rather useful in order to obtain a monochromatic X-ray source based on bremsstrahlung diffraction from moderately relativistic electrons.

Cyclic fatigue and fracture in pyrolytic carbon-coated graphite mechanical heart-valve prostheses: role of small cracks in life prediction.

PubMed

Dauskardt, R H; Ritchie, R O; Takemoto, J K; Brendzel, A M

1994-07-01

A fracture-mechanics based study has performed to characterize the fracture toughness and rates of cyclic fatigue-crack growth of incipient flaws in prosthetic heart-valve components made of pyrolytic carbon-coated graphite. Such data are required to predict the safe structural lifetime of mechanical heart-valve prostheses using damage-tolerant analysis. Unlike previous studies where fatigue-crack propagation data were obtained using through-thickness, long cracks (approximately 2-20 mm long), growing in conventional (e.g., compact-tension) samples, experiments were performed on physically small cracks (approximately 100-600 microns long), initiated on the surface of the pyrolytic-carbon coating to simulate reality. Small-crack toughness results were found to agree closely with those measured conventionally with long cracks. However, similar to well-known observations in metal fatigue, it was found that based on the usual computations of the applied (far-field) driving force in terms of the maximum stress intensity, Kmax, small fatigue cracks grew at rates that exceeded those of long cracks at the same applied stress intensity, and displayed a negative dependency on Kmax; moreover, they grew at applied stress intensities less than the fatigue threshold value, below which long cracks are presumed dormant. To resolve this apparent discrepancy, it is shown that long and small crack results can be normalized, provided growth rates are characterized in terms of the total (near-tip) stress intensity (incorporating, for example, the effect of residual stress); with this achieved, in principle, either form of data can be used for life prediction of implant devices. Inspection of the long and small crack results reveals extensive scatter inherent in both forms of growth-rate data for the pyrolytic-carbon material.

High-Pressure Liquid Chromatograph with Mass Spectrometric Detection for Analysis of Supercritical Fuels Pyrolysis Products

DTIC Science & Technology

2006-08-01

conditions will necessarily be supercritical fluids . These temperatures and pressures will also cause the fuel to undergo pyrolytic reactions, which...Spectrometric Detection for 5a. CONTRACT NUMBER Analysis of Supercritical Fuels Pyrolysis Products 5b. GRANT NUMBER FA9550-05-1-0253 5c... supercritical pyrolysis experiments with the model fuels 1-methylnaphthalene and toluene. The HPLC/UV/MS instrument facilitated the identification of fifteen 5

High capacity anode materials for lithium ion batteries

DOEpatents

Lopez, Herman A.; Anguchamy, Yogesh Kumar; Deng, Haixia; Han, Yongbon; Masarapu, Charan; Venkatachalam, Subramanian; Kumar, Suject

2015-11-19

High capacity silicon based anode active materials are described for lithium ion batteries. These materials are shown to be effective in combination with high capacity lithium rich cathode active materials. Supplemental lithium is shown to improve the cycling performance and reduce irreversible capacity loss for at least certain silicon based active materials. In particular silicon based active materials can be formed in composites with electrically conductive coatings, such as pyrolytic carbon coatings or metal coatings, and composites can also be formed with other electrically conductive carbon components, such as carbon nanofibers and carbon nanoparticles. Additional alloys with silicon are explored.

Assessment of polycyclic aromatic hydrocarbons (PAHs) in mussels (Mytilus galloprovincialis) of Prince Islands, Marmara Sea.

PubMed

Balcıoğlu, Esra Billur

2016-08-15

In this study, PAH analyses have been conducted on indigenous mussels. Mussel samples (Mytilus galloprovincialis) have been collected from seven stations of Prince Islands during September 2015. Concentrations of total determined PAHs (sum of 16 compounds) ranged between 664 and 9083ngg(-1). The origin of PAHs has been found to be pyrolytic according to the PHE/ANT and FA/PYR ratios in Büyükada. For other islands, PAH origins have been observed as pyrolytic and petrogenic together according to the PHE/ANT, FA/PYR and BaA/CHR ratios. Copyright © 2016 Elsevier Ltd. All rights reserved.

Spring Constants for Stacks of Curved Leaves of Pyrolytic Boron Nitride

NASA Technical Reports Server (NTRS)

Kaforey, M. L.; Deeb, C. W.; Matthiesen, D. H.

1999-01-01

Stacks of curved leaves of pyrolytic boron nitride (PBN) were deflected and the force versus deflection data was recorded. From this data, the spring constant for a given spring geometry (radius of curvature of a leaf, width of a leaf, thickness of a leaf, and number of leaves in the stack) was determined. These experiments were performed at room temperature, 500 C and 1000 C. However, temperature was not found to affect the spring constant. The measured values were generally within one order of magnitude of predictions made using a previously derived equation for a simply supported cylindrical section with a line force at the center.

Fission Product Release and Survivability of UN-Kernel LWR TRISO Fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Besmann, Theodore M; Ferber, Mattison K; Lin, Hua-Tay

2014-01-01

A thermomechanical assessment of the LWR application of TRISO fuel with UN kernels was performed. Fission product release under operational and transient temperature conditions was determined by extrapolation from range calculations and limited data from irradiated UN pellets. Both fission recoil and diffusive release were considered and internal particle pressures computed for both 650 and 800 m diameter kernels as a function of buffer layer thickness. These pressures were used in conjunction with a finite element program to compute the radial and tangential stresses generated with a TRISO particle as a function of fluence. Creep and swelling of the innermore » and outer pyrolytic carbon layers were included in the analyses. A measure of reliability of the TRISO particle was obtained by measuring the probability of survival of the SiC barrier layer and the maximum tensile stress generated in the pyrolytic carbon layers as a function of fluence. These reliability estimates were obtained as functions of the kernel diameter, buffer layer thickness, and pyrolytic carbon layer thickness. The value of the probability of survival at the end of irradiation was inversely proportional to the maximum pressure.« less

Fission product release and survivability of UN-kernel LWR TRISO fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

T. M. Besmann; M. K. Ferber; H.-T. Lin

2014-05-01

A thermomechanical assessment of the LWR application of TRISO fuel with UN kernels was performed. Fission product release under operational and transient temperature conditions was determined by extrapolation from fission product recoil calculations and limited data from irradiated UN pellets. Both fission recoil and diffusive release were considered and internal particle pressures computed for both 650 and 800 um diameter kernels as a function of buffer layer thickness. These pressures were used in conjunction with a finite element program to compute the radial and tangential stresses generated within a TRISO particle undergoing burnup. Creep and swelling of the inner andmore » outer pyrolytic carbon layers were included in the analyses. A measure of reliability of the TRISO particle was obtained by computing the probability of survival of the SiC barrier layer and the maximum tensile stress generated in the pyrolytic carbon layers from internal pressure and thermomechanics of the layers. These reliability estimates were obtained as functions of the kernel diameter, buffer layer thickness, and pyrolytic carbon layer thickness. The value of the probability of survival at the end of irradiation was inversely proportional to the maximum pressure.« less

The effects of temperature and catalysts on the pyrolysis of industrial wastes (herb residue).

PubMed

Wang, Pan; Zhan, Sihui; Yu, Hongbing; Xue, Xufang; Hong, Nan

2010-05-01

Pyrolysis of herb residue was investigated in a fixed-bed to determine the effects of pyrolysis temperature and catalysts (ZSM-5, Al-SBA-15 and alumina) on the products yields and the qualities of bio-oils. The results indicated that the maximum bio-oil yield of 34.26% was obtained at 450 degrees Celsius with 10 wt.% alumina catalyst loaded. The pyrolytic oils were examined by ultimate analysis and calorific values determination, and the results indicated that the presence of all catalysts decreased the oxygen content of bio-oils and increased the calorific values. The order of the catalytic effect for upgrading the pyrolytic oil was Al(2)O(3)>Al-SBA-15>ZSM-5. The bio-oil with the lowest oxygen content (26.71%) and the highest calorific value (25.94 MJ kg(-1)) was obtained with 20 wt.% alumina catalyst loaded. Furthermore, the gas chromatography/mass spectrometry (GC/MS) was used in order to investigate the components of obtained pyrolytic oils. It was found that the alumina catalyst could clearly enhance the formation of aliphatics and aromatics. Crown Copyright 2009. Published by Elsevier Ltd. All rights reserved.

Bactericidal activity of self-assembled palmitic and stearic fatty acid crystals on highly ordered pyrolytic graphite.

PubMed

Ivanova, Elena P; Nguyen, Song Ha; Guo, Yachong; Baulin, Vladimir A; Webb, Hayden K; Truong, Vi Khanh; Wandiyanto, Jason V; Garvey, Christopher J; Mahon, Peter J; Mainwaring, David E; Crawford, Russell J

2017-09-01

The wings of insects such as cicadas and dragonflies have been found to possess nanostructure arrays that are assembled from fatty acids. These arrays can physically interact with the bacterial cell membranes, leading to the death of the cell. Such mechanobactericidal surfaces are of significant interest, as they can kill bacteria without the need for antibacterial chemicals. Here, we report on the bactericidal effect of two of the main lipid components of the insect wing epicuticle, palmitic (C16) and stearic (C18) fatty acids. Films of these fatty acids were re-crystallised on the surface of highly ordered pyrolytic graphite. It appeared that the presence of two additional CH 2 groups in the alkyl chain resulted in the formation of different surface structures. Scanning electron microscopy and atomic force microscopy showed that the palmitic acid microcrystallites were more asymmetric than those of the stearic acid, where the palmitic acid microcrystallites were observed to be an angular abutment in the scanning electron micrographs. The principal differences between the two types of long-chain saturated fatty acid crystallites were the larger density of peaks in the upper contact plane of the palmitic acid crystallites, as well as their greater proportion of asymmetrical shapes, in comparison to that of the stearic acid film. These two parameters might contribute to higher bactericidal activity on surfaces derived from palmitic acid. Both the palmitic and stearic acid crystallite surfaces displayed activity against Gram-negative, rod-shaped Pseudomonas aeruginosa and Gram-positive, spherical Staphylococcus aureus cells. These microcrystallite interfaces might be a useful tool in the fabrication of effective bactericidal nanocoatings. Nanostructured cicada and dragonfly wing surfaces have been discovered to be able physically kill bacterial cells. Here, we report on the successful fabrication of bactericidal three-dimensional structures of two main lipid components of the epicuticle of insect wings, palmitic (C16) and stearic (C18) acids. After crystallisation onto highly ordered pyrolytic graphite, both the palmitic and stearic acid films displayed bactericidal activity against both Gram-negative Pseudomonas aeruginosa and Gram-positive Staphylococcus aureus cells. The simplicity of the production of these microcrystallite interfaces suggests that a fabrication technique, based on solution deposition, could be an effective technique for the application of bactericidal nanocoatings. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Physical and chemical behavior of flowing endothermic jet fuels

NASA Astrophysics Data System (ADS)

Ward, Thomas Arthur

Hydrocarbon fuels have been used as cooling media for aircraft jet engines for decades. However, modern aircraft engines are reaching a practical heat transfer limit beyond which the convective heat transfer provided by fuels is no longer adequate. One solution is to use an endothermic fuel that absorbs heat through a series of pyrolytic chemical reactions. However, many of the physical and chemical processes involved in endothermic fuel degradation are not well understood. The purpose of this dissertation is to study different characteristics of endothermic fuels using experiments and computational models. In the first section, data from three flow experiments using heated Jet-A fuel and additives were analyzed (with the aid of CFD calculations) to study the effects of treated surfaces on surface deposition. Surface deposition is the primary impediment in creating an operational endothermic fuel heat exchanger system, because deposits can obstruct fuel pathways causing a catastrophic system failure. As heated fuel flows through a fuel system, trace species within the fuel react with dissolved O2 to form surface deposits. At relatively higher fuel temperatures, the dissolved O2 is depleted, and pyrolytic chemistry becomes dominant (at temperatures greater than ˜500 °C). In the first experiment, the dissolved O2 consumption of heated fuel was measured on different surface types over a range of temperatures. It is found that use of treated tubes significantly delays oxidation of the fuel. In the second experiment, the treated length of tubing was progressively increased, which varied the characteristics of the thermal-oxidative deposits formed. In the third experiment, pyrolytic surface deposition in either fully treated or untreated tubes is studied. It is found that the treated surface significantly reduced the formation of surface deposits for both thermal oxidative and pyrolytic degradation mechanisms. Moreover, it is found that the chemical reactions resulting in pyrolytic deposition on the untreated surface are more sensitive to pressure level than those causing pyrolytic deposition on the treated surface. The second section describes the development of a two-dimensional computational model of the heat and mass transport associated with a flowing fuel using a unique global chemical kinetics model. This model calculates the changing flow properties of a supercritical reacting fuel by use of experimentally derived proportional product distributions. The third section studies the effects of pressure on flowing; mildly-cracked, supercritical n-decane. The experimental results are studied with the aid of the computational model described in section 2, expanded to deal with variable pressures. The experiments indicate that increasing pressure enhances the processes in which n-decane converts to (C5--C9) n-alkane products instead of decomposing into lower molecular weight products (C1--C4): Increasing pressure also increases the overall conversion rate of supercritical n-decane flowing through a reactor. Computational modeling of the experiment shows how the flow properties are influenced by pressure. (Abstract shortened by UMI.)

A new oxidation based technique for artifact free TEM specimen preparation of nuclear graphite

NASA Astrophysics Data System (ADS)

Johns, Steve; Shin, Wontak; Kane, Joshua J.; Windes, William E.; Ubic, Rick; Karthik, Chinnathambi

2018-07-01

Graphite is a key component in designs of current and future nuclear reactors whose in-service lifetimes are dependent upon the mechanical performance of the graphite. Irradiation damage from fast neutrons creates lattice defects which have a dynamic effect on the microstructure and mechanical properties of graphite. Transmission electron microscopy (TEM) can offer real-time monitoring of the dynamic atomic-level response of graphite subjected to irradiation; however, conventional TEM specimen-preparation techniques, such as argon ion milling itself, damage the graphite specimen and introduce lattice defects. It is impossible to distinguish these defects from the ones created by electron or neutron irradiation. To ensure that TEM specimens are artifact-free, a new oxidation-based technique has been developed. Bulk nuclear grades of graphite (IG-110 and NBG-18) and highly oriented pyrolytic graphite (HOPG) were initially mechanically thinned to ∼60 μm. Discs 3 mm in diameter were then oxidized at temperatures between 575 °C and 625 °C in oxidizing gasses using a new jet-polisher-like set-up in order to achieve optimal oxidation conditions to create self-supporting electron-transparent TEM specimens. The quality of these oxidized specimens were established using optical and electron microscopy. Samples oxidized at 575 °C exhibited large areas of electron transparency and the corresponding lattice imaging showed no apparent damage to the graphite lattice.

Formation, dissolution and properties of surface nanobubbles.

PubMed

Che, Zhizhao; Theodorakis, Panagiotis E

2017-02-01

Surface nanobubbles are stable gaseous phases in liquids that form on solid substrates. While their existence has been confirmed, there are many open questions related to their formation and dissolution processes along with their structures and properties, which are difficult to investigate experimentally. To address these issues, we carried out molecular dynamics simulations based on atomistic force fields for systems comprised of water, air (N 2 and O 2 ), and a Highly Oriented Pyrolytic Graphite (HOPG) substrate. Our results provide insights into the formation/dissolution mechanisms of nanobubbles and estimates for their density, contact angle, and surface tension. We found that the formation of nanobubbles is driven by an initial nucleation process of air molecules and the subsequent coalescence of the formed air clusters. The clusters form favorably on the substrate, which provides an enhanced stability to the clusters. In contrast, nanobubbles formed in the bulk either move randomly to the substrate and spread or move to the water-air surface and pop immediately. Moreover, nanobubbles consist of a condensed gaseous phase with a surface tension smaller than that of an equivalent system under atmospheric conditions, and contact angles larger than those in the equivalent nanodroplet case. We anticipate that this study will provide useful insights into the physics of nanobubbles and will stimulate further research in the field by using all-atom simulations. Copyright © 2016 Elsevier Inc. All rights reserved.

A new oxidation based technique for artifact free TEM specimen preparation of nuclear graphite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johns, Steve; Shin, Wontak; Kane, Joshua J.

Graphite is a key component in designs of current and future nuclear reactors whose in-service lifetimes are dependent upon the mechanical performance of the graphite. Irradiation damage from fast neutrons creates lattice defects which have a dynamic effect on the microstructure and mechanical properties of graphite. Transmission electron microscopy (TEM) can offer real-time monitoring of the dynamic atomic-level response of graphite subjected to irradiation; however, conventional TEM specimen-preparation techniques, such as argon ion milling itself, damage the graphite specimen and introduce lattice defects. It is impossible to distinguish these defects from the ones created by electron or neutron irradiation. Thus,tomore » ensure that TEM specimens are artifact-free, a new oxidation-based technique has been developed. Bulk nuclear grades of graphite (IG-110 and NBG-18) and highly oriented pyrolytic graphite (HOPG) were initially mechanically thinned to ~60μm. Discs 3mm in diameter were then oxidized at temperatures between 575°C and 625°C in oxidizing gasses using a new jet-polisher-like set-up in order to achieve optimal oxidation conditions to create self-supporting electron-transparent TEM specimens. The quality of these oxidized specimens were established using optical and electron microscopy. Samples oxidized at 575°C exhibited large areas of electron transparency and the corresponding lattice imaging showed no apparent damage to the graphite lattice.« less

Light-Induced Contraction/Expansion of 1D Photoswitchable Metallopolymer Monitored at the Solid-Liquid Interface.

PubMed

Garah, Mohamed El; Borré, Etienne; Ciesielski, Artur; Dianat, Arezoo; Gutierrez, Rafael; Cuniberti, Gianaurelio; Bellemin-Laponnaz, Stéphane; Mauro, Matteo; Samorì, Paolo

2017-10-01

The use of a bottom-up approach to the fabrication of nanopatterned functional surfaces, which are capable to respond to external stimuli, is of great current interest. Herein, the preparation of light-responsive, linear supramolecular metallopolymers constituted by the ideally infinite repetition of a ditopic ligand bearing an azoaryl moiety and Co(II) coordination nodes is described. The supramolecular polymerization process is followed by optical spectroscopy in dimethylformamide solution. Noteworthy, a submolecularly resolved scanning tunneling microscopy (STM) study of the in situ reversible trans-to-cis photoisomerization of a photoswitchable metallopolymer that self-assembles into 2D crystalline patterns onto a highly oriented pyrolytic graphite surface is achieved for the first time. The STM analysis of the nanopatterned surfaces is corroborated by modeling the physisorbed species onto a graphene slab before and after irradiation by means of density functional theory calculation. Significantly, switching of the monolayers consisting of supramolecular Co(II) metallopolymer bearing trans-azoaryl units to a novel pattern based on cis isomers can be triggered by UV light and reversed back to the trans conformer by using visible light, thereby restoring the trans-based supramolecular 2D packing. These findings represent a step forward toward the design and preparation of photoresponsive "smart" surfaces organized with an atomic precision. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Physical vapor deposition of one-dimensional nanoparticle arrays on graphite: seeding the electrodeposition of gold nanowires.

PubMed

Cross, C E; Hemminger, J C; Penner, R M

2007-09-25

One-dimensional (1D) ensembles of 2-15 nm diameter gold nanoparticles were prepared using physical vapor deposition (PVD) on highly oriented pyrolytic graphite (HOPG) basal plane surfaces. These 1D Au nanoparticle ensembles (NPEs) were prepared by depositing gold (0.2-0.6 nm/s) at an equivalent thickness of 3-4 nm onto HOPG surfaces at 670-690 K. Under these conditions, vapor-deposited gold nucleated selectively at the linear step edge defects present on these HOPG surfaces with virtually no nucleation of gold particles on terraces. The number density of 2-15 nm diameter gold particles at step edges was 30-40 microm-1. These 1D NPEs were up to a millimeter in length and organized into parallel arrays on the HOPG surface, following the organization of step edges. Surprisingly, the deposition of more gold by PVD did not lead to the formation of continuous gold nanowires at step edges under the range of sample temperature or deposition flux we have investigated. Instead, these 1D Au NPEs were used as nucleation templates for the preparation by electrodeposition of gold nanowires. The electrodeposition of gold occurred selectively on PVD gold nanoparticles over the potential range from 700-640 mV vs SCE, and after optimization of the electrodeposition parameters continuous gold nanowires as small as 80-90 nm in diameter and several micrometers in length were obtained.

Ion irradiation induced surface modification studies of polymers using SPM

NASA Astrophysics Data System (ADS)

Tripathi, A.; Kumar, Amit; Singh, F.; Kabiraj, D.; Avasthi, D. K.; Pivin, J. C.

2005-07-01

Various types of scanning probe microscopy (SPM) techniques: atomic force microscopy (AFM) (contact and tapping in height and amplitude mode), scanning tunnelling microscopy (STM) and conducting atomic force microscopy (C-AFM) are used for studying ion beam induced surface modifications, nanostructure/cluster formation and disintegration in polymers and similar soft carbon based materials. In the present study, the results of studies on four materials, namely, (A) methyltriethoxysilane/phenyltriethoxysilane (MTES/PTES) based gel, (B) triethoxisilane (TH) based gel, (C) highly oriented pyrolytic graphite (HOPG) bulk and (D) fullerene (C60) thin films are discussed. In the case of Si based gels prepared from pre-cursors containing organic groups (MTES/PTES), hillocks are observed at the surface and their size decreases from 70 to 25 nm with increasing fluence, whereas, in the case of a gel with a stoichiometry SiO1.25H1, prepared from TH, an increases in the size of hillocks is observed. Hillocks are also formed at the surface of HOPG irradiated with 120 MeV Au beam at a low fluence, whereas, formation of craters and a re-organisation of surface features is observed at a higher fluence. In the case of C60 films, 120 MeV Au ion irradiation induces the formation of conducting ion tracks, which is attributed to the transformation from insulating C60 to conducting graphite like carbon.

Spectra of electrons emitted as a result of the sticking and annihilation of low energy positrons to the surfaces of graphene and highly oriented pyrolytic graphite (HOPG)

NASA Astrophysics Data System (ADS)

Chrysler, M.; Chirayath, V.; McDonald, A.; Lim, Z.; Shastry, K.; Gladen, R.; Fairchild, A.; Koymen, A.; Weiss, A.

Positron annihilation induced Auger electron spectroscopy (PAES) was used to study the positron induced low energy electron spectra from HOPG and a sample composed of 6-8 layers of graphene grown on polycrystalline copper. A low energy (~2eV) beam of positrons was used to implant positrons into a surface localized state on the graphene and HOPG samples. Measurements of the energy spectra of the positron induced electrons obtained using a TOF spectrometer indicate the presence of an annihilation induced KLL C Auger peak (at ~263 eV) along with a narrow low energy secondary peak due to an Auger mediated positron sticking (AMPS) process. A broad spectral feature was also observed below ~15 eV which we believe may be due to a VVV C Auger transition not previously observed. The energy dependence of the integrated intensity of the AMPS peak was measured for a series of incident positron kinetic energies ranging from ~1.5 eV up to 11 eV from which the binding energy of the surface localized positron state on graphene and HOPG was estimated. The implication of our results regarding the applicability of AMPS and PAES to the study of graphene surfaces and interfaces will be discussed. This work was supported by NSF Grant No. DMR 1508719 and DMR 1338130.

A new oxidation based technique for artifact free TEM specimen preparation of nuclear graphite

DOE PAGES

Johns, Steve; Shin, Wontak; Kane, Joshua J.; ...

2018-04-03

Graphite is a key component in designs of current and future nuclear reactors whose in-service lifetimes are dependent upon the mechanical performance of the graphite. Irradiation damage from fast neutrons creates lattice defects which have a dynamic effect on the microstructure and mechanical properties of graphite. Transmission electron microscopy (TEM) can offer real-time monitoring of the dynamic atomic-level response of graphite subjected to irradiation; however, conventional TEM specimen-preparation techniques, such as argon ion milling itself, damage the graphite specimen and introduce lattice defects. It is impossible to distinguish these defects from the ones created by electron or neutron irradiation. Thus,tomore » ensure that TEM specimens are artifact-free, a new oxidation-based technique has been developed. Bulk nuclear grades of graphite (IG-110 and NBG-18) and highly oriented pyrolytic graphite (HOPG) were initially mechanically thinned to ~60μm. Discs 3mm in diameter were then oxidized at temperatures between 575°C and 625°C in oxidizing gasses using a new jet-polisher-like set-up in order to achieve optimal oxidation conditions to create self-supporting electron-transparent TEM specimens. The quality of these oxidized specimens were established using optical and electron microscopy. Samples oxidized at 575°C exhibited large areas of electron transparency and the corresponding lattice imaging showed no apparent damage to the graphite lattice.« less

Surface modification of GC and HOPG with diazonium, amine, azide, and olefin derivatives.

PubMed

Tanaka, Mutsuo; Sawaguchi, Takahiro; Sato, Yukari; Yoshioka, Kyoko; Niwa, Osamu

2011-01-04

Surface modification of glassy carbon (GC) and highly oriented pyrolytic graphite (HOPG) was carried out with diazonium, amine, azide, and olefin derivatives bearing ferrocene as an electroactive moiety. Features of the modified surfaces were evaluated by surface concentrations of immobilized molecule, blocking effect of the modified surface against redox reaction, and surface observation using cyclic voltammetry and electrochemical scanning tunneling microscope (EC-STM). The measurement of surface concentrations of immobilized molecule revealed the following three aspects: (i) Diazonium and olefin derivatives could modify substrates with the dense-monolayer concentration. (ii) The surface concentration of immobilized amine derivative did not reach to the dense-monolayer concentration reflecting their low reactivity. (iii) The surface modification with the dense-monolayer concentration was also possible with azide derivative, but the modified surface contained some oligomers produced by the photoreaction of azides. Besides, the blocking effect against redox reaction was observed for GC modified with diazonium derivative and for HOPG modified with diazonium and azide derivatives, suggesting fabrication of a densely modified surface. Finally, the surface observation for HOPG modified with diazonium derivative by EC-STM showed a typical monolayer structure, in which the ferrocene moieties were packed densely at random. On the basis of those results, it was demonstrated that surface modification of carbon substrates with diazonium could afford a dense monolayer similar to the self-assembled monolayer (SAM) formation.

Gasification Characterization of Ionic Liquids as Propellants

DTIC Science & Technology

2008-05-25

the droplet is the dominant mode of heat transfer. Furthermore, substantial liquid-phase pyrolytic reaction is initiated when the droplet is heated to...experimental apparatus is shown in Fig. 12. Here a column of a high-boiling-point liquid (Krytox 143AD, a fluorinated oil from DuPont. Density: 1.95 g...6 heating oil (if it were pure, without any volatile component). Because of the very low vapor pressure, the droplet will simply be heated up

Microwave Tube Reliability

DTIC Science & Technology

1976-06-01

t’ibes discussed demonstrate a 2000-hour life in the laboratory but exhibit only a 200- hour i’fc in systems. The tubes reported on were broadband , helix ...control. Two such critical operations are helix winding and pyrolytic deposition. The ,slow-wave structureof .he modem TWT -is rarely a simple uniform...Il No customer complaint (2) 1I Open helix (1) 1 High harmonics, low power<l) The group A and B -symptoms indicated by the failure report data weL

Pyrolytic synthesis and characterization of N-doped carbon nanoflakes for electrochemical applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Savilov, S.V., E-mail: savilov@chem.msu.ru; N.S. Kurnakov Institute of General and Inorganic Chemistry Of Russian Academy of Sciences, Leninsky avenue, 31, Moscow 119991; Arkhipova, E.A.

2015-09-15

Highlights: • Carbon nanoflakes doped with nitrogen were produced by a pyrolytic technique. • Quarternary, pyrrolic and pyridinic types of nitrogen are confirmed by XPS. • Nitrogen content depends on precursor used and temperature processed. • Specific surface area values decrease with increasing of synthesis duration. • N-doped carbon nanoflakes may be suitable for electrochemical applications. - Abstract: Nitrogen doped carbon nanoflakes, which are very important for many electrochemical applications, were synthesized by pyrolysis of nitrogen containing organic compounds over metal oxide template. Acetonitrile, pyridine and butylamine, which are of different volatility were tested as N-containing precursors. Morphology, structure andmore » chemical composition of the as-synthesized materials were investigated by scanning electron microscopy (SEM), high resolution transmission electron microscopy (TEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). It was found that materials are highly defective and consist of a few malformed graphene layers. X-ray photoelectron spectra reflect the dominant graphitic and pyridinic N-bonding configuration. It was also noted that specific surface area depends on the duration and temperature of the reaction. Increase in duration and temperature led to decrease of the specific surface area from 1000 to 160 m{sup 2}/g, 1170 to 210 m{sup 2}/g and 1180 to 480 m{sup 2}/g for acetonitrile, butylamine and pyridine precursors, respectively.« less

Pyrolytic boron nitride coatings on ceramic yarns and fabrication of insulations

NASA Technical Reports Server (NTRS)

Moore, Arthur W.

1992-01-01

Pyrolytic boron nitride (PBN) was deposited on Nicalon NL 202 silicon carbide yarns at 1000 to 1200 C with the goal of improving the resistance of the Nicalon to deterioration in an aerodynamic environment at temperatures up to 1000 C. For continuous coating, the yarns were fed through the deposition chamber of a pilot plant sized CVD furnace at a rate of about 2 feet per minute. PBN coatings were obtained by reacting boron trichloride and ammonia gases inside the deposition chamber. Most of the PBN coatings were made at around 1080 C to minimize thermal degradation of the Nicalon. Pressures were typically below 0.1 Torr. The coated yarns were characterized by weight per unit length, tensile strength and modulus, scanning electron microscopy, and scanning Auger microscopy. The PBN coated Nicalon was woven into cloth, but was not entirely satisfactory as a high temperature sizing. Several 13 in. square pieces of Nicalon cloth were coated with PBN in a batch process in a factory sized deposition furnace. Samples of cloth made from the PBN coated Nicalon were sewn into thermal insulation panels, whose performance is being compared with that of panels made using uncoated Nicalon.

Evolution of soil organic matter changes using pyrolysis and metabolic indices: a comparison between organic and mineral fertilization.

PubMed

Marinari, S; Masciandaro, G; Ceccanti, B; Grego, S

2007-09-01

The aim of this study was to evaluate chemical and biochemical changes of organic matter in fertilized (ammonium nitrate) and amended (vermicompost and manure) soils using pyrolysis and metabolic indices. The metabolic potential [dehydrogenase (DH-ase)/water soluble organic carbon (WSOC)], the metabolic quotient (qCO2) and the microbial quotient (Cmic:Corg) were calculated as indices of soil organic matter evolution. Pyrolysis-gas chromatography (Py-GC) was used to study structural changes in the organic matter. Carbon forms and microbial biomass have been measured by dichromate oxidation and fumigation-extraction methods, respectively. Dehydrogenase activity has been tested using INT (p-Iodonitrotetrazolium violet) as substrate. The results showed that organic amendment increased soil microbial biomass and its activity which were strictly related to pyrolytic mineralization and humification indices (N/O, B/E3). Mineral fertilization caused a greater alteration of native soil organic matter than the organic amendments, in that a high release of WSOC and relatively large amounts of aliphatic pyrolytic products, were observed. Therefore, the pyrolysis and metabolic indices provided similar and complementary information on soil organic matter changes after mineral and organic fertilization.

Evaluation of Melanogenesis in A-375 Cells in the Presence of DMSO and Analysis of Pyrolytic Profile of Isolated Melanin

PubMed Central

Chodurek, Ewa; Orchel, Arkadiusz; Orchel, Joanna; Kurkiewicz, Sławomir; Gawlik, Natalia; Dzierżewicz, Zofia; Stępień, Krystyna

2012-01-01

The increase of a skin malignant melanoma (melanoma malignum) incidence in the world has been observed in recent years. The tumour, especially in advanced stadium with metastases, is highly resistant to conventional treatment. One of the strategies is to modulate melanogenesis using chemical compounds. In this study, the processes of differentiation and melanogenesis induced by dimethylsulfoxide (DMSO) in human melanoma cells (A-375) were investigated. Natural melanin isolated from A-375 melanoma cell line treated with 0.3% DMSO was analyzed by pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) method. The products derived from pheomelanin have not been stated in the pyrolytic profile of analyzed melanin. Within all products derived from eumelanins, 1,2-benzenediol has been predominated. It has been shown that in the melanoma cells stimulated with 0.3% and 1% DMSO, the increase of transcriptional activity of the tyrosinase gene took place. It was accompanied by the rise of tyrosinase activity and an accumulation of melanin in the cells. The better knowledge about the structure of melanins can contribute to establish the uniform criteria of malignant melanoma morbidity risk. PMID:22654640

Microrobot with passive diamagnetic levitation for microparticle manipulations

NASA Astrophysics Data System (ADS)

Feng, Lin; Zhang, Shengyuan; Jiang, Yonggang; Zhang, Deyuan; Arai, Fumihito

2017-12-01

In this paper, an innovative microrobot with passive diamagnetic levitation is presented. Based on theoretical analysis, finite element method simulation, and experiments, the shape of pyrolytic graphite is redesigned, which improves the stability of passive diamagnetic levitation significantly. Therefore, passive diamagnetic levitation is able to be applied for 3-D control of the microrobot. Compared with the traditional microrobots driven by permanent magnets in a microfluidic chip, the microrobot made of pyrolytic graphite and driven by magnetic force has two advantages, no friction and 3-D control, which is able to expand the scope of the microrobot applications. Finally, the microrobot with passive diamagnetic levitation was demonstrated by being encapsulated in a microfluidic chip for microparticle manipulations.

Liquid hydrocarbon fuels obtained by the pyrolysis of soybean oils.

PubMed

Junming, Xu; Jianchun, Jiang; Yanju, Lu; Jie, Chen

2009-10-01

The pyrolysis reactions of soybean oils have been studied. The pyrolytic products were analyzed by GC-MS and FTIR and show the formation of olefins, paraffins, carboxylic acids and aldehydes. Several kinds of catalysts were compared. It was found that the amounts of carboxylic acids and aldehydes were significantly decreased by using base catalysts such as Na(2)CO(3) and K(2)CO(3). The low acid value pyrolytic products showed good cold flow properties and good solubility in diesel oil at low temperature. The results presented in this work have shown that the pyrolysis of soybean oils generates fuels that have chemical composition similar to petroleum based fuels.

Ion sputter textured graphite electrode plates

NASA Technical Reports Server (NTRS)

Curren, A. N.; Forman, R.; Sovey, J. S.; Wintucky, E. G. (Inventor)

1983-01-01

A specially textured surface of pyrolytic graphite exhibits extremely low yields of secondary electrons and reduced numbers of reflected primary electrons after impingement of high energy primary electrons. Electrode plates of this material are used in multistage depressed collectors. An ion flux having an energy between 500 iV and 1000 iV and a current density between 1.0 mA/sq cm and 6.0 mA/sq cm produces surface roughening or texturing which is in the form of needles or spires. Such textured surfaces are especially useful as anode collector plates in high tube devices.

Analysis of Low-Pressure Gas-Phase Pyrolytic Reactions by Mass Spectrometric Techniques,

DTIC Science & Technology

1989-01-01

temperatures and pressures known only as a polymeric substance, is similarly obtained in high purity by heating the polymer to its melting point (105-110’ C...filaments for Curie- point pyrolysis’ J.Anal.Appl.Pyrolysis. 5 (1983) 1-7 (with Helge Egsgaard) 4) ’Heterogeneous catalysis in gas phase reactions studied...by Curie- point pyrolysis. Gas phase pyrolysis of methyl dithio- acetat’ J.Anal.Appl.Pyrolysis. 5 (1983) 257-259 (with Helge Egsgaard) 5) ’Continuous

Pyrolytic carbon membranes containing silica: morphological approach on gas transport behavior

NASA Astrophysics Data System (ADS)

Park, Ho Bum; Lee, Sun Yong; Lee, Young Moo

2005-04-01

Pyrolytic carbon membrane containing silica (C-SiO 2) is a new-class material for gas separation, and in the present work we will deal with it in view of the morphological changes arising from the difference in the molecular structure of the polymeric precursors. The silica embedded carbon membranes were fabricated by a predetermined pyrolysis step using imide-siloxane copolymers (PISs) that was synthesized from benzophenone tetracarboxylic dianhydrides (BTDA), 4,4'-oxydianiline (ODA), and amine-terminated polydimethylsiloxane (PDMS). To induce different morphologies at the same chemical composition, the copolymers were prepared using one-step (preferentially a random segmented copolymer) sand two-step polymerization (a block segmented copolymer) methods. The polymeric precursors and their pyrolytic C-SiO 2 membranes were analyzed using thermal analysis, atomic force microscopy, and transmission electron microscopy, etc. It was found that the C-SiO 2 membrane derived from the random PIS copolymer showed a micro-structure containing small well-dispersed silica domains, whereas the C-SiO 2 membrane from the block PIS copolymer exhibited a micro-structure containing large silica domains in the continuous carbon matrix. Eventually, the gas transport through these C-SiO 2 membranes was significantly affected by the morphological changes of the polymeric precursors.

Electrostatically Driven Guest Binding in a Self-Assembled Porous Network at the Liquid/Solid Interface.

PubMed

Iritani, Kohei; Ikeda, Motoki; Yang, Anna; Tahara, Kazukuni; Anzai, Masaru; Hirose, Keiji; De Feyter, Steven; Moore, Jeffrey S; Tobe, Yoshito

2018-05-29

We present here the construction of a self-assembled two-dimensional (2D) porous monolayer bearing a highly polar 2D space to study guest co-adsorption through electrostatic interactions at the liquid/solid interface. For this purpose, a dehydrobenzo[12]annulene (DBA) derivative, DBA-TeEG, having tetraethylene glycol (TeEG) groups at the end of the three alternating alkoxy chains connected by p-phenylene linkers was synthesized. As a reference host molecule, DBA-C10, having nonpolar C 10 alkyl chains at three alternating terminals, was employed. As guest molecules, hexagonal phenylene-ethynylene macrocycles (PEMs) attached by triethylene glycol (TEG) ester and hexyl ester groups, PEM-TEG and PEM-C6, respectively, at each vertex of the macrocyclic periphery were used. Scanning tunneling microscopy observations at the 1,2,4-trichlorobenzene/highly oriented pyrolytic graphite interface revealed that PEM-TEG was immobilized in the pores formed by DBA-TeEG at higher probability because of electrostatic interactions such as dipole-dipole and hydrogen bonding interactions between oligoether units of the host and guest, in comparison to PEM-C6 with nonpolar groups. These observations are discussed based on molecular mechanics simulations to investigate the role of the polar functional groups. When a nonpolar host matrix formed by DBA-C10 was used, however, only phase separation and preferential adsorption were observed; virtually no host-guest complexation was discernible. This is ascribed to the strong affinity between the guest molecules which form by themselves densely packed van der Waals networks on the surface.

The nucleation and growth of uranium on the basal plane of graphite studied by scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Tench, R. J.

1992-11-01

For the first time, nanometer scale uranium clusters were created on the basal plane of highly oriented pyrolytic graphite by laser ablation under ultra-high vacuum conditions. The physical and chemical properties of these clusters were investigated by scanning tunneling microscopy (STM) as well as standard surface science techniques. Auger electron and X-ray photoelectron spectroscopies found the uranium deposit to be free of contamination and showed that no carbide had formed with the underlying graphite. Clusters with sizes ranging from 42 to 630 sq A were observed upon initial room temperature deposition. Surface diffusion of uranium was observed after annealing the substrate above 800 K, as evidenced by the decreased number density and the increased size of the clusters. Preferential depletion of clusters on terraces near step edges as a result of annealing was observed. The activation energy for diffusion deduced from these measurements was found to be 15 Kcal/mole. Novel formation of ordered uranium thin films was observed for coverages greater than two monolayers after annealing above 900 K. These ordered films displayed islands with hexagonally faceted edges rising in uniform step heights characteristic of the unit cell of the P-phase of uranium. In addition, atomic resolution STM images of these ordered films indicated the formation of the (beta)-phase of uranium. The chemical properties of these surfaces were investigated and it was shown that these uranium films had a reduced oxidation rate in air as compared to bulk metal and that STM imaging in air induced a polarity-dependent enhancement of the oxidation rate.

Soluble Flavanthrone Derivatives: Synthesis, Characterization, and Application to Organic Light-Emitting Diodes.

PubMed

Kotwica, Kamil; Bujak, Piotr; Data, Przemyslaw; Krzywiec, Wojciech; Wamil, Damian; Gunka, Piotr A; Skorka, Lukasz; Jaroch, Tomasz; Nowakowski, Robert; Pron, Adam; Monkman, Andrew

2016-06-01

Simple modification of benzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine-8,16-dione, an old and almost-forgotten vat dye, by reduction of its carbonyl groups and subsequent O-alkylation, yields solution-processable, electroactive, conjugated compounds of the periazaacene type, suitable for the use in organic electronics. Their electrochemically determined ionization potential and electron affinity of about 5.2 and -3.2 eV, respectively, are essentially independent of the length of the alkoxyl substituent and in good agreement with DFT calculations. The crystal structure of 8,16-dioctyloxybenzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine (FC-8), the most promising compound, was solved. It crystallizes in space group P1‾ and forms π-stacked columns held together in the 3D structure by dispersion forces, mainly between interdigitated alkyl chains. Molecules of FC-8 have a strong tendency to self-organize in monolayers deposited on a highly oriented pyrolytic graphite surface, as observed by STM. 8,16-Dialkoxybenzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridines are highly luminescent, and all have photoluminescence quantum yields of about 80 %. They show efficient electroluminescence, and can be used as guest molecules with a 4,4'-bis(N-carbazolyl)-1,1'-biphenyl host in guest/host-type organic light-emitting diodes. The best fabricated diodes showed a luminance of about 1900 cd m(-12) , a luminance efficiency of about 3 cd A(-1) , and external quantum efficiencies exceeding 0.9 %. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox-dependent spatially resolved electrochemistry at graphene and graphite step edges.

PubMed

Güell, Aleix G; Cuharuc, Anatolii S; Kim, Yang-Rae; Zhang, Guohui; Tan, Sze-yin; Ebejer, Neil; Unwin, Patrick R

2015-04-28

The electrochemical (EC) behavior of mechanically exfoliated graphene and highly oriented pyrolytic graphite (HOPG) is studied at high spatial resolution in aqueous solutions using Ru(NH3)6(3+/2+) as a redox probe whose standard potential sits close to the intrinsic Fermi level of graphene and graphite. When scanning electrochemical cell microscopy (SECCM) data are coupled with that from complementary techniques (AFM, micro-Raman) applied to the same sample area, different time-dependent EC activity between the basal planes and step edges is revealed. In contrast, other redox couples (ferrocene derivatives) whose potential is further removed from the intrinsic Fermi level of graphene and graphite show uniform and high activity (close to diffusion-control). Macroscopic voltammetric measurements in different environments reveal that the time-dependent behavior after HOPG cleavage, peculiar to Ru(NH3)6(3+/2+), is not associated particularly with any surface contaminants but is reasonably attributed to the spontaneous delamination of the HOPG with time to create partially coupled graphene layers, further supported by conductive AFM measurements. This process has a major impact on the density of states of graphene and graphite edges, particularly at the intrinsic Fermi level to which Ru(NH3)6(3+/2+) is most sensitive. Through the use of an improved voltammetric mode of SECCM, we produce movies of potential-resolved and spatially resolved HOPG activity, revealing how enhanced activity at step edges is a subtle effect for Ru(NH3)6(3+/2+). These latter studies allow us to propose a microscopic model to interpret the EC response of graphene (basal plane and edges) and aged HOPG considering the nontrivial electronic band structure.

Chronic dietary exposure to pyrolytic and petrogenic mixtures of PAHs causes physiological disruption in zebrafish--part II: behavior.

PubMed

Vignet, Caroline; Le Menach, Karyn; Lyphout, Laura; Guionnet, Tiphaine; Frère, Laura; Leguay, Didier; Budzinski, Hélène; Cousin, Xavier; Bégout, Marie-Laure

2014-12-01

In the last 10 years, behavior assessment has been developed as an indicator of neurotoxicity and an integrated indicator of physiological disruption. Polycyclic aromatic hydrocarbon (PAH) release into the environment has increased in recent decades resulting in high concentrations of these compounds in the sediment of contaminated areas. We evaluated the behavioral consequences of long-term chronic exposure to PAHs, by exposing zebrafish to diets spiked with three PAH fractions at environmentally relevant concentrations. Fish were exposed to these chemicals from their first meal (5 days postfertilization) until they became reproducing adults (at 6 months old). The fractions used were representative of PAHs of pyrolytic (PY) origin and of two oils differing in composition (a heavy fuel oil (HO) and a light crude oil (LO)). Several tests were carried out to evaluate circadian spontaneous swimming activity, responses to a challenge (photomotor response), exploratory tendencies, and anxiety levels. We found that dietary PAH exposure was associated with greater mobility, lower levels of exploratory activity, and higher levels of anxiety, particularly in fish exposed to the HO fraction and, to a lesser extent, the LO fraction. Finally, our results indicate that PAH mixtures of different compositions, representative of situations encountered in the wild, can induce behavioral disruptions resulting in poorer fish performance.

Rheological properties and tunable thermoplasticity of phenolic rich fraction of pyrolysis bio-oil.

PubMed

Sahaf, Amir; Laborie, Marie-Pierre G; Englund, Karl; Garcia-Perez, Manuel; McDonald, Armando G

2013-04-08

In this work we report on the preparation, characterization, and properties of a thermally treated lignin-derived, phenolic-rich fraction (PRF) of wood pyrolysis bio-oil obtained by ethyl acetate extraction. The PRF was characterized for viscoelastic and rheological behavior using dynamic mechanical analysis (DMA) and cone and plate rheology. A unique thermoplastic behavior was evidenced. Heat-treated PRFs acquire high modulus but show low temperatures of thermal flow which can be systematically manipulated through the thermal pretreatment. Loss of volatiles, changes in molecular weight, and glass transition temperature (Tg) were investigated using thermogravimetric analysis (TGA), mass spectrometry (MS), and differential scanning calorimetry (DSC), respectively. Underlying mechanisms for the thermal and rheological behavior are discussed with regard to interactions between pyrolytic lignin nanoparticles present in the system and the role of volatile materials on determining the properties of the material resembling in several aspects to colloidal suspension systems. Low thermal flow temperatures and reversible thermal effects can be attributed to association of pyrolytic lignin particles due to intermolecular interactions that are easily ruptured at higher temperatures. The thermoplastic behavior of PRF and its low Tg is of particular interest, as it gives opportunities for application of this fraction in several melt processing and adhesive technologies.

Engineering of Corynebacterium glutamicum for growth and succinate production from levoglucosan, a pyrolytic sugar substrate.

PubMed

Kim, Eun-Mi; Um, Youngsoon; Bott, Michael; Woo, Han Min

2015-10-01

Thermochemical processing provides continuous production of bio-oils from lignocellulosic biomass. Levoglucosan, a pyrolytic sugar substrate C6H10O5 in a bio-oil, has been used for ethanol production using engineered Escherichia coli. Here we provide the first example for succinate production from levoglucosan with Corynebacterium glutamicum, a well-known industrial amino acid producer. Heterologous expression of a gene encoding a sugar kinase from Lipomyces starkeyi, Gibberella zeae or Pseudomonas aeruginosa was employed for levoglucosan conversion in C. glutamicum because the wild type was unable to utilize levoglucosan as sole carbon source. As result, expression of a levoglucosan kinase (LGK) of L. starkeyi only enabled growth with levoglucosan as sole carbon source in CgXII minimal medium by catalyzing conversion of levoglucosan to glucose-6-phosphate. Subsequently, the lgk gene was expressed in an aerobic succinate producer of C. glutamicum, strain BL-1. The recombinant strain showed a higher succinate yield (0.25 g g(-1)) from 2% (w/v) levoglucosan than the reference strain BL-1 from 2% (w/v) glucose (0.19 g g(-1)), confirming that levoglucosan is an attractive carbon substrate for C. glutamicum producer strains. In summary, we demonstrated that a pyrolytic sugar could be a potential carbon source for microbial cell factories. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Investigation of chemical modifications of micro- and macromolecules in bio-oil during hydrodeoxygenation with Pd/C catalyst in supercritical ethanol.

PubMed

Oh, Shinyoung; Hwang, Hyewon; Choi, Hang Seok; Choi, Joon Weon

2014-12-01

Miscanthus bio-oil was subjected to hydrodeoxygenation (HDO) with Pd/C at different temperatures (250, 300 and 350°C) and times (30, 45 and 60 min) to investigate the chemical modification of micro- and macromolecules in bio-oil. Four main products - char, gas and two immiscible oils (light and heavy oil) - were obtained from the HDO reaction. Yields of heavy oil as a targeting product of HDO varied from 60% to 13%, whereas those of gas and char were ranged from 7% to 36% and 6% to 17%, respectively. Water content was estimated to<1% and heating value was 26-31 MJ kg(-1). Reduction of unstable oxygen-containing compounds such as acids (2-hydroxy-butanoic acid), aldehydes (furfural), alcohols (butanedial) and sugars (levoglucosan) were characteristic in heavey oil. Apart from hydrogenation and deoxygenation, micromolecules in bio-oil were plausibly modified to stable ketones, esters and saturated components via demethoxylation, dealkylation, decarbonylation, dehydroxylation and ring opening. Macromolecular lignin fragments (referred to as pyrolytic lignins in bio-oil and phenol polymers in heavy oil) were extracted and subjected to several analyses. Approximately 60% of the pyrolytic lignins were decomposed into low molecular weight compounds during HDO reaction. Moreover, essential functional groups, OCH3 and phen-OH groups attached to pyrolytic lignin, were severely modified during HDO reaction. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sustainable pyrolytic sludge-char preparation on improvement of closed-loop sewage sludge treatment: Characterization and combined in-situ application.

PubMed

Jin, Zhengyu; Chang, Fengmin; Meng, Fanlin; Wang, Cuiping; Meng, Yao; Liu, Xiaoji; Wu, Jing; Zuo, Jiane; Wang, Kaijun

2017-10-01

Aiming at closed-loop sustainable sewage sludge treatment, an optimal and economical pyrolytic temperature was found at 400-450 °C considering its pyrolysis efficiency of 65%, fast cracking of hydrocarbons, proteins and lipids and development of aromatized porous structure. Fourier-transform infrared (FTIR) and X-ray diffraction (XRD) tests demonstrated the development of adsorptive functional groups and crystallographic phases of adsorptive minerals. The optimal sludge-char, with a medium specific surface area of 39.6 m 2  g -1 and an iodine number of 327 mgI 2 g -1 , performed low heavy metals lixiviation. The application of sludge-char in raw sewage could remove 30% of soluble chemical oxygen demand (SCOD), along with an acetic acid adsorption capacity of 18.0 mg g -1 . The developed mesopore and/or macropore structures, containing rich acidic and basic functional groups, led to good biofilm matrices for enhanced microbial activities and improved autotrophic nitrification in anoxic stage of an A/O reactor through adsorbed extra carbon source, and hence achieved the total nitrogen (TN) removal up to 50.3%. It is demonstrated that the closed-loop sewage sludge treatment that incorporates pyrolytic sludge-char into in-situ biological sewage treatment can be a promising sustainable strategy by further optimization. Copyright © 2017 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fedrigo, Anna, E-mail: anna.fedrigo@nbi.ku.dk; Istituto dei Sistemi Complessi, Consiglio Nazionale delle Ricerche, 50019 Sesto Fiorentino; European Spallation Source ESS AB, SE-221 00 Lund

VESPA, Vibrational Excitation Spectrometer with Pyrolytic-graphite Analysers, aims to probe molecular excitations via inelastic neutron scattering. It is a thermal high resolution inverted geometry time-of-flight instrument designed to maximise the use of the long pulse of the European Spallation Source. The wavelength frame multiplication technique was applied to provide simultaneously a broad dynamic range (about 0-500 meV) while a system of optical blind choppers allows to trade flux for energy resolution. Thanks to its high flux, VESPA will allow the investigation of dynamical and in situ experiments in physical chemistry. Here we describe the design parameters and the corresponding McStasmore » simulations.« less

Reexamination of Basal Plane Thermal Conductivity of Suspended Graphene Samples Measured by Electro-Thermal Micro-Bridge Methods

DOE PAGES

Jo, Insun; Pettes, Michael; Lindsay, Lucas R.; ...

2015-05-18

Thermal transport in suspended graphene samples has been measured in prior works and this work with the use of a suspended electro-thermal micro-bridge method. These measurement results are analyzed here to evaluate and eliminate the errors caused by the extrinsic thermal contact resistance. It is noted that the thermal resistance measured in a recent work increases linearly with the suspended length of the single-layer graphene samples synthesized by chemical vapor deposition (CVD), and that such a feature does not reveal the failure of Fourier s law despite the increase in the apparent thermal conductivity with length. The re-analyzed thermal conductivitymore » of a single-layer CVD graphene sample reaches about ( 1680 180 )Wm-1K-1 at room temperature, which is close to the highest value reported for highly oriented pyrolytic graphite. In comparison, the thermal conductivity values measured for two suspended exfoliated bi-layer graphene samples are about ( 880 60 ) and ( 730 60 ) Wm-1K-1 at room temperature, and approach that of the natural graphite source above room temperature. However, the low-temperature thermal conductivities of these suspended graphene samples are still considerably lower than the graphite values, with the peak thermal conductivities shifted to much higher temperatures. Analysis of the thermal conductivity data reveals that the low temperature behavior is dominated by phonon scattering by polymer residue instead of by the lateral boundary.« less

Detailed line shape analysis of the C KVV Auger peak of two carbon allotropes measured using a time of flight positron annihilation induced Auger electron spectrometer

NASA Astrophysics Data System (ADS)

Fairchild, A. J.; Chirayath, V. A.; Chrysler, M. D.; Gladen, R. W.; Imam, S. K.; Koymen, A. R.; Weiss, A. H.

We report a detailed line shape analysis of the positron induced C KVV Auger line shape from highly oriented pyrolytic graphite (HOPG) and a single layer of graphene grown on polycrystalline Cu. A model consisting of the self-fold of the one-electron density of states including terms for hole-hole interactions, charge screening effects, and intrinsic loss mechanisms is compared to experimental C KVV line shapes measured using a positron induced Auger electron spectrometer (PAES). In traditional Auger spectroscopies which use an electron or photon to initiate the Auger process, extracting the relatively small Auger signal from the large secondary background can be quite difficult. Using a very low energy positron beam to create the core hole through an anti-matter matter annihilation entirely eliminates this background. Additionally, PAES has sensitivity to the top most atomic layer since the positron becomes trapped in an image potential well at the surface before annihilation. Therefore, the PAES signal from a single layer of graphene on polycrystalline Cu is primarily from the graphene overlayer with small contributions from the Cu substrate while the PAES signal from HOPG can be viewed as a single graphene layer with a graphite substrate. The influence of these two substrates on C KVV line shape is discussed. This work was supported by NSF Grant No. DMR 1508719 and DMR 1338130.

Efficient Synthesis of Ir-Polyoxometalate Cluster Using a Continuous Flow Apparatus and STM Investigation of Its Coassembly Behavior on HOPG Surface.

PubMed

Zhang, Junyong; Chang, Shaoqing; Suryanto, Bryan H R; Gong, Chunhua; Zeng, Xianghua; Zhao, Chuan; Zeng, Qingdao; Xie, Jingli

2016-06-06

Taking advantage of a continuous-flow apparatus, the iridium(III)-containing polytungstate cluster K12Na2H2[Ir2Cl8P2W20O72]·37H2O (1) was obtained in a reasonable yield (13% based on IrCl3·H2O). Compound 1 was characterized by Fourier transform IR, UV-visible, (31)P NMR, electrospray ionization mass spectrometry (ESI-MS), and thermogravimetric analysis measurements. (31)P NMR, ESI-MS, and elemental analysis all indicated 1 was a new polytungstate cluster compared with the reported K14[(IrCl4)KP2W20O72] compound. Intriguingly, the successful isolation of 1 relied on the custom-built flow apparatus, demonstrating the uniqueness of continuous-flow chemistry to achieve crystalline materials. The catalytic properties of 1 were assessed by investigating the activity on catalyzing the electro-oxidation of ruthenium tris-2,2'-bipyridine [Ru(bpy)3](2+/3+). The voltammetric behavior suggested a coupled catalytic behavior between [Ru(bpy)3](3+/2+) and 1. Furthermore, on the highly oriented pyrolytic graphite surface, 1,3,5-tris(10-carboxydecyloxy) benzene (TCDB) was used as the two-dimensional host network to coassemble cluster 1; the surface morphology was observed by scanning tunneling microscope technique. "S"-shape of 1 was observed, indicating that the cluster could be accommodated in the cavity formed by two TCDB host molecules, leading to a TCDB/cluster binary structure.

Development of simulation approach for two-dimensional chiral molecular self-assembly driven by hydrogen bond at the liquid/solid interface

NASA Astrophysics Data System (ADS)

Qin, Yuan; Yao, Man; Hao, Ce; Wan, Lijun; Wang, Yunhe; Chen, Ting; Wang, Dong; Wang, Xudong; Chen, Yonggang

2017-09-01

Two-dimensional (2D) chiral self-assembly system of 5-(benzyloxy)-isophthalic acid derivative/(S)-(+)-2-octanol/highly oriented pyrolytic graphite was studied. A combined density functional theory/molecular mechanics/molecular dynamics (DFT/MM/MD) approach for system of 2D chiral molecular self-assembly driven by hydrogen bond at the liquid/solid interface was thus proposed. Structural models of the chiral assembly were built on the basis of scanning tunneling microscopy (STM) images and simplified for DFT geometry optimization. Merck Molecular Force Field (MMFF) was singled out as the suitable force field by comparing the optimized configurations of MM and DFT. MM and MD simulations for hexagonal unit model which better represented the 2D assemble network were then preformed with MMFF. The adhesion energy, evolution of self-assembly process and characteristic parameters of hydrogen bond were obtained and analyzed. According to the above simulation, the stabilities of the clockwise and counterclockwise enantiomorphous networks were evaluated. The calculational results were supported by STM observations and the feasibility of the simulation method was confirmed by two other systems in the presence of chiral co-absorbers (R)-(-)-2-octanol and achiral co-absorbers 1-octanol. This theoretical simulation method assesses the stability trend of 2D enantiomorphous assemblies with atomic scale and can be applied to the similar hydrogen bond driven 2D chirality of molecular self-assembly system.

Surface confined metallosupramolecular architectures: formation and scanning tunneling microscopy characterization.

PubMed

Li, Shan-Shan; Northrop, Brian H; Yuan, Qun-Hui; Wan, Li-Jun; Stang, Peter J

2009-02-17

Metallosupramolecular compounds have attracted a great deal of attention over the past two decades largely because of their unique, highly complex structural characteristics and their potential electronic, magnetic, optical, and catalytic properties. These molecules can be prepared with relative ease using coordination-driven self-assembly techniques. In particular, the use of electron-poor square-planar Pt(II) transition metals in conjunction with rigid, electron-rich pyridyl donors has enabled the spontaneous self-assembly of a rich library of 2D metallacyclic and 3D metallacage assemblies via the directional-bonding approach. With this progress in the preparation and characterization of metallosupramolecules, researchers have now turned their attention toward fully exploring and developing their materials properties. Assembling metallosupramolecular compounds on solid supports represents a vitally important step toward developing their materials properties. Surfaces provide a means of uniformly aligning and orienting these highly symmetric metallacycles and metallacages. This uniformity increases the level of coherence between molecules above that which can be achieved in the solution phase and provides a way to integrate adsorbed layers, or adlayers, into a solid-state materials setting. The dynamic nature of kinetically labile Pt(II)-N coordination bonds requires us to adjust deposition and imaging conditions to retain the assemblies' stability. Toward these aims, we have used scanning tunneling microscopy (STM) to image these adlayers and to understand the factors that govern surface self-assembly and the interactions that influence their structure and stability. This Account describes our efforts to deposit 2D rectangular and square metallacycles and 3D trigonal bipyramidal and chiral trigonal prism metallacages on highly oriented pyrolytic graphite (HOPG) and Au(111) substrates to give intact assemblies and ordered adlayers. We have investigated the effects of varying the size, symmetry, and dimensionality of supramolecular adsorbates, the choice of substrate, the use of a molecular template, and the effects of chirality. Our systematic investigations provide insights into the various adsorbate-adsorbate and substrate-adsorbate interactions that largely determine the architecture of each assembly and affect their performance in a materials setting. Rational control over adlayer formation and structure will greatly enhance the potential of these supramolecules to be used in a variety of applications such as host-guest sensing/diagnostic systems, molecular electronic devices, and heterogeneous stereoselective synthesis and catalysis.

Characterization and Catalytic Upgrading of Crude Bio-oil Produced by Hydrothermal Liquefaction of Swine Manure and Pyrolysis of Biomass

NASA Astrophysics Data System (ADS)

Cheng, Dan

The distillation curve of crude bio-oil from glycerol-assisted hydrothermal liquefaction of swine manure was measured using an advanced distillation apparatus. The crude bio-oil had much higher distillation temperatures than diesel and gasoline and was more distillable than the bio-oil produced by the traditional liquefaction of swine manure and the pyrolysis of corn stover. Each 10% volumetric fraction was analyzed from aspects of its chemical compositions, chemical and physical properties. The appearance of hydrocarbons in the distillates collected at the temperature of 410.9°C and above indicated that the thermal cracking at a temperature from 410°C to 500°C may be a proper approach to upgrade the crude bio-oil produced from the glycerol-assisted liquefaction of swine manure. The effects of thermal cracking conditions including reaction temperature (350-425°C), retention time (15-60 min) and catalyst loadings (0-10 wt%) on the yield and quality of the upgraded oil were analyzed. Under the optimum thermal cracking conditions at 400°C, a catalyst loading of 5% by mass and the reaction time of 30 min, the yield of bio-oil was 46.14% of the mass of the crude bio-oil and 62.5% of the energy stored in the crude bio-oil was recovered in the upgraded bio-oil. The upgraded bio-oil with a heating value of 41.4 MJ/kg and viscosity of 3.6 cP was comparable to commercial diesel. In upgrading crude bio-oil from fast pyrolysis, converting organic acids into neutral esters is significant and can be achieved by sulfonated activated carbon/bio-char developed from fermentation residues. Acitivated carbon and bio-char were sulfonated by concentrated sulfuric acid at 150°C for 18 h. Sulfonation helped activated carbon/bio-char develop acid functional groups. Sulfonated activated carbon with BET surface area of 349.8 m2/g, was effective in converting acetic acid. Acetic acid can be effectively esterified by sulfonated activated carbon (5 wt%) at 78°C for 60 min with the ethanol to acetic acid ratio of 3. Crude pyrolytic oil obtained from the RTI International had distillation temperatures from 164.8°C to 365.5°C and 50% volumetric fraction of the crude bio-oil was distillable. Esterified pyrolytic bio-oil had an increased distillability up to 55% volumetric fraction. The esterified pyrolytic bio-oil had an increased pH of 6.12. Diesel range pyrolytic bio-oil distilled from esterified pyrolytic bio-oil had quite comparable properties with commercial diesel, with an energy content of 41.41 MJ/kg, water content of 0.58 wt%, and viscosity of 7.45 cP.

Hydrotreating Pyrolytic Lignin to Produce a Refinery Feedstock (Poster)

DOE Office of Scientific and Technical Information (OSTI.GOV)

French, R. J.

2013-09-01

Fast pyrolysis of biomass followed by water separation to produce pyrolytic lignin and hydrotreating of the lignin could be used to produce a stable volatile low-oxygen intermediate liquid. Such a liquid could be converted into a finished motor-fuel in a refinery, taking advantage of the existing infrastructure and economies of scale of refineries. Hydrotreating just the lignin would consume less hydrogen while preserving about half of the energy of the original oil. The aqueous by-products could be reformed to produce the needed hydrogen and would contain much of the unwanted acids and unstable oxygenates. To assess such intermediate liquids, severalmore » pyrolytic lignins were prepared by mixing pyrolysis oil with water at 1:1 and 3:1 ratios. The carboxylic acidity in the pyrolytic lignin was reduced to 24 and 10 mg-KOH/g-lignin compared to 81 in the whole oil. These lignins were hydrotreated using Ni-Mo(S)/alumina, Pt/char, or Pd/C(activated) in a semi-batch 1 L stirred autoclave. The oil was stabilized under hydrogen at 150-280 degrees C, then water and light organics were removed by partial depressurization. Hydrodeoxygenation was then performed at 340-400 degrees C. Total pressure was controlled at 70 or 170 bar with hydrogen gas. Organic liquid yields of 39-56% were obtained. For many experiments the organic oxygen content was <7%, acidity was < 7 mg-KOH/g-oil, the volatility was greater than or equal to 94% and, on a carbon basis, the total yield of organic products miscible in hydrocarbons at a 1:10 ratio was over 50%. These properties are probably acceptable to a refinery.The residual liquids left in the reactor at the end of the experiment comprised 60-85% of the organic-phase product while the rest was condensate. 13C-NMR of the residual liquids showed that they were 50-80% aliphatic. 13C-NMR coupled with GC-MS identified phenolic compounds as the main oxygenates in most residual liquids.« less

Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene

NASA Astrophysics Data System (ADS)

Broderick, Bernadette M.; McCaslin, Laura; Moradi, Christopher P.; Stanton, John F.; Douberly, Gary E.

2015-04-01

Singlet dihydroxycarbene ( HO C ̈ OH ) is produced via pyrolytic decomposition of oxalic acid, captured by helium nanodroplets, and probed with infrared laser Stark spectroscopy. Rovibrational bands in the OH stretch region are assigned to either trans,trans- or trans,cis-rotamers on the basis of symmetry type, nuclear spin statistical weights, and comparisons to electronic structure theory calculations. Stark spectroscopy provides the inertial components of the permanent electric dipole moments for these rotamers. The dipole components for trans, trans- and trans, cis-rotamers are (μa, μb) = (0.00, 0.68(6)) and (1.63(3), 1.50(5)), respectively. The infrared spectra lack evidence for the higher energy cis,cis-rotamer, which is consistent with a previously proposed pyrolytic decomposition mechanism of oxalic acid and computations of HO C ̈ OH torsional interconversion and tautomerization barriers.

Process development of beam-lead silicon-gate COS/MOS integrated circuits

NASA Technical Reports Server (NTRS)

Baptiste, B.; Boesenberg, W.

1974-01-01

Two processes for the fabrication of beam-leaded COS/MOS integrated circuits are described. The first process utilizes a composite gate dielectric of 800 A of silicon dioxide and 450 A of pyrolytically deposited A12O3 as an impurity barrier. The second process utilizes polysilicon gate metallization over which a sealing layer of 1000 A of pyrolytic Si3N4 is deposited. Three beam-lead integrated circuits have been implemented with the first process: (1) CD4000BL - three-input NOR gate; (2) CD4007BL - triple inverter; and (3) CD4013BL - dual D flip flop. An arithmetic and logic unit (ALU) integrated circuit was designed and implemented with the second process. The ALU chip allows addition with four bit accuracy. Processing details, device design and device characterization, circuit performance and life data are presented.

Recycling of waste engine oil for diesel production.

PubMed

Maceiras, R; Alfonsín, V; Morales, F J

2017-02-01

The aim of this work was to recycle waste engine oil until converting it into reusable product, diesel fuel. The waste oil was treated using pyrolytic distillation. The effect of two additives (sodium hydroxide and sodium carbonate) in the purification of the obtained fuel was also studied. Moreover, the influence of the number of distillations were analysed. Some thermal and physicochemical properties (density, viscosity, colour, turbidity, acidity value, distillation curves, cetane number, corrosiveness to Cu, water content, flash point and hydrocarbons) were determined to analyse the quality of the obtained fuel. The best results were obtained with 2% of sodium carbonate and two successive distillations. The obtained results showed that pyrolytic distillation of waste engine oil is an excellent way to produce diesel fuel to be used in engines. Copyright © 2016 Elsevier Ltd. All rights reserved.

Elastic Moduli of Pyrolytic Boron Nitride Measured Using 3-Point Bending and Ultrasonic Testing

NASA Technical Reports Server (NTRS)

Kaforey, M. L.; Deeb, C. W.; Matthiesen, D. H.; Roth, D. J.

1999-01-01

Three-point bending and ultrasonic testing were performed on a flat plate of PBN. In the bending experiment, the deformation mechanism was believed to be shear between the pyrolytic layers, which yielded a shear modulus, c (sub 44), of 2.60 plus or minus .31 GPa. Calculations based on the longitudinal and shear wave velocity measurements yielded values of 0.341 plus or minus 0.006 for Poisson's ratio, 10.34 plus or minus .30 GPa for the elastic modulus (c (sub 33)), and 3.85 plus or minus 0.02 GPa for the shear modulus (c (sub 44)). Since free basal dislocations have been reported to affect the value of c (sub 44) found using ultrasonic methods, the value from the bending experiment was assumed to be the more accurate value.

Ultrathin pyrolytic carbon films on a magnetic substrate

NASA Astrophysics Data System (ADS)

Umair, Ahmad; Raza, Tehseen Z.; Raza, Hassan

2016-07-01

We report the growth of ultrathin pyrolytic carbon (PyC) films on nickel substrate by using chemical vapor deposition at 1000 °C under methane ambience. We find that the ultra-fast cooling is crucial for PyC film uniformity by controlling the segregation of carbon on nickel. We characterize the in-plane crystal size of the PyC film by using Raman spectroscopy. The Raman peaks at ˜1354 and ˜1584 cm-1 wavenumbers are used to extract the D and G bands. The corresponding peak intensities are then used in an excitation energy dependent equation to calculate the in-plane crystal size. Using Raman area mapping, the mean value of in-plane crystal size over an area of 100 μm × 100 μm is about 22.9 nm with a standard deviation of about 2.4 nm.

ICP-MS measurement of silver diffusion coefficient in graphite IG-110 between 1048K and 1284K

NASA Astrophysics Data System (ADS)

Carter, L. M.; Seelig, J. D.; Brockman, J. D.; Robertson, J. D.; Loyalka, S. K.

2018-01-01

Silver-110m has been shown to permeate intact silicon carbide and pyrolytic carbon coating layers of the TRISO fuel particles during normal High Temperature Gas-Cooled Reactor (HTGR) operational conditions. The diffusion coefficients for silver in graphite IG-110 measured using a release method designed to simulate HTGR conditions of high temperature and flowing helium in the temperature range 1048-1253 K are reported. The measurements were made using spheres milled from IG-110 graphite that were infused with silver using a pressure vessel technique. The Ag diffusion was measured using a time release technique with an ICP-MS instrument for detection. The results of this work are:

Preparation of pyrolytic carbon coating on graphite for inhibiting liquid fluoride salt and Xe135 penetration for molten salt breeder reactor

NASA Astrophysics Data System (ADS)

Song, Jinliang; Zhao, Yanling; He, Xiujie; Zhang, Baoliang; Xu, Li; He, Zhoutong; Zhang, DongSheng; Gao, Lina; Xia, Huihao; Zhou, Xingtai; Huai, Ping; Bai, Shuo

2015-01-01

A fixed-bed deposition method was used to prepare rough laminar pyrolytic carbon coating (RLPyC) on graphite for inhibiting liquid fluoride salt and Xe135 penetration during use in molten salt breeder reactor. The RLPyC coating possessed a graphitization degree of 44% and had good contact with graphite substrate. A high-pressure reactor was constructed to evaluate the molten salt infiltration in the isostatic graphite (IG-110, TOYO TANSO CO., LTD.) and RLPyC coated graphite under 1.01, 1.52, 3.04, 5.07 and 10.13 × 105 Pa for 12 h. Mercury injection and molten-salt infiltration experiments indicated the porosity and the salt-infiltration amount of 18.4% and 13.5 wt% under 1.52 × 105 Pa of IG-110, which was much less than 1.2% and 0.06 wt% under 10.13 × 105 Pa of the RLPyC, respectively. A vacuum device was constructed to evaluate the Xe135 penetration in the graphite. The helium diffusion coefficient of RLPyC coated graphite was 2.16 × 10-12 m2/s, much less than 1.21 × 10-6 m2/s of the graphite. Thermal cycle experiment indicated the coatings possessed excellent thermal stability. The coated graphite could effectively inhibit the liquid fluoride salt and Xe135 penetration.

Characterization of ultralow thermal conductivity in anisotropic pyrolytic carbon coating for thermal management applications

DOE PAGES

Wang, Yuzhou; Hurley, David H.; Luther, Erik Paul; ...

2017-12-11

Pyrolytic carbon (PyC) is an important material used in many applications including thermal management of electronic devices and structural stability of ceramic composites. Accurate measurement of physical properties of structures containing textured PyC layers with few-micrometer thickness poses new challenges. Here a laser-based thermoreflectance technique is used to measure thermal conductivity in a 30-μm-thick textured PyC layer deposited using chemical vapor deposition on the surface of spherical zirconia particles. Raman spectroscopy is used to confirm the graphitic nature and characterize microstructure of the deposited layer. Room temperature radial and circumferential thermal conductivities are found to be 0.28 W m –1more » K –1 and 11.5 W m –1 K –1, corresponding to cross-plane and in-plane conductivities of graphite. While the anisotropic ratio of the in-plane to cross-plane conductivities is smaller than previous results, the magnitude of the smallest conductivity is noticeably smaller than previously reported values for carbon materials and offers opportunities in thermal management applications. Very low in-plane and cross-plane thermal conductivities are attributed to strong grain boundary scattering, high defect concentration, and small inter-laminar porosity. Lastly, experimental results agree with the prediction of thermal transport model informed by the microstructure information revealed by Raman spectroscopy.« less

Analytical pyrolysis mass spectrometry: new vistas opened by temperature-resolved in-source PYMS

NASA Astrophysics Data System (ADS)

Boon, Jaap J.

1992-09-01

Analytical pyrolysis mass spectrometry (PYMS) is introduced and its applications to the analysis of synthetic polymers, biopolymers, biomacromolecular systems and geomacromolecules are critically reviewed. Analytical pyrolysis inside the ionisation chamber of a mass spectrometer, i.e. in-source PYMS, gives a complete inventory of the pyrolysis products evolved from a solid sample. The temperature-resolved nature of the experiment gives a good insight into the temperature dependence of the volatilisation and pyrolytic dissociation processes. Chemical ionisation techniques appear to be especially suitable for the analysis of oligomeric fragments released in early stages of the pyrolysis of polymer systems. Large oligomeric fragments were observed for linear polymers such as cellulose (pentadecamer), polyhydroxyoctanoic acid (tridecamer) and polyhydroxybutyric acid (heneicosamer). New in-source PYMS data are presented on artists' paints, the plant polysaccharides cellulose and xyloglucan, several microbial polyhydroxyalkanoates, wood and enzyme-digested wood, biodegraded roots and a fossil cuticle of Miocene age. On-line and off-line pyrolysis chromatography mass spectrometric approaches are also discussed. New data presented on high temperature gas chromatography--mass spectrometry of deuterio-reduced permethylated pyrolysates of cellulose lead to a better understanding of polysaccharide dissociation mechanisms. Pyrolysis as an on-line sample pretreatment method for organic macromolecules in combination with MS techniques is a very challenging field of mass spectrometry. Pyrolytic dissociation and desorption is not at all a chaotic process but proceeds according to very specific mechanisms.

The historical record of atmospheric pyrolytic pollution over Europe registered in the sedimentary PAH from remote mountain lakes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fernandez, P.; Vilanova, R.M.; Martinez, C.

2000-05-15

Historical records of the deposition fluxes of polycyclic aromatic hydrocarbons (PAH) in 10 remote high altitude lakes distributed throughout Europe have been studied. Cores from each site were dated radiometrically, and the results were used for the reconstruction of the pollutant changes between 1830 and present. In general, both PAH pyrolytic fluxes and concentrations increased from uniform background levels at the turn of the century to maximum values in 1960--1980. After these peak values a slight decrease to present day levels has been observed in some lakes, though they are still 3--20 times greater than the preindustrial period. Distinctive featuresmore » in the downcore PAH profiles and concentrations between sites allowed for differentiation between five regions in Europe: peripheral areas (Norway and the Liberian Peninsula), Pyrenees and western Alps, central Alps, Tatra Mountains, and the Arctic. Atmospheric PAH inventories were estimated from the vertical integration of sedimentary inventories using {sup 210}Pb to correct for post depositional transport processes. This approach consistently reduces variability among lakes from the same region. The results obtained define the lakes in the Tatra mountains and that on Spits Bergen Island as those of highest and lowest atmospheric PAH input. The other lakes exhibit lower differences although their atmospheric inventory values group consistently with the above-mentioned regions.« less

Characterization of ultralow thermal conductivity in anisotropic pyrolytic carbon coating for thermal management applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yuzhou; Hurley, David H.; Luther, Erik Paul

Pyrolytic carbon (PyC) is an important material used in many applications including thermal management of electronic devices and structural stability of ceramic composites. Accurate measurement of physical properties of structures containing textured PyC layers with few-micrometer thickness poses new challenges. Here a laser-based thermoreflectance technique is used to measure thermal conductivity in a 30-μm-thick textured PyC layer deposited using chemical vapor deposition on the surface of spherical zirconia particles. Raman spectroscopy is used to confirm the graphitic nature and characterize microstructure of the deposited layer. Room temperature radial and circumferential thermal conductivities are found to be 0.28 W m –1more » K –1 and 11.5 W m –1 K –1, corresponding to cross-plane and in-plane conductivities of graphite. While the anisotropic ratio of the in-plane to cross-plane conductivities is smaller than previous results, the magnitude of the smallest conductivity is noticeably smaller than previously reported values for carbon materials and offers opportunities in thermal management applications. Very low in-plane and cross-plane thermal conductivities are attributed to strong grain boundary scattering, high defect concentration, and small inter-laminar porosity. Lastly, experimental results agree with the prediction of thermal transport model informed by the microstructure information revealed by Raman spectroscopy.« less

Pyrolytic indices of diagenetic transformation of lignin as biogeochemical proxies for soil organic matter quality and C storage potential

NASA Astrophysics Data System (ADS)

Jiménez-González, Marco A.; Almendros, Gonzalo; Álvarez, Ana M.; Jiménez-Morillo, Nicasio T.; González-Vila, Francisco J.

2017-04-01

The environmental factors involved in soil organic carbon sequestration remain unclear. The functional relationships between the macromolecular structure of the soil organic matter (SOM) and its resilience has been a constant in classical biogeochemical models. Other more recent hypotheses have postulated that preservation by soil minerals may play a chief role in the accumulation of stable SOM forms. However, additional experimental data are required to demonstrate a cause-to-effect relationship between preservation and stabilization. Some authors might consider that models neglecting the role of macromolecular structure are swapping cause and effect i.e., that SOM structurally flexible, weakly condensed and having 'open' structures is the one with high potential to interact with the soil mineral matrix, leading to stable microaggregates. In this study up to 35 topsoil samples (0-5 cm) were collected from different Spanish soils with contrasted values of organic C (the dependent variable), geological substrate and vegetation type. A wide array of uni- and multivariate chemometric models were applied to independent variables consisting of total abundances of the major aromatic compounds, i.e., alkylbenzenes and methoxyphenols released from whole soil samples using pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS). These two families of compounds were selected since they are classically considered to inform on the degree of microbial reworking of lignins, which is an important precursor of the aromatic moiety of the SOM. A series of pyrolytic surrogate indices (aiming to express SOM diagenetic transformation in relation to the original biogenic molecular composition) were especially successful in forecasting SOC, viz: a) ratio between alkylbenzenes and methoxyphenols, b) ratio between short-chain (C0-C4) and long-chain (>C4) alkylbenzenes, c) ratio between methoxyphenols and short-chain alkylbenzenes, and d) ratios between methoxyphenols with different side-chain length, i.e., methyl-, ethyl-, vinyl-, propenyl- and aceto- derivatives of guaiacyl and syringyl rings. In particular partial least squares regression (PLS) models led to very significant prediction of SOC based exclusively on the major aromatic pyrolytic compounds as predictors, i.e, methoxyphenols and alkylbenzenes. The PLS coefficients showed high positive loadings for methoxyphenols (i.e., these compounds were diagnostic for soils with high C-storage potential), and negative for alkylbenzenes (which were characteristic for C-depleted soils). This may be explained as if selective preservation of lignin were the most efficient process in soils behaving as active C sinks. Conversely, the progressive smoothing in the lignin signature and the accumulation of methoxyl-lacking aromatics (i.e., short-chain alkylbenzenes) was typical in the soils with low SOC content but high levels of diagenetic alteration of lignin. The progressive alteration of C6-C3 phenylpropanoid lignin units also corresponded to the fact that heavily altered lignin, presumptively accumulated in SOM depleted soils, tended to release typical pyrolytic markers consisting of C0-C1 methoxyphenols instead of its vinyl and propenyl counterparts, in addition to major proportions of short-chain (

Process to minimize cracking of pyrolytic carbon coatings

DOEpatents

Lackey, Jr., Walter J.; Sease, John D.

1978-01-01

Carbon-coated microspheroids useful as fuels in nuclear reactors are produced with a low percentage of cracked coatings and are imparted increased strength and mechanical stability characteristics by annealing immediately after the carbon coating processes.

Spectroscopic investigation of the wettability of multilayer graphene using highly ordered pyrolytic graphite as a model material.

PubMed

Ashraf, Ali; Wu, Yanbin; Wang, Michael C; Aluru, Narayana R; Dastgheib, Seyed A; Nam, SungWoo

2014-11-04

We report the intrinsic water contact angle (WCA) of multilayer graphene, explore different methods of cleaning multilayer graphene, and evaluate the efficiency of those methods on the basis of spectroscopic analysis. Highly ordered pyrolytic graphite (HOPG) was used as a model material system to study the wettability of the multilayer graphene surface by WCA measurements. A WCA value of 45° ± 3° was measured for a clean HOPG surface, which can serve as the intrinsic WCA for multilayer graphene. A 1 min plasma treatment (100 W) decreased the WCA to 6°, owing to the creation of surface defects and functionalization by oxygen-containing groups. Molecular dynamics simulations of water droplets on the HOPG surface with or without the oxygen-containing defect sites confirmed the experimental results. Heat treatment at near atmospheric pressure and wet chemical cleaning methods using hydrofluoric acid and chloroform did not change the WCA significantly. Low-pressure, high-temperature annealing under argon and hydrogen reduced the WCA to 54°, close to the intrinsic WCA of HOPG. Raman spectroscopy and atomic force microscopy did not show any significant change for the HOPG surface after this treatment, confirming low-pressure, high-temperature annealing as an effective technique to clean multilayer graphene without damaging the surface. Time-of-flight secondary ion mass spectrometry indicated the existence of hydrocarbon species on the surface of the HOPG sample that was exposed to air for <5 min and the absence of these impurities in the bulk. X-ray photoelectron spectroscopy analyses of the sample surfaces after the different cleaning techniques were performed to correlate the WCA to the surface chemistry. X-ray photoelectron spectroscopy results revealed that the WCA value changed drastically, depending on the amounts of oxygen-containing and hydrocarbon-containing groups on the surface.

Structural and optical characterization of pyrolytic carbon derived from novolac resin.

PubMed

Theodoropoulou, S; Papadimitriou, D; Zoumpoulakis, L; Simitzis, J

2004-07-01

The structural and optical properties of technologically interesting pyrolytic carbons formed from cured novolac resin and cured novolac/biomass composites were studied by X-Ray Diffraction Analysis (XRD), and Fourier Transform Infrared (FTIR), Raman and Photoluminescence (PL) spectroscopy. Pyrolysis of the cured materials took place at temperatures in the range 400-1000 degrees C. The most important weight loss, shrinkage and structural changes of pyrolyzed composites are observed at temperatures up to 600 degrees C due to the olive stone component. In the same temperature range, the changes in pyrolyzed novolac are smaller. The spectroscopic analysis shows that novolac pyrolyzed up to 900 ( degrees )C has less defects and disorder than the composites. However, above 900 ( degrees )C, pyrolyzed novolac becomes more disordered compared to the pyrolyzed composites. It is concluded that partial replacement of novolac by olive stone in the composite materials leads to the formation of a low cost, good quality product.

Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene

DOE PAGES

Broderick, Bernadette M.; McCaslin, Laura; Moradi, Christopher P.; ...

2015-04-14

Singlet dihydroxycarbene (HOmore » $$\\ddot C$$OH) is produced via pyrolytic decomposition of oxalic acid, captured by helium nanodroplets, and probed with infrared laser Stark spectroscopy. Rovibrational bands in the OH stretch region are assigned to either trans, trans-or trans, cis-rotamers on the basis of symmetry type, nuclear spin statistical weights, and comparisons to electronic structure theory calculations. Stark spectroscopy provides the inertial components of the permanent electric dipole moments for these rotamers. The dipole components for trans, trans-and trans, cis-rotamers are (μ a, μ b) = (0.00,0.68(6)) and (1.63(3), 1.50(5)), respectively. The infrared spectra lack evidence for the higher energy cis,cis-rotamer, which is consistent with a previously proposed pyrolytic decomposition mechanism of oxalic acid and computations of HO$$\\ddot C$$OH torsional interconversion and tautomerization barriers.« less

Pyrolytic and Kinetic Characteristics of the Thermal Decomposition of Perilla frutescens Polysaccharide

PubMed Central

Zhou, Quancheng; Sheng, Guihua

2012-01-01

The thermal decomposition of Perilla frutescens polysaccharide was examined by thermogravimetry, differential thermogravimetry, and differential thermal analysis. The results showed that the mass loss of the substance proceeded in three steps. The first stage can be attributed to the expulsion of the water from ambient temperature to 182°C. The second stage corresponded to devolatilization from 182°C to 439°C. The residue slowly degraded in the third stage. The weight loss in air is faster than that in nitrogen, because the oxygen in air accelerated the pyrolytic reaction speed reaction. The heating rate significantly affected the pyrolysis of the sample. Similar activation energies of the degradation process (210–211 kJ mol−1) were obtained by the FWO, KAS, and Popescu techniques. According to Popescu mechanism functions, the possible kinetic model was estimated to be Avrami–Erofeev 20 g(α) = [−ln(1–α)]4. PMID:23300715

Fast pyrolysis of potassium impregnated poplar wood and characterization of its influence on the formation as well as properties of pyrolytic products.

PubMed

Hwang, Hyewon; Oh, Shinyoung; Cho, Tae-Su; Choi, In-Gyu; Choi, Joon Weon

2013-12-01

TGA results indicated that the maximum decomposition temperature of the biomass decreased from 373.9 to 359.0°C with increasing potassium concentration. For fast pyrolysis, char yield of potassium impregnated biomass doubled regardless of pyrolysis temperature compared to demineralized one. The presence of potassium also affected bio-oil properties. Water content increased from 14.4 to 19.7 wt% and viscosity decreased from 34 to 16.2 cSt, but the pH value of the bio-oil remained stable. Gas chromatography/mass spectroscopy (GC/MS) analysis revealed that potassium promoted thermochemical reactions, thus causing a decrease of levoglucosan and an increase of small molecules and lignin-derived phenols in bio-oil. Additionally, various forms of aromatic hydrocarbons, probably derived from lignins, were detected in non-condensed pyrolytic gas fractions. Copyright © 2013 Elsevier Ltd. All rights reserved.

Impact of the lignocellulosic material on fast pyrolysis yields and product quality.

PubMed

Carrier, Marion; Joubert, Jan-Erns; Danje, Stephen; Hugo, Thomas; Görgens, Johann; Knoetze, Johannes Hansie

2013-12-01

The paper describes the fast pyrolysis conversion of lignocellulosic materials inside a bubbling fluidized bed. The impact of biopolymers distribution in the biomass feed, namely hemicelluloses, cellulose and lignin, on the yields and properties of pyrolytic bio-oils and chars was investigated. Although it is not possible to deconvoluate chemical phenomena from transfer phenomena using bubbling fluidized bed reactors, the key role of hemicelluloses in biomass feedstocks was illustrated by: (i) its influence on the production of pyrolytic water, (ii) its impact on the production of organics, apparently due to its bonding relationship with the lignin and (iii) its ability to inhibit the development of chars porosity, while the cellulose appeared to be the precursor for the microporous character of the biochars. These results are of interest for the selection of suitable feedstocks aimed at producing bio-oil and char as fuels and soil amendment, respectively. Copyright © 2013 Elsevier Ltd. All rights reserved.

[Study on anti-coagulant property of radio frequency sputtering nano-sized TiO2 thin films].

PubMed

Tang, Xiaoshan; Li, Da

2010-12-01

Nano-TiO2 thin films were prepared by Radio frequency (RF) sputtering on pyrolytic carbon substrates. The influences of sputtering power on the structure and the surface morphology of TiO2 thin films were investigated by X-ray diffraction (XRD), and by scanning electron microscopy (SEM). The results show that the TiO2 films change to anatase through the optimum of sputtering power. The mean diameter of nano-particle is about 30 nm. The anti-coagulant property of TiO2 thin films was observed through platelet adhesion in vitro. The result of experiment reveals the amount of thrombus on the TiO2 thin films being much less than that on the pyrolytic carbon. It also indicates that the RF sputtering Nano-sized TiO2 thin films will be a new kind of promising materials applied to artificial heart valve and endovascular stent.

Surface-induced dissociation and chemical reactions of C2D4(+) on stainless steel, carbon (HOPG), and two different diamond surfaces.

PubMed

Feketeová, Linda; Zabka, Jan; Zappa, Fabio; Grill, Verena; Scheier, Paul; Märk, Tilmann D; Herman, Zdenek

2009-06-01

Surface-induced interactions of the projectile ion C(2)D(4)(+) with room-temperature (hydrocarbon covered) stainless steel, carbon highly oriented pyrolytic graphite (HOPG), and two different types of diamond surfaces (O-terminated and H-terminated) were investigated over the range of incident energies from a few eV up to 50 eV. The relative abundance of the product ions in dependence on the incident energy of the projectile ion [collision-energy resolved mass spectra, (CERMS) curves] was determined. The product ion mass spectra contained ions resulting from direct dissociation of the projectile ions, from chemical reactions with the hydrocarbons on the surface, and (to a small extent) from sputtering of the surface material. Sputtering of the surface layer by low-energy Ar(+) ions (5-400 eV) indicated the presence of hydrocarbons on all studied surfaces. The CERMS curves of the product ions were analyzed to obtain both CERMS curves for the products of direct surface-induced dissociation of the projectile ion and CERMS curves of products of surface reactions. From the former, the fraction of energy converted in the surface collision into the internal excitation of the projectile ion was estimated as 10% of the incident energy. The internal energy of the surface-excited projectile ions was very similar for all studied surfaces. The H-terminated room-temperature diamond surface differed from the other surfaces only in the fraction of product ions formed in H-atom transfer surface reactions (45% of all product ions formed versus 70% on the other surfaces).

Closer look at the effect of AFM imaging conditions on the apparent dimensions of surface nanobubbles.

PubMed

Walczyk, Wiktoria; Schönherr, Holger

2013-01-15

To date, TM AFM (tapping mode or intermittent contact mode atomic force microscopy) is the most frequently applied direct imaging technique to visualize surface nanobubbles at the solid-aqueous interface. On one hand, AFM is the only profilometric technique that provides estimates of the bubbles' nanoscopic dimensions. On the other hand, the nanoscopic contact angles of surface nanobubbles estimated from their apparent dimensions that are deduced from AFM "height" images of nanobubbles differ markedly from the macrocopic water contact angles on the identical substrates. Here we show in detail how the apparent bubble height and width of surface nanobubbles on highly oriented pyrolytic graphite (HOPG) depend on the free amplitude of the cantilever oscillations and the amplitude setpoint ratio. (The role of these two AFM imaging parameters and their interdependence has not been studied so far for nanobubbles in a systematic way.) In all experiments, even with optimal scanning parameters, nanobubbles at the HOPG-water interface appeared to be smaller in the AFM images than their true size, which was estimated using a method presented herein. It was also observed that the severity of the underestimate increased with increasing bubble height and radius of curvature. The nanoscopic contact angle of >130° for nanobubbles on HOPG extrapolated to zero interaction force was only slightly overestimated and hence significantly higher than the macroscopic contact angle of water on HOPG (63 ± 2°). Thus, the widely reported contact angle discrepancy cannot be solely attributed to inappropriate AFM imaging conditions.

In-situ observation of sputtered particles for carbon implanted tungsten during energetic isotope ion implantation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oya, Y.; Sato, M.; Uchimura, H.

2015-03-15

Tungsten is a candidate for plasma facing materials in future fusion reactors. During DT plasma operations, carbon as an impurity will bombard tungsten, leading to the formation of tungsten-carbon (WC) layer and affecting tritium recycling behavior. The effect of carbon implantation for the dynamic recycling of deuterium, which demonstrates tritium recycling, including retention and sputtering, has been investigated using in-situ sputtered particle measurements. The C{sup +} implanted W, WC and HOPG were prepared and dynamic sputtered particles were measured during H{sub 2}{sup +} irradiation. It has been found that the major hydrocarbon species for C{sup +} implanted tungsten is CH{submore » 3}, while for WC and HOPG (Highly Oriented Pyrolytic Graphite) it is CH{sub 4}. The chemical state of hydrocarbon is controlled by the H concentration in a W-C mixed layer. The amount of C-H bond and the retention of H trapped by carbon atom should control the chemical form of hydrocarbon sputtered by H{sub 2}{sup +} irradiation and the desorption of CH{sub 3} and CH{sub 2} are due to chemical sputtering, although that for CH is physical sputtering. The activation energy for CH{sub 3} desorption has been estimated to be 0.4 eV, corresponding to the trapping process of hydrogen by carbon through the diffusion in W. It is concluded that the chemical states of hydrocarbon sputtered by H{sub 2}{sup +} irradiation for W is determined by the amount of C-H bond on the W surface. (authors)« less

Formation and composition of adsorbates on hydrophobic carbon surfaces from aqueous laccase-maltodextrin mixture suspension

NASA Astrophysics Data System (ADS)

Corrales Ureña, Yendry Regina; Lisboa-Filho, Paulo Noronha; Szardenings, Michael; Gätjen, Linda; Noeske, Paul-Ludwig Michael; Rischka, Klaus

2016-11-01

A robust procedure for the surface bio-functionalization of carbon surfaces was developed. It consists on the modification of carbon materials in contact with an aqueous suspension of the enzyme laccase from Trametes versicolor and the lyophilization agent maltodextrin, with the pH value adjusted close to the isoelectric point of the enzyme. We report in-situ investigations applying Quartz Crystal Microbalance with Dissipation (QCM-D) for carbon-coated sensor surfaces and, moreover, ex-situ measurements with static contact angle measurements, X-ray Photoelectron Spectroscopy (XPS) and Scanning Force Microscopy (SFM) for smooth Highly Oriented Pyrolytic Graphite (HOPG) substrates, for contact times between the enzyme formulation and the carbon material surface ranging from 20 s to 24 h. QCM-D studies reveals the formation of rigid layer of biomaterial, a few nanometers thin, which shows a strongly improved wettability of the substrate surface upon contact angle measurements. Following spectroscopic characterization, these layers are composed of mixtures of laccase and maltodextrin. The formation of these adsorbates is attributed to attractive interactions between laccase, the maltodextrin-based lyophilization agent and the hydrophobic carbon surfaces; a short-term contact between the aqueous laccase mixture suspension and HOPG surfaces is shown to merely result in de-wetting patterns influencing the results of contact angle measurements. The new enzyme-based surface modification of carbon-based materials is suggested to be applicable for the improvement of not only the wettability of low energy substrate surfaces with fluid formulations like coatings or adhesives, but also their adhesion in contact with hardened polymers.

Feasibility Studies of Parametric X-rays Use in a Medical Environment

NASA Astrophysics Data System (ADS)

Sones, Bryndol; Danon, Yaron; Blain, Ezekiel

2009-03-01

Parametric X-rays (PXR) are produced from the interaction of relativistic electrons with the periodic structure of crystal materials. Smooth X-ray energy tunability is achieved by rotating the crystal with respects to the electron beam direction. Experiments at the Rensselaer Polytechnic Institute 60-MeV LINAC produce quasi-monochromatic X-rays (6-35 keV) from various target crystals to include highly oriented pyrolytic graphite (HOPG), LiF, Si, Ge, Cu, and W using electron beam currents up to 6 uA. These experiments demonstrate the first PXR images and some of the merits of thin metallic crystals. Recent experiments with a 100-μm thick Cu crystal improve the Cu PXR (with energy ˜12 keV) to Cu fluorescence ratio by a factor of 20 compared to a 1 mm-thick Cu crystal. This study uses Monte Carlo techniques to investigate (1) PXR dose compared to emissions from simulated Mo, Rh, and W anodes for mammography applications and (2) electron scattering effects when considering LiF111, Si111, and Cu111 PXR production using electron beams with energies of 20-30 MeV. Advantages in using monochromatic PXR compared to X-rays from Mo and Rh anodes in mammography applications result in a dose per incident photon reduction by a factor of 2. Using 20 MeV electrons, the thinner Cu111 crystal for 15 keV PXR production results in an electron scattering angle of 30.7+/-0.2 mrad offering the best potential for PXR from lower energy electrons.

Stiffness and evolution of interfacial micropancakes revealed by AFM quantitative nanomechanical imaging.

PubMed

Zhao, Binyu; Wang, Xingya; Song, Yang; Hu, Jun; Lü, Junhong; Zhou, Xingfei; Tai, Renzhong; Zhang, Xuehua; Zhang, Lijuan

2015-05-28

Micropancakes are quasi-two-dimensional micron-sized domains on crystalline substrates (e.g. highly oriented pyrolytic graphite (HOPG)) immersed in water. They are only a few nanometers thick, and are suspected to come from the accumulation of dissolved air at the solid-water interface. However, the exact chemical nature and basic physical properties of micropancakes have been under debate ever since their first observation, primarily due to the lack of a suitable characterization technique. In this study, the stiffness of micropancakes at the interface between HOPG and ethanol-water solutions was investigated by using PeakForce Quantitative NanoMechanics (PF-QNM) mode Atomic Force Microscopy (AFM). Our measurements showed that micropancakes were stiffer than nanobubbles, and for bilayer micropancakes, the bottom layer in contact with the substrate was stiffer than the top one. Interestingly, the micropancakes became smaller and softer with an increase in the ethanol concentration in the solution, and were undetectable by AFM above a critical concentration of ethanol. But they re-appeared after the ethanol concentration in the solution was reduced. Clearly the evolution and stiffness of the micropancakes were dependent on the chemical composition in the solution, which could be attributed to the correlation of the mechanical properties of the micropancakes with the surface tension of the liquid phase. Based on the "go-and-come" behaviors of micropancakes with the ethanol concentration, we found that the micropancakes could actually tolerate the ethanol concentration much higher than 5%, a value reported in the literature. The results from this work may be helpful in alluding the chemical nature of micropancakes.

Cyclic fatigue-crack propagation, stress-corrosion, and fracture-toughness behavior in pyrolytic carbon-coated graphite for prosthetic heart valve applications.

PubMed

Ritchie, R O; Dauskardt, R H; Yu, W K; Brendzel, A M

1990-02-01

Fracture-mechanics tests were performed to characterize the cyclic fatigue, stress-corrosion cracking, and fracture-toughness behavior of a pyrolytic carbon-coated graphite composite material used in the manufacture of cardiac valve prostheses. Testing was carried out using compact tension C(T) samples containing "atomically" sharp precracks, both in room-temperature air and principally in a simulated physiological environment of 37 degrees C Ringer's lactate solution. Under sustained (monotonic) loads, the composite exhibited resistance-curve behavior, with a fracture toughness (KIc) between 1.1 and 1.9 MPa square root of m, and subcritical stress-corrosion crack velocities (da/dt) which were a function of the stress intensity K raised to the 74th power (over the range approximately 10(-9) to over 10(-5) m/s). More importantly, contrary to common perception, under cyclic loading conditions the composite was found to display true (cyclic) fatigue failure in both environments; fatigue-crack growth rates (da/dN) were seen to be a function of the 19th power of the stress-intensity range delta K (over the range approximately 10(-11) to over 10(-8) m/cycle). As subcritical crack velocities under cyclic loading were found to be many orders of magnitude faster than those measured under equivalent monotonic loads and to occur at typically 45% lower stress-intensity levels, cyclic fatigue in pyrolytic carbon-coated graphite is reasoned to be a vital consideration in the design and life-prediction procedures of prosthetic devices manufactured from this material.

Characterization of pyrolytic products obtained from fast pyrolysis of chromated copper arsenate (CCA)- and alkaline copper quaternary compounds (ACQ)-treated wood biomasses.

PubMed

Kim, Jae-Young; Kim, Tae-Sung; Eom, In-Yong; Kang, Sung Mo; Cho, Tae-Su; Choi, In Gyu; Choi, Joon Weon

2012-08-15

In this study, chromated copper arsenate-treated wood (CCA-W) and alkaline copper quaternary compounds-treated wood (ACQ-W) were subjected to fast pyrolysis at 500°C for ca. 2s to produce bio-oil and char. The physicochemical properties of the pyrolytic products as well as the distribution of heavy metals - arsenic, copper and chrome - during fast pyrolysis were investigated. The water content, viscosity, pH and higher heating value (HHV) of bio-oil from CCA-W were 24.8 wt%, 13.5 cSt, 2.1 and 16 MJ/kg, respectively, whereas those of bio-oil from ACQ-W were 27.9 wt%, 16 cSt, 3.0 and 14.1 MJ/kg, respectively. The yields of bio-oil from CCA-W and ACQ-W were 43.3% and 46.6%, respectively, significantly lower than that of control (61.6%). In the pyrolytic products of CCA-W, the concentrations of arsenic, copper and chromium were determined to be 36.4 wt%, 74.0 wt% and 75.4 wt% in char, respectively, 34.5 wt%, 10.3 wt% and 9.0 wt% in bio-oil, respectively, and 29.0 wt%, 15.7 wt% and 15.5 wt% in gas, respectively. In addition, most of the copper appeared in the char (98.8 wt%) and only a trace amount of copper was detected in the bio-oil (0.2 wt%) produced by ACQ-W. Copyright © 2012 Elsevier B.V. All rights reserved.

Method of making carbon-carbon composites

DOEpatents

Engle, Glen B.

1993-01-01

A process for making 2D and 3D carbon-carbon composites having a combined high crystallinity, high strength, high modulus and high thermal and electrical conductivity. High-modulus/high-strength mesophase derived carbon fibers are woven into a suitable cloth. Layers of this easily graphitizible woven cloth are infiltrated with carbon material to form green composites. The carbonized composite is then impregnated several times with pitch by covering the composite with hot pitch under pressure. The composites are given a heat treatment between each impregnant step to crack up the infiltrated carbon and allow additional pitch to enter the microstructure during the next impregnation cycle. The impregnated composites are then given a final heat treatment in the range 2500.degree. to 3100.degree. C. to fully graphitize the fibers and the matrix carbon. The composites are then infiltrated with pyrolytic carbon by chemical vapor deposition in the range 1000.degree. C. to 1300.degree. C. at a reduced. pressure.

ENGINEERING BULLETIN: PYROLYSIS TREATMENT

EPA Science Inventory

Pyrolysis is formally defined as chemical decomposition induced in organic materials by heat in the absence of oxygen. In practice, it is not possible to achieve a completely oxygen-free atmosphere; actual pyrolytic systems are operated with less than stoichiometric quantities of...

Direct Observation of Asphaltene Nanoparticles on Model Mineral Substrates.

PubMed

Raj, Gijo; Lesimple, Alain; Whelan, Jamie; Naumov, Panče

2017-06-27

The propensity for adherence to solid surfaces of asphaltenes, a complex solubility class of heteropolycyclic aromatic compounds from the heavy fraction of crude oil, has long been the root cause of scale deposition and remains an intractable problem in the petroleum industry. Although the adhesion is essential to understanding the process of asphaltene deposition, the relationship between the conformation of asphaltene molecules on mineral substrates and its impact on adhesion and mechanical properties of the deposits is not completely understood. To rationalize the primary processes in the process of organic scale deposition, here we use atomic force microscopy (AFM) to visualize the morphology of petroleum asphaltenes deposited on model mineral substrates. High imaging contrast was achieved by the differential adhesion of the tip between asphaltenes and the mineral substrate. While asphaltenes form smooth continuous films on all substrates at higher concentrations, they deposit as individual nanoparticles at lower concentrations. The size, shape, and spatial distribution of the nanoaggregates are strongly affected by the nature of the substrate; while uniformly distributed spherical particles are formed on highly polar and hydrophilic substrates (mica), irregular islands and thicker patches are observed with substrates of lower polarity (silica and calcite). Asphaltene nanoparticles flatten when adsorbed on highly oriented pyrolytic graphite due to π-π interactions with the polycyclic core. Force-distance profiles provide direct evidence of the conformational changes of asphaltene molecules on hydrophilic/hydrophobic substrates that result in dramatic changes in adhesion and mechanical properties of asphaltene deposits. Such an understanding of the nature of adhesion and mechanical properties tuned by surface properties, on the level of asphaltene nanoaggregates, would contribute to the design of efficient asphaltene inhibitors for preventing asphaltene fouling on targeted surfaces. Unlike flat surfaces, the AFM phase contrast images of defected calcite surfaces show that asphaltenes form continuous deposits to fill the recesses, and this process could trigger the onset for asphaltene deposition.

Characterization and distribution of polycyclic aromatic hydrocarbon contaminations in surface sediment and water from Gao-ping River, Taiwan.

PubMed

Doong, Ruey-An; Lin, Yu-Tin

2004-04-01

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) in water and sediment samples collected from 12 locations in Gao-ping River, Taiwan were analyzed. Molecular ratios and principal component analysis (PCA) were used to characterize the possible pollution sources. Concentrations of total 16 PAHs (SigmaPAHs) in water samples ranged from below method detection limits (

Supercooling of Hydrogen on Template Materials to Deterministically Seed Ignition-Quality Solid Fuel Layers

DOE PAGES

Shin, S. J.; Zepeda-Ruiz, L. A.; Lee, J. R. I.; ...

2016-09-01

In this study, we explored templating effects of various materials for hydrogen (H 2 and D 2) solidification by measuring the degree of supercooling required for liquid hydrogen to solidify below each triple point. The results show high supercooling (>100 mK) for most metallic, covalent, and ionic solids, and low supercooling (<100 mK) for van der Waals (vdW) solids. We attribute the low supercooling of vdW solids to the weak interaction of the substrate and hydrogen. Highly ordered pyrolytic graphite showed the lowest supercooling among materials that are solid at room temperature, but did not exhibit a templating effect withinmore » a fill-tube and capsule assembly.« less

Bandgap engineering through nanocrystalline magnetic alloy grafting on reduced graphene oxide.

PubMed

De, D; Chakraborty, M; Majumdar, S; Giri, S

2014-09-28

High conductivity and the absence of ferromagnetism in pristine graphene fail to satisfy primary criteria for possible technological application in spintronics. Opening of the bandgap in graphene is primarily desirable for such applications. We report a simplified and novel approach of controlled grafting of a magnetic alloy on reduced graphene oxide. This eventually leads to ferromagnetism of the stable hybrid material at room temperature, with a large moment (∼1.2 μB) and a remarkable decrease in conductivity (∼10 times) compared to highly ordered pyrolytic graphite. Our model band-structure calculation indicates that the combined effect of controlled vacancies and impurities attributed to the nanocrystalline alloy grafting leads to a promising step toward band gap engineering.

Producing graphite with desired properties

NASA Technical Reports Server (NTRS)

Dickinson, J. M.; Imprescia, R. J.; Reiswig, R. D.; Smith, M. C.

1971-01-01

Isotropic or anisotropic graphite is synthesized with precise control of particle size, distribution, and shape. The isotropic graphites are nearly perfectly isotropic, with thermal expansion coefficients two or three times those of ordinary graphites. The anisotropic graphites approach the anisotropy of pyrolytic graphite.

Method and apparatus for pyrolysis of atactic polypropylene

DOEpatents

Staffin, H. Kenneth; Roaper, R. B.

1986-09-23

This invention relates to an apparatus and a method for pyrolytic decomposition of polymeric materials into lower molecular weight products involving the heat treatment of raw polymeric material within reactive conduits submerged in a fluidized bed furnace operated at pyrolizing temperatures.

Boron nitride solid state neutron detector

DOEpatents

Doty, F. Patrick

2004-04-27

The present invention describes an apparatus useful for detecting neutrons, and particularly for detecting thermal neutrons, while remaining insensitive to gamma radiation. Neutrons are detected by direct measurement of current pulses produced by an interaction of the neutrons with hexagonal pyrolytic boron nitride.

Chronic dietary exposure to pyrolytic and petrogenic mixtures of PAHs causes physiological disruption in zebrafish--part I: Survival and growth.

PubMed

Vignet, Caroline; Le Menach, Karyn; Mazurais, David; Lucas, Julie; Perrichon, Prescilla; Le Bihanic, Florane; Devier, Marie-Hélène; Lyphout, Laura; Frère, Laura; Bégout, Marie-Laure; Zambonino-Infante, José-Luis; Budzinski, Hélène; Cousin, Xavier

2014-12-01

The release of polycyclic aromatic hydrocarbons (PAHs) into the environment has increased very substantially over the last decades leading to high concentrations in sediments of contaminated areas. To evaluate the consequences of long-term chronic exposure to PAHs, zebrafish were exposed, from their first meal at 5 days post fertilisation until they became reproducing adults, to diets spiked with three PAH fractions at three environmentally relevant concentrations with the medium concentration being in the range of 4.6-6.7 μg g(-1) for total quantified PAHs including the 16 US-EPA indicator PAHs and alkylated derivatives. The fractions used were representative of PAHs of pyrolytic (PY) origin or of two different oils of differing compositions, a heavy fuel (HO) and a light crude oil (LO). Fish growth was inhibited by all PAH fractions and the effects were sex specific: as determined with 9-month-old adults, exposure to the highest PY inhibited growth of females; exposure to the highest HO and LO inhibited growth of males; also, the highest HO dramatically reduced survival. Morphological analysis indicated a disruption of jaw growth in larvae and malformations in adults. Intestinal and pancreatic enzyme activities were abnormal in 2-month-old exposed fish. These effects may contribute to poor growth. Finally, our results indicate that PAH mixtures of different compositions, representative of situations encountered in the wild, can promote lethal and sublethal effects which are likely to be detrimental for fish recruitment.

The transport phase of pyrolytic oil exiting a fast fluidized bed reactor

NASA Astrophysics Data System (ADS)

Daugaard, Daren Einar

An unresolved and debated aspect in the fast pyrolysis of biomass is whether the bio-oil exits as a vapor or as an aerosol from the pyrolytic reactor. The determination of the bio-oil transport phase will have direct and significant impact on the design of fast pyrolysis systems. Optimization of both the removal of particulate matter and collection of bio-oil will require this information. In addition, the success of catalytic reforming of bio-oil to high-value chemicals will depend upon this transport phase. A variety of experimental techniques were used to identify the transport phase. Some tests were as simple as examining the catch of an inline filter while others attempted to deduce whether vapor or aerosol predominated by examining the pressure drop across a flow restriction. In supplementary testing, the effect of char on aerosol formation and the potential impact of cracking during direct contact filtering are evaluated. The study indicates that for pyrolysis of red oak approximately 90 wt-% of the collected bio-oil existed as a liquid aerosol. Conversely, the pyrolysis of corn starch produced bio-oil predominately in the vapor phase at the exit of the reactor. Furthermore, it was determined that the addition of char promotes the production of aerosols during pyrolysis of corn starch. Direct contact filtering of the product stream did not collect any liquids and the bio-oil yield was not significantly reduced indicating measurable cracking or coking did not occur.

Biochar characteristics produced from rice husks and their sorption properties for the acetanilide herbicide metolachlor.

PubMed

Wei, Lan; Huang, Yufen; Li, Yanliang; Huang, Lianxi; Mar, Nyo Nyo; Huang, Qing; Liu, Zhongzhen

2017-02-01

Rice husk biochar (RHBC) was prepared for use as adsorbents for the herbicide metolachlor. The characteristics and sorption properties of metolachlor adsorbed by the RHBC prepared at different pyrolysis temperatures were determined by analysis of physico-chemical characteristics, Fourier transform infrared spectroscopy (FTIR), Boehm titration, scanning electron microscopy (SEM), and thermodynamics and kinetics adsorption. With increasing pyrolysis temperature, the RHBC surface area greatly increased (from 2.57 to 53.08 m 2  g -1 ). RHBC produced at the highest temperature (750 °C) had the greatest surface area; SEM also showed the formation of a porous surface on RH-750 biochar. The sorption capacity of RHBC also increased significantly with increasing pyrolysis temperature and was characterized by the Freundlich constant K f for the adsorption capacity increasing from 125.17-269.46 (pyrolysis at 300 °C) to 339.94-765.24 (pyrolysis at 750 °C). The results indicated that the surface area and pore diameter of RHBC produced with high pyrolysis temperature (i.e., 750 °C) had the greatest impact on the adsorption of metolachlor. The FTIR, Boehm titration, and SEM analysis showed that the greatest number of surface groups were on RHBC produced at the lowest temperature (300 °C). The biochars produced at different pyrolysis temperatures had different mechanisms of adsorbing metolachlor, which exhibited a transition from hydrogen bonds dominant at low pyrolytic temperature to pore-filling dominant at higher pyrolytic temperature.

Surface Confined Metallosupramolecular Architectures: Formation and STM Characterization

PubMed Central

Li, Shan-Shan; Northrop, Brian H.; Yuan, Qun-Hui; Wan, Li-Jun; Stang, Peter J.

2009-01-01

CONSPECTUS Metallosupramolecular compounds have attracted a great deal of attention over the past two decades largely because of their unique, highly-complex structural characteristics, the fact that they can be prepared with relative ease using coordination-driven self-assembly techniques, and their potential electronic, magnetic, optical, and catalytic properties. In particular, the use of electron-poor square planar Pt(II) transition metals in conjunction with rigid, electron-rich pyridyl donors had enabled the spontaneous self-assembly of a rich library of 2D metallacyclic and 3D metallacage assemblies via the directional-bonding approach. With the tremendous progress that has been made in the preparation and characterization of metallosupramolecules, much attention is now being turned toward fully exploring and developing their materials properties. Assembling metallosupramolecular compounds on solid supports represents a vitally important step toward developing their materials properties. Surfaces provide a means of uniformly aligning and orienting these highly symmetric metallacycles and metallacages, which increases the level of coherence between molecules above that which can be achieved in the solution phase and affords a means of integrating adlayers into a solid-state materials setting. The dynamic nature of kinetically labile Pt(II)-N coordination bonds, however, requires that deposition and imaging conditions be appropriate to retain the assemblies' stability. Toward these aims it is imperative to understand the factors that govern surface self-assembly and the interactions that influence the structure and stability of the resulting adlayer. Such insight can be obtained from Scanning Tunneling Microscopy (STM), which has emerged as a powerful technique for the imaging and characterization of self-assembled adlayers. This account describes the means by which 2D rectangular and square metallacycles and 3D trigonal bipyrimidal and chiral trigonal prism metallacages can be deposited on Highly Oriented Pyrolytic Graphite (HOPG) and Au(111) substrates such that the assemblies remain intact and result in ordered adlayers. The effects of varying the size, symmetry, and dimensionality of supramolecular adsorbates, the choice of substrate, the use of a molecular template, and the effects of chirality have been investigated. These systematic investigations provide much insight into the various adsorbate-adsorbate and substrate-adsorbate interactions that largely determine the architecture of each assembly and affect their performance in a materials setting. Exhibiting the ability to rationally control adlayer formation and structure will greatly enhance the potential of these supramolecules to be used in a variety of applications such as in host-guest sensing/diagnostic systems, molecular electronic devices, and in heterogeneous stereoselective synthesis and catalysis. PMID:19072706

Microcontact Printing Patterning of an HOPG Surface by an Inverse Electron Demand Diels-Alder Reaction.

PubMed

Zhu, Jun; Hiltz, Jonathan; Tefashe, Ushula M; Mauzeroll, Janine; Lennox, R Bruce

2018-06-21

The chemical modification of an sp 2 hybridized carbon surface in a controllable manner is very challenging but also crucial for many applications. An inverse electron demand Diels-Alder (IEDDA) reaction using microcontact printing technique is introduced to spatially control the modification of a highly ordered pyrolytic graphite (HOPG) surface under ambient conditions. The covalent modification was characterized by Raman spectroscopy, XPS, and SECM. Tetrazine derivatives can effectively react with an HOPG surface and with microcontact printing methods resulting in spatially patterned surfaces being produced with micrometer-scale resolution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method and apparatus for pyrolysis of atactic polypropylene

DOEpatents

Staffin, H.K.; Roaper, R.B.

1986-09-23

This invention relates to an apparatus and a method for pyrolytic decomposition of polymeric materials into lower molecular weight products involving the heat treatment of raw polymeric material within reactive conduits submerged in a fluidized bed furnace operated at pyrolyzing temperatures. 1 fig.

High resolution x-ray Thomson scattering measurements from cryogenic hydrogen jets using the linac coherent light source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fletcher, L. B., E-mail: lbfletch@slac.stanford.edu; Galtier, E.; Gamboa, E. J.

2016-11-15

We present the first spectrally resolved measurements of x-rays scattered from cryogenic hydrogen jets in the single photon counting limit. The 120 Hz capabilities of the LCLS, together with a novel hydrogen jet design [J. B. Kim et al., Rev. Sci. Instrum. (these proceedings)], allow for the ability to record a near background free spectrum. Such high-dynamic-range x-ray scattering measurements enable a platform to study ultra-fast, laser-driven, heating dynamics of hydrogen plasmas. This measurement has been achieved using two highly annealed pyrolytic graphite crystal spectrometers to spectrally resolve 5.5 keV x-rays elastically and inelastically scattered from cryogenic hydrogen and focusedmore » on Cornell-SLAC pixel array detectors [S. Herrmann et al., Nucl. Instrum. Methods Phys. Res., Sect. A 718, 550 (2013)].« less

Fixed-bed adsorption study of methylene blue onto pyrolytic tire char

NASA Astrophysics Data System (ADS)

Makrigianni, Vassiliki; Giannakas, Aris; Papadaki, Maria; Albanis, Triantafyllos; Konstantinou, Ioannis

2016-04-01

In this work, the adsorption efficiency of acid treated pyrolytic tire char to cationic methylene blue (MB) dye adsorption from aqueous solutions was investigated by fixed-bed adsorption column experiments. The effects of the initial dye concentration (10 - 40 mg L-1) and feed flow rate (50 - 150 mL min -1) with a fixed bed height (15 cm) were studied in order to determine the breakthrough characteristics of the adsorption system. The Adams-Bohart, Yoon-Nelson and Thomas model were applied to the adsorption of MB onto char at different operational conditions to predict the breakthrough curves and to determine the characteristic parameters of the column. The results showed that the maximum adsorbed quantities decreased with increasing flow rate and increased with increasing initial MB concentration. Breakthrough time and exhaustion time increased with decreasing inlet dye concentration and flow rate. In contrast with Adams-Bohart model, Yoon-Nelson model followed by Thomas model were found more suitable to describe the fixed-bed adsorption of methylene blue by char. The correlation coefficient values R2 for both models at different operating conditions are higher than 0.9 and the low average relative error values provided very good fittings of experimental data at different operating conditions. Higher adsorption capacity of 3.85 mg g -1 was obtained at 15 cm of adsorbent bed height, flow rate of 100 mL min -1and initial MB concentration of 40 mg L-1. Although that activated carbons exhibited higher adsorption capacities in the literature, acid-treated pyrolytic tire char was found to be considerably efficient adsorbent for the removal of MB dye column taking into account the advantages of the simpler production process compared to activated carbons, as well as, the availability of waste tire feedstock and concurrent waste tire management.

Preparation and rheological behavior of polymer-modified asphalts

NASA Astrophysics Data System (ADS)

Yousefi, Ali Akbar

1999-09-01

Different materials and methods were used to prepare and stabilize polymer-modified asphalts. Addition of thermoplastic elastomers improved some technically important properties of asphalt. Due to inherent factors like large density difference between asphalt and polyethylene, many physical methods in which the structure of asphalt is unchanged, failed to stabilize this system. The effect of addition of copolymers and a pyrolytic oil residue derived from used tire rubber were also studied and found to be ineffective on the storage stability of the polymer-asphalt emulsions while high and moderate temperature properties of the asphalt were found to be improved. Finally, the technique of catalytic grafting of polymer on the surface of high-density particles (e.g. carbon black) was used to balance the large density difference between asphalt and polymer. The resulting polymer-asphalts were stable at high temperatures and showed enhanced properties at low and high temperatures.

NUCLEAR REACTOR COOLANT

DOEpatents

Colichman, E.L.

1959-10-20

The formation of new reactor coolants which suppress polymerization resulting from pyrolytic and radiation decomposition is described. The coolants consist of polyphenyls and condensed ring compounds having from two to about four carbon rings and from 0.1 to about 5% of beryllium or magnesium dispersed in the hydrocarbon.

SEM and EDS investigation of a pyrolytic carbon covered C/C composite maxillofacial implant retrieved from the human body after 8 years.

PubMed

Sebők, Béla; Kiss, Gábor; Szabó, Péter J; Rigler, Dániel; Molnár, Milán L; Dobos, Gábor; Réti, Ferenc; Szőcs, Hajnal; Joób, Arpád F; Bogdán, Sándor; Szabó, György

2013-03-01

The long term effect of the human body on a pyrolytic carbon covered C/C composite maxillofacial implant (CarBulat(Tm)) was investigated by comparing the structure, the surface morphology and composition of an implant retrieved after 8 years to a sterilized, but not implanted one. Although the thickness of the carbon fibres constituting the implants did not change during the 8 year period, the surface of the implant retrieved was covered with a thin surface layer not present on the unimplanted implant. The composition of this layer is identical to the composition of the underlying carbon fibres. Calcium can only be detected on the surface as a trace element implying that the new layer is not formed by bone tissue. Residual soft tissue penetrating the bulk material between the carbon fibre bunches was found on the retrieved implant indicating the importance of the surface morphology in tissue growth and adhering to implants.

Effect of oxygen and hydrogen on microstructure of pyrolytic carbon deposited from thermal decomposition of methane and ethanol

NASA Astrophysics Data System (ADS)

Ren, Biyun; Zhang, Shouyang; He, LiQun; Gu, Shengyue

2018-05-01

Chemical vapor infiltration (CVI) is the most extensive industrial preparation of carbon/carbon (C/C) composites. Precursor affects the CVI process considerably. In the present study, using carbon fiber bundles as preforms, methane and ethanol as precursors, the C/C composites were densified by decomposition of various gases in CVI. The thickness and texture of deposited pyrolytic carbon (PyC) were characterized by polarized light microscopy (PLM). The microstructure of PyC was analyzed by Raman spectroscopy. The morphologies of PyC were characterized by scanning electron microscopy (SEM). The composition of PyC was detected by X-ray photoelectron spectroscopy (XPS). Adding hydrogen in methane precursor resulted in a sharp decrease in the deposition rate and texture of PyC. Mixture of methane and ethanol as the precursor improved the deposition rate and texture remarkably. Besides, O element in ethanol was not remained as a constitution of PyC, and it was removed before the formation of PyC.

Effect of Ar{sup +} ion irradiation on the microstructure of pyrolytic carbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Shanglei; Zhang, Dongsheng; Yang, Xinmei

2015-03-21

Pyrolytic carbon (PyC) coatings prepared by chemical vapor deposition were irradiated by 300 keV Ar{sup +} ions. Then, atomic force microscopy, synchrotron-based grazing incidence X-ray diffraction, Raman spectroscopy, X-ray photoemission spectroscopy, and transmission electron microscopy were employed to study how Ar{sup +} irradiation affects the microstructure of PyC, including the microstructural damage mechanisms and physics driving these phenomena. The 300 keV Ar{sup +} ion irradiation deteriorated the structure along the c-axis, which increased the interlayer spacing between graphene layers. With increasing irradiation dose, the density of defect states on the surface of PyC coating increases, and the basal planes gradually loses theirmore » initial ordering resulting in breaks in the lattice and turbulence at the peak damage dose reaches 1.58 displacement per atom (dpa). Surprisingly, the PyC becomes more textured as it becomes richer in structural defects with increasing irradiation dose.« less

A thermochemical-biochemical hybrid processing of lignocellulosic biomass for producing fuels and chemicals.

PubMed

Shen, Yanwen; Jarboe, Laura; Brown, Robert; Wen, Zhiyou

2015-12-01

Thermochemical-biological hybrid processing uses thermochemical decomposition of lignocellulosic biomass to produce a variety of intermediate compounds that can be converted into fuels and chemicals through microbial fermentation. It represents a unique opportunity for biomass conversion as it mitigates some of the deficiencies of conventional biochemical (pretreatment-hydrolysis-fermentation) and thermochemical (pyrolysis or gasification) processing. Thermochemical-biological hybrid processing includes two pathways: (i) pyrolysis/pyrolytic substrate fermentation, and (ii) gasification/syngas fermentation. This paper provides a comprehensive review of these two hybrid processing pathways, including the characteristics of fermentative substrates produced in the thermochemical stage and microbial utilization of these compounds in the fermentation stage. The current challenges of these two biomass conversion pathways include toxicity of the crude pyrolytic substrates, the inhibition of raw syngas contaminants, and the mass-transfer limitations in syngas fermentation. Possible approaches for mitigating substrate toxicities are discussed. The review also provides a summary of the current efforts to commercialize hybrid processing. Copyright © 2015 Elsevier Inc. All rights reserved.

Inhibitors removal from bio-oil aqueous fraction for increased ethanol production.

PubMed

Sukhbaatar, Badamkhand; Li, Qi; Wan, Caixia; Yu, Fei; Hassan, El-Barbary; Steele, Philip

2014-06-01

Utilization of 1,6-anhydro-β-d-glucopyranose (levoglucosan) present (11% w/v) in the water fraction of bio-oil for ethanol production will facilitate improvement in comprehensive utilization of total carbon in biomass. One of the major challenges for conversion of anhydrous sugars from the bio-oil water fraction to bio-ethanol is the presence of inhibitory compounds that slow or impede the microbial fermentation process. Removal of inhibitory compounds was first approached by n-butanol extraction. Optimal ratio of n-butanol and bio-oil water fraction was 1.8:1. Removal of dissolved n-butanol was completed by evaporation. Concentration of sugars in the bio-oil water fraction was performed by membrane filtration and freeze drying. Fermentability of the pyrolytic sugars was tested by fermentation of hydrolyzed sugars with Saccharomyces pastorianus lager yeast. The yield of ethanol produced from pyrolytic sugars in the bio-oil water fraction reached a maximum of 98% of the theoretical yield. Copyright © 2014 Elsevier Ltd. All rights reserved.

Inferring sources of polycyclic aromatic hydrocarbons (PAHs) in sediments from the western Taiwan Strait through end-member mixing analysis.

PubMed

Li, Tao; Sun, Guihua; Ma, Shengzhong; Liang, Kai; Yang, Chupeng; Li, Bo; Luo, Weidong

2016-11-15

Concentration, spatial distribution, composition and sources of polycyclic aromatic hydrocarbons (PAHs) were investigated based on measurements of 16 PAH compounds in surface sediments of the western Taiwan Strait. Total PAH concentrations ranged from 2.41 to 218.54ngg -1 . Cluster analysis identified three site clusters representing the northern, central and southern regions. Sedimentary PAHs mainly originated from a mixture of pyrolytic and petrogenic in the north, from pyrolytic in the central, and from petrogenic in the south. An end-member mixing model was performed using PAH compound data to estimate mixing proportions for unknown end-members (i.e., extreme-value sample points) proposed by principal component analysis (PCA). The results showed that the analyzed samples can be expressed as mixtures of three end-members, and the mixing of different end-members was strongly related to the transport pathway controlled by two currents, which alternately prevail in the Taiwan Strait during different seasons. Copyright © 2016. Published by Elsevier Ltd.

Co-pyrolysis kinetics of sewage sludge and bagasse using multiple normal distributed activation energy model (M-DAEM).

PubMed

Lin, Yan; Chen, Zhihao; Dai, Minquan; Fang, Shiwen; Liao, Yanfen; Yu, Zhaosheng; Ma, Xiaoqian

2018-07-01

In this study, the kinetic models of bagasse, sewage sludge and their mixture were established by the multiple normal distributed activation energy model. Blending with sewage sludge, the initial temperature declined from 437 K to 418 K. The pyrolytic species could be divided into five categories, including analogous hemicelluloses I, hemicelluloses II, cellulose, lignin and bio-char. In these species, the average activation energies and the deviations situated at reasonable ranges of 166.4673-323.7261 kJ/mol and 0.1063-35.2973 kJ/mol, respectively, which were conformed to the references. The kinetic models were well matched to experimental data, and the R 2 were greater than 99.999%y. In the local sensitivity analysis, the distributed average activation energy had stronger effect on the robustness than other kinetic parameters. And the content of pyrolytic species determined which series of kinetic parameters were more important. Copyright © 2018 Elsevier Ltd. All rights reserved.

Pyrolytic characteristics of biomass acid hydrolysis residue rich in lignin.

PubMed

Huang, Yanqin; Wei, Zhiguo; Yin, Xiuli; Wu, Chuangzhi

2012-01-01

Pyrolytic characteristics of acid hydrolysis residue (AHR) of corncob and pinewood (CAHR, WAHR) were investigated using a thermo-gravimetric analyzer (TGA) and a self-designed pyrolysis apparatus. Gasification reactivity of CAHR char was then examined using TGA and X-ray diffractometer. Result of TGA showed that thermal degradation curves of AHR descended smoothly along with temperature increasing from 150 °C to 850 °C, while a "sharp mass loss stage" for original biomass feedstock (OBF) was observed. Char yield from AHR (42.64-30.35 wt.%) was found to be much greater than that from OBF (26.4-19.15 wt.%). In addition, gasification reactivity of CAHR char was lower than that of corncob char, and there was big difference in micro-crystallite structure. It was also found that CAHR char reactivity decreased with pyrolysis temperature, but increased with pyrolysis heating rate and gasification temperature at 850-950 °C. Furthermore, CAHR char reactivity performed better under steam atmosphere than under CO2 atmosphere. Copyright © 2011 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wertsching, Alan Kevin; Trantor, Troy Joseph; Ebner, Matthias Anthony

A method and device for producing secure, high-density tritium bonded with carbon. A substrate comprising carbon is provided. A precursor is intercalated between carbon in the substrate. The precursor intercalated in the substrate is irradiated until at least a portion of the precursor, preferably a majority of the precursor, is transmutated into tritium and bonds with carbon of the substrate forming bonded tritium. The resulting bonded tritium, tritium bonded with carbon, produces electrons via beta decay. The substrate is preferably a substrate from the list of substrates consisting of highly-ordered pyrolytic graphite, carbon fibers, carbon nanotunes, buckministerfullerenes, and combinations thereof.more » The precursor is preferably boron-10, more preferably lithium-6. Preferably, thermal neutrons are used to irradiate the precursor. The resulting bonded tritium is preferably used to generate electricity either directly or indirectly.« less

Alternate Fuel and Power in the Forward Deployed Environment

DTIC Science & Technology

2011-05-01

biomass with a Carbon Footprint will do… 10 PM LAV...Global Vision - Global Mission 5/12/2011 UNCLASSIFIED UNCLASSIFIED Waste to Energy Conversion Grind...pyrolytic gasification *) and harvested as SYNGAS * Patents pending PM LAV...Global Vision - Global Mission 5/12/2011 UNCLASSIFIED UNCLASSIFIED Waste to

Structural analysis of pyrolytic lignins isolated from switchgrass fast pyrolysis oil

USDA-ARS?s Scientific Manuscript database

Structural characterization of lignin extracted from the bio-oil produced by fast pyrolysis of switchgrass (Panicum virgatum) is reported. This new information is important to understanding the utility of lignin as a chemical feedstock in a pyrolysis based biorefinery. Pyrolysis induces a variety of...

Microwave-Mediated Synthesis of Bulky Lanthanide Porphyrin-Phthalocyanine Triple-Deckers: Electrochemical and Magnetic Properties.

PubMed

Jin, Hong-Guang; Jiang, Xiaoqin; Kühne, Irina A; Clair, Sylvain; Monnier, Valérie; Chendo, Christophe; Novitchi, Ghenadie; Powell, Annie K; Kadish, Karl M; Balaban, Teodor Silviu

2017-05-01

Five heteroleptic lanthanide porphyrin-bis-phthalocyanine triple-decker complexes with bulky peripheral groups were prepared via microwave-assisted synthesis and characterized in terms of their spectroscopic, electrochemical, and magnetic properties. These compounds, which were easily obtained under our preparative conditions, would normally not be accessible in large quantities using conventional synthetic methods, as a result of the low yield resulting from steric congestion of bulky groups on the periphery of the phthalocyanine and porphyrin ligands. The electrochemically investigated triple-decker derivatives undergo four reversible one-electron oxidations and three reversible one-electron reductions. The sites of oxidation and reduction were assigned on the basis of redox potentials and UV-vis spectral changes during electron-transfer processes monitored by thin-layer spectroelectrochemistry, in conjunction with assignments of electronic absorption bands of the neutral compounds. Magnetic susceptibility measurements on two derivatives containing Tb III and Dy III metal ions reveal the presence of ferromagnetic interactions, probably resulting from magnetic dipolar interactions. The Tb III derivative shows SMM behavior under an applied field of 0.1 T, where the direct and Orbach process can be determined, resulting in an energy barrier of U eff = 132.0 K. However, Cole-Cole plots reveal the presence of two relaxation processes, the second of which takes place at higher frequencies, with the data conforming to a 1/t ∝ T 7 relation, thus suggesting that it can be assigned to a Raman process. Attempts were made to form two-dimensional (2D) self-assembled networks on a highly oriented pyrolytic graphite (HOPG) surface but were unsuccessful due to bulky peripheral groups on the two Pc macrocycles.

Search for d0-Magnetism in Amorphous MB6 (M = Ca, Sr, Ba) Thin Films

NASA Astrophysics Data System (ADS)

Suter, Andreas; Ackland, Karl; Stilp, Evelyn; Prokscha, Thomas; Salman, Zaher; Coey, Michael

In the past decade there have been various reports on insulating or semi-conducting compounds showing weak ferromagnetic-like properties, even though none of their constituent have partially occupied d or f shells. Among them are HfO2 [1], highly oriented pyrolytic graphite [2], CaB2C2 [3], CaB6 [4,5], and ZnO2 [6]. From the very beginning it has been speculated that lattice defects might play a significant role. These effects can potentially be amplified when these materials are grown in thin film form, due to strain and interface effects. With low-energy μSR (LE-μSR) we studied various amorphous thin films of alkaline earth hexaborides MB6 (M = Ca, Sr, Ba) grown on Al2O3. Furthermore, we studied the starting materials which were used for the pulsed laser deposition (PLD) targets for the films with bulk μSR to ensure the quality of these powders. Similar to the results in Ref. [5] we find an increased second moment of the static width (ZF/LF dynamic Kubo-Toyabe function) compared to the nuclear width which suggest a very weak magnetic contribution which must originate from the electronic system (defect polarization, grain boundary effects, etc.). Two complications arise from the fact that a strong quadrupolar level crossing resonance is found in the hexaborides at rather low field values, and muon diffusion sets in at rather low temperature. The thin film results demonstrate a strong suppression of the muon diffusion which makes it more suitable to search for weak magnetic signatures. Indeed we find essentially a temperature independent second moment equal to the low temperature value found in the starting powders. This indicates that the weak magnetic state is stabilized up to much higher temperatures.

Effect of molecular mass on supramolecular organisation of poly(4,4''-dioctyl-2,2':5',2''-terthiophene).

PubMed

Jaroch, Tomasz; Knor, Marek; Nowakowski, Robert; Zagórska, Małgorzata; Proń, Adam

2008-10-28

The effect of the chain length on the type and extent of the 2D supramolecular organization in poly(4,4''-dioctyl-2,2':5',2''-terthiophene) (PDOTT) monomolecular layers deposited on highly oriented pyrolytic graphite (HOPG) is studied by scanning tunneling microscopy (STM) and analyzed in terms of molecular modeling. The strictly monodispersed fractions of increasing molecular mass used in this study were obtained by chromatographic fractionation of the crude product of 4,4''-dioctyl-2,2':5',2''-terthiophene oxidative polymerization. STM investigations of PDOTT layers, deposited on HOPG from poly- and monodispersed fractions, show that polydispersity can be considered as a key factor seriously limiting supramolecular ordering. This is a consequence of significant differences in the type of supramolecular order observed for molecules of different chain length. It has been demonstrated that shorter molecules (consisting of 6 and 9 thiophene units) form well-defined two-dimensional islands, while the interactions between longer molecules (consisting of 12 and 15 thiophene units) become anisotropic. Consequently, for higher molecular mass fractions, the supramolecular organization is one-dimensional and consists of more or less separated rows of ordered macromolecules. In this case an increase of the chain length leads to amplification of the intermolecular interactions proceeding via interdigitation of the alkyl substituents of adjacent molecules. Polydispersed fractions show much less ordered organization because of the incompatibility of the supramolecular structures of molecules of different molecular masses. This finding is of crucial importance for the application of polythiophene derivatives in organic and molecular electronics since ordered supramolecular organization constitutes the condition sine qua non of good electrical transport properties.

Transport of high intensity laser-generated hot electrons in cone coupled wire targets

NASA Astrophysics Data System (ADS)

Beg, Farhat

2008-04-01

In this talk, we present results from a series of experiments where cone-wire targets were employed both to assess hot electron coupling efficiency, and to reveal the source temperature of the hot electrons. Experiments were performed on the petawatt laser at the Rutherford Appleton Laboratory. A 500J, 1ps laser (I ˜ 4 x 10^20 W/cm-2) was focused by an f/3 off-axis parabolic mirror into hollow aluminum cones joined at their tip to Cu wires of diameters from 10 to 40 μm. The three main diagnostics fielded were a copper Kalpha Bragg crystal imager, a single hit CCD camera spectrometer and a Highly Oriented Pyrolytic Graphite (HOPG) spectrometer. The resulting data were cross-calibrated to obtain the absolute Kalpha yield. Comparison of the axially diminishing absolute Cu Kα intensity with modeling shows that the penetration of the hot electrons is consistent with one dimensional ohmic potential limited transport (1/e length ˜ 100 μm). The laser coupling efficiency to electron energy within the wire is shown to be proportional to the cross sectional area of the wire, reaching 15% for 40 μm wires. We find that the hot electron temperature within the wire was <=750 keV, significantly lower than that predicted by the ponderomotive scaling. A comparison of the experimental results with 2D hybrid PIC simulations using e-PLAS code will be presented and relevance to Fast Ignition will be discussed at the meeting. *In collaboration with J.A. King, M.H. Key, K.U. Akli, R.R. Freeman, J. Green, S. P. Hatchett, D. Hey, P. Jaanimagi, J. Koch, K. L. Lancaster, T. Ma, A.J. MacKinnon, A. MacPhee, R. Mason, P.A. Norreys, P.K Patel, T. Phillips, R. Stephens, W. Theobald, R.P.J. Town, M. Wei, L. Van Woerkom, B. Zhang.

Nucleation, aggregative growth and detachment of metal nanoparticles during electrodeposition at electrode surfaces† †Electronic supplementary information (ESI) available: S1 Scharifker–Hills model, S2 tapping mode-atomic force microscopy (TM-AFM) image of AM grade HOPG, after exposure to a droplet of 50 mM KNO3, S3 distribution of induction times, S4 results of the modified Cottrell fits at different potentials, S5 FE-SEM images of HOPG after control tip breaking, S6 extended current–time trace. See DOI: 10.1039/c4sc02792b Click here for additional data file.

PubMed Central

Lazenby, Robert A.; Kirkman, Paul M.

2015-01-01

The nucleation and growth of metal nanoparticles (NPs) on surfaces is of considerable interest with regard to creating functional interfaces with myriad applications. Yet, key features of these processes remain elusive and are undergoing revision. Here, the mechanism of the electrodeposition of silver on basal plane highly oriented pyrolytic graphite (HOPG) is investigated as a model system at a wide range of length scales, spanning electrochemical measurements from the macroscale to the nanoscale using scanning electrochemical cell microscopy (SECCM), a pipette-based approach. The macroscale measurements show that the nucleation process cannot be modelled as either truly instantaneous or progressive, and that step edge sites of HOPG do not play a dominant role in nucleation events compared to the HOPG basal plane, as has been widely proposed. Moreover, nucleation numbers extracted from electrochemical analysis do not match those determined by atomic force microscopy (AFM). The high time and spatial resolution of the nanoscale pipette set-up reveals individual nucleation and growth events at the graphite basal surface that are resolved and analysed in detail. Based on these results, corroborated with complementary microscopy measurements, we propose that a nucleation-aggregative growth-detachment mechanism is an important feature of the electrodeposition of silver NPs on HOPG. These findings have major implications for NP electrodeposition and for understanding electrochemical processes at graphitic materials generally. PMID:29560200

High-throughput characterization of sediment organic matter by pyrolysis-gas chromatography/mass spectrometry and multivariate curve resolution: A promising analytical tool in (paleo)limnology.

PubMed

Tolu, Julie; Gerber, Lorenz; Boily, Jean-François; Bindler, Richard

2015-06-23

Molecular-level chemical information about organic matter (OM) in sediments helps to establish the sources of OM and the prevalent degradation/diagenetic processes, both essential for understanding the cycling of carbon (C) and of the elements associated with OM (toxic trace metals and nutrients) in lake ecosystems. Ideally, analytical methods for characterizing OM should allow high sample throughput, consume small amounts of sample and yield relevant chemical information, which are essential for multidisciplinary, high-temporal resolution and/or large spatial scale investigations. We have developed a high-throughput analytical method based on pyrolysis-gas chromatography/mass spectrometry and automated data processing to characterize sedimentary OM in sediments. Our method consumes 200 μg of freeze-dried and ground sediment sample. Pyrolysis was performed at 450°C, which was found to avoid degradation of specific biomarkers (e.g., lignin compounds, fresh carbohydrates/cellulose) compared to 650°C, which is in the range of temperatures commonly applied for environmental samples. The optimization was conducted using the top ten sediment samples of an annually resolved sediment record (containing 16-18% and 1.3-1.9% of total carbon and nitrogen, respectively). Several hundred pyrolytic compound peaks were detected of which over 200 were identified, which represent different classes of organic compounds (i.e., n-alkanes, n-alkenes, 2-ketones, carboxylic acids, carbohydrates, proteins, other N compounds, (methoxy)phenols, (poly)aromatics, chlorophyll and steroids/hopanoids). Technical reproducibility measured as relative standard deviation of the identified peaks in triplicate analyses was 5.5±4.3%, with 90% of the RSD values within 10% and 98% within 15%. Finally, a multivariate calibration model was calculated between the pyrolytic degradation compounds and the sediment depth (i.e., sediment age), which is a function of degradation processes and changes in OM source type. This allowed validation of the Py-GC/MS dataset against fundamental processes involved in OM cycling in aquatic ecosystems. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrically conducting polymers for aerospace applications

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Gaier, James R.; Good, Brian S.; Sharp, G. R.; Meador, Michael A.

1991-01-01

Current research on electrically conducting polymers from 1974 to the present is reviewed focusing on the development of materials for aeronautic and space applications. Problems discussed include extended pi-systems, pyrolytic polymers, charge-transfer systems, conductive matrix resins for composite materials, and prospects for the use of conducting polymers in space photovoltaics.

Huyen Dinh | NREL

Science.gov Websites

.; Dinh, H.N. T. Gennett and R. O' (2013). "Nitrogen: unraveling the secret to stable carbon .; Gennett, (2011). "Tuning carbon-based fuel cell catalyst support structures via nitrogen pyrolytic graphite doped with nitrogen." J Phys Chem (C 2011 115:28); pp. 13676-13684. Dinh, H.N.; Ren

Fuels from Recycling Systems

ERIC Educational Resources Information Center

Tillman, David A.

1975-01-01

Three systems, operating at sufficient scale, produce fuels that may be alternatives to oil and gas. These three recycling systems are: Black Clawson Fiberclaim, Franklin, Ohio; Union Carbide, South Charleston, West Virginia; and Union Electric, St. Louis, Missouri. These produce a wet fuel, a pyrolytic gas, and a dry fuel, respectively. (BT)

High resolution x-ray Thomson scattering measurements from cryogenic hydrogen jets using the linac coherent light source

DOE PAGES

Fletcher, L. B.; Zastrau, U.; Galtier, E.; ...

2016-08-15

Here, we present the first spectrally resolved measurements of x-rays scattered from cryogenic hydrogen jets in the single photon counting limit. The 120 Hz capabilities of the LCLS, together with a novel hydrogen jet design [J. B. Kim et al., Rev. Sci. Instrum. (these proceedings)], allow for the ability to record a near background free spectrum. Such high-dynamic-range x-ray scattering measurements enable a platform to study ultra-fast, laser-driven, heating dynamics of hydrogen plasmas. This measurement has been achieved using two highly annealed pyrolytic graphite crystal spectrometers to spectrally resolve 5.5 keV x-rays elastically and inelastically scattered from cryogenic hydrogen andmore » focused on Cornell-SLAC pixel array detectors [S. Herrmann et al., Nucl. Instrum. Methods Phys. Res., Sect. A 718, 550 (2013)].« less

Diffusion, Thermal Properties and Chemical Compatibilities of Select MAX Phases with Materials For Advanced Nuclear Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barsoum, Michel; Bentzel, Grady; Tallman, Darin J.

2016-04-04

The demands of Gen IV nuclear power plants for long service life under neutron irradiation at high temperature are severe. Advanced materials that would withstand high temperatures (up to 1000+ ºC) to high doses in a neutron field would be ideal for reactor internal structures and would add to the long service life and reliability of the reactors. The objective of this work is to investigate the chemical compatibility of select MAX with potential materials that are important for nuclear energy, as well as to measure the thermal transport properties as a function of neutron irradiation. The chemical counterparts chosenmore » for this work are: pyrolytic carbon, SiC, U, Pd, FLiBe, Pb-Bi and Na, the latter 3 in the molten state. The thermal conductivities and heat capacities of non-irradiated MAX phases will be measured.« less

Interfacial nanobubbles on atomically flat substrates with different hydrophobicities.

PubMed

Wang, Xingya; Zhao, Binyu; Ma, Wangguo; Wang, Ying; Gao, Xingyu; Tai, Renzhong; Zhou, Xingfei; Zhang, Lijuan

2015-04-07

The dependence of the morphology of interfacial nanobubbles on atomically flat substrates with different wettability ranges was investigated by using PeakForce quantitative nanomechanics. Interfacial nanobubbles were formed and imaged on silicon nitride (Si3N4), mica, and highly ordered pyrolytic graphite (HOPG) substrates that were partly covered by reduced graphene oxide (rGO). The contact angles and sizes of those nanobubbles were measured under the same conditions. Nanobubbles with the same lateral width exhibited different heights on the different substrates, with the order Si3N4≈mica>rGO>HOPG, which is consistent with the trend of the hydrophobicity of the substrates. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Approaches to flame resistant polymeric materials

NASA Technical Reports Server (NTRS)

Liepins, R.

1975-01-01

Four research and development areas are considered for further exploration in the quest of more flame-resistant polymeric materials. It is suggested that improvements in phenolphthalein polycarbonate processability may be gained through linear free energy relationship correlations. Looped functionality in the backbone of a polymer leads to both improved thermal resistance and increased solubility. The guidelines used in the pyrolytic carbon production constitute a good starting point for the development of improved flame-resistant materials. Numerous organic reactions requiring high temperatures and the techniques of protected functionality and latent functionality constitute the third area for exploration. Finally, some well-known organic reactions are suggested for the formation of polymers that were not made before.

Effect of mechanical and electrical stimuli in conductive atomic force microscopy with noble metal-coated tips

NASA Astrophysics Data System (ADS)

Zade, Vishal; Kang, Hung-Sen; Lee, Min Hwan

2018-01-01

Conductive atomic force microscopy has been widely employed to study the localized electrical properties of a wide range of substrates in non-vacuum conditions by the use of noble metal-coated tips. However, quantitative characterization of the electrical properties was often precluded by unpredictable changes in the tip apex morphology, and/or electronic transport characteristics of undesired oxide overcoats on the tip. In this paper, the impact of mechanical and electrical stimuli on the apex geometry of gold coated tips and electrical conduction properties at the tip-substrate contact is discussed by choosing gold and highly ordered pyrolytic graphite as the representative tip and substrate materials, respectively.

Femtosecond laser-induced ripple patterns for homogenous nanostructuring of pyrolytic carbon heart valve implant

NASA Astrophysics Data System (ADS)

Stępak, Bogusz; Dzienny, Paulina; Franke, Volker; Kunicki, Piotr; Gotszalk, Teodor; Antończak, Arkadiusz

2018-04-01

Laser-induced periodic surface structures (LIPSS) are highly periodic wavy surface features which are frequently smaller than incident light wavelength that bring possibility of nanostructuring of many materials. In this paper the possibility of using them to homogeneously structure the surface of artificial heart valve made of PyC was examined. By changing laser irradiation parameters such like energy density and pulse separation the most suitable conditions were established for 1030 nm wavelength. A wide spectrum of periodicities and geometries was obtained. Interesting side effects like creating a thin shell-like layer were observed. Modified surfaces were examined using EDX and Raman spectroscopy to determine change in elemental composition of surface.

Investigations by Protein Film Electrochemistry of Alternative Reactions of Nickel-Containing Carbon Monoxide Dehydrogenase.

PubMed

Wang, Vincent C-C; Islam, Shams T A; Can, Mehmet; Ragsdale, Stephen W; Armstrong, Fraser A

2015-10-29

Protein film electrochemistry has been used to investigate reactions of highly active nickel-containing carbon monoxide dehydrogenases (CODHs). When attached to a pyrolytic graphite electrode, these enzymes behave as reversible electrocatalysts, displaying CO2 reduction or CO oxidation at minimal overpotential. The O2 sensitivity of CODH is suppressed by adding cyanide, a reversible inhibitor of CO oxidation, or by raising the electrode potential. Reduction of N2O, isoelectronic with CO2, is catalyzed by CODH, but the reaction is sluggish, despite a large overpotential, and results in inactivation. Production of H2 and formate under highly reducing conditions is consistent with calculations predicting that a nickel-hydrido species might be formed, but the very low rates suggest that such a species is not on the main catalytic pathway.

SUMMARY OF THE SEVENTH MEETING OF THE REFRACTORY COMPOSITES WORKING GROUP

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gibeaut, W.A.; Ogden, H.R.

1963-05-30

Information on refractory composites for use above 2500 deg F is summarized. Reports are concerned with protective coatings, insulating ceramics, materials for rocket thrust chambers, dispersion strengthening of metals, joining of refractory materials, and testing techniques. The problem of accelerated failure of silicide coatings under conditions of very low air pressure at high temperatures is studied. Although the maximum temperature capability of most silicide coatings is reduced about 50 theta deg at low air pressures, several coatings can protect molybdenum for 1/2 hr at 2800 to 3000 deg F under these conditions. The tin-aluminum coating also is susceptible to earlymore » failure at reduced pressure. An evaluation of the mechanical properties of 6-mil foils of D- 36, B-68, and TZM coated with commercial coatings demonstrated that some coatings seriously degrade substrate mechanical properties. Research on thermal- protection systems for re-entry vehicles whose surface temperatures reach from 3300 to 5500 deg F has resulted in agreement upon oxide coatings and thick metal- reinforced oxide composites. Simple plasmaarc-sprayed oxide coatings have demonstrated adequate oxidation resistance, but their structural stability in cyclic thermal exposure is inferior to metal-reinforced oxide. Thin unreinforced oxide coatings tend to spall in tests involving cyclic heating. A metal- reinforced oxide composite (reinforcement welded to substrate) has survived cyclic tests such as five 3-minute exposures at 4500 deg F without failing. A new carbon material called glassy carbon has demonstrnted better oxidation resistance than pyrolytic graphite at very high temperatures. The erosion resistance of pyrolytic graphite coatings on regular graphite in rocket firing tests using solid propellants is encouraging. There is considerable interest in fabricating small radiation-cooled rocket thrust chambers by plasma arc spraying. The design concept of internal reinforcement of sprayed-metal rocket chambers with wrought ductile wife appears impractical because of poor bonding and porosity around the wire. (auth)« less

Thermal Decomposition Model Development of EN-7 and EN-8 Polyurethane Elastomers.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keedy, Ryan Michael; Harrison, Kale Warren; Cordaro, Joseph Gabriel

Thermogravimetric analysis - gas chromatography/mass spectrometry (TGA- GC/MS) experiments were performed on EN-7 and EN-8, analyzed, and reported in [1] . This SAND report derives and describes pyrolytic thermal decomposition models for use in predicting the responses of EN-7 and EN-8 in an abnormal thermal environment.

Materials Characteristics and Surface Morphology of a Cesium Iodide Coated Carbon Velvet Cathode (POSTPRINT)

DTIC Science & Technology

2009-03-31

cathodes consist of an array of carbon fibers pyrolytically bonded to a carbon substrate. The fibers then receive a CsI coating using either a...the oil side of the vacuum interface along the cathode shank. Current transformers provide current measurements of the cathode current, again

Electron microscopy study of Pd, Ag, and Cs in carbon areas in the locally corroded SiC layer in a neutron-irradiated TRISO fuel particle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wen, Haiming; van Rooyen, Isabella J.; Hunn, John D.

Here, a detailed electron microscopy study was performed on focused ion beam-prepared lamellae from different locations relative to a crack across the inner pyrolytic carbon layer of a neutron-irradiated tristructural isotropic-coated particle. The distribution and composition of fission products across the inner pyrolytic carbon and silicon carbide (SiC) layers were studied. Previously, this crack was identified in the particle that released significant inventory fractions of cesium and silver during irradiation and displayed localized palladium pileup with SiC degradation. In this study, carbon areas were found in the SiC layer close to the crack tip and they had precipitates that consistedmore » mostly of palladium silicides or palladium, with silver and/or cadmium frequently identified. Results confirmed that areas in the SiC layer close to the crack tip with localized accumulation of palladium were corroded by palladium, forming pure carbon areas and palladium silicide that provided pathways for silver, cadmium and cesium migration.« less

Diffraction of real and virtual photons in a pyrolytic graphite crystal as source of intensive quasimonochromatic X-ray beam

NASA Astrophysics Data System (ADS)

Bogomazova, E. A.; Kalinin, B. N.; Naumenko, G. A.; Padalko, D. V.; Potylitsyn, A. P.; Sharafutdinov, A. F.; Vnukov, I. E.

2003-01-01

A series of experiments on the parametric X-rays radiation (PXR) generation and radiation soft component diffraction of relativistic electrons in pyrolytic graphite (PG) crystals have been carried out at the Tomsk synchrotron. It is shown that the experimental results with PG crystals are explained by the kinematic PXR theory if we take into account a contribution of the real photons diffraction (transition radiation, bremsstrahlung and PXR photons as well). The measurements of the emission spectrum of channeled electrons in the photon energy range much smaller than the characteristic energy of channeling radiation have been performed with a crystal-diffraction spectrometer. For electrons incident along the <1 1 0> axis of a silicon crystal, the radiation intensity in the energy range 30⩽ ω⩽360 keV exceeds the bremsstrahlung one almost by an order of magnitude. Different possibilities to create an effective source of the monochromatic X-ray beam based on the real and virtual photons diffraction in the PG crystals have been considered.

Voltammetric studies of hemoglobin-coated polystyrene latex bead films on pyrolytic graphite electrodes.

PubMed

Sun, Hong; Hu, Naifei

2004-08-01

A novel hemoglobin (Hb)-coated polystyrene (PS) latex bead film was deposited on pyrolytic graphite (PG) electrode surface. In the first step, positively charged Hb molecules in pH 5.0 buffers were adsorbed on the surface of negatively charged, 500 nm diameter PS latex beads bearing sulfate groups by electrostatic interaction. The aqueous dispersion of Hb-coated PS particles was then deposited on the surface of PG electrodes and, after evaporation of the solvent, Hb-PS films were formed. The Hb-PS film electrodes exhibited a pair of well-defined, quasi-reversible cyclic voltammetric (CV) peaks at about -0.36 V vs. SCE in pH 7.0 buffers, characteristic of Hb heme Fe(III)/Fe(II) redox couples. Positions of Soret absorption band of Hb-PS films suggest that Hb retains its near-native structure in the films in its dry form and in solution at medium pH. The Hb in PS films was also acted as a catalyst to catalyze electrochemical reduction of various substrates such as trichloroacetic acid (TCA), nitrite, oxygen and hydrogen peroxide.

Potential of genetically engineered hybrid poplar for pyrolytic production of bio-based phenolic compounds.

PubMed

Toraman, Hilal E; Vanholme, Ruben; Borén, Eleonora; Vanwonterghem, Yumi; Djokic, Marko R; Yildiz, Guray; Ronsse, Frederik; Prins, Wolter; Boerjan, Wout; Van Geem, Kevin M; Marin, Guy B

2016-05-01

Wild-type and two genetically engineered hybrid poplar lines were pyrolyzed in a micro-pyrolysis (Py-GC/MS) and a bench scale setup for fast and intermediate pyrolysis studies. Principal component analysis showed that the pyrolysis vapors obtained by micro-pyrolysis from wood of caffeic acid O-methyltransferase (COMT) and caffeoyl-CoA O-methyltransferase (CCoAOMT) down-regulated poplar trees differed significantly from the pyrolysis vapors obtained from non-transgenic control trees. Both fast micro-pyrolysis and intermediate pyrolysis of transgenic hybrid poplars showed that down-regulation of COMT can enhance the relative yield of guaiacyl lignin-derived products, while the relative yield of syringyl lignin-derived products was up to a factor 3 lower. This study indicates that lignin engineering via genetic modifications of genes involved in the phenylpropanoid and monolignol biosynthetic pathways can help to steer the pyrolytic production of guaiacyl and syringyl lignin-derived phenolic compounds such as guaiacol, 4-methylguaiacol, 4-ethylguaiacol, 4-vinylguaiacol, syringol, 4-vinylsyringol, and syringaldehyde present in the bio-oil. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fast pyrolysis of palm kernel shells: influence of operation parameters on the bio-oil yield and the yield of phenol and phenolic compounds.

PubMed

Kim, Seon-Jin; Jung, Su-Hwa; Kim, Joo-Sik

2010-12-01

Palm kernel shells were pyrolyzed in a pyrolysis plant equipped with a fluidized-bed reactor and a char-separation system. The influence of reaction temperature, feed size and feed rate on the product spectrum was also investigated. In addition, the effect of reaction temperature on the yields of phenol and phenolic compounds in the bio-oil was examined. The maximum bio-oil yield was 48.7 wt.% of the product at 490 degrees C. The maximum yield of phenol plus phenolic compounds amounted to about 70 area percentage at 475 degrees C. The yield of pyrolytic lignin after its isolation from the bio-oil was approximately 46 wt.% based on the water and ash free oil. The pyrolytic lignin was mainly composed of phenol, phenolic compounds and oligomers of coniferyl, sinapyl and p-coumaryl alcohols. From the result of a GPC analysis, the number average molecular weight and the weight average molecular weight were 325 and 463 g/mol, respectively. 2010 Elsevier Ltd. All rights reserved.

Enhancing the quality of bio-oil and selectivity of phenols compounds from pyrolysis of anaerobic digested rice straw.

PubMed

Liang, Jiajin; Lin, Yunqin; Wu, Shubin; Liu, Chao; Lei, Ming; Zeng, Chao

2015-04-01

This study investigated the thermal decomposition characteristics and pyrolytic products of anaerobic digested rice straw (ADRS) by thermogravimetric (TG) and pyrolysis-gas chromatograph/mass spectrometry (Py-GC/MS) analysis. Compared with the raw rice straw (RS), the thermal decomposition temperature of ADRS was shifted to higher temperature zone and the second decomposition zone of cellulose (Toffset(c)-Tpeak) became narrower (14 °C less), which indicated that the composition of rice straw were changed significantly by the anaerobic digestion pretreatment. Py-GC/MS analysis showed that the quality of the bio-oil and the selectivity of pyrolytic products could be obviously improved by anaerobic digestion. The total yields of alcohols, acids, aldehydes, furans, anhydrosugars, and ketones pyrolysis substances decreased, while the yield of phenols increased. The yield of 4-Vinylphenol (4-VP) increased from 29.33%, 8.21% and 5.76% to 34.93%, 12.46% and 7.68% at 330, 450 and 650 °C, respectively, after anaerobic digestion. Copyright © 2015 Elsevier Ltd. All rights reserved.

Co-pyrolysis of lignocellulosic biomass and microalgae: Products characteristics and interaction effect.

PubMed

Chen, Wei; Chen, Yingquan; Yang, Haiping; Xia, Mingwei; Li, Kaixu; Chen, Xu; Chen, Hanping

2017-12-01

Co-pyrolysis of biomass has a potential to change the quality of pyrolytic bio-oil. In this work, co-pyrolysis of bamboo, a typical lignocellulosic biomass, and Nannochloropsis sp. (NS), a microalgae, was carried out in a fixed bed reactor at a range of mixing ratio of NS and bamboo, to find out whether the quality of pyrolytic bio-oil was improved. A significant improvement on bio-oil after co-pyrolysis of bamboo and NS was observed that bio-oil yield increased up to 66.63wt% (at 1:1) and the content of long-chain fatty acids in bio-oil also dramatically increased (the maximum up to 50.92% (13.57wt%) at 1:1) whereas acetic acid, O-containing species, and N-containing compounds decreased greatly. Nitrogen transformation mechanism during co-pyrolysis also was explored. Results showed that nitrogen in microalgae preferred to transform into solid char and gas phase during co-pyrolysis, while more pyrrolic-N and quaternary-N generated with diminishing protein-N and pyridinic-N in char. Copyright © 2017 Elsevier Ltd. All rights reserved.

Contamination of polycyclic aromatic hydrocarbons (PAHs) in surface sediments and plants of mangrove swamps in Shenzhen, China.

PubMed

Li, Fenglan; Zeng, Xiaokang; Yang, Junda; Zhou, Kai; Zan, Qijie; Lei, Anping; Tam, Nora F Y

2014-08-30

The concentrations of 16 individual and total polycyclic aromatic hydrocarbons (∑PAHs) in sediments, roots and leaves of three mangrove swamps in Shenzhen, China, namely Futian, Baguang and Waterlands, were determined. The mean concentration of ∑PAHs in Futian (4480 ng g(-1)) was significantly higher than that in Baguang (1262 ng g(-1)) and Waterlands (2711 ng g(-1)). Among the 16 PAHs, the concentration of naphthalene was the highest. Based on the ratios of phenanthrene/anthracene and fluoranthene/pyrene, PAHs in Futian and Waterlands came from petrogenic and pyrolytic sources, while Baguang was mainly from pyrolytic. More PAHs were accumulated in leaves, as reflected by its higher mean concentration of ∑PAHs (3697 ng g(-1)) and bioconcentration factor of PAHs (BCF) (>1.5) than that in roots. The BCF values in plants collected from Futian were significantly higher than that from Waterlands. These results indicated that more attention should be paid to the PAH contamination in Futian. Copyright © 2014 Elsevier Ltd. All rights reserved.

Pyrolytic Treatment and Fertility Enhancement of Soils Contaminated with Heavy Hydrocarbons.

PubMed

Vidonish, Julia E; Zygourakis, Kyriacos; Masiello, Caroline A; Gao, Xiaodong; Mathieu, Jacques; Alvarez, Pedro J J

2016-03-01

Pyrolysis of contaminated soils at 420 °C converted recalcitrant heavy hydrocarbons into "char" (a carbonaceous material similar to petroleum coke) and enhanced soil fertility. Pyrolytic treatment reduced total petroleum hydrocarbons (TPH) to below regulatory standards (typically <1% by weight) within 3 h using only 40-60% of the energy required for incineration at 600-1200 °C. Formation of polycyclic aromatic hydrocarbons (PAHs) was not observed, with post-pyrolysis levels well below applicable standards. Plant growth studies showed a higher biomass production of Arabidopsis thaliana and Lactuca sativa (Simpson black-seeded lettuce) (80-900% heavier) in pyrolyzed soils than in contaminated or incinerated soils. Elemental analysis showed that pyrolyzed soils contained more carbon than incinerated soils (1.4-3.2% versus 0.3-0.4%). The stark color differences between pyrolyzed and incinerated soils suggest that the carbonaceous material produced via pyrolysis was dispersed in the form of a layer coating the soil particles. Overall, these results suggest that soil pyrolysis could be a viable thermal treatment to quickly remediate soils impacted by weathered oil while improving soil fertility, potentially enhancing revegetation.

Electron microscopy study of Pd, Ag, and Cs in carbon areas in the locally corroded SiC layer in a neutron-irradiated TRISO fuel particle

DOE PAGES

Wen, Haiming; van Rooyen, Isabella J.; Hunn, John D.; ...

2018-05-07

Here, a detailed electron microscopy study was performed on focused ion beam-prepared lamellae from different locations relative to a crack across the inner pyrolytic carbon layer of a neutron-irradiated tristructural isotropic-coated particle. The distribution and composition of fission products across the inner pyrolytic carbon and silicon carbide (SiC) layers were studied. Previously, this crack was identified in the particle that released significant inventory fractions of cesium and silver during irradiation and displayed localized palladium pileup with SiC degradation. In this study, carbon areas were found in the SiC layer close to the crack tip and they had precipitates that consistedmore » mostly of palladium silicides or palladium, with silver and/or cadmium frequently identified. Results confirmed that areas in the SiC layer close to the crack tip with localized accumulation of palladium were corroded by palladium, forming pure carbon areas and palladium silicide that provided pathways for silver, cadmium and cesium migration.« less

Pyrolysis reaction models of waste tires: Application of Master-Plots method for energy conversion via devolatilization.

PubMed

Irmak Aslan, Dilan; Parthasarathy, Prakash; Goldfarb, Jillian L; Ceylan, Selim

2017-10-01

Land applied disposal of waste tires has far-reaching environmental, economic, and human health consequences. Pyrolysis represents a potential waste management solution, whereby the solid carbonaceous residue is heated in the absence of oxygen to produce liquid and gaseous fuels, and a solid char. The design of an efficient conversion unit requires information on the reaction kinetics of pyrolysis. This work is the first to probe the appropriate reaction model of waste tire pyrolysis. The average activation energy of pyrolysis was determined via iso-conversional methods over a mass fraction conversion range between 0.20 and 0.80 to be 162.8±23.2kJmol -1 . Using the Master Plots method, a reaction order of three was found to be the most suitable model to describe the pyrolytic decomposition. This suggests that the chemical reactions themselves (cracking, depolymerization, etc.), not diffusion or boundary layer interactions common with carbonaceous biomasses, are the rate-limiting steps in the pyrolytic decomposition of waste tires. Copyright © 2017 Elsevier Ltd. All rights reserved.

Co-pyrolysis behaviour and kinetic of two typical solid wastes in China and characterisation of activated carbon prepared from pyrolytic char.

PubMed

Ma, Yuhui; Niu, Ruxuan; Wang, Xiaona; Wang, Qunhui; Wang, Xiaoqiang; Sun, Xiaohong

2014-11-01

This is the first study on the co-pyrolysis of spent substrate of Pleurotus ostreatus and coal tar pitch, and the activated carbon prepared from the pyrolytic char. Thermogravimetry (TG) analysis was carried out taking spent substrate, coal tar pitch and spent substrate-coal tar pitch mixture. The activation energies of pyrolysis reactions were obtained via the Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose methods. The kinetic models were determined by the master-plots method. The activated carbons were characterised by N2-adsorption, Fourier transform infrared spectroscopy and X-ray diffraction. Experimental results demonstrated a synergistic effect happened during co-pyrolysis, which was characterised by a decreased maximum decomposition rate and an enhanced char yield. The average activation energies of the pyrolysis reactions of spent substrate, coal tar pitch and the mixture were 115.94, 72.92 and 94.38 kJ mol(-1) for the Flynn-Wall-Ozawa method, and 112.17, 65.62 and 89.91 kJ mol(-1) for the Kissinger-Akahira-Sunose method. The reaction model functions were f(α) = (1-α)(3.42), (1-α)(1.72) and (1-α)(3.07) for spent substrate, coal tar pitch and the mixture, respectively. The mixture char-derived activated carbon had a Brunauer-Emmett-Teller surface area up to 1337 m(2) g(-1) and a total pore volume of 0.680 cm(3) g(-1). Mixing spent substrate with coal tar pitch led to the creation of more micropores and a higher surface area compared with the single spent substrate and coal tar pitch char. Also, the mixture char-derived activated carbon had a higher proportion of aromatic stacking. This study provides a reference for the utilisation of spent substrate and coal tar pitch via co-pyrolysis, and their pyrolytic char as a promising precursor of activated carbon. © The Author(s) 2014.

Effect of high surface area activated carbon on thermal degradation of jet fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gergova, K.; Eser, S.; Arumugam, R.

1995-05-01

Different solid carbons added to jet fuel during thermal stressing cause substantial changes in pyrolytic degradation reactions. Activated carbons, especially high surface area activated carbons were found to be very effective in suppressing solid deposition on metal reactor walls during stressing at high temperatures (425 and 450{degrees}C). The high surface area activated carbon PX-21 prevented solid deposition on reactor walls even after 5h at 450{degrees}C. The differences seen in the liquid product composition when activated carbon is added indicated that the carbon surfaces affect the degradation reactions. Thermal stressing experiments were carried out on commercial petroleum-derived JPTS jet fuel. Wemore » also used n-octane and n-dodecane as model compounds in order to simplify the study of the chemical changes which take place upon activated carbon addition. In separate experiments, the presence of a hydrogen donor, decalin, together with PX-21 was also studied.« less

Development of a Scanning Microscale Fast Neutron Irradiation Platform for Examining the Correlation Between Local Neutron Damage and Graphite Microstructure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pinhero, Patrick; Windes, William

2015-03-10

The fast particle radiation damage effect of graphite, a main material in current and future nuclear reactors, has significant influence on the utilization of this material in fission and fusion plants. Atoms on graphite crystals can be easily replaced or dislocated by fast protons and result in interstitials and vacancies. The currently accepted model indicates that after most of the interstitials recombine with vacancies, surviving interstitials form clusters and furthermore gather to create loops with each other between layers. Meanwhile, surviving vacancies and interstitials form dislocation loops on the layers. The growth of these inserted layers cause the dimensional increase,more » i.e. swelling, of graphite. Interstitial and vacancy dislocation loops have been reported and they can easily been observed by electron microscope. However, observation of the intermediate atom clusters becomes is paramount in helping prove this model. We utilize fast protons generated from the University of Missouri Research Reactor (MURR) cyclotron to irradiate highly- oriented pyrolytic graphite (HOPG) as target for this research. Post-irradiation examination (PIE) of dosed targets with high-resolution transmission electron microscopy (HRTEM) has permit observation and analysis of clusters and dislocation loops to support the proposed theory. Another part of the research is to validate M.I. Heggie’s Ruck and Tuck model, which introduced graphite layers may fold under fast particle irradiation. Again, we employed microscopy to image irradiated specimens to determine how the extent of Ruck and Tuck by calculating the number of folds as a function of dose. Our most significant accomplishment is the invention of a novel class of high-intensity pure beta-emitters for long-term lightweight batteries. We have filed four invention disclosure records based on the research conducted in this project. These batteries are lightweight because they consist of carbon and tritium and can be fabricated to conform to many geometric shapes. In addition, we have published eight peer-reviewed American Nuclear Society (ANS) transactions, and presented our findings at ANS National Meetings, and several universities.« less

NANOWIRE CATHODE MATERIAL FOR LITHIUM-ION BATTERIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

John Olson, PhD

2004-07-21

This project involved the synthesis of nanowire ã-MnO2 and characterization as cathode material for high-power lithium-ion batteries for EV and HEV applications. The nanowire synthesis involved the edge site decoration nanowire synthesis developed by Dr. Reginald Penner at UC Irvine (a key collaborator in this project). Figure 1 is an SEM image showing ã-MnO2 nanowires electrodeposited on highly oriented pyrolytic graphite (HOPG) electrodes. This technique is unique to other nanowire template synthesis techniques in that it produces long (>500 um) nanowires which could reduce or eliminate the need for conductive additives due to intertwining of fibers. Nanowire cathode for lithium-ionmore » batteries with surface areas 100 times greater than conventional materials can enable higher power batteries for electric vehicles (EVs) and hybrid electric vehicles (HEVs). The synthesis of the ã-MnO2 nanowires was successfully achieved. However, it was not found possible to co-intercalate lithium directly in the nanowire synthesis. Based on input from proposal reviewers, the scope of the project was altered to attempt the conversion into spinel LiMn2O4 nanowire cathode material by solid state reaction of the ã-MnO2 nanowires with LiNO3 at elevated temperatures. Attempts to perform the conversion on the graphite template were unsuccessful due to degradation of the graphite apparently caused by oxidative attack by LiNO3. Emphasis then shifted to quantitative removal of the nanowires from the graphite, followed by the solid state reaction. Attempts to quantitatively remove the nanowires by several techniques were unsatisfactory due to co-removal of excess graphite or poor harvesting of nanowires. Intercalation of lithium into ã-MnO2 electrodeposited onto graphite was demonstrated, showing a partial demonstration of the ã-MnO2 material as a lithium-ion battery cathode material. Assuming the issues of nanowires removal can be solved, the technique does offer potential for creating high-power lithium-ion battery cathode needed for advanced EV and HEVs. Several technical advancements will still be required to meet this goal, and are likely topics for future SBIR feasibility studies.« less

Stacked graphene nanofibers for electrochemical oxidation of DNA bases.

PubMed

Ambrosi, Adriano; Pumera, Martin

2010-08-21

In this article, we show that stacked graphene nanofibers (SGNFs) demonstrate superior electrochemical performance for oxidation of DNA bases over carbon nanotubes (CNTs). This is due to an exceptionally high number of accessible graphene sheet edges on the surface of the nanofibers when compared to carbon nanotubes, as shown by transmission electron microscopy and Raman spectroscopy. The oxidation signals of adenine, guanine, cytosine, and thymine exhibit two to four times higher currents than on CNT-based electrodes. SGNFs also exhibit higher sensitivity than do edge-plane pyrolytic graphite, glassy carbon, or graphite microparticle-based electrodes. We also demonstrate that influenza A(H1N1)-related strands can be sensitively oxidized on SGNF-based electrodes, which could therefore be applied to label-free DNA analysis.

Characterization of fast pyrolysis products generated from several western USA woody species

Treesearch

Jacqueline M. Jarvis; Deborah S. Page-Dumroese; Nathaniel M. Anderson; Yuri Corilo; Ryan P. Rodgers

2014-01-01

Woody biomass has the potential to be utilized at an alternative fuel source through its pyrolytic conversion. Here, fast pyrolysis bio-oils derived from several western USA woody species are characterized by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to determine molecular-level composition. The...

Laser-assisted solar-cell metallization processing

NASA Technical Reports Server (NTRS)

Dutta, S.

1984-01-01

A photolytic metal deposition system using a focused continuous wave ultraviolet laser, a photolytic metal deposition system using a mask and ultraviolet flood illumination, and a pyrolytic metal deposition system using a focused continuous wave laser were studied. Fabrication of solar cells, as well as characterization to determine the effects of transient heat on solar cell junctions were investigated.

Packed-bed catalytic cracking of oak derived pyrolytic vapors

USDA-ARS?s Scientific Manuscript database

Catalytic upgrading of pyrolysis vapors derived from oak was carried out using a fixed-bed catalytic column at 425 deg C. The vapors were drawn by splitting a fraction from the full stream of vapors produced at 500 deg C in a 5 kg/hr bench-scale fast pyrolysis reactor system downstream the cyclone s...

Sorption of four hydrophobic organic contaminants by biochars derived from maize straw, wood dust and swine manure at different pyrolytic temperatures

USDA-ARS?s Scientific Manuscript database

To study the interactions between biochars and hydrophobic organic compounds (HOCs), the adsorption of HOCs with varied physical-chemical properties on biochars produced from three feedstock sources (maize straw (MABs), pine wood dust (WDBs) and swine manure (SWBs)) was evaluated. The biochars produ...

Moiré-Modulated Conductance of Hexagonal Boron Nitride Tunnel Barriers.

PubMed

Summerfield, Alex; Kozikov, Aleksey; Cheng, Tin S; Davies, Andrew; Cho, Yong-Jin; Khlobystov, Andrei N; Mellor, Christopher J; Foxon, C Thomas; Watanabe, Kenji; Taniguchi, Takashi; Eaves, Laurence; Novoselov, Kostya S; Novikov, Sergei V; Beton, Peter H

2018-06-27

Monolayer hexagonal boron nitride (hBN) tunnel barriers investigated using conductive atomic force microscopy reveal moiré patterns in the spatial maps of their tunnel conductance consistent with the formation of a moiré superlattice between the hBN and an underlying highly ordered pyrolytic graphite (HOPG) substrate. This variation is attributed to a periodc modulation of the local density of states and occurs for both exfoliated hBN barriers and epitaxially grown layers. The epitaxial barriers also exhibit enhanced conductance at localized subnanometer regions which are attributed to exposure of the substrate to a nitrogen plasma source during the high temperature growth process. Our results show clearly a spatial periodicity of tunnel current due to the formation of a moiré superlattice and we argue that this can provide a mechanism for elastic scattering of charge carriers for similar interfaces embedded in graphene/hBN resonant tunnel diodes.

Pyrolytic Waste Plastic Oil and Its Diesel Blend: Fuel Characterization.

PubMed

Khan, M Z H; Sultana, M; Al-Mamun, M R; Hasan, M R

2016-01-01

The authors introduced waste plastic pyrolysis oil (WPPO) as an alternative fuel characterized in detail and compared with conventional diesel. High density polyethylene, HDPE, was pyrolyzed in a self-designed stainless steel laboratory reactor to produce useful fuel products. HDPE waste was completely pyrolyzed at 330-490°C for 2-3 hours to obtain solid residue, liquid fuel oil, and flammable gaseous hydrocarbon products. Comparison of the fuel properties to the petrodiesel fuel standards ASTM D 975 and EN 590 revealed that the synthetic product was within all specifications. Notably, the fuel properties included a kinematic viscosity (40°C) of 1.98 cSt, density of 0.75 gm/cc, sulphur content of 0.25 (wt%), and carbon residue of 0.5 (wt%), and high calorific value represented significant enhancements over those of conventional petroleum diesel fuel.

Catalytic upgrading of oil fractions separated from food waste leachate.

PubMed

Heo, Hyeon Su; Kim, Sang Guk; Jeong, Kwang-Eun; Jeon, Jong-Ki; Park, Sung Hoon; Kim, Ji Man; Kim, Seung-Soo; Park, Young-Kwon

2011-02-01

In this work, catalytic cracking of biomass waste oil fractions separated from food waste leachate was performed using microporous catalysts, such as HY, HZSM-5 and mesoporous Al-MCM-48. The experiments were carried out using pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) to allow the direct analysis of the pyrolytic products. Most acidic components, especially oleic acid, contained in the food waste oil fractions were converted to valuable products, such as oxygenates, hydrocarbons and aromatics. High yields of hydrocarbons within the gasoline-range were obtained when microporous catalysts were used; whereas, the use of Al-MCM-48, which exhibits relatively weak acidity, resulted in high yields of oxygenated and diesel-range hydrocarbons. The HZSM-5 catalyst produced a higher amount of valuable mono aromatics due to its strong acidity and shape selectivity. Especially, the addition of gallium (Ga) to HZSM-5 significantly increased the aromatics content. Copyright © 2010 Elsevier Ltd. All rights reserved.

Pyrolytic Waste Plastic Oil and Its Diesel Blend: Fuel Characterization

PubMed Central

Sultana, M.; Al-Mamun, M. R.; Hasan, M. R.

2016-01-01

The authors introduced waste plastic pyrolysis oil (WPPO) as an alternative fuel characterized in detail and compared with conventional diesel. High density polyethylene, HDPE, was pyrolyzed in a self-designed stainless steel laboratory reactor to produce useful fuel products. HDPE waste was completely pyrolyzed at 330–490°C for 2-3 hours to obtain solid residue, liquid fuel oil, and flammable gaseous hydrocarbon products. Comparison of the fuel properties to the petrodiesel fuel standards ASTM D 975 and EN 590 revealed that the synthetic product was within all specifications. Notably, the fuel properties included a kinematic viscosity (40°C) of 1.98 cSt, density of 0.75 gm/cc, sulphur content of 0.25 (wt%), and carbon residue of 0.5 (wt%), and high calorific value represented significant enhancements over those of conventional petroleum diesel fuel. PMID:27433168

Imaging surface nanobubbles at graphite-water interfaces with different atomic force microscopy modes.

PubMed

Yang, Chih-Wen; Lu, Yi-Hsien; Hwang, Ing-Shouh

2013-05-08

We have imaged nanobubbles on highly ordered pyrolytic graphite (HOPG) surfaces in pure water with different atomic force microscopy (AFM) modes, including the frequency-modulation, the tapping, and the PeakForce techniques. We have compared the performance of these modes in obtaining the surface profiles of nanobubbles. The frequency-modulation mode yields a larger height value than the other two modes and can provide more accurate measurement of the surface profiles of nanobubbles. Imaging with PeakForce mode shows that a nanobubble appears smaller and shorter with increasing peak force and disappears above a certain peak force, but the size returns to the original value when the peak force is reduced. This indicates that imaging with high peak forces does not cause gas removal from the nanobubbles. Based on the presented findings and previous AFM observations, the existing models for nanobubbles are reviewed and discussed. The model of gas aggregate inside nanobubbles provides a better explanation for the puzzles of the high stability and the contact angle of surface nanobubbles.

Fuel Composition Analysis of Endothermically Heated JP-8 Fuel for Use in a Pulse Detonation Engine

DTIC Science & Technology

2008-06-01

detonation engine (PDE) was extracted via zeolite catalyst coated concentric tube-counter flow heat exchangers to produce supercritical pyrolytic conditions...gas chromatography flame ionization and thermal conductivity detectors ............................................. 68 Table B.1. Elemental bias... chromatography ...................... 98 Table D.1b. Products found in the liquid sample by gas chromatography (continued) ... 99 Table D.1c

Thermally stable laminating resins

NASA Technical Reports Server (NTRS)

Jones, R. J.; Vaughan, R. W.; Burns, E. A.

1972-01-01

Improved thermally stable laminating resins were developed based on the addition-type pyrolytic polymerization. Detailed monomer and polymer synthesis and characterization studies identified formulations which facilitate press molding processing and autoclave fabrication of glass and graphite fiber reinforced composites. A specific resin formulation, termed P10P was utilized to prepare a Courtaulds HMS reinforced simulated airfoil demonstration part by an autoclave molding process.

Pyrolytic reactions of carbohydrates. Part I. Mutarotation of molten D-glucose

Treesearch

A. Broido; Y. Houminer; S. Patai

1966-01-01

The mutarotation of α- and β-D-glucose near their melting points has been studied in the neat materials as well as in the presence of water, and at low temperature in the presence of H3BO3 and NaHCO3. The process of mutarotation was found to become very fast as soon as the bulk of...

WSTF electrical arc projects

NASA Technical Reports Server (NTRS)

Linley, Larry

1994-01-01

The objectives of these projects include the following: validate method used to screen wire insulation with arc tracking characteristics; determine damage resistance to arc as a function of source voltage and insulation thickness; investigate propagation characteristics of Kapton at low voltages; and investigate pyrolytic properties of polyimide insulated (Kapton) wire for low voltage (less than 35 VDC) applications. Supporting diagrams and tables are presented.

Selective removal of polycyclic aromatic hydrocarbons (PAHs) from soil washing effluents using biochars produced at different pyrolytic temperatures.

PubMed

Li, Helian; Qu, Ronghui; Li, Chao; Guo, Weilin; Han, Xuemei; He, Fang; Ma, Yibing; Xing, Baoshan

2014-07-01

Wheat straw biochars produced at 400, 600 and 800°C (BC400, BC600 and BC800) were used to selectively adsorb PAHs from soil washing effluents. For soil washing effluents contained Phenanthrene (PHE), Fluoranthene (FLU), Pyrene (PYR) and Triton X-100 (TX100), biochars at 2 (for BC800) or 6 g L(-1) (for BC400 and BC600) can remove 71.8-98.6% of PAHs while recover more than 87% of TX100. PAH removals increase with increasing biochar dose. However, excess biochar is detrimental to the recovery of surfactant. For a specific biochar dose, PAH removal and TX100 loss increase with increasing pyrolytic temperature. For BC400 and BC600, PAH removal follows the order of PHE>FLU>PYR, while the order is reversed with PYR>FLU>PHE for BC800. Biochars have much higher sorption affinity for PAHs than for TX100. It is therefore suggested that biochar is a good alternative for selective adsorption of PAHs and recovery of TX100 in soil washing process. Copyright © 2014 Elsevier Ltd. All rights reserved.

Fabrication and Vibration Results of 30-cm Pyrolytic Graphite Ion Optics

NASA Technical Reports Server (NTRS)

DePano, Michael K.; Hart, Stephen L.; Hanna, Andrew A.; Schneider, Analyn C.

2004-01-01

Boeing Electron Dynamic Devices, Inc. is currently developing pyrolytic graphite (PG) grids designed to operate on 30-cm NSTAR-type thrusters for the Carbon Based Ion Optics (CBIO) program. The PG technology effort of the CBIO program aims to research PG as a flightworthy material for use in dished ion optics by designing, fabricating, and performance testing 30-cm PG grids. As such, PG grid fabrication results will be discussed as will PG design considerations and how they must differ from the NSTAR molybdenum grid design. Surface characteristics and surface processing of PG will be explored relative to effects on voltage breakdown. Part of the CBIO program objectives is to understand the erosion of PG due to Xenon ion bombardment. Discussion of PG and CC sputter yields will be presented relative to molybdenum. These sputter yields will be utilized in the life modeling of carbon-based grids. Finally, vibration results of 30-cm PG grids will be presented and compared to a first-order model generated at Boeing EDD. Performance testing results of the PG grids will not be discussed in this paper as it has yet to be completed.

Raman studies of the interactions of fibrous carbon nanomaterials with albumin

NASA Astrophysics Data System (ADS)

Wesełucha-Birczyńska, Aleksandra; Morajka, Krzysztof; Stodolak-Zych, Ewa; Długoń, Elżbieta; Dużyja, Maria; Lis, Tomasz; Gubernat, Maciej; Ziąbka, Magdalena; Błażewicz, Marta

2018-05-01

Adsorption or immobilization of proteins on synthetic surfaces is a key issue in the context of the biocompatibility of implant materials, especially those intended for the needs of cardiac surgery but also for the construction of biosensors or nanomaterials used as drug carriers. The subject of research was the analysis of Raman spectra of two types of fibrous carbon nanomaterials, of great potential for biomedical applications, incubated with human serum albumin (HSA). The first nanomaterial has been created on the layer of MWCNTs deposited by electrophoretic method (EPD) and then covered by thin film of pyrolytic carbon introduced by chemical vapor deposition process (CVD). The second material was formed from carbonized nanofibers prepared via electrospinning (ESCNFs) of polyacrylonitrile (PAN) precursor and then covered with pyrolytic carbon (CVD). The G-band blue-shift towards the position of about 1600 cm-1, observed for both studied surfaces, clearly indicates the albumin (HSA) adhesion to the surface. The G and G' (2D) peak shift was employed to assess the stress build up on the carbon nanomaterials. The surface nano- and micro-topography as well as the method of ordering the carbon nanomaterial has a significant influence on the mode of surface-protein interaction.

Removal of copper by oxygenated pyrolytic tire char: kinetics and mechanistic insights.

PubMed

Quek, Augustine; Balasubramanian, Rajashekhar

2011-04-01

The kinetics of copper ion (Cu(II)) removal from aqueous solution by pyrolytic tire char was modeled using five different conventional models. A modification to these models was also developed through a modified equation that accounts for precipitation. Conventional first- and second-order reaction models did not fit the copper sorption kinetics well, indicating a lack of simple rate-order dependency on solute concentration. Instead, a reversible first-order rate reaction showed the best fit to the data, indicating a dependence on surface functional groups. Due to the varying solution pH during the sorption process, modified external and internal mass transfer models were employed. Results showed that the sorption of copper onto oxygenated chars was limited by external mass transfer and internal resistance with and without the modification. However, the modification of the sorption process produced very different results for unoxygenated chars, which showed neither internal nor external limitation to sorption. Instead, its slow sorption rate indicates a lack of surface functional groups. The sorption of Cu(II) by oxygenated and unoxygenated chars was also found to occur via three and two distinct stages, respectively. Copyright © 2010 Elsevier Inc. All rights reserved.

Fish Reproduction Is Disrupted upon Lifelong Exposure to Environmental PAHs Fractions Revealing Different Modes of Action

PubMed Central

Vignet, Caroline; Larcher, Thibaut; Davail, Blandine; Joassard, Lucette; Le Menach, Karyn; Guionnet, Tiphaine; Lyphout, Laura; Ledevin, Mireille; Goubeau, Manon; Budzinski, Hélène; Bégout, Marie-Laure; Cousin, Xavier

2016-01-01

Polycyclic aromatic hydrocarbons (PAHs) constitute a large family of organic pollutants emitted in the environment as complex mixtures, the compositions of which depend on origin. Among a wide range of physiological defects, PAHs are suspected to be involved in disruption of reproduction. In an aquatic environment, the trophic route is an important source of chronic exposure to PAHs. Here, we performed trophic exposure of zebrafish to three fractions of different origin, one pyrolytic and two petrogenic. Produced diets contained PAHs at environmental concentrations. Reproductive traits were analyzed at individual, tissue and molecular levels. Reproductive success and cumulative eggs number were disrupted after exposure to all three fractions, albeit to various extents depending on the fraction and concentrations. Histological analyses revealed ovary maturation defects after exposure to all three fractions as well as degeneration after exposure to a pyrolytic fraction. In testis, hypoplasia was observed after exposure to petrogenic fractions. Genes expression analysis in gonads has allowed us to establish common pathways such as endocrine disruption or differentiation/maturation defects. Taken altogether, these results indicate that PAHs can indeed disrupt fish reproduction and that different fractions trigger different pathways resulting in different effects. PMID:29051429

Remediation of Petroleum-Contaminated Soil and Simultaneous Recovery of Oil by Fast Pyrolysis.

PubMed

Li, De-Chang; Xu, Wan-Fei; Mu, Yang; Yu, Han-Qing; Jiang, Hong; Crittenden, John C

2018-05-01

Petroleum-contaminated soil (PCS) caused by the accidental release of crude oil into the environment, which occurs frequently during oil exploitation worldwide, needs efficient and cost-effective remediation. In this study, a fast pyrolysis technology was implemented to remediate the PCS and concurrently recover the oil. The remediation effect related to pyrolytic parameters, the recovery rate of oil and its possible formation pathway, and the physicochemical properties of the remediated PCS and its suitability for planting were systematically investigated. The results show that 50.9% carbon was recovered in oil, whose quality even exceeds that of crude oil. Both extractable total petroleum hydrocarbon (TPH) and water-soluble organic matter (SOM) in PCS were completely removed at 500 °C within 30 min. The remaining carbon in remediated PCS was determined to be in a stable and innocuous state, which has no adverse effect on wheat growth. On the basis of the systematically characterizations of initial PCS and pyrolytic products, a possible thermochemical mechanism was proposed which involves evaporation, cracking and polymerization. In addition, the energy consumption analysis and remediation effect of various PCSs indicate that fast pyrolysis is a viable and cost-effective method for PCS remediation.

Atomic Oxygen Erosion Yield Predictive Tool for Spacecraft Polymers in Low Earth Orbit

NASA Technical Reports Server (NTRS)

Bank, Bruce A.; de Groh, Kim K.; Backus, Jane A.

2008-01-01

A predictive tool was developed to estimate the low Earth orbit (LEO) atomic oxygen erosion yield of polymers based on the results of the Polymer Erosion and Contamination Experiment (PEACE) Polymers experiment flown as part of the Materials International Space Station Experiment 2 (MISSE 2). The MISSE 2 PEACE experiment accurately measured the erosion yield of a wide variety of polymers and pyrolytic graphite. The 40 different materials tested were selected specifically to represent a variety of polymers used in space as well as a wide variety of polymer chemical structures. The resulting erosion yield data was used to develop a predictive tool which utilizes chemical structure and physical properties of polymers that can be measured in ground laboratory testing to predict the in-space atomic oxygen erosion yield of a polymer. The properties include chemical structure, bonding information, density and ash content. The resulting predictive tool has a correlation coefficient of 0.914 when compared with actual MISSE 2 space data for 38 polymers and pyrolytic graphite. The intent of the predictive tool is to be able to make estimates of atomic oxygen erosion yields for new polymers without requiring expensive and time consumptive in-space testing.

Hollow carbon nanobubbles: monocrystalline MOF nanobubbles and their pyrolysis.

PubMed

Zhang, Wei; Jiang, Xiangfen; Zhao, Yanyi; Carné-Sánchez, Arnau; Malgras, Victor; Kim, Jeonghun; Kim, Jung Ho; Wang, Shaobin; Liu, Jian; Jiang, Ji-Sen; Yamauchi, Yusuke; Hu, Ming

2017-05-01

While bulk-sized metal-organic frameworks (MOFs) face limits to their utilization in various research fields such as energy storage applications, nanoarchitectonics is believed to be a possible solution. It is highly challenging to realize MOF nanobubbles with monocrystalline frameworks. By a spatially controlled etching approach, here, we can achieve the synthesis of zeolitic imidazolate framework (ZIF-8) nanobubbles with a uniform size of less than 100 nm. Interestingly, the ZIF-8 nanobubbles possess a monocrystalline nanoshell with a thickness of around 10 nm. Under optimal pyrolytic conditions, the ZIF-8 nanobubbles can be converted into hollow carbon nanobubbles while keeping their original shapes. The structure of the nanobubble enhances the fast Na + /K + ion intercalation performance. Such remarkable improvement cannot be realized by conventional MOFs or their derived carbons.

Hydrocarbons and trace metals in mussels in the Macaé coast: Preliminary assessment for a coastal zone under influence of offshore oil field exploration in southeastern Brazil.

PubMed

Santiago, Igor U; Molisani, Mauricio M; Nudi, Adriana H; Scofield, Artur L; Wagener, Angela de L R; Limaverde Filho, Aricelso M

2016-02-15

Concentrations of PAHs and metals were obtained from mussels collected in beaches, coastal island and estuary of the Macaé coast, the main operational basin for offshore oil exploration in Brazil. This survey provides reference levels for scenarios of increasing exploration, as well as for other areas of the coast undergoing urbanization to support exploration. As expected, urban areas such as the Macaé river estuary presented high concentrations of PAHs, although unsuspected sites such the island also presented signs of contamination. PAH in mussels originated from pyrolytic and petrogenic sources. Metals were typical of non-contaminated coastal environments, although Cr concentrations were above Brazilian Reference Levels. Copyright © 2015 Elsevier Ltd. All rights reserved.

Positron annihilation studies in ZnO nanoparticles

NASA Astrophysics Data System (ADS)

Sharma, S. K.; Pujari, P. K.; Sudarshan, K.; Dutta, D.; Mahapatra, M.; Godbole, S. V.; Jayakumar, O. D.; Tyagi, A. K.

2009-04-01

We report results on positron annihilation spectroscopic (PAS) studies using lifetime and coincidence Doppler broadening techniques in zinc oxide (ZnO) nanoparticles (4 to 40 nm) synthesized by solid state pyrolytic reaction followed by annealing in the temperature range of 200 ∘C to 800 ∘C. Positron lifetime in the nanoparticles are observed to be higher than bulk lifetime in all the cases. Theoretical calculation of lifetime indicates the presence of either Zn or (Zn, O) vacancy clusters which migrate and anneal out at high temperature. Comparison of ratio spectra from coincidence Doppler broadening measurement and calculated electron momentum distribution indicates the presence of either Zn or (Zn, O) vacancies. In addition, photoluminescence (PL) measurements have been carried out to examine the role of defects on the intensity of emission in the visible region.

Method and article for primary containment of cesium wastes. [DOE patent application

DOEpatents

Angelini, P.; Lackey, W.J.; Stinton, D.P.; Blanco, R.E.; Bond, W.D.; Arnold, W.D. Jr.

1981-09-03

A method for producing a cesium-retentive waste form, characterized by a high degree of compositional stability and mechanical integrity, is provided by subjecting a cesium-loaded zeolite to heat under conditions suitable for stabilizing the zeolite and immobilizing the cesium, and coating said zeolite for sufficient duration within a suitable environment with at least one dense layer of pyrolytic carbon to seal therein said cesium to produce a final, cesium-bearing waste form. Typically, the zolite is stabilized and the cesium immobilized in less than four hours by confinement within an air environment maintained at about 600/sup 0/C. Coatings are thereafter applied by confining the calcined zeolite within a coating environment comprising inert fluidizing and carbon donor gases maintained at 1000/sup 0/C for a suitable duration.

Method for primary containment of cesium wastes

DOEpatents

Angelini, Peter; Lackey, Walter J.; Stinton, David P.; Blanco, Raymond E.; Bond, Walter D.; Arnold, Jr., Wesley D.

1983-01-01

A method for producing a cesium-retentive waste form, characterized by a high degree of compositional stability and mechanical integrity, is provided by subjecting a cesium-loaded zeolite to heat under conditions suitable for stabilizing the zeolite and immobilizing the cesium, and coating said zeolite for sufficient duration within a suitable environment with at least one dense layer of pyrolytic carbon to seal therein said cesium to produce a final, cesium-bearing waste form. Typically, the zeolite is stabilized and the cesium immobilized in less than four hours by confinement within an air environment maintained at about 600.degree. C. Coatings are thereafter applied by confining the calcined zeolite within a coating environment comprising inert fluidizing and carbon donor gases maintained at 1,000.degree. C. for a suitable duration.

High viscosity environments: an unexpected route to obtain true atomic resolution with atomic force microscopy.

PubMed

Weber, Stefan A L; Kilpatrick, Jason I; Brosnan, Timothy M; Jarvis, Suzanne P; Rodriguez, Brian J

2014-05-02

Atomic force microscopy (AFM) is widely used in liquid environments, where true atomic resolution at the solid-liquid interface can now be routinely achieved. It is generally expected that AFM operation in more viscous environments results in an increased noise contribution from the thermal motion of the cantilever, thereby reducing the signal-to-noise ratio (SNR). Thus, viscous fluids such as ionic and organic liquids have been generally avoided for high-resolution AFM studies despite their relevance to, e.g. energy applications. Here, we investigate the thermal noise limitations of dynamic AFM operation in both low and high viscosity environments theoretically, deriving expressions for the amplitude, phase and frequency noise resulting from the thermal motion of the cantilever, thereby defining the performance limits of amplitude modulation, phase modulation and frequency modulation AFM. We show that the assumption of a reduced SNR in viscous environments is not inherent to the technique and demonstrate that SNR values comparable to ultra-high vacuum systems can be obtained in high viscosity environments under certain conditions. Finally, we have obtained true atomic resolution images of highly ordered pyrolytic graphite and mica surfaces, thus revealing the potential of high-resolution imaging in high viscosity environments.

High viscosity environments: an unexpected route to obtain true atomic resolution with atomic force microscopy

NASA Astrophysics Data System (ADS)

Weber, Stefan A. L.; Kilpatrick, Jason I.; Brosnan, Timothy M.; Jarvis, Suzanne P.; Rodriguez, Brian J.

2014-05-01

Atomic force microscopy (AFM) is widely used in liquid environments, where true atomic resolution at the solid-liquid interface can now be routinely achieved. It is generally expected that AFM operation in more viscous environments results in an increased noise contribution from the thermal motion of the cantilever, thereby reducing the signal-to-noise ratio (SNR). Thus, viscous fluids such as ionic and organic liquids have been generally avoided for high-resolution AFM studies despite their relevance to, e.g. energy applications. Here, we investigate the thermal noise limitations of dynamic AFM operation in both low and high viscosity environments theoretically, deriving expressions for the amplitude, phase and frequency noise resulting from the thermal motion of the cantilever, thereby defining the performance limits of amplitude modulation, phase modulation and frequency modulation AFM. We show that the assumption of a reduced SNR in viscous environments is not inherent to the technique and demonstrate that SNR values comparable to ultra-high vacuum systems can be obtained in high viscosity environments under certain conditions. Finally, we have obtained true atomic resolution images of highly ordered pyrolytic graphite and mica surfaces, thus revealing the potential of high-resolution imaging in high viscosity environments.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hallerman, G.; Gray, R.J.

An instrument for crushing-strength determinations of uncoated and pyrolytic-carbon-coated fuel particles (50 to 500 mu in diameter) was developed to relate the crushing strength of the particles to their fabricability. The instrument consists of a loading mechanism, load cell, and a power supply-readout unit. The information that can be obtained by statistical methods of the data analysis is illustrated by results on two batches of fuel particles. (auth)

Bismaleimide/Preceramic Polymer Blends for Hybrid Material Transition Regions. Part 1. Processing and Characterization (Postprint)

DTIC Science & Technology

2014-01-01

and placed in a bea- ker with a silicone oil bath at 150C for 10 min while slowly adding the component A of the Matrimid A/B pow- der. To prepare the... pyrolytic cera- mic conversion reaction that was essentially completed at 700C. The observed 62% char yield for RD-730 is reason- ably close to the 67

Carbon Dioxide Corrosion and Acetate: A Hypothesis on the Influence of Microorganisms

DTIC Science & Technology

2008-11-01

thermocatalytic degradation of kero- gen,5 oxidation of suitable acid precursors," "and the pyrolytic destruction of kerogen or oil components.*IS... oil industry. Both chemical compounds can be produced and consumed by microorganisms during the anaerobic biodegradation of organic matter- including...hydrocarbons. We contend that the principles governing anaerobic biodegration activity can be extrapolated to above ground oil production facilities

Annealed CVD molybdenum thin film surface

DOEpatents

Carver, Gary E.; Seraphin, Bernhard O.

1984-01-01

Molybdenum thin films deposited by pyrolytic decomposition of Mo(CO).sub.6 attain, after anneal in a reducing atmosphere at temperatures greater than 700.degree. C., infrared reflectance values greater than reflectance of supersmooth bulk molybdenum. Black molybdenum films deposited under oxidizing conditions and annealed, when covered with an anti-reflecting coating, approach the ideal solar collector characteristic of visible light absorber and infrared energy reflector.

Comparison of ethanol production from corn cobs and switchgrass following a pyrolysis-based biorefinery approach.

PubMed

Luque, Luis; Oudenhoven, Stijn; Westerhof, Roel; van Rossum, Guus; Berruti, Franco; Kersten, Sascha; Rehmann, Lars

2016-01-01

One of the main obstacles in lignocellulosic ethanol production is the necessity of pretreatment and fractionation of the biomass feedstocks to produce sufficiently pure fermentable carbohydrates. In addition, the by-products (hemicellulose and lignin fraction) are of low value, when compared to dried distillers grains (DDG), the main by-product of corn ethanol. Fast pyrolysis is an alternative thermal conversion technology for processing biomass. It has recently been optimized to produce a stream rich in levoglucosan, a fermentable glucose precursor for biofuel production. Additional product streams might be of value to the petrochemical industry. However, biomass heterogeneity is known to impact the composition of pyrolytic product streams, as a complex mixture of aromatic compounds is recovered with the sugars, interfering with subsequent fermentation. The present study investigates the feasibility of fast pyrolysis to produce fermentable pyrolytic glucose from two abundant lignocellulosic biomass sources in Ontario, switchgrass (potential energy crop) and corn cobs (by-product of corn industry). Demineralization of biomass removes catalytic centers and increases the levoglucosan yield during pyrolysis. The ash content of biomass was significantly decreased by 82-90% in corn cobs when demineralized with acetic or nitric acid, respectively. In switchgrass, a reduction of only 50% for both acids could be achieved. Conversely, levoglucosan production increased 9- and 14-fold in corn cobs when rinsed with acetic and nitric acid, respectively, and increased 11-fold in switchgrass regardless of the acid used. After pyrolysis, different configurations for upgrading the pyrolytic sugars were assessed and the presence of potentially inhibitory compounds was approximated at each step as double integral of the UV spectrum signal of an HPLC assay. The results showed that water extraction followed by acid hydrolysis and solvent extraction was the best upgrading strategy. Ethanol yields achieved based on initial cellulose fraction were 27.8% in switchgrass and 27.0% in corn cobs. This study demonstrates that ethanol production from switchgrass and corn cobs is possible following a combined thermochemical and fermentative biorefinery approach, with ethanol yields comparable to results in conventional pretreatments and fermentation processes. The feedstock-independent fermentation ability can easily be assessed with a simple assay.

Selective CO2 Sequestration with Monolithic Bimodal Micro/Macroporous Carbon Aerogels Derived from Stepwise Pyrolytic Decomposition of Polyamide-Polyimide-Polyurea Random Copolymers.

PubMed

Saeed, Adnan M; Rewatkar, Parwani M; Majedi Far, Hojat; Taghvaee, Tahereh; Donthula, Suraj; Mandal, Chandana; Sotiriou-Leventis, Chariklia; Leventis, Nicholas

2017-04-19

Polymeric aerogels (PA-xx) were synthesized via room-temperature reaction of an aromatic triisocyanate (tris(4-isocyanatophenyl) methane) with pyromellitic acid. Using solid-state CPMAS 13 C and 15 N NMR, it was found that the skeletal framework of PA-xx was a statistical copolymer of polyamide, polyurea, polyimide, and of the primary condensation product of the two reactants, a carbamic-anhydride adduct. Stepwise pyrolytic decomposition of those components yielded carbon aerogels with both open and closed microporosity. The open micropore surface area increased from <15 m 2 g -1 in PA-xx to 340 m 2 g -1 in the carbons. Next, reactive etching at 1,000 °C with CO 2 opened access to the closed pores and the micropore area increased by almost 4× to 1150 m 2 g -1 (out of 1750 m 2 g -1 of a total BET surface area). At 0 °C, etched carbon aerogels demonstrated a good balance of adsorption capacity for CO 2 (up to 4.9 mmol g -1 ), and selectivity toward other gases (via Henry's law). The selectivity for CO 2 versus H 2 (up to 928:1) is suitable for precombustion fuel purification. Relevant to postcombustion CO 2 capture and sequestration (CCS), the selectivity for CO 2 versus N 2 was in the 17:1 to 31:1 range. In addition to typical factors involved in gas sorption (kinetic diameters, quadrupole moments and polarizabilities of the adsorbates), it is also suggested that CO 2 is preferentially engaged by surface pyridinic and pyridonic N on carbon (identified with XPS) in an energy-neutral surface reaction. Relatively high uptake of CH 4 (2.16 mmol g -1 at 0 °C/1 bar) was attributed to its low polarizability, and that finding paves the way for further studies on adsorption of higher (i.e., more polarizable) hydrocarbons. Overall, high CO 2 selectivities, in combination with attractive CO 2 adsorption capacities, low monomer cost, and the innate physicochemical stability of carbon render the materials of this study reasonable candidates for further practical consideration.

The role of mineral surface chemistry in modified dextrin adsorption.

PubMed

Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka M; Harmer, Sarah L; Beattie, David A

2011-05-15

The adsorption of two modified dextrins (phenyl succinate dextrin--PS Dextrin; styrene oxide dextrin--SO Dextrin) on four different mineral surfaces has been studied using X-ray photoelectron spectroscopy (XPS), in situ atomic force microscopy (AFM) imaging, and captive bubble contact angle measurements. The four surfaces include highly orientated pyrolytic graphite (HOPG), freshly cleaved synthetic sphalerite (ZnS), and two surfaces produced through surface reactions of sphalerite: one oxidized in alkaline solution (pH 9, 1 h immersion); and one subjected to metal ion exchange between copper and zinc (i.e. copper activation: exposed to 1×10(-3) M CuSO(4) solution for 1 h). XPS measurements indicate that the different sphalerite surfaces contain varying amounts of sulfur, zinc, oxygen, and copper, producing substrates for polymer adsorption with a range of possible binding sites. AFM imaging has shown that the two polymers adsorb to a similar extent on HOPG, and that the two polymers display very different propensities for adsorption on the three sphalerite surface types, with freshly cleaved sphalerite encouraging the least adsorption, and copper activated and oxidized sphalerite encouraging significantly more adsorption. Contact angle measurements of the four surfaces indicate that synthetic sphalerite has a low contact angle upon fracture, and that oxidation on the timescale of one hour substantially alters the hydrophobicity. HOPG and copper-activated sphalerite were the most hydrophobic, as expected due to the carbon and di/poly-sulfide rich surfaces of the two samples, respectively. SO Dextrin is seen to have a significant impact on the wettability of HOPG and the surface reacted sphalerite samples, highlighting the difficulty in selectively separating sphalerite from carbonaceous unwanted minerals in flotation. PS Dextrin has the least effect on the hydrophobicity of the reacted sphalerite surfaces, whilst still significantly increasing the wettability of graphite, and thus has more potential for use as a polymer depressant in this separation. Copyright © 2011 Elsevier Inc. All rights reserved.

The effect of PeakForce tapping mode AFM imaging on the apparent shape of surface nanobubbles.

PubMed

Walczyk, Wiktoria; Schön, Peter M; Schönherr, Holger

2013-05-08

Until now, TM AFM (tapping mode or intermittent contact mode atomic force microscopy) has been the most often applied direct imaging technique to analyze surface nanobubbles at the solid-aqueous interface. While the presence and number density of nanobubbles can be unequivocally detected and estimated, it remains unclear how much the a priori invasive nature of AFM affects the apparent shapes and dimensions of the nanobubbles. To be able to successfully address the unsolved questions in this field, the accurate knowledge of the nanobubbles' dimensions, radii of curvature etc is necessary. In this contribution we present a comparative study of surface nanobubbles on HOPG (highly oriented pyrolytic graphite) in water acquired with (i) TM AFM and (ii) the recently introduced PFT (PeakForce tapping) mode, in which the force exerted on the nanobubbles rather than the amplitude of the resonating cantilever is used as the AFM feedback parameter during imaging. In particular, we analyzed how the apparent size and shape of nanobubbles depend on the maximum applied force in PFT AFM. Even for forces as small as 73 pN, the nanobubbles appeared smaller than their true size, which was estimated from an extrapolation of the bubble height to zero applied force. In addition, the size underestimation was found to be more pronounced for larger bubbles. The extrapolated true nanoscopic contact angles for nanobubbles on HOPG, measured in PFT AFM, ranged from 145° to 175° and were only slightly underestimated by scanning with non-zero forces. This result was comparable to the nanoscopic contact angles of 160°-175° measured using TM AFM in the same set of experiments. Both values disagree, in accordance with the literature, with the macroscopic contact angle of water on HOPG, measured here to be 63° ± 2°.

RESEARCH ON PHYSICAL AND CHEMICAL PRINCIPLES AFFECTING HIGH TEMPERATURE MATERIALS FOR ROCKET NOZZLES. Quarterly Progress Report, April 1, 1963-June 30, 1963

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lowrie, R.

1963-10-31

The development and properties of refractory materials are described. Corrosion of zirconium carbide, niobium carbide, and niobium carbide-zirconium carbide systems by carbon dioxide and hydrochloric acid at 2250 deg C is reported. Corrosion of silver-tungsten alloys by carbon dioxide and oxygen at 2150 to 2440 deg K is summarized. Measurements of pyrolytic and ZTA graphite corrosion by carbon dioxide and oxygen at 2100 to 2800 deg K are shown. At 2300 deg C the rate of formation of methane from graphite and hydrogen is greatly reduced by the addition of helium, at constant hydrogen pressure. Up to 2000 deg Cmore » the effect of helium is small. The pyrolysis of methane on graphite at 2000 deg C is tabulated. Oxidation of tungsten to form WO/sub 2/ and WO/sub 3/ is reported. Vaporization of hafnium borides at 2297 to 2538 deg K is analyzed. The lattice parameters of ZrB/sub 2/ at of TiN/sub 0.6/ and TiN/sub 0.75/ are discussed. Powder metallurgical techniques are used to prepare TiB/sub 2/, ZrB/sub 2/, HfB/ sub 2/, NbB/sub 2/, a nd TaB/sub 2/ for detailed x-ray characterization. The electric conductivity of NbC-ZrC systems is reported. General descriptions are given of analytical techniques for free carbon in carbides and spectrographic methods for metallic impurities in carbides and borides. Preliminary roomtemperature measurements are reported of the elastic properties of polycrystalline ZrB/sub 2/. Titanium carbide is brazed to tungsten with a platinum-boron system. A largegrained polycrystalline specimen of ZrC is plastically deformed in creep at 2134 deg C. Metallographic and x-ray examinations of polycrystalline TiC specimens deformed in creep reveal an increasing development with deformation of subgrains having preferred orientation. (N.W.R.)« less

Nucleation, growth, and repair of a cobalt-based oxygen evolving catalyst.

PubMed

Surendranath, Yogesh; Lutterman, Daniel A; Liu, Yi; Nocera, Daniel G

2012-04-11

The mechanism of nucleation, steady-state growth, and repair is investigated for an oxygen evolving catalyst prepared by electrodeposition from Co(2+) solutions in weakly basic electrolytes (Co-OEC). Potential step chronoamperometry and atomic force microscopy reveal that nucleation of Co-OEC is progressive and reaches a saturation surface coverage of ca. 70% on highly oriented pyrolytic graphite substrates. Steady-state electrodeposition of Co-OEC exhibits a Tafel slope approximately equal to 2.3 × RT/F. The electrochemical rate law exhibits a first order dependence on Co(2+) and inverse orders on proton (third order) and proton acceptor, methylphosphonate (first order for 1.8 mM ≤ [MeP(i)] ≤ 18 mM and second order dependence for 32 mM ≤ [MeP(i)] ≤ 180 mM). These electrokinetic studies, combined with recent XAS studies of catalyst structure, suggest a mechanism for steady state growth at intermediate MeP(i) concentration (1.8-18 mM) involving a rapid solution equilibrium between aquo Co(II) and Co(III) hydroxo species accompanied with a rapid surface equilibrium involving electrolyte dissociation and deprotonation of surface bound water. These equilibria are followed by a chemical rate-limiting step for incorporation of Co(III) into the growing cobaltate clusters comprising Co-OEC. At higher concentrations of MeP(i) ([MeP(i)] ≥ 32 mM), MePO(3)(2-) equilibrium binding to Co(II) in solution is suggested by the kinetic data. Consistent with the disparate pH profiles for oxygen evolution electrocatalysis and catalyst formation, NMR-based quantification of catalyst dissolution as a function of pH demonstrates functional stability and repair at pH values >6 whereas catalyst corrosion prevails at lower pH values. These kinetic insights provide a basis for developing and operating functional water oxidation (photo)anodes under benign pH conditions. © 2012 American Chemical Society

Method of making carbon-carbon composites

DOEpatents

Engle, Glen B.

1991-01-01

A process for making a carbon-carbon composite having a combination of high crystallinity, high strength, high modulus and high thermal and electrical conductivity. High-modulus/high-strength mesophase derived carbon fibers are woven into a suitable cloth. Layers of this easily graphitizable woven cloth are covered with petroleum or coal tar pitch and pressed at a temperature a few degrees above the softening point of the pitch to form a green laminated composite. The green composite is restrained in a suitable fixture and heated slowly to carbonize the pitch binder. The carbonized composite is then impregnated several times with pitch by covering the composite with hot pitch under pressure. The composites are given a heat treatment between each impregnation step to crack up the infiltrated carbon and allow additional pitch to enter the microstructure during the next impregnation cycle. The impregnated composites are then given a final heat treatment in the range 2500.degree. to 3000.degree. C. to fully graphitize the fibers and the matrix carbon. The composites are then infiltrated with pyrolytic carbon by chemical vapor deposition in the range 1000.degree. to 1300.degree. C. at a reduced pressure for approximately one hundred and fifty (150) hours.

An isotopic biogeochemical study of the Green River oil shale

NASA Technical Reports Server (NTRS)

Collister, J. W.; Summons, R. E.; Lichtfouse, E.; Hayes, J. M.

1992-01-01

Thirty-five different samples from three different sulfur cycles were examined in this stratigraphically oriented study of the Shell 22x-l well (U.S.G.S. C177 core) in the Piceance Basin, Colorado. Carbon isotopic compositions of constituents of Green River bitumens indicate mixing of three main components: products of primary photoautotrophs and their immediate consumers (delta approximately -30% vs PDB), products of methanotrophic bacteria (delta approximately -85%), and products of unknown bacteria (delta approximately -40%). For individual compounds synthesized by primary producers, delta-values ranged from -28 to -32%. 13C contents of individual primary products (beta-carotane, steranes, acyclic isoprenoids, tricyclic triterpenoids) were not closely correlated, suggesting diverse origins for these materials. 13C contents of numerous hopanoids were inversely related to sulfur abundance, indicating that they derived both from methanotrophs and from other bacteria, with abundances of methanotrophs depressed when sulfur was plentiful in the paleoenvironment. gamma-Cerane coeluted with 3 beta(CH3),17 alpha(H),21 beta(H)-hopane, but delta-values could be determined after deconvolution. gamma-Cerane (delta approximately -25%) probably derives from a eukaryotic heterotroph grazing on primary materials, the latter compound (delta approximately -90%) must derive from methanotrophic organisms. 13C contents of n-alkanes in bitumen differed markedly from those of paraffins generated pyrolytically. Isotopic and quantitative relationships suggest that alkanes released by pyrolysis derived from a resistant biopolymer of eukaryotic origin and that this was a dominant constituent of total organic carbon.

Inexpensive Method for Coating the Interior of Silica Growth Ampoules with Pyrolytic Boron Nitride

NASA Technical Reports Server (NTRS)

Wang, Jianbin; Regel, Liya L.; Wilcox, William R.

2003-01-01

An inexpensive method was developed for coating the interior of silica ampoules with hexagonal boron nitride. An aqueous solution of boric acid was used to coat the ampoule prior to drying in a vacuum at 200 C. This coating was converted to transparent boron nitride by heating in ammonia at 1000 C. Coated ampoules were used to achieve detached solidification of indium antimonide on earth.

Reaction mechanisms in cellulose pyrolysis: a literature review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Molton, P.M.; Demmitt, T.F.

1977-08-01

A bibliographic review of 195 references is presented outlining the history of the research into the mechanisms of cellulose pyrolysis. Topics discussed are: initial product identification, mechanism of initial formation of levoglucosan, from cellulose and from related compounds, decomposition of cellulose to other compounds, formation of aromatics, pyrolysis of levoglucosan, crosslinking of cellulose, pyrolytic reactions of cellulose derivatives, and the effects of inorganic salts on the pyrolysis mechanism. (JSR)

Pyrolytic carbon black composite and method of making the same

DOEpatents

Naskar, Amit K.; Paranthaman, Mariappan Parans; Bi, Zhonghe

2016-09-13

A method of recovering carbon black includes the step of providing a carbonaceous source material containing carbon black. The carbonaceous source material is contacted with a sulfonation bath to produce a sulfonated material. The sulfonated material is pyrolyzed to produce a carbon black containing product comprising a glassy carbon matrix phase having carbon black dispersed therein. A method of making a battery electrode is also disclosed.

Beam Technologies for Integrated Processing

DTIC Science & Technology

1992-03-01

Ohki et al., 1988). Initially, they were used in ion Table 3-3 Ceramic Materials Produced by CVD Coating Chemical Mixture Deposition Temp. (* C ) Method...inner coating , deposited from tungsten hexafluoride, providing strength and creep resistance , and the outer layer, deposited from the chloride, has a (110...1971. Structure and Mechanical Properties of Co - deposited Pyrolytic C -SiC Alloys. Journal of the American Ceramic Society 54:605. Kashu, S., M. Nagase

Impact of biochar produced from post-harvest residue on the adsorption behavior of diesel oil on loess soil.

PubMed

Jiang, Yu Feng; Sun, Hang; Yves, Uwamungu J; Li, Hong; Hu, Xue Fei

2016-02-01

The primary objective of this study was to investigate the effect of biochar, produced from wheat residue at different temperatures, on the adsorption of diesel oil by loess soil. Kinetic and equilibrium data were processed to understand the adsorption mechanism of diesel by biochar-affected loess soil; dynamic and thermodynamic adsorption experiments were conducted to characterize this adsorption. The surface features and chemical structure of biochar, modified at varying pyrolytic temperatures, were investigated using surface scanning electron microscopy and Fourier transform infrared analysis. The kinetic data showed that the adsorption of diesel oil onto loess soil could be described by a pseudo-second-order kinetic model, with the rate-controlling step being intraparticle diffusion. However, in the presence of biochar, boundary layer control and intraparticle diffusion were both involved in the adsorption. Besides, the adsorption equilibrium data were well described by the Freundlich isothermal model. The saturated adsorption capacity weakened as temperature increased, suggesting a spontaneous exothermic process. Thermodynamic parameter analysis showed that adsorption was mainly a physical process and was enhanced by chemical adsorption. The adsorption capacity of loess soil for diesel oil was weakened with increasing pH. The biochar produced by pyrolytic wheat residue increased the adsorption behavior of petroleum pollutants in loess soil.

Comparative Studies of the Pyrolytic and Kinetic Characteristics of Maize Straw and the Seaweed Ulva pertusa

PubMed Central

Ye, Naihao; Li, Demao; Chen, Limei; Zhang, Xiaowen; Xu, Dong

2010-01-01

Seaweed has attracted considerable attention as a potential biofuel feedstock. The pyrolytic and kinetic characteristics of maize straw and the seaweed Ulva pertusa were studied and compared using heating rates of 10, 30 and 50°C min−1 under an inert atmosphere. The activation energy, and pre-exponential factors were calculated by the Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) and Popescu methods. The kinetic mechanism was deduced by the Popescu method. The results indicate that there are three stages to the pyrolysis; dehydration, primary devolatilization and residual decomposition. There were significant differences in average activation energy, thermal stability, final residuals and reaction rates between the two materials. The primary devolatilization stage of U. pertusa can be described by the Avramic-Erofeev equation (n = 3), whereas that of maize straw can be described by the Mampel Power Law (n = 2). The average activation energy of maize straw and U. pertusa were 153.0 and 148.7 KJ mol−1, respectively. The pyrolysis process of U.pertusa would be easier than maize straw. And co-firing of the two biomass may be require less external heat input and improve process stability. There were minor kinetic compensation effects between the pre-exponential factors and the activation energy. PMID:20844751

Mathematical modeling of the fermentation of acid-hydrolyzed pyrolytic sugars to ethanol by the engineered strain Escherichia coli ACCC 11177.

PubMed

Chang, Dongdong; Yu, Zhisheng; Islam, Zia Ul; Zhang, Hongxun

2015-05-01

Pyrolysate from waste cotton was acid hydrolyzed and detoxified to yield pyrolytic sugars, which were fermented to ethanol by the strain Escherichia coli ACCC 11177. Mathematical models based on the fermentation data were also constructed. Pyrolysate containing an initial levoglucosan concentration of 146.34 g/L gave a glucose yield of 150 % after hydrolysis, suggesting that other compounds were hydrolyzed to glucose as well. Ethyl acetate-based extraction of bacterial growth inhibitors with an ethyl acetate/hydrolysate ratio of 1:0.5 enabled hydrolysate fermentation by E. coli ACCC 11177, without a standard absorption treatment. Batch processing in a fermenter exhibited a maximum ethanol yield and productivity of 0.41 g/g and 0.93 g/L·h(-1), respectively. The cell growth rate (r x ) was consistent with a logistic equation [Formula: see text], which was determined as a function of cell growth (X). Glucose consumption rate (r s ) and ethanol formation rate (r p ) were accurately validated by the equations [Formula: see text] and [Formula: see text], respectively. Together, our results suggest that combining mathematical models with fermenter fermentation processes can enable optimized ethanol production from cellulosic pyrolysate with E. coli. Similar approaches may facilitate the production of other commercially important organic substances.

Assessment of polycyclic aromatic hydrocarbons (PAHs) contamination in surface soil of coal stockpile sites in South Kalimantan, Indonesia.

PubMed

Mizwar, Andy; Priatmadi, Bambang Joko; Abdi, Chairul; Trihadiningrum, Yulinah

2016-03-01

Concentrations, spatial distribution, and sources of 16 polycyclic aromatic hydrocarbons (PAHs), listed as priority pollutants by the United States Environmental Protection Agency (USEPA), were investigated in surface soils of three different coal stockpile, agricultural, and residential sites in South Kalimantan Province, Indonesia. Total PAHs concentration ranged from 4.69 to 22.67 mg kg(-1)-dw. PAHs concentrations in soil of coal stockpile sites were higher than those in agricultural and residential soil. A complex of petrogenic origin and pyrolytic sources was found within the study area, as suggested by the isomeric ratios of PAHs. The results of principal component analysis and multiple linear regressions (PCA/MLR) showed that three sources contributed to the PAHs in the study area, including biomass and coal combustion (48.46%), raw coal (35.49%), and vehicular emission (16.05%). The high value of total benzo[a]pyrene equivalent concentration (B[a]Peq) suggests that local residents are exposed to a high carcinogenic potential.

Space processing of composite materials

NASA Technical Reports Server (NTRS)

Steurer, W. H.; Kaye, S.

1975-01-01

Materials and processes for the testing of aluminum-base fiber and particle composites, and of metal foams under extended-time low-g conditions were investigated. A wetting and dispersion technique was developed, based on the theory that under the absence of a gas phase all solids are wetted by liquids. The process is characterized by a high vacuum environment and a high temperature cycle. Successful wetting and dispersion experiments were carried out with sapphire fibers, whiskers and particles, and with fibers of silicon carbide, pyrolytic graphite and tungsten. The developed process and facilities permit the preparation of a precomposite which serves as sample material for flight experiments. Low-g processing consists then merely in the uniform redistribution of the reinforcements during a melting cycle. For the preparation of metal foams, gas generation by means of a thermally decomposing compound was found most adaptable to flight experiments. For flight experiments, the use of compacted mixture of the component materials limits low-g processing to a simple melt cycle.

Metastable nanobubbles at the solid-liquid interface due to contact angle hysteresis.

PubMed

Nishiyama, Takashi; Yamada, Yutaka; Ikuta, Tatsuya; Takahashi, Koji; Takata, Yasuyuki

2015-01-27

Nanobubbles exist at solid-liquid interfaces between pure water and hydrophobic surfaces with very high stability, lasting in certain cases up to several days. Not only semispherical but also other shapes, such as micropancakes, are known to exist at such interfaces. However, doubt has been raised as to whether or not the nanobubbles are gas-phase entities. In this study, surface nanobubbles at a pure water-highly ordered pyrolytic graphite (HOPG) interface were investigated by peak force quantitative nanomechanics (PF-QNM). Multiple isolated nanobubbles generated by the solvent-exchange method were present on the terraced areas, avoiding the steps of the HOPG surface. Adjacent nanobubbles coalesced and formed metastable nanobubbles. Coalescence was enhanced by the PF-QNM measurement. We determined that nanobubbles can exist for a long time because of nanoscale contact angle hysteresis at the water-HOPG interface. Moreover, the hydrophilic steps of HOPG were avoided during coalescence, providing evidence that the nanobubbles are truly gas phase.

Surface rearrangement of water-immersed hydrophobic solids by gaseous nanobubbles.

PubMed

Tarábková, Hana; Bastl, Zdeněk; Janda, Pavel

2014-12-09

Interactions of gaseous (ambient) nanobubbles (10-100 nm diameter) with different hydrophobic materials-Teflon, polystyrene, paraffin, and basal plane highly ordered pyrolytic graphite (HOPG)-are studied by AFM in situ and ex situ. Exactly identical surface locations are examined before and after exposure to ambient gas nanobubbles in deionized water and compared for nanomorphological changes. While freely flooded/immersed surfaces, regularly occupied by nanobubbles, do not exhibit resolvable alterations, significant surface rearrangement is found on whole flooded area after mild pressure drop (10 kPa) applied on the solid-liquid interface. Nanopattern and its characteristic dimension appear to be material specific and solely reflect surface-nanobubble interaction. Mild, nonswelling, noncorrosive conditions (20 °C, deionized water) prevent intervention of chemical reaction and high-energy-demanding processes. Experimental results, in accordance with the presented model, indicate that the mild pressure drop triggers expansion of pinned nanobubbles, imposing local tensile stress on the solid surface. Consequently, nanobubbles should be considered as large-area nanoscale patterning elements.