Large-deformation and high-strength amorphous porous carbon nanospheres
NASA Astrophysics Data System (ADS)
Yang, Weizhu; Mao, Shimin; Yang, Jia; Shang, Tao; Song, Hongguang; Mabon, James; Swiech, Wacek; Vance, John R.; Yue, Zhufeng; Dillon, Shen J.; Xu, Hangxun; Xu, Baoxing
2016-04-01
Carbon is one of the most important materials extensively used in industry and our daily life. Crystalline carbon materials such as carbon nanotubes and graphene possess ultrahigh strength and toughness. In contrast, amorphous carbon is known to be very brittle and can sustain little compressive deformation. Inspired by biological shells and honeycomb-like cellular structures in nature, we introduce a class of hybrid structural designs and demonstrate that amorphous porous carbon nanospheres with a thin outer shell can simultaneously achieve high strength and sustain large deformation. The amorphous carbon nanospheres were synthesized via a low-cost, scalable and structure-controllable ultrasonic spray pyrolysis approach using energetic carbon precursors. In situ compression experiments on individual nanospheres show that the amorphous carbon nanospheres with an optimized structure can sustain beyond 50% compressive strain. Both experiments and finite element analyses reveal that the buckling deformation of the outer spherical shell dominates the improvement of strength while the collapse of inner nanoscale pores driven by twisting, rotation, buckling and bending of pore walls contributes to the large deformation.
Amorphous Carbon-Boron Nitride Nanotube Hybrids
NASA Technical Reports Server (NTRS)
Kim, Jae Woo (Inventor); Siochi, Emilie J. (Inventor); Wise, Kristopher E. (Inventor); Lin, Yi (Inventor); Connell, John (Inventor)
2016-01-01
A method for joining or repairing boron nitride nanotubes (BNNTs). In joining BNNTs, the nanotube structure is modified with amorphous carbon deposited by controlled electron beam irradiation to form well bonded hybrid a-C/BNNT structures. In repairing BNNTs, the damaged site of the nanotube structure is modified with amorphous carbon deposited by controlled electron beam irradiation to form well bonded hybrid a-C/BNNT structures at the damage site.
Structural Coloration of a Colloidal Amorphous Array is Intensified by Carbon Nanolayers.
Takeoka, Yukikazu; Iwata, Masanori; Seki, Takahiro; Nueangnoraj, Khanin; Nishihara, Hirotomo; Yoshioka, Shinya
2018-04-10
In this study, we introduce the possibility of applying a colloidal amorphous array composed of fine silica particles as a structural-color material to invisible information technology. The appearance of a thick filmlike colloidal amorphous array formed from fine silica particles is considerably influenced by incoherent light scattering across the entire visible region. Therefore, regardless of the diameter of the fine silica particles, the thick colloidal amorphous array exhibits a white color to the naked eye. When carbon is uniformly deposited in the colloidal amorphous array by a pressure-pulsed chemical vapor deposition method, incoherent light scattering in the colloidal amorphous array is suppressed. As a result, coherent light scattering due to the short-range order in the colloidal amorphous array becomes conspicuous and the array exhibits a vivid structural color. As structures, such as letters and pictures, can be drawn using this technology, the colloidal amorphous array as a structural-colored material may also be applicable for invisible information technology.
Understanding the corrosion behavior of amorphous multiple-layer carbon coating
NASA Astrophysics Data System (ADS)
Guo, Lei; Gao, Ying; Xu, Yongxian; Zhang, Renhui; Madkour, Loutfy H.; Yang, Yingchang
2018-04-01
The corrosion behavior of multiple-layer carbon coating that contained hydrogen, fluorine and silicon, possessed dual amorphous structure with sutured interfaces was investigated using potentiodynamic polarization and electrochemical impedances (ETS) in 3.5 wt.% NaCl solution. The coating exhibited good resistance to corrosion in 3.5 wt.% NaCl solution due to its amorphous and dense structures.
Synthesis of quenchable amorphous diamond
Zeng, Zhidan; Yang, Liuxiang; Zeng, Qiaoshi; ...
2017-08-22
Diamond owes its unique mechanical, thermal, optical, electrical, chemical, and biocompatible materials properties to its complete sp 3-carbon network bonding. Crystallinity is another major controlling factor for materials properties. Although other Group-14 elements silicon and germanium have complementary crystalline and amorphous forms consisting of purely sp 3 bonds, purely sp 3-bonded tetrahedral amorphous carbon has not yet been obtained. In this letter, we combine high pressure and in situ laser heating techniques to convert glassy carbon into “quenchable amorphous diamond”, and recover it to ambient conditions. Our X-ray diffraction, high-resolution transmission electron microscopy and electron energy-loss spectroscopy experiments on themore » recovered sample and computer simulations confirm its tetrahedral amorphous structure and complete sp 3 bonding. This transparent quenchable amorphous diamond has, to our knowledge, the highest density among amorphous carbon materials, and shows incompressibility comparable to crystalline diamond.« less
Synthesis of quenchable amorphous diamond
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zeng, Zhidan; Yang, Liuxiang; Zeng, Qiaoshi
Diamond owes its unique mechanical, thermal, optical, electrical, chemical, and biocompatible materials properties to its complete sp 3-carbon network bonding. Crystallinity is another major controlling factor for materials properties. Although other Group-14 elements silicon and germanium have complementary crystalline and amorphous forms consisting of purely sp 3 bonds, purely sp 3-bonded tetrahedral amorphous carbon has not yet been obtained. In this letter, we combine high pressure and in situ laser heating techniques to convert glassy carbon into “quenchable amorphous diamond”, and recover it to ambient conditions. Our X-ray diffraction, high-resolution transmission electron microscopy and electron energy-loss spectroscopy experiments on themore » recovered sample and computer simulations confirm its tetrahedral amorphous structure and complete sp 3 bonding. This transparent quenchable amorphous diamond has, to our knowledge, the highest density among amorphous carbon materials, and shows incompressibility comparable to crystalline diamond.« less
Raman studied of undoped amorphous carbon thin film deposited by bias assisted-CVD
NASA Astrophysics Data System (ADS)
Ishak, A.; Fadzilah, A. N.; Dayana, K.; Saurdi, I.; Malek, M. F.; Nurbaya, Z.; Shafura, A. K.; Rusop, M.
2018-05-01
The undoped amorphous carbon thin film carbon was deposited at 200°C-350°C by bias assisted-CVD using palm oil as a precursor material. The effect of different substrate deposition temperatures on structural and electrical properties of undoped doped amorphous carbon film was discussed. The structural of undoped amorphous carbon films were correlated with Raman analysis through the evolution of D and G bands, Fourier spectra, and conductivity measurement. The spectral evolution observed showed the increase of upward shift of D and G peaks as substrate deposition temperatures increased. The spectral evolution observed at different substrate deposition temperatures show progressive formation of crystallites. It was predicted that small number of hydrogen is terminated with carbon at surface of thin film as shown by FTIR spectra since palm oil has high number of hydrogen (C67H127O8). These structural changes were further correlated with conductivity and the results obtained are discussed and compared. The conductivity is found in the range of 10-8 Scm-1. The increase of conductivity is correlated by the change of structural properties as correlated with characteristic parameters of Raman spectra including the position of G peak, full width at half maximum of G peak, and ID/IG and FTIR result.
Tetrahedral bonding in amorphous carbon
NASA Astrophysics Data System (ADS)
McKenzie, D. R.
1996-12-01
Electron configurations close to the tetrahedral 0034-4885/59/12/002/img1 hybridization are found in pure amorphous carbon at a concentration which depends on preparation conditions. Tetrahedral bonding at levels of approximately 80% is found in amorphous carbons formed from beams of carbon ions with energies in a `window' between 20 eV and approximately 500 eV. Suitable techniques for its formation include cathodic arc deposition, ion beam deposition and laser ablation. Similar material appears to be formed by pressure treatment of fullerene precursors and by displacement damage in diamond. Highly tetrahedral forms of amorphous carbon (ta-C) show electronic, optical and mechanical properties which approach those of diamond and are quite different from amorphous carbons with low 0034-4885/59/12/002/img1 content. Useful techniques for determining the 0034-4885/59/12/002/img1 content include electron energy loss spectroscopy, electron and neutron diffraction and Raman spectroscopy. Considerable progress has been made in the understanding of this material by simulating its structure in the computer with a range of techniques from empirical potentials to ab initio quantum mechanics. The structure shows departures from an idealized glassy state of diamond which would have a random tetrahedral network structure as used to describe amorphous silicon and germanium. A surprising feature of the structure simulated using ab initio methods is the presence of small rings containing three or four 0034-4885/59/12/002/img1 carbon atoms. The electronic and optical properties are strongly influenced by the residual of 0034-4885/59/12/002/img5 carbon. Applications to electronic devices are at an early stage with the demonstration of photoconductivity and some simple junction devices. Applications as a wear resistant coating are promising, since the theoretically predicted high values of elastic constants, comparable to but less than those of diamond, are achieved experimentally, together with low friction coefficients.
Carbon atom clusters in random covalent networks: PAHs as an integral component of interstellar HAC
NASA Astrophysics Data System (ADS)
Jones, A. P.
1990-11-01
Using a random covalent network (RCN) model for the structure of hydrogenated amorphorous carbon (HAC) and the available laboratory data, it is shown that aromatic species are a natural consequence of the structure of amorphous carbons formed in the laboratory. Amorphous carbons in the interstellar medium are therefore likely to contain a significant fraction of Polycyclic aromatic hydrocarbons (PAH) species within the 'amorphous' matrix making up these materials. This aromatic component can be produced in situ during the accretion of gas phase carbon species on to grains in the interstellar medium under hydrogen-poor conditions, or subsequent to deposition as a result of photolysis (photodarkening). The fraction of interstellar carbon present in HAC in the form of PAHs, based upon a RCN model, is consistent with the observed Unidentified infrared (UIR) emission features.
Hydrogenated nanostructure boron doped amorphous carbon films by DC bias
NASA Astrophysics Data System (ADS)
Ishak, A.; Dayana, K.; Saurdi, I.; Malek, M. F.; Rusop, M.
2018-03-01
Hydrogenated nanostructure-boron doped amorphous carbon thin film carbon was deposited at different negative bias using custom-made deposition bias assisted-CVD. Solid of boron and palm oil were used as dopant and carbon source, respectively. The hydrogenated nanostructure amorphous films were characterized by Field emission scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, while the photo-response studies of thin film is done by I-V measurement under light measurement. The results showed the carbon film were in nanostructure with hydrogen and boron might be incorporated in the film. The Raman spectra observed the increase of upward shift of D and G peaks as negative bias increased which related to the structural change as boron incorporated in carbon network. These structural changes were further correlated with photo-response study and the results obtained are discussed and compared.
Direct /TEM/ observation of the catalytic oxidation of amorphous carbon by Pd particles
NASA Technical Reports Server (NTRS)
Moorhead, R. D.; Poppa, H.; Heinemann, K.
1980-01-01
The catalytic oxidation of amorphous carbon substrates by Pd particles is observed by in situ transmission electron microscopy. Various modes of selective attack of the carbon substrate in the immediate neighborhood of Pd particles are observed, which can be correlated with different degrees of particle mobility. Using amorphous substrates we have been able to demonstrate that the particle-substrate interaction is influenced by the structure of the particle. This has not previously been noted.
On the structure of amorphous calcium carbonate--a detailed study by solid-state NMR spectroscopy.
Nebel, Holger; Neumann, Markus; Mayer, Christian; Epple, Matthias
2008-09-01
The calcium carbonate phases calcite, aragonite, vaterite, monohydrocalcite (calcium carbonate monohydrate), and ikaite (calcium carbonate hexahydrate) were studied by solid-state NMR spectroscopy ( (1)H and (13)C). Further model compounds were sodium hydrogencarbonate, potassium hydrogencarbonate, and calcium hydroxide. With the help of these data, the structure of synthetically prepared additive-free amorphous calcium carbonate (ACC) was analyzed. ACC contains molecular water (as H 2O), a small amount of mobile hydroxide, and no hydrogencarbonate. This supports the concept of ACC as a transient precursor in the formation of calcium carbonate biominerals.
Yang, Yisu; Liang, Fengli; Li, Mengran; Rufford, Thomas E; Zhou, Wei; Zhu, Zhonghua
2015-07-08
Amorphous nickel carbonate particles are catalysts for the oxygen evolution reaction (OER), which plays a critical role in the electrochemical splitting of water. The amorphous nickel carbonate particles can be prepared at a temperature as low as 60 °C by an evaporation-induced precipitation (EIP) method. The products feature hierarchical pore structures. The mass-normalized activity of the catalysts, measured at an overpotential of 0.35 V, was 55.1 A g(-1) , with a Tafel slope of only 60 mV dec(-1) . This catalytic activity is superior to the performance of crystalline NiOx particles and β-Ni(OH)2 particles, and compares favorably to state-of-the-art RuO2 catalysts. The activity of the amorphous nickel carbonate is remarkably stable during a 10 000 s chronoamperometry test. Further optimization of synthesis parameters reveals that the amorphous structure can be tuned by adjusting the H2 O/Ni ratio in the precursor mixture. These results suggest the potential application of easily prepared hierarchical basic nickel carbonate particles as cheap and robust OER catalysts with high activity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Room-temperature low-voltage electroluminescence in amorphous carbon nitride thin films
NASA Astrophysics Data System (ADS)
Reyes, R.; Legnani, C.; Ribeiro Pinto, P. M.; Cremona, M.; de Araújo, P. J. G.; Achete, C. A.
2003-06-01
White-blue electroluminescent emission with a voltage bias less than 10 V was achieved in rf sputter-deposited amorphous carbon nitride (a-CN) and amorphous silicon carbon nitride (a-SiCN) thin-film-based devices. The heterojunction structures of these devices consist of: Indium tin oxide (ITO), used as a transparent anode; amorphous carbon film as an emission layer, and aluminum as a cathode. The thickness of the carbon films was about 250 Å. In all of the produced diodes, a stable visible emission peaked around 475 nm is observed at room temperature and the emission intensity increases with the current density. For an applied voltage of 14 V, the luminance was about 3 mCd/m2. The electroluminescent properties of the two devices are discussed and compared.
NASA Astrophysics Data System (ADS)
Sullivan, J. P.
2002-03-01
Pure carbon films can exhibit surprising complexity in structure and properties. Amorphous diamond (tetrahedrally-coordinated amorphous carbon) is an amorphous quasi-two phase mixture of four-fold and three-fold coordinated carbon which is produced by pulsed excimer laser deposition, an energetic deposition process that leads to film growth by sub-surface carbon implantation and the creation of local metastability in carbon bonding. Modest annealing, < 900K, produces significant irreversible strain relaxation which is thermally activated with activation energies ranging from < 1 eV to > 2 eV. During annealing the material remains amorphous, but there is a detectable increase in medium-range order as measured by fluctuation microscopy. The strain relaxation permits the residual strain in the films to be reduced to < 0.00001, which is a critical requirement for the fabrication of microelectromechanical systems (MEMS). Amorphous diamond MEMS have been fabricated in order to evaluate the mechanical properties of this material under tension and flexure, and this has enabled the determination of elastic modulus (800 GPa), tensile strength (8 GPa), and fracture toughness (8 MPa m^1/2). In addition, amorphous diamond MEMS structures have been fabricated to measure internal dissipation and surface adhesion. The high hardness and strength and hydrophobic nature of the surface makes this material particularly suitable for the fabrication of high wear resistance and low stiction MEMS. Sandia is a multiprogram laboratory operated by Sandia Corp., a Lockheed Martin Co., for the U.S. Dept. of Energy under contract DE-AC04-94AL85000.
Properties of Amorphous Carbon Microspheres Synthesised by Palm Oil-CVD Method
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zobir, S. A. M.; Nano-SciTech Centre,; Zainal, Z.
2011-03-30
Amorphous carbon microspheres were synthesized using a dual-furnace chemical vapour deposition method at 800-1000 deg. C. Palm oil-based cooking oil (PO) and zinc nitrate solution was used as a carbon source and catalyst precursor, respectively with PO to zinc nitrate ratio of 30:20 (v/v) and a silicon wafer as the sample target. Regular microsphere shape of the amorphous carbons was obtained and a uniform microsphere structure improved as the carbonization temperature increased from 800 to 1000 deg. C. At 800 deg. C, no regular microspheres were formed but more uniform structure is observed at 900 deg. C. Generally the microspheresmore » size is uniform when the heating temperature was increased to 1000 deg. C, but the presence of mixed sizes can still be observed. X-ray diffraction patterns show the presence of oxide of carbon, ZnO phase together with Zn oxalate phase. Raman spectra show two broad peaks characteristic to amorphous carbon at 1344 and 1582 cm{sup -1} for the D and G bands, respectively. These bands become more prominent as the preparation temperature increased from 800 to 1000 deg. C. This is in agreement with the formation of amorphous carbon microspheres as shown by the FESEM study and other Zn-based phases as a result of the oxidation process of the palm oil as the carbon source and the zinc nitrate as the catalyst precursor, respectively.« less
In Situ Mechanical Property Measurements of Amorphous Carbon-Boron Nitride Nanotube Nanostructures
NASA Technical Reports Server (NTRS)
Kim, Jae-Woo; Lin, Yi; Nunez, Jennifer Carpena; Siochi, Emilie J.; Wise, Kristopher E.; Connell, John W.; Smith, Michael W.
2011-01-01
To understand the mechanical properties of amorphous carbon (a-C)/boron nitride nanotube (BNNT) nanostructures, in situ mechanical tests are conducted inside a transmission electron microscope equipped with an integrated atomic force microscope system. The nanotube structure is modified with amorphous carbon deposited by controlled electron beam irradiation. We demonstrate multiple in situ tensile, compressive, and lap shear tests with a-C/BNNT hybrid nanostructures. The tensile strength of the a-C/BNNT hybrid nanostructure is 5.29 GPa with about 90 vol% of a-C. The tensile strength and strain of the end-to-end joint structure with a-C welding is 0.8 GPa and 5.2% whereas the lap shear strength of the side-by-side joint structure with a-C is 0.25 GPa.
Creation and formation mechanism of new carbon phases constructed by amorphous carbon
NASA Astrophysics Data System (ADS)
Yao, Mingguang; Cui, Wen; Liu, Bingbing
Our recent effort is focusing on the creation of new hard/superhard carbon phases constructed by disordered carbons or amorphous carbon clusters under high pressure. We showed that the pressure-induced amorphous hard carbon clusters from collapsed fullerenes can be used as building blocks (BBs) for constructing novel carbon structures. This new strategy has been verified by compressing a series of intercalated fullerides, pre-designed by selecting various dopants with special features. We demonstrate that the boundaries of the amorphous BBs are mediated by intercalated dopants and several new superhard materials have been prepared. We also found that the dopant-mediated BBs can be arranged in either ordered or disordered structures, both of which can be hard enough to indent the diamond anvils. The hardening mechanisms of the new phases have also been discussed. For the glassy carbon (GC) constructructed by disordered fullerene-like nanosized fragments, we also found that these disordered fragments can bond and the compressed GC transformed into a transparent superhard phase. Such pressure-induced transformation has been discovered to be driven by a novel mechanism (unpublished). By understanding the mechanisms we can clarify the controversial results on glassy carbon reported recently. The authors would like to thank the financial support from the National Natural Science Foundation of China (No. 11474121, 51320105007).
Ion beam deposition of amorphous carbon films with diamond like properties
NASA Technical Reports Server (NTRS)
Angus, John C.; Mirtich, Michael J.; Wintucky, Edwin G.
1982-01-01
Carbon films were deposited on silicon, quartz, and potassium bromide substrates from an ion beam. Growth rates were approximately 0.3 micron/hour. The films were featureless and amorphous and contained only carbon and hydrogen in significant amounts. The density and carbon/hydrogen ratio indicate the film is a hydrogen deficient polymer. One possible structure, consistent with the data, is a random network of methylene linkages and tetrahedrally coordinated carbon atoms.
Adu, Kofi W; Li, Qixiu; Desai, Sharvil C; Sidorov, Anton N; Sumanasekera, Gamini U; Lueking, Angela D
2009-01-06
The response of two carbide derived carbons (CDCs) films to NH(3), N(2)O, and room air is investigated by four probe resistance at room temperature and pressures up to 760 Torr. The two CDC films were synthesized at 600 (CDC-600) and 1000 degrees C (CDC-1000) to vary the carbon morphology from completely amorphous to more ordered, and determine the role of structure, surface area, and porosity on sensor response. Sensor response time followed kinetic diameter and indicated a more ordered carbon structure slowed response due to increased tortuosity caused by the formation of graphitic layers at the particle fringe. Steady state sensor response was greater for the less-ordered material, despite its decreased surface area, decreased micropore volume, and less favorable surface chemistry, suggesting carbon structure is a stronger predictor of sensor response than surface chemistry. The lack of correlation between adsorption of the probe gases and sensor response suggests chemical interaction (charge transfer) drive sensor response within the material; N(2)O response, in particular, did not follow simple adsorption behavior. Based on Raman and FTIR characterization, carbon morphology (disorder) appeared to be the determining factor in overall sensor response, likely due to increased charge transfer between gases and carbon defects of amorphous or disordered regions. The response of the amorphous CDC-600 film to NH(3) was 45% without prior oxidation, showing amorphous CDCs have promise as chemical sensors without additional pretreatment common to other carbon sensors.
Enamel-like apatite crown covering amorphous mineral in a crayfish mandible
Bentov, Shmuel; Zaslansky, Paul; Al-Sawalmih, Ali; Masic, Admir; Fratzl, Peter; Sagi, Amir; Berman, Amir; Aichmayer, Barbara
2012-01-01
Carbonated hydroxyapatite is the mineral found in vertebrate bones and teeth, whereas invertebrates utilize calcium carbonate in their mineralized organs. In particular, stable amorphous calcium carbonate is found in many crustaceans. Here we report on an unusual, crystalline enamel-like apatite layer found in the mandibles of the arthropod Cherax quadricarinatus (freshwater crayfish). Despite their very different thermodynamic stabilities, amorphous calcium carbonate, amorphous calcium phosphate, calcite and fluorapatite coexist in well-defined functional layers in close proximity within the mandible. The softer amorphous minerals are found primarily in the bulk of the mandible whereas apatite, the harder and less soluble mineral, forms a wear-resistant, enamel-like coating of the molar tooth. Our findings suggest a unique case of convergent evolution, where similar functional challenges of mastication led to independent developments of structurally and mechanically similar, apatite-based layers in the teeth of genetically remote phyla: vertebrates and crustaceans. PMID:22588301
Amorphous Calcium Carbonate Based-Microparticles for Peptide Pulmonary Delivery.
Tewes, Frederic; Gobbo, Oliviero L; Ehrhardt, Carsten; Healy, Anne Marie
2016-01-20
Amorphous calcium carbonate (ACC) is known to interact with proteins, for example, in biogenic ACC, to form stable amorphous phases. The control of amorphous/crystalline and inorganic/organic ratios in inhalable calcium carbonate microparticles may enable particle properties to be adapted to suit the requirements of dry powders for pulmonary delivery by oral inhalation. For example, an amorphous phase can immobilize and stabilize polypeptides in their native structure and amorphous and crystalline phases have different mechanical properties. Therefore, inhalable composite microparticles made of inorganic (i.e., calcium carbonate and calcium formate) and organic (i.e., hyaluronan (HA)) amorphous and crystalline phases were investigated for peptide and protein pulmonary aerosol delivery. The crystalline/amorphous ratio and polymorphic form of the inorganic component was altered by changing the microparticle drying rate and by changing the ammonium carbonate and HA initial concentration. The bioactivity of the model peptide, salmon calcitonin (sCT), coprocessed with alpha-1-antitrypsin (AAT), a model protein with peptidase inhibitor activity, was maintained during processing and the microparticles had excellent aerodynamic properties, making them suitable for pulmonary aerosol delivery. The bioavailability of sCT after aerosol delivery as sCT and AAT-loaded composite microparticles to rats was 4-times higher than that of sCT solution.
Xie, Wenhe; Li, Suyuan; Wang, Suiyan; Xue, Song; Liu, Zhengjiao; Jiang, Xinyu; He, Deyan
2014-11-26
N-doped amorphous carbon coated Fe3O4/SnO2 coaxial nanofibers were prepared via a facile approach. The core composite nanofibers were first made by electrospinning technology, then the shells were conformally coated using the chemical bath deposition and subsequent carbonization with polydopamine as a carbon source. When applied as a binder-free self-supported anode for lithium ion batteries, the coaxial nanofibers displayed an enhanced electrochemical storage capacity and excellent rate performance. The morphology of the interwoven nanofibers was maintained even after the rate cycle test. The superior electrochemical performance originates in the structural stability of the N-doped amorphous carbon shells formed by carbonizing polydopamine.
NASA Astrophysics Data System (ADS)
Chen, Jing; Hong, Min; Chen, Jiafu; Hu, Tianzhao; Xu, Qun
2018-06-01
Porous amorphous carbons with large number of defects and dangling bonds indicate great potential application in energy storage due to high specific surface area and strong adsorption properties, but poor conductivity and pore connection limit their practical application. Here few-layer graphene framework with high electrical conductivity is embedded and meanwhile hierarchical porous structure is constructed in amorphous hollow carbon spheres (HCSs) by catalysis of Fe clusters of angstrom scale, which are loaded in the interior of crosslinked polystyrene via a novel method. These unique HCSs effectively integrate the inherent properties from two-dimensional sp2-hybridized carbon, porous amorphous carbon, hierarchical pore structure and thin shell, leading to high specific capacitance up to 561 F g-1 at a current density of 0.5 A g-1 as an electrode of supercapacitor with excellent recyclability, which is much higher than those of other reported porous carbon materials up to present.
Carbide-derived carbons - From porous networks to nanotubes and graphene
DOE Office of Scientific and Technical Information (OSTI.GOV)
Presser, V.; Heon, M.; Gogotsi, Y.
2011-02-09
Carbide-derived carbons (CDCs) are a large family of carbon materials derived from carbide precursors that are transformed into pure carbon via physical (e.g., thermal decomposition) or chemical (e.g., halogenation) processes. Structurally, CDC ranges from amorphous carbon to graphite, carbon nanotubes or graphene. For halogenated carbides, a high level of control over the resulting amorphous porous carbon structure is possible by changing the synthesis conditions and carbide precursor. The large number of resulting carbon structures and their tunability enables a wide range of applications, from tribological coatings for ceramics, or selective sorbents, to gas and electrical energy storage. In particular, themore » application of CDC in supercapacitors has recently attracted much attention. This review paper summarizes key aspects of CDC synthesis, properties, and applications. It is shown that the CDC structure and properties are sensitive to changes of the synthesis parameters. Understanding of processing–structure–properties relationships facilitates tuning of the carbon material to the requirements of a certain application.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
None
Amorphous carbon nanosphere used as the anode material for Li-intercalation in Lithium-ion energy storage. This structure was obtained through a thermal annealing process at a temperature of 3000 degree Kelvin, simulated using the LAMMPS molecular dynamics code on the LCRC Fusion resource. Science: Kah Chun Lau and Larry Curtiss Visualization: Aaron Knoll, Mark Hereld and Michael E. Papka
Ye, ShuJun; Song, MingHui; Kumakura, Hiroaki
2015-01-30
A 3 nm coronene coating and a 4 nm amorphous carbon coating with a uniform shell-core encapsulation structure for nanosized boron (B) powders are formed by a simple process in which coronene is directly mixed with boron particles without a solvent and heated at 520 °C for 1 h or at 630 °C for 3 h in a vacuum-sealed silica tube. Coronene has a melting point lower than its decomposition temperature, which enables liquid coronene to cover B particles by liquid diffusion and penetration without the need for a solvent. The diffusion and penetration of coronene can extend to the boundaries of particles and to inside the agglomerated nanoparticles to form a complete shell-core encapsulated structure. As the temperature is increased, thermal decomposition of coronene on the B particles results in the formation of a uniform amorphous carbon coating layer. This novel and simple nanometer-level uniform amorphous carbon coating method can possibly be applied to many other powders; thus, it has potential applications in many fields at low cost.
Raman spectra boron doped amorphous carbon thin film deposited by bias assisted-CVD
NASA Astrophysics Data System (ADS)
Ishak, A.; Fadzilah, A. N.; Dayana, K.; Saurdi, I.; Malek, M. F.; Nurbaya, Z.; Shafura, A. K.; Rusop, M.
2018-05-01
Boron doped amorphous carbon thin film carbon was deposited at 200°C-350°C by bias assisted-CVD using palm oil as a precursor material. The structural boron doped amorphous carbon films were discussed by Raman analysis through the evolution of D and G bands. The spectral evolution observed showed the increase of upward shift of D and G peaks as substrate deposition temperatures increased. These structural changes were further correlated with optical gap and the results obtained are discussed and compared. The estimated optical band gap is found to be 1.9 to 2.05 eV and conductivity is to be in the range of 10-5 Scm-1 to 10-4 Scm-1. The decrease of optical band gap is associated to conductivity increased which change the characteristic parameters of Raman spectra including the position of G peak, full width at half maximum of G peak, and ID/IG.
Coaxial carbon plasma gun deposition of amorphous carbon films
NASA Technical Reports Server (NTRS)
Sater, D. M.; Gulino, D. A.; Rutledge, S. K.
1984-01-01
A unique plasma gun employing coaxial carbon electrodes was used in an attempt to deposit thin films of amorphous diamond-like carbon. A number of different structural, compositional, and electrical characterization techniques were used to characterize these films. These included scanning electron microscopy, scanning transmission electron microscopy, X ray diffraction and absorption, spectrographic analysis, energy dispersive spectroscopy, and selected area electron diffraction. Optical absorption and electrical resistivity measurements were also performed. The films were determined to be primarily amorphous, with poor adhesion to fused silica substrates. Many inclusions of particulates were found to be present as well. Analysis of these particulates revealed the presence of trace impurities, such as Fe and Cu, which were also found in the graphite electrode material. The electrodes were the source of these impurities. No evidence of diamond-like crystallite structure was found in any of the film samples. Details of the apparatus, experimental procedure, and film characteristics are presented.
NASA Astrophysics Data System (ADS)
Wang, Zhong; Tian, Wenhuai; Liu, Xiaohe; Yang, Rong; Li, Xingguo
2007-12-01
The amorphous carbon coating on the Sn-Sb particles was prepared from aqueous glucose solutions using a hydrothermal method. Because the outer layer carbon of composite materials is loose cotton-like and porous-like, it can accommodate the expansion and contraction of active materials to maintain the stability of the structure, and hinder effectively the aggregation of nano-sized alloy particles. The as-prepared composite materials show much improved electrochemical performances as anode materials for lithium-ion batteries compared with Sn-Sb alloy and carbon alone. This amorphous carbon-coated Sn-Sb particle is extremely promising anode materials for lithium secondary batteries and has a high potentiality in the future use.
Choi, Ji-Seub; Lee, Hoi-Jin; Ha, Jong-Keun; Cho, Kwon-Koo
2018-09-01
Sn is one of the promising anode material for lithium-ion and sodium-ion batteries because of Sn has many advantages such as a high theoretical capacity of 994 mAh/g, inexpensive, abundant and nontoxic. However, Sn-based anodes have a critical problem from pulverization of the particles due to large volume change (>300% in lithium-ion battery and 420% in the sodium-ion battery) during alloying/dealloying reaction. To overcome this problem, we fabricate Sn/C particle of core/shell structure. Sn powder was produced by pulsed wire explosion in liquid media, and amorphous carbon coating process was prepared by hydrothermal synthesis. The charge capacity of Sn electrode and amorphous carbon coated Sn electrode was 413 mAh/g and 452 mAh/g after 40 cycles in lithium half-cell test. The charge capacity of Sn electrode and amorphous carbon coated Sn electrode was 240 mAh/g and 487 mAh/g after 40 cycles in sodium half-cell test. Amorphous carbon coating contributed to the improvement of capacity in lithium and sodium battery systems. And the effect of amorphous carbon coating in sodium battery system was superior to that in lithium battery system.
Thermally induced evolution of hydrogenated amorphous carbon
NASA Astrophysics Data System (ADS)
Mangolini, Filippo; Rose, Franck; Hilbert, James; Carpick, Robert W.
2013-10-01
The thermally induced structural evolution of hydrogenated amorphous carbon (a-C:H) films was investigated in situ by X-ray photoelectron spectroscopy for annealing temperatures up to 500 °C. A model for the conversion of sp3- to sp2-hybridized carbon in a-C:H vs. temperature and time was developed and applied to determine the ranges of activation energies for the thermally activated processes occurring. The energies are consistent with ordering and clustering of sp2 carbon, scission of sp3 carbon-hydrogen bonds and formation of sp2 carbon, and direct transformation of sp3- to sp2-hybridized carbon.
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.
Hwang, Jeongwoon; Ihm, Jisoon; Lee, Kwang-Ryeol; Kim, Seungchul
2015-01-01
We investigate the structural, mechanical, and electronic properties of graphite-like amorphous carbon coating on bulky silicon to examine whether it can improve the durability of the silicon anodes of lithium-ion batteries using molecular dynamics simulations and ab-initio electronic structure calculations. Structural models of carbon coating are constructed using molecular dynamics simulations of atomic carbon deposition with low incident energies (1–16 eV). As the incident energy decreases, the ratio of sp2 carbons increases, that of sp3 decreases, and the carbon films become more porous. The films prepared with very low incident energy contain lithium-ion conducting channels. Also, those films are electrically conductive to supplement the poor conductivity of silicon and can restore their structure after large deformation to accommodate the volume change during the operations. As a result of this study, we suggest that graphite-like porous carbon coating on silicon will extend the lifetime of the silicon anodes of lithium-ion batteries. PMID:28347087
Hwang, Jeongwoon; Ihm, Jisoon; Lee, Kwang-Ryeol; Kim, Seungchul
2015-10-13
We investigate the structural, mechanical, and electronic properties of graphite-like amorphous carbon coating on bulky silicon to examine whether it can improve the durability of the silicon anodes of lithium-ion batteries using molecular dynamics simulations and ab-initio electronic structure calculations. Structural models of carbon coating are constructed using molecular dynamics simulations of atomic carbon deposition with low incident energies (1-16 eV). As the incident energy decreases, the ratio of sp ² carbons increases, that of sp ³ decreases, and the carbon films become more porous. The films prepared with very low incident energy contain lithium-ion conducting channels. Also, those films are electrically conductive to supplement the poor conductivity of silicon and can restore their structure after large deformation to accommodate the volume change during the operations. As a result of this study, we suggest that graphite-like porous carbon coating on silicon will extend the lifetime of the silicon anodes of lithium-ion batteries.
Template-assisted mineral formation via an amorphous liquid phase precursor route
NASA Astrophysics Data System (ADS)
Amos, Fairland F.
The search for alternative routes to synthesize inorganic materials has led to the biomimetic route of producing ceramics. In this method, materials are manufactured at ambient temperatures and in aqueous solutions with soluble additives and insoluble matrix, similar to the biological strategy for the formation of minerals by living organisms. Using this approach, an anionic polypeptide additive was used to induce an amorphous liquid-phase precursor to either calcium carbonate or calcium phosphate. This precursor was then templated on either organic or inorganic substrates. Non-equilibrium morphologies, such as two-dimensional calcium carbonate films, one-dimensional calcium carbonate mesostructures and "molten" calcium phosphate spherulites were produced, which are not typical of the traditional (additive-free) solution grown crystals in the laboratory. In the study of calcium carbonate, the amorphous calcium carbonate mineral formed via the liquid-phase precursor, either underwent a dissolution-recrystallization event or a pseudo-solid-state transformation to produce different morphologies and polymorphs of the mineral. Discrete or aggregate calcite crystals were formed via the dissolution of the amorphous phase to allow the reprecipitation of the stable crystal. Non-equilibrium morphologies, e.g., films, mesotubules and mesowires were templated using organic and inorganic substrates and compartments. These structures were generated via an amorphous solid to crystalline solid transformation. Single crystalline tablets and mesowires of aragonite, which are reported to be found only in nature as skeletal structures of marine organisms, such as mollusk nacre and echinoderm teeth, were successfully synthesized. These biomimetic structures were grown via the polymer-induced liquid-phase precursor route in the presence of magnesium. Only low magnesium-bearing calcite was formed in the absence of the polymer. A similar approach of using a polymeric additive was implemented in calcium phosphate. Spherulitic crystals and films, seemingly formed from a molten state, were produced. These structures served as nucleating surfaces for the radial formation of calcium oxalate minerals. The composite calcium phosphate-calcium oxalate assemblies are similar to the core-shell structures found in certain kidney stones.
Tritiated amorphous silicon for micropower applications
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kherani, N.P.; Kosteski, T.; Zukotynski, S.
1995-10-01
The application of tritiated amorphous silicon as an intrinsic energy conversion semiconductor for radioluminescent structures and betavoltaic devices is presented. Theoretical analysis of the betavoltaic application shows an overall efficiency of 18% for tritiated amorphous silicon. This is equivalent to a 330 Ci intrinsic betavoltaic device producing 1 mW of power for 12 years. Photoluminescence studies of hydrogenated amorphous silicon, a-Si:H, show emission in the infra-red with a maximum quantum efficiency of 7.2% at 50 K; this value drops by 3 orders of magnitude at a temperature of 300 K. Similar studies of hydrogenated amorphous carbon show emission in themore » visible with an estimated quantum efficiency of 1% at 300 K. These results suggest that tritiated amorphous carbon may be the more promising candidate for room temperature radioluminescence in the visible. 18 refs., 5 figs.« less
Wang, Yixian; Tian, Wei; Wang, Luhai; Zhang, Haoran; Liu, Jialiang; Peng, Tingyue; Pan, Lei; Wang, Xiaobo; Wu, Mingbo
2018-02-14
Amorphous carbon is regarded as a promising alternative to commercial graphite as the lithium-ion battery anode due to its capability to reversibly store more lithium ions. However, the structural disorder with a large number of defects can lead to low electrical conductivity of the amorphous carbon, thus limiting its application for high power output. Herein, ultrathin amorphous carbon nanosheets were prepared from petroleum asphalt through tuning the carbonization temperature in a molten-salt medium. The amorphous nanostructure with expanded carbon interlayer spacing can provide substantial active sites for lithium storage, while the two-dimensional (2D) morphology can facilitate fast electrical conductivity. As a result, the electrodes deliver a high reversible capacity, outstanding rate capability, and superior cycling performance (579 and 396 mAh g -1 at 2 and 5 A g -1 after 900 cycles). Furthermore, full cells consisting of the carbon anodes coupled with LiMn 2 O 4 cathodes exhibit high specific capacity (608 mAh g -1 at 50 mA g -1 ) and impressive cycling stability with slow capacity loss (0.16% per cycle at 200 mA g -1 ). The present study not only paves the way for industrial-scale synthesis of advanced carbon materials for lithium-ion batteries but also deepens the fundamental understanding of the intrinsic mechanism of the molten-salt method.
Effect of Ni Core Structure on the Electrocatalytic Activity of Pt-Ni/C in Methanol Oxidation
Kang, Jian; Wang, Rongfang; Wang, Hui; Liao, Shijun; Key, Julian; Linkov, Vladimir; Ji, Shan
2013-01-01
Methanol oxidation catalysts comprising an outer Pt-shell with an inner Ni-core supported on carbon, (Pt-Ni/C), were prepared with either crystalline or amorphous Ni core structures. Structural comparisons of the two forms of catalyst were made using transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and methanol oxidation activity compared using CV and chronoamperometry (CA). While both the amorphous Ni core and crystalline Ni core structures were covered by similar Pt shell thickness and structure, the Pt-Ni(amorphous)/C catalyst had higher methanol oxidation activity. The amorphous Ni core thus offers improved Pt usage efficiency in direct methanol fuel cells. PMID:28811402
Microstructural evolution of ion-irradiated sol–gel-derived thin films
Shojaee, S. A.; Qi, Y.; Wang, Y. Q.; ...
2017-07-17
In this paper, the effects of ion irradiation on the microstructural evolution of sol–gel-derived silica-based thin films were examined by combining the results from Fourier transform infrared, Raman, and X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, and elastic recoil detection. Variations in the chemical composition, density, and structure of the constituent phases and interfaces were studied, and the results were used to propose a microstructural model for the irradiated films. It was discovered that the microstructure of the films after ion irradiation and decomposition of the starting organic materials consisted of isolated hydrogenated amorphous carbon clusters within an amorphous and carbon-incorporatedmore » silica network. A decrease in the bond angle of Si–O–Si bonds in amorphous silica network along with an increase in the concentration of carbon-rich SiO x C y tetrahedra were the major structural changes caused by ion irradiation. Finally, in addition, hydrogen release from free carbon clusters was observed with increasing ion energy and fluence.« less
Moghimian, Pouya; Srot, Vesna; Rothenstein, Dirk; Facey, Sandra J; Harnau, Ludger; Hauer, Bernhard; Bill, Joachim; van Aken, Peter A
2014-09-30
A versatile method for the directional assembly of M13 phage using amorphous carbon and SiO2 thin films was demonstrated. A high affinity of the M13 phage macromolecules for incorporation into aligned structures on an amorphous carbon surface was observed at the concentration range, in which the viral nanofibers tend to disorder. In contrast, the viral particles showed less freedom to adopt an aligned orientation on SiO2 films when deposited in close vicinity. Here an interpretation of the role of the carbon surface in significant enhancement of adsorption and generation of viral arrays with a high orientational order was proposed in terms of surface chemistry and competitive electrostatic interactions. This study suggests the use of amorphous carbon substrates as a template for directional organization of a closely-packed and two-dimensional M13 viral film, which can be a promising route to mineralize a variety of smooth and homogeneous inorganic nanostructure layers.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Shojaee, S. A.; Qi, Y.; Wang, Y. Q.
In this paper, the effects of ion irradiation on the microstructural evolution of sol–gel-derived silica-based thin films were examined by combining the results from Fourier transform infrared, Raman, and X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, and elastic recoil detection. Variations in the chemical composition, density, and structure of the constituent phases and interfaces were studied, and the results were used to propose a microstructural model for the irradiated films. It was discovered that the microstructure of the films after ion irradiation and decomposition of the starting organic materials consisted of isolated hydrogenated amorphous carbon clusters within an amorphous and carbon-incorporatedmore » silica network. A decrease in the bond angle of Si–O–Si bonds in amorphous silica network along with an increase in the concentration of carbon-rich SiO x C y tetrahedra were the major structural changes caused by ion irradiation. Finally, in addition, hydrogen release from free carbon clusters was observed with increasing ion energy and fluence.« less
Synthesis and high temperature stability of amorphous Si(B)CN-MWCNT composite nanowires
NASA Astrophysics Data System (ADS)
Bhandavat, Romil; Singh, Gurpreet
2012-02-01
We demonstrate synthesis of a hybrid nanowire structure consisting of an amorphous polymer-derived silicon boron-carbonitride (Si-B-C-N) shell with a multiwalled carbon nanotube core. This was achieved through a novel process involving preparation of a boron-modified liquid polymeric precursor through a reaction of trimethyl borate and polyureasilazane under atmospheric conditions; followed by conversion of polymer to glass-ceramic on carbon nanotube surfaces through controlled heating. Chemical structure of the polymer was studied by liquid-NMR while evolution of various ceramic phases was studied by Raman spectroscopy, solid-NMR, Fourier transform infrared and X-ray photoelectron spectroscopy. Electron microscopy and X-ray diffraction confirms presence of amorphous Si(B)CN coating on individual nanotubes for all specimen processed below 1400 degree C. Thermogravimetric analysis, followed by TEM revealed high temperature stability of the carbon nanotube core in flowing air up to 1300 degree C.
NASA Astrophysics Data System (ADS)
Nadutov, V. M.; Vashchuk, D. L.; Karbivskii, V. L.; Volosevich, P. Yu.; Davydenko, O. A.
2018-04-01
The effect of cold plastic deformation by upsetting (e = 1.13) on structure and hybridised bonds of carbon in the fcc Invar Fe-30.9%Ni-1.23% C alloy was studied by means of X-ray phase analysis and X-ray photoelectron spectroscopy. Carbon precipitates along grain boundaries and inside of grains in the alloy after annealing and plastic deformation were revealed. The presence of mainly sp2- and sp3-hybridised C-C bonds attributing to graphite and amorphous carbon as well as the carbon bonds with impurity atoms and metallic Fe and Ni atoms in austenitic phase were revealed in the annealed and deformed alloy. It was shown for the first time that plastic deformation of the alloy results in partial destruction of the graphite crystal structure, increasing the relative part of amorphous carbon, and redistribution of carbon between structural elements as well as in a solid solution of austenitic phase.
Li, Xiaowei; Li, Lei; Zhang, Dong; Wang, Aiying
2017-11-29
Amorphous carbon (a-C) films composited with transition layers exhibit the desirable improvement of adhesion strength between films and substrate, but the further understanding on the interfacial structure transformation of a-C structure induced by transition layers is still lacked. In this paper, using ab initio calculations, we comparatively studied the interfacial structure between Ti, Cr, or W transition layers and a-C film from the atomic scale, and demonstrated that the addition of Ti, Cr, or W catalyzed the graphitic transformation of a-C structure at different levels, which provided the theoretical guidance for designing a multilayer nanocomposite film for renewed application.
Method and structure for passivating semiconductor material
Pankove, Jacques I.
1981-01-01
A structure for passivating semiconductor material comprises a substrate of crystalline semiconductor material, a relatively thin film of carbon disposed on a surface of the crystalline material, and a layer of hydrogenated amorphous silicon deposited on the carbon film.
A shear localization mechanism for lubricity of amorphous carbon materials
Ma, Tian-Bao; Wang, Lin-Feng; Hu, Yuan-Zhong; Li, Xin; Wang, Hui
2014-01-01
Amorphous carbon is one of the most lubricious materials known, but the mechanism is not well understood. It is counterintuitive that such a strong covalent solid could exhibit exceptional lubricity. A prevailing view is that lubricity of amorphous carbon results from chemical passivation of dangling bonds on surfaces. Here we show instead that lubricity arises from shear induced strain localization, which, instead of homogeneous deformation, dominates the shearing process. Shear localization is characterized by covalent bond reorientation, phase transformation and structural ordering preferentially in a localized region, namely tribolayer, resulting in shear weakening. We further demonstrate an anomalous pressure induced transition from stick-slip friction to continuous sliding with ultralow friction, due to gradual clustering and layering of graphitic sheets in the tribolayer. The proposed shear localization mechanism sheds light on the mechanism of superlubricity, and would enrich our understanding of lubrication mechanism of a wide variety of amorphous materials. PMID:24412998
Phase transitions in biogenic amorphous calcium carbonate.
Gong, Yutao U T; Killian, Christopher E; Olson, Ian C; Appathurai, Narayana P; Amasino, Audra L; Martin, Michael C; Holt, Liam J; Wilt, Fred H; Gilbert, P U P A
2012-04-17
Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC · H(2)O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC · H(2)O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC · H(2)O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC · H(2)O in vitro.
Phase transitions in biogenic amorphous calcium carbonate
Gong, Yutao U. T.; Killian, Christopher E.; Olson, Ian C.; Appathurai, Narayana P.; Amasino, Audra L.; Martin, Michael C.; Holt, Liam J.; Wilt, Fred H.; Gilbert, P. U. P. A.
2012-01-01
Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC·H2O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC·H2O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC·H2O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC·H2O in vitro. PMID:22492931
NASA Astrophysics Data System (ADS)
Lazar, G.; Bouchet-Fabre, B.; Zellama, K.; Clin, M.; Ballutaud, D.; Godet, C.
2008-10-01
The structural properties of nitrogenated amorphous carbon deposited by radiofrequency magnetron sputtering of graphite in pure N2 plasma are investigated as a function of the substrate temperature and radiofrequency discharge power. The film composition is derived from x-ray photoemission spectroscopy, nuclear reaction analysis and elastic recoil detection measurements and the film microstructure is discussed using infrared, Raman, x-ray photoemission and near edge x-ray absorption fine structure spectroscopic results. At low deposition temperature and low radiofrequency power, the films are soft, porous, and easily contaminated with water vapor and other atmospheric components. The concentration of nitrogen in the films is very large for low deposition temperatures (˜33.6at.% N at 150°C) but decreases strongly when the synthesis temperature increases (˜15at.% N at 450°C). With increasing deposition temperature and discharge power values, the main observed effects in amorphous carbon nitride alloys are a loss of nitrogen atoms, a smaller hydrogen and oxygen contamination related to the film densification, an increased order of the aromatic sp2 phase, and a strong change in the nitrogen distribution within the carbon matrix. Structural changes are well correlated with modifications of the optical and transport properties.
Shi, Peipei; Li, Li; Hua, Li; Qian, Qianqian; Wang, Pengfei; Zhou, Jinyuan; Sun, Gengzhi; Huang, Wei
2017-01-24
Solid-state fiber-based supercapacitors have been considered promising energy storage devices for wearable electronics due to their lightweight and amenability to be woven into textiles. Efforts have been made to fabricate a high performance fiber electrode by depositing pseudocapacitive materials on the outer surface of carbonaceous fiber, for example, crystalline manganese oxide/multiwalled carbon nanotubes (MnO 2 /MWCNTs). However, a key challenge remaining is to achieve high specific capacitance and energy density without compromising the high rate capability and cycling stability. In addition, amorphous MnO 2 is actually preferred due to its disordered structure and has been proven to exhibit superior electrochemical performance over the crystalline one. Herein, by incorporating amorphous MnO 2 onto a well-aligned MWCNT sheet followed by twisting, we design an amorphous MnO 2 @MWCNT fiber, in which amorphous MnO 2 nanoparticles are distributed in MWCNT fiber uniformly. The proposed structure gives the amorphous MnO 2 @MWCNT fiber good mechanical reliability, high electrical conductivity, and fast ion-diffusion. Solid-state supercapacitor based on amorphous MnO 2 @MWCNT fibers exhibits improved energy density, superior rate capability, exceptional cycling stability, and excellent flexibility. This study provides a strategy to design a high performance fiber electrode with microstructure control for wearable energy storage devices.
NASA Astrophysics Data System (ADS)
Kayed, Kamal
2018-06-01
The aim of this paper is to investigate the relationship between the micro structure and the surface charge effect resulted during XPS surface analysis of amorphous carbon nitride thin films prepared by laser ablation method. The study results show that the charge effect coefficient (E) is not just a correction factor. We found that the changes in this coefficient value due to incorporation of nitrogen atoms into the carbon network are related to the spatial configurations of the sp2 bonded carbon atoms, order degree and sp2 clusters size. In addition, results show that the curve E vs. C(sp3)-N is a characteristic curve of the micro structure. This means that using this curve makes it easy to sorting the samples according to the micro structure (hexagonal rings or chains).
Rodríguez-Navarro, Alejandro B; Marie, Pauline; Nys, Yves; Hincke, Maxwell T; Gautron, Joel
2015-06-01
Avian eggshell mineralization is the fastest biogenic calcification process known in nature. How this is achieved while producing a highly crystalline material composed of large calcite columnar single crystals remains largely unknown. Here we report that eggshell mineral originates from the accumulation of flat disk-shaped amorphous calcium carbonate (ACC) particles on specific organic sites on the eggshell membrane, which are rich in proteins and sulfated proteoglycans. These structures known as mammillary cores promote the nucleation and stabilization of a amorphous calcium carbonate with calcitic short range order which predetermine the calcite composition of the mature eggshell. The amorphous nature of the precursor phase was confirmed by the diffuse scattering of X-rays and electrons. The nascent calcitic short-range order of this transient mineral phase was revealed by infrared spectroscopy and HRTEM. The ACC mineral deposited around the mammillary core sites progressively transforms directly into calcite crystals without the occurrence of any intermediate phase. Ionic speciation data suggest that the uterine fluid is equilibrated with amorphous calcium carbonate, throughout the duration of eggshell mineralization process, supporting that this mineral phase is constantly forming at the shell mineralization front. On the other hand, the transient amorphous calcium carbonate mineral deposits, as well as the calcite crystals into which they are converted, form by the ordered aggregation of nanoparticles that support the rapid mineralization of the eggshell. The results of this study alter our current understanding of avian eggshell calcification and provide new insights into the genesis and formation of calcium carbonate biominerals in vertebrates. Copyright © 2015 Elsevier Inc. All rights reserved.
Molding mineral within microporous hydrogels by a polymer-induced liquid-precursor (PILP) process.
Cheng, Xingguo; Gower, Laurie B
2006-01-01
Natural biominerals often have exquisite morphologies, where the cells exercise a high degree of crystallographic control through secretion of biological macromolecules and regulation of ion transport. One important example is the sea urchin spine. It has recently been shown to be formed through deposition of a transient amorphous calcium carbonate (ACC) precursor phase that later transforms to single-crystalline calcite, ultimately forming an elaborate three-dimensional microporous calcium carbonate structure with interconnected pores. Macromolecules associated with the mineral phase are thought to play a key role in regulating this transformation. The work described here mimics this type of morphological control by "molding" an amorphous calcium carbonate precursor within a porous poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogel that has been prepared as a negative replica from the void space of an urchin spine. Using an acidic biomimetic polymer as a process-directing agent, we show that polyaspartic acid induces amorphous calcium carbonate (ACC) nanoparticles, which have fluidic character and therefore are able to infiltrate the PHEMA hydrogel replica and coalesce into the convoluted morphology that replicates the original microporous structure of the sea urchin spine. By "molding" calcium carbonate into a complex morphology at room temperature, using a precursor process that is induced by a biomimetic acidic macromolecule, the PILP process is a useful in vitro model for examining different aspects of the amorphous-to-crystalline transformation process that is apparently used by a variety of biomineralizing organisms. For example, although we were able to replicate the overall morphology of the spine, it had polycrystalline texture; further studies with this system will focus on controlling the nucleation event, which may help to elucidate how such a convoluted structure can be prepared with single-crystalline texture via an amorphous precursor. Through a better understanding of the mechanisms used by organisms to regulate crystal properties, such biomimetic processes can lead to the synthesis of materials with superior electronic, mechanical, and optical properties.
Ogata, K; Salager, E; Kerr, C J; Fraser, A E; Ducati, C; Morris, A J; Hofmann, S; Grey, C P
2014-01-01
Nano-structured silicon anodes are attractive alternatives to graphitic carbons in rechargeable Li-ion batteries, owing to their extremely high capacities. Despite their advantages, numerous issues remain to be addressed, the most basic being to understand the complex kinetics and thermodynamics that control the reactions and structural rearrangements. Elucidating this necessitates real-time in situ metrologies, which are highly challenging, if the whole electrode structure is studied at an atomistic level for multiple cycles under realistic cycling conditions. Here we report that Si nanowires grown on a conducting carbon-fibre support provide a robust model battery system that can be studied by (7)Li in situ NMR spectroscopy. The method allows the (de)alloying reactions of the amorphous silicides to be followed in the 2nd cycle and beyond. In combination with density-functional theory calculations, the results provide insight into the amorphous and amorphous-to-crystalline lithium-silicide transformations, particularly those at low voltages, which are highly relevant to practical cycling strategies.
He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong
2016-08-09
The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.
An early-branching microbialite cyanobacterium forms intracellular carbonates.
Couradeau, Estelle; Benzerara, Karim; Gérard, Emmanuelle; Moreira, David; Bernard, Sylvain; Brown, Gordon E; López-García, Purificación
2012-04-27
Cyanobacteria have affected major geochemical cycles (carbon, nitrogen, and oxygen) on Earth for billions of years. In particular, they have played a major role in the formation of calcium carbonates (i.e., calcification), which has been considered to be an extracellular process. We identified a cyanobacterium in modern microbialites in Lake Alchichica (Mexico) that forms intracellular amorphous calcium-magnesium-strontium-barium carbonate inclusions about 270 nanometers in average diameter, revealing an unexplored pathway for calcification. Phylogenetic analyses place this cyanobacterium within the deeply divergent order Gloeobacterales. The chemical composition and structure of the intracellular precipitates suggest some level of cellular control on the biomineralization process. This discovery expands the diversity of organisms capable of forming amorphous calcium carbonates.
A near-wearless and extremely long lifetime amorphous carbon film under high vacuum
Wang, Liping; Zhang, Renhui; Jansson, Ulf; Nedfors, Nils
2015-01-01
Prolonging wear life of amorphous carbon films under vacuum was an enormous challenge. In this work, we firstly reported that amorphous carbon film as a lubricant layer containing hydrogen, oxygen, fluorine and silicon (a-C:H:O:F:Si) exhibited low friction (~0.1), ultra-low wear rate (9.0 × 10–13 mm3 N–1 mm–1) and ultra-long wear life (>2 × 106 cycles) under high vacuum. We systematically examined microstructure and composition of transfer film for understanding of the underlying frictional mechanism, which suggested that the extraordinarily excellent tribological properties were attributed to the thermodynamically and structurally stable FeF2 nanocrystallites corroborated using first-principles calculations, which were induced by the tribochemical reaction. PMID:26059254
Li-Ion Localization and Energetics as a Function of Anode Structure.
McNutt, Nicholas W; McDonnell, Marshall; Rios, Orlando; Keffer, David J
2017-03-01
In this work, we study the effect of carbon composite anode structure on the localization and energetics of Li-ions. A computational molecular dynamics study is combined with experimental results from neutron scattering experiments to understand the effect of composite density, crystallite size, volume fraction of crystalline carbon, and ion loading on the nature of ion storage in novel, lignin-derived composite materials. In a recent work, we demonstrated that these carbon composites display a fundamentally different mechanism for Li-ion storage than traditional graphitic anodes. The edges of the crystalline and amorphous fragments of aromatic carbon that exist in these composites are terminated by hydrogen atoms, which play a crucial role in adsorption. In this work, we demonstrate how differences in composite structure due to changes in the processing conditions alter the type and extent of the interface between the amorphous and crystalline domains, thus impacting the nature of Li-ion storage. The effects of structural properties are evaluated using a suite of pair distribution functions as well as an original technique to extract archetypal structures, in the form of three-dimensional atomic density distributions, from highly disordered systems. The energetics of Li-ion binding are understood by relating changes in the energy and charge distributions to changes in structural properties. The distribution of Li-ion energies reveals that some structures lead to greater chemisorption, while others have greater physisorption. Carbon composites with a high volume fraction of small crystallites demonstrate the highest ion storage capacity because of the high interfacial area between the crystalline and amorphous domains. At these interfaces, stable H atoms, terminating the graphitic crystallites, provide favorable sites for reversible Li adsorption.
Phase transitions in biogenic amorphous calcium carbonate
NASA Astrophysics Data System (ADS)
Gong, Yutao
Geological calcium carbonate exists in both crystalline phases and amorphous phases. Compared with crystalline calcium carbonate, such as calcite, aragonite and vaterite, the amorphous calcium carbonate (ACC) is unstable. Unlike geological calcium carbonate crystals, crystalline sea urchin spicules (99.9 wt % calcium carbonate and 0.1 wt % proteins) do not present facets. To explain this property, crystal formation via amorphous precursors was proposed in theory. And previous research reported experimental evidence of ACC on the surface of forming sea urchin spicules. By using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), we studied cross-sections of fresh sea urchin spicules at different stages (36h, 48h and 72h after fertilization) and observed the transition sequence of three mineral phases: hydrated ACC → dehydrated ACC → biogenic calcite. In addition, we unexpectedly found hydrated ACC nanoparticles that are surrounded by biogenic calcite. This observation indicates the dehydration from hydrated ACC to dehydrated ACC is inhibited, resulting in stabilization of hydrated ACC nanoparticles. We thought that the dehydration was inhibited by protein matrix components occluded within the biomineral, and we designed an in vitro assay to test the hypothesis. By utilizing XANES-PEEM, we found that SM50, the most abundant occluded matrix protein in sea urchin spicules, has the function to stabilize hydrated ACC in vitro.
Ternary graphene/amorphous carbon/nickel nanocomposite film for outstanding superhydrophobicity
NASA Astrophysics Data System (ADS)
Zhu, Xiaobo; Zhou, Shengguo; Yan, Qingqing
2018-04-01
A novel superhydrophobic ternary graphene/amorphous carbon/nickel (G-Ni/a-C:H) carbon-based film was fabricated by a green approach of high-voltage electrochemical deposition without using aqueous solution, which was systematically investigated including the structure and relating applications on self-cleaning and corrosion resistance. Graphene and nickel nano-particle inserts were effective to tailor the feature of nanocrystallite/amorphous microstructure as well as micro-nanoscale hierarchical rose-petal-like surface for G-Ni/a-C:H carbon-based film. Surprisingly, this deposit could present outstanding superhydrophobicity with the contact angle of 158.98 deg and sliding angle of 2.75 deg without any further surface modification meanwhile it could possess fairly well adhesion. Furthermore, the superhydrophobic G-Ni/a-C:H carbon-based film could exhibit excellent corrosion resistance and self-cleaning performances compared to no graphene incorporated deposit. The procedure of fabricating deposit might be simple, scalable, and environmental friendly, indicating a promising prospect for industrial applications in the field of anti-fouling, anti-corrosion and drag resistance.
NASA Astrophysics Data System (ADS)
Wang, Yongfu; Gao, Kaixiong; Zhang, Junyan
2016-07-01
In this study, fullerene like carbon (FL-C) is introduced in hydrogenated amorphous carbon (a-C:H) film by employing a direct current plasma enhanced chemical vapor deposition. The film has a low friction and wear, such as 0.011 and 2.3 × 10-9mm3/N m in the N2, and 0.014 and 8.4 × 10-8mm3/N m in the humid air, and high hardness and elasticity (25.8 GPa and 83.1%), to make further engineering applications in practice. It has several nanometers ordered domains consisting of less frequently cross-linked graphitic sheet stacks. We provide new evidences for understanding the reported Raman fit model involving four vibrational frequencies from five, six, and seven C-atom rings of FL-C structures, and discuss the structure evolution before or after friction according to the change in the 1200 cm-1 Raman band intensity caused by five- and seven-carbon rings. Friction inevitably facilitates the transformation of carbon into FL-C nanostructures, namely, the ultra low friction comes from both such structures within the carbon film and the sliding induced at friction interface.
Deduced elasticity of sp3-bonded amorphous diamond
NASA Astrophysics Data System (ADS)
Ballato, J.; Ballato, A.
2017-11-01
Amorphous diamond was recently synthesized using high temperature and pressure techniques [Z. Zeng, L. Yang, Q. Zeng, H. Lou, H. Sheng, J. Wen, D. J. Miller, Y. Meng, W. Yang, W. L. Mao, and H. K. Mao, Nat. Commun. 8, 322 (2017)]. Here, selected physical properties of this new phase of carbon are deduced using an extension of the Voigt-Reuss-Hill (VRHx) methodology whereby single crystal values are averaged over all orientations to yield values for the amorphous analog. Specifically, the elastic constants were deduced to be c11 = 1156.5 GPa, c12 = 87.6 GPa, and c44 = 534.5 GPa, whereas the Young's modulus, bulk modulus, and Poisson's ratio were also estimated to be 1144.2 GPa, 443.9 GPa, and 0.0704, respectively. These numbers are compared with experimental and theoretical literature values for other allotropic forms, specifically, Lonsdaleite, and two forms each of graphite and amorphous carbon. It is unknown at this time how the high temperature and pressure synthesis approach employed influences the structure, hence properties, of amorphous diamond at room temperature. However, the values provided herein constitute a baseline against which future structure/property/processing analyses can be compared.
Toughening Fe-based Amorphous Coatings by Reinforcement of Amorphous Carbon.
Wang, Wei; Zhang, Cheng; Zhang, Zhi-Wei; Li, Yi-Cheng; Yasir, Muhammad; Wang, Hai-Tao; Liu, Lin
2017-06-22
Toughening of Fe-based amorphous coatings meanwhile maintaining a good corrosion resistance remains challenging. This work reports a novel approach to improve the toughness of a FeCrMoCBY amorphous coating through in-situ formation of amorphous carbon reinforcement without reducing the corrosion resistance. The Fe-based composite coating was prepared by high velocity oxy-fuel (HVOF) thermal spraying using a pre-mixed Fe-based amorphous/nylon-11 polymer feedstock powders. The nylon-11 powders were in-situ carbonized to amorphous carbon phase during thermal spraying process, which homogeneously distributed in the amorphous matrix leading to significant enhancement of toughness of the coating. The mechanical properties, including hardness, impact resistance, bending and fatigue strength, were extensively studied by using a series of mechanical testing techniques. The results revealed that the composite coating reinforced by amorphous carbon phase exhibited enhanced impact resistance and nearly twice-higher fatigue strength than that of the monolithic amorphous coating. The enhancement of impact toughness and fatigue properties is owed to the dumping effect of the soft amorphous carbon phase, which alleviated stress concentration and decreased crack propagation driving force.
NASA Astrophysics Data System (ADS)
Mergelsberg, S. T.; Ulrich, R. N.; Michel, F. M.; Dove, P. M.
2017-12-01
Recent advances in high-resolution imaging show the widespreadd occurrence of multistep pathways to mineralization in biological and geological settings (De Yoreo et al., 2015, Science). For example, carbonate biomineralization often involves precipitation of amorphous calcium carbonate (ACC) as a reactive intermediate that subsequently transforms to crystalline products with diverse structures. Although current carbonate mineral proxies are based upon the composition of final crystalline products, the final signatures may be recording the properties of the initial amorphous phase. Thus, it is critical to establish the physical properties of ACC and understand the factors that influence its evolution to final products at conditions that approximate biological environments. This disconnect limits our ability to build a process-based understanding of when/how minor and trace elements are recorded in mineral composition proxies. In this experimental study, we quantified the chemical and physical properties of ACC and its evolution to final products. We first determined ACC solubility under controlled chemical conditions using a new type of flow-through reactor developed by our research group (Blue and Dove, 2015, GCA; Blue et al., 2017, GCA). The experimental design varied Mg concentration and total alkalinity while maintaining a mild pH that approximates biological environments. ACC solubility was measured at specific time points during the precipitation (from super- and undersaturated conditions) and during its subsequent evolution. Parallel experiments characterized the structure of the corresponding amorphous products using in situ pair distribution function (PDF) and small-angle x-ray scattering (SAXS) analyses. The measurements demonstrate at least two types of ACC can be produced by tuning Mg concentration and alkalinity. Each "phase" exhibits distinct short-range ordering that demonstrates structure-specific solubility. We also find temporal changes in the short-range order of each type of ACC that are dependent upon Mg content. Insights from this study hold promise for quantifying the chemical and structural properties of ACC and reconcile discrepancies in the literature.
Abraham, Anuji; Crull, George
2014-10-06
A simple and robust method for obtaining fluorine-carbon proximities was established using a (19)F-(13)C heteronuclear correlation (HETCOR) two-dimensional (2D) solid-state nuclear magnetic resonance (ssNMR) experiment under magic-angle spinning (MAS). The method was applied to study a crystalline active pharmaceutical ingredient (API), avagacestat, containing two types of fluorine atoms and its API-polymer composite drug product. These results provide insight into the molecular structure, aid with assigning the carbon resonances, and probe API-polymer proximities in amorphous spray dried dispersions (SDD). This method has an advantage over the commonly used (1)H-(13)C HETCOR because of the large chemical shift dispersion in the fluorine dimension. In the present study, fluorine-carbon distances up to 8 Å were probed, giving insight into the API structure, crystal packing, and assignments. Most importantly, the study demonstrates a method for probing an intimate molecular level contact between an amorphous API and a polymer in an SDD, giving insights into molecular association and understanding of the role of the polymer in API stability (such as recrystallization, degradation, etc.) in such novel composite drug products.
Method of forming a stress relieved amorphous tetrahedrally-coordinated carbon film
Friedmann, Thomas A.; Sullivan, John P.
2000-01-01
A stress-relieved amorphous-diamond film is formed by depositing an amorphous diamond film with specific atomic structure and bonding on to a substrate, and annealing the film at sufficiently high temperature to relieve the compressive stress in said film without significantly softening said film. The maximum annealing temperature is preferably on the order of 650.degree. C., a much lower value than is expected from the annealing behavior of other materials.
Song, Yu; Liu, Tian-Yu; Yao, Bin; Kou, Tian-Yi; Feng, Dong-Yang; Liu, Xiao-Xia; Li, Yat
2017-04-01
Previous studies show that vanadium oxides suffer from severe capacity loss during cycling in the liquid electrolyte, which has hindered their applications in electrochemical energy storage. The electrochemical instability is mainly due to chemical dissolution and structural pulverization of vanadium oxides during charge/discharge cyclings. In this study the authors demonstrate that amorphous mixed-valence vanadium oxide deposited on exfoliated carbon cloth (CC) can address these two limitations simultaneously. The results suggest that tuning the V 4+ /V 5+ ratio of vanadium oxide can efficiently suppress the dissolution of the active materials. The oxygen-functionalized carbon shell on exfoliated CC can bind strongly with VO x via the formation of COV bonding, which retains the electrode integrity and suppresses the structural degradation of the oxide during charging/discharging. The uptake of structural water during charging and discharging processes also plays an important role in activating the electrode material. The amorphous mixed-valence vanadium oxide without any protective coating exhibits record-high cycling stability in the aqueous electrolyte with no capacitive decay in 100 000 cycles. This work provides new insights on stabilizing vanadium oxide, which is critical for the development of vanadium oxide based energy storage devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Zhang, Lina; Zhang, Haoxu; Zhou, Ruifeng; Chen, Zhuo; Li, Qunqing; Fan, Shoushan; Ge, Guanglu; Liu, Renxiao; Jiang, Kaili
2011-09-23
A novel grid for use in transmission electron microscopy is developed. The supporting film of the grid is composed of thin graphene oxide films overlying a super-aligned carbon nanotube network. The composite film combines the advantages of graphene oxide and carbon nanotube networks and has the following properties: it is ultra-thin, it has a large flat and smooth effective supporting area with a homogeneous amorphous appearance, high stability, and good conductivity. The graphene oxide-carbon nanotube grid has a distinct advantage when characterizing the fine structure of a mass of nanomaterials over conventional amorphous carbon grids. Clear high-resolution transmission electron microscopy images of various nanomaterials are obtained easily using the new grids.
NASA Astrophysics Data System (ADS)
Liu, Boyang; Shao, Yingfeng; Xiang, Xin; Zhang, Fuhua; Yan, Shengchang; Li, Wenge
2017-08-01
Various carbon encapsulated nanocrystals, including MnS and MnO, Cr2O3, MoO2, Fe7S8 and Fe3O4, and ZrO2, are prepared in one step and in situ by a simple and highly efficient synthesis approach. The nanocrystals have an equiaxed morphology and a median size smaller than 30 nm. Tens and hundreds of these nanocrystals are entirely encapsulated by a wormlike amorphous carbon shell. The formation of a core-shell structure depends on the strongly exothermic reaction of metal π-complexes with ammonium persulfate in an autoclave at below 200 °C. During the oxidation process, the generated significant amounts of heat will destroy the molecular structure of the metal π-complex and cleave the ligands into small carbon fragments, which further transform into an amorphous carbon shell. The central metal atoms are oxidized to metal oxide/sulfide nanocrystals. The formation of a core-shell structure is independent of the numbers of ligands and carbon atoms as well as the metal types, implying that any metal π-complex can serve as a precursor and that various carbon encapsulated nanocrystals can be synthesized by this method.
NASA Astrophysics Data System (ADS)
Wang, Yongfu; Gao, Kaixiong; Wang, Qi; Zhang, Junyan
2018-01-01
Fullerene-like hydrogenated carbon films have outstanding mechanical and frictional properties, but their structures have never enjoyed elaboration. In this study, we investigate the relation between nano-hardness and elasticity and fullerene-like clusters by changing energy supply form (direct current and pulse) and H2 concentration in the feedstock. It is found that the films have a network of H-rich amorphous carbon and H-poor or -deficient fullerene-like carbon, and the network change can affect hardness and elastic recovery. This is due to the energy minimization process of the film growing system in a very short pulse period at low temperature.
Electron diffraction and microscopy study of nanotubes and nanowires
NASA Astrophysics Data System (ADS)
Deniz, Hakan
Carbon nanotubes have many excellent properties that are strongly influenced by their atomic structure. The realization of the ultimate potential of carbon nanotubes in technological applications necessitates a precise control of the structure of as-grown nanotubes as well as the identification of their atomic structures. Transmission electron microscopy (TEM) is a technique that can deliver this by combining the high resolution imaging and electron diffraction simultaneously. In this study, a new catalyst system (the Co/Si) was investigated in the production of single-walled carbon nanotubes (SWNTs) by laser ablation. It was discovered that the Co/Si mixture as a catalyst was as successful as the Ni/Co in the synthesis of SWNTs. The isolated individual SWNTs were examined by using nanobeam electron diffraction for the structure identification and it was found that carbon nanotubes grown by this catalyst mixture tend to be slightly more metallic. The electron diffraction technique has been refined to establish a new methodology to determine the chirality of each shell in a carbon nanotube and it has been applied to determine the atomic structure of double-walled carbon nanotubes (DWNT), few-walled carbon nanotubes (FWNT) and multi-walled carbon nanotubes (MWNT). We observed that there is no strong correlation in the structure of two adjacent shells in DWNTs. Several FWNTs and MWNTs have been examined by our new electron diffraction method to determine their atomic structures and to test the efficiency and the reliability of this method for structure identification. We now suggest that a carbon nanotube of up to 25 shells can be studied and the chirality of each shell can be identified by this new technique. The guidelines for the automation of such procedure have been laid down and explained in this work. The atomic structure of tungsten disulfide (WS2) nanotubes was studied by using the methods developed for the structure determination of carbon nanotubes. The WS2 nanotubes are another example of the tube forming ability of the layered structures and a member of the family of inorganic fullerene-like structures. These nanotubes are much larger in diameter than carbon nanotubes. The tubes studied here have helicities less than 18° and usually have near zigzag structure. The short-range order (SRO) in the atomic structure of carbon soot produced by laser ablation was investigated using electron diffraction and radial distribution function (RDF) analysis. The effects of the furnace temperature and the metal catalyst on the SRO in the carbon soot were also studied. It was discovered that the SRO structure is the same for all carbon soot samples studied and is very similar to that of amorphous carbon. These techniques were also applied to determine the atomic structure of amorphous boron nanowires. We found out that the atomic structure of these boron nanowires agree well with the previously reported structure of bulk amorphous boron.
Cellular control over spicule formation in sea urchin embryos: A structural approach.
Beniash, E; Addadi, L; Weiner, S
1999-03-01
The spicules of the sea urchin embryo form in intracellular membrane-delineated compartments. Each spicule is composed of a single crystal of calcite and amorphous calcium carbonate. The latter transforms with time into calcite by overgrowth of the preexisting crystal. Relationships between the membrane surrounding the spiculogenic compartment and the spicule mineral phase were studied in the transmission electron microscope (TEM) using freeze-fracture. In all the replicas observed the spicules were tightly surrounded by the membrane. Furthermore, a variety of structures that are related to the material exchange process across the membrane were observed. The spiculogenic cells were separated from other cell types of the embryo, frozen, and freeze-dried on the TEM grids. The contents of electron-dense granules in the spiculogenic cells were shown by electron diffraction to be composed of amorphous calcium carbonate. These observations are consistent with the notion that the amorphous calcium carbonate-containing granules contain the precursor mineral phase for spicule formation and that the membrane surrounding the forming spicule is involved both in transport of material and in controlling spicule mineralization. Copyright 1999 Academic Press.
Protein adsorption on thin films of carbon and carbon nitride monitored with in situ ellipsometry.
Berlind, T; Tengvall, P; Hultman, L; Arwin, H
2011-03-01
Thin films of amorphous carbon and amorphous, graphitic and fullerene-like carbon nitride were deposited by reactive magnetron sputtering and optically characterized with spectroscopic ellipsometry. Complementary studies using scanning electron microscopy and atomic force microscopy were performed. The films were exposed to human serum albumin (HSA) and the adsorption was monitored in situ using dynamic ellipsometry. From the ellipsometric data the adsorbed amount of proteins was quantified in terms of surface mass density using de Feijter's model. The results indicate larger adsorption of proteins onto the amorphous films compared to the films with a more textured structure. Complementary studies with 125I-labeled HSA showed an apparent protein adsorption up to six times larger compared to the ellipsometry measurement. In addition, the four types of films were incubated in blood plasma followed by exposure to anti-fibrinogen, anti-HMWK or anti-C3c, revealing the materials' response to complement and contact activation. The amorphous and graphitic carbon nitride exhibit rather high immune activity compared to a titanium reference, whereas the amorphous carbon and the fullerene-like CNx show less immune complement deposition. Compared to the reference, all films exhibit indications of a stronger ability to initiate the intrinsic pathway of coagulation. Finally, the surfaces' bone-bonding ability was investigated by examination of their ability to form calcium phosphate crystals in a simulated body fluid, with a-CNx depositing most calcium phosphate after 21 days of incubation. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Jones, A. P.
2012-04-01
Context. The compositional properties of hydrogenated amorphous carbons are known to evolve in response to the local conditions. Aims: We present a model for low-temperature, amorphous hydrocarbon solids, based on the microphysical properties of random and defected networks of carbon and hydrogen atoms, that can be used to study and predict the evolution of their properties in the interstellar medium. Methods: We adopt an adaptable and prescriptive approach to model these materials, which is based on a random covalent network (RCN) model, extended here to a full compositional derivation (the eRCN model), and a defective graphite (DG) model for the hydrogen poorer materials where the eRCN model is no longer valid. Results: We provide simple expressions that enable the determination of the structural, infrared and spectral properties of amorphous hydrocarbon grains as a function of the hydrogen atomic fraction, XH. Structural annealing, resulting from hydrogen atom loss, results in a transition from H-rich, aliphatic-rich to H-poor, aromatic-rich materials. Conclusions: The model predicts changes in the optical properties of hydrogenated amorphous carbon dust in response to the likely UV photon-driven and/or thermal annealing processes resulting, principally, from the radiation field in the environment. We show how this dust component will evolve, compositionally and structurally in the interstellar medium in response to the local conditions. Appendices A and B are available in electronic form at http://www.aanda.org
NASA Astrophysics Data System (ADS)
da Silva, D. S.; Côrtes, A. D. S.; Oliveira, M. H.; Motta, E. F.; Viana, G. A.; Mei, P. R.; Marques, F. C.
2011-08-01
We report on the investigation of the potential application of different forms of amorphous carbon (a-C and a-C:H) as an antireflective coating for crystalline silicon solar cells. Polymeric-like carbon (PLC) and hydrogenated diamond-like carbon films were deposited by plasma enhanced chemical vapor deposition. Tetrahedral amorphous carbon (ta-C) was deposited by the filtered cathodic vacuum arc technique. Those three different amorphous carbon structures were individually applied as single antireflective coatings on conventional (polished and texturized) p-n junction crystalline silicon solar cells. Due to their optical properties, good results were also obtained for double-layer antireflective coatings based on PLC or ta-C films combined with different materials. The results are compared with a conventional tin dioxide (SnO2) single-layer antireflective coating and zinc sulfide/magnesium fluoride (ZnS/MgF2) double-layer antireflective coatings. An increase of 23.7% in the short-circuit current density, Jsc, was obtained using PLC as an antireflective coating and 31.7% was achieved using a double-layer of PLC with a layer of magnesium fluoride (MgF2). An additional increase of 10.8% was obtained in texturized silicon, representing a total increase (texturization + double-layer) of about 40% in the short-circuit current density. The potential use of these materials are critically addressed considering their refractive index, optical bandgap, absorption coefficient, hardness, chemical inertness, and mechanical stability.
Bond topography and nanostructure of hydrogenated fullerene-like carbon films: A comparative study
NASA Astrophysics Data System (ADS)
Wang, Yongfu; Gao, Kaixiong; Shi, Jing; Zhang, Junyan
2016-09-01
Fullerene-like nanostructural hydrogenated amorphous carbon (FL-C:H) films were prepared by dc- and pulse- plasma enhanced chemical vapor deposition technique (PECVD). Both the films exhibit relatively stresses (0.63 GPa) in spite of their FL features and nanostructural bonding configurations, especially the pentagonal carbon rings. The creation of pentagonal rings is not fully driven by thermodynamics, but is closely related to compressive stress determined by the ion bombardment at the discharged state of the pulse- and dc- discharged plasmas methods. The dc method leads to FL's basal planes which contain less cross-linkages, and causes amorphous strongly hydrogenated structures.
Structure and properties of carbon black particles
NASA Astrophysics Data System (ADS)
Xu, Wei
Structure and properties of carbon black particles were investigated using atomic force microscopy, gas adsorption, Raman spectroscopy, and X-ray diffraction. Supplementary information was obtained using TEM and neutron scattering. The AFM imaging of carbon black aggregates provided qualitative visual information on their morphology, complementary to that obtained by 3-D modeling based on TEM images. Our studies showed that carbon black aggregates were relatively flat. The surface of all untreated carbon black particles was found to be rough and its fractal dimension was 2.2. Heating reduced the roughness and fractal dimension for all samples heat treated at above 1300 K to 2.0. Once the samples were heat treated rapid cooling did not affect the surface roughness. However, rapid cooling reduced crystallite sizes, and different Raman spectra were obtained for carbon blacks of various history of heat treatment. By analyzing the Raman spectra we determined the crystallite sizes and identified amorphous carbon. The concentration of amorphous carbon depends on hydrogen content. Once hydrogen was liberated at increased temperature, the concentration of amorphous carbon was reduced and crystallites started to grow. Properties of carbon blacks at high pressure were also studied. Hydrostatic pressure did not affect the size of the crystallites in carbon black particles. The pressure induced shift in Raman frequency of the graphitic component was a result of increased intermolecular forces and not smaller crystallites. Two methods of determining the fractal dimension, the FHH model and the yardstick technique based on the BET theory were used in the literature. Our study proved that the FHH model is sensitive to numerous assumptions and leads to wrong conclusions. On the other hand the yardstick method gave correct results, which agreed with the AFM results.
Growth and structure of hydrogenated carbon films containing fullerene-like structure
NASA Astrophysics Data System (ADS)
Wang, Peng; Wang, Xia; Liu, Weimin; Zhang, Junyan
2008-04-01
Hydrogenated carbon films were prepared by magnetron sputtering of a titanium target in methane and argon atmosphere. The film grown at -800 V bias exhibits excellent mechanical properties with a hardness of 20.9 GPa and an elastic recovery as high as 85%. Its structure, characterized by high-resolution transmission electron microscopy, Raman spectrum, and x-ray photoelectron spectroscopy, can be described as fullerene-like structures uniformly dispersed in an amorphous carbon matrix. In order to reveal the evolution of fullerene-like structures in our films, different bias voltages were introduced. The results show that high bias voltage leads to the accumulation of high compressive internal stress in the film and promotes the evolution of fullerene-like structures. Although the film grown at -800 V bias presents high sp2 bonding content, it exhibits good mechanical properties with high hardness and high elasticity at the same time; we attribute it to the unique structure of the film, in which a fullerene-like structure, just like a molecule spring dispersed in the film, reserves the elastic energy during distortion through reversible bond rotation and bond angle deflection, while the amorphous carbon matrix restrains the relaxation of the rigid C-C network and compressive stress and restricts the slip of graphene sheets.
Deposition of amorphous carbon thin films by aerosol-assisted CVD method
NASA Astrophysics Data System (ADS)
Fadzilah, A. N.; Dayana, K.; Rusop, M.
2018-05-01
This paper reports on the deposition of amorphous carbon (a-C) by Aerosol-assisted Chemical Vapor Deposition (AACVD) using natural source of camphor oil as the precursor material. 4 samples were deposited at 4 different deposition flow rate from 15 sccm to 20 sccm, with 5 sccm interval for each sample. The analysis includes the electrical, optical and structural analysis of the data. The a-C structure which came from the manipulation of synthesis parameter was characterized by the solar simulator system, UV-VIS-NIR, Raman spectroscope and AFM. The properties of a-C are highly dependent on the deposition techniques and deposition parameters; hence the influences of gas flow rate were studied.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Arendt, Paul N.; DePaula, Ramond F.; Zhu, Yuntian T.
An array of carbon nanotubes is prepared by exposing a catalyst structure to a carbon nanotube precursor. Embodiment catalyst structures include one or more trenches, channels, or a combination of trenches and channels. A system for preparing the array includes a heated surface for heating the catalyst structure and a cooling portion that cools gas above the catalyst structure. The system heats the catalyst structure so that the interaction between the precursor and the catalyst structure results in the formation of an array of carbon nanotubes on the catalyst structure, and cools the gas near the catalyst structure and alsomore » cools any carbon nanotubes that form on the catalyst structure to prevent or at least minimize the formation of amorphous carbon. Arrays thus formed may be used for spinning fibers of carbon nanotubes.« less
NASA Astrophysics Data System (ADS)
Nimmo, John Paul, II
Silicon oxycarbide (SiCO) is an amorphous ceramic material widely used in industrial applications, for its useful electronic and biologically-compatible properties. SiCO is resistant to crystallization, remaining amorphous even above temperatures at which amorphous SiO2 would crystallize. Though silica (SiO2) and silicon carbide (SiC) are almost immiscible, it is useful to consider the material as a phase composition of these along with carbon, according to the formula below. The first two terms in braces can be considered as being the "SiCO glass" into which a third term representing excess or "free" carbon is incorporated as graphite-like nano-flakes and bands.
NASA Technical Reports Server (NTRS)
King, James D.
2004-01-01
Using high resolution transmission electron images of carbon nanotubes and carbon particles, we are able to use image analysis program to determine several carbon fringe properties, including length, separation, curvature and orientation. Results are shown in the form of histograms for each of those quantities. The combination of those measurements can give a better indication of the graphic structure within nanotubes and particles of carbon and can distinguish carbons based upon fringe properties. Carbon with longer, straighter and closer spaced fringes are considered graphite, while amorphous carbon contain shorter, less structured fringes.
NASA Astrophysics Data System (ADS)
Gueorguiev, G. K.; Broitman, E.; Furlan, A.; Stafström, S.; Hultman, L.
2009-11-01
The energy cost for dangling bond formation in Fullerene-like Carbon Nitride (FL-CN x) and Phosphorus carbide (FL-CP x) as well as their amorphous counterparts: a-CN x, a-CP x, and a-C has been calculated within the framework of Density Functional Theory and compared with surface water adsorption measurements. The highest energy cost is found in the FL-CN x (about 1.37 eV) followed by FL-CP x compounds (0.62-1.04 eV).
Synthesis and structure of synthetically pure and deuterated amorphous (basic) calcium carbonates
Wang, Hsiu-Wen; Daemen, Luke L.; Cheshire, Michael C.; ...
2017-02-17
It is generally believed that H 2O and OH - are the key species stabilizing and controlling amorphous calcium carbonate “polyamorph” forms, and may in turn control the ultimate crystallization products during synthesis and in natural systems. Yet, the locations and hydrogen-bonding network of these species in ACC have never been measured directly using neutron diffraction. In this paper, we report a synthesis route that overcomes the existing challenges with respect to yield quantities and deuteration, both of which are critically necessary for high quality neutron studies.
Electric measurements of PV heterojunction structures a-SiC/c-Si
NASA Astrophysics Data System (ADS)
Perný, Milan; Šály, Vladimír; Janíček, František; Mikolášek, Miroslav; Váry, Michal; Huran, Jozef
2018-01-01
Due to the particular advantages of amorphous silicon or its alloys with carbon in comparison to conventional crystalline materials makes such a material still interesting for study. The amorphous silicon carbide may be used in a number of micro-mechanical and micro-electronics applications and also for photovoltaic energy conversion devices. Boron doped thin layers of amorphous silicon carbide, presented in this paper, were prepared due to the optimization process for preparation of heterojunction solar cell structure. DC and AC measurement and subsequent evaluation were carried out in order to comprehensively assess the electrical transport processes in the prepared a-SiC/c-Si structures. We have investigated the influence of methane content in deposition gas mixture and different electrode configuration.
NASA Technical Reports Server (NTRS)
Duley, W. W.; Jones, A. P.; Taylor, S. D.; Williams, D. A.
1993-01-01
The correlations deduced by Boulanger et al. (1990) from IRAS maps of the Chamaeleon, Taurus and Ursa Major molecular cloud complexes are interpreted in terms of the evolutionary hydrogenated amorphous carbon model of interstellar dust. In particular, regions of relatively strong 12-micron emission may be regions where recently accreted carbon is being converted by ambient UV to small PAHs in situ. Regions of weak 12-micron emission are probably quiescent regions where carbon has been annealed to amorphous carbon. Observational consequences of these inferences are briefly described.
Dehydration-induced amorphous phases of calcium carbonate.
Saharay, Moumita; Yazaydin, A Ozgur; Kirkpatrick, R James
2013-03-28
Amorphous calcium carbonate (ACC) is a critical transient phase in the inorganic precipitation of CaCO3 and in biomineralization. The calcium carbonate crystallization pathway is thought to involve dehydration of more hydrated ACC to less hydrated ACC followed by the formation of anhydrous ACC. We present here computational studies of the transition of a hydrated ACC with a H2O/CaCO3 ratio of 1.0 to anhydrous ACC. During dehydration, ACC undergoes reorganization to a more ordered structure with a significant increase in density. The computed density of anhydrous ACC is similar to that of calcite, the stable crystalline phase. Compared to the crystalline CaCO3 phases, calcite, vaterite, and aragonite, the computed local structure of anhydrous ACC is most-similar to those of calcite and vaterite, but the overall structure is not well described by either. The strong hydrogen bond interaction between the carbonate ions and water molecules plays a crucial role in stabilizing the less hydrated ACC compositions compared to the more hydrated ones, leading to a progressively increasing hydration energy with decreasing water content.
NASA Astrophysics Data System (ADS)
Mikhalev, K. N.; Germov, A. Yu; Uimin, M. A.; Yermakov, A. E.; Konev, A. S.; Novikov, S. I.; Gaviko, V. S.; Ponosov, Yu S.
2018-05-01
59Co, 13C NMR spectra, magnetization and Raman spectra of Co@C nanoparticles encapsulated in carbon have been analyzed. It has been shown that the cores of the nanoparticles consist of metallic cobalt with FCC structure and perhaps the carbide of cobalt Co3C. Carbon shell have been characterized as a highly defective structure similar to amorphous or glassy-like carbon, however, it may include a small amount of the carbon nanotubes.
Constantinou, Marios; Nikolaou, Petros; Koutsokeras, Loukas; Avgeropoulos, Apostolos; Moschovas, Dimitrios; Varotsis, Constantinos; Patsalas, Panos; Kelires, Pantelis; Constantinides, Georgios
2018-03-30
This study aimed to develop hydrogenated amorphous carbon thin films with embedded metallic nanoparticles (a-C:H:Me) of controlled size and concentration. Towards this end, a novel hybrid deposition system is presented that uses a combination of Plasma Enhanced Chemical Vapor Deposition (PECVD) and Physical Vapor Deposition (PVD) technologies. The a-C:H matrix was deposited through the acceleration of carbon ions generated through a radio-frequency (RF) plasma source by cracking methane, whereas metallic nanoparticles were generated and deposited using terminated gas condensation (TGC) technology. The resulting material was a hydrogenated amorphous carbon film with controlled physical properties and evenly dispersed metallic nanoparticles (here Ag or Ti). The physical, chemical, morphological and mechanical characteristics of the films were investigated through X-ray reflectivity (XRR), Raman spectroscopy, Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Transmission Electron Microscopy (TEM) and nanoscratch testing. The resulting amorphous carbon metal nanocomposite films (a-C:H:Ag and a-C:H:Ti) exhibited enhanced nanoscratch resistance (up to +50%) and low values of friction coefficient (<0.05), properties desirable for protective coatings and/or solid lubricant applications. The ability to form nanocomposite structures with tunable coating performance by potentially controlling the carbon bonding, hydrogen content, and the type/size/percent of metallic nanoparticles opens new avenues for a broad range of applications in which mechanical, physical, biological and/or combinatorial properties are required.
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.
Si-FeSi2/C nanocomposite anode materials produced by two-stage high-energy mechanical milling
NASA Astrophysics Data System (ADS)
Yang, Yun Mo; Loka, Chadrasekhar; Kim, Dong Phil; Joo, Sin Yong; Moon, Sung Whan; Choi, Yi Sik; Park, Jung Han; Lee, Kee-Sun
2017-05-01
High capacity retention Silicon-based nanocomposite anode materials have been extensively explored for use in lithium-ion rechargeable batteries. Here we report the preparation of Si-FeSi2/C nanocomposite through scalable a two-stage high-energy mechanical milling process, in which nano-scale Si-FeSi2 powders are besieged by the carbon (graphite/amorphous phase) layer; and investigation of their structure, morphology and electrochemical performance. Raman analysis revealed that the carbon layer structure comprised of graphitic and amorphous phase rather than a single amorphous phase. Anodes fabricated with the Si-FeSi2/C showed excellent electrochemical behavior such as a first discharge capacity of 1082 mAh g-1 and a high capacity retention until the 30th cycle. A remarkable coulombic efficiency of 99.5% was achieved within a few cycles. Differential capacity plots of the Si-FeSi2/C anodes revealed a stable lithium reaction with Si for lithiation/delithiation. The enhanced electrochemical properties of the Si-FeSi2/C nanocomposite are mainly attributed to the nano-size Si and stable solid electrolyte interface formation and highly conductive path driven by the carbon layer.
Lin, Zhiqiang; Gui, Xuchun; Gan, Qiming; Chen, Wenjun; Cheng, Xiaoping; Liu, Ming; Zhu, Yuan; Yang, Yanbing; Cao, Anyuan; Tang, Zikang
2015-01-01
Carbon nanotube (CNT) and graphene-based sponges and aerogels have an isotropic porous structure and their mechanical strength and stability are relatively lower. Here, we present a junction-welding approach to fabricate porous CNT solids in which all CNTs are coated and welded in situ by an amorphous carbon layer, forming an integral three-dimensional scaffold with fixed joints. The resulting CNT solids are robust, yet still highly porous and compressible, with compressive strengths up to 72 MPa, flexural strengths up to 33 MPa, and fatigue resistance (recovery after 100,000 large-strain compression cycles at high frequency). Significant enhancement of mechanical properties is attributed to the welding-induced interconnection and reinforcement of structural units, and synergistic effects stemming from the core-shell microstructures consisting of a flexible CNT framework and a rigid amorphous carbon shell. Our results provide a simple and effective method to manufacture high-strength porous materials by nanoscale welding. PMID:26067176
Lin, Zhiqiang; Gui, Xuchun; Gan, Qiming; Chen, Wenjun; Cheng, Xiaoping; Liu, Ming; Zhu, Yuan; Yang, Yanbing; Cao, Anyuan; Tang, Zikang
2015-06-11
Carbon nanotube (CNT) and graphene-based sponges and aerogels have an isotropic porous structure and their mechanical strength and stability are relatively lower. Here, we present a junction-welding approach to fabricate porous CNT solids in which all CNTs are coated and welded in situ by an amorphous carbon layer, forming an integral three-dimensional scaffold with fixed joints. The resulting CNT solids are robust, yet still highly porous and compressible, with compressive strengths up to 72 MPa, flexural strengths up to 33 MPa, and fatigue resistance (recovery after 100,000 large-strain compression cycles at high frequency). Significant enhancement of mechanical properties is attributed to the welding-induced interconnection and reinforcement of structural units, and synergistic effects stemming from the core-shell microstructures consisting of a flexible CNT framework and a rigid amorphous carbon shell. Our results provide a simple and effective method to manufacture high-strength porous materials by nanoscale welding.
NASA Astrophysics Data System (ADS)
Lin, Zhiqiang; Gui, Xuchun; Gan, Qiming; Chen, Wenjun; Cheng, Xiaoping; Liu, Ming; Zhu, Yuan; Yang, Yanbing; Cao, Anyuan; Tang, Zikang
2015-06-01
Carbon nanotube (CNT) and graphene-based sponges and aerogels have an isotropic porous structure and their mechanical strength and stability are relatively lower. Here, we present a junction-welding approach to fabricate porous CNT solids in which all CNTs are coated and welded in situ by an amorphous carbon layer, forming an integral three-dimensional scaffold with fixed joints. The resulting CNT solids are robust, yet still highly porous and compressible, with compressive strengths up to 72 MPa, flexural strengths up to 33 MPa, and fatigue resistance (recovery after 100,000 large-strain compression cycles at high frequency). Significant enhancement of mechanical properties is attributed to the welding-induced interconnection and reinforcement of structural units, and synergistic effects stemming from the core-shell microstructures consisting of a flexible CNT framework and a rigid amorphous carbon shell. Our results provide a simple and effective method to manufacture high-strength porous materials by nanoscale welding.
The liquid⟷amorphous transition and the high pressure phase diagram of carbon
NASA Astrophysics Data System (ADS)
Robinson, David R.; Wilson, Mark
2013-04-01
The phase diagram of carbon is mapped to high pressure using a computationally-tractable potential model. The use of a relatively simple (Tersoff-II) potential model allows a large range of phase space to be explored. The coexistence (melting) curve for the diamond crystal/liquid dyad is mapped directly by modelling the solid/liquid interfaces. The melting curve is found to be re-entrant and belongs to a conformal class of diamond/liquid coexistence curves. On supercooling the liquid a phase transition to a tetrahedral amorphous form (ta-C) is observed. The liquid ⟷ amorphous coexistence curve is mapped onto the pT plane and is found to also be re-entrant. The entropy changes for both melting and the amorphous ⟶ liquid transitions are obtained from the respective coexistence curves and the associated changes in molar volume. The structural change on amorphization is analysed at different points on the coexistence curve including for transitions that are both isochoric and isocoordinate (no change in nearest-neighbour coordination number). The conformal nature of the melting curve is highlighted with respect to the known behaviour of Si. The relationship of the observed liquid/amorphous coexistence curve to the Si low- and high-density amorphous (LDA/HDA) transition is discussed.
Nanotribological performance of fullerene-like carbon nitride films
NASA Astrophysics Data System (ADS)
Flores-Ruiz, Francisco Javier; Enriquez-Flores, Christian Ivan; Chiñas-Castillo, Fernando; Espinoza-Beltrán, Francisco Javier
2014-09-01
Fullerene-like carbon nitride films exhibit high elastic modulus and low friction coefficient. In this study, thin CNx films were deposited on silicon substrate by DC magnetron sputtering and the tribological behavior at nanoscale was evaluated using an atomic force microscope. Results show that CNx films with fullerene-like structure have a friction coefficient (CoF ∼ 0.009-0.022) that is lower than amorphous CNx films (CoF ∼ 0.028-0.032). Analysis of specimens characterized by X-ray photoelectron spectroscopy shows that films with fullerene-like structure have a higher number of sp3 CN bonds and exhibit the best mechanical properties with high values of elastic modulus (E > 180 GPa) and hardness (H > 20 GPa). The elastic recovery determined on specimens with a fullerene-like CNx structure was of 95% while specimens of amorphous CNx structure had only 75% elastic recovery.
Chemical and structural characterization of boron carbide powders and ceramics
NASA Astrophysics Data System (ADS)
Kuwelkar, Kanak Anant
Boron carbide is the material of choice for lightweight armor applications due to its extreme hardness, high Young's modulus and low specific weight. The homogeneity range in boron carbide extends from 9 to 20 at% carbon with the solubility limits not uniquely defined in literature. Over the homogeneity range, the exact lattice positions of boron and carbon atoms have not been unambiguously established, and this topic has been the consideration of significant debate over the last 60 years. The atomic configuration and positions of the boron and carbon atoms play a key role in the crystal structure of the boron carbide phases. Depending on the atomic structure, boron carbide exhibits different mechanical properties which may alter its ballistic performance under extreme dynamic conditions. This work focusses on refinement and development of analytical and chemical methods for an accurate determination of the boron carbide stoichiometry. These methods were then utilized to link structural changes of boron carbide across the solubility range to variations in mechanical properties. After an extensive assessment of the currently employed characterization techniques, it was discerned that the largest source of uncertainty in the determination of the boron carbide stoichiometry was found to arise from the method utilized to evaluate the free carbon concentration. To this end, a modified spiking technique was introduced for free carbon determination where curve fitting techniques were employed to model the asymmetry of the 002 free carbon diffraction peak based on the amorphous, disordered and graphitic nature of carbon. A relationship was then established between the relative intensities of the carbon and boron carbide peaks to the percentage of added carbon and the free-carbon content was obtained by extrapolation. Samples with varying chemistry and high purity were synthesized across the solubility range by hot pressing mixtures of amorphous boron and boron carbide. Vibrational mode frequencies and lattice parameter measurements from Rietveld refinement were correlated to the respective B:C ratios calculated using the developed characterization techniques. An expansion of the unit cell and change in slope in the lattice parameter-stoichiometry relationship were observed at more boron rich stoichiometries. These observations were justified through the proposal of a simplified structural model considering preferential substitution of boron atoms for carbon atoms in the icosahedra from 20 at% to 13.3 at% carbon, followed by formation of B-B bonds from 13.3 at % C to 9 at% C. Hardness measurements uncovered decreased hardness values in boron rich boron carbide which was attributed to the formation of weaker unit cells. Load induced amorphization was also detected in all the indented materials. Finally, experimental observations have shown that failure in boron carbide may be governed by a mechanism other than amorphization and synthesizing boron carbide with a modified microstructure at stoichiometries close to B4C may be the way forward to attain improved ballistic performance.
Atomic resolution Z-contrast imaging and energy loss spectroscopy of carbon nanotubes and bundles
NASA Astrophysics Data System (ADS)
Lupini, A. R.; Chisholm, M. F.; Puretzky, A. A.; Eres, G.; Melechko, A. V.; Schaaff, G.; Lowndes, D. H.; Geohegan, D. B.; Schittenhelm, H.; Pennycook, S. J.; Wang, Y.; Smalley, R. E.
2002-03-01
Single-wall carbon nanotubes and bundles were studied by a combination of techniques, including conventional imaging and diffraction, atomic resolution Z-contrast imaging in an aberration corrected STEM and electron energy loss spectroscopy (EELS). EELS is ideally suited for the analysis of carbon based structures because of the ability to distinguish between the different forms, specifically nanotubes, graphite, amorphous carbon and diamond. Numerous attempts were made to synthesize crystals of single walled carbon nanotubes, using both solution and vapor deposition of precursor structures directly onto TEM grids for in-situ annealing. The range of structures produced will be discussed.
NASA Astrophysics Data System (ADS)
Catena, Alberto; McJunkin, Thomas; Agnello, Simonpietro; Gelardi, Franco M.; Wehner, Stefan; Fischer, Christian B.
2015-08-01
Silicon (1 0 0) has been gradually covered by amorphous hydrogenated carbon (a-C:H) films via an industrial process. Two types of these diamond-like carbon (DLC) coatings, one more flexible (f-DLC) and one more robust (r-DLC), have been investigated. Both types have been grown by a radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD) technique with acetylene plasma. Surface morphologies have been studied in detail by atomic force microscopy (AFM) and Raman spectroscopy has been used to investigate the DLC structure. Both types appeared to have very similar morphology and sp2 carbon arrangement. The average height and area for single grains have been analyzed for all depositions. A random distribution of grain heights was found for both types. The individual grain structures between the f- and r-type revealed differences: the shape for the f-DLC grains is steeper than for the r-DLC grains. By correlating the average grain heights to the average grain areas for all depositions a limited region is identified, suggesting a certain regularity during the DLC deposition mechanisms that confines both values. A growth of the sp2 carbon entities for high r-DLC depositions is revealed and connected to a structural rearrangement of carbon atom hybridizations and hydrogen content in the DLC structure.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Yongfu; University of Chinese Academy of Sciences, Beijing 100049; Gao, Kaixiong
In this study, fullerene like carbon (FL-C) is introduced in hydrogenated amorphous carbon (a-C:H) film by employing a direct current plasma enhanced chemical vapor deposition. The film has a low friction and wear, such as 0.011 and 2.3 × 10{sup −9}mm{sup 3}/N m in the N{sub 2}, and 0.014 and 8.4 × 10{sup −8}mm{sup 3}/N m in the humid air, and high hardness and elasticity (25.8 GPa and 83.1%), to make further engineering applications in practice. It has several nanometers ordered domains consisting of less frequently cross-linked graphitic sheet stacks. We provide new evidences for understanding the reported Raman fit model involving four vibrational frequenciesmore » from five, six, and seven C-atom rings of FL-C structures, and discuss the structure evolution before or after friction according to the change in the 1200 cm{sup −1} Raman band intensity caused by five- and seven-carbon rings. Friction inevitably facilitates the transformation of carbon into FL-C nanostructures, namely, the ultra low friction comes from both such structures within the carbon film and the sliding induced at friction interface.« less
Thermally Tunable Hydrogels Displaying Angle-Independent Structural Colors.
Ohtsuka, Yumiko; Seki, Takahiro; Takeoka, Yukikazu
2015-12-14
We report the preparation of thermally tunable hydrogels displaying angle-independent structural colors. The porous structures were formed with short-range order using colloidal amorphous array templates and a small amount of carbon black (CB). The resultant porous hydrogels prepared using colloidal amorphous arrays without CB appeared white, whereas the hydrogels with CB revealed bright structural colors. The brightly colored hydrogels rapidly changed hues in a reversible manner, and the hues varied widely depending on the water temperature. Moreover, the structural colors were angle-independent under diffusive lighting because of the isotropic nanostructure generated from the colloidal amorphous arrays. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.
NASA Astrophysics Data System (ADS)
Wang, Yongfu; Wang, Yan; Zhang, Xingkai; Shi, Jing; Gao, Kaixiong; Zhang, Bin; Zhang, Junyan
2017-10-01
In this study, we prepared hydrogenated amorphous carbon films on steel balls and Si substrates (steel ball- and Si substrate-films) with different deposition time, and discussed their carbon nanostructural evolutions and tribological behaviors. The steel ball-film structure started to be graphite-like structure and then gradually transformed into fullerene-like (FL) structure. The Si substrate-film structure began in FL structure and kept it through the thickness. The difference may be result from the competition between high starting substrate temperature after additional nitriding applied on the steel balls (its supply power is higher than that in the film deposition), and relaxation of compressive stress from energized ion bombardment in film deposition process. The FL structural film friction couples could achieve ultra-low friction in open air. In particular, the Si substrate-film with 3 h, against the steel ball-film with 2 h and 3 h, exhibited super-low friction (∼0.009) and superlong wear life (∼5.5 × 105 cycles). Our result could widen the superlubricity scope from previously high load and velocity, to middle load and velocity.
Emission of blue light from hydrogenated amorphous silicon carbide
NASA Astrophysics Data System (ADS)
Nevin, W. A.; Yamagishi, H.; Yamaguchi, M.; Tawada, Y.
1994-04-01
THE development of new electroluminescent materials is of current technological interest for use in flat-screen full-colour displays1. For such applications, amorphous inorganic semiconductors appear particularly promising, in view of the ease with which uniform films with good mechanical and electronic properties can be deposited over large areas2. Luminescence has been reported1 in the red-green part of the spectrum from amorphous silicon carbide prepared from gas-phase mixtures of silane and a carbon-containing species (usually methane or ethylene). But it is not possible to achieve blue luminescence by this approach. Here we show that the use of an aromatic species-xylene-as the source of carbon during deposition results in a form of amorphous silicon carbide that exhibits strong blue luminescence. The underlying structure of this material seems to be an unusual combination of an inorganic silicon carbide lattice with a substantial 'organic' π-conjugated carbon system, the latter dominating the emission properties. Moreover, the material can be readily doped with an electron acceptor in a manner similar to organic semiconductors3, and might therefore find applications as a conductivity- or colour-based chemical sensor.
Whittaker, Michael L; Smeets, Paul J M; Asayesh-Ardakani, Hasti; Shahbazian-Yassar, Reza; Joester, Derk
2017-12-11
The direct observation of amorphous barium carbonate (ABC), which transforms into a previously unknown barium carbonate hydrate (herewith named gortatowskite) within a few hundred milliseconds of formation, is described. In situ X-ray scattering, cryo-, and low-dose electron microscopy were used to capture the transformation of nanoparticulate ABC into gortatowskite crystals, highly anisotropic sheets that are up to 1 μm in width, yet only about 10 nm in thickness. Recrystallization of gortatowskite to witherite starts within 30 seconds. We describe a bulk synthesis and report a first assessment of the composition, vibrational spectra, and structure of gortatowskite. Our findings indicate that transient amorphous and crystalline precursors can play a role in aqueous precipitation pathways that may often be overlooked owing to their extremely short lifetimes and small dimensions. However, such transient precursors may be integral to the formation of more stable phases. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Silicon/Carbon Anodes with One-Dimensional Pore Structure for Lithium-Ion Batteries
2013-08-31
Connected by Single-Wall Carbon Nanotubes for Sodium Ion Battery Cathodes, Nano Letters 12, 5664, 2012. ( § equal contribution) Chao Luo,§ Yunhua...is superior to that of those conductive additive-incorporated iron oxide anodes, such as amorphous carbon , graphene as well as carbon nanotubes ...electrochemical performance. The C/S composite cathodes were prepared by mixing C/S powders with carbon black and sodium carboxymethyl cellulose (CMC
Multi-layer carbon-based coatings for field emission
Sullivan, John P.; Friedmann, Thomas A.
1998-01-01
A multi-layer resistive carbon film field emitter device for cold cathode field emission applications. The multi-layered film of the present invention consists of at least two layers of a conductive carbon material, preferably amorphous-tetrahedrally coordinated carbon, where the resistivities of adjacent layers differ. For electron emission from the surface, the preferred structure can be a top layer having a lower resistivity than the bottom layer. For edge emitting structures, the preferred structure of the film can be a plurality of carbon layers, where adjacent layers have different resistivities. Through selection of deposition conditions, including the energy of the depositing carbon species, the presence or absence of certain elements such as H, N, inert gases or boron, carbon layers having desired resistivities can be produced.
HRTEM low dose: the unfold of the morphed graphene, from amorphous carbon to morphed graphenes.
Calderon, H A; Okonkwo, A; Estrada-Guel, I; Hadjiev, V G; Alvarez-Ramírez, F; Robles Hernández, F C
We present experimental evidence under low-dose conditions transmission electron microscopy for the unfolding of the evolving changes in carbon soot during mechanical milling. The milled soot shows evolving changes as a function of the milling severity or time. Those changes are responsible for the transformation from amorphous carbon to graphenes, graphitic carbon, and highly ordered structures such as morphed graphenes, namely Rh6 and Rh6-II. The morphed graphenes are corrugated layers of carbon with cross-linked covalently nature and sp 2 - or sp 3 -type allotropes. Electron microscopy and numerical simulations are excellent complementary tools to identify those phases. Furthermore, the TEAM 05 microscope is an outstanding tool to resolve the microstructure and prevent any damage to the sample. Other characterization techniques such as XRD, Raman, and XPS fade to convey a true identification of those phases because the samples are usually blends or mixes of the mentioned phases.
Theoretical Study of Diamond-Like Carbons and Nucleation of Diamond
NASA Astrophysics Data System (ADS)
Lee, Choon-Heung
Different forms of amorphous carbon and hydrocarbons with varying elastic and optical properties, hardness, density and hydrogen content exist depending on the preparation technique. The structure can vary from graphitic to diamond -like, i.e., from mainly threefold coordinated to mainly four-fold coordinated. In order to study the properties of such materials, microscopic models must be developed. These studies include the modelling of crosslinked defective graphite, diamond nucleation along the graphite edges, and diamond-like carbons. Tamor's proposed structure for diamondlike carbon consists of crosslinked graphitic regions. We studied a concrete realization of this model in which the cross -links are produced by shortening the interplanar bond lengths. The model study was accomplished with a pure rhombohedral graphite cell. For this study we used a semi-empirical potential based on Tersoff's environment-dependent potential which contains angular terms. It is enhanced by a long-range potential which describes the interplanar interactions. We found a configuration corresponding to a local minimum. More general features such as the randomness of the distribution of cross-links are needed for a realistic model. A model study of diamond/graphite interfaces was motivated by recent observations by Li and Angus. They observed a significant enhancement of diamond nucleation on the graphite edge planes with the preferential orientation relationship: {0001} _{g} | {111 }_{d}, < 1120 >_{g} | < 101>_{d}. Two possible interface structures were studied using the Tersoff potential. We found that the models have comparable low interface energies even if they contain some dangling bonds. Moreover, lower interface energies were found when the dangling bonds of the non-bonded diamond layer were satisfied with hydrogen. We have proposed a growth mechanism based on this study. Finally, we constructed realistic models of dense amorphous carbon. The WWW (introduced earlier for a-Si by Wooten, Winer and Weaire) model was the starting structure. The effects of clustering of the threefold coordinated atoms in pairs, chains, or graphitic (planar hexagonal clusters) were studied. The resulting models were relaxed using the Tersoff potential. Their electronic structures were studied using an empirical tight-binding scheme with parameters adjusted to reproduce the diamond and graphite band-structures. The models were found to have densities of ~ 3 g/cm^3 and bulk moduli of ~3.1 Mbar. Localized dangling bonds and pi - pi^* states were found within the wide gap of the WWW model consistent with optical gaps of the order of 0.5-2 eV. Hydrogen atoms were introduced to remove some of the dangling bonds. The models were found to account for the essential features of ion-beam deposited amorphous carbon and hydrogenated amorphous carbon.
Adsorption of selected volatile organic vapors on multiwall carbon nanotubes.
Shih, Yang-hsin; Li, Mei-syue
2008-06-15
Carbon nanotubes are expected to play an important role in sensing, pollution treatment and separation techniques. This study examines the adsorption behaviors of volatile organic compounds (VOCs), n-hexane, benzene, trichloroethylene and acetone on two multiwall carbon nanotubes (MWCNTs), CNT1 and CNT2. Among these VOCs, acetone exhibits the highest adsorption capacity. The highest adsorption enthalpies and desorption energies of acetone were also observed. The strong chemical interactions between acetone and both MWCNTs may be the result from chemisorption on the topological defects. The adsorption heats of trichloroethylene, benzene, and n-hexane are indicative of physisorption on the surfaces of both MWCNTs. CNT2 presents a higher adsorption capacity than CNT1 due to the existence of an exterior amorphous carbon layer on CNT2. The amorphous carbon enhances the adsorption capacity of organic chemicals on carbon nanotubes. The morphological and structure order of carbon nanotubes are the primary affects on the adsorption process of organic chemicals.
Microstructure, hardness and modulus of carbon-ion-irradiated new SiC fiber (601-4)
NASA Astrophysics Data System (ADS)
Huang, Qing; Lei, Guanhong; Liu, Renduo; Li, Jianjian; Yan, Long; Li, Cheng; Liu, Weihua; Wang, Mouhua
2018-05-01
Two types of SiC fibers, one is low-oxygen and carbon-rich fiber denoted by 601-4 and the other is low-oxygen and near-stoichiometric Tyranno SA, were irradiated with 450 keV C+ ions at room temperature. The Raman spectra indicate that irradiation induced distortion and amorphization of SiC crystallites in fibers. TEM characterization of Tyranno SA suggests that SiC crystallites undergo a continued fragmentation into smaller crystalline islands and a continued increase of surrounding amorphous structure. The SiC nano-crystallites (<15 nm) in 601-4 fiber are more likely to be amorphized than larger crystallites (∼200 nm) in Tyranno SA. The hardness and modulus of 601-4 continuously decreases with increasing fluence, while that of Tyranno SA first increases and then decreases.
NASA Astrophysics Data System (ADS)
Zhou, Xilin; Wu, Liangcai; Song, Zhitang; Rao, Feng; Zhu, Min; Peng, Cheng; Yao, Dongning; Song, Sannian; Liu, Bo; Feng, Songlin
2012-10-01
Carbon-doped Ge2Sb2Te5 material is proposed for high-density phase-change memories. The carbon doping effects on electrical and structural properties of Ge2Sb2Te5 are studied by in situ resistance and x-ray diffraction measurements as well as optical spectroscopy. C atoms are found to significantly enhance the thermal stability of amorphous Ge2Sb2Te5 by increasing the degree of disorder of the amorphous phase. The reversible electrical switching capability of the phase-change memory cells is improved in terms of power consumption with carbon addition. The endurance of ˜2.1 × 104 cycles suggests that C-doped Ge2Sb2Te5 film will be a potential phase-change material for high-density storage application.
Nam, Inho; Kim, Nam Dong; Kim, Gil-Pyo; Park, Junsu; Yi, Jongheop
2012-07-01
A supercapacitor has the advantages of both the conventional capacitors and the rechargeable batteries. Mn oxide is generally recognized one of the potential materials that can be used for a supercapacitor, but its low conductivity is a limiting factor for electrode materials. In this study, a hybrid of amorphous Mn oxide (AMO) and ordered mesoporous carbon (OMC) was prepared and characterized using X-ray diffraction, transmission electron microscopy, N2/77 K sorption techniques, and electrochemical analyses. The findings indicate that the electrochemical activities of Mn oxide were facilitated when it was in the hybrid state because OMC acted as a pathway for both the electrolyte ions and the electrons due to the characteristics of the ordered mesoporous structure. The ordered mesoporous structure of OMC was well maintained even after hybridization with amorphous Mn oxide. The electrochemical-activity tests revealed that the AMO/OMC hybrid had a higher specific capacitance and conductivity than pure Mn oxide. In the case where the Mn/C weight ratio was 0.75, the composite showed a high capacitance of 153 F/g, which was much higher than that for pure Mn oxide, due to the structural effects of OMC.
McMullan, G; Vinothkumar, K R; Henderson, R
2015-11-01
We have recorded dose-fractionated electron cryo-microscope images of thin films of pure flash-frozen amorphous ice and pre-irradiated amorphous carbon on a Falcon II direct electron detector using 300 keV electrons. We observe Thon rings [1] in both the power spectrum of the summed frames and the sum of power spectra from the individual frames. The Thon rings from amorphous carbon images are always more visible in the power spectrum of the summed frames whereas those of amorphous ice are more visible in the sum of power spectra from the individual frames. This difference indicates that while pre-irradiated carbon behaves like a solid during the exposure, amorphous ice behaves like a fluid with the individual water molecules undergoing beam-induced motion. Using the measured variation in the power spectra amplitude with number of electrons per image we deduce that water molecules are randomly displaced by a mean squared distance of ∼1.1 Å(2) for every incident 300 keV e(-)/Å(2). The induced motion leads to an optimal exposure with 300 keV electrons of 4.0 e(-)/Å(2) per image with which to observe Thon rings centred around the strong 3.7 Å scattering peak from amorphous ice. The beam-induced movement of the water molecules generates pseudo-Brownian motion of embedded macromolecules. The resulting blurring of single particle images contributes an additional term, on top of that from radiation damage, to the minimum achievable B-factor for macromolecular structure determination. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.
Diamond Composite Films for Protective Coatings on Metals and Method of Formation
NASA Technical Reports Server (NTRS)
Ong, Tiong P. (Inventor); Shing, Yuh-Han (Inventor)
1997-01-01
Composite films consisting of diamond crystallites and hard amorphous films such as diamond-like carbon, titanium nitride, and titanium oxide are provided as protective coatings for metal substrates against extremely harsh environments. A composite layer having diamond crystallites and a hard amorphous film is affixed to a metal substrate via an interlayer including a bottom metal silicide film and a top silicon carbide film. The interlayer is formed either by depositing metal silicide and silicon carbide directly onto the metal substrate, or by first depositing an amorphous silicon film, then allowing top and bottom portions of the amorphous silicon to react during deposition of the diamond crystallites, to yield the desired interlayer structure.
Equilibrium structures and flows of polar and nonpolar liquids in different carbon nanotubes
NASA Astrophysics Data System (ADS)
Abramyan, Andrey K.; Bessonov, Nick M.; Mirantsev, Leonid V.; Chevrychkina, Anastasiia A.
2018-03-01
Molecular dynamics (MD) simulations of equilibrium structures and flows of polar water and nonpolar methane confined by single-walled carbon nanotubes (SWCNTs) with circular and square cross sections and bounding walls with regular graphene structure and random (amorphous) distribution of carbon atoms have been performed. The results of these simulations show that equilibrium structures of both confined liquids depend strongly on the shape of the cross section of SWCNTs, whereas the structure of their bounding walls has a minor influence on these structures. On contrary, the external pressure driven water and methane flows through above mentioned SWCNTs depend significantly on both the shape of their cross sections and the structure of their bounding walls.
Tu, Zhiming; Yang, Gongzheng; Song, Huawei; Wang, Chengxin
2017-01-11
Due to its high theoretical capacity (978 mA h g -1 ), natural abundance, environmental friendliness, and low cost, zinc oxide is regarded as one of the most promising anode materials for lithium-ion batteries (LIBs). A lot of research has been done in the past few years on this topic. However, hardly any research on amorphous ZnO for LIB anodes has been reported despite the fact that the amorphous type could have superior electrochemical performance due to its isotropic nature, abundant active sites, better buffer effect, and different electrochemical reaction details. In this work, we develop a simple route to prepare an amorphous ZnO quantum dot (QDs)/mesoporous carbon bubble composite. The composite consists of two parts: mesoporous carbon bubbles as a flexible skeleton and monodisperse amorphous zinc oxide QDs (smaller than 3 nm) encapsulated in an amorphous carbon matrix as a continuous coating tightly anchored on the surface of mesoporous carbon bubbles. With the benefits of abundant active sites, amorphous nature, high specific surface area, buffer effect, hierarchical pores, stable interconnected conductive network, and multidimensional electron transport pathways, the amorphous ZnO QD/mesoporous carbon bubble composite delivers a high reversible capacity of nearly 930 mA h g -1 (at current density of 100 mA g -1 ) with almost 90% retention for 85 cycles and possesses a good rate performance. This work opens the possibility to fabricate high-performance electrode materials for LIBs, especially for amorphous metal oxide-based materials.
NASA Astrophysics Data System (ADS)
Choi, Young Chul; Lim, Seong Chu
2013-11-01
Single wall carbon nanotubes (SWCNTs) were synthesized by arc discharge, and then purified by selective oxidation of amorphous carbon layers that were found to encase SWCNT bundles and catalyst metal particles. In order to remove selectively the amorphous carbon layers with SWCNTs being intact, we have systematically investigated the thermal treatment conditions; firstly, setting the temperature by measuring the activation energies of SWCNTs and amorphous carbon layers, and then, secondly, finding the optimal process time. As a consequence, the optimal temperature and time for the thermal treatment was found to be 460 °C and 20 min, respectively. The complete elimination of surrounding amorphous carbon layers makes it possible to efficiently disperse the SWCNT bundles, resulting in high absorbance of SWCNT-ink. The SWCNTs which were thermal-treated at optimized temperature (460 °C) and duration (20 min) showed much better crystallinity, dispersibility, and transparent conducting properties, compared with as-synthesized and the nanotubes thermal-treated at different experimental conditions.
The Metastable Persistence of Vapor-Deposited Amorphous Ice at Anomalously High Temperatures
NASA Technical Reports Server (NTRS)
Blake, David F.; Jenniskens, Peter; DeVincenzi, Donald L. (Technical Monitor)
1995-01-01
Studies of the gas release, vaporization behavior and infrared (IR) spectral properties of amorphous and crystalline water ice have direct application to cometary and planetary outgassing phenomena and contribute to an understanding of the physical properties of astrophysical ices. Several investigators report anomalous phenomena related to the warming of vapor-deposited astrophysical ice analogs. However gas release, ice volatilization and IR spectral features are secondary or tertiary manifestations of ice structure or morphology. These observations are useful in mimicking the bulk physical and chemical phenomena taking place in cometary and other extraterrestrial ices but do not directly reveal the structural changes which are their root cause. The phenomenological interpretation of spectral and gas release data is probably the cause of somewhat contradictory explanations invoked to account for differences in water ice behavior in similar temperature regimes. It is the microstructure, micromorphology and microchemical heterogeneity of astrophysical ices which must be characterized if the mechanisms underlying the observed phenomena are to be understood. We have been using a modified Transmission Electron Microscope to characterize the structure of vapor-deposited astrophysical ice analogs as a function of their deposition, temperature history and composition. For the present experiments, pure water vapor is deposited at high vacuum onto a 15 K amorphous carbon film inside an Hitachi H-500H TEM. The resulting ice film (approx. 0.05 micrometers thick) is warmed at the rate of 1 K per minute and diffraction patterns are collected at 1 K intervals. These patterns are converted into radial intensity distributions which are calibrated using patterns of crystalline gold deposited on a small part of the carbon substrate. The small intensity contributed by the amorphous substrate is removed by background subtraction. The proportions of amorphous and crystalline material in each pattern are determined by subtracting a percentage of crystalline component relative to amorphous and pure crystalline endmembers. Vapor-deposited water ice undergoes two amorphous to amorphous structural transformations in the temperature range 15-130 K with important astrophysical implications. The onset of cubic crystallization occurs at 142-160 K (at 1K per minute heating rates) during which the 220 and 311 diffraction maxima appear and 0.1 micrometer crystallites can be seen in bright field images. This transition is time dependent.
Structure and function of matrix proteins and peptides in the biomineral formation in crustaceans.
Nagasawa, Hiromichi
2011-01-01
Crustaceans have hard cuticle with layered structure, which is composed mainly of chitin, proteins, and calcium carbonate. Crustaceans grow by shedding the old cuticle and replacing it with a new one. Decalcification in the cuticle during the pre-molt stage and concomitant calcification in the stomach to form gastroliths observed in some crustacean species are triggered by the molting hormone. Various proteins and peptides have been identified from calcified cuticle and gastroliths, and their functions have been examined in terms of calcification and interaction with chitin. Acidic nature of matrix proteins is important for recruitment of calcium ions and interaction with calcium carbonate. Examination of the relationship between amino acid sequence containing acidic amino acid residues and calcification inhibitory activity revealed that the potency did not depend on the sequence but on the number of acidic amino acid residues. Calcium carbonate in the calcified tissues of crustaceans is amorphous in many cases. Crustaceans take a strategy to induce and maintain amorphous calcium carbonate by using low-molecular-weight phosphorus compounds.
Recent Progress in Some Amorphous Materials for Supercapacitors.
Li, Qing; Xu, Yuxia; Zheng, Shasha; Guo, Xiaotian; Xue, Huaiguo; Pang, Huan
2018-05-14
A breakthrough in technologies having "green" and sustainable energy storage conversion is urgent, and supercapacitors play a crucial role in this area of research. Owing to their unique porous structure, amorphous materials are considered one of the best active materials for high-performance supercapacitors due to their high specific capacity, excellent cycling stability, and fast charging rate. This Review summarizes the synthesis of amorphous materials (transition metal oxides, carbon-based materials, transition metal sulfides, phosphates, hydroxides, and their complexes) to highlight their electrochemical performance in supercapacitors. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Modeling of Amorphous Calcium Carbonate
NASA Astrophysics Data System (ADS)
Sinha, Sourabh; Rez, Peter
2011-10-01
Many species (e.g. sea urchin) form amorphous calcium carbonate (ACC) precursor phases that subsequently transform into crystalline CaCO3. It is certainly possible that ACC might have up to 10 wt% Mg and ˜3 wt% of water. The structure of ACC and mechanisms by which it transforms to crystalline phase are still unknown. Our goal here is to determine an atomic structure model that is consistent with diffraction and IR measurements of ACC. For this purpose a calcite supercell with 24 formula units (120 atoms) was constructed. Various configurations with 6 Mg atoms substituting for Ca (6 wt%) and 3-5 H2O molecules (2.25- 3.75 wt%) inserted in the spaces between Ca atoms, were relaxed using VASP. Most noticeable effects were the tilts of CO3 groups and distortion of Ca sub-lattice, especially in the case of water. The distributions of nearest Ca-Ca distance and CO3 tilts were extracted from those configurations. We also performed the same analysis starting with aragonite. Sampling from above distributions we built models for amorphous calcite/aragonite of size ˜1700 nm^3. We found that the induced distortions were not enough to generate a diffraction pattern typical of an amorphous material. Next we studied diffraction pattern of several nano-crystallites as recent studies suggest that amorphous calcite might be composed of nano- crystallites. We could then generate a diffraction pattern that appeared similar to that from ACC, for a nano-crystallite of size ˜2 nm^3.
Multi-layer carbon-based coatings for field emission
Sullivan, J.P.; Friedmann, T.A.
1998-10-13
A multi-layer resistive carbon film field emitter device for cold cathode field emission applications is disclosed. The multi-layered film of the present invention consists of at least two layers of a conductive carbon material, preferably amorphous-tetrahedrally coordinated carbon, where the resistivities of adjacent layers differ. For electron emission from the surface, the preferred structure can be a top layer having a lower resistivity than the bottom layer. For edge emitting structures, the preferred structure of the film can be a plurality of carbon layers, where adjacent layers have different resistivities. Through selection of deposition conditions, including the energy of the depositing carbon species, the presence or absence of certain elements such as H, N, inert gases or boron, carbon layers having desired resistivities can be produced. 8 figs.
Antonelou, Aspasia; Benekou, Vasiliki; Dracopoulos, Vasileios; Kollia, Mary; Yannopoulos, Spyros N
2018-06-27
Laser processing of carbon containing compounds towards the formation of graphene-based structures gains ground over the last years in view of the practicality that lasers offer against other conventional graphene preparation methods. The current work explores the viability of low-cost lasers, operating at ambient conditions, for the transformation of various graphitic materials to structures with graphene-like atomic arrangement. Starting materials are at two opposing sides. On one side stand typical graphite powder with Bernal stacking and strong sp2 character, while nanocrystalline or quasi-amorphous graphitic powders such as carbon black and activated carbon are also investigated. Electron microscopies are employed to observe post-irradiation morphological changes while Raman scattering identifies details on atomic arrangement. It is demonstrated that graphene-like structures can be prepared either by starting from a well-organized Bernal-stacked network or by irradiating the quasi-amorphous forms of nanocrystalline carbon. Mild structural changes in the former case pertain to increase of the interlayer spacing, which could possibly be rationalized by considering a mechanism based on Coulomb expansion. For less organized carbon structures, reorganization of the atomic arrangement with an appreciable sp3 to sp2 transformation is observed. The findings of this work confirm that laser processing at minimal chamber conditions demonstrate high potential for preparing high-quality graphene-based structures starting from low cost materials. The proposed method being easily scalable adaptable to current technological platforms is expected to be transformed to a viable and eco-friendly graphene production technology. © 2018 IOP Publishing Ltd.
Revealing the 1 nm/s extensibility of nanoscale amorphous carbon in a scanning electron microscope.
Zhang, Wei
2013-01-01
In an ultra-high vacuum scanning electron microscope, the edged branches of amorphous carbon film (∼10 nm thickness) can be continuously extended with an eye-identifying speed (on the order of ∼1 nm/s) under electron beam. Such unusual mobility of amorphous carbon may be associated with deformation promoted by the electric field, which resulted from an inner secondary electron potential difference from the main trunk of carbon film to the tip end of branches under electron beam. This result demonstrates importance of applying electrical effects to modify properties of carbon materials. It may have positive implications to explore some amorphous carbon as electron field emission device. © Wiley Periodicals, Inc.
On diamond, graphitic and amorphous carbons in primitive extraterrestrial solar system materials
NASA Technical Reports Server (NTRS)
Rietmeijer, Frans J. M.
1990-01-01
Carbon is among the most abundant elements in the universe and carbon chemistry in meteorites and comets is an important key to understanding many Solar System and interstellar processes. Yet, the mineralogical properties and interrelations between various structural forms of elemental carbon remain ambiguous. Crystalline elemental carbons include rhombohedral graphite, hexagonal graphite, cubic diamond, hexagonal diamond (i.e., lonsdaleite or carbon-2H) and chaoite. Elemental carbon also occurs as amorphous carbon and poorly graphitized (or turbostratic) carbon but of all the forms of elemental carbon only graphite is stable under physical conditions that prevail in small Solar System bodies and in the interstellar medium. The recent discovery of cubic diamond in carbonaceous chondrites and hexagonal diamond in chondritic interplanetary dust particles (IDPs) have created a renewed interest in the crystalline elemental carbons that were not formed by shock processes on a parent body. Another technique, Raman spectroscopy, confirms a widespread occurrence of disordered graphite in the Allende carbonaceous chondrite and in chondritic IDPs. Elemental carbons have also been identified by their characteristic K-edge features in electron energy loss spectra (EELS). However, the spectroscopic data do not necessarily coincide with those obtained by selected area electron diffraction (SAED). In order to interpret these data in terms of rational crystalline structures, it may be useful to consider the principles underlying electron diffraction and spectroscopic analyses. Electron diffraction depends on electron scattering, on the type of atom and the distance between atoms in a crystal lattice. Spectroscopic data are a function of the type of atom and the energy of bonds between atoms. Also, SAED is a bulk sampling technique when compared to techniques such as Raman spectroscopy or EELS. Thus, it appears that combined analyses provide contradictory results and that amorphous, or short-range ordered, carbon identified by conventional TEM imaging and SAED may show evidence for sp(3) bonds in EELS spectra. It is suggested that complex, nanometer-scale, mineralogical interrelations are common to all elemental carbons irrespective of their origin. The subsequent thermal history, or energy balance, will determine the ultimate microstructure.
Jin, Rencheng; Cui, Yuming; Wang, Qingyao; Li, Guihua
2017-12-15
Amorphous MoSe 2 and Se anchored on amorphous carbon coated multiwalled carbon nanotubes (CNTs@C@MoSe 2 @Se) have been synthesized by a facile solvothermal strategy. The one dimensional CNTs@C@MoSe 2 @Se can effectively buffer the volume variation, prohibit the aggregation and facilitate electron and ion transport throughout the electrode. Furthermore, the combination of MoSe 2 and Se also provides buffer spaces for the volumetric change during cycling. Thus, the obtained CNTs@C@MoSe 2 @Se hybrids display the enhanced cycle stability and excellent high rate capacity. The reversible capacity of 1010mAhg -1 can be achieved after 100 cycles at the current density of 0.1Ag -1 . Even after 500 cycles, a reversible capacity of 508mAhg -1 is still retained at 5Ag -1 . Copyright © 2017 Elsevier Inc. All rights reserved.
Structure-property relationships of a biological mesocrystal in the adult sea urchin spine
Seto, Jong; Ma, Yurong; Davis, Sean A.; Meldrum, Fiona; Gourrier, Aurelien; Kim, Yi-Yeoun; Schilde, Uwe; Sztucki, Michael; Burghammer, Manfred; Maltsev, Sergey; Jäger, Christian; Cölfen, Helmut
2012-01-01
Structuring over many length scales is a design strategy widely used in Nature to create materials with unique functional properties. We here present a comprehensive analysis of an adult sea urchin spine, and in revealing a complex, hierarchical structure, show how Nature fabricates a material which diffracts as a single crystal of calcite and yet fractures as a glassy material. Each spine comprises a highly oriented array of Mg-calcite nanocrystals in which amorphous regions and macromolecules are embedded. It is postulated that this mesocrystalline structure forms via the crystallization of a dense array of amorphous calcium carbonate (ACC) precursor particles. A residual surface layer of ACC and/or macromolecules remains around the nanoparticle units which creates the mesocrystal structure and contributes to the conchoidal fracture behavior. Nature’s demonstration of how crystallization of an amorphous precursor phase can create a crystalline material with remarkable properties therefore provides inspiration for a novel approach to the design and synthesis of synthetic composite materials. PMID:22343283
Structure-property relationships of a biological mesocrystal in the adult sea urchin spine.
Seto, Jong; Ma, Yurong; Davis, Sean A; Meldrum, Fiona; Gourrier, Aurelien; Kim, Yi-Yeoun; Schilde, Uwe; Sztucki, Michael; Burghammer, Manfred; Maltsev, Sergey; Jäger, Christian; Cölfen, Helmut
2012-03-06
Structuring over many length scales is a design strategy widely used in Nature to create materials with unique functional properties. We here present a comprehensive analysis of an adult sea urchin spine, and in revealing a complex, hierarchical structure, show how Nature fabricates a material which diffracts as a single crystal of calcite and yet fractures as a glassy material. Each spine comprises a highly oriented array of Mg-calcite nanocrystals in which amorphous regions and macromolecules are embedded. It is postulated that this mesocrystalline structure forms via the crystallization of a dense array of amorphous calcium carbonate (ACC) precursor particles. A residual surface layer of ACC and/or macromolecules remains around the nanoparticle units which creates the mesocrystal structure and contributes to the conchoidal fracture behavior. Nature's demonstration of how crystallization of an amorphous precursor phase can create a crystalline material with remarkable properties therefore provides inspiration for a novel approach to the design and synthesis of synthetic composite materials.
Tang, Dai-Ming; Ren, Cui-Lan; Lv, Ruitao; Yu, Wan-Jing; Hou, Peng-Xiang; Wang, Ming-Sheng; Wei, Xianlong; Xu, Zhi; Kawamoto, Naoyuki; Bando, Yoshio; Mitome, Masanori; Liu, Chang; Cheng, Hui-Ming; Golberg, Dmitri
2015-08-12
The hollow core of a carbon nanotube (CNT) provides a unique opportunity to explore the physics, chemistry, biology, and metallurgy of different materials confined in such nanospace. Here, we investigate the nonequilibrium metallurgical processes taking place inside CNTs by in situ transmission electron microscopy using CNTs as nanoscale resistively heated crucibles having encapsulated metal nanowires/crystals in their channels. Because of nanometer size of the system and intimate contact between the CNTs and confined metals, an efficient heat transfer and high cooling rates (∼10(13) K/s) were achieved as a result of a flash bias pulse followed by system natural quenching, leading to the formation of disordered amorphous-like structures in iron, cobalt, and gold. An intermediate state between crystalline and amorphous phases was discovered, revealing a memory effect of local short-to-medium range order during these phase transitions. Furthermore, subsequent directional crystallization of an amorphous iron nanowire formed by this method was realized under controlled Joule heating. High-density crystalline defects were generated during crystallization due to a confinement effect from the CNT and severe plastic deformation involved.
Theoretical studies of structure-property relations in graphene-based carbon nanostructures
NASA Astrophysics Data System (ADS)
Maroudas, Dimitrios
2014-03-01
This presentation focuses on establishing relations between atomic structure, electronic structure, and properties in graphene-based carbon nanostructures through first-principles density functional theory calculations and molecular-dynamics simulations. We have analyzed carbon nanostructure formation from twisted bilayer graphene, upon creation of interlayer covalent C-C bonds due to patterned hydrogenation or fluorination. For small twist angles and twist angles near 30 degrees, interlayer covalent bonding generates superlattices of diamond-like nanocrystals and of fullerene-like configurations, respectively, embedded within the graphene layers. The electronic band gaps of these superlattices can be tuned through selective chemical functionalization and creation of interlayer bonds, and range from a few meV to over 1.2 eV. The mechanical properties of these superstructures also can be precisely tuned by controlling the extent of chemical functionalization. Importantly, the shear modulus is shown to increase monotonically with the fraction of sp3-hybridized C-C bonds. We have also studied collective interactions of multiple defects such as random distributions of vacancies in single-layer graphene (SLG). We find that a crystalline-to-amorphous structural transition occurs at vacancy concentrations of 5-10% over a broad temperature range. The structure of our defect-induced amorphized graphene is in excellent agreement with experimental observations of SLG exposed to a high electron irradiation dose. Simulations of tensile tests on these irradiated graphene sheets identify trends for the ultimate tensile strength, failure strain, and toughness as a function of vacancy concentration. The vacancy-induced amorphization transition is accompanied by a brittle-to-ductile transition in the failure response of irradiated graphene sheets and even heavily damaged samples exhibit tensile strengths near 30 GPa, in significant excess of those typical of engineering materials.
Sutphin, David M.; Bliss, James D.
1990-01-01
On the basis of differences derived from genetic, descriptive, and grade-tonnage data, graphite deposits are classified here into three deposit types: disseminated flake, amorphous (microcrystalline), or graphite veins. Descriptive models have been constructed for each of these deposit types, and grade-tonnage models are constructed for disseminated flake and amorphous deposit types. Grade and tonnage data are used also to construct grade-tonnage models that assist in predicting the size and grade of undiscovered graphite deposits. The median tonnage and carbon grade of disseminated flake deposits are 240 000 tonnes and 9% carbon and for amorphous deposits, 130 000 tonnes and 40% carbon. The differences in grade between disseminated flake and amorphous deposit types are statistically significant, whereas the differences in amount of contained carbon are not.
Study for new hardmask process scheme
NASA Astrophysics Data System (ADS)
Lee, Daeyoup; Tatti, Phillip; Lee, Richard; Chang, Jack; Cho, Winston; Bae, Sanggil
2017-03-01
Hardmask processes are a key technique to enable low-k semiconductors, but they can have an impact on patterning control, influencing defectivity, alignment, and overlay. Specifically, amorphous carbon layer (ACL) hardmask schemes can negatively affect overlay by creating distorted alignment signals. A new scheme needs to be developed that can be inserted where amorphous carbon is used but provide better alignment performance. Typical spin-on carbon (SOC) materials used in other hardmask schemes have issues with DCD-FCD skew. In this paper we will evaluate new spin-on carbon material with a higher carbon content that could be a candidate to replace amorphous carbon.
Dynamic molecular structure of plant biomass-derived black carbon (biochar)
DOE Office of Scientific and Technical Information (OSTI.GOV)
Keiluweit, M.; Nico, P.S.; Johnson, M.G.
2009-11-15
Char black carbon (BC), the solid residue of incomplete combustion, is continuously being added to soils and sediments due to natural vegetation fires, anthropogenic pollution, and new strategies for carbon sequestration ('biochar'). Here we present a molecular-level assessment of the physical organization and chemical complexity of biomass-derived chars and, specifically, that of aromatic carbon in char structures. BET-N{sub 2} surface area, X-ray diffraction (XRD), synchrotron-based Near-edge X-ray Absorption Fine Structure (NEXAFS), and Fourier transform infrared (FT-IR) spectroscopy are used to show how two plant materials (wood and grass) undergo analogous, but quantitatively different physical-chemical transitions as charring temperature increases frommore » 100 to 700 C. These changes suggest the existence of four distinct categories of char consisting of a unique mixture of chemical phases and physical states: (i) in transition chars the crystalline character of the precursor materials is preserved, (ii) in amorphous chars the heat-altered molecules and incipient aromatic polycondensates are randomly mixed, (iii) composite chars consist of poorly ordered graphene stacks embedded in amorphous phases, and (iv) turbostratic chars are dominated by disordered graphitic crystallites. The molecular variations among the different char categories translate into differences in their ability to persist in the environment and function as environmental sorbents.« less
Bonding structure in amorphous carbon nitride: A spectroscopic and nuclear magnetic resonance study
NASA Astrophysics Data System (ADS)
Sánchez-López, J. C.; Donnet, C.; Lefèbvre, F.; Fernández-Ramos, C.; Fernández, A.
2001-07-01
Since the prediction of Liu and Cohen [Science 245, 841 (1989)] of the potential extraordinary mechanical properties of crystalline β-C3N4, many authors have attempted its synthesis. However, in most cases, the obtained materials are amorphous phases with a complex bonding structure. Their characterization is complicated due to the absence of a reference compound, the lack of long-range order, and the poor knowledge about their bonding structure. In this article, we present 1H, 13C, and 15N solid-state nuclear magnetic resonance (NMR) measurements for the determination of the bonding types in amorphous CNx films. NMR measurements do not require long-range order and are able to clearly identify the signals from the sp2- and sp3-bonded phases. The analysis of the data obtained by other characterization techniques, such as infrared spectroscopy, x-ray photoelectron spectroscopy, electron energy-loss spectroscopy, and x-ray absorption near-edge spectroscopy on the same sample, based on the information acquired by NMR, enables the description of a structure model for the studied amorphous-CNx phase prepared by dc-magnetron sputtering and to revise the interpretation found in the literature.
NASA Astrophysics Data System (ADS)
Mergelsberg, S. T.; Ulrich, R. N.; Michel, F. M.; Dove, P. M.
2016-12-01
Calcium carbonate minerals are an essential component in the exoskeletons of crustaceans and mollusks. The onset of exoskeleton mineralization includes the precipitation of amorphous calcium carbonate (ACC) as a reactive intermediate that later transforms to produce diverse structures. Despite the importance of ACC as a critical phase during skeleton formation, the chemical and physical properties are not well characterized at conditions that approximate biological environments. Of particular interest are the solubility of ACC, the short-range structure at the time of formation, and the evolution of ACC structure to final products. Recent advances showing the widespread occurrence of multistep pathways to mineralization in biological and geological settings (De Yoreo et al., 2015) underline the importance of understanding amorphous intermediates. Using quantitative laboratory techniques developed by our research group (Blue et al., 2013; Blue and Dove, 2015; Blue et al., in press), this experimental study quantifies the solubility of ACC in parallel with the physical characterization of the corresponding structure. We measured ACC solubility at specific time points during the precipitation and during its subsequent evolution under the mild pH conditions that approximate biological and environmental conditions. In parallel experiments, structural data were collected from in situ pair distribution function (PDF) analyses were conducted to follow the evolution of individual samples from initial precipitation to final product. The measurements are leading to a quantitative solubility function for ACC with variable Mg contents and an x-ray based understanding of ACC structure in the same particles. We are also finding temporal changes in the short-range order of ACC after precipitation and this order is dependent upon Mg content. Moreover, the data show Mg distribution through the ACC particles is dependent upon total alkalinity. Insights from this study hold promise for better understanding the nature of the initial ACC that forms and factors that influence its structural evolution to final products.
Synthesis of amorphous carbon from bio-products by drying method
NASA Astrophysics Data System (ADS)
Pamungkas, Diajeng I.; Haikal, Anas; Baqiya, Malik A.; Cahyono, Yoyok; Darminto
2018-04-01
Amorphous carbon (a-C) has extensively been studied in the last two decades due to many superior properties. Amorphous carbon was successfully prepared by carbonization of organic compounds exposed up to 200°C. Organic compounds that used in this research were coconut sap, lontar palm sap and their derivatives. The X-ray diffraction pattern shows that carbonization of organic compounds produce amorphous carbon phase at 2θ =20°. The infrared absorption in the region from 500 to 4000 cm-1 were resolved into several peaks, which were assigned to C-H, C=C, C-O, C=O and O-H. Four point probe method was also used to measure the conductivity and band gap of each material, resulting in 1.73 - 29.6 S/m and 0.08 - 0.49 eV respectively.
Structure Evolution and Thermoelectric Properties of Carbonized Polydopamine Thin Films.
Li, Haoqi; Aulin, Yaroslav V; Frazer, Laszlo; Borguet, Eric; Kakodkar, Rohit; Feser, Joseph; Chen, Yan; An, Ke; Dikin, Dmitriy A; Ren, Fei
2017-03-01
Carbonization of nature-inspired polydopamine can yield thin films with high electrical conductivity. Understanding of the structure of carbonized PDA (cPDA) is therefore highly desired. In this study, neutron diffraction, Raman spectroscopy, and other techniques indicate that cPDA samples are mainly amorphous with some short-range ordering and graphite-like structure that emerges with increasing heat treatment temperature. The electrical conductivity and the Seebeck coefficient show different trends with heat treatment temperature, while the thermal conductivity remains insensitive. The largest room-temperature ZT of 2 × 10 -4 was obtained on samples heat-treated at 800 °C, which is higher than that of reduced graphene oxide.
Modeling of amorphous SiCxO6/5 by classical molecular dynamics and first principles calculations.
Liao, Ningbo; Zhang, Miao; Zhou, Hongming; Xue, Wei
2017-02-14
Polymer-derived silicon oxycarbide (SiCO) presents excellent performance for high temperature and lithium-ion battery applications. Current experiments have provided some information on nano-structure of SiCO, while it is very challenging for experiments to take further insight into the molecular structure and its relationship with properties of materials. In this work, molecular dynamics (MD) based on empirical potential and first principle calculation were combined to investigate amorphous SiC x O 6/5 ceramics. The amorphous structures of SiCO containing silicon-centered mix bond tetrahedrons and free carbon were successfully reproduced. The calculated radial distribution, angular distribution and Young's modulus were validated by current experimental data, and more details on molecular structure were discussed. The change in the slope of Young's modulus is related to the glass transition temperature of the material. The proposed modeling approach can be used to predict the properties of SiCO with different compositions.
Modeling of amorphous SiCxO6/5 by classical molecular dynamics and first principles calculations
NASA Astrophysics Data System (ADS)
Liao, Ningbo; Zhang, Miao; Zhou, Hongming; Xue, Wei
2017-02-01
Polymer-derived silicon oxycarbide (SiCO) presents excellent performance for high temperature and lithium-ion battery applications. Current experiments have provided some information on nano-structure of SiCO, while it is very challenging for experiments to take further insight into the molecular structure and its relationship with properties of materials. In this work, molecular dynamics (MD) based on empirical potential and first principle calculation were combined to investigate amorphous SiCxO6/5 ceramics. The amorphous structures of SiCO containing silicon-centered mix bond tetrahedrons and free carbon were successfully reproduced. The calculated radial distribution, angular distribution and Young’s modulus were validated by current experimental data, and more details on molecular structure were discussed. The change in the slope of Young’s modulus is related to the glass transition temperature of the material. The proposed modeling approach can be used to predict the properties of SiCO with different compositions.
Yang, Jianping; Wang, Yunxiao; Li, Wei; Wang, Lianjun; Fan, Yuchi; Jiang, Wan; Luo, Wei; Wang, Yang; Kong, Biao; Selomulya, Cordelia; Liu, Hua Kun; Dou, Shi Xue; Zhao, Dongyuan
2017-12-01
Smart surface coatings of silicon (Si) nanoparticles are shown to be good examples for dramatically improving the cyclability of lithium-ion batteries. Most coating materials, however, face significant challenges, including a low initial Coulombic efficiency, tedious processing, and safety assessment. In this study, a facile sol-gel strategy is demonstrated to synthesize commercial Si nanoparticles encapsulated by amorphous titanium oxide (TiO 2 ), with core-shell structures, which show greatly superior electrochemical performance and high-safety lithium storage. The amorphous TiO 2 shell (≈3 nm) shows elastic behavior during lithium discharging and charging processes, maintaining high structural integrity. Interestingly, it is found that the amorphous TiO 2 shells offer superior buffering properties compared to crystalline TiO 2 layers for unprecedented cycling stability. Moreover, accelerating rate calorimetry testing reveals that the TiO 2 -encapsulated Si nanoparticles are safer than conventional carbon-coated Si-based anodes. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Preparation and analysis of particulate metal deposits
NASA Technical Reports Server (NTRS)
Poppa, H.; Moorhead, D.; Heinemann, K.
1985-01-01
Small particles and clusters of palladium were grown by deposition from the vapor phase under ultrahigh vacuum conditions. Amorphous and crystalline support films of Al2O3 and ultrathin amorphous carbon films were used as substrate materials. The growth of the metal deposit was monitored in situ by scanning transmission diffraction of energy-filtered 100 kV electrons and high resolution transmission electron microscopy (TEM) analysis was performed in a separate instrument. It was established by in situ TEM, however, that the transfer of specimens in this case did not unduly affect the size and distribution of deposit particles. It was found that the cleanness, stoichiometry, crystallinity and structural perfection of the support surface play an essential role in determining the crystalline perfection and structure of the particles. The smallest palladium clusters reproducibly prepared contained not more than six atoms but size determinations below 1 nm average particle diameter are very problematic with conventional TEM. Palladium particles grown on carbon supports feature an impurity-stabilized mosaic structure.
NASA Astrophysics Data System (ADS)
Reyes, R.; Cremona, M.; Achete, C. A.
2011-01-01
Amorphous silicon carbon nitride (a-SiC:N) thin films deposited by magnetron sputtering were used in the structure of an organic light emitting diode (OLED), obtaining an OLED operating in forward and reverse bias mode. The device consist of the heterojunction structure ITO/a-SiC:N/Hole Transport Layer (HTL)/ Electron Transport Layer (ETL)/a-SiC:N/Al. As hole transporting layer was used a thin film of 1-(3-methylphenyl)-1,2,3,4 tetrahydroquinoline - 6 - carboxyaldehyde - 1,1'- diphenylhydrazone (MTCD), while the tris(8-hydroxyquinoline aluminum) (Alq3) is used as electron transport and emitting layer. A significant increase in the voltage operation compared to the conventional ITO/MTCD/Alq3/Al structure was observed, so the onset of electroluminescence occurs at about 22 V in the forward and reverse bias mode of operation. The electroluminescence spectra is similar in both cases, only slightly shifted 0.14 eV to lower energies in relation to the conventional device.
Kroh, M; Hendriks, H; Kirby, E G; Sassen, M M
1976-08-01
Development of haploid meiospores of Allomyces arbuscula into germling cells with rhizoids and hyphae was followed during incubation in complete growth medium. The surface structure of encysted meiospores, rhizoids and hyphae before and after extraction of amorphous materials with ethanolic KOH was studied by means of carbon-platinum replicas. After 2--3 min incubation in complete medium 10% of the meiospores were surrounded by a cell wall containing microfibrils embedded in a matrix. Structure of cell walls of encysted meiospores, rhizoids, and hyphae differ from one another by the location of amorphous materials and by the arrangement of chitin microfibrils.
Li, Yinhui; Li, Kunyu; Su, Min; Ren, Yanmei; Li, Ying; Chen, Jianxin; Li, Liang
2016-11-20
In this work, carbon/SiO2 composites, using amylose and tetraethyl orthosilicate (TEOS) as raw materials, were successfully prepared by a facial hydrothermal carbonization process. The carbon/SiO2 composites were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), Energy Dispersive Spectroscopy (EDS), transmission electron microscope (TEM), N2 adsorption and Thermogravimetric (TG) analysis. The composites, which were made up of amorphous SiO2 and amorphous carbon, were found to have hierarchical porous structures. The mass ratios of amylose and SiO2 and the hydrothermal carbonization time had significant effects on the morphology of the composites, which had three shapes including monodispersed spheres, porous pieces and the nano-fibers combined with nano-spheres structures. The adsorption performance of the composites was studied using Pb(2+) as simulated contaminants from water. When the mass ratio of amylose and SiO2 was 9/1, the hydrothermal time was 30h and the hydrothermal temperature was 180°C, the adsorption capacity of the composites achieved to 52mg/g. Experimental data show that adsorption kinetics of the carbon/SiO2 composites can be fitted well by the Elovich model, while the isothermal data can be perfectly described by the Langmuir adsorption model and Freundlich adsorption model. The maximum adsorption capacity of the carbon/SiO2 composites is 56.18mgg(-1). Copyright © 2016 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Konicek, A. R.; Grierson, D. S.; Sumant, A. V.; Friedmann, T. A.; Sullivan, J. P.; Gilbert, P. U. P. A.; Sawyer, W. G.; Carpick, R. W.
2012-04-01
Highly sp3-bonded, nearly hydrogen-free carbon-based materials can exhibit extremely low friction and wear in the absence of any liquid lubricant, but this physical behavior is limited by the vapor environment. The effect of water vapor on friction and wear is examined as a function of applied normal force for two such materials in thin film form: one that is fully amorphous in structure (tetrahedral amorphous carbon, or ta-C) and one that is polycrystalline with <10 nm grains [ultrananocrystalline diamond (UNCD)]. Tribologically induced changes in the chemistry and carbon bond hybridization at the surface are correlated with the effect of the sliding environment and loading conditions through ex situ, spatially resolved near-edge x-ray absorption fine structure (NEXAFS) spectroscopy. At sufficiently high relative humidity (RH) levels and/or sufficiently low loads, both films quickly achieve a low steady-state friction coefficient and subsequently exhibit low wear. For both films, the number of cycles necessary to reach the steady-state is progressively reduced for increasing RH levels. Worn regions formed at lower RH and higher loads have a higher concentration of chemisorbed oxygen than those formed at higher RH, with the oxygen singly bonded as hydroxyl groups (C-OH). While some carbon rehybridization from sp3 to disordered sp2 bonding is observed, no crystalline graphite formation is observed for either film. Rather, the primary solid-lubrication mechanism is the passivation of dangling bonds by OH and H from the dissociation of vapor-phase H2O. This vapor-phase lubrication mechanism is highly effective, producing friction coefficients as low as 0.078 for ta-C and 0.008 for UNCD, and wear rates requiring thousands of sliding passes to produce a few nanometers of wear.
Multi-Functions of Carbonated Calcium Deficient Hydroxyapatite (CDHA)
NASA Astrophysics Data System (ADS)
Zhou, Huan
Natural bone is a complex composite mainly constituted of inorganic minerals and organic collagen molecules. Calcium phosphate (CaP) based materials have been proposed as the predominant bone substitute for bone tissue engineering applications due to their chemical similarity to bone mineral. Amorphous carbonated calcium deficient hydroxyapatite (CDHA) is an important compound among CaP materials because of the amorphous crystallite structure. The presence of extra ions in its lattice structure not only influences cell attachment and proliferation of osteoblasts, but also helps in bone metabolism. Biomimetic coating approach is the most widely used approach to produce CDHA coatings to implant. It is a process using simulated body fluid (SBF) to deposit bone-like CDHA coating to various material surfaces. The CDHA formation mechanism, SBF compositions and reacting conditions of biomimetic coating have already been sufficiently studied and compared in the past 20 years. It is an attempt in this thesis to explore new applications of SBF in biomedical research, focusing on different biomaterial applications: 1) based on the low temperature reaction condition of SBF, bisphosphonate incorporated CDHA coatings were deposited onto Ti6Al4V surface for the treatment of osteoporosis; 2) amorphous calcium phosphate nanospheres with extra elements in the lattice structure were prepared by a novel microwave assisted approach, providing a new potential of CaP materials production; 3) CDHA particles formed in SBF can be used as great fillers with biopolymers for preparing biocomposites for biomedical applications; 4) based on the high activity of CDHA amorphous structure and the stabilization ability of ethanol, yttrium and europium doped calcium phosphates were prepared using CDHA as a sacrificing template. In the end, future work based on these observations in the thesis is addressed, including areas of drug delivery, biocomposite fabrication and preparation of functionalized calcium phosphate materials.
In Situ Observations of Phase Transitions in Metastable Nickel (Carbide)/Carbon Nanocomposites
2016-01-01
Nanocomposite thin films comprised of metastable metal carbides in a carbon matrix have a wide variety of applications ranging from hard coatings to magnetics and energy storage and conversion. While their deposition using nonequilibrium techniques is established, the understanding of the dynamic evolution of such metastable nanocomposites under thermal equilibrium conditions at elevated temperatures during processing and during device operation remains limited. Here, we investigate sputter-deposited nanocomposites of metastable nickel carbide (Ni3C) nanocrystals in an amorphous carbon (a-C) matrix during thermal postdeposition processing via complementary in situ X-ray diffractometry, in situ Raman spectroscopy, and in situ X-ray photoelectron spectroscopy. At low annealing temperatures (300 °C) we observe isothermal Ni3C decomposition into face-centered-cubic Ni and amorphous carbon, however, without changes to the initial finely structured nanocomposite morphology. Only for higher temperatures (400–800 °C) Ni-catalyzed isothermal graphitization of the amorphous carbon matrix sets in, which we link to bulk-diffusion-mediated phase separation of the nanocomposite into coarser Ni and graphite grains. Upon natural cooling, only minimal precipitation of additional carbon from the Ni is observed, showing that even for highly carbon saturated systems precipitation upon cooling can be kinetically quenched. Our findings demonstrate that phase transformations of the filler and morphology modifications of the nanocomposite can be decoupled, which is advantageous from a manufacturing perspective. Our in situ study also identifies the high carbon content of the Ni filler crystallites at all stages of processing as the key hallmark feature of such metal–carbon nanocomposites that governs their entire thermal evolution. In a wider context, we also discuss our findings with regard to the much debated potential role of metastable Ni3C as a catalyst phase in graphene and carbon nanotube growth. PMID:27746852
Synthesis of Antimony Doped Amorphous Carbon Films
NASA Astrophysics Data System (ADS)
Okuyama, H.; Takashima, M.; Akasaka, H.; Ohtake, N.
2013-06-01
We report the effects of antimony (Sb) doping on the electrical and optical properties of amorphous carbon (a-C:H) films grown on silicon and copper substrates by magnetron sputtering deposition. For film deposition, the mixture targets fabricated from carbon and antimony powders was used. The atomic concentration of carbon, hydrogen, and antimony, in the film deposited from the 1.0 mol% Sb containing target were 81, 17, 2 at.%, respectively. These elements were homogeneously distributed in the film. On the structural effect, the average continuous sp2 carbon bonding networks decreased with Sb concentration increasing, and defects in the films were increased with the Sb incorporation because atomic radius of Sb atoms is twice larger size than that of carbon. The optical gap and the electrical resistivity were carried out before and after the Sb doping. The results show that optical gap dropped from 3.15 to 3.04 eV corresponding to non-doping to Sb-doping conditions, respectively. The electrical resistivity reduced from 10.5 to 1.0 MΩm by the Sb doping. These results suggest the doping level was newly formed in the forbidden band.
Calcium phosphate mineralization is widely applied in crustacean mandibles.
Bentov, Shmuel; Aflalo, Eliahu D; Tynyakov, Jenny; Glazer, Lilah; Sagi, Amir
2016-02-24
Crustaceans, like most mineralized invertebrates, adopted calcium carbonate mineralization for bulk skeleton reinforcement. Here, we show that a major part of the crustacean class Malacostraca (which includes lobsters, crayfishes, prawns and shrimps) shifted toward the formation of calcium phosphate as the main mineral at specified locations of the mandibular teeth. In these structures, calcium phosphate is not merely co-precipitated with the bulk calcium carbonate but rather creates specialized structures in which a layer of calcium phosphate, frequently in the form of crystalline fluorapatite, is mounted over a calcareous "jaw". From a functional perspective, the co-existence of carbonate and phosphate mineralization demonstrates a biomineralization system that provides a versatile route to control the physico-chemical properties of skeletal elements. This system enables the deposition of amorphous calcium carbonate, amorphous calcium phosphate, calcite and apatite at various skeletal locations, as well as combinations of these minerals, to form graded composites materials. This study demonstrates the widespread occurrence of the dual mineralization strategy in the Malacostraca, suggesting that in terms of evolution, this feature of phosphatic teeth did not evolve independently in the different groups but rather represents an early common trait.
Calcium phosphate mineralization is widely applied in crustacean mandibles
Bentov, Shmuel; Aflalo, Eliahu D.; Tynyakov, Jenny; Glazer, Lilah; Sagi, Amir
2016-01-01
Crustaceans, like most mineralized invertebrates, adopted calcium carbonate mineralization for bulk skeleton reinforcement. Here, we show that a major part of the crustacean class Malacostraca (which includes lobsters, crayfishes, prawns and shrimps) shifted toward the formation of calcium phosphate as the main mineral at specified locations of the mandibular teeth. In these structures, calcium phosphate is not merely co-precipitated with the bulk calcium carbonate but rather creates specialized structures in which a layer of calcium phosphate, frequently in the form of crystalline fluorapatite, is mounted over a calcareous “jaw”. From a functional perspective, the co-existence of carbonate and phosphate mineralization demonstrates a biomineralization system that provides a versatile route to control the physico-chemical properties of skeletal elements. This system enables the deposition of amorphous calcium carbonate, amorphous calcium phosphate, calcite and apatite at various skeletal locations, as well as combinations of these minerals, to form graded composites materials. This study demonstrates the widespread occurrence of the dual mineralization strategy in the Malacostraca, suggesting that in terms of evolution, this feature of phosphatic teeth did not evolve independently in the different groups but rather represents an early common trait. PMID:26906263
Wei, Helin; Wei, Sihang; Tian, Weifeng; Zhu, Daming; Liu, Yuhao; Yuan, Lili; Li, Xin
2014-01-01
Hybrid carbon films composed of graphene film and porous carbon film may give full play to the advantages of both carbon materials, and have great potential for application in energy storage and conversion devices. Unfortunately, there are very few reports on fabrication of hybrid carbon films. Here we demonstrate a simple approach to fabricate free-standing sandwich-structured hybrid carbon film composed of porous amorphous carbon film and multilayer graphene film by chemical vapor deposition in a controllable and scalable way. Hybrid carbon films reveal good electrical conductivity, excellent flexibility, and good compatibility with substrate. Supercapacitors assembled by hybrid carbon films exhibit ultrahigh rate capability, wide frequency range, good capacitance performance, and high-power density. Moreover, this approach may provide a general path for fabrication of hybrid carbon materials with different structures by using different metals with high carbon solubility, and greatly expands the application scope of carbon materials. PMID:25394410
High rate chemical vapor deposition of carbon films using fluorinated gases
Stafford, Byron L.; Tracy, C. Edwin; Benson, David K.; Nelson, Arthur J.
1993-01-01
A high rate, low-temperature deposition of amorphous carbon films is produced by PE-CVD in the presence of a fluorinated or other halide gas. The deposition can be performed at less than 100.degree. C., including ambient room temperature, with a radio frequency plasma assisted chemical vapor deposition process. With less than 6.5 atomic percent fluorine incorporated into the amorphous carbon film, the characteristics of the carbon film, including index of refraction, mass density, optical clarity, and chemical resistance are within fifteen percent (15%) of those characteristics for pure amorphous carbon films, but the deposition rates are high.
Method of depositing multi-layer carbon-based coatings for field emission
Sullivan, John P.; Friedmann, Thomas A.
1999-01-01
A novel field emitter device for cold cathode field emission applications, comprising a multi-layer resistive carbon film. The multi-layered film of the present invention is comprised of at least two layers of a resistive carbon material, preferably amorphous-tetrahedrally coordinated carbon, such that the resistivities of adjacent layers differ. For electron emission from the surface, the preferred structure comprises a top layer having a lower resistivity than the bottom layer. For edge emitting structures, the preferred structure of the film comprises a plurality of carbon layers, wherein adjacent layers have different resistivities. Through selection of deposition conditions, including the energy of the depositing carbon species, the presence or absence of certain elements such as H, N, inert gases or boron, carbon layers having desired resistivities can be produced. Field emitters made according the present invention display improved electron emission characteristics in comparison to conventional field emitter materials.
Method of depositing multi-layer carbon-based coatings for field emission
Sullivan, J.P.; Friedmann, T.A.
1999-08-10
A novel field emitter device is disclosed for cold cathode field emission applications, comprising a multi-layer resistive carbon film. The multi-layered film of the present invention is comprised of at least two layers of a resistive carbon material, preferably amorphous-tetrahedrally coordinated carbon, such that the resistivities of adjacent layers differ. For electron emission from the surface, the preferred structure comprises a top layer having a lower resistivity than the bottom layer. For edge emitting structures, the preferred structure of the film comprises a plurality of carbon layers, wherein adjacent layers have different resistivities. Through selection of deposition conditions, including the energy of the depositing carbon species, the presence or absence of certain elements such as H, N, inert gases or boron, carbon layers having desired resistivities can be produced. Field emitters made according the present invention display improved electron emission characteristics in comparison to conventional field emitter materials. 8 figs.
Disordered amorphous calcium carbonate from direct precipitation
Farhadi Khouzani, Masoud; Chevrier, Daniel M.; Güttlein, Patricia; ...
2015-06-01
Amorphous calcium carbonate (ACC) is known to play a prominent role in biomineralization. Different studies on the structure of biogenic ACCs have illustrated that they can have distinct short-range orders. However, the origin of so-called proto-structures in synthetic and additive-free ACCs is not well understood. In the current work, ACC has been synthesised in iso-propanolic media by direct precipitation from ionic precursors, and analysed utilising a range of different techniques. The data suggest that this additive-free type of ACC does not resemble clear proto-structural motifs relating to any crystalline polymorph. This can be explained by the undefined pH value inmore » iso-propanolic media, and the virtually instantaneous precipitation. Altogether, this work suggests that aqueous systems and pathways involving pre-nucleation clusters are required for the generation of clear proto-structural features in ACC. Experiments on the ACC-to-crystalline transformation in solution with and without ethanol highlight that polymorph selection is under kinetic control, while the presence of ethanol can control dissolution re-crystallisation pathways.« less
Atomic scale simulations of vapor cooled carbon clusters
NASA Astrophysics Data System (ADS)
Bogana, M. P.; Colombo, L.
2007-03-01
By means of atomistic simulations we observed the formation of many topologically non-equivalent carbon clusters formed by the condensation of liquid droplets, including: (i) standard fullerenes and onion-like structures, (ii) clusters showing extremely complex surfaces with both positive and negative curvatures and (iii) complex endohedral structures. In this work we offer a thorough structural characterization of the above systems, as well as an attempt to correlate the resulting structure to the actual protocol of growth. The IR and Raman responses of some exotic linear carbon structures have been further investigated, finding good agreement with experimental evidence of carbinoid structures in cluster-assembled films. Towards the aim of fully understanding the process of cluster-to-cluster coalescence dynamics, we further simulated an aerosol of amorphous carbon clusters at controlled temperatures. Various annealing temperatures and times have been observed, identifying different pathways for cluster ripening, ranging from simple coalescence to extensive reconstruction.
Covalently Bonded Three-Dimensional Carbon Nanotube Solids via Boron Induced Nanojunctions
2012-04-13
Novel Carbon Morphologies: From Covalent Y-Junctions to Sea - Urchin -Like Structures. Adv. Func. Mater. 19, 1193–1199 (2009). 15. Sumpter, B. G. et al...amorphous carbon as depicted from SEM (Fig. 1c). The X-ray powder diffraction pattern shows that as-produced CBXMWNT sponges are indeed crystalline and...material as-produced; (b) shows photograph of the flexibility and mechanical stablility upon bending the sample (a) by hand; (c) SEM image after ion
NASA Astrophysics Data System (ADS)
Sugiura, Hirotsugu; Jia, Lingyun; Kondo, Hiroki; Ishikawa, Kenji; Tsutsumi, Takayoshi; Hayashi, Toshio; Takeda, Keigo; Sekine, Makoto; Hori, Masaru
2018-06-01
Quadruple mass spectrometric measurements of CH3 density during radical-injection plasma-enhanced chemical vapor deposition to consider the sp2 fraction of amorphous carbon (a-C) films were performed. The sp2 fraction of the a-C films reached a minimum of 46%, where the CH3 density was maximum for a residence time of 6 ms. The sp2 fraction of the a-C films was tailored with the gaseous phase CH3 density during the deposition. This knowledge is useful for understanding the formation mechanism of bonding structures in the a-C films, which enables the precise control of their electronic properties.
Disorder and Urbach energy in hydrogenated amorphous carbon: A phenomenological model
NASA Astrophysics Data System (ADS)
Fanchini, G.; Tagliaferro, A.
2004-08-01
We develop a phenomenological model describing the structural and topological effects of the disorder in hydrogenated amorphous carbons (a-C :H), through the analysis of the Raman G-peak width and the optical absorption spectra, providing information on the densities of electronic π ad π* states (πDOS). We show that the Urbach energy is not related to topological disorder but to the Gaussian width (σπ) of the πDOS, peaked at ±Eπ energies above/below the Fermi level. σπ, on its turn, is not related in a straightforward manner to the disorder. The disorder is better represented by the σπ/Eπ ratio, expressing the disorder-induced narrowing of the Tauc optical gap.
Structure evolution and thermoelectric properties of carbonized polydopamine thin films
Li, Haoqi; Aulin, Yaroslav V.; Frazer, Laszlo; ...
2017-02-13
Carbonization of nature-inspired polydopamine can yield thin films with high electrical conductivity. Understanding of the structure of carbonized PDA (cPDA) is therefore highly desired. In this study, neutron diffraction, Raman spectroscopy, and other techniques indicate that cPDA samples are mainly amorphous with some short-range ordering and graphite-like structure that emerges with increasing heat treatment temperature. The electrical conductivity and the Seebeck coefficient show different trends with heat treatment temperature, while the thermal conductivity remains insensitive. Finally, the largest room-temperature ZT of 2 × 10 –4 was obtained on samples heat-treated at 800 °C, which is higher than that of reducedmore » graphene oxide.« less
Protective Effects of Fluoride and Amorphous Calcium Phosphate Against Acid Erosion
2012-07-01
CO3 ...These carbonate-‐rich regions of the enamel contain areas where the substitution of carbonate ( CO3 ...for some of the phosphate (PO43-‐) disturbs the crystal lattice structure. The irregular
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sun, Shengtong; Chevrier, Daniel M.; Zhang, Peng
Amorphous intermediate phases are vital precursors in the crystallization of many biogenic minerals. While inherent short-range orders have been found in amorphous calcium carbonates (ACCs) relating to different crystalline forms, it has never been clarified experimentally whether such orders already exist in very small clusters less than 2 nm in size. Here, we studied the stability and structure of 10,12-pentacosadiynoic acid (PCDA) protected ACC clusters with a core size of ca. 1.4 nm consisting of only seven CaCO 3 units. Ligand concentration and structure are shown to be key factors in stabilizing the ACC clusters. More importantly, even in suchmore » small CaCO 3 entities, a proto-calcite short-range order can be identified but with a relatively high degree of disorder that arises from the very small size of the CaCO 3 core. Our findings support the notion of a structural link between prenucleation clusters, amorphous intermediates, and final crystalline polymorphs, which appears central to the understanding of polymorph selection.« less
NASA Astrophysics Data System (ADS)
Novoselova, Inessa A.; Oliinyk, Nikolai F.; Voronina, Anastasiya B.; Volkov, Sergei V.
2008-08-01
An electrochemical study of mechanisms of electrodeposition of carbon solid phases from halide melts (Na,K|Cl; Na,K,Cs|Cl), saturated with carbon dioxide under an excessive pressure of up to 1.5 MPa, has been carried out in the temperature range 550 - 850 °C by cyclic voltammetry. It has been found that the cathode process occurs in three steps at sweep rates of less than 0.1 Vs-1, and its electrochemical-chemical-electrochemical (ECE) mechanism is suggested. It has furthermore been found that cathodic deposits contain nano-sized carbon particles of different forms and structure: blocks of amorphous carbon, crystalline graphite, carbon nanotubes (CNT), and nanofibres. The outer diameter of the tubes is 5 - 250 nm, and the internal diameter is 2 - 140 nm. A correlation between the product structure and yield against electrolysis conditions and regimes has been established.
Structural and spectroscopic studies of a commercial glassy carbon
NASA Astrophysics Data System (ADS)
Parker, Stewart F.; Imberti, Silvia; Callear, Samantha K.; Albers, Peter W.
2013-12-01
Glassy carbon is a form of carbon made by heating a phenolic resin to high temperature in an inert atmosphere. It has been suggested that it is composed of fullerene-like structures. The aim of the present work was to characterize the material using both structural (neutron diffraction and transmission electron microscopy) and spectroscopic (inelastic neutron scattering, Raman and X-ray photoelectron spectroscopies) methods. We find no evidence to support the suggestion of fullerene-like material being present to a significant extent, rather the model that emerges from all of the techniques is that the material is very like amorphous carbon, consisting of regions of small graphite-like basic structural units of partly stacked but mismatched structure with the edges terminated by hydrogen or hydroxyls. We do find evidence for the presence of a small quantity of water trapped in the network and suggest that this may account for batch-to-batch variation in properties that may occur.
Coal as an abundant source of graphene quantum dots
NASA Astrophysics Data System (ADS)
Ye, Ruquan; Xiang, Changsheng; Lin, Jian; Peng, Zhiwei; Huang, Kewei; Yan, Zheng; Cook, Nathan P.; Samuel, Errol L. G.; Hwang, Chih-Chau; Ruan, Gedeng; Ceriotti, Gabriel; Raji, Abdul-Rahman O.; Martí, Angel A.; Tour, James M.
2013-12-01
Coal is the most abundant and readily combustible energy resource being used worldwide. However, its structural characteristic creates a perception that coal is only useful for producing energy via burning. Here we report a facile approach to synthesize tunable graphene quantum dots from various types of coal, and establish that the unique coal structure has an advantage over pure sp2-carbon allotropes for producing quantum dots. The crystalline carbon within the coal structure is easier to oxidatively displace than when pure sp2-carbon structures are used, resulting in nanometre-sized graphene quantum dots with amorphous carbon addends on the edges. The synthesized graphene quantum dots, produced in up to 20% isolated yield from coal, are soluble and fluorescent in aqueous solution, providing promise for applications in areas such as bioimaging, biomedicine, photovoltaics and optoelectronics, in addition to being inexpensive additives for structural composites.
Coal as an abundant source of graphene quantum dots.
Ye, Ruquan; Xiang, Changsheng; Lin, Jian; Peng, Zhiwei; Huang, Kewei; Yan, Zheng; Cook, Nathan P; Samuel, Errol L G; Hwang, Chih-Chau; Ruan, Gedeng; Ceriotti, Gabriel; Raji, Abdul-Rahman O; Martí, Angel A; Tour, James M
2013-01-01
Coal is the most abundant and readily combustible energy resource being used worldwide. However, its structural characteristic creates a perception that coal is only useful for producing energy via burning. Here we report a facile approach to synthesize tunable graphene quantum dots from various types of coal, and establish that the unique coal structure has an advantage over pure sp2-carbon allotropes for producing quantum dots. The crystalline carbon within the coal structure is easier to oxidatively displace than when pure sp2-carbon structures are used, resulting in nanometre-sized graphene quantum dots with amorphous carbon addends on the edges. The synthesized graphene quantum dots, produced in up to 20% isolated yield from coal, are soluble and fluorescent in aqueous solution, providing promise for applications in areas such as bioimaging, biomedicine, photovoltaics and optoelectronics, in addition to being inexpensive additives for structural composites.
Zhai, Zihao; Shen, Honglie; Chen, Jieyi; Li, Xuemei; Jiang, Ye
2018-05-23
Direct growth of graphene films on glass is of great importance but has so far met with limited success. The noncatalytic property of glass results in the low decomposition ability of hydrocarbon precursors, especially at reduced temperatures (<1000 °C), and therefore amorphous carbon (a-C) films are more likely to be obtained. Here, we report the hydrogen influence on the structural and electrical properties of carbon films deposited on quartz glass at 850 °C by hot-filament chemical vapor deposition (HFCVD). The results revealed that the obtained a-C films were all graphitelike carbon films. Structural transition of the deposited films from a-C to nanocrystalline graphene was achieved by raising the hydrogen dilution ratios from 10 to over 80%. On the basis of systematic structural and chemical characterizations, a schematic process with three steps including sp 2 chain aggregation, aromatic ring formation, and sp 3 bond etching was proposed to interpret the structural evolution. The nanocrystalline graphene films grown on glass by HFCVD exhibited good electrical performance with a carrier mobility of 36.76 cm 2 /(V s) and a resistivity of 5.24 × 10 -3 Ω cm over an area of 1 cm 2 . Temperature-dependent electrical characterizations revealed that the electronic transport in carbon films was dominated by defect, localized, and extended states, respectively, when increasing the temperature from 75 to 292 K. The nanocrystalline graphene films presented higher carrier mobility and lower carrier concentration than those of a-C films, which was mainly attributed to their smaller conductive activation energy. The present investigation provides an effective way for direct growth of graphene films on glass at reduced temperatures and also offers useful insights into the understanding of structural and electrical relationship between a-C and graphene.
NanoSIMS Reveals New Structural and Elemental Signatures of Early Life
NASA Technical Reports Server (NTRS)
Oehler, Dorothy Z.; Mostefaoui, Smail; Meibom, Anders; Selo, Madeleine; Robert, Francois; McKay, David S.
2006-01-01
The young technology of NanoSIMS is unlocking new information from organic matter in ancient sediments. We have used this technique to characterize sub-micron scale element composition of Proterozoic organics that are clearly biogenic as a guide for interpreting problematic structures in terrestrial or extraterrestrial samples. We used the NanoSIMS 50 of the National Museum of Natural History in Paris to map carbon, nitrogen (as CN), and sulfur in organic structures from the approximately 0.8 Ga Bitter Springs Formation. We analyzed spheroidal and filamentous microfossils as well as organic laminae that appeared amorphous by optical and scanning electron microscopy. In clear-cut microfossils, a coincidence between optical images and NanoSIMS element maps suggests a biological origin for the mapped carbon, sulfur, and nitrogen; this conclusion is supported by high resolution NanoSIMS maps showing identical spatial distributions of C, CN and S. High resolution images also demonstrate distinctive nano structure of the filaments and spheroids. In the amorphous laminae, NanoSIMS reveals morphologies reminiscent of compressed microfossils. Distinct CN/C ratios of the spheroids, filaments, and laminae may reflect their biological precursors (cell walls, cyanobacterial sheaths, and microbial communities/biofilms, respectively). Similar amorphous laminae comprise a preponderance of the organic matter in many Precambrian deposits. Thus it is possible that NanoSIMS will provide fresh insight into a large body of previously uninterpretable material. Additionally, NanoSIMS analysis may establish new biosignatures that will be helpful for assessing the origin and biogenicity of controversial Archean structures and any organic materials that may occur in Martian or other extraterrestrial samples.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Feng, Kai; Wang, Yibo; Li, Zhuguo, E-mail: lizg@sjtu.edu.cn
Austenitic stainless steel 316L is ion implanted by carbon with implantation fluences of 1.2 × 10{sup 17} ions-cm{sup −} {sup 2}, 2.4 × 10{sup 17} ions-cm{sup −} {sup 2}, and 4.8 × 10{sup 17} ions-cm{sup −} {sup 2}. The ion implantation induced graded microstructure and phase transformation in stainless steel is investigated by X-ray diffraction, X-ray photoelectron spectroscopy and high resolution transmission electron microscopy. The corrosion resistance is evaluated by potentiodynamic test. It is found that the initial phase is austenite with a small amount of ferrite. After low fluence carbon ion implantation, an amorphous layer and ferrite phase enrichedmore » region underneath are formed. Nanophase particles precipitate from the amorphous layer due to energy minimization and irradiation at larger ion implantation fluence. The morphology of the precipitated nanophase particles changes from circular to dumbbell-like with increasing implantation fluence. The corrosion resistance of stainless steel is enhanced by the formation of amorphous layer and graphitic solid state carbon after carbon ion implantation. - Highlights: • Carbon implantation leads to phase transformation from austenite to ferrite. • The passive film on SS316L becomes thinner after carbon ion implantation. • An amorphous layer is formed by carbon ion implantation. • Nanophase precipitate from amorphous layer at higher ion implantation fluence. • Corrosion resistance of SS316L is improved by carbon implantation.« less
Nemati, Narguess; Bozorg, Mansoor; Penkov, Oleksiy V; Shin, Dong-Gap; Sadighzadeh, Asghar; Kim, Dae-Eun
2017-09-06
A novel functional multilayer coating with periodically stacked nanolayers of amorphous carbon (a:C)/tungsten carbide (WC) and an adhesion layer of chromium (Cr) was deposited on 304 stainless steel using a dual magnetron sputtering technique. Through process optimization, highly densified coatings with high elasticity and shear modulus, excellent wear resistance, and minimal susceptibility to corrosive and caustic media could be acquired. The structural and mechanical properties of the optimized coatings were studied in detail using a variety of analytical techniques. Furthermore, finite element method simulations indicated that the stress generated due to contact against a steel ball was distributed well within the coating, which allowed the stresses to be lower than the yield threshold of the coating. Thus, an ultralow wear rate of ∼10 -12 mm 3 /N mm could be achieved in dry sliding conditions under relatively high Hertzian contact pressures of ∼0.4-0.9 GPa. The amorphous and pinhole-free structure of the individual layers, sufficient number of pairs, and the relatively dense stacked layers resulted in significant polarization resistance (Z″ = 5.5 × 10 6 Ω cm 2 ) and increased the corrosion resistance of the coating by 10-fold compared to that of recently reported corrosion-resistant coatings.
NASA Astrophysics Data System (ADS)
Dubkov, S.; Trifonov, A.; Shaman, Yu; Pavlov, A.; Shulyat'ev, A.; Skorik, S.; Kirilenko, E. P.; Rygalin, B.
2016-08-01
This research shows the possibility of carbon nanotubes (CNTs) formation on the surface of low nickel (∼ 10 at.%) Ni-Nb-N amorphous metal alloy film by CVD method at 550 °C of the gas mixture based on acetylene. The structure of CNT were studied by transmission and scanning-electron microscopy, energy-dispersive X-ray and the Raman spectroscopy.
Evolution of the secondary electron emission during the graphitization of thin C films
NASA Astrophysics Data System (ADS)
Larciprete, Rosanna; Grosso, Davide Remo; Di Trolio, Antonio; Cimino, Roberto
2015-02-01
The relation between the atomic hybridization and the secondary electron emission yield (SEY) in carbon materials has been investigated during the thermal graphitization of thin amorphous carbon layers deposited by magnetron sputtering on Cu substrates. C1s core level, valence band and Raman spectroscopy were used to follow the sp3→sp2 structural reorganization while the SEY curves as a function of the kinetic energy of the incident electron beam were measured in parallel. We found that an amorphous C layer with a thickness of a few tens of nanometers is capable to modify the secondary emission properties of the clean copper surface, reducing the maximum yield from 1.4 to 1.2. A further SEY decrease observed with the progressive conversion of sp3 hybrids into six-fold aromatic domains was related to the electronic structure close to the Fermi level of the C-films. We found that a moderate structural quality of the C layer is sufficient to notably decrease the SEY as aromatic clusters of limited size approach the secondary emission properties of graphite.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Morandeau, Antoine E.; White, Claire E.
Calcium–silicate–hydrate (C–S–H) gel is the main binder component in hydrated ordinary Portland cement (OPC) paste, and is known to play a crucial role in the carbonation of cementitious materials, especially for more sustainable alternatives containing supplementary cementitious materials. However, the exact atomic structural changes that occur during carbonation of C–S–H gel remain unknown. Here, we investigate the local atomic structural changes that occur during carbonation of a synthetic calcium–silicate–hydrate gel exposed to pure CO₂ vapour, using in situ X-ray total scattering measurements and subsequent pair distribution function (PDF) analysis. By analysing both the reciprocal and real-space scattering data as themore » C–S–H carbonation reaction progresses, all phases present during the reaction (crystalline and non-crystalline) have been identified and quantified, with the results revealing the emergence of several polymorphs of crystalline calcium carbonate (vaterite and calcite) in addition to the decalcified C–S–H gel. Furthermore, the results point toward residual calcium being present in the amorphous decalcified gel, potentially in the form of an amorphous calcium carbonate phase. As a result of the quantification process, the reaction kinetics for the evolution of the individual phases have been obtained, revealing new information on the rate of growth/dissolution for each phase associated with C–S–H gel carbonation. Moreover, the investigation reveals that the use of real space diffraction data in the form of PDFs enables more accurate determination of the phases that develop during complex reaction processes such as C–S–H gel carbonation in comparison to the conventional reciprocal space Rietveld analysis approach.« less
Low-energy electron irradiation induced top-surface nanocrystallization of amorphous carbon film
NASA Astrophysics Data System (ADS)
Chen, Cheng; Fan, Xue; Diao, Dongfeng
2016-10-01
We report a low-energy electron irradiation method to nanocrystallize the top-surface of amorphous carbon film in electron cyclotron resonance plasma system. The nanostructure evolution of the carbon film as a function of electron irradiation density and time was examined by transmission electron microscope (TEM) and Raman spectroscopy. The results showed that the electron irradiation gave rise to the formation of sp2 nanocrystallites in the film top-surface within 4 nm thickness. The formation of sp2 nanocrystallite was ascribed to the inelastic electron scattering in the top-surface of carbon film. The frictional property of low-energy electron irradiated film was measured by a pin-on-disk tribometer. The sp2 nanocrystallized top-surface induced a lower friction coefficient than that of the original pure amorphous film. This method enables a convenient nanocrystallization of amorphous surface.
USDA-ARS?s Scientific Manuscript database
Calcium supplementation is a widely recognized strategy for achieving adequate calcium intake. We designed this blinded, randomized, crossover interventional trial to compare the bioavailability of a new stable synthetic amorphous calcium carbonate (ACC) with that of crystalline calcium carbonate (C...
The solid film lubrication by carbon ion implantation into α-Al 2O 3
NASA Astrophysics Data System (ADS)
Jun, Tian; Qizu, Wang; Qunji, Xue
1998-10-01
Improvement in tribological performance by C +110 keV implantation can be achieved by having a more graphite-like carbon structure on Al 2O 3. It was shown that fracture toughness and critical peeling load increased for a fluence of 5 × 10 17C +/cm 2 because of residual compression stress and amorphism of surface. The testing in a different implantation dose indicated that the friction and wear mechanism in Optimol fretting wear machine (SRV) was a combination of surface structure and its abrasive wear. Raman shift shows that the amorphous graphite with 5 × 10 17-1 × 10 18 C +/cm 2 implantation dose was formed on Al 2O 3 surface, so that it reduced friction coefficient and wear of Al 2O 3, also it is noticed that the failure of lubrication due to graphite-like film wear is much earlier in the implantation sample with 1 × 10 17C +/cm 2 dose.
Mechanical properties of graphene oxides.
Liu, Lizhao; Zhang, Junfeng; Zhao, Jijun; Liu, Feng
2012-09-28
The mechanical properties, including the Young's modulus and intrinsic strength, of graphene oxides are investigated by first-principles computations. Structural models of both ordered and amorphous graphene oxides are considered and compared. For the ordered graphene oxides, the Young's modulus is found to vary from 380 to 470 GPa as the coverage of oxygen groups changes, respectively. The corresponding variations in the Young's modulus of the amorphous graphene oxides with comparable coverage are smaller at 290-430 GPa. Similarly, the ordered graphene oxides also possess higher intrinsic strength compared with the amorphous ones. As coverage increases, both the Young's modulus and intrinsic strength decrease monotonically due to the breaking of the sp(2) carbon network and lowering of the energetic stability for the ordered and amorphous graphene oxides. In addition, the band gap of the graphene oxide becomes narrower under uniaxial tensile strain, providing an efficient way to tune the electronic properties of graphene oxide-based materials.
Thermally activated diffusion of copper into amorphous carbon
Appy, David; Wallingford, Mark; Jing, Dapeng; ...
2017-07-11
Using x-ray photoelectron spectroscopy, the authors characterize the thermally activated changes that occur when Cu is deposited on amorphous carbon supported on Si at 300 K, then heated to 800 K. The authors compare data for Cu on the basal plane of graphite with pinning defects, where scanning tunneling microscopy reveals that coarsening is the main process in this temperature range. Coarsening begins at 500–600 K and causes moderate attenuation of the Cu photoelectron signal. For Cu on amorphous carbon, heating to 800 K causes Cu to diffuse into the bulk of the film, based on the strong attenuation ofmore » the Cu signal. Diffusion into the bulk of the amorphous carbon film is confirmed by changes in the shape of the Cu 2 p inelastic tail, and by comparison of attenuation between Cu 2 p and Cu 3 p lines. The magnitude of the photoelectron signal attenuation is compatible with Cu distributed homogeneously throughout the amorphous carbon film, and is not compatible with Cu at or below the C–Si interface under the conditions of our experiments. As a result, desorption is not significant at temperatures up to 800 K.« less
Politi, Yael; Metzler, Rebecca A; Abrecht, Mike; Gilbert, Benjamin; Wilt, Fred H; Sagi, Irit; Addadi, Lia; Weiner, Steve; Gilbert, P U P A; Gilbert, Pupa
2008-11-11
Sea urchin larval spicules transform amorphous calcium carbonate (ACC) into calcite single crystals. The mechanism of transformation is enigmatic: the transforming spicule displays both amorphous and crystalline properties, with no defined crystallization front. Here, we use X-ray photoelectron emission spectromicroscopy with probing size of 40-200 nm. We resolve 3 distinct mineral phases: An initial short-lived, presumably hydrated ACC phase, followed by an intermediate transient form of ACC, and finally the biogenic crystalline calcite phase. The amorphous and crystalline phases are juxtaposed, often appearing in adjacent sites at a scale of tens of nanometers. We propose that the amorphous-crystal transformation propagates in a tortuous path through preexisting 40- to 100-nm amorphous units, via a secondary nucleation mechanism.
NASA Astrophysics Data System (ADS)
Venugopalan, Ramani; Roy, Mainak; Thomas, Susy; Patra, A. K.; Sathiyamoorthy, D.; Tyagi, A. K.
2013-02-01
Carbon-carbon composites may find applications in critical parts of advanced nuclear reactors. A series of carbon-carbon composites were prepared using polyacrylonitrile (PAN) based carbon fibers. The materials were densified by impregnating two-dimensional (2D) preforms with liquid phenol formaldehyde resin at different pressures and for different periods of time and then carbonizing those by slowly heating at 1000 °C. Effects of the processing parameters on the structure of the composites were extensively studied. The study showed conclusively that open porosity decreased with increasing impregnation pressure, whereas impregnation time had lesser effect. Matrix-resin bonding also improved at higher pressure. d002 spacing decreased and ordering along c-axis increased with concomitant increase in sp2-carbon fraction at higher impregnation pressures. The fiber reinforced composites exhibited short range ordering of carbon atoms and satisfied structural conditions (d002 values) of amorphous carbon according to the turbostratic model for non-graphitic carbon materials. The composites had pellet-density of ˜85% of the theoretical value, low thermal expansion and negligible neutron-poisoning. They maintained structural integrity and retained disordered nature even on heat-treatment at ca. 1800 °C.
Thermal decomposition of fullerene nanowhiskers protected by amorphous carbon mask
NASA Astrophysics Data System (ADS)
Guo, Hongxuan; Wang, Chengxiang; Miyazawa, Kun'Ichi; Wang, Hongxin; Masuda, Hideki; Fujita, Daisuke
2016-12-01
Fullerene nanostructures are well known for their unique morphology, physical and mechanical properties. The thermal stability of fullerene nanostructures, such as their sublimation at high temperature is also very important for studying their structures and applications. In this work, We observed fullerene nanowhiskers (FNWs) in situ with scanning helium ion microscopy (HIM) at elevated temperatures. The FNWs exhibited different stabilities with different thermal histories during the observation. The pristine FNWs were decomposed at the temperatures higher than 300 °C in a vacuum environment. Other FNWs were protected from decomposition with an amorphous carbon (aC) film deposited on the surface. Based on high spacial resolution, aC film with periodic structure was deposited by helium ion beam induced deposition (IBID) on the surface of FNWs. Annealed at the high temperature, the fullerene molecules were selectively sublimated from the FNWs. The periodic structure was formed on the surface of FNWs and observed by HIM. Monte Carlo simulation and Raman characterization proved that the morphology of the FNWs was changed by helium IBID at high temperature. This work provides a new method of fabricating artificial structure on the surface of FNWs with periodic aC film as a mask.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gago, R.; Centro de Micro-Analisis de Materiales, Universidad Autonoma de Madrid, Campus de Cantoblanco, 28049 Madrid; Vinnichenko, M.
2005-07-01
The evolution of sp{sup 2} hybrids in amorphous carbon (a-C) films deposited at different substrate temperatures was studied experimentally and theoretically. The bonding structure of a-C films prepared by filtered cathodic vacuum arc was assessed by the combination of visible Raman spectroscopy, x-ray absorption, and spectroscopic ellipsometry, while a-C structures were generated by molecular-dynamics deposition simulations with the Brenner interatomic potential to determine theoretical sp{sup 2} site distributions. The experimental results show a transition from tetrahedral a-C (ta-C) to sp{sup 2}-rich structures at {approx}500 K. The sp{sup 2} hybrids are mainly arranged in chains or pairs whereas graphitic structures aremore » only promoted for sp{sup 2} fractions above 80%. The theoretical analysis confirms the preferred pairing of isolated sp{sup 2} sites in ta-C, the coalescence of sp{sup 2} clusters for medium sp{sup 2} fractions, and the pronounced formation of rings for sp{sup 2} fractions >80%. However, the dominance of sixfold rings is not reproduced theoretically, probably related to the functional form of the interatomic potential used.« less
Nitrogen doping, optical characterization, and electron emission study of diamond
NASA Astrophysics Data System (ADS)
Park, Minseo
Nitrogen-doped chemical vapor deposited (CVD) diamond films were synthesized with N2 (nitrogen) and C3H6N6 (melamine) as doping sources. More effective substitutional nitrogen doping was achieved with C3H6N6 than with N 2. Since a melamine molecule has an existing cyclic C-N bonded ring, it is expected that the incorporation of nitrogen on substitution diamond lattice should be facilitated. The diamond film doped with N2 contained a significant amount of non-diamond carbon phases. The samples were analyzed by scanning electron microscopy, Raman scattering, photoluminescence spectroscopy, and field emission measurements. The sample produced using N 2 exhibited a lower field emission turn-on field than the sample produced using C3H6N6. It is believed that the presence of the graphitic phases (or amorphous sp2 carbon) at the grain boundaries of the diamond and/or the nanocrystallinity (or microcrystallinity) of the diamond play a significant role in lowering the turn-on field of the film produced using N2. The nature of the nitrogen-related 1190 cm-1 Raman peak was investigated. Nitrogen is incorporated predominantly to the crystalline or amorphous sp2 phases when nitrogen is added to the growing diamond. Field emission characteristics from metallic field emitter coated with type Ia and Ib diamond powders were also investigated. No significant difference in electron emission characteristics were found in these samples. Voltage-dependent field emission energy distribution (V-FEED) measurement was performed to analyze the energy distribution of the emitted electrons. It is believed that substitutional nitrogen doping plays only a minor role in changing field emission characteristics in diamond. Discontinuous diamond films were deposited on silicon using a microwave plasma chemical vapor deposition (MPCVD) system. The diamond deposits were sharpened by argon ion beam etching. Raman spectroscopy was carried out to study the structural change of the diamond after ion beam bombardment. Field emission measurements were performed in-situ with an electron beam induced current (EBIC) probe inside the chamber of the scanning electron microscope. It was found that amorphous sp2 carbon is produced as the diamond is sputtered by the Ar ion beam. The field emission turn-on field was also significantly lowered after sharpening, which, it is speculated, is caused by field enhancement due to a change in geometry and/or structural changes (such as amorphization of crystalline diamond into graphitic or amorphous sp2 carbon) by Ar ion irradiation. Secondary electron emission patterning of single crystal diamond surfaces with hydrogen and oxygen plasma treatments was demonstrated. Hydrogen plasma treated regions were much brighter than the oxygen terminated regions. Results of atomic force microscopy confirmed that the observed contrast is not topographical. Several other possible negative electron affinity (or low positive electron affinity) materials such as chemical vapor deposited (CVD) diamond, aluminum nitride and tetrahedrally bonded amorphous carbon [tx a-C 1-x] were also investigated. Faint image contrast (patterning) was also observed from polycrystalline CVD diamond, single crystal aluminum nitride films, and polycrystalline aluminum nitride films; however, no contrast at all was obtained from tetrahedrally bonded amorphous carbon [tx a-C1-x] films.
Pathways for Metastable Carbonate Synthesis
NASA Astrophysics Data System (ADS)
Whittaker, Michael L.
Carbonate minerals are integral to life on earth, as reservoirs for CO 2 in the earth's natural carbon cycle and as the skeletal elements of abundant organisms like corals and plankton. Because of its relevance, availability, and low toxicity, calcium carbonate is also an important model system for phase transformations in aqueous solutions. However, it often does not conform to classical theories of nucleation, prompting a critical reevaluation of both the pathways of carbonate mineralization and the theories that describe them. Most importantly, it has been shown that amorphous calcium carbonate (ACC) is frequently a precursor to crystalline calcium carbonate during precipitation, in both biological and inorganic systems. Amorphous precursors influence phase transformations in several ways, including decoupling densification of ions in solution from their arrangement on a crystalline lattice, altering solution thermodynamics, creating new interfaces, and changing kinetic barriers. To exert control over these processes in vivo, organisms generally confine precipitation reactions to small volumes, often within lipid membrane vesicles. Herein, I describe in vitro model systems designed to elucidate and replicate biological mineralization pathways. Giant unilamellar vesicles are shown to slow the rate of crystallization of ACC by excluding nucleation accelerants, and by preserving the high kinetic barriers to lower energy phases that result. Phosphatidylcholine, one of the most abundant natural lipids, does not interact strongly with ACC, but the interfacial chemistry canbe tuned by changing the lipid charge or reducing steric shielding. Microfluidically produced water-in-oil emulsions were used as liposome analogs to study crystallization kinetics. In ensembles of hundreds of emulsion drops, we show that vaterite forms from ACC via a classical, two-step nucleation process. We also extend the classical theory of nucleation to highly confined aqueous systems, where the formation of a nucleus changes the system composition. In systems chemically similar to ACC, amorphous strontium carbonate (ASC) is also observed in liposomes, but crystallizes rapidly, while amorphous barium carbonate (ABC) is not. We show that ACC can be made with over 50% barium, forming ACBC, but crystallizes at a dramatically faster rate with increasing barium. I demonstrate that this process dramatically departs from the classical description applied to ACC crystallization. It can be explained by the increasing short- and mid-range order in ACBC with increasing barium, which resembles that of crystalline Ca1-xBaxCO3 and selectively lowers the barrier to its formation relative to lower-energy structures. This Ca1-xBaxCO3 phase has been misidentified as calcite in the literature, but we solve the structure, assign the new spacegroup R3m, and call it balcite. Balcite is only thermodynamically stable above 525°C, and is over 30% harder than calcite. In the absence of calcium, I show that ABC is a highly transient precursor to a previously uncharacterized BaCO3·H2 O phase. This phase forms as very thin (10 nm) and extremely anisotropic platelets, which themselves recrystallize rapidly into witherite (BaCO 3). These examples demonstrate the power of amorphous precursors to enable metastable crystalline materials through thermodynamically downhill transformations, and the ability of confined volumes to reduce the rate of these transformations and enable their quantification.
Nuth, Joseph A.; Johnson, Natasha M.; Ferguson, Frank T.; Carayon, Alicia
2018-01-01
We report the ratio of the initial carbon available as CO that forms gas-phase compounds compared to the fraction that deposits as a carbonaceous solid (the gas/solid branching ratio) as a function of time and temperature for iron, magnetite, and amorphous iron silicate smoke catalysts during surface-mediated reactions in an excess of hydrogen and in the presence of N2. This fraction varies from more than 99% for an amorphous iron silicate smoke at 673 K to less than 40% for a magnetite catalyst at 873 K. The CO not converted into solids primarily forms methane, ethane, water, and CO2, as well as a very wide range of organic molecules at very low concentration. Carbon deposits do not form continuous coatings on the catalytic surfaces, but instead form extremely high surface area per unit volume “filamentous” structures. While these structures will likely form more slowly but over much longer times in protostellar nebulae than in our experiments due to the much lower partial pressure of CO, such fluffy coatings on the surfaces of chondrules or calcium aluminum inclusions could promote grain–grain sticking during low-velocity collisions. PMID:29563766
NASA Technical Reports Server (NTRS)
Nuth, Joseph A.; Johnson, Natasha M.; Ferguson, Frank T.; Carayon, Alicia
2016-01-01
We report the ratio of the initial carbon available as CO that forms gas-phase compounds compared to the fraction that deposits as a carbonaceous solid (the gas solid branching ratio) as a function of time and temperature for iron, magnetite, and amorphous iron silicate smoke catalysts during surface-mediated reactions in an excess of hydrogen and in the presence of N2. This fraction varies from more than 99 for an amorphous iron silicate smoke at 673 K to less than 40% for a magnetite catalyst at 873 K. The CO not converted into solids primarily forms methane, ethane, water, and CO2, as well as a very wide range of organic molecules at very low concentration. Carbon deposits do not form continuous coatings on the catalytic surfaces, but instead form extremely high surface area per unit volume filamentous structures. While these structures will likely form more slowly but over much longer times in protostellar nebulae than in our experiments due to the much lower partial pressure of CO, such fluffy coatings on the surfaces of chondrules or calcium aluminum inclusions could promote grain-grain sticking during low-velocity collisions.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Whittaker, Michael L.; Joester, Derk
2017-04-28
Energy-efficient synthesis of materials locked in compositional and structural states far from equilibrium remains a challenging goal, yet biomineralizing organisms routinely assemble such materials with sophisticated designs and advanced functional properties, often using amorphous precursors. However, incorporation of organics limits the useful temperature range of these materials. Herein, the bioinspired synthesis of a highly supersaturated calcite (Ca0.5Ba0.5CO3) called balcite is reported, at mild conditions and using an amorphous calcium–barium carbonate (ACBC) (Ca1- x Ba x CO3·1.2H2O) precursor. Balcite not only contains 50 times more barium than the solubility limit in calcite but also displays the rotational disorder on carbonate sitesmore » that is typical for high-temperature calcite. It is significantly harder (30%) and less stiff than calcite, and retains these properties after heating to elevated temperatures. Analysis of balcite local order suggests that it may require the formation of the ACBC precursor and could therefore be an example of nonclassical nucleation. These findings demonstrate that amorphous precursor pathways are powerfully enabling and provide unprecedented access to materials far from equilibrium, including high-temperature modifications by room-temperature synthesis.« less
Becker, Alexander; Ziegler, Andreas; Epple, Matthias
2005-05-21
The cuticules (shells) of the woodlice Porcellio scaber and Armadillidium vulgare were analysed with respect to their content of inorganic material. It was found that the cuticles consist of crystalline magnesium calcite, amorphous calcium carbonate (ACC), and amorphous calcium phosphate (ACP), besides small amounts of water and an organic matrix. It is concluded that the cuticle, which constitutes a mineralized protective organ, is chemically adapted to the biological requirements by this combination of different materials.
Thin-Film Phase Plates for Transmission Electron Microscopy Fabricated from Metallic Glasses.
Dries, Manuel; Hettler, Simon; Schulze, Tina; Send, Winfried; Müller, Erich; Schneider, Reinhard; Gerthsen, Dagmar; Luo, Yuansu; Samwer, Konrad
2016-10-01
Thin-film phase plates (PPs) have become an interesting tool to enhance the contrast of weak-phase objects in transmission electron microscopy (TEM). The thin film usually consists of amorphous carbon, which suffers from quick degeneration under the intense electron-beam illumination. Recent investigations have focused on the search for alternative materials with an improved material stability. This work presents thin-film PPs fabricated from metallic glass alloys, which are characterized by a high electrical conductivity and an amorphous structure. Thin films of the zirconium-based alloy Zr65.0Al7.5Cu27.5 (ZAC) were fabricated and their phase-shifting properties were evaluated. The ZAC film was investigated by different TEM techniques, which reveal beneficial properties compared with amorphous carbon PPs. Particularly favorable is the small probability for inelastic plasmon scattering, which results from the combined effect of a moderate inelastic mean free path and a reduced film thickness due to a high mean inner potential. Small probability plasmon scattering improves contrast transfer at high spatial frequencies, which makes the ZAC alloy a promising material for PP fabrication.
NASA Astrophysics Data System (ADS)
Sun, Shih-Jye; Hsu, Hua-Shu; Ovchinnikov, Sergei; Chen, Guan-Long
2017-06-01
Based on the experimental finding of the exchange bias in amorphous carbon samples with embedded Co nanoparticles and on the graphited character of the amorphous carbon interface confirmed by molecular dynamics simulations we have proposed the interface of graphited carbon to be antiferromagnetic. A theoretical model, which comprises the Kondo interactions in the interfaces of Co nanoparticles and the induced antiferromagnetic interactions in the graphited carbons, is employed to evaluate the ferromagnetism of the interfaces of Co nanoparticles. We have shown that the ferromagnetism of interfaces of Co nanoparticles will be enhanced by the increase of antiferromagnetic interaction as well as the increase of electron density in the graphited carbons. In particular, we found that the antiferromagnetic interactions in graphited carbons will change the spin-wave excitation in interfaces of Co nanoparticles from the quasiacoustic mode to the quasioptical one.
Politi, Yael; Metzler, Rebecca A.; Abrecht, Mike; Gilbert, Benjamin; Wilt, Fred H.; Sagi, Irit; Addadi, Lia; Weiner, Steve; Gilbert, P. U. P. A.
2008-01-01
Sea urchin larval spicules transform amorphous calcium carbonate (ACC) into calcite single crystals. The mechanism of transformation is enigmatic: the transforming spicule displays both amorphous and crystalline properties, with no defined crystallization front. Here, we use X-ray photoelectron emission spectromicroscopy with probing size of 40–200 nm. We resolve 3 distinct mineral phases: An initial short-lived, presumably hydrated ACC phase, followed by an intermediate transient form of ACC, and finally the biogenic crystalline calcite phase. The amorphous and crystalline phases are juxtaposed, often appearing in adjacent sites at a scale of tens of nanometers. We propose that the amorphous-crystal transformation propagates in a tortuous path through preexisting 40- to 100-nm amorphous units, via a secondary nucleation mechanism. PMID:18987314
NASA Astrophysics Data System (ADS)
Kamaruzaman, Dayana; Ahmad, Nurfadzilah; Annuar, Ishak; Rusop, Mohamad
2013-11-01
Nanostructured iodine-post doped amorphous carbon (a-C:I) thin films were prepared from camphor oil using a thermal chemical vapor deposition (TCVD) technique at different doping temperatures. The structural properties of the films were studied by field-emission scanning electron microscopy (FESEM), energy-dispersive spectroscopy (EDS), Raman, and Fourier transform infrared (FTIR) studies. FESEM and EDS studies showed successful iodine doping. FTIR and Raman studies showed that the a-C:I thin films consisted of a mixture of sp2- and sp3-bonded carbon atoms. The optical and electrical properties of a-C:I thin films were determined by UV-vis-NIR spectroscopy and current-voltage (I-V) measurement respectively. The optical band gap of a-C thin films decreased upon iodine doping. The highest electrical conductivity was found at 400 °C doping. Heterojunctions are confirmed by rectifying the I-V characteristics of an a-C:I/n-Si junction.
Structure of single-wall carbon nanotubes purified and cut using polymer
NASA Astrophysics Data System (ADS)
Zhang, M.; Yudasaka, M.; Koshio, A.; Jabs, C.; Ichihashi, T.; Iijima, S.
2002-01-01
Following on from our previous report that a monochlorobenzene solution of polymethylmethacrylate is useful for purifying and cutting single-wall carbon nanotubes (SWNTs) and thinning SWNT bundles, we show in this report that polymer and residual amorphous carbon can be removed by burning in oxygen gas. The SWNTs thus obtained had many holes (giving them a worm-eaten look) and were thermally unstable. Such severe damage caused by oxidation is unusual for SWNTs; we think that they were chemically damaged during ultrasonication in the monochlorobenzene solution of polymethylmethacrylate.
Mechanochemical synthesis of fluorescent carbon dots from cellulose powders
NASA Astrophysics Data System (ADS)
Chae, Ari; Ram Choi, Bo; Choi, Yujin; Jo, Seongho; Kang, Eun Bi; Lee, Hyukjin; Park, Sung Young; In, Insik
2018-04-01
A novel mechanochemical method was firstly developed to synthesize carbon nanodots (CNDs) or carbon nano-onions (CNOs) through high-pressure homogenization of cellulose powders as naturally abundant resource depending on the treatment times. While CNDs (less than 5 nm in size) showed spherical and amorphous morphology, CNOs (10-50 nm in size) presented polyhedral shape, and onion-like outer lattice structure, graphene-like interlattice spacing of 0.36 nm. CNOs showed blue emissions, moderate dispersibility in aqueous media, and high cell viability, which enables efficient fluorescence imaging of cellular media.
The organic matrix of gallstones
Sutor, D. June; Wooley, Susan E.
1974-01-01
Dissolution of gallstones consisting of cholesterol, calcium carbonate, or calcium phosphate in different solvents left an amorphous organic gel-like substance (the matrix). Matrix from cholesterol stones could be colourless but was usually orange, yellow, or brown while that from calcium carbonate and calcium phosphate stones was almost invariably coloured black or dark brown. These pigments were also shown to be organic and amorphous. The amount of matrix present and its structure varied with the texture of the crystalline material. Irrespective of their composition, laminated pieces of material yielded compact laminated matrix of the same shape as the original piece and areas of loose crystalline material gave small pieces of non-cohesive matrix. Only large cholesterol crystals which usually radiate from the stone nucleus had no associated matrix. ImagesFig 1Fig 2Fig 3Fig 4Fig 5 PMID:4854981
2016-01-01
The origin of the diffuse interstellar bands (DIBs), one of the longest-standing mysteries of the interstellar medium (ISM), is explored within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS). The likely nature of the DIB carriers and their evolution is here explored within the framework of the structures and sub-structures inherent to doped hydrogenated amorphous carbon grains in the ISM. Based on the natural aromatic-rich moieties (asphaltenes) recovered from coal and oil, the likely structure of their interstellar analogues is investigated within the context of the diffuse band problem. It is here proposed that the top-down evolution of interstellar carbonaceous grains, and, in particular, a-C(:H) nanoparticles, is at the heart of the formation and evolution of the DIB carriers and their associations with small molecules and radicals, such as C2, C3, CH and CN. It is most probable that the DIBs are carried by dehydrogenated, ionized, hetero-cyclic, olefinic and aromatic-rich moieties that form an integral part of the contiguous structure of hetero-atom-doped hydrogenated amorphous carbon nanoparticles and their daughter fragmentation products. Within this framework, it is proposed that polyene structures in all their variants could be viable DIB carrier candidates. PMID:28083089
NASA Astrophysics Data System (ADS)
Jones, A. P.
2016-12-01
The origin of the diffuse interstellar bands (DIBs), one of the longest-standing mysteries of the interstellar medium (ISM), is explored within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS). The likely nature of the DIB carriers and their evolution is here explored within the framework of the structures and sub-structures inherent to doped hydrogenated amorphous carbon grains in the ISM. Based on the natural aromatic-rich moieties (asphaltenes) recovered from coal and oil, the likely structure of their interstellar analogues is investigated within the context of the diffuse band problem. It is here proposed that the top-down evolution of interstellar carbonaceous grains, and, in particular, a-C(:H) nanoparticles, is at the heart of the formation and evolution of the DIB carriers and their associations with small molecules and radicals, such as C2, C3, CH and CN. It is most probable that the DIBs are carried by dehydrogenated, ionized, hetero-cyclic, olefinic and aromatic-rich moieties that form an integral part of the contiguous structure of hetero-atom-doped hydrogenated amorphous carbon nanoparticles and their daughter fragmentation products. Within this framework, it is proposed that polyene structures in all their variants could be viable DIB carrier candidates.
Structures and properties of fluorinated amorphous carbon films
NASA Astrophysics Data System (ADS)
Huang, K. P.; Lin, P.; Shih, H. C.
2004-07-01
Fluorinated amorphous carbon (a-C:F) films were deposited by radio frequency bias assisted microwave plasma electron cyclotron resonance chemical vapor deposition with tetrafluoromethane (CF4) and acetylene (C2H2) as precursors. The deposition process was performed at two flow ratios R=0.90 and R=0.97, where R=CF4/(CF4+C2H2). The samples were annealed at 300 °C for 30 min. in a N2 atmosphere. Both Fourier transform infrared and electron spectroscopy for chemical analyzer were used to characterize the a-C:F film chemical bond and fluorine concentration, respectively. A high resolution electron energy loss spectrometer was applied to detect the electronic structure. The higher CF4 flow ratio (R=0.97) produced more sp3 linear structure, and it made the a-C:F film smoother and softer. A lifetime of around 0.34 μs and an energy gap of ˜2.75 eV were observed in both the as-deposited and after annealing conditions. The short carriers lifetime in the a-C:F film made the photoluminescence peak blueshift. The annealing changed both the structure and composition of the a-C:F film. The type of fluorocarbon bond and electronic structure characterized the mechanical and physical properties of a-C:F film.
NASA Astrophysics Data System (ADS)
Kim, Min-Uk; Kim, Do-Hyang; Han, Seung-hee; Fleury, Eric; Seok, Hyun-Kwang; Cha, Pil-Ryung; Kim, Yu-Chan
2011-04-01
Ni-based amorphous alloys with surface modification by carbon ion implantation are proposed as an alternative bipolar plate material for polymer electrolyte membrane fuel cells (PEMFCs). Both Ni60Nb20Ti10Zr10 alloys with and without carbon ion implantation have corrosion resistance as good as graphite as well as much lower contact resistance than 316L stainless steel in the PEMFC environment. The formation of conductive surface carbide due to carbon ion implantation results in a decrease in the contact resistance to a level comparable to that of graphite. This combination of excellent properties indicates that carbon ion implanted Ni-based amorphous alloys can be potential candidate materials for bipolar plates in PEMFCs.
Composition, structure and chemistry of interstellar dust
NASA Technical Reports Server (NTRS)
Tielens, Alexander G. G. M.; Allamandola, Louis J.
1986-01-01
The observational constraints on the composition of the interstellar dust are analyzed. The dust in the diffuse interstellar medium consists of a mixture of stardust (amorphous silicates, amorphous carbon, polycyclic aromatic hydrocarbons, and graphite) and interstellar medium dust (organic refractory material). Stardust seems to dominate in the local diffuse interstellar medium. Inside molecular clouds, however, icy grain mantles are also important. The structural differences between crystalline and amorphous materials, which lead to differences in the optical properties, are discussed. The astrophysical consequences are briefly examined. The physical principles of grain surface chemistry are discussed and applied to the formation of molecular hydrogen and icy grain mantles inside dense molecular clouds. Transformation of these icy grain mantles into the organic refractory dust component observed in the diffuse interstellar medium requires ultraviolet sources inside molecular clouds as well as radical diffusion promoted by transient heating of the mantle. The latter process also returns a considerable fraction of the molecules in the grain mantle to the gas phase.
Tali, S A Safiabadi; Soleimani-Amiri, S; Sanaee, Z; Mohajerzadeh, S
2017-02-10
We report successful deposition of nitrogen-doped amorphous carbon films to realize high-power core-shell supercapacitor electrodes. A catalyst-free method is proposed to deposit large-area stable, highly conformal and highly conductive nitrogen-doped amorphous carbon (a-C:N) films by means of a direct-current plasma enhanced chemical vapor deposition technique (DC-PECVD). This approach exploits C 2 H 2 and N 2 gases as the sources of carbon and nitrogen constituents and can be applied to various micro and nanostructures. Although as-deposited a-C:N films have a porous surface, their porosity can be significantly improved through a modification process consisting of Ni-assisted annealing and etching steps. The electrochemical analyses demonstrated the superior performance of the modified a-C:N as a supercapacitor active material, where specific capacitance densities as high as 42 F/g and 8.5 mF/cm 2 (45 F/cm 3 ) on silicon microrod arrays were achieved. Furthermore, this supercapacitor electrode showed less than 6% degradation of capacitance over 5000 cycles of a galvanostatic charge-discharge test. It also exhibited a relatively high energy density of 2.3 × 10 3 Wh/m 3 (8.3 × 10 6 J/m 3 ) and ultra-high power density of 2.6 × 10 8 W/m 3 which is among the highest reported values.
NASA Astrophysics Data System (ADS)
Popescu, C.; Dorcioman, G.; Bita, B.; Besleaga, C.; Zgura, I.; Himcinschi, C.; Popescu, A. C.
2016-12-01
Thin films of carbon were synthesized by ns pulsed laser deposition in vacuum on silicon substrates, starting from graphite targets. Further on, the films were irradiated with a picosecond laser source emitting in visible at 532 nm. After tuning of laser parameters, we obtained a film surface covered by laser induced periodical surface structures (LIPSS). They were investigated by optical, scanning electron and atomic force microscopy. It was observed that changing the irradiation angle influences the LIPSS covered area. At high magnification it was revealed that the LIPSS pattern was quite complex, being composed of other small LIPSS islands, interconnected by bridges of nanoparticles. Raman spectra for the non-irradiated carbon films were typical for a-C type of diamond-like carbon, while the LIPSS spectra were characteristic to nano-graphite. The pristine carbon film was hydrophilic, while the LIPSS covered film surface was hydrophobic.
Gong, Feilong; Lu, Shuang; Peng, Lifang; Zhou, Jing; Kong, Jinming; Jia, Dianzeng; Li, Feng
2017-11-23
Porous Mn₂O₃ microspheres have been synthesized and in-situ coated with amorphous carbon to form hierarchical C@Mn₂O₃ microspheres by first producing MnCO₃ microspheres in solvothermal reactions, and then annealing at 500 °C. The self-assembly growth of MnCO₃ microspheres can generate hollow structures inside each of the particles, which can act as micro-reservoirs to store biomass-glycerol for generating amorphous carbon onto the surfaces of Mn₂O₃ nanorods consisting of microspheres. The C@Mn₂O₃ microspheres, prepared at 500 °C, exhibit highly enhanced pseudocapacitive performances when compared to the particles after annealed at 400 °C and 600 °C. Specifically, the C@Mn₂O₃ microspheres prepared at 500 °C show high specific capacitances of 383.87 F g -1 at current density of 0.5 A g -1 , and excellent cycling stability of 90.47% of its initial value after cycling for 5000 times. The asymmetric supercapacitors assembled with C@Mn₂O₃ microspheres after annealed at 500 °C and activated carbon (AC) show an energy density of up to 77.8 Wh kg -1 at power density of 500.00 W kg -1 , and a maximum power density of 20.14 kW kg -1 at energy density of 46.8 Wh kg -1 . We can attribute the enhanced electrochemical performances of the materials to their three-dimensional (3D) hierarchical structure in-situ coated with carbon.
NASA Astrophysics Data System (ADS)
Ramkumar, B.; Yuvaraj, S.; Surendran, S.; Pandi, K.; Ramasamy, Hari Vignesh; Lee, Y. S.; Kalai Selvan, R.
2018-01-01
For the fabrication of aqueous Li-ion hybrid supercapacitor, carbon coated LiCo1/3Ni1/3Mn1/3O2 (or LiCo1/3Ni1/3Mn1/3O2@C composite) is synthesized by polymeric precursor method with subsequent thermal decomposition procedures for carbon coating. Graphene like porous carbon is obtained by chemical activation from the biomass of Agave Americana. The XRD analysis reveals that LiCo1/3Ni1/3Mn1/3O2 is having a hexagonal layered structure and activated carbon exists in both amorphous and graphitic nature. The TEM image infers that LiCo1/3Ni1/3Mn1/3O2 particles having the non-uniform shape with sub-micron size and the LiCo1/3Ni1/3Mn1/3O2 particles are embedded into amorphous carbon cloud in the composite. The activated carbon shows the specific surface area of 1219 m2 g-1. Finally, the fabricated aqueous LiCo1/3Ni1/3Mn1/3O2@C‖AC hybrid supercapacitor delivers the specific capacitance of 56 F g-1 with good capacity retention even after 5000 cycles.
Rajbhandari, Rinita; Shrestha, Lok Kumar; Pradhananga, Raja Ram
2012-09-01
Activated carbons were prepared from Lapsi (Choerospondias axillaris) seed stone by zinc chloride (ZnCl2) activation at three different Lapsi seed powder (LSP):ZnCl2 ratios: 1:0.5 (AC-0.5), 1:1 (AC-1), and 1:2 (AC-2). The properties of these activated carbons (ACs), including effective surface areas, pore volumes, and pore size distributions were characterized from N2 adsorption-desorption isotherms. The ACs obtained were essentially nanoporous (including both micro- and mesoporous) with effective surface area ranging from 1167 to 1328 m2/g. Fourier-transform infrared (FTIR) spectroscopy showed the presence of functional groups on the surface of ACs. Scanning electron microscopy (SEM) images showed a high pore development in the ACs. X-ray diffraction (XRD) patterns showed that, in addition to the amorphous structure, ACs contains crystalline ZnO formed during the carbonization. Presence of amorphous carbon is further confirmed by Raman scattering, where we observed only D and G bands. Iron impregnated nanoporous AC has been found to be very effective for arsenic removal from ground water; amount of arsenic is decreased from ca. 200 ppb to 10 ppb. These experimental results indicate the potential use of Lapsi seed as a precursor material for the preparation of high surface area nanoporous activated carbons.
Carbon stardust: From soot to diamonds
NASA Technical Reports Server (NTRS)
Tielens, Alexander G. G. M.
1990-01-01
The formation of carbon dust in the outflow from stars and the subsequent evolution of this so called stardust in the interstellar medium is reviewed. The chemical and physical processes that play a role in carbon stardust formation are very similar to those occurring in sooting flames. Based upon extensive laboratory studies of the latter, the structure and physical and chemical properties of carbon soot are reviewed and possible chemical pathways towards carbon stardust are discussed. Grain-grain collisions behind strong interstellar shocks provide the high pressures required to transform graphite and amorphous carbon grains into diamond. This process is examined and the properties of shock-synthesized diamonds are reviewed. Finally, the interrelationship between carbon stardust and carbonaceous meteorites is briefly discussed.
Shieh, Sean R.; Jarrige, Ignace; Wu, Min; Hiraoka, Nozomu; Tse, John S.; Mi, Zhongying; Kaci, Linada; Jiang, Jian-Zhong; Cai, Yong Q.
2013-01-01
Knowledge of the high-pressure behavior of carbon dioxide (CO2), an important planetary material found in Venus, Earth, and Mars, is vital to the study of the evolution and dynamics of the planetary interiors as well as to the fundamental understanding of the C–O bonding and interaction between the molecules. Recent studies have revealed a number of crystalline polymorphs (CO2-I to -VII) and an amorphous phase under high pressure–temperature conditions. Nevertheless, the reported phase stability field and transition pressures at room temperature are poorly defined, especially for the amorphous phase. Here we shed light on the successive pressure-induced local structural changes and the molecular-to-nonmolecular transition of CO2 at room temperature by performing an in situ study of the local electronic structure using X-ray Raman scattering, aided by first-principle exciton calculations. We show that the transition from CO2-I to CO2-III was initiated at around 7.4 GPa, and completed at about 17 GPa. The present study also shows that at ∼37 GPa, molecular CO2 starts to polymerize to an extended structure with fourfold coordinated carbon and minor CO3 and CO-like species. The observed pressure is more than 10 GPa below previously reported. The disappearance of the minority species at 63(±3) GPa suggests that a previously unknown phase transition within the nonmolecular phase of CO2 has occurred. PMID:24167283
NASA Astrophysics Data System (ADS)
Utama, P. S.; Saputra, E.; Khairat
2018-04-01
Palm Oil Mill Fly Ash (POMFA) the solid waste of palm oil industry was used as a raw material for synthetic amorphous silica and carbon zeolite composite synthesis in order to minimize the wastes of palm oil industry. The alkaline extraction combine with the sol-gel precipitation and mechanical fragmentation was applied to produce synthetic amorphous silica. The byproduct, extracted POMFA was rich in carbon and silica content in a significant amount. The microwave heated hydrothermal process used to synthesize carbon zeolite composite from the byproduct. The obtained silica had chemical composition, specific surface area and the micrograph similar to commercial precipitated silica for rubber filler. The microwave heated hydrothermal process has a great potential for synthesizing carbon zeolite composite. The process only needs one-step and shorter time compare to conventional hydrothermal process.
Lithographically defined porous Ni-carbon nanocomposite supercapacitors.
Xiao, Xiaoyin; Beechem, Thomas; Wheeler, David R; Burckel, D Bruce; Polsky, Ronen
2014-03-07
Ni was deposited onto lithographically-defined conductive three dimensional carbon networks to form asymmetric pseudo-capacitive electrodes. A real capacity of above 500 mF cm(-2), or specific capacitance of ∼2100 F g(-1) near the theoretical value, has been achieved. After a rapid thermal annealing process, amorphous carbon was partially converted into multilayer graphene depending on the annealing temperature and time duration. These annealed Ni-graphene composite structures exhibit enhanced charge transport kinetics relative to un-annealed Ni-carbon scaffolds indicated by a reduction in peak separation from 0.84 V to 0.29 V at a scan rate of 1000 mV s(-1).
Zhang, Zailei; Zhang, Meiju; Wang, Yanhong; Tan, Qiangqiang; Lv, Xiao; Zhong, Ziyi; Li, Hong; Su, Fabing
2013-06-21
We report the preparation and characterization of amorphous silicon-carbon (Si-C) nanospheres as anode materials in Li-ion batteries. These nanospheres were synthesized by a chemical vapor deposition at 900 °C using methyltrichlorosilane (CH3SiCl3) as both the Si and C precursor, which is a cheap byproduct in the organosilane industry. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, nitrogen adsorption, thermal gravimetric analysis, Raman spectroscopy, and X-ray photoelectron spectroscopy. It was found that the synthesized Si-C nanospheres composed of amorphous C (about 60 wt%) and Si (about 40 wt%) had a diameter of 400-600 nm and a surface area of 43.8 m(2) g(-1). Their charge capacities were 483.6, 331.7, 298.6, 180.6, and 344.2 mA h g(-1) at 50, 200, 500, 1000, and 50 mA g(-1) after 50 cycles, higher than that of the commercial graphite anode. The Si-C amorphous structure could absorb a large volume change of Si during Li insertion and extraction reactions and hinder the cracking or crumbling of the electrode, thus resulting in the improved reversible capacity and cycling stability. The work opens a new way to fabricate low cost Si-C anode materials for Li-ion batteries.
The role of amorphous precursors in the crystallization of La and Nd carbonates
NASA Astrophysics Data System (ADS)
Vallina, Beatriz; Rodriguez-Blanco, Juan Diego; Brown, Andrew P.; Blanco, Jesus A.; Benning, Liane G.
2015-07-01
Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have characterized these precursors and the crystallization pathways and products with solid-state, spectroscopic and microscopic techniques to explain the differences in crystallization mechanisms between the La and Nd systems. ALC and ANC consist of highly hydrated, 10-20 nm spherical nanoparticles with a general formula of REE2(CO3)3.5H2O (REE = La, Nd). The stabilities differ by ~2 orders of magnitude, with ANC being far more stable than ALC. This difference is due to the Nd3+ ion having a far higher hydration energy compared to the La3+ ion. This, together with temperature and reaction times, leads to clear differences not only in the kinetics and mechanisms of crystallization of the amorphous precursor La- and Nd-carbonate phases but also in the resulting crystallite sizes and morphologies of the end products. All crystalline La and Nd carbonates developed spherulitic morphologies when crystallization occurred from hydrous phases in solution at temperatures above 60 °C (La system) and 95 °C (Nd system). We suggest that spherulitic growth occurs due to a rapid breakdown of the amorphous precursors and a concurrent rapid increase in supersaturation levels in the aqueous solution. The kinetic data show that the crystallization pathway for both La and Nd carbonate systems is dependent on the reaction temperature and the ionic potential of the REE3+ ion.Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have characterized these precursors and the crystallization pathways and products with solid-state, spectroscopic and microscopic techniques to explain the differences in crystallization mechanisms between the La and Nd systems. ALC and ANC consist of highly hydrated, 10-20 nm spherical nanoparticles with a general formula of REE2(CO3)3.5H2O (REE = La, Nd). The stabilities differ by ~2 orders of magnitude, with ANC being far more stable than ALC. This difference is due to the Nd3+ ion having a far higher hydration energy compared to the La3+ ion. This, together with temperature and reaction times, leads to clear differences not only in the kinetics and mechanisms of crystallization of the amorphous precursor La- and Nd-carbonate phases but also in the resulting crystallite sizes and morphologies of the end products. All crystalline La and Nd carbonates developed spherulitic morphologies when crystallization occurred from hydrous phases in solution at temperatures above 60 °C (La system) and 95 °C (Nd system). We suggest that spherulitic growth occurs due to a rapid breakdown of the amorphous precursors and a concurrent rapid increase in supersaturation levels in the aqueous solution. The kinetic data show that the crystallization pathway for both La and Nd carbonate systems is dependent on the reaction temperature and the ionic potential of the REE3+ ion. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01497b
Models for Amorphous Calcium Carbonate
NASA Astrophysics Data System (ADS)
Sinha, Sourabh
Many species e.g. sea urchin form amorphous calcium carbonate (ACC) precursor phases that subsequently transform into crystalline CaCO3. It is certainly possible that the biogenic ACC might have more than 10 wt% Mg and ˜3 wt% of water. The structure of ACC and the mechanisms by which it transforms to crystalline phase are still poorly understood. In this dissertation our goal is to determine an atomic structure model that is consistent with diffraction and IR measurements of ACC. For this purpose a calcite supercell with 24 formula units, containing 120 atoms, was constructed. Various configurations with substitution of Ca by 6 Mg ions (6 wt.%) and insertion of 3-5 H 2O molecules (2.25-3.75 wt.%) in the interstitial positions of the supercell, were relaxed using a robust density function code VASP. The most noticeable effects were the tilts of CO3 groups and the distortion of Ca sub-lattice, especially in the hydrated case. The distributions of Ca-Ca nearest neighbor distance and CO3 tilts were extracted from various configurations. The same methods were also applied to aragonite. Sampling from the calculated distortion distributions, we built models for amorphous calcite/aragonite of size ˜ 1700 nm3 based on a multi-scale modeling scheme. We used these models to generate diffraction patterns and profiles with our diffraction code. We found that the induced distortions were not enough to generate a diffraction profile typical of an amorphous material. We then studied the diffraction profiles from several nano-crystallites as recent studies suggest that ACC might be a random array of nano-cryatallites. It was found that the generated diffraction profile from a nano-crystallite of size ˜ 2 nm3 is similar to that from the ACC.
Asphaltenes as new objects for nanoelectronics
NASA Astrophysics Data System (ADS)
Dolomatov, M. Yu; Petrov, A. M.; Bakhtizin, R. Z.; Dolomatova, M. M.; Khairudinov, I. R.; Shutkova, S. A.; Kovaleva, E. A.; Paymurzina, N. Kh
2017-05-01
Abstract. Modern carbon nanomaterials (carbon nanotubes, graphenes, fullerenes, polycyclic molecules) are products of rather complicated technologies. Therefore development of new not expensive materials on the basis of natural substances, in particular high-molecular compounds of oil - asphaltenes, is actual for nanoelectronics. Asphaltenes are complex materials that are found in crude oil, bitumen and high-boiling hydrocarbons distillates. Usually asphaltenes are composed mainly of polyaromatic carbon with a small amount of vanadium and nickel, which are in porphyrin structures. Molecules of asphaltenes may contain 5-10-member benzene and naphthenic rings in their structure and also have paramagnetic centers. A variety of techniques: electronic phenomenological spectroscopy (EPS), atomic force microscopy (AFM) and quantum chemistry calculations were used to define the structure of oil asphaltenes. It was supposed that asphaltene fraction is a strong donor (ionization potential 4.10-6.70 eV) and an acceptor (electron affinity 1.80-2.50 eV). The structures of asphaltenes fragments were calculated by RHF-6-31G** methods. AFM images of asphaltenes obtained from crude oil showed the presence of structure fragments ranged from 3 to 10 nm, disposed to strong intermolecular interactions. We used doped compounds for formation of wide band gap amorphous semiconductors from a concentrates of asphaltens. Changes of conductivity in dispersed petroleum systems (DPS) were studied during a pyrolysis at 500 K. The numerous experiments defined of conductivity testify about phase transitions dielectric - semiconductor in DPS for range of 360 - 400 K. The main conclusion is paramagnetic phase of asphaltenes is organic amorphous wide band gap semiconductor. Besides this substance can be consider as an organic spin glasses.
Constraints on Biogenic Emplacement of Crystalline Calcium Carbonate and Dolomite
NASA Astrophysics Data System (ADS)
Colas, B.; Clark, S. M.; Jacob, D. E.
2015-12-01
Amorphous calcium carbonate (ACC) is a biogenic precursor of calcium carbonates forming shells and skeletons of marine organisms, which are key components of the whole marine environment. Understanding carbonate formation is an essential prerequisite to quantify the effect climate change and pollution have on marine population. Water is a critical component of the structure of ACC and the key component controlling the stability of the amorphous state. Addition of small amounts of magnesium (1-5% of the calcium content) is known to promote the stability of ACC presumably through stabilization of the hydrogen bonding network. Understanding the hydrogen bonding network in ACC is fundamental to understand the stability of ACC. Our approach is to use Monte-Carlo simulations constrained by X-ray and neutron scattering data to determine hydrogen bonding networks in ACC as a function of magnesium doping. We have already successfully developed a synthesis protocol to make ACC, and have collected X-ray data, which is suitable for determining Ca, Mg and O correlations, and have collected neutron data, which gives information on the hydrogen/deuterium (as the interaction of X-rays with hydrogen is too low for us to be able to constrain hydrogen atom positions with only X-rays). The X-ray and neutron data are used to constrain reverse Monte-Carlo modelling of the ACC structure using the Empirical Potential Structure Refinement program, in order to yield a complete structural model for ACC including water molecule positions. We will present details of our sample synthesis and characterization methods, X-ray and neutron scattering data, and reverse Monte-Carlo simulations results, together with a discussion of the role of hydrogen bonding in ACC stability.
NASA Astrophysics Data System (ADS)
Moraes, Kevin V.
Allylhydridopolycarbosilane is a precursor of growing importance in the fabrication of silicon carbide ceramics. However, prior to this study few details were available about the processing-structure-property relationships for this material. In Part 1 of this study the processes of densification and microstructural transformation of the partially pyrolysed amorphous AHPCS-SiC was investigated in the temperature region of 800°C to 1600°C. In Part 2 of this study, mechanical properties, specifically fracture toughness (K1c) and Vickers hardness, were measured on bulk specimens in the temperature range of 1000°C to 1600°C. A combination of X-Ray diffraction (XRD), Transmission Electron Microscopy (TEM), 29Si Nuclear Magnetic Resonance (NMR) and micro Raman spectroscopy, along with simultaneous Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA) were used to follow the structural transformation of the partially pyrolysed AHPCS-SiC on several length scales between the temperature of 800 to 1600°C. It was determined that the rate of densification of amorphous AHPCS-SiC, partially pyrolysed to 600°C, depends on the surface to volume ratio. Calculations were preformed that suggested that nucleation of the SiC crystals should occur preferentially on the surface of the powder particles rather than in the bulk. However, TEM on samples heat-treated to 1600°C did not show a preponderance of crystals on the surface of the particles compared to their bulk. Crystallization of beta-SiC occurs at ca. 1250°C, as determined by DSC and supported by NMR and electron diffraction. The average size of the beta-SiC crystallites, as determined by XRD, was ca. 5 nm at 1600°C. Prior to the crystallization of beta-SiC, Raman spectroscopy indicates the presence of carbon clusters in the otherwise amorphous matrix. These carbon clusters have predominantly sp3 bonding at 1100°C that gradually converts to predominantly sp 2 bonded carbon at higher temperatures, with average basal plane sizes of 20--25 A between 1100 in addition to 1600°C. The amorphous structure formed at temperatures below the crystallization temperature is unstable. It is seen from DSC that amorphous AHPCS-SiC undergoes two distinct exothermic events: a broad, irreversible, exotherm that corresponds to structural relaxation and chemical condensation and a second, much sharper, exotherm that corresponds to crystallization. Fracture toughness values measured on cold-pressed and infiltrated AHPCS-SiC samples were in the range of 1.4 to 1.67 MPam1/2. It appears that toughness increases with increasing heat treatment temperature. The Vickers hardness at 10 N was ca. 8.7 to 12.6 MPa. The Vickers hardness does not appear to vary significantly with the heat-treatment temperature.
Latifi, Seyed Mohsen; Fathi, Mohammadhossein; Sharifnabi, Ali; Varshosaz, Jaleh
2017-06-01
Design and synthesis of materials with better properties and performance are essential requirements in the field of biomaterials science that would directly improve patient quality of life. For this purpose, in situ silica-coated silicate and carbonate co-doped hydroxyapatite (Sc/S.C.HA) nanopowder was synthesized via the sol-gel method. Characterisation of the prepared nanopowder was carried out by XRD, FTIR, TEM, SEM, EDX, ICP, zeta potential, acid dissolution test, and cell culture test. The substitution of the silicate and carbonate ions into hydroxyapatite structure was confirmed by FTIR analysis. XRD analysis showed that silica is an amorphous phase, which played a role in covering the surface of the S.C.HA nanoparticles as confirmed by acid dissolution test. Low thickness and low integrity of the amorphous silica surface layer facilitated ions release from S.C.HA nanoparticles into physiological saline solution. Zeta potential of the prepared nanopowder suspended in physiological saline solution was -27.3±0.2mV at pH7.4. This negatively charged surface, due to the presence of amorphous silica layer upon the S.C.HA nanoparticles, not only had an accelerating effect on in vitro biomineralization of apatite, but also had a positive effect on cell attachment. Copyright © 2017 Elsevier B.V. All rights reserved.
Synthesis of carbon nanofibres from waste chicken fat for field electron emission applications
DOE Office of Scientific and Technical Information (OSTI.GOV)
Suriani, A.B., E-mail: absuriani@yahoo.com; Department of Physics, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, Tanjung Malim, Perak 35900; Dalila, A.R.
Highlights: • Waste chicken fat is used as a starting material to produce CNFs via TCVD method. • High heating rate applied resulted in aggregation of catalyst particles. • Aggregated catalyst produced sea urchin-like CNFs with amorphous nature. • The as-grown CNFs presented a potential for field electron emission applications. - Abstract: Carbon nanofibres (CNFs) with sea urchin-like morphology were synthesised from waste chicken fat precursor via catalytic thermal chemical vapour deposition method at 750 °C. The CNFs showed amorphous structures under high-resolution transmission electron microscopy, micro-Raman spectroscopy and X-ray diffraction examination. X-ray photoelectron spectroscopy analysis confirmed that the coremore » of the sea urchin-like CNFs was composed of Fe{sub 3}C formed within the first 20 min of synthesis time. The growth of amorphous CNFs from agglomerated Fe{sub 3}C particles was favourable due to the high heating rate applied during the synthesis. Field electron emission examination of the CNFs indicated turn-on and threshold field values of 5.4 and 6.6 V μm{sup −1} at current density of 1 and 10 μA cm{sup −2}, respectively. This study demonstrates that waste chicken fat, a low-cost and readily available resource, can be used as an inexpensive carbon source for the production of CNFs with a potential application in field electron emitters.« less
Tachikawa, Hiroto; Shimizu, Akira
2005-07-14
Diffusion processes of the Li+ ion on a model surface of amorphous carbon (Li+C96H24 system) have been investigated by means of the direct molecular orbital (MO) dynamics method at the semiempirical AM1 level. The total energy and energy gradient on the full-dimensional AM1 potential energy surface were calculated at each time step in the dynamics calculation. The optimized structure, where Li+ is located in the center of the cluster, was used as the initial structure at time zero. The dynamics calculation was carried out in the temperature range 100-1000 K. The calculations showed that the Li+ ion vibrates around the equilibrium point below 200 K, while the Li+ ion moves on the surface above 250 K. At intermediate temperatures (300 K < T < 400 K), the ion moves on the surface and falls in the edge regions of the cluster. At higher temperatures (600 K < T), the Li+ ion transfers freely on the surface and edge regions. The diffusion pathway of the Li+ ion was discussed on the basis of theoretical results.
Biomineral nanoparticles are space-filling
NASA Astrophysics Data System (ADS)
Yang, Li; Killian, Christopher E.; Kunz, Martin; Tamura, Nobumichi; Gilbert, P. U. P. A.
2011-02-01
Sea urchin biominerals have been shown to form from aggregating nanoparticles of amorphous calcium carbonate (ACC), which then crystallize into macroscopic single crystals of calcite. Here we measure the surface areas of these biominerals and find them to be comparable to those of space-filling macroscopic geologic calcite crystals. These biominerals differ from synthetic mesocrystals, which are invariably porous. We propose that space-filling ACC is the structural precursor for echinoderm biominerals.Sea urchin biominerals have been shown to form from aggregating nanoparticles of amorphous calcium carbonate (ACC), which then crystallize into macroscopic single crystals of calcite. Here we measure the surface areas of these biominerals and find them to be comparable to those of space-filling macroscopic geologic calcite crystals. These biominerals differ from synthetic mesocrystals, which are invariably porous. We propose that space-filling ACC is the structural precursor for echinoderm biominerals. This article was submitted as part of a Themed Issue on Crystallization and Formation Mechanisms of Nanostructures. Other papers on this topic can be found in issue 11 of vol. 2 (2010). This issue can be found from the Nanoscale homepage [http://www.rsc.org/nanoscale
Re-crystallization of ITO films after carbon irradiation
NASA Astrophysics Data System (ADS)
Usman, Muhammad; Khan, Shahid; Khan, Majid; Abbas, Turab Ali
2017-01-01
2.0 MeV carbon ion irradiation effects on Indium Tin Oxide (ITO) thin films on glass substrate are investigated. The films are irradiated with carbon ions in the fluence range of 1 × 1013 to 1 × 1015 ions/cm2. The irradiation induced effects in ITO are compared before and after ion bombardment by systematic study of structural, optical and electrical properties of the films. The XRD results show polycrystalline nature of un-irradiated ITO films which turns to amorphous state after 1 × 1013 ions/cm2 fluence of carbon ions. Further increase in ion fluence to 1 × 1014 ions/cm2 re-crystallizes the structure and retains for even higher fluences. A gradual decrease in the electrical conductivity and transmittance of irradiated samples is observed with increasing ion fluence. The band gap of the films is observed to be decreased after carbon irradiation.
NASA Astrophysics Data System (ADS)
Qian, Min; Niu, Yue Ping; Gong, Shang Qing
2018-01-01
Pulsed Nd:YAG (532 nm) and Excimer (248 nm) lasers were employed to produce freestanding, two-dimensional (2D), carbon nanosheets (CNSs) from naphthalene, through laser-induced exfoliation. The polymer-to-carbon transition was investigated in terms of laser wavelengths, fluences, as well as target preparations. Continuous and porous CNSs of several nanometers in thickness and micrometers in size were obtained from 532 and 248 nm pulsed laser exfoliation of spin-coated naphthalene films, respectively. The porous morphology is ascribed to the photon-induced dissociation of chemical bonds dominated in 248 nm laser interaction with ablated naphthalene. With the increase of laser fluences from 1 to 5 J cm-2, amorphous carbon and ultrathin CNS structures were obtained in sequence. This work revealed a general mechanism of producing 2D structured carbon materials from pulsed laser exfoliation.
He, Y.; Zhuang, Q.; Harden, Jennifer W.; McGuire, A. David; Fan, Z.; Liu, Y.; Wickland, Kimberly P.
2014-01-01
The large amount of soil carbon in boreal forest ecosystems has the potential to influence the climate system if released in large quantities in response to warming. Thus, there is a need to better understand and represent the environmental sensitivity of soil carbon decomposition. Most soil carbon decomposition models rely on empirical relationships omitting key biogeochemical mechanisms and their response to climate change is highly uncertain. In this study, we developed a multi-layer microbial explicit soil decomposition model framework for boreal forest ecosystems. A thorough sensitivity analysis was conducted to identify dominating biogeochemical processes and to highlight structural limitations. Our results indicate that substrate availability (limited by soil water diffusion and substrate quality) is likely to be a major constraint on soil decomposition in the fibrous horizon (40–60% of soil organic carbon (SOC) pool size variation), while energy limited microbial activity in the amorphous horizon exerts a predominant control on soil decomposition (>70% of SOC pool size variation). Elevated temperature alleviated the energy constraint of microbial activity most notably in amorphous soils, whereas moisture only exhibited a marginal effect on dissolved substrate supply and microbial activity. Our study highlights the different decomposition properties and underlying mechanisms of soil dynamics between fibrous and amorphous soil horizons. Soil decomposition models should consider explicitly representing different boreal soil horizons and soil–microbial interactions to better characterize biogeochemical processes in boreal forest ecosystems. A more comprehensive representation of critical biogeochemical mechanisms of soil moisture effects may be required to improve the performance of the soil model we analyzed in this study.
Confocal Raman Microscopy: new perspective on the weathering of anhydrous cement
NASA Astrophysics Data System (ADS)
Torres-Carrasco, M.; del Campo, A.; de la Rubia, MA; Reyes, E.; Moragues, A.; Fernández, JF
2017-10-01
Raman spectroscopy when is combined with Confocal microscopy is a non-destructive technique that allow us to obtain information in cementitious materials. In this study, we present non-destructive image and structural analysis of anhydrous cement with carbonation evidences by Confocal Raman Microscopy (CRM). The results obtained by CRM show a direct relationship between the presence of the weathering processes of an anhydrous cement with the presence of sulphates and surprisingly, with the existence of amorphous carbon in the medium.
NASA Astrophysics Data System (ADS)
Croitoru, C.; Pascu, A.; Roata, I. C.; Stanciu, E. M.
2017-06-01
In order to obtain high performance calcium carbonate-reinforced HDPE and PP composites, the dispersibility and compatibility of the inorganic phase in the polymer has been achieved through surface treatment of the amorphous calcium carbonate filler with stearic acid. The surface coating of the inorganic phase has been proved by XRD and FTIR spectroscopy, through forming of an intermediate layer of calcium stearate which acts as a surfactant, efficient in providing an optimum compatibility with the dominatingly hydrophobic polymer matrix, as determined from the structural information obtained through samples cross-sections analysing.
Solution-grown silicon nanowires for lithium-ion battery anodes.
Chan, Candace K; Patel, Reken N; O'Connell, Michael J; Korgel, Brian A; Cui, Yi
2010-03-23
Composite electrodes composed of silicon nanowires synthesized using the supercritical fluid-liquid-solid (SFLS) method mixed with amorphous carbon or carbon nanotubes were evaluated as Li-ion battery anodes. Carbon coating of the silicon nanowires using the pyrolysis of sugar was found to be crucial for making good electronic contact to the material. Using multiwalled carbon nanotubes as the conducting additive was found to be more effective for obtaining good cycling behavior than using amorphous carbon. Reversible capacities of 1500 mAh/g were observed for 30 cycles.
Oxidation-Based Continuous Laser Writing in Vertical Nano-Crystalline Graphite Thin Films
Loisel, Loïc; Florea, Ileana; Cojocaru, Costel-Sorin; Tay, Beng Kang; Lebental, Bérengère
2016-01-01
Nano and femtosecond laser writing are becoming very popular techniques for patterning carbon-based materials, as they are single-step processes enabling the drawing of complex shapes without photoresist. However, pulsed laser writing requires costly laser sources and is known to cause damages to the surrounding material. By comparison, continuous-wave lasers are cheap, stable and provide energy at a more moderate rate. Here, we show that a continuous-wave laser may be used to pattern vertical nano-crystalline graphite thin films with very few macroscale defects. Moreover, a spatially resolved study of the impact of the annealing to the crystalline structure and to the oxygen ingress in the film is provided: amorphization, matter removal and high oxygen content at the center of the beam; sp2 clustering and low oxygen content at its periphery. These data strongly suggest that amorphization and matter removal are controlled by carbon oxidation. The simultaneous occurrence of oxidation and amorphization results in a unique evolution of the Raman spectra as a function of annealing time, with a decrease of the I(D)/I(G) values but an upshift of the G peak frequency. PMID:27194181
Oxidation-Based Continuous Laser Writing in Vertical Nano-Crystalline Graphite Thin Films
NASA Astrophysics Data System (ADS)
Loisel, Loïc; Florea, Ileana; Cojocaru, Costel-Sorin; Tay, Beng Kang; Lebental, Bérengère
2016-05-01
Nano and femtosecond laser writing are becoming very popular techniques for patterning carbon-based materials, as they are single-step processes enabling the drawing of complex shapes without photoresist. However, pulsed laser writing requires costly laser sources and is known to cause damages to the surrounding material. By comparison, continuous-wave lasers are cheap, stable and provide energy at a more moderate rate. Here, we show that a continuous-wave laser may be used to pattern vertical nano-crystalline graphite thin films with very few macroscale defects. Moreover, a spatially resolved study of the impact of the annealing to the crystalline structure and to the oxygen ingress in the film is provided: amorphization, matter removal and high oxygen content at the center of the beam; sp2 clustering and low oxygen content at its periphery. These data strongly suggest that amorphization and matter removal are controlled by carbon oxidation. The simultaneous occurrence of oxidation and amorphization results in a unique evolution of the Raman spectra as a function of annealing time, with a decrease of the I(D)/I(G) values but an upshift of the G peak frequency.
Amorphous calcium carbonate: A precursor phase for aragonite in shell disease of the pearl oyster.
Huang, Jingliang; Liu, Chuang; Xie, Liping; Zhang, Rongqing
2018-02-26
Amorphous calcium carbonate (ACC) has long been shown to act as an important constituent or precursor phase for crystalline material in mollusks. However, the presence and the role of ACC in bivalve shell formation are not fully studied. In this study, we found that brown deposits containing heterogeneous calcium carbonates were precipitated when a shell disease occurred in the pearl oyster Pinctada fucata. Calcein-staining of the brown deposits indicated that numerous amorphous calcium deposits were present, which was further confirmed by Fourier-transform infrared spectroscopy (FTIR), Raman spectrum and X-ray difraction (XRD) analyses. So we speculate that ACC plays an important role in rapid calcium carbonate precipitation during shell repair process in diseased oysters. Copyright © 2018 Elsevier Inc. All rights reserved.
The IR emission features - Emission from PAH molecules and amorphous carbon particles
NASA Technical Reports Server (NTRS)
Allamandola, L. J.; Tielens, A. G. G. M.; Barker, J. R.
1987-01-01
Techniques for the assessment of the importance of the various forms of PAHs, and recent infrared observations concerning the PAH problem, are considered. Spectroscopic data suggest that the observed interstellar spectrum is due to both free molecule-sized PAHs producing the narrow features, and amorphous carbon particles contributing to the broad underlying components. Explanations for the multicomponent emission spectrum are discussed. A model of the emission mechanism for the example of chrysene is presented, and an exact treatment of the IR fluorescence from highly vibrationally excited large molecules shows that species containing 20-30 carbon atoms are responsible for the narrow features, although the spectra more closely resemble those of amorphous carbon particles. It is suggested that future emphasis should be placed on the spatial characteristics of the component spectra.
Stabilization of organic matter in soils: role of amorphous mineral phases
NASA Astrophysics Data System (ADS)
Zewde Tamrat, Wuhib; Rose, Jérôme; Levard, Clément; Chaurand, Perrine; Basile-Doelsch, Isabelle
2016-04-01
Soil organic matter (SOM) globally contributes the largest portion of continental carbon stock. One major issue concerning this large C pool includes its instability by mineralization and erosion due to land use. The main hypothesis of this work is that physicochemical stabilization of SOM is mainly driven by interactions of organic compounds, not with mineral surfaces as classically considered, but with amorphous polymers continuously formed by the alteration of soil minerals(1-3). Our objective is to understand how nano-organomineral complexes (nCOMx) are structured at the nanoscale, assess mechanisms of their formation, and quantify the effects of their occurrence on SOM turnovers. Due to inherent high complexity of natural samples, our methodology is based on the formation of nCOMx from both synthetic systems and natural mineral-weathered components. For the mineral component, biotite (from Bancroft, Canada) was selected. For the organic component, 3,4-Dihydroxy-L-phenylalanine, an amino acid with hydroxyl (pKa=9.95), carboxyl (pKa=2,58), amino (pKa=9,24) and an aromatic functions was chosen. The methodology aimed at developing conditions that generate biotite dissolution and nCOMx precipitation. The second step of the experiment consisted of the precipitation of nCOMx by slowly increasing pH over 3 to 12 hours of hydrolysis. Three final pH conditions were tested (4.2, 5 and 7) with Metal/Carbon ratios of 0.01, 0.1, 1, 10 and 'No Carbon'. The first results of dissolution rates and congruency, AFM imaging, ICPMS, HR-TEM and XRD as well as XAS characterizations (transmission and florescence mode at the Fe K-edge) of nCOMx will be presented. Experiments and analysis techniques were designed to study these synthetic phases with regard to Si, Al, Fe and OM proportions to increase the OM proportion (as in natural soil phases) and also increase the stability of the OM phase (as in increased residence time of OM in the soil). We will focus particularly on the Fe state probed by XAS as a proxy of nCOMx polymerization state. Results showed the Fe atomic structure within the nCOMx was strongly affected by the presence of carbon and the final pH state. Higher pH allowed Fe to polymerize even at a relatively higher carbon content. The increase in concentration of OM led to a decrease in the polymerisation level of Fe amorphous polymers. High carbon composition (M:C=0.1) totally hindered development of Fe-Fe polymers. Whereas, in relatively lower carbon concentrations (M:C=1) iron polymers were exhibited for only highest pH values of 7. For an even lower concentration (M:C=10) iron polymers started to form at lower pH values of 5 and also higher. These suggest the strong dependence of soil OM complexation to inorganic amorphous polymers on pH state and relative availability of these counter parts; and thus giving a better understanding of protection of the carbon from various forms of mineralization. 1-Basile-Doelsch, I., 2015 Environmental Science & Technology, 49(7). 2-Keiluweit, M. et al., 2015. Nature Clim. Change, 5(6). 3-Kleber, M. et al., 2015. In: Donald, L.S. (Ed.), Advances in Agronomy. Key words : soil organic matter (OM), organo-mineral interactions, amorphous minerals, pH
Lu, Ping; Huang, Qing; Mukherjee, Amiya; Hsieh, You-Lo
2010-12-01
Silicon oxycarbide (SiCO) glass-doped carbon fibers with an average diameter of 163 nm were successfully synthesized by electrospinning polymer mixtures of preceramic precursor polyureasilazane (PUS) and carbon precursor polyacrylonitrile (PAN) into fibers then converting to ceramic/carbon hybrid via cross-linking, stabilization, and pyrolysis at temperatures up to 1000 °C. The transformation of PUS/PAN polymer precursors to SiCO/carbon structures was confirmed by EDS and FTIR. Both carbon and SiCO/carbon fibers were amorphous and slightly oxidized. Doping with SiCO enhanced the thermal stability of carbon fibers and acquired new ductile behavior in the SiCO/carbon fibers with significantly improved flexibility and breaking elongation. Furthermore, the SiCO/carbon fibers exhibited dual superhydrophilicity and superoleophilicity with water and decane absorbing capacities of 873 and 608%, respectively. The cyclic voltammetry also showed that SiCO/carbon composite fibers possess better capacitor properties than carbon fibers.
Wang, Chengbing; Ling, San; Yang, Jin; Rao, Dewei; Guo, Zhiguang
2018-01-01
Phase transformation between carbon allotropes usually requires high pressures and high temperatures. Thus, the development of low-temperature phase transition approaches between carbon allotropes is highly desired. Herein, novel amorphous carbon nanocapsules are successfully synthesized by pulsed plasma glow discharge. These nanocapsules are comprised of highly strained carbon clusters encapsulated in a fullerene-like carbon matrix, with the formers serving as nucleation sites. These nucleation sites favored the formation of a diamond unit cell driven by the self-nanoscopic local excessive pressure, thereby significantly decreasing the temperature required for its transformation into a diamond nanocrystal. Under moderate electron beam irradiation (10-20 A cm -2 ) without external heating, self-organization of the energetic carbon clusters into diamond nanocrystals is achieved, whereas the surrounding fullerene-like carbon matrix remains nearly unchanged. Molecular dynamics simulations demonstrate that the defective rings as the active sites dominate the phase transition of amorphous carbon to diamond nanocrystal. The findings may open a promising route to realize phase transformation between carbon allotropes at a lower temperature. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Magnetic Properties and the Giant Magnetoimpedance of Amorphous Co-Based Wires with a Carbon Coating
NASA Astrophysics Data System (ADS)
Golubeva, E. V.; Stepanova, E. A.; Balymov, K. G.; Volchkov, S. O.; Kurlyandskaya, G. V.
2018-04-01
A comparative analysis of the magnetic properties and specific features of the giant magnetoimpedance has been carried out for amorphous rapidly quenched wires with a composition of (Co0.94Fe0.06)72.5Si12.5B15 in the initial state and after the deposition of a carbon coating. The deposition of the defective graphene-like carbon layer was carried out under normal conditions during the exposure in toluene (methylbenzene). The method of the energy-dispersive X-ray spectroscopy made it possible to reliably show that after the modification in toluene, the carbon content on the surface significantly exceeds the natural amount of carbon. The deposition of the carbon coating induced changes in the distribution of the initial quenching stresses in the near-surface layer of amorphous wires. A comparative analysis of the magnetic and magnetoimpedance properties of the samples before and after exposure in the aromatic solvent confirms the occurrence of changes in the effective magnetic anisotropy as a result of this surface treatment.
Foran, Elizabeth; Weiner, Steve; Fine, Maoz
2013-01-01
The main source of calcium carbonate (CaCO3) in the ocean comes from the shells of calcifying planktonic organisms, but substantial amounts of CaCO3 are also produced in fish intestines. The precipitation of CaCO3 assists fish in intestinal water absorption and aids in whole body Ca2+ homeostasis. Here we report that the product formed in the intestinal lumen of the gilt-head seabream, Sparus aurata, is an amorphous calcium carbonate (ACC) phase. With FTIR spectroscopy and SEM imaging, our study shows that the fish-derived carbonates from S. aurata are maintained as a stable amorphous phase throughout the intestinal tract. Moreover, intestinal deposits contained up to 54 mol% Mg2+, the highest concentration yet reported in biogenic ACC. Mg is most likely responsible for stabilizing this inherently unstable mineral. The fish carbonates also displayed initial rapid dissolution when exposed to seawater, exhibiting a significant increase in carbonate concentration. PMID:23609008
Impact Ignition and Combustion Behavior of Amorphous Metal-Based Reactive Composites
NASA Astrophysics Data System (ADS)
Mason, Benjamin; Groven, Lori; Son, Steven
2013-06-01
Recently published molecular dynamic simulations have shown that metal-based reactive powder composites consisting of at least one amorphous component could lead to improved reaction performance due to amorphous materials having a zero heat of fusion, in addition to having high energy densities and potential uses such as structural energetic materials and enhanced blast materials. In order to investigate the feasibility of these systems, thermochemical equilibrium calculations were performed on various amorphous metal/metalloid based reactive systems with an emphasis on commercially available or easily manufactured amorphous metals, such as Zr and Ti based amorphous alloys in combination with carbon, boron, and aluminum. Based on the calculations and material availability material combinations were chosen. Initial materials were either mixed via a Resodyn mixer or mechanically activated using high energy ball milling where the microstructure of the milled material was characterized using x-ray diffraction, optical microscopy and scanning electron microscopy. The mechanical impact response and combustion behavior of select reactive systems was characterized using the Asay shear impact experiment where impact ignition thresholds, ignition delays, combustion velocities, and temperatures were quantified, and reported. Funding from the Defense Threat Reduction Agency (DTRA), Grant Number HDTRA1-10-1-0119. Counter-WMD basic research program, Dr. Suhithi M. Peiris, program director is gratefully acknowledged.
Gong, Feilong; Lu, Shuang; Peng, Lifang; Zhou, Jing; Kong, Jinming; Jia, Dianzeng; Li, Feng
2017-01-01
Porous Mn2O3 microspheres have been synthesized and in-situ coated with amorphous carbon to form hierarchical C@Mn2O3 microspheres by first producing MnCO3 microspheres in solvothermal reactions, and then annealing at 500 °C. The self-assembly growth of MnCO3 microspheres can generate hollow structures inside each of the particles, which can act as micro-reservoirs to store biomass-glycerol for generating amorphous carbon onto the surfaces of Mn2O3 nanorods consisting of microspheres. The C@Mn2O3 microspheres, prepared at 500 °C, exhibit highly enhanced pseudocapacitive performances when compared to the particles after annealed at 400 °C and 600 °C. Specifically, the C@Mn2O3 microspheres prepared at 500 °C show high specific capacitances of 383.87 F g−1 at current density of 0.5 A g−1, and excellent cycling stability of 90.47% of its initial value after cycling for 5000 times. The asymmetric supercapacitors assembled with C@Mn2O3 microspheres after annealed at 500 °C and activated carbon (AC) show an energy density of up to 77.8 Wh kg−1 at power density of 500.00 W kg−1, and a maximum power density of 20.14 kW kg−1 at energy density of 46.8 Wh kg−1. We can attribute the enhanced electrochemical performances of the materials to their three-dimensional (3D) hierarchical structure in-situ coated with carbon. PMID:29168756
Lueking, Angela [State College, PA; Narayanan, Deepa [Redmond, WA
2011-03-08
A process for making a hydrogenated carbon material is provided which includes forming a mixture of a carbon source, particularly a carbonaceous material, and a hydrogen source. The mixture is reacted under reaction conditions such that hydrogen is generated and/or released from the hydrogen source, an amorphous diamond-like carbon is formed, and at least a portion of the generated and/or released hydrogen associates with the amorphous diamond-like carbon, thereby forming a hydrogenated carbon material. A hydrogenated carbon material including a hydrogen carbon clathrate is characterized by evolution of molecular hydrogen at room temperature at atmospheric pressure in particular embodiments of methods and compositions according to the present invention.
NASA Astrophysics Data System (ADS)
Cao, Chuntao
The aim of this research was to explore new directions for carbon dioxide. The first project emphasized silyl monolayer synthesis. Silylation reactions were performed in both liquid and supercritical carbon dioxide. Different monofunctional organosilanes reacted with silica surfaces, forming covalently attached monolayers. These monolayers were characterized using contact angle measurements, X-ray photoelectron spectroscopy, and ellipsometry. Reaction kinetics were established, and compared with silylations in organic solvents. The reaction rate in CO2 is higher than that in conventional solvents while the final coverage is slightly lower than the optimized conditions for conventional solvents. Other multi-functional silanes were also studied. The silylation of nanoporous silica surfaces showed bonding densities almost as high as the maximum value reported in literature for small-pore substrates. Overall, CO2 is a good solvent for silylations on silica surfaces. The second project was to synthesize polymer/polymer nanocomposites using a CO2-assisted templating method. Semicrystalline polymers are composed of tens-of-nanometer thick crystalline lamellae and an amorphous matrix. CO2 normally swells only the amorphous and interlamellar regions. The goal of this research was to selectively bring monomers to the amorphous and interlamellar regions with the help of CO2. In situ polymerization and precipitation fixes the structure, replicating the nano-structure of the semicrystalline polymer substrate. Ring-opening metathesis polymerization was performed inside of CO2-swollen poly(4-methyl-1-pentene) (PMP) of high crystallinity. Several polymer/polymer nanocomposites were successfully produced using this method. They were characterized by a variety of techniques, such as transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA) and wide angle X-ray diffraction (WAXD). Infrared studies and TEM indicated that one type of composite, polynorbomene/PMP, had a gradient distribution of polynorbornene inside of the PMP matrix. Another composite, polyoctenamer/PMP prepared by cis-cyclooctene polymerization, exhibited very interesting mechanical properties. The poly(dicyclopentadiene)/PMP composites are unique nanometer-scale blends of a highly crosslinked thermoset with a thermoplastic polymer.
Carbonation of Clay Minerals Exposed to scCO2/Water at 200 degrees and 250 degrees C
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sugama, T.; Ecker, L.; Gill, S.
2010-11-01
To clarify the mechanisms of carbonation of clay minerals, such as bentonite, kaolinite, and soft clay, we exposed them to supercritical carbon dioxide (scCO2)/water at temperatures of 200 and 250 C and pressures of 1500 and 2000 psi for 72- and 107-hours. Bentonite, comprising three crystalline phases, montmorillonite (MMT), anorthoclase-type albite, and quartz was susceptible to reactions with ionic carbonic acid yielded by the interactions between scCO2 and water, particularly MMT and anorthoclase-type albite phases. For MMT, the cation-exchangeable ions, such as Na+ and Ca2+, present in its basal interplanar space, were replaced by proton, H+, from ionic carbonic acid;more » thereafter, the cations leaching from MMT directly reacted with CO32- as a counter ion of H+ to form carbonate compounds. Such in-situ carbonation process in basal space caused the shrinkage and breakage of the spacing structure within MMT. In contrast, the wet carbonation of anorthoclase-type albite, categorized as rock minerals, entailed the formation of three amorphous by-products, such as carbonates, kaolinite-like compounds, and silicon dioxide. Together, these two different carbonations caused the disintegration and corruption of bentonite. Kaolinite clay containing the amorphous carbonates and silicon dioxide was inert to wet carbonation. We noted only a gain in weight due to its water uptake, suggesting that kaolinite-like by-products generated by the wet carbonation of rock minerals might remain unchanged even during extended exposure. Soft clay consisting of two crystalline phases, dolomite and silicon dioxide, also was unaltered by wet carbonation, despite the uptake of water.« less
Preparation of mesoporous carbon nitride structure by the dealloying of Ni/a-CN nanocomposite films
NASA Astrophysics Data System (ADS)
Zhou, Han; Shen, Yongqing; Huang, Jie; Liao, Bin; Wu, Xianying; Zhang, Xu
2018-05-01
The preparation of mesoporous carbon nitride (p-CN) structure by the selective dealloying process of Ni/a-CN nanocomposite films is investigated. The composition and structure of the Ni/a-CN nanocomposite films and porous carbon nitride (p-CN) films are determined by scan electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Phase separated structure including nickel carbide phase and the surrounding amorphous carbon nitride (a-CN) matrix are detected for the as-deposited films. Though the bulk diffusion is introduced in the film during the annealing process, the grain sizes for the post-annealed films are around 10 nm and change little comparing with the ones of the as-deposited films, which is associated with the thermostability of the CN surrounding in the film. The p-CN skeleton with its pore size around 12.5 nm is formed by etching the post-annealed films, indicative of the stability of the phase separated structure during the annealing process.
Carbonized Micro- and Nanostructures: Can Downsizing Really Help?
Naraghi, Mohammad; Chawla, Sneha
2014-01-01
In this manuscript, we discuss relationships between morphology and mechanical strength of carbonized structures, obtained via pyrolysis of polymeric precursors, across multiple length scales, from carbon fibers (CFs) with diameters of 5–10 μm to submicron thick carbon nanofibers (CNFs). Our research points to radial inhomogeneity, skin–core structure, as a size-dependent feature of polyacrylonitrile-based CFs. This inhomogeneity is a surface effect, caused by suppressed diffusion of oxygen and stabilization byproducts during stabilization through skin. Hence, reducing the precursor diameters from tens of microns to submicron appears as an effective strategy to develop homogeneous carbonized structures. Our research establishes the significance of this downsizing in developing lightweight structural materials by comparing intrinsic strength of radially inhomogeneous CFs with that of radially homogeneous CNF. While experimental studies on the strength of CNFs have targeted randomly oriented turbostratic domains, via continuum modeling, we have estimated that strength of CNFs can reach 14 GPa, when the basal planes of graphitic domains are parallel to nanofiber axis. The CNFs in our model are treated as composites of amorphous carbon (matrix), reinforced with turbostratic domains, and their strength is predicted using Tsai–Hill criterion. The model was calibrated with existing experimental data. PMID:28788651
NASA Astrophysics Data System (ADS)
Yanase, Takashi; Uwabe, Hiroaki; Hasegawa, Koki; Nagahama, Taro; Yamaguchi, Makoto; Shimada, Toshihiro
2018-03-01
We synthesized semitransparent conducting thin films of amorphous carbon from sp3-rich network polymer. The films showed a reasonable optical transparency (58-73% transmission in the wavelength range of 380-2200 nm), a low electric resistivity (6.7 × 10-3 Ω cm), and durability against corrosive chemical reagents. The sintering of the amorphous films results in the formation of a carbon honeycomb lattice in the films.
Carbon-silicon core-shell nanowires as high capacity electrode for lithium ion batteries.
Cui, Li-Feng; Yang, Yuan; Hsu, Ching-Mei; Cui, Yi
2009-09-01
We introduce a novel design of carbon-silicon core-shell nanowires for high power and long life lithium battery electrodes. Amorphous silicon was coated onto carbon nanofibers to form a core-shell structure and the resulted core-shell nanowires showed great performance as anode material. Since carbon has a much smaller capacity compared to silicon, the carbon core experiences less structural stress or damage during lithium cycling and can function as a mechanical support and an efficient electron conducting pathway. These nanowires have a high charge storage capacity of approximately 2000 mAh/g and good cycling life. They also have a high Coulmbic efficiency of 90% for the first cycle and 98-99.6% for the following cycles. A full cell composed of LiCoO(2) cathode and carbon-silicon core-shell nanowire anode is also demonstrated. Significantly, using these core-shell nanowires we have obtained high mass loading and an area capacity of approximately 4 mAh/cm(2), which is comparable to commercial battery values.
The IR emission features - Emission from PAH molecules and amorphous carbon particles
NASA Technical Reports Server (NTRS)
Allamandola, L. J.; Tielens, A. G. G. M.; Barker, J. R.
1987-01-01
Given the current understanding of polycyclic aromatic hydrocarbons (PAHs), the spectroscopic data suggest that are at least two components which contribute to the interstellar emission spectrum: (1) free molecule-sized PAHs producing the narrow features and (2) amorphous carbon particles (which are primarily composed of an irregular 'lattice' of PAHs) contributing to the broad underlying components. An exact treatment of the IR fluorescence from highly vibrationally excited large molecules demonstrates that species containing between 20 and 30 carbon atoms are responsible for the narrow features, although the spectra match more closely with the spectra of amorphous carbon particles. It is concluded that, since little is known about the spectroscopic properties of free PAHs and PAH clusters, much laboratory work is required along with an observational program focusing on the spatial characteristics of the spectra.
Investigating the stability of cathode materials for rechargeable lithium ion batteries
NASA Astrophysics Data System (ADS)
Huang, Yiqing
Lithium ion batteries are widely used in portable electronic devices and electric vehicles. However, safety is one of the most important issues for the Li-ion batteries' use. Some cathode materials, such as LiCoO 2, are thermally unstable in the charged state. Upon decomposition these cathode materials release O2, which could react with organic electrolyte, leading to a thermal runaway. Thus understanding the stability of the cathode materials is critical to the safety of lithium ion batteries. Olivine-type LiMnPO4 is a promising cathode material for lithium ion batteries because of its high energy density. We have revealed the critical role of carbon in the stability and thermal behaviour of olivine MnPO 4 obtained by chemical delithiation of LiMnPO4. (Li)MnPO 4 samples with various particle sizes and carbon contents were studied. Carbon-free LiMnPO4 obtained by solid state synthesis in O 2 becomes amorphous upon delithiation. Small amounts of carbon (0.3 wt.%) help to stabilize the olivine structure, so that completely delithiated crystalline olivine MnPO4 can be obtained. Larger amount of carbon (2 wt.%) prevents full delithiation. Heating in air, O2, or N 2 results in structural disorder (< 300 °C), formation of an intermediate sarcopside Mn3(PO4)2 phase (350 -- 450 °C), and complete decomposition to Mn2P2O 7 on extended heating at 400 °C. Carbon protects MnPO4 from reacting with environmental water, which is detrimental to its structural stability. We not only studied the crystalline olivine MnPO4, but also investigated the amorphous products obtained from carbon-free LiMnPO 4. We have revealed the Mn dissolution phenomenon during chemical delithiation of LiMnPO4, which causes the amorphization of olivine MnPO 4. Properties of crystalline-MnPO4 obtained from carbon-coated LiMnPO4 and of amorphous product resulting from the delithiation of pure LiMnPO4 were studied and compared. The P-rich amorphous phases in the latter are considered to be MnHP2O7 and MnH2P2O7 from XAS and XPS analysis. Safety of batteries not only depends on the stability of the active materials, but also the interactions between the active materials and electrolyte. Thus we study the stability between the cathode materials and the electrolyte. The thermal stability of electrochemically delithiated Li0.1N 0.8C0.15Al0.05O2 (NCA), FePO4 (FP), Mn0.8Fe0.2PO4 (MFP), hydrothermally synthesized VOPO4, LiVOPO4 and electrochemically lithiated Li2VOPO4 is investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis, coupled with mass spectrometry (TGA-MS). The thermal stability is found in the order: NCA< VOPO4< MFP< FP=LiVOPO4=Li2VOPO4. Sealed capsule high pressure experiments show a phase transformation of VOPO4 → HVOPO4 → H2VOPO4 when VOPO4 reacts with electrolyte (1 M LiPF6 in EC: DMC=1:1) between 200 and 300 °C. Finally, we characterize the lithium storage and release mechanism of V2O5 aerogels by x-ray photoelectron spectroscopy (XPS). We study the influence of n--butyllithium (n--BuLi) treatments on the electrochemical performance of the aerogel. In addition to fully reversible V reduction and oxidation due to the intercalation reaction, we observe the formation of LiOH species that are only partially reversible. This is attributed to reaction with the interlayer water and is considered responsible for the gradual capacity fade. The n--BuLi treated aerogels display a higher capacity than those without and our XPS analysis reveals an additional reversible formation of Li2O.
MnO2/carbon nanowalls composite electrode for supercapacitor application
NASA Astrophysics Data System (ADS)
Hassan, Sameh; Suzuki, Masaaki; Mori, Shinsuke; El-Moneim, Ahmed Abd
2014-03-01
Amorphous MnO2/carbon nanowalls composite films are developed for the supercapacitor applications. Synthesis of carbon nanowalls template is performed by plasma-enhanced chemical vapor deposition in a CO/H2 microwave discharge system. A well dispersion of amorphous MnO2 domains throughout carbon nanowalls template is obtained by potentiostatic anodic deposition technique. Carbon nanowalls enable to improve the capacitive behavior and rate capability of MnO2, a specific capacitance of 851 F g-1 at a current density of 1 mA cm-2 and charge transfer resistance of 1.02 Ω are obtained. MnO2/carbon nanowalls composite film exhibits energy density of 118 wh kg-1, power density of 783 wh kg-1, and capacitance retention of 92% after long cycle life of 2000 cycles by charging and discharging at 3 mA cm-2. The high density of atomic scale graphitic edges and large surface area of carbon nanowalls in conjunction with the presence of amorphous MnO2 domains facilitate rapid electron and ion transport and hence offering the potential of the improved capacitive behavior.
Functionally gradient hard carbon composites for improved adhesion and wear
NASA Astrophysics Data System (ADS)
Narayan, Roger Jagdish
A new approach is proposed for fabricating biomedical devices that last longer and are more biocompatible than those presently available. In this approach, a bulk material is chosen that has desirable mechanical properties (low modulus, high strength, high ductility and high fatigue strength). This material is coated with corrosion-resistant, wear-resistant, hard, and biocompatible hard carbon films. One of the many forms of carbon, tetrahedral amorphous carbon, consists mainly of sp3-bonded atoms. Tetrahedral amorphous carbon possesses properties close to diamond in terms of hardness, atomic smoothness, and inertness. Tetrahedral amorphous carbon and diamond films usually contain large amounts of compressive and sometimes tensile stresses; adhesive failure from these stresses has limited widespread use of these materials. This research involves processing, characterization and modeling of functionally gradient tetrahedral amorphous carbon and diamond composite films on metals (cobalt-chromium and titanium alloys) and polymers (polymethylmethacrylate and polyethylene) used in biomedical applications. Multilayer discontinuous thin films of titanium carbide, titanium nitride, aluminum nitride, and tungsten carbide have been developed to control stresses and graphitization in diamond films. A morphology of randomly interconnected micron sized diamond crystallites provides increased toughness and stress reduction. Internal stresses in tetrahedral amorphous carbon were reduced via incorporation of carbide forming elements (silicon and titanium) and noncarbide forming elements (copper, platinum, and silver). These materials were produced using a novel target design during pulsed laser deposition. These alloying atoms reduce hardness and sp3-bonded carbon content, but increase adhesion and wear resistance. Silver and platinum provide the films with antimicrobial properties, and silicon provides bioactivity and aids bone formation. Bilayer coatings were created that couple the adherence, biocompatibility, erosion resistance, and long term release of functional elements from hard carbon coatings with bioactive properties of nanocrystalline hydroxyapatite and short term drug release properties of resorbable poly (D,L) lactide-based materials. Finally, these hard carbon coatings have a variety of non-medical applications, including use in microelectronics packaging, sensors, flat panel displays, photodiodes, cutting tools, optical switches, and wear-resistant magnetic disks.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Arenal, Raul; Lopez-Bezanilla, Alejandro
2014-07-25
We report experimental evidence of the formation by in situ electron-irradiation of single-walled carbon nanotubes (C NT) confined within boron nitride nanotubes (BN-NT). The electron radiation stemming from the microscope supplies the energy required by the amorphous carbonaceous structures to crystallize in a tubular form in a catalyst free procedure, at room temperature and high vacuum. The structural defects resulting from the interaction of the shapeless carbon with the BN nanotube are corrected in a self-healing process throughout the crystallinization. Structural changes developed during the irradiation process such as defects formation and evolution, shrinkage, and shortness of the BN-NT weremore » in situ monitored. The outer BN wall provides a protective and insulating shell against environmental Perturbations to the inner C-NT without affecting their electronic properties, as demonstrated by first principles calculations.« less
Structural Studies of Amorphous Materials by Fluctuation Electron Microscopy
DOE Office of Scientific and Technical Information (OSTI.GOV)
Treacy, Michael M. J.
Fluctuation Electron Microscopy (FEM) is a technique that examines the fluctuations in electron scattering across a uniformly thin amorphous sample. The statistics of the intensity fluctuations, mean and variance, reveal any underlying medium-range order present in the structure. The goals of this project were: (1) To determine the fundamentals of the scattering physics that gives rise to the variance signal in fluctuation electron microscopy (FEM); (2) To use these discoveries to find ways to quantify FEM; (3) To apply the FEM method to interesting and technologically important families of amorphous materials, particularly those with important applications in energy-related processes. Excellent progress was made in items (1) and (2). In stage (3) we did not examine the metamict zircons, as proposed. Instead, we examined films of polycrystalline and amorphous semi-conducting diamond. Significant accomplishments are: (1) A Reverse Monte Carlo procedure was successfully implemented to invert FEM data into a structural model. This is computer-intensive, but it demonstrated that diffraction and FEM data from amorphous silicon are most consistent with a paracrystallite model. This means that there is more diamond-like topology present in amorphous silicon than is predicted by the continuous random network model. (2) There is significant displacement decoherence arising in diffraction from amorphous silicon and carbon. The samples are being bombarded by the electron beam and atoms do not stay still while being irradiated – much more than was formerly understood. The atom motions cause the destructive and constructive interferences in the diffraction pattern to fluctuate with time, and it is the time-averaged speckle that is being measured. The variance is reduced by a factor m, 4 ≤ m ≤ 1000, relative to that predicted by kinematical scattering theory. (3) Speckle intensity obeys a gamma distribution, where the mean intensitymore » $$ \\overline{I}\\ $$ and m are the two parameters governing the shape of the gamma distribution profile. m is determined by the illumination spatial coherence, which is normally very high, and mostly by the displacement decoherence within the sample. (4) Amorphous materials are more affected by the electron beam than are crystalline materials. Different samples exhibit different disruptibility, as measured by the effective values of m that fit the data. (5) Understanding the origin of the displacement decoherence better should lead to efficient methods for computing the observed variance from amorphous materials.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rajachidambaram, Jaana Saranya; Sanghavi, Shail P.; Nachimuthu, Ponnusamy
Amorphous zinc tin oxide (ZTO) was investigated to determine the effect of deposition and post annealing conditions on film structure, composition, surface contamination, and thin film transistor (TFT) device performance. X-ray diffraction results indicated that the ZTO films remain amorphous even after annealing to 600 °C. We found that the bulk Zn:Sn ratio of the sputter deposited films were slightly tin rich compared to the composition of the ceramic sputter target, and there was a significant depletion of zinc at the surface. X-ray photoelectron spectroscopy also indicated that residual surface contamination depended strongly on the sample post-annealing conditions where water,more » carbonate and hydroxyl species were absorbed to the surface. Electrical characterization of ZTO films, using TFT test structures, indicated that mobilities as high as 17 cm2/Vs could be obtained for depletion mode devices.« less
NASA Astrophysics Data System (ADS)
Podlesak, David; Amato, Ronald; Dattelbaum, Dana; Firestone, Millicent; Gustavsen, Richard; Huber, Rachel; Ringstrand, Bryan
2015-06-01
The detonation of high explosives (HE) produces a dense fluid of molecular gases and solid carbon. The solid detonation carbon contains various carbon allotropes such as detonation nanodiamonds, ``onion-like'' carbon, graphite and amorphous carbon, with the formation of the different forms dependent upon pressure, temperature and the environmental conditions of the detonation. We have collected solid carbon residues from controlled detonations of three HE formulations (Composition B-3, PBX 9501, and PBX 9502). Soot was collected from experiments designed to produce both steady and overdriven conditions, and from detonations in both an ambient (air) atmosphere and in an inert Ar atmosphere. Structural studies to glean the features of the solid carbon products have been performed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), Raman spectroscopy, small-angle X-ray scattering (SAXS), and X-Ray Pair Distribution Function measurements (PDF). Bulk soot was also analyzed for elemental and isotopic compositions. We will discuss differences in the structure and composition of the detonation carbon as a function of formulation, detonation conditions, and the surrounding atmosphere.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tester, Chantel C.; Brock, Ryan E.; Wu, Ching-Hsuan
2012-02-07
We show that amorphous calcium carbonate (ACC) can be synthesized in phospholipid bilayer vesicles (liposomes). Liposome-encapsulated ACC nanoparticles are stable against aggregation, do not crystallize for at least 20 h, and are ideally suited to investigate the influence of lipid chemistry, particle size, and soluble additives on ACC in situ.
NASA Astrophysics Data System (ADS)
Hu, Jingtian; Zhao, Tingkai; Ji, Xianglin; Peng, Xiarong; Jin, Wenbo; Yang, Wenbo; Zhang, Lei; Gao, Junjie; Dang, Alei; Li, Hao; Li, Tiehu
2017-11-01
Amorphous carbon nanotube (ACNT)/sulfur composites were prepared by solution reaction method. The electrochemical results showed that both ACNT/S composite and ACNT/S mixture had a first reversible capacity of 1020 mA h·g-1, and the capacity retention of ACNT/S composite was 77% after 100 cycles while that of ACNT/S mixture was only 35% with the initial capacity being 850 mA h·g-1. The experimental results showed that the reversible lithium insertion capacity of the composite was obviously high and the cycling stability was good, which was mainly due to the solid and uniform dispersion of the sulfur and amorphous carbon nanotube matrix in the composite.
Room-temperature Electrochemical Synthesis of Carbide-derived Carbons and Related Materials
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gogotsi, Yury
2015-02-28
This project addresses room-temperature electrochemical etching as an energy-efficient route to synthesis of 3D nanoporous carbon networks and layered 2D carbons and related structures, as well as provides fundamental understanding of structure and properties of materials produced by this method. Carbide-derived-carbons (CDCs) are a growing class of nanostructured carbon materials with properties that are desirable for many applications, such as electrical energy and gas storage. The structure of these functional materials is tunable by the choice of the starting carbide precursor, synthesis method, and process parameters. Moving from high-temperature synthesis of CDCs through vacuum decomposition above 1400°C and chlorination abovemore » 400°C, our studies under the previous DOE BES support led to identification of precursor materials and processing conditions for CDC synthesis at temperatures as low as 200°C, resulting in amorphous and highly reactive porous carbons. We also investigated synthesis of monolithic CDC films from carbide films at 250-1200°C. The results of our early studies provided new insights into CDC formation, led to development of materials for capacitive energy storage, and enabled fundamental understanding of the electrolyte ions confinement in nanoporous carbons.« less
Glycolytic intermediates induce amorphous calcium carbonate formation in crustaceans.
Sato, Ai; Nagasaka, Seiji; Furihata, Kazuo; Nagata, Shinji; Arai, Isao; Saruwatari, Kazuko; Kogure, Toshihiro; Sakuda, Shohei; Nagasawa, Hiromichi
2011-04-01
It has been thought that phosphorus in biominerals made of amorphous calcium carbonate (ACC) might be related to ACC formation, but no such phosphorus-containing compounds have ever been identified. Crustaceans use ACC biominerals in exoskeleton and gastroliths so that they will have easy access to calcium carbonate inside the body before and after molting. We have identified phosphoenolpyruvate and 3-phosphoglycerate, intermediates of the glycolytic pathway, in exoskeleton and gastroliths and found them important for stabilizing ACC.
Mangolini, Filippo; Krick, Brandon A.; Jacobs, Tevis D. B.; ...
2017-12-27
Harsh environments pose materials durability challenges across the automotive, aerospace, and manufacturing sectors, and beyond. While amorphous carbon materials have been used as coatings in many environmentally-demanding applications owing to their unique mechanical, electrical, and optical properties, their limited thermal stability and high reactivity in oxidizing environments have impeded their use in many technologies. Silicon- and oxygen-containing hydrogenated amorphous carbon (a-C:H:Si:O) films are promising for several applications because of their higher thermal stability and lower residual stress compared to hydrogenated amorphous carbon (a-C:H). However, an understanding of their superior thermo-oxidative stability compared to a-C:H is lacking, as it has beenmore » inhibited by the intrinsic challenge of characterizing an amorphous, multi-component material. Here, we show that introducing silicon and oxygen in a-C:H slightly enhances the thermal stability in vacuum, but tremendously increases the thermo-oxidative stability and the resistance to degradation upon exposure to the harsh conditions of low Earth orbit (LEO). The latter is demonstrated by having mounted samples of a-C:H:Si:O on the exterior of the International Space Station via the Materials International Space Station (MISSE) mission 7b. Exposing lightly-doped a-C:H:Si:O to elevated temperatures under aerobic conditions or to LEO causes carbon volatilization in the near-surface region, producing a silica surface layer that protects the underlying carbon from further removal. In conclusion, these findings provide a novel physically-based understanding of the superior stability of a-C:H:Si:O in harsh environments compared to a-C:H.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mangolini, Filippo; Krick, Brandon A.; Jacobs, Tevis D. B.
Harsh environments pose materials durability challenges across the automotive, aerospace, and manufacturing sectors, and beyond. While amorphous carbon materials have been used as coatings in many environmentally-demanding applications owing to their unique mechanical, electrical, and optical properties, their limited thermal stability and high reactivity in oxidizing environments have impeded their use in many technologies. Silicon- and oxygen-containing hydrogenated amorphous carbon (a-C:H:Si:O) films are promising for several applications because of their higher thermal stability and lower residual stress compared to hydrogenated amorphous carbon (a-C:H). However, an understanding of their superior thermo-oxidative stability compared to a-C:H is lacking, as it has beenmore » inhibited by the intrinsic challenge of characterizing an amorphous, multi-component material. Here, we show that introducing silicon and oxygen in a-C:H slightly enhances the thermal stability in vacuum, but tremendously increases the thermo-oxidative stability and the resistance to degradation upon exposure to the harsh conditions of low Earth orbit (LEO). The latter is demonstrated by having mounted samples of a-C:H:Si:O on the exterior of the International Space Station via the Materials International Space Station (MISSE) mission 7b. Exposing lightly-doped a-C:H:Si:O to elevated temperatures under aerobic conditions or to LEO causes carbon volatilization in the near-surface region, producing a silica surface layer that protects the underlying carbon from further removal. In conclusion, these findings provide a novel physically-based understanding of the superior stability of a-C:H:Si:O in harsh environments compared to a-C:H.« less
Sunlight activated anodic freestanding ZrO2 nanotube arrays for Cr(VI) photoreduction.
Bashirom, Nurulhuda; Tan, Wai Kian; Go, Kawamura; Matsuda, Atsunori; Abdul Razak, Khairunisak; Lockman, Zainovia
2018-06-14
Visible-light-active freestanding zirconia (ZrO2) nanotube (FSZNT) arrays were fabricated by a facile electrochemical anodization method in fluoride containing ethylene glycol electrolyte added to it 1 vol.% of potassium carbonate (K2CO3) at 60 V for 1 h. Poor adhesion at metal|oxide interface was induced by K2CO3 leading to formation of the FSZNT flakes. The effect of crystal structures of FSZNTs e.g., amorphous, amorphous/tetragonal, and tetragonal/monoclinic was investigated towards the photocatalytic reduction of 10 ppm hexavalent chromium, Cr(VI) at pH 2 under sunlight. The results demonstrate the amorphous FSZNTs exhibited the highest Cr(VI) removal efficiency than the crystalline FSZNTs (95 % versus 33 % after 5 h). The high photocatalytic activity of the amorphous FSZNTs can be attributed to enhanced Cr(VI) adsorption, high visible light absorption, and better charge carriers separation. The low photocatalytic activity of the crystalline FSZNTs annealed at 500 °C was mainly attributed to poor Cr(VI) adsorption, low visible light absorption, and less photoactive monoclinic-ZrO2. © 2018 IOP Publishing Ltd.
Reaction mechanisms for enhancing carbon dioxide mineral sequestration
NASA Astrophysics Data System (ADS)
Jarvis, Karalee Ann
Increasing global temperature resulting from the increased release of carbon dioxide into the atmosphere is one of the greatest problems facing society. Nevertheless, coal plants remain the largest source of electrical energy and carbon dioxide gas. For this reason, researchers are searching for methods to reduce carbon dioxide emissions into the atmosphere from the combustion of coal. Mineral sequestration of carbon dioxide reacted in electrolyte solutions at 185°C and 2200 psi with olivine (magnesium silicate) has been shown to produce environmentally benign carbonates. However, to make this method feasible for industrial applications, the reaction rate needs to be increased. Two methods were employed to increase the rate of mineral sequestration: reactant composition and concentration were altered independently in various runs. The products were analyzed with complete combustion for total carbon content. Crystalline phases in the product were analyzed with Debye-Scherrer X-ray powder diffraction. To understand the reaction mechanism, single crystals of San Carlos Olivine were reacted in two solutions: (0.64 M NaHCO3/1 M NaCl) and (5.5 M KHCO3) and analyzed with scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), and fluctuation electron microscopy (FEM) to study the surface morphology, atomic crystalline structure, composition and amorphous structure. From solution chemistry studies, it was found that increasing the activity of the bicarbonate ion increased the conversion rate of carbon dioxide to magnesite. The fastest conversion, 60% conversion in one hour, occurred in a solution of 5.5 M KHCO3. The reaction product particles, magnesium carbonate, significantly increased in both number density and size on the coupon when the bicarbonate ion activity was increased. During some experiments reaction vessel corrosion also altered the mineral sequestration mechanism. Nickel ions from vessel corrosion led to nickel precipitation in the carbonate particles and the lack of an amorphous silica reaction layer on the olivine. It was concluded that nickel ions destabilized the silica passivation layer and led to faster growth of carbonate precipitates. Overall, nickel ions increased the reaction rate of mineral sequestration of carbon dioxide.
Falabella, S.
1998-06-09
Amorphous diamond films having a significant reduction in intrinsic stress are prepared by biasing a substrate to be coated and depositing carbon ions thereon under controlled temperature conditions. 1 fig.
NASA Technical Reports Server (NTRS)
Anton, R.; Poppa, H.; Flanders, D. C.
1982-01-01
The graphoepitaxial alignment of vapor-deposited discrete metal crystallites is investigated in the nucleation and growth stages and during annealing by in situ UHV/TEM techniques. Various stages of nucleation, growth and coalescence of vapor deposits of Au, Ag, Pb, Sn, and Bi on amorphous, topographically structured C substrates are analyzed by advanced dark-field techniques to detect preferred local orientations. It is found that the topography-induced orientation of metal crystallites depends strongly on their mobility and their respective tendency to develop pronounced crystallographic shapes. Lowering of the average surface free energies and increasing the crystallographic surface energy anisotropies cause generally improved graphoepitaxial alignments.
Zhang, Rujing; Li, Xiao; Zhang, Li; Lin, Shuyuan
2016-01-01
It is of great significance to design a platform with large surface area and high electrical conductivity for poorly conductive catalyst for hydrogen evolution reaction (HER), such as molybdenum sulfide (MoSx), a promising and cost‐effective nonprecious material. Here, the design and preparation of a free‐standing and tunable graphene mesoporous structure/single‐walled carbon nanotube (GMS/SWCNT) hybrid membrane is reported. Amorphous MoSx is electrodeposited on this platform through a wet chemical process under mild temperature. For MoSx@GMS/SWCNT hybrid electrode with a low catalyst loading of 32 μg cm−2, the onset potential is near 113 mV versus reversible hydrogen electrode (RHE) and a high current density of ≈71 mA cm−2 is achieved at 250 mV versus RHE. The excellent HER performance can be attributed to the large surface area for MoSx deposition, as well as the efficient electron transport and abundant active sites on the amorphous MoSx surface. This novel catalyst is found to outperform most previously reported MoSx‐based HER catalysts. Moreover, the flexibility of the electrode facilitates its stable catalytic performance even in extremely distorted states. PMID:27980998
Characterization of DC Magnetron Sputtering Plasma Used for Deposition of Amorphous Carbon Nitride
NASA Astrophysics Data System (ADS)
Camps, Enrique; Escobar-Alarcón, Luis; López, J.; Zambrano, G.; Prieto, P.
2006-12-01
Amorphous carbon nitride (a-CNx) thin films are attractive due to their potential applications, in different areas. This material can be hard and used as a protective coating, or can be soft and porous and used as the active element in gas sensors, it can also be used as a radiation detector due to its thermoluminescent response. The use of this material for one or another application, will depend on the material's structure, which can be changed by changing the deposition parameters. When using the d.c. magnetron sputtering technique it means mainly the change of discharge power, type of Ar/N2 gas mixture, and the working gas pressure. The variation of these deposition parameters has an important influence on the characteristics of the plasma formed in the discharge. In this work we studied the plasma characteristics, such as the type of excited species, plasma density, and electron temperature under different deposition conditions, using Optical Emission Spectroscopy (OES), and a single Langmuir probe. These parameters were correlated with the properties of a-CNx films deposited under those characterized regimes, in order to establish the role that the plasma parameters play on the formation of the different structures of CNx films.
Method of produce ultra-low friction carbon films
Erdemir, Ali; Fenske, George R.; Eryilmaz, Osman Levent; Lee, Richard H.
2003-04-15
A method and article of manufacture of amorphous diamond-like carbon. The method involves providing a substrate in a chamber, providing a mixture of a carbon containing gas and hydrogen gas with the mixture adjusted such that the atomic molar ratio of carbon to hydrogen is less than 0.3, including all carbon atoms and all hydrogen atoms in the mixture. A plasma is formed of the mixture and the amorphous diamond-like carbon film is deposited on the substrate. To achieve optimum bonding an intervening bonding layer, such as Si or SiO.sub.2, can be formed from SiH.sub.4 with or without oxidation of the layer formed.
Kinetic Monte Carlo (kMC) simulation of carbon co-implant on pre-amorphization process.
Park, Soonyeol; Cho, Bumgoo; Yang, Seungsu; Won, Taeyoung
2010-05-01
We report our kinetic Monte Carlo (kMC) study of the effect of carbon co-implant on the pre-amorphization implant (PAL) process. We employed BCA (Binary Collision Approximation) approach for the acquisition of the initial as-implant dopant profile and kMC method for the simulation of diffusion process during the annealing process. The simulation results implied that carbon co-implant suppresses the boron diffusion due to the recombination with interstitials. Also, we could compare the boron diffusion with carbon diffusion by calculating carbon reaction with interstitial. And we can find that boron diffusion is affected from the carbon co-implant energy by enhancing the trapping of interstitial between boron and interstitial.
NASA Astrophysics Data System (ADS)
Wang, D.; Lee, J. R.; Talley, C. E.; Murphy, K. E.; Han, T. Y.; Deyoreo, J. J.; Dove, P. M.
2006-12-01
Calcium carbonate biominerals are particularly significant because of their direct role in regulating the global carbon cycle, as well as their ubiquitous occurrence across earth environments. Biogenic carbonates are further distinguished by their broad phlyogenetic distribution; hence it has been suggested that unrelated eukaryotes must have used similar biochemical strategies to control mineralization. Recent studies have shown that an amorphous calcium carbonate (ACC) phase potentially plays a key role in the initial formation of carbonate minerals and in "shaping" them into complex morphologies widely seen in biominerals. Echinoderms, mollusks, and possibly many other organisms use ACC as a precursor phase that is first nucleated in cellularly controlled environments such as vesicles and subsequently transforms into a fully crystalline material. Recent studies on sea urchin embryos have shown that during transformation ACC develops short range that resembles calcite before fully crystallizing and serve as inspiration for our studies in synthetic systems. Self-assembled monolayers (SAM) on gold and silver have been used as simple model systems that approximate biological surfaces. Many studies have shown that thiol monolayers with hydroxyl termination stabilize a transitory ACC film that with prolonged exposure to aqueous solution transforms into calcite nucleated on {104} faces. Using Near Edge X-ray Absorption Fine Structure (NEXAFS) we studied SAM/mineral interactions with well ordered mercaptophenol monolayers showed that when these films are first exposed to calcium carbonate solutions, they become disordered and remain so after subsequent deposition of an ACC over-layer. Yet calcite nucleates and grows from the surface bound ACC with predominantly {104} orientation, which suggests a dynamic structural relationship between the SAMs and the mineral phase. While the monolayer/mineral phase interaction has been characterized, the mechanism for nucleating calcite from ACC on these SAMs remains unknown and is the objective of this research. Our preliminary observations of the transforming ACC film with in situ Raman spectroscopy have shown a strengthening of the symmetric mode of the carbonate ion suggesting ordering of the ACC. To fully determine the structural evolution of the mineral phase we will use both Raman and Extended X-Ray Absorption Fine Structure (EXAFS) measurements, coupled with morphological analysis using SEM.
Corrosion resistant amorphous metals and methods of forming corrosion resistant amorphous metals
Farmer, Joseph C.; Wong, Frank M.G.; Haslam, Jeffery J.; Yang, Nancy; Lavernia, Enrique J.; Blue, Craig A.; Graeve, Olivia A.; Bayles, Robert; Perepezko, John H.; Kaufman, Larry; Schoenung, Julie; Ajdelsztajn, Leo
2014-07-15
A system for coating a surface comprises providing a source of amorphous metal, providing ceramic particles, and applying the amorphous metal and the ceramic particles to the surface by a spray. The coating comprises a composite material made of amorphous metal that contains one or more of the following elements in the specified range of composition: yttrium (.gtoreq.1 atomic %), chromium (14 to 18 atomic %), molybdenum (.gtoreq.7 atomic %), tungsten (.gtoreq.1 atomic %), boron (.ltoreq.5 atomic %), or carbon (.gtoreq.4 atomic %).
Corrosion resistant amorphous metals and methods of forming corrosion resistant amorphous metals
Farmer, Joseph C [Tracy, CA; Wong, Frank M. G. [Livermore, CA; Haslam, Jeffery J [Livermore, CA; Yang, Nancy [Lafayette, CA; Lavernia, Enrique J [Davis, CA; Blue, Craig A [Knoxville, TN; Graeve, Olivia A [Reno, NV; Bayles, Robert [Annandale, VA; Perepezko, John H [Madison, WI; Kaufman, Larry [Brookline, MA; Schoenung, Julie [Davis, CA; Ajdelsztajn, Leo [Walnut Creek, CA
2009-11-17
A system for coating a surface comprises providing a source of amorphous metal, providing ceramic particles, and applying the amorphous metal and the ceramic particles to the surface by a spray. The coating comprises a composite material made of amorphous metal that contains one or more of the following elements in the specified range of composition: yttrium (.gtoreq.1 atomic %), chromium (14 to 18 atomic %), molybdenum (.gtoreq.7 atomic %), tungsten (.gtoreq.1 atomic %), boron (.ltoreq.5 atomic %), or carbon (.gtoreq.4 atomic %).
Continuous method of producing silicon carbide fibers
NASA Technical Reports Server (NTRS)
Barnard, Thomas Duncan (Inventor); Nguyen, Kimmai Thi (Inventor); Rabe, James Alan (Inventor)
1999-01-01
This invention pertains to a method for production of polycrystalline ceramic fibers from silicon oxycarbide (SiCO) ceramic fibers wherein the method comprises heating an amorphous ceramic fiber containing silicon and carbon in an inert environment comprising a boron oxide and carbon monoxide at a temperature sufficient to convert the amorphous ceramic fiber to a polycrystalline ceramic fiber. By having carbon monoxide present during the heating of the ceramic fiber, it is possible to achieve higher production rates on a continuous process.
Tunable carbon nanotube-tungsten carbide nanoparticles heterostructures by vapor deposition
DOE Office of Scientific and Technical Information (OSTI.GOV)
Xia, Min; Guo, Hongyan; Ge, Changchun
2014-05-14
A simple, versatile route for the synthesis of carbon nanotube (CNT)-tungsten carbide nanoparticles heterostructures was set up via vapor deposition process. For the first time, amorphous CNTs (α-CNTs) were used to immobilized tungsten carbide nanoparticles. By adjusting the synthesis and annealing temperature, α-CNTs/amorphous tungsten carbide, α-CNTs/W{sub 2}C, and CNTs/W{sub 2}C/WC heterostructures were prepared. This approach provides an efficient method to attach other metal carbides and other nanoparticles to carbon nanotubes with tunable properties.
Spectral characteristics and the extent of paleosols of the Palouse formation
NASA Technical Reports Server (NTRS)
Frazier, B. E.; Busacca, Alan; Cheng, Yaan; Wherry, David; Hart, Judy; Gill, Steve
1987-01-01
Three spectral models defining the spatial distribution of soil areas by levels of amorphous iron, organic carbon, and the ratio of amorphous iron to organic carbon were developed and field verification studies were conducted. The models used particular Thematic Mapper band ratios selected by statistical correlation with soil chemical data. The ability of the models to indicate erosion severity and to differentiate between iron enriched and carbonate paleosols is discussed. In addition, the effect of vegetation cover on paleosols is addressed.
Template confined synthesis of amorphous carbon nanotubes and its confocal Raman microscopy
DOE Office of Scientific and Technical Information (OSTI.GOV)
Maity, Supratim; Roychowdhury, Tuhin; Chattopadhyay, Kalyan Kumar, E-mail: kalyan-chattopadhyay@yahoo.com
2014-04-24
Amorphous carbon nanotubes (aCNTs) were synthesized by AAO (anodic aluminum oxide) template at a temperature 500 °C in nitrogen atmosphere using the citric acid as a carbon source without the help of any catalyst particles. Morphological analysis of the as prepared samples was carried out by field emission scanning electron microscopy (FESEM). Confocal Raman imaging has been studied and an attempt has been made to find out the graphitic (sp{sup 2}) and disordered phase of the CNTs.
Monolithic porous graphitic carbons obtained through catalytic graphitization of carbon xerogels
NASA Astrophysics Data System (ADS)
Kiciński, Wojciech; Norek, Małgorzata; Bystrzejewski, Michał
2013-01-01
Pyrolysis of organic xerogels accompanied by catalytic graphitization and followed by selective-combustion purification was used to produce porous graphitic carbons. Organic gels impregnated with iron(III) chloride or nickel(II) acetate were obtained through polymerization of resorcinol and furfural. During the pyrolysis stage graphitization of the gel matrix occurs, which in turn develops mesoporosity of the obtained carbons. The evolution of the carbon into graphitic structures is strongly dependent on the concentrations of the transition metal. Pyrolysis leads to monoliths of carbon xerogel characterized by substantially enhanced mesoporosity resulting in specific surface areas up to 400 m2/g. Removal of the amorphous carbon by selective-combustion purification reduces the xerogels' mesoporosity, occasionally causing loss of their mechanical strength. The graphitized carbon xerogels were investigated by means of SEM, XRD, Raman scattering, TG-DTA and N2 physisorption. Through this procedure well graphitized carbonaceous materials can be obtained as bulk pieces.
Sea urchin spine calcite forms via a transient amorphous calcium carbonate phase.
Politi, Yael; Arad, Talmon; Klein, Eugenia; Weiner, Steve; Addadi, Lia
2004-11-12
The skeletons of adult echinoderms comprise large single crystals of calcite with smooth convoluted fenestrated morphologies, raising many questions about how they form. By using water etching, infrared spectroscopy, electron diffraction, and environmental scanning electron microscopy, we show that sea urchin spine regeneration proceeds via the initial deposition of amorphous calcium carbonate. Because most echinoderms produce the same type of skeletal material, they probably all use this same mechanism. Deposition of transient amorphous phases as a strategy for producing single crystals with complex morphology may have interesting implications for the development of sophisticated materials.
Goh, P S; Ng, B C; Ismail, A F; Aziz, M; Hayashi, Y
2012-11-15
Mixed matrix hollow fibers composed of multi-walled carbon nanotubes (MWCNTs) and polyetherimide (PEI) were fabricated. Pre-treatment of MWCNTs was carried out prior to the incorporation into the polymer matrix using a simple and feasible two stages approach that involved dry air oxidation and surfactant dispersion. The characterizations of the surface treated MWCNTs using TEM and Raman spectroscopy have evidenced the effectiveness of dry air oxidation in eliminating undesired amorphous carbon and metal catalyst while surfactant dispersion using Triton X100 has suppressed the agglomeration of MWCNTs. The resultant mixed matrix hollow fibers were applied for O(2)/N(2) pure gas separation. Interestingly, it was found that removal of disordered amorphous carbons and metal particles has allowed the hollow structures to be more accessible for the fast and smooth transport of gas molecules, hence resulted in noticeable improvement in the gas separation properties. The composite hollow fibers embedded with the surface modified MWCNTs showed increase in permeability as much as 60% while maintaining the selectivity of the O(2)/N(2) gas pair. This study highlights the necessity to establish an appropriate pre-treatment approach for MWCNTs in order to fully utilize the beneficial transport properties of this material in mixed matrix polymer nanocomposite for gas separation. Copyright © 2012 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Novoselova, I. A.; Oliinyk, N. F.; Volkov, S. V.; Konchits, A. A.; Yanchuk, I. B.; Yefanov, V. S.; Kolesnik, S. P.; Karpets, M. V.
2008-05-01
Carbon nanotubes (CNTs) were synthesized from CO 2 dissolved in molten salts using the novel electrolytic method developed by the authors. The electrolysis were carried out under current and potential controls. To establish the actual current and potential ranges, the electroreduction of carbon dioxide dissolved in the halide melts under an excess pressure up to 15 bar was studied by cyclic voltammetry on glassy-carbon (GC) electrode at a temperature of 550 °C. The electrochemical-chemical-electrochemical mechanism of CO 2 electroreduction was offered for explanation of the obtained results. The structure, morphology, and electronic properties of the CNTs obtained were studied using SEM, TEM, X-ray and electron diffraction analysis, Raman and ESR spectroscopy. It was found that the majority of the CNTs are multi-walled (MWCNTs), have curved form, and most often agglomerate into bundles. Almost all CNTs are filled partly with electrolyte salt. Except MWCNTs the cathode product contains carbon nanofibers, nanographite, and amorphous carbon. The dependences of CNT's yield, their diameter, and structure peculiarities against the electrolysis regimes were established.
Amorphous carbon for photovoltaics
NASA Astrophysics Data System (ADS)
Risplendi, Francesca; Grossman, Jeffrey C.
2015-03-01
All-carbon solar cells have attracted attention as candidates for innovative photovoltaic devices. Carbon-based materials such as graphene, carbon nanotubes (CNT) and amorphous carbon (aC) have the potential to present physical properties comparable to those of silicon-based materials with advantages such as low cost and higher thermal stability.In particular a-C structures are promising systems in which both sp2 and sp3 hybridization coordination are present in different proportions depending on the specific density, providing the possibility of tuning their optoelectronic properties and achieving comparable sunlight absorption to aSi. In this work we employ density functional theory to design suitable device architectures, such as bulk heterojunctions (BHJ) or pn junctions, consisting of a-C as the active layer material.Regarding BHJ, we study interfaces between aC and C nanostructures (such as CNT and fullerene) to relate their optoelectronic properties to the stoichiometry of aC. We demonstrate that the energy alignment between the a-C mobility edges and the occupied and unoccupied states of the CNT or C60 can be widely tuned by varying the aC density to obtain a type II interface.To employ aC in pn junctions we analyze the p- and n-type doping of a-C focusingon an evaluation of the Fermi level and work function dependence on doping.Our results highlight promising features of aC as the active layer material of thin-film solar cells.
Fabrication of amorphous diamond films
Falabella, S.
1995-12-12
Amorphous diamond films having a significant reduction in intrinsic stress are prepared by biasing a substrate to be coated and depositing carbon ions thereon under controlled temperature conditions. 1 fig.
NASA Astrophysics Data System (ADS)
Sun, Xiangcheng; Brückner, Christian; Lei, Yu
2015-10-01
Very brief microwave heating of aniline, ethylene diamine, and phosphoric acid in water at ambient pressure generated nitrogen and phosphorus co-doped carbon dots (N,P-CDs) that exhibit bright dual blue (centred at 450 nm; 51% quantum yield) and green (centred at 510 nm, 38% quantum yield) fluorescence emission bands. The N,P-CDs were characterized using TEM, XRD, XPS, IR, UV-vis, and fluorescence spectroscopy, demonstrating their partially crystalline carbon, partially amorphous structures, and the incorporation of O, N, and P into the carbogenic scaffold. The N,P-CDs demonstrated excitation-dependent and nearly pH-independent emission properties. The unique dual emission properties lay the foundation for the use of N,P-CDs in ratiometric sensing applications.Very brief microwave heating of aniline, ethylene diamine, and phosphoric acid in water at ambient pressure generated nitrogen and phosphorus co-doped carbon dots (N,P-CDs) that exhibit bright dual blue (centred at 450 nm; 51% quantum yield) and green (centred at 510 nm, 38% quantum yield) fluorescence emission bands. The N,P-CDs were characterized using TEM, XRD, XPS, IR, UV-vis, and fluorescence spectroscopy, demonstrating their partially crystalline carbon, partially amorphous structures, and the incorporation of O, N, and P into the carbogenic scaffold. The N,P-CDs demonstrated excitation-dependent and nearly pH-independent emission properties. The unique dual emission properties lay the foundation for the use of N,P-CDs in ratiometric sensing applications. Electronic supplementary information (ESI) available: Detailed experimental section, XRD, FTIR, explosive sensing and the applications results. See DOI: 10.1039/c5nr05549k
Organic matter variations in transgressive and regressive shales
Pasley, M.A.; Gregory, W.A.; Hart, G.F.
1991-01-01
Organic matter in the Upper Cretaceous Mancos Shale adjacent to the Tocito Sandstone in the San Juan Basin of New Mexico was characterized using organic petrology and organic geochemistry. Differences in the organic matter found in these regressive and transgressive offshore marine sediments have been documented and assessed within a sequence stratigraphic framework. The regressive Lower Mancos Shale below the Tocito Sandstone contains abundant well preserved phytoclasts and correspondingly low hydrogen indices. Total organic carbon values for the regressive shale are low. Sediments from the transgressive systems tract (Tocito Sandstone and overlying Upper Mancos Shale) contain less terrestrially derived organic matter, more amorphous non-structured protistoclasts, higher hydrogen indices and more total organic carbon. Advanced stages of degradation are characteristic of the phytoclasts found in the transgressive shale. Amorphous material in the transgressive shale fluoresces strongly while that found in the regressive shale is typically non-fluorescent. Data from pyrolysis-gas chromatography confirm these observations. These differences are apparently related to the contrasting depositional styles that were active on the shelf during regression and subsequent transgression. It is suggested that data from organic petrology and organic geochemistry provide greater resolution in sedimentologic and stratigraphic interpretations, particularly when working with basinward, fine-grained sediments. Petroleum source potential for the regressive Lower Mancos Shale below the Tocito Sandstone is poor. Based on abundant fluorescent amorphous material, high hydrogen indices, and high total organic carbon, the transgressive Upper Mancos Shale above the Tocito Sandstone possesses excellent source potential. This suggests that appreciable source potential can be found in offshore, fine-grained sediments of the transgressive systems tract below the condensed section and associated downlap surface. Organic petrology can be used to accurately predict petroleum source potential. The addition of simple fluorescence microscopy greatly enhances this predictive ability because non-generative amorphous material is generally non-fluorescent. Organic petrology must also be used to properly evaluate the utility of Tmax from programmed pyrolysis as a thermal maturity indicator. Organic matter dominated by autochthonous amorphous protistoclasts exhibits lower Tmax values than that which is composed of mostly phytoclasts. ?? 1991.
Controlled epitaxial graphene growth within removable amorphous carbon corrals
DOE Office of Scientific and Technical Information (OSTI.GOV)
Palmer, James; Hu, Yike; Hankinson, John
2014-07-14
We address the question of control of the silicon carbide (SiC) steps and terraces under epitaxial graphene on SiC and demonstrate amorphous carbon (aC) corrals as an ideal method to pin SiC surface steps. aC is compatible with graphene growth, structurally stable at high temperatures, and can be removed after graphene growth. For this, aC is first evaporated and patterned on SiC, then annealed in the graphene growth furnace. There at temperatures above 1200 °C, mobile SiC steps accumulate at the aC corral that provide effective step flow barriers. Aligned step free regions are thereby formed for subsequent graphene growth atmore » temperatures above 1330 °C. Atomic force microscopy imaging supports the formation of step-free terraces on SiC with the step morphology aligned to the aC corrals. Raman spectroscopy indicates the presence of good graphene sheets on the step-free terraces.« less
NASA Astrophysics Data System (ADS)
Ahmed, Sk Faruque; Alam, Md Shahbaz; Mukherjee, Nillohit
2018-03-01
The effect of temperature on the electron field emission properties of copper incorporated amorphous diamond like carbon (a-Cu:DLC) thin films have been reported. The a-Cu:DLC thin films have been deposited on indium tin oxide (ITO) coated glass and silicon substrate by the radio frequency sputtering process. The chemical composition of the films was investigated using X-ray photoelectron spectroscopy and the micro structure was established using high resolution transmission electron microscopy. The sp2 and sp3 bonding ratio in the a-Cu:DLC have been analyzed by the Fourier transformed infrared spectroscopy studies. The material showed excellent electron field emission properties; which was optimized by varying the copper atomic percentage and temperature of the films. It was found that the threshold field and effective emission barrier were reduced significantly by copper incorporation as well as temperature and a detailed explanation towards emission mechanism has been provided.
Photoluminescence of etched SiC nanowires
NASA Astrophysics Data System (ADS)
Stewart, Polite D., Jr.; Rich, Ryan; Zerda, T. W.
2010-10-01
SiC nanowires were produced from carbon nanotubes and nanosize silicon powder in a tube furnace at temperatures between 1100^oC and 1350^oC. SiC nanowires had average diameter of 30 nm and very narrow size distribution. The compound possesses a high melting point, high thermal conductivity, and excellent wear resistance. The surface of the SiC nanowires after formation is covered by an amorphous layer. The composition of that layer is not fully understood, but it is believed that in addition to amorphous SiC it contains various carbon and silicon compounds, and SiO2. The objective of the research was to modify the surface structure of these SiC nanowires. Modification of the surface was done using the wet etching method. The etched nanowires were then analyzed using Fourier Transform Infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and photoluminescence (PL). FTIR and TEM analysis provided valid proof that the SiC nanowires were successfully etched. Also, the PL results showed that the SiC nanowire core did possess a fluorescent signal.
NASA Astrophysics Data System (ADS)
Sarkar, S.; Banerjee, D.; Das, N. S.; Ghorai, U. K.; Sen, D.; Chattopadhyay, K. K.
2018-03-01
Cadmium Selenide (CdSe) quantum dot (QD) decorated amorphous carbon nanotubes (a-CNTs) hybrids have been synthesized by simple chemical process. The samples were characterized by field emission scanning and transmission electron microscopy, Fourier transformed infrared spectroscopy, Raman and UV-Vis spectroscopy. Lattice image obtained from transmission electron microscopic study confirms the successful attachment of CdSe QDs. It is seen that hybrid samples show an enhanced cold emission properties with good stability. The results have been explained in terms of increased roughness, more numbers of emitting sites and favorable band bending induced electron transport. ANSYS software based calculation has also supported the result. Also a first principle based study has been done which shows that due to the formation of hybrid structure there is a profound upward shift in the Fermi level, i.e. a decrease of work function, which is believed to be another key reason for the observed improved field emission performance.
NASA Astrophysics Data System (ADS)
Takeichi, Satoshi; Nishiyama, Takashi; Tabara, Mitsuru; Kawawaki, Shuichi; Kohno, Masamichi; Takahashi, Koji; Yoshitake, Tsuyoshi
2018-06-01
Ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) composite (UNCD/a-C:H) and UNCD/non-hydrogenated amorphous carbon (a-C) composite (UNCD/a-C) films were prepared via coaxial arc plasma deposition, and their thermal conductivity and interfacial conductance in grain boundaries were measured using a time-domain thermoreflectance method. The interfacial conductance was estimated to be 1,010 and 4,892 MW/(m2·K) for UNCD/a-C:H and UNCD/a-C films, respectively. The reasons for the hydrogenated film having lower interfacial conductance than the non-hydrogenated film are 1) the reduced number of carriers that contribute to heat transport and 2) the hydrogen atoms, which are preferentially located at the grain boundaries and enhance phonon scattering.
Fast-moving dislocations trigger flash weakening in carbonate-bearing faults during earthquakes.
Spagnuolo, Elena; Plümper, Oliver; Violay, Marie; Cavallo, Andrea; Di Toro, Giulio
2015-11-10
Rupture fronts can cause fault displacement, reaching speeds up to several ms(-1) within a few milliseconds, at any distance away from the earthquake nucleation area. In the case of silicate-bearing rocks the abrupt slip acceleration results in melting at asperity contacts causing a large reduction in fault frictional strength (i.e., flash weakening). Flash weakening is also observed in experiments performed in carbonate-bearing rocks but evidence for melting is lacking. To unravel the micro-physical mechanisms associated with flash weakening in carbonates, experiments were conducted on pre-cut Carrara marble cylinders using a rotary shear apparatus at conditions relevant to earthquakes propagation. In the first 5 mm of slip the shear stress was reduced up to 30% and CO2 was released. Focused ion beam, scanning and transmission electron microscopy investigations of the slipping zones reveal the presence of calcite nanograins and amorphous carbon. We interpret the CO2 release, the formation of nanograins and amorphous carbon to be the result of a shock-like stress release associated with the migration of fast-moving dislocations. Amorphous carbon, given its low friction coefficient, is responsible for flash weakening and promotes the propagation of the seismic rupture in carbonate-bearing fault patches.
Origin of melting point depression for rare gas solids confined in carbon pores
DOE Office of Scientific and Technical Information (OSTI.GOV)
Morishige, Kunimitsu, E-mail: morishi@chem.ous.ac.jp; Kataoka, Takaaki
To obtain insights into the mechanism of the melting-point depression of rare gas solids confined in crystalline carbon pores, we examined the freezing and melting behavior of Xe and Ar confined to the crystalline pores of ordered mesoporous carbons as well as compressed exfoliated graphite compared to the amorphous pores of ordered mesoporous silicas, by means of X-ray diffraction. For the Xe and Ar confined to the crystalline carbon pores, there was no appreciable thermal hysteresis between freezing and melting. Furthermore, the position of the main diffraction peak did not change appreciably on freezing and melting. This strongly suggests thatmore » the liquids confined in the carbon pores form a multilayered structure parallel to the smooth walls. For the Xe and Ar confined to the amorphous silica pores, on the other hand, the position of the main diffraction peak shifted into higher scattering angle on freezing suggested that the density of the confined solid is distinctly larger than for the confined liquid. Using compressed exfoliated graphite with carbon walls of higher crystallinity, we observed that three-dimensional (3D) microcrystals of Xe confined in the slit-shaped pores melted to leave the unmelted bilayers on the pore walls below the bulk triple point. The lattice spacing of the 3D microcrystals confined is larger by ∼0.7% than that of the bilayer next to the pore walls in the vicinity of the melting point.« less
Composition, structure, and chemistry of interstellar dust
NASA Technical Reports Server (NTRS)
Tielens, A. G. G. M.; Allamandola, L. J.
1987-01-01
Different dust components present in the interstellar medium (IM) such as amorphous carbon, polycyclic aromatic hydrocarbons, and those IM components which are organic refractory grains and icy grain mantles are discussed as well as their relative importance. The physical properties of grain surface chemistry are discussed with attention given to the surface structure of materials, the adsorption energy and residence time of species on a grain surface, and the sticking probability. Consideration is also given to the contribution of grains to the gas-phase composition of molecular clouds.
High-Temperature Corrosion Behavior of SiBCN Fibers for Aerospace Applications.
Ji, Xiaoyu; Wang, Shanshan; Shao, Changwei; Wang, Hao
2018-06-13
Amorphous SiBCN fibers possessing superior stability against oxidation have become a desirable candidate for high-temperature aerospace applications. Currently, investigations on the high-temperature corrosion behavior of these fibers for the application in high-heat engines are insufficient. Here, our polymer-derived SiBCN fibers were corroded at 1400 °C in air and simulated combustion environments. The fibers' structural evolution after corrosion in two different conditions and the potential mechanisms are investigated. It shows that the as-prepared SiBCN fibers mainly consist of amorphous networks of SiN 3 C, SiN 4 , B-N hexatomic rings, free carbon clusters, and BN 2 C units. High-resolution transmission electron microscopy cross-section observations combined with energy-dispersive spectrometry/electron energy-loss spectroscopy analysis exhibit a trilayer structure with no detectable cracks for fibers after corrosion, including the outermost SiO 2 layer, the h-BN grain-contained interlayer, and the uncorroded fiber core. A high percentage of water vapor contained in the simulated combustion environment triggers the formation of abundant α-cristobalite nanoparticles dispersing in the amorphous SiO 2 phase, which are absent in fibers corroded in air. The formation of h-BN grains in the interlayer could be ascribed to the sacrificial effects of free carbon clusters, Si-C, and Si-N units reacting with oxygen diffusing inward, which protects h-BN grains formed by networks of B-N hexatomic rings in original SiBCN fibers. These results improve our understanding of the corrosion process of SiBCN fibers in a high-temperature oxygen- and water-rich atmosphere.
The Effect of PtRuIr Nanoparticle Crystallinity in Electrocatalytic Methanol Oxidation
Ma, Yanjiao; Wang, Rongfang; Wang, Hui; Liao, Shijun; Key, Julian; Linkov, Vladimir; Ji, Shan
2013-01-01
Two structural forms of a ternary alloy PtRuIr/C catalyst, one amorphous and one highly crystalline, were synthesized and compared to determine the effect of their respective structures on their activity and stability as anodic catalysts in methanol oxidation. Characterization techniques included TEM, XRD, and EDX. Electrochemical analysis using a glassy carbon disk electrode for cyclic voltammogram and chronoamperometry were tested in a solution of 0.5 mol L−1 CH3OH and 0.5 mol L−1 H2SO4. Amorphous PtRuIr/C catalyst was found to have a larger electrochemical surface area, while the crystalline PtRuIr/C catalyst had both a higher activity in methanol oxidation and increased CO poisoning rate. Crystallinity of the active alloy nanoparticles has a big impact on both methanol oxidation activity and in the CO poisoning rate. PMID:28809233
NASA Astrophysics Data System (ADS)
Bushuev, N.; Yafarov, R.; Timoshenkov, V.; Orlov, S.; Starykh, D.
2015-08-01
The self-organization effect of diamond nanocrystals in polymer-graphite and carbon films is detected. The carbon materials deposition was carried from ethanol vapors out at low pressure using a highly non-equilibrium microwave plasma. Deposition processes of carbon film structures (diamond, graphite, graphene) is defined. Deposition processes of nanocrystalline structures containing diamond and graphite phases in different volume ratios is identified. The solid film was obtained under different conditions of microwave plasma chemical synthesis. We investigated the electrical properties of the nanocrystalline carbon films and identified it's from various factors. Influence of diamond-graphite film deposition mode in non-equilibrium microwave plasma at low pressure on emission characteristics was established. This effect is justified using the cluster model of the structure of amorphous carbon. It was shown that the reduction of bound hydrogen in carbon structures leads to a decrease in the threshold electric field of emission from 20-30 V/m to 5 V/m. Reducing the operating voltage field emission can improve mechanical stability of the synthesized film diamond-graphite emitters. Current density emission at least 20 A/cm2 was obtained. Nanocrystalline carbon film materials can be used to create a variety of functional elements in micro- and nanoelectronics and photonics such as cold electron source for emission in vacuum devices, photonic devices, cathodoluminescent flat display, highly efficient white light sources. The obtained graphene carbon net structure (with a net size about 6 μm) may be used for the manufacture of large-area transparent electrode for solar cells and cathodoluminescent light sources
Insights into Silicate Carbonation Processes in Water-Bearing Supercritical CO2 Fluids
DOE Office of Scientific and Technical Information (OSTI.GOV)
Miller, Quin RS; Thompson, Christopher J.; Loring, John S.
2013-07-01
Long-term geologic storage of carbon dioxide (CO2) is considered an integral part to moderating CO2 concentrations in the atmosphere and subsequently minimizing effects of global climate change. Although subsurface injection of CO2 is common place in certain industries, deployment at the scale required for emission reduction is unprecedented and therefore requires a high degree of predictability. Accurately modeling geochemical processes in the subsurface requires experimental derived data for mineral reactions occurring between the CO2, water, and rocks. Most work in this area has focused on aqueous-dominated systems in which dissolved CO2 reacts to form crystalline carbonate minerals. Comparatively little laboratorymore » research has been conducted on reactions occurring between minerals in the host rock and the wet supercritical fluid phase. In this work, we studied the carbonation of wollastonite [CaSiO3] exposed to variably hydrated supercritical CO2 (scCO2) at a range of temperatures (50, 55 and 70 °C) and pressures (90,120 and 160 bar) that simulate conditions in geologic repositories. Mineral transformation reactions were followed by three novel in situ high pressure techniques, including x-ray diffraction that tracked the rate and extents of wollastonite conversion to calcite. Increased dissolved water concentrations in the supercritical CO2 resulted in increased silicate carbonation approaching ~50 wt. %. Development of thin water films on the mineral surface were directly observed with infrared spectroscopy and determined to be critical for facilitating carbonation processes. Even in extreme low water conditions, magic angle spinning nuclear magnetic resonance detected formation of Q3 [Si(OSi)3OH] and Q4 [Si(OSi)4] amorphous silica species. Unlike the thick (<10 μm) passivating silica layers observed in the fully water saturated scCO2 experiments, images obtained from a focused ion beam sectioned sample indicted these coatings were chemically wollastonite but structurally amorphous. In addition, evidence of an intermediate hydrated amorphous calcium carbonate forming under these conditions further emphasize the importance of understanding geochemical processes occurring in water bearing scCO2 fluids.« less
Huang, Yifeng; Deng, Zexiang; Wang, Weiliang; Liang, Chaolun; She, Juncong; Deng, Shaozhi; Xu, Ningsheng
2015-01-01
Nano-scale vacuum channel transistors possess merits of higher cutoff frequency and greater gain power as compared with the conventional solid-state transistors. The improvement in cathode reliability is one of the major challenges to obtain high performance vacuum channel transistors. We report the experimental findings and the physical insight into the field induced crystalline-to-amorphous phase transformation on the surface of the Si nano-cathode. The crystalline Si tip apex deformed to amorphous structure at a low macroscopic field (0.6~1.65 V/nm) with an ultra-low emission current (1~10 pA). First-principle calculation suggests that the strong electrostatic force exerting on the electrons in the surface lattices would take the account for the field-induced atomic migration that result in an amorphization. The arsenic-dopant in the Si surface lattice would increase the inner stress as well as the electron density, leading to a lower amorphization field. Highly reliable Si nano-cathodes were obtained by employing diamond like carbon coating to enhance the electron emission and thus decrease the surface charge accumulation. The findings are crucial for developing highly reliable Si-based nano-scale vacuum channel transistors and have the significance for future Si nano-electronic devices with narrow separation. PMID:25994377
Luo, Chengzhi; Li, Fangying; Li, Delong; Fu, Qiang; Pan, Chunxu
2016-11-16
Due to its unique hierarchical structure, natural spider silk features exceptional mechanical properties such as high tensile strength and great extensibility, making it one of the toughest materials. Herein, we design bioinspired spider silk single-walled carbon nanotubes (BISS-SWCNTs) that combine the hierarchical structure of spider silk and the high strength and conductivity of SWCNTs. To imitate the hierarchical structure, Fe nanoparticles are embedded on the surface of directly synthesized SWCNTs skeleton followed by coating an amorphous carbon layer. The carbon layer forms the spider silk-featured skin-core structure with SWCNTs, thus making the tube junction tougher. The embedded Fe nanoparticles act as glue spots for preventing interfacial slippages between the BISS-SWCNTs and the reinforced matrix. With only 2.1 wt % BISS-SWCNTs added, the tensile strength and Young's modulus of the BISS-SWCNTs/PMMA composites can be improved by 300%. More importantly, the BISS-SWCNTs also retain the high conductivity and transmittance of the pristine SWCNTs film. This unique bioinspired material will be of great importance in applications of multifunctional composite materials and has important implications for the future of biomimetic materials.
Effect of Pt and Fe catalysts in the transformation of carbon black into carbon nanotubes
NASA Astrophysics Data System (ADS)
Asokan, Vijayshankar; Myrseth, Velaug; Kosinski, Pawel
2015-06-01
In this research carbon nanotubes and carbon nano onion-like structures were synthesized from carbon black using metal catalysts at 400 °C and 700 °C. Platinum and iron-group metals were used as catalysts for the transformation of CB into graphitized nanocarbon and the effect of both metals was compared. The synthesized products were characterized using X-ray diffraction (XRD), transmission electron microscope (TEM), high resolution transmission electron microscope (HRTEM) and Raman spectroscopy. The characterization shows that this process is very efficient in the synthesis of high quality graphitized products from amorphous carbon black, even though the process temperature was relatively low in comparison with previous studies. Distinguished graphitic walls of the newly formed carbon nanostructures were clearly visible in the HRTEM images. Possible growth difference related to the type of catalyst used is briefly explained with the basis of electron vacancies in d-orbitals of metals.
Nanopillar arrays of amorphous carbon nitride
NASA Astrophysics Data System (ADS)
Sai Krishna, Katla; Pavan Kumar, B. V. V. S.; Eswaramoorthy, Muthusamy
2011-07-01
Nanopillar arrays of amorphous carbon nitride have been prepared using anodic aluminum oxide (AAO) membrane as a template. The amine groups present on the surface of these nanopillars were exploited for functionalization with oleic acid in order to stabilize the nanostructure at the aqueous-organic interface and also for the immobilization of metal nanoparticles and protein. These immobilised nanoparticles were found to have good catalytic activity.
Jin, Rencheng; Zhai, Qinghe; Wang, Qingyao
2017-10-09
Cobalt sulfide and molybdenum sulfide, with high theoretical capacities, have been considered as one of most promising anode materials for lithium-ion batteries (LIBs). However, the poor cyclability and low rate performances originating from the large volume expansion and poor electrical conductivity extremely inhibit their practical application. Here, the electrochemical performances are effectively improved by growing amorphous cobalt sulfide and molybdenum sulfide onto amorphous carbon-coated multiwalled carbon nanotubes (CNTs@C@CoS 2 and CNTs@C@MoS 2 ). The CNTs@C@CoS 2 presents a high reversible specific capacity of 1252 mAh g -1 at 0.2 Ag -1 , excellent rate performance of 672 mAh g -1 (5 Ag -1 ), and enhanced cycle life of 598 mAh g -1 after 500 cycles at 2 Ag -1 . For CNTs@C@MoS 2 , it exhibits a specific capacity of 1395 mAh g -1 , superior rate performance of 727 mAh g -1 at 5 Ag -1 , and long cycle stability (796 mAh g -1 after 500 cycles at 2 Ag -1 ). The enhanced electrochemical properties of the electrodes are probably ascribed to their amorphous nature, the combination of CNTs@C that adhered and hindered the agglomeration of CoS 2 and MoS 2 as well as the enhanced electronic conductivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
NASA Astrophysics Data System (ADS)
Dwivedi, Neeraj; Dhand, Chetna; Rawal, Ishpal; Kumar, Sushil; Malik, Hitendra K.; Lakshminarayanan, Rajamani
2017-06-01
A longstanding concern in the research of amorphous carbon films is their poor electrical conductivity at room temperature which constitutes a major barrier for the development of cost effective electronic and optoelectronic devices. Here, we propose metal/carbon hybrid multijunction devices as a promising facile way to overcome room temperature electron transport issues in amorphous carbon films. By the tuning of carbon thickness and swapping metal layers, we observe giant (upto ˜7 orders) reduction of electrical resistance in metal/carbon multijunction devices with respect to monolithic amorphous carbon device. We engineer the maximum current (electrical resistance) from about 10-7 to 10-3 A (˜107 to 103 Ω) in metal (Cu or Ti)/carbon hybrid multijunction devices with a total number of 10 junctions. The introduction of thin metal layers breaks the continuity of relatively higher resistance carbon layer as well as promotes the nanostructuring of carbon. These contribute to low electrical resistance of metal/carbon hybrid multijunction devices, with respect to monolithic carbon device, which is further reduced by decreasing the thickness of carbon layers. We also propose and discuss equivalent circuit model to explain electrical resistance in monolithic carbon and metal/carbon multijunction devices. Cu/carbon multijunction devices display relatively better electrical transport than Ti/carbon devices owing to low affinity of Cu with carbon that restricts carbide formation. We also observe that in metal/carbon multijunction devices, the transport mechanism changes from Poole-Frenkel/Schottky model to the hopping model with a decrease in carbon thickness. Our approach opens a new route to develop carbon-based inexpensive electronic and optoelectronic devices.
Synthesis and Performance of Tungsten Disulfide/Carbon (WS2/C) Composite as Anode Material
NASA Astrophysics Data System (ADS)
Yuan, Zhengyong; Jiang, Qiang; Feng, Chuanqi; Chen, Xiao; Guo, Zaiping
2018-01-01
The precursors of an amorphous WS2/C composite were synthesized by a simple hydrothermal method using Na2WO4·2H2O and CH3CSNH2 as raw materials, polyethylene glycol as dispersant, and glucose as the carbon source. The as-synthesized precursors were further annealed at a low temperature in flowing argon to obtain the final materials (WS2/C composite). The structure and morphology of the WS2/C composite were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, and scanning electron microscopy. The electrochemical properties were tested by galvanostatic charge/discharge testing and alternating current (AC) impedance measurements. The results show that the as-prepared amorphous WS2/C composite features both high specific capacity and good cycling performance at room temperature within the potential window from 3.0 V to 0.01 V (versus Li+/Li) at current density of 100 mAg-1. The achieved initial discharge capacity was 1080 mAhg-1, and 786 mAhg-1 was retained after 170 cycles. Furthermore, the amorphous WS2/C composite exhibited a lower charge/discharge plateau than bare WS2, which is more beneficial for use as an anode. The cyclic voltammetry and AC impedance testing further confirmed the change in the plateau and the decrease in the charge transfer resistance in the WS2/C composite. The chemical formation process and the electrochemical mechanism of the WS2/C composite are also presented. The amorphous WS2/C composite can be used as a new anode material for future applications.
High temperature superconductivity in distinct phases of amorphous B-doped Q-carbon
NASA Astrophysics Data System (ADS)
Narayan, Jagdish; Bhaumik, Anagh; Sachan, Ritesh
2018-04-01
Distinct phases of B-doped Q-carbon are formed when B-doped and undoped diamond tetrahedra are packed randomly after nanosecond laser melting and quenching of carbon. By changing the ratio of doped to undoped tetrahedra, distinct phases of B-doped Q-carbon with concentration varying from 5.0% to 50.0% can be created. We have synthesized three distinct phases of amorphous B-doped Q-carbon, which exhibit high-temperature superconductivity following the Bardeen-Cooper-Schrieffer mechanism. The first phase (QB1) has a B-concentration ˜17 at. % (Tc = 37 K), the second phase (QB2) has a B-concentration ˜27 at. % (Tc = 55 K), and the third phase (QB3) has a B-concentration ˜45 at. % (Tc expected over 100 K). From geometrical modeling, we derive that QB1 consists of randomly packed tetrahedra, where one out of every three tetrahedra contains a B atom in the center which is sp3 bonded to four carbon atoms with a concentration of 16.6 at. %. QB2 consists of randomly packed tetrahedra, where one out of every two tetrahedra contains a B atom in the center which is sp3 bonded to four carbon atoms with a concentration of 25 at. %. QB3 consists of randomly packed tetrahedra, where every tetrahedron contains a B atom in the center which is sp3 bonded to four carbon atoms with a concentration of 50 at. %. We present detailed high-resolution TEM results on structural characterization, and EELS and Raman spectroscopy results on the bonding characteristics of B and C atoms. From these studies, we conclude that the high electronic density of states near the Fermi energy level coupled with moderate electron-phonon coupling result in high-temperature superconductivity in B-doped Q-carbon.
NASA Astrophysics Data System (ADS)
Zhou, Yun; Liu, Boyang; Shao, Yingfeng; Fan, Chunhua; Fan, Runhua; Wen, Bosheng
A highly efficient and convenient strategy is developed for the one-step in-situ synthesis of carbon encapsulated Cr2O3 nanocrystals with core-shell structure (Cr2O3@C). The explosive reaction of chromocene with ammonium persulfate in an autoclave at 200∘C is crucial for the formation of this nanostructure. The Cr2O3 nanocrystals have a diameter of 5 to 20nm, which are entirely encapsulated by the amorphous carbon shell. The Cr2O3@C anode can retain a stable reversible capacity of 397mAhg-1 after 50 cycles at a current density of 119mA g-1.
NASA Astrophysics Data System (ADS)
Rotunno, E.; Fabbri, F.; Cinquanta, E.; Kaplan, D.; Longo, M.; Lazzarini, L.; Molle, A.; Swaminathan, V.; Salviati, G.
2016-06-01
MoS2 multi-layer flakes, exfoliated from geological molybdenite, have been exposed to high dose electron irradiation showing clear evidence of crystal lattice and stoichiometry modifications. A massive surface sulfur depletion is induced together with the consequent formation of molybdenum nanoislands. It is found that a nanometric amorphous carbon layer, unwillingly deposited during the transmission electron microscope experiments, prevents the formation of the nanoislands. In the absence of the carbon layer, the formation of molybdenum grains proceeds both on the top and bottom surfaces of the flake. If carbon is present on both the surfaces then the formation of Mo grains is completely prevented.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kawasaki, Masahiro; Sompetch, Kanganit; Sarakonsri, Thapanee, E-mail: tsarakonsri@gmail.com
2015-12-15
Analytical electron microscopy has revealed the structure of particles that were synthesized by chemical reaction of GeO{sub 2} with NaBH{sub 4} in the basic solution including graphitic carbon nitride (g-C{sub 3}N{sub 4}) powders. The g-C{sub 3}N{sub 4} was arranged by recrystallization of melamine at 600 °C under N{sub 2} gas atmosphere. The samples were dried at 60 °C or 180 °C for 4 h. The g-C{sub 3}N{sub 4} was observed as lamellae of several ten nm or less in size and had an amorphous-like structure with a distorted lattice in an area as small as a few hundred pm inmore » size. The reaction product was Ge(O) particles as fine as several nm in size and composed of Ge and O atoms. Most of the particles must be of GeO{sub 2−x} with the amorphous-like structure that has also a distorted lattice in an area of a few hundred pm in size. In the sample dried at 60 °C, the particles were found to be dispersed in a wide area on the g-C{sub 3}N{sub 4} lamella. It is hard to recognize those particles in TEM images. The particles in the sample dried at 180 °C became larger and were easily observed as isolated lumps. Hence, these powders can be regarded as GeO{sub 2}/g-C{sub 3}N{sub 4} or Ge/GeO{sub 2}/g-C{sub 3}N{sub 4} nanocomposites, and expected to be applicable to anode materials for high energy Li-ion batteries due to Ge catalysis effect, accordingly. - Graphical abstract: STEM analysis of Ge(O)/(graphitic carbon nitride) nanocomposite powder. - Highlights: • Graphitic (g)-C{sub 3}N{sub 4} powder was prepared at 600 °C by recrystallization of melamine. • Ge(O) was prepared by chemical reaction in a solution including the g-C{sub 3}N{sub 4} powders. • The products can be regarded as GeO{sub 2}/g-C{sub 3}N{sub 4} or Ge/GeO{sub 2}/g-C{sub 3}N{sub 4} nanocomposites. • GeO{sub 2} was amorphous several-nm particles and g-C{sub 3}N{sub 4} was amorphous lamella of several 10 nm in size. • We expect them to be applicable for high energy Li-ion battery anode materials.« less
NASA Astrophysics Data System (ADS)
Liu, Xiaoqiang; Hao, Junying; Xie, Yuntao
2016-08-01
Polymeric amorphous carbon films were prepared by radio frequency (R.F. 13.56 MHz) magnetron sputtering deposition. The microstructure evolution of the deposited polymeric films induced by silicon (Si) and aluminum(Al) doping were scrutinized through infrared spectroscopy, multi-wavelength Raman spectroscopy, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). The comparative results show that Si doping can enhance polymerization and Al doping results in an increase in the ordered carbon clusters. Si and Al co-doping into polymeric films leads to the formation of an unusual dual nanostructure consisting of cross-linked polymer-like hydrocarbon chains and fullerene-like carbon clusters. The super-high elasticity and super-low friction coefficients (<0.002) under a high vacuum were obtained through Si and Al co-doping into the films. Unconventionally, the co-doped polymeric films exhibited a superior wear resistance even though they were very soft. The relationship between the microstructure and properties of the polymeric amorphous carbon films with different elements doping are also discussed in detail.
Xiang, Liang; Kong, Wei; Su, Jingtan; Liang, Jian; Zhang, Guiyou; Xie, Liping; Zhang, Rongqing
2014-01-01
The growth of molluscan shell crystals is generally thought to be initiated from the extrapallial fluid by matrix proteins, however, the cellular mechanisms of shell formation pathway remain unknown. Here, we first report amorphous calcium carbonate (ACC) precipitation by cellular biomineralization in primary mantle cell cultures of Pinctada fucata. Through real-time PCR and western blot analyses, we demonstrate that mantle cells retain the ability to synthesize and secrete ACCBP, Pif80 and nacrein in vitro. In addition, the cells also maintained high levels of alkaline phosphatase and carbonic anhydrase activity, enzymes responsible for shell formation. On the basis of polarized light microscopy and scanning electron microscopy, we observed intracellular crystals production by mantle cells in vitro. Fourier transform infrared spectroscopy and X-ray diffraction analyses revealed the crystals to be ACC, and de novo biomineralization was confirmed by following the incorporation of Sr into calcium carbonate. Our results demonstrate the ability of mantle cells to perform fundamental biomineralization processes via amorphous calcium carbonate, and these cells may be directly involved in pearl oyster shell formation. PMID:25405357
Plasma-deposited amorphous hydrogenated carbon films and their tribological properties
NASA Technical Reports Server (NTRS)
Miyoshi, Kazuhisa; Pouch, John J.; Alterovitz, Samuel A.
1989-01-01
Recent work on the properties of diamondlike carbon films and their dependence on preparation conditions are reviewed. The results of the study indicate that plasma deposition enables one to deposit a variety of amorphous hydrogenated carbon (a-C:H ) films exhibiting more diamondlike behavior to more graphitic behavior. The plasma-deposited a-C:H can be effectively used as hard, wear-resistant, and protective lubricating films on ceramic materials such as Si(sub 3)N(sub 4) under a variety of environmental conditions such as moist air, dry nitrogrn, and vacuum.
NASA Astrophysics Data System (ADS)
Taer, E.; Iwantono, Yulita, M.; Taslim, R.; Subagio, A.; Salomo, Deraman, M.
2013-09-01
In this paper, a composite electrode was prepared from a mixture of activated carbon derived from precarbonization of cassava peel (CP) and carbon nanotubes (CNTs). The activated carbon was produced by pyrolysis process using ZnCl2 as an activation agent. A N2 adsorption-desorption analysis for the sample indicated that the BET surface area of the activated carbon was 1336 m2 g-1. Difference percentage of CNTs of 0, 5, 10, 15 and 20% with 5% of PVDF binder were added into CP based activated carbon in order to fabricate the composite electrodes. The morphology and structure of the composite electrodes were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The SEM image observed that the distribution of CNTs was homogeneous between carbon particles and the XRD pattern shown the amorphous structure of the sample. The electrodes were fabricated for supercapacitor cells with 316L stainless steel as current collector and 1 M sulfuric acid as electrolyte. An electrochemical characterization was performed by using an electrochemical impedance spectroscopy (EIS) method using a Solatron 1286 instrument and the addition of CNTs revealed to improve the resistant and capacitive properties of supercapacitor cell.
NASA Astrophysics Data System (ADS)
Huang, Zan; Luo, Peifang; Wang, Daxiang
2017-03-01
Core-shell structured LiFePO4/C1 cathode material is synthesized via a rapid microwave irradiation route using ethylene diamine tetraacetic acid (EDTA) as the novel carbon source. XRD results reveal that all the patterns can be indexed as the olivine-type structured LiFePO4 with the space group of Pnma. TEM images show that the obtained carbon is an amorphous layer with a thickness of about 3-4 nm. When the LiFePO4/C1 used as cathode material for lithium-ion battery, it delivers an initial discharge capacity of 163.1 mAh g-1 at 0.1 C which is about 96% of the theoretical capacity. Moreover, it also shows excellent rate performance and good cycle stability due to the enhanced electronic conductivity as proved by the electrochemical impedance spectroscopy (EIS). Thus, this carbon decorated LiFePO4 composite synthesized via the rapid microwave irradiation method is a promising cathode material for high-performance lithium-ion battery.
Hierarchical Model for the Analysis of Scattering Data of Complex Materials
Oyedele, Akinola; Mcnutt, Nicholas W.; Rios, Orlando; ...
2016-05-16
Interpreting the results of scattering data for complex materials with a hierarchical structure in which at least one phase is amorphous presents a significant challenge. Often the interpretation relies on the use of large-scale molecular dynamics (MD) simulations, in which a structure is hypothesized and from which a radial distribution function (RDF) can be extracted and directly compared against an experimental RDF. This computationally intensive approach presents a bottleneck in the efficient characterization of the atomic structure of new materials. Here, we propose and demonstrate an approach for a hierarchical decomposition of the RDF in which MD simulations are replacedmore » by a combination of tractable models and theory at the atomic scale and the mesoscale, which when combined yield the RDF. We apply the procedure to a carbon composite, in which graphitic nanocrystallites are distributed in an amorphous domain. We compare the model with the RDF from both MD simulation and neutron scattering data. Ultimately, this procedure is applicable for understanding the fundamental processing-structure-property relationships in complex magnetic materials.« less
Effect of dose and size on defect engineering in carbon cluster implanted silicon wafers
NASA Astrophysics Data System (ADS)
Okuyama, Ryosuke; Masada, Ayumi; Shigematsu, Satoshi; Kadono, Takeshi; Hirose, Ryo; Koga, Yoshihiro; Okuda, Hidehiko; Kurita, Kazunari
2018-01-01
Carbon-cluster-ion-implanted defects were investigated by high-resolution cross-sectional transmission electron microscopy toward achieving high-performance CMOS image sensors. We revealed that implantation damage formation in the silicon wafer bulk significantly differs between carbon-cluster and monomer ions after implantation. After epitaxial growth, small and large defects were observed in the implanted region of carbon clusters. The electron diffraction pattern of both small and large defects exhibits that from bulk crystalline silicon in the implanted region. On the one hand, we assumed that the silicon carbide structure was not formed in the implanted region, and small defects formed because of the complex of carbon and interstitial silicon. On the other hand, large defects were hypothesized to originate from the recrystallization of the amorphous layer formed by high-dose carbon-cluster implantation. These defects are considered to contribute to the powerful gettering capability required for high-performance CMOS image sensors.
NASA Astrophysics Data System (ADS)
Ji, Xiaoyu; Cheng, Hiu Yan; Grede, Alex J.; Molina, Alex; Talreja, Disha; Mohney, Suzanne E.; Giebink, Noel C.; Badding, John V.; Gopalan, Venkatraman
2018-04-01
Conformally coating textured, high surface area substrates with high quality semiconductors is challenging. Here, we show that a high pressure chemical vapor deposition process can be employed to conformally coat the individual fibers of several types of flexible fabrics (cotton, carbon, steel) with electronically or optoelectronically active materials. The high pressure (˜30 MPa) significantly increases the deposition rate at low temperatures. As a result, it becomes possible to deposit technologically important hydrogenated amorphous silicon (a-Si:H) from silane by a simple and very practical pyrolysis process without the use of plasma, photochemical, hot-wire, or other forms of activation. By confining gas phase reactions in microscale reactors, we show that the formation of undesired particles is inhibited within the microscale spaces between the individual wires in the fabric structures. Such a conformal coating approach enables the direct fabrication of hydrogenated amorphous silicon-based Schottky junction devices on a stainless steel fabric functioning as a solar fabric.
NASA Technical Reports Server (NTRS)
Lamontia, Mark A.; Gruber, Mark B.; Jensen, Brian J.
2006-01-01
Thermoplastic laminates in situ consolidated via tape or tow placement require full mechanical properties. Realizing full properties requires resin crystallinity to be controlled - partial crystallinity leads to unacceptably low laminate compression properties. There are two approaches: utilize an amorphous matrix resin; or place material made from a semi-crystalline resin featuring kinetics faster than the process. In this paper, a matrix resin evaluation and trade study was completed with commercial and NASA amorphous polyimides on the one hand, and with PEKK mixed with POSS nanoparticles for accelerated crystallinity growth on the other. A new thermoplastic impregnated material, 6 mm wide (0.25-in) AS-4 carbon/LaRC(TradeMark)8515 dry polyimide tow, was fabricated. Since LaRC(TradeMark)8515 is fully amorphous, it attains full properties following in situ consolidation, with no post processing required to build crystallinity. The tow in situ processing was demonstrated via in situ thermoplastic filament winding it into rings.
Dutta, Arghya; Wong, Raymond A; Park, Woonghyeon; Yamanaka, Keisuke; Ohta, Toshiaki; Jung, Yousung; Byon, Hye Ryung
2018-02-14
The major challenge facing lithium-oxygen batteries is the insulating and bulk lithium peroxide discharge product, which causes sluggish decomposition and increasing overpotential during recharge. Here, we demonstrate an improved round-trip efficiency of ~80% by means of a mesoporous carbon electrode, which directs the growth of one-dimensional and amorphous lithium peroxide. Morphologically, the one-dimensional nanostructures with small volume and high surface show improved charge transport and promote delithiation (lithium ion dissolution) during recharge and thus plays a critical role in the facile decomposition of lithium peroxide. Thermodynamically, density functional calculations reveal that disordered geometric arrangements of the surface atoms in the amorphous structure lead to weaker binding of the key reaction intermediate lithium superoxide, yielding smaller oxygen reduction and evolution overpotentials compared to the crystalline surface. This study suggests a strategy to enhance the decomposition rate of lithium peroxide by exploiting the size and shape of one-dimensional nanostructured lithium peroxide.
Fast-moving dislocations trigger flash weakening in carbonate-bearing faults during earthquakes
Spagnuolo, Elena; Plümper, Oliver; Violay, Marie; Cavallo, Andrea; Di Toro, Giulio
2015-01-01
Rupture fronts can cause fault displacement, reaching speeds up to several ms−1 within a few milliseconds, at any distance away from the earthquake nucleation area. In the case of silicate-bearing rocks the abrupt slip acceleration results in melting at asperity contacts causing a large reduction in fault frictional strength (i.e., flash weakening). Flash weakening is also observed in experiments performed in carbonate-bearing rocks but evidence for melting is lacking. To unravel the micro-physical mechanisms associated with flash weakening in carbonates, experiments were conducted on pre-cut Carrara marble cylinders using a rotary shear apparatus at conditions relevant to earthquakes propagation. In the first 5 mm of slip the shear stress was reduced up to 30% and CO2 was released. Focused ion beam, scanning and transmission electron microscopy investigations of the slipping zones reveal the presence of calcite nanograins and amorphous carbon. We interpret the CO2 release, the formation of nanograins and amorphous carbon to be the result of a shock-like stress release associated with the migration of fast-moving dislocations. Amorphous carbon, given its low friction coefficient, is responsible for flash weakening and promotes the propagation of the seismic rupture in carbonate-bearing fault patches. PMID:26552964
Wu, Ying; Liu, Zheng; Zhong, Xiongwu; Cheng, Xiaolong; Fan, Zhuangjun; Yu, Yan
2018-03-01
The red P anode for sodium ion batteries has attracted great attention recently due to the high theoretical capacity, but the poor intrinsic electronic conductivity and large volume expansion restrain its widespread applications. Herein, the red P is successfully encapsulated into the cube shaped sandwich-like interconnected porous carbon building (denoted as P@C-GO/MOF-5) via the vaporization-condensation method. Superior cycling stability (high capacity retention of about 93% at 2 A g -1 after 100 cycles) and excellent rate performance (502 mAh g -1 at 10 A g -1 ) can be obtained for the P@C-GO/MOF-5 electrode. The superior electrochemical performance can be ascribed to the successful incorporation of red P into the unique carbon matrix with large surface area and pore volume, interconnected porous structure, excellent electronic conductivity and superior structural stability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
NASA Technical Reports Server (NTRS)
Buckley, D. H.
1973-01-01
Sliding friction experiments were conducted with amorphous and fully graphitized carbons sliding on copper and on films of chromium and aluminum on copper. Auger emission spectroscopy analysis was used to monitor carbon transfer to the metal surfaces. Friction and wear were also measured. Metal surfaces were examined both in the clean state and with normal oxides present. Results indicate that different metals have an important effect on friction, wear, and transfer characteristics. With amorphous carbon, the least chemically active metal gave the highest wear and amount of carbon transfer. Both forms of carbon gave lower friction and wear and lower transfer rates when in contact with clean, as opposed to oxide-covered, chromium surfaces. With copper, the reverse was true; cleaning was detrimental.
Park, Sangeun; Song, Wooseok; Kim, Yooseok; Song, Inkyung; Kim, Sung Hwan; Lee, Su Il; Jang, Sung Won; Parkl, Chong-Yun
2014-07-01
When vertically aligned carbon nanotubes (VACNTs) are synthesized by thermal chemical vapor deposition (TCVD), their structural features such as height and density can be determined by TCVD growth conditions. In this study we investigated the effect of growth pressure on the structural features of VACNTs. Changes in growth pressure significantly affected the height, density, and crystalinity of synthesized VACNTs. In addition, we suggest that the growth termination of VACNTs could be due to the lack of carbon feedstock supply to the center of the VACNT film induced by the pressure-dependent adsorption of amorphous carbon at the edge of the VACNT film. In addition, the field emission characteristics of the VACNT film were carried out. The turn-on voltage of the VACNT film was 1.62 V/microm and the field enhancement factor (beta) was 2478. These results provide useful information for practical applications of VACNTs, such as field emission display and X-ray source.
NASA Astrophysics Data System (ADS)
Wu, Ling; Hu, Yong; Zhang, Xiaoping; Liu, Jiequn; Zhu, Xing; Zhong, Shengkui
2018-01-01
Hollow sphere structure Na2MnPO4F/C composite is synthesized through spray drying, following in-situ pyrolytic carbon coating process. XRD results indicate that the well crystallized composite can be successfully synthesized, and no other impurity phases are detected. SEM and TEM results reveal that the Na2MnPO4F/C samples show intact hollow spherical architecture, and the hollow spherical shells with an average thickness of 150 nm-250 nm are composed of nanosized primary particles. Furthermore, the amorphous carbon layer is uniformly coated on the surface of the hollow sphere, and the nanosized Na2MnPO4F particles are well embedded in the carbon networks. Consequently, the hollow sphere structure Na2MnPO4F/C shows enhanced electrochemical performance. Especially, it is the first time that the obvious potential platforms (∼3.6 V) are observed during the charge and discharge process at room temperature.
NASA Astrophysics Data System (ADS)
Dinca-Balan, Virginia; Vladoiu, Rodica; Mandes, Aurelia; Prodan, Gabriel
2017-11-01
The synthesis of Ag, Mg and Si nanocrystalline, embedded in a hydrogen-free amorphous carbon (a-C) matrix, deposited by a high vacuum and free buffer gas technique, were investigated. The films with compact structures and extremely smooth surfaces were prepared using the thermionic vacuum arc method in one electron gun configuration, on glass and silicon substrates. The surface morphology and wettability of the obtained multifunctional thin films were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and free surface energy (FSE) by See System. The results from the TEM measurements show how the Ag, Mg and Si interacted with carbon and the influence these materials have on the thin film structure formation and the grain size distribution. SEM correlated with EDX results reveal a very precise comparative study, regarding the quantity of the elements that morphed into carbides nanostructures. Also, the FSE results prove how different materials in combination with carbon can make changes to the surface properties.
NASA Astrophysics Data System (ADS)
Guan, Jiwen; Daljeet, Roshan; Kieran, Arielle; Song, Yang
2018-06-01
Conjugated polymers are prominent semiconductors that have unique electric conductivity and photoluminescence. Synthesis of conjugated polymers under high pressure is extremely appealing because it does not require a catalyst or solvent used in conventional chemical methods. Transformation of acetylene and many of its derivatives to conjugated polymers using high pressure has been successfully achieved, but not with dimethyl acetylene (DMA). In this work, we present a high-pressure study on solid DMA using a diamond anvil cell up to 24.4 GPa at room temperature characterized by in situ Fourier transform infrared and Raman spectroscopy. Our results show that solid DMA exists in a phase II crystal structure and is stable up to 12 GPa. Above this pressure, amorphization was initiated and the process was completed at 24.4 GPa. The expected polymeric transformation was not evident upon compression, but only observed upon decompression from a threshold compression pressure (e.g. 14.4 GPa). In situ florescence measurements suggest excimer formation via crystal defects, which induces the chemical reactions. The vibrational spectral analysis suggests the products contain the amorphous poly(DMA) and possibly additional amorphous hydrogenated carbon material.
Guan, Jiwen; Daljeet, Roshan; Kieran, Arielle; Song, Yang
2018-06-06
Conjugated polymers are prominent semiconductors that have unique electric conductivity and photoluminescence. Synthesis of conjugated polymers under high pressure is extremely appealing because it does not require a catalyst or solvent used in conventional chemical methods. Transformation of acetylene and many of its derivatives to conjugated polymers using high pressure has been successfully achieved, but not with dimethyl acetylene (DMA). In this work, we present a high-pressure study on solid DMA using a diamond anvil cell up to 24.4 GPa at room temperature characterized by in situ Fourier transform infrared and Raman spectroscopy. Our results show that solid DMA exists in a phase II crystal structure and is stable up to 12 GPa. Above this pressure, amorphization was initiated and the process was completed at 24.4 GPa. The expected polymeric transformation was not evident upon compression, but only observed upon decompression from a threshold compression pressure (e.g. 14.4 GPa). In situ florescence measurements suggest excimer formation via crystal defects, which induces the chemical reactions. The vibrational spectral analysis suggests the products contain the amorphous poly(DMA) and possibly additional amorphous hydrogenated carbon material.
Fracture of Carbon Nanotube - Amorphous Carbon Composites: Molecular Modeling
NASA Technical Reports Server (NTRS)
Jensen, Benjamin D.; Wise, Kristopher E.; Odegard, Gregory M.
2015-01-01
Carbon nanotubes (CNTs) are promising candidates for use as reinforcements in next generation structural composite materials because of their extremely high specific stiffness and strength. They cannot, however, be viewed as simple replacements for carbon fibers because there are key differences between these materials in areas such as handling, processing, and matrix design. It is impossible to know for certain that CNT composites will represent a significant advance over carbon fiber composites before these various factors have been optimized, which is an extremely costly and time intensive process. This work attempts to place an upper bound on CNT composite mechanical properties by performing molecular dynamics simulations on idealized model systems with a reactive forcefield that permits modeling of both elastic deformations and fracture. Amorphous carbon (AC) was chosen for the matrix material in this work because of its structural simplicity and physical compatibility with the CNT fillers. It is also much stiffer and stronger than typical engineering polymer matrices. Three different arrangements of CNTs in the simulation cell have been investigated: a single-wall nanotube (SWNT) array, a multi-wall nanotube (MWNT) array, and a SWNT bundle system. The SWNT and MWNT array systems are clearly idealizations, but the SWNT bundle system is a step closer to real systems in which individual tubes aggregate into large assemblies. The effect of chemical crosslinking on composite properties is modeled by adding bonds between the CNTs and AC. The balance between weakening the CNTs and improving fiber-matrix load transfer is explored by systematically varying the extent of crosslinking. It is, of course, impossible to capture the full range of deformation and fracture processes that occur in real materials with even the largest atomistic molecular dynamics simulations. With this limitation in mind, the simulation results reported here provide a plausible upper limit on achievable CNT composite properties and yield some insight on the influence of processing conditions on the mechanical properties of CNT composites.
Wear and Friction Behavior of Metal Impregnated Microporous Carbon Composites
NASA Technical Reports Server (NTRS)
Goller, Gultekin; Koty, D. P.; Tewari, S. N.; Singh, M.; Tekin, A.
1996-01-01
Metal-matrix composites have been prepared by pressure-infiltration casting of copper-base alloy melts into microporous carbon preforms. The carbon preforms contained varying proportions of amorphous carbon and graphite. Load dependence of the wear and friction behavior of the composite pins has been examined under ambient conditions against cast-iron plates, using a pin-on-plate reciprocating wear tester. The wear resistance of the composite is significantly improved, as compared with the base alloy. Contrary to the normally expected behavior, the addition of graphite to the amorphous carbon does not reduce the friction coefficient, especially at high loads. The wear and friction behavior of the composites is very sensitive to the size and distribution of the microstructural constituents.
Surface and corrosion characteristics of carbon plasma implanted and deposited nickel-titanium alloy
DOE Office of Scientific and Technical Information (OSTI.GOV)
Poon, R.W.Y.; Liu, X.Y.; Chung, C.Y.
2005-05-01
Nickel-titanium shape memory alloys (NiTi) are potentially useful in orthopedic implants on account of their super-elastic and shape memory properties. However, the materials are prone to surface corrosion and the most common problem is out-diffusion of harmful Ni ions from the substrate into body tissues and fluids. In order to improve the corrosion resistance and related surface properties, we used the technique of plasma immersion ion implantation and deposition to deposit an amorphous hydrogenated carbon coating onto NiTi and implant carbon into NiTi. Both the deposited amorphous carbon film and carbon plasma implanted samples exhibit much improved corrosion resistances andmore » surface mechanical properties and possible mechanisms are suggested.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pashkin, E. Y.; Pankov, A. M.; Kulnitskiy, B. A.
The behavior of multiwall carbon nanotubes under a high pressure (up to 55 GPa) combined with shear deformation was studied by experimental and theoretical methods. The unexpectedly high stability of the nanotubes' structure under high stresses was observed. After the pressure was released, we observed that the nanotubes had restored their shapes. Atomistic simulations show that the hydrostatic and shear stresses affect the nanotubes' structure in a different way. It was found that the shear stress load in the multiwall nanotubes' outer walls can induce their connection and formation of an amorphized sp{sup 3}-hybridized region but internal core keeps the tubularmore » structure.« less
Kadirova, Zukhra C; Hojamberdiev, Mirabbos; Katsumata, Ken-Ichi; Isobe, Toshihiro; Matsushita, Nobuhiro; Nakajima, Akira; Sharipov, Khasan; Okada, Kiyoshi
2014-01-01
The spherical granular activated carbon-carbon composites (GAC-Fe) with different iron oxide contents (Fe mass% = 0.6-10) were prepared by a pore volume impregnation method. The X-ray diffraction (XRD), scanning electron microscopy (SEM), and N2-adsorption results confirm the presence of amorphous iron oxide, pyrolytic carbon, and graphitized globular carbon nanoparticles covered with amorphous carbon in the CAG-Fe. The rate of photodegradation of methylene blue (MB) in aqueous solution under UV light in the presence of oxalic acid correlates with porosity of the prepared materials. The total MB removal includes the combination of adsorption and photodegradation without the addition of H2O2. The results of total organic carbon (TOC) analysis reveal that the decolorization of MB in aqueous solution containing oxalic acid corresponds to the decomposition of organic compounds to CO2 and H2O.
Bioinspired mineralization of inorganics from aqueous media controlled by synthetic polymers.
Gorna, Katarzyna; Muñoz-Espí, Rafael; Gröhn, Franziska; Wegner, Gerhard
2007-02-12
The formation of inorganic structures in nature is commonly controlled by biogenic macromolecules. The understanding of mineralization phenomena and the nucleation and growth mechanisms involved is still a challenge in science but also of great industrial interest. This article focuses on the formation and mineralization of two archetypical inorganic materials: zinc oxide and amorphous calcium carbonate (ACC). Zinc oxide is selected as a model compound to investigate the role that polymers play in mineralization. Most of the effort has been devoted to the investigation of the effects of double-hydrophilic block and graft copolymers. Recent work has demonstrated that latex particles synthesized by miniemulsion polymerization, properly functionalized by various chemical groups, have similar effects to conventional block copolymers and are excellently suited for morphology control of ZnO crystals. Latex particles might serve as analogues of natural proteins in biomineralization. The second example presented, ACC, addresses the issue of whether this amorphous phase is an intermediate in the biomineralization of calcite, vaterite, or aragonite. Conditions under which amorphous calcium carbonate can be obtained as nanometer-sized spheres as a consequence of a liquid-liquid phase segregation are presented. Addition of specific block copolymers allows control of the particle size from the micrometer to the submicrometer length scale. The physical properties of novel materials synthesized from concentrated solution and their potential applications as a filler of polymers are also discussed.
NASA Astrophysics Data System (ADS)
Abedi, Mohammad; Abdollah-zadeh, Amir; Bestetti, Massimiliano; Vicenzo, Antonello; Serafini, Andrea; Movassagh-Alanagh, Farid
2018-06-01
In the present study, the effects of phase transformations on the structure and mechanical properties of TiSiCN coatings were investigated. TiSiCN nanocomposite coatings were deposited on AISI H13 hot-work tool steel by a pulsed direct current plasma-enhanced chemical vapor deposition process at 350 or 500 °C, using TiCl4 and SiCl4 as the precursors of Ti and Si, respectively, in a CH4/N2/H2/Ar plasma as the source of carbon and nitrogen and reducing environment. Some samples deposited at 350 °C were subsequently annealed at 500 °C under Ar atmosphere. Super hard self-lubricant TiSiCN coatings, having nanocomposite structure consisting of TiCN nanocrystals and amorphous carbon particles embedded in an amorphous SiCNx matrix, formed through spinodal decomposition in the specimens deposited or annealed at 500 °C. In addition, it was revealed that either uncomplete or relatively coarse phase segregation of titanium compounds was achieved during deposition at 350 °C and 500 °C, respectively. On the contrary, by deposition at 350 °C followed by annealing at 500 °C, a finer structure was obtained with a sensible improvement of the mechanical properties of coatings. Accordingly, the main finding of this work is that significant enhancement in key properties of TiSiCN coatings, such as hardness, adhesion and friction coefficient, can be obtained by deposition at low temperature and subsequent annealing at higher temperature, thanks to the formation of a fine grained nanocomposite structure.
Biomineral nanoparticles are space-filling.
Yang, Li; Killian, Christopher E; Kunz, Martin; Tamura, Nobumichi; Gilbert, P U P A
2011-02-01
Sea urchin biominerals have been shown to form from aggregating nanoparticles of amorphous calcium carbonate (ACC), which then crystallize into macroscopic single crystals of calcite. Here we measure the surface areas of these biominerals and find them to be comparable to those of space-filling macroscopic geologic calcite crystals. These biominerals differ from synthetic mesocrystals, which are invariably porous. We propose that space-filling ACC is the structural precursor for echinoderm biominerals.
NASA Astrophysics Data System (ADS)
Guan, J. J.; Wang, H. Q.; Qin, L. Z.; Liao, B.; Liang, H.; Li, B.
2017-04-01
The CrCN coatings were fabricated onto Si (1 1 1) wafers and SUS304 stainless steel plates using filtered cathodic vacuum arc deposition (FCVAD) technique under different flow ratios of N2/C2H2 gas mixture. The morphology, crystalline structure and chemical composition of the coatings were characterized. It was found that the grain size reduce with increasing carbon content, which makes the CrCN coatings refined and smooth. The quasi-one-dimensional carbolite phase was also found in CrN host lattice with C2H2 content ranging from 5% to 20%, and it will be evolved into amorphous carbon and amorphous CNx phases as C2H2 content exceeds 20%. Moreover, we examined the mechanical and tribological properties of the CrCN coatings, and the experimental results confirmed that the friction coefficient of the coatings descend to the lowest value as 0.39 with 30% C2H2 content, due to the graphite (sp2 Csbnd C) phase embed in CrN host lattice; while the chromium carbon (Cr3C2) and diamond (sp3 Csbnd C) phases may give rise to the increase of the coating hardness with the highest value at 23.97 GPa under 20% C2H2 content.
Thermal conductivity and nanocrystalline structure of platinum deposited by focused ion beam.
Alaie, Seyedhamidreza; Goettler, Drew F; Jiang, Ying-Bing; Abbas, Khawar; Baboly, Mohammadhosein Ghasemi; Anjum, D H; Chaieb, S; Leseman, Zayd C
2015-02-27
Pt deposited by focused ion beam (FIB) is a common material used for attachment of nanosamples, repair of integrated circuits, and synthesis of nanostructures. Despite its common use little information is available on its thermal properties. In this work, Pt deposited by FIB is characterized thermally, structurally, and chemically. Its thermal conductivity is found to be substantially lower than the bulk value of Pt, 7.2 W m(-1) K(-1) versus 71.6 W m(-1) K(-1) at room temperature. The low thermal conductivity is attributed to the nanostructure of the material and its chemical composition. Pt deposited by FIB is shown, via aberration corrected TEM, to be a segregated mix of nanocrystalline Pt and amorphous C with Ga and O impurities. Ga impurities mainly reside in the Pt while O is homogeneously distributed throughout. The Ga impurity, small grain size of the Pt, and the amorphous carbon between grains are the cause for the low thermal conductivity of this material. Since Pt deposited by FIB is a common material for affixing samples, this information can be used to assess systematic errors in thermal characterization of different nanosamples. This application is also demonstrated by thermal characterization of two carbon nanofibers and a correction using the reported thermal properties of the Pt deposited by FIB.
NASA Astrophysics Data System (ADS)
Kurniati, M.; Nurhayati, D.; Maddu, A.
2017-03-01
The important part of fuel cell is the gas diffusion layer who made from carbon based material porous and conductive. The main goal of this research is to obtain carbon material from sugarcane bagasse with hydrothermal carbonization and chemical-physics activation. There were two step methods in this research. The first step was sample preparation which consisted of prepare the materials, hydrothermal carbonization and chemical-physics activation. The second one was analyze character of carbon using EDS, SEM, XRD, and LCR meter. The amount of carbon in sugarcane bagasse-carbon was about 85%-91.47% with pore morphology that already form. The degree of crystallinity of sugarcane bagasse carbon was about 13.06%-20.89%, leaving the remain as the amorphous phase. Electrical conductivity was about 5.36 x 10-2 Sm-1 - 1.11 Sm-1. Sugarcane bagasse-carbon has porous characteristic with electrical conductivity property as semiconductor. Sugarcane bagasse-carbon with hydrothermal carbonization potentially can be used as based material for fuel cell if only time of hydrothermal carbonization hold is increased.
Photo-oxidation of polymer-like amorphous hydrogenated carbon under visible light illumination
Baxamusa, Salmaan; Laurence, Ted; Worthington, Matthew; ...
2015-11-10
Amorphous hydrogenated carbon (a-C:H), a polymer-like network typically synthesized by plasma chemical vapor deposition, has long been understood to exhibit optical absorption of visible light (λ > 400 nm). In this report we explain that this absorption is accompanied by rapid photo-oxidation (within minutes) that behaves in most respects like classic polymer photo-oxidation with the exception that it occurs under visible light illumination rather than ultraviolet illumination.
NASA Astrophysics Data System (ADS)
Li, Xiao; Tian, Xiaodong; Yang, Tao; Wang, Wei; Song, Yan; Guo, Quangui; Liu, Zhanjun
2018-05-01
Inferior cycling stability and rate performance respectively caused by rigorous volume change and poor electrical conductivity were the main challenge of state-of-the-art Silicon-based electrode. In this work, silylated functionalized exfoliated graphite oxide (EGO)/silicon@amorphous carbon (3-APTS-EGO/Si@C) was synthesized by adopting silane as intermediate to connect Si particles with EGO sheets followed by introduction of amorphous carbon. The result suggested that 3-Aminopropyltriethoxysilan connected the EGO sheets and Si nanoparticles via covalent bonds. Owing to the strong covalent interaction and the synergistic effect between the silicon, EGO sheets and amorphous carbon, 3-APTS-EGO/Si@C composite possessed a high capacity of 774 mAh g-1 even after 450 cycles at 0.4 A g-1 with the retention capacity of 97%. This work also provided an effective strategy to improve the long cycling life performance of Si-based electrode.
Interfacial Li-ion localization in hierarchical carbon anodes
McNutt, Nicholas W.; Rios, Orlando; Maroulas, Vasileios; ...
2016-10-24
An understanding of the nanoscale structure and energetics of carbon composites is critical for their applications in electric energy storage. Here, we study the properties of carbon anodes synthesized from low-cost renewable lignin biopolymers for use in energy storage applications such as Li-ion batteries. The anodes possess both nanoscale and mesoscale order, consisting of carbon nanocrystallites distributed within an amorphous carbon matrix. Molecular dynamics simulations of an experimentally validated model of the anode is used to elucidate the nature of Li-ion storage. We report the discovery of a novel mechanism of Li-ion storage, one in which Li+ is not intercalatedmore » between layers of carbon (as is the case in graphitic anodes), but rather is localized at the interface of crystalline carbon domains. In particular, the effects of Li-ion binding energy on the Li-Li, Li-H, and Li-C pair distribution functions are revealed, along with the effect on charge distribution. As a result, the atomic environments surrounding the Li-ions are grouped on the basis of ion energy and then convolved into archetypal structural motifs that reveal deep insight into the geometry of ion localization in disordered systems.« less
Distortion of Local Atomic Structures in Amorphous Ge-Sb-Te Phase Change Materials
NASA Astrophysics Data System (ADS)
Hirata, A.; Ichitsubo, T.; Guan, P. F.; Fujita, T.; Chen, M. W.
2018-05-01
The local atomic structures of amorphous Ge-Sb-Te phase-change materials have yet to be clarified and the rapid crystal-amorphous phase change resulting in distinct optical contrast is not well understood. We report the direct observation of local atomic structures in amorphous Ge2Sb2Te5 using "local" reverse Monte Carlo modeling dedicated to an angstrom-beam electron diffraction analysis. The results corroborated the existence of local structures with rocksalt crystal-like topology that were greatly distorted compared to the crystal symmetry. This distortion resulted in the breaking of ideal octahedral atomic environments, thereby forming local disordered structures that basically satisfied the overall amorphous structure factor. The crystal-like distorted octahedral structures could be the main building blocks in the formation of the overall amorphous structure of Ge-Sb-Te.
NASA Astrophysics Data System (ADS)
Erich, M.; Kokkoris, M.; Fazinić, S.; Petrović, S.
2018-02-01
This work reports on the induced diamond crystal amorphization by 4 MeV carbon ions implanted in the 〈1 0 0〉 oriented crystal and its determination by application of RBS/C and EBS/C techniques. The spectra from the implanted samples were recorded for 1.2, 1.5, 1.75 and 1.9 MeV protons. For the two latter ones the strong resonance of the nuclear elastic scattering 12C(p,p0)12C at 1.737 MeV was explored. The backscattering channeling spectra were successfully fitted and the ion beam induced crystal amorphization depth profile was determined using a phenomenological approach, which is based on the properly defined Gompertz type dechanneling functions for protons in the 〈1 0 0〉 diamond crystal channels and the introduction of the concept of ion beam amorphization, which is implemented through our newly developed computer code CSIM.
Thermal reaction of sonochemically prepared amorphous Fe/C
NASA Astrophysics Data System (ADS)
Miyatani, R.; Kobayashi, Y.; Yamada, Y.
2017-11-01
An amorphous iron/carbon mixture was prepared by sonolysis of ferrocene in diphenylmethane. Heating of the amorphous mixture at 900 or 1200 °C produced nanoparticles, which were then analyzed using Mössbauer spectroscopy, X-ray diffraction, and transmission electron microscopy. The nanoparticles obtained after heating were spherical with diameters of about 50 nm. The sample obtained after heating at 900 °C consisted of α-Fe and Fe 3C, whereas the sample obtained after heating at 1200 °C consisted of α-Fe and γ-Fe. The reaction of the mixture during the heating process was accompanied by the formation of carbon nanotubes catalyzed by the iron or iron carbide nanoparticles.
Time Dependent Structural Evolution of Porous Organic Cage CC3
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lucero, Jolie; Elsaidi, Sameh; Anderson, Ryther
Porous organic cage compounds are emerged with remarkable structural diversity and functionality that have applications in gas separation, catalysis and energy storage. Fundamental understanding of nucleation and growth of such materials have significant implications for understanding molecularly directed self-assembly phenomena. Herein we followed the structural evolution of a prototypical type of porous organic cage, CC3 as a function of synthesis time. Three distinctive crystal formation stages were identified: at short synthesis times, a rapid crystal growth stage in which amorphous agglomerates transformed into larger irregular particles was observed. At intermediate synthesis times, a decrease in crystal size over time wasmore » observed presumably due to crystal fragmentation, redissolution and/or homogeneous nucleation led. Finally, at longer synthesis times, a regrowth process was observed in which particles coalesced through Ostwald ripening leading to a continuous increase in crystal size. Molecular simulation studies, based on the construction of in silico CC3 models and simulation of XRD patterns and nitrogen isotherms, confirm the samples at different synthesis times to be a mixture of CC3α and CC3 amorphous phases. The CC3α phase is found to contract at different synthesis times, and the amorphous phase is found to essentially disappear at the longest synthesis time. Nitrogen and carbon dioxide adsorption properties of these CC3 phases were evaluated, and were highly dependent on synthesis time.« less
Horowitz, Yonatan; Han, Hui-Ling; Soto, Fernando A; Ralston, Walter T; Balbuena, Perla B; Somorjai, Gabor A
2018-02-14
Fluorinated compounds are added to carbonate-based electrolyte solutions in an effort to create a stable solid electrolyte interphase (SEI). The SEI mitigates detrimental electrolyte redox reactions taking place on the anode's surface upon applying a potential in order to charge (discharge) the lithium (Li) ion battery. The need for a stable SEI is dire when the anode material is silicon as silicon cracks due to its expansion and contraction upon lithiation and delithiation (charge-discharge) cycles, consequently limiting the cyclability of a silicon-based battery. Here we show the molecular structures for ethylene carbonate (EC): fluoroethylene carbonate (FEC) solutions on silicon surfaces by sum frequency generation (SFG) vibrational spectroscopy, which yields vibrational spectra of molecules at interfaces and by ab initio molecular dynamics (AIMD) simulations at open circuit potential. Our AIMD simulations and SFG spectra indicate that both EC and FEC adsorb to the amorphous silicon (a-Si) through their carbonyl group (C═O) oxygen atom with no further desorption. We show that FEC additives induce the reorientation of EC molecules to create an ordered, up-right orientation of the electrolytes on the Si surface. We suggest that this might be helpful for Li diffusion under applied potential. Furthermore, FEC becomes the dominant species at the a-Si surface as the FEC concentration increases above 20 wt %. Our finding at open circuit potential can now initiate additive design to not only act as a sacrificial compound but also to produce a better suited SEI for the use of silicon anodes in the Li-ion vehicular industry.
Impact of laser power density on tribological properties of Pulsed Laser Deposited DLC films
NASA Astrophysics Data System (ADS)
Gayathri, S.; Kumar, N.; Krishnan, R.; AmirthaPandian, S.; Ravindran, T. R.; Dash, S.; Tyagi, A. K.; Sridharan, M.
2013-12-01
Fabrication of wear resistant and low friction carbon films on the engineered substrates is considered as a challenging task for expanding the applications of diamond-like carbon (DLC) films. In this paper, pulsed laser deposition (PLD) technique is used to deposit DLC films on two different types of technologically important class of substrates such as silicon and AISI 304 stainless steel. Laser power density is one of the important parameter used to tailor the fraction of sp2 bonded amorphous carbon (a-C) and tetrahedral amorphous carbon (ta-C) made by sp3 domain in the DLC film. The I(D)/I(G) ratio decreases with the increasing laser power density which is associated with decrease in fraction of a-C/ta-C ratio. The fraction of these chemical components is quantitatively analyzed by EELS which is well supported to the data obtained from the Raman spectroscopy. Tribological properties of the DLC are associated with chemical structure of the film. However, the super low value of friction coefficient 0.003 is obtained when the film is predominantly constituted by a-C and sp2 fraction which is embedded within the clusters of ta-C. Such a particular film with super low friction coefficient is measured while it was deposited on steel at low laser power density of 2 GW/cm2. The super low friction mechanism is explained by low sliding resistance of a-C/sp2 and ta-C clusters. Combination of excellent physical and mechanical properties of wear resistance and super low friction coefficient of DLC films is desirable for engineering applications. Moreover, the high friction coefficient of DLC films deposited at 9GW/cm2 is related to widening of the intergrain distance caused by transformation from sp2 to sp3 hybridized structure.
A molecular dynamics analysis of ion irradiation of ultrathin amorphous carbon films
NASA Astrophysics Data System (ADS)
Qi, J.; Komvopoulos, K.
2016-09-01
Molecular dynamics (MD) simulations provide insight into nanoscale problems where continuum description breaks down, such as the modeling of ultrathin films. Amorphous carbon (a-C) films are commonly used as protective overcoats in various contemporary technologies, including microelectromechanical systems, bio-implantable devices, optical lenses, and hard-disk drives. In all of these technologies, the protective a-C film must be continuous and very thin. For example, to achieve high storage densities (e.g., on the order of 1 Tb/in.2) in magnetic recording, the thickness of the a-C film used to protect the magnetic media and the recording head against mechanical wear and corrosion must be 2-3 nm. Inert ion irradiation is an effective post-deposition method for reducing the film thickness, while preserving the mechanical and chemical characteristics. In this study, MD simulations of Ar+ ion irradiated a-C films were performed to elucidate the effects of the ion incidence angle and ion kinetic energy on the film thickness and structure. The MD results reveal that the film etching rate exhibits a strong dependence on the ion kinetic energy and ion incidence angle, with a maximum etching rate corresponding to an ion incidence angle of ˜20°. It is also shown that Ar+ ion irradiation mainly affects the structure of the upper half of the ultrathin a-C film and that carbon atom hybridization is a strong function of the ion kinetic energy and ion incidence angle. The results of this study elucidate the effects of important ion irradiation parameters on the structure and thickness of ultrathin films and provide fundamental insight into the physics of dry etching.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tiwari, Pragya; Srivastava, A. K.; Khattak, B. Q.
Polymethyl methacrylate (PMMA) is characterized for electron beam interactions in the resist layer in lithographic applications. PMMA thin films (free standing) were prepared by solvent casting method. These films were irradiated with 30keV electron beam at different doses. Structural and chemical properties of the films were studied by means of X-ray diffraction and Fourier transform infra-red (FTIR) spectroscopy The XRD results showed that the amorphization increases with electron beam irradiation dose. FTIR spectroscopic analysis reveals that electron beam irradiation promotes the scission of carbonyl group and depletes hydrogen and converts polymeric structure into hydrogen depleted carbon network.
NASA Astrophysics Data System (ADS)
Wang, Chengbing; Yang, Shengrong; Wang, Qi; Wang, Zhou; Zhang, Junyan
2008-06-01
Hydrogenated carbon films were grown by a plasma-enhanced chemical vapor deposition (PECVD) technique using CH4 and H2 as feedstock at ambient temperature. The microstructure of the films was characterized by high resolution transmission electron microscopy (HRTEM). The images showed the presence of curved basal planes in fullerene-like arrangements. An apparent amorphous graphene structure with nm-sized packages of basal planes in a turbostratic feature was observed. The fabricated fullerene-like hydrogenated carbon films (FL-C:H) possess superior mechanical properties, i.e. high hardness (19 GPa) and high elasticity (elastic recovery of 85%). More importantly, the films exhibit ultra-low friction (μ = 0.009) under ambient conditions with 20% relative humidity.
Wang, Chengbing; Yang, Shengrong; Wang, Qi; Wang, Zhou; Zhang, Junyan
2008-06-04
Hydrogenated carbon films were grown by a plasma-enhanced chemical vapor deposition (PECVD) technique using CH(4) and H(2) as feedstock at ambient temperature. The microstructure of the films was characterized by high resolution transmission electron microscopy (HRTEM). The images showed the presence of curved basal planes in fullerene-like arrangements. An apparent amorphous graphene structure with nm-sized packages of basal planes in a turbostratic feature was observed. The fabricated fullerene-like hydrogenated carbon films (FL-C:H) possess superior mechanical properties, i.e. high hardness (19 GPa) and high elasticity (elastic recovery of 85%). More importantly, the films exhibit ultra-low friction (μ = 0.009) under ambient conditions with 20% relative humidity.
NASA Technical Reports Server (NTRS)
DeGregorio, B. T.; Sharp, T. G.
2003-01-01
For over a decade, the oldest evidence for life on this planet has been microfossils in the 3.5 Ga Apex Chert in Western Australia. Recently, the biogenicity of these carbon-rich structures has been called into question through reanalysis of the local geology and reinterpretation of the original thin sections. Although initially described as a stratiform, bedded chert of siliceous clasts, the unit is now thought to be a brecciated hydrothermal vein chert. The high temperatures of a hydrothermal environment would probably have detrimental effects to early non-hyperthermophilic life, compared to that of a shallow sea. Conversely, a hydrothermal origin would suggest that if the microfossils were valid, they might have been hyperthermophilic. Apex Chert controversy. The Apex Chert microfossils were originally described as septate filaments composed of kerogen similar in morphology to Proterozoic and modern cyanobacteria. However new thin section analysis shows that these carbonaceous structures are not simple filaments. Many of the original microfossils are branched and have variable thickness when the plane of focus is changed. Hydrothermal alteration of organic remains has also been suggested for the creation of these strange morphologies. Another point of contention lies with the nature of the carbon material in these proposed microfossils. Kerogen is structurally amorphous, but transforms into well-ordered graphite under high pressures and temperatures. Raman spectrometry of the carbonaceous material in the proposed microfossils has been interpreted both as partially graphitized kerogen and amorphous graphite. However, these results are inconclusive, since Raman spectrometry cannot adequately discriminate between kerogen and disordered graphite. There are also opposing views for the origin of the carbon in the Apex Chert. The carbon would be biogenic if the proposed microfossils are indeed the remains of former living organisms. However, an inorganic Fischer- Tropsch-type synthesis is also a possible explanation for the formation of large-aggregate carbonaceous particles and could also account for the depletion of (13)C observed.
Hosono, Eiji; Wang, Yonggang; Kida, Noriyuki; Enomoto, Masaya; Kojima, Norimichi; Okubo, Masashi; Matsuda, Hirofumi; Saito, Yoshiyasu; Kudo, Tetsuichi; Honma, Itaru; Zhou, Haoshen
2010-01-01
A triaxial LiFePO4 nanowire with a multi wall carbon nanotube (VGCF:Vapor-grown carbon fiber) core column and an outer shell of amorphous carbon was successfully synthesized through the electrospinning method. The carbon nanotube core oriented in the direction of the wire played an important role in the conduction of electrons during the charge-discharge process, whereas the outer amorphous carbon shell suppressed the oxidation of Fe2+. An electrode with uniformly dispersed carbon and active materials was easily fabricated via a single process by heating after the electrospinning method is applied. Mossbauer spectroscopy for the nanowire showed a broadening of the line width, indicating a disordered coordination environment of the Fe ion near the surface. The electrospinning method was proven to be suitable for the fabrication of a triaxial nanostructure.
Vertical electric field stimulation of neural cells on porous amorphous carbon electrodes
NASA Astrophysics Data System (ADS)
Jain, Shilpee; Sharma, Ashutosh; Basu, Bikramjit
2014-03-01
We demonstrate the efficacy of amorphous macroporous carbon substrates as electrodes to stimulate neuronal cell proliferation in presence of external electric field. The electric field was applied perpendicular to carbon electrode, while growing mouse neuroblastoma (N2a) cells in vitro. The placement of the second electrode outside of the cell culture medium allows the investigation of cell response to electric field without the concurrent complexities of submerged electrodes such as potentially toxic electrode reactions, electro-kinetic flows and charge transfer (electrical current) in the cell medium. The macroporous carbon electrodes are uniquely characterized by a higher specific charge storage capacity (0.2 mC/cm2) and low impedance (3.3 k Ω at 1 kHz). When a uniform or a gradient electric field was applied perpendicular to the amorphous carbon substrate, it was found that the N2a cell viability and neurite length were higher at low electric field strengths (<= 2.5 V/cm) compared to that measured without an applied field (0 V/cm). Overall, the results of the present study unambiguously establish the uniform/gradient vertical electric field based culture protocol to stimulate neurite outgrowth and viability of nerve cells.
NASA Astrophysics Data System (ADS)
Liu, Yongchang; Lan, Feng; Ma, Zongqing; Chen, Ning; Li, Huijun; Barua, Shaon; Patel, Dipak; Shahriar, M.; Hossain, Al; Acar, S.; Kim, Jung Ho; Xue Dou, Shi
2015-05-01
High performance MgB2 bulks using carbon-coated amorphous boron as a boron precursor were fabricated by Cu-activated sintering at low temperature (600 °C, below the Mg melting point). Dense nano-MgB2 grains with a high level of homogeneous carbon doping were formed in these MgB2 samples. This type of microstructure can provide a stronger flux pinning force, together with depressed volatility and oxidation of Mg owing to the low-temperature Cu-activated sintering, leading to a significant improvement of critical current density (Jc) in the as-prepared samples. In particular, the value of Jc for the carbon-coated (Mg1.1B2)Cu0.05 sample prepared here is even above 1 × 105 A cm-2 at 20 K, 2 T. The results herein suggest that the combination of low-temperature Cu-activated sintering and employment of carbon-coated amorphous boron as a precursor could be a promising technique for the industrial production of practical MgB2 bulks or wires with excellent Jc, as the carbon-coated amorphous boron powder can be produced commercially at low cost, while the addition of Cu is very convenient and inexpensive.
Zhan, Hualin; Garrett, David J.; Apollo, Nicholas V.; Ganesan, Kumaravelu; Lau, Desmond; Prawer, Steven; Cervenka, Jiri
2016-01-01
High surface area electrode materials are of interest for a wide range of potential applications such as super-capacitors and electrochemical cells. This paper describes a fabrication method of three-dimensional (3D) graphene conformally coated on nanoporous insulating substrate with uniform nanopore size. 3D graphene films were formed by controlled graphitization of diamond-like amorphous carbon precursor films, deposited by plasma-enhanced chemical vapour deposition (PECVD). Plasma-assisted graphitization was found to produce better quality graphene than a simple thermal graphitization process. The resulting 3D graphene/amorphous carbon/alumina structure has a very high surface area, good electrical conductivity and exhibits excellent chemically stability, providing a good material platform for electrochemical applications. Consequently very large electrochemical capacitance values, as high as 2.1 mF for a sample of 10 mm3, were achieved. The electrochemical capacitance of the material exhibits a dependence on bias voltage, a phenomenon observed by other groups when studying graphene quantum capacitance. The plasma-assisted graphitization, which dominates the graphitization process, is analyzed and discussed in detail. PMID:26805546
Zhan, Hualin; Garrett, David J; Apollo, Nicholas V; Ganesan, Kumaravelu; Lau, Desmond; Prawer, Steven; Cervenka, Jiri
2016-01-25
High surface area electrode materials are of interest for a wide range of potential applications such as super-capacitors and electrochemical cells. This paper describes a fabrication method of three-dimensional (3D) graphene conformally coated on nanoporous insulating substrate with uniform nanopore size. 3D graphene films were formed by controlled graphitization of diamond-like amorphous carbon precursor films, deposited by plasma-enhanced chemical vapour deposition (PECVD). Plasma-assisted graphitization was found to produce better quality graphene than a simple thermal graphitization process. The resulting 3D graphene/amorphous carbon/alumina structure has a very high surface area, good electrical conductivity and exhibits excellent chemically stability, providing a good material platform for electrochemical applications. Consequently very large electrochemical capacitance values, as high as 2.1 mF for a sample of 10 mm(3), were achieved. The electrochemical capacitance of the material exhibits a dependence on bias voltage, a phenomenon observed by other groups when studying graphene quantum capacitance. The plasma-assisted graphitization, which dominates the graphitization process, is analyzed and discussed in detail.
Li, Xufan; Chi, Miaofang; Mahurin, Shannon Mark; ...
2016-01-18
Hard-sphere-templating method has been widely used to synthesize hollow carbon spheres (HCSs), in which the spheres were firstly coated with a carbon precursor, followed by carbonization and core removal. The obtained HCSs are generally amorphous or weakly graphitized (with the help of graphitization catalysts). In this work, we report on the fabrication of graphitized HCSs and yolk–shell Au@HCS nanostructures using a modified templating method, in which smooth, uniform graphene layers were grown on SiO 2 spheres or Au@SiO 2 nanoparticles via metal-catalyst-free chemical vapor deposition (CVD) of methane. Furthermore, our work not only provides a new method to fabricate high-quality,more » graphitized HCSs but also demonstrates a reliable approach to grow quality graphene on oxide surfaces using CVD without the presence of metal catalysts.« less
Sun, Zhimei; Zhou, Jian; Pan, Yuanchun; Song, Zhitang; Mao, Ho-Kwang; Ahuja, Rajeev
2011-06-28
Ge(2)Sb(2)Te(5) (GST) is a technologically very important phase-change material that is used in digital versatile disks-random access memory and is currently studied for the use in phase-change random access memory devices. This type of data storage is achieved by the fast reversible phase transition between amorphous and crystalline GST upon heat pulse. Here we report pressure-induced reversible crystalline-amorphous and polymorphic amorphous transitions in NaCl structured GST by ab initio molecular dynamics calculations. We have showed that the onset amorphization of GST starts at approximately 18 GPa and the system become completely random at approximately 22 GPa. This amorphous state has a cubic framework (c-amorphous) of sixfold coordinations. With further increasing pressure, the c-amorphous transforms to a high-density amorphous structure with trigonal framework (t-amorphous) and an average coordination number of eight. The pressure-induced amorphization is investigated to be due to large displacements of Te atoms for which weak Te-Te bonds exist or vacancies are nearby. Upon decompressing to ambient conditions, the original cubic crystalline structure is restored for c-amorphous, whereas t-amorphous transforms to another amorphous phase that is similar to the melt-quenched amorphous GST.
Characterization and evaluation of amorphous carbon thin film (ACTF) for sodium ion adsorption
NASA Astrophysics Data System (ADS)
Fathy, Mahmoud; Mousa, Mahmoud Ahmed; Moghny, Th. Abdel; Awadallah, Ahmed E.
2017-12-01
The removal of sodium ions from aqueous solutions by adsorption onto amorphous carbon thin film (ACTF) has been studied in batch mode. In this work, the ACTF as new adsorbent was synthesized based on rice straw, then its structure and properties were taken into consideration to study its ability to adsorb sodium ions from synthetic water. The influence of pH, contact time, and temperature of the ion adsorption on ACTF was also studied using batch tests. We found that the contact time of sodium adsorption and its isothermal adsorption studied were described by pseudo-second-order kinetic model and Langmuir isotherm, respectively. Our results indicated that the adsorption of sodium ions on ACTF become be stronger and depends on pH, furthermore, the maximum adsorption capacities of sodium on ACTF recorded 107, 120 and 135 mg g-1 at 35, 45, and 65 °C. The thermodynamic parameters explain that the adsorption of sodium ions on ACTF is a spontaneous process and endothermic reaction. According to adsorption studies, we found that the ACTF can be used effectively for ion chromatography or desalinate sodium ion using ion exchange process in the hybrid desalination process with insignificant loss of adsorption capacity. However, the ACTF has better properties than any other carbon materials obtained from an agricultural byproduct.
Huber, Julia; Griesshaber, Erika; Nindiyasari, Fitriana; Schmahl, Wolfgang W; Ziegler, Andreas
2015-05-01
In arthropods the cuticle forms an exoskeleton with its physical and chemical properties adapted to functions of distinct skeletal elements. The cuticle of the partes incisivae (PI) in mandibles of terrestrial isopods is a composite of chitin-protein fibrils/fibres and minerals. It consists of an unmineralized tip, a middle region with organic fibrils reinforced mainly with amorphous calcium phosphate and a base region mineralized with amorphous calcium carbonate and calcite. In this study we extend our work on the structure and material properties of the incisive cuticle employing electron backscatter diffraction (EBSD), and investigate calcite orientation patterns in the PI of two terrestrial isopod species from different habitats. We trace small-scale differences in texture sharpness and calcite microstructure, and compare calcite organization and orientation patterns in the PI with those in the tergites of the same isopod species. We observe that in the PI calcite orientation, the degree of crystal alignment, and mode of crystalline domain assemblage is highly varied within short length scales. This contrasts to calcite organization in the tergite cuticle, where calcite has only one specific texture pattern. Such a large range in the variation of calcite organization has not been observed in other carbonate biological hard tissues, such as shells and teeth, where one specific texture and microstructure prevails. Thus, the investigated isopod species are able to control crystallization of the amorphous carbonate precursor in a differential way, most probably related to the function of the individual skeletal element and the animals' behavior. Copyright © 2015 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Hiroki, K.; Muralidhar, M.; Koblischka, M. R.; Murakami, M.
2017-07-01
The object of this investigation is to reduce the cost of bulk production and in the same time to increase the critical current performance of bulk MgB2 material. High-purity commercial powders of Mg metal (99.9% purity) and two types of crystalline (99% purity) and 16.5 wt% carbon-coated, nanometer-sized amorphous boron powders (98.5% purity) were mixed in a nominal composition of MgB2 to reduce the boron cost and to see the effect on the superconducting and magnetic properties. Several samples were produced mixing the crystalline boron and carbon-coated, nanometer-sized amorphous boron powders in varying ratios (50:50, 60:40, 70:30, 80:20, 90:10) and synthesized using a single-step process using the solid state reaction around 800 °C for 3 h in pure argon atmosphere. The magnetization measurements exhibited a sharp superconducting transition temperature with T c, onset around 38.6 K to 37.2 K for the bulk samples prepared utilizing the mixture of crystalline boron and 16.5% carbon-coated amorphous boron. The critical current density at higher magnetic field was improved with addition of carbon-coated boron to crystalline boron in a ratio of 80:20. The highest self-field Jc around 215,000 A/cm2 and 37,000 A/cm2 were recorded at 20 K, self-field and 2 T for the sample with a ratio of 80:10. The present results clearly demonstrate that the bulk MgB2 performance can be improved by adding carbon-coated nano boron to crystalline boron, which will be attractive to reduce the cost of bulk MgB2 material for several industrial applications.
Nanostructural evolution during emission of CsI-coated carbon fiber cathodes
NASA Astrophysics Data System (ADS)
Drummy, Lawrence F.; Apt, Scott; Shiffler, Don; Golby, Ken; LaCour, Matt; Maruyama, Benji; Vaia, Richard A.
2010-06-01
Carbon-based nanofiber and microfiber cathodes exhibit very low voltages for the onset of electron emission, and thus provide exciting opportunities for applications ranging from high power microwave sources to field emission displays. CsI coatings have been experimentally shown to lower the work function for emission from the fiber tips, although little is known about the microstructure of the fibers themselves in their as-received state, after coating with CsI, or after being subjected to high voltage cycling. Longitudinal cross sections of the original, unused CsI-coated fibers produced by focused ion beam lift-out revealed a nanostructured graphitic core surrounded by an amorphous carbon shell with submicron sized islands of crystalline CsI on the outer surface. Aberration-corrected high resolution electron microscopy (HREM) of the fiber core achieved 0.10 nm resolution, with the graphite (200) clearly visible in digital fast Fourier transformations of the 2-4 nm highly ordered graphitic domains. As the cathode fibers are cycled at high voltage, HREM demonstrates that the graphitic ordering of the core increases with the number of cycles, however the structure and thickness of the amorphous carbon layer remains unchanged. These results are consistent with micro-Raman measurements of the fiber disordered/graphitic (D/G) band ratios. After high voltage cycling, a uniform ˜100 nm film at the fiber tip was evident in both bright field transmission electron microscopy (TEM) and high angle annular dark field scanning TEM (STEM). Low-dose electron diffraction techniques confirmed the amorphous nature of this film, and STEM with elemental mapping via x-ray energy dispersive spectroscopy indicates this layer is composed of CsIO. The oxidative evolution of tip composition and morphology due to impurities in the chamber, along with increased graphitization of the fiber core, contributes to changes in emission behavior with cycling.
NASA Astrophysics Data System (ADS)
Fan, Fuqiang; Fang, Guoqing; Zhang, Ruixue; Xu, Yanhui; Zheng, Junwei; Li, Decheng
2014-08-01
A series of core-shell carbon coated amorphous CoSnO3 (CoSnO3@C) with different carbon content are synthesized. Effects of carbon content and coating carbon thickness on the physical and electrochemical performances of the samples were studied in detail. The samples were analyzed by X-ray diffraction (XRD), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), galvanostatic charge-discharge and AC impedance spectroscopy, respectively. The results indicate that controlling the concentration of aqueous glucose solution influences the generation of in-situ carbon layer thickness. The optimal concentration of aqueous glucose solution, carbon content and carbon layer thickness are suggested as 0.25 M, 35.1% and 20 nm, respectively. CoSnO3@C composite prepared under the optimal conditions exhibits excellent cycling performance, whose reversible capacity could reach 491 mA h g-1 after 100 cycles.
NASA Astrophysics Data System (ADS)
Vasin, Andriy V.; Ishikawa, Yukari; Shibata, Noriyoshi; Salonen, Jarno; Lehto, Vesa-Pekka
2007-05-01
A new approach to development of light-emitting SiO2:C layers on Si wafer is demonstrated. Carbon-incorporated silicon oxide was fabricated by three-step procedure: (1) formation of the porous silicon (por-Si) layer by ordinary anodization in HF:ethanol solution; (2) carbonization at 1000 °C in acetylene flow (formation of por-Si:C layer); (3) oxidation in the flow of moisturized argon at 800 °C (formation of SiO2:C layer). Resulting SiO2:C layer exhibited very strong and stable white photoluminescence at room temperature. It is shown that high reactivity of water vapor with nano-crystalline silicon and inertness with amorphous carbon play a key role in the formation of light-emitting SiO2:C layer.
NASA Astrophysics Data System (ADS)
Jin, Chuanyu; Zhou, Lingping; Fu, Licai; Zhu, Jiajun; Li, Deyi
2017-04-01
The high solubility in molten salt and low conductivity of NiCl2, compared with traditional FeS2 and CoS2, have become the restrictions for its extensive application in cathode materials of thermal batteries. In this study, carbon coated NiCl2 cathode is successfully fabricated by the carbonization of stearic acid. The high specific energy of 641 Wh kg-1 at current densities of 0.5 A cm-2 are observed for the carbon coated NiCl2 thermal batteries, which is higher than the pure NiCl2 with 475 Wh kg-1. The high specific energies and high-current discharge ability are attribute to the graphite and amorphous carbon layers on the surface of NiCl2 crystalline, which were detected by TEM after carbonization. The graphite layers can improve the conductivity of NiCl2. Meanwhile the coated carbon structure could reduce the solubility of NiCl2 in molten salt.
Surface topographical and structural analysis of Ag+-implanted polymethylmethacrylate
NASA Astrophysics Data System (ADS)
Arif, Shafaq; Rafique, M. Shahid; Saleemi, Farhat; Naab, Fabian; Toader, Ovidiu; Sagheer, Riffat; Bashir, Shazia; Zia, Rehana; Siraj, Khurram; Iqbal, Saman
2016-08-01
Specimens of polymethylmethacrylate (PMMA) were implanted with 400-keV Ag+ ions at different ion fluences ranging from 1 × 1014 to 5 × 1015 ions/cm2 using a 400-kV NEC ion implanter. The surface topographical features of the implanted PMMA were investigated by a confocal microscope. Modifications in the structural properties of the implanted specimens were analyzed in comparison with pristine PMMA by X-ray diffraction (XRD) and Raman spectroscopy. UV-Visible spectroscopy was applied to determine the effects of ion implantation on optical transmittance of the implanted PMMA. The confocal microscopic images revealed the formation of hillock-like microstructures along the ion track on the implanted PMMA surface. The increase in ion fluence led to more nucleation of hillocks. The XRD pattern confirmed the amorphous nature of pristine and implanted PMMA, while the Raman studies justified the transformation of Ag+-implanted PMMA into amorphous carbon at the ion fluence of ⩾5 × 1014 ions/cm2. Moreover, the decrease in optical transmittance of PMMA is associated with the formation of hillocks and ion-induced structural modifications after implantation.
Carbon nanotube: nanodiamond Li-ion battery cathodes with increased thermal conductivity
NASA Astrophysics Data System (ADS)
Salgado, Ruben; Lee, Eungiee; Shevchenko, Elena V.; Balandin, Alexander A.
2016-10-01
Prevention of excess heat accumulation within the Li-ion battery cells is a critical design consideration for electronic and photonic device applications. Many existing approaches for heat removal from batteries increase substantially the complexity and overall weight of the battery. Some of us have previously shown a possibility of effective passive thermal management of Li-ion batteries via improvement of thermal conductivity of cathode and anode material1. In this presentation, we report the results of our investigation of the thermal conductivity of various Li-ion cathodes with incorporated carbon nanotubes and nanodiamonds in different layered structures. The cathodes were synthesized using the filtration method, which can be utilized for synthesis of commercial electrode-active materials. The thermal measurements were conducted with the "laser flash" technique. It has been established that the cathode with the carbon nanotubes-LiCo2 and carbon nanotube layered structure possesses the highest in-plane thermal conductivity of 206 W/mK at room temperature. The cathode containing nanodiamonds on carbon nanotubes structure revealed one of the highest cross-plane thermal conductivity values. The in-plane thermal conductivity is up to two orders-of-magnitude greater than that in conventional cathodes based on amorphous carbon. The obtained results demonstrate a potential of carbon nanotube incorporation in cathode materials for the effective thermal management of Li-ion high-powered density batteries.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Killian, Christopher; Metzler, Rebecca; Gong, Y. U. T.
Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO{sub 3}) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin (Strongylocentrotus purpuratus), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction ({mu}XRD).more » All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO{sub 3} is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.« less
Mechanism of calcite co-orientation in the sea urchin tooth.
Killian, Christopher E; Metzler, Rebecca A; Gong, Y U T; Olson, Ian C; Aizenberg, Joanna; Politi, Yael; Wilt, Fred H; Scholl, Andreas; Young, Anthony; Doran, Andrew; Kunz, Martin; Tamura, Nobumichi; Coppersmith, Susan N; Gilbert, P U P A
2009-12-30
Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO(3)) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin ( Strongylocentrotus purpuratus ), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction (muXRD). All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO(3) is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.
Sun, Zhimei; Zhou, Jian; Pan, Yuanchun; Song, Zhitang; Mao, Ho-Kwang; Ahuja, Rajeev
2011-01-01
Ge2Sb2Te5 (GST) is a technologically very important phase-change material that is used in digital versatile disks-random access memory and is currently studied for the use in phase-change random access memory devices. This type of data storage is achieved by the fast reversible phase transition between amorphous and crystalline GST upon heat pulse. Here we report pressure-induced reversible crystalline-amorphous and polymorphic amorphous transitions in NaCl structured GST by ab initio molecular dynamics calculations. We have showed that the onset amorphization of GST starts at approximately 18 GPa and the system become completely random at approximately 22 GPa. This amorphous state has a cubic framework (c-amorphous) of sixfold coordinations. With further increasing pressure, the c-amorphous transforms to a high-density amorphous structure with trigonal framework (t-amorphous) and an average coordination number of eight. The pressure-induced amorphization is investigated to be due to large displacements of Te atoms for which weak Te–Te bonds exist or vacancies are nearby. Upon decompressing to ambient conditions, the original cubic crystalline structure is restored for c-amorphous, whereas t-amorphous transforms to another amorphous phase that is similar to the melt-quenched amorphous GST. PMID:21670255
Arie, Arenst Andreas; Lee, Joong Kee
2011-07-01
A nano carbon coating layer was prepared by the thermal evaporation of fullerene C60 on the surface of lithium metal anodes for rechargeable lithium batteries. The morphology and structure of the carbon layer was firstly investigated by Raman spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The effects of the nano-carbon coating layer on the electrochemical performance of the lithium electrode were then examined by charge-discharge tests and impedance spectroscopy. Raman spectra of carbon coating layer showed two main peaks (D and G peaks), indicating the amorphous structure of the film. A honey comb-like structure of carbon film was observed by TEM photographs, providing a transport path for the transport of lithium ions at the electrode/electrolyte interface. The carbon coated lithium electrodes exhibited a higher initial coulombic efficiency (91%) and higher specific capacity retention (88%) after the 30th cycle at 0.2 C-rate between 3.4 and 4.5 V. Impedance measurements showed that the charge transfer resistance was significantly reduced after cycle tests for the carbon coated electrodes, revealing that the more stable solid electrolyte (SEI) layer was established on their surface. Based on the experimental results, it suggested that the presence of the nano-carbon coating layer might suppress the dendritic growth on the surface of lithium metal electrodes, as confirmed by the observation of SEM images after cycle tests.
NASA Astrophysics Data System (ADS)
Avotina, Liga; Lungu, Mihail; Dinca, Paul; Butoi, Bogdan; Cojocaru, Gabriel; Ungureanu, Razvan; Marcu, Aurelian; Luculescu, Catalin; Hapenciuc, Claudiu; Ganea, Paul C.; Petjukevics, Aleksandrs; Lungu, Cristian P.; Kizane, Gunta; Ticos, C. M.; Antohe, Stefan
2018-01-01
Be-C-W mixed materials with variable atomic ratios were exposed to high power (TW) laser induced filamentation plasma in air in normal conditions and in deuterium at a reduced pressure of 20 Torr. Morphological and structural investigations were performed on the irradiated zones for both ambient conditions. The presence of low-pressure deuterium increased the overall ablation rate for all samples. From the elemental concentration point of view, the increase of the carbon percentage has led to an increase in the ablation rate. An increase of the tungsten percentage had the opposite effect. From structural spectroscopic investigations using XPS, Raman and FT-IR of the irradiated and non-irradiated sample surfaces, we conclude that deuterium-induced enhancement of the ablation process could be explained by preferential amorphous carbon removal, possibly by forming deuterated hydrocarbons which further evaporated, weakening the layer structure.
Titanyl phthalocyanine ambipolar thin film transistors making use of carbon nanotube electrodes
NASA Astrophysics Data System (ADS)
Coppedè, Nicola; Valitova, Irina; Mahvash, Farzaneh; Tarabella, Giuseppe; Ranzieri, Paolo; Iannotta, Salvatore; Santato, Clara; Martel, Richard; Cicoira, Fabio
2014-12-01
The capability of efficiently injecting charge carriers into organic films and finely tuning their morphology and structure is crucial to improve the performance of organic thin film transistors (OTFTs). In this work, we investigate OTFTs employing carbon nanotubes (CNTs) as the source-drain electrodes and, as the organic semiconductor, thin films of titanyl phthalocyanine (TiOPc) grown by supersonic molecular beam deposition (SuMBD). While CNT electrodes have shown an unprecedented ability to improve charge injection in OTFTs, SuMBD is an effective technique to tune film morphology and structure. Varying the substrate temperature during deposition, we were able to grow both amorphous (low substrate temperature) and polycrystalline (high substrate temperature) films of TiOPc. Regardless of the film morphology and structure, CNT electrodes led to superior charge injection and transport performance with respect to benchmark Au electrodes. Vacuum annealing of polycrystalline TiOPc films with CNT electrodes yielded ambipolar OTFTs.
NASA Astrophysics Data System (ADS)
Maia da Costa, M. E. H.; Baumvol, I. J. R.; Radke, C.; Jacobsohn, L. G.; Zamora, R. R. M.; Freire, F. L.
2004-11-01
Hard amorphous fluorinated carbon films (a-C:F) deposited by plasma enhanced chemical vapor deposition were annealed in vacuum for 30 min in the temperature range of 200-600 °C. The structural and compositional modifications were followed by several analytical techniques: Rutherford backscattering spectrometry (RBS), elastic recoil detection analysis (ERDA), x-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Nanoidentation measurements and lateral force microscopy experiments were carried out in order to provide the film hardness and the friction coefficient, respectively. The internal stress and contact angle were also measured. RBS, ERDA, and XPS results indicate that both fluorine and hydrogen losses occur for annealing temperatures higher than 300 °C. Raman spectroscopy shows a progressive graphitization upon annealing, while the surface became slightly more hydrophobic as revealed by the increase of the contact angle. Following the surface wettability reduction, a decrease of the friction coefficient was observed. These results highlight the influence of the capillary condensation on the nanoscale friction. The film hardness and the internal stress are constant up to 300 °C and decrease for higher annealing temperatures, showing a direct correlation with the atomic density of the films. Since the thickness variation is negligible, the mass loss upon thermal treatment results in amorphous structures with a lower degree of cross-linking, explaining the deterioration of the mechanical properties of the a-C:F films.
Platelet adhesion on phosphorus-incorporated tetrahedral amorphous carbon films
NASA Astrophysics Data System (ADS)
Liu, Aiping; Zhu, Jiaqi; Liu, Meng; Dai, Zhifei; Han, Xiao; Han, Jiecai
2008-11-01
The haemocompatibility of phosphorus-incorporated tetrahedral amorphous carbon (ta-C:P) films, synthesized by filtered cathodic vacuum arc technique with PH 3 as the dopant source, was assessed by in vitro platelet adhesion tests. Results based on scanning electron microscopy and contact angle measurements reveal that phosphorus incorporation improves the wettability and blood compatibility of ta-C film. Our studies may provide a novel approach for the design and synthesis of doped ta-C films to repel platelet adhesion and reduce thrombosis risk.
Capillarity creates single-crystal calcite nanowires from amorphous calcium carbonate.
Kim, Yi-Yeoun; Hetherington, Nicola B J; Noel, Elizabeth H; Kröger, Roland; Charnock, John M; Christenson, Hugo K; Meldrum, Fiona C
2011-12-23
Single-crystal calcite nanowires are formed by crystallization of morphologically equivalent amorphous calcium carbonate (ACC) particles within the pores of track etch membranes. The polyaspartic acid stabilized ACC is drawn into the membrane pores by capillary action, and the single-crystal nature of the nanowires is attributed to the limited contact of the intramembrane ACC particle with the bulk solution. The reaction environment then supports transformation to a single-crystal product. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
MoO2 nanosheets embedded in amorphous carbon matrix for sodium-ion batteries
NASA Astrophysics Data System (ADS)
He, Hong; Man, Yuhong; Yang, Jingang; Xie, Jiale; Xu, Maowen
2017-10-01
MoO2 nanosheets embedded in the amorphous carbon matrix (MoO2/C) are successfully synthesized via a facile hydrothermal method and investigated as an anode for sodium-ion batteries. Because of the efficient ion transport channels and good volume change accommodation, MoO2/C delivers a discharge/charge capacity of 367.8/367.0 mAh g-1 with high coulombic efficiency (99.4%) after 100 cycles at a current density of 50 mA g-1.
Amorphous calcium carbonate transforms into calcite during sea urchin larval spicule growth
Beniash, E.; Aizenberg, J.; Addadi, L.; Weiner, S.
1997-01-01
Sea urchin larvae form an endoskeleton composed of a pair of spicules. For more than a century it has been stated that each spicule comprises a single crystal of the CaCO3 mineral, calcite. We show that an additional mineral phase, amorphous calcium carbonate, is present in the sea urchin larval spicule, and that this inherently unstable mineral transforms into calcite with time. This observation significantly changes our concepts of mineral formation in this well-studied organism.
Rapid Annealing Of Amorphous Hydrogenated Carbon
NASA Technical Reports Server (NTRS)
Alterovitz, Samuel A.; Pouch, John J.; Warner, Joseph D.
1989-01-01
Report describes experiments to determine effects of rapid annealing on films of amorphous hydrogenated carbon. Study represents first efforts to provide information for applications of a-C:H films where rapid thermal processing required. Major finding, annealing causes abrupt increase in absorption and concomitant decrease in optical band gap. Most of change occurs during first 20 s, continues during longer annealing times. Extend of change increases with annealing temperature. Researchers hypothesize abrupt initial change caused by loss of hydrogen, while gradual subsequent change due to polymerization of remaining carbon into crystallites or sheets of graphite. Optical band gaps of unannealed specimens on silicon substrates lower than those of specimens on quartz substrates.
NASA Astrophysics Data System (ADS)
Murata, H.; Toko, K.; Saitoh, N.; Yoshizawa, N.; Suemasu, T.
2017-01-01
Multilayer graphene (MLG) growth on arbitrary substrates is desired for incorporating carbon wiring and heat spreaders into electronic devices. We investigated the metal-induced layer exchange growth of a sputtered amorphous C layer using Ni as a catalyst. A MLG layer uniformly formed on a SiO2 substrate at 600 °C by layer exchange between the C and Ni layers. Raman spectroscopy and electron microscopy showed that the resulting MLG layer was highly oriented and contained relatively few defects. The present investigation will pave the way for advanced electronic devices integrated with carbon materials.
Prebiotic carbon in clays from Orgueil and Ivuna (CI), and Tagish Lake (C2 ungrouped) meteorites
NASA Astrophysics Data System (ADS)
Garvie, Laurence A. J.; Buseck, Peter R.
Transmission electron microscopic (TEM) and electron energy-loss spectroscopic (EELS) study of the Ivuna and Orgueil (CI), and Tagish Lake (C2 ungrouped) carbonaceous chondrite meteorites shows two types of C-clay assemblages. The first is coarser-grained (to 1 μm) clay flakes that show an intense O K edge from the silicate together with a prominent C K edge, but without discrete C particles. Nitrogen is common in some clay flakes. Individual Orgueil and Tagish Lake meteorite clay flakes contain up to 6 and 8 at% C, respectively. The C K-edge spectra from the clays show fine structure revealing aromatic, aliphatic, carboxylic, and carbonate C. The EELS data shows that this C is intercalated with the clay flakes. The second C-clay association occurs as poorly crystalline to amorphous material occurring as nanometer aggregates of C, clay, and Fe-O-rich material. Some aggregates are dominated by carbonaceous particles that are structurally and chemically similar to the acid insoluble organic matter. The C K-edge shape from this C resembles that of amorphous C, but lacking the distinct peaks corresponding to aliphatic, carboxylic, and carbonate C groups. Nanodiamonds are locally abundant in some carbonaceous particles. The abundance of C in the clays suggest that molecular speciation in the carbonaceous chondrites is partly determined by the effects of aqueous processing on the meteorite parent bodies, and that clays played an important role. This intricate C-clay association lends credence to the proposal that minerals were important in the prebiotic chemical evolution of the early solar system.
Stable prenucleation mineral clusters are liquid-like ionic polymers
Demichelis, Raffaella; Raiteri, Paolo; Gale, Julian D.; Quigley, David; Gebauer, Denis
2011-01-01
Calcium carbonate is an abundant substance that can be created in several mineral forms by the reaction of dissolved carbon dioxide in water with calcium ions. Through biomineralization, organisms can harness and control this process to form various functional materials that can act as anything from shells through to lenses. The early stages of calcium carbonate formation have recently attracted attention as stable prenucleation clusters have been observed, contrary to classical models. Here we show, using computer simulations combined with the analysis of experimental data, that these mineral clusters are made of an ionic polymer, composed of alternating calcium and carbonate ions, with a dynamic topology consisting of chains, branches and rings. The existence of a disordered, flexible and strongly hydrated precursor provides a basis for explaining the formation of other liquid-like amorphous states of calcium carbonate, in addition to the non-classical behaviour during growth of amorphous calcium carbonate. PMID:22186886
NASA Astrophysics Data System (ADS)
Howe, Jane Y.; Puretzky, Alex A.; Geohegan, David B.; Cui, Hongtao; Eres, Varela; Maria, Alex A.; Lowndes, Douglas H.
2003-03-01
The structure of single-wall and multiwall carbon nanotubes and associated metal catalyst nanoparticles produced during chemical vapor deposition from multilayered metal films deposited on Si and Mo substrates were studied by high-resolution TEM and EDS. Electron beam-evaporated metal multilayer films (e.g. Al-Fe-Mo, typically 11-50 nm total thickness) roughen upon heat treatment to form a variety of catalyst particle sizes suitable for carbon nanotube growth by chemical vapor deposition using acetylene, hydrogen, and argon flow gases. This study investigates these nanoparticles, the type of nanotubes grown, their wall, tip, and basal structures, as well as the associated amounts of amorphous carbon deposited on their walls in different temperature and pressure ranges. Mixtures of SWNT and MWNT are found even for low growth temperatures (650-700 C), while rapid growth of vertically-aligned multiwall nanotubes (VA-MWNTs) predominate in a narrow temperature range at a given pressure. Arrested growth experiments were performed to determine the time periods for SWNT vs. MWNT growth. The nature of the catalyst nanoparticles, their support structure, and insights on the mechanisms of growth will be discussed.
Molecular Dynamical Simulation of Thermal Conductivity in Amorphous Structures
NASA Astrophysics Data System (ADS)
Deangelis, Freddy; Henry, Asegun
While current descriptions of thermal transport exists for well-ordered materials such as crystal latices, new methods are needed to describe thermal transport in disordered materials, including amorphous solids. Because such structures lack periodic, long-range order, a group velocity cannot be defined for thermal modes of vibration; thus, the phonon gas model cannot be applied to these structures. Instead, a new framework must be applied to analyze such materials. Using a combination of density functional theory and molecular dynamics, we have analyzed thermal transport in amorphous structures, chiefly amorphous germanium. The analysis allows us to categorize vibrational modes as propagons, diffusons, or locons, and to determine how they contribute to thermal conductivity within amorphous structures. This method is also being extended to other disordered structures such as amorphous polymers. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1148903.
NASA Astrophysics Data System (ADS)
Gies, Hermann; Happel, Marian; Niedermayr, Andrea; Immenhauser, Adrian
2017-04-01
We present results from a structural study of the transformation of freeze dried amorphous calcium carbonate, ACC, in crystalline material using pair distribution function analysis, PDF analysis, of X-ray powder diffraction data, XPD data. PDF analysis allows for the analysis of local order of structural subunit in the range between molecular unit (1. and 2. coordination sphere) and long range periodicity as in crystalline materials. ACC was precipitated from aqueous solutions at 298 K and 278 K using different amounts of Mg cations as stabilizer. The samples were immediately separated from the solution and freeze dried. For the transformation study, the samples were heated and analysed using XPD until they were crystallized. The radial distribution obtained from the XPD data were compared to simulated radial distributions of the calcium carbonate polymorphs and their hydrated phases. An ACC precipitated from a solution with Ca:Mg:CO3 = 1:5:4 at 298 K (ration in mmol, pH = 8.2) and freeze dried right after isolation from the solution revealed a close resemblance with ikaite in its local order. Another ACC with Ca:Mg:CO3 = 1:10:1.4 (T = 298, pH = 8.7) showed distinctly different local order resembling monohydrocalcite. Both ACC, however, still had considerable amounts of water dominating the Ca-coordination sphere. During the transformation to calcite, the structural changes in the sample concerned the hydrate water coordinating Ca which was removed and replaced by the carbonate oxygens. The study shows that ACC obtained from different starting solutions show specific local order. Freeze drying leads to solid ACC powder which still contain considerable amounts of hydrate water. Structural subunits are distinct in ACC and different from the crystalline phase. The study supplements recent reports presented by Konrad et al., Purgstaller et al., and Tobler et al.. F. Konrad et al., Cryst. Growth Des. 16, 6310-6317(2016) B. Purgstaller et al., Geochimica et Cosmochimica Acta 174, 180-195(2016) DJ. Tobler et al., Cryst. Growth Des. 16, 4500-4508(2016)
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gao, Juan-Li; Gao, Shuang; Liu, Chun-Ling
2014-11-15
Graphical abstract: The ordered mesoporous carbon–niobium oxide composites have been synthesized by a multi-component co-assembly method associated with a carbonization process. - Highlights: • Ordered mesoporous carbon–niobium oxide composites were synthesized. • The content of Nb{sub 2}O{sub 5} in the composites could be tuned from 38 to 75%. • Niobium species were highly dispersed in amorphous carbon framework walls. • The composites exhibited good catalytic performance in the dehydration of fructose. - Abstract: Ordered mesoporous carbon–niobium oxide composites have been synthesized by a multi-component co-assembly method associated with a carbonization process using phenolic resol as carbon source, niobium chloride asmore » precursor and amphiphilic triblock copolymer Pluronic F127 as template. The resulting materials were characterized using a combination of techniques including differential scanning calorimetry–thermogravimetric analysis, N{sub 2} physical adsorption, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results show that with increasing the content of Nb{sub 2}O{sub 5} from 38 to 75% the specific surface area decreases from 306.4 to 124.5 m{sup 2} g{sup −1}, while the ordered mesoporous structure is remained. Niobium species is well dispersed in the amorphous carbon framework. The mesoporous carbon–niobium oxide composites exhibit high catalytic activity in the dehydration of fructose to 5-hydroxymethylfurfural. A 100% conversion of fructose and a 76.5% selectivity of 5-hydroxymethylfurfural were obtained over the carbon–niobium oxide composite containing 75% Nb{sub 2}O{sub 5} under the investigated reaction conditions.« less
Room temperature vortex fluidic synthesis of monodispersed amorphous proto-vaterite.
Peng, Wenhong; Chen, Xianjue; Zhu, Shenmin; Guo, Cuiping; Raston, Colin L
2014-10-11
Monodispersed particles of amorphous calcium carbonate (ACC) 90 to 200 nm in diameter are accessible at room temperature in ethylene glycol and water using a vortex fluidic device (VFD). The ACC material is stable for at least two weeks under ambient conditions.
Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate.
Radha, A V; Forbes, Tori Z; Killian, Christopher E; Gilbert, P U P A; Navrotsky, Alexandra
2010-09-21
Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC ⇒ anhydrous ACC ∼ biogenic anhydrous ACC ⇒ vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO(2) sequestration.
Femtosecond pulsed laser deposition of amorphous, ultrahard boride thin films
NASA Astrophysics Data System (ADS)
Stock, Michael; Molian, Pal
2004-05-01
Amorphous thin films (300-500 nm) of ultrahard AlMgB10 with oxygen and carbon impurities were grown on Si (100) substrates at 300 K using a solid target of AlMgB14 containing a spinel phase (MgAl2O4) and using a 120 fs pulsed, 800 nm wavelength Ti:sapphire laser. The films were subsequently annealed in argon gas up to 1373 K for 2 h. Scanning electron microscopy (SEM) was used to examine the particulate formation, atomic force microscopy was employed to characterize the film surface topography, x-ray diffraction and transmission electron microscopy were used to determine the microstructure, x-ray photoelectron spectroscopy was performed to examine the film composition, and nanoindentation was employed to study the hardness of thin films. The as-deposited and postannealed films (up to 1273 K) had a stochiometry of AlMgB10 with a significant amount of oxygen and carbon impurities and exhibited amorphous structures for a maximum hardness of 40+/-3 GPa. However, postannealing at higher temperatures led to crystallization and transformation of the film to SiB6 with a substantial loss in hardness. Results are also compared with our previous study on 23 ns, 248 nm wavelength (KrF excimer) pulsed laser deposition of AlMgB14 reported in this journal [Y. Tian, A. Constant, C. C. H. Lo, J. W. Anderegg, A. M. Russell, J. E. Snyder, and P. A. Molian, J. Vac. Sci. Technol. A 21, 1055 (2003)]. .
NASA Astrophysics Data System (ADS)
Zeinali-Rad, M.; Allahkaram, S. R.; Mahdavi, S.
2015-09-01
Nano-crystalline and amorphous Co-P coatings were deposited on plain carbon steel substrates by using direct current. Effects of electrolyte pH on morphology, current efficiency, phosphorus content, hardness, and preferred orientation of the nano-crystalline coatings were investigated. Moreover, the effects of heat treatment on microstructure and hardness of the nano-crystalline and the amorphous coatings were studied. The results showed that, phosphorus content and hardness of the nano-crystalline coatings were decreased by increasing of the pH, in spite of a current efficiency enhancement to as much as 98%. Grain size and preferred orientation were also changed from 13 to 31 nm and from mostly [002] to [100] by increasing the pH from 1 to 4, respectively. Smoother coatings and higher current efficiencies were obtained by the addition of 1 g/L sodium dodecyl sulfate (SDS) to the bath. Highest hardness of the nano-crystalline and the amorphous coatings was about 600 and 750 HV, which increased and reached 760 and 1090 HV after heat treatment, respectively.
Salvatierra, Rodrigo Villegas; Zakhidov, Dante; Sha, Junwei; Kim, Nam Dong; Lee, Seoung-Ki; Raji, Abdul-Rahman O; Zhao, Naiqin; Tour, James M
2017-03-28
Here we show that a versatile binary catalyst solution of Fe 3 O 4 /AlO x nanoparticles enables homogeneous growth of single to few-walled carbon nanotube (CNT) carpets from three-dimensional carbon-based substrates, moving past existing two-dimensional limited growth methods. The binary catalyst is composed of amorphous AlO x nanoclusters over Fe 3 O 4 crystalline nanoparticles, facilitating the creation of seamless junctions between the CNTs and the underlying carbon platform. The resulting graphene-CNT (GCNT) structure is a high-density CNT carpet ohmically connected to the carbon substrate, an important feature for advanced carbon electronics. As a demonstration of the utility of this approach, we use GCNTs as anodes and cathodes in binder-free lithium-ion capacitors, producing stable devices with high-energy densities (∼120 Wh kg -1 ), high-power density capabilities (∼20,500 W kg -1 at 29 Wh kg -1 ), and a large operating voltage window (4.3 to 0.01 V).
Lei, Yu; Huang, Zheng-Hong; Yang, Ying; Shen, Wanci; Zheng, Yongping; Sun, Hongyu; Kang, Feiyu
2013-01-01
Li4Ti5O12/activated carbon hybrid supercapacitor can combine the advantages of both lithium-ion battery and supercapacitor, which may meet the requirements for developing high-performance hybrid electric vehicles. Here we proposed a novel “core-shell” porous graphitic carbon (PGC) to replace conventional activated carbon for achieving excellent cell performance. In this PGC structure made from mesocarbon microbead (MCMB), the inner core is composed of porous amorphous carbon, while the outer shell is graphitic carbon. The abundant porosity and the high surface area not only offer sufficient reaction sites to store electrical charge physically, but also can accelerate the liquid electrolyte to penetrate the electrode and the ions to reach the reacting sites. Meanwhile, the outer graphitic shells of the porous carbon microbeads contribute to a conductive network which will remarkably facilitate the electron transportation, and thus can be used to construct a high-rate, high-capacity cathode for hybrid supercapacitor, especially at high current densities. PMID:23963328
Formation Pathways of Carbon Allotropes in Detonation Condensates
NASA Astrophysics Data System (ADS)
Nielsen, Michael; Bagge-Hansen, Michael; Hammons, Josh; Lauderbach, Lisa; Hodgin, Ralph; Bastea, Sorin; Fried, Larry; Lee, Jonathan; van Buuren, Tony; Pagoria, Phil; May, Chadd; Aloni, Shaul; Willey, Trevor
2017-06-01
Time-resolved small-angle scattering (TR-SAXS) data reveal evolution in the size and morphology of nano-carbon particles that form during the first microsecond during the detonation of high explosive (HE) materials, but do not provide chemical or phase information. Herein, we present analysis of complementary post-detonation soots collected with minimal environmental carbon or other contamination: HE samples are detonated whithin clean ice capture layers to yield aqueous dispersions of the carbonaceous soot. We report substantial variation in soots formed through the detonation of HE materials that attain a variety of temperatures and pressures during detonation. Transmission electron microscopy analysis of these recovered soots provides physical and chemical information that we compare directly to TR-SAXS data and SAXS measurements from recovered soots. We observe various structures including graphitic and amorphous carbon, nanodiamond, and spherical carbon onions. These experimental data correlate to models of how products from HE materials traverse the carbon phase diagram during detonation. Prepared by LLNL under Contract DE-AC52-07NA27344.
NASA Astrophysics Data System (ADS)
Kryazhev, Yu. G.; Vorob'ev, M. S.; Koval', N. N.; Trenikhin, M. V.; Solodovnichenko, V. S.; Sulakshin, S. A.; Likholobov, V. A.
2016-10-01
This work shows the possibility in principle of forming hydrocarbon structures in polyvinyl chloride films free of admixtures and polyvinyl chloride films modified with 5-mass % ferrocene via a radiation chemical transformation in the atmosphere with the use of an electron accelerator with a plasma cathode operating in the pulsed-periodic mode maximal electron energy no higher than 160 keV, pulse length of 40 μs, and current density of 5 mA/cm2. According to the results of semiquantitative X-ray microanalysis, an irradiated polyvinyl chloride film free of admixtures contains 92 of carbon, 6 of oxygen, and 2 mass % of chlorine; the irradiated polyvinyl chloride is an amorphous carbon material. A possible mechanism of the phenomenon is discussed.
Magnetic carbon nanostructures: microwave energy-assisted pyrolysis vs. conventional pyrolysis.
Zhu, Jiahua; Pallavkar, Sameer; Chen, Minjiao; Yerra, Narendranath; Luo, Zhiping; Colorado, Henry A; Lin, Hongfei; Haldolaarachchige, Neel; Khasanov, Airat; Ho, Thomas C; Young, David P; Wei, Suying; Guo, Zhanhu
2013-01-11
Magnetic carbon nanostructures from microwave assisted- and conventional-pyrolysis processes are compared. Unlike graphitized carbon shells from conventional heating, different carbon shell morphologies including nanotubes, nanoflakes and amorphous carbon were observed. Crystalline iron and cementite were observed in the magnetic core, different from a single cementite phase from the conventional process.
Memristive effects in oxygenated amorphous carbon nanodevices
NASA Astrophysics Data System (ADS)
Bachmann, T. A.; Koelmans, W. W.; Jonnalagadda, V. P.; Le Gallo, M.; Santini, C. A.; Sebastian, A.; Eleftheriou, E.; Craciun, M. F.; Wright, C. D.
2018-01-01
Computing with resistive-switching (memristive) memory devices has shown much recent progress and offers an attractive route to circumvent the von-Neumann bottleneck, i.e. the separation of processing and memory, which limits the performance of conventional computer architectures. Due to their good scalability and nanosecond switching speeds, carbon-based resistive-switching memory devices could play an important role in this respect. However, devices based on elemental carbon, such as tetrahedral amorphous carbon or ta-C, typically suffer from a low cycling endurance. A material that has proven to be capable of combining the advantages of elemental carbon-based memories with simple fabrication methods and good endurance performance for binary memory applications is oxygenated amorphous carbon, or a-CO x . Here, we examine the memristive capabilities of nanoscale a-CO x devices, in particular their ability to provide the multilevel and accumulation properties that underpin computing type applications. We show the successful operation of nanoscale a-CO x memory cells for both the storage of multilevel states (here 3-level) and for the provision of an arithmetic accumulator. We implement a base-16, or hexadecimal, accumulator and show how such a device can carry out hexadecimal arithmetic and simultaneously store the computed result in the self-same a-CO x cell, all using fast (sub-10 ns) and low-energy (sub-pJ) input pulses.
Tarasenka, Natalie; Stupak, Aleksandr; Tarasenko, Nikolai; Chakrabarti, Supriya; Mariotti, Davide
2017-05-05
In this paper, we report the one-step synthesis of luminescent carbon nanoparticles (NPs) via laser irradiation of a graphite target in a solvent [H 2 O, ethanol, or a 0.008 m aqueous diethylenetriaminepentaacetic acid (DTPA) solution]. This is a simple approach for the fabrication of carbon dots with tunable photoluminescence (PL) that differs from other preparation methods, as no post-passivation step is required. The unfocused beam of the second harmonic (wavelength 532 nm) of the Nd:YAG laser was used in our experiments. The sizes of the prepared NPs were mainly distributed in the range of 1-8 nm with an average value of 3 nm. Carbon NPs of different inner structure were prepared: hexagonal diamond phase in aqueous DTPA solution, orthorhombic carbon phase in ethanol, and amorphous carbon in water. The synthesized carbon NPs have strong luminescence in the visible region, which makes them attractive for numerous biological applications. The photoluminescence of the synthesized NPs was investigated at different excitation wavelengths, from 260 to 450 nm. The highest intensities of the emission bands were detected for an excitation wavelength of 400 nm. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Neues, Frank; Hild, Sabine; Epple, Matthias; Marti, Othmar; Ziegler, Andreas
2011-07-01
The main mineral components of the isopod cuticle consists of crystalline magnesium calcite and amorphous calcium carbonate. During moulting isopods moult first the posterior and then the anterior half of the body. In terrestrial species calcium carbonate is subject to resorption, storage and recycling in order to retain significant fractions of the mineral during the moulting cycle. We used synchrotron X-ray powder diffraction, elemental analysis and Raman spectroscopy to quantify the ACC/calcite ratio, the mineral phase distribution and the composition within the anterior and posterior tergite cuticle during eight different stages of the moulting cycle of Porcellio scaber. The results show that most of the amorphous calcium carbonate (ACC) is resorbed from the cuticle, whereas calcite remains in the old cuticle and is shed during moulting. During premoult resorption of ACC from the posterior cuticle is accompanied by an increase within the anterior tergites, and mineralization of the new posterior cuticle by resorption of mineral from the anterior cuticle. This suggests that one reason for using ACC in cuticle mineralization is to facilitate resorption and recycling of cuticular calcium carbonate. Furthermore we show that ACC precedes the formation of calcite in distal layers of the tergite cuticle. Copyright © 2011 Elsevier Inc. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Liu, Zheng; Li, Zhilin; Institute of Carbon Fibers and Composites, Beijing University of Chemical Technology, Beijing 100029
Graphical abstract: The MWCNT/Ni-B catalyst has been successfully prepared by an electroless deposition process. The Ni-B nanoparticles on the supporter are amorphous and are well-distributed. The catalytic conversion towards hydrogenation of styrene shows excellent catalytic activity of the obtained materials. Highlights: Black-Right-Pointing-Pointer A two-step treatment of MWCNTs enabled the homogeneous growth of Ni-B nanoparticles. Black-Right-Pointing-Pointer Ni-B nanoparticles were amorphous with an average size of 60 nm. Black-Right-Pointing-Pointer There were electron transfer between Ni and B. Black-Right-Pointing-Pointer The catalyst had excellent catalytic activity towards hydrogenation of styrene. -- Abstract: Nickel-boron (Ni-B) nanoparticles supported on multi-walled carbon nanotubes (MWCNTs) were successfully synthesizedmore » through an electroless deposition process using the plating bath with sodium borohydride as a reducing agent. The structural and morphological analyses using field-emission scanning electron microscopy, X-ray diffractometry and high-resolution transmission electron microscopy have shown that the Ni-B nanoparticles deposited on the sidewalls of MWCNTs are fine spheres comprised of amorphous structure with the morphologically unique fine-structure like flowers, and homogenously dispersed with a narrow particle size distribution centered at around 60 nm diameter. The catalytic activity of MWCNT/Ni-B nanoparticles was evaluated with respect to hydrogenation of styrene. The hydrogenation catalyzed by MWCNT-supported Ni-B nanoparticles has been found to make styrene selectively converted into ethylbenzene. The highest conversion reaches 99.8% under proper reaction conditions, which demonstrates the high catalytic activity of MWCNT/Ni-B nanoparticles.« less
NASA Astrophysics Data System (ADS)
Giampouras, Manolis; Garcia-Ruiz, Juan Manuel; Garrido, Carlos J.
2017-04-01
Numerous forms of hydrated or basic magnesium carbonates occur in the complex MgO-CO2-H2O system. Mineral saturation states from low temperature hydrothermal fluids in Semail Ophiolite (Oman), Prony Bay (New Caledonia) and Lost City hydrothermal field (mid-Atlantic ridge) strongly indicate the presence of magnesium hydroxy-carbonate hydrates (e.g. hydromagnesite) and magnesium hydroxides (brucite). Study of formation mechanisms and morphological features of minerals forming in the MgO-CO2-H2O system could give insights into serpentinization-driven, hydrothermal, alkaline environments, which are related to early Earth conditions. Temperature, hydration degree, pH and fluid composition are crucial factors regarding the formation, coexistence and transformation of such mineral phases. The rate of supersaturation, on the other hand, is a fundamental parameter to understand nucleation and crystal growth processes. All these parameters can be examined in a solution using different crystallization techniques. In the present study, we applied different crystallization techniques to synthesize and monitor the crystallization of Mg-bearing carbonates and hydroxides under abiotic conditions. Various crystallization techniques (counter-diffusion, vapor diffusion and unseeded solution mixing) were used to screen the formation conditions of each phase, transformation processes and structural development. Mineral and textural characterization of the different synthesized phases were carried out by X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy coupled to dispersive energy spectroscopy (FE-SEM-EDS). Experimental investigation of the effect of pH level and silica content under variable reactant concentrations revealed the importance of Amorphous Magnesium Carbonate (AMC) in the formation of hydroxy-carbonate phases (hydromagnesite and dypingite). Micro-structural resemblance between AMC precursors and later stage crystalline phases highlights the critical role of internal molecule re-organization to form crystalline structures. Aggregation of AMC spherulites triggers biomimetic morphologies forming curling laminar structures and rings. The size and number of nesquehonite (MgCO3.3H2O) crystals are controlled by pH and Mg2+ ions at pH < 9. As pH increases, nesquehonite transforms to spherical, rosette-like dypingite and/or hydromagnesite. Crystallization experiments within silica gel impedes the normal growth of prismatic nesquehonite crystals and generates peculiar dendritic crystalline structures. Finally, vapor diffusion techniques resulted in synthesis of NH4+-bearing hydrated compounds after ammonium incorporation when [NH4+]/[Mg2+] ≥ 1 and ≥ 0.5M [NH4+]. Funding: We acknowledge funding from the People programme (Marie Curie Actions - ITN) of the European Union FP7 under REA Grant Agreement n˚ 608001.
Molecular dynamics simulations of hydrogen bombardment of tungsten carbide surfaces
NASA Astrophysics Data System (ADS)
Träskelin, P.; Juslin, N.; Erhart, P.; Nordlund, K.
2007-05-01
The interaction between energetic hydrogen and tungsten carbide (WC) is of interest both due to the use of hydrogen-containing plasmas in thin-film manufacturing and due to the presence of WC in the divertor of fusion reactors. In order to study this interaction, we have carried out molecular dynamics simulations of the low-energy bombardment of deuterium impinging onto crystalline as well as amorphous WC surfaces. We find that prolonged bombardment leads to the formation of an amorphous WC surface layer, regardless of the initial structure of the WC sample. Loosely bound hydrocarbons, which can erode by swift chemical sputtering, are formed at the surface. Carbon-terminated surfaces show larger sputtering yields than tungsten-terminated surfaces. In both cumulative and noncumulative simulations, C is seen to sputter preferentially. Implications for mixed material erosion in ITER are discussed.
New applications of carbon nanostructures in microbial fuel cells (MFC)
NASA Astrophysics Data System (ADS)
Kaca, W.; Żarnowiec, P.; Keczkowska, Justyna; Suchańska, M.; Czerwosz, E.; Kozłowski, M.
2014-11-01
In the studies presented we proposed a new application for nanocomposite carbon films (C-Pd). These films were evaluated as an anode material for Microbial Fuel Cells (MFCs) used for electrical current generation. The results of characterization of C-Pd films composed of carbon and palladium nanograins were obtained using the Physical Vapor Deposition (PVD) method. The film obtained by this method exhibits a multiphase structure composed of fullerene nanograins, amorphous carbon and palladium nanocrystals. Raman Spectroscopy (RS) and scanning electron microscopy (SEM) are used to characterize the chemical composition, morphology and topography of these films. We observed, for MFC with C-Pd anode, the highest electrochemical activity and maximal voltage density - 458 mV (20,8 mV/cm2) for Proteus mirabilis, 426 mV (19,4 mV/cm2) for Pseudomonas aeruginosa and 652 mV (29,6 mV/cm2) for sewage bacteria as the microbial catalyst.
NASA Astrophysics Data System (ADS)
Zhang, Chuanfang (John); Maloney, Ryan; Lukatskaya, Maria R.; Beidaghi, Majid; Dyatkin, Boris; Perre, Emilie; Long, Donghui; Qiao, Wenming; Dunn, Bruce; Gogotsi, Yury
2015-01-01
Herein we report on the hydrothermal synthesis of niobium pentoxide on carbide-derived carbon (Nb2O5/CDC) with a layered structure. The presence of phenylphosphonic acid guides the deposition during preparation, leading to the formation of amorphous Nb2O5 particles which are 4-10 nm in diameter and homogeneously distributed on the CDC framework. Electrochemical testing of the Nb2O5/CDC electrode indicated that the highest capacitance and Coulombic efficiency occurred using an electrolyte comprised of 1 M lithium perchlorate in ethylene carbonate/dimethyl carbonate. Subsequent heat treatment of Nb2O5/CDC in CO2 environment led to crystallization of the Nb2O5, allowing reversible Li+ intercalation/de-intercalation. For sweep rates corresponding to charging and discharging in under 3 min, a volumetric charge of 180 C cm-3 and Coulombic efficiency of 99.2% were attained.
Deformation-induced localized solid-state amorphization in nanocrystalline nickel.
Han, Shuang; Zhao, Lei; Jiang, Qing; Lian, Jianshe
2012-01-01
Although amorphous structures have been widely obtained in various multi-component metallic alloys, amorphization in pure metals has seldom been observed and remains a long-standing scientific curiosity and technological interest. Here we present experimental evidence of localized solid-state amorphization in bulk nanocrystalline nickel introduced by quasi-static compression at room temperature. High-resolution electron microscope observations illustrate that nano-scale amorphous structures present at the regions where severe deformation occurred, e.g. along crack paths or surrounding nano-voids. These findings have indicated that nanocrystalline structures are highly desirable for promoting solid-state amorphization, which may provide new insights for understanding the nature of the crystalline-to-amorphous transformation and suggested a potential method to produce elemental metallic glasses that have hardly been available hitherto through rapid solidification.
Deformation-induced localized solid-state amorphization in nanocrystalline nickel
Han, Shuang; Zhao, Lei; Jiang, Qing; Lian, Jianshe
2012-01-01
Although amorphous structures have been widely obtained in various multi-component metallic alloys, amorphization in pure metals has seldom been observed and remains a long-standing scientific curiosity and technological interest. Here we present experimental evidence of localized solid-state amorphization in bulk nanocrystalline nickel introduced by quasi-static compression at room temperature. High-resolution electron microscope observations illustrate that nano-scale amorphous structures present at the regions where severe deformation occurred, e.g. along crack paths or surrounding nano-voids. These findings have indicated that nanocrystalline structures are highly desirable for promoting solid-state amorphization, which may provide new insights for understanding the nature of the crystalline-to-amorphous transformation and suggested a potential method to produce elemental metallic glasses that have hardly been available hitherto through rapid solidification. PMID:22768383
Qi, Chao; Zhu, Ying-Jie; Chen, Feng
2014-03-26
Calcium carbonate and calcium phosphate are the main components of biominerals. Among all of the forms of biominerals, amorphous calcium carbonate (ACC) and amorphous calcium phosphate (ACP) are the most important forms because they play a pivotal role in the process of biomineralization and are the precursors to the crystalline polymorphs. In this work, we first synthesized ACC in vitro using adenosine 5'-triphosphate disodium salt (ATP) as the stabilizer and investigated the transformation of the ACC under microwave hydrothermal conditions, and ACC/ACP composite nanospheres and carbonated hydroxyapatite (CHA) nanospheres were successfully prepared. In this novel strategy, ATP has two main functions: it serves as the stabilizer for ACC and the phosphorus source for ACP and CHA. Most importantly, the morphology and the size of the ACC precursor can be well-preserved after microwave heating, so it provides a new method for the preparation of calcium phosphate nanostructured materials using phosphorus-containing biomolecule-stabilized ACC as the precursor. Furthermore, the as-prepared ACC/ACP composite nanospheres have excellent biocompatibility and high protein adsorption capacity, indicating that they are promising for applications in biomedical fields such as drug delivery and protein adsorption.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jiang, Y. C.; Gao, J., E-mail: jugao@hku.hk
2016-08-22
Co-doped amorphous carbon (Co-C)/silicon heterostructures were fabricated by growing Co-C films on n-type Si substrates using pulsed laser deposition. A photovoltaic effect (PVE) has been observed at room temperature. Open-circuit voltage V{sub oc} = 320 mV and short-circuit current density J{sub sc }= 5.62 mA/cm{sup 2} were measured under illumination of 532-nm light with the power of 100 mW/cm{sup 2}. In contrast, undoped amorphous carbon/Si heterostructures revealed no significant PVE. Based on the PVE and photoconductivity (PC) investigated at different temperatures, it was found that the energy conversion efficiency increased with increasing the temperature and reached the maximum at room temperature, while the photoconductivity showed amore » reverse temperature dependence. The observed competition between PVE and PC was correlated with the way to distribute absorbed photons. The possible mechanism, explaining the enhanced PVE and PC in the Co-C/Si heterostructures, might be attributed to light absorption enhanced by localized surface plasmons in Co nanoparticles embedded in the carbon matrix.« less
Amorphous metal formulations and structured coatings for corrosion and wear resistance
Farmer, Joseph C.
2014-07-15
A system for coating a surface comprising providing a source of amorphous metal that contains more than 11 elements and applying the amorphous metal that contains more than 11 elements to the surface by a spray. Also a coating comprising a composite material made of amorphous metal that contains more than 11 elements. An apparatus for producing a corrosion-resistant amorphous-metal coating on a structure comprises a deposition chamber, a deposition source in the deposition chamber that produces a deposition spray, the deposition source containing a composite material made of amorphous metal that contains more than 11 elements, and a system that directs the deposition spray onto the structure.
Amorphous metal formulations and structured coatings for corrosion and wear resistance
Farmer, Joseph C [Tracy, CA
2011-12-13
A system for coating a surface comprising providing a source of amorphous metal that contains more than 11 elements and applying the amorphous metal that contains more than 11 elements to the surface by a spray. Also a coating comprising a composite material made of amorphous metal that contains more than 11 elements. An apparatus for producing a corrosion-resistant amorphous-metal coating on a structure comprises a deposition chamber, a deposition source in the deposition chamber that produces a deposition spray, the deposition source containing a composite material made of amorphous metal that contains more than 11 elements, and a system that directs the deposition spray onto the structure.
High-Density Amorphous Ice, the Frost on Interstellar Grains
NASA Technical Reports Server (NTRS)
Jenniskens, P.; Blake, D. F.; Wilson, M. A.; Pohorille, A.
1995-01-01
Most water ice in the universe is in a form which does not occur naturally on Earth and of which only minimal amounts have been made in the laboratory. We have encountered this 'high-density amorphous ice' in electron diffraction experiments of low-temperature (T less than 30 K) vapor-deposited water and have subsequently modeled its structure using molecular dynamics simulations. The characteristic feature of high-density amorphous ice is the presence of 'interstitial' oxygen pair distances between 3 and 4 A. However, we find that the structure is best described as a collapsed lattice of the more familiar low-density amorphous form. These distortions are frozen in at temperatures below 38 K because, we propose, it requires the breaking of one hydrogen bond, on average, per molecule to relieve the strain and to restructure the lattice to that of low-density amorphous ice. Several features of astrophysical ice analogs studied in laboratory experiments are readily explained by the structural transition from high-density amorphous ice into low-density amorphous ice. Changes in the shape of the 3.07 gm water band, trapping efficiency of CO, CO loss, changes in the CO band structure, and the recombination of radicals induced by low-temperature UV photolysis all covary with structural changes that occur in the ice during this amorphous to amorphous transition. While the 3.07 micrometers ice band in various astronomical environments can be modeled with spectra of simple mixtures of amorphous and crystalline forms, the contribution of the high-density amorphous form nearly always dominates.
Nanostructural characterization of amorphous diamondlike carbon films
DOE Office of Scientific and Technical Information (OSTI.GOV)
SIEGAL,MICHAEL P.; TALLANT,DAVID R.; MARTINEZ-MIRANDA,L.J.
2000-01-27
Nanostructural characterization of amorphous diamondlike carbon (a-C) films grown on silicon using pulsed-laser deposition (PLD) is correlated to both growth energetic and film thickness. Raman spectroscopy and x-ray reflectivity probe both the topological nature of 3- and 4-fold coordinated carbon atom bonding and the topographical clustering of their distributions within a given film. In general, increasing the energetic of PLD growth results in films becoming more ``diamondlike'', i.e. increasing mass density and decreasing optical absorbance. However, these same properties decrease appreciably with thickness. The topology of carbon atom bonding is different for material near the substrate interface compared to materialmore » within the bulk portion of an a-C film. A simple model balancing the energy of residual stress and the free energies of resulting carbon topologies is proposed to provide an explanation of the evolution of topographical bonding clusters in a growing a-C film.« less
Diamond structure recovery during ion irradiation at elevated temperatures
NASA Astrophysics Data System (ADS)
Deslandes, Alec; Guenette, Mathew C.; Belay, Kidane; Elliman, Robert G.; Karatchevtseva, Inna; Thomsen, Lars; Riley, Daniel P.; Lumpkin, Gregory R.
2015-12-01
CVD diamond is irradiated by 5 MeV carbon ions, with each sample held at a different temperature (300-873 K) during irradiations. The defect structures resulting from the irradiations are evident as vacancy, interstitial and amorphous carbon signals in Raman spectra. The observed variation of the full width at half maximum (FWHM) and peak position of the diamond peak suggests that disorder in the diamond lattice is reduced for high temperature irradiations. The dumbbell interstitial signal is reduced for irradiations at 873 K, which suggests this defect is unstable at these temperatures and that interstitials have migrated to crystal surfaces. Near edge X-ray absorption fine structure (NEXAFS) spectroscopy results indicate that damage to the diamond structure at the surface has occurred for room temperature irradiations, however, this structure is at least partially recovered for irradiations performed at 473 K and above. The results suggest that, in a high temperature irradiation environment such as a nuclear fusion device, in situ annealing of radiation-created defects can maintain the diamond structure and prolong the lifetime of diamond components.
Chemically synthesized boron carbon oxynitride as a new cold cathode material
NASA Astrophysics Data System (ADS)
Banerjee, Diptonil; Maity, Supratim; Chattopadhyay, K. K.
2015-11-01
Synthesis of boron carbon oxynitride (BCNO) nanosheets at different temperature from amorphous to crystalline regime has been reported. The synthesis was done by a simple molten salt process using sodium borohydride and urea as precursors. Transmission electron microscopic study confirms the formation of sheet-like structure of the as-synthesized material. The performances of the as-synthesized BCNO nanosheets as cold cathode materials have been studied for the first time in the high vacuum electron field emission set up. It has been seen that the material gives considerable field emission current with turn on field as low as 2.95 V/μm with good stability and thus a new cold cathode material can be postulated.
Single-walled carbon nanotubes (SWCNTs) with proper functionalization are desirable for applications that require dispersion in aqueous and biological environments, and functionalized SWCNTs also serve as building blocks for conjugation with specific molecules in these applicatio...
NASA Astrophysics Data System (ADS)
Naradikian, H.; Petrov, M.; Katranchev, B.; Milenov, T.; Tinchev, S.
2017-01-01
Diamond-like carbon (DLC) and amorphous carbon films are very promising type of semiconductor materials. Depending on the hybridization sp2/sp3 ratio, the material’s band gap varies between 0.8 and 3 eV. Moreover carbon films possess different interesting for practice properties: comparable to the Silicon, Diamond like structure has 22-time better thermal conductivity etc. Here we present one type of implementation of such type nanostructure. That is one attempt for orientation of dimeric LC by using of pre-deposited DLC layer with different ratio of sp2/sp3 hybridized carbon content. It could be expected a pronounced π1-π2interaction between s and p orbital levels on the surface and the dimeric ring of LC. We present comparison of surface anchoring strengths of both orientation inter-surfaces DLC/dimeric LC and single wall carbon nanotubes (SWCNT)/dimeric LC. The mechanism of interaction of dimeric LC and activated surfaces with DLC or SWCNT will be discussed. In both cases we have π-π interaction, which in combination with hydrogen bonding, typical for the dimeric LCs, influence the LC alignment. The Raman spectroscopy data evidenced the presence of charge transfer between contacting hexagonal rings of DLC and the C = O groups of the LC molecules.
Zhang, Rui; Santangelo, Saveria; Fazio, Enza; Neri, Fortunato; D'Arienzo, Massimiliano; Morazzoni, Franca; Zhang, Yihe; Pinna, Nicola; Russo, Patrícia A
2015-10-12
TiO2 is frequently combined with carbon materials, such as reduced graphene oxide (RGO), to produce composites with improved properties, for example for photocatalytic applications. It is shown that heating conditions significantly affect the interface and photocatalytic properties of TiO2 @C, and that microwave irradiation can be advantageous for the synthesis of carbon-based materials. Composites of TiO2 with RGO or amorphous carbon were prepared from reaction of titanium isopropoxide with benzyl alcohol. During the synthesis of the TiO2 nanoparticles, the carbon is involved in reactions that lead to the covalent attachment of the oxide, the extent of which depends on the carbon characteristics, heating rate, and mechanism. TiO2 is more efficiently stabilized at the surface of RGO than amorphous carbon. Rapid heating of the reaction mixture results in a stronger coupling between the nanoparticles and carbon, more uniform coatings, and smaller particles with narrower size distributions. The more efficient attachment of the oxide leads to better photocatalytic performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Quantitative nondestructive evaluation of materials and structures
NASA Technical Reports Server (NTRS)
Smith, Barry T.
1991-01-01
An experimental investigation was undertaken to quantify damage tolerance and resistance in composite materials impacted using the drop-weight method. Tests were conducted on laminates of several different carbon-fiber composite systems, such as epoxies, modified epoxies, and amorphous and semicrystalline thermoplastics. Impacted composite specimens were examined using destructive and non-destructive techniques to establish the characteristic damage states. Specifically, optical microscopy, ultrasonic, and scanning electron microscopy techniques were used to identify impact induced damage mechanisms. Damage propagation during post impact compression was also studied.
WWW database of optical constants for astronomy
NASA Astrophysics Data System (ADS)
Henning, Th.; Il'In, V. B.; Krivova, N. A.; Michel, B.; Voshchinnikov, N. V.
1999-04-01
The database we announce contains references to the papers, data files and links to the Internet resources related to measurements and calculations of the optical constants of the materials of astronomical interest: different silicates, ices, oxides, sulfides, carbides, carbonaceous species from amorphous carbon to graphite and diamonds, etc. We describe the general structure and content of the database which has now free access via Internet: http://www.astro.spbu.ru/JPDOC/entry.html\\ or \\ http:// www. astro.uni-jena.de/Users/database/entry.html
DOE Office of Scientific and Technical Information (OSTI.GOV)
Persson, P. O. A.; Ryves, L.; Tucker, M. D.
2008-10-01
Ti/C and TiC/C multilayers with periods ranging from 2 to 18 nm were grown by filtered high current pulsed cathodic arc. The growth was monitored in situ by ellipsometry and cantilever stress measurements. The ellipsometry results reveal that the optical properties of the carbon vary as a function of thickness. Correspondingly, the stress in each carbon layer as measured in situ exhibits two well defined values: initially the stress is low and then takes on a higher value for the remainder of the layer. Transmission electron microscopy shows that the initial growth of carbon on Ti or TiC layer ismore » oriented with graphitic basal planes aligned parallel to the interface. After 2-4 nm of growth, the graphitic structure transforms to amorphous carbon. Electron energy loss spectroscopy shows that the carbon layer simultaneously undergoes a transition from sp{sup 2} rich to sp{sup 3} rich material.« less
[Study on solid dispersion of precipitated calcium carbonate-based oleanolic acid].
Yan, Hong-mei; Zhang, Zhen-hai; Jia, Xiao-bin; Jiang, Yan-rong; Sun, E
2015-05-01
Oleanolic acid-precipitated calcium carbonate solid dispersion was prepared by using solvent evaporation method. The microscopic structure and physicochemical properties of solid dispersion were analyzed using differential scanning calorimetry and scanning electron microscopy (SEM). And its in vitro release also was investigated. The properties of the precipitated calcium carbonate was studied which was as a carrier of oleanolic acid solid dispersion. Differential scanning calorimetry analysis suggested that oleanolic acid may be present in solid dispersion as amorphous substance. The in vitro release determination results of oleanolic acid-precipitated calcium carbonate (1: 5) solid dispersion showed accumulated dissolution rate of.oleanolic acid was up to 90% at 45 min. Accelerating experiment showed that content and in vitro dissolution of oleanolic acid solid dispersion did not change after storing over 6 months. The results indicated that in vitro dissolution of oleanolic acid was improved greatly by the solid dispersion with precipitated calcium carbonate as a carrier. The solid dispersion is a stabilizing system which has actual applied value.
Overview of the amorphous precursor phase strategy in biomineralization
NASA Astrophysics Data System (ADS)
Weiner, Steve; Mahamid, Julia; Politi, Yael; Ma, Yurong; Addadi, Lia
2009-06-01
It was assumed for a long time that organisms produce minerals directly from a saturated solution. A few exceptions were known, including the well documented mineralized teeth of the chiton. In 1997 it was demon-strated that sea urchin larvae form their calcitic spicules by first depositing a highly unstable mineral phase called amorphous calcium carbonate. This strategy has since been shown to be used by animals from other phyla and for both aragonite and calcite. Recent evidence shows that vertebrate bone mineral may also be formed via a precursor phase of amorphous calcium carbonate. This strategy thus appears to be widespread. The challenge now is to understand the mechanisms by which these unstable phases are initially formed, how they are temporarily stabilized and how they are destabilized and transform into a crystalline mature product.
NASA Astrophysics Data System (ADS)
Raut, U.; Fulvio, D.; Loeffler, M. J.; Baragiola, R. A.
2012-06-01
We report the synthesis of carbon dioxide on an amorphous carbon-13 substrate coated with amorphous water ice from irradiation with 100 keV protons at 20 K and 120 K. The quantitative studies show that the CO2 is dispersed in the ice; its column density increases with ion fluence to a maximum value (in 1015 molecules cm-2) of ~1 at 20 K and ~3 at 120 K. The initial yield is 0.05 (0.1) CO2 per incident H+ at 20 (120) K. The CO2 destruction process, which limits the maximum column density, occurs with an effective cross section of ~2.5 (4.1) × 10-17 cm2 at 20 (120) K. We discuss radiation-induced oxidation by reactions of radicals in water with the carbon surface and demonstrate that these reactions can be a significant source of condensed carbon dioxide in interstellar grains and in icy satellites in the outer solar system.
Synthesis and acid catalysis of cellulose-derived carbon-based solid acid
NASA Astrophysics Data System (ADS)
Suganuma, Satoshi; Nakajima, Kiyotaka; Kitano, Masaaki; Yamaguchi, Daizo; Kato, Hideki; Hayashi, Shigenobu; Hara, Michikazu
2010-06-01
SO 3H-bearing amorphous carbon, prepared by partial carbonization of cellulose followed by sulfonation in fuming H 2SO 4, was applied as a solid catalyst for the acid-catalyzed hydrolysis of β-1,4 glucan, including cellobiose and crystalline cellulose. Structural analyses revealed that the resulting carbon material consists of graphene sheets with 1.5 mmol g -1 of SO 3H groups, 0.4 mmol g -1 of COOH, and 5.6 mmol g -1 of phenolic OH groups. The carbon catalyst showed high catalytic activity for the hydrolysis of β-1,4 glycosidic bonds in both cellobiose and crystalline cellulose. Pure crystalline cellulose was not hydrolyzed by conventional strong solid Brønsted acid catalysts such as niobic acid, Nafion ® NR-50, and Amberlyst-15, whereas the carbon catalyst efficiently hydrolyzes cellulose into water-soluble saccharides. The catalytic performance of the carbon catalyst is due to the large adsorption capacity for hydrophilic reactants and the adsorption ability of β-1,4 glucan, which is not adsorbed to other solid acids.
Oxygen ion-beam microlithography
Tsuo, Y.S.
1991-08-20
A method of providing and developing a resist on a substrate for constructing integrated circuit (IC) chips includes the following steps: of depositing a thin film of amorphous silicon or hydrogenated amorphous silicon on the substrate and exposing portions of the amorphous silicon to low-energy oxygen ion beams to oxidize the amorphous silicon at those selected portions. The nonoxidized portions are then removed by etching with RF-excited hydrogen plasma. Components of the IC chip can then be constructed through the removed portions of the resist. The entire process can be performed in an in-line vacuum production system having several vacuum chambers. Nitrogen or carbon ion beams can also be used. 5 figures.
Oxygen ion-beam microlithography
Tsuo, Y. Simon
1991-01-01
A method of providing and developing a resist on a substrate for constructing integrated circuit (IC) chips includes the following steps: of depositing a thin film of amorphous silicon or hydrogenated amorphous silicon on the substrate and exposing portions of the amorphous silicon to low-energy oxygen ion beams to oxidize the amorphous silicon at those selected portions. The nonoxidized portions are then removed by etching with RF-excited hydrogen plasma. Components of the IC chip can then be constructed through the removed portions of the resist. The entire process can be performed in an in-line vacuum production system having several vacuum chambers. Nitrogen or carbon ion beams can also be used.
Peltola, Emilia; Wester, Niklas; Holt, Katherine B; Johansson, Leena-Sisko; Koskinen, Jari; Myllymäki, Vesa; Laurila, Tomi
2017-02-15
We hypothesize that by using integrated carbon nanostructures on tetrahedral amorphous carbon (ta-C), it is possible to take the performance and characteristics of these bioelectrodes to a completely new level. The integrated carbon electrodes were realized by combining nanodiamonds (NDs) with ta-C thin films coated on Ti-coated Si-substrates. NDs were functionalized with mixture of carboxyl and amine groups ND andante or amine ND amine , carboxyl ND vox or hydroxyl groups ND H and drop-casted or spray-coated onto substrate. By utilizing these novel structures we show that (i) the detection limit for dopamine can be improved by two orders of magnitude [from 10µM to 50nM] in comparison to ta-C thin film electrodes and (ii) the coating method significantly affects electrochemical properties of NDs and (iii) the ND coatings selectively promote cell viability. ND andante and ND H showed most promising electrochemical properties. The viability of human mesenchymal stem cells and osteoblastic SaOS-2 cells was increased on all ND surfaces, whereas the viability of mouse neural stem cells and rat neuroblastic cells was improved on ND andante and ND H and reduced on ND amine and ND vox. The viability of C6 cells remained unchanged, indicating that these surfaces will not cause excess gliosis. In summary, we demonstrated here that by using functionalized NDs on ta-C thin films we can significantly improve sensitivity towards dopamine as well as selectively promote cell viability. Thus, these novel carbon nanostructures provide an interesting concept for development of various in vivo targeted sensor solutions. Copyright © 2016 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Stevens, Kimberly A.; Esplin, Christian D.; Davis, Taylor M.; Butterfield, D. Jacob; Ng, Philip S.; Bowden, Anton E.; Jensen, Brian D.; Iverson, Brian D.
2018-05-01
The use of carbon nanotubes to create superhydrophobic coatings has been considered due to their ability to offer a relatively uniform nanostructure. However, carbon nanotubes (CNTs) may be considered delicate with a typical diameter of tens of nanometers for a multi-walled CNT; as-grown carbon nanotubes often require the addition of a thin-film hydrophobic coating to render them superhydrophobic. Furthermore, fine control over the diameter of the as-grown CNTs or the overall nanostructure is difficult. This work demonstrates the utility of using carbon infiltration to layer amorphous carbon on multi-walled nanotubes to improve structural integrity and achieve superhydrophobic behavior with tunable geometry. These carbon-infiltrated carbon nanotube (CICNT) surfaces exhibit an increased number of contact points between neighboring tubes, resulting in a composite structure with improved mechanical stability. Additionally, the native surface can be rendered superhydrophobic with a vacuum pyrolysis treatment, with contact angles as high as 160° and contact angle hysteresis on the order of 1°. The CICNT diameter, static contact angle, sliding angle, and contact angle hysteresis were examined for varying levels of carbon-infiltration to determine the effect of infiltration on superhydrophobicity. The same superhydrophobic behavior and tunable geometry were also observed with CICNTs grown directly on stainless steel without an additional catalyst layer. The ability to tune the geometry while maintaining superhydrophobic behavior offers significant potential in condensation heat transfer, anti-icing, microfluidics, anti-microbial surfaces, and other bio-applications where control over the nanostructure is beneficial.
Iwata, Masanori; Teshima, Midori; Seki, Takahiro; Yoshioka, Shinya; Takeoka, Yukikazu
2017-07-01
Inspired by Steller's jay, which displays angle-independent structural colors, angle-independent structurally colored materials are created, which are composed of amorphous arrays of submicrometer-sized fine spherical silica colloidal particles. When the colloidal amorphous arrays are thick, they do not appear colorful but almost white. However, the saturation of the structural color can be increased by (i) appropriately controlling the thickness of the array and (ii) placing the black background substrate. This is similar in the case of the blue feather of Steller's jay. Based on the knowledge gained through the biomimicry of structural colored materials, colloidal amorphous arrays on the surface of a black particle as the core particle are also prepared as colorful photonic pigments. Moreover, a structural color on-off system is successfully built by controlling the background brightness of the colloidal amorphous arrays. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Mechanically Induced Graphite-Nanodiamonds-Phase Transformations During High-Energy Ball Milling
NASA Astrophysics Data System (ADS)
El-Eskandarany, M. Sherif
2017-05-01
Due to their unusual mechanical, chemical, physical, optical, and biological properties, nearly spherical-like nanodiamonds have received much attention as desirable advanced nanomaterials for use in a wide spectrum of applications. Although, nanodiamonds can be successfully synthesized by several approaches, applications of high temperature and/or high pressure may restrict the real applications of such strategic nanomaterials. Distinct from the current preparation approaches used for nanodiamonds preparation, here we show a new process for preparing ultrafine nanodiamonds (3-5 nm) embedded in a homogeneous amorphous-carbon matrix. Our process started from high-energy ball milling of commercial graphite powders at ambient temperature under normal atmospheric helium gas pressure. The results have demonstrated graphite-single wall carbon nanotubes-amorphous-carbon-nanodiamonds phase transformations carried out through three subsequent stages of ball milling. Based on XRD and RAMAN analyses, the percentage of nanodiamond phase + C60 (crystalline phase) produced by ball milling was approximately 81%, while the amorphous phase amount was 19%. The pressure generated on the powder together the with temperature increase upon the ball-powder-ball collision is responsible for the phase transformations occurring in graphite powders.
Amorphous calcium carbonate particles form coral skeletons
NASA Astrophysics Data System (ADS)
Mass, Tali; Giuffre, Anthony J.; Sun, Chang-Yu; Stifler, Cayla A.; Frazier, Matthew J.; Neder, Maayan; Tamura, Nobumichi; Stan, Camelia V.; Marcus, Matthew A.; Gilbert, Pupa U. P. A.
2017-09-01
Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO3). We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO2 increases, such as the Paleocene-Eocene Thermal Maximum that occurred 56 Mya.
Amorphous calcium carbonate particles form coral skeletons.
Mass, Tali; Giuffre, Anthony J; Sun, Chang-Yu; Stifler, Cayla A; Frazier, Matthew J; Neder, Maayan; Tamura, Nobumichi; Stan, Camelia V; Marcus, Matthew A; Gilbert, Pupa U P A
2017-09-12
Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed "vital effects," that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO 3 ). We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO 2 increases, such as the Paleocene-Eocene Thermal Maximum that occurred 56 Mya.
Amorphous calcium carbonate particles form coral skeletons
Mass, Tali; Giuffre, Anthony J.; Sun, Chang-Yu; Stifler, Cayla A.; Frazier, Matthew J.; Neder, Maayan; Tamura, Nobumichi; Stan, Camelia V.; Marcus, Matthew A.
2017-01-01
Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO3). We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO2 increases, such as the Paleocene–Eocene Thermal Maximum that occurred 56 Mya. PMID:28847944
Kalra, Arjun; Lubach, Joseph W; Munson, Eric J; Li, Tonglei
2018-02-07
Molecular understanding of phase stability and transition of the amorphous state helps in formulation and manufacturing of poorly-soluble drugs. Crystallization of a model compound, 2-phenylamino nicotinic acid (2PNA), from the amorphous state was studied using solid-state analytical methods. Our previous report suggests that 2PNA molecules mainly develop intermolecular -COOH∙∙∙pyridine N (acid-pyridine) interactions in the amorphous state. In the current study, the molecular speciation is explored with regard to the phase transition from the amorphous to the crystalline state. Using spectroscopic techniques, the molecular interactions and structural evolvement during the recrystallization from the glassy state were investigated. The results unveiled that the structurally heterogeneous amorphous state contains acid-pyridine aggregates - either as hydrogen-bonded neutral molecules or as zwitterions - as well as a population of carboxylic acid dimers. Phase transition from the amorphous state results in crystal structures composed of carboxylic acid dimer (acid-acid) synthon or acid-pyridine chains depending on the crystallization conditions employed. The study underlines the structural evolvement, as well as its impact on the metastability, of amorphous samples from local, supramolecular assemblies to long-range intermolecular ordering through crystallization.
NASA Technical Reports Server (NTRS)
Miyoshi, Kazuhisa
1999-01-01
This chapter describes three studies on the surface design, surface engineering, and tribology of chemical-vapor-deposited (CVD) diamond films and coatings toward wear-resistant, self-lubricating diamond films and coatings. Friction mechanisms and solid lubrication mechanisms of CVD diamond are stated. Effects of an amorphous hydrogenated carbon on CVD diamond, an amorphous, nondiamond carbon surface layer formed on CVD diamond by carbon and nitrogen ion implantation, and a materials combination of cubic boron nitride and CVD diamond on the adhesion, friction, and wear behaviors of CVD diamond in ultrahigh vacuum are described. How surface modification and the selected materials couple improved the tribological functionality of coatings, giving low coefficient of friction and good wear resistance, is explained.
NASA Astrophysics Data System (ADS)
Keiluweit, M.; Nico, P. S.; Johnson, M. G.; Kleber, M.
2009-12-01
Solid residues of incomplete combustion (biochar or char) are continuously being added to soils due to natural vegetation fires in many ecosystems. However, new strategies for carbon sequestration in soils are likely to include the active addition of biochar to soils. Since biochar is a highly aromatic organic material such additions will modify the native molecular structure of soil organic matter and thus alter interactions with the global atmosphere and hydrosphere. Here we present a molecular level assessment of the physical organization and chemical complexity of biomass-derived chars and, specifically, that of aromatic carbon in char structures. Differences among wood and grass charred at temperatures from 100 to 700°C are investigated. BET-N2 surface area, X-ray diffraction (XRD), synchrotron-based Near-edge X-ray Absorption Fine Structure (NEXAFS) and Fourier transform infrared (FT-IR) spectroscopy results demonstrate how the two plant precursor materials undergo analogous, but quantitatively different physical-chemical transitions as charring intensity increases. These changes suggest the existence of four distinct physical and chemical categories of char. We find that each category of char consists of a unique mixture of chemical phases and physical states: (i) in transition chars the crystalline character of the precursor materials is preserved, (ii) in amorphous chars the heat-altered molecules and incipient aromatic polycondensates are randomly mixed, (iii) composite chars consist of poorly ordered graphene stacks embedded in amorphous phases, and (iv) turbostratic chars are dominated by turbostratic (disordered) graphitic crystallites. There is wide variation in both the chemical and the physical nature of aromatic carbon among these char categories. In this presentation we will point out how molecular variations among the aromatic components of the different char categories translate into differences in their ability to: (i) persist in the environment, (ii) function as environmental sorbents, and (iii) to enable the soil to provide environmental services.
Large Scale Synthesis and Light Emitting Fibers of Tailor-Made Graphene Quantum Dots
Park, Hun; Hyun Noh, Sung; Hye Lee, Ji; Jun Lee, Won; Yun Jaung, Jae; Geol Lee, Seung; Hee Han, Tae
2015-01-01
Graphene oxide (GO), which is an oxidized form of graphene, has a mixed structure consisting of graphitic crystallites of sp2 hybridized carbon and amorphous regions. In this work, we present a straightforward route for preparing graphene-based quantum dots (GQDs) by extraction of the crystallites from the amorphous matrix of the GO sheets. GQDs with controlled functionality are readily prepared by varying the reaction temperature, which results in precise tunability of their optical properties. Here, it was concluded that the tunable optical properties of GQDs are a result of the different fraction of chemical functionalities present. The synthesis approach presented in this paper provides an efficient strategy for achieving large-scale production and long-time optical stability of the GQDs, and the hybrid assembly of GQD and polymer has potential applications as photoluminescent fibers or films. PMID:26383257
Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate
Radha, A. V.; Forbes, Tori Z.; Killian, Christopher E.; Gilbert, P. U. P. A.; Navrotsky, Alexandra
2010-01-01
Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC⇒anhydrous ACC ∼ biogenic anhydrous ACC⇒vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO2 sequestration. PMID:20810918
Chemical Mapping of Proterozoic Organic Matter at Sub-Micron Spatial Resolution
NASA Technical Reports Server (NTRS)
Oehler, Dorothy Z.; Robert, Francois; Mostefaoui, Smail; Meibom, Anders; Selo, Madeleine; McKay, David S.
2006-01-01
We have used a NanoSIMS ion microprobe to map sub-micron-scale distributions of carbon, nitrogen, sulfur, silicon, and oxygen in organic microfossils and laminae from the approximately 0.85 Ga Bitter Springs Formation of Australia. The data provide clues about the original chemistry of the microfossils, the silicification process, and biosignatures of specific microorganisms and microbial communities. Chemical maps of fossil unicells and filaments reveal distinct wall-and sheath-like structures enriched in C, N and S, consistent with their accepted biological origin. Surprisingly, organic laminae, previously considered to be amorphous, also exhibit filamentous and apparently compressed spheroidal structures defined by strong enrichments in C, N and S. By analogy to data from the well-preserved microfossils, these structures are interpreted as being of biological origin, most likely representing densely packed remnants of microbial mats. Because the preponderance of organic matter in Precambrian sediments is similarly "amorphous," our findings open a large body of generally neglected material to in situ structural, chemical, and isotopic study. Our results also offer new criteria for assessing biogenicity of problematic kerogenous materials and thus can be applied to assessments of poorly preserved or fragmentary organic residues in early Archean sediments and any that might occur in meteorites or other extraterrestrial samples.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kudoyarova, V. Kh., E-mail: kudoyarova@mail.ioffe.ru; Tolmachev, V. A.; Gushchina, E. V.
2013-03-15
Rutherford backscattering, IR spectroscopy, ellipsometry, and atomic-force microscopy are used to perform an integrated study of the composition, structure and optical properties of a-Si{sub 1-x}C{sub x}:H Left-Pointing-Angle-Bracket Er Right-Pointing-Angle-Bracket amorphous films. The technique employed to obtain the a-Si{sub 1-x}C{sub x}:H Left-Pointing-Angle-Bracket Er Right-Pointing-Angle-Bracket amorphous films includes the high-frequency decomposition of a mixture of gases, (SiH{sub 4}){sub a} + (CH{sub 4}){sub b}, and the simultaneous thermal evaporation of a complex compound, Er(pd){sub 3}. It is demonstrated that raising the amount of CH{sub 4} in the gas mixture results in an increase in the carbon content of the films under study andmore » an increase in the optical gap E{sub g}{sup opt} from 1.75 to 2.2 eV. Changes in the composition of a-Si{sub 1-x}C{sub x}:H Left-Pointing-Angle-Bracket Er Right-Pointing-Angle-Bracket amorphous films, accompanied, in turn, by changes in the optical constants, are observed in the IR spectra. The ellipsometric spectra obtained are analyzed in terms of multiple-parameter models. The conclusion is made on the basis of this analysis that the experimental and calculated spectra coincide well when variation in the composition of the amorphous films with that of the gas mixture is taken into account. The existence of a thin (6-8 nm) silicon-oxide layer on the surface of the films under study and the validity of using the double-layer model in ellipsometric calculations is confirmed by the results of structural analyses by atomic-force microscopy.« less
The nature and origin of interstellar diamond
NASA Technical Reports Server (NTRS)
Blake, David F.; Freund, Friedemann; Shipp, Ruth; Krishnan, Kannan F. M.; Echer, Charles J.
1988-01-01
The C-delta component of the Allende meteorite is a microscopic diamond some of whose properties seem in conflict with those expected of diamond. High spatial resolution analytical data are presented here which may help explain such results. Surface and interfacial carbon atoms in the component, which may comprise as much as 25 percent of the total, impart an 'amorphous' character to some spectral data. These data support the proposed high-pressure conversion of amorphous carbon and graphite into diamonds due to grain-grain collisions in the ISM, although a low-pressure mechanism of formation cannot be ruled out.
Characteristics of amorphous kerogens fractionated from terrigenous sedimentary rocks
NASA Astrophysics Data System (ADS)
Suzuki, Noriyuki
1984-02-01
A preliminary attempt to fractionate amorphous kerogens from terrigenous bulk kerogen by a benzene-water two phase partition method under acidic condition was made. Microscopic observation revealed that amorphous kerogens and structured kerogens were fractionated effectively by this method. Characteristics of the amorphous and structured kerogens fractionated by this method were examined by some chemical analyses and compared with those of the bulk kerogen and humic acid isolated from the same rock sample (Haizume Formation, Pleistocene, Japan). The elemental and infrared (IR) analyses showed that the amorphous kerogen fraction had the highest atomic H/C ratio and the lowest atomic N/C ratio and was the richest in aliphatic structures and carbonyl and carboxyl functional groups. Quantities of fatty acids from the saponification products of each geopolymer were in agreement with the results of elemental and IR analyses. Distribution of the fatty acids was suggestive that more animal lipids participate in the formation of amorphous kerogens because of the abundance of relatively lower molecular weight fatty acids (such as C 16 and C 18 acids) in saponification products of amorphous kerogens. On the other hand, although the amorphous kerogen fraction tends to be rich in aliphatic structures compared with bulk kerogen of the same rock samples, van Krevelen plots of elemental compositions of kerogens from the core samples (Nishiyama Oil Field, Tertiary, Japan) reveal that the amorphous kerogen fraction is not necessarily characterized by markedly high atomic H/C ratio. This was attributed to the oxic environment of deposition and the abundance of biodegraded terrestrial amorphous organic matter in the amorphous kerogen fraction used in this work.
Thermal degradation of hexachlorobenzene in the presence of calcium oxide at 340-400 °C.
Yin, Keqing; Gao, Xingbao; Sun, Yifei; Zheng, Lei; Wang, Wei
2013-11-01
Hexachlorobenzene (HCB) in the milligram range was co-heated with calcium oxide (CaO) powder in sealed glass ampoules at 340-400 °C. The heated samples were characterized and analyzed by Raman spectroscopy, elemental analysis, gas chromatography/mass spectrometry, ion chromatography, and thermal/optical carbon analysis. The degradation products of HCB were studied at different temperatures and heated times. The amorphous carbon was firstly quantitatively evaluated and was thought to be important fate of the C element of HCB. The yield of amorphous carbon in products increased with heating time, for samples treated for 8h at 340, 380 °C and 400 °C, the value were 17.5%, 34.8% and 50.2%, respectively. After identification of the dechlorination products, the HCB degradation on CaO at 340-400 °C was supposed to through dechlorination/polymerization pathway, which is induced by electron transfer, generate chloride ions and form high-molecular weight intermediates with significant levels of both hydrogen and chlorine, and finally form amorphous carbon. Higher temperature was beneficial for the dechlorination/polymerization efficiency. The results are helpful for clarifying the reaction mechanism for thermal degradation of chlorinated aromatics in alkaline matrices. Copyright © 2013 Elsevier Ltd. All rights reserved.
Huang, J Y
2007-08-01
Because of technique difficulties in achieving the extreme high-pressure and high-temperature (HPHT) simultaneously, direct observation of the structures of carbon at extreme HPHT conditions has not been possible. Banhart and Ajayan discovered remarkably that carbon onions can act as nanoscopic pressure cells to generate high pressures. By heating carbon onions to approximately 700 degrees C and under electron beam irradiation, the graphite-to-diamond transformation was observed in situ by transmission electron microscopy (TEM). However, the highest achievable temperature in a TEM heating holder is less than 1000 degrees C. Here we report that, by using carbon nanotubes as heaters and carbon onions as high-pressure cells, temperatures higher than 2000 degrees C and pressures higher than 40 GPa were achieved simultaneously in carbon onions. At such HPHT conditions and facilitated by electron beam irradiation, the diamond formed in the carbon onion cores frequently changed its shape, size, orientation, and internal structure and moved like a fluid, implying that it was in a quasimelting state. The fluctuation between the solid phase of diamond and the fluid/amorphous phase of diamond-like carbon, and the changes of the shape, size, and orientation of the solid diamond, were attributed to the dynamic crystallization of diamond crystal from the quasimolten state and the dynamic graphite-diamond phase transformations. Our discovery offers unprecedented opportunities to studying the nanostructures of carbon at extreme conditions in situ and at an atomic scale.
Electrical and galvanomagnetic properties of nanoporous carbon samples impregnated with bromine
NASA Astrophysics Data System (ADS)
Danishevskii, A. M.; Popov, V. V.; Kyutt, R. N.; Gordeev, S. K.
2013-07-01
Nanoporous carbon samples with a large specific surface area can be filled with heavier elements or their compounds, which makes it possible to investigate the interaction of their electronic subsystems with carbon. One of the elements convenient for filling pores of carbon materials is bromine. Impregnation of nanoporous carbon samples with bromine causes the occurrence of the processes of micropore filling, monolayer adsorption, and intercalation. It has been found that samples impregnated with bromine substantially change their electrical and galvanomagnetic properties, and these changes depend on the structure of the samples. It has been shown that, if in the skeleton of a porous carbon sample there is a fraction of graphite clusters, the impregnation of the sample with bromine increases the concentration of charged carriers (holes). But when the sample has a quasi-amorphous structure, the injection of bromine into the sample leads to the appearance of a certain concentration of electrons in addition to charged mobile holes of the initial sample; i.e., the electrical conductivity becomes bipolar. In the former case, bromine molecules intercalate graphite clusters and, since bromine is an acceptor during intercalation of graphite, the hole concentration in the carbon skeleton network increases. In the latter case, bromine molecules can only be adsorbed on pore walls. As a result, the adsorption interaction between the electron shells of bromine molecules and the carbon surface leads to the formation of a donor layer near the surface and to the generation of electrons in the carbon skeleton network.
Influence of amorphous structure on polymorphism in vanadia
DOE Office of Scientific and Technical Information (OSTI.GOV)
Stone, Kevin H.; Schelhas, Laura T.; Garten, Lauren M.
Normally we think of the glassy state as a single phase and therefore crystallization from chemically identical amorphous precursors should be identical. Here we show that the local structure of an amorphous precursor is distinct depending on the initial deposition conditions, resulting in significant differences in the final state material. Using grazing incidence total x-ray scattering, we have determined the local structure in amorphous thin films of vanadium oxide grown under different conditions using pulsed laser deposition (PLD). Here we show that the subsequent crystallization of films deposited using different initial PLD conditions result in the formation of different polymorphsmore » of VO 2. Ultimately this suggests the possibility of controlling the formation of metastable polymorphs by tuning the initial amorphous structure to different formation pathways.« less
Influence of amorphous structure on polymorphism in vanadia
Stone, Kevin H.; Schelhas, Laura T.; Garten, Lauren M.; ...
2016-07-13
Normally we think of the glassy state as a single phase and therefore crystallization from chemically identical amorphous precursors should be identical. Here we show that the local structure of an amorphous precursor is distinct depending on the initial deposition conditions, resulting in significant differences in the final state material. Using grazing incidence total x-ray scattering, we have determined the local structure in amorphous thin films of vanadium oxide grown under different conditions using pulsed laser deposition (PLD). Here we show that the subsequent crystallization of films deposited using different initial PLD conditions result in the formation of different polymorphsmore » of VO 2. Ultimately this suggests the possibility of controlling the formation of metastable polymorphs by tuning the initial amorphous structure to different formation pathways.« less
Core-level photoabsorption study of defects and metastable bonding configurations in boron nitride
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jimenez, I.; Jankowski, A.F.; Terminello, L.J.
1997-04-01
Boron nitride is an interesting material for technological applications and for fundamental solid state physics investigations. It is a compound isoelectronic with carbon and, like carbon can possess sp{sup 2} and sp{sup 3} bonded phases resembling graphite and diamond. BN crystallizes in the sp{sup 2}-bonded hexagonal (h-BN), rhombohedral (r-BN) and turbostratic phases, and in the sp{sup 3}-bonded cubic (c-BN) and wurtzite (w-BN) phases. A new family of materials is obtained when replacing C-C pairs in graphite with isoelectronic B-N pairs, resulting in C{sub 2}BN compounds. Regarding other boron compounds, BN is exceptional in the sense that it has standard two-centermore » bonds with conventional coordination numbers, while other boron compounds (e.g. B{sub 4}C) are based on the boron icosahedron unit with three-center bonds and high coordination numbers. The existence of several allotropic forms and fullerene-like structures for BN suggests a rich variety of local bonding and poses the questions of how this affects the local electronic structure and how the material accommodates the stress induced in the transition regions between different phases. One would expect point defects to play a crucial role in stress accommodation, but these must also have a strong influence in the electronic structure, since the B-N bond is polar and a point defect will thus be a charged structure. The study of point defects in relationship to the electronic structure is of fundamental interest in these materials. Recently, the authors have shown that Near-Edge X-ray Absorption Fine Structure (NEXAFS) is sensitive to point defects in h-BN, and to the formation of metastable phases even in amorphous materials. This is significant since other phase identification techniques like vibrational spectroscopies or x-ray diffraction yield ambiguous results for nanocrystalline and amorphous samples. Serendipitously, NEXAFS also combines chemical selectivity with point defect sensitivity.« less
Deposition and properties of cobalt- and ruthenium-based ultra-thin films
NASA Astrophysics Data System (ADS)
Henderson, Lucas Benjamin
Future copper interconnect systems will require replacement of the materials that currently comprise both the liner layer(s) and the capping layer. Ruthenium has previously been considered as a material that could function as a single material liner, however its poor ability to prevent copper diffusion makes it incompatible with liner requirements. A recently described chemical vapor deposition route to amorphous ruthenium-phosphorus alloy films could correct this problem by eliminating the grain boundaries found in pure ruthenium films. Bias-temperature stressing of capacitor structures using 5 nm ruthenium-phosphorus film as a barrier to copper diffusion and analysis of the times-to-failure at accelerated temperature and field conditions implies that ruthenium-phosphorus performs acceptably as a diffusion barrier for temperatures above 165°C. The future problems associated with the copper capping layer are primarily due to the poor adhesion between copper and the current Si-based capping layers. Cobalt, which adheres well to copper, has been widely proposed to replace the Si-based materials, but its ability to prevent copper diffusion must be improved if it is to be successfully implemented in the interconnect. Using a dual-source chemistry of dicobaltoctacarbonyl and trimethylphosphine at temperatures from 250-350°C, amorphous cobalt-phosphorus can be deposited by chemical vapor deposition. The films contain elemental cobalt and phosphorus, plus some carbon impurity, which is incorporated in the film as both graphitic and carbidic (bonded to cobalt) carbon. When deposited on copper, the adhesion between the two materials remains strong despite the presence of phosphorus and carbon at the interface, but the selectivity for growth on copper compared to silicon dioxide is poor and must be improved prior to consideration for application in interconnect systems. A single molecule precursor containing both cobalt and phosphorus atoms, tetrakis(trimethylphosphine)cobalt(0), yields cobalt-phosphorus films without any co-reactant. However, the molecule does not contain sufficient amounts of amorphizing agents to fully eliminate grain boundaries, and the resulting film is nanocrystalline.
NASA Astrophysics Data System (ADS)
Jiang, N.; Deguchi, M.; Wang, C. L.; Won, J. H.; Jeon, H. M.; Mori, Y.; Hatta, A.; Kitabatake, M.; Ito, T.; Hirao, T.; Sasaki, T.; Hiraki, A.
1997-04-01
A transmission electron microscope (TEM) study of ion-implanted chemical-vapor-deposited (CVD) diamond is presented. CVD diamond used for transmission electron microscope observation was directly deposited onto Mo TEM grids. As-deposited specimens were irradiated by C (100 keV) ions at room temperature with a wide range of implantation doses (10 12-10 17/cm 2). Transmission electron diffraction (TED) patterns indicate that there exists a critical dose ( Dc) for the onset of amorphization of CVD diamond as a result of ion induced damage and the value of critical dose is confirmed to be about 3 × 10 15/cm 2. The ion-induced transformation process is clearly revealed by high resolution electron microscope (HREM) images. For a higher dose implantation (7 × 10 15/cm 2) a large amount of diamond phase is transformed into amorphous carbon and many tiny misoriented diamond blocks are found to be left in the amorphous solid. The average size of these misoriented diamond blocks is only about 1-2 nm. Further bombardment (10 17/cm 2) almost kills all of the diamond phase within the irradiated volume and moreover leads to local formation of micropolycrystalline graphite.
NASA Astrophysics Data System (ADS)
Ferguson, P. P.; Martine, M. L.; George, A. E.; Dahn, J. R.
Samples of Sn 30TM 30C 40 and of Sn 30Co 15TM 15C 40, with TM = 3d transition metals, were prepared by vertical-axis attritor milling. The structure and performance of these samples were studied by X-ray diffraction (XRD) and by electrochemical testing. The XRD patterns of Sn 30TM 30C 40 show an amorphous-like diffraction pattern only for the sample with TM = Co. The other prepared samples show broadened Bragg peaks of their main starting material, along with an amorphous-like background, even after 32 h of milling. Samples with TM = Co and TM = Ni show stable differential capacity versus potential plots and stable cycling for at least 100 cycles with reversible capacities of 425 and 250 mAh g -1, respectively. All samples prepared with 15 at.% Co show good capacity retention for at least 100 cycles ranging from 270 mAh g -1 for samples with TM = Ni to 500 mAh g -1 for samples with TM = Ti. The differential capacity versus potential plots for all the prepared Sn 30Co 15TM 15C 40 samples show similar structure to that of Sn 30Co 30C 40 except when TM = Cu. This shows the possibility of preparing tin-based negative electrode materials using a combination of cobalt and TM, especially if one looks to reduce the cobalt content.
Understanding heterogeneity in Genesis diamond-like carbon film using SIMS analysis of implants
Jurewicz, Amy J. G.; Burnett, Don S.; Rieck, Karen D.; ...
2017-07-05
An amorphous diamond-like carbon film deposited on silicon made at Sandia National Laboratory by pulsed laser deposition was one of several solar wind (SW) collectors used by the Genesis Mission (NASA Discovery Class Mission #5). The film was ~1 μm thick, amorphous, anhydrous, and had a high ratio of sp 3–sp 2 bonds (>50%). For 27 months of exposure to space at the first We passively irradiated lagrange point, the collectors, with SW (H fluence ~2 × 10 16 ions cm -2; He fluence ~8 × 10 14 ions cm -2). The radiation damage caused by the implanted H ionsmore » peaked at 12–14 nm below the surface of the film and that of He about 20–23 nm. To enable quantitative measurement of the SW fluences by secondary ion mass spectroscopy, minor isotopes of Mg ( 25Mg and 26Mg) were commercially implanted into flight-spare collectors at 75 keV and a fluence of 1 × 10 14 ions cm -2. Furthermore, the shapes of analytical depth profiles, the rate at which the profiles were sputtered by a given beam current, and the intensity of ion yields are used to characterize the structure of the material in small areas (~200 × 200 ± 50 μm). Data were consistent with the hypothesis that minor structural changes in the film were induced by SW exposure.« less
Understanding heterogeneity in Genesis diamond-like carbon film using SIMS analysis of implants
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jurewicz, Amy J. G.; Burnett, Don S.; Rieck, Karen D.
An amorphous diamond-like carbon film deposited on silicon made at Sandia National Laboratory by pulsed laser deposition was one of several solar wind (SW) collectors used by the Genesis Mission (NASA Discovery Class Mission #5). The film was ~1 μm thick, amorphous, anhydrous, and had a high ratio of sp 3–sp 2 bonds (>50%). For 27 months of exposure to space at the first We passively irradiated lagrange point, the collectors, with SW (H fluence ~2 × 10 16 ions cm -2; He fluence ~8 × 10 14 ions cm -2). The radiation damage caused by the implanted H ionsmore » peaked at 12–14 nm below the surface of the film and that of He about 20–23 nm. To enable quantitative measurement of the SW fluences by secondary ion mass spectroscopy, minor isotopes of Mg ( 25Mg and 26Mg) were commercially implanted into flight-spare collectors at 75 keV and a fluence of 1 × 10 14 ions cm -2. Furthermore, the shapes of analytical depth profiles, the rate at which the profiles were sputtered by a given beam current, and the intensity of ion yields are used to characterize the structure of the material in small areas (~200 × 200 ± 50 μm). Data were consistent with the hypothesis that minor structural changes in the film were induced by SW exposure.« less
Atypical dust species in the ejecta of classical novae
NASA Astrophysics Data System (ADS)
Helton, L. A.; Evans, A.; Woodward, C. E.; Gehrz, R. D.
2011-03-01
A classical nova outburst arises from a thermonuclear runaway in the hydrogen-rich material accreted onto the surface of a white dwarf in a binary system. These explosions can produce copious amounts of heavy element enriched material that are ejected violently into the surrounding interstellar medium. In some novae, conditions in the ejecta are suitable for the formation of dust of various compositions, including silicates, amorphous carbon, silicon carbide, and hydrocarbons. Multiple dust grain types are sometimes produced in the same system. CO formation in novae may not reach saturation, thus invalidating the usual paradigm in which the C:O ratio determines the dust species. A few novae, such as V705 Cas and DZ Cru, have exhibited emission features near 6, 8, and 11 μmthat are similar to "Unidentified Infrared" (UIR) features, but with significant differences in position and band structure. Here, we present Spitzer IRS spectra of two recent dusty novae, V2361 Cyg and V2362 Cyg, that harbor similar peculiar emission structures superimposed on features arising from carbonaceous grains. In other astronomical objects, such as star forming regions and young stellar objects, emission peaks at 6.2, 7.7, and 11.3 μmhave been associated with polycyclic aromatic hydrocarbon (PAH) complexes. We suggest that hydrogenated amorphous carbon (HAC) may be the source of these features in novae based upon the spectral behavior of the emission features and the conditions under which the dust formed.
Recrystallization-Induced Surface Cracks of Carbon Ions Irradiated 6H-SiC after Annealing.
Ye, Chao; Ran, Guang; Zhou, Wei; Shen, Qiang; Feng, Qijie; Lin, Jianxin
2017-10-25
Single crystal 6H-SiC wafers with 4° off-axis [0001] orientation were irradiated with carbon ions and then annealed at 900 °C for different time periods. The microstructure and surface morphology of these samples were investigated by grazing incidence X-ray diffraction (GIXRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Ion irradiation induced SiC amorphization, but the surface was smooth and did not have special structures. During the annealing process, the amorphous SiC was recrystallized to form columnar crystals that had a large amount of twin structures. The longer the annealing time was, the greater the amount of recrystallized SiC would be. The recrystallization volume fraction was accorded with the law of the Johnson-Mehl-Avrami equation. The surface morphology consisted of tiny pieces with an average width of approximately 30 nm in the annealed SiC. The volume shrinkage of irradiated SiC layer and the anisotropy of newly born crystals during annealing process produced internal stress and then induced not only a large number of dislocation walls in the non-irradiated layer but also the initiation and propagation of the cracks. The direction of dislocation walls was perpendicular to the growth direction of the columnar crystal. The longer the annealing time was, the larger the length and width of the formed crack would be. A quantitative model of the crack growth was provided to calculate the length and width of the cracks at a given annealing time.
Batra, Nitin M; Patole, Shashikant P; Abdelkader, Ahmed; Anjum, Dalaver H; Deepak, Francis L; Costa, Pedro M F J
2015-11-06
The use of electron and ion beam deposition to make devices containing discrete nanostructures as interconnectors is a well-known nanofabrication process. Classically, one-dimensional materials such as carbon nanotubes (CNTs) have been electrically characterized by resorting to these beam deposition methods. While much attention has been given to the interconnectors, less is known about the contacting electrodes (or leads). In particular, the structure and chemistry of the electrode-interconnector interface is a topic that deserves more attention, as it is critical to understand the device behavior. Here, the structure and chemistry of Pt electrodes, deposited either with electron or ion beams and contacted to a CNT, are analyzed before and after thermally annealing the device in a vacuum. Free-standing Pt nanorods, acting as beam-deposited electrode models, are also characterized pre- and post-annealing. Overall, the as-deposited leads contain a non-negligible amount of amorphous carbon that is consolidated, upon heating, as a partially graphitized outer shell enveloping a Pt core. This observation raises pertinent questions regarding the definition of electrode-nanostructure interfaces in electrical devices, in particular long-standing assumptions of metal-CNT contacts fabricated by direct beam deposition methods.
Xiao, H. Y.; Weber, W. J.; Zhang, Y.; Zu, X. T.; Li, S.
2015-01-01
The response of titanate pyrochlores (A2Ti2O7, A = Y, Gd and Sm) to electronic excitation is investigated utilizing an ab initio molecular dynamics method. All the titanate pyrochlores are found to undergo a crystalline-to-amorphous structural transition under a low concentration of electronic excitations. The transition temperature at which structural amorphization starts to occur depends on the concentration of electronic excitations. During the structural transition, O2-like molecules are formed, and this anion disorder further drives cation disorder that leads to an amorphous state. This study provides new insights into the mechanisms of amorphization in titanate pyrochlores under laser, electron and ion irradiations. PMID:25660219
Xiao, H Y; Weber, W J; Zhang, Y; Zu, X T; Li, S
2015-02-09
The response of titanate pyrochlores (A2Ti2O7, A = Y, Gd and Sm) to electronic excitation is investigated utilizing an ab initio molecular dynamics method. All the titanate pyrochlores are found to undergo a crystalline-to-amorphous structural transition under a low concentration of electronic excitations. The transition temperature at which structural amorphization starts to occur depends on the concentration of electronic excitations. During the structural transition, O2-like molecules are formed, and this anion disorder further drives cation disorder that leads to an amorphous state. This study provides new insights into the mechanisms of amorphization in titanate pyrochlores under laser, electron and ion irradiations.
On Structure and Properties of Amorphous Materials
Stachurski, Zbigniew H.
2011-01-01
Mechanical, optical, magnetic and electronic properties of amorphous materials hold great promise towards current and emergent technologies. We distinguish at least four categories of amorphous (glassy) materials: (i) metallic; (ii) thin films; (iii) organic and inorganic thermoplastics; and (iv) amorphous permanent networks. Some fundamental questions about the atomic arrangements remain unresolved. This paper focuses on the models of atomic arrangements in amorphous materials. The earliest ideas of Bernal on the structure of liquids were followed by experiments and computer models for the packing of spheres. Modern approach is to carry out computer simulations with prediction that can be tested by experiments. A geometrical concept of an ideal amorphous solid is presented as a novel contribution to the understanding of atomic arrangements in amorphous solids. PMID:28824158
Sainio, S.; Nordlund, D.; Gandhiraman, R.; ...
2016-09-15
Understanding the chemical nature of the surface of carbon nanofibers (CNF) is critical in assessing their fundamental properties and tailoring them for the right application. To gain such knowledge, we present here a detailed X-ray adsorption spectroscopy (XAS) study accompanied by high resolution transmission electron microscopy (TEM) micrographs of two morphologically different CNF pairs (tetrahedral amorphous carbon (ta-C) grown “open structured” fibers and traditional bamboo-like “closed structured” fibers), where the surface chemical properties and structural features of the fibers are investigated in depth and the effects of nitric acid treatment on the fibers are revealed. The morphology of the fibermore » and/or the original seed- and adhesion layers markedly affect the response of the fibers to the acid treatment. Results also show that the nitric acid treatment increases the observed sp 2 intensity and modifies the two types of fibers to become more-alike both structurally and with respect to their oxygen functionalities. Furthermore, the XAS and HRTEM results confirm that a short nitric acid treatment does not remove the Ni catalyst particle but, instead, oxidizes their surfaces, especially in the case of ta-C grown fibers.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sainio, S.; Nordlund, D.; Gandhiraman, R.
Understanding the chemical nature of the surface of carbon nanofibers (CNF) is critical in assessing their fundamental properties and tailoring them for the right application. To gain such knowledge, we present here a detailed X-ray adsorption spectroscopy (XAS) study accompanied by high resolution transmission electron microscopy (TEM) micrographs of two morphologically different CNF pairs (tetrahedral amorphous carbon (ta-C) grown “open structured” fibers and traditional bamboo-like “closed structured” fibers), where the surface chemical properties and structural features of the fibers are investigated in depth and the effects of nitric acid treatment on the fibers are revealed. The morphology of the fibermore » and/or the original seed- and adhesion layers markedly affect the response of the fibers to the acid treatment. Results also show that the nitric acid treatment increases the observed sp 2 intensity and modifies the two types of fibers to become more-alike both structurally and with respect to their oxygen functionalities. Furthermore, the XAS and HRTEM results confirm that a short nitric acid treatment does not remove the Ni catalyst particle but, instead, oxidizes their surfaces, especially in the case of ta-C grown fibers.« less
Effects of argon addition on a-CNx film deposition by hot carbon filament chemical vapor deposition
NASA Astrophysics Data System (ADS)
Watanabe, Yoshihisa; Aono, Masami; Yamazaki, Ayumi; Kitazawa, Nobuaki; Nakamura, Yoshikazu
2002-07-01
Using a carbon filament which supplies carbon and heat, amorphous carbon nitride (a-CNx) films were prepared on Si (100) substrates by hot filament chemical vapor deposition. Deposition was performed in a low-pressure atmosphere of pure nitrogen and a gas mixture of nitrogen and argon. Effects of argon additions to the nitrogen atmosphere on the film microstructure and interface composition between the film and substrate were studied by field-emission scanning electron microscopy (FESEM) and x-ray photoelectron spectroscopy (XPS). FESEM observations reveal that the film prepared in a pure nitrogen atmosphere has uniform nucleation and a densely packed columnar pieces structure. The film prepared in the nitrogen and argon gas mixture exhibits preferential nucleation and a tapered structure with macroscopic voids. Depth analyses using XPS reveal that the film prepared in pure nitrogen possesses a broad interface, which includes silicon carbide as well as a-CNx, whereas a sharp interface is discerned in the film prepared in the mixed nitrogen and argon gas. We observed that silicon carbide formation is suppressed by an argon addition to the nitrogen atmosphere during deposition. copyright 2002 American Vacuum Society.
Zhang, Linji; Ren, Yang; Liu, Xiuru; Han, Fei; Evans-Lutterodt, Kenneth; Wang, Hongyan; He, Yali; Wang, Junlong; Zhao, Yong; Yang, Wenge
2018-03-14
Amorphous sulfur was prepared by rapid compression of liquid sulfur at temperatures above the λ-transition for to preserve the high-temperature liquid structure. We conducted synchrotron high-energy X-ray diffraction and Raman spectroscopy to diagnose the structural evolution of amorphous sulfur from room temperature to post-λ-transition temperature. Discontinuous changes of the first and second peaks in atomic pair-distribution-function, g(r), were observed during the transition from amorphous to liquid sulfur. The average first-neighbor coordination numbers showed an abrupt drop from 1.92 to 1.81. The evolution of the chain length clearly shows that the transition was accompanied by polymeric chains breaking. Furthermore, a re-entry of the λ-transition structure was involved in the heating process. The amorphous sulfur, which inherits the post-λ-transition structure from its parent melts, transformed to the pre-λ-transition liquid structure at around 391 K. Upon further heating, the pre-λ-transition liquid transformed to a post-λ-transition structure through the well-known λ-transition process. This discovery offers a new perspective on amorphous sulfur's structural inheritance from its parent liquid and has implications for understanding the structure, evolution and properties of amorphous sulfur and its liquids.
Guillemet, Baptiste; Faatz, Michael; Gröhn, Franziska; Wegner, Gerhard; Gnanou, Yves
2006-02-14
Particles of amorphous calcium carbonate (ACC), formed in situ from calcium chloride by the slow release of carbon dioxide by alkaline hydrolysis of dimethyl carbonate in water, are stabilized against coalescence in the presence of very small amounts of double hydrophilic block copolymers (DHBCs) composed of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blocks. Under optimized conditions, spherical particles of ACC with diameters less than 100 nm and narrow size distribution are obtained at a concentration of only 3 ppm of PEO-b-PAA as additive. Equivalent triblock or star DHBCs are compared to diblock copolymers. The results are interpreted assuming an interaction of the PAA blocks with the surface of the liquid droplets of the concentrated CaCO3 phase, formed by phase separation from the initially homogeneous reaction mixture. The adsorption layer of the block copolymer protects the liquid precursor of ACC from coalescence and/or coagulation.
Graphene nanocomposites for electrochemical cell electrodes
Zhamu, Aruna; Jang, Bor Z.; Shi, Jinjun
2015-11-19
A composite composition for electrochemical cell electrode applications, the composition comprising multiple solid particles, wherein (a) a solid particle is composed of graphene platelets dispersed in or bonded by a first matrix or binder material, wherein the graphene platelets are not obtained from graphitization of the first binder or matrix material; (b) the graphene platelets have a length or width in the range of 10 nm to 10 .mu.m; (c) the multiple solid particles are bonded by a second binder material; and (d) the first or second binder material is selected from a polymer, polymeric carbon, amorphous carbon, metal, glass, ceramic, oxide, organic material, or a combination thereof. For a lithium ion battery anode application, the first binder or matrix material is preferably amorphous carbon or polymeric carbon. Such a composite composition provides a high anode capacity and good cycling response. For a supercapacitor electrode application, the solid particles preferably have meso-scale pores therein to accommodate electrolyte.
Direct-patterned optical waveguides on amorphous silicon films
Vernon, Steve; Bond, Tiziana C.; Bond, Steven W.; Pocha, Michael D.; Hau-Riege, Stefan
2005-08-02
An optical waveguide structure is formed by embedding a core material within a medium of lower refractive index, i.e. the cladding. The optical index of refraction of amorphous silicon (a-Si) and polycrystalline silicon (p-Si), in the wavelength range between about 1.2 and about 1.6 micrometers, differ by up to about 20%, with the amorphous phase having the larger index. Spatially selective laser crystallization of amorphous silicon provides a mechanism for controlling the spatial variation of the refractive index and for surrounding the amorphous regions with crystalline material. In cases where an amorphous silicon film is interposed between layers of low refractive index, for example, a structure comprised of a SiO.sub.2 substrate, a Si film and an SiO.sub.2 film, the formation of guided wave structures is particularly simple.
Carbon Nanostructure of Kraft Lignin Thermally Treated at 500 to 1000 °C.
Zhang, Xuefeng; Yan, Qiangu; Leng, Weiqi; Li, Jinghao; Zhang, Jilei; Cai, Zhiyong; Hassan, El Barbary
2017-08-21
Kraft lignin (KL) was thermally treated at 500 to 1000 °C in an inert atmosphere. Carbon nanostructure parameters of thermally treated KL in terms of amorphous carbon fraction, aromaticity, and carbon nanocrystallites lateral size ( L a ), thickness ( L c ), and interlayer space ( d 002 ) were analyzed quantitatively using X-ray diffraction, Raman spectroscopy, and high-resolution transmission electron microscopy. Experimental results indicated that increasing temperature reduced amorphous carbon but increased aromaticity in thermally treated KL materials. The L c value of thermally treated KL materials averaged 0.85 nm and did not change with temperature. The d 002 value decreased from 3.56 Å at 500 °C to 3.49 Å at 1000 °C. The L a value increased from 0.7 to 1.4 nm as temperature increased from 500 to 1000 °C. A nanostructure model was proposed to describe thermally treated KL under 1000 °C. The thermal stability of heat treated KL increased with temperature rising from 500 to 800 °C.
Purification Procedures for Single-Wall Carbon Nanotubes
NASA Technical Reports Server (NTRS)
Gorelik, Olga P.; Nikolaev, Pavel; Arepalli, Sivaram
2001-01-01
This report summarizes the comparison of a variety of procedures used to purify carbon nanotubes. Carbon nanotube material is produced by the arc process and laser oven process. Most of the procedures are tested using laser-grown, single-wall nanotube (SWNT) material. The material is characterized at each step of the purification procedures by using different techniques including scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), Raman, X-ray diffractometry (XRD), thermogravimetric analysis (TGA), nuclear magnetic resonance (NMR), and high-performance liquid chromatography (HPLC). The identified impurities are amorphous and graphitic carbon, catalyst particle aggregates, fullerenes, and hydrocarbons. Solvent extraction and low-temperature annealing are used to reduce the amount of volatile hydrocarbons and dissolve fullerenes. Metal catalysts and amorphous as well as graphitic carbon are oxidized by reflux in acids including HCl, HNO3 and HF and other oxidizers such as H2O2. High-temperature annealing in vacuum and in inert atmosphere helps to improve the quality of SWNTs by increasing crystallinity and reducing intercalation.
NASA Astrophysics Data System (ADS)
Tan, Hui-Gee; Duh, Jenq-Gong
2016-12-01
A vast quantity of waste sludge is generated during the silicon wafers slicing process in semiconductor and photovoltaic industries. Turning the waste powder into high-value products is of strategic importance for industrial processes. The purified Si microparticles (Si-MP) are recycled by a simple and fast procedure, Rapid Thermal Process (RTP). A prominent anodic material of Si-MP/Carbon composite with porous structure is obtained via in-spaced carbonization of water-soluble binder sodium carboxymethyl cellulose during RTP. This strategy provides buffer space, which is constructed by carbon porous continuous conductive framework throughout the entire electrode, to resist local stress and intense volume variation. In addition, a sufficiently electrochemically stable solid-electrolyte interphase layer is accomplished with the coating of SiOx film and amorphous carbon on the surface of Si-MP. Under these circumstances, the enhanced electrodes achieve a first cycle efficiency of approximately 80% and a reversible charge capacity of 800 mAhg-1 over 100 cycles at 0.5 Ag-1 with good retention. Through a green and simple procedure, a remarkable Si-MP embedded carbon-matrix with porous structure is established to achieve commercially high performance Si-MP/C composite anodes and also to resolve the issues of waste disposal.
Synthesis and characterization of carbon-coated cobalt ferrite nanoparticles
NASA Astrophysics Data System (ADS)
Bakhshi, Hamed; Shokuhfar, Ali; Vahdati, Nima
2016-09-01
Cobalt ferrite nanoparticles (CFNPs) were prepared via a reverse micelle method. The CFNPs were subsequently coated with carbon shells by means of thermal chemical vapor deposition (TCVD). In this process, acetylene gas (C2H2) was used as a carbon source and the coating was carried out for 1, 2, or 3 h at 750°C. The Ar/C2H2 ratio was 10:1. Heating during the TCVD process resulted in a NP core size that approached 30 nm; the thickness of the shell was less than 10 nm. The composition, structure, and morphology of the fabricated composites were characterized using X-ray diffraction, simultaneous thermal analysis, transmission electron microscopy, high-resolution transmission electron microscopy, and selected-area diffraction. A vibrating sample magnetometer was used to survey the samples' magnetic properties. The deposited carbon shell substantially affected the growth and magnetic properties of the CFNPs. Micro-Raman spectroscopy was used to study the carbon coating and revealed that the deposited carbon comprised graphite, multiwalled carbon nanotubes, and diamond- like carbon. With an increase in coating time, the intensity ratio between the amorphous and ordered peaks in the Raman spectra decreased, which indicated an increase in crystallite size.
Structural simplicity as a restraint on the structure of amorphous silicon
NASA Astrophysics Data System (ADS)
Cliffe, Matthew J.; Bartók, Albert P.; Kerber, Rachel N.; Grey, Clare P.; Csányi, Gábor; Goodwin, Andrew L.
2017-06-01
Understanding the structural origins of the properties of amorphous materials remains one of the most important challenges in structural science. In this study, we demonstrate that local "structural simplicity", embodied by the degree to which atomic environments within a material are similar to each other, is a powerful concept for rationalizing the structure of amorphous silicon (a -Si) a canonical amorphous material. We show, by restraining a reverse Monte Carlo refinement against pair distribution function (PDF) data to be simpler, that the simplest model consistent with the PDF is a continuous random network (CRN). A further effect of producing a simple model of a -Si is the generation of a (pseudo)gap in the electronic density of states, suggesting that structural homogeneity drives electronic homogeneity. That this method produces models of a -Si that approach the state-of-the-art without the need for chemically specific restraints (beyond the assumption of homogeneity) suggests that simplicity-based refinement approaches may allow experiment-driven structural modeling techniques to be developed for the wide variety of amorphous semiconductors with strong local order.
Effects of heating time on the growth and behavior of amorphous carbon nanostructures from ferrocene
NASA Astrophysics Data System (ADS)
Rafiqul Islam, Md; Rashid, A. K. M. B.; Ferdous, Md; Shafiul Azam, Md
2017-05-01
Heating time is one of the crucial factors in various methods employed for the synthesis of carbon nanostructures (CNSs) from ferrocene. However, the effects of heating time on the growth and morphology of the nanostructured materials has not been well explored yet, particularly for amorphous carbon. Herein, we investigate how the variation of heating time impacts the growth of CNSs by carrying out the reaction between ferrocene and ammonium chloride in a solvent free condition at 250 °C. Several different forms of carbon nanostructures yielded from this reaction at 25 min (CNS-25), 30 min (CNS-30), 35 min (CNS-35) and 40 min (CNS-40) were analyzed by means of field emission scanning electron microscopy (FESEM) coupled with energy-dispersive x-ray (EDX), Fourier transform infrared (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy. The final product CNS-40 was washed several times with concentrated hydrochloric acid solution to remove the impurities and then characterized by the means of similar techniques. FTIR spectra of all the nanostructures confirmed the presence of several functional groups such as C = C, C-O and -OH etc, which are common in carbonaceous nanostructures. However, the FESEM images obtained are significantly different and suggest a gradual growth of the carbon nanostructures ending up with long carbon nanotubes after 40 min. No absorption peak in the visible region of the UV-Vis spectra of the final product confirms the amorphous nature, which is also supported by XRD of the synthesized nanotube. Moreover, a noteworthy redshift in the UV-Vis peaks reflecting a huge increase in length and diameter of the nanostructures indicates the maximum longitudinal growth of the carbon nanotubes occurs during 35 min to 40 min.
Wu, Xue-Qian; Zhao, Jun; Wu, Ya-Pan; Dong, Wen-Wen; Li, Dong-Sheng; Li, Jian-Rong; Zhang, Qichun
2018-04-18
The development of novel strategy to produce new porous carbon materials is extremely important because these materials have wide applications in energy storage/conversion, mixture separation, and catalysis. Herein, for the first time, a novel 3D carbon substrate with hierarchical pores derived from commercially available Cu-MOF (metal-organic framework) (HKUST-1) through carbonization and chemical etching has been employed as the catalysts' support. Highly dispersed Pt nanoparticles and amorphous nickel were evenly dispersed on the surface or embedded within carbon matrix. The corresponding optimal composite catalyst exhibits a high mass-specific peak current of 1195 mA mg -1 Pt and excellent poison resistance capacity ( I F / I B = 1.58) for methanol oxidation compared to commercial Pt/C (20%). Moreover, both composite catalysts manifest outstanding properties in the reduction of nitrophenol and demonstrate diverse selectivities for 2/3/4-nitrophenol, which can be attributed to different integrated forms between active species and carbon matrix. This attractive route offers broad prospects for the usage of a large number of available MOFs in fabricating functional carbon materials as well as highly active carbon-based electrocatalysts and heterogeneous organic catalysts.
Lala, S; Brahmachari, S; Das, P K; Das, D; Kar, T; Pradhan, S K
2014-09-01
Single phase nanocrystalline biocompatible A-type carbonated hydroxyapatite (A-cHAp) powder has been synthesized by mechanical alloying the stoichiometric mixture of CaCO3 and CaHPO4.2H2O powders in open air at room temperature within 2h of milling. The A-type carbonation in HAp is confirmed by FTIR analysis. Structural and microstructure parameters of as-milled powders are obtained from both Rietveld's powder structure refinement analysis and transmission electron microscopy. Size and lattice strain of nanocrystalline HAp particles are found to be anisotropic in nature. Mechanical alloying causes amorphization of a part of crystalline A-cHAp which is analogous to native bone mineral. Some primary bond lengths of as-milled samples are critically measured. MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] assay test reveals high percentage of cell viability and hence confirms the biocompatibility of the sample. The overall results indicate that the processed A-cHAp has a chemical composition very close to that of biological apatite. Copyright © 2014 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Wang, Jun; Zhu, Fei; Zhang, Bei; Liu, Huixian; Jia, Guangyi; Liu, Changlong
2012-11-01
Polymethylmethacrylate (PMMA) specimens were implanted with 30 keV carbon ions in a fluence range of 1 × 1016 to 2 × 1017 cm-2, and photoluminescence (PL) and reflectivity of the implanted samples were examined. A luminescent band with one peak was found in PL spectra excited by 480 nm line, but its intensity did not vary in parallel with ion fluence. The strongest PL occurred at the fluence of 5 × 1016 cm-2. Results from visible-light-excited micro-Raman spectra indicated that the formation of hydrogenated amorphous carbon structures in subsurface layer and their evolutions with ion fluence could be responsible for the observed PL responses. Measurements of the small-angle reflectance spectra from both the implanted and rear surfaces of samples in the ultraviolet-visible (UV-vis) range demonstrated a kind of both fluence-dependent and wavelength-related reflectivity variations, which were attributed to the structural changes induced by ion implantation. A noticeable reflectivity modification, which may be practically used, could be found at the fluence of 1 × 1016 cm-2.
NASA Technical Reports Server (NTRS)
Furton, Douglas G.; Witt, Adolf N.
1993-01-01
We report on new laboratory results which relate directly to the observation of strongly enhanced extended red emission (ERE) by interstellar dust in H2 photodissociation zones. The ERE has been attributed to photoluminescence by hydrogenated amorphous carbon (HAC). We are demonstrating that exposure to thermally dissociated atomic hydrogen will restore the photoluminescence efficiency of previously annealed HAC. Also, pure amorphous carbon (AC), not previously photoluminescent, can be induced to photoluminesce by exposure to atomic hydrogen. This conversion of AC into HAC is greatly enhanced by the presence of UV irradiation. The presence of dense, warm atomic hydrogen and a strong UV radiation field are characteristic environmental properties of H2 dissociation zones. Our results lend strong support to the HAC photoluminescence explanation for ERE.
Microanalysis of vitrous char and associated polymers: reference and ancient assemblages
NASA Astrophysics Data System (ADS)
Allue, E.; Bonnamy, S.; Courty, M. M.; Gispert I Guirado, F.
2012-12-01
Formation of vitrous char that occur in ancient charcoal assemblages have remained unsolved. Laboratory experiments refuted vitrification to resulting from high temperature charring of green or resinous wood. This puzzling problem has been refreshed by showing the association to the charcoal and vitrous char of plastics that were originally supposed to only be produced by petroleum industry. Extraction of similar polymers within geological glassy products from cosmic airbursts has suggested impact processes to possibly forming the carbonaceous polymorphs. The pulverisation at the ground in the Angles village (French Eastern Pyrenees) following the 2011 August 2nd high altitude meteor explosion of exotic debris with vitrous char and polymers, just alike the puzzling ones of the geological and archaeological records, has provided potential reference materials. We present here their microanalysis by Environmental SEM with EDS, Raman micro-spectrometry and FTIR, XRD, TEM, ICP-MS and isotope analyses. The characterization helps elucidating how the carbonaceous polymorphs formed by transient heating and transient high pressure of atmospheric aerosols. Under TEM the vesicular, dense, vitrous char show high structural organization with a dense pattern of nano-sized graphitized domains, metals and mineral inclusions. The coupled Raman-ESEM has allowed identifying a complex pattern at micro scales of ordered "D" peak at 1320-1350 cm-1 and the graphitic, ordered peak at 1576-1590 cm-1, in association to amorphous and poorly graphitic ordered carbon. The later occurs within plant cells that have been extracted from the dense vitrous char by performing controlled combustion under nitrogen up to 1000°C. In contrast, the brittle, vesicular vitrous char and the polymers encountered at the rear of the pulverised airburst debris reveal to be formed of agglutinated micro spherules of amorphous carbon with rare crystallized carbon nano-domains and scattered mineral inclusions. They completely vaporised at 300°C under stepped-heating without leaving extractable residues. The link established between the structure of these exceptional carbon polymorphs and their forming processes provide diagnostic keys for interpreting vitrous carbon in ancient charcoal assemblage. The hardest ones offer reliable impact markers with their distinctive nanostructure produced by the transient high pressure and heating of carbonaceous aerosols by cosmic airbursts. In contrast, the weakly graphitised ones with distinctive plant structures would possibly express moderate effects of the airburst shock wave on vegetation at the ground. Thus micro-structural characterization of charcoal in archaeological assemblages would help tracing possible exploitation of blasted wood forest and related fossil fuel produced by ancient cosmic airbursts.
Synthesis and characterization of bulk metallic glasses prepared by laser direct deposition
NASA Astrophysics Data System (ADS)
Ye, Xiaoyang
Fe-based and Zr-based metallic glasses have attracted extensive interest for structural applications due to their excellent glass forming ability, superior mechanical properties, unique thermal and corrosion properties. In this study, the feasibility of synthesizing metallic glasses with good ductility by laser direct deposition is explored. Both in-situ synthesis with elemental powder mixture and ex-situ synthesis with prealloyed powder are discussed. Microstructure and properties of laser direct deposited metallic glass composites are analyzed. Synthesis of Fe-Cr-Mo-W-Mn-C-Si-B metallic glass composite with a large fraction of amorphous phase was accomplished using laser direct deposition. X-ray diffraction (XRD) and transmission electron microscopy investigations revealed the existence of amorphous structure. Microstructure analyses by optical microscopy and scanning electron microscopy (SEM) indicated the periodically repeated microstructures of amorphous and crystalline phases. Partially crystallized structure brought by laser reheating and remelting during subsequent laser scans aggregated in the overlapping area between each scan. XRD analysis showed that the crystalline particle embedded in the amorphous matrix was Cr 1.07Fe18.93 phase. No significant microstructural differences were found from the first to the last layer. Microhardness of the amorphous phase (HV0.2 1591) showed a much higher value than that of the crystalline phase (HV0.2 947). Macrohardness of the top layer had a value close to the microhardness of the amorphous region. Wear resistance property of deposited layers showed a significant improvement with the increased fraction of amorphous phase. Zr65Al10Ni10Cu15 amorphous composites with a large fraction of amorphous phase were in-situ synthesized by laser direct deposition. X-ray diffraction confirmed the existence of both amorphous and crystalline phases. Laser parameters were optimized in order to increase the fraction of amorphous phase. The microstructure analysis by scanning electron microscopy revealed the deposited structure was composed of periodically repeated amorphous and crystalline phases. Overlapping regions with nanoparticles aggregated were crystallized by laser reheating and remelting processes during subsequent laser scans. Vickers microhardness of the amorphous region showed around 35% higher than that of crystalline region. Average hardness obtained by a Rockwell macrohardness tester was very close to the microhardness of the amorphous region. The compression test showed that the fracture strain of Zr65Al10Ni10Cu15 amorphous composites was enhanced from less than 2% to as high as 5.7%, compared with fully amorphous metallic glass. Differential scanning calorimetry test results further revealed the amorphous structure and glass transition temperature Tg was observed to be around 655K. In 3 mol/L NaCl solution, laser direct deposited amorphous composites exhibited distinctly improved corrosion resistance, compared with fully-crystallized samples.
NASA Astrophysics Data System (ADS)
Zhang, Haiyan; Li, Liuqing; Li, Zhaopeng; Zhong, Weihao; Liao, Haiyang; Li, Zhenghui
2018-06-01
Constructing hollow structure and nano-sized SnO2 particles are two normal strategies to improve lithium storage performance of SnO2-based electrode. But it is still challengeable to fabricate ultrasmall SnO2 embedded in carbon hollow sphere in a controllable way. Herein, we have synthesized a kind of SnO2@carbon hollow sphere via a confined Friedel-Crafts crosslinking of a novel metal-organic compound (triphenyltin chloride, named Sn-Ph) on the surface of SiO2 template. The as-prepared SnO2@carbon hollow sphere has 10 nm-sized SnO2 particles embedded in amorphous carbon wall. Furthermore, 100, 200 and 400 nm-sized SnO2@carbon hollow spheres can be obtained by regulating the size of SiO2 template. When they are applied in lithium-ion batteries, the carbon structure can act as barriers to protect SnO2 particles from pulverization, and hollow core stores electrolyte and very small SnO2 particles of 10 nm shorten the diffusion distance of lithium ions. Thus, SnO2@carbon hollow sphere presents superior electrochemical performance. The first discharge and charge capacities reach 1378.5 and 507.3 mAh g-1 respectively, and 100 cycles later, its capacity remains 501.2 mAh g-1, indicating a capacity retention of 98.8% (C100th/C2nd).
Formation of carbon nitride — a novel hard coating
NASA Astrophysics Data System (ADS)
Chubaci, J. F. D.; Ogata, K.; Fujimoto, F.; Watanabe, S.; Biersack, J. P.
1996-08-01
Increasing efforts have been reported on the formation of carbon nitride. Vapor deposition and simultaneous ion bombardment from accelerators or plasmas (IBAD) proved to be a successful technique for the preparation of this material. In our preparation, the properties of the films were controlled by varying the nitrogen ion energy and the flux composition ratio {C}/{N}. The deposited films with high nitrogen incorporation ( {C}/{N} = 0.6 ˜ 0.7 ) and low implantation energies (< 1.0 keV) showed high Knoop hardnesses of up to 63 GPa. XPS and FT-IR measurements indicated a high fraction of triple bonded CN. X-ray diffraction showed an amorphous structure. Computer simulations by the dynamic TRIM code are used to study the formation parameters, nitrogen ion energy and {C}/{N} ratio. This turned on to be useful in understanding the formation process of the carbon nitride films grown on silicon wafers, fused silica and tungsten carbide substrates.
Substitution reactions of carbon nanotube template
NASA Astrophysics Data System (ADS)
Li, Chi Pui; Chen, Ying; Gerald, John Fitz
2006-05-01
Substitution reactions between carbon nanotube (CNT) template and SiO with the formation of carbon rich silicon oxide nanowires (SiO-C-NWs) have been investigated using transmission electron microscopy and x-ray energy dispersive spectroscopy. The reaction was carried out by thermal annealing at 1200°C for 1h of a mixture of silicon monoxide (SiO) and iron (II) phthalocyanine, FeC32N8H16 (FePc) powders. Multiwalled CNTs were produced first via pyrolysis of FePc at a lower temperature (1000°C ). SiO vapors reacted with the CNTs at higher temperatures to produce amorphous SiO-C-NWs with a uniform diameter and a length in tens of micrometers. The special bamboolike structure of the CNTs allows the reaction to start from the external surface of the tubes and transform each CNT into a solid nanowire section by section.
NASA Astrophysics Data System (ADS)
Sharp, J.; Castillo Muller, I.; Mandal, P.; Abbas, A.; West, G.; Rainforth, W. M.; Ehiasarian, A.; Hovsepian, P.
2015-10-01
A FIB lift-out sample was made from a wear-resistant carbon coating deposited by high power impulse magnetron sputtering (HIPIMS) with Mo and W. TEM analysis found columnar grains extending the whole ∼1800 nm thick film. Within the grains, the carbon was found to be organised into clusters showing some onion-like structure, with amorphous material between them; energy dispersive X-ray spectroscopy (EDS) found these clusters to be Mo- and W-rich in a later, thinner sample of the same material. Electron energy-loss spectroscopy (EELS) showed no difference in C-K edge, implying the bonding type to be the same in cluster and matrix. These clusters were arranged into stripes parallel to the film plane, of spacing 7-8 nm; there was a modulation in spacing between clusters within these stripes that produced a second, coarser set of striations of spacing ∼37 nm.
Daghrir, Rimeh; Drogui, Patrick; Tshibangu, Joel; Delegan, Nazar; El Khakani, My Ali
2014-05-01
The performance of the electrochemical oxidation process for efficient treatment of domestic wastewater loaded with organic matter was studied. The process was firstly evaluated in terms of its capability of producing an oxidant agent (H2O2) using amorphous carbon (or carbon felt) as cathode, whereas Ti/BDD electrode was used as anode. Relatively high concentrations of H2O2 (0.064 mM) was produced after 90 min of electrolysis time, at 4.0 A of current intensity and using amorphous carbon at the cathode. Factorial design and central composite design methodologies were successively used to define the optimal operating conditions to reach maximum removal of chemical oxygen demand (COD) and color. Current intensity and electrolysis time were found to influence the removal of COD and color. The contribution of current intensity on the removal of COD and color was around 59.1 and 58.8%, respectively, whereas the contribution of treatment time on the removal of COD and color was around 23.2 and 22.9%, respectively. The electrochemical treatment applied under 3.0 A of current intensity, during 120 min of electrolysis time and using Ti/BDD as anode, was found to be the optimal operating condition in terms of cost/effectiveness. Under these optimal conditions, the average removal rates of COD and color were 78.9 ± 2 and 85.5 ± 2 %, whereas 70% of total organic carbon removal was achieved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Xiao, Haiyan Y.; Weber, William J.; Zhang, Yanwen
2015-02-09
In this study, the response of titanate pyrochlores (A 2Ti 2O 7, A = Y, Gd and Sm) to electronic excitation is investigated utilizing an ab initio molecular dynamics method. All the titanate pyrochlores are found to undergo a crystalline-to-amorphous structural transition under a low concentration of electronic excitations. The transition temperature at which structural amorphization starts to occur depends on the concentration of electronic excitations. During the structural transition, O 2-like molecules are formed, and this anion disorder further drives cation disorder that leads to an amorphous state. This study provides new insights into the mechanisms of amorphization inmore » titanate pyrochlores under laser, electron and ion irradiations.« less
First principles prediction of amorphous phases using evolutionary algorithms
DOE Office of Scientific and Technical Information (OSTI.GOV)
Nahas, Suhas, E-mail: shsnhs@iitk.ac.in; Gaur, Anshu, E-mail: agaur@iitk.ac.in; Bhowmick, Somnath, E-mail: bsomnath@iitk.ac.in
2016-07-07
We discuss the efficacy of evolutionary method for the purpose of structural analysis of amorphous solids. At present, ab initio molecular dynamics (MD) based melt-quench technique is used and this deterministic approach has proven to be successful to study amorphous materials. We show that a stochastic approach motivated by Darwinian evolution can also be used to simulate amorphous structures. Applying this method, in conjunction with density functional theory based electronic, ionic and cell relaxation, we re-investigate two well known amorphous semiconductors, namely silicon and indium gallium zinc oxide. We find that characteristic structural parameters like average bond length and bondmore » angle are within ∼2% of those reported by ab initio MD calculations and experimental studies.« less
Structure and Properties of SiO x Films Prepared by Chemical Etching of Amorphous Alloy Ribbons
NASA Astrophysics Data System (ADS)
Fedorov, V. A.; Berezner, A. D.; Beskrovnyi, A. I.; Fursova, T. N.; Pavlikov, A. V.; Bazhenov, A. V.
2018-04-01
The structure and the physical properties of amorphous SiO x films prepared by chemical etching of an iron-based amorphous ribbon alloy have been studied. The neutron diffraction and also the atomicforce and electron microscopy show that the prepared visually transparent films have amorphous structure, exhibit dielectric properties, and their morphology is similar to that of opals. The samples have been studied by differential scanning calorimetry, Raman and IR spectroscopy before and after their heat treatment. It is found that annealing of the films in air at a temperature of 1273 K leads to a change in their chemical compositions: an amorphous SiO2 compound with inclusions of SiO2 nanocrystals (crystobalite) forms.
NASA Astrophysics Data System (ADS)
Simos, N.; Zhong, Z.; Dooryhee, E.; Ghose, S.; Gill, S.; Camino, F.; Şavklıyıldız, İ.; Akdoğan, E. K.
2017-06-01
The study revealed that loss of ductility in an amorphous Fe-alloy coating on a steel substrate composite structure was essentially prevented from occurring, following radiation with modest neutron doses of ∼2 × 1018 n/cm2. At the higher neutron dose of ∼2 × 1019, macroscopic stress-strain analysis showed that the amorphous Fe-alloy nanostructured coating, while still amorphous, experienced radiation-induced embrittlement, no longer offering protection against ductility loss in the coating-substrate composite structure. Neutron irradiation in a corrosive environment revealed exemplary oxidation/corrosion resistance of the amorphous Fe-alloy coating, which is attributed to the formation of the Fe2B phase in the coating. To establish the impact of elevated temperatures on the amorphous-to-crystalline transition in the amorphous Fe-alloy, electron microscopy was carried out which confirmed the radiation-induced suppression of crystallization in the amorphous Fe-alloy nanostructured coating.
Amorphous calcium carbonate particles form coral skeletons
Mass, Tali; Giuffre, Anthony J.; Sun, Chang -Yu; ...
2017-08-28
Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO 3).more » We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO 2 increases, such as the Paleocene–Eocene Thermal Maximum that occurred 56 Mya.« less
Amorphous calcium carbonate particles form coral skeletons
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mass, Tali; Giuffre, Anthony J.; Sun, Chang -Yu
Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO 3).more » We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO 2 increases, such as the Paleocene–Eocene Thermal Maximum that occurred 56 Mya.« less
High conductivity a-C:N thin films prepared by electron gun evaporation
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rebollo-Plata, B.; Lozada-Morales, R.; Palomino-Merino, R.
2007-08-15
By employing electron beam evaporation, amorphous carbon nitride (a-C:N) thin films, with a low nitrogen content ({approx} 1%), were prepared on Si(110) and glass substrates at about 150 deg. C. The source was a graphite target and an ambient of N{sub 2} was introduced into the growing chamber. The source-substrate distance (SSD) was the main parameter that was intentionally varied. Electron dispersion spectroscopy measurements indicate the nitrogen concentration in the layer as {approx} 1%. The dark electrical conductivity ({sigma}) of layers was very sensitive to SSD variation, changing up to six orders of magnitude when this parameter was varied frommore » 10.5 to 23.5 cm. A maximum value of {sigma} = 1 x 10{sup 3} {omega}{sup -1} cm{sup -1} at room temperature was obtained when the SSD was equal to 15.5 cm. We have deduced that, in accordance with the Ferrari-Robertson model (FRM), our samples are localized in the second stage of the amorphization trajectory of FRM. When the SSD increases the C atoms have more probability to collide with N{sub 2} molecules, and the content of nitrogen in the a-C film increases. The amorphization trajectory followed by the films with an SSD increase is from nanocrystalline graphite to amorphous carbon. The changes in the amorphization are due to the nitrogen content in the layers.« less
NASA Technical Reports Server (NTRS)
Jensen, Benjamin D.; Wise, Kristopher E.; Odegard, Gregory M.
2015-01-01
The fracture of carbon materials is a complex process, the understanding of which is critical to the development of next generation high performance materials. While quantum mechanical (QM) calculations are the most accurate way to model fracture, the fracture behavior of many carbon-based composite engineering materials, such as carbon nanotube (CNT) composites, is a multi-scale process that occurs on time and length scales beyond the practical limitations of QM methods. The Reax Force Field (ReaxFF) is capable of predicting mechanical properties involving strong deformation, bond breaking and bond formation in the classical molecular dynamics framework. This has been achieved by adding to the potential energy function a bond-order term that varies continuously with distance. The use of an empirical bond order potential, such as ReaxFF, enables the simulation of failure in molecular systems that are several orders of magnitude larger than would be possible in QM techniques. In this work, the fracture behavior of an amorphous carbon (AC) matrix reinforced with CNTs was modeled using molecular dynamics with the ReaxFF reactive forcefield. Care was taken to select the appropriate simulation parameters, which can be different from those required when using traditional fixed-bond force fields. The effect of CNT arrangement was investigated with three systems: a single-wall nanotube (SWNT) array, a multi-wall nanotube (MWNT) array, and a SWNT bundle system. For each arrangement, covalent bonds are added between the CNTs and AC, with crosslink fractions ranging from 0-25% of the interfacial CNT atoms. The SWNT and MWNT array systems represent ideal cases with evenly spaced CNTs; the SWNT bundle system represents a more realistic case because, in practice, van der Waals interactions lead to the agglomeration of CNTs into bundles. The simulation results will serve as guidance in setting experimental processing conditions to optimize the mechanical properties of CNT composites.
Large-Scale Structure and Hyperuniformity of Amorphous Ices
NASA Astrophysics Data System (ADS)
Martelli, Fausto; Torquato, Salvatore; Giovambattista, Nicolas; Car, Roberto
2017-09-01
We investigate the large-scale structure of amorphous ices and transitions between their different forms by quantifying their large-scale density fluctuations. Specifically, we simulate the isothermal compression of low-density amorphous ice (LDA) and hexagonal ice to produce high-density amorphous ice (HDA). Both HDA and LDA are nearly hyperuniform; i.e., they are characterized by an anomalous suppression of large-scale density fluctuations. By contrast, in correspondence with the nonequilibrium phase transitions to HDA, the presence of structural heterogeneities strongly suppresses the hyperuniformity and the system becomes hyposurficial (devoid of "surface-area fluctuations"). Our investigation challenges the largely accepted "frozen-liquid" picture, which views glasses as structurally arrested liquids. Beyond implications for water, our findings enrich our understanding of pressure-induced structural transformations in glasses.
NASA Astrophysics Data System (ADS)
Li, Sijie; Ge, Peng; Zhang, Chenyang; Sun, Wei; Hou, Hongshuai; Ji, Xiaobo
2017-10-01
Na3V2(PO4)3 (NVP) is a very promising cathode material in sodium ion battery for rapidly emerging large-scale energy storage with its classical 3D NASCION structure. However, the cycling life and rate performances are restricted its low electronic conductivity. To overcome these, the double carbon-wrapped Na3V2(PO4)3 composite is firstly designed through rheological phase approach, delivering enhanced electrochemical properties. The unique double carbon layers are composed of uniform amorphous carbons as protecting framework for stabilizing the structure, as well as the graphitized carbon sheets playing the role of conductive network for better electronic conductivity. This double carbon-wrapped Na3V2(PO4)3 composite exhibits a high reversible capacity of 99.8 mAh g-1 over 500 cycles at 1 C (110 mA g-1), yielding the coulombic efficiency of ∼99.8%. Meanwhile, it displays an initial capacity of 73 mAh g-1 at 100 C and remains 55 mAh g-1 at an ultra-rate of 200 C. Even after cycling at 200 C over 12 000 cycles, the Na+-storage capacity of 40 mAh g-1 with a retention of 72.7% is still obtained, highlighting its excellent long cycling life and remarkable rate performances.
Small diameter carbon nanopipettes
NASA Astrophysics Data System (ADS)
Singhal, Riju; Bhattacharyya, Sayan; Orynbayeva, Zulfiya; Vitol, Elina; Friedman, Gary; Gogotsi, Yury
2010-01-01
Nanoscale multifunctional carbon probes facilitate cellular studies due to their small size, which makes it possible to interrogate organelles within living cells in a minimally invasive fashion. However, connecting nanotubes to macroscopic devices and constructing an integrated system for the purpose of fluid and electrical signal transfer is challenging, as is often the case with nanoscale components. We describe a non-catalytic chemical vapor deposition based method for batch fabrication of integrated multifunctional carbon nanopipettes (CNPs) with tip diameters much smaller (10-30 nm) than previously reported (200 nm and above) and approaching those observed for multiwalled carbon nanotubes. This eliminates the need for complicated attachment/assembly of nanotubes into nanofluidic devices. Variable tip geometries and structures were obtained by controlled deposition of carbon inside and outside quartz pipettes. We have shown that the capillary length and gas flow rate have a marked effect on the carbon deposition. This gives us a flexible protocol, useful for growing carbon layers of different thicknesses at selective locations on a glass pipette to yield a large variety of cellular probes in bulk quantities. The CNPs possess an open channel for fluid transfer with the carbon deposited inside at 875 °C behaving like an amorphous semiconductor. Vacuum annealing of the CNP tips at temperatures up to 2000 °C yields graphitic carbon structures with an increase in conductivity of two orders of magnitude. Penetration of the integrated carbon nanoprobes into cells was shown to produce minimal Ca2+ signals, fast recovery of basal Ca2+ levels and no adverse activation of the cellular metabolism during interrogation times as long as 0.5-1 h.
Small diameter carbon nanopipettes.
Singhal, Riju; Bhattacharyya, Sayan; Orynbayeva, Zulfiya; Vitol, Elina; Friedman, Gary; Gogotsi, Yury
2010-01-08
Nanoscale multifunctional carbon probes facilitate cellular studies due to their small size, which makes it possible to interrogate organelles within living cells in a minimally invasive fashion. However, connecting nanotubes to macroscopic devices and constructing an integrated system for the purpose of fluid and electrical signal transfer is challenging, as is often the case with nanoscale components. We describe a non-catalytic chemical vapor deposition based method for batch fabrication of integrated multifunctional carbon nanopipettes (CNPs) with tip diameters much smaller (10-30 nm) than previously reported (200 nm and above) and approaching those observed for multiwalled carbon nanotubes. This eliminates the need for complicated attachment/assembly of nanotubes into nanofluidic devices. Variable tip geometries and structures were obtained by controlled deposition of carbon inside and outside quartz pipettes. We have shown that the capillary length and gas flow rate have a marked effect on the carbon deposition. This gives us a flexible protocol, useful for growing carbon layers of different thicknesses at selective locations on a glass pipette to yield a large variety of cellular probes in bulk quantities. The CNPs possess an open channel for fluid transfer with the carbon deposited inside at 875 degrees C behaving like an amorphous semiconductor. Vacuum annealing of the CNP tips at temperatures up to 2000 degrees C yields graphitic carbon structures with an increase in conductivity of two orders of magnitude. Penetration of the integrated carbon nanoprobes into cells was shown to produce minimal Ca(2+) signals, fast recovery of basal Ca(2+) levels and no adverse activation of the cellular metabolism during interrogation times as long as 0.5-1 h.
Gas sorption in poly-(2,6-dimethyl-1,4-phenylene)oxide containing nanoporous crystalline phases
NASA Astrophysics Data System (ADS)
Galizia, M.; Daniel, C.; Fasano, G.; Guerra, G.; Mensitieri, G.
2012-07-01
In this contribution is presented an analysis of mass transport properties of low molecular weight compounds in amorphous PPO and in semi-crystalline PPO obtained by treating with benzene and carbon tetrachloride the amorphous sample. It is found that semi-crystalline samples are endowed with larger gas sorption capacity and diffusivity as compared to the amorphous ones: this behaviour has been attributed to the nanoporous nature of the crystalline phases induced by treatment with solvents. In particular, sorption experiments, carried out at 30°C with methane, carbon dioxide, propane and propylene, have shown that both semi-crystalline PPOs display rather interesting features which make them suitable for use as membrane materials in gas separation processes, in view of the relatively high values of solubility and diffusivity. Moreover, these peculiar sorption and mass transport properties have been found to be virtually unaffected by thermal ageing: in fact, sorption experiments conducted on amorphous and semi-crystalline PPO after treatment at 65°C for three months showed that sorption properties of aged samples are the same as for the untreated samples. This is an important feature to assure the stability of performances in membrane applications.
Preparation and uses of amorphous boron carbide coated substrates
Riley, Robert E.; Newkirk, Lawrence R.; Valencia, Flavio A.
1981-09-01
Cloth is coated at a temperature below about 1000.degree. C. with amorphous boron-carbon deposits in a process which provides a substantially uniform coating on all the filaments making up each yarn fiber bundle of the cloth. The coated cloths can be used in the as-deposited condition for example as wear surfaces where high hardness values are needed; or multiple layers of coated cloths can be hot-pressed to form billets useful for example in fusion reactor wall armor. Also provided is a method of controlling the atom ratio of B:C of boron-carbon deposits onto any of a variety of substrates, including cloths.
Preparation and uses of amorphous boron carbide coated substrates
Riley, R.E.; Newkirk, L.R.; Valencia, F.A.; Wallace, T.C.
1979-12-05
Cloth is coated at a temperature below about 1000/sup 0/C with amorphous boron-carbon deposits in a process which provides a substantially uniform coating on all the filaments making up each yarn fiber bundle of the cloth. The coated cloths can be used in the as-deposited condition for example as wear surfaces where high hardness values are needed; or multiple layers of coated cloths can be hot-pressed to form billets useful for example in fusion reactor wall armor. Also provided is a method of controlling the atom ratio of B:C of boron-carbon deposits onto any of a variety of substrates, including cloths.
Wolf, Stephan E.; Müller, Lars; Barrea, Raul; Kampf, Christopher J.; Leiterer, Jork; Panne, Ulrich; Hoffmann, Thorsten
2011-01-01
During the mineralisation of metal carbonates MCO3 (M = Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed. PMID:21218241
Neon ion beam induced pattern formation on amorphous carbon surfaces
NASA Astrophysics Data System (ADS)
Bobes, Omar; Hofsäss, Hans; Zhang, Kun
2018-02-01
We investigate the ripple pattern formation on amorphous carbon surfaces at room temperature during low energy Ne ion irradiation as a function of the ion incidence angle. Monte Carlo simulations of the curvature coefficients applied to the Bradley-Harper and Cater-Vishnyakov models, including the recent extensions by Harrison-Bradley and Hofsäss predict that pattern formation on amorphous carbon thin films should be possible for low energy Ne ions from 250 eV up to 1500 eV. Moreover, simulations are able to explain the absence of pattern formation in certain cases. Our experimental results are compared with prediction using current linear theoretical models and applying the crater function formalism, as well as Monte Carlo simulations to calculate curvature coefficients using the SDTrimSP program. Calculations indicate that no patterns should be generated up to 45° incidence angle if the dynamic behavior of the thickness of the ion irradiated layer introduced by Hofsäss is taken into account, while pattern formation most pronounced from 50° for ion energy between 250 eV and 1500 eV, which are in good agreement with our experimental data.
The nature of cometary dust as determined from infrared observations
NASA Technical Reports Server (NTRS)
Swamy, K. S. Krishna; Sandford, Scott A.; Allamandola, Louis J.; Witteborn, Fred C.; Bregman, Jesse D.
1989-01-01
The infrared measurements of comets, the compositional information available from interplanetary dust particles (IDPs), and the recent results of flybys to Comet Halley can help in restricting the nature and composition of cometary dust models (c.f., Proceedings of the 20th ESLAB Symposium on Exploration of Halley's Comet, 1986). Researchers tried to incorporate some of these results into a coherent model to account for the observed cometary infrared emission. The presence of 10 and 3.4 micron features in Comet Halley (c.f. Bregman et al. 1987; Wickramasinghe and Allen 1986) indicated the presence of at least two components in the grain material, namely silicates and some form of amorphous carbon. These two components could reside in separate grains or may be parts of composite particles. Both these cases have been considered (see Krishna Swamy el a. 1988a, 1988b). In the absence of refractive index data for cometary analogs, the authors used the optical constants of olivine-rich lunar material 12009.48 (Perry et al. 1972) for the infrared region and that of alpha:C-H film for amorphous carbon (angus et al. 1986). For the visible region, a value of m = 1.38-0.39i was used for the silicates, and values published by Arakawa et al. (1985) were used for the amorphous carbon. These materials should give a representative behavior of the expected results. The model results were compared to observational data. The strength of the 3.4 micron and 10 micron features relative to the adjacent continuum, as well as the slope of the continuum between 2500 and 1250 cm(exp -1) (4 to 8 microns), were used as criteria for comparison. Model calculations with alpha approx. equals -3.5, and also the size distribution function inferred for Comet Halley, with a mass fraction (X) of silicate to amorphous carbon grains of about 40 to 1 can fit the data. A good match is obtained for the infrared spectra of Comets Halley and West from a 40 to 1 mixture of silicate and amorphous carbon grains with a a(exp -3.5) size distribution function. The results are consistent with compositional constraints provided by interplanetary dust particles (IPDs) and Halley flyby data. The variation of grain temperature with heliocentric distance appears to account for the major changes observed in cometary spectra.
NASA Astrophysics Data System (ADS)
Duley, W. W.
1995-05-01
A formalism based on the theory of random covalent networks (RCNs) in amorphous solids is developed for carbonaceous dust grains. RCN solutions provide optimized structures and relative compositions for amorphous materials. By inclusion of aliphatic, aromatic, and diamond clusters, solutions specific to interstellar materials can be obtained and compared with infrared spectral data. It is found that distinct RCN solutions corresponding to diffuse cloud and molecular cloud materials are possible. Specific solutions are derived for three representative objects: VI Cyg No. 12, NGC 7538 (IRS 9), and GC IRS 7. While diffuse cloud conditions with a preponderance of sp2 and sp3 bonded aliphatic CH species can be reproduced under a variety of RCN conditions, the presence of an abundant tertiary CH or diamond component is highly constrained. These solutions are related quantitatively to carbon depletions and can be used to provide a quantitative estimate of carbon in these various dust components. Despite the abundance of C6 aromatic rings in many RCN solutions, the infrared absorption due to the aromatic stretch at approximately 3.3 micrometers is weak under all conditions. The RCN formalism is shown to provide a useful method for tracing the evolutionary properties of interstellar carbonaceous grains.
NASA Astrophysics Data System (ADS)
Dai, Hongyu; Li, Lee; Peng, Ming-yang; Xiong, Jiaming; Wu, Haibo; Yu, Bin
2017-12-01
In order to reduce the effect of residual carbon on the insulation performance, after the GW-hundreds kiloampere graphite-electrode switch turning on, the chemical kinetics of the carbon-oxygen reaction is analyzed. The capacitive pulsed experimental circuit is used to reconstruct the actual condition of high power and high current discharge. The carbon-oxygen reaction efficiency is analyzed using a Fourier transform infrared spectrometer and a flue gas analyzer. The research shows that the gas products include NOX, O3, CH4, and COX. Through the quantitative analysis, the conversion efficiency of COX increases with the augment of the accumulated transferred charge, and the change law of the CO generation efficiency has an extreme value. With the corresponding calculation and the observation of the scanning electron microscope, it is found that most of the carbon consumed from the graphite electrodes is converted to amorphous elemental carbon, and the insufficiency of the carbon-oxygen reaction leads to the problem of carbon residue, for 20%-45% of elemental carbon is not oxidized. The size of amorphous elemental carbon is about several micrometers to tens micrometers by the analysis of metallographic microscope. In the condition of compressed air, changing the amount of transferred charge is helpful to improve the carbon-oxygen reaction efficiency and inhibit the problem of carbon residue.
NASA Astrophysics Data System (ADS)
Hadamcik, E.; Renard, J.-B.; Lasue, J.; Levasseur-Regourd, A. C.
2007-08-01
1- Introduction Cometary and possibly interplanetary dust particles seem to be mainly made of agglomerates of submicron and micron-sized grains. These particles are among the most primitive in our solar system. Regoliths on asteroidal and planetary surfaces seem to be loose materials produced by impinging meteorites on the surface of small bodies. Comparing their physical properties is thus fundamental to understand their evolution. To interpret remote observations of solar light scattered by dust particles and regoliths, it is necessary to use numerical and experimental simulations [1,2,3]. 2- PROGRA2 experiment PROGRA2 instruments are polarimeters; the light sources are two randomly polarized lasers (632.8 nm and 543.5 nm). Levitating particles (in microgravity or lifted by an air-draught) are studied by imaging polarimetry. Details on the instruments can be found in [4,5]. 3- Samples Two kinds of samples are studied: compact particles in the (1-400) micrometer size range and fluffy aggregates in the same size range, made from submicron and micronsized grains. The materials are transparent silica and absorbing carbon. Some deposited particles are huge agglomerates of micron-sized grains produced by random ballistic deposition of single grains [6,7] or produced by evaporation of mixtures in alcohol of fluffy aggregates of submicron-sized grains. Two samples are made of silica spheres coated by a carbonaceous black compound. Cometary analogues are mixtures of silica and amorphous carbon or Mg-Fe silicates mixed with amorphous carbon. 4- Results Phase curves and their main parameters (negative polarization at small phase angles and maximum polarization, Pmax, at 90-100° phase angle) for the different materials will be compared and related to the physical properties. For example, it is well known by numerical simulations and/or by experiments that the maximum polarization decreases when the size (submicrometer range) of the grains increases [2,8,9]. An inverse rule is found for compact grains, larger than the wavelength. Mixtures of fluffy silica and fined grained amorphous carbon or better Mg-Fe silicates with amorphous carbon are excellent cometary particles analogues (as light scattering is concerned) if they are mixed with some compact micron-sized grains [9]. Nevertheless the structure of the aggregates seems to play a major role to obtain the negative branch found on the polarimetric phase curves for comets [10]. 5- Discussion and conclusions The experiments purpose is to help to disentangle the different physical properties of dust particles that can be deduced from remote observations (cometary dust, regoliths). Differences between the main parameters influencing the variations of Pmax and the presence of a negative branch on the polarimetric phase curves for lifted and deposited particles (in huge agglomerates or not) will be discussed. Acknowledgments: Technische Universität Carolo-Wilhelmina, Braunschweig, Deutschland (Pr Blum, Dr Schräpler); University of New Mexico, Albuquerque, USA (Pr Rietmeijer); NASA Goddard Space Flight Center, Maryland, USA (Dr Nuth) References [1] A.C. Levasseur-Regourd, E. Hadamcik, JQSRT 79-80, 903 (2003) [2] J. Lasue, A.C. Levasseur-Regourd, JQSRT 100, 220 (2006) [3] J.-B. Renard et al., ASR 31, 2511 (2003) [4] J.-B. Renard et al., Appl. Opt. 91, 609 (2002) [5] E. Hadamcik et al., JQSRT 106, 74 (2007) [6] J. Blum, R. Schreapler, Phys. Rev Let 93:115031 (2004) [7] J. Blum et al., Astrophys J 652, 1768 (2006) [8] R. West, Appl. Opt. 30, 5216 (1991) [9] E. Hadamcik et al., JQSRT 100, 143 (2006) [10] E. Hadamcik et al., Icarus, in press (2007)
Advanced Survivable Radiator Development Program
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